JP2012118466A - Production method of toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner having a wide fixable range from a low temperature region to a high temperature region and high heat-resistant storage property of the toner and giving high-quality images.SOLUTION: A production method of toner comprising a dissolution suspension method is provided, including a step of heat treating a toner material at a heating temperature t (°C) satisfying Tp'-15.0≤t≤Tp'-5.0 for 0.5 hour or longer after an organic solvent is removed. A binder resin included in the toner contains a block polymer having a crystalline structure as a main component. The proportion of moieties capable of forming a crystalline structure in the binder resin is 50 mass% or more and 85 mass% or less. In an endothermic quantity measurement by differential scanning calorimetry (DSC) of the toner, a peak temperature Tp of the maximum endothermic peak derived from the binder resin is 50°C or higher and 80°C or lower.

Description

  The present invention relates to a toner manufacturing method used in a recording method using an electrophotographic method, an electrostatic recording method, and a toner jet recording method. Specifically, after forming a toner image on an electrostatic latent image carrier, it is transferred onto a transfer material to form a toner image, and fixed under a thermal pressure to obtain a fixed image. It relates to a manufacturing method.

  In recent years, energy saving has been considered as a major technical issue, and the amount of heat applied to a fixing device in an electrophotographic apparatus has been greatly reduced. Therefore, there is an increasing need for low-temperature fixability in which toner can provide sufficient fixing performance with a lower heat quantity.

  Conventionally, in order to enable fixing at a low temperature, a technique of making the binder resin more sharp melt is known as one of the effective methods. Crystalline materials are not considered to exhibit a clear glass transition due to the regular arrangement of molecular chains, and are difficult to soften to the crystalline melting point. It has been broken.

  When crystalline polyester is used as the binder resin for the toner as the crystalline material, sharp melt properties can be imparted to the toner. On the other hand, when crystalline polyester is used alone as the binder resin for the toner, the elasticity of the toner on the high temperature side is lost, and the glossiness decreases due to hot offset and soaking into the paper. The width becomes narrower. Therefore, in continuous image formation with a printer, offset and gloss unevenness are likely to occur, and a stable image cannot be obtained.

  Patent Document 1 proposes a pulverized toner using a mixture of a crystalline polyester and an amorphous polyester as a binder resin. Although the amorphous polyester is introduced to ensure the elasticity on the high temperature side, the crystalline polyester has the spreadability, so that the crystalline polyester as the binder resin is deposited alone on the toner surface. For this reason, there are problems such as suppression of member contamination in the developing device and improvement of heat-resistant storage.

  Therefore, a toner production method using a block polymer in which a crystalline part and an amorphous part are bonded has been proposed.

  Patent Document 2 shows that an emulsion aggregation method toner using a block polymer having a crystalline polyester block and an amorphous polyester block as a binder resin, and can be pressure-fixed by low-temperature heating due to improved plasticity. Has been.

  However, the content of the crystalline polyester block in the binder resin is small, and the sharp melt property for achieving low-temperature fixability is not sufficiently ensured.

  Patent Document 3 proposes a solution suspension method toner using a block polymer in which a polyester resin, a polyurethane resin, a polyurea resin, a polyamide resin, and a polyether resin are used for a crystalline part and an amorphous part as a binder resin. Has been.

  For block polymers, control the viscoelastic behavior in the temperature range before and after the endothermic peak temperature Ta derived from the block polymer and the melting start temperature X in the descending flow tester by differential scanning calorimetry (DSC) heat of fusion measurement. Has proposed. Thereby, the heat resistant storage stability and the hot offset resistance are improved.

  However, since the heating is performed at a temperature equal to or higher than the melting point of the crystalline part in the step of dissolving the toner material in the solvent, the crystal structure in the block polymer is partially broken. For this reason, the sharp melt property of the toner is not sufficiently exhibited, and the low-temperature fixability is hindered. Further, when the crystal structure of the toner is broken, the heat resistant storage stability is likely to be lowered.

  As a method for improving the crystallinity of a crystalline material, Patent Document 4 discloses an emulsion aggregation method toner containing a crystalline polyester, and improves the crystallinity of the crystalline polyester through a temporary heating step of aggregation. It is stated that it will be possible to However, the crystalline polyester that can be introduced has a high softening point, and the temperature difference from the treatment temperature in the heating step becomes large. For this reason, in order to sufficiently improve the crystallinity of the crystalline polyester, it is necessary to control the temperature difference between the softening point at which the resin motion is activated and the processing temperature of the heating process, thereby realizing further low-temperature fixing. Not suitable for.

  Therefore, in order to further improve the sharp melt property of the block polymer containing crystalline polyester as the main component, the crystallinity of the portion that can take the crystal structure in the block polymer is improved, and the low-temperature fixability and heat-resistant storage stability are improved. There is a demand for a toner production method that achieves both of these requirements.

Japanese Patent No. 4270557 JP 2007-114635 A International Publication No. 2009-122687 Japanese Patent No. 4439005

  An object of the present invention is to provide a method for producing a toner having a wide fixable temperature range. Furthermore, the present invention provides a toner production method that has high heat-resistant storage stability, lightly contaminated members, and can obtain a high-quality image.

A process of forming oil droplets by emulsifying and / or dispersing a toner material in which a binder resin mainly composed of a block polymer having a crystal structure, a colorant and a wax are dissolved and / or dispersed in an organic solvent in an aqueous medium. And the step of removing the organic solvent from the oil droplets, and after removing the organic solvent, the following formula (1)
Tp′-15.0 ≦ t ≦ Tp′−5.0 (1)
(Tp ′ represents the peak temperature of the maximum endothermic peak of the block polymer in the endothermic measurement by DSC.)
A heat treatment for 0.5 hours or more at a heating temperature t (° C.) that satisfies
The binder resin contains polyester as a main component,
The ratio of the part that can take the crystal structure in the binder resin is 50% by mass or more and 85% by mass or less,
The present invention relates to a method for producing a toner, wherein a peak temperature Tp of a maximum endothermic peak derived from a binder resin is 50 ° C. or higher and 80 ° C. or lower in the measurement of the endothermic amount using a differential scanning calorimeter (DSC).

  According to the present invention, toner particles having a wide fixable temperature range can be obtained. Furthermore, according to the present invention, it is possible to obtain toner particles that have high heat-resistant storage stability, lightly contaminated members, and a high-quality image.

  The method for producing a toner of the present invention comprises an oil material prepared by emulsifying and / or dispersing a toner material in which an organic solvent is dissolved and / or dispersed at least in a binder resin mainly composed of polyester, a colorant, and a wax. In this manufacturing method, after forming the droplets, the organic solvent is removed to obtain a toner.

  In the production method of the present invention, at least a binder resin, a colorant and a wax are used, but other additives may be included as necessary. The binder resin contains polyester as a main component. Here, “main component” means occupying 50% by mass or more with respect to the total amount of the binder resin. The binder resin containing polyester as a main component contains a portion that can take a large amount of crystal structure, and the portion that can take a crystal structure is made of crystalline polyester.

  The binder resin mainly composed of polyester in the production method of the present invention is composed mainly of a block polymer having a crystal structure. The block polymer is preferably a block polymer in which a portion that can take a crystal structure and a portion that does not take a crystal structure are chemically bonded.

  The block polymer is a polymer in which polymers are linked by a covalent bond within one molecule. Here, the part which can take a crystal structure is a part which arranges regularly and expresses crystallinity when a large number of itself is assembled, and means a crystalline polymer chain. Here, it is a crystalline polyester chain.

  Moreover, the site | part which cannot take the said crystal structure is a site | part which does not arrange regularly even if it collects itself but takes a random structure, and means an amorphous polymer.

  The block polymer is an AB-type diblock polymer, an ABA-type triblock polymer, an BAB-type triblock polymer, an ABAB type, which is a portion that can take a crystal structure, and is a crystalline polyester (A) and an amorphous polymer (B). -A type multi-block polymer is mentioned, and the above effects can be exhibited in any form.

  In the block polymer, examples of the bonding form in which a portion that can take a crystal structure and a portion that cannot take a crystal structure are connected by a covalent bond include an ester bond, a urea bond, and a urethane bond. Among these, a block polymer in which a portion that can have crystallinity and a portion that cannot take a crystal structure are bonded by a urethane bond is more preferable. By being a block polymer bonded with a urethane bond, elasticity is easily maintained even in a high temperature range of the fixing process.

  In the toner of the present invention, as the binder resin, a binder resin having a ratio of a portion capable of forming a crystal structure of 50% by mass to 85% by mass is used.

  When the portion where the binder resin can take a crystal structure is less than 50% by mass with respect to the binder resin, the sharp melt property due to the crystallinity becomes difficult to be expressed effectively, and the Tg of the amorphous portion is reduced. It becomes easy to be affected. Further, the crystalline domain in the toner becomes too small, and the sharp melt property is hardly exhibited, which is not preferable. By being in this range, sharp melt properties accompanying crystallinity are effectively expressed, and sufficient fixing in a low temperature range is possible. A more preferable range of the portion capable of taking a crystal structure with respect to the binder resin is 60% by mass or more and 80% by mass or less.

  Note that the binder resin may be formed of a block polymer alone or may be mixed with other resins. Preferably, the ratio of the block polymer in the binder resin is 70% by mass or more, and more preferably 85% by mass or more. In addition, when using crystalline resin as other resin used together, resin used together is also contained as a site | part which can take a crystal structure.

  In the present invention, the acid value of the block polymer is preferably 3.0 mgKOH / g or more and 30.0 mgKOH / g or less, more preferably 5.0 mgKOH / g or more and 20.0 mgKOH / g or less. By giving the acid value, the presence of droplets during granulation in an aqueous medium is stabilized, and a more uniform particle size distribution can be obtained.

  In the present invention, in order to adjust the acid value of the block polymer, polycarboxylic acids, polyhydric alcohols, polyisocyanates, polyfunctionals with respect to the terminal isocyanate group, hydroxyl group and carboxyl group of the block polymer. The terminal of the block polymer can be modified using epoxies, polyanhydrides, polyvalent amines, and the like.

  The block polymer preferably contains 45% by mass or more and 90% by mass or less, and more preferably 50% by mass or more and 85% by mass or less, of a portion capable of taking a crystal structure. Within this range, it is preferable in terms of achieving both low-temperature fixability and heat-resistant storage stability.

  The toner in the production method of the present invention preferably has an endothermic peak temperature (Tp ′) of 50 to 80 ° C. of the block polymer determined from an endothermic measurement with a differential scanning calorimeter (DSC). If the peak temperature is less than 50 ° C., the toner is affected by the temperature increase during operation in the printer. As a result, toner adheres to the developer carrying member or the like. On the other hand, when the peak temperature exceeds 80 ° C., the sharp melt property of the toner is impaired, and fixing in a low temperature range becomes difficult.

  Further, the peak temperature (Tp) of the endothermic peak derived from the binder resin, which is obtained from the measurement of the endothermic amount with a differential scanning calorimeter (DSC) of the toner particles, is preferably 50 ° C. or higher and 80 ° C. or lower. The fact that the peak temperature of the endothermic peak of the binder resin in the toner is within the above range means that the resin in the toner is present in a state exhibiting crystallinity. Further, the total endothermic amount (ΔH) of the endothermic peak derived from the binder resin is preferably 30 J / g or more and 80 J / g or less per 1 g of the binder resin. ΔH reflects the ratio of the portion of the binder resin that can have a crystal structure that exists in a state where the crystallinity in the toner is maintained. Even when the toner particles contain a large amount of sites capable of forming a crystal structure, ΔH is small when the crystallinity is impaired.

  When ΔH is within the above range, uniform melting of the toner proceeds and better fixing becomes possible. Further, the amount of heat necessary for fixing is suitably suppressed.

  When a component having a crystal structure is used as a toner material, if there is a process in the manufacturing process that dissolves in an organic solvent together with other materials or gives a thermal history higher than the melting point, the crystal structure is maintained while maintaining the crystallinity. It is difficult to incorporate a component having a toner in the toner.

  This is because the crystallinity of the portion where the crystal structure can be taken is lowered, and it is necessary to control the crystallinity after obtaining the particles. Specifically, the heat treatment is performed at a temperature lower than the melting point of the crystalline component. Hereinafter, this heat treatment is referred to as “annealing treatment”. By providing the annealing treatment step, it is possible to improve the degree of crystallinity of a portion that can take a crystal structure in the toner particles. The annealing process is set after the organic solvent is removed from the obtained oil droplets.

  In general, it is known that the crystalline material has higher crystallinity at a portion where a crystalline structure can be obtained by further performing an annealing process. The principle is considered as follows. During the annealing process, the molecular mobility of the polymer chain of the crystalline component is increased to some extent, so that recrystallization occurs when the molecular chain reorients to a stable structure, that is, a regular crystal structure. That's it. At temperatures above the melting point, recrystallization does not occur because the molecular chain has more energy than the crystalline structure.

  Therefore, it is important that the annealing treatment in the present invention is performed within a limited temperature range with respect to the melting point of the crystalline component in order to activate the molecular motion of the crystalline polyester component in the toner as much as possible. .

  Therefore, as the annealing temperature, in order to make molecular motion as active as possible, the melting point of the crystalline component represented by the peak temperature of the maximum endothermic peak of the block polymer is 5.0 ° C. or higher and 15.0 ° C. or lower. Must be at a low temperature.

That is, when the peak temperature Tp ′ of the maximum endothermic peak of the block polymer is used, it is necessary to perform the heat treatment step at a heating temperature t (° C.) that satisfies the following formula (1).
Tp′-15.0 ≦ t ≦ Tp′−5.0 (1)
Furthermore, the temperature satisfying the following formula (2) is more preferable than the melting point.
Tp′−11.0 ≦ t ≦ Tp′−6.0 (2)
And the time (heating time) of an annealing process needs to be 0.5 hour or more. When the time of the heat treatment step is less than 0.5 hour, recrystallization of a portion that can take a crystal structure in the toner becomes insufficient. The annealing treatment time is more preferably in the range of 1.0 hours to 50.0 hours, and still more preferably in the range of 5.0 hours to 24.0 hours.

  The heat treatment step (annealing step) may be performed at any stage after the particles are formed. For example, the particles in a slurry state may be treated, and externally added to the toner base particles. It may be performed before the external addition step of adding the agent, or may be performed after the external addition step.

  The annealing process can be a dry process or a wet process. The dissolution suspension method is a method for producing a toner obtained by emulsifying and / or dispersing in an aqueous medium to form oil droplets and then removing the organic solvent. For this reason, it is possible to continuously perform wet annealing in an aqueous medium after the toner is produced, leading to a reduction in time required for the production of the toner.

  In the heat-treated toner, the full width at half maximum of the maximum endothermic peak derived from the binder resin in the DSC endotherm measurement is preferably 5.0 ° C. or less. If it is 5.0 degrees C or less, the recrystallization of the site | part which can take the crystal structure in binder resin will be performed favorably.

  Hereinafter, the crystalline polyester part, which is a part capable of taking a crystal structure in the block polymer, will be described.

  The crystalline polyester part preferably uses an aliphatic diol having 4 to 20 carbon atoms and a polyvalent carboxylic acid as at least raw materials. Furthermore, the aliphatic diol is preferably linear. It becomes easy to improve crystallinity by being a linear type.

  Examples of the aliphatic diol that can be used in the present invention include, but are not limited to, the following. Depending on the case, it is also possible to use a mixture. 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1 , 11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,18-octadecanediol, 1,20-eicosanediol. Among these, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol are more preferable from the viewpoint of the melting point.

  An aliphatic diol having a double bond can also be used. Examples of the aliphatic diol having a double bond include the following. 2-butene-1,4-diol, 3-hexene-1,6-diol, 4-octene-1,8-diol.

  Next, the acid component used for the preparation of the crystalline polyester will be described. The acid component used for the preparation of the crystalline polyester is preferably a polyvalent carboxylic acid. As the polyvalent carboxylic acid, an aromatic dicarboxylic acid and an aliphatic dicarboxylic acid are preferable. Among them, an aliphatic dicarboxylic acid is preferable, and a linear aliphatic dicarboxylic acid is particularly preferable from the viewpoint of crystallinity.

  Examples of the aliphatic dicarboxylic acid include, but are not limited to, the following. Depending on the case, it is also possible to use a mixture. Succinic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid, 1,11-undecanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, 1,13-tridecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 1,16-hexadecanedicarboxylic acid, 1,18-octadecanedicarboxylic acid. Or its lower alkyl ester and acid anhydride. Of these, sebacic acid, adipic acid, 1,10-decanedicarboxylic acid or its lower alkyl ester and acid anhydride are preferred.

  Examples of the aromatic dicarboxylic acid include the following. Terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid. Of these, terephthalic acid is preferred because it is readily available and can easily form a low-melting polymer.

  A dicarboxylic acid having a double bond can also be used. A dicarboxylic acid having a double bond can be suitably used in order to prevent hot offset at the time of fixing, because the entire resin can be crosslinked using the double bond.

  Examples of such dicarboxylic acids include, but are not limited to, fumaric acid, maleic acid, 3-hexenedioic acid, and 3-octenedioic acid. Moreover, these lower alkyl esters and acid anhydrides are also included. Among these, fumaric acid and maleic acid are preferable in terms of cost.

  The method for producing the crystalline polyester part is not particularly limited, and can be produced by a general polyester polymerization method in which an acid component and an alcohol component are reacted. For example, direct polycondensation or transesterification can be performed using a monomer. Produced separately for different types.

  The production of the crystalline polyester part is preferably carried out at a polymerization temperature of 180 ° C. or higher and 230 ° C. or lower, and the reaction system is reacted under reduced pressure as necessary to remove water and alcohol generated during condensation. Is preferred. When the monomer is not dissolved or compatible at the reaction temperature, a solvent having a high boiling point is preferably added as a solubilizer and dissolved. In the polycondensation reaction, the dissolution auxiliary solvent is distilled off. In the case where a monomer having poor compatibility exists in the copolymerization reaction, it is preferable to condense the monomer having poor compatibility with the monomer and the acid or alcohol to be polycondensed in advance and then polycondense together with the main component.

  Examples of the catalyst that can be used in the production of the crystalline polyester include the following. Titanium catalyst of titanium tetraethoxide, titanium tetrapropoxide, titanium tetraisopropoxide, titanium tetrabutoxide. Tin catalyst of dibutyltin dichloride, dibutyltin oxide, diphenyltin oxide.

  The crystalline polyester is preferably alcohol-terminated to prepare the block polymer. Therefore, in the preparation of the crystalline polyester, the molar ratio of the acid component to the alcohol component (alcohol component / carboxylic acid component) is preferably 1.02 or more and 1.20 or less.

  In the present invention, it is possible to maintain the elasticity after the crystalline part is sharp-melted by including the amorphous part within a range not affecting the low-temperature fixability as the binder resin.

  The portion where the crystal structure cannot be taken is not particularly limited as long as it is amorphous, and an amorphous binder resin for toner can be used as it is. However, the Tg of the amorphous material is preferably 50 ° C. or higher and 130 ° C. or lower. More preferably, it is 70 degreeC or more and 130 degrees C or less. By being in this range, the elasticity in the fixing region is easily maintained.

  Examples of the site that cannot take the crystal structure include, but are not limited to, polyurethane resin, polyester resin, styrene acrylic resin, polystyrene, and styrene butadiene resin. These resins may be modified with urethane, urea, or epoxy. Of these, polyester resins and polyurethane resins are preferably used from the viewpoint of maintaining elasticity.

  Examples of the monomer used in the polyester resin as a site that cannot take the crystal structure include conventionally known divalent or trivalent or higher carboxylic acids and divalent or trivalent or higher alcohols. Specific examples of these monomer components include the following. Examples of divalent carboxylic acids include succinic acid, adipic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, malonic acid, dodecenyl succinic acid dibasic acid, anhydrides thereof and lower alkyl esters thereof, maleic acid, Aliphatic unsaturated dicarboxylic acids of fumaric acid, itaconic acid and citraconic acid. Examples of trivalent or higher carboxylic acids include 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, anhydrides thereof, and lower alkyl esters thereof. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the dihydric alcohol include the following. Bisphenol A, hydrogenated bisphenol A, ethylene oxide oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, ethylene glycol, propylene glycol. Examples of trihydric or higher alcohols include the following. Glycerin, trimethylol ethane, trimethylol propane, pentaerythritol. These may be used individually by 1 type and may use 2 or more types together. If necessary, monovalent acids such as acetic acid and benzoic acid, and monovalent alcohols such as cyclohexanol and benzyl alcohol can be used for the purpose of adjusting the acid value and the hydroxyl value.

  The said polyester resin can be synthesize | combined using a general method by arbitrary combinations from the said monomer component, and can use the transesterification method and the direct polycondensation method individually or in combination.

  The polyurethane resin as a site where the crystal structure cannot be taken will be described. The polyurethane resin is a reaction product of a diol and a substance containing a diisocyanate group, and the functionality of the resulting resin can be changed by changing the diol or diisocyanate.

  Examples of the diisocyanate component include the following.

  C6-C20 aromatic diisocyanate, C2-C18 aliphatic diisocyanate, C4-C15 alicyclic diisocyanate, C8 or more (except for carbon in the NCO group) 15 or less aromatic hydrocarbon diisocyanates and modified products of these diisocyanates (urethane group, carbodiimide group, allophanate group, urea group, burette group, uretdione group, uretoimine group, isocyanurate group, oxazolidone group-containing modified product) , Also called modified diisocyanate), and mixtures of two or more thereof.

  Examples of the aliphatic diisocyanate include the following. Ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate.

  Examples of the alicyclic diisocyanate include the following. Isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4'-diisocyanate, cyclohexylene diisocyanate, methylcyclohexylene diisocyanate.

  Examples of the aromatic hydrocarbon diisocyanate include the following. m- and / or p-xylylene diisocyanate (XDI), α, α, α ', α'-tetramethylxylylene diisocyanate.

  Among these, preferred are aromatic diisocyanates having 6 to 15 carbon atoms, aliphatic diisocyanates having 4 to 12 carbon atoms, alicyclic diisocyanates having 4 to 15 carbon atoms, and araliphatic diisocyanates, which are particularly preferred. Are HDI, IPDI, and XDI. Moreover, in addition to the above-mentioned diisocyanate component, the said polyurethane resin can also use a trifunctional or more than trifunctional isocyanate compound.

  Moreover, the following are mentioned as a diol component which can be used for the said urethane resin.

  Alkylene glycol (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol); alkylene ether glycol (polyethylene glycol, polypropylene glycol); alicyclic diol (1,4-cyclohexanedimethanol); bisphenols (bisphenol) A); alkylene oxide (ethylene oxide, propylene oxide) adduct of the alicyclic diol. The alkyl part of the alkylene ether glycol may be linear or branched. In the present invention, an alkylene glycol having a branched structure can also be preferably used.

  As a method for preparing the block polymer, a method (two-stage method) in which a unit for forming a crystal part and a unit for forming an amorphous part are separately prepared and both are combined can be used. Further, a method (one-step method) in which raw materials of a unit for forming a crystal part and a unit for forming an amorphous part are simultaneously charged and prepared at a time can be used.

  The block polymer in the present invention can be synthesized by selecting from various methods in consideration of the reactivity of each terminal functional group.

  In the case of a block polymer in which both the crystal part and the amorphous part are polyester resins, each unit can be prepared separately and then bonded using a binder. In particular, when the acid value of one polyester is high and the hydroxyl value of the other polyester is high, it is not necessary to use a binder, and the condensation reaction can proceed while heating and reducing pressure as it is. At this time, the reaction temperature is preferably about 200 ° C.

  When the binder is used, the following binders are exemplified. Polyvalent carboxylic acid, polyhydric alcohol, polyvalent isocyanate, polyfunctional epoxy, polyhydric acid anhydride. These binders can be used for synthesis by dehydration reaction or addition reaction.

  In the case of a block polymer in which the crystal part is a polyester resin and the amorphous part is a polyurethane resin, after each unit is prepared separately, the alcohol terminal of the crystalline polyester and the isocyanate terminal of the polyurethane are urethanated. Can be prepared. The synthesis can also be performed by mixing a crystalline polyester having an alcohol terminal and a diol and diisocyanate constituting polyurethane and heating. In this case, at the initial stage of the reaction when the concentrations of the diol and the diisocyanate are high, these selectively react to form a polyurethane, and after the molecular weight increases to some extent, the urethane between the isocyanate end of the polyurethane and the alcohol end of the crystalline polyester. Happens.

  The block polymer is obtained by reacting an isocyanate-modified polyester, which is a site that cannot take a crystal structure, with an isocyanate-modified polyester, which is a site that can take a crystal structure, by reacting a polyvalent amine (crosslinking agent) with a urea bond. A block polymer may be used.

  The isocyanate-modified polyester component that is a part capable of taking a crystal structure is preferably 50 to 80% by mass, more preferably 60 to 80% by mass with respect to the binder resin.

  The toner particles obtained by the production method of the present invention are preferably toners having a core / shell structure having a surface layer on the surface of the core particles. The surface layer may be formed at the same time as the core particle forming step or after the core particles are formed. From the viewpoint of simplicity, it is preferable to simultaneously perform the core particle manufacturing step and the surface layer forming step. The heat treatment is performed after the surface layer is formed.

  Further, the step of forming the surface layer is not limited at all. For example, when the surface layer is provided after the formation of the core particles, the core particles and the resin fine particles are dispersed in an aqueous medium, and then the surface of the core particles is formed. There is a method of agglomerating and adsorbing resin fine particles. The resin forming the surface layer is preferably 2.0 parts by mass or more and 20.0 parts by mass or less, more preferably 3.0 parts by mass with respect to 100 parts by mass of the binder resin (resin contained in the core particles). It is preferable to be used at 13.0 parts by mass.

  In the present invention, toner particles having a core-shell structure can be prepared in one stage, and a spherical toner having a small particle size and a sharp particle size distribution can be easily obtained. The turbidity method is preferred.

  As another method for forming a surface layer on individual toner particles, reactive monomers are mixed in the core particles and in the aqueous medium, respectively, and a reaction is caused at the interface between the toner and the aqueous medium. A so-called interfacial polymerization method for forming a surface layer is also possible.

  Examples of the solvent that can be used as an organic medium for dissolving the binder resin in the production method of the present invention include hydrocarbon solvents such as ethyl acetate, xylene, and hexane, halogenated hydrocarbon solvents such as methylene chloride, chloroform, and dichloroethane. Examples thereof include ester solvents such as methyl acetate, ethyl acetate, butyl acetate and isopropyl acetate, ether solvents such as diethyl ether, and ketone solvents such as acetone, methyl ethyl ketone, diisobutyl ketone, cyclohexanone and methylcyclohexane.

  As an aqueous medium used in the present invention, water alone may be used, but a solvent miscible with water may be used in combination. Examples of miscible solvents include alcohol (methanol, isopropanol, ethylene glycol), dimethylformamide, tetrahydrofuran, cellosolves (methylcellosolve), and lower ketones (acetone, 1-butanone).

  A dispersant is added to the aqueous medium. As the dispersant, not only the above-described resin fine particles but also known surfactants, polymer dispersants, and solid dispersants can be used. In the present invention, the dispersant is used for the following reason. That is, the dispersant surrounds the oil droplets formed by finely dispersing the organic solvent in which the binder resin, which is the main component of the toner, is dissolved with high shearing force, and prevents the oil droplets from reaggregating. This is for stabilization.

  Examples of the surfactant include an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and a nonionic surfactant, which can be arbitrarily selected in accordance with the polarity at the time of toner particle formation. .

  Examples of the anionic surfactant include alkylbenzene sulfonate, α-olefin sulfonate, and phosphate ester.

  Examples of cationic surfactants include aliphatic primary, secondary or secondary amine acids having fluoroalkyl groups, aliphatic quaternary ammonium salts such as perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salts, and benzas. Examples thereof include a ruconium salt, a benzethonium chloride, a pyridinium salt, and an imidazolinium salt.

  Examples of nonionic surfactants include fatty acid amide derivatives and polyhydric alcohol derivatives.

  Examples of amphoteric surfactants include alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine and N-alkyl-N, N-dimethylammonium betaine.

  A polymer dispersant may be used as the dispersant. Examples thereof include acids such as acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid, and maleic anhydride. Or, for example, β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, γ-hydroxypropyl acrylate, γ-hydroxypropyl methacrylate, 3-chloroacrylate 2-hydroxypropyl, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate, glycerol monomethacrylate, N-methylolacrylamide, N-methylolmethacrylate Examples thereof include acrylic monomers or methacrylic monomers containing a hydroxyl group such as amide. Next, for example, vinyl alcohol such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, or ethers with vinyl alcohol can be mentioned. Alternatively, for example, vinyl acetate, vinyl propionate, vinyl butyrate and the like, and esters of vinyl alcohol and a compound containing a carboxyl group such as acrylamide, methacrylamide, diacetone acrylamide, and the like can be given. Examples thereof include acid chlorides such as acrylic acid chloride and methacrylic acid chloride. Next, for example, a homopolymer or copolymer having a nitrogen atom of pinylviridine, vinylpyrrolidone, vinylimidazole, ethyleneimine, or a heterocyclic ring thereof.

  And, for example, polyoxyethylene, polyoxypropylene, polyoxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonyl phenyl ether, polyoxyethylene lauryl phenyl ether, Examples thereof include polyoxyethylene compounds such as polyoxyethylene stearyl phenyl ester and polyoxyethylene nonyl phenyl ester. In addition, celluloses such as methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose can be used.

  In the case of an inorganic dispersant, toner particles are granulated in a state of being adhered to the particle surface after dispersion, and therefore, those that can be removed by an acid having no affinity with a solvent are preferable. For example, calcium carbonate, calcium chloride, hydrocarbon Sodium, potassium hydrocarbon, sodium hydroxide, potassium hydroxide, hydroxyapatite, and calcium triphosphate can be used.

  When a dispersant other than the resin fine particles is used, the dispersant can remain on the surface of the toner particles, but it is preferable to remove it by washing from the charged surface of the toner.

  In the present invention, it is also preferable that the carboxylic acid residue of the polyester in the binder resin is dissociated to exhibit a surface active effect. Specifically, the carboxylic acid of the polyester can be dissociated by allowing amines to be present in the oil phase or the aqueous phase. As amines that can be used at this time, amines of relatively low molecular weight such as aqueous ammonia, triethylamine, and triethanolamine are preferable.

  The dispersion method is not particularly limited, and general-purpose devices such as a low-speed shear method, a high-speed shear method, a friction method, a high-pressure jet method, and an ultrasonic wave can be used. Anything can be used.

  For example, Ultra Turrax (manufactured by IKA), Polytron (manufactured by Kinematica), TK Auto Homo Mixer (manufactured by Special Mechanized Industry Co., Ltd.), Ebara Milder (manufactured by Ebara Corporation), TK Homomic Line Flow (Made by Special Machine Industries Co., Ltd.), colloid mill (made by Shinko Pantech Co., Ltd.), thrasher, trigonal wet pulverizer (made by Mitsui Miike Chemical Co., Ltd.), Cavitron (made by Eurotech), fine flow mill Examples thereof include a continuous emulsifier (manufactured by Taiheiyo Kiko Co., Ltd.), a clear mix (manufactured by M Technique Co., Ltd.), a batch type of Philmix (manufactured by Tokushu Kika Kogyo Co., Ltd.), or a continuous-use emulsifier.

  When a high-speed shearing disperser is used, the number of rotations is not particularly limited, but is usually 1000 rpm to 30000 rpm, preferably 3000 rpm to 20000 rpm. In the case of a batch method, the dispersion time is usually from 0.1 minutes to 5 minutes. The temperature during dispersion is usually 10 ° C. or higher and 90 ° C. or lower (under pressure), preferably 10 ° C. or higher and 70 ° C. or lower.

  The method for preparing the resin fine particles to be the surface layer is not particularly limited, and the emulsion polymerization method or the resin is dissolved in a solvent or melted to be liquefied and suspended in an aqueous medium. It can be prepared by granulation. At this time, known surfactants, dispersants, and the like can be used, and the resin constituting the fine particles can be made self-emulsifying.

  The resin fine particles may be any resin as long as it can form an aqueous dispersion, and may be a thermoplastic resin or a thermosetting resin. For example, vinyl resin, polyurethane resin, epoxy resin, polyester resin, polyamide resin, Examples include polyimide resins, silicon resins, phenol resins, melamine resins, urea resins, aniline resins, ionomer resins, and polycarbonate resins. As the resin fine particles, two or more of the above resins may be used in combination. Among these, a vinyl resin, a polyurethane resin, an epoxy resin, a polyester resin, and a combination thereof are preferable because an aqueous dispersion of resin fine particles is easily obtained.

  Solvents that can be used when fine particles are prepared by dissolving a resin in a solvent are not particularly limited, but hydrocarbon solvents such as ethyl acetate, xylene, and hexane, halogenated hydrocarbon systems such as methylene chloride, chloroform, and dichloroethane. Solvents, ester solvents such as methyl acetate, ethyl acetate, butyl acetate and isopropyl acetate, ether solvents such as diethyl ether, ketone solvents such as acetone, methyl ethyl ketone, diisobutyl ketone, cyclohexanone and methylcyclohexane, methanol, ethanol and butanol Examples of the alcohol solvent are as follows. The resin fine particles preferably have a number average particle diameter of 5 nm or more and 500 nm or less so that the toner particles form a capsule structure. Moreover, as the resin fine particles, those having a glass transition temperature of preferably 30 ° C. or higher and 100 ° C. or lower and those having a weight average molecular weight of 5,000 or higher and 200,000 or lower are preferably used.

  In the present invention, among the methods called interfacial polymerization, it is also possible to subject the isocyanate group-containing prepolymer to elongation reaction and crosslinking reaction with amines in the presence of the resin fine particles.

  For the purpose of introducing a modified polyester resin having a urethane or / and urea group, when a modified polyester resin having an isocyanate group at the terminal and an amine capable of reacting with the polyester resin are added, the toner composition is placed in an aqueous medium. Before dispersion, amines may be mixed in the oil phase, or amines may be added to the aqueous medium.

  The time required for the reaction is selected depending on the isocyanate group structure of the polyester prepolymer and the reactivity between the added amines, but is 1 minute to 40 hours, preferably 1 hour to 24 hours. The reaction temperature is usually 0 ° C. or higher and 150 ° C. or lower, preferably 20 ° C. or higher and 98 ° C. or lower. This reaction may be included in a step of adhering or / and aggregating the resin fine particles and other resin fine particles and then fusing them.

  As a specific production method, there is a reaction between a polyester prepolymer having an isocyanate group and amines. Other examples of the polyester prepolymer having an isocyanate group include a polycondensate of a polyol and a polycarboxylic acid, and a polyester obtained by further reacting a polyester having an active hydrogen group with a polyisocyanate. Examples of the active hydrogen group possessed by the polyester include hydroxyl groups (alcoholic hydroxyl groups and phenolic hydroxyl groups), amino groups, carboxyl groups, mercapto groups, and the like. Among these, alcoholic hydroxyl groups are preferred.

  As the polyester, urea-modified polyester (UMPE) can be used, and this polyester may contain a urethane bond together with a urea bond.

  The urea-modified polyester can be produced by a one-shot method. The weight average molecular weight of the urea-modified polyester is preferably 10,000 or more, more preferably 20,000 to 10,000,000, and still more preferably 30,000 to 1,000,000.

  In the present invention, the urea-modified polyester can also contain unmodified polyester or the block polymer as a binder resin, which improves low-temperature fixability and gloss when used in a full-color device. preferable. As the unmodified polyester, the urea-modified polyester includes a polycondensate of the polyol and the polycarboxylic acid similar to the polyester component, and the preferable one is the same as the urea-modified polyester. The unmodified polyester is not limited to unmodified polyester, but may be modified with a chemical bond other than a urea bond, and may be modified with a urethane bond, for example. The urea-modified polyester and the unmodified polyester are preferably at least partially compatible from the viewpoint that the low-temperature fixability and the hot offset resistance can be improved. Accordingly, the polyester component of the urea-modified polyester and the unmodified polyester preferably have similar compositions. The hydroxyl value of the unmodified polyester is preferably 5 mgKOH / g or more.

  The acid value of the unmodified polyester is usually 1 mgKOH / g or more and 30 mgKOH / g or less, preferably 5 mgKOH / g or more and 20 mgKOH / g or less. By giving the acid value in the above range, it tends to be negatively charged, and further, the affinity between the paper and the toner is good when fixing to paper, and the low-temperature fixability is improved.

Examples of the wax used in the present invention include the following.
Low molecular weight polyethylene, low molecular weight polypropylene, low molecular weight olefin copolymer, aliphatic hydrocarbon wax such as microcrystalline wax, paraffin wax, Fischer-Tropsch wax; oxide of aliphatic hydrocarbon wax such as oxidized polyethylene wax; fat A wax mainly composed of a fatty acid ester such as an aromatic hydrocarbon ester wax; and a partially or completely deoxidized fatty acid ester such as a deoxidized carnauba wax; a partial ester of a fatty acid and a polyhydric alcohol such as behenic acid monoglyceride A methyl ester compound having a hydroxyl group obtained by hydrogenating vegetable oils and fats.

  The wax particularly preferably used in the present invention is, in the dissolution suspension method, easy preparation of the wax dispersion, easy incorporation into the prepared toner, seepage from the toner during fixing, release From the viewpoint of properties, aliphatic hydrocarbon waxes and ester waxes are preferred.

  In the present invention, the ester wax only needs to have at least one ester bond in one molecule, and either natural ester wax or synthetic ester wax may be used.

Examples of the synthetic ester wax include a monoester wax synthesized from a long-chain linear saturated fatty acid and a long-chain linear saturated alcohol. The long-chain linear saturated fatty acid is represented by the general formula C _n H _{2n + 1} COOH, and those having n = 5 to 28 are preferably used. The long-chain straight-chain saturated alcohol is represented by C _n H _{2n + 1} OH, and n = 28 or more is preferably used.

  Examples of natural ester waxes include candelilla wax, carnauba wax, rice wax, and derivatives thereof.

  Among the above, more preferable waxes are synthetic ester waxes composed of long-chain linear saturated fatty acids and long-chain linear saturated aliphatic alcohols, or natural waxes based on the above esters. Further, in the present invention, it is more preferable that the ester is a monoester in addition to the linear structure described above.

  In the present invention, the use of a hydrocarbon wax is also one of the preferred modes.

  The content of the wax in the toner particles is preferably 2.0 parts by mass or more and 20.0 parts by mass or less, more preferably 2.0 parts by mass or more and 15.0 parts by mass with respect to 100 parts by mass of the binder resin. .

  In the present invention, the wax preferably has a peak temperature of a maximum endothermic peak at 60 ° C. or higher and 120 ° C. or lower in differential scanning calorimetry (DSC). More preferably, it is 60 degreeC or more and 90 degrees C or less.

  The toner contains a colorant in order to impart coloring power. Preferred examples of the colorant include the following organic pigments, organic dyes, and inorganic pigments, and other colorants conventionally used in toners can be used. The colorant used in the present invention is selected from the viewpoints of hue angle, saturation, brightness, light resistance, OHP transparency, and dispersibility in the toner. In the present invention, it is preferable to use a dye or pigment having high solubility in water as the colorant.

  The following are mentioned as a coloring agent used for this invention.

  Examples of the colorant for yellow include compounds typified by condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds.

  Specific examples include the following. C. I. Pigment Yellow 12, 13, 14, 15, 17, 62, 74, 83, 93, 94, 95, 97, 109, 110, 111, 120, 128, 129, 138, 147, 150, 151, 154, 155, 168, 180, 185, 213, 214. These can be used alone or in combination of two or more.

  Examples of the colorant for magenta include condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds.

  Specific examples include the following. C. I. Pigment Red 2, 3, 5, 6, 7, 23, 48: 2, 48: 3, 48: 4, 57: 1, 81: 1, 122, 146, 150, 166, 169, 177, 184, 185, 202, 206, 220, 221, 238, 254, 269, C.I. I. Pigment Bio Red 19. These can be used alone or in combination of two or more.

Examples of the colorant for cyan include copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, and basic dye lake compounds.
Specific examples include the following. C. I. Pigment blue 1, 7, 15, 15: 1, 15: 2, 15: 3, 15: 4, 60, 62, 66. These can be used alone or in combination of two or more.

  Examples of black colorants include the following. Carbon black such as furnace black, channel black, acetylene black, thermal black, lamp black. Further, metal oxides such as magnetite and ferrite are also used.

  The colorant is preferably used in an amount of 1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the binder resin. When magnetic powder is used as the colorant, the addition amount is preferably 40 parts by mass or more and 150 parts by mass or less with respect to the toner mass.

  The toner may contain a charge control agent as necessary. By adding a charge control agent, the charge characteristics can be stabilized, and the optimum triboelectric charge amount can be controlled according to the development system.

  As the charge control agent, known ones can be used, and a charge control agent that has a high charging speed and can stably maintain a constant charge amount is particularly preferable.

  Examples of the charge control agent for controlling the toner to be negatively charged include the following. Organic metal compounds and chelate compounds are effective, and examples include monoazo metal compounds, acetylacetone metal compounds, aromatic oxycarboxylic acids, aromatic dicarboxylic acids, oxycarboxylic acids, and dicarboxylic acid-based metal compounds. These charge control agents can be contained alone or in combination of two or more.

  A preferable blending amount of the charge control agent is 0.01 parts by mass or more and 20 parts by mass or less, more preferably 0.5 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the binder resin. However, it is not essential to add a charge control agent to the toner of the present invention, and the toner does not necessarily contain a charge control agent by actively utilizing frictional charging with the toner layer thickness regulating member or the toner carrier. There is no need to let it.

  It is preferable that an inorganic fine powder is added to the toner as a fluidity improver.

  Examples of the inorganic fine powder added to the toner of the present invention include fine powder of fine oxide such as fine silica powder, fine titanium oxide powder, fine alumina powder, fine strontium titanate powder, and fine powder. Among the inorganic fine powders, silica fine powder and titanium oxide fine powder are preferable.

  Among these, inorganic fine powder treated with silicone oil is preferable. More preferably, when the inorganic fine powder is hydrophobized with a coupling agent, or simultaneously with the treatment, the hydrophobized inorganic fine powder treated with silicone oil treated with silicone oil increases the charge amount of the toner even in a high humidity environment. It is good for maintaining and reducing selective developability.

  The amount of the inorganic fine powder added is preferably 0.1 parts by weight or more and 4.0 parts by weight or less, more preferably 0.2 parts by weight or more and 3. parts by weight or less with respect to 100 parts by weight of the toner before addition. 5 parts by mass or less.

  The toner obtained by the production method of the present invention preferably has a weight average particle diameter (D4) of 3.0 μm or more and 8.0 μm or less. More preferably, they are 5.0 micrometers or more and 7.0 micrometers or less. The use of a toner having such a weight average particle diameter (D4) is preferable from the viewpoint of sufficiently satisfying the dot reproducibility while improving the handleability.

  Further, the ratio D4 / D1 of the weight average particle diameter (D4) and the number average particle diameter (D1) of the toner is preferably 1.25 or less. More preferably, it is 1.20 or less.

  The toner preferably has a number average molecular weight (Mn) of 8,000 or more and 30,000 or less and a weight average molecular weight (Mw) of 15,000 or more and 60,000 or less in GPC measurement of THF-soluble matter. . By being in this range, the heat resistant storage stability can be kept good, and further appropriate viscoelasticity can be obtained. A more preferable range of Mn is 10,000 or more and 20,000 or less, and a more preferable range of Mw is 20,000 or more and 50,000 or less. Further, Mw / Mn is preferably 6 or less. A more preferable range of Mw / Mn is 3 or less.

  A method for measuring various physical properties will be described below.

<Measurement method of Tp, Tp ′, ΔH, half width>
The Tp, Tp ′, ΔH, and half-value width of the toner and its material are measured using DSC Q1000 (manufactured by TA Instruments) under the following conditions.
Temperature increase rate: 10 ° C / min
Measurement start temperature: 20 ° C
Measurement end temperature: 200 ° C
The temperature correction of the device detection unit uses the melting points of indium and zinc, and the correction of heat uses the heat of fusion of indium.

  Specifically, about 5 mg of a sample is precisely weighed, placed in a silver pan, and measured once. A silver empty pan is used as a reference.

  When measuring the toner as a sample, if the maximum endothermic peak derived from the binder resin does not overlap the endothermic peak of the wax, the obtained maximum endothermic peak is treated as an endothermic peak derived from the binder resin as it is. On the other hand, in the toner measurement, when the endothermic peak derived from the binder resin overlaps with the endothermic peak of the wax, it is necessary to subtract the endothermic amount derived from the wax from the endothermic amount of the maximum endothermic peak.

  For example, the endothermic peak derived from the binder resin can be obtained by subtracting the endothermic amount derived from the wax from the maximum endothermic peak obtained by the following method.

  First, the DSC measurement of a single wax is separately performed to determine the endothermic characteristics. Next, the wax content in the toner is determined. The method for measuring the wax content in the toner particles is not particularly limited, but can be performed by, for example, peak separation in DSC measurement or known structural analysis. Thereafter, the endothermic amount resulting from the wax is calculated from the wax content in the toner, and this amount may be subtracted from the maximum endothermic peak. When the wax is easily compatible with the resin component, it is necessary to calculate and subtract the amount of heat absorbed due to the wax after multiplying the content of the wax by the compatibility rate. The compatibility is calculated from the endothermic amount of the molten mixture obtained in advance and the endothermic amount of the wax alone, which is obtained by mixing the molten mixture of the resin component and the wax at a predetermined ratio. Calculated from the value divided by the endothermic amount.

  Further, in the measurement, in order to obtain an endothermic amount per 1 g of the binder resin, it is necessary to remove the mass of components other than the binder resin from the mass of the sample.

  The content of components other than the resin component may be calculated from the proportion of the prescription, but when the proportion of the prescription is unknown, it can be measured by a known analysis means. If the analysis is difficult, determine the amount of residual ash from the toner, and add the amount of components other than the binder resin to be incinerated, such as wax, as the content of components other than the binder resin. It can be determined by subtracting from the toner mass.

  The incineration residual ash content in the toner is obtained by the following procedure. About 2 g of sample is placed in a 30 ml magnetic crucible that has been pre-weighed. Put the crucible in an electric furnace, heat at about 900 ° C. for about 3 hours, let cool in the electric furnace, let it cool in a desiccator at room temperature for more than 1 hour, weigh the mass of the crucible containing the incineration residual ash, Incineration residual ash is calculated by subtracting the mass of the crucible.

  The maximum endothermic peak is a peak where the endothermic amount is maximum when there are a plurality of peaks. Further, the half width is the temperature width at the half value of the peak height of the endothermic peak.

<Measurement method of melting point of wax>
The melting point of the wax was measured using a DSC Q1000 (TA Instruments) under the following conditions.
Temperature increase rate: 10 ° C / min
Measurement start temperature: 20 ° C
Measurement end temperature: 180 ° C
The temperature correction of the device detection unit uses the melting points of indium and zinc, and the correction of heat uses the heat of fusion of indium.

  Specifically, about 2 mg of wax is precisely weighed and placed in a silver pan, and an empty silver pan is used as a reference to perform differential scanning calorimetry. In the measurement, the temperature is once raised to 200 ° C., subsequently lowered to 30 ° C., and then heated again. In the second temperature raising process, the peak temperature of the maximum endothermic peak of the DSC curve in the temperature range of 30 ° C. to 200 ° C. is defined as the melting point of the wax. The maximum endothermic peak means a peak having the largest endothermic amount when there are a plurality of peaks.

<Measuring method of weight average particle diameter (D4) and number average particle diameter (D1)>
The weight average particle diameter (D4) and number average particle diameter (D1) of the toner are calculated as follows. As a measuring device, a precise particle size distribution measuring device “Coulter Counter Multisizer 3” (registered trademark, manufactured by Beckman Coulter, Inc.) using a pore electrical resistance method equipped with a 100 μm aperture tube is used. For setting the measurement conditions and analyzing the measurement data, the attached dedicated software “Beckman Coulter Multisizer 3 Version 3.51” (manufactured by Beckman Coulter, Inc.) is used. The measurement is performed with 25,000 effective measurement channels.

  As the electrolytic aqueous solution used for the measurement, special grade sodium chloride is dissolved in ion-exchanged water so as to have a concentration of about 1% by mass, for example, “ISOTON II” (manufactured by Beckman Coulter, Inc.) can be used.

  Prior to measurement and analysis, the dedicated software was set as follows.

  On the “Change Standard Measurement Method (SOM)” screen of the dedicated software, set the total count in the control mode to 50,000 particles, set the number of measurements once, and set the Kd value to “standard particles 10.0 μm” (Beckman Coulter Set the value obtained using By pressing the “Threshold / Noise Level Measurement Button”, the threshold and noise level are automatically set. In addition, the current is set to 1600 μA, the gain is set to 2, the electrolyte is set to ISOTON II, and the “aperture tube flush after measurement” is checked.

  In the “Pulse to particle size conversion setting” screen of the dedicated software, the bin interval is set to logarithmic particle size, the particle size bin is set to 256 particle size bin, and the particle size range is set to 2 μm to 60 μm.

  The specific measurement method is as follows.

  (1) About 200 ml of the electrolytic solution is placed in a glass 250 ml round bottom beaker exclusively for Multisizer 3, set on a sample stand, and the stirrer rod is stirred counterclockwise at 24 rpm. Then, the dirt and bubbles in the aperture tube are removed by the “aperture flush” function of the dedicated software.

  (2) About 30 ml of the electrolytic aqueous solution is put into a glass 100 ml flat bottom beaker. In this, "Contaminone N" (nonionic surfactant, anionic surfactant, 10% by weight aqueous solution of neutral detergent for pH7 precision measuring instrument cleaning, made by organic builder, manufactured by Wako Pure Chemical Industries, Ltd. About 0.3 ml of a diluted solution obtained by diluting 3) with ion-exchanged water is added.

  (3) Two oscillators with an oscillation frequency of 50 kHz are incorporated with the phase shifted by 180 degrees, and an ultrasonic disperser “Ultrasonic Dissipation System Tetora 150” (manufactured by Nikki Bios Co., Ltd.) having an electrical output of 120 W is prepared. About 3.3 l of ion-exchanged water is placed in the water tank of the ultrasonic disperser, and about 2 ml of Contaminone N is added to the water tank.

  (4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. In the beaker, the height position of the beaker is adjusted so that the resonance state of the liquid surface of the electrolytic aqueous solution is maximized.

  (5) In a state where the electrolytic aqueous solution in the beaker of (4) is irradiated with ultrasonic waves, about 10 mg of toner is added to the electrolytic aqueous solution little by little and dispersed. Then, the ultrasonic dispersion process is continued for another 60 seconds. In the ultrasonic dispersion, the temperature of the water tank is appropriately adjusted so as to be 10 ° C. or higher and 40 ° C. or lower.

  (6) To the round bottom beaker of (1) installed in the sample stand, the electrolyte solution of (5) in which the toner is dispersed is dropped using a pipette, and the measurement concentration is adjusted to about 5%. . Measurement is performed until the number of measured particles reaches 50,000.

  (7) The measurement data is analyzed with the dedicated software attached to the apparatus, and the weight average particle diameter (D4) and the number average particle diameter (D1) are calculated. The “average diameter” on the “analysis / volume statistic (arithmetic average)” screen when the graph / volume% is set in the dedicated software is the weight average particle size (D4). When the number% is set, the “average diameter” on the “analysis / number statistics (arithmetic average)” screen is the number average particle diameter (D1).

<Measurement Method of Number Average Molecular Weight Mn and Weight Average Molecular Weight Mw>
The molecular weight (Mn, Mw) of the THF soluble content of the toner and its material used in the present invention is measured by gel permeation chromatography (GPC) as follows.

First, a sample is dissolved in tetrahydrofuran (THF) at room temperature over 24 hours. The obtained solution is filtered through a solvent-resistant membrane filter “Maescho Disc” (manufactured by Tosoh Corporation) having a pore diameter of 0.2 μm to obtain a sample solution. The sample solution is adjusted so that the concentration of the component soluble in THF is about 0.8% by mass. Using this sample solution, measurement is performed under the following conditions.
Apparatus: HLC8120 GPC (detector: RI) (manufactured by Tosoh Corporation)
Column: Seven series of Shodex KF-801, 802, 803, 804, 805, 806, 807 (manufactured by Showa Denko KK)
Eluent: Tetrahydrofuran (THF)
Flow rate: 1.0 ml / min
Oven temperature: 40.0 ° C
Sample injection volume: 0.10 ml
In calculating the molecular weight of the sample, standard polystyrene resin (for example, trade name “TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F— 10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500 ", manufactured by Tosoh Corporation) are used.

<Measuring method of the ratio of the part which can take a crystal structure>
The ratio of the part having a crystal structure in the binder resin is calculated from the ratio of the part having a crystal structure in the raw resin.

The ratio of the part which can take the crystal structure in raw material resin is measured on condition of the following by 1H-NMR.
Measuring apparatus: FT NMR apparatus JNM-EX400 (manufactured by JEOL Ltd.)
Measurement frequency: 400MHz
Pulse condition: 5.0μs
Frequency range: 10500Hz
Integration count: 64 times Measurement temperature: 30 ° C
Sample: 50 mg of a measurement sample is put into a sample tube having an inner diameter of 5 mm, deuterated chloroform (CDCl ₃ ) is added as a solvent, and this is dissolved in a constant temperature bath at 40 ° C. to prepare.

From the obtained 1H-NMR chart, a peak independent of the peaks attributed to other elements is selected from the peaks attributed to the constituent elements of the portion capable of forming a crystal structure, and the integrated value S of the peaks is selected. ₁ is calculated. Similarly, among the peaks attributed to the components of the site do not take a crystal structure, and select the independent peaks and peak attributable to other components, an integrated value S ₂ is calculated for this peak.

The ratio of the part that can take the crystal structure is obtained as follows using the integrated values S ₁ and S ₂ . Note that n ₁ and n ₂ are the numbers of hydrogens in the constituent elements to which the peaks focused on the respective sites belong.
Percentage of sites that can have a crystal structure (%) =
_{{(S 1 / n 1)} / ((S 1 / n 1) + (S 2 / n 2))} × 100
In addition, the analysis of the structure of the part which can take a crystal structure is performed by a publicly known method. In the block polymers described in the examples, the integrated value of the peak derived from the diol component contained in the crystalline polyester component was used as a site capable of taking a crystal structure. In addition, as a portion not taking a crystalline portion, an integrated value of a peak derived from an isocyanate component was used.

<Method for measuring acid value of resin>
The acid value is the number of mg of potassium hydroxide necessary to neutralize the acid contained in 1 g of the resin sample. The acid value of the resin is measured according to JIS K 0070-1966, and specifically, it is measured according to the following procedure.

(1) Preparation of Reagent 1.0 g of phenolphthalein is dissolved in 90 ml of ethyl alcohol (95 vol%), and ion exchange water is added to make 100 ml to obtain a “phenolphthalein solution”.

  7 g of special grade potassium hydroxide is dissolved in 5 ml of water, and ethyl alcohol (95 vol%) is added to make 1 l. Place in an alkali-resistant container so as not to touch carbon dioxide gas, leave it for 3 days, and filter to obtain a “potassium hydroxide solution”. The obtained potassium hydroxide solution is stored in an alkali-resistant container. The orientation is performed according to JIS K 0070-1996.

(2) Operation (A) Main test 2.0 g of the pulverized resin sample is precisely weighed into a 200 ml Erlenmeyer flask, and 100 ml of a toluene / ethanol (2: 1) mixed solution is added and dissolved over 5 hours. Subsequently, several drops of the phenolphthalein solution is added as an indicator, and titration is performed using the potassium hydroxide solution. The end point of titration is when the light red color of the indicator lasts for about 30 seconds.

(B) Blank test Titration is performed in the same manner as above except that no sample is used (that is, only a mixed solution of toluene / ethanol (2: 1) is used).

(3) The acid value is calculated by substituting the obtained result into the following formula.
A = {(BC) × f × 5.61} / S
(here,
A: Acid value (mgKOH / g)
B: Amount of added potassium hydroxide solution for blank test (ml)
C: Amount of potassium hydroxide solution added in this test (ml)
f: Factor of potassium hydroxide solution S: Sample (g)
It is. )

  Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.

(Synthesis of crystalline polyester 1)
The following raw materials were charged into a heat-dried two-necked flask while introducing nitrogen.
Sebacic acid 136.8 parts by mass 1,4-butanediol 63.2 parts by mass Dibutyltin oxide 0.1 part by mass After the system was purged with nitrogen by depressurization, the water produced under a nitrogen stream at 180 ° C was distilled off. The mixture was stirred for 6 hours. Thereafter, the temperature was gradually raised to 230 ° C. under reduced pressure while continuing stirring, and the mixture was further maintained for 2 hours while distilling off water under a nitrogen stream. Crystalline polyester 1 was synthesize | combined by air-cooling when it became a viscous state and stopping reaction. Table 1 shows the physical properties of the crystalline polyester 1.

(Synthesis of crystalline polyesters 2 to 4)
In the synthesis of the crystalline polyester 1, crystalline polyesters 2 to 4 were synthesized in the same manner except that the raw material charge was changed as shown in Table 1. Table 1 shows the physical properties of the crystalline polyesters 2 to 4.

(Crystalline polyester 5 synthesis)
In the synthesis of the crystalline polyester 1, the crystalline polyester 5 was synthesized in the same manner except that the amount of raw material charged was changed as follows. Table 1 shows the physical properties of the crystalline polyester 5.
Succinic acid 130.0 parts by mass Ethylene glycol 70.0 parts by mass Dibutyltin oxide 0.1 parts by mass

(Synthesis of amorphous polyester 1)
Bisphenol A ethylene oxide 2 mol adduct 700.0 parts by mass Isophthalic acid 250.0 parts by mass Fumaric acid 50.0 parts by mass Dibutyltin oxide 2.0 parts by mass In a reaction vessel equipped with a stirrer and a nitrogen inlet tube, The above raw materials were added, reacted at 230 ° C. under normal pressure for 8 hours, and further reacted under reduced pressure of 12 mmHg for 5 hours. Then, it cooled to 160 degreeC, 30 mass parts of phthalic anhydrides were then added, and it was made to react for 2 hours, and the amorphous polyester 1 was obtained.

  This amorphous polyester 1 had a glass transition temperature Tg of 60 ° C., a softening point temperature of 120 ° C., a number average molecular weight (Mn) of 7000, and a weight average molecular weight (Mw) of 25,000.

(Synthesis of amorphous polyester 2)
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe,
Bisphenol A ethylene oxide 2-mole adduct 724.0 parts by mass Terephthalic acid 276.0 parts by mass, polycondensation under normal pressure at 230 ° C. for 8 hours, then reaction under reduced pressure of 10-15 mmHg for 5 hours to produce amorphous A functional polyester was obtained. Amorphous polyester 2 having a glass transition temperature Tg of 64 ° C., a number average molecular weight (Mn) of 17,000, and a weight average molecular weight of 24,000 (Mw) was obtained.

(Synthesis of block polymer 1)
Crystalline polyester 1 210.0 parts by mass Xylylene diisocyanate (XDI) 56.0 parts by mass Cyclohexanedimethanol (CHDM) 34.0 parts by mass Tetrahydrofuran (THF) 300.0 parts by mass A reaction vessel equipped with a stirrer and a thermometer The above materials were charged with nitrogen substitution. The mixture was heated to 50 ° C. and subjected to urethanization reaction for 15 hours. Thereafter, 3.0 parts by mass of salicylic acid was added to modify the isocyanate terminal. The solvent, THF, was distilled off to obtain block polymer 1. Table 3 shows the physical properties of the obtained block polymer 1.

(Synthesis of block polymers 2 to 10)
In the synthesis of block polymer 1, block polymers 2 to 10 were synthesized in the same manner except that the materials, blending amounts, and reaction conditions shown in Table 2 were changed. Table 3 shows the physical properties of the obtained block polymers 2 to 10.

(Synthesis of block polymer 11)
Crystalline polyester 1 195.0 parts by mass Amorphous polyester 1 105.0 parts by mass Dibutyltin oxide 0.1 parts by mass Tetrahydrofuran (THF) 300.0 parts by mass In a reaction vessel equipped with a stirrer and a thermometer, nitrogen substitution was performed. The above materials were charged while The mixture was heated to 60 ° C. and subjected to esterification reaction over 10 hours. Thereafter, THF as a solvent was distilled off to obtain a block polymer 11. Table 3 shows the physical properties of the obtained block polymer 11.

(Production of resin fine particle dispersion S1)
Water 690.0 parts by weight Sodium salt of ethylene oxide methacrylate adduct sulfate (Eleminol RS-30, manufactured by Sanyo Chemical Industries) 9.0 parts by weight styrene 90.0 parts by weight Methacrylic acid 90.0 parts by weight Butyl acrylate 110 0.0 part by mass Ammonium persulfate 1.0 part by mass The above materials were charged in a reaction vessel equipped with a stir bar and a thermometer, and stirred at 350 rpm for 15 minutes to obtain a white emulsion. The system was heated to raise the system temperature to 75 ° C. and reacted for 5 hours. Further, 30 parts of a 1% ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 5 hours to be a vinyl resin (a copolymer of styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt). A fine particle dispersion S1 was obtained. The volume average particle size of the particles dispersed in the resin fine particle dispersion S1 was 105 nm as measured using a laser diffraction / scattering particle size distribution analyzer LA-920 (manufactured by Horiba, Ltd.). A part of the resin fine particle dispersion S1 was taken out and measured for Tg and weight average molecular weight. As a result, Tg was 65 ° C. and the weight average molecular weight was 150,000.

(Preparation of wax dispersion W1)
Carnauba wax (melting point: 84 ° C.) 20.0 parts by mass 1-butanone 80.0 parts by mass The above was put into a reaction vessel capable of being sealed, and heated and stirred at 80 ° C. Next, the system was cooled to 25 ° C. over 3 hours while gently stirring at 50 rpm to obtain a milky white liquid.

  This solution was put into a heat-resistant container together with 30 parts by mass of glass beads having a diameter of 1 mm, dispersed for 3 hours with a paint shaker (manufactured by Toyo Seiki), glass beads were removed with a nylon mesh, and a wax dispersion W1 was obtained. .

(Preparation of colorant dispersion C1)
C. I. Pigment Blue 15: 3 100.0 parts by mass 1-butanone 150.0 parts by mass glass beads (1 mm) 200.0 parts by mass The above materials were put into a heat-resistant glass container and dispersed for 5 hours using a paint shaker. The glass beads were removed with a nylon mesh to obtain a colorant dispersion C1.

<Preparation Example 1 of Particles before Treatment>
(Preparation of oil phase 1)
Block polymer 1 100.0 parts by mass 1-butanone 85.0 parts by mass The above materials were placed in a beaker and stirred at 3000 rpm for 1 minute using a disper (manufactured by Tokushu Kika).
Wax dispersion W1 (solid content 20%) 50.0 parts by mass Colorant dispersion C1 (solid content 40%) 12.5 parts by mass 1-butanone 5.0 parts by mass Oil Phase 1 was prepared by stirring for 3 minutes while cooling at 6000 rpm to 5 ° C. or lower.

(Preparation of aqueous phase 1)
Resin fine particle dispersion S1 (solid content 30%) 26.7 parts by mass 50% aqueous solution of sodium dodecyl diphenyl ether disulfonate (Eleminol MON-7, manufactured by Sanyo Chemical Industries) 30.0 parts by mass 1% by mass aqueous solution of carboxymethyl cellulose 100.0 Part by mass Propylamine (manufactured by Kanto Chemical Co., Ltd.) 5.0 parts by mass Ion-exchanged water 400.0 parts by mass 1-butanone 50.0 parts by mass The aqueous phase 1 was prepared by stirring for 1 minute.

(Emulsification / desolvation)
The oil phase 1 was added to the water phase 1, the number of revolutions of the TK homomixer was increased to 10,000 rpm, and stirring was continued for 1 minute. The oil phase 1 was suspended in the water phase to obtain a pre-treatment particle dispersion 1. Subsequently, the solvent was removed under reduced pressure at 30 ° C. and 50 mmHg.

  Hydrochloric acid was added until the pre-treatment particle dispersion 1 had a pH of 1.5, and the mixture was stirred for 30 minutes and then filtered. The operations of filtration and redispersion in ion-exchanged water were repeated until the conductivity of the slurry reached 100 μS. In this way, the surfactant remaining in the slurry was removed to obtain a filter cake.

  The filter cake was vacuum-dried and subjected to air classification to obtain pre-treatment particles 1. Sampling was performed, and it was confirmed that the peak temperature of the maximum endothermic peak derived from the binder resin contained in the pre-treatment particle 1 was 58 ° C.

<Production Examples 2 to 12 of pre-treatment particles>
Pre-treatment particles 2 to 12 were obtained in the same manner except that the pre-treatment particle production example 1 was changed to the formulation shown in Table 4. Table 4 shows the peak temperature of the maximum endothermic peak derived from the binder resin contained in each pre-treatment particle.

<Preparation example 13 of pre-treatment particles>
(Synthesis example of isocyanate-modified crystalline polyester)
In a reaction vessel equipped with a stirrer and a nitrogen introduction tube,
Add 200.0 parts by weight of ethyl acetate 100.0 parts by weight of crystalline polyester 1 and raise the temperature to 80 ° C.
Isophorone dicyanate (18.0 parts by mass) was added and reacted for 2 hours to obtain an isocyanate-modified crystalline polyester.

(Synthesis example of isocyanate-modified amorphous polyester)
In a reaction vessel equipped with a stirrer and a nitrogen introduction tube,
Amorphous polyester 1 100.0 parts by mass Ethyl acetate 200.0 parts by mass Isophorone diisocyanate 10.0 parts by mass was added and reacted at 80 ° C. for 2 hours to obtain an isocyanate-modified amorphous polyester.

(Preparation of oil phase 2)
Next, in a mixing tank fitted with a liquid seal (circulator) and a stirrer,
1-butanone 450.0 parts by mass Isocyanate-modified crystalline polyester 220.0 parts by mass Isocyanate-modified amorphous polyester 95.0 parts by mass Isophorone diamine 20.0 parts by mass C.I. I. Pigment Blue 15: 3 4.0 parts by mass Carnauba wax 15.0 parts by mass was mixed at a mixing temperature of 20 ° C. for 2 hours to obtain Oil Phase 2.

(Preparation of aqueous phase 2)
Meanwhile, in another reaction tank
Ion-exchanged water 600.0 parts by mass 1-butanone 60.0 parts by mass Resin fine particle dispersion S1 90.0 parts by mass Sodium dodecylbenzenesulfonate 0.3 parts by mass was added, and a TK homomixer (made by Tokushu Kika Kogyo Co., Ltd.) The aqueous phase 2 was prepared by stirring at 12,000 rpm for 3 minutes at a temperature of 30 ° C.

(Emulsification / desolvation)
The oil phase 2 was added and dispersed in an aqueous medium, and then the temperature was raised to 80 ° C. and a urea reaction treatment was performed for 10 hours. Subsequently, the solvent was removed under reduced pressure at 30 ° C. and 50 mmHg.

  Thereafter, it was separated into solid and liquid, dehydrated, redispersed in ion-exchanged water, and stirred at room temperature at 50 rpm for 4 hours. After separation by filtration, vacuum drying was carried out to obtain pre-treatment particles 13 after air classification. The peak temperature of the maximum endothermic peak derived from the binder resin contained in the pre-treatment particles 13 was 58 ° C.

<Preparation Example 14 of Pre-treatment Particles>
(Synthesis of isocyanate-containing prepolymer)
Bisphenol A ethylene oxide 2 mol adduct 724.0 parts by mass Isophthalic acid 276.0 parts by mass Dibutyltin oxide 2.0 parts by mass In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, the above materials were put, After reacting at 230 ° C. for 8 hours under normal pressure, the reaction was performed for 5 hours under a reduced pressure of 15 mmHg. This was cooled to 160 ° C., 32 parts of phthalic anhydride was added and reacted for 2 hours. Further, this was cooled to 80 ° C. and reacted with 188 parts of isophorone diisocyanate in ethyl acetate for 2 hours to obtain an isocyanate group-containing prepolymer 1 having a weight average molecular weight of 12,000.

(Synthesis of ketimine compounds)
Isophoronediamine 30.0 parts by mass Methyl ethyl ketone 70.0 parts by mass The above materials were charged into a reaction vessel equipped with a stirrer and a thermometer, and reacted at 50 ° C. for 5 hours to obtain ketimine compound 1.

(Production of toner using isocyanate group-containing prepolymer)
Isocyanate-containing prepolymer 1 15.0 parts by mass Block polymer 1 100.0 parts by mass Crystalline polyester 1 60.0 parts by mass Ethyl acetate 150.0 parts by mass The above materials were placed in a beaker and stirred to dissolve.

Then
Carnauba wax 20.0 parts by mass C.I. I. Pigment Blue 15: 3 4.0 parts by mass was added and stirred at 12000 rpm with a TK homomixer at 60 ° C. to uniformly dissolve and disperse. Finally, 2.7 parts by mass of ketimine compound 1 was added and dissolved. This is designated as toner material solution 1.

The following materials were placed in a beaker and dissolved uniformly.
Ion-exchanged water 706.0 parts by mass Hydroxyapatite 10% suspension 294.0 parts by mass (Nippon Chemical Industry Co., Ltd. Superite 10)
Sodium dodecylbenzenesulfonate 0.2 part by mass Then, the temperature was raised to 60 ° C., and the toner material solution 1 was added while stirring at 12000 rpm with a TK homomixer, followed by stirring for 10 minutes. Then, this mixed solution was transferred to a Kolben equipped with a stirring bar and a thermometer, and the temperature was raised to 98 ° C. to cause a urea reaction. After cooling the 98 ° C. dispersion to room temperature, the solvent was removed under reduced pressure at 30 ° C. and 50 mmHg.

  Next, the dispersion was filtered, washed and dried, followed by air classification to obtain pre-treated particles 14. The peak temperature of the maximum endothermic peak derived from the binder resin contained in the pre-treatment particles 14 was 58 ° C.

(Preparation Example 15 of Pre-treatment Particles)
Isocyanate-containing prepolymer 1 15.0 parts by mass Crystalline polyester 1 74.0 parts by mass Amorphous polyester 2 10.0 parts by mass Ethyl acetate 150.0 parts by mass The above materials were placed in a beaker and stirred to dissolve.

Then
Carnauba wax 20.0 parts by mass C.I. I. Pigment Blue 15: 3 4.0 parts by mass was added and stirred at 12000 rpm with a TK homomixer at 60 ° C. to uniformly dissolve and disperse. Finally, 2.7 parts by mass of ketimine compound 1 was added and dissolved. This is designated as toner material solution 2.

  Pre-treatment particles 15 were produced in the same manner as in Preparation Example 14 for pre-treatment particles, except that the toner material solution 1 was changed to the toner material solution 2. The peak temperature of the maximum endothermic peak derived from the binder resin contained in the pre-treatment particles 15 was 58 ° C.

(Preparation Example 16 of pre-treatment particles)
Isocyanate-containing prepolymer 1 15.0 parts by mass Crystalline polyester 1 24.0 parts by mass Amorphous polyester 2 60.0 parts by mass Ethyl acetate 150.0 parts by mass The above materials were placed in a beaker and stirred to dissolve.

Then
Carnauba wax 20.0 parts by mass C.I. I. Pigment Blue 15: 3 4.0 parts by mass was added and stirred at 12000 rpm with a TK homomixer at 60 ° C. to uniformly dissolve and disperse. Finally, 2.7 parts by mass of ketimine compound 1 was added and dissolved. This is designated as toner material solution 3.

  Pre-treatment particles 16 were produced in the same manner as in Preparation Example 14 for pre-treatment particles, except that the toner material solution 1 was changed to the toner material solution 3. The peak temperature of the maximum endothermic peak derived from the binder resin contained in the pre-treatment particles 16 was 58 ° C.

<Toner Production Example 1>
(Annealing treatment)
The annealing treatment was performed using a constant temperature dryer (Satake Chemical 41-S5). The internal temperature of the constant temperature dryer was adjusted to 51 ° C. The pre-treatment particles 1 were spread evenly in a stainless steel vat, placed in the constant temperature dryer and allowed to stand for 12 hours, and then taken out. In this way, annealed particles 1 were obtained.

(External processing)
Next, anatase-type titanium oxide fine powder (BET specific surface area 80 m ² / g, number-based average primary particle size (D1): 15 nm, isobutyltrimethoxysilane 12 mass with respect to 100 parts by mass of the treated particles 1 above. % treatment) 0.9 parts by weight, oil-treated silica fine particles (BET specific surface area ^{95 m} 2 / g, silicone oil treated with 15 mass%) 1.2 parts by weight, the inorganic fine particles (sol-gel silica fine particles: BET specific surface area of ^24m 2 / g, Toner 1 was obtained by mixing 1.5 parts by mass of a number-based average primary particle size (D1): 110 nm) with a Henschel mixer (manufactured by Mitsui Miike Chemical Co., Ltd.) FM-10B.

  The obtained toner 1 was confirmed to have a weight average particle diameter of 6.0 μm, a number average particle diameter of 5.5 μm, and a Tp of 61 ° C. Incidentally, in the maximum endothermic peak of the toner 1 by differential scanning calorimeter (DSC), the endothermic peak derived from the wax and the peak derived from the binder resin did not overlap. Therefore, the maximum endothermic peak was analyzed as an endothermic peak derived from the binder resin. Table 5 shows the physical properties of Toner 1.

<Toner Production Examples 2-12, 14, 16, 18, 20-22, 25, 28, 30-35>
As shown in Table 5, the toners 2 to 12, 14, 16, 18, 20 to 22, 25 are prepared in the same manner as in the toner production example 1 except that the kind of the pre-treatment particles to be used and the annealing conditions are changed. 28, 30 to 35 were obtained. Table 5 shows the physical properties of each toner.

<Toner Production Example 13>
(Annealing treatment)
While continuing to stir the pre-treatment particle dispersion 1 in Production Example 1 for pre-treatment particles, the water temperature was raised to 51 ° C., and wet annealing was performed in water for 24.0 hours. Using the resulting treated particles, an external addition treatment was performed in the same manner as in Toner Production Example 1 to obtain a toner 13. Table 5 shows the physical properties of Toner 13.

<Toner Production Examples 15, 17, 19, 29>
Toners 15, 17, 19, and 29 were obtained in the same manner as in Toner Production Example 13 except that the wet annealing treatment conditions were changed as shown in Table 5. Table 5 shows the physical properties of each toner.

<Toner Production Example 23>
Toner 23 was obtained in the same manner as in Toner Production Example 1 except that the annealing treatment was not performed. Table 5 shows the physical properties of Toner 23.

<Toner Production Examples 24, 26, and 27>
As shown in Table 5, toners 24, 26, and 27 were obtained in the same manner as in Toner Production Example 23, except that the type of pre-treatment particles was changed. Table 5 shows the physical properties of each toner.

<Example of production of carrier particles>
4.0% by mass of a silane coupling agent (3- (2-aminoethylaminopropyl) trimethoxysilane) is added to magnetite powder having a number average particle size of 0.25 μm, and 100 ° C. or higher in a container. The mixture was stirred at a high speed to make oleophilic. Similarly, the lipophilic treatment was applied to the hematite powder having a number average particle size of 0.60 μm.
-10.0 parts by mass of phenol-Formaldehyde solution (formaldehyde 40% by mass, methanol 10% by mass, water 50% by mass) 6.0 parts by mass-Lipophilicized magnetite 63.0 parts by mass-Lipophilicized 21.0 parts by mass of the above hematite The above material, 5.0 parts by mass of 28% ammonia water, and 10.0 parts by mass of water were placed in a flask, heated to 85 ° C. over 30 minutes while stirring and mixing. The mixture was polymerized for 3 hours and cured. Then, after cooling to 30 degreeC and adding water, the supernatant liquid was removed, the precipitate was washed with water, and then air-dried. Subsequently, this was dried under reduced pressure (5 mmHg or less) at 60 ° C. to obtain spherical magnetic resin particles in which a magnetic material was dispersed.

As the coating resin, a copolymer of methyl methacrylate and a methyl methacrylate having a perfluoroalkyl group (copolymerization molar ratio 8: 1 weight average molecular weight 45,000) was used. 10.0 parts by mass of melamine particles (number average particle size 290 nm) and carbon particles (specific resistance 1 × 10 ⁻² Ω · cm, number average particle size 30 nm) are added to 100.0 parts by mass of the coating resin. Part by mass was mixed. Furthermore, 500.0 parts by mass of methyl ethyl ketone and 100.0 parts by mass of toluene were added and mixed with an ultrasonic disperser for 30 minutes to prepare a mixed solvent coating solution having a resin concentration of 10% by mass.

The coating solution is resin-coated such that the solvent is volatilized at 70 ° C. while continuously applying a shear stress, and the amount of the coating resin is 2.5 parts by mass with respect to 100 parts by mass of the carrier core (magnetic resin particles). Went. The resin-coated magnetic carrier was heat-treated at 100 ° C. for 2 hours while stirring. After cooling and crushing, it is passed through a 200-mesh (mesh size 77 μm) sieve, the volume-based 50% particle size 33 μm, the true specific gravity 3.53 g / cm ³ , the apparent specific gravity 1.84 g / cm ³ , and the strength of magnetization A carrier of 42 Am ² / kg was obtained.

<Evaluation>
A two-component developer was prepared by mixing 8 parts by mass of toners 1 to 35 and 92 parts by mass of the carrier. The following evaluation was performed using this two-component developer. The evaluation results are shown in Table 6.

[Low temperature fixability]
A commercially available color laser copier CLC5000 (manufactured by Canon Inc.) was used for evaluation of low-temperature fixability. In a normal temperature and humidity environment (23 ° C./60% RH), the development contrast of the copying machine is adjusted so that the amount of toner on the paper is 0.6 / cm ² , and the front margin is 5 mm and the width is 100 mm in the single color mode. An unfixed solid image having a length of 280 mm was prepared. A4 paper (“GF-R200”: 105 g / m ² , manufactured by Canon Inc.) was used as the transfer paper.

  The fixing device of LBP5900 (manufactured by Canon Inc.) was modified so that the fixing temperature can be manually set, and modified so that the sheet feeding speed was 150 mm / s. Using the modified fixing device, in a normal temperature and humidity environment (23 ° C./60%), while fixing the fixing temperature in increments of 5 ° C. in the range of 80 ° C. to 180 ° C., Obtained.

  The image area of the obtained fixed image is covered with a soft thin paper (trade name “Dasper”, manufactured by Ozu Sangyo Co., Ltd.), and the image area is rubbed three times while applying a load of 1.0 kPa on the thin paper. did. The image density before and after rubbing was measured, respectively, and the reduction rate ΔD (%) of the image density was calculated by the following formula. The temperature when this ΔD (%) was less than 10% was defined as the fixing start temperature, and the low temperature fixability was evaluated according to the following evaluation criteria.

The image density was measured with a color reflection densitometer (Color reflection densitometer X-Rite 404A: manufacturer X-Rite).
ΔD (%) = (image density before rubbing−image density after rubbing) / image density before rubbing × 100
(Evaluation criteria)
A: The fixing start temperature is 100 ° C. or lower.
B: The fixing start temperature is 105 ° C. or higher and 110 ° C. or lower.
C: The fixing start temperature is 115 ° C. or higher and 120 ° C. or lower.
D: The fixing start temperature is 125 ° C. or higher.

[High temperature offset]
Similarly to the evaluation of the low-temperature fixability, an unfixed solid image having a front end margin of 5 mm, a width of 100 mm, and a length of 20 mm was prepared in a single color mode using a commercially available color laser copying machine CLC5000 (manufactured by Canon Inc.). Next, A4 paper (“GF-R300”: “GF-R300”: under the condition that the unfixed solid image is heated from 160 ° C. to 5 ° C. at a process speed of 230 mm / s using the fixing device used in the low-temperature fixability evaluation. 66 g / m ² , manufactured by Canon Inc.). The obtained fixed image was evaluated for occurrence of high temperature offset (a phenomenon in which the fixed image adheres from the paper to the fixing roller, and the fixing roller rotates once and reattaches to the paper). When the difference between the image density of the portion where the offset occurred and the image density of the non-image portion showed a density of 0.05 times or more of the solid image portion density, the high temperature offset was generated. The maximum temperature lower than the high temperature offset start temperature was defined as the upper limit temperature at which fixing is possible, and evaluation was performed according to the following criteria. The image density was measured using a reflection densitometer (500 Series Spectrodensitometer; manufactured by X-Rite).

(Evaluation criteria)
A: The upper limit temperature for fixing is 175 ° C. or higher. Or even if it exceeds 180 degreeC, an offset does not generate | occur | produce.
B: Fixable upper limit temperature is 170 ° C.
C: Fixable upper limit temperature is 165 ° C.
D: The fixable upper limit temperature is 160 ° C. or lower.

[Image density]
Similarly to the evaluation of the low temperature fixability, an unfixed solid image having a tip margin of 5 mm, a width of 20 mm, and a length of 20 mm was formed in a single color mode using a commercially available color laser copying machine CLC5000 (manufactured by Canon Inc.). Next, an unfixed solid image was printed on A4 paper (at a process speed of 230 mm / s and a set temperature of 140 ° C.) using a fixing device used in the evaluation of low-temperature fixability in a normal temperature and humidity environment (23 ° C./60%). “CS-814”: 81.4 g / m ² , manufactured by Canon Inc.). The image density d of the fixed image is measured. The image density d is measured with a reflection densitometer (500 Series Spectrodensitometer; manufactured by X-Rite).

(Evaluation criteria)
A: d is 1.60 or more B: d is 1.55 or more and less than 1.60 C: d is 1.50 or more and less than 1.55 D: d is less than 1.50

[Toner durability]
LBP5400 (manufactured by Canon) was used as an image forming apparatus, and 150 g of each toner was charged in the developing device of the apparatus. In a high-temperature and high-humidity environment (30 ° C., 80 RH%), A4 paper (“GF-R300”: 66 g / m ² , manufactured by Canon Inc.) was used as transfer paper, and 20000 charts with a printing ratio of 1% were output. After the output, the developing container was disassembled and the surface of the toner carrier was visually observed. The evaluation criteria are shown below.

(Evaluation criteria)
A: No filming due to toner destruction or coloring compound adhesion.
B: 1 to 5 streaks in the circumferential direction are generated at the end portion due to toner destruction or coloring compound adhesion.
C: Six to ten circumferential streaks are generated at the end due to toner destruction or pigment compound adhesion.
D: The toner is fused to the surface of the toner carrying member, the end of the carrying member is scraped, and the toner leaks.

[Heat resistant storage stability]
About 10 g of toner was put in a 100 ml polycup and allowed to stand at 50 ° C. and 55 ° C. for 3 days, and then visually evaluated.

(Evaluation criteria)
A: Aggregates are not seen.
B: Although aggregates are seen, they break apart easily.
C: Aggregates can be grasped and do not collapse easily.
D: Almost all aggregates.

Claims (6)

A process of forming oil droplets by emulsifying and / or dispersing a toner material in which a binder resin mainly composed of a block polymer having a crystal structure, a colorant and a wax are dissolved and / or dispersed in an organic solvent in an aqueous medium. And the step of removing the organic solvent from the oil droplets, and after removing the organic solvent, the following formula (1)
Tp′-15.0 ≦ t ≦ Tp′−5.0 (1)
(Tp ′ represents the peak temperature of the maximum endothermic peak of the block polymer in the endothermic measurement by DSC.)
And a step of performing a heat treatment for 0.5 hour or more at a heating temperature t (° C.) satisfying
The binder resin contains polyester as a main component,
The ratio of the part that can take the crystal structure in the binder resin is 50% by mass or more and 85% by mass or less,
A method for producing a toner, wherein a peak temperature Tp of a maximum endothermic peak derived from a binder resin is 50 ° C. or more and 80 ° C. or less in the measurement of an endothermic amount by a differential scanning calorimeter (DSC) of the toner. The temperature at which the heat treatment is performed is the following formula (2)
Tp′−11.0 ≦ t ≦ Tp′−6.0 (2)
The toner production method according to claim 1, wherein:   The toner manufacturing method according to claim 1, wherein the heating time in the heat treatment step is 1.0 hour or more and 50.0 hours or less.   4. The toner manufacturing method according to claim 1, wherein the block polymer has a portion that can take a crystal structure and a portion that does not take a crystal structure bonded by a urethane bond. 5.   5. The half-value width of an endothermic peak derived from the binder resin is 5.0 ° C. or less when measuring the endothermic amount of the toner using a differential scanning calorimeter (DSC). The toner production method according to one item.   When measuring the endothermic amount of the toner using a differential scanning calorimeter (DSC), the total endothermic amount (ΔH) of the endothermic peak derived from the binder resin is 30 J / g or more and 80 J / g or less per gram of the binder resin. The method for producing a toner according to any one of claims 1 to 5, wherein: