JP2018185471A - toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner that achieves both low-temperature fixability and storage stability and has good chargeability even under a high-temperature and high-humidity environment.SOLUTION: A toner contains an amorphous resin having an aromatic ring and crystalline polyester. The crystalline polyester has the following formula (1) as a structural unit; one of Aand Bdescribed in the formula (1) has the structure of the formula 2, and the other of A and B is alkylene having 4 to 12 carbon atoms, inclusive.SELECTED DRAWING: None

Description

  The present invention relates to a toner for developing an electrostatic charge image used in electrophotography, electrostatic recording method and the like.

  In recent years, with increasing demands for energy saving in image formation, efforts have been made to lower the toner fixing temperature. As one means, a technique has been proposed in which a fixing temperature can be further lowered by using a polyester resin having a low softening temperature as a binder resin. However, since the softening temperature of the polyester resin is low, blocking may occur because the toners are fused together in a stationary state such as during storage or transportation.

  Therefore, Patent Documents 1 to 3 propose a technique using a crystalline compound having a sharp melt property in which the viscosity greatly decreases when the melting point is exceeded, as a means for achieving both blocking resistance and low-temperature fixability. However, when a crystalline polyester, which is a crystalline compound, is used alone as a binder resin, a major problem is that the charge gradually escapes from the toner after frictional charging due to the low electrical resistance of the crystalline polyester. Met.

  Therefore, Patent Document 4 reports a technique in which an amorphous resin and a crystalline compound are mixed and used as a binder resin as a means for achieving both low-temperature fixability and charge retention of toner.

  In order to realize further low-temperature fixability in the above method, Patent Document 5 reports a technique of using a crystalline polyester having a low melting point as a crystalline compound.

  Patent Document 6 reports an example in which a monomer component having an aromatic ring as a dicarboxylic acid component is introduced into polyester, thereby improving compatibility with an amorphous resin and improving low-temperature fixability. .

  On the other hand, in Patent Document 7, as a method for improving the chargeability, the number of carbon atoms of the alkylene group of the aliphatic dicarboxylic acid and aliphatic diol that are constituent monomers is increased, and the proportion of the ester group that is a polar group is reduced. Techniques using crystalline polyester have been reported.

Japanese Patent Publication No. 56-13943 Japanese Examined Patent Publication No.62-39428 Japanese Patent Laid-Open No. 4-120554 Japanese Patent Laid-Open No. 2003-50478 JP 2009-180931 A JP 2002-284866 A JP 2011-81355 A

  When a low-melting crystalline polyester as described in Patent Document 5 is used, the fixing temperature of the toner can be lowered. However, since the crystalline polyester melts at a low temperature and the viscosity of the toner is lowered, there is a problem that the storage stability is deteriorated.

  When the monomer component having an aromatic ring as described in Patent Document 6 is increased as a constituent component of the crystalline polyester, the proportion of the ester group that is a polar group does not increase, so that the chargeability is not deteriorated. It is possible to improve the compatibility with the amorphous resin. However, when the introduction rate of the aromatic ring is increased in order to improve compatibility, the melting point increases with the introduction rate, resulting in a problem that the low-temperature fixability of the toner is not sufficient.

  Further, as in Patent Document 7, when a crystalline polyester having a long-chain alkylene group as a structural unit and having a low ester group concentration is used, the crystalline polyester has a high resistance due to a decrease in polarity, and is charged. Will improve. However, in general, compatibility with an amorphous resin having a polarity higher than that of crystalline polyester is deteriorated. For this reason, the low-temperature fixability may not be sufficient.

  In other words, the conventionally proposed crystalline polyester has sufficient compatibility with an amorphous resin, and has a melting point sufficient for low-temperature fixability, and reduces the concentration of polar groups such as ester groups. It was difficult. Therefore, it has not been sufficient to achieve both low-temperature fixability and chargeability at a high level as a toner.

The present invention is
A toner having toner particles containing an amorphous resin having an aromatic ring and a crystalline polyester,
The crystalline polyester has a unit represented by the following formula (1),
One of A ¹ and B ^{1 in} the formula (1) is a divalent group represented by the following formula (2),
The other of A ¹ and B ¹ is an alkylene group having 4 to 12 carbon atoms.

  The crystalline polyester of the present invention has the structure of the formula (2) and has an alkylene skeleton between the aromatic ring and the ester bond, unlike a conventional structural unit having an aromatic ring such as terephthalic acid. . Therefore, it is considered that the lower melting point was induced by the planarity being weaker than the conventional crystalline polyester having an aromatic ring and the intermolecular interaction being lowered. Combined use of an amorphous resin having an aromatic ring and a crystalline polyester having the above structure increases compatibility with the similarity of chemical structure without increasing the concentration of polar groups, and provides low-temperature fixability, chargeability, and storage It was revealed that a toner having excellent properties can be obtained.

That is, the toner of the present invention is a toner containing an amorphous resin having an aromatic ring and a crystalline polyester, and the crystalline polyester has at least the formula (1) as a structural unit, and the formula (1) One of A ¹ and B ¹ described has the structure of formula (2). In addition, the toner is characterized in that the other of A ¹ and B ¹ is alkylene having 4 to 12 carbon atoms.

  According to the present invention, it is possible to provide a toner having excellent low-temperature fixability, chargeability, and storage stability.

  In the present invention, the description of “XX or more and XX or less” or “XX to XX” representing a numerical range means a numerical range including a lower limit and an upper limit as endpoints unless otherwise specified.

  First, the crystalline polyester used in the present invention will be described.

<Crystalline polyester>
Crystalline polyester is a resin in which molecular chains are regularly arranged and has a glass transition temperature and a melting point. The crystalline polyester used in the present invention is obtained by polycondensation of at least one dicarboxylic acid component and at least one dialcohol component, and has at least the formula (1) as a structural unit. In the crystalline polyester, one of A ¹ and B ¹ described in the formula (1) has a structure of the formula (2), and the other of A and B is an alkylene group having 4 to 12 carbon atoms. Features. Further, R ¹ and R ² according to the structure of the formula (2) is an alkylene group having 1 to 4 carbon atoms, R ¹ and R ² according to the structure of the formula (2) is, is methylene It is preferable.

  Unlike the conventional structural unit having an aromatic ring such as terephthalic acid, the crystalline polyester has an alkyl skeleton between the aromatic ring and the ester bond. Therefore, it is considered that the lower melting point was induced by the planarity being weaker than the conventional crystalline polyester having an aromatic ring and the intermolecular interaction being lowered. Combined use of an amorphous resin having an aromatic ring and a crystalline polyester having the above structure increases compatibility with the similarity of chemical structure without increasing the concentration of polar groups, and provides low-temperature fixability, chargeability, and storage A toner having excellent properties can be obtained.

  Specific examples of the dialcohol component used when A in Formula (1) has the structure of Formula (2) include 1,4-benzenedimethanol, 1,3-benzenedimethanol, 1,2- Benzenedimethanol, 1,4-benzenediethanol, 1,3-benzenediethanol, 1,2-benzenediethanol, 1,4-benzenedipropanol, 1,3-benzenedipropanol, 1,2-benzenedipropanol, 1 , 4-benzenedibutanol, 1,3-benzenedibutanol, 1,2-benzenedibutanol and the like. These may be used alone or in combination of two or more.

  Specific examples of the dicarboxylic acid component used when B in Formula (1) has the structure of Formula (2) include 1,4-phenylenediacetic acid, 1,3-phenylenediacetic acid, 1,2- Phenylenediacetic acid, 1,4-phenylenedipropionic acid, 1,3-phenylenedipropionic acid, 1,2-phenylenedipropionic acid, 1,4-phenylenedibutyric acid, 1,3-phenylenedibutyric acid, 1,2 -Phenylene dibutyric acid and the like. These may be used alone or in combination of two or more.

  As the dialcohol component used when A in Formula (1) has an alkylene structure having 4 to 12 carbon atoms, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, , 7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 2-methyl-1,3-propanediol, cyclohexanediol, cyclohexanedimethanol, etc. Is mentioned. These may be used alone or in combination of two or more.

  As a dicarboxylic acid component used when B in Formula (1) has an alkylene structure having 4 to 12 carbon atoms, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1,9-nonanedicarboxylic acid 1,10-decanedicarboxylic acid, 1,1-cyclopentenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid and other divalent carboxylic acids. These may be used alone or in combination of two or more.

  Further, when producing the crystalline resin of the present invention, other alcohol components and carboxylic acid components may be used in combination so as not to impair the physical properties as necessary.

  Specific examples of the alcohol component include the following. Ethylene glycol, 1,3-propanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,18-octadecanediol, 1,20-icosanediol, 2-methyl-1,3-propanediol And diols such as cyclohexanediol and cyclohexanedimethanol.

  Trihydric or higher alcohols can also be used, and examples thereof include glycerin, pentaerythritol, hexamethylol melamine, and hexaethylol melamine.

  Specific examples of the carboxylic acid include the following. Oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, glutaric acid, 1,13-tridecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 1,16-hexadecanedicarboxylic acid Acid, 1,18-octadecanedicarboxylic acid; 1,1-cyclopentenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,3-adamantanedicarboxylic acid and other alicyclic dicarboxylic acids; phthalates Examples thereof include aromatic dicarboxylic acids such as acid, isophthalic acid, terephthalic acid, naphthalene-1,4-dicarboxylic acid, and naphthalene-1,5-dicarboxylic acid. It is also possible to use a trivalent or higher polyvalent carboxylic acid such as trimellitic acid, pyromellitic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, pyrenetricarboxylic acid, and pyrenetetracarboxylic acid. And polyvalent carboxylic acid.

  From the viewpoint of improving the compatibility with the amorphous resin having an aromatic ring, the crystalline polyester has 10 mol as a structural unit of the unit represented by the formula (1) with respect to all units of the crystalline polyester. % To 100 mol% is preferable. More preferably, it is contained in an amount of 25 mol% or more and 100 mol% or less.

  It is known that a crystalline polyester generally used for toner is a resin having a lower volume resistance than a conventional amorphous resin. The present inventors consider this reason as follows.

  In general, a crystalline resin forms a crystal structure in which molecular chains exhibit a regular arrangement, and when viewed macroscopically, a state in which molecular motion is restricted in a temperature region below the melting point is maintained. Conceivable. However, when viewed microscopically, the crystalline resin is not necessarily composed of a 100% crystal structure part, but a crystal structure part having a crystal structure in which molecular chains exhibit a regular arrangement, and other than that. And an amorphous structure portion. In the case of a crystalline polyester having a melting point in the range normally used for toner, the glass transition temperature (Tg) of the crystalline polyester is much lower than room temperature. It is thought that the amorphous structure part has caused molecular motion. Thus, in an environment where the molecular mobility of the resin is high, it is possible to transfer charges through an ester bond or the like that is a polar group, and as a result, the volume resistance of the resin is considered to decrease. Therefore, since it is presumed that the volume resistance can be increased by keeping the concentration of the ester group that is a polar group low, a resin having a low ester group concentration is preferably used. The concentration value of the ester group is mainly determined by the type of diol and dicarboxylic acid, and can be designed to a low value by selecting one having a large number of carbons.

  The concentration of the ester group in the present invention can be calculated as follows.

Ester group concentration (mass%) = [molecular weight of crystalline polyester structural unit (molecular weight 44) × 2] / [total molecular weight of crystalline polyester structural unit] × 100
The concentration of the ester group in the present invention is preferably 20% by mass or more and 35% by mass or less. From the viewpoint of improving the chargeability, it is preferably 35% by mass or less, and more preferably 32% by mass or less. Moreover, it is preferable that an ester group density | concentration is 20 mass% or more from a compatible viewpoint.

  The structural unit of the crystalline polyester of the present invention can be identified by isolating the crystalline polyester component from the resin contained in the toner and measuring the NMR spectrum. Examples of a method for isolating the crystalline polyester component include a method in which the toner is isolated as a residue by Soxhlet extraction with an ethyl acetate solvent.

  The weight average molecular weight (Mw) measured using the gel permeation chromatography of the crystalline polyester of the present invention is from 5,000 to 50,000, preferably from 5,000 to 20,000.

  When the weight average molecular weight (Mw) of the crystalline polyester is larger than 5000, the strength as a resin is improved and the toner strength is improved. On the other hand, when the weight average molecular weight (Mw) of the crystalline polyester is 50000 or less, the low-temperature fixability as a toner is improved.

  The weight average molecular weight (Mw) of the crystalline polyester can be easily controlled by various known production conditions for the crystalline polyester.

  Moreover, the weight average molecular weight (Mw) of the said crystalline polyester is measured as follows using gel permeation chromatography (GPC).

To o-dichlorobenzene for gel chromatography, special grade 2,6-di-t-butyl-4-methylphenol (BHT) is added so that the concentration becomes 0.10 wt / vol%, and dissolved at room temperature. Crystalline polyester and o-dichlorobenzene to which BHT is added are placed in a sample bottle and heated on a hot plate set at 150 ° C. to dissolve the crystalline polyester. When the crystalline polyester melts, put it in a preheated filter unit and place it on the main body. The sample that has passed through the filter unit is used as a GPC sample. The sample solution is adjusted so that the concentration is about 0.15% by mass. Using this sample solution, measurement is performed under the following conditions.
Apparatus: HLC-8121GPC / HT (manufactured by Tosoh Corporation)
Detector: RI for high temperature
Column: TSKgel GMHHR-H HT 2 series (manufactured by Tosoh Corporation)
Temperature: 135.0 ° C
Solvent: o-dichlorobenzene for gel chromatography
(BHT added at 0.10wt / vol%)
Flow rate: 1.0 ml / min
Injection volume: 0.4ml
In calculating the molecular weight of the crystalline polyester, standard polystyrene resin (for example, trade names “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. .

  Moreover, it is preferable that melting | fusing point of the crystalline polyester of this invention is 40 to 100 degreeC. From the viewpoint of low temperature fixability and storage stability, it is preferably 40 ° C. or higher and 100 ° C. or lower. When the melting point is 100 ° C. or lower, low temperature fixing becomes possible. Further, the melting point is preferably 90 ° C. or lower from the viewpoint of lower temperature fixing. On the other hand, when the melting point is higher than 40 ° C., the storage stability is improved.

  In addition, the said melting | fusing point can be measured using a scanning scanning calorimeter (DSC). Specifically, 0.01 to 0.02 g of the sample is weighed into an aluminum pan, and calorimetry is performed while the sample is heated from room temperature at a heating rate of 10 ° C./min. Then, from the obtained DSC curve, the peak temperature of the endothermic peak is defined as the melting point. Further, the melting point of the crystalline polyester present in the toner can be measured by the same method. At that time, the melting point due to the release agent present in the toner may be observed. Discrimination between the melting point of the release agent and the melting point of the crystalline polyester is obtained by extracting the release agent from the toner by Soxhlet extraction using a hexane solvent, and performing the scanning scanning calorimetry of the release agent alone by the above method. This is done by comparing the melting point of the toner and the melting point of the toner.

  In the present invention, the toner preferably contains 1% by mass to 40% by mass of the crystalline polyester, and from the viewpoint of achieving both low-temperature fixability and chargeability, the toner may contain 10% by mass to 30% by mass. preferable. When the toner contains 1% by mass or more of the crystalline polyester, the low-temperature fixability of the toner is improved. In addition, the toner is improved in chargeability by adjusting the crystalline polyester to 40% by weight or less.

  Next, the amorphous resin having an aromatic ring used in the present invention will be described.

<Amorphous resin having an aromatic ring>
In the present invention, as the amorphous resin having an aromatic ring, a known polymer that is usually used for a toner is used as long as it is an amorphous resin having an aromatic ring and high compatibility with the crystalline polyester. It is possible. Here, the amorphous resin is a resin having an irregular molecular chain and a glass transition temperature but no melting point.

  Specifically, the following polymers can be used.

  Styrene such as polystyrene, poly-p-chlorostyrene, polyvinyltoluene, and homopolymers thereof; styrene-p-chlorostyrene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene -Acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer Styrene copolymers such as styrene-acrylonitrile-indene copolymer, phenol resin, naturally modified phenol resin, acrylic resin, methacrylic resin, polyester, polyurethane, polyamide, furan resin, epoxy resin, xylene resin, polyvinyl chloride Butyral, terpene resins, coumarone - indene resins, and the like. Among these, a polyester having high compatibility with the crystalline polyester and excellent in strength even with a low molecular weight is preferable.

  As the polyester resin having an aromatic ring, a resin obtained by condensation polymerization of an alcohol monomer and / or a carboxylic acid monomer having at least an aromatic ring is used.

  Examples of the alcohol monomer having an aromatic ring include the following. Polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (3.3) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2. 0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (2.0) -polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (6) Alkylene oxide adducts of bisphenol A such as -2,2-bis (4-hydroxyphenyl) propane, bisphenol A, hydrogenated bisphenol A, 1,3,5-trihydroxymethylbenzene, 1,4-benzene Dimethanol, 1,3-benzenedimethanol, 1,2-benzenedimethanol, 1,4-benzenedie 1,3-benzenediethanol, 1,2-benzenediethanol, 1,4-benzenedipropanol, 1,3-benzenedipropanol, 1,2-benzenedipropanol, 1,4-benzenedibutanol, 1, 3-benzenedibutanol, 1,2-benzenedibutanol. These may be used alone or in combination of two or more.

  On the other hand, the following are mentioned as a carboxylic acid monomer which has an aromatic ring. Phthalic acid, isophthalic acid and terephthalic acid, 1,4-phenylenediacetic acid, 1,3-phenylenediacetic acid, 1,2-phenylenediacetic acid, 1,4-phenylenedipropionic acid, 1,3-phenylenedipropionic acid Aromatic dicarboxylic acids such as 1,2-phenylene dipropionic acid, 1,4-phenylene dibutyric acid, 1,3-phenylene dibutyric acid, 1,2-phenylene dibutyric acid, or anhydrides thereof. These may be used alone or in combination of two or more.

  In addition to the monomer having an aromatic ring, the following aliphatic monomers can be used in combination. Examples of the aliphatic alcohol monomer include the following. Ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, 1,4-butenediol, 1,5-pentanediol, 1, 6-hexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol.

  The following are mentioned as an aliphatic carboxylic acid monomer. Alkyldicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid or anhydrides thereof; succinic acid or anhydrides substituted with alkyl or alkenyl groups having 6 to 18 carbon atoms; fumaric acid, maleic acid and citracone Unsaturated dicarboxylic acids such as acids or anhydrides thereof.

  In addition, the following monomers can be used. Glycerin, sorbit, sorbitan, and polyhydric alcohols such as oxyalkylene ethers of novolac-type phenol resins; polyhydric carboxylic acids such as trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid and anhydrides thereof.

  Among these, in particular, a bisphenol derivative represented by the following general formula (3) is a dihydric alcohol monomer component, and a carboxylic acid component comprising a divalent or higher carboxylic acid or an acid anhydride thereof, or a lower alkyl ester thereof ( For example, fumaric acid, maleic acid, maleic anhydride, phthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, etc.) are used as acid monomer components, and resins obtained by condensation polymerization with these polyester unit components are preferable.

(In the formula, R represents an ethylene group or a propylene group, x and y are each an integer of 1 or more, and the average value of x + y is 2 to 10.)
The aromatic ring concentration in the amorphous resin in the present invention can be calculated as follows.

Concentration of aromatic ring (mass%) = [total molecular weight of aromatic ring portion of structural unit of amorphous polyester] / [total molecular weight of structural unit of amorphous polyester] × 100
The concentration of the aromatic ring in the amorphous resin in the present invention is preferably 20% by mass or more and 70% by mass or less. The concentration of the aromatic ring in the amorphous resin is preferably 20% by mass or more, and more preferably 25% by mass or more from the viewpoint of compatibility with the crystalline polyester. The concentration of the aromatic ring in the amorphous resin is preferably 70% by mass or less, and more preferably 65% by mass or less, from the viewpoint of the glass transition temperature of the amorphous resin described later.

  The structural unit of the amorphous resin of the present invention can be identified by isolating the amorphous resin component from the resin contained in the toner and measuring the NMR spectrum. Examples of the method for isolating the amorphous resin component include a method in which the toner is isolated by Soxhlet extraction using an ethyl acetate solvent as the amorphous resin component.

Examples of the compatibility index between the amorphous resin having an aromatic ring and the crystalline polyester include an absolute value (ΔSP value) of a difference in solubility parameter value (SP value) of each resin. The ΔSP value is preferably 0 or more and 1.5 or less, more preferably 0 or more and 1.0 or less, and even more preferably 0 or more and 0.90 or less. The SP value is represented by the Fedors equation. It can be obtained using. Here, the values of Δei and Δvi are the evaporation energy and molar volume of atoms and atomic groups according to Tables 3 to 9 described on pages 54 to 57 of “Basic Science of Coating” (1986 (Tsubaki Shoten)) ( 25 ° C.) ”.
Formula: δi = [Ev / V] ^1/2 = [Δei / Δvi] ^1/2
Ev: Evaporation energy V: Molar volume Δei: Evaporation energy of atom or atomic group of i component Δvi: Molar volume of atom or atomic group of i component For example, a crystalline polyester composed of nonanediol and sebacic acid is used as a repeating unit. It is composed of atomic groups (—COO) × 2 + (— CH ₂ ) × 17, and the calculated SP value is obtained by the following formula.

δi = [Δei / Δvi] ^ (1/2) = [{(4300) × 2 + (1180) × 17} / {(18) × 2 + (16.1) × 17}] ^ (1/2)
The SP value (δi) is 9.63.

  The glass transition temperature of the amorphous resin having an aromatic ring of the present invention is preferably 30 ° C. or higher and 80 ° C. or lower. When the glass transition temperature is higher than 30 ° C., the storage stability is improved. On the other hand, when the glass transition temperature is lower than 80 ° C., the fixability is improved. Further, the glass transition temperature of the amorphous resin having an aromatic ring of the present invention is more preferably 40 ° C. or more from the viewpoint of storage stability, and it is more preferably 70 ° C. or less from the viewpoint of fixability.

  The glass transition temperature (Tg) is measured using DSC (manufactured by METTLER TOLEDO: DSC822 / EK90). Specifically, 0.01 to 0.02 g of a sample is weighed in an aluminum pan, heated to 200 ° C., and the sample cooled from the temperature to −100 ° C. at a temperature decreasing rate of 10 ° C./min is heated up. Calorimetry is performed while raising the temperature at 10 ° C./min. Next, from the obtained DSC curve, the temperature at the intersection of a straight line obtained by extending the base line on the low temperature side to the high temperature side and the tangent line drawn at the point where the slope of the stepped change portion of the glass transition becomes maximum. Is the glass transition temperature.

  In the present invention, the softening temperature (Tm) of the amorphous resin having an aromatic ring is preferably 70 ° C or higher and 150 ° C or lower, more preferably 80 ° C or higher and 140 ° C or lower, and 80 ° C or higher and 130 ° C or lower. More preferably, it is as follows. If Tm is within the above temperature range, both anti-blocking and anti-offset properties can be achieved, and further, the toner melt component can be soaked into the paper at the time of fixing at a high temperature. Surface smoothness is obtained.

  In the present invention, the softening temperature of the amorphous resin having an aromatic ring was measured using a constant-load extrusion type capillary rheometer “Flow Characteristic Evaluation Apparatus Flow Tester CFT-500D” (manufactured by Shimadzu Corporation). The CFT-500D melts while raising the temperature of the measurement sample filled in the cylinder while applying a constant load with the piston from the top and pushes it out from the narrow tube hole at the bottom of the cylinder. It is an apparatus that can graph a flow curve from temperature (° C.).

In the present invention, the “melting temperature in the 1/2 method” described in the manual attached to the “flow characteristic evaluation apparatus Flow Tester CFT-500D” is defined as the softening temperature (Tm).
The melting temperature in the 1/2 method is calculated as follows.
First, ½ of the difference between the piston descent amount (outflow end point, Smax) when the outflow is completed and the piston descent amount (lowest point, Smin) when the outflow starts is obtained. (This is assumed to be X. X = (Smax−Smin) / 2). And the temperature of the flow curve when the amount of piston descent becomes the sum of X and Smin was taken as the melting temperature in the 1/2 method.

The measurement sample is an amorphous resin having an aromatic ring of about 1.2 g under an environment of 25 ° C., using a tablet molding compressor (for example, a standard manual Newton press NT-100H, manufactured by NPA Corporation). Compression molding was performed at about 10 MPa for about 60 seconds. A cylindrical shape having a diameter of about 8 mm was used. The specific operation in the measurement was performed according to the manual attached to the apparatus.
The measurement conditions of CFT-500D are as follows.
Test mode: Temperature rising start temperature: 60 ° C
Achieving temperature: 200 ° C
Measurement interval: 1.0 ° C
Temperature increase rate: 4.0 ° C./min
Piston cross-sectional area: 1.000cm2
Test load (piston load): 5.0 kgf
Preheating time: 300 seconds Die hole diameter: 1.0 mm
Die length: 1.0mm
The toner of the present invention has toner particles containing at least the crystalline polyester and the amorphous resin having an aromatic ring.

  The toner of the present invention can be produced by a known production method such as a pulverization method, suspension polymerization method, emulsion aggregation method, or dissolution suspension method, and the production method is not particularly limited. Hereinafter, the toner production methods in the suspension polymerization method and the emulsion aggregation method are specifically exemplified, but the present invention is not limited thereto.

<Suspension polymerization method>
In the suspension polymerization method, a polymerizable monomer and a crystalline polyester constituting an amorphous resin having an aromatic ring, and other materials such as a colorant and a release agent are uniformly dissolved or dispersed as necessary. Thus, a polymerizable monomer composition is obtained. Thereafter, the polymerizable monomer composition is dispersed in an aqueous medium containing a dispersion stabilizer as necessary using a suitable stirrer. Thereafter, the polymerizable monomer is polymerized to obtain particles having a desired particle size. The toner can be obtained by filtering, washing, and drying the obtained particles by a known method.

  Specific examples of the polymerizable monomer constituting the amorphous resin having an aromatic ring are shown below, but are not limited thereto.

  Styrene, α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, p- Styrene derivatives such as n-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, p-phenyl styrene, vinyl Naphthalene, p-chlorostyrene. These may be used alone or in combination of two or more.

  In addition to the above polymerizable monomers, the following aliphatic polymerizable monomers can be used in combination. Specifically, methyl acrylate, ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate Acrylic polymer such as n-octyl acrylate, n-nonyl acrylate, cyclohexyl acrylate, benzyl acrylate, dimethyl phosphate ethyl acrylate, diethyl phosphate ethyl acrylate, dibutyl phosphate, ethyl acrylate, 2-benzoyloxyethyl acrylate Polymers; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, iso-propyl methacrylate Rate, n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, n-amyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, n-nonyl methacrylate, diethyl phosphate ethyl methacrylate, dibutyl phosphate Methacrylic polymerizable monomers such as fetoethyl methacrylate.

<Emulsion aggregation method>
In the emulsion aggregation method, an aqueous dispersion of fine particles composed of a toner constituent material, which is sufficiently small with respect to the target particle size, is prepared in advance, and the fine particles are aggregated in an aqueous medium until the particle size of the toner is reached. The toner is manufactured by fusing a resin by heating.

  Specifically, at least a crystalline polyester dispersion in which the crystalline polyester is dispersed in an aqueous medium, an amorphous resin dispersion in which the amorphous resin having an aromatic ring is dispersed in an aqueous medium, and a colorant A colorant dispersion is prepared in which is dispersed in an aqueous medium. Furthermore, if necessary, a dispersion step for producing a release agent dispersion in which a release agent is dispersed in an aqueous medium, a mixing step for mixing each dispersion to obtain a mixture, and agglomeration of each fine particle in the mixture Thus, toner particles are manufactured through an aggregation process for forming aggregated particles having a desired particle diameter. After the aggregation process, a fusion process for melting and fusing the resin contained in the obtained aggregated particles and a cooling process are performed.

  Hereinafter, each step of the emulsion aggregation method will be further described.

<Dispersing process>
The aqueous dispersion of the crystalline polyester can be prepared by a known method. Known methods include, for example, a self-emulsification method and a phase inversion emulsification method in which a resin is emulsified by adding an aqueous medium to a resin solution dissolved in a hydrophilic organic solvent. In addition, a resin solution dissolved in a hydrophobic organic solvent is dispersed in an aqueous medium by mechanical shearing, and a high-temperature treatment is performed in an aqueous medium without using an organic solvent. The forced emulsification method of forcibly emulsifying the resin is mentioned.

  Specifically, the crystalline polyester is heated and dissolved in an organic solvent that dissolves at a temperature equal to or higher than the melting point, and then mixed with an aqueous medium in which a surfactant is dissolved. When the crystalline polyester has an acidic polar group such as carboxylic acid, a base such as ammonia may be added as a neutralizing agent as necessary. Subsequently, the resin solution is finely divided with a homogenizer (for example, “Clearmix W motion” manufactured by M Technique Co., Ltd.) or a pressure discharge type disperser (for example, “Gorin homogenizer manufactured by Gorin”) having a strong shearing ability. To disperse. Thereafter, the solvent is removed by heating or decompression to prepare an aqueous dispersion of crystalline polyester fine particles. As the organic solvent used for dissolving the crystalline polyester, any organic solvent can be used as long as it can dissolve the crystalline polyester at a temperature equal to or higher than the melting point. From the viewpoint of solubility in the crystalline polyester and the boiling point of the solvent, tetrahydrofuran, acetone, toluene, and chloroform are preferable.

  The surfactant used at the time of emulsification is not particularly limited, but examples thereof include anionic surfactants such as sulfate ester, sulfonate, carboxylate, phosphate, and soap. Can be mentioned. Also, cationic surfactants such as amine salt type and quaternary ammonium salt type; nonionic surfactants such as polyethylene glycol type, alkylphenol ethylene oxide adduct type, polyhydric alcohol type and the like can be mentioned. These surfactants may be used alone or in combination of two or more.

  The volume-based 50% particle size (d50) of the crystalline polyester fine particles is preferably 0.05 to 1.0 μm, and more preferably 0.05 to 0.4 μm.

  By adjusting the volume-based 50% particle size (d50) to the above range, it becomes easy to obtain toner particles having a volume average particle size of 3 μm or more and 10 μm or less, which are suitable as toner particles. The volume-based 50% particle size (d50) can be measured by using a dynamic light scattering particle size distribution analyzer (Nanotrack UPA-EX150: manufactured by Nikkiso).

  The aqueous dispersion of the amorphous resin having an aromatic ring can be prepared by a known method. Known methods include, for example, an emulsion polymerization method, a self-emulsification method, and a phase inversion emulsification method in which a resin is emulsified by adding an aqueous medium to a resin solution dissolved in a hydrophilic organic solvent. Further, a resin solution dissolved in a hydrophobic organic solvent is dispersed in an aqueous medium by mechanical shearing, and a high-temperature treatment is performed in an aqueous medium without using an organic solvent. The forced emulsification method of forcibly emulsifying the resin is mentioned.

  Specifically, it is dissolved in an organic solvent in which the amorphous resin having an aromatic ring is dissolved and mixed with an aqueous medium in which the surfactant is dissolved. When the amorphous resin having an aromatic ring has an acidic polar group such as carboxylic acid, a base may be added as a neutralizing agent as necessary. Subsequently, the resin solution is finely divided with a homogenizer (for example, “Clearmix W motion” manufactured by M Technique Co., Ltd.) or a pressure discharge type disperser (for example, “Gorin homogenizer manufactured by Gorin”) having a strong shearing ability. To disperse. Thereafter, the solvent is removed by heating or decompression to prepare an aqueous dispersion of resin fine particles. As the organic solvent used for dissolving the amorphous resin having an aromatic ring, any organic solvent can be used as long as it can dissolve the amorphous resin. For example, tetrahydrofuran, acetone, toluene, and chloroform are preferable from the viewpoint of solubility in an amorphous resin and the boiling point of the solvent.

  The surfactant used at the time of emulsification is not particularly limited, but examples thereof include anionic surfactants such as sulfate ester, sulfonate, carboxylate, phosphate, and soap. Can be mentioned. Moreover, an amine salt type, quaternary ammonium salt type cationic surfactant, etc. are mentioned. Further, nonionic surfactants such as polyethylene glycol-based, alkylphenol ethylene oxide adduct-based, polyhydric alcohol-based and the like can be mentioned. These surfactants may be used alone or in combination of two or more.

  The volume-based 50% particle size (d50) of the fine particles of the amorphous resin having an aromatic ring is preferably 0.05 to 1.0 μm, and more preferably 0.05 to 0.4 μm.

  By adjusting the volume-based 50% particle size (d50) to the above range, it becomes easy to obtain toner particles having a volume average particle size of 3 μm or more and 10 μm or less, which are suitable as toner particles. The volume-based 50% particle size (d50) can be measured by using a dynamic light scattering particle size distribution analyzer (Nanotrack UPA-EX150: manufactured by Nikkiso).

  The aqueous dispersion of colorant fine particles can be prepared by the following known methods, but is not limited to these methods.

  It can be prepared by mixing a colorant, an aqueous medium, and a dispersant with a known mixer such as a stirrer, an emulsifier, and a disperser. As the dispersant used here, known ones such as a surfactant and a polymer dispersant can be used.

  Both the surfactant and the polymer dispersant can be removed in the washing step described later, but the surfactant is preferred from the viewpoint of washing efficiency.

  Examples of the surfactant include anionic surfactants such as sulfate ester, sulfonate, phosphate, and soap. In addition, cationic surfactants such as amine salt type and quaternary ammonium salt type may be mentioned. Nonionic surfactants such as polyethylene glycol, alkylphenol ethylene oxide adducts, and polyhydric alcohols are also included.

  Among these, nonionic surfactants or anionic surfactants are preferable. Further, a nonionic surfactant and an anionic surfactant may be used in combination. These surfactants may be used alone or in combination of two or more. The concentration of the surfactant in the aqueous medium is preferably 0.5 to 5% by mass.

  The content of the colorant in the aqueous dispersion of colorant fine particles is not particularly limited, but is preferably 1 to 30% by mass with respect to the total mass of the aqueous dispersion of colorant fine particles.

  The dispersion particle diameter of the colorant fine particles in the aqueous dispersion is such that the volume-based 50% particle diameter (d50) is 0.5 μm or less from the viewpoint of dispersibility of the colorant in the finally obtained toner particles. It is preferable that For the same reason, the volume-based 90% particle size (d90) is preferably 2.0 μm or less. The dispersed particle diameter of the colorant fine particles dispersed in the aqueous medium can be measured by a dynamic light scattering particle size distribution diameter (Nanotrack: manufactured by Nikkiso).

  Known mixers used to disperse the colorant in the aqueous medium include mixers such as an ultrasonic homogenizer, a jet mill, a pressure homogenizer, a colloid mill, a ball mill, a sand mill, and the like. Paint shaker. These may be used alone or in combination.

  The aqueous dispersion of release agent fine particles used as necessary can be prepared by the following known methods, but is not limited to these methods.

  The aqueous dispersion of release agent fine particles is prepared by adding a release agent to an aqueous medium containing a surfactant and heating to a temperature equal to or higher than the melting point of the release agent. A homogenizer (for example, “Clearmix W motion” manufactured by M Technique Co., Ltd.) or a pressure discharge type disperser (for example, “Gorin homogenizer manufactured by Gorin”) having a strong shearing ability can be used. After being dispersed in the form of particles with these apparatuses, it can be produced by cooling to the melting point or lower.

  The dispersion particle diameter of the release agent fine particles in the aqueous dispersion is preferably 0.03 to 1.0 [mu] m, and preferably 0.1 to 0.5 [mu] m, based on a volume-based 50% particle diameter (d50). More preferred. More preferably, there are no coarse particles larger than 1.0 μm.

  When the dispersion particle size of the release agent fine particles is within the above range, release of the release agent at the time of fixing is improved, the hot offset temperature can be increased, and filming on the photosensitive member can be prevented. It becomes possible to suppress. The dispersed particle diameter of the release agent fine particles dispersed in the aqueous medium can be measured by a dynamic light scattering particle size distribution diameter (Nanotrack: manufactured by Nikkiso).

<Mixing process>
In the mixing step, the aqueous dispersion of the crystalline polyester resin fine particles, the aqueous dispersion of the amorphous resin fine particles having an aromatic ring, the aqueous dispersion of the colorant fine particles, and the aqueous release agent fine particles as necessary. A mixed solution is prepared by mixing the dispersion. The order of mixing the fine particles may be any order, and all materials may be mixed at one time. The fine particles can be mixed using a known mixing apparatus such as a homogenizer and a mixer.

<Aggregation process>
In the aggregation step, the fine particles contained in the mixed solution prepared in the mixing step are aggregated to form aggregated particles having a target particle size. At this time, a flocculant is added and mixed, and if necessary, heating and / or mechanical power is appropriately applied to thereby produce crystalline polyester resin fine particles, amorphous resin fine particles having aromatic rings, colorant fine particles, and mold release. Aggregated particles in which the agent particles are aggregated are formed.

  As the flocculant, it is preferable to use a flocculant containing a divalent or higher valent metal ion.

  An aggregating agent containing a divalent or higher valent metal ion has a high aggregating force, and can exhibit an effect when added in a small amount. This aggregating agent can ionically neutralize the particles of the aqueous dispersion of crystalline polyester resin fine particles, amorphous resin fine particles having aromatic rings, colorant fine particles, and release agent fine particles. Furthermore, this flocculant can ionically neutralize the ionic surfactant and the carboxylic acid component contained in the resin. As a result, the crystalline polyester resin fine particles, the amorphous resin fine particles having an aromatic ring, the colorant fine particles, and the release agent fine particles are aggregated by the effects of salting out and ionic crosslinking.

  Examples of the aggregating agent containing a divalent or higher metal ion include a divalent or higher metal salt or a polymer of a metal salt. Specific examples include divalent inorganic metal salts such as calcium chloride, calcium nitrate, magnesium chloride, magnesium sulfate, and zinc chloride. Also, trivalent metal salts such as iron (III) chloride, iron (III) sulfate, aluminum sulfate, and aluminum chloride, and inorganic metal salt weights such as polyaluminum chloride, polyaluminum hydroxide, and calcium polysulfide Coalescence is mentioned. However, it is not limited to these. These may be used alone or in combination of two or more.

  The flocculant may be added in the form of a dry powder or an aqueous solution dissolved in an aqueous medium, but it is preferably added in the form of an aqueous solution in order to cause uniform aggregation.

  Moreover, it is preferable to add and mix the said flocculant at the temperature below the glass transition temperature or melting | fusing point of resin contained in a liquid mixture. By mixing under this temperature condition, aggregation proceeds relatively uniformly. Mixing of the flocculant into the mixed solution can be performed using a known mixing apparatus such as a homogenizer and a mixer.

  As described above, the average particle diameter of the aggregated particles formed in the aggregation process is preferably controlled so that the volume average particle diameter is 3 μm or more and 10 μm or less. The particle size control of the aggregated particles can be easily performed by appropriately adjusting the temperature, the solid content concentration, the concentration of the aggregating agent, and the stirring conditions.

  Further, by adding resin fine particles for forming a shell phase to the dispersion liquid of the aggregated particles obtained in the aggregation step, the resin fine particles can be attached to the surface of the aggregated particles. In the case of forming a shell phase, toner particles having a core-shell structure can be produced by passing through a shell adhesion step and a coalescence step in which resin fine particles are adhered to the surface through a fusion step described later. The resin fine particles for forming the shell phase added here may be resin fine particles having the same structure as the resin contained in the aggregated particles, or may be resin fine particles having a different structure.

<Fusion process>
In the fusion step, an aggregation terminator is added to the dispersion containing the aggregated particles obtained in the aggregation step under the same stirring as in the aggregation step. As the aggregation terminator, there are basic compounds that stabilize the aggregated particles by moving the acidic polar group of the amorphous resin having crystalline polyester or aromatic ring and the acidic polar group of the surfactant to the dissociation side. Can be mentioned. Also included are chelating agents that stabilize the aggregated particles by partially dissociating the ionic bridge between the acidic polar group of the surfactant and the metal ion that is an aggregating agent to form a coordinate bond with the metal ion. It is done. Among these, a chelating agent having a greater effect of stopping aggregation is preferable.

  After the dispersion state of the aggregated particles in the dispersion is stabilized by the action of the aggregation terminator, the aggregated particles are heated to a temperature higher than the glass transition temperature of the amorphous resin having an aromatic ring or the melting point of the crystalline polyester. To merge.

  The chelating agent is not particularly limited as long as it is a known water-soluble chelating agent. Specifically, oxycarboxylic acids such as tartaric acid, citric acid, and gluconic acid, and their sodium salts; iminodic acid (IDA), nitrilotriacetic acid (NTA), and ethylenediaminetetraacetic acid (EDTA), and these Sodium salt of

  The chelating agent coordinates with the metal ions of the aggregating agent present in the dispersion of the agglomerated particles, so that the environment in the dispersion is electrostatically unstable and easily aggregated. It can be changed to a stable state in which further aggregation is unlikely to occur. Thereby, the further aggregation of the aggregated particles in the dispersion can be suppressed and the aggregated particles can be stabilized.

  The chelating agent is effective even when added in a small amount, and toner particles having a sharp particle size distribution can be obtained. Therefore, an organic metal salt having a trivalent or higher carboxylic acid is preferable.

  Toner particles can be obtained by washing, filtering, drying, etc. the particles produced through the fusing step. Then, if necessary, add inorganic fine particles such as silica, alumina, titania, and calcium carbonate, and resin fine particles such as vinyl resin, polyester resin, and silicone resin by applying shearing force in a dry state. Also good. These inorganic fine particles and resin fine particles function as external additives such as fluidity aids and cleaning aids.

<Colorant>
Examples of the colorant of the present invention include known organic pigments or dyes, carbon black, and magnetic powder.

  Examples of cyan colorants include copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, and basic dye lake compounds. Specifically, C.I. I. Pigment blue 1, C.I. I. Pigment blue 7, C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 1, C.I. I. Pigment blue 15: 2, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 60, C.I. I. Pigment blue 62, C.I. I. And CI Pigment Blue 66.

  Examples of the magenta colorant include condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds. Specifically, C.I. I. Pigment red 2, C.I. I. Pigment red 3, C.I. I. Pigment red 5, C.I. I. Pigment red 6, C.I. I. Pigment red 7, C.I. I. Pigment violet 19, C.I. I. Pigment red 23, C.I. I. Pigment red 48: 2, C.I. I. Pigment red 48: 3, C.I. I. Pigment red 48: 4, C.I. I. Pigment red 57: 1, C.I. I. Pigment red 81: 1, C.I. I. Pigment red 122, C.I. I. Pigment red 144, C.I. I. Pigment red 146, C.I. I. Pigment red 166, C.I. I. Pigment red 169, C.I. I. Pigment red 177, C.I. I. Pigment red 184, C.I. I. Pigment red 185, C.I. I. Pigment red 202, C.I. I. Pigment red 206, C.I. I. Pigment red 220, C.I. I. Pigment red 221, C.I. I. Pigment red 254.

  Examples of the yellow colorant include condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds. Specifically, C.I. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 14, C.I. I. Pigment yellow 15, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 62, C.I. I. Pigment yellow 74, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 94, C.I. I. Pigment yellow 95, C.I. I. Pigment yellow 97, C.I. I. Pigment yellow 109, C.I. I. Pigment yellow 110, C.I. I. Pigment yellow 111, C.I. I. Pigment yellow 120, C.I. I. Pigment yellow 127, C.I. I. Pigment yellow 128, C.I. I. Pigment yellow 129, C.I. I. Pigment yellow 147, C.I. I. Pigment yellow 151, C.I. I. Pigment yellow 154, C.I. I. Pigment yellow 155, C.I. I. Pigment yellow 168, C.I. I. Pigment yellow 174, C.I. I. Pigment yellow 175, C.I. I. Pigment yellow 176, C.I. I. Pigment yellow 180, C.I. I. Pigment yellow 181, C.I. I. Pigment yellow 191, C.I. I. Pigment yellow 194.

  Examples of the black colorant include carbon black, magnetic powder, and those prepared in a black color using the yellow colorant, magenta colorant, and cyan colorant.

  These colorants can be used alone or in combination, and further in a solid solution state. The colorant used in the present invention is selected from the viewpoints of hue angle, saturation, brightness, light resistance, OHP transparency, and dispersibility in toner.

  The content of the cyan colorant, the magenta colorant, the yellow colorant, or the black colorant is 1 to 20 parts by mass with respect to 100 parts by mass of the crystalline polyester and the amorphous resin that constitute the toner particles. preferable.

<Release agent>
Examples of the release agent of the present invention include low molecular weight polyolefins such as polyethylene; silicones having a melting point (softening point) upon heating; fatty acid amides such as oleic acid amide, erucic acid amide, ricinoleic acid amide, and stearic acid amide; Ester waxes such as stearyl stearate; plant waxes such as carnauba wax, rice wax, candelilla wax, tree wax, jojoba oil; animal waxes such as beeswax; montan wax, ozokerite, ceresin, paraffin wax, microcrystalline wax , Mineral-petroleum waxes such as Fischer-Tropsch wax and ester wax; and modified products thereof.

  The content of the release agent is preferably 1 to 25 parts by mass with respect to 100 parts by mass of the crystalline polyester and the amorphous resin which are the resins constituting the toner particles. When the amount is less than 1 part by mass, the fixability at high temperature becomes insufficient, and when it exceeds 25 parts by mass, the toner surface layer may be exposed.

[Example]
Hereinafter, although the present invention is explained still in detail using an example and a comparative example, the mode of the present invention is not limited to these. In addition, all the parts and% of an Example and a comparative example are mass references | standards unless there is particular notice.

(Manufacture of resin)
<Production of crystalline polyester 1>
Dicarboxylic acid component:
1,8-octanedicarboxylic acid 100 mol parts diol component:
200 parts by mole of 1,4-benzenedimethanol The above monomer component is charged into a two-necked flask that has been sufficiently dried by heating, and 0.10 parts by weight of tetraisopropyl orthotitanate is added to 100 parts by weight of the mixture. Nitrogen gas was introduced into the reactor and the temperature was raised while maintaining an inert atmosphere, followed by a condensation polymerization reaction at 230 ° C. Further, the temperature was raised to 250 ° C. under reduced pressure to obtain crystalline polyester 1 (weight average molecular weight [Mw]: 21000, melting point [Mp]: 85 ° C.). The physical property values of the obtained crystalline polyester 1 are shown in Table 1.

<Production of crystalline polyester 2>
A crystalline polyester 2 (Mw: 21500, melting point: 79 ° C.) was obtained in the same manner as in the production of the crystalline polyester 1 except that 1,8-hexanedicarboxylic acid was changed to 1,6-octanedicarboxylic acid. The physical property values of the obtained crystalline polyester 2 are shown in Table 1.

<Production of crystalline polyester 3>
Crystalline polyester 3 (Mw: 20500, melting point: 91 ° C.) was obtained in the same manner as in the production of crystalline polyester 1, except that 1,8-octanedicarboxylic acid was changed to 1,10-decanedicarboxylic acid. The physical property values of the obtained crystalline polyester 3 are shown in Table 1.

<Production of crystalline polyester 4>
Crystalline polyester 4 (Mw: 19500, melting point: 102 ° C.) was obtained in the same manner as in the production of crystalline polyester 1, except that 1,8-octanedicarboxylic acid was changed to 1,12-dodecanedicarboxylic acid. The physical property values of the obtained crystalline polyester 4 are shown in Table 1.

<Production of crystalline polyester 5>
A crystalline polyester 5 (Mw: 22500, melting point: 70 ° C.) was obtained in the same manner as in the production of the crystalline polyester 1 except that 1,8-octanedicarboxylic acid was changed to adipic acid. The physical property values of the obtained crystalline polyester 5 are shown in Table 1.

<Production of crystalline polyester 6>
The crystalline polyester 6 (Mw: 17900) was prepared in the same manner as in the production of the crystalline polyester 1 except that 1,8-octanedicarboxylic acid was changed to adipic acid and 1,4-benzenedimethanol was changed to 1,4-benzenediethanol. , Melting point: 76 ° C.). The physical property values of the obtained crystalline polyester 6 are shown in Table 1.

<Production of crystalline polyester 7>
Crystalline polyester 7 (Mw: Mw :) except that 1,8-octanedicarboxylic acid was changed to phenylenediacetic acid and 1,4-benzenedimethanol was changed to 1,6-hexanediol 16600, melting point: 77 ° C.). The physical property values of the obtained crystalline polyester 7 are shown in Table 1.

<Production of crystalline polyester 8>
Dicarboxylic acid component:
1,8-octanedicarboxylic acid 100 mol parts diol component:
1,4-benzenedimethanol 150 mol parts 1,8-octanediol 50 mol parts The above-mentioned monomer component was put into a well-heated and dried two-necked flask, and tetraisopropyl orthotitanate was added to 100 parts by mass of the mixture. .10 parts by mass was added, and the temperature was raised while introducing nitrogen gas into the container while maintaining an inert atmosphere, followed by condensation polymerization reaction at 230 ° C. Further, the temperature was raised to 250 ° C. under reduced pressure to obtain crystalline polyester 8 (weight average molecular weight [Mw]: 20900, melting point [Mp]: 83 ° C.). The physical property values of the obtained crystalline polyester 1 are shown in Table 1.

<Production of crystalline polyester 9>
Crystalline polyester 9 (similar to the production of crystalline polyester 8) except that 150 mol parts of 1,4-benzenedimethanol was changed to 100 mol parts and 50 mol parts of 1,8-octanediol was changed to 100 mol parts. Mw: 17000, melting point: 81 ° C.). The physical property values of the obtained crystalline polyester 9 are shown in Table 1.

<Production of crystalline polyester 10>
150 mol parts of 1,4-benzenedimethanol was changed to 100 mol parts, and 50 mol parts of 1,8-octanediol was changed to 100 mol parts of 1,2-octanediol. Otherwise in the same manner as in the production of crystalline polyester 8, crystalline polyester 10 (Mw: 10,000, melting point: 53 ° C.) was obtained. The physical property values of the obtained crystalline polyester 10 are shown in Table 1.

<Production of crystalline polyester 11>
Dicarboxylic acid component:
Adipic acid 100 mol parts diol component:
200 parts by weight of 1,6-hexanediol The above monomer component is put into a two-necked flask that has been sufficiently heated and dried, and 0.10 parts by weight of tetraisopropyl orthotitanate is added to 100 parts by weight of the above mixture. Nitrogen gas was introduced and the temperature was raised while maintaining an inert atmosphere, followed by a condensation polymerization reaction at 230 ° C. Further, the temperature was raised to 250 ° C. under reduced pressure to obtain crystalline polyester 11 (weight average molecular weight [Mw]: 15600, melting point [Mp]: 60 ° C.). The physical property values of the obtained crystalline polyester 11 are shown in Table 1.

<Production of crystalline polyester 12>
Crystalline polyester 11 (Mw: 18900, Mw: 18900), except that adipic acid was changed to 1,12-dodecanedicarboxylic acid and 1,6-hexanediol was changed to 1,8-octanediol Melting point: 89 ° C.). The physical property values of the obtained crystalline polyester 12 are shown in Table 1.

<Production of crystalline polyester 13>
Crystalline polyester 12 (Mw: 14900, melting point: 128 ° C.) as in the production of crystalline polyester 11 except that adipic acid was changed to terephthalic acid and 1,6-hexanediol was changed to 1,8-octanediol Got. The physical property values of the obtained crystalline polyester 13 are shown in Table 1.

<Production of crystalline polyester 14>
Dicarboxylic acid component:
1,12-dodecanedicarboxylic acid 90 mol parts terephthalic acid 10 mol parts diol component:
200 parts by mole of 1,8-octanediol The above monomer component is put into a two-necked flask that has been sufficiently heated and dried, and 0.10 parts by weight of tetraisopropyl orthotitanate is added to 100 parts by weight of the mixture. Nitrogen gas was introduced and the temperature was raised while maintaining an inert atmosphere, followed by a condensation polymerization reaction at 230 ° C. Further, the temperature was raised to 250 ° C. under reduced pressure to obtain crystalline polyester 14 (weight average molecular weight [Mw]: 18600, melting point [Mp]: 95 ° C.). The physical property values of the obtained crystalline polyester 14 are shown in Table 1.

<Production of amorphous polyester resin 1 having an aromatic ring>
Dicarboxylic acid component:
Dimethyl terephthalate 100 mole part diol component:
Polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl) propane
100 mol parts Into a two-necked flask that has been sufficiently heated and dried, the above monomer components are added, 0.10 parts by mass of tetraisopropyl orthotitanate is added to 100 parts by mass of the above mixture, and nitrogen gas is introduced into the container. The temperature was raised while maintaining an inert atmosphere, and then a condensation polymerization reaction was carried out at 230 ° C. The amorphous polyester resin 1 (weight average molecular weight [Mw]: 18600, glass transition temperature [Tg]: 60 ° C.) having an aromatic ring was obtained by further reducing the pressure and raising the temperature to 250 ° C.

<Production of amorphous polyester resin 2 having an aromatic ring>
Dicarboxylic acid component:
Dimethyl fumarate 100 mole part diol component:
Polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl) propane
100 mol parts Into a two-necked flask that has been sufficiently heated and dried, the above monomer components are added, 0.10 parts by mass of tetraisopropyl orthotitanate is added to 100 parts by mass of the above mixture, and nitrogen gas is introduced into the container. The temperature was raised while maintaining an inert atmosphere, and then a condensation polymerization reaction was carried out at 230 ° C. The amorphous polyester resin 2 (weight average molecular weight [Mw]: 25200, glass transition temperature [Tg]: 55 ° C.) having an aromatic ring was obtained by further reducing the pressure and raising the temperature to 250 ° C.

<Production of dispersion of crystalline polyester 1>
120 parts by mass of crystalline polyester 1 was added to 200 parts by mass of toluene (manufactured by Wako Pure Chemical Industries, Ltd.), heated to 95 ° C., and stirred for 3 hours to dissolve. In a toluene solution in which crystalline polyester 1 is dissolved, 12 parts by mass of an anionic surfactant (Daiichi Kogyo Seiyaku: Neogen RK) and 6 parts by mass of an anionic surfactant (Nippon Yushi Co., Ltd .: Non-Sal LN1) are dissolved at 80 ° C. 360 parts by mass of ion-exchanged water was added. Thereafter, this dispersion was added to an ultra-high speed stirring device T.I. K. The mixture was sufficiently stirred at 4000 rpm using Robomix (manufactured by Primemics). Then, after disperse | distributing for about 1 hour using the high pressure impact type | formula disperser nanomizer (made by Yoshida Kikai Kogyo), toluene was removed using the evaporator and the dispersion liquid of the crystalline polyester 1 was obtained.

  The volume-based 50% particle diameter (d50) of the crystalline polyester 1 fine particles was measured using a dynamic light scattering particle size distribution diameter (Nanotrack: Nikkiso Co., Ltd.) and found to be 0.19 μm.

<Production of dispersion of crystalline polyester 2-14>
A crystalline polyester 2-14 dispersion was obtained in the same manner as the crystalline polyester 1 dispersion except that the crystalline polyester 1 was changed to the crystalline polyester 2-14.

<Manufacture of dispersion liquid of amorphous polyester resin 1 having aromatic ring>
Tetrahydrofuran (manufactured by Wako Pure Chemical Industries) 200 parts by weight Amorphous polyester resin 1 having an aromatic ring 120 parts by weight Anionic surfactant (Daiichi Kogyo Seiyaku: Neogen RK) 0.6 parts by weight And dissolved.

  Next, 25 parts by mass of a 1 mol / L aqueous ammonia solution was added. K. The mixture was stirred at 4000 rpm using Robomix (manufactured by Primemics).

  Furthermore, 360 parts by mass of ion-exchanged water was added at a rate of 1 g / min to precipitate resin fine particles. Thereafter, tetrahydrofuran was removed using an evaporator to obtain a dispersion of amorphous polyester resin 1 having an aromatic ring.

  The volume distribution standard 50% particle size (d50) of the fine particles of the amorphous polyester resin 1 having an aromatic ring was measured using a dynamic light scattering particle size distribution meter (Nanotrack: manufactured by Nikkiso). .13 μm.

<Manufacture of dispersion liquid of amorphous polyester resin 2 having aromatic ring>
Amorphous polyester resin 1 is produced in the same manner as the dispersion of amorphous polyester resin 1 having an aromatic ring, except that amorphous polyester resin 1 having an aromatic ring is changed to amorphous polyester resin 2 having an aromatic ring. A dispersion of Resin 2 was obtained.

<Manufacture of dispersion of cyclic polyolefin resin (amorphous resin containing no aromatic ring)>
To 200 parts by mass of toluene (manufactured by Wako Pure Chemical Industries, Ltd.), 120 parts by mass of cyclic polyolefin resin (manufactured by Polyplastics: TOPAS ™) was added as an amorphous resin not containing an aromatic ring, and the mixture was stirred for 3 hours to dissolve. Ion-exchanged water 360 in which 12 parts by mass of an anionic surfactant (Daiichi Kogyo Seiyaku: Neogen RK) and 6 parts by mass of an anionic surfactant (Nippon Yushi Co., Ltd .: Non-Sal LN1) are dissolved in a toluene solution in which a cyclic polyolefin resin is dissolved. Part by weight was added. Thereafter, an ultra-high speed stirring device T.I. K. The mixture was sufficiently stirred at 4000 rpm using Robomix (manufactured by Primemics). Then, after disperse | distributing for about 1 hour using the high pressure impact type | formula disperser nanomizer (made by Yoshida Kikai Kogyo), toluene was removed using the evaporator and the dispersion liquid of cyclic polyolefin resin was obtained.

  The volume-based 50% particle diameter (d50) of the cyclic polyolefin resin fine particles was measured using a dynamic light scattering particle size distribution diameter (Nanotrack: Nikkiso Co., Ltd.) and found to be 0.19 μm.

<Manufacture of colorant fine particles>
Coloring agent 10.0 parts by mass (Cyan pigment, manufactured by Dainichi Seika: Pigment Blue 15: 3)
・ Anionic surfactant (Daiichi Kogyo Seiyaku: Neogen RK) 1.5 parts by mass ・ Ion-exchange water 88.5 parts by mass A dispersion of colorant fine particles prepared by dispersing the colorant for about 1 hour was prepared.

  The volume distribution standard 50% particle size (d50) of the obtained colorant fine particles was measured using a dynamic light scattering particle size distribution meter (Nanotrack: Nikkiso Co., Ltd.) and found to be 0.20 μm.

<Manufacture of release agent fine particles>
Mold release agent (HNP-51, melting point 78 ° C., manufactured by Nippon Seiwa) 20.0 parts by mass Anionic surfactant (Daiichi Kogyo Seiyaku: Neogen RK) 1.0 part by mass Ion-exchanged water 79. After 0 parts by mass or more was put into a mixing vessel equipped with a stirrer, it was heated to 90 ° C. and circulated to Claremix W-Motion (M Technique). The mixture was stirred for 60 minutes at a shear stirring portion having a rotor outer diameter of 3 cm and a clearance of 0.3 mm under the conditions of a rotor rotation speed of 19000 r / min and a screen rotation speed of 19000 r / min.

  Then, the dispersion liquid of mold release agent microparticles | fine-particles was obtained by cooling to 40 degreeC on the cooling process conditions of rotor rotation speed 1000r / min, screen rotation speed 0r / min, and cooling rate 10 degreeC / min.

  The 50% particle size (d50) based on the volume distribution of the release agent fine particles was measured using a dynamic light scattering particle size distribution meter (Nanotrack: manufactured by Nikkiso Co., Ltd.), and was 0.15 μm.

<Production Example 1 of Toner Particles>
Amorphous polyester resin 1 dispersion 320 parts by weight Crystalline polyester 1 dispersion 80 parts by weight Colorant fine particle dispersion 50 parts by weight Release agent fine particle dispersion 50 parts by weight ion-exchanged water 400 Part by mass After each material described above was charged and mixed in a round stainless steel flask, an aqueous solution in which 2 parts by mass of magnesium sulfate was dissolved was added to 98 parts by mass of ion-exchanged water. And this solution was disperse | distributed for 10 minutes at 5000 r / min using the homogenizer (the product made by IKA: Ultra Talux T50).

  Thereafter, the mixture was heated to 55 ° C. using a stirring blade in a heating water bath while appropriately adjusting the number of revolutions so that the mixture was stirred. Holding at 55 ° C. for 1 hour, aggregated particles having a volume average particle diameter of about 6.0 μm were obtained. An aqueous solution in which 20 parts by mass of trisodium citrate was dissolved in 380 parts by mass of ion-exchanged water was added to the dispersion containing the aggregated particles, and then heated to 85 ° C. After being held at 90 ° C. for 2 hours, the obtained particles had a volume average particle size of about 5.8 μm and an average circularity of 0.968, and sufficiently fused toner particles were obtained.

  The average circularity was calculated by performing measurement according to an operation manual of the apparatus using a flow type particle image measuring apparatus “FPIA-3000” (manufactured by Sysmex Corporation).

  Thereafter, the mixture is cooled to 25 ° C. with stirring, and after filtration and solid-liquid separation, the filtrate is sufficiently washed with ion-exchanged water and dried using a vacuum dryer, so that the volume average particle size is 5.5 μm. Toner particles 1 were obtained. The formulation and characteristics of toner particles 1 are shown in Table 2.

<Toner Particle Production Example 2>
Toner particles 2 were obtained in the same manner as in Example 1 except that the dispersion of crystalline polyester 1 was changed to the dispersion of crystalline polyester 2. The obtained toner particles 2 had a volume average particle size of 5.5 μm. The formulation and properties of toner particles 2 are shown in Table 2.

<Production Example 3 of Toner Particles>
The toner is the same as in Example 1 except that the dispersion of the crystalline polyester 1 is changed to the dispersion of the crystalline polyester 3 and the heating temperature in the fusion process is changed from 90 ° C. to 95 ° C. Particle 3 was obtained. The obtained toner particles 3 had a volume average particle size of 5.4 μm. Table 2 shows the formulation and characteristics of the toner particles 3.

<Toner Particle Production Example 4>
The toner particles 4 were prepared in the same manner as in Example 1 except that the dispersion of the crystalline polyester 1 was changed to the dispersion of the crystalline polyester 4 and the heating temperature in the fusion process was changed from 90 ° C. to 100 ° C. Obtained. The obtained toner particles 4 had a volume average particle size of 5.4 μm. Table 2 shows the formulation and characteristics of the toner particles 3.

<Toner Particle Production Example 5>
Toner particles 5 were obtained in the same manner as in Example 1 except that the dispersion of crystalline polyester 1 was changed to the dispersion of crystalline polyester 5. The obtained toner particles 5 had a volume average particle size of 5.5 μm. Table 2 shows the formulation and characteristics of the toner particles 5.

<Toner Particle Production Example 6>
Toner particles 6 were obtained in the same manner as in Example 1 except that the dispersion of crystalline polyester 1 was changed to the dispersion of crystalline polyester 6. The obtained toner particles 6 had a volume average particle size of 5.5 μm. Table 2 shows the formulation and characteristics of the toner particles 6.

<Toner Particle Production Example 7>
Toner particles 7 were obtained in the same manner as in Example 1, except that the crystalline polyester 1 dispersion was changed to the crystalline polyester 7 dispersion. The obtained toner particles 7 had a volume average particle size of 5.5 μm. Table 2 shows the formulation and characteristics of the toner particles 7.

<Production Example 8 of Toner Particles>
Toner particles 8 were obtained in the same manner as in Example 1 except that the dispersion of crystalline polyester 1 was changed to the dispersion of crystalline polyester 8. The obtained toner particles 8 had a volume average particle size of 5.5 μm. Table 2 shows the formulation and characteristics of the toner particles 8.

<Production Example 9 of Toner Particles>
Toner particles 9 were obtained in the same manner as in Example 1 except that the dispersion of crystalline polyester 1 was changed to the dispersion of crystalline polyester 9. The obtained toner particles 9 had a volume average particle size of 5.5 μm. Table 2 shows the formulation and characteristics of the toner particles 9.

<Toner Particle Production Example 10>
The toner particles 10 are obtained in the same manner as in Example 1 except that the dispersion of the crystalline polyester 1 is changed to the dispersion of the crystalline polyester 10 and the temperature of the aggregation process is changed from 55 ° C. to 48 ° C. It was. The obtained toner particles 9 had a volume average particle size of 5.5 μm. Table 2 shows the formulation and characteristics of the toner particles 10.

<Toner Particle Production Example 11>
Toner particles 11 were obtained in the same manner as in Example 1 except that the dispersion of amorphous polyester 1 was changed to a dispersion of amorphous polyester 2 and the temperature of the aggregation process was changed from 55 ° C. to 53 ° C. Got. The obtained toner particles 11 had a volume average particle size of 5.5 μm. Table 2 shows the formulation and characteristics of the toner particles 11.

<Toner Particle Production Example 12>
-Amorphous polyester resin 1 dispersion 285 parts by weight-Crystalline polyester 1 dispersion 115 parts by weight-Colorant fine particle dispersion 50 parts by weight-Release agent fine particle dispersion 50 parts by weight-Ion exchange water 400 Part by mass After each material described above was charged and mixed in a round stainless steel flask, an aqueous solution in which 2 parts by mass of magnesium sulfate was dissolved was added to 98 parts by mass of ion-exchanged water. And this dispersion | distribution aqueous solution was disperse | distributed for 10 minutes at 5000 r / min using the homogenizer (the product made by IKA: Ultra Turrax T50).

  Thereafter, the mixture was heated to 55 ° C. using a stirring blade in a heating water bath while appropriately adjusting the number of revolutions so that the mixture was stirred. Holding at 55 ° C. for 1 hour, aggregated particles having a volume average particle diameter of about 6.0 μm were obtained. An aqueous solution in which 20 parts by mass of trisodium citrate was dissolved in 380 parts by mass of ion-exchanged water was added to the dispersion containing the aggregated particles, and then heated to 85 ° C. After being held at 90 ° C. for 2 hours, the obtained particles had a volume average particle size of about 5.8 μm and an average circularity of 0.968, and sufficiently fused toner particles were obtained.

  The average circularity was calculated by performing measurement according to an operation manual of the apparatus using a flow type particle image measuring apparatus “FPIA-3000” (manufactured by Sysmex Corporation).

  Thereafter, after filtration and solid-liquid separation, the residue was sufficiently washed with ion-exchanged water and dried using a vacuum dryer to obtain toner particles 12 having a volume average particle size of 5.5 μm. Table 2 shows the formulation and characteristics of the toner particles 12.

<Toner Particle Production Example 13>
-Amorphous polyester resin 1 dispersion 350 parts by weight-Crystalline polyester 1 dispersion 50 parts by weight-Colorant fine particle dispersion 50 parts by weight-Release agent fine particle dispersion 50 parts by weight-Ion exchange water 400 Part by mass After each material described above was charged and mixed in a round stainless steel flask, an aqueous solution in which 2 parts by mass of magnesium sulfate was dissolved was added to 98 parts by mass of ion-exchanged water. And this dispersion liquid was disperse | distributed for 10 minutes at 5000 r / min using the homogenizer (the product made by IKA: Ultra Talux T50).

  Thereafter, the mixture was heated to 55 ° C. using a stirring blade in a heating water bath while appropriately adjusting the number of revolutions so that the mixture was stirred. Holding at 55 ° C. for 1 hour, aggregated particles having a volume average particle diameter of about 6.0 μm were obtained. An aqueous solution in which 20 parts by mass of trisodium citrate was dissolved in 380 parts by mass of ion-exchanged water was added to the dispersion containing the aggregated particles, and then heated to 90 ° C. After maintaining at 90 ° C. for 4 hours, the obtained particles had a volume average particle diameter of about 5.8 μm and an average circularity of 0.968, and thus fully fused toner particles were obtained.

  The average circularity was calculated by performing measurement according to an operation manual of the apparatus using a flow type particle image measuring apparatus “FPIA-3000” (manufactured by Sysmex Corporation).

  Thereafter, the mixture is cooled to 25 ° C. with stirring, and after filtration and solid-liquid separation, the filtrate is sufficiently washed with ion-exchanged water and dried using a vacuum dryer, so that the volume average particle size is 5.5 μm. Toner particles 13 were obtained. Table 2 shows the formulation and characteristics of the toner particles 13.

<Toner Particle Production Example 14>
18.0 parts by mass of a cyan pigment (manufactured by Dainichi Seika: Pigment Blue 15: 3) as a colorant, 180 parts by mass of styrene as a polymerizable monomer, and 130 parts by mass of glass beads (1 mm in diameter) were mixed in an attritor. . It was dispersed for 3 hours with an attritor [manufactured by Nihon Coke Kogyo Co., Ltd.] and filtered through a mesh to obtain a colorant dispersion in which the colorant was dispersed in the polymerizable monomer.
-Colorant dispersion 132 parts by mass-Styrene 44 parts by mass-N-butyl acrylate 36 parts by mass-Release agent (HNP-51, melting point 78 ° C, manufactured by Nippon Seiwa) 25 parts by mass-Aluminum salicylate compound 2 parts by mass ( Bontron E-88, manufactured by Orient Chemical Co.)
-Divinylbenzene 0.1 part by mass-Amorphous polyester resin 1 10 parts by mass-Crystalline polyester 1 36 parts by mass K. 710 parts by mass of ion-exchanged water and 450 parts by mass of 0.1 mol / L-Na ₃ PO ₄ aqueous solution were added to a 2-liter four-necked flask equipped with a homomixer [manufactured by Primix Co., Ltd.], and the rotational speed was adjusted to 12000 rpm. And heated to 60 ° C.

To this, 68 parts by mass of 1.0 mol / L-CaCl ₂ aqueous solution was gradually added to prepare an aqueous medium containing a minute hardly water-soluble dispersion stabilizer Ca ₃ (PO ₄ ) ₂ .

  Next, the above composition was heated to 60 ° C. K. Using a homomixer [manufactured by Primix Co., Ltd.], the mixture was uniformly dissolved and dispersed at 5000 rpm.

To this was added 10 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator, and the mixture was put into the aqueous medium and granulated for 15 minutes while maintaining the rotation speed of 12000 rpm. Thereafter, the stirrer is changed from a high-speed stirrer to a propeller stirring blade, the polymerization is continued for 5 hours at a liquid temperature of 60 ° C., and then the temperature of the liquid is increased to 80 ° C. and the polymerization is continued for 8 hours to obtain toner particles. It was. Thereafter, the mixture was cooled to 25 ° C. with stirring, diluted hydrochloric acid was added, and the mixture was stirred at pH 1.5 for 2 hours to dissolve a compound of phosphoric acid and calcium containing Ca ₃ (PO ₄ ) ₂ . Thereafter, solid-liquid separation was performed with a filter to obtain toner particles.

This was poured into water and stirred to obtain a dispersion again, followed by solid-liquid separation with a filter. The redispersion of toner particles in water and solid-liquid separation were repeated until the phosphoric acid and calcium compound containing Ca ₃ (PO ₄ ) ₂ was sufficiently removed.

  Thereafter, the toner particles finally solid-liquid separated were sufficiently dried with a dryer to obtain toner particles 14 having a volume average particle diameter of 7.2 μm. Table 2 shows the formulation and characteristics of the toner particles 14.

<Toner Particle Production Example 15>
-Amorphous polyester resin 1 dispersion 320 parts by weight-Crystalline polyester 11 dispersion 80 parts by weight-Colorant fine particle dispersion 50 parts by weight-Release agent fine particle dispersion 50 parts by weight-Ion exchange water 400 Part by mass After each material described above was charged and mixed in a round stainless steel flask, an aqueous solution in which 2 parts by mass of magnesium sulfate was dissolved was added to 98 parts by mass of ion-exchanged water. And this dispersion | distribution aqueous solution was disperse | distributed for 10 minutes at 5000 r / min using the homogenizer (the product made by IKA: Ultra Turrax T50).

  Thereafter, the mixture was heated to 55 ° C. using a stirring blade in a heating water bath while appropriately adjusting the number of revolutions so that the mixture was stirred. Holding at 55 ° C. for 1 hour, aggregated particles having a volume average particle diameter of about 6.0 μm were obtained. An aqueous solution in which 20 parts by mass of trisodium citrate was dissolved in 380 parts by mass of ion-exchanged water was added to the dispersion containing the aggregated particles, and then heated to 85 ° C. After being held at 75 ° C. for 2 hours, the obtained particles had a volume average particle size of about 5.8 μm and an average circularity of 0.968, and sufficiently fused toner particles were obtained.

  The average circularity was calculated by performing measurement according to an operation manual of the apparatus using a flow type particle image measuring apparatus “FPIA-3000” (manufactured by Sysmex Corporation).

  Thereafter, the mixture is cooled to 25 ° C. with stirring, and after filtration and solid-liquid separation, the filtrate is sufficiently washed with ion-exchanged water and dried using a vacuum dryer, so that the volume average particle size is 5.5 μm. Toner particles 15 were obtained. Table 2 shows the formulation and characteristics of the toner particles 15.

<Toner Particle Production Example 16>
The dispersion of crystalline polyester 11 was changed to a dispersion of crystalline polyester 12, and the heating temperature in the fusion process was changed from 75 ° C. to 90 ° C. Except for this, toner particles 16 were obtained in the same manner as in Production Example 15. The obtained toner particles 16 had a volume average particle size of 5.4 μm. Table 2 shows the formulation and characteristics of the toner particles 16.

<Toner Particle Production Example 17>
-Amorphous polyester resin 1 dispersion 320 parts by weight-Crystalline polyester 13 dispersion 80 parts by weight-Colorant fine particle dispersion 50 parts by weight-Release agent fine particle dispersion 50 parts by weight-Ion exchange water 400 Part by mass After each material described above was charged and mixed in a pressure-resistant round bottom stainless steel container, an aqueous solution in which 2 parts by mass of magnesium sulfate was dissolved was added to 98 parts by mass of ion-exchanged water. And this dispersion | distribution aqueous solution was disperse | distributed for 10 minutes at 5000 r / min using the homogenizer (the product made by IKA: Ultra Turrax T50). Thereafter, the mixture was heated to 58 ° C. using a stirring blade in a heating water bath while appropriately adjusting the number of revolutions so that the mixed solution was stirred. After maintaining at 58 ° C. for 1 hour, the volume average particle diameter of the formed aggregated particles was measured using a flow type particle image analyzer (manufactured by Sysmex Corporation: FPIA-3000) according to the operation manual of the apparatus. As a result, it was confirmed that aggregated particles having a volume average particle diameter of about 6.0 μm were formed. After adding an aqueous solution in which 20 parts by mass of trisodium citrate is dissolved in 380 parts by mass of ion-exchanged water to the dispersion of aggregated particles obtained in the aggregation process, the above pressure-resistant round bottom stainless steel container is sealed, The dispersion liquid of the aggregated particles in the container was heated and pressurized to 110 ° C. and 0.18 MPa. After maintaining at 110 ° C. for 5 hours, the volume average particle diameter and average circularity of the obtained particles were measured using a flow type particle image analyzer (manufactured by Sysmex Corporation: FPIA-3000) according to the operation manual of the apparatus. did. As a result, a sufficiently fused toner having a volume average particle diameter of about 5.8 μm and an average circularity of 0.950 was obtained. Thereafter, the mixture is cooled to 25 ° C. with stirring, and after filtration and solid-liquid separation, the filtrate is sufficiently washed with ion-exchanged water and dried using a vacuum dryer, whereby the volume-based median diameter is 5. 8 μm toner particles 17 were obtained. Table 2 shows the formulation and characteristics of the toner particles 17 obtained.

<Toner Particle Production Example 18>
The dispersion of crystalline polyester 11 was changed to a dispersion of crystalline polyester 14, and the heating temperature in the fusion process was changed from 75 ° C. to 100 ° C. Except for this, toner particles 18 were obtained in the same manner as in Example 14. The obtained toner particles 18 had a volume average particle size of 5.4 μm. Table 2 shows the formulation and characteristics of the toner particles 18.

<Toner Production Example 19 (Toner using amorphous resin not containing aromatic ring)>
-Dispersion liquid of cyclic polyolefin resin 320 parts by weight-Dispersion liquid of crystalline polyester 1 80 parts by weight-Dispersion liquid of colorant fine particles 50 parts by weight-Dispersion liquid of release agent fine particles 50 parts by weight-400 parts by weight of ion-exchanged water Each material was put into a pressure-resistant round bottom stainless steel container and mixed, and then an aqueous solution in which 8 parts by mass of magnesium sulfate was dissolved in 98 parts by mass of ion-exchanged water was added. And this dispersion | distribution aqueous solution was disperse | distributed for 10 minutes at 5000 r / min using the homogenizer (the product made by IKA: Ultra Turrax T50). Thereafter, the mixture was heated to 53 ° C. using a stirring blade in a heating water bath while appropriately adjusting the number of revolutions so that the mixture was stirred. After maintaining at 53 ° C. for 1 hour, the volume average particle diameter of the formed aggregated particles was measured using a flow type particle image analyzer (manufactured by Sysmex Corporation: FPIA-3000) according to the operation manual of the apparatus. As a result, it was confirmed that aggregated particles having a volume average particle diameter of about 6.0 μm were formed. An aqueous solution in which 20 parts by mass of trisodium citrate was dissolved in 380 parts by mass of ion-exchanged water was added to the dispersion of aggregated particles obtained in the aggregation process, and then the mixture was heated to 100 ° C. After maintaining at 100 ° C. for 5 hours, the volume average particle diameter and average circularity of the obtained particles were measured using a flow type particle image analyzer (manufactured by Sysmex Corporation: FPIA-3000) according to the operation manual of the apparatus. did. As a result, a sufficiently fused toner having a volume average particle diameter of about 5.8 μm and an average circularity of 0.948 was obtained. Thereafter, the mixture is cooled to 25 ° C. with stirring, and after filtration and solid-liquid separation, the filtrate is sufficiently washed with ion-exchanged water and dried using a vacuum dryer, whereby the volume-based median diameter is 5. 8 μm toner particles 19 were obtained. Table 2 shows the formulation and characteristics of the obtained toner particles 19.

<Examples 1 to 14>
The following evaluation was performed using the toner particles 1 to 14. The results are shown in Table 2.

<Comparative Examples 1-5>
The following evaluation was carried out using the toner particles 15 to 19. The results are shown in Table 2.

<Evaluation of preservability>
To 100 parts by mass of toner particles, 1.8 parts by mass of silica fine particles having a specific surface area measured by the BET method of 200 m ² / g and hydrophobized with silicone oil are dry-mixed with a Henschel mixer (Mitsui Mine). Thus, a toner to which an external additive was added was prepared.

  The amount of toner remaining on the sieve when the toner is left in a constant temperature and humidity chamber for 3 days and sieved for 300 seconds with a shaking width of 1 mm using a sieve having an opening of 75 μm is based on the following criteria. Evaluated. The evaluation results are shown in Table 2.

(Evaluation criteria)
A: The amount of toner remaining on the sieve is 10% or less after sieving after standing in a constant temperature and humidity chamber at a temperature of 50 ° C. and a humidity of 54% RH for 3 days. B: a temperature of 50 ° C. and a humidity of 54% RH After standing in a constant temperature and humidity chamber for 3 days and then sieving, the amount of toner remaining on the sieve is 10% or more, but after standing in a constant temperature and humidity chamber at a temperature of 50 ° C. and a humidity of 10% RH for 3 days The amount of toner remaining on the sieve after sieving was 10% or less. C: left for 3 days in a constant temperature and humidity chamber with a temperature of 50 ° C. and a humidity of 10% RH, and remained on the sieve when sieving. Toner amount is 10% or more

<Evaluation of low-temperature fixability>
100 parts by mass of toner particles having a specific surface area measured by the BET method of 200 m ² / g and 1.8 parts by mass of silica fine powder hydrophobized with silicone oil are dry-mixed with a Henschel mixer (Mitsui Mine). Thus, a toner to which an external additive was added was prepared.

  The toner and a ferrite carrier (average particle size 42 μm) surface-coated with a silicone resin were mixed so that the toner concentration was 8% by mass to prepare a two-component developer.

The two-component developer was filled in a commercially available full-color digital copying machine (CLC1100, manufactured by Canon Inc.) to form an unfixed toner image (0.6 mg / cm ² ) on the image receiving paper (64 g / m ² ).

A fixing unit removed from a commercially available full-color digital copying machine (imageRUNNER ADVANCE C5051, manufactured by Canon) was remodeled so that the fixing temperature could be adjusted, and a fixing test of an unfixed image was performed using the fixing unit. Under normal temperature and humidity, the process speed was set to 246 mm / sec, and the state when the unfixed image was fixed was visually evaluated. The evaluation results are shown in Table 2.
(Evaluation criteria)
A: Fixing is possible in a temperature range of 120 ° C. or lower B: Fixing is possible in a temperature range higher than 120 ° C. and 130 ° C. or lower C: Fixing is possible in a temperature range higher than 130 ° C. and 140 ° C. or lower D: 140 ° C. There is a fixable area only in a higher temperature range

<Evaluation of electrification>
100 parts by mass of toner particles having a specific surface area measured by the BET method of 200 m ² / g and 1.8 parts by mass of silica fine powder hydrophobized with silicone oil are dry-mixed with a Henschel mixer (Mitsui Mine). Thus, a toner to which an external additive was added was prepared.

0.01 g of toner was weighed into an aluminum pan and charged to −600 V using a strocolon charging device. Subsequently, the change behavior of the surface potential was measured for 30 minutes using a surface potential meter (manufactured by Trek Japan: model 347) in an atmosphere of a temperature of 25 ° C. and a humidity of 50% RH. The charge retention was calculated by substituting the measurement results into the following formula and evaluated according to the following criteria. The evaluation results are shown in Table 2.
Charge retention (%) after 30 minutes = [surface potential after 30 minutes] / [initial surface potential] × 100
(Evaluation criteria)
A: Charge retention after 30 minutes is 80% or more B: Charge retention after 30 minutes is less than 80% and 65% or more C: Charge retention after 30 minutes is less than 65% and 50% or more
D: Less than 50% charge retention after 30 minutes

Claims (8)

A toner having toner particles containing an amorphous resin having an aromatic ring and a crystalline polyester,
The crystalline polyester has a unit represented by the following formula (1),
One of A ¹ and B ^{1 in} the formula (1) is a divalent group represented by the following formula (2),
The toner, wherein the other of A ¹ and B ¹ is an alkylene group having 4 to 12 carbon atoms.

  The toner according to claim 1, wherein the crystalline polyester has a melting point of 40 ° C. or higher and 100 ° C. or lower.   The toner according to claim 1, wherein the concentration of the ester group of the crystalline polyester is 20% by mass to 35% by mass with respect to the total molecular weight of the structural unit of the crystalline polyester.   The said crystalline polyester contains 25 mol% or more and 100 mol% or less of the unit shown by said Formula (1) as a structural unit with respect to all the units which the said crystalline polyester has. Toner described in   The toner according to claim 1, wherein the amorphous resin having an aromatic ring is an amorphous polyester.   The density | concentration of the aromatic ring of the amorphous resin which has the said aromatic ring is 20 to 70 mass% with respect to the total molecular weight of the structural unit of the said amorphous polyester, The any one of Claims 1-5 The toner according to item.   The toner according to claim 1, wherein the toner contains 1% by mass to 40% by mass of the crystalline polyester. The toner according to claim 1, wherein R ¹ and R ² in the structure in the formula (2) are methylene.