JP6027865B2 - Method for producing toner for developing electrostatic image - Google Patents

Description

  The present invention relates to a method for producing an electrostatic charge image developing toner and an electrostatic charge image developing toner obtained thereby.

In the field of electrophotography, with the development of an electrophotographic system, development of toner for electrophotography corresponding to higher image quality and higher speed is required.
Corresponding to high image quality, a method of obtaining a toner having a narrow particle size distribution and a small particle size is obtained by aggregating and fusing fine resin particles in an aqueous medium to obtain a toner. A toner is manufactured by an aggregation method or an aggregation fusion method. In particular, attempts have been made to use a mixture of a plurality of resins in order to improve thermal characteristics such as low-temperature fixability and offset resistance.

For example, Patent Document 1 discloses an amorphous polyester having 2.0 to 12.0 mol% of a structural unit derived from a trivalent or higher carboxylic acid and crystallinity for the purpose of improving low-temperature fixability and hot offset resistance. A step of emulsifying a raw material polyester containing polyester in an aqueous medium, or after mixing the raw material polyester with an organic solvent, an aqueous medium is added and emulsified to obtain a polyester particle dispersion, and the polyester particle dispersion is obtained. An electrophotographic toner obtained by aggregation and coalescence is disclosed.
Patent Document 2 discloses a toner formed by agglomerating resin particles in a liquid medium for the purpose of improving fixing strength, offset resistance, and heat-resistant storage stability. The toner includes a radical polymer resin, a colorant, and the like. And a toner inner layer containing a release agent, and a toner outer layer containing a grafted polyester resin formed by graft polymerization of a radical polymerizable monomer on a polyester having an unsaturated bond in the main chain at the outer edge. Toner is disclosed.
Patent Document 3 discloses that a polyhydric alcohol and an unsaturated polycarboxylic acid are condensed in order to eliminate offset and excessive gloss and to obtain a toner that does not have toner peeling at the crease portion, that is, insufficient fixing strength. A step of dispersing a polyester resin in an aqueous medium to prepare a polyester resin particle dispersion, and after adding a vinyl polymerizable monomer and a radical polymerization initiator to the polyester resin particle dispersion, a radical polymerization reaction is performed, and a polyester is obtained. A step of preparing a dispersion of resin particles made of a resin in which a vinyl polymerizable monomer is reacted with a resin, a resin particle made of a resin in which a vinyl polymerizable monomer is reacted with the polyester resin, and a dispersion of colorant particles And a step of agglomerating the resin particles and the colorant particles to form toner particles. .

International Publication No. 2010/27071 JP 2006-215312 A JP 2011-95736 A

The toner for electrophotography is desired to have a thermal property (low temperature fixability) for fixing at a low temperature. If the toner is fixed at a low temperature, the power consumption of the printing press can be reduced, and further high-speed printing is possible. As a technique for this purpose, by using crystalline polyester or a release agent in the toner, the fixing temperature of the obtained toner can be lowered due to its melting characteristics. However, a toner containing crystalline polyester or a release agent also has a problem that heat resistant storage stability, which is stability at high temperature storage, is lowered. In order to satisfy these compatibility and other performances at the same time, mixing with different resins causes variations in the composition of the particles, resulting in a deterioration in the fluidity, which is the basic performance of the toner, and the scattering of the toner. The problem of (toner cloud) also arises, and there arises a problem that heat resistant storage stability and low-temperature fixability cannot be compatible.
An object of the present invention is to provide a method for producing an electrostatic charge image developing toner capable of achieving both good low-temperature fixability and heat-resistant storage stability and suppressing toner scattering, and an electrostatic charge image developing toner obtained by the production method. There is to do.

  The inventors of the present invention considered that the factors affecting low-temperature fixability, heat-resistant storage stability, and toner scattering are related to the surface layer resin and the internal resin constituting the toner, and their relationship. As a result, in the production of toner in the cohesive fusion method, a graft polymer composed of a main chain segment made of a polyester resin and a side chain segment made of an addition polymerization resin, with a crystalline polyester and a release agent as a core part. It has been found that by using resin particles or the like so as to form a shell portion, it is possible to obtain a toner for developing an electrostatic image that can achieve both good low-temperature fixability and heat-resistant storage stability and can suppress toner scattering.

That is, the present invention provides the following [1] and [2].
[1] A method for producing a core-shell type electrostatic image developing toner comprising the following steps (1) to (3):
Step (1): Step of aggregating resin particles (A) containing crystalline polyester (a) and release agent particles containing a release agent to obtain aggregated particles (1) Step (2): Polyester A step of obtaining aggregated particles (2) by adding resin particles (C) made of a graft polymer composed of a main chain segment (A1) made of resin and a side chain segment (A2) made of an addition polymerization resin. 3) Step of fusing the agglomerated particles (2) to obtain core-shell particles [2] A toner for developing electrostatic images obtained by the production method according to [1].

  According to the present invention, there is provided a method for producing an electrostatic charge image developing toner having both good low-temperature fixability and heat-resistant storage stability and suppressing toner scattering, and an electrostatic charge image developing toner obtained by the production method. can do.

The method for producing a core-shell type electrostatic image developing toner of the present invention includes the following steps (1) to (3).
Step (1): Step of aggregating resin particles (A) containing crystalline polyester (a) and release agent particles containing a release agent to obtain aggregated particles (1) Step (2): Aggregation Resin particles (C) made of a graft polymer composed of a main chain segment (A1) made of a polyester resin and side chain segments (A2) made of an addition polymerization resin are added to the particles (1), and agglomerated particles ( Step 2) Step (3): Fusing the agglomerated particles (2) to obtain core-shell particles

The reason why the toner for developing an electrostatic charge image obtained by the production method of the present invention can achieve both good low-temperature fixability and heat-resistant storage stability and suppress toner scattering is not clear, but is considered as follows.
In step (1) in the method of the present invention, the resin particles (A) containing the crystalline polyester (a) and the release agent particles containing the release agent are aggregated to obtain aggregated particles (1). This is a step of forming a core portion of the toner of the present invention, and has a crystalline polyester and a release agent in the core portion, so that the toner melts sharply in each melting point region during printing and has excellent low-temperature fixability. It is considered to be.
In steps (2) and (3), resin particles (C) composed of a graft polymer composed of a main chain segment (A1) composed of a polyester resin and a side chain segment (A2) composed of an addition polymerization resin are added. The agglomerated particles (2) are obtained and fused to obtain core-shell particles. As a result, a toner having the graft polymer on the surface can be obtained. In this graft polymer, the main chain is a polyester resin and the side chain is an addition polymerization resin, so the main chain part has high affinity with the core containing crystalline polyester, and the side chain part Is considered to be easily oriented to the toner surface. Therefore, the toner of the present invention has a homogeneous addition-polymerized resin film in the outermost layer and has a crystalline polyester resin or the like inside, so that good heat-resistant storage is maintained while maintaining good low-temperature fixability. It is considered that the toner can be compatible and the toner scattering can be suppressed.
Hereinafter, each component and process used in the present invention will be described.

[Resin particles (A)]
The resin particles (A) of the present invention contain a crystalline polyester (a) from the viewpoint of improving the low-temperature fixability of the obtained toner.
[Crystalline polyester (a)]
In the present invention, the crystalline polyester is defined as the ratio between the softening point and the maximum endothermic peak temperature measured by a differential scanning calorimeter (DSC), (softening point (° C.)) / (Maximum endothermic peak temperature (° C.)). The crystallinity index is 0.6 to 1.4, and from the viewpoint of low-temperature fixability of the toner, 0.8 to 1.3 is preferable, and 0.9 to 1.2 is more preferable. 0.9 to 1.1 is more preferable.
The crystalline polyester (a) preferably has an acid group at the molecular end from the viewpoint of facilitating emulsification of the resin particle dispersion and enhancing the dispersion stability. Examples of the acid group include a carboxy group, a sulfonic acid group, a phosphonic acid group, and a sulfinic acid. Among these, a carboxy group is preferable from the viewpoint of achieving both the dispersion stability of the resin and the heat-resistant storage stability of the obtained toner.

The melting point of the crystalline polyester (a) is preferably from 50 to 150 ° C., more preferably from 55 to 130 ° C., from the viewpoint of improving the low-temperature fixability and heat-resistant storage stability of the toner and suppressing toner scattering. ° C is more preferable, and 60-80 ° C is still more preferable.
From the same viewpoint, the softening point of the crystalline polyester (a) is preferably 50 to 140 ° C, more preferably 55 to 130 ° C, still more preferably 60 to 110 ° C, and further preferably 60 to 85 ° C.
The number average molecular weight of the crystalline polyester (a) is preferably 1,500 to 50,000, more preferably 2,000 to 10,000, from the viewpoint of improving the low-temperature fixability and heat-resistant storage stability of the toner. 000 to 5,000 are more preferable.
The acid value of the crystalline polyester (a) is preferably 5 to 30 mg KOH / g, and preferably 10 to 25 mg KOH / g from the viewpoint of improving the dispersion stability of the resin particle dispersion of the toner and the low-temperature fixability and heat-resistant storage stability of the toner. Is more preferable, 15-25 mgKOH / g is still more preferable, and 15-22 mgKOH / g is still more preferable.
In addition, crystalline polyester (a) can be used individually or in combination of 2 or more types.
In the present invention, the melting point, softening point and number average molecular weight of the crystalline polyester (a) are determined by the methods described in the examples. When two or more kinds are used in combination, the melting point of the crystalline polyester (a) having the largest weight ratio in the crystalline polyester (a) contained in the obtained toner is the melting point of the crystalline polyester (a) in the present invention. The melting point. When all have the same ratio, the lowest value is set. A softening point and a number average molecular weight are calculated | required by the method as described in an Example using the mixture mixed by the ratio which uses all the crystalline polyester (a).

The crystalline polyester (a) can be produced by subjecting an acid component and an alcohol component to a polycondensation reaction. A catalyst can be preferably used in the polycondensation reaction.
Examples of the acid component include aliphatic dicarboxylic acid, alicyclic dicarboxylic acid, aromatic dicarboxylic acid, and trivalent or higher polyvalent carboxylic acid. Among them, the low-temperature fixing property, heat-resistant storage property and charging property of the toner are improved. From the viewpoint, an aliphatic dicarboxylic acid is preferable.
The acid component includes not only a free acid but also an anhydride that decomposes during the reaction to produce an acid, and an alkyl ester having 1 to 3 carbon atoms.
The aliphatic dicarboxylic acid preferably has 2 to 18 carbon atoms and more preferably 8 to 12 carbon atoms from the viewpoint of improving low-temperature fixability and heat-resistant storage stability of the toner and suppressing toner scattering.
Examples of the aliphatic carboxylic acid having 2 to 18 carbon atoms include oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, adipic acid, sebacic acid, 1,12-dodecanedioic acid. , Azelaic acid, n-dodecyl succinic acid, n-dodecenyl succinic acid, etc. Among them, from the viewpoint of improving low-temperature fixability and heat-resistant storage stability of the toner and suppressing toner scattering, sebacic acid, 1,12-dodecane Diacid is preferable, sebacic acid is preferable from the viewpoint of heat-resistant storage stability, and 1,12-dodecanedioic acid is preferable from the viewpoint of suppressing toner scattering.
Examples of the alicyclic dicarboxylic acid include cyclohexane dicarboxylic acid.
Examples of the aromatic dicarboxylic acid include phthalic acid, isophthalic acid, terephthalic acid and the like.
Examples of the trivalent or higher polyvalent carboxylic acid include trimellitic acid and pyromellitic acid.
These can be used alone or in combination of two or more.

Examples of alcohol components include aliphatic diols, aromatic diols, hydrogenated bisphenol A, and trihydric or higher polyhydric alcohols, among others, promoting the crystallization of polyester and improving the low-temperature fixability of the toner. From the viewpoint of making them, an aliphatic diol is preferable.
Among the aliphatic diols, α, ω-alkanediol is preferable from the viewpoint of promoting the crystallization of polyester and improving the low-temperature fixability of the toner.
The α, ω-alkanediol preferably has 2 to 18 carbon atoms, more preferably 4 to 12 carbon atoms, and more preferably 4 to 12 carbon atoms from the viewpoint of improving low-temperature fixability and heat-resistant storage stability of the obtained toner and suppressing toner scattering. 6-12 are still more preferable.
Examples of the α, ω-alkanediol having 2 to 18 carbon atoms include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1, Examples include 6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, and the like. 1,6-Hexanediol and 1,9-nonanediol are preferable from the viewpoint of improving low-temperature fixability and heat-resistant storage stability and suppressing toner scattering, and 1,9-nonanediol is preferable from the viewpoint of improving heat-resistant storage stability. From the viewpoint of suppressing toner scattering, 1,6-hexanediol is preferable.
The α, ω-alkanediol having 2 to 18 carbon atoms can be used alone or in combination of two or more.
Examples of aromatic diols include alkylene (2 to 3 carbon) oxide adducts (average number of added moles 1 to 16) of bisphenol A.
Examples of the trihydric or higher polyhydric alcohol include glycerin and pentaerythritol.

  The alcohol component can be used alone or in combination of two or more. From the viewpoint of promoting the crystallization of the polyester, the alcohol component contains 80 to 100 α, ω-alkanediol having 2 to 18 carbon atoms. It is preferable that it is mol%, and it is more preferable that it is 90-100 mol%.

  The combination of the acid component and the alcohol component is preferably a combination of an aliphatic dicarboxylic acid and an aliphatic diol from the viewpoint of improving the low-temperature fixability and heat-resistant storage stability of the resulting toner and suppressing toner scattering. A combination of 2 to 18 α, ω-alkanediol and an aliphatic dicarboxylic acid having 8 to 12 carbon atoms is more preferable.

From the viewpoint of improving the efficiency of the condensation polymerization reaction, the catalyst is preferably a tin compound or a titanium compound, more preferably a tin compound, and further preferably di (2-ethylhexanoic acid) tin or dibutyltin oxide.
Examples of the titanium compound include titanium diisopropylate bistriethanolamate.
The amount of the catalyst used is preferably 0.01 to 1 part by weight, more preferably 0.05 to 0.8 part by weight, with respect to 100 parts by weight of the total amount of the acid component and the alcohol component, and 0.1 to 0. 6 parts by weight is more preferable.

  The polycondensation reaction is preferably carried out by putting an acid component and an alcohol component in a reaction vessel and maintaining the reaction at 140 to 200 ° C. for 5 to 15 hours. Further, after that, the catalyst is added and the reaction is allowed to proceed at 140 to 200 ° C. for 1 to 5 hours, and the reaction is preferably carried out under the condition that the pressure is reduced to 5.0 to 20 kPa and maintained for 1 to 10 hours.

[Amorphous polyester (b)]
The resin particles (A) of the present invention are amorphous in addition to the crystalline polyester (a) from the viewpoint of improving adhesion to the shell portion of the obtained toner, improving heat-resistant storage stability and suppressing toner scattering. It is preferable to contain polyester (b). In the present invention, the amorphous polyester is a resin having a crystallinity index of more than 1.4 or less than 0.6.
The total amount of the crystalline polyester (a) and the amorphous polyester (b) in the resin particles (A) is preferably from 50 to 50 in the resin constituting the resin particles (A) from the viewpoint of improving the low-temperature fixability of the toner. It is 100% by weight, more preferably 80 to 100% by weight, still more preferably 90 to 100% by weight, and still more preferably substantially 100% by weight. The weight ratio ((a) / (b)) between the crystalline polyester (a) and the amorphous polyester (b) in the resin particles (A) improves the low-temperature fixability and heat-resistant storage stability of the toner, and the toner scattering. From the viewpoint of suppressing the viscosity, it is preferably 5/95 to 50/50, more preferably 5/95 to 30/70, further preferably 10/90 to 25/75, and more preferably 15/85 to 20/80. Further preferred.

The amorphous polyester (b) can be produced by polycondensation reaction between an acid component and an alcohol component.
Examples of the acid component include dicarboxylic acids and trivalent or higher polyvalent carboxylic acids. Among these, dicarboxylic acids are preferable, and dicarboxylic acids and trivalent or higher polyvalent carboxylic acids are more preferably used in combination.
As the dicarboxylic acid, an alkyl succinic acid having a branched alkyl group having 9 to 14 carbon atoms and / or a branched alkenyl having 9 to 14 carbon atoms is used from the viewpoint of enhancing affinity with the crystalline polyester and improving low-temperature fixability of the toner. Preferred are alkenyl succinic acid and aromatic dicarboxylic acid having a group, alkyl succinic acid having a branched alkyl group having 9 to 14 carbon atoms and / or alkenyl succinic acid having a branched alkenyl group having 9 to 14 carbon atoms and aromatic dicarboxylic acid. It is more preferable to use together. As the dicarboxylic acid, unsaturated aliphatic dicarboxylic acids such as fumaric acid and maleic acid can also be used.

Among alkyl succinic acid having a branched alkyl group having 9 to 14 carbon atoms and / or alkenyl succinic acid having a branched alkenyl group having 9 to 14 carbon atoms, the affinity with a crystalline polyester is increased, and the low-temperature fixability of the toner is also improved. From the viewpoint of increasing the alkenyl succinic acid having a branched alkenyl group having 9 to 14 carbon atoms is preferable.
Further, from the viewpoint of enhancing the affinity with the crystalline polyester and thus enhancing the low-temperature fixability of the toner, the number of carbon atoms of the branched alkyl group or branched alkenyl group is preferably 10-14, more preferably 12-14.
Specific examples of the alkyl succinic acid having a branched alkyl group having 9 to 14 carbon atoms and / or the alkenyl succinic acid having a branched alkenyl group having 9 to 14 carbon atoms include dodecyl succinic acid, dodecenyl succinic acid, octenyl succinic acid, From the viewpoint of improving the low-temperature fixability of the toner, dodecenyl succinic acid is preferable.
The branched structure may exist in any part of the alkyl group and the alkenyl group, but a mixture having a plurality of branched structures is preferable from the viewpoint of enhancing the compatibility with the crystalline polyester.
Alkyl succinic acid having a branched alkyl group having 9 to 14 carbon atoms and / or alkenyl succinic acid having a branched alkenyl group having 9 to 14 carbon atoms increases the affinity with the crystalline polyester, thereby lowering the low-temperature fixability of the toner. From the viewpoint of increasing, it is preferably contained in the acid component in an amount of 5 to 60 mol%, more preferably 30 to 50 mol%, still more preferably 35 to 40 mol%.
As the unsaturated aliphatic dicarboxylic acid, as the aromatic dicarboxylic acid such as fumaric acid and maleic acid, terephthalic acid is preferable from the viewpoint of improving the heat-resistant storage stability and charging stability of the toner and suppressing toner scattering.

Examples of the trivalent to pentavalent aromatic carboxylic acid include trimellitic acid, 2,5,7-naphthalenetricarboxylic acid, pyromellitic acid, and the like. Among them, the heat resistant storage stability of the toner is improved and the toner scattering is suppressed. From the viewpoint, trimellitic acid is preferable.
The trivalent to pentavalent aromatic carboxylic acid is preferably contained in the acid component in an amount of 5 to 30 mol%, more preferably 7 to 20 mol% from the viewpoint of improving the heat-resistant storage stability of the toner and suppressing toner scattering. Contained, more preferably 8 to 15 mol%, and still more preferably 9 to 11 mol%.

  Preferred alcohol components include aromatic diols from the viewpoint of improving heat-resistant storage stability and charging stability of the toner and suppressing toner scattering, and include an alkylene (carbon number 2-3) oxide adduct (average addition) of bisphenol A. Mole number 1-16) is preferred.

The glass transition point of the amorphous polyester (b) is preferably from 50 to 70 ° C., more preferably from 55 to 68 ° C., from the viewpoint of improving toner durability, low-temperature fixability and heat-resistant storage stability and suppressing toner scattering. Preferably, it is 58-66 degreeC.
The softening point of the amorphous polyester (b) is preferably 70 to 165 ° C., more preferably 70 to 140 ° C., and more preferably 90 to 140 ° C. from the viewpoint of improving low-temperature fixability and heat-resistant storage stability of the toner and suppressing toner scattering. 140 degreeC is still more preferable and 100-130 degreeC is still more preferable.
In addition, when using 2 or more types of amorphous polyesters (b) mixed, the glass transition point and the softening point are each described in the examples as a mixture of 2 or more types of amorphous polyesters (b). The value obtained by the method.

The number average molecular weight of the amorphous polyester (b) is preferably 1,000 to 50,000, more preferably 1,500 to 10,000, from the viewpoint of improving the durability, low-temperature fixability and heat-resistant storage stability of the toner. Preferably, 2,000 to 8,000 are more preferable, and 2,000 to 4,000 are more preferable.
The acid value of the amorphous polyester (b) is preferably 6 to 35 mgKOH / g, more preferably 10 to 35 mgKOH / g, and still more preferably 15 to 35 mgKOH / g, from the viewpoint of easily emulsifying the resin in an aqueous medium. .
Amorphous polyester (b) may be used alone or in combination of two or more.

[Colorant]
The resin particles (A) may be particles composed only of a resin, or may be colorant-containing resin particles containing a colorant. The resin particles (A) preferably contain a colorant from the viewpoint of sharpening the particle size distribution of the toner, suppressing toner scattering, and obtaining a high-quality image, and the colorant-containing resin particles containing the colorant It is preferable that
When the resin particles (A) are colorant-containing resin particles, the content of the colorant is selected from the viewpoint of improving the image density of the printed matter obtained using the toner and improving the low-temperature fixability of the toner. 1 to 20 parts by weight is preferable with respect to 100 parts by weight of the resin constituting (A), and 5 to 10 parts by weight is more preferable.

Examples of the colorant used in the present invention include pigments and dyes, and pigments are preferable from the viewpoint of improving the image density of the obtained printed matter.
Examples of the pigment include a cyan pigment, a yellow pigment, a magenta pigment, and a black pigment.
The cyan pigment is preferably a phthalocyanine pigment, and more preferably copper phthalocyanine. The yellow pigment is preferably a monoazo pigment, isoindoline pigment, or benzimidazolone pigment, and the magenta pigment is preferably a soluble azo pigment such as a quinacridone pigment or a BONA lake pigment, or an insoluble azo pigment such as a naphthol AS pigment. The black pigment is preferably carbon black.
Examples of the dye include acridine dyes, azo dyes, benzoquinone dyes, azine dyes, anthraquinone dyes, indigo dyes, phthalocyanine dyes, aniline black dyes, and the like.
A coloring agent can be used individually by 1 type or in combination of 2 or more types.

[Production of resin particles (A)]
Resin particles (A) are a resin containing crystalline polyester (a) (preferably a resin containing crystalline polyester (a) and amorphous polyester (b)) and an optional component such as a colorant dispersed in an aqueous medium. From the viewpoint of improving the low-temperature fixability of the toner.
Examples of the method for obtaining a dispersion include a method in which a resin or the like is added to an aqueous medium and dispersed using a disperser, a phase inversion emulsification method in which an aqueous medium is gradually added to the resin and emulsified, and the like. From the viewpoint of improving the low-temperature fixability of the toner, the phase inversion emulsification method is preferable. Hereinafter, the phase inversion emulsification method will be described.

First, the resin containing the crystalline polyester (a), the alkaline aqueous solution, and the optional components such as the colorant are melted and mixed to obtain a resin mixture.
When the resin containing the crystalline polyester (a) contains other resins, a mixture of the crystalline polyester (a) and other resins may be used in advance. It may be obtained by adding at the same time when adding, melting and mixing. For example, when the resin containing the crystalline polyester (a) contains the amorphous polyester (b), the crystalline polyester (a), the amorphous polyester (b), the alkaline aqueous solution, and the above optional components From the viewpoint of improving the low-temperature fixability of the toner, it is preferable to melt and mix them to obtain a resin mixture.
In mixing, it is preferable to add a surfactant from the viewpoint of improving the emulsion stability of the resin.

  The alkali in the alkaline aqueous solution is preferably an alkali metal hydroxide such as potassium hydroxide or sodium hydroxide, or ammonia, and more preferably potassium hydroxide or sodium hydroxide from the viewpoint of improving the dispersion stability of the resin. Moreover, 1-30 weight% is preferable, as for the density | concentration of the alkali in aqueous alkali solution, 1-25 weight% is more preferable, and 1.5-20 weight% is still more preferable.

Examples of the surfactant include nonionic surfactants, anionic surfactants, cationic surfactants, etc. Among them, nonionic surfactants are preferable, and nonionic surfactants and anionic surfactants or It is more preferable to use a cationic surfactant in combination, and it is more preferable to use a nonionic surfactant and an anionic surfactant in combination from the viewpoint of improving the emulsion stability of the resin.
When a nonionic surfactant and an anionic surfactant are used in combination, the weight ratio of the nonionic surfactant to the anionic surfactant (nonionic surfactant / anionic surfactant) is the emulsification of the resin. From the viewpoint of improving stability, 0.3 to 10 is preferable, and 0.5 to 5 is more preferable.

Examples of nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene fatty acid esters, oxyethylene / oxypropylene block copolymers, among others, improving the emulsion stability of resins. From the viewpoint of making it, polyoxyethylene alkyl ether is preferable.
Examples of the polyoxyethylene alkyl ether include polyoxyethylene oleyl ether and polyoxyethylene lauryl ether.
Examples of the polyoxyethylene alkyl aryl ether include polyoxyethylene nonyl phenyl ether.
Examples of the polyoxyethylene fatty acid ester include polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol monooleate and the like.

Examples of anionic surfactants include dodecyl benzene sulfonate, dodecyl sulfate, alkyl ether sulfate, and the like. From the viewpoint of improving the emulsion stability of the resin, dodecyl benzene sulfonate, alkyl ether sulfate. Is preferred.
As dodecylbenzenesulfonate, an alkali metal salt of dodecylbenzenesulfonate is preferable, and sodium dodecylbenzenesulfonate is more preferable. As dodecyl sulfate, an alkali metal salt of dodecyl sulfate is preferable, and sodium dodecyl sulfate is more preferable. As the alkyl ether sulfate, an alkali metal salt of alkyl ether sulfate is preferable, and sodium alkyl ether sulfate is more preferable.

  Examples of the cationic surfactant include alkylbenzyldimethylammonium chloride, alkyltrimethylammonium chloride, dialkyldimethylammonium chloride and the like.

  From the viewpoint of improving the dispersion stability of the resin particles, the content of the surfactant is preferably 20 parts by weight or less, more preferably 15 parts by weight or less with respect to 100 parts by weight of the resin constituting the resin particles (A). 0.1 to 10 parts by weight is more preferable, and 0.5 to 10 parts by weight is further preferable.

As a method for obtaining a resin mixture, a resin containing crystalline polyester (a), an aqueous alkali solution, and the above optional components, preferably a surfactant, are placed in a container, and the resin is melted uniformly while stirring with a stirrer. It is preferable to mix them.
The temperature at which the resin is melted and mixed is preferably equal to or higher than the melting point of the crystalline polyester (a) from the viewpoint of obtaining homogeneous resin particles, and the resin containing the crystalline polyester (a) is an amorphous polyester (b). When it contains, the glass transition point or more is preferable.

Next, an aqueous medium is added to the resin mixture and phase inversion is performed to obtain a dispersion containing resin particles (A).
As the aqueous medium, those containing water as a main component are preferable. From the viewpoint of improving the emulsion stability of the resin, the content of water in the aqueous medium is preferably 80% by weight or more, more preferably 90% by weight or more, and 95 More preferably, it is more preferably at least 100% by weight. The water is preferably deionized water or distilled water.
Components other than water include aliphatic alcohols having 1 to 5 carbon atoms such as ethanol and isopropanol; dialkyl (carbon numbers 1 to 3) ketones such as acetone and methyl ethyl ketone; organic solvents that dissolve in water such as cyclic ethers such as tetrahydrofuran Is used.

The temperature at which the aqueous medium is added is preferably equal to or higher than the glass transition point of the amorphous polyester (b) when the resin containing the crystalline polyester (a) contains the amorphous polyester (b). From the viewpoint of obtaining resin particles, the melting point of the crystalline polyester (a) is more preferable.
From the viewpoint of obtaining resin particles having a small particle size, the addition rate of the aqueous medium is 0.1 to 50 parts by weight / 100 parts by weight of the resin constituting the resin particles (A) until the phase inversion is completed. Preferably 0.1 to 30 parts by weight / minute, more preferably 0.5 to 10 parts by weight / minute, and 0.5 to 5 parts by weight / minute. Is more preferable. There is no restriction | limiting in the addition rate of the aqueous medium after phase inversion.
The amount of the aqueous medium used is 100 to 2000 parts by weight with respect to 100 parts by weight of the resin constituting the resin particles (A) from the viewpoint of improving the productivity of the toner and obtaining uniform aggregated particles in the subsequent aggregation process. Is preferable, 150-1500 weight part is more preferable, 150-500 weight part is still more preferable. From the viewpoint of improving the stability of the resulting resin particle dispersion, the solid content is preferably 7 to 50% by weight, more preferably 10 to 40% by weight, still more preferably 20 to 40% by weight, and still more preferably. 25 to 35% by weight. In addition, solid content is the total amount of non-volatile components, such as resin and surfactant.

The volume median particle size of the resin particles (A) in the dispersion containing the obtained resin particles (A) is preferably 0.02 to 2 μm. From the viewpoint of sharpening the particle size distribution of the toner, suppressing toner scattering, and obtaining a toner capable of obtaining a high-quality image, 0.02 to 1.5 μm is preferable, 0.05 to 1 μm is more preferable, and More preferably, it is 05-0.5 micrometer. Here, the volume-median particle diameter is a particle diameter at which the cumulative volume frequency calculated by the volume fraction is 50% calculated from the smaller particle diameter, and is obtained by the method described in the examples.
Further, the coefficient of variation (CV value) (%) of the particle size distribution of the resin particles is 40% from the viewpoint of sharpening the particle size distribution of the toner, suppressing toner scattering, and obtaining a toner capable of obtaining a high-quality image. Or less, more preferably 35% or less, still more preferably 30% or less, and even more preferably 28% or less. The CV value is a value represented by the following formula, and is determined by the method described in the examples.
CV value (%) = [standard deviation of particle size distribution (μm) / volume median particle size (μm)] × 100

In addition, the resin particles (A) may be particles composed only of a resin, but from the viewpoint of sharpening the particle size distribution of the toner, suppressing toner scattering, and obtaining a high-quality image, as described above, the resin particles (A) are colored. It is preferable to be obtained from a mixed resin containing a colorant, that is, it is preferable to contain a colorant, and colorant-containing resin particles containing a colorant are preferred.
When the resin particles (A) are colorant-containing resin particles, the content of the colorant is selected from the viewpoint of improving the image density of the printed matter obtained using the toner and improving the low-temperature fixability of the toner. 1 to 20 parts by weight is preferable, 3 to 15 parts by weight is more preferable, and 5 to 10 parts by weight is more preferable with respect to 100 parts by weight of the resin constituting (A).

The resin particles (A) are preferably crosslinked from the polyester resin contained in the resin particles (A) from the viewpoint of improving the heat resistant storage stability and low-temperature fixability of the toner, and more preferably crosslinked by a compound having an oxazoline group. preferable.
The compound having an oxazoline group preferably contains a plurality of oxazoline groups in the molecule, and more preferably a polymer containing an oxazoline group. The weight average molecular weight of the polymer containing an oxazoline group is preferably 500 to 2,000,000, more preferably 1,000 to 1,000,000, from the viewpoint of increasing the reactivity with the polyester resin.
Examples of commercially available polymers containing oxazoline groups include EPOCROSS WS series (water-soluble type, main chain acrylic), K series (emulsion type, main chain styrene / acrylic) manufactured by Nippon Shokubai Co., Ltd. Also product name).
The content or addition amount of the compound having an oxazoline group is preferably 0 as a solid content with respect to 100 parts by weight of the resin in the resin dispersion from the viewpoint of enhancing the crosslinking reactivity with the resin and improving the productivity. 0.1 to 30 parts by weight, more preferably 0.5 to 20 parts by weight, still more preferably 1 to 10 parts by weight.

  By adding and mixing a compound having an oxazoline group, the polyester resin contained in the resin particles (A) dispersed in the resin dispersion is crosslinked. The temperature at the time of mixing becomes like this. Preferably it is 60-100 degreeC, More preferably, it is 70-98 degreeC. The presence of the crosslink can be confirmed by the amide group.

[Releasing agent particles]
The release agent particles preferably contain a surfactant from the viewpoint of aggregation. As the surfactant, sodium polycarboxylate is preferable. In the case of using the surfactant, the content is preferably 0.01 to 10 parts by weight with respect to 100 parts by weight of the release agent, and preferably 0.1 to 5 parts from the viewpoint of aggregation properties and chargeability of the obtained toner. Part by weight is more preferred.
The volume median particle size of the release agent particles is preferably 0.1 to 1 μm, more preferably 0.1 to 0.7 μm, and more preferably 0.1 to 0 μm from the viewpoint of improving the chargeability of the toner and preventing hot offset. More preferably, it is 5 μm.
The CV value of the release agent particles is preferably 15 to 50%, more preferably 15 to 40%, and still more preferably 15 to 35% from the viewpoint of improving the chargeability of the toner and the productivity.

〔Release agent〕
As release agents, low molecular weight polyolefins such as polyethylene, polypropylene and polybutene; silicone waxes; fatty acid amides such as oleic amides and stearic amides; plant waxes; animal waxes such as beeswax; mineral or petroleum waxes; Examples include synthetic waxes such as ester waxes.
Examples of plant waxes include carnauba wax, rice wax, and candelilla wax. Carnauba wax is preferred from the viewpoint of improving the low-temperature fixability of the toner.
Examples of the mineral-based or petroleum-based wax include montan wax, paraffin wax, and Fischer-Tropsch wax. Paraffin wax is preferable from the viewpoint of improving low-temperature fixability of the toner.
These release agents can be used alone or in combination of two or more, and it is preferable to use in combination of two or more. In particular, it is preferable to use a plant wax and a mineral or petroleum wax in combination from the viewpoint of improving the low-temperature fixability of the toner, and it is more preferable to use a carnauba wax and a paraffin wax in combination.
The melting point of the release agent is preferably 60 to 100 ° C., more preferably 60 to 90 ° C., further preferably 75 to 90 ° C., and 80 to 90 ° C. from the viewpoint of improving the low-temperature fixability and heat-resistant storage stability of the toner. Is even more preferable. When using 2 or more types together, it is preferable that melting | fusing point of all is 60-90 degreeC from a viewpoint of improving the low temperature fixability of a toner.
In the present invention, the melting point of the release agent is determined by the method described in the examples. When two or more kinds are used in combination, the melting point of the release agent having the largest weight ratio among the release agents contained in the obtained toner is the melting point of the release agent in the present invention. When all have the same ratio, the lowest value is set.
The amount of the release agent used is usually 1 to 20 with respect to 100 parts by weight of the resin in the toner from the viewpoint of improving the releasability of the toner to improve the low temperature fixability and improving the heat resistant storage stability of the toner. Part by weight is preferable, and 2 to 15 parts by weight is more preferable.

[Manufacture of release agent particles]
The release agent particles are preferably obtained as a dispersion of release agent particles by dispersing the release agent in an aqueous medium.
The dispersion of the release agent particles is preferably obtained by dispersing the release agent and the aqueous medium using a disperser in the presence of a surfactant at a temperature equal to or higher than the melting point of the release agent. As the disperser to be used, a homogenizer, an ultrasonic disperser or the like is preferable.
As the aqueous medium used in this production, those used when obtaining a resin mixture are preferably used.
As the surfactant, an anionic surfactant is preferable, and a polycarboxylate is more preferable.
Examples of polycarboxylates include polyacrylates, acrylic acid-maleic acid copolymer salts, polymaleic acid salts, and the like, from the viewpoint of enhancing cohesiveness during toner preparation, and acrylic acid-maleic acid copolymers. The salt of is preferred. As the salt, an alkali metal salt is preferable, and a sodium salt is preferable.
The sodium salt is preferably sodium polyacrylate, sodium salt of acrylic acid-maleic acid copolymer, sodium polymaleate or the like, and from the same viewpoint, sodium salt of acrylic acid-maleic acid copolymer is more preferable.
The solid content concentration of the release agent particle dispersion is preferably 5% by weight or more, more preferably 10% by weight or more from the viewpoint of improving the productivity of the toner and the dispersion stability of the resin particle dispersion. 15% by weight or more, more preferably 40% by weight or less, more preferably 30% by weight or less, and further preferably 25% by weight or less. In addition, solid content is the total amount of non-volatile components, such as a mold release agent and surfactant.

[Resin particles (C)]
In the present invention, the resin particles (C) are used in the step (2) to improve the low-temperature fixability and heat-resistant storage stability of the toner, and from the viewpoint of suppressing toner scattering, the main chain segment (A1) made of a polyester resin. And a graft polymer composed of side chain segments (A2) made of an addition polymerization resin.

(Main chain segment (A1) made of polyester resin)
The segment (A1) constituting the graft polymer is a main chain in the graft polymer, a segment made of a polyester resin, and a segment made of a polyester resin obtained by condensation polymerization of an alcohol component and a carboxylic acid component. . The raw material monomer from which the structural unit of segment (A1) is derived (hereinafter also simply referred to as “raw material monomer of segment (A1)”) is an alcohol component and a carboxylic acid component.

  The alcohol component that is a raw material monomer of the segment (A1) includes an alkylene oxide adduct of 2,2-bis (4-hydroxyphenyl) propane, a non-aromatic carbon-carbon unsaturated bond, and both ends thereof. Examples include diols having a hydroxyl group, and use of an alkylene oxide adduct of 2,2-bis (4-hydroxyphenyl) propane from the viewpoint of improving heat-resistant storage stability and charge stability of the toner and suppressing toner scattering. Is preferred.

Specifically, the alkylene oxide adduct of 2,2-bis (4-hydroxyphenyl) propane is preferably a compound represented by the following general formula (I).

In the general formula (I), R ¹ O and R ² O are both oxyalkylene groups, preferably each independently an oxyalkylene group having 1 to 4 carbon atoms, more preferably an oxyethylene group or an oxypropylene group. It is.
x and y correspond to the added mole number of alkylene oxide, and are positive numbers. Furthermore, from the viewpoint of increasing the reactivity with the carboxylic acid component, the average value of the sum of x and y is preferably 2 to 7, more preferably 2 to 5, and still more preferably 2 to 3.
Further, x R ¹ O or y R ² O may be the same or different from each other, but may be the same from the viewpoint of improving the low-temperature fixability and heat-resistant storage stability of the toner. Preferably, it is an oxypropylene group. The alkylene oxide adduct of 2,2-bis (4-hydroxyphenyl) propane may be used alone or in combination of two or more.

  From the viewpoint of improving the heat-resistant storage stability of the toner, the content of the oxypropylene group in the oxyalkylene group is preferably 50 to 100 mol%, more preferably 60 to 100 mol%, more preferably 70 to 100 mol. %, More preferably substantially 100 mol%. The other oxyalkylene group is preferably an oxyethylene group or an oxytrimethylene group, and more preferably an oxyethylene group, from the viewpoint of improving the low-temperature fixability and heat-resistant storage stability of the toner.

  The alkylene oxide adduct of 2,2-bis (4-hydroxyphenyl) propane is contained in the alcohol component in an amount of 60 mol% or more, preferably 70 mol%, from the viewpoint of improving the low-temperature fixability and heat-resistant storage stability of the toner. More preferably, it is 80 mol% or more, and still more preferably 100 mol%. In the present invention, the alkylene oxide adduct means the whole structure in which an oxyalkylene group is added to 2,2-bis (4-hydroxyphenyl) propane.

As the diol having a non-aromatic carbon-carbon unsaturated bond and having hydroxyl groups at both ends, for example, an alcohol component containing an unsaturated aliphatic diol is preferably used. The portion of the carbon-carbon unsaturated bond in the unsaturated aliphatic diol can be a bonding portion with the segment (A2) in the graft polymer, and in this case, the unsaturated bond becomes a saturated bond. .
Other alcohol components include, for example, ethylene glycol, propylene glycol (1,2-propanediol), glycerin, pentaerythritol, trimethylolpropane, hydrogenated bisphenol A, sorbitol, allyl alcohol or alkylene thereof (2 to 2 carbon atoms). 4) Oxide adduct (average number of added moles of 1 to 16) and the like. You may use the said alcohol component individually or in combination of 2 or more types.

  The carboxylic acid component which is a raw material monomer of the segment (A1) includes a dicarboxylic acid having a non-aromatic carbon-carbon unsaturated bond and having a carboxy group at both ends thereof, such as an unsaturated aliphatic dicarboxylic acid and / or It is preferable to contain unsaturated alicyclic dicarboxylic acid. The carbon-carbon unsaturated bond portion is preferably a bond portion with the segment (A2) in the graft polymer. In this case, the unsaturated bond is a saturated bond. A carbon-carbon unsaturated bond can be introduced into the main chain of the polyester obtained by using a dicarboxylic acid having a non-aromatic carbon-carbon unsaturated bond and having a carboxy group at both ends thereof.

  Examples of dicarboxylic acids (unsaturated aliphatic dicarboxylic acids and unsaturated alicyclic dicarboxylic acids) having a non-aromatic carbon-carbon unsaturated bond and having a carboxy group at both ends include fumaric acid and maleic acid. Unsaturated aliphatic dicarboxylic acid; unsaturated alicyclic dicarboxylic acid such as tetrahydrophthalic acid. From the viewpoint of reactivity, fumaric acid, maleic acid and tetrahydrophthalic acid are preferable, and fumaric acid is more preferable.

  In the carboxylic acid component, the content of the dicarboxylic acid having a non-aromatic carbon-carbon unsaturated bond and having a carboxy group at both ends thereof is preferably 20 to 100 from the viewpoint of improving the heat resistant storage stability of the toner. It is mol%, More preferably, it is 20-50 mol%, More preferably, it is 35-45 mol%.

Examples of other carboxylic acids include aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, and terephthalic acid; aliphatic dicarboxylic acids such as adipic acid, succinic acid, succinic acid having an alkyl group and / or alkenyl group; cyclohexanedicarboxylic acid Alicyclic dicarboxylic acids such as acids and decalin dicarboxylic acids; Trivalent or higher polyvalent carboxylic acids such as trimellitic acid and pyromellitic acid, and anhydrides of these acids and their alkyl (1 to 3 carbon atoms) esters Etc. From the viewpoint of suppressing toner scattering and improving heat-resistant storage stability, aromatic dicarboxylic acids are preferred, and terephthalic acid is more preferred. The said carboxylic acid component may be individual or 2 or more types may be contained.
Among the raw material monomers derived from the structural unit of the main chain segment (A1) made of polyester resin, as the raw material monomer having a non-aromatic carbon-carbon unsaturated bond, unsaturated aliphatic dicarboxylic acid, unsaturated fat One or more selected from cyclic dicarboxylic acids and unsaturated aliphatic diols may be included, but from the viewpoint of reactivity, it is preferable to include unsaturated aliphatic dicarboxylic acids and / or unsaturated alicyclic dicarboxylic acids, More preferably, it is only unsaturated aliphatic dicarboxylic acid.

The glass transition point of the segment (A1) is preferably 50 ° C. or higher, more preferably 60 ° C. or higher, and 80 ° C. or lower from the viewpoint of improving low-temperature fixability and heat-resistant storage stability of the toner and suppressing toner scattering. Preferably, 70 degrees C or less is more preferable.
The softening point of the segment (A1) is preferably 70 ° C. or higher, more preferably 90 ° C. or higher, and further preferably 100 ° C. or higher, from the viewpoint of improving the low-temperature fixability and heat-resistant storage stability of the toner and suppressing toner scattering. Moreover, 165 degrees C or less is preferable, 140 degrees C or less is more preferable, and 130 degrees C or less is still more preferable.
From the viewpoint of improving the dispersion stability of the resin particles, suppressing toner scattering, and improving the heat resistant storage stability, the acid value of the segment (A1) is preferably 5 to 40 mgKOH / g, more preferably 15 to 30 mgKOH / g. g, more preferably 20 to 25 mg KOH / g.
Further, from the viewpoint of improving the low-temperature fixability and heat-resistant storage stability of the toner, the number average molecular weight of the segment (A1) is preferably 1,000 to 10,000, more preferably 2,000 to 8,000, still more preferably. Is 2,000 to 4,000.
In the present invention, as the acid group contained in the segment (A1), from the viewpoint of achieving both the dispersion stability of the resin and the heat resistant storage stability of the obtained toner, the carboxy group is 90 mol% or more of the acid group. It is preferable that it is substantially 100 mol%.

(Side chain segment (A2) made of addition polymerization resin)
The segment (A2) constituting the graft polymer is a segment made of an addition polymerization resin composed of a structural unit derived from an addition polymerizable monomer (c2) (hereinafter also referred to as “monomer (c2)”). The segment (A2) is a side chain in the graft polymer.
Examples of the addition polymerizable monomer (c2) that can be used in the present invention include styrenes such as styrene, methylstyrene, α-methylstyrene, β-methylstyrene, and t-butylstyrene; alkyl (meth) acrylate (having 1 carbon atom). -18), (meth) acrylic acid esters such as benzyl (meth) acrylate; olefins such as ethylene, propylene and butadiene; halovinyls such as vinyl chloride; vinyl esters such as vinyl acetate; vinyl ethers such as vinyl methyl ether A vinylidene halide such as vinylidene chloride; and an N-vinyl compound such as N-vinylpyrrolidone.
Among these, styrenes and (meth) acrylic acid esters are preferable from the viewpoint of improving low-temperature fixability and heat-resistant storage stability of the toner and suppressing toner scattering, and among these, addition polymerizable monomers having an aromatic group. Are more preferable, and styrene, methylstyrene, benzyl methacrylate and benzyl acrylate are more preferable. Among these, styrene is preferable from the viewpoint of the raw material price of the monomer and from the viewpoint of suppressing toner scattering and improving heat-resistant storage stability.
The content of the structural unit derived from the addition-polymerizable monomer having an aromatic group is preferably 85 in the segment (A2) from the viewpoint of suppressing toner scattering and improving the low-temperature fixability and heat-resistant storage stability of the toner. % By weight or more, more preferably 90% by weight or more, still more preferably 95% by weight or more, and still more preferably substantially 100% by weight.

The weight ratio of the main chain segment (A1) and the side chain segment (A2) constituting the graft polymer [main chain segment (A1) / side chain segment (A2)] suppresses toner scattering and fixes the toner at low temperature. From the viewpoint of improving the stability and heat-resistant storage stability, it is preferably 55/45 to 99/1, more preferably 80/20 to 99/1, more preferably 90/10 to 99/1, and still more preferably 95/5 to 5/5. 98/2, more preferably 96/4 to 97/3.
Since there are more main chain segments (A1) than side chain segments (A2), the addition polymerization resin can be present in the outermost layer while maintaining the adhesion to the core, and the low-temperature fixability of the toner can be reduced. It is considered that both heat-resistant storage stability can be achieved and toner scattering can also be suppressed.
In addition, the softening point of the graft polymer is preferably 80 to 165 ° C. from the viewpoint of suppressing toner scattering and improving the low-temperature fixability and heat-resistant storage stability of the toner.

[Production Method of Resin Particle (C)]
As a method for producing the resin particles (C) comprising the graft polymer used in the present invention, a polyester resin (c1) having a non-aromatic carbon-carbon unsaturated bond by polycondensing an alcohol component and a carboxylic acid component. ) (Hereinafter also referred to as resin (c1)) and addition polymerization of the addition polymerizable monomer (c2) in the presence of the polyester resin (c1) is from the viewpoint of the productivity of the resin particles (C). preferable.

(Polyester resin (c1))
The resin (c1) is a polyester resin having a non-aromatic carbon-carbon unsaturated bond in the main chain, and is preferable for constituting the main chain segment (A1) made of the polyester resin. The “non-aromatic carbon-carbon unsaturated bond” is derived from one or more selected from the above-mentioned unsaturated aliphatic dicarboxylic acid, unsaturated alicyclic dicarboxylic acid and unsaturated aliphatic diol. It is. The resin (c1) is preferably an amorphous resin.

The resin (c1) is preferably an alkylene oxide adduct of 2,2-bis (4-hydroxyphenyl) propane as a raw material component from the viewpoint of improving the heat-resistant storage stability and charging stability of the toner and suppressing toner scattering. Is obtained using an alcohol component containing 50 mol% or more.
Here, the alkylene oxide adduct of 2,2-bis (4-hydroxyphenyl) propane is the same as the segment (A1), and the preferred structure and the preferred content are also the same.

As an alcohol component which is a raw material component of the resin (c1), an alcohol component other than this can be used together with an alkylene oxide adduct of 2,2-bis (4-hydroxyphenyl) propane. The resin (c1) has a non-aromatic carbon-carbon unsaturated bond in the main chain, uses a diol having a non-aromatic carbon-carbon unsaturated bond and having hydroxyl groups at both ends. be able to.
Other alcohols are the same as those in the segment (A1). You may use alcohol individually or in combination of 2 or more types.

The resin (c1) has a non-aromatic carbon-carbon unsaturated bond, and has a non-aromatic carbon-carbon unsaturated bond as a carboxylic acid component as a raw material component of the polyester. A dicarboxylic acid having a carboxy group at both ends can be preferably used.
The dicarboxylic acid having a non-aromatic carbon-carbon unsaturated bond and having a carboxy group at both ends thereof is the same as in the case of the segment (A1), and the preferred structure and preferred content are also the same. And fumaric acid is more preferred.
The content of the dicarboxylic acid having a non-aromatic carbon-carbon unsaturated bond in the carboxylic acid component is preferably 5 to 50 mol%, more preferably 15 to 45 mol%, still more preferably 20 to 40 mol%. It is. In addition, when resin (c1) contains several polyester, content of the dicarboxylic acid which has a non-aromatic carbon-carbon unsaturated bond shall satisfy | fill said range in the carboxylic acid component of all the polyesters. Is preferred.
The other carboxylic acid is the same as in the case of the segment (A1), and the preferred structure and the preferred content are the same. An aromatic dicarboxylic acid is preferred, and terephthalic acid is more preferred. Carboxylic acids may be used alone or in combination of two or more.

The polyester resin (c1) is produced, for example, by subjecting the alcohol component and the carboxylic acid component to condensation polymerization at a temperature of 180 to 250 ° C. using an esterification catalyst as necessary in an inert gas atmosphere. be able to.
From the viewpoint of suppressing toner scattering and improving heat resistant storage stability, it is preferable to perform condensation polymerization using a catalyst. Examples of the catalyst include a tin catalyst and a titanium catalyst. From the viewpoint of increasing the reaction efficiency of the esterification reaction in the synthesis of polyester, a tin catalyst is preferable, and dibutyltin oxide and di (2-ethylhexanoic acid) tin are preferable.
In the present invention, since a carboxylic acid having a non-aromatic carbon-carbon unsaturated bond is used, it is preferable to use a radical polymerization inhibitor. The radical polymerization inhibitor is preferably 4-t-butylcatechol.

From the viewpoint of suppressing toner scattering and improving the low-temperature fixability and heat-resistant storage stability of the toner, the softening point of the resin (c1) is preferably 80 to 165 ° C., and the glass transition point is preferably 50 to 85 ° C. . From the viewpoint of improving the dispersion stability of the resin particle dispersion, suppressing toner scattering, and improving the low-temperature fixability and heat-resistant storage stability of the toner, the acid value of the resin (c1) is preferably 5 to 40 mgKOH / g. More preferably, it is 15-30 mgKOH / g, More preferably, it is 20-25 mgKOH / g.
The glass transition point, softening point, and acid value can all be obtained by appropriately adjusting the type of monomer used, the blending ratio, the temperature of condensation polymerization, and the reaction time.
Further, from the viewpoint of suppressing toner scattering and improving the low-temperature fixability and heat-resistant storage stability of the toner, the number average molecular weight of the resin (c1) is preferably 1,000 to 10,000, more preferably 2,000. 8,000 to 8,000, more preferably 2,000 to 4,000.

(Addition polymerizable monomer (c2))
The addition polymerizable monomer (c2) used in the present invention is preferably the same as that described as the raw material monomer for the segment (A2) made of the above addition polymerization resin, suppresses scattering of the toner, and preserves heat. From the viewpoint of improving the properties, the addition polymerizable monomer having an aromatic group is preferably 85% by weight or more, more preferably 90% by weight or more, still more preferably 95% by weight or more, and further preferably substantially 100% by weight. To do. As the addition polymerizable monomer having an aromatic group, styrene, benzyl methacrylate, and benzyl acrylate are preferable. Among these, styrene is preferable from the viewpoint of suppressing the raw material price of the monomer, scattering of the toner, and improving the heat resistant storage stability.

(Production of resin particles (C))
As described above, the method for producing the resin particles (C) comprising the graft polymer used in the present invention has a non-aromatic carbon-carbon unsaturated bond by polycondensing an alcohol component and a carboxylic acid component. A method of preparing the polyester resin (c1) and subjecting the addition polymerizable monomer (c2) to addition polymerization in the presence of the polyester resin (c1) is preferable from the viewpoint of productivity of the resin particles (C). Specific examples include a method in which the resin (c1) and the monomer (c2) are directly mixed and polymerized, and a method in which the resin (c1) and the monomer (c2) are dissolved in an organic solvent and polymerized. In particular, the graft polymer used in the present invention is prepared by preparing a polyester resin (c1) having a non-aromatic carbon-carbon unsaturated bond and mixing the polyester resin (c1) with an aqueous medium. A step of obtaining an aqueous dispersion of (c1), and a step of adding an addition polymerizable monomer (c2) to the aqueous dispersion and polymerizing to obtain an aqueous dispersion of resin particles (C) comprising a graft polymer. Preferably obtained by a method.

A step of mixing the polyester resin (c1) with an aqueous medium to obtain an aqueous dispersion of the polyester resin (c1) will be described.
As with the resin particles (A), the dispersion is obtained by adding a resin or the like to an aqueous medium and dispersing it using a disperser, or by gradually adding the aqueous medium to the resin or the like and emulsifying it. From the viewpoint of improving the low-temperature fixability of the obtained toner, the phase inversion emulsification method is preferable. Hereinafter, the phase inversion emulsification method will be described.

First, a resin containing a polyester resin (c1), an alkaline aqueous solution, and the like are melted and mixed to obtain a resin mixture. In mixing, it is preferable to add a surfactant from the viewpoint of improving the emulsion stability of the resin.
Examples of the alkali in the alkaline aqueous solution include hydroxides of alkali metals such as potassium hydroxide and sodium hydroxide, and ammonia. From the viewpoint of improving the dispersion stability of the resin, potassium hydroxide and sodium hydroxide. Is preferred. Moreover, 1-30 weight% is preferable, as for the density | concentration of the alkali in aqueous alkali solution, 1-25 weight% is more preferable, and 1.5-20 weight% is still more preferable.

The type of the surfactant is as described in the above-mentioned “Production of the resin fine particles (A)”. Anionic surfactant) 0.5 to 5 is preferably used in combination. The nonionic surfactant is preferably polyoxyethylene alkyl ether, and the anionic surfactant is preferably dodecylbenzene sulfonate, and more preferably used in combination.
The content of the surfactant is preferably 20 parts by weight or less, more preferably 15 parts by weight or less, still more preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the polyester resin (c1). 10 parts by weight is more preferable.
As a method for obtaining a resin mixture, a method in which a polyester resin (c1) and an aqueous alkaline solution, preferably a surfactant, are placed in a container and the resin is melted and mixed uniformly while stirring with a stirrer is used. From the viewpoint of improving the properties, it is preferable.
The temperature at which the resin is melted and mixed is preferably equal to or higher than the glass transition point of the polyester resin (c1).

Next, an aqueous medium is added to the resin mixture and phase inversion is performed to obtain a dispersion containing resin particles (C).
The type and content of the aqueous medium are as described in the above-mentioned “Production of resin fine particles (A)”.

The temperature at which the aqueous medium is added is preferably at least the glass transition point of the polyester resin (c1) from the viewpoint of obtaining homogeneous resin particles.
The addition rate of the aqueous medium is 0.1 to 50 parts by weight / min with respect to 100 parts by weight of the polyester resin (c1) until the phase inversion is completed from the viewpoint of obtaining resin particles having a small particle size. Preferably, it is 0.1 to 30 parts by weight / minute, more preferably 0.5 to 10 parts by weight / minute, and further preferably 0.5 to 5 parts by weight / minute. There is no restriction | limiting in the addition rate of the aqueous medium after phase inversion.
The amount of the aqueous medium used is preferably from 100 to 2000 parts by weight, more preferably from 150 to 1500 parts by weight, based on 100 parts by weight of the polyester resin (c1), from the viewpoint of obtaining uniform aggregated particles in the subsequent aggregation step. More preferred is ~ 500 parts by weight. From the viewpoint of improving the productivity of the toner and the stability of the resulting resin particle dispersion, the solid concentration is preferably 7 to 50% by weight, more preferably 10 to 40% by weight, and still more preferably. It is 20 to 40 weight%, More preferably, it is 25 to 35 weight%. In addition, solid content is the total amount of non-volatile components, such as resin and surfactant.

The volume median particle size of the resin particles of the polyester resin (c1) in the obtained dispersion is preferably 0.02 to 2 μm. From the viewpoint of sharpening the particle size distribution of the toner, suppressing toner scattering, and obtaining a toner capable of obtaining a high-quality image, 0.02 to 1.5 μm is preferable, 0.05 to 1 μm is more preferable, and More preferably, it is 05-0.5 micrometer.
Further, the coefficient of variation (CV value) (%) of the particle size distribution of the resin particles is 40% from the viewpoint of sharpening the particle size distribution of the toner, suppressing toner scattering, and obtaining a toner capable of obtaining a high-quality image. Or less, more preferably 35% or less, still more preferably 30% or less, and even more preferably 28% or less.

Next, the addition polymerizable monomer (c2) is added to the obtained aqueous dispersion and polymerized to obtain an aqueous dispersion of resin particles (C) made of a graft polymer.
Addition polymerizable monomer (c2) is added to the aqueous dispersion of polyester resin (c1). The addition amount is a weight ratio of the polyester resin (c1) and the addition polymerizable monomer (c2) [polyester resin (c1) / addition polymerizable monomer (c2)], which suppresses the scattering of the toner and reduces the low temperature fixability of the toner. From the viewpoint of improving the heat resistant storage stability, it is preferably 55/45 to 99/1, more preferably 80/20 to 99/1, more preferably 90/10 to 99/1, and still more preferably 95/5 to 98. / 2, more preferably 96/4 to 97/3.
Moreover, you may add water etc. further from the point of the efficiency of stirring.

Further, the addition polymerizable monomer (c2) is polymerized in the presence of the polyester resin (c1).
Arbitrary radical polymerization initiators, crosslinking agents and the like are added to the polymerization as necessary. As the radical polymerization initiator, a water-soluble radical polymerization initiator is preferably used, and a persulfate is more preferably used.
The polymerization reaction is advanced by heating the mixed solution containing the polyester resin (c1) and the addition polymerizable monomer (c2). The polymerization temperature depends on the type of polymerization initiator used, but for example, when sodium persulfate is used, it is preferably 60 to 100 ° C., more preferably 70 to 90, from the viewpoint of efficiently performing the polymerization reaction. ° C.

The glass transition point of the graft polymer in the aqueous dispersion of the resin particles (C) obtained in the above manner suppresses the storage stability and scattering of the toner, thereby reducing the low-temperature fixability and heat-resistant storage stability of the toner. From a viewpoint of improving, Preferably it is 40-80 degreeC, More preferably, it is 50-70 degreeC, More preferably, it is 55-65 degreeC. The softening point of the graft polymer is preferably 80 to 250 ° C, more preferably 100 to 130 ° C.
The solid content concentration of the aqueous dispersion of the resin particles (C) is preferably 10 to 40% by weight, more preferably 15 to 35% by weight, from the viewpoint of improving the dispersion stability of the resin particles and improving the productivity. Preferably it is 20-30 weight%. When used in step (2) of the present invention, it is preferably adjusted to the above concentration and used as an aqueous dispersion.
The pH of the aqueous dispersion of resin particles (C) at 25 ° C. is preferably 5 to 10, more preferably 5 to 8, from the viewpoint of improving the storage stability of the aqueous dispersion of resin particles (C). More preferably, it is 6-7.

The volume-median particle size (D ₅₀ ) of the resin particles in the aqueous dispersion of the resin particles (C) obtains a toner having a sharp particle size distribution, and thus obtains a high-quality image in terms of suppressing toner scattering. From the viewpoint, it is preferably 0.02 μm to 1 μm, more preferably 0.05 μm to 0.8 μm, and still more preferably 0.08 μm to 0.5 μm.
The coefficient of variation (CV value) (%) of the particle size distribution of the resin particles (C) is 40% from the viewpoint of sharpening the particle size distribution of the toner and suppressing toner scattering and obtaining a high-quality image. Or less, more preferably 35% or less, still more preferably 30% or less, and even more preferably 28% or less.

[Method for producing toner for developing electrostatic image]
The method for producing a core-shell type electrostatic image developing toner of the present invention includes the following steps (1) to (3).
Step (1): Step of aggregating resin particles (A) containing crystalline polyester (a) and release agent particles containing a release agent to obtain aggregated particles (1) Step (2): Aggregation Resin particles (C) made of a graft polymer composed of a main chain segment (A1) made of a polyester resin and side chain segments (A2) made of an addition polymerization resin are added to the particles (1), and agglomerated particles ( Step 2) Step (3): Fusing the agglomerated particles (2) to obtain core-shell particles

[Step (1)]
Step (1) is a step of obtaining aggregated particles (1) by aggregating resin particles (A) containing crystalline polyester (a) and release agent particles containing a release agent.
In this step, first, the resin particles (A) and the release agent particles are mixed in an aqueous medium to obtain a mixed dispersion.
In addition, although it is preferable to mix a colorant as an arbitrary component, the colorant may be mixed as a separate particle by itself, or may be contained in the resin particle (A), but controls aggregation. From the viewpoint of obtaining agglomerated particles having a desired particle size, the resin particles (A) are preferably contained.
There is no restriction | limiting in order of mixing, You may add any in order and may add simultaneously.

In the mixed dispersion, the resin particles (A) are preferably 10 to 40 parts by weight from the viewpoint of improving the productivity of the toner and controlling the aggregation to obtain aggregated particles having a desired particle size. Part is more preferred. The aqueous medium is preferably 60 to 90 parts by weight, more preferably 70 to 80 parts by weight.
In addition, the colorant is used in an amount of 1 to 100 parts by weight of the resin constituting the resin particles (A) from the viewpoint of improving the image density of the printed matter obtained using the toner and improving the low-temperature fixability of the toner. 20 parts by weight is preferable, and 3 to 15 parts by weight is more preferable. From the viewpoint of improving the toner releasability and improving the low-temperature fixability, and from the viewpoint of improving the heat-resistant storage stability and chargeability of the toner, the release agent particles are based on a total of 100 parts by weight of the resin and the colorant. 1 to 20 parts by weight is preferable, and 2 to 15 parts by weight is more preferable.
The mixing temperature is preferably 0 to 40 ° C. from the viewpoint of controlling aggregation and obtaining aggregated particles having a target particle size.

Next, the particles in the mixed dispersion are aggregated to obtain a dispersion of aggregated particles (1). It is preferable to add a flocculant for efficient aggregation.
The aggregating agent is preferably an electrolyte, and more preferably a salt, for the purpose of obtaining a toner having a target particle size while preventing excessive aggregation. The valence is preferably 1 to 5, more preferably 1 to 2, and even more preferably 1. That is, a monovalent salt is preferable.
As the monovalent salt, an ammonium salt is preferable.
Specific examples of the flocculant include quaternary salt cationic surfactants, organic flocculants such as polyethyleneimine; inorganic flocculants such as inorganic metal salts, inorganic ammonium salts, and bivalent or higher metal complexes. It is done. From the viewpoint of improving the charging stability of the toner, an inorganic flocculant is preferable, an inorganic metal salt and an inorganic ammonium salt are more preferable, and an inorganic ammonium salt is further preferable from the viewpoint of increasing the aggregation speed.
Examples of the inorganic metal salt include metal salts such as sodium sulfate, sodium chloride, calcium chloride and calcium nitrate, and inorganic metal salt polymers such as polyaluminum chloride and polyaluminum hydroxide. Examples of the inorganic ammonium salt include ammonium sulfate, ammonium chloride, ammonium nitrate and the like, and ammonium sulfate is more preferable.
The amount of the flocculant used is preferably 50 parts by weight or less, more preferably 40 parts by weight or less, still more preferably from 100 parts by weight of the resin constituting the resin particles (A), from the viewpoint of improving the chargeability of the toner. Is 30 parts by weight or less. In addition, from the viewpoint of controlling the aggregation of the resin particles to obtain a target particle size, it is preferably 1 part by weight or more, more preferably 3 parts by weight or more, with respect to 100 parts by weight of the resin constituting the resin particles (A). More preferably, it is 5 parts by weight or more. In consideration of the above points, the amount of the monovalent salt used is preferably 1 to 50 parts by weight, more preferably 3 to 40 parts by weight with respect to 100 parts by weight of the resin constituting the resin particles (A). More preferably, it is 5-30 weight part.

As an aggregating method, an aggregating agent is preferably added dropwise as an aqueous solution to a container containing a mixed dispersion. The flocculant may be added at one time, or may be added intermittently or continuously. However, it is preferable to perform sufficient stirring at the time of addition and after completion of the addition. From the viewpoint of controlling the aggregation to obtain a desired particle size and shortening the toner production time, the dropping time of the aggregating agent is preferably 1 to 120 minutes. Moreover, 0-50 degreeC is preferable from a viewpoint of dripping temperature controlling aggregation and obtaining the target particle size.
Further, from the viewpoint of promoting aggregation and obtaining aggregated particles having a target particle size and particle size distribution, it is preferable to increase the temperature of the dispersion after adding the aggregating agent. As temperature to maintain, 50-70 degreeC is preferable.
The volume-median particle size of the obtained aggregated particles (1) is preferably 1 to 10 μm, more preferably 2 to 9 μm, and even more preferably 3 from the viewpoint of suppressing toner scattering and obtaining a high-quality image. ~ 6 μm. The CV value is preferably 30% or less, more preferably 28% or less, and still more preferably 25% or less from the viewpoint of sharpening the particle size distribution of the toner and suppressing toner scattering and obtaining a high-quality image. It is.

[Step (2)]
Step (2) is composed of a main chain segment (A1) made of a polyester resin and a side chain segment (A2) made of an addition polymerization resin in the dispersion of the aggregated particles (1) obtained in step (1). In this step, resin particles (C) made of a graft polymer are added to obtain aggregated particles (2).
In this step, the dispersion of resin particles (C) made of the graft polymer is added to the dispersion of aggregated particles (1) obtained in step (1), and resin particles are further added to the aggregated particles (1). It is preferable to attach (C) to obtain aggregated particles (2).

Before adding the dispersion liquid (resin particle (C) dispersion liquid) containing the resin particles (C) to the dispersion liquid (aggregated particle (1) dispersion liquid) containing the aggregated particles (1), the aggregated particle (1) An aqueous medium may be added to the dispersion for dilution, and an aqueous medium is preferably added. By adding an aqueous medium to obtain a predetermined coagulant concentration, the resin particles (C) can be more uniformly adhered to the aggregated particles (1).
When the resin particle (C) dispersion is added to the aggregated particle (1) dispersion, the aggregating agent may be used in order to efficiently attach the resin particle (C) to the aggregated particle (1).
As a preferable addition method in the case of adding the resin particle (C) dispersion to the aggregated particle (1) dispersion, a method of simultaneously adding the coagulant and the resin particle (C) dispersion, the coagulant and the resin particle (C ) A method of alternately adding the dispersion liquid, and a method of adding the resin particle (C) dispersion liquid while gradually raising the temperature of the aggregated particle (1) dispersion liquid. By doing in this way, the cohesiveness fall of the coagulated particle (1) and the resin particle (C) by the coagulant | flocculant density | concentration fall can be prevented. From the viewpoint of toner productivity and manufacturing simplicity, it is preferable to add the resin particle (C) dispersion while gradually raising the temperature of the aggregated particle (1) dispersion.

  The temperature in the system in this step is 5 ° C. from the melting point of the crystalline polyester (a) contained in the resin particles (A) from the viewpoint of improving the low-temperature fixability and heat-resistant storage stability of the toner and suppressing the scattering of the toner. It is preferably lower than the glass transition point of the polyester (c) by 3 ° C. or more, more preferably 5 ° C. or more. When the aggregated particles (2) are produced in this temperature range, the low-temperature fixability and heat-resistant storage stability of the obtained toner are improved. The reason for this is not clear, but because the agglomeration of the aggregated particles (2) does not occur, the generation of coarse particles is suppressed, and the crystallinity of the crystalline polyester (a) can be maintained. Conceivable.

The amount of the resin particles (C) added is such that the weight ratio of the resin particles (C) to the resin particles (A) (resin particles) is improved from the viewpoint of improving the low-temperature fixability and heat-resistant storage stability of the toner and suppressing the scattering of the toner. The amount of (C) / resin particles (A)) is preferably 0.1 to 0.9, more preferably 0.1 to 0.5, and still more preferably 0.2 to 0.4.
Compared with the resin particles (A), by adding a small amount of the resin particles (C), the effect of the core portion of the toner of the present invention in which the crystalline polyester (a) and the amorphous polyester (b) are mixed is sufficiently obtained. And can improve heat-resistant storage stability.

  The resin particle (C) dispersion may be added continuously over a certain period of time, may be added at a time, or may be added in a plurality of divided portions. It is preferable to add them continuously or in several divided portions. By adding as described above, the resin particles (C) are likely to selectively adhere to the aggregated particles (1). Among these, it is preferable to add continuously over a certain time from the viewpoint of promoting selective adhesion and efficient production. The time for continuous addition is preferably 1 to 10 hours, more preferably 2 to 7 hours from the viewpoint of obtaining uniform aggregated particles (2) and shortening the production time.

The total amount of the resin particles (C) is added, and the aggregation is stopped when the toner particles grow to an appropriate particle size.
As the particle size for stopping the aggregation, the volume median particle size of the aggregated particles (2) is preferably 1 to 10 μm, more preferably 2 to 2 from the viewpoint of suppressing toner scattering and obtaining a high-quality image. It is 10 micrometers, More preferably, it is 3-9 micrometers, More preferably, it is 4-6 micrometers.
Examples of the method for stopping the aggregation include a method of cooling the dispersion, a method of adding an aggregation stopper, and a method of diluting the dispersion. From the viewpoint of reliably preventing unnecessary aggregation, the aggregation stopper A method of stopping the aggregation by adding is preferable.
As the aggregation terminator, a surfactant is preferable, and an anionic surfactant is more preferable. Examples of the anionic surfactant include alkyl ether sulfates such as sodium alkyl ether sulfate, alkyl sulfates, and linear alkylbenzene sulfonates. The aggregation terminators can be used alone or in combination of two or more.
The addition amount of the aggregation terminator is preferably 0.1 to 15 parts by weight with respect to 100 parts by weight of the total amount of the resin in the system, from the viewpoint of the property of stopping aggregation and from the viewpoint of reducing residual toner. Preferably it is 0.1-10 weight part, More preferably, it is 0.1-8 weight part. The aggregation terminator is preferably added as an aqueous solution from the viewpoint of improving productivity.

The volume-median particle size of the agglomerated particles (2) obtained in the step (2) is preferably 1 to 10 μm, preferably 2 to 10 μm from the viewpoint of suppressing toner scattering and obtaining a high-quality printed matter. More preferably, 3-9 micrometers is still more preferable, and 4-6 micrometers is still more preferable.
The circularity of the core-shell aggregated particles is preferably from 0.93 to 0.96, and more preferably from 0.93 to 0.95, from the viewpoint of obtaining a high-quality printed matter with toner and further suppressing toner scattering.

[Step (3)]
The step (3) is a step of fusing the aggregated particles (2) obtained in the step (2) to obtain core-shell particles. Each particle that was in a state of being in a fused state is united to form core-shell particles.

From the viewpoint of promoting fusing and improving the productivity of the toner, in this step, the temperature is preferably 10 ° C. or more, more preferably the glass transition point or more, more preferably the glass transition point, more than the glass transition point of the graft polymer. Hold at a temperature of 5 ° C. or higher. From the viewpoint of improving the heat-resistant storage stability while maintaining the core-shell state of the toner and maintaining the low-temperature fixability, in this step, the temperature is preferably 30 ° C. or lower, more preferably 20 ° C. higher than the glass transition point of the graft polymer. The temperature is kept at a high temperature or lower, more preferably 15 ° C. or higher.
When the glass transition point of the graft polymer is Tg and the holding temperature is T, T ≧ Tg−10 ° C., more preferably T ≧ Tg, more preferably T ≧ Tg + 5 ° C., preferably T ≦ Tg + 30 ° C. More preferably, T ≦ Tg + 20 ° C., and further preferably T ≦ Tg + 15 ° C.
Further, from the viewpoint of improving the low-temperature fixability of the toner, in this step, the temperature is preferably maintained at a temperature not higher than 5 ° C., more preferably not higher than the melting point of the crystalline polyester (a).
Further, from the viewpoint of improving the low-temperature fixability of the toner, in this step, it is preferably maintained at a temperature not higher than the melting point of the release agent, more preferably not higher than 3 ° C., more preferably not higher than 5 ° C.
In this step, the viewpoint of promoting the fusion of the particles and improving the productivity of the toner, and the viewpoint of maintaining the core-shell state of the toner particles, improving the low-temperature fixability and heat-resistant storage stability of the toner, and suppressing the scattering of the toner. Therefore, it hold | maintains at 55-85 degreeC, More preferably, it is 60-80 degreeC, More preferably, it is 65-75 degreeC.
The holding time in this step is preferably 0.5 to 24 hours, more preferably 0.7 from the viewpoint of improving particle fusing property, low-temperature fixability of the toner, heat-resistant storage stability, chargeability and toner productivity. -18 hours, more preferably 1-12 hours.

From the viewpoint of suppressing toner scattering and obtaining a high-quality image, the volume-median particle size of the core-shell particles obtained in this step is preferably 2 to 10 μm, more preferably 2 to 8 μm, and more preferably 2 to 2 μm. It is 7 μm, more preferably 3 to 8 μm, and further preferably 4 to 6 μm.
The average particle size of the fused core-shell particles obtained in this step is preferably equal to or less than the average particle size of the aggregated particles (2). That is, in this step, it is preferable that the core shell particles do not aggregate and fuse.

[Post-processing process]
In the present invention, a post-treatment step may be performed after step (3), and it is preferable to obtain toner particles by isolating the core-shell particles.
Since the core-shell particles obtained in the step (3) are present in the aqueous medium, it is preferable to first perform solid-liquid separation. For solid-liquid separation, a suction filtration method or the like is preferably used.
It is preferable to perform washing after the solid-liquid separation. When a nonionic surfactant is used in the production of the resin particles (A) and (C), it is preferable to remove the added nonionic surfactant, so that it is aqueous below the cloud point of the nonionic surfactant. Washing with a solution is preferred. The washing is preferably performed a plurality of times.
Next, it is preferable to perform drying. From the viewpoint of improving the low-temperature fixability of the toner, it is preferable that the temperature of the core-shell particles themselves be 5 ° C. or more lower than the melting point of the crystalline polyester. More preferably, the temperature is lowered by 10 ° C. or more. As a drying method, it is preferable to use a vibration type fluidized drying method, a spray drying method, a freeze drying method, a flash jet method, or the like. The water content after drying is preferably adjusted to 1.5% by weight or less, more preferably 1.0% by weight or less, from the viewpoint of suppressing toner scattering and improving the chargeability.

[Toner for electrostatic image development]
(toner)
Although the toner particles obtained by drying or the like can be used as they are as the toner of the present invention, it is preferable to use toner particles whose surfaces have been treated as described below as electrostatic charge image developing toner.
The softening point of the obtained toner is preferably 60 to 140 ° C., more preferably 60 to 130 ° C., and still more preferably 60 to 120 ° C. from the viewpoint of improving the low-temperature fixability and heat-resistant storage stability of the toner. Further, the glass transition point is preferably 30 to 80 ° C., more preferably 40 to 70 ° C., from the viewpoint of improving the low-temperature fixability, durability and heat-resistant storage stability of the toner.
The volume median particle size of the toner is preferably 1 to 10 μm, more preferably 2 to 8 μm, and still more preferably from the viewpoint of suppressing toner scattering and obtaining a high-quality printed matter with the toner and improving productivity. It is 3-7 micrometers, More preferably, it is 4-6 micrometers.
The CV value of the toner is preferably 30% or less, more preferably 27% or less, from the viewpoint of sharpening the particle size distribution of the toner, suppressing toner scattering and obtaining a high-quality printed matter, and improving productivity. More preferably, it is 25% or less, and more preferably 22% or less.
The degree of circularity of the toner is preferably 0.955 to 0.980, more preferably 0.958 to 0.975, from the viewpoint of improving the heat resistant storage stability of the toner, suppressing toner scattering, and improving cleaning properties. 0.960 to 0.970 is more preferable.
BET specific surface area of the toner suppresses the scattering of the toner is preferably 1.2~2.5m ² / g from the viewpoint of improving the heat-resistant storage stability of the toner, more preferably 1.4~2.2m ² / g 1.6 to 2.0 m ² / g is more preferable.

(External additive)
In the toner for developing an electrostatic charge image of the present invention, the toner particles can be used as the toner as they are, but it is preferable to use a toner obtained by adding a fluidizing agent or the like to the toner particle surface as an external additive.
Examples of the external additive include hydrophobic silica, titanium oxide fine particles, alumina fine particles, cerium oxide fine particles, inorganic fine particles such as carbon black, and polymer fine particles such as polycarbonate, polymethyl methacrylate, and silicone resin. Among these, hydrophobic Silica is preferred.
When the surface treatment of toner particles is performed using an external additive, the amount of the external additive added is preferably 1 to 5 parts by weight, more preferably 2 to 4 parts by weight with respect to 100 parts by weight of the toner particles. .

  The electrostatic image developing toner obtained by the present invention can be used as a one-component developer or mixed with a carrier and used as a two-component developer.

  Each property value of polyester, resin particles, toner, etc. was measured and evaluated by the following method.

[Acid value of polyester]
It measured according to JIS K0070. However, the measurement solvent was chloroform.

[Polyester softening point, crystallinity index, melting point and glass transition point]
(1) Softening point Using a flow tester (manufactured by Shimadzu Corporation, trade name: CFT-500D), a load of 1.96 MPa was applied by a plunger while heating a 1 g sample at a heating rate of 6 ° C / min. And extruded from a nozzle with a diameter of 1 mm and a length of 1 mm. A flow tester drop amount of the flow tester was plotted against the temperature, and the temperature at which half of the sample flowed out was defined as the softening point.

(2) Melting point and glass transition point Sample heated to 200 ° C. using a differential scanning calorimeter (manufactured by PerkinElmer, trade name: Pyris 6 DSC), and cooled to 0 ° C. at a temperature decreasing rate of 50 ° C./min. Was measured at a heating rate of 10 ° C./min. Among the observed endothermic peaks, the temperature of the peak having the maximum peak area was defined as the maximum endothermic temperature (1). In the case of crystalline polyester, the peak temperature was taken as the melting point. In the case of an amorphous polyester, when an endothermic peak is observed, the temperature of the peak is measured. The glass transition point was defined as the temperature at the intersection with the base line extension line on the high temperature side.

(3) Crystallinity Index Using a differential scanning calorimeter (manufactured by PerkinElmer, trade name: Pyris 6 DSC), a sample cooled from room temperature (20 ° C.) to 0 ° C. at a temperature decrease rate of 10 ° C./min is left still for 1 minute. Then, the temperature was raised to 180 ° C. at a temperature raising rate of 10 ° C./min. Of the observed peaks, the peak temperature with the maximum peak area is defined as the endothermic maximum peak temperature (2), and the crystallinity is expressed by (softening point (° C)) / (maximum endothermic peak temperature (2) (° C)). The index was determined.

[Number average molecular weight of polyester]
The molecular weight distribution was measured by gel permeation chromatography and the number average molecular weight was calculated by the following method.
(1) Preparation of sample solution Polyester was dissolved in chloroform so that the concentration was 0.5 g / 100 ml. Subsequently, this solution was filtered using a fluororesin filter having a pore size of 2 μm (manufactured by Sumitomo Electric Industries, Ltd., trade name: FP-200) to remove insoluble components to obtain a sample solution.
(2) Molecular weight distribution measurement Chloroform was allowed to flow as a lysis solution at a flow rate of 1 ml / min, and the column was stabilized in a constant temperature bath at 40 ° C. 200 μl of the sample solution was injected there for measurement. The molecular weight of the sample was calculated based on a calibration curve prepared in advance. In the calibration curve at this time, several types of monodisperse polystyrene (monodisperse polystyrene manufactured by Tosoh Corporation); molecular weights 1.11 × 10 ⁶ , 3.97 × 10 ⁵ , 1.89 × 10 ⁵ , 9.89 × 10 ⁴ , 1.71 × 10 ⁴ , 9.49 × 10 ³ , 5.87 × 10 ³ , 1.01 × 10 ³ , 5.00 × 10 ² ) were used as standard samples.
Measuring apparatus: HPLC LC-9130NEXT (trade name, manufactured by Nippon Analytical Industries, Ltd.)
Analytical column: JAIGEL-2.5-HA + JAIGEL-MH-A (both trade names, manufactured by Nippon Analytical Industries, Ltd.)

[Glass transition point and softening point of resin particles]
When measuring the glass transition point of the resin particles, the solvent was removed from the resin particle dispersion by freeze-drying, and the obtained solid was measured by the same method as the glass transition point and softening point of the polyester.
The lyophilization of the resin particle dispersion was carried out using a freeze dryer (manufactured by Tokyo Rika Kikai Co., Ltd., trade names: FDU-2100 and DRC-1000) with 30 g of the resin particle dispersion at −25 ° C. for 1 hour. It vacuum-dried at -10 degreeC for 10 hours and 25 degreeC for 4 hours, and was dried until it became the moisture content of 1 weight% or less. The moisture content was determined by using an infrared moisture meter (trade name: FD-230, manufactured by Kett Scientific Laboratory), drying 5 g of the sample at a drying temperature of 150 ° C. and a measurement mode 96 (monitoring time 2.5 minutes). / Fluctuation range 0.05%).

[Melting point of release agent]
Sample that was heated to 200 ° C. using a differential scanning calorimeter (trade name: Q-20, manufactured by TA Instruments Japan Co., Ltd.), and cooled to 0 ° C. at a temperature decreasing rate of 10 ° C./min. Was heated at a heating rate of 10 ° C./min, and the maximum peak temperature of the heat of fusion was taken as the melting point.

[Volume Median Particle Size (D ₅₀ ) and Particle Size Distribution of Aggregated Particles]
The volume median particle size of the aggregated particles was measured as follows.
Measuring instrument: Coulter Multisizer III (trade name, manufactured by Beckman Coulter)
・ Aperture diameter: 50μm
・ Analysis software: Multisizer III version 3.51 (trade name, manufactured by Beckman Coulter)
Electrolyte: Isoton II (trade name, manufactured by Beckman Coulter)
Measurement conditions: 30,000 particles are measured after adjusting the particle size of 30,000 particles to a concentration that can be measured in 20 seconds by adding a sample dispersion containing aggregated particles to 100 mL of the electrolyte. The volume-median particle size (D ₅₀ ) was determined from the particle size distribution.
Further, the CV value (%) as a particle size distribution was calculated according to the following formula.
CV value (%) = (standard deviation of particle size distribution / volume median particle size (D ₅₀ )) × 100

[Volume Median Particle Size (D ₅₀ ) and Particle Size Distribution of Toner (Particles)]
The volume median particle size of the toner (particles) was measured as follows.
The measuring instrument, aperture diameter, analysis software, and electrolyte solution were the same as the volume median particle diameter of the aggregated particles.
-Dispersion: Polyoxyethylene lauryl ether (manufactured by Kao Corporation, trade name: Emulgen 109P, HLB: 13.6) was dissolved in the electrolytic solution to obtain a dispersion having a concentration of 5% by weight.
-Dispersion condition: 10 mg of a toner measurement sample is added to 5 mL of the dispersion, and dispersed for 1 minute with an ultrasonic disperser, and then 25 mL of electrolyte is added, and further dispersed for 1 minute with an ultrasonic disperser. A sample dispersion was prepared.
Measurement conditions: The sample dispersion is added to 100 mL of the electrolytic solution to adjust the particle size of 30,000 particles to a concentration that can be measured in 20 seconds, and then 30,000 particles are measured and the particle size distribution thereof. From this, the volume median particle size (D ₅₀ ) was determined.
The CV value (%) was calculated according to the following formula.
CV value (%) = (standard deviation of particle size distribution / volume median particle size (D ₅₀ )) × 100

[Volume Median Particle Size (D ₅₀ ) and Particle Size Distribution of Resin Particles, Release Agent Particles]
(1) Measuring device: Laser diffraction particle size measuring machine (Horiba, Ltd., trade name: LA-920)
(2) Measurement conditions: Distilled water was added to the measurement cell, and the volume-median particle size (D ₅₀ ) was measured at a concentration at which the absorbance was in an appropriate range. The CV value was calculated according to the following formula.
CV value (%) = (standard deviation of particle size distribution / volume median particle size) × 100

[Solid content concentration of resin particle dispersion and release agent particle dispersion]
Using an infrared moisture meter (trade name: FD-230, manufactured by Ketto Scientific Laboratory Co., Ltd.), a measurement sample 5 g was dried at a temperature of 150 ° C. and a measurement mode 96 (monitoring time 2.5 minutes / variation width 0.05%). ) To measure the moisture percentage. The solid content concentration was calculated according to the following formula.
Solid content concentration (% by weight) = 100-M
M: moisture (%) = [(W−W ₀ ) / W] × 100
W: Sample weight before measurement (initial sample weight)
W ₀ : Sample weight after measurement (absolute dry weight)

[Core shell particle, toner circularity]
-Preparation of dispersion: The dispersion of core-shell particles was prepared by diluting with deionized water so that the solid content concentration of the core-shell particles was 0.001 to 0.05%. The toner dispersion was prepared by adding 50 mg of toner to 5 ml of 5% by weight polyoxyethylene lauryl ether (Emulgen 109P) aqueous solution, dispersing for 1 minute with an ultrasonic disperser, adding 20 ml of distilled water, It was prepared by dispersing for 1 minute with a sonic disperser.
Measurement device: Flow-type particle image analyzer (manufactured by Sysmex Corporation, trade name: FPIA-3000)
・ Measurement mode: HPF measurement mode

[BET specific surface area of toner particles]
The BET specific surface area was measured using Micromeritics FlowSorbIII (trade name, manufactured by Shimadzu Corporation) under the following conditions.
Toner sample amount: 0.09 to 0.11 g
・ Deaeration condition: 40 ° C., 10 minutes ・ Adsorption gas: Nitrogen gas

[Evaluation of low-temperature fixability of toner]
Using a commercially available printer (trade name: Microline 5400, manufactured by Fuji Xerox Co., Ltd., J paper A4 size), the toner adhesion amount on the paper is 0.42 to 0.48 mg. A solid image of / cm ² was output without being fixed at a length of 50 mm, leaving a margin of 5 mm from the top edge of the A4 paper.
Next, the same printer with the temperature-variable fixing device prepared was prepared, the temperature of the fixing device was set to 90 ° C., and fixing was performed at a speed of 1.5 seconds per sheet in the A4 longitudinal direction, thereby obtaining a printed matter.
In the same manner, the temperature of the fixing device was increased by 5 ° C., and the fixing was performed to obtain a printed matter.
A 500 g weight is applied to the margin at the top of the printed image, after lightly pasting a piece of mending tape (product name: Scotch mending tape 810, width 18 mm) cut to a length of 50 mm. It was loaded and pressed once and again at a speed of 10 mm / sec. Thereafter, the affixed tape was peeled off from the lower end side at a peeling angle of 180 degrees and a speed of 10 mm / second to obtain a printed matter after the tape was peeled off. 30 sheets of high quality paper (Oki Data Co., Ltd., Excellent White Paper A4 size) is placed under the printed material before and after the tape is applied, and the reflected image density of the fixed image portion before and after the tape is applied to each printed material. , Using a colorimeter (GretagMacbeth, trade name: SpectroEye, light condition; standard light source D ₅₀ , observation field of view 2 °, density standard DINNB, absolute white standard), and calculating the fixing rate using the following formula did.
Fixing rate = (reflected image density after peeling tape / reflected image density before applying tape) × 100
The temperature at which the fixing rate was 90% or more was defined as the minimum fixing temperature. The lower the minimum fixing temperature, the better the low-temperature fixing property.

[Evaluation of heat-resistant storage stability of toner]
20 g of toner was put in a wide-mouthed polybin with an internal volume of 100 ml, sealed, and allowed to stand for 24 hours in an environment at a temperature of 53 ° C. Thereafter, it was allowed to stand for 12 hours or more while being sealed at a temperature of 25 ° C. and cooled. Next, a sieve having a mesh size of 250 μm is set on a powder tester (trade name, manufactured by Hosokawa Micron Co., Ltd.), and 20 g of the toner is placed on the shaker for 30 seconds. The remaining toner weight on the sieve is measured. It was measured. The smaller the value, the better the heat resistant storage stability of the toner.

[Toner scattering evaluation method]
The following operations were all performed in an environment of room temperature of 25 ° C. and relative humidity of 50%. First, 0.7 g of toner and 9.3 g of a silicone ferrite carrier (manufactured by Kanto Denka Kogyo Co., Ltd., average particle size: 40 μm) are placed in a 20-ml cylindrical polypropylene bottle (Nikko Corporation). And shaken 10 times each. Then, it stirred for 10 minutes with the ball mill.
An external developing roller device in which a developing roller (42 mm in diameter) mounted on a commercially available printer (trade name: Microline 5400, manufactured by Oki Data Co., Ltd.) was taken out and modified to be rotatable was used. The developing roller of the external developing roller device was rotated at a speed of 10 revolutions / minute, and the developer was deposited on the developing roller. After uniformly attaching, the rotation was once stopped. The number of scattering toner particles when the rotation speed of the developing roller was changed to 45 rotations / minute and rotated for 1 minute was measured with a digital dust meter (manufactured by Shibata Kagaku Co., Ltd., model: P-5).
The toner scattering property was evaluated from the number of scattered toner particles. The scattering property indicates that the smaller the toner scattering particle number, the better.

[Production of polyester]
Production Example 1
(Production of crystalline polyester X1)
The inside of a four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was purged with nitrogen, and 3936 g of 1,9-nonanediol and 4848 g of sebacic acid were added. While stirring, the temperature was raised to 140 ° C., maintained at 140 ° C. for 3 hours, and then heated from 140 ° C. to 200 ° C. over 10 hours. Thereafter, 50 g of di (2-ethylhexanoic acid) tin was added, and the mixture was further maintained at 200 ° C. for 1 hour. Then, the pressure in the flask was lowered and maintained at 8.3 kPa for 4 hours to obtain crystalline polyester X1. . The physical properties are shown in Table 1.

Production Example 2
(Production of crystalline polyester X2)
The inside of a four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was purged with nitrogen, and 2419 g of 1,6-hexanediol and 4957 g of 1,12-dodecanedioic acid were added. While stirring, the temperature was raised to 140 ° C., maintained at 140 ° C. for 3 hours, and then heated from 140 ° C. to 200 ° C. over 10 hours. Thereafter, 30 g of di (2-ethylhexanoic acid) tin was added, and the mixture was further maintained at 200 ° C. for 1 hour. Then, the pressure in the flask was lowered and maintained at 8.3 kPa for 3 hours to obtain crystalline polyester X2. . The physical properties are shown in Table 1.

Production Example 3
(Production of amorphous polyester Y1)
The inside of a four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was replaced with nitrogen, and 3528 g of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, Put 1404 g of polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl) propane, 1248 g of terephthalic acid, 1541 g of dodecenyl succinic anhydride, and 40 g of di (2-ethylhexanoic acid) tin under a nitrogen atmosphere. While stirring, the temperature was raised to 230 ° C. and maintained at 230 ° C. for 6 hours, and then the pressure in the flask was further lowered and maintained at 8.3 kPa for 1 hour. Then, after cooling to 215 ° C. and returning to atmospheric pressure, 300 g of trimellitic anhydride was added and maintained at 215 ° C. for 1 hour, then the pressure in the flask was further lowered and maintained at 8.3 kPa for 3 hours. As a result, amorphous polyester Y1 was obtained. The physical properties are shown in Table 1.

Production Example 4
(Production of amorphous polyester Y2)
The inside of a four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was replaced with nitrogen, and 3322 g of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, Polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl) propane (31 g), terephthalic acid (662 g) and di (2-ethylhexanoic acid) tin (25 g) were added and stirred at 230 ° C. in a nitrogen atmosphere. Then, the pressure in the flask was further lowered and maintained at 8.0 kPa for 1 hour. After returning to atmospheric pressure, the mixture was cooled to 190 ° C., 685 g of fumaric acid and 2.4 g of tert-butylcatechol (polymerization inhibitor) were added, and maintained at a temperature of 190 ° C. for 1 hour, followed by 210 ° C. over 2 hours. The temperature was raised to. Further, the pressure in the flask was lowered and maintained at 8.0 kPa for 4 hours to obtain amorphous polyester Y2. The physical properties are shown in Table 1.

Production Example 5
(Production of amorphous polyester Y3)
The inside of a four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was replaced with nitrogen, and 1750 g of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, Put 1625 g of polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl) propane, 1145 g of terephthalic acid, 161 g of dodecenyl succinic anhydride, and 25 g of di (2-ethylhexanoic acid) tin under a nitrogen atmosphere. While stirring, the temperature was raised to 230 ° C. and maintained at 230 ° C. for 5 hours, and then the pressure in the flask was further lowered and maintained at 8.0 kPa for 1 hour. After returning to atmospheric pressure, it was cooled to 220 ° C. and 480 g of trimellitic anhydride was added. Then, after confirming that the softening point measured according to ASTM D36-86 reached 120 ° C., the reaction was stopped by lowering the temperature to obtain amorphous polyester Y3. The physical properties are shown in Table 1.

Production Example 6
(Production of amorphous polyester Y4)
The inside of a four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was replaced with nitrogen, and 3487 g of polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl) propane, 1247 g of terephthalic acid and 25 g of di (2-ethylhexanoic acid) tin were added and the temperature was raised to 230 ° C. with stirring in a nitrogen atmosphere and maintained for 5 hours. Then, the pressure in the flask was further lowered to 8.0 kPa. For 1 hour. After returning to atmospheric pressure, the mixture was cooled to 190 ° C., 411 g of fumaric acid and 2.5 g of tert-butylcatechol (polymerization inhibitor) were added, maintained at 190 ° C. for 1 hour, and then 210 ° C. over 2 hours. The temperature was raised to. Further, the pressure in the flask was lowered and maintained at 8.0 kPa for 4 hours to obtain amorphous polyester Y4. The physical properties are shown in Table 1.

Production Example 7
(Production of amorphous polyester Y5)
The inside of a four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was replaced with nitrogen, and 32 g of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, Polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl) propane (2896 g), terephthalic acid (1524 g), glycerin (83 g), and di (2-ethylhexanoic acid) tin (20 g) were added and stirred in a nitrogen atmosphere. However, the temperature was raised to 230 ° C. and maintained at 230 ° C. for 4 hours, and then the pressure in the flask was further lowered and maintained at 8.0 kPa for 1 hour to obtain amorphous polyester Y5. The physical properties are shown in Table 1.

[Production of resin particles]
Production Example 8
(Production of resin particle dispersion A-1)
In a flask equipped with a stirrer, 90 g of crystalline polyester X1, 510 g of amorphous polyester Y1, copper phthalocyanine pigment (trade name: ECB301, manufactured by Dainichi Seika Kogyo Co., Ltd.), polyoxyethylene alkyl ether (nonionic) Surfactant, trade name: Emulgen 150, manufactured by Kao Corporation) 8.5 g, 15 wt% sodium dodecylbenzenesulfonate aqueous solution (anionic surfactant, trade name: Neoperex G-15, manufactured by Kao Corporation) ) 80 g, 225 g of a 5 wt% potassium hydroxide aqueous solution was added, and the mixture was heated to 98 ° C. with melting and melted, and mixed at 98 ° C. for 2 hours to obtain a resin mixture.
Next, 1118 g of deionized water was added dropwise at a rate of 6 g / min while stirring to obtain an emulsion. Next, the obtained emulsion was cooled to 25 ° C., and stirred at 25 ° C., while stirring the oxazoline group-containing polymer aqueous solution (trade name: Epocross WS-700, manufactured by Nippon Shokubai Co., Ltd., nonvolatile content 25% by weight, acrylic 28 g of the main chain) was added, and then the temperature was raised to 95 ° C. and held at 95 ° C. for 1 hour. Next, the mixture was cooled to 25 ° C., and the obtained emulsion was passed through a 200 mesh (mesh opening 105 μm) wire mesh to obtain a resin particle dispersion A-1. The physical properties are shown in Table 2.

Production Example 9
(Production of resin particle dispersion A-2)
In a flask equipped with a stirrer, 90 g of crystalline polyester X2, 510 g of amorphous polyester Y1, 45 g of copper phthalocyanine pigment (ECB301), 8.5 g of polyoxyethylene alkyl ether (Emulgen 150), 15% by weight sodium dodecylbenzenesulfonate An aqueous solution (Neopelex G-15) 80 g, a 5 wt% potassium hydroxide aqueous solution 232 g were added, and the mixture was heated to 98 ° C. with stirring and melted, and mixed at 98 ° C. for 2 hours to obtain a resin mixture.
Next, 1111 g of deionized water was added dropwise at a rate of 6 g / min while stirring to obtain an emulsion. Next, the obtained emulsion is cooled to 25 ° C., and stirred at 25 ° C., 28 g of an aqueous solution of an oxazoline group-containing polymer (Epocross WS-700) is added, and then the temperature is raised to 95 ° C. for 1 hour at 95 ° C. Retained. Next, the mixture was cooled to 25 ° C., and the obtained emulsion was passed through a 200-mesh wire mesh to obtain a resin particle dispersion A-2. The physical properties are shown in Table 2.

Production Example 10
(Production of resin particle dispersion A-3)
Resin in the same manner as in Example 1 except that 90 g of crystalline polyester X1 and 510 g of amorphous polyester Y1 were changed to 90 g of crystalline polyester X1, 300 g of amorphous polyester Y2 and 210 g of amorphous polyester Y3 in Production Example 7. A particle dispersion A-3 was obtained. The physical properties are shown in Table 2.

Production Example 11
(Production of resin particle dispersion B-1)
In a flask having an internal volume of 5 liters, 390 g of amorphous polyester Y2, 210 g of amorphous polyester Y3, polyoxyethylene alkyl ether (nonionic surfactant, trade name: Emulgen 430, manufactured by Kao Corporation) 6 g, 15 A 40% by weight aqueous sodium dodecylbenzenesulfonate solution (anionic surfactant, trade name: Neoperex G-15, manufactured by Kao Corporation) and 268 g of 5% by weight potassium hydroxide were added and the temperature was raised to 95 ° C. with stirring. The mixture was warmed and melted and mixed at 95 ° C. for 2 hours to obtain a resin mixture.
Next, 1145 g of deionized water was added dropwise at a rate of 6 g / min while stirring to obtain an emulsion. Next, the obtained emulsion was cooled to 25 ° C., passed through a 200-mesh wire mesh, deionized water was added, the solid content was adjusted to 28.0 wt%, and resin particle dispersion B-1 was obtained. Obtained. The physical properties are shown in Table 2.

Production Example 12
(Production of resin particle dispersion B-2)
In a flask having an internal volume of 5 liters, 390 g of amorphous polyester Y4, 210 g of amorphous polyester Y3, polyoxyethylene alkyl ether (nonionic surfactant, trade name: Emulgen 430, manufactured by Kao Corporation) 6 g, 15 40% by weight of sodium dodecylbenzenesulfonate aqueous solution (anionic surfactant, trade name: Neoperex G-15, manufactured by Kao Corporation) and 225 g of 5% by weight potassium hydroxide were added and the temperature was raised to 95 ° C. with stirring. The mixture was warmed and melted and mixed at 95 ° C. for 2 hours to obtain a resin mixture.
Next, 1151 g of deionized water was added dropwise at a rate of 6 g / min while stirring to obtain an emulsion. Next, the obtained emulsion was cooled to 25 ° C., passed through a 200-mesh wire mesh, deionized water was added to adjust the solid content to 28.0 wt%, and resin particle dispersion B-2 was obtained. Obtained. The physical properties are shown in Table 2.

Production Example 13
(Production of resin particle dispersion B-3)
In a flask having an internal volume of 5 liters, amorphous polyester Y5 600 g, polyoxyethylene alkyl ether (nonionic surfactant, trade name: Emulgen 430, manufactured by Kao Corp.) 6 g, 15 wt% sodium dodecylbenzenesulfonate 40 g of an aqueous solution (anionic surfactant, trade name: Neoperex G-15, manufactured by Kao Corporation) and 166 g of 5 wt% potassium hydroxide were added, and the mixture was heated to 95 ° C. with melting and melted. The mixture was mixed at 0 ° C. for 2 hours to obtain a resin mixture.
Next, 1207 g of deionized water was added dropwise at a rate of 6 g / min while stirring to obtain an emulsion. Next, the obtained emulsion was cooled to 25 ° C., passed through a 200-mesh wire mesh, deionized water was added to adjust the solid content to 28.0% by weight, and a resin particle dispersion B-3 was obtained. Obtained. The physical properties are shown in Table 2.

Production Example 14
(Production of resin particle dispersion C-1)
679 g of resin particle dispersion B-1 was added to a 2-liter four-necked flask equipped with a condenser, a stirrer, and a thermocouple, and stirred and mixed at 25 ° C. and a stirring speed of 200 r / min in a nitrogen atmosphere. Went. Thereafter, 6.9 g of styrene was added and further mixed for 30 minutes. Next, the temperature was raised to 80 ° C. with stirring for 1 hour, and 3.9 g of a 1% by weight ammonium persulfate aqueous solution was added as an initiator to perform polymerization for 3 hours. Then, add 3.9g of 1% by weight aqueous ammonium persulfate solution, mix for 3 hours, cool to 25 ° C, pass through a 200 mesh wire mesh, add deionized water, and adjust the solid content to 23.5% by weight. Thus, a resin particle dispersion C-1 was obtained. Table 3 shows the physical properties.

Production Example 15
(Production of resin particle dispersion C-2)
679 g of resin particle dispersion B-1 was added to a 2-liter four-necked flask equipped with a condenser, a stirrer, and a thermocouple, and stirred and mixed at 25 ° C. and a stirring speed of 200 r / min in a nitrogen atmosphere. Went. Thereafter, 4.9 g of styrene was added and further mixed for 30 minutes. Next, the temperature was raised to 80 ° C. with stirring for 1 hour, and 3.9 g of a 1% by weight ammonium persulfate aqueous solution was added as an initiator to perform polymerization for 3 hours. Then add 3.9g of 1wt% ammonium persulfate aqueous solution, mix for 3 hours, cool to 25 ° C, pass through 200 mesh wire net, add deionized water to adjust the solid content to 23.5wt%. Thus, a resin particle dispersion C-2 was obtained. Table 3 shows the physical properties.

Production Example 16
(Production of resin particle dispersion C-3)
679 g of resin particle dispersion B-1 was added to a 2-liter four-necked flask equipped with a condenser, a stirrer, and a thermocouple, and stirred and mixed at 25 ° C. and a stirring speed of 200 r / min in a nitrogen atmosphere. Went. Thereafter, 2.9 g of styrene was added and further mixed for 30 minutes. Next, the temperature was raised to 80 ° C. with stirring for 1 hour, and 3.9 g of a 1% by weight ammonium persulfate aqueous solution was added as an initiator to perform polymerization for 3 hours. Then, add 3.9g of 1% by weight aqueous ammonium persulfate solution, mix for 3 hours, cool to 25 ° C, pass through a 200 mesh wire mesh, add deionized water, and adjust the solid content to 23.5% by weight. Thus, a resin particle dispersion C-3 was obtained. Table 3 shows the physical properties.

Production Example 17
(Production of resin particle dispersion C-4)
679 g of resin particle dispersion B-2 was added to a 4-liter flask with an internal volume of 2 liters equipped with a condenser, a stirrer, and a thermocouple, and stirred and mixed at 25 ° C. and a stirring speed of 200 r / min in a nitrogen atmosphere. Went. Thereafter, 9.0 g of styrene was added and further mixed for 30 minutes. Next, the temperature was raised to 80 ° C. with stirring for 1 hour, and 3.9 g of a 1% by weight ammonium persulfate aqueous solution was added as an initiator to perform polymerization for 3 hours. Then, add 3.9g of 1% by weight aqueous ammonium persulfate solution, mix for 3 hours, cool to 25 ° C, pass through a 200 mesh wire mesh, add deionized water, and adjust the solid content to 23.5% by weight. Thus, a resin particle dispersion C-4 was obtained. Table 3 shows the physical properties.

Production Example 18
(Production of resin particle dispersion C-5)
679 g of resin particle dispersion B-2 was added to a 4-liter flask with an internal volume of 2 liters equipped with a condenser, a stirrer, and a thermocouple, and stirred and mixed at 25 ° C. and a stirring speed of 200 r / min in a nitrogen atmosphere. Went. Thereafter, 4.9 g of styrene was added and further mixed for 30 minutes. Next, the temperature was raised to 80 ° C. with stirring for 1 hour, and 3.9 g of a 1% by weight ammonium persulfate aqueous solution was added as an initiator to perform polymerization for 3 hours. Then, add 3.9g of 1% by weight aqueous ammonium persulfate solution, mix for 3 hours, cool to 25 ° C, pass through a 200 mesh wire mesh, add deionized water, and adjust the solid content to 23.5% by weight. Thus, a resin particle dispersion C-5 was obtained. Table 3 shows the physical properties.

Production Example 19
(Production of resin particle dispersion C-6)
Add 679 g of resin particle dispersion B-3 to a 4-liter flask with an internal volume of 2 liters equipped with a condenser, a stirrer and a thermocouple, and stir and mix in a nitrogen atmosphere at 25 ° C. and a stirring speed of 200 r / min. Went. Thereafter, 6.9 g of styrene was added and further mixed for 30 minutes. Next, the temperature was raised to 80 ° C. with stirring for 1 hour, and 3.9 g of a 1% by weight ammonium persulfate aqueous solution was added as an initiator to perform polymerization for 3 hours. Then, add 3.9g of 1% by weight aqueous ammonium persulfate solution, mix for 3 hours, cool to 25 ° C, pass through a 200 mesh wire mesh, add deionized water, and adjust the solid content to 23.5% by weight. Thus, a resin particle dispersion C-6 was obtained. However, since the resin particles in the dispersion C-6 have non-aromatic carbon-carbon unsaturated bonds in the main chain, the amorphous polyester Y5 used in the resin particle dispersion B-3 No graft polymer is formed. Table 3 shows the physical properties.

Production Example 20
(Production of resin particle dispersion C-7)
679 g of resin particle dispersion B-1 was added to a 2-liter four-necked flask equipped with a condenser, a stirrer, and a thermocouple, and stirred and mixed at 25 ° C. and a stirring speed of 200 r / min in a nitrogen atmosphere. Went. Thereafter, 21.1 g of styrene was added and further mixed for 30 minutes. Next, the temperature was raised to 80 ° C. with stirring for 1 hour, and 3.9 g of a 1% by weight ammonium persulfate aqueous solution was added as an initiator to perform polymerization for 3 hours. Then, add 3.9g of 1% by weight aqueous ammonium persulfate solution, mix for 3 hours, cool to 25 ° C, pass through a 200 mesh wire mesh, add deionized water, and adjust the solid content to 23.5% by weight. Thus, a resin particle dispersion C-6 was obtained. Table 3 shows the physical properties.

[Manufacture of release agent particles]
Production Example 21
(Production of release agent particle dispersion)
2. In a 1 liter beaker, sodium acrylate-sodium maleate copolymer aqueous solution (trade name: Poise 521, effective concentration 40% by weight, manufactured by Kao Corporation) as a sodium polycarboxylate aqueous solution in 200 g of deionized water After 8 g was dissolved, 5 g of carnauba wax (manufactured by Hiroyuki Kato, product name: carnauba wax No. 1, melting point 83 ° C.) and paraffin wax (manufactured by Nippon Seiki Co., Ltd., product name: HNP) were dissolved therein. −9, melting point 75 ° C.) 45 g was added, and the mixture was melted while maintaining the temperature at 90 to 95 ° C. to obtain a molten mixture in which carnauba wax and paraffin wax were melted together.
The aqueous solution containing the obtained molten mixture was further subjected to a dispersion treatment for 30 minutes with an ultrasonic homogenizer (trade name: US-600T, manufactured by Nippon Seiki Seisakusho Co., Ltd.) while maintaining the temperature at 90 to 95 ° C. After cooling to room temperature, ion exchange water was added thereto to adjust the release agent solid content to 20% by weight to obtain a release agent particle dispersion. The volume median particle size (D ₅₀ ) of the release agent particles in the release agent particle dispersion was 0.45 μm, and the CV value was 30%.

[Production of toner]
Example 1
(Preparation of Toner 1)
250 g of resin particle dispersion A-1, 64.8 g of deionized water, and 42 g of release agent particle dispersion are placed at a temperature of 25 ° C. in a three-liter four-necked flask equipped with a dehydrating tube, a stirrer, and a thermocouple. Mixed under. Next, while stirring the mixture, an aqueous solution obtained by dissolving 23 g of ammonium sulfate in 194 g of deionized water was dropped at 25 ° C. over 5 minutes, and then the temperature was raised to 63 ° C. It was kept at 63 ° C. until it became 6 μm to obtain a dispersion liquid (1) containing aggregated particles.
33 g of deionized water was added to the aggregated particle dispersion (1) (total amount), and the temperature of the dispersion was cooled to 53 ° C. Next, 94.3 g of the resin particle dispersion C-1 was dropped at a rate of 0.5 ml per minute while raising the temperature of the dispersion at 53 ° C. at a rate of 1.6 ° C. per hour, and the aggregated particle dispersion (2) Got. Table 4 shows the physical properties of the aggregated particle dispersion (2). Moreover, the temperature of the dispersion liquid after completion | finish of dripping was 58 degreeC.
An aqueous solution obtained by mixing 16.6 g of an anionic surfactant (trade name: EMAL (registered trademark) E27C, effective concentration 27% by weight), deionized water 1310 g with the aggregated particle dispersion (2) is added. did. The temperature was raised to 70 ° C. and held at 70 ° C. for 2 hours to fuse the particles to obtain core-shell particles.
The obtained core-shell particle dispersion was cooled to 25 ° C., the solid content of the dispersion was separated by suction filtration, washed with deionized water, and dried at 33 ° C. to obtain toner particles. 100 parts by weight of the toner particles, 2.5 parts by weight of hydrophobic silica (manufactured by Nippon Aerosil Co., Ltd., trade name: RY50, average particle size; 0.04 μm), and hydrophobic silica (manufactured by Cabot Corporation, trade name: Cabo Seal TS720) , Average particle size; 0.012 μm) 1.0 part by weight was put into a Henschel mixer, stirred, and passed through a 150 mesh sieve to obtain a toner. Table 4 shows the physical properties and evaluation of the toner.

Examples 2-8
(Production of toners 2 to 8)
A toner was obtained in the same manner as in Example 1 except that the resin particle dispersions A-1 and C-1 were changed to the resin particle dispersions shown in Table 4 in Example 1. Table 4 shows the physical properties and evaluation of the toner.

Comparative Example 1
(Preparation of Toner 9)
In Example 1, 94.4 g of the resin particle dispersion C-1 was changed to a dispersion obtained by mixing 79.1 g of the resin particle dispersion B-1 and 15.3 g of deionized water. The toner was obtained. Table 4 shows the physical properties and evaluation of the toner.

Comparative Example 2
(Production of Toner 10)
In Example 1, 94.4 g of the resin particle dispersion C-1 was changed to a dispersion obtained by mixing 79.1 g of the resin particle dispersion B-2 and 15.3 g of deionized water. The toner was obtained. Table 4 shows the physical properties and evaluation of the toner.

Comparative Example 3
(Production of Toner 11)
In Example 1, resin particle dispersion A-1 was changed to resin particle dispersion A-2, 94.4 g of resin particle dispersion C-1 was 79.1 g of resin particle dispersion B-1 and deionized water 15 A toner was obtained in the same manner as in Example 1 except that the dispersion was changed to a mixture mixed with 3 g. Table 4 shows the physical properties and evaluation of the toner.

Comparative Example 4
(Preparation of Toner 12)
In Example 1, resin particle dispersion A-1 was changed to resin particle dispersion A-3, 94.4 g of resin particle dispersion C-1 was 79.1 g of resin particle dispersion B-1 and deionized water 15 A toner was obtained in the same manner as in Example 1 except that the dispersion was changed to a mixture mixed with 3 g. Table 4 shows the physical properties and evaluation of the toner.

Comparative Example 5
(Preparation of Toner 13)
A toner was obtained in the same manner as in Example 1 except that the resin particle dispersion C-1 was changed to C-6 in Example 1. Table 4 shows the physical properties and evaluation of the toner.

  From Table 4, it can be seen that the toner for developing an electrostatic charge image of the example has both excellent low-temperature fixability and heat-resistant storage stability and can suppress toner scattering as compared with the toner for developing an electrostatic charge image of the comparative example. .

  The toner for developing an electrostatic image obtained by the production method of the present invention can be suitably used as a toner used in electrophotography because it can achieve both good low-temperature fixability and heat-resistant storage stability and suppress toner scattering. According to the method of the present invention, a toner having such characteristics can be produced efficiently.

Claims (11)

A method for producing a core-shell type electrostatic image developing toner comprising the following steps (1) to (3):
Step (1): Step of aggregating resin particles (A) containing crystalline polyester (a) and release agent particles containing a release agent to obtain aggregated particles (1) Step (2): Aggregation Resin particles (C) made of a graft polymer composed of a main chain segment (A1) made of a polyester resin and side chain segments (A2) made of an addition polymerization resin are added to the particles (1), and agglomerated particles ( Step 2) Step (3): Fusing the agglomerated particles (2) to obtain core-shell particles   A polyester resin (c1) in which the graft polymer has a non-aromatic carbon-carbon unsaturated bond in the main chain is prepared, the polyester resin (c1) is mixed with an aqueous medium, and the polyester resin (c1) Obtained by adding an addition polymerizable monomer (c2) to the aqueous dispersion and polymerizing to obtain an aqueous dispersion of resin particles (C) comprising a graft polymer. The method for producing a toner for developing an electrostatic image according to claim 1.   The electrostatic charge image according to claim 1 or 2, wherein the weight ratio of the main chain segment (A1) to the side chain segment (A2) [segment (A1) / segment (A2)] is 95/5 to 99/1. A method for producing a developing toner.   The raw material monomer from which the structural unit of the main chain segment (A1) is derived contains at least one selected from unsaturated aliphatic dicarboxylic acids, unsaturated alicyclic dicarboxylic acids, and unsaturated aliphatic diols. 4. A method for producing a toner for developing an electrostatic charge image according to any one of 3 above.   The electrostatic charge of Claim 4 which contains 20-100 mol% of unsaturated aliphatic dicarboxylic acid and / or unsaturated alicyclic dicarboxylic acid in the carboxylic acid component of the said principal chain segment (A1) as said raw material monomer. A method for producing a toner for image development.   The electrostatic charge image developing toner according to any one of claims 1 to 5, wherein the addition polymerizable monomer derived from the structural unit of the addition polymerization resin comprises a styrene monomer and / or a (meth) acrylic acid ester. Production method.   The crystalline polyester (a) is a crystalline polyester obtained by polycondensation of an α, ω-alkanediol having 4 to 12 carbon atoms and an aliphatic dicarboxylic acid having 8 to 12 carbon atoms. A method for producing a toner for developing an electrostatic image according to any one of the above.   The method for producing a toner for developing an electrostatic charge image according to claim 1, wherein the resin particles (A) contain an amorphous polyester (b).   The toner for developing an electrostatic charge image according to claim 8, wherein the weight ratio [(a) / (b)] of the crystalline polyester (a) to the amorphous polyester (b) is 5/95 to 30/70. Manufacturing method.   The amorphous polyester (b) comprises an acid component and an alcohol component containing an alkyl succinic acid having a branched alkyl group having 9 to 14 carbon atoms and / or an alkenyl succinic acid having a branched alkenyl group having 9 to 14 carbon atoms. The method for producing a toner for developing an electrostatic charge image according to claim 8, wherein the toner is an amorphous polyester obtained by condensation polymerization.   The method for producing a toner for developing an electrostatic charge image according to claim 1, wherein the resin particles (A) contain a colorant.