JP6267579B2 - Toner for electrostatic image development - Google Patents

Description

  The present invention relates to a toner for developing an electrostatic image and a method for producing the same.

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. The toner is manufactured by a coagulation method or an aggregation fusion method), and studies are being made to improve the performance of the toner by incorporating resins having different physical properties into the core and the shell.
In addition, in order to satisfy a plurality of performances simultaneously, an attempt to combine a plurality of resins has been studied.

As an example of a toner having a core and a shell, Patent Document 1 discloses a core particle containing at least a binder resin and a wax and a shell formed by coating the core particle for the purpose of improving low-temperature fixing characteristics and the like. In the toner for developing an electrostatic charge image having a core-shell structure having a layer, the binder resin contains at least a crystalline polyester resin and a styrene-acrylic resin, and the binder resin contains 5 crystalline polyester resin. The styrene-acrylic resin contains a structural unit derived from methyl methacrylate as a constituent component in an amount of 1% by mass to 10% by mass with respect to the total of the binder resin and the wax. In addition, a toner for developing an electrostatic charge image is disclosed in which the resin constituting the shell layer contains a styrene-acryl-modified polyester resin.
In Patent Document 2, an alcohol component containing an aliphatic diol having 2 to 12 carbon atoms and an aliphatic dicarboxylic acid having 8 to 12 carbon atoms is used for the purpose of improving low-temperature fixability, carrier contamination resistance, and charging rate. A crystalline polyester obtained by polycondensation of a carboxylic acid component containing 70 to 100 mol% of an acid compound, an alcohol component, alkyl (carbon number 9 to 18) succinic acid and alkenyl (carbon number 9 to 18) succinic acid An amorphous resin (A) obtained by polycondensation with a carboxylic acid component containing 3 to 60 mol% of at least one selected succinic acid compound, and the shell portion has a carboxylic acid component and a carbon number of 2 Disclosed is a binder resin for toner comprising core-shell particles, which is an amorphous resin (B) obtained by polycondensation with an alcohol component containing 80 mol% or more of -5 aliphatic dialcohol. It has been.
In addition, as an example of an attempt to combine a plurality of resins, Patent Document 3 discloses that a diol having 8 to 12 carbon atoms and a dicarboxylic acid having 10 to 12 carbon atoms are used for the purpose of improving low temperature fixability, heat resistant storage stability, and the like. A crystalline polyester (1-1) obtained by using a raw material monomer containing a compound and having a total content of 80 mol% or more, an alcohol component, and a carboxylic acid component containing an aromatic dicarboxylic acid compound Amorphous polycondensation resin raw material monomer, addition polymerization resin raw material monomer, and addition polymerization resin raw material monomer of 3 to 15 parts by weight of amorphous polycondensation resin raw material monomer And an amorphous hybrid comprising an amorphous polycondensation resin component and an addition polymerization resin component obtained by polymerizing a compound capable of reacting with any of the raw material monomers of the addition polymerization resin An electrostatic charge image developing toner containing a binder resin containing a fat (2-1), the crystalline polyester (1-1) and the amorphous hybrid resin (2-1) Is a toner for developing an electrostatic image having a weight ratio (crystalline polyester (1-1) / amorphous hybrid resin (2-1)) of 1/99 to 40/60.
Patent Document 4 discloses a binder resin for an electrophotographic toner containing a polycondensation resin and a styrene resin for the purpose of improving low temperature fixability, charging stability under high temperature and high humidity, and storage stability. The polycondensation resin is a resin obtained by polycondensation of an alcohol component containing an aliphatic polyhydric alcohol (alcohol A) having two or more secondary carbon atoms bonded with a hydroxyl group and a carboxylic acid component. A certain binder resin for electrophotographic toner is disclosed.

JP 2012-255957 A JP 2011-197193 A JP2013-109237A JP 2010-107670 A

As the speed of electrophotographic printing increases, it is necessary to fix with less energy at the time of printing. For this reason, the toner to be used is required to have fixability at a low temperature. However, in order to fix at low temperature, it is necessary to lower the softening point of the resin used for the toner and the glass transition temperature, which causes the toner to break easily due to friction with the toner during printing, and lowers durability. There was a problem.
Furthermore, in order to achieve both low-temperature fixability and durability, attempts have been made to use crystalline resins that are solid at normal storage temperatures and low viscosity at high temperatures during fixing. However, when the crystalline resin is exposed to the toner surface, the crystalline resin is detached from the toner, and toner filming on the photosensitive member occurs.
In order to suppress the exposure of the crystalline resin to the toner surface, when the crystalline resin is mixed with another resin having high compatibility with the crystalline resin, crystallization of the crystalline resin does not occur. The durability is inferior.
An object of the present invention is to provide a toner for developing an electrostatic image having both low-temperature fixability and durability and excellent filming resistance, and a method for producing the same.

  The inventor considered that the factors affecting the low-temperature fixability, durability, and filming resistance are the dispersion state of the resin in the toner. As a result, by using a core-shell type toner with crystalline polyester and vinyl resin in the core and a specific amorphous composite resin in the shell, both low-temperature fixability and durability are achieved, and filming resistance is improved. It was found that it can be improved.

That is, the present invention provides the following [1] and [2].
[1] An electrostatic charge image developing toner having a core and a shell,
The core includes a crystalline polyester and a vinyl-based resin, and the shell includes an amorphous composite resin;
The amorphous composite resin contains a polyester resin portion and a vinyl resin portion,
A toner for developing an electrostatic charge image, wherein the polyester resin portion is obtained by polycondensation of an alcohol component containing an aliphatic diol having a hydroxyl group bonded to a secondary carbon atom and a carboxylic acid component.
[2] It has the following steps 1 and 2, wherein the amorphous composite resin contains a polyester resin portion and a vinyl resin portion, and the raw material monomer of the polyester resin portion is bonded to a secondary carbon atom. A method for producing a toner for developing an electrostatic image, comprising an aliphatic diol having a hydroxyl group.
Step 1: An aqueous dispersion of resin particles I containing crystalline polyester and vinyl resin and an aqueous dispersion of resin particles A containing an amorphous composite resin are mixed and agglomerated to form an aqueous dispersion of resin particles II. Step 2: Step of fusing the resin particles II obtained in Step 1

  According to the present invention, it is possible to provide a toner for developing an electrostatic image having both low-temperature fixability and durability and excellent filming resistance, and a method for producing the same.

[Toner for electrostatic image development]
The electrostatic image developing toner of the present invention is an electrostatic image developing toner having a core and a shell, wherein the core includes a crystalline polyester and a vinyl resin, and the shell is an amorphous composite resin. The amorphous composite resin contains a polyester resin part and a vinyl resin part, and the polyester resin part contains an aliphatic diol having a hydroxyl group bonded to a secondary carbon atom and a carboxyl component. An electrostatic charge image developing toner obtained by polycondensation with an acid component.

The reason why the electrostatic image developing toner of the present invention (hereinafter also simply referred to as “toner”) has both low-temperature fixability and durability and excellent filming resistance is not clear, but is as follows. Conceivable.
The toner of the present invention includes an aliphatic diol having a core containing a crystalline polyester and a vinyl resin, and a shell having a hydroxyl group bonded to a secondary carbon atom (hereinafter also referred to as “secondary hydroxyl group”). It has a core-shell structure including an amorphous composite resin containing a derived polyester resin portion and a vinyl resin portion.
Since the core contains crystalline polyester, it has a low viscosity at a high temperature during fixing, and is considered to be excellent in low-temperature fixability.
On the other hand, the amorphous composite resin contained in the shell has a polyester resin portion made of an aliphatic diol having a secondary hydroxyl group as a raw material, and the polyester resin portion is in contact with the crystalline polyester contained in the core. Since the compatibility is poor, it is considered that the exposure of the crystalline polyester to the toner surface is efficiently suppressed and the filming resistance is also excellent.
Further, the core contains a vinyl resin, but the vinyl resin has a molecular weight suitable for a toner and a softening point, and has excellent affinity with the vinyl resin portion of the amorphous composite resin contained in the shell. It is thought that it is excellent also in durability, without causing cracking or interface peeling between the core and the shell.

<Core>
The core constituting the toner of the present invention contains a crystalline polyester and a vinyl resin.

(Crystalline polyester)
The crystalline polyester is a crystallinity index defined by the ratio of the softening point and the maximum endothermic peak temperature (softening point (° C.) / Maximum endothermic peak temperature (° C.)) in the measurement method described in the examples described later. Is a polyester of 0.6 or more and 1.3 or less, preferably 0.8 or more and 1.2 or less, more preferably 0.9 or more and 1.1 or less. In crystalline polyester, the melting point is the maximum endothermic peak temperature.

[Softening point]
The softening point of the crystalline polyester is preferably 55 ° C. or higher, more preferably 60 ° C. or higher, more preferably 65 ° C. or higher, from the viewpoint of low-temperature fixability, durability, and filming resistance of the toner. Preferably it is 120 degrees C or less, More preferably, it is 100 degrees C or less, More preferably, it is 75 degrees C or less.
The softening point of the crystalline polyester is preferably lower than the softening point of the amorphous composite resin described later from the viewpoint of low-temperature fixability of the toner. The difference in softening point between the crystalline polyester and the amorphous composite resin is preferably 5 ° C. or higher, more preferably 20 ° C. or higher, and further preferably 35 ° C. or higher, from the viewpoint of low-temperature fixability of the toner. Further, from the viewpoint of toner durability, it is preferably 60 ° C. or lower, more preferably 50 ° C. or lower, and further preferably 45 ° C. or lower.

[Melting point]
The melting point of the crystalline polyester is preferably 40 ° C. or higher, more preferably 50 ° C. or higher, more preferably 60 ° C. or higher, and preferably from the viewpoint of low-temperature fixability, durability, and filming resistance of the toner. Is 120 ° C. or lower, more preferably 90 ° C. or lower, and still more preferably 75 ° C. or lower.

[Acid value]
The acid value of the crystalline polyester is preferably 10 mgKOH / g or more, more preferably 15 mgKOH / g or more, still more preferably 22 mgKOH / g or more, from the viewpoints of productivity and low-temperature fixability of the toner, and preferably It is 40 mgKOH / g or less, More preferably, it is 30 mgKOH / g or less, More preferably, it is 25 mgKOH / g or less.

  The desired softening point, melting point, and acid value of the crystalline polyester can be obtained by adjusting the charging ratio of the alcohol component and the acid component, the polycondensation temperature, the reaction time, etc., which are the raw material monomers for the crystalline polyester. Can do. The softening point, melting point, and acid value are determined by the methods described in the examples.

  The crystalline polyester is produced by a polycondensation reaction between an alcohol component (hereinafter also referred to as “alcohol component (a-al)”) and an acid component (hereinafter also referred to as “acid component (a-ac)”). can do.

≪Alcohol component (a-al) ≫
Examples of the alcohol component (a-al) include aliphatic diols, aromatic diols, hydrogenated products of bisphenol A, and trivalent or higher alcohols. Among these, aliphatic diols are preferable from the viewpoint of promoting crystallization of polyester and improving low-temperature fixability of the toner.
The carbon number of the aliphatic diol is preferably 2 or more, more preferably 4 or more, still more preferably 6 or more, and preferably 14 from the viewpoint of low-temperature fixability, durability, and filming resistance of the toner. Hereinafter, it is more preferably 12 or less, and still more preferably 10 or less.
The aliphatic diol preferably has a hydroxyl group at the end of the carbon chain from the viewpoint of low-temperature fixability, durability, and filming resistance of the toner, and is preferably an α, ω-linear alkanediol. More preferred.

  Aliphatic diols include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol and the like. Among these, 1,4-butanediol and 1,6-hexanediol are preferable, and 1,6-hexanediol is more preferable from the viewpoint of low-temperature fixability, durability, and filming resistance of the toner. .

Examples of the aromatic diol include an adduct of bisphenol A with an alkylene (2 to 3 carbon atoms) oxide (an average addition mole number of 1 to 16).
Examples of trihydric or higher alcohols include sorbitol, pentaerythritol, glycerin, trimethylolpropane and the like.

  These alcohol components (a-al) can be used alone or in combination of two or more. From the viewpoint of promoting the crystallization of polyester, the alcohol component (a-al) has 6 or more carbon atoms. The content of the aliphatic diol of 12 or less is preferably 60 mol% or more, more preferably 80 mol% or more, still more preferably 95 mol% or more, and still more preferably 100 mol%.

≪Acid component (a-ac) ≫
Examples of the acid component (a-ac) include aliphatic dicarboxylic acid compounds, alicyclic dicarboxylic acid compounds, aromatic dicarboxylic acid compounds, and trivalent or higher carboxylic acid compounds. Among these, from the viewpoint of low-temperature fixability, durability, and filming resistance of the toner, an aliphatic dicarboxylic acid compound is preferable, and a saturated aliphatic dicarboxylic acid compound is more preferable.
The number of carbon atoms of the aliphatic dicarboxylic acid compound is preferably 4 or more, more preferably 6 or more, and still more preferably 8 or more, from the viewpoint of low-temperature fixability, durability, and filming resistance of the toner. Is 16 or less, more preferably 14 or less, and still more preferably 12 or less.
In addition, the carbon number of the aliphatic dicarboxylic acid compound includes the carbon number of the carboxy group in the carbon number of the linear or branched hydrocarbon group, and does not include the carbon number of the alkyl ester.

  Examples of the aliphatic dicarboxylic acid compound include oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, adipic acid, sebacic acid, 1,8-octanedicarboxylic acid, 1,12 -Dodecanedioic acid, azelaic acid, n-dodecyl succinic acid, n-dodecenyl succinic acid, etc. are mentioned. Among these, from the viewpoint of low-temperature fixability, durability, and filming resistance of the toner, fumaric acid, adipic acid, and 1,8-octanedicarboxylic acid are preferable, and adipic acid and 1,8-octanedicarboxylic acid are more preferable. An acid, more preferably 1,8-octanedicarboxylic acid.

Examples of the alicyclic dicarboxylic acid compound include cyclohexane dicarboxylic acid.
Examples of the aromatic dicarboxylic acid compound include terephthalic acid, phthalic acid, and isophthalic acid. Among these, terephthalic acid is preferred from the viewpoints of low-temperature fixability, durability, and filming resistance of the toner.
Examples of the trivalent or higher carboxylic acid compound include trimellitic acid and pyromellitic acid.
In the present specification, the acid includes not only a free acid but also an anhydride that decomposes during the reaction to produce an acid, and an alkyl ester.

  These acid components (a-ac) can be used alone or in combination of two or more. From the viewpoint of promoting crystallization of polyester, the acid component (a-ac) has 4 or more carbon atoms. The content of the aliphatic dicarboxylic acid compound of 12 or less is preferably 80 mol% or more, more preferably 90 mol% or more, still more preferably 95 mol% or more, and still more preferably 100 mol%.

≪Reaction conditions≫
Crystalline polyester is formed by the polycondensation reaction of the alcohol component (a-al) and the acid component (a-ac).
From the viewpoint of reactivity, the temperature during the polycondensation reaction is preferably 130 ° C. or higher, more preferably 145 ° C. or higher, still more preferably 160 ° C. or higher, and preferably 240 ° C. or lower, more preferably 230 ° C. or lower. More preferably, it is 220 ° C. or lower.
The molar ratio of the acid component (a-ac) and the alcohol component (a-al) during the polycondensation reaction [acid component (a-ac) / alcohol component (a-al)] is the low-temperature fixability and durability of the toner. From the viewpoints of film property and filming resistance, it is preferably 0.80 or more, more preferably 0.90 or more, still more preferably 0.95 or more, and preferably 1.20 or less, more preferably 1. 15 or less, more preferably 1.10 or less.

  The polycondensation reaction may be performed in an inert gas atmosphere in the presence of an esterification catalyst, an esterification cocatalyst, a polymerization inhibitor, or the like, if necessary.

{Esterification catalyst}
Examples of the esterification catalyst suitably used for the polycondensation reaction include a titanium compound and a tin (II) compound having no Sn—C bond, and these should be used alone or in combination of two or more. Can do.

  As the titanium compound, a titanium compound having a Ti—O bond is preferable, and a compound having an alkoxy group, an alkenyloxy group or an acyloxy group having 1 to 28 carbon atoms in total is more preferable.

  Examples of the tin (II) compound having no Sn—C bond include a tin (II) compound having a Sn—O bond, a tin (II) compound having a Sn—X (X represents a halogen atom) bond, and the like. Preferred is a tin (II) compound having a Sn-O bond, and among them, di (2-ethylhexanoic acid) tin (II) salt from the viewpoints of reactivity, molecular weight adjustment and physical property adjustment of crystalline polyester. Is more preferable.

  The amount of the esterification catalyst used is preferably 100 parts by mass with respect to the total amount of the alcohol component (a-al) and the acid component (a-ac) from the viewpoints of reactivity, molecular weight adjustment, and resin physical property adjustment. 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, still more preferably 0.4 parts by mass or more, and preferably 1.5 parts by mass or less, more preferably 1.0 parts by mass or less, More preferably, it is 0.6 parts by mass or less.

{Esterification cocatalyst}
Examples of esterification promoters include pyrogallol compounds such as pyrogallol, gallic acid, and gallic acid esters; benzophenone derivatives such as 2,3,4-trihydroxybenzophenone and 2,2 ′, 3,4-tetrahydroxybenzophenone; epigallocatechin And catechin derivatives such as epigallocatechin gallate, and gallic acid is preferred from the viewpoint of reactivity.
The amount of the esterification cocatalyst used is preferably based on 100 parts by mass of the total amount of the alcohol component (a-al) and the acid component (a-ac) from the viewpoints of reactivity, molecular weight adjustment, and resin physical property adjustment. Is 0.001 part by mass or more, more preferably 0.01 part by mass or more, further preferably 0.04 part by mass or more, and preferably 0.15 part by mass or less, more preferably 0.10 part by mass or less. More preferably, it is 0.06 parts by mass or less.

{Polymerization inhibitor}
The polymerization inhibitor is not particularly limited, but 4-t-butylcatechol is preferable.
The polymerization inhibitor is preferably used in an amount of 100 parts by mass of the total amount of the alcohol component (a-al) and the acid component (a-ac) from the viewpoints of reactivity, molecular weight adjustment, and resin physical property adjustment. 0.0004 parts by mass or more, more preferably 0.004 parts by mass or more, further preferably 0.016 parts by mass or more, and preferably 0.06 parts by mass or less, more preferably 0.04 parts by mass or less, More preferably, it is 0.024 mass part or less.

(Vinyl resin)
The vinyl resin is not particularly limited as long as it is a vinyl resin having physical properties and the like generally used for toner.
The vinyl resin can be produced by subjecting a starting vinyl monomer to an addition polymerization reaction. In addition polymerization reaction, you may use a radical polymerization initiator and a polymerization inhibitor as needed.

Examples of the raw material vinyl monomer for the vinyl resin include vinyl monomers having an alkyl group.
The number of carbon atoms of the alkyl group of the vinyl monomer having an alkyl group is not particularly limited, but is preferably 1 or more, more preferably 2 or more, still more preferably 3 or more, and preferably 20 or less, more preferably 10 or less. More preferably, it is 5 or less. The vinyl monomer having an alkyl group is preferably a (meth) acrylate having an alkyl group, more preferably an acrylate having an alkyl group, from the viewpoint of low-temperature fixability, durability, and filming resistance of the toner. Is n-butyl acrylate.

Moreover, as a raw material vinyl monomer, another vinyl monomer can be used together with the vinyl monomer having the alkyl group. Examples of the other vinyl monomers include styrene compounds such as styrene and α-methylstyrene; ethylenically unsaturated monoolefins such as ethylene and propylene; diolefins such as butadiene; halovinyls such as vinyl chloride; vinyl acetate and propion. Vinyl esters such as vinyl acid; esters of ethylenic monocarboxylic acid such as dimethylaminoethyl (meth) acrylate; vinyl ethers such as vinyl methyl ether; vinylidene halides such as vinylidene chloride; N- such as N-vinylpyrrolidone; Examples include vinyl compounds. Among these, from the viewpoint of low-temperature fixability, durability, and filming resistance of the toner, a styrene compound is preferable, and styrene is more preferable.
Further, from the viewpoint of low-temperature fixability, durability, and filming resistance of the toner, it is preferable to use a vinyl monomer having an alkyl group and a styrene compound in combination, and it is more preferable to use n-butyl acrylate and styrene in combination. preferable.

  The content of the vinyl monomer having an alkyl group in the raw vinyl monomer, which is a component derived from the vinyl resin, is preferably 15% by mass or more from the viewpoint of low-temperature fixability, durability, and filming resistance of the toner. More preferably, it is 20 mass% or more, More preferably, it is 25 mass% or more, More preferably, it is 30 mass% or more, Preferably it is 55 mass% or less, More preferably, it is 50 mass% or less, More preferably, it is 45 mass% Hereinafter, it is still more preferably 40% by mass or less.

  The content of the styrene compound in the starting vinyl monomer, which is a component derived from the vinyl resin, is preferably 45% by mass or more, more preferably 50%, from the viewpoints of low-temperature fixability, durability, and filming resistance of the toner. % By mass or more, more preferably 55% by mass or more, still more preferably 60% by mass or more, and preferably 85% by mass or less, more preferably 80% by mass or less, still more preferably 75% by mass or less, and still more. Preferably it is 70 mass% or less.

  The temperature of the addition polymerization reaction is preferably 100 ° C. or higher, more preferably 110 ° C. or higher, further preferably 130 ° C. or higher, and preferably 160 ° C. or lower, more preferably 150 ° C. or lower, still more preferably 140 ° C. or lower. It is.

[Softening point]
The softening point of the vinyl resin is preferably 100 ° C. or higher, more preferably 110 ° C. or higher, more preferably 115 ° C. or higher, from the viewpoint of low-temperature fixability, durability, and filming resistance of the toner. Preferably it is 140 degrees C or less, More preferably, it is 130 degrees C or less, More preferably, it is 125 degrees C or less.
〔Glass-transition temperature〕
The glass transition temperature of the vinyl resin is preferably 30 ° C. or higher, more preferably 40 ° C. or higher, more preferably 50 ° C. or higher, from the viewpoints of low-temperature fixability, durability, and filming resistance of the toner. The temperature is preferably 80 ° C. or lower, more preferably 70 ° C. or lower, and still more preferably 60 ° C. or lower.
[Crystallinity index]
The crystallinity index of the vinyl resin is preferably 1.7 or more, more preferably 1.8 or more, and still more preferably 1.9 or more, from the viewpoint of low-temperature fixability, durability, and filming resistance of the toner. Yes, and preferably 2.5 or less, more preferably 2.3 or less, and still more preferably 2.1 or less.

(Other ingredients)
The core constituting the toner of the present invention may contain a known resin used for the toner, for example, epoxy, polycarbonate, polyurethane, etc., in addition to the crystalline polyester and the vinyl resin.
The core may contain a colorant, a release agent, and a charge control agent as long as the effects of the present invention are not impaired. Furthermore, you may contain additives, such as reinforcement fillers, such as a fibrous material, antioxidant, and anti-aging agent, as needed.

[Colorant]
As the colorant, all of dyes and pigments used as toner colorants can be used, such as carbon black, phthalocyanine blue, permanent brown FG, brilliant first scarlet, pigment green B, rhodamine-B base, Solvent Red 49, Solvent Red 146, Solvent Blue 35, Quinacridone, Carmine 6B, Disazo Yellow and the like can be used, and the toner of the present invention may be either black toner or color toner.
The content of the colorant is preferably from 100 parts by mass of the resin component constituting the core from the viewpoint of improving the image density of the toner and from the viewpoint of low-temperature fixability, durability, and filming resistance of the toner. 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, further preferably 1.0 parts by mass or more, and preferably 40 parts by mass or less, more preferably 20 parts by mass or less, still more preferably 5 parts by mass. It is below mass parts.

〔Release agent〕
As the release agent, low molecular weight polypropylene, low molecular weight polyethylene, low molecular weight polypropylene polyethylene copolymer, aliphatic hydrocarbon wax such as microcrystalline wax, paraffin wax, Fischer-Tropsch wax and oxides thereof, carnauba wax, Examples include ester waxes such as montan wax, sazol wax and their deoxidized waxes, fatty acid ester waxes, fatty acid amides, fatty acids, higher alcohols, fatty acid metal salts, and the like. It can be used by mixing.
The melting point of the release agent is preferably 60 ° C. or higher, more preferably 65 ° C. or higher, and further preferably 70 ° C. or higher, from the viewpoint of low-temperature fixability, durability, and filming resistance of the toner. Is 90 ° C. or lower, more preferably 85 ° C. or lower, and still more preferably 80 ° C. or lower.
The content of the release agent is preferably 100 parts by mass of the resin component constituting the core from the viewpoints of dispersibility in the resin and low temperature fixability, durability, and filming resistance of the toner. Is 1 part by mass or more, more preferably 3 parts by mass or more, still more preferably 5 parts by mass or more, and preferably 15 parts by mass or less, more preferably 12 parts by mass or less, still more preferably 9 parts by mass or less. .

[Charge control agent]
The charge control agent is not particularly limited, and may contain either a positively chargeable charge control agent or a negatively chargeable charge control agent.
Examples of positively chargeable charge control agents include nigrosine dyes such as “Nigrosine Base EX”, “Oil Black BS”, “Oil Black SO”, “Bontron (registered trademark) N-01”, “Bontron N-04”, “ Bontron N-07 "," Bontron N-09 "," Bontron N-11 "(manufactured by Orient Chemical Industry Co., Ltd.), etc .; triphenylmethane dyes containing quaternary amines as side chains, quaternary ammonium salts Compounds such as “Bontron P-51” (manufactured by Orient Chemical Co., Ltd.), cetyltrimethylammonium bromide, “COPY CHARGE PX VP435” (manufactured by Clariant), etc .; polyamine resins such as “AFP-B” (Orient Chemical Industries Ltd.) Imidazole derivatives such as “PLZ-2001”, “P Z-8001 "(all, made by Shikoku Kasei Co., Ltd.); styrene - acrylic resin, for example," FCA-701PT "(manufactured by Fujikura Kasei), and the like.
Examples of the negatively chargeable charge control agent include metal-containing azo dyes such as “Varifast Black 3804”, “Bontron S-31”, “Bontron S-32”, “Bontron S-34”, “Bontron S-”. 36 ”(manufactured by Orient Chemical Co., Ltd.),“ Eisenspiron Black TRH ”,“ T-77 ”(manufactured by Hodogaya Chemical Co., Ltd.), etc .; metal compounds of benzylic acid compounds such as“ LR-147 ” ”,“ LR-297 ”(manufactured by Nippon Carlit Co., Ltd.) and the like; metal compounds of salicylic acid compounds such as“ Bontron E-81 ”,“ Bontron E-84 ”,“ Bontron E-88 ”,“ E- ” 304 "(above, manufactured by Orient Chemical Co., Ltd.)," TN-105 "(manufactured by Hodogaya Chemical Co., Ltd.), etc .; copper phthalocyanine dye; quaternary ammonia Salts, for example, "COPY CHARGE NX VP434" (manufactured by Clariant), nitroimidazole derivatives; organometallic compounds such as "TN105" (manufactured by Hodogaya Chemical Co., Ltd.).
The content of the charge control agent is preferably based on 100 parts by mass of the resin component constituting the core, from the viewpoint of charging stability of the toner and from the viewpoint of low-temperature fixability, durability, and filming resistance of the toner. 0.0005 parts by mass or more, more preferably 0.001 parts by mass or more, further preferably 0.005 parts by mass or more, and preferably 1 part by mass or less, more preferably 0.1 parts by mass or less, still more preferably Is 0.01 parts by mass or less.

(Content of resin component in the core)
The content of the resin component in the core is preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably 95% by mass or more, from the viewpoints of low-temperature fixability, durability, and filming resistance of the toner. And preferably 100% by mass or less, more preferably 99% by mass or less, and still more preferably 98% by mass or less.
The resin component in the core includes crystalline polyester, vinyl resin, and other resins that are optionally used.

(Total content of crystalline polyester and vinyl resin in resin component)
The total content of the crystalline polyester and the vinyl resin in the resin component constituting the core is preferably 80% by mass or more, more preferably from the viewpoint of low-temperature fixability, durability, and filming resistance of the toner. Is 90% by mass or more, more preferably 99% by mass or more, and still more preferably 100% by mass.

(Mass ratio of crystalline polyester to vinyl resin)
In the resin component constituting the core, the mass ratio of crystalline polyester to vinyl resin (crystalline polyester / vinyl resin) is preferably from the viewpoint of low-temperature fixability, durability, and filming resistance of the toner. It is 40/60 or more, more preferably 50/50 or more, further preferably 60/40 or more, and preferably 95/5 or less, more preferably 90/10 or less, still more preferably 80/20 or less.

<Shell>
The shell constituting the toner of the present invention contains an amorphous composite resin, and the amorphous composite resin contains a polyester resin portion and a vinyl resin portion, and the polyester resin portion has secondary carbon atoms. It is obtained by polycondensation of an alcohol component containing an aliphatic diol having a bonded hydroxyl group and a carboxylic acid component.

(Amorphous composite resin)
The amorphous composite resin contains a polyester resin portion and a vinyl resin portion.
In the present invention, amorphous is defined as the ratio of the softening point to the maximum endothermic peak temperature (softening point (° C.) / Maximum endothermic peak temperature (° C.)) in the measurement method described in the examples described later. The polyester has a crystallinity index of greater than 1.3 or less than 0.6, preferably greater than 1.3 and 4 or less, more preferably 1.5 or more and 3 or less.
[Softening point]
The softening point of the amorphous composite resin is preferably 60 ° C. or higher, more preferably 90 ° C. or higher, and still more preferably 107 ° C. or higher, from the viewpoint of low-temperature fixability, durability, and filming resistance of the toner. And preferably it is 170 degrees C or less, More preferably, it is 120 degrees C or less, More preferably, it is 115 degrees C or less.
〔Glass-transition temperature〕
The glass transition temperature of the amorphous composite resin is preferably 40 ° C. or higher, more preferably 50 ° C. or higher, and further preferably 55 ° C. or higher, from the viewpoint of low-temperature fixability, durability, and filming resistance of the toner. . Further, from the viewpoint of low-temperature fixability of the toner, it is preferably 80 ° C. or less, more preferably 70 ° C. or less, and further preferably 60 ° C. or less.
[Acid value]
The acid value of the amorphous composite resin is preferably 10 mgKOH / g or more, more preferably 15 mgKOH / g or more, still more preferably 18 mgKOH / g or more, from the viewpoints of productivity and toner durability. Is 40 mgKOH / g or less, more preferably 30 mgKOH / g or less, still more preferably 25 mgKOH / g or less.

  The amorphous composite resin includes a raw material monomer for a polyester resin part, a raw material monomer for a vinyl resin part, a bireactive monomer capable of reacting with both a raw material monomer for a polyester resin part and a raw material monomer for a vinyl resin part; It is preferable to be obtained by polymerizing.

≪Polyester resin part≫
The polyester resin portion comprises an alcohol component (hereinafter also referred to as “alcohol component (b-al)”) and a carboxylic acid component (hereinafter referred to as “acid component (hereinafter referred to as“ acid component ”) having a hydroxyl group bonded to a secondary carbon atom. b-ac) ")) and obtained by polycondensation.

{Alcohol component (b-al)}
Examples of the aliphatic diol having a hydroxyl group bonded to a secondary carbon atom include 1,2-propanediol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, and 1,2-pentane. Diols, 1,3-pentanediol, 2,3-pentanediol, 2,4-pentanediol, and the like. Among these, from the viewpoint of low-temperature fixability, durability, and filming resistance of the toner, 1 is preferable. 1,2-propanediol and 2,3-butanediol, more preferably 1,2-propanediol.
The number of carbon atoms of the aliphatic diol having a hydroxyl group bonded to a secondary carbon atom is preferably 3 or more from the viewpoint of low-temperature fixability, durability, and filming resistance of the toner, and preferably It is 6 or less, more preferably 5 or less, and still more preferably 4 or less.
The content of the aliphatic diol having a hydroxyl group bonded to a secondary carbon atom is preferably 80 mol in the alcohol component (b-al) from the viewpoint of low-temperature fixability, durability, and filming resistance of the toner. % Or more, more preferably 90 mol% or more, still more preferably 95 mol% or more, and still more preferably 100 mol%.
Examples of the alcohol component (b-al) other than the aliphatic diol having a hydroxyl group bonded to a secondary carbon atom include aromatic diols such as α, ω-aliphatic diols and alkylene oxide adducts of bisphenol A, sorbitol, penta Examples include trihydric or higher polyhydric alcohols such as erythritol, glycerin, and trimethylolpropane.

{Acid component (b-ac)}
The acid component (b-ac) preferably contains an aromatic dicarboxylic acid compound from the viewpoints of low-temperature fixability, durability, and filming resistance of the toner.
Examples of the aromatic dicarboxylic acid compound include phthalic acid, isophthalic acid, terephthalic acid, anhydrides of these acids, and alkyl (1 to 3 carbon atoms) esters of these acids. Among these, terephthalic acid and isophthalic acid are preferable from the viewpoint of durability of the toner, and terephthalic acid is more preferable.
The content of the aromatic dicarboxylic acid compound is preferably 30 mol% or more, more preferably 40 mol% or more, still more preferably 60 mol% or more in the alcohol component (b-al) from the viewpoint of toner durability. is there. Further, from the viewpoint of low-temperature fixability of the toner, it is preferably 95 mol% or less, more preferably 90 mol% or less, and still more preferably 80 mol% or less.

The acid component (b-ac) preferably further contains an aliphatic dicarboxylic acid compound from the viewpoint of low-temperature fixability of the toner.
The number of carbon atoms of the aliphatic dicarboxylic acid compound is preferably 2 or more, more preferably 3 or more, and further preferably 4 or more, from the viewpoint of low-temperature fixability, durability, and filming resistance of the toner. Is 6 or less, more preferably 5 or less.
In addition, the carbon number of the aliphatic dicarboxylic acid compound includes the carbon number of the carboxy group in the carbon number of the linear or branched hydrocarbon group, and does not include the carbon number of the alkyl ester.
Examples of the aliphatic dicarboxylic acid compound having 2 to 6 carbon atoms include fumaric acid, maleic acid, malonic acid, succinic acid, glutaric acid, glutaconic acid, adipic acid, anhydrides of these acids, and 1 to 3 carbon atoms. The following alkyl esters and the like can be mentioned, and among these, fumaric acid is preferable from the viewpoint of low-temperature fixability, durability, and filming resistance of the toner.
The molar ratio between the aromatic dicarboxylic acid compound and the aliphatic dicarboxylic acid compound having 2 to 6 carbon atoms (aromatic dicarboxylic acid compound / aliphatic dicarboxylic acid compound) is the low-temperature fixability and durability of the toner. From the viewpoints of film property and filming resistance, it is preferably 40/60 or more, more preferably 50/50 or more, still more preferably 60/40 or more, and preferably 90/10 or less, more preferably 85 / 15 or less, more preferably 80/20 or less.
Examples of acid components (b-ac) other than aromatic dicarboxylic acid compounds and aliphatic dicarboxylic acid compounds having 2 to 6 carbon atoms include aliphatic dicarboxylic acid compounds having 7 or more carbon atoms, trimellitic acid, pyromellitic acid, and the like And trivalent or higher polyvalent carboxylic acid compounds.

≪Reaction conditions≫
A polyester resin portion is formed by a polycondensation reaction between the alcohol component (b-al) and the acid component (b-ac).
From the viewpoint of reactivity, the temperature during the polycondensation reaction is preferably 180 ° C. or higher, more preferably 190 ° C. or higher, still more preferably 200 ° C. or higher, and preferably 250 ° C. or lower, more preferably 240 ° C. or lower. More preferably, it is 230 ° C. or lower.
The molar ratio of the acid component (b-ac) to the alcohol component (b-al) [acid component (b-ac) / alcohol component (b-al)] is the low-temperature fixability, durability, and fill resistance of the toner. From the viewpoint of the mining property, it is preferably 0.70 or more, more preferably 0.80 or more, still more preferably 0.90 or more, and preferably 1.10 or less, more preferably 1.05 or less, still more preferably. Is 1.00 or less.

  The polycondensation reaction may be performed in an inert gas atmosphere in the presence of an esterification catalyst, an esterification cocatalyst, a polymerization inhibitor, or the like, if necessary.

Examples of the esterification catalyst used for the synthesis of the polyester resin portion include the same esterification catalysts used for the synthesis of the crystalline polyester, and the preferred embodiments are also the same.
The amount of the esterification catalyst used is preferably 100 parts by mass with respect to the total amount of the alcohol component (b-al) and the acid component (b-ac) from the viewpoint of reactivity, molecular weight adjustment, and resin physical property adjustment. 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, further preferably 0.6 parts by mass or more, and preferably 1.5 parts by mass or less, more preferably 1.2 parts by mass or less, More preferably, it is 1.0 mass part or less.

{Esterification cocatalyst}
Examples of the esterification co-catalyst used for the synthesis of the polyester resin portion include the same esterification catalysts used for the synthesis of the crystalline polyester, and the preferred embodiments are also the same.
The amount of esterification cocatalyst used in the polycondensation reaction is 100 parts by mass with respect to the total amount of alcohol component (b-al) and acid component (b-ac) used in the polycondensation reaction, from the viewpoint of reactivity. , Preferably 0.005 parts by mass or more, more preferably 0.01 parts by mass or more, further preferably 0.05 parts by mass or more, and preferably 1 part by mass or less, more preferably 0.5 parts by mass or less. More preferably, it is 0.15 parts by mass or less.
From the viewpoint of reactivity, the mass ratio of the esterification cocatalyst to the esterification catalyst [esterification cocatalyst / esterification catalyst] is preferably 0.01 or more, more preferably 0.03 or more, and still more preferably 0.8. It is 05 or more, and preferably 0.5 or less, more preferably 0.3 or less, and still more preferably 0.15 or less.

{Polymerization inhibitor}
The polymerization inhibitor is not particularly limited, but 4-t-butylcatechol is preferable.
The amount of the polymerization inhibitor used is preferably from the viewpoint of reactivity to 100 parts by mass of the total amount of the alcohol component (b-al) and acid component (b-ac) subjected to the polycondensation reaction. 002 parts by mass or more, more preferably 0.004 parts by mass or more, further preferably 0.02 parts by mass or more, and preferably 0.4 parts by mass or less, more preferably 0.2 parts by mass or less, still more preferably. Is 0.06 parts by mass or less.

≪Vinyl resin part≫
Although it does not specifically limit as a vinyl-type resin part, For example, what consists of a polymer of a polystyrene, a styrene derivative, a polyacrylic acid ester, a styrene-acryl copolymer, polyolefin, a polyhalogenated vinyl, a polyvinyl ester etc. is mentioned. . Among these, from the viewpoint of low-temperature fixability, durability, and filming resistance of the toner, it is preferable to include a structural unit derived from styrene such as polystyrene or a styrene-acrylic copolymer.
The content of the structural unit derived from styrene in the vinyl resin portion is preferably 50% by mass or more, more preferably 65% by mass or more, from the viewpoint of low-temperature fixability, durability, and filming resistance of the toner. Preferably it is 75 mass% or more, and preferably is 100 mass% or less, More preferably, it is 95 mass% or less, More preferably, it is 85 mass% or less.

Raw material monomers other than styrene include styrene derivatives such as α-methylstyrene; ethylenically unsaturated monoolefins such as ethylene and propylene; diolefins such as butadiene; halovinyls such as vinyl chloride; vinyl acetate and vinyl propionate. Vinyl esters such as (meth) acrylic acid, esters of ethylenic monocarboxylic acid such as dimethylaminoethyl (meth) acrylate; vinyl ethers such as vinyl methyl ether; vinylidene halides such as vinylidene chloride; N -N-vinyl compounds, such as vinylpyrrolidone, etc. are mentioned.
Of these, alkyl (meth) acrylic acid is preferred from the viewpoint of low-temperature fixability, durability, and filming resistance of the toner.
The number of carbon atoms of the alkyl group of the alkyl ester of (meth) acrylic acid is preferably 1 or more, more preferably 3 or more, and still more preferably 6 or more, from the viewpoints of low-temperature fixability, durability, and filming resistance of the toner. And is preferably 18 or less, more preferably 14 or less, and still more preferably 10 or less.
The content of the structural unit derived from the alkyl ester of (meth) acrylic acid in the vinyl resin portion is preferably 0% by mass or more, more preferably from the viewpoint of low-temperature fixability, durability, and filming resistance of the toner. Is 5% by mass or more, more preferably 15% by mass or more, and preferably 50% by mass or less, more preferably 35% by mass or less, and still more preferably 25% by mass or less.

{Reaction conditions}
The vinyl resin portion is formed by addition polymerization of raw material monomers.
The temperature during the addition polymerization reaction is preferably 140 ° C. or higher, more preferably 150 ° C. or higher, further preferably 155 ° C. or higher, and preferably 180 ° C. or lower, more preferably from the viewpoints of reactivity and molecular weight adjustment. Is 170 ° C. or lower, more preferably 165 ° C. or lower.
Moreover, you may perform addition polymerization reaction in presence of a polymerization initiator etc. as needed. Examples of the polymerization initiator include peroxides such as tert-butyl peroxide, dibutyl peroxide, and dicumyl peroxide.
The amount of the polymerization initiator used is preferably 1 part by mass or more, more preferably 2 parts by mass or more, still more preferably 3 parts by mass or more, with respect to 100 parts by mass of the raw material monomer of the vinyl resin part, and preferably 15 parts by mass or less, more preferably 10 parts by mass or less, and still more preferably 5 parts by mass or less.

≪Amotropic monomer≫
Both reactive monomers can react with either the raw material monomer of the polyester resin portion or the raw material monomer of the vinyl resin portion. By performing the polycondensation reaction and / or the addition polymerization reaction in the presence of the both reactive monomers, the polyester resin portion and the vinyl resin portion are chemically bonded via the structural unit derived from the both reactive monomers, and the polyester resin. A resin in which the vinyl resin is more finely and uniformly dispersed is obtained.
As the both-reactive monomer, from the viewpoint of improving the bond between the polyester resin component and the vinyl resin portion, (meth) acrylic acid, fumaric acid, maleic acid, more preferably (meth) acrylic acid, still more preferably Is acrylic acid.
The amount of both reactive monomers used is preferably 1 mol part or more, more preferably 2 mol parts or more, still more preferably 3 mol parts or more with respect to 100 mol parts of the alcohol component (b-al), and Preferably it is 15 mol parts or less, More preferably, it is 10 mol parts or less, More preferably, it is 5 mol parts or less.

  Specifically, the amorphous composite resin obtained using the both reactive monomers is preferably produced by the following method. Both reactive monomers are preferably used in the addition polymerization reaction together with the raw material monomer for the vinyl resin portion from the viewpoint of expressing the effects of the present invention by controlling the addition polymerization reaction and the polycondensation reaction.

(i) A method of performing a step (B) of an addition polymerization reaction with a raw material monomer and an amphoteric monomer of a vinyl resin portion after the step (A) of the polycondensation reaction with the raw material monomer of the polyester resin portion. The step (A) is performed under a reaction temperature condition suitable for the condensation reaction, the reaction temperature is lowered, and the step (B) is performed under a temperature condition suitable for the addition polymerization reaction. It is preferable to add the raw material monomer of the vinyl resin part and the both reactive monomers to the reaction system at a temperature suitable for the addition polymerization reaction. Both reactive monomers undergo an addition polymerization reaction and also react with the polyester resin portion.
After the step (B), the reaction temperature is raised again to polymerize a dicarboxylic acid compound having an unsaturated bond such as fumaric acid or a raw material monomer of a trivalent or higher polyester resin portion that becomes a cross-linking agent if necessary. To the polycondensation reaction in step (A) and the reaction with both reactive monomers.

(ii) A method in which a step (A) of a polycondensation reaction using a raw material monomer for a polyester resin portion is performed after a step (B) of an addition polymerization reaction using a raw material monomer and an amphoteric monomer for a vinyl resin portion. The step (B) is performed under a reaction temperature condition suitable for the polymerization reaction, the reaction temperature is increased, and the polycondensation reaction of the step (A) is performed under a temperature condition suitable for the polycondensation reaction. Both reactive monomers are involved in the polycondensation reaction as well as the addition polymerization reaction.
The raw material monomer for the polyester resin portion may be present in the reaction system during the addition polymerization reaction, or may be added to the reaction system under temperature conditions suitable for the polycondensation reaction. In the former case, the progress of the polycondensation reaction can be controlled by adding an esterification catalyst at a temperature suitable for the polycondensation reaction.

(iii) A method in which the step (A) of the polycondensation reaction with the raw material monomer in the polyester resin portion and the step (B) of the addition polymerization reaction with the raw material monomer and the both reactive monomers in the vinyl resin portion are performed in parallel. The step (A) and the step (B) are carried out under the reaction temperature conditions suitable for the addition polymerization reaction, the reaction temperature is increased, and the esterification catalyst is optionally produced under the temperature conditions suitable for the polycondensation reaction. It is preferable to further add an esterification co-catalyst and a raw material monomer of a trivalent or higher-valent polyester resin portion serving as a cross-linking agent to the polymerization system to further perform the polycondensation reaction in the step (A). At that time, under a temperature condition suitable for the polycondensation reaction, a radical polymerization inhibitor can be added to advance only the polycondensation reaction. Both reactive monomers are involved in the polycondensation reaction as well as the addition polymerization reaction.

  In the method (i), a prepolymerized polycondensation resin may be used in place of the step (A) for performing the polycondensation reaction. In the method (iii), when the step (A) and the step (B) are performed in parallel, a mixture containing the raw material monomer for the vinyl resin part in the mixture containing the raw material monomer for the polyester resin part. It can also be made to react by dripping.

The methods (i) to (iii) are preferably performed in the same container.
Among these methods, the method (i) is preferable from the viewpoint of promoting the binding reaction between the polyester resin portion and the vinyl resin portion.

(Resin component content in shell)
In the shell constituting the toner of the present invention, a known resin may be used in combination as long as the effects of the present invention are not impaired.
The content of the resin component in the shell is preferably 80% by mass or more, more preferably 90% by mass or more, and further preferably 99% by mass or more, from the viewpoint of low-temperature fixability, durability, and filming resistance of the toner. More preferably, it is 100 mass%.
The resin component in the shell includes an amorphous composite resin and a known resin that is optionally used in combination.

(Total content of amorphous composite resin in resin component)
In the resin component constituting the shell, the content of the amorphous composite resin is preferably 80% by mass or more, more preferably 90% by mass or more, from the viewpoint of low-temperature fixability, durability, and filming resistance of the toner. More preferably, it is 99 mass% or more, and still more preferably 100 mass%.

≪Mass ratio of polyester resin part and vinyl resin part≫
The mass ratio of the polyester resin portion to the vinyl resin portion in the amorphous composite resin (polyester resin portion / vinyl resin portion) is preferably from the viewpoint of low-temperature fixability, durability, and filming resistance of the toner. 50/50 or more, more preferably 60/40 or more, still more preferably 70/30 or more, and preferably 95/5 or less, more preferably 90/10 or less, and still more preferably 85/15 or less.
In this mass ratio, the mass of both reactive monomers is not included in either the polyester resin portion or the vinyl resin portion.

<Mass ratio between core and shell>
The mass ratio (core / shell) of the core and the shell constituting the toner of the present invention is preferably 50/50 or more, more preferably 65, from the viewpoint of low-temperature fixability, durability, and filming resistance of the toner. / 35 or more, more preferably 75/25 or more, and preferably 95/5 or less, more preferably 90/10 or less, still more preferably 85/15 or less.

(External additive)
In the toner of the present invention, an external additive is preferably used in order to improve transferability, and inorganic fine particles are preferably used as the external additive. Examples of the inorganic fine particles include silica, alumina, titania, zirconia, tin oxide, and suboxide, and silica is preferable.
Silica is preferably hydrophobic silica that has been subjected to a hydrophobization treatment from the viewpoint of toner transferability.
Examples of the hydrophobizing agent for hydrophobizing the surface of silica particles include hexamethyldisilazane (HMDS), dimethyldichlorosilane (DMDS), silicone oil, octyltriethoxysilane (OTES), and methyltriethoxysilane. Of these, hexamethyldisilazane is preferred.
The average particle diameter of the external additive is preferably 10 nm or more, more preferably 13 nm or more, still more preferably 15 nm or more, and preferably 200 nm or less, from the viewpoint of toner chargeability, fluidity, and transferability. Preferably it is 90 nm or less, More preferably, it is 50 nm or less.
The content of the external additive is preferably 0.05 parts by mass or more, more preferably 0.3 parts by mass or more, and further preferably 1 part by mass or more with respect to 100 parts by mass of the toner before processing with the external additive. And preferably 5 parts by mass or less, more preferably 4 parts by mass or less, and still more preferably 3 parts by mass or less.

<Volume-median particle size _(D 50)>
The volume median particle size (D ₅₀ ) of the toner of the present invention is preferably 3 μm or more, more preferably 4 μm or more, still more preferably 4.5 μm or more, and preferably 15 μm or less, more preferably 10 μm or less. More preferably, it is 6 μm or less.
In the present specification, the volume-median particle size (D ₅₀ ) means a particle size at which the cumulative volume frequency calculated by the volume fraction is 50% calculated from the smaller particle size. Also, when processing a toner external additive, the volume median particle size of the toner particles prior to treatment with an external additive (D ₅₀₎ a toner having a volume-median particle size (D ₅₀₎ .

[Method for producing toner for developing electrostatic image]
The method for producing an electrostatic charge image developing toner of the present invention includes the following steps 1 and 2, wherein the amorphous composite resin contains a polyester resin portion and a vinyl resin portion, and the raw material monomer for the polyester resin portion Is a method for producing a toner for developing an electrostatic charge image, which contains an aliphatic diol having a hydroxyl group bonded to a secondary carbon atom.
Step 1: An aqueous dispersion of resin particles I containing crystalline polyester and vinyl resin and an aqueous dispersion of resin particles A containing an amorphous composite resin are mixed and agglomerated to form an aqueous dispersion of resin particles II. Step 2: Step of fusing the resin particles II obtained in Step 1

<Step 1>
Step 1 mixes and aggregates an aqueous dispersion of resin particles I containing crystalline polyester and a vinyl resin and an aqueous dispersion of resin particles A containing an amorphous composite resin, thereby dispersing the aqueous dispersion of resin particles II. This is a step of obtaining a liquid.

(Aqueous dispersion of resin particles I)
As a method for producing an aqueous dispersion of resin particles I, a method of adding an aqueous medium to a composition containing at least a crystalline polyester and a vinyl resin and suspending the composition using a disperser, and an aqueous medium in the composition Examples include a method of gradually adding and phase inversion emulsification. From the viewpoint of low-temperature fixability, durability, and filming resistance of the obtained toner, a method by phase inversion emulsification is preferable. Or process 1-I 'is more preferable and process 1-I is still more preferable.
Step 1-I: A step of obtaining an aqueous dispersion of resin particles I by mixing and aggregating an aqueous dispersion of resin particles B containing crystalline polyester and an aqueous dispersion of resin particles C containing a vinyl resin. 1-I ′: a step of adding an aqueous medium to a solution containing a crystalline polyester, a vinyl resin, and an organic solvent and phase-emulsifying to obtain an aqueous dispersion of the resin particles I. “Aqueous dispersion” means that the medium in which the resin is dispersed may contain a solvent such as an organic solvent, but water is preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably 90%. More than mass%, more preferably 99 mass% or more, still more preferably 100 mass%.
Hereinafter, step 1-I will be described.

[Step 1-I]
Step 1-I is a step of mixing and aggregating an aqueous dispersion of resin particles B containing crystalline polyester and an aqueous dispersion of resin particles C containing a vinyl resin to obtain an aqueous dispersion of resin particles I. It is.

<< Aqueous dispersion of resin particles B >>
The method for obtaining the aqueous dispersion of the resin particles B is not limited. From the viewpoint of low-temperature fixability, durability, and filming resistance of the obtained toner, an aqueous medium is added to the solution containing the crystalline polyester and the organic solvent. Is preferably added, and a phase inversion emulsification method (hereinafter also referred to as “Method 1-B”) is preferable. An aqueous medium is added to a solution containing a crystalline polyester neutralized with a base and an organic solvent, and phase inversion is performed. A method of emulsifying is more preferable.
Hereinafter, the method 1-B will be described.

<< Method 1-B >>
In Method 1-B, first, a crystalline polyester, an organic solvent, and optional components such as a basic substance, a surfactant, and a colorant added as necessary are mixed to prepare a mixed solution for phase inversion emulsification. obtain.
As a method for obtaining a mixed solution for phase inversion emulsification, the crystalline polyester, the organic solvent, and the optional components such as a basic substance, a surfactant, and a colorant that are added as necessary are placed in a container and stirred. A method of dissolving and mixing the crystalline polyester while stirring with a machine is preferred.
Examples of the crystalline polyester used in Method 1-B include those similar to the crystalline polyester used as a raw material for the toner of the present invention, and preferred embodiments thereof are also the same.
Examples of the colorant optionally used in Method 1-B include the same colorants that can be contained in the toner of the present invention, and preferred embodiments thereof are also the same.

{Organic solvent}
From the viewpoint of improving the dispersibility of the resin particles B, the organic solvent is preferably 15.0 MPa ^1/2 when expressed by a solubility parameter (SP value: POLYMER HANDBOOK THIRD EDITION 1989 by John Wiley & Sons, Inc). or more, more preferably 16.0MPa ^1/2, and even more preferably at 17.0MPa ^1/2 or more, and, preferably 26.0MPa ^1/2 or less, more preferably 24.0MPa ^1/2 or less, further Preferably, it is 22.0 MPa ^1/2 or less.
Specific examples include the following organic solvents. The parentheses on the right side of the name of the next organic solvent are SP values, and the unit is MPa ^1/2 . That is, specific examples include alcohol solvents such as ethanol (26.0), isopropanol (23.5), and isobutanol (21.5); acetone (20.3), methyl ethyl ketone (19.0), methyl Ketone solvents such as isobutyl ketone (17.2) and diethyl ketone (18.0); ether solvents such as dibutyl ether (16.5), tetrahydrofuran (18.6) and dioxane (20.5); Examples thereof include acetate solvents such as ethyl acetate (18.6) and isopropyl acetate (17.4). Among these, from the viewpoint of low-temperature fixability, durability, and filming resistance of the obtained toner, a ketone solvent and an acetate solvent are preferable, and at least selected from the group consisting of methyl ethyl ketone, ethyl acetate, and isopropyl acetate. One is more preferable, and ethyl acetate is still more preferable.
The mass ratio of the organic solvent to the crystalline polyester [organic solvent / crystalline polyester] is preferably 0.03 or more, more preferably from the viewpoint of low-temperature fixability, durability, and filming resistance of the obtained toner. It is 0.1 or more, more preferably 0.3 or more, and preferably 5 or less, more preferably 2 or less, still more preferably 1 or less, and still more preferably 0.7 or less.

{Basic substance}
The crystalline polyester contained in the resin particle B is preferably treated with a basic substance.
Examples of the basic substance include hydroxides of alkali metals such as lithium hydroxide, sodium hydroxide and potassium hydroxide, and nitrogen-containing substances such as ammonia, trimethylamine, ethylamine, diethylamine, triethylamine, triethanolamine and tributylamine. Examples include salt substances. Among these, from the viewpoint of dispersion stability and cohesiveness, ammonia and sodium hydroxide are preferable, and sodium hydroxide is more preferable.

The degree of neutralization of the crystalline polyester with a basic substance is preferably at least 30 mol%, more preferably at least 50 mol%, still more preferably from the viewpoint of low-temperature fixability, durability, and filming resistance of the obtained toner. Is 70 mol% or more, and preferably 100 mol% or less, more preferably 90 mol% or less, and still more preferably 85 mol% or less.
In addition, the neutralization degree (mol%) of resin can be calculated | required by a following formula.
Degree of neutralization = {[mass of basic substance (g) / equivalent of basic substance] / [[acid value of resin (mgKOH / g) × mass of resin (g)] / (56 × 1000)]} × 100

{Surfactant}
Examples of the surfactant include nonionic surfactants, anionic surfactants, and cationic surfactants. Among these, from the viewpoint of resin dispersibility, nonionic surfactants and / or anionic surfactants are preferable, and anionic surfactants are more preferable.
Nonionic surfactants include polyoxyethylene alkylaryl ethers such as polyoxyethylene lauryl ether, polyoxyethylene alkyl ethers, polyoxyethylene fatty acid esters such as polyethylene glycol monolaurate, oxyethylene / oxypropylene Examples thereof include block copolymers, and among these, polyoxyethylene alkyl ethers are preferred from the viewpoint of emulsion stability of the resin.
Examples of the anionic surfactant include alkylbenzene sulfonates such as sodium alkylbenzene sulfonate, alkyl sulfates such as sodium alkyl sulfate, polyoxyalkylene alkyl ether sulfates such as sodium polyoxyalkylene alkyl ether sulfate, and the like. Among these, from the viewpoint of emulsion stability of the resin, sodium alkylbenzene sulfonate and polyoxyalkylene alkyl ether sulfate are preferable, sodium alkylbenzene sulfonate is more preferable, and sodium dodecylbenzene sulfonate is more preferable.
Examples of the cationic surfactant include alkyltrimethylammonium chloride and dialkyldimethylammonium chloride.
The amount of the surfactant used is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, still more preferably 0.8 parts by mass or more with respect to 100 parts by mass of the resin. Is 5 parts by mass or less, more preferably 3 parts by mass or less, and still more preferably 1 part by mass or less.

{Mixing conditions}
The temperature at the time of mixing is preferably 20 ° C. or higher, more preferably 40 ° C. or higher, more preferably 60 ° C. or higher, from the viewpoints of stabilizing the process temperature, shortening the process time, reducing the viscosity of the solution, and the like. Preferably, it is 90 degrees C or less, More preferably, it is 80 degrees C or less, More preferably, it is 75 degrees C or less.
The stirring is preferably performed until there is no significant phase separation or insoluble matter, and the stirring time depends on the stirring speed and temperature conditions, but is preferably 0.1 hour or more, more preferably It is 0.2 hours or more, more preferably 0.3 hours or more, and preferably 5 hours or less, more preferably 3 hours or less, still more preferably 1 hour or less.

  Next, an aqueous medium is added to the mixed solution for phase inversion emulsification obtained above to perform phase inversion emulsification. By this phase inversion emulsification, an aqueous dispersion of resin particles B is obtained.

{Aqueous medium}
As the aqueous medium, those mainly containing water are preferable.
Components other than water include aliphatic alcohols having 1 to 5 carbon atoms such as methanol, ethanol, isopropanol and butanol; dialkyl (1 to 3 carbon atoms) ketones such as acetone and methyl ethyl ketone; cyclic ethers such as tetrahydrofuran Examples thereof include organic solvents that dissolve in water. Among these, alcohol-based organic solvents such as methanol, ethanol, isopropanol, and butanol, which are organic solvents that do not dissolve the resin, can be more preferably used from the viewpoint of preventing mixing into the toner.
The content of water in the aqueous medium is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, and still more preferably 100% by mass, from the viewpoint of improving the emulsion stability of the resin. %. The water is preferably deionized water or distilled water.

The temperature at which the aqueous medium is added is preferably 20 ° C. or higher, more preferably 30 ° C. or higher, still more preferably 50 ° C. or higher, and still more preferably 60 ° C. or higher, from the viewpoint of improving the emulsion stability of the resin. And, it is preferably 85 ° C. or lower, more preferably 80 ° C. or lower, and further preferably 75 ° C. or lower.
The addition rate of the aqueous medium is preferably 0.5 parts by mass / min or more, more preferably 1 part by mass / min with respect to 100 parts by mass of the crystalline polyester until the phase inversion is completed from the viewpoint of particle size control. Min. Or more, more preferably 3 parts by mass / min or more, and preferably 20 parts by mass / min or less, more preferably 10 parts by mass / min or less, still more preferably 5 parts by mass / min or less. There is no restriction | limiting in the addition rate of the aqueous medium after phase inversion.

The use amount of the aqueous medium is preferably 100 parts by mass or more, more preferably 200 parts by mass or more, and further preferably 250 parts by mass with respect to 100 parts by mass of the crystalline polyester from the viewpoint of obtaining uniform resin particles in the subsequent aggregation step. It is at least 1000 parts by mass, more preferably at most 500 parts by mass, and even more preferably at most 300 parts by mass.
Further, from the viewpoint of obtaining uniform resin particles in the subsequent aggregation step, the mass ratio of the aqueous medium to the organic solvent [aqueous medium / organic solvent] is preferably 70/30 or more, more preferably 75/25 or more, and further The ratio is preferably 80/20 or more, and preferably 98/2 or less, more preferably 95/5 or less, and still more preferably 90/10 or less.

You may have the process of removing an organic solvent from the dispersion obtained by phase inversion emulsification after phase inversion emulsification.
The method for removing the organic solvent is not particularly limited, and any method can be used. However, since it is dissolved in water, it is preferably distilled. Further, the organic solvent may not be completely removed and may remain in the aqueous dispersion. In this case, the remaining amount of the organic solvent is preferably 1% by mass or less, more preferably 0.5% by mass or less, and still more preferably substantially 0% by mass in the aqueous dispersion.
When removing the organic solvent by distillation, it is preferable to raise the temperature to a temperature equal to or higher than the boiling point of the organic solvent to be used while stirring. Further, from the viewpoint of maintaining the dispersion stability of the resin particles B, it is more preferable to raise the temperature to a temperature equal to or higher than the boiling point of the organic solvent to be used under reduced pressure and to distill it off. Note that the temperature may be increased after the pressure is reduced, or the pressure may be decreased after the temperature is increased. From the viewpoint of maintaining the dispersion stability of the resin particles B, it is preferable to distill off at a constant temperature and pressure.

After the phase inversion emulsification or the step of removing the organic solvent, a step of mixing a surfactant with the aqueous dispersion obtained in these steps may be included.
In addition, the amount of the surfactant to be added in this step is preferably 0.5% by mass with respect to 100 parts by mass of the crystalline polyester from the viewpoint of low-temperature fixability, durability, and filming resistance of the obtained toner. Part or more, more preferably 1 part by weight or more, still more preferably 1.5 parts by weight or more, and preferably 6 parts by weight or less, more preferably 4.5 parts by weight or less, still more preferably 3 parts by weight or less. is there.
When the surfactant is added, it is preferable to stir with a commonly used mixing and stirring device such as an anchor blade or an external circulation stirring device.

≪Solid concentration of resin particle B≫
The solid content concentration of the resin particles B in the aqueous dispersion is preferably 5% by mass or more, more preferably 10% by mass or more, from the viewpoint of improving the productivity of the toner and the dispersion stability of the aqueous dispersion. Further, it is preferably 15% by mass or more, and preferably 40% by mass or less, more preferably 30% by mass or less, and further preferably 25% by mass or less.

«Volume median particle size _{(D 50)} of the resin particles B»
The volume median particle size (D ₅₀ ) of the resin particles B is preferably 50 nm or more, more preferably 120 nm or more, still more preferably 160 nm or more, and preferably 300 nm or less, from the viewpoint of toner productivity. Preferably it is 200 nm or less, More preferably, it is 180 nm or less.

[Aqueous dispersion of resin particles C]
Although there is no restriction | limiting in the method of obtaining the aqueous dispersion of the resin particle C, From the viewpoint of the low-temperature fixability, durability, and filming resistance of the toner obtained, the aqueous medium is added to the solution containing the vinyl resin and the organic solvent. Is preferably added and then phase inversion emulsified (hereinafter also referred to as “Method 1-C”).

<< Method 1-C >>
In Method 1-C, first, a vinyl resin, an organic solvent, and optional components such as a basic substance, a surfactant, and a colorant that are added as necessary are mixed to prepare a mixed solution for phase inversion emulsification. obtain.
As a method for obtaining a mixed solution for phase inversion emulsification, a vinyl resin, an organic solvent, and any optional components such as a basic substance, a surfactant, and a colorant that are added as necessary are placed in a container and stirred. A method of dissolving and mixing the vinyl resin while stirring with a machine is preferred.
Examples of the vinyl resin used in Method 1-C include the same vinyl resins as those used as a raw material for the toner of the present invention, and preferred embodiments thereof are also the same.
The aspect of mixing conditions and the basic substance, surfactant, and colorant that are added as necessary are the same as in Method 1-B, and the preferred aspects are also the same.

{Organic solvent}
The kind of the organic solvent is the same as that mentioned in Method 1-B, and the preferred embodiment is also the same.
The mass ratio of the organic solvent to the vinyl resin (organic solvent / vinyl resin) is preferably 0.05 or more, more preferably from the viewpoint of low-temperature fixability, durability, and filming resistance of the obtained toner. It is 0.1 or more, more preferably 0.3 or more, and preferably 3.0 or less, more preferably 1.0 or less, and still more preferably 0.7 or less.

  Next, an aqueous medium is added to the mixed solution for phase inversion emulsification obtained above to perform phase inversion emulsification. By this phase inversion emulsification, an aqueous dispersion of resin particles C is obtained.

{Aqueous solvent}
The type of the aqueous medium, the addition temperature, and the addition rate are the same as in Step 1-B, and the preferred embodiment is also the same.
From the viewpoint of obtaining uniform particles, the amount of the aqueous medium to be added is preferably 100 parts by mass or more, more preferably 300 parts by mass or more, and further preferably 500 parts by mass or more with respect to 100 parts by mass of the vinyl resin. Yes, and preferably 1500 parts by mass or less, more preferably 1000 parts by mass or less, and still more preferably 700 parts by mass or less.

≪Solid content concentration of resin particles C≫
The solid content concentration of the aqueous dispersion of the resin particles C is preferably 5% by mass or more, more preferably 10% by mass or more, from the viewpoint of improving the productivity of the toner and the dispersion stability of the aqueous dispersion. More preferably, it is 15 mass% or more, and preferably 40 mass% or less, More preferably, it is 30 mass% or less, More preferably, it is 25 mass% or less.

«Volume median particle size _{(D 50)} of the resin particles C»
The volume median particle size (D ₅₀ ) of the resin particles C is preferably 70 nm or more, more preferably 80 nm or more, still more preferably 95 nm or more, and preferably 120 nm or less, from the viewpoint of toner productivity. Preferably it is 110 nm or less, More preferably, it is 105 nm or less.

Next, the aqueous dispersion of resin particles B and the aqueous dispersion of resin particles C are mixed and aggregated to obtain an aqueous dispersion of resin particles I. From the viewpoint of efficiently performing the aggregation, it is preferable to add an aggregating agent.
In addition, aggregation may be performed after adding additives such as a coloring agent, a charge control agent, a release agent, a conductivity adjusting agent, a reinforcing filler such as a fibrous substance, an antioxidant, and an anti-aging agent. These additives can be used as an aqueous dispersion.
The step of mixing and aggregating the aqueous dispersion of resin particles B and the aqueous dispersion of resin particles C may be referred to as “aggregation step (1)”.

[Mass ratio of resin particle B and resin particle C]
The mixing ratio of the aqueous dispersion of the resin particles B and the aqueous dispersion of the resin particles C is such that the resin particles B and the resin particles C have a low temperature fixability, durability, and filming resistance. The mass ratio is preferably 40/60 or more, more preferably 50/50 or more, still more preferably 60/40 or more, and preferably 95/5 or less, more preferably 90/10 or less, still more preferably 80. / 20 or less.

[Flocculant]
As the flocculant, a quaternary salt cationic surfactant, an organic flocculant such as polyethyleneimine; and an inorganic flocculant such as inorganic metal salt and inorganic ammonium salt are used. From the viewpoint of low-temperature fixability, durability, and filming resistance of the obtained toner, an inorganic flocculant is preferable, and an inorganic metal salt is more preferable.
Examples of the inorganic metal salt include sodium sulfate, sodium chloride, calcium chloride, calcium nitrate, barium chloride, magnesium chloride, zinc chloride, and aluminum chloride. The valence of the central metal of the inorganic metal salt is preferably 2 or more from the viewpoint of low-temperature fixability, durability, and filming resistance of the obtained toner.
When the flocculant is added, the addition amount is preferably from the viewpoint of low-temperature fixability, durability, and filming resistance of the obtained toner with respect to 100 parts by mass of the resin particles B and resin particles C in total. 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, further preferably 0.2 parts by mass or more, and preferably 10 parts by mass or less, more preferably 1.0 parts by mass or less, still more preferably. Is 0.3 parts by mass or less.
The flocculant is preferably added after being dissolved in an aqueous medium, and it is preferable that the flocculant is sufficiently stirred at the time of addition of the flocculant and after completion of the addition.
The solid content concentration in the system in the aggregation step (1) is preferably 3% by mass or more, more preferably 7% by mass or more, and further preferably 10% by mass or more in order to cause uniform aggregation. Preferably it is 50 mass% or less, More preferably, it is 20 mass% or less, More preferably, it is 15 mass% or less.
The temperature at the time of addition of the flocculant is preferably 5 ° C. or higher, more preferably 10 ° C. or higher, further preferably 15 ° C. or higher, from the viewpoint of uniformly dispersing the flocculant and causing uniform aggregation. Is 40 ° C. or lower, more preferably 30 ° C. or lower, and further preferably 25 ° C. or lower.

[Colorant]
Examples of the colorant include the same ones as those described in the section of the toner of the present invention, and preferred embodiments are also the same.
The addition amount of the colorant is based on 100 parts by mass of the resin particles B and the resin particles C from the viewpoint of improving the image density of the toner and from the viewpoint of low-temperature fixability, durability, and filming resistance of the toner. , Preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, still more preferably 1.0 parts by mass or more, and preferably 40 parts by mass or less, more preferably 20 parts by mass or less, further Preferably it is 5 mass parts or less.
The colorant may be added as a colorant dispersion containing colorant fine particles. The volume median particle size (D ₅₀ ) of the fine colorant particles is preferably 50 nm or more, more preferably 70 nm or more, still more preferably 100 nm or more, and preferably 200 nm or less, more preferably 170 nm or less, still more preferably. 150 nm or less.

[Charge control agent]
Examples of the charge control agent include the same ones as mentioned in the section of the toner of the present invention, and preferred embodiments are also the same.
When the charge control agent is added, the addition amount is 100 in total of resin particles B and resin particles C from the viewpoint of charging stability of the toner and from the viewpoint of low-temperature fixability, durability, and filming resistance of the toner. Preferably it is 0.0005 mass part or more with respect to a mass part, More preferably, it is 0.001 mass part or more, More preferably, it is 0.005 mass part or more, Preferably it is 1 mass part or less, More preferably, it is 0 .1 parts by mass or less, more preferably 0.01 parts by mass or less.
The charge control agent may be added as a charge control agent dispersion containing charge control agent fine particles. The volume median particle size (D ₅₀ ) of the charge control agent fine particles is preferably 100 nm or more, more preferably 200 nm or more, still more preferably 300 nm or more, and preferably 800 nm or less, more preferably 600 nm or less, Preferably it is 500 nm or less.

〔Release agent〕
Examples of the release agent include the same as those described in the section of the toner of the present invention, and preferred embodiments are also the same.
The amount of the release agent used is 100 parts by mass in total of the resin particles B and the resin particles C from the viewpoint of dispersibility in the resin and from the viewpoint of low-temperature fixability, durability, and filming resistance of the toner. Preferably, it is 1 part by mass or more, more preferably 3 parts by mass or more, further preferably 5 parts by mass or more, and preferably 15 parts by mass or less, more preferably 12 parts by mass or less, still more preferably 9 parts by mass. It is as follows.

Additives such as the colorant, charge control agent, and release agent may be mixed in advance with the crystalline polyester and / or vinyl resin, and each additive is separately dispersed in a dispersion medium such as water. You may prepare a liquid and use for an aggregation process.
When an additive is mixed in advance with the crystalline polyester and / or vinyl resin, it is preferable to melt-knead the crystalline polyester and / or vinyl resin and the additive in advance.
For melt kneading, it is preferable to use an open roll type biaxial kneader. An open roll type biaxial kneader is a kneader in which two rolls are arranged close to each other in parallel, and a heating function or a cooling function can be imparted by passing a heat medium through each roll. Therefore, the open roll type biaxial kneader is an open type part to be melt kneaded, and is provided with a heating roll and a cooling roll, so that it occurs during melt kneading unlike a normal biaxial kneader. The kneading heat can be easily dissipated.
In addition, an aqueous dispersion of each additive can be obtained by mixing each additive, a surfactant, and water and dispersing the mixture with a disperser.

[Volume Median Particle Size (D ₅₀ ) of Resin Particle I]
The volume median particle size (D ₅₀ ) of the resin particles I obtained by the step 1-I is preferably 1 μm or more, more preferably from the viewpoint of low-temperature fixability, durability, and filming resistance of the obtained toner. It is 3 μm or more, more preferably 4 μm or more, and preferably 10 μm or less, more preferably 8 μm or less, and further preferably 6 μm or less.

  Next, the manufacturing method of the aqueous dispersion liquid of the resin particle A used at the process 1 is demonstrated.

(Aqueous dispersion of resin particles A)
Although there is no limitation on the method for obtaining the aqueous dispersion of the resin particles A, from the viewpoint of low-temperature fixability, durability, and filming resistance of the obtained toner, the solution containing the amorphous composite resin and the organic solvent is used. A method of adding an aqueous medium and performing phase inversion emulsification (hereinafter also referred to as “Method 1-A”) is preferable, and an aqueous solution is added to a solution containing an amorphous composite resin neutralized with a base and an organic solvent. A method of adding a medium and performing phase inversion emulsification is preferred.

<< Method 1-A >>
In Method 1-A, first, an amorphous composite resin, an organic solvent, and optional components such as a basic substance, a surfactant, and a colorant that are added as necessary are mixed to mix for phase inversion emulsification. Obtain a solution.
As a method for obtaining a mixed solution for phase inversion emulsification, an amorphous composite resin, an organic solvent, and optional components such as a basic substance, a surfactant, and a colorant that are added as necessary are put in a container. A method of dissolving and mixing the amorphous composite resin while stirring with a stirrer is preferable.
Examples of the amorphous composite resin used in Method 1-A include those similar to the amorphous composite resin used as a raw material for the toner of the present invention, and preferred embodiments thereof are also the same.
The aspect of mixing conditions and the basic substance, surfactant, and colorant that are added as necessary are the same as in Method 1-B, and the preferred aspects are also the same.

Next, an aqueous medium is added to the mixed solution for phase inversion emulsification obtained above to perform phase inversion emulsification. By this phase inversion emulsification, an aqueous dispersion of resin particles A is obtained.
The conditions for phase inversion emulsification are the same as in Method 1-B, and the preferred embodiments are also the same.

≪Solid content concentration of resin particles A≫
The solid content concentration of the resin particles A in the aqueous dispersion is preferably 5% by mass or more, more preferably 10% by mass or more from the viewpoint of improving the productivity of the toner and the dispersion stability of the aqueous dispersion. More preferably, it is 15% by mass or more, and preferably 40% by mass or less, more preferably 30% by mass or less, and still more preferably 25% by mass or less.

«Volume median particle size _{(D 50)} of the resin particles A»
The volume median particle size (D ₅₀ ) of the resin particles A is preferably 50 nm or more, more preferably 70 nm or more, still more preferably 90 nm or more, and preferably 200 nm or less, from the viewpoint of toner productivity. Preferably it is 150 nm or less, More preferably, it is 130 nm or less, More preferably, it is 105 nm or less.

Next, the aqueous dispersion of resin particles I obtained by the above method and the aqueous dispersion of resin particles A are mixed and aggregated to obtain resin particles II.
As a result, a core-shell type toner can be obtained through step 2 described later. That is, the resin particles I mainly constitute the core part, and the aggregated resin particles A mainly constitute the shell part.
In addition, the process of aggregating the resin particles A on the resin particles I to obtain the resin particles II may be referred to as “aggregation process (2)”.

Before adding the aqueous dispersion of resin particles A to the aqueous dispersion of resin particles I, an aqueous medium may be added to the aqueous dispersion of resin particles I and diluted. In addition, when the aqueous dispersion of resin particles A is added to the aqueous dispersion of resin particles I, the flocculant may be used in this step in order to efficiently attach the resin particles A to the resin particles I.
(Drip temperature)
The temperature at the time of dropping the aqueous dispersion of the resin particles A is preferably 35 ° C. or higher, more preferably 40 ° C. or higher, and still more preferably, from the viewpoint of low-temperature fixability, durability, and filming resistance of the obtained toner. It is 45 ° C. or higher, and preferably 80 ° C. or lower, more preferably 65 ° C. or lower, and further preferably 55 ° C. or lower.
(Drip rate)
The aqueous dispersion of resin particles A may be added continuously over a certain period of time, may be added at a time, or may be added in multiple portions, but it takes a certain period of time. It is preferable to add them continuously or in several divided portions. By adding as described above, the resin particles A easily adhere selectively to the resin particles I. Among these, from the viewpoint of promoting selective adhesion and improving the productivity of toner, it is preferable to add continuously over a certain period of time.

(Mass ratio of resin particle I and resin particle A)
The addition amount of the aqueous dispersion of the resin particles A is the mass ratio of the resin particles I and the resin particles A from the viewpoint of low-temperature fixability, durability, and filming resistance of the obtained toner [resin particles I / resin particles A] is preferably 50/50 or more, more preferably 65/35 or more, still more preferably 75/25 or more, and preferably 95/5 or less, more preferably 90/10 or less, and still more preferably 85. / 15 or less.

(Volume Median Particle Size (D ₅₀ ) of Resin Particle II)
The volume median particle size (D ₅₀ ) of the resin particles II is preferably 3 μm or more, more preferably 4 μm or more, and still more preferably 4 from the viewpoints of low-temperature fixability, durability, and filming resistance of the obtained toner. 0.5 μm or more, and preferably 15 μm or less, more preferably 10 μm or less, and even more preferably 6 μm or less.

The total amount of the aqueous dispersion of resin particles A may be added, and the aggregation may be stopped when the toner particles have grown to an appropriate particle size.
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, a method of stopping aggregation by adding an aggregation stopper is preferable.

(Flocculation terminator)
The aggregation terminator is preferably a surfactant, more preferably an anionic surfactant. Examples of the anionic surfactant include alkylbenzene sulfonates, alkyl sulfates, alkyl ether sulfates, polyoxyalkylene alkyl ether sulfates, preferably polyoxyalkylene alkyl ether sulfates, more preferably polyoxyethylene. Lauryl ether sulfate, more preferably sodium polyoxyethylene lauryl ether sulfate. An aggregation terminator can be used individually or in combination of 2 or more types.
The amount of the aggregation terminator used is preferably 0.5 parts by mass or more, more preferably 1.0 parts by mass or more, still more preferably 1.8 parts by mass or more, with respect to 100 parts by mass of the resin. Is 8 parts by mass or less, more preferably 4 parts by mass or less, and still more preferably 2.5 parts by mass or less.

<Process 2>
Step 2 is a step of fusing the resin particles II obtained in Step 1.
Here, the fusion includes an amorphous composite resin in which a plurality of resin particles existing inside the resin particles II are fused to form a core by heating or the like, and the resin particles I are agglomerated and coated. The resin is fused to form a shell, and the core and the shell are appropriately bonded to form a core-shell structure.

(Fusion temperature)
The fusing temperature is preferably amorphous from the viewpoint of the target toner particle size, particle size distribution, shape control and fusing property of the toner, and low temperature fixing property, durability and filming resistance of the toner. The softening point of the porous composite resin is −60 ° C. or higher, more preferably the softening point of the amorphous composite resin is −50 ° C. or higher, more preferably the softening point of the amorphous composite resin is −40 ° C. or higher. The softening point of the crystalline composite resin or lower, more preferably the softening point of the amorphous composite resin is −10 ° C. or lower, and still more preferably the softening point of the amorphous composite resin is −20 ° C. or lower.
Specifically, it is preferably 65 ° C. or higher, more preferably 70 ° C. or higher, further preferably 75 ° C. or higher, and preferably 100 ° C. or lower, more preferably 90 ° C. or lower, still more preferably 85 ° C. or lower. .

[Post-process]
By subjecting the fused particles obtained in step 2 to a solid-liquid separation step such as filtration, a washing step, and a drying step, the electrostatic image developing toner of the present invention can be obtained.
In the washing step, it is preferable to completely remove the added nonionic surfactant by washing, and washing with an aqueous solution below the cloud point of the nonionic surfactant is preferred. The washing is preferably performed a plurality of times.
In the drying step, any method such as a vibration type fluidized drying method, a spray drying method, a freeze drying method, a flash jet method, or the like can be employed. The water content after drying of the toner is preferably adjusted to 1.5% by mass or less and more preferably adjusted to 1.0% by mass or less from the viewpoint of chargeability.

Further, an external additive may be added for the purpose of improving fluidity. Examples of the external additive include those similar to those that can be contained in the toner of the present invention, and preferred embodiments thereof are also the same.
When the external additive is added, the addition amount is preferably 0 with respect to 100 parts by mass of the toner before the processing with the external additive, from the viewpoint of the fluidity of the toner, the environmental stability of the charging degree, and the storage stability. .05 parts by mass or more, more preferably 0.3 parts by mass or more, further preferably 1 part by mass or more, and preferably 5 parts by mass or less, more preferably 4 parts by mass or less, still more preferably 3 parts by mass or less. It is.

  In relation to the above-described embodiment, the present invention discloses the following toner for developing an electrostatic image and a method for producing the same.

<1> An electrostatic charge image developing toner having a core and a shell,
The core includes a crystalline polyester and a vinyl-based resin, and the shell includes an amorphous composite resin;
The amorphous composite resin contains a polyester resin portion and a vinyl resin portion,
A toner for developing an electrostatic charge image, wherein the polyester resin portion is obtained by polycondensation of an alcohol component containing an aliphatic diol having a hydroxyl group bonded to a secondary carbon atom and a carboxylic acid component.

<2> The crystalline polyester polycondenses an alcohol component containing an aliphatic diol having 6 to 12 carbon atoms and a carboxylic acid component containing an aliphatic dicarboxylic acid compound having 4 to 12 carbon atoms. The toner for developing an electrostatic charge image according to the above <1>, which is obtained by causing the toner to develop.
<3> The electrostatic image developing toner according to <2>, wherein the aliphatic dicarboxylic acid compound having 4 to 12 carbon atoms, which is a raw material monomer of the crystalline polyester, is a saturated aliphatic dicarboxylic acid compound.
<4> The static according to <2> or <3>, wherein the carboxylic acid component, which is a raw material monomer of the crystalline polyester, contains an aliphatic dicarboxylic acid compound having 4 to 12 carbon atoms in an amount of 80 mol% or more. Toner for charge image development.
<5> The electrostatic image developing toner according to any one of <2> to <4>, wherein the aliphatic dicarboxylic acid compound which is a raw material monomer of the crystalline polyester has 8 or more and 12 or less carbon atoms. .
<6> The static component according to any one of <2> to <5>, wherein the alcohol component which is a raw material monomer of the crystalline polyester contains an aliphatic diol having 6 to 12 carbon atoms in an amount of 80 mol% or more. Toner for charge image development.
<7> The electrostatic image developing toner according to any one of <2> to <6>, wherein the aliphatic diol which is a raw material monomer of the crystalline polyester has 6 to 10 carbon atoms.
<8> The toner for developing an electrostatic charge image according to any one of <1> to <7>, wherein a mass ratio of the core to the shell is 60/40 or more and 90/10 or less.
<9> Both reactions in which the amorphous composite resin can react with the raw material monomer of the polyester resin part, the raw material monomer of the vinyl resin part, and the raw material monomer of the polyester resin part and the raw material monomer of the vinyl resin part The toner for developing an electrostatic charge image according to any one of <1> to <8>, which is obtained by polymerizing a functional monomer.
<10> The static electricity according to <9>, wherein the amount of the both reactive monomers used is 1 mol part or more and 15 mol parts or less with respect to 100 mol parts of the alcohol component that is a raw material monomer of the polyester resin portion. Toner for charge image development.
<11> In the above <9> or <10>, the amount of the both reactive monomers used is 1 mol part or more and 5 mol parts or less with respect to 100 mol of the alcohol component which is a raw material monomer of the polyester resin portion. The toner for developing an electrostatic image according to the description.
<12> The <1> to <1>, wherein the alcohol component, which is a raw material monomer of the polyester resin portion of the amorphous composite resin, contains 80 mol% or more of an aliphatic diol having a hydroxyl group bonded to a secondary carbon atom. 11> The toner for developing an electrostatic charge image according to any one of the above.
<13> The above <1> to <1>, wherein the aliphatic diol having a hydroxyl group bonded to a secondary carbon atom that is a raw material monomer of the polyester resin portion of the amorphous composite resin has 3 to 5 carbon atoms. The toner for developing an electrostatic image according to any one of 12).
<14> The <1> to <1>, wherein a mass ratio of the polyester resin portion to the vinyl resin portion [polyester resin portion / vinyl resin portion] in the amorphous composite resin is 50/50 or more and 95/5 or less. <13> The electrostatic image developing toner according to any one of the above.
<15> The electrostatic charge image development according to any one of <1> to <14>, wherein the carboxylic acid component which is a raw material monomer of the polyester resin portion of the amorphous composite resin contains an aromatic dicarboxylic acid compound. Toner.
<16> The electrostatic image developing toner according to <15>, wherein the aromatic dicarboxylic acid compound is terephthalic acid.
<17> Any of the above <1> to <16>, wherein the carboxylic acid component that is a raw material monomer of the polyester resin portion of the amorphous composite resin contains an aliphatic dicarboxylic acid compound having 2 to 6 carbon atoms The electrostatic image developing toner according to claim 1.
<18> The electrostatic image developing toner according to any one of <9> to <17>, wherein the bireactive monomer which is a raw material monomer of the amorphous composite resin is (meth) acrylic acid.
<19> The electrostatic image developing toner according to any one of <1> to <18>, wherein the vinyl-based resin portion of the amorphous composite resin includes a structural unit derived from styrene.
<20> The vinyl resin portion of the amorphous composite resin includes a structural unit derived from styrene and a structural unit derived from an alkyl (meth) acrylate having an alkyl group having 6 to 18 carbon atoms. The toner for developing an electrostatic charge image according to any one of 1> to <19>.
<21> The toner for developing an electrostatic charge image according to any one of <1> to <20>, wherein the amorphous composite resin has a softening point of 80 ° C. or higher and 170 ° C. or lower.
<22> The electrostatic image developing toner according to any one of <1> to <21>, wherein the crystalline polyester has a softening point of 65 ° C. or higher and 120 ° C. or lower.
<23> The electrostatic image developing toner according to any one of <1> to <22>, wherein the crystalline polyester has a melting point of 60 ° C. or higher and 105 ° C. or lower.

<24> A hydroxyl group having the following steps 1 and 2, wherein the amorphous composite resin contains a polyester resin portion and a vinyl resin portion, and the raw material monomer of the polyester resin portion is bonded to a secondary carbon atom. A method for producing a toner for developing an electrostatic image, which comprises an aliphatic diol having the following formula.
Step 1: An aqueous dispersion of resin particles I containing crystalline polyester and vinyl resin and an aqueous dispersion of resin particles A containing an amorphous composite resin are mixed and agglomerated to form an aqueous dispersion of resin particles II. Step 2: Fusing the resin particles II obtained in Step 1 <25> A method for obtaining an aqueous dispersion of the resin particles A is a solution containing an amorphous composite resin and an organic solvent. The method for producing a toner for developing an electrostatic charge image according to <24>, wherein the aqueous medium is added and phase inversion emulsification is performed.
<26> The method for producing a toner for developing an electrostatic charge image according to <24> or <25>, wherein the step of obtaining an aqueous dispersion of the resin particles I includes the following step 1-I.
Step 1-I: Step of obtaining an aqueous dispersion of resin particles I by mixing and aggregating an aqueous dispersion of resin particles B containing crystalline polyester and an aqueous dispersion of resin particles C containing a vinyl resin <27> The electrostatic charge according to the above <26>, wherein the method of obtaining an aqueous dispersion of the resin particles B is a method of adding an aqueous medium to a solution containing a crystalline polyester and an organic solvent, followed by phase inversion emulsification. A method for producing a toner for image development.
<28> The method according to <26> or <27>, wherein the method of obtaining an aqueous dispersion of the resin particles C is a method in which an aqueous medium is added to a solution containing a vinyl resin and an organic solvent, and phase inversion emulsification is performed. A method for producing a toner for developing an electrostatic image as described in 1.
<29> The method for producing a toner for developing an electrostatic charge image according to any one of <26> to <28>, wherein the resin particles C have a volume-median particle size of 70 to 120 nm.
<30> The method for producing a toner for developing an electrostatic charge image according to <24>, wherein the step of obtaining an aqueous dispersion of the resin particles I includes the following step 1-I ′.
Step 1-I ′: A step of adding an aqueous medium to a solution containing crystalline polyester, vinyl resin, and organic solvent, and phase-emulsifying to obtain an aqueous dispersion of resin particles I.

  Each property such as resin, resin particles, and toner was measured and evaluated by the following method.

[Acid value of resin]
The acid value of the resin was measured based on the method of JIS K 0070. However, only the measurement solvent was changed from the mixed solvent of ethanol and ether specified in JIS K 0070 to a mixed solvent of acetone and toluene (acetone: toluene = 1: 1 (volume ratio)).

[Resin softening point, endothermic maximum peak temperature, crystallinity index, melting point, and glass transition temperature]
(1) Softening point Using a flow tester “CFT-500D” (manufactured by Shimadzu Corporation), a 1 g sample was heated at a heating rate of 6 ° C./min, and a load of 1.96 MPa was applied by a plunger. The nozzle was extruded from a nozzle having a length of 1 mm and a length of 1 mm. The amount of plunger drop of the flow tester was plotted against the temperature, and the temperature at which half of the sample flowed out was taken as the softening point.
(2) Maximum endothermic peak temperature Using a differential scanning calorimeter “Q-100” (manufactured by TA Instruments Japan Co., Ltd.), it is 0 ° C. at a temperature decreasing rate of 10 ° C./min from room temperature (20 ° C.). The sample cooled to 0 ° C. was allowed to stand for 1 minute, and then measured while heating up to 180 ° C. at a heating rate of 10 ° C./min. Of the endothermic peaks observed, the peak temperature on the highest temperature side was defined as the maximum endothermic peak temperature.
(3) Crystallinity index The ratio between the softening point measured as described above and the maximum endothermic peak temperature, that is, “softening point (° C.) / Maximum endothermic peak temperature (° C.)” was calculated, and the crystallinity It was an index.
(4) Melting point Using a differential scanning calorimeter “Q-100” (manufactured by TA Instruments Japan Co., Ltd.), 0.01 to 0.02 g of a sample was weighed into an aluminum pan, and the temperature was raised to 200 ° C. Then, the temperature was cooled to 0 ° C. at a rate of temperature decrease of 10 ° C./min. Next, the measurement was performed while increasing the temperature to 150 ° C. at a temperature increase rate of 10 ° C./min. Of the endothermic peaks observed, the temperature of the peak with the largest peak area was taken as the melting point.
(5) Glass transition temperature Using a differential scanning calorimeter “Q-100” (manufactured by TA Instruments Japan Co., Ltd.), 0.01 to 0.02 g of a sample is weighed into an aluminum pan, and 200 ° C. The temperature was raised to 0 ° C. from the temperature at a temperature drop rate of 10 ° C./min. Next, the measurement was performed while increasing the temperature to 150 ° C. at a temperature increase rate of 10 ° C./min. The glass transition temperature was defined as the temperature at the intersection of the base line extension below the maximum temperature of the endothermic peak and the tangent line indicating the maximum slope from the peak rising portion to the peak apex.

[Volume Median Particle Size of Toner and Resin Particles I (D ₅₀ )]
The volume median particle size (D ₅₀ ) of the resin particles was measured as follows.
・ Measuring machine: "Coulter Multisizer III" (Beckman Coulter, Inc.)
・ Aperture diameter: 50μm
・ Analysis software: “Multisizer III version 3.51” (manufactured by Beckman Coulter)
・ Electrolyte: “Isoton II” (Beckman Coulter, Inc.)
-Dispersion: Polyoxyethylene lauryl ether "Emulgen (registered trademark) 109P" (manufactured by Kao Corporation, HLB: 13.6) was dissolved in the electrolytic solution to obtain a dispersion having a concentration of 5% by mass.
Dispersion condition: 10 mg of sample (converted to solid content) is added to 5 mL of the dispersion, and dispersed for 1 minute with an ultrasonic disperser, then 25 mL of electrolyte is added, and further for 1 minute with an ultrasonic disperser. A sample dispersion was prepared by dispersing.
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.

[Volume Median Particle Size (D ₅₀ ) of Resin Particles, Colorant Particles, Release Agent Particles, Charge Control Agent Particles]
(1) Measuring apparatus: Laser diffraction type particle size measuring instrument “LA-920” (manufactured by Horiba, Ltd.)
(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.

[Solid content concentration of aqueous dispersion, colorant dispersion, release agent particles, charge control agent dispersion]
Using an infrared moisture meter “FD-230” (manufactured by Kett Science Laboratory Co., Ltd.), 5 g of the sample was subjected to a drying temperature of 150 ° C. and a measurement mode of 96 (monitoring time 2.5 minutes / variation width 0.05%). The sample was dried and the moisture content (% by mass) of the sample was measured. The solid content was calculated according to the following formula.
Solid content concentration (% by mass) = 100-M
M: moisture of the sample (% by mass)

[Low-temperature fixability of toner]
The toner was mounted on an apparatus in which the fixing machine of the copying machine “AR-505” (manufactured by Sharp Corporation) was improved so that fixing outside the apparatus was possible, and a printed matter was obtained in an unfixed state (printing area: 2 cm). × 12 cm, adhesion amount: 0.5 mg / cm ² ). After that, using a fixing machine (fixing speed 300 mm / sec) adjusted so that the total fixing pressure becomes 40 kgf, the fixing roll temperature is gradually increased from 80 ° C. to 240 ° C. by 5 ° C., and unfixed at each temperature. A fixing test of the printed matter in the state was performed. A cellophane adhesive tape “UNICEF Cellophane” (Mitsubishi Pencil Co., Ltd., width: 18 mm, JIS Z1522) was attached to the image portion of the obtained printed matter, passed through a fixing roller set at 30 ° C., and then the tape was peeled off. . The optical reflection density before and after the tape was peeled was measured using a reflection densitometer “RD-915” (manufactured by Gretag Macbeth Co.), and the ratio between the two (after peeling / before sticking × 100) was initially 90%. The temperature of the fixing roller that exceeded the minimum fixing temperature. The lower the minimum fixing temperature, the better the low-temperature fixing property. In addition, “CopyBond SF-70NA” (manufactured by Sharp Corporation, 75 g / m ² ) was used as the fixing paper.

[Toner durability]
A toner is mounted on a non-magnetic one-component development type printer “OKI Microline 18” (manufactured by Oki Data Co., Ltd.) and obliquely blackened to A4 size paper at a temperature of 30 ° C. and a humidity of 80% with a blackening rate of 5.5%. A stripe pattern was printed continuously. A black solid image was printed every 500 sheets, and streaks (white lines) on the image were confirmed. The number of printed sheets up to the time when the streak was visually observed on the image was defined as the number of printed sheets. It shows that it is excellent in durability, so that the number of printing durability is large.

[Film resistance of toner]
A toner is mounted on a non-magnetic one-component development type printer “OKI Microline 18” (manufactured by Oki Data Co., Ltd.) and obliquely blackened to A4 size paper at a temperature of 30 ° C. and a humidity of 80% with a blackening rate of 5.5%. A stripe pattern was printed continuously. The photoreceptor was visually observed every 1000 sheets printed, and white spots caused by filming of toner on the photoreceptor were visually observed. The test was stopped when the occurrence of white spots was confirmed, up to 20,000 sheets were evaluated, and evaluated according to the following evaluation criteria.
〔Evaluation criteria〕
A: White spots do not occur even at 20,000 sheets.
B: White spots occur between 16,000 and 20,000 sheets.
C: White spots occur between 11,000 and 15,000 sheets.
D: White spots occur between 6,000 and 10,000 sheets.
E: A white spot occurs when the number is less than 5,000.

[Manufacture of resin for shell]
Synthesis Examples 1 to 3 and 6 to 8
(Production of amorphous composite resins A-1 to A-3, A-7 to A-8, and comparative resin A-6)
Equip the raw material monomer of the polyester resin part other than fumaric acid shown in Table 1, the esterification catalyst and the esterification cocatalyst with a thermometer, a stainless steel stirring bar, and a reflux condenser piped with water at 25 ° C. at the top, Place in a 10-liter four-necked flask equipped with a fractionation tube, dehydration tube, and nitrogen introduction tube with hot water of 98 ° C at the bottom, and polycondensate at 160 ° C for 2 hours in a mantle heater in a nitrogen atmosphere. After making it react, it heated up to 220 degreeC over 10 hours. Thereafter, it was confirmed that the reaction rate reached 95% at 220 ° C., and after cooling to 160 ° C., a mixed solution of the raw material monomer of the vinyl-based resin part, the bireactive monomer and the radical polymerization initiator shown in Table 1 was 1 It was added dropwise over time. Then, after maintaining at 160 ° C. for 30 minutes, the temperature was raised to 200 ° C. over 1 hour, and further reacted under reduced pressure of 8 kPa for 1 hour. Thereafter, after cooling to 190 ° C., fumaric acid and a radical polymerization inhibitor were added, the temperature was raised to 210 ° C. over 3 hours, and the reaction was carried out at 210 ° C. and 40 kPa until the softening point shown in Table 1 was reached, Amorphous composite resins A-1 to A-3, A-7 to A-8, and comparative resin A-6 were obtained. The physical properties are shown in Table 1. In addition, the reaction rate in this invention means the value of production | generation reaction water amount (mol) / theoretical production | generation water amount (mol) x100.

Synthesis example 4
(Production of Comparative Resin A-4)
Equipped with a reflux condenser tube with a thermometer, a stainless steel stirring rod, and water at 25 ° C. in the upper part, as shown in Table 1, the raw material monomer of polyester other than fumaric acid, esterification catalyst and esterification co-catalyst. Into a 10-liter four-necked flask equipped with a fractionation tube, dehydration tube, and nitrogen introduction tube with 98 ° C warm water flowing in, and a polycondensation reaction at 160 ° C for 2 hours in a mantle heater in a nitrogen atmosphere Then, the temperature was raised to 220 ° C. over 10 hours. After confirming that the reaction rate reached 95% at 220 ° C., it was cooled to 190 ° C., fumaric acid and a radical polymerization inhibitor were added, the temperature was raised to 210 ° C. over 3 hours, 210 ° C., 40 kPa The reaction was carried out until the softening point shown in Table 1 was reached to obtain a comparative resin A-4. The physical properties are shown in Table 1.

Synthesis example 5
(Production of Comparative Resin A-5)
A 10-liter four-necked flask equipped with a thermometer, a stainless steel stir bar, a flow-down condenser, and a nitrogen inlet tube with raw material monomers, esterification catalyst and esterification co-catalyst other than fumaric acid shown in Table 1 And heated up to 235 ° C. over 2 hours in a mantle heater in a nitrogen atmosphere. Thereafter, it was confirmed that the reaction rate reached 95% or higher at 235 ° C., cooled to 160 ° C., and a mixed solution of the raw material monomer of the vinyl-based resin part, both reactive monomers and the radical polymerization initiator shown in Table 1 was obtained. The solution was added dropwise over 1 hour. Then, after maintaining at 160 ° C. for 30 minutes, the temperature was raised to 200 ° C., further reacted for 1 hour under a reduced pressure of 8 kPa, and then cooled to 180 ° C. Thereafter, a radical polymerization inhibitor (4-t-butylcatechol) and fumaric acid were added, and the temperature was raised to 210 ° C. over 2 hours. Then, after reacting at 210 ° C. for 1 hour, the reaction was performed at 40 kPa until the softening point shown in Table 1 was reached, to obtain Comparative Resin A-5.

[Manufacture of core resin]
Synthesis Examples 9-13
(Production of crystalline polyesters B-1 to B-5)
Put all the raw material monomers of the crystalline polyester shown in Table 2, the esterification catalyst and the radical polymerization inhibitor into a 10-liter four-necked flask equipped with a thermometer, a stainless stir bar, a flow-down condenser and a nitrogen inlet tube. After heating up to 135 ° C. in a mantle heater in a nitrogen atmosphere, the temperature was raised to 210 ° C. over 10 hours. Furthermore, it was made to react under reduced pressure of 8 kPa for 2 hours, and crystalline polyester B-1 to B-5 was obtained. The physical properties are shown in Table 2.

Synthesis Example 14
(Vinyl resin C-1)
2 liters of xylene are put into a 10 liter four-necked flask equipped with a thermometer, a stainless steel stirring rod, a falling condenser, a dropping funnel and a nitrogen introducing tube, and the vinyl resin raw material monomer and the radical polymerization initiator are mixed. It was placed in a dropping funnel equipped with a three-necked flask. Thereafter, xylene in the four-necked flask was heated to 135 ° C. in a nitrogen atmosphere, and a mixture of the raw material monomer and the polymerization initiator was dropped into xylene from the dropping funnel over 1 hour. Furthermore, the temperature was raised to 200 ° C. and held at 200 ° C. for 2 hours. Thereafter, the pressure was reduced to 8 kPa for 1 hour to remove xylene to obtain a vinyl resin C-1. Table 3 shows the physical properties.

[Production of aqueous resin dispersion]
Production Examples 1-13
(Production of aqueous dispersions a-1 to a-8 and aqueous dispersions b-1 to b-5)
In a 3 L container equipped with a stirrer, reflux condenser, dropping funnel, thermometer and nitrogen introduction tube, 50 g of ethyl acetate and 100 g of the resin shown in Tables 4 and 5 were charged and dissolved at 70 ° C. over 2 hours. I let you. A 5% by mass aqueous sodium hydroxide solution was added to the resulting solution so that the degree of neutralization was 80 mol% with respect to the acid value of the resin, and the mixture was stirred for 30 minutes. While stirring at 280 r / min (peripheral speed 88 m / min), anionic surfactant “Neopelex (registered trademark) G-15” (manufactured by Kao Corporation, sodium dodecylbenzenesulfonate) was added to 270 g of ion-exchanged water. An aqueous solution mixed with 0.9 g as a solid content was added over 70 minutes. Next, while maintaining the temperature at 65 to 75 ° C., ethyl acetate was distilled off under reduced pressure. After cooling to 30 ° C., the solid content concentration of the dispersion was measured and adjusted with ion-exchanged water so as to be 20% by mass to obtain an aqueous dispersion. Then, while stirring at 280 r / min (peripheral speed 88 m / min), 2.1 g of an anionic surfactant “Neopelex G-15” (manufactured by Kao Corporation) was mixed with the aqueous dispersion as a solid content. The mixture was stirred for 30 minutes to obtain aqueous dispersions a-1 to a-8 and aqueous dispersions b-1 to b-5 containing resin particles, respectively. Tables 4 and 5 show the volume-median particle diameters (D ₅₀ ) of the resin particles.

Production Example 14
(Production of aqueous dispersion c-1)
100 g of vinyl-based resin C-1, 55 g of ethyl acetate, anionic surfactant “Neoperex G-15” (manufactured by Kao Corporation) as a solid content are mixed at 3.0 g at 25 ° C., and at 70 ° C. It was dissolved over 2 hours. The obtained solution was mixed with 600 g of ion-exchanged water at 70 ° C. and treated with an ultrasonic homogenizer (trade name: “UP-400S” manufactured by Dr. Heelscher) at an output of 350 W for 30 minutes. Thereafter, ethyl acetate was distilled off under reduced pressure at 70 ° C. to obtain an aqueous dispersion c-1 containing resin particles. Table 6 shows the volume-median particle size (D ₅₀ ) of the resin particles.

[Production of colorant dispersion]
Production Example 15
50 g of copper phthalocyanine “ECB-301” (manufactured by Dainichi Seika Kogyo Co., Ltd.), 5 g of nonionic surfactant “Emulgen 150” (manufactured by Kao Corporation, polyoxyethylene lauryl ether) and 200 g of ion-exchanged water are mixed. Dispersion treatment was performed at an output of 350 W for 30 minutes using an ultrasonic homogenizer (manufactured by Dr. Heelscher, trade name: “UP-400S”) to obtain a colorant dispersion containing colorant particles. The volume median particle size (D ₅₀ ) of the colorant particles was 120 nm, and the solid content concentration was 22% by mass.

[Production of release agent particle dispersion]
Production Example 16
Paraffin wax “HNP9” (produced by Nippon Seiwa Co., Ltd.) 50 g, cationic surfactant “Sanisol (registered trademark) B50” (produced by Kao Corporation, alkylbenzyldimethylammonium chloride) and ion-exchanged water 200 g at 95 ° C. A release agent dispersion containing release agent particles by heating and dispersing using an ultrasonic homogenizer (trade name: “UP-400S” manufactured by Dr. Heelscher, Inc.) at an output of 350 W for 30 minutes. Got. The volume median particle size (D ₅₀ ) of the paraffin wax (release agent particles) was 550 nm, and the solid content concentration was 22% by mass.

[Production of charge control agent dispersion]
Production Example 17
50 g of salicylic acid compound “Bontron (registered trademark) E-84” (manufactured by Orient Chemical Co., Ltd.) as a charge control agent, 5 g of “Emulgen 150” (manufactured by Kao Corporation) as nonionic surfactant, and 200 g of ion-exchanged water Were mixed using a glass bead and a sand grinder for 10 minutes to obtain a charge control agent dispersion containing charge control agent particles. The volume median particle size (D ₅₀ ) of the charge control agent particles was 400 nm, and the solid content concentration was 22% by mass.

[Manufacture of toner for developing electrostatic image]
Example 1
(Manufacture of toner A)
90 g of crystalline polyester aqueous dispersion b-1, 210 g of vinyl resin aqueous dispersion c-1, 8 g of colorant dispersion, 20 g of release agent particle dispersion, 2 g of charge control agent dispersion, and deionized water 52 g was put in a 2 L container, and 150 g of a 0.1 mass% calcium chloride aqueous solution was added dropwise at 30 ° C. over 30 minutes while stirring at 100 r / min (peripheral speed 31 m / min) with an anchor-type stirrer. Then, it heated up to 50 degreeC, stirring. It was held at 50 ° C. until the volume median particle size (D ₅₀ ) was 5 μm. After confirming that the volume median particle size (D ₅₀ ) reached 5 μm, 60 g of the aqueous dispersion a-1 of the amorphous composite resin was immediately added and dispersed by stirring. Thereafter, a dilute solution obtained by diluting 4.2 g of anionic surfactant “Emar E27C” (manufactured by Kao Corporation, solid content: 28% by mass) with 37 g of deionized water was added as an aggregation terminator. Next, the temperature was raised to 80 ° C., and after maintaining at 80 ° C. for 1 hour from the time when the temperature reached 80 ° C., the heating was terminated. As a result, fused particles were formed, and then slowly cooled to 20 ° C., filtered through a 150 mesh (mesh 150 μm) wire mesh, suction filtered, and washed and dried to obtain toner particles. .

(External addition process)
Hydrophobic silica “NAX-50” (manufactured by Nippon Aerosil Co., Ltd., number average particle diameter 40 nm) 1.0 part by mass, hydrophobic silica “R972” (manufactured by Nippon Aerosil Co., Ltd.) A 10 L Henschel mixer equipped with ST and A0 stirring blades (number average particle diameter 16 nm) 0.6 parts by mass, titanium oxide “JMT-150IB” (manufactured by Teika Co., Ltd., number average particle diameter 15 nm) The toner 1 was obtained by stirring at 3000 rpm for 2 minutes. Table 7 shows the evaluation results of the toner.

Examples 2-11, 13, 14 and Comparative Examples 1-3
(Manufacture of toners B to K, M, N and toners O to Q)
In Example 1, the toners B to K, M, and N and the toners O to Q are the same as in Example 1 except that the aqueous dispersions are changed to the types and ratios of the aqueous dispersions shown in Tables 7 and 8. Got. The total amount of the aqueous dispersion used for the core was the same as that in Example 1 (300 g). The evaluation results of the obtained toner are shown in Tables 7 and 8.

Example 12
(Manufacture of toner L)
18 g of crystalline polyester B-1, 42 g of vinyl resin C-1, colorant (copper phthalocyanine “ECB-301” (manufactured by Dainichi Seika Kogyo Co., Ltd.)), release agent (paraffin wax “HNP9” ( 4.4g, charge control agent (salicylic acid compound “Bontron E-84” (Orient Chemical Industries, Ltd.)) 0.4g, ethyl acetate 60g, and anionic surfactant “Neo” 1.0 g of PELEX G-15 ”(manufactured by Kao Corporation) was mixed and dissolved at 70 ° C. for 2 hours. To the obtained solution, 315 g of ion-exchanged water at 70 ° C. was mixed and treated for 20 minutes at an output of 200 W using an ultrasonic homogenizer (trade name: “UP-400S” manufactured by Dr. Heelscher). Thereafter, ethyl acetate was distilled off under reduced pressure at 70 ° C. to prepare core particles by a suspension method. The volume median particle size (D ₅₀ ) was 5.0 μm. After cooling this suspension to 50 ° C., 150 g of a 0.1 mass% calcium chloride aqueous solution was added dropwise over 30 minutes. Thereafter, 60 g of the aqueous dispersion a-1 of the amorphous composite resin was added and dispersed by stirring. Thereafter, a dilute solution obtained by diluting 4.2 g of anionic surfactant “Emar E27C” (manufactured by Kao Corporation, solid content: 28% by mass) with 37 g of deionized water was added as an aggregation terminator. Next, the temperature was raised to 80 ° C., and after maintaining at 80 ° C. for 1 hour from the time when the temperature reached 80 ° C., the heating was terminated. As a result, fused particles were formed, and then slowly cooled to 20 ° C., filtered through a 150 mesh (mesh 150 μm) wire mesh, suction filtered, and washed and dried to obtain toner particles. . Further, an external addition step similar to that in Example 1 was performed on the toner particles to obtain a toner L. Table 7 shows the evaluation results of the toner.

  From Tables 7 and 8, it can be seen that the toner for developing an electrostatic charge image of the example has both low-temperature fixability and durability and excellent filming resistance. On the other hand, the toner of the comparative example was inferior in durability and filming resistance.

  The toner for developing an electrostatic charge image of the present invention is excellent in low-temperature fixability, durability and filming resistance, and therefore can be suitably used as a toner used in electrophotography. Further, according to the manufacturing method of the present invention, a toner having such characteristics can be efficiently manufactured.

Claims (12)

An electrostatic charge image developing toner having a core and a shell,
The core includes a crystalline polyester and a vinyl-based resin, and the shell includes an amorphous composite resin;
The amorphous composite resin contains a polyester resin portion and a vinyl resin portion,
A toner for developing an electrostatic charge image, wherein the polyester resin portion is obtained by polycondensation of an alcohol component containing an aliphatic diol having a hydroxyl group bonded to a secondary carbon atom and a carboxylic acid component.   The crystalline polyester is obtained by polycondensing an alcohol component containing an aliphatic diol having 6 to 12 carbon atoms and a carboxylic acid component containing an aliphatic dicarboxylic acid compound having 4 to 12 carbon atoms. The toner for developing an electrostatic charge image according to claim 1, wherein   The electrostatic charge image developing toner according to claim 2, wherein the alcohol component which is a raw material monomer of the crystalline polyester contains 80 mol% or more of an aliphatic diol having 6 to 12 carbon atoms.   The amorphous composite resin is a polyester resin part raw material monomer, a vinyl resin part raw material monomer, a polyester resin part raw material monomer and a vinyl resin part raw material monomer capable of reacting with both The toner for developing an electrostatic image according to claim 1, which is obtained by polymerizing a toner.   5. The electrostatic charge image developing according to claim 4, wherein the amount of the both reactive monomers used is 1 mol part or more and 15 mol parts or less with respect to 100 mol parts of the alcohol component which is a raw material monomer of the polyester resin portion. toner.   The alcohol component which is a raw material monomer of the polyester resin portion of the amorphous composite resin contains 80 mol% or more of an aliphatic diol having a hydroxyl group bonded to a secondary carbon atom. The toner for developing an electrostatic image according to the description.   The toner for developing an electrostatic charge image according to claim 1, wherein the carboxylic acid component, which is a raw material monomer of the polyester resin portion of the amorphous composite resin, contains an aromatic dicarboxylic acid compound.   The electrostatic charge in any one of Claims 1-7 in which the carboxylic acid component which is a raw material monomer of the polyester resin part of the said amorphous composite resin contains C2-C6 aliphatic dicarboxylic acid compound. Toner for image development.   The vinyl resin portion of the amorphous composite resin includes a structural unit derived from styrene and a structural unit derived from an alkyl (meth) acrylate having an alkyl group having 6 to 18 carbon atoms. The toner for developing an electrostatic image according to any one of the above. A fat having the following steps 1 and 2, wherein the amorphous composite resin contains a polyester resin portion and a vinyl resin portion, and the raw material monomer of the polyester resin portion has a hydroxyl group bonded to a secondary carbon atom For producing a toner for developing an electrostatic image, which contains a group diol.
Step 1: An aqueous dispersion of resin particles I containing crystalline polyester and vinyl resin and an aqueous dispersion of resin particles A containing an amorphous composite resin are mixed and agglomerated to form an aqueous dispersion of resin particles II. Step 2: Step of fusing the resin particles II obtained in Step 1 The method for producing a toner for developing an electrostatic charge image according to claim 10, comprising the following step 1-I as a step of obtaining an aqueous dispersion of the resin particles I.
Step 1-I: A step of obtaining an aqueous dispersion of resin particles I by mixing and aggregating an aqueous dispersion of resin particles B containing crystalline polyester and an aqueous dispersion of resin particles C containing a vinyl resin. The method for producing a toner for developing an electrostatic charge image according to claim 10, comprising the following step 1-I ′ as a step of obtaining an aqueous dispersion of the resin particles I.
Step 1-I ′: A step of adding an aqueous medium to a solution containing crystalline polyester, vinyl resin, and organic solvent, and phase-emulsifying to obtain an aqueous dispersion of resin particles I.