JP2020173318A - Liquid developer - Google Patents

Abstract

To provide a liquid developer that is excellent in low-temperature fixability, hot offset resistance, and crushability.SOLUTION: A liquid developer has toner particles containing a binder resin and a pigment dispersed in an insulating liquid under the presence of a dispersant, and the binder resin contains at least one selected from a polyester resin that has a silicone chain and is obtained through polycondensation of an alcohol component containing at least di- or more valent alcohol and a carboxylic acid component including a di- or more valent carboxylic acid compound, and a composite resin that has s silicone chain and has a polyester resin segment and an addition polymerization resin segment.SELECTED DRAWING: None

Description

The present invention relates to a liquid developer used for developing a latent image formed by an electrophotographic method, an electrostatic recording method, an electrostatic printing method, or the like.

The electrophotographic developer includes a dry developer that uses a toner component made of a material containing a colorant and a binder resin in a dry state, and a liquid developer in which the toner component is dispersed in an insulating carrier liquid.
The liquid developer is excellent in terms of image quality because it can reduce the particle size of toner particles, and is suitable for commercial printing applications.

In Patent Document 1, in the process of developing an electrostatic latent image with a liquid toner applied on a belt or a roller member, the liquid toner is a copolymer of a colorant and at least a reactive silicone compound and a non-aqueous dispersion medium. An image forming method characterized by comprising the above is disclosed.

Patent Document 2 is a liquid developer for electrophotographic, which is obtained by dispersing a toner or ink containing a colorant and a resin as main components in a highly insulating carrier liquid, and is characterized by containing a reactive silicone compound. The electrophotographic developer described above is disclosed.

Japanese Unexamined Patent Publication No. 11-160918 Japanese Unexamined Patent Publication No. 2000-206738

In recent years, there has been an increasing demand for high speed and high image quality, and therefore, a liquid developer having excellent low temperature fixability, hot offset resistance, and pulverizability is required.
The present invention relates to a liquid developer having excellent low temperature fixability, pulverization property, and hot offset resistance.

One embodiment of the present invention is a liquid developer in which toner particles containing a binder resin and a pigment according to the following [1] are dispersed in an insulating liquid in the presence of a dispersant. A polyester resin obtained by polycondensing an alcohol component having a silicone chain and containing at least divalent alcohol and a carboxylic acid component containing a divalent or higher carboxylic acid compound, and silicone. A liquid developer having a chain and containing at least one selected from a composite resin having a polyester resin segment and a polycondensation resin segment.

According to the present invention, it is possible to provide a liquid developer having excellent low temperature fixability, hot offset resistance, and pulverization property.

[Liquid developer]
The liquid developer of one embodiment of the present invention (hereinafter, also simply referred to as “developer”) is an insulating liquid (hereinafter, “carrier oil”) in which toner particles containing a binder resin and a pigment are in the presence of a dispersant. A liquid developer dispersed in (also referred to as), wherein the binder resin contains an alcohol component having a silicone chain and containing at least a divalent or higher alcohol and a divalent or higher carboxylic acid compound. It contains at least one selected from a polyester resin obtained by polycondensing a carboxylic acid component and a composite resin having a silicone chain and having a polyester resin segment and an addition polymerization resin segment.
According to the present invention, a liquid developer having excellent low temperature fixability, pulverization property, and hot offset resistance can be obtained.
The reason for achieving such an effect is not clear, but it is considered as follows.
In the present invention, by using at least one selected from a polyester resin having a silicone chain and a composite resin having a silicone chain as the binder resin, the silicone chain can be present in the toner particles with good dispersibility. It is considered that the presence of the silicone chain portion having high hydrophobicity and low surface free energy improved the releasability of the toner particles and made it possible to achieve both low temperature fixability and hot offset resistance.
Further, in the liquid developer, the toner particles are pulverized in an insulating liquid, but since the binder resin has a silicone chain, the toner particles are less likely to reaggregate during pulverization, and the pulverizability during wet pulverization. Is expected to improve.

Definitions of various terms in the present specification are shown below.
Whether the resin is crystalline or amorphous is determined by the crystallinity index. The crystallinity index is defined by the ratio of the softening point of the resin to the maximum endothermic peak temperature (softening point (° C.) / maximum endothermic peak temperature (° C.)) in the measurement method described in Examples described later. The crystalline resin is a resin having a crystallinity index of 0.6 or more and less than 1.4, preferably 0.7 or more, more preferably 0.9 or more, and preferably 1.2 or less. Amorphous resin is a resin having a crystallinity index of 1.4 or more or less than 0.6, preferably 1.5 or more, or 0.5 or less, more preferably 1.6 or more, or 0.5 or less. Is. The crystallinity index can be appropriately adjusted depending on the type and ratio of the raw material monomers, and the production conditions such as reaction temperature, reaction time, and cooling rate. The maximum endothermic peak temperature refers to the temperature of the peak on the highest temperature side among the observed endothermic peaks. The crystallinity index can be calculated from the values obtained by the method for measuring the softening point of the resin and the maximum peak temperature of endothermic reaction described in Examples.
The "carboxylic acid compound" includes not only the carboxylic acid but also an anhydride that decomposes during the reaction to produce an acid, and an alkyl ester of each carboxylic acid (alkyl group having 1 or more and 3 or less carbon atoms).
"Bisphenol A" is 2,2-bis (4-hydroxyphenyl) propane.
The "polyester resin" is a general term for a polyester resin, a silicone-modified polyester resin, and a modified polyester resin such as a composite resin containing a polyester resin segment and an addition polymerization resin segment.

<Toner particles>
The liquid developer of the present invention comprises toner particles dispersed in an insulating liquid in the presence of a dispersant. The toner particles contain a binder resin and a pigment.
(Bundling resin)
In the present invention, the binder resin contained in the toner particles (hereinafter, also simply referred to as “binding resin”) is at least one selected from the following (1) and (2) (hereinafter, the following (1) and (hereinafter, the following (1)). At least one binder resin selected from 2) contains (also referred to as "resin A").
(1) A polyester resin having a silicone chain and obtained by polycondensing an alcohol component containing at least divalent or higher alcohol and a carboxylic acid component containing a divalent or higher carboxylic acid compound (2) Silicone chain. Composite resin having and having a polyester resin segment and an addition polymerization resin segment In the above (2), the polyester resin segment may have a silicone chain, and the addition polymerization resin segment has a silicone chain. You may.
When the liquid developer of the present invention contains the toner particles containing the above-mentioned binder resin, excellent low-temperature fixability, pulverization property, and hot offset resistance can be obtained.

Further, in the present invention, it is preferable that the binder resin contains any of the following (i) to (iv). That is, it is preferable that the resin A is any of the following (i) to (iv).
(I) An alcohol component containing a divalent or higher valent alcohol, a carboxylic acid component containing a divalent or higher carboxylic acid compound, and at least one functional group selected from a hydroxy group, a carboxy group, an amino group, and an epoxy group. , Reactant with silicone compound at one end or both ends (ii) Alcohol component containing divalent or higher alcohol, carboxylic acid component containing divalent or higher carboxylic acid compound, hydroxy group, carboxy group, amino group , And a reaction product with a silicone compound having at least one functional group selected from epoxy groups in the side chain (iii) A composite resin having a polyester resin segment and an addition polymerized resin segment, wherein the polyester resin segment is divalent. An alcohol component containing the above alcohol, a carboxylic acid component containing a divalent or higher carboxylic acid compound, and a silicone compound having at least one functional group selected from a hydroxy group, a carboxy group, an amino group, and an epoxy group. Composite resin as a reactant (iv) A composite resin having a polyester resin segment and an addition polymer resin segment, wherein the polyester resin segment contains an alcohol component containing a divalent or higher alcohol and a divalent or higher carboxylic acid compound. A composite resin which is a polycondensate with a carboxylic acid component and whose addition polymer resin segment is an addition polymer of a raw material monomer containing a silicone compound having an ethylenically unsaturated group. The binder resin of the above (1) is It is preferably at least one selected from (i) and (ii). Further, the binder resin of (2) is preferably at least one selected from (iii) and (iv), and more preferably (iii).
In the present invention, the binder resin is preferably (iii) or (iv), and the binder resin of (iii) or (iv) is an amorphous resin and is used in combination with a crystalline polyester resin. Is more preferable.

In the present invention, when the resin A is the binder resin of (1), the resin A is an alcohol component containing a divalent or higher alcohol (hereinafter, also simply referred to as “alcohol component”) and a divalent or higher carboxylic acid. A silicone compound having a carboxylic acid component (hereinafter, also simply referred to as "carboxylic acid component") and at least one functional group selected from a hydroxy group, a carboxy group, an amino group, and an epoxy group at one end or both ends of the compound. It is a reaction product with (hereinafter, also referred to as "silicone compound-1") (hereinafter, also referred to as "resin A1"), or the alcohol component, the carboxylic acid component, a hydroxy group, a carboxy group, and an amino. It is a reaction product (hereinafter, also referred to as “resin A2”) with a silicone compound (hereinafter, also referred to as “silicone compound-2”) having at least one functional group selected from a group and an epoxy group in the side chain.
When the resin A is the binder resin of (2), the resin A is a composite resin containing a polyester resin segment and a polycondensation resin segment, and the polyester resin segment is an alcohol component containing a divalent or higher valent alcohol. A composite resin which is a polycondensate of a carboxylic acid component containing a divalent or higher carboxylic acid component and a silicone compound having at least one functional group selected from a hydroxy group, a carboxy group, an amino group, and an epoxy. Hereinafter, it is also referred to as “resin A3”), or the polycondensation resin segment is an addition polymer of a raw material monomer containing a silicone compound having an ethylenically unsaturated group (hereinafter, silicone compound-3). It is a composite resin (hereinafter, also referred to as "resin A4"). When the resin A is the resin A3, examples of the silicone compound used include the above-mentioned silicone compound-1 and silicone compound-2.

Therefore, the above (i) to (iv) can be described as follows.
(I) Polyester resin which is a reaction product of an alcohol component, a carboxylic acid component and a silicone compound-1 (ii) A polyester resin which is a reaction product of an alcohol component, a carboxylic acid component and a silicone compound-2 (iii) ) It has a polyester resin segment and an addition polymerized resin segment, and the polyester resin segment is a reaction product of an alcohol component, a carboxylic acid component, and at least one selected from silicone compound-1 and silicone compound-2. Composite resin (iv) A composite resin having a polyester resin segment and an addition polymerized resin segment, wherein the added polymerized resin segment is an addition polymer of a raw material monomer containing a silicone compound-3. Hereinafter, it is used for the binder resin A. The alcohol component, the carboxylic acid component, the silicone compound-1 to the silicone compound-3, and other raw material monomers used for the addition polymerization segment will be described.

The resin A may be an amorphous polyester resin or a crystalline polyester resin. The alcohol component and the carboxylic acid component suitable for each are as follows.
-When using amorphous polyester resin-
[Alcohol component]
The alcohol component includes divalent or higher alcohol.
The content of the divalent or higher alcohol is preferably 80% by mass or more, more preferably 90% by mass or more, further preferably 95% by mass or more, and 100% by mass or less.
Examples of the dihydric or higher alcohol include aromatic diols, alkylene oxide adducts of aromatic diols, linear or branched aliphatic diols, alicyclic diols, and trihydric or higher polyhydric alcohols. Among these, an alkylene oxide adduct of an aromatic diol or a linear or branched aliphatic diol is preferable, and an alkylene oxide adduct of an aromatic diol is more preferable.

The alkylene oxide adduct of the aromatic diol is preferably the alkylene oxide adduct of bisphenol A, and more preferably the formula (I) :.

(In the formula, OR ¹ and R ² O are oxyalkylene groups, R ¹ and R ² are independently ethylene or propylene groups, and x and y indicate the average number of moles of alkylene oxide added, respectively, which are positive. The value of the sum of x and y is 1 or more, preferably 1.5 or more, and 16 or less, preferably 8 or less, more preferably 4 or less). It is an alkylene oxide adduct of.
Examples of the alkylene oxide adduct of bisphenol A include a propylene oxide adduct of bisphenol A and an ethylene oxide adduct of bisphenol A. One or more of these may be used. Among these, a combination of a propylene oxide adduct of bisphenol A and an ethylene oxide adduct of bisphenol A is preferable.
The molar ratio of the propylene oxide adduct of bisphenol A to the ethylene oxide adduct of bisphenol A (propylene oxide adduct of bisphenol A / ethylene oxide adduct of bisphenol A) is preferably 10/90 or more, more preferably 15/85. Above, it is more preferably 20/80 or more, and preferably 90/10 or less, more preferably 70/30 or less, still more preferably 60/40 or less.
The amount of the alkylene oxide adduct of bisphenol A is preferably 70 mol% or more, more preferably 90 mol% or more, further preferably 95 mol% or more, and 100 mol% or less, and further, in the alcohol component. It is preferably 100 mol%.

As the linear or branched aliphatic diol, an aliphatic diol having a hydroxyl group bonded to a secondary carbon atom is preferable.
The number of carbon atoms of the aliphatic diol having a hydroxyl group bonded to the secondary carbon atom is preferably 3 or more and 4 or less.
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, and 2,3-butanediol.
The amount of the aliphatic diol having a hydroxyl group bonded to the secondary carbon atom is preferably 70 mol% or more, more preferably 90 mol% or more, still more preferably 95 mol% or more, and 100 in the alcohol component. It is less than or equal to mol%, more preferably 100 mol%.

Other linear or branched aliphatic diols include, for example, ethylene glycol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol, 1,6-hexanediol, 1,8-. Examples thereof include octanediol, 1,9-nonanediol, 1,10-decanediol, and 1,12-dodecanediol.

Examples of the alicyclic diol include hydrogenated bisphenol A [2,2-bis (4-hydroxycyclohexyl) propane] and alkylene oxide having 2 or more and 4 or less carbon atoms of hydrogenated bisphenol A (average addition molar number 2 or more and 12). The following) Additives can be mentioned.
Examples of the trihydric or higher polyhydric alcohol include glycerin, pentaerythritol, trimethylolpropane, and sorbitol.
As these alcohol components, one kind or two or more kinds may be used.

[Carboxylic acid component]
The carboxylic acid component contains a divalent or higher carboxylic acid compound.
The content of the divalent or higher carboxylic acid compound is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, and 100% by mass or less.
Examples of the divalent or higher carboxylic acid compound include an aromatic dicarboxylic acid compound, a linear or branched aliphatic dicarboxylic acid compound, an alicyclic dicarboxylic acid compound, and a trivalent or higher polyvalent carboxylic acid compound. Among these, aromatic dicarboxylic acid compounds are preferable.

Examples of the aromatic dicarboxylic acid include phthalic acid, isophthalic acid, and terephthalic acid. Among these, isophthalic acid or terephthalic acid is preferable, and terephthalic acid is more preferable.
The amount of aromatic dicarboxylic acid in the carboxylic acid component is preferably 30 mol% or more, more preferably 50 mol% or more, still more preferably 70 mol% or more, still more preferably 90 mol% or more, and 100 mol. % Or less.

The linear or branched aliphatic dicarboxylic acid has preferably 2 or more, more preferably 4 or more, still more preferably 8 or more, still more preferably 10 or more, and preferably 22 or less, more preferably 16 or more. It is as follows.
Examples of the linear or branched aliphatic dicarboxylic acid include oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, adipic acid, sebacic acid, dodecanedioic acid, and tetradecanedi. Examples thereof include an acid, succinic acid substituted with an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an anhydride thereof, or an alkyl ester having 1 to 3 carbon atoms.
Examples of the succinic acid substituted with an aliphatic hydrocarbon group having 1 to 20 carbon atoms include dodecyl succinic acid, dodecenyl succinic acid, and octenyl succinic acid. Among these, succinic acid substituted with an aliphatic hydrocarbon group having 1 to 20 carbon atoms, or an anhydride thereof is preferable.
Among these, dodecenyl succinic acid or an anhydride thereof is preferable.
The amount of the linear or branched aliphatic dicarboxylic acid is preferably 2 mol% or more, more preferably 3 mol% or more, still more preferably 5 mol% or more, and preferably 30 mol% or more in the carboxylic acid component. Below, it is more preferably 20 mol% or less, still more preferably 10 mol% or less.

The trivalent or higher valent carboxylic acid is preferably a trivalent carboxylic acid, and examples thereof include trimellitic acid or an anhydride thereof. Of these, trimellitic acid or its anhydride is preferable.
When a trivalent or higher polyvalent carboxylic acid is contained, the amount of the trivalent or higher polyvalent carboxylic acid is preferably 1 mol% or more, more preferably 2 mol% or more, still more preferably 5 mol% in the carboxylic acid component. The above is even more preferably 10 ru% or more, still more preferably 15 mol% or more, and preferably 35 mol% or less, more preferably 30 mol% or less, still more preferably 25 mol% or less, still more preferably. Is less than 20 mol%.
One kind or two or more kinds of these carboxylic acid components may be used.

The ratio of the carboxy group of the carboxylic acid component to the hydroxy group of the alcohol component (COOH group / OH group) is preferably 0.7 or more, more preferably 0.8 or more, and preferably 1.3 or less. It is preferably 1.2 or less.

-When it is a crystalline polyester resin-
[Alcohol component]
The alcohol component contains a divalent or higher alcohol.
The alcohol component preferably contains α, ω-aliphatic diol.
The α, ω-aliphatic diol is preferably an α, ω-linear aliphatic diol.
The number of carbon atoms of the α, ω-aliphatic diol is preferably 2 or more, more preferably 4 or more, still more preferably 6 or more, and preferably 16 or less, more preferably 14 or less, still more preferably 12 or less. Yes, and even more preferably 10 or less.
Examples of the α, ω-aliphatic diol include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and 1,7-heptanediol. 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol Can be mentioned. Among these, ethylene glycol, 1,6-hexanediol, 1,9-nonanediol, 1,10-decanediol, and 1,12-dodecanediol are preferable.

The amount of α, ω-aliphatic diol is preferably 80 mol% or more, more preferably 85 mol% or more, still more preferably 90 mol% or more, still more preferably 95 mol% or more, and 100 in the alcohol component. It is less than or equal to mol%, more preferably 100 mol%.

The alcohol component may contain other alcohol components different from the α, ω-aliphatic diol. Other alcohol components include, for example, aliphatic diols other than α, ω-aliphatic diols such as 1,2-propylene glycol and neopentyl glycol; aromatic diols such as alkylene oxide adducts of bisphenol A; glycerin and penta. Examples thereof include trihydric or higher alcohols such as erythritol and trimethylol propane. One or more of these alcohol components may be used.

[Carboxylic acid component]
The carboxylic acid component contains a divalent or higher carboxylic acid compound.
The carboxylic acid component preferably contains an aliphatic dicarboxylic acid compound.
The aliphatic dicarboxylic acid compound is preferably a linear aliphatic dicarboxylic acid compound.
The aliphatic dicarboxylic acid compound preferably has 4 or more carbon atoms, more preferably 8 or more carbon atoms, still more preferably 10 or more carbon atoms, and preferably 14 or less, more preferably 12 or less carbon atoms.
Examples of the aliphatic dicarboxylic acid compound include fumaric acid, sebacic acid, dodecanedioic acid, and tetradecanedioic acid. Among these, fumaric acid, sebacic acid, and dodecanedioic acid are preferable, and sebacic acid is more preferable. One kind or two or more kinds of these carboxylic acid components may be used.

The amount of the aliphatic dicarboxylic acid compound is preferably 80 mol% or more, more preferably 85 mol% or more, still more preferably 90 mol% or more, still more preferably 95 mol% or more, and 100 in the carboxylic acid component. It is less than or equal to mol%, more preferably 100 mol%.

The carboxylic acid component may contain another carboxylic acid component different from the aliphatic dicarboxylic acid compound. Examples of other carboxylic acid components include aromatic dicarboxylic acid compounds such as terephthalic acid and isophthalic acid; and polyvalent carboxylic acid compounds having a trivalent or higher valence. These carboxylic acid components may be used alone or in combination of two or more.

The equivalent ratio of the carboxy group of the carboxylic acid component to the hydroxyl group of the alcohol component (COOH group / OH group) is preferably 0.7 or more, more preferably 0.8 or more, and preferably 1.3 or less. It is preferably 1.2 or less.

[Silicone compound-1]
Silicone compound-1 is a silicone compound used in the production of resin A1 and resin A3, and has at least one functional group selected from a hydroxy group, a carboxy group, an amino group, or an epoxy group at one end or both ends. It is a silicone compound having.

More specifically, the silicone compound-1 preferably has the formula (1-1):

[In the formula (1-1), R ¹¹ is a hydrocarbon group having 1 to 5 carbon atoms independently, and * is a binding site. ] Has a repeating unit represented by
At one end or both ends, formula (1-2):

[In the formula (1-2), R ¹² is an alkylene group having 1 to 10 carbon atoms independently, and X is a hydroxy group, a hydroxyalkyloxy group, a carboxy group, a carboxyalkyloxy group, and an amino group. , A glycidyl group, or a glycidyloxy group, and * is a binding site. ] Has a group represented by.

When one end is a group represented by the formula (1-2), the other end is the formula (1-3) :.

[In formula (1-3), R ¹³ is a hydrocarbon group having 1 or more and 10 or less carbon atoms, and * is a binding site. ] May be a group represented by.

The hydrocarbon group of R ¹¹ has 5 or less carbon atoms, preferably 4 or less, more preferably 3 or less, still more preferably 2 or less, still more preferably 1.
Examples of the hydrocarbon group of R ¹¹ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group and a pentyl group. Of these, a methyl group is preferred.
The number of carbon atoms of the alkylene group R ¹² is 10 or less, preferably 8 or less, more preferably 5 or less, more preferably 4 or less, more preferably 3 or less, more preferably 2 or less, more preferably 1.
Examples of the alkylene group of R ¹² include a methanediyl group, an ethane-1,2-diyl group, an ethane-1,1-diyl group, an n-propane-1,3-diyl group, and an n-propane-1,2-diyl group. Examples thereof include a diyl group, a 2-methylethane-1,2-diyl group, a 1,4-n-butyl group, a 1,2-tert-butyl group and a 1,5-pentyl group. Among these, a methanediyl group is preferable.
The hydrocarbon group of R ¹³ has 10 or less carbon atoms, more preferably 8 or less, still more preferably 6 or less, still more preferably 4 or less, still more preferably 3 or less, still more preferably 2 or less, still more preferably 1. ..
Examples of the hydrocarbon group of R ¹³ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, a pentyl group and a benzyl group.

The weight average molecular weight (Mw) of the silicone compound-1 is preferably 600 or more, more preferably 800 or more, still more preferably 1,000 or more, and preferably 20,000 or less, more preferably 10,000 or less. , More preferably 7,000 or less, still more preferably 6,000 or less, still more preferably 5,000 or less, still more preferably 4,000 or less.
The number average molecular weight (Mn) of the silicone compound-1 is preferably 500 or more, more preferably 700 or more, still more preferably 800 or more, and preferably 10,000 or less, more preferably 5,000 or less, further. It is preferably 4,000 or less, more preferably 3,000 or less, still more preferably 2,000 or less.

The kinematic viscosity of the silicone compound-1, at 25 ° C., preferably from 10 mm ² / s or more, more preferably 15 mm ² / s or more, more preferably 20 mm ² / s or greater, and preferably not more than 500 mm ² / s , More preferably 400 mm ² / s or less, still more preferably 300 mm ² / s or less.
The kinematic viscosity of the silicone compound is measured at 25 ° C. using a fully automatic microdynamic viscometer (manufactured by Viscotech Co., Ltd.).

The functional group equivalent of the silicone compound-1 is preferably 10 g / mol or more, more preferably 100 g / mol or more, still more preferably 200 g / mol or more, and preferably 5000 g / mol or less, more preferably 4000 g / mol or more. Below, it is more preferably 3000 g / mol or less.
The functional group equivalent means the mass of the silicone compound per mole of the functional group.

From the viewpoint of obtaining toner particles having excellent storage stability, the silicone compound-1 is a silicone compound (1-a) having a hydroxy group at one end or both ends (hereinafter, also simply referred to as “silicone compound (1-a)”). ) Is preferable.
That is, the silicone compound (1-a) preferably has a repeating unit represented by the above formula (1-1), and has the formula (1-2a): at one end or both ends.

[In the formula (1-2a), R ^12a and * have the same definition as R ¹² and * in the above formula (1-2), respectively, and X ¹¹ is a hydroxy group or a hydroxyalkyloxy group. is there. ] Has a group represented by.

Examples of the group represented by the formula (1-2a) include the following substituents 1-2a-1 to 1-2a-3. Among these, substituent 1-2a-1 or substituent 1-2a-2 is preferable, and substituent 1-2a-1 is more preferable.

When one end is a group represented by the formula (1-2a), the other end may be a group represented by the above formula (1-3).
The silicone compound (1-a) preferably has a hydroxy group at both ends from the viewpoint of further improving the storage stability. That is, the silicone compound (1-a) has a group represented by the formula (1-2a) at both ends from the viewpoint of further improving the storage stability.
Examples of the silicone compound (1-a) include both-terminal carbinol-modified silicones (commercially available products include, for example, "X-22-160AS", "KF-6000", "KF-6001", and "KF-6002". , "KF-6003" (manufactured by Shin-Etsu Chemical Co., Ltd.), one-terminal carbinol-modified silicone (commercially available products include, for example, "X-22-170BX", "X-22-170DX", "X-""22-176DX" and "X-22-176GX-A" (all manufactured by Shin-Etsu Chemical Co., Ltd.) can be mentioned.

The silicone compound-1 is preferably a silicone compound (1-b) having an epoxy group at one end or both ends from the viewpoint of obtaining toner particles having excellent durability.
That is, the silicone compound (1-b) preferably has a repeating unit represented by the above formula (1-1), and has the formula (1-2b): at one end or both ends.

In [Equation ^{(1-2b), R 12b,} and *, ^{R 12} in the formula (1-2) described above, and * and have the same definition, ^{respectively, X 12} is a glycidyl group, a glycidyloxy group .. ] Has a group represented by.
Examples of the group represented by the formula (1-2b) include the following substituents 1-2b-1 to 1-2b-3. Of these, substituent 1-2b-1 is preferable.

When one end is a group represented by the formula (1-2b), the other end may be a group represented by the above formula (1-3).
The silicone compound (1-b) preferably has an epoxy group at one end from the viewpoint of further improving low temperature fixability and hot offset resistance. That is, the silicone compound (1-b) has a group represented by the formula (1-2b) at one end from the viewpoint of further improving low temperature fixability and hot offset resistance.
The silicone compound (1-b) preferably has epoxy groups at both ends from the viewpoint of further improving durability. That is, the silicone compound (1-b) has a group represented by the formula (1-2b) at both ends from the viewpoint of further improving durability.
Examples of the silicone compound (1-b) include both-terminal epoxy-modified silicones (commercially available products include "KF-105", "X-22-163A", "X-22-163B", and "X-22-". 163C ”,“ X-22-169AS ”,“ X-22-169B ”(above, manufactured by Shin-Etsu Chemical Co., Ltd.), one-ended epoxy-modified silicone (commercially available products,“ X-22-173BX ”,“ X-22-173DX ”(above, manufactured by Shin-Etsu Chemical Co., Ltd.)).

The silicone compound-1 is preferably a silicone compound (1-c) having a carboxy group at one end or both ends from the viewpoint of obtaining toner particles having excellent durability.
That is, the silicone compound (1-c) preferably has a repeating unit represented by the above formula (1-1), and has the formula (1-2c): at one end or both ends.

[In the formula (1-2c), R ^12c and * have the same definition as R ¹² and * in the above formula (1-2), respectively, and X ¹³ is a carboxy group or a carboxyalkyloxy group. is there. ] Has a group represented by.
Examples of the group represented by the formula (1-2c) include the following substituents 1-2c-1.

When one end is a group represented by the formula (1-2c), the other end may be a group represented by the above formula (1-3).
The silicone compound (1-c) preferably has a carboxy group at both ends from the viewpoint of further improving low temperature fixability and hot offset resistance. That is, the silicone compound (1-c) has a group represented by the formula (1-2c) at both ends from the viewpoint of further improving low temperature fixability and hot offset resistance.
Examples of the silicone compound (1-c) include both-terminal carboxy-modified silicone (commercially available product, "X-22-162C" (manufactured by Shin-Etsu Chemical Co., Ltd.)).

[Silicone compound-2]
Silicone compound-2 is a silicone compound used in the production of resin A2 and resin A3, and is a silicone compound having at least one functional group selected from a hydroxy group, a carboxy group, an amino group, or an epoxy group in a side chain. is there.

More specifically, the silicone compound-2 is preferably of the formula (2-1):

[In the formula (2-1), R ²¹ is independently a hydrocarbon group having 1 or more and 5 or less carbon atoms, and R ²² is independently an alkylene group having 1 or more and 5 or less carbon atoms, a1. Is 1 or 0, X ² is a hydroxy group, a carboxy group, an amino group, or an epoxy group, respectively, and * is a binding site. ] And the formula (2-2):

[In the formula (2-2), R ²¹ is a hydrocarbon group having 1 to 5 carbon atoms independently, and * is a binding site. ] Has a repeating unit represented by.

The terminal of the silicone compound-2 is represented by the formula (2-3) :.

[In formula (2-3), R ²³ is a hydrocarbon group having 1 or more and 10 or less carbon atoms, and * is a binding site. ] May be a group represented by.

The hydrocarbon group of R ²¹ has 5 or less carbon atoms, preferably 4 or less, more preferably 3 or less, still more preferably 2 or less, still more preferably 1.
Examples of the hydrocarbon group of R ²¹ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group and a pentyl group. Of these, a methyl group is preferred.
The alkylene group of R ²² has 10 or less carbon atoms, preferably 8 or less, more preferably 5 or less, still more preferably 4 or less, still more preferably 3 or less, still more preferably 2 or less, still more preferably 1.
Examples of the alkylene group of R ²² include a methanediyl group, an ethane-1,2-diyl group, an ethane-1,1-diyl group, an n-propane-1,3-diyl group, and an n-propane-1,2-diyl group. Examples thereof include a diyl group, a 2-methylethane-1,2-diyl group, a 1,4-n-butyl group, a 1,2-tert-butyl group and a 1,5-pentyl group. Among these, a methanediyl group is preferable.
The hydrocarbon group of R ²³ has 10 or less carbon atoms, preferably 8 or less, more preferably 6 or less, still more preferably 4 or less, still more preferably 3 or less, still more preferably 2 or less, still more preferably 1.
Examples of the hydrocarbon group of R ²³ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, a pentyl group and a benzyl group.

The preferable ranges of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the silicone compound-2 are the same as the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the silicone compound-1 described above.
The kinematic viscosity of the silicone compound-2, at 25 ° C., preferably from 10 mm ² / s or more, more preferably 15 mm ² / s or more, more preferably 20 mm ² / s or more, and, preferably 3,000 mm ² / s or less, more preferably 2,000 mm ² / s or less, even more preferably 1,000mm ² / s, more preferably not more than 500 mm ² / s.
Among them, the kinematic viscosity of the silicone compound-2 having an amino group is preferably 500 mm ² / s or more, more preferably 1,000 mm ² / s or more, and further preferably 1,500 mm ² / s or more at 25 ° C. And preferably, it is 3,000 mm ² / s or less, more preferably 2,000 mm ² / s or less, and further preferably 1800 mm ² / s or less.

The functional group equivalent of the silicone compound-2 is preferably 300 g / mol or more, more preferably 500 g / mol or more, still more preferably 1,000 g / mol or more, still more preferably 2,000 g / mol or more, and preferably. Is 6,000 g / mol or less, more preferably 5,000 g / mol or less, still more preferably 4,000 g / mol or less.

Silicone compound-2 is preferably used from the viewpoint of obtaining a liquid developer having excellent low-temperature fixability.
(I) A silicone compound having an amino group in the side chain, and the mass ratio of the silicone compound is 1% by mass or more and 7% by mass with respect to the total amount of the alcohol component, the carboxylic acid component and the silicone compound. % Or less, or
(II) A silicone compound having at least one selected from a carboxy group, an epoxy group, and a hydroxy group in a side chain, and the mass ratio of the silicone compound is the alcohol component, the carboxylic acid component, and the silicone compound. It is 1% by mass or more and 30% by mass or less with respect to the total amount of.

Among these, a silicone compound (2-a) having an amino group in the side chain (hereinafter, also simply referred to as “silicone compound (2-a)”) is preferable from the viewpoint of obtaining a liquid developer having better low-temperature fixability. ..
That is, the silicone compound (2-a) is preferably represented by the following formula (2-1a):

[In the formula (2-1a), R ^21a , R ^22a , a2, and * have the same definitions as R ²¹ , R ²² , a1, and * in the above formula (2-1). ] And a repeating unit represented by the above formula (2-2).
In the formula (2-1a), examples of the group represented by *-(R ^22a ) _a2- NH ₂ include the following substituents 2-1a-1 to 2-1a-3.

The end of the silicone compound (2-a) may be a group represented by the above formula (2-3).

Examples of the silicone compound (2-a) include modified silicone having an amino group in the side chain (for example, "KF-864" (manufactured by Shin-Etsu Chemical Co., Ltd.) as a commercially available product).

The mass ratio of the silicone compound (2-a) in the resin A is preferably 1% by mass or more, more preferably 2% by mass or more, still more preferably 2% by mass or more, based on the total amount of the alcohol component, the carboxylic acid component and the silicone compound. It is 3% by mass or more, more preferably 4% by mass or more, and preferably 7% by mass or less, more preferably 6% by mass or less.

Silicone compound-2 is a silicone compound (2-b) having at least one selected from a carboxy group, an epoxy group, and a hydroxy group in the side chain from the viewpoint of obtaining a liquid developer having better low-temperature fixability (hereinafter, hereinafter, It is also preferably simply a "silicone compound (2-b)").
More specifically, the silicone compound (2-b) is preferably of the formula (2-1b):

[In the formula (2-1b), R ^21b , R ^22b , a3, and * have the same definitions as R ²¹ , R ²² , a1, and * in the above formula (2-1), respectively, and X ^2b is , Each independently is a carboxy group, an epoxy group, or a hydroxy group, and * is a binding site. ] And a repeating unit represented by the above formula (2-2).

Examples of the group represented by *-(R ^22b ) _a3- X ^2b in the formula (2-1b) include the following substituents 2-1b-1 to 2-1b-9.

The end of the silicone compound may be a group represented by the above formula (2-3).

Examples of the silicone compound (2-b) include modified silicone having a carboxy group in the side chain (as a commercial product, for example, "X-22-3701E" (manufactured by Shin-Etsu Chemical Co., Ltd.)), "BY16-880". (Manufactured by Toray Dow Corning Co., Ltd.), Modified silicone having an epoxy group in the side chain (commercially available "X-22-343" (manufactured by Shin-Etsu Chemical Co., Ltd.)), having a hydroxy group in the side chain Modified silicone (commercially available product is "X-22-4039" (manufactured by Shin-Etsu Chemical Co., Ltd.)).

The mass ratio of the silicone compound (2-b) in the resin A is preferably 1% by mass or more, more preferably 2% by mass or more, still more preferably 2% by mass or more, based on the total amount of the alcohol component, the carboxylic acid component and the silicone compound. 3% by mass or more, more preferably 4% by mass or more, and preferably 30% by mass or less, more preferably 20% by mass or less, still more preferably 15% by mass or less, still more preferably 10% by mass or less, still more preferable. Is 7% by mass or less.

[Silicone compound-3]
Silicone compound-3 is a silicone compound used for producing the resin A4, and is a silicone compound having at least one ethylenically unsaturated group. The ethylenically unsaturated group may be contained in the main chain composed of the organopolysiloxane, in the side chain, or at the end of the main chain or the side chain. Although not particularly limited, it is preferable to have an ethylenically unsaturated group at the end of the side chain or the main chain, and more preferably at the end of the main chain, from the viewpoint of availability and reactivity. That is, the silicone compound-3 more preferably has an ethylenically unsaturated group at one end or both ends of the main chain terminal, and mainly contains an ethylenically unsaturated group from the viewpoint of obtaining a liquid developer having better low-temperature fixability. It is more preferred to have it at one end of the chain.

Silicone compound-3 preferably has a repeating unit represented by the following formula (3-1) and has a group represented by the following formula (3-2) at one end or both ends.

In the formula (3-1), R ³¹ is a hydrocarbon group having 1 to 5 carbon atoms independently, and * is a binding site.

In the formula (3-2), R ³² represents an alkylene group having 1 or more and 10 or less carbon atoms, R ³³ is a hydrogen atom or a hydrocarbon group having 1 or more carbon atoms and 5 or less carbon atoms, and * is a binding site. ..

In the formula (3-1), the hydrocarbon group of R ³¹ has 5 or less carbon atoms, preferably 4 or less carbon atoms, more preferably 3 or less, still more preferably 2 or less, and even more preferably 1.
The hydrocarbon group of R ³¹ is preferably an alkyl group, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group and a pentyl group. Of these, the methyl group is more preferred.

In the formula ^(3-2), the number of carbon atoms in the alkylene group for ^{R 32,} 10 or less, preferably 8 or less, more preferably 6 or less, more preferably 4 or less, and one or more, preferably 2 or more Yes, most preferably 3. The alkylene group represented by R ¹ may be linear or branched.
In the formula (3-2), the hydrocarbon group of R ³³ has 5 or less carbon atoms, preferably 4 or less carbon atoms, more preferably 3 or less carbon atoms, still more preferably 2 or less, and even more preferably 1.
The hydrocarbon group of R ³³ is preferably an alkyl group, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group and a pentyl group. Of these, the methyl group is more preferred. As R ³³ , a hydrogen atom or a methyl group is more preferable, and a methyl group is even more preferable. That is, the silicone compound has an acryloyloxy group (CH ₂ = CH-C (= O) -O-) or a methacryloyloxy group (CH ₂ = C (CH ₃ ) -C (= O) -O-) at the end of the main chain. ), And more preferably having a methacryloyloxy group.

The kinematic viscosity of the silicone compounds -3, from the viewpoint of easy production of the composite resin, at 25 ° C., preferably ^{1 mm} 2 / s or more, more preferably ^{3 mm} 2 / s or more, more preferably it is ^{5 mm} 2 / s or more And, preferably 500 mm ² / s or less, more preferably 300 mm ² / s or less, still more preferably 100 mm ² / s or less.

The functional group equivalent of the silicone compound-3 is preferably 100 g / mol or more, more preferably 500 g / mol or more, still more preferably 800 g / mol or more, and preferably 10 from the viewpoint of ease of production of the resin A4. It is 3,000 g / mol or less, more preferably 4,000 g / mol or less, still more preferably 2,500 g / mol or less.
The functional group equivalent means the mass of the silicone compound per mole of the ethylenically unsaturated group.

As the above-mentioned silicone compound-3, a commercially available product may be used, and as the silicone compound having a methacryloyloxy group as an ethylenically unsaturated group at one end of the main chain, "X-22-174ASX" and " Examples include X-22-174BX, KF-2012, X-22-2426, and X-22-2404 (all manufactured by Shin-Etsu Chemical Industry Co., Ltd.). Among these, X-22-174-ASX , X-22-174-BX is preferred.
Silicone compounds having a methacryloyloxy group as an ethylenically unsaturated group at both ends of the main chain include "X-22-164", "X-22-164AS", "X-22-164A", and "X-22-164B". Examples thereof include "X-22-164C" and "X-22-164E" (all manufactured by Shin-Etsu Chemical Industry Co., Ltd.), and among these, X-22-164C is preferable. Examples of the silicone compound having an acryloyloxy group as an ethylenically unsaturated group at both ends of the main chain include "X-22-2445" (manufactured by Shin-Etsu Chemical Co., Ltd.).

[Other ethylenically unsaturated compounds]
As the raw material monomer of the addition polymerization resin segment, other ethylenically unsaturated compounds used in addition to the above-mentioned silicone compound-3 will be described.
When the resin A is the above (iii), the raw material monomer of the addition polymerization resin segment contains other ethylenically unsaturated compounds. In the case of (iv) above, the raw material monomer of the addition polymerization resin segment preferably contains other ethylenically unsaturated compounds in addition to the above-mentioned silicone compound-3.
The other ethylenic compound preferably contains a styrene compound from the viewpoint of obtaining a liquid developer having excellent pulverizability.
Examples of the styrene-based compound include substituted or unsubstituted styrene. Examples of the substituent include an alkyl group having 1 to 5 carbon atoms, a halogen atom, an alkoxy group having 1 to 5 carbon atoms, a sulfonic acid group or a salt thereof and the like.
Examples of styrene-based compounds include styrenes such as styrene, methylstyrene, α-methylstyrene, β-methylstyrene, tert-butylstyrene, chlorostyrene, chloromethylstyrene, methoxystyrene, styrenesulfonic acid or salts thereof. Be done. Of these, styrene is preferable.

The total content of the silicone compound-3 and the styrene compound is preferably 50% by mass or more, more preferably 65% by mass or more, still more preferably 80% by mass or more, still more preferably 80% by mass or more, in the raw material monomer of the addition polymerization resin segment. Is 90% by mass or more, and may be 100% by mass.

As the other ethylenic compound, an ethylenically unsaturated compound having an aliphatic hydrocarbon group may be contained. The number of carbon atoms of the aliphatic hydrocarbon group is preferably 3 or more, more preferably 4 or more, still more preferably 6 or more, from the viewpoint of further improving the low temperature fixability and hot offset resistance of the liquid developer. It is preferably 22 or less, more preferably 20 or less, still more preferably 18 or less.
Examples of the aliphatic hydrocarbon group include an alkyl group, an alkynyl group, and an alkenyl group. Among these, an alkyl group and an alkenyl group are preferable, and an alkyl group is preferable. The aliphatic hydrocarbon group may be either branched or linear.

The ethylenically unsaturated compound having an aliphatic hydrocarbon group is preferably an alkyl ester of (meth) acrylic acid. In the case of alkyl esters of (meth) acrylic acid, the hydrocarbon group is the alcohol-side residue of the ester.
Examples of the alkyl ester of (meth) acrylic acid include (meth) acrylic acid (iso) propyl, (meth) acrylic acid (iso) butyl, (meth) acrylic acid (iso) hexyl, and (meth) acrylic acid cyclohexyl. (Meta) Acrylic Acid (Iso) Octyl (hereinafter, also referred to as (Meta) Acrylic Acid 2-Ethylhexyl), (Meta) Acrylic Acid (Iso) Decyl, (Meta) Acrylic Acid (Iso) Dodecyl (hereinafter, (Meta) Acrylic) Examples include acid (iso) lauryl), (meth) acrylic acid (iso) palmityl, (meth) acrylic acid (iso) stearyl, and (meth) acrylic acid (iso) behenyl.
Here, "alkyl (meth) acrylate" means alkyl acrylate or alkyl methacrylate. Further, with respect to the alkyl moiety, "(iso)" means normal alkyl or isoalkyl.

Examples of other raw material monomers include ethylenically unsaturated monoolefins such as ethylene and propylene; conjugated dienes such as butadiene; halovinyls such as vinyl chloride; vinyl esters such as vinyl acetate and vinyl propionate; (meth). ) (Meta) acrylic acid aminoalkyl esters such as dimethylaminoethyl acrylate; vinyl ethers such as methyl vinyl ether; vinylidene halides such as vinylidene chloride; N-vinyl compounds such as N-vinylpyrrolidone.

[Constituent units derived from bireactive monomers]
When the resin A is a composite resin, it has a structural unit derived from a bireactive monomer bonded to the polyester resin segment and the addition polymerization resin segment via a covalent bond in order to connect the polyester resin segment and the addition polymerization resin segment. Is preferable.
The "constituent unit derived from a bireactive monomer" means a structural unit in which a carboxy group of the bireactive monomer, a functional group capable of reacting with a hydroxyl group, and an ethylenically unsaturated group have reacted.
Examples of the bireactive monomer include an ethylenically unsaturated compound having at least one functional group selected from a hydroxyl group, a carboxy group, an epoxy group, a primary amino group and a secondary amino group in the molecule. Be done. Among these, from the viewpoint of reactivity, an ethylenically unsaturated compound having a hydroxyl group or a carboxy group is preferable, and an ethylenically unsaturated compound having a carboxy group is more preferable.
Examples of the bireactive monomer include acrylic acid, methacrylic acid, fumaric acid, maleic acid and the like. Among these, acrylic acid and methacrylic acid are preferable, and acrylic acid is more preferable, from the viewpoint of reactivity of both the polycondensation reaction and the addition polymerization reaction.
The amount of the structural unit derived from both reactive monomers is preferably 0.5 mol parts or more, more preferably 1 mol part or more, still more preferably 3 mol parts or more, based on 100 mol parts of the alcohol component of the polyester resin segment. Yes, and preferably 30 mol parts or less, more preferably 10 mol parts or less, still more preferably 5 mol parts or less.
When the resin A is a composite resin, the content of the polyester resin segment raw material in the resin raw material is preferably 50% by mass or more, more preferably 50% by mass or more, from the viewpoint of further improving the low-temperature fixability and hot offset resistance of the liquid developer. Is 65% by mass or more, more preferably 75% by mass or more, and preferably 99% by mass or less, more preferably 98% by mass or less, still more preferably 96% by mass or less.

When the resin A is a composite resin, the content of the addition polymerization resin segment raw material in the raw material of the composite resin is preferably 3% by mass or more, more preferably from the viewpoint of further improving the low-temperature fixability and pulverizability of the liquid developer. It is preferably 4.5% by mass or more, further preferably 10% by mass or more, still more preferably 15% by mass or more, still more preferably 18% by mass or more, and preferably 50% by mass or less, more preferably 40% by mass or more. It is mass% or less, more preferably 30 mass% or less, still more preferably 20 mass% or less.
When the resin A is a composite resin, the content of the bireactive monomer in the raw material of the composite resin is preferably 0.1% by mass or more from the viewpoint of further improving the low temperature fixability and durability of the liquid developer. It is more preferably 0.2% by mass or more, further preferably 0.4% by mass or more, and preferably 10% by mass or less, more preferably 5% by mass or less, still more preferably 3% by mass or less.
When the resin A is a composite resin, the total amount of the polyester resin segment and the addition polymerization resin segment in the composite resin and the structural units derived from the bireactive monomers further improves the low temperature fixability and pulverizability of the liquid developer. From the viewpoint, it is preferably 80% by mass or more, more preferably 90% by mass or more, further preferably 93% by mass or more, still more preferably 95% by mass or more, and 100% by mass or less, preferably 99% by mass. % Or less.
The above content is calculated based on the ratio of the amounts of the alcohol component and the carboxylic acid component of the polyester resin segment, the raw material monomer of the addition polymerization resin segment, the bireactive monomer, and the polymerization initiator, and polycondensation in the polyester resin segment and the like. The amount of dehydration due to resin is not considered. When a polymerization initiator is used, the mass of the polymerization initiator is included in the addition polymerization resin segment for calculation.

Hereinafter, the resins A1 to A4 will be described.
The resin A is preferably an amorphous polyester resin. In particular, when the resin A is the resin A3 or A4, it is preferably an amorphous polyester resin.
In the present invention, the resin A is preferably resin A3 or A4, more preferably resin A3, and even more preferably resin A3 which is an amorphous polyester resin.
When the resin A is an amorphous polyester resin, it is preferable to use a crystalline polyester resin described later in combination as the binder resin.

(Resin A1)
Resin A1 contains an alcohol component containing a divalent or higher alcohol, a carboxylic acid component containing a divalent or higher carboxylic acid compound, and at least one functional group selected from a hydroxy group, a carboxy group, an amino group, and an epoxy group. , A reaction product with a silicone compound (silicone compound-1) having one end or both ends.

The amount of the silicone compound-1 in the raw material of the resin A1 is preferably 0.1% by mass or more, more preferably 1% by mass or more, and further, with respect to the total amount of the alcohol component, the carboxylic acid component and the silicone compound-1. It is preferably 2% by mass or more, more preferably 4% by mass or more, and preferably 30% by mass or less, more preferably 20% by mass or less, still more preferably 10% by mass or less, still more preferably 7% by mass or less. , More preferably 6% by mass or less.

The amount of the alcohol component and the carboxylic acid component in the raw material of the resin A1 is preferably 70% by mass or more, more preferably 80% by mass or more, based on the total amount of the alcohol component, the carboxylic acid component and the silicone compound-1. It is more preferably 90% by mass or more, still more preferably 93% by mass or more, still more preferably 94% by mass or more, and preferably 99.9% by mass or less, more preferably 99% by mass or less, still more preferably. It is 98% by mass or less, more preferably 94% by mass or less.
The above amount is calculated based on the alcohol component, the carboxylic acid component and the silicone compound, and the amount of dehydration due to condensation is not taken into consideration.
When the silicone compound has a hydroxy group or a carboxy group, it can be understood as an alcohol component or a carboxylic acid component, but when the compound having a hydroxy group or a carboxy group contains a silicone skeleton, it is a silicone compound. For example, when calculating the total amount of the alcohol component and the carboxylic acid component, the silicone compound having a hydroxy group or a carboxy group is not included in the total amount.

The number average molecular weight of the resin A1 is preferably 500 or more, more preferably 1,000 or more, still more preferably 1,500 or more, still more preferably 2,000 or more, from the viewpoint of obtaining excellent hot offset resistance. Then, preferably 30,000 or less, more preferably 20,000 or less, still more preferably 10,000 or less, still more preferably 8,000 or less, still more preferably 6,000 or less from the viewpoint of obtaining excellent low temperature fixability. , More preferably 5,000 or less.
However, when the silicone compound-1 is a silicone compound having a hydroxy group at one end or both ends, the number average molecular weight of the resin A1 is preferably 1,000 or more from the viewpoint of obtaining excellent hot offset resistance. , More preferably 1,500 or more, still more preferably 2,000 or more, and from the viewpoint of obtaining excellent low temperature fixability, preferably 10,000 or less, more preferably 8,000 or less, still more preferably 6. It is 5,000 or less, more preferably 5,000 or less.

The acid value of the resin A1 is preferably 0.1 mgKOH / g or more, more preferably 0.5 mgKOH / g or more, still more preferably 1 mgKOH / g or more, and preferably 40 mgKOH / g or less, more preferably 30 mgKOH / g. It is g or less, more preferably 20 mgKOH / g or less. When the resin A1 is an amorphous polyester resin, the hydroxyl value of the resin A1 is preferably 0.1 mgKOH / g or more, more preferably 10 mgKOH / g or more, still more preferably 20 mgKOH / g or more, and , Preferably 60 mgKOH / g or less, more preferably 50 mgKOH / g or less, still more preferably 40 mgKOH / g or less.

The softening point of the resin A1 is preferably 70 ° C. or higher, more preferably 90 ° C. or higher, still more preferably 100 ° C. or higher, and further improving the low temperature fixability, from the viewpoint of further improving the hot offset resistance. Therefore, it is preferably 140 ° C. or lower, more preferably 130 ° C. or lower, still more preferably 125 ° C. or lower, still more preferably 120 ° C. or lower, still more preferably 110 ° C. or lower.
Further, the softening point of the resin A1 is preferably 60 ° C. or higher, more preferably 70 ° C. or higher, further preferably 80 ° C. or higher, and further improving the low temperature fixability, from the viewpoint of further improving the hot offset resistance. From the viewpoint of the temperature, it is preferably 120 ° C. or lower, more preferably 110 ° C. or lower, still more preferably 100 ° C. or lower, still more preferably 90 ° C. or lower.

The resin A glass transition temperature is preferably 45 ° C. or higher, more preferably 48 ° C. or higher, still more preferably 50 ° C. or higher, still more preferably 55 ° C. or higher, from the viewpoint of further improving hot offset resistance and storage stability. Then, from the viewpoint of further improving the low temperature fixability, the temperature is preferably 80 ° C. or lower, more preferably 70 ° C. or lower, and further preferably 65 ° C. or lower.

The number average molecular weight, acid value, softening point, and glass transition temperature of the resin A1 can be appropriately adjusted according to the type and amount of the raw material monomer used, and the production conditions such as reaction temperature, reaction time, and cooling rate. , Those values are determined by the method described in the examples.
When two or more types of resin A1 are used in combination, the values of the number average molecular weight, acid value, hydroxyl value, softening point, and glass transition temperature obtained as a mixture thereof must be within the above ranges. preferable.

[Manufacturing method of resin A1]
The resin A1 can be obtained, for example, by reacting an alcohol component, a carboxylic acid component, and a silicone compound-1. In the reaction, if necessary, an esterification catalyst such as di (2-ethylhexanoic acid) tin (II), dibutyltin oxide, and titanium diisopropirate bistriethanolamineate is used as the total amount of the alcohol component and the carboxylic acid component. 0.01 part by mass or more and 5 parts by mass or less with respect to 100 parts by mass; total amount of alcohol component and carboxylic acid component of esterification co-catalyst such as gallic acid (same as 3,4,5-trihydroxybenzoic acid) 100 The reaction may be carried out using 0.001 part by mass or more and 0.5 part by mass or less with respect to parts by mass.
The temperature of the reaction is preferably 120 ° C. or higher, more preferably 160 ° C. or higher, still more preferably 180 ° C. or higher, and preferably 250 ° C. or lower, more preferably 240 ° C. or lower.
The reaction may be carried out in an inert gas atmosphere.

The content of the resin A1 is preferably 10% by mass or more, more preferably 20% by mass or more, still more preferably 20% by mass or more in the binder resin of the toner particles from the viewpoint of further improving the low temperature fixability and the hot offset resistance of the liquid developer. Is 30% by mass or more, more preferably 40% by mass or more, still more preferably 50% by mass or more, and 100% by mass or less, preferably 90% by mass or less, more preferably 80% by mass or less, still more preferably 70. It is mass% or less.

(Resin A2)
Resin A2 is an alcohol component containing a divalent or higher alcohol, a carboxylic acid component containing a divalent or higher carboxylic acid compound, and at least one functional group selected from a hydroxy group, a carboxy group, an amino group, and an epoxy group. It is a reaction product with a silicone compound (silicone compound-2) having.

The acid value of the resin A2 is preferably 0.1 mgKOH / g or more, more preferably 0.5 mgKOH / g or more, still more preferably 1 mgKOH / g or more, and preferably 40 mgKOH / g or less, more preferably 30 mgKOH / g or more. It is g or less, more preferably 20 mgKOH / g or less. When the resin A2 is an amorphous polyester resin, the hydroxyl value of the resin A2 is preferably 0.1 mgKOH / g or more, more preferably 10 mgKOH / g or more, still more preferably 20 mgKOH / g or more, and preferably. Is 60 mgKOH / g or less, more preferably 50 mgKOH / g or less, still more preferably 40 mgKOH / g or less.

The preferable range of the softening point and the glass transition temperature of the resin A2 is the same as the preferable range of the softening point and the glass transition temperature of the resin A1.
The number average molecular weight of the resin A2 is preferably 1,000 or more, more preferably 1,500 or more, still more preferably 2,000 or more, still more preferably 2,500 or more, from the viewpoint of excellent document offset resistance. From the viewpoint of excellent low temperature fixability, it is preferably 10,000 or less, more preferably 8,000 or less, still more preferably 6,000 or less, still more preferably 4,000 or less.

The acid value, softening point, glass transition temperature, and number average molecular weight of the resin A2 can be appropriately adjusted depending on the type and amount of the raw material monomer used, and the production conditions such as reaction temperature, reaction time, and cooling rate. , Those values are determined by the method described in the examples.
When two or more kinds of reactants are used in combination, it is preferable that the acid value, the hydroxyl value, the softening point, and the glass transition temperature obtained as a mixture thereof are within the above ranges.

The resin A2 can be obtained in the same manner as the resin A-1 except that the silicone compound-2 is used instead of the silicone compound-1 as the silicone compound.
The preferable range of the content of the resin A2 in the binder resin of the toner particles is the same as the content of the resin A1.

(Resin A3)
Resin A3 is a composite resin having a polyester resin segment and an addition polymerized resin segment, and the polyester resin segment contains an alcohol component containing a divalent or higher alcohol, a carboxylic acid component containing a divalent or higher carboxylic acid compound, and the like. It is a reaction product with a silicone compound having at least one functional group selected from a hydroxy group, a carboxy group, an amino group, and an epoxy group.
Here, as the silicone compound, a silicone compound selected from the group consisting of silicone compound-1 and silicone compound-2 may be used.
Further, as the polyester resin constituting the polyester resin segment, the above-mentioned resins A1 and A2 can be applied. The polyester resin segment is preferably amorphous.
The content of the silicone compound in the raw material of the polyester resin segment of the resin A3 is preferably 0.3% by mass or more, more preferably 0.5% by mass or more, from the viewpoint of low temperature fixability, offset resistance, and pigment dispersibility. , More preferably 1.5% by mass or more, still more preferably 2.5% by mass or more, still more preferably 3.5% by mass or more, still more preferably 4% by mass or more, and preferably 8% by mass. % Or less, more preferably 7.5% by mass or less, still more preferably 7% by mass or less, still more preferably 6% by mass or less, still more preferably 5% by mass or less.
Here, the content of the silicone compound in the raw material of the polyester resin segment of the resin A3 is the content of the silicone compound in the alcohol component, the carboxylic acid component, and the silicone compound in which the polyester resin segment is blended at the time of synthesis. The raw material of the resin A3 is a raw material of a polyester resin segment containing an alcohol component, a carboxylic acid component, and a silicone compound, a raw material monomer of the addition polymerization resin segment, a polymerization initiator at the time of synthesizing the addition polymerization resin segment, and the above-mentioned description. Contains bireactive monomers.

The acid value of the resin A3 is preferably 1 mgKOH / g or more, more preferably 3 mgKOH / g or more, still more preferably 5 mgKOH / g or more, from the viewpoint of obtaining a liquid developer having excellent chargeability and dispersion stability of toner particles. , And preferably 40 mgKOH / g or less, more preferably 30 mgKOH / g or less.
The hydroxyl value of the resin A3 is preferably 5 mgKOH / g or more, more preferably 15 mgKOH / g or more, still more preferably 20 mgKOH / g or more, still more preferably 25 mgKOH / g or more, and preferably 60 mgKOH / g or less. It is preferably 50 mgKOH / g or less, more preferably 40 mgKOH / g or less.

In the present invention, the softening point of the resin A3 is preferably 90 ° C. or higher, more preferably 100 ° C. or higher, further preferably 110 ° C. or higher, and preferably 150 ° C. or lower, from the viewpoint of further improving low temperature fixability. , More preferably 140 ° C. or lower, still more preferably 135 ° C. or lower, still more preferably 130 ° C. or lower.

The glass transition temperature of the resin A3 is preferably 45 ° C. or higher, more preferably 50 ° C. or higher, still more preferably 55 ° C. or higher, further, from the viewpoint of obtaining a liquid developer having excellent dispersion stability and low-temperature fixability of toner particles. It is preferably 60 ° C. or higher, and preferably 80 ° C. or lower, more preferably 70 ° C. or lower, still more preferably 65 ° C. or lower, still more preferably 64 ° C. or lower.

The number average molecular weight of the resin A3 is preferably 1,000 or more, more preferably 2,000 or more, still more preferably 2, from the viewpoint of obtaining a liquid developer having excellent low temperature fixability, hot offset resistance, and pulverizability. It is 500 or more, and preferably 8,000 or less, more preferably 5,000 or less, still more preferably 3,500 or less, still more preferably 3,000 or less.

The acid value, hydroxyl value, softening point, glass transition temperature, and number average molecular weight of the resin A3 can be appropriately adjusted according to the type and amount of the raw material monomer used, and the production conditions such as reaction temperature, reaction time, and cooling rate. Yes, and their values are determined by the method described in the examples.
When two or more types of resin A3 are used in combination, the acid value, hydroxyl value, softening point, glass transition temperature, and number average molecular weight of any of the resins must be within the above ranges. It is more preferable that the acid value, hydroxyl value, softening point, glass transition temperature, and number average molecular weight of all the resins A3 are within the above ranges.

[Manufacturing method of resin A3]
The method for producing the resin A3 includes, for example, polycondensation of the alcohol component and the carboxylic acid component, and addition polymerization with the raw material monomer and the bireactive monomer of the addition polymerization resin segment. The methods I) to (III) can be mentioned.
(I) Method of performing addition polymerization with a raw material monomer and a bireactive monomer of an addition polymerization resin segment after polycondensation with an alcohol component and a carboxylic acid component (II) Addition with a raw material monomer and a bireactive monomer of an addition polymerization resin segment After polymerization, polycondensation of polyester resin segment with raw material monomer (III) Addition polymerization of alcohol component and carboxylic acid component and addition polymerization resin segment with raw material monomer and bireactive monomer are performed in parallel. Method The polycondensation and addition polymerization of the methods (I) to (III) above are preferably carried out in the same container.
The resin A3 is preferably produced by the method (I) or (II) above because of the high degree of freedom in the reaction temperature of the polycondensation reaction, and the resin A3 is more preferable. In the production of the resin A3, the silicone compound-1 and / or the silicone compound-2 are allowed to coexist together with the alcohol component and the carboxylic acid component to introduce the silicone chain into the polyester resin segment.
From the viewpoint of reactivity, catalysts such as an esterification catalyst and an esterification co-catalyst may be used, and a polymerization initiator and a polymerization inhibitor may be used. The esterification catalyst, the esterification auxiliary catalyst, and the preferable addition amounts thereof are as described in Resin A1.
In the production of the resin A3, if necessary, a radical polymerization inhibitor such as 4-tert-butylcatechol is added in an amount of 0.001 part by mass or more and 0.5 part by mass or less based on 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component. May be used for polycondensation.
The temperature of the polycondensation is preferably 120 ° C. or higher, more preferably 140 ° C. or higher, still more preferably 155 ° C. or higher, and preferably 250 ° C. or lower, more preferably 240 ° C. or lower.
The polycondensation may be carried out in an inert gas atmosphere.
From the viewpoint of further advancing the polycondensation and, if necessary, the reaction with the bireactive monomers, a part of the carboxylic acid component is subjected to polycondensation, then addition polymerization is carried out, and then the reaction temperature is raised again, and the rest is reacted. It is preferable to add it to the system.

In the addition polymerization, the raw material monomer and the bireactive monomer of the addition polymerization resin segment are addition-polymerized.
The temperature of the addition polymerization is preferably 110 ° C. or higher, more preferably 130 ° C. or higher, and preferably 220 ° C. or lower, more preferably 210 ° C. or lower. Further, it is preferable to accelerate the reaction by reducing the pressure of the reaction system in the latter half of the polymerization.
Examples of the polymerization initiator for addition polymerization include peroxides such as di-tert-butyl peroxide, persulfates such as sodium persulfate, and 2,2'-azobis (2,4-dimethylvaleronitrile). A known polymerization initiator such as an azo compound can be used.
The preferable ranges of the acid value, hydroxyl value, softening point, glass transition temperature, and number average molecular weight of the resin A4 are the same as the preferable ranges of the acid value, hydroxyl value, softening point, glass transition temperature, and number average molecular weight of the resin A3, respectively. Is.
The acid value, hydroxyl value, softening point, glass transition temperature, and number average molecular weight of the resin A4 can be appropriately adjusted according to the type and amount of the raw material monomer used, and the production conditions such as reaction temperature, reaction time, and cooling rate. Yes, and their values are determined by the method described in the examples.
When two or more types of resin A4 are used in combination, the acid value, hydroxyl value, softening point, glass transition temperature, and number average molecular weight of any of the resins must be within the above ranges. It is more preferable that the acid value, hydroxyl value, softening point, glass transition temperature, and number average molecular weight of all the resins A4 are within the above ranges.

[Manufacturing method of resin A4]
As a method for producing the resin A4, the same production method as that for the resin A3 is exemplified. The resin A4 can be produced by the same production method as the resin A3 except that the silicone compound-3 is used as the raw material monomer of the addition polymerization segment and the silicone compound-1 and the silicone compound-2 are not used.

(Other binding resins)
In the present invention, in addition to the resin A described above, it is preferable to contain a resin having no silicone chain, and other binder resins do not have the amorphous polyester resin B having no silicone chain and the silicone chain. A crystalline polyester resin C is exemplified.
[Resin B]
Resin B is a polycondensate of an alcohol component and a carboxylic acid component.
However, the case of the above resin A is excluded. That is, the resin B does not contain a silicone chain. The alcohol component and the carboxylic acid component are as exemplified above.

≪Physical properties of resin B≫
The acid value of the resin B is preferably 0.1 mgKOH / g or more, more preferably 0.5 mgKOH / g or more, still more preferably 1 mgKOH / g or more, and preferably 40 mgKOH / g or less, more preferably 35 mgKOH / g. It is g or less, more preferably 30 mgKOH / g or less, still more preferably 23 mgKOH / g or less, still more preferably 20 mgKOH / g or less.

The difference between the softening point of the resin B and the softening point of the resin A is preferably 5 ° C. or higher, more preferably 10 ° C. or higher, still more preferably 20 ° C. or higher, further preferably 30 ° C. or higher, and preferably 60 ° C. or higher. ° C. or lower, more preferably 50 ° C. or lower, still more preferably 40 ° C. or lower. At this time, from the viewpoint of further improving the hot offset resistance, it is preferable that the softening point of the resin A is low.
The softening point of the resin B is preferably 70 ° C. or higher, more preferably 90 ° C. or higher, still more preferably 100 ° C. or higher, still more preferably 110 ° C. or higher, from the viewpoint of further improving hot offset resistance and storage stability.
The softening point of the resin B is preferably 160 ° C. or lower, more preferably 150 ° C. or lower, further preferably 140 ° C. or lower, still more preferably 130 ° C. or lower, still more preferably, from the viewpoint of further improving hot offset resistance and storage stability. Is 120 ° C. or lower, more preferably 110 ° C. or lower.

The glass transition temperature of the resin B is preferably 50 ° C. or higher, more preferably 60 ° C. or higher, further preferably 63 ° C. or higher, and preferably 80 ° C. or lower, more preferably 75 ° C. or lower, still more preferably 70 ° C. or higher. It is as follows.

The acid value, softening point, and glass transition temperature of the resin B can be appropriately adjusted according to the type and amount of the raw material monomer used, and the production conditions such as the reaction temperature, reaction time, and cooling rate, and their values. Is determined by the method described in the examples.
When two or more kinds of resin B are used in combination, it is preferable that the acid value, the softening point, and the glass transition temperature obtained as a mixture thereof are within the above ranges.

Resin B is obtained, for example, by polycondensation of an alcohol component and a carboxylic acid component. As the polycondensation conditions, for example, the reaction conditions shown in the above-mentioned method for producing resin A can be applied.

When the resin B is contained, the mass ratio of the resin A to the resin B [resin A / resin B] is preferably 20/80 or more, more preferably 20/80 or more, from the viewpoint of improving low temperature fixability and hot offset resistance. It is 30/70 or more, more preferably 40/60 or more, still more preferably 50/50 or more, and preferably 90/10 or less, more preferably 80/20 or less.

When the resin B is contained, the content of the resin B is preferably 10% by mass or more, more preferably 20% by mass, from the viewpoint of improving the low-temperature fixability and the hot offset resistance in the binder resin of the toner particles. The above is more preferably 30% by mass or more, and preferably 90% by mass or less, more preferably 80% by mass or less, still more preferably 70% by mass or less, still more preferably 60% by mass or less, still more preferably 50% by mass. % Or less.

[Resin C]
The toner particles of the present invention may contain a crystalline polyester resin (resin C) from the viewpoint of obtaining a liquid developer having excellent low-temperature fixability, hot offset resistance, and pigment dispersibility. The crystalline polyester resin C is, for example, a polycondensate of an alcohol component and a carboxylic acid component. As the alcohol component and the carboxylic acid component, the alcohol component and the carboxylic acid component exemplified in the case where the polyester resin is a crystalline polyester resin are exemplified in the resin A, and the preferred embodiment is also the same.

The ratio of the carboxy group of the carboxylic acid component to the hydroxyl group of the alcohol component (COOH group / OH group) is preferably 0.7 or more, more preferably 0.8 or more, and preferably 1.3 or less, more preferably. Is 1.2 or less.

≪Physical properties of resin C≫
The softening point of the crystalline polyester resin (resin C) is preferably 60 ° C. or higher, more preferably 70 ° C. or higher, further preferably 75 ° C. or higher, and low temperature fixability, from the viewpoint of further improving durability. From the viewpoint of further improvement, the temperature is preferably 150 ° C. or lower, more preferably 120 ° C. or lower, still more preferably 100 ° C. or lower.
The melting point of the resin C is preferably 50 ° C. or higher, more preferably 60 ° C. or higher, further preferably 70 ° C. or higher from the viewpoint of further improving durability, and preferably from the viewpoint of further improving low temperature fixability. Is 100 ° C. or lower, more preferably 90 ° C. or lower.

The acid value of the resin C is preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g or more, and preferably 35 mgKOH / g or less, more preferably 25 mgKOH, from the viewpoint of further improving durability and low-temperature fixability. / G or less, more preferably 20 mgKOH / g or less.
The hydroxyl value of the resin C is preferably 1 mgKOH / g or more, more preferably 2 mgKOH / g or more, still more preferably 3 mgKOH / g or more, and preferably 35 mgKOH / g or more, from the viewpoint of further improving durability and low temperature fixability. / G or less, more preferably 30 mgKOH / g or less, still more preferably 20 mgKOH / g or less.

The softening point, melting point, acid value, and hydroxyl value of the resin C can be appropriately adjusted according to the type and ratio of the raw material monomers, and the production conditions such as reaction temperature, reaction time, and cooling rate. Those values are obtained by the method described in Examples described later. When two or more kinds of crystalline resins are used in combination, it is preferable that the softening point, melting point, acid value, and hydroxyl value obtained as a mixture thereof are within the above ranges.

Resin C is obtained, for example, by polycondensation of an alcohol component and a carboxylic acid component. As the polycondensation condition, for example, the condition shown in the polycondensation of the polyester resin segment in the resin A3 described above can be applied.

When the binder resin contains the crystalline polyester resin C, the mass ratio of the crystalline polyester resin C to the total of the composite resin A and the polyester resin B [(C) / ((A) + (B))] Is preferably 1/99 or more, more preferably 2/98 or more, still more preferably 5/95 or more, still more preferably 8/92, from the viewpoint of further improving the low temperature fixability and hot offset resistance of the liquid developer. The above, and preferably 50/50 or less, more preferably 40/60 or less, still more preferably 30/70 or less, still more preferably 20/80 or less, still more preferably 15/85 or less.

When the binder resin contains a crystalline polyester resin (resin C), the mass ratio of the resin C to the resin A [resin C / resin A] further improves the low temperature fixability and hot offset resistance of the liquid developer. From the viewpoint of making the resin, it is preferably 10/90 or more, more preferably 20/90 or more, further preferably 25/75 or more, and preferably 70/30 or less, more preferably 60/40 or less, still more preferably 55. It is / 45 or less.

When the binder resin of the toner particles contains at least one selected from the resin B and the resin C, the content of the resin A, the resin B and the resin C is preferably 80% by mass or more, more preferably. Is 90% by mass or more, more preferably 95% by mass or more, and 100% by mass or less, and preferably 100% by mass.

In the liquid developer of the present invention, the toner particles may contain resins other than the resins A to C shown above as long as the effects of the present invention are not impaired. The content is preferably 90% by mass or more, more preferably 95% by mass or more, preferably 100% by mass or less, more preferably substantially 100% by mass, still more preferably 100% by mass, based on the total amount of the resin. Yes, that is, it is more preferable to use only resins A to C as the resin.
Examples of resins other than these resins include polyester resins other than resins A to C, polystyrene, styrene-propylene copolymer, styrene-butadiene copolymer, styrene-vinyl chloride copolymer, and styrene-vinyl acetate copolymer. Styrene-based resin, epoxy which is a homopolymer or copolymer containing a styrene or a styrene substituent such as a coalescence, a styrene-maleic acid copolymer, a styrene-acrylic acid ester copolymer, or a styrene-methacrylate copolymer Examples thereof include resins, rosin-modified maleic acid resins, styrene resins, polypropylenes, polyurethanes, silicone resins, phenol resins, aliphatic or alicyclic hydrocarbon resins.

(Pigment)
In the present invention, the toner particles contain a binder resin and a pigment.
As the pigment, all pigments used as colorants for toner can be used, such as carbon black, phthalocyanine blue, permanent brown FG, brilliant first scarlet, pigment green B, rodamine-B base, solvent red 49, Solvent Red 146, Solvent Blue 35, quinacridone, carmine 6B, isoindoline, disazoero and the like can be used. In the present invention, the toner particles may be either black toner particles or color toner particles.

The content of the pigment determines the pulverizability of the toner particles to obtain a liquid developer having a small particle size, the viewpoint of improving the low-temperature fixability of the liquid developer, and the dispersion stability of the toner particles in the liquid developer. From the viewpoint of improving and improving storage stability, preferably 100 parts by mass or less, more preferably 70 parts by mass or less, still more preferably 50 parts by mass or less, still more preferably 25 parts by mass with respect to 100 parts by mass of the binder resin. From the viewpoint of improving the image density of the liquid developer, the content is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and further preferably 15 parts by mass or more with respect to 100 parts by mass of the binder resin. is there.

In the present invention, the toner particles are further used as a release agent, a charge control agent, a magnetic powder, a fluidity improver, a conductivity adjuster, a reinforcing filler such as a fibrous substance, an antioxidant, a cleanability improver and the like. Additives may be appropriately contained.

<Liquid developer>
The liquid developer of the present invention is obtained by dispersing toner particles containing a binder resin and a pigment in an insulating liquid in the presence of a dispersant.

(Dispersant)
The liquid developer of the present invention is dispersed from the viewpoint of improving the dispersion stability of toner particles to improve storage stability and improving the pulverizability of toner particles during wet pulverization to obtain a liquid developer having a small particle size. Contains the agent. In the present invention, the dispersant is preferably a basic dispersant having a basic nitrogen-containing group from the viewpoint of high adsorptivity to a resin having an acidic group. Examples of the basic nitrogen-containing group include an amino group (-NH ₂ , -NHR, -NHRR'), an amide group (-C (= O) -NRR'), an imide group (-N (COR) ₂ ), and a nitro group. From the group consisting of (-NO ₂ ), imino group (= NH), cyano group (-CN), azo group (-N = N-), diazo group (= N ₂ ), and azi group (-N ₃ ). At least one selected is preferred. Here, R and R'represent a hydrocarbon group having 1 to 5 carbon atoms. From the viewpoint of the adsorptivity of the dispersant to the toner particles, the amino group and / or the imino group is preferable, and from the viewpoint of the chargeability of the toner particles, the imino group is more preferable.
Examples of the functional group contained in addition to the basic nitrogen-containing group include a hydroxy group, a formyl group, an acetal group, an oxime group, a thiol group and the like.

From the viewpoint of dispersion stability, the proportion of the basic nitrogen-containing group in the basic dispersant is preferably 70% or more, more preferably 80% or more, still more preferably 90, in terms of the number of heteroatoms. % Or more, more preferably 95% by number or more, still more preferably 100% by number.

From the viewpoint of dispersibility of the liquid developer, the basic dispersant is a hydrocarbon having 16 or more carbon atoms, a hydrocarbon having 16 or more carbon atoms partially substituted with a halogen atom, and 16 carbon atoms having a reactive functional group. The above hydrocarbons, polymers of hydroxycarboxylic acids with 16 or more carbon atoms, polymers of dibasic acids with 2 or more and 22 or less carbon atoms and diols with 2 or more and 22 or less carbon atoms, alkyl (meth) acrylates with 16 or more carbon atoms. It is preferable to contain a group derived from the polymer, polyolefin, etc. (hereinafter, also referred to as “dispersible group”).
As the hydrocarbon having 16 or more carbon atoms, a hydrocarbon having 16 or more carbon atoms and 24 or less carbon atoms is preferable, and examples thereof include hexadecene, octadecene, icosane, and docosane.
As the hydrocarbon having 16 or more carbon atoms partially substituted with a halogen atom, a hydrocarbon having 16 to 24 carbon atoms partially substituted with a halogen atom is preferable, and for example, chlorohexadecane, bromohexadecane, chlorooctadecane, bromo Examples thereof include octadecane, chloroeicosan, bromoeikosan, chlorodocane, and bromodocosan.

As the hydrocarbon having a reactive functional group and having 16 or more carbon atoms, a hydrocarbon having a reactive functional group and having 16 or more and 24 or less carbon atoms is preferable, and for example, hexadecenyl succinic acid and octadecenyl succinic acid. Examples thereof include acids, eicosenyl succinic acid, docosenyl succinic acid, hexadecyl glycidyl ether, octadecyl glycidyl ether, eicosyl glycidyl ether, docosyl glycidyl ether and the like.
As the polymer of hydroxycarboxylic acid having 16 or more carbon atoms, a polymer of hydroxycarboxylic acid having 16 or more carbon atoms and 24 or less carbon atoms is preferable, and examples thereof include a polymer of 18-hydroxystearic acid.
Examples of the polymer of a dibasic acid having 2 to 22 carbon atoms and a diol having 2 to 22 carbon atoms include a polymer of ethylene glycol and sebacic acid, a polymer of 1,4-butanediol and fumaric acid, and 1 , 6-Hexanediol and fumaric acid polymer, 1,10-decanediol and sebacic acid polymer, 1,12-dodecanediol and 1,12-dodecanedioic acid polymer and the like.

As the polymer of alkyl (meth) acrylate having 16 or more carbon atoms, a polymer of alkyl (meth) acrylate having 16 or more carbon atoms and 24 or less carbon atoms is preferable, for example, a polymer of hexadecyl methacrylate, a polymer of octadecyl methacrylate, and doco. Examples thereof include polymers of silmethacrylate.
Examples of the polyolefin include polyethylene, polypropylene, polybutylene, polyisobutene, polymethylpentene, polytetradecene, polyhexadecene, polyoctadecene, polyeicosene, polydocene and the like.

The basic dispersant preferably has a polyolefin skeleton from the viewpoint of dispersibility of toner particles, more preferably has a polypropylene skeleton and / or a polyisobutene skeleton, and from the viewpoint of solubility of the dispersant in carriers, polyisobutene. It is more preferable to have a skeleton. Therefore, among the dispersible groups, a group derived from polyolefin is preferable, a group derived from polypropylene and / or a group derived from polyisobutene is more preferable, and a group derived from polyisobutene is further preferable.

The basic dispersant is not particularly limited, but is obtained, for example, by reacting a basic nitrogen-containing group raw material with a dispersible group raw material.
Examples of the basic nitrogen-containing group raw material include polyalkyleneimine such as polyethyleneimine, polyallylamine, and polyaminoalkylmethacrylate such as polydimethylaminoethylmethacrylate.
The number average molecular weight of the basic nitrogen-containing group raw material is preferably 100 or more, more preferably 500 or more, further preferably 1,000 or more, and the toner particles from the viewpoint of the adsorptivity of the acidic group to the resin. From the viewpoint of dispersibility, it is preferably 15,000 or less, more preferably 10,000 or less, and further preferably 5,000 or less.

Dispersible group raw materials include halogenated hydrocarbons having 16 or more carbon atoms, hydrocarbons having a reactive functional group having 16 or more carbon atoms, polymers of hydroxycarboxylic acids having 16 or more carbon atoms, and 2 or more carbon atoms. A polymer of 22 or less dibasic acid and a diol having 2 or more and 22 or less carbon atoms, a polymer of an alkyl (meth) acrylate having 16 or more carbon atoms having a reactive functional group, a polyolefin having a reactive functional group, etc. Can be mentioned. Among these, from the viewpoint of raw material availability and reactivity, it has a halogenated hydrocarbon having 16 or more carbon atoms, a hydrocarbon having a reactive functional group and having 16 or more carbon atoms, and a reactive functional group. A polymer of an alkyl (meth) acrylate having 16 to 24 carbon atoms or a polyolefin having a reactive functional group is preferable. Examples of the reactive functional group include a carboxy group, an epoxy group, a formyl group, an isocyanate group and the like, and among these, a carboxy group or an epoxy group is preferable from the viewpoint of safety and reactivity. Therefore, as the compound having a reactive functional group, a carboxylic acid compound is preferable. Examples of the carboxylic acid compound include fumaric acid, maleic acid, ethane acid, propanoic acid, butanoic acid, succinic acid, oxalic acid, malonic acid, tartaric acid, their anhydrides, or alkyl esters having 1 to 3 carbon atoms. And so on. Specific examples of the dispersible group raw material include halogenated alkanes such as chlorooctadecane, epoxy-modified polyoctadecane methacrylate, polyethylene succinic anhydride, chlorinated polypropylene, polypropylene succinic anhydride, polyisobutene succinic anhydride and the like.
The content of the compound having a polyolefin skeleton in the dispersibility base raw material is preferably 70% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, still more preferably 90% by mass or more, from the viewpoint of dispersibility of the toner particles. It is 100% by mass.

From the viewpoint of the dispersibility of the toner particles, the number average molecular weight of the dispersible base material is preferably 500 or more, more preferably 700 or more, still more preferably 900 or more, and the adsorptivity of the dispersant to the toner particles. From the viewpoint, it is preferably 5,000 or less, more preferably 4,000 or less, and further preferably 3,000 or less.

The mass ratio of the basic nitrogen-containing group to the dispersible group (basic nitrogen-containing group / dispersible group) in the basic dispersant is preferably 3/97 or more from the viewpoint of adsorptivity to toner particles, and more. It is preferably 5/95 or more, and is preferably 20/80 or less, more preferably 15/85 or less, from the viewpoint of dispersion stability of toner particles. The mass ratio of the basic nitrogen-containing group to the dispersible group in the basic dispersant can be measured by NMR of the basic dispersant, but the basic dispersion in which the basic nitrogen-containing group raw material reacts with the dispersible group raw material. In the production of the agent, the mass ratio of the reacted raw material compound can also be regarded as the mass ratio of the basic nitrogen-containing group and the dispersible group (basic nitrogen-containing group / dispersible group) in the dispersant.

The number average molecular weight of the basic dispersant is preferably 2,000 or more, more preferably 2,500 or more, still more preferably 3,000 or more, still more preferably 3,000 or more, from the viewpoint of low viscosity and low temperature fixability. It is 3,500 or more, and from the same viewpoint, it is preferably 10,000 or less, more preferably 9,000 or less, still more preferably 8,000 or less.

The content of the basic dispersant is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and further preferably 2 parts by mass with respect to 100 parts by mass of the toner particles from the viewpoint of dispersion stability of the toner particles. It is preferably 10 parts by mass or less, more preferably 8 parts by mass or less, and further preferably 5 parts by mass or less from the viewpoint of the chargeability of the toner.

The liquid developer of the present invention may contain a known dispersant other than the basic dispersant, but the content of the basic dispersant is preferably 50% by mass or more in the dispersant. It is more preferably 70% by mass or more, further preferably 90% by mass or more, still more preferably 95% by mass or more, preferably 100% by mass or less, more preferably substantially 100% by mass, still more preferably 100% by mass. Is.

(Insulating liquid)
In the present invention, the insulating liquid means a liquid through which electricity does not easily flow, but in the present invention, the conductivity of the insulating liquid is preferably 1.0 × ^10-11 S / m or less. It is preferably 5.0 × ^10-12 S / m or less, and preferably 1.0 × ^10-13 S / m or more. Further, the insulating liquid preferably has a dielectric constant of 3.5 or less.

Specific examples of the insulating liquid include hydrocarbon-based solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, and halogenated hydrocarbons, polysiloxanes, vegetable oils, and the like. One or more selected from the group consisting of a solvent and a polysiloxane is preferable, and among these, a hydrocarbon-based solvent is more preferable from the viewpoint of low-temperature fixability, has low viscosity, and has pulverizability, low-temperature fixability, and resistance. Aliphatic hydrocarbons are more preferred because they have an excellent balance of scraping properties. Examples of the aliphatic hydrocarbon include paraffinic hydrocarbons and olefins having 12 or more and 18 or less carbon atoms. One or a combination of two or more of these can be used. Among the aliphatic hydrocarbons, paraffinic hydrocarbons are preferable from the viewpoint of improving the dispersion stability of the toner particles in the liquid developer, improving the low temperature fixability of the liquid developer, and increasing the resistance. Examples of paraffin-based hydrocarbons include liquid paraffin and isoparaffin.

Commercially available aliphatic hydrocarbons include Isopar G, Isopar H, Isopar L, Isopar K, Isopar M (all manufactured by Exxon Mobile Co., Ltd.), Shellsol 71, and Shellsol TM (all of which are Shell Chemicals Japan). (Made by Co., Ltd.), IP Solvent 1620, IP Solvent 2028, IP Solvent 2835 (all manufactured by Idemitsu Kosan Co., Ltd.), Moresco White P-55, Moresco White P-70, Moresco White P-100, More Sco White P-150, Moresco White P-260 (all manufactured by MORESCO), Cosmo White P-60, Cosmo White P-70 (all manufactured by Cosmo Oil Lubricants Co., Ltd.), Lightol (Sonneborn) , Isosol 400 (manufactured by JXTG Energy Co., Ltd.), Linearlen 14, Linearlen 16, Linearlen 18, Linearlen 124, Linearlen 148, Linearlen 168 (all manufactured by Idemitsu Kosan Co., Ltd.) and the like.

The content of the hydrocarbon solvent in the insulating liquid is preferably 60% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, still more preferably 95% by mass or more, and preferably 95% by mass or more. It is 100% by mass or less, more preferably substantially 100% by mass, and even more preferably 100% by mass.

The viscosity of the insulating liquid at 25 ° C. is preferably 100 mPa · s or less, more preferably 50 mPa · s or less, still more preferably 20 mPa · s or less, still more preferably 10 mPa, from the viewpoint of improving the developability of the liquid developer. · S or less, more preferably 5 mPa · s or less, preferably 1 mPa · s or more, more preferably 1.5 mPa · s or more from the viewpoint of improving the dispersion stability of toner particles in a liquid developer. is there. The viscosity of the insulating liquid is measured by the method described in Examples described later.

(Manufacturing method of liquid developer)
In the present invention, as a method of obtaining toner particles, a method of melt-kneading a toner raw material containing resin A or a pigment and crushing the obtained melt-kneaded product, or mixing an aqueous resin dispersion liquid and an aqueous pigment dispersion liquid. Examples thereof include a method of coalescing the resin particles and the pigment particles, and a method of stirring the aqueous resin dispersion and the pigment at high speed. From the viewpoint of improving the developability and fixability of the liquid developer, a method in which the toner raw material is melt-kneaded and then pulverized is preferable.
From this point of view, the liquid developer of the present invention is:
Step 1: At least, the resin A and the pigment are melt-kneaded and the obtained kneaded product is pulverized to obtain toner particles, and Step 2: the toner particles are subjected to an insulating liquid in the presence of a dispersant. It is preferably produced by a method including a step of dispersing the particles therein.

The melt kneading in step 1 can be carried out using a known kneader such as a closed kneader, a single-screw or twin-screw extruder, or an open roll type kneader. It is preferable to use an open roll type kneader from the viewpoint that the pigment can be efficiently and highly dispersed in the resin without repeating kneading or using a dispersion aid.
It is preferable that the resin A and the pigment are mixed in advance with a mixer such as a Henschel mixer or a ball mill, and then supplied to the kneader. Further, if necessary, additives such as a mold release agent and a charge control agent may be subjected to melt-kneading together with a resin or the like.
The kneaded product obtained by melt-kneading is appropriately cooled and pulverized until it reaches a hardness that can be pulverized. The pulverization may be performed in multiple stages. For example, the resin kneaded product may be roughly pulverized to about 1 to 5 mm and then finely pulverized to a desired particle size.
In step 1, it is preferable that the toner particles obtained after pulverization are classified as necessary.

The volume median particle diameter (D ₅₀ ) of the toner particles obtained in step 1 is preferably 3 μm or more, more preferably 4 μm or more, and preferably 15 μm or less from the viewpoint of improving the productivity of the wet pulverization step described later. , More preferably 12 μm or less. In the present specification, the volume median particle size (D ₅₀ ) means a particle size in which the cumulative volume frequency calculated by the volume fraction is 50% calculated from the smaller particle size.

Step 2 is a step of dispersing the toner particles obtained in Step 1 in an insulating liquid in the presence of a dispersant. In the present invention, from the viewpoint of reducing the particle size of the toner particles in the liquid developer and reducing the viscosity of the liquid developer, step 2 is carried out by a method including the following steps 2-1 and 2-2. It is preferable to do so.
Step 2-1: A step of adding a dispersant to the toner particles obtained in Step 1 and dispersing them in an insulating liquid to obtain a toner particle dispersion liquid, and Step 2-2: Toner obtained in Step 2-1. A process of wet-grinding a particle dispersion to obtain a liquid developer

In step 2-1 the mixing method of the toner particles, the insulating liquid, and the dispersant is preferably a method of stirring with a stirring / mixing device.
By mixing the toner particles with the insulating liquid and the dispersant with a high-speed stirring / mixing device, the toner particles are pre-dispersed, the toner particle dispersion liquid can be obtained, and the productivity of the liquid developer by the next wet grinding is improved. To do.

Subsequent step 2-2 is a step of wet pulverizing the toner particle dispersion obtained in step 2-1 to obtain a liquid developer. Wet pulverization is a method of mechanically pulverizing toner particles dispersed in an insulating liquid in a state of being dispersed in the insulating liquid.

The solid content concentration of the toner particle dispersion liquid to be subjected to wet grinding is preferably 20% by mass or more, more preferably 30% by mass or more, still more preferably 33% by mass or more, from the viewpoint of improving the image density of the liquid developer. From the viewpoint of improving the dispersion stability of the toner particles in the liquid developer and improving the storage stability, the content is preferably 50% by mass or less, more preferably 45% by mass or less, still more preferably 40% by mass or less. The solid content concentration of the toner particle dispersion is measured by the method described in Examples described later.

From the viewpoint of improving the image density of the liquid developer, the solid content concentration of the liquid developer is preferably 10% by mass or more, more preferably 15% by mass or more, still more preferably 20% by mass or more, and is contained in the liquid developer. From the viewpoint of improving the dispersion stability of the toner particles and improving the storage stability, the content is preferably 50% by mass or less, more preferably 45% by mass or less, still more preferably 40% by mass or less. The solid content concentration of the liquid developer is measured by the method described in Examples described later. If there is no operation such as dilution or concentration after preparing the toner particle dispersion, the solid content concentration of the toner particle dispersion will be the solid content concentration of the liquid developer. However, after wet pulverization, the solid content concentration is diluted with an insulating liquid. May be adjusted.

The content of the resin A in the liquid developer of the present invention is preferably 3% by mass or more, more preferably 5% by mass, from the viewpoint of improving the dispersion stability of the toner particles in the liquid developer and reducing the viscosity. The above is more preferably 10% by mass or more, still more preferably 15% by mass or more, and from the viewpoint of improving the pulverizability of the liquid developer, it is preferably 40% by mass or less, more preferably 30% by mass or less, still more preferably. Is 25% by mass or less. The content of the polyester resin P in the liquid developer here means that when the liquid developer is produced, the liquid developer in which the toner particles are dispersed in the insulating liquid is obtained and then diluted. , The content in the liquid developer after dilution.

The content of the pigment in the liquid developer of the present invention is preferably 1% by mass or more, more preferably 1.5% by mass or more, still more preferably 2% by mass or more, from the viewpoint of improving the image density of the liquid developer. From the viewpoint of improving the dispersion stability of the toner particles in the liquid developer and reducing the viscosity, the content is preferably 10% by mass or less, more preferably 8% by mass or less, and further preferably 6% by mass or less.

The content of the dispersant in the liquid developer of the present invention is preferably 0.05% by mass from the viewpoint of improving the dispersion stability of the toner particles in the liquid developer, reducing the viscosity and the scratch resistance. The above is more preferably 0.1% by mass or more, further preferably 0.2% by mass or more, still more preferably 0.3% by mass or more, and is preferable from the viewpoint of improving the low-temperature fixability of the liquid developer. It is 8% by mass or less, more preferably 6% by mass or less, still more preferably 4% by mass or less.

The volume median particle size (D ₅₀ ) of the toner particles in the liquid developer is preferably 5 μm or less from the viewpoint of reducing the particle size of the toner particles in the liquid developer and improving the image quality of the liquid developer. It is preferably 3 μm or less, more preferably 2.5 μm or less, and preferably 0.5 μm or more, more preferably 1.0 μm or more, still more preferably 1.5 μm or more from the viewpoint of reducing the viscosity of the liquid developer. .. The volume median particle diameter (D50) of the toner particles in the liquid developer is measured by the method described in Examples described later.

The viscosity of the liquid developer at 25 ° C. is preferably 30 mPa · s or less, more preferably 20 mPa · s or less, still more preferably 15 mPa · s or less, still more preferably 10 mPa, from the viewpoint of improving the fixability of the liquid developer. -S or less, preferably 1 mPa · s or more, more preferably 2 mPa · s or more, still more preferably 3 mPa · s, from the viewpoint of improving the dispersion stability of the toner particles in the liquid developer and improving the storage stability. It is s or more, more preferably 4 mPa · s or more. The viscosity of the liquid developer is measured by the method described in Examples described later.

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples. The physical properties of the resin and the like were measured by the following methods.

[Resin softening point]
Using a flow tester "CFT-500D" (manufactured by Shimadzu Corporation), while heating a 1 g sample at a heating rate of 6 ° C./min, a load of 1.96 MPa was applied by a plunger, and the diameter was 1 mm and the length was 1 mm. Extruded from the nozzle of. 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 used as the softening point.

[Melting point and glass transition temperature]
Using a differential scanning calorimeter "Q100" (manufactured by TA Instruments Japan Co., Ltd.), weigh 0.02 g of a sample into an aluminum pan, raise the temperature to 200 ° C, and then lower the temperature from that temperature to 10 ° C. It was cooled to 0 ° C. at / min. Next, the temperature of the sample was raised at a heating rate of 10 ° C./min, and the amount of heat was measured. Among the observed endothermic peaks, the temperature of the peak having the largest peak area was defined as the maximum endothermic peak temperature (2). In the case of a crystalline resin, the peak temperature was taken as the melting point.
Further, in the case of an amorphous resin, when a peak is observed, the temperature of the peak is observed, and when a step is observed without a peak, a tangent line indicating the maximum inclination of the curve of the step portion and the step are shown. The temperature at the intersection with the extension of the baseline on the low temperature side of the glass transition temperature was defined as the glass transition temperature.

[Acid value of resin]
The acid value of the resin was measured according to the neutralization titration method described in JIS K 0070: 1992. However, the measurement solvent was chloroform.

[Hydroxyl value of resin]
Measured according to the method described in JIS K 0070: 1992.

[Number average molecular weight of resin]
The molecular weight distribution was measured by the gel permeation chromatography (GPC) method by the following method, and the number average molecular weight was determined.
(1) Preparation of sample solution The sample was dissolved in tetrahydrofuran at 25 ° C. so that the concentration was 0.5 g / 100 ml. Next, this solution was filtered using a fluororesin filter "DISMIC-25JP" (manufactured by ADVANTEC) having a pore size of 0.2 μm to remove insoluble components, and used as a sample solution.
(2) Molecular Weight Measurement Using the following measuring device and analytical column, tetrahydrofuran was flowed as an eluent at a flow rate of 1 ml per minute, and the column was stabilized in a constant temperature bath at 40 ° C. 100 μl of the sample solution was injected therein and the measurement was carried out. The molecular weight of the sample was calculated based on a calibration curve prepared in advance. The calibration curve of the several kinds of monodisperse polystyrene (Tosoh Corp. of ^{A-500 (5.0 × 10 2} ), A-1000 (1.01 × 10 3), A-2500 (2.63 × 10 ³ ), A-5000 (5.97 × 10 ³ ), F-1 (1.02 × 10 ⁴ ), F-2 (1.81 × 10 ⁴ ), F-4 (3.97 × 10) ⁴ ), F-10 (9.64 × 10 ⁴ ), F-20 (1.90 × 10 ⁵ ), F-40 (4.27 × 10 ⁵ ), F-80 (7.06 × 10 ⁵ ) , F-128 (1.09 × 10 ⁶ )) was used as a standard sample.
Measuring device: HLC-8220GPC (manufactured by Tosoh Corporation)
Analytical column: GMHXL + G3000HXL (manufactured by Tosoh Corporation)

[Medium particle size of toner]
Measuring machine: Coulter Multi-Sizar II (manufactured by Beckman Coulter Co., Ltd.)
Aperture diameter: 50 μm
Analysis software: Coulter Multi-Sizar AccuComp version 1.19 (manufactured by Beckman Coulter Co., Ltd.)
Electrolyte: Isoton II (manufactured by Beckman Coulter Co., Ltd.)
Dispersion solution: Emulgen 109P (manufactured by Kao Co., Ltd., polyoxyethylene lauryl ether, HLB (griffin): 13.6) was dissolved in an electrolytic solution to adjust to 5% by mass. Dispersion condition: Measurement sample in 5 ml of the dispersion solution 10 mg was added and dispersed with an ultrasonic disperser for 1 minute, then 25 ml of the electrolytic solution was added and further dispersed with an ultrasonic disperser for 1 minute to prepare a sample dispersion.
Measurement conditions: Add the sample dispersion to 100 ml of the electrolytic solution so that the particle size of 30,000 particles can be measured in 20 seconds, measure 30,000 particles, and measure the volume from the particle size distribution. The medium particle size (D ₅₀ ) was determined.

Resin Production Example A1 [Amorphous Resin A-1]
The inside of a four-necked flask with an internal volume of 10 L equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was replaced with nitrogen, and 2854 g of a polyoxypropylene (2.2) adduct of bisphenol A and poly of bisphenol A were prepared. 2650 g of oxyethylene (2.2) adduct, 1760 g of terephthalic acid, and 219 g of dodecenyl succinic anhydride were added, and the temperature was raised to 160 ° C. and kept at 160 ° C., 365 g of styrene, 47 g of acrylic acid, and 27 g of dibutyl peroxide. The mixture was added dropwise over 1 hour. Then, after holding at 160 ° C. for 30 minutes, the temperature was raised to 200 ° C., the pressure in the flask was further lowered, and the temperature was maintained at 8 kPa for 1 hour. Then, after returning to atmospheric pressure, 40 g of di (2-ethylhexanoic acid) tin (II) and 1.6 g of 3,4,5-trihydroxybenzoic acid were added, and the temperature was 235 ° C. with stirring under a nitrogen atmosphere. After raising the temperature to 235 ° C. and holding at 235 ° C. for 5 hours, 392 g of X-22-162C (silicone manufactured by Shin-Etsu Chemical Co., Ltd.) was added, and after holding for 0.5 hours, the pressure inside the flask was lowered to 8 kPa. It was held for 1 hour. Then, after returning to atmospheric pressure, the mixture was cooled to 200 ° C., 470 g of trimellitic anhydride was added, and the reaction was carried out at 200 ° C. for 0.5 hours. Then, the pressure in the flask was lowered to reach the desired softening point at 20 kPa. The reaction was carried out to obtain an amorphous resin A-1. The physical properties are shown in Table 1.

Resin Production Examples A2 to A3 [Amorphous Resins A-2 to A-3]
Amorphous resins A-2 to A-3 were obtained in the same manner as in Production Example 1 except that the raw material composition was changed as shown in Table 1. The physical properties are shown in Table 1.

Resin Production Example A4 [Amorphous Resin A-4]
The inside of a four-necked flask with an internal volume of 10 L equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was replaced with nitrogen, and 2854 g of a polyoxypropylene (2.2) adduct (BPA-PO) of bisphenol A. , 2650 g of bisphenol A polyoxyethylene (2.2) adduct (BPA-EO), 1760 g of terephthalic acid, and 219 g of dodecenyl succinic anhydride, and the temperature was raised to 160 ° C. and kept at 160 ° C., styrene 365 g. , 47 g of acrylic acid, and 27 g of dibutyl peroxide was added dropwise over 1 hour. Then, after holding at 160 ° C. for 30 minutes, the temperature was raised to 200 ° C., the pressure in the flask was further lowered, and the temperature was maintained at 8 kPa for 1 hour. Then, after returning to atmospheric pressure, 40 g of di (2-ethylhexanoic acid) tin (II) and 1.6 g of 3,4,5-trihydroxybenzoic acid were added, and the temperature was 235 ° C. with stirring under a nitrogen atmosphere. After raising the temperature to 235 ° C. and holding at 235 ° C. for 5 hours, 392 g of X-22-170BX (silicone manufactured by Shin-Etsu Chemical Co., Ltd.) was added, and after holding for 0.5 hours, the pressure inside the flask was lowered to 8 kPa. It was held for 1 hour. Then, after returning to atmospheric pressure, the mixture is cooled to 200 ° C., 470 g of trimellitic anhydride is added, the reaction is carried out at 200 ° C. for 30 minutes, then the pressure in the flask is lowered, and the reaction is carried out at 20 kPa to the desired softening point. The process was carried out to obtain an amorphous resin A-4. The physical properties are shown in Table 1.

Resin Production Example A5 [Amorphous Resin A-5]
The inside of a four-necked flask with an internal volume of 10 L equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was replaced with nitrogen, and 2854 g of a polyoxypropylene (2.2) adduct of bisphenol A and poly of bisphenol A were prepared. 2650 g of oxyethylene (2.2) adduct, 1760 g of terephthalic acid, and 219 g of dodecenyl succinic anhydride were added, and the temperature was raised to 160 ° C. and kept at 160 ° C., 365 g of styrene, 47 g of acrylic acid, and 27 g of dibutyl peroxide. The mixture was added dropwise over 1 hour. Then, after holding at 160 ° C. for 30 minutes, the temperature was raised to 200 ° C., the pressure in the flask was further lowered, and the temperature was maintained at 8 kPa for 1 hour. Then, after returning to atmospheric pressure, 40 g of di (2-ethylhexanoic acid) tin (II) and 1.6 g of 3,4,5-trihydroxybenzoic acid were added, and the temperature was 235 ° C. with stirring under a nitrogen atmosphere. After raising the temperature to 235 ° C. and holding at 235 ° C. for 5 hours, 392 g of X-22-173BX (silicone manufactured by Shin-Etsu Chemical Co., Ltd.) was added, and after holding for 0.5 hours, the pressure inside the flask was lowered to 8 kPa. It was held for 1 hour. Then, after returning to atmospheric pressure, the mixture was cooled to 200 ° C., 470 g of trimellitic anhydride was added, and the reaction was carried out at 200 ° C. for 0.5 hours. Then, the pressure in the flask was lowered to reach the desired softening point at 20 kPa. The reaction was carried out to obtain an amorphous resin A-5. The physical properties are shown in Table 2.

Resin Production Example A6 [Amorphous Resin A-6]
The inside of a four-necked flask with an internal volume of 10 L equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was replaced with nitrogen, and 2854 g of a polyoxypropylene (2.2) adduct of bisphenol A and poly of bisphenol A were prepared. 2650 g of oxyethylene (2.2) adduct, 1760 g of terephthalic acid, and 219 g of dodecenyl succinic anhydride were added, and the temperature was raised to 160 ° C. and kept at 160 ° C., 365 g of styrene, 47 g of acrylic acid, and 27 g of dibutyl peroxide. The mixture was added dropwise over 1 hour. Then, after holding at 160 ° C. for 30 minutes, the temperature was raised to 200 ° C., the pressure in the flask was further lowered, and the temperature was maintained at 8 kPa for 1 hour. Then, after returning to atmospheric pressure, 40 g of di (2-ethylhexanoic acid) tin (II) and 1.6 g of 3,4,5-trihydroxybenzoic acid were added, and the temperature was 235 ° C. with stirring under a nitrogen atmosphere. After raising the temperature to 235 ° C. and holding at 235 ° C. for 5 hours, 392 g of KF-864 (silicone manufactured by Shin-Etsu Chemical Co., Ltd.) was added, and after holding for 0.5 hours, the pressure inside the flask was lowered and the pressure inside the flask was lowered for 1 hour at 8 kPa. Retained. Then, after returning to atmospheric pressure, the mixture was cooled to 200 ° C., 470 g of trimellitic anhydride was added, and the reaction was carried out at 200 ° C. for 0.5 hours. Then, the pressure in the flask was lowered to reach the desired softening point at 20 kPa. The reaction was carried out to obtain an amorphous resin A-6. The physical properties are shown in Table 2.

Resin Production Example A7 [Amorphous Resin A-7]
The inside of a four-necked flask with an internal volume of 10 L equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was replaced with nitrogen, and 2854 g of a polyoxypropylene (2.2) adduct of bisphenol A and poly of bisphenol A were prepared. 2650 g of oxyethylene (2.2) adduct, 1760 g of terephthalic acid, and 219 g of dodecenyl succinic anhydride were added, and the temperature was raised to 160 ° C. and kept at 160 ° C., 365 g of styrene, 47 g of acrylic acid, and 27 g of dibutyl peroxide. The mixture was added dropwise over 1 hour. Then, after holding at 160 ° C. for 30 minutes, the temperature was raised to 200 ° C., the pressure in the flask was further lowered, and the temperature was maintained at 8 kPa for 1 hour. Then, after returning to atmospheric pressure, 40 g of di (2-ethylhexanoic acid) tin (II) and 1.6 g of 3,4,5-trihydroxybenzoic acid were added, and the temperature was 235 ° C. with stirring under a nitrogen atmosphere. After raising the temperature to 235 ° C. and holding at 235 ° C. for 5 hours, 392 g of KF-6000 (silicone manufactured by Shin-Etsu Chemical Co., Ltd.) was added, and after holding for 0.5 hours, the pressure inside the flask was lowered and the pressure inside the flask was lowered for 1 hour at 8 kPa. Retained. Then, after returning to atmospheric pressure, the mixture was cooled to 200 ° C., 470 g of trimellitic anhydride was added, and the reaction was carried out at 200 ° C. for 0.5 hr. Then, the pressure in the flask was lowered to reach the desired softening point at 20 kPa. The reaction was carried out to obtain an amorphous resin A-7. The physical properties are shown in Table 2.

Resin Production Example A8 [Amorphous Resin A-8]
The inside of a four-necked flask with an internal volume of 10 L equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was replaced with nitrogen, and 2854 g of a polyoxypropylene (2.2) adduct of bisphenol A and poly of bisphenol A were prepared. 2650 g of oxyethylene (2.2) adduct, 1760 g of terephthalic acid, and 219 g of dodecenyl succinic anhydride were added, and the temperature was raised to 160 ° C. and kept at 160 ° C., 365 g of styrene, 47 g of acrylic acid, and 27 g of dibutyl peroxide. The mixture was added dropwise over 1 hour. Then, after holding at 160 ° C. for 30 minutes, the temperature was raised to 200 ° C., the pressure in the flask was further lowered, and the temperature was maintained at 8 kPa for 1 hour. Then, after returning to atmospheric pressure, 40 g of di (2-ethylhexanoic acid) tin (II) and 1.6 g of 3,4,5-trihydroxybenzoic acid were added, and the temperature was 235 ° C. with stirring under a nitrogen atmosphere. After raising the temperature to 235 ° C. and holding at 235 ° C. for 5 hours, 392 g of KF-6003 (silicone manufactured by Shin-Etsu Chemical Co., Ltd.) was added, and after holding for 0.5 hours, the pressure inside the flask was lowered and the pressure inside the flask was lowered for 1 hour at 8 kPa. Retained. Then, after returning to atmospheric pressure, the mixture was cooled to 200 ° C., 470 g of trimellitic anhydride was added, and the reaction was carried out at 200 ° C. for 0.5 hours. Then, the pressure in the flask was lowered to reach the desired softening point at 20 kPa. The reaction was carried out to obtain an amorphous resin A-8. The physical properties are shown in Table 2.

Resin Production Example A9 [Amorphous Resin A-9]
The inside of a four-necked flask with an internal volume of 10 L equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was replaced with nitrogen, and 2854 g of a polyoxypropylene (2.2) adduct of bisphenol A and poly of bisphenol A were prepared. 2650 g of oxyethylene (2.2) adduct, 1760 g of terephthalic acid, and 219 g of dodecenyl succinic anhydride were added, the temperature was raised to 160 ° C, and the temperature was maintained at 160 ° C. A mixture of 415 g of (Styrene Co., Ltd.), 47 g of acrylic acid, and 27 g of dibutyl peroxide was added dropwise over 1 hour. Then, after holding at 160 ° C. for 30 minutes, the temperature was raised to 200 ° C., the pressure in the flask was further lowered, and the temperature was maintained at 8 kPa for 1 hour. Then, after returning to atmospheric pressure, 40 g of di (2-ethylhexanoic acid) tin (II) and 1.6 g of 3,4,5-trihydroxybenzoic acid were added, and the temperature was 235 ° C. with stirring under a nitrogen atmosphere. After raising the temperature to 235 ° C. and holding at 235 ° C. for 5 hours, the pressure in the flask was lowered and held at 8 kPa for 1 hour. Then, after returning to atmospheric pressure, the mixture was cooled to 200 ° C., 470 g of trimellitic anhydride was added, and the reaction was carried out at 200 ° C. for 0.5 hr. Then, the pressure in the flask was lowered to reach the desired softening point at 20 kPa. The reaction was carried out to obtain an amorphous resin A-9. The physical properties are shown in Table 3.

Resin Production Example A10 [Amorphous Resin A-10]
Nitrogen is substituted inside a four-necked flask with an internal volume of 10 L equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple, and 2655 g of 1,2-propanediol, 3770 g of terephthalic acid, and 468 g of dodecenyl succinic anhydride are added. A mixture of 233 g of styrene, 100 g of butyl acrylate, and 25 g of dibutyl peroxide was added dropwise over 1 hour while the temperature was raised to 160 ° C. and maintained at 160 ° C. Then, after keeping the temperature at 160 ° C. for 30 minutes, 40 g of tin (II) di (2-ethylhexanoic acid) was added, and the temperature was gradually raised from 180 ° C. to 220 ° C. over 6 hours with stirring under a nitrogen atmosphere. It was. After adding 359 g of X-22-162C (silicone manufactured by Shin-Etsu Chemical Co., Ltd.) and holding for 0.5 hour, the temperature was lowered to 210 ° C., 1006 g of trimellitic anhydride was added, and the mixture was held for 0.5 hours. Then, the reaction was carried out at 8.0 kPa to a desired softening point to obtain an amorphous resin A-10. The physical properties are shown in Table 3.

Resin Production Example A11 [Amorphous Resin A-11]
The inside of a four-necked flask with an internal volume of 10 L equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was replaced with nitrogen, and 2854 g of a polyoxypropylene (2.2) adduct of bisphenol A and poly of bisphenol A were prepared. 2650 g of oxyethylene (2.2) adduct, 1760 g of terephthalic acid, and 219 g of dodecenyl succinic anhydride were added, and the temperature was raised to 160 ° C. and kept at 160 ° C., 365 g of styrene, 47 g of acrylic acid, and 27 g of dibutyl peroxide. The mixture was added dropwise over 1 hour. Then, after holding at 160 ° C. for 30 minutes, the temperature was raised to 200 ° C., the pressure in the flask was further lowered, and the temperature was maintained at 8 kPa for 1 hour. Then, after returning to atmospheric pressure, 40 g of di (2-ethylhexanoic acid) tin (II) and 1.6 g of 3,4,5-trihydroxybenzoic acid were added, and the temperature was 235 ° C. with stirring under a nitrogen atmosphere. After raising the temperature to 235 ° C. and holding at 235 ° C. for 5 hours, the pressure in the flask was lowered and held at 8 kPa for 1 hour. Then, after returning to atmospheric pressure, the mixture was cooled to 200 ° C., 470 g of trimellitic anhydride was added, and the reaction was carried out at 200 ° C. for 0.5 hours. The reaction was carried out to obtain an amorphous resin A-11. The physical properties are shown in Table 3.

Resin Production Example A12 [Amorphous Resin A-12]
The inside of a four-necked flask with an internal volume of 10 L equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was replaced with nitrogen, and 70 parts of L-lactide (5091 g), 30 parts of D-lactide (2182 g), and screws were replaced. 10 parts (727 g) of (2-hydroxypropyl) terephthalate (BHPT) was added, the internal temperature was gradually raised, and dehydration treatment was performed under reduced pressure conditions. Then, the temperature was further raised under a nitrogen purge, and after visually confirming that the system was homogenized, 24 g of tin (II) di (2-ethylhexanoic acid) was added to the system to carry out a polymerization reaction. At this time, the internal temperature of the system was controlled so as not to exceed 190 ° C. After the reaction time of 2 hours had elapsed, the system was switched to the outflow line again, unreacted lactide was removed under reduced pressure conditions, and the polymerization reaction was completed to obtain a resin oligomer. Then, 100 parts (5882 g) of the resin oligomer and 10 parts (588 g) of X22-160AS (manufactured by Shin-Etsu Chemical Co., Ltd.) were put into the flask, and the internal temperature was gradually raised. After confirming the homogenization of the system, dehydration treatment was performed under reduced pressure. Then, the temperature is further raised, and 24 g of tin (II) di (2-ethylhexanoic acid) is added to the system at 170 ° C., and then 9 parts (529 g) of an extender [isophorone diisocyanate (IPDI)] is gradually added to carry out an extension reaction. A-12 was obtained. The physical properties are shown in Table 3.

The components used in Tables 1 to 3 are as follows.
-BPA-PO: Polyoxypropylene (2.2) adduct-BPA-EO: Polyoxyethylene (2.2) adduct of bisphenol A-1,2-PD: 1,2-propanediol-BHPT: Bis (2-Hydroxypropyl) terephthalate-X-22-162C: Modified silicone oil "X-22-162C" (silicone having carboxy groups at both ends [the above-mentioned silicone (1-c) (one end is the formula (1-1)) It is a group represented by 2c), and the group is a substituent 1-2c-1)], kinematic viscosity (25 ° C.) = 220 mm ² / s, number average molecular weight Mn = 2,600, weight average molecular weight Mw = 7,800, functional group equivalent = 2,300 g / mol, manufactured by Shin-Etsu Chemical Industry Co., Ltd.)
X-22-170BX: Modified silicone oil "X-22-170BX" (Silicone having a carbinol group (hydroxy group) at one end [Silicone (1-a) mentioned above (only one end is of formula (1-2a)) ), The group is * -C3H6OC2H4OH)], kinematic viscosity (25 ° C.) = 40 mm ² / s, number average molecular weight Mn = 1,900, weight average molecular weight Mw = 3,500, functional Base equivalent 20 g / mol, manufactured by Shin-Etsu Chemical Industry Co., Ltd.)
X-22-173BX: Modified silicone oil "X-22-173BX" (silicone having a glycidyl group at one end [the above-mentioned silicone (1-b) (only one end is represented by the formula (1-2b)). The group is a substituent 1-2b-1)], kinematic viscosity (25 ° C.) = 30 mm ² / s, number average molecular weight Mn = 1,900, weight average molecular weight Mw = 3,300, functional group. Equivalent = 2,500 g / mol, manufactured by Shin-Etsu Chemical Industry Co., Ltd.)
-KF-864: Silicone "KF-864" (silicone having an amino group in the side chain, viscosity (25 ° C.) = 1,700 mm ² / s, functional group equivalent = 3,800 g / mol, manufactured by Shin-Etsu Chemical Co., Ltd. )
-KF-6000: Modified silicone oil "KF-6000" (silicone having a carbinol group at both ends [the above-mentioned silicone (1-a) (both ends are groups represented by the formula (1-2a), and is a group represented by the formula (1-2a). The group is a substituent 1-2a-1)], kinematic viscosity (25 ° C.) = 35 mm ² / s, number average molecular weight Mn = 1,000, weight average molecular weight Mw = 1,400, functional group equivalent = 467 g / mol, manufactured by Shin-Etsu Chemical Industry Co., Ltd.)
KF-6003: Modified silicone oil "KF-6003" (silicone having a carbinol group at both ends [the above-mentioned silicone (1-a) (both ends are groups represented by the formula (1-2a), and is a group represented by the formula (1-2a). The groups are substituents 1-2a-1)], kinematic viscosity (25 ° C.) = 110 mm ² / s, number average molecular weight Mn = 2800, weight average molecular weight Mw = 7900, functional group equivalent = 2545 g / mol, Shinetsu Chemicals. Made by Kogyo Co., Ltd.)
X-22-160AS: Modified silicone oil "X-22-160AS" (silicone having a carbinol group (hydroxy group) at both ends [the above-mentioned silicone (1-a) (both ends are of the formula (1-2a)) The group is represented by * -C ₃ H ₆ OC ₂ H ₄ OH)], kinematic viscosity (25 ° C) = 35 mm ² / s, number average molecular weight Mn = 1,000, weight average molecular weight. Mw = 1,400, functional group equivalent = 470 g / mol, manufactured by Shin-Etsu Chemical Industry Co., Ltd.)
・ IPDI: Isophorone diisocyanate

Resin Production Example C1 [Crystalline Resin C-1]
The inside of a four-necked flask with an internal volume of 10 L equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was replaced with nitrogen, and 1,6-hexanediol 4034 g, fumaric acid 3966 g, and tertiary butylcatecol 2.4 g. Was added, and the temperature was raised to 140 ° C. while stirring under a nitrogen atmosphere, and the temperature was maintained for 1 hour. Then, the temperature was raised at 10 ° C./hour, and after reaching 200 ° C., 24 g of di (2-ethylhexanoic acid) tin (II) was added and held for 1 hour. After holding, the pressure in the flask was lowered, and the reaction was carried out at 8 kPa to a desired acid value to obtain a crystalline resin C-1. The physical properties are shown in Table 4.

Resin Production Example C2 [Crystalline Resin C-2]
Nitrogen is substituted inside a four-necked flask with an internal volume of 10 L equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple, and 4638 g of 1,9-nonanediol and 3362 g of sebacic acid are added and stirred under a nitrogen atmosphere. While doing so, the temperature was raised to 140 ° C. and maintained for 1 hour. Then, the temperature was raised at 10 ° C./hour, and after reaching 200 ° C., 24 g of di (2-ethylhexanoic acid) tin (II) was added and held for 1 hour. After holding, the pressure in the flask was lowered, and the reaction was carried out at 8 kPa to a desired acid value to obtain a crystalline resin C-2. The physical properties are shown in Table 4.

Resin Production Examples C3 to C5 [Crystalline Resins C-3 to C-5]
Crystalline resins C-3 to C-5 were obtained in the same manner as in Production Example C1 except that the raw material composition was changed as shown in the table. The physical properties are shown in Table 4.

Example 1
Toner Production Example 1 [Mother Particle 1]
20 parts by mass of binder resin 1 (A-1 / C-1 = 90/10) and 20 parts by mass of pigment "ECB-301" (manufactured by Dainichiseika Kogyo Co., Ltd., phthalocyanine blue 15: 3) in advance. After stirring and mixing for 3 minutes at a rotation speed of 1500 r / min (peripheral speed 21.6 m / sec) using the Henchel mixer of the above, melt-kneading was performed under the following conditions.
[Melting and kneading conditions]
A continuous double open roll type kneader "Kneedex" (manufactured by Nippon Coke Industries Co., Ltd., roll outer diameter: 14 cm, effective roll length: 55 cm) was used. The operating conditions of the continuous double open roll type kneader are high rotation side roll (front roll) peripheral speed 75r / min (32.4m / min) and low rotation side roll (back roll) peripheral speed 35r / min (15). .0 m / min), and the roll gap at the end on the side of the kneaded material supply port was 0.1 mm. The heating medium temperature and the cooling medium temperature in the roll are 90 ° C. on the raw material input side of the high rotation side roll and 85 ° C. on the kneaded material discharge side, 35 ° C. on the raw material input side of the low rotation side roll and 35 ° C. on the kneaded material discharge side. there were. The supply speed of the raw material mixture to the kneader was 10 kg / h, and the average residence time in the kneader was about 3 minutes.
The kneaded product obtained above was rolled and cooled with a cooling roll, and then roughly pulverized to about 1 mm using a hammer mill. The obtained coarsely pulverized product was finely pulverized and classified by an air flow jet mill "IDS" (manufactured by Nippon Pneumatic Industries Co., Ltd.) to obtain toner particles having a volume median particle diameter (D ₅₀ ) of 10 μm.

Dispersant Production Example 1 [Dispersant A]
A 2L four-necked flask equipped with a cooling tube, nitrogen introduction tube, stirrer, dehydration tube and thermocouple using polyethyleneimine (polyethyleneimine 600, manufactured by Genuine Chemical Co., Ltd.) shown in Table 5 as a basic nitrogen-containing base material. The inside of the reaction vessel was replaced with nitrogen gas. While stirring, a solution of polyisobutene succinic anhydride (PIBSA) (H1000, manufactured by Dover) shown in Table 5 as a dispersible base raw material in xylene shown in Table 5 was added dropwise at 25 ° C. over 1 hour. After completion of the dropping, the mixture was kept at room temperature for 30 minutes. Then, the inside of the reaction vessel was heated to 150 ° C. and held for 1 hour, then heated to 160 ° C. and held for 1 hour. When xylene was distilled off by reducing the pressure to 8.3 kPa at 160 ° C., the peak of the acid anhydride derived from PIBSA (1780 cm ^-1 ) disappeared from the IR analysis, and the peak derived from the imide bond (1700 cm ^-1 ) was generated. Was used as the reaction end point, and a dispersant A having the physical properties shown in Table 5 was obtained.

[Liquid developer]
35 parts by mass of the obtained toner particles and the insulating liquid "NAS-4" (manufactured by Nichiyu Co., Ltd., polyisobutene, conductivity: 1.52 × ^10-12 S / m, boiling point: 247 ° C, viscosity at 25 ° C: 2 mPa · s) 63.95 parts by mass and 1.05 parts by mass of the dispersant A are placed in a 1 L polyethylene container and ice-cooled using "TK Robomix" (manufactured by Primix Co., Ltd.). Below, stirring was carried out at a rotation speed of 7,000 r / min for 30 minutes to obtain a toner particle dispersion having a solid content concentration of 36% by mass.
Next, the obtained toner particle dispersion was rotated by a 6-cylinder sand mill "TSG-6" (manufactured by Imex Co., Ltd.) using zirconia beads having a diameter of 0.8 mm and a volume filling rate of 60% by volume. Wet pulverization was performed at 1300 r / min (peripheral speed 4.8 m / sec). After removing the beads by filtration, 44 parts by mass of the insulating liquid "NAS-4" (manufactured by Nichiyu Co., Ltd.) is added to 100 parts by mass of the filtrate to dilute it, and a liquid developer having a solid content concentration of 25% by mass is added. Got

Test Example 1 [Minimum fixing temperature (low temperature fixing property)]
A liquid developer was dropped onto "OK top coated paper" (manufactured by Oji Paper Co., Ltd., basis weight: 127.9 g / m ² , paper thickness: about 103 μm), and the toner mass after drying with a wire bar was 3.4 g / m. A thin film was prepared so as to be m ² . Then, it was held in a constant temperature bath at 80 ° C. for 10 seconds.
Subsequently, using a fixing machine taken out from "OKI MICROLINE 3010" (manufactured by Oki Data Corporation), the fixing process was performed at a fixing roll temperature of 70 ° C. and a fixing speed of 280 mm / sec. Then, while raising the fixing roll temperature to 150 ° C. by 5 ° C., the fixing treatment was carried out in the same manner, and a fixing image was obtained at each temperature.
A mending tape "Scotch Mending Tape 810" (manufactured by 3M Japan Ltd., width 18 mm) is attached to the obtained fixed image, pressure is applied to the tape with a roller so that a load of 500 g is applied, and then the tape is peeled off. did. The image densities before and after the tape peeling were measured using a colorimeter "Gretag Macbeth Spectroeye" (manufactured by Gretag). The image print portion was measured at three points each, and the average value was calculated as the image density. The fixing rate (%) is calculated from the value of the image density after peeling / the image density before peeling × 100, and the lowest temperature in the temperature range where the fixing rate is 90% or more and no offset occurs is defined as the minimum fixing temperature. did. It is shown that the lower the minimum fixing temperature, the better the low temperature fixing property.

Test Example 2 [Hot offset (HO resistance) resistance]
The fixing image of 70 ° C. to 150 ° C. obtained in the fixing property test of Test Example 1 was visually confirmed, and the maximum temperature of the fixing roll in which no hot offset was observed was defined as the maximum fixing temperature. It is shown that the higher the maximum fixing temperature, the better the hot offset (HO resistance) resistance.

Test Example 3 [Wet grindability]
Using zirconia beads with a diameter of 0.8 mm, the toner particle dispersion liquid has a volume filling rate of 60% by volume, and the rotation speed is 1300 r / min (peripheral speed) with a 6-cylinder sand mill "TSG-6" (manufactured by Imex Co., Ltd.). Wet pulverization was performed at 4.8 m / sec). The conditions are as described above, and the smaller the particle size after 1 hour from the start of wet pulverization, the better the wet pulverization property.

Examples 2-14 and Comparative Examples 1-2
A toner for liquid development was prepared and evaluated in the same manner as in Example 1 except that the binder resin used was changed as shown in the table below. The results are shown in Table 6 below.

From the above results, it can be seen that the liquid developer containing the toner particles of Examples 1 to 14 has good low-temperature fixability, hot offset resistance, and wet pulverization property. In Comparative Example 1, the minimum fixing temperature was higher than that in the example, the hot offset resistance was inferior, and the wet pulverization property was also inferior. Further, in Comparative Example 2, since the minimum fixing temperature was 150 ° C. or higher, the minimum fixing temperature and the hot offset resistance could not be evaluated. The toner particles of Comparative Example 2 were inferior in wet pulverizability.

The liquid developer of the present invention is suitably used for developing a latent image formed by an electrophotographic method, an electrostatic recording method, an electrostatic printing method or the like.

Claims (5)

A liquid developer in which toner particles containing a binder resin and a pigment are dispersed in an insulating liquid in the presence of a dispersant.
A polyester resin obtained by polycondensing an alcohol component having a silicone chain and containing an alcohol having at least divalent or higher and a carboxylic acid component containing a carboxylic acid compound having divalent or higher valence, and silicone. A liquid developer containing at least one selected from a composite resin having a chain and having a polyester resin segment and an addition polymerization resin segment. The liquid developer according to claim 1, wherein the binder resin contains any of the following (i) to (iv).
(I) An alcohol component containing a divalent or higher valent alcohol, a carboxylic acid component containing a divalent or higher carboxylic acid compound, and at least one functional group selected from a hydroxy group, a carboxy group, an amino group, and an epoxy group. , Reactant with silicone compound at one end or both ends (ii) Alcohol component containing divalent or higher alcohol, carboxylic acid component containing divalent or higher carboxylic acid compound, hydroxy group, carboxy group, amino group , And a reaction product with a silicone compound having at least one functional group selected from epoxy groups in the side chain (iii) A composite resin having a polyester resin segment and an addition polymerized resin segment, wherein the polyester resin segment is divalent. An alcohol component containing the above alcohol, a carboxylic acid component containing a divalent or higher carboxylic acid compound, and a silicone compound having at least one functional group selected from a hydroxy group, a carboxy group, an amino group, and an epoxy group. Composite resin as a reactant (iv) A composite resin having a polyester resin segment and an addition polymer resin segment, wherein the polyester resin segment contains an alcohol component containing a divalent or higher alcohol and a divalent or higher carboxylic acid compound. A composite resin that is a polycondensate with a carboxylic acid component and in which the addition polymerized resin segment is an added polymer of a raw material monomer containing a silicone compound having an ethylenically unsaturated group. The binder resin is at least one selected from an alcohol component containing a divalent or higher alcohol, a carboxylic acid component containing a divalent or higher carboxylic acid compound, and a hydroxy group, a carboxy group, an amino group, and an epoxy group. A reaction product with a silicone compound having a functional group at one end or both ends, or a composite resin having a polyester resin segment and an addition polymer resin segment, and the polyester resin segment is an alcohol component containing a divalent or higher alcohol. A composite resin which is a reaction product of a carboxylic acid component containing a divalent or higher carboxylic acid compound and a silicone compound having at least one functional group selected from a hydroxy group, a carboxy group, an amino group, and an epoxy group. The silicone compound has a repeating unit represented by the following formula (1-1), and has a group represented by the following formula (1-2) at one end or both ends, according to claim 1 or 2. The liquid developer described in.

[In the formula (1-1), R ¹¹ is a hydrocarbon group having 1 to 5 carbon atoms independently, and * is a binding site. ]

[In the formula (1-2), R ¹² is an alkylene group having 1 to 10 carbon atoms independently, and X is a hydroxy group, a hydroxyalkyloxy group, a carboxy group, a carboxyalkyloxy group, and a glycidyl group. , Or a glycidyloxy group, where * is the binding site. ] The binder resin is a reaction product of an alcohol component containing a divalent or higher alcohol, a carboxylic acid component containing a divalent or higher carboxylic acid compound, and a silicone compound.
The silicone compound is a reaction product with a silicone compound having at least one functional group selected from a hydroxy group, a carboxy group, an amino group, and an epoxy group in the side chain, or a composite having a polyester resin segment and an addition polymerized resin segment. The polyester resin segment is a resin, and the polyester resin segment is selected from an alcohol component containing a divalent or higher alcohol, a carboxylic acid component containing a divalent or higher carboxylic acid compound, and a hydroxy group, a carboxy group, an amino group, and an epoxy group. A composite resin that is a reaction product with a silicone compound having at least one functional group.
The liquid developer according to claim 1 or 2, wherein the silicone compound has a repeating unit represented by the following formula (2-1) and a repeating unit represented by the formula (2-2).

[In the formula (2-1), R ²¹ is independently a hydrocarbon group having 1 or more and 5 or less carbon atoms, and R ²² is independently an alkylene group having 1 or more and 5 or less carbon atoms, a1. Is 1 or 0, X ² is a hydroxy group, a carboxy group, an amino group, or an epoxy group, respectively, and * is a binding site. ]

[In the formula (2-2), R ²¹ is a hydrocarbon group having 1 to 5 carbon atoms independently, and * is a binding site. ] The binder resin is a composite resin having a polyester resin segment and an addition polymerization resin segment, and the polyester resin segment contains an alcohol component containing a divalent or higher alcohol and a carboxylic acid component containing a divalent or higher carboxylic acid compound. The addition polymerization resin segment is an addition polymerization of a raw material monomer containing a silicone compound having an ethylenically unsaturated group, and the silicone compound having an ethylenically unsaturated group is the following formula (3). The liquid developer according to claim 1 or 2, which has a repeating unit represented by -1) and has a group represented by the following formula (3-2) at one end or both ends.

[In the formula (3-1), R ³¹ is a hydrocarbon group having 1 to 5 carbon atoms independently, and * is a binding site. ]

[In formula (3-2), R ³² represents an alkylene group having 1 to 10 carbon atoms, R ³³ is a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, and * is a binding site. is there. ]