JP2011013548A - Dispersant for toner, resin composition for toner, and method for producing resin composition for toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a dispersant for toner, which uniformly and finely disperses wax in a toner, and to provide a resin composition for toner, and a method for producing a resin composition for toner, using the dispersant.SOLUTION: The dispersant for toner is used for dispersing a wax for toner in a medium, and the dispersant comprises a terminal branched copolymer expressed by general formula (1) and having a number average molecular weight of not more than 2.5×10. In formula (1), A represents a polyolefin chain; Rand Reach represent a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, and at least one of them is a hydrogen atom; and Xand Xare identical or different from each other, each representing a straight-chain or branched polyalkyleneglycol group.

Description

  The present invention relates to a toner dispersant, a toner resin composition, and a method for producing a toner resin composition.

  Conventionally, as a method for preventing the offset phenomenon and filming, there is a method in which a wax is contained in the toner and the toner itself has releasability. In this case, the dispersion state of the wax inside the toner has a significant influence on the properties of the toner, so that it is desired to be fine and uniform. For example, Patent Document 1 discloses a technique for improving the low-temperature fixability and high-temperature offset resistance of toner by finely and uniformly dispersing wax.

JP 2005-157343 A

  However, even with the technique described in the patent document, there is room for improvement in the fine particle formation and uniform dispersibility of the wax dispersed in the toner.

An object of the present invention is a dispersant used for dispersing a wax for toner in a medium, which is a terminal branched type having a number average molecular weight represented by the following general formula (1) of 2.5 × 10 ⁴ or less. Provided are a toner dispersant that uniformly and finely disperses wax inside the toner by using a toner dispersant made of a copolymer, a toner resin composition using the same, and a method for producing the toner resin composition There is to do.

  That is, the present invention includes the following inventions.

[1] Dispersing agent used to disperse toner wax in a medium and having a number average molecular weight of 2.5 × 10 ⁴ or less represented by the following general formula (1) A toner dispersant.

(In the formula, A represents a polyolefin chain. R ¹ and R ² represent a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, and at least one of them is a hydrogen atom. X ¹ and X ² are the same. Or, differently, it represents a linear or branched polyalkylene glycol group.)

[2] In the terminal branched copolymer represented by the general formula (1), X ¹ and X ² are the same or different, and the general formula (2)

(In the formula, E represents an oxygen atom or a sulfur atom. X ³ represents a polyalkylene glycol group or the following general formula (3).

(In the formula, R ³ represents an m + 1 valent hydrocarbon group. G is the same or different and is represented by —OX ⁴ , —NX ⁵ X ⁶ (X ^{4 to} X ⁶ represent a polyalkylene glycol group). M represents the number of bonds between R ³ and G, and represents an integer of 1 to 10). )
Or general formula (4)

(Wherein, X ⁷ and X ⁸ are the same or different and represent a polyalkylene glycol group or a group represented by the above general formula (3)).

[3] In the terminal branched copolymer represented by the general formula (1), either X ¹ or X ² is represented by the following general formula (5).

[Wherein X ⁹ and X ¹⁰ are the same or different and each represents a polyalkylene glycol group. Q ¹ and Q ² are the same or different and each represents a divalent alkylene group] [1] or The toner dispersant according to [2].

[4] In the terminal branched copolymer represented by the general formula (1), at least one of X ¹ and X ² is represented by the general formula (6).

(Wherein X ¹¹ represents a polyalkylene glycol group). The toner dispersant according to any one of [1] to [3].

[5] The toner dispersant according to any one of [1] to [4], wherein the terminally branched copolymer is represented by the following general formula (1a);

(In the formula, R ⁴ and R ⁵ represent a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, and at least one of them is a hydrogen atom. R ⁶ and R ⁷ represent a hydrogen atom or a methyl group, At least one of them is a hydrogen atom, R ⁸ and R ⁹ represent a hydrogen atom or a methyl group, and at least one of them is a hydrogen atom, l + m represents an integer of 2 to 450, n is 20 Represents an integer of 300 or more.)

[6] The dispersant for toner according to any one of [1] to [4], wherein the terminal branched copolymer is represented by the following general formula (1b);

(In the formula, R ⁴ and R ⁵ represent a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, and at least one of them is a hydrogen atom. R ⁶ and R ⁷ represent a hydrogen atom or a methyl group, At least one of them is a hydrogen atom, R ⁸ and R ⁹ represent a hydrogen atom or a methyl group, at least one of them is a hydrogen atom, R ¹⁰ and R ¹¹ represent a hydrogen atom or a methyl group, At least one of them is a hydrogen atom, l + m + o represents an integer of 3 to 450, and n represents an integer of 20 to 300.)

[7] A resin composition for toner containing the toner dispersant according to any one of [1] to [6], a wax, and a binder resin.

[8] The resin composition for toner according to [7], wherein the wax has an average particle size of 0.01 μm to 3 μm.

[9] A method for producing a resin composition for a toner, comprising a step of dispersing a wax in a medium using the toner dispersant according to any one of [1] to [6].

[10] The method for producing a resin composition for toner according to [9], wherein the medium is the binder resin or an organic solvent that dissolves the binder resin.

The TEM image of the resin composition produced in Example 1 is shown. The TEM image of the resin composition produced in the comparative example 1 is shown. The TEM image of the resin composition produced in Example 2 is shown. The TEM image of the resin composition produced in the comparative example 2 is shown. The TEM image of the resin composition produced in Example 3 is shown. The TEM image of the resin composition produced in the comparative example 3 is shown. The TEM image of the resin composition produced in Example 4 is shown. The TEM image of the resin composition produced in the comparative example 4 is shown.

In the dispersant for toner according to the present invention, the polyolefin chain portion represented by A of the terminally branched copolymer having the structure represented by the general formula (1) is oriented inward, and a wax is contained in the polymer particles. Is dispersed in the toner in a state of being encapsulated.
Hereinafter, the terminal branched copolymer in the present invention will be described.

[Terminal branched copolymer]
The terminally branched copolymer used in the present invention has a structure represented by the following general formula (1).

(In the formula, A represents a polyolefin chain. R ¹ and R ² are a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, and at least one of them is a hydrogen atom, and X ¹ and X ² are the same. Or, differently, it represents a linear or branched polyalkylene glycol group.)

The number average molecular weight of the terminal branched copolymer represented by the general formula (1) is 2.5 × 10 ⁴ or less, preferably 5.5 × 10 ^{2 to} 1.5 × 10 ⁴ , more preferably 8 × 10. ^{2 to} 4.0 × 10 ³ . The number average molecular weight is the number average molecular weight of the polyolefin chain represented by A, the number average molecular weight of the polyalkylene glycol group represented by X ¹ and X ² , and the molecular weight of R ¹ , R ² and C ₂ H. It is expressed as the sum of

  When the number average molecular weight of the terminal branched copolymer is in the above range, the dispersibility of the wax tends to be good, which is preferable.

  The polyolefin chain represented by A in the general formula (1) is obtained by polymerizing an olefin having 2 to 20 carbon atoms. Examples of the olefin having 2 to 20 carbon atoms include α-olefins such as ethylene, propylene, 1-butene and 1-hexene. In the present invention, it may be a homopolymer or copolymer of these olefins, and may be copolymerized with other polymerizable unsaturated compounds as long as the properties are not impaired. Among these olefins, ethylene, propylene, and 1-butene are particularly preferable.

  In general formula (1), the number average molecular weight measured by GPC of the polyolefin chain represented by A is 400 to 8000, preferably 500 to 4000, and more preferably 500 to 2000. Here, the number average molecular weight is a value in terms of polystyrene.

  When the number average molecular weight of the polyolefin chain represented by A is in the above range, the hydrophobicity of the polyolefin portion becomes appropriate and the affinity with the wax increases, so that the dispersibility of the wax becomes good.

The ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by GPC of the polyolefin chain represented by A in the general formula (1), that is, the molecular weight distribution (Mw / Mn) is not particularly limited. However, it is usually 1.0 to several tens, more preferably 4.0 or less, and still more preferably 3.0 or less.
When the molecular weight distribution (Mw / Mn) of the group represented by A in the general formula (1) is in the above range, it is preferable from the viewpoint of the shape of dispersed wax particles and the uniformity of particle diameter.

The number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) of the group represented by A by GPC can be measured under the following conditions using, for example, GPC-150 manufactured by Millipore.
Separation column: TSK GNH HT (column size: diameter 7.5 mm, length: 300 mm)
Column temperature: 140 ° C
Mobile phase: Orthodichlorobenzene (Wako Pure Chemical Industries, Ltd.)
Antioxidant: Butylhydroxytoluene (manufactured by Takeda Pharmaceutical Company Limited) 0.025% by mass
Movement speed: 1.0 ml / min Sample concentration: 0.1% by mass
Sample injection volume: 500 microliters Detector: Differential refractometer

  The molecular weight of the polyolefin chain represented by A can be measured by measuring the molecular weight of a polyolefin having an unsaturated group at one terminal, which will be described later, and subtracting the molecular weight corresponding to the terminal.

R ¹ and R ² are a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, which is a substituent bonded to a double bond of the olefin constituting A, preferably a hydrogen atom or 1 to 18 carbon atoms. It is an alkyl group. As the alkyl group, a methyl group, an ethyl group, and a propyl group are preferable.

In the general formula (1), X ¹ and X ² are the same or different and each represents a linear or branched polyalkylene glycol group having a number average molecular weight of 50 to 10,000. The branching mode of the branched alkylene glycol group includes a branching via a polyvalent hydrocarbon group or a nitrogen atom. For example, branching by a hydrocarbon group bonded to two or more nitrogen atoms, oxygen atoms or sulfur atoms in addition to the main skeleton, branching by a nitrogen atom bonded to two alkylene groups in addition to the main skeleton, and the like can be given.

  When the number average molecular weight of the polyalkylene glycol group is within the above range, the affinity with the binder resin is increased and the dispersibility of the wax is improved.

When X ¹ and X ^{2 in} the general formula (1) have the above structure, a terminal branched copolymer that improves the dispersibility of the wax in the binder resin can be obtained.
In the general formula (1), preferred examples of X ¹ and X ² are the same or different from each other, and the general formula (2),

(In the formula, E represents an oxygen atom or a sulfur atom, X ³ represents a polyalkylene glycol group, or the following general formula (3)

(Wherein R ³ represents an m + 1 valent hydrocarbon group, G is the same or different, and is represented by —OX ⁴ , —NX ⁵ X ⁶ (X ^{4 to} X ⁶ represent a polyalkylene glycol group). M represents the number of bonds between R ³ and G, and represents an integer of 1 to 10.). )
Or general formula (4)

(Wherein X ⁷ and X ⁸ are the same or different and represent a polyalkylene glycol group or a group represented by the above general formula (3)).

In the general formula (3), the group represented by R ³ is an m + 1 valent hydrocarbon group having 1 to 20 carbon atoms. m is 1-10, 1-6 are preferable and 1-2 are especially preferable.

Preferable examples of the general formula (1) include terminal branched copolymers in which either X ¹ or X ² is a group represented by the general formula (4) in the general formula (1). . More preferable examples include a terminal branched copolymer in which ^one of X ¹ and X ² is represented by the general formula (4) and the other is a group represented by the general formula (2).

As another preferable example of the general formula (1), ^one of X ¹ and X ^{2 in} the general formula (1) is a group represented by the general formula (2), and more preferably X ¹ and X ^2. And a terminal branched copolymer in which both are groups represented by the general formula (2).
As a more preferable structure of X ¹ and X ² represented by the general formula (4), the general formula (5)

(Wherein X ⁹ and X ¹⁰ are the same or different and each represents a polyalkylene glycol group, and Q ¹ and Q ² are the same or different and each represents a divalent hydrocarbon group). It is.

In the general formula (5), the divalent hydrocarbon group represented by Q ¹ and Q ² is preferably a divalent alkylene group, and more preferably an alkylene group having 2 to 20 carbon atoms. The alkylene group having 2 to 20 carbon atoms may or may not have a substituent, for example, ethylene group, methylethylene group, ethylethylene group, dimethylethylene group, phenylethylene group, chloromethylethylene group, bromo Examples thereof include a methylethylene group, a methoxymethylethylene group, an aryloxymethylethylene group, a propylene group, a trimethylene group, a tetramethylene group, a hexamethylene group, and a cyclohexylene group. A preferable alkylene group is a hydrocarbon-based alkylene group, particularly preferably an ethylene group or a methylethylene group, and still more preferably an ethylene group. Q ¹ and Q ² may be one kind of alkylene group, or two or more kinds of alkylene groups may be mixed.
As a more preferable structure of X ¹ and X ² represented by the general formula (2), the general formula (6)

(Wherein X ¹¹ represents a polyalkylene glycol group).

The polyalkylene glycol group represented by X ^{3 to} X ¹¹ is a group obtained by addition polymerization of alkylene oxide. Examples of the alkylene oxide constituting the polyalkylene glycol group represented by X ^{3 to} X ¹¹ include ethylene oxide, propylene oxide, butylene oxide, styrene oxide, cyclohexene oxide, epichlorohydrin, epibromohydrin, methyl glycidyl ether, allyl A glycidyl ether etc. are mentioned. Of these, propylene oxide, ethylene oxide, butylene oxide, and styrene oxide are preferable. More preferred are propylene oxide and ethylene oxide, and particularly preferred is ethylene oxide. The polyalkylene glycol group represented by X ^{3 to} X ¹¹ may be a group obtained by homopolymerization of these alkylene oxides or a group obtained by copolymerization of two or more kinds. Examples of preferred polyalkylene glycol groups are polyethylene glycol groups, polypropylene glycol groups, or groups obtained by copolymerization of polyethylene oxide and polypropylene oxide, and particularly preferred groups are polyethylene glycol groups.

In the general formula (1), it is preferable that X ¹ and X ² have the above structure because the dispersibility of the wax in the binder resin becomes good.
As the terminal branched copolymer that can be used in the present invention, a polymer represented by the following general formula (1a) or (1b) is preferably used.

(In the formula, R ⁴ and R ⁵ represent a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, and at least one of them is a hydrogen atom. The alkyl group is preferably an alkyl group having 1 to 9 carbon atoms. And an alkyl group having 1 to 3 carbon atoms is more preferable.)

R ⁶ and R ⁷ represent a hydrogen atom or a methyl group, and at least one of them is a hydrogen atom. R ⁸ and R ⁹ represent a hydrogen atom or a methyl group, and at least one of them is a hydrogen atom.
l + m represents an integer of 2 to 450, preferably 5 to 200.
n represents an integer of 20 to 300, preferably 25 to 200.

(In the formula, R ⁴ and R ⁵ represent a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, and at least one of them is a hydrogen atom. The alkyl group is preferably an alkyl group having 1 to 9 carbon atoms. And an alkyl group having 1 to 3 carbon atoms is more preferable.)

R ⁶ and R ⁷ represent a hydrogen atom or a methyl group, and at least one of them is a hydrogen atom. R ⁸ and R ⁹ represent a hydrogen atom or a methyl group, and at least one of them is a hydrogen atom. R ¹⁰ and R ¹¹ represent a hydrogen atom or a methyl group, and at least one of them is a hydrogen atom.
l + m + o represents an integer of 3 to 450, preferably 5 to 200.
n represents an integer of 20 to 300, preferably 25 to 200.
As the polymer represented by the general formula (1b), it is more preferable to use a polymer represented by the following general formula (1c).

(In the formula, l + m + o and n are the same as those in the general formula (1b).)

  The number of ethylene units (n) in the polyethylene chain was calculated by dividing the number average molecular weight (Mn) of the polyolefin group A in the general formula (1) by the molecular weight of the ethylene unit. The total number of ethylene glycol units (l + m or l + m + o) of the polyethylene glycol chain is such that the weight ratio of the polymer raw material to the ethylene oxide used during the polyethylene glycol group addition reaction is the number average molecular weight of the polymer raw material and the polyethylene glycol group (Mn ) And the ratio was calculated assuming that the ratio was the same.

  For example, in the terminal branched copolymer (T-1) obtained in Synthesis Example 1 of this example, since the weight ratio of the polymer raw material (I-1) and the ethylene oxide used is 1: 1, The Mn of the expanded ethylene glycol unit becomes 1223 with respect to Mn1223 of the combined raw material (I-1). By dividing this by the molecular weight of the ethylene glycol unit, the total number of ethylene glycol units (l + m + o) of the PEG chain can be calculated.

N, l + m or l + m + o can also be measured by ¹ H-NMR. For example, in the terminal branched copolymer (T-1) obtained in Synthesis Example 1, the integral value of the terminal methyl group (shift value: 0.87 ppm) of the polyolefin group A in the general formula (1) is 3 protons. Can be calculated from the integral value of the methylene group (shift value: 1.04-1.71 ppm) of the polyolefin group A and the integral value of the alkylene group of PEG (shift value: 3.10-4.16 ppm). .

  Specifically, since the molecular weight of the methyl group is 15, the molecular weight of the methylene group is 14, and the molecular weight of the alkylene group is 44, the number average molecular weights of the polyolefin group A and the alkylene group can be calculated from the values of the respective integral values. By dividing the number average molecular weight of the polyolefin group A thus obtained by the molecular weight of the ethylene unit, n is divided by the number average molecular weight of the alkylene group by the molecular weight of the ethylene glycol unit, whereby the total number of ethylene glycol units (l + m Alternatively, l + m + o) can be calculated.

When the polyolefin group A is composed of an ethylene-propylene copolymer, n and l + m or l + m + o can be obtained by using both the propylene content that can be measured by IR, ¹³ C-NMR, and the integral value in ¹ H-NMR. Can be calculated. ^{In 1} H-NMR, a method using an internal standard is also effective.

[Method for producing terminally branched copolymer]
The terminally branched copolymer can be produced by the following method.
First, as a polymer corresponding to the structure of A represented by the general formula (1) in the target terminal branched copolymer, the general formula (7)

(In the formula, A is a group having a polymerized number average molecular weight of 400 to 8000 of an olefin having 2 to 20 carbon atoms, R ¹ and R ² are a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, and at least either of them. One of them represents a hydrogen atom.), And a polyolefin having a double bond at one end is produced.
This polyolefin can be produced by the following method.

(1) A transition metal compound having a salicylaldoimine ligand as shown in JP-A Nos. 2000-239312, 2001-27331, 2003-73412, etc. is used as a polymerization catalyst. Polymerization method.
(2) A polymerization method using a titanium catalyst comprising a titanium compound and an organoaluminum compound.
(3) A polymerization method using a vanadium catalyst comprising a vanadium compound and an organoaluminum compound.
(4) A polymerization method using a Ziegler-type catalyst comprising a metallocene compound such as zirconocene and an organoaluminum oxy compound (aluminoxane).

  Among the above methods (1) to (4), particularly according to the method (1), the polyolefin can be produced with high yield. In the method (1), a polyolefin having a double bond at one end is produced by polymerizing or copolymerizing the olefin described above in the presence of the transition metal compound having the salicylaldoimine ligand. be able to.

  The polymerization of the olefin by the method (1) can be carried out by either a liquid phase polymerization method such as solution polymerization or suspension polymerization or a gas phase polymerization method. Detailed conditions and the like are already known, and the above-mentioned patent documents can be referred to.

  The molecular weight of the polyolefin obtained by the method (1) can be adjusted by allowing hydrogen to be present in the polymerization system, changing the polymerization temperature, or changing the type of catalyst used.

  Next, the polyolefin is epoxidized, that is, the double bond at the terminal of the polyolefin is oxidized to obtain a polymer containing an epoxy group at the terminal represented by the general formula (8).

(In the formula, A, R ¹ and R ² are as described above.)
Although the epoxidation method is not particularly limited, the following methods can be exemplified.
(1) Oxidation with peracids such as performic acid, peracetic acid, perbenzoic acid (2) Oxidation with titanosilicate and hydrogen peroxide (3) Oxidation with rhenium oxide catalyst such as methyltrioxorhenium and hydrogen peroxide ( 4) Oxidation with a porphyrin complex catalyst such as manganese porphyrin or iron porphyrin and hydrogen peroxide or hypochlorite (5) Salen complex such as manganese Salen and oxidation with hydrogen peroxide or hypochlorite (6) Manganese- Oxidation with a TACN complex such as a triazacyclononane (TACN) complex and hydrogen peroxide (7) Oxidation with hydrogen peroxide in the presence of a group VI transition metal catalyst such as a tungsten compound and a phase transfer catalyst

Among the methods (1) to (7), the methods (1) and (7) are particularly preferable in terms of the active surface.
For example, VIKOLOX ^™ (registered trademark, manufactured by Arkema) can be used as a low molecular weight terminal epoxy group-containing polymer having a Mw of about 400 to 600.

By reacting the terminal epoxy group-containing polymer represented by the general formula (8) obtained by the above-mentioned method with various reaction reagents, the polymer terminal α, β-position represented by the general formula (9) A polymer (polymer (I)) into which various substituents Y ¹ and Y ² are introduced can be obtained.

(In the formula, A, R ¹ and R ² are as described above. Y ¹ and Y ² are the same or different and represent a hydroxyl group, an amino group, or the following general formulas (10a) to (10c)).

(In the general formulas (10a) to (10c), E represents an oxygen atom or a sulfur atom, R ³ represents an m + 1 valent hydrocarbon group, T represents the same or different hydroxyl group and amino group, and m represents 1 Represents an integer of 10 to 10.)

For example, by hydrolyzing the terminal epoxy group-containing polymer represented by the general formula (8), a polymer in which both Y ¹ and Y ² are hydroxyl groups in the general formula (9) is obtained, and ammonia is reacted. By doing so, a polymer in which ^one of Y ¹ and Y ² is an amino group and the other is a hydroxyl group is obtained.

Further, by reacting the terminal epoxy group-containing polymer represented by the general formula (8) with the reaction reagent A represented by the general formula (11a), ^one of Y ¹ and Y ² in the general formula (9) A polymer having a group represented by the general formula (10a) and the other hydroxyl group is obtained.

(In the formula, E, R ³ , T and m are as described above.)

Further, by reacting the terminal epoxy group-containing polymer with the reaction reagent B represented by the general formulas (11b) and (11c), ^one of Y ¹ and Y ² in the general formula (9) is represented by the general formula (10b) or A polymer having the group shown in (10c) and the other hydroxyl group is obtained.

(Wherein R ³ , T and m are as described above.)

  Examples of the reaction reagent A represented by the general formula (11a) include glycerin, pentaerythritol, butanetriol, dipentaerythritol, polypentaerythritol, dihydroxybenzene, and trihydroxybenzene.

Examples of the reaction reagent B represented by the general formulas (11b) and (11c) include ethanolamine, diethanolamine, aminophenol, hexamethyleneimine, ethylenediamine, diaminopropane, diaminobutane, diethylenetriamine, N- (aminoethyl) propanediamine, and imino. Bispropylamine, spermidine, spermine, triethylenetetramine, polyethyleneimine and the like can be mentioned.
Addition reactions of epoxy compounds with alcohols and amines are well known and can be easily performed by ordinary methods.

  The general formula (1) can be produced by addition polymerization of alkylene oxide using the polymer (I) represented by the general formula (9) as a raw material. Examples of the alkylene oxide include propylene oxide, ethylene oxide, butylene oxide, styrene oxide, cyclohexene oxide, epichlorohydrin, epibromohydrin, methyl glycidyl ether, and allyl glycidyl ether. Two or more of these may be used in combination. Of these, propylene oxide, ethylene oxide, butylene oxide, and styrene oxide are preferable. More preferred are propylene oxide and ethylene oxide.

For the catalyst, polymerization conditions, etc., known ring-opening polymerization methods of alkylene oxides can be used. For example, Takayuki Otsu, “Chemistry of Revised Polymer Synthesis”, Kagaku Dojin, January 1971, p. . 172-180 discloses an example in which a polyol is obtained by polymerizing various monomers. Catalysts used for ring-opening polymerization include Lewis acids such as AlCl ₃ , SbCl ₅ , BF ₃ , and FeCl ₃ for cationic polymerization and alkali metal hydroxides for anionic polymerization as disclosed in the above document. Alternatively, alkaline earth metal oxides, carbonates, alkoxides, or alkoxides such as Al, Zn, and Fe can be used for alkoxides, amines, phosphazene catalysts, and coordination anionic polymerization. Here, as the phosphazene catalyst, for example, an anion of a compound disclosed in JP-A-10-77289, specifically, a commercially available tetrakis [tris (dimethylamino) phosphoranylideneamino] phosphonium chloride is alkalinized. The thing made into the alkoxy anion using the metal alkoxide etc. can be utilized.

  When a reaction solvent is used, the polymer (I) can be inert to the alkylene oxide, alicyclic hydrocarbons such as n-hexane and cyclohexane, and aromatic hydrocarbons such as toluene and xylene. And ethers such as dioxane, and halogenated hydrocarbons such as dichlorobenzene.

Except for the phosphazene catalyst, the catalyst is used in an amount of preferably 0.05 to 5 mol, more preferably 0.1 to 3 mol, relative to 1 mol of the starting polymer (I). The amount of phosphazene catalyst, polymerization rate, in terms of economy and the like, preferably 1 × ¹⁰ -4 ~5 × ^{10 -1} moles per mole of the polymer (I), more preferably 5 × 10 ^{- 4} to 1 × 10 ⁻¹ mol.

  The reaction temperature is usually 25 to 180 ° C., preferably 50 to 150 ° C., and the reaction time varies depending on the reaction conditions such as the amount of catalyst used, reaction temperature, reactivity of olefins, etc., but is usually several minutes to 50 hours. .

  As described above, the number average molecular weight of the general formula (1) depends on the method of calculating from the number average molecular weight of the polymer (I) represented by the general formula (8) and the weight of the alkylene oxide to be polymerized, or a method using NMR. Can be calculated.

[Toner Resin Composition]
The toner resin composition using the toner dispersant of the present invention will be described below.
The toner resin composition in the present invention contains the toner dispersant in the present invention, a wax, and a binder resin.

The following are mentioned as binder resin used for this invention.
For example, a homopolymer of styrene such as polyester resin, polystyrene, poly-p-chlorostyrene, polyvinyltoluene, or a substituted product thereof; styrene-p-chlorostyrene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene Copolymer, styrene-acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ether copolymer, Styrene copolymers such as styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer; polychlorinated Vinyl, pheno Resin, natural modified phenolic resin, natural resin modified maleic acid resin, acrylic resin, methacrylic resin, polyvinyl acetate resin, polyether resin, silicone resin, polyurethane resin other than the above resins, polyamide resin, furan resin, epoxy resin, xylene resin And resins such as polyvinyl butyral, terpene resin, coumarone indene resin, petroleum resin, and cross-linked styrene copolymer. Preferred binder materials include polyester resins or styrene copolymers. An elongation reaction or a polymerization reaction may be performed in the process of forming toner particles by using a low molecular weight monomer or monomer of the binder resin.

  As the wax in the present invention, those usually added to the toner can be used, for example, olefin wax such as polypropylene wax, polyethylene wax, microcrystalline wax, polyethylene oxide wax, paraffin wax; carnauba wax, sazol. Aliphatic ester waxes such as wax and montanic acid ester wax; Deacidified carnauba wax; Saturated aliphatic acid waxes such as baltimic acid, stearic acid and montanic acid; Unsaturation such as pracidic acid, eleostearic acid and valinalic acid Aliphatic acid waxes; saturated alcohol waxes such as stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnauvyl alcohol, seryl alcohol, melyl alcohol, and aliphatic alcohol waxes Polyhydric alcohol wax such as sorbitol; saturated fatty acid amide wax such as linoleic acid amide, oleic acid amide, lauric acid amide; methylene bis stearic acid amide, ethylene biscapric acid amide, ethylene bis lauric acid amide, hexamethylene Saturated fatty acid bisamide waxes such as bis-stearic acid amide; Unsaturated ethylene bisoleic acid amide, hexamethylene bis-oleic acid amide, N, N′-dioleyl adipic acid amide, N, N′-dioleyl sebacic acid amide, etc. Acid amide waxes; aromatic bisamide waxes such as m-xylene bis stearamide, N, N′-distearylisophthalamide; calcium stearate, calcium laurate, zinc stearate, magnesium stearate, etc. Fatty acid metal salt; Graft-modified wax obtained by graft polymerization of vinyl monomers such as styrene and acrylic acid onto polyolefin; Partial ester wax obtained by reacting fatty acid such as behenic acid monoglyceride with polyhydric alcohol; Hydrogenation of vegetable oil Methyl ester wax having a hydroxyl group obtained; ethylene-vinyl acetate copolymer wax having a high ethylene component content; long-chain alkyl acrylate wax such as saturated stearyl acrylate wax such as acrylic acid; aroma such as benzyl acrylate wax Group acrylate wax, Fischer-Tropsch wax and the like. These waxes may be used alone or in combination of two or more.

  From the viewpoint of obtaining good toner characteristics, the average particle size of the wax contained in the resin composition for toner of the present invention is 0.01 μm or more, more preferably 0.1 μm or more. From the viewpoint of improving uniform dispersibility. 3 μm or less, more preferably 2 μm or less. The maximum particle size of the wax is preferably 5 μm or less from the viewpoint of obtaining good toner characteristics. The size of the wax in the toner can be appropriately adjusted by a known method such as changing the dispersant content.

In the present invention, the average particle size and the maximum particle size of the wax are values measured as follows.
100 wax particles were arbitrarily selected on a 40 μm × 60 μm TEM photograph of the resin composition for toner of the present invention or a toner using the same, and the particle size of each wax particle was calculated. And the average value was computed and it was set as the average particle diameter of wax. In addition, three regions of 40 μm × 60 μm on the TEM photograph of the resin composition for toner of the present invention or the toner using the same were selected, and the maximum length of the wax particles in each region was calculated. And the average value was computed and it was set as the largest particle size of wax.

  In the toner using the toner resin composition of the present invention, a charge adjusting agent, a colorant such as a pigment, and other additives as required may be added internally or externally. As the charge adjusting agent, known charge adjusting agents can be used alone or in combination. The charge adjusting agent may be an amount necessary to make the toner have a desired charge amount. For example, it is preferably about 0.05 to 10 parts by weight with respect to 100 parts by weight of the toner resin composition. More specifically, examples of the positive charge regulator include nigrosine dyes, quaternary ammonium salt compounds, triphenylmethane compounds, imidazole compounds, and polyamine resins. Examples of negative charge regulators include metal-containing azo dyes such as Cr, Co, Al, and Fe, salicylic acid metal compounds, alkyl salicylic acid metal compounds, and curixarene compounds.

  As the colorant that can be used in the toner using the resin composition for toner of the present invention, any colorant known to be used in the production of conventional toners can be used. Examples of these colorants include fatty acid metal salts, various carbon blacks, phthalocyanine series, rhodamine series, quinacridone series, triallylmethane series, anthraquinone series, azo series and diazo series. The colorants can be used alone or in combination of two or more. The blending amount of these colorants is usually preferably 1 to 10 parts by weight with respect to 100 parts by weight of the toner resin composition.

  Toners using the resin composition for toners of the present invention are further known as used in the production of toners such as lubricants, fluidity improvers, abrasives, conductivity-imparting agents, and image peeling prevention agents as required. Additives can be added internally or externally. As examples of these additives, as the lubricant, polyvinylidene fluoride, zinc stearate, etc., as the fluidity improver, colloidal silica, aluminum oxide, titanium oxide, etc., as the abrasive, cerium oxide, silicon carbide, Examples of the conductivity imparting agent include strontium titanate, tungsten carbide, calcium carbonate, and carbon black and tin oxide. In addition, fine powders of fluorine-containing polymers such as polyvinylidene fluoride are preferable from the viewpoints of fluidity, abrasiveness, charge stability, and the like.

[Method for Producing Toner Resin Composition]
Hereinafter, a method for producing a resin composition for toner using the toner dispersant composed of the terminally branched copolymer described above will be described.

  The method for producing a resin composition for a toner of the present invention includes a step of dispersing wax in a medium using the toner dispersant of the present invention. Examples of the step of dispersing the wax in the medium include a case where a binder resin is used as a medium, and a case where an organic solvent which dissolves the binder resin is used as a medium.

  More specifically, when a binder resin is used as a medium, first, a material such as a toner dispersant, a binder resin, and a wax comprising the terminally branched copolymer of the present invention is used in a microcompounder, a biaxial kneader or the like. Dissolve and knead using a kneader to disperse the wax in the binder resin. The kneading temperature should just be more than the temperature which a binder resin fuse | melts, Preferably it is 80-180 degreeC, More preferably, it is 100-160 degreeC. In addition, the blending order and melt-kneading order of the materials at the time of melt-kneading are arbitrary, for example, all materials may be blended together and melt-kneaded, or after each material is separately blended and melt-kneaded, The obtained plurality of kneaded products may be further melt-kneaded together. Subsequently, the melt-kneaded product obtained is extruded as it is and extruded into a desired shape such as a strand, a pellet, or a powder. Thereafter, the resultant is appropriately coarsely pulverized and then finely pulverized using a jet mill or the like and classified by a classifier such as an elbow jet to obtain toner particles of a predetermined size. Further, from the viewpoint of toner characteristics, a toner is manufactured by externally adding generally used inorganic fine powders such as silica, alumina, and titanium oxide as external additives.

  When an organic solvent that dissolves the binder resin is used as a medium, first, a material such as a toner dispersant, a binder resin, and a wax comprising the terminally branched copolymer of the present invention is dissolved in an organic solvent to obtain a resin solution. Is made. Subsequently, water or the like is added to the obtained resin solution to disperse the resin solution in an aqueous medium. The order of addition is not particularly limited, and the resin solution may be added to the aqueous phase and dispersed. Thereby, the organic solvent and the binder resin are dispersed in the solution as oil droplets. Furthermore, the organic solvent is removed by heating or reduced pressure to obtain resin particles. Thereafter, drying is performed, and in the same manner as described above, an inorganic fine powder such as silica, alumina, titanium oxide or the like is externally added as an external additive to produce a toner.

  The organic solvent that dissolves the binder resin may be any one that dissolves each material. For example, aromatic hydrocarbon solvents such as toluene, xylene, ethylbenzene, and tetralin; n-hexane, n-heptane, mineral spirit, cyclohexane Aliphatic or alicyclic hydrocarbon solvents such as methyl chloride, methyl bromide, methyl iodide, methylene dichloride, carbon tetrachloride, trichloroethylene, perchloroethylene, and other halogen solvents; ethyl acetate, butyl acetate, methoxybutyl Ester or ester ether solvents such as acetate, methyl cellosolve acetate, ethyl cellosolve acetate; diethyl ether, tetrahydrofuran, dioxane, ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, etc. Ether solvents; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, di-n-butyl ketone, cyclohexanone; methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, 2-ethylhexyl alcohol , Alcohol solvents such as benzyl alcohol; amide solvents such as dimethylformamide and dimethylacetamide; sulfoxide solvents such as dimethyl sulfoxide; heterocyclic compounds such as N-methylpyrrolidone and 1,3-dimethyl-2-imidazolidinone Examples thereof include system solvents and mixed solvents of two or more of these.

  When manufacturing toner with the above method, a relatively low molecular weight binder resin is used when dissolving in an organic solvent, and the binder resin is increased in molecular weight by an extension reaction after being dispersed as oil droplets in an aqueous solution. May be performed. Further, a polymerizable monomer composition is obtained by uniformly dissolving or dispersing a polymerizable monomer, a polymerization initiator, a dispersant for toner comprising the terminally branched copolymer of the present invention, and a wax. Thereafter, the dispersion is carried out in an aqueous medium containing a dispersion stabilizer using an appropriate stirrer, and a polymerization reaction is performed, whereby a toner particle suspension having a desired particle diameter can be obtained. The toner can be produced by drying the suspension and adding an external additive.

  The dispersion in the present invention can be performed by a method in which a resin solution obtained by dissolving a material such as a terminal branched copolymer, a binder resin, and a wax in an organic solvent is physically dispersed in water by mechanical shearing force.

  The dispersion method is not particularly limited as long as it is commercially available as an emulsifier or a disperser. For example, a homogenizer (manufactured by IKA), polytron (manufactured by Kinematica), TK auto homomixer (specialized machinery industry) Etc.) batch type emulsifiers, Ebara Milder (made by Aihara Seisakusho Co., Ltd.), TK Philmix, TK Pipeline Homo Mixer (made by Special Machine Industries), Colloid Mill (made by Shinko Pantech Co., Ltd.), Thrasher, Continuous emulsifiers such as Trigonal wet milling machine (Mitsui Miike Chemical Co., Ltd.), Captron (Eurotech Co., Ltd.), Fine Flow Mill (Pacific Kiko Co., Ltd.), Microfluidizer (Mizuho Kogyo Co., Ltd.), Nanomizer ( Nanomizer), APV Gaurin (Gaurin) and other high pressure emulsifiers, Membrane Emulsifier (Chilling Industries) and other membrane emulsifiers Vibro Mixer (Hiyaka Kogyo) vibrating emulsifier such as, ultrasonic emulsifier such as an ultrasonic homogenizer (manufactured by Branson Co., Ltd.). Among these, APV Gaurin, homogenizer, TK auto homomixer, Ebara milder, TK fill mix, and TK pipeline homomixer are preferable from the viewpoint of uniform particle size.

  The time required for dispersion varies depending on the dispersion temperature and other dispersion conditions, but is about 1 to 300 minutes.

  The above stirring time is preferable because dispersion can be sufficiently performed and the toner resin composition is hardly deteriorated. A method for removing the organic solvent from the obtained aqueous dispersion is not particularly limited, and a rotary evaporator, a film evaporator, or the like can be used.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the scope of the present invention is not limited to these examples.

<Synthesis example of terminal branched copolymer>
Number average molecular weight (Mn), weight average molecular weight (Mw), and molecular weight distribution (Mw / Mn) were measured by GPC using the method described in the text. Moreover, the peak top temperature obtained by measuring using DSC was employ | adopted for melting | fusing point (Tm). In addition, although melting | fusing point of a polyalkylene glycol part is also confirmed by measurement conditions, here, unless there is particular notice, it refers to melting | fusing point of a polyolefin part. ^{For 1} H-NMR, the polymer was completely dissolved in deuterated 1,1,2,2-tetrachloroethane serving as a lock solvent and a solvent in a measurement sample tube, and then measured at 120 ° C. did. The chemical shift was determined by setting the peak of deuterated 1,1,2,2-tetrachloroethane to 5.92 ppm and determining the chemical shift value of other peaks. The shape of the resin was observed with an electron microscope (TEM) by the following method. First, the sample was trimmed to an appropriate size, and an ultrathin section was prepared after ruthenium tetroxide staining. This sample was observed with TEM (H-7650 manufactured by Hitachi, Ltd.) under the condition of 100 kV. Observation of the shape of the resin was performed using an optical microscope (manufactured by Keyence Corporation; VH-Z450 and VH-7000). A micro compounder (manufactured by DSM; DSM-Xplore) was used for kneading the resin.

[Synthesis Example 1]
(Synthesis of polyolefin end-branched copolymer (T-1))
A terminal epoxy group-containing ethylene polymer (E-1) was synthesized according to the following procedure (for example, see Synthesis Example 2 of JP-A-2006-131870).

A stainless steel autoclave with an internal volume of 2000 ml sufficiently purged with nitrogen was charged with 1000 ml of heptane at room temperature, and the temperature was raised to 150 ° C. Subsequently, 30 kg / cm ² G was pressurized with ethylene in the autoclave to maintain the temperature. A hexane solution (1.00 mmol / ml of aluminum atom equivalent) of MMAO (manufactured by Tosoh Finechem) was injected with 0.5 ml (0.5 mmol), and then a toluene solution (0.0002 mmol / ml) of a compound of the following formula: 0.5 ml (0.0001 mmol) was injected to initiate the polymerization. Polymerization was carried out at 150 ° C. for 30 minutes in an ethylene gas atmosphere, and then a small amount of methanol was injected to stop the polymerization. The obtained polymer solution was added to 3 liters of methanol containing a small amount of hydrochloric acid to precipitate a polymer. After washing with methanol, it was dried under reduced pressure at 80 ° C. for 10 hours to obtain a one-terminal double bond-containing ethylene polymer (P-1).

In a 500 ml separable flask, 100 g of the ethylene polymer (P-1) containing one terminal double bond (Mn850, vinyl group 108 mmol), toluene 300 g, Na ₂ WO ₄ 0.85 g (2.6 mmol), CH ₃ ( nC ₈ H ₁₇ ) ₃ NHSO ₄ 0.60 g (1.3 mmol) and phosphoric acid 0.11 g (1.3 mmol) were charged, and the mixture was heated to reflux with stirring for 30 minutes to completely melt the polymer. After the internal temperature was set to 90 ° C., 37 g (326 mmol) of 30% hydrogen peroxide solution was added dropwise over 3 hours, and the mixture was stirred at an internal temperature of 90 to 92 ° C. for 3 hours. Thereafter, 34.4 g (54.4 mmol) of a 25% aqueous sodium thiosulfate solution was added while maintaining the temperature at 90 ° C., and the mixture was stirred for 30 minutes. The peroxide in the reaction system was completely decomposed with the peroxide test paper. It was confirmed. Subsequently, 200 g of dioxane was added at an internal temperature of 90 ° C. to crystallize the product, and the solid was collected by filtration and washed with dioxane. The obtained solid was stirred in a 50% aqueous methanol solution at room temperature, and the solid was collected by filtration and washed with methanol. Further, the solid was stirred in 400 g of methanol, collected by filtration and washed with methanol. By drying at room temperature under reduced pressure of 1 to 2 hPa, 96.3 g of a white solid of a terminal epoxy group-containing ethylene polymer (E-1) was obtained (yield 99%, olefin conversion 100%).

  The obtained terminal epoxy group-containing ethylene polymer (E-1) was Mw = 2058, Mn = 1118, Mw / Mn = 1.84 (GPC). (Terminal epoxy group content: 90 mol%)

¹ H-NMR: δ (C ₂ D ₂ Cl ₄ ) 0.88 (t, 3H, J = 6.92 Hz), 1.18-1.66 (m), 2.38 (dd, 1H, J = 2.64, 5.28 Hz), 2.66 (dd, 1H, J = 4.29, 5.28 Hz) 2.80-2.87 (m, 1H)
Melting point (Tm): 121 ° C
Mw = 2058, Mn = 1118, Mw / Mn = 1.84 (GPC)

A 1000 mL flask was charged with 84 parts by weight of a terminal epoxy group-containing ethylene polymer (E-1), 39.4 parts by weight of diethanolamine, and 150 parts by weight of toluene, and stirred at 150 ° C. for 4 hours. Thereafter, acetone was added while cooling to precipitate the reaction product, and the solid was collected by filtration. The obtained solid was stirred and washed once with an aqueous acetone solution and further three times with acetone, and then the solid was collected by filtration. Thereafter, the polymer (I-1) (Mn = 1223, A: group formed by polymerization of ethylene (Mn = 1075) in the general formula (9) (Mn = 1075), R ¹ = R by drying under reduced pressure at room temperature. ² = hydrogen atom, ^one of Y ¹ and Y ² is a hydroxyl group, and the other is a bis (2-hydroxyethyl) amino group).

¹ H-NMR: δ (C ₂ D ₂ Cl ₄ ) 0.88 (t, 3H, J = 6.6 Hz), 0.95-1.92 (m), 2.38-2.85 (m , 6H), 3.54-3.71 (m, 5H)
Melting point (Tm): 121 ° C

  A 500 mL flask equipped with a nitrogen introduction tube, a thermometer, a cooling tube, and a stirring device was charged with 20.0 parts by weight of the polymer (I-1) and 100 parts by weight of toluene, and heated in an oil bath at 125 ° C. while stirring. The solid was completely dissolved. After cooling to 90 ° C., 0.323 parts by weight of 85% KOH previously dissolved in 5.0 parts by weight of water was added to the flask and mixed for 2 hours under reflux conditions. Thereafter, water and toluene were distilled off while gradually raising the temperature in the flask to 120 ° C. Further, while supplying a slight amount of nitrogen to the flask, the inside of the flask was depressurized, and the internal temperature was further raised to 150 ° C. and maintained for 4 hours to further distill off water and toluene in the flask. After cooling to room temperature, the solidified solid in the flask was crushed and taken out.

A stainless steel 1.5 L pressure reactor equipped with a heating device, a stirring device, a thermometer, a pressure gauge, and a safety valve was charged with 18.0 parts by weight of the obtained solid and 200 parts by weight of dehydrated toluene. After substituting with nitrogen, the temperature was raised to 130 ° C. with stirring. After 30 minutes, 18.0 parts by weight of ethylene oxide was added, and the mixture was further maintained at 130 ° C. for 5 hours, and then cooled to room temperature to obtain a reaction product. The solvent is removed from the obtained reaction product by drying, and a terminal branched copolymer (T-1) (Mn = 2446, in formula (1), A: a group formed by polymerization of ethylene (Mn = 1075). , R ¹ = R ² = hydrogen atom, ^one of X ¹ and X ² is polyethylene glycol, and the other is a group represented by the general formula (5) (Q ¹ = Q ² = ethylene group, X ⁹ = X ¹⁰ = polyethylene glycol )).

¹ H-NMR: δ (C ₂ D ₂ Cl ₄ ) 0.87 (3H, t, J = 6.8 Hz), 1.04-1.71 (m), 3.10-3.40 (m ), 3.54-4.16 (m)
Melting point (Tm): 27 ° C. (polyethylene glycol), 118 ° C.

[Synthesis Example 2]
(Synthesis of polyolefin end-branched copolymer (T-2))
100 parts by weight of terminal branched copolymer (T-1) and 0.74 parts by weight of acetic acid are added to a micro compounder, kneaded for 2 minutes at a kneading temperature of 140 ° C. and a rotational speed of 100 rpm, and then the strand is maintained while maintaining the rotational speed. Extruded in the form of a terminal branched copolymer (T-2).

(Measurement method of average particle size and maximum particle size of wax)
100 wax particles were arbitrarily selected on a 40 μm × 60 μm TEM photograph, and the particle size of each wax particle was calculated. And the average value was computed and it was set as the average particle diameter of wax. Three regions of 40 μm × 60 μm were selected on the TEM photograph, and the maximum length of the wax particles was calculated on the TEM photograph in each region. And the average value was computed and it was set as the largest particle size of wax.

(Preparation of resin composition for toner A)
[Example 1]
5 parts by weight of paraffin wax (HNP-9 manufactured by Nippon Seiwa Co., Ltd.), 0.5 parts by weight of a charge control agent (TN-105 manufactured by Hodogaya Chemical Co., Ltd.) per 100 parts by weight of polyester resin (XPE2587 manufactured by Mitsui Chemicals) 1 part by weight of a branched copolymer (T-2) is added to a microcompounder, and after kneading for 5 minutes at a kneading temperature of 120 ° C. and a rotational speed of 100 rpm, the resin composition is extruded into a strand while maintaining the rotational speed. Obtained. A TEM observation of the obtained resin composition is shown in FIG. The average particle size of the wax was 0.6 μm, and the maximum particle size was 2.5 μm.

[Example 2]
5 parts by weight of paraffin wax (HNP-9 manufactured by Nippon Seiwa Co., Ltd.) and 0.5 parts by weight of charge control agent (TN-105 manufactured by Hodogaya Chemical Co., Ltd.) per 100 parts by weight of styrene-acrylic resin (CPR300 manufactured by Mitsui Chemicals) , 1 part by weight of a terminal branched copolymer (T-2) was added to a micro compounder, kneaded at a kneading temperature of 120 ° C. and a rotation speed of 100 rpm for 5 minutes, and then extruded into a strand shape while maintaining the rotation speed. I got a thing. What obtained TEM observation about the obtained resin composition was shown in FIG. The average particle size of the wax was 0.2 μm, and the maximum particle size was 0.8 μm.

[Example 3]
5 parts by weight of paraffin wax (HNP-9 manufactured by Nippon Seiwa Co., Ltd.), 6 parts by weight of carbon black (Regal 330R manufactured by Cabot), and 100 parts by weight of a polyester resin (XPE2587 manufactured by Mitsui Chemicals), charge control agent (Hodogaya Chemical) TN-105) 0.5 part by weight and 1 part by weight of terminal branched copolymer (T-2) were added to the microcompounder and kneaded at a kneading temperature of 120 ° C. and a rotational speed of 100 rpm for 5 minutes, followed by the rotational speed. The resin composition was obtained by extruding into a strand while maintaining the above. What obtained TEM observation about the obtained resin composition was shown in FIG. The average particle size of the wax was 0.5 μm, and the maximum particle size was 2.4 μm. A toner was prepared from the obtained resin composition.

[Comparative Example 1]
5 parts by weight of paraffin wax (HNP-9 manufactured by Nippon Seiwa Co., Ltd.), 0.5 parts by weight of a charge control agent (TN-105 manufactured by Hodogaya Chemical Co., Ltd.) per 100 parts by weight of polyester resin (XPE2587 manufactured by Mitsui Chemicals) 1 part by weight of a branched copolymer (T-2) is added to a microcompounder, and after kneading for 5 minutes at a kneading temperature of 120 ° C. and a rotational speed of 100 rpm, the resin composition is extruded into a strand while maintaining the rotational speed. Obtained. A TEM observation of the obtained resin composition is shown in FIG. The average particle size of the wax was 1.5 μm, and the maximum particle size was 13 μm.

[Comparative Example 2]
5 parts by weight of paraffin wax (HNP-9 manufactured by Nippon Seiwa Co., Ltd.) and 0.5 parts by weight of charge control agent (TN-105 manufactured by Hodogaya Chemical Co., Ltd.) per 100 parts by weight of styrene-acrylic resin (CPR300 manufactured by Mitsui Chemicals) Was added to a micro compounder, kneaded at a kneading temperature of 120 ° C. and a rotation speed of 100 rpm for 5 minutes, and then extruded into a strand shape while maintaining the rotation speed to obtain a resin composition. What obtained TEM observation about the obtained resin composition was shown in FIG. The average particle size of the wax was 0.3 μm, and the maximum particle size was 5.5 μm.

[Comparative Example 3]
5 parts by weight of paraffin wax (HNP-9 manufactured by Nippon Seiwa Co., Ltd.), 6 parts by weight of carbon black (Regal 330R manufactured by Cabot), and 100 parts by weight of a polyester resin (XPE2587 manufactured by Mitsui Chemicals), charge control agent (Hodogaya Chemical) TN-105) 0.5 parts by weight was added to a microcompounder, kneaded at a kneading temperature of 120 ° C. and a rotational speed of 100 rpm for 5 minutes, and then extruded into a strand shape while maintaining the rotational speed to obtain a resin composition. . What obtained TEM observation about the obtained resin composition was shown in FIG. The average particle size of the wax was 1.0 μm, and the maximum particle size was 6.0 μm. A toner was prepared from the obtained resin composition.

(Preparation of resin composition for toner B)
[Example 4]
A 200 mL flask equipped with a nitrogen introduction tube, a thermometer, a cooling tube, and a stirrer, 100 parts by weight of a polyester resin (XPE2587 manufactured by Mitsui Chemicals), 5 parts by weight of paraffin wax (HNP-9 manufactured by Nippon Seiwa Co., Ltd.), charge control 0.5 parts by weight of the agent (TN-105 manufactured by Hodogaya Chemical Co., Ltd.), 1 part by weight of the terminal branched copolymer (T-2) and 800 parts by weight of ethyl acetate are added and mixed under a reflux condition in a nitrogen atmosphere for 30 minutes. Thus, an ethyl acetate solution (resin solution 1) was obtained. In a 1 L beaker, 240 parts by weight of distilled water and 10 parts by weight of a surfactant (PEX SS-L manufactured by Kao Corporation) are added and stirred at 6000 rpm using a high-speed shearing stirring device (TK Robotics manufactured by PRIMIX Corporation). While continuing stirring in this aqueous solution, 100 parts by weight of the resin solution 1 prepared above was added and dispersion operation was performed for 1 minute. Further, the solvent was removed using a rotary evaporator, and the obtained aqueous resin dispersion was filtered, washed with water, and dried to obtain resin particles. The particle diameter of the obtained resin particles was 5 μm to 30 μm as a result of observation with an optical microscope. Furthermore, what dried the resin solution 1 under reduced pressure and performed TEM observation about the obtained resin composition was shown in FIG. The average particle size of the wax was 1.0 μm, and the maximum particle size was 2.0 μm.

[Comparative Example 4]
A 100 mL flask equipped with a nitrogen inlet tube, thermometer, condenser, and stirrer, 100 parts by weight of polyester resin (XPE2587 made by Mitsui Chemicals), 5 parts by weight paraffin wax (HNP-9 made by Nippon Seiwa Co., Ltd.), charge control 0.5 parts by weight of an agent (TN-105 manufactured by Hodogaya Chemical Co., Ltd.) and 800 parts by weight of ethyl acetate were added and mixed for 30 minutes under a nitrogen atmosphere under reflux conditions to obtain an ethyl acetate solution (resin solution 2). In a 1 L beaker, 240 parts by weight of distilled water and 10 parts by weight of a surfactant (PEX SS-L manufactured by Kao Corporation) are added and stirred at 6000 rpm using a high-speed shearing stirring device (TK Robotics manufactured by PRIMIX Corporation). While continuing stirring in this aqueous solution, 100 parts by weight of the resin solution 2 prepared above was added, and dispersion operation was performed for 1 minute. However, the aqueous phase and the resin solution were separated without emulsification, and no resin particles were obtained. Furthermore, what dried the resin solution 2 under reduced pressure and performed TEM observation about the obtained resin composition was shown in FIG. The average particle size of the wax was 1.8 μm, and the maximum particle size was 5.2 μm.

(Evaluation)
1 (Example 1), FIG. 2 (Comparative Example 1), FIG. 3 (Example 2), FIG. 4 (Comparative Example 2), FIG. 5 (Example 3), FIG. 6 (Comparative Example 3), FIG. When (Example 4) and FIG. 8 (Comparative Example 4) are respectively compared, the resin composition (FIGS. 1, 3 and 7) containing the terminally branched copolymer (T-2) and the toner (FIG. It was found that 5) had a smaller wax particle size and the wax particles were uniformly dispersed. Therefore, toner using such a resin composition as a binder resin can improve the storage stability of the toner because wax aggregation in the toner and exposure to the toner surface are reduced. Moreover, since the offset phenomenon and filming can be suppressed, durability corresponding to continuous printing can be improved and productivity can be improved. In particular, in a color toner, since a toner material such as wax can be uniformly and finely dispersed, good transparency can be obtained.

Claims (10)

A toner used for dispersing a wax for toner in a medium, comprising a terminal branched copolymer having a number average molecular weight of 2.5 × 10 ⁴ or less represented by the following general formula (1) Dispersant.
(In the formula, A represents a polyolefin chain. R ¹ and R ² represent a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, and at least one of them is a hydrogen atom. X ¹ and X ² are the same. Or, differently, it represents a linear or branched polyalkylene glycol group.) In the terminal branched copolymer represented by the general formula (1), X ¹ and X ² are the same or different, and the general formula (2)
(In the formula, E represents an oxygen atom or a sulfur atom. X ³ represents a polyalkylene glycol group or the following general formula (3).
(In the formula, R ³ represents an m + 1 valent hydrocarbon group. G is the same or different and is represented by —OX ⁴ , —NX ⁵ X ⁶ (X ^{4 to} X ⁶ represent a polyalkylene glycol group). M represents the number of bonds between R ³ and G, and represents an integer of 1 to 10). )
Or general formula (4)
The toner dispersant according to claim 1, wherein X ⁷ and X ⁸ are the same or different and represent a polyalkylene glycol group or a group represented by the general formula (3). In the terminal branched copolymer represented by the general formula (1), either X ¹ or X ² is represented by the following general formula (5).
(Wherein X ⁹ and X ¹⁰ are the same or different and each represents a polyalkylene glycol group; Q ¹ and Q ² are the same or different and each represents a divalent alkylene group). 2. The toner dispersant according to 2. In the terminal branched copolymer represented by the general formula (1), at least one of X ¹ and X ² is represented by the general formula (6).
The toner dispersant according to claim 1, wherein X ¹¹ represents a polyalkylene glycol group. The dispersant for toner according to any one of claims 1 to 4, wherein the terminally branched copolymer is represented by the following general formula (1a);
(In the formula, R ⁴ and R ⁵ represent a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, and at least one of them is a hydrogen atom. R ⁶ and R ⁷ represent a hydrogen atom or a methyl group, At least one of them is a hydrogen atom, R ⁸ and R ⁹ represent a hydrogen atom or a methyl group, and at least one of them is a hydrogen atom, l + m represents an integer of 2 to 450, n is 20 Represents an integer of 300 or more.) The dispersant for toner according to claim 1, wherein the terminal branched copolymer is represented by the following general formula (1b):
(In the formula, R ⁴ and R ⁵ represent a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, and at least one of them is a hydrogen atom. R ⁶ and R ⁷ represent a hydrogen atom or a methyl group, At least one of them is a hydrogen atom, R ⁸ and R ⁹ represent a hydrogen atom or a methyl group, at least one of them is a hydrogen atom, R ¹⁰ and R ¹¹ represent a hydrogen atom or a methyl group, At least one of them is a hydrogen atom, l + m + o represents an integer of 3 to 450, and n represents an integer of 20 to 300.)   A toner resin composition comprising the toner dispersant according to any one of claims 1 to 6, a wax, and a binder resin.   The toner resin composition according to claim 7, wherein the wax has an average particle size of 0.01 μm or more and 3 μm or less.   A method for producing a resin composition for a toner, comprising a step of dispersing a wax in a medium using the toner dispersant according to claim 1.   The method for producing a resin composition for a toner according to claim 9, wherein the medium is the binder resin or an organic solvent that dissolves the binder resin.