JPH07225496A - Electric charge controlling agent, toner binder composition and electrophotographic toner - Google Patents

Abstract

PURPOSE:To obtain a toner using a practically colorless electric charge controlling agent not contg. a metal and having such high performance as superior dispersibility, a large extent of electrostatic charge, rapid kick-off of electrostatic charge and satisfactory environmental stability. CONSTITUTION:This electrophotographic toner contains a binder and an electric charge controlling agent made of a polymer having acid groups. In this toner, at least a part of the binder forms a continuous phase, at least a part of the electric charge controlling agent forms a discontinuous domain and the difference between the SP value of a polymer chain part in the doamin forming electric charge controlling agent and the SP value of the continuous phase forming binder is -2.5 to 0. The acid value of the polymer chain part is 50-400 and at least 3% of acid groups imparting the acid value are free acid groups.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a charge control agent, a toner binder composition containing the same, and an electrophotographic toner. More specifically, it relates to a charge control agent for negative charging, a toner binder composition containing the same, and an electrophotographic toner.

[0002]

2. Description of the Related Art Conventionally, a charge control agent has been added to control the electric charge of an electrophotographic toner. Among the charge control agents known today, negative charge control agents include azo dye compounds and salicylic acid metal complexes. However, these compounds are originally colored (for example, azo dye-based compounds) or contain heavy metals such as chromium, cobalt, and zinc, and have recently become a problem from the viewpoint of safety. Also,
Since it is a low-molecular crystal, it is difficult to finely disperse it in the toner, and when it is used as a toner, the charge amount distribution becomes wide.

To improve the above problems, α-
Olefin / maleic anhydride copolymer (USP 4,44
2,189), styrene / maleic anhydride copolymer (JP-A-60-108861), methyl methacrylate / methacrylic acid block copolymer (USP).
4,925,765) and other polymer compounds have been proposed.

[0004]

However, although the polymer compound disclosed in (1) has solved the problems of coloring and safety, its dispersibility in the toner is poor, and other performance aspects (charge amount, charge amount, Charge rise and environmental stability) are also insufficient.
Further, since it is poor in transparency when used as a toner, it adversely affects the color tone when used as a color toner. The compound disclosed in 1) has been improved in terms of dispersibility in addition to coloring and safety, but the charge control agent and charge buildup are insufficient because the charge control agent is difficult to expose on the toner surface. .

[0005]

DISCLOSURE OF THE INVENTION The present inventors have found that the present invention is substantially colorless and contains no metal, and is excellent in charge amount, charge buildup, environmental stability, and dispersibility and transparency. The inventors arrived at the present invention through extensive studies to develop a charge control agent that does not have a charge control agent. That is, the present invention is constituted by the following [1] to [4]. [1] In an electrophotographic toner containing a toner binder, a coloring material, and a charge control agent composed of a polymer having an acid group, at least a part of the toner binder forms a continuous phase, and at least one of the charge control agents is used. The toner forms a continuous phase in the toner and the SP value (SPa) of the polymer chain portion (α) forming the discontinuous domain in the charge control agent. SP value of binder (β) (SP
b) difference (SPa-SPb) is 0 to -2.5, the acid value of (α) is 50 to 400, and at least 3% of the acid groups giving the acid value are free acid groups. An electrophotographic toner characterized by the following. [2] An α, β-unsaturated dicarboxylic acid comprising a polymer (A) having an alkyl group having 6 to 50 carbon atoms and a carboxyl group, wherein (A) has an alkyl group having 6 to 50 carbon atoms as an essential constituent unit. (Co) polymer (A1) containing at least 5 mol% of acid monoalkyl ester (1), and ethylenically unsaturated monomer (2) 6-having an alkyl group having 6 to 50 carbon atoms as an essential constituent unit 80 mol% and α, β-
Unsaturated mono- or dicarboxylic acid (3) 5-75 mol%
A charge control agent, which is a polymer selected from the copolymers (A2) containing and. [3] A toner binder composition containing a toner binder and the charge control agent described in [2]. [4] In an electrophotographic toner containing a toner binder, a coloring material and a charge control agent, the charge control agent is [2]
A toner for electrophotography, which is the charge control agent as described above.

In the present invention, examples of the toner binder include styrene-based polymers, polyester-based polymers, epoxy-based polymers, polyolefin-based polymers and polyurethane-based polymers, which are known as toner binders. The styrene-based polymer may be a copolymer of styrene, a (meth) acrylic acid ester and other monomer copolymerizable therewith, a styrene-diene-based monomer (butadiene, isoprene, etc.) Examples thereof include copolymers of other polymerizable monomers. Examples of the polyester polymer include polycondensates of aromatic dicarboxylic acids and alkylene oxide adducts of bisphenols. Examples of the epoxy polymer include a reaction product of an aromatic diol and epichlorohydrin and a modified product thereof. Examples of the polyolefin-based polymer include polyethylene, polypropylene, and a copolymer of ethylene or propylene with another copolymerizable monomer. Examples of polyurethane-based polymers include polyaddition products of aromatic diisocyanates and alkylene oxide adducts of aromatic diols.

In the present invention, known pigments and dyes can be used as the coloring material. Specifically, carbon black, iron black, Sudan black SM, first yellow-G, benzidine yellow, pigment yellow, indian first orange, irgasin red, balanitoaniline red, toluidine red, carmine F
B, Pigment Orange R, Lake Red 2G, Rhodamine FB, Rhodamine B Lake, Methyl Violet B
Lake, phthalocyanine blue, pigment blue, priliant green, phthalocyanine green, oil yellow GG, Kayaset YG, orazole brown B, oil pink OP and the like can be mentioned.

In the toner of the present invention [1], at least a part of the toner binder forms a continuous phase,
The fact that at least a part of the charge control agent forms a discontinuous domain can be confirmed by the presence or absence of an interface when observing a section of the toner with a transmission electron microscope or the like. In order to clearly observe the interface, it is also effective to perform electron microscope observation after dyeing the toner section with ruthenium tetroxide, osmium tetroxide or the like. The dispersed particle size of the domain in the above is preferably 0.01 to 0.8 μm, and more preferably 0.05 to 0.5 μm. When it exceeds 0.8 μm, the dispersibility is insufficient, the charge amount distribution is widened, and the transparency of the toner is deteriorated. Further, when the dispersed particle size is less than 0.01 μm or when the particles are completely compatible with each other in the toner binder without forming discontinuous domains, the content of the charge control agent on the toner surface becomes small,
Insufficient amount of charge. Further, a compatibilizing agent may be used in combination for controlling the dispersed particle diameter to 0.8 μm or less. The compatibilizer has compatibility with the polymer portion (α),
Further, the polymer (γ) having compatibility with the toner binder (β) forming the continuous phase is also effective.

The SP value (SPa) of (α) and the SP value (SPb) of (β) in the item [1] of the present invention are known methods, for example, the calculation method of Fedors (Polym. Eng. Sc).
i., 14 [2] 147 (1974))). SPa-SPb is usually -2.5 to 0,
It is preferably -2.0 to -0.2. When the SP value of more than 0 (α) becomes larger than the SP value of (β), the content of the charge control agent on the toner surface becomes small and the charge amount becomes insufficient. If the absolute value becomes larger than | -2.5 |,
There is a problem that the dispersibility becomes insufficient, the charge amount distribution becomes wide, and the transparency of the toner deteriorates.

The acid group of the polymer in the charge control agent of the present invention [1] is a carboxylic acid group, a sulfonic acid group,
Examples thereof include a phosphoric acid group and a boric acid group. Of these, a carboxylic acid group is preferred. Further, a part of the acid group may be acid anhydride, but usually at least 3% is a free acid group which is not acid anhydride, preferably 10%.
% Or more is a free acid group. If the ratio of free acid groups is less than 3%, the charge amount will be insufficient and the rise of charging will be insufficient. The acid group may be contained in a portion other than (α) in the charge control agent, but the acid value given by the acid group in (α) is usually 50 to 400. When it is less than 50, the charge amount becomes insufficient, and when it exceeds 300, the charge control agent is hard to be exposed on the toner surface, so that the charge amount becomes insufficient again and the environmental dependence is deteriorated. Further, the preferable range of the acid value varies depending on the ratio of the free acid group in the acid group, and the ratio of the acid anhydride increases, that is, as the ratio of the free acid group decreases, the acid value becomes relatively high. Higher is preferable. That is, when 70% or more of the acid groups are free acid groups, the acid value is preferably in the range of 50 to 300, more preferably 70 to 250, and particularly 80 to 200.
Is. When 30% or more and less than 70% of the acid group is a free acid group, the acid value is preferably 60 to 350, and more preferably 80 to 3.
00, especially 100-250. 3% or more to 3 of acid groups
When less than 0% is a free acid group, the acid value is preferably 80
To 400, more preferably 100 to 350, and especially 150 to 300. The acid value of (α) can be determined by titrating a charge control agent containing (α) with an alkali (potassium hydroxide, sodium hydroxide, etc.) according to a standard method. If some of the acid groups are converted to acid anhydride, neutralize with excess alkali and then remove the remaining alkali with a strong acid (such as hydrochloric acid).
It is preferable to titrate with. When the charge control agent also has an acid group in a portion other than (α), the acid can be obtained by titrating after isolating at least a portion of the portion forming (α) or the portion other than (α). You can ask for a price. When the structure of (α) is clear by a spectroscopic method such as NMR, the acid value can be calculated from the content of the acid group. As a method for determining the ratio of free acid groups when a part of the organic acid groups are acid anhydride, the acid value and the acid anhydride value are determined by titration, and the method is determined from the difference,
Infrared absorption spectra, spectroscopic methods such as NMR and the like can be mentioned.

(Α) is 25 to 100 ° C., especially 35 to 10
Has a melting point of 0 ° C or no melting point but 25-1
It preferably has a glass transition point of 00 ° C, particularly 35 to 100 ° C. If the melting point is lower than 25 ° C. or has no melting point and the glass transition point is lower than 25 ° C., the fluidity of the toner,
It tends to adversely affect the storage stability. When the melting point is higher than 100 ° C. or the glass transition point is higher than 100 ° C. without a melting point, it becomes difficult to knead the charge control agent into the toner, and the charge amount distribution tends to be wide. Also,
It is more preferable that (α) is a crystalline polymer chain having a melting point because the charge control agent is less likely to be exposed on the toner surface, and the required charge amount is easily obtained by adding a small amount of the charge control agent. Melting point and glass transition point are determined by DSC according to standard methods.
Is obtained by observing the endothermic peak or change in specific heat of the charge control agent or the electrophotographic toner containing (α).

As the charge control agent that gives the above physical property values,
Examples thereof include polymers (A) having an alkyl group having 6 to 50 carbon atoms and a carboxyl group. As the polymer (A), a (co) polymer (A1) containing at least 5 mol% of an α, β-unsaturated dicarboxylic acid monoalkyl ester (1) having an alkyl group having 6 to 50 carbon atoms as an essential constituent unit. ), 6 to 80 mol% of an ethylenically unsaturated monomer (2) having an alkyl group having 6 to 50 carbon atoms as an essential constituent unit and an α, β-unsaturated mono- or dicarboxylic acid (3) 5
The copolymer (A2) and the like are included.

The (co) polymer (A1) is also a homopolymer of an α, β-unsaturated dicarboxylic acid monoalkyl ester (1) having an alkyl group having 6 to 50 carbon atoms, and (1) and (1) It may be a copolymer with another monomer (4) copolymerizable with.
Examples of (1) include maleic acid monoalkyl ester, itaconic acid monoalkyl ester, and fumaric acid monoalkyl ester. Among these, preferred are maleic acid monoalkyl ester and itaconic acid monoalkyl ester, and more preferred is itaconic acid monoalkyl ester. The alkyl group has usually 6 to 50 carbon atoms, and preferably 10 to 40 carbon atoms. Further, the alkyl group is preferably a linear alkyl group rather than a branched one. The number of carbon atoms of the alkyl group in (1) is 6
If it is less than the above value, the SP value of (α) becomes large, the charge control agent is hard to be exposed on the toner surface, the charge amount becomes insufficient, and the glass transition point becomes high, which makes it difficult to disperse in the toner. When it exceeds 50, the concentration of the carboxyl group in (α) decreases, so that the charge amount becomes insufficient and the rise of charging becomes poor. When the alkyl group has a large number of branches, the fluidity and storage stability of the toner are likely to be adversely affected.

Other monomers (4) copolymerizable with (1) include α, β-unsaturated dicarboxylic acid and its acid anhydride (4-1), and α, β-unsaturated dicarboxylic acid dialkyl. Examples thereof include esters (4-2) and other monomers (4-3). Examples of (4-1) include maleic acid, itaconic acid, fumaric acid and their anhydrides. Among these, preferred are the same dicarboxylic acids as those constituting (1) and their acid anhydrides. As the α, β-unsaturated dicarboxylic acid dialkyl ester (4-2), the above (4
-1) dialkyl ester can be mentioned, and the preferred one is the dialkyl ester of dicarboxylic acid which constitutes (1) as in (4-1). The preferred alkyl group is also the same as in (1).

Other monomers (4-3) include lower olefins (ethylene, propylene, 1-butene, isobutylene, etc.), vinyl ether (methyl vinyl ether,
Butyl vinyl ether, etc.), vinyl halides (vinyl chloride, etc.), vinyl esters (vinyl acetate, vinyl propionate, etc.), aromatic vinyl hydrocarbons (styrene,
(α-methylstyrene, p-cumylstyrene, etc.), (meth)
Acrylic acid, (meth) acrylic acid ester [methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, etc.], diene (butadiene, isoprene, etc.), nitrile group-containing monomer [(meth ) Acrylonitrile and the like] and the like. Of these, preferred are lower olefins and aromatic vinyl hydrocarbons when (1) is maleic acid monoalkyl ester. When (1) is another α, β-unsaturated dicarboxylic acid monoalkyl ester, it is a lower olefin, aromatic vinyl hydrocarbon, (meth) acrylic acid or (meth) acrylic acid ester.

The (A) of (1) which constitutes the (co) polymer (A1)
When (1) is maleic acid monoalkyl ester, the mol% in 1) is usually 5 to 100 mol%, preferably 1
It is 0 to 60 mol%. When (1) is another α, β-unsaturated dicarboxylic acid monoalkyl ester, it is usually 5
˜100 mol%, preferably 20 to 100 mol%. If (1) is less than 5 mol%, the charge amount will be insufficient.
When (4-1) or (4-2) is used together with (1), the copolymerization molar ratio is usually (1): [(4-1) + (4-2)] is 1
0: 0 to 2: 8, and [(1) +2 (4-1)]:
[(1) +2 (4-2)] is in the range of 5: 1 to 1: 3, preferably (1): [(4-1) + (4-2)] is 10:
0 to 4: 6, and [(1) +2 (4-1)]: [(1) +
2 (4-2)] is in the range of 2: 1 to 1: 2. (4-
When (3) is used, the copolymerization mol% is usually 0 to 7 when (1) is a maleic acid monoalkyl ester.
It is 0 mol%, preferably 40 to 60 mol%. Also,
When (1) is another α, β-unsaturated dicarboxylic acid monoalkyl ester, (4-3) is usually 0 to 60 mol%, preferably 0 to 20 mol%.

As the ethylenically unsaturated monomer (2) having an alkyl group having 6 to 50 carbon atoms, which constitutes (A2),
It has an ester-based ethylenically unsaturated monomer (2-1) having an alkyl group having 6 to 50 carbon atoms, an α-olefin (2-2) having 8 to 52 carbon atoms, and an alkyl group having 6 to 50 carbon atoms. Examples thereof include alkyl vinyl ether (2-3).

Examples of (2-1) include a carboalkoxy group-containing monomer (2-1a) and an acyloxy group-containing monomer (2-1b), and (2-1a) is preferred. Examples of (2-1a) include (meth) acrylic acid alkyl ester and α, β-unsaturated dicarboxylic acid (mono or di) alkyl ester. (2-1b)
Examples thereof include alkanoic acid vinyl ester, alkanoic acid allyl ester, and the like. As alkanoic acids forming these esters, linear alkanoic acid (octanoic acid, lauric acid, stearic acid, behenic acid, etc.), branched alkanoic acid ( Isostearic acid, etc.) and the like.

(2-2) includes 1-octene and 1-
Decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene, 1-dococene, 1-tetracocene, 1-hexacocene, 1-octacocene, 1-triacontene and mixtures of two or more thereof. Is mentioned. Of these, preferred are α-olefins having 12 to 40 carbon atoms and mixtures of two or more thereof.

Examples of (2-3) include hexyl vinyl ether, octyl vinyl ether, lauryl vinyl ether, cetyl vinyl ether, stearyl vinyl ether and behenyl vinyl ether. Of these, preferred is vinyl ether having an alkyl group having 10 to 22 carbon atoms.

Examples of the α, β-unsaturated monocarboxylic acid or dicarboxylic acid (3) constituting (A2) include α, β-unsaturated dicarboxylic acid monoester (3-1) and α, β-unsaturated dicarboxylic acid monoamide. (3-2), (meth) acrylic acid (3-
3), α, β-unsaturated dicarboxylic acid (3-4) and the like. Among these, preferable ones are (3-1),
(3-2) and (3-3).

Examples of the α, β-unsaturated dicarboxylic acid (3-4) include maleic acid, fumaric acid and itaconic acid.

The α, β-unsaturated dicarboxylic acid monoester (3-1) includes the above α, β-unsaturated dicarboxylic acid (3-4) and alcohols, phenols, mercaptans, oxyalkylenes and the like. The monoester of is mentioned. Alcohols include C1-C20 alkanols (methanol, ethanol, butanol, octanol, lauryl alcohol, stearyl alcohol, etc.), cycloalkyl alcohols (cyclohexyl alcohol, etc.), aralkyl alcohols (benzyl alcohol, etc.), fluoroalkyl alcohols (perfluorobutyl). Ethanol, perfluorohexyl ethanol, perfluorooctyl ethanol, etc.) and the like. Examples of phenols include phenol, cresol and salicylic acid. Examples of mercaptans include alkyl mercaptans (such as lauryl mercaptan) and thiophenol. Examples of oxyalkylenes include alkylene oxide (ethylene oxide, propylene oxide, etc.) adducts of the above alcohols, phenols, or mercaptans.

Α, β-unsaturated dicarboxylic acid monoamide (3
-2) includes the above α, β-unsaturated dicarboxylic acid (3-
Monoamides of 4) with primary or secondary amines can be mentioned.

The primary amines include alkylamines (ethylamine, butylamine, octylamine, laurylamine, stearylamine, etc.), cycloalkylamines (cyclohexylamine, etc.), aralkylamines (benzylamine, etc.), arylamines (aniline, etc.). ) And the like. Examples of secondary amines include dialkylamines (diethylamine, dibutylamine, etc.), saturated nitrogen-containing heterocyclic compounds (piperidine, morpholine, etc.), arylamines (N-methylaniline, etc.), and the like.

The copolymer (A2) may be a copolymer of (2) and (3), and other monomer (5) copolymerizable with (2) and (3) is also a constituent unit. It may also be a copolymer. Examples of the other monomer (5) include α, β-unsaturated dicarboxylic acid anhydride (5-1) and other monomer (5-2).

Α, β-unsaturated dicarboxylic acid anhydride (5-
Examples of 1) include the acid anhydride of (3-4). Other monomers (5-2) include lower olefins (ethylene, propylene, 1-butene, isobutylene, etc.), lower vinyl ethers (methyl vinyl ether, butyl vinyl ether, etc.), vinyl halides (vinyl chloride, etc.), lower vinyl Ester (vinyl acetate, vinyl propionate, etc.), aromatic vinyl hydrocarbon (styrene, α-methylstyrene, p-cumylstyrene, etc.), (meth) acrylic acid lower ester [methyl (meth) acrylate, (meth) acrylic acid Ethyl, butyl (meth) acrylate, etc.], dienes (butadiene, isoprene, etc.), nitrile group-containing monomers [(meth) acrylonitrile, etc.], and the like. When (5) is used, preferred ones among them are lower olefins, aromatic vinyl hydrocarbons,
And (meth) acrylic acid ester.

In the copolymer (A2), (2) and (3)
The copolymerization molar ratio of (5) is usually 6 to 80 mol% for (2), 5 to 75 mol% for (3), and 0 to 89 mol% for (5).
And does not contain (5-1) as (5),
Preferably, (2) is 30 to 70 mol% and (3) is 30 to 70 mol%.
70 mol% and (5-2) are 0 to 40 mol%.
When (5-1) is contained as (5), preferably (2) is 30 to 70 mol%, (3) is 5 to 50 mol%,
(5-1) is 5 to 60 mol% and (5-2) is 0 to 40 mol%. When the copolymerization ratio of (2) is less than 6 mol%, the charge control agent is hard to be exposed on the toner surface, resulting in insufficient charge amount.
If it exceeds 80 mol%, the charge amount becomes insufficient and the rise of charge becomes poor. Similarly, when the copolymerization ratio of (3) is less than 5 mol%, the charge amount becomes insufficient and the charging rise becomes worse. When the copolymerization molar ratio of (5-1) is 5 mol% or more, the copolymerization molar ratio of (3) is relatively at least less likely to cause insufficient charge amount, but the copolymerization ratio of (3) is less than 5 mol%. Is not enough.

In the present invention, the weight average molecular weight of (A) is usually 1,000 to 500,000, preferably 2,000 to 200,000. If it is less than 1,000, it is completely compatible with the toner binder and it becomes difficult to form discontinuous domains, resulting in insufficient charge amount and adversely affecting the fluidity of the toner. Further, if it exceeds 500,000, it becomes difficult to disperse it in the toner.

The polymer (A) may be a polymer (AA) consisting only of a polymer portion having an alkyl group having 6 to 50 carbon atoms and a carboxyl group, but an alkyl group having 6 to 50 carbon atoms and a carboxyl group. A copolymer (AB) in which a polymer portion (b) selected from a styrene polymer portion (b1) and a polyester polymer portion (b2) is further bonded to the polymer portion (a) having ) Can also be used. The use of (AB) is preferable because (a) can easily reduce the particle size of the discontinuous domains (α) formed in the toner. Further, in order to exert this effect, it is more preferable that (b) has a structure similar to that of the toner binder. That is, when a styrene-based polymer is used as the toner binder, (b1) is preferable as (b), and (b2) is preferable as (b) when the toner binder is a polyester-based polymer. To reduce the particle size, the total amount of (A) should be (AB)
Does not have to be, and it is sufficient if a part is (AB). That is, it may contain (AA) together with (AB). In this case, (α) is formed by (a) and (A
Both of A). Further, in addition to (AB) and (AA), a styrene-based polymer (B1) not bound to (a),
It may contain a polymer (B) selected from polyester-based polymers (B2).

Preferred as (AA) and (a) are the same as (A).

The weight ratio of (AB), (AA) and (B) when they are combined in a graft or block form is usually 1 to 100% by weight for (AB) and 0 to 99 for (AA).
% By weight, (B) is 0 to 90%, preferably (A
B) is 10 to 100% by weight, (AA) is 0 to 90% by weight, and (B) is 0 to 50% by weight. If the weight ratio of (AB) is less than 1% by weight, it is difficult to reduce the particle size of (α), and if the content of (B) exceeds 90% by weight, a large amount of charge control agent for obtaining a sufficient charge amount. Is necessary and not economical.
Ratio (Wa / Wb) of total weight (Wa) of (a) and (AA) and total weight (Wb) of (b) and (B)
Is usually 99/1 to 10/90, preferably 90/10
~ 20/80. When (Wa) is less than 10%, a large amount of charge control agent is required to obtain a sufficient charge amount, which is not economical, and when it exceeds 99%, it becomes difficult to reduce the particle size of (α).

In the present invention, the styrene polymer constituting (b1) may be a homopolymer of styrene or a copolymer with another monomer (6) copolymerizable with styrene. Other copolymerizable monomers (6) include aromatic vinyl hydrocarbons other than styrene, (meth) acrylic monomers,
Other vinyl monomers may be mentioned. Examples of aromatic vinyl hydrocarbons other than styrene include substituted styrene [alkyl-substituted styrene (α-methylstyrene,
p-methylstyrene, p-cumylstyrene, etc.), halogen-substituted styrene (chlorostyrene, chloromethylstyrene, etc.), acetoxystyrene, hydroxystyrene, etc.].

Examples of the (meth) acrylic monomer include (meth) acrylate [alkyl (meth) acrylate having 1 to 18 carbon atoms {methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2- Ethylhexyl (meth) acrylate, lauryl (meth) acrylate,
Stearyl (meth) acrylate, etc .; Hydroxyl group-containing (meth) acrylate {Hydroxyethyl (meth) acrylate; Epoxy group-containing (meth) acrylate {Glycidyl (meth) acrylate, etc.}; Isocyanate group-containing
(Meth) acrylate {methacryloyl isocyanate, etc.]; nitrile group-containing monomer {(meth) acrylonitrile, etc.} and the like.

Other vinyl monomers include vinyl esters (vinyl acetate, vinyl propionate, etc.), diene monomers (butadiene, isoprene, etc.), halogenated olefins (vinyl chloride, vinyl bromide, etc.), α ,
β-unsaturated mono- or polycarboxylic acids {(meth) acrylic acid, crotonic acid, sorbic acid, maleic acid, itaconic acid, cinnamic acid, etc.}, their anhydrides (maleic anhydride, etc.), their partial esters ( Maleic acid monomethyl ester etc.) and the like.

Among the examples of the styrene-based polymer constituting (b1), preferred are styrene homopolymers, copolymers of styrene and (meth) acrylic monomers, styrene and diene monomers. And copolymers of these with small amounts of other copolymerizable monomers.
When the styrene polymer constituting (b1) is a copolymer, the copolymerization ratio of styrene and the other monomer (6) is usually 40 mol% or more of styrene, preferably 60 mol. % Or more.

In the present invention, examples of the polyester polymer constituting (b2) include polycondensates of polyol (7) and polycarboxylic acid (8).

As the polyol (7), a diol (7-1) is used.
And trivalent or higher valent polyols (7-2), and (7-1)
And a mixture of (7-1) and a small amount of (7-2) is preferred. The diol (7-1) is an alkylene glycol having 2 to 12 carbon atoms [ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol,
1,6-hexanediol, etc.], alkylene ether glycol [diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, etc.], alicyclic diol [1,4-cyclohexanedimethanol, hydrogen Additive bisphenol A, etc.], bisphenols [bisphenol A, bisphenol F,
Bisphenol S] and alkylene oxide [ethylene oxide, propylene oxide, butylene oxide, etc.] adducts of the above bisphenols. Of these, preferred ones have 2 to 2 carbon atoms.
A 12-alkylene glycol and an alkylene oxide adduct of a bisphenol are particularly preferable, and an alkylene oxide adduct of a bisphenol and a combination thereof with an alkylene glycol having 2 to 12 carbon atoms are preferable.

Examples of the trivalent or higher valent polyol (7-2) include aliphatic polyhydric alcohols having 3 to 20 carbon atoms [glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, etc.] and trivalent or higher phenols. Examples thereof include trisphenol PA, phenol novolac, cresol novolac and the like, and alkylene oxide adducts of the above trivalent or more polyphenols.

Examples of the polycarboxylic acid (8) include dicarboxylic acid (8-1) and polycarboxylic acid having a valence of 3 or more (8-2), and a small amount of (8-1) and (8-1). The mixture of (8-2) is preferable. The dicarboxylic acid (8-1) has 2 to 20 carbon atoms.
Alkylenedicarboxylic acid [succinic acid, adipic acid, sebacic acid, etc.], alkenylenedicarboxylic acid having 4 to 20 carbon atoms [maleic acid, fumaric acid, etc.] and 8 carbon atoms
To 20 aromatic dicarboxylic acids [phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, etc.] and the like. Of these, preferred ones have 4 carbon atoms.
~ 20 alkenylene dicarboxylic acid and 8 to 2 carbon atoms
It is 0 aromatic dicarboxylic acid. Examples of the trivalent or higher polycarboxylic acid (8-2) include aromatic polycarboxylic acids having 9 to 20 carbon atoms [trimellitic acid, pyromellitic acid, etc.] and the like.

The molar ratio of (7) and (8) constituting the polyester polymer portion (b2) is usually 1: 2 to 2: 1, preferably 1: 1.5 to 1.5: 1. . With (7-1) in (7)
The molar ratio of (7-2) is usually 100: 0 to 80:20, preferably 100: 0 to 90:10. (8-1) in (8)
The preferable molar ratio of (7-2) to (8-2) is the same as that of (7-1) to (7-2). Further, preferred as (B1) and (B2) are the same as (b1) and (b2).

The following are examples of the method of bonding the copolymer (AB) in which (a) and (b) are bonded in a graft form and / or a block form. Graft copolymer obtained by grafting the branch polymer of (b) onto the trunk polymer of (a) Graft copolymer obtained by grafting the branch polymer of (a) onto the trunk polymer of (b) Block copolymer of (a) and (b) Polymer Of these, the preferred one is a graft copolymer with.

The weight average molecular weights of (a) and (b) constituting (AB) are usually 1,000 to 100, for (a).
000 and (b) are 1,000 to 500,000, preferably (a) is 2,000 to 50,000 and (b) is 3,000 to 100,000. (A) or (b)
Of less than 1,000 adversely affects the fluidity of the toner,
(A) exceeds 100,000, or (b) is 5
If it exceeds 0.000, it becomes difficult to disperse it in the toner.

Specific examples of (AA) in the polymer (A) include the following. 1) Monostearyl itaconic acid homopolymer 2) Monolauryl itaconic acid homopolymer 3) Monostearyl itaconic acid / itaconic anhydride (80 /
20) Copolymer 4) Monostearyl Itaconic Acid / Distearyl Itaconate (90/10) Copolymer 5) Monostearyl Itaconic Acid / Acrylic Acid / Butyl Acrylate (98/1/1) Copolymer 6) Itacone Monolauryl acid / acrylic acid / methyl acrylate (98/1/1) copolymer 7) Monocetyl maleate / maleic anhydride / styrene (30/20/50) copolymer 8) Stearyl methacrylate / methacrylic acid (60
/ 40) copolymer 9) stearyl acrylate / methacrylic acid / styrene (50/30/20) copolymer 10) 1-alkene mixture of C12 and C14 / maleic acid monostearyl ester / maleic anhydride (50 / Two
0/30) Copolymer 11) C16, C18 1-alkene mixture / maleic acid monoperfluorooctylethyl ester (50/5
0) Copolymer 12) C16, C18 1-alkene mixture / maleic acid monobutyl ester / maleic anhydride (50/25 /
25) Copolymer 13) 1-octadecene / maleic acid monostearyl ester / maleic anhydride (50/15/35) copolymer 14) C20-C28 1-alkene mixture / maleic acid monobutyl ester / maleic acid Anhydrous (50/15 /
35) Copolymer 15) C30-C40 1-alkene mixture / maleic acid monobutyl ester / maleic anhydride (50/12 /
38) Copolymer 16) Stearyl vinyl ether / maleic acid monobutyl ester / maleic anhydride (50/15/35) Copolymer 17) Isobutylene / maleic acid monostearyl ester / maleic anhydride (50/30/20) ) Copolymer

Specific examples of the copolymer (AB) of (a) and (b) include the above-mentioned (AA) portion and the following graft copolymer (b). 1) Styrene homopolymer part 2) Styrene / butyl acrylate (95/5) copolymer part 3) Styrene / butyl acrylate (87/13) copolymer part 4) Styrene / butyl methacrylate (75/25) ) Copolymer part 5) Styrene / butadiene (90/10) copolymer part 6) Bisphenol A propylene oxide 2 mol adduct / isophthalic acid polycondensate part 7) Bisphenol A propylene oxide 2 mol adduct / terephthalic acid polycondensate Condensate part 8) Bisphenol A ethylene oxide 2 mol adduct /
Maleic acid polycondensate part 9) Bisphenol A propylene oxide 3 mol adduct / maleic acid polycondensate part 10) Bisphenol A ethylene oxide 3 mol adduct / terephthalic acid polycondensate part

Examples of the method for producing the polymer (A) of the present invention include the following methods. The polymer (AA) can be obtained by copolymerizing the monomers required to form the desired structure from the beginning according to a known method. For example, it can be obtained by polymerizing (1) using azobisisobutyronitrile as an initiator. Further, after copolymerizing a monomer having a functional group capable of being derived to the target (AA), the monomer may be further reacted to obtain the target copolymer (AA). That is, for example, in the case of the copolymer of (2) and (3-1), (2) and (5-
After copolymerizing 1), alcohols may be reacted to obtain the desired copolymer.

The following method is mentioned as an example of the method for producing the copolymer (AB) bonded in the form of graft or block. Monomer constituting styrene or polyester polymer part (b) having a polymerizable functional group (for example, allyl group) at the terminal and (a) before becoming copolymer part (a) A macromer method in which a polymer is copolymerized to obtain a graft copolymer. A styrene-based or polyester-based polymer part (b) having a functional group (for example, an amino group or a hydroxyl group) capable of reacting with the copolymer part (a) at the terminal and the side of the copolymer part (a) A polymer reaction method for obtaining a copolymer by reacting with a functional group of a chain (for example, a carboxyl group or an acid anhydride group). A styrene-based or polyester-based polymer part (b) having a side chain having a polymerization initiating group (for example, a peroxide group) and a monomer constituting (a) before becoming a copolymer part (a). By reacting with a monomer or by reacting a copolymer moiety (a) having a side chain with a polymerization initiating group with styrene and optionally another copolymerizable monomer. A main chain initiation polymerization method for obtaining a graft copolymer.

The manufacturing method of (a) is basically the same as the above (A).
It is similar to the manufacturing method of A). For example, as a method of introducing a functional group capable of reacting with the terminal functional group of (b) such as a carboxyl group or an acid anhydride group into the side chain of (a),
Since the carboxyl group always contains (a), the production method is the same as that of (AA) above. To introduce the acid anhydride group, (5) is used when the monomer constituting (a) is polymerized. It can be obtained by copolymerizing an acid anhydride group-containing monomer such as 1) in the same manner as in the production method of (AA). Examples of the method of providing a side chain of (a) with a polymerization initiation group include a method of reacting (a) having the acid anhydride group with hydroperoxide. The same effect can be obtained by copolymerizing a small amount of a monomer such as acrylic acid and a lower ester thereof which easily causes chain transfer in (a).

The styrene polymer portion (b1) having the above-mentioned reactive functional group at the terminal or side chain can be synthesized by a known method. For example, a compound having a hydroxyl group at the terminal of (b1) is obtained by radically copolymerizing styrene and another monomer (f) copolymerizable therewith in the presence of a chain transfer agent containing a hydroxyl group (such as mercaptoethanol). Can be obtained at. Polyester polymer part (b
The product having the above-mentioned reactive functional group at the end of 2) can be synthesized by a known method. For example, (b
The compound having a hydroxyl group at the terminal of 2) can be obtained by using the polyol (7) in excess when polycondensing the polyol (7) constituting the (b2) and the polycarboxylic acid (8). Moreover, what has a methacryloyl group at the terminal of (b2) can be obtained by reacting methacryloyl isocyanate with (b2) having a hydroxyl group at the terminal. Also,
(B2) is not necessarily polyol (7) and polycarboxylic acid
It is not necessary to polycondense (8) itself, and the derivative of (7) [lower monocarboxylic acid (acetic acid, etc.) ester, alcoholate, etc.] and / or the derivative of (8) [lower alcohol (methanol, etc.) ester, acid anhydride Object, acid halide, etc.] and the desired polyester polymer part (b
It may be 2).

The charge control agent of the present invention [2] can be mixed with the toner binder in advance before forming the toner and used as the toner binder composition of the present invention having the charge control ability. Examples of the toner binder include the same as those described above, and the same is preferable as the combination of the toner binder and (b) when the charge control agent contains (AB).

Examples of the method for producing the toner binder composition of the present invention include the following methods. A method of polymerizing a monomer capable of obtaining each of the toner binders exemplified above in the presence of the charge control agent. The toner binder and the charge control agent are mixed with a solvent (toluene,
Solution mixing using aromatic hydrocarbons such as xylene, halides such as chloroform and ethylene dichloride, ketones such as acetone and methyl ethyl ketone, and amides such as dimethylformamide, etc. A toner binder and the charge control agent are heat-melted and mixed. Method

The charge control agent of the present invention or the toner binder composition of the present invention can be used as the electrophotographic toner of the present invention containing the same. In the toner binder composition and the electrophotographic toner of the present invention, the weight ratio of the toner binder to the charge control agent is usually 0.1.
-20% by weight, preferably 0.3-10% by weight.
When the weight ratio of (A) is less than 0.1% by weight, the charge amount when used as a toner is low, and when it exceeds 20% by weight, environmental stability when used as a toner is deteriorated.

The composition ratio of the electrophotographic toner of the present invention is based on the weight of the toner. Usually, the total amount of the charge control agent and the toner binder is 40 to 97% by weight, and the coloring material is 0 to 15% by weight. Therefore, 60% by weight or less of magnetic powder (powder of ferromagnetic metal such as iron, cobalt, nickel or a compound such as magnetite, hematite, ferrite) may also be included, which also functions as a coloring material. Further various additives {lubricant (polytetrafluoroethylene,
Low molecular weight polyolefins, fatty acids, or metal salts or amides thereof, etc.) and other charge control agents (metal-containing azo dyes, metal salicylate salts, etc.)} can be contained. In addition, hydrophobic colloidal silica fine powder or the like may be used to improve the fluidity of the toner. The amount of these additives is usually 10% by weight or less based on the weight of the toner.

Further, for the purpose of reducing the particle size of (α) formed by (A), a polymer (γ) having compatibility with (A) and also with a toner binder. Can also be included as a compatibilizer. As (γ), a polymer chain containing 50 mol% or more of a monomer having substantially the same structure as the constituent monomer of (A) and a structure substantially the same as the constituent monomer of the toner binder. A polymer having a polymer chain containing 50 mol% or more of a monomer having a is bonded in a graft or block form. That is, the above (AB) is the most effective compatibilizer, but (γ)
Does not necessarily have charge control ability itself like (AB). Therefore, (γ) does not necessarily have to contain a carboxyl group and may have an alkyl group having 6 to 50 carbon atoms. The amount of (γ) used is usually 0.1 to 30% by weight, preferably 1 to 1 with respect to (A).
It is 0% by weight.

The method for obtaining the electrophotographic toner of the present invention is not particularly limited, but it can be obtained by the following method. Kneading / Pulverizing Method Components constituting a toner are dry-blended, melt-kneaded, coarsely pulverized, and finally atomized by using a jet pulverizer or the like. Further classification is carried out to obtain a toner as fine particles having a particle size of usually 5 to 20 μm. External Addition Method The charge control agent of the present invention is dry-blended with a toner binder, a coloring material and, if necessary, a lubricant and magnetic powder having a particle size of 5 to 20 μm, and then strongly mixed with a mixer while heating if necessary. As a result, externally added toner can be obtained. Polymerization method The charge control agent, the coloring material and the like of the present invention are dispersed and dissolved in the monomer of the toner binder raw material, and then suspended and polymerized in water and dried to obtain a toner having a particle diameter of usually 5 to 20 μm. Is obtained.

The electrophotographic toner of the present invention is mixed with carrier particles such as iron powder, glass beads, nickel powder and ferrite, if necessary, and used as a developer for an electric latent image. The electrophotographic toner of the present invention is fixed on a support (paper, polyester film, etc.) by a copying machine or the like to be used as a recording material. As a method for fixing to the support, a known heat roll fixing method or the like can be applied.

[0057]

The present invention will be further described with reference to the following examples.
The present invention is not limited to this. Hereinafter, parts are parts by weight.

Example A1 Stearyl methacrylate 663 under boiling point in toluene
Parts, methacrylic acid 170 parts and styrene 167 parts,
Polymerization was carried out for 4 hours using 30 parts of azobisisobutyronitrile as an initiator, and then toluene was distilled off to obtain a weight average molecular weight of 1
5,000 charge control agents of the invention (A1) were obtained.

Comparative Example CA1 and Comparative Example CA2 Reaction was carried out in the same manner as in Example A1 except that methacrylic acid was not added to obtain a comparative charge control agent (CA1). A comparative charge control agent (CA2) was obtained by reacting in the same manner as in Example A1 except that stearyl methacrylate was not added.

Example A2 1000 parts of itaconic anhydride was subjected to bulk polymerization at 80 ° C. for 4 hours using 30 parts of azobisisobutyronitrile as an initiator, dissolved in acetone and then precipitated in chloroform. The precipitate was filtered off and dried under reduced pressure to obtain poly (itaconic anhydride) (a).
Then, itaconic anhydride (a) 3 in MIBK under boiling point
695 parts of stearyl alcohol was added to 05 parts of the mixture to carry out a half-esterification reaction for 5 hours to obtain a charge control agent (A2) of the present invention having a weight average molecular weight of 10,000. Charge control agent (A
When the DSC of 2) was measured, an endothermic peak associated with the melting point was shown at 43 ° C.

Comparative Example CA3 Butanol 1 in place of 695 parts of stearyl alcohol
Example A2 except half-esterification using 90 parts
A similar reaction was performed to obtain a comparative charge control agent (CA3).

Example A3 Monolauryl itaconate (980 parts), acrylic acid (10 parts) and methyl acrylate (10 parts) were bulk polymerized at 95 ° C. for 20 hours with 10 parts of azobiscyclohexanecarbonitrile as an initiator. Then, it was dissolved in THF, precipitated in acetone, filtered and dried to obtain a charge control agent (A3) of the present invention having a weight average molecular weight of 12,000. Charge control agent (A3)
The DSC was measured to show a glass transition point at 50 ° C.

Example A4 Monostearyl itaconate (990 parts), acrylic acid (5 parts) and butyl acrylate (5 parts) were polymerized in the same manner as in Example A3 to obtain the charge control agent (A4) of the present invention having a weight average molecular weight of 15,000. Obtained. When the DSC of the charge control agent (A4) was measured, it showed an endothermic peak at 41 ° C. with its melting point.

Example A5 208 parts of maleic anhydride and 220 parts of styrene were copolymerized in EDC at the boiling point with 30 parts of azobisisobutyronitrile as an initiator, and then 572 parts of stearyl alcohol were added to carry out a half-esterification reaction for 5 hours. Then, the charge control agent (A5) of the present invention was obtained.

Comparative Example CA4 Butanol 1 in place of 572 parts of stearyl alcohol
Example A5 except that 57 parts were used for half esterification.
The reaction was carried out in the same manner as above to obtain a comparative charge control agent (CA4).

Example A6 C20-C28 1-alkene mixture (dialene 20)
8: Mitsubishi Kasei Co., Ltd.) 767 parts, maleic anhydride 2
33 parts of the mixture was subjected to polymerization in toluene at a boiling point for 8 hours using 200 parts of azobisisobutyronitrile as an initiator to obtain a copolymer having a weight average molecular weight of 10,000. Then, 26 parts of n-butanol was added and a half-esterification reaction was carried out for 5 hours, and toluene was distilled off to obtain a charge control agent (A6) of the present invention.

Comparative Example CA5 The reaction was performed in the same manner as in Example A6 except that n-butanol was not added to obtain a comparative charge control agent (CA5).

Example A7 C12, C14 1-alkene mixture (dialene 12
4: Mitsubishi Kasei Co., Ltd.) 649 parts, maleic anhydride 3
51 parts were polymerized in the same manner as in Example A6 to give a weight average molecular weight of 1
6,000 copolymers were obtained. Next, 193 parts of stearyl alcohol was added and a half-esterification reaction was carried out for 5 hours, and toluene was distilled off to obtain a charge control agent (A7) of the present invention.

Comparative Example CA6 A comparative charge control agent (CA6) was obtained by the same reaction as in Example A7 except that stearyl alcohol was not added.

Example A8 C30-C40 1-Alkene Mixture (Dialene 3
0: 832 parts by Mitsubishi Kasei Co., Ltd., maleic anhydride 1
68 parts were polymerized in the same manner as in Example A6 to obtain a copolymer having a weight average molecular weight of 9,000. Then n-butanol 1
After adding 5 parts, a half-esterification reaction was carried out for 5 hours, and toluene was distilled off to obtain a charge control agent (A8) of the present invention. When the DSC of the charge control agent (A8) was measured, it showed an endothermic peak at 65 ° C. associated with the melting point.

Comparative Example CA7 In an autoclave, 351 parts of 1-butene and 649 parts of maleic anhydride were polymerized in the same manner as in Example A6 to obtain a copolymer having a weight average molecular weight of 20,000. Then, 59 parts of n-butanol was added and a half-esterification reaction was carried out for 5 hours, and toluene was distilled off to obtain a comparative charge control agent (CA7).

Example A9 C16-C18 1-alkene mixture (dialene 16
8: Mitsubishi Kasei Co., Ltd.) 702 parts, maleic anhydride 2
98 parts were polymerized in the same manner as in Example A6 to give a weight average molecular weight of 1
4,000 copolymers were obtained. Then n-butanol 5
Six parts were added and a half-esterification reaction was carried out for 5 hours, and toluene was distilled off to obtain a charge control agent (A9) of the present invention.

Example A10 900 parts of styrene, 40 parts of maleic anhydride and 60 parts of butyl acrylate were polymerized in toluene under boiling point for 3 hours with 30 parts of azobisisobutyronitrile as an initiator. Toluene was distilled off to obtain a styrene polymer (a) having a weight average molecular weight of 16,000. Styrene-based polymer (a) 500
In the presence of 1 part, at a boiling point in toluene, 398 parts of stearyl methacrylate and 102 parts of methacrylic acid are graft-polymerized for 4 hours by using 13 parts of cumyl hydroperoxide as an initiator, and then toluene is distilled off to control the charge of the present invention. An agent (A10) was obtained.

Comparative Example CA8 and Comparative Example CA9 The reaction was carried out in the same manner as in Example A10 except that methacrylic acid was not added to obtain a comparative charge control agent (CA8). Further, a reaction was carried out in the same manner as in Example A10 except that stearyl methacrylate was not added to obtain a comparative charge control agent (CA9).

Example A11 930 parts of styrene and 70 parts of butyl acrylate were added to 2-
Polymerization was carried out in the presence of 24 parts of mercaptoethanol at a boiling point in toluene with 10 parts of azobisisobutyronitrile as an initiator for 4 hours. Toluene is distilled off and the weight average molecular weight is 1
A styrene-based polymer (b) having a hydroxyl value of 000 and a hydroxyl value of 19 mgKOH / g was obtained. 183 parts of poly (itaconic anhydride) (a) and 400 parts of styrene-based polymer (b) under boiling point in MIBK
Part and 417 parts of stearyl alcohol are added and half-esterification and graft reaction are carried out for 5 hours, then MIBK
Was distilled off to obtain the charge control agent (A11) of the present invention. When the DSC of the charge control agent (A11) was measured, it showed an endothermic peak at 40 ° C. with its melting point.

Comparative Example CA10 Butanol 1 was used instead of 417 parts of stearyl alcohol.
Example A1 except that 14 parts are used for half esterification.
The reaction was performed in the same manner as in 1 to obtain a comparative charge control agent (CA10).

Example A12 To 800 parts of the charge control agent (A3), 200 parts of styrene was further graft-polymerized in xylene at 180 ° C. for 2 hours with 2 parts of ditertiarybutyl peroxide as an initiator, and then xylene was distilled off. The charge control agent (A12) of the invention was obtained.

Example A13 500 parts of the charge control agent (A4) was further graft-polymerized with 500 parts of styrene in the same manner as in Example A12 to obtain the charge control agent (A13) of the present invention. When the DSC of the charge control agent (A13) was measured, an endothermic peak with a melting point was shown at 39 ° C.

Example A14 Maleic anhydride / isobutylene (50/50) copolymer {Isoban-04, manufactured by Kuraray Co., Ltd.} 341 parts, styrene-based polymer (b) 300 parts and stearyl alcohol 3
After adding 59 parts, half-esterification and graft reaction were carried out for 5 hours to obtain the charge control agent (A14) of the present invention.

Comparative Example CA11 Butanol 9 was used instead of 359 parts of stearyl alcohol.
Example CA1 except half esterification using 8 parts
The reaction was performed in the same manner as in 4 to obtain a comparative charge control agent (CA11).

Example A15 860 parts of styrene and 140 parts of butyl acrylate are polymerized for 4 hours at a boiling point in toluene in the presence of 15 parts of 2-aminoethylmercaptan with 5 parts of azobisisobutyronitrile as an initiator, then Toluene was distilled off to obtain a styrene polymer (c) having a weight average molecular weight of 20,000 and an amine value of 11 mgKOH / g. C20-C28 1-alkene mixture (Dialen 208: manufactured by Mitsubishi Kasei Co., Ltd.)
767 parts and 233 parts of maleic anhydride were polymerized in toluene under boiling point using 200 parts of azobisisobutyronitrile as an initiator to obtain a copolymer having a weight average molecular weight of 10,000. Next, 1000 parts of styrene polymer (c) and n
-Butanol (20 parts) was added, half-esterification and graft reaction were carried out for 5 hours, and toluene was distilled off to obtain the charge control agent (A15) of the present invention.

Example A16 C12, C14 1-alkene mixture (dialen 12
4: Mitsubishi Kasei Co., Ltd.) 649 parts, maleic anhydride 3
51 parts were polymerized in the same manner as in Example A15 to obtain a copolymer having a weight average molecular weight of 16,000. Next, 193 parts of stearyl alcohol and 500 parts of styrene-based polymer (b) are added, and half-esterification and graft reaction are carried out for 5 hours,
Toluene was distilled off to obtain the charge control agent (A16) of the present invention.

Example A17 C30-C40 1-alkene mixture (dialen 3
0: 832 parts by Mitsubishi Kasei Co., Ltd., maleic anhydride 1
68 parts were polymerized in the same manner as in Example A15 to obtain a copolymer having a weight average molecular weight of 9,000. Next, 500 parts of styrene-based polymer (b) and 15 parts of n-butanol were added, and 10
Half-esterification reaction was carried out for a period of time, and toluene was distilled off to obtain the charge control agent (A17) of the present invention. When the DSC of the charge control agent (A17) was measured, it showed an endothermic peak at 64 ° C. with its melting point.

Comparative Example CA12 C30-C40 1-alkene mixture was mixed with 1-butene 96
The reaction was performed in the same manner as in Example A17 except that the parts were changed to obtain a comparative charge control agent (CA12).

Example A18 C16-C18 1-alkene mixture (dialene 16
8: Mitsubishi Kasei Co., Ltd.) 702 parts, maleic anhydride 2
98 parts were polymerized in the same manner as in Example A15 to obtain a copolymer having a weight average molecular weight of 14,000. Next, 500 parts of styrene-based polymer (b) and 82 parts of stearyl alcohol were added, and half-esterification and graft reaction were carried out for 10 hours,
Toluene was distilled off to obtain the charge control agent (A18) of the present invention.

Example A19 Bisphenol A Propylene Oxide 2 Mole Adduct 7
40 parts and 330 parts of terephthalic acid were polycondensed at 230 ° C. using 2 parts of dibutyltin oxide as a catalyst, and then 24 parts of methacryloyl isocyanate were reacted in toluene to produce a polyester polymer (a) having a weight average molecular weight of 8,000. Got Polyester polymer (a) 500
In the presence of 1 part, at a boiling point in toluene, 398 parts of stearyl methacrylate and 102 parts of methacrylic acid are polymerized with 30 parts of azobisisobutyronitrile as an initiator, and then toluene is distilled off to graft-charge the present invention. A control agent (A19) was obtained.

Comparative Example CA13 and Comparative Example CA14 A comparative charge control agent (CA13) was obtained by the same reaction as in Example A19 except that methacrylic acid was not added. A comparative charge control agent (CA14) was obtained by the same reaction as in Example A19 except that stearyl methacrylate was not added.

Example A20 Bisphenol A Propylene oxide 2 mole adduct 7
23 parts and 348 parts of isophthalic acid were polycondensed at 230 ° C. using 2 parts of dibutyltin oxide as a catalyst to obtain a polyester polymer (b) having a weight average molecular weight of 6,000 and a hydroxyl value of 20 mgKOH / g. Under a boiling point in MIBK, 400 parts of a polyester polymer (b) and 413 parts of stearyl alcohol are added to 187 parts of poly (itaconic anhydride) (a), and half-esterification and graft reaction are carried out for 5 hours,
A charge control agent (A20) of the present invention was obtained. Charge control agent (A2
When the DSC of 0) was measured, an endothermic peak with a melting point was shown at 40 ° C.

Comparative Example CA15 Butanol 1 was used in place of 413 parts of stearyl alcohol.
Example A2 except half esterification using 13 parts
Reaction was performed in the same manner as in 0 to obtain a comparative charge control agent (CA15).

Example A21 Monolauryl itaconate (784 parts), acrylic acid (8 parts) and methyl acrylate (8 parts) were added to a polyester polymer (a).
Polymerization was carried out in the presence of 200 parts at a boiling point in MEK using 10 parts of azobiscyclohexanecarbonitrile as an initiator for 20 hours, and then MEK was distilled off to obtain a grafted charge control agent (A21) of the present invention.

Example A22 494 parts of monostearyl itaconic acid, 3 parts of acrylic acid and 3 parts of butyl acrylate were polymerized in the presence of 500 parts of the polyester polymer (a) in the same manner as in Example A21, and grafted. The charge control agent (A22) of the invention was obtained. When the DSC of the charge control agent (A22) was measured, it was 4
An endothermic peak with a melting point was shown at 0 ° C.

Example A23 Maleic anhydride / isobutylene (50/50) copolymer {Isoban-04, manufactured by Kuraray Co., Ltd.} To 341 parts were added 300 parts of the polyester polymer (b) and 359 parts of stearyl alcohol. Reaction was carried out in the same manner as in Example A14 to obtain the charge control agent (A23) of the present invention.

Comparative Example CA16 Comparative charge control agent (CA16) was obtained in the same manner as in Example A23 except that 359 parts of stearyl alcohol were replaced with 98 parts of butanol.

Example A24 Bisphenol A Propylene Oxide 2 Mole Adduct 7
40 parts and 330 parts of terephthalic acid were polycondensed at 230 ° C. using 2 parts of dibutyltin oxide as a catalyst to obtain a polyester polymer (c) having a weight average molecular weight of 8,000. 380 parts of a C20-C28 1-alkene mixture (Dialene 208: manufactured by Mitsubishi Kasei Co., Ltd.) and 115 parts of maleic anhydride were polymerized with 100 parts of azobisisobutyronitrile as an initiator under a boiling point in toluene, and weighted. Average molecular weight 1
A copolymer of 0,000 was obtained. Then, 495 parts of the polyester polymer (c) and 10 parts of n-butanol were added, and a half-esterification and graft reaction were carried out for 5 hours, and toluene was distilled off to obtain the charge control agent (A24) of the present invention.

Example A25 1-alkene mixture of C12 and C14 (dialen 12
4: Mitsubishi Kasei Co., Ltd.) 389 parts, maleic anhydride 21
1 part was polymerized in the same manner as in Example A24 to give a weight average molecular weight of 1
6,000 copolymers were obtained. Next, 116 parts of stearyl alcohol and 400 of a polyester-based polymer (b)
Was added to carry out half-esterification and graft reaction for 5 hours, and toluene was distilled off to obtain a charge control agent (A25) of the present invention.

Example A26 C30-C40 1-alkene mixture (dialen 3
0: Mitsubishi Kasei Co., Ltd.) 413 parts, maleic anhydride 83
Parts were polymerized as in Example A24 to give a weight average molecular weight of 9,
000 copolymers were obtained. Next, 496 parts of the polyester-based polymer (b) and 8 parts of n-butanol were added, and a half-esterification and graft reaction were carried out for 10 hours, and toluene was distilled off to obtain a charge control agent (A26) of the present invention.

COMPARATIVE EXAMPLE CA17 C30-C40 1-alkene mixture was mixed with 1-butene 48.
A reaction was performed in the same manner as in Example A26 except for changing parts to obtain a comparative charge control agent (CA17).

Example A27 C16-C18 1-alkene mixture (dialene 16
8: Mitsubishi Kasei Co., Ltd.) 337 parts, maleic anhydride 14
3 parts were polymerized as in Example A24 to give a weight average molecular weight of 1
4,000 copolymers were obtained. Next, 480 parts of the polyester polymer (b) and 40 parts of stearyl alcohol were added and a half-esterification and graft reaction were carried out for 10 hours, and toluene was distilled off to obtain the charge control agent (A27) of the present invention.

Example B1 30 parts of the charge control agent (A2), and a styrene-based toner binder {Haimer UNI-3000, Sanyo Chemical Industry Co., Ltd.
(Manufactured by Co., Ltd.) 1000 parts was dissolved and mixed in toluene. Toluene was removed to obtain a toner binder composition (B1) of the present invention.

Example B2 Instead of 30 parts of the charge control agent (A2), the charge control agent (A2)
9) Mix as in Example B1 except that 25 parts are used,
A toner binder composition (B2) of the present invention was obtained.

Example B3 A charge control agent (A1) was used in place of 30 parts of the charge control agent (A2).
1) Mix as in Example B1 except that 40 parts are used,
A toner binder composition (B3) of the present invention was obtained.

Example B4 A charge control agent (A1) was used instead of 30 parts of the charge control agent (A2).
8) Mix as in Example B1 except that 40 parts are used,
A toner binder composition (B4) of the present invention was obtained.

Example B5 Bisphenol A Propylene Oxide 2 Mol Adduct 4
Polyester toner binder (a) having a weight average molecular weight of 8,000, obtained by polycondensing 17 parts, 341 parts of a 2 mol adduct of bisphenol A ethylene oxide and 310 parts of terephthalic acid with 2 parts of dibutyltin oxide as a catalyst.
Got 40 parts of the charge control agent (A20) and 1000 parts of the toner binder (a) were mixed in the same manner as in Example B1 to obtain a toner binder composition (B5) of the present invention.

Example B6 50 parts of the charge control agent (A27) and 1000 parts of the toner binder (a) were mixed in the same manner as in Example B1 to obtain a toner binder composition (B6) of the present invention.

Examples T1 to T12 and Comparative Examples CT1 to
CT7 A charge control agent having the composition shown in Table 1 and a styrene-based toner binder {Heimer UNI-3000, manufactured by Sanyo Chemical Industry Co., Ltd.} 1
000 parts, carbon black {MA-100, Mitsubishi Kasei
Toner of 80 parts of low molecular weight polypropylene {Viscole 660P, manufactured by Sanyo Kasei Kogyo Co., Ltd.} was produced by the following method. First, Henschel mixer {FM10
B, manufactured by Mitsui Miike Kakoki Co., Ltd.} after premixing,
The kneading was performed using a biaxial kneader {PCM-30, manufactured by Ikegai Co., Ltd.}.
Then, after finely pulverizing using a supersonic jet crusher Lab Jet {made by Nippon Pneumatic Mfg. Co., Ltd.}, it was classified by an air stream classifier {MDS-I, made by Japan Pneumatic Mfg. Co., Ltd.} to 5-20 μm. To obtain a powder having a particle size of, and the toners (T1) to (T12) of the present invention and the comparative toner (CT1) to
(CT7) was obtained. The physical properties of the toner are shown in Table 1, and the evaluation results are shown in Table 2.

Example T13 (Synthesis of Compatibilizer) 500 parts of stearyl acrylate were polymerized with 20 parts of azobisisobutyronitrile as an initiator in xylene under boiling point. In the presence of the polymer, 500 parts of styrene was further graft polymerized at 180 ° C. with 5 parts of ditert-butyl peroxide as an initiator to obtain a compatibilizer (a). (Preparation and Evaluation of Toner) Toner of the present invention (T13) was obtained in the same manner as in Example T1 except that 6 parts of the compatibilizer (a) was further added. Toner physical property values are shown in Table 1, and evaluation results are shown in Table 2.

[0109]

[Table 1] Toner composition and physical property values ------------------------------------------------------------------------ Toner No Charge control agent Acid value of SP value difference (α) Average No. of free acid groups (α) Addition amount (SPa-SPb) [mgKOH / g] Ratio [%] Particle size [μm] −−−−−−−−−−−−−−−−−−−−−−−−−−−−−− −−−−−− (T1) (A1) 30 parts −0.76 111 100 0.7 (T2) (A2) 15 parts −0.66 160 91 0.7 (T3) (A2) 30 parts −0 .66 160 91 0.8 (T4) (A2) 45 parts -0.66 160 91 91 0.8 (T5) (A3) 30 parts -0.30 192 100 0.6 (T6) (A4) 30 parts- 0.68 149 100 0.7 (T7) (A5) 30 parts -0.48 119 100 0.5 (T8) (A6) 25 parts -1.25 241 8 0.6 (T9) (A7) 25 parts -1.03 304 11 0.5 (T10) (A8) 13 parts -1.45 177 6 0.7 (T11) (A8) 25 parts -1.45 177 6 0.7 (T12) (A8) 50 parts -1.45 177 6 0.7 (T13) (A1) 30 parts * -0.76 111 111 100 0.3 --------------------------- −−−−−−−−−−−−−−−− (CT1) (CA1) 25 parts −1.240 −0.9 (CT2) (CA2) 10 parts +0.15 329 100 5 (CT3) ) (CA3) 22 parts +1.00 327 89 8 (CT4) (CA4) 30 parts +0.80 204 100 7 (CT5) (CA5) 25 parts −1.29 2660 0.6 (CT6) (CA6) 25 Part −0.96 4020 0.5 (CT7) (CA7) 25 parts +0.23 660 6 10 −−−−−−−−−−−−−−−−−−−−−−−−−−−− −−−−−−−−− *: Further, 6 parts of compatibilizer (a) was added.

[0110]

[Table 2] Evaluation results −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− Toner name Charge amount Standing environment Copy (μC / g) Increase Dependency test --------------------------------- (-)-(-)-(T1) -19BA (T2) -17BB (T3) ) -30 A A (T4) -43 A A (T5) -27 A A A (T6) -31 A A A (T7) -24 B A (T8) -30 A A A (T9) -26 A A A (T10) -13 BB (T11) -33 A A A (T12) -49 A A (T13) -18 B A ------------------------- −−−−−−−−−−− (CT1) −8 C B (CT2) −12 B C (CT3) −13 B B (CT4) −7 B B (CT5) −14 B B C (CT6) -1 B B C (CT7) -8 C B C C --------------------------- (Evaluation method) Developer adjustment 1 part of toner and ferrite carrier for electrophotography {F-1
50 parts, manufactured by Powder Tech Co., Ltd.} 24 parts were mixed to prepare a developer. Measurement of saturation charge amount (charge amount) H. After conditioning the humidity for 8 hours or more, use a Turbula shaker mixer at 50 rpm.
Friction stirring was conducted for × 1, 3, 7, 20, 60 and 120 minutes, and the charge amount was measured at each time. The amount of charge during the friction time when the increase in the amount of charge disappeared was defined as the saturated amount of charge. Measuring device: Blow-off charge amount measuring device {Toshiba Chemical
Evaluation Co., Ltd. of Charge Rise (Rise) Evaluation Based on the above charge amount measurement results, the following criteria were evaluated. A: A friction time of less than 20 minutes to reach a charge amount of 80% of the saturated charge amount B: A friction time of 20 to 60 minutes to reach a charge amount of 80% of the saturated charge amount C: A saturated charge amount Of which the friction time of reaching 80% of the charge amount is more than 60 minutes. Measurement of environmental dependence The charge amount of the above developer whose humidity was adjusted for 8 hours or more at high temperature and high humidity and low temperature and low humidity was measured. Low temperature and low humidity: 10 ° C., 40% R. H. High temperature and high humidity: 30 ° C., 80% R. H. Evaluation criteria A: Small change in charge amount at low temperature and low humidity and high temperature and high humidity B: Medium change in charge amount at low temperature and low humidity and high temperature and high humidity C: Charge amount at low temperature and low humidity and high temperature and high humidity The copying test was carried out by using a copying machine for evaluation. Evaluator: Electrophotographic copying machine for toner using negative charge toner using selenium photoconductor Continuous copying number: 20,000 Evaluation criteria A: 20,000 sheets Good image after continuous copying B: 20,000 sheets after continuous copying, Deteriorated image quality C: Defect image from the beginning of copying

Examples T14 to T25 and Comparative Example CT8
-CT13 Toners (T14) to (T25) of the present invention and comparative toner (CT8) were formed into toner with the compositions shown in Table 3 in the same manner as in Example T1.
(CT13) was obtained. The physical properties of the toner are shown in Table 3, and the evaluation results are shown in Table 4.

[0112]

[Table 3] Toner composition and physical property values -------------------------------------------------------- Toner No Charge control agent SP Acid value of value difference (α) Average No. of free acid groups (α) Addition amount (SPa-SPb) [mgKOH / g] Ratio [%] Particle size [μm] −−−−−−−−−−−−−−−−−−−−−−−−−−−−−− −−−−−− (T14) (A10) 50 parts −0.97 132 100 0.3 (T15) (A11) 20 parts −0.69 152 99 0.2 (T16) (A11) 40 parts −0 .66 160 99 0.2 (T17) (A11) 60 parts −0.66 160 99 0.2 (T18) (A12) 30 parts −0.30 192 100 0.1 (T19) (A13) 50 parts − 0.68 149 100 0.08 (T20) (A14) 40 parts -0.57 230 54 0.4 (T21) (A15) 50 parts -1.25 217 8 0.3 (T22) (A16) 40 parts -1.03 295 15 0.3 (T23) (A17) 20 parts -1.45 168 12 0.4 (T24) (A17) 40 parts -1.45 168 12 0.4 (T25) (A17) Part 0 -1.45 168 12 0.4 ---------------------------- (-). (CT8) ( CA8) 45 parts -1.53 0-0.5 (CT9) (CA9) 30 parts +2.11 652 100 3 (CT10) (CA10) 35 parts +0.94 299 99 0.8 (CT11) (CA11) 30 Part +0.44 368 54 0.9 (CT12) (CA12) 40 parts +1.39 651 12 0.4 (CT13) -No addition --- --- ------------------- −−−−−−−−−−−−−−−−−−−−

[0113]

[Table 4] Evaluation results --------------------------------------------- toner name charge amount standing environment copy environment charge amount (μC / g) Rising dependence test Distribution −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− (T14) −19 B A A A (T15) -16 B B B B (T16) -26 A A A A (T17) -36 A A A (T18) -23 A A A A (T19) -22 A A A A (T20) -24 B A A A (T21) -25 A A A A A (T22) -21 B A A A (T23) -16 B B B B (T24) -28 A A A A A (T25) -44 A A A A −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− (CT8) −8 C B C B (CT9) −12 B C C C (CT10) -14 B B C (CT11) -13 BBCB (CT12) -11 CBBA (CT13) -8CCCCB -------------------------------- −−−−−−−−−−−−− (Evaluation method) Adjustment of developer Measurement of saturated charge amount (charge amount) Evaluation criterion of rise of charge (rise) Measurement of environment dependence The copy test was conducted in Example T1. The same was done. The charge amount distribution was measured by the following method. Measurement of charge amount distribution The above-mentioned developer was heated at 23 ° C. and 50% R.V. H. After conditioning the humidity for 8 hours or more, use a Turbula shaker mixer at 50 rpm.
The mixture was friction stirred for 20 minutes, and the charge amount distribution was measured. Device: Particle charge distribution measuring device {EST-1, manufactured by Hosokawa Micron Co., Ltd.} Evaluation criteria A: Narrow charge distribution B: Medium charge distribution C: Wide charge distribution

Examples T26 to T37 and Comparative Example CT1
4-CT19 (Synthesis of toner binder) 751 parts of bisphenol A propylene oxide 2 mol adduct, terephthalic acid 10
4 parts and 167 parts of trimellitic anhydride were polycondensed using 2 parts of dibutyltin oxide as a catalyst, and the softening point was 127 ° C.
To obtain a polyester toner binder (b). (Preparation and Evaluation of Toners) Toners of the present invention (T26) to (T37) and toners of the compositions shown in Table 5 were prepared in the same manner as in Example T1 except that the toner binder was changed to the polyester toner binder (b). Comparative toner (CT1
4) to (CT19) were obtained. The physical properties of the toner are shown in Table 5, and the evaluation results are shown in Table 6.

Examples T38 and T39 1000 parts of a polyester-based toner binder (a), 40 parts of a charge control agent (A20), and 50 parts of a colorant {FastGen Magenta R-11, manufactured by Dainippon Ink and Chemicals, Inc.} were carried out. The toner of the present invention (T
38) was obtained. Similarly, 50 parts of the charge control agent (A27) was used to form a toner, and the toner (T39) of the present invention was obtained. The evaluation results are shown in Table 6.

[0116]

[Table 5] Toner composition and physical property values ----------------------------------------------------------------------------- Toner No Charge control agent Acid value of SP value difference (α) Average No. of free acid groups (α) Addition amount (SPa-SPb) [mgKOH / g] Ratio [%] Particle size [μm] −−−−−−−−−−−−−−−−−−−−−−−−−−−−−− ---------- (T26) (A19) 50 parts -1.51 132 100 0.4 (T27) (A20) 20 parts -1.27 152 99 0.3 (T28) (A20) 40 parts -1 .27 152 99 0.3 (T29) (A20) 60 parts −1.27 152 99 0.3 (T30) (A21) 30 parts −0.88 192 100 0.2 (T31) (A22) 50 parts − 1.26 149 100 0.1 (T32) (A23) 40 parts -1.15 230 54 0.6 (T33) (A24) 50 parts -1.83 217 8 0.6 (T34) (A25) 25 parts -1.61 295 15 0.4 (T35) (A25) 50 parts -1.61 295 12 0.4 (T36) (A25) 75 parts -1.61 295 12 0.4 (T37) (A26) 5 Part -2.05 168 12 0.7 ----------------------------------------------- (CT14) -Not Addition ----- (CT15) (CA13) 45 parts -2.110 -0.7 (CT16) (CA14) 30 parts +1.53 329 100 0.5 (CT17) (CA15) 35 parts +0.36 299 99 0.5 (CT18) (CA16) 30 parts -0.14 368 54 0.9 (CT19) (CA17) 50 parts +0.81 651 12 0.5 ----------------- −−−−−−−−−−−−−−−−−−−−−−

[0117]

[Table 6] Evaluation results ------------------------------------------------ toner name charge amount standing environment copy environment charge amount Transparency (μC / g) rise Dependency test Distribution −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− (T26) -20 B A A A A (T27) -18 B B B A (T28) -28 A A A A A (T29) -39 A A A A A (T30) -26 A A A A A A (T31) -26 A A A A A A (T32) -25 B A A A A B (T33) -27 A A A A A B (T34) -19 B A A A A (T35) -28 A A A A A A (T36) -39 A B A A (T37) −32 A A A A B (T38) −27 A A A A A A (T39) −27 A A A A A −−−−−−−−−−−−−−−−−− −−−−−−−−−−− −−−−−−− (CT14) −11 C C C B B A (CT 15) −13 C B C B B B (CT 16) −15 B C C B B A (CT 17) −15 B C C B B A (CT 18) -14 B B C B B (CT19) -16 B B C B B --- --- --- --- --- --- --- --- --- --- --- --------------- -(Evaluation method) Adjustment of developer Measurement of saturated charge amount (charge amount) Evaluation standard of charge rise (rise) Measurement of environmental dependence Copy test Measurement of charge amount distribution was performed in the same manner as in Example T14. The transparency was measured by the following method. Evaluation of Transparency Only the toner binder and the charge control agent are kneaded without adding a colorant and low molecular weight polypropylene, and then the kneaded product is molded into a cylinder of about 5 mm by using a melt indexer and its transparency is improved. It was visually judged. Evaluation criteria A: Transparent B: Slightly turbid C: White turbid state

Examples T40 to T45 Toner binder compositions (B1) to (B6) having the compositions shown in Table 7 were made into toner in the same manner as in Example T1. The evaluation results are shown in Table 8.

[0119]

[Table 7] Toner composition ----------------------------------------------------------- Toner binder composition Coloring agent Low molecular weight polypropylene toner name ----------------------------------- Addition amount type Addition amount type Addition amount −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− (T40) (B1) 1030 parts MA -100 * 80 copies 660P ** 40 copies (T41) (B2) 1025 copies MA-100 * 80 copies 660P ** 40 copies (T42) (B3) 1040 copies MA-100 * 80 copies 660P ** 40 copies (T43) ) (B4) 1040 parts MA-100 * 80 parts 660P ** 40 parts (T44) (B5) 1040 parts R-11 *** 50 parts-No addition (T45) (B5) 1050 parts R-11 *** 50 parts-non-added --------------------------------------- *: Carbon black MA-100, Mitsubishi Kasei Co., Ltd. ) **: Viscole 660P, Sanyo Kasei Co., Ltd. ***: Fast Gen Magenta R-11, Dainippon Ink and Co., Ltd.

[0120]

[Table 8] Evaluation results --------------------------------------------- toner name charge amount standing environment copy environment charge amount Transparency (μC / g) rise Dependence test Distribution −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− (T40) -32 A A (T41) -28 A A A (T42) -25 A A A A (T43) -24 A A A A (T44) -26 A A A A A (T45) -25 A A A A A A ------------------------------------- (Evaluation method) The evaluation was performed in the same manner as in Example T26.

[0121]

The charge control agent, toner binder composition and electrophotographic toner of the present invention have the following effects. 1. Since it does not contain heavy metals, it has excellent safety. 2. Since the charge control agent is weakly colored, the color tone of the color toner is excellent. 3. The transparency of the toner is high, and the color tone of the color toner is excellent. 4. The charge control agent has high dispersibility and a toner having a sharp charge amount distribution can be obtained. 5. The charge amount of the charge control agent is high, and a toner having an appropriate charge amount can be obtained by using a small amount of the charge control agent. 6. It is possible to obtain a toner that is excellent in charging rise and reaches a certain amount of charge with a short time friction. 7. It is possible to obtain a toner that is excellent in environmental dependence and has a small change in charge amount even under various environments. 8. Even when repeated continuous copying for a long period of time, a toner with little fogging and stably holding a clear image can be obtained.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (31) Priority claim number Japanese Patent Application No. 5-307227 (32) Priority date Hei 5 (1993) November 12 (33) Country of priority claim Japan (JP) (31) Priority Claim number Japanese Patent Application No. 5-309867 (32) Priority date No. 5 (1993) November 16 (33) Country of priority claim Japan (JP) (31) No. of priority application Japanese Patent Application No. 5-309868 (32) Priority Hihei 5 (1993) November 16 (33) Priority claiming country Japan (JP) (72) Inventor Naoki Takase 1-11, Hitotsubashi-honcho, Higashiyama-ku, Kyoto Sanyo Chemical Industry Co., Ltd. (72) Inventor Otani 1 Sanyo Kasei Kogyo Co., Ltd., 1-11, Hitotsubashi-honmachi, Higashiyama-ku, Kyoto

Claims (21)

[Claims] 1. An electrophotographic toner containing a toner binder, a coloring material, and a charge control agent comprising a polymer having an acid group, wherein at least a part of the toner binder forms a continuous phase, and the charge control agent At least a part of the charge control agent forms a discontinuous domain, and the SP value (SPa) of the polymer chain portion (α) forming the discontinuous domain in the charge control agent and the continuous phase in the toner are formed. SP value of toner binder (β) (SP
b) difference (SPa-SPb) is -2.5 to 0, the acid value of (α) is 50 to 400, and at least 3% of the acid groups giving the acid value are free acid groups. An electrophotographic toner characterized by the following. 2. The electrophotographic toner according to claim 1, wherein the particle size of the domain formed by (α) is 0.01 to 0.8 μm. 3. The electrophotographic use according to claim 1, wherein (α) has a melting point of 25 to 100 ° C. or a polymer chain portion having no glass melting point but a glass transition point of 25 to 100 ° C. toner. 4. Further, it has compatibility with (α),
The toner for electrophotography according to claim 1, further comprising a polymer (γ) having a compatibility with (β) as a compatibilizing agent. 5. The toner for electrophotography according to claim 1, wherein the polymer having an acid group is a polymer (A) having an alkyl group having 6 to 50 carbon atoms and a carboxyl group. 6. A polymer (A) having an alkyl group having 6 to 50 carbon atoms and a carboxyl group, wherein (A) is an α, β-unsubstituted compound having an alkyl group having 6 to 50 carbon atoms as an essential constituent unit. (Co) polymer (A) containing at least 5 mol% of saturated dicarboxylic acid monoalkyl ester (1)
1), and an ethylenically unsaturated monomer having an alkyl group having 6 to 50 carbon atoms as an essential constituent unit (2) 6 to 80
A charge control agent, which is a polymer selected from a copolymer (A2) containing mol% and α, β-unsaturated mono- or dicarboxylic acid (3) of 5 to 75 mol%. 7. The charge control agent according to claim 6, wherein (1) is an itaconic acid monoalkyl ester. 8. (2) is an alkyl ester-based ethylenically unsaturated monomer (2-1) having an alkyl group having 6 to 50 carbon atoms and an α-olefin (2-
The charge control agent according to claim 6, which is 2) or an alkyl vinyl ether (2-3) having an alkyl group having 6 to 50 carbon atoms. 9. (3) is an α, β-unsaturated dicarboxylic acid monoester (3-1), an α, β-unsaturated dicarboxylic acid monoamide (3-2) or a (meth) acrylic acid (3-).
The charge control agent according to claim 6, which is 3). 10. (A) is selected from a styrene-based polymer portion (b1) and a polyester-based polymer portion (b2) in addition to the polymer portion (a) having an alkyl group having 6 to 50 carbon atoms and a carboxyl group. The charge control agent according to any one of claims 6 to 9, wherein the polymer portion (b) to be formed is a copolymer (AB) bonded in a graft or block form. 11. A styrene-based polymer comprising 1 to 100% by weight of (AB), 0 to 99% by weight of a polymer (AA) consisting only of a polymer portion having an alkyl group having 6 to 50 carbon atoms and a carboxyl group. The charge control agent according to claim 10, which contains 0 to 90% of a polymer (B) selected from (B1) and a polyester polymer (B2). 12. The charge control agent according to claim 11, which contains 50 mol% or more of styrene as a constituent unit of each of (b1) and (B1). 13. (b2) is a polyester polymer portion of a polyol composed of an alkylene oxide adduct of a bisphenol and a polycarboxylic acid, and (B2) is a polyol composed of an alkylene oxide adduct of a bisphenol and a polycarboxylic acid. The charge control agent according to claim 11, which is a polyester polymer with an acid. 14. The total weight of (a) and (AA) (W
The charge control agent according to any one of claims 11 to 13, wherein a ratio (Wa / Wb) of a) to the total weight (Wb) of (b) and (B) is 99/1 to 10/90. 15. A toner binder composition comprising a toner binder and the charge control agent according to claim 6. 16. A toner binder and a toner binder.
The charge control agent according to any one of (1) to (4) is used, the toner binder is a styrene-based polymer, and (b) is (b).
The toner binder composition of 1). 17. A toner binder and a toner binder.
A toner binder composition comprising the charge control agent according to any one of 1 to 3, the toner binder is a polyester polymer, and (b) is (b2). 18. An electrophotographic toner containing a toner binder, a coloring material, and a charge control agent, wherein the electrophotographic toner contains the charge control agent according to any one of claims 5 to 13. 19. A toner binder and the charge control agent according to claim 6, further comprising:
An electrophotographic toner comprising a polymer having compatibility with (A) and also having compatibility with a toner binder as a compatibilizing agent. 20. A toner binder and any one of claims 10 to 14.
The charge control agent according to any one of (1) to (4) is used, the toner binder is a styrene-based polymer, and (b) is (b).
1) An electrophotographic toner. 21. A toner binder and claims 10-14
An electrophotographic toner comprising the charge control agent according to any one of 1 to 3, the toner binder is a polyester polymer, and (b) is (b2).