JPH1115192A - Production of electrostatic charge image developing toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the developer superior in positive charge stability and small in deterioration of image quality due to fluctuation of a charge amount at the time of long-running printing. SOLUTION: This electrostatic charge image developing toner is manufactured by suspension polymerizing a polymerizable monomer in a suspension liquid medium containing a colorant and an inorganic dispersant in the presence of a quaternary ammonium base-containing copolymer having vinylarylhydrocarbon units and quaternary ammonium base-containing (meth)acrylate units, and the inorganic dispersant is a cationic dispersant, and the quaternary ammonium base-containing copolymer has a weight average molecular weight of 25,000-1,000,000 and contains the quaternary ammonium base-containing (meth) acrylate units in a mode fraction of 0.01-0.4 mol.%, and this quaternary ammonium base-containing copolymer is contained in an amount of 0.01-10 weight% of the monomer to be suspension polymerized.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a toner which is excellent in positive charging stability and hardly deteriorates image quality due to fluctuations in the amount of charge during durable printing.

[0002]

2. Description of the Related Art Conventionally, an electrostatic latent image formed in an image forming apparatus such as an electrophotographic apparatus or an electrostatic recording apparatus is first developed by a developer, and then the formed developer image Is transferred onto a transfer material such as paper, and then fixed by various methods such as heating, pressing, and solvent vapor.

An image formed by an image forming apparatus is
Every year, the demand for its definition is increasing. Conventionally, a pulverizing developer obtained by melting, pulverizing, and classifying a resin containing a colorant or the like has been mainly used as a developer used in the apparatus. However, particle size control is easy, and complicated steps such as classification are required. Attention has been paid to a polymerization method developer which is said to require no complicated production steps. In the positively charged developing method, the formation of a latent image on a photoreceptor is more precise than in the negatively charged method, and a high-resolution image can be formed by combining with a polymerization toner having a small particle diameter.

As a non-magnetic one-component positively charged polymerization method developer,
JP-A-59-123852 proposes a method in which a polymerizable monomer and a cationic polymer are subjected to suspension polymerization in an anionic dispersant. She lacked gender. For unknown reasons,
It is considered that the ionic attraction between the cationic polymer and the anionic dispersant was too large, the anionic dispersant was taken into the toner, and the washing was not sufficient. In such a developer, a developing method based on frictional charging from a sleeve or a blade, such as a non-magnetic one-component, has a drawback that the developer does not have sufficient charging ability and fog occurs. JP-A-3-175456 proposes a method of obtaining a toner by suspension polymerization in the presence of a quaternary ammonium base-containing copolymer. However, such a developer has a large charge amount and a low print density. Since the copolymer is low and the weight average molecular weight of the quaternary ammonium group-containing copolymer is low, there is a problem that the fluidity of the developer is insufficient and the storage stability is reduced.
Japanese Patent Application Laid-Open No. 6-27740 proposes a toner in which a quaternary ammonium salt-containing thermoplastic resin is chemically bonded to a negatively chargeable charge controlling agent. There is a disadvantage that it cannot be used for a one-component positively charged developer.

[0005]

SUMMARY OF THE INVENTION Based on such prior art, the present inventors have developed a developing method which has good preservability, excellent positive charge stability, and little image quality deterioration due to fluctuations in the amount of charge during durable printing. As a result of intensive studies to obtain the agent, an oil-soluble monomer consisting of a vinyl aromatic hydrocarbon monomer and a (meth) acrylate monomer and a certain quaternary ammonium base-containing (meth) acrylate monomer It has been found that the above object can be achieved by using a non-magnetic one-component positively charging developer which polymerizes a polymerizable monomer in the presence of a quaternary ammonium base-containing copolymer obtained by copolymerization. Based on this, the present invention has been completed.

[0006]

Thus, according to the present invention, at least a repeating structural unit derived from a vinyl aromatic hydrocarbon (hereinafter referred to as a vinyl aromatic hydrocarbon unit) and a repeating structural unit derived from a (meth) acrylate (hereinafter referred to as a "method"). ,
(Meth) acrylate unit) and a quaternary ammonium base-containing copolymer having a quaternary ammonium base-containing (meth) acrylate-derived repeating structural unit (hereinafter referred to as a quaternary ammonium base-containing (meth) acrylate unit). A method for producing a toner for electrostatic image development in which a polymerizable monomer is suspension-polymerized in a suspension medium containing a colorant and an inorganic dispersant, wherein the inorganic dispersant is a cationic dispersant. The weight average molecular weight A of the quaternary ammonium base-containing copolymer in terms of polystyrene measured by gel permeation chromatography using tetrahydrofuran is 25,000 to 1,000,
The quaternary ammonium salt group-containing copolymer has a molar fraction B of 0.01 to 0.4 mol% of the repeating structural unit of the quaternary ammonium salt group-containing (meth) acrylate structure. A method for producing a toner for developing an electrostatic image, wherein the amount (parts by weight) C of the copolymer is 0.01 to 10 parts by weight based on 100 parts by weight of the monomer to be subjected to suspension polymerization. Is done. Hereinafter, the present invention will be described in detail.

The quaternary ammonium salt group-containing copolymer used in the present invention is:
It has a vinyl aromatic hydrocarbon unit, a (meth) acrylate unit, and a quaternary ammonium salt group-containing (meth) acrylate unit.

(Vinyl aromatic hydrocarbon unit) The vinyl aromatic hydrocarbon unit referred to in the present invention is a structural unit represented by the following formula (1A).

[0009]

Embedded image In the formula (1A), R ¹ is a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms, preferably a hydrogen atom or a methyl group, and R ² and R ³ are a hydrogen atom, a halogen atom, or a carbon atom. It is a linear or branched alkyl group of the formulas 1-3, preferably a hydrogen atom or a methyl group. In the present invention, a halogen atom is a fluorine atom, a chlorine atom,
A bromine atom or an iodine atom, preferably a chlorine atom or a bromine atom.

[0010] These vinyl aromatic hydrocarbon units may be used alone or in combination of two or more.

((Meth) acrylate unit) The (meth) acrylate unit referred to in the present invention is a structural unit represented by the following formula (2A).

Embedded image In the formula (2A), R ¹ is a hydrogen atom or a methyl group;
R ² is a linear, branched, or cyclic alkyl group having 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms, or a carbon atom having 1 or more hydrogen atoms substituted with a halogen atom or a hydroxyl group. 12, preferably a linear, branched or cyclic substituted alkyl group having 1 to 6 carbon atoms. These (meth) acrylic rate units can be used alone,
It may be a combination of two or more.

(Quaternary ammonium salt group-containing (meth) acrylate unit) The quaternary ammonium salt group-containing (meth) acrylate unit in the present invention is a structural unit represented by the following formula (3A). These (meth) acrylate units containing a quaternary ammonium base may be used alone or in combination of two or more.

[0013]

Embedded image In the formula (3A), R ¹ is a hydrogen atom or a methyl group, R ² is the following formula (3a1), and R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom or a carbon atom having 1 to 6 carbon atoms. Straight chain,
It is a branched or cyclic alkyl group, and X is a halogen atom or the following formula (3a2).

[0014]

Embedded image In the formula (3a1), R ′ and R ″ are a hydrogen atom, a halogen atom, or an alkyl group having 1 to 3 carbon atoms which may be branched.

[0015]

Embedded image In the formula (3a2), R ¹ is a hydrogen atom, a linear, branched, or cyclic alkyl group or a halogen atom having 1 to 6 carbon atoms, and A is a hydrogen atom, a linear, branched, or branched chain having 1 to 6 carbon atoms. ,
Or a cyclic alkylene, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms or phenylene which may have a halogen atom, or a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms Or naphthylene which may have a halogen atom, and M is SO ₃ ⁻ ,
PO ₃ ^-, or BO ₃ ^- is.

In the formula (3A), R ³ and R ⁴ are each independently preferably a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms, and R ⁵ is a linear alkyl group having 1 to 3 carbon atoms. X is a halogen atom or the following formula (3a
2 ′) is preferred.

Embedded image In the formula (3a2 ′), R ¹ is a hydrogen atom or a group having 1 to 6 carbon atoms.
R ² and R ³ are linear, branched or cyclic alkylene having 1 to 6 carbon atoms, a halogen atom or an alkyl group having 1 to 3 carbon atoms. Phenylene, which may be
Or have a halogen atom or an alkyl group having 1 to 3 carbon atoms is also good naphthylene, M is SO ₃ ^- is.

The quaternary ammonium salt group-containing copolymer having such a structural unit includes (1) a monomer which gives a vinyl aromatic hydrocarbon unit (hereinafter, referred to as a vinyl aromatic hydrocarbon monomer) and (meth) A) a monomer that provides an acrylate unit (hereinafter referred to as a (meth) acrylate monomer) and N, N
-Disubstituted aminoalkyl (meth) acrylate (hereinafter, referred to as
A (meth) acrylate monomer containing an amino group) in the presence of a polymerization initiator, and then quaternizing the amino group using a quaternizing agent, (2) vinyl aromatic hydrocarbon Monomers, monomers that give (meth) acrylate units,
And an amino group-containing (meth) acrylate monomer obtained by quaternizing an amino group-containing (meth) acrylate monomer with a halogenated organic compound (hereinafter, a halogenated quaternary ammonium group-containing (meth) acrylate monomer) ) In the presence of a polymerization initiator and then reacting with an organic acid to form a salt.
And (3) vinyl aromatic hydrocarbon monomers, monomers that give (meth) acrylate units, and (meth) acrylate monomers containing quaternary ammonium bases (4) a copolymer of a vinyl aromatic hydrocarbon monomer and an alkyl (meth) acrylate halide, and a vinyl aromatic hydrocarbon monomer. A method of mixing a copolymer with an amino group-containing (meth) acrylate monomer and quaternizing between the polymers may be mentioned. In addition, a quaternary ammonium base-containing (meth) compound represented by the formula (3A) may be used. The copolymer having a unit in which X in the acrylate unit is a halogen does not require a reaction with an organic acid or a derivative thereof in the method (2). The ratio of each structural unit can be arbitrarily set by changing the charge ratio of each monomer.

(Vinyl Aromatic Hydrocarbon Monomer) The vinyl aromatic hydrocarbon monomer used in the above method is a compound having a structure in which a vinyl group is bonded to an aromatic hydrocarbon. , Styrene, α-methylstyrene,
2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2-ethylstyrene, 3-ethylstyrene,
4-ethylstyrene, 2-propylstyrene, 3-propylstyrene, 4-propylstyrene, 2-isopropylstyrene, 3-isopropylstyrene, 4-isopropylstyrene, 2-chlorostyrene, 3-chlorostyrene, 4-chlorostyrene, 2-methyl-α-methylstyrene, 3-methyl-α-methylstyrene, 4-methyl-
α-methylstyrene, 2-ethyl-α-methylstyrene, 3-ethyl-α-methylstyrene, 4-ethyl-α
-Methylstyrene, 2-propyl-α-methylstyrene, 3-propyl-α-methylstyrene, 4-propyl-α-methylstyrene, 2-isopropyl-α-methylstyrene, 3-isopropyl-α-methylstyrene,
-Isopropyl-α-methylstyrene, 2-chloro-α
-Methylstyrene, 3-chloro-α-methylstyrene,
4-chloro-α-methylstyrene, 2,3-dimethylstyrene, 3,4-dimethylstyrene, 2,4-dimethylstyrene, 2,6-dimethylstyrene, 2,3-diethylstyrene, 3,4-diethylstyrene , 2,4-diethylstyrene, 2,6-diethylstyrene, 2-methyl-3-ethylstyrene, 2-methyl-4-ethylstyrene, 2-chloro-4-methylstyrene, 2,3-dimethyl-α- Methylstyrene, 3,4-dimethyl-α-methylstyrene, 2,4-dimethylstyrene, 2,6-dimethyl-α-methylstyrene, 2,3-diethyl-α-methylstyrene, 3,4-diethyl-α -Methylstyrene, 2,4-diethyl-α-methylstyrene, 2,6-
Diethyl-α-methylstyrene, 2-ethyl-3-methyl-α-methylstyrene, 2-methyl-4-propyl-
Substitutable styrenes represented by the following formula (1B) such as α-methylstyrene and 2-chloro-4-ethyl-α-methylstyrene are exemplified.

[0019]

Embedded image Each symbol in the formula (1B) is the same as in the formula (1A).

These vinyl aromatic hydrocarbon monomers are:
They may be used alone or in combination of two or more.

((Meth) acrylate monomer) The (meth) acrylate monomer used in the above method is an acrylate ester or a methacrylate ester, and specific examples include methyl acrylate, ethyl acrylate, Propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, n-acrylate
Acrylates such as amyl, isoamyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, hydroxypropyl acrylate, lauryl acrylate; methyl methacrylate, ethyl methacrylate;
Propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-amyl methacrylate, isoamyl methacrylate, n-hexyl methacrylate, methacryl 2-ethylhexyl,
And methacrylic esters such as hydroxypropyl methacrylate and lauryl methacrylate; and compounds represented by the following formula (2B). These vinyl aromatic hydrocarbon monomers may be used alone or in combination of two or more.

[0022]

Embedded image Each symbol in the formula (2B) is the same as in the formula (2A).

(Amino Group-Containing (Meth) acrylate Monomer) The amino group-containing (meth) acrylate monomer used in the above-mentioned method is an N, N-disubstituted aminoalkyl compound represented by the following formula (4): (Meth) acrylate compounds.

Embedded image In formula (4), R ¹ is a hydrogen atom or a methyl group, R ²
Is the same as in the above formula (3a1), and R ³ and R ⁴ are each independently a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms. Preferred examples of R ² are the same as those in the above formula (3a2), and R ³ and R ⁴ are each independently preferably a straight-chain or branched alkyl group having 1 to 3 carbon atoms.

Specific examples of such a compound include dimethylaminomethyl (meth) acrylate, diethylaminomethyl (meth) acrylate, dipropylaminomethyl (meth) acrylate, diisopropylaminomethyl (meth) acrylate, and ethylmethylaminomethyl ( (Meth) acrylate, methylpropylaminomethyl (meth) acrylate, dimethylamino-1-ethyl (meth) acrylate, diethylamino-1-ethyl (meth) acrylate, dipropylamino-1-ethyl (meth) acrylate, diisopropylamino-1 -Ethyl (meth) acrylate, ethylmethylamino-1-ethyl (meth) acrylate, methylpropylamino-1-
Ethyl (meth) acrylate, dimethylamino-2-ethyl (meth) acrylate, diethylamino-2-ethyl (meth) acrylate, dipropylamino-2-ethyl (meth) acrylate, diisopropylamino-2-
Ethyl (meth) acrylate, ethylmethylamino-2
-Ethyl (meth) acrylate, methylpropylamino-2-ethyl (meth) acrylate, dimethylamino-
1-propyl (meth) acrylate, diethylamino-
1-propyl (meth) acrylate, dipropylamino-1-propyl (meth) acrylate, diisopropylamino-1-propyl (meth) acrylate, ethylmethylamino-1-propyl (meth) acrylate, methylpropylamino-1-propyl (Meth) acrylate, dimethylamino-2-propyl (meth) acrylate, diethylamino-2-propyl (meth) acrylate, dipropylamino-2-propyl (meth) acrylate, diisopropylamino-2-propyl (meth) acrylate, ethyl N, N-disubstituted aminoalkyl (meth) acrylate compounds such as methylamino-2-propyl (meth) acrylate and methylpropylamino-2-propyl (meth) acrylate.

(Quaternary Ammonium Base-Containing (Meth) acrylate Monomer) The amino group-containing (meth) acrylate compound can be obtained by using a halogenated organic compound described below to obtain a quaternary ammonium base-containing (meth) acrylate. (Meth) acrylate compounds containing quaternary ammonium halide bases, such as dimethylaminoethyl methyl methacrylate chloride (DMC) and dimethylaminoethyl benzyl methacrylate (DMC)
L) can also be used directly. Further, by using directly a commercially available sulfonated compound such as sulfate, dimethyl sulfate, diethyl sulfate, and paratoluene sulfonate, an organic acid salt described later can be used. Can be omitted.

(Polymerization Initiator) The polymerization initiator used for obtaining the quaternary ammonium salt group-containing copolymer by the above-mentioned method includes 2,2'-azobisisobutyronitrile,
2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobisisobutyrate, 4,4 Azo compounds such as' -azobis (4-cyanopentanoic acid); 2,2'-azobis (2-aminodipropane) dihydrochloride, 2,2'-azobis (N, N'-dimethyleneisobutylamidine) ,
Diamine compounds such as 2,2'-azobis (N, N'-dimethyleneisobutylamidine) dihydrochloride are used. Examples of the peroxide-based radical polymerization initiator include persulfates such as potassium persulfate and ammonium persulfate; 4,4-azobis (4-cyanovaleric acid);
-Azobis (2-amidinopropane) dihydrochloride, 2,2
-Azobis-2-methyl-N-1,1-bis (hydroxymethyl) -2-hydroxyethylpropioamide,
2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile,
1'-azobis (1-cyclohexanecarbonitrile)
Azo compounds such as methyl ethyl peroxide, di-t-
Butyl peroxide, acetyl peroxide, dicumyl peroxide, lauroyl peroxide, benzoyl peroxide, t-butylperoxy-2-ethylhexanoate, di-isopropylperoxydicarbonate, di-t-butylperoxyiso Peroxides such as phthalate can be exemplified. Further, a redox initiator obtained by combining these polymerization initiators and a reducing agent can be exemplified. The amount of the polymerization initiator can be arbitrarily selected according to the intended weight average molecular weight. Specifically, the amount of the polymerization initiator used is 100
The amount is 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight based on parts by weight. When the amount of the polymerization initiator is less than 0.001% by weight based on the aqueous medium, the polymerization rate is slow. When the amount is more than 3% by weight, particles having a particle diameter of less than 1 μm tend to be produced as by-products.

Further, solution polymerization using an anionic polymerization initiator such as an alkali metal, butyllithium, or a reaction product of an alkali metal and naphthalene is preferable because the molecular weight can be easily controlled.

(Quaternizing agent) The quaternizing agent used in the above method is a halogenated organic compound or an acid ester compound.
Specifically, examples of the halogenated organic compound include chloromethane, dichloromethane, trichloromethane, chloroethane, 1,1-dichloroethane, 1,2-dichloroethane, hexachloroethane, chloropropane, 1,1-dichloropropane, and 1,2-dichloroethane. Dichloropropane, 1,3-
Dichloropropane, 1,1,3,3-tetrachloropropane, chloroisopropane, chlorobutane, 1,4-dichlorobutane, 1,1-dichloroisobutane, chlorohexane, chlorocyclohexane, bromomethane, dibromomethane, tribromomethane, bromoethane , 1,1-
Dibromoethane, 1,2-dibromoethane, hexachloroethane, chloropropane, 1,1-dichloropropane, 1,2-dibromopropane, 1,3-dibromopropane, 1,1,3,3-tetrabromopropane, bromoisopropane Bread, bromobutane, 1,2-dibromobutane, 1,4-dibromoisobutane, 1,1,4,4-tetrabromobutane, 1,5-dibromopentane, bromocyclopentane, carbon such as 1,6-dibromohexane Linear, branched, or cyclic alkyl halide of formulas 1 to 6; chlorobenzene, bromobenzene, 4-chlorotoluene, 4-bromotoluene, 4-ethylchlorobenzene, 4-ethyltoluene, 1-chloronaphthalene, 2-
Aromatic halides such as chloronaphthalene, 1-bromonaphthalene, and 2-bromonaphthalene; and the like.
Particularly, a halogenated organic compound having two or more halogens bonded thereto is advantageous for obtaining a quaternary ammonium salt group-containing copolymer having a high weight average molecular weight by crosslinking.

Specific examples of the acid ester include methyl methyl sulfonate, ethyl methyl sulfonate, propyl methyl sulfonate, isopropyl methyl sulfonate,
Methyl ethyl sulfonate, ethyl ethyl sulfonate, propyl ethyl sulfonate, isopropyl ethyl sulfonate, methyl propyl sulfonate, ethyl propyl sulfonate, propyl propyl sulfonate, isopropyl propyl sulfonate, methyl isopropyl sulfonate, ethyl isopropyl sulfonate, Alkyl sulfonic acid alkyl esters such as isopropyl isopropyl sulfonic acid and isopropyl isopropyl sulfonic acid; alkyl benzene sulfonic acid such as methyl benzene sulfonic acid, ethyl benzene sulfonic acid, propyl benzene sulfonic acid, and isopropyl benzene sulfonic acid; Such as ethyl paratoluenesulfonate, propyl paratoluenesulfonate, and propyl paratoluenesulfonate. Aromatic sulfonic acid esters such as toluenesulfonic acid alkyl ester; trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri (2-ethylhexyl) phosphate, tributoxyethyl phosphate, trioleyl phosphate, triphenyl phosphate, tricresyl phosphate, triquine Seal phosphate, tris (isopropylphenyl) phosphate, tris (O-phenylphenyl) phosphate, tris (p-phenylphenyl) phosphate, trinaphthylphosphate, cresyldiphenylphosphate, xyenyldiphenylphosphate, diphenyl (2-ethylhexyl) phosphate , Di (isopropylphenyl) phosphate, O-
Phosphate esters such as phenylphenylcresyl phosphate, dibutyl phosphate, monobutyl phosphate, di (2-ethylhexyl) phosphate, and monoisodecyl phosphate; borate esters such as trimethoxyborane, triethoxyborane, and tripropoxyborane; Is exemplified. Among these, straight-chain, branched alkyl halides and sulfonic acid esters having 1 to 3 carbon atoms are preferable from the viewpoint of obtaining a toner having excellent positive charging stability, and having little deterioration in image quality due to fluctuation in the amount of charge during durable printing,
Particularly, an aromatic sulfonic acid ester is preferable.

(Halogenated Organic Compound) The halogenated organic compound used in the above-mentioned method is the same as the halogenated organic compound used as the quaternizing agent.

(Organic acid or derivative thereof) Examples of the organic acid or derivative thereof used in the above-mentioned method include methylsulfonic acid, ethylethylsulfonic acid, ethylsulfonic acid, ethyl propylsulfonic acid, propylsulfonic acid propyl, and propylsulfonic acid. Alkyl sulfonic acids such as isopropyl sulfonic acid and the like; aromatic sulfonic acids such as benzene sulfonic acid and para-toluene sulfonic acid; trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri (2-ethylhexyl) phosphate, tributoxyethyl phosphate and trioleyl phosphate , Triphenyl phosphate, tricresyl phosphate, triquin seal phosphate, tris (isopropylphenyl) phosphate, tris (O-
Phenylphenyl) phosphate, tris (p-phenylphenyl) phosphate, trinaphthylphosphate, cresyldiphenylphosphate, xyenyldiphenylphosphate, diphenyl (2-ethylhexyl) phosphate, di (isopropylphenyl) phosphate, O-phenylphenylcresyl Phosphate,
Phosphoric acid esters such as dibutyl phosphate, monobutyl phosphate, di (2-ethylhexyl) phosphate and monoisodecyl phosphate; boric acid esters such as trimethoxyborane, triethoxyborane, and tripropoxyborane; Among them, a linear or branched alkyl halide or sulfonic acid ester having 1 to 3 carbon atoms is preferable from the viewpoint of chargeability, and an aromatic sulfonic acid ester is particularly preferable.

(Polymerization) The above-mentioned method may be any method such as emulsion polymerization, dispersion polymerization, suspension polymerization, and solution polymerization. However, solution polymerization is particularly preferable because a desired weight average molecular weight can be obtained. . The solvent and dispersant used in each polymerization can be appropriately selected. Specifically, examples of the hydrocarbon compound include aromatic hydrocarbon compounds such as benzene, toluene, and xylene; n-hexane, cyclohexane, and methylcyclohexane. , Ethylcyclohexane, nonane, decane, decalin, dodecane and the like; and hydrocarbon-containing organic compounds such as nitroethane, 1-nitropropane, 2-nitropropane, acetonitrile, triethylamine and cyclohexylamine. And nitrogen-containing organic compounds such as pyridine, monoethanolamine, diethanolamine, phorphorin, N, N-dimethylformamide and N-methylpyrrolidone. Examples of the oxygen-containing organic compound include methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, secondary butyl alcohol, amyl alcohol, isoamyl alcohol, methyl isobutyl carbinol,
Compounds having a hydroxyl group such as 2-ethylbutanol, 2-ethylhexanol, cyclohexanol, furfuryl alcohol, tetrahydrofurfuryl alcohol, ethylene glycol, hexylene glycol, glycerin; propyl ether, isopropyl ether,
Butyl ether, isobutyl ether, n-amyl ether, isoamyl ether, methyl butyl ether, methyl isobutyl ether, methyl n-amyl ether,
Methyl isoamyl ether, ethyl propyl ether,
Ethyl isopropyl ether, ethyl butyl ether,
Aliphatic saturated ethers such as ethyl isobutyl ether, ethyl n-amyl ether and ethyl isoamyl ether; aliphatic unsaturated ethers such as allyl ether and ethyl allyl ether; aromatics such as anisole, phenetole, phenyl ether and benzyl ether Aromatic ethers; cyclic ethers such as tetrahydrofuran, tetrahydropyran and dioxane; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether;
Ethylene glycols such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether and diethylene glycol monobutyl ether; organic acids such as formic acid, acetic acid, acetic anhydride and butyric acid; butyl formate, amyl formate, propyl acetate, isopropyl acetate, butyl acetate and sec-butyl acetate , Amyl acetate, isoamyl acetate, 2-ethylhexyl acetate, cyclohexyl acetate, butylcyclohexyl acetate, ethyl propionate, butyl propionate, amyl propionate, butyl butyrate, diethyl carbonate, diethyl oxalate, methyl lactate, ethyl lactate, butyl lactate, Organic acid esters such as triethyl phosphate; methyl isopropyl ketone, methyl isobutyl ketone, methyl isobutyl ketone, diisobutyl ketone,
Acetylacetone, diacetone alcohol, cyclohexanone, cyclopentanone, methylcyclohexanone,
Ketones such as cycloheptanone; and other oxygen-containing organic compounds such as 1,4-dioxane, isophorone, and furfural. As the chlorine-containing organic compound,
Examples thereof include chlorine-substituted aliphatic hydrocarbons having 2 to 6 carbon atoms, such as tetrachloroethane, trichloroethylene, perchloroethylene, dichloropropane, amyl chloride, and dichloropentane. Examples of the sulfur-containing organic compound include thiophene, sulfolane, dimethyl sulfoxide and the like.

The polymerization temperature and the polymerization time can be arbitrarily selected depending on the polymerization method and the kind of the polymerization initiator to be used.
Usually, the temperature is about 50 to 200 ° C, and the polymerization time is 0.5 to 20.
About an hour. Further, at the time of polymerization, a generally known additive, for example, a polymerization aid such as an amine can be used in combination. A method for obtaining a quaternary salt copolymer from a system after polymerization is a method of dropping into a poor solvent, a method of removing a solvent with steam,
A method of removing under reduced pressure, a method of polymerizing at a high concentration and directly adding it to a toner polymerization system are used.

(Weight average molecular weight A) Gel of quaternary ammonium base-containing copolymer using tetrahydrofuran
The weight average molecular weight Mw in terms of polystyrene measured by permeation chromatography is 25,000.
0-1,000,000, preferably 25,000-8
00,000, more preferably 25,000 to 100,
000. If the weight average molecular weight is too large, the handling during the production of the toner particles is poor and the size of the droplets may vary, so that uniform toner particles may not be obtained,
Conversely, if the weight average molecular weight is too small, the fluidity of the developer is insufficient, and there is a problem that the storage stability is reduced.

(Ratio B of Quaternary Ammonium Group-Containing (Meth) acrylate Units) Further, the quaternary ammonium group-containing copolymer used in the present invention has a molar fraction of quaternary ammonium group-containing (meth) acrylate units (hereinafter referred to as "molar fraction"). , The functional group molar fraction) is 0.01 to 0.4 mol%, preferably 0.03 to 0.3 mol%. If the proportion of the (meth) acrylate unit containing a quaternary ammonium base is too large, the charge tends to be excessive, and the printing characteristics tend to deteriorate.

The quaternary ammonium salt group-containing copolymer of the present invention described above is used as a charge controlling agent, but is not more than 50% by weight, preferably not more than 30% by weight, based on the copolymer. Preferably, they can be used together at a ratio of 10% by weight or less. Specific examples of charge control agents that can be used in combination include Nigrosine Bontron N-01 (manufactured by Orient Chemical), Nigrosine Base EX (manufactured by Orient Chemical), quaternary ammonium salt P-51 (manufactured by Orient Chemical), Copy Blue-PR (Hoechst)
And the like.

2. Polymerizable monomer As the monomer used in the present invention, a monovinyl monomer can be exemplified. Specifically, styrene monomers such as styrene, vinyltoluene and α-methylstyrene; acrylic acid, methacrylic acid; methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, acrylic Acrylic acid or methacrylic acid such as dimethylaminoethyl methacrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, dimethylaminoethyl methacrylate, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, etc. Derivatives of ethylene; ethylenically unsaturated monoolefins such as ethylene, propylene and butylene; vinyl halides such as vinyl chloride, vinylidene chloride and vinyl fluoride; vinyls such as vinyl acetate and vinyl propionate Monovinyl compounds such as vinyl ethers such as vinyl methyl ether and vinyl ethyl ether; vinyl ketones such as vinyl methyl ketone and methyl isopropenyl ketone; nitrogen-containing vinyl compounds such as 2-vinyl pyridine, 4-vinyl pyridine and N-vinyl pyrrolidone; Monomers. These monovinyl monomers may be used alone, or a plurality of monomers may be used in combination. Of these monovinyl monomers, styrene monomers or derivatives of acrylic acid or methacrylic acid are preferably used.

As a monomer used in the present invention, a crosslinkable monomer is preferably used for improving hot offset. The crosslinkable monomer is a monomer having two or more polymerizable carbon-carbon unsaturated double bonds. Specifically, aromatic divinyl compounds such as divinylbenzene, divinylnaphthalene, and derivatives thereof; diethylenically unsaturated carboxylic esters such as ethylene glycol dimethacrylate and diethylene glycol dimethacrylate; N, N
Divinyl compounds such as divinylaniline and divinyl ether; compounds having three or more vinyl groups; These crosslinkable monomers can be used alone or in combination of two or more.

In the present invention, it is preferable to use a macromonomer as a monomer in order to improve the balance between storage stability and low-temperature fixability. The macromonomer has a vinyl polymerizable functional group at the terminal of the molecular chain and is an oligomer or polymer having a number average molecular weight of usually 1,000 to 30,000. When a polymer having a small number average molecular weight is used, the surface portion of the polymer particles becomes soft, and the storage stability decreases. On the other hand, when a polymer having a large number average molecular weight is used, the meltability of the macromonomer is deteriorated, and the fixability and the storage stability are reduced. Examples of the vinyl polymerizable functional group at the terminal of the macromonomer molecular chain include an acryloyl group and a methacryloyl group, and a methacryloyl group is preferable from the viewpoint of easy copolymerization.

The macromonomer preferably has a glass transition temperature higher than the glass transition temperature of the polymer obtained by polymerizing the monovinyl monomer.

The level of Tg between the polymer obtained by polymerizing the monovinyl monomer and the macromonomer is relative. For example, when the monovinyl monomer has Tg = 70
In the case of forming a polymer at a temperature of ° C, the macromonomer may have a Tg exceeding 70 ° C. When the monovinyl monomer forms a polymer having a Tg of 20 ° C., the macromonomer is, for example, Tg = 6.
It may be at 0 ° C. The macromonomer T
g is a value measured by a measuring instrument such as a normal DSC.

Specific examples of the macromonomer used in the present invention include polymers obtained by polymerizing styrene, styrene derivatives, methacrylates, acrylates, acrylonitrile, methacrylonitrile, etc., alone or in combination of two or more. Macromonomers having a polysiloxane skeleton, and those disclosed on pages 4 to 7 of JP-A-3-203746 can be exemplified. Among these macromonomers, polymers obtained by polymerizing hydrophilic ones, particularly methacrylic esters or acrylic esters, alone or in combination thereof are suitable for the present invention.

When a macromonomer is used, its amount is usually based on 100 parts by weight of the monovinyl monomer.
0.01 to 10 parts by weight, preferably 0.03 to 5 parts by weight,
More preferably, it is 0.05 to 1 part by weight. When the amount of the macromonomer is too small, the balance between the storability and the fixability may not be improved. When the amount of the macromonomer is extremely large, the fixing property is reduced.

3. Colorants Colorants include carbon black, titanium white,
Dyes and pigments such as nigrosine base, aniline blue, calco oil blue, chrome yellow, ultramarine blue, orient oil red, phthalocyanine blue, malachite green oxalate; cobalt, nickel, iron sesquioxide, iron tetroxide, iron manganese oxide And magnetic particles such as zinc iron oxide and nickel iron oxide;

Further, as a colorant for a magnetic color toner, C.I. I. Direct Red 1, C.I. I. Direct Red 4, C.I. I. Acid Red 1, C.I. I. Basic Red 1, C.I. I. Modant Red 30, C.I.
I. Direct Blue 1, C.I. I. Direct Blue 2, C.I. I. Acid Blue 9, C.I. I. Acid Blue 15, C.I. I. Basic Blue 3, C.I. I. Basic Blue 5, C.I. I. Modant Blue 7, C.I. I.
Direct Green 6, C.I. I. Basic Green 4, C.I. I. Basic Green 6 and the like include, as pigments, graphite, cadmium yellow, mineral first yellow, navel yellow, neftol yellow S, hanziero G,
Permanent yellow NCG, tartrazine lake, red lead graphite, molybdenum orange, permanent orange GT
R, pyrazolone orange, benzidine orange G, cadmium red, permanent red 4R, watching red calcium salt, eosin lake, brilliant carmine 3B, manganese purple, fast violet B, methyl violet lake, navy blue, cobalt blue, alkaline blue lake, Victoria Blue Lake, Phthalocyanine Blue, Fast Sky Blue, Induslen Blue BC, Chromium Green, Chromium Oxide, Pigment Green B, Malachite Green Lake, Final Yellow Green G and the like. Examples of the magenta coloring pigment for full-color toner include C.I. I. Pigment Red 1,
2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12,
13, 14, 15, 16, 17, 18, 19, 21, 2
2, 23, 30, 31, 32, 37, 38, 39, 4,
0, 41, 48, 49, 50, 51, 52, 53, 5
4, 55, 57, 58, 60, 63, 64, 68, 8
1, 83, 87, 88, 89, 90, 112, 114,
122, 123, 163, 202, 206, 207 and 209, C.I. I. Pigment Violet 19, C.I.
I. Butt Red 1,2,10,13,15,23,2
And magenta dyes such as C.I. I. Solvent red 1, 3, 8, 23, 24, 25, 27,
30, 49, 81, 82, 83, 84, 100, 109
And 121, C.I. I. Disperse Red 9, C.I.
I. Solvent Violet 8, 13, 14, 21 and 27, C.I. I. Oil-soluble dyes such as Disperse Violet 1; I. Basic Red 1, 2, 9, 12,
13, 14, 15, 17, 18, 22, 23, 24, 2
7, 29, 32, 34, 35, 36, 37, 38, 39
And 40, C.I. I. Basic violet 1, 3,
Basic dyes such as 7, 10, 14, 15, 21, 25, 26, 27 and 28;

Cyan color pigments for full-color toners include C.I. I. Pigment Blue 2, 3, 15, 16 and 17, C.I. I. Bat Blue 6, C.I. I. Acid Blue 45 and a copper phthalocyanine pigment in which 1 to 5 phthalimidomethyl groups are substituted on the phthalocyanine skeleton.

The yellow color pigments for full-color toners include C.I. I. Pigment Yellow 1, 2, 3, 4,
5, 6, 7, 10, 11, 12, 13, 14, 15, 1,
6, 17, 23, 65, 73, 83, 138 and 18
0, C.I. I. Bat Yellow 1, 3, and 20 and the like.

5. Production of Toner In the presence of the above-described quaternary ammonium base-containing copolymer, a polymerizable monomer, a colorant, and other additives, if necessary, are added with water containing an inorganic dispersant to initiate polymerization. At this time 4
The use ratio C of the quaternary ammonium salt group-containing copolymer is 0.01 to 10 parts by weight based on 100 parts by weight of the monomer to be subjected to suspension polymerization. The weight average molecular weight A of the quaternary ammonium salt group-containing copolymer described above and the molar fraction B of the repeating structural unit of the quaternary ammonium salt group-containing (meth) acrylate structure in the quaternary ammonium salt group-containing copolymer and the quaternary amount The relationship of the use ratio C of the ammonium base-containing copolymer is
2.5 ≦ A × B × C ≦ 5,000,000, preferably 50 ≦ A × B × C ≦ 200,000, more preferably 1
When 00 ≦ A × B × C ≦ 150,000, an excellent toner is obtained, which is particularly excellent in the positive charging stability and in which the image quality is hardly degraded due to the fluctuation of the charge amount during the durability printing.

The inorganic dispersant used in the present invention is a cationic dispersant usually used in suspension polymerization. Specific examples include metal hydroxides such as aluminum hydroxide, magnesium hydroxide, and ferric hydroxide. The cationic dispersant is preferable because the dispersant is hardly adsorbed on the toner surface, the particle shape is excellent, the image quality is excellent, and the durability is excellent.

The inorganic dispersant containing a colloid of a poorly water-soluble metal hydroxide is not limited by its manufacturing method, but the poorly water-soluble polyhydric metal compound obtained by adjusting the pH of the aqueous solution of the polyvalent metal compound to 7 or more can be used. Colloidal metal hydroxide,
In particular, it is preferable to use a colloid of a poorly water-soluble metal hydroxide generated by a reaction of a water-soluble polyvalent metal compound and an alkali metal hydroxide in an aqueous phase.

The colloid of the poorly water-soluble metal compound used in the present invention has a number particle size distribution D50 (50% cumulative value of the number particle size distribution) of 0.5 μm or less and a D90 (9% of the number particle size distribution).
(0% cumulative value) is preferably 1 μm or less. When the particle size of the colloid is large, the stability of polymerization is lost, and the storage stability of the toner is reduced.

The inorganic dispersant is generally used in a proportion of 0.1 to 20 parts by weight based on 100 parts by weight of the polymerizable monomer. If this proportion is less than 0.1 part by weight, it is difficult to obtain sufficient polymerization stability, and a polymer aggregate is easily generated. Conversely, if the amount exceeds 20 parts by weight, the viscosity in the aqueous dispersion medium increases, and the distribution of the polymerized toner particle size is unfavorably widened.

In the present invention, usually, a polymerization auxiliary material such as a radical polymerization initiator and a molecular weight modifier, and various additives such as a release agent and a wax are compounded in order to polymerize the polymerizable monomer. be able to.

Examples of the radical polymerization initiator include persulfates such as potassium persulfate and ammonium persulfate; 4,4-azobis (4-cyanovaleric acid), 2,2-azobis (2-amidinopropane) dihydrochloride, 2,2-azobis-2-methyl-N-1,1-bis (hydroxymethyl) -2-hydroxyethylpropioamide, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2 ′ Azo compounds such as -azobisisobutyronitrile and 1,1'-azobis (1-cyclohexanecarbonitrile); methyl ethyl peroxide, di-t-butyl peroxide, acetyl peroxide, dicumyl peroxide, lauroyl peroxide Oxide, benzoyl peroxide, t-butylperoxy-2-ethylhexanoate, di-isopropylperoxydica Boneto, and the like can be exemplified peroxides di -t- butyl peroxy isophthalate and the like. Further, a redox initiator obtained by combining these polymerization initiators and a reducing agent can be exemplified. Among these, an oil-soluble radical initiator, particularly an oil-soluble radical initiator selected from organic peroxides having a 10-hour half-life temperature of 60 to 80 ° C, preferably 65 to 80 ° C and a molecular weight of 250 or less. In particular, t-butyl peroxy-2-ethylhexanoate is preferable because it has a low odor during printing and has little environmental destruction due to volatile components such as odor.

The amount of the polymerization initiator used for producing the toner is usually 0.001 to 3% by weight based on the aqueous medium.
If the amount is less than 0.001% by weight, the polymerization rate is low and 3% by weight.
Excess is not preferable because the molecular weight becomes low.

Examples of the molecular weight regulator include mercaptans such as t-dodecyl mercaptan, n-dodecyl mercaptan and n-octyl mercaptan; carbon tetrachloride;
Halogenated hydrocarbons such as carbon tetrabromide; and the like. These molecular weight regulators can be added before the start of polymerization or during the polymerization. The molecular weight modifier is usually 0.01 to 1 based on 100 parts by weight of the monomer.
0 parts by weight, preferably 0.1 to 5 parts by weight.

Examples of the release agent include polyfunctional ester compounds such as pentaerythritol tetrastearate; low molecular weight polyethylene, low molecular weight polypropylene,
Low molecular weight polyolefins such as low molecular weight polybutylene; paraffin waxes; Of these, polyfunctional ester compounds, particularly those comprising pentaerythritol and a carboxylic acid having 10 to 30 carbon atoms, specifically, pentaerythritol tetrastearate are preferred. The release agent is used in an amount of usually 0.1 to 40 parts by weight, preferably 1 to 2 parts by weight, per 100 parts by weight of the monomer.
Used in a proportion of 0 parts by weight.

Further, a lubricant such as oleic acid and stearic acid; a dispersing aid such as a silane-based or titanium-based coupling agent; and the like may be used for the purpose of, for example, uniformly dispersing the colorant in the toner particles. . Such a lubricant or dispersant is usually 1/1000 to 100% based on the weight of the colorant.
Used at a rate of about 1/1.

When starting the suspension polymerization, the suspension is usually stirred. The stirring may be performed before or after the addition of the polymerization initiator. The stirring is not particularly limited as long as the monomer composition is uniformly dispersed in the aqueous medium.However, the stirring is performed in a gap between the rotor rotating at high speed and the stator surrounding the rotor and having small holes or comb teeth. A method of distributing and granulating is preferable.

The dispersion state of the monomer composition dispersion is such that the volume average particle diameter of the droplets of the monomer composition is 0.1 to 20 μm, preferably 0.5 to 10 μm. If the droplets are too large, the toner particles will be large and the resolution of the image will be reduced.

The volume average particle diameter / number average particle diameter of the droplet is 1
To 3.0, preferably 1 to 2.0. If the particle size distribution of the droplets is wide, a variation in fixing temperature occurs, causing problems such as fogging and filming. The droplet is
Preferably, it has a particle size distribution of 50% by volume or more, preferably 60% by volume or more in the range of the volume average particle size ± 1 μm.

Further, in the production method of the present invention, it is preferable that after the monomer composition dispersion liquid is obtained, it is charged into a polymerization reactor and polymerized. Specifically, the monomer composition is added to the aqueous medium in a dispersion preparation container to prepare a monomer composition dispersion, and the monomer composition is placed in another container (a polymerization reaction container). )
And polymerized in the container, and polymerized. In a method in which a dispersion is obtained in a polymerization reactor and the polymerization reaction is carried out as it is, as in the conventional suspension polymerization method, scale is generated in the reactor, and large amounts of coarse particles are easily generated.

In the polymerization of the monomer in the production method of the present invention, the polymerization conversion is usually at least 80%, preferably at least 85%, more preferably at least 90%. If it is less than 80%, if the monomer remains, the remaining monomer volatilizes when the toner is heat-fixed, thereby deteriorating the working environment.

The present invention can be applied to the production of a toner having a core-shell structure.

Depending on the method for producing the toner of the present invention, the volume average particle diameter of the particles is usually 0.5 to 20 μm, preferably 1 to 20 μm.
To 10 μm are obtained. In addition, volume average particle size (dv) /
Those having a number average particle size (dp) of usually 1.7 or less, preferably 1.5 or less, more preferably 1.4 or less are obtained.

Examples of the external additive used for producing the developer containing the toner of the present invention include inorganic particles and organic resin particles. Examples of the inorganic particles include silicon dioxide, aluminum oxide, titanium oxide, zinc oxide, tin oxide, barium titanate, and strontium titanate.
As the organic resin particles, methacrylate polymer particles, acrylate polymer particles, styrene-methacrylate copolymer particles, styrene-acrylate copolymer particles, the core is a methacrylate copolymer, Core-shell type particles whose shell is formed of a styrene polymer are exemplified. Of these, inorganic oxide particles, particularly silicon dioxide particles, are preferred. Moreover, the surface of these particles can be subjected to a hydrophobic treatment, and silicon dioxide particles subjected to the hydrophobic treatment are particularly suitable. The amount of the external additive is not particularly limited, but is usually 0.1 to 6 parts by weight based on 100 parts by weight of the toner particles.

The external additives may be used in combination of two or more kinds. When an external additive is used in combination, a method of combining two kinds of inorganic oxide particles or organic resin particles having different average particle diameters is preferable. Specifically, particles having an average particle diameter of 5 to 20 nm, preferably 7 to 18 nm (preferably inorganic oxide particles), and an average particle diameter of more than 20 nm and 2 μm
m and preferably 30 nm to 1 μm (preferably inorganic oxide particles). The average particle diameter of the particles for the external additive is an average value obtained by observing the particles with a transmission electron microscope, randomly selecting 100 particles, and measuring the particle diameter.

The amount of the two types of external additives (particles) is usually 0.1 to 3 parts by weight, preferably 0.1 to 3 parts by weight, based on 100 parts by weight of the toner particles. Two
2 parts by weight, particles having an average particle diameter of more than 20 nm and 2 μm or less are usually 0.1 to 3 parts by weight, preferably 0.2 to 2 parts by weight. The weight ratio between the particles having an average particle diameter of 5 to 20 nm and the particles having an average particle diameter of more than 20 nm and 2 μm or less is usually 1: 1:
The range is from 5 to 5: 1, preferably from 3:10 to 10: 3. The attachment of the external additive is usually performed by putting the external additive and the toner particles into a mixer such as a Henschel mixer and stirring the mixture.

[0069]

EXAMPLES The present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these examples. The parts and percentages are
Unless otherwise specified, it is based on weight.

In this example, evaluation was made by the following method. (Weight average molecular weight) Quaternary ammonium base-containing (meta)
The weight average molecular weight of the acrylate unit is a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography using tetrahydrofuran (hereinafter, simply referred to as weight average molecular weight or Mw). Specifically, the following method was used. 1) Sample preparation About 10 mg of a sample was dissolved in 5 ml of a tetrahydrofuran solvent, left at 25 ° C. for 16 hours, and passed through a 0.45 μm membrane filter to obtain a sample. 2) Measurement conditions: temperature: 35 ° C, solvent: tetrahydrofuran, flow rate: 1.
0 ml / min, concentration: 0.2 wt%, sample injection amount: 1
00 μl. 3) Column Showa Denko K.K., Showdex GPC KF80
6M (30 cm × 2) was used.

(Fluidity) 3 types of sieves (openings: 150, 7)
5, 45 μm) are stacked in this order from the top, and 4 g of the developer to be measured is precisely weighed and placed on the uppermost sieve. These three types of sieves are used as a powder measuring machine (manufactured by Hosokawa Micron Co., Ltd .; trade name "REOSTA").
T "), the developer was vibrated for 15 seconds under the condition of vibration intensity 4, and then the weight of the developer passed through the sieve was measured and calculated by the following formula. The measurement was performed three times per sample, and the average value was used as an index of fluidity. Calculation formula: a = (weight of developer remaining on 150 μm sieve (g)) / 4 g
× 100 b = (weight of developer remaining on 75 μm sieve (g)) / 4 g ×
100 × 0.2 c = (weight of developer remaining on 45 μm sieve (g)) / 4 g ×
100 × 0.6 Fluidity (%) = 100− (a + b + c)

(Preservability) The developer was placed in a sealed container, sealed, then immersed in a thermostatic water bath at a temperature of 55 ° C., and after a certain period of time, the developer was gently taken out of the container. After being transferred onto a mesh sieve so as not to destroy the structure as much as possible, the sample was vibrated for 30 seconds under the condition of a vibration intensity of 4.5 using a powder measuring device (manufactured by Hosokawa Micron Co., Ltd .; trade name “REOSTAT”). The weight of the developer remaining on the sieve was measured and defined as the weight of the aggregation developer. The weight ratio (% by weight) of the aggregation developer to all the developers was calculated. 1
The measurement was performed three times for each sample, and the average value was used as an index of storage stability.

(Environmental Dependence of Charge Amount) L / L (Temperature 10
C., humidity 20% RH) or H / H (temperature 35 ° C., humidity 80% RH) environment. Five tone print patterns were printed, and then the developer on the developing roller was sucked into a suction-type charge amount measuring device, and the charge amount per unit weight was measured from the charge amount and the suction amount. The state of the environmental change of the developer was evaluated from the change of the charge amount under each environment.

(Environment Dependency of Image Quality) The above-mentioned printer was used at 35 ° C. × 85 RH% (H / H) environment and at 10 ° C. × 15%.
Continuous printing is performed from the beginning in an environment of RH% (L / L), the print density is 1.3 or more with a reflection densitometer (manufactured by Macbeth), and the fog of the non-image portion is 10 or more with a whiteness meter (manufactured by Nippon Denshoku) %, The developer that can be continued for 1000 sheets or more was evaluated as (○), and the developer that could not be continued was evaluated as (X).

(Durability of image quality)
Continuous printing is performed from the beginning under an environment of 50 ° C x 50 RH% (H / H), the print density is 1.3 or more with a reflection densitometer (manufactured by Macbeth), and the fog of non-image areas is a whiteness meter (manufactured by Nippon Denshoku) At 10
% Of the developer that can be continued for 10,000 sheets or more (O),
A developer that can continue 5,000 sheets or more was evaluated as (Δ), and a developer that could not continue 5,000 sheets or more was evaluated as (x).

Example 1 90 parts of styrene, 10 parts of a releasing agent (manufactured by Shell MDS; trade name "FT-100"), and 0.09 part of a polymerization inhibitor (t-butylcatechol) were wet-milled by a media type. Wet pulverization was performed using a mill to prepare a styrene monomer release agent dispersion in which the release agent was uniformly dispersed. The volume average particle diameter of the release agent in this dispersion is 3.2 μm for D50 and 7.2 for D90.
μm. The solid content of the dispersion is 10.
1%.

In a 3 liter flask, 900 parts of toluene,
88 parts of styrene, 12.8 parts of butyl acrylate, dimethylaminoethyl benzyl methacrylate 0.
After 7 parts and 2 parts of azobisdimethylvaleronitrile were stirred and reacted at 80 ° C. for 8 hours, the solvent was removed by distillation under reduced pressure to obtain a quaternary ammonium salt group-containing copolymer having Mw of 40,000.

Then, 20 parts of the release agent dispersion obtained above, 65 parts of styrene, 17 parts of n-butyl acrylate, and carbon black (trade name: Monarch 120, manufactured by Cabot Corporation)
7 parts, quaternary ammonium base-containing copolymer (MW = 4
000, styrene ratio 89.775 mol%, n-butyl acrylate ratio 9.975 mol%, quaternary ammonium group-containing monomer ratio 0.25 mol%) 5 parts, divinylbenzene 0.3 part After stirring and mixing, the mixture was uniformly dispersed by a media type disperser, and 4 parts of a polymerization initiator (t-butylperoxy-2-ethylhexanoate, manufactured by NOF CORPORATION) was dissolved therein to obtain a polymerizable monomer. A body mixture was obtained.

On the other hand, in an aqueous solution obtained by dissolving 9.5 parts of magnesium chloride (water-soluble polyvalent metal salt) in 250 parts of ion-exchanged water, 5.8 parts of sodium hydroxide (alkali metal hydroxide) in 50 parts of ion-exchanged water The aqueous solution in which was dissolved was gradually added under stirring to prepare a magnesium hydroxide colloid (poorly water-soluble metal hydroxide colloid) dispersion. The particle size distribution of the produced colloid was measured with a Microtrac particle size distribution analyzer (manufactured by Nikkiso Co., Ltd.).
(50% cumulative value of number particle size distribution) is 0.37 μm and D
90 (90% cumulative value of the number particle size distribution) was 0.81 μm. The measurement by the Microtrac particle size distribution analyzer was performed under the following conditions: measurement range = 0.12 to 704 μm, measurement time = 30 seconds, and medium = ion-exchanged water.

The above monomer mixture was charged into the magnesium hydroxide colloidal dispersion obtained as described above, and the mixture was stirred at 12,000 rpm with a high shear using a TK homomixer. Droplets were granulated. The aqueous dispersion of the granulated monomer mixture is put into a reactor equipped with a stirring blade, and a polymerization reaction is started at 90 ° C., and after 8 hours, the reaction is stopped. A dispersion was obtained.

While the aqueous dispersion of the polymer particles for a developer thus obtained was stirred, the pH of the system was adjusted to about 5.5 with sulfuric acid, and acid washing (25 ° C., 10 minutes) was performed. Next, filtration and dehydration were performed, and after dehydration, washing water was sprinkled to perform water washing. Thereafter, drying was performed for two days and nights in a drier (45 ° C.) to obtain polymer particles.

The polymer particles 1 for a developer obtained as described above
In 00 parts, silica having an average particle diameter of 8 nm subjected to hydrophobization treatment (manufactured by PACKER CHEMIE Co .; trade name "HVK
2150 ”) and mixed using a Henschel mixer to produce a non-magnetic one-component developer.

The volume average particle diameter (dv) of the developer obtained by the above formulation was 6.9 μm. In the image evaluation, under both high-temperature and high-humidity conditions and low-temperature and low-humidity conditions, a very good image with good color tone, high image density and no fog was obtained. Other evaluation results are shown in Table 1.

Comparative Example 1 In Example 1, Aerosil # 200 was used as the inorganic dispersant.
Was obtained in the same manner as in Example 1 except that 2 parts were dispersed and used in 300 parts of ion-exchanged water. Table 1 shows the evaluation results.

[0085]

[Table 1]

In the table, Mw is the weight average molecular weight of the quaternary ammonium salt group-containing copolymer, and the mole fraction is the quaternary ammonium salt group-containing (meth) acrylate unit in the quaternary ammonium salt group-containing copolymer. Is the ratio (mol%), and the part is the ratio of the quaternary ammonium salt group-containing copolymer to the composition such as the monomer to be subjected to suspension polymerization. Table 2 below
The same applies to ４4.

Example 2 900 parts of toluene and styrene 88 were placed in a 3 liter flask.
Part 12.8 parts butyl acrylate 0.7 part dimethylaminoethylbenzyl methacrylate and 5 parts azobisdimethylvaleronitrile are charged and stirred,
After 8 hours of reaction at ℃, the solvent was removed by distillation under reduced pressure
6,000 quaternary ammonium base-containing copolymers were obtained. A developer was obtained in the same manner as in Example 1 except that the quaternary ammonium base-containing copolymer having a molecular weight of 26,000 was used. Table 2 shows the evaluation results.

Example 3 900 parts of toluene and 88 parts of styrene were placed in a 3 liter flask.
Parts, butyl acrylate 12.8 parts, dimethylaminoethyl benzyl methacrylate 0.7 parts, 1,4
-0.1 part of butanediol diacrylate and 2 parts of azobisdimethyl valeronitrile were charged, stirred, reacted at 80 ° C for 8 hours, and then the solvent was removed by distillation under reduced pressure.
000 quaternary ammonium base-containing copolymer was obtained. A developer was obtained in the same manner as in Example 1, except that the quaternary ammonium salt group-containing copolymer having a molecular weight of 162,000 was used. Table 2 shows the evaluation results.

Comparative Example 2 A developer was obtained in the same manner as in Example 1, except that the quaternary ammonium salt group-containing copolymer having a molecular weight of 21,000 was used. Table 2 shows the evaluation results. The charge was high, the print density of LL was low, and there was a problem in the image even in durability.

Comparative Example 3 A developer was obtained in the same manner as in Example 1 except that the quaternary ammonium salt group-containing copolymer having a molecular weight of 1,500,000 was used. Table 2 shows the evaluation results. Because of the high molecular weight of the quaternary ammonium salt group-containing copolymer, the viscosity of the composition such as a polymerizable monomer was high, the particle size was large, and the distribution was disordered.

[0091]

[Table 2]

Example 4 The procedure of Example 1 was repeated except that the quaternary ammonium salt group-containing copolymer used had a molecular weight of 41,000 and a functional group mole fraction of 0.01%. To obtain a developer. Table 3 shows the evaluation results.

Example 5 The procedure of Example 1 was repeated except that the quaternary ammonium salt group-containing copolymer used had a molecular weight of 42,000 and a functional group mole fraction of 0.4%. To obtain a developer. Table 3 shows the evaluation results.

Comparative Example 4 The procedure of Example 1 was repeated except that the quaternary ammonium salt group-containing copolymer used had a molecular weight of 40,000 and a functional group molar fraction of 0.005 part. To obtain a developer. Table 3 shows the evaluation results.

Comparative Example 5 The procedure of Example 1 was repeated except that the quaternary ammonium salt group-containing copolymer used had a molecular weight of 42,000 and a functional group mole fraction of 0.5%. To obtain a developer. Table 3 shows the evaluation results.

[0096]

[Table 3]

Example 6 In Example 1, a quaternary ammonium salt group-containing copolymer having a molecular weight of 41,000, a functional group mole fraction of 0.2%, and a copolymer content of 0.01 part was used. A developer was obtained in the same manner as in Example 1 except for the fact that the developer was present. Table 4 shows the evaluation results.

Example 7 In Example 1, a quaternary ammonium salt group-containing copolymer having a molecular weight of 40,000, a functional group mole fraction of 0.2%, and a copolymer content of 10.0 parts was used. A developer was obtained in the same manner as in Example 1 except for the fact that the developer was present. Table 4 shows the evaluation results.

Comparative Example 6 In Example 1, a quaternary ammonium salt group-containing copolymer having a molecular weight of 42,000, a functional group mole fraction of 0.2%, and a copolymer content of 0.005 part was used. A developer was obtained in the same manner as in Example 1 except for the fact that the developer was present. Table 4 shows the evaluation results.
It was shown to.

Comparative Example 7 In Example 1, a quaternary ammonium salt group-containing copolymer having a molecular weight of 41,000, a functional group mole fraction of 0.2%, and a copolymer content of 12.0 parts was used. A developer was obtained in the same manner as in Example 1 except for the fact that the developer was present. Table 4 shows the evaluation results.

[0101]

[Table 4]

[0102]

According to the present invention, the charge amount does not change much and the image quality is hardly degraded under both low temperature, low humidity and high temperature, high humidity environments. Therefore, it can be suitably used for a printing machine of a non-magnetic one-component developing system and a copying machine.

Claims (1)

[Claims] 1. A quaternary ammonium base-containing copolymer having a repeating unit derived from a vinyl aromatic hydrocarbon, a repeating unit derived from (meth) acrylate, and a repeating unit derived from (meth) acrylate containing quaternary ammonium base. A method for producing a toner for developing an electrostatic image, in which a polymerizable monomer is suspension-polymerized in a suspension medium containing a colorant and an inorganic dispersant in the presence of coalescence, wherein the inorganic dispersant is cationic. A quaternary ammonium base-containing copolymer having a weight average molecular weight A in terms of polystyrene of 25,000 to 1,000, as measured by gel permeation chromatography using tetrahydrofuran.
000, and the molar fraction B of the repeating structural unit of the quaternary ammonium salt group-containing (meth) acrylate structure in the quaternary ammonium salt group-containing copolymer is 0.01 to 0.4.
%, And the amount (parts by weight) C of the quaternary ammonium salt group-containing copolymer is 0.01 to 10 parts by weight based on 100 parts by weight of the monomer to be subjected to suspension polymerization. A method for producing an image developing toner.