CN1105946C - Charge controller, toner binder composition and electrophotographic toner - Google Patents

Abstract

The present invention discloses a charge regulator for toner, for example, the present invention comprises an olefinic bond unsaturated monomer polymer which is provided with 0.008 to 0.3 dielectric loss tangent in 100khz and at most 10%(weight) degree of water absorption. The present invention is adopted from: (1) polymer (A1) which is provided with one aromatic ring monomer (1) which is at least substituted by an electron-withdrawing group (X) selected from a halogen atom, a nitro group and a cyano group, and copolymer (A2) which is provided with a monomer (2) having organic acid group or the salt thereof and another monomer. The xerographic toner has the properties of excellent electrostatic charge quantity, charge rate, environmental stability, etc. by the charge regulator of the present invention. Besides, the charge regulator is colorless, and does not contain heavy metal.

Description

Charge adjusting agent, toner binder composition and electrostatic duplication toner

1. Invention field

The present invention relates to a kind of charge adjusting agent and a kind of method for producing toner and toner and a kind of toner that is used for electrostatic latent image.Or rather, the present invention relates to can electronegative charge adjusting agent and a kind of toner binder composition and a kind of electrostatic duplication toner.

2. Prior art

Existing people of past utilizes and adds the electric charge that charge adjusting agent is regulated electrostatic duplication toner.As the electronegative charge adjusting agent in the known charge correctives, known have azo dyes compounds, a salicylic acid-metal complex etc.

As the modified compound, following compound has been proposed:

(1) multipolymer of styrene and vinylbenzenesulfonic acid sodium salt (Jap.P. KOKAI No.88564/1985).

(2) potpourri of acrylic acid perfluoroalkyl polymerizable methacrylate thing and styrene, methyl acrylate and 2-acrylamide-2-methyl propane sulfonic acid multipolymer (Jap.P. KOKAI No.230609/1994).

(3) segmented copolymer of methyl methacrylate and methacrylic acid (USP4,925,765).

But, use the potpourri that discloses in (1)-(3), because the static charge of toner is very low, thus need a large amount of charge adjusting agents, and this is uneconomic.And this has also damaged other performance (low temperature fixation performance, anti--thermal migration etc.) of the toner that requires.Charged speed (using the mixing time of friction force when electric charge reaches aequum) is also fast inadequately.So duplicating machine needs one section long warm-up period, and the copy video variation when duplicating continuously.The charge variation that humidity causes is very big, thereby its environmental stability deficiency.

And because the transparency that is made into behind the toner is relatively poor, being found when using color toner has harmful effect to tone.

One of purpose of the present invention provides a kind of metal-free colourless substantially charge adjusting agent.

Another object of the present invention provides a kind of outstanding charge adjusting agent of performance that comprises the amount of electrostatic charge of toner, charged speed and environmental stability.

A further object of the present invention provides a kind of charge adjusting agent that does not have about above-mentioned dispersive property and transparency problem.

These and other purpose of the present invention will be further illustrated in explanation hereinafter.

Summary of the invention

Mainly can reach above-mentioned purpose of the present invention substantially by aspect, following (1) of the present invention-(3).

(1) contain the charge adjusting agent that is used for toner of the polymkeric substance that certain ethylene linkage unsaturated monomer forms, it is 0.008 to 0.3 the dielectric loss angle tangent (tan δ) and the absorption of water of maximum 10% (weight) that described polymkeric substance has at 100kHz, and is selected from:

(1) is selected from the polymkeric substance (A1) that the monomer (1) of the aromatic rings that the electron withdraw group (X) of halogen atom, nitro and cyano group replaces forms by having one by at least one;

(2) multipolymer (A2) that forms by the monomer with an organic acid group or its salt (2) and another monomer.

(2) a kind of toner binder composition that contains described charge adjusting agent and toner binder resin,

(3) a kind of toner that contains toner binder resin, colorant and charge adjusting agent.

Specifying of preferred embodiment

According to the present invention, the dielectric loss angle tangent (tan δ) of measuring 100kHz is as follows:

With agate mortar polymkeric substance is ground to form the powder that mean diameter is not more than 50 μ m, compression moulding is prepared into a test pieces in a dielectric loss angle tangent mensuration electrode.The related electrode of test pieces is placed on the surveying instrument, and the electricity when measuring 100kHz is led and electric capacity, then measures thickness.Calculate dielectric loss angle tangent by conductivity, electric capacity and thickness.

Suitable dielectric loss angle tangent in the 0.008-0.3 scope, is good with 0.008-0.2 usually, is best with 0.015-0.1.Dielectric loss angle tangent can cause charged underspeed less than 0.008 polymkeric substance, and dielectric loss angle tangent can cause the amount of electrostatic charge deficiency of toner greater than 0.3 polymkeric substance.

According to the present invention, it is as follows to measure absorption of water (%):

With agate mortar polymkeric substance is ground to form the powder that mean diameter is not more than 50 μ m with upper type.The 2g test powders, is controlled at humidity 85%R.H.12 hour at 35 ℃ after 4 hours at 35 ℃ of drying under reduced pressure.And then weigh and increase number percent (dry preceding and dried weight differential) and calculate absorption of water by weight with respect to weight before dry.

The scope of absorption of water (%) is at most 10% (weight) usually, is good with 5% (weight) at the most, and 2% (weight) is better at the most.Absorption of water can cause relatively poor environmental stability greater than the polymkeric substance of 10% (weight).

Suitable polymers of the present invention comprises the polymkeric substance (A) that is formed by one or more ethylene linkage unsaturated monomers.

Suitable polymers (A) comprising:

(i) be selected from the polymkeric substance (A1) that the monomer (1) of the aromatic rings that the electron withdraw group (X) of halogen atom, nitro and cyano group replaces forms by having one by at least one;

The (ii) multipolymer (A2) that forms by the monomer with an organic acid group or its salt (2) and another monomer.

Suitable electron withdraw group comprises, for example, and halogen atom (as chlorine atom, bromine atoms, iodine atom and fluorine atom), nitro and cyano group.Wherein, preferred halogen atom and nitro.

The suitable example by the monomer (1) of the aromatic rings of at least one electron withdraw group (X) replacement that has comprises: phenylethylene (as chlorostyrene, dichlorostyrene, bromstyrol, fluorobenzene ethene, nitrostyrolene, cyano styrene); The maleimide (as chlorphenyl maleimide, dichlorophenyl maleimide, nitrobenzophenone maleimide, nitroxyl chloride phenyl maleimide) that contains aromatic rings; The clothing health acid imide (as chlorphenyl clothing health acid imide, dichlorophenyl clothing health acid imide, nitrobenzophenone clothing health acid imide, nitroxyl chloride phenyl clothing health acid imide) that contains aromatic ring; (methyl) esters of acrylic acid (representing acrylate and methacrylate with this identical expression hereinafter) (as (methyl) acrylic acid chlorobenzene ester, (methyl) acrylic acid bromobenzene ester, (methyl) acrylic acid nitro phenyl ester, (methyl) acrylic acid chlorobenzene 2-ethoxyethyl acetate, (methyl) acrylic acid bromobenzene 2-ethoxyethyl acetate, (methyl) acrylic acid nitrobenzene 2-ethoxyethyl acetate) that contains aromatic ring; (methyl) acrylamide (as chlorphenyl (methyl) acrylamide, bromophenyl (methyl) acrylamide, nitrobenzophenone (methyl) acrylamide) that contains aromatic ring; The vinethene (as chlorphenyl vinethene, nitrobenzophenone vinethene) that contains aromatic ring.Wherein, the maleimide and the clothing health acid imide that contains aromatic ring that preferably contain aromatic ring.

Polymkeric substance (A1) comprises homopolymer or the multipolymer that is formed by a kind of described monomer (1) at least, and the multipolymer of other copolymerisable monomer formation of monomer (1) and one or more.

Suitable copolymerisable monomer example comprises the monomer (2) that contains an organic acid group or its salt, the monomer (3-1) that contains perfluoroalkyl, the monomer (3-2) and other copolymerisable monomer (4) that contain siloxy group, and preferred two or more potpourri in these monomers.

Quilt is preferred because the charged speed of toner is fast for the multipolymer that described monomer (1) and described monomer (2) form.

The multipolymer of described monomer (1) and described monomer (3-1) or described monomer (3-2) because improving the carried charge of toner, charged speed and environmental stability by preferred.

Multipolymer (A2) comprises the multipolymer that other monomer of described monomer (2) and one or more forms.

Suitable monomers (2) example comprises and contains sulfonic monomer (2-1), contains carboxylic acid group's monomer (2-2), and the sulfonic monomer of amino-contained (2-3) contains sour sulfur acid group class monomer (2-4), contains acid phosphorus acid group class monomer (2-5) and their salt.

Suitable monomers (2-1) example comprises the monomer (as styrene sulfonic acid, sulfophenyl acrylamide, sulfophenyl maleimide, sulfophenyl clothing health acid imide) that contains the aromatic sulfonic acid base, contains the monomer (as vinyl sulfonic acid, allyl sulphonic acid, 2-acrylamide-2-methyl-propyl sulfonic acid, methacryloyl base oxethyl sulfonic acid) of aliphatic sulfonic acid base etc.

The example of monomer (2-2) comprises (methyl) acrylic acid, maleic acid, itaconic acid, butyl maleate, maleic acid list perfluoroalkyl ethyl ester, itaconic acid list perfluoroalkyl ethyl ester etc.

Suitable monomers (2-3) example comprises allyl amino sulfonic acid, styryl sulfaminic acid, vinyl sulfaminic acid etc.

Suitable monomers (2-4) example comprises the sulfuric acid monoester of hydroxyl monomer (as (methyl) hydroxy-ethyl acrylate, hydroxyethyl vinethene, vinylphenol) etc.

Suitable monomers (2-5) example comprises the phosphate monoester of above-mentioned hydroxyl monomer or diester etc.

The salt example of suitable described monomer (2) comprises its alkali metal salt (as lithium, sodium, potassium), alkali salt (as magnesium, calcium, barium), amine (as triethylamine, tri-butylamine, N, N-3,5-dimethylphenyl amine), quaternary ammonium salt (as tributyl phenyl ammonium, etamon, TBuA) etc.

Wherein, the monomer that contains organic hydrochlorate is better than containing the monomer of organic acid groups.And therein, the monomer of alkali metal containing salt, alkali salt or amine preferably.About the kind of acidic group, preferably described monomer (2-1), (2-2) and (2-4), especially monomer (2-1).That is, therein, the monomer that contains the aromatic sulfonic acid base of alkali metal salt, alkali salt or amine salt form most preferably.Heavy metallic salt (as nickel, copper, zinc, mercury, chromium) is because dangerous and nonconforming.

The suitable monomer that contains perfluoroalkyl (3-1) example comprises perfluoroalkyl ethene, (methyl) acrylic acid perfluoroalkyl ethyl ester, maleic acid list (perfluoroalkyl ethyl) ester, itaconic acid list (perfluoroalkyl ethyl) ester etc.

The suitable monomer that contains siloxy group (3-2) example comprises the ester that the silicone oil of (methyl) acrylic acid or maleic acid and terminal hydroxyl modification forms; Acid amides that the silicone oil of (methyl) acrylic acid or maleic acid and terminal hydroxyl modification forms or acid imide etc.

Wherein, the monomer that preferably contains perfluoroalkyl.The monomer that most preferably contains the C8-16 perfluoroalkyl.

Suitable other copolymerisable monomer (4) example also comprises alkene (as ethene, propylene, 1-butylene, isobutylene, dodecylene) except that described monomer (3); Vinethene (as ethylene methacrylic ether, butyl vinyl ether, stearoyl vinethene); Aromatic vinyl hydrocarbon (as styrene, α-Jia Jibenyixi, to cumyl styrene); (methyl) acrylic acid, (methyl) acrylate (as (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) butyl acrylate); Dienes (as butadiene, isoprene); Vinyl acetate (as vinyl acetate, propionate); Nitrile group-containing monomer (as (methyl) vinyl cyanide) etc.

With regard to the enough quantities of electric charge of toner were provided, polymkeric substance (A1) contained described monomer (1) unit of at least 5% (weight) usually, is good with at least 10% (weight), and 20-89% (weight) is better.

Polymkeric substance (A1) contains described monomer (2) unit of 0-20% (weight) usually, is good with 0.1-20% (weight), and 1-10% (weight) is better.

Polymkeric substance (A1) contains described monomer (3) unit of 0-95% (weight) usually, is good with 10-90% (weight), and 10-79% (weight) is better.

Polymkeric substance (A1) contains described monomer (4) unit of 0-95% (weight) usually, is good with 0-50% (weight), and 0-30% (weight) is better.

Multipolymer (A2) comprises the multipolymer that other copolymerisable monomer of described monomer (2) and one or more forms.

Suitable can comprise above-mentioned monomer (3-1), monomer (3-2) and monomer (4) with the copolymerisable monomer example of monomer (2) copolymerization.

Suitable and more suitably example may with identical about described in the polymkeric substance (A1) above.

The multipolymer that monomer (2) and monomer (3) form because improving toner performance such as the carried charge as toner, charged speed and environmental stability by preferred.

Polymkeric substance (A2) contains described monomer (2) unit of at least 0.1% (weight) usually, is good with 0.1-20% (weight), and 1-10% (weight) is better.If content is less than 0.1% (weight), dielectric loss angle tangent can diminish and the charged speed meeting deficiency of toner.Content is bigger, and dielectric loss angle tangent can be bigger, and the carried charge of toner and environmental stability can be not enough.

According to the present invention, the weight-average molecular weight of polymkeric substance (A) is generally 1,000 to 500,000, is good with 2,000 to 200,000.If less than 1,000, its understands compatible with bonding agent and the carried charge deficiency.Simultaneously, if greater than 500,000, polymkeric substance (A) is difficult in the toner and disperses.

In a preferred embodiment of the invention, except above-mentioned polymkeric substance (A), also used a kind of multipolymer that constitutes by following composition (AB):

The polymeric components (a) that polymkeric substance (A) constitutes, it is selected from polymkeric substance (A1) and (A2), and polymkeric substance (A1) is the individual aromatic ring that is replaced by an electron withdraw group (X) that is selected from halogen atom, nitro and cyano group at least that contains at least; Polymkeric substance (A2) contains an organic acid group or their salt;

With the polymeric components (b) that at least a polymkeric substance (B) constitutes, it is selected from styrene polymer (B1) and polyester (B2).

Component (b) combines with component (a) with grafting or block form.

(AB) because can be easily with toner in component (a) form less discontinuous regional structure particle and by preferred.

Suitable styrene polymer (B1) comprises the multipolymer that styrene homopolymers or styrene and another copolymerisable monomer (6) form.

Suitable other copolymerisable monomer (6) example comprises the aromatic vinyl hydrocarbon except that styrene, (methyl) acrylic monomers and other vinyl monomer.

Other suitable aromatic vinyl hydrocarbon example comprises the styrene that alkyl replaces (as α-Jia Jibenyixi, p-methylstyrene, to cumyl styrene); Halogenated styrenes (as chlorostyrene, 1-chloro-4-methyl-benzene); Acetoxy-styrene, hydroxy styrenes etc.

Suitable (methyl) acrylic monomers example comprises the acrylate (as (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) butyl acrylate, (methyl) 2-EHA, (methyl) lauryl acrylate, (methyl) acrylic acid octadecane ester) that alkyl replaces; (methyl) acrylate of hydroxyl (as (methyl) hydroxy-ethyl acrylate); (methyl) acrylate (as (methyl) glycidyl acrylate) that contains oxo group; The monomer (as isocyanic acid methacryloyl ester) that contains isocyanate group; With monomer (as (methyl) vinyl cyanide) of nitrile group-containing etc.

Other suitable vinyl monomer example comprises: vinyl acetate (as vinyl acetate, propionate); Diene monomers (as butadiene, isoprene); Alkenyl halide (as vinyl chloride, bromine ethene); α, unsaturated monobasic of β-ethylene linkage or polybasic carboxylic acid (as (methyl) acrylic acid, crotonic acid, sorbic acid, maleic acid, itaconic acid, cinnamic acid); Their acid anhydrides (as maleic anhydride); Their half ester (as ethyl maleate) etc.

Wherein, preferred styrene polymer (B1) is the multipolymer of multipolymer, styrene and diene monomers of styrene homopolymers, styrene and (methyl) acrylic monomers and the multipolymer of these monomers and other copolymerisable monomer.

Styrene polymer (B2) contains the styrene units that is no less than 40% (mol) usually, is good with 60% (mol).

Suitable polyvalent alcohol (7) example comprises dibasic alcohol (7-1) and contains 3 or more polyhydric polyvalent alcohol (7-2), preferably (7-1) and (7-1) and the potpourri of a small amount of (7-2).

Suitable dibasic alcohol (7-1) example comprises the alkylidene ethylene glycol (as ethylene glycol, 1,2-trimethylene glycol, 1,3-trimethylene glycol, 1,4-butylene glycol, 1,6-hexanediol) that contains 2-12 carbon; Alkylene ether glycol (as diglycol, triethylene glycol, dipropylene glycol, polyglycol, polypropylene glycol, polytetramethylene glycol); Alicyclic diol (as bisphenol-A, Bisphenol F, bisphenol S); The alkylene oxide of above-mentioned diphenol (as oxirane, epoxypropane, oxidation butane) adduct etc.Wherein, preferably contain the aklylene glycol of 2-12 carbon, the alkylene oxide adduct of diphenol and their potpourri.

Suitable contain 3 or more polyhydric polyvalent alcohol (7-2) example and comprise the aliphatic polyol (as glycerine, trimethylolethane, trimethylolpropane, pentaerythrite, sorbierite) that contains 3-20 carbon; Contain 3 or more polyhydric phenols (as triphenol PA, novolac, line style cresol-novolak varnish); The oxyalkylene ether of above-mentioned phenols.

Suitable polybasic carboxylic acid (8) example comprises dicarboxylic acid (8-1) and contains the polybasic carboxylic acid (8-2) of 3 or more carboxyls, preferably (8-1) and (8-1) and the potpourri of a small amount of (8-2).

Suitable dicarboxylic acid (8-1) example comprises the alkylene dicarboxylic acids (as succinic acid, hexane diacid, decanedioic acid) that contains 2-20 carbon; Alkenyl dicarboxylic acid (as maleic acid, fumaric acid); Contain the aromatic dicarboxylic acid (as phthalic acid, m-phthalic acid, terephthalic acid (TPA), naphthalenedicarboxylic acid) of 8-20 carbon etc.Wherein, the alkylene dicarboxylic acids and the aromatic dicarboxylic acid that contains 8-20 carbon that preferably contain 2-20 carbon.

Suitable polybasic carboxylic acid (8-2) example that contains 3 or more carboxyls comprises the aromatic polycarboxylic acid (as trimellitic acid, 1,2,4, the 5-benzenetetracarboxylic acid) that contains 9-20 carbon; Deng.

During preparation polyester (B2), the mol ratio (7) of polyvalent alcohol (7) and dicarboxylic acid (8): (8) are generally 1: 2 to 2: 1, are good with 1: 1.5 to 1.5: 1.

(7) (7-1) in: mol ratio (7-2) is generally 100: 0 to 80: 20, is good with 100: 0 to 90: 10.

(8) (8-1) in: mol ratio (8-2) usually with (7-1): (7-2) identical.

Press (AB) weight ratio of the total restatement of charge adjusting agent, if grafting or block combination, be generally 1-100%, be good with 10-100%.If weight ratio (AB) less than 1%, will be difficult to form less discontinuous regional structure particle size.

Weight ratio by (A) of the total restatement of charge adjusting agent is generally 0-99%, is good with 0-90%, and weight ratio (B) is generally 0-90%, is good with 0-50%.If weight ratio (B) greater than 99%, just needs a large amount of charge adjusting agents to obtain enough electric charges, and this is uneconomic.

In charge adjusting agent of the present invention, (Wa) ((A) and general assembly (TW) content (a)) is generally 10-99%, is good with 20-90%.If (Wa) less than 10%, just need a large amount of charge adjusting agents to obtain enough electric charges, and this is uneconomic.If (Wa) greater than 99%, the DeGrain of grafting or block combination.

Suitable copolymers (AB) example, (b) wherein is connected with (a) grafting or block, comprising:

(1) graft copolymer that forms of upper strata polymer chain (b) wherein and matrix polymer chain (a) grafting;

(2) graft copolymer that forms of upper strata polymer chain (a) wherein and matrix polymer chain (b) grafting;

(3) (a) with (b) segmented copolymer;

Wherein, preferably above-mentioned graft copolymer (1) and multipolymer (2).

The weight-average molecular weight of component (a) is generally 1,000-100, and 000, with 2,000-50,000 is good.

The weight-average molecular weight of component (b) is generally 1,000-500, and 000, with 3,000-100,000 is good.

If (a) or weight-average molecular weight (b) less than 1,000, will cause harmful effect to the flowability of toner, if and weight-average molecular weight (a) is greater than 100,000 or weight-average molecular weight (b) greater than 500,000, charge adjusting agent will almost can not disperse in toner.

In order to reduce particle size, polymkeric substance (A) needn't all be (AB), and (A) part in is that (AB) is just much of that.That is, can contain (A) and (AB) simultaneously.And can contain the polymkeric substance (B) that is not connected with component (a).

In order to obtain this effect, the person is better to be similar to the toner binder for structure (b).So if use styrene polymer as toner binder, then preferred (b1) is as component (b).Simultaneously, if use polyester as toner binder, then preferred (b2) is as component (b).

According to the present invention, charge adjusting agent can together use with certain acylate (α) that contains perfluoroalkyl.Use salt (α) will help improving charged speed simultaneously.

The suitable acylate that contains perfluoroalkyl (α) example comprises the sulfonate (α-1) that contains perfluoroalkyl, the carboxylate (α-2) that contains perfluoroalkyl, the amidosulfonic acid salt (α-3) that contains perfluoroalkyl contains the sulfate (α-4) of perfluoroalkyl and contains phosphate (α-5) of perfluoroalkyl etc.

Suitable salt (α-1) is certain salt that contains perfluoroalkyl sulfonic acid and the formation of kation component.

The suitable example that contains perfluoroalkyl sulfonic acid comprises perfluoroparaffin sulfonic acid (as the own sulfonic acid of perfluor, perfluorooctane sulfonate); Perfluoroalkyl ethyl sulfonic acid (as perfluoro capryl ethyl sulfonic acid, perfluor decyl ethyl sulfonic acid); Perfluorinated alkenyl oxygen benzene sulfonic acid (as perfluorinated nonene base oxygen benzene sulfonic acid) etc.

Suitable kation component example comprises alkaline metal (as lithium, sodium, potassium), earth alkali metal (as magnesium, calcium, barium), amine (as triethylamine, tri-n-butylamine, N, N-3,5-dimethylphenyl amine), quaternary ammonium (as tributyl phenyl ammonium, tetraethyl ammonium, TBuA) etc.

Suitable salt (α-2) is to contain the carboxylic acid of perfluoroalkyl and the salt that above-mentioned kation component forms.

The suitable carboxylic acid example that contains perfluoroalkyl comprises perfluoroalkane acid (as perfluor caproic acid, perfluoro caprylic acid); Perfluorinated alkenyl oxybenzoic acid (as the perfluorinated nonene yl benzoic acid) etc.

Suitable salt (α-3) is to contain the sulfaminic acid of perfluoroalkyl and the salt that above-mentioned kation component forms.

The suitable perfluoroalkyl sulfaminic acid example that contains comprises perfluoroalkyl ethyl amidosulfonic acid (as perfluoro capryl ethylamino sulfonic acid, perfluor decyl ethylamino sulfonic acid) etc.

Suitable salt (α-4) is to contain the acid sulfate of perfluoroalkyl and the salt that above-mentioned kation component forms.

The suitable perfluoroalkyl acid sulfate example that contains comprises sulfuric acid monoester (as perfluoro octyl ethanol, perfluor decyl ethanol, perfluoro hexyl methyl alcohol) that contains perfluoroalkyl alcohol etc.

Suitable salt (α-5) is to contain the acid phosphoric acid ester of perfluoroalkyl and the salt that above-mentioned kation component forms.

The suitable perfluoroalkyl acid phosphoric acid ester example that contains comprises the above-mentioned phosphate monoester that contains perfluoroalkyl alcohol or diester etc.

In salt (α), preferably contain the sulfonate (α-1) of perfluoroalkyl, more preferably contain alkaline metal, earth alkali metal or the amine salt of the sulfonic acid of perfluoroalkyl.Heavy metal (as nickel, copper, zinc, mercury, chromium) salt is because dangerous and nonconforming.

In the charge adjusting agent composition, press the weight ratio of the total restatement of charge adjusting agent composition usually in 0-80% to 20-100% scope with respect to the acylate that contains perfluoroalkyl (α) of polymkeric substance (A) or multipolymer (B), with 1-80% to 20-99% is good, and 3-50 to 50-97% is better.If (α) content is less than 1% (weight), charged underspeed.If greater than 80% (weight), saturation charge and environmental stability deficiency.

The example of suitable polymers (A) comprises

(1) dichlorophenyl maleimide homopolymer.

(2) multipolymer of the potpourri/maleic anhydride (49/48/3) of the 1-alkene of nitrobenzophenone maleimide/C12-C14.

(3) multipolymer of the potpourri/maleic anhydride (51/45/4) of the 1-alkene of dichlorophenyl maleimide/C12-C14.

(4) multipolymer of nitrobenzophenone maleimide/methacrylic acid perfluoroalkyl (potpourri of C8-C12) ethyl ester (55/45).

(5) multipolymer of chlorphenyl maleimide/methacrylic acid perfluoroalkyl (potpourri of C8-C12) ethyl ester (55/45).

(6) multipolymer of dichlorophenyl maleimide/methacrylic acid perfluoroalkyl (potpourri of C8-C12) ethyl ester (48/52).

(7) multipolymer of dichlorophenyl clothing health acid imide/methacrylic acid perfluoroalkyl (potpourri of C8-C12) ethyl ester (49/51).

(8) multipolymer of dichlorophenyl clothing health acid imide/maleic acid list fluoroalkyl (potpourri of C8-C12) ester/ethylene methacrylic ether (34/42/14).

(9) multipolymer of methacrylic acid perfluoroalkyl (potpourri of C8-C12) ethyl ester/Sodium styrene sulfonate (91/1).

(10) multipolymer of methacrylic acid perfluoroalkyl (potpourri of C8-C12) ethyl ester/styrene sulfonic acid barium (89/11).

(11) multipolymer of methacrylic acid perfluoroalkyl (potpourri of C8-C12) ethyl ester/styrene tri-n-butylamine salt (85/15).

(12) multipolymer of acrylic acid perfluoroalkyl (potpourri of C8-C12) ethyl ester/Sodium styrene sulfonate (91/1).

(13) multipolymer of nitrobenzophenone maleimide/methacrylic acid perfluoroalkyl (potpourri of C8-C12) ethyl ester/2-acrylamide-2-methyl propane sulfonic acid (51/41/8).

(14) multipolymer of chlorphenyl maleimide/acrylic acid perfluoroalkyl (potpourri of C8-C12) ethyl ester/Sodium styrene sulfonate (50/45/5).

(15) multipolymer of dichlorophenyl maleimide/Sodium styrene sulfonate (96/4).

(16) multipolymer of dichlorophenyl maleimide/methacrylic acid perfluoroalkyl (potpourri of C8-C12) ethyl ester/Sodium styrene sulfonate (46/50/4).

(17) multipolymer of dichlorophenyl maleimide/methacrylic acid perfluoroalkyl (potpourri of C8-C12) ethyl ester/styrene sulfonic acid tri-n-butylamine salt (45/50/5).

(18) multipolymer of dichlorophenyl clothing health acid imide/acrylic acid perfluoroalkyl (potpourri of C8-C12) ethyl ester/styrene sulfonic acid magnesium (65/30/5).

(19) multipolymer of dichlorophenyl clothing health acid imide/acrylic acid perfluoroalkyl (potpourri of C8-C12) ethyl ester/sulfophenyl sodium itaconate (56/40/6).

(20) multipolymer of dichlorophenyl clothing health acid imide/methacrylic acid perfluoroalkyl (potpourri of C8-C12) ethyl ester/sulfophenyl sodium itaconate (30/64/6).

(21) multipolymer of dichlorophenyl maleimide/maleic acid perfluoroalkyl (potpourri of C8-C12) ethyl ester/sulfophenyl sodium itaconate/ethylene methacrylic ether (39/42/5/14).

Suitable (a) and multipolymer (AB) example that (b) constitutes comprise the graft copolymer of above-mentioned component (a) and following component (b):

(1) styrene homopolymers component.

(2) the multipolymer component of styrene/acrylic butyl ester (95/5).

(3) the multipolymer component of styrene/acrylic butyl ester (87/13).

(4) the multipolymer component of styrene/methacrylic acid butyl ester (75/25).

(5) the multipolymer component of phenylethylene/butadiene (90/10).

(6) bisphenol-A epoxy propane 2mol adduct/m-phthalic acid condensed polymer component.

(7) bisphenol-A epoxy propane 2mol adduct/m-phthalic acid condensed polymer component.

(8) bisphenol-A epoxy propane 2mol adduct/terephthalic acid (TPA) condensed polymer component.

(9) bisphenol-A epoxy ethane 2mol adduct/maleic acid condensed polymer component.

(10) bisphenol-A epoxy propane 3mol adduct/maleic acid condensed polymer component.

(11) bisphenol-A epoxy ethane 3mol adduct/terephthalic acid (TPA) condensed polymer component.

The illustrative preparation method of polymkeric substance among the present invention (A) is as follows:

The self-reacting phase one, carry out polymerization by the monomer that object construction is required, obtain polymkeric substance (A).For example, in the presence of azoisobutyronitrile, monomer (1) and monomers (2) such as copolymerization itaconic acid make polymkeric substance (A) with the aniline reaction that a quilt (X) group replaces then.

The illustrative preparation method of grafting or segmented copolymer (AB) comprises following method among the present invention:

1) by carrying out copolymerization to obtain to make the macromonomer method of graft copolymer with the monomer that contains (a) that can introduce copolymerization component (a) at the compound that styrene or polyester component (b) end contain the structure that can introduce polymerizable groups such as allyl.

2) by will contain styrene component or polyester component (b) terminal introduced can carry out the polymer reaction method that copolymerization makes multipolymer with the compound of the group of copolymerization component (a) reaction and the group that can react on copolymerization component (a) side chain as amino or hydroxyl etc. as carboxyl or anhydride group etc.

3) react to obtain the main chain initiated polymerization method of graft copolymer with the monomer that can introduce the formation (a) of multipolymer component (a) by having the compound that introduction contains as polyreaction initiating radical structures such as peroxies on styrene polymer component (b1) or polyester component (b2) side chain; Or by containing on the side chain of (a) compound and the styrene of introducing polyreaction initiating radical structure, if necessary and another copolymerisable monomer react.

(a) preparation method is basic identical with the preparation method of above-mentioned polymkeric substance (A).For example, carboxyl or anhydride group etc. can be identical with above-mentioned preparation method with the introducing method of the group of (b) end group reaction, and in order to introduce anhydride group, can be before the polymerization of the monomer that constitutes (a) monomer with anhydride group be carried out copolymerization and make (a) with the method that is same as preparation method polymkeric substance (A).

The method of introducing polymerization initiating group at the side chain of (a) comprises, for example, and the method that makes hydroperoxides and (a) with anhydride group react.

Can utilize conventional method to prepare to have the compound of on the end of styrene type polymer component (b1) or side chain, introducing the structure of above-mentioned reactive group.

For example, can in the presence of hydroxyl side chain transfer agent, prepare the compound that has hydroxyl at (b1) end by radiation copolymerization styrene and another copolymerisable monomer.

Also can utilize conventional method to prepare the compound that has hydroxyl at component (b2) end.

For example, can prepare the compound that has a hydroxyl at (b2) end by in the polycondensation reaction of polyvalent alcohol (7) that constitutes (b2) and polybasic carboxylic acid (8), using excessive polyvalent alcohol (7).Can make the compound that has methacrylyl at component (b2) end by isocyanic acid methacrylyl ester and above-mentioned (b2) reaction with hydroxyl.

And, in the preparation of (b2), polyvalent alcohol (7) and polybasic carboxylic acid (8) might not be used for polycondensation reaction.The derivant (as low-carbon-ester, acid anhydrides, carboxylic acid halides) of the derivant (as rudimentary monocarboxylate, alkoxide) of (7) and (8) can be used for polycondensation reaction and prepare target polyesters component (b2).

Charge adjusting agent of the present invention can mix with toner binder earlier before the preparation toner, to be used as the toner binder composition with electric charge adjusting function of the present invention.

Suitable toner binder comprises that styrene type polymer, polyester, epoxy resin, polyene, polyurethanes etc. be used as the polymkeric substance of toner binder in the past.

Suitable styrene type polymer comprises: styrene and the multipolymer of multipolymer, styrene and the diene monomers (as butadiene and isoprene) of (methyl) acrylate and the multipolymer of styrene and other copolymerisable monomer.

Suitable polyester comprises the condensed polymer of the oxyalkylene ether of aromatic dicarboxylic acid and bis-phenol.

Suitable epoxy resin comprises the reaction product of aromatic diol and chloropropylene oxide class; With their modified compound.

Suitable polyalkenes comprises: tygon, polypropylene, the multipolymer of ethene, propylene and other copolymerisable monomer.

Suitable polyurethanes comprises: the polyaddition compounds of the alkylene oxide adduct of aromatics two cyanates and aromatic diol.

The illustrative preparation method of toner binder composition of the present invention comprises following method:

(1) polymerization is above-mentioned for preparing the monomer methods that toner binder is used in the presence of charge adjusting agent.

(2) method of mixing toner binder and charge adjusting agent in solvent, solvent can be for example hydro carbons (toluene, dimethylbenzene etc.), halides (chloroform, ethylene dichloride etc.), ketone (acetone, butanone etc.) or acid amides (dimethyl formamide etc.).

(3) heat fusing and mix toner binder and the method for charge adjusting agent.

Charge adjusting agent of the present invention mixes the back as method for producing toner and toner of the present invention with toner binder and colorant.

Suitable colorant example comprises pigment and the dyestuff that had been used before following,, Baranito aniline red red as carbon black, iron oxide black, the yellow G of sudan black SM, First, benzidine yellow, pigment yellow, India's first orange, Irgasine, toluidine red, fuchsin FB, pigment orange R, Raykired 2G, rhodamine FB, rhodamine B lake, methyl violet B color lake, phthalocyanine blue, alizarol saphirol, bright green, phthalocyanine green, oil yellow GG, Kayaset YG, Orasol palm fibre B, the red OP of oil-bound distemper etc.

The weight content of polymkeric substance in toner binder of the present invention and electrostatic duplication toner is generally 0.1-20%, is good with 0.3-10%, by the weight of toner.

If the content of polymkeric substance is less than 0.1%, the carried charge of toner tails off, if content greater than 20%, the environmental stability variation.

By the weight of toner, toner contains the 0.1-20% charge adjusting agent usually, the 30-95% toner binder, and the 0-15% colorant is less than 60% magnetic if necessary in addition.Suitable magnetic comprises ferromagnetism metal powder (as iron, cobalt, nickel), magnetite powder, and ground hematite, iron oxide etc., these magnetics have the performance of colorant.

In addition, can also contain various adjuvants, for example, lubricant (as teflon, low-molecular-weight polyene, fatty acid or their slaine or acid amides) and other charge adjusting agent (as the azo dyes of containing metal, salicylic acid metal salt).And the fine particle of dewatering silica gel can be used to improve the flowability of toner.These content of additive are less than 10% of toner gross weight usually.

Contain in the preferred adhesive composition:

(1) by the locus of discontinuity domain structure that constitutes to small part toner charge correctives; With

(2) by an external phase that constitutes to the small part toner binder.

Charge adjusting agent is easy to be exposed to the surface, compares with the charge adjusting agent compatible with toner binder, even add a spot of charge adjusting agent, toner also can provide enough carried charges.

Can utilize transmission electron microscope by inspection have or not the existence at the interface by the toner tangent plane measure above-mentioned (1) and (2) mutually or regional structure.Check the interface with will be clear that, can be at the tangent plane of tangent plane dyeing back being used the electron microscopy toner with ruthenium tetroxide, osmium tetroxide etc.

The particle diameter of described regional structure is generally 0.01-4 μ m, is good with 0.05-2 μ m.Greater than the particle of 4 μ m can cause being difficult for diffusion and wider CHARGE DISTRIBUTION, relatively poor transparency when using color toner, simultaneously, can be compatible less than the particle of 0.01 μ m can not form the locus of discontinuity domain structure with bonding agent.So the charge adjusting agent of toner surface tails off, it is not enough that carried charge becomes.

The preparation method of electrostatic duplication toner of the present invention there is no specific restriction.The preparation method is as follows for its illustrative:

(1) kneading and polishing

Mix in dry atmosphere behind the each component of toner its kneading, carry out coarse crushing and correct grinding with jet mill etc. then, it is the smart powder of 5-20 μ m that the product gradation is become average particulate diameter, thereby makes toner.

(2) add the blending method

In dry atmosphere, advance to contain the particle that diameter is 5-20 μ m at charge adjusting agent of the present invention and middle blending, they contain toner binder and colorant, with or without lubricant and magnetic, mix the good product of blending with mixer is randomly violent under heating condition then, thereby make toner.

(3) polymerization

Charge adjusting agent of the present invention, colorant and other component disperseed and be dissolved in the starting monomer of toner binder, then in water with they polymerizations.The toner of diameter 5-20 μ m will can be obtained after the product drying.

If necessary, toner of the present invention can be mixed with support powders such as iron powder, nickel powder, beaded glasses, thereby can be used as the developer of electrostatic latent image in the electrofax.

Can utilize duplicating machine or printing machine that toner of the present invention is fixed on the matrix such as paper, polyester film.The illustrative method on the matrix of being fixed on comprises that heat rolls fixation and hurried fixation.

Charge adjusting agent of the present invention also can be used for liquid developer and powder coating etc.

Above roughly described the present invention, can obtain more comprehensively to understand by following particular specific embodiment, the purpose that embodiment is included just illustrates rather than limits the present invention for example, except as otherwise noted.Hereinafter, part refers to weight portion.

(evaluation method)

(1) mensuration of dielectric loss angle tangent (tan δ)

With agate mortar charge adjusting agent is ground to form the powder that mean diameter is not more than 50 μ m, test pieces of compression moulding preparation in electrode.

The equipment that is used for this mensuration:

Main frame: TR-1100 (by Ando Denki Co., Ltd. provides)

Electrode: SE-43 (by Ando Denki Co., Ltd. provides)

Frequency: 100kHz

(2) mensuration of absorption of water (%)

With same upper type, with agate mortar charge adjusting agent is being ground to form after mean diameter is not more than the powder of 50 μ m, take by weighing 2g powder to be measured 35 ℃ of drying under reduced pressure 4 hours, at 35 ℃ humidity was controlled at 85%R.H.12 hour then.Then, weigh once more and calculate absorption of water (%) by increase (weight differentials before and after dry) percent with respect to the weight before dry.

(3) preparation of developer

Mix 1 part of toner and 24 parts of ferrite carriers (FL961-150 is provided by Powdertec Ltd.) that are used for xerographi outsourcing silicone resin with the preparation developer.

(4) mensuration of amount of electrostatic charge (saturated electric weight)

The humidity of above-mentioned developer is controlled at 23 ℃, 50%R.H. at least 8 hours, the friction force during with 50r.p.m. stirs 1,3,7,20 respectively to each duplicate samples with the terbler vibromixer then, 60 and 120 minutes, measures the amount of electrostatic charge of each section period.To not have the amount of electrostatic charge that period of rising appreciably records in amount of electrostatic charge and be decided to be saturated electric weight.

The equipment that is used for this mensuration: formula coulometry device (providing by Toshiba Chemical Co.Ltd.) is provided

(5) evaluation criterion of charged speed

According to the above-mentioned electric weight result who records, charged speed is defined the level according to following standard:

A: when electric weight reach capacity electric weight 80% the time, the used friction stir time is less than 7 minutes.

B: the used friction stir time is 7-20 minute.

C: the used friction stir time is 20-60 minute.

D: the used friction stir time was greater than 60 minutes.

(6) environmental factor dependence is measured

The humidity of above-mentioned developer is controlled at the amount of electrostatic charge of measuring these samples behind hot and humid degree and the low temperature and low humidity degree.

Low temperature and low humidity: 10 ℃, 40%R.H.

Hot and humid: 35 ℃, 85%R.H.

Evaluation criterion:

Amount of electrostatic charge in low temperature and low humidity and the hot and humid environment is changed to ... A: little, B: medium, C: big.

(7) mensuration of CHARGE DISTRIBUTION

The humidity of above-mentioned developer is controlled at 23 ℃, and 50%R.H. is no less than 8 hours, and the friction force biased sample when using the terbler vibromixer with 50r.p.m. then 20 minutes is measured CHARGE DISTRIBUTION then.

Equipment: particle charge distribution tests instrument (EST-1, by Hosokawa Micron Co., Ltd. provides)

Evaluation criterion:

A: charge amount distribution is narrower.

B: charge amount distribution is medium.

C: charge amount distribution broad.

(8) copy test

Carry out the continuous copy test of above-mentioned developer with a duplicating machine that is used to estimate.

The duplicating machine that is used to estimate:

Use the electronegative Xerox of the sensitized material of selenium.The copy paper number is 20,000 continuously.

Evaluation criterion:

A: it is good to duplicate after 20,000 the duplicating imaging on paper continuously.

B: duplicate continuously that the duplicating image quality on paper slightly descends after 20,000.

C: duplicate continuously that the duplicating image quality on paper obviously descends after 20,000.

D: it is just very poor to duplicate image quality from the beginning.

(9) evaluation of transparency

Do not adding kneading toner binder and charge adjusting agent under the sharp low-molecular-weight polypropylene condition of colorant, the sample cast after will mediating with melt indexer is then made the post sheet of 5mm and is estimated the transparency of post sheet.

Evaluation criterion:

A: transparent

B: slightly muddy

C: muddiness is white in color

Embodiment A 1

In the dimethylbenzene of boiling temperature, make 1-alkene mixture/copolymer-maleic anhydride (PA-124 of 733 parts of C12-14, by Mitsubishi Chemical Co., Ltd. provide) removed water in 4 hours simultaneously to form acid imide with 307 parts of meta nitro aniline reactions, boil off dimethylbenzene then and obtain charge adjusting agent of the present invention (A1).

Embodiment A 2

Repeat embodiment A 1, but with 360 part 3, the 4-dichloroaniline replaces meta nitro aniline to obtain charge adjusting agent A2 of the present invention.

Embodiment A 3

In the dimethylbenzene of boiling temperature, make the 1-alkene mixture/copolymer-maleic anhydride (PA-124) and 130 parts of perfluoroalkyl ethanol (Cheminox FA-M (C10up) of 647 parts of C12-14, by Japan MectronCo., Ltd. provides) carried out the half ester reaction 5 hours.

Add 256 parts of meta nitro aniline reactions then and removed water in 5 hours simultaneously, boil off dimethylbenzene then and obtain charge adjusting agent of the present invention (A3) to form acid imide.

Embodiment A 4

In autoclave, potpourri/copolymer-maleic anhydride (the PA-124 that adds the 1-alkene of 800 parts of C12-14, by Mitsubishi Chemical Industries, Ltd. provide) and 200 parts of styrene, carry out graft polymerization at 80 ℃ at 0.4 part in the presence of as the di-t-butyl peroxide of initiating agent, with preparation graft polymer (1).

Repeat embodiment A 3, but with 1-alkene mixture/copolymer-maleic anhydride (PA-124) of 809 parts of above-mentioned graft polymer (1) replaced C 12-14 to make charge adjusting agent of the present invention (A4).

Embodiment A 5

(dibutyltin oxide) is catalyzer with 2 parts of dibutyl tin oxides, is 6,000 at 230 ℃ of polycondensations, 723 parts of bisphenol-A epoxy propane 2mol adduct and 348 parts of terephthalic acid (TPA)s to make weight-average molecular weight, and hydroxyl value is the polyester (1) of 20mg KOH/g.

In the dimethylbenzene of boiling temperature, 1-alkene mixture/copolymer-maleic anhydride (PA-124) of 647 parts of C12-14,162 parts of polyester (1) and 130 parts of perfluoroalkyl ethanol (Cheminox FA-M (C10up)) half ester reaction 5 hours.

Add 256 parts of meta nitro aniline reactions then and removed water in 5 hours simultaneously, boil off dimethylbenzene then and obtain charge adjusting agent of the present invention (A5) to form acid imide.

Embodiment A 6

N in boiling temperature, in the dinethylformamide (DMF), with the di-t-butyl peroxide is initiating agent, make 508 parts of m-nitro base maleimides, 412 parts of methacrylic acid perfluoroalkyl ethyl ester (CheminoxFAMAC-C8, by Japan Mectron Co., Ltd. provides) and 80 parts of 2-acrylamides-2-methyl propane sulfonic acid polymerization 8 hours, boil off DMF then to make charge adjusting agent of the present invention (A6).

Embodiment A 7

Repeat embodiment A 6, but with 457 part 3,4-dichlorophenyl maleimide, 503 parts of methacrylic acid perfluoroalkyl ethyl esters and 40 parts of Sodium styrene sulfonate replace m-nitro base maleimide, 412 parts of methacrylic acid perfluoroalkyl ethyl esters and 2-acrylamide-2-methyl propane sulfonic acid are to make charge adjusting agent A7 of the present invention.

Embodiment A 8

Adding 500 parts of styrene and DMF in 500 parts of charge adjusting agents (A7) again, is initiating agent graft polymerization 4 hours with the di-t-butyl peroxide, boils off DMF then to make charge adjusting agent of the present invention (A8).

Embodiment A 9

Repeat embodiment A 6, but with 960 part 3,4-dichlorophenyl maleimide, 40 parts of Sodium styrene sulfonate replace m-nitro base maleimide, methacrylic acid perfluoroalkyl ethyl ester and 2-acrylamide-2-methyl propane sulfonic acid are to make charge adjusting agent A9 of the present invention.

Embodiment A 10

In butanone (MEK), with 50 parts of azoisobutyronitriles is initiating agent, make 511 parts of acrylic acid perfluoroalkyl ethyl ester (FLUOWET AC-812, by Hechst Industries Co., Ltd. provide) and 223 parts of itaconic anhydride polyreactions 4 hours be 18,000 multipolymer (1) to make weight-average molecular weight.

In autoclave, add 800 parts of multipolymers (1) and 1,000 part of styrene, in the presence of as the di-t-butyl peroxide of initiating agent 180 ℃ of graft polymerizations 4 hours, pressure reducing and steaming MEK then, thus make graft polymer (2).

With 262 part 3, the 4-dichloroaniline, 37 parts of sodium sulfanilates and DMF add 1734 parts of graft copolymers (2), and reaction boiled off DMF, thereby makes charge adjusting agent of the present invention (A10) to form acid imide in 8 hours then in the DMF of boiling temperature.

Embodiment A 11

In the DMF of boiling temperature, with the azoisobutyronitrile is initiating agent, make 912 parts of methacrylic acid perfluoroalkyl ethyl esters (Cheminox FAMAC-C8) and 88 parts of Sodium styrene sulfonate polyreactions 4 hours, boil off DMF then to make charge adjusting agent of the present invention (A11).

Embodiment A 12

Repeat embodiment A 6, but with 476 part 3,4-dichlorophenyl maleimide, 524 parts of methacrylic acid perfluoroalkyl ethyl esters replace m-nitro base maleimide, 412 parts of methacrylic acid perfluoroalkyl ethyl esters and 2-acrylamide-2-methyl propane sulfonic acid are to make multipolymer (1).

200 parts of perfluorooctane sulfonate sodium are added multipolymer (1), and uniform dissolution boils off DMF then, to make charge adjusting agent of the present invention (A12).

Embodiment A 13

Repeat embodiment A 6, but only with 1,000 part 3,4-dichlorophenyl maleimide replaces m-nitro base maleimide, methacrylic acid perfluoroalkyl ethyl ester and 2-acrylamide-2-methyl propane sulfonic acid are to make homopolymer (1).

200 parts of perfluorooctane sulfonate barium are added homopolymer (1), and uniform dissolution boils off DMF then, to make charge adjusting agent of the present invention (A13).

Reference examples CA1

Repeat embodiment A 1, but replace meta nitro aniline, to make contrast charge adjusting agent (CA1) with 243 parts of m-aminophenols.

Reference examples CA2

In toluene and methanol mixture, be initiating agent with the azoisobutyronitrile, made 920 parts of styrene and 80 parts of 2-acrylamides-2-methyl propane sulfonic acid polyreaction 8 hours, pressure reducing and steaming solvent then is to make contrast charge adjusting agent (CA2).

Reference examples CA3

In the DMF of boiling temperature, be initiating agent with the azoisobutyronitrile, make 912 parts of styrene and 88 parts of Sodium styrene sulfonate polyreactions 4 hours, pressure reducing and steaming DMF then is to make contrast charge adjusting agent (CA3).

Reference examples CA4

In the toluene of boiling temperature, be initiating agent with the azoisobutyronitrile, make 1,000 part of methacrylic acid perfluoroalkyl polymerizable methacrylate reaction 4 hours, pressure reducing and steaming DMF contrasts charge adjusting agent (CA4) to make then.

Reference examples CA5

Repeat embodiment A 11, but replace 912 parts of methacrylic acid perfluoroalkyl ethyl esters and 88 parts of Sodium styrene sulfonate, to make contrast charge adjusting agent (CA5) with 721 parts of methacrylic acid perfluoroalkyl ethyl esters and 278 parts of Sodium styrene sulfonate.

Reference examples CA6

With perfluorooctane sulfonate sodium with comparing charge adjusting agent (CA6).

Table 1

Charge adjusting agent dielectric loss angle tangent (tan δ) absorption of water (%)

(A1) 0.012 0.7

(A2) 0.010 0.6

(A3) 0.014 0.6

(A4) 0.009 0.5

(AS) 0.013 0.8

(A6) 0.015 1.7

(A7) 0.039 1.5

(A8) 0.017 0.9

(A9) 0.016 1.6

(A10) 0.015 0.9

(A11) 0.050 1.6

(A12) 0.088 1.3

(A13) 0.084 0.9

(CA1) 0.007 3.1

(CA2) 0.006 4.3

(CA3) 0.006 5.7

(CA4) 0.007 0.1

(CA5) 0.420 8.4

(CA6) - -

Embodiment B 1

40 parts of charge adjusting agents (A4) and 1000 parts of styrene toner binders (Himer UNI-3000 is provided by Sanyo Chemical Industies Ltd.) are dissolved and be blended in the toluene.Once removing toluene, get final product toner binder of the present invention (B1).

Embodiment B 2

20 parts of charge adjusting agents (A8) and 1000 parts of styrene toner binders (Himer UNI-3000) are dissolved and be blended among the DMF.Once removing DMF, get final product toner binder of the present invention (B2).

After with the tangent plane dyeing of ruthenium tetroxide, can be observed the discrete particles of about 1 μ m with transmission electron microscope (TEM) to toner binder composition (B2).But, in Himer UNI-3000, do not observe the existence of discrete particles.

Embodiment B 3

With 2 parts of dibutyl tin oxides is the polycondensation reaction that catalyzer carries out 417 parts of bisphenol-A epoxy propane 2mol adducts, 341 parts of bisphenol-A epoxy ethane 2mol adducts and 310 parts of terephthalic acid (TPA)s, is 8000 polyester toner bonding agent (1) to make weight-average molecular weight.

Mix 10 parts of charge adjusting agents (A7) and 1,000 part of toner binder (1) in the mode that is same as Embodiment B 2, to make toner binder of the present invention (B3).

Can be observed the discrete particles of about 2 μ m with TEM.

Embodiment T1-T4 and reference examples CT1

Prepare various toners with following component: the charge adjusting agent shown in the table 2 (umber), 1000 parts of styrene type toner binder (Himer UNI-3000, provide by Sanyo Chemical Industies Ltd.), 50 parts of carbon black (MA-100, provide by Mitsubishi Chemical Industies Ltd.) and 40 parts of low-molecular-weight polypropylene (Viscol 660P, by Sanyo Chemical Industries, Ltd. provides), method is as follows:

At first, with mediating with double screw extrusion machine (PCM-30, by Ikegai, Ltd. provides) behind Henschel mixer (FM10B, by Mitsuimiike kakouki, Ltd provides) these components of premixed.With ultrasound wave jet mill Labo jet (by Japan Pneumatic Industries, Ltd. provide) product is further ground to form respectively behind the smart powder with air-flow sizer (MDS-I, Japan Pneumatic Industries, Ltd. providing) gradation obtains each powdered product that particle diameter is 5-20 μ m, toner T1-T4 promptly of the present invention and contrast toner (CT1).

Evaluation result is as shown in table 2.

Embodiment T5

Repeat embodiment T1, but replace Himer UNI-3000 and do not add any charge adjusting agent, to make toner of the present invention (TB5) with 1040 parts of toner binder compositions (B1).

Evaluation result is as shown in table 2.

Embodiment T6-T13 and reference examples

Repeat embodiment T1, but replace 50 parts, to make toner of the present invention (T6)-(T13) and contrast toner (CT2)-(CT8) with 80 parts of carbon blacks.

Evaluation result is as shown in table 2.

Embodiment T14

Repeat embodiment T6, but replace Himer UNI-3000 and do not add any charge adjusting agent, to make toner of the present invention (T14) with 1020 parts of toner binder compositions (B2).

Evaluation result is as shown in table 2.

2 ( ) *1 *2 *3 *4 *5 ( T1 ) ( A1 ) 25-24 B A A B ( T2 ) ( A2 ) 25-26 B A A B ( T3 ) ( A3 ) 25-26 B A A A ( T4 ) ( A4 ) 30-24 B A A A ( T5 ) ( B1 ) 1040-23 B A A A ( T6 ) ( A6 ) 10-24 B B B A ( T7 ) ( A7 ) 10-21 A A B A ( T8 ) ( A8 ) 20-22 A A A A ( T9 ) ( A9 ) 10-18 B A B A ( T10 ) ( A10 ) 20-22 A A A A ( T11 ) ( A11 ) 10-17 A B B A ( T12 ) ( A12 ) 10-19 A A B A ( T13 ) ( A13 ) 10-19 A A B B ( T14 ) ( B2 ) 1020-21 A A A A ( CT1 ) ( CA1 ) 30-15 C B A D ( CT2 ) ( CA2 ) 50-18 C C A C ( CT3 ) ( CA3 ) 10-11 C C B D ( CT4 ) ( CA4 ) 10-10 C B B D ( CT5 ) ( CA5 ) 10-12 A C C D ( CT6 ) ( CA6 ) 10-11 A C B D ( CT7 ) ( CA4 ) / ( CA2 ) 10/50-17 C C B C ( CT8 ) -9 D C B D

* 1: saturated electric weight (μ C/g)

* 2: charged speed

* 3: environmental factor dependence

* 4: CHARGE DISTRIBUTION

* 5: copy test

Embodiment T15-T19

(preparation of toner)

With 2 parts of dibutyltin oxides is catalyzer, carries out the polycondensation reaction of 751 parts of bisphenol-A epoxy propane 2mol adducts and 104 parts of trimellitic anhydrides, is 127 ℃ polyester toner bonding agent (2) to make softening point.

(preparation of toner and evaluation)

Repeat embodiment T1, but replace the styrene type toner binder,, make toner of the present invention (T15) and (T16) according to the prescription shown in the table 3 with polyester toner bonding agent (2).

Repeat embodiment T6 again, but replace the styrene type toner binder,, make toner of the present invention (T17)-(T19) according to the prescription shown in the table 3 with polyester toner bonding agent (2).

Evaluation result sees Table 3.

Table 3 toner charge adjusting agent number amount (part) * 1 * 2 * 3 * 4 * 5 (T15) are (A5) (A7) (A10) (A12) 10-18 A A B A of 20-21 A A A A (T19) of 10-20 A A B A (T18) of 30-24 B A A B (T17) of 25-27 B A B B (T16) (A3)

* 1: saturated electric weight (μ C/g)

* 2: charged speed

* 3: environmental factor dependence

* 4: CHARGE DISTRIBUTION

* 5: copy test

Embodiment T20

Repeat embodiment T1, but with 1,000 part of polyester toner bonding agent (1), 40 parts of colorant (Firstgenmazenta R-11, by Dainippon Ink Industries, Ltd. provide) and according to the replacement of the charge adjusting agent in the prescription shown in the table 3 styrene type toner binder, to make toner of the present invention (T20).

Evaluation result sees Table 4.

Embodiment T21

Repeat embodiment T20, but replace toner binder (1) and do not add any charge adjusting agent, to make toner of the present invention (T21) with toner binder composition (B3).

Evaluation result sees Table 4.Toner charge adjusting agent number amount (part) * 1 * 2 * 3 * 4 * 6 (T20) are (B3) 1020-20 A A A of 20-22 A A A B (T21) (A10)

* 1: saturated electric weight (μ C/g)

* 2: charged speed

* 3: environmental factor dependence

* 4: CHARGE DISTRIBUTION

* 6: transparency

Claims (20)

1. charge adjusting agent that is used for toner, it is characterized in that, it contains a kind of polymkeric substance of ethylene linkage unsaturated monomer, the dielectric loss angle tangent of 0.008 to 0.3 when described polymkeric substance has 100kHz (tan δ) and the absorption of water of 10% (weight) at the most, and also it is selected from:

(i) has the polymkeric substance (A1) of the monomer (1) of an aromatic ring that is replaced by at least a electron-withdrawing group (X) that is selected from halogen atom, nitro and cyano group; With

(ii) have the monomer (2) of organic acidic group or its salt and the multipolymer (A2) of another monomer,

Wherein said polymkeric substance (A1) contains described monomer (1) unit of 5% (weight) at least, and described multipolymer (A2) contains the described monomer of 0.1-20% (weight) (2) unit, other monomeric unit of 80-99.9% (weight).

2. charge adjusting agent according to claim 1, its feature also is, wherein said monomer (1) be selected from styrene, contain aromatic ring maleimide, contain the clothing health acid imide of aromatic ring, the acrylate that contains aromatic ring or methacrylate, the acrylamide that contains aromatic ring or Methacrylamide and contain the ethylene linkage type unsaturated monomer of the vinethene of aromatic ring, the aromatic ring of described monomer is replaced by electron withdraw group (X).

3. charge adjusting agent according to claim 1, its feature are that also wherein said monomer (1) is phenyl maleimide or phenyl clothing health acid imide, and aromatic ring is wherein replaced by an electron withdraw group (X).

4. charge adjusting agent according to claim 1, its feature are that also wherein said polymkeric substance (A1) also contains the monomer with an organic acidic group or its salt (2) unit of 0.1-20% (weight).

5. charge adjusting agent according to claim 1, its feature also be, wherein said polymkeric substance (A1) also contains and is selected from monomer (3) unit that contains perfluoroalkyl monomer and siloxanyl monomers.

6. charge adjusting agent according to claim 4, its feature also be, wherein said polymkeric substance (A1) also contains and is selected from monomer (3) unit that contains perfluoroalkyl monomer and siloxanyl monomers.

7. charge adjusting agent according to claim 4, its feature are that also the content of wherein said monomer (3) unit is 10-94.9% (weight).

8. charge adjusting agent according to claim 1, its feature are that also wherein said organic acid is selected from sulfonic acid, sulfaminic acid, acid sulfate, carboxylic acid and acid phosphoric acid ester.

9. charge adjusting agent according to claim 1, its feature are that also wherein said organic acid is a sulfonic acid.

10. charge adjusting agent according to claim 1, its feature are that also wherein said monomer (2) is the monomer that contains the aromatic sulphonate group.

11. charge adjusting agent according to claim 1, its feature are that also wherein said sulfonic acid is selected from styrene sulfonic acid, sulfophenyl acrylamide, sulfophenyl maleimide and sulfophenyl clothing health acid imide.

12. charge adjusting agent according to claim 1, its feature are that also wherein said salt is to be selected from salt at least a in alkaline metal, earth alkali metal, amine and the ammonium.

13. charge adjusting agent according to claim 1, its feature are that also wherein said other monomer is to be selected from the monomer that contains the perfluoroalkyl monomer and contain the siloxy group monomer.

14. charge adjusting agent according to claim 1, its feature are that also wherein said polymkeric substance contains the multipolymer (AB) with following component:

Component (a) by polymkeric substance (A) formation that is selected from described polymkeric substance (A1) and described multipolymer (A2), with the component (b) that is made of the polymkeric substance (B) that is selected from styrene polymer (B1) and polyester (B2), described component (b) combines by grafting or block fashion with component (a).

15. charge adjusting agent according to claim 1, its feature are that also the weight-average molecular weight of wherein said polymkeric substance is 1,000 to 500,000.

16. charge adjusting agent according to claim 14, its feature are that also the weight-average molecular weight of wherein said component (a) is 1,000-100, and 000, the weight-average molecular weight of component (b) is 1,000-500,000.

17. a charge adjusting agent composition is characterized in that, it contains charge adjusting agent according to claim 1 and a kind of perfluoroalkyl acylate (α) that contains.

18. a toner binder composition is characterized in that, it contains charge adjusting agent according to claim 1 and a kind of toner binder resin.

19. a toner is characterized in that, it contains a kind of toner binder resin, a kind of colorant and charge adjusting agent according to claim 1.

20. toner according to claim 19, its feature are that also wherein said toner binder constitutes a continuous phase, and described charge adjusting agent constitutes discontinuous regional structure.