CN1759102A

CN1759102A - Monoazo iron complex compound, charge control agent containing the same, and toner

Info

Publication number: CN1759102A
Application number: CN 200380110218
Authority: CN
Inventors: 大塚英之; 根本一男; 大谷伸二; 鈴木教之; 山田英祐; 大久保正樹
Original assignee: Hodogaya Chemical Co Ltd
Current assignee: Hodogaya Chemical Co Ltd
Priority date: 2003-03-31
Filing date: 2003-11-20
Publication date: 2006-04-12
Anticipated expiration: 2023-11-20
Also published as: CN100402504C

Abstract

To provide an electrostatic charge regulator without containing a harmful metal, without having a fear of easy ignition or explosion and excellent in electrostatic charge-imparting effect, and a negatively electrostatic charged toner. This monoazo iron complex compound is expressed by formula (1) [wherein, A<SB>1</SB>, A<SB>2</SB>, B<SB>1</SB>, B<SB>2</SB>are each independently H, an alkyl or a halogen atom; Js are each H, an alkali metal, NH<SB>4</SB>or an alkylammonium and may be >=2 kinds of them; X<SB>1</SB>, X<SB>2</SB>are each independently H, an alkyl or a halogen atom; Y<SB>1</SB>, Y<SB>2</SB>are each independently H, an alkyl or an aromatic group having a substituent; but the case that A<SB>1</SB>, A<SB>2</SB>, B<SB>1</SB>, B<SB>2</SB>, X<SB>1</SB>, X<SB>2</SB>, Y<SB>1</SB>and Y<SB>2</SB>are H at the same time is excluded].

Description

Monoazo/iron complex compound, the charge control agent that has used this compound and toning agent

Technical field

The present invention relates in fields such as electrofax, electrostatic recording, to be used for electrostatic latent image development the employed charge control agent of image processing system and contain the electronegativity toning agent of charge control agent.

Background technology

Form by the electrofax mode in the step of image, form electrostatic latent image on by inorganic or photoreceptor that organic materials forms, this sub-image utilizes toner development again, and transfer-fixing is gone up in paper and plastics film etc. and formed visual image then.According to its formation, photoreceptor possesses electronegativity and positive polarity, when remaining, utilizes the charging property toner development of contrary sign as electrostatic latent image by exposure lettering portion.On the other hand, when lettering portion is developed except that electricity overturns, utilize the charging property toner development of same-sign.

Toning agent is made of binder resin, tinting material and other additive.In order to give desirable charged characteristic (charged speed, charged level, charged stability etc.), ageing stability, environmental stability etc., generally add charge control agent.Can improve the characteristic of toning agent largely by adding this charge control agent.

What proposed has a controlled charge control agent of giving effect of negative electricity as practicability in the past, can exemplify central metal and be chromium the Monoazo metal coordination compound or same be the Monoazo metal coordination compound of central metal with iron, but the also metal complex or the salt of exemplified by alkyl groups Whitfield's ointment or aromatic series hydroxy acid.

But, it is not ideal enough that these charge control agents are given effect to the affinity of the binder resin of toning agent and frictional electrification, the speed that electrifies is fast inadequately, and the copy image at initial stage is distinct inadequately, the labile shortcoming of quality of the copy image in duplicating continuously so exist.In addition, the charge control agent that is composition with metal complex or its salt of alkyl salicylate or aromatic series hydroxy acid exist vary within wide limits corresponding to the toning agent charged characteristic of envrionment conditions, because of season the reason image quality change significant disadvantages.

The compound existence that has part to solve these problems in the monoazo chromium coordination compound, but fail to generate the possibility of the deleterious 6 valency chromium of denier when negative fully burning is discarded, so have pair environment and human body to cause dysgenic danger.Therefore, wish to find safer metal of use and the charge control agent that can fully be met at aspect of performance.

In addition, open to have disclosed in the clear 61-155464 communique the Japanese Patent spy and use with the toning agent of iron as the charge control agent of central metal.Though do not use chromium to have practical carried charge (μ c/g at least-10) as the electronegativity charge control agent of central metal, it rises electrically not as chromium complex, and the problem that the carried charge under the high humidity environment descends is still unresolved.In addition, in the flat 8-500912 communique of the special table of Japanese Patent, disclosed some azo iron complexs, but because well behaved complex compound is the azo complex compound with a plurality of nitros all, therefore in compound synthetic often with the danger of blast on fire.When particularly central metal was iron, explosion phenomenon on fire was obvious, and drying and pulverising step all become extremely dangerous operation.In addition, the crush type toning agent generally by extruding mixing roll etc. by mixing, and it is pulverized and makes, so the possibility of the powder blast when toning agent is made is also not little.Though the danger of the blast on fire when being central metal with chromium is lower than iron, the great majority of the azo chromium complex with nitro of gained are autoreactivity material (the 5th class hazardous material) in this case.

The announcement of invention

The purpose of this invention is to provide novel Monoazo/iron complex compound (complex compound), especially provide not contain the such poisonous metal of chromium and compound easy to be on fire of nitro can not occur containing and the charging property of the phenomenon of blast is given respond well charge control agent, also provide use this charge control agent have an electrical electronegativity toning agent of high-band.

The present invention is the invention of finishing after to achieve these goals and conscientiously studying, and its major technique thes contents are as follows described.

1. the Monoazo/iron complex compound of formula [1] expression,

In the formula [1], A ₁, A ₂, B ₁, B ₂Mutually independent, expression H, alkyl or halogen atom, alkyl is preferably the alkyl of carbonatoms 1～8, the alkyl of carbonatoms 1～4 more preferably, halogen atom is preferably the chlorine atom; J represents H, basic metal, NH ₄Or alkylammonium, also can be wherein more than 2 kinds, the alkyl of alkylammonium is the alkyl of carbonatoms 1～12, is preferably the alkyl of carbonatoms 3～8, can also be that 1～4 identical or different alkyl combines with nitrogen-atoms and the group that forms; X ₁, X ₂Independent mutually, expression H, alkyl, halogen atom; Y ₁, Y ₂Independent mutually, to represent H, alkyl, can have substituent aromatic group, alkyl is preferably the alkyl of carbonatoms 1～8, more preferably the group of carbonatoms 1～4; But A ₁, A ₂, B ₁, B ₂, X ₁, X ₂, Y ₁, Y ₂Be except the situation of hydrogen atom simultaneously.

2. the Monoazo/iron complex compound of formula [2] expression,

In the formula [2], J represents H, Na, NH ₄Or alkylammonium, also can be wherein more than 2 kinds, the alkyl of alkylammonium is the alkyl of carbonatoms 1～12, is preferably the alkyl of carbonatoms 3～8, can also be that 1～4 identical or different alkyl combines with nitrogen-atoms and the group that forms; X ₁, X ₂Independent mutually, expression H, alkyl or halogen atom; Y ₁, Y ₂Mutually independent, expression H, alkyl or halogen atom, alkyl is preferably the alkyl of carbonatoms 1～8, the group of carbonatoms 1～4 more preferably, halogen atom is preferably the chlorine atom.

3. the Monoazo/iron complex compound of formula [3] expression,

In the formula [3], J represents H, Na, NH ₄Or alkylammonium, also can be wherein more than 2 kinds, the alkyl of alkylammonium is the alkyl of carbonatoms 1～12, is preferably the alkyl of carbonatoms 3～8, can also be that 1～4 identical or different alkyl combines with nitrogen-atoms and the group that forms.

4. the Monoazo/iron complex compound of formula [4] expression,

In the formula [4], J represents H, Na, NH ₄Or alkylammonium, also can be wherein more than 2 kinds.

5. the Monoazo/iron complex compound of formula [5] expression.

6. charge control agent is an effective constituent with each described Monoazo/iron complex compound in above-mentioned 1～5.

7. the charge control agent of above-mentioned 6 records, the volume average particle size of this charge control agent is 0.1～20 μ m.

8. toning agent contains each described Monoazo/iron complex compound, tinting material and binder resin in above-mentioned 1～5 at least.

9. the toning agents of above-mentioned 8 records, Monoazo/iron complex compound are that the amount of 0.1～10 mass parts is added in toner particle with the binder resin corresponding to 100 mass parts.

10. above-mentioned 8 described toning agents, Monoazo/iron complex compound are that the amount of 0.2～5 mass parts is added in toner particle with the binder resin corresponding to 100 mass parts.

11. each described toning agent in above-mentioned 8～10, the acid number of binder resin is 0.1～100mgKOH/g.

12. each described toning agent in above-mentioned 8～11, tinting material is a magnetic substance.

13. above-mentioned 12 described toning agents, magnetic substance are martial ethiops.

14. above-mentioned 12 or 13 described toning agents contain the magnetic substance of 10～200 mass parts corresponding to the binder resin of 100 mass parts.

15. each described toning agent in above-mentioned 8～11, tinting material is non magnetic tinting material, contains 0.1～20 mass parts corresponding to the binder resin of 100 mass parts.

16. each described toning agent also contains wax in above-mentioned 8～15.

17. above-mentioned 16 described toning agents, the fusing point of wax are 70 ℃～140 ℃.

18. above-mentioned 16 or 17 described toning agents contain the wax of 0.2～20 mass parts corresponding to the binder resin of 100 mass parts.

19. each described toning agent in above-mentioned 8～18, the volume average particle size of toning agent are 2～15 μ m.

20. each described toning agent in above-mentioned 8～18, the volume average particle size of toning agent are 3～12 μ m.

21.1 composition is a photographic developer, is formed by each described electronegativity toning agent in above-mentioned 8～20.

22.2 composition is a photographic developer, it is that 2 compositions with electronegativity toning agent and carrier are photographic developer, wherein, this toning agent contains binder resin, tinting material and Monoazo/iron complex compound at least, and this Monoazo/iron complex compound is each described Monoazo/iron complex compound in above-mentioned 1～5.

23. above-mentioned 22 described 2 compositions are photographic developer, Monoazo/iron complex compound is being that the amount of 0.1～10 mass parts is added in toner particle corresponding to 100 mass parts binder resins.

24. above-mentioned 22 described 2 compositions are photographic developer, Monoazo/iron complex compound is being that the amount of 0.2～5 mass parts is added in toner particle corresponding to 100 mass parts binder resins.

25. described 2 compositions of each in above-mentioned 22～24 are photographic developer, it is that resin is as binder resin that toning agent contains styrene-propene acid.

26. above-mentioned 25 described 2 compositions are photographic developer, the acid number of binder resin is 0.1～100mgKOH/g.

27. above-mentioned 25 described 2 compositions are photographic developer, the acid number of binder resin is 0.1～50mgKOH/g.

28. each described 2 compositions are photographic developer in above-mentioned 22～27, the second-order transition temperature of binder resin (Tg) is 35～80 ℃.

29. each described 2 compositions are photographic developer in above-mentioned 22～28, also contain wax.

30. above-mentioned 29 described toning agents, the fusing point of wax are 70 ℃～140 ℃.

31. above-mentioned 29 or 30 described toning agents contain the wax of 0.2～20 mass parts corresponding to the binder resin of 100 mass parts.

32. each described 2 compositions are photographic developer in above-mentioned 22～31, the volume average particle size of toning agent is 2～15 μ m.

33. each described 2 compositions are photographic developer in above-mentioned 22～31, the volume average particle size of toning agent is 3～12 μ m.

34. each described 2 compositions are photographic developer in above-mentioned 22～33, carrier is the resin coating carrier.

35. above-mentioned 34 described 2 compositions are photographic developer, the resin coating carrier is by the carrier core particle and as the resin formation of this carrier core particle surface of coating (coating) of coating material, this lining (coating) material has the resin more than a kind that is selected from tetrafluoroethylene, a chlorotrifluoroethylene polymers, poly(vinylidene fluoride), silicone resin, polyester, phenylethylene resin series, acrylic resin, polymeric amide, polyvinyl butyral acetal, the amino acrylates resin.

The charged speed of charge control agent of the present invention is fast, compare with charge control agent in the past, can toning agent be electrified, its carried charge has the higher charged effect of giving, and carried charge is stable corresponding to the variation maintenance of environment such as temperature and humidity on every side.In addition, may not cause dysgenic metal to environment owing to do not contain chromium etc., and do not have nitro such play the higher substituting group of bad temper, so the security of compound is higher.

The toning agent that contains this charge control agent can obtain all good images of picture characteristics evaluation such as image color, photographic fog concentration, some reproducibility or hachure reproducibility in the visualization way of 1 composition system or 2 compositions system.

The simple declaration of accompanying drawing

Fig. 1 is the infrared absorpting light spectra of compound of the No.1 of table 1 of the present invention.

Fig. 2 is the infrared absorpting light spectra of compound of the No.2 of table 1 of the present invention.

Fig. 3 is the infrared absorpting light spectra of compound of the No.3 of table 1 of the present invention.

Fig. 4 is the infrared absorpting light spectra of compound of the No.4 of table 1 of the present invention.

Fig. 5 is the infrared absorpting light spectra of compound of the No.5 of table 1 of the present invention.

Fig. 6 is the infrared absorpting light spectra of compound of the No.6 of table 1 of the present invention.

Fig. 7 is the infrared absorpting light spectra of compound of the No.11 of table 1 of the present invention.

Fig. 8 is the infrared absorpting light spectra of compound of the No.12 of table 2 of the present invention.

Fig. 9 is the infrared absorpting light spectra of compound of the No.13 of table 2 of the present invention.

Figure 10 is the infrared absorpting light spectra of compound of the No.14 of table 2 of the present invention.

Figure 11 is the infrared absorpting light spectra of compound of the No.15 of table 2 of the present invention.

Figure 12 is the infrared absorpting light spectra of compound of the No.19 of table 2 of the present invention.

Figure 13 is the infrared absorpting light spectra of compound of the No.21 of table 2 of the present invention.

Figure 14 is the infrared absorpting light spectra of compound of the No.22 of table 2 of the present invention.

The best mode that carries out an invention

Monoazo/iron complex compound of the present invention is the good compound of environmental stability, and is the respond well compound of charged control.By Monoazo/iron complex compound of the present invention is used for toning agent, can obtain to rise fast electrically and the high-band electric weight, consequently, can obtain distinct image.

Monoazo/iron complex compound of the present invention can adopt the preparation method of known Monoazo/iron complex compound to make, and below record possesses representational preparation method, but is not limited in this.At first, in diazonium compositions such as 4-chloro-2-amino-phenol, add mineral acids such as hydrochloric acid and sulfuric acid, if below the interior temperature drop to 5 ℃, then during keeping temperature below 10 ℃ in the water-soluble Sodium Nitrite of dropping.By reacting in 30 minutes and even 3 hours, make 4-chloro-2-amino-phenol diazotization in stirring below 10 ℃.Add thionamic acid then, it is remaining to confirm not have superfluous nitrous acid with potassium iodide starch test paper.

Then, add 3-methyl isophthalic acid-(4-chloro-phenyl-)-organic solvents such as coupling composition, aqueous sodium hydroxide solution, yellow soda ash and butanols such as 5-pyrazolone, stirring and dissolving under the room temperature.Then, add aforementioned diazonium compound therein, stirred for several hour is carried out coupling under the room temperature.After the stirring, confirm no diazonium compound and resorcin reaction, illustrate that reaction finishes.Fully stir after adding water, leave standstill the back separatory.Then, add aqueous sodium hydroxide solution, agitator treating carries out separatory again.

Spendable any solvent when the organic solvent beyond the butanols when carrying out above-mentioned coupling can adopt coupling is preferably monohydroxy-alcohol or dibasic alcohol.Monohydroxy-alcohol can exemplify methyl alcohol, ethanol, n-propyl alcohol, 2-propyl alcohol, propyl carbinol, isopropylcarbinol, sec-butyl alcohol, Pentyl alcohol, primary isoamyl alcohol, ethylene glycol one alkyl oxide (carbonatoms 1～4) etc.Dibasic alcohol can exemplify ethylene glycol etc., and wherein, solvent is preferably butanols.

Adding water, Whitfield's ointment, propyl carbinol, yellow soda ash in the butanol solution of above-mentioned Monoazo compound stirs.Add ferric chloride in aqueous solution and yellow soda ash again, with interior temperature rise to 30～40 ℃, with the TLC following response.After 5～10 hours, confirm that the spot of raw material disappears, proved response finishes.It is static that stirring stops the back, carries out separatory.Then, add entry, butanols, aqueous sodium hydroxide solution, carry out neutralizing treatment.Filter again, take out filter cake, wash with water.

Then, add ammonium sulfate in water, stir on intensification limit, limit, if interior temperature reaches 85～90 ℃, then drips the dispersion soln of above-mentioned filter cake.While steam at 97～99 ℃ and to remove butanols and stirred 1 hour, behind the cold filtration, wash filter cake with water.Vacuum-drying is confirmed to reach constant, can obtain Monoazo/iron complex compound of the present invention.

Below, in table 1 and table 2, exemplify the object lesson of Monoazo/iron complex compound of the present invention, but the present invention is not limited in the compound of being put down in writing.Symbol A in table 1 and the table 2 ₁, A ₂, B ₁, B ₂, J, X ₁, X ₂, Y ₁, Y ₂Corresponding with the implication of record in the aforementioned formula [1] respectively, the combining site in the table is digital corresponding with the middle the position of substitution put down in writing of aforementioned formula [1].In addition, the compound N in the table 2 o.19, the Bu as counterion J, the Pr of No.20 represent normal-butyl and n-propyl respectively, and compound N counterion J o.21 is 90% NH ₄, 5% Na and 5% H.

Table 1

Table 2

Charge control agent of the present invention is aforementioned formula [1], be preferably aforementioned formula [2], more preferably aforementioned formula [4], be preferably aforementioned formula [3], the Monoazo/iron complex compound of [5] expression, and the Monoazo/iron complex compound of aforementioned formula [1]～[5] expression can more than a kind or 2 kinds and be used.In addition, also can sneak into unreacted raw material or intermediate or the such reaction promotor of Whitfield's ointment below 10%.

The electric charge control characteristic of charge control agent of the present invention, environment resistant and weather resistance is good, when being used for toning agent, can obtain not can fogged, image color, some reproducibility and hachure reproducibility preferable image.

No matter the variation of the toning agent that contains Monoazo/iron complex compound of the present invention its charged characteristic under high humidity or low wet environment all seldom, can keep stable developing property.

Charge control agent of the present invention better is that its volume average particle size is adjusted into 0.1～20 μ m and re-uses, and is more preferably and is adjusted into 0.1～10 μ m.If above-mentioned volume average particle size is less than 0.1 μ m, this charge control agent that then appears at toner surface is few, can't obtain desirable electric charge control effect, if greater than 20 μ m, then the charge control agent that is scattered from toning agent increases, and so the interior contaminated detrimentally affect that waits of generation machine is undesirable.

Make the method that is contained in toning agent as the Monoazo/iron complex compound that is used for charge control agent of the present invention, comprise when in binder resin, adding tinting material etc. add, mixing, the method (crushed toner) pulverized or in the monomer of polymerizability, add Monoazo/iron complex compound, make its polymerization obtain the method (polymerization toner) of toning agent, in advance in the inner method of adding of toner particle (in add) and make toner particle in advance, in the method for the surface of toner particle interpolation (outside add).In add the binder resin of the addition of the Monoazo/iron complex compound of the present invention when toner particle corresponding to 100 mass parts, be preferably 0.1～10 mass parts, more preferably 0.2～5 mass parts.Add outward when toner particle, be preferably 0.01～5 mass parts, more preferably 0.01～2 mass parts.In addition, preferably the method by mechanochemistry makes Monoazo/iron complex compound be bonded to surfaces of toner particles.

In addition, be that the charge control agent of effective constituent can and be used with known other electronegativity charge control agent with Monoazo/iron complex compound of the present invention.And the charge control agent preferably of usefulness can to exemplify azo beyond the present invention be that iron complex or complex salt, azo are that chromium complex or complex salt, azo are that manganese complex or complex salt, azo are that cobalt complex or complex salt, azo are the zirconium complex or the complex salt of the aluminium complex of the zinc complex of the chromium complex of zirconium complex or complex salt, carboxylic acid derivative or complex salt, carboxylic acid derivative or complex salt, carboxylic acid derivative or complex salt, carboxylic acid derivative.Aforementioned carboxylic acid derivative is preferably aromatic hydroxy-carboxylic, and more preferably 3, the 5-di-tert-butyl salicylic acid.In addition, can exemplify boron complex or complex salt, electronegativity resin type charge control agent etc.

And the addition during with charge control agent of the present invention and other charge control agent is the binder resin corresponding to 100 mass parts, is preferably 0.1～10 mass parts as the charge control agent beyond the Monoazo/iron complex compound of the present invention of charge control agent.

Be used to binder resin of the present invention and can adopt known resin.Can exemplify vinyl polymer such as styrenic monomers, acrylic monomer, metha crylic monomer or these monomeric multipolymers that forms more than 2 kinds etc., the polyester based polymer, the polyalcohols resin, resol, silicone resin, urethane resin, polyamide resin, furane resin, Resins, epoxy, xylene resin, terpine resin, coumarone-indene resin, polycarbonate resin, petroleum line resin etc.

The monomeric example of styrenic monomers, acrylic monomer, metha crylic of aforementioned vinyl polymer or formation multipolymer exemplifies as follows, but is not limited thereto.

Styrenic monomers can exemplify vinylbenzene, o-methyl styrene, a vinyl toluene, p-methylstyrene, to styryl phenyl, to ethyl styrene, 2, the 4-dimethyl styrene, to n-amylbenzene ethene, to t-butyl styrene, to positive hexyl phenenyl ethene, to n-octyl vinylbenzene, align nonyl benzene ethene, align decyl vinylbenzene, align dodecyl vinylbenzene, to methoxy styrene, to chloro-styrene, 3, vinylbenzene or derivatives thereofs such as 4-dichlorostyrene, m-nitro ethene, ortho-nitrophenyl ethene, p-nitrophenyl ethene etc.

But vinylformic acid such as acrylic monomer exemplified by acrylic or methyl acrylate, ethyl propenoate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, vinylformic acid n-octyl, vinylformic acid dodecyl ester, 2-EHA, stearyl acrylate alcohol ester, vinylformic acid 2-chloroethene ester, phenyl acrylate or its ester class etc.

But methacrylic acids such as metha crylic monomer exemplified by methyl vinylformic acid, methyl methacrylate, Jia Jibingxisuanyizhi, propyl methacrylate, n-BMA, Propenoic acid, 2-methyl, isobutyl ester, n octyl methacrylate, methacrylic acid dodecyl ester, methacrylic acid 2-ethylhexyl, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethyl aminoethyl methacrylate or its ester class etc.

Other monomeric example of aforementioned vinyl polymer or formation multipolymer can exemplify following (1)～(18).(1) ethene, propylene, butylene, monoene hydro carbons such as iso-butylene, (2) divinyl, Polyene Hydrocarbonses such as isoprene, (3) vinylchlorid, vinylidene chloride, bromine ethene, vinyl halides classes such as vinyl fluoride, (4) vinyl-acetic ester, propionate, vinyl esters such as vinyl benzoate, (5) methoxy ethylene, ethyl vinyl ether, vinyl ethers such as VINYL ISOBUTYL ETHER, (6) ethenyl methyl ketone, the vinyl hexyl ketone, vinyl ketones such as methyl isopropenyl ketone, (7) N-vinyl pyrrole, the N-vinylcarbazole, N-vinyl indoles, N-vinyl compounds such as N-vinyl pyrrolidone, (8) vinyl naphthalene, (9) vinyl cyanide, methacrylonitrile, acrylic or methacrylic acid derivatives such as acrylamide etc., (10) toxilic acid, citraconic acid, methylene-succinic acid, alkenyl succinic acid, fumaric acid, the unsaturated dibasic acid that methylfumaric acid is such, (11) maleic anhydride, citraconic anhydride, itaconic anhydride, the unsaturated dicarboxylic acid anhydride that alkenyl succinic anhydride is such, (12) toxilic acid one methyl esters, toxilic acid one ethyl ester, toxilic acid one butyl ester, citraconic acid one methyl esters, citraconic acid one ethyl ester, citraconic acid one butyl ester, methyl ester of itaconic acid, alkenyl succinic acid one methyl esters, fumaric acid one methyl esters, the monoesters of the unsaturated dibasic acid that methylfumaric acid one methyl esters is such, (13) dimethyl maleate, the unsaturated dibasic acid ester that dimethyl fumarate is such, (14) Ba Dousuan, the α that styracin is such, beta-unsaturated acid, (15) crotonic anhydride, the α that cinnamic anhydride is such, the beta-unsaturated acid acid anhydride, (16) this α, the acid anhydrides of beta-unsaturated acid and lower fatty acid, the thiazolinyl propanedioic acid, the thiazolinyl pentanedioic acid, the thiazolinyl hexanodioic acid, the monomer that their acid anhydrides and their monoesters are such with carboxyl, (17) vinylformic acid 2-hydroxy methacrylate, 2-hydroxyethyl methacrylate, acrylic or methacrylics such as methacrylic acid 2-hydroxy propyl ester acid hydroxyalkyl acrylate class, (18) 4-(1-hydroxyl-1-methyl butyl) vinylbenzene, 4-(1-hydroxyl-1-methyl hexyl) the such monomer of vinylbenzene with hydroxyl.

In the toning agent of the present invention, vinyl polymer or multipolymer as binder resin can possess by the crosslinked crosslinking structure of the linking agent with the vinyl more than 2, can exemplify Vinylstyrene, divinyl naphthalene as the divinyl aromatic compound of used in this case linking agent.As exemplifying glycol diacrylate, 1 with alkyl chain bonded diacrylate compounds, 3-butylene glycol diacrylate, 1,4-butylene glycol diacrylate, 1, the dimethacrylate of 5-pentanediol diacrylate, 1,6 hexanediol diacrylate, neopentylglycol diacrylate or above-mentioned alcohol.

Can exemplify the dimethacrylate of diethylene glycol diacrylate, triethylene glycol diacrylate, Viscoat 335HP, polyoxyethylene glycol #400 diacrylate, polyoxyethylene glycol #600 diacrylate, dipropylene glycol diacrylate or above-mentioned alcohol with the alkyl chain bonded diacrylate ester cpds that contains ehter bond.

In addition, can exemplify with the diacrylate ester cpds of the chain combination that contains aromatic group and ehter bond or dimethacrylate compound etc.Can exemplify the product of commodity MANDA (Nippon Kayaku K. K) by name as polyester type diacrylate class.

Compound, triallyl cyanurate, trimellitic acid triallyl that multifunctional linking agent can exemplify pentaerythritol triacrylate, trimethylolethane trimethacrylate acrylate, Viscoat 295, tetramethylol methane tetraacrylate, oligomer ester acrylate and obtain with the acrylate of the alternative above compound of methacrylic ester.

The consumption of these linking agents is preferably 0.01～10 mass parts corresponding to other monomer component of 100 mass parts, particularly preferably 0.03～5 mass parts.In these cross-linkable monomers, from fixation performance and the consideration of anti-skew (offset) property to resin for toner, better be adopt divinyl aromatic compound (particularly Vinylstyrene), to contain the marriage chain bonded diacrylate compounds of aromatic group and 1 ehter bond.Wherein, be preferably styrene based copolymer, form the combination of monomers that styrene-propene acid is interpolymer.

Polymerization starter as the preparation that is used for vinyl polymer of the present invention or multipolymer can exemplify 2; 2 '-Diisopropyl azodicarboxylate; 2; 2 '-azo two (4-methoxyl group-2; the 4-methyl pentane nitrile); 2; 2 '-azo two (2; the 4-methyl pentane nitrile); 2; 2 '-azo two (2-methylbutyronitrile); 2; 2 '-azo-bis-iso-dimethyl; 1; 1 '-azo two (1-cyclohexanenitrile); 2-(formamyl azo)-isopropyl cyanide; 2; 2 '-azo two (2; 4; the 4-trimethylpentane); 2-phenylazo-2 '; 4 '-dimethyl-4 '-methoxyl group valeronitrile; 2; 2 '-azo two (2-methylpropane); the peroxidation ethyl methyl ketone; the acetyl peroxide benzylacetone; peroxidation ketones such as cyclohexanone peroxide; 2; 2-two (t-butyl peroxy) butane; t-butyl hydroperoxide; cumene hydroperoxide; 1; 1; 3; the 3-tetramethyl butyl hydroperoxide; di-t-butyl peroxide; the tert-butyl peroxide cumenyl; peroxidation two cumenyls; α-(t-butyl peroxy) isopropyl benzene; the peroxidation isobutyl-; the peroxidation decoyl; the peroxidation nonanoyl; lauroyl peroxide; 3; 5,5-trimethylammonium peroxidation hexanoyl; benzoyl peroxide; m-toluyl peroxide; the peroxy dicarbonate diisopropyl ester; peroxy dicarbonate two-2-(ethyl hexyl) ester; di-n-propyl peroxydicarbonate; peroxidation carbonic acid two-2-ethoxyethyl group ester; peroxy dicarbonate diethoxy isopropyl esters; peroxidation carbonic acid two (3-methyl-3-methoxyl group butyl) ester; acetyl peroxide cyclohexyl sulphonyl; the peroxidation ra-butyl acetate; peroxidation isopropylformic acid tertiary butyl ester; peroxidation-2 ethyl hexanoic acid tertiary butyl ester; peroxidation lauric acid tertiary butyl ester; peroxidation phenylformic acid tertiary butyl ester; peroxidation carbonic acid tertiary butyl isopropyl esters; peroxidation m-phthalic acid di-t-butyl ester; peroxidation carbonic acid tertiary butyl allyl ester; peroxidation-2 ethyl hexanoic acid isopentyl ester; peroxidation six hydrogen terephthalic acid di-t-butyl esters; peroxidation nonane diacid tertiary butyl ester etc.

When binder resin is resin for styrene-propene acid, dissolve in the molecular weight distribution that the components utilising GPC of tetrahydrofuran (THF) (THF) measures in the resinous principle, have 1 peak at least, have the resin at 1 peak in the zone of molecular weight 100,000 or more at least, its fixation performance, skew property and have good keeping qualities in molecular weight 3,000～50,000 (being converted into number-average molecular weight) zone.In addition, to be preferably molecular weight distribution be 50～90% binder resin at the composition below 100,000 to the THF soluble components.Be more preferably the resin that in the zone of molecular weight 5,000～30,000, preferably has main peak in 5,000～20,000 the zone.

Binder resin is that the acid number of the vinyl polymer of resin etc. is preferably 0.1mgKOH/g～100mgKOH/g for styrene-propene acid, and more preferably 0.1mgKOH/g～70mgKOH/g is preferably 0.1mgKOH/g～50mgKOH/g.

Monomer as constituting the polyester based polymer can exemplify following compound.

Glycol component can exemplify ethylene glycol, propylene glycol, 1,3-butyleneglycol, 1,4-butyleneglycol, 2,3-butyleneglycol, glycol ether, triglycol, 1,5-pentanediol, 1,6-hexylene glycol, neopentyl glycol, 2-ethyl-1, cyclic ether polymerization such as 3-hexylene glycol, Hydrogenated Bisphenol A or dihydroxyphenyl propane and oxyethane, propylene oxide and glycol of obtaining etc.

For making vibrin crosslinked, preferably also with the above alcohol of ternary.The above polyvalent alcohol of ternary can exemplify Sorbitol Powder, 1,2,3, the own tetrol of 6-, 1,4-sorbitan, tetramethylolmethane, Dipentaerythritol, tripentaerythritol, 1,2,4-trihydroxybutane, 1,2,5-penta triol, glycerine, 2-methyl-prop triol, 2-methyl isophthalic acid, 2,4-trihydroxybutane, trimethylolethane, TriMethylolPropane(TMP), 1,3,5-trihydroxybenzene etc.

The sour composition that forms above-mentioned polyester based polymer can exemplify benzene dicarboxylic acid class or its acid anhydrides such as phthalic acid, m-phthalic acid, terephthalic acid, alkyl dicarboxylic aid's class or its acid anhydrides such as succsinic acid, hexanodioic acid, sebacic acid, nonane diacid, unsaturated dibasic acids such as toxilic acid, citraconic acid, methylene-succinic acid, alkenyl succinic acid, fumaric acid, methylfumaric acid, unsaturated dicarboxylic acid anhydrides such as maleic anhydride, citraconic anhydride, itaconic anhydride, alkenyl succinic anhydride etc.In addition, the above polycarboxylic acid composition of ternary can exemplify trimellitic acid, Pyromellitic Acid, 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 2,5,7-naphthalene three acid, 1,2,4-naphthalene three acid, 1,2,4-butane tricarboxylic acid, 1,2,5-hexane tricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylene radical carboxyl propane, four (methylene radical carboxyl) methane, 1,2,7,8-octane tetracarboxylic acid, the エ Application Port-acid of Le tripolymer or their acid anhydrides, part lower alkyl esters etc.

When binder resin is polyester based resin, exist the fixation performance and the anti-skew of toning agent of resin at 1 peak good in the molecular weight distribution of the THF soluble components of resinous principle, in the zone of molecular weight 3,000～50,000 at least.In addition, it is 60～100% binder resin that the THF soluble components is preferably the composition of molecular weight below 100,000, is more preferably the resin that has 1 peak in the zone of molecular weight 5,000～20,000 at least.

When binder resin was vibrin, its acid number was preferably 0.1mgKOH/g～100mgKOH/g, and more preferably 0.1mgKOH/g～70mgKOH/g is preferably 0.1mgKOH/g～50mgKOH/g.

Among the present invention, the molecular weight distribution of binder resin is by with THF being gel permeation chromatography (CPC) mensuration of solvent.

As the binder resin that can be used for toning agent of the present invention, also can adopt contain in aforementioned vinyl polymer composition and/or the polyester based resin composition can with the resin of the monomer component of this two kinds of resinous principles reaction.Constitute unsaturated dicarboxylic acids such as to exemplify phthalic acid, toxilic acid, citraconic acid, methylene-succinic acid in the monomer of polyester based resin composition with the monomer of vinyl polymer reaction or its acid anhydrides etc.The monomer that constitutes the vinyl polymer composition can exemplify monomer or the acrylic or methacrylic esters of gallic acid with carboxyl or hydroxyl.

In addition, polyester based polymer, vinyl polymer and other binder resin and time spent better are that the acid number that contains the above whole binder resin of 60 quality % is the resin of 0.1～50mgKOH/g.

Among the present invention, the acid number of the binder resin composition of method for producing toner and toner is tried to achieve by following method, and elementary operation is a benchmark with JIS K-0070.

(1) from sample, removes binder resin (component of polymer) additive in addition in advance and re-use, perhaps obtain the acid number and the content of the composition beyond binder resin and the crosslinked binder resin in advance.The pulverizing product 0.5～2.0g of precision weighing sample is designated as Wg with the weight of component of polymer.For example, when measuring the acid number of binder resin, measure the acid number and the content of tinting material or magnetic substance etc. in addition, try to achieve the acid number of binder resin by calculating by toning agent.

(2) sample is packed in the beaker of 300ml, the mixed solution 150ml that adds toluene/ethanol (volume ratio 4/1) dissolves.

(3) ethanolic soln of the KOH of employing 0.1mol/l is measured by the potential difference titration apparatus.

(4) the consumption of KOH solution that will this moment is measured blank value simultaneously as S (ml), as B (ml), utilizes following formula (1) to calculate the consumption of the KOH solution of this moment.F is the coefficient of KOH.

Acid number (mgKOH/g)=[(S-B) * f * 5.61]/W (1)

Consider that from the keeping quality of toning agent the binder resin of toning agent and the second-order transition temperature (Tg) that contains the composition of binder resin are preferably 35～80 ℃, particularly preferably 40～75 ℃.If Tg is lower than 35 ℃, then the easy deterioration of toning agent under the high-temperature atmosphere easily is offset during photographic fixing.In addition, if Tg surpasses 80 ℃, then fixation performance has the tendency of decline.

As can be used for magnetic substance of the present invention, can exemplify the such martial ethiops of (1) magnetite, maghemite, ferrite and contain the ferric oxide of other metal oxide, or the alloy of metal such as the such metal of (2) iron, cobalt, nickel or these metals and aluminium, cobalt, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, vanadium, the mixture of (3) these metals etc.

Specifically can exemplify Fe as magnetic substance ₃O ₄, γ-Fe ₂O ₃, ZnFe ₂O ₄, Y ₃Fe ₅O ₁₂, CdFe ₂O ₄, Gd ₃Fe ₅O ₁₂, CuFe ₂O ₄, PbFe ₁₂O, NiFe ₂O ₄, NdFe ₂O, BaFe ₁₂O ₁₉, MgFe ₂O ₄, MnFe ₂O ₄, LaFeO ₃, iron powder, cobalt powder, nickel powder etc.Above-mentioned magnetic substance can use separately also and can be used in combination more than 2 kinds.Special good magnetic substance is the micro mist of Z 250 or γ-ferric oxide.

In addition, can use magnetic ferric oxide or its mixtures such as the magnetite that contains the xenogenesis element, maghemite, ferrite.This xenogenesis element can exemplify lithium, beryllium, boron, magnesium, aluminium, silicon, phosphorus, germanium, zirconium, tin, sulphur, calcium, scandium, titanium, vanadium, chromium, manganese, cobalt, nickel, copper, zinc, gallium etc.The xenogenesis element can be selected from magnesium, aluminium, silicon, phosphorus or zirconium preferably.The xenogenesis element can embed in the ferric oxide lattice, also can be used as oxide compound and is embedded in the ferric oxide, perhaps is present in the surface as oxide compound or oxyhydroxide, but preferably is included in the ferric oxide as oxide compound.

Above-mentioned xenogenesis element can be when magnetic substance generates be sneaked into the form of the salt of xenogenesis element respectively, and the adjustment by pH can enter into particle.In addition, the magnetic substance particle generate the back by carrying out pH adjustment or add the salt of each element, carry out the adjustment of pH again, above-mentioned xenogenesis element is separated out in particle surface.

The consumption of above-mentioned magnetic substance is 10～200 mass parts corresponding to the binder resin of 100 mass parts, more preferably 20～150 mass parts.The number average particle diameter of these magnetic substances is preferably 0.1～2 μ m, more preferably 0.1～0.5 μ m.Can try to achieve number average particle diameter with mensuration such as quanxtizers by the photo of transmission electron microscope bust shot.

In addition, as the magnetic properties of magnetic substance, the magnetic properties that has applied 10KOe (oersted) better is respectively that Coercive Force is 20～150Oe, saturation magnetization 50～200emu/g, residual magnetization 2～20emu/g.

Aforementioned magnetic substance also can be used as tinting material and uses.During for black toner, can be used for tinting material of the present invention and can exemplify black or blue dyestuff or pigment particles.As black or blue pigment, can exemplify carbon black, nigrosine, acetylene black, phthalocyanine blue, indanthrene blue etc.As black or blue dyestuff, can exemplify azo based dye, anthraquinone based dye, xanthene based dye, methyne based dye etc.

When using as color toner, tinting material can exemplify following example.As pinkish red tinting material, can exemplify condensation azo-compound, Diketopyrrolo-pyrrole compounds, anthraquinone compounds, quinacridone compound, basic dyestuff, lake dyes, naphthol dye, benzimidazolone compound, thioindigo compound, perylene compound.Specifically, the pinkish red tinting material as pigment system can exemplify C.I. Pigment red 1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19,21,22,23,30,31,32,37,38,39,40,41,48,49,50,51,52,53,54,55,57,58,60,63,64,68,81,83,87,88,89,90,112,114,122,123,163,202,206,207,209, C.I. pigment violet 19, C.I. pad dyeing red (padred) 1,2,10,13,15,23,29,35 etc.

Above-mentioned pigment can use separately, but considers from the image quality of full-colour image, and better is and with dyestuff and pigment the boldness of image is increased.

As dyestuff is pinkish red tinting material, can exemplify C.I. solvent red 1,3,8,23,24,25,27,30,49,81,82,83,84,100,109,121, C.I. Disperse Red 9, C.I. solvent purple 8,13,14,21,27, oil-soluble dyes such as C.I. 63 ,DIS,PER,SE ,Vio,let, 63 1, C.I. basis red 1,2,9,12,13,14,15,17,18,22,23,24,27,29,32,34,35,36,37,38,39,40, the C.I. basis purple 1,3,7,10,14,15,21,25,26,27,28 basic dyestuffs such as grade.

As blue colorant, can utilize copper phthalocyanine compound and derivative thereof, anthraquinone, basic dyestuff color lake compound.Specifically, be blue colorant as pigment, comprise C.I. Pigment blue 2,3,15,16,17, pad dyeing indigo plant 6, C.I. acid blue 45 or in phthalocyanine frame, replaced the copper phthalocyanine of 1～5 phthalimide-based methyl.

As yellow colorants, can adopt condensation azo-compound, isoindoline ketone compound, anthraquinone compounds, azo metal complex, methylidyne compound, allyl group amide compound.Specifically,, can exemplify C.I. Pigment Yellow 73 1,2,3,4,5,6,7,10,11,12,13,14,15,16,17,23,65,73,83, C.I. pad dyeing Huang 1,3,20 etc. as yellow ultramarine.

The consumption of above-mentioned tinting material is preferably 0.1～20 mass parts corresponding to 100 mass parts binder resins.

Toning agent of the present invention also can mix with carrier as 2 component developers and uses.Be used for carrier of the present invention and can use carrier or resin coating carriers such as ferrite commonly used, magnetite.

The resin coating carrier is by the carrier core particle with as the resin formation of covering (coating) the carrier core particle surface of coating material, resin as this coating material use, be preferably copolymer in cinnamic acrylic ester, styrene-propene acid such as vinylbenzene-alkylmethacrylate polymer are resin, acrylate copolymer, acrylic resins such as alkylmethacrylate polymer, tetrafluoroethylene, one chlorotrifluoroethylene polymers, poly-inclined to one side 1, fluorine resins such as 1-difluoroethylene, silicone resin, vibrin, polyamide resin, polyvinyl butyral acetal, the amino acrylates resin, can use アイオ monomer resin in addition, the resin that poly-p-phenylene sulfide resin etc. can use as lining (coating) material of carrier, these resins can use separately or multiple and usefulness.

In addition, can use the adhesion type carrier core that is dispersed with magnetic powder in the resin.

In the resin coating carrier, with resin-coated dose of method that covers the surface of carrier core, can adopt to make resin dissolves or be suspended in the solvent and make its method that is attached to the carrier core of coating as at least, or simply with powder state blended method.Resin-coated material can suitably determine corresponding to the ratio of resin coating carrier, better is to be 0.01～5 quality % corresponding to the resin coating carrier, more preferably 0.1～1 quality %.

Cover the use-case that makes of magnetic substance as lining (coating) agent with the mixture more than 2 kinds, can exemplify the example that handle with mixture 12 mass parts of dimethyldichlorosilane(DMCS) and dimethyl silicone oil (mass ratio 1: 5) corresponding to the titanium oxide fine powder body of 100 mass parts (1), the example that handle with mixture 20 mass parts of dimethyldichlorosilane(DMCS) and dimethyl silicone oil (mass ratio 1: 5) corresponding to the fine silica powder body of 100 mass parts (2).

In the above-mentioned resin, be preferably the mixture or the silicone resin that adopt styrene-methylmethacrylate copolymer, fluorine resin and styrene based copolymer, particularly preferably silicone resin.

Mixture as fluorine resin and styrene based copolymer, can exemplify poly-inclined to one side 1, the mixture of 1-difluoroethylene and styrene-methylmethacrylate copolymer, the mixture of tetrafluoroethylene and styrene-methylmethacrylate copolymer, (copolymer quality is than 20～60: 5～30: mixture 10～50) for vinylidene fluoride-TFE copolymer (copolymer quality part 10: 90～90: 10) and styrene-propene acid 2-ethylhexyl multipolymer (copolymer quality was than 10: 90～90: 10) and styrene-propene acid 2-ethylhexyl-methylmethacrylate copolymer partially.

As silicone resin, can exemplify the reaction of nitrogenated silicon resin and nitrogenous silane coupling agent and silicone resin and the modified silicone resin of generation.

As the magneticsubstance of carrier core, can use ferrite, iron excess type ferrite, magnetite, oxide compounds such as gamma-iron oxide, the metal that iron, cobalt and nickel are such or their alloy.In addition, as the element that is included in these magneticsubstances, can exemplify iron, cobalt, nickel, aluminium, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, calcium, manganese, selenium, titanium, tungsten, vanadium.Being preferably with copper, zinc and ferrous components is that the copper-zinc-iron of principal constituent is ferrite, is that the manganese-magnesium-iron of principal constituent is ferrite with manganese, magnesium and ferrous components.

The resistance value of carrier is preferably 10 by the concavo-convex degree on the surface of carrier and the adjustment of coated with resin amount ⁶～10 ¹⁰Ω cm.The particle diameter of carrier is generally 4～200 μ m, is preferably 10～150 μ m, more preferably 20～100 μ m.50% particle diameter of good especially is resin coating carrier is 20～70 μ m.

Be 2 compositions when being photographic developer,, better be to use the toning agent of the present invention of 1～200 mass parts, be more preferably carrier, use the toning agent of 2～50 mass parts corresponding to 100 mass parts corresponding to the carrier of 100 mass parts.

Toning agent of the present invention also can contain wax.Being used to wax of the present invention is following material.For example, low molecular weight polyethylene, low-molecular-weight polypropylene, polyolefin-wax, Microcrystalline Wax, paraffin, the fatty hydrocarbon system wax that サゾ-Le wax is such, the oxide compound of the fatty hydrocarbon system wax that oxidized polyethlene wax is such or their segmented copolymer, gama wax, carnauba wax, haze tallow, department of botany's wax that ホホバ wax is such, beeswax, lanolin, the such animal of spermaceti is a wax, ceresine, cerosin, the such mineral of white vaseline are wax, the montanic acid ester type waxes, what カス -wax was such is the wax class of principal constituent with the fatty acid ester, the wax of the part or all of deoxygenated of fatty acid ester that the deoxidation carnauba wax is such.

The object lesson of wax also comprises palmitinic acid, stearic acid, montanic acid or have the such saturated straight chain lipid acid of straight-chain alkyl carboxylic acid's class of straight chained alkyl, the acid of プラ Application ジ Application, eleostearic acid, the unsaturated fatty acids that parinaric acid is such, stearyl alcohol, eicosanol, V-1326, Tetracosyl alcohol, ceryl alcohol, メシリ Le alcohol or the such saturated alcohol of long chain alkanol, the polyvalent alcohol that Sorbitol Powder is such, inferior oleylamide, the alkene acid amides, the fatty amide that laurylamide is such, methylene radical two decyl amide, the ethylene laurylamide, the saturated fatty acid diamide that hexa-methylene distearyl acid amides is such, the ethylene oleylamide, hexa-methylene two oleylamide, N, N '-two oleyl adipamide, N, the such unsaturated fatty acids amides of N '-two oleyl sebacoyl amine, m-xylene distearyl acid amides, N, the aromatic series diamide that N-distearyl isophthaloyl amine is such, calcium stearate, calcium laurate, Zinic stearas, the fatty acid metal salt that Magnesium Stearate is such, the wax that adopts vinylbenzene or the such ethene base system monomer of vinylformic acid to make aliphatics hydrocarbon system wax grafting and form, the partial esterification compound of lipid acid that the docosoic acid monoglyceryl ester is such and polyvalent alcohol, the methyl compound that vegetative grease obtains by hydrogenation with hydroxyl.

Spendable preferably wax is under the high pressure alkene to be carried out the polyolefine that forms after the radical polymerization, during the high molecular polyolefine polymerization low molecular weight by-products of gained refining and polyolefine, adopt Z-type catalyst under the low pressure, the polyolefine that the such polymerization catalyst of metalloscene catalyst forms, utilize radioactive rays, the polyolefine that hertzian wave or photopolymerization form, with the high molecular polyolefine thermolysis and low-molecular-weight polyolefin, paraffin, Microcrystalline Wax, Fischer-Tropsch wax, pass through synthol process, Hydrocol process, ア-synthetic such as ゲ method synthesize chloroflo, with carbonatoms is that 1 compound is a monomer synthetic wax, hydrocarbon system wax with the such functional group of hydroxyl or carboxyl, hydrocarbon system wax and mixture with hydrocarbon system wax of functional group, with these waxes be parent through vinylbenzene, maleic acid ester, acrylate, methacrylic ester, the vinyl monomer-grafted modification that maleic anhydride is such and wax.

In addition, be preferably use and make wax after the molecular weight distribution of these waxes narrows down by pressurization sweating process, solvent method, recrystallization method, vacuum distillation method, supercritical gas extraction method or solution crystallization, the solid shape lipid acid of lower molecular weight, the solid shape alcohol of lower molecular weight, the solid shape mixture of lower molecular weight has been removed the wax behind other the impurity.

Consider that from the balance that obtains fixation performance and anti-skew the fusing point that is used for wax of the present invention is preferably 70～140 ℃, more preferably 70～120 ℃.If less than 70 ℃, the tendency that then has anti-adhesive to descend if surpass 140 ℃, then is difficult to manifest anti-offset effect.

In addition, with the different types of wax more than 2 kinds, can manifest plasticized effect and demoulding effect by also simultaneously as the effect of wax.

Wax with plasticized effect can exemplify the wax that has the wax of side chain and have the structure of polar group in low melt wax or the molecular structure, and the wax with demoulding effect can exemplify the nonpolarity wax that has the wax of linear chain structure in high melting-point wax, the molecular structure or do not have functional group.As making use-case, the fusing point difference that can exemplify the different waxes more than 2 kinds is 10 ℃～100 ℃ combination, the combination of polyolefine and graft-modified polyolefin etc.

When selecting 2 kinds of waxes, under situation with the wax of spline structure, the wax performance plasticized effect that relatively fusing point is lower, the wax performance demoulding effect that fusing point is higher.At this moment, the fusing point difference is under 10～100 ℃ the situation, can effectively manifest the separation of function.If less than 10 ℃, then the function separating effect is difficult to manifest, if surpass 100 ℃, then is difficult to carry out emphasizing of function because of interaction.In this case, the fusing point of at least a wax is preferably 70～120 ℃, more preferably 70～100 ℃, at this moment has the easily tendency of performance of function separating effect.

In addition, comparatively speaking, have the wax of branched structure in the wax or have the wax of the such polar group of functional group or the wax that obtains with the composition modification that is different from principal constituent performance plastification, the wax of linear chain structure or do not have the non-polar wax or the unmodified straight waxes performance demoulding effect of functional group.Combination preferably is to be the Natene of principal constituent or multipolymer with ethene and to be the polyolefin homopolymer of principal constituent or the combination of multipolymer with the alkene beyond the ethene, the polyolefinic combination of polyolefine and graft modification, the combination of alcohol wax, fatty acid wax or ester type waxes and hydrocarbon system wax, the combination of Fischer-Tropsch wax or polyolefin-wax and paraffin or Microcrystalline Wax, the combination of Fischer-Tropsch wax and polyolefin-wax, the combination of paraffin and Microcrystalline Wax, the combination of carnauba wax, gama wax, rice wax or montanin wax and hydrocarbon system wax.

There is the summit temperature of maximum peak in 70～120 ℃ zone in the endotherm(ic)peak that observes during the DSC that is preferably toning agent under arbitrary situation measures, is more preferably in 70～110 ℃ zone to have maximum peak.The balance of so easy acquisition toning agent keeping quality and fixation performance.

The total content of these waxes in the toning agent of the present invention is preferably 0.2～20 mass parts corresponding to the binder resin of 100 mass parts, more preferably 0.5～10 mass parts.

Among the present invention, the fusing point of wax is the fusing point of wax of summit temperature of maximum peak with endotherm(ic)peak of wax determined among the DSC.

The DSC of wax of the present invention or toning agent preferably utilizes high-precision internal heat type input offset type differential scanning calorimeter to measure in measuring.Measuring method carries out according to ASTM D3418-82.The DSC curve that the used DSC curve utilization of the present invention is taked to heat up for 1 time, measure behind the hot resume before the cooling, when heating up with the heat-up rate of 10 ℃/min.

Can add flow improver additive in the toning agent of the present invention.Flow improver additive can improve the flowability of (become and easily flow) toning agent by being added on toner surface.For example, carbon black, vinylidene fluoride micro mist, the such fluorine resin powder of ptfe micropowder, wet method silicon-dioxide, the such fine particle silica of dry method silicon-dioxide, the micro mist titanium oxide, the micro mist aluminum oxide, these powder have been implemented the treated silicon-dioxide of surface-treated, treated titanium oxide, treated aluminum oxide with silane coupling agent, titanium coupling agent or silicone oil.Wherein, be preferably fine particle silica, micro mist titanium oxide, micro mist aluminum oxide.In addition, be more preferably these powder and carry out the treated silicon-dioxide that obtains after the surface treatment through silane coupling agents or silicone oil.The particle diameter of flow improver additive is preferably 0.001～2 μ m in average primary particle diameter, particularly preferably 0.002～0.2 μ m.

Fine particle silica is to utilize the gaseous oxidation of halogen compounds of silicon and the powder body that generates preferably, is called as the micro mist of so-called dry method silicon-dioxide or pyrogenic silica.

The commercially available fine silica powder that the gaseous oxidation of the halogen compounds by silicon generates for example has with the commercially available micro mist of following trade(brand)name.AEROSIL (Japanese アエロジ Le Co., Ltd. trade(brand)name, down with)-130 ,-300 ,-380 ,-TT600 ,-MOX170 ,-MOX80 ,-COK84:Ca-O-SiL (CABOT Co., Ltd. trade(brand)name)-M-5 ,-MS-7 ,-MS-75 ,-HS-5 ,-EH-5, Wacker HDK (WACKER-CHEMIEGMBH Co., Ltd. trade(brand)name)-N20V15 ,-N20E ,-T30 ,-T40:D-CFineSilica (ダウコ-ニ Application グ Co., Ltd. trade(brand)name): Fransol (Fransil Co., Ltd. trade(brand)name) etc.

More preferably the fine silica powder that the gaseous oxidation of the halogen compounds by silicon is generated carries out the treated fine silica powder that hydrophobic treatment obtains.In the treated fine silica powder, special good be that the fine silica powder that the hydrophobic deg of measuring by the methyl alcohol burette test is preferably 30～80% value is handled the micro mist that obtains.Hydrophobization is by giving with the chemistry of the silicoorganic compound of fine silica powder reaction or physical adsorption etc. or the processing of physical method.Method is the method for handling with the fine silica powder that silicoorganic compound generate the gaseous oxidation of the halogen compounds by silicon preferably.

Silicoorganic compound can exemplify the hydroxypropyl Trimethoxy silane, phenyltrimethoxysila,e, the n-hexadecyl Trimethoxy silane, Octadecane base Trimethoxy silane, the vinyl methoxy silane, vinyltriethoxysilane, vinyltriacetoxy silane, the dimethyl vinyl chlorosilane, the divinyl chlorosilane, γ-methacryloxypropyl trimethoxy silane, hexamethyldisilane, trimethyl silane, trimethylchlorosilane, dimethyldichlorosilane(DMCS), METHYL TRICHLORO SILANE, allyldimethylcholrosilane, the allyl phenyl dichlorosilane, the benzyl dimethyl chlorosilane, the brooethyl dimethylchlorosilane, α-chloroethyl trichlorosilane, β-chloroethyl trichlorosilane, CMDMCS chloromethyl dimethyl chlorosilane, three organic radical silyl mercaptan, trimethyl silyl mercaptan, three organic radical silyl acrylate, vinyl-dimethyl base acetoxysilane, dimethylethoxysilane, trimethylethoxysilane, the trimethylammonium methoxy silane, Union carbide A-162, the isobutyl-Trimethoxy silane, dimethyldimethoxysil,ne, the phenylbenzene diethoxy silane, hexamethyldisiloxane, 1, the 3-divinyl tetramethyl disiloxane, 1, have 2～12 siloxane units in 3-phenylbenzene tetramethyl disiloxane and 1 molecule, being arranged in terminal unit contains with the dimethyl polysiloxane of 0～1 of Si bonded hydroxyl respectively etc.Also can exemplify the such silicone oil of dimethyl silicone oil.These silicoorganic compound can a kind independent use also can be more than 2 kinds the form of mixture use.

The number average particle diameter of flow improver additive is preferably 5～100nm, more preferably 5～50nm.The specific surface area that the nitrogen of measuring by the BET method adsorbs is preferably 30m ²More than/the g, 60～400m more preferably ²/ g, surface treated powder body is preferably 20m ²More than/the g, 40～300m particularly preferably ²/ g.The desirable consumption of these micro mists is preferably 0.03～8 mass parts corresponding to the toner particle of 100 mass parts.

Raising of the adjustment of protection that can the photoreceptor carrier in the toning agent of the present invention, the raising of spatter property, thermal property electrical characteristic physical property, resistance adjustment, softening temperature adjustment, photographic fixing rate etc. is a purpose, adds various metallic soaps, fluorine as other additive as required and be tensio-active agent, dioctyl phthalate (DOP) or as the stannic oxide of electroconductibility imparting agent, zinc oxide, carbon black, weisspiessglanz etc. or inorganic micro powder bodies such as titanium oxide, aluminum oxide etc.Perhaps, can make these inorganic micro powder body hydrophobizations as required.In addition, also can use tetrafluoroethylene, Zinic stearas, poly-inclined to one side 1 on a small quantity, lubricants such as 1-difluoroethylene, abrasives such as Cs2O, silicon carbide, strontium titanate, anti-hard caking agent and as development accelerant and opposite polarity white particles and black particle toner particle.

These additives can carried charge control etc. be handled with treatment agents such as silicon lacquer, various modification silicon lacquer, silicone oil, various modified silicon oil, silane coupling agent, the silane coupling agent with functional group and other silicoorganic compound or various treatment agent for purpose.

Charge control agent of the present invention is with above-mentioned additive and toning agent, utilize mixing machine thorough mixing such as Henschel mixer, ball mill, nauta mixer, V-Mixer, Wtypeofblender, super mixing machine to stir, outside surfaces of toner particles being carried out equably, add processing, also can obtain development of static charge toning agent as the purpose product.

Toning agent of the present invention can not accepted the thermal distortion in the electronics shooting process to thermally-stabilised, can keep stable charged characteristic.In addition, owing to all be homodisperse in any binder resin, therefore fresh the charged of toning agent distributes very evenly.So the toning agent (used toner) of the not transfer printing of toning agent of the present invention, recovery is compared with fresh toning agent, saturated frictional electrification amount and charged distribution all do not have any variation.But, when the used toner from electrostatic charge image developing toner of the present invention is utilized again, vibrin by selecting fatty family glycol as binder resin or the styrene-propene acid copolymer of selecting metal corsslinking as binder resin, add a large amount of polyolefinic methods therein when making toning agent, can further reduce the difference of fresh toning agent and used toner.

Method as making toning agent of the present invention can adopt known manufacture method.If manufacture method is carried out illustration, then mixing machine such as useful ball mill carries out thorough mixing to above-mentioned toning agent constituent materials such as binder resin, charge control agent and tinting materials preferably, this mixture is carried out mixing well with the such heating kneading device of hot-rolling kneader then, cooling curing is pulverized back fractionated method (comminuting method) again.

In addition, also can adopt to make said mixture be dissolved in solvent, carry out micronize by spraying, drying, the fractionated method is made.In addition, comprise that also employing sneaks into the material of regulation in constituting the monomer of binder resin, emulsification or form suspension after make its polymerization and the polymerization that obtains toning agent is made the method for toning agent; The so-called micro-capsule toning agent that is formed by core and shell material can adopt the method that makes core or shell material or both contain prescribed material to make.In addition, with the such mixing machine of Henschel mixer desirable additive and toner particle are carried out thorough mixing as required and can make toning agent of the present invention.

The method that adopts above-mentioned comminuting method to carry out the manufacturing of toning agent of the present invention is illustrated in greater detail, at first uniform mixing binder resin and tinting material, charge control agent and other necessary additive.Mixing can be adopted known stirrer, for example enforcements such as Henschel mixer, super mixing machine, ball mill.It is mixing that the gained mixture carries out hot melt with the extrusion machine of closed kneader or single shaft or twin shaft.After cooling off mixing thing, carry out coarse reduction with crusher or beater grinder, it is broken to carry out micro mist with pulverizers such as injector-type mill, high-speed rotary grinding machines again.Then, use air classifier, for example utilize ミ Network ロプレッ Network ス, DS grading machine of bending spraying machine, whirlwind (centrifugal) hierarchical approaches of the inertial classification mode of attached wall effect etc., carry out classification until designated size.When with additive etc. toner surface being handled, use homogenizer, for example Henschel mixer, super mixing machine etc. mix toning agent and additive.

Toning agent of the present invention also can make by suspension polymerization or emulsion polymerization.In the suspension polymerization, the linking agent and other additive uniform dissolution or the dispersion that make polymerizable monomer, tinting material, polymerization starter, charge control agent and add as required, after forming monomer composition, with suitable stirrer and dispersion machine, for example homomixer, homogenizer, spraying gun, miniature fluidizer, single liquid fluid tip, gas-liquid fluid tip, electric mulser etc., make this monomer composition be scattered in the external phase that contains dispersion stabilizer, for example aqueous phase.Be preferably to have desirable toner particle and be of a size of purpose, adjustment stirring velocity, temperature and time carry out granulation to the drop of polymerizable monomer composition.Simultaneously carry out polyreaction, can obtain to have the toner particle of desirable particle diameter at 40～90 ℃.The gained toner particle is washed the leaching after drying.Outer after the manufacturing of toner particle added processing can adopt preceding method.

The gained particle is compared with the particle that above-mentioned suspension polymerization obtains when utilizing the letex polymerization manufactured, though its homogeneity is better, but median size is 0.1～1.0 μ m, minimum, so can be nuclear with the emulsified particle, add polymerizable monomer then, the so-called seeding polymerization that particle is grown up according to the different situations utilization, perhaps emulsified particle is merged into suitable median size, its fused method also can be made.

When utilizing above-mentioned polymerization to make, because without pulverising step, thus do not give toner particle with brittle necessity, and can use unworkable low softening point material in the past the comminuting method in a large number, so the selection face of material is wideer.Owing to the releasing agent and the tinting material that are difficult to expose at surfaces of toner particles as hydrophobic material, so can reduce the pollution of exchanging colorant load member, photoreceptor, transfer roll and fuser.

Toning agent of the present invention utilizes the polymerization manufacturing, can further improve the reconstruction of image, transfer printing, the such characteristic of color rendition, for the small point of correspondence, the particle diameter of toning agent is diminished, and can obtain the toning agent of narrow particle size distribution with comparalive ease.

Employed polymerizable monomer when utilizing polymerization process to make toning agent of the present invention can adopt the vinyl polymerized monomer that can carry out radical polymerization.This vinyl polymerized monomer can use simple function polymerizable monomer or multi-functional polymerizable monomer.

The simple function polymerizable monomer can exemplify vinylbenzene, alpha-methyl styrene, Beta-methyl vinylbenzene, o-methyl styrene, between vinyl toluene, p-methylstyrene, 2, the 4-dimethyl styrene, align butylstyrene, to t-butyl styrene, to positive hexyl phenenyl ethene, to the such polystyrene polymerizable monomer of styryl phenyl, methyl acrylate, ethyl propenoate, the vinylformic acid n-propyl, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, the vinylformic acid n-pentyl ester, the just own ester of vinylformic acid, 2-EHA, the vinylformic acid n-octyl, the vinylformic acid benzene methyl, vinylformic acid dimethyl phosphoric acid ester methyl esters, vinylformic acid dibutylphosphoric acid ester ethyl ester, the acrylic polymerizable monomer that vinylformic acid 2-benzoyloxy ethyl ester is such, methyl methacrylate, Jia Jibingxisuanyizhi, n propyl methacrylate, isopropyl methacrylate, n-BMA, Propenoic acid, 2-methyl, isobutyl ester, the methacrylic tert-butyl acrylate, the methacrylic acid n-pentyl ester, the just own ester of methacrylic acid, methacrylic acid 2-ethylhexyl, n octyl methacrylate, methacrylic acid diethyl phosphoric acid ester, the metha crylic polymerizable monomer that methacrylic acid dibutylphosphoric acid ester ethyl ester is such, unsaturated aliphatic monocarboxylate class, vinyl-acetic ester, propionate, the vinyl ester that vinyl benzoate is such, methoxy ethylene, the vinyl ethers that VINYL ISOBUTYL ETHER is such, ethenyl methyl ketone, the vinyl hexyl ketone, the vinyl ketones that the vinyl nezukone is such.

Multi-functional polymerizable monomer can exemplify diethylene glycol diacrylate, triethylene glycol diacrylate, Viscoat 335HP, polyethyleneglycol diacrylate, 1, the 6-hexanediyl ester, neopentylglycol diacrylate, tripropylene glycol diacrylate, polypropyleneglycol diacrylate, 2, two [4-(acryloxy diethoxy) phenyl] propane of 2-, Viscoat 295, the tetramethylol methane tetraacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1, the 3-butylene glycol dimethacrylate, 1, the 6-hexanediol dimethacrylate, the neopentyl glycol methacrylic ester, polypropylene glycol dimethacrylate, 2, two [4-(methacryloxy diethoxy) phenyl] propane of 2-, 2, two [4-(the many oxyethyl groups of the methacryloxy) phenyl] propane of 2-, trimethylolpropane trimethacrylate, tetramethylol methane tetramethyl-acrylate, Vinylstyrene, the divinyl naphthalene, divinyl ether etc.

Among the present invention, aforementioned simple function polymerizable monomer can be used singly or two or more kinds in combination, or is used in combination simple function polymerizable monomer and multi-functional polymerizable monomer.In addition, aforementioned multi-functional polymerizable monomer also can be used as the linking agent use.Polymerization starter when being used for the polymerization of above-mentioned polymerizable monomer can adopt oil-soluble initiator and/or water soluble starter.For example; oil-soluble initiator can exemplify 2; 2 '-Diisopropyl azodicarboxylate; 2; 2 '-azo two-2; the 4-methyl pentane nitrile; 1; 1 '-azo two (hexanaphthene-1-nitrile); 2; 2 '-azo, two-4-methoxyl group-2; the azo-compound that the 4-methyl pentane nitrile is such, acetyl peroxide cyclohexyl sulphonyl; the peroxidation dimethyl isopropyl ester; peroxidation carbonic acid decyl ester; the decyl superoxide; the superoxide propionyl; acetyl peroxide; peroxide-2-ethyl hexanoic acid tert-butyl; benzoyl peroxide; the peroxidation tert-butyl isobutyrate; cyclohexanone peroxide; the peroxidation ethyl methyl ketone; tert-butyl peroxide; ditertiary butyl peroxide; the superoxide series initiators that cumene hydroperoxide is such.

Water soluble starter can exemplify ammonium persulphate, Potassium Persulphate, 2,2 '-azo, two (N, N '-dimethylene NSC 18620) hydrochloride, 2,2 '-azo two (amino two propane of 2-) hydrochloride, azo two (isobutyl amidine) hydrochloride, 2,2 '-Diisopropyl azodicarboxylate sodium sulfonate, ferrous sulfate or hydrogen peroxide.

The addition of polymerization starter is 0.5～20 mass parts corresponding to the polymerizable monomer of 100 mass parts, can use separately or and use.

Used dispersion agent when making polymerization toner, for example inorganic is that oxide compound can exemplify tricalcium phosphate, trimagnesium phosphate, aluminum phosphate, zinc phosphate, lime carbonate, magnesiumcarbonate, aluminium hydroxide, Calucium Silicate powder, calcium sulfate, barium sulfate, wilkinite, silicon-dioxide, aluminum oxide etc.The organic system compound can exemplify sodium salt, starch of polyvinyl alcohol, gelatin, methylcellulose gum, methyl hydroxy propyl cellulose, ethyl cellulose, carboxymethyl cellulose etc.The consumption of these dispersion agents is preferably 0.2～2.0 mass parts corresponding to 100 mass parts polymerizable monomers.

These dispersion agents can directly use commercially available product, but in order to obtain the fine dispersed particle with homogeneous granularity, this mineral compound are generated.

Compare with the toning agent that obtains by comminuting method by the toning agent that above-mentioned polymerization obtains without special processing, the concavo-convex degree of toner particle has the tendency that diminishes, owing to be unbodied, so by increasing the contact area of electrostatic latent image carrier and toning agent, can improve toning agent sticking power, consequently, the pollution in the machine reduces, and easily obtains higher, the more high-grade image of image color.

In addition, the hot bath method that the toning agent that utilizes comminuting method to obtain also can heat in the water by toner particle is scattered in, make toner particle by the heat treating process in the hot gas flow or give the mechanical shock method of toner particle with the processing of mechanical energy etc., reduce the concavo-convex degree of toner surface.As the efficient apparatus that is used to reduce concavo-convex degree, can exemplify メカノ Off-ジヨ Application system (ホソカワミ Network ロ Co., Ltd. system) of having adopted the dry type mechanochemical reaction, I formula injector-type mill, as the mixing machine with mixing device of rotor and lining ring (nara machinery is made Co., Ltd. of institute system), as the Henschel mixer of mixing machine etc. with high-speed stirring blade.

As one of the value of the concavo-convex degree of the aforementioned toner particle of expression, can represent by average roundness.Average roundness (C) is meant by following formula (2) obtains circularity (Ci), for another example shown in the following formula (3), with the circularity summation of all particles of measuring divided by all particles number of measuring (m) value.

The girth (2) of the projection image of the girth/particle of the circle of circularity (Ci)=the have shadow area identical with particle

Average roundness

C = Σ_{i = 1}^{m} Ci / m - - - (3)

Above-mentioned circularity (Ci) is measured with fluid-type particle image analytical equipment (for example, East Asia medical electric system FPIA-1000).Measuring method is the toning agent that disperses about 5mg in the water 10ml of the nonionic surfactant that has dissolved about 0.1mg, modulate dispersion liquid, use ultrasonic wave (20kHz then, 50W) to dispersion liquid irradiation 5 minutes, making dispersion liquid concentration is 5000～20000/μ l, adopt above-mentioned fluid-type particle image determinator, the circularity of measuring the particle with the above particle diameter that is equivalent to circular diameter less than 159.21 μ m of 0.60 μ m distributes.

Make above-mentioned average roundness value be preferably 0.955～0.990 if adjust toner particle, more preferably 0.960～0.985, then can alleviate the phenomenon that remaining toner increases when causing transfer printing, the tendency that is difficult to transfer printing is again arranged.

Consider from the productivity of picture characteristics and toning agent, toning agent of the present invention for example used the micron sizing mill (ミ Network ロ Application サイザ-, for example, Co., Ltd. of セイシ Application enterprise system) in the mensuration of etc. laser particle size measure of spread machine, the particle diameter of toning agent is preferably 2～15 μ m in the median size of volume reference, more preferably 3～12 μ m.If median size surpasses 15 μ m, then resolution and distinctiveness have the tendency of passivation, if median size is less than 2 μ m, though then resolution is better, but the qualification rate deterioration when toning agent is made, cause the cost problem of higher, and organic interior toning agent disperses, soaks into the tendency of insalubrity such as skin.

Size-grade distribution about toning agent, toning agent of the present invention for example utilizes コ-Le -counter (コ-Le -system TA-II of Co., Ltd.) to carry out particle size measurement, the following particle content of 2 μ m is preferably 10～90% in the number benchmark, and the content of the particle that 12.7 μ m are above is preferably 0～30% in volume reference.

Development of static charge of the present invention is being to take off in the BET specific area measuring of adsorbed gas with nitrogen with the specific surface area of toning agent, and its value is preferably 1.2～5.0m ²/ g, more preferably 1.5～3.0m ²/ g.The mensuration of specific surface area (is for example for example used BET specific area measuring device, Shimadzu Corporation's system, FlowSorbII2300), in 50 ℃ break away from the adsorbed gas that made toner surface in 30 minutes after, utilize the liquid nitrogen chilling, nitrogen is adsorbed again, and then be warming up to 50 ℃, the value that the amount of gas evolved in the time of is thus obtained is specific surface area.

The apparent specific gravity of toning agent of the present invention (high density) for example adopts powder to measure machine (for example, ホソカワミ Network ロ Application Co., Ltd. system) and measures, and the apparent specific gravity of nonmagnetic toner is preferably 0.2～0.6g/cm ³, the apparent specific gravity of magnetic color tuner is different and different because of magnetic powder kind and content, but is preferably 0.2～2.0g/cm ³

True specific gravity when toning agent of the present invention is nonmagnetic toner is preferably 0.9～1.2g/cm ³, the true specific gravity during for magnetic color tuner is different and different because of magnetic powder kind and content, but is preferably 0.9～4.0g/cm ³The true specific gravity of toning agent is calculated according to following steps.The toning agent of accurate weighing 1.000g is in the tablet former with its 10mm Φ that packs into, Yi Bian apply 200kgf/cm under the vacuum ²Pressure compressed moulding on one side.Measure the height of this cylindric forming composition with milscale, calculate true specific gravity thus.

Mobile slope of repose and the definition of static slope of repose that the flowability of toning agent is for example measured by slope of repose determinator (for example, tube well physics and chemistry Co., Ltd. system).The mobile slope of repose of the development of static charge that has used charge control agent of the present invention during with toning agent is preferably 5 degree～45 degree, and static slope of repose is preferably 10～50 degree.

The mean value of the shape factor when toning agent of the present invention is the crush type toning agent (SF-1) is preferably 100～400, and the mean value of shape factor 2 (SF-2) is preferably 100～350.

Among the present invention, SF-1, the SF-2 of shape factor of expression toning agent for example adopt possess the CCD photographic camera opticmicroscope (for example, the system BH-2 of Olympus Co., Ltd), through amplify 1000 times toner particle group with a visual field in about 30 as sample, the gained image (is for example transferred to image analysis apparatus, system Le-ゼッ Network ス the FS of Nikon Corp.), toner particle is repeated same operation until about 1000, calculate shape factor.Shape factor (SF-1) and shape factor 2 (SF-2) are calculated according to following formula.

SF-1＝((ML ²×π)/4A)×100

(in the formula, ML represents the maximum length of particle, and A represents the shadow area of a particle)

SF-2＝(PM ²/4Aπ)×100

(in the formula, PM represents the girth of particle, and A represents the shadow area of a particle)

SF-1 represents particles Deformation, particle approaching more spherical it more near 100, elongated particle numerical value is big more.SF-2 represents the concavo-convex of particle, particle approaching more spherical it more near 100, the complicated more numerical value of the shape of particle is big more.

The volume specific resistance of toning agent of the present invention, the volume specific resistance during for nonmagnetic toner is preferably 1 * 10 ¹²～1 * 10 ¹⁶Ω cm, the volume specific resistance during for magnetic color tuner is different and different because of magnetic powder kind and content, is preferably 1 * 10 ⁸～1 * 10 ¹⁶Ω cm.The compression toner particle makes it be shaped to the discoid test film of diameter 50mm, thick 2mm, it with electrode (for example is positioned over solid, the system SE-70 of Ando Electric Co., Ltd), with high insulating-resistance meter (for example, ヒユ-レットパッカッ De Co., Ltd. system, 4339A), when applying volts DS 100V continuously through the volume specific resistance of the value after 1 hour as toning agent.

The dielectric loss tangent of toning agent of the present invention, its dielectric loss tangent is preferably 1.0 * 10 during for nonmagnetic toner ^-3～15.0 * 10 ^-3, the dielectric loss tangent during for magnetic color tuner is different and different because of magnetic powder kind and content, is preferably 2 * 10 ^-3～30 * 10 ^-3Compression makes its moulding to toner particle, make the discoid test film of diameter 50mm, thick 2mm, it is positioned over the solid electrode, with the LCR tester (for example, ヒユ-レットパッカッ De Co., Ltd. system, 4284A), measure to measure frequency 1KHz, peak-to-peak voltage 0.1KV, with income value as dielectric loss tangent (Tan δ).

The Ai Zuoshi impact value of toning agent of the present invention is preferably 0.1～30kgcm/cm.The toner particle heat fusing is made tabular test film, is benchmark with JIS standard K-7110 (the shock test method of rigid plastics), test film is measured, with the Ai Zuoshi impact value of income value as toning agent.

The melt index of toning agent of the present invention (MI value) is preferably 10～150g/10min.The melt index (MI value) of toning agent of this moment is to be the value that benchmark records with JIS standard K-7210 (A method).At this moment, measuring temperature is 125 ℃, heavy burden 10kg.

The melt initiation temperature degree of toning agent of the present invention is preferably 80～180 ℃, and 4mm decline temperature is preferably 90～220 ℃.Toner particle compression is made its moulding, make the cylindric test film of diameter 10mm, thick 20mm, it is positioned over the heat fusing characteristic detecting apparatus, for example in the hydrometry device (for example, the system CFT-500C of Shimadzu Corporation), heavy burden 20kgf/cm ²Begin fusion when measuring, the temperature when piston is begun to descend is as the melt initiation temperature degree of toning agent.In addition, utilize same measuring method, the temperature when piston is descended 4mm is as the 4mm temperature that descends.

The second-order transition temperature of toning agent of the present invention (Tg) is preferably 35～80 ℃, more preferably 40～75 ℃.(DSC) measures with the differential thermal analysis device, is warming up to chilling after the certain temperature, and the temperature that the peak value of the phase transformation that will manifest when heating up is again tried to achieve is as the second-order transition temperature of the toning agent of this moment.If the Tg of toning agent is lower than 35 ℃, then anti-skew and storage stability have the tendency of decline, if surpass 80 ℃, then the fixing strength of image has the tendency of decline.

Be preferably in the summit temperature that there is maximum peak in 70～120 ℃ zone in the endotherm(ic)peak that the DSC of toning agent of the present invention observes in measuring.

The melt viscosity of toning agent of the present invention is preferably 1000～50000 pools, more preferably 1500～38000 pools.The toner particle compression is made its moulding, make the cylindric test film of diameter 10mm, thick 20mm, it is positioned over the heat fusing characteristic detecting apparatus, for example in the hydrometry device (the system CFT-500C of Shimadzu Corporation), heavy burden 20kgf/cm ²Measure the melt viscosity of the value of gained as the toning agent of this moment.

The amount as the Monoazo/iron complex compound of charge control agent that is present in toner surface of the present invention preferably is at least more than the 1mg corresponding to the 1g toning agent.The quantitative of the Monoazo/iron complex compound of toner surface is insoluble to resin, tinting material, the wax of toning agent and only makes Monoazo/iron complex compound dissolved organic solvent by use, methyl alcohol for example, after the Monoazo/iron complex compound of toner surface carried out thorough washing, with extinction photometer etc. the concentration of this washing soln is measured, adopted the lubber-line of making in advance to carry out colorimetric and implement.

The median size of volume reference that is present in the Monoazo/iron complex compound of toner surface of the present invention is preferably 0.05 μ m～3 μ m, more preferably 0.1 μ m～1 μ m.If the median size of the charge control agent of toner surface is less than 0.05 μ m, then charge control agent is not brought into play effect of sufficient, and median size is when 3 μ m are above, the ratio regular meeting that charge control agent is scattered when frictional electrification increases, because of making carried charge, carrier contamination descends, increase generation photographic fog because of opposite polarity toning agent causes the problem that toning agent disperses in machine.The particle size measurement that is present in the Monoazo/iron complex compound of toner surface is carried out by the following method.Promptly, a certain amount of toning agent of heat fusing also makes its filming, for example it is amplified about 500 times, and only can discern the Monoazo/iron complex compound particle in the toning agent with the polarizing microscope that possesses the CCD photographic camera (for example, the system BH-2 of Olympus Co., Ltd).The gained image is transferred to image analysis apparatus (for example, the system Le-ゼッ Network ス FS of Nikon Corp.), utilize image analysis to calculate the size-grade distribution of Monoazo/iron complex compound particle.In addition,, make from toner surface and only extracted the toning agent heat fusing of Monoazo/iron complex compound out and made its filming, measure the size-grade distribution of this moment by same method.By the size-grade distribution of the Monoazo/iron complex compound that is present in toning agent integral body of above acquisition with exist only in distribution poor of the Monoazo/iron complex compound of toning agent inside, infer the size-grade distribution of the Monoazo/iron complex compound that is present in toner surface.The median size of this moment is defined as the median size of the Monoazo/iron complex compound that is present in toner surface.

In the dissolution with solvents residual component of toning agent of the present invention, the THF insoluble composition is preferably 0～30 quality %, and the ethyl acetate insoluble composition is preferably 0～40 quality %, and the chloroform insoluble composition is preferably 0～30 quality %.This dissolution with solvents residual component is to make the 1g toning agent dissolve and/or be scattered in each 10ml of THF, ethyl acetate and chloroform equably, this solution and/or dispersion liquid are carried out pressure filtration, make filtrate quantitatively dry, calculate the value of the ratio of the material that is insoluble to organic solvent in the toning agent by this value.

Toning agent of the present invention can be used for the 1 composition visualization way of one of image forming method.1 composition visualization way is to supply with the toning agent of filming to latent image carrier, makes the mode of image development.The filming of toning agent is utilized usually possesses toning agent transmission member, toning agent bed thickness control member and toner replenishing auxiliary part, and this supply auxiliary part is finished with the device that the toning agent transmission member is connected respectively with toning agent transmission member and toning agent bed thickness control member.

The situation that toning agent of the present invention is used for 2 composition development methods is specifically described.2 composition visualization way are to use the mode of toning agent and carrier (possessing the material of giving the effect of material and toning agent transmission material as charged), and carrier uses above-mentioned magneticsubstance and granulated glass sphere.Photographic developer (toning agent and carrier) is by the stirring of agitating member, and the quantity of electric charge of regulation is produced, and utilizes magnetic roller etc. to be transferred into the development position.Be held in the roller surface by the magnetic force photographic developer on the magnetic roller, utilize formation such as photographic developer switchboard to be controlled as the magnetic brush of suitable height.Photographic developer follows being rotated on the roller of developer roll to move, and keeps body to contact with the static charge sub-image or opposed with the contactless state at certain interval, makes image development visual.When developing with contactless state, by keeping producing DC electric field between the body at photographic developer and sub-image, toning agent can obtain to stride across the spatial motivating force of certain intervals, but forms distinct image in order to develop usually, preferably adopts the eclipsed mode that exchanges that makes.

In addition, charge control agent of the present invention can be used as charge control agent (charge enhancers) use in the static powder body coating usefulness coating.That is, used the electrostatic coating of this charge enhancers good with environment resistant, storage stability, particularly thermostability and the weather resistance of coating, coating efficiency reaches 100%, can form the thick film of no paint film defect.

In addition, it is also extremely effective charge control agent of the present invention to be made an addition to 2 composition developing carrier coating agents.At this moment, the static charge of giving toning agent forms positive electricity type opposite when being generally used for toning agent, but play electrical good charge control agent of the present invention and can give the charged effect of giving from carrier side, and when using with toning agent similarly, play electrical good charged control effect.In addition, thermotolerance and stability are good, and long-time running (anti-brush) is good.

Embodiment

Below, the present invention will be described by embodiment, but these do not limit the present invention." part " expression " mass parts " among the embodiment.

[Production Example 1] (Production Example o.1 of the compound N in the table 1)

10 parts of 4-chloro-2-amino-phenols are added in 15.2 parts of 76.5 parts of entry and 35% hydrochloric acid, and cooling is stirring and dissolving down.In the aforementioned salt aqueous acid, splash into 13.6 parts of Sodium Nitrites that are dissolved in 24.6 parts of water below 10 ℃ in interior temperature, while add then 10 parts of suitable trash ices with temperature maintenance at 5～10 ℃.After dripping end, reaction is carried out in 10 ℃ of stirrings.The thionamic acid reaction that adds 0.2 part confirmed that with potassium iodide starch test paper no excessive nitrous acid is remaining after 10 minutes, modulation diazonium solution.

Then, in the mixing solutions of 104.6 parts of 87 parts in water, 12.1 parts in 25% sodium hydroxide, 4.9 parts in yellow soda ash and propyl carbinols, add 12.0 parts of 3-methyl isophthalic acid-phenyl-5-pyrazolone, stirring and dissolving under the room temperature.Then, add above-mentioned diazonium solution therein, stir in 20～22 ℃ and carried out linked reaction in 4 hours.After 4 hours, confirm not react with Resorcinol, reaction finishes.Fully stir after adding 30.4 parts of entry, leave standstill the back water layer of bottom is carried out separatory.Then, add 92.8 parts of entry, 8.7 parts of agitator treatings of 25% sodium hydroxide, the bottom water layer is carried out separatory.

In above-mentioned reaction solution, add 42.2 parts of entry, 5.9 parts of Whitfield's ointments, 24.6 parts of propyl carbinols and 48.5 parts of stirrings of 15% yellow soda ash.Then, add 48.5 parts in 15.1 parts of 38% ferric chloride in aqueous solution and 15% yellow soda ash,, carry out the coordination reaction stirring 8 hours after the interior temperature rise to 30 ℃.After 8 hours, confirm that by TLC the spot of raw material disappears, reaction finishes.Stirring is left standstill after stopping, and the bottom water layer is carried out separatory.Then, add 8.7 parts in 92.8 parts of entry, 12.3 parts of propyl carbinols and 25% sodium hydroxide, agitator treating carries out separatory to the bottom water layer.Filter the back and take out iron complex, 253 parts of washings of water.

In 82.3 parts in water, add 5.9 parts of ammonium sulfate, stir while heat up.After interior temperature reaches 90 ℃, utilize pipette to drip the mixed solution that above-mentioned iron complex is scattered in 113.9 parts of water and form.Then, removing propyl carbinol in 97～99 ℃ of steamings stirred 1 hour simultaneously.Behind the cold filtration, water washs filter cake for 253 parts.After 60 ℃ of vacuum-dryings, confirm to reach constant, obtain 24.8 parts of purpose compounds.

The gained compound is carried out infrared absorption spectrum, visible absorption spectrum, ultimate analysis, and (C, H N), atomic absorption analysis, mass spectroscopy, confirm that this compound is a compound N compound o.1.

In addition, utilize pressed disc method (KBr) to measure infrared absorption spectrum.Below carry out the mensuration of infrared absorption spectrum by same method.

[Production Example 2] (manufacturing process o.2 of the compound N in the table 1)

Then, in the mixing solutions of 104.6 parts of 87 parts in water, 12.1 parts in 25% sodium hydroxide, 4.9 parts in yellow soda ash and propyl carbinols, add 14.4 parts of 3-methyl isophthalic acids-(4-chloro-phenyl-)-5-pyrazolone, stirring and dissolving under the room temperature.Then, add above-mentioned diazonium solution therein, stir in 20～22 ℃ and carried out linked reaction in 4 hours.After 4 hours, confirm not react with Resorcinol, reaction finishes.Fully stir after adding 30.4 parts of entry, leave standstill the back water layer of bottom is carried out separatory.Then, add 92.8 parts of entry, 8.7 parts of agitator treatings of 25% sodium hydroxide, the bottom water layer is carried out separatory.

In 82.3 parts in water, add 5.9 parts of ammonium sulfate, stir while heat up.After interior temperature reaches 90 ℃, utilize pipette to drip the solution that above-mentioned iron complex is scattered in 113.9 parts of water and form.Then, removing propyl carbinol in 97～99 ℃ of steamings stirred 1 hour simultaneously.Behind the cold filtration, water washs filter cake for 253 parts.After 60 ℃ of vacuum-dryings, confirm to reach constant, obtain 27.1 parts of purpose compounds.

The gained compound is carried out infrared absorption spectrum, visible absorption spectrum, ultimate analysis, and (C, H N), atomic absorption analysis, mass spectroscopy, confirm that this compound is a compound N compound o.2.

[Production Example 3] (manufacturing process o.3 of the compound N in the table 1)

Add 15.2 parts of 10 parts of 4-chloro-2-amino-phenols, 76.5 parts in water and 35% hydrochloric acid, cooling is stirring and dissolving down.In the aforementioned salt aqueous acid, splash into 13.6 parts of Sodium Nitrites that are dissolved in 24.6 parts of water below 10 ℃ in interior temperature, while add then 10 parts of suitable trash ices with temperature maintenance at 5～10 ℃.After dripping end, reaction is carried out in 10 ℃ of stirrings.The thionamic acid reaction that adds 0.2 part confirmed that with potassium iodide starch test paper no excessive nitrous acid is remaining after 10 minutes, modulation diazonium solution.

Then, add 104.6 parts of 3-methyl isophthalic acid-14.4 parts of (4-chloro-phenyl-)-5-pyrazolones, 87 parts in water, 12.1 parts in 25% sodium hydroxide, 4.9 parts in yellow soda ash and propyl carbinols, stirring and dissolving under the room temperature.Then, add above-mentioned diazonium solution therein, stir in 20～22 ℃ and carried out linked reaction in 4 hours.After 4 hours, confirm not react with Resorcinol, reaction finishes.Fully stir after adding 30.4 parts of entry, leave standstill the back water layer of bottom is carried out separatory.Then, add 92.8 parts of entry, 8.7 parts of agitator treatings of 25% sodium hydroxide, the bottom water layer is carried out separatory.

In above-mentioned reaction solution, add 42.2 parts of entry, 5.9 parts of Whitfield's ointments, 24.6 parts of propyl carbinols and 48.5 parts of stirrings of 15% yellow soda ash.Then, add 18.0 parts in 15.1 parts of 38% ferric chloride in aqueous solution and 15% yellow soda ash, pH is adjusted into 4.5 with acetate.With stirring 8 hours after the interior temperature rise to 30 ℃, carry out the coordination reaction.After 8 hours, confirm that by TLC the spot of raw material disappears, reaction finishes.Stirring is left standstill after stopping, and the bottom water layer is carried out separatory.Then, add 189.9 parts of agitator treatings of entry, the bottom water layer is carried out separatory.Filtering back filter cake water washs for 253 parts.After 60 ℃ of vacuum-dryings, confirm to reach constant, obtain 26.5 parts of purpose compounds.

The gained compound is carried out infrared absorption spectrum, visible absorption spectrum, ultimate analysis, and (C, H N), atomic absorption analysis, mass spectroscopy, confirm that this compound is a compound N compound o.3.

[Production Example 4] (Production Example o.4 of the compound N in the table 1)

Add 15.2 parts of 10 parts of 4-chloro-2-amino-phenols, 76.5 parts in water and 35% hydrochloric acid, cooling is stirring and dissolving down.Drip 13.6 parts of Sodium Nitrites that are dissolved in 24.6 parts of water below 10 ℃ in interior temperature, while add then 10 parts of suitable trash ices with temperature maintenance at 5～10 ℃.After dripping end, reaction is carried out in 10 ℃ of stirrings.The thionamic acid reaction that adds 0.2g confirmed that with potassium iodide starch test paper no excessive nitrous acid is remaining after 10 minutes, modulation diazonium solution.

Then, add 104.6 parts of 3-methyl isophthalic acid-phenyl-12.0 parts of 5-pyrazolones, 87 parts in water, 12.1 parts in 25% sodium hydroxide, 4.9 parts in yellow soda ash and propyl carbinols, stirring and dissolving under the room temperature.Then, add above-mentioned diazonium solution therein, stir in 20～22 ℃ and carried out linked reaction in 4 hours.After 4 hours, confirm not react with Resorcinol, reaction finishes.Fully stir after adding 30.4 parts of entry, leave standstill the back water layer of bottom is carried out separatory.Then, add 92.8 parts of entry, 8.7 parts of agitator treatings of 25% sodium hydroxide, the bottom water layer is carried out separatory.

In above-mentioned reaction solution, add 42.2 parts of entry, 5.9 parts of Whitfield's ointments, 24.6 parts of propyl carbinols and 48.5 parts of stirrings of 15% yellow soda ash.Then, add 18.0 parts in 15.1 parts of 38% ferric chloride in aqueous solution and 15% yellow soda ash, pH is adjusted into 4.5 with acetate.With stirring 8 hours after the interior temperature rise to 30 ℃, carry out the coordination reaction.After 8 hours, confirm that by TLC the spot of raw material disappears, reaction finishes.Stirring is left standstill after stopping, and the bottom water layer is carried out separatory.Then, add 189.9 parts of agitator treatings of entry, the bottom water layer is carried out separatory.Filtering back filter cake water washs for 253 parts.After 60 ℃ of vacuum-dryings, confirm to reach constant, obtain 24.2 parts of purpose compounds.

The gained compound is carried out infrared absorption spectrum, visible absorption spectrum, ultimate analysis, and (C, H N), atomic absorption analysis, mass spectroscopy, confirm that this compound is a compound N compound o.4.

In addition, by the method same, make the compound 5～20 and the compound 22 of record in table 1 and the table 2 with Production Example 1～4.

Except the consumption with the ammonium sulfate in the Production Example 2 reduced by half, other operation was identical with Production Example 2, makes compound 21.

[relatively charge control agent 1]

Iron azo complex compound (Baotugu Chemical Industrial Co., Ltd's system, trade(brand)name: T-77) as the following structure of having of known charge control agent.In the following formula, a+b+c is 1.

[relatively charge control agent 2]

Chromium azo complex compound (Baotugu Chemical Industrial Co., Ltd's system, trade(brand)name: T-95) as the following structure of having of known charge control agent.

[relatively Production Example 3]

In 0.5 molar sodium hydroxide and water, add 0.4 mole 3,5-di-tert-butyl salicylic acid, heating for dissolving.Then, in this solution, add 0.1 mole of Al ₂(SO ₄) ₃The aqueous solution make the reaction carry out.In 50 ℃ the reaction 3 hours after, the white crystals that leaching is separated out.After crystallization washed, decompression was down in 40 ℃ of dryings 24 hours.The gained reactant is to combine 3 of 2 molecules corresponding to the aluminium atom as purpose, the compound of 5-di-tert-butyl salicylic acid.

[embodiment 1]

Styrene-propene acid acrylic copolymer resin (acid number 0.1mgKOH/g) 91 parts

(Mitsui Chemicals, Inc's system, trade(brand)name CPR-100)

1 part of the compound that Production Example 1 obtains

5 parts of carbon blacks (Mitsubishi chemical Co., Ltd's system, trade(brand)name MA-100)

Low-molecular-weight polypropylene (Sanyo Chemical Industries Co., Ltd.'s system, 3 parts

Trade(brand)name PVC スコ-Le 550P)

Utilize 130 ℃ heating and mixing device (twin shaft pressurization mixing roll) that said mixture is carried out melting mixing, with beater grinder to carrying out coarse reduction through overcooled mixture.Carry out the broken back classification of micro mist with injector-type mill, obtaining volume average particle size is the nonmagnetic toner of 9 ± 0.5 μ m.Ferrite carrier (trade(brand)name F96-100 to this toning agent and silicon coating system, パウダ-テッ Network Co., Ltd. system) (toning agent: ratio carrier) was mixed vibration with 4: 100 mass parts, after making toning agent electronegative, measure with ejection (blow-off) body of powder electrification amount determining device.

In addition, calculate as the time constant (τ) that plays electrical index.With ejection carried charge determinator the charged carried charge that reaches capacity is measured at regular intervals, according to [electronic photography association will, P307, the 27th volume, No. 3 (1988)] record following formula calculate ln (qmax-q), with the relation of curve representation time t and ln (qmax-q), obtain time constant (τ).

(qmax-q)/(qmax-q0)＝exp(-t/τ)

Here, qmax represents the saturation zone electric weight, and q0 represents initial stage carried charge (when electrification time is 10 seconds), and t is each minute, and the carried charge of this moment is q.

Play electrically good toning agent, its time constant is littler, and the unit of time constant is second.

In addition, charged environmental stability is estimated.The evaluation method of environmental stability, except common the mensuration under the environment of 25 ℃-50%RH (relative humidity), also by low wet environment (10 ℃-30%RH) and high humidity environment (35 ℃-carried charge mensuration under 85%RH) is judged.It is exactly to make at the photographic developer that exposes 24 hours under the various environment to the open air fully chargedly in this environment that carried charge is measured, and utilizes ejection carried charge tester to measure the saturation zone electric weight.The variation of carried charge is less than 10% be designated as good (zero) under 3 kinds of environment, and 10～20% be designated as slightly poor (△) surpasses 20% be designated as poor (*).Carried charge, time constant and environmental stability the results are shown in table 3.

[embodiment 2～22]

Except o.2～22 substituting " compound that Production Example 1 obtains " with the compound N in table 1 and the table 2 respectively, the method that comprises addition and embodiment 1 is same, the modulation nonmagnetic toner, estimate carried charge, time constant and environmental stability that ejection body of powder electrification amount determining device is measured, as embodiment 2～embodiment 22, show the result in table 3 respectively.

[comparative example 1～3]

Except respectively with charge control agent 1 relatively, relatively charge control agent 2 and relatively the compound of Production Example 3 substitute " compound that Production Example 1 obtains ", the method that comprises addition and embodiment 1 is same, the modulation nonmagnetic toner, estimate carried charge, time constant and environmental stability that ejection body of powder electrification amount determining device is measured, respectively as a comparative example 1～3, show the result in table 3.

Table 3

	Carried charge (μ C/g)	Timeconstant (s)	Environmental stability
	Carried charge (μ C/g)	Timeconstant (s)	Environmental stability	Embodiment 1	-15.5	93	○
Embodiment 2	-17.6	83	○	Embodiment 1	-15.5	93	○
Embodiment 2	-17.6	83	○	Embodiment 3	-20.9	74	○
Embodiment 4	-16.8	71	○	Embodiment 3	-20.9	74	○
Embodiment 4	-16.8	71	○	Embodiment 5	-17.0	109	○
Embodiment 6	-16.8	110	○	Embodiment 5	-17.0	109	○
Embodiment 6	-16.8	110	○	Embodiment 7	-17.4	116	○
Embodiment 8	-15.7	124	○	Embodiment 7	-17.4	116	○
Embodiment 8	-15.7	124	○	Embodiment 9	-17.0	114	○
Embodiment 10	-15.9	101	○	Embodiment 9	-17.0	114	○
Embodiment 10	-15.9	101	○	Embodiment 11	-15.6	137	○
Embodiment 12	-15.2	119	○	Embodiment 11	-15.6	137	○
Embodiment 12	-15.2	119	○	Embodiment 13	-15.3	117	○
Embodiment 14	-16.7	139	○	Embodiment 13	-15.3	117	○
Embodiment 14	-16.7	139	○	Embodiment 15	-18.1	88	○
Embodiment 16	-17.9	130	○	Embodiment 15	-18.1	88	○
Embodiment 16	-17.9	130	○	Embodiment 17	-18.0	124	○
Embodiment 18	-17.5	85	○	Embodiment 17	-18.0	124	○
Embodiment 18	-17.5	85	○	Embodiment 19	-16.5	81	○
Embodiment 20	-16.3	95	○	Embodiment 19	-16.5	81	○
Embodiment 20	-16.3	95	○	Embodiment 21	-17.8	85	○
Embodiment 22	-16.3	113	○	Embodiment 21	-17.8	85	○
Embodiment 22	-16.3	113	○	Comparative example 1	-16.3	286	△
Comparative example 2	-19.7	245	○	Comparative example 1	-16.3	286	△
Comparative example 2	-19.7	245	○	Comparative example 3	-7.9	225	×

Can find out obviously that from table 3 nonmagnetic toner of embodiment 1～22 has the carried charge of enough practicalities, and time constant is less, thus be electrically and environmental stability well, have the toning agent of highly charged ability concurrently.

(evaluating characteristics of the image that obtains by non magnetic 2 composition developing methods)

Employing is ferrite carrier (パウダ-テッ Network Co., Ltd. system with 4: 100 parts mixed embodiment 1～4 and comparative example 1～3 used nonmagnetic toner and silicon coating, F96-100) photographic developer that forms carries out evaluating characteristics to the image that utilizes non magnetic 2 composition developing methods to obtain.The device that the image processing system that is used for the picture characteristics evaluation is the duplicating machine that improves commercially available non magnetic 2 composition visualization way, can control the photosensitive surface current potential arbitrarily, developer roll applies voltage, transfer voltage, fixing temperature, the image setting lettering at initial stage reaches each condition of optimum regime.Continuous supply toning agent during printing, begin to attempt (test chart) printing simultaneously, respectively with the 10th (initial stage image), print behind 5 thousand sheets continuously, the image that prints after 20,000 continuously is sample, carries out the picture characteristics evaluation, with them respectively as embodiment 23～26, comparative example 4～6.

Use common paper (75g/m ²), will print image behind the regulation number as sample, (サカイ Application Network ス Co., Ltd. system RD-918) is partly measured as image color complete blacking with the Macbeath reflection of the concentration.Photographic fog concentration is exactly to measure the reflection density of the part of lettering not, deducts value as reflection density (0.05) gained of the common paper before the printing of basic value by this value.About line reproducibility, estimate the 30 μ m fine rules of attempting and can verily reproduce, the results are shown in table 4.In the table 4, for line reproducibility, being designated as of can verily reproducing is good, and being designated as of can't verily reproducing is bad.

Table 4

	Line reproducibility			Image color			Photographic fog concentration
	Line reproducibility			Image color			Photographic fog concentration				Initial stage	Behind 5 thousand sheets	After 20,000	Initial stage	Behind 5 thousand sheets	After 20,000	Initial stage	Behind 5 thousand sheets	After 20,000
Embodiment 23	Well	Well	Well	1.45	1.45	1.45	0.01	0.00	0.01		Initial stage	Behind 5 thousand sheets	After 20,000	Initial stage	Behind 5 thousand sheets	After 20,000	Initial stage	Behind 5 thousand sheets	After 20,000
Embodiment 23	Well	Well	Well	1.45	1.45	1.45	0.01	0.00	0.01	Embodiment 24	Well	Well	Well	1.44	1.45	1.43	0.01	0.01	0.02
Embodiment 25	Well	Well	Well	1.45	1.44	1.45	0.01	0.02	0.03	Embodiment 24	Well	Well	Well	1.44	1.45	1.43	0.01	0.01	0.02
Embodiment 25	Well	Well	Well	1.45	1.44	1.45	0.01	0.02	0.03	Embodiment 26	Well	Well	Well	1.45	1.44	1.44	0.01	0.01	0.02
Comparative example 4	Well	Well	Bad	1.40	1.35	1.31	0.02	0.06	0.07	Embodiment 26	Well	Well	Well	1.45	1.44	1.44	0.01	0.01	0.02
Comparative example 4	Well	Well	Bad	1.40	1.35	1.31	0.02	0.06	0.07	Comparative example 5	Well	Well	Bad	1.41	1.42	1.29	0.01	0.03	0.10
Comparative example 6	Well	Bad	Bad	1.38	1.34	1.18	0.02	0.04	0.12	Comparative example 5	Well	Well	Bad	1.41	1.42	1.29	0.01	0.03	0.10

Among the embodiment 23～26, image color reaches comparatively ideal 1.40～1.45 for duplicating machine, and is good.Concentration does not almost change in printing continuously for a long time, and is stable.The photographic fog concentration value is also extremely low, and does not also have increase when printing continuously.Line reproducibility is good, and is stable.

In the comparative example 4～6, the initial stage image can obtain can gratifying image, but image color slightly descends after printing 5 thousand sheets continuously, and photographic fog concentration rises.After printing 20,000 continuously, image deterioration is more obvious, and printing goes wrong.Long-term printing continuously back line reproducibility is deterioration significantly.

[embodiment 27]

100 parts of styrene-propene acid acrylic copolymer resin

(acid number 0.1mgKOH/g)

(Mitsui Chemicals, Inc's system, trade(brand)name CPR-100)

2 parts of the compounds that Production Example 1 obtains

Martial ethiops (titanium Industrial Co., Ltd system, 90 parts

Trade(brand)name BL-200)

Trade(brand)name PVC スコ-Le 550P)

Utilize 130 ℃ heating and mixing device (twin shaft pressurization mixing roll) that said mixture is carried out melting mixing, with beater grinder to carrying out coarse reduction through overcooled mixture.Carry out the broken back classification of micro mist with injector-type mill again, obtaining volume average particle size is the magnetic color tuner of 9 ± 0.5 μ m.

[embodiment 28～30]

Substitute " compound that Production Example 1 obtains " except using " compounds of Production Example 2 gained ", " compound that Production Example 3 obtains " to reach " compound that Production Example 4 obtains " respectively, comprise that addition is all identical with embodiment 27, the modulation magnetic color tuner, with them respectively as embodiment 28, embodiment 29 and embodiment 30.

[comparative example 7～9]

Except substituting " compound of Production Example 1 acquisition " with the compound that compares charge control agent 1, relatively charge control agent 2, relatively Production Example 3 acquisitions respectively, comprise that addition is all identical with embodiment 27, the modulation magnetic color tuner, with their respectively as a comparative example 7～9.

(evaluating characteristics of the image that forms by magnetic 1 composition visualization way)

The magnetic color tuner that adopts embodiment 27～30 and comparative example 7～9 to make is estimated the characteristic of the image that forms by magnetic 1 composition visualization way.

The image processing system that is applicable to present embodiment be improve commercially available magnetic 1 composition visualization way printing press (resolution 600dpi), can control the photosensitive surface current potential arbitrarily, device that developer roll applies voltage, transfer voltage, fixing temperature, initial stage image setting lettering reaches each condition of optimum regime.

Continuous supply toning agent during printing is attempted by the computer transmission simultaneously, with the printing beginning to the 10th initial stage image, print behind 1 thousand sheets continuously, the image that prints continuously behind 5 thousand sheets is sample, carries out the picture characteristics evaluation.

Will be to common paper (75g/m ²) printed image behind the regulation number as sample, (サカイ Application Network ス Co., Ltd. system RD-918) is partly measured as image color complete blacking with the Macbeath reflection of the concentration.Photographic fog concentration is exactly to measure the reflection density of the part of lettering not, deducts value as reflection density (0.05) gained of the common paper before the printing of basic value by this value.About a reproducibility, to estimate the point of attempting and can verily reproduce, point reproduces according to the isolated point figure of about 50 μ m and can the reproduction of N/D ground judge.In about 50 points, be judged as in the situation more than 1 one-tenth in damaged o'clock bad, good being judged as below 1 one-tenth, the results are shown in table 5.

Table 5

	The point reproducibility			Image color			Photographic fog concentration
	The point reproducibility			Image color			Photographic fog concentration				Initial stage	Behind 1 thousand sheets	Behind 5 thousand sheets	Initial stage	Behind 1 thousand sheets	Behind 5 thousand sheets	Initial stage	Behind 1 thousand sheets	Behind 5 thousand sheets
Embodiment 27	Well	Well	Well	1.45	1.46	1.45	0.00	0.00	0.00		Initial stage	Behind 1 thousand sheets	Behind 5 thousand sheets	Initial stage	Behind 1 thousand sheets	Behind 5 thousand sheets	Initial stage	Behind 1 thousand sheets	Behind 5 thousand sheets
Embodiment 27	Well	Well	Well	1.45	1.46	1.45	0.00	0.00	0.00	Embodiment 28	Well	Well	Well	1.47	1.46	1.47	0.00	0.01	0.01
Embodiment 29	Well	Well	Well	1.45	1.47	1.47	0.00	0.01	0.00	Embodiment 28	Well	Well	Well	1.47	1.46	1.47	0.00	0.01	0.01
Embodiment 29	Well	Well	Well	1.45	1.47	1.47	0.00	0.01	0.00	Embodiment 30	Well	Well	Well	1.46	1.45	1.45	0.00	0.01	0.01
Comparative example 7	Well	Well	Bad	1.41	1.35	1.35	0.02	0.09	0.10	Embodiment 30	Well	Well	Well	1.46	1.45	1.45	0.00	0.01	0.01
Comparative example 7	Well	Well	Bad	1.41	1.35	1.35	0.02	0.09	0.10	Comparative example 8	Well	Well	Bad	1.43	1.34	1.18	0.01	0.07	0.12
Comparative example 9	Well	Bad	Bad	1.39	1.37	1.22	0.00	0.06	0.11	Comparative example 8	Well	Well	Bad	1.43	1.34	1.18	0.01	0.07	0.12

Among the embodiment 27～30, image color reaches comparatively ideal 1.45～1.50 for printing press, and is good.Concentration does not almost change in printing continuously for a long time, and is stable.The photographic fog concentration value is also extremely low, and does not also have increase when printing continuously.The point reproducibility is good, and is stable.

In the comparative example 7～9, the initial stage image can obtain can gratifying image, but image color slightly descends after printing 1 thousand sheets continuously, and photographic fog concentration rises.Behind printing 5 thousand sheets, image deterioration is more obvious continuously, and printing goes wrong.Long-term printing continuously back point reproducibility is deterioration significantly.

Claims

1. the Monoazo/iron complex compound of formula [1] expression,

In the formula [1], A ₁, A ₂, B ₁, B ₂Independent mutually, expression H, alkyl or halogen atom; J represents H, basic metal, NH ₄Or alkylammonium, also can be wherein more than 2 kinds; X ₁, X ₂Independent mutually, expression H, alkyl, halogen atom; Y ₁, Y ₂Independent mutually, represent H, alkyl, can have substituent aromatic group; But A ₁, A ₂, B ₁, B ₂, X ₁, X ₂, Y ₁, Y ₂Be except the situation of hydrogen atom simultaneously.

2. the Monoazo/iron complex compound of formula [2] expression,

In the formula [2], J represents H, Na, NH ₄Or alkylammonium, also can be wherein more than 2 kinds; X ₁, X ₂Independent mutually, expression H, alkyl or halogen atom; Y ₁, Y ₂Independent mutually, expression H, alkyl or halogen atom.

3. the Monoazo/iron complex compound of formula [3] expression,

In the formula [3], J represents H, Na, NH ₄Or alkylammonium, also can be wherein more than 2 kinds.

4. the Monoazo/iron complex compound of formula [4] expression,

5. the Monoazo/iron complex compound of formula [5] expression.

6. charge control agent is characterized in that, is effective constituent with each described Monoazo/iron complex compound in the claim 1～5.

7. charge control agent as claimed in claim 6, its feature are that also the volume average particle size of charge control agent is 0.1～20 μ m.

8. the electronegativity toning agent is characterized in that, contains each described Monoazo/iron complex compound, tinting material and binder resin in the claim 1～5.

9. toning agent as claimed in claim 8, its feature also be, Monoazo/iron complex compound is that the amount of 0.1～10 mass parts is added in toner particle with the binder resin corresponding to 100 mass parts.

10. toning agent as claimed in claim 8 or 9, its feature is that also the acid number of binder resin is 0.1～100mgKOH/g.

11. as each described toning agent in the claim 8～10, its feature is that also tinting material is a magnetic substance.

12. as each described toning agent in the claim 8～10, its feature is that also tinting material is non magnetic tinting material, contains 0.1～20 mass parts corresponding to the binder resin of 100 mass parts.

13. as each described toning agent in the claim 8～12, its feature also is, also contains wax.

14. as each described toning agent in the claim 8～13, its feature is that also the volume average particle size of toning agent is 2～15 μ m.

15.1 composition is a photographic developer, it is characterized in that, is formed by each described toning agent in the claim 8～14.

16.2 composition is a photographic developer, it is that 2 compositions with electronegativity toning agent and carrier are photographic developer, it is characterized in that, this toning agent contains binder resin, tinting material and Monoazo/iron complex compound at least, and this Monoazo/iron complex compound is each described Monoazo/iron complex compound in the claim 1～5.

17. 2 compositions as claimed in claim 16 are photographic developer, its feature also is, Monoazo/iron complex compound is being that the amount of 0.1～10 mass parts is added in toner particle corresponding to 100 mass parts binder resins.

18. as claim 16 or 17 described 2 compositions is photographic developer, its feature is that also it is that resin is as binder resin that toning agent contains styrene-propene acid.

19. 2 compositions as claimed in claim 18 are photographic developer, its feature is that also the acid number of binder resin is 0.1～100mgKOH/g.

20. as each described 2 compositions in the claim 16～19 is photographic developer, its feature also is, also contains wax.

21. as each described 2 compositions in the claim 16～20 is photographic developer, its feature is that also the volume average particle size of toning agent is 2～15 μ m.

22. as each described 2 compositions in the claim 16～21 is photographic developer, its feature is that also carrier is the resin coating carrier.