CN102652287B

CN102652287B - Method for producing toner

Info

Publication number: CN102652287B
Application number: CN201080056507.9A
Authority: CN
Inventors: 水田浩司
Original assignee: Kao Corp
Current assignee: Kao Corp
Priority date: 2009-12-14
Filing date: 2010-12-14
Publication date: 2015-03-18
Anticipated expiration: 2030-12-14
Also published as: CN102652287A; DE112010004799T5; JP5552493B2; WO2011074580A1; JPWO2011074580A1

Abstract

Disclosed are: a toner for electrophotography, which has excellent storage stability and excellent fixability including fixability at low temperatures and hot offset resistance; and a method for producing the toner for electrophotography. Specifically disclosed is a method for producing a toner, which comprises: (1) a step in which release agent particles are obtained by emulsifying (A) a release agent and (B) a release agent having a melting point higher than that of the release agent (A) by 5 DEG C or more in an aqueous medium in the presence of a polycarboxylic acid salt; and (2) a step in which the thus-obtained release agent particles and resin particles are agglomerated and coalesced together.

Description

The manufacture method of toner

Technical field

The manufacture method that the present invention relates to toner and the electrophoto-graphic toner obtained by this manufacture method.

Background technology

In the field of electrophoto-graphic toner, along with the development of electrophotographic system, require the toner that exploitation is corresponding with high image quality and high speed.From the view point of high image quality, need toner small particle diameter, disclose the melting mixing method in the past of substituting and the so-called chemical toner that obtained by chemical methods such as polymerization or emulsion dispersion methods.And then, from the view point of high speed, report in order to improve low-temperature fixability in fixation performance and in add the chemical toner having release agent, but due to chemical method different from melting mixing comminuting method, it does not have compounding procedure, so the dispersiveness of release agent in toner is insufficient.

In patent documentation 1, disclose the releasing agent dispersion improving this problem points, namely contain release agent and there is the dibasic acid of alkyl and/or alkenyl or the toner releasing agent dispersion of its salt.On the other hand, disclosing the anti-hot-offset property (hotoffset resistance) from the view point of improving further in fixation performance in patent documentation 2,3, release agent melting mixing of more than two kinds being made the technology that dispersion liquid uses.

Prior art document

Patent documentation

Patent documentation 1: Japanese Unexamined Patent Publication 2008-33139 publication

Patent documentation 2: Japanese Unexamined Patent Publication 2006-267280 publication

Patent documentation 3: Japanese Unexamined Patent Publication 2007-218961 publication

Summary of the invention

Invent problem to be solved

But, make resin particle and release agent particle coacervation and coalescent and obtain chemical toner time, in order to obtain wider can fixing temperature rrange and use release agent particle of more than two kinds when, if make itself and resin particle jointly condense, because the stability of release agent particle is different separately, so cannot condense with resin particle, or become the cohesion of the non-constant width of size-grade distribution.

In addition, on the other hand, according to the kind of release agent, sometimes low with the compatibility of resin particle, such as namely allow to condense but agglomerated process after cohesion process time there is release agent particle from the free problem of aggregated particle.

Namely, problem of the present invention is the manufacture method providing a kind of toner, make resin particle and release agent particle coacervation and coalescent and in the manufacture of the chemical toner obtained, even if when using two or more release agent, also controlling the cohesion under the small particle diameter when manufacturing toner, there is no the free of release agent when agglomerated process.

In addition, problem of the present invention is that providing a kind of comprises the fixation performance of low-temperature fixability and anti-hot-offset property and the electrophoto-graphic toner of excellent storage stability.

For the means of dealing with problems

The present invention relates to:

[1] manufacture method for toner, it comprises following operation: (1) by release agent (A) and there is high more than 5 DEG C of the fusing point than this release agent (A) the release agent (B) of fusing point in water-medium, the existing emulsified and obtain the operation of release agent particle of polycarboxylate; And (2) make obtained release agent particle and resin particle condense and coalescent operation; And

[2] electrophoto-graphic toner, it is obtained by the manufacture method described in above-mentioned [1].

The effect of invention

According to the present invention, can provide a kind of manufacture method of toner, its cohesion that can control under small particle diameter when manufacturing toner generates the aggregated particle of narrow particle size distribution, and does not have the free of release agent when agglomerated process.

In addition, according to the present invention, the electrophoto-graphic toner of low-temperature fixability and anti-hot-offset property and fixation performance and excellent storage stability can be provided.

Embodiment

[manufacture method of toner]

The manufacture method of toner of the present invention comprises following operation: (1) by release agent (A) and there is high more than 5 DEG C of the fusing point than this release agent (A) the release agent (B) of fusing point in water-medium, the existing emulsified and obtain the operation of release agent particle of polycarboxylate; And (2) make obtained release agent particle and resin particle condense and coalescent operation.

Namely, in the past, make resin particle and release agent particle coacervation and coalescent and in the chemical toner obtained, if use release agent particle of more than two kinds, then prepare release agent particle and make it and resin particle condenses time, because the stability of each release agent particle is different, so the suitable cohesion realizing two or more release agent particle above-mentioned and resin particle, the aggregated particle that namely generates narrow particle size distribution are difficult.In addition, in this case, also easily there is the free of release agent when condensing or time coalescent.That is, according to the kind of release agent, such as, namely allow to cohesion, due to low with the compatibility of resin particle, thus also easily occur release agent particle dissociating from aggregated particle when agglomerated process.In the present invention, by providing the manufacture method employing and at least make above-mentioned specific 2 kinds of release agents there is the toner of emulsified release agent particle at polycarboxylate, above-mentioned problem can be solved.

(operation (1))

Operation (1) in the manufacture method of toner of the present invention is by release agent (A) and the release agent (B) of fusing point the existing emulsified and obtaining the operation of release agent particle in polycarboxylate in water-medium with high more than 5 DEG C of the fusing point than this release agent (A).

release agent (A) and release agent (B)

In the present invention, release agent particle obtains with the form of the dispersion liquid and releasing agent dispersion that comprise its release agent particle usually, as used release agent (A) and release agent (B), from the view point of the low-temperature fixability of toner, its fusing point of preferred use is the release agent of less than 100 DEG C, more preferably fusing point is the release agent of 60 ~ 95 DEG C, and preferably fusing point is the release agent of 65 ~ 90 DEG C further.Particularly in the present invention, from the view point of above-mentioned, the fusing point of release agent (B) is less than 100 DEG C, preferred fusing point is the release agent of 60 ~ 95 DEG C, more preferably fusing point is the release agent of 65 ~ 90 DEG C, preferably fusing point is the release agent of 75 ~ 90 DEG C further, and further preferably fusing point is the release agent of 80 ~ 85 DEG C.In addition, the fusing point of release agent (A) is less than 100 DEG C, and preferred fusing point is the release agent of 60 ~ 95 DEG C, and more preferably fusing point is the release agent of 65 ~ 90 DEG C, and preferably fusing point is the release agent of 65 ~ 85 DEG C further, and further preferably fusing point is the release agent of 70 ~ 80 DEG C.

As release agent (A) and release agent (B), specifically, the low-molecular-weight polyolefin classes such as tygon, polypropylene, polybutylene can be listed; There is by heating the silicone of softening point; The fatty acid acyl amines such as oleamide, erucyl amide, ricinoleic acid amide, stearmide; Department of botany's waxes such as Brazil wax, rice bran wax, candelila wax, haze tallow, Jojoba Oil; The animal system waxes such as beeswax; The synthetic waxs etc. such as the mineral such as montan wax, ceresine, ceresin, paraffin, microcrystalline wax, Fischer-Tropsch wax/petroleum wax, ester type waxes.As release agent (A), preferred mineral/petroleum wax, synthetic wax, wherein, from the view point of the low-temperature fixability of toner, more preferably paraffin, ester type waxes, from the view point of the storage stability improving toner, preferred paraffin further.As release agent (B), preferred plant system wax, more preferably Brazil wax.

In the present invention, as long as the release agent of different melting points more than 5 DEG C (A) and release agent (B) in such as these release agents of choice for use, as limit, release agent (A) and release agent (B) can be one species, also can be variety classeses.In the present invention, by the release agent using at least 2 kinds of such fusing points different, the fixation performance of the toner obtained becomes good.

Release agent (B) is the release agent of the fusing point of high more than 5 DEG C of the fusing point had than release agent (A), from the release agent particle that can obtain the cohesion that can control small particle diameter when manufacturing toner, and the viewpoint of the fixation performance excellence of the toner obtained is set out, be preferably its fusing point than the release agent of high more than 6 DEG C of release agent (A), be more preferably the release agent of its fusing point than high more than 8 DEG C of release agent (A).In addition, be not particularly limited the higher limit of release agent (A) with the difference of the fusing point of release agent (B), from the view point of the low-temperature fixability of toner, its higher limit is preferably 30 DEG C, is more preferably 20 DEG C.That is, from the view point of the fixation performance of toner, release agent (A) is preferably 6 ~ 30 DEG C with the difference of the fusing point of release agent (B), is more preferably 7 ~ 20 DEG C, more preferably 8 ~ 20 DEG C, is further preferably 8 ~ 9 DEG C.

By using, there is the release agent of such fusing point, though utilize low-temperature fixing fixing in, release agent also can ooze out and promote stripping result from toner, thus can realize low-temperature fixing.

In addition, in the present invention, the fusing point of release agent can use differential scanning calorimeter to measure, and can be measured particularly by method described later.

In the present invention, from the view point of the fixation performance of obtained toner, above-mentioned release agent (A) and release agent (B) are preferably selected from any one in Brazil wax, paraffin, polyolefin and Fischer-Tropsch wax separately, more preferably its any one be Brazil wax, preferably release agent (B) is Brazil wax further, and release agent (A) is for being selected from any one in paraffin, polyolefin and Fischer-Tropsch wax.

For the release agent particle in releasing agent dispersion, from the view point of the fixation performance of toner, preferably count 5/95 ~ 95/5 containing release agent (A) and release agent (B) with weight ratio (release agent (A)/release agent (B)), more preferably contain with 10/90 ~ 90/10, preferably further to contain with 15/85 ~ 85/15, further preferably to contain with 40/60 ~ 50/50.

By making release agent particle contain 2 kinds of different release agents of above-mentioned fusing point, thus play effect of the present invention, but only otherwise damage effect of the present invention, can other release agent be contained.

From the view point of the electrophoto-graphic toner obtaining fixation performance and excellent storage stability, release agent (A) in the present invention in whole release agent and the total amount of this release agent (B) are preferably more than 90 % by weight, be more preferably more than 99 % by weight, more preferably 100 % by weight.

polycarboxylate

The releasing agent dispersion comprising above-mentioned release agent particle with containing above-mentioned release agent (A) and release agent (B) and polycarboxylate for feature.Thinking by using polycarboxylate, utilizing the interaction of above-mentioned release agent (A) and release agent (B) and polycarboxylate, the cohesion of the appropriateness of resin particle and release agent particle and coalescent can be realized.

As the preferred object lesson of the polycarboxylate used in the present invention, from the view point of make toner time coherency or prevent from dissociating, preferably list the salt, poly salt etc. of polyacrylate, acid-co-maleic acid, the salt of preferred acid-co-maleic acid.As salt, preferred as alkali salt, particular certain cancers.Specifically, preferably can list the sodium salt, poly sodium etc. of the sodium polyacrylate shown in following formula (I) ~ (III), acid-co-maleic acid, from the same viewpoint, be more preferably the sodium salt of acid-co-maleic acid.

From the view point of the effect as spreading agent, the degree of neutralization of the polymer ends base of polycarboxylate is preferably 50 ~ 100%, is more preferably 70 ~ 100%, and more preferably 90 ~ 100%.Here, so-called degree of neutralization refers to the value measured by the potential difference (PD) titration of polycarboxylate aqueous solution.

From the view point of obtaining fine release agent particle, the weight-average molecular weight of polycarboxylate is preferably 3000 ~ 90000, is more preferably 10000 ~ 50000.This weight-average molecular weight can be passed through gel permeation chromatography (GPC) and measure.

As forming the kation of polycarboxylate, being not particularly limited, except the ion of the alkali-metal ion such as sodium, potassium and the alkaline-earth metal such as magnesium, calcium, can ammonium ion or alkyl phosphate ion etc. being used.In the middle of these, from the view point of the dispersiveness of release agent, the ion of preferred as alkali, more preferably sodion.

In releasing agent dispersion, from the view point of the dispersiveness of the cohesion during cohesion process controlled when toner makes and the release agent in the toner that obtains, preferably containing 0.1 ~ 5 % by weight, more preferably containing 0.5 ~ 2.5 % by weight polycarboxylate.In addition, in releasing agent dispersion, from the same viewpoint, relative to release agent total amount 100 weight portion, the polycarboxylate preferably containing 0.2 ~ 15 weight portion, more preferably containing 0.4 ~ 10 weight portion, further preferably containing 0.6 ~ 6 weight portion.

release agent particle

Release agent particle obtains with the form of the dispersion liquid and releasing agent dispersion that comprise its release agent particle usually.

From the view point of the storage stability of emulsibility and dispersion liquid, the solid component concentration of the release agent in releasing agent dispersion is preferably 5 ~ 40 % by weight, is more preferably 10 ~ 35 % by weight, and more preferably 15 ~ 35 % by weight.In addition, from the view point of the storage stability of releasing agent dispersion, the pH of releasing agent dispersion is preferably 5 ~ 10, is more preferably 6 ~ 9.5.

In addition, in releasing agent dispersion, from the view point of the dispersiveness of the cohesion during cohesion process controlled when toner makes and the release agent in the toner that obtains, release agent (A) and release agent (B) amount to containing 5 ~ 40 % by weight, more preferably containing 10 ~ 35 % by weight, further preferably containing 15 ~ 30 % by weight.

In addition, the release agent (A) forming the release agent particle in releasing agent dispersion and release agent (B) containing proportional also as described above.

Together with above-mentioned release agent (A), release agent (B), polycarboxylate, known emulsifying agent can be used in the scope not hindering effect of the present invention in releasing agent dispersion.As such emulsifying agent, include, for example out the unitary hydrochlorates such as odium stearate, potassium oleate, neopelex, the macromolecule dispersing agents etc. such as polyvinyl alcohol.

From the view point of fixation performance and the permanance of toner, the volume medium (D50) of release agent particle is preferably less than 1 μm, is more preferably 0.05 ~ 1 μm, more preferably 0.1 ~ 0.85 μm.In addition, in this instructions, so-called volume medium (D50), refers to that the cumulative volume frequency calculated with volume fraction calculates from the side that particle diameter is little the particle diameter reaching 50%.

Releasing agent dispersion is by having above-mentioned formation, and emulsifiability is excellent.From the fixation performance of toner, permanance and coherent viewpoint, release agent particle in releasing agent dispersion is preferably the particle of its narrow particle size distribution, specifically, less than 50% is preferably in CV value (standard deviation/volume medium (50) × 100 of size-grade distribution), be more preferably less than 45%, more preferably less than 40%.Here, the particle diameter of release agent particle and size-grade distribution can use light scattering formula particle size distribution machine to measure in particular by method described later.

The releasing agent dispersion obtained like this has good emulsifiability and emulsion stability, through also stablizing for a long time.In addition, because cohesion during cohesion process when this toner makes controls to improve, so the particle shape of toner can be controlled, electrophoto-graphic toner can be suitably used for.In addition, release agent particle for by resin particle and release agent particle coacervation and coalescent and toner that is that obtain, plays effect of the present invention as described later thus.

Above-mentioned release agent particle obtains by release agent (A) and the release agent (B) of fusing point with high more than 5 DEG C of the fusing point than this release agent (A) being carried out the method for emulsification under the existence of polycarboxylate in water-medium.

Specifically, above-mentioned release agent (A) and above-mentioned release agent (B) are disperseed in water-medium under the existence of polycarboxylate, preferred while be heated to more than the fusing point of release agent (B), such as while be dispersed into microgranular with the homogenizer, pressure squirt-type homogenizer, ultrasonic dispersing machine etc. with Strong shear power, the dispersion liquid of release agent particle can be made.

Above-mentioned water-medium is using water as principal ingredient.From the view point of Environmental, the content of the water in water-medium is preferably more than 80 % by weight, is more preferably more than 90 % by weight, and more preferably 100 % by weight.

As the composition than water in water-medium, the organic solvent that alcohol system organic solvent or acetone, MEK, the tetrahydrofurans etc. such as methyl alcohol, ethanol, isopropyl alcohol, butanols are dissolved in water can be listed.In the middle of these, from the view point of preventing from being mixed in toner, the alcohol system organic solvent such as organic solvent and methyl alcohol, ethanol, isopropyl alcohol, butanols of not dissolving resin can be used.In the present invention, preferably in fact not with an organic solvent, water is only used to make resin particle.

In addition, from the aspect of the emulsibility of release agent, dispersion temperature is preferably 60 ~ 120 DEG C, is more preferably 80 ~ 110 DEG C, more preferably 80 ~ 100 DEG C.

(operation (2))

Operation (2) is that obtained release agent particle and resin particle are condensed and coalescent operation.That is, electrophoto-graphic toner of the present invention makes aforesaid release agent particle and resin particle condense and coalescent and obtain.

resin particle

Resin particle in the present invention obtains with the form of the resin particle dispersion liquid of this resin particles dispersion in water-medium.From the view point of low-temperature fixability and the permanance of toner, the resin particle in the present invention is preferably containing polyester.From the same viewpoint, the content of polyester is preferably more than 50 % by weight in resin, is more preferably more than 60 % by weight, is more preferably more than 70 % by weight, and more preferably more than 80 % by weight, further preferably essence is 100 % by weight.As the resin forming resin particle, except polyester, the known resin used in toner can be used, such as polyester, styrene acrylic copolymer, epoxy, polycarbonate, polyurethane etc.

When using polyester, its starting monomer is not particularly limited, and can use the known carboxylic acid compositions such as known alcohol composition and carboxylic acid, carboxylic acid anhydrides, carboxylate.

As carboxylic acid, the dicarboxylic acid such as phthalic acid, m-phthalic acid, terephthalic acid (TPA), fumaric acid, maleic acid, hexane diacid, succinic acid can be listed, dodecenyl succinic acid, ocentyl succinic etc. by carbon number be 1 ~ 20 alkyl or carbon number be 2 ~ 20 the carboxylic acid of succinic acid etc. 2 yuan that replaces of alkenyl, the polybasic carboxylic acid that trimellitic acid, Pyromellitic Acid etc. are more than 3 yuan, alkyl (carbon number is 1 ~ 3) ester etc. of the acid anhydride of these acid and these acid.

This carboxylic acid composition can be used alone a kind, also can combine two or more and use.

In addition, as alcohol composition, specifically, polyoxypropylene-2 can be listed, 2-two (4-hydroxyphenyl) propane, polyoxyethylene-2, oxyalkylene (carbon number 2 ~ 3) (average addition molal quantity 1 ~ 16) addition product, hydrogenated bisphenol A, ethylene glycol, propylene glycol, the neopentyl glycol, 1 of the bisphenol-As such as two (4-hydroxyphenyl) propane of 2-, 4-butylene glycol, 1,3-butylene glycol, 1,6-hexanediol, glycerine, pentaerythrite, trimethylolpropane, D-sorbite or their oxyalkylene (carbon number 2 ~ 4) (average addition molal quantity 1 ~ 16) addition product etc.Above-mentioned alcohol can combine two or more and use.

Polyester such as can manufacture by alcohol composition and carboxylic acid composition being used as required in inactive gas atmosphere esterification catalyst polycondensation at the temperature of about 180 ~ 250 DEG C.

As esterification catalyst, the esterification catalysts such as titanium compound such as the tin compound such as dibutyltin oxide, two tin octoates, two (triethanolamine) metatitanic acid diisopropyl ester can be used.The use amount of esterification catalyst, relative to total amount 100 weight portion of alcohol composition and carboxylic acid composition, is preferably 0.01 ~ 1 weight portion, is more preferably 0.1 ~ 0.6 weight portion.

Polyester can be any one of crystalline polyester and noncrystalline polyester, from the view point of fixation performance and the charging property of toner, and preferred noncrystalline polyester.

In the present invention, so-called " noncrystalline polyester ", refer to refer to crystallinity index that softening point and the ratio (maximum peak temperature of softening point/heat absorption) of the maximum peak temperature of heat absorption define be preferably greater than 1.3 and below 4, be more preferably 1.5 ~ 3 polyester.From the view point of fixation performance and the storage stability of toner, the softening point of polyester is preferably 70 ~ 165 DEG C, is more preferably 90 ~ 165 DEG C, and glass transition temperature is preferably 50 ~ 85 DEG C, is more preferably 55 ~ 85 DEG C.From the same viewpoint, acid number is preferably 6 ~ 35mgKOH/g, is more preferably 10 ~ 35mgKOH/g, more preferably 15 ~ 35mgKOH/g.Softening point or acid number can by regulating the ratio that feeds intake of alcohol and carboxylic acid, the temperature of polycondensation, the reaction time obtains desired value.

In addition, in the present invention, in polyester, not only comprise unmodified polyester, also comprise the polyester of degree through modification not damage in fact its characteristic.As the polyester of modification, the method that include, for example out by recording in Japanese Unexamined Patent Publication 11-133668 publication, Japanese Unexamined Patent Publication 10-239903 publication, Japanese Unexamined Patent Publication 8-20636 publication etc. utilizes the graftings such as phenol, carbamate, epoxy radicals or blocked polyester, has the compound resin of two or more resin unit comprising polyester unit.

In addition, when resin particle contains various kinds of resin, form softening point, glass transition temperature, acid number that the softening point of the resin of above-mentioned resin particle, glass transition temperature and acid number refer to the potpourri as each resin, each value is preferably the value same with the value of above-mentioned polyester.

And then, when containing polyester, from the view point of the low-temperature fixability of toner and anti-hot-offset property and permanance, the resin forming resin particle can contain 2 kinds of different polyester of softening point, the softening point of one polyester (I) is preferably more than 70 DEG C and lower than 115 DEG C, the softening point of the polyester of the softening point of another polyester (II) is preferably more than 115 DEG C and is less than 165 DEG C.Polyester (I) is preferably 10/90 ~ 90/10 with the weight ratio (I/II) of polyester (II), is more preferably 50/50 ~ 90/10.

In the present invention, when making the resin dispersion of formation resin particle, preferably carry out in water-medium.Make the water-medium of resin dispersion using water as principal ingredient, the medium same with the medium used in aforesaid releasing agent dispersion can be used.

The adjuvant such as above-mentioned resin and colorant as required, charge control agent can be contained in resin particle dispersion liquid.

As colorant, be not particularly limited, known colorant all can use.Specifically, the various dyestuffs such as carbon black, inorganic system complex oxide, chrome yellow, benzidine yellow, pyrazolone orange, resistance to sulfuration orange, Wo Qiuge red (Watchung Red), bright carmine 3B, brilliant carmine 6B, lake red C, rose-bengal (ベ Application ガ Le), the various pigment such as phthalocyanine blue, phthalocyanine green or acridine system, azo system, benzoquinones system, azine system, anthraquinone system, indigo system, phthalocyanine system, nigrosine system can be used alone a kind or combine two or more and use.

Relative to resin 100 weight portion, the content of colorant is preferably below 20 weight portions, is more preferably 0.01 ~ 10 weight portion.

As charge control agent, include, for example out benzoic slaine, salicylic slaine, the slaine of alkyl salicylate, the slaine, containing metal bisazo dye, quaternary ammonium salt etc. of catechol.They can be used alone a kind, also can combine two or more and use.

Relative to resin 100 weight portion, the content of charge control agent in toner is preferably below 10 weight portions, is more preferably 0.01 ~ 5 weight portion.

In the present invention, when manufacturing resin particle with the form of dispersion liquid, from the viewpoint such as dispersion stabilization improving resin, relative to resin 100 weight portion, preferably there are below 10 weight portions, be more preferably below 5 weight portions, be more preferably 0.1 ~ 3 weight portion, the surfactant of more preferably 0.5 ~ 2 weight portion.

As surfactant, include, for example out the anionic surfactants such as sulfuric ester system, sulfonate system, soap system; The cationic surfactants such as amine salt type, quaternary; The nonionic surfactants etc. such as polyglycol system, alkylphenol ethylene oxide adduct system, polyvalent alcohol system.In the middle of these, preferred anionic surfactant, cationic surfactant isoiony surfactant.Preferably nonionic surfactant and anionic surfactant or cationic surfactant are used.Above-mentioned surfactant can be used alone a kind, also can combine two or more and use.

As the object lesson of above-mentioned anionic surfactant, dodecylbenzene sulfonic acid, neopelex, lauryl sodium sulfate, sodium alkylether sulphate etc. can be listed.In the middle of these, preferred neopelex.

In addition, as the object lesson of above-mentioned cationic surfactant, alkyl benzene alkyl dimethyl ammonium chloride, alkyl trimethyl ammonium chloride, distearyl ammonium chloride etc. can be listed.

As nonionic surfactant, include, for example out polyoxyethylene alkylaryl ether class or the polyoxyethylene alkyl ether classes such as ethylene nonyl phenyl ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, the polyoxyethylene fatty acid ester classes such as polyethylene glycol monolaurate, polyethylene glycol mono stearate, polyethylene glycol monooleate, ethylene oxide/propylene oxide segmented copolymer etc.

When preparing above-mentioned resin particle with the form of dispersion liquid, preferably in resin, add aqueous alkali, make resin and the adjuvant dispersion used as required.

Above-mentioned aqueous alkali is preferably the aqueous alkali of the concentration of 1 ~ 20 % by weight, is more preferably the aqueous alkali of the concentration of 1 ~ 10 % by weight, more preferably the aqueous alkali of concentration of 1.5 ~ 7.5 % by weight.About used alkali, when preferably using resin to form salt, improve the alkali of its interfacial energy.Specifically, 1 alkali-metal oxyhydroxide etc. of valency such as potassium hydroxide, NaOH can be listed.

After dispersion, at the temperature preferably more than the glass transition temperature of resin and after, add water-medium at the temperature more than the glass transition temperature of resin, make its emulsification, can resin particle be manufactured thus.

From the aspect effectively can implementing emulsification, the interpolation speed of above-mentioned water-medium is preferably 0.1 ~ 50g/ minute in every 100g resin, is more preferably 0.5 ~ 40g/ minute, more preferably 1 ~ 30g/ minute.As long as this interpolation speed is usually maintained until till essence forms the emulsion of O/W type, the interpolation speed of the water after the dispersion liquid of the resin particle of formation O/W type is not particularly limited.

As the water-medium for manufacturing this resin particle with the form of dispersion liquid, the material identical with forming the water-medium that uses in the dispersion of the resin of aforesaid resin particle can being listed, being preferably deionized water or distilled water.

From the view point of agglomeration process afterwards, obtain uniform aggregated particle, relative to resin 100 weight portion, the amount of water-medium is preferably 100 ~ 2000 weight portions, is more preferably 150 ~ 1500 weight portions.From the viewpoint such as stability and treatability of the dispersion liquid of obtained resin particle, be preferably 7 ~ 50 % by weight according to the solid component concentration of the dispersion liquid of resin particle, be more preferably the amount of the way selection water-medium of 7 ~ 40 % by weight, more preferably 10 ~ 35 % by weight.In addition, the involatile compositions such as resin, pigment, nonionic surfactant are comprised in solid constituent.

In addition, from the view point of the fine resin particle of preparation, temperature during emulsification is preferably more than the glass transition temperature of the resin forming resin particle and scope below softening point.By carrying out at the temperature of above-mentioned scope, thus emulsification is successfully carried out, and does not need special device in this external heat.From this starting point, said temperature is preferably, and (forming the glass transition temperature+10 DEG C of the resin of resin particle) (refers to " temperature of higher than glass transition temperature 10 DEG C ", same explanation is done in record same below) more than, in addition, (softening point of above-mentioned resin-5 DEG C) is preferably below.

In order to condense uniformly in agglomeration process afterwards, the volume medium (D50) of the resin particle obtained like this is preferably 0.02 ~ 2 μm, is more preferably 0.05 ~ 1 μm, more preferably 0.05 ~ 0.6 μm.

As other method obtaining resin particle with the form of dispersion liquid, include, for example out to have and first in water-medium, make the method for the operation of its emulsion dispersion by such as mechanical shearing (シエア) or ultrasound wave etc. using as the polycondensation monomer of target resin particle raw material.Now, as required the adjuvant such as polycondensation catalyst, surfactant is also added in water-soluble medium.Then, by obtained solutionExample as heating etc., thus carry out polycondensation.When resin is polyester, can use polycondensation monomer, the polycondensation catalyst of aforesaid polyester, as surfactant, aforesaid surfactant can use equally.

Usually, condensation resin due to be polymerized time along with dehydration, so be generally difficult to carry out in water-medium.But, such as, together with the surfactant making polycondensation monomer such with forming micella in water-medium in water-medium during emulsification, because monomer is positioned in the hydrophobic region of the microcosmic in micella, thus dehydration becomes and easily carries out, the water generated is discharged in the water-medium outside micella, can be polymerized.Like this, the resin particle dispersion liquid of the resin particle being dispersed with condensation resin in water-medium can low-yieldly be obtained.

cohesion process

In the manufacture method of toner of the present invention, the release agent particle that obtains as previously mentioned and resin particle are condensed and coalescent, specifically, by above-mentioned releasing agent dispersion and the mixing of above-mentioned resin particle dispersion liquid, preferably add polycoagulant wherein and after obtaining aggregated particle dispersion liquid, by coalescent for the aggregated particle in obtained aggregated particle dispersion liquid and obtain agglomerated particle, can manufacture thus.

From the view point of low-temperature fixability and the storage stability of guaranteeing toner, release agent in the blending ratio of release agent particle and resin particle when releasing agent dispersion and resin particle dispersion liquid mixing or the aggregated particle that obtains and resin particle contained the proportional weight ratio (release agent/resin) by release agent and resin preferably 1/99 ~ 15/85, be more preferably 2/98 ~ 12/88, more preferably 3/97 ~ 10/90.

As polycoagulant, in the polycoagulant of organic system, can organic salt, polyethyleneimine etc. be used, in the polycoagulant of inorganic system, inorganic metal salt, inorganic ammonium salt, metal complex etc. can be used.As organic salt, include, for example out sodium acetate, ammonium acetate, as inorganic metal salt, include, for example out the inorganic metal salt such as slaine and the polyaluminium chloride polymkeric substance such as sodium sulphate, sodium chloride, lime chloride, magnesium chloride, zinc chloride, aluminum chloride, aluminium sulphate.As inorganic ammonium salt, include, for example out ammonium sulfate, ammonium chloride, ammonium nitrate etc.

In the present invention, from the view point of realizing the size controlling of high-precision toner and narrow size-grade distribution, in above-mentioned polycoagulant, preferably use the salt of 1 valency.Here, the salt of 1 valency means that the metallic ion of this salt of formation or cationic valence mumber are 1.As the salt of 1 valency, can use the inorganic system polycoagulant such as above-mentioned inorganic metal salt, ammonium salt, in the present invention, preferably use molecular weight is the water-soluble nitrogen-containing compound of less than 350.

From the view point of making primary particle condense rapidly, molecular weight is the water-soluble nitrogen-containing compound compound that preferably display is acid of less than 350, and the pH value at 25 DEG C of its 10 % by weight aqueous solution is preferably 4 ~ 6, is more preferably 4.2 ~ 6.In addition, the charging property of the toner under hot and humid from the view point of maintenance, its molecular weight is preferably less than 350, is more preferably less than 300.As so water-soluble nitrogen-containing compound, include, for example out the quaternary ammonium salts such as ammonium salt, quaternary alkylammonium halides etc. such as ammonium halide, ammonium sulfate, ammonium acetate, ammonium salicylate, from the aspect of the size controlling of toner, preferably list ammonium sulfate (pH value at 25 DEG C of 10 % by weight aqueous solution, hereinafter referred to as pH value: 5.4), ammonium chloride (pH value: 4.6), tetraethylammonium bromide (pH value: 5.6), tetrabutyl ammonium bromide (pH value: 5.8).

The use amount of polycoagulant is different according to the valence mumber of polycoagulant, usually, as long as make the concentration of the polycoagulant in aggregated particle dispersion liquid be the amount of 0.0001 ~ 10 mole/L.Usually, from the view point of the charged characteristic of the charging property of toner, particularly hot and humid environment, relative to resin 100 weight portion, be preferably below 50 weight portions, be more preferably below 40 weight portions, more preferably below 30 weight portions.In addition, from coherent viewpoint, be preferably more than 1 weight portion relative to resin 100 weight portion, be more preferably more than 3 weight portions, more preferably more than 5 weight portions.Consider above aspect, the use amount of polycoagulant is preferably 1 ~ 50 weight portion relative to resin 100 weight portion, is more preferably 3 ~ 40 weight portions, more preferably 5 ~ 30 weight portions.

When condensing, control as small particle diameter and narrow size-grade distribution from the view point of coherency and by aggregated particle, preferably the temperature in above-mentioned coacervated system is set as the temperature below (forming the glass transition temperature+25 of resin of resin particle) DEG C, from the view point of suppression oversize grain, be more preferably (glass transition temperature-30) DEG C ~ (glass transition temperature+25 DEG C), more preferably 25 DEG C ~ (glass transition temperature+15) DEG C, be further preferably the 35 DEG C ~ scope of (glass transition temperature+5) DEG C.

When adding polycoagulant, polycoagulant adds after can making water-medium solution.Polycoagulant can disposablely add, and also can add continuously or intermittently.In addition, also can add in batches.Preferably when the interpolation of polycoagulant and interpolation terminate after stir fully.

From the view point of the storage stability of toner, the glass transition temperature of the aggregated particle in aggregated particle dispersion liquid is preferably 50 ~ 80 DEG C, is more preferably 52 ~ 75 DEG C, more preferably 55 ~ 70 DEG C.

From the view point of the small particle diameter of obtained toner, the volume medium (D50) of aggregated particle contained in this aggregated particle dispersion liquid is preferably 1 ~ 10 μm, is more preferably 2 ~ 9 μm, more preferably the scope of 2 ~ 5 μm.In addition, the coefficient of alteration (CV value) of size-grade distribution is preferably less than 30%, is more preferably less than 28%, and more preferably less than 25%.

Control from the view point of the cohesion of aggregated particle dispersion liquid, the solid component concentration in the dispersion liquid of aggregated particle is preferably 5 ~ 50 % by weight, is more preferably 5 ~ 40 % by weight.

In the present invention, from preventing release agent etc. from the outflow of toner particle or the carried charge between color each in color toner being controlled in viewpoints such as phase same levels, preferably via operation that is disposable in above-mentioned aggregated particle dispersion liquid or that repeatedly add dispersing resin microparticles liquid and obtain the aggregated particle being attached with resin particle in batches to manufacture toner.

In the present invention, relative to the resin particle (following, be sometimes referred to as " resin particle in the present invention ") forming aggregated particle, later by the resin particle that is attached on aggregated particle referred to as " resin particle ".

When repeatedly adding resin particle, the amount of each resin particle is preferably equivalent in batches, and in addition, when adding resin particle, the amount of each resin particle is preferably equivalent in batches.In addition, when repeatedly adding resin particle, its number of times is not particularly limited in batches, from the view point of the size-grade distribution of formed aggregated particle, is preferably 2 ~ 10 times, is more preferably 2 ~ 8 times.

In the present invention, as the resin particle added in aggregated particle, be not particularly limited, such as, can use the resin particle prepared in the same manner as the resin particle in the present invention.

In the present invention, resin particle can be identical with the resin particle in the present invention, also can be different, from the view point of low-temperature fixability and the storage stability of toner, preferably there is the resin particle of the physical property different from the glass transition temperature of the resin particle in the present invention, softening point, molecular weight etc.

About the interpolation period of above-mentioned resin particle, as long as can be attached on aggregated particle, then be not particularly limited, from the view point of the size controlling of aggregated particle being attached with resin particle, preferably after the interpolation of initial polycoagulant terminates to the manufacturing process of agglomerated particle during.

From the view point of low-temperature fixability, the storage stability of toner, the match ratio (aggregated particle/resin particle) of the aggregated particle in aggregated particle dispersion liquid and resin particle is preferably 0.1 ~ 3.0 with mass ratio range, be more preferably 0.2 ~ 2.5, more preferably 0.3 ~ 2.0.

From the view point of high image quality, the volume medium (D50) being attached with the aggregated particle of resin particle is preferably 1 ~ 10 μm, is more preferably 2 ~ 10 μm, more preferably 3 ~ 9 μm.

In the present invention, from the view point of after cohesion or resin particle add terminate after prevent further unnecessary cohesion, preferably add cohesion stopping agent before coalescent.Stop agent as cohesion, preferably use surfactant, more preferably use anionic surfactant.In anionic surfactant, preferably add at least a kind that is selected from the group be made up of alkyl ether sulfate, alkyl sulfate and linear alkylbenzene sulfonate further.

Above-mentioned cohesion stops agent can using a kind, also can combine two or more and use.

From the view point of cohesion stopping property and the residual in toner, resin (total amount of the resin namely forming aggregated particle and the resin forming resin particle) 100 weight portions of the aggregated particle of resin particle are attached with relative to the resin or formation that form aggregated particle, above-mentioned cohesion stops the addition of agent to be preferably 0.1 ~ 15 weight portion, be more preferably 0.1 ~ 10 weight portion, more preferably 0.1 ~ 8 weight portion.As long as cohesion stops the above-mentioned addition of agent, then can add with any form, from the view point of throughput rate, preferably add with aqueous solution.Above-mentioned each salt can disposablely add, and also can intermittently or continuously add.

agglomerated process

In the present invention, preferably manufacture above-mentioned aggregated particle or be attached with resin particle aggregated particle after, their meltings are adhered, coalescent and obtain agglomerated particle.

Infer that the aggregated particle being attached with resin particle is when coalescent, resin particle in aggregated particle or release agent particle each other, be attached with resin particle in the aggregated particle of resin particle or release agent particle each other, resin particle each other and the aggregated particle be attached with in the aggregated particle of resin particle and the resin particle state of mainly physically adhering to, aggregated particle becomes to be integrated and coalescent, and resin particle each other and aggregated particle and resin particle melting adhere to form and be integrated, thus become agglomerated particle.

Heating-up temperature time coalescent is preferably more than the glass transition temperature of aggregated particle and less than 100 DEG C such temperature, be more preferably more than the glass transition temperature of aggregated particle and less than 90 DEG C such temperature, more than the glass transition temperature of more preferably aggregated particle and less than 85 DEG C such temperature.At the temperature lower than this, the adhesion of melting is not sometimes carried out.If temperature is higher than this in addition, then sometimes there is release agent dissociating from aggregated particle.

When being attached with the dispersion liquid of aggregated particle of resin particle, from shape controlling, the adhesive viewpoint of melting of target toner, its heating-up temperature be preferably form resin particle resin glass transition temperature more than and (softening point of this resin+20 DEG C) below, be more preferably more than (glass transition temperature of this resin+5 DEG C) and (softening point of this resin+15 DEG C) below, more preferably more than (glass transition temperature of this resin+10 DEG C) and (softening point of this resin+10 DEG C) below.

toner particle

The agglomerated particle obtained is via the solid-liquid separation process such as filtration, washing procedure, drying process and become toner particle.

Above-mentioned drying process is the operation agglomerated particle obtained in above-mentioned agglomerated process being obtained as required toner particle via rear dryings such as solid-liquid separation process, washing procedure such as filtrations.As drying means, oscillating mode flowing seasoning, spray drying process, freeze-drying can be adopted, spray the arbitrary methods such as (flash jet) method instantaneously.From the view point of the charging property of toner, the dried moisture of toner particle is adjusted to and is preferably less than 1.5 % by weight, more preferably less than 1.0 % by weight.

From the view point of the high image quality of toner, the volume medium (D50) of agglomerated particle and toner particle is preferably 1 ~ 10 μm, is more preferably 2 ~ 8 μm, more preferably 3 ~ 8 μm.In addition, the CV value of above-mentioned agglomerated particle and toner particle is all preferably less than 30%, is more preferably less than 25%.The particle diameter of toner (particle) and size-grade distribution can be measured by method described later.

[electrophoto-graphic toner]

Electrophoto-graphic toner of the present invention is obtained by the manufacture method of above-mentioned toner.

From the view point of low-temperature fixability, the softening point of electrophoto-graphic toner of the present invention is preferably 60 ~ 140 DEG C, is more preferably 65 ~ 130 DEG C, more preferably 70 ~ 120 DEG C.In addition, from the view point of the permanance of toner, glass transition temperature is preferably 30 ~ 80 DEG C, is more preferably 40 ~ 70 DEG C.In addition, the assay method of softening point and glass transition temperature is according to their assay method in resin.

About the release agent in electrophoto-graphic toner of the present invention, from the view point of the fixation performance of toner, its content is preferably 0.5 ~ 20 weight portion relative to adhering resin 100 weight portion in toner, is more preferably 1 ~ 18 weight portion, more preferably 1.5 ~ 15 weight portions.During containing colorant and charge control agent, about colorant, its content is preferably below 20 weight portions relative to adhering resin 100 weight portion in toner, be more preferably 0.01 ~ 10 weight portion, about charge control agent, relative to adhering resin 100 weight portion in toner, be preferably below 10 weight portions, be more preferably 0.01 ~ 5 weight portion.

About toner of the present invention, toner particle obtained above directly can be used as toner, also the auxiliary agents such as the flowing agent as external additive can be added to the treated and material that obtains of surfaces of toner particles as toner.As external additive, the known particulates such as the surperficial inorganic particles such as silicon dioxide microparticle, titanium oxide microparticle, alumina particulate through hydrophobization process or the polymer particles such as polymethylmethacrylate, silicone resin can be used.

Relative to utilizing external additive to carry out toner particle 100 weight portion before treatment, the use level of external additive is preferably 1 ~ 5 weight portion, is more preferably 1.5 ~ 3.5 weight portions.

The electrophoto-graphic toner obtained by the present invention can be used as one component system developer, or mixes with carrier and use as two-component system developer.

Embodiment

In following embodiments etc., each character value is measured by method below, is evaluated.

[acid number of resin]

Measure according to JIS K0070.Wherein, the mixed solvent (acetone: toluene=1: 1(volume ratio) that solvent is acetone and toluene is measured).

[softening point of resin and glass transition temperature]

(1) softening point

Use Flowtester(Shimadzu Seisakusho Ltd. Inc., " CFT-500D "), with programming rate 6 DEG C/min, the sample of 1g is heated, is applied the load of 1.96MPa simultaneously by plunger, from diameter be 1mm, length is that the nozzle of 1mm is extruded.The plunger slippage of Flowtester is marked and drawed mapping relative to temperature, and the temperature flowed out using the half amount of sample is as softening point.

(2) glass transition temperature

Use differential scanning calorimeter (Parkin Elmer Inc., Pyris 6DSC) to be warming up to 200 DEG C, be cooled to-10 DEG C from this temperature with cooling rate 10 DEG C/min, this sample is measured with programming rate 10 DEG C/min.When observing peak at the temperature of low more than 20 DEG C than softening point, read the temperature at this peak as glass transition temperature, in addition, when not observing peak but observe step difference at the temperature of low more than 20 DEG C than softening point, read the temperature of the intersection point representing the tangent line of maximum inclination of curve of this step difference part and the extended line of the baseline of the high temperature side of this step difference as glass transition temperature.In addition, glass transition temperature be resin amorphous fraction specific to physical property, generally observe in noncrystalline polyester, crystalline polyester also observed sometimes when there is amorphous fraction.

[fusing point of release agent]

Differential scanning calorimeter (Seiko Electronics Industry Company system, DSC210) is used to measure, using maximum peak temperature as fusing point from 20 DEG C with programming rate 10 DEG C/min.

[molecular weight of polyacrylate]

GPC(gel permeation chromatography)

Determinator: by CO-8010(Dong Cao Inc.), measure under the following conditions.In addition, the molecular weight of sample calculates based on the standard lines using polyglycol to make in advance as standard substance.

Post: TSK PWXL+G4000PWXL+G2500PWXL(is Dong Cao Inc.)

Column temperature: 40 DEG C

Eluent: 0.2mol/L phosphate buffer/acetonitrile (9/1)

Flow velocity: 1.0mL/ minute

Injection rate IR: 0.1mL

[particle diameter of resin particle, resin particle and release agent particle]

(1) determinator: laser light scattering type particle size determination machine (Ku Chang manufacturing company system, LA-920)

(2) condition determination: add distilled water in mensuration absorption cell, measures volume medium (D50) in absorbance under reaching the temperature of proper range.Size-grade distribution represents with CV value (standard deviation/volume medium (D50) × 100 of size-grade distribution).

[solid component concentration of dispersion liquid]

Use infrared moisture meter (Inc. of Kett Science Institute: FD-230), by dispersion liquid 5g in baking temperature 150 DEG C, mode determination 96(Looking Out Time 2.5 minutes/amplitude of fluctuation 0.05%) under measure moisture %.Solid constituent calculates according to following formula.

Solid constituent (%)=100-M

M: moisture (%)=[(W-W0)/W] × 100

W: the sample weight (initial stage sample weight) before mensuration

W0: the sample weight (adiabatic drying weight) after mensuration

[aggregated particle, be attached with the aggregated particle of resin particle, the particle diameter of agglomerated particle]

Analyzer: Coulter Multisizer III(Beckman Coulter Inc.)

Aperture: 50 μm

Analysis software: Multisizer III Version 3.51(Beckman Coulter Inc.)

Electrolytic solution: Isotone II(Beckman Coulter Inc.)

Condition determination: aggregated particle dispersion liquid, the aggregated particle dispersion liquid being attached with resin particle or agglomerated particle dispersion liquid are added in above-mentioned electrolytic solution 100mL, be adjusted to after measuring the concentration of the particle diameter of 30,000 particles with 20 seconds, measure 30,000 particles, obtain volume medium (D50) by its size-grade distribution.Size-grade distribution represents with CV value (standard deviation/volume medium (D50) × 100 of size-grade distribution).In addition, micro mist amount representing containing proportional (number %) with the composition of the particle diameter below 2 in number average bead diameter μm.

[particle diameter of toner]

Analyzer: Coulter Multisizer III(Beckman Coulter Inc.)

Aperture: 50 μm

Analysis software: Multisizer III Version 3.51(Beckman Coulter Inc.)

Electrolytic solution: Isotone II(Beckman Coulter Inc.)

Dispersion liquid: by Emulgen 109P(Kao Corp system, polyoxyethylene lauryl ether, HLB:13.6) be dissolved in above-mentioned electrolytic solution according to the mode reaching 5 % by weight concentration, obtain dispersion liquid.

Dispersion condition: add in above-mentioned dispersion liquid 5mL and measure sample 10mg, disperse 1 minute with ultrasonic dispersing machine, then, adds electrolytic solution 25mL, then disperses 1 minute with ultrasonic dispersing machine, make sample dispersion liquid.

Condition determination: by being added in above-mentioned electrolytic solution 100mL by said sample dispersion liquid, is adjusted to after measuring the concentration of the particle diameter of 30,000 particles with 20 seconds, measures 30,000 particles, obtain volume medium (D50) by its size-grade distribution.

Size-grade distribution represents with CV value (standard deviation/volume medium (D50) × 100 of size-grade distribution) (%).

The manufacture of polyester Production Example 1(polyester A)

By polyoxypropylene (2.2)-2,2-two (4-hydroxyphenyl) propane 8320g, polyoxyethylene (2.0)-2,2-two (4-hydroxyphenyl) propane 80g, terephthalic acid (TPA) 1592g and dibutyltin oxide (esterification catalyst) 32g under nitrogen atmosphere, reaction 5 hours at lower 230 DEG C of normal pressure (101.3kPa), reaction under decompression (8.3kPa) further.Be cooled to 210 DEG C, add fumaric acid 1672g, quinhydrones 8g, react after 5 hours, under reduced pressure react further, obtain polyester A.The softening point of polyester A is 110 DEG C, and glass transition temperature is 66 DEG C, and acid number is 24.4mgKOH/g.

The manufacture of polyester Production Example 2(polyester B)

By polyoxypropylene (2.2)-2,2-two (4-hydroxyphenyl) propane 4176g, polyoxyethylene (2.0)-2, two (4-hydroxyphenyl) the propane 3881g of 2-, terephthalic acid (TPA) 2253g, dodecenylsuccinic anhydride 322g, trimellitic anhydride 945g and dibutyltin oxide 15g add in the four-hole boiling flask being equipped with nitrogen ingress pipe, dehydrating tube, stirrer and thermopair, under nitrogen atmosphere, stir at 220 DEG C, reaction reaches till 120 DEG C until the softening point measured according to ASTM D36-86, obtains polyester B.The softening point of polyester B is 121 DEG C, and glass transition temperature is 65 DEG C, and acid number is 21.0mgKOH/g.

The manufacture of resin particle dispersion liquid Production Example 1(resin particle dispersion liquid A)

In the stainless steel still of 2 liters of capacity, by polyester A 390.0g, polyester B 210.0g, copper phthalocyanine (ECB-301: industrial group's system of refining day greatly) 45g and anionic surfactant's (Kao Corp's system " Neopelex G-15 " neopelex 15 % by weight aqueous solution) 20.0g, nonionic surfactant " Emulgen 430(Kao Corp system) " polyoxyethylene (26mol) oleyl ether (HLB:16.2) 6.0g and 5 % by weight potassium hydroxide aqueous solution 278.5g utilizes paddle stirrer to disperse at 95 DEG C under the stirring of 200r/ minute.Keep 2 hours under utilizing paddle stirrer with the stirring of 200r/ minute.Then, utilize paddle stirrer with under the stirring of 200r/ minute, drip deionized water 1222g with 6g/ minute.In addition, the temperature of system remains on 95 DEG C.After being cooled to 25 DEG C, utilizing paddle stirrer with under the stirring of 200r/ minute, adding polymkeric substance " the Japanese catalyst Inc. EPOCROS WS-700 " 28g of water miscible Han You oxazolinyl, then temperature is increased to 95 DEG C, 95 DEG C are being kept 1 hour.

After cooling, by the wire gauze of 200 orders (mesh size: 105 μm), obtain micronized resin particle dispersion liquid A.The volume medium (D50) of the resin particle in the resin particle dispersion liquid A obtained for 180nm, CV value be 28%, solid component concentration is 31 % by weight.

The manufacture of resin particle dispersion liquid Production Example 2(resin particle dispersion liquid B)

In the stainless steel still of 2 liters of capacity, utilize paddle stirrer to disperse at 95 DEG C under the stirring of 200r/ minute polyester A 390.0g, polyester B 210.0g and anionic surfactant's (Kao Corp's system " Neopelex G-15 " neopelex 15 % by weight aqueous solution) 20.0g, nonionic surfactant " Emulgen 430(Kao Corp system) " polyoxyethylene (26mol) oleyl ether (HLB:16.2) 6.0g and 5 % by weight potassium hydroxide aqueous solution 278.5g.Keep 2 hours under utilizing paddle stirrer with the stirring of 200r/ minute.Then, utilize paddle stirrer with under the stirring of 200r/ minute, drip deionized water with 6g/ minute.In addition, the temperature of system remains on 95 DEG C.After cooling, by the wire gauze of 200 orders (mesh size: 105 μm), obtain micronized resin particle dispersion liquid B.The volume medium (D50) of the resin particle in the resin particle dispersion liquid B obtained for 141nm, CV value be 24%, solid component concentration is 31 % by weight.

The manufacture of releasing agent dispersion Production Example 1(releasing agent dispersion A)

In the beaker of 1 liter of capacity, in 400g deionized water, dissolve sodium-salt aqueous solution (chemical formula (II), Kao Corp system " POIZ 521 ", the weight-average molecular weight: 2.0 × 10 of 7.5g as the acid-co-maleic acid of poly carboxylic acid sodium water solution ⁴, effective concentration is 40 % by weight) after, add the Japanese Jing La Inc. of 58g Brazil wax (Inc. of Jia Teng foreign firm, fusing point are 83 DEG C) and 42g paraffin HNP-9(wherein, fusing point be 75 DEG C) and make it disperse.While the temperature of this dispersion liquid is remained on 90 ~ 95 DEG C, while after carrying out 30 minutes dispersion treatment with " Ultrasonic Homogenizer 600W " (Hitachi Machinery Co. Ltd's system), be cooled to room temperature (25 DEG C), add ion exchange water wherein, being adjusted to release agent solid constituent is 20 % by weight, obtains releasing agent dispersion A.

The manufacture of releasing agent dispersion Production Example 2(releasing agent dispersion B)

Except using paraffin HNP-51(Japan Jing La Inc., fusing point to be 77 DEG C in releasing agent dispersion Production Example 1) replace paraffin HNP-9, and (chemical formula (I), Kao Corp's system " POIZ 530 ", weight-average molecular weight are 3.8 × 10 to use aqueous sodium polyacrylate ⁴, effective concentration is 40 % by weight) beyond the sodium-salt aqueous solution that replaces acid-co-maleic acid, obtain releasing agent dispersion B by same step.

The manufacture of releasing agent dispersion Production Example 3(releasing agent dispersion C)

Except using ester type waxes WEP-3(You Inc. in releasing agent dispersion Production Example 1, fusing point is 73 DEG C) replace, except paraffin HNP-9, obtaining releasing agent dispersion C by same step.

Relatively Production Example 1

In releasing agent dispersion Production Example 1, as release agent, do not use paraffin HNP-9 and use Brazil wax (Inc. of Jia Teng foreign firm, fusing point are 83 DEG C) 100g, aqueous sodium polyacrylate (compound of above-mentioned formula (I), Kao Corp's system " POIZ 530 ", weight-average molecular weight are 3.8 × 104, effective concentration be 40 % by weight) is used to replace the sodium-salt aqueous solution of acid-co-maleic acid, similarly carry out dispersion treatment, but viscosity rises, and does not obtain dispersion liquid.

Relatively Production Example 2

In releasing agent dispersion Production Example 1, as release agent, do not use Brazil wax and use paraffin HNP-9(Japan Jing La Inc., fusing point to be 75 DEG C) 100g, similarly carry out dispersion treatment, but release agent is separated with water, does not obtain dispersion liquid.

The relatively manufacture of Production Example 3(releasing agent dispersion D)

Except using Neopelex G15(neopelex in releasing agent dispersion Production Example 1, effective constituent concentration is 15%, Kao Corp's system) 6.7g except sodium-salt aqueous solution " POIZ 521 " (the Kao Corp's system) that replace acid-co-maleic acid, obtain releasing agent dispersion D by same step.

The relatively manufacture of Production Example 4(releasing agent dispersion E)

Except in releasing agent dispersion Production Example 1, as release agent, do not use paraffin HNP-9 and use Brazil wax (Inc. of Jia Teng foreign firm, fusing point are 83 DEG C) 100g, and use ラテ system Le ASK(alkenyl succinic dipotassium, effective constituent concentration is 28%, Kao Corp's system) 3.6g beyond sodium-salt aqueous solution " POIZ 521 " (the Kao Corp's system) that replace acid-co-maleic acid, obtain releasing agent dispersion E by same step.

The relatively manufacture of Production Example 5(releasing agent dispersion F)

Except in releasing agent dispersion Production Example 1, as release agent, Brazil wax (Inc. of Jia Teng foreign firm, fusing point are 83 DEG C) is not used to use paraffin HNP-9(Japan Jing La Inc., fusing point to be 75 DEG C) 100g, and use ラテ system Le ASK(alkenyl succinic dipotassium, effective constituent concentration is 28%, Kao Corp's system) 3.6g beyond sodium-salt aqueous solution " POIZ 521 " (the Kao Corp's system) that replace acid-co-maleic acid, obtain releasing agent dispersion F by same step.

Relatively Production Example 6

In releasing agent dispersion Production Example 1, as release agent, do not use paraffin HNP-9 and use Brazil wax (Inc. of Jia Teng foreign firm, fusing point are 83 DEG C) 100g, similarly carrying out dispersion treatment, but viscosity rises, and does not obtain dispersion liquid.

For each releasing agent dispersion Production Example 1 ~ 3 and compare each releasing agent dispersion A ~ F obtained in Production Example 1 ~ 6, to be formed and proterties is shown in Table 1.

Embodiment 1

Resin particle dispersion liquid A250g, deionized water 58g and releasing agent dispersion A 41g are added in 4 mouthfuls of flasks of the 2 liters of capacity being equipped with dehydrating tube, stirring machine and thermopair, at room temperature (25 DEG C) mixing.Then, utilizing paddle stirrer under agitation, at room temperature with dripping in 30 points of these potpourris of clockwise, ammonium sulfate 18.2g being dissolved into the aqueous solution obtained in the deionized water of 162g.Then, obtained mixed solution is warming up to 55 DEG C, keeps at 55 DEG C, form the aggregated particle that volume medium is 4.0 μm.

Then, dripped with 60 minutes the mixed liquor mixed as resin particle dispersion liquid B 23g and the deionized water 7.5g of dispersing resin microparticles liquid.This operation is amounted to repetition 3 times.Then, using in the mixed liquor mixed as resin particle dispersion liquid A 28g and the deionized water 9.0g of dispersing resin microparticles liquid and deionized water ammonium sulfate 1.5g being dissolved into 15g and the aqueous solution obtained dripped with 60 minutes simultaneously.This operation is amounted to repetition 2 times, obtains the aggregated particle dispersion liquid being attached with resin particle that volume medium is 5.0 μm.

Be attached with in the aggregated particle dispersion liquid of resin particle to obtained, add sodium laureth sulfate (EMAL E27C, solid constituent: 28 % by weight) 11.6g deionized water 450g dilutes and the aqueous solution that obtains, then 80 DEG C were warming up to 2 hours, keep after 2 hours, obtain the agglomerated particle that volume medium is 5.0 μm.Then, room temperature (25 DEG C) is cooled to.During this, the aggregated particle being attached with resin particle is changing into agglomerated particle.

By obtained agglomerated particle via being used for the filter progress of Separation of Solid and Liquid, drying process, washing procedure and obtain toner particle.Relative to this toner particle 100 weight portion, carry out outside with hydrophobic silica (Japanese Aerosil Inc.: RY50, number average bead diameter: 0.04 μm) 2.5 parts, hydrophobic silica (Cabot Inc.: CAB-O-SIL TS720, number average bead diameter: 0.012 μm) 1.0 parts and organic fine particles (Japanese PAINT Inc.: Fine Sphere P2000, number average bead diameter: 0.5 μm) 0.8 part with Henschel mixer and add process, using by the particulate after 150 object sieves as cyan toner.

Embodiment 2

Except using releasing agent dispersion B 41g to replace, except releasing agent dispersion A 41g, obtaining toner by same step in embodiment 1.

Embodiment 3

Except using releasing agent dispersion C 41g to replace, except releasing agent dispersion A 41g, obtaining toner by same step in embodiment 1.

Comparative example 1

Except using releasing agent dispersion D 41g to replace, except releasing agent dispersion A 41g, obtaining toner by same step in embodiment 1.

Comparative example 2

Except using releasing agent dispersion E 24g and releasing agent dispersion F 17g to replace, except releasing agent dispersion A41g, obtaining toner by same step in embodiment 1.

For the toner obtained in each embodiment 1 ~ 3 and comparative example 1,2, by following method, micro mist when evaluating the cohesion in toner manufacturing process, time coalescent, the state of supernatant, fixation performance and storage stability.Show the result in table 2.

[micro mist during cohesion and the state of supernatant]

About the coherency of release agent particle during cohesion in toner manufacturing process and resin particle, the mensuration confirming the size-grade distribution of the aggregated particle in the aggregated particle dispersion liquid gathered and the muddiness of the supernatant of aggregated particle dispersion liquid gathered.In the size-grade distribution of aggregated particle, micro mist amount (particle diameter is the ratio (number %) of the particle of less than 2 μm) is more, then represent that the coherency of release agent particle and resin particle is poorer, and in addition, supernatant gonorrhoea represents that release agent dissociates.

A: supernatant is transparent

B: some gonorrhoea of supernatant

C: supernatant gonorrhoea

[micro mist time coalescent and the state of supernatant]

Free about release agent during coalescent in toner manufacturing process, according to the method same with the evaluation method of state of micro mist during cohesion and supernatant, the mensuration confirming the size-grade distribution of the agglomerated particle in gathered agglomerated particle dispersion liquid and the muddiness of the supernatant of agglomerated particle dispersion liquid gathered.In the size-grade distribution of agglomerated particle, micro mist amount (particle diameter is the ratio (number %) of the particle of less than 2 μm) is more, then represent that release agent particle is more free or free when coalescent from aggregated particle, in addition, supernatant gonorrhoea represents that release agent dissociates.

[the fixation performance evaluation of toner]

With commercially available printer (Oki Data Inc., " ML5400 ") at the upper output image of good quality paper (Xerox Inc. of Fuji, J paper A4 size), upper end apart from A4 paper remains the blank parts of 5mm, reaches 0.45 ± 0.03mg/cm with the length of 50mm with the adhesion amount of State-output toner on paper of unfixed image ²solid image.Transforming the fuser of carrying in this printer as variable temperatures, is 34/minute (A4 longitudinally) carry out fixing with temperature fixation rate.The fixation performance of the fixing image obtained is evaluated by following tape stripping method.

(tape stripping method)

It is 50mm that correction tape (Mending tape) (3M Scotch correction tape 810, width are 18mm) is cut into length, after attaching to the blank parts of the upper end on fixing image gently, carries the counterweight of upper 500g, promotes 1 second come and go with speed 10mm/.Then, by the adhesive tape of attaching from lower end side with peel angle be 180 degree, speed peels off for 10mm/ second, according to said determination method measure adhesive tape attach before and after reflected image concentration, then calculate fixing rate by following formula.

Fixing rate=(image color before the image color after tape stripping/adhesive tape attaching) × 100

Being set to fixing rate when image color after peeling off is reached the identical value of the image color before attaching with adhesive tape is 100, and along with value diminishes, expression fixation performance is low.Be that more than 90 to be defined as fixation performance good by fixing rate.

Under each fixing temperature of 5 DEG C, carrying out above-mentioned test, coming into effect till there is hot sticky dirty temperature from there is the dirty temperature of cold bonding or the fixing rate temperature lower than 90.In addition, it is so-called that cold bonding is dirty refers to, when fixing temperature is low, toner on unfixed image is fully melting not, the phenomenon of adhering toner on fixing roller, on the other hand, so-called hot stickyly dirtyly to refer to, when fixing temperature is set as high temperature, because the viscoelasticity of the toner on unfixed image reduces, thus on fixing roller the phenomenon of adhering toner.Dirty or the hot sticky dirty generation of cold bonding, whether, when can be rotated a circle by fixing roller, on paper, again whether adhering toner judges, have toner to adhere to judge in this test by the part of distance solid image upper end 87mm.Here, so-called hot sticky dirty occurrence temperature refers to and starts hot sticky dirty temperature occurs, and the highest fixing temperature is hot sticky dirty-5 DEG C.In addition, so-called minimum fixing temperature refers to that the dirty or fixing rate of cold bonding does not occur reaches minimum temperature in the temperature of more than 90, is evaluated in this test by the temperature range temperature (the highest fixing temperature-minimum fixing temperature) that the energy of minimum fixing temperature and toner is fixing.

[the storage stability evaluation of toner]

Toner 10g is added in the polyethylene bottle of 20ml capacity, under the environment of temperature 50 C, relative humidity 40Rh%, place 48 hours with open state.After placement, measure condensation degree, according to following benchmark evaluation storage stability with powder property tester (Powder tester) (Hosokawa Micron Inc.).

Condensation degree is less, represents that storage stability is more excellent.

A: condensation degree is lower than 10%.

B: condensation degree is more than 10% and lower than 20%.

C: condensation degree is more than 20%.

In addition, specifically, powder property tester is used to obtain condensation degree as follows.

On the shaking table of powder property tester, the order of the sieve of 3 different mesh sizes according to epimere 250 μm, 150 μm, stage casing, hypomere 75 μm is arranged, place toner 2g thereon and carry out vibration in 60 seconds, measure toner weight residual on each sieve.

Application following formula calculates the toner weight measured, and obtains condensation degree [%].

Condensation degree [%]=a+b+c

The toner weight of a=(epimere Sieve residue)/2 [g] × 100

The toner weight of b=(stage casing Sieve residue)/2 [g] × 100 × (3/5)

The toner weight of c=(hypomere Sieve residue)/2 [g] × 100 × (1/5)

Utilizability in industry

Manufacturing method according to the invention, owing to can control cohesion, so can obtain the electrophoto-graphic toner being suitable for xerography, electrostatic recording, videograph etc. with small particle diameter when toner manufactures.

Claims

1. a manufacture method for toner, it comprises following operation: the release agent (B) of release agent (A) and the fusing point with high more than 5 DEG C of the fusing point than this release agent (A) is carried out emulsification and obtains the operation of release agent particle by (1) in water-medium under the existence of polycarboxylate; And (2) make obtained release agent particle and resin particle condense and coalescent operation, wherein, described release agent (A) for fusing point be the paraffin of 65 ~ 85 DEG C, described release agent (B) is Brazil wax, and described resin particle comprises polyester.

2. the manufacture method of toner according to claim 1, wherein, the fusing point of described release agent (B) is less than 100 DEG C.

3. the manufacture method of toner according to claim 1 and 2, wherein, described polycarboxylate is the salt of acid-co-maleic acid.

4. the manufacture method of toner according to claim 1 and 2, wherein, described polycarboxylate is the sodium salt of acid-co-maleic acid.

5. the manufacture method of toner according to claim 1 and 2, wherein, makes described polycarboxylate exist with 0.2 ~ 15 weight portion relative to release agent total amount 100 weight portion.

6. the manufacture method of toner according to claim 1, wherein, described polyester comprises noncrystalline polyester.

7. the manufacture method of toner according to claim 1 and 2, wherein, the fusing point of release agent (B) is 80 ~ 85 DEG C.

8. the manufacture method of toner according to claim 1 and 2, wherein, the fusing point of release agent (A) is 70 ~ 80 DEG C.

9. the manufacture method of toner according to claim 1 and 2, wherein, release agent (A) is 8 ~ 20 DEG C with the difference of the fusing point of release agent (B).

10. the manufacture method of toner according to claim 1 and 2, wherein, weight ratio and release agent (the A)/release agent (B) of release agent (A) and release agent (B) are 40/60 ~ 50/50.

The manufacture method of 11. toners according to claim 1 and 2, wherein, the weight-average molecular weight of polycarboxylate is 10000 ~ 50000.

The manufacture method of 12. toners according to claim 1 and 2, wherein, the volume medium D50 of release agent particle is 0.1 ~ 0.85 μm.

The manufacture method of 13. toners according to claim 1 and 2, wherein, the content of the water in water-medium is 100 % by weight.

The manufacture method of 14. toners according to claim 1 and 2, wherein, the CV value of the release agent particle obtained in described operation (1) is less than 40%.

The manufacture method of 15. toners according to claim 1 and 2, wherein, described (2) to comprise the releasing agent dispersion of release agent particle and to comprise the resin particle dispersion liquid mixing of resin particle, and after adding polycoagulant and obtaining aggregated particle dispersion liquid, by operation coalescent for the aggregated particle in obtained aggregated particle dispersion liquid.

The manufacture method of 16. toners according to claim 1 and 2, wherein, the weight ratio of release agent and resin and release agent/resin are 3/97 ~ 10/90.

The manufacture method of 17. toners according to claim 15, wherein, polycoagulant to be molecular weight be less than 350 water-soluble nitrogen-containing compound.

The manufacture method of 18. toners according to claim 17, wherein, the pH value at 25 DEG C of 10 % by weight aqueous solution of described water-soluble nitrogen-containing compound is 4 ~ 6.

The manufacture method of 19. toners according to claim 15, wherein, the use amount of polycoagulant is 5 ~ 30 weight portions relative to resin 100 weight portion.

The manufacture method of 20. toners according to claim 15, wherein, is included in disposable in described aggregated particle dispersion liquid or repeatedly adds dispersing resin microparticles liquid in batches and obtain being attached with the operation of the aggregated particle of resin particle.

The manufacture method of 21. toners according to claim 20, wherein, the match ratio of aggregated particle and resin particle and aggregated particle/resin particle with mass ratio range for 0.3 ~ 2.0.

The manufacture method of 22. toners according to claim 20, wherein, after cohesion or resin particle add terminate after and before coalescent, add cohesion and stop agent.

The manufacture method of 23. toners according to claim 1 and 2, wherein, the content of release agent is 1.5 ~ 15 weight portions relative to adhering resin 100 weight portion in toner.

24. 1 kinds of electrophoto-graphic toners, it is obtained by the manufacture method according to any one of claim 1 ~ 23.

25. 1 kinds of toners are used for the purposes of electrofax, described toner is obtained by the manufacture method of following toner, and the manufacture method of described toner comprises following operation: the release agent (B) of release agent (A) and the fusing point with high more than 5 DEG C of the fusing point than this release agent (A) is carried out emulsification and obtains the operation of release agent particle by (1) in water-medium under the existence of polycarboxylate; And (2) make obtained release agent particle and resin particle condense and coalescent operation, wherein, described release agent (A) for fusing point be the paraffin of 65 ~ 85 DEG C, described release agent (B) is Brazil wax, and described resin particle comprises polyester.