CN106896654A - Toner - Google Patents

Abstract

The present invention relates to a kind of toner.A kind of toner is provided, it includes the toner-particle containing resin glue, wax and colouring agent.The softening point of toner is more than 80 DEG C and less than 140 DEG C.The average circularity of toner is more than 0.940.It it is more than 78gm/ seconds by using the integrated value of the stress of toner at 150 DEG C of adhesiveness tester measurement.

Description

Toner

Technical field

The present invention relates to a kind of record for being adapted for use with electrofax, electrostatic recording or toner jet system record etc. The toner of method.

Background technology

In view of the energy and space-saving, the compact in size of main body for printer and duplicator is had resulted in recently Demand.The simplification of fixation facility is one of method compact in size of main body.The simplified appearance that thermal source and equipment are constituted can be made It is the method for simplifying fixation facility that easy film is fixed.In film is fixing, in addition to the simplification for constituting thermal source and equipment is easy, As result of the film as fixing member is used, pyroconductivity is improved.Therefore, it can shorten the printout time for starting. However, due to using film by being compressed to roller under pressure relatively high, so film is intended to be worn and torn in long-term use.

Even if needs display that the toner of satisfied low-temperature fixability to solve the problem at low pressures.However, working as The problem caused when the pressure reduction at fusing nip (fixing nip) place and image with printing rate high are with speedy carding process It is：Toner is intended to be peeled off from paper due to supplying to a small amount of hot and not enough toner deformation of toner (cold to be stained).

The interfacial adhesion or the suitable technical proposal of internal cohesive force measured by particular measurement method are will ensure that To improve the cold-resistant biofouling method of toner.

Japanese patent application discloses 2006-330706 publications and advises a kind of toner, wherein by particular measurement side Interfacial adhesion (Fr) between the toner and polytetrafluoroethylene (PTFE) of method measurement is for more than 1.0N and below 3.5N and by spy The inside cohesive force (Ft) for determining the toner that measuring method is similarly measured is more than 10N and below 18N.Additionally, Japan Patent Application discloses 2014-071332 publications and advises a kind of toner, wherein internal cohesive force (F) is more than 5N and below 10N And interfacial adhesion (f) is the toner of more than 0.5N and below 1N, the power is measured using particular measurement method.

The content of the invention

Japanese patent application discloses toner disclosed in 2006-330706 publications in common fixing device composition With excellent cold-resistant biofouling.However, in addition to the further reduction of the pressure at fusing nip, being printed with height The image of rate is so that under the occasion of speedy carding process, toner shows bad meltbility and cold-resistant dirt under small pressurization and heat Damage property is still not enough.

Additionally, the measurement that Japanese patent application is disclosed described in 2014-071332 publications is related to pressurize toner The step of with heating, but in addition to the fact that heating carries testing stand (stage) of toner, in the pressurized, heated of 30 seconds The moment heat for deviateing and being provided in being actually fixed is provided to the heat of toner in the time.Therefore, when with printing rate high Image is when in the case of the fusing nip of low pressure with speedy carding process, even if the toner with above-mentioned physical property still shows deficiency It is cold-resistant biofouling.

The present invention provides the toner for solving the above problems.More specifically, there is provided even if in the fixation unit of low-pressure type, Also there is excellent cold-resistant biofouling and heat-resisting biofouling toner when the image with printing rate high is with speedy carding process.

Based on widely studied result, the inventors discovered that above mentioned problem can by using adhesiveness tester (tackiness tester), and under conditions of moment supplies big calorimetric, the moment melting characteristic of toner is adjusted to More than particular value and the average circularity of toner and softening point also are adjusted into particular range to solve.The discovery causes this to send out Bright completion.

Thus, the present invention provides a kind of toner, and it includes the toner containing resin glue, wax and colouring agent Grain, wherein

The softening point of the toner is more than 80 DEG C and less than 140 DEG C；

The average circularity of the toner is more than 0.940；With

It is described at 150 DEG C when being measured the toner pellet obtained by compressing the toner using adhesiveness tester The integrated value of the stress of toner is more than 78gm/ seconds.

Even if the present invention is provided in the fixation unit of low-pressure type, when the image with printing rate high is with speedy carding process With excellent cold-resistant biofouling and heat-resisting biofouling toner.

Further characteristic of the invention will become aobvious and easy from the description of following exemplary embodiment (refer to the attached drawing) See.

Brief description of the drawings

Fig. 1 is the schematic diagram for measuring the adhesiveness tester of the integrated value of stress.

Specific embodiment

Toner of the invention includes the toner-particle containing resin glue, wax and colouring agent.Additionally, toner It is typically characterized by：The softening point of toner in particular range and average circularity and by using adhesiveness tester to logical It is more than each comfortable particular value of integrated value of the stress of the toner of the toner pellet measurement that overcompression toner is obtained.

Inventors believe that the reason for being solved the above problems the following is the present invention.It is excellent cold-resistant biofouling in order to obtain, It is important that the surface of toner appropriate deformation and toner-particle when heat and pressure is received is melted and is bonded by heat Together.Especially, because the thermal deformation of toner is not easy to appearance in the fusing nip of low pressure, so being adjusted during melting The importance degree of the surface adhesiveness of toner is improved.On the cohesive force between toner-particle during melting, due to because of toning The contact area of the toner-particle that agent moment in itself plastifies and deforms and cause increases and increases cohesive force.Additionally, with The surface property of toner-particle may also have relation during melting.

Therefore, it is cold-resistant biofouling in order to increase under low pressure, it is necessary to increase response moment heat toner-particle it Between cohesive force.Therefore, the cohesive force between the toner-particle of response moment heat can be surveyed by using adhesiveness tester Measure the integrated value of the stress of toner and control the value to increase.

It is important that being carried out under the conditions of in detail below using the measurement of adhesiveness tester.

Pressed temperature：150℃

Pressurization and retention time：1s

Thus, it was found that the numerical value with the integrated value of cold-resistant biofouling closely related stress can be by above-mentioned condition Under measure and obtain.On details, the present inventor is presumed as follows.

First, on pressed temperature, because heat is pulled away by continuing through for paper media, expression is supplied to toning The heat for being transferred to paper of the heat of agent is speculated corresponding to the temperature lower than actual fixing design temperature.Thus, it is suitable to add Pressure temperature is 150 DEG C, and under occasion of the pressed temperature higher or lower than 150 DEG C, in the image forming apparatus of low-pressure system It is intended to reduction with cold-resistant biofouling associating.Additionally, it is contemplated that under actual conditions of the medium by fusing nip, preferably Pressurization and retention time are to be short to 1s.

Softening point on toner, regulation softening point to certain limit for improve it is cold-resistant it is biofouling be important. Under the too low occasion of softening point, the phenomenon (heat is stained) that toner is peeled off when carrying out image at high temperature and exporting is easier to out It is existing, and under softening point occasion too high, thermal deformation unlikely, and is peeled off and is easy to appearance in small heat.

Increase average circularity for obtain it is excellent it is cold-resistant biofouling be also necessary.In average circularity occasion high Under, toner during height printout on medium can more densely be piled up.As a result, the space between toner-particle is unlikely Occur, therefore heat loss is reduced and heat is definitely transferred to toner.

For that reason, it was found that, under the occasion for meeting above-mentioned condition, even if available also have under low pressure Excellent cold-resistant biofouling toner.The discovery causes completion of the invention.In the present invention, for example, 69kgm/ seconds following Pressure Range Representation low pressure concrete numerical value.

The present invention is hereinafter illustrated in greater detail, but is not limited to the explanation.

In the present invention, it is necessary that the toner pellet obtained by compressing toner is measured when using adhesiveness tester When 150 DEG C at stress integrated value be more than 78gm/ seconds.Under occasion of the value less than 78gm/ seconds, toner is in melting The cohesive force of period is bad and can not obtain cold-resistant biofouling under excellent low pressure.The integrated value of stress at for 150 DEG C Preferred scope, in the case where the value was for the occasion of more than 78gm/ seconds, can obtain intended effect, but when toner is adjusted to During enforceable scope, while softening point is controlled into desired scope, preferably the integrated value of stress is 200g M/ seconds following.The scope of more than 80gm/ seconds and less than 130gm/ seconds is preferred.

In addition to the amount or type of regulation resin glue, crystalline polyester and wax, regulation toner can also be used Pyroconductivity method as control 150 DEG C at toner stress integrated value method.

Additionally, above-mentioned cold-resistant biofouling in order to obtain, it is necessary that the softening point of toner be more than 80 DEG C and 140 DEG C with The average circularity of lower and toner is more than 0.940.Under occasion of the softening point less than 80 DEG C, even if when fusing nip exists When under low pressure, the pressure in roll gap end also increases.As a result, in image under the occasion exported under high temperature, mainly in end Heat is stained and is easy to appearance.Additionally, under occasion of the softening point more than 140 DEG C, the deformation in nip portion is not enough.As a result, toner Easily from medium peel off, and it is cold-resistant it is biofouling be intended to reduce.It is thus impossible to obtain intended effect under low pressure. Softening point is preferably more than 90 DEG C and less than 120 DEG C.

Under the occasion of the average circularity less than 0.940 of toner, substantial amounts of space appears in the toner on medium Between particle and heat be easy to dissipate.As a result, cold-resistant biofouling during speedy carding process is intended to reduce.The upper limit of average circularity It is not particularly limited, but usually less than 1.00.More preferably lower limit is more than 0.950, because being easier to suppress because upper The heat loss stated the space between toner-particle and cause.

The softening point of toner can be controlled by the type of crosslinking agent or amount.Additionally, when toner is by following When suspension polymerization is produced, softening point can also be adjusted by the type of initiator or amount with reaction temperature.

Additionally, average circularity can be by toner production process, for example, hot spheroidization treatment side after breaking method Method or suspension or emulsion polymerization are set in desired scope.It is preferred from improving in addition to adjusting average circularity For the angle of the material scatter of the crystalline polyester and ester type waxes in the present invention etc., preferably toner is by being suspended in water It is method in medium, is more preferably produced by using suspension polymerization.

It is described below and can be used for the specific material of toner of the invention.

From the angle that the integrated value of stress is controlled to desired value, the toner-particle in the present invention is preferably used for Including crystalline polyester.

Hereinafter illustrate the structure of crystalline polyester.The crystalline polyester that can be used in the present invention preferably has specific journey Degree hydrocarbon chain long as main chain part-structure.Preferably crystalline polyester has the part-structure represented by following formula (1).

Formula (1)

Wherein m is 4 to 14 integer；N is 6 to 16 integer.

The length of main chain determined by the m and the value of n in part-structure, and from by crystalline polyester in water-medium In be encapsulated in toner and improve the angle of bin stability, preferably m is that more than 4 and n is more than 6.Additionally, from increase Crystalline polyester deliquescent angle, especially preferably m in itself is that less than 14 and n is less than 16.On the part-structure, From the angle being set in the integrated value of stress in desired number range, preferably include relative to all crystalline polyesters It is the part-structures more than 50 mass %.

Can be using known crystalline polyester, it is preferred that the condensation polymer of aliphatic dicarboxylic acid and aliphatic diol.Very To more preferably saturated polyester.The example of suitable monomer presented below.

The example of aliphatic dicarboxylic acid include oxalic acid, malonic acid, butanedioic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, Azelaic acid, decanedioic acid and dodecanedioic acid.

The instantiation of aliphatic diol includes ethylene glycol, diethylene glycol (DEG), triethylene glycol, 1,2- propane diols, 1,3- propane diols, two Propane diols, trimethylene, neopentyl glycol, 1,4- butanediols, 1,6-HD, 1,7- heptandiols, 1,8- ethohexadiols, 1,9- Nonanediol, 1,10- decanediols, 1,11- undecanes and 1,12- dodecanediols.

Can be produced by common polyester synthesis method for the crystalline polyester in the present invention.For example, crystallinity Polyester can be by carrying out the esterification or ester exchange of dicarboxylic acid component and diol component, then by under reduced pressure or by means of leading The commonsense method for entering nitrogen carries out polycondensation to obtain.

During esterification or ester exchange, can be aoxidized using such as sulfuric acid, tert-butyl group titanium butylate, dibutyl as needed The common esterification catalyst such as tin, manganese acetate and magnesium acetate or ester exchange catalyst.In addition it is possible to use known polymerization catalyzed Agent, for example, tert-butyl group titanium butylate, Dibutyltin oxide, tin acetate, zinc acetate, stannic disulfide, antimony trioxide and germanium dioxide To be polymerized.The amount of polymerization temperature and catalyst is not particularly limited, and can select as needed.

Catalyst is preferably titanium catalyst, more preferably chelate type titanium catalyst.Because titanium catalyst has fitting Suitable reactivity, and the polyester with desired molecular weight distribution in the present invention can be obtained.

The weight average molecular weight (Mw) of crystalline polyester is preferably 10, more than 000 and 40, less than 000, and more preferably 10, More than 000 and less than 30,000.Under weight average molecular weight (Mw) occasion within the above range, can be in fix steps immediately The plasticizing effect of crystalline polyester is obtained, while maintaining the high-crystallinity of crystalline polyester.

The weight average molecular weight (Mw) of crystalline polyester can be controlled by the various working conditions of crystalline polyester.

Additionally, when dispersed in toner is considered, the acid number of crystalline polyester is preferably controlled to low value.Specifically Ground, acid number is below 8.0mgKOH/g, more preferably below 5.0mgKOH/g, and still more preferably from below 3.5mgKOH/g.

The amount of crystalline polyester is preferably more than 1.0 mass parts and below 30.0 mass parts, viscous based on every 100.0 mass parts Knot agent resin.

Hereinafter illustrate wax.

First, in order to the integrated value of stress is controlled into desired value, preferably wax includes ester type waxes.According to the present inventor Design on this feature, under the occasion during ester type waxes is included in toner, the dispersiveness of the crystalline polyester in toner Improve, and the low-molecular-weight component of ester type waxes also takes the lead in dissolving during heating, thereby assists in crystalline polyester and is exposed to toner Surface on.

Additionally, known ester type waxes can be used in the present invention.Suitable example includes：Such as Brazil wax and montanate Wax etc. containing fatty acid ester as key component wax class；Such as deoxidation Brazil wax is by will come from sour group of fatty acid ester Divide partially or completely wax obtained from deoxidation；For example, by the methyl compound with hydroxyl that the hydrogenation of vegetable fat is obtained； Such as stearyl stearate and behenic acid behenyl alcohol ester saturated fat acid monoester class；Such as decanedioic acid Er behenyl alcohols ester, dodecane two The class product of the saturated aliphatic dicarboxylic acids such as sour distearyl ester and octadecane diacid distearyl ester and representative examples of saturated aliphatic alcohol；With Such as Er behenic acids nonanediol ester and distearyl acid dodecanediol ester representative examples of saturated aliphatic glycol and representative examples of saturated aliphatic monocarboxylic acid Class product.

In the middle of these waxes, preferred value is controlled to from the dispersiveness for improving crystalline material and by the integrated value of stress Angle, preferably includes in molecular structure there is two difunctionality ester type waxes (diester) of ester bond.

Difunctionality ester type waxes is the monocarboxylic ester compounds of binary alcohols and fatty or dicarboxylic acids and aliphatic monobasic alcohol Ester compounds.

The monocarboxylic instantiation of aliphatic includes myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acids, 20 Tetracid, cerinic acid, montanic acid, melissic acid, oleic acid, vaccenic acid, linoleic acid plus linolenic acid.

The instantiation of aliphatic monobasic alcohol includes myristyl alcohol, cetanol, stearyl alcohol, arachidic alcohol, behenyl alcohols, 24 Alkanol, hexacosanol, n-octacosanol and triacontanol.

The instantiation of dicarboxylic acids includes butanedioic (butanedioic acid) (butanedioic acid), pentane diacid (pentanedioic acid) (glutaric acid (glutaric acid)), hexane diacid (hexanedioic acid) (adipic acid (adipic acid)), heptane diacid (heptanedioic acid) (pimelic acid (pimelic acid)), octane diacid (octanedioic acid) (suberic acid (suberic acid)), nonane diacid (nonanedioic acid) (azelaic acid (azelaic acid)), decane diacid (decanedioic acid) (decanedioic acid (sebacic acid)), dodecanedioic acid, Tridecandioic acid, tetracosandioic acid, hexadecandioic acid (hexadecane diacid), octadecane diacid, eicosane diacid, phthalic acid, M-phthalic acid And terephthalic acid (TPA).

The instantiation of dihydroxylic alcohols includes ethylene glycol, propane diols, 1,3- propane diols, 1,4- butanediols, 1,5- pentanediols, 1, 6- hexylene glycols, 1,10- decanediols, 1,12- dodecanediols, 1,14- tetradecane diols, 1,16- hexadecane diols, 1,18- ten Eight alkane glycol, 1,20- icosane diols, 1,30- melissanes glycol, diethylene glycol (DEG), DPG, 2,2,4- trimethyls -1,3- penta Glycol, neopentyl glycol, 1,4 cyclohexane dimethanol, the spiroglycol, 1,4- Benzenediols, bisphenol-A and hydrogenated bisphenol A.

In the present invention, other waxes in addition to ester type waxes can not weaken in the range of effect of the invention therewith Use.

Known wax can serve as being intended to other waxes for being combined with ester type waxes, but from fixing roller and the angle of the release property of toner Degree, it can be advantageous to use aliphatic chloroflo such as Fischer-Tropsch wax.

Ester type waxes (A) is preferably more than 0.25 and less than 4.0 with mass ratio (A)/(B) of aliphatic chloroflo (B) in toner, More preferably more than 0.40 and less than 2.3.

The amount of wax is preferably more than 5.0 mass parts and below 30.0 mass parts, based on every 100.0 mass parts binding agent tree Fat.Additionally, the amount of ester type waxes is preferably more than 1.0 mass parts and below 30.0 mass parts, based on every 100.0 mass parts binding agent tree Fat.

Example for the resin glue in toner of the invention includes：Such as polystyrene and polyvinyl-toluene The homopolymers of styrene and its substitution product；Such as ethylene-propylene copolymer, styrene-vinyltoluene copolymer, benzene second Alkene-vinyl naphthalene copolymer, styrene-methylacrylate copolymer, Styrene And Chloroalkyl Acrylates methacrylate copolymers, styrene-propene Butyl acrylate copolymer, Styrene And Chloroalkyl Acrylates monooctyl ester copolymer, Styrene And Chloroalkyl Acrylates copolymer of dimethylaminoethyl, styrene- Methylmethacrylate copolymer, styrene-t methacrylate copolymers, styrene-t acrylate copolymer, Styrene-t copolymer of dimethylaminoethyl, styrene-ethylene ylmethyl ether copolymer, styrene-ethylene base second Base ether copolymer, styrene-ethylene ylmethyl ketone copolymers, SB, styrene-isoprene copolymerization The styrene based copolymers such as thing, styrene-maleic acid copolymer and styrene-maleic acid ester copolymer；Poly-methyl methacrylate Ester, polybutyl methacrylate, polyvinyl acetate, polyethylene, polypropylene, polyvinyl butyral resin, organic siliconresin, polyester Resin, polyamide, epoxy resin and polyacrylic resin.These resins various can be applied in combination individually or with its. Wherein, from the angle that the integrated value of stress is controlled to desired scope, the benzene second for preferably being represented by Styrene And Butyl-acrylate Alkene based copolymer.

More preferably styrene-acrylic, the example includes styrene-methylacrylate copolymer, styrene-the third Olefin(e) acid methacrylate copolymers, Styrene And Butyl-acrylate copolymer, Styrene And Chloroalkyl Acrylates monooctyl ester copolymer, Styrene And Chloroalkyl Acrylates Copolymer of dimethylaminoethyl, styrene-methylmethacrylate copolymer, styrene-t methacrylate copolymers, benzene Ethylene-methyl methacrylate acrylate copolymer and styrene-t copolymer of dimethylaminoethyl.

The example of the colouring agent that can be used in the present invention includes following organic pigment, organic dyestuff and inorganic pigment.

The example of cyan colorant includes copper phthalocyanine compound and its derivative, anthraquinone compounds and basic dye lake Compound.Instantiation presented below.C.I. pigment blue 1,7,15,15:1、15:2、15:3、15:4th, 60,62 and 66.

The example of magenta coloring agent include condensation azo-compound, diketopyrrolo-pyrrole compound, anthraquinone compounds, Quinacridone compound, basic dye lake compound, naphthol compound, benzimidazolone compound, thioindigo compound He perylene Compound.Instantiation presented below.C.I. paratonere 2,3,5,6,7,23,48:2、48:3、48:4、57:1、81:1、122、 144th, 146,150,166,169,177,184,185,202,206,220,221,254, and C.I. pigment violet 1s 9.

The example of yellow colorants includes condensation azo-compound, isoindolinone compounds, anthraquinone compounds, azo gold Metal complex, methylidyne compound and allyl amide compound.Instantiation presented below.C.I. pigment Yellow 12,13,14, 15、17、62、74、83、93、94、95、97、109、110、111、120、127、128、129、147、151、154、155、168、 174th, 175,176,180,181,185,191 and 194.

The example of black colorant is included carbon black and by using foregoing yellow colorants, magenta coloring agent, cyan Toner and magnetic toning are the colouring agent of black.

These colouring agents individually or as mixture, and can also be used in the state of solid solution.For the present invention In colouring agent consider that the dispersiveness in hue angle, chroma, brightness, light resistance, the OHP transparencys and toner-particle is selected.

In the middle of above-mentioned colouring agent, from the angle that the pyroconductivity of toner is adjusted to desired scope, preferably magnetic Body.In view of controlling pyroconductivity, toner preferably of the invention is produced in water-medium.

The addition of colouring agent is preferably more than 1.0 mass parts and below 20.0 mass parts, is bonded based on every 100 mass parts Agent resin.When using magnetic, its amount is preferably more than 20.0 mass parts and below 200.0 mass parts, and more preferably More than 40.0 mass parts and below 150.0 mass parts, based on every 100 mass parts resin glue.

The value of the pyroconductivity of toner of the invention is preferably more than 0.190W/mK and below 0.300W/mK, and more excellent Elect more than 0.230W/mK and below 0.270W/mK as.In pyroconductivity under the occasion of more than 0.190W/mK, heat is in toner Easily shifted between particle, the caking property of toner during improving melting, even and if the toner when friction fixing image It is also not susceptible to be peeled off from medium.Additionally, under the occasion of below pyroconductivity 0.300W/mK, improving wherein under high temperature Pressure during fixing fusing nip end high it is heat-resisting biofouling.

The pyroconductivity of toner can be controlled by the surface treatment of the amount of magnetic, the particle diameter of magnetic and magnetic System.

When magnetic is used for toner of the invention, magnetic is preferably included as key component such as ferroso-ferric oxide With the magnetic iron oxide such as gamma-iron oxide, and can be including such as phosphorus, cobalt, nickel, copper, magnesium, manganese, aluminium and this dvielement etc. silicon.Pass through The BET specific surface area of these magnetics that nitrogen adsorption method determines is preferably 2m²/ g to 30m²/ g, and more preferably 3m²/ g is extremely 28m²/g.Additionally, Mohs' hardness is preferably 5 to 7.The shape of magnetic can be polyhedron, octahedron, hexahedron, spherical, pin Shape and flakey, but from the angle of image color is increased, preferably with small anisotropic shape, such as polyhedron, octahedral Body, hexahedron and spherical.

The number average bead diameter of magnetic is preferably 0.10 μm to 0.40 μm.Although the particle diameter of less magnetic generally yields increasing Plus tinting strength, tinting power, but from prevent magnetic assemble and ensure dispersed angle of the magnetic in toner, it is preferably above-mentioned Scope.Under the occasion that number average bead diameter is more than 0.10 μm, magnetic is not easy to reddish black in itself.Especially, blush It is unlikely to be significant in half tone image, and the image of high-quality can be obtained.At the same time, it is in number average bead diameter Under less than 0.40 μm of occasion, improve the tinting strength, tinting power of toner and promote uniform dispersion in suspension polymerization.

The number average bead diameter of magnetic can be measured by using transmission electron microscope.More specifically, will be to be seen Toner-particle is fully scattered in epoxy resin, and then solidfied material solidifies over 2 days by under the atmosphere of 40 DEG C of temperature Obtain.Gained solidfied material slicer is cut into thin sample, and 10 under transmission electron microscope (TEM), 000 times Measurement is present in 100 particle diameters of the particle of magnetic in the visual field under to 40,000 times of image enlargement ratio.Then with Number average bead diameter is calculated on the basis of the equivalent diameter of the equal circle of the projected area of magnetic.Particle diameter can also be shown with image and be filled Put measurement.

For example, the magnetic that be used in toner of the invention can be prepared by the following method.Initially, will be such as hydrogen-oxygen Change the alkali such as sodium with equivalent to or more than iron component amount added to ferrous salt the aqueous solution, to prepare the water-soluble of ferrous hydroxide Liquid.Air is blown into aqueous solution while maintaining its pH to be more than 7 to preparation, the aqueous solution is being heated to more than 70 DEG C The oxidation reaction of ferrous hydroxide is carried out simultaneously, and the kind crystalline substance of the core as magnetic iron oxide powder is firstly generated.

Then, will include that the aqueous solution of the ferrous sulfate of the amount of about 1 equivalent determined with the addition based on aforementioned bases adds In adding to the slurries including kind of crystalline substance.Ferrous hydroxide is carried out while maintaining the pH of liquid 5 to 10 and being blown into air Reaction, and the growth on the kind crystalline substance as core of magnetic iron oxide powder.Now, the shape and magnetic characteristic of magnetic can pass through PH, reaction temperature and stirring condition is selected to control as one sees fit.As oxidation reaction is advanced, the pH of liquid shifts to acidic side, but excellent What is selected is that the pH of liquid is not less than 5.Thus obtained magnetic can be filtered, washed by magnetic by by means of commonsense method Wash and dry to obtain.

Additionally, when toner is produced in water-medium in the present invention, the surface of particularly preferably magnetic is Hydrophobization.Under the occasion being surface-treated by dry process, washing, filtering and the treatment of dried magnetic pass through Carried out using coupling agent.Under the occasion being surface-treated by damp process, dry material is completed it in oxidation reaction Redisperse afterwards, or after being completed in oxidation reaction by washing and the iron oxide being filtrated to get without in the case of dry It is redispersed in another water-medium, then carries out coupling processing.In the present invention, selection dry process and damp process can be taken the circumstances into consideration.

The example of the coupling agent in the surface treatment of the magnetic that can be used in the present invention includes silane coupler, silane Compound and titanium coupling agent.Preferably with silane coupler and silane compound.The example is represented by following logical formula (I)s.

R_mSiY_n (I)

[in formula, R represents alkoxy；M represents 1 to 3 integer；Y represent such as alkyl, phenyl, vinyl, epoxy radicals and The functional groups such as (methyl) acryloyl group；N represents 1 to 3 integer.However, m+n=4.]

The silane coupler or the example of silane compound represented by logical formula (I) include vinyltrimethoxy silane, second Alkenyl triethoxysilane, vinyl three ('beta '-methoxy ethyoxyl) silane, β-(3,4- epoxidations cyclohexyl) ethyl trimethoxy Base silane, γ-glycidoxypropyltrimethoxy silane, γ-glycidoxypropyl diethoxy silane, γ-aminopropyl Triethoxysilane, N- phenyl-γ-aminopropyltrimethoxysilane, γ-methacryloxypropyl trimethoxy silane, Vinyltriacetoxy silane, MTMS, dimethyldimethoxysil,ne, phenyltrimethoxysila,e, two Phenyidimethoxysilane, MTES, dimethyldiethoxysilane, phenyl triethoxysilane, diphenyl Diethoxy silane, n-propyl trimethoxy silane, isopropyltri-methoxysilane, n-butyltrimethoxysilane, isobutyl group Trimethoxy silane, trimethylmethoxysilane, n-hexyl trimethoxy silane, n-octyl trimethoxy silane, n-octyl three Ethoxysilane, positive decyl trimethoxy silane, hydroxypropyl trimethylammonium TMOS, n-hexadecyl trimethoxy silane and positive ten Eight alkyl trimethoxysilanes.Present invention it is preferred that the use of the Y in logical formula (I) being the compound of alkyl.Wherein, from To the angle of the value of desired pyroconductivity, preferably Y is the alkyl that carbon number is more than 3 and less than 6, and particularly preferably carbon Number is 3 or 4 alkyl.

When using silane coupler, can be processed with a kind of reagent or by using its polytype.When making During with its polytype, can independently or simultaneously be processed with each coupling agent.

Total treating capacity of coupling agent to be used is preferably 0.9 mass parts to 3.0 mass parts, based on every 100 mass parts magnetic Gonosome.The amount of inorganic agent can be adjusted according to reactivity of the surface area of magnetic and coupling agent etc..

In the present invention, other colouring agents can be used together with magnetic.The colouring agent that can be used together with magnetic Example include above-mentioned known dyestuff and pigment and be also magnetic and nonmagnetic inorganic compound.Instantiation includes all Such as cobalt and nickel ferromagnetic metal particle, and obtained by the way that chromium, manganese, copper, zinc, aluminium and rare earth metal are added to wherein Alloy.The particle of bloodstone etc., black titanium, aniline black byestuffs/pigment, carbon black and phthalocyanine etc. can also be used.Preferably this A little colouring agents can be further surface-treated.

The amount of magnetic can be used by PerkinElmer in toner, and the apparatus for thermal analysis TGA 7 of Inc. manufactures is surveyed Amount.Measure in the following manner.Toner is heated to 900 with 25 DEG C/min of programming rate from normal temperature under nitrogen atmosphere ℃.Rate of mass reduction (%) from 100 DEG C to 750 DEG C regards the amount of resin glue as, and residual qualities regard magnetic as The approximate quantity of body.

Additionally, the weight average particle diameter (D4) of toner produced according to the invention is preferably more than 3.0 μm and less than 12.0 μm, More preferably more than 4.0 μm and less than 10.0 μm.In the occasion that weight average particle diameter (D4) is more than 3.0 μm and less than 12.0 μm Under, obtain good mobility and sub-image can be made faithfully to develop.

Toner of the invention can also be produced by by the hot spheroidization of the toner-particle obtained by comminuting method, but It is the angle from the control such as existence of crystalline polyester and ester type waxes material, toner is produced preferably in water-medium Method.In particular it is preferred to suspension polymerization, because crystalline polyester is obtained with the state of fine dispersion and can be easy The progress of ground control crystallization.

Hereinafter illustrate suspension polymerization.

In by using the method for suspension polymerization production toner, polymerizable monomer composition is bonded by that will constitute The polymerizable monomer of agent resin, wax and colouring agent (and also have, crystalline polyester as needed, polymerization initiator, crosslinking Agent, charge control agent and other additives) uniform dissolution or dispersion obtain.Subsequent treatment includes combining polymerizable monomer Thing is dispersed in the continuous phase including dispersant (for example, water phase) and the shape in water-medium by using suitable mixer Into polymerizable monomer composition particle the step of, and make the polymerizable monomer that the particle of polymerizable monomer composition includes The step of polymerization.It is single in the toner (being hereinafter properly termed as " toner of polymerization ") obtained by suspension polymerization Toner-particle there is generally spherical in shape shape.As a result, the distribution of carried charge is also relatively uniform, therefore, it is expected to improvement figure As quality.In the step of making polymerizable monomer be polymerized, polymerization temperature can be set as more than 40 DEG C, and be typically set at 50 More than DEG C and less than 90 DEG C.

It is listed below the example of the polymerizable monomer of composition polymerizable monomer composition.

Therefore, the example of polymerizable monomer includes：As styrene, o-methyl styrene, a methyl styrene, to methylbenzene Ethene, to styrenic monomers such as methoxy styrene and p -ethyl-styrenes；Such as methyl acrylate, ethyl acrylate, propylene Sour N-butyl, isobutyl acrylate, n-propyl, n-octyl, lauryl ester, acrylic acid 2- ethyl hexyls The acrylic ester monomers such as ester, stearyl acrylate ester, acrylic acid 2- chloroethenes ester and phenyl acrylate；As methyl methacrylate, EMA, n propyl methacrylate, n-BMA, Isobutyl methacrylate, methacrylic acid N-octyl, lauryl ester, 2-Ethylhexyl Methacrylate, stearyl methacrylate, methacrylic acid benzene The methacrylate ester monomer of ester, dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate etc.；And Also acrylonitrile, methacrylonitrile and acrylamide.These monomers can be used individually or with mixture.In these monomers, From toner development characteristic and the angle of durability, preferably styrene is used alone or makes with other simplex method mixtures With.

Half-life period passes through polymerization for the polymerization initiator of 0.5h to 30h is preferred for toner of the invention in polymerisation In the production of method.It is 0.5 mass parts to 20 mass parts to be based on every 100 mass parts polymerizable monomer by addition in polymerisation The occasion that carries out of polymerization initiator under, the maximum of molecular weight can be obtained 5,000 and 50, the polymer between 000 is simultaneously And desired intensity and suitable melting characteristic can be assigned to toner.

The example of specific polymerization initiator includes：Such as 2,2'- azos pair-(2,4- methyl pentane nitriles), 2,2'- azos two Isobutyronitrile, 1,1'- azos double (hexamethylene -1- formonitrile HCNs), the double -4- methoxyl group -2,4- methyl pentane nitriles of 2,2'- azos and azo two The azos such as isobutyronitrile or diazonium Type of Collective initiator；It is different with such as benzoyl peroxide, methyl ethyl ketone peroxide, peroxidating carbonic acid two Propyl ester.Cumene hydroperoxide, peroxidating 2,4 dichloro benzene formyl, lauroyl peroxide, the tertiary fourth of peroxidating -2 ethyl hexanoic acid Ester, tert-Butyl peroxypivalate, (2- ethylhexyls) ester of peroxidating carbonic acid two and peroxidating carbonic acid two (sec-butyl) ester were waited Oxide-based polymerization initiator.

When toner of the invention is produced by polymerization, crosslinking agent, and its preferred addition can be added For more than 0.001 mass parts and below 15 mass parts, based on every 100 mass parts polymerizable monomer.

Compound with more than two polymerizable double bonds is mainly used as crosslinking agent.The example includes：Such as divinyl The divinyl aromatic compound such as base benzene and divinyl naphthalene；Such as glycol diacrylate, ethyleneglycol dimethacrylate Ester and 1,3 butylene glycol dimethylacrylate etc. are with two carboxylates of double bond；As divinyl aniline, divinyl ether, The divinyl compound such as vinyl thioether and divinylsulfone；With with more than three compounds of vinyl.These are changed Compound can be used individually or with its two or more combination.

When the medium used during the polymerization of polymerizable monomer is water-medium, dispersion stabilizer can be used for stabilization The particle of polymerizable monomer composition.Following dispersion stabilizer can be used.

The example of inorganic dispersion stabilizer include tricalcium phosphate, magnesium phosphate, trbasic zinc phosphate, aluminum phosphate, calcium carbonate, magnesium carbonate, Calcium hydroxide, magnesium hydroxide, aluminium hydroxide, calcium metasilicate, calcium sulfate, barium sulfate, bentonite, silica and aluminum oxide.

The example of organic dispersion stabilizer includes polyvinyl alcohol, gelatin, methylcellulose, methylhydroxypropylcellulose, second Base cellulose, sanlose and starch.

In addition it is also possible to use the nonionic, anion and cationic surfactant that are obtained commercially.Live on suitable surface Property agent example include lauryl sodium sulfate, sodium tetradecyl sulfate, pentadecyl sodium sulphate, sodium octyl sulfate, enuatrol, Sodium laurate and potassium stearate.

When preparing water-medium using the water miscible inorganic dispersion stabilizer of hardly possible in the present invention, dispersion stabilizer adds Dosage is preferably based on every 100.0 mass parts polymerizable monomer for 0.2 mass parts to 2.0 mass parts.Moreover it is preferred that water system is situated between Matter is that 300 mass parts are prepared to the water of 3,000 mass parts using based on every 100 mass parts polymerizable monomer composition.

When the water-medium of such difficult water miscible inorganic dispersion stabilizer being wherein dispersed with is prepared in the present invention, can It is used as received commercially available dispersion stabilizer.Additionally, in order to obtain the dispersion stabilizer with fine and uniform granularity, difficult water The inorganic dispersion stabilizer of dissolubility can be generated in water-medium such as water under high velocity agitation.More specifically, working as tricalcium phosphate During as dispersion stabilizer, preferred dispersion stabilizer can by by the aqueous solution of the aqueous solution of sodium phosphate and calcium chloride at a high speed The lower mixing of stirring is obtained so as to form the fine grained of tricalcium phosphate.

In the present invention, by using the method for the integrated value of the stress of following control toners, integrated value can be easy It is controlled to above range.

For example, after resin particle is obtained by making polymerizable monomer be polymerized, wherein resin particle will be scattered in Dispersion in water-medium is heated to the temperature higher than the fusing point of crystalline polyester and wax.However, when polymerization temperature compares fusing point Gao Shi, it is not necessary to the operation.

On the cooling velocity in subsequent cooling step, its preferred scope will be complete for toner in the present invention Body production method, rather than illustrating only for polymerization.

It is noted here that power concentrate on purpose be make crystal material, especially crystalline polyester crystallization toner production Method.

For example, when toner is produced by comminuting method, suspension polymerisation or emulsion polymerization, preferably including wherein temperature It is disposable to raise so that the step of crystalline polyester or wax are melted, are then cooled to normal temperature.In cooling step, by raising Molecular motion in the liquefied crystalline polyester of temperature decays with temperature reduction, and starts knot when close to crystallization temperature It is brilliant.Under the occasion for continuing to cool down, propulsion is crystallized and reaches complete solidification at normal temperatures.Carried out according to by the present inventor Research, the crystallinity of crystal material depends on cooling velocity and different.

More specifically, from the temperature (for example, 100 DEG C) fully high for fusion-crystallization polyester and wax to toner Below glass transition temperature, under the occasion that temperature is cooled down with more than 5.0 DEG C/min of speed, included crystallinity The crystallinity of material is intended to increase.Under above-mentioned cooling condition, it is above-mentioned model that the integrated value of the stress of toner is easily controlled Enclose.

Again more specifically, as noted, cooling velocity fully high is sufficiently above 5.0 DEG C/min of speed. Such cooling velocity is preferably more than 10.0 DEG C/min, more preferably more than 30.0 DEG C/min, and still more preferably from 50.0 DEG C/ More than minute.The upper limit of cooling velocity is for about 3,000 DEG C/min, now its effect saturation.

Further preferably dispersion is cooled to below the glass transition temperature of toner with cooling velocity fully high Temperature, then at the temperature below the glass transition temperature of toner keep more than 30 minutes, then with 1.0 DEG C/minute Relatively low cooling velocity cooling below clock.

As the result that more than 30 minutes are kept at the temperature below the glass transition temperature of toner, annealed And the crystallinity of crystalline polyester can be increased.Retention time is preferably more than 100 minutes, and more preferably 180 minutes with On.The upper limit of retention time is for about Isosorbide-5-Nitrae 40 minutes, now its effect saturation.

In the present invention, progressive cooling is referred to as with the cooling of less than 1.0 DEG C/min of cooling velocity.As a result, can obtain with Annealing identical effect, can further increase the crystallinity of crystalline polyester, and the integrated value of the stress in toner is held It is easily-controllable to be made as above range.Cooling velocity is preferably less than 0.50 DEG C/min, and more preferably less than 0.01 DEG C/min.Will bag Include by carrying out the progressive dispersion for cooling down the toner-particle for obtaining by conventional process filtration, washing and drying, so that To toner-particle.

In the present invention, toner-particle can include polar resin.The preferred embodiment of polar resin includes saturation or insatiable hunger And polyester resin.Further preferably polar resin is non-crystalline resin.

The polyester resin obtained by the polycondensation of following carboxyl acid components and alkoxide component can be used.

The example of carboxyl acid component includes terephthalic acid (TPA), M-phthalic acid, phthalic acid, fumaric acid, maleic acid, hexamethylene Alkane dicarboxylic acids and trimellitic acid.

The example of alkoxide component includes bisphenol-A, A Hydrogenated Bisphenol A, the ethylene oxide adduct of bisphenol-A, the expoxy propane of bisphenol-A Addition product, glycerine, trimethylolpropane and pentaerythrite.

Polyester resin can include urea groups.In the present invention, the weight average molecular weight (Mw) of polar resin is preferably 4, more than 000 And less than 100,000.The amount of polar resin is preferably more than 3.0 mass parts and below 70.0 mass parts, more preferably 3.0 mass More than part and below 50.0 mass parts, and still more preferably from more than 5.0 mass parts and below 30.0 mass parts, based on every 100 matter Amount part resin glue.

In the present invention, toner can include charge control agent.Known charge control agent can be used.Particularly preferred energy Enough make powered speed high and the charge control agent of the quantity of electric charge for remaining constant can be stablized.Additionally, when toner-particle is by straight When connecing polymerization to produce, particularly preferred water-medium is substantially insoluble and with the Charge controlled of low Inhibition of polymerization Agent.

Toner-particle can be controlled to the charge control agent of negative electrical charge for below citing.Therefore, Organometallic compounds The example of thing and chelate compound includes Monoazo metal compound, acetylacetone metallic compound, and aromatic hydroxy-carboxylic The metallic compound of (aromatic oxycarboxylic acids), aromatic dicarboxylic acid, hydroxycarboxylic acid and dicarboxylic acids.Other Example includes aromatic hydroxy-carboxylic, aromatic monocarboxylate and polycarboxylic acid, its slaine, acid anhydrides and ester, and such as bis-phenol phenol Derivative.In addition it is possible to use urea derivative, the salicylic acid compound containing metal, the naphthoic acid compound containing metal, boronation conjunction Thing, quaternary ammonium salt and calixarenes.

At the same time, below toner-particle can be controlled to the charge control agent of positive charge for citing.Nigrosine and The nigrosine being modified by fatty acid metal salts；Guanidine compound；Imidazolium compounds；Tributyl hexadecyldimethyl benzyl ammonium -1- hydroxyl -4- naphthalene sulfonic acids Salt；Such as tetrabutyl ammonium tetrafluoroborate quaternary ammonium salt, such as the analog phosphonium salts salt and its mordant pigment of quaternary ammonium salt；Three (color lake agent includes phosphotungstic acid, phosphomolybdic acid, phosphotungstomolybdic acid, tannic acid, no laurate, food for phenylmethane dyestuff and its mordant pigment Sub- acid, the iron cyanide and ferrocyanide)；The slaine of higher fatty acids；With resin system charge control agent.

These charge control agents can be used individually or with its two or more combination.In the middle of charge control agent, preferably Salicylic acid compound containing metal, and particularly preferably wherein metal is the compound of aluminium or zirconium.3,5- di-tert-butyl salicylic acids Aluminium compound be even more preferred charge control agent.

In the middle of resin system charge control agent, preferably with the polymer of functional group of sulfonic acid system.As referred to herein, with sulphur The polymer of Suan Xi functional groups is polymer or copolymer with sulfonic group, sulphonate-base or sulfonate group.

The example of polymer or copolymer with sulfonic group, sulphonate-base or sulfonate group includes thering is sulfonic acid in side chain The polymer electrolyte compound of base.In particular it is preferred to include as the copolymerization ratio with more than 2 mass %, preferably more than 5 mass % Containing the styrene that sulfonic (methyl) acrylamide monomer and glass transition temperature (Tg) are 40 DEG C to 90 DEG C and/or The polymer electrolyte compound of styrene-(methyl) acrylate copolymer.In this case, improve at high humidity is powered steady It is qualitative.

It is preferred that the compound represented by following logical formula (X)s is used as containing sulfonic (methyl) acrylamide monomer, its tool Body example includes 2- acrylamide-2-methyl propane sulfonics and 2- Methacrylamide -2- methyl propane sulfonic acids.

[C2]

(in logical formula (X), R₁Represent hydrogen atom or methyl；R₂And R₃Each represent hydrogen atom, carbon number be 1 to 10 alkyl, Alkenyl, pi-allyl or alkoxy；N is 1 to 10 integer.)

By in the toner-particle with based on every 100 mass parts resin glue as more than 0.1 mass parts and 10.0 matter Amount part is included below with sulfonic polymer, can further improve the electriferous state of toner-particle.

The addition of these charge control agents is preferably more than 0.01 mass parts and below 10.00 mass parts, based on every 100.00 mass parts resin glues.

Various organic fine powder ends or inorganic fine powder can be added to toner in the purpose lower outer portion for assigning various performances Particle.

Organic fine powder end or the superficiality and hot melt property of inorganic fine powder influence toner-particle, but it is believed that by inciting somebody to action The addition control of powder only produces slight influence in suitable scope to the integrated value of stress.Thus, from promotion stress Integrated value is adjusted to the angle of desired scope, the addition of organic fine powder end or inorganic fine powder be preferably 0.01 mass parts with Below upper and 10.00 mass parts, more than more preferably 0.02 mass parts and below 5.00 mass parts, and still more preferably from 0.03 matter More than amount part and below 1.00 mass parts, based on every 100.00 mass parts toner-particle.

Following material can serve as organic fine powder end or inorganic fine powder.

(1) mobility donor：Silica, aluminum oxide, titanium oxide, carbon black and fluorocarbons.

(2) grinding agent：Such as strontium titanates, cerium oxide, aluminum oxide, magnesia and chromium oxide metal oxide；Such as silicon nitride Deng nitride；Such as carborundum carbide；With the slaine such as such as calcium sulfate, barium sulfate and calcium carbonate.

(3) lubricant：Such as vinylidene fluoride and polytetrafluoroethylene (PTFE) fluororesin powder, and such as zinc stearate and stearic acid The fatty acid metal salts such as calcium.

(4) Charge controlling particles：Such as tin oxide, titanium oxide, zinc oxide, silica and aluminum oxide metal oxide, And carbon black.

Organic fine powder end or inorganic fine powder are used to process the mobility of the surface of toner-particle so as to improve toner With the charging uniformity of toner.By the way that by organic fine powder end or inorganic fine powder hydrophobization, the powered of toner can be adjusted Property and improve charged characteristic under high humidity environment.It is therefore preferable that last or inorganic using the organic fine powder of hydrophobization Fine powder.For by organic fine powder end or inorganic fine powder hydrophobization inorganic agent example include unmodified silicone varnish, Various modified silicone varnish, unmodified silicone oil, various modified silicone oil, silane compound, silane coupler, other are organic Silicon compound and organic titanic compound.These inorganic agents can be used alone or in combination.

Wherein, the inorganic fine powder for preferably being processed with silicone oil.More preferably with the silicic acid anhydride by coupling agent simultaneously Or thereafter with silicone oil treatment inorganic fine powder.It is preferred that the inorganic fine powder of the hydrophobization processed with silicone oil, because such powder Even if end also maintains charged toner amount high under high humidity environment and reduces selection developability.Organic fine powder is last or inorganic Fine powder can be used individually or with its various combination.

In the present invention, the BET specific surface area of organic fine powder end or inorganic fine powder is preferably 10m²/ more than g and 450m²/g Below.

The BET specific surface area of organic fine powder end or inorganic fine powder can be by according to BET method (preferably, BET multiple spots Method) the cryogenic gas absorption method realized by means of dynamic level pressure method determine.For example, BET specific surface area (m²/ g) can lead to Crossing makes sample surfaces absorption nitrogen and by using specific surface area meter " Ver.5.0 of GEMINI 2375 " (Shimadzu Corporation systems) measure to calculate by BET multipoint methods.

Organic fine powder end or inorganic fine powder set or can be attached to toner-particle surface securely.For will be organic The example of fine powder or inorganic fine powder set or the external mix machine for being attached to toner-particle surface securely includes prosperous house That mixer, mechanical fusion machine (Mechanofusion), high speed whirlwind formula mixer (Cyclomix), turbulizer (Turbulizer), mixed granulation machine (Flexomix), heterozygosis mixer (Hybridization), mechanical mixer And Nobilta (Mechanohybrid).Organic fine powder end or inorganic fine powder can be by increasing the peripheral speed of rotation or prolonging Process time long comes set securely or attachment.

The amount of the tetrahydrofuran insoluble (except colouring agent and inorganic fine powder) in toner of the invention is preferably small In 50.0 mass %, more preferably 0.0 mass % less than 45.0 mass %, and still more preferably from more than 5.0 mass % And less than 40.0 mass %, relative to the toner component in toner in addition to colouring agent and inorganic fine powder.Work as tetrahydrochysene When the amount of furans insoluble matter is less than 50.0 mass %, low-temperature fixability can be improved.

The amount of the tetrahydrofuran insoluble in toner refers to be changed into insoluble supra polymer in tetrahydrofuran solvent The mass ratio of weight polymers (crosslinked substance polymer).The amount of tetrahydrofuran insoluble can be by the polymerization of resin glue Spend with the degree of cross linking to adjust.

<The measuring method of the integrated value of the stress of toner>

(1) preparation of toner pellet

Toner pellet is placed on the survey that internal diameter is 27mm by by about 3g toners (proportion that can be dependent on sample changes) Amount with vinyl chloride ring, by using such as sample pressure forming machine " MAEKAWA Testing Machine " (MFG Co., Ltd. make) pressurizeed 60 seconds under 200kN and prepare sample formation.

(2) measurement of the integrated value of stress

The integrated value of the stress of toner is by using adhesiveness tester " TAC-1000 " (Rhesca Corporation System) measured according to device operation manual.The schematic diagram of adhesiveness tester is shown in Figure 1.

As specific measuring method, toner pellet is placed on sample increased pressure board 205, and probe tip 203 is led to Cross and be set as 150 DEG C using probe unit 202.

By adjusting head unit 200, probe tip then is down into wherein probe tip can pressurize toner pellet 204 Position at.

Then toner pellet is pressurizeed under the following conditions, and stress value in pull-up probe tip is passed with load Sensor 201 is detected.

- pressing speed：5mm/ seconds

- compression load：19.7kgm/ seconds

- pressurization the retention time：1 second

- pull-up speed：15mm/ seconds

The integrated value of stress is calculated by the way that the stress value determined by load sensor is integrated.

More specifically, can be by by from the moment of the power for applying to make sensor from pellet separate, (stress value is 0gm/ Second²Moment) the stress value integration of the time interval of moment that from pellet separate to sensor calculated.

<The measuring method of the average circularity of toner>

The average circularity of toner uses streaming particle image analyzer " FPIA-3000 " (SysmexCorporation System) measured (also with identical in the case of magnetic color tuner under identical measurement and analysis condition when with calibration process Mode is measured).

Specific measuring method is as follows.First, by about 20mL, therefrom the ion exchange water of removal solid impurity etc. has been put in advance In entering glass container.Then, it is added to (be used to clean precision measuring instrument by by " Contaminon N " as dispersant Device, pH are the 10 mass % aqueous solution of 7 mild detergent, the mild detergent include nonionic surfactant, it is cloudy from Sub- surfactant and organic washing-assisting detergent；Wako Pure Chemical Industries, Ltd. system) it is dilute with ion exchange water Release the dilution of the about 0.2mL that about three mass are prepared again.Then about 0.02g measurement samples are added, and uses ultrasonic dispersing machine Decentralized processing is carried out 2 minutes, so as to obtain measurement dispersion liquid.Now, suitably cooling dispersion liquid is 10 to cause its temperature More than DEG C and less than 40 DEG C.By using frequency of oscillation and the desktop ultrasonic cleaner of the electricity output of 150W with 50kHz/ Dispersion machine (for example, " VS-150 ", Velvo-Clear Co., Ltd.s system) hands over the ion of ormal weight as ultrasonic dispersing machine Change water and be put into tank, then the Contaminon N of about 2mL are added in tank.

During measuring, using being provided with " UPlanApro " (enlargement ratio：10 times, numerical value oral pore：0.40) as object lens Foregoing streaming particle image analyzer, and particle sheath (Particle Sheath) " PSE-900A " (Sysmex Corporation systems) it is used for sheath fluid.The dispersion liquid that will be prepared according to said process is imported in streaming particle image analyzer, and And 3,000 toner-particles of tale mode counting are used under HPF measurement patterns.By by two during grading analysis Value threshold value is set as 85% and the particle diameter of analysis is defined into the equivalent circle diameter that 1.985 μm less than 39.69 μm Determine the average circularity of toner.

In measurement process, before measurement starts, standard latex particle (" RESEARCH AND TEST are used PARTICLES, Latex Microsphere Suspensions 5200A ", Duke Scientific Corporation systems, And diluted using ion exchange water) adjust automatically focus.Then, Focussing is implemented within every 2 hours preferably since measurement.

Further, in the present invention, using being calibrated and by SysmexCorporation by Sysmex Corporation Issue the streaming particle image analyzer of calibration certificate.Except the particle diameter of analysis is defined into 1.985 μm less than 39.69 μm equivalent circle diameter outside, with when receiving calibration certificate identical measurement and analysis condition under measure.

The measuring principle of streaming particle image analyzer " FPIA-3000 " (Sysmex Corporation systems) flows to shoot The image of dynamic particle is as rest image and carries out graphical analysis.The sample that sample room will be had been added to aspirates note by sample Emitter is drawn and is fed to flat sheath flow cell.The sample for being fed to flat sheath flow cell forms the flat stream clamped by sheath fluid. By the sample of flat sheath flow cell with 1/60 second interval by stroboscopic light irradiation, and the image work of the particle of flowing can be shot It is rest image.Additionally, because flowing is flat, photographing the image of focusing.Particle image is clapped with CCD camera Take the photograph, and the image that will be photographed is located under the image procossing resolution ratio of 512 × 512 pixels (0.37 μm of 0.37 μ m of every pixel) Reason；And by extracting the profile of each particle image, measure the projected area S and perimeter L of particle image.

Next, obtaining equivalent circle diameter and circularity by using area S and perimeter L.Equivalent circle diameter refers to With the diameter of a circle with the projected area identical area of particle image.Circularity is defined as by that will be obtained by equivalent circle diameter The girth of the circle for arriving is calculated divided by value obtained from the girth of particle projection by following formula.

Circularity=2 × (π × S)^1/2/L

When particle image is circle, circularity is 1.000.Concavo-convex degree with the circumference of particle image increases, circle Shape degree declines.After the circularity for calculating each particle, 0.200 to 1.000 circularity scope is divided into 800 parts, counted The arithmetic mean of instantaneous value of gained circularity is calculated, and regards average circularity as.

<The measuring method of pyroconductivity>

(1) preparation of sample is measured

By respective a diameter of 25mm and highly for two cylindric measurement samples of 6mm are used by the environment of 25 DEG C About 5g toners (quality changes according to the proportion of sample) is compressed 60 seconds to make by lozenge compression forming device under about 20MPa It is standby.

(2) measurement of pyroconductivity

Measuring apparatus：The hot physical property meter TPS 2500S of hot plate method

Sample-holder：Room temperature sample-holder

Sensor：Standard accessory (RTK) sensor

Software：Hot plate analyzes (Hot disk analysis) 7

Measurement sample is placed on the erecting bed of room temperature sample-holder.The height of estrade is adjusted so that measuring sample Horizontal plane of the surface in sensor.

Second measurement sample is put on a sensor, a piece of annex metal is then placed thereon, and using in sensing The screw rod at the top of device applies pressure.Pressure torque wrench is adjusted to 30cNm.Confirm to measure sample and sensor Center is immediately below screw rod.

Start hot plate analysis, and select " Bulk (I types) " as test-types.

Cuit is as follows.

Feasible exploration depth：6mm

Time of measuring：40s

Heating power：60mW

Sample temperature：23℃

TCR：0.004679K-1

Sensor type：Disk

Sensor material type：Kapton

Sensor Design：5465

Radius sensor：3.189mm

After input, start measurement.After being measured, " calculating " button is selected, be input into " starting point：10 " and " terminal： 200 ", " standard analysis " button is selected, and calculates " pyroconductivity " [W/mK].

<The measuring method of the softening point of toner>

It is incidental according to instrument by using Flow Tester CFT-500D (Shimadzu Corporation systems) Operation manual measures the softening point of the toner determined by flowing test instrument temperature-raising method under the following conditions.

In the device, while constant loading is applied from the top of measurement sample using piston, cylinder will be filled in Measurement sample in body rises gentle melting, and the measurement sample for melting is extruded from the mould in the bottom of cylinder.This When, can obtain representing the flow curve of the relation between piston slippage and temperature.

In the present invention, " melt temperature of 1/2 method " described in incidental handbook regards softening point as.1/2 method Melt temperature be calculated as described below.

First, it is determined that flow out complete when piston slippage Smax with when beginning to flow out piston slippage Smin it Between difference 1/2 (see X as by poor 1/2；X=(Smax-Smin)/2).When the piston slippage in flow curve reaches X When flow curve temperature be 1/2 method melt temperature.

Sample：By 1.0g toners of weighing, and by with the pressing shaping device of diameter 1cm under the load of 20kN Pressurization 1 minute is molded, and obtains sample

The diameter of die orifice：1.0mm

Die length：1.0mm

Cylinder pressure：9.807×10⁵(Pa)

Measurement pattern：Temperature-raising method

Programming rate：4.0 DEG C/min

Using the above method, gained piston slippage (slamp value)-temperature curve is drawn, and measure softening point as right Should be in the temperature (temperature that half resin has flowed out) of h/2, the height of the wherein curve of S- shapes regards h as.

Embodiment

Hereinafter the present invention will be illustrated in greater detail with reference to Production Example and embodiment, but the invention is not restricted to this. Part and percentage in formula as below are entirely on the basis of quality, unless otherwise prescribed.

<The production of magnetic iron oxide 1>

The aqueous solution of the ferrous salt including ferrous hydroxide colloid by by the 4.0mol/L sodium hydrate aqueous solutions of 55L with The Fe including 2.0mol/L of 50L²⁺Ferrous sulfate aqueous solution mixing and stirring obtain.Obtained aqueous solution is maintained 85 DEG C Under, and oxidation reaction is carried out, while air was blown under 20L/ minutes, so as to obtain including the slurry of nuclear particle.

By gained slurry Filter Press and wash, be then redispersed in water and slurried again nuclear particle.Tool The magnetic iron oxide particle for having Silicon-rich surface is scaled 0.20 mass % with based on every 100 parts of nuclear particles by by sodium metasilicate by silicon In the liquid slurried again, the pH of regulation slurry is 6.0 and to stir and obtain.By gained slurry filter press mistake Filter, washing are then slurried again in ion exchange water.Will altogether 500g (relative to magnetic iron oxide be 10 mass %) from Sub-exchange resin SK110 (Mitsubishi Chemical Corporation systems) inputs liquid slurried again (Gu composition 50g/L), and by stirring 2h ion exchange is carried out.Then by with screen filtration and remove ion exchange resin, use press filtration Machine is filtered and washing, the magnetic iron oxide 1 that number average diameter that is dry and crushing to obtain primary particle is 190nm.

<The production of magnetic iron oxide 2 and 3>

Except in the production in magnetic iron oxide 1 adjust magnetic iron oxide number average bead diameter in addition to, with magnetic iron oxide 1 Production in identical mode obtain magnetic iron oxide 2 and 3.The physical property of gained magnetic iron oxide 2 and 3 is shown in Table 2.

<The production of silane compound 1>

70 parts of ion exchange waters will under agitation be dropped to by 30 parts of trimethoxysilanes altogether.Then by gained water Solution is maintained at a temperature of pH5.5 and 55 DEG C, and disperses 120 under peripheral speed at 0.46m/ seconds by using distribution blade Minute and hydrolysis.Then the aqueous solution is adjusted to pH7.0 and is cooled to 10 DEG C, so that hydrolysis stops.Therefore made It is the silane compound 1 for including the aqueous solution form of hydrolysate.

<The production of silane compound 2 and 3>

Except in the production of silane compound 1 silane compound type become as shown in table 1 change in addition to, with silanization The identical mode of compound 1 obtains silane compound 2 and 3.The working condition of gained silane compound 2 and 3 is shown in Table 1.

[table 1]

<The production of magnetic 1>

Magnetic iron oxide 1 (100 parts) is put into high-speed mixer (LFS-2, Fukae Powtec Corporation systems) In, and silane compound 1 (8.0 parts) was added dropwise through 2 minutes under the stirring of the rotary speed of 2,000rpm.Then mix and stir Mixing is carried out 5 minutes.In order to increase the anchorage of silane compound 1, then drying carries out 1h at 40 DEG C, reduces amount of moisture, and And mixture is dried into 3h at 110 DEG C, advance the condensation reaction of silane compound 1.Then magnetic 1 by grinding and by Mesh size is that 100 μm of sieve sieves to obtain.

<The production of magnetic 2 to 6>

In addition to magnetic iron oxide and silane compound are changed into the magnetic iron oxide that is shown in table 2 and silane compound, Magnetic 2 to 6 is produced with identical mode in the production of magnetic 1.

[table 2]

Surface silicon amount represents the amount (quality %) of the silicon based on every 100 mass parts magnetic iron oxide.

<The production of crystalline polyester 1>

230.0 parts altogether are put into as the decanedioic acid of carboxylic acid monomer and 242.1 parts as the 1,10- decanediols of alcohol monomer It is equipped with the reactive tank of nitrogen ingress pipe, dehydrating tube, agitator and thermocouple.Temperature is increased to 140 DEG C under agitation, Carry out being heated to 140 DEG C under blanket of nitrogen, and reaction is carried out into 8h at ambient pressure while water outlet is distilled.Then, base is added In two tin octoates that the total amount of every 100 mass parts monomer is 1 part, then carried out while being warming up to 200 DEG C with 10 DEG C/h anti- Should.Being reacted after 200 DEG C of temperature is reached further carries out 2h, and the pressure in reactive tank then is reduced into below 5kPa, And reaction carries out 3h at 200 DEG C, so as to obtain crystalline polyester 1.The weight average molecular weight (Mw) of gained crystalline polyester 1 is 20,100 and acid number be 2.2mgKOH/g.

<The production of crystalline polyester 2 to 8>

In addition to alcohol monomer and acid monomers are changed into those shown in table 3, with identical with the production of crystalline polyester 1 Mode obtain crystalline polyester 2 to 8.The physical property and structure of gained crystalline polyester are shown in Table 3.

[table 3]

<The production of toner-particle 1>

To 450 parts of 0.1mol/L-Na altogether₃PO₄The aqueous solution is put into 720 parts of ion exchange waters, is then heated to 60 DEG C. Then 67.7 parts of 1.0mol/L-CaCl altogether are added₂The aqueous solution, so as to obtain including the water-medium of dispersion stabilizer.

It is (anti-with the condensation of the oxirane (2mol) and expoxy propane (2mol) addition product of bisphenol-A by terephthalic acid (TPA) Amorphism saturated polyester resin obtained from answering；Mw=9500, acid number=2.2mgKOH/g, and glass transition temperature=68 ℃)

By above-mentioned formula with grater (Mitsui Miike Chemical Engineering Machinery Co., Ltd.) dispersed and mixing, and obtain monomer composition.Monomer composition is heated to 63 DEG C, and add, mix and The crystalline polyester 1 and 10.0 parts of decanedioic acid behenyl alcohol ester (fusing point Tm provided in 10.0 parts of tables 3 of dissolving：73.0℃).

TK- formulas homogeneous mixer (Tokushu Kika will be used in monomer composition input water-medium and at 60 DEG C Kogyo Co., Ltd.) 10 minutes are stirred so as to granulate under 12,000rpm in nitrogen atmosphere.Then, oar blade type is being used 9.0 parts of tert-Butyl peroxypivalates as polymerization initiator are put under the stirring of stirring vane, suspension is heated to 70 DEG C, and reaction carries out 4h at 70 DEG C.After reaction is completed, suspension is heated to 100 DEG C and is kept for 120 minutes.Then, By in 5 DEG C of water input water-medium, and cooled down from 100 DEG C to 50 DEG C with 50.0 DEG C/min of cooling velocity.Then Water-medium is kept for 120 minutes at 50 DEG C, it is naturally cooled to 25 DEG C at room temperature.Cooling in this case Speed is 1.0 DEG C/min.Toner-particle 1 is produced in then cooling, filtering and drying.Formula is shown in Table 4.

<The production of toner-particle 2 to 24>

Except the type and number of magnetic, the type of crystalline polyester and number, the type of ester type waxes and number, crosslinking agent Number and beyond cooling condition changes as shown in table 4 and 5, produce tune with identical mode in the production of toner-particle 1 Toner particles 2 to 24.Formula is shown in Table 4.

[table 4]

HNP-9：Paraffin (Nippon Seiro Co., Ltd. system)

[table 5]

<The production of toner 1>

Toner 1 is by by toner-particle 1 (100 parts) and 0.3 part of hydrophobic silica and 0.1 part of aluminum oxide FM Mixer (Nippon Coke＆Engineering Co., Ltd.) mixes to obtain.Hydrophobic silica is true by BET method Fixed specific surface area is 200m²/ g, and its surface 3.0 mass % HMDSs and 3 mass %100-cps silicone oil Carry out hydrophobization.Aluminum oxide is 50m by the specific surface area that BET method determines²/g.The physical property of toner 1 is shown in Table 6.

<The production of toner 2 to 24>

In addition to toner-particle changes as shown in table 6, toning is produced with identical mode in the production of toner 1 Agent 2 to 24.Physical property is shown in Table 6.

[table 6]

<Compare the production of toner-particle 1>

By above-mentioned parent material Mitsui Henschel mixers (Mitsui Miike Chemical Engineering Machinery Co., Ltd.s system) preliminary mixing, then knead extruder with the twin-screw for being set as 200rpm and 130 DEG C and pinch With.Gained mixture is rapidly cooled to normal temperature.Rough lapping is carried out with cutting machine, and by the material of gained rough lapping by making T-250 (Turbo Kogyo Co., Ltd. system) is ground with turbine and gas temperature is adjusted in such mode that delivery temperature is 50 DEG C Come finely divided.Then compare toner-particle 1 by using the classification of the multi-stage classifier using Coanda effect to obtain.

<Compare the production of toner-particle 2 to 6>

Except the type and number of magnetic, the type of crystalline polyester and number, the type of ester type waxes and number, crosslinking agent Number and cooling condition as shown in table 7 change beyond, adjusted with identical mode comparision of production in the production of toner-particle 1 Toner particles 2 to 6.

<Compare the production of toner 1 to 6>

In addition to toner-particle changes as shown in table 8, with identical mode comparision of production in the production of toner 1 Toner 1 to 6.Physical property is shown in Table 8.

[table 7]

<Compare the production of toner 7>

(preparation of resin particle A) has the preparation of the resin particle of three-decker

8g lauryl sodium sulfate input will be equipped with agitator, temperature sensor, cooling tube and nitrogen ingress pipe altogether Reaction vessel in 3,000g ion exchange waters in, while stirring under the mixing speed of 230rpm under nitrogen flowing, will Internal temperature is increased to 80 DEG C.After intensification, addition is dissolved in obtained in 200g ion exchange waters molten by 10g potassium peroxydisulfates Liquid, temperature is set as 80 DEG C again, following liquid monomer mix is added dropwise through 1h, then by the heating 2h at 80 DEG C It is polymerized under agitation, so as to be prepared for resin particle.These particles are referred to as " resin particle (1H) ".

The dispersion liquid of the particle (oil droplet) including emulsifying passes through preparation of such as getting off：Will be by means of 7g polyoxyethylene (2) 12 Sodium alkylether sulphate is dissolved in the solution input obtained in 800g ion exchange waters and is equipped with agitator, temperature sensor, cooling In the reaction vessel of pipe and nitrogen ingress pipe, 98 DEG C are heated to, then add 260g resin particles (1H) and by means of at 90 DEG C The solution that the following monomer solutions of lower dissolving are obtained, and with mechanical dispersion machine " the CLEARMIX " (M with peripheral passage Technique Co., Ltd. system) mix and dispersion 1h.

Then 6g potassium peroxydisulfates are dissolved in the polymerization initiator solution prepared in 200g ion exchange waters and are added to dispersion liquid In, it is polymerized by the way that system to be heated and stirred 1h at 82 DEG C, and obtained resin particle.These particles are referred to as " Resin particle (1HM) ".

Further addition is dissolved in the solution prepared in 400g ion exchange waters by 11g potassium peroxydisulfates, and exists through 1h Being added dropwise under 82 DEG C of temperature conditionss includes the liquid mixture of following monomer.

After being added dropwise to complete, it is polymerized by heating and stirring 2h, system is then cooled to 28 DEG C so as to obtain Resin particle.These particles are referred to as " resin particle A ".The Tg of resin particle A is 48 DEG C and softening point is 88 DEG C.

(preparation of resin particle B)

2.3g lauryl sodium sulfate input will be equipped with the importing of agitator, temperature sensor, cooling tube and nitrogen altogether In 3,000g ion exchange waters in the reaction vessel of pipe, while stirring under the mixing speed of 230rpm under nitrogen flowing, Internal temperature is increased to 80 DEG C.After intensification, addition is dissolved in what is obtained in 200g ion exchange waters by 10g potassium peroxydisulfates Solution, liquid temperature is set as 80 DEG C again, following liquid monomer mix is added dropwise through 1h, then by the heating at 80 DEG C 2h is polymerized under agitation, so as to be prepared for resin particle.These particles are referred to as " resin particle B ".

(preparation of colorant dispersion)

90g lauryl sodium sulfate will stir and be dissolved in 1,600g ion exchange waters altogether.In the same of agitating solution When gradually add 420g carbon blacks altogether.Then the dispersion liquid of coloring agent particle is by using dispersion machine " CLEARMIX " (M Technique Co., Ltd. system) disperse to prepare.The solution is referred to as " colorant dispersion ".

(aggegation and melting attachment steps)

Resin particle A, 1,400g ion exchange water, the 120g " colorant dispersion " of 300g will be scaled by solid altogether Assembling is put into the solution prepared in 120g ion exchange waters is dissolved in by 3g polyoxyethylene (2) sodium lauryl tri(oxyethyl) sulfate In having a reaction vessel of agitator, temperature sensor, cooling tube and nitrogen gatherer, and liquid temperature is adjusted to 30 DEG C.So PH is adjusted to 10 by adding the 5N aqueous solution of NaOH afterwards.Then, pass through through addition in 10 minutes under 30 DEG C, stirring 35g magnesium chlorides are dissolved in the aqueous solution prepared in 35g ion exchange waters.Kept for 3 minutes afterwards, started to warm up, by system temperature Degree was increased to 90 DEG C through 60 minutes, and granular grows reaction continues while maintaining the temperature at 90 DEG C.

In this condition, aggegation is measured with " Coulter Multisizer III " (Beckman Coulter, Inc. system) Particle diameter, when the median particle diameter (D50) based on dimension criteria is changed into 3.1 μm, add 260g resin particles B and Grain growth response is continued to.When desired particle diameter is reached, addition is dissolved in 600g ion exchanges by 150g sodium chloride The aqueous solution obtained in water, so that granular grows stop.Then, in attachment steps are melted, the melting of particle is attached by Heat and stir to advance until obtaining " FPIA-3000 " (Sysmex Corporation systems) measurement under 98 DEG C of liquid temperature Circularity is 0.96.Then carry out being cooled to 30 DEG C of liquid temperature, be 4.0 by adding salt acid for adjusting pH, and stop stirring.

(washing and drying steps)

The particle that will be prepared in aggegation and melting attachment steps is with basket centrifugation separator " MARKType-III, No.60 × 40 " (Matsumoto Kikaki Co., Ltd.s system) separation of solid and liquid, and form the wet cake of toner base particle.This is wet Cake is washed in basket centrifugation separator until the conductance of filtrate is changed into 5 μ S/cm, and the pie then is transferred into " Flash Jet Dryer " (Seishin Enterprise Co., Ltd.s system) and the dry amount of moisture to 0.5 mass %, so as to produce Median particle diameter (D50) based on dimension criteria is 6.2 μm of toner base particle.

(the addition step of external additive)

Will 1 mass % hydrophobic silicas silicon (number average diameter=12nm of primary particle, hydrophobic deg=68) and 0.3 matter altogether Amount % hydrophobic titanium oxides (number average diameter=20nm of primary particle, hydrophobic deg=63) added to gained toner base particle And with Mitsui Henschel mixers (Mitsui Miike Chemical Engineering Machinery Co., Ltd. System) mixing, so as to prepare compare toner 7.The physical property for comparing toner 7 is shown in Table 8.

[table 8]

<Embodiment 1>

Printer LBP3100 (Canon Inc. systems) is transformed and is used to print out evaluation.Transformation is related to treatment speed Degree increases to 200mm/ seconds from traditional processing speed and reduces to 69kgm/ seconds the contact of fixing film and backer roll. Also transformed in the way of the fixing temperature of the fixation unit in the LBP3100 that can adjust transformation.

<Fixing evaluation>

(25.0 DEG C of temperature and 50%RH's is wet in normal temperature and pressure environment for cold-resistant biofouling in above-mentioned image forming apparatus Degree) under evaluate.FOX RIVER BOND paper (110g/m²) it is used for fixing medium.By using recessed with relatively large surface The medium of convex paper form, can strictly evaluate the fixation performance under conditions of promoting to peel off and rub.

(cold-resistant biofouling)

The bearing capacity of the toner on fixing medium is adjusted to 0.90mg/cm².Then fixation unit is cooled to room temperature (15 DEG C), continuous 20 printings solid image, the heter temperature of fixation unit is random be set in more than 190 DEG C and 250 DEG C with Under scope in (hereinafter referred to fixing temperature), and be fixed.Cold dirt is visually determined in the 20th image of printing Damage and according to following bioassay standard evaluation.

A：There is not cold being stained at a temperature of up to 200 DEG C

B：200 DEG C less than 210 DEG C at a temperature of there is cold being stained

C：210 DEG C less than 220 DEG C at a temperature of there is cold being stained

D：Occur cold being stained at a temperature of more than 220 DEG C

(friction test)

Regulation half tone image concentration is so that the image color on fixing medium (uses Macbeth reflection of the concentration (Macbeth Co. systems) is measured) it is more than 0.75 and less than 0.80, and be imaged under 150 DEG C of fixing temperature.

Then, by fixing half tone image applying 55g/cm²Load lens cleaning paper rub 10 times.150℃ Under concentration rate of descent calculated by the half tone image concentration before and after friction by using below equation.

Concentration rate of descent (%)=[(image color before friction)-(image color after friction)]/(image before friction Concentration) × 100

Concentration rate of descent is similarly calculated by the way that fixing temperature is increased into 200 DEG C with 5 DEG C.Concentration rate of descent is changed into Temperature when 15% is calculated by the evaluation result to fixing temperature and concentration rate of descent obtained by sequence of operations, and The temperature of calculating is regarded as the fixing lower limit temperature of threshold value when showing that temperature fixing performance is satisfactory.

A：Fixing lower limit temperature is less than 160 DEG C

B：Fixing lower limit temperature is 160 DEG C less than 170 DEG C

C：Fixing lower limit temperature is 170 DEG C less than 180 DEG C

D：Fixing lower limit temperature is more than 180 DEG C

(heat-resisting biofouling)

In heat-resisting biofouling evaluation, the half tone image of height 2.0cm and width 15.0cm is in normal temperature and pressure environment Passing through direction apart from the part of upper end 2.0cm and under relative to paper under (25 DEG C of temperature and the humidity of 50%RH) 90g/m is formed in the part of end 2.0cm²A4 sizes paper on.In imaging, Macbeth reflection densities will be used The image color of meter (Macbeth Co. systems) measurement is adjusted to more than 0.75 and less than 0.80.By by the setting of fixation unit Temperature raises to be imaged with 5 DEG C from 170 DEG C.Visually evaluated according to following bioassay standard.

A：There is not heat at a temperature of up to 200 DEG C to be stained

B：190 DEG C less than 200 DEG C at a temperature of there is heat and be stained

C：180 DEG C less than 190 DEG C at a temperature of there is heat and be stained

D：There is heat at a temperature of less than 180 DEG C to be stained

<The evaluation of bin stability>

(long-term depot evaluation)

10g toners 1 will be put into 100mL vials altogether, and it is placed 3 at 45 DEG C of temperature and 95% humidity Individual month, and visual valuation.

A：Do not change

B：Aggregation is formed, but it is loose immediately

C：Formation is not easy to loose aggregation

D：There is no mobility

E：Clearly there is caking

<Embodiment 2 to 24>

In addition to using toner 2 to 24, evaluated in the same manner as in example 1.Evaluation result is shown in In table 9.

<Comparative example 1 to 7>

In addition to using toner 1 to 7 is compared, evaluated in the same manner as in example 1.Evaluation result is shown In table 9.

[table 9]

Claims (9)

1. a kind of toner, it is characterised in that including the toner-particle containing resin glue, wax and colouring agent, wherein：

The softening point of the toner is more than 80 DEG C and less than 140 DEG C；

The average circularity of the toner is more than 0.940；With

The toning at 150 DEG C when being measured the toner pellet obtained by compressing the toner using adhesiveness tester The integrated value of the stress of agent is more than 78gm/ seconds.

2. toner according to claim 1, wherein the wax includes ester type waxes.

3. toner according to claim 1 and 2, wherein the toner-particle further includes crystalline polyester.

4. toner according to claim 3, wherein there is the crystalline polyester part represented by following formula (1) to tie Structure：

Formula (1)

Wherein m is 4 to 14 integer；N is 6 to 16 integer.

5. toner according to claim 2, wherein the ester type waxes is the monocarboxylic esterification of binary alcohols and fatty closing Thing, or dicarboxylic acids and aliphatic monobasic alcohol ester compounds.

6. toner according to claim 1 and 2, wherein the resin glue is styrene-acrylic.

7. toner according to claim 1 and 2, wherein the colouring agent is magnetic.

8. toner according to claim 1 and 2, wherein the pyroconductivity of the toner be more than 0.190W/mK and Below 0.300W/mK.

9. toner according to claim 1 and 2, wherein the average circularity of the toner is more than 0.950.