CN106483781A - Toner dispersing agent for wax and toner - Google Patents

Abstract

The present invention relates to toner dispersing agent for wax and toner.A kind of toner dispersing agent for wax, it include the polymer by obtaining the resin glycerol polymerization of styrene acrylic system on hydrocarbon compound, and wherein described styrene acrylic system resin has the structure position from saturation alicyclic compound；With a kind of toner, which includes the toner-particle containing resin glue, wax and the polymer by obtaining the resin glycerol polymerization of styrene acrylic system on hydrocarbon compound, and wherein described styrene acrylic system resin has the structure position from saturation alicyclic compound.

Description

Toner dispersing agent for wax and toner

Technical field

The present invention relates to toner dispersing agent for wax and the toner including the toner dispersing agent for wax.

Background technology

In recent years, the panchromatic duplicator of electrofax has become widely used, and also begins to be applied to printing market.Print The adaptability of brush market demands high speed, high image quality and high production rate and the medium (paper type) to wide scope.

One instantiation of such requirement is " medium constant speed ability "：In " the medium constant speed ability ", even if working as Paper type becomes thin from thickness, is not changing the processing speed of coupling paper type or is changing the setting heating-up temperature of fixing device In the case of, it is also possible to carry out continuous printing.

Viewpoint from the medium constant speed ability, it is desirable to which toner ensures can be in the wide scope fixing temperature from low temperature to high temperature Inside it is properly completed fixing.

Release property is given the method for toner in wide scope fixing temperature by including wax in toner Suitably fusing toner.In such circumstances it is desirable to the wax in toner is in good and homogeneously dispersed state, because dispersed The quality of state has significant impact to toner property.

Japanese Patent Application Laid-Open 2011-13548 proposes one kind includes dispersing agent for wax to control wax to exist in toner The technology of the dispersity in toner.

Additionally, Japanese Patent Application Laid-Open 2007-264349 is proposed to use by high viscosity resins, low viscosity resin and is divided The toner adhesive that powder is constituted, to improve the dispersiveness of wax, so as to suppress image deterioration.

Even if however, control toner in wax dispersity in the case of, if by toner be placed on high temperature and Under high humidity, the chargeding performance of toner is likely to deteriorate, this is because therefore wax dissolution to toner surface and may make tune Toner mobility deteriorates.

Additionally, Japanese Patent Application Laid-Open 2011-123352 proposes various toners, wherein by having The crystalline resin of Flashmelt property adds to toner and improves low-temperature fixability such that it is able to default in wide temperature range Shadow.

However, in the high speed machines of printing market are suitable for, there is low-temperature fixability still inadequate and toner in height Temperature is lower to place the situation that may cause to lump.Further, since not controlling shape of toner, transfer efficiency may be not enough.

In this respect, Japanese Patent Application Laid-Open 2013-15830 is proposed by Heat Treatment Control shape of toner and drop The adhesive force of low-key toner, to improve transfer efficiency.

Here, although Heat Treatment Control shape of toner, but the known process causes wax dissolution with high tack extremely Vicinity of toner surfaces.As a result, under the influence of the wax of dissolution to vicinity of toner surfaces, the mobility of toner deteriorates, And deteriorate may the chargeding performance of toner.

From the above it follows that, the dispersity for wax in control toner is while guarantee chargeding performance, the low temperature of toner The research of fixation performance and anticaking capacity yet suffers from leeway.

Content of the invention

The present invention provides the toner dispersing agent for wax for solving the above problems.More specifically, the present invention provides toner using Dispersing agent for wax, the dispersity of the wax that its controllable toner-particle includes and also control wax are to toner-particle surface Dissolution.

The present invention is also provided and is solved the above problems and while low-temperature fixability and anticaking capacity is guaranteed, though with Under the related harsh situation of chargeding performance, it is also possible to show the toner of sufficient chargeding performance.

Therefore, the present invention relates to toner dispersing agent for wax, which includes by gathering styrene-acrylic grafting The polymer obtained on hydrocarbon compound is closed,

Wherein described styrene-acrylic has the structure position from saturation alicyclic compound.

The invention further relates to the toner comprising toner-particle, the toner-particle contain resin glue, wax and By the polymer that will be obtained in styrene-acrylic glycerol polymerization to hydrocarbon compound, wherein described styrene-the third Olefin(e) acid system resin has the structure position from saturation alicyclic compound.

According to the present invention it is possible to provide toner dispersing agent for wax, the wax that its controllable toner-particle includes point Bulk state and control dissolution of the wax to toner-particle surface.

It is also possible according to the present invention to provide while low-temperature fixability and anticaking capacity is guaranteed, though with charging property Under harsh situation that can be related, it is also possible to show the toner of sufficient chargeding performance.

From the description (with reference to the accompanying drawing) of following illustrative embodiments, further aspect of the present invention will become bright Aobvious.

Description of the drawings

Fig. 1 is the sectional view of annealing device.

Specific embodiment

Toner dispersing agent for wax (can be also simply referred to as " dispersing agent for wax " below) according to the present invention is included by by benzene The polymer that the resin glycerol polymerization of ethylene-acrylic acid system is obtained on hydrocarbon compound, wherein styrene-acrylic have The structure position of active self-saturation alicyclic compound.

In the dispersing agent for wax of the present invention, styrene-acrylic has the resin to constituting toner-particle Compatibility, and compatibility of the hydrocarbon compound position with the wax included by toner-particle.Therefore, wax can be well dispersed into In toner-particle.

Additionally, when styrene-acrylic has the structure position from saturation alicyclic compound, wax can be good It is dispersed in toner-particle well, meanwhile, even if work as toner is placed under high temperature and high humidity, it is also possible to keep toner Chargeding performance.

The result of the research that the present inventor is carried out proposes following mechanism.

In the case of being placed on toner under high temperature and high humidity, wax is generally migrated to toner-particle surface.

Meanwhile, in the case that toner-particle includes the dispersing agent for wax of the present invention, when wax is migrated to toner-particle table During face, dispersing agent for wax seems also to migrate together with wax to toner-particle surface.

When compared with conventional dispersing agent for wax, the dispersing agent for wax of the present invention has chemical combination alicyclic from bulky saturation The structure position of thing.Therefore, even if dispersing agent for wax is migrated to toner-particle surface, also suppress the dissolution of wax.As a result, even if working as When toner is placed under high temperature and high humidity, the mobility of toner does not also decline, and therefore toner has improved resistive connection Block, and think that its chargeding performance does not reduce.

Additionally, when dispersing agent for wax is migrated to toner-particle surface, due to being derived from the structure of saturation alicyclic compound Position shows hydrophobicity, thus improves the hydrophobicity of toner-particle, even and if toner is placed under high temperature and high humidity When, also it is not considered as that chargeding performance deteriorates.

Toner dispersing agent for wax according to the present invention is included by by styrene-acrylic glycerol polymerization to hydrocarbon The polymer obtained on compound, wherein styrene-acrylic have the structure from saturation alicyclic compound Position.

Hydrocarbon compound is not particularly limited, but the viewpoint from the compatibility to the wax in toner-particle, its be selected from The wax of the toner for the present invention of lower description.

In hydrocarbon compound, the peak temperature of the maximum endothermic peak measured using differential scanning calorimetry (DSC) is preferably at least 60 DEG C and no more than 110 DEG C.The weight average molecular weight (Mw) of further preferably hydrocarbon compound is at least 900 and no more than 50,000.

In the present invention, hydrocarbon compound can suitably be exemplified by chloroflo, such as low molecular weight polyethylene, low-molecular-weight poly- third Alkene, alkylene base co-polymer (alkylene copolymer), microwax, paraffin and fischer-tropsch wax.

From the viewpoint of reactivity when preparing dispersing agent for wax, preferably hydrocarbon compound has branched structure such as polypropylene.

Closed by the hydrocarbonylation in the polymer that obtains the resin glycerol polymerization of styrene acrylic system on hydrocarbon compound The content of thing is than preferably at least 5.0 mass % and no more than 20.0 mass %, and more preferably at least 8.0 mass % and is not more than 12.0 quality %.

Additionally, in the present invention, the method in styrene-acrylic glycerol polymerization to hydrocarbon compound do not had spy Do not limit, conventional known method can be used.

In the dispersing agent for wax of the present invention, styrene-acrylic is not particularly limited, and condition is that resin has source The structure position of self-saturation alicyclic compound.

For example, styrene-acrylic can be the form with the monomer represented by following formula (1).

Monomeric unit is the form obtained by the monomer reaction in polymer as mentioned herein.

(in formula (1), R₁Represent hydrogen atom or methyl, and R₂Represent saturation alicyclic group.)

R₂Saturation alicyclic group be preferably saturated alicyclic hydrocarbon group, more preferably carbon number is at least 3 and no more than 18 Saturated alicyclic hydrocarbon group, and more preferably carbon number is at least 4 and no more than 12 saturated alicyclic hydrocarbon group.Saturated alicyclic hydrocarbon group bag Polynucleation hydrocarbon group, bridged ring hydrocarbyl group and the volution hydrocarbyl group for include cycloalkyl, condensing.

The example of such saturation alicyclic group include cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, tert-butylcyclohexyl, Suberyl, cyclooctyl, adamantyl, decahydro -2- naphthyl, three rings [5.2.1.02,6] decyl- 8- base, pentacyclopentadecandimethanol base, different Bornyl, adamantyl, bicyclopentane base and three cyclopenta.

Saturation alicyclic group can be with alkyl, halogen atom, carboxyl, carbonyl and hydroxyl as substituent.Alkyl is preferred Alkyl with 1 to 4 carbon number.

Among these saturation alicyclic groups, preferably cycloalkyl, fused polycycle alkyl and bridge joint cyclic hydrocarbon radical, more preferably have There are at least 3 and the cycloalkyl of no more than 18 carbon number, substituted or unsubstituted bicyclopentane base and substituted or unsubstituted three ring Amyl group, even more preferably carbon number are at least 4 and no more than 12 cycloalkyl, and particularly preferably carbon number is at least 6 and no more than 10 Cycloalkyl.

The position of substituent and quantity are not limited, and in the case of it there is two or more substituent, substituent is permissible Identical or different.

In the present invention, the total amount based on the monomeric unit for constituting styrene-acrylic, is represented by formula (1) The content of monomeric unit is than preferably at least 1.5mol% and no more than 45.0mol%, more preferably at least 3.0mol% and less In 25.0mol%.

Styrene-acrylic can be containing the vinyl list of the structure position having from saturation alicyclic compound The homopolymers of body (a), but can also contain the copolymer with other monomers (b).

The example of vinyl monomer (a) include monomer for example acrylic acid ring propyl ester, acrylic acid ring butyl ester, acrylic acid ring pentyl ester, Cyclohexyl acrylate, acrylic acid cycloheptyl ester, acrylic acid ring monooctyl ester, methacrylic acid ring propyl ester, methacrylic acid ring butyl ester, methyl Acrylic acid ring pentyl ester, cyclohexyl methacrylate, methacrylic acid cycloheptyl ester, methacrylic acid ring monooctyl ester, propylene acid dihydride ring Penta diethylester, two ring pentyl ester of acrylic acid and two ring pentyl ester of methacrylic acid, and combinations thereof.

Among these, from hydrophobic viewpoint, preferably cyclohexyl acrylate, acrylic acid cycloheptyl ester, acrylic acid ring monooctyl ester, first Base cyclohexyl acrylate, methacrylic acid cycloheptyl ester and methacrylic acid ring monooctyl ester.

The example of other monomers (b) include styrenic monomers for example styrene, AMS, p-methylstyrene, Between methyl styrene, to methoxy styrene, 4-Vinyl phenol, to acetoxy-styrene, vinyltoluene, ethylo benzene second Alkene, styryl phenyl and benzyl styrene；The Arrcostab (carbon number of alkyl is at least 1 and no more than 18) of unsaturated carboxylic acid, As methyl acrylate, ethyl acrylate, butyl acrylate, 2-EHA, methyl methacrylate, methacrylic acid Ethyl ester, butyl methacrylate and 2-Ethylhexyl Methacrylate；Vinyl esters system monomer such as vinylacetate；Vinyl ethers It is monomer such as vinyl methyl ether；Halogen-containing vinyl monomer such as vinyl chloride；Diene monomer such as butadiene and isobutene, And combinations thereof.

Can also be containing component of the monomer as the copolymer adjusted for polarity for adding acidic group or hydroxyl.Add acidic group Or the example of the monomer of hydroxyl includes acrylic acid, methacrylic acid, maleic anhydride, acid half ester and acrylic acid 2- ethyl hexyl Ester.

In the present invention, from the viewpoint of the low-temperature fixability of toner, optimization styrene-acrylic resin have by under The monomeric unit that formula (2) represents.

In the case that styrene-acrylic has the monomeric unit represented by formula (2), the glass of dispersing agent for wax Change transition temperature (Tg) to tend to reduce.As a result, when in toner-particle containing dispersing agent for wax, even if work as toner is placed When under high temperature and high humidity, the chargeding performance of toner does not also reduce, and improves low-temperature fixability further.

In the present invention, the total amount based on the monomeric unit for constituting styrene-acrylic, is represented by formula (2) The content of monomeric unit is than preferably at least 5.0mol% and no more than 30.0mol%, more preferably at least 10.0mol% and less In 20.0mol%.

(in formula (2), R₃Represent hydrogen atom or methyl, n represents at least 1 and no more than 18 integer (n preferably at least 3 And no more than 12 integer))

The acid number of dispersing agent for wax is preferably at least 5mg KOH/g and no more than 50mg KOH/g, and more preferably at least 15mg KOH/g and no more than 35mg KOH/g.

Dispersing agent for wax acid number within the above range in the case of, further improve toner in dispersing agent for wax and tree The compatibility of fat, and improve dispersiveness of the wax in toner further.Additionally, the hydrophobicity of toner-particle becomes appropriate, And improve high temperature and the chargeding performance under high humidity.

In the present invention, in the molecular weight distribution measured by gel permeation chromatography (GPC) of dispersing agent for wax, weight average divides Son amount (Mw) preferably at least 5000 and no more than 70,000, and more preferably at least 10,000 and no more than 50,000.

Dispersing agent for wax weight average molecular weight (Mw) within the above range in the case of, improve wax in toner-particle Dispersiveness.Meanwhile, also improve anticaking capacity and heat-resisting biofouling.

When the weight average molecular weight (Mw) of dispersing agent for wax is less than 5000, dispersing agent for wax can be easily in toner-particle Mobile.As a result, when toner is placed under high temperature and high humidity, wax to the dissolution on toner-particle surface tends to increase, and The chargeding performance of toner and anticaking capacity tend to reduce.

Meanwhile, when the weight average molecular weight (Mw) of dispersing agent for wax is more than 70,000, fine dispersion is in toner-particle Wax can not possibly be promptly migrated to toner-particle surface in fixing and melting.Therefore, release property when being fixed tends to drop Low, and tend to more likely high-temperature offset.

The toner of the present invention has the toner-particle for including resin glue, wax and toner dispersing agent for wax.

Additionally, resin glue preferably includes non-crystalline polyester resin.

More preferably resin glue includes crystalline polyester resin and non-crystalline polyester resin.

When polyester resin is as resin glue, the compatibility between polyester resin and wax is low.Therefore, when in toner In particle add and including former state wax when, wax is present in toner-particle with the state of uneven distribution, and also produce Free wax.As a result, it may occur however that for example poor charging property of undesirable problem.

Meanwhile, include that above-mentioned toner dispersing agent for wax and resin glue include crystallinity in the toner of the present invention In the case of polyester resin, control the dispersity of wax and crystalline polyester resin in toner-particle.As a result, guarantee low While warm fixation performance, heat-resisting biofouling and anticaking capacity, even if under the harsh situation related to chargeding performance, it is also possible to aobvious Enough chargeding performances are shown.

With respect to 100.0 mass parts non-crystalline polyester resin, the amount of the crystalline polyester resin in toner-particle is excellent Choosing is at least 1.0 mass parts and no more than 15.0 mass parts, and more preferably at least 2.0 mass parts and no more than 10.0 mass parts.

Crystalline polyester amount within the above range in the case of, improve low-temperature fixability.

In the case that the amount of crystalline polyester resin is more than 15.0 mass parts, it is intended to be difficult to obtain crystalline polyester tree Fine dispersion of the fat in toner-particle, and low-temperature fixability tends to reduction.

With respect to 100.0 mass parts non-crystalline polyester resin, the amount of the dispersing agent for wax in toner-particle is preferably extremely Few 2.0 mass parts and no more than 15.0 mass parts, and more preferably at least 4.0 mass parts and no more than 7.5 mass parts.

In the present invention, resin glue preferably includes crystalline polyester resin.

In the present invention, crystalline resin is the resin for observing endothermic peak in differential scanning calorimetry (DSC).

Crystalline polyester resin can be obtained by the reaction of polybasic carboxylic acid more than binary and glycol.Such method it In, preferred resin is obtained by the polycondensation of aliphatic diol and aliphatic dicarboxylic acid, because degree of crystallinity is high.Additionally, at this In bright, crystalline polyester resin can be used alone, or be used with its multiple combination.

In the present invention, crystalline polyester resin is preferably by including selected from the carbon number with least 2 and no more than 22 Aliphatic diol and its derivative composition group at least one compound alkoxide component with include selected from have at least 2 and The contracting of the carboxyl acid component of at least one compound of the group of the aliphatic dicarboxylic acid of no more than 22 carbon number and its derivative composition Gather to obtain.

Among them, from low-temperature fixability and the viewpoint of anticaking capacity, preferably crystalline polyester resin is by including choosing Freely there is at least one compound of at least 6 and the group of the aliphatic diol of no more than 12 carbon number and its derivative composition Alkoxide component and the group included selected from the aliphatic dicarboxylic acid of carbon number with least 6 and no more than 12 and its derivative composition The polycondensation of the carboxyl acid component of at least one compound is obtaining.

The aliphatic diol with the carbon number of at least 2 and no more than 22 (preferably, at least 6 and no more than 12) is not especially limited System, which can be chain (preferably, straight-chain) aliphatic diol.

The example of such glycol includes ethylene glycol, diethylene glycol (DEG), triethylene glycol, 1,2- propane diols, DPG, 1,3- the third two Alcohol, 1,4- butanediol, 1,4- butadiene glycol, 1,5- pentanediol, neopentyl glycol, 1,6-HD, 1,7- heptandiol, 1,8- are pungent Glycol, 1,9- nonanediol, 1,10- decanediol, 1,11- undecane and 1,12- dodecanediol.

Among these, preferably straight-chain aliphatic α, omega-diol such as 1,6- hexylene glycol, 1,7- heptandiol, 1,8- ethohexadiol, 1, 9- nonanediol, 1,10- decanediol, 1,11- undecane and 1,12- dodecanediol.

In the present invention, derivative is not particularly limited, and condition is to obtain identical resin structure by polycondensation.Example bag Include and the derivative for obtaining is esterified by glycol.

In the present invention, it is preferred to be at least 50 mass % with respect to whole alkoxide components, more preferably at least 70 mass % bags Contain selected from constituting carbon number in the alkoxide component of crystalline polyester resin and be at least 2 and no more than 22 (preferably carbon number is at least 6 and not More than 12) aliphatic diol and its derivative composition group at least one compound.

In the present invention, in addition to aliphatic diol, polyalcohol can also be used.

Among polyalcohol, the example of the glycol in addition to aliphatic diol includes for example polyoxyethylated bisphenol-A of aromatic alcohol With polyoxypropylene bisphenol-A, and 1,4-CHDM.

Among polyalcohol, the example of ternary and more polynary polyalcohol includes aromatic alcohol such as 1,3,5- trihydroxytoluenes, and Aliphatic alcohol such as pentaerythrite, dipentaerythritol, tripentaerythritol, 1,2,4- butantriol, penta triol of 1,2,5-, glycerine, 2- first Base glycerine, 2- methyl isophthalic acid, 2,4- butantriol, trimethylolethane and trimethylolpropane.

Additionally, in the present invention, monohydric alcohol can also be used under the degree of property of crystalline polyester resin is not damaged. The example of monohydric alcohol includes n-butanol, isobutanol, sec-butyl alcohol, n-hexyl alcohol, n-octyl alcohol, 2-Ethylhexyl Alcohol, cyclohexanol and benzylalcohol.

Meanwhile, with least 2 and no more than 22 carbon number (preferably, at least 6 and no more than 12 carbon numbers) aliphatic two Carboxylic acid is not particularly limited, it is possible to use chain (preferably, straight chain) aliphatic dicarboxylic acid.

The example of such acid includes ethanedioic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, amylene Diacid, azelaic acid, decanedioic acid, nonane dicarboxylic acid, decane dicarboxylic acid, heneicosane dicarboxylic acid, dodecanedicarboxylic acid, maleic acid, richness Horse acid, mesaconic acid, citraconic acid and itaconic acid.

Can also be using the hydrolysis lower alkyl esters of these acid or acid anhydrides.

In the present invention, derivative is not particularly limited, and condition is to obtain identical resin structure by polycondensation.Therefore, Suitable example is included the acid anhydrides of dicarboxylic acid component and is obtained by the methyl-esterified of dicarboxylic acid component, esterified or chlorination Derivative.

In the present invention, it is preferred to be at least 50 mass %, more preferably at least 70 mass % with respect to whole carboxyl acid component Comprising be at least 2 and no more than 22 (preferably carbon number is at least 6 and little selected from constituting carbon number in the carboxyl acid component of polyester resin In 12) aliphatic dicarboxylic acid and its derivative composition group at least one compound.

In the present invention, the polybasic carboxylic acid in addition to above-mentioned aliphatic dicarboxylic acid can also be used.Among polybasic carboxylic acid, remove The example of the dicarboxylic acids beyond aliphatic dicarboxylic acid includes aromatic carboxylic acid such as M-phthalic acid and terephthalic acid (TPA)；Aliphatic carboxylic Acid such as dodecyl succinic acid and positive dodecenyl succinic succinic acid；With alicyclic carboxylic acid such as cyclohexane dicarboxylic acid.Above-mentioned list Also their acid anhydrides and lower alkyl esters are included.

Additionally, among other polybasic carboxylic acids, the example of polybasic carboxylic acid more than ternary includes aromatic carboxylic acid such as 1,2,4- benzene Tricarboxylic acids (trimellitic acid), 2,5,7- naphthalene tricarboxylic acids, 1,2,4- naphthalene tricarboxylic acids and PMA；With aliphatic carboxylic acid such as 1,2,4- Butane tricarboxylic acid, 1,2,5- hexane tricarboxylic acid and 1,3- dicarboxyl -2- methyl -2- methylene carboxyl propane.Above-mentioned list is also wrapped Include acid anhydrides and the lower alkyl ester derivatives of above-mentioned carboxylic acid.

Additionally, in the present invention, monocarboxylic acid can also be made under the degree of property of crystalline polyester resin is not damaged With.Monocarboxylic example includes benzoic acid, naphthalene-carboxylic acid, salicylic acid, 4- methyl benzoic acid, 3- methyl benzoic acid, phenoxy group second Acid, biphenyl acid, acetic acid, propionic acid, butyric acid and octanoic acid.

In the present invention, crystalline polyester resin can be prepared according to normal polyester synthetic method.For example, crystalline polyester tree Then fat in decompression or can introduce nitrogen by conventional method by carrying out esterification or the ester exchange of carboxyl acid component and alkoxide component Lower initiation polycondensation reaction is obtaining.

If necessary, esterification or ester exchange can be by using conventional esterification catalyst or ester exchange catalyst such as sulfuric acid, titanium Sour four butyl esters, 2 ethyl hexanoic acid tin, Dibutyltin oxide, manganese acetate and magnesium acetate are carrying out.

Polycondensation can be by using typical polymerization catalyst, for example known catalyst such as butyl titanate, 2 ethyl hexanoic acid Tin, Dibutyltin oxide, tin acetate, zinc acetate, stannic disulfide, antimony trioxide and germanium dioxide are carrying out.Polymerization temperature and urge The amount of agent is not particularly limited, as needed determining.

In order to improve the intensity of the crystalline polyester resin of acquisition, in esterification or ester exchange reaction, or in polycondensation reaction In, all monomers can be fed with single batch of form, or so that bivalent monomer is reacted to reduce lower-molecular-weight component, Ran Houke Reacted by valency monomer more than interpolation ternary.

In the discussion below present invention by using crystalline polyester resin improve toner low-temperature fixability the reason for.

Therefore, this is because as crystalline polyester resin is compatible with non-crystalline polyester resin, increasing non-knot The interval of crystalline substance polyester resin strand, reduces intermolecular force, thus substantially reduces the glass transition temperature of toner The state of degree (Tg) and acquisition with low melting viscosity.

In order to improve the compatibility of crystalline polyester resin and non-crystalline polyester resin, it is possible to reduce constitute crystallinity and gather The aliphatic diol of ester resin and/or the carbon number of aliphatic dicarboxylic acid, increase the concentration of ester group and increase polarity.

Even if however, in the toner with significantly reduced glass transition temperature (Tg), it is also desirable to guarantee in height Anticaking capacity used in gentle high humidity environment, in transport etc..For the purpose, when toner is exposed to high temperature and high humidity, The glass transition temperature (Tg) for making the compatible crystalline polyester resin in toner recrystallize and make toner is needed to reply Arrive the glass transition temperature (Tg) close to non-crystalline polyester resin.

In this case, when ester group concentration high and crystalline polyester resin and the amorphism in crystalline polyester resin When the compatibility of polyester resin is also high, it becomes difficult to recrystallize crystalline polyester resin, and the anticaking capacity of toner inclines To in reduction.

It follows from the foregoing that conclusion：From low-temperature fixability and the viewpoint of anticaking capacity, crystalline polyester resin is preferably comprised The carbon number of aliphatic diol is at least 6 and no more than 12, and constitutes the carbon number of the aliphatic dicarboxylic acid of crystalline polyester resin It is at least 6 and no more than 12.

Additionally, in the present invention, as the result for being used together dispersing agent for wax and crystalline polyester resin, carry further High/low temperature fixation performance.

Generally, as described above, plasticizer as crystalline polyester resin enter non-crystalline polyester resin in gap, thus Prevent non-crystalline polyester resin from having rule orientation, so as to show plasticization effect.Therefore, the plasticizer warp with bulky side chain Often show useful property.

Because the dispersing agent for wax of the present invention has the structure position for being derived from bulky saturation alicyclic compound, therefore may be used Speculate, used as the result of the dispersing agent for wax in toner and the interaction of crystalline polyester resin, dispersing agent for wax becomes to have The plasticizer of bulky side chain.In the present invention, as the result for being used together dispersing agent for wax and crystalline polyester resin, It is obvious that low-temperature fixability obtains further improved reason.

In the present invention, the dissolubility ginseng of the solubility parameter SP1 of crystalline polyester resin and toner dispersing agent for wax Number SP2 meets relation 0≤SP1-SP2≤1.3.

The parent in the case that two solubility parameters meet relation above, improving dispersing agent for wax and crystalline polyester resin And property, and also improve the dispersiveness of wax and crystalline polyester resin.The dispersiveness of improved wax causes the heat-resisting of increase to be stained Property, the improved dispersiveness of crystalline polyester resin causes improved low-temperature fixability.

When the value of SP1-SP2 is less than zero, the solubility parameter of dispersing agent for wax becomes too big, and wax dispersiveness tends to drop Low.Meanwhile, when the value of SP1-SP2 is more than 1.3, the difference of solubility parameter increases, crystalline polyester resin and dispersing agent for wax Compatibility is tended to reduce.

Solubility parameter [unit；(card/cm³)^1/2] calculated using Fedors method.Evaporation for calculating can (Δ ei [card/mole]) and molal volume (Δ vi [cm³/ mole]) for being present in the Minoru of " Kobunshi Kankokai " publication IMOTO " Fundamental Theory of Adhesion ", V chapter and R.F.Fedors, Polym.Eng.Sci.14,147 (1974) numerical value in.Additionally, in the present invention, calculated based on the structure of constitutional unit.

In the present invention, resin glue preferably includes non-crystalline polyester resin.

Content ratio preferably at least 50 mass % of the non-crystalline polyester resin in resin glue, more preferably at least 70 Quality %, and even more desirably at least 90 mass %.

Similar with crystalline polyester resin, non-crystalline polyester resin can be prepared according to normal polyester synthetic method.

Be suitable for prepare non-crystalline polyester resin monomer example include polyalcohol (binary, ternary or more Gao Yuan's Polyalcohol) and polycarboxylic acids (polybasic carboxylic acid of binary, ternary or more Gao Yuan) and their acid anhydrides or their lower alkyl esters.

Partial cross-linked in non-crystalline polyester resin molecule is effective for branched polymer is prepared, and therefore can use Polynary polyfunctional compound more than ternary.Therefore, it may include polybasic carboxylic acid more than ternary and their acid anhydrides or they Lower alkyl esters, and/or ternary and more polynary polyalcohol are used as monomer.

Described below it is suitable for preparing the polyalcohol of non-crystalline polyester resin and the example of polycarboxylic acids.

The example of dihydroxylic alcohols include ethylene glycol propane diols, 1,3 butylene glycol, 1,4- butanediol, 2,3- butanediol, diethylene glycol (DEG), Triethylene glycol, 1,5- pentanediol, 1,6-HD, neopentyl glycol, 2- ethyl -1,3- hexylene glycol, hydrogenated bisphenol A, by following formula (A) table The bis-phenol for showing and its derivative, and the glycol represented by following formula (B).

(in formula, R is ethylidene or propylidene；X and y are at least 0 integer, and the mean value of x+y is at least 0 and less In 10)

(in formula, R' is The mean value of x'+y' is at least 0 and no more than 10)

The example of dicarboxylic acids include maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconate, phthalic acid, Phthalic acid, terephthalic acid (TPA), succinic acid, adipic acid, decanedioic acid, azelaic acid, malonic acid, positive dodecenyl succinic succinic acid, different Dodecenyl succinic succinic acid, dodecyl succinic acid, Permethyl 99A base succinic acid, positive octenyl succinic acid, n-octyl fourth two Acid, isooctene base succinic acid and iso-octyl succinic acid.Can also be using their acid anhydrides and lower alkyl esters.

Among these, maleic acid, fumaric acid, terephthalic acid (TPA), adipic acid and positive dodecenyl succinic succinic acid is preferably used.

The example of ternary and more polynary polyalcohol includes D-sorbite, 1,2,3,6- hexane tetrol, 1,4- anhydrosorbitol Sugar alcohol, pentaerythrite, dipentaerythritol, tripentaerythritol, 1,2,4- butantriol, penta triol of 1,2,5-, glycerine, 2- methyl-prop three Alcohol, 2- methyl isophthalic acid, 2,4- butantriol, trimethylolethane, trimethylolpropane and 1,3,5- trihydroxy methyl benzene.

Among these, glycerine, trimethylolpropane and pentaerythrite are favourable examples.

The example of polybasic carboxylic acid more than ternary includes 1,2,4- benzene tricarbonic acid, 2,5,7- naphthalene tricarboxylic acids, 1,2,4- naphthalene three Carboxylic acid, 1,2,4- butane tricarboxylic acid, 1,2,5- hexane tricarboxylic acids, 1,3- dicarboxyl -2- methyl -2- methylene carboxyl propane, 1, 2,4- cyclohexanetricarboxylic acid, four (methylene carboxyl) methane, 1,2,7,8- octane tetrabasic carboxylic acid, PMA and Empol trimer acid. Can also be using their acid anhydrides and lower alkyl esters.

Among these, because inexpensive and easy reaction controlling, preferably use 1,2,4- benzene tricarbonic acids' (trimellitic acid) or Its derivative.

Polyalcohol more than above-mentioned dihydroxylic alcohols and ternary can be used alone, or be used with its multiple combination.Similarly, above-mentioned Polybasic carboxylic acid more than dicarboxylic acids and ternary can be used alone, or be used with its multiple combination.

In the present invention, non-crystalline polyester resin can be hybrid resin.For example, hybrid resin can be by will be noncrystalline Property polyester resin is obtained with vinyl resin or vinyl based copolymer chemical bond.

In this case, the non-crystalline polyester resin in hybrid resin content than be preferably at least 50 mass % and More preferably at least 70 mass %.

Under the hybrid resin of non-crystalline polyester resin and vinyl resin or vinyl based copolymer for example can pass through State method to prepare：Guaranteeing to include can be with the monomer component of vinyl resin or any one reaction of vinyl based copolymer Polymer and the presence of polyester resin, and carry out the resin polymerisation of any one or two kinds of.

Among the monomer for constituting non-crystalline polyester resin, can be anti-with vinyl resin or vinyl based copolymer The example of those that answers includes unsaturated dicarboxylic such as phthalic acid, maleic acid, citraconic acid, itaconic acid and their acid Acid anhydride.

Among the monomer for constituting vinyl resin or vinyl based copolymer, can be anti-with non-crystalline polyester resin The example of those that answers includes monomer with carboxyl or hydroxyl, acrylate and methacrylate.

Additionally, in the present invention, the resin in addition to non-crystalline polyester resin can not damage effect of the present invention It is used as resin glue under degree.

The resin is not particularly limited, and the example of suitable resin includes to have been used as the resin glue for toner Those.Instantiation includes vinyl resin, phenolic resin, with the modified phenolic resin of natural resin, changed with natural resin The maleic resin of property, acrylic resin, methacrylic resin, polyvinyl acetate resins, silicone resin, polyurethane resin, Polyamide, furane resins, epoxy resin, xylene resin, polyvinyl butyral resin, terpene resin, coumarone-indene resin And Petropols.

In the present invention, in the gel permeation chromatography (GPC) of tetrahydrofuran (THF) DDGS of non-crystalline polyester resin In the molecular weight distribution of measurement, peak molecular weight preferably at least 4000 and no more than 13,000.From low-temperature fixability and heat-resisting Biofouling viewpoint, the preferably scope.

Additionally, from the viewpoint of the chargeding performance under high temperature and high humidity environment, the preferably acid number of non-crystalline polyester resin It is at least 2mg KOH/g and no more than 30mg KOH/g.

From low-temperature fixability and the viewpoint of anticaking capacity, the hydroxyl value of preferably non-crystalline polyester resin is at least 2mg KOH/g and no more than 20mg KOH/g.

In the present invention, non-crystalline polyester resin can also be the peak value for including to have at least 4500 and no more than 7000 Non-crystalline polyester resin C of the low-molecular-weight of molecular weight and with least 8500 and no more than 9500 peak molecular weight height The form of non-crystalline polyester resin B of molecular weight.

In this case, from low-temperature fixability and heat-resisting biofouling viewpoint, based on quality, preferably HMW is non- Crystalline polyester resin B is at least 10/90 and is not more than with the mixing ratio (B/C) of non-crystalline polyester resin C of low-molecular-weight 60/40.

From heat-resisting biofouling viewpoint, the peak molecular weight of preferably HMW non-crystalline polyester resin B be at least 8500 and no more than 9500.Additionally, from the viewpoint of the chargeding performance under high temperature and high humidity environment, preferably HMW is noncrystalline The acid number of property polyester resin B is at least 10mg KOH/g and no more than 30mg KOH/g.

From the viewpoint of low-temperature fixability, the peak molecular weight of preferably low-molecular-weight non-crystalline polyester resin C be at least 4500 and no more than 7000.Additionally, from the viewpoint of the chargeding performance under high temperature and high humidity environment, preferably low-molecular-weight is noncrystalline Property polyester resin C acid number be not more than 10mg KOH/g.

Acid number is the milligram number for neutralizing the potassium hydroxide required for the acid contained in 1g sample.The acid number of resin is basis JIS K0070-1992 is determined.

In the present invention, toner-particle includes wax.It is listed below the suitable example of wax.

Chloroflo such as low molecular weight polyethylene, low-molecular-weight polypropylene, alkylene base co-polymer, microwax, paraffin and Fischer-Tropsch Wax；The oxide of chloroflo such as polyethylene glycol oxide wax or its block copolymer；The main wax such as babassu being made up of fatty acid ester Wax；Fatty acid ester such as deoxidation Brazil wax with part or all of deoxidation.

It is listed below other examples.Saturated straight chain fatty acid such as palmitic acid, stearic acid and montanic acid；Unrighted acid Class such as brassidic acid, eleostearic acid and parinaric acid；Saturated alcohols such as stearyl alcohol, aralkyl alcohol, mountain alcohol, carnaubyl alcohol, wax Alcohol and melissyl alcohol；Polyalcohols such as D-sorbite；Fatty acid such as palmitic acid, stearic acid, behenic acid and montanic acid and alcohol are as firmly The ester of lipidol, aralkyl alcohol, mountain alcohol, carnaubyl alcohol, ceryl alcohol and melissyl alcohol；Fatty acid acyl amine such as linoleamide, oil Sour acid amides and lauric amide；Saturated fatty acid bisamide class such as di-2-ethylhexylphosphine oxide stearic amide, ethylenebis capric acid acidamide, Asia Ethyl dilaurate acid amides and hexamethylene bis stearic amide；Unrighted acid amide-type such as ethylenebisoleaamide, Hexamethylene bis oleamide, N, bis- oil base adipic acid acid amides of N'- and bis- oil base decanedioic acid acid amides of N, N'-；Aromatics bisamide class As the double stearic amides of meta-xylene and N, N'- distearyl M-phthalic acid acid amides；Aliphatic metal salt such as calcium stearate, the moon Cinnamic acid calcium, zinc stearate and magnesium stearate (commonly referred to metallic soap those)；By by vinyl monomer such as styrene and third Olefin(e) acid is grafted to the wax class that obtain on aliphatic chloroflo；The partial esterification products of aliphatic acid and polyalcohol such as behenic acid list glycerine Ester；It is hydrogenated with, with by vegetable fat, the methyl ester compound with hydroxyl for obtaining.

Among these waxes, from improvement low-temperature fixability and heat-resisting biofouling viewpoint, preferably chloroflo such as low-molecular-weight poly- third Alkene, paraffin and fischer-tropsch wax and fatty acid ester wax such as Brazil wax.In the present invention, heat-resisting biofouling from improving further Viewpoint, more preferably chloroflo.

In the present invention, every 100.0 mass parts resin glue, the amount of wax are preferably at least 1.0 mass parts and are not more than 20.0 mass parts.

Preferably at least 45 DEG C of the peak temperature of the highest endothermic peak of the wax measured using differential scanning calorimetry (DSC) and not More than 140 DEG C, more preferably at least 70 DEG C and no more than 100 DEG C.The scope of the peak temperature of the maximum endothermic peak of wax be more preferably Because ensure toner anticaking capacity and heat-resisting biofouling both.

In the present invention, toner-particle may include colouring agent.The example of suitable colouring agent described below.

Include carbon black and by using yellow colorants, magenta coloring agent for the example of the colouring agent of black toner Adjust with cyan colorant to the colouring agent of black.Pigment can be individually used for colouring agent, but the viewpoint from full-colour image quality, It is preferred that dyestuff is used together with pigment.

The example of the pigment for magenta toner described below.C.I. paratonere 1,2,3,4,5,6,7,8,9,10, 11、12、13、14、15、16、17、18、19、21、22、23、30、31、32、37、38、39、40、41、48:2、48:3、48:4、 49、50、51、52、53、54、55、57:1、58、60、63、64、68、81:1、83、87、88、89、90、112、114、122、123、 146th, 147,150,163,184,202,206,207,209,238,269 and 282；C.I. pigment violet 19；With C.I. vat red 1, 2nd, 10,13,15,23,29 and 35.

The example of the dyestuff for magenta toner described below.C.I. solvent red 1,3,8,23,24,25,27,30, 49th, 81,82,83,84,100,109 and 121；C.I. disperse red 9；C.I. solvent purple 8,13,14,21 and 27；Oil-soluble dyes are such as C.I. disperse violet 1；With basic-dyeable fibre for example C.I. alkali red 1:1,2,9,12,13,14,15,17,18,22,23,24,27,29,32, 34th, 35,36,37,38,39 and 40；With C.I. alkaline purple 1,3,7,10,14,15,21,25,26,27 and 28.

The example of the pigment for cyan toner described below.C.I. alizarol saphirol 2,3,15:2、15:3、15:4th, 16 and 17；C.I. reductive blue 6；C.I. acid blue 45, and wherein 1 to 5 phthalimidomethyl has been substituted by phthalocyanine frame Copper phthalocyanine.

C.I. solvent blue 70 is suitable as the dyestuff for cyan toner.

The example of the pigment for Yellow toner described below.C.I. pigment yellow 1,2,3,4,5,6,7,10,11,12, 13、14、15、16、17、23、62、65、73、74、83、93、94、95、97、109、110、111、120、127、128、129、147、 151st, 154,155,168,174,175,176,180,181 and 185；C.I. Vat Yellow 1,3 and 20.

C.I. solvent yellow 16 2 is suitable as the dyestuff for Yellow toner.

Every 100.0 mass parts resin glue, the amount of colouring agent are preferably at least 0.1 mass parts and no more than 30.0 mass Part.

In the present invention, toner-particle can optionally include charge control agent.

Known reagent can be used as charge control agent.Particularly, colourless, with high charged toner speed and can stablize It is preferred that ground keeps the metallic compound of the aromatic carboxylic acid of constant carried charge.

The example of negative charge controlling agent includes metal salicylate compound, naphthoic acid metallic compound, dicarboxylate metal's chemical combination Polymer-type in polymer type compounds, side chain with sulfonic acid or carboxylic acid in thing, side chain with sulfonate or sulphonic acid ester Polymer type compounds, boron compound, carbamide compound, silicon compound and cup with carboxylate or carboxylate in compound, side chain Aromatic hydrocarbons.

The example of positive charge control agent includes polymer type compounds in quaternary ammonium salt, side chain with quaternary ammonium salt, guanidine chemical combination Thing and imidazolium compounds.

Charge control agent internal or external can add to toner-particle.

Every 100.0 mass parts resin glue, the amount of charge control agent are preferably at least 0.2 mass parts and no more than 10.0 Mass parts.

The toner of the present invention can optionally include fine inorganic particles.

Fine inorganic particles internal can add to toner-particle, or can mix with toner-particle as external additive.

When particle is included as outside agent, preferred fine inorganic particles such as silica fine particles, titanium oxide fine particle And aluminum oxide fine particles.Fine inorganic particles are preferably carried out with hydrophobic agents such as silane compound, silicone oil or their mixture Hydrophobization.

When fine inorganic particles are used for the mobility for improving toner, the specific surface area of particle is preferably at least 50m²/ g and No more than 400m²/g.

Meanwhile, when fine inorganic particles are used for the durability for improving toner, the specific surface area of particle is preferably at least 10m²/ g and no more than 50m²/g.

The fine inorganic particles with specific surface area within the above range are can be combined for improving mobility and durability two Person.

When fine inorganic particles are included as external additive, every 100.0 mass parts toner-particle, preferably comprise at least The particle of 0.1 mass parts and no more than 10.0 mass parts.Known mixer such as Henschel mixer can be used for toner Grain is mixed with inorganic particle.

The toner of the present invention also is used as monocomponent toner, but for further improvement repeatability, and in order to Long-time ensures picture steadiness, and toner also can be mixed with magnetic carrier, and is used as two-component developing agent.

The example of magnetic carrier includes ferriferous oxide；Metal such as iron, lithium, calcium, magnesium, nickel, copper, zinc, cobalt, manganese, chromium and rare earth The particle of metal, the particle of their alloy, and the particle of their oxide；Magnetic such as ferrite；With include magnetic Scattered resin carrier (so-called resin carrier) with the magnetic of the resin glue that magnetic is kept dispersity.Can make Use generally well-known carrier.

When the toner of the present invention is by mixing with magnetic carrier as two-component developing agent, magnetic carrier and toner Mixing ratio be preferably toner concentration preferably at least 2 mass % and no more than 15 mass % for making in two-component developing agent, more Preferably at least 4 mass % and no more than 13 mass %.

In the present invention, the preparation method of toner-particle is not particularly limited, but in order to fully show dispersing agent for wax Effect, preferably uses melt kneading method or emulsification aggregation method.Additionally, from the viewpoint of wax dispersiveness, more preferably using melt kneading Method.

Here, melt kneading method is the preparation method of the toner-particle for comprising the following steps：Melt and mediate including viscous Knot agent resin, wax and toner dispersing agent for wax mixture with obtain melt kneading product the step of (hereinafter referred to as " molten Melt kneading step ").

In the case of toner-particle being prepared by melt kneading step, improve the dispersiveness of wax.

In melt kneading step, under heating and shear inference, tempestuously the original material of mixing toner-particle is (special It is not, resin glue, dispersing agent for wax and wax), thus improve the dispersiveness of wax.As a result, the wax in toner-particle is fine Ground dispersion, improves heat-resisting biofouling.

Even if additionally, when being placed on toner under high temperature and high humidity, dispersing agent for wax suppression wax dissolution is to toner Grain surface, improves the anticaking capacity of toner, and does not reduce chargeding performance.

In the present invention, the melting that the preparation method of toner-particle preferably includes to obtain in cooling melt kneading step is pinched The product of conjunction, the step of crush and be heat-treated obtained resin particle (hereinafter referred to as " heat treatment step ").

In the case of heat treatment step is carried out, compared with those of conventional dispersing agent for wax, chargeding performance and resistive connection is improved Block.

Generally, when heat treatment step is carried out, as the dissolution of high tack wax is to toner-particle surface, thus reduces and adjust The anticaking capacity of toner, and there are charged defects as toner fluidity reduces.

However, when heat treatment includes the toner-particle of dispersing agent for wax of the present invention, as wax and hydrophobic wax are disperseed Agent is migrated simultaneously to toner-particle surface, even if thus under high temperature and high humidity, do not deteriorate the mobility of toner yet, and Chargeding performance is not deteriorated.Further, since the dispersing agent for wax of the present invention has the knot for being derived from bulky saturation alicyclic compound Structure position, thus wax dissolution during heating treatment can be suppressed, and improve the anticaking capacity of toner.

Will be described hereinafter the step of toner-particle being prepared using melt kneading method.

First, in raw material blend step, weighed including crystalline polyester resin and amorphism polyester with scheduled volume The resin glue of resin etc., wax and toner dispersing agent for wax are blended and mix as raw material for toner.

Be suitable for mix device example include Henschel mixer (by Nippon Coke＆Engineering Co., Ltd. manufacture)；High-speed mixer (is manufactured by Kawata MFG Co., Ltd.)；Ribocone (by Okawara MFG.Co., Ltd. manufacture)；Nauta mixer, Turbulizer, Cyclomix (being manufactured by Hosokawa Micron Corporation)； Screw pin mixer (Pacific Machinery＆Engineering Co., Ltd.)；With Loedige mixer (by Matsubo Corporation is manufactured).

Then, formed mixture is melted and mediate so that resin melting, and wax and toner are divided with dispersing agent for wax It is dispersed in wherein (melt kneading step).

The example for being suitable for the device of melt kneading includes TEM type extruder (by Toshiba Machine Co., Ltd. Manufacture)；TEX Dual-screw kneader (is manufactured by The Japan Steel Works, Ltd.)；PCM kneader is (by Ikegai Ironworks Corp. is manufactured)；(manufactured by Mitsui Mining Co., Ltd.) with Kneadex.With respect to batch kneading Machine, preferably continuous kneader such as single-screw or double screw extruder, because they continuously can produce.

Then, with the product of the so obtained melt kneading of the roll-ins such as two rollers, and by the cooling such as water cooling.

Obtained cooled product is crushed to desired particle diameter.Initially, with disintegrating machine, hammer-mill or feather grinding machine (feather mill) is roughly ground, then with Kryptron system (by Kawasaki Heavy Industries, Ltd. system Make) and Super rotor (by Nisshin Engineering Inc. manufacture) carry out fine grinding, to obtain resin particle.

Then, obtained resin particle is divided into desired particle diameter, can be used as toner-particle.It is suitable for the dress being classified The example that puts includes Turboplex, Faculty, TSP, TTSP (being manufactured by hosokawa Micron Corporation)；With Elbow Jet (is manufactured by Nittetsu Mining Co., Ltd.).

Resin particle to being obtained is heat-treated, and can be used as toner-particle.

Exist after the heat treatment coarse grained in the case of, if it is desired, can by classification or screening remove coarse granule. Said apparatus can be used to be classified.Meanwhile, the example for being suitable for the device of screening includes Ultra Sonic (by Koei Sangyo Co., Ltd. manufacture)；Resonasieve and Gyrosifter (is manufactured by Tokuju Corporation)；Turbo Screener (is manufactured by Turbo Kogyo Co., Ltd.)；Hi-Bolter (is manufactured by Toyo Hitec Co., Ltd.).

Meanwhile, the resin particle before heat treatment step, obtained by optionally being added to fine inorganic particles etc..

The method for illustrating the annealing device heat treatment resin particle that describes using Fig. 1 in detail below.

By the compressed gas adjusted by compressed gas flow rate adjustment device 2, make by raw material distributor 1 to make a reservation for The resin particle of amount distribution is entered and is arranged in the ingress pipe 3 on the plumb line of raw material supplier.By through ingress pipe 3 Resin particle is uniformly dispersed by being arranged on the conical projections shape component 4 in raw material supplier centre, Ran Houyin The supply pipe 5 of the radial distribution being directed at along 8 direction orientations, and be directed to wherein by the process chamber 6 being heat-treated.

At this moment, the adjusting means 9 for adjusting the stream of resin particle by being arranged in process chamber 6, adjusts supply Resin particle stream in process chamber 6.As a result, the resin particle in process chamber 6 is supplied to while 6 internal rotating of process chamber Heat treatment, then cools down.

Hot blast for being heat-treated the resin particle of supply is supplied by hot air supply device 7, and is entered by allocation member 12 Row distribution.Hot blast is introduced in process chamber 6, while carrying out helical form rotation by the rotating member 13 for making hot blast rotation. As this composition is used for, for making the rotating member 13 of hot blast rotation with multiple blades, can be by the number of change blade Rotation with setting angle control hot blast (reference 11 represents hot air supply device outlet).When in hot air supply device 7 When measuring in outlet, the temperature for being supplied to the hot blast of process chamber 6 is preferably at least 100 DEG C and no more than 300 DEG C, more preferably at least 130 DEG C and no more than 170 DEG C.When the temperature in the outlet of hot air supply device 7 within the above range when, equably can process Particle, while prevent fusion and the coalescence due to excessively thermally-induced resin particle.

Hot blast is supplied by hot air supply device 7.The thermally treated resin particle being heat-treated is by being supplied by cold wind To the cold front heavy rain that device 8 is supplied.The temperature of the cold wind supplied by cold wind feedway 8 is preferably at least -20 DEG C and is not more than 30℃.When cold wind temperature within the above range when, thermally treated resin particle can be cooled efficiently, and be prevented from Thermally treated resin particle fusion and coalescence, and do not suppress the uniform heat treatment of resin particle.Absolute amount of moisture in cold wind Preferably at least 0.5g/m³And no more than 15.0g/m³.

The thermally treated resin particle for having cooled down is reclaimed using the retracting device 10 of the lower end for being located at process chamber 6.Returning The top of receiving apparatus 10 arranges air blast (in figure is not described), and is configured to attract and convey particle.

Powder particle supply mouth 14 is set, so that the direction of rotation of resin particle of supply and the direction of rotation phase of hot blast With, and also retracting device 10 is set in the tangential direction of the peripheral part of process chamber 6, to maintain the rotation of the resin particle of rotation Turn direction.Additionally, being supplied by cold wind with tangential direction supply from the peripheral part of device in the horizontal direction to the inner peripheral surface of process chamber The cold wind that device 8 is supplied.The direction of rotation of the resin particle of the pre-heat treatment supplied by powder particle supply mouth 14, supplied by cold wind The direction of rotation of the direction of rotation of the cold wind supplied to device 8 and the hot blast supplied by hot air supply device 7 is all in phase Tongfang Upwards.As a result, the eddy flow inside aggrandizement apparatus, and do not cause turbulent flow in process interior, strong centrifugal force is applied to the pre-heat treatment Resin particle, and further improve the pre-heat treatment resin particle dispersiveness.Thus, it is possible to obtain having seldom coalescence The thermally treated resin particle of the uniform shapes of grain.

In the present invention, the average circularity of toner preferably at least 0.960, and more preferably at least 0.965.In toning The average circularity of agent within the above range in the case of, improve toner transfer efficiency.

The measuring method of the various physical propertys of toner explained below and raw material.

<The measurement of the glass transition temperature (Tg) of resin>

According to ASTM D3418-82, surveyed using differential scanning calorimeter " Q2000 " (being manufactured by TA Instruments.) The glass transition temperature of amount resin.

The temperature correction of device detector, and the fusing thermal recalibration heat using indium are carried out using the fusing point of indium and zinc.

More specifically, being precisely weighed about 5mg resin, and it is put in aluminium dish.The aluminium dish of sky is used as reference.With 10 DEG C/ The programming rate of min, at least 30 DEG C and in no more than 180 DEG C of measurement range, implements measurement.

To 180 DEG C and after holding 10min, temperature is reduced to 30 DEG C, is then raised again in liter high-temperature.Second During rising high-temperature, obtain within the temperature range of at least 30 DEG C and no more than 100 DEG C and compare thermal change.By in DSC curve The curve of the stage shape changing unit of glass transition is vertical with the edge of line now than being obtained by prolongation baseline before and after thermal change The temperature at point that the equidistant line of direction of principal axis intersects is used as the glass transition temperature (Tg of resin：℃).

<The measurement of the peak temperature of the endothermic peak of wax and crystalline polyester resin>

According to ASTM D3418-82, (manufactured by TA Instruments.) using differential scanning calorimeter " Q1000 ", survey The summit temperature of the endothermic peak of amount wax and crystalline polyester resin.

The temperature correction of device detector, and the fusing thermal recalibration heat using indium are carried out using the fusing point of indium and zinc.

More specifically, being precisely weighed about 5mg sample, and it is put in silver plate.Measure once.Use the silver plate conduct of sky Reference.Measuring condition described below.

Heating rate：10℃/min

Measurement started temperature：20℃

Measurement end temp：180℃

Using toner as in the case of sample, when endothermic peak (from the endothermic peak of resin glue) not with except knot During the heat absorption overlap of peaks of the resin beyond crystalline substance resin and wax, obtained maximum endothermic peak can be treated as such as from wax Endothermic peak with crystalline resin.

Meanwhile, using toner as in the case of sample, by using hexane solvent by Soxhlet extractron from tune Toner extracts wax, carries out the measure of the endothermic peak of wax and the endothermic peak of crystalline resin, individually carries out wax by said method Scanning calorimetry is measured, and the endothermic peak by the endothermic peak for being obtained with toner is compared.

When there is multiple peaks, maximum endothermic peak as referred to herein represents the peak with maximum caloric receptivity.By maximum suction The peak temperature of thermal spike is used as fusing point.

<The measurement of weight average molecular weight (Mw)>

By using gel permeation chromatography (GPC), the molecular weight distribution of dispersing agent for wax etc. is measured in the following manner.

Initially, sample is put in tetrahydrofuran (THF), allow which that several hours are placed at 25 DEG C, then commove Well to mix with THF.Then, system is placed 12 hours or longer under steady state condition, until there is no sample coalescence.

In this case, the standing time in THF is 24h.Then, obtained solution is passed through sample treatment mistake Filter (at least 0.2 μm of aperture and no more than 0.5 μm；Such as Myshori disk H-25-2 is (by Tosoh Corporation system Make)), and using by solution as GPC sample.

Sample concentration is adjusted at least 0.5mg/mL and no more than 5.0mg/mL.Using sample solution, in following conditions Under measure.

At 40 DEG C, in heating chamber, make post stable, the tetrahydrofuran (THF) as solvent is made with the speed of 1mL/ minute Stream enters post at such a temperature, and injects about 100mL sample solution for measuring.

The combination of multiple commercially available Aquapak A-440 posts is used as post.Therefore, using Showa Denko The combination of the shodex GPC KF-801,802,803,804,805,806,807 and the 800P that K.K. manufacture, or Tosoh Corporation manufacture TSKgel G1000H (HXL), G2000H (HXL), G3000H (HXL), G4000H (HXL), The combination of G5000H (HXL), G6000H (HXL), G7000H (HXL) and TSKgurd post.

When the molecular weight of sample is measured, made with several monodisperse polystyrene standard samples are used by count value Relation between the logarithm value of calibration curve, calculates the molecular weight distribution of sample.

The molecular weight that Tosoh Corporation or Showa Denko K.K., Ltd. are manufactured is for about 1 × 10²To 1 × 10⁷Sample with act on make calibration curve standard polystyrene sample.Using at least about 10 kinds polystyrene standard samples Product.Detector can be RI (refractive index) detector.

<The measurement of the weight average particle diameter (D4) of toner-particle>

The weight average particle diameter (D4) of toner-particle is measured using 25,000 effective Measurement channel numbers, using based on hole resistive square Method is simultaneously provided with accurate particle diameter distribution measurement apparatus " the Coulter Counter Multisizer of 100 μm of hole pipes" (by Beckman Coulter, Inc. are manufactured) and for setting measurement condition and the attached special-purpose software of analysis measurement data " Beckman Coulter Multisizer 3Version 3.51 " (being manufactured by Beckman Coulter, Inc.) is measured Data analysis and calculating.

By reagent grade sodium chloride to be dissolved in ion exchange water to the concentration of about 1 mass %, obtain for measurement Electrolytic aqueous solution.For example, can be using " ISOTON II " (being manufactured by Beckman Coulter, Inc.).

Before measuring, special-purpose software is set in the following manner, and is analyzed.

" the changing the interface (SOM) of standard method of measurement " of special-purpose software, the tale of control model is set to 50, 000 particle, measurement period are set to 1, Kd value and are set to using " 10.0 μm of standard particle " (Beckman Coulter, Inc.) The value of acquisition.By pressing the measurement button of lower threshold value/noise level, automatic given threshold and noise level.Additionally, electric current is set For 1600mA, gain is set to 2, and electrolytic aqueous solution is set to ISOTON II, and is input into " inspection " for flushing hole pipe after measurement.

In " interface being set from pulse to the conversion of particle diameter " of special-purpose software, element spacing is set to logarithm particle diameter, grain Footpath element is set to 256, and particle size range is set as at least 2 μm and no more than 60 μm.

Concrete measuring method is as follows.

(1) electrolysis for being put into a total of about 200mL in the special 250-mL glass round bottom beaker of Multisizer 3 is water-soluble Liquid, and be installed on sample stage.To be stirred the stirring of rod counterclockwise under 24 turns/s.By " the hole flushing " of special-purpose software Function, removes dirt and the bubble of Kong Guanzhong.

(2) in 100mL flat bottom glass beaker, be put into the electrolytic aqueous solution of a total of about 30mL, be added to by " Contaminon the N " (use with pH 7 and including nonionic surfactant, anion surfactant and organic washing-assisting detergent The aqueous solution in 10 mass % of the neutral detergent of precision measurement apparatus；By Wako Pure Chemical Industries, Ltd. manufacturing) the weak solution about 0.3mL that dilutes about 3 mass times with ion exchange water and obtain is used as dispersant.

(3) with 120W electricity output and including two with the built-in frequency of oscillation of the state of phase shift 180 degree as 50kHz The ultrasonic disperser " Ultrasonic Dispersion System Tetora 150 " of oscillator is (by Nikkaki Bios Co., Ltd. manufacture) tank in, be put into the ion exchange water of scheduled volume, and about 2mLContaminon N added to tank.

(4) beaker as disclosed in above-mentioned project (2) is arranged in the beaker fixing hole of ultrasonic disperser, and starts Ultrasonic disperser.The height and position of beaker is adjusted, so that the resonance state of the liquid level of the electrolytic aqueous solution in beaker is maximized.

(5) in the state of with the electrolytic aqueous solution in the beaker disclosed in Ultrasonic Radiation such as above-mentioned project (4), will about 10mg toner-particle is by being partly added to electrolytic aqueous solution, and makes its dispersion.Then proceed to ultrasonic wave decentralized processing 60s. During ultrasonic wave disperses, optionally, by the lower water temperature in tank at least 10 DEG C and no more than 40 DEG C.

(6) electrolytic aqueous solution as disclosed in above-mentioned project (5) of toner has wherein been dispersed with pipette, dropping To being placed in the round bottom beaker as disclosed in above-mentioned project (1) in sample stage, and measurement concentration is adjusted to about 5%.Enter Row measurement, reaches 50,000 until measuring numbers of particles.

(7) the special-purpose software analysis measurement data by being included with device, calculate weight average particle diameter (D4).Special soft when setting During chart/volume % in part, " average diameter " on analysis/volume statistical value (arithmetic average) interface is weight average particle diameter (D4).

<The measurement of average circularity>

(manufactured by Sysmex Corporation) using streaming particle image analyzer " FPIA-3000 ", in calibration behaviour Under measurement and analysis condition when making, the average circularity of toner-particle is measured.

Concrete measuring method is as follows.First, the ion exchange water for about 20mL having been removed solid impurity in advance is put into glass In glass container.It is added to " Contaminon N " (with pH 7 and including nonionic surfactant, anionic surface The aqueous solution of 10 mass % of the neutral detergent for precision measurement apparatus of activating agent and organic washing-assisting detergent,；By Wako Pure Chemical Industries, Ltd. are manufactured) weak solution that dilutes about 3 mass times with ion exchange water and obtain is about 0.2mL is used as dispersant.Then add about 0.02g measurement sample, and decentralized processing is carried out 2 minutes using ultrasonic disperser, To obtain the dispersion liquid for measuring.Now, appropriate cooling is carried out, so that the temperature of dispersion liquid becomes at least 10 DEG C and less In 40 DEG C.By with 50kHz frequency of oscillation and 150W electricity output desk-top ultrasonic cleaner disperser " VS-150 " (by VELVO-CLEAR is manufactured) it is used as ultrasonic disperser, the ion exchange water of scheduled volume is put in tank, and by about 2mL's Contaminon N adds screw clamp.

The streaming particle image analyzer with the standard object lens (10 times) that installs is used for measuring, and by particle sheath " PSE-900A " (being manufactured by Sysmex Corporation) is used as sheath fluid.The dispersion liquid prepared according to above-mentioned steps is imported stream Formula particle image analyzer, and under HPF measurement pattern, 3000 toner-particles are amounted to amount to digital modeling measurement.General Binary-state threshold during grain analysis is set to 85%, as equivalent circle diameter, analysis particle diameter is limited at least 1.985 μm and is less than 39.69 μm, and determine the average circularity of toner-particle.

In the measurements, before the start of the measurement, using standard latex particle (with the water-reducible " RESEARCH of ion exchange AND TEST PARTICLES Latex Microsphere Suspensions 5200A is " (by Duke Scientific Corp. manufacture)) carry out automatic focusing.It is preferred that after measurement starts, being focused per 2 hours thereafter.

Streaming particle image analyzer used in the embodiment of the present application is calibrated by Sysmex Corporation, and is received The calibration certificate that is signed and issued by Sysmex Corporation.Remove as equivalent circle diameter, analysis particle diameter is limited at least 1.985 μm And less than 39.69 μm in addition, measure under measurement when calibration certificate is received and analysis condition.

<The measurement of the acid number of dispersing agent for wax>

The acid number of dispersing agent for wax is measured by following methods.Acid number is to neutralize the hydrogen-oxygen required for the acid contained in 1g sample Change the milligram number of potassium.The acid number of resin is determined according to JIS K0070-1992.Measured comprises the following steps that.

(1) preparation of reagent

By 1.0g phenolphthalein is dissolved in 90mL ethanol (95vol%), and add deionized water to 100mL, obtain phenol Phthalein solution.

7g reagent grade sodium chloride will be amounted to 5mL deionized water is dissolved in, and 1L is obtained by adding ethanol (95vol%).Will Solution is put in alkaline-resisting container, and so which is there placed 3 days, to prevent from contacting with carbon dioxide etc., is then filtered, is obtained Potassium hydroxide solution.Obtained potassium hydroxide solution is stored in alkaline-resisting container.The 0.1mol/L salt of 25mL will be amounted to Acid is added in triangular flask, is added a few drop phenolphthalein solutions, is titrated with potassium hydroxide solution, and the potassium hydroxide needed by neutralization is molten The amount of liquid obtains the factor of potassium hydroxide solution.0.1mol/L hydrochloric acid is prepared to use according to JIS K 8001-1998.

(2) operate

(A) master trip

The 2.0g accurate weight sample of dispersing agent for wax is put in 200mL triangular flask, and interior during 5h, add 100mL Toluene:Ethanol (4:1) mixed solution is to dissolve dispersing agent for wax.Then add a few drop phenolphthalein solutions as indicator, and use Potassium hydroxide solution is titrated.When the terminal of titration is that the light red of indicator keeps about 30s.

(B) blank test

Removing does not use sample (that is, only to use toluene:Ethanol (4:1) mixed solution) beyond, by identical operate into Row titration.

(3) following equatioies are substituted into the result for obtaining, and calculates acid number.

A=[(C B) × f × 5.61]/S

Here, A：Acid number (mg KOH/g)；B：The addition (mL) of potassium hydroxide solution in blank test；C：In master trip The addition (mL) of potassium hydroxide solution；f：The factor of potassium hydroxide solution；And S：Sample (g).

[embodiment]

The present invention is illustrated in greater detail below with reference to preparation example and embodiment, but the present invention does not limit this.Unless another External declaration, the part in following formulas and percentage are all based on quality.

<The preparation example of dispersing agent for wax A1>

The dimethylbenzene and 10.0 parts of polypropylene (90 DEG C of fusing point) that amount to 300.0 parts are put into and are equipped with thermometer and agitator Autoclave reaction vessel, and so that polypropylene is thoroughly dissolved.After nitrogen displacement, at 180 DEG C, through 3h, 68.0 are dripped Part styrene, 5.0 parts of methacrylic acids, 5.0 parts of cyclohexyl methacrylates, 12.0 parts of butyl acrylates and 250.0 parts of diformazans The mixed solution of benzene, to be polymerized.Then, reaction system is held at 30 minutes, solvent is removed, is obtained wax and divides Powder A1.The composition of obtained dispersing agent for wax, weight average molecular weight and acid number are shown in table 1.The SP value of dispersing agent for wax A1 is 10.0.

<The preparation example of dispersing agent for wax A2>

The dimethylbenzene and 10.0 parts of polypropylene (90 DEG C of fusing point) that amount to 300.0 parts are put into and are equipped with thermometer and agitator Autoclave reaction vessel, and so that polypropylene is thoroughly dissolved.After nitrogen displacement, at 180 DEG C, through 3h, 63.0 are dripped Part styrene, 10.0 parts of methacrylic acids, 5.0 parts of cyclohexyl methacrylates, 12.0 parts of butyl acrylates and 250.0 parts of diformazans The mixed solution of benzene, to be polymerized.Then, reaction system is held at 30 minutes, solvent is removed, is obtained wax and divides Powder A2.The composition of obtained dispersing agent for wax, weight average molecular weight and acid number are shown in table 1.The SP value of dispersing agent for wax A2 is 10.0.

<The preparation example of dispersing agent for wax A3>

The dimethylbenzene and 10.0 parts of polypropylene (90 DEG C of fusing point) that amount to 300.0 parts are put into and are equipped with thermometer and agitator Autoclave reaction vessel, and so that polypropylene is thoroughly dissolved.After nitrogen displacement, at 180 DEG C, through 3h, 73.0 are dripped Part styrene, the mixed solution of 5.0 parts of cyclohexyl methacrylates, 12.0 parts of butyl acrylates and 250.0 parts of dimethylbenzene, to enter Row polymerization.Then, reaction system is held at 30 minutes, solvent is removed, obtains dispersing agent for wax A3.Obtained wax The composition of dispersant, weight average molecular weight and acid number are shown in table 1.The SP value of dispersing agent for wax A3 is 10.0.

<The preparation example of dispersing agent for wax A4 to A7>

Except the condition in the preparation example for optionally changing dispersing agent for wax A3 is to obtain weight average molecular weight as shown in table 1 (Mw), beyond, by carrying out identical operation in the preparation example with dispersing agent for wax A3, dispersing agent for wax A4 to A7 is obtained.Obtained The composition of dispersing agent for wax, weight average molecular weight and acid number are shown in table 1.

<The preparation example of dispersing agent for wax A8 to A10>

Except the condition in the preparation example for optionally changing dispersing agent for wax A3 is to obtain weight average molecular weight as shown in table 1 (Mw), and beyond hydrocarbon compound, by carrying out identical operation in the preparation example with dispersing agent for wax A3, dispersing agent for wax A8 is obtained extremely A10.The composition of obtained dispersing agent for wax, weight average molecular weight and acid number are shown in table 1.

<The preparation example of dispersing agent for wax A11 to A14>

Except the condition in the preparation example for optionally changing dispersing agent for wax A3 is to obtain weight average molecular weight as shown in table 1 (Mw), beyond the composition of hydrocarbon compound and styrene-acrylic, by carrying out phase in the preparation example with dispersing agent for wax A3 Same operation, obtains dispersing agent for wax A11 to A14.The composition of obtained dispersing agent for wax, weight average molecular weight and acid number are shown in table In 1.

<The preparation example of dispersing agent for wax A15 to A19>

Except the condition in the preparation example for optionally changing dispersing agent for wax A3 is to obtain weight average molecular weight as shown in table 1 (Mw), beyond the composition of hydrocarbon compound and styrene-acrylic, by carrying out phase in the preparation example with dispersing agent for wax A3 Same operation, obtains dispersing agent for wax A15 to A19.The composition of obtained dispersing agent for wax, weight average molecular weight and acid number are shown in table In 1.

<The preparation example of dispersing agent for wax A20>

The dimethylbenzene and 120.0 parts of polyethylene (128 DEG C of fusing point) that amount to 600.0 parts are put into and are equipped with thermometer and stirring The autoclave reaction vessel of device, and so that these is thoroughly dissolved.After nitrogen displacement, at 160 DEG C, through 2h, drip 1900.0 parts of styrene, 170.0 parts of acrylonitrile, 240.0 parts of butyl maleates, 78.0 parts of peroxidating hexahydro terephthalic acids two The mixed solution of the tert-butyl ester, 24.0 parts of butyl acrylates and 455.0 parts of dimethylbenzene, to be polymerized.Then, reaction system is protected Hold 30 minutes at such a temperature, solvent is removed, obtains dispersing agent for wax A20.The SP value of dispersing agent for wax A20 is 10.4.Obtained The composition of dispersing agent for wax, weight average molecular weight and acid number are shown in table 1.

<The preparation example of dispersing agent for wax A21>

In addition to the composition of the styrene-acrylic described in table 1, by carrying out and dispersing agent for wax A20 Preparation example in identical operation, prepare dispersing agent for wax A21.The composition of obtained dispersing agent for wax, weight average molecular weight and acid number It is shown in table 1.

[table 1]

<The preparation example of crystalline polyester resin C1>

- 1,6-HD：34.5 parts of (0.29mol；Total mole number based on polyalcohol is 100.0mol%)

- dodecanedioic acid：65.5 parts of (0.28mol；Total mole number based on polybasic carboxylic acid is 100.0mol%)

- 2 ethyl hexanoic acid tin：0.5 part

Above-mentioned material is weighed in the reaction vessel for being equipped with cooling tube, agitator, nitrogen ingress pipe and thermocouple.Anti- After answering container internal atmosphere nitrogen displacement, under agitation, temperature gradually risen, and under agitation, in 140 DEG C of temperature Under, carry out reaction 3h.

Then, by the reduced pressure of reaction vessel to 8.3kPa, and reaction 4h is carried out, while maintaining the temperature at 200 DEG C.

Then, by the reduced pressure of reaction vessel to below 5kPa, and reaction 3h is carried out at 200 DEG C, obtain crystallinity Polyester resin C1.

<The preparation of crystalline polyester resin C2 to C5>

In addition to the glycol in the preparation example for changing crystalline polyester resin C1 as shown in table 2 and dicarboxylic acids, by carrying out Operate with identical in the preparation example of crystalline polyester resin C1, obtain crystalline polyester resin C2 to C5.

[table 2]

Crystalline polyester resin	Glycol	Dicarboxylic acids	SP value (SP1)
				C1	1,6-HD (C6)	Dodecanedioic acid (C12)	11.3
C2	1,12- dodecanediol (C12)	Adipic acid (C6)	11.4
				C3	1,10- decanediol (C10)	Decanedioic acid (C10)	11.0
C4	1,6-HD (C6)	Decanedioic acid (C10)	11.5
				C5	1,6-HD (C6)	Fumaric acid (C4)	12.7

<The preparation example of non-crystalline polyester resin>

<The preparation example of low-molecular-weight non-crystalline polyester resin (L)>

Double (4- hydroxy phenyl) propane of-PPOX (2.8) -2,2-：76.6 parts of (0.17mol；Based on the total of polyalcohol Molal quantity is 100.0mol%)

- terephthalic acid (TPA)：17.4 parts of (0.10mol；Total mole number based on polybasic carboxylic acid is 72.0mol%)

- adipic acid：6.0 parts of (0.04mol；Total mole number based on polybasic carboxylic acid is 28.0mol%)

- butyl titanate (esterification catalyst)：0.5 part

Above-mentioned material is weighed in the reaction vessel for being equipped with cooling tube, agitator, nitrogen ingress pipe and thermocouple.

After reaction vessel interior atmosphere nitrogen displacement, under agitation, temperature gradually risen, and under agitation, At a temperature of 200 DEG C, reaction 4h is carried out.

Then, by the reduced pressure of reaction vessel to 8.3kPa, and 1h is maintained.Then, carry out being cooled to 180 DEG C, and will Pressure returns to atmospheric pressure (the first reactions steps).

- tert-butyl catechol (polymerization inhibitor)：0.1 part

Then, add above-mentioned material, by the reduced pressure of reaction vessel to 8.3kPa, and reaction 1h is carried out, while keeping Temperature is at 180 DEG C.Confirming 90 DEG C to be reached afterwards according to the softening point of the product of ASTM D36-86 measurement, reducing temperature To stop reaction (second reaction step), non-crystalline polyester resin (L) is obtained.Obtained non-crystalline polyester resin (L) Peak molecular weight (Mp) be 5000, it is 52 DEG C that softening temperature (Tm) is 90 DEG C and glass transition temperature (Tg).

<The preparation example of HMW non-crystalline polyester resin (H)>

Double (4- hydroxy phenyl) propane of-polyethylene glycol oxide (2.2) -2,2-：72.2 parts of (0.20mol；Based on the total of polyalcohol Molal quantity is 100.0mol%)

- terephthalic acid (TPA)：13.2 parts of (0.08mol；Total mole number based on polybasic carboxylic acid is 48.0mol%)

- adipic acid：8.2 parts of (0.06mol；Total mole number based on polybasic carboxylic acid is 34.0mol%)

- butyl titanate (esterification catalyst)：0.5 part

Above-mentioned material is weighed in the reaction vessel for being equipped with cooling tube, agitator, nitrogen ingress pipe and thermocouple.

After reaction vessel interior atmosphere nitrogen displacement, under agitation, temperature gradually risen, and under agitation, At a temperature of 200 DEG C, reaction 2h is carried out.

Then, by the reduced pressure of reaction vessel to 8.3kPa, and 1h is maintained.Then, carry out being cooled to 160 DEG C, and will Pressure returns to atmospheric pressure (the first reactions steps).

- trimellitic acid：6.3 parts of (0.03mol；Total mole number based on polybasic carboxylic acid is 18.0mol%)

- tert-butyl catechol (polymerization inhibitor)：0.1 part

Then, add above-mentioned material, by the reduced pressure of reaction vessel to 8.3kPa, and reaction 15h is carried out, while keeping Temperature is at 160 DEG C.Confirming 140 DEG C to be reached afterwards according to the softening point of the product of ASTM D36-86 measurement, reducing temperature To stop reaction (second reaction step), non-crystalline polyester resin (H) is obtained.Obtained non-crystalline polyester resin (H) Peak molecular weight (Mp) be 8700, it is 57 DEG C that softening temperature (Tm) is 142 DEG C and glass transition temperature (Tg).

<The preparation example of toner 1：Melt kneading method including heat treatment step>

- low-molecular-weight non-crystalline polyester resin (L)：70.0 parts

- HMW non-crystalline polyester resin (H)：30.0 parts

- crystalline polyester resin C1：7.5 part

- dispersing agent for wax A1：5.0 part

- fischer-tropsch wax：5.0 parts (chloroflo, the peak temperature of maximum endothermic peak is 90 DEG C)

- C.I. pigment blue 15:3：7.0 part

- 3,5- di-tert-butyl salicylic acid aluminium compound：0.3 part

Using Henschel mixer (FM-75 type is manufactured by Mitsui Mining Co., Ltd.), in 20s^-1Rotating speed Under, by above-mentioned material mixing rotational time 5 minutes, then with the Dual-screw kneader of the temperature for being set to 150 DEG C (PCM-30, Manufactured by Ikegai Corp) melted and mediated.The product of the melt kneading obtained by cooling, then using hammer-mill, slightly No more than 1mm is crushed to roughly, so as to obtain the product for crushing.Using mechanical crusher, (T-250, by Turbo Kogyo Co., Ltd. manufacture) subtly crush obtained crushing product.Then, using Faculty F-300 (by Hosokawa Micron Corporation is manufactured) it is classified, so as to obtain resin particle 1.The operating condition of Faculty F-300 is set It is set to 130s^-1Grading rotor rotating speed and 120s^-1Dispersion rotor rotating speed.

Using annealing device shown in Fig. 1, the resin particle 1 obtained by heat treatment, so as to obtain toner-particle 1.Will Operating condition is set as the inlet amount of 5kg/h, 150 DEG C of hot blast temperature, 6m³The hot blast flow velocity of/min, -5 DEG C of cold wind temperature, 4m³The cold wind flow velocity of/min, 20m³The blower air quantity of/min, and 1m³The injection air velocity of/min.

Using Henschel mixer (FM-75 type is manufactured by Mitsui Mining Co., Ltd.), in 30s^-1Rotating speed Under, 100 parts of toner-particles, 1,1.0 parts of hydrophobic silica (BET will be amounted to：200m²/ g) and 1.0 parts use isobutyl group three Titanium oxide fine particle (the BET of methoxy silane surface treatment：80m²/ g) mix rotational time 10 minutes, obtain toner 1.

In the dsc measurement of obtained toner 1, the endothermic peak from crystalline polyester resin is observed.

<The preparation example of toner 2：Melt kneading method>

In addition in the preparation example of toner 1, resin particle 1 is not heat-treated, by preparing with 1 identical of toner Method, obtains toner 2.

In the dsc measurement of obtained toner 2, the endothermic peak from crystalline polyester resin is observed.

<The preparation example of toner 3：Emulsification aggregation method>

(non-crystalline polyester resin dispersion liquid)

70.0 parts of low-molecular-weight non-crystalline polyester resin (L), 30.0 parts of HMW amorphisms will be amounted to ammonia The pH of polyester resin (H) and 400.0 parts of ion exchange waters is adjusted to 8.5, is then operated under 150 DEG C of heating condition Cavitron, so as to obtain non-crystalline polyester resin dispersion liquid (solid fraction：20%).(crystalline polyester dispersion liquid)

80 parts of crystalline polyester resin C1 will be amounted to and 720 parts of ion exchange waters are put into stainless steel beaker, and be heated to 99 ℃.When crystalline polyester resin C1 is melted, which is stirred with homogenizer.Then, emulsified and disperseed, be simultaneously added dropwise 2.0 parts of anion surfactants (Neogen RK, solid fraction：20%；Manufactured by DKS Co.LTD.), so as to be crystallized Property polyester resin C1 dispersion liquid (solid fraction：10%).

(colorant dispersion)

- C.I. pigment blue 15:3：1000 parts

- anion surfactant：150 parts

- ion exchange water：9000 parts

Above-mentioned material is mixed and is dissolved, then disperseed using impacting with high pressure type dispersion machine.

In obtained colorant dispersion, volume average particle size D50 of coloring agent particle is 0.16 μm, and colouring agent is dense Spend for 23%.

(wax dispersion)

- fischer-tropsch wax：45 parts (chloroflo, the peak temperature of maximum endothermic peak is 90 DEG C)

- dispersing agent for wax A1：45 parts

- anion surfactant：5 parts

- ion exchange water：150 parts

Above-mentioned material is heated to 95 DEG C, is disperseed using homogenizer, then carried out with pressure venting type Gaulin homogenizer Decentralized processing, so as to prepare wax dispersion (the wax concentration for being wherein dispersed with volume average particle size for the wax of 210nm：20%).

- non-crystalline polyester resin dispersion liquid：500 parts

- crystalline polyester resin C1 dispersion liquid：75 parts

With homogenizer, in circular stainless steel flask, above-mentioned material is mixed and is disperseed.It is added to amount to 0.15 part Poly- (aluminium chloride), and continue scatter operation with Ultra-Turrax.

Then, add

- colorant dispersion：30.5 parts

- wax dispersion：25 parts,

Add 0.05 part poly- (aluminium chloride) further, and continue scatter operation with Ultra-Turrax.

Then agitator and mantle heater are installed, temperature is increased to 60 DEG C, while adjusting turning for agitator Speed is maintained at system 15 minutes at 60 DEG C, per 10 minutes with Coulter Multisizer II (hole with fully stirring slurry Footpath：50 μm, manufactured by Beckman Coulter Inc.) measurement particle diameter, while high-temperature is risen with 0.05 DEG C/min, work as volume When average grain diameter becomes 5.0 μm, 75 parts of (additional resin) non-crystalline polyester resin dispersion liquids were put into 3 minutes.

Kept for 30 minutes after feeding intake, the sodium hydrate aqueous solution with 5% adjusts pH to 9.0.Then, with 1 DEG C/min Heating rate, temperature being increased to 96 DEG C, while adjusting pH to 9.0 per 5 DEG C, and system being maintained at 96 DEG C.Per 30 points Clock light microscope and SEM (FE-SEM) observation grain shape and surface nature.Due in the 5th hour There is spheroidization, thus temperature is reduced to 20 DEG C with 1 DEG C/min, and make particles cured.

Then, product is filtered, is fully washed with ion exchange water, then dry with vacuum desiccator, adjusted Toner particles 2.

Using Henschel mixer (FM-75 type is manufactured by Mitsui Mining Co., Ltd.), in 30s^-1Rotating speed Under, 1.0 parts of hydrophobic silica (BET will be amounted to：200m²/ g) and 1.0 parts with trimethoxysilane surface Titanium oxide fine particle (the BET of reason：80m²/ g) mix rotational time 10 minutes with 100 parts of toner-particles 2, obtain toner 3.

In the dsc measurement of obtained toner 3, the endothermic peak from crystalline polyester resin is observed.

<The preparation example of toner 4 and 5>

In addition to the dispersing agent for wax type in the preparation example for changing toner 3 as shown in table 3, the system with toner 3 is carried out In standby example, identical operation, obtains toner 4 and 5.

In the dsc measurement of obtained toner 4 and 5, the endothermic peak from crystalline polyester resin is observed.

<The preparation example of toner 6 to 8>

Except the dispersing agent for wax type in the preparation example for changing as shown in table 3 toner 3 and crystalline polyester resin amount with Outward, identical operation in the preparation example with toner 3 is carried out, obtains toner 6 to 8.

In the dsc measurement of obtained toner 6 to 8, the endothermic peak from crystalline polyester resin is observed.

<The preparation example of toner 9 to 13>

Except the dispersing agent for wax type in the preparation example for changing toner 3 as shown in table 3 and the class of crystalline polyester resin Beyond type and amount, identical operation in the preparation example with toner 3 is carried out, obtains toner 9 to 13.

In the dsc measurement of obtained toner 9 to 13, the endothermic peak from crystalline polyester resin is observed.

<Toner 14 to 30 and the preparation example of toner 32>

Except the dispersing agent for wax type in the preparation example for not using crystalline polyester resin and change toner 3 as shown in table 3 In addition, identical operation in the preparation example with toner 3 is carried out, obtains toner 14 to 30 and toner 32.

<The preparation example of toner 31>

Except the crystalline polyester resin in the preparation example for changing toner 3 as shown in table 3 and type and the amount of dispersing agent for wax In addition, identical operation in the preparation example with toner 3 is carried out, obtains toner 31.Survey in the DSC of obtained toner 31 In amount, the endothermic peak from crystalline polyester resin is observed.

<The preparation example of toner 33>

In addition to crystalline polyester resin and dispersing agent for wax is not used in the preparation example in toner 3, carry out and toner 3 Preparation example in identical operation, obtain toner 33.

[table 3]

<The preparation example of magnetic nuclear particle 1>

- step 1 (is weighed and blend step)：

Ferrite raw material weigh to obtain the above-mentioned material of above-mentioned ratio of components.Then, in dry type vibratory mill, using straight Footpath is 1/8 inch of stainless shot, is crushed and mixed 5h.

- step 2 (pre- calcination step)

In roll squeezer (roller compactor), obtained comminution of material is processed into about 1 millimeter of square grain Material.With the vibratory sieve being open with 3mm, coarse granule is removed from pellet, then removed with the vibratory sieve being open with 0.5mm Fine grained, and burner calcining furnace is used, in blanket of nitrogen (oxygen concentration 0.01vol%), at a temperature of 1000 DEG C, it is calcined grain Material 4h, so as to prepare the ferrite of pre- calcination.The ferritic composition of pre- calcination described below.

(MnO)_a(MgO)_b(SrO)_c(Fe₂O₃)_d

In the formula, a=0.257, b=0.117, c=0.007 and d=0.393.

- step 3 (pulverising step)

After about 0.3mm is crushed to disintegrating machine, 30 parts of water are added to the ferrite of 100 parts of pre- calcination, and In wet ball mill, using a diameter of 1/8 inch of zirconium oxide bead, crushing 1h is carried out.In wet ball mill, using a diameter of 1/16 inch of alumina bead, the slurry 4h obtained by crushing, so as to obtain ferrite slurry (the ferritic fine powder of pre- calcination Broken product).

- step 4 (granulation step)

1.0 parts will be amounted to as the polycarboxylic acid ammonium of dispersant and 2.0 parts as gluing based on the ferrite of the pre- calcination per 100 parts The polyvinyl alcohol of knot agent adds to ferrite slurry, then with spray dryer (by Ohkawara Kakohki Co., Ltd. system Make) it is a granulated into spherical particle.The particle diameter of the particle obtained by adjustment, heats 2h at 650 DEG C using rotary furnace, and removes dispersion Agent and the organic principle of binding agent.

- step 5 (calcination step)

In order to control calcination atmosphere, in electric furnace, in blanket of nitrogen (oxygen concentration 1.00vol%), through 2h by temperature from room The temperature of temperature rise to 1300 DEG C, then at a temperature of 1150 DEG C, carries out calcination 4h.Then, 60 are reduced to temperature through 4h DEG C, nitrogen atmosphere is recovered to air, at a temperature of less than 40 DEG C, takes out product.

- step 6 (selection step)

The particle of aggregation is crushed, low magnetic force product is removed by magnetic dressing, and by being sieved with 250 μm of purpose sieves, Coarse granule is removed, 50% particle diameter (D50) so as to obtain based on volume distributed median is 37.0 μm of magnetic nuclear particle 1.

<The preparation of coating resin 1>

26.8 mass % of cyclohexyl methacrylate monomer

0.2 mass % of methyl methacrylate monomer

8.4 mass % of Polymethyl Methacrylate Macromonomer

(weight average molecular weight for having methylacryloyl an end is 5000 macromonomer)

31.3 mass % of toluene

31.3 mass % of methyl ethyl ketone

2.0 mass % of azodiisobutyronitrile

Among above-mentioned material, by cyclohexyl methacrylate monomer, methyl methacrylate monomer, methyl methacrylate Macromonomer, toluene and methyl ethyl ketone put into and are equipped with reflux cooler, thermometer, nitrogen ingress pipe and agitator Four mouthfuls of separable flasks.Then, nitrogen is imported, sufficient nitrogen atmosphere is obtained, then carries out being heated to 80 DEG C.Then, add Azodiisobutyronitrile, and carry out polymerization 5h under reflux.By hexane injection obtained by product, cause copolymer precipitation and Separate out, and sediment is filtered and is vacuum dried, obtain coating resin 1.

Coating resin 1 obtained by amounting to 30 parts is dissolved in 40 parts of toluene and 30 parts of methyl ethyl ketones, obtains polymer molten 1 (solid fraction of liquid：30 mass %).

<The preparation of coating resin solution 1>

1 (resin solid concentration of polymer solution：30%) 33.3 mass %

66.4 mass % of toluene

Carbon black (Regal 330；Manufactured by Cabot Corporation) 0.3 mass %

(primary particle size 25nm, N2 adsorption specific surface area 94m²/ g, DBP oil absorption 75mL/100g)

In paint shaker, by using the zirconium oxide bead of a diameter of 0.5mm, above-mentioned material is disperseed 1h.With 5.0 μm Film filter filter obtained by dispersion liquid, obtain coating resin solution 1.

<The preparation example of magnetic carrier 1>

(resin-coated step)

Coating resin solution 1 is put in the vacuum outgas type kneader for keeping at normal temperatures.Per 100 parts of magnetic nuclear particles 1, the amount of the resin Composition of input is 2.5 parts.After feeding intake, it is stirred under 30rpm rotating speed 15 minutes, and certain After the evaporation of (80 mass %) or greater amount solvent, high-temperature is risen to 80 DEG C, while mix under reduced pressure, through 2h by toluene distillation Go out, then cool down.

The low magnetic product of obtained magnetic carrier is classified by magnetic dressing so as to by 70 μm of purpose sieves. Subsequently produced based on the magnetic carrier 1 that 50% particle diameter (D50) of volume distributed median is 38.2 μm with the classification of air classifier.

Toner 1 to 33 is added to magnetic carrier 1, toner concentration is obtained for 8.0 mass %, and is mixed using V-type Machine (V-10 is manufactured by Tokuju Corporation), in 0.5s^-1Under, mixing rotational time 5 minutes, obtain dual component development Agent 1 to 33.

<Embodiment 1 to 30, comparative example 1 to 3>

Using two-component developing agent 1 to 33, evaluated.

The Canon printer imageRUNNER ADVANCE C9075PRO of the transformation for digital commercial printing is used as Image forming apparatus, and by two-component developing agent to be put in the developing cell of cyan position and adjusts developer bearing member D/C voltage V_DC, electrified voltage V on electrostatic latent image bearing carrier_DWith laser power obtaining in electrostatic latent image bearing components or Desired toner bearing capacity on paper, carries out evaluation described below.Transformation printer is can freely set fixing temperature And processing speed.

Based on following evaluation methods, evaluated.As a result it is shown in table 4.

<Evaluate 1：Chargeding performance>

Using round metal bobbin and cylinder filter, suck and collect the toner on electrostatic latent image bearing carrier, by terms of Calculate the friction belt electricity of toner and the bearing capacity of toner.

More specifically, using toner on the faraday cup measurement friction belt electricity of toner and electrostatic latent image bearing carrier Bearing capacity.

In faraday cup, due to coaxial bitubular configuration, inner and outer tubes are electric insulations.By with carried charge Q's Electrical body is placed in inner tube, equivalent to the metallic cylinder existed due to electrostatic induction with carried charge Q.Use electrometer (Keithley 6517A is manufactured by Keithley Instruments) measures induction band electricity, will be by by carried charge Q (mC) Divided by value (Q/M) obtained from toner qualities M (kg) in inner tube as the friction belt electricity of toner.

Additionally, sucking surface area S and by toner qualities M divided by suction surface area S (cm by measuring²), obtain every list The bearing capacity of the toner of bit surface area.

Before toner layer on it will be formed in electrostatic latent image bearing carrier is transferred to intermediate transfer member, stop quiet The rotation of electric latent image bearing member, the toner image on electrostatic latent image bearing carrier is directly attracted to be surveyed with air Amount.

Toner bearing capacity (mg/cm²)=M/S

Friction belt electricity (the mC/kg)=Q/M of toner

Image forming apparatus are adjusted, so that under high temperature and high humidity environment (32.5 DEG C, 80%RH), electrostatic latent image carries structure On part, the bearing capacity of toner is 0.35mg/cm², and attract and collect toning by using round metal bobbin and cylinder cylinder filter Agent.Now, the carried charge Q that store in the capacitor and toner qualities M collected of the measurement by round metal cylindrical tube, and count The carried charge Q/M (mC/kg) of per unit mass is calculated, as the carried charge Q/ of per unit mass on electrostatic latent image bearing carrier M (mC/kg) (initial evaluation).

After above-mentioned evaluation (initial evaluation) is carried out, developing apparatus is removed from printer, and places it in high temperature With 72h under high humidity environment (32.5 DEG C, 80%RH).Then, then by developing apparatus install on a printer, with initial evaluation in Identical D/C voltage V_DCThe carried charge Q/M (placement post-evaluation) of per unit mass on lower measurement electrostatic latent image bearing carrier.

Using the carried charge Q/M on electrostatic latent image bearing carrier in initial evaluation per element quality as 100%, 72h is calculated After placement, on electrostatic latent image bearing carrier, the conservation rate of the carried charge Q/M (placement post-evaluation) of per unit mass [(is commented after placement Valency)/(initial evaluation) × 100], and evaluated according to following standards.

(evaluation criterion)

<Evaluate 2：Low-temperature fixability>

Paper：CS-680(68.0g/m²) (can obtain from Canon Marketing Japan Inc.)

Toner bearing capacity：1.20mg/cm²

Evaluation image：By 10-cm²Image is placed into the center of A4 paper

Fixing Test environment：Low temperature and low moisture environments, 15 DEG C/10%RH (hereinafter referred to as " L/L ")

Processing speed：The 450mm/ second

Fixing temperature：130℃

The low-temperature fixability for being fixed image output under these conditions is evaluated using above-mentioned image forming apparatus.

By the value of following image density reduced rates as the index for evaluating low-temperature fixability.

(500 series, by X-Rite Inc. system by using X-Rite color reflective densitometer for image color reduced rate Make), and be first fixed the concentration of image in measuring center portion to determine.Then, by 4.9kPa (50g/cm²) load applies to measurement The part of the concentration of fixing image, is wiped with the paper of cleaning camera lens and is fixed image (reciprocal 5 times), and measures fixing image again Concentration.Then the reduced rate (%) of image is fixed before and after measurement is wiped.

(evaluation criterion)

<Evaluate 3：Anticaking capacity (bin stability)>

The toner for amounting to 5g is put in 100mL plastic containers, container is placed on variable temperature and humidity Thermostat (set：55 DEG C, 41%RH) in 48h, and evaluate the cohesion after toner is placed.

The evaluation index of cohesion is worked as in the Powder manufactured by Hosokawa Micron Corporation In Tester PT-X, under 0.5-mm amplitude, the residual rate that 20- μm of purpose screens the toner remained during 10s is carried out.

(evaluation criterion)

<Evaluate 4：Heat-resisting biofouling>

Paper：CS-680(68.0g/m²) (can obtain from Canon Marketing Japan Inc.)

Toner bearing capacity：0.08mg/cm²

Evaluation image：By 10-cm²Image is placed into the two ends of A4 paper

Fixing Test environment：Normal temperature and low moisture environments, 23 DEG C/5%RH (hereinafter referred to as " N/L ")

Processing speed：The 450mm/ second

Fixing temperature：210℃

10 common paper postcards of total are made by the center of the fixing band of the fixing device of image forming apparatus, above-mentioned Under the conditions of output be fixed image, and using fixing image rise haze value as heat-resisting biofouling evaluation index.

By using reflectometer, (" REFLECTOMETER MODEL TC-6DS ", by Tokyo Denshoku Co., Ltd. Manufacture), the average reflectance Dr (%) of paper and the reflectivity of white background portions after Fixing Test is evaluated before measuring image reproducing Ds (%), and hazed using following formula calculating.According to hazing obtained by following evaluation criterion evaluations.

Haze (%)=Dr (%)-Ds (%)

(evaluation criterion)

[table 4]

In embodiment 1, chargeding performance, low-temperature fixability, anticaking capacity and heat-resisting biofouling it is entirely.

In example 2, as toner-particle is heat-treated, thus compared with Example 1, wax and dispersing agent for wax Do not migrate to toner-particle surface, anticaking capacity somewhat reduces.

In embodiment 3, as the preparation method of toner-particle is emulsification aggregation method, thus the dispersiveness of wax somewhat drops Low and heat-resisting biofouling reduction.

In example 4, as the acid number of dispersing agent for wax increases to 60 (mg KOH/g) from 30 (mg KOH/g), thus with Embodiment 3 is compared, and hydrophobicity reduces, and chargeding performance somewhat reduces.

In embodiment 5, as the acid number for making dispersing agent for wax is 0, thus compared with Example 3, the dispersiveness reduction of wax Biofouling somewhat reduce with heat-resisting.

In embodiment 6, as the addition of crystalline polyester resin is reduced to 5.0 mass parts, thus crystallization is reduced The plasticization effect of property polyester resin and toner-particle hardening.As a result, compared with Example 5, low-temperature fixability reduces and resistive connection Block increases.

In embodiment 7, as the addition of crystalline polyester resin increases to 15.0 mass parts, thus crystallization is enhanced Property the plasticization effect of polyester resin and toner-particle soften.As a result, compared with Example 5, low-temperature fixability strengthens and resistive connection Block reduces.

In embodiment 8, as the addition of crystalline polyester resin is reduced to 1.0 mass parts, thus crystallization is reduced Property polyester resin plasticization effect, compared with Example 5 low-temperature fixability reduce, and anticaking capacity strengthen.

In embodiment 9, the type of crystalline polyester resin is become by the glycol that carbon number is 6 and dicarboxylic acids that carbon number is 12 Carbon number is 12 glycol and dicarboxylic acids that carbon number is 6, but the plasticization effect of crystalline polyester resin is not changed in.However, SP2- The value of SP1 becomes 1.4, and the difference of solubility parameter increases, and does not improve the compatibility of crystalline polyester resin and dispersing agent for wax, and Compared with Example 8, dispersion of the wax in toner-particle is somewhat deteriorated.As a result, heat-resisting biofouling reduction.

In embodiment 10, the type of crystalline polyester resin is become the glycol that carbon number is 10 and the dicarboxyl that carbon number is 10 Acid.As a result, the plasticization effect of crystalline polyester resin somewhat reduces and reduces with low-temperature fixability.

In embodiment 11, the type of crystalline polyester resin is become the glycol that carbon number is 6 and the dicarboxyl that carbon number is 10 Acid.As a result, the plasticization effect of crystalline polyester resin strengthens and low-temperature fixability increases.Additionally, the value of SP2-SP1 becomes 1.5, The difference of solubility parameter increases, and does not improve the compatibility of crystalline polyester resin and dispersing agent for wax, and compared with Example 8, Dispersion of the wax in toner-particle is somewhat deteriorated.As a result, heat-resisting biofouling reduction.

In embodiment 12, the type of crystalline polyester resin is become the glycol that carbon number is 6 and the dicarboxyl that carbon number is 10 Acid, and its addition increases to 16.0 mass parts.As a result, the plasticization effect of crystalline polyester resin strengthens, and toner-particle becomes Soft, and low-temperature fixability increase.However, anticaking capacity and heat-resisting biofouling reduction.

In embodiment 13, the type of crystalline polyester resin is become the glycol that carbon number is 6 and the dicarboxyl that carbon number is 4 Acid, and its addition increases to 16.0 mass parts.As a result, the plasticization effect of crystalline polyester resin strengthens, and toner-particle becomes Soft, and low-temperature fixability increase.However, anticaking capacity and heat-resisting biofouling reduction.

In embodiment 14, without crystalline polyester resin.As a result, anticaking capacity increases, but low-temperature fixability reduces.

In embodiment 15, the weight average molecular weight for making dispersing agent for wax is 70,000.Therefore, dispersing agent for wax is unlikely is adjusting Move in toner particles.As a result, the dispersiveness reduction of wax, and compared with embodiment 14, heat-resisting biofouling reduction.

In embodiment 16, the weight average molecular weight for making dispersing agent for wax is 5000.Therefore, dispersing agent for wax easily can adjusted Move in toner particles, compared with embodiment 14, wax somewhat increases to oozing out for toner-particle surface, and chargeding performance is somewhat Reduce.

In embodiment 17, the weight average molecular weight for making dispersing agent for wax is 80,000.Therefore, it is dispersed in toner-particle Wax is unlikely during fixing and melting promptly to be migrated to toner-particle surface, heat-resisting biofouling reduction.

In embodiment 18, the weight average molecular weight for making dispersing agent for wax is 4000.Therefore, dispersing agent for wax easily can adjusted Move in toner particles, compared with embodiment 14, wax somewhat increases to oozing out for toner-particle surface, anticaking capacity and powered Performance reduces.

In embodiment 19,20 and 21, it is 90 DEG C that hydrocarbon compound is respectively become the fischer-tropsch wax, fusing point that fusing point is 105 DEG C Fischer-tropsch wax and paraffin that fusing point is 77 DEG C.As a result, compared with the polyacrylic embodiment 18 for using fusing point being 90 DEG C, wax Dispersiveness reduces and heat-resisting biofouling also reduces.

In embodiment 22,23,24 and 25, the composition of styrene-acrylic is respectively become acryllic acid different Butyl ester, 2-EHA, ethyl acrylate and methyl acrylate.As a result, the glass transition temperature of toner-particle (Tg) reduction reduces, and low-temperature fixability reduces.

In embodiment 26,27,28,29 and 30, by saturation alicyclic compound respectively become methacrylic acid cycloheptyl ester, Methacrylic acid ring monooctyl ester, methacrylic acid ring pentyl ester, methacrylic acid ring butyl ester and methacrylic acid ring propyl ester.As a result, exist In embodiment 26 and 27, the hydrophobicity of toner-particle reduces, and therefore chargeding performance reduces.Additionally, in embodiment 28 and 29 In, the hydrophobicity of toner-particle reduces further and reduces with chargeding performance.In embodiment 30, hydrophobicity reduce further and Chargeding performance reduces.Additionally, in embodiment 29 and 30, the circulus of saturation alicyclic compound is little.As a result, dispersing agent for wax Easily can move with wax, wax is to the increase of oozing out on toner-particle surface, and anticaking capacity reduces.

In comparative example 1, toner-particle is prepared so that toner-particle includes crystalline polyester resin, but dispersing agent for wax Saturation alicyclic compound is not included.As a result, although low-temperature fixability is improved by the plasticization effect of crystalline polyester resin, but Chargeding performance and anticaking capacity are in the unacceptable level of the present invention.

In comparative example 2, toner-particle is prepared, wherein dispersing agent for wax does not include saturation alicyclic compound.Therefore, carry Electrical property, anticaking capacity and low-temperature fixability are in the unacceptable level of the present invention.

In comparative example 3, dispersing agent for wax is not used.As a result, wax does not disperse, chargeding performance, low-temperature fixability, agglomeration resistance Property and heat-resisting biofouling it is in the unacceptable level of the present invention.

Although describe the present invention by reference to exemplary embodiment, it should be understood that the present invention be not limited to disclosed Exemplary embodiment.Scope of the following claims should give most wide explanation, to include all such modifications and wait Same 26S Proteasome Structure and Function.

Claims (12)

1. a kind of toner dispersing agent for wax, it is characterised in which includes by by styrene-acrylic glycerol polymerization The polymer obtained on hydrocarbon compound,

Wherein, the styrene-acrylic has the structure position from saturation alicyclic compound.

2. toner dispersing agent for wax according to claim 1, wherein described styrene-acrylic have by under The monomeric unit that formula (1) represents：

Wherein R₁Represent hydrogen atom or methyl；R₂Represent saturation alicyclic group.

3. toner dispersing agent for wax according to claim 1 and 2, wherein described styrene-acrylic have The monomeric unit represented by following formula (2)：

Wherein R₃Represent hydrogen atom or methyl；N represents at least 1 and no more than 18 integer.

4. toner dispersing agent for wax according to claim 1 and 2, is wherein passing through the toner dispersing agent for wax In the molecular weight distribution that gel permeation chromatography is determined, weight average molecular weight is at least 5000 and no more than 70,000.

5. a kind of toner, it is characterised in which includes

Containing resin glue, wax and by by styrene-acrylic glycerol polymerization to hydrocarbon compound obtain The toner-particle of polymer,

Wherein, the styrene-acrylic has the structure position from saturation alicyclic compound.

6. toner according to claim 5, wherein described styrene-acrylic have and are represented by following formula (1) Monomeric unit：

Wherein R₁Represent hydrogen atom or methyl；R₂Represent saturation alicyclic group.

7. the toner according to claim 5 or 6, wherein described styrene-acrylic have by following formula (2) table The monomeric unit for showing：

Wherein R₃Represent hydrogen atom or methyl, n represents at least 1 and no more than 18 integer.

8. the toner according to claim 5 or 6, wherein by means of styrene-acrylic to be grafted It is aggregated in the molecular weight distribution of gel permeation chromatography measure of the polymer obtained on hydrocarbon compound, weight average molecular weight is At least 5000 and no more than 70,000.

9. the toner according to claim 5 or 6, wherein described resin glue is comprising crystalline polyester resin and non-knot Crystalline substance polyester resin.

10. toner according to claim 9, wherein described crystalline polyester resin by include selected from carbon number be to Few 6 and the alkoxide component of at least one compound of the group of no more than 12 aliphatic diol and its derivative composition be selected from including The carboxylic acid of at least one compound of the group being made up of the aliphatic dicarboxylic acid that carbon number is at least 6 and no more than 12 and its derivative The polycondensation of component and obtain, and

Based on non-crystalline polyester resin described in every 100.0 mass parts, the amount of the crystalline polyester resin is at least 1.0 mass Part and no more than 15.0 mass parts.

11. toners according to claim 9, the solubility parameter SP1 of wherein described crystalline polyester resin and pass through By in styrene-acrylic glycerol polymerization to hydrocarbon compound obtain polymer solubility parameter SP2 meet by The relation that following formula (3) represents：

0≤SP1-SP2≤1.3 formula (3).

12. toners according to claim 5 or 6, wherein pass through by styrene-acrylic glycerol polymerization to hydrocarbon The acid number of the polymer obtained on compound is at least 5mg KOH/g and no more than 50mg KOH/g.