CN100504628C - Polyester resin for toner, toner composition - Google Patents

Abstract

Disclosed is a heat-fusible electrostatic image developing toner which has an excellent balance between fixability at low temperatures and grindability and is excellent in glossiness after fixation. Also disclosed is a resin for toners. A polyester resin for toners which is obtained by polycondensing a polyol component and a polycarboxylic acid component is characterized by containing 20-100 weight% of one or more polyester resins (A1) having a storage elastic modulus from 2.5 x 10<3> Pa to 5 x 10<6> Pa at 150 1/2 C wherein the molar average cohesive energy of the polyol component is between 7.0 x 10<4> and 1.4 x 10<5> J.

Description

Polyester resin for toner and method for producing toner and toner

Technical field

The present invention relates to be used for the resin for toner and the method for producing toner and toner of electrofax, electrostatic recording and xeroprinting.

In addition, the invention still further relates to resin particle.In more detail, the present invention relates to be used for the resin particle of various uses, described purposes for example: slush molding is with resin, powdery paints, electrofax tinter, electrostatic recording toner, xeroprinting toner or hot melt adhesive.

Background technology

Even the toner for developing electrostatic image that uses in hot fixation method is required also can not melted by hot-rolling (heat-resistant inks contamination property under high fixing temperature, hot offset resistance) and even can under low fixing temperature, carry out photographic fixing (low-temperature fixing characteristic), also require the comminuted good of when the preparation toner its resin.The comminuted of resin was to tend to the characteristic of opposition mutually when usually, low-temperature fixing characteristic and toner were made.Have excellent low-temperature fixing characteristic and when toner is made, have the smashing toner of good resin as a kind of, existing document discloses the toner that contains following resin for toner, and it is that 10～24 unit price fatty compound is as monomer component (referring to Patent Document 1) that described resin contains carbon number with specified quantitative.

And, satisfy the low-temperature fixing characteristic and do not produce high temperature ink in order to attempt to provide a kind of

Dirty toner, existing document discloses a kind of toner, its loss modulus is at G "=1 * 10 ⁴Pa～1 * 10 ⁶During the Pa scope, loss tangent tan δ is more than or equal to 1.0 and be lower than 2.0 scope, and loss modulus is at G "=1 * 10 ³During Pa, loss tangent tan δ is more than or equal to 0.5 and be lower than 1.0 scope (referring to Patent Document 2).

Yet,, but still be necessary its low-temperature fixing characteristic and comminuted the improvement to realize high speed and energy conservation characteristic although the toner of mentioning in documents 1 has excellent low-temperature fixing characteristic.Equally, the toner of mentioning in documents 2 has good low-temperature fixing characteristic and high temperature ink and stains characteristic, yet also is not enough to obtain the picture quality of being satisfied with when it needing to be used for the coloured image of glossiness.

For moisture-proof and the fixing performance that improves polyester toner, knownly can carry out cocondensation, thereby long-chain fat family hydrocarbon unit be introduced in the main chain or side chain of vibrin (referring to Patent Document 3) by the dicarboxylic acid that makes ternary or the polyvalent alcohol more than the ternary and long-chain fat family dicarboxylic acid or have a long-chain fat family side chain.

Yet, in these vibrin, because use decanedioic acid etc. have the dicarboxylic acid of long-chain fat family side chain as conducts such as long-chain fat family dicarboxylic acid, use dodecylene succinic acids, thereby the carbon number of the long-chain fat family hydrocarbon unit of being introduced is too high, although this moment, the moisture-proof and the fixing performance of toner improved, but the glass transition temperature of vibrin (Tg) is lowered, and the problem that storage stability worsens appears in toner.

Even the toner for developing electrostatic image that uses in hot fixation method is required also can not melted (heat-resistant inks contamination) by hot-rolling under high fixing temperature; And even can under low fixing temperature, carry out photographic fixing (low-temperature fixing characteristic).In order to prevent that the deep fat China ink from staiing, the use of wax is effectively, and in order to improve the low-temperature fixing characteristic, using polyester resin is effective as the toner bonding agent.

Yet the compatibility of wax and polyester resin is relatively poor, makes that the dispersion particle diameter of wax becomes big in the toner.Therefore cause the set and the film forming and damage picture quality of wax on photoreceptor, perhaps cause charged bad and damage picture quality.In order to address these problems, proposed in the patent documentation 4 to use graft polymer with Grafting Structure, it forms by graft phenylethene type polymer chain or styrene on the wax component-(methyl) acrylate copolymer chain.The particle diameter of the wax in the may command toner thus, thereby the toner that has proposed to have the superior heat resistance offset and can not cause film forming or image degradation.

Yet, be effective although the toner that proposes in the document stains property and do not cause aspect film forming or the image degradation at heat-resistant inks, be not enough from the viewpoint of low-temperature fixing characteristic.

As the particle that has homogeneous particle diameter and shape and have excellent electrical property, thermal property and chemical stability, known have a resin particle that obtains by following suspension method: remove organic solvent (referring to Patent Document 5) from the suspending liquid of aqueous medium and the mixed solution that contains resin and organic solvent.

Yet, for the resin particle that is used for hot fixation method/heat treatment method, from energy-conservation viewpoint, at low temperatures also can photographic fixing and fusing even further require it to be fit to.And the resin particle of describing in patent documentation 5 might not be enough to be used in slush molding resin, powdery paints, electrofax tinter, electrostatic recording toner, xeroprinting toner or hot melt adhesive.

Patent documentation 1:JP-A 2003-337443

Patent documentation 2:JP-A 2003-280241

Patent documentation 3:JP-A 62-78568

Patent documentation 4:JP-A 2001-134009

Patent documentation 5:JP-A 2001-166538

Summary of the invention

One object of the present invention is to provide has excellent low-temperature fixing characteristic and the good resin for toner particle of resin-oatmeal fragility when toner is made.

Another object of the present invention is to provide the particle of the resin for toner with good gloss.

Another object of the present invention is to provide the resin for toner particle, and described resin particle makes toner have good moisture resistance and photographic fixing characteristic, can give the storage stability of toner with excellence simultaneously.

Another object of the present invention is to provide the resin for toner composition, and described composition makes toner have excellent heat-resistant inks contamination property, can not cause image bad, and makes it have excellent low-temperature fixing characteristic.

Further, another object of the present invention is to provide a kind of toner of non-magnetic mono-component type, and this toner has excellent low-temperature fixing characteristic, the resin-oatmeal fragility well and as color toner (color toner) has the fabulous glossiness and the transparency when toner is made.

Further, another object of the present invention is to provide resin particle, and this resin particle has excellent photographic fixing characteristic and heat fusing characteristic and particle diameter and shape homogeneous, and described resin particle obtains by suspension method.

The inventor studies the above-mentioned problem that should solve, thereby has finished the present invention.

Also promptly, the present invention includes following 8 aspects:

[1] a kind of polyester resin for toner, it obtains by making polyol component and polybasic carboxylic acid component carry out polycondensation, it is characterized in that described polyol component has 7.0 * 10 ⁴J～1.4 * 10 ⁵The average cohesive energy (molar average cohesive energy) of the mole of J; Described vibrin comprises at least a vibrin (A1) of 20～100 weight %, and this vibrin (A1) has 2.5 * 10 at 150 ℃ ³Pa～5 * 10 ⁶The storage modulus of Pa.

[2] a kind of polyester resin for toner, it obtains by making polyol component and polybasic carboxylic acid component carry out polycondensation, it is characterized in that, described vibrin comprises at least a vibrin (A2) of 20～100 weight %, the softening point of this vibrin (A2) be 120 ℃～180 ℃ and at 130 ℃～200 ℃ loss tangent more than or equal to 0.9.

[3] a kind of polyester resin for toner (A3), it obtains by making polyol component and polybasic carboxylic acid component carry out polycondensation, it is characterized in that described polybasic carboxylic acid component contains terephthalic acid (TPA), m-phthalic acid and/or their low alkyl group (the alkyl carbon atoms number is 1～4) ester of (a) 80 moles of %～100 mole %; Described polyol component contains the aliphatic diol (80 moles of %～100 mole % in this aliphatic diol are 1, the 2-propylene glycol) of (b) 20 moles of %～100 mole %; 0.1 mole of %～20 mole % of the total amount of polyol component and polybasic carboxylic acid component is the above polyvalent alcohol of (c) ternary or ternary and/or ternary or the above polybasic carboxylic acid of ternary; And the softening point of described vibrin is that 95～160 ℃, glass transition temperature (Tg) are 45～75 ℃.

[4] a kind of polyester resin composition for toner, it contains any described polyester resin for toner and toner adjuvant (B) in above-mentioned [1]～[3], described adjuvant (B) comprises modified waxes (w1), and described modified waxes (w1) is to prepare by utilizing vinyl monomer (m) that at least a portion of wax (w) is carried out modification.

[5] a kind of method for producing toner and toner, it contains any described polyester resin for toner in above-mentioned [1]～[3], and contain colorant, and also containing as required the adjuvant that adds, described adjuvant is selected from least a in release agent, charge control agent and the fluidizing agent.

[6] one non-magnetic mono-component toners, in the formation method that this toner is used to by toner is offered latent image carrier sub-image be developed, it is characterized in that, described toner comprises any described polyester resin for toner (A1) in the claim 1～3, (A2) or (A3), and comprises colorant; If with (A1), (A2) or glass transition temperature (A3) (Tg) as x axle variable, softening point (sp) as y axle variable, when mapping with the xy coordinate, then described toner has by the interior physical characteristics of the defined straight line in following equation (1)～(4) institute area surrounded; And have one or more particulate additives on this toner-particle surface;

Equation (1): sp=4Tg-110,

Equation (2): sp=4Tg-170,

Equation (3): sp=90 and

Equation (4): sp=130.

[7] a kind of resin particle, this resin particle is to obtain by removing to desolvate from the aqueous liquid dispersion of oiliness mixed liquor (I) and aqueous medium (II), the adjuvant that this resin particle comprises resin (K) and adds as required, described oiliness mixed liquor (I) contains resin (K) and organic solvent at least, it is characterized in that, wherein resin (K) comprises at least a vibrin (K1), described vibrin (K1) obtains by making polyol component and polybasic carboxylic acid component carry out polycondensation, and the number-average molecular weight of this resin (K1) solubilized part in tetrahydrofuran is 1000～9500; The carbon number that described polyol component comprises 85 moles of %～100 mole % is 1 of 2～6 aliphatic diol or 70 moles of %～100 mole %, the 2-propylene glycol.

[8] a kind of resin particle, it is characterized in that, this resin particle is the composite resin particle that forms attached to the surface of resin particle (P) by with resin particle (Q), the adjuvant that described resin particle (P) comprises resin (p) and adds as required, the adjuvant that described resin particle (Q) comprises resin (q) and adds as required, described resin (p) comprises at least a vibrin (p1), this vibrin (p1) obtains by making polyol component and polybasic carboxylic acid component carry out polycondensation, the carbon number that wherein said polyol component comprises 85 moles of %～100 mole % is 1 of 2～6 aliphatic diol or 70 moles of %～100 mole %, the 2-propylene glycol, and the number-average molecular weight of this vibrin (p1) solubilized part in tetrahydrofuran is 1000～9500; Perhaps described resin (p) comprises resin (p2), and this resin (p2) contains (p1) as constituting the unit.

Toner with excellent low-temperature fixing characteristic can obtain by using polyester resin for toner and method for producing toner and toner in above-mentioned the 1st, 2 and 5 invention.Further since in toner is produced this resin comminuted also very excellent, thereby can make toner production when commercial production, be able to economic enforcement.Further, because the high temperature ink contamination does not appear 130 ℃～200 ℃ temperature range, thus thereby can make toner surface after photographic fixing, still can keep flatness that glossiness image is provided.

Even the vibrin of mentioning in the 3rd invention also has excellent resistance to blocking, melt fluidity, low-temperature fixing and static characteristic under high humidity.Further, even it still has good resin property under as the situation of catalyzer not using tin compound.

Have excellent heat-resistant inks contamination property by using the polyester and resin composition of mentioning in the 4th invention to obtain, can not cause the toner that image is bad and have excellent low-temperature fixing characteristic.

The toner that uses in the 6th invention shows excellent low-temperature fixing characteristic and as the fabulous glossiness and the transparency of color toner.Further, owing to the comminuted excellence of resin in toner is produced, thereby make toner production when commercial production, be able to economic carrying out.

Resin particle in the 7th and the 8th invention has following effect:

1. You Yi watery fusion and low-temperature fixing characteristic, thus when melt-processed and printing, can reduce energy consumption;

2. uniform particle diameter, powder fluidity excellence, bin stability excellence;

3. can obtain by being dispersed in the water owing to it, thereby realize the low cost of preparation;

4. good, the filming of heating and melting of thermotolerance also has the favorable mechanical performance.

Description of drawings

Fig. 1 is the glass transition temperature (Tg) of explanation vibrin of the present invention and the figure of the relation between the softening point (sp).

Embodiment

To be explained in detail the present invention hereinafter.

In the 1st invention, be generally 7.0 * 10 as the average cohesive energy of mole of the polyol component of the constituent of vibrin (A1) ⁴J～1.4 * 10 ⁵J.Its lower limit is preferably 7.05 * 10 ⁴J, more preferably 7.1 * 10 ⁴J.The upper limit is preferably 1.25 * 10 ⁵J, more preferably 1 * 10 ⁵J.If the average cohesive energy of mole is more than or equal to 7.0 * 10 ⁴J, then resin has good heat-resisting keeping quality (heatresistant storage property), if the average cohesive energy of mole is smaller or equal to 1.4 * 10 ⁵J, then comminuted excellence.

The vibrin (A1) that is made of the polyvalent alcohol with the average cohesive energy of above-mentioned mole has 2.5 * 10 in the time of 150 ℃ ³Pa～5 * 10 ⁶The storage modulus of Pa.Lower limit is preferably 3 * 10 ³Pa, more preferably 3.2 * 10 ³Pa, the upper limit is preferably 4.5 * 10 ⁶Pa, more preferably 4.3 * 10 ⁶Pa.If storage modulus is 2.5 * 10 ³Pa or higher, then resin has good heat-resistant inks contamination property, if storage modulus is 5 * 10 ⁶Pa or lower, then low-temperature fixing excellent.

Using under the situation of two or more polyvalent alcohols, the amount of the polyvalent alcohol that the amount of the formation molar ratio of each polyvalent alcohol by employed polyvalent alcohol reclaimed during with reaction is calculated and is tried to achieve.

About the average cohesive energy of mole, corresponding description is arranged in following document: people such as Fedors, Polymer Engineering and Science, February, 1974, vol.14, No.2,147-154 page or leaf.

Because cohesive energy is an eigenvalue to each polyvalent alcohol, in order to regulate a mole average cohesive energy, should control the mol ratio of polyvalent alcohol.In order to regulate the storage modulus of resin, for example, should regulate the molecular weight of resin and the quantity of crosslinking points.

Vibrin (A3) in vibrin (A2) in the 2nd invention that after this vibrin (A1) in the 1st invention is preferably described and/or the 3rd invention.

The softening point of the vibrin (A2) among the 2nd of the present invention is usually at 120～180 ℃.Lower limit is preferably 125 ℃, more preferably 130 ℃, and the upper limit is preferably 175 ℃.If softening point is 120 ℃ or higher, then the heat-resistant inks of resin contamination property is improved, if softening point is 180 ℃ or lower, then the low-temperature fixing characteristic improves.

Except as otherwise noted, the softening point among the present invention is to measure under constant heatingrate's condition as described below by the flow tester CFT-500 that Tianjin, island company makes, and is that 1/2 o'clock temperature is as softening point with discharge.

Load: 20kg

Nib: 1mm φ-1mm

Programming rate: 6 ℃/min.

The loss tangent of resin (A2) when temperature is 130～200 ℃ be generally more than or equal to 0.9, be preferably more than equal 1.0, more preferably more than or equal to 1.02, more preferably 1.05～30, most preferably be 1.1～20.Along with loss tangent can make glossiness be improved more than or equal to 0.9.

For softening point and the loss tangent of regulating resin, for example, need the molecular weight of corresponding adjusting resin and the quantity of crosslinking points.

The storage modulus of vibrin and loss tangent are to measure by elastic modulus measurement mechanism as described below among the present invention:

Device: ARES-24A (Rheometric Ltd.),

Instrument: the 25mm parallel-plate,

Frequency: 20Hz,

Rate of strain: 5% and

Programming rate: 5 ℃/min.

Draw the curve of displays temperature-loss tangent relation by measured value, by reading the loss tangent of temperature when being 130～200 ℃ in this curve map.

Vibrin (A2) among the 2nd of the present invention is the vibrin (A3) among the 3rd of the vibrin (A1) in the 1st invention and/or the present invention of after this describing preferably.

Used vibrin (A1) and vibrin (A2) obtained by polycondensation by at least a polyol component and at least a polybasic carboxylic acid component usually in the present invention the 1st and the 2nd.

Being used for resin (A1) or polyol component (A2), to be preferably the carbon number that comprises 30～100 moles of % be 2～6 aliphatic diol.Further, contain 1, the 2-propylene glycol to small part in the preferred diol.In the polyol component carbon number be 2～6 aliphatic diol content range more preferably 70～100 moles of %, more preferably 85～100 moles of %, again be preferably 90～100 moles of %, most preferably be 100 moles of %.When this content during more than or equal to 30 moles of %, the intensity of resin is improved, the low-temperature fixing characteristic is improved.

Carbon number is that the example of 2～6 aliphatic diol has: such as ethylene glycol, 1,2-propylene glycol, 1, ammediol, 1,4-butylene glycol, 2,3-butylene glycol, 1,5-pentanediol, 2,3-pentanediol, 1,6-hexanediol, 2,3-hexanediol, 3, alkanediol such as 4-hexanediol, neopentyl glycol and above-mentioned two or more combination.Wherein, be preferably ethylene glycol, 1,2-propylene glycol and neopentyl glycol, ethylene glycol and 1 more preferably, the 2-propylene glycol further is preferably 1, the 2-propylene glycol.

The preferred polyol component comprises 1 of 30～100 moles of %, and other carbon number of 2-propylene glycol and 0～30 mole of % is 2～6 aliphatic diol.In this case, contained 1 in the polyol component, the amount of 2-propylene glycol be preferably 70～100 moles of %, more preferably 85～100 moles of %, more preferably 90～100 moles of %, most preferably be 100 moles of %.When this content during more than or equal to 30 moles of %, the intensity of resin is improved, the low-temperature fixing characteristic is improved.

Also can contain the polyvalent alcohol except that carbon number is 2～6 aliphatic diol in the polyol component.

In described polyvalent alcohol, the example of dibasic alcohol (glycol) can comprise aliphatic diol with 7～36 carbon atoms (for example, 1,7-heptandiol and dodecyl glycol); Polyalkylene glycol ethers (for example, diethylene glycol, dipropylene glycol, polyglycol, polypropylene glycol) with 4～36 carbon atoms; Oxyalkylene (being abbreviated as AO hereinafter) [for example, ethylene oxide (being abbreviated as EO hereinafter), propylene oxide (being abbreviated as PO hereinafter) and butylene oxide] and addition product (the addition molal quantity is 2～30) with 2～4 carbon atoms with aliphatic diol of 2～6 and 7～36 carbon atoms; Alicyclic diol (for example, the bisphenol-A of 1,4 cyclohexane dimethanol, hydrogenation) with 6～36 carbon atoms; Carbon number is 2～4 the AO and the addition product (the addition molal quantity is 2～30) of alicyclic diol; Carbon number is 2～4 the AO and the addition product (the addition molal quantity is 2～30) of bis-phenol (for example, bisphenol-A, Bisphenol F, bisphenol S).

In polyvalent alcohol, the example of 3 yuan to 8 yuan or more polynary alcohol comprises: carbon number is 3～36 3 yuan to 8 yuan or more polynary alcohol (for example, glycerine, trihydroxyethyl ethane, trimethylolpropane, pentaerythrite, sorbierite, 1,2,4-butantriol, 2-methyl isophthalic acid, 2,3-glycerine, 2-methyl isophthalic acid, 2,4-butantriol, 1,2,5-penta triol and 1,3,5-trihydroxy methyl benzene); Have the AO of 2～4 carbon atoms and the addition product of above-mentioned aliphatic polyol (the addition molal quantity is 2～30); Have the AO of 2～4 carbon atoms and the addition product (the addition molal quantity is 2～30) of trisphenol (for example, trisphenol PA); Addition product (the addition molal quantity is 2～30) with the AO of 2～4 carbon atoms and novolac resin (for example], phenol novolac resin and cresols novolac resin, average degree of polymerization are 3～60).

Preferred example is polyalkylene glycol ethers, alicyclic diol, AO with 2～4 carbon atoms and the addition product with the addition product of the alicyclic diol of 6～36 carbon atoms, the AO with 2～4 carbon atoms and bis-phenol with 4～36 carbon atoms, has the AO of 2～4 carbon atoms and the addition product of novolac resin in the above-mentioned polyvalent alcohol; Preferred example is AO (EO and PO) with 2～3 carbon atoms with the addition product of bis-phenol, has the AO (EO and PO) of 2～3 carbon atoms and the addition product of novolac resin.

In the polybasic carboxylic acid component, the example of aliphatics (comprising alicyclic) dicarboxylic acid comprises: the alkane dicarboxylic acid with 2～50 carbon atoms (for example, oxalic acid, malonic acid, succinic acid, hexane diacid, azelaic acid, decanedioic acid) and have the chain docosene dicarboxylic acid (for example, alkenyl succinic, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid and glutaconic acid such as dodecylene succinic acid) of 4～50 carbon atoms.

The example of aromatic dicarboxylic acid comprises the aromatic dicarboxylic acid (for example, phthalic acid, m-phthalic acid, terephthalic acid (TPA) and naphthalene dicarboxylic acids) with 8～36 carbon atoms.

In the polybasic carboxylic acid component, the example of 3 yuan to 6 yuan or more polynary aliphatics (comprising alicyclic) polybasic carboxylic acid comprises: the alicyclic tricarboxylic acid with 6～36 carbon atoms (for example, oneself three acid), the polyvinyl [the number-average molecular weight Mn that records by gel permeation chromatography (GPC) is 450～10000] (for example, alpha-olefin/maleic acid) of unsaturated carboxylic acid.

In the polybasic carboxylic acid component, the example of 3 yuan to 6 yuan or more polynary aromatic series polybasic carboxylic acid comprises the aromatic series polybasic carboxylic acid (trihemellitic acid and pyromellitic acid) with 9～20 carbon atoms, the ethene polymers [Mn:450～10000] (for example, styrene/maleic acid, styrene/acrylic acid co-polymer and styrene/fumaric acid multipolymer) of unsaturated carboxylic acid.

The acid anhydrides of these polybasic carboxylic acids and low alkyl group (having 1～4 carbon atom) ester (as methyl esters, ethyl ester, isopropyl ester) can be used as the polybasic carboxylic acid component equally.

In these polybasic carboxylic acid components, preferred example comprises: have 2～50 carbon atoms the alkane dicarboxylic acid, have 4～50 carbon atoms the chain docosene dicarboxylic acid, have 8～20 carbon atoms aromatic dicarboxylic acid, have the aromatic series polybasic carboxylic acid of 9～20 carbon atoms; More preferably hexane diacid, alkenyl succinic, terephthalic acid (TPA), m-phthalic acid, maleic acid, fumaric acid, trihemellitic acid, pyromellitic acid, and the combination of these acid with 16～50 carbon atoms; Be preferably hexane diacid, terephthalic acid (TPA), trihemellitic acid again, and the combination of these acid.Acid anhydrides that these are sour and lower alkyl esters are preferred too.

Further, as the polybasic carboxylic acid component, preferably contain the carboxylic acid of the content of aromatic series polybasic carboxylic acid and alicyclic polybasic carboxylic acid and aromatic series polybasic carboxylic acid more than or equal to 60 moles of %.The lower limit of aromatic series polybasic carboxylic acid content is 70 moles of %, 80 moles of % more preferably more preferably, and the upper limit is preferably 99 moles of %, 98 moles of % more preferably.When the content of aromatic series polybasic carboxylic acid during more than or equal to 60 moles of %, the intensity of resin is improved, and the low-temperature fixing characteristic further is improved simultaneously.

Polyester resin for toner (A3) among the 3rd of the present invention obtains by making one or more polyol components and one or more polybasic carboxylic acid components carry out polycondensation.Wherein said polybasic carboxylic acid component contains terephthalic acid (TPA), m-phthalic acid and/or their low alkyl group (the alkyl carbon atoms number is 1～4) ester of (a) 80～100 moles of %; Described polyol component contains the aliphatic diol (80～100 moles of % in this aliphatic diol are 1, the 2-propylene glycol) of (b) 20～100 moles of %; 0.1～20 mole of % of the total amount of polyol component and polybasic carboxylic acid component is the above polyvalent alcohol of (c) ternary or ternary and/or ternary or the above polybasic carboxylic acid of ternary.

Vibrin (A3) among the 3rd of the present invention is the vibrin (A2) in the vibrin (A1) among the 1st of the present invention and/or the 2nd invention preferably also.

Above-mentioned (a) means terephthalic acid (TPA), m-phthalic acid and/or their low alkyl group (the alkyl carbon atoms number is 1～4) ester, and wherein low alkyl group (the alkyl carbon atoms number is 1～4) ester comprises hydroxy alkyl ester.

The concrete example of lower alkyl esters is dimethyl terephthalate (DMT), dimethyl isophthalate, diethyl terephthalate, dimethyl isophthalate, dibutyl terephthalate, m-phthalic acid dibutyl ester, terephthalic acid (TPA) propylene glycol diesters and m-phthalic acid propylene glycol diesters, in (a), consider reaction velocity and expense, be preferably terephthalic acid (TPA), m-phthalic acid, dimethyl terephthalate (DMT), dimethyl isophthalate, terephthalic acid (TPA) propylene glycol diesters and m-phthalic acid propylene glycol diesters.

Because component (a) has the effect of the vibrin glass transition temperature (hereinafter being called Tg) that increase obtains, thereby improved the resistance to blocking of toner, thus its content based on whole polybasic carboxylic acid components be generally 80～100 moles of %, be preferably 85～100 moles of %, 90～100 moles of % more preferably.

In the polybasic carboxylic acid component that constitutes vibrin, available dicarboxylic acids example except that (a) has: aforesaid alkane dicarboxylic acid with 2～50 carbon atoms, have the chain docosene dicarboxylic acid of 4～50 carbon atoms, the aromatic binary carboxylic acid with 8～36 carbon atoms except that (a) (for example, naphthalene diacid); And the acid anhydrides of above-mentioned dicarboxylic acids and low alkyl group (carbon number is 1～4) ester [for example, phthalic acid (acid anhydride)].They can be separately or at least two kinds be used in combination.

In the 3rd invention, aliphatic diol (b) comprises aforementioned aliphatic diol with 2～6 carbon atoms, has the aliphatic diol of 7～36 carbon atoms, has the polyalkylene glycol ethers of 4～36 carbon atoms; Carbon number is 2～4 AO and the addition product with aliphatic diol of 2～6 and 7～36 carbon atoms; Carbon number is 3～36 alicyclic diol; Carbon number is 2～4 the AO and the addition product of described alicyclic diol.They can be separately or at least two kinds be used in combination.

Particularly considering the balance between the interdependent characteristic of toner fixing characteristic and environment, is 1 more than or equal to 80 moles of % in the preferred employed aliphatic diol, the 2-propylene glycol.Other aliphatic diol is preferably ethylene glycol, 1,4-butylene glycol, neopentyl glycol and 1,4 cyclohexane dimethanol.Because these dibasic alcohol as (b) produce effect for the melt viscosity that reduces vibrin, thereby improved the photographic fixing characteristic of toner.Its content range is preferably 20～100 moles of %, 45～100 moles of % more preferably based on whole polyol components, further is preferably 60～100 moles of %, most preferably is 70～100 moles of %.When (b) content during, can make toner have good photographic fixing characteristic and can suppress the reduction of its moisture-proof more than or equal to 20 moles of %.

As the polyol component that constitutes vibrin, wherein can to exemplify out aforementioned carbon number be 2～4 the AO and the addition product of bis-phenol to the dibasic alcohol except that (b).

As the 3rd employed ternary of the present invention or more than the polyvalent alcohol of ternary (3 yuan to 8 yuan or more polynary) and/or ternary or more than the polybasic carboxylic acid (c) of ternary (3 yuan to 8 yuan or more polynary), for example can enumerate: foregoing 3 yuan to 8 yuan or more polynary aliphatic polyol with 3～36 carbon atoms; Have the AO of 2～4 carbon atoms and the addition product of above-mentioned aliphatic polyol; Have the AO of 2～4 carbon atoms and the addition product of above-mentioned trisphenol; Have the AO of 2～4 carbon atoms and the addition product of above-mentioned novolac resin; Aliphatics tricarboxylic acid with 6～36 carbon atoms; The polyvinyl of above-mentioned unsaturated carboxylic acid; Carbon number is 9～20 3 yuan to 6 yuan or the more polynary aromatic series polybasic carboxylic acid of having; And the polyvinyl of above-mentioned unsaturated carboxylic acid.

Wherein preferred example is: have the AO of 2～4 carbon atoms and the addition product of novolac resin (average addition molal quantity is 2～30); Carbon number is 9～20 3 yuan to 6 yuan or more polynary aromatic series polybasic carboxylic acid (trihemellitic acid and pyromellitic acid); Preferred example is AO (particularly EO and/or PO) with 2～4 carbon atoms and the addition product (average addition molal quantity is 2～30) of novolac resin.These compounds can be separately or at least two kinds be used in combination.These compounds (c) have been given play to the effect of the anti-offset that improves toner by making the crosslinked or branching of vibrin.

The content of compound (c) is preferably 0.1～20 mole of %, 0.5～18 mole of % more preferably based on whole polyol components and polybasic carboxylic acid component.When this content is controlled in more than or equal to 0.1 mole of %, can accesses viscosity and Tg and be fit to the vibrin of scope separately, thereby make the anti-offset and the bin stability of toner be met.When content was controlled in smaller or equal to 20 moles of %, it was crosslinked to prevent that in the scope that is less than or equal to above-mentioned suitable viscosity vibrin from carrying out, thus the scope that can widen no offset.

In a third aspect of the present invention, under the condition of not damaging the vibrin characteristic,, can use other monomer smaller or equal to 10 moles of % with respect to the total amount of polyol component and polybasic carboxylic acid component.Described other monomer is for example: monocarboxylic acid such as benzoic acid, contraposition substituted benzoic acid, ortho position substituted benzoic acid, acetate, propionic acid, butyric acid, and their methyl esters and ethyl ester and acid anhydrides; Monohydroxy alcohol such as phenmethylol, contraposition substituted benzyl alcohol, ortho position substituted benzyl alcohol, lauryl alcohol, myristyl alcohol and octadecanol; And alpha-hydroxy carboxylic acid derivatives such as 6-caprolactone, methylpent lactone and its ring-opening polymerization polymer.

The vibrin of third aspect present invention obtains by the said components polycondensation, its softening point generally 95～160 ℃, be preferably 100 ℃ of the lower limits and 150 ℃ of the upper limits, more preferably be lower than 120 ℃, its Tg generally 45～75 ℃, be preferably 70 ℃ of 50 ℃ of lower limits and the upper limits.

If softening point is controlled in more than or equal to 95 ℃, then vibrin can obtain good toughness; On the other hand, if softening point is controlled in smaller or equal to 160 ℃, then toner can obtain desirable melt flow characteristics and low-temperature fixing characteristic.

If Tg is controlled in more than or equal to 45 ℃, then toner has good resistance to blocking; If Tg is controlled in smaller or equal to 75 ℃, then toner will obtain desirable photographic fixing characteristic.

Tg measures by the DSC method of stipulating among the ASTM D3418-82, and used measuring equipment is: DSC20, and SSC/580, Seiko Instruments Inc produces.

Vibrin among the present invention (A1)～(A3) can obtain by the preparation process of polyester of routine.For example, can be in inert gas (for example, nitrogen etc.), temperature of reaction be preferably 150～280 ℃, more preferably 160～250 ℃, more preferably 170～235 ℃ implement preparation down.Consider the reliability that polycondensation is carried out, the reaction time be preferably 30 minutes or longer, be preferably 2 hours～40 hours especially.

In this case, if necessary can use esterification catalyst.The example of esterification catalyst have tin-containing catalyst (as, Dibutyltin oxide, dioctyl tin oxide, two lauric acid dioctyl tins), antimony-containing catalyst (as, antimony oxide), titanium-containing catalyst (as, alkyl dioxide, titanyl ethane diacid potassium (potassium titanyl oxalate), terephthalic acid (TPA) titanium), zirconium-containing catalyst (as, zirconyl acetate), nickel-containing catalyst (as, acetoacetate nickel), contain Al catalysts (as, aluminium hydroxide and aluminum isopropylate), zinc acetate, manganese acetate.Wherein, consider reaction capacity and environmental health, preferably contain the metal that one or more are selected from titanium, antimony, zirconium, nickel and aluminium in the catalyzer.It also is effective improving reaction velocity at end reaction stage reduction pressure.

The suitable addition of preferred definite catalyzer is to obtain maximum reaction velocity.The content of addition in whole raw materials is preferably 10ppm～1.9%, 100ppm～1.7% more preferably.If addition more than or equal to 10ppm, is preferred therefore owing to increased reaction velocity.Hereinafter except as otherwise noted, " % " is weight %.

In the situation of the vibrin (A1) to (A3) [(A1) being collectively referred to as (A) hereinafter] for preparing the 1st～the 3rd of the present invention to (A3), the reactive ratio of polyol component and polycarboxylic acid component is preferably 2:1～1:2 based on equivalent proportion [OH]/[COOH] of hydroxyl and carboxyl, more preferably 1.5:1～1:1.3, more preferably 1.3:1～1:1.2.

The Mn of resin (A) solubilized part in tetrahydrofuran (THF) is preferably 1000～9500, more preferably 1200～9300, more preferably 1400～9100.If Mn is more than or equal to 1000, then mechanical strength of resin is improved; If Mn is smaller or equal to 9500, the then low-temperature fixing of resin and comminuted improving.

Consider resin intensity, low-temperature fixing and comminuted between balance, the peak molecular weight (hereinafter being called Mp) of resin (A) solubilized part in tetrahydrofuran (THF) is preferably 1200～50000, more preferably 1500～40000.

The resin (A) that obtains by gel permeation chromatography (GPC) in tetrahydrofuran (THF) in the solubilized chromatogram partly, molecular weight smaller or equal to 500 components contents be preferably smaller or equal to 3%, more preferably smaller or equal to 2.5%.If smaller or equal to 3%, then with resin (A) when being used for toner, its flowability further improves molecular weight smaller or equal to 500 component concentration in the resin (A), the stability of image also is improved when printing continuously simultaneously.When using two or more resin as resin (A), even molecular weight is many smaller or equal to 500 component concentration in the resin, also still preferably in all resins (A) its content in above-mentioned scope.

Mn, Mp of soluble composition in tetrahydrofuran (THF) that has in the resin and molecular weight adopt the GPC method to record under the following conditions smaller or equal to 500 components contents.

Device: HLC-8120, Tosho Co., Ltd. system

Cylinder: TSK GEL GMH6 post, 2, Tosho Co., Ltd. system

Measure temperature: 40 ℃

Sample solution: 0.25% THF solution

Solution injection rate IR: 100 μ L

Pick-up unit: refractive index detector

Primary standard substance: polystyrene standard

The molecular weight at the top in the chromatogram that obtains is called as peak molecular weight.Molecular weight smaller or equal to 500 components contents by to 0～500 carrying out integration and try to achieve in the molecular weight distribution curve.In order to finish mensuration, an optional particle is dissolved among the THF to obtain sample solution from resin particle.Finish mensuration to the sample solution of 10 particles.

In the 1st and the 2nd invention, consider hot keeping quality (thermal storage), low-temperature fixing, vibrin (A1) and Tg (A2) are preferably 40～90 ℃, more preferably 45～85 ℃, more preferably 50～80 ℃.

Consider low-temperature fixing, the THF in the resin (A) does not dissolve part and is preferably smaller or equal to 70%.Lower limit more preferably 1%, especially more preferably 2%, most preferably be 3%, the upper limit more preferably 40%, more preferably 30%.

Above-mentioned THF does not dissolve part and measures by the following method.At first, the sample with 0.5g adds among the THF of 50ml gained solution stirring and backflow 3 hours.After the cooling insoluble part filtered by glass filter and separates, with the resin Composition in the glass filter 80 ℃ of vacuum drying 3 hours.The ratio that does not dissolve the weight of part by calculating the dry resin in the glass filter and sample resins weight obtains.

The hydroxyl value (mgKOH/g) of resin (A) is preferably smaller or equal to 70, more preferably 5～40, more preferably 10～30.If hydroxyl value is smaller or equal to 70, the environmental stability of resin and electrically charged amount improve.The acid number (mgKOH/g) of resin (A) is preferably smaller or equal to 40, more preferably 1～30, more preferably 2～25, most preferably is 5～20.If acid number is that then environmental stability is improved smaller or equal to 40.If resin has suitable acid number, then electric charge increase aspect improves, and is preferred therefore.

Consider in order to obtain satisfied low-temperature fixing and heat-resistant inks contamination property simultaneously, can unite and use two or more vibrin (A) among the present invention, also can unite and use at least a linear polyester resin (Aa) and at least a non-linearity vibrin (Ab).

Linear polyester resin (Aa) generally obtains by above-mentioned dibasic alcohol and dicarboxylic acids polycondensation.It can carry out the molecular end modification by the acid anhydrides of aforementioned polybasic carboxylic acid (comprise ternary or more than the polybasic carboxylic acid of ternary).

Non-linearity vibrin (Ab) generally obtains by making ternary that above-mentioned dicarboxylic acids and dibasic alcohol and front mention equally or reacting more than the polybasic carboxylic acid of ternary and/or ternary or more than the polyvalent alcohol of ternary.

As ternary or more than the polybasic carboxylic acid of ternary and/or ternary or more than the polyvalent alcohol of ternary, for example be preferably: have the AO of 2～4 carbon atoms and the addition product of novolac resin (average addition molal quantity is 2～30); Carbon number is 9～20 3 yuan to 6 yuan or more polynary aromatic series polybasic carboxylic acid (for example, trihemellitic acid and pyromellitic acid); More preferably 3 yuan to 6 yuan or more polynary aromatic series polybasic carboxylic acid.

Just obtain the situation of resin (Ab), ternary or be preferably 0.1～40 mole of % with respect to the molar ratio of the total molal quantity of whole polyol components and polybasic carboxylic acid component, more preferably 1～25 mole of %, 3～20 moles of % more preferably more than the polybasic carboxylic acid of ternary and ternary or more than the total molal quantity of the polyvalent alcohol of ternary.

The THF of resin (Aa) do not dissolve part be preferably smaller or equal to 3%, more preferably smaller or equal to 1%, more preferably 0%.Because the THF of resin (Aa) does not dissolve partly few more, then preferred more aspect low-temperature fixing.

The THF of resin (Ab) does not dissolve part and is preferably 1～70%.Lower limit more preferably 2%, more preferably 5%, the upper limit more preferably 60%, more preferably 50%.Stain aspect the property improving deep fat China ink, being included in THF in the above-mentioned scope, not dissolve part be preferred.

Polyester resin for toner of the present invention can contain other vibrin in the scope of the characteristic of not damaging vibrin (A).As described other resin for example: Mn is 1000～1,000,000, be preferably 1000～9500 vibrin (not comprising resin (A1)～(A3)).If resin (A) is non-linear polyester resin (Ab), it is preferred that the linear polyester resin that another kind is different from resin (Aa) is used in combination with it.

In vibrin, content (A) generally 20～100%, be preferably 25～100%, more preferably 30～90%.If content more than or equal to 20%, then can be given full play to characteristic of the present invention.

Polyester resin composition for toner contains above-mentioned polyester resin for toner (A) and toner with adjuvant (B) among the 4th of the present invention, adjuvant (B) comprises modified waxes (w1), and described modified waxes (w1) is to prepare by utilizing vinyl monomer (m) that at least a portion of wax (w) is carried out modification.

The wax (w) that is used as the parent material of adjuvant (B) can comprise polyolefin-wax, natural wax, have the fatty alcohol of 30～50 carbon atoms, the fatty acid with 30～50 carbon atoms and their potpourri.

The example of polyolefin-wax has: (being total to) polymkeric substance of alkene (for example, ethene, propylene, 1-butylene, isobutylene, 1-hexene, 1-dodecylene, 1-vaccenic acid and their potpourri) [its obtain by (being total to) polymerization and contain thermal degradation polyolefin]; The oxide of (being total to) polymkeric substance that obtains by oxygen and/or ozone; The maleic acid modified product of alkene (being total to) the polymkeric substance product of maleic acid and derivant (as maleic anhydride, maleic acid monomethyl ester, maleic acid monobutyl ester and maleic acid dimethyl esters) modification thereof [for example, by]; Alkene and unsaturated carboxylic acid are [for example, (methyl) acrylic acid, itaconic acid, maleic anhydride] and/or the multipolymer of unsaturated carboxylic acid alkyl ester [for example, (methyl) acrylic acid alkyl (alkyl with 1～18 carbon atom) ester, maleic acid alkyl (alkyl with 1～18 carbon atom) ester] etc.; And husky rope wax (sasol wax).

From film forming and the stripping feature to supporting body, the Mn of polyolefin-wax is preferably 400～40000, more preferably 1000～30000, more preferably 1500～2000.

The example of natural wax has Brazil wax, montan wax, paraffin and rice bran wax.Fatty alcohol with 30～50 carbon atoms can comprise triacontanol.Fatty acid with 30～50 carbon atoms can comprise the melissyl carboxylic acid.

Wherein preferred example is polyolefin-wax, natural wax and their potpourri, and preferred example is that thermal degradation polyolefin, further preferred example are thermal degradation tygon and thermal degradation polypropylene.

The softening point of wax (w) is preferably 50～170 ℃.More preferably 80 ℃, more preferably 90 ℃ of lower limits, be preferably 100 ℃ especially, more preferably 160 ℃, more preferably 155 ℃ of the upper limits.If softening point is more than or equal to 50 ℃, then toner has good flowability; If softening point smaller or equal to 170 ℃, then can obtain enough stripping results.

Softening point is measured by the method for stipulating among the JIS K 2207-1996.

From the viewpoint of toner fixing characteristic, wax (w) is generally 2～10000mPaS at 160 ℃ melt viscosity, is preferably 3～7000mPaS, 5～4500mPaS more preferably.

From the viewpoint of toner development characteristic, the pen. of wax (w) is generally smaller or equal to 5.0, be preferably smaller or equal to 3.5, more preferably smaller or equal to 1.0.

Pen. is measured by the method for stipulating among the JIS K 2207-1996.

The example that can be used as vinyl monomer (m) is the monomer and the combination thereof of following (a)～(f):

(a) carboxylic vinyl monomer:

(a-1) has the unsaturated monocarboxylic acid of 3～20 carbon atoms, for example (methyl) acrylic acid, crotonic acid, cinnamic acid;

What (a-2) have the unsaturated dicarboxylic acid of 4～30 carbon atoms and they becomes ester derivant [acid anhydrides and monoalkyl or two Arrcostab, wherein alkyl has 1～18 carbon atom], maleic acid, fumaric acid, itaconic acid, citraconic acid and their acid anhydrides and monoalkyl or two alkyl (wherein alkyl has 1～18 carbon atom) ester (as methyl esters, ethyl ester) for example.

(a-3) has the unsaturated carboxylic acid alkyl ester (wherein the alkyl carbon atoms number is 1～24) of 3～30 carbon atoms, for example, (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) 2-ethylhexyl acrylate, (methyl) dodecylacrylate, (methyl) acrylic acid stearyl, (methyl) acrylic acid cetyl ester, (methyl) acrylic acid heptadecyl ester, (methyl) acrylic acid eicosyl ester, (methyl) acrylic acid cyclohexyl ester, (methyl) benzyl acrylate ester, (methyl) phenyl acrylate, (methyl) acrylic acid ethyl-α-ethoxylated ester;

(a-4) has polyvalent alcohol (binary～ternary) ester of the unsaturated carboxylic acid of 3～30 carbon atoms, for example, two (methyl) acrylic acid glycol ester, two (methyl) acrylic acid propylene glycol ester, two (methyl) acrylic acid DOPCP, three (methyl) acrylic acid trihydroxy methyl propyl ester, 1,6 hexanediol diacrylate, polyglycol two (methyl) acrylate; With

(a-5) (for example have the monobasic of 1～12 carbon atom or polybasic carboxylic acid and unsaturated alcohol, vinyl alcohol and isopentene group alcohol) ester: for example, vinyl acetate, vinyl butyrate (vinylbutylate), propionate, vinyl butyrate, diallyl phthalate, diallyl adipate, isopropenyl acetate, benzoic acid methyl 4-vinyl esters, Methoxy acetic acid vinyl acetate and vinyl benzoate.

(b) vinyl monomer of hydroxyl:

(b-1) have (methyl) acrylic acid hydroxy alkyl esters of 5～16 carbon atoms, for example, (methyl) hydroxyethyl acrylate, (methyl) acrylic acid hydroxypropyl ester;

(b-2) have the enol of 2～12 carbon atoms, for example, (methyl) allyl alcohol, the pure and mild 2-butene-1-alcohol of 1-butylene-3-;

(b-3) have the enediol of 4～12 carbon atoms, for example, 2-butene-1,4-glycol; With

(b-4) have the alkenyl ether of 3～30 carbon atoms, for example, 2-hydroxyethyl propenyl ether, sucrose allyl ether.

(c) vinyl hydro carbons:

(c-1) aromatic ethenyl hydro carbons (carbon number is 8～20): as styrene, specifically enumerate as, alkyl (as, alkyl, naphthenic base, aralkyl and/or thiazolinyl) styrene that replaces, as α-Jia Jibenyixi, vinyltoluene, 2,4-dimethyl styrene, ethyl styrene, cumene ethene, butylstyrene, styryl phenyl, cyclohexyl benzene ethene, benzyl styrene, crotyl benzene, divinylbenzene, divinyl toluene, divinyl dimethylbenzene, trivinylbenzene, vinylnaphthalene;

(c-2) aliphatic ethylene base hydro carbons; The alkene that for example has 2～20 carbon atoms is as the alpha-olefin beyond ethene, propylene, butylene, isobutylene, amylene, heptene, diisobutylene, octene, dodecylene, vaccenic acid and the above-mentioned example; Diolefin with 4～20 carbon atoms is as butadiene, isoprene, 1,4-pentadiene, 1,5-hexadiene and 1,7-octadiene;

(c-3) cycloaliphatic vinyl hydro carbons; Illustrate, monocycle-, dicyclo-alkene and diolefin, as cyclohexene, (two) cyclopentadiene, vinyl cyclohexene and ethidine bicycloheptene; Terpenes is as sobrerone, limonene and indenes.

(d) contain the vinyl monomer of epoxy radicals: for example, (methyl) glycidyl acrylate;

(e) vinyl monomer of nitrile group-containing: for example, (methyl) vinyl cyanide;

(f) contain amino vinyl monomer: for example, (methyl) acrylic-amino ethyl ester, (methyl) acrylic acid dimethyl aminoethyl ester, (methyl) acrylic acid diethylamino ethyl ester, (methyl) acrylic acid tert-butyl group amino-ethyl ester, (methyl) acrylic acid N-amino-ethyl ester, (methyl) allylamine, (methyl) acrylic acid morpholino ethyl ester, 4-vinylpridine, 2-vinylpyridine, crotylamine, alpha-acetamido-methyl acrylate, vinyl imidazole, N-vinyl pyrrole and N-vinyl thiopyrrolidone.

Preferred example is styrene and styrene and other monomer [be preferably (a) and (b), especially preferred is (a-3) and (b-1)] usefulness also in them.

Modified waxes (w1) obtains by utilizing vinyl monomer (m) that wax (w) is carried out modification, toner used among the present invention can comprise the wax (w1) that utilizes monomer (m) to carry out graft modification with adjuvant (B), (being total to) polymkeric substance that in addition, wherein can also contain unreacted wax (w) and/or monomer (m).

When (w1), consider the flowability of the toner that will obtain at the preparation modified waxes, the part by weight of wax (w) and monomer (m) is preferably (1～30): (70～99), more preferably (2～27): (83～98).

The Tg of modified waxes (w1) is preferably 40～90 ℃, more preferably 50～80 ℃, especially is preferably 55～75 ℃.If Tg is 40～90 ℃, then can realize excellent hot storage stability and low-temperature fixing.

The Mn of modified waxes (w1) is preferably 2000～10000, more preferably 2500～9000.If Mn is 2000～10000, then the toner of Huo Deing has excellent permanance and comminuted.

The toner adjuvant (B) that contains modified waxes (w1), can obtain by for example following method: wax (w) is dissolved or be dispersed in the solvent (for example toluene or dimethylbenzene), be heated to 100～200 ℃, drip simultaneously then monomer (m) and peroxide initiator (as, benzoyl peroxide, di-tert-butyl peroxide, tert butyl peroxy benzoate) carry out continuous polymerization, remove solvent after the polymerization, obtain described adjuvant (B).

The use amount of peroxide initiator is generally 0.2～10%, is preferably 0.5～5% with respect to the general assembly (TW) of wax (w) and monomer (m).

Resin for toner composition among the 4th of the present invention contains vibrin (A) and toner with adjuvant (B).In order to control the particle diameter of wax in the toner, the weight ratio of resin (A) and adjuvant (B) is preferably (25～99.9): (0.1～75), more preferably (50～99): (1～50), especially be preferably (75～98): (2～25).

In addition, except vibrin (A) and adjuvant (B), polyester resin composition for toner of the present invention can contain other resin and release agent (they will be explained hereinafter) as required.In the present invention, toner has the effect of compatilizer with adjuvant (B), and it is used to improve the compatibility of vibrin and release agent.

In order to obtain the 4th of the present invention's polyester and resin composition, toner can mix in the mode of powder with adjuvant (B) and vibrin (A), also can carry out melting mixing, can under the condition that vibrin (A) exists, prepare toner adjuvant (B) by the mixing kettle that biaxial extruder maybe can heat and stir.

The method for producing toner and toner that the present invention is the 5th comprises polyester resin for toner (A), the colorant as adhesive resin, and can also comprise one or more adjuvants as required, as release agent, charge control agent and fluidizing agent.

As colorant, can use all dyestuffs and the pigment that use with colorant as toner.Concrete example has, carbon black, iron oxide black, sudan black SM, fast yellow (First Yellow) G, benzidine yellow, pigment yellow, Indian fast orange (Indian First Orange), Irgasin are red, paranitraniline red, toluidine red, carmine FB, pigment orange R, C lake red CAN'T 2G, rhodamine FB, rhodamine B lake, methyl violet B color lake, phthalocyanine blue, alizarol saphirol, bright green, phthalocyanine green, oil yellow GG, Kayaset YG, Orazol Brawn B and oil-bound distemper red (Oil Pink) OP, and these dyestuffs can use separately or at least two kinds mix and use.Further, also can add the function of magnetic (feeromagnetic metal powder such as iron, cobalt and nickel, or compounds such as magnetic iron ore, haematite and ferrite) as required with the performance colorant.In per 100 parts of vibrin of the present invention, the amount of colorant is preferably 1～40 part, more preferably 3～10 parts.Under the situation of using magnetic, its use amount is preferably 20～150 parts, more preferably 40～120 parts.In this manual, " part " represents weight portion.

As release agent, preferably its softening point is 50～170 ℃, and described release agent for example is polyolefin-wax, natural wax, the fatty alcohol with 30～50 carbon atoms, the fatty acid with 30～50 carbon atoms and their potpourri.

The example that is exemplified in concrete example and the aforementioned wax (w) is identical.

The example of natural wax has Brazil wax, montan wax, paraffin and rice bran wax.Fatty alcohol with 30～50 carbon atoms can comprise triacontanol.Fatty acid with 30～50 carbon atoms can comprise the melissyl carboxylic acid.

The example of charge control agent is the polymkeric substance of triphenylmethane type dye, quaternary ammonium salt, polyamine resin, imdazole derivatives, the polymkeric substance that contains quaternary ammonium salt, metallic azo dyes, copper phthalocyaine dye, salicylic acid metal salt, benzoic boron complex, the polymkeric substance that contains sulfonic acid group, fluoropolymer and halogen-containing substituted aroma ring with tertiary amine of aniline black byestuffs, side chain.

The example of fluidizing agent is colloidal silica, alumina powder, titanium dioxide powder and calcium carbonate powder.

For the ratio of each component in the 5th of the present invention's the method for producing toner and toner, based on the weight of toner, the ratio of vibrin of the present invention is preferably 30～97%, more preferably 40～95%, especially is preferably 45～92%; The ratio of colorant is preferably 0.05～60%, more preferably 0.1～55%, especially is preferably 0.5～50%; For adjuvant, the ratio of release agent is preferably 0～30%, more preferably 0.5～20%, especially is preferably 1～10%; The ratio of charge control agent is preferably 0～20%, more preferably 0.1～10%, especially is preferably 0.5～7.5%; The ratio of fluidizing agent is preferably 0～10%, more preferably 0～5%, especially is preferably 0.1～4%.Additive level is preferably 3～70%, more preferably 4～58%, especially is preferably 5～50%.If the ratio of toner each component all satisfies above-mentioned scope, then obtain having the toner of good charged characteristic easily.

Method for producing toner and toner can obtain by any known method among the present invention, described method such as mixing comminuting method, emulsification phase conversion method, polymerization.For example; obtaining in the situation of method for producing toner and toner by the comminuting method of kneading; each composition except that fluidizing agent that constitutes toner is at first mixed by dry type; then be melted and knead,, carry out micronize by jet pulverizer at last then with the molten mixture coarse crushing; and further the powder of granulation is carried out classification; obtain the particulate that particle diameter (D50) is preferably 5～20 μ m, add fluidizing agent this moment, can obtain toner.Particle diameter (D50) is measured [trade name: Multisizer III, Coulter corporate system] by Ku Erte particle collector (Coulter Counter).

Obtaining by the emulsification phase conversion method in the situation of method for producing toner and toner, it is dissolved or be dispersed in the organic solvent to constitute each composition except that fluidizing agent of toner, carry out the emulsification or the dispersion of solution by adding modes such as water, the particle to gained separates and classification subsequently.The volume average particle size of toner is preferably 3～15 μ m.

Method for producing toner and toner among the present invention also can have resin (for example with iron powder, beaded glass, nickel powder, ferrite, magnetic iron ore or surface-coated as required; acryl resin and silicones) carrier granulars such as ferrite mix, to be used for the developer of electric sub-image.The weight ratio of toner and carrier granular is generally 1/99～100/0.Also can not use carrier granular and rub and form electric sub-image with parts such as charged scraper plates.

Method for producing toner and toner of the present invention can by duplicating machine or printer photographic fixing supporter (as, paper and polyester film) go up and become recording materials.The known method of photographic fixing is heat roller fixation method and flash fusing (flash fixing) method on support.

The method for producing toner and toner of the application of the invention, when on fixing device, uncertain image being carried out photographic fixing, the temperature difference that the deep fat China ink stains between occurrence temperature and the minimum fixing temperature is reached more than or equal to 95 ℃ (particularly more than or equal to 100 ℃), thereby in described very wide temperature difference scope, implement photographic fixing easily.

In the 6th of the present invention, non-magnetic mono-component toner contains vibrin (A) [vibrin (A1) among the 1st～3 of the present invention, (A2) or (A3)] and colorant at least.

For the vibrin (A) in the 6th invention, can use the point (sp, Tg) of those softening points (sp) and glass transition temperature (Tg) to be in the vibrin of [inside of parallelogram among Fig. 1] in following equation (1)～(4) scope that defined straight line surrounded, preferably be in the scope of being surrounded, more preferably be in the scope that equation (1 '), (2 '), (3 ") and (4 ') defined straight line surrounded by equation (1), (2), (3 ') and (4 ') defined straight line.

Equation (1): sp=4Tg-110

Equation (2): sp=4Tg-170

Equation (3): sp=90

Equation (4): sp=130

Equation (1 '): sp=4Tg～114

Equation (2 '): sp=4Tg-166

Equation (3 '): sp=93

Equation (3 "): sp=95

Equation (4 '): sp=127.

Also promptly, the sp of vibrin (A) is 90-130 ℃.Lower limit is preferably 93 ℃, more preferably 95 ℃, and the upper limit is preferably 127 ℃.If sp is 90 ℃, then Tg is preferably 50-65 ℃, more preferably 51-64 ℃; If sp is 130 ℃, then Tg is preferably 60-75 ℃, more preferably 61-74 ℃.

In this case, if sp is lower than above-mentioned scope, the offset phenomenon takes place probably when photographic fixing; And if sp is higher than above-mentioned scope, the photographic fixing energy is increased, for color toner, may damage its glossiness and the transparency easily.If Tg is lower than above-mentioned scope, what may cause toner is condensed into piece and adhesion, if Tg is higher than above-mentioned scope, the fixing strength during hot photographic fixing may descend, and therefore preferred sp and Tg are in above-mentioned scope.Sp mainly can regulate by the molecular weight of resin, preferably Mn is adjusted to 2000～20000, more preferably 3000～12000.Tg mainly can assign to regulate by the set of monomers of selecting to constitute resin, specifically, can increase Tg as the principal ingredient of polybasic carboxylic acid component by using the aromatic series polybasic carboxylic acid.

Different with the assay method of softening point among the 2nd of the present invention, the sp of above-mentioned vibrin (A) measures by the flow tester of describing among JIS K7210 and the K6719.Specifically, measure following carrying out: adopting flow tester (CFT-500, Shimadzu Seisakusho Ltd.'s system), heat with the sample of 3 ℃/min programming rate to about 1g, is 1cm with the surface area simultaneously ²Piston apply 30kg/cm ²Load, sample is extruded from the die orifice of aperture 1mm, length 10mm.Therefore, the stroke temperature curve of the piston that draws is represented by h as if the height of sigmoid curve, then the pairing temperature of h/2 is defined as softening point.

Vibrin (A) can two kinds be used in combination at least, for satisfy low-temperature fixing simultaneously, heat-resistant inks stains property and comminuted, resin (A) preferably comprises above-mentioned linear polyester resin (Aa) and non-linearity vibrin (Ab).Vibrin (Aa) and (Ab) can comprise two or more resin respectively.

(Aa) and weight ratio (Ab) be preferably 10/90～80/20, more preferably 20/80～75/25, especially be preferably 25/75～70/30.

The vibrin that uses among the 6th of the present invention is preferably and only comprises resin (A), but also can add other vibrin in the scope of not damaging the vibrin characteristic.Other resin can be resin (A) vibrin in addition, and its Mn is 1000～1,000,000.The content of other resin is preferably smaller or equal to 10%, more preferably smaller or equal to 5%.

In the situation of resin (A) and the use of other resin combination, preferred polyester resin for toner of the present invention keeps the physical characteristics (molecular weight, Tg and THF do not dissolve part) of the preferable range of above-mentioned (A) on the whole.

The example of used colorant can be identical with the description of front in the nonmagnetic toner of the present invention.

Nonmagnetic toner of the present invention comprises the particulate of at least a particulate additives (fluidizing agent) on the toner-particle surface.The adding of these particulates is mainly used in coherency, stickability and the flowability of improving toner-particle, also is used to improve simultaneously frictional electrification and permanance as toner.Can to use average primary particle diameter in practice be 0.001～5 μ m, be preferably the organic or inorganic particulate of 0.002～3 μ m, and can choose wantonly and carry out surface-treated organic or inorganic particulate, the example of described organic or inorganic particulate comprises fluorinated resin particle, as polyvinylidene fluoride and teflon; Fatty acid metal salts is as zinc stearate and calcium stearate; The resin particle that mainly contains polymethylmethacrylate and silicones; Mineral are as talcum and hydrotalcite; And metal oxide, as silicon dioxide (colloidal silica etc.), aluminium oxide, titanium dioxide, zinc paste and tin oxide.

Nonmagnetic toner of the present invention can also contain a kind of or at least 2 kinds of above-mentioned normally used adjuvants as required, as release agent and charge control agent.

For the ratio of components of nonmagnetic toner of the present invention, based on the weight of toner, the ratio of vibrin of the present invention (A) is preferably 30～97%, more preferably 40～95%, especially is preferably 45～92%; The ratio of colorant is preferably 0.05～60%, more preferably 0.1～55%, especially is preferably 0.5～50%; And with regard to adjuvant, the ratio ranges of preferred particulate additives is 0.01～10%, more preferably 0.05～5%, especially is preferably 0.1～4%; The ratio of release agent is preferably 0～30%, more preferably 0.5～20%, especially is preferably 1～10%; The ratio of charge control agent is preferably 0～20%, more preferably 0.1～10%, especially is preferably 0.5～7.5%; Wherein the total content of all adjuvants (comprising particulate additives) is preferably 3～70%, more preferably 4～58%, especially is preferably 5～50%.If the ratio of components of toner each component all is in above-mentioned restricted portion, then obtain to have the toner of good charged characteristic easily.

Nonmagnetic toner of the present invention can be by any known method, as the comminuting method of kneading, emulsification phase conversion method and polymerization obtain.

Nonmagnetic toner of the present invention can by duplicating machine or printer photographic fixing support (as, paper and polyester film) go up and become recording materials.The known method of photographic fixing is heat roller fixation method and flash fusing method on support.

Secondly, the resin particle among the 7th of the present invention comprises vibrin (K1) with vibrin (K), and described vibrin (K1) obtains by making one or more polyol components and one or more polybasic carboxylic acid components carry out polycondensation.In the dibasic alcohol of vibrin (K1), contain have 2～6 carbon atoms aliphatic dihydroxy alcohol as necessary component.

Aliphatic dihydroxy alcohol with 2～6 carbon atoms can comprise the material that lists previously, and can two or more be used in combination.Preferred example comprises ethylene glycol, 1,2-propylene glycol and neopentyl glycol; Ethylene glycol and 1 more preferably, the 2-propylene glycol; Especially be preferably 1, the 2-propylene glycol.

In the polyol component of preparation vibrin (K1), the content with aliphatic dihydroxy alcohol of 2～6 carbon atoms is generally 85～100 moles of %, is preferably 90～100 moles of %, more preferably 95～100 moles of %, especially be preferably 100 moles of %.If the content of aliphatic dihydroxy alcohol with 2～6 carbon atoms then can increase the intensity of resin itself more than or equal to 85 moles of %, improve low-temperature fixing simultaneously.If use 1, the 2-propylene glycol is as having the aliphatic dihydroxy alcohol of 2～6 carbon atoms, then its content be generally 70～100 moles of %, be preferably 75～100 moles of %, more preferably 90～100 moles of %, more preferably 95～100 moles of %, especially be preferably 100 moles of %.If 1, the content of 2-propylene glycol then can increase the intensity of resin itself more than or equal to 70 moles of %, improves low-temperature fixing simultaneously.

Except having the aliphatic dihydroxy alcohol of 2～6 carbon atoms, can also contain in the polyol component smaller or equal to 15 moles of other polyvalent alcohols of % (using 1, this content is smaller or equal to 30 moles of % during the 2-propylene glycol).

In polyvalent alcohol, the example of dibasic alcohol can comprise, the aliphatic diol with 7～36 carbon atoms described above, has the polyalkylene glycol ethers of 4～36 carbon atoms; Carbon number is 2～4 AO and the addition product with aliphatic diol of 2～6 and 7～36 carbon atoms; Alicyclic diol with 6～36 carbon atoms; Carbon number is 2～4 the AO and the addition product of alicyclic diol; And carbon number is 2～4 the AO and the addition product of bis-phenol.

In polyvalent alcohol, as cited those in the example of 3 yuan～8 yuan or more polynary polyvalent alcohol such as front.

In these polyvalent alcohols, the AO that be preferably polyalkylene glycol ethers, alicyclic diol, has 2～4 carbon atoms with 4～36 carbon atoms with addition product with the addition product of the alicyclic diol of 6～36 carbon atoms, AO and bis-phenol with 2～4 carbon atoms, have the AO of 2～4 carbon atoms and the addition product of novolac resin; Preferred example is AO (EO and PO) with 2～3 carbon atoms with the addition product of bis-phenol and has the AO (EO and PO) of 2～3 carbon atoms and the addition product of novolac resin.

It is identical to constitute cited those in example and the front of polybasic carboxylic acid component of (K1).

In the polybasic carboxylic acid component, preferred example is the alkane dicarboxylic acid with 2～50 carbon atoms; Chain docosene dicarboxylic acid with 4～50 carbon atoms; Aromatic binary carboxylic acid with 8～20 carbon atoms; Aromatic series polybasic carboxylic acid with 9～20 carbon atoms; Preferred example is hexane diacid, has the alkenyl succinic of 16～50 carbon atoms, terephthalic acid (TPA), m-phthalic acid, maleic acid, fumaric acid, trihemellitic acid, pyromellitic acid, and the combination of these acid; Preferred example is the combination of hexane diacid, terephthalic acid (TPA), trihemellitic acid and these acid.Acid anhydrides that these are sour and lower alkyl esters are preferred too.

In addition, the polybasic carboxylic acid component also preferably comprises polynary (2 yuan～6 yuan or more polynary) carboxylic acid of aromatic series and aliphatics polynary (2 yuan～6 yuan or more polynary) carboxylic acid, and wherein the content of aromatic series polybasic carboxylic acid is more than or equal to 60 moles of %.The lower limit of aromatic series polybasic carboxylic acid content is 70 moles of %, 80 moles of % more preferably more preferably, and the upper limit is preferably 99 moles of %, 98 moles of % more preferably.When the content of aromatic series polybasic carboxylic acid during more than or equal to 60 moles of %, then can increase the intensity of resin, can further improve the low-temperature fixing characteristic simultaneously.

Among the present invention, vibrin (K1) can be by the conventional method preparation of preparation vibrin.Described method such as front are cited.

The Mn of the THF solubilized part of resin (K1) is 1000-9500.Lower limit is preferably 1200, more preferably 1400; The upper limit is preferably 9300, more preferably 9100.If Mn is more than or equal to 1000, then the intensity of resin is good; If Mn is smaller or equal to 9500, then the low-temperature fixing of resin is good.

Consider the balance between mechanical strength of resin and low-temperature fixing, the Mp of the THF solubilized part of resin (K1) is preferably 1200～250000.Lower limit more preferably 1500, the upper limit more preferably 23000.

In the THF solubilized of resin (K1) part, the molecular weight that records by gel permeation chromatography (GPC) smaller or equal to 500 components contents be preferably smaller or equal to 3%, more preferably smaller or equal to 2.5%.If molecular weight,, can further improve liquidity when then resin being used for toner smaller or equal to 3% smaller or equal to 500 components contents in the resin (K1), the stability of image is improved when making printing continuously.When using at least two kinds of resins as (K1), even molecular weight is higher smaller or equal to 500 components contents in a kind of resin, as long as molecular weight then also allows smaller or equal to the satisfied top content range that is limited of 500 components contents in resin (K1) integral body.

Consider hot keeping quality (thermal storage) and low-temperature fixing, the Tg of vibrin (K1) is preferably 40～90 ℃, more preferably 45～85 ℃, more preferably 50～80 ℃.

Consider low-temperature fixing, the THF of resin (K1) does not dissolve part and is preferably smaller or equal to 70%.Lower limit more preferably 1%, especially be preferably 3%, the upper limit is more preferably 40%, especially be preferably 30%.

The hydroxyl value (mgKOH/g) of resin (K1) is preferably smaller or equal to 70, more preferably 5～40, more preferably 10～30.If hydroxyl value is smaller or equal to 70, the carried charge in the time of then can increasing environmental stability and be used for resin.The acid number (mgKOH/g) of resin (K1) is preferably smaller or equal to 40, more preferably 1～30, more preferably 2～25, most preferably is 5～20.If acid number is smaller or equal to 40, then can makes and improve environmental stability.If resin has suitable acid number, then electric charge raises and improves, and is preferred therefore.

Two or more resins can be united among the present invention and be used for vibrin (K1), and for obtaining satisfied low-temperature fixing and heat-resistant inks contamination property simultaneously, resin (K1) preferably comprises linear polyester resin (K1a) and non-linearity vibrin (K1b).Resin (K1a) and (K1b) can distinguish and with at least two kinds of resins.

(K1a) and weight ratio (K1b) be preferably 10/90～80/20, more preferably 20/80～75/25, especially be preferably 25/75～70/30.

And, because same reason, the Mn of the THF solubilized of resin (K1b) part be preferably Mn than the THF solubilized part of resin (K1a) high at least by 200, more preferably high at least 300.

Linear polyester resin (K1a) generally obtains by making above-mentioned dibasic alcohol and dicarboxylic acids carry out polycondensation.Its molecular end can utilize the acid anhydrides of aforementioned polybasic carboxylic acid (ternary or more than the polybasic carboxylic acid of ternary) to carry out modification.

Non-linearity vibrin (K1b) generally obtains by above-mentioned dicarboxylic acids and dibasic alcohol and ternary or more than the polybasic carboxylic acid of ternary and/or ternary or more than the reaction of the polyvalent alcohol of ternary.Ternary or be preferably the AO with 2～4 carbon atoms and the addition product (average addition molal quantity is 2～30) of novolac resin more than the polybasic carboxylic acid of ternary and/or ternary or more than the example of the polyvalent alcohol of ternary; Carbon number is 9～20 3 yuan～6 yuan or more polynary aromatic series polybasic carboxylic acid (for example, trihemellitic acid and pyromellitic acid); More preferably 3 yuan to 6 yuan or more polynary aromatic series polybasic carboxylic acid.

In the situation that obtains resin (K1b), total molal quantity with respect to whole polyol components and polybasic carboxylic acid component, ternary or be preferably 0.1～40 mole of %, more preferably 1～25 mole of %, 3～20 moles of % more preferably more than the polybasic carboxylic acid of ternary and ternary or more than the molar ratio of the polyvalent alcohol of ternary.

Vibrin (K1) is preferably the vibrin (A2) among the 2nd of vibrin (A1) among the 1st of the present invention and/or the present invention.

The THF of resin (K1a) do not dissolve part be preferably smaller or equal to 3%, more preferably smaller or equal to 1%, more preferably 0%.Do not lack if the THF of resin (K1a) does not dissolve part, then have better low-temperature fixing.

The THF of resin (K1b) does not dissolve part and is preferably 1～70%.Lower limit more preferably 2%, more preferably 5%, the upper limit more preferably 60%, more preferably 50%.Stain aspect the property improving deep fat China ink, the resin (K1b) of content in above-mentioned scope that THF does not dissolve part is preferred.

In the scope of not damaging vibrin (K1) characteristic, the resin in the resin particle (K) can comprise one or more other resins (K2).The example of other resin (K2) comprises that resin (K1) vibrin, vinylite, urethane resin, epoxy resin, vibrin, polyamide, polyimide resin, silicon in addition is resin, phenolics, melamine resin, Lauxite, anline resin, ionomer resin and polycarbonate resin; Wherein preferred example is the combination of vinylite, urethane resin, epoxy resin, vibrin and these resins.The object lesson of vinylite, urethane resin, epoxy resin and vibrin has detailed description in the open WO03/106541 in the world.

The Mn of resin (K2) is preferably 500～2, and 000,000,1000-1 more preferably, 000,000.The content of (K2) is preferably smaller or equal to 10%, more preferably 0.1～8% in the resin (K).

If also contain other resin (K2) in the resin (K), then preferred resin (K) has the preferred physical characteristics (molecular weight, Tg, THF solubilized part) of (K1) in above-mentioned scope as a whole.

Resin particle of the present invention can also contain one or more adjuvants as required except that containing resin (K), described adjuvant is colorant, release agent, charge control agent and fluidizing agent for example.If resin particle is used for powdery paints, electrofax tinter, electrostatic recording toner or xeroprinting toner, then must contain colorant.

As colorant, can use all dyestuffs and the pigment that use with colorant as toner.Listed those that enumerate in concrete example such as front, they can use separately or two or more mix use.In addition, also can add the function of magnetic (feeromagnetic metal powder such as iron, cobalt and nickel, or compounds such as magnetic iron ore, haematite and ferrite) as required with the performance colorant.In resin particle of the present invention, with respect to per 100 parts of resins (K), the content of colorant is preferably 1～40 part, more preferably 3～10 parts.Under the situation of using magnetic, its use amount is preferably 20～150 parts, more preferably 40～120 parts.

The example of release agent, charge control agent and fluidizing agent as previously described.

For the ratio of components of resin particle of the present invention, based on the weight of composition, the ratio of resin (K) is preferably 30～97%, more preferably 40～95%, especially is preferably 45～92%; For adjuvant, the ratio of colorant is preferably 0.05～60%, more preferably 0.1～55%, especially is preferably 0.5～50%; The ratio of release agent is preferably 0～30%, more preferably 0.5～20%, especially is preferably 1～10%; The ratio of charge control agent is preferably 0～20%, more preferably 0.1～10%, especially is preferably 0.5～7.5%; The ratio of fluidizing agent is preferably 0～10%, more preferably 0～5%, especially is preferably 0.1～4%.Simultaneously, wherein all additive levels are preferably 3～70%, more preferably 5～60%, especially are preferably 8～55%.If each ratio of components all is in above-mentioned institute restricted portion, then obtain to have the toner of good charged characteristic easily.

Can followingly obtain resin particle of the present invention: will comprise the each component dissolving of resin (K) or be dispersed in preparation oiliness mixed liquor (I) in the organic solvent, then utilize aqueous medium (II) that oiliness mixed liquor (I) is changed into aqueous liquid dispersion, from aqueous liquid dispersion, remove solvent (as organic solvent and water) then, thereby obtain resin particle of the present invention.

The volume average particle size of resin particle is preferably 2～20 μ m.Lower limit more preferably 3 μ m, especially be preferably 4 μ m, the upper limit more preferably 15 μ m, especially be preferably 12 μ m.

Volume average particle size (D50) is by laser class particle size distribution device [for example, trade name: LA-920 (the hole field makes made); And trade name: Multisizer III (Coulter corporate system)] measure.

In order in aqueous liquid dispersion, to be easy to form the oil droplet of oiliness mixed liquor (I), and keep the stability of the oil droplet that forms simultaneously, can contain emulsifying agent and spreading agent in the aqueous medium (II).The example of emulsifying agent and spreading agent can use known surfactant (S), particulate (M), water-soluble polymers (T).Solvent (U) and plastifier (V) can be used as the auxiliary agent of emulsification and dispersion and unite use.

Can use the known surface activating agent of widespread use as surfactant (S), its example comprises anionic surfactant (S-1), cationic surfactant (S-2), amphoteric surfactant (S-3) and nonionic surfactant (S-4).Can and use at least two kinds of surfactants as surfactant (S).

The example of anionic surfactant (S-1) comprising: salt, sulfonate and the phosphate ester salt of carboxylic acid and salt thereof, sulfuric acid, carboxymethylation compound.

The example of cationic surfactant (S-2) comprising: quaternary ammonium salt cationic surfactant and amine salt type surfactant.

The example of amphoteric surfactant (S-3) comprising: carboxylic acid type amphoteric surfactant, sulfuric acid type amphoteric surfactant, sulfonate amphoteric surfactant and phosphate ester salt type amphoteric surfactant.

The example of nonionic surfactant (S-4) comprising: AO addition product type nonionic surfactant and polyvalent alcohol type nonionic surfactant.

The instantiation of these surfactants (S) has corresponding description in the open WO03/106541 in the world.

The content of surfactant (S) is preferably 0.01～30%, more preferably 0.1～20% in aqueous medium (II).

If particulate (M) is the resin particle that is fit to form water-borne dispersions, then there is no particular limitation to particulate (M), can be the particulate of thermoplastic resin, also can be the particulate of thermoset resin.The instantiation of microparticle material comprises vinylite, urethane resin, epoxy resin, vibrin, polyamide, polyimide resin, silicones, phenolics, melamine resin, Lauxite, anline resin, ionomer resin, polycarbonate resin, and at least two kinds of resin combination in the above-mentioned resin can be used.Consider that from the angle of the water-borne dispersions of easy acquisition microspheroidal resin particle wherein preferred example is vinylite, urethane resin, epoxy resin, vibrin and and with the resin particle of these resins.The instantiation of these resins has corresponding description in the open WO03/106541 in the world.

The volume average particle size of particulate (M) is preferably 20～500nm, 25～300nm more preferably.

The content of particulate (M) in aqueous medium (II) is preferably 0.01～30%, more preferably 0.1～

20％。

The example of water-soluble polymers (T) (for example has cellulose-based compound, methylcellulose, ethyl cellulose, hydroxyethyl cellulose, ethylhydroxyethylcellulose, carboxymethyl cellulose, hydroxypropyl cellulose, and theirs is saponified), gelatin, starch, dextrin, gum arabic, chitin, shitosan, polyvinyl alcohol (PVA), polyvinylpyrrolidone, polyglycol, polyethyleneimine, polyacrylamide, the polymkeric substance that contains acrylic acid (salt) (for example, sodium polyacrylate, polyacrylic acid potassium, ammonium polyacrylate, the polyacrylic acid that is partly neutralized by NaOH, and the multipolymer of PAA-acrylate), by the styrene-maleic anhydride copolymer of NaOH (part) neutralization, and soluble polyurethane (for example, the reaction product of polyisocyanates and polyglycol or pcl-diol acid lactone).

The number-average molecular weight of water-soluble polymers (T) is preferably 1,000～10,000,000.

The content of water-soluble polymers (T) in aqueous medium (II) is preferably 0.01～20%, more preferably 0.1～10%.

The example of the solvent that uses among the present invention (U) can comprise: aromatic hydrocarbon solvent, for example toluene, dimethylbenzene, ethylbenzene and tetralin; Fat hydrocarbon solvent or alicyclic hydrocarbon type solvent, for example normal hexane, normal heptane, Mineral spirits and cyclohexane; Halogen-type solvent, for example methyl chloride, bromomethane, iodomethane, methylene chloride, phenixin, triclene and perchloro-ethylene; Ester or solvent of ether ester type, for example ethyl acetate, butyl acetate, acetate methoxyl butyl fat, methylcellosolve acetate and ethyl cellosolve acetate; Ether solvent, for example diethyl ether, tetrahydrofuran, dioxane, ethyl cellosolve, butyl cellosolve and propylene glycol monomethyl ether; Ketones solvent, for example acetone, methyl ethyl ketone, methyl isobutyl ketone, di-n-butyl ketone, cyclohexanone; Alcohols solvent, for example methyl alcohol, ethanol, n-propanol, isopropyl alcohol, normal butyl alcohol, isobutyl alcohol, the tert-butyl alcohol, 2-Ethylhexyl Alcohol and phenmethylol; Amide solvent is as dimethyl formamide and dimethyl acetamide; The sulfoxide kind solvent is as dimethyl sulfoxide; The heterogeneous ring compound kind solvent is as N-Methyl pyrrolidone; And at least two kinds mixed solvent in the above-mentioned solvent.

The content of solvent (U) in aqueous medium (II) is preferably 0.01～50%, more preferably 0.1～30%.

There is no particular limitation for plastifier (V), can list following example:

(V1) have 8～60 carbon atoms phthalic ester [as, dibutyl phthalate, dioctyl phthalate, butyl phthalate benzyl ester and diisooctyl phthalate];

(V2) has the fatty group dibasic acid [as, two (2-ethylhexyl) adipate and (2-ethylhexyl) sebacate] of 6～60 carbon atoms;

(V3) have 10～70 carbon atoms tritrimellitate [as, three (2-ethylhexyl) tritrimellitate, trioctyl trimellate];

(V4) have 8～60 carbon atoms phosphate [as, triethyl phosphate, tri-2-ethylhexyl phosphate and tricresyl phosphate];

(V5) has the fatty acid ester [as, butyl oleate] of 8～50 carbon atoms; And

(V6) at least two kinds potpourri in above-mentioned these compounds.

The content of plastifier (V) in aqueous medium (II) is preferably 0.01～10%, more preferably 0.1～8%.

Among the present invention, when obtaining aqueous liquid dispersion by oiliness mixed solution (I) and aqueous medium (II), as the blending ratio of the two, with respect to per 100 parts of oiliness mixed solutions (I), the content of corresponding aqueous medium (II) is preferably 50～500 parts, more preferably 80～300 parts.There is no particular limitation in order by merging, (II) can be joined in (I), otherwise also can, perhaps both are added simultaneously.Mixing can be carried out under stirring or dispersion condition, or stirs and dispersion treatment after both are mixed again.

Among the present invention,, can use diverting device in order to obtain aqueous liquid dispersion by solution (I) and aqueous medium (II).There is no particular limitation to employed diverting device, general commercially available mulser and diverting device get final product, the example of employed device comprises: mulser in batches, as homogenizer (IKA society system), Polytron (Kinematica corporate system) and the automatic homogeneous mixer of TK (special machine chemical industry society system); The continuous emulsification machine is as Ebara Milder (in society of former making institute system), TK Fillmix and TK Pipe Line homogeneous mixer (special machine chemical industry society system), colloid mill (refreshing steel Pantech society system), shredding machine and triangle wet type atomizer (Mitsui three pond chemical industry machine society systems), Cabitron (Eurotech corporate system) and meticulous mobile mill (Pacific Ocean machine worker society system); The high-pressure emulsification machine is as micro-fluidized bed (Mizuho industry society system), Nanomizer (Nanomizer corporate system) and APV Gaulin (Gaulin corporate system); The membrane type mulser is as membrane type mulser (cold chemical industry society system); The oscillatory type mulser is as Vibro Mixer (cold chemical industry society system); And the ultrasonic type mulser, as ultrasonic homogenizer (BRANSON corporate system).Consider preferred APV Gaulin, homogenizer, the automatic homogeneous mixer of TK, EbaraMilder, TK Filmix and the TK Pipeline homogeneous mixer of using in the said apparatus from the angle of grain diameter homogenization.

As required, from the aqueous liquid dispersion that contains resin (K) that adopts above-mentioned preparation method to obtain, remove organic solvent, obtain the aqueous liquid dispersion of resinous particle, carry out Separation of Solid and Liquid (if desired subsequently, can add water and carry out Separation of Solid and Liquid repeatedly), and carry out drying to remove organic solvent and water equal solvent, then can obtain resin particle of the present invention.

Can adopt the method for the combination of following method [1]～[3] and described method as the removal solvent:

[1] water-borne dispersions is carried out dry method under decompression or condition of normal pressure;

[2] carry out Separation of Solid and Liquid by centrifugal separator, Supakura filtrator and/or pressure filter, then the gained solid is carried out dry method; With

[3] water-borne dispersions is carried out freezing, carry out dry method (so-called freeze-dried method) then.

In said method of the present invention [1] and [2], spendable known drier unit as, fluid-bed drier, vacuum drier and drying by circulating air machine.

If desired, can use air classifier or screen cloth that resin particle is carried out classification to obtain desirable size distribution.

After removing solvent, in the resin particle of the present invention, the content of residual solvent is preferably smaller or equal to 200ppm with respect to the content of organic solvent, and the content of water is preferably smaller or equal to 0.5%.

When the resin particle with the 7th of the present invention is used for toner, as required, it can have resin (for example with iron powder, beaded glass, nickel powder, ferrite, magnetic iron ore and surface-coated, acryl resin and silicones) carrier granulars such as ferrite mix, to be used for the developer of electric sub-image.The weight ratio of toner and carrier granular is generally 1/99～100/0.Also can not use carrier granular and rub and form electric sub-image with charged scraper plate etc.

When the resin particle with the 7th of the present invention is used for toner, its can by duplicating machine or printer photographic fixing support (as, paper and polyester film) go up and become recording materials.The known method of photographic fixing is heat roller fixation method and flash fusing method on support.

Composite resin particle among the 8th of the present invention comprises as the resin particle (P) of nuclear and attached to the resin particle (Q) on resin particle (P) surface, and wherein resin particle (P) comprises resin (p).

Resin (p) contains specific vibrin (p1) and/or resin (p2), and vibrin (p1) obtains by making at least a polyol component and at least a polybasic carboxylic acid component carry out polycondensation, and resin (p2) contains (p1) as constituting the unit.(p1) and (p2) two or more can be used respectively.

Resin (p1) can for the identical material of the listed material of enumerating of above-mentioned vibrin (K1).

Consider hot keeping quality, watery fusion and low-temperature fixing, the Tg of resin (p1) is preferably 30～120 ℃, more preferably 35～100 ℃, especially is preferably 40～90 ℃.

The hydroxyl value (mgKOH/g) of resin (p1) is preferably smaller or equal to 70, more preferably 5～50, especially is preferably 10～40.If hydroxyl value is smaller or equal to 70, then the environmental stability of resin and the carried charge when being used for toner can be improved.The acid number (mgKOH/g) of resin (p1) is preferably smaller or equal to 45, more preferably 1～40, more preferably 2～35, most preferably is 5～30.If acid number smaller or equal to 45, then can improve environmental stability.If resin has suitable acid number, then electric charge increase aspect improves, and is preferred therefore.

Vibrin (p1) is preferably the 2nd of the 1st of the present invention's vibrin (A1) and/or the present invention's vibrin (A2).

The resin (p) that contains in resin particle of the present invention (P) can be to contain the resin (p2) of above-mentioned vibrin (p1) as polymer backbone formation unit, and resin (p1) and resin (p2) can be used in combination.

Resin (p2) can be the urethane resin that comprises resin (p1) and polyisocyanates described later (15); Can be the epoxy resin that comprises resin (p1) and polyepoxide described later (18); It also can be the polyamide that comprises resin (p1) and aftermentioned polyamide (16).

Wherein, be preferably urethane resin and epoxy resin, more preferably urethane resin.

In resin (p1) and the resin (p2),, thereby be more preferably because resin (p2) has better watery fusion and low-temperature fixing.

For resin (p2), for example can contain vibrin (p1) in the molecule and obtain, perhaps can contain vibrin (p1) and carry out composite reaction as prepolymer that contains reactive group (α) that constitutes the unit and hardening agent (β) and obtain by making by making as precursor (p0) that constitutes the unit and hardening agent reaction.

Wherein, containing the reactive group that the prepolymer (α) of reactive group had and the combination of hardening agent (β) can be following combination [1] and combination [2]:

Combination [1]: prepolymer (α 1) that contains reactive group and the combination that contains compound bearing active hydrogen (β 1), wherein (α 1) have can with the functional group that contains the active hydrogen group reaction;

Combination [2]: have the combination of the prepolymer that contains reactive group (α 2) that contains active hydrogen group and hardening agent (β 2), wherein (β 2) have can with the functional group that contains the active hydrogen group reaction.

As can with the functional group that contains active hydrogen group reaction, for example can enumerate: isocyanate groups, blocked isocyanate groups, epoxide group, anhydride group, acyl halide group (as, acyl chlorides and acylbromide).

Wherein be preferably isocyanate groups, blocked isocyanate groups and epoxide group, more preferably isocyanate groups, blocked isocyanate groups.

What need in this to indicate is that blocked isocyanate groups means by the isocyanate groups of end-capping reagent end-blocking.

End-capping reagent comprises those well-known examples, for example oxime (as, acetoxime, methyl isobutyl ketoxime, the diethyl ketoxime, cyclopentanone oxime, cyclohexanone-oxime, methyl ethyl ketone oxime), lactams (as, butyrolactam, epsilon-caprolactams, and γ-valerolactam), have 1～20 carbon atom fatty alcohol (as, ethanol, methyl alcohol and octanol), phenol (as, phenol, metacresol, xylenols, and nonylphenol), activity methene compound (as, diacetone, malonic ester, and ethyl acetoacetate), basic nitrogen compound (as, N, the N-diethyl hydroxylamine, 2 hydroxy pyrimidine, the N-pyridine oxide, and 2-mercaptopyridine), and two or more the potpourri in them.

In the described end-capping reagent, be preferably oxime, methyl ethyl ketone oxime more preferably.

Reactive group is introduced method in the vibrin (p1), and there is no particular limitation, for example, can adopt the method that following compound and vibrin (p1) are reacted, described compound contains and can go up functional group's (reactive group) that remaining functional group reacts with vibrin (p1).

According to described method, react the prepolymer that obtains to contain isocyanate groups by making vibrin (p1) and polyisocyanates; React the prepolymer that obtains to contain blocked isocyanate groups by polyisocyanates with end-blocking; By reacting the prepolymer that obtains to contain epoxide group with polyepoxide; By reacting the prepolymer that obtains to contain anhydride group with the compound that contains at least two anhydride groups.

The ratio of vibrin (p1) and polyisocyanates is calculated with mol ratio [NCO]/[OH] of isocyanates [NCO] and hydroxyl [OH] and is preferably 5/1～1/1, more preferably 4/1～1.2/1, especially is preferably 2.5/1～1.5/1.In other words, the upper limit of [NCO]/[OH] mol ratio is preferably 5/1, more preferably 4/1, especially is preferably 2.5/1, and same, lower limit is preferably 1/1, more preferably 1.2/1, especially is preferably 1.5/1.

For having other prepolymer that simple constituent changes, its preferred proportionate relationship is also identical with it.

The number that per molecule contains the reactive group that is contained in the prepolymer (α) of reactive group is preferably 1～3, more preferably 1.5～3, especially is preferably 1.8～2.5.If this numerical value is in above-mentioned scope, then itself and hardening agent (β) react resulting resin (q) and have high mechanical properties easily.

The Mn that contains the prepolymer (α) of reactive group is preferably 1,000～30, and 000, more preferably 1,500～20,000, especially be preferably 2,000～10,000.

The Mw that contains the prepolymer (α) of reactive group is preferably 1,500～50, and 000, more preferably 2,000～40,000, especially be preferably 4,000～20,000.

The viscosity of prepolymer (α) in the time of 100 ℃ that contains reactive group is preferably 50～50, and 000MPaS, more preferably 100～5, especially is preferably 150～3,000MPaS at 000MPaS.

When viscosity is in described scope,, also be easy to obtain the spindle composite resin particle of narrow size-grade distribution even the use amount of solvent seldom.

As the compound that contains active hydrogen group (β 1), for example can enumerate, water, glycol (11), 3 yuan～6 yuan or more polynary polyvalent alcohol (12), dicarboxylic acids (13), 3 yuan～4 yuan or more polynary polybasic carboxylic acid (14), polyamine (16) and polythiol (17) adopt can to break away from compound and carry out the polyamine of end-blocking or optionally adopt breaking away from the polyvalent alcohol that compound carries out end-blocking in addition selectively.

The example that adopts departing compound to carry out the polyamine of end-blocking comprises: by polyamine (16) and ketone with 3～8 carbon atoms (as, acetone, MEK and methyl isobutyl ketone) between carry out dehydration and the ketimine compound that obtains; By polyamine and aldehyde compound with 2～8 carbon atoms (as, formaldehyde and acetaldehyde) between carry out dehydration and the aldimine compound that obtains; By polyamine and ketone or the enamine compound that obtains with aldehyde with 2～8 carbon atoms with 3～8 carbon atoms; Yi is Ji the oxazolidine compound.

Contain in the compound bearing active hydrogen (β 1) at these, preferred end-blocking or not polyamine, end-blocking or the polynary alcohol and water of end-blocking not of end-blocking of using, more preferably end-blocking or the not polyamine and the water of end-blocking, be preferably polyamine, ketimine compound and water especially, most preferably be 4,4 '-diaminodiphenyl-methane, xylylene diamines, isophorone diamine, ethylenediamine, Diethylenetriamine, three second tetramines, the ketimine compound and the water that obtain by above-mentioned polyamine and ketone.

(during the preparation composite resin particle) if desired, can use reaction terminating agent (β s) when use contains the compound (β 1) of active hydrogen group when preparation resin particle (P).Use compound (β 1) and reaction terminating agent (β s) by uniting in certain proportion, can regulate the molecular weight of the resin (q) that constitutes resin particle (Q) at an easy rate.

As reaction terminating agent (β s), for example can enumerate: have 1～40 carbon atom monoamine (as, diethylamine, dibutylamine, butylamine, lauryl amine, monoethanolamine and diethanolamine); End-blocking product (as, kitimine compound) with monoamine of 3～40 carbon atoms; Have 1～40 carbon atom monohydroxy alcohol (as, methyl alcohol, ethanol, isopropyl alcohol, butanols and phenol); Have 2～40 carbon atoms monobasic mercaptan (as, butyl mercaptan and lauryl mercaptan); Have 5～40 carbon atoms monoisocyanates (as, butyl isocyanate, lauryl isocyanates and phenyl isocyanate); And mono-epoxy compounds (as, butyl glycidyl ether) with 2～40 carbon atoms.

The combination of Miao Shuing in the above [2] (promptly, combination with the prepolymer that contains reactive group (α 2) that contains active hydrogen group and hardening agent (β 2), wherein (β 2) have can with the functional group that contains active hydrogen group reaction) in, contain that the contained example that contains active hydrogen group comprises amino in the prepolymer (α) of reactive group, hydroxyl (alcoholic hydroxyl and phenolic hydroxyl), sulfydryl, carboxyl, and by can break away from compound (as, ketone and aldehyde) carry out the organic group that end-blocking obtained (as, contain the group of ketimide, the group that contains the group Han oxazolidine of aldimine, the group that contains enamine, the group that contains acetal, the group that contains ketal, the group that contains mercaptal, and the group that contains thioketal).

Contain in the active hydrogen group described, be preferably amino, hydroxyl and carry out the organic group that end-blocking obtained, more preferably hydroxyl by breaking away from compound.

As have can with the hardening agent (β 2) of the functional group that contains active hydrogen group reaction, for example can enumerate: polyisocyanates (15), polyepoxide (18), dicarboxylic acids (13), polybasic carboxylic acid (14), the compound that has the compound of at least two anhydride groups and have at least two acyl halide groups.

In described hardening agent (β 2), be preferably polyisocyanates (15) and polyepoxide (18), more preferably polyisocyanates.

Example with compound of at least two anhydride groups is PMA and maleic anhydride (being total to) polymkeric substance.

Example with compound of at least two acyl halide groups is the carboxylic acid halides (acyl chlorides, acylbromide and acyl iodides) of dicarboxylic acids (13) or polybasic carboxylic acid (14).

At the preparation resin particle when (P) (during the preparation composite resin particle), if desired, can use have can with the hardening agent (β 2) of the functional group that contains the active hydrogen group reaction in use reaction terminating agent (β s).Use compound (β 2) and reaction terminating agent (β s) by uniting in certain proportion, can regulate the molecular weight of the resin (q) that constitutes resin particle (Q) at an easy rate.

Use amount for hardening agent (β), preferably making the equivalent [α] of the reactive group in the prepolymer (α) that contains reactive group and equivalent proportion [α]/[β] of the equivalent that contains active hydrogen group [β] in the hardening agent (β) is 1/2～2/1, more preferably 1.5/1～1/1.5, especially be preferably 1.2/1～1/1.2.Also promptly, the upper limit of equivalent proportion [α]/[β] is preferably 2/1, and more preferably 1.5/1, be preferably 1.2/1 especially; Equally, lower limit is preferably 1/2, and more preferably 1/1.5, be preferably 1/1.2 especially.

In addition, if hardening agent (β) is a water, then water is considered to have the compound of divalence active hydrogen group.

For by making the prepolymer (α) that contains reactive group and hardening agent (β) react resulting resin (p), its Mw is preferably more than and equals 3,000, and more preferably 3,000～10,000,000, be preferably 5,000～1,000,000 especially.That is, the upper limit of Mw (p) is preferably 10,000,000, and more preferably 1,000,000; Equally, its lower limit is preferably 3,000, and more preferably 5,000.

The selection in the prepolymer (α) that contains reactive group and the reaction time of hardening agent (β) is the reactivity decision of making up according to the kind of the contained reactive group of prepolymer (α) and with hardening agent (β), it is preferably 10 minutes～and 40 hours, more preferably 30 minutes～24 hours, be preferably 30 minutes especially～8 hours.

In addition, temperature of reaction is preferably 0～150 ℃, more preferably 50～120 ℃.

As required, can use well-known catalysts.Specifically, when isocyanates reacts with the compound that contains active hydrogen group, can use for example lauric acid two fourth tin, dioctyltin laurate etc.

Except that (p1) and/or (p2), the resin (p) that is used for resin particle of the present invention also can comprise one or more other resins (p3), and prerequisite is that the adding of (p3) does not damage (p1) and performance (p2).

(p3) example is, (p1) and (p2) vibrin, vinylite, urethane resin, epoxy resin, polyamide, polyimide resin, silicones, phenolics, melamine resin, Lauxite, anline resin, ionomer resin and polycarbonate resin in addition.Wherein be preferably the combination of vinylite, urethane resin, epoxy resin, vibrin and above-mentioned resin.The concrete example of vinylite, urethane resin, epoxy resin and vibrin discloses cited material among the WO03/106541 referring to the world.

The Mn of resin (p3) is preferably 500～2, and 000,000, more preferably 1,000～1,000,000.In the resin (p), content (p3) is preferably smaller or equal to 80%, more preferably smaller or equal to 60%, be preferably 5～40% especially.

The Mn of resin (p), fusing point, Tg, SP value can be adjusted in the suitable preferable range according to purposes.

For example, when composite resin particle of the present invention was used for slush molding with resin and powder coating resin, the Mn of resin (p) was generally 1,000～500,00, is preferably 1,500～200,000, more preferably 2,000～100,000, is preferably 2,500～10,000 especially.The fusing point of resin (p) (measure with DSC, following fusing point is the measured value of DSC method) is generally 0～200 ℃, is preferably 35～150 ℃, more preferably 40～120 ℃, is preferably 45～100 ℃ especially.The Tg of resin (p) is generally-60～100 ℃, be preferably-50～90 ℃, more preferably-40～80 ℃, be preferably-30～60 ℃ especially.The SP value of resin (p) is generally 7～18, is preferably 8～16, more preferably 9～14.

When resin (p) was used as the toner of electrofax, electrostatic recording, xeroprinting etc., the Mn of resin (p) was generally 1,000～5,000,000, is preferably 1,500～500,000, more preferably 2,000～100,000, is preferably 2,500～50,000 especially.The fusing point of resin (p) is generally 20～300 ℃, is preferably 40～250 ℃, more preferably 60～220 ℃, is preferably 80～200 ℃ especially.The Tg of resin (p) is generally 20～200 ℃, is preferably 30～180 ℃, more preferably 35～160 ℃, is preferably 40～100 ℃ especially.The SP value of resin (p) is generally 7～16, is preferably 8～15, is preferably 9～14 especially.

In the resin particle of the present invention (P), except that resin (p), can also contain one or more adjuvants (T) (for example various adjuvants such as filling agent, colorant, plastifier, release agent, charge control agent, ultraviolet light absorber, antioxidant, antistatic agent, fire retardant, antiseptic, antiseptic) as required.

As filling agent, for example can enumerate: silicon dioxide, aluminium oxide, titanium dioxide, barium titanate, magnesium titanate, calcium titanate, strontium titanates, zinc paste, tin oxide, silica sand, clay, mica, wollastonite, zeyssatite, chromium oxide, cerium oxide, chromium oxide, cerium oxide, bengals, antimony trioxide, magnesium oxide, zirconia, barium sulphate, barium carbonate, lime carbonate, silit, silicon nitride etc.

As colorant, known dyestuff and pigment all can use, the material of putting down in writing among for example above-mentioned material and the international open WO03/106541.

As plastifier (V), can use foregoing material.

As release agent, the dynamic viscosity in the time of for example can using wax and 25 ℃ is 30～100, the silicone oil of 000cSt.

As wax, can use known material, for example: polyolefin-wax (as Tissuemat E and polypropylene wax); Long chain hydrocarbon (as paraffin and Sha Suo wax); With the wax that contains carbonyl.The wax that preferably contains carbonyl in the above-mentioned wax.As the wax that contains carbonyl, for example can enumerate: multichain alkanoic acid ester (as Brazil wax, montan wax, trimethylolpropane tris behenate, pentaerythrite four behenates, pentaerythrite diacetate esters two behenates, glycerol tri-docosanoic acid ester and 1,18-octacosanol distearate); Many alkanols ester (as three stearyl trimellitates and distearyl maleate); Multichain alkane acid amides (for example ethylenediamine two mountain Yu base acid amides); Many alkylamides (for example tri trimellitate (stearmide)); Dialkyl ketone (as distearyl ketone).Contain in the example of wax of carbonyl preferred multichain alkanoic acid ester.

As charge control agent, known charge control agent all can be used for the present invention, can enumerate the material of putting down in writing among for example aforesaid material and the international open WO03/106541.

For the composition ratio in the resin particle of the present invention (P), based on the weight of composition, the ratio of resin (p) is preferably 30～97%, more preferably 40～95%, most preferably is 45～92%; For adjuvant, the ratio of colorant is preferably 0.05～60%, is preferably 0.1～55%,, most preferably be 0.5～50%; The ratio of release agent is preferably 0～30%, more preferably 0.5～20%, most preferably is 1～10%; The ratio of charge control agent is preferably 0～20%, more preferably 0.1～10%, most preferably is 0.5～7.5%; The ratio of fluidizing agent is preferably 0～10%, more preferably 0～5%, most preferably is 0.1～4%.Total content of all adjuvants is preferably 3～70%, more preferably 5～60%, most preferably is 8～55%.If each composition ratio all is in above-mentioned institute restricted portion, then obtain to have the toner of good charged characteristic easily.

The volume average particle size of resin particle of the present invention (P) can be according to the present invention in the purposes of composite resin particle and suitably design.

When resin particle of the present invention is used for powdery paints, slush molding and hot melt adhesive, its particle diameter is generally 10～300 μ m, is preferably 50～300 μ m, more preferably 50～200 μ m, most preferably be 80～180 μ m.When resin particle of the present invention is used for electrofax tinter, electrostatic recording toner, xeroprinting toner, its particle diameter is generally 0.1～100 μ m, is preferably 0.5～50 μ m, more preferably 1～10 μ m, most preferably be 2～8 μ m.

Volume average particle size can be by laser type granulometry device LA-920 (hole field make made), electrophoresis particle size distribution device ELS-8000 (Da mound electronics system) or Multisizer III (Coulter corporate system) measure.

Contain resin (q) in the resin particle of the present invention (Q).

Resin (q) can be thermoplastic resin, also thermoset resin be can be, vinylite, urethane resin, epoxy resin, polyester, polyamide, polyimide, silicones, phenolics, melamine resin, Lauxite, ionomer resin, polycarbonate and their potpourri for example can be.Viewpoint from the microspheroidal resin particle of easy acquisition homogeneous is preferably vinylite, polyurethane, epoxy resin, polyester and their potpourri, more preferably vinylite, epoxy resin, polyester and their potpourri.

Below will be that vinylite, polyurethane, epoxy resin and polyester are described to the preferred resin in the resin (q), equally also can use other resins.(q) object lesson both can be the material of putting down in writing below, also can be the material of putting down in writing among the international open WO03/106541.

Vinylite can comprise the polymkeric substance that is obtained by vinyl monomer homopolymerization or copolymerization.In polymerization, can use known polymerization catalyst.

Following compound (1)～(10) can be used as vinyl monomer and use.

(1) vinyl hydro carbons:

(1-1) aliphatic ethylene base hydro carbons:

Carbon number is 2～12 olefine (for example ethene, propylene, butylene, isobutylene, amylene, heptene, diisobutylene, octene, dodecylene, vaccenic acid and a alpha-olefin with 3～24 carbon atoms); And carbon number is 4～12 alkadiene hydrocarbon (for example butadiene, isoprene, 1,4-pentadiene and 1,6-hexadiene).

(1-2) cycloaliphatic vinyl hydro carbons:

Carbon number is 6～15 monocycle or dicyclo olefine (for example cyclohexene, vinyl cyclohexene and ethidine double-heptene); Carbon number is 5～12 monocycle or dicyclo alkadiene hydrocarbon (for example (two) cyclopentadiene); Terpenes (for example sobrerone, limonene, indenes); Deng.

(1-3) aromatic ethenyl hydro carbons: styrene; The styrene that alkyl (carbon number is 1～24 alkyl, naphthenic base, aralkyl and/or alkenyl) replaces (for example α-Jia Jibenyixi, vinyltoluene, 2,4-dimethyl styrene, ethyl styrene, butylstyrene, styryl phenyl, cyclohexyl benzene ethene, benzyl styrene, crotyl benzene, divinylbenzene); Vinyl naphthalene etc.

(2) contain the vinyl monomer and the salt thereof of carboxyl:

Carbon number is 3～30 unsaturated monocarboxylic acid (for example (methyl) acrylic acid, crotonic acid, iso-crotonic acid, cinnamic acid); Carbon number is 3～30 unsaturated dicarboxylic acid and acid anhydrides (for example maleic acid (acid anhydride), fumaric acid, itaconic acid, citraconic acid (acid anhydride), mesaconic acid) thereof; Carbon number is monoalkyl (having 1～24 carbon atom) ester (for example maleic acid monomethyl ester, maleic acid list stearyl, fumaric acid list ethyl ester, itaconic acid monobutyl ester, itaconic acid glycol monoether) of 3～30 unsaturated dicarboxylic acid etc.

As the salt of the vinyl monomer that contains carboxyl, for example can enumerate: alkali metal salt (sodium salt, sylvite etc.), alkali salt (calcium salt, magnesium salts etc.), ammonium salt, amine salt, quaternary ammonium salt.Amine salt is so long as amines gets final product, and there is no particular limitation, for example can be primary amine salt (ethylamine salt, butylamine salt and octylamine salt etc.), secondary amine salt (diethyl amine salt and dibutylamine salt etc.) and tertiary ammonium salt (triethylamine salt and tri-n-butylamine salt etc.).Tetraethyl ammonium salt, lauryl triethyl ammonium salt etc. can be used as the example of quaternary ammonium salt.

The concrete example of salt that contains the vinyl monomer of carboxyl can be: PAA, Sodium methacrylate, maleic acid list sodium, maleic acid disodium, potassium acrylate, methacrylic acid potassium, maleic acid monopotassium salt, acrylic acid lithium, acrylic acid cerium, ammonium acrylate, calcium acrylate, acrylic acid aluminium etc.

(3) contain the vinyl monomer and the salt thereof of sulfo group:

Carbon number is 2～14 alkene sulfonic acid (for example vinyl sulfonic acid, (methyl) allyl sulphonic acid and methyl ethylene sulfonic acid); Styrene sulfonic acid and alkyl thereof (having 2～24 carbon atoms) derivant (for example α-Jia Jibenyixi sulfonic acid); Carbon number is (methyl) acrylic acid sulfo group (hydroxyl) Arrcostab (for example (methyl) acrylic acid sulfo group propyl diester, 2-hydroxyl-3-(methyl) acryloxy propane sulfonic acid) of 5～18; Carbon number is 5～18 sulfo group (hydroxyl) alkyl (methyl) acrylamide (for example 2-(methyl) acrylamido-2,2-dimethyl ethane sulfonic acid, 2-(methyl) acrylamide-2-methyl propane sulfonic acid); Alkyl (carbon number is 3～18) allyl sulfosuccinic acid (for example, propyl group allyl sulfosuccinic acid, butyl allyl sulfosuccinic acid); Poly-(n=2～30) oxyalkylene (oxygen ethene, oxypropylene, oxygen butylene: homopolymerization, random, block all can) single (methyl) acrylate sulfuric ester (for example poly-(n=5～15) oxygen ethene monomethacrylates sulfuric ester); Polyoxyethylene encircle more the phenylate sulfuric ester (for example by general formula (1-1) or (2-2) expression sulfuric ester; By sulfonic acid and the salt thereof shown in the general formula (1-3)).

As salt, can use the gegenion shown in " vinyl monomer and salt thereof that (2) contain carboxyl ".

Wherein R represents to have the alkyl of 1～15 carbon atom, and AO represents to have the oxyalkylene of 2～4 carbon atoms; When n is during greater than 1 integer, n oxyalkylene can be identical or different; When n oxyalkylene not simultaneously, can be the combination of random, block and/or random and block; Ar represents phenyl ring, and n represents 1～50 integer, and it is 1～15 alkyl that R ' expression has or do not have the substituent carbon number of fluorine atom.

(4) contain the vinyl monomer and the salt thereof of phosphono:

(methyl) acryloxyalkyl (having 1～24 carbon atom) Monophosphate (for example] 2-hydroxyethyl (methyl) acryloyl phosphate and phenyl-2-acryloxy ethyl phosphonic acid ester); (methyl) acryloxyalkyl (having 1～24 carbon atom) phosphoric acid (for example 2-acryloxy ethyl phosphonic acid).

(5) contain the vinyl monomer of hydroxyl:

The allyl ether of hydroxy styrenes, N-methylol (methyl) acrylamide, (methyl) hydroxyethyl acrylate, (methyl) acrylic acid hydroxypropyl ester, polyethyleneglycol (methyl) acrylate, (methyl) allyl alcohol, crotonyl alcohol, different crotonyl alcohol, 1-butylene-3-alcohol, propargyl alcohol, 2-hydroxyethyl propenyl ether, sucrose etc.

(6) nitrogenous vinyl monomer:

(6-1) contain amino vinyl monomer:

(methyl) acrylic-amino ethyl ester, (methyl) acrylic acid dimethyl aminoethyl ester, (methyl) acrylic acid diethylamino ethyl ester, methacrylic acid tert-butyl group amino-ethyl ester, N-amino-ethyl (methyl) acrylamide, (methyl) allyl amine, (methyl) acrylic acid morpholinyl ethyl ester, 4-vinylpridine, the 2-vinylpyridine, crotylamine, N, N-dimethylamino styrene, methyl alpha-acetamido-acrylate, vinyl imidazole, the N-vinyl pyrrole, N-vinyl thiopyrrolidone, N-aryl phenylenediamine, aminocarbazole, and the salt of above-mentioned substance etc.

(6-2) contain the vinyl monomer of acylamino-:

(methyl) acrylamide, N-methyl (methyl) acrylamide, N-butyl acrylamide, diacetone acrylamide, N-methylol (methyl) acrylamide, N, N '-methylene-two (methyl) acrylamide, cinnamamide, N,N-DMAA etc.

(6-3) carbon number is 3～10 the vinyl monomer that contains itrile group:

(methyl) vinyl cyanide, cyano styrene, cyanoacrylate etc.

(6-4) contain the vinyl monomer of quaternary ammonium cation:

(methyl) acrylic acid dimethyl aminoethyl ester, (methyl) acrylic acid diethylamino ethyl ester, dimethyl aminoethyl (methyl) acrylamide, diethylamino ethyl (methyl) acrylamide, diallylamine etc. contain the quaternized products (being undertaken quaternized and material that obtain, for example dimethyl diallyl ammonium chloride and trimethyl allyl ammonium chloride by quaternizing agents such as chloromethanes, dimethyl suflfate, benzyl chloride, dimethyl carbonates) of the vinyl monomer of uncle's amino.

(6-5) carbon number is 8～12 the vinyl monomer that contains nitro:

Nitrostyrolene etc.

(7) carbon number is 6～18 the vinyl monomer that contains epoxy radicals:

(methyl) glycidyl acrylate, (methyl) acrylic acid tetrahydro furfuryl ester are to vinyl benzene base oxide (p-vinylphenyl oxide) etc.

(8) carbon number is 2～16 the vinyl monomer that contains halogen:

Vinyl chloride, bromine ethene, vinylidene chloride, allyl chloride, chlorostyrene, bromstyrol, dichlorostyrene, 1-chloro-4-methyl-benzene, phenyl tetrafluoride ethene, chlorbutadiene etc.

(9) vinyl esters, vinyl (sulphur) ether, vinyl ketone and vinyl sulfone:

(9-1) carbon number is 4～16 vinyl esters:

Vinyl acetate, vinyl butyrate, propionate, the butyric acid vinyl acetate, diallyl phthalate, diallyl adipate, methylvinyl acetate, the metering system vinyl acetate, cyclohexyl methacrylate, the methacrylic acid benzyl ester, (methyl) phenyl acrylate, the methoxyacetic acid vinyl acetate, vinyl benzoate, carbon number is (methyl) alkyl acrylate of 1～50 ((methyl) methyl acrylate for example, (methyl) ethyl acrylate, (methyl) butyl acrylate, (methyl) dodecylacrylate, (methyl) acrylic acid heptadecyl ester), (two alkyl is that carbon number is 2～8 straight chain to dialkyl fumarate, branching or ester ring type group), (two alkyl is that carbon number is 2～8 straight chain to dialkyl maleate, branching or ester ring type group), many (methyl) allyloxy alkanes (two allyloxy ethane for example, three allyloxy ethane, tetraene propoxyl group propane), vinyl monomer (single (methyl) acrylate of polyglycol (molecular weight is 300) for example with polyalkylene glycol chain, polypropylene glycol (molecular weight is 500) mono acrylic ester, methyl alcohol-ethylene oxide (10 moles) addition products (methyl) acrylate, lauryl alcohol-ethylene oxide (30 moles) addition products (methyl) acrylate), many (methyl) acrylate (many (methyl) acrylate of polyvalent alcohol for example: ethylene glycol bisthioglycolate (methyl) acrylate, propylene glycol two (methyl) acrylate, polyglycol two (methyl) acrylate) etc.

(9-2) carbon number is 3～16 vinyl (sulphur) ether:

Vinyl methyl ether, EVE, vinyl butyl ether, vinyl 2-ethylhexyl ether, vinyl phenyl ether, vinyl 2-methoxy ethyl ether, methoxyl butadiene, phenoxy group styrene etc.

(9-3) carbon number is 4～12 vinyl ketone (for example ethenyl methyl ketone, vinyl ethyl ketone, ethenylphenyl ketone);

Carbon number is vinyl sulfone of 2～16 (for example vinyl thioether, to vinyl diphenylsulfide, vinyl ethyl sulfide, vinyl ethyl sulfone, divinylsulfone and divinyl sulfoxide) etc.

(10) other vinyl monomer:

Isocyanato-(methyl) ethyl acrylate, isopropenyl-α, α-Er Jiajibianji isocyanates etc.

In these vinyl monomers, preferred use vinyl hydro carbons, vinyl monomer that contains carboxyl and salt thereof, contain sulfonic vinyl monomer and salt thereof, contain hydroxyl vinyl monomer, contain the vinyl monomer of nitrogen, more preferably vinyl hydro carbons, the vinyl monomer that contains carboxyl and salt thereof, contain sulfonic vinyl monomer and salt thereof, be preferably the aromatic ethenyl hydro carbons especially, contain carboxyl vinyl monomer and salt thereof, contain sulfonic vinyl monomer and salt thereof.

In vinylite,, can arbitrary proportion use in aforementioned (1)～(10) 2 kinds or carry out copolymerization and obtain more than any monomer of 2 kinds for the polymkeric substance that obtains by the vinyl monomer copolymerization (ethylene monomer copolymer).The example of multipolymer comprises styrene-(methyl) acrylate copolymer, Styrene-Butadiene, (methyl) acrylic acid-(methyl) acrylate copolymer, styrene-acrylonitrile copolymer, styrene-maleic acid (acid anhydride) multipolymer, styrene-(methyl) acrylic copolymer, styrene-(methyl) acrylic acid-divinyl benzene copolymer and styrene-styrene sulfonic acid-(methyl) acrylate copolymer etc.

Composite resin particle is preferably made by following method: the precursor (p0) or their solution of resin (p), resin (p) are disperseed in the water-borne dispersions that contains resin particle (Q), resin particle (Q) is dispersed in the water-borne dispersions.Therefore, when forming water-borne dispersions, resin (Q) is not exclusively dissolving in water at least preferably at least.Therefore, when vinylite is multipolymer, though constitute the kind that the ratio of the hydrophobic monomer of this vinylite and hydrophilic monomer depends on monomer, if be benchmark with the general assembly (TW) of monomer, then the ratio of hydrophobic monomer is preferably more than and equals 10%, more preferably more than or equal to 30%.If the ratio of hydrophobic monomer is lower than 10% then vinylite is easy to be water-soluble, the uniform particle diameter of composite resin particle is easy to be damaged.

At this, hydrophilic monomer is can be with the monomer of arbitrary proportion dissolving in water, and hydrophobic monomer is except that the monomer the former (at 25 ℃, the amount of being dissolved in the water of 100g is less than the monomer of 100g) (also being like this for following resin hereinafter).

As polyester, can use the polycondensation product that forms by polyvalent alcohol and polybasic carboxylic acid, its acid anhydrides or low alkyl group (carbon number is 1～4) ester.

Known polycondensation catalyst can be used for this polycondensation reaction.

The polyvalent alcohol that can use is dibasic alcohol (11) and 3 yuan～8 yuan or more polynary polyvalent alcohol (12).

The polybasic carboxylic acid that can use, their acid anhydrides or lower alkyl esters are dicarboxylic acids (13), 3 yuan～6 yuan or more polynary polybasic carboxylic acid (14), their acid anhydrides and lower alkyl esters.

The example of dibasic alcohol (11) and 3 yuan～8 yuan or more polynary polyvalent alcohol (12) is for constituting the polyvalent alcohol of aforementioned polyol component.

The AO addition product of preferred aliphat polyvalent alcohol and novolac resin in them, more preferably the AO addition product of novolac resin.

The example of the dicarboxylic acids that can use (13) is aforesaid aliphatics (comprising alicyclic) dicarboxylic acid and an aromatic dicarboxylic acid.

In them, be preferably alkylene dicarboxylic acids and aromatic dicarboxylic acid, more preferably aromatic dicarboxylic acid.

The example of can use 3 yuan～6 yuan or more polynary polybasic carboxylic acid (14) is above-mentioned aliphatics (comprising alicyclic) polybasic carboxylic acid and aromatic series polybasic carboxylic acid.

The acid anhydrides of the acid anhydrides of the dicarboxylic acids that can use (13) or 3 yuan～6 yuan or more polynary polybasic carboxylic acid (14) is trimellitic anhydride and pyromellitic acid acid anhydride.The example of their lower alkyl esters is methyl esters, ethyl ester and isopropyl ester.

For polyester, dibasic alcohol, 3 yuan～8 yuan or more polynary polyvalent alcohol, dicarboxylic acids, 3 yuan～6 yuan or more polynary polybasic carboxylic acid and their potpourri can arbitrary proportion mix and use.Equivalent proportion [OH]/[COOH] of hydroxyl [OH] and carboxyl [COOH] is preferably (2/1)～(1/1), and more preferably (1.5/1)～(1/1) is preferably (1.3/1)～(1.02/1) especially.

Equally, the ester group equivalent in the polyester (each equivalent ester group corresponding molecular weight) is preferably 50～2,000, and more preferably 60～1,000, be preferably 70～500 especially.

As polyurethane, can use polyisocyanates (15) and contain the polyaddition products of compound bearing active hydrogen (β 1) (for example water, dibasic alcohol (11), 3 yuan～8 yuan or more polynary polyvalent alcohol (12), dicarboxylic acids (13), 3 yuan～6 yuan or more polynary polybasic carboxylic acid (14), polyamine (16) and polythiol (17)).

Known addition polymerization catalyst can be used for this addition polymerization.

The example of polyisocyanates (15) comprises that carbon number is 6～20 (not comprise the carbon atom in the NCO group; Below identical) aromatic polyisocyanate, carbon number is 2～18 aliphatic polyisocyante, carbon number is 4～15 alicyclic polyisocyanates, carbon number is 8～15 aromatic-aliphatic polyisocyanates, and the modified product of these polyisocyanates (modified polyisocyanate that for example contains following group: carbamate groups, carbodiimide, allophanate group, urea groups, the biuret base, urea diketone (urethodione) base, urea imines (urethoimine), the isocyanuric acid ester group; or the oxazolidine ketone group), and in them 2 kinds or multiple potpourri etc.

The example of aromatic polyisocyanate comprises 1,3-or 1,4-phenylene vulcabond, 2,4-or 2,6-inferior cresyl vulcabond (TDI), thick TDI, 2,4 '-or 4,4 '-methyl diphenylene diisocyanate (MDI), thick (MDI) (rough tetramethyl triaminotriphenyl methane NH2 (condensation product of formaldehyde and aromatic amine (aniline) or its potpourri; Diaminodiphenyl-methane and a small amount of (for example 5-20%) have 3 or a potpourri of the polyamine of polyamino more) the phosphinylidyne chloride: polyenoid propyl group polyisocyanates (PAPI)), 1; 5-naphthalene diisocyanate, 4; 4 ', 4 "-triphenylmethane triisocyanate ,-or right-isocyanato-benzenesulfonyl isocyanates and 2 kinds or multiple potpourri etc. in them.

The example of aliphatic polyisocyante comprises ethylidene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), ten dimethylene diisocyanates, 1,6,11-undecane triisocyanate, 2,2, the 4-trimethyl hexamethylene diisocyanate, lysinediisocyanate, 2,6-two isocyanato-methylhexanoic acid esters, two (2-isocyanatoethyl) fumarate, two (2-isocyanatoethyl) carbonic ester, 2-isocyanatoethyl-2,6-two isocyanato-capronates, and 2 kinds or multiple potpourri in them.

The example of alicyclic polyisocyanates comprises isofoer diisocyanate (IPDI), dicyclohexyl methyl hydride-4,4 '-diisocyanate (hydrogenation MDI), cyclohexene diisocyanate, methylcyclohexene diisocyanate (hydrogenation TDI), two (2-isocyanatoethyl)-4-cyclohexene-1,2-dicarboxylic ester, 2,5-or 2,6-norcamphane diisocyanate and in them 2 kinds or multiple potpourri etc.

Between the example of aromatic-aliphatic polyisocyanates comprises-and or right-eylylene diisocyanate (XDI), α, α, α ', α '-tetramethyl eylylene diisocyanate (TMXDI) and in them 2 kinds or multiple potpourri etc.

The example of the modified product of polyisocyanates comprise have carbamate groups, the modified polyisocyanate of carbodiimide, allophanate group, urea groups, biuret base, uretdion, urea imido grpup, isocyanate group and/or oxazolidine ketone group, as modification MDI (for example urethane-modified MDI, carbodiimide modified MDI and the phosphate modified MDI of trialkyl), urethane-modified TDI, and in them 2 kinds or multiple potpourri (for example potpourri of modification MDI and urethane-modified TDI (prepolymer that contains isocyanates)) etc.

In these polyisocyanates, optimization aromatic polyisocyanates, aliphatic polyisocyante and alicyclic polyisocyanates, more preferably TDI, MDI, HDI, hydrogenation MDI and IPDI.As polyamine (16), can use carbon number is that 2～18 aliphatic polyamine, carbon number are 6～20 aromatic polyamine.

As carbon number is 2～18 aliphatic polyamine, and can use the alkyl (having 1～4 carbon atom) of (1) aliphatic polyamine, (2) described aliphatic polyamine or hydroxyalkyl (having 2～4 carbon atoms) substitution product, (3) aliphatic polyamine, (4) carbon number alicyclic or that contain heterocycle is fatty amine that contains aromatic rings of 8～15 etc.

(1) example of aliphatic polyamine comprises that carbon number is 2～12 Alkylenediamine (for example ethylenediamine, propane diamine, trimethylene diamines, tetra-methylenedimine and hexamethylene diamine), polyalkylene (carbon number is 2～6) polyamine (for example diethylene triamine, the two propylamine of imino group, two (hexa-methylene) triamine, trien and penten) etc.

(2) as the alkyl (having 1～4 carbon atom) or hydroxyalkyl (having 2～4 carbon atoms) substitution product of described aliphatic polyamine, for example comprise the amino propylamine of dialkyl group (having 1～3 carbon atom), tri-methyl hexamethylene diamine, amino ethyl ethanolamine, 2,5-dimethyl-2, the two propylamine of 5-hexamethylene diamine and methyl-imino etc.

(3) example alicyclic or that contain the aliphatic polyamine of heterocycle comprises that carbon number is 4～15 a alicyclic polyamine (for example 1,3-diamino-cyclohexane, different Fu Er ketone diamines, menthene diamines, 4,4 '-methylene bicyclohexane diamines (hydrogenation methylene dianiline (MDA)) and 3, two (the 3-aminopropyls)-2 of 9-, 4,8,10-four oxa-volutions [5,5] undecane), carbon number is 4～15 heterocycle polyamine (for example piperazine, a N-aminoethyl piperazine, 1,4-diaminoethyl piperazine and 1, two (the 2-amino-2-methyl propyl group) piperazines of 4-) etc.

(4) example that contains the fatty amine (having 8～15 carbon atoms) of aromatic rings comprises xylylene amine, tetrachloro-to xylylene amine etc.

As foregoing carbon number is 6～20 aromatic polyamine, can use (1) unsubstituted aromatic polyamine; (2) has the aromatic polyamine of one or more nuclear substituted alkyls (alkyl with 1～4 carbon atom is as methyl, ethyl, n-pro-pyl or isopropyl and butyl); (3) has the aromatic polyamine that one or more nuclears replace electron withdraw group (as halogen (for example Cl, Br, I and F), alkoxy (for example methoxyl and ethoxy) and nitro); (4) has the aromatic polyamine etc. of parahelium group.

(1) example of unsubstituted aromatic polyamine comprises 1,2-, 1,3-or 1,4-phenylenediamine, 2,4 '-or 4,4 '-diphenyl methane diamines, rough diphenyl methane diamines (polyphenyl polymethylene polyamine), diamino diphenyl sulfone, benzidine, phenyl disulfide amine, two (3, the 4-diamino-phenyl) sulfone, 2, the 6-diamino-pyridine ,-aminobenzyl amine, triphenylmethane-4,4 ', 4 "-triamine, naphthylenediamine, and in them 2 kinds or multiple potpourri etc.

(2) (for example carbon number is 1～4 alkyl to have the nuclear substituted alkyl, as methyl, ethyl, n-pro-pyl or isopropyl and butyl) the example of aromatic polyamine comprise: 2,4-or 2,6-methylene phenylenediamine, rough methylene phenylenediamine, diethyl methylene phenylenediamine, 4,4 '-diamido-3,3 '-dimethyl diphenylmethane, 4,4 '-two (ortho-aminotoluenes), dianisidine, 1,3-dimethyl-2,4-diaminobenzene, and their potpourri.

(3) have nuclear and replace electron withdraw group (halogens such as Cl, Br, I and F for example; Alkoxy such as methoxyl and ethoxy; The example of aromatic polyamine and nitro) comprises: di-2-ethylhexylphosphine oxide (o-chloraniline), the adjacent phenylenediamine of 4-chloro-, 2-chloro-1,4-phenylenediamine, 3-amino-4-chloroaniline and 4-bromo-1,3-phenylenediamine.

(4) example with aromatic polyamine of parahelium group comprises: part or all of aromatic polyamine (1)～(3)-NH ₂(wherein R ' represents alkyl to group quilt-NH-R ' group, the low alkyl group that has 1～4 carbon atom as methyl, ethyl etc.) displacement and the aromatic polyamine that obtains, as 4,4 '-two (methylamino) diphenyl methane, 1-methyl-2-methylamino-4-aminobenzene etc.; The polyamide polyamine is as the low molecular polyamides polyamine that is obtained by dicarboxylic acid (for example dimer acid) and excessive (corresponding 2 moles or more moles of every equimolar acid) polyamine (for example foregoing Alkylenediamine and polyalkylene polyamine) condensation; The polyethers polyamine is as hydride of the cyanoethylation product of polyether glycol (for example poly alkylene glycol) etc.

As polythiol (17), can use carbon number is that 2～24 two mercaptan, carbon number are 5～30 3 yuan～6 yuan or more polynary polythiol etc.

The example of two mercaptan comprises ethylene mercaptan, 1,4-succinimide mercaptans, 1,6-ethanthiol etc.

The example of polythiol comprises Capcure-3800 (manufacturing of japan epoxy resin Co., Ltd.), polyvinyl mercaptan etc.

Have in the compound bearing active hydrogen (β 1) at these, preferably make water, glycol (11), polyvalent alcohol (12), dicarboxylic acid (13) and polyamine (16), more preferably glycol (11), polyvalent alcohol (12) and polyamine (16), special preferred diol (11), polyvalent alcohol (12) and polyamine (16).

As epoxy resin, can use ring-opening polymerization product, the polyepoxide (18) of polyepoxide (18) and contain the polyaddition products of compound bearing active hydrogen (β 1) and the acid anhydrides of polyepoxide (18) and dicarboxylic acid (13) or with the curing reaction product of the acid anhydrides of 3 yuan～4 yuan or more polynary polybasic carboxylic acid (14) etc.

In ring-opening polymerization, addition polymerization and curing reaction, can use known catalyzer etc.

As polyepoxide (18), as long as molecule has at least 2 epoxy radicals, just have no particular limits, the angle from the mechanical property of cured product has 2～6 epoxy radicals in the preferred molecule.

The epoxide equivalent of polyepoxide (18) (each epoxy radicals corresponding molecular weight) is preferably 65～1000, more preferably 70～500, is preferably 90～300 especially.The upper limit that is to say epoxide equivalent is preferably 1000, more preferably 500, is preferably 300 especially, and same, lower limit is preferably 65, more preferably 70, is preferably 90 especially.If epoxide equivalent surpasses 1000, cross-linked structure is loose easily, and rerum naturas such as the water proofing property of cured product, chemical resistance and physical strength suffer damage easily, and on the other hand, epoxide equivalent is lower than 65 polyepoxide (18) and is difficult to obtain (being difficult to synthesize).

As polyepoxide (18), can use the aromatic series polyepoxide, contain the polycyclic heteroaryl oxide, alicyclic polyepoxide, aliphatics polyepoxide etc.

As the aromatic series polyepoxide, can use the diglycidyl product of polyhydric phenol glycidol ether, polyhydric phenol ethylene oxidic ester, glycidyl aromatic polyamine and amino phenol etc.

The example of polyhydric phenol glycidol ether is the glycidol ether of Bisphenol F diglycidyl ether, bisphenol A diglycidyl ether, bisphenol b diglycidyl ether, bisphenol-A D diglycidyl ether, bisphenol-S diglycidyl ether, phenol or cresols-novolac resin.

The example of polyhydric phenol ethylene oxidic ester comprises o-phthalic acid diglycidyl ester, m-phthalic acid 2-glycidyl ester, terephthalic acid diglycidyl ester etc.

The example of glycidyl aromatic polyamine comprises N, N-diglycidylaniline, N, N, N ', N '-four glycidyl group xylylene amine, N, N, N ', N '-four glycidyl group diphenyl methane diamines etc.

As epoxide, also can further use: the triglycidyl group ether of para-aminophenol, carry out addition reaction and the diglycidyl ether (for example diglycidyl ether of the EO of bisphenol-A (4 moles) addition product) of oxyalkylene (ethylene oxide or propylene oxide, 2～20 moles) addition product of the diglycidyl urethane compound that obtains, bisphenol-A by inferior cresyl vulcabond or methyl diphenylene diisocyanate and diglycidyl.

As the polycyclic heteroaryl oxide, can use the triglycidyl group melamine.

As alicyclic polyepoxide, can use for example nuclear hydrogenated products (for example A Hydrogenated Bisphenol A F diglycidyl ether and hydrogenated bisphenol A diglycidyl ether) of vinyl cyclohexene dioxide, limonene dioxide, bicyclopentadiene dioxide, two (2,3-epoxide ring pentenyl) ether, ethylene glycol bisthioglycolate epoxy radicals dicyclopentenyl ether, dimer acid 2-glycidyl ester and aromatic series polyepoxide.

As the aliphatics polyepoxide, can use many ethylene oxidic esters, glycidyl fatty amine of polyglycidyl ether, the polyhydric aliphatic acid of multi-alcohol etc.

The example of the polyglycidyl ether of multi-alcohol comprises ethylene glycol diglycidylether, propylene glycol diglycidylether, tetramethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, polyethyleneglycol diglycidylether, polypropylene glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether, neopentylglycol diglycidyl ether, trimethylolpropane polyglycidylether, glycerol polyglycidylether, pentaerythrite polyglycidyl ether, sorbitol polyglycidylether, polyglycerol polyglycidyl ether etc.

The example of many ethylene oxidic esters of polyhydric aliphatic acid comprises diglycidyl oxalate, diglycidyl maleate, diglycidyl succinate, diglycidyl adipate etc.

The glycidyl fatty amine comprises N, N, N ', N '-four glycidyl group hexamethylene diamine and N, N, N ', N '-four glycidyl group ethylene diamine etc.

The aliphatics polyepoxide comprises (being total to) polymkeric substance of diglycidyl ether and (methyl) glycidyl acrylate.

In these polyepoxides, preferably use aliphatics polyepoxide and aromatic series polyepoxide.In the present invention, polyepoxide can use in them two or more combination.

The Mn of resin (q) is preferably 200～5, and 000,000, more preferably 2,000～1,000,000, be preferably 3,000～500,000 especially.

In the 8th of the present invention, Mn and weight-average molecular weight can be measured (THF solvent, primary standard substance: polystyrene) by gel permeation chromatography (GPC).Hereinafter, weight-average molecular weight is abbreviated as Mw.

The SP value of resin (q) is preferably 7～18, and more preferably 8～16, be preferably 8.5～14 especially.

The SP value is by Polymer Engineering and Science, February, and 1974, Vol.14, No.2, the method for 147-154 page or leaf record is calculated.

When resin (q) was crystalline polymer, the fusing point of resin (q) was preferably more than and equals 35 ℃, more preferably 40～250 ℃, was preferably 50～200 ℃ especially.

Fusing point is measured (programming rate: 20 ℃/min) by DSC.

For further improving thermotolerance, water proofing property, chemical resistance and the uniform particle diameter of composite resin particle, can import cross-linked structure in the resin (q).Described cross-linked structure can be any one the crosslinked form in covalent bonding, coordination bonding, ionic bonding, the hydrogen bonding.

Can adopt conventional method to import cross-linked structure.

The acid number of resin (q) is preferably 0～400, and more preferably 1～300, be preferably 1～200 especially, most preferably be 5～50.

When composite resin particle is used for coating adjuvant, coating additive, powder coating, slush molding with resin or hot melt adhesive, from to the tack of base material and the viewpoint of levelability, the acid number of resin (q) is preferably 0～400, more preferably 1～300, be preferably 1～200 especially, most preferably be 1～100.

When it was used for the toner of electrofax, electrostatic recording, xeroprinting etc., from the viewpoint of charged characteristic and the photographic fixing characteristic on paper, the acid number of resin (q) was preferably 0～400, and more preferably 1～300, be preferably 1～200 especially.

Resin particle (Q) must have enough intensity, thereby makes that the precursor (p0) of resin (p), resin (p) and/or their solution can be not destroyed because of shearing force when disperseing; And resin particle (Q) is difficult to dissolving or swelling in water; Resin particle (Q) also is difficult to dissolving or swelling in the precursor (p0) of resin (p), resin (p) and/or their solution.

In order to prevent that resin particle (Q) from dissolving or swelling taking place in the employed solvent, preferably suitably adjust molecular weight (Mn, Mw), SP value, crystallinity, the cross-linked structure of resin (p) in water or when disperseing.

From the viewpoint of shape, uniform particle diameter, powder fluidity, thermotolerance (during storage) and the proof stress of composite resin particle, the Tg of resin (Q) be preferably 0～300 ℃, more preferably 20～250 ℃, especially be preferably 45～200 ℃, most preferably be 50～200 ℃.

Tg in the 8th of the present invention by DSC (20 ℃ of differential scanning calorimetries, programming rate/min) try to achieve.

Except that resin (q), resin particle (Q) also can contain aforesaid adjuvant (T) (for example various adjuvants such as filling agent, colorant, plastifier, release agent, charge control agent, ultraviolet light absorber, antioxidant, antistatic agent, fire retardant, antiseptic, antiseptic).

The content of adjuvant (T) can suitably be adjusted according to various uses, and for example the weight with resin particle (Q) is benchmark, and this content is preferably 0.01～150%, more preferably 0.2～100%, is preferably 0.5～80% especially.

The preparation method of resin particle (Q) has no particular limits, and for example, can use method [1]～[8] that exemplify below.Method [1]～[8] are the methods that obtains the aqueous liquid dispersion of resin particle (Q), wherein the aqueous liquid dispersion of resin particle (Q) can be directly used in preparation composite resin particle of the present invention, perhaps resin particle (Q) can be separated from aqueous liquid dispersion separately, perhaps can in the process of preparation aqueous liquid dispersion resin particle (Q) be separated.Separation method can adopt filtration method, decantation and centrifugal separation.

[1] for the situation of vinylite: with monomer as initiation material, in the presence of polymerization catalyst, utilize suspension polymerization, emulsion polymerization, seeding polymerization method or dispersion copolymerization method etc. to carry out polyreaction, directly prepare the aqueous liquid dispersion of resin particle (Q).

[2] for polyester, the polyaddition resin of polyurethane and epoxy resin etc. or condensation resin: with the precursor (p0) of resin (p) [as, previously described dibasic alcohol (11), polyvalent alcohol (13), dicarboxylic acids (14), polyisocyanates (15), polyamine (16], polythiol (17), polyepoxide monomers such as (18), and the Mn that obtains by the reaction of monomer dimerization or poly is smaller or equal to 1000 oligomer (comprising the polymerization reactant of monomer of the same race or the polymerization reactant of at least two kinds of monomers)] or the solution of precursor (p0) in the presence of suitable spreading agent, be dispersed in the aqueous medium, heat then or add hardening agent (as, have at least two in molecule and have the compound of reactive functional group with precursor) be cured the aqueous liquid dispersion of preparation resin particle (Q).

[3] for the polyaddition resin or the condensation resin of polyester, polyurethane and epoxy resin etc.: precursor (p0) (as, monomer or oligomer) or the solution of precursor (p0) (be preferably liquid, maybe can be) by heating liquefaction in the suitable emulsifying agent of dissolving, add water then and carry out Phase inversion emulsification.

[4] in advance by polyreaction (as any polyreaction mode such as addition polymerization, ring-opening polymerization, addition polymerization, addition condensation and polycondensation) preparation resin (q), adopt mechanical rotation formula or injecting type atomizer to pulverize aforementioned resin (q), carry out classification then, obtain resin particle (Q), then in the presence of suitable spreading agent, it is scattered in the water.

[5] pass through the solution that polyreaction (as any polyreaction mode such as addition polymerization, ring-opening polymerization, addition polymerization, addition condensation and polycondensation) prepares resin (q) in advance, the solution of resin (q) is sprayed, so that from the solution of resin (q), remove solvent, obtain resin particle (Q) with this, in the presence of suitable spreading agent, it is scattered in the water then.

[6] pass through the solution that polyreaction (as any polyreaction mode such as addition polymerization, ring-opening polymerization, addition polymerization, addition condensation and polycondensation) prepares resin (q) in advance, adding poor solvent [at the solvent of 25 ℃ of resin (q) less thaies 1% of being dissolved down] then in the solution of resin (q) separates out resin particle or resin (q) heating for dissolving is made solution in solvent, separate out resin particle by cooling then, remove solvent subsequently to obtain resin particle (Q), in the presence of suitable spreading agent, it is scattered in the water then.

[7] pass through the solution that polyreaction (as any polyreaction mode such as addition polymerization, ring-opening polymerization, addition polymerization, addition condensation and polycondensation) prepares resin (q) in advance, solution with resin (q) in the presence of suitable spreading agent is dispersed in the aqueous medium, removes wherein solvent by the mode of heating or decompression.

[8] pass through the solution that polyreaction (as any polyreaction mode such as addition polymerization, ring-opening polymerization, addition polymerization, addition condensation and polycondensation) prepares resin (q) in advance, in the solution of resin (q), dissolve examples of suitable emulsifiers, add water and carry out Phase inversion emulsification, remove wherein solvent by the mode of heating or decompression.

In method [1]～[8], method for optimizing [1]～[3], [7] and [8], more preferably method [1]～[3] and [7], especially method for optimizing [2], [3] and [7].

In preceding method [1]～[8], can use known surfactant (S) and water-soluble polymers (T) as emulsifying agent and spreading agent.

Under the situation of using surfactant (S), based on the weight of resin (p) and precursor (p0), the use amount of surfactant is preferably 0.1～20%, and more preferably 1～15%, be preferably 2～10% especially.

Under the situation of using water-soluble polymers (T), based on the weight of resin (p) and precursor (p0), the use amount of water-soluble polymers (T) is preferably 0.01～20%, and more preferably 0.1～15%, be preferably 0.2～10% especially.

Further, can unite the auxiliary agent as emulsification or dispersion such as use solvent (U) and/or plastifier (V).

Under the situation of using solvent (U), based on the weight of resin (p) and precursor (p0), the use amount of solvent (U) is preferably 0.1～20%, and more preferably 0.5～15%, especially be preferably 1～10%.

Under the situation of using plastifier (V), based on the weight of resin (p) and precursor (p0), the use amount of plastifier (V) is preferably 0.01～10%, and more preferably 0.1～8%, especially be preferably 1.0～5%.

As required, solvent (U) and/or plastifier (V) can be added to the water in emulsification or dispersion process or join in the resin (p).

The example of surfactant (S), water-soluble polymers (T), solvent (U) and plastifier (V) is as follows.

The polymkeric substance that the example of water-soluble polymers (T) is preferably cellulose, starch, polyvinyl alcohol (PVA), polyvinylpyrrolidone, polyglycol and contains acrylic acid (salt).

Just remove the easy degree of solvent, the preferred example of solvent (U) is aromatic solvent, halogen solvent, ester or solvent of ether ester type, ketones solvent and alcohols solvent, more preferably ester or solvent of ether ester type, ketones solvent and alcohols solvent.

The particle diameter of resin particle (Q) is usually less than resin particle (P), and from the viewpoint of uniform particle diameter, particle diameter ratio ([volume average particle size of particulate (Q)]/[volume average particle size of particle (P)]) is preferably 0.001～0.3.The lower limit of particle diameter ratio more preferably 0.003, the upper limit more preferably 0.25.If particle diameter ratio surpasses 0.3, because resin particle (Q) can not be adsorbed on the resin particle (P) efficiently, therefore the composite resin particle that is obtained trends towards having wide size distribution.

The volume average particle size of resin particle (Q) can be carried out the adjusting of appropriateness so that obtain the composite resin particle of desired size distribution in the scope of above-mentioned particle diameter ratio.

The volume average particle size of resin particle (Q) in general is preferably 0.0005～30 μ m.The upper limit more preferably 20 μ m, especially be preferably 10 μ m, lower limit more preferably 0.01 μ m, more preferably 0.02 μ m, especially be preferably 0.04 μ m.Yet if the volume average particle size of the composite resin particle that obtained is 1 μ m, the particle diameter of resin particle (Q) is preferably 0.0005～0.3 μ m, 0.001～0.2 μ m more preferably; If the volume average particle size of the composite resin particle that obtained is 10 μ m (C), then the preferable particle size of resin particle (Q) is 0.005～3 μ m, 0.05～2 μ m more preferably; If the volume average particle size of the composite resin particle that obtained is 100 μ m, then resin particle (Q) preferable particle size is 0.05～30 μ m, 0.1～20 μ m more preferably.Volume average particle size can be measured by laser class particle size distribution device LA-920 (the hole field makes made), electrophoresis-type particle size distribution device ELS-8000 (big mound electronics system) or Ku Erte particle collector [as trade name: Multisizer III (Coulter corporate system)].

There is no particular limitation for the preparation method of composite resin particle of the present invention, for example can implement: resin (p) or its organic solvent solution and the adjuvant that adds as required are dispersed in contain resin (q) and as required in the aqueous liquid dispersion (W) of the resin particle (Q) of the adjuvant of interpolation by following method, in the aqueous liquid dispersion of resin particle (Q), form the resin particle (P) that contains resin (p), thereby obtain the aqueous resin dispersion of composite resin particle, described composite resin particle is made of attached to resin particle (P) surface resin particle (Q).

Perhaps can implement: precursor (p0) or its organic solvent solution of resin (p) are dispersed in the aqueous liquid dispersion of the resin particle (Q) that contains resin (q) by following method, make precursor (p0) reaction, in the aqueous liquid dispersion of resin particle (Q), form the resin particle (P) that contains resin (p), thereby obtain the aqueous resin dispersion of resin particle, described resin particle is made of attached to resin particle (P) surface resin particle (Q).These two kinds of methods also can and be used (for example, using (p) or solvent solution (p0)).

The aqueous liquid dispersion of the composite resin particle that obtains by said method is carried out Separation of Solid and Liquid (if desired, can carry out Separation of Solid and Liquid repeatedly by adding water etc.), carry out drying removal aqueous medium then, thereby obtain composite resin particle of the present invention.

Do not have special restriction for diverting device that uses among the above-mentioned preparation method and/or the device that applies shearing force, can adopt general commercially available emulsifier unit and/or diverting device, its instantiation with list previously identical.

Consider from the viewpoint of uniform particle diameter, in the example that lists in front, be preferably APVGaulin, homogenizer, the automatic homogeneous mixer of TK, Ebara Milder, TK Filmix and TKPipeline homogeneous mixer, more preferably the automatic homogeneous mixer of TK, Ebara Milder, TKFilmix and TK Pipeline homogeneous mixer especially are preferably the automatic homogeneous mixer of TK, TK Filmix and TK Pipeline homogeneous mixer.

In aforementioned preparation method, from improving uniform particle diameter and considering from the viewpoint of the storage stability of composite resin particle, the weight ratio (Q/P) of resin particle (Q) and resin particle (P) is preferably (0.01～60)/(40～99.99), more preferably (0.05～55)/(45～99.95) especially are preferably (0.1～50)/(50～99.9).That is to say that the upper limit of weight ratio (P/B) is preferably 60/40, more preferably 55/45, especially be preferably 50/50, same, its weight ratio lower limit (P/B) is preferably 0.01/99.99, and more preferably 0.05/99.95 especially is preferably 0.1/99.9.

Therefore, the weight ratio of preferably regulating resin (q), resin (p) and precursor (p0) makes it to be in the above-mentioned scope.

Resin with respect to 100 parts (p) and/or precursor (p0), the use amount of aqueous medium is preferably 50～2,000 part, more preferably 100～1,000 part, especially be preferably 100～500 parts.That is to say that the use amount upper limit of aqueous medium is preferably 2,000 parts, more preferably 1,000 part, especially be preferably 500 parts, same, its lower limit is preferably 50 parts, more preferably 100 parts.If lower limit is less than 50 parts, then the disperse state of resin (q) is tended to worsen, and if the upper limit surpasses 2,000 parts, consider it is worthless from economic angle.

Resin with respect to 100 parts (p), the use amount of aqueous medium is preferably 50～2,000 part, more preferably 100～1,000 part, especially be preferably 100～500 parts.If be less than 50 parts, the disperse state of resin (q) is tended to worsen, and if surpass 2,000 parts, considers it is worthless from economic angle.

To the use of aqueous medium without any restriction, as long as it is to contain the liquid of water as necessary component.Water, solvent-laden aqueous solution be can make, the aqueous solution of surfactant (S), the aqueous solution that contains water-soluble polymers (T) and their potpourri contained.

In above-mentioned solvent (U), the example of spendable solvent comprises ester or solvent of ether ester type, ether solvent, ketones solvent, alcohols solvent, amide solvent, sulfoxide kind solvent, heterogeneous ring compound kind solvent and two or more mixed solvent in them.

Containing under the situation of solvent, based on the weight of aqueous medium, the content of solvent is preferably 1～80%, and more preferably 2～70%, especially be preferably 5～30%.

Under the situation of using surfactant (S), based on the weight of aqueous medium, the content of surfactant is preferably 0.1～20%, and more preferably 0.5～10%, especially be preferably 1.0～8%.

If use water-soluble polymers (T), then based on the weight of aqueous medium, the content of water-soluble polymers is preferably 0.01～10%, more preferably 0.05～7%, especially be preferably 0.1～5%.

The volume average particle size of composite resin particle (DV) can be regulated by the volume average particle size (DVQ) of suitably regulating resin particle (Q).For example, if will to obtain volume average particle size (DV) be the composite resin particle of 1 μ m, then (DVQ) is preferably 0.0005～0.4 μ m, 0.001～0.3 μ m more preferably; If will to obtain volume average particle size (DV) is the composite resin particle of 10 μ m, then (DVQ) is preferably 0.005～4 μ m, 0.05～3 μ m more preferably.

When resin (p) and/or precursor (p0) being dispersed in the aqueous medium of resin particle (Q), resin (p) and precursor (p0) are preferably liquid.If resin (p) and precursor (p0) are solid at normal temperatures, then can disperse by the state with liquid state under more than or equal to the temperature of its fusing point, also can adopt the solution form of resin (p) and precursor (p0).

Consider that from the angle of uniform particle diameter the precursor (p0) of resin (p), (p) and the viscosity of their solution are preferably 10～50,000mPaS, more preferably 100～30,000mPaS especially is preferably 200～20,000mPaS.That is to say that the upper limit of viscosity is preferably 50,000mPaS, more preferably 30,000mPaS especially is preferably 20,000mPaS, same, lower limit is preferably 10mPaS, and more preferably 100mPaS especially is preferably 200mPaS.

Viscosity be utilize the rotator type viscosity meter (as, BL type viscosity meter, BM type viscosity meter, BH type viscosity meter, Tokyo gauge society system), under the condition of 25 ℃ and 30rpm, measure.

Temperature during dispersion is preferably 0～150 ℃, more preferably 5～98 ℃, especially is preferably 10～60 ℃.When temperature surpassed 100 ℃, shown was to add the temperature of depressing.When dispersion viscosity was higher, the temperature that preferably raises was carried out emulsification and dispersion then so that viscosity is reduced to above-mentioned preferable range.

There is no particular limitation for the solvent of the solution of solution that is used for resin (p) and precursor (p0), as long as it can dissolving resin (p) under normal temperature or heating condition.Listed identical of concrete example and front solvent (U).In them, although different according to the meetings such as type of resin (p) and precursor (p0), the difference of the SP value of preferred solvent and resin (p) or precursor (p0) is smaller or equal to 3, and this characteristic is different according to the meetings such as type of resin (p) and precursor (p0); Consider from the viewpoint of the uniform particle diameter of composite resin particle, more preferably can dissolving resin (p) but be difficult to make resin particle (Q) dissolving that contains resin (Q) or the solvent of swelling.

In above-mentioned method, can use emulsifying agent and spreading agent, above-mentioned surfactant (S) and water-soluble polymers (T) can be used as emulsifying agent and spreading agent simultaneously.Further, solvent above-mentioned (U) and plastifier (V) can be used as emulsification or dispersing aid is used in combination.

In order to increase the adhesion between resin particle in the composite resin particle (Q) and the resin particle (P), when being dispersed in them in the aqueous medium, preferably make resin particle (Q) have opposite positive and negative charge with resin particle (P), if resin particle (Q) and resin particle (P) have with a kind of electric charge, then use the surfactant (S) or the water-soluble polymers (T) of the opposite charge of institute electrically charged and resin particle (Q) and resin particle (P); And the difference of the SP value of adjusting resin (p) and resin (q) is smaller or equal to 2.If the adhesion height because (TQ/TR) value becomes big, generally is preferred therefore.The implication of (TQ/TR) is the ratio of projected area (TR) with the projected area (TQ) of resin particle (Q) of composite resin particle herein, projected area is measured as follows: utilize electron microscope (enlargement ratio 30,000 times) sample surfaces is carried out 10 photographies, import in the image analysis apparatus by the image information of interface then, projected area is measured each surface image.

The method of removing aqueous medium can be the combination of following method [1]～[3] or these methods:

[1] method of dry water-borne dispersions under decompression or normal pressure;

[2] utilize centrifugal separator, Supakura filtrator and/or pressure filter to carry out Separation of Solid and Liquid, the dry then solid that is separated; And

[3] freezing water-borne dispersions carries out dry method (so-called freeze-drying) then.

In said method of the present invention [1] and [2], can adopt known equipment such as fluid-bed drier, vacuum drier and drying by circulating air machine as drying device.

If desired, can use air classifier or screen cloth that resin particle is carried out classification to obtain desirable size distribution.

For resin particle of the present invention, the degree of depth that particle diameter ratio (DVQ/DVP) by changing resin particle (Q) and resin particle (P) and change resin particle (Q) are imbedded in resin particle (P) can make resin particle have level and smooth particle surface or makes particle surface have desirable roughness.

The degree of depth that resin particle (Q) is imbedded in resin particle (P) can be controlled by the following method.

[1] if resin particle (Q) has opposite positive and negative charge with resin particle (P), then the degree of depth imbedded in the resin particle (P) of resin particle (Q) deepens.At this moment, resin particle (Q) is high more with the electric charge that resin particle (P) respectively carries, and then corresponding length of embedment is just dark more.

[2] if resin particle (Q) and resin particle (P) have the electric charge (being positive charge or negative charge) of identical polar, then (TQ/TR) of resin particle (Q) is more little, and the degree of depth is tended to shoal more.In this case, a highest wisdom is used surfactant (S) and/or water-soluble polymers (T) [the particularly material of the electrically charged opposite charge with resin particle (Q) and resin particle (P) of institute], then can increase (TQ/TR).If use water-soluble polymers (T), then the molecular weight of water-soluble polymers (T) is big more, and the corresponding degree of depth is shallow more.

[3] if resin (p) has acidic functionalities (molecular weight of each acidic functionality is preferably smaller or equal to 1,000 usually) such as carboxyl, phosphono or sulfo group, then the pH value of aqueous medium is low more, and is (TQ/TR) just big more with the degree of depth.Otherwise the pH value of aqueous medium is high more, and is (TQ/TR) just more little with the degree of depth.

[4] if resin (p) has basic functionalities (molecular weight of each basic functionality is preferably smaller or equal to 1,000 usually) such as primary amino radical, secondary amino group, uncle's amino and quaternary ammonium salt, then the pH value of aqueous medium is high more, and is (TQ/TR) just big more with the degree of depth.Otherwise the pH value of aqueous medium is low more, and is (TQ/TR) just more little with the degree of depth.

[5] difference of the SP value of resin (p) and resin (q) is more little, and then corresponding (TQ/TR) and the degree of depth are just big more.

For improving the powder fluidity of resin particle, the BET specific surface area of preferred resin particle is 0.5～5.0m ²/ g.

The BET specific surface area can be passed through specific surface area instrument (as trade name: QUANTASORB, Yuasa Ionics corporate system) and measure (test gas: He/Kr=99.9/0.1 volume %, calibration gas: nitrogen).

Equally, consider that from the angle of powder fluidity the surperficial average centerline roughness (Ra) of resin particle (P) is preferably 0.01～0.8 μ m.

(Ra) implication is the arithmetic mean of absolute value of the deviation of roughness curve and center line, and it can be measured by for example sweep type probe microscope system (as Toyo Technica corporate system).

Embodiment

The present invention will be described in more detail below by embodiment, yet the present invention is not limited to embodiment described below.

Below the method for testing by every inventive embodiment of the application and comparative example resulting polyester resin properties is described.

1, hydroxyl value

Method according to JIS K 1557 (version in 1970) defined

If have in the sample because crosslinked and can't be dissolved in part in the solvent, the sample after then will kneading according to following method fusion is used for measuring.

Kneading machine: the smart machine of Japan (strain) is made LaboPlast Mill MODEL 30R150

The condition of kneading: under 130 ℃, 70rpm, carried out 30 minutes

2, acid number

Method according to JIS K 0070 (version in 1992) defined

If have in the sample because crosslinked and can't be dissolved in part in the solvent, then carry out fusion to knead according to same method in measuring with hydroxyl value, the sample after fusion is kneaded is used for measuring.

3, softening point (hereinafter being also referred to as Tm)

Determination method according to the softening point in aforesaid the 2nd invention is measured.

About the 1st～3rd inventive embodiment: embodiment 1～4, comparative example 1～4

Embodiment 1

[synthesizing of linear polyesters]

In the reactive tank that cooling tube, stirrer and nitrogen ingress pipe have been installed, add 639 parts (24.5 moles) 1, the hexane diacid of 2-propylene glycol (hereinafter only being called propylene glycol), bisphenol-A 2 mole ethylene oxides (EO) addition product of 180 parts (1.6 moles), the terephthalic acid (TPA) dimethyl esters of 653 parts (9.8 moles), 10 parts (0.2 moles) and 3 parts of four titanium butoxide acid esters as condensation catalyst, be reflected under 180 ℃ and in nitrogen stream, carried out 8 hours, remove the methyl alcohol that is produced simultaneously.Then reaction system is heated gradually until 230 ℃, reaction is 4 hours in nitrogen stream, removes the propylene glycol and the water that are produced simultaneously, further pressure is reduced to 5～20mmHg and reacts, and takes out product when softening point reaches 90 ℃.The propylene glycol that reclaims is 263 parts (10.1 moles).After the resin that takes out is cooled to room temperature, be ground into graininess.The product that is obtained is linear polyesters (Aa-1).

The Mn of linear polyesters (Aa-1) is 1500, Mp is 2500, molecular weight is 3.0% smaller or equal to the content of 500 composition, it is 0% that THF does not dissolve part, the average cohesive energy (hereinafter referred is En) of the mole of polyol component is 82KJ, storage modulus under 150 ℃ (being reduced to G ' later on) is 300, Tm is 90 ℃, loss tangent in the time of 130～200 ℃ (hereinafter referred is tan δ) is 5～11 (when temperature surpasses 150 ℃, because elasticity is crossed low and can not be measured, thereby the value when adopting 130～150 ℃.In each linear polyesters hereinafter, unless detailed description is arranged in addition, identical therewith.)。

Molal quantity in the bracket is represented the relative mol ratio (identical with it in the embodiment of back) of each raw material.

[synthesizing of non-linearity polyester]

In reactive tank as hereinbefore, add 614 parts of (23.8 moles) propylene glycol, 156 parts of (1.4 moles) bisphenol-A 2 mole ethylene oxide addition products, 627 parts of (9.5 moles) terephthalic acid (TPA) dimethyl esters, 25 parts of (0.5 mole) hexane diacids, 3 part of four titanium butoxide acid esters is reflected under 180 ℃ and carried out 8 hours in nitrogen stream, removes the methyl alcohol that is produced simultaneously.Then reaction system is heated gradually until 230 ℃, reaction is 4 hours in nitrogen stream, removes the propylene glycol and the water that are produced simultaneously, further pressure is reduced to 5～20mmHg reaction 1 hour, and the propylene glycol of recovery is 288 parts (11.2 moles).Then be cooled to 180 ℃, add 98 parts of trimellitic anhydrides (1.5 moles), the normal pressure airtight condition reacted 2 hours down, under normal pressure, continue reaction then in 220 ℃, when softening point reaches 180 ℃, take out product, the resin that takes out is cooled to room temperature after, be ground into graininess.The product that is obtained is non-linearity polyester (Ab-1).

The Mn of non-linearity polyester (Ab-1) is 4000, and Mp is 8000, and molecular weight is 1.3% smaller or equal to the content of 500 composition, and it is 30% that THF does not dissolve part, and En is 82KJ, and G ' is 3.6 * 10 ⁵, Tm is 180 ℃, tan δ is 1.2～2.0.

[preparation of polyester resin for toner]

Making 600 parts of linear polyesters (Aa-1) and 400 parts of non-linearity polyester (Ab-1) is that 150 ℃, hold-up time are to carry out fusion under 3 minutes the condition to knead at jacket temperature in continuous kneading machine.The gained molten resin is cooled to room temperature, pulverizes with comminutor then, make it granulating, obtain polyester resin for toner of the present invention (1).

The Tg of polyester resin for toner (1) is 64 ℃, and Mn is 2200, and Mp is 3200, and molecular weight is 2.3% smaller or equal to the content of 500 composition, and it is 13% that THF does not dissolve part.

Embodiment 2

[synthesizing of linear polyesters]

In the reactive tank identical with embodiment 1, add 720 parts of (23.8 moles) propylene glycol, 735 parts of (9.8 moles) terephthalic acid (TPA) dimethyl esters, 29 parts of (0.5 mole) hexane diacids, 3 part of four titanium butoxide acid esters, reaction conditions is identical with the condition of synthetic linear polyesters (Aa-1) in the previous embodiment 1, takes out product when softening point reaches 94 ℃.The propylene glycol that reclaims is 235 parts (7.8 moles).After the resin that takes out is cooled to room temperature, be ground into graininess.The product that is obtained is linear polyesters (Aa-2).

The Mn of linear polyesters (Aa-2) is 2700, and Mp is 5800, and molecular weight is 2.0% smaller or equal to the content of 500 composition, and it is 0% that THF does not dissolve part, and En is 73KJ, and G ' is 300, and Tm is 90 ℃, and tan δ is 5～11.

[synthesizing of non-linearity polyester]

In the reactive tank identical with embodiment 1, add 663 parts of (22.5 moles) propylene glycol, 677 parts of (9.0 moles) terephthalic acid (TPA) dimethyl esters, 57 parts of (1.0 moles) hexane diacids, 3 part of four titanium butoxide acid esters, reaction conditions is identical with the condition of synthetic linear polyesters (Ab-1) in the previous embodiment 1, and the propylene glycol of recovery is 251 parts (8.5 moles).After being cooled to 180 ℃, add 112 parts of trimellitic anhydrides (1.5 moles), under the condition identical, react, when softening point reaches 180 ℃, take out product, be cooled to room temperature and be crushed to graininess with aforementioned preparation linear polyesters (Ab-1).The product that is obtained is non-linearity polyester (Ab-2).

The Mn of non-linearity polyester (Ab-2) is 3900, and Mp is 8000, and molecular weight is 1.3% smaller or equal to the content of 500 composition, and it is 29% that THF does not dissolve part, and En is 73KJ, and G ' is 3.6 * 10 ⁵, Tm is 180 ℃, tan δ is 1.2～2.1.

[preparation of polyester resin for toner]

Making 600 parts of linear polyesters (Aa-2) and 400 parts of non-linearity polyester (Ab-2) carry out fusion under 150 ℃ of jacket temperatures, hold-up time are 3 minutes condition in continuous kneading machine kneads.The gained molten resin is cooled to room temperature, pulverizes with comminutor then, make it granulating, obtain polyester resin for toner of the present invention (2).

The Tg of polyester resin for toner (2) is 64 ℃, and Mn is 3200, and Mp is 6700, and molecular weight is 1.6% smaller or equal to the content of 500 composition, and it is 13% that THF does not dissolve part.

Embodiment 3

[synthesizing of linear polyesters]

In the reactive tank identical with embodiment 1, add 701 parts of (18.8 moles) propylene glycol, 716 parts of (7.5 moles) terephthalic acid (TPA) dimethyl esters, 180 parts of (2.5 moles) hexane diacids, 3 part of four titanium butoxide acid esters, reaction conditions is identical with the condition of synthetic linear polyesters (Aa-1) in the previous embodiment 1, takes out product when softening point arrives 150 ℃.The propylene glycol that reclaims is 316 parts (8.5 moles).After the resin that takes out is cooled to room temperature, be ground into graininess.The product that is obtained is linear polyesters (Aa-3).

The Mn of linear polyesters (Aa-3) is 8000, and Mp is 20000, and molecular weight is 1.6% smaller or equal to the content of 500 composition, and it is 0% that THF does not dissolve part, and En is 73KJ, and G ' is 1.6 * 10 ⁶, Tm is 150 ℃, tan δ is 5～11.

[synthesizing of non-linearity polyester]

In the reactive tank identical with embodiment 1, add 557 parts of (17.5 moles) propylene glycol, 569 parts of (7.0 moles) terephthalic acid (TPA) dimethyl esters, 184 parts of (3.0 moles) hexane diacids, 3 part of four titanium butoxide acid esters, reaction conditions is identical with the condition of synthetic linear polyesters (Ab-1) in the previous embodiment 1, the propylene glycol that reclaims is 175 parts (5.5 moles), after being cooled to 180 ℃, add 121 parts of trimellitic anhydrides (1.5 moles), under the condition identical, react with aforementioned preparation linear polyesters (Ab-1), when softening point reaches 180 ℃, take out product, be cooled to room temperature and be crushed to graininess.The product that is obtained is non-linearity polyester (Ab-3).

The Mn of non-linearity polyester (Ab-3) is 8500, and Mp is 23000, and molecular weight is 0.9% smaller or equal to the content of 500 composition, and it is 30% that THF does not dissolve part, and En is 73KJ, and G ' is 3.6 * 10 ⁵, Tm is 180 ℃, tan δ is 1.2～1.9.

[preparation of polyester resin for toner]

Making 600 parts of linear polyesters (Aa-3) and 400 parts of non-linearity polyester (Ab-3) is that 150 ℃, hold-up time are to carry out fusion under 3 minutes the condition to knead at jacket temperature in continuous kneading machine.The gained molten resin is cooled to room temperature, pulverizes with comminutor then, make it granulating, obtain polyester resin for toner of the present invention (3).

The Tg of polyester resin for toner (3) is 62 ℃, and Mn is 8100, and Mp is 22000, and molecular weight is 1.3% smaller or equal to the content of 500 composition, and it is 13% that THF does not dissolve part.

Embodiment 4

[synthesizing of linear polyesters]

In the reactive tank identical with embodiment 1, add 540 parts of (25.0 moles) propylene glycol, 372 parts of (4.0 moles) bisphenol-A 2 mole ethylene oxide addition products, 551 parts of (10.0 moles) terephthalic acid (TPA) dimethyl esters, 3 part of four titanium butoxide acid esters, be reflected under 180 ℃ and in nitrogen stream, carried out 8 hours, remove the methyl alcohol that is produced simultaneously.Then reaction system is heated gradually until 230 ℃, reaction is 4 hours in nitrogen stream, removes the propylene glycol and the water that are produced simultaneously, further pressure is reduced to 5～20mmHg and reacts, and takes out product when softening point arrives 94 ℃.The propylene glycol that reclaims is 281 parts (13.0 moles).After the resin that takes out is cooled to room temperature, be ground into graininess.The product that obtains is linear polyesters (Aa-4).

The Mn of linear polyesters (Aa-4) is 2700, and Mp is 5800, and molecular weight is 2.5% smaller or equal to the content of 500 composition, and it is 0% that THF does not dissolve part, and En is 96KJ, and G ' is 300, and Tm is 94 ℃, and tan δ is 5～11.

[synthesizing of non-linearity polyester]

In the reactive tank identical with embodiment 1, add 531 parts of (24.3 moles) propylene glycol, 330 parts of (3.5 moles) bisphenol-A 2 mole ethylene oxide addition products, 542 parts of (9.7 moles) terephthalic acid (TPA) dimethyl esters, 13 parts of (0.3 mole) hexane diacids, 3 part of four titanium butoxide acid esters, be reflected under 180 ℃ and in nitrogen stream, carried out 8 hours, remove the methyl alcohol that is produced simultaneously.Then reaction system is heated gradually until 230 ℃, reaction is 4 hours in nitrogen stream, removes the propylene glycol and the water that are produced simultaneously, further pressure is reduced to 5～20mmHg reaction 1 hour, the propylene glycol that reclaims is 301 parts (13.8 moles), after being cooled to 180 ℃, add 83 parts of (1.5 moles) trimellitic anhydrides, the normal pressure airtight condition reacted 2 hours down, then, under normal pressure, continue to react, when softening point reaches 180 ℃, take out product, be cooled to room temperature and be crushed to graininess in 220 ℃.The product that is obtained is non-linearity polyester (Ab-4).

The Mn of non-linearity polyester (Ab-4) is 4000, and Mp is 8000, and molecular weight is 1.3% smaller or equal to the content of 500 composition, and it is 31% that THF does not dissolve part, and En is 96KJ, and G ' is 3.6 * 10 ⁵, Tm is 180 ℃, tan δ is 1.1～1.4.

[preparation of polyester resin for toner]

Making 600 parts of linear polyesters (Aa-4) and 400 parts of non-linearity polyester (Ab-4) is that 150 ℃, hold-up time are to carry out fusion under 3 minutes the condition to knead at jacket temperature in continuous kneading machine.The gained molten resin is cooled to room temperature, pulverizes with comminutor then, make it granulating, obtain polyester resin for toner of the present invention (4).

The Tg of polyester resin for toner (4) is 63 ℃, and Mn is 3200, and Mp is 6700, and molecular weight is 1.9% smaller or equal to the content of 500 composition, and it is 14% that THF does not dissolve part.

Comparative example 1

[synthesizing of linear polyesters]

In the reactive tank identical with embodiment 1, add 2 moles of PO addition products of 466 parts of (9.0 moles) bisphenol-As, 2 moles of EO addition products of 341 parts of (7.0 moles) bisphenol-As, 247 parts of (10.0 moles) terephthalic acid (TPA)s, 3 part of four titanium butoxide acid esters, be reflected under 230 ℃ and in nitrogen stream, carried out 5 hours, remove the water that is produced simultaneously.Further pressure is reduced to 5～20mmHg and react, when acid number is 2, temperature of reaction system is cooled to 180 ℃, add 74 parts of (2.6 moles) trimellitic anhydrides, normal pressure airtight condition down reaction took out product after 2 hours, the resin that takes out is cooled to room temperature after, be ground into graininess.The product that is obtained is non-linearity polyester (Aa '-5).

The Mn of linear polyesters (Aa '-5) is 1500, and Mp is 2500, and molecular weight is 4.2% smaller or equal to the content of 500 composition, and it is 0% that THF does not dissolve part, and En is 166KJ, and G ' is 300, and Tm is 90 ℃, and tan δ is 5～11.

[synthesizing of non-linearity polyester]

In the reactive tank identical with embodiment 1, add 3 moles of PO addition products of 679 parts of (10.8 moles) bisphenol-As, 47 parts of (0.37 mole) phenol novolac resin EO addition products, 260 parts of (10.0 moles) terephthalic acid (TPA)s, 3 part of four titanium butoxide acid esters, be reflected under 230 ℃ and in nitrogen stream, carried out 7 hours, remove the water that is produced simultaneously.Further pressure being reduced to 5～20mmHg reacts, when acid number when being less than or equal to 2, temperature of reaction system is cooled to 180 ℃, add 87 parts of (2.9 moles) trimellitic anhydrides, the normal pressure airtight condition reacted 2 hours down, continued reaction at 220 ℃ under normal pressure then, took out product when softening point is 180 ℃, be cooled to room temperature, be crushed to graininess.The product that obtains is non-linear polyesters (Ab '-5).

The Mn of non-linearity polyester (Ab '-5) is 4200, and Mp is 7400, and molecular weight is 3.2% smaller or equal to the content of 500 composition, and it is 42% that THF does not dissolve part, and En is 184KJ, and G ' is 5.0 * 10 ⁵, Tm is 94 ℃, tan δ is 0.3～0.7.

[preparation of polyester resin for toner]

Is that 150 ℃, hold-up time be 3 minute condition under carry out fusion knead at jacket temperature with 600 parts of linear polyesters (Aa '-5) and 400 parts of non-linearity polyester (Ab '-5) in continuous kneading machine.The gained molten resin is cooled to room temperature, pulverizes with comminutor then, make it granulating, obtain contrast polyester resin for toner (1).

The Tg of contrast polyester resin for toner (1) is 64 ℃, and Mn is 2600, and Mp is 4500, and molecular weight is 3.8% smaller or equal to the content of 500 composition, and it is 16% that THF does not dissolve part.

Comparative example 2

[synthesizing of linear polyesters]

In the reactive tank identical with embodiment 1, add 2 moles of PO addition products of 404 parts of (7.0 moles) bisphenol-As, 2 moles of EO addition products of 380 parts of (7.0 moles) bisphenol-As, 276 parts of (10.0 moles) terephthalic acid (TPA)s, 3 part of four titanium butoxide acid esters, be reflected under 230 ℃ and in nitrogen stream, carried out 5 hours, remove the water that is produced simultaneously.Further pressure being reduced to 5～20mmHg reacts, when acid number smaller or equal to 2 the time, temperature of reaction system is cooled to 180 ℃, add 74 parts of (2.3 moles) trimellitic anhydrides, normal pressure airtight condition reaction down took out product after 2 hours, be cooled to room temperature, the resin of taking-up is crushed to graininess, and the product of acquisition is linear polyesters (Aa '-6).

The Mn of linear polyesters (Aa '-6) is 1900, and Mp is 4200, and molecular weight is 4.0% smaller or equal to the content of 500 composition, and it is 0% that THF does not dissolve part, and En is 90KJ, and G ' is 300, and Tm is 90 ℃, and tan δ is 5～11.

[preparation of polyester resin for toner]

Is that 150 ℃, hold-up time be 3 minute condition under carry out fusion knead at jacket temperature with 600 parts of linear polyesters (Aa '-6) and 400 parts of non-linearity polyester (Ab '-5) in continuous kneading machine.The gained molten resin is cooled to room temperature, pulverizes with comminutor then, make it granulating, obtain contrast polyester resin for toner (2).

The Tg of contrast polyester resin for toner (2) is 64 ℃, and Mn is 2800, and Mp is 5500, and molecular weight is 3.7% smaller or equal to the content of 500 composition, and it is 17% that THF does not dissolve part.

Comparative example 3

[synthesizing of linear polyesters]

In the reactive tank identical with embodiment 1, add 692 parts of (25.0 moles) propylene glycol, 707 parts of (10.0 moles) terephthalic acid (TPA) dimethyl esters and 3 parts of four titanium butoxide acid esters as condensation catalyst, be reflected under 180 ℃ and in nitrogen stream, carried out 8 hours, remove the methyl alcohol that is produced simultaneously.Then reaction system is heated gradually until 230 ℃, reaction is 4 hours in nitrogen stream, removes the propylene glycol and the water that are produced simultaneously, further pressure is reduced to 5～20mmHg reaction 1 hour, takes out product.The propylene glycol that reclaims is 166 parts (6.0 moles).Then product is cooled to room temperature, yet product is not converted into resin-like and becomes paste.The product that obtains is named as linear polyesters (Aa '-7).

The Mn of linear polyesters (Aa '-7) is 800, and Mp is 1200, and it is 0% that THF does not dissolve part, because polyester (Aa '-7) is not converted into resin, can not be used as product of toner.

Comparative example 4

[synthesizing of linear polyesters]

In the reactive tank identical with embodiment 1, add 2 moles of EO addition products of 722 parts of (10.3 moles) bisphenol-As, 356 parts of (10.0 moles) terephthalic acid (TPA)s and 3 parts of four titanium butoxide acid esters as condensation catalyst, be reflected under 230 ℃ and in nitrogen stream, carried out 5 hours, remove the water that is produced simultaneously.Further pressure is reduced to 5～20mmHg and reacts, when acid number smaller or equal to 2 the time, temperature of reaction system is cooled to 180 ℃, add 25 parts of (0.6 mole) trimellitic anhydrides, normal pressure airtight condition reaction down took out product after 2 hours, was cooled to room temperature, was crushed to graininess.The product called after linear polyesters (Aa '-8) that obtains.

The Mn of linear polyesters (Aa '-8) is 7000, and Mp is 19000, and molecular weight is 3.3% smaller or equal to the content of 500 composition, and it is 0% that THF does not dissolve part, and En is 164KJ, and G ' is 1.0 * 10 ⁵, Tm is 140 ℃, is 0.8～4 at 130～200 ℃ tan δ.

[synthesizing of non-linearity polyester]

In the reactive tank identical with embodiment 1, add 3 moles of PO addition products of 693 parts of (10.8 moles) bisphenol-As, 48 parts of (0.37 mole) phenol novolac resin EO addition products, 239 parts of (9.0 moles) terephthalic acid (TPA)s and 3 parts of four titanium butoxide acid esters as condensation catalyst, be reflected under 230 ℃ and in nitrogen stream, carried out 7 hours, remove the water that is produced simultaneously.Further pressure being reduced to 5～20mmHg reacts, when acid number smaller or equal to 2 the time, temperature of reaction system is cooled to 180 ℃, add 89 parts of (2.9 moles) trimellitic anhydrides, the down reaction 2 hours of normal pressure airtight condition, then 220 ℃ under normal pressure, react to softening point be 180 ℃, take out product, be cooled to room temperature, be crushed to graininess.The product that obtains is called as non-linearity polyester (Ab '-8).

The Mn of non-linearity polyester (Ab '-8) is 8800, and Mp is 22000, and molecular weight is 3.3% smaller or equal to the content of 500 composition, and it is 42% that THF does not dissolve part, and En is 184KJ, and G ' is 5.0 * 10 ⁵, Tm is 180 ℃, tan δ is 0.3～0.7.

[preparation of polyester resin for toner]

Fusion is kneaded under 150 ℃ of jacket temperatures, the condition of 3 minutes hold-up times in continuous kneading machine with 600 parts of linear polyesters (Aa '-8) and 400 parts of non-linearity polyester (Ab '-8).The gained molten resin is cooled to room temperature, pulverizes with comminutor then, make it granulating, obtain the vibrin (4) that the contrast toner is used.

The Tg of contrast polyester resin for toner (4) is 63 ℃, and Mn is 8000, and Mp is 21000, and molecular weight is 3.3% smaller or equal to the content of 500 composition, and it is 16% that THF does not dissolve part.

Embodiment (1) to (4) and comparative example (1), (2) and (4)

Polyester resin for toner of the present invention (1)～(4) with respect to 100 parts and contrast polyester resin for toner (1)～(2), (4), add 8 parts of carbon black MA-100 (making), 5 parts of Brazil waxs, 1 part of charge control agent T-77 (making) respectively, prepare toner as follows by protecting scholar paddy chemical company by Mitsubishi chemical Co., Ltd.

At first, with every kind of potpourri with Henschel mixer (FM10B, make by Mitsui three pond chemical machinery companies) carry out premixed, use double screw extrusion machine (PCM-30 then, make by pond shellfish Co., Ltd.) knead, use ultrasonic jet mill Labo-jet (Japanese Pneumatic Co., Ltd. make) to carry out meticulous pulverizing subsequently, use air classifier (MDS-I then, Japan Pneumatic Co., Ltd. makes) carry out classification, acquisition particle diameter D50 is 8 microns a toner-particle.Then in per 100 parts of gained toner-particles, add 0.5 part of colloidal silica (Aersoil R972: make) by Japanese Aersoil Co., Ltd., use sample mill (sample mill) to mix then, obtain toner of the present invention (1)～(4) and contrast toner (1), (2), (4).

Toner is estimated with following evaluation method, and evaluation result is listed in the table 1.

[table 1]

The toner sequence number	MFT (℃)	Gross (℃)	HOT (℃)	Mobile	Comminuted mean grain size (μ m)
						Toner (1)	125	145	230	○	11
Toner (2)	120	140	230	○	11
						Toner (3)	125	145	230	○	12
Toner (4)	130	145	230	○	11
						Contrast toner (1)	135	165	215	△×	12
Contrast toner (2)	130	165	230	△×	12
						Contrast toner (4)	130	175	230	△	16

[evaluation method]

[1] minimum fixing temperature (MFT)

Utilize the fixing device of commercially available duplicating machine (AR5030:SHARP CORP manufacturing) that the uncertain image that is developed by commercially available duplicating machine (AR5030:SHARP CORP manufacturing) is estimated.After the image fixing, with a cushion (pat) wiping image, the survival rate of image color is defined as minimum fixing temperature (MFT) more than or equal to 70% o'clock fixing roller temperature.

[2] the deep fat China ink stains occurrence temperature (HOT)

According to the mode that above-mentioned MFT is same photographic fixing is estimated, the deep fat China ink that the photographic fixing image is taken place stains the visual method observation of employing.The temperature of the fixing roller the when contamination of deep fat China ink takes place is defined as the deep fat China ink and stains occurrence temperature.

[3] gloss presents temperature (Gross)

Adopt and the identical mode of the minimum fixing temperature of aforementioned evaluation, the fixing device that utilizes commercially available duplicating machine (LBP2160: made by CANON INC) to oneself development and the not image of photographic fixing carries out the photographic fixing evaluation.Be that 60 ° part is defined as gloss more than or equal to 10% fixing roller temperature and presents temperature with the glossiness of photographic fixing image.

[4] toner flowability

Utilize powder tester (manufacturing of Hosokawa Micron company) that the quiet bulk density of every kind of toner is measured, by the flowability of following standard determination toner.But be considered to practical application with △ mark or higher grade toner.

Quiet bulk density (g/100ml): toner flowability

More than or equal to 36: zero

More than or equal to 33～less than 36: zero △

More than or equal to 30～and less than 33: △

More than or equal to 27～and less than 30: △ *

Less than 27: *

[5] comminuted

Mince in (by 8.6 orders～end in, 30 orders) for the toner meal of kneading through double shaft kneader and cool off, it is broken to adopt ultrasonic jet mill Labo-Jet (being made by Japanese Pneumatic Industrial Co., Ltd) to carry out fine powder under the following conditions:

Pulverize pressure: 0.5MPa

Regulating ring (Adjuster ring): 15mm

Vent hole (louvers) size: in

The pulverizing time: 10 minutes

Do not carry out classification, utilize Ku Erte particle collector (Coulter Counter) TA II (U.S. Coulter electronics corporation system) to measure the volume average particle size of crushed products, check it comminuted.In this assay method, if volume average particle size smaller or equal to 12 μ m, then can think have good comminuted.

[embodiment 11 and 12 and comparative example 11 to 13]

Embodiment 11

[synthesizing of non-linearity polyester]

In the reactive tank identical with embodiment 1, add 817 parts of (22.6 moles) propylene glycol, 831 parts of (9.0 moles) terephthalic acid (TPA) dimethyl esters, 70 parts of (1.0 moles) hexane diacids and 3 parts of four titanium butoxide acid esters as condensation catalyst, be reflected under 180 ℃ and in nitrogen stream, carried out 8 hours, remove the methyl alcohol that is produced simultaneously.Then reaction system is heated gradually until 230 ℃, reaction is 4 hours in nitrogen stream, removes the propylene glycol and the water that are produced simultaneously, further pressure is reduced to 5～20mmHg reaction 1 hour.When softening point arrives 85 ℃, product is cooled to 180 ℃, add 37 parts of (0.4 mole) trimellitic anhydrides, the normal pressure airtight condition reacted 2 hours down, reacted under normal pressure at 220 ℃ then, took out product when softening point arrives 160 ℃.The propylene glycol that reclaims is 450 parts (12.0 moles).After the resin that takes out is cooled to room temperature, be crushed to graininess.The product that is obtained is non-linearity polyester (Ab-11).

The Tg of non-linearity polyester (Ab-11) is 60 ℃, and Mn is 5800, and peak molecular weight is 10000, and it is 3% that THF does not dissolve part, and En is 73KJ, and G ' is 1.6 * 10 ⁵, Tm is 160 ℃, tan δ is 1.2～2.5.

[synthesizing of linear polyesters]

In the reactive tank identical with embodiment 1, add 782 parts of (22.7 moles) 1,2-propylene glycol, 834 parts of (9.5 moles) terephthalic acid (TPA) dimethyl esters, 33 parts of (0.5 mole) hexane diacids and 3 parts of four titanium butoxide acid esters as condensation catalyst, be reflected under 180 ℃ and in nitrogen stream, carried out 8 hours, remove the methyl alcohol that is produced simultaneously.Then reaction system is heated gradually until 230 ℃, reaction is 4 hours in nitrogen stream, removes the propylene glycol and the water that are produced simultaneously, further pressure is reduced to 5～20mmHg and reacts, cooling reaction system when softening point arrives 95 ℃.The propylene glycol of Hui Shouing is 380 parts (11.0 moles) thus.When temperature to 180 ℃, add 17 parts of trimellitic anhydrides, take out product at 180 ℃ after keeping 1.5 hours, the resin that obtains is cooled to room temperature after, be crushed to graininess.The product that is obtained is linear polyesters (Aa-11).

The Tg of linear polyesters (Aa-11) is 60 ℃, and Mn is 2800, and peak molecular weight is 5800, and En is 73KJ, and G ' is 140, and Tm is 100 ℃, and tan δ is 4～20.

[preparation of polyester resin for toner]

Is that 150 ℃, hold-up time be 3 minute condition under carry out fusion knead at jacket temperature with 400 parts of non-linearity polyester (Ab-11) and 600 parts of linear polyesters (Aa-11) in continuous kneading machine.The gained molten resin is cooled to room temperature, pulverizes with comminutor then, make it granulating, obtain polyester resin for toner of the present invention (11).

Embodiment 12

[synthesizing of non-linearity polyester]

In the reactive tank identical with embodiment 1, add 391 parts of (22.3 moles) propylene glycol, 358 parts of (8.0 moles) terephthalic acid (TPA) dimethyl esters, 67 parts of (2.0 moles) hexane diacids and 3 parts of four titanium butoxide acid esters as condensation catalyst, be reflected under 180 ℃ and in nitrogen stream, carried out 8 hours, remove the methyl alcohol that is produced simultaneously.Then reaction system is heated gradually until 230 ℃, reaction is 4 hours in nitrogen stream, remove the propylene glycol and the water that are produced simultaneously, further add 561 parts of (7 moles) bisphenol-A 2 mole propylene oxide addition products, 56 parts of (0.3 mole) phenol novolac resins (the nucleome number is 5.6) ethylene oxide adduct then, reacted 4 hours under normal pressure at 230 ℃, further pressure is reduced to 5～20mmHg and react.When softening point arrived 90 ℃, cooling reaction system when being cooled to temperature to 180 ℃, added 20 parts of (0.45 mole) trimellitic anhydrides, in 180 ℃ of maintenances 1.5 hours, is warming up to 220 ℃ then.Then pressure is suitably reduced to 5～20mmHg and react, when softening point temperature reaches 135 ℃, take out product.So the propylene glycol that reclaims is 314 parts (17.5 moles).After the resin that takes out is cooled to room temperature, be crushed to graininess.The product that obtains is non-linearity polyester (Ab-12).

The Tg of non-linearity polyester (Ab-12) is 60 ℃, and Mn is 4200, and peak molecular weight is 7800, and it is 3% that THF does not dissolve part, and En is 97KJ, and G ' is 1.36 * 10 ⁴, Tm is 135 ℃, tan δ is 1.2～1.9.

[polyester resin for toner]

To be used as toner vibrin (12) by the synthetic non-linearity polyester (Ab-12) of preceding method.

Comparative example 11

[synthesizing of non-linearity polyester]

In the reactive tank that cooling tube, stirrer and nitrogen ingress pipe have been installed, add 552 parts of (2.5 moles) bisphenol-A 2 mole propylene oxide addition products, 184 parts of (8 moles) bisphenol-A 2 mole ethylene oxide addition products, 287 parts of (8.2 moles) terephthalic acid (TPA)s, 3 parts of dibutyl tin oxides, the esterification of in nitrogen stream, under 230 ℃, dewatering, when not having water to discharge, reduce pressure, promote that esterification is 1.0 until acid number.After this temperature is adjusted to 220 ℃, adds 49 parts of (1.2 moles) trimellitic anhydrides, kept 1 hour in this temperature.After this suitably pressure is reduced to 5～20mmHg and react, when softening point is 115 ℃, from reactive tank, take out product, obtain the polyester (Ab '-13) of non-linearity.The Tg of non-linearity polyester (Ab '-13) is 60 ℃, and Mn is 3200, and peak molecular weight is 5800, and it is 0% that THF does not dissolve part, and En is 165KJ, and G ' is 5.8 * 10 ³, Tm is 115 ℃, tan δ is 1.1～5.2.

[polyester resin for toner]

To be used as contrast polyester resin for toner (11) according to the synthetic non-linearity polyester (Ab '-13) of preceding method.

Comparative example 12

[synthesizing of non-linearity polyester]

In the reactive tank identical with embodiment 1, add 138 parts of (2.2 moles) bisphenol-A 2 mole propylene oxide addition products, 616 parts of (8.5 moles) bisphenol-A 2 mole propylene oxide addition products, 224 parts of (7.5 moles) terephthalic acid (TPA)s and 3 parts of dibutyl tin oxides as condensation catalyst, be reflected under 230 ℃ and in nitrogen stream, carried out 7 hours, remove the water that is produced simultaneously.Then pressure being reduced to 5～20mmHg reacts, when acid number is 1, reaction system is cooled to 180 ℃, adds the trimellitic anhydride of 87 parts (2.5 moles) then, the normal pressure sealing condition reacted 2 hours down, under normal pressure, continue reaction subsequently in 220 ℃, then pressure is reduced to 5～20mmHg and react, when softening point arrives 185 ℃, from reactive tank, take out product, be cooled to room temperature, pulverize granulating.Obtain the polyester (Ab '-14) of non-linearity thus.

The Mn of non-linearity polyester (Ab '-14) is 6000, and Mp is 10000, and En is 183KJ, and G ' is 5.0 * 10 ⁵, Tm is 185 ℃, tan δ is 0.1～0.4.

[synthesizing of linear polyesters]

In the reactive tank identical with embodiment 1, add 552 parts of (10.0 moles) bisphenol-A 2 mole propylene oxide addition products, 208 parts of (4.0 moles) bisphenol-A 2 mole ethylene oxide addition products, 263 parts of (10.0 moles) terephthalic acid (TPA)s and 3 parts of dibutyl tin oxides as condensation catalyst, be reflected under 230 ℃ and in nitrogen stream, carried out 5 hours, remove the water that is produced simultaneously.When acid number is 1.5, reaction system is cooled to 180 ℃, add 34 parts trimellitic anhydride then, the normal pressure airtight condition reacted 2 hours down, then took out product from reactive tank, was cooled to room temperature, pulverized granulating then.Obtain linear polyesters (Aa '-14).

The Mn of linear polyesters (Aa '-14) is 2800, and Mp is 5200, and En is 166KJ, and G ' is 1.4 * 10 ², Tm is 100 ℃, tan δ is 3～15.

[preparation of polyester resin for toner]

Is that 150 ℃, hold-up time be 3 minute condition under carry out fusion knead at jacket temperature with 400 parts of non-linearity polyester (Ab '-14) and 600 parts of linear polyesters (Aa '-14) in continuous kneading machine.The gained molten resin is cooled to room temperature, pulverizes with comminutor then, make it granulating, obtain contrast polyester resin for toner (12).

Comparative example 13

[synthesizing of non-linearity polyester]

In the reactive tank identical with embodiment 1, add 137 parts of (2.2 moles) bisphenol-A 2 mole propylene oxide addition products, 612 parts of (8.5 moles) bisphenol-A 2 mole propylene oxide addition products, 267 parts of (9.0 moles) terephthalic acid (TPA)s and 3 parts of dibutyl tin oxides as condensation catalyst, be reflected under 230 ℃ and in nitrogen stream, carried out 7 hours, remove the water that is produced simultaneously.Then pressure being reduced to 5～20mmHg reacts, when acid number is 1, reaction system is cooled to 180 ℃, adds the trimellitic anhydride of 52 parts (1.5 moles) then, the normal pressure sealing condition reacted 2 hours down, under normal pressure, continue reaction subsequently in 220 ℃, then suitably pressure is reduced to 5～20mmHg and react, when softening point arrives 160 ℃, from reactive tank, take out product, be cooled to room temperature, pulverize granulating.Obtain the polyester (Ab '-15) of non-linearity thus.

The Mn of non-linearity polyester (Ab '-15) is 11000, and Mp is 240000, and En is 183KJ, and G ' is 2.4 * 10 ⁵, Tm is 160 ℃, tan δ is 0.5～0.9.

[preparation of polyester resin for toner]

Is that 150 ℃, hold-up time be 3 minute condition under carry out fusion knead at jacket temperature with the polyester (Ab '-15) of 400 parts of non-linearity and 600 parts of linear polyesters (Aa '-14) in continuous kneading machine.The gained molten resin is cooled to room temperature, pulverizes with comminutor then, make it granulating, obtain contrast polyester resin for toner (13).

Embodiment (11) and (12), and comparative example (11)～(13)

Polyester resin for toner of the present invention (11)～(12) with respect to 100 parts and contrast polyester resin for toner (11)～(13) add 8 parts of phthalocyanine blue KRO (adret pigment system) and 5 parts of Brazil waxs respectively, prepare toner as follows.

At first, with every kind of potpourri with Henschel mixer (FM10B, make by Mitsui three pond chemical machinery companies) carry out premixed, use double screw extrusion machine (PCM-30 then, make by pond shellfish Co., Ltd.) knead, it is broken to use ultrasonic jet mill Labo-jet (Japanese Pneumatic Co., Ltd. make) to carry out fine powder subsequently, uses air classifier (MDS-I then, Japan Pneumatic Co., Ltd. makes) carry out classification, acquisition particle diameter D50 is 8 microns a toner-particle.Then in per 100 parts of gained toner-particles, add 0.5 part of colloidal silica (Aersoil R972: make) by Japanese Aersoil Co., Ltd., use sample mill (sample mill) to mix then, obtain toner of the present invention (11)～(12) and contrast toner (11)～(13).

Toner is estimated with above mentioned evaluation method, and evaluation result is as shown in table 2.

[table 2]

The toner sequence number	MFT (℃)	Gross(℃)	HOT (℃)	Mobile	Comminuted mean grain size (μ m)
						Toner (11)	125	145	More than or equal to 230	○	11
Toner (12)	125	145	220	○	11
						Contrast toner (11)	130	145	170	△×	11
Contrast toner (12)	145	180	More than or equal to 230	△×	15
						Contrast toner (13)	125	180	More than or equal to 230	△	13

[embodiment 21～24, comparative example 21～22]

Embodiment 21

In the reactive tank identical with embodiment 1, add 127 parts of propylene glycol, 454 parts of terephthalic acid (TPA) dimethyl esters, 38 parts of hexane diacids, 452 parts of bisphenol-A 2 mole propylene oxide addition products, 2.3 parts of phenol novolac resin (average degree of polymerization 5.6) EO addition products and 3 parts as condensation catalyst four titanium butoxide acid esters, be reflected under 180 ℃ and in nitrogen stream, carried out 12 hours, remove the methyl alcohol that is produced simultaneously.Then reaction system is heated gradually until 230 ℃, reaction is 4 hours in nitrogen stream, removes the water that is produced simultaneously, further pressure is reduced to 5～20mmHg and reacts.When softening point arrives 98 ℃, cool off.When temperature reaches 180 ℃, add 17 parts of trimellitic anhydrides, be reflected at and carried out under the stirring condition 1 hour, take out product.The Mn of the vibrin that is taken out [21] is 3600, and Mp is 8000, and Tg is 60 ℃, and En is 114KJ, and G ' is 140, and Tm is 102 ℃, and tan δ is 6～11.

Embodiment 22

In the reactive tank identical with embodiment 1, add 347 parts of propylene glycol, 317 parts of terephthalic acid (TPA) dimethyl esters, 60 parts of hexane diacids and 3 parts of four titanium butoxide acid esters as condensation catalyst, be reflected under 180 ℃ and in nitrogen stream, carried out 8 hours, remove the methyl alcohol that is produced simultaneously.Then add 596 parts of bisphenol-As, 2 mole propylene oxide addition products, 2.3 parts of phenol novolac resins (average degree of polymerization 5.6) EO addition product, reaction system is heated gradually until 230 ℃, reaction is 4 hours in nitrogen stream, remove the propylene glycol and the water that are produced simultaneously, further pressure is reduced to 5～20mmHg and react, when softening point arrives 98 ℃, cool off.The propylene glycol that reclaims is 295 parts.When temperature arrives 180 ℃, add 17 parts of trimellitic anhydrides, under agitation reacted 1 hour, take out product.The Mn of the vibrin that is taken out [22] is 3700, and Mp is 7900, and Tg is that 60 ℃, En are 140KJ, and G ' is 150, and Tm is 102 ℃, and tan δ is 5～11.

Embodiment 23

In the reactive tank identical with embodiment 1, add 380 parts of propylene glycol, 46 parts of phenol novolac resins (average degree of polymerization 5.6)-EO addition product, 351 parts of terephthalic acid (TPA) dimethyl esters, 28 parts of hexane diacids and 3 parts of four titanium butoxide acid esters as condensation catalyst, be reflected under 180 ℃ and in nitrogen stream, carried out 8 hours, remove the methyl alcohol that is produced simultaneously.Then reaction system is heated gradually until 230 ℃, reaction is 4 hours in nitrogen stream, removes the propylene glycol and the water that are produced simultaneously, further pressure is reduced to 5～20mmHg and reacts.When softening point arrives 141 ℃, take out product.The propylene glycol that reclaims is 190 parts.The Mn of the vibrin that is taken out [23] is 3700, and Mp is 11000, and Tg is 65 ℃, and En is 73KJ, and G ' is 8.7 * 10 ³, Tm is 142 ℃, tan δ is 1.6～1.8.

Comparative example 21

In the reactive tank identical with embodiment 1, add 453 parts of terephthalic acid (TPA) ethylene glycol diester, 36 parts of hexane diacids and 3 parts of dibutyl tin oxides as condensation catalyst, then to wherein adding 596 parts of bisphenol-As, 2 mole propylene oxide addition products, 0.9 part of trimellitic anhydride, reaction system is heated gradually until 230 ℃, reaction is 7 hours in nitrogen stream, remove the ethylene glycol and the water that are produced simultaneously, further pressure is reduced to 1～20mmHg and react, when softening point arrives 98 ℃, cool off.The ethylene glycol that reclaims is 239 parts.When temperature arrives 180 ℃, add 17 parts of trimellitic anhydrides, under agitation reacted 1 hour, take out product.The Mn of the contrast vibrin [21 '] that is taken out is 4200, and Mp is 8100, and Tg is 58 ℃, and En is 167KJ, and G ' is 140, and Tm is 101 ℃, and tan δ is 4～11.

Embodiment 24 and comparative example 22

Polyester resin for toner of the present invention [21]～[23] with respect to 100 parts and contrast polyester resin for toner [21 '] add 8 parts of phthalocyanine blue KRO (adret pigment system) and 5 parts of Brazil waxs respectively, prepare toner as follows.

At first, with every kind of potpourri with Henschel mixer (FM10B, make by Mitsui three pond chemical machinery companies) carry out premixed, use double screw extrusion machine (PCM-30 then, make by pond shellfish Co., Ltd.) knead, it is broken to use ultrasonic jet mill Labo-jet (Japanese Pneumatic Co., Ltd. make) to carry out fine powder subsequently, uses air classifier (MDS-I then, Japan Pneumatic Co., Ltd. makes) carry out classification, acquisition particle diameter D50 is 8 microns a toner-particle.Then in per 100 parts of gained toner-particles, add 0.5 part of colloidal silica (Aersoil R972: make) by Japanese Aersoil Co., Ltd., use sample mill (sample mill) to mix then, obtain toner of the present invention (21)～(23) and contrast toner (21).

Toner is estimated with above mentioned evaluation method, and evaluation result is as shown in table 3.For image color wherein, carry out same photographic fixing evaluation with above-mentioned MFT, (Macbeth Densitometer) measures image color in the Macbeth optical concentration.

[table 3]

The toner sequence number	MFT (℃)	Gross (℃)	HOT (℃)	Mobile	Comminuted mean grain size (μ m)	Image color
							Toner (21)	135	145	200	○	11	1.31
Toner (22)	135	145	200	○	11	1.30
							Toner (23)	130	145	230	○	11	1.35
Contrast toner (21)	140	145	200	△×	12	1.18

About the 5th inventive embodiment:

Production Example 31～33, contrast Production Example 31 and 32

Production Example 31 (vibrin)

[synthesizing of linear polyesters]

The linear polyesters (Aa-1) of synthetic embodiment 1 is used as linear polyesters (Aa-31).

[synthesizing of non-linearity polyester]

The non-linearity polyester (Ab-1) of synthetic embodiment 1 is used as non-linearity polyester (Ab-31).

Production Example 32 (vibrin)

[synthesizing of linear polyesters]

The linear polyesters (Aa-2) of synthetic embodiment 2 is used as linear polyesters (Aa-32).

[synthesizing of non-linearity polyester]

The non-linearity polyester (Ab-2) of synthetic embodiment 2 is used as non-linearity polyester (Ab-32).

Production Example 33 (toner adjuvant)

In the autoclave reactive tank of thermometer and stirrer has been installed, add 600 parts of dimethylbenzene, (Viscol440P: softening point is 153 ℃ to 480 parts of thermal degradation type low-molecular-weight polypropylenes, Sanyo Chemical Industries, Ltd.'s system), and 120 parts of thermal degradation type low molecular weight polyethylenes (SanwaxLEL-400: softening point is 128 ℃, Sanyo Chemical Industries, Ltd.'s system), fully dissolve, and feeding nitrogen replacement air wherein, then under 175 ℃ temperature conditions, to contain 1992 parts of styrene with 3 hours, 168 parts of vinyl cyanide, 240 parts of maleic acid monobutyl esters, the potpourri of 78 part of six hydrogen terephthalic acid (TPA) di-t-butyl peroxide ester and 455 parts of dimethylbenzene drops in the reactive tank, carry out polymerization with this, drip and finish the back continuation this temperature maintenance 30 minutes.Then carry out desolvation and handle, obtain toner adjuvant (B-1) as modified waxes.

The Mn of adjuvant (B-1) is 2950, weight-average molecular weight is 10900, acid number is 20.9mgKOH/g.

Contrast Production Example 31 (vibrin)

[synthesizing of linear polyesters]

The linear polyesters (Aa '-6) of synthetic comparative example 2 is used as comparing linear polyesters (Aa '-31).

[synthesizing of non-linearity polyester]

The non-linearity polyester (Ab '-5) of synthetic comparative example 1 is used as comparing non-linearity polyester (Ab '-31).

Contrast Production Example 32

The 1200 parts of dimethylbenzene of in the autoclave reactive tank of thermometer and stirrer has been installed, packing into, and feed nitrogen with displacement air wherein, then under 175 ℃ temperature conditions, the potpourri that will contain 1992 parts of styrene, 168 parts of vinyl cyanide, 240 parts of maleic acid monobutyl esters, 78 part of six hydrogen terephthalic acid (TPA) di-t-butyl peroxide ester and 455 parts of dimethylbenzene with 3 hours drops in the reactive tank, carry out polymerization with this, drip and finish the back continuation this temperature maintenance 30 minutes.Then carry out desolvation and handle, obtain contrast toner adjuvant (B '-1).

The Mn of adjuvant (B '-1) is 2900, weight-average molecular weight is 9800, acid number is 25.8mgKOH/g.

Embodiment 31 and 32, and comparative example 31 and 32

Embodiment 31

[preparation of polyester resin composition for toner]

Making 580 parts of linear polyesters (Aa-31), 400 parts of non-linearity polyester (Ab-31) and 20 parts of toners is that 150 ℃, hold-up time be 3 minute condition under carry out fusion knead at jacket temperature with adjuvant (B-1) in continuous kneading machine.The gained molten resin is cooled to room temperature, pulverizes with comminutor then, make it granulating, obtain polyester resin composition for toner of the present invention (31).

The Tg of polyester resin composition for toner (31) is that 64 ℃, Mn are 2200, Mp is 3200, and it is 13% that THF does not dissolve part.

Embodiment 32

[preparation of polyester resin composition for toner]

Making 580 parts of linear polyesters (Aa-32), 400 parts of non-linearity polyester (Ab-32) and 20 parts of toners is that 150 ℃, hold-up time be 3 minute condition under carry out fusion knead at jacket temperature with adjuvant (B-1) in continuous kneading machine.The gained molten resin is cooled to room temperature, pulverizes with comminutor then, make it granulating, obtain polyester resin composition for toner of the present invention (32).

The Tg of polyester resin composition for toner (32) is that 64 ℃, Mn are 3200, Mp is 6700, and it is 13% that THF does not dissolve part.

Contrast Production Example 31

[preparation of polyester resin composition for toner]

Making 580 parts of linear polyesters (Aa '-31), 400 parts of non-linearity polyester (Ab '-31) and 20 parts of toners is that 150 ℃, hold-up time be 3 minute condition under carry out fusion knead at jacket temperature with adjuvant (B-1) in continuous kneading machine.The gained molten resin is cooled to room temperature, pulverizes with comminutor then, make it granulating, obtain contrast polyester resin composition for toner (31).

The Tg of contrast polyester resin composition for toner (31) is that 64 ℃, Mn are 3200, Mp is 6700, and it is 13% that THF does not dissolve part.

Contrast Production Example 32

[preparation of polyester resin composition for toner]

Making 580 parts of linear polyesters (Aa-32), 400 parts of non-linearity polyester (Ab-32) and 20 parts of contrast toners is that 150 ℃, hold-up time be 3 minute condition under carry out fusion knead at jacket temperature with adjuvant (B '-1) in continuous kneading machine.The gained molten resin is cooled to room temperature, pulverizes with comminutor then, make it granulating, obtain contrast polyester resin composition for toner (32).

The Tg of contrast polyester resin composition for toner (32) is that 64 ℃, Mn are 3200, Mp is 6700, and it is 13% that THF does not dissolve part.

Estimate embodiment (31)～(32) and comparative evaluation's example (31)～(32)

Polyester resin composition for toner of the present invention (31)～(32) with respect to 100 parts and contrast polyester resin composition for toner (31)～(32), add 8 parts of carbon black MA-100 (making), 5 parts of Brazil waxs, 1 part of charge control agent T-77 (making) respectively, prepare toner as follows by protecting scholar paddy chemical company by Mitsubishi chemical Co., Ltd.

At first, with every kind of potpourri with Henschel mixer (FM10B, make by Mitsui three pond chemical machinery companies) carry out premixed, use double screw extrusion machine (PCM-30 then, make by pond shellfish Co., Ltd.) knead, it is broken to use ultrasonic jet mill Labo-jet (Japanese Pneumatic Co., Ltd. make) to carry out fine powder subsequently, uses air classifier (MDS-I then, Japan Pneumatic Co., Ltd. makes) carry out classification, acquisition particle diameter D50 is 8 microns a toner-particle.Then in per 100 parts of gained toner-particles, add 0.5 part of colloidal silica (Aersoil R972: make) by Japanese Aersoil Co., Ltd., use sample mill (sample mill) to mix then, obtain toner of the present invention (31)～(32) and contrast toner (31)～(32).

Toner is estimated with following evaluation method, and evaluation result is listed in the table 4.

[table 4]

The toner sequence number	MFT(℃)	HOT(℃)	The toner flowability	Picture steadiness
					Toner (31)	120	230	○	○
Toner (32)	120	230	○	○
					Contrast toner (31)	135	230	△	△
Contrast toner (32)	130	210	×	×

[evaluation method]

[1] minimum fixing temperature (MFT)

According to the top method of putting down in writing.

[2] the deep fat China ink stains occurrence temperature (HOT)

According to the top method of putting down in writing.

[3] toner flowability

According to the top method of putting down in writing.

[4] picture steadiness

Use commercially available printing machine (LP-1300), insert prepared various toners, print mute light image then continuously.Image to the 5000th printing carries out visualization, by following standard picture steadiness is estimated.

Do not have unevenness and do not have white stripes: zero

Can be observed slight white stripes but do not have unevenness: △

Can be observed tangible white stripes and unevenness: *

The 6th embodiment that invention is related

Production Example 41～43, contrast Production Example 41～44

Production Example 41

[synthesizing of linear polyesters]

In the reactive tank identical with embodiment 1, add 792 parts of (22.8 moles) propylene glycol, 868 parts of (9.8 moles) terephthalic acid (TPA) dimethyl esters, 13 parts of (0.2 mole) hexane diacids and 3 parts of four titanium butoxide acid esters as condensation catalyst, be reflected under 180 ℃ and in nitrogen stream, carried out 8 hours, remove the methyl alcohol that is produced simultaneously.Then reaction system is heated gradually until 230 ℃, reaction is 4 hours in nitrogen stream, remove the propylene glycol and the water that are produced simultaneously, further pressure being reduced to 5～20mmHg reacts, when softening point (Tm) arrives 80 ℃, reaction system is cooled to 180 ℃, add 26 parts of (0.3 mole) trimellitic anhydrides, product is taken out in the airtight reaction down of normal pressure 2 hours.The propylene glycol that reclaims is 410 parts (11.8 moles).After the product that will take out is cooled to room temperature, be crushed to graininess.The product of gained is linear polyesters (Aa-41).

The Tg of linear polyesters (Aa-41) is 56 ℃, and Mn is 2200, and Mp is 4000, and it is 0% that THF does not dissolve part, and En is 73KJ, and G ' is 2.0 * 10 ², Tm is 82 ℃, tan δ is 4～12.

[synthesizing of non-linearity polyester]

In the reactive tank identical with embodiment 1, add 810 parts of (22.4 moles) propylene glycol, 774 parts of (8.4 moles) terephthalic acid (TPA) dimethyl esters, 111 parts of (1.6 moles) hexane diacids and 3 parts of four titanium butoxide acid esters as condensation catalyst, be reflected under 180 ℃ and in nitrogen stream, carried out 8 hours, remove the methyl alcohol that is produced simultaneously.Then reaction system is heated gradually until 230 ℃, reaction is 4 hours in nitrogen stream, removes the propylene glycol and the water that are produced simultaneously, further pressure is reduced to 5～20mmHg reaction 1 hour, and the propylene glycol of recovery is 427 parts (11.8 moles).Then reaction system is cooled to 180 ℃, add 18 parts of trimellitic anhydrides (0.2 mole), the normal pressure airtight condition reacted 2 hours down, be that 220 ℃, pressure are to continue reaction under the reduced pressure of 5～20mmHg in temperature then, when softening point (Tm) arrives 125 ℃, take out product and be cooled to room temperature, the resin-oatmeal that obtains is broken into graininess.The product that is obtained is non-linearity polyester (Ab-41).

The Tg of non-linearity polyester (Ab-41) is 55 ℃, and Mn is 7000, and Mp is 16000, and it is 3% that THF does not dissolve part, and En is 73KJ, and G ' is 6.8 * 10 ², Tm is 125 ℃, tan δ is 2.8～4.

[preparation of polyester resin for toner]

Making 600 parts of linear polyesters (Aa-41) and 400 parts of non-linearity polyester (Ab-41) is that 150 ℃, hold-up time are to carry out fusion under 3 minutes the condition to knead at jacket temperature in continuous kneading machine.The gained molten resin is cooled to room temperature, pulverizes with comminutor then, make it granulating, obtain polyester resin for toner of the present invention (A-41).

The Tg of polyester resin for toner (A-41) is 55 ℃, and Sp is 98 ℃, and Mn is 4500, and Mp is 5000, and it is 2% that THF does not dissolve part.As shown in Figure 1, Tg and Sp are the interior value of scope by formula (1)～(4) are surrounded.

Production Example 42

[synthesizing of linear polyesters]

In the reactive tank identical with embodiment 1, add 803 parts of (22.6 moles) propylene glycol, 816 parts of (9.0 moles) terephthalic acid (TPA) dimethyl esters, 68 parts of (1.0 moles) hexane diacids and 3 parts of four titanium butoxide acid esters as condensation catalyst, be reflected under 180 ℃ and in nitrogen stream, carried out 8 hours, remove the methyl alcohol that is produced simultaneously.Then reaction system is heated gradually until 230 ℃, reaction is 4 hours in nitrogen stream, remove the propylene glycol and the water that are produced simultaneously, further pressure being reduced to 5～20mmHg reacts, when softening point (Tm) arrives 93 ℃, reaction system is cooled to 180 ℃, add 26 parts of (0.3 mole) trimellitic anhydrides, the normal pressure airtight condition reacted 2 hours down, took out product.The propylene glycol that reclaims is 427 parts (12.0 moles).After the product that will take out is cooled to room temperature, the resin-oatmeal that obtains is broken to graininess.The product that is obtained is linear polyesters (Aa-42).

The Tg of linear polyesters (Aa-42) is 55 ℃, and Mn is 3000, and Mp is 5800, and it is 0% that THF does not dissolve part, and En is 73KJ, and G ' is 2.2 * 10 ², Tm is 95 ℃, tan δ is 5～11.

[synthesizing of non-linearity polyester]

In the reactive tank identical with embodiment 1, add 780 parts of (22.6 moles) propylene glycol, 793 parts of (9.0 moles) terephthalic acid (TPA) dimethyl esters, 66 parts of (1.0 moles) hexane diacids and 3 parts of four titanium butoxide acid esters as condensation catalyst, be reflected under 180 ℃ and in nitrogen stream, carried out 8 hours, remove the methyl alcohol that is produced simultaneously.Then reaction system is heated gradually until 230 ℃, reaction is 4 hours in nitrogen stream, removes the propylene glycol and the water that are produced simultaneously, further pressure is reduced to 5～20mmHg reaction 1 hour.The propylene glycol that reclaims is 397 parts (11.5 moles).Temperature of reaction system is cooled to 180 ℃ then, add 44 parts of (0.5 mole) trimellitic anhydrides, the normal pressure airtight condition reacts after 2 hours down, be that 220 ℃, pressure are to react under the reduced pressure of 5～20mmHg then in temperature, when softening point (Tm) reaches 145 ℃, take out product and be cooled to room temperature, the resin-oatmeal that obtains is broken to graininess.The product that is obtained is non-linearity polyester (Ab-42).

The Tg of non-linearity polyester (Ab-42) is 66 ℃, and Mn is 6800, and Mp is 10500, and it is 2% that THF does not dissolve part, and En is 73KJ, and G ' is 2.0 * 10 ³, Tm is 145 ℃, tan δ is 1.5～1.9.

[preparation of polyester resin for toner]

Making 600 parts of linear polyesters (Aa-42) and 400 parts of non-linearity polyester (Ab-42) is that 150 ℃, hold-up time are to carry out fusion under 3 minutes the condition to knead at jacket temperature in continuous kneading machine.The gained molten resin is cooled to room temperature, pulverizes with comminutor then, make it granulating, obtain polyester resin for toner of the present invention (A-42).

The Tg of polyester resin for toner (A-42) is 60 ℃, and Sp is 110 ℃, and Mn is 5000, and Mp is 6500, and it is 1% that THF does not dissolve part.As showing among Fig. 1, Tg and Sp are the interior value of scope by equation (1)～(4) are surrounded.

Production Example 43

[synthesizing of linear polyesters]

In the reactive tank identical with embodiment 1, add 634 parts of (22.7 moles) propylene glycol, 2 moles of PO addition products of 256 parts of (2.0 moles) bisphenol-As, 658 parts of (9.2 moles) terephthalic acid (TPA) dimethyl esters, 43 parts of (0.8 mole) hexane diacids and 3 parts of four titanium butoxide acid esters as condensation catalyst, be reflected under 180 ℃ and in nitrogen stream, carried out 8 hours, remove the methyl alcohol that is produced simultaneously.Then reaction system is heated gradually until 230 ℃, reaction is 4 hours in nitrogen stream, remove the propylene glycol and the water that are produced simultaneously, further pressure being reduced to 5～20mmHg reacts, when softening point (Tm) arrives 93 ℃, reaction system is cooled to 180 ℃, add 26 parts of trimellitic anhydrides (0.4 mole), the normal pressure airtight condition reacted 2 hours down, took out product.The propylene glycol that reclaims is 390 parts (13.9 moles).After the product that will take out is cooled to room temperature, the resin-oatmeal that obtains is broken to graininess.The product that is obtained is linear polyesters (Aa-43).

The Tg of linear polyesters (Aa-43) is 65 ℃, and Mn is 3300, and Mp is 6200, and it is 0% that THF does not dissolve part, and En is 90KJ, and G ' is 2.2 * 10 ², Tm is 95 ℃, tan δ is 5～11.

[synthesizing of non-linearity polyester]

In the reactive tank identical with embodiment 1, add 582 parts of (22.7 moles) propylene glycol, 3 moles of PO addition products of 326 parts of (2.4 moles) bisphenol-As, 603 parts of (9.2 moles) terephthalic acid (TPA) dimethyl esters, 39 parts of (0.8 mole) hexane diacids and 3 parts of four titanium butoxide acid esters as condensation catalyst, be reflected under 180 ℃ and in nitrogen stream, carried out 8 hours, remove the methyl alcohol that is produced simultaneously.Then reaction system is heated gradually until 230 ℃, reaction is 4 hours in nitrogen stream, removes the propylene glycol and the water that are produced simultaneously, further pressure is reduced to 5～20mmHg reaction 1 hour.The propylene glycol that reclaims is 360 parts (14.0 moles).Reaction system is cooled to 180 ℃ then, add 23 parts of trimellitic anhydrides (0.4 mole), the normal pressure airtight condition reacts after 2 hours down, be that 220 ℃, pressure are to react under the reduced pressure of 5～20mmHg then in temperature, when softening point (Tm) arrives 160 ℃, take out product and be cooled to room temperature, the resin-oatmeal that obtains is broken to graininess.The product that is obtained is non-linearity polyester (Ab-43).

The Tg of non-linearity polyester (Ab-43) is 65 ℃, and Mn is 7000, and Mp is 13200, and it is 3% that THF does not dissolve part, and En is 97KJ, and G ' is 9.5 * 10 ³, Tm is 160 ℃, tan δ is 1.2～2.2.

[preparation of polyester resin for toner]

Making 600 parts of linear polyesters (Aa-43) and 400 parts of non-linearity polyester (Ab-43) is that 150 ℃, hold-up time are to carry out fusion under 3 minutes the condition to knead at jacket temperature in continuous kneading machine.The gained molten resin is cooled to room temperature, pulverizes with comminutor then, make it granulating, obtain polyester resin for toner of the present invention (A-43).

The Tg of polyester resin for toner (A-43) is 65 ℃, and Sp is 125 ℃, and Mn is 5100, and Mp is 6500, and it is 2% that THF does not dissolve part.As shown in Figure 1, Tg and Sp are the interior value of scope by equation (1)～(4) are surrounded.

Contrast Production Example 41

[synthesizing of linear polyesters]

In the reactive tank identical with embodiment 1, add 2 moles of PO addition products of 642 parts of (11.9 moles) bisphenol-As, 3 moles of PO addition products of 131 parts of (2.1 moles) bisphenol-As, 257 parts of (10.0 moles) terephthalic acid (TPA)s and 3 parts of four titanium butoxide acid esters as condensation catalyst, be reflected under 230 ℃ and in nitrogen stream, carried out 5 hours, remove the water that is produced simultaneously.Further pressure is reduced to 5～20mmHg and reacts, when acid number smaller or equal to 2 the time, temperature of reaction system is cooled to 180 ℃, add 26 parts of (0.9 mole) trimellitic anhydrides, product is taken out in the reaction 2 hours down of normal pressure airtight condition.After the product that will take out is cooled to room temperature, the resin-oatmeal that obtains is broken to graininess.The product that is obtained is linear polyesters (Aa '-41).

The Tg of linear polyesters (Aa '-41) is 55 ℃, and Mn is 2000, and Mp is 4000, and the little dissolving part of THF is 0%, and En is 170KJ, and G ' is 2.0 * 10 ², Tm is 82 ℃, tan δ is 4～12.

[synthesizing of non-linearity polyester]

In the reactive tank identical with embodiment, add 3 moles of PO addition products of 777 parts of (12.5 moles) bisphenol-As, 171 parts of (6.7 moles) terephthalic acid (TPA)s, 59 parts of (2.0 moles) trimellitic anhydrides and 3 parts of four titanium butoxide acid esters as condensation catalyst, be reflected under 230 ℃ and in nitrogen stream, carried out 7 hours, remove the water that is produced simultaneously.Further pressure being reduced to 5～20mmHg reacts, when acid number smaller or equal to 2 the time, temperature of reaction system is cooled to 180 ℃, add 60 parts of (3.3 moles) fumaric acid, reaction is 4 hours under normal pressure, then pressure is reduced to 5～20mmHg and reacts, when softening point (Tm) is 115 ℃, take out product and be cooled to room temperature, the resin-oatmeal that obtains is broken to graininess.The product that is obtained is non-linearity polyester (Ab '-41).

The Tg of non-linearity polyester (Ab '-41) is 56 ℃, and Mn is 6500, and Mp is 9500, and it is 5% that THF does not dissolve part, and En is 184KJ, and G ' is 6.8 * 10 ², Tm is 125 ℃, tan δ is 0.7～1.1.

[preparation of polyester resin for toner]

Is that 150 ℃, hold-up time be 3 minute condition under carry out fusion knead at jacket temperature with 600 parts of linear polyesters (Aa '-41) and 400 parts of non-linearity polyester (Ab '-41) in continuous kneading machine.The gained molten resin is cooled to room temperature, pulverizes with comminutor then, make it granulating, obtain contrast polyester resin for toner (A '-41).

The Tg of contrast polyester resin for toner (A '-41) is 56 ℃, and Sp is 96 ℃, and Mn is 4000, and Mp is 5000, and it is 3% that THF does not dissolve part.As shown in Figure 1, Tg and Sp are in the scope that equation (1)～(4) are surrounded.

Contrast Production Example 42

[synthesizing of linear polyesters]

In the reactive tank identical with embodiment 1, add 2 moles of PO addition products of 490 parts of (8.4 moles) bisphenol-As, 3 moles of PO addition products of 266 parts of (4.0 moles) bisphenol-As, 278 parts of (10.0 moles) terephthalic acid (TPA)s and 3 parts of four titanium butoxide acid esters as condensation catalyst, be reflected under 230 ℃ and in nitrogen stream, carried out 5 hours, remove the water that is produced simultaneously.Further pressure is reduced to 5～20mmHg and reacts, when acid number smaller or equal to 2 the time, temperature of reaction system is cooled to 180 ℃, add 26 parts of (0.8 mole) trimellitic anhydrides, product is taken out in the reaction 2 hours down of normal pressure airtight condition.After the product that will take out is cooled to room temperature, the resin-oatmeal that obtains is broken to graininess.The product that is obtained is linear polyesters (Aa '-42).

The Tg of linear polyesters (Aa '-42) is 65 ℃, and Mn is 3000, and Mp is 5900, and it is 0% that THF does not dissolve part, and En is 172KJ, and G ' is 2.3 * 10 ², Tm is 95 ℃, tan δ is 5～11.

[synthesizing of non-linearity polyester]

In the reactive tank identical with embodiment 1, add 2 moles of PO addition products of 210 parts of (4.2 moles) bisphenol-As, 3 moles of PO addition products of 567 parts of (9.8 moles) bisphenol-As, 159 parts of (6.7 moles) terephthalic acid (TPA)s, 56 parts of (3.3 moles) fumaric acid and 3 parts of four titanium butoxide acid esters as condensation catalyst, be reflected under 210 ℃ and in nitrogen stream, carried out 7 hours, remove the water that is produced simultaneously.Further pressure being reduced to 5～20mmHg reacts, when acid number smaller or equal to 2 the time, temperature of reaction system is cooled to 180 ℃, add 74 parts of (2.7 moles) trimellitic anhydrides, reaction is after 2 hours under normal pressure, is that 220 ℃, pressure are to react under the reduced pressure of 5～20mmHg in temperature then, when softening point (Tm) reaches 160 ℃, take out product and be cooled to room temperature, the resin-oatmeal that obtains is broken to graininess.The product that is obtained is non-linearity polyester (Ab '-42).

The Tg of non-linearity polyester (Ab '-42) is 67 ℃, and Mn is 4000, and Mp is 7500, and it is 45% that THF does not dissolve part, and En is 179KJ, and G ' is 1.2 * 10 ⁴, Tm is 160 ℃, tan δ is 0.5～0.8.

[preparation of polyester resin for toner]

Is that 150 ℃, hold-up time be 3 minute condition under carry out fusion knead at jacket temperature with 600 parts of linear polyesters (Aa '-42) and 400 parts of non-linearity polyester (Ab '-42) in continuous kneading machine.The gained molten resin is cooled to room temperature, pulverizes with comminutor then, make it granulating, obtain contrast polyester resin for toner (A '-42).

The Tg of polyester resin for toner (A '-42) is 66 ℃, and Sp is 125 ℃, and Mn is 3500, and Mp is 6000, and it is 23% that THF does not dissolve part.As shown in Figure 1, the value of Tg and Sp is in the scope that equation (1)～(4) are surrounded.

Contrast Production Example 43

[synthesizing of linear polyesters]

In the reactive tank identical with embodiment 1, add 385 parts of (22.6 moles) propylene glycol, 2 moles of PO addition products of 156 parts of (2.0 moles) bisphenol-As, 3 moles of PO addition products of 451 parts of (5.0 moles) bisphenol-As, 391 parts of (9.0 moles) dimethyl terephthalate (DMT), 33 parts of (1.0 moles) hexane diacids and 3 parts of four titanium butoxide acid esters as condensation catalyst, be reflected under 180 ℃ and in nitrogen stream, carried out 8 hours, remove the methyl alcohol that is produced simultaneously.Then reaction system is heated gradually until 230 ℃, reaction is 4 hours in nitrogen stream, remove the propylene glycol and the water that are produced simultaneously, further pressure being reduced to 5～20mmHg reacts, when softening point (Tm) is 93 ℃, reaction system is cooled to 180 ℃, add 26 parts of (0.6 mole) trimellitic anhydrides, the normal pressure airtight condition reacted 2 hours down, took out product.The propylene glycol that reclaims is 304 parts (17.9 moles).After the product that will take out is cooled to room temperature, the resin-oatmeal that obtains is broken to graininess.The product that is obtained is linear polyesters (Aa '-43).

The Tg of linear polyesters (Aa '-43) is 52 ℃, and Mn is 2900, and Mp is 5800, and it is 0% that THF does not dissolve part, and En is 136KJ, and G ' is 2.3 * 10 ², Tm is 95 ℃, tan δ is 5～11.

[synthesizing of non-linearity polyester]

In the reactive tank identical with embodiment 1, add 132 parts of (8.0 moles) propylene glycol, 3 moles of PO addition products of 653 parts of (7.5 moles) bisphenol-As, 140 parts of (3.3 moles) dimethyl terephthalate (DMT), 83 parts of (2.0 moles) trimellitic anhydrides and 3 parts of four titanium butoxide acid esters as condensation catalyst, be reflected under 180 ℃ and in nitrogen stream, carried out 8 hours, remove the methyl alcohol that is produced simultaneously.Then reaction system is heated gradually until 230 ℃, reaction is 4 hours in nitrogen stream, removes the propylene glycol and the water that are produced simultaneously, further pressure is reduced to 5～20mmHg reaction 1 hour.The propylene glycol that reclaims is 61 parts (3.7 moles).Then reaction system is cooled to 180 ℃, adds 167 parts of (6.7 moles) fumaric acid, reaction is after 4 hours under normal pressure, then pressure being reduced to 5～20mmHg reacts, when softening point (Tm) is 130 ℃, take out product and be cooled to room temperature, the resin-oatmeal that obtains is broken to graininess.The product that is obtained is non-linearity polyester (Ab '-43).

The Tg of non-linearity polyester (Ab '-43) is 52 ℃, and Mn is 6500, and Mp is 10000, and it is 5% that THF does not dissolve part, and En is 143KJ, and G ' is 1.8 * 10 ³, Tm is 130 ℃, tan δ is 0.7～1.1.

[preparation of polyester resin for toner]

Making 600 parts of linear polyesters (Aa '-43) and 400 parts of non-linearity polyester (Ab '-43) is that 150 ℃, hold-up time are to carry out fusion under 3 minutes the condition to knead at jacket temperature in continuous kneading machine.The gained molten resin is cooled to room temperature, pulverizes with comminutor then, make it granulating, obtain polyester resin for toner of the present invention (A '-43).

The Tg of polyester resin for toner (A '-43) is 52 ℃, and Sp is 108 ℃, and Mn is 4500, and Mp is 6500, and it is 3% that THF does not dissolve part.As shown in Figure 1, the value of Tg and Sp is outside the scope that equation (1)～(4) are surrounded.

Contrast Production Example 44

[synthesizing of linear polyesters]

In the reactive tank identical with embodiment 1, add 329 parts of (22.9 moles) propylene glycol, 2 moles of PO addition products of 395 parts of (6.0 moles) bisphenol-As, 3 moles of PO addition products of 304 parts of (4.0 moles) bisphenol-As, 363 parts of (9.9 moles) dimethyl terephthalate (DMT), 3 parts of (0.1 mole) hexane diacids and 3 parts of four titanium butoxide acid esters as condensation catalyst, be reflected under 180 ℃ and in nitrogen stream, carried out 8 hours, remove the methyl alcohol that is produced simultaneously.Then reaction system is heated gradually until 230 ℃, reaction is 4 hours in nitrogen stream, remove the propylene glycol and the water that are produced simultaneously, further pressure being reduced to 5～20mmHg reacts, when softening point (Tm) is 95 ℃, reaction system is cooled to 180 ℃, add 26 parts of (0.7 mole) trimellitic anhydrides, the normal pressure airtight condition reacted 2 hours down, took out product.The propylene glycol that reclaims is 299 parts (20.8 moles).After the product that will take out is cooled to room temperature, the resin-oatmeal that obtains is broken to graininess.The product that is obtained is linear polyesters (Aa '-44).

The Tg of linear polyesters (Aa '-44) is 77 ℃, and Mn is 3000, and Mp is 6000, and it is 0% that THF does not dissolve part, and En is 156KJ, and G ' is 2.4 * 10 ², Tm is 97 ℃, tan δ is 2～8.

[synthesizing of non-linearity polyester]

In the reactive tank identical with embodiment 1, add 330 parts of (22.6 moles) propylene glycol, 2 moles of PO addition products of 656 parts of (9.8 moles) bisphenol-As, 373 parts of (10.0 moles) dimethyl terephthalate (DMT) and 3 parts of four titanium butoxide acid esters as condensation catalyst, be reflected under 180 ℃ and in nitrogen stream, carried out 8 hours, remove the methyl alcohol that is produced simultaneously.Then reaction system is heated gradually until 230 ℃, reaction is 4 hours in nitrogen stream, removes the propylene glycol and the water that are produced simultaneously, further pressure is reduced to 5～20mmHg reaction 1 hour.The propylene glycol that reclaims is 297 parts (20.3 moles).Then reaction system is cooled to 180 ℃, add 74 parts of (2.0 moles) trimellitic anhydrides, reaction is after 2 hours under normal pressure, be that 230 ℃, pressure are reduced under the reduced pressure of 5～20mmHg and reacted then in temperature, when softening point (Tm) is 132 ℃, take out product and be cooled to room temperature, the resin-oatmeal that obtains is broken to graininess.The product that is obtained is non-linearity polyester (Ab '-44).

The Tg of non-linearity polyester (Ab '-44) is 77 ℃, and Mn is 6600, and Mp is 9800, and it is 5% that THF does not dissolve part, and En is 149KJ, and G ' is 1.9 * 10 ³, Tm is 132 ℃, tan δ is 0.7～1.1.

[preparation of polyester resin for toner]

Making 600 parts of linear polyesters (Aa '-44) and 400 parts of non-linearity polyester (Ab '-44) is that 150 ℃, hold-up time are to carry out fusion under 3 minutes the condition to knead at jacket temperature in continuous kneading machine.The gained molten resin is cooled to room temperature, pulverizes with comminutor then, make it granulating, obtain polyester resin for toner of the present invention (A ,-44).

The Tg of polyester resin for toner (A '-44) is 77 ℃, and Sp is 110 ℃, and Mn is 4200, and Mp is 6600, and it is 3% that THF does not dissolve part.As shown in Figure 1, the value of Tg and Sp is outside the scope that equation (1)～(4) are surrounded.

[embodiment 41～43, comparative example 41～44]

Polyester resin for toner of the present invention (A-41)～(A-43) with respect to 100 parts and contrast polyester resin for toner (A '-41)～(A '-44), add 4 parts of yellow uitramarine (toner yellow HGVP2155 respectively, Clariant Japan K.K. Co., Ltd. system), 5 parts of Brazil waxs, 1 part of charge control agent T-77 (protecting scholar paddy chemical company system), prepare toner as follows.

At first, with every kind of potpourri with Henschel mixer (FM10B, make by Mitsui three pond chemical machinery companies) carry out premixed, use double screw extrusion machine (PCM-30 then, make by pond shellfish Co., Ltd.) knead, it is broken to use ultrasonic jet mill Labo-jet (Japanese Pneumatic Co., Ltd. make) to carry out fine powder subsequently, uses air classifier (MDS-I then, Japan Pneumatic Co., Ltd. makes) carry out classification, acquisition particle diameter D50 is 8 microns a toner-particle.Then in per 100 parts of gained toner-particles, add 0.5 part of colloidal silica (Aersoil R972: make) by Japanese Aersoil Co., Ltd., use sample mill (sample mill) to mix then, obtain toner of the present invention (41)～(43) and contrast toner (41)～(44).

Toner is with following evaluation method evaluation, and evaluation result is listed in the table 5.

[table 5]

The toner sequence number	MFT(℃)	HOT(℃)	Tone	Comminuted mean grain size (μ m)
					Toner (41)	120	225	○	11
Toner (42)	120	230	○	11
					Toner (43)	120	230	○	11
Contrast toner (41)	120	225	△	13
					Contrast toner (42)	125	230	×	15
Contrast toner (43)	120	215	△	12
					Contrast toner (44)	130	225	×	14

[evaluation method]

[1] minimum fixing temperature (MFT)

The method of putting down in writing according to the front.

[2] the deep fat China ink stains occurrence temperature (HOT)

The method of putting down in writing according to the front.

[3] tone

Adopt with above-mentioned MFT in identical mode, when the fixing roller temperature is 170 ℃ with image fixing on ohp film, show by the image after the photographic fixing by overhead projector then, estimate tone by visualization.

Criterion:

Zero: faint yellow clearly,

△: yellow clearly,

*: the yellow that some is fuzzy

[4] comminuted

The method of putting down in writing according to the front.

The 7th and the 8th embodiment that relates to of the present invention

[Production Example 51～53]

Production Example 51 (preparation of aqueous medium)

In the reaction vessel of being furnished with stirring rod and thermometer, add 753 parts of water, 8 parts of succinic acid alkyl allyl ester sulfonate sodium (alkylallylsulfosuccinic acid sodium salt, trade name Eleminol JS-2, Sanyo changes into industry system), 58 parts of styrene, 58 parts of methacrylic acids, 77 parts of butyl acrylates, 1 part of ammonium persulfate and 9 parts of surfactants (polyoxygenated sorbitan monoleate), the gained potpourri stirred 15 minutes under the 400rpm condition, obtained white emulsion.Emulsion is warmed up to 75 ℃ of system temperatures, and reacted 5 hours.Further add 30 part of 1% ammonium persulfate aqueous solution, thus with reactor product at 75 ℃ of water-borne dispersions that obtained vinylite (multipolymer of styrene-methacrylic acid-butyl acrylate-succinic acid alkyl allyl ester sulfonate sodium) in aging 5 hours.

Further, 48.5% aqueous solution (Eleminol MON-7 with 2 parts of sodium carboxymethyl celluloses, 40 parts of disodium 4-dodecyl-2,4 '-oxydibenzenesulfonates, Sanyo changes into industry system) and 443 parts of ion exchange waters join in 15 parts of above-mentioned water-borne dispersions, and evenly stir, obtain aqueous medium.The volume average particle size that the gained aqueous medium records by LA-920 is 0.05 μ m.

Production Example 52 (preparation of colorant dispersion)

In beaker, add 20 parts of copper phthalocyanines, (Solsperse 28000 for 4 parts of colorant dispersion, Avecia Co., Ltd. system) and 76 parts of ethyl acetate, stir and evenly dispersion, by the bead comminutor copper phthalocyanine is carried out differential then and loose to obtain " colorant dispersion ".The volume average particle size that " colorant dispersion " that is obtained records by LA-920 is 0.3 μ m.

Production Example 53 (preparation of releasing agent dispersion)

In beaker, add 20 parts of paraffin and 80 parts of ethyl acetate, stir and evenly dispersion, by the bead comminutor paraffin is carried out differential then and loose to obtain " releasing agent dispersion ".The volume average particle size that " releasing agent dispersion " that is obtained records by LA-920 is 0.5 μ m.

[embodiment 51～55 and comparative example 51～54]

Embodiment 51

[synthesizing of linear polyesters]

Linear polyesters (Aa-1) among the synthetic embodiment 1 is as linear polyesters (K1a-51).

[synthesizing of non-linearity polyester]

Non-linearity polyester (Ab-1) among the synthetic embodiment 1 is as non-linearity polyester (K1b-51).

[preparation of oiliness mixed liquor]

" releasing agent dispersion " and 25 parts of ethyl acetate of 24 parts of linear polyesters (K1a-51), 16 parts of non-linearity polyester (K1b-51), " colorant dispersion " of 10 parts of Production Example 52 preparations, 25 parts of Production Example 53 preparations are mixed and evenly stirring, obtain oiliness mixed liquor (I-1).

[preparation of resin particle]

In " aqueous medium " of 60 parts of embodiment, 51 preparations, add 40 portions of oiliness mixed liquors (I-1), stirred 3 minutes at 12000rpm by TK type homogeneous mixer.Then mixed liquor is transferred in the flask of being furnished with paddle and thermometer, heated 40 ℃ hot bath, ethyl acetate is removed in decompression simultaneously, thereby obtains the aqueous liquid dispersion of resin particle.Filter dispersion liquid then, with isolated particle by through circulation dryer 40 ℃ of dryings 18 hours, obtain resin particle (51).

Embodiment 52

[synthesizing of linear polyesters]

Linear polyesters (Aa-2) among the synthetic embodiment 2 is as linear polyesters (K1a-52).

[synthesizing of non-linearity polyester]

Non-linearity polyester (Ab-2) among the synthetic embodiment 2 is as non-linearity polyester (K1b-52).

[preparation of oiliness mixed liquor]

Oiliness mixed liquor (I-2) obtains by the mode identical with embodiment 51, and difference only is to adopt linear polyesters (K1a-52) to replace linear polyesters (K1a-51), adopts non-linearity polyester (K1b-52) to replace non-linearity polyester (K1b-51).

[preparation of polyester granulate]

Polyester granulate (52) adopts the mode identical with embodiment 51 to obtain, and difference only is to adopt oiliness mixed liquor (I-2) replacement oiliness mixed liquor (I-1).

Embodiment 53

[synthesizing of linear polyesters]

Linear polyesters (Aa-3) among the synthetic embodiment 3 is as linear polyesters (K1a-53).

[synthesizing of non-linearity polyester]

Non-linearity polyester (Ab-3) among the synthetic embodiment 3 is as non-linearity polyester (K1b-53).

[preparation of oiliness mixed liquor]

Oiliness mixed liquor (I-3) obtains by the mode identical with embodiment 51, and difference only is to adopt linear polyesters (K1a-53) to replace linear polyesters (K1a-51), adopts non-linearity polyester (K1b-53) to replace non-linearity polyester (K1b-51).

[preparation of polyester granulate]

Polyester granulate (53) adopts the mode identical with embodiment 51 to obtain, and difference only is to adopt oiliness mixed liquor (I-3) replacement oiliness mixed liquor (I-1).

Embodiment 54

[synthesizing of linear polyesters]

Linear polyesters (Aa-4) among the synthetic embodiment 4 is as linear polyesters (K1a-54).

[synthesizing of non-linearity polyester]

Non-linearity polyester (Ab-4) among the synthetic embodiment 4 is as non-linearity polyester (K1b-54).

[preparation of oiliness mixed liquor]

Oiliness mixed liquor (I-4) obtains by the mode identical with embodiment 51, and difference only is to adopt linear polyesters (K1a-54) to replace linear polyesters (K1a-51), adopts non-linearity polyester (K1b-54) to replace non-linearity polyester (K1b-51).

[preparation of polyester granulate]

Polyester granulate (54) adopts the mode identical with embodiment 51 to obtain, and difference only is to adopt oiliness mixed liquor (I-4) replacement oiliness mixed liquor (I-1).

Embodiment 55

[synthesizing of styrene-propene acid resin]

Air in the autoclave of 1L by behind the nitrogen replacement, is added 150 parts of dimethylbenzene, under the state of airtight stirring, be heated to 150 ℃.The mixed liquor that will contain 425 parts of styrene, 75 parts of n-butyl acrylates, 5 parts of di-t-butyl peroxides and 95 parts of dimethylbenzene with 3 hours drops to autoclave, and to keep the temperature of autoclave simultaneously be 150 ℃, to carry out polyreaction.Keep 1 hour to finish polyreaction in this temperature afterwards.Resulting polymers solution is carried out vacuum drying at 180 ℃ be cooled to room temperature then, obtain polymkeric substance (G1) after the pulverizing.The Mn of the styrene-propene acid resin (G1) that is obtained is 7500, and Mp is 1400.

[making of oiliness mixed liquor]

" releasing agent dispersion " and 25 parts of ethyl acetate of 20 parts of linear polyesters (K1a-51), 17 parts of non-linearity polyester (K1b-51), 3 parts of styrene-propene acid resins (G1), " colorant dispersion " of 10 parts of embodiment 52 preparations, 25 parts of embodiment 53 preparations are mixed and evenly stirring, obtain oiliness mixed liquor (I-5).

[preparation of resin particle]

In " aqueous medium " of 51 preparations of 60 parts of Production Examples, add 40 portions of oiliness mixed liquors (I-5), stirred 3 minutes at 12000rpm by TK type homogeneous mixer.Then mixed liquor is transferred in the flask of being furnished with paddle and thermometer, heated 40 ℃ water-bath, ethyl acetate is removed in decompression simultaneously, thereby obtains the aqueous liquid dispersion of resin particle.Filter dispersion liquid then, with isolated particle by through circulation dryer 40 ℃ of dryings 18 hours, obtain resin particle (55).

Comparative example 51

[synthesizing of linear polyesters]

Linear polyesters (Aa '-5) in the synthetic comparative example 1, linear polyesters (K1a '-55) as a comparison.

[synthesizing of non-linearity polyester]

Non-linearity polyester (Ab '-5) in the synthetic comparative example 1, non-linearity polyester (K1b '-55) as a comparison.

[preparation of oiliness mixed liquor]

Oiliness mixed liquor (I-6) obtains by the mode identical with embodiment 51, and difference only is to adopt linear polyesters (K1a '-55) to replace linear polyesters (K1a-51), adopts non-linearity polyester (K1b '-55) to replace non-linearity polyester (K1b-51).

[preparation of resin particle]

Comparative resin particle (51) adopts the mode identical with embodiment 51 to obtain, and difference only is to adopt oiliness mixed liquor (I-6) replacement oiliness mixed liquor (I-1).

Comparative example 52

[synthesizing of linear polyesters]

Linear polyesters (Aa '-6) in the synthetic comparative example 2, linear polyesters (K1a '-56) as a comparison.

[preparation of oiliness mixed liquor]

Oiliness mixed liquor (I-7) obtains by the mode identical with embodiment 51, and difference only is to adopt linear polyesters (K1a '-56) to replace linear polyesters (K1a-51), adopts non-linearity polyester (K1b '-55) to replace non-linearity polyester (K1b-51).

[preparation of resin particle]

Comparative resin particle (52) adopts the mode identical with embodiment 51 to obtain, and difference only is to adopt oiliness mixed liquor (I-7) replacement oiliness mixed liquor (I-1).

Comparative example 53

[synthesizing of linear polyesters]

Linear polyesters (Aa '-7) in the synthetic comparative example 3 is as linear polyesters (K1a '-57).Because polyester (K1a '-57) can not be changed into resin, so it can not be used for preparing corresponding resin particle.

Comparative example 54

[synthesizing of linear polyesters]

The linear polyesters (Aa '-8) of synthetic comparative example 4, with it as linear polyesters (K1a '-58).

[synthesizing of non-linearity polyester]

Non-linearity polyester (Ab '-8) in the synthetic comparative example 4, with it as non-linearity polyester (K1b '-58).

[making of oiliness mixed liquor]

Oiliness mixed liquor (I-8) obtains by the mode identical with embodiment 51, and difference only is to adopt linear polyesters (K1a '-58) to replace linear polyesters (K1a-51), adopts non-linearity polyester (K1b '-58) to replace non-linearity polyester (K1b-51).

[preparation of resin particle]

Comparative resin particle (54) adopts the mode identical with embodiment 51 to obtain, and difference only is to adopt oiliness mixed liquor (I-8) replacement oiliness mixed liquor (I-1).

Adopt following evaluation method to estimate, evaluation result is listed in the table 6.

Table 6

The toner sequence number	MFT (℃)	HOT (℃)	The toner flowability	Volume average particle size (μ m)
					Resin particle (51)	125	230	○△	5.8
Resin particle (52)	120	230	○	5.7
					Resin particle (53)	125	230	○	5.8
Resin particle (54)	125	230	○	6.0
					Resin particle (55)	125	230	○	5.8
Comparative resin particle (51)	135	215	△×	5.9
					Comparative resin particle (52)	130	230	△×	5.8
Comparative resin particle (54)	130	230	△	5.6

[evaluation method]

[1] minimum fixing temperature (MFT)

The method of putting down in writing according to the front.

[2] the deep fat China ink stains occurrence temperature (HOT)

The method of putting down in writing according to the front.

[3] toner flowability

The method of putting down in writing according to the front.

[4] volume average particle size

The volume averaging primary particle diameter of resin particle utilizes Ku Erte particle collector TAII (U.S. Coulter electronics corporation system) to measure.

[Production Example 61～68]

Production Example 61 (containing the preparation of the aqueous liquid dispersion of resin particle (Q-1))

In the reaction vessel of being furnished with stirring rod and thermometer, add 48 parts of phenylethene modified phenol polyoxyethylene addition product (Eleminol HB-12, Sanyo changes into industrial society system) and 232 parts of bisphenol A diglycidyl ethers (Epikote 828, and uniform dissolution oiling Shell Epoxy Co., Ltd. system).Drip water at stirring condition downhill reaction container.When the water that adds 31 parts, reaction system generation emulsification and become the opaque solution of milky.Further be added dropwise to 224 parts of water, obtain emulsion.After system temperature is heated to 70 ℃, keep this temperature, will add in the reaction system by the drips of solution that 20 parts of ethylenediamines are dissolved in gained in 446 parts of water with 2 hours.After being added dropwise to complete, reaction system obtained the aqueous liquid dispersions of amine cured epoxy resin (Q-1) 70 ℃ of reactions 5 hours in 5 hours thereby then wear out at 90 ℃.

Further, 48.5% aqueous solution (the Eleminol MON-7 that in 18 parts of above-mentioned water-borne dispersions, adds 2 parts of sodium carboxymethyl celluloses, 40 parts of disodium 4-dodecyl-2,4 '-oxydibenzenesulfonates, Sanyo changes into the industry system) and 443 parts of ion exchange waters, and evenly stir, obtain the aqueous liquid dispersion of resinous particulate (Q-1).

The volume average particle size of the resin particle (Q-1) that records by laser class particle size distribution device LA-920 (hole field make made) is 0.81 μ m.In addition, the aqueous liquid dispersion that a part is contained resin particle (Q-1) carries out centrifuging, and the further step that repeats to add the water centrifuging for 2 times is carried out drying, the separation resin component then.The Tg of described resin Composition (by dsc measurement, identical therewith hereinafter) is 120 ℃.

Production Example 62 (containing the preparation of the aqueous liquid dispersion of resin particle (Q-2))

In the reaction vessel of being furnished with stirring rod and thermometer, add 38 parts of phenylethene modified phenol polyoxyethylene addition product (Eleminol HB-12, Sanyo changes into industrial society system), (Epikote 828 for 232 parts of bisphenol A diglycidyl ethers, and uniform dissolution oiling Shell Epoxy Co., Ltd. system) and 10 parts of dioctyl phthalates.Drip water at stirring condition downhill reaction container.When the water that adds 31 parts, reaction system generation emulsification and become the opaque solution of milky.Further be added dropwise to 224 parts of water, obtain emulsion (1).After system temperature is heated to 70 ℃, keep this temperature, will add in the reaction system by the drips of solution that 20 parts of ethylenediamines are dissolved in gained in 446 parts of water with 2 hours.After being added dropwise to complete, reaction system obtained the aqueous liquid dispersions of amine cured epoxy resin (Q-2) 70 ℃ of reactions 5 hours in 5 hours thereby then wear out at 90 ℃.

Further, 48.5% aqueous solution (the Eleminol MON-7 that in 18 parts of above-mentioned water-borne dispersions, adds 2 parts of sodium carboxymethyl celluloses, 40 parts of disodium 4-dodecyl-2,4 '-oxydibenzenesulfonates, Sanyo changes into the industry system) and 443 parts of ion exchange waters, and evenly stir, obtain the aqueous liquid dispersion of resinous particulate (Q-2).

The volume average particle size of the resin particle (Q-2) that records by laser class particle size distribution device LA-920 (hole field make made) is 0.75 μ m.In addition, the aqueous liquid dispersion that a part is contained resin particle (Q-2) carries out centrifuging, and the further step that repeats to add the water centrifuging for 2 times is carried out drying, the separation resin component then.The Tg of described resin Composition (by dsc measurement, identical therewith hereinafter) is 114 ℃.

Production Example 63 (containing the preparation of the aqueous liquid dispersion of resin particle (Q-3))

In the reaction vessel of being furnished with stirring rod and thermometer, add 753 parts of water, 8 parts of succinic acid alkyl allyl ester sulfonate sodium (Eleminol JS-2, Sanyo changes into industry system), 58 parts of styrene, 58 parts of methacrylic acids, 77 parts of butyl acrylates, 1 part of ammonium persulfate and 9 parts of surfactants (polyoxygenated sorbitan monoleate), the gained potpourri stirred 15 minutes under the 400rpm condition, obtained white emulsion.Emulsion is warmed up to 75 ℃ of system temperatures, and reacted 5 hours.Further add 30 part of 1% ammonium persulfate solution, thereby reaction product was obtained vinylites (multipolymer of styrene-methacrylic acid-butyl acrylate-succinic acid alkyl allyl ester sulfonate sodium) water-borne dispersions (Q-3) in aging 5 hours at 75 ℃.

Further, 48.5% aqueous solution (Eleminol MON-7 with 2 parts of sodium carboxymethyl celluloses, 40 parts of disodium 4-dodecyl-2,4 '-oxydibenzenesulfonates, Sanyo changes into industry system) and 443 parts of ion exchange waters join in 15 parts of above-mentioned water-borne dispersions, and evenly stir, obtain containing the water-borne dispersions of vinylite (Q-3).

This water-borne dispersions is by electrophoresis-type particle size distribution device ELS-8000 (Da mound electronics system) volume average particle size that records is 0.05 μ m.In addition, the aqueous liquid dispersion that a part is contained resin particle (Q-3) carries out centrifuging, and the further step that repeats to add the water centrifuging for 2 times is carried out drying, the separation resin component then.The Tg of described resin Composition is 75 ℃.

Production Example 64 (containing the preparation of the aqueous liquid dispersion of resin particle (Q-4))

In the reaction vessel of being furnished with stirring rod and thermometer, add 753 parts of water, 8 parts of succinic acid alkyl allyl ester sulfonate sodium (Eleminol JS-2, Sanyo changes into industry system), 58 parts of styrene, 58 parts of methacrylic acids, 72 parts of butyl acrylates, 5 parts of E-84 (salicylic acid type metal complexs, Olient science Industrial Co., Ltd system), 1 part of ammonium persulfate and 9 parts of surfactants (polyoxygenated sorbitan monoleate), the gained potpourri stirred 15 minutes under the 400rpm condition, obtained white emulsion.Emulsion is warmed up to 75 ℃ of system temperatures, and reacted 5 hours.Further add 30 part of 1% ammonium persulfate solution, thereby reactor product was obtained vinylites (multipolymer that contains the styrene-methacrylic acid-butyl acrylate-succinic acid alkyl allyl ester sulfonate sodium of salicylic acid type metal complex) water-borne dispersions (Q-4) in aging 5 hours at 75 ℃.

Further, 48.5% aqueous solution (Eleminol MON-7 with 2 parts of sodium carboxymethyl celluloses, 40 parts of disodium 4-dodecyl-2,4 '-oxydibenzenesulfonates, Sanyo changes into industry system) and 443 parts of ion exchange waters join in 15 parts of above-mentioned water-borne dispersions, and evenly stir, contained the water-borne dispersions of (Q-4).

This water-borne dispersions is by electrophoresis-type particle size distribution device ELS-8000 (Da mound electronics system) volume average particle size that records is 0.05 μ m.In addition, the aqueous liquid dispersion that a part is contained resin particle (Q-4) carries out centrifuging, and the further step that repeats to add the water centrifuging for 2 times is carried out drying, the separation resin component then.The Tg of described resin Composition is 80 ℃.

Production Example 65 (preparation of hardening agent (β-1))

In the reaction vessel of being furnished with stirring rod and thermometer, add 50 parts of ethylenediamines and 50 parts of MIBK, 50 ℃ of reactions 5 hours.The ketimine compound that is obtained is used as hardening agent (β-1).

Production Example 66 (preparation of hardening agent (β-2))

In the reaction vessel of being furnished with stirring rod and thermometer, add 45 parts of isoflurane chalcone diisocyanates and 55 parts of MEK, 50 ℃ of reactions 5 hours.The ketimine compound that is obtained is used as hardening agent (β-2).

Production Example 67 (preparation of colorant dispersion)

In beaker, add 20 parts of copper phthalocyanines, (Solsperse 28000 for 4 parts of colorant dispersion, Avecia Co., Ltd. system) and 76 parts of ethyl acetate, stir and evenly dispersion, by the bead comminutor copper phthalocyanine is carried out differential then and loose to obtain " colorant dispersion ".The volume average particle size that " colorant dispersion " that is obtained records by LA-920 is 0.3 μ m.

Production Example 68 (preparation of releasing agent dispersion)

In beaker, add 20 parts of paraffin and 80 parts of ethyl acetate, stir and evenly dispersion, by the bead comminutor paraffin is carried out differential then and loose to obtain " releasing agent dispersion ".The volume average particle size that " releasing agent dispersion " that is obtained records by LA-920 is 0.5 μ m.

[embodiment 61～66 and comparative example 61～64]

Embodiment 61

[synthesizing of polyester (61)]

Linear polyesters (Aa-1) among the synthetic embodiment 1 is as polyester (61).Its hydroxyl value is 75, acid number is 1.

[synthesizing of urethane resin (61)]

In the reactive tank identical with embodiment 1, add 68 parts of polyester (61), 10 parts of isoflurane chalcone diisocyanates and 78 parts of ethyl acetate, be reflected in the stream of nitrogen gas in 75 ℃ and carried out 18 hours, obtain the ethyl acetate solution of urethane resin (61).The Mn of urethane resin (61) is 3300, and in the ethyl acetate solution of urethane resin (61), solid matter content is 50%, and viscosity is 2,400mPaS.

[synthesizing of polyester (62)]

Linear polyesters (Aa-2) among the synthetic embodiment 2 is as polyester (62).Its hydroxyl value is 42, acid number is 1.

[preparation of the solvent solution (p-1) of resin (p)]

" colorant dispersion " of the ethyl acetate solution of 14 parts of polyester (62), 52 parts of urethane resins (61), 10 parts of Production Example 65 preparations, " releasing agent dispersion " and 25 parts of ethyl acetate of 25 parts of Production Example 63 preparations are mixed mutually, and evenly stir, obtain the solvent solution (p-1) of resin (p).

[preparation of resin particle]

In the aqueous liquid dispersion that contains resin particle (Q-1) of 60 parts of Production Examples, 61 preparations, add the solvent solution (p-1) of 40 parts of resins (p), under 12000rpm, stirred 3 minutes by TK type homogeneous mixer.Then, mixed liquor is moved on in the flask of being furnished with paddle and thermometer, heat 40 ℃ water-bath, ethyl acetate is removed in decompression simultaneously, thereby obtains the aqueous liquid dispersion of resin particle.Filter dispersion liquid then, with isolated particle by through circulation dryer 40 ℃ of dryings 18 hours, obtain resin particle (61).The Tg of resin particle (61) is 65 ℃, and particle diameter is 95 μ m, and the ratio of the volume average particle size of itself and resin particle (Q-1) is 0.0085.

Further, in 100 parts of resin particles (61), add the HDI of 20 parts of MEK oxime end-blockings, the potpourri that obtains was mixed 30 minutes by Henschel mixer, thereby obtain coating composition (1).

Embodiment 62

[prepolymer (α-1) synthetic that contains isocyanate group]

In the reactive tank identical with embodiment 1, add 31 parts of polyester (p-1), 19 parts of isoflurane chalcone diisocyanates and 50 parts of ethyl acetate, be reflected in the stream of nitrogen gas in 75 ℃ and carried out 18 hours, obtain containing the ethyl acetate solution of the prepolymer (α-1) of isocyanate group.Contain in the ethyl acetate solution of prepolymer (α-1) of isocyanate group, the content of solid matter is 50%, the content of isocyanates is 2.1%.

[preparation of the solvent solution (p-2) of resin (p)]

Adopt the mode identical to prepare the solvent solution (p-2) of resin (p) with embodiment 61, difference only is to adopt 52 parts of ethyl acetate solutions that contain the prepolymer (α-1) of isocyanate group to replace the ethyl acetate solution of 52 parts of urethane resins (61), also used the hardening agent (β-1) of preparation in 5.3 parts of Production Examples 65 simultaneously.

[preparation of resin particle]

Adopt the mode identical with embodiment 61 to prepare resin particle (62) and coating composition (62), difference only is to adopt the aqueous liquid dispersion of resinous particulate (Q-2) to substitute the solvent solution (p-1) of solvent solution (p-2) the replacement resin (p) of the aqueous liquid dispersion of resinous particulate (Q-1) and employing resin (p).The Tg of resin particle (62) is 70 ℃, and particle diameter is 120 μ m, with the ratio of the volume average particle size of resin particle (Q-2) be 0.0063.

Embodiment 63

[synthesizing of styrene-propene acid copolymer]

Is being furnished with condenser pipe, add 160 parts of ethyl acetate in the reaction vessel of stirrer and nitrogen conduit, after reaction vessel is warmed up to 75 ℃, to contain 40 parts of styrene with 4 hours, 120 parts of butyl methacrylates, 60 parts of acrylic acid, 60 parts of ethyl acetate, and the mixed liquor of 0.3 part of azoisobutyronitrile drops in the reaction vessel, and further add 0.5 part of azoisobutyronitrile, make reaction system 75 ℃ of slakings 8 hours then, acquisition contains the resin solution of styrene-propene acid copolymer, wherein the Mn of styrene-propene acid copolymer is 4,200, hydroxyl value is 0, acid number is 210, and the solids content of resin solution is 50%.

[preparation of the solvent solution (p-3) of resin (p)]

Adopt the mode identical with embodiment 61 to prepare the solvent solution (p-3) of resin (p), difference only is that the resin solution that contains the styrene-propene acid copolymer that adopts 28 parts of solids contents 50% replaces 14 parts of polyester (62), adopts 52 parts of ethyl acetate solutions that contain the prepolymer (α-1) of isocyanate group to replace the ethyl acetate solution of 52 parts of urethane resins (61), also used the hardening agent (β-1) for preparing in 5.3 parts of Production Examples 65 simultaneously.

[preparation of resin particle]

Adopt the mode identical with embodiment 61 to prepare resin particle (63) and coating composition (63), difference only is to adopt the aqueous liquid dispersion of resinous particulate (Q-2) to substitute the solvent solution (p-1) of solvent solution (p-3) the replacement resin (p) of the aqueous liquid dispersion of resinous particulate (Q-1) and employing resin (p).The Tg of resin particle (63) is 81 ℃, and particle diameter is 142 μ m, with the ratio of the volume average particle size of resin particle (Q-1) be 0.0057.

Embodiment 64

[synthesizing of polyester (63)]

Linear polyesters (Aa-4) among the synthetic embodiment 4 is as polyester (63).

[preparation of the solvent solution (p-4) of resin (p)]

70 parts of polyester (63), 30 parts are contained " releasing agent dispersion " and 25 parts of ethyl acetate that " colorant dispersion " that the hardening agent (β-2) of the ethyl acetate solution of the prepolymer (α-1) of isocyanates, 1.8 parts of Production Example 66 preparations, 25 parts of Production Examples 67 obtain, 50 parts of Production Examples 68 obtain to be mixed mutually, evenly stir, obtain the solvent solution (p-4) of resin (p).

[preparation of resin particle]

Adopt the mode identical to prepare resin particle (64), the solvent solution (p-1) that difference only is to adopt the aqueous liquid dispersion of resinous particulate (Q-3) to substitute the aqueous liquid dispersion of resinous particulate (Q-1) and adopt solvent solution (p-4) the replacement resin (p) of resin (p) with embodiment 61.The Tg of resin particle (64) is 48 ℃, and particle diameter is 4.8 μ m, with the ratio of the volume average particle size of resin particle (Q-3) be 0.010.

Further, utilize sample mill with 100 parts of resin particles (64) and 0.5 part of colloidal silica (Aerosil R972: Japanese Aerosil Co., Ltd. system) mix, to obtain method for producing toner and toner (64).

Embodiment 65

[synthesizing of polyester (64)]

In the reaction vessel of being furnished with condenser pipe, stirrer and nitrogen conduit, add 570 parts of bisphenol-A 2 mole ethylene oxide addition products and 217 parts of terephthalic acid (TPA)s, under normal pressure, carry out polycondensation 6 hours at 230 ℃, then under reduced pressure, carry out polycondensation 6 hours at 230 ℃, the Mn of gained polyester is 2600, hydroxyl value is 48, acid number is 2, add 26 parts of trimellitic anhydrides then, make it with polyester at 180 ℃ of openings that under normal pressure, carry out 2 hours, finally obtain the polyester (64) of terminal carboxyl groupization, its Mn is 2700, hydroxyl value is 35, and acid number is 26, and Tg is 48 ℃.

[preparation of the solvent solution of resin (p-5)]

Adopt the mode identical with embodiment 64 to prepare the solvent solution (p-5) of resin (p), difference only is to adopt polyester (64) replacement polyester (63).

[preparation of resin particle]

Adopt the mode identical to prepare resin particle (65) and method for producing toner and toner (65), the solvent solution (p-4) that difference only is to adopt the aqueous liquid dispersion of resinous particulate (Q-4) to substitute the aqueous liquid dispersion of resinous particulate (Q-1) and adopt solvent solution (p-5) the replacement resin (p) of resin (p) with embodiment 64.The Tg of resin particle (65) is 48 ℃, and particle diameter is 5.2 μ m, with the ratio of the volume average particle size of resin particle (Q-4) be 0.01.

Embodiment 66

[preparation of the solvent solution of resin (p-6)]

Adopt the mode identical with embodiment 64 to prepare the solvent solution (p-6) of resin (p), difference only is to adopt the ethyl acetate solution of the urethane resin (61) of 30 parts of embodiment, 61 preparations to replace the hardening agent (β-2) for preparing in the ethyl acetate solution of 30 parts of prepolymers (α-1) that contain isocyanate group and the Production Example 66.

[preparation of resin particle]

Adopt the mode identical with embodiment 64 to prepare resin particle (66) and method for producing toner and toner (66), difference only is to adopt the aqueous liquid dispersion of resinous particulate (Q-4) to substitute the solvent solution (p-4) of solvent solution (p-6) the replacement resin (p) of the aqueous liquid dispersion of resinous particulate (Q-1) and employing resin (p).The Tg of resin particle (66) is 53 ℃, and particle diameter is 5.0 μ m, with the ratio of the volume average particle size of resin particle (Q-4) be 0.010.

Comparative example 61

[synthesizing of polyester (65)]

The linear polyesters (Aa '-5) of synthetic comparative example 1, polyester (65) as a comparison.

[synthesizing of polyester (66)]

The non-linearity polyester (Ab '-5) of synthetic comparative example 1, polyester (66) as a comparison.

[preparation of the solvent solution of resin]

The solvent solution of comparative resin (X-1) adopts the mode identical with embodiment 61 to obtain, difference only is to adopt polyester (65) to replace polyester (62), and adopts 26 parts of polyester (66) and 26 parts of ethyl acetate to replace the ethyl acetate solution of 52 parts of urethane resins (1).

[preparation of resin particle]

Adopt the mode identical to prepare resin particle (X1) and coating composition (X1), distinguish the solvent solution (p-1) of solvent solution (X-1) instead of resins (p) that only is to adopt comparative resin with embodiment 61.The Tg of resin particle (X1) is 61 ℃, and particle diameter is 88 μ m, with the ratio of the volume average particle size of resin particle (Q-1) be 0.009.

Comparative example 62

[synthesizing of polyester (67)]

The linear polyesters (Aa '-6) of synthetic comparative example 2, linear polyesters (67) as a comparison.

[preparation of oiliness mixed solution]

Adopt the mode identical with embodiment 64 to prepare the solvent solution (X-2) of comparative resin, difference only is to adopt the polyester (63) in polyester (67) alternate embodiment 64 and adopts 15 parts of polyester (66) and hardening agent (β-2) that the ethyl acetate solution of the alternative 30 parts of prepolymers (α-1) that contain isocyanate group of 15 parts of ethyl acetate and 1.8 parts of Production Examples 66 are prepared.

[preparation of resin particle]

Adopt the mode identical to prepare resin particle (X2) and method for producing toner and toner (X2), distinguish the solvent solution (p-4) of solvent solution (X-2) instead of resins (p) that only is to adopt comparative resin with embodiment 64.The Tg of resin particle (X2) is 47 ℃, and particle diameter is 5.5 μ m, with the ratio of the volume average particle size of resin particle (Q-3) be 0.011.

Comparative example 63

[synthesizing of polyester (P67)]

The linear polyesters (Aa '-7) of synthetic comparative example 3, linear polyesters (P67) as a comparison.Because polyester (P67) can not be converted into resin, so it can not be used to prepare corresponding resin particle.

Comparative example 64

[synthesizing of polyester (68)]

The linear polyesters (Aa '-8) of synthetic comparative example 4, polyester (68) as a comparison.

[synthesizing of polyester (69)]

The non-linearity polyester (Ab '-8) of synthetic comparative example 4, polyester (69) as a comparison.

[preparation of oiliness mixed liquor]

Adopt the mode identical with embodiment 64 to prepare the solvent solution (X-3) of comparative resin, difference only is to adopt the polyester (63) in polyester (68) alternate embodiment 64 and adopts the ethyl acetate solution of the alternative 30 parts of prepolymers (α-1) that contain isocyanate group of polyester (69) and hardening agent (β-2) that 1.8 parts of Production Examples 66 are prepared.

[preparation of resin particle]

Adopt the mode identical to prepare resin particle (X3) and method for producing toner and toner (X3), distinguish the solvent solution (p-4) of solvent solution (X-3) instead of resins (p) that only is to adopt comparative resin with embodiment 64.The Tg of resin particle (X3) is 51 ℃, and particle diameter is 5.3 μ m, with the ratio of the volume average particle size of resin particle (Q-3) be 0.009.

Adopt following evaluation method to estimate, evaluation result is listed in the table 7.

[1] volume average particle size

The comparative resin particle (X1) that obtains in resin particle (61)～(63) that obtain among the embodiment 61～63 and the comparative example 61 is dispersed in the water, adopt Ku Erte particle collector (Multisizer III, U.S. Coulter electronics corporation system) to measure volume average particle size.

[2] levelability

Use commercially available corona discharge type spray gun, contrast coating composition (X1) electrostatic coating that obtains in coating composition (61)～(63) that obtain among the embodiment 61～63 and the comparative example 61 is handled on the plate specification plate (Japanese Test Panel Co., Ltd. system) at trbasic zinc phosphate, making coating thickness is 40～60 μ m, then 180 ℃ of bakings 20 minutes, by the visualization surface smoothing, estimate by following standard:

◎: surface smoothing is also glossy

Zero: the surface has slight concavo-convex, has gloss

△: rough surface, lackluster

*: rough surface, there is the vestige of bubble and lackluster.

[3] heat-resisting keeping quality

Various coating compositions were preserved 7 days in 40 ℃ atmosphere gas, and a situation arises to observe its melt bonded property then.This observation is following enforcement: be respectively vibration 15 minutes on the standard sieve of 150 μ m at mesh with the various coating compositions that 50g preserved, measure the amount of its residual resin particle on screen cloth then, in following standard residual ratio is estimated:

◎: condensation product is lower than 0.2%

Zero: condensation product is lower than 1%

△: condensation product is lower than 2.0%

*: condensation product is more than or equal to 2.0%.

[4] adhesiveness (cohesive)

Use commercially available corona discharge type spray gun, each coating composition electrostatic coating is handled on the plate specification plate (Japanese Test Panel Co., Ltd. system) at trbasic zinc phosphate, making coating thickness is 40～60 μ m, then 180 ℃ of bakings 20 minutes.Carry out the shear adhesion experiment according to the method for JIS K6830 regulation.Adhesiveness (cohesive) is estimated according to following standard:

Zero: aggegation completely destroys

△: contact interface is partly destroyed, stays damaged vestige

*: contact interface is destroyed fully.

[5] water-fast adhesiveness

Adopt top mode to apply and toast each coating composition of embodiment and comparative example, in 40 ℃ warm water, flooded 10 days then.Shear the experiment of aggegation according to the method for JIS K6830 regulation.Evaluation criterion is identical with the evaluation criterion of above-mentioned adhesiveness (compendency).

[table 7]

The resin particle sequence number	Surface smoothing	Heat-resisting keeping quality	Adhesiveness	Water-fast adhesiveness	Volume average particle size (μ m)
						Resin particle (61)	◎	◎	○	○	95
Resin particle (62)	○	◎	○	△	120
						Resin particle (63)	◎	○	○	△	142
Comparative resin particle (X1)	×	△	△	×	88

Adopt following evaluation method to estimate, evaluation result is listed in the table 8.

[6] minimum fixing temperature (MFT)

The method of putting down in writing according to the front.

[7] the deep fat China ink stains occurrence temperature (HOT)

The method of putting down in writing according to the front.

[8] toner flowability

The method of putting down in writing according to the front.

[9] volume average particle size

The method of putting down in writing according to the front [1].

[table 8]

The resin particle sequence number	MFT(℃)	HOT(℃)	The toner flowability	Volume average particle size (μ m)
					Resin particle (64)	125	240	○△	5.1
Resin particle (65)	125	240	○	5.0
					Resin particle (66)	125	240	○	5.3
Comparative resin particle (X2) comparative resin particle (X3)	135 140	230 240	△× ○△	5.5 5.8

Industrial applicibility

Method for producing toner and toner of the present invention has used polyester resin for toner of the present invention, make thus its low-temperature fixability, heat-resistant inks contamination and comminuted between have excellent harmony, therefore can be used for electrostatic image developing toner, be particularly useful for color toner.

The toner that the present invention is the 6th low-temperature fixability, heat-resistant inks contamination and comminuted between have good harmony, therefore can be used for electrostatic image developing toner, consider that from the viewpoint of glossiness and the transparency it is particularly useful for color toner.

The 7th of the present invention and the 8th 's composite resin particle be specially adapted to powdery paints, hollow molding with resin, electrophoto-graphic toner, electrostatic recording with toner, electrostatic printing with toner, PUR and other moulding material.

Claims (8)

1, a kind of polyester resin for toner, it obtains by making polyol component and polybasic carboxylic acid component carry out polycondensation, and described polyol component has 7.0 * 10 ⁴J～1.4 * 10 ⁵The average cohesive energy of the mole of J; Described vibrin comprises at least a vibrin A1 of 20 weight %～100 weight %, and this vibrin A1 has 2.5 * 10 at 150 ℃ ³Pa～5 * 10 ⁶The storage modulus of Pa, wherein, described vibrin A1 is following vibrin A3, in described vibrin A3, described polybasic carboxylic acid component contains terephthalic acid (TPA), m-phthalic acid and/or their lower alkyl esters of (a) 80 moles of %～100 mole %, and the carbon number of alkyl is 1～4 in the described lower alkyl esters; Described polyol component contains the aliphatic diol of (b) 20 moles of %～100 mole %, and 80 moles of %～100 mole % in this aliphatic diol are 1, the 2-propylene glycol; 0.1 mole of %～20 mole % of the total amount of described polyol component and polybasic carboxylic acid component is the above polyvalent alcohol of (c) ternary or ternary and/or ternary or the above polybasic carboxylic acid of ternary; And the softening point of described vibrin A3 is that 95 ℃～160 ℃, glass transition temperature Tg are 45 ℃～75 ℃.

2, polyester resin for toner as claimed in claim 1, wherein vibrin A3 is that the number-average molecular weight of solubilized part in the tetrahydrofuran is 1000～9500 vibrin.

3, polyester resin for toner as claimed in claim 1, wherein Resin A 3 comprises linear polyester resin and non-linearity vibrin.

4, polyester resin for toner as claimed in claim 1, wherein Resin A 3 is to obtain by polycondensation in the presence of polymerization catalyst, described polymerization catalyst contains one or more metals that are selected from the group of being made up of titanium, antimony, zirconium, nickel and aluminium.

5, a kind of polyester resin composition for toner, it contains described polyester resin for toner of claim 1 and toner additive B, described additive B comprises modified waxes w1, and described modified waxes w1 prepares by utilizing vinyl monomer m that at least a portion of wax w is carried out modification.

6, a kind of method for producing toner and toner, it contains the described polyester resin for toner of claim 1, and contains colorant, also contains as required the adjuvant that adds, and described adjuvant is selected from least a in release agent, charge control agent and the fluidizing agent.

7, as method for producing toner and toner as described in the claim 6, when wherein using described method for producing toner and toner on fixing device uncertain image to be carried out photographic fixing, the deep fat China ink stains temperature difference between occurrence temperature and the minimum fixing temperature more than or equal to 95 ℃.

8, a non-magnetic mono-component toner, this toner is used for the image forming method that sub-image developed by toner is offered latent image carrier, it is characterized in that described toner comprises the described polyester resin for toner A3 of claim 1, and comprises colorant; If with the glass transition temperature Tg of A3 as x axle variable, softening point sp as y axle variable, when map with the xy coordinate, then described toner has by the interior physical characteristics of following equation (1)～(4) scope that defined straight line surrounded; And have one or more particulate additives on this toner-particle surface;

Equation (1): sp=4Tg-110,

Equation (2): sp=4Tg-170,

Equation (3): sp=90 and

Equation (4): sp=130.