SPFCIFICATION
BINDER RESIN EOK COLOR TONERS AND COLOR TONER USING THE SAME
TECHNICAL FIELD
[1001]
The present invention relates to a binder resin for color toners and a color toner using the same.
BACKGROUND ART
[0002]
In general, electrophotography in a PPC (Plain Paper Copy) copier or printer for transferring a toner image formed on a phicro-sensirive marerial to recording paper is carried out in the 13 formeo on one ohoto-sens:rive material, the latent image is developed by using a toner, the toner image is transferred onto a sneet to be fixed such as paper or the like, and then the transferred toner im.aoe i.- 'ined by heating v/ith a heat roll or a film.. Sinoe the fixation is carried out under heat in a state that the heat roll or the flim. is directly brought into contact with the toner on the sheet to be fixed according to this method, it is performed in a short period of time and with a very high thermal effioiency tnereby achieving a very good fixing efficiency. However, though naving a good thermal efficiency, the heat fixing method has a problem, of a so-called offset phenom.enon since the toner is brought into contact with the surface of the

heat roll or the fi.lra in the melt state. 10003]
In order to obtain a resin excellent in the fixing properties and offset resistance, there has been known a resin obtained by using a high molecular weigh r resin and a low molecular weight resin in mixture and crosslinking rt high; m.olecular weight portion. Furthermore, to exhibit both the lov; temperature fixing properties and. offset resistance, various techniques have been disclosed in the documents (for example, Patent Documents 1 to 4). However, these documents disclose a design suitable for a toner for monochrome use. The techniques disclosed in these documents are effective in both the low temperature fixing properties and offset resistance, but a design different from that of a toner for monochrome use is required v;hen such a toner is applied to a color toner.
[0004]
Gloss is required as an object to achieve specific to a color toner. When a toner for monochrome use is applied to a color toner, there has been still room for improvement in view of the gloss. In particular, even though a toner for monochrome use requires high elasticity in order to improve offset resistance, there has been a problem such that the unevenness on the printed surface in the color toner is caused, theret'y impairing the gloss.
[0005]
In Patent Document 5, there has been disclosed a binder resin without containing a gel portion, while in Patent Document 6, there has been disclosed a color toner having the content of a gel

co.Tiponent of less than 5 weight t. Hov^ever, in these documents, since the range of Mw/Mn is narrow, offset resistance is not the gloss and offset resistance. Furthermore, v/hen a high miolecular component ratio and gel content are reduced in order to enhance rhe gloss, there is also a problem, of reduction of djrability.
Patent P'ocument ]: Japanese Patent Laid-open No. 2002-189316 Patent Docuraent 2: Japanese Patent Laid-open No. 2004-144660 Patent Document 3: Japanese Patent Laid-open No. HlO-90943 Parent Document 4: International Publication Pamphlet No. 2 0 0 4-015498
Patent Docum.ent 5: Japanese Patent Laid-open No. 2004-177969 Patent Document 6: Japanese Patent Laid-open No. HlO-171162
DISCLOSURE OF THE INVENTION
I 0006]
The present invention is to solve a prcblem specific to a color toner. Specifically, the present invention is to provide a binder resin for color toners and a color toner excellent in balancing the gloss, durability and various properties reguired for a toner.
>0007j
The present invention provides a binder resin for color toners, wherein the binder resin contains at least a carboxyl group-containing vinyl resin (C), a glycidyl group-containing vinyl resin (E) and a reaction product thereof, the storage m.odulus G' at 160 degrees centigrade is not less than 20 Pa and less than

Pa measured at a rrequency of c.26 rad/sec, the tetrahydrofiiran
-THF) soluble portion in the binder resin has a main peak in the
uLolecular v/eight region of not less than 20, 000 and less than 40, 000
m the molecular weight distribution measured by gel permeation
5 chromaoography (GFC), and the binder resin contains at least one
cf releasing aqents havinq a melting point not lower than 60 degrees
centigrade and not higher ther 120 degrees centigrade in an am.ount
of not less than 3.5 mass l an^i not more than 12 mass % based on
100 mass i of the ratal amount of the carboxyl group-containing
LO viny]. resin fC), ;:he givcidyl qronp-containing vinyl resin (E) and
a reaction producr thereof.
: 0 0 0 s 1
In the aforemienui_oned binder resin for color toners, the inregratea value cf the contenr of tne ueurahydrofuran (THF) 5 siiuble portion in the bindei resin in the molecular weight region of not xm.ore than 2,000 m.ay be not more than 7.0 mass % based on the total THF soluble portion.
[00091
In the aforemientioned cinder resin fcr color toners, the '0 weight-average miolecular v.'eight [Mw) may be not more than 170,000 and the weight-average m.olecular weight (Mw) /the number-average m.olecular -weight (Mn) may not less than 5 and not more than 40.
[0010]
Meanwhile, the present ir.vention provides a binder resin for 5 color toners, wherein Lne binder resin contains at least a carboxyl group-containing vinyl resin (C), a glycidyl group-containing vinyl resin (E) and a reaction product thereof.

the storage modulus G' at 160 degrees centigrade is not less than 20 Pa and less than 800 Pa measured at a frequency of 6.28 rad/sec,
the tetrahydrofuran (THF) soluble portion in the binder resin has a main peak in the miolecular weight region of not less than 20,000 and less than 40,000 in the molecular weight distribution measured by gel perm.eation chromatography (GPC) ,
the binder resin contains at least one of releasing agents having a m.elting point not lower t::in 60 degrees centigrade and not higher than 120 degrees centigrade in an amount of not less than 3.5 mass % and not more than 12 m.ass ?- based on 100 mass % of the total amount of the carboxyl grcup-containing vinyl resin (C), the glycidyl group-convaining vinyl resin (E) and a reaction product thereof,
the integrated value of the content of the tetrahydrofuran (THF) soluble portion in the binder resin in the molecular weight region of not more than 2,000 is not more than 7.0 mass % based on the total THF soluble portion, and
~he weight-average molecular weight (Mw) is not more than 170,000 and the weight-average molecular weight (Mw)/the num.ber-average molecular weight (Mn) is not less than 5 and not more than 4 0.
[0011]
In rhe aforementioned binder resin for color toners, the content of a volatile comoonent ned in the binder resin may be not more than 200 ppm.
(0012]
In the afcremem:ioned bindei resin for color toners, the softening point m.ay be not m_ore than 130 degrees centigrade.

[0013].
In the aforementioned binder resin for color toners, the releasing agent in the binder ];esin may be dispersed with an average diameter of not more than 1 micro-meter. [0014]
The aforementioned binder resin for color toners satisfies the following conditions: the carboxyl group-containing vinyl resin (C) contains a high molecular vjeight vinyl resin (H) in which the THF soluble portion has a m the molecular weight region of not less than 150,000 and less than 350,000 in the GPC chromatogram^ and a low molecular weight vinyl resin (L) in which the THF soluble portion has a peak in the miolecular weight region of not less than 20,000 and less than 40,000 in the GPC chromatogram;
the mass ratio (H/L) of the high molecular weight vinyl resin (H) to the lovi m.olecular v/eight vinyl resin (L) in the carboxyl group-containing vinyl resin iC) is from 10/90 to 30/70;
the acid value of the high molecular weight vinyl resin (H) in the carboxyl group-contaminq vinyl resin (C) is not less than 10 mgKOH/g and not more than 2c mgKOK/g and the acid value of the low miolecular weight vinyl resin (L) is not less than 6 mgKOH/g and not more than 30 m.gfvOH/a;
the acid value of the carboxyl group-containing vinyl resin (C) IS not less than 6 mgKOH/g and not more than 30 mgKOH/g;
the TH? soluble portion in the glycidyl group-containing vinyl resin (E) has a peak in tne molec._:lar weight region of not less than 20,000 and not more than 80,000 in the GPC chromatogram and the epoxy value of the glycidyl group-containing vinyl resin (E)

13 not J-ess than 0.003 Eq/lOOg and not more than 0.022 Eq/lOOg; and
resin {C] zc' the qiycid\l orour)-containing vinyl resin (E) is from 01/13 to 59/1.
[ C 015 ]
The aforementioned binde^" resin for color toners may contain a block copolymer IncludinQn a block comprising a sequence of erhylenic nydrocart'Cn. derived constituent units and/or conjugated diene type hydrocarbon-cler L >'V--el '?,onstituent units, and a block com.prising a sequence of styrene-derived constituent units, and/or tne hydrogenated product of the click copolymer, in an amount of not less than 0.05 miass *. and not miore than 0.5 mass % based on 100 mass 1 of the carboxyl group-conitaining vinyl resin (C) .
L0016J
Fuithermore, the present invention provides a method for producing the aforem.entioned binder resin for color toners including a polymerizing the low m.olecular weight vinyl resin (L) in the presence of at least cne of releasing agents having a melting point of net lower than 60 degrees centigrade and not higher than 120 degrees centigrade, and an am.ount of not less than 2 mass 1 and not more than 13 mass ^; based on 100 mass % of the constituent monomer of the low m.olecular weight vinyl resin (L) .
[0017]
Furtherrriore, the present invention provides a method for producing the aforemientioned binder resin for color toners including a melt-knead„ng at least one of the carboxyl

group-containing vinyl resins (C) and at least one of the glycidyi qroup-conta ining ""Vinyl resins (E) at a temperature range of not lower than 14 0 oegrees centigrade and not higher than 210 degrees centigrade, and reacting a carboxyl group with a glycidyi group.
[0018]
Besides, the present indention provides a color toner containing at least tine aforemtentioned binder resin for color toners, a :;oloring agent and a chirne contiolling agent.
[0019]
The aforementioned color toner may be obtained by a grinding net h o d.
[0020]
In tne aioremientioned color toner, the storage modulus G' at 160 dearees ceuitigrade m_ay be not loss than 100 Pa and less than 800 ?a measured an a rrequenc; if 6.2'^- rad/sec.
[0021]
According to the present invenoion, there are provided a binder resin for color toners and a color toner excellent in balancing the gloss, durability and various properties required for a toner.
BEST MODE EOR CARRYING OUT THE INVENTION
[0022]
The present inventio^^ will be described in more detail below.
[0023]
In the present invention, the term "polym.erization" may include the meaning of copolymierir' t ion, and the term "polymer" may have the meaning of a copolymior.

[0024]
The binder resin for color toners of the present invention contains a carboxyl aroup-containing vinyl resin (C), a glycidyl Qrcnp-containing vinyl resin CT^) and a reaction product thereof, and a releasing aaent. It is possible to obtain a toner excellent in balancing the fixing properties and offset resistance by containing such a resin. Furthermore, in a reaction product of the carboxyl group-contain.inq vinyl resin (C) and the glycidyl group-containing vinyl lesir (E), nolecuJes at the reaction site may move relatively freely. Therefore, even though the molecular weight increases, moderate elasticity can be imparted vvithout excessively increasing 'ihe ;hasticicy. Furrhermore, it is possible ro obtain a toner excellent in unprecedented balancing gloss and offset resic+'^nce becauise of the releasing agent contained in the toner.
[0025]
Furthermore, in the binder resin for color toners of the present invention, the storage modulus G' at 160 degrees centigrade is not less than 20 Pa and less than SOO Pa, preferably not less than 30 Pa and less than '"'CO Pa and further preferably not less than 50 Pa and less Chan 600 Pa measured at a freguency of 6.28 rad/sec. Herein, in a general grinded roner for monochrome use of the related art, a resin has been designee so as to increase rhe storage modulus ar a temperature higher th^m 1 60 deorees centigrade for the purpose of achievina both one low temiperature fixing properties and hot offset resistance. However, in case of high elasticity at a high

is a problem of deterioration of the gloss. That is, when the general grinded toner for monochrome use is used for a color toner, even though a smooth surface is temporarily formed by using a heat roll or the like during fi>'.ation of the toner, the printed surface becomes uneven due to the restoring force on the surface attributable to the resin elasticity. As a result, there is a problem, of reduction of the gloss. In particular, a binder resin for monochrome use of the related art contains lots of high molecular component and gel portion so that the elastic modulus at a temperature of 160 dc-grees centigrade becomes excessively high. Thus, the gloss is reduced. When it is used for a color toner, there has been a problemi such that the gloss is impaired. In order to achieve the gloss, jt is .uapoi tant to have a resin with lovi elasticity. In the present invention, it is possible to obtain a binder resin for colo^^ toners excellent in the gloss because of the storage modulus G' in a predetermined range.
[0026]
Meanwhile, in the binder resin for color toners of the present invention, the tetrahydrofuran (THF) soluble portion in the binder resin has a main peak in the molecular weight region of not less than 20,000 and less than 40,000 and preferably in the molecular weight region of not less than 20,000 and less than 37,000 in the molecular weight distribution measured by gel permeation chromatography (GPC). In the binder resin of the present invention, a balance among the glcss and durability and other various properties of the toner becomes excellent by having a main peak in this region. The toner durability is greatly affected by the
leculai v/eight ot the low molecular weight component is exsessively high, the toner is excessively hard so that the toner is hardly ground in the procuction thereof. As a result, the producti^^iry miighr possibly oe lowered. Furtheimore, the storage modulus and loss noduJus become high durina mielting so that the fixing properties and the gloss are damaged in som^e cases. Therefore, -when the THF solubile portion is within the above region, dererioraticn of the durability can be prevented in the production of the toner and an excellenT: balance among the gloss and other various properties can be jxn.ibired. [0027]
iMeanwhile, the binder resin for color toners of the present invention contains at least one of releasing agent having a melting point of not lower than 60 degrees centigrade and not higher than 120 degrees centigrade. The content of the releasing agent is not less than 3.5 mass % and not more than 12 mass % and preferably not less than 4 mass % and not more than 10 mass % based on 100 m.ass 1 of the total amount of the carboxyl group-containing vinyl resin (C), the glycidyl group-containing vinyl resin (E) and a reaction product thereof. Further, the melting point of the releasing agent is preferably not lower than 60 degrees centigrade and not higher than 120 cegr-es centigrade, and further preferably not lower than 70 degrees centigrade and not higher than 115 degrees

centigrade. When the content of the releasing agent is excessively small, hoc offset easj Ly o^";curs and the gloss is further easily deteriorated presumably because of rhe occurrence of micro offset phenomenon. On the other hand, when the content of the releasing agent is excessively high, the releasing agent component is easily agglomerated in the resin or the toner. As a result, a wax is easily fallen off from ohe toner in the ^'reduction of the toner so th.at contamination of the insioie of a device or deterioration of the storage stability might possibly b= caused. Furtherm.ore, the toner is attached inside of the de^-ice in the production of the toner so thar the proolucti'^ity is ioweied in som.e cases. On the other haiid, when the mielting poinh>_ is excessively low, the storage suability of the toner is v/orsened in some cases. When the m.elting point is excessive] y high, "^he compaolbility of the releasing agent comiDonent ;vmth the resi.. is if':Ju;ed so that the fixing properties are easily insufficient. Furtherm.ore, by increasing the resin elasticity, the gloss mi jh" possibly be deteriorated. Accordingly, the binder resin of the present invention can achieve an excellent balance am.ong the gloss, offset resistance, storage stability, productivity and other various properties by a releasing agent having the melting point and the content within the above region.
[0028]
The afo]~em_entioned releasing agent is preferably dispersed in the binder resin. More preferably, the aforementioned releasing agent is finely dispersed m the binder resin in a state that an average diameter is not more than 1 micro-meter. Thus the releasing agent having a low melting j: oint is internally added in the resin

and finely dispersed, wneie;.'y it ^.s possible to improve offseu resistance v;hile retaining the storage stability and cleaning properties.
[0029]
In the present invention, the integrated value of the content of the tetrahydrofuran (THF) soluble portion in the binder resin in the molecular weight region of not more than 2,000 is preferably not more than 7.0 mass % and more preferably not more than 6.5 mass % Dased on the total THF soluble portion. Furtherm.ore, the lower limit of tlie integrated value of the content is not particularly lim.ited, but it is, for example, not less than 2 mass %. A releasing agent having a low melting point is internally added to the binder resin of the present iP-vention. The releasing agent having a low melting point is compatible v/ith the low molecular weight component having a m.olecular weight of not more than 2,000 so that the entire binder resin is easily plasc.ciied. As a result of the com.patibility, deterioration of the storage stability or contamination of the inside at a de^^ice easily occurs. Accordingly, the low m.olecular weight cem.ponent having a miolecular weight of not more than 2,000 is prv.-;ferably contained in a smaller amount. When the low molecular weight component is within the above range, comipatibili ty of the lov; molecular v/eight component with the releasino agent caui be prcented. As a result, the storage stability of the toner can be improved and contamination of the inside of a device can be prevenued.
[00301
In the binder resin fc^r color toners of the present invenoion,

the vveighr-average weight (Mw) is preferably not more than 170,000 and more orefera;jly r.ot less than 40,000 and not more rhan 155,000. W!ien rhe weight-average m^olecular v/eight (Mw; is wirhin the above ranoe, a t^jner excellent in balancing the fixing properties, the toner productivity and the gloss is obtained. In particular,, when Mw is excessively high,, the elasticity of the meited toner becom.es large and the gloss is easily damaged. So, Mw is preferably v;ithin the above range.
Besides, in the binder resin for color toners of the present invention, the weight-average molecular weight (Mw)/the numiber-average molecular weight (Mnb is preferably from 5 to 10 and more preferably not less tnan 6 and not more than 25. When Mw/Mn is within the above range, it is possible to obtain a binder resin excellent in balancing offset resistance and various properties of the color toner.
[0031]
Meanv/hile, in the binder resin for color toners of the present invention, the content cf a volatile component remained in the binder resin is prefera'^ly vic'c more than 200 ppm and more preferably nor more than 190 ppm. Besides, the lower limat of the content of the residual volatile som.psnent is not particularly limiited, but it is, for example, not less than 10 ppm. When the conrent of the residual volatile component is excessively high, dereriorauion of the storage stability or contamination of the inside of a device is easily caused presumiably because the compatibility of the releasing agent having a low mielting point is further accelerated. Accordingly, when the contenr of the

residual voJ^atile componeni is within the aforementioned range, ir is preferable because tl'e storage stability and cleaning properties of the toner becom.e exiellent. Besides, within the aoove ranae, it is preferable because attachment of the toner onto a ioner production facility is suppressed and the toner productirity is thus improvt'd as well. Besides, one of preferable reasons is that odor during toner printing is also suppressed.
[0032]
The binder resin for cclcr toners of the present invention has a scftenma point of not more than 130 degrees centigrade, preferably not lower than 90 degrees centigrade and not higher than 127 degrees centigrade and more p">referably not lower than 100 degrees centigrade and nc't higher than 123 degrees centigrade. In case of a color toner, the softening point is also important in addition to control of the storage modulus. The sofuening point represents the deformability of the resin due to heat under a load, and is an index of rhe def ormability of the toner due to the pressure and ieat '.vi'ille passing a fixing unit. Therefore, as the softening point is lower, the printed surface is smoothed while passing the fixing unit and the gloss of the toner is easily imiproved. When the softening peine is within the aforementioned range, a binder resin excellent in balancing the gloss and various properties suited for use in color toners is obtained.
[0033]
Hereinafter, the carboxyl group-containing vinyl resin (C) and the glycidyl group-containing vinyl resin (E) contained in the binder resin for color toners of the present invention will further

be described in detail.
[0031 1

The carboxyl group-contaionning vinyl resin (C) is obtained by usina a known polynierizatic n method employing at least one of carboxyl group-containing nonomers, at least one of styrene based monomers and at least one of acrylic based monomiers (including methacrylic based monomers, hereinafter the same) .
[0035 I
Examiples of the carboxyl croup-containing monomier in the present .^nvention include acrylic acid, methacrylic acid, mialeic anhydride, raleic acid, fu'.^iaric acici, cinnamic acid, miono esters of an unsaturated dibasic acid such as m.ethyl fum.arate, ethyl fum.arate, propyl fumarate, butyl f am? rate, octyl fumiarate, methyl maleate, erhyl m.aleate, propyl maleate, butyl maleate, octyl maleade and tne like. Preferaijly use^i are acrylic acid, methacrylic acid, fumaiic acid, m.ethyl fumarate, ethyl fumarate, propyl fumarate, butyl fumLarate and octyl ".carafe. Particularly preferably used are acrylic acid and mf'thacrylic acid.
[0036]
invention include styrene, p-metnylstyrene, m-methylstyrene, o-methylstyrene, p-phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene, p-ethylstyrene, 2,4-dimethylstyrene, p-n-butylstyrene, p-tert-butylstyrene, p-n-hexylstyrene, p-n-octylstyrene, p-n-nonylstyrene, p-n-decylstyrene, p-n-dodecylstyrene and the like. Particularly

preferably used is styrene.
[0037]
Examples of the acrylic based monomior to be used in the present invention include acrylic esters such as methyl acrylate, ethyl acrylate, propyl acrylate, b-.;tyl acrylate, ocryl acrylate, cyclohexyl acrylate, stearyl acrylate, benzyl acrylate, furfuryl acrylate, hydroxyethyl acrylate, hydroxybutyl acrylate, dimethylaninomethyl aery]ate, diraethylaminoethyl acrylate and the j.ike; methacrylic esters such as miethyl methacrylate, ethyl mechacrylate, propyl methacr ylfite, butyl methacrylate, octyl methacrylate, cyclohexyl miothacrylate, stearyl methacrylate, benzyl methacrylate, furfuryl methacrylate, hydroxyethyl m.etliacrylate, hydroxybutyl mLethacrylate, dimethylaminomethyl FiCthacrylate, dimethylaminoethyl miethacrylate and the like; and ariides such as acrylonitrile, acrylam.ide, methacrylonitrile, methacrylamide, N-substituced acrylamide, N-substituted methacrylamide and the like. .^maong these, preferably used are acrylic esters, methacrylic esters, acrylonitrile and meccacryloni tril e . Par!; i:,'_. larl y preferably used are butyl acrylate, mietLhyl methacry] ate, butyl methacrylate and h y d r o x y e t h y 1 a c r y 1 a t e .
[0038]
In the present ievent ion, in addition to the aforementioned :'isnomier3, r:iere may also be used di esters of an unsaturated dibasic acid, such as dimerhyl fumarace, dibLityl fumarate, dioctyl fum.arate, dim.ethyl m.aleate, dibutyl I'laleate, dioctyl maleate and the like as m.onomers .

[0039]
A crossImkinq monomer /.aving tn'o oi more double bonds may be used, as necessary, for the carboxyl group-containing vinyl resin I'C; of the present inventron as a monomer. Examples of the crosslinkinq monomer inciuie aromatic divinyl compounds such as divinyl benzene, divinyl naphthalene and the like; diacrylate compounds and methacrylate compounds thereof such as ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,5~hexanediol diacrylate, neopentylglycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyoxyethylene;1)-2,2-bis(4-hydroxyphenyl)propane diacrylate, polyoxyethylene(4)-2,2-bis(4-hydroxyphenyl)propane diacrylate and the like; and polyfunctional crosslinking monom.ers and methacrylate compounds thereof such as pentaerythritol triacrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, tetramethylolmiethane tetraacrylate and the like. When these crosslinking monomers are used, the content of the crosslinking monomer is preferably less than 0.5 m.ass % based on 100 mass 1 of other m.onomers contained in the carboxyl group-containing vinyl resin (Cj . When the content of the crosslinking monomier is excessi\'ely high, a crosslinked body is easily produced by the reaction of a carboxyl group with a glycidyl group to be described belcvv'. In order to suppress production of such a crcsslinked body, co suppress increasing the elasticity at a high temperature and to suppress deterioration of the gloss, the content of the crosslinking monomier is preferably within the above
range.
[ 0 0 - 0 :
Glycidyl Grcup-containmr! v'lnyl Resin (E):;
Besides^ the glycidyl cntaining vinyl resin (E) m^ay be cbtained by a knc)V/n ion method employing at least one ;,f glycidyl ar ou[;-ccin i i! _''n i :. ^ I'l 'C-umers and at least one of other mionomiers. As tne utonoinar consoicucing the glycidyl group-containing vinyl resin (E;, there can be exemplified the aforementioned monomers in addition to the glycidyl
[00411
The THE soluble portion of the glycidyl group-containing ^^inyl resin (E) has a peak preferablv iii the molecular v;eight region of not less than 20,000 and not more than 80,000, m.ore preferably in ohe molecular weight region C'f not less than 30,000 and not more than 70,000 and further preferably in the molecular weight region of not less than 40,000 and not more than 60,000 in the GPC chromatcgrami. Furtherm.or-^', the epoxy value of the glycidyl group-containing vinyl resin (E) is not less than 0.003 Eg/lOOg and not miore than 0.022 Eq/lOOg, more preferably not less than 0.004 Eq/lOOg and not m.ore than C),015 Eq/lOOg and further preferably not less than 0.006 not more than 0.^'L3 Eq/lOOg. In the binder resin, when the peak m.olecular weight and the epoxy value of the glycidyl group-containing "inyl resin (E) is not less than the above lower limit, the durability becomes excellent and the feature of maintaining development is enhanced when it is used for a toner. Furtherm.ore, at the same timio, by the reaction of the carboxyl

group-containing vinyl resin (C) v/ith the glycidyl group-containing vinyl resin (E) , the molecular weight of the high miolecular vjeight component further increases and appropriate elasticity is impartevd to ':he binder resin so that offset resistance performance becomes excellent. When the peak molecular v;eight is excessively small or the epoxy value is excessively smiall, elasticity of the binder ; :. r-in is not sufficient and offset resistance becomes deteriorated i;i some cases. On the other hand, '.vhen the peak miolecular weight is excessively high or the epoxy value is excessively high, elasticity of the binder resin becomes excessively high so that the gloss is deteriorated in some cases. In the present invention, the epoxy value refers to mole of rhe epoxy grC'Up present in 100 g of the resin, and it can be measured
accord
[0042 J
Examples of the glycidyl qroup-containing monomer in the present invention include glycioyl- aciylare, p-methyl glycidyl acrylate, glycidyl m.ethacrylate, p-mLCthyl glycidyl methacrylate and the like, and preferably used are glycidyl m.ethaciylate and {3-methyl glycidyl m.ethacrylate .
[0043]
The glycidyl group-conraiming vinyl resin (E) may not necessarily be single of the glycidyl-containing vinyl resins, and tv/o or m.ore glycidyl group-containing vinyl resins may be used. In that case, the glycidyl group-containing vinyl resin (E) miay preferably satisfy the above properties as a whole. Further, to produce a single polymer, the glycidyl group-containing monomer

IS added in the middle of polymerization or added separately at the beginning and end of polymerization, whereby it is also possible to keep the width of the glycidyl group in the molecules. [0 0 4 4]
Besides, it is prefej-abi-^ than the carboxyl group-containing vinyl resin (C) of the present inveo.tion contains a high molecular weight vinyl resin (H) and a low mclecular weight vinyl resin (L).
The ratio (H/L) of th~ ni;,h miolecular weight vinyl resin (H) to uhe low m.olecular weight vinyl lesin (L) in the carboxyl group-containing \rinyl resin (C) is preferably from 10/90 to 30/70 and m_ore preferably fromL il/S5 to 25/75 from the viewpoint of a general balance among the toner productivity, fixing properties, offset resistance, durability and the like, in addition to the aloss for the color toner. When the ratio of the high molecular weight vinyl resin (14) is higri, offset resistance and durability are im.proved v/hen it is used for a toner. On the other hand, the ratio of the ihigh. molecular vjeight vinyl resin (H) is preferably not more than a predeterm.ined value from, the viev/point of im.provem-ent o t the gloss. Accordingly, when H/L is within the above range, it is possible ti t;Loduce a cclo: toner excellent in balancing the above pertoiTaances .
[0045:
In the carboxyl group- vinyl resin (C) , the acid value 13 preierably not less man 6 and not m.ore than 30 mgKOH/g, mere preferably not less than 7 m.gKOH/g and not more than 28 migKOH/g and further preferably not less than 8 mgKOH/g and not more than 26 mgKOH/g. i-Jhen the acid value is not less than the above lower
liinit, tne appropriate elasticity can be imparted to the binder resin by the reaction with i:he glycidyl group-containing vinyl resin ^E; so that offset itsistance becomes excellent when it is ijsed foa" a toner. When th.T' acid value is excessively high, excessive elasticicy is imtpaited to r,he binder resin and the gloss is impaired when it is useci r ~u- a tonei" in some cases. Accordingly, rhe acid value is preferably within the above range. [0046]

In the present invention, the high molecular weight vinyl resin (H) contained in the carboxyl gioup-containing vinyl resin (C) contains the THF soluble portion having a peak preferably in the molecular weight region of not less than 150,000 and less than 350,000 and more preferably in the molecular weight region of not less than I'^O,OOQ and less than 320,000 in the GPC chromatogram. When the peak miolecular weight is excessively small, the elasticity of the binder resin is insufficient without sufficiently increasing the molecular weight m the reaction with the glycidyl group-containing vinyl resin (,Ej in some case. Accordingly, in order to prevent deterioration of offset resistance, the peak molecular weight is preferably not less th3n the above lower limit. Furthermore, when the peak m.olecular weight is excessively high, a crosslinked structure is excessively formed with ease by the reaction with the glycidyi aroup-containing vinyl resin (E). Accordingly, in order the suppress deterioration of the gloss when it is used for a "roner, the peak m.olecular 'weight is preferably not more rhan the above upoer iimit.
^0047 1
In the liiari micJecular v/eic^nJ; vinyl resin (H) , the acid value ,111H) is preferably not less than 10 mgKOH/g and not more than 2 5 mgKOH/g. The acid value is preferably within the above range from, the viewpoint of a balance among tb.e gloss and various properties such as che fixing properties, otTset resistance and the like of the toner. Vjhen "he acid v_-lu6 is not less than the above lov/er limit, the appropriate elasticiLy can be imparted to the binder resin by the reaction with the glycidyl group-containing vinyl resin to be described belc; a;, tha"! offset resistance of the toner becomes excej.ient. On the othei hand, when the acid value is not miore than che above upper limit, it is possible to prevent the reaction with the glycidyl aroup-containing vinyl resin from excessively taking place to excessi^^^ely increase its viscosity, and it is possible ro prevent the loss modulus in the fixing temperature region of the toner from becoming excessively high. As a result, uhe gloss of the toner becom.es excellent. Incidentally, in the present invention, the acid value refers to mg of potassium hydroxide necessary to neutralice 1 g of the resin. r0048]
The high miolecular weight vinyl resin (H) may not necessarily be a single polymer, and two or more high m.olecular weight vinyl resins may also be used. In chat case, the high molecular weight vinyl resin (H) may preferably satisfy the above properties as a whole. Further, to produce single polymer, the carboxyl group-containing monomer is added in the middle of polymerization or added separately at the beginning and end of polymierization.

whereby it is also possible lo keep the width of the distribution of the carboxyl group in the molecules.
L 0 0 4 9]

In the present inventiori, the low niolecular i/eight vinyl zresin (L; contained in the carboxvj qroup-containing vinyl resin (C; contains the THF soluble portion haAd,ng a peak preferably in the molecular -weight region c:f ru^t less than 20,000 and less than 40,000 and more preferably in the molecuJar v;eight region of not less than 21,000 and less than 36,000 in the GPC chromatogram. When the peak m.o].ecular weJ.ght is not les-. i-;un t;:e above lower limiit, cleaning properties, storaoe stabiiicy and durability of the toner can be maintair.ed excellent f'^the'". cl^.e ijeak miolecular weight is not more than the above upper limiv, the fixing perfcrniance can be iT'ainrained excellent.
^0050]
In the lov;/Tn")lecular weight vimyl resin (L) , the acid value (AVL) is preferably not less than 1 r:i(jKOH/q and not m.ore than 30 m.aKCH/a. When the acid value (AVLl is within the above region, excellent durabiliry, fixing performance, gloss and offset resistance performance are exhibited. Herein, the durability of the toner is improved presumiably by increased molecular weight of the low m.olecular v/eight vinyl -jesin wdiich is reacted with the glycidyl group-containing vinyl resin (E) or a hydrogen bond of the carboxyl group. FurrheriTiore, the fixation performance is easily improved due to imiprovement of w'ith paper. Furthermore, when the acid value is within the above range, che reactivity of rhe

glycidyl group-containing vinyl resin (E) with the high molecular weight vinyl resin (H) can be prevented from being excessively increased so that deterioration of the gloss of the toner can be prevented.
[0051]
The low molecular weight vinyl resin (L) may not necessarily be a single polymer, and tv/o or more lovj molecular weight vinyl resins m.ay be used. In that case, the lev; molecular weight vinyl resin (L) may preferably satisty the above properties as a whole. Further, to produce a single polymer, the ca.rboxyl group-containing monomer is added in the miiddle of pclyrn'Orization or added separately at the beginning and end c^f pc ] ymeri zation, whereby it is also possible to keep the width of the distribution of the carboxyl group in the m.olecules.
[0052]
Meanwhile, the binder resin for color roners of the present invention may further contain a block copolym^er including: a block comprising a seguenoe of ethylenic hydrocarbon derived constituent units and/or conjugated diene type hydrocarbon-derived constituent units, arid a oloc)-: cori.iprising a sequence of scyrene-derived constituenr units, and/or the hydrogenated product cf the block copolymer. The content of the block copolymer and hydrogenated block copolymer is preferably not less than 0.05 mass 1 and :iot more char- 0.1 m_ass \ and miore preferably not less than 0.1 m.ass -' and not mare than 0.5 mass % based on 100 m.ass 1 of the carboxyl group-containing -'inyl resin (C) . ViJhen the content is within rhe above ra^'g? , "he r-leasing agent can be finely

dispersed in the cruder resin v.d thour impairing storage stability, ""luidity and the li.ke of i no t'^^ner. Therefore, a toner excellent in cleaning properties is easily achieved.
[0053i
lu- order to obtain Liiese l^loci: lopolymers, there may be used one or m.ore Icinds selecced from eihyienio hydrocarbons such as ethylene, propylene, 1-butene, 2-butene, isobutylene, 1-pentene, 2-pentene, 2-methyl-l-butene, 3-methyl-1-butene, 2-mechyl-2-butene, 1-hexene, 2, 3-dimethyl-2-butene or the like, and conjugated diene based hydrocarbons such as butadiene, isoprene or the like. The block copolymer is produced by using a reactive group of a block copolymer obtained in accotrdance '.-;ith a knov/n living anionic polymerization or a lining polymerization, and then blocking this reactive group '//ith styrene. However, the production method is not restrict'^-d thereto and other conventionally knovm miethods may also be employed. In addition, some kinds of the aforementioned block copolvm.ers ha^'e unsaturated double bonds; the block copolymer may be used as a hydrogenated product obtained by reacting the unsaturated double bonds of the block copolymer v/ith hydrogen in accordance v/ith a known process.
[0054]
Examples of a commercial product used for the aforementioned block copolymer include Kraton
(styrene-ethylene/butylene-styrene based block copolymer (SEBS), styrene-butadiene-£ tyrt ne i ased i^lock copolymer, styrene-iscprene-styrene based block copolymier, styrene-ethylene/propylene-styrene based block copolymer or

styrene-ethylene/prcpy"-n? based block copolymer) produced by hraton Pclymer Co., Ltd., Septon istyrene-ethylene/propylene cased bloch copolymer or he'dioqeriateo styrene-isoprene based block cooolymier; produced by Kuraray C?., Ltd. and Tufprene ' styrene-butadiene based bicuck copolymer) produced by Asahi Kasei
In the presenr in.verition, as a men hod for producing the carboxyl croup-containing v-inyl resin (C) and the glycidyl group-containing vinyl resin (E), there can be adopted any of knov/n polymerization '^..ethods such as solution pc-lymeriza t.i on, bulk polymerization, suspension polym.eriza tion, emu-lsicn polymerization and the like, or the combination there'll. ScL.ution polymerization, bulk polymerization and the comt_: nat i',mi thereof are suitably adopted from the viewpoincs of aojustment of the molecular weight distribution, mixing pr:^oerties oi the high molecular weight vinyl resin (H) and the low miolecular weight vinyl resin (L), and convenience of distribution adjustmient of the carboxyl group and "Cihe glycidyl group.
[0056]
The carboxyl group-containing vinyl resin (C) may be obtained by polymerizing each of the high m.olecular weight vinyl resin (H) and the low molecular weight vinyl resin (L) alone in advance, and then mixing these resins in the m^eit state or the solution stare. Further, it may be obtained by polymerizing any one of the high m.olecular weight vinyl resin IH) or che low molecular weight vinyl resin (L) alone, and then polymerizing the other vinyl resin in

the presence of rhe formei vinyl resin. [00571
Examples of the solvent used for solution polymerization include aromatic hydrocarbons such as benzene, toluene, ethylbenzene, xylene, cumene and the like. These miay be used alone or a miixture thereof may be used, and preferably used is xylene.
The lov: moleculai: v/eicht vinyl resin (L) easily contains lots of low molecular \/eight ccm.ponent having a molecular weight of not micre than 2,000 as compared to other resin components such as the high mLolecular v/eiqht vinyl resin (R) or the glycidyl group-cc'nraining vinyl resin (E) . Accordingly, to produce the low m.olecular weight vinyl resin (Li by solution polymerization, a solvent is preferably used in. an amiount of not less than 20 m^ass parts ani nor more than "'? mass parts and further preferably not less than 35 m.ass parts and le't :;-ore than 55 mass parts based on 100 mass parts of the cc-~:s tituent mLonomer in order to reduce the low molecular weiahr c -vpc^ent ha"ing a molecular weight of not more than 2,000.
[00531
Polymerization may be carried out by using a polymerization initiator or so-called thermal polym.erization may be carried out \^'ithout using a polymerization initiator. As a polymerization initiator, any polymerizacion initiators can be usually used as far as they can be used as radical polymerization initiators. Examples thereof include azo type initiators such as 2,2' -azobisisobutyronitrile, 2,2' -azobis ( 4-methoxy-^ , 4-':;imethylvaleronitrile) ,

dimethyl-2, 2 ' -azobisi scbuty^^a ve,
1,1'-azobis(l-cyclohexaneca rbonltrile) ,
2- ', carbamoylazo) -iscbul _ r: ibd; i lie,
2,2' -azobis (2,4,4-rrimethy]pentane) ,
2-phenylazo-2, 4-dimethyl-'^' -nethoxyvaleronitrile,
2 , 2 '-azobis ( 2-methyl-propar,e ) and the like; ketone peroxides such
as rr.ethylethylketone peroxide, acetylacetone peroxide,
cyclohexanone peroxide and the like; peroxy ketals such as
1,1-bis(t-butylperoxy)-3,3,o-trimethylcyclohexane,
1,1-bis(butylperoxy)cyclohexane, 2,2-bis(t-butylperoxy)butane
and the like; hydroperoxides such as r-butyl hydroperoxide, cumene
hydroperoxide, 1, 1, 3 , 3-tetia;i;ethylbatyl hydroperoxide and the
like; dialkyl peroxides such as dJ-;:-buLyl peroxide, n-butylcumyl
peroxide, di-cumyl peroxide,
2, 5-diinethyl-2 , 5-di (t-butylperoxy) hexane,
«, o''-bis ( t-butylperoxy: sop. :i;\'I } benzene and the like; diacyl
peroxides such as isobutyiyl peroxide, octanoylperoxide, decanoyl
peroxide, lauroyl per'jride, 3 , 5 , 5-trimethylhexanoyl peroxide,
benzoyl peroxide, m-toluoyl peroxide and the like;
peroxydicaroonates such a\s diisopropyl peroxydicarbonate,
di-2-ethylnexyi peroxydicarbonate, di-n-propyl peroxydicarbonate,
di-2-ethoxyethyl peroxycarbonate, di-methoxyisopropyl
peroxydicarbonate, di(S-methy1-3-methoxybutyl)peroxycarbonate
and tne like; sulfC'uyl peroxides such as acetylcyclohexyl sulfonyl
peroxide ano the like; ar_d i:-ero;-rng zV.^ solvere or the like, can be adopted. In particular, preferably used is a m.ethod em.ploying a rv/in screw kneader. Concrete examples thereof include a method involving mdxing pov/ders of the carboxyl group-containing vin^'l resin (C) and the glycidyl group-conoaining vinyl resin (E) by the use of a Henschei m.ixer or rhe 'i :e and rhen conducting mLelt-kneading and reaction using a t'uin sore.-; kneader, and a method involving feeding the carboxyl group-containing vinyl resin (C) and the glycidyl group-ccntarn^ng .vinyl resin (E) in the melt state to a twin screw kneader for conducting m.elt-kneading and reaction. The temperature for conducting melt-kneading and reaction is different depending on the type of the carboxyl group-containing vinyl resin (C; and the glycidyl group-containing vinyl resin (E), but it is in the range of 140 degrees centigrade to 210 degrees centigrade and preferably in the range of 150 degrees centigrade to 200 degrees cenrigrade. When the reaction temperature is excessively lov.p tlie

reaction speed miight possibly be lowered. As a result, the reaction is not sufficiently carried cut so that offset resistance might possibly be insufficient . Or the other hand, v;hen the reacrion uemiperarure is excessix^ely high, depolymerization occurs so that the volatile content remained in the binder resin or the lov: m.clecular weight comipcnent having a molecular weight of not more than 2,000 m.iqht possibly be increased, hs a result, defects such as deterioration of storage stability, contamh-nation of the inside of a device, the occurrence af odor and the like easily occur. [00 61]
As a m.ethod for miel t-bneadi ng and reacting using a twin screw bneader, water is injected into a twin screw kneader in an amount of not less than C.^ mass narts an.d n.ot more than 2.5 mass parts ana preferably not less than 1.0 mass parts and not more than 2.0 r-^_ss parrs based on 100 mass oari:s of the resin at a pressure of not less zhar. 1 MPa and nor :ri?re than 3 MPa and preferably not less than 1. 7 MPa and net m.ore thr.n 2.3 MPa. Then, water and the volatile ccm.ponent are preferably- ram.o^-ed by reducing the pressure to O.OCl PIPe CO 0.20 0 MPa and p;ef^-racly P.'^SO MPa to 0.150 MPa from a pressure reducing port insrailed 30 an outlet side from a water inlet. Incidentally, m_ th'- presenr invention, the pressure refers to a gauge pressure, than is, a value subtracting an atmospheric pressure from an absolute pressure based on a vacuum otherwise particularly specified. 5y having the injection pressure within the above range, water is fully mixed in the resin so that the volatile component is easily removed when reducing the pressure. Furthermiore, vjhen the amount of water injected is excessively sm.all.

the volatile comiponent cannot be fully remioved in some cases. On the other hand, when the amount of water injected is excessively high, the state of water dispersed in the resin is deteriorated and as a result, the volaLJ le ocriponent is hardly removed in some cases. Furthermore, the v._latile component can be fully removed from the resin by having the vacuum pressure within the above range. Besides, such a mLethod is preferable because the volatile content remcaineo in the binder resin can be not miore than 200 ppm and the low molecular weight com.ponent having a molecular weight of not more than 2,000 can be reduced at the same time. [0062]
For the purpose of improving dispersion of the releasing agent in the toner, the releasing agent contained in the binder resin of the present invention is preferably added in the following mianner. That is, in a step of producing the carboxyl group-containing vinyl resin (C;, the releasing agent is added in the co-presence of a solvenu and a block copolymLcr including: a block comprising a sequence of ethylenic hydrocarbon derived constituent units and/or c:.tijugated diene type ydrocarbon-derived constituent unifs, and a block comprising a sequence of styrene-derived constitueno units, and/or the hydrogenated product of the tdock Cupo^ymer, for removing the solvent. It is preferable thar the carboxyl group-containing vinyl resin (C) containing a releasing agent is produced in this way. Even v/hen tne aforementioned melt-kneadina and reaction are carried out ihereafter, the r-eleasing agent can be in an excellent dispersion siate. Furthermore, rhe carboxyl group-containing vinyl resin (C)

cc';iralning a releasiriO agent :nay be produced by polyrrierizing the Icn inoleculcL v/ej.~;hr "inyl "ecin 'L; ro:itaining a releasing agent in che presf^^me of at least cy\e or releasing agents having a melring point of list lower rhan 60 degrees centigrade a^nd not higher than 120 degrees centigraae, ct^^'" au 'jinount of not less than 2 mass ? and not more than 13 mass . based r^n 100 mass % of the constituent mc'nomier of the low molecular weight vinyl resin (L) , and using the pclym.erized low m.olecurar i;eight vinyl resin. Such a method is preferable for dispersion of the releasing agent is improved. Furthermore, during polymerization of the low molecular weight vinyl resin (L) containing a releasing agent, a block copolymer including: a block com.prising a seguence of ethylenic hydrocarbon derived constituent units and/or ccnjugated diene type hydrocarbon-derived constiruent units, and a block comprising a seguence of styrene-derived constituent units, and/or the hydrogenated product of the block copolymer, may be contained. [00 63]
The thus-obtained resin is cooled and ground to give a binder resin for a toner. As a m.ethod for cooling and grinding, any of conventionally known meth^is may be adopted, and as a method for cooling, a steel belt C'-oler or the like may also be used for rapid cooling. [0064]
The color toner of the present invention contains at least the binder resin for color toners of the present invention, a coloring agent and a charge controlling agent.
The color toner of the oresent invention is oroduced accordina

to a conventionally known method. The color toner of the present invention is preferably obtained by a grinding method. For example, at least tne binoer lesin for colC'i toners of the present invention, a ccloT.ing agent ar.d a charae conti:olling agent are added, and as Oiocessary other -driitives sucli as a releasing agent or the like are added, which are sn'^f i''i'^n^.l\' mdxed using a powder mixer. Thereafter, the resultijig mixture is melt-kneaded using a kneading mac:iir.~- suck as a h"-;at r^jll, a kneader or an extruder for sufficienuly mixing indi^'idual constituent components. The m.elt-kneaded material is cooled, and then ground and classified to collect particles having a particle diameter of ordinarily 4 to 15 micro-meters. The collected particles are coated with a surface treatnient agenu according to the powder mixing method, to obtain a toner. Or, as necessary, the toner may be subjected to sphercidicing treatment using a surface treatment device or the like. As a surface treatm.ent m.ethod, there can be mentioned, for example, a method of spheroidicing the toner by inflowing it in a hot air jet, a miethod of chamfering the toner by mechanical impact and the like.
[0065]
The color toner of the pr'=^sen.t invention has a glass transition temperature (Tg) obtaii.ed accorc'ing to JIS K-7121 standard is preferably from 45 to 75 degrees centigrade and more preferably from 50 to 65 degrees centigrade. When Tg is excessively lov;, the storage stability is not sufficient in some cases. When Tg is excessively high, the fixing properties are not sufficient in somiO cases.

[00661
The color toner of the present innoention has a softening point of preferably not m.ore than 125 degrees centigrade and further preferably not lov;et: than ^".' ieq:--,es centigrade and not higher than 120 degrees centigrade from the viewpoint of a balance among the oloss and other peiformanoes.
[0067 J
Meanwhrle, in tne color t.^ner of the present invention, the storaq miodulus G' at 160 degrees centigrade is preferably not less "iian 100 Pa and not more than 800 Pa and more preferably not less than 200 Pa and not m.ore than /OO Pa m.easured at a frequency of 6.28 rad/s. When the stoia^e miodulus G' is v/ithin th,e above range, a color toner excellent on balancing the gloss and various properties is obrained.
1 0 0 6 e [
Furthermore, in the or lor to-ner of the present invention, the integrated value of the content of the tetrahydrofuran (TidF) soluble portion in the m.olecular \veiqht region of not more than 1,000 is preferably not m.ore than ".0 m.-: 3s % based on the ootal IHF soluble portion frooi the vieo-points of the storage stability and cleaning prooerties.
[0059]

Any conventionally bncon releasing aoents satisfying the condition of a m.elting point of init lower than 60 degrees centigrade and not higher thar; 120 degrees centigrade may be used as the releasing agent v/hich may be used in the present invention.

Examples thereof include aliphatic hydrocarbon based wax such as low molecular weiaht polyethylene, lev/ molecular weight polypropylene, polyolefin copolymer, polyolefin wax, paraffin "wax, mmsrocrystalline wax, Fisher-jh;opsch wax and the like; oxides of aliphatic hydrocarbon based 're>: such as oxidized polyethylene -wax; vegetable based wax such as candelilla wax, carnauba wax, Japan wax, rice v/ax and jojoba wax; animial based wax such as bee wax, lanoiine and whale wax; m:ierj] tased wax such as ozokerite, ceresine and petrolatum; wax principally constituted of aliphatic esters such as miontanic acid ester and castor wax; and partially or totally deacidified aliphatic esters such as deacidified carnauba wax. Further, examples include saturated linear allpriatic acids such as palmitic acid, stearic acid and montanic acid or long-chain alkyl carboxylic acids having a long-chain alkyl group; unsaturated aliphatic acids such as brassidic acid, eleostearic acid and parinaric acih; saturated alcohols such as stearyl alcohol, eicosyl alcohiol, behenyl alcohol, carnaubyl alcohol, ceryl alcohol and melissyl alcohol, or long-chain alkyl alcohol having a long-chaini alkyl group; polyhydric alcohols such as sorbitol; aliphatic acid am.ides such as linolej.c amide, oleic amide and lauric amide; saturated aliphatic acid bis amides such '\s methylene bis stearamdde, ethylene bis capramide, ethylene bis lauramide and hexamethylen-'- bis stearamide; unsaturated aliphatic acio amides such as ethylene bis cleamide, hexamethylene bis Co-eamide, K, U -Jioieyl adicamide and M,N'-dioleyl sebacamide; aromatic based bisam.ides such as t-xylene bis stearamvide and
on; aiichatic mecal salts such as

calciui'i stearate, oalci.nii; lanicte, sine srearate and magnesium stearate; v/ax fziyo'ed by arafrincr vinyl based monomers such as a :rUyrene based mionomer, an acryJir based mtonomer, a carboxyl uroup-containino m.onoraer and a glycidyl group-containing monomer to aliphatic hydrocarbon v.'ax; partially esterified compounds of fatty acids ano polyhydric alcohols such as behenic acid m.onoglyceride; and mLOthyl ester comipounds having a hydroxyl group obtaineol by hydj'ogenating vegetable oils and fats. Further, examples include an n-paral lin mixture obtained from petroleum fraction or higher aliphatic hydrocarbon having one or more double bonds obrained by an ethylene polym.erization method or an olefination mechod by pyrolysis of petroleum based hydrocarbons; wax having a funccional group such as a hydroxyl group, an ester group, a carboxyl group or the lixe obtained by subjecting polyethylene wax obtained by an ethylene polymerization method or higher aliphatic hydrocarbon obrained by a Fisher-Tropsch synthesis method to liguid-phase oxidation with a molecular oxygen-containing gas in the presence of boric acid and boric anhydride; wax synthesized by a metallocene catalyst such as polyethylene, polypropylene, polybutene, polypentene, polyhexene, polyheptane, polyoctene, ethylene-propyxene copolymer, ethylene-butene copolymer and butene-propylene copolym.er; and ester group-containing wax obtained by the reaction of a halide of long-chain alkylcarboxy] j.c acid with polyhydric alcohol or condensation wirh long-chain alky^ carboxylic acid with polyhydric alcohol. These releasing agents may be used singly or in combination of z-/:'-?^ or more kinds. The binder resin of the present

invention conrair^? 3 releasi-na aqeric in an amount of not less than 3.5 inass I and not ir.ore thian 12 mass 1 based on 100 mass % of tne to'ral amount of the carbox\'l group-containing vinyl resin (C) , the ciLyoidyl oroup-co)";"aininq' '/ln^'l resin (E) and a reaction product. Thes:^ roloasinq acents aro ?(ui-d in the production of the binder resin. Kov.-ever, the above releasing agent m.ay be added in a small amC'Unt in the ranges in vni :h the fun.ctions are not impaired in tne product 1 an of the toner
hO 0 7 0 I

The color toner of the piesent invention contains a coloring agent. As a colorirg aqeni, conventionally known pigments and dyes i^ay be used. Exav'ples if the pigmenc include m.ineral fast yellow, !:a^'el yellow, hapnihcvl "ell ^v/ i, I'ania Ye^lov/ G, Permanent Yeilov/ dCG, Tartrazine Laice, m.olyodenui' orange. Permanent Orange GTPv, pyrazolone Orange, Benzidine Orange G, Permanent Red 4R, V:atchunq Red C3_.zium sa_v;, eicsi"s 1 !: , Brilliant Carmine 3B, mLanaanese

violet, Fast Violet B, Methyls Violet Lake, cobalt blue, Alkali 31ue L = ke, Victoria BJ.ue Lake, thrhalocyanine Blue, Fast Sky Blue, Indantlirene Slue BC, chrome c,y.een, -igment Green B, Malachite Green Late, Final Yellcv.' Green G '-nod the l:ke. Examples of the magenta coloring pigm^ent include C.I. Pigment Red 1, 2, 3, 4, 5, 6, ""'', ?', 9, 10, 11, 12, 13, 14, 15, 11, 17, 13, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48, 4°, 50, 51, 52, 53, 54, 55, 57, 58, 60, 63, 64, 6S, SI, 33, 8^, 88, 3-), 90, 112, 114, ]22, 123, 163, 202, 206, 207, 209, 238; C.I. Pigment Violet 19; C.I. Violet 1, 2, 10, 13, 15, 23, 29, 35 and the lilce. Examples of the cyan coloring pigment include C.I. Pigment Blue 2, 3, 15, 15:1, 15:2, 15:3, 16, 17; C.I. Acid Blue 6; C.I. Acid Blue 45; copper phthalocyanine pigm.ents v;hose phthalocyani. - skeleton has been substituted with 1 10 5 phthallmide m.ethyl gioup(s) and the like. Examples of the yellow coloring pigment in.clude C.I. Pigm.ent Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 1., 15, 16, 17, 23, 65, 73, 74, 83, 93, 97, 155, 180, 185; C.I. Vat Yellow 1, 3, 20 and the like. Exam.ples of the black pigmient include carbon black such as furnace black, channel black, acetylene blacJ:, thermal black, lamip black and the like. Exam^ples of tlie dye include C.I. Direct Red 1; C.I. Direct Red 4; C.I. Acid Red 1; C.I. Basic Red 1; C.I. Mordant Red 30; C.I. Direct Blue 1; C.I. Direct Blue 2; C.I. Acid Blue 9; C.I. Acid Blue 15; C.I. Basic Blue 3; C.I. Basic Blue 5; C.I. Mordant Blue 7; C.I. Direct Green 6; C.I. Basic Green 4; C.I. Basic Green 6; Solvent Yellow 162 and i:he like. These coloring agents may be used singly or in combination of cwo or m_ore kinds. The amount of the coloring agent added to the roner is preferably from 0.05 to 20 m.ass %, more

preferably from 0.1 ro ^ r:ass i a;id further preferably from. 0.2 ro 10 mass % based on 100 mass 'z of the binder resin.
[0072i
Meanvv'hile, the cclor toner of the present invention may be used as necessary by partially addinq, for example, polyvinyl chloride, polyvinyl acetate, pclyester, oo'lyvinyl butyral, polyurethane, pcdyam.ide, rosin, polymerized rosin, modified rosin, terpene resin, p^nenolic resin, aromiatic petroleum resin, vinyl chloride resin, s tvrene-butadiene resin, s '^yrerie-erhylene-butadiene-styrene block copolymer, styrene-imeth)acrylic copolymer, chromiane-indene resin, meiaiaine resin or the like, in the ranges in which the effect of the present invention is not impaired.
: 00731

When the color toner cf the? present invention is used as a tvjo-com.ponent developing' .;jen+:, conventionally knov^n carriers may be used as a carrier. For example, there may be used particles having a number average paiticle diameter of 15 to 300 micro-m.eters comiposed of metals such as surface-oxidated or non-oxidated iron, cobalt, m.anganese, chromi\:n., copper, zinc, nickel, magnesium, lithium, and rare earths, and alloys thereof or oxides. As the carrier, there may be used carriers ivith its surface coated by a styrene based resin, an acrylic based resin, a silicone based resin, a polyester resin, a fluorine based resin or the like. Furtherm.ore, there may be usee maanetic carriers having a m.agnetic m.icroparticle dispersed based core obrained by dispersing magnetic m.icropartides in the resin and a coated layer containing a coated resin no be applied on the surf a re of the miagnetic miicroparticle

[ 0 0 7 5 1]
The lecuitirig ■roi'^r loner according to the present invention raav be a.pplied tj I'arir^us }:no\;n developinent methods. Examples thereof include, thouah not restrict r-d thereto, a cascade dei^elopm.ent mLethod, a magnetic brush metnod, a powder cicud method, a touch-down methoo, a so-called micro-toning method using, as a cairrier, a maanetic toner produced by grindina miethod, and a so-called bipolar miagnetic toner method in which a required amiount of toner charges are obtained by the frictional electrification between magnetic toners. The resulting color toner according to the present invention may also be applied to various cleaning methods such as a conventiondlly known fur brush method, a blade m_ethod and the like. Further, the resulting color toner according to the present invention can be applied to various conventionally known fixing mtethods. CCi\:rete examples thereof include an oil-free heat roll miOthod, ^n oi]-coated heat roll m.ethod, a thermal belt fixing method, a flasn method, an oven method, a pressure fixing miethod ano the like. It may also be applied to a fixing apparatus using an electromagnetic induction heating miethod. Turther, it m.ay also be applied to an image forming method ixcvolving an interm.ediate transfer step.
EXAMPLES [0076]
The present inccention is now illustrated in detail below with reference to Examples. However, the present invention is not

restricted to these Examples. Evirthermore, miethods of measuring ar:a judgina data are as , Further, in Tables, St represents styrene, Mac represents n^eiihaci yri s, acid, BA repiresents n-buryl acrylate, G-Ei represents g]//crd\'d_ methacrylate, and Xy represents
- I <^ 7 '7 "I
•.ricid Value>
The acid value 'AV; in t■^e Example v/as calculated in the tollcwing mianner. A.n accurately v.'eighed sam.ple was dissolved in a mrlxed s:lvenr or x-/lene aud n—):>utanol (miass ratio = 1:1) . The solution ;,.'as titrateci with slcohoJ of standardized N/10 potassium hydroxide (7g of specJ.al class potassium hydroxide was added to 5a of ion excnange v;ater, diluted to IL (litter) with first class ethyl alcohol, and then tj'"r.= ted with N/lOhydrochloric acid and 1: phenolphrhcilein solution zo determine titer^F) for calculating che acid value from, its neurralization amount according to the following equation.
Acid value (mcgKOH/g'i = hh/dO KOH titration amount (ml) x v x 5.61)/(sample g x 0.01)
[0078]

Tmi in the Example was measured by using an elevated flow tester CFT-500 manufactured b^ Shim.adzu Corporation. A sample having a volum.e of 1 cm^ was m.elted and flowed under conditions of a diam.eter of a die pore of 1 min, a pressure of 20 kg/cm" and a temperature increase speed of 6 degrees centigrade/min and Tm v/as determined as the temperatures when +:he sample is half-size between started and finished flowing.
I 0082i

The epoxy value u'as measured in the following procedure. 0.2 to 5 a of a resin sam.ple was weighed accurately and put into a 20G-miL Erlenmeyer flask, and then 2,1 ml- of dioxane was added thereto and dissolved therein. 25 m.L of a 1/5 normal hydrochloric acid solution (dioxane solvent) Vv'as added, and the resulting solution was sealed ar,c, fully mdxed, ana then allowed to stand for 30 minutes. Next, 5'j ml- of a mixed solution of ccd_uene and ethanol (1:1 volume ratio) i.'as added, and then th.e reacrion solution was titrated with a 1/10 normal aqueous sodium^ hydroxide solution using cresol red as an indicator. Based on the tirraLion results, the epoxy value (Eq/100 g) was calculated accordino to the following equation. Epoxy value (Eg/100 g; = :(B-S) ^ H x E!/(10 x W) Herein, /- refers co the am/ount of collected sample (g) , B refers 0 1 the amicunt or one aqueous sodium, hydroxide solution (ml, required for a blank test, S refers to the amiount of the aauaous

and .Tiixed to dissolve the resin (resin: XQ gram, internal standard solution: yn graml . After id'ie di ssol'jt ion, the solution was allowed Lo stand t:- separate the pr'voi}:>r L a to and che supernatant lipoid. 3 micro-liters c-f the supernatannc lipuid was analyzed using gas chromatography under the fcdlowinq conditions.
11-353 colnmn : 11 ui x 1'. 3 3 u^ia
ULPON HF^-1
Column te;npeiat jre : "oO degrees cerjtigrade
Inject;: on temperature: 13Ci de'„~!rees cencicrade
P- gas flow rare: 10 ml Iriiri.
lample soluoJ.cn: 5% ao-C'jne soluoion
amiount of so'lutlon iniocted: 3 m.icro-liters
Detectoi: FID
[-085J
A volatile component contained in the resin was specified from the obtained gas ohromsitogramt. oubseguently, the volatile comiponents were weicflied. HerelT": ^ styrene v;as explained as an example and the sam^e procedure was applied to other m.onomers or other components such as a solvent or the like to be used in the production.
Firstly, a calibration curve of the specified component was prepared.
The calibration curve was prepared in the following manner.
1. 0 . 2 g of 1, 2-dichlorobenzene and 0.1 g of styrene are weighed accurately in a lO-miL screw tube and diluted with 10 g of acetone, and then m.ixed wel

2. G . 2 g of 1, 2--dichlorobenzene and 0.2 g of styrene are weighed accurately in a 2 0-iiiL screw tube and diluted with 10 g of acetone, and then mixed well.
2. 0.2 g of 1, 2-dichl' rclTcn;:en-- and 0.3 g of styrene are weighed accurately in a 20-mL screiv tube and diluted with 10 g of acetone, and then mixed well.
4. One micro-litter o" Or'ch scmrle regulated in the above steps 1 to 3 is fed f:o ?. 20-nL sere''/ tube usrnq a rriicro syringe and dilured with ]0 g of acetone, and ^dien rrixed well.
5. Sam.ples obtained in the step -'. are respectively injected into gas chrom.atograph under the above conditions.

6. An AREA vaxue is obtained according to the concentrations cf eacli sam.p.le respectively by the gas chromatograph.
7. Wrtn respect to th.e ratio tx-' of .AREA values of styrene to ],2-dichlorobenzene, the weight ratio (=yi) of styrene to
1, 2-dichlorobenzene is plotted arc a first-order approxirr.ate expression (Y = ax - b) is calcuj.ated using the least square m.ethod CO prepare a calit^'ration ::vzve.
R~ an this time is confirmed be not less than 0.9800. When it is less than 0.2300, a aalibiration curve is prepared again.
L 0 0 8 6 J
Tf.e amLC^unt of styrene 'vas calculateti in the following p a n PL e r
1. The ratio cf the A^REA value of styrene to the AREA value of 1, 2-diclorocenzene in the samiple oo.tained by gas chromatograoh is defined as x-.
2. 3y the substitutior: cf x^. for the first-order approximate

expression of the calibration curve, the weight ratio (=y?) of
styrene to 1,2~-dichlorobericene is calculated.
3. The amount of styrene in che resin is calculated by the
following eguation.
Amount of styrene tppm) =^ y^ x c x y.j / (1,000,000 x XQ) The toner was also measured in the same m^anner.

Using a transmLission electron miicroscope H-7000 (a product of Hirachi Ltd.), the dispersion state of the releasing agent v/as confirmed an xlOOOO magnification. When a m.easurement sample was a binder rein, the binder resin was trimmed, surface-developed, and then dyed with RuO^, whereby a super slice piece was prepared and observed. The major axis diameters of the releasing agent to be observed v/ere measured and a mean value thereof was defined, as a dispersed-particle diameter. When a measurement sam.ple was a toner, the toner was v/rapped with an epoxy resin and was observed in che sam.e m.anner as in the resin.
[0088]
I-iext, e^'aluation mechods jf the toner carried out in the present invention are described below.
[0089]
1. Evaluation of Fixinp PrC'perties
An unfixed image v/as forme 1 using a copier produced by remodeling a commercial electroohotearachic copier. Then, the unfixed image v;as fixed using a heat rollet fixing apparatus produced by reirodeling of the fixmcf section of a comin.ercial copier at a fixing

sreea or the hta" i";-iier of i-'C n[;i/s.-c respectively at a uemperatuie o:: 11 Of 160 and HO degrees centigrade. The fixed image obtained '.v^s rubbed ■: times by apply:; nc a Iccui of 1.0 kgf using a sand eraser ;a piodnit of Tomoou Pencil Co., Ltd.), and the image densities before and cdrcer one rubh'ii:;- oes'r vreie measured using a MaobetOi reflection densitomieter . Th? imig-o density after the rubbing rest - image ciensity before the rubbing test >^ 100 ivas taken as the change raoio at its temperature. The average value of the each change ratio at lO'^', 160 and l"'j IcVJte^-^ centigrade v;as calculated as a fixing ratio which was then deoermined on the basis of the follov.'ing evaluation standard. Incidentally, the heat roller fixing apparatus used herein had no silicone oil feeder. Further the environmental conditions ^vere undei norm.al temperature and normial pressure (temperature of 22 degrees centigrade, reiati^^e humidiiy of 5 5%) .
(Evaluation Standard)
A: 67% < (not less than) Fixing ratio E: 63% < (more than) Fixing ratio < (less than) 67=^
C: Fixing ratio d (not more than) 63% [0090]
2. Offset Resistance
The offset resistance was evaluated as follov;s according to the above measurement of the lov/est fixing temperature. That is after an unfixed imiage \v'as firmio utina the above copier; then the toner image was fixed using the above heat roller fixing apparatus; and the appearance of toner staining on the non-image portion was examined. Tbiis operation \.'as repeated by gradually increasing the

set teiiiperature cf the heat roller of the heat roller fixing apparatus. T'lie lov/est s-u temperature at which toner staining appeared was taken as the temperature of offset appearance. Further, the atm:0sphere C'f Lhe above copier was a temperature of 12 degrees centigrade and a relati.ve humidity of 55%. (E V a 1 u a t i o n S t a a d
appearance < (less ahanj) Ic'O degrees centiaraae
Teir.rera Orre of cftser ajipesrcnce < (less than) 160 degrees
T
ntrgrace
I 0 0 911
3. Cleaning properties
After continuous copying of 20,000 copies was conducted at a temperature of 22 degrees centigrade and a relative humidity of 55% using the abc-ve copier, contammnation of a photo-sensitise m.aterial -was evaluated visually.
(Evaluation Standard)
A: Not contaminated at all
C: Contamination confirmed
[0092]
4. Storage Stability
5 g of the toner was allowed to stand under the environm.ental conditions of a remipera+urc ,nt 50 degrees centigrade and a relative humidity of 50% for 24 hours, and the toner was fed into a sieve of 150 mesh. Then, th^^ scale of a rheostat of a powder tester

(Hcsokawa Pender Technoloq\- Reseaich Institute) was set to 3 for vibrating ir for a miinute, After vibration, the mass remained en the sieve of 150 mesh was m.easured ro obtain the residual mass
■ PLvaluation Standard)
A: Residual mass ratio '■ (less than) 25%
3: 251 < (not less than) Residual mass ratio < (less than) 30v C: 301 1 (not less than) Residual m^ass ratio
L J U b J j
5. Durability
To a 10-md glass sam:3le ' u.j? Wr_s fed 24 g of a stainless steel ball, and 0.05 g of a toner v/as added thereto. The tube was lidded and the resulting me.ceiia; ;;as stirred while rotating at a race of 3C0 rpm for 20 minutes. Toe partisle size distributions of the tonei before and afrer S'r.irring were measured by the use of a coulrer counter, d^umber miedian dramLeter D50 before stirring -nur(oer median dlam.erer D50 after stirring) ~ number median diameter 150 oefore stirrina ^ 100 v-r s iH);en as r)ne particle diam.erer change raric which was Oten oetermiined according to the following standard,
(Revaluation standard)
h: Particle diamieter change ratio < (not less than) 211
5: 215 <- (m.ore than) Part' u.e diam.ecer change ratio ^ (not less
: 23l <- (maire chan! PF^rricle diameter change ratio
0 0 94)
. Producrivitv

In the production of a roner, tne m.ixture kneaded using a tv/in screw kneader and cooled was parrially collected and arranged ar 10 mesh under and 16 mesh on particle size, and then ground under predetermdned conditions using a jet miill to measure the toner yield. The particle size distribution was measured using a coulter counter, and (yield g of the toner per unit hour) - (weight g of one toner particle obtained from yolume median diameter D50) - 10 '.;as taken as the productiv-ity which was then determd.ned according to the fojlowing standard.
A: 100 ^ (not less than' Productivity
3: 95 S (not less than} Productivity < (less than) 100
C: Productivity < (.less iMani 95
[0095]
7. Gloss
An unfixed image was formed using a copier produced by remodeling a commiercial electrophotc^jraphic copier. Then, the unfixed imiage was fixed using a heat belt fixing apparatus produced by remodeling the fixing section of the commercial copier at a fixing speed of 125 iTUTi/ses of the heat roller at a temperature of 150 degrees centigrade. The im.age density of che fixed im.age obtained at this time was measured using a 'lacbeth reflection densitometer and adjusted so as to be 1.4. The glossiness of the resulting fixed image was m.easured at an incident angle of 75° by means of a Variable Glcss Meter G1I-3D (a product of liuraKami Color Research Laboratory to., Ltd.'. Further, the einosphere of the above copier was a temperature c;f 21 deoree= '^entJqrade and a relative humidit\' of

(E\'3 ]_n^r j on
A; 30/ i (n-jo less the'/; Gloss:! ness
B: 251 1 (not less tn.an : Glossiness t (less than) 30%
C: Gilessiness •- (less than) 211 r 0 0 Q t: ]
[Producrion Examples ol C4lycidyl Group-containing Vinyl Resin
(E) ]
(Production Example E~J)
50 miass % of xylene base! on 100 xmass % of monomiers v/as fed into a flask purged with nitrogen and the resulting material was heated, finder xylene reflux, 0.5 mass i of di-t-butylperoxide was continuously added in the rotal amiOunt of 100 mass % of monomers previously mixed and d'ssolved as illustrated in Table 1 over 5 hours, and further continaously refluxed for 1 hour. Thereafter, while an internal tem^i: stature was maintained at 130 degrees centigrade, 0.5 mass % of di-t-butylperoxide was added and the reaction was continued for 2 hours to obtain a polymerization solution. The resulting polymerization solution was flashed in a vessel at 160 degrees centigrade and 1.33 kPa for removing a solvent or the lil-ce to obtain a resin E-1. The physical properties thereof are shown in Table 1.
[0097]
(Production Example E-2)
50 mass 1 of xylene based on 100 m.ass % of monomers was fed into a flask purged with nitrogen and the resulting miaterial was heated. Under xylene reflux, 0.4 miass % of di-t-butylperoxide was
previously mixed ar.a -_ ssc'-ved as illusrrated in Table 1 over 5 hours, and further coiitinuc^usly refluxed for 1 hour. Thereafter, i.^hrle an inve^:nal temper;-,: i: re v/as m.aintained at 130 degrees cenrigraae, 0.5 mass - of cii-t-butyl per oxide vjas added and the reaction vjas continued for 2 hours to obtain a polymerization sol'jtion. The resulting polymioriiation solution was flashed in 3 vessel a r IGO tear^es ce];ticjrade and 1.3 3 kPa for removin.g a br^v-zenu ;v she 11!:-= hi Ldrra^ r a resin E-2. The physical properties C'lereof are shov/n in Tahlr 1.
[ 0 0 9 8 :
(Prodaction Exampie E-3^
H resrn E-3 v/ae obtained in the same mianner as m Production Example E-1, except xr-z ir'. ^^m^er coii;position as described in Table 1. The physical prope;ties hT?r-jf are shown in Table 1.
[ 0 0 9 9 J
i" Production Example E- '■ '
A resin E-4 was obtarndd in uhe same mianner as in Produccion ExampJ.e E-1, except for rru^nomer com^position as described in Table 1. The physical properties tliereof are shov/n in Table 1.
[OlOOj
fProduction Example E-c)
R resin E-5 was obtained in the same mianner as in Production Example E-1, except for monomter composition as described in Table 1. The physical properties thereof are shown in Table 1.
[0101]
[Production Examples of Low Molecular tveight Vinyl Resin (L) ]
(Production Examiple L-: )

50 miass 1 of x\xlene based on 100 mass % of monomers was fed into a flask purged witn nit^-A^pen and tdxe resulting material was heated. Under xylene reflux, 1.8 luass % of t-butylperoxy-2-ethylhexancate was continuously added in rne total amount of 100 mass % of monomers previously mixed and dissolved as illustrated in Table 2 over 5 hours, and further continuously refluxed for 1 hour. Thereafter, while an internal temperature was maintained at 98 degrees centigrade, 0.5 m.ass 1 of t-l-utyi rieroxy-2-ethylhexanoate was added and the reaction v:as continued for 1 hour, and 0.5 mass 1 of r-butylpercxy-2-ethylhexanoate was further added and the reaction was continued for i hours to obtain a polymerization solution L-1. The physical properties thereof are shown in Table 2.
[01021
'Produorion Exan,ple T.-'h
A polymeritation soltu:ien >,-;. -as obtained in the sam.e m.anner as in Production Example h-J, except for monomer composition as described in Table 2. "h-: pl'iysical properties thereof are shown in Table 2.
! 010 3 I
(Froctactlcn Example L-3'
50 mass '^ of xylene based on 100 mass % of monomiers v;as fed into a flask purged with nitrogen and the resulting miaterial v;as heated. Tnder xylene reflux, 1.0 mass 1 of t-butylperoxy-2-ethylhexanoate was continuously added in the total amount of 100 mass % of monomers previously mixed and dissolved as illustrated in Table 2 over 7 hours, and further continuously refluxed for 1 hour. Thereafter, •while an mternai tem.peratu^e was miaintaaned at 9S degrees

centigrade, 0,5 mass ° 2-ethylhexanoate v/as further added and the reaction i^jas continued for 1 hour^ and 0,5 mass 1 of t-buty] peroKj' -.l-e ch\ Ih.exanoate ivas further added and the reaction a'as ccnrinued fr r 5 iicris to obtain a polymerization solution L-3. The physicaj, properries thereof are shown in Table
[0104T
(Production Example L--'b
6.72 miass % of tJAX-1 as descrified in Table 3 and 50 m.ass 1 of xylene were fed into a flask purged v:ith nitrogen and the resulting m.aterial was heated. Under xylene refluxp 1.8 mass % of u-butylP'eroxy-2-ethylhexanoate was continuously added in the cecal amiounc of 100 mass -' of monomers preriously mixed and dissolved as illustrated in Table 2 over 5 hours, and further continuously refluxea fir ' h.iur. Thereafrer, while an internal tem.perature was maintained ac 9? degrees centigrade, 0.5 miass % of L-bucylperoxy-l-ethylhiexanoate 'cas further added and the reaccion v;as concinuet loi 1 houi , and 0.5 mass 1 of t-butylperoxy-2-ethylhexanoate v/as further added and the reaccion was continued for 2 hours to obtain a polymerization solution L-4 . The physical p.roperries thereof are shown in Table 2.
[0105]
(ProdLMcion Exam^ples L-5 to L-7^
Polymerisaticii solutions L-5 to L-7 were obtained in the sam^e m.anner as in Produce ion Ex Simple t-1 v;ith feeding comLpositions as
a L.'j:.
snccn

L' 10 6 J
cor tinuoi:s]r/ added ii^i the toral air.ount of 100 mass "; of monomers
previously mixed and disscr'X'ed as illustrated in Table 2 over 5
hours, and further scntinuously retJ.uxed for 1 hour. Thereafter,
while an internal temperature was maintained at 130 degrees
centigrade, 0.5 m ]
(Production Example H-1
100 mass 1 of m.onomLecs ds illucnrated in Table 4 was fed into a flask purged \/ith nitrogen. An internal temperature was ele^'ated to 120 degrees centigrade 5;ia kepL at the same temperature, and bulk polym.erizaticn v:as caimied out for 8 hours. Subsequently, 50 m.ass °- of xylene was added to 100 m.ass % of mionomers, 0.2 mass ^ O'f tetraethylene gj.ycol diaorylate was added, and then the temperature was elevated to ilO degrees centigrade. 0.35 m.ass 1 of 1, i--bis''o-but ylperoxy) oyclohexane and cO mass % of xylene previously mixed and dissol^'ed were continuously added thereto over 9 hours vnhile miainta.i ning the temperature at 110 degrees cenrigtade, and then the reaction '.-/as continued for 1 hour. C'.ll n-aso ~'. of " , 1-bis ; c-bnty] r arcxy) cvclohexane was added and the re-.-,;': ion was continued tci 2 hours. 0.5 2 mass 1 of 1,1-bis(t-butylpercxy)cyclohoxane was further added and the reaction '.-.'as continuc,d ±' .: Z h'auis, •■inereby the reacoion was coicoleted to obtain a Imah m'.loCiilar weicfht polymerization solccion H-1. The rjh^'sical prco'eitres are show-n in Table 4.
[ 0111J
iProduation Example H--2)
100 mass -: of monom.ers as illustrated in Table 4 was fed into a flask puruei v.'ith niorogen. An internal temperature was elevated to 128 degrees cenoiarade ana kept an the sam.e temperature, and bulk polyiTierization was carried out for 3 hours. Subsequently, 50 mass 1 af xylene Vv'as added to 100 mioss % of mionomers . Thereafter,
the temperarure was elevated tv,> 110 degrees centigrade. 0.35 miass % of 1,1-bis(t-butyloeroxy)cyclohexane and 60 mass % of xylene previously mdxed and dissolved were continuously added thereto over 9 hours while m^aintalj"'-h-g th- temperature at 110 degrees centigrade, and then the reacrioii was continued for 1 hour. 0.21 mass % of 1,1-bis(t-butylperoxy)cyclohexane was added and the reaction was continued for 2 hours. 0.52 mass % of 1f1-bis(t-butylperoxy)cyclchexane was further added and the reaction v/as continued for 2 hours, whereby the reaction was comLpleted to obtain a high molecular weight polymerization solution H-2. The physical properries are shown in Table 4.
[0112]
I Production Example H-3)
r\ high mLolecular w;eight polymerization solution H-3 was obtained in the sam.e manner as in Production Example H-1 with feeding composition as indicated in Table 4. The physical properties thereof are shown in Table 4.
[01131
(Production Example H-'^
A high m.clecular weight polymerization solution H-4 was obtained in the same mLanner as in Production Example K-2 with feeding composition as indiiazed in Table 4. The physical properties thereof are shown in Table 4.
(Table Removed)
Production Exanp.ples of Carboxyl Group-containing Vinyl Pxesin (C) and Mixture of Carooxyl Group-containing Vinyl Pvesin (C) v.ith Releasing Agent]
(Production Example C-1)
Respective polym;erization solutions were m.ixed such that the miass ratio of a high molecular weight vinyl resin (H) to a low molecular weight vinyl resin (L) v;as the ratio as described in Tables 5-1 and 5-2. Furthermore, 3.2 3 mass % of WAX-1 and 5.38 m.ass ': of l''JAX-2 as releasing agents, 0.5 mass % of styrene-ethylene-butylene-styrene block copolymer (SEBS)

(produce name: Kraton G1652; a product of Kraton Polymers J"apan LTD) as an addj cive were mixed in 100 mass x- of the total amount of the high molec;:lar weight vinyl resin (H) and the low molecular weight vinyl resin (L) . Tlnra-eafter, under xylene reflux, the resultino: .mixture v.'as mixed for 30 minutes and flashed in a vessel at 190 degrees cenrigrade and 1.33 kPa for removing a solvent or Ine like no obtain resin C~~ ' . The physical properties thereof are snov/n in Tables 5-1 and 5-1.
[01191
(Production Examples C-2 to C-29)
A high m.clecular weight vinyl resin (H) , a low molecular v/eight vinyl resin ''L) , a releasino agent and an additive were mixed such that the m.ass ratio thereof v/as the ratio as described in Tables 5-1 and 5-2 to obtain resins 1-2 to C-25 in the same manner as in Prcriuction Example C-1. The physical properties thereof are shovjn m Tables 5-1 anb 5-2.
'012 01

Table 5-1
(Mixture or carboxyl gicup-containing resin C and releasin.g
agentntaming resin C and releasing
(Table Removed)
Production Exarr.ples of Binder Resin (R!^
(Production Examples E-1 to R-2" and R-29 to R-34)
F^espective resins were mixed such that the mass ratio of a

mirture of ere carboryl groir:'-containing viryl lesin (C) and a releasinc ^gent to the glyoldyl group-contain,ing vinyl resin ;E) \:as the lario as describee in Taj^le 6, Thereafter, the inixrure vas kneaded and reacted at Tf t.o/hr and 1^-400 rpm by the use of a rv;in sere'.-; kneader (KEbd S-qt trpe, a product of Kurimoto Loo.) ivooh its teriporatnre set to ziie reaotiC'n temperature as described. Thereafter, rhe resultinn naLcriai v;as cooled and ground to obtain oir;der res.ins R-1 to --27 ana i'-29 to R-?4. The physical properties are snown in Table '> . As ^^ v'runcd for cooling, a steel belt cooler Mas used. The device W3S user under conditions of the cooling v/ater cemperature of 10 degrees cenaigraoe, the arriount of cooling water of 20 liter per 1 kg of the resin, a thermal conductivity of 0.08 kcal 'inhrs for rapid cooling. Tne physical properties are shown rn Table 7.
[0122]
(Production Example R-28)
Respective resrns \'je"e nixed such that the mass ratio of the carboxyl group-containing ninyl resin C-2 6 to the glycidyl group-containing vinyl resin (S) was the ratio as described in Table 6. Thereafter, the nitu-ure 'was kneaded and reacted at 25 kg/hr and 1,400 rpmi by the use of a twin screw kneader (KEXN S-40 type, a product of Kurimoto Ttd.) witn its temperature set to the

reaction temperature as described in Table 7. In the middle of the reaction, v/ater v;as injected tiiereinto at 2 MPa and 380 g/hr. 'liie pressure was reduced do\.'n to 0.095 MPa based on an absolute pressure by a pressure reducing oump equipped with a pressure reducing port installed at an outlet side from a water inlet to remiove the volatile component. Thereafter, the resulting material v:as cooled and ground to obtain a binder resin R-28. As a method for coolinq, a steel belt "v-oler was used. The device v/as used under conditions of the cooling \/ecer temperature of 10 degrees centigrade, the am.ount of water of 20 liter per 1 kg of the resin, a thermial conda.;'!": \md"u.- of 0.08 kcal/mhrs for rapid cooling. The physical properties are shown in Table 7.
:0123 I
(Production Examiple R-35)
A resin R-3J was obtaineo in tfie same manner as in Production Example ;'-12, e?rcept that i;ater -..'as not added during kneading and reaction. The physical preperr.j.es are snov/n in Table 7.

(Table Removed)

[01261
[Production Example cf Toner for Electrophotography (Til
(Production Example T-1)
6 mass I of carbon black (MAIOO, a product of Mitsubishi Kasei Corporation) as a colorinc agent and 0.5 m.ass % of a charge oo;itro]_lino: age^it 'T-77, a producr of Hodogaya Chemdcai Co., Ltd. ) ',;eie aidtd to 100 miass -" of the }?inder resin (R) as illustrated in Table 3. The resultina irnxture v/as mixed by means of a Henschel nixer, and then nneaded by means of a twin screw kneader (PCM-30 :yp'e, a product ':z IJ-.eaai .torporarion) at 90 degrees centigrade :b; the lesm temiperature -.r toe disaharge portion of the tv/in screw xneader for 30 seconds of the residence timie. Next, after cooling, arindinja and classify, 1 . : -^ ass ''- of hydrophobic fine silica powder T-.erosil R-Slf, a C'rod.L _.t. o'_ '\i.;p;' n Aerosil Co., Ltd.) was added fa 100 m.ass 1 of the "orer particle, whereby a toner T-1 having a volume median diameta" C'SC of about 7 micro-mceters measured using a coulter counter was obtained. The physical properties are shown in Table 8.
[012~[
(Production Example T-2;
A toner T-2 'was obtained in the same manner as in Production Examiple T-1, except that 5 mass ? of a cyan pigment (Toner Cyan 3G; a product of Clariant) as a coloring agent and 0.5 mass % of a salicylic acid based m_ecal com^piex (EZ8 4; a product of Orient Chemical Industries Co., Ltd.) as a charge controlling agent were used. The physical properties are shown in Table 8. [0128)

(Production E:-:a:rple T-3/
A toner T-3 was c-btaind; :u the same manner as in Production Exannie T-2, except that '•:. :TC!SS '- of a m.agenta pigment (Toner Magenta ECi; a producx of :]'. riant! i/as used as a coloring agent. The physical properties ave shovjn in Table 8.
[012«]
(Production Example T-4
T\ toner T-4 '-/as cbtaineci in the same manner as in Production Example T-2, oxcepi that 1 miss : or a yellow pigment (Toner Yellow HG; a product of tlarian':( was used as a coloring agent. The physjcal piopeL'ties are sii'i-'rr. in Table 3.
obtained in the same msionei as J n Production Example T-1, excer.'t for the ohanae to 100 rmis? 4 of the l^inder resin (F) as illustraied in Table '^'. The cloysi ' 1 Eloper LIS'S ace snown in Table 8. :0J31:
vProduiilon Examole T-11,
5 mass parts of a cyan pigment (Toner C'/an BG; a product of Glacianr'' as a coloring agent, 0.5 mass 1 of a salicylic acid based

tact of C';:ient Chemmcal Industries Go., LOO' agent and 2.5 mass % of a releasing •duct of Mitsui Ghem.icals Inc. ) '•"ere addct no 10 ^ mass -=-: :f the blinder resin (Ri as illustrated in Table rd The resolting r-nlxrure I'.'as mixed by means of a Henschel mixer, and then hdeaded by m.eans of a twin screw kneader (PCM-30

type, a product :f at 90 degiees centig of the resic temperaLoro a. t!ro dlac^'Srge portion of the tv/in screv; kneader for 30 seconds tr:o residence time. Next, after ccclmQ, prinding and classifying, 1 . 3 moss of hydrophobic fine silica pov^'der (Aerosil R-812, a p'roduco of Nippon Aerosil Co., Ltd.^ was added to 100 mass parts of fhe tonei particle, whereby a toner T-31 having DSC) of abour 7 micio-meters was obtained. The physical properties are shown in Table 8.
[0132i
Toners T-32 to T-38 having D50 of about 7 micro-mieters were obtained in the sam.e manne : as i ri Production Example T-1, except for the change to 100 mass - of the binder resin (R) as illustrated in Table 8. The pnysical propercies are shown in Table 3.
[0133]
'.Examples 1 to 2 5 anf C ^mpara ri^^e Examiples 1 to 13)
97 m.ass b of a carrier (E-15C, a product of Powdertech Corp.) 'was mixed no 3 m.ass % oi the toner as described in Table 8 to give a de^'-eloping ag-^rnt. Varrsus evaluations were performed for the resulting developing agenc. The results are shown in Table 9.
[ 013 4 [
(Table Removed)
As clear from the results in Table 9, all of the binder resin for color toners and the color toner using the resin to be produced according to the present invention were excellent in balancing various properuies required for a color toner.

1. A binder resin for color toners, ivherein the binder resin comprises at lease a carborvi-' group-containing vinyl resin (C) glycldyl group-containing vinyl, resin (E) and a reaction product rhereof,
the storage modulus G'' an 160 degrees centigrade is not less than 2C Pa and less than SOC Pa measured at a freguency of 6.28 rad/sec,
the tetrahydrofuran (THF) soluble portion in the binder resin has a main peak in the molecular weight region of not less than 20,000 and less than 40,000 m the molecular weight distribution m.easured by gel permeation chromatography (GPC) , and
the binder resin contains at least one of releasing agents having a m^elting point of not lower than 60 degrees centigrade and not higher than 12 0 degrees centigrade in an amiount of not less than 3.5 mass and not m.ore than 12 irass ° based on 100 m.ass % of the total amount of said carboxyl group-containing vinyl resin (C), said glycidyl group-containing vinyl resin (E) and the reaction
2. The binder resin for color toners as set forth in claim 1, wherein the integraced value of the content of the tetrahydrofuran (THF) soluble porrion m said binder resin in the molecular weight region of not m/ore than 2,000 is not more than 7.0 mass % based on rhe r o r a1 THE soluble protion.
3. The binder resin for color toners as set forth in claim 1, wherein
he weighu-average molecular wej.ght (MvO is not more than 170,000 nd the weigh t-avei aqe mo].iCu]ar v;eight (Mv;)/the number-average iiecular weight :Mn; is not J.ess rhan 5 and not more than 40.
. The binder resin for cole-" ^'inr:rs as set forth in claim 1, wherein the content C'f a volatile compcment remained in said binder resin is not m.ore than 200 ppm.
5. The binder resin for color toners as set forth in claim 1, wherein the softening point is not more than 130 degrees centigrade.
6. The binder resin for color toners as set forth in claim 1, wherein said releasing agent in said binder resin is dispersed with an average diameter of not miore uhan 1 mioro-m_eter.
7. The binder resin for color toners as set forth in claim 1, satisfying the following cc^nditicns: said carboxyl group-containing vinyl resin (C) contains a high molecular weight vinyl resin (.4) in ivhich the THF soluble portion has a peak in the miolecular weight region of not less than 150,000 and less than 350,000 in the GPC chrom.atogram. and a low molecular weight vinyl resin (L) in which the THF soluble portion has a peak in the m.olecular weight region of nor less than 20,000 and less than 40,000 in the GPC chromarogram.;
the mass ratio (H/L) of the high m.olecular v/eight vinyl resin (H) to the low molecular v/eight vinyl resin (L) in said carboxyl group-containing vinyl resin (C) is from. 10/90 to 30/70;

the acid value of the high molecular weight vinyl resin (H) in said carboxyl group-containing vinyl resin (C) is not less than 10 mgKOH/g and not more ttian 26 ngKOH/g and the acid value of the low molecular weight vinyl resm (L) is nor less than 6 mgKOH/g and not m.ore than 3 0 mgKOH/g;
the acid value of said carboxyl group-containing vinyl resin (C) is not less than 6 mgKCH/g and not more than 30 mgKOH/g;
the TKF soluble portion m said glycidyl group-containing vinyl resin (E) has a peak in the m.olecular weight region of nor less man 20,000 and not more than 8 0,000 in the GPC chromatogram and v,':ie epoxy value of said glycidyl groun-conraining vinyl resin (E) is not less than 0.003 Eq/lOOg and not more than 0.022 Eq/lGOg;
rhe mass ratio (C/E) of said carboxyl group-containing vinyl resin {C) to said glycidyl group-containing vinyl resin (E) is from 87/13 to 9 9/1.
S . The binder resin for color toners as set forth in claim 1, wherein the binder resin contains a block copolym.er comprising:
a block comprising a sequence of ethylenically unsaturated hydrocarbon derived consurtuent units and/or conjugated diene type hydrocarbon-derived constituent units, and
a block comiprising a sequence of styrene-derived constituent units, and/or
the hydrogenated product of the block copolymer, in an amount of not less than 0.05 mass % and not more than 0.6 mass % based on 100 mass % of said carboxyl group-containing vinyl resin (C).
9. A method for producing the binder resin for color toners as set
forth In claim 7, comprising a polymerizing said low m.olecnlar
weight vinyl resin (L; in tnc presence of at least one of releasing
agents having a m.eltlng point of not lower than 60 degrees
centigrade and not higher than 12 0 degrees centigrade, and an
am.ount of not less than 2 mass % and not more than 13 mass % based
on 100 mass % of the constltuenr mionomer of said low molecular
weight vinyl resin (L).
10. A method for producing the binder resin for color toners as
set forth in claim. 1, comprising a m.elt-kneading at least one of
the carboxyl group-containing vinyl resins (C) and at least one
of the glycidyl grouo-containing vinyl resins (E) at a temperature
range of not lower than 14 0 degrees centigrade and not higher than
210 degrees centigrade, ano reacting a carboxyl group with a
glycidyl group.
11. A color toner comprising at least the binder resin for color toners as set forth in claim 1, a coloring agent and a charge controlling agent.
12. The color toner as set forth m claim 11, wherein said color toner- is obtained by a grinding miethod .
13. The color toner as set forth in claim 11 or 12, wherein the storaae miodulus G' at 160 degrees centigraide is not less than 100

and less than 8 00 Pa measured at a frequency of 6.2 8 rad/sec.
14. A binder resin for color toners, v^herein the binder resin comprises at least a carboxyl group-containing vinyl resin (C), a glycidyl group-containing viny]. resin (E) and a reaction product thereof,
the storage modulus G' at 160 degrees centigrade is not less than 20 Pa and less than 800 Pa meuaired an a frequency of 6.28 rad/sec,
the tetrahydrofuran (THE) soluble portion in the binder resin has a main peak in the molecular weight region of not less than 20,000 and less than 40,000 in the molecular weight distribution measured by gel permieation chromiatography (GPC) ,
the binder resin contains at least one of releasing agents having a melting point of not lower than 60 degrees centigrade and not higher than 120 degrees centigrade in an amount of not less than 3.5 mass land not more than 12 mass % based on 100 mass % of the total am.ount of said carboxyl group-containing vinyl resin (C), said glycidyl group-containing vinyl resin (E) and a reaction product thereof,
rhe integrated value of the content of the tetrahydrof uran (THE) soluble portion in the binder resin in the molecular weight region of not more than 2,000 is not more than 7.0 mass % based on the tonal THE soluble portion, an:]
the v/eight-average molecular weight (Mw) is not more than 170,000 and the weight-average miolecular weight (Mw)/the number-average molecular weignt (Mn) is not less than 5 and not more than 4 0.

15. Ihe binder resi.n for color toners as set torth in claim 14, wherein the contenc of a volar i].e component remained in said binder
.6. The binder resin to: cclo]; toners as set forth in claim 11, dierein the softenJnrq point: is not more than 130 degrees
ntrgxade.
1^. The bir;der resin for color toners as set forth in claim 14, wherein said releasing agent, in said binder resin is dispersed with an average diameter of not more than 1 micro-meter.
13. The binder resin for color toners as set forth in claim. 14, sanlsfying the fol].owing conditions: said carboxyl group-containing vinyl resin (C) contains a high molecular weight vinyl resin (H) in wlnich the THF soluble portion has a peak in the molecular vjeight region of not less than 150,000 and less than 350,000 in one GPC chromatogram. and a low molecular weight vinyl resin (L) rn w^hich the THF soluble portion has a peak in the molecular weight region of not less than 20, 000 and less than 40, 000 in the GPC chromatogram;
the mass ratio (H/L) of ohe high m.olecular weight vinyl .resin (H) to the low molecular v.e ' get vinyl resin (L) in said carboxyl group-containing vinyl resin (C) is from 10/90 to 30/70;
the acid value of the high m.olecular weight vinyl resin (H) in said carboxyl group-containing vinyl .resin (C) is not less than

10 mgKOH/g and not more th.an 2 6 mgKOH/g and the acid value of the low molecular weight vinyl resin (L) is not less than 6 mgKOH/g and not more than 3 0 m.gKOH/g;
rhe acid value of said carooxyl group-containing vinyl resin (C) is not less than 6 mgKOH/g and not m.ore than 30 mgKOH/g;
the THF soluble portion in said glycidyl group-containing vinyl resin (E) has a peak m the molecular weight region of not less than 20,000 and nor more than 80,000 in the GPC chromiatogrami and the epoxy value of said glycidyl group-containing vinyl resin :E) is not less rhan 0.003 Eq/100g and not m.ore than G.022 Eq/lOOg;
a n a
tiie mass ratio (C/E) of said carboxyl group-containing vinyl m (C] to said glycidyl group-conraining vinyl resin (E) is from

37/13 to

;.' rj! _.

19, The binder resin for color toners as set forth in claimi 14,
wherein the binder resin conrains a block copolymer comiprising:
a block comprising a sequence of ethylenically unsaturated hydrocarbon derived constituent units and/or conjugated diene type hydrocarbon-derived constituent unrts, and
a block com.prising a sequence of styrene-derived constituent unirs, and/or
the hydrogenated product of the block copolymer, in an amount of not less than 0.05 mass % and not more than 0.6 mass % based on 100 mass % of said carboxy group-containing vinyl resin (C) .
20. A method for producing the binder resin for color toners as

set forth in claim 18, comprising a polym.erizing said low molecular weight vinyl resin (L) in the presence of at least one of releasing agents having a melting point of not lower than 60 degrees centigrade and not higher than 120 degrees centigrade, and an amount of not less than 2 mass % and not more than 13 m.ass % based on 100 mass % of the constituent monomer of said low molecular weight vinyl resin (L) ,
21. A method for producing the binder resin for color toners as set forth in claim 14, comprising a melt-kneading at least one of the carboxyl group-containing vinyl resias (C) _and at least one of the glycidyl group-containing vinyl resins (E) at a temperature range of not lower than 140 degrees centigrade and not higher than 210 degrees centigrade, and reacting a carboxyl group with a glycidyl group.
22. A color toner com.prising at least the binder resin for color toners as set forth in claim 14, a coloring agent and a charge controlling agent.
23. The color toner as set forth in claim 22, wherein the color toner is obtained by a grinding method.

24. The color toner as set forth in claim. 22 or 23, wherein the storage miodulus G' at 160 degrees centigrade is not less than 100 Pa and less than 800 Pa measured at a freguency of 6.28 rad/sec.