CN1178109C - Toner for electrostaic image development, electrostatic image developer and imaging method thereof - Google Patents
Toner for electrostaic image development, electrostatic image developer and imaging method thereof Download PDFInfo
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- CN1178109C CN1178109C CNB981251250A CN98125125A CN1178109C CN 1178109 C CN1178109 C CN 1178109C CN B981251250 A CNB981251250 A CN B981251250A CN 98125125 A CN98125125 A CN 98125125A CN 1178109 C CN1178109 C CN 1178109C
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- toner
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- latent image
- aromatic hydrocarbon
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- 238000003384 imaging method Methods 0.000 title abstract description 5
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- 239000003208 petroleum Substances 0.000 claims abstract description 73
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 58
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 40
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 20
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- -1 m-pentadiene Chemical compound 0.000 claims description 43
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- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
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- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 1
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- Developing Agents For Electrophotography (AREA)
Abstract
The present invention relates to a toner for electrostatic image development, an electrostatic image developer and an imaging method thereof by the developer. The toner for electrostatic image development comprises a coloring agent, adhesive resin and copolymerization petroleum resin of fatty hydrocarbon, namely aromatic hydrocarbon with the carbon number of more than nine. The electrostatic image developer is composed of a carrier and the toner. The Imaging method has the working procedure of forming a keeping body of an electrostatic latent image and an electrostatic latent image by the developer, and the working procedure of developing the electrostatic latent image on the keeping body of an electrostatic latent image by a developer layer on the carrier of the developer.
Description
The present invention relates to a kind of toner for developing electrostatic latent image that is used for xerography, electrostatic recording, videograph etc., use the electrostatic charge image developer of this toner for developing electrostatic latent image and use the formation method of this electrostatic charge image developer.
The photographic fixing mode of existing toner for developing electrostatic latent image, what extensively adopt is the warm-up mill mode, but in recent years along with the high speed of duplicating machine, the requirement of low power consumingization, propose in order to improve the thermal efficiency of warm-up mill, with the roller minor diameterization with carry out the motion of photographic fixing by film.And since the warm-up mill mode be roller directly with fusion toner contact, transfer to the roller surface so toner takes place easily, be transferred to again on the duplicatings body such as paper and cause the duplicating pollution, heat penetration promptly takes place easily print phenomenon.
In order to keep low-temperature fixing, to prevent heat penetration seal phenomenon, the viscoelastic method when having proposed to enlarge molecular weight distribution, the fusion of control toner of the binding resin that constitutes toner and in toner, add release agent such as paraffin, reduce the method for the bounding force of warm-up mill and film.But these methods can not be controlled the dispersiveness of paraffin fully.At release agent is under the situation of polyolefin paraffin, because polyolefin is dissolved in the toner hardly, so be difficult to disperse, forms bigger polyolefin distribution range in vibrin.During pulverizing, pulverized at this zone toner, polyolefin easily exposes or dissociates on the surface of toner.Particularly under the situation of using magnetic developer, polyolefin pollutes toner carrier (axle), and it is inhomogeneous that the toner transmission can take place, and the charged ability of giving reduces, and causes that image color reduces.In the small-sized machine that uses the magnet unit developer, owing to need to reduce the price of machinery itself, to do very simply so clean the mechanism of photoreceptor, the polyolefin paraffin that has dissociated pollutes photoreceptor, causes that image is damaged.Therefore caused the anti-print through of toner bad, powder fluidity and paraffin composition are to secondary drawbacks such as photoreceptor, carrier transfers.Still left over above-mentioned open question at present.
Promptly in No. 86699/1995 communique of patent announcement, recorded in No. 86700/1995 communique of patent announcement, No. 86701/1995 communique of patent announcement by importing cross-linked structure, satisfy low-temperature fixing, comminuted, anti-adhesive technology thereby the vibrin that has enlarged molecular weight distribution used with binding resin as toner.But in order to satisfy anti-print through fully, need be with release agents such as low-molecular-weight polypropylenes, fine being dispersed in the vibrin, but the intermiscibility of the stronger vibrin of paraffin such as low-molecular-weight polypropylene and polarity is bad, is difficult to disperse equably.
In order to address this problem, in No. 244402/1995 communique of patent disclosure, record use and have the oxidized form polyolefin paraffin of polar group in molecular end, strengthen the intermiscibility of vibrin and paraffin, improve the technical scheme of paraffin dispersiveness.In the method, use oxidized form polyolefin paraffin, can improve the dispersiveness of paraffin, but the powder fluidity of toner and hot keeping quality worsen.No. 199534/1995 communique of patent disclosure records the motion that aliphatic petroleum resin is used as release agent, but has the powder fluidity of toner and the problem of hot keeping quality difference equally.Moreover because vibrin self tough, be restricted on comminuted improving, so, must make the toner of small particle diameter, so just reduced production efficiency widely in order to obtain the high-quality copy image.
In order to address the above problem, in No. 257868/1992 communique of patent disclosure, put down in writing the compatible comminuted and hot keeping quality technology of use aromatic petroleum resin, in No. 278658/1996 communique of patent disclosure, disclose the compatible comminuted and hot conservatory technical scheme of use hydrogenated petroleum resin, can improve comminuted in the above-mentioned technology but do not improve the dispersiveness of release agent, also produce the problem that the charging property of toner worsens.
Fundamental purpose of the present invention is, a kind of toner for developing electrostatic latent image, electrostatic charge image developer are provided, and it can compatible comminuted and hot retentivity, has good low-temperature fixing and anti-print through.
Another object of the present invention is to, a kind of toner for developing electrostatic latent image, electrostatic charge image developer and formation method are provided, it can not produce image deflects because of the film forming to photoreceptor, can not produce defectives such as charging property difference because of the impulsive force (イ Application パ Network シ ョ Application) to carrier.
To achieve these goals, electrostatic image toner for developing of the present invention contains colorant, binding resin and the aliphatic hydrocarbon-carbon number aromatic hydrocarbon copolymerization petroleum resin more than 9.
In addition, electrostatic image developer of the present invention is in the electrostatic charge image developer that is made of carrier and toner, and this toner contains colorant, binding resin, the aliphatic hydrocarbon-carbon number aromatic hydrocarbon copolymerization petroleum resin more than 9.
Formation method of the present invention, have the operation that forms electrostatic latent image maintenance body and electrostatic latent image and on developer carrier, using developer layer, aforementioned electrostatic latent image is kept in the formation method of operation of the electrostatic latent image development on the body, and aforementioned image developer contains colorant, binding resin, the aliphatic hydrocarbon-carbon number aromatic hydrocarbon copolymerization petroleum resin more than 9.
By adding the aromatic hydrocarbon copolymerization petroleum resin of aliphatic hydrocarbon-carbon number more than 9 that use in the present invention, these petroleum resin play a part the disperse additive as paraffin, so can improve significantly the paraffin kept in the resin disperses, low-temperature fixing is constant anti-print through, comminuted, by paraffin film forming to image-carrier, the reason that can significantly improve owing to charged difference causes that image color reduces, passes through the film forming to photoreceptor, can significantly improve by the damaged phenomenon of image of seal body and take place.In addition, when adding magnetic developer, also can obtain same effect.
The aromatic hydrocarbon copolymerization petroleum resin of aliphatic hydrocarbon-carbon number more than 9 that the present invention uses, with diolefin and mono-olefin is raw material and synthetic, this diolefin and mono-olefin are included in by the steam cracking of petroleum-type and make ethene, in the decomposition oil distillate of by-product, preferably select for use in the ethylene units such as propylene from isoprene, m-pentadiene, 2-methyl butene-1, at least a above aliphatic hydrocarbon monomer of selecting in the 2-methyl butene-2 and from vinyltoluene, α-Jia Jibenyixi, indenes, at least a above aromatic hydrocarbon monomer of selecting in the isopropenyl toluene carries out the co-polymer that copolymerization forms.
If use the high pure monomer of monomer purity, so the foul smell in the time of can suppressing the painted of resin and heating better is even more ideal as the aromatic hydrocarbon monomer.The purity of aromatic hydrocarbon monomer is better more than 95%, then better more than 98%.Constitute by the monomer of carbon number more than 9 at the aromatic hydrocarbon monomer, and when obtaining the copolymerization petroleum resin by this monomer and aliphatic hydrocarbon monomer, with be lower than the copolymerization petroleum resin that 9 aromatic hydrocarbon and aliphatic hydrocarbon monomer obtain by carbon number and compare, with binding resin, for example the intermiscibility of vibrin is higher.
And then in order to satisfy the comminuted and hot retentivity of toner, the formation as the aromatic hydrocarbon co-polymer of aliphatic hydrocarbon-carbon number more than 9 mostly is with the aromatic hydrocarbon amount of monomer.But if the aromatic hydrocarbon amount of monomer is too much, the dispersed variation of release agent, on the other hand, if the aliphatic hydrocarbon amount of monomer is too much, hot retentivities etc. can reduce, so the weight ratio of aromatic hydrocarbon amount of monomer and aliphatic hydrocarbon amount of monomer be 99: 1 to 50: 50 o'clock more suitable, be 98: 2 to 60: 40 o'clock better, be 98: 2 to 90: 10 o'clock best.
Even aliphatic hydrocarbon-carbon number used in the present invention is the aromatic hydrocarbon copolymerization petroleum resin low-molecular-weight more than 9, its glass branchpoint is also high, and then it is good with the intermiscibility balance of various resins, elastic body, paraffin, by with the binding resin melting mixing, can compatible hot retentivity and comminuted, also can not produce harmful effect to the charged characteristic of toner.
And then, use the used aliphatic hydrocarbon-aromatic hydrocarbon copolymerization petroleum resin of the present invention, binding resin and in order to prevent the paraffin of print through, because the aromatic hydrocarbon copolymerization petroleum resin of aliphatic hydrocarbon-carbon number more than 9 play a part the spreading agent as paraffin, so the paraffin that can improve significantly in the resin disperses, improve significantly and keep the constant anti-print through of low-temperature fixing, comminuted good, also can improve for photoreceptor, duplicate the damaged situation of volume image and improve the situation that makes the charging property variation for carrier owing to impulsive force because the film forming of paraffin makes.
As the use amount of the aromatic hydrocarbon copolymerization petroleum resin of aliphatic hydrocarbon-carbon number used herein more than 9, are 2 to 50 weight portions for toner binding resin 100 weight portions.3 to 30 weight portions preferably.When aforementioned petroleum resin amount is lower than 2 weight portions, the dispersion of paraffin there is not effect, if when being higher than 50 weight portions, the easy mistake of toner pulverized, and the toner particle diameter in the developing machine diminishes, and image blurring, image color is low, the development reduction.
The global formula softening point of the aromatic hydrocarbon copolymerization petroleum resin of aliphatic hydrocarbon-carbon number used in the present invention more than 9,80 to 170 ℃ better, 100 to 150 ℃ best.When softening point is lower than 80 ℃, hot retentivity variation, when softening point is higher than 170 ℃, the low-temperature fixing variation.
Be meant the value of measuring according to JIS K6863-1994 (the softening point test method of heat fusing cementing agent) at this said ring type softening point.
As binding resin used in the present invention, can use existing known resin.For example can select vibrin, styrene resin, styrene-(methyl) acryl resin, styrene-butadiene resin, epoxy resin, urethane resin etc.From low-temperature fixing, preferably select vibrin for use.
Vibrin used in the present invention can synthesize by polyvalent alcohol composition and poly carboxylic acid composition are concentrated.Can enumerate ethylene glycol, propylene glycol, 1 as employed polyvalent alcohol composition, 3-butylene glycol, 1,4-butylene glycol, 2,3-butylene glycol, diethylene glycol, triethylene glycol, 1, the 5-butylene glycol, 1,6-hexylene glycol, neopentyl glycol, cyclohexanedimethanol, hydrogenation bisphenol-A, bisphenol-A ethylene oxide addition product, the bisphenol-A third alkylene oxide addition product etc.As the polyvalent alcohol composition, can enumerate maleic acid, fumaric acid, phthalic acid, m-phthalic acid, terephthalic acid (TPA), succinic acid, dodecylene succinic acid, triphen six (first) acid, petroleum benzene six (first) acid, thiacyclohexane tricarboxylic acids, 2,5,7-naphthalene tricarboxylic acids, 1,2,4-naphthalene tricarboxylic acids, 1,2,5-hexane tricarboxylic acids, 1,3-dicarboxyl-2-methylene carboxyl propane tetramethylene carboxylic acid and acid anhydride thereof.
The softening point of binding resin used in the present invention, 80 to 150 ℃ are better, and 100 to 140 ℃ are better.When the softening point of binding resin is lower than 80 ℃, hot retentivity variation, if when being higher than 150 ℃, the low-temperature fixing variation.The glass branchpoint of binding resin is preferably 55 to 75 ℃.When the glass branchpoint is lower than 55 ℃, hot retentivity variation, if when being higher than 75 ℃, the low-temperature fixing variation.
As paraffin used in the present invention (release agent), can enumerate the fatty acid wax etc. of the paraffin, Carnauba wax, montanic acid ester type waxes etc. of aliphatics hydrocarbon systems such as low molecular weight polyethylene, low-molecular-weight polypropylene, microcrystalline wax, paraffin wax.Wherein, select for use low molecular weight polyethylene, aliphatic hydrocarbon through-stone wax better, select for use low molecular weight polyethylene then better.By using low molecular weight polyethylene, can obtain embrocating the good toner of image intensity after the photographic fixing, can prevent because the automatic friction original copys such as standardized writing paper with squares or lines device and the interior paper-feed roll of duplicating machine that transmit cause to wipe and rub imaging surface, increase dirty or image contamination etc., image quality is reduced.
Paraffin used in the present invention (release agent), the heat absorption peak of DSC are better in 70 ℃ to 100 ℃ scopes, and is then better in 80 ℃ to 95 ℃ scopes.Have the paraffin at the heat absorption peak of this low-temperature region by use, can improve release property at low-temperature region, suppress since separation claw cause peel off scratch, can not damage the good low-temperature fixing of vibrin, but and guarantee broad fixing temperature zone.When the heat absorption peak is lower than 70 ℃, hot retentivity variation, during in 100 ℃, can not obtain the release property of sufficient low-temperature region at the heat absorption peak height.In addition, the heat absorption peak of DSC herein is to use DSC-50 (Shimadzu Seisakusho Ltd.'s system), and the intensification degree is measured with 10 ℃/min, the temperature as the heat absorption peak when the highest.
The use amount of these release agents, the toner resin composition of per 100 weight portions is 0.1 to 20 weight portions, preferably 2 to 10 weight portions.If the use amount of release agent is lower than 0.1 weight portion, the release property of toner reduces, if be higher than 20 weight portions, the charging property of toner, hot retentivity reduce.
As toner of the present invention, can use known colorants such as carbon black, phthalocyanine blue, quinoline a word used for translation ketone, benzidine yellow.
Toner of the present invention also can add charged controlling agent, magnetic etc. as required.As charged controlling agent, can use chromium azo color series, iron azo color series, aluminium azo dyes, salicylic acid metal complex etc.
As magnetic, can use metal alloy, Fe such as ferromagnetism metal, cobalt, iron, nickel, aluminium, lead, magnesium, zinc, manganese such as cobalt, iron, nickel
3O
4, γ-Fe
2O
3, add known magnetics such as various ferrites such as metal oxide, MnZn ferrite, NiZn ferrite, four oxidations, two iron, haematite such as cobalt oxidation iron.And select for use their surface is handled with surface conditioning agents such as organosilane coupling agent, titanate organosilane coupling agents, or it is then better to use polymer-coated.
The blending ratio of Magnaglo is overall for toner, and is better, better in 35 to 65 weight % scopes in 30 to 70 weight % scopes.When Magnaglo was lower than 30 weight %, toner carrier was because the magnetic body, reduced for the sorptive force of toner, produced toner and dispersed, wipes problem such as rub.On the other hand, if when being higher than 70 weight %, exist the problem that image color reduces.In addition, the mean grain size of these Magnaglos is considered from the dispersiveness of binding resin, preferably in 0.05 to 0.35 mu m range.
For toner of the present invention,, also can add flowing agent and handle at surfaces of toner particles.As flowing agent, can use known inorganic fine particles such as silicon dioxide particles that the surface handled through hydrophobization, titanium oxide microparticle, alumina particulate.
Manufacture method as toner of the present invention, available Henschel mixer, as required, with release agent, colorant, charged controlling agent, after binding resin, the aliphatic hydrocarbon-carbon number aromatic hydrocarbon copolymerization petroleum resin more than 9 mix, carry out melting mixing with mixing rolls such as extruders, after mixing thing cooling, use the beating crusher coarse crushing, broken with the jet mill micro mist, use the air classifier split pole, flowing agent is mixed, make toner with Henschel mixer.
Electrostatic charge image developer of the present invention is that the two components that are made of above-mentioned toner and carrier are developer.For carrier, be not particularly limited, can use known carrier, for example the carrier of coated with resin.This coated with resin carrier is the resin that has been covered on the surface of core, as core, can enumerate the powder that for example iron powder, ferrite powder, nickel powder etc. have magnetic.As the resin that is overlayed on the core surface, can enumerate for example fluororesin, vinylite, silicone-based resin etc.
In addition, electrostatic charge image developer of the present invention according to purpose, also can contain the adjuvant of suitable selection etc.For example, be purpose to obtain magnetic, also can contain ferromagnetic metal, alloy that shows iron class, nickel, cobalt etc. or compound, magnetic material, the magnetisable material that contains these metals.
Image forming method of the present invention, have the operation that forms electrostatic latent image and keep body and electrostatic latent image, the developer layer on the use developer carrier, when making aforementioned electrostatic latent image keep the formation method of operation of the electrostatic latent image development on the body, aforementioned developer is to use the electrostatic charge image developer that contains the aromatic hydrocarbon copolymerization petroleum resin of above-mentioned aliphatic hydrocarbon-carbon number more than 9, in this image forming method, can directly bring into play the advantage of above-mentioned electrostatic charge image developer.
Below, use embodiment, explain the present invention, but the present invention is not subjected to the restriction of these embodiment.
In addition, be used for aliphatic hydrocarbon-aromatic hydrocarbon copolymerization petroleum resin of embodiment, as follows.
(A): C
5Through-stone oil distillate (isoprene)/C
5Through-stone oil distillate (m-pentadiene)/isopropenyl toluene=monomer weight ratio (1.5/1.5/97), softening point (125 ℃)
(B): C
5Through-stone oil distillate (isoprene)/C
5Isopropenyl toluene=the monomer weight ratio (1.5/1.5/97) of petroleum fraction (m-pentadiene)/purity 98%, softening point (125 ℃)
(C): C
5Indenes=the monomer weight ratio (3/50/47) of the isopropenyl toluene/purity 98% of through-stone oil distillate (isoprene)/purity 98%, softening point (150 ℃)
(D): C
5α-Jia Jibenyixi=the monomer weight ratio (5/50/45) of the isopropenyl toluene/purity 98% of through-stone oil distillate (isoprene)/purity 98%, softening point (125 ℃)
(E): C
5α-Jia Jibenyixi=the monomer weight ratio (30/35/35) of the isopropenyl toluene/purity 98% of through-stone oil distillate (isoprene)/purity 98%, softening point (115 ℃)
The softening point of aliphatic hydrocarbon-aromatic hydrocarbon copolymerization petroleum resin is represented global formula softening point.
In addition, the used paraffin (release agent) of embodiment is as follows.
Release agent A: Tissuemat E 1 (87.7 ℃ of fusing points)
(number-average molecular weight 1500)
Release agent B: Tissuemat E 2 (82.1 ℃ of fusing points)
(number-average molecular weight 1200)
Release agent C: oxidized polyethlene wax (90.3 ℃ of fusing points)
(number-average molecular weight 1000)
Release agent D: oxidized polyethlene wax (138.8 ℃ of fusing points)
(number-average molecular weight 3500)
Release agent E: polypropylene wax (142.6 ℃ of fusing points)
(number-average molecular weight 3000)
Release agent F: take a holder wax (85.0 ℃ of fusing points)
(number-average molecular weight 2000)
Release agent G: Carnauba wax (83.5 ℃ of fusing points)
(number-average molecular weight 2000)
Release agent H: paraffin wax (80.0 ℃ of fusing points)
(number-average molecular weight 1000)
In addition, fusing point is equivalent to the absorption heat peak of DSC.
Embodiment 1
Vibrin (bisphenol-A ethylene oxide addition product/bisphenol-A third alkylene oxide addition product/terephthalic acid (TPA)/fumaric acid condensation product, weight average molecular weight 6000,
100 ℃ of softening points, 58 ℃ of glass branchpoints, acid number 15) 84 weight portions
Aliphatic hydrocarbon-aromatic hydrocarbon copolymerization petroleum resin (A) 10 weight portions
Carbon black [adding the system BPL of Bert commercial firm (キ ヤ ボ Star ト society)] 6 weight portions
The melting mixing said mixture, then, calendering/cooling is carried out coarse crushing with the hammer comminution, and it is broken to carry out micro mist with jet mill, uses the air classifier classification, obtains the toner coatingparticles of volume average particle size 9.0 μ m.Use mixer,, mix, obtain toner particle with this toner coatingparticles of 100 weight portions with titanium dioxide 1.0 weight portions and hydrophobic silica 0.3 weight portion.
With above-mentioned toner particle 6 weight portions and on iron core carrier 100 weight portions of 50 μ m of coating 2% styrene/acrylic resin mix, obtain developer.
Embodiment 2
Except using aliphatic hydrocarbon-aromatic hydrocarbon copolymerization petroleum resin (B), replace outside aliphatic hydrocarbon-aromatic hydrocarbon copolymerization petroleum resin (A) of embodiment 1, other and embodiment 1 obtain toner and developer in the same manner.
Embodiment 3
Vibrin (bisphenol-A ethylene oxide addition product/bisphenol-A third alkylene oxide addition product/terephthalic acid (TPA)/fumaric acid/triphen six (first) acid/dodecylene succinic acid condensation product, weight average molecular weight 30000,
130 ℃ of softening points, 62 ℃ of glass branchpoints, acid number 15) 79 weight portions
Aliphatic hydrocarbon-aromatic hydrocarbon copolymerization petroleum resin (A) 10 weight portions
Release agent E 5 weight portions
Carbon black (adding the system BPL of Bert commercial firm) 6 weight portions
With said mixture, carry out 1 identical operations with embodiment, obtain toner particle and developer.
Embodiment 4
Vibrin (bisphenol-A ethylene oxide addition product/bisphenol-A third alkylene oxide addition product/terephthalic acid (TPA)/fumaric acid/triphen six (first) acid/dodecylene succinic acid condensation product, weight average molecular weight 30000,
130 ℃ of softening points, 62 ℃ of glass branchpoints, acid number 15) 86 weight portions
Aliphatic hydrocarbon-aromatic hydrocarbon copolymerization petroleum resin (B) 3 weight portions
Release agent E 5 weight portions
Carbon black (adding the system BPL of Bert commercial firm) 6 weight portions
With said mixture, carry out 1 identical operations with embodiment, obtain toner particle and developer.
Embodiment 5
Vibrin (bisphenol-A ethylene oxide addition product/bisphenol-A third alkylene oxide addition product/terephthalic acid (TPA)/fumaric acid/triphen six (first) acid/dodecylene succinic acid condensation product, weight average molecular weight 30000,
130 ℃ of softening points, 62 ℃ of glass branchpoints, acid number 15) 79 weight portions
Aliphatic hydrocarbon-aromatic hydrocarbon copolymerization petroleum resin (B) 10 weight portions
Release agent E 5 weight portions
Carbon black (adding the system BPL of Bert commercial firm) 6 weight portions
With said mixture, carry out 1 identical operations with embodiment, obtain toner particle and developer.
Embodiment 6
Vibrin (bisphenol-A ethylene oxide addition product/bisphenol-A third alkylene oxide addition product/terephthalic acid (TPA)/fumaric acid/triphen six (first) acid/dodecylene succinic acid condensation product, weight average molecular weight 30000,
130 ℃ of softening points, 62 ℃ of glass branchpoints, acid number 15) 69 weight portions
Aliphatic hydrocarbon-aromatic hydrocarbon copolymerization petroleum resin (B) 20 weight portions
Release agent E 5 weight portions
Carbon black (adding the system BPL of Bert commercial firm) 6 weight portions
With said mixture, carry out 1 identical operations with embodiment, obtain toner particle and developer.
Embodiment 7
Vibrin (bisphenol-A ethylene oxide addition product/bisphenol-A third alkylene oxide addition product/terephthalic acid (TPA)/fumaric acid/triphen six (first) acid/dodecylene succinic acid condensation product, weight average molecular weight 30000,
130 ℃ of softening points, 62 ℃ of glass branchpoints, acid number 15) 79 weight portions
Aliphatic hydrocarbon-aromatic hydrocarbon copolymerization petroleum resin (C) 10 weight portions
Release agent E 5 weight portions
Carbon black (adding the system BPL of Bert commercial firm) 6 weight portions
With said mixture, carry out 1 identical operations with embodiment, obtain toner particle and developer.
Embodiment 8
Vibrin (bisphenol-A ethylene oxide addition product/bisphenol-A third alkylene oxide addition product/terephthalic acid (TPA)/fumaric acid/triphen six (first) acid/dodecylene succinic acid condensation product, weight average molecular weight 30000,
130 ℃ of softening points, 62 ℃ of glass branchpoints, acid number 15) 79 weight portions
Aliphatic hydrocarbon-aromatic hydrocarbon copolymerization petroleum resin (D) 10 weight portions
Release agent E 5 weight portions
Carbon black (adding the system BPL of Bert commercial firm) 6 weight portions
With said mixture, carry out 1 identical operations with embodiment, obtain toner particle and developer.
Embodiment 9
Vibrin (bisphenol-A ethylene oxide addition product/bisphenol-A third alkylene oxide addition product/terephthalic acid (TPA)/fumaric acid/triphen six (first) acid/dodecylene succinic acid condensation product, weight average molecular weight 30000,
130 ℃ of softening points, 62 ℃ of glass branchpoints, acid number 15) 79 weight portions
Aliphatic hydrocarbon-aromatic hydrocarbon copolymerization petroleum resin (E) 10 weight portions
Release agent E 5 weight portions
Carbon black (adding the system BPL of Bert commercial firm) 6 weight portions
With said mixture, carry out 1 identical operations with embodiment, obtain toner particle and developer.
Embodiment 10
Except using styrene/acrylic butyl ester multipolymer (80/20, number-average molecular weight 3500, weight average molecular weight 300000), replace outside the vibrin, other and embodiment 5 obtain toner particle and developer in the same manner.
Comparative example 1
Vibrin (bisphenol-A ethylene oxide addition product/bisphenol-A third alkylene oxide addition product/terephthalic acid (TPA)/fumaric acid condensation product, weight average molecular weight 6000,
100 ℃ of softening points, 58 ℃ of glass branchpoints, acid number 15) 84 weight portions
The aliphatic hydrocarbon petroleum resin
(C5 through-stone oil distillate: isoprene/m-pentadiene=50/50) 10 weight portions
Carbon black (adding the system BPL of Bert commercial firm) 6 weight portions
With said mixture, carry out 1 identical operations with embodiment, obtain toner particle and developer.
Comparative example 2
Vibrin (bisphenol-A ethylene oxide addition product/bisphenol-A third alkylene oxide addition product/terephthalic acid (TPA)/fumaric acid condensation product, weight average molecular weight 6000,
100 ℃ of softening points, 58 ℃ of glass branchpoints, acid number 15) 84 weight portions
The aromatic hydrocarbon petroleum resin
(C9 through-stone oil distillate: α-Jia Jibenyixi) 10 weight portions
Carbon black (adding the system BPL of Bert commercial firm) 6 weight portions
Said mixture is carried out 1 identical operations with embodiment, obtain toner particle and developer.
Comparative example 3
Vibrin (bisphenol-A ethylene oxide addition product/bisphenol-A third alkylene oxide addition product/terephthalic acid (TPA)/fumaric acid/triphen six (first) acid/dodecylene succinic acid condensation product, weight average molecular weight 30000,
130 ℃ of softening points, 62 ℃ of glass branchpoints, acid number 15) 89 weight portions
Release agent E 5 weight portions
Carbon black (adding the system BPL of Bert commercial firm) 6 weight portions
Said mixture is carried out 1 identical operations with embodiment, obtain toner particle and developer.
Comparative example 4
Vibrin (bisphenol-A ethylene oxide addition product/bisphenol-A third alkylene oxide addition product/terephthalic acid (TPA)/fumaric acid/triphen six (first) acid/dodecylene succinic acid condensation product, weight average molecular weight 30000,
130 ℃ of softening points, 62 ℃ of glass branchpoints, acid number 15) 89 weight portions
Release agent D 5 weight portions
Carbon black (adding the system BPL of Bert commercial firm) 6 weight portions
Said mixture is carried out 1 identical operations with embodiment, obtain toner particle and developer.
Comparative example 5
Vibrin (bisphenol-A ethylene oxide addition product/bisphenol-A third alkylene oxide addition product/terephthalic acid (TPA)/fumaric acid/triphen six (first) acid/dodecylene succinic acid condensation product, weight average molecular weight 30000,
130 ℃ of softening points, 62 ℃ of glass branchpoints, acid number 15) 79 weight portions
The aliphatic hydrocarbon petroleum resin
(C5 through-stone oil distillate: isoprene/m-pentadiene=50/50) 10 weight portions
Release agent E 5 weight portions
Carbon black (adding the system BPL of Bert commercial firm) 6 weight portions
Said mixture is carried out 1 identical operations with embodiment, obtain toner particle and developer.
Comparative example 6
Vibrin (bisphenol-A ethylene oxide addition product/bisphenol-A third alkylene oxide addition product/terephthalic acid (TPA)/fumaric acid/triphen six (first) acid/dodecylene succinic acid condensation product, weight average molecular weight 30000,
130 ℃ of softening points, 62 ℃ of glass branchpoints, acid number 15) 79 weight portions
The aromatic hydrocarbon petroleum resin
(C9 through-stone oil distillate: α-Jia Jibenyixi) 10 weight portions
Release agent E 5 weight portions
Carbon black (adding the system BPL of Bert commercial firm) 6 weight portions
Said mixture is carried out 1 identical operations with embodiment, obtain toner particle and developer.
Comminuted for release agent dispersiveness, toner flowability, the hot retentivity of toner, the toner of the toner of above-mentioned embodiment that obtains 1 to 10 and comparative example 1 to 6 and development respectively, photoreceptor film forming, image color, fixation performance are estimated.
＜release agent dispersiveness 〉
Use the transparent type electron microscope, observe the toner section.No problem in the practicality be roughly below the 0.5 μ m.
＜toner flowability 〉
Start continuously with Fuji Xerox Co., Ltd (ゼ ロ Star Network ス society) system V500 transformation apparatus and to be determined at the toning dosage that falls from the toner tube in 1 minute.No problem in the practicality be roughly more than the 15g.
The hot retentivity of＜toner 〉
In 50 ℃, the environment of 50%RH, place after 24 hours, measure the toning dosage % that remains on the 106 μ m meshes (order is opened I メ Star シ ユ).No problem in the practicality be roughly below 5%.
The comminuted index of＜toner 〉
When pulverizing mixing meal with jet-O-Mizer and mince, the ratio (embodiment 1) that reaches 9.0 μ m quantity delivereds with volume average particle size (call meter (コ-Le カ ウ Application )-TA-II type, aperture are 100 μ m) calculates divided by other with this quantity delivered as 1.0.The comminuted index of toner is big more, easy more pulverizing, and in practicality, no problem is roughly more than 0.8.
＜photoreceptor film forming 〉
After duplicating 100,000 with Fuji Xerox Co., Ltd system V500 transformation apparatus, will be damaged by the image that the photoreceptor film forming causes, graduation (G5 bad → G1 is good)
Minimum image color in＜10 ten thousand 〉
Duplicating in 100,000, think the densimeter evaluation because the image color that developer variation (electric charge increases) causes reduces with Mike's ratio with Fuji Xerox Co., Ltd's system V500 transformation apparatus.In practicality, no problem is roughly more than 1.20.
Foul smell takes place during＜photographic fixing 〉
The smell of sensory evaluation during by the photographic fixing machine.
＜minimum fixing temperature 〉
Change fixing temperature with Fuji Xerox Co., Ltd's system V500 transformation apparatus, test.When solid images is made doubling, its level of visual grade evaluation.Mensuration reaches the minimum temperature of allowing level.In practicality, no problem roughly is below 135 ℃.
＜print through temperature 〉
The system V500 of Fuji Xerox Co., Ltd transformation apparatus changes fixing temperature, tests.Its print through level of visual grade evaluation.
Only on the fixing roller of embodiment 1, embodiment 2 and comparative example 1, comparative example 2, supply with oil in addition.
Its result is shown in table 1 and table 2.
Table 1
| Sequence number | The dispersion of release agent in the toner | The toner flowability | The hot retentivity of toner | The toner Hardgrove grindability index | The photoreceptor film forming | |||||
| Disperse particle diameter | Estimate | Mobile | Estimate | Hot retentivity | Estimate | Hardgrove grindability index | Estimate | Film forming | Estimate | |
| Embodiment 1 | - | - | 24g | ○ | 0.2 | ○ | 1 | ○ | G1 | ○ |
| Embodiment 2 | - | - | 24g | ○ | 0.2 | ○ | 1 | ○ | G1 | ○ |
| Embodiment 3 | 0.04μm | ○ | 22g | ○ | 0.3 | ○ | 1.2 | ○ | G1 | ○ |
| Embodiment 4 | 0.49μm | ○ | 19g | ○ | 0.5 | ○ | 0.9 | ○ | G1 | ○ |
| Embodiment 5 | 0.39μm | ○ | 22g | ○ | 0.3 | ○ | 1.2 | ○ | G1 | ○ |
| Embodiment 6 | 0.33μm | ○ | 24g | ○ | 0.2 | ○ | 1.4 | ○ | G1 | ○ |
| Embodiment 7 | 0.40μm | ○ | 23g | ○ | 0.2 | ○ | 1.1 | ○ | G1 | ○ |
| Embodiment 8 | 0.41μm | ○ | 22g | ○ | 0.3 | ○ | 1.2 | ○ | G1 | ○ |
| Embodiment 9 | 0.44μm | ○ | 19g | ○ | 0.4 | ○ | 1.2 | ○ | G1 | ○ |
| Embodiment 10 | 0.37μm | ○ | 23g | ○ | 0.3 | ○ | 1.4 | ○ | G1 | ○ |
| Comparative example 1 | - | - | 11g | × | 10.3 | × | 0.6 | × | G1 | ○ |
| Comparative example 2 | - | - | 20g | ○ | 0.3 | ○ | 0.9 | ○ | G1 | ○ |
| Comparative example 3 | 3.2μm | ×× | 7g | × | 20.1 | × | 0.4 | × | G4 | ×× |
| Comparative example 4 | 0.68μm | × | 11g | × | 31.3 | × | 0.36 | × | G2 | × |
| Comparative example 5 | 1.2μm | × | 8g | × | 35.8 | × | 1 | ○ | G3 | × |
| Comparative example 6 | 1.4μm | × | 11g | × | 28.7 | × | 0.8 | △ | G3 | × |
Table 2
| Sequence number | Print minimum image color in 100,000 | The foul smell that takes place during photographic fixing | Minimum photographic fixing concentration | The print through temperature | Overall merit | ||||
| Concentration | Estimate | Foul smell takes place | Estimate | Temperature | Estimate | Temperature | Estimate | ||
| Embodiment 1 | 1.35 | ○ | Have slightly | △ | 110℃ | ○ | 220 ℃ of actual no problems that use | ○ | ○ |
| Embodiment 2 | 1.36 | ○ | Do not have | ○ | 110℃ | ○ | 220 ℃ of actual no problems that use | ○ | ◎ |
| Embodiment 3 | 1.34 | ○ | Do not have | △ | 130℃ | ○ | Do not take place up to 250 ℃ | ○ | ○ |
| Embodiment 4 | 1.35 | ○ | Do not have | ○ | 130℃ | ○ | Do not take place up to 250 ℃ | ○ | ◎ |
| Embodiment 5 | 1.34 | ○ | Do not have | ○ | 130℃ | ○ | Do not take place up to 250 ℃ | ○ | ◎ |
| Embodiment 6 | 1.34 | ○ | Do not have | ○ | 133℃ | ○ | Do not take place up to 250 ℃ | ○ | ◎ |
| Embodiment 7 | 1.35 | ○ | Do not have | ○ | 133℃ | ○ | Do not take place up to 250 ℃ | ○ | ◎ |
| Embodiment 8 | 1.33 | ○ | Do not have | ○ | 130℃ | ○ | Do not take place up to 250 ℃ | ○ | ◎ |
| Embodiment 9 | 1.35 | ○ | Do not have | ○ | 128℃ | ○ | Do not take place up to 250 ℃ | ○ | ◎ |
| Embodiment 10 | 1.35 | ○ | Do not have | ○ | 136℃ | △ | Do not take place up to 250 ℃ | ○ | ○ |
| Comparative example 1 | 1.30 | ○ | Do not have | ○ | 110℃ | ○ | 220 ℃ of actual no problems that use | ○ | × |
| Comparative example 2 | 1.30 | ○ | Have slightly | △ | 140℃ | × | 220 ℃ of actual no problems that use | ○ | × |
| Comparative example 3 | 0.87 | × | Do not have | ○ | 130℃ | ○ | Do not take place up to 250 ℃ | ○ | × |
| Comparative example 4 | 0.97 | × | Do not have | ○ | 130℃ | ○ | Do not take place up to 250 ℃ | ○ | × |
| Comparative example 5 | 1.01 | × | Do not have | ○ | 130℃ | ○ | Do not take place up to 250 ℃ | ○ | × |
| Comparative example 6 | 1.03 | × | Have slightly | △ | 130℃ | ○ | Do not take place up to 250 ℃ | ○ | × |
Show from table 1 and table 2, above-mentioned any one characteristic of embodiment 1 to 10 all is good, particularly during the aromatic hydrocarbon copolymerization petroleum resin of aliphatic hydrocarbon-carbon number more than 9, the embodiment that uses the high aromatic hydrocarbon monomer of carbon number more than 9 of purity 2,4,5,6,7,8,9 o'clock, do not produce foul smell during photographic fixing, as binding resin, when using vibrin (embodiment 1 to embodiment 9), be good on low-temperature fixing in addition.
Embodiment 11
Vibrin (bisphenol-A ethylene oxide addition product/bisphenol-A third alkylene oxide addition product/terephthalic acid (TPA)/fumaric acid/triphen six (first) acid/dodecylene succinic acid condensation product, weight average molecular weight 30000,
130 ℃ of softening points, 62 ℃ of glass branchpoints, acid number 15) 79 weight portions
Aliphatic hydrocarbon-aromatic hydrocarbon copolymerization petroleum resin (A) 10 weight portions
Release agent A 5 weight portions
Carbon black (adding the system BPL of Bert commercial firm) 6 weight portions
Said mixture is carried out 1 identical operations with embodiment, obtain toner particle and developer.
Embodiment 12
Vibrin (bisphenol-A ethylene oxide addition product/bisphenol-A third alkylene oxide addition product/terephthalic acid (TPA)/fumaric acid/triphen six (first) acid/dodecylene succinic acid condensation product, weight average molecular weight 30000,
130 ℃ of softening points, 62 ℃ of glass branchpoints, acid number 15) 79 weight portions
Aliphatic hydrocarbon-aromatic hydrocarbon copolymerization petroleum resin (B) 10 weight portions
Release agent A 5 weight portions
Carbon black (adding the system BPL of Bert commercial firm) 6 weight portions
Said mixture is carried out 1 identical operations with embodiment, obtain toner particle and developer.
Embodiment 13
Vibrin (bisphenol-A ethylene oxide addition product/bisphenol-A third alkylene oxide addition product/terephthalic acid (TPA)/fumaric acid/triphen six (first) acid/dodecylene succinic acid condensation product, weight average molecular weight 30000,
130 ℃ of softening points, 62 ℃ of glass branchpoints, acid number 15) 69 weight portions
Aliphatic hydrocarbon-aromatic hydrocarbon copolymerization petroleum resin (B) 20 weight portions
Release agent A 5 weight portions
Carbon black (adding the system BPL of Bert commercial firm) 6 weight portions
Said mixture is carried out 1 identical operations with embodiment, obtain toner particle and developer.
Embodiment 14
Vibrin (bisphenol-A ethylene oxide addition product/bisphenol-A third alkylene oxide addition product/terephthalic acid (TPA)/fumaric acid/triphen six (first) acid/dodecylene succinic acid condensation product, weight average molecular weight 30000,
130 ℃ of softening points, 62 ℃ of glass branchpoints, acid number 15) 89 weight portions
Aliphatic hydrocarbon-aromatic hydrocarbon copolymerization petroleum resin (B) 3 weight portions
Release agent A 5 weight portions
Carbon black (adding the system BPL of Bert commercial firm) 6 weight portions
Said mixture is carried out 1 identical operations with embodiment, obtain toner particle and developer.
Embodiment 15
Vibrin (bisphenol-A ethylene oxide addition product/bisphenol-A third alkylene oxide addition product/terephthalic acid (TPA)/fumaric acid/triphen six (first) acid/dodecylene succinic acid condensation product, weight average molecular weight 30000,
130 ℃ of softening points, 62 ℃ of glass branchpoints, acid number 15) 79 weight portions
Aliphatic hydrocarbon-aromatic hydrocarbon copolymerization petroleum resin (C) 10 weight portions
Release agent A 5 weight portions
Carbon black (adding the system BPL of Bert commercial firm) 6 weight portions
Said mixture is carried out 1 identical operations with embodiment, obtain toner particle and developer.
Embodiment 16
Vibrin (bisphenol-A ethylene oxide addition product/bisphenol-A third alkylene oxide addition product/terephthalic acid (TPA)/fumaric acid/triphen six (first) acid/dodecylene succinic acid condensation product, weight average molecular weight 30000,
130 ℃ of softening points, 62 ℃ of glass branchpoints, acid number 15) 79 weight portions
Aliphatic hydrocarbon-aromatic hydrocarbon copolymerization petroleum resin (D) 10 weight portions
Release agent A 5 weight portions
Carbon black (adding the system BPL of Bert commercial firm) 6 weight portions
Said mixture is carried out 1 identical operations with embodiment, obtain toner particle and developer.
Embodiment 17
Vibrin (bisphenol-A ethylene oxide addition product/bisphenol-A third alkylene oxide addition product/terephthalic acid (TPA)/fumaric acid/triphen six (first) acid/dodecylene succinic acid condensation product, weight average molecular weight 30000,
130 ℃ of softening points, 62 ℃ of glass branchpoints, acid number 15) 79 weight portions
Aliphatic hydrocarbon-aromatic hydrocarbon copolymerization petroleum resin (E) 10 weight portions
Release agent A 5 weight portions
Carbon black (adding the system BPL of Bert commercial firm) 6 weight portions
Said mixture is carried out 1 identical operations with embodiment, obtain toner particle and developer.
Embodiment 18
Vibrin (bisphenol-A ethylene oxide addition product/bisphenol-A third alkylene oxide addition product/terephthalic acid (TPA)/fumaric acid/triphen six (first) acid/dodecylene succinic acid condensation product, weight average molecular weight 30000,
130 ℃ of softening points, 62 ℃ of glass branchpoints, acid number 15) 79 weight portions
Aliphatic hydrocarbon-aromatic hydrocarbon copolymerization petroleum resin (B) 10 weight portions
Release agent B 5 weight portions
Carbon black (adding the system BPL of Bert commercial firm) 6 weight portions
Said mixture is carried out 1 identical operations with embodiment, obtain toner particle and developer.
Embodiment 19
Vibrin (bisphenol-A ethylene oxide addition product/bisphenol-A third alkylene oxide addition product/terephthalic acid (TPA)/fumaric acid/triphen six (first) acid/dodecylene succinic acid condensation product, weight average molecular weight 30000,
130 ℃ of softening points, 62 ℃ of glass branchpoints, acid number 15) 79 weight portions
Aliphatic hydrocarbon-aromatic hydrocarbon copolymerization petroleum resin (B) 10 weight portions
Release agent F 5 weight portions
Carbon black (adding the system BPL of Bert commercial firm) 6 weight portions
Said mixture is carried out 1 identical operations with embodiment, obtain toner particle and developer.
Embodiment 20
Vibrin (bisphenol-A ethylene oxide addition product/bisphenol-A third alkylene oxide addition product/terephthalic acid (TPA)/fumaric acid/triphen six (first) acid/dodecylene succinic acid condensation product, weight average molecular weight 30000,
130 ℃ of softening points, 62 ℃ of glass branchpoints, acid number 15) 79 weight portions
Aliphatic hydrocarbon-aromatic hydrocarbon copolymerization petroleum resin (B) 10 weight portions
Release agent G 5 weight portions
Carbon black (adding the system BPL of Bert commercial firm) 6 weight portions
Said mixture is carried out 1 identical operations with embodiment, obtain toner particle and developer.
Embodiment 21
Vibrin (bisphenol-A ethylene oxide addition product/bisphenol-A third alkylene oxide addition product/terephthalic acid (TPA)/fumaric acid/triphen six (first) acid/dodecylene succinic acid condensation product, weight average molecular weight 30000,
130 ℃ of softening points, 62 ℃ of glass branchpoints, acid number 15) 79 weight portions
Aliphatic hydrocarbon-aromatic hydrocarbon copolymerization petroleum resin (B) 10 weight portions
Release agent H 5 weight portions
Carbon black (adding the system BPL of Bert commercial firm) 6 weight portions
With said mixture, carry out 1 identical operations with embodiment, obtain toner particle and developer.
Comparative example 7
Vibrin (bisphenol-A ethylene oxide addition product/bisphenol-A third alkylene oxide addition product/terephthalic acid (TPA)/fumaric acid/triphen six (first) acid/dodecylene succinic acid condensation product, weight average molecular weight 30000,
130 ℃ of softening points, 62 ℃ of glass branchpoints, acid number 15) 89 weight portions
Release agent A 5 weight portions
Carbon black (adding the system BPL of Bert commercial firm) 6 weight portions
With said mixture, carry out 1 identical operations with embodiment, obtain toner particle and developer.
Comparative example 8
Vibrin (bisphenol-A ethylene oxide addition product/bisphenol-A third alkylene oxide addition product/terephthalic acid (TPA)/fumaric acid/triphen six (first) acid/dodecylene succinic acid condensation product, weight average molecular weight 30000,
130 ℃ of softening points, 62 ℃ of glass branchpoints, acid number 15) 79 weight portions
The aliphatic hydrocarbon petroleum resin
(C5 through-stone oil distillate: isoprene/m-pentadiene=50/50) 10 weight portions
Release agent A 5 weight portions
Carbon black (adding the system BPL of Bert commercial firm) 6 weight portions
With said mixture, carry out 1 identical operations with embodiment, obtain toner particle and developer.
Comparative example 9
Vibrin (bisphenol-A ethylene oxide addition product/bisphenol-A third alkylene oxide addition product/terephthalic acid (TPA)/fumaric acid/triphen six (first) acid/dodecylene succinic acid condensation product, weight average molecular weight 30000,
130 ℃ of softening points, 62 ℃ of glass branchpoints, acid number 15) 79 weight portions
The aromatic hydrocarbon petroleum resin
(C9 through-stone oil distillate: α-Jia Jibenyixi) 10 weight portions
Release agent A 5 weight portions
Carbon black (adding the system BPL of Bert commercial firm) 6 weight portions
With said mixture, carry out 1 identical operations with embodiment, obtain toner particle and developer.
Comparative example 10
Vibrin (bisphenol-A ethylene oxide addition product/bisphenol-A third alkylene oxide addition product/terephthalic acid (TPA)/fumaric acid/triphen six (first) acid/dodecylene succinic acid condensation product, weight average molecular weight 30000,
130 ℃ of softening points, 62 ℃ of glass branchpoints, acid number 15) 89 weight portions
The aliphatic hydrocarbon petroleum resin
(C5 through-stone oil distillate: isoprene/m-pentadiene=50/50) 10 weight portions
Release agent C 5 weight portions
Carbon black (adding the system BPL of Bert commercial firm) 6 weight portions
With said mixture, carry out 1 identical operations with embodiment, obtain toner particle and developer.
For the toner particle and the developer of the embodiment 11 to 21 that obtains as mentioned above, comparative example 7 to 10, carry out identical evaluation with embodiment 1 to 10, comparative example 1 to 6 respectively, and for peeling off the disappearance temperature of scratching, wiping and to rub image color and also estimate.
＜peel off the disappearance temperature of scratching 〉
With the system V500 of Fuji Xerox Co., Ltd transformation apparatus, change fixing temperature, carry out photographic fixing.Mensuration reaches to peel off on the image apex all black picture partly scratches the minimum temperature of no problem level in practicality.Minimum temperature no problem in the practicality is about below 135 ℃.
＜wipe and rub image color
Use the automatic manuscript handling device of the system V500 of Fuji Xerox Co., Ltd transformation apparatus, measure.With 5 original copys, be fixed on the device, estimate the 2nd later original copy with the method for visual grade evaluation.(G5 bad → G1 is good)
Its result is shown in table 3 and table 4.
Table 3
| Sequence number | The dispersion of release agent in the toner | The toner flowability | The hot retentivity of toner | The toner Hardgrove grindability index | The photoreceptor film forming | |||||
| Disperse particle diameter | Estimate | Mobile | Estimate | Hot retentivity | Estimate | Hardgrove grindability index | Estimate | Film forming | Estimate | |
| Embodiment 11 | 0.22μm | ○ | 20g | ○ | 0.5 | ○ | 1.0 | ○ | G1 | ○ |
| Embodiment 12 | 0.26μm | ○ | 20g | ○ | 0.5 | ○ | 1.0 | ○ | G1 | ○ |
| Embodiment 13 | 0.21μm | ○ | 22g | ○ | 0.4 | ○ | 1.2 | ○ | G1 | ○ |
| Embodiment 14 | 0.40μm | ○ | 17g | ○ | 0.8 | ○ | 0.8 | ○ | G1 | ○ |
| Embodiment 15 | 0.27μm | ○ | 21g | ○ | 0.3 | ○ | 0.9 | ○ | G1 | ○ |
| Embodiment 16 | 0.30μm | ○ | 20g | ○ | 0.5 | ○ | 1.0 | ○ | G1 | ○ |
| Embodiment 17 | 0.27μm | ○ | 18g | ○ | 0.7 | ○ | 1.0 | ○ | G1 | ○ |
| Embodiment 18 | 0.30μm | ○ | 18g | ○ | 0.7 | ○ | 1.0 | ○ | G1 | ○ |
| Embodiment 19 | 0.31μm | ○ | 18g | ○ | 0.7 | ○ | 1.0 | ○ | G1 | ○ |
| Embodiment 20 | 0.11μm | ○ | 17g | ○ | 0.7 | ○ | 1.0 | ○ | G1 | ○ |
| Embodiment 21 | 0.40μm | ○ | 18g | ○ | 0.4 | ○ | 1.0 | ○ | G1 | ○ |
| Comparative example 7 | 2.1μm | × | 7g | × | 32.4 | × | 0.4 | × | G5 | ×× |
| Comparative example 8 | 0.52μm | △ | 8g | × | 30.8 | × | 0.5 | × | G3 | × |
| Comparative example 9 | 1.42μm | × | 11g | × | 29.6 | × | 0.5 | ○ | G3 | × |
| Comparative example 10 | 1.20μm | × | 11g | × | 31.3 | × | 0.3 | × | G2 | △ |
Table 4
| Sequence number | Print minimum image color in 100,000 | The foul smell that takes place during photographic fixing | Minimum photographic fixing concentration | The print through temperature | Peel off the disappearance temperature of scratching | Image color is rubbed in wiping | Overall merit | ||||||
| Concentration | Estimate | Foul smell takes place | Estimate | Temperature | Estimate | Temperature | Estimate | Temperature | Estimate | Concentration | Estimate | ||
| Embodiment 11 | 1.33 | ○ | Have slightly | △ | 130℃ | ○ | Do not take place up to 250 ℃ | ○ | Do not take place | ○ | G0 | ○ | ○ |
| Embodiment 12 | 1.34 | ○ | Do not have | ○ | 130℃ | ○ | Do not take place up to 250 ℃ | ○ | Do not take place | ○ | G0 | ○ | ◎ |
| Embodiment 13 | 1.33 | ○ | Do not have | △ | 133℃ | ○ | Do not take place up to 250 ℃ | ○ | Do not take place | ○ | G1 | ○ | ◎ |
| Embodiment 14 | 1.28 | ○ | Do not have | ○ | 130℃ | ○ | Do not take place up to 250 ℃ | ○ | Do not take place | ○ | G0 | ○ | ◎ |
| Embodiment 15 | 1.34 | ○ | Do not have | ○ | 133℃ | ○ | Do not take place up to 250 ℃ | ○ | Do not take place | ○ | G0 | ○ | ◎ |
| Embodiment 16 | 1.35 | ○ | Do not have | ○ | 130℃ | ○ | Do not take place up to 250 ℃ | ○ | Do not take place | ○ | G0 | ○ | ◎ |
| Embodiment 17 | 1.31 | ○ | Do not have | ○ | 128℃ | ○ | Do not take place up to 250 ℃ | ○ | Do not take place | ○ | G0 | ○ | ◎ |
| Embodiment 18 | 1.30 | ○ | Do not have | ○ | 130℃ | ○ | Do not take place up to 250 ℃ | ○ | Do not take place | ○ | G0 | ○ | ◎ |
| Embodiment 19 | 1.31 | ○ | Do not have | ○ | 130℃ | ○ | Do not take place up to 250 ℃ | ○ | Do not take place | ○ | G2 | △ | ○ |
| Embodiment 20 | 1.30 | ○ | Have slightly | △ | 128℃ | ○ | Do not take place up to 250 ℃ | ○ | Do not take place | ○ | G2 | △ | ○ |
| Embodiment 21 | 1.31 | ○ | Do not have | ○ | 130℃ | ○ | Do not take place up to 250 ℃ | ○ | Do not take place | ○ | G2 | △ | ○ |
| Comparative example 7 | 0.80 | × | Do not have | ○ | 130℃ | ○ | Do not take place up to 248 ℃ | ○ | Do not take place | ○ | G0 | ○ | × |
| Comparative example 8 | 0.99 | × | Do not have | ○ | 130℃ | ○ | Do not take place up to 249 ℃ | ○ | Do not take place | ○ | G0 | ○ | × |
| Comparative example 9 | 1.00 | × | Have slightly | △ | 130℃ | ○ | Do not take place up to 250 ℃ | ○ | Do not take place | ×× | G0 | ○ | × |
| Comparative example 10 | 0.97 | × | Do not have | ○ | 130℃ | ○ | Up to 230 ℃ of generations | △ | 138℃ | × | G2 | △ | × |
The various characteristics of each embodiment 11 to 21 shown in table 3 and table 4 is good, particularly in the aromatic hydrocarbon copolymerization petroleum resin of aliphatic hydrocarbon-carbon number more than 9, use under the situation of the high aromatic hydrocarbon monomer of carbon number more than 9 of purity, when photographic fixing, do not produce foul smell, in addition, when tygon was used as release agent, it is good that image color is rubbed in its wiping.
Embodiment 22
Vibrin (bisphenol-A ethylene oxide addition product/bisphenol-A third alkylene oxide addition product/maleic anhydride/terephthalic acid (TPA) condensation product, weight average molecular weight 20000,
120 ℃ of softening points, 65 ℃ of glass branchpoints, acid number 15) 39.5 weight portions
Aliphatic hydrocarbon-aromatic hydrocarbon copolymerization petroleum resin (A) 6.0 weight portions
Release agent E 3.0 weight portions
Tri-iron tetroxide (particle diameter 0.2 μ m) 50.0 weight portions
The charged controlling agent of negative charging (iron content azo based dye) 1.5 weight portions
Using Henschel mixer, above-mentioned material is carried out powder mix, is 140 ℃ extruder by design temperature, after its mixing cooling, carry out coarse crushing, micro mist broken, obtain 50% particle volume diameter D
50It is the crushed material of 6.6 μ m.And then, this crushed material is carried out classification, obtain D
50=7.2 μ m, below the 5 μ m: 22% classification product.In toner classification product 100 weight portions that obtain, use Henschel mixer, add mean grain size 0.42 μ m, be 5 number % below the 0.2 μ m, be that magnetic 0.5 weight portion of 1 number % and the silicone oil of particle diameter 12nm are handled silica 1 .0 weight portion more than the 1.0 μ m, obtain toner.
With above-mentioned toner particle 6 weight portions and on iron core carrier 100 weight portions of 50 μ m of lining styrene/acrylic resin mix, obtain developer.
Embodiment 23
Vibrin (bisphenol-A ethylene oxide addition product/bisphenol-A third alkylene oxide addition product/maleic anhydride/terephthalic acid (TPA) condensation product, weight average molecular weight 20000,
120 ℃ of softening points, 65 ℃ of glass branchpoints, acid number 15) 43.5 weight portions
Aliphatic hydrocarbon-aromatic hydrocarbon copolymerization petroleum resin (A) 2.0 weight portions
Release agent E 3.0 weight portions
Tri-iron tetroxide (particle diameter 0.2 μ m) 50.0 weight portions
The charged controlling agent of negative charging (iron content azo based dye) 1.5 weight portions
With said mixture, carry out 22 identical operations with embodiment, obtain toner particle and developer.
Embodiment 24
Vibrin (bisphenol-A ethylene oxide addition product/bisphenol-A third alkylene oxide addition product/maleic anhydride/terephthalic acid (TPA) condensation product, weight average molecular weight 20000,
120 ℃ of softening points, 65 ℃ of glass branchpoints, acid number 15) 30.5 weight portions
Aliphatic hydrocarbon-aromatic hydrocarbon copolymerization petroleum resin (A) 15.0 weight portions
Release agent E 3.0 weight portions
Tri-iron tetroxide (particle diameter 0.2 μ m) 50.0 weight portions
The charged controlling agent of negative charging (iron content azo based dye) 1.5 weight portions
With said mixture, carry out 22 identical operations with embodiment, obtain toner particle and developer.
Embodiment 25
Vibrin (bisphenol-A ethylene oxide addition product/bisphenol-A third alkylene oxide addition product/maleic anhydride/terephthalic acid (TPA) condensation product, weight average molecular weight 20000,
120 ℃ of softening points, 65 ℃ of glass branchpoints, acid number 15) 39.5 weight portions
Aliphatic hydrocarbon-aromatic hydrocarbon copolymerization petroleum resin (B) 6.0 weight portions
Release agent E 3.0 weight portions
Tri-iron tetroxide (particle diameter 0.2 μ m) 50.0 weight portions
The charged controlling agent of negative charging (iron content azo based dye) 1.5 weight portions
With said mixture, carry out 22 identical operations with embodiment, obtain toner particle and developer.
Embodiment 26
Vibrin (bisphenol-A ethylene oxide addition product/bisphenol-A third alkylene oxide addition product/maleic anhydride/terephthalic acid (TPA) condensation product, weight average molecular weight 20000,
120 ℃ of softening points, 65 ℃ of glass branchpoints, acid number 15) 39.5 weight portions
Aliphatic hydrocarbon-aromatic hydrocarbon copolymerization petroleum resin (C) 6.0 weight portions
Release agent E 3.0 weight portions
Tri-iron tetroxide (particle diameter 0.2 μ m) 50.0 weight portions
The charged controlling agent of negative charging (iron content azo based dye) 1.5 weight portions
With said mixture, carry out 22 identical operations with embodiment, obtain toner particle and developer.
Embodiment 27
Vibrin (bisphenol-A ethylene oxide addition product/bisphenol-A third alkylene oxide addition product/maleic anhydride/terephthalic acid (TPA) condensation product, weight average molecular weight 20000,
120 ℃ of softening points, 65 ℃ of glass branchpoints, acid number 15) 39.5 weight portions
Aliphatic hydrocarbon-aromatic hydrocarbon copolymerization petroleum resin (D) 6.0 weight portions
Release agent E 3.0 weight portions
Tri-iron tetroxide (particle diameter 0.2 μ m) 50.0 weight portions
The charged controlling agent of negative charging (iron content azo based dye) 1.5 weight portions
With said mixture, carry out 22 identical operations with embodiment, obtain toner particle and developer.
Embodiment 28
Vibrin (bisphenol-A ethylene oxide addition product/bisphenol-A third alkylene oxide addition product/maleic anhydride/terephthalic acid (TPA) condensation product, weight average molecular weight 20000,
120 ℃ of softening points, 65 ℃ of glass branchpoints, acid number 15) 39.5 weight portions
Aliphatic hydrocarbon-aromatic hydrocarbon copolymerization petroleum resin (E) 6.0 weight portions
Release agent E 3.0 weight portions
Tri-iron tetroxide (particle diameter 0.2 μ m) 50.0 weight portions
The charged controlling agent of negative charging (iron content azo based dye) 1.5 weight portions
With said mixture, carry out 22 identical operations with embodiment, obtain toner particle and developer.
Comparative example 11
Vibrin (bisphenol-A ethylene oxide addition product/bisphenol-A third alkylene oxide addition product/maleic anhydride/terephthalic acid (TPA) condensation product, weight average molecular weight 20000,
120 ℃ of softening points, 65 ℃ of glass branchpoints, acid number 15) 55.5 weight portions
Release agent E 3.0 weight portions
Tri-iron tetroxide (particle diameter 0.2 μ m) 50.0 weight portions
The charged controlling agent of negative charging (iron content azo based dye) 1.5 weight portions
With said mixture, carry out 22 identical operations with embodiment, obtain toner particle and developer.
Comparative example 12
Vibrin (bisphenol-A ethylene oxide addition product/bisphenol-A third alkylene oxide addition product/maleic anhydride/terephthalic acid (TPA) condensation product, weight average molecular weight 20000,
120 ℃ of softening points, 65 ℃ of glass branchpoints, acid number 15) 39.5 weight portions
The aliphatic hydrocarbon petroleum resin
(C5 through-stone oil distillate: isoprene/m-pentadiene=50/50) 6.0 weight portions
Release agent E 3.0 weight portions
Tri-iron tetroxide (particle diameter 0.2 μ m) 50.0 weight portions
The charged controlling agent of negative charging (iron content azo based dye) 1.5 weight portions
With said mixture, carry out 22 identical operations with embodiment, obtain toner particle and developer.
Comparative example 13
Vibrin (bisphenol-A ethylene oxide addition product/bisphenol-A third alkylene oxide addition product/maleic anhydride/terephthalic acid (TPA) condensation product, weight average molecular weight 20000,
120 ℃ of softening points, 65 ℃ of glass branchpoints, acid number 15) 39.5 weight portions
The aromatic hydrocarbon petroleum resin
(C9 through-stone oil distillate: α-Jia Jibenyixi) 6.0 weight portions
Release agent E 3.0 weight portions
Tri-iron tetroxide (particle diameter 0.2 μ m) 50.0 weight portions
The charged controlling agent of negative charging (iron content azo based dye) 1.5 weight portions
With said mixture, carry out 22 identical operations with embodiment, obtain toner particle and developer.
Toner particle and the release agent dispersiveness of developer, minimum fixing temperature and print through temperature for the embodiment 22 to 28 that obtains as mentioned above, comparative example 11 to 13, carry out identical evaluation with embodiment 1 to 10 respectively, picture appraisal (image color, image striped, axle film forming, photoreceptor film forming), as described below.
＜picture appraisal 〉
Use the electrophotographic toner composition, under high temperature wets (30 ℃/RH 80%),, estimate more with the system duplicating machine ABLE of Fuji Xerox Co., Ltd 3321.
Evaluation content is the initial stage image quality and duplicates image quality after 5000.Image color is measured with the X-rite densimeter, for image quality, with the full images after duplicating 5000, estimates.
＜photoreceptor film forming 〉
With above-mentioned picture appraisal method, duplicated the film forming on the photoreceptor that produces behind 5000 copies with visual valuation.
＜axle film forming 〉
With above-mentioned picture appraisal method, with the film forming on the axle that produces behind 5000 copies of visual valuation duplicating.
Its result is shown in table 5 and table 6.
Table 5
| Sequence number | Release agent in the toner disperses | Minimum fixing temperature | The print through temperature | |||
| Disperse particle diameter | Estimate | Temperature | Estimate | Temperature | Estimate | |
| Embodiment 22 | 0.42μm | ○ | 130℃ | ○ | Do not take place up to 250 ℃ | ○ |
| Embodiment 23 | 0.48μm | ○ | 132℃ | ○ | Do not take place up to 251 ℃ | ○ |
| Embodiment 24 | 0.35μm | ○ | 133℃ | ○ | Do not take place up to 252 ℃ | ○ |
| Embodiment 25 | 0.41μm | ○ | 131℃ | ○ | Do not take place up to 253 ℃ | ○ |
| Embodiment 26 | 0.45μm | ○ | 130℃ | ○ | Do not take place up to 254 ℃ | ○ |
| Embodiment 27 | 0.46μm | ○ | 134℃ | ○ | Do not take place up to 255 ℃ | ○ |
| Embodiment 28 | 0.38μm | ○ | 133℃ | ○ | Do not take place up to 250 ℃ | ○ |
| Comparative example 11 | 2.5μm | × | 132℃ | × | Do not take place up to 250 ℃ | ○ |
| Comparative example 12 | 1.3μm | × | 132℃ | × | Do not take place up to 251 ℃ | ○ |
| Comparative example 13 | 0.8μm | × | 131℃ | × | Do not take place up to 250 ℃ | ○ |
Table 6
| Sequence number | Initial stage image quality (how down wet high temperature is) | Image quality after printing 5000 (how down wet high temperature is) | Overall merit | |||||
| Image color | The image striped | The photoreceptor film forming | The axle film forming | |||||
| Concentration (SDA) | Estimate | Concentration (SDA) | Estimate | |||||
| Embodiment 22 | 1.55 | ○ | 1.45 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 23 | 1.53 | ○ | 1.43 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 24 | 1.46 | ○ | 1.37 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 25 | 1.48 | ○ | 1.39 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 26 | 1.48 | ○ | 1.41 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 27 | 1.45 | ○ | 1.38 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 28 | 1.46 | ○ | 1.39 | ○ | ○ | ○ | ○ | ○ |
| Comparative example 11 | 1.32 | × | 0.85 | × | ×× | ×× | × | ×× |
| Comparative example 12 | 1.21 | × | 0.98 | × | × | × | × | × |
| Comparative example 13 | 1.15 | × | 0.87 | × | × | × | × | × |
Annotate) 1 image striped notes) 2 photoreceptor film forming and axle film forming
Zero does not take place can not use Visual Confirmation on zero photoreceptor
Have on * the image problem is arranged on problem * image slightly
On the * * image problem is arranged
Show by table 5 and table 6, in magnetic developer, add the aromatic hydrocarbon copolymerization petroleum resin of aliphatic hydrocarbon-carbon number more than 9, can improve above-mentioned each characteristic.
The present invention, can provide and take into account comminuted and hot retentivity, it is constant to keep sufficient low-temperature fixing, significantly improve anti-print through, comminuted good, can not take place to make toner for developing electrostatic latent image, electrostatic charge image developer and the formation method thereof that image is damaged, make the charging property variation owing to the impulsive force to carrier because of the photoreceptor film forming.
Claims (14)
1. toner for developing electrostatic latent image, it is characterized in that containing colorant, binding resin and the aliphatic hydrocarbon-carbon number aromatic hydrocarbon copolymerization petroleum resin more than 9, wherein, the aromatic hydrocarbon amount of monomer of the aromatic hydrocarbon copolymerization petroleum resin of aliphatic hydrocarbon-carbon number more than 9 and the weight ratio of aliphatic hydrocarbon amount of monomer are 99: 1 to 50: 50.
2. toner for developing electrostatic latent image according to claim 1 is characterized in that it contains paraffin.
3. toner for developing electrostatic latent image according to claim 2, the absorption heat peak value of DSC that it is characterized in that aforementioned paraffin is 70 to 100 ℃ scope.
4. toner for developing electrostatic latent image according to claim 1 is characterized in that for binding resin 100 weight portions, the copolymerization petroleum resin contain 2 to 50 weight portions.
5. toner for developing electrostatic latent image according to claim 1 is characterized in that described copolymerization petroleum resin have 80 to 170 ℃ global formula softening point.
6. toner for developing electrostatic latent image according to claim 1 is characterized in that binding resin is a vibrin.
7. toner for developing electrostatic latent image according to claim 3 is characterized in that binding resin is a vibrin.
8. toner for developing electrostatic latent image according to claim 1, the softening point that it is characterized in that described binding resin are that 80 to 150 ℃, glass transition temperature are 55 to 75 ℃.
9. toner for developing electrostatic latent image according to claim 2 is characterized in that for binding resin 100 weight portions, paraffin contains 0.1 to 20 weight portion.
10. electrostatic charge image developer according to claim 1 and 2, it is characterized in that the aromatic hydrocarbon copolymerization petroleum resin of aliphatic hydrocarbon-carbon number more than 9, as the aliphatic hydrocarbon composition, contain in isoprene, m-pentadiene, 2-methyl butene-1, the 2-methyl butene-2 at least a above monomer and as the aromatic hydrocarbon composition, contain at least a above monomer in vinyltoluene, α-Jia Jibenyixi, indenes, the isopropenyl toluene.
11. toner for developing electrostatic latent image according to claim 1 is characterized in that colorant is a magnetic.
12. electrostatic charge image developer, it is characterized in that in the electrostatic charge image developer that constitutes by carrier and toner, this toner contains colorant, binding resin, the aliphatic hydrocarbon-carbon number aromatic hydrocarbon copolymerization petroleum resin more than 9, wherein, the aromatic hydrocarbon amount of monomer of the aromatic hydrocarbon copolymerization petroleum resin of aliphatic hydrocarbon-carbon number more than 9 and the weight ratio of aliphatic hydrocarbon amount of monomer are 99: 1 to 50: 50.
13. electrostatic charge image developer according to claim 12 is characterized in that carrier has resin-coated layer.
14. formation method, it is characterized in that having the operation that forms electrostatic latent image and keep body and electrostatic latent image, the developer layer on the use developer carrier, aforementioned electrostatic latent image is kept in the formation method of operation of the electrostatic latent image development on the body, aforementioned developer contains colorant, binding resin, the aliphatic hydrocarbon-carbon number aromatic hydrocarbon copolymerization petroleum resin more than 9, wherein, the aromatic hydrocarbon amount of monomer of the aromatic hydrocarbon copolymerization petroleum resin of aliphatic hydrocarbon-carbon number more than 9 and the weight ratio of aliphatic hydrocarbon amount of monomer are 99: 1 to 50: 50.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB981251250A CN1178109C (en) | 1998-11-24 | 1998-11-24 | Toner for electrostaic image development, electrostatic image developer and imaging method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB981251250A CN1178109C (en) | 1998-11-24 | 1998-11-24 | Toner for electrostaic image development, electrostatic image developer and imaging method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1254864A CN1254864A (en) | 2000-05-31 |
| CN1178109C true CN1178109C (en) | 2004-12-01 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB981251250A Expired - Lifetime CN1178109C (en) | 1998-11-24 | 1998-11-24 | Toner for electrostaic image development, electrostatic image developer and imaging method thereof |
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| Country | Link |
|---|---|
| CN (1) | CN1178109C (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003195566A (en) * | 2001-12-28 | 2003-07-09 | Toyo Ink Mfg Co Ltd | Electrostatic image developing toner and image forming method using the same |
| CN114989372A (en) * | 2022-05-30 | 2022-09-02 | 张家港威迪森化学有限公司 | Solvent-free grafted powdered ink resin and preparation method thereof |
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1998
- 1998-11-24 CN CNB981251250A patent/CN1178109C/en not_active Expired - Lifetime
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| CN1254864A (en) | 2000-05-31 |
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