Toner composition

The disclosure herein relates to a composition comprising a polymerization initiator and an unsaturated sulfopolyesteramine resin, and to methods for preparing and using the composition.

Recent developments in the printing industry are towards xerographic packaging applications. Fused deposition toner is generally used in such applications. However, some problems arise with the use of Fused Deposition Toners in those applications. One problem concerns fixing toner on a rough or thick substrate, such as a cardboard material, or on an aluminum substrate. In addition, the heat of the heat-roll fuser system is difficult to transfer through heavy, rough-surfaced paper, and when the print area is very large, such as in color printing. Even more so.

Furthermore, when printing a large number of products for packaging purposes, it is necessary to use a material that is durable and can withstand various conditions and environmental factors. Traditional package printing uses curable inks, such as UV-curable or heat-curable inks, to "toughen" the resulting printed image or indicia, thereby resulting in the final. Make sure that the image or display on the packaging is durable and wear resistant. In addition, many offset prints use a heated overcoat to protect the image from abrasion. However, applying an overcoat to a frozen and unfused image can also result in poor image quality. Therefore, there is a need for a toner composition that does not require a protective overcoat in embodiments.

Electrophotographic toners generally include resins such as styrene-acrylate or polyester, colorants and, in some cases, charge modifiers. Many toner formulations are known, and more specifically, one toner formulation contains an unsaturated polyester resin, thereby obtaining the desired low fixing temperatures and offset properties. ing. For this, refer to Patent Document 1, for example.

Some toners, including unsaturated polyester-based toner resins, can be crosslinked by UV light at high temperatures in the presence of a UV polymerization initiator after fixing (after fusing). The UV polymerization initiator can be applied on top of the toner image as a lacquer in a post application, or it can be applied to the toner developer in the form of an external additive, or manufactured. It can also be added into the toner dispersion during the process. However, in the case of UV curable toners, it is necessary to use a UV device system for post-fixing, which is not currently available in commercially available xerographic engines.

<patcit num="1"><text>U.S. Pat. No. 5,227,460</text></patcit>

<p> There is a need for robust toners with a wide range of fusing latitudes, high gloss, and non-document offset properties. It is still necessary to be able to cure the fixed image so that the resulting image is not worn or smeared. There is still a need for toner that can be crosslinked during the fixing process without the need for UV light.</p>

<p> The composition of the present invention comprises a polymerization initiator and an unsaturated sulfopolyesteramine resin, wherein the unsaturated sulfopolyesteramine resin contains (i) an amine residue, (ii) an alkali sulfonate residue, and (iii) unsaturated. The amine residue comprises a saturated residue.<u style="single">Derived from dialkanolamine</u>Contains aromatic functional amines.</p>

In some embodiments, the disclosure is a composition comprising a polymerization initiator and an unsaturated sulfopolyesteramine resin; a toner composition comprising a colorant, a polymerization initiator, and an unsaturated sulfopolyesteramine resin; and a toner. The process for preparing the composition includes (a) a step of preparing a latex emulsion containing particles from an unsaturated sulfopolyesteramine resin, and (b) a colorant of the latex emulsion. A step of combining with a dispersion and a polymerization initiator dispersion, (c) a step of adding a flocculating agent to the dispersion, and a step of heating the mixture to a temperature lower than the glass transition temperature of the resin, and a step of heating the mixture to a temperature lower than the glass transition temperature of the resin. (d) A step of heating a latex emulsion containing a resin to a temperature lower than the glass transition temperature of the resin, and then heating the latex emulsion containing the resin to a temperature higher than the glass transition temperature of the resin. ..

Disclosed in other embodiments are the steps of forming an image, developing the image with a toner composition comprising a colorant, a polymerization initiator, and an unsaturated sulfopolyesteramine resin, and the toner. An image forming process comprising a step of fixing the formed image; a toner curing process comprising a step of fixing a toner composition containing a colorant, a polymerization initiator, and an unsaturated sulfopolyesteramine resin; the polymerization initiator is , Crosslinking unsaturated residues of the resin; and fixing the toner composition formed by the emulsion aggregation process, wherein the toner composition is a colorant, a polymerization initiator. , And a method of cross-linking a toner composition comprising an unsaturated sulfopolyester amine resin.

The disclosed compositions can include a polymerization initiator and an unsaturated sulfopolyesteramine resin. The unsaturated sulfopolyester amine resin contains a polyester backbone having a polymerized amine residue in the polyester backbone. The disclosed toner composition can be prepared by the emulsion polymerization agglutination method.

The polymerization initiator can be selected from the group consisting of a thermal polymerization initiator, a free radical polymerization initiator, an ultraviolet polymerization initiator and the like. Non-limiting examples of polymerization initiators include benzoin ethers, acetophenone derivatives such as 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2, There are 2,2-trichloroacetophenone and so on. Suitable hydrogen abstraction type polymerization initiators include benzophenone and its derivatives, anthraquinone, 4,4'-bis (dimethylamino) benzophenone, thioxanthone and quinoline sulfonyl chloride (quinoline). Combination with sulfonylchloride), 2,4,6-trimethylbenzoyl-diphenyl-phosphinoxide, (2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one), (hydroxycyclohexyl) Phenyl Ketone, (2-benzyl-2-N-dimethylamino-1- (4-morpholinophenyl) -1-butanone), (benzyldimethylketal), 2- (carbamoylazo) -substituted (-substituted), 2 Included are -n-propoxy-9H-thioxanthene-9-one, and ethyl 4- (dimethylamino) benzoate. Suitable donor-acceptor Complexes) include a combination of a donor such as triethanolamine and an acceptor such as benzophenone. Other suitable sensitizers or polymerization initiators include combinations of thioxanthone with quinoline sulfonyl chloride; alcines, phosphones, thioureas, benzyl acetals, α-haloacetphenones, 2,4, 6-trimethylbenzoyldiphenylphosphine oxide, (2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one), (hydroxycyclohexyl) phenylketone, (2-benzyl-2-N- Dimethylamino-1- (4-morpholinophenyl) -1-butanone), (benzyldimethylketal), 2- (carbamoylazo) -substituted, 2-n-propoxy-9H-thioxanthene-9-one and 4- (Dimethylamino) Ethyl benzoate and the like.

The polymerization initiator may be further selected from the group consisting of peroxides, azo compounds, pinacols and the like. Non-limiting examples of peroxides include inorganic or organic peroxides, such as potassium peroxide peroxides, organic hydroperoxides, benzoyl peroxides, lauryl peroxides, 1,1- (t-butylperoxy) -3,3. , 5-trimethylcyclohexane, n-butyl-4,4-di- (t-butylperoxy) valerate, dicumyl peroxide, dibenzoyl peroxide, di- (n-propyl) peroxydicarbonate, t-butylbenzoate , T-amyl (2-ethylhexyl) monoperoxydicarbonate, 2,2-di- (t-butyl-peroxy) butane, dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) -Hexane, 1,3-bis (t-butylperoxyisopropyl) benzene, 1,3-bis (cumylperoxyisopropyl) benzene, 2,4-dichlorobenzoyl peroxide, caprylyl peroxide Peroxide), lauroyl peroxide, t-butylperoxyisobutyrate, p-chlorobenzoyl peroxide, hydroxyheptylperoxide, di-t-butyldiperphthalate, 1,1-di (t-butylperoxy) -3,3,5 -Trimethylcyclohexane, di-t-butyl peroxide, benzoyl peroxides, lauryl peroxide, n-butyl-4,4-di- (t-butylperoxy) peroxide, hydrogen peroxide, acetyl peroxide, cumyl peroxide, tert-butyl Peroxide, propionyl peroxide, chlorobenzoyl peroxide, dichlorobenzoyl peroxide, bromomethylbenzoyl peroxide, ammonium persulfate, sodium persulfate, potassium persulfate, diisopropyl peroxycarbonate, tetraline hydroperoxide, 1-phenyl-2-methylpropyl- 1-Hydroperoxide, tert-butyl triphenylperacetate Hydroperoxide, tert-butyl peroxide performate), tert-butyl acetate, tert-butyl perbenzoate (tert-butyl perbenzoate), tert-butyl phenyl acetate, tert-butyl methoxy peracetate, and tert-butyl N- (3-toluyl) percarbamate ( Percarbamate), and mixtures thereof.

Non-limiting examples of azo compounds and diazo compounds are 2,2'-azobispropane, 2,2'-dichloro-2,2'-azobispropane, 1,1'-azo (methylethyl). Diacetate, 2,2'-azobis (2-amidinopropane) hydrochloride, 2,2'-azobis (2-amidinopropane) nitrate, 2,2'-azobisisobutane, 2,2'-azobisisobutyry Amid, 2,2'-azobisisobutyronitrile, 2,2'-azobis-2-methylpropionate, 2,2'-dichloro-2,2'-azobisbutane, 2,2'-azobis-2 -Methylbutyronitrile, dimethyl 2,2'-azobisisobutyrate, 1,1'-azobis (sodium 1-methylbutyronitrile-3-sulfonate), 2- (4-methylphenylazo) -2-methylmalono Dinitrile, 4,4'-azobis-4-cyanovaleric acid, 3,5-dihydroxymethylphenylazo-2-methylmalonodinitrile, 2- (4-bromophenylazo) -2-allylmalononitrile, 2, 2'-azobis-2-methylvaleronitrile, 4,4'-azobis-4-cyanovalerate dimethyl, 2,2'-azobis-2,4-dimethylvaleronitrile, 1,1'-azobiscyclohexanenitrile, 2,2'-azobis-2-propylbutyronitrile, 1,1'-azobis-1-chlorophenylethane, 1,1'-azobis-1-cyclohexanecarbonitrile, 1,1'-azobis-1-cycloheptane Nitrile, 1,1'-azobis-1-phenylethane, 1,1'-azobisisobutymen, 4-nitrophenylazobenzylcyanoacetate, phenylazodiphenylmethane, phenylazotriphenylmethane, 4-nitrophenylazotriphenylmethane, 1,1'-azobis-1,2-diphenylethane, poly (bisphenol A-4,4-azobis-4-cyanopentanoate), poly (tetraethylene glycol-2,2'-azobisisobutyrate), azoisobutyronitrile, azodimethylvaleronitrile, diazoamine azobenzene, 2,2'-azodimethylvaleronitrile (diazoamineazobenzene 2,2'-azodimethylvaleronitrile), 2,2'-azo Isobutyronitrile, azobiscyclohexanenitrile, 2-methylbutyronitrile, 2-t-butylazo-2-cyanopropane, 2,2'-azobis (2,4-dimethyl-4-methoxyvaleronitrile), 2, There are 2'-azobis (isobutyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 1,1'-azobis (cyclohexanecarbonitrile), and mixtures thereof.

Non-limiting examples of pinacols, including substituted or unsubstituted pinacols, are benzopinacol, 4,4'-dichlorobenzopinacol, 4,4'-dibromobenzopinacol, 4,4. '-Diodebenzopinacol, 4,4', 4'', 4'''-Tetrachlorobenzopinacol, 2,2', 4,4'-Tetrachlorobenzopinacol, 4,4'-Dimethylbenzopinacol, 3,3'-dimethylbenzopinacol, 2,2'-dimethylbenzopinacol, 3,3', 4,4'-tetramethylbenzopinacol, 4,4'-dimethoxybenzopinacol, 4,4', 4'' , 4'''-Tetramethoxybenzopinacol, 4,4'-diphenylbenzopinacol, 4,4'-dichloro-4'', 4'''-dimethylbenzopinacol, 4,4'-dimethyl-4'' , 4'''-diphenylbenzopinacol, xanthonpinacol, fluorenonepinacol, acetophenonpinacol, 4,4'-dimethylacetophenone-pinacol, 4,4'-dichloroacetophenonepinacol, 1,1,2-triphenyl- Propane-1,2-diol, 1,2,3,4-tetraphenylbutane-2,3-diol, 1,2-diphenylcyclobutane-1,2-diol, propiophenone-pinacol, 4,4'- Dimethylpropiophenone pinacol, 2,2'-diethyl-3,3'-dimethoxypropiophenone-pinacol, 1,1,1,4,4,4-hexafluoro-2,3-diphenyl-butane-2, These include 3-diol, benzopinacol-monomethyl ether, benzopinacol-mono-phenyl ether, benzopinacol and monoisopropyl ether, benzopinacol monoisobutyl ether, benzopinacol mono (diethoxymethyl) ether, and mixtures thereof.

The polymerization initiator can be present in the toner composition in an amount of about 1 to about 10 weight percent, eg, about 2 to about 7 weight percent, based on the total weight of the toner composition. The amount of the polymerization initiator may be outside the above range as long as the polymerization initiator can initiate cross-linking polymerization of unsaturated residues of the resin. The half-life of the polymerization initiator is preferably about 80 ° C to 120 ° C.

The unsaturated sulfopolyester amine resin is (i) an amine residue present in an amount of about 0.1 to about 10 weight percent, eg, about 2 to about 7 weight percent, based on the total weight of the resin; (ii) the total weight of the resin. Alkali sulfonate residues present in an amount of about 1.5 to about 5 weight percent by weight, eg, about 2 to about 4 weight percent; and (iii) about 5 relative to the total weight of the resin. It may contain unsaturated residues, which are present in an amount of ~ about 45% by weight, eg, about 15 ~ about 30% by weight. The amine residue may function as a cross-linking accelerator or sensitizer with a polymerization initiator such as peroxide, and the unsaturated residue of the resin may allow cross-linking of the toner. See Brauer et al., "Initiator-Accelerator Systems for Dental Resin" (FEJr. ed.) ACS, p.359-371 (1983).

Amine residues can reduce the time or temperature at which a dissociation to generate free radicals of a polymerization initiator such as peroxide occurs. Amine residues can be incorporated into a normal polyester backbone, for example, to form an image when anchoring toner on a substrate, eg paper, or in a post fusing process. In some cases, the crosslinked toner resin can be easily prepared.

In some embodiments, the amine residues that can be used in preparing the unsaturated sulfopolyester amine resin include primary functional alkyl amines, secondary functional alkyl. Included are amines and tertiary functional alkylamines. In one embodiment, tertiary functional alkylamines can be used. In yet another embodiment, aromatic functional amines can be used. In addition, the amine residue is a chemical functional group for incorporating the amine residue into the polyester main chain. group) may be included. For example, the chemically reactive functional group may be a hydroxyl group and, as a further example, two hydroxyl functional groups per molecule to allow incorporation into the entire backbone chain. Examples of aromatic functional amines are N-phenyldiethanolamine, N, N-di (2-hydroxyethyl) -p-toluidine, N, N-di (2-hydroxypropyl) -p-toluidine, 2, 6-Dimethanolpyridine, 2,4-dihydroxy-5,6-dimethylpyrimidine, 2,4-dihydroxydihydroxy-6-methylpyrimidine, 2,4-dihydroxy-6-methylpyrimidine, 4,6-dihydroxypyrimidine, 2 , 4-Dihydroxypyridine, phenylethylethanolamine, etc., but are not limited thereto. Examples of tertiary alkylamines include, but are not limited to, methyldiethanolamine, ethyldiethanolamine, dimethylisopropanolamine, and diisopropylethanolamine. Examples of secondary and primary functional amines include, but are not limited to, the following alkanolamines: diethanolamine, diisopropanolamine, di-sec-butanolamine, 2-amino-2- Ethyl-1,3-propanediol, methylethanolamine, phenylethanolamine, 2-aminoethanol, and 2-amino-2-methyl-1-propanol.

Alkaline sulfonate residues are hydrophilic as required to prepare toner by known aggregation coalescence processes in aqueous media as disclosed in US Pat. No. 5,227,460. Gender can be imparted. More specifically, alkaline sulfonate residues help dissipate the resin into water, thereby ranging from about 5 nm to about 250 nm when heated in water to temperatures above the Tg of the resin. Submicron size polyester particles can be produced.

The unsaturated residue may be a linear unsaturated polyester or a low molecular weight condensed polymer. It should be understood that the low molecular weight here means about 4000 to about 20,000. This polymer is formed by reacting both saturated and unsaturated diacids (or acid anhydrides) with dihydric alcohols (glycols or diols) in the presence of a polycondensation catalyst. Can be done. The resulting unsaturated polyesters can react (eg, crosslink) at two sites (for example, crosslinks): (i) unsaturated sites (double bonds) in the main chain of polyester, and ( ii) Functional groups such as carboxyl groups, hydroxy groups, etc., which can participate in acid-base reactions.

In order to form the unsaturated sulfopolyesteramine resin disclosed in the present specification, various diacids or esters of diacids can be selected, and are selected from the group consisting of, for example, the following. : Fumaric acid, malonic acid, itaconic acid, 2-methylitaconic acid, maleic acid, maleic anhydride, adipic acid, succinic acid, suberic acid, 2-ethylsuccinic acid, glutaric acid, dodecylsuccinic acid, 2-methyladic acid Pimelic acid, azelaic acid), succinic acid, terephthalic acid, isophthalic acid, phthalic acid, 1,2-cyclohexanedioic acid, 1,3-cyclohexanediic acid, 1,4-cyclohexanediic acid, dialkyl ester, the alkyl of which is about. Contains 2 to about 22 carbon atoms, malonate, succinate, fumarate, itaconic acid, terephthalate, isophthalate, phthalate , Cyclohexanedioate, and mixtures thereof. The diacid can optionally be selected in an amount of 35 mol percent to about 0.45 mol percent, relative to about 100 mole percent of the resin, provided that the unsaturated sulfopolyester amine resin disclosed herein. Etc., at least about 5 to about 35 mole percent of the selected acid residues need to be unsaturated. In embodiments, the diacid can be selected from the group consisting of fumaric acid, malonic acid, itaconic acid, 2-methylitaconic acid, maleic acid, and maleic anhydride.

In embodiments, examples of sulfonated organic diacids or esters of sulfonic acids include sodium 5-sulfoisophthalate (sodio), potassium 5-sulfoisophthalate (potasio), sodium 2-sulfoterephthalate. , 2-Sulfonelephthalate, Sodium dimethyl 5-sulfoisophthalate, Potassium 5-sulfoisophthalate, and mixtures thereof. In some cases, these diacids can be present in an amount of 1 mol percent to about 10 mole percent, relative to about 100 mole percent of the resin.

Examples of organic diols that may be used to prepare unsaturated sulfopolyesteramine resins include, for example, alkylene glycols having a carbon chain length of, for example, about 1 to about 25 carbon atoms, as well as, for example, ethylene. Glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, 1,2-pentylene glycol, 1,3-penti Lene glycol, 1,4-pentylene glycol, 1,5-pentylene glycol, hexylene glycol, heptalene glycol, diethylene glycol, dipropylene glycol, cyclohexanediol, 2,2-dimethylpropanediol, 1,2-propanediol , But not limited to, diols or glycols such as, neopentylene glycol, octylene glycol, cyclohexanedimethanol, and mixtures thereof. Organic diols, including diols or glycols, can be used in various effective amounts, eg, in an amount of about 45 to about 55 mole percent of the resin.

Suitable polycondensation catalysts are tetraalkyl titanates, such as dialkyltin oxides such as dibutyltin oxide, tetraalkyltin such as dibutyltin dilaurate, for example butyltin oxide hydroxides. It may be selected from the group comprising dialkyltin oxide catalysts such as oxide catalysts, aluminum alkoxides, alkyl zincs, dialkyl zincs, zinc oxides, stannous oxides, or mixtures thereof. .. The polycondensation catalyst can be present in an amount of about 0.01 mol percent to about 5 mole percent relative to the starting material diacid or diester used to produce the polyester.

Unsaturated sulfopolyesteramine resins can be expressed in embodiments by the following equations:<chemistry num="1"><img file="JP5501547B2_D0001.tif" /></chemistry>

In Chemical formula 1, A contains about 6 to about 36, for example, about 10 to about 28 carbon atoms, such as benzylene, bisphenylene or bisphenylene, bis (alkyloxy) bisphenylene, etc. Can be arylene, such as; l can be about 10 to about 1,000, for example, about 100 to about 700 segments; B can be about 2 to about 25 carbons. It may contain an atom, eg, an organic alkali sulfonate such as metalo 5-sulfoisophthalte, metallosulfoethylene, metallosulfopropylene, etc., where metalo ion) can be, for example, an alkali metal such as lithium, sodium, potassium, magnesium, or a transition metal such as zinc; m is a number of segments of about 10 to about 1,000, for example about 100 to about 700. C may be an unsaturated alkene containing about 2 to about 25 carbon atoms, such as ethene, propene, butene, etc .; R may be about 2 to about 25. An alkylene such as ethylene, propylene, butylene, oxy sintered diethylene oxide, or a dialkanol amine as represented by the following formula, which contains carbon atoms;<chemistry num="2"><img file="JP5501547B2_D0002.tif" /></chemistry>

In Chemical formula 2, R may be any suitable substituent as defined above, and R'is about 2 to about 25 carbon atoms, such as phenyl, benzyl, methyl, ethyl, propyl, etc. , For example, an alkyl containing about 8 to about 16 carbon atoms, or an aryl containing about 2 to about 25 carbon atoms, for example about 8 to about 16 carbon atoms; n (Chemical formula 1). ) May be about 10 to about 1,000, for example, about 100 to about 700 segments.

In the embodiments disclosed herein, the unsaturated sulfopolyesteramine resin can be represented by the following equation;<chemistry num="3"><img file="JP5501547B2_D0003.tif" /></chemistry>

Where R is an alkylene containing about 2 to about 25 carbon atoms, such as ethylene, propylene, butylene, oxyalkylene diethylene oxide, or, for example, a dialkanol amine;<chemistry num="4"><img file="JP5501547B2_D0004.tif" /></chemistry>

Here R may be as defined above, and R'can be an alkyl or aryl containing about 2 to about 25 carbon atoms, such as phenyl.

The unsaturated sulfopolyesteramine resin has a number average molecular weight (Mn) in the range of about 1,500 to about 50,000 g / mol, and has a weight average molecular weight (weight average molecular weight) measured by gel permeation chromatography using polystyrene as a standard substance. It is preferable that Mw) is in the range of about 6,000 g / mol to about 150,000 g / mol and its polydispersity is about 2 to about 12.

The unsaturated sulfopolyester amine resin can be present in the composition in an amount of about 75 to about 95 weight percent, eg, about 80 to about 90 weight percent, based on the total weight of the toner composition.

In some cases, but usually, the toner composition may include a colorant. The colorants are, for example, US Pat. No. 4,788,123; US Pat. No. 4,828,956; US Pat. No. 4,894,308; US Pat. No. 4,948,686; US Pat. No. 4,963,455; and US Pat. No. 4,965,158. It can be selected from the group consisting of dyes and pigments disclosed in the specification. Non-limiting examples of pigments include black, cyan, magenta, yellow, green, orange, brown, violet, blue, red, purple, white and silver. To give a non-limiting example of colorants, carbon black (eg Regal 3300 (registered trademark)), Flexiverse Pigment (Flexiverse) Pigment) BFD1121, Niglosin Dye, Aniline Blue, Magnetite and Colored Magnetite, eg Mobay Magnetite, MO8029 , MO8060 ; Columbian Magnetite MAPICO BLACKS CB4799 , CB5300 , CB5600 , MCX6369 ; Bayer Magnetite, BAYFERROX 8600 , Trademark), 8610 (Trademark); Northern Pigments (Northern) Pigments) Magnetite, NP-604 , NP-608 ; Magnox Magnetite TMB-100 or TMB-104 ; Phthalocyanine, 2,9-dimethyl-substituted quinacridone (quinacridone) and anthraquinone dyes classified as CI60710 in the Color Index, CI Disperst Red 15, diazo dyes classified as CI26050 in the Color Index, CI Solvent Red 19, Copper Tetra (Octadecylsulfone) Amid) phthalocyanine, x-copper phthalocyanine pigments classified as CI74160 in the Color Index, CI Pigment Blue, Anthradanthrene Blue classified as CI69810 in the Color Index, Special Blue X-2137 (Special Blue) X-2137), diallylide yellow 3,3-dichlorobenzidine acetoacetanilide, monoazo pigments classified as CI12700 in color index, CI solvent yellow 16, nitrophenylamine sulfonamide in color index foron yellow SE Classified as / GLN (Foron Yellow SE / GLN), CI Disperst Yellow 33,2,5-dimethoxy-4-sulfonanilide phenylazo-4'-chloro-2,5-dimethoxyacetoacetanilide, permanent -Yellow FGL, Pigment Yellow 74, B15: 3 Cyan pigment dispersion (commercially available from Sun Chemicals), Magenta Red 81: 3 pigment dispersion (commercially available from Sun Chemicals), Yellow 180 pigment dispersion (Commercially available from Sun Chemicals), cyan components, and even mixtures thereof. Other commercially available pigment raw materials include Sun Chemical (Sun). Available as an aqueous pigment dispersion from either Chemical or Ciba, Pigment Yellow 17, Pigment Yellow 14, Pigment Yellow 93, Pigment Yellow 74, Pigment Violet 23, Pigment Violet 1, Pigment Green 7, Pigment Orange 36, Pigment Orange 21, Pigment Orange 16, Pigment Red 185, Pigment Red 122, Pigment Red 81: 3, Pigment Blue 15: 3, and Pigment Blue 61, and other pigments that allow the reproduction of the maximum Pantone color space, but are not limited to these. To give a non-limiting example of other suitable colorants, Cinquasia Magenta (DuPont), Levanyl Black A-SF (Miles). (Miles), made by Bayer, Sunsperse Carbon Black LHD9303 (Sunsperse) Carbon Black LHD 9303), Sunsperse Blue BHD 6000 and Sunsperse Yellow YHD 6001 (available from Sun Chemicals); Normandy Magenta RD-2400 (Normandy Magenta RD-) 2400), Permanent Yellow YE 0305, Permanent Violet VT2645, Argyle Green XP-111-S, Resole Rubine Toner (Lithol Rubine Toner), Royal Brilliant Red RD-8192, Brilliant Green Toner GR 0991, and Ortho Orange OR 2673) (all available from Paul Uhlich); Sudan Orange G, Tolidine Red, and ED Toluidine Red (Aldrich) Available from); Sudan III, Sudan II and Sudan IV (all available from Matheson, Coleman, Bell); Scarlet Fore · Thermoplast · NSD · PS · PA (Scarlet for Thermoplast NSD PS PA) (available from Ugine Kuhlman, Canada); Bon Red C (Dominion Color Company) Available from Dominion Color Co.); Lumogen Yellow D0790, Suco-Gelb L1250), Sco-Yellow D1355, Paliogen Violet 5100, Paliogen Orange 3040, Paliogen Yellow 152, Neopen Yellow 152 Yellow (Neopen Yellow), Paliogen Red 3871K (Paliogen Red 3871 K), Paliogen Red 3340 (Paliogen Red 3340), Paliogen Yellow 1560 (Paliogen Yellow 1560), Paliogen Violet 5890 (Paliogen Violet 5890) , Paliogen Blue 6470 (Paliogen Blue 6470), Resole Scarlet 4440 (Lithol Scarlet 4440), Resole Fast Scarlet L4300 (Lithol Fast Scarlet L4300), Resole Scarlet D3700 (Lithol Scarlet) D3700), Lithol Fast Yellow 0991K, Paliotol Yellow 1840, Heliogen Green L8730, Heliogen Blue L6900, L7202, D6840, D7080, Neopen Blue, Sudan Blue OS, Sudan Orange 220, and Fanal Pink D4830 (all above) , Available from BASF); Cinquasia Magenta (available from DuPont); Novoperm Yellow FG1 (available from Hoechst); Hosta Palm Pink E (Hostaperm Pink E) and PV / Fast Blue / B2G01 (PV Fast Blue) B2G01) (all available from American Hoechst); Irgalite Blue BCA, and Oracet pink RF (all from Ciba-Geigy) Available) and so on. Mixtures of colorants can also be used.

When present, the colorant of any component may be present in the toner composition in any desired amount or effective amount, for example, from about 1 to about 25% by weight of the toner composition, for example from about 2 to about. It is present in an amount of 15% by weight, or about 5 to about 12% by weight based on the total weight of the toner composition to give a further example. However, the amount may be outside the above range.

The toner composition may optionally contain an additive for charge control, such as, for example, cetylpyridinium chloride, which is disclosed in US Pat. No. 4,298,672. Alkylpyridinium halide, including others; for example, distearyldimethylammonium methyl sulfate as disclosed in US Pat. No. 4,560,635; US Pat. No. 4,937,157; US Pat. No. 4,560,635, and simultaneously. Sulfates and persulfates, including distearyldimethylammonium bisulfate, as disclosed in pending US Patent Application No. 07 / 396,497 (Abandonment); eg Bontron E-84 (Bontron) Disclosure in 3,5-di-tert-butyl salicylate zinc compound, such as E-84) (available from Orient Chemical Company, Japan), or US Pat. No. 4,656,112. Zinc compounds such as; for example, Bontron E-88 (Bontron) It is disclosed in 3,5-di-tert-butylsalicylate aluminum compound, such as E-88) (available from the Orient Chemical Company in Japan), or in US Pat. No. 4,845,003. Aluminum compounds such as; US Pat. No. 3,944,493; US Pat. No. 4,007,293; US Pat. No. 4,079,014; US Pat. No. 4,394,430; US Pat. No. 4,464,452; US Pat. No. 4,480,021. Specifications; Charge regulating additives as disclosed in US Pat. No. 4,560,635, and the like, as well as mixtures thereof.

The charge adjusting additive of an arbitrary component is present in the toner composition in an amount of about 0.1 to about 10% by weight, for example, about 1 to about 5% by weight, based on the total weight of the toner composition. Good. However, the amount may be outside the above range.

In some cases, the toner composition may further include an external surface additive, such as, for example, a flow aid additives. Additives are present on the surface of the toner. To give a non-limiting example of external surface additives, metal oxides such as titanium oxide, tin oxide and mixtures thereof, colloidal silica such as Aerosil (registered trademark), metal salts of fatty acids, for example. These include zinc stearate, aluminum oxide, cerium oxide, and mixtures thereof. Some of the additives mentioned above are described in US Pat. No. 3,590,000 and US Pat. No. 3,800,588. Further, the external surface additive may be the coated silica described in US Pat. No. 6,004,714, US Pat. No. 6,190,815 and US Pat. No. 6,214,507. This external surface additive is an aggregation process. It may be added in process) or blended onto the formed toner particles.

The optional external surface additive may be present in any desired amount or effective amount, for example, from about 0.1 to about 5% by weight based on the total weight of the toner composition, and as a further example, about 0.1. ~ Exist in an amount of about 1% by weight. However, the amount may be outside the above range.

This toner composition may contain wax. To give a non-limiting example of waxes, polypropylene and polyethylene (commercially available from Allied Chemical and Petrolite Corporation), wax emulsions (Michaelman Inc.) and (Available from Daniels Products Company), EPOLENE N-15 (trademark) (Eastman Chemical Products, Inc.) (Commercially available from Inc.)), VISCOL 550-P (trademark), low weight average molecular weight polypropylene (available from Sanyo Kasei KK) and their equivalents. Commercially available polyethylenes that can be selected have a molecular weight of about 700 to about 2,500, whereas commercially available polypropylenes preferably have a molecular weight of about 4,000 to about 7,000. Examples of functionalized waxes such as amines and amides include aqua superslip 6550 (AQUA SUPERSLIP 6550, trademark) and superslip 6530 (SUPERSLIP 6530, trademark) (micro powder). · Incorporated (available from Micro Powder Inc.), fluorinated waxes such as Polyfluo 190 (POLYFLUO 190, trademark), Polyfluo 200 (POLYFLUO 200, trademark), Polyfluo 523XF (POLYFLUO 523XF, trademark), Aqua Polyfluo 411 (AQUA) POLYFLUO 411 (Trademark), AQUA POLYSILK 19 (Trademark), POLYSILK 14 (Trademark) (Available from Micro Powder Inc.), Mixed Fluorinated Amide Waxes (mixed fluorinated, amide waxes), such as MICROSPERSION 19, trademark (also available from Micro Powder Inc.), imides, esters, quaternary amines. From quaternary amines, carboxylic acid or acrylic polymer emulsions, such as JONCRYL 74 (TM), 89, 130, 537 and 538 (all from SC Johnson Wax). (Available), chlorinated polypropylene and polyethylene (available from Allied Chemical and Petrolite Corporation and SC Johnson Wax), and the like.

The disclosed toner composition can be prepared by an emulsion (polymerization) agglutination method. This emulsion (polymerization) aggregation method generally includes (a) a step of preparing a latex emulsion containing resin particles, (b) a colorant as needed, and in some cases a polymerization initiator. The step of combining with, (c) the step of heating the latex emulsion containing the resin to a temperature lower than the glass transition temperature of the resin, and (d) the step of heating the latex emulsion containing the resin to the glass transition temperature of the resin. A step of heating a latex emulsion containing the resin to a temperature higher than the glass transition temperature of the resin after heating to a lower temperature. In certain embodiments, the emulsion (polymerization) aggregation method includes (a) a step of preparing a dispersion of a colorant which is an optional component, and (b) a flow of the dispersion as resin particles and an optional component. It mixes with a latex emulsion containing a curating agent, thereby causing the formed colorant and resin particles to undergo emulsion or heterocoagulation to form electrostatically bound aggregates. Steps to make (c) the electrostatically bonded aggregate to the glass transition temperature of the resin (T)_g) To form a stable aggregate by heating to a temperature below, and (d) the stable aggregate to the glass transition temperature (T) of the resin._g) Is a step of heating to a temperature higher than (above) to coreless its stable aggregates into the toner particles.

In yet another embodiment, the emulsion (polymerization) aggregation method includes (a) an ionic surfactant of any component, a colorant of any component, and any of them in a solvent such as water. Steps of Preparing a Dispersion, Containing a Charge Regulator of Ingredients; (b) (i) (1) Counterionic with Charge Polarity Having a Sign Opposite to the Polarity of the Ionic Surfactant. A surfactant, which is either (2) nonionic, and (ii) a resin, thereby formed from a colorant, a resin, and an optional charge regulator. The step of shearing the dispersion with a latex emulsion, which contains a resin, which causes the flow-curation or heterocoagulation of the particles to form electrostatically bonded aggregates; (c) stable. Aggregates (this aggregate has an average particle diameter in the range of about 1 μm to about 25 μm, eg, about 2 μm to about 10 μm, but its particle size may be outside this range; its stable aggregate. Typically has a relatively narrow particle size with a GSD of about 1.16 to about 1.25. A step of heating an electrostatically coupled aggregate to a temperature lower than the glass transition temperature of the resin so as to form a distribution), but the particle size distribution may be outside this range). , And (d) the step of adding an additional amount of ionic surfactant to the aggregate to further stabilize them, suppress further growth, and not lose the desired narrow particle size distribution, Then, it is a step of heating the aggregate to a temperature higher than the glass transition temperature of the resin so as to obtain coreless toner particles containing the resin, the colorant of an arbitrary component, and the charge modifier of an arbitrary component.

The heating to coreless the electrostatically coupled aggregate may be in the range of about 5 ° C to about 50 ° C higher (above) than the glass transition temperature of the resin. It may be out of this range.

The main difference between coreless particles and pre-coreless aggregates is in their morphology; that is, pre-coreless particles have a large surface area, eg, "grape clusters". On the other hand, the surface area of the particles after being coreless is reduced, for example, in a "potato" shape or a more spherical shape. It is possible to adjust the morphology of the particles, depending on the conditions during the coalescing process, namely the temperature, coalessing time, and so on. Next, the toner particles are washed to remove excess water-soluble surfactant and surfactant adhering to the surface, and further dried to obtain toner particles.

Another embodiment of the emulsion (polymerization) agglutination method is a counterionic surfactant having the opposite polarity to at least one ionic surfactant in forming the latex. It involves the use of a floculating agent or coagulating agent such as polyaluminum chloride or poly (aluminum sulfosilicate) instead of surfactant). In this process, aggregation of submicron-sized latex and colorants and other optional ingredients is adjusted by the amount of coagulant added and then the temperature at which the resulting blend is heated. For example, the closer the temperature is to Tg of the resin, the larger the particle size. Included in this process are (1) the step of preparing a dispersion containing an ionic surfactant; (2) (a) a floculating agent, (b) a nonionic surfactant, and (c) a resin. Flocculation of the surfactant and resin particles formed to share the dispersion with a latex emulsion containing, thereby forming electrostatically bound aggregates. A step of causing a ration or heterocoagulation (causing;) and (3) a step of heating the electrostatically coupled aggregate to form a stable aggregate. Aggregates thus obtained generally have an average particle size in the range of about 1 to about 25 μm, for example about 2 to about 10 μm, but the particle size may be outside these ranges, and the particles. The diameter distribution is relatively narrow.

Alkali metal bases such as aqueous sodium hydroxide solution are added to this aggregation to raise the pH of the aggregate from a pH range of about 2.0 to about 3.0 to a pH range of about 7.0 to about 9.0. If desired, it is also possible to adjust the pH to the more acidic side in the solution in order to regulate the morphology of the particles during the core resensing step. The coagulation agent is added to the mixture of ionic latex and dispersion as an acidic solution (eg, 1M (molar) nitric acid solution), but the viscosity of the mixture increases during the addition. Then, by heating and stirring, aggregation is promoted to form micron-sized particles. Once the desired particle size is reached, the pH of the mixture can be frozen to this size, for example by raising it to the range of about 7 to about 9, but the pH may be outside this range. .. The temperature of the mixture can then be raised to the desired core resolution temperature, eg, about 80 ° C to about 95 ° C, but the temperature may be outside this range. The pH of the mixture can then be lowered to, for example, a pH value of about 3.5 to about 5.5 to adjust the morphology of the particles, but the pH may be outside this range.

Examples of such ionic surfactants include anionic surfactants such as sodium dodecyl sulfate, sodium dodecylbenzene sulfate, sodium dodecylnaphthalene sulfate, dialkyl benzenealkyl sulfate and dialkyl benzenealkyl sulfonate, abitic. acid), NEOGEN R (registered trademark) and NEOGEN SC (registered trademark) (available from Kao), DOWFAX (registered trademark) (Dow Chemical Co. ), Etc., and mixtures thereof, but are not limited to these. The anionic surfactant may be used in any desired or effective amount, eg, from about 0.01 to about 10% by weight, for example about 0.1 to about 5% by weight, of the monomer used to prepare the copolymer resin. It is used, but the amount may be outside these ranges.

To give further examples of ionic surfactants, cationic surfactants such as dialkylbenzenealkylammonium chloride, lauryltrimethylammonium chloride, alkylbenzylmethylammonium chloride, alkylbenzyldimethylammonium bromide, benzalkonium chloride, cetylpyridinium bromide. , C₁₂Trimethylammonium bromide, C₁₅Trimethylammonium bromide, C₁₇Trimethylammonium bromide, quaternized polyoxyethylalkylamine halide salt, dodecylbenzyltriethylammonium chloride, MIRAPOL (registered trademark) and ALKAQUAT (registered trademark) (Aklaril Chemical Company) (Available from), SANIZOL (registered trademark) (available from benzalkonium chloride, Kao Chemicals), and even mixtures thereof, but are not limited to these. The cationic surfactant may be used in any desired amount or effective amount, for example, about 0.1% to about 5% by weight of water, but the amount may be out of this range. The molar ratio of the cationic surfactant used for floculation to the anionic surfactant used for latex preparation may be from about 0.5: 1 to about 4: 1, for example from about 0.5: 1 to about 2: 1, but this relative The ratio may be outside these ranges.

Examples of suitable nonionic surfactants are polyvinyl alcohol, polyacrylic acid, metalose, methyl cellulose, ethyl cellulose, propyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, polyoxyethylene cetyl ether, polyoxyethylene lauryl ether, polyoxyethylene octyl. Ether, polyoxyethylene octylphenyl ether, polyoxyethylene oleyl ether, polyoxyethylene sorbitan monolaurate, polyoxyethylene stearyl ether, polyoxyethylene nonylphenyl ether, dialkylphenoxypoly (ethyleneoxy) ethanol (Rhone-Pourin) -Poulenc), Igepearl CA-210 (IGEPAL CA-210, registered trademark), Igepearl CA-520 (IGEPAL CA-520, registered trademark), Igepearl CA-720 (IGEPAL CA-720, registered trademark) Trademark), Igepearl CO-890 (IGEPAL CO-890, registered trademark), Igepearl CO-720 (IGEPAL) CO-720 (registered trademark), Igepearl CO-290 (IGEPAL CO-290, registered trademark), Antarox 890 (ANTAROX 890, registered trademark), and Antarox 897 (ANTAROX 897, registered trademark), etc. , And even mixtures thereof. The nonionic surfactant may be present in any desired or effective amount, eg, from about 0.01 to about 10% by weight of the monomer used to prepare the copolymer resin, and more examples from about 0.1 to about 0.1. It can be present in 5% by weight, but the amount may be outside these ranges.

US patent 5,916,725; US patent 5,919,595; US patent 5,922,501; US patent 5,925,488; US patent 5,945,245; US patent 5,977,210; US patent 6,017,671; US Pat. No. 6,020,101; US Pat. No. 6,045,240; US Pat. No. 6,132,924; US Pat. No. 6,143,457; and US Pat. No. 6,210,853. The ingredients and processes in those patents can be selected for disclosure in embodiments of the present invention.

The toner composition disclosed in the present invention is adhered onto an electrostatic latent image on an image forming member using a suitable conventional electrophotographic development method to form an image, and then thereby. The formed image can be developed. Known electrophotographic development methods include a magnetic brush development method, a cascade development method, a powder cloud development method, an electrophoresis development method, and the like.

The adhered toner image is bonded to an image receiving member, such as paper or transparency material, by any suitable method conventionally used in electrophotographic, such as corona transfer, pressure transfer, or adhesion. It can be transferred by a transfer method, a bias roll transfer method, or the like. After the transfer, the transferred toner image can be fixed on the substrate. The fixing step may be the same as a step conventionally used for forming an electrophotographic image. Well-known electrographic fusing techniques include heated roll fixing method (fusing), flash fixing method, oven fixing method, laminating method, adhesive spray fixing method, and the like. Be done. For example, the image formed by the toner can be generated by an electrophotographic (xerographic) process or a digital image forming process.

The toner compositions disclosed herein can be applied on a wide array of substrates. For example, such a substrate may be paper, cardboard, plastic, foil, metal, or a combination thereof.

[Preparation of unsaturated resin A] In a 1 liter Parr Reactor equipped with a mechanical double turbine agitator, a distiller and a bottom drain valve, Dimethyl terephthalate (263g), fumaric acid (27.75g), sodium salt of dimethyl 5-sulfo-isophthalate (38.5g), 1,2-propanediol (243g) , Diethylene glycol (36.3g), N-phenyldiethanolamine (2.9g), Fascat 4100 (fascat) 4100) (1 g) and hydroquinone (0.2 g) were charged. The reactor was heated while purging with carbon dioxide (to prevent cross-linking) to a temperature of about 140 ° C. and the solids melted. The rotation speed of the stirrer was about 100 rpm. The reactor temperature was then raised to 165 ° C over 20 minutes, where methanol / water by-products began to distillate. Then, the reaction temperature was gradually raised to 190 ° C over 3 hours, and the speed of the stirrer was also raised to 200 rpm. Then raise the temperature to 200 ° C, gradually reduce the pressure from atmospheric pressure to about 1 torr (torr, 1 torr is about 133.32 pascals) over 2 hours, keep for another 2 hours under that condition, and then use carbon dioxide. The reactor was pressurized to atmospheric pressure and the reaction mixture was discharged through a bottom drain valve into a cooled metal pan. (The bread was cooled on the outside with dry ice.) Then, when the physical properties of the resin (that is, the reaction mixture) were measured, the Tg (onset) was 52 ° C and the softening point was 137 ° C. Met. This resin is hereinafter referred to as unsaturated resin A.

[Preparation of unsaturated resin B] Dimethyl terephthalate (263 g), fumaric acid (27.75 g), sodium 5-sulfo-isophthalate in a 1 liter pearl reactor equipped with a mechanical double turbine agitator, distillation unit and bottom drain valve. Salt (41 g), 1,2-propanediol (249 g), diethylene glycol (31.3 g), N-phenyldiethanolamine (2.9 g), Fascat 4100 (1 g), and hydroquinone (0.2 g) were charged. The reactor was heated while purging with carbon dioxide (to prevent cross-linking) at a temperature of about 140 ° C. and the solids melted. The rotation speed of the stirrer was about 100 rpm. The temperature of the reactor was then raised to 165 ° C over 20 minutes, where methanol / water by-products began to distillate. Then, the reaction temperature was gradually raised to 190 ° C over 3 hours, and the speed of the stirrer was also raised to 200 rpm. The temperature is then raised to 200 ° C, the pressure is gradually lowered from atmospheric pressure to about 1 torr over 2 hours, kept for another 2 hours under those conditions, and then the reactor is pressurized with carbon dioxide to atmospheric pressure. , The reaction mixture was drained into a cooled metal pan through the bottom drain valve. (The outside of the bread was cooled with dry ice.) Then, when the physical properties of the resin (that is, the reaction mixture) were measured, the Tg (rise) was 61 ° C and the softening point was 155 ° C. .. This resin is hereinafter referred to as unsaturated resin B.

[Preparation of Emulsion Aggregation Toner Composite (Composite) I] 1 liter of water in a 1 liter kettle equipped with a mechanical stirrer, a heating mantle and a distillation apparatus. And heated to 60 ° C. A solution of unsaturated resin A (105 g) and thermal initiator VAZO 88 (2 g) dissolved in 1500 g of acetone was added dropwise over 3 hours. Heating of the mixture was continued for an additional 2 hours and then cooling to give an emulsion with a particle size of 54 nm.

In a 2 liter glass reactor equipped with an overhead stirrer and a mantle heater, the above emulsion 956.02 g (solid content: 10.46%) and cyan flexiverse pigment BFD1121 (cyan Flexiverse pigment BFD1121) 10.49g (solid content: 48.9%) was charged. The mixture was heated to 58 ° C with stirring at 200 rpm. 266.67 g of zinc acetate (3 wt% aqueous solution) was added dropwise over 5.5 hours. When the particle size was measured using a Coulter counter, the volume average particle size was 5.7 μm, the GSD was 1.18, and the circularity was 0.9. The toner slurry was then cooled to room temperature, separated by sieving (25 μm) filtration, then washed and lyophilized to give the emulsion aggregation toner composite I.

[Preparation of Emulsion Aggregation Toner Composite Material II] 1 liter of water was placed in a 1 liter kettle equipped with a mechanical stirrer, mantle heater, and distillation apparatus, and heated to 60 ° C. A solution prepared by dissolving the crystalline resin (30 g) and the thermal polymerization initiator BPO (5.28 g) in 300 g of acetone was added dropwise over 1 hour. Heating of the mixture was continued for an additional 2 hours and then cooling to give an emulsion with a particle size of 62.7 nm.

302.34 g of the above emulsion (solid content: 6.96%) and 908.97 g of unsaturated resin A emulsion (solid content: 9.26%) in a 2 liter glass reactor equipped with an overhead stirrer and a mantle heater. , 55.48 g of wax (solid content: 20.08%) and 28.35 g of cyan pigment (solid content: 26.20%) were charged. 210.43 g (3 wt% aqueous solution) of zinc acetate was added dropwise into the above mixture with homogenization. The mixture was heated to 60 ° C. and stirred at 600 rpm for at least 2 hours. When the particle size was measured using a Coulter counter (monitor), the volume average particle size was 4.31 μm and the GSD was 1.27. The toner slurry is then cooled to about 23 ° C to about 25 ° C, separated by sieve (25 μm) filtration, then washed 3 times with water and then lyophilized to form an emulsion-aggregation toner composite. Material II was obtained.