JP2019045525A - toner - Google Patents

Abstract

To provide a toner excellent in durability and fixability.SOLUTION: A toner includes toner particles containing a binder resin, a graft polymer, and a fatty acid metal salt; the graft polymer has a degree of compatibility of 70% or more to the binder resin.SELECTED DRAWING: None

Description

  The present invention relates to toners used in imaging methods such as electrophotography, electrostatic recording and toner jet methods.

  The electrophotographic technology used for copiers, printers, facsimile receivers, etc. is becoming more and more demanding from users as the devices are developed. In recent trends, it has been strongly demanded that a large number of sheets can be printed. Further, with the recent increase in environmental awareness, energy saving has been recognized as an essential issue, and from the viewpoint of energy saving, the demand for reduction of energy required for establishment has further increased. The toner used for that purpose is required to have excellent durability and low temperature fixability.

  In order to realize a highly durable toner, it is required to impart toughness to the binder resin of the toner. When a resin lacking toughness is used, the toner may be broken or chipped by contact stress in the development process. The toner fine powder that has been chipped out remains due to high electrostatic and / or non-electrostatic adhesion on the developing roller, and the developing roller contaminated with the toner fine powder has a reduced ability to charge the toner, As a result, so-called background smearing occurs where toner is printed on a white paper portion. In addition, when the toner is broken, the low melting point wax component inside the toner is exposed. When the toner in which the wax is exposed passes through the regulating blade, it adheres to the regulating blade, which causes a phenomenon called toner sticking, in which toner and external additives are deposited on the regulating blade. When toner sticking on the regulating blade occurs, streaks that do not transport the toner are generated on the developing roller, and white lines appear like streaks on the portion to be printed in the printed image.

  In order to satisfy the above-mentioned requirements, a toner having excellent durability and low temperature fixability is required more than ever, and many improvements have been made to solve the above-mentioned problems.

  For example, a toner obtained by performing suspension polymerization in the presence of a macromonomer is disclosed (Patent Document 1). In this toner, a graft polymer is formed in the toner particles, and physical entanglement of side chains of the graft polymer occurs, so that it is possible to achieve hot offset resistance even in a low temperature fixing design toner. Further, the toughness of the binder resin of the toner can be improved by the physical entanglement. However, there is still room for improvement in terms of toughness at higher levels.

  In addition, in order to obtain a highly durable toner, a method of producing a toner in which a fatty acid metal salt is added to a polymerizable monomer in a suspension polymerization toner is disclosed (Patent Document 2). According to this method, since the manufactured toner itself has excellent cleaning properties, no cleaning failure occurs and no image failure occurs even if a large number of sheets are printed. However, this technique can not suppress toner breakage and chipping, and there is room for improvement in terms of toughness.

JP-A-3-136065 Unexamined-Japanese-Patent No. 1-167764

  The present invention is to provide a toner which solves the above background art. That is, the present invention is to provide a toner having excellent durability and fixability.

  The above object is achieved by the present invention described below. That is, it is a toner having toner particles containing a binder resin, a graft polymer, and a fatty acid metal salt, wherein the graft polymer has a compatibility of 70% or more with respect to the binder resin. toner.

  As described above, according to the present invention, it is possible to provide a toner excellent in durability and fixability.

  Specifically, while maintaining good fixability, toughness can be improved, cracking and chipping can be reduced, and durability can be improved.

  As a result of intensive studies to solve the problems of the prior art described above, the inventors of the present invention are toners having toner particles containing a binder resin, a graft polymer, and a fatty acid metal salt, wherein the graft polymer is a binder. It was found that a toner having excellent durability and fixability can be obtained by setting the compatibility to 70% or more with respect to the adhesion resin.

  Although the detailed mechanism has not been clarified, the present inventors believe that the effect of the present invention is obtained by the following action. That is, it is considered that the specific graft polymer and the fatty acid metal salt interact with each other with a stronger force than the conventional entanglement between graft polymer chains. As a result, it is considered that toughness has been improved more than before, cracking and chipping have been reduced, and durability has been improved.

  Further, with regard to the fixing property, generally, when the crosslinking point of the resin is increased in the binder resin of the toner, the Tg of the toner is increased and the fixing property is deteriorated. However, it was found that the toner of the present invention did not deteriorate in the fixing property. It is considered that the interaction between the graft polymer and the fatty acid metal salt in the present invention is not a chemical crosslink having a bond but a reversible physical crosslink. Although this physical crosslinking is a sufficiently strong interaction in terms of durability than in the past, the interaction is easily eliminated at the time of fixing (that is, at the time of heating), and the toner Tg is lowered. I believe it has become.

<Graft polymer>
The effect of the present invention is poor if the graft polymer is not sufficiently compatible with the binder resin. If there is not sufficient melting and spreading of the graft polymer, the above interaction only exists locally in the binder resin and the effect is reduced. It has been found that the required compatibility of the graft polymer for the above interactions to be present throughout the binder resin is at least 70% relative to the binder resin. The compatibility is more preferably 80% or more in order to obtain higher durability.

  In addition, the combination of the graft polymer and the fatty acid metal salt is preferred to produce a proper interaction. Specifically, the compatibility of the fatty acid metal salt to the side chain of the graft polymer is preferably 5.0% or more and 15.0% or less in order to achieve high compatibility between durability and fixability.

  The graft polymer is not limited as long as the compatibility with the binder resin is 70% or more, but the main chain of the graft polymer preferably has a structure close to that of the binder resin to be used. The closer the structure is, the better the compatibility is. For example, if the binder resin is a styrene acrylic resin, the compatibility of the graft polymer is also improved if the styrene acrylic resin is used.

  The side chains of the graft polymer are not particularly limited as long as they can interact with the fatty acid metal salt. For example, resins having relatively high polarity such as acrylic resin, polyester resin, polyurethane resin, melamine resin, polybutylene terephthalate resin, polyethylene terephthalate resin, polycarbonate resin, polyacetal resin, polyarylate resin, epoxy resin can be used. In addition, copolymers of polar monomers constituting these resins with nonpolar monomers such as styrene can also be used, if necessary. Among these, polymethyl acrylate, polymethyl methacrylate, and styrene acrylonitrile copolymer can be suitably used in view of the interaction with the fatty acid metal salt.

  The number average molecular weight (Mn) of the graft polymer is preferably in the range of 5,000 to 50,000. When the number average molecular weight (Mn) is in the above range, the interaction with the fatty acid metal salt is appropriate, and the compatibility with the binder resin is also appropriate.

  In addition, the number average molecular weight (Mn) of the side chain of the graft polymer is in the range of 500 to 40,000, preferably 2000 to 8000. When the number average molecular weight (Mn) is in the above range, the interaction with the fatty acid metal salt is particularly appropriate, and the compatibility with the binder resin is also particularly appropriate.

  In the graft polymer, the ratio of side chains to the main chain is preferably in the range of 10% by mass to 50% by mass. When the proportion of side chains is within the above range, the interaction point between the graft polymer and the fatty acid metal salt can be increased while suppressing the addition amount of the graft polymer, and the graft polymer itself relative to the binder resin It is preferable because the compatibility can be maintained well.

  The addition amount of the graft polymer is preferably 10 parts by mass or more with respect to 100 parts by mass of the binder resin from the viewpoint of obtaining an appropriate interaction.

<Fatty acid metal salt>
The fatty acid metal salt used in the present invention may be a poorly water-soluble fatty acid metal salt consisting of a polyvalent metal having two or more valences and a fatty acid, and conventionally known fatty acid metal salts can be used. Specifically, as fatty acids, straight chain saturated fatty acids such as nonanoic acid, lauric acid, stearic acid and cerotic acid, straight chain unsaturated fatty acids such as oleic acid and linoleic acid, and branched structures such as 15-methylhexadecanoic acid Known fatty acids may be used, such as fatty acids having a fatty acid, 2-hydroxydodecanoic acid, and fatty acids having other functional groups such as 12-hydroxystearic acid. The fatty acid preferably has 8 to 28 carbon atoms, and more preferably 12 to 22 carbon atoms, in view of the interaction with the graft polymer and the availability.

  As the metal, a metal having a valence of 2 or more and known can be used. Among the typical elements, those having a high valence and a small ionic radius are considered to have a high interaction force with the graft polymer, and Al, Ba, Ca, Mg, and Zn are preferable. In addition, transition elements such as Fe, Ti, Co, and Zr are preferable because they can have stable unpaired electrons in the d orbital, and are considered to have a high interaction force with the graft polymer. Among these, Al, Mg, Zn, Fe and Co are particularly preferable.

  The amount of fatty acid metal salt added to the toner of the present invention is preferably 0.2% by mass or more and 50.0% by mass or less with respect to the graft polymer. When the content is 0.2% by mass or more, the interaction amount between the graft polymer and the fatty acid metal salt is sufficient. When the content is 50.0% by mass or less, the interaction between the fatty acid metal salts can be reduced. More preferably, it is 0.5 mass% or more and 20.0 mass% or less.

<Binder resin>
A known binder resin can be used for the toner of the present invention. For example, the following resins can be used as the binder resin. Polystyrene, homopolymers of styrene such as polyvinyl toluene and their substitution products; styrene-propylene copolymer, styrene-vinyl toluene copolymer, styrene-vinyl naphthalene copolymer, styrene-methyl acrylate copolymer, styrene -Ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-dimethylaminoethyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-methacrylic acid Ethyl copolymer, styrene-butyl methacrylate copolymer, styrene-dimethylaminoethyl methacrylate copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer Combined, styrene-pig Styrene copolymers such as ene copolymer, styrene-isoprene copolymer, styrene-maleic acid copolymer, styrene-maleic acid ester copolymer; polymethyl methacrylate, polybutyl methacrylate, polyvinyl acetate, polyethylene Polypropylene, polyvinyl butyral, silicone resin, polyester resin, polyamide resin, epoxy resin, polyacrylic resin, rosin, modified rosin, terpene resin, phenol resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin. These can be used alone or in combination.

<Pigment>
The toner can contain known pigments.

  Examples of yellow pigments include yellow iron oxide, navels yellow, naphthol yellow S, hanza yellow G, hanza yellow 10 G, benzidine yellow G, benzidine yellow GR, quinoline yellow lake, permanent yellow NCG, condensed azo compounds such as tartrazine lake, Isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds and allylamide compounds are used. Specifically, the following may be mentioned. C. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 14, C.I. I. Pigment yellow 15, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 62, C.I. I. Pigment yellow 74, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 94, C.I. I. Pigment yellow 95, C.I. I. Pigment yellow 109, C.I. I. Pigment yellow 110, C.I. I. Pigment yellow 111, C.I. I. Pigment yellow 128, C.I. I. Pigment yellow 129, C.I. I. Pigment yellow 147, C.I. I. Pigment yellow 155, C.I. I. Pigment yellow 168, C.I. I. Pigment yellow 180.

  The following may be mentioned as orange pigments. Permanent orange GTR, pyrazolone orange, Vulcan orange, benzidine orange G, Industlen brilliant orange RK, Industlen brilliant orange GK.

  Examples of red pigments include bengala, permanent red 4R, resole red, pyrazolone red, watching red calcium salt, lake red C, laked D, brilliant carmine 6B, brilant carmine 3B, eoxin lake, rhodamine lake B, alizarin lake and the like Azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds and perylene compounds can be mentioned. Specifically, the following may be mentioned. C. I. Pigment red 2, C.I. I. Pigment red 3, C.I. I. Pigment red 5, C.I. I. Pigment red 6, C.I. I. Pigment red 7, C.I. I. Pigment red 23, C.I. I. Pigment red 48: 2, C.I. I. Pigment red 48: 3, C.I. I. Pigment red 48: 4, C.I. I. Pigment red 57: 1, C.I. I. Pigment red 81: 1, C.I. I. Pigment red 122, C.I. I. Pigment red 144, C.I. I. Pigment red 146, C.I. I. Pigment red 166, C.I. I. Pigment red 169, C.I. I. Pigment red 177, C.I. I. Pigment red 184, C.I. I. Pigment red 185, C.I. I. Pigment red 202, C.I. I. Pigment red 206, C.I. I. Pigment red 220, C.I. I. Pigment red 221, C.I. I. Pigment red 254.

  As blue pigments, alkali blue lake, Victoria blue lake, phthalocyanine blue, metal free phthalocyanine blue, phthalocyanine blue partial chloride, copper phthalocyanine compounds such as fast sky blue, indaslen blue BG and derivatives thereof, anthraquinone compounds, basic dyes A lake compound etc. are mentioned. Specifically, the following may be mentioned. C. I. Pigment blue 1, C.I. I. Pigment blue 7, C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 1, C.I. I. Pigment blue 15: 2, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 60, C.I. I. Pigment blue 62, C.I. I. Pigment blue 66.

  Purple pigments include fast violet B and methyl violet lake.

  Examples of green pigments include pigment green B, malachite green lake, and final yellow green G. Examples of white pigments include zinc white, titanium oxide, antimony white and zinc sulfide.

  Examples of the black pigment include carbon black, aniline black, nonmagnetic ferrite, magnetite, the above-mentioned yellow pigment, red pigment and blue pigment, which are toned in black. These pigments can be used alone or in combination, or in the form of a solid solution.

  When used as a nonmagnetic toner, the content of the pigment is preferably 3.0 parts by mass or more and 10.0 parts by mass or less with respect to 100 parts by mass of the binder resin or the polymerizable monomer. When used as a magnetic toner, the content of the pigment (magnetite) is preferably 30 parts by mass or more and 150 parts by mass or less with respect to 100 parts by mass of the binder resin or the polymerizable monomer.

<Charge control agent>
The toner may contain a charge control agent. As a charge control agent, metal compounds of aromatic carboxylic acids represented by salicylic acid, alkylsalicylic acids, dialkylsalicylic acids, naphthoic acids, dicarboxylic acids and the like; metal salts or metal complexes of azo dyes or azo pigments; boron compounds, silicon compounds And calixarene. Moreover, the following quaternary ammonium salt and the polymeric type compound which has a quaternary ammonium salt in the side chain as a positive charge control agent; guanidine compound; nigrosine compound; imidazole compound is mentioned. The amount of charge control agent used is determined according to the type of binder resin, the presence or absence of other additives, and the toner production method including the dispersing method, and is not uniquely limited.

<Release agent>
The toner may contain a wax as a release agent. Types of waxes include petroleum waxes such as paraffin wax, microcrystalline wax, petrolatum and derivatives thereof; montan waxes and derivatives thereof; hydrocarbon waxes and derivatives thereof by the Fischer-Tropsch method; polyolefin waxes such as polyethylene wax and polypropylene wax; Derivatives thereof, natural waxes such as carnauba wax and candelilla wax, and derivatives thereof; higher aliphatic alcohols; fatty acids such as stearic acid and palmitic acid; acid amide waxes; ester waxes; hardened castor oil and derivatives thereof; Sex wax etc. are mentioned. Among them, paraffin wax, ester wax and hydrocarbon wax are preferable from the viewpoint of excellent releasability.

<External additive>
The toner may be externally added with a flowability improver for the purpose of improving the flowability. Types of flow improvers include fluorine resin powders such as non-vinylidene fluoride fine powder and polytetrafluoroethylene fine powder; fatty acid metal salts such as zinc stearate, calcium stearate and zinc stearate; titanium oxide powder, aluminum oxide Powder, metal oxide such as zinc oxide powder, or powder obtained by hydrophobizing the above metal oxide; and silica fine powder such as wet process silica, dry process silica or the like, silane coupling agent to these silicas, titanium coupling agent And surface-treated fine silica powder surface-treated with a treating agent such as silicone oil.

<Method of manufacturing toner>
The toner of the present invention may be produced by any known method, and can be produced by, for example, a suspension polymerization method, a dissolution suspension method, an emulsion aggregation method, or a pulverization method.

  An example of preparation by the suspension polymerization method is described below. In the suspension polymerization method, particles obtained by granulating and granulating a polymerizable monomer composition containing a polymerizable monomer, a graft polymer (or macromonomer) and a fatty acid metal salt in an aqueous medium Toner particles are obtained by polymerizing the polymerizable monomer contained therein.

  The polymerizable monomer used in the suspension polymerization method is preferably a monovinyl monomer. Specifically, as polymerizable monomers, for example, aromatic vinyl monomers such as styrene, vinyl toluene, α-methylstyrene, etc .; α, β-unsaturated carboxylic acids such as acrylic acid and methacrylic acid; methyl acrylate Ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, isobonyl acrylate, dimethylaminoethyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, methacrylic Derivatives of acrylic acid or methacrylic acid such as 2-ethylhexyl acid, cyclohexyl methacrylate, isobonyl methacrylate, dimethylaminoethyl methacrylate, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide; ethylene, Ethylenically unsaturated monoolefins such as ropylene and butylene; vinyl halides such as vinyl chloride, vinylidene chloride and vinyl fluoride; vinyl esters such as vinyl acetate and vinyl propionate; vinyl ethers such as vinyl methyl ether and vinyl ethyl ether; vinyl Vinyl ketones such as methyl ketone and methyl isopropenyl ketone; nitrogen-containing vinyl compounds such as 2-vinylpyridine, 4-vinylpyridine, N-vinylpyrrolidone and the like; The polymerizable monomers can be used alone or in combination of two or more. Among the monovinyl monomers, it is preferable to use an aromatic vinyl monomer in combination with an acrylic ester or methacrylic ester.

  As the polymerization initiator, an oil soluble initiator and / or a water soluble initiator are used. Preferably, the half life at the reaction temperature in the polymerization reaction is 0.5 to 30 hours. Further, when the polymerization reaction is carried out in an addition amount of 0.5 to 20.0 parts by mass with respect to 100.0 parts by mass of the polymerizable monomer, a polymer having a peak molecular weight of 10000 to 100,000 is usually obtained. A toner having melting characteristics can be obtained.

  Specific polymerization initiators include 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexane-1-carbo) Azo or diazo polymerization initiators such as nitrile), 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile, azobisisobutyronitrile, etc .; benzoyl peroxide, t-butylperoxy 2- Ethyl hexanoate, t-butyl peroxypiperate, t-butyl peroxyisobutyrate, t-butyl peroxy neodecanoate, methyl ethyl ketone peroxide, diisopropyl peroxy carbonate, cumene hydroperoxide, Peroxides such as 2,4-dichlorobenzoyl peroxide and lauroyl peroxide Initiator, and the like. Moreover, in order to control the polymerization degree of a polymerizable monomer, it is also possible to further add and use a well-known chain transfer agent, a polymerization inhibitor, etc.

  In addition, in order to control the molecular weight of the binder resin constituting the toner particles, a crosslinking agent may be added at the time of polymerization. Examples of the crosslinkable monomer include the following. Divinylbenzene, bis (4-acryloxypolyethoxyphenyl) propane, ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6 -Hexanediol diacrylate, neopentyl glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 200, # 400, # 600 each diacrylate, dipropylene glycol diacrylate, polypropylene Converted glycol diacrylate, polyester diacrylate (MANDA Nippon Kayaku), and the above acrylate into methacrylate The.

  The following are mentioned as polyfunctional crosslinkable monomers. Pentaerythritol triacrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, oligoester acrylate and its methacrylate, 2,2-bis (4-methacryloxypolyethoxyphenyl) propane, diacrylic phthalate, Triallyl cyanurate, triallyl isocyanurate, triallyl trimellitate, diarylchlorendate. The preferable addition amount is 0.001% by mass or more and 15,000% by mass or less with respect to the polymerizable monomer.

  An inorganic or organic dispersion stabilizer may be added to the aqueous medium. Types of inorganic compounds used as a dispersion stabilizer include hydroxyapatite, calcium phosphate tribasic, calcium phosphate dibasic, magnesium phosphate, aluminum phosphate, zinc phosphate, calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, Aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate, bentonite, silica, alumina and the like can be mentioned. Examples of the type of organic compound used as a dispersion stabilizer include polyvinyl alcohol, gelatin, methyl cellulose, methyl hydroxypropyl cellulose, ethyl cellulose, sodium salt of carboxymethyl cellulose, polyacrylic acid and salts thereof, starch and the like. Surfactants may also be used for the fine dispersion of these dispersion stabilizers. It is for promoting the initial action of the dispersion stabilizer. Examples of surfactants include sodium dodecyl benzene sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, potassium stearate, calcium oleate and the like. When an inorganic compound is used as a dispersion stabilizer, a commercially available product may be used as it is, but in order to obtain finer particles, the above-mentioned inorganic compound may be produced in an aqueous medium and used. For example, in the case of calcium phosphates such as hydroxyapatite and tribasic calcium phosphate, it is preferable to mix a phosphate aqueous solution and a calcium salt aqueous solution under high agitation.

  Hereinafter, various measurement methods related to the present invention will be described.

<Compatibility test of graft polymer for binder resin (S1)>
10 g of the binder resin is placed in a glass container and heated to 180 ° C. using a hot plate. The graft polymer is added thereto with stirring little by little and dissolved there, and the total addition amount of the graft polymer at the time of white turbidity (loss of compatibility) is determined as W1 (g) by the following formula.
Compatibility S1 (%) = W1 (g) / 10 (g) x 100

  When the binder resin can be obtained, the binder resin may be used as a sample as it is, but when it can not be obtained, the composition is the same and the weight average molecular weight is in the range of ± 10%. A test resin may be prepared and the compatibility with the resin may be measured.

<Compatibility test of fatty acid metal salt to graft polymer side chain (S2)>
10 g of a resin (including macromonomer) of the same type as the side chain of the graft polymer is placed in a glass container and heated to 180 ° C. using a hot plate. The fatty acid metal salt is added little by little while stirring there and dissolved, and the total addition amount of the fatty acid metal salt at the time of white turbidity (loss of compatibility) is determined as W2 (g) according to the following formula.
Compatibility S2 (%) = W2 (g) / 10 (g) x 100

  As a resin of the same type as the side chain of the graft polymer, a test resin having the same composition may be prepared, and the compatibility with the resin may be measured. Alternatively, the macromonomer used in synthesizing the graft polymer may be used as a test resin.

<Molecular weight measurement of resin>
The molecular weight and molecular weight distribution of the resin are calculated by gel permeation chromatography (GPC) in terms of polystyrene. The measurement of molecular weight by GPC is performed as follows. The above resin is added to THF (tetrahydrofuran), and the solution left at room temperature for 24 hours is filtered with a solvent resistant membrane filter “Misholy Disc” (manufactured by Tosoh Corporation) having a pore diameter of 0.2 μm to obtain a sample solution, Measure under the following conditions. In addition, sample solution preparation adjusts the quantity of THF so that the density | concentration of resin may be 0.8 mass%. When the resin is difficult to dissolve in THF, it is also possible to use a basic solvent such as DMF.

Device: HLC8120 GPC (detector: RI) (made by Tosoh Corporation)
Column: 7 series of Shodex KF-801, 802, 803, 804, 805, 806, 807 (made by Showa Denko)
Eluent: Tetrahydrofuran (THF)
Flow rate: 1.0 mL / min
Oven temperature: 40.0 ° C
Sample injection volume: 0.10 mL
In calculating the molecular weight of the sample, a molecular weight calibration curve prepared using the standard polystyrene resin columns listed below is used. Specifically, a trade name "TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F-10, F" manufactured by Higashi-Soh Co. -4, F-2, F-1, A-5000, A-2500, A-1000, A-500 ".

  Hereinafter, the present invention will be described in more detail by way of specific production methods, examples, and comparative examples, but the present invention is not limited in any way. All parts in the following formulation are parts by mass.

Synthesis Example of Graft Polymer G-1
-Styrene: 70.0 parts-butyl acrylate: 30.0 parts-Polymethyl methacrylate having terminal methacryloyl group (manufactured by Toagosei Co., Ltd., trade name: AA-6, Mn = 6000): 30.0 parts -Azobis isobutyro nitrile: After mixing and stirring 2.0 parts of nitrogen for 30 minutes, nitrogen substitution was carried out for 30 minutes, and it was heated so that the internal temperature would be 60 ° C and held for 15 hours as it was, to obtain a resin solid . Then, the resin solid was dissolved in tetrahydrofuran, reprecipitated with methanol, and the precipitated solid was separated by filtration to obtain a graft polymer G-1. The molecular weight (Mn) of graft polymer G-1 was 10,600.

Synthesis Example of Graft Polymer G-2
A graft polymer G-2 was obtained in the same manner as in the synthesis example of the graft polymer G-1 except that azobisisobutyronitrile was changed to 0.50 parts. The molecular weight (Mn) of graft polymer G-2 was 42000.

Synthesis Example of Graft Polymer G-3
-Styrene: 90.0 parts-Acrylonitrile: 10.0 parts-Polymethyl methacrylate having terminal methacryloyl group (made by Toagosei Co., Ltd., trade name: AA-6, Mn = 6000): 30.0 parts-Azo After mixing and stirring 2.0 parts of bisisobutyronitrile, nitrogen substitution was carried out for 30 minutes while stirring, and then heated so as to attain an internal temperature of 60 ° C. and held for 15 hours as it is, to obtain a resin solid. Then, the resin solid was dissolved in tetrahydrofuran, reprecipitated with methanol, and the precipitated solid was separated by filtration to obtain a graft polymer G-3. The molecular weight (Mn) of graft polymer G-3 was 10,500.

Synthesis Example of Graft Polymer G-4
Styrene: 70.0 parts Butyl acrylate: 30.0 parts 51% toluene solution of a copolymer of styrene and acrylonitrile whose terminal group is a methacryloyl group (manufactured by Toagosei Co., Ltd., trade name: AN-6S, Mn = 6000): 20.0 parts · Azobisisobutyronitrile: 2.0 parts are mixed and nitrogen substitution is carried out for 30 minutes while stirring, and then heated to an internal temperature of 60 ° C and maintained for 15 hours as it is The resin solid was obtained. Then, the resin solid was dissolved in tetrahydrofuran, reprecipitated with methanol, and the precipitated solid was separated by filtration to obtain a graft polymer G-4. The molecular weight (Mn) of graft polymer G-4 was 9000.

Synthesis Example of Graft Polymer G-5
A graft polymer G-5 was obtained in the same manner as in the synthesis example of the graft polymer G-3 except that the addition amount of styrene was changed to 50.0 parts and the addition amount of acrylonitrile to 50.0 parts. . The molecular weight (Mn) of graft polymer G-5 was 10,200.

<Production of Toner 1>
(Preparation of aqueous medium)
9.0 parts by mass of tricalcium phosphate is added to 1300.0 parts by mass of ion exchange water heated to a temperature of 60 ° C. K. The mixture was stirred at a stirring speed of 15,000 rpm using a homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) to prepare an aqueous medium.

(Preparation of Polymerizable Monomer Composition)
The polymerizable monomer composition was produced using the following raw materials.
Styrene: 70.0 parts by mass n-butyl acrylate: 30.0 parts by mass Carbon black: 7.5 parts by mass Polyester (polycondensate of propylene oxide-modified bisphenol A and phthalic acid, Tg = 75.9 ° C. Mw = 11,000, Mn = 4200, acid value = 11 mg KOH / g): 5.0 parts by mass Hydrocarbon wax (Tm = 78 ° C.): 9.0 parts by mass 3,5-di-tert-butyl salicylic acid Zinc compound [Bontron E84 (manufactured by Orient Chemical Industries, Ltd.)]: 3.0 parts by mass Graft polymer G-1: 30.0 parts by mass Aluminum stearate (trade name SA-1000, manufactured by Sakai Chemical Industry Co., Ltd.): 1.0 mass part The said raw material was melt | dissolved and disperse | distributed for 3 hours with Atorita (made by Nippon Coke Kogyo Co., Ltd.), and it was set as the polymerizable monomer composition.

(Production of Toner Particles 1)
The polymerizable monomer composition is charged into the aqueous medium, and 9.0 parts by mass of perbutyl PV [10-hour half-life temperature 54.6 ° C. (made by NOF Corporation)] is added as a polymerization initiator. The At a temperature of 60.degree. C., a high speed stirrer T.I. K. Using a homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), the mixture was stirred for 20 minutes at a stirring speed of 10,000 rpm for granulation.

  Then, it was transferred to a propeller type stirring device and reacted at a temperature of 70 ° C. for 5 hours while stirring at 100 rpm, and then heated up to a temperature of 80 ° C. and reacted for another 2 hours.

  Next, 200.0 parts by mass of ion exchange water was added, the reflux tube was removed, and a distillation apparatus was attached. The distillation in the vessel at a temperature of 100 ° C. was performed for 5 hours. The distillate fraction was 700.0 parts by mass. After completion of the distillation, the mixture was cooled to 30 ° C., diluted hydrochloric acid was added to the vessel to lower the pH to 1.5, and the dispersion stabilizer was dissolved. Further, the resultant was separated by filtration, washed and dried to obtain toner particles 1.

(External processing)
1.0 parts by mass of hydrophobic silica fine particles (number average diameter of primary particles: 7 nm) treated with dimethyl silicone oil with respect to 100.0 parts by mass of the toner particles 1 described above, an FM mixer (manufactured by Nippon Coke Kogyo Co., Ltd.) ) For 10 minutes to obtain Toner 1.

<Production of Toners 2 and 3>
Toners 2 and 3 were obtained in the same manner as in the production of toner 1 except that graft polymer G-1 was changed to graft polymers G-2 and G-3, respectively.

<Production of Toners 4 to 12>
Toners 4 to 12 were obtained in the same manner as in the production of Toner 1 except that each of the fatty acid metal salts, aluminum stearate, was changed to that shown in Table 1.

<Production of Toner 13>
Styrene-acrylic resin (styrene: n-butyl acrylate = 70: 30 (mass ratio)) (Mw = 30,000): 100.0 parts by mass Carbon black: 7.5 parts by mass 3,5-di- Zinc compound of tert-butyl salicylic acid [Bontron E84 (manufactured by Orient Chemical Industry Co., Ltd.)]: 3.0 parts by mass, graft polymer G-1: 30.0 parts by mass, aluminum stearate (trade name SA-1000, Sakai Chemical Industry Co., Ltd. Made by Co., Ltd .: 1.0 parts by mass The raw materials having the above-mentioned mixing ratio were mixed by a super mixer, and after hot-melt kneading by a twin-screw kneader, they were crushed by a jet mill. Thereafter, the resultant was classified with a dry air flow classifier to obtain toner particles 13.

  A toner 13 was obtained in the same manner as in the production of the toner 1 except that the obtained toner particles 13 were used.

<Production of Comparative Toner 1>
Comparative toner 1 was obtained in the same manner as in the production of toner 1 except that graft polymer G-1 and aluminum stearate were not added.

<Production of Comparative Toner 2>
Comparative toner 2 was obtained in the same manner as in the preparation of Toner 1 except that aluminum stearate was not added.

<Production of Comparative Toner 3>
Comparative toner 3 was obtained in the same manner as in the production of Toner 1 except that the graft polymer G-1 was not added.

<Production of Comparative Toner 4>
A comparative toner 4 was obtained in the same manner as in the production of the toner 1 except that the graft polymer G-1 was changed to the graft polymer G-5.

<Production of Comparative Toner 5>
Comparative toner 5 was obtained in the same manner as in the production of toner 13 except that graft polymer G-1 and aluminum stearate were not added.

<Compatibility test (S1 and S2)>
The compatibility of the graft polymer obtained in the above synthesis example with the binder resin was measured. In the toners 1 to 12 and comparative toners 1 to 4, styrene-acrylic resin (styrene: n-butyl acrylate = 70:30 (mass ratio), Mw = 100,000) was used as a binder resin. The toners 1 to 12 and the comparative toners 1 to 4 each had a Mw of a THF soluble content, and the Mw was in the range of ± 10% of the Mw 100,000. Further, in the toner 13 and the comparative toner 5, the resin of the raw material was used as it is as the binder resin. The results are shown in Table 1 below.

  Moreover, the compatibility with respect to the side chain of the graft polymer of each fatty acid metal salt was measured. In the toner using graft polymers G-1, G-2, G-3, and G-5 as the side chain of the graft polymer, "polymethyl methacrylate having a methacryloyl group as the end group" is used as the graft polymer In the toner using G-4, "copolymer of styrene and acrylonitrile in which the terminal group is a methacryloyl group" was used. The results are shown in Table 1 below.

[Examples 1 to 13 and Comparative Examples 1 to 5]
The evaluations described below were performed using Toners 1 to 13 and Comparative Toners 1 to 5. The results are shown in Table 2.

<Evaluation of durability>
Canon full-color copier CLC5000 remodeled machine (image carrier changed, laser spot diameter squeezed, output at 600dpi enabled, surface layer of fixing roller of fixing unit was changed to silicone tube, oil coating mechanism removed Were used in a CLC 5000), and under the normal temperature and normal humidity (25.degree. C./50% RH) environment, durability drawing evaluation (A4 horizontal, 5% printing ratio, 100,000 sheets) was performed. The evaluation method and evaluation criteria of the development streak after passing 100,000 sheets are shown below.

[Development streak]
A halftone image (toning amount: 0.6 mg / cm ² ) was printed out on CLC paper (manufactured by Canon Inc., 80 g / m ² ), and evaluated by the number of developed streaks.

(Evaluation criteria)
A: Not generated B: 1 or more, 3 or less C: 4 or more, 6 or less D: 7 or more, or a width of 0.5 mm or more

<Evaluation of fixability>
Low temperature fixability
The fixing unit of the Canon laser beam printer LBP 9600C has been modified so that the fixing temperature can be adjusted. Using this LBP 9600C after modification, an unfixed toner image of 0.40 mg / cm ² was formed at a process speed of 300 mm / sec under a normal temperature and normal humidity (25 ° C./50% RH) environment. The unfixed toner image was heated and pressurized without oil to form a fixed image on an image receiving sheet. At this time, the fixing temperature was changed in steps of 5 ° C. to form a fixed image. A fixed image obtained by applying a load of 75 g / cm ² was rubbed 10 times using Kimwipe [S-200 (Cresia Co., Ltd.)], and the fixability was evaluated at a temperature at which the density reduction rate before and after rubbing was less than 5%. did. The lower the temperature, the better the low temperature fixability.

(Evaluation criteria)
A: 130 ° C. or less B: 135 ° C.
C: 140 ° C
D: 145 ° C or higher

  From the results of Examples 1 to 8 and Comparative Examples 10 to 13 for Comparative Example 1, it was found that the combination of the graft polymer and the fatty acid metal salt can achieve both durability and fixability. In particular, it has been found that when the compatibility S1 is 80% or more and the compatibility S2 is in the range of 5 to 15%, both the durability and the fixability can be achieved at a higher level. Further, it was found that when the compatibility S1 is lower than Comparative Example 4, since the interaction between the side chain of the graft polymer and the fatty acid metal salt does not spread over the entire binder resin, the durability is hardly improved.

  The durability was improved in Example 9, but when the compatibility S2 exceeds 20% (if the interaction between the side chain of the graft polymer and the fatty acid metal salt is too strong), the fixability may be somewhat impaired. I understood.

From the results of Comparative Example 2 to Comparative Example 1, although the durability was somewhat improved, it did not reach a satisfactory level. Further, from the results of Comparative Example 3 to Comparative Example 1, the effects as in the present invention are not obtained. Therefore, it was found that the effect (the high compatibility of the durability and the fixability) of the present invention can not be obtained with the graft polymer alone or with the fatty acid metal salt alone.

Claims (6)

A toner comprising toner particles comprising a binder resin, a graft polymer, and a fatty acid metal salt,
The toner according to claim 1, wherein the graft polymer has a compatibility of 70% or more with respect to the binder resin.   The toner according to claim 1, wherein the compatibility of the fatty acid metal salt with the side chain of the graft polymer is 5.0% or more and 15.0% or less.   3. The toner according to claim 1, wherein the main chain of the graft polymer is a styrene acrylic resin, and the side chain of the graft polymer is polymethyl acrylate, polymethyl methacrylate, or a styrene acrylonitrile copolymer.   The metal salt of a fatty acid with a metal selected from the group consisting of Al, Ba, Ca, Mg, Zn, Fe, Ti, Co, Zr, according to any one of claims 1 to 3, Toner.   The toner according to claim 4, wherein the fatty acid is a fatty acid having 8 to 28 carbon atoms. The toner according to any one of claims 1 to 5, wherein the binder resin is a styrene acrylic resin.