JP2019020492A - toner - Google Patents

Abstract

To provide a toner that has a wide fixable temperature range and a heat-resistant storage property and prevents fogging in both a low-temperature and low-humidity environment and a high-temperature and high-humidity environment.SOLUTION: A toner includes toner particles containing a binder resin, a colorant, a fatty acid metal salt, and a crystalline polyester part. The crystalline polyester part has an alkyl group having 7 or more carbon atoms at the terminal, and when the number of carbon atoms in the alkyl group is C1, and the number of carbon atoms in a fatty acid constituting the fatty acid metal salt is C2, C1 and C2 satisfy the following relational expression (1). Relational expression (1) 0.25≤C1/C2≤3.90.SELECTED DRAWING: None

Description

  The present invention relates to a toner used in an image forming method such as an electrophotographic method, an electrostatic recording method, and a toner jet method.

  In recent years, printers and copiers are required to have high speed and low power consumption, and development of toner having excellent low-temperature fixability and heat-resistant storage stability is required. In response to this demand, a method has been proposed in which crystalline polyester is used for the toner and both low-temperature fixability and heat-resistant storage stability are achieved by utilizing the sharp melt property of the crystalline polyester. However, when crystalline polyester is used for the toner, the chargeability is deteriorated, and there is a case in which an adverse effect such as fog deterioration is caused.

On the other hand, Patent Documents 1 and 2 disclose toners using crystalline polyester having a low acid value and hydroxyl value.
Regarding the toners disclosed in Patent Documents 1 and 2, although the deterioration of the charging property is suppressed, there remains a problem in the stability in a harsh environment under high temperature and high humidity. Further, it has been found by the present inventors that there is a problem of occurrence of electrostatic offset in fixing in a low temperature and low humidity environment. If electrostatic offset occurs during fixing, the fixable temperature range is narrowed. Now that multifunction devices and printers have become widespread and are now used in various regions and environments, there is a demand for toners having excellent stability in both low temperature and low humidity environments and high temperature and high humidity environments.

Japanese Patent No. 2931899 JP 2002-318471 A

  An object of the present invention is to provide a toner having a wide fixable temperature range and heat-resistant storage stability and suppressing fogging in both a low temperature and low humidity environment and a high temperature and high humidity environment.

The above object is achieved by the present invention described below. That is, a toner having toner particles containing a binder resin, a colorant, a fatty acid metal salt, and a crystalline resin having a crystalline polyester moiety,
The crystalline polyester portion has an alkyl group having 7 or more carbon atoms at the terminal, the carbon number of the alkyl group is C1, and the fatty acid constituting the fatty acid metal salt is C2, and C1 and C2 Satisfies the following relational expression (1).
0.25 ≦ C1 / C2 ≦ 3.90 Formula (1)

According to the present invention, it is possible to provide a toner that has a wide fixable temperature range and heat-resistant storage stability and suppresses fogging in both a low temperature and low humidity environment and a high temperature and high humidity environment.

1 is an example of a schematic cross-sectional view of an electrophotographic apparatus to which the present invention can be applied. It is an example which showed the relationship between the back contrast and fog density in the Example of this invention. It is an example which showed the relationship between the back contrast and fog density in the comparative example of this invention.

Hereinafter, the present invention will be described in detail.
The toner of the present invention is a toner having toner particles containing a binder resin, a colorant, a fatty acid metal salt, and a crystalline resin having a crystalline polyester moiety,
The crystalline polyester portion has an alkyl group having 7 or more carbon atoms at the end,
The toner is characterized in that C1 and C2 satisfy the following relational expression (1), where C1 is the carbon number of the alkyl group and C2 is the carbon number of the fatty acid constituting the fatty acid metal salt.
0.25 ≦ C1 / C2 ≦ 3.90 Formula (1)

As a result, a toner having a wide fixable temperature range and heat-resistant storage stability and suppressing fogging in both a low temperature and low humidity environment and a high temperature and high humidity environment can be obtained.
The toner of the present invention contains a crystalline resin having a crystalline polyester moiety having an alkyl group having 7 or more carbon atoms at the terminal. That is, the crystalline polyester is a crystalline resin having few terminal carboxy groups and terminal hydroxy groups and low acid value and hydroxyl value. By using a crystalline polyester having a low acid value and hydroxyl value, fixability and fog are improved if the polyester is not allowed to stand in a harsh environment, whereas fog is liable to deteriorate if it is left in a harsh environment. As this factor, the affinity with the binder resin is increased by reducing the carboxy group or hydroxy group of the crystalline polyester, or the interaction between these polar groups is reduced, etc. in the binder resin. It is conceivable that the crystalline polyester became easier to bleed.

  In addition, electrostatic offset is likely to occur during fixing in a low temperature and low humidity environment. The electrostatic offset is a phenomenon in which the toner or toner layer flies or adheres from the paper to the fixing device side by electrostatic force. If a crystalline polyester having a low acid value and a low hydroxyl value is used under low temperature and low humidity, the toner or toner layer is likely to be easily charged up at the fixing nip. When the electrostatic offset occurs, a low temperature offset or a high temperature offset at the time of fixing is induced, and the fixable temperature range is narrowed.

  The low temperature offset is a phenomenon that the toner in the lower layer of the fixed image near the interface with the paper is not sufficiently dissolved and adheres to the surface of the fixing device. Regarding the low temperature offset, since the low temperature fixing effect of the crystalline polyester can cover to some extent, the high temperature offset is particularly problematic. Here, the high temperature offset is a phenomenon in which a part of the fixed image adheres to the surface of the member of the fixing device in a region where the temperature of the fixing member is high, and is further fixed on the paper (recording material) in the next round. Hereinafter, it is described as hot offset in this specification.

At this time, the crystalline polyester portion in the crystalline resin has an alkyl group having 7 or more carbon atoms at the terminal, and there is a fatty acid metal salt that satisfies the following relational expression (1).
As a toner, the present inventors have found that fog deterioration under a high-temperature and high-humidity environment is suppressed and a wider fixing temperature range can be obtained.
0.25 ≦ C1 / C2 ≦ 3.90 Formula (1)
(C1 in Formula (1) represents the carbon number of the said alkyl group, C2 represents the carbon number of the fatty acid which comprises the said fatty-acid metal salt.)
In the case where there are a plurality of alkyl groups having a plurality of carbon atoms or a fatty acid having a plurality of carbon atoms, the carbon number of the alkyl group having the highest abundance ratio or the fatty acid having the most abundance ratio is defined as C1 and C2.

The reason why the effect of the present invention is obtained is not clear, but the interaction between the terminal alkyl group of the crystalline polyester part of the crystalline resin and the fatty acid part of the fatty acid metal salt works, and the dispersion of the crystalline resin in the toner It is thought that it improves the performance.
Since C1 and C2 satisfy | fill the following relational expression (2), interaction becomes still larger, and it is more preferable.
0.75 ≦ C1 / C2 ≦ 1.30 Formula (2)

The crystalline resin contained in the toner of the present invention is characterized by including a crystalline polyester portion having an alkyl group having 7 or more carbon atoms at the terminal.
As a method for obtaining a crystalline polyester having an alkyl group having 7 or more carbon atoms at the terminal, a monovalent alcohol or monovalent acid having an alkyl chain having 7 or more carbon atoms is used, and a carboxy group or a hydroxy group at the terminal of the polymer is used. The method of sealing is mentioned.

  Examples of the monovalent alcohol include octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol and the like. Examples of the monovalent acid include caprylic acid, capric acid, lauric acid, stearic acid, and behenic acid. Thereby, the effect of improving the heat resistant storage stability is easily obtained. The acid value and hydroxyl value of the crystalline polyester are preferably 4.0 mgKOH / g or less and the hydroxyl value is 7.0 mgKOH / g or less. Thereby, deterioration of charging property is suppressed, and generation of fog is suppressed.

The crystalline polyester can be obtained by reaction of a divalent or higher polyvalent carboxylic acid with a polyhydric alcohol. From the viewpoints of melting point and crystallinity, a crystalline polyester using aliphatic dicarboxylic acid and aliphatic diol as main raw materials is preferable.
The following are mentioned as a polyhydric alcohol. Ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, trimethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, octamethylene glycol, nonamethylene glycol , Decamethylene glycol, dodecamethylene glycol, neopentyl glycol, 1,4-butadiene glycol and the like.

  The following are mentioned as polyvalent carboxylic acid. Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, speric acid, glutaconic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, maleic acid, fumaric acid Acid, mesaconic acid, citraconic acid, itaconic acid, isophthalic acid, terephthalic acid, n-dodecyl succinic acid, n-dedecenyl succinic acid, cyclohexanedicarboxylic acid, anhydrides or lower alkyl esters of these acids, and the like.

Further, the crystalline resin contained in the toner of the present invention may be a simple crystalline polyester consisting of only a crystalline polyester portion, but it is a block polymer having a crystalline polyester portion and an amorphous vinyl portion. Preferably there is. The amorphous vinyl moiety is preferably generated from one or more polymerizable monomers selected from the following group.
Examples of the polymerizable monomer include the following styrenic polymerizable monomers, acrylic polymerizable monomers, and methacrylic polymerizable monomers. Styrene is preferred from the viewpoint of ease of polymer production.

  Styrene, α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, p- Styrenic polymerizability such as n-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, and p-phenyl styrene Monomer.

  Methyl acrylate, ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate , N-nonyl acrylate, cyclohexyl acrylate, benzyl acrylate, dimethyl phosphate ethyl acrylate, diethyl phosphate ethyl acrylate, dibutyl phosphate ethyl acrylate, and acrylic polymerizable monomers such as 2-benzoyloxyethyl acrylate.

  Methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, iso-propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, n-amyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate Methacrylic polymerizable monomers such as n-nonyl methacrylate, diethyl phosphate ethyl methacrylate, and dibutyl phosphate ethyl methacrylate.

  As a method for producing a modified crystalline polyester modified with an amorphous vinyl moiety, the following known production methods can be applied. A method in which an amorphous vinyl moiety is elongated by, for example, atom transfer radical polymerization after first synthesizing a crystalline polyester moiety. A method in which a crystalline polyester portion is elongated after synthesizing an amorphous vinyl portion having a reactive functional group introduced therein. A method in which a crystalline polyester portion and an amorphous vinyl portion are first synthesized separately and then bonded together.

The weight average molecular weight (Mw) of the crystalline resin is preferably from 15,000 to 45,000. When the weight average molecular weight is less than 15,000, the heat resistance is deteriorated, and when it is greater than 45,000, the low-temperature fixability is deteriorated.
The content of the crystalline resin in the toner is preferably 1% by mass or more and 30% by mass or less with respect to the binder resin. When the content is 1% by mass or more, the low-temperature fixability is improved, and when the content is 30% by mass or less, charging properties and heat-resistant storage stability with no practical problems can be obtained.

  As the fatty acid metal salt used in the present invention, a conventionally known fatty acid metal salt can be used without any particular limitation. Specifically, the following known fatty acids can be used as the fatty acid. Linear saturated fatty acids such as octanoic acid, nonanoic acid, lauric acid, stearic acid, behenic acid, and montanic acid. Linear unsaturated fatty acids such as oleic acid and linoleic acid. Fatty acids having a branched structure such as 15-methylhexadecanoic acid. In addition, the same effect can be obtained regardless of whether one or more of these fatty acids are bonded to one central metal.

  As the central metal, Al, Ba, Ca, Mg, and Zn are preferable because typical elements having a high valence and a small ionic radius are more stable. 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 have high stability.

  The content of the fatty acid metal salt in the toner is preferably 0.2% by mass or more and 20.0% by mass or less with respect to the mass of the crystalline resin. When the content is 0.2% by mass or more, the fixable temperature range is widened, and when the content is 20.0% by mass or less, chargeability having no practical problem can be obtained.

  Next, components contained in the toner particles of the present invention will be described. As the toner particles, those used in general toners can be used without limitation. In addition to the above-described crystalline resin and fatty acid metal salt, a binder resin, a colorant, a charge control agent, a release agent are used. Contains agents.

  The following can be used as the binder resin. Styrene such as polystyrene and polyvinyltoluene and homopolymers thereof; styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene 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-ethyl methacrylate Copolymer, Styrene-acrylic copolymer such as styrene-butyl methacrylate copolymer, styrene-dimethylaminoethyl methacrylate copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer , Styrene-vinyl me Styrene copolymers such as luketone copolymer, styrene-butadiene 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 acid resin. These can be used alone or in combination of two or more. Among these, a styrene acrylic copolymer represented by styrene-butyl acrylate is particularly preferable in terms of development characteristics, fixability and the like.

It does not specifically limit as a coloring agent, The well-known thing shown below can be used.
The following are mentioned as a yellow pigment. Condensed azo compounds such as yellow iron oxide, navel yellow, naphthol yellow S, hansa yellow G, hansa yellow 10G, benzidine yellow G, benzidine yellow GR, quinoline yellow lake, permanent yellow NCG, tartrazine lake, isoindolinone compounds, Anthraquinone compounds, azo metal complexes, methine compounds, allylamide compounds. Specific examples include the following. C. I. Pigment Yellow 12, 13, 14, 15, 17, 62, 74, 83, 93, 94, 95, 109, 110, 111, 128, 129, 147, 155, 168, 180.

  Examples of the orange pigment include the following. Permanent orange GTR, pyrazolone orange, Vulcan orange, benzidine orange G, indanthrene brilliant orange RK, indanthrene brilliant orange GK.

  The following are mentioned as a red pigment. Bengala, Permanent Red 4R, Resol Red, Pyrazolone Red, Watching Red Calcium Salt, Lake Red C, Lake D, Brilliant Carmine 6B, Brilliant Carmine 3B, Eoxin Lake, Rhodamine Lake B, Alizarin Lake, etc. Pyrrolopyrrole compound, anthraquinone, quinacridone compound, basic dye lake compound, naphthol compound, benzimidazolone compound, thioindigo compound, perylene compound. Specific examples include the following. C. I. Pigment Red 2, 3, 5, 6, 7, 23, 48: 2, 48: 3, 48: 4, 57: 1, 81: 1, 122, 144, 146, 166, 169, 177, 184, 185, 202, 206, 220, 221, 254.

  The following are mentioned as a blue pigment. Copper phthalocyanine compounds such as alkali blue lake, Victoria blue lake, phthalocyanine blue, metal-free phthalocyanine blue, phthalocyanine blue partial chloride, first sky blue, indanthrene blue BG and their derivatives, anthraquinone compounds, basic dye lake compounds, and the like. Specific examples include the following. C. I. Pigment Blue 1, 7, 15, 15: 1, 15: 2, 15: 3, 15: 4, 60, 62, 66.

Examples of purple pigments include fast violet B and methyl violet lake.
Examples of the green pigment 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, non-magnetic ferrite, magnetite, the above-described yellow colorant, red colorant, and blue colorant, and those that have been adjusted to black. These colorants can be used alone or in combination and further in the form of a solid solution.
In addition, it is preferable that content of a coloring agent is 3.0-15.0 mass parts with respect to 100 mass parts of binder resin or a polymerizable monomer.

Further, the toner may contain a charge control agent. A well-known thing can be used as a charge control agent. For example, the following are mentioned. Aromatic carboxylic acid metal compounds typified by salicylic acid, alkyl salicylic acid, dialkyl salicylic acid, naphthoic acid, dicarboxylic acid, etc .; metal salts or metal complexes of azo dyes or azo pigments; boron compounds, silicon compounds, calixarenes . Further, the following quaternary ammonium salts and polymer compounds having a quaternary ammonium salt in the side chain as a positive charge control agent; guanidine compounds; nigrosine compounds; imidazole compounds.
The addition amount of these charge control agents is preferably 0.01 to 10.00 parts by mass with respect to 100 parts by mass of the binder resin or polymerizable monomer.

  The toner of the present invention may contain a wax as a release agent. Examples of the wax include the following. Petroleum wax such as paraffin wax, microcrystalline wax, petrolatum and derivatives thereof; montan wax and derivatives thereof; hydrocarbon wax and derivatives thereof according to Fischer-Tropsch method; polyolefin wax and derivatives thereof such as polyethylene wax and polypropylene wax; carnauba wax; Natural waxes such as 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; plant waxes; Of these, paraffin wax, ester wax and hydrocarbon wax are particularly preferred from the viewpoint of excellent releasability.

In the toner of the present invention, various organic or inorganic fine powders may be externally added to the toner particles as necessary. The organic or inorganic fine powder preferably has a particle size of 1/10 or less of the weight average particle size of the toner particles in view of durability when added to the toner particles.
As organic or inorganic fine powder, the following are used, for example.

(1) Fluidity imparting agent: silica, alumina, titanium oxide, carbon black, and carbon fluoride.
(2) Abrasive: metal oxide (eg strontium titanate, cerium oxide, alumina, magnesium oxide, chromium oxide), nitride (eg silicon nitride), carbide (eg silicon carbide), metal salt (eg calcium sulfate, sulfuric acid) Barium, calcium carbonate).
(3) Lubricant: fluororesin powder (for example, vinylidene fluoride, polytetrafluoroethylene), fatty acid metal salt (for example, zinc stearate, calcium stearate).
(4) Charge controllable particles: metal oxide (for example, tin oxide, titanium oxide, zinc oxide, silica, alumina), carbon black.

  The organic or inorganic fine powder can also treat the surface of the toner particles in order to improve the fluidity of the toner and to make the charge of the toner particles uniform. Examples of the treatment agent for the hydrophobic treatment of the organic or inorganic fine powder include the following. Unmodified silicone varnish, various modified silicone varnishes, unmodified silicone oil, various modified silicone oils, silane compounds, silane coupling agents, other organosilicon compounds, and organotitanium compounds. These treatment agents may be used alone or in combination.

  As a means for producing the toner particles, a conventionally known method can be used without any particular limitation. In particular, the suspension polymerization method or the dissolution suspension method in which toner is produced by granulating in an aqueous medium can obtain a toner having a spherical shape or a shape close to a sphere and a uniform surface property. The charge amount distribution is excellent, and an excellent effect of expanding the fog latitude can be obtained.

  Preferred examples of the polymerizable monomer in the suspension polymerization method include the following vinyl polymerizable monomers. Styrene; α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, p- Styrene derivatives such as n-hexyl styrene, pn-octyl, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, p-phenyl styrene; methyl acrylate, ethyl Acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-nonyl Acrylic polymerizable monomers such as acrylate, cyclohexyl acrylate, benzyl acrylate, dimethyl phosphate ethyl acrylate, diethyl phosphate ethyl acrylate, dibutyl phosphate ethyl acrylate, 2-benzoyloxyethyl acrylate; methyl methacrylate, ethyl methacrylate, n- Propyl methacrylate, iso-propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, n-amyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, n-nonyl methacrylate, diethylphos Fate ethyl methacrylate, dibutyl phosphate ethyl Methacrylic polymerizable monomers such as acrylate; methylene aliphatic monocarboxylic esters; vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate, vinyl butyrate, vinyl benzoate, vinyl formate; vinyl methyl ether, vinyl Vinyl ethers such as ethyl ether and vinyl isobutyl ether; vinyl methyl ketone, vinyl hexyl ketone, vinyl isopropyl ketone.

  Moreover, the following are mentioned as a polymerization initiator used in the case of superposition | polymerization. 2,2′-azobis- (2,4-divaleronitrile), 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis Azo or diazo polymerization initiators such as -4-methoxy-2,4-dimethylvaleronitrile and azobisisobutyronitrile; benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyloxy carbonate, cumene hydroperoxide, 2,4-dichloro Peroxide polymerization initiators such as benzoyl peroxide and lauroyl peroxide. These polymerization initiators are preferably added in an amount of 0.5 to 30.0% by mass relative to the polymerizable monomer, and may be used alone or in combination.

  In order to control the molecular weight of the binder resin constituting the toner particles, a chain transfer agent may be added during the polymerization. As a preferable addition amount, it is 0.001-15,000 mass% of a polymerizable monomer.

On the other hand, in order to control the molecular weight of the binder resin constituting the toner particles, a crosslinking agent may be added during the polymerization. The following are mentioned as a crosslinkable monomer. 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 diacrylate _{(CH 2 = CHCOO (CH 2} CH 2 O) nOCCH = CH 2 n = 4 molecular weight 308), polyethylene glycol # 400 diacrylate _{(CH 2 = CHCOO (CH 2} CH 2 O) nOCCH = CH 2 n = 9 molecular weight 5 8), the diacrylate and polyethylene glycol # 600 diacrylate _{(CH 2 = CHCOO (CH 2} CH 2 O) nOCCH = CH 2 n = 14 molecular weight 708), dipropylene glycol diacrylate, polypropylene glycol diacrylate, polyester-type Diacrylate (trade name: MANDA, manufactured by Nippon Kayaku Co., Ltd.) and those obtained by replacing the above acrylate with methacrylate.

  The following are mentioned as a polyfunctional crosslinking monomer. Pentaerythritol triacrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, oligoester acrylate and methacrylate thereof, 2,2-bis (4-methacryloxy-polyethoxyphenyl) propane, diacrylphthalate, Triallyl cyanurate, triallyl isocyanurate, triallyl trimellitate, diaryl chlorendate. A preferable addition amount is 0.001 to 15,000 mass% with respect to the polymerizable monomer.

  When the medium used in the suspension polymerization is an aqueous medium, the following can be used as the dispersion stabilizer for the particles of the polymerizable monomer composition. Tricalcium phosphate, magnesium phosphate, zinc phosphate, aluminum phosphate, calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate, bentonite, silica, alumina . Examples of the organic dispersant include the following. Polyvinyl alcohol, gelatin, methyl cellulose, methyl hydroxypropyl cellulose, ethyl cellulose, carboxymethyl cellulose sodium salt, starch.

Commercially available nonionic, anionic and cationic surfactants can also be used. Examples of such surfactants include the following. Sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, potassium stearate.
Hereinafter, various measurement methods related to the present invention will be described.

<Measurement method of molecular weight>
The weight average molecular weight (Mw) of the resin is measured by gel permeation chromatography (GPC) as follows.
First, a sample is dissolved in tetrahydrofuran (THF) at room temperature. Then, the obtained solution is filtered through a solvent-resistant membrane filter “Mysholy disk” (manufactured by Tosoh Corporation) having a pore diameter of 0.2 μm to obtain a sample solution. The sample solution is adjusted so that the concentration of the component soluble in THF is 0.8% by mass. Using this sample solution, measurement is performed under the following conditions.
Equipment: High-speed GPC equipment “HLC-8220GPC” [manufactured by Tosoh Corporation]
Column: Duplex of LF-604 [manufactured by Showa Denko KK]
Eluent: THF
Flow rate: 0.6 mL / min Oven temperature: 40 ° C
Sample injection amount: 0.020 mL
In calculating the molecular weight of the sample, standard polystyrene resin (for example, trade name “TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F— 10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500 ", manufactured by Tosoh Corporation) are used.

<Method for measuring acid value and hydroxyl value of crystalline polyester>
The acid value and hydroxyl value of the crystalline polyester are measured by potentiometric titration according to JIS-K0070-1992.

  Hereinafter, the present invention will be described in more detail with specific production methods, examples, and comparative examples, but this does not limit the present invention in any way. In addition, all the parts in the following mixing | blending are a mass part.

<Example of production of crystalline resin 1>
In a reaction vessel equipped with a stirrer, a thermometer, a nitrogen introduction tube, and a decompression device, 100 parts by mass of xylene was heated while being purged with nitrogen, and refluxed at a liquid temperature of 140 ° C. A mixture of 100 parts by mass of styrene and 8.00 parts by mass of dimethyl 2,2′-azobis (2-methylpropionate) as a polymerization initiator was added dropwise to the solution over 3 hours. After completion of the addition, the solution was stirred for 3 hours. did. Thereafter, xylene and residual styrene were distilled off at 160 ° C. and 1 hPa to obtain a vinyl polymer.

Next, the following materials were added to a reaction vessel equipped with a stirrer, a thermometer, a nitrogen introduction tube, a dehydration tube, and a decompression device, and reacted at 150 ° C. for 4 hours in a nitrogen atmosphere.
94.3 parts by mass of the vinyl polymer obtained above, 80.0 parts of xylene as the organic solvent, 78.2 parts by mass of 1,12-dodecanediol, 0.500 parts of titanium (IV) isopropoxide as the esterification catalyst.

  Then, 65.1 parts by mass of sebacic acid was added and reacted at 150 ° C. for 3 hours, and 9.3 parts by mass of stearic acid was added and reacted at 180 ° C. for 4 hours. Then, it was made to react until it became a desired acid value and a hydroxyl value at 180 degreeC and 1 hPa further, and the crystalline resin 1 was obtained. The physical properties are shown in Table 1.

<Production example of crystalline resins 2 to 13>
In the production example of the crystalline resin 1, the crystalline resins 2 to 13 were obtained in the same manner except that the raw materials shown in Table 1 were changed and the reaction time was adjusted so that the desired acid value, hydroxyl value, and molecular weight were obtained. It was. The physical properties are shown in Table 1.

<Examples of polyester resin production>
-Terephthalic acid: 11.0 mol part-Bisphenol A-propylene oxide 2-mol adduct (PO-BPA):
10.9 mol parts The above monomer was charged into an autoclave together with an esterification catalyst, and a decompression device, a water separation device, a nitrogen gas introduction device, a temperature measurement device, and a stirring device were attached to the autoclave. While reducing the pressure in a nitrogen atmosphere, the reaction was performed at 210 ° C. according to a conventional method to obtain a polyester resin. The obtained polyester resin had a glass transition temperature (Tg) of 68 ° C., a weight average molecular weight (Mw) of 7,400, and a number average molecular weight (Mn) of 3,020.

<Example 1>
In a four-necked vessel equipped with a reflux tube, a stirrer, a thermometer, and a nitrogen introduction tube, 700 parts by mass of ion-exchanged water, 1,000 parts by mass of a 0.1 mol / liter Na ₃ PO ₄ aqueous solution and 1.0 part by mass. 24.0 parts by mass of an aqueous HCl / liter HCl solution was added. And it maintained at the temperature of 60 degreeC, stirring at 12,000 rpm using the high-speed stirring apparatus TK homomixer (Special Machine Industries Co., Ltd.). To this, 85 parts by mass of a 1.0 mol / liter CaCl ₂ aqueous solution was gradually added to prepare an aqueous dispersion medium containing a fine hardly water-soluble dispersion stabilizer Ca ₃ (PO ₄ ) ₂ . Thereafter, a polymerizable monomer composition was prepared using the following raw materials.

Styrene 75.0 parts by mass n-butyl acrylate 25.0 parts by mass Divinylbenzene 0.05 parts by mass Copper phthalocyanine pigment (CI Pigment Blue 15: 3) 6.5 parts by mass The above polyester resin 4.0 parts by mass, crystalline resin 1 5.0 parts by mass, charge control agent 0.1 parts by mass (aluminum compound of 3,5-di-tert-butylsalicylic acid)
-Release agent (behenyl behenate) 10.0 parts by mass-Aluminum stearate 2.0% by mass based on crystalline resin

  The above raw materials were dispersed for 3 hours with an attritor (manufactured by Nippon Coke Industry Co., Ltd.) to prepare a polymerizable monomer composition. Next, this polymerizable monomer composition is transferred to another container and kept at a temperature of 60 ° C. for 20 minutes with stirring. Thereafter, 16.0 parts by mass of t-butyl peroxypivalate as a polymerization initiator ( Toluene solution 50%) was added and held for 5 minutes with stirring. Next, the polymerizable monomer composition was put into an aqueous dispersion medium and granulated for 10 minutes while stirring with a high-speed stirring device.

Thereafter, the high-speed stirrer was changed to a propeller stirrer, the internal temperature was raised to 72 ° C., and the reaction was allowed to proceed for 5 hours with slow stirring.
Next, the temperature inside the container was raised to 90 ° C. and maintained for 8.0 hours.
Thereafter, 300 parts by mass of ion-exchanged water was added, the reflux tube was removed, and a distillation apparatus was attached. Distillation at a temperature in the vessel of 100 ° C. was performed for 5 hours to remove residual monomers and toluene, thereby obtaining a polymer slurry.
Dilute hydrochloric acid was added to the container containing the polymer slurry after cooling to a temperature of 30 ° C. to remove the dispersion stabilizer. Further, after filtration, washing, and drying, fine coarse powder was cut by air classification to obtain toner 1 composed of toner particles. The formulation and conditions of Toner 1 are shown in Table 2, and the physical properties are shown in Table 3.

<Examples 2 to 27>
According to the formulation of the crystalline resin and fatty acid metal salt shown in Table 2, toners 2 to 27 were obtained in the same manner as in toner 1 except that.
Evaluation was performed in the same manner as in Example 1 by using the obtained toners 2 to 27.

<Comparative Examples 1-2>
Comparative toners 1 and 2 were obtained by the same production method as toner 1 except that the crystalline resin and fatty acid metal salt shown in Table 2 were used.
Further, evaluation was performed in the same manner as in Example 1 using the obtained comparative toners 1 and 2.

The following evaluation was performed using the obtained toner particles and comparative toner particles.
[Evaluation of cab latitude]
FIG. 1 shows an example of a schematic cross-sectional view of an electrophotographic apparatus that can use the toner of the present invention.
The four photoreceptors 1 and the devices around them are responsible for four colors (yellow, magenta, cyan, and black). The photoreceptor 1 rotates in the direction of arrow A (clockwise). Then, it is charged by the charging device 8 and an electrostatic charge image (latent image) is formed by exposure with the laser beam 7. The toner 4 in the developing device 6 is stirred by the stirring blade 11 and supplied to the developing roller 2 by the toner supply roller 3. Then, the electrostatic charge image is developed by the developing roller 2 to form a toner image.

  The transfer conveyance belt 16 is stretched around the driving roller 12, the tension roller 15, and the driven roller 17, and the image transfer surface moves in the direction of arrow B as the driving roller 12 rotates. When a color image is formed, a toner image formed by development processing on each photoconductor 1 is transferred to each photoconductor at a nip portion where each photoconductor 1 and the transfer roller 13 are formed with the transfer conveyance belt 16 interposed therebetween. 1 is sequentially transferred to the transfer conveyance belt 16. The color image formed by being sequentially transferred is transported to a nip formed by the driven roller 17 and the suction roller 20 with the transfer transport belt 16 in between, transferred to a recording material (paper) 18, and then inside the fixing device 21. The fixing process is performed by heating and pressing.

  A tandem laser beam printer LBP9660Ci manufactured by Canon Inc. having the configuration as shown in FIG. 1 has been modified so that printing can be performed using only the cyan station. In addition, it was modified so that the back contrast can be set arbitrarily. Furthermore, it was modified so that the process speed could be set and set to 200 mm / sec. The LBP9660Ci toner cartridge was filled with 150 g of toner 1 and evaluated.

  The back contrast (potential difference between the non-image portion of the electrostatic charge image carrier and the toner carrier) was changed from 40 V to 400 V in increments of 10 V, and a white background image (an image with a print ratio of 0%) was printed on each. Then, using “REFLECTOMETER MODEL TC-6DS” (manufactured by Tokyo Denshoku) equipped with an amber filter, the reflectance (%) of the unused paper and the reflectance (%) of the entire white background image are measured. The fog density (%) was calculated from the difference between the two reflectances.

The above operation was performed in the following environments and at the initial stage and after printing 20,000 sheets.
・ Low temperature and low humidity environment (LL environment; temperature 15 ° C, relative humidity 10%)
・ Normal temperature and humidity environment (NN environment; temperature 23 ° C, relative humidity 50%)
・ High temperature and high humidity environment (HH environment; temperature 30 ° C, relative humidity 80%)
FIG. 2 and FIG. 3 show measurement examples. The potential difference between the lower limit (V) and the upper limit (V) of the back contrast at which the fog density is 2.0% or less is defined as fog latitude (fog tolerance). . If the fog latitude is 100 V or more, it is determined that the fog control design is superior. The results are shown in Table 3.

[Fog after standing in harsh environment]
A toner cartridge for LBP9660Ci was filled with 150 g of the toner that was allowed to stand for 168 hours in a harsh environment (temperature 40 ° C./relative humidity 95%).
In a normal temperature and humidity environment (temperature 23 ° C./relative humidity 50%), 100 horizontal-line images with a printing rate of 1% are printed out, and the reflectance (%) of the non-image area of the 100th image is obtained. It was measured with “REFLECTOMETER MODEL TC-6DS” (manufactured by Tokyo Denshoku). A numerical value (%) obtained by subtracting the obtained reflectance (%) from the reflectance (%) of an unused printout paper (plain paper) measured in the same manner was evaluated based on the following criteria. The smaller the numerical value, the more image fog is suppressed. In the present invention, C or higher is an acceptable level.

(Evaluation criteria)
A: Less than 0.3% B: 0.3% or more and less than 0.8% C: 0.8% or more and less than 1.3% D: 1.3% or more and less than 2.0% E: 2.0% or more

[Fixable temperature margin]
The difference between the following (1) hot offset end temperature and (2) low temperature offset end temperature is defined as (3) fixable temperature margin.

(1) Hot offset end temperature (hot offset resistance)
The fixing unit of the laser beam printer LBP9600C manufactured by Canon Inc. was modified so that the fixing temperature could be adjusted. Using this modified LBP9600C, the fixing temperature was changed from 210 ° C. in increments of 5 ° C. at a process speed of 300 mm / sec.
For toner 1, a square solid image of 5 cm in length and 5 cm in width with a toner loading of 0.40 mg / cm ^{2 was formed} at the center of the position in cm from the front end of the image receiving paper in the sheet passing direction. Then, hot offset at the rear end of the image receiving paper after passing through the fixing device (a phenomenon in which a part of the fixed image adheres to the member surface of the fixing device and is fixed on the image receiving paper in the next round) Was confirmed. When no hot offset occurred, the temperature of the surface of the fixing heating unit at that time was measured, and the measured temperature was defined as the hot offset end temperature. When hot offset occurred, the fixing temperature (set value) was lowered by 5 ° C. as described above, and the above-described formation of a solid image and confirmation of the presence or absence of hot offset were repeated. When hot offset did not occur, the temperature of the surface of the fixing heating part at that time was measured and used as the hot offset end temperature.
As the image receiving paper, A4 color laser copier paper (manufactured by Canon Inc., weight 80 g / m ² ) was used.
Evaluation was carried out in a low-temperature and low-humidity environment (temperature 15 ° C./relative humidity 10%).

(2) Low temperature offset end temperature (low temperature fixability)
The fixing unit of the laser beam printer LBP9600C manufactured by Canon Inc. was modified so that the fixing temperature could be adjusted. Using this modified LBP9600C, the fixing temperature was changed from 145 ° C. in increments of 5 ° C. at a process speed of 300 mm / sec.
For Toner 1, a solid image having a toner loading of 0.40 mg / cm ² was formed on the image receiving paper, and heated and pressurized oillessly to form a fixed image on the image receiving paper. The size and shape of the solid image and the position where the solid image was formed were the same as those described in “(1) Hot offset end temperature (hot offset resistance)”.

As the image receiving paper, busyness 4200 (manufactured by Xerox, weight of 105 g / m ² ) was used.
Using Kimwipe (S-200, manufactured by Nippon Paper Crecia Co., Ltd.), rub the fixed image 10 times with a load of 75 g / cm ² , and lower the temperature at which the reduction rate of image density before and after rubbing is less than 5%. The offset end temperature was used.
For the measurement of the image density, a color reflection densitometer X-RITE 404A (manufactured by X-Rite Co.) was used to measure the relative density with respect to the printout image of the white background portion having an image density of 0.00. The reduction rate of the image density was calculated.
Evaluation was carried out in a low-temperature and low-humidity environment (temperature 15 ° C./relative humidity 10%).

(3) Fixable temperature margin The difference between the above (1) hot offset end temperature and (2) low temperature offset end temperature is defined as a fixable temperature margin.
(Evaluation criteria)
A: 50 ° C. or more B: 40 ° C. or more and less than 50 ° C. C: 25 ° C. or more and less than 40 ° C. D: 15 ° C. or more and less than 25 ° C. E: Less than 15 ° C. In the present invention, C or more is an acceptable level.

[Heat resistant storage stability]
5 g of each toner was placed in a 50 cc resin cup and allowed to stand for 3 days at a temperature of 55 ° C./relative humidity of 10%, and the presence or absence of aggregates was examined and evaluated.
(Evaluation criteria)
A: No agglomerate is generated B: Minor agglomerate is generated, and when it is lightly pressed with a finger, it collapses without feeling C: A slight agglomerate is generated, and when it is lightly pressed with a finger, it feels but collapses D: An agglomerate It is generated and does not collapse even when lightly pressed with a finger. E: Completely agglomerated, and does not collapse even when strongly pressed with a finger.

1: Photoconductor, 2: Developing roller, 3: Toner supply roller, 4: Toner, 5: Regulating blade, 6: Developing device, 7: Laser beam, 8: Charging device, 9: Cleaning device, 10: Charging for cleaning Device: 11: stirring blade, 12: driving roller, 13: transfer roller, 14: bias power source, 15: tension roller, 16: transfer conveying belt, 17: driven roller, 18: paper, 19: paper feeding roller, 20: Adsorption roller, 21: fixing device

Claims (5)

A toner having toner particles containing a binder resin, a colorant, a fatty acid metal salt, and a crystalline resin having a crystalline polyester portion,
The crystalline polyester portion has an alkyl group having 7 or more carbon atoms at the end,
A toner wherein C1 and C2 satisfy the following relational expression (1), where C1 is a carbon number of the alkyl group and C2 is a carbon number of a fatty acid constituting the fatty acid metal salt.
0.25 ≦ C1 / C2 ≦ 3.90 Formula (1)   The acid value of the crystalline resin is 4.0 mgKOH / g or less, the hydroxyl value of the crystalline resin is 7.0 mgKOH / g or less, and the weight average molecular weight (Mw) of the crystalline resin is 15,000 or more. The toner according to claim 1, wherein the toner is 45,000 or less.   The toner according to claim 1, wherein the content of the fatty acid metal salt in the toner particles is 0.2% by mass or more and 20.0% by mass or less with respect to the mass of the crystalline resin. The toner according to claim 1, wherein the C1 and the C2 satisfy the following relational expression (2).
0.75 ≦ C1 / C2 ≦ 1.30 Formula (2) The toner according to claim 1, wherein the fatty acid metal salt contains any one of Al, Ba, Ca, Mg, Zn, Fe, Ti, Co, and Zr.