JP6900262B2 - toner - Google Patents

Description

The present invention relates to toners used in image forming methods such as electrophotographic, electrostatic recording, and toner jet methods.

In recent years, printers and copiers have been required to have high speed and low power consumption, and development of toners having excellent low-temperature fixability and heat-resistant storage stability has been required. In response to this demand, a method has been proposed in which crystalline polyester is used as the toner and the sharp melt property of the crystalline polyester is utilized to achieve both low-temperature fixability and heat-resistant storage stability. However, when crystalline polyester is used for the toner, the chargeability is deteriorated, and adverse effects such as fog deterioration may occur.

On the other hand, Patent Documents 1 and 2 disclose toners using crystalline polyester having a low acid value and hydroxyl value.
Although deterioration of chargeability of the toners disclosed in Patent Documents 1 and 2 is suppressed, there remains a problem in stability in a harsh environment under high temperature and high humidity. In addition, it was found by the studies of the present inventors that there is a problem of generation of electrostatic offset in fixing in a low temperature and low humidity environment. If an electrostatic offset occurs during fixing, the fixable temperature range becomes narrow. Today, with the spread of multifunction devices and printers, they are being used in various regions and environments, and there is a demand for toner with excellent stability in both low-temperature and low-humidity environments as well as high-temperature and high-humidity environments.

Japanese Patent No. 2931899 Japanese Unexamined Patent Publication No. 2002-318471

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

The above object is achieved by the following invention.
That is,
Bundling resin,
Colorant,
Fatty acid metal salts, and
A toner having toner particles containing a binding-crystalline resin,
The crystalline resin is a block polymer having a crystalline polyester moiety and an amorphous vinyl moiety.
The acid value of the crystalline resin is 4.0 mgKOH / g or less, and the acid value is 4.0 mgKOH / g or less.
The hydroxyl value of the crystalline resin is 7.0 mgKOH / g or less, and the hydroxyl value is 7.0 mgKOH / g or less.
The crystalline polyester moiety has an alkyl group having 7 or more carbon atoms at the terminal and has an alkyl group.
The fatty acid constituting the fatty acid metal salt is octanoic acid, nonanoic acid, lauric acid, stearic acid, behenic acid, or montanic acid.
When the carbon number of the alkyl group is C1 and the carbon number of the alkyl portion of the fatty acid constituting the fatty acid metal salt is C2, C1 and C2 satisfy the relationship represented by the following formula (2). It is a toner.
0.75 ≤ C1 / C2 ≤ 1.30 Equation ( 2 )

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

This is an example of a schematic cross-sectional view of an electrophotographic apparatus to which the present invention can be applied. This is an example showing the relationship between the back contrast and the fog density in the examples of the present invention. This is an example showing the relationship between the back contrast and the fog density in the comparative example of the present invention.

Hereinafter, the present invention will be described in detail.
The toner of the present invention
Bundling resin,
Colorant,
Fatty acid metal salts, and
A toner having toner particles containing a binding-crystalline resin,
The crystalline resin is a block polymer having a crystalline polyester moiety and an amorphous vinyl moiety.
The acid value of the crystalline resin is 4.0 mgKOH / g or less, and the acid value is 4.0 mgKOH / g or less.
The hydroxyl value of the crystalline resin is 7.0 mgKOH / g or less, and the hydroxyl value is 7.0 mgKOH / g or less.
The crystalline polyester moiety has an alkyl group having 7 or more carbon atoms at the terminal and has an alkyl group.
The fatty acid constituting the fatty acid metal salt is octanoic acid, nonanoic acid, lauric acid, stearic acid, behenic acid, or montanic acid.
When the carbon number of the alkyl group is C1 and the carbon number of the alkyl portion of the fatty acid constituting the fatty acid metal salt is C2, C1 and C2 satisfy the relationship represented by the following formula (2). It is a toner.
0.75 ≤ C1 / C2 ≤ 1.30 Equation ( 2 )

As a result, it is possible to obtain a toner having a wide fixable temperature range and heat-resistant storage stability, and suppressing fog in both a low temperature and low humidity environment to a high temperature and high humidity environment.
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, it is a crystalline resin having few terminal carboxy groups and terminal hydroxy groups of crystalline polyester and low acid value and hydroxyl value. By using a crystalline polyester having a low acid value and a hydroxyl value, the fixability and fog are improved unless it is left to stand in a harsh environment, but the fog tends to worsen if it is left to stand in a harsh environment. The reason for this is that the carboxy group and hydroxy group of the crystalline polyester are reduced to increase the affinity with the binder resin, or the interaction between these polar groups is reduced, so that the binder resin is contained. It is considered that the crystalline polyester became easier to bleed.

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

The low temperature offset is a phenomenon in which the toner in the lower layer of the fixed image near the interface with the paper is not sufficiently melted and therefore adheres to the surface of the member of the fixing device. The low temperature offset can be covered to some extent by the low temperature fixing effect of the crystalline polyester, so that the high temperature offset is a particular problem. Here, the high temperature offset is a phenomenon in which a part of the fixing image adheres to the surface of the fixing device member in a region where the temperature of the fixing member is high, and further fixed on the paper (recording material) in the next round. Hereinafter referred to as hot offset in this specification.

At this time, the crystalline polyester moiety in the crystalline resin has an alkyl group having 7 or more carbon atoms at the terminal, and a fatty acid metal salt satisfying the following relational expression (1) is present.
The present inventors have found that as a toner, deterioration of fog in a high temperature and high humidity environment is suppressed, and a wider fixable temperature range can be obtained.
0.25 ≤ C1 / C2 ≤ 3.90 Equation (1)
(C1 in the formula (1) represents the carbon number of the alkyl group, and C2 represents the carbon number of the fatty acid constituting the fatty acid metal salt.)
When an alkyl group having a plurality of carbon atoms or a fatty acid having a plurality of carbon atoms is present, the alkyl group having the highest abundance ratio or the fatty acid having the highest abundance ratio is defined as C1 and C2.

Although the reason why the effect of the present invention can be obtained is not clear, the interaction between the terminal alkyl group of the crystalline polyester moiety of the crystalline resin and the fatty acid moiety of the fatty acid metal salt works to disperse the crystalline resin in the toner. I think this is to improve the sex.
It is more preferable that C1 and C2 satisfy the following relational expression (2) to further increase the interaction.
0.75 ≤ C1 / C2 ≤ 1.30 Equation (2)

The crystalline resin contained in the toner of the present invention is characterized by containing a crystalline polyester moiety 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 monohydric alcohol or a monovalent acid having an alkyl chain having 7 or more carbon atoms is used, and a carboxy group or a hydroxy group at the polymer terminal is used. There is a method of sealing.

Examples of the monohydric 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, behenic acid and the like. This makes it easier to obtain the effect of improving heat-resistant storage stability. 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. As a result, deterioration of chargeability is suppressed and fog is suppressed.

The crystalline polyester can be obtained by reacting a polyvalent carboxylic acid having a divalent value or higher with a polyhydric alcohol. From the viewpoint of melting point and crystallinity, crystalline polyester containing an aliphatic dicarboxylic acid and an aliphatic diol as main raw materials is preferable.
Examples of the polyhydric alcohol include the following. 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, etc.

Examples of the polyvalent carboxylic acid include the following. Shuic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelli acid, speric acid, glutaconic acid, azelaic acid, sebacic acid, nonandicarboxylic acid, decandicarboxylic acid, undecandicarboxylic acid, dodecandicarboxylic acid, maleic acid, fumal Acids, mesaconic acid, citraconic acid, itaconic acid, isophthalic acid, terephthalic acid, n-dodecylsuccinic acid, n-dedosinel 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 moiety, but may be a block polymer having a crystalline polyester moiety and an amorphous vinyl moiety. It is preferable to have. The amorphous vinyl moiety is preferably produced from one or more polymerizable monomers selected from the following groups.
Examples of the polymerizable monomer include the following styrene-based polymerizable monomers, acrylic-based polymerizable monomers, and methacrylic-based polymerizable monomers. Styrene is preferable 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- Styrene-based polymerizable properties such as n-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene, p-methoxystyrene, and p-phenylstyrene. 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 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 , N-Nonyl methacrylate, diethyl phosphate ethyl methacrylate, and methacrylic polymerizable monomers such as dibutyl phosphate ethyl methacrylate.

As a method for producing a modified crystalline polyester modified with an amorphous vinyl moiety, the following known production methods and the like can be applied. A method of first synthesizing a crystalline polyester moiety and then extending an amorphous vinyl moiety by atom transfer radical polymerization or the like. A method of first synthesizing an amorphous vinyl moiety into which a reactive functional group has been introduced and then extending a crystalline polyester moiety. A method in which a crystalline polyester moiety and an amorphous vinyl moiety are first synthesized separately and then bonded to each other.

The weight average molecular weight (Mw) of the crystalline resin is preferably 15,000 or more and 45,000 or less. If the weight average molecular weight is less than 15,000, the heat resistance is deteriorated, and if it is more 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 it is 1% by mass or more, the low temperature fixability is improved, and when it is 30% by mass or less, it is possible to obtain chargeability and heat-resistant storage property which are not practically problematic.

As the fatty acid metal salt used in the present invention, conventionally known fatty acid metal salts can be used without particular limitation. Specifically, as the fatty acid, the following known fatty acids can be used. 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 acid with a branched structure such as 15-methylhexadecanoic acid. Further, the same effect can be obtained regardless of whether one of these fatty acids is bound to one central metal or a plurality of these fatty acids are bound 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 have higher stability. Further, 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 it is 0.2% by mass or more, the fixable temperature range is widened, and when it is 20.0% by mass or less, it is possible to obtain chargeability without a problem in practical use.

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

As the binder resin, the following can be used. Monopolymers of styrene such as polystyrene and polyvinyltoluene and its substituents; styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalin copolymer, styrene-methylacrylate copolymer, styrene- Ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, dimethylaminoethyl styrene-acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer Styrene-acrylic copolymers such as copolymers, styrene-butyl methacrylate copolymers, styrene-dimethylaminoethyl methacrylate copolymers, styrene-vinyl methyl ether copolymers, styrene-vinyl ethyl ether copolymers , Styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-maleic acid copolymer, styrene-maleic acid ester copolymer and other styrene-based copolymers; polymethyl Methacrylate, polybutylmethacrylate, polyvinylacetate, styrene, polypropylene, polyvinylbutyral, silicone resin, polyester resin, polyamide resin, epoxy resin, polyacrylic acid resin. These can be used alone or in combination of two or more. Of these, a styrene-acrylic copolymer represented by styrene-butyl acrylate is particularly preferable in terms of development characteristics, fixability, and the like.

The colorant is not particularly limited, and the following known colorants can be used.
Examples of the yellow pigment include the following. Condensed azo compounds such as Yellow Iron Oxide, Nabres Yellow, Naftor Yellow S, Hansa Yellow G, Hansa Yellow 10G, Benzidine Yellow G, Benzidine Yellow GR, Kinolin Yellow Lake, Permanent Yellow NCG, Tartradin Lake, Isoindolinone Compounds Anthracinone 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, Balkan Orange, Benzidine Orange G, Indanthrone Brilliant Orange RK, Indanthrone Brilliant Orange GK.

Examples of the red pigment include the following. Condensed azo compounds such as Bengala, Permanent Red 4R, Resole Red, Pyrazolone Red, Watching Red Calcium Salt, Lake Red C, Lake D, Brilliant Carmine 6B, Brilliant Carmine 3B, Eoxin Lake, Rhodamin Lake B, Alizarin Lake, Diketo Pyrrolopyrrole compound, anthracinone, 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 and 254.

Examples of the blue pigment include the following. Alkaline blue lake, Victoria blue lake, phthalocyanine blue, metal-free phthalocyanine blue, phthalocyanine blue partial chloride, first sky blue, copper phthalocyanine compounds such as induslen blue BG and their derivatives, anthracinone 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 the purple pigment 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 the white pigment include zinc white, titanium oxide, antimony white, and zinc sulfide.
Examples of the black pigment include carbon black, aniline black, non-magnetic ferrite, magnetite, and those toned to black using the yellow colorant, red colorant, and blue colorant. These colorants can be used alone or in admixture, and even in the form of a solid solution.
The content of the colorant is preferably 3.0 to 15.0 parts by mass with respect to 100 parts by mass of the binder resin or the polymerizable monomer.

Further, the toner may contain a charge control agent. As the charge control agent, known ones can be used. For example, the following can be mentioned. Metal compounds of aromatic carboxylic acids typified by salicylic acid, alkylsalicylic acid, dialkylsalicylic acid, naphthoic acid, dicarboxylic acid, etc .; metal salts or metal complexes of azo dyes or azo pigments; boron compounds, silicon compounds, calix arenes, etc. .. Further, as a positive charge control agent, the following polymer type compounds having a quaternary ammonium salt or a quaternary ammonium salt in the side chain; a guanidine compound; a niglosin compound; an imidazole compound.
The amount of these charge control agents added is preferably 0.01 to 10.00 parts by mass with respect to 100 parts by mass of the binder resin or the polymerizable monomer.

The toner of the present invention may contain wax as a release agent. Examples of the type of wax include the following. Petroleum waxes such as paraffin wax, microcrystallin wax, petrolatum and their derivatives; Montan wax and its derivatives; hydrocarbon waxes by the Fisher Tropsch method and their derivatives; polyolefin waxes such as polyethylene wax and polypropylene wax and their derivatives, 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 wax; ester wax; cured castor oil and its derivatives; plant waxes; animal waxes and the like. Of these, paraffin wax, ester wax and hydrocarbon wax are particularly preferable from the viewpoint of excellent mold releasability.

The toner of the present invention may be supplemented with various organic or inorganic fine powders to the toner particles, if 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 from the viewpoint of durability when added to the toner particles.
As the organic or inorganic fine powder, for example, the following is used.

(1) Fluidity imparting agent: silica, alumina, titanium oxide, carbon black and carbon fluoride.
(2) Abrasive: Metal oxide (for example, strontium titanate, cerium oxide, alumina, magnesium oxide, chromium oxide), nitride (for example, silicon nitride), carbide (for example, silicon carbide), metal salt (for example, calcium sulfate, sulfuric acid) Barium, calcium carbonate).
(3) Lubricating agent: Fluorine-based resin powder (for example, vinylidene fluoride, polytetrafluoroethylene), fatty acid metal salt (for example, zinc stearate, calcium stearate).
(4) Charge-controllable particles: metal oxides (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 homogenize the charge of the toner particles. Examples of the treatment agent for hydrophobizing 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, organic titanium 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 particular limitation. In particular, the suspension polymerization method and the dissolution suspension method, in which toner is produced by granulating in an aqueous medium, can obtain toner having a spherical shape or a shape close to a sphere and having a uniform surface property, so that the durability of the toner is improved. It has an excellent charge distribution and can obtain a more excellent effect of cavitation toner expansion.

As the polymerizable monomer in the suspension polymerization method, the vinyl-based polymerizable monomer shown below can be preferably exemplified. 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-hexylstyrene, pn-octyl, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene, p-methoxystyrene, p-phenylstyrene; methylacrylate, 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 Methacrylate-based polymerizable monomers such as fate ethyl methacrylate and dibutyl phosphate ethyl methacrylate; methylene aliphatic monocarboxylic acid esters; vinyl acetate, vinyl propionate, vinyl benzoate, vinyl butyrate, vinyl benzoate, vinyl formate, etc. Vinyl ester; Vinyl ether such as vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether; Vinyl methyl ketone, vinyl hexyl ketone, vinyl isopropyl ketone.

Further, examples of the polymerization initiator used in the polymerization include the following. 2,2'-azobis- (2,4-divaleronitrile), 2,2'-azobisisobutyronitrile, 1,1'-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis Azo-based or diazo-based 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-based 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 based on the polymerizable monomer, and may be used alone or in combination.

Further, in order to control the molecular weight of the binder resin constituting the toner particles, a chain transfer agent may be added at the time of polymerization. The preferable addition amount is 0.001 to 15.000% by mass of the polymerizable monomer.

On the other hand, in order to control the molecular weight of the binder resin constituting the toner particles, a cross-linking 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 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 508), polyethylene glycol # 600 diacrylate (CH ₂ = CHCOO (CH ₂₎₎ CH ₂ O) nOCCH = CH ₂ n = 14 Molecular weight 708) and other diacrylates, dipropylene glycol diacrylate, polypropylene glycol diacrylate, polyester type diacrylate (trade name: MANDA, manufactured by Nippon Kayaku Co., Ltd.), And the above acrylate changed to methacrylate.

Examples of the polyfunctional crosslinkable monomer include the following. Pentaerythritol triacrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, tetramethylolmethanetetraacrylate, oligoester acrylate and its methacrylate, 2,2-bis (4-methacryloxy-polyethoxyphenyl) propane, diacrylic phthalate, Triallyl cyanurate, triallyl isocyanurate, triallyl trimellitate, diallyl chlorendate. The preferable addition amount is 0.001 to 15.000% by 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 .. In addition, examples of the organic dispersant include the following. Polyvinyl alcohol, gelatin, methyl cellulose, methyl hydroxypropyl cellulose, ethyl cellulose, sodium salt of carboxymethyl cellulose, starch.

It is also possible to use commercially available nonionic, anionic and cationic surfactants. Examples of such a surfactant 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, the sample is dissolved in tetrahydrofuran (THF) at room temperature. Then, the obtained solution is filtered through a solvent-resistant membrane filter "Myshori Disc" (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. This sample solution is used for measurement under the following conditions.
Equipment: High-speed GPC equipment "HLC-8220GPC" [manufactured by Tosoh Corporation]
Column: LF-604 double [Made by Showa Denko KK]
Eluent: THF
Flow velocity: 0.6 mL / min Oven temperature: 40 ° C
Sample injection volume: 0.020 mL
In calculating the molecular weight of the sample, standard polystyrene resin (for example, trade names "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) is used.

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

Hereinafter, the present invention will be described in more detail with reference to specific manufacturing methods, examples, and comparative examples, but this does not limit the present invention in any way. The number of copies in the following formulations is all parts by mass.

<Production example of crystalline resin 1>
A reaction vessel equipped with a stirrer, a thermometer, a nitrogen introduction tube, and a decompression device was heated with 100 parts by mass of xylene substituted with nitrogen, and the mixture was 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, and the solution was stirred for 3 hours after completion of the addition. did. Then, 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 the mixture was reacted at 150 ° C. for 4 hours under a nitrogen atmosphere.
94.3 parts by mass of the vinyl polymer obtained above, 80.0 parts by mass of xylene as an organic solvent, 78.2 parts by mass of 1,12-dodecanediol, and 0.500 parts of titanium (IV) isopropoxide as an 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, the reaction was further carried out at 180 ° C. and 1 hPa until a desired acid value and hydroxyl value were obtained to obtain a crystalline resin 1. The physical characteristics 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 were changed to those shown in Table 1 and the reaction time was adjusted so as to obtain the desired acid value, hydroxyl value and molecular weight. It was. The physical characteristics are shown in Table 1.

<Production example of polyester resin>
-Terephthalic acid: 11.0 mol parts-Bisphenol A-propylene oxide 2 mol adduct (PO-BPA):
10.9 mol part The above-mentioned 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 measuring device and a stirring device were mounted on the autoclave. The reaction was carried out at 210 ° C. according to a conventional method while reducing the pressure in a nitrogen atmosphere 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>
_{700 parts by mass of ion-exchanged water and 1,000 parts by mass of 0.1 mol / liter Na 3} PO ₄ aqueous solution and 1.0 in a four-port container equipped with a recirculation tube, a stirrer, a thermometer, and a nitrogen introduction tube. 24.0 parts by mass of a molar / liter aqueous HCl solution was added. Then, the temperature was maintained at 60 ° C. while stirring at 12,000 rpm using a high-speed stirring device TK homomixer (Special Machinery Chemical Industry 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 water-insoluble dispersion stabilizer Ca ₃ (PO ₄ ) _2. Then, 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 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 with respect to crystalline resin

The above raw materials were dispersed with an attritor (manufactured by Nippon Coke Industries, Ltd.) for 3 hours to prepare a polymerizable monomer composition. Next, the polymerizable monomer composition was transferred to another container and held at a temperature of 60 ° C. for 20 minutes with stirring, and then 16.0 parts by mass of t-butylperoxypivalate (a polymerization initiator) was used. 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.

Then, the high-speed stirrer was changed to a propeller-type stirrer, the internal temperature was raised to 72 ° C., and the reaction was carried out for 5 hours with slow stirring.
Next, the temperature inside the container was raised to 90 ° C. and maintained for 8.0 hours.
Then, 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 of 100 ° C. in the container was carried out for 5 hours to remove residual monomers and toluene to obtain a polymer slurry.
Dilute hydrochloric acid was added to the container containing the polymer slurry cooled to a temperature of 30 ° C. to remove the dispersion stabilizer. Further, after filtering, washing, and drying, fine coarse powder was cut by wind power 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 2-27>
Toners 2 to 27 were obtained in the same manner as in Toner 1 except for the formulations of the crystalline resin and the fatty acid metal salt shown in Table 2.
Moreover, the evaluation was performed in the same manner as in Example 1 using the obtained toners 2-27.
In addition, Examples 2, 3, 6, 7, 13 and 15 are described as reference examples.

<Comparative Examples 1-2>
Comparative toners 1 and 2 were obtained by the same production method as that of toner 1 except for the formulations of the crystalline resin and the fatty acid metal salt shown in Table 2.
Moreover, the 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 the comparative toner particles.
[Evaluation of cab latitude]
FIG. 1 shows an example of a schematic cross-sectional view of an electrophotographic apparatus capable of using the toner of the present invention.
The four photoconductors 1 and their surrounding devices are responsible for each of the four colors (yellow, magenta, cyan, and black). The photoconductor 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 agitated by the stirring blade 11, and is 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 transfer belt 16 is stretched on the drive roller 12, the tension roller 15, and the driven roller 17, and the image transfer surface moves in the direction of the arrow B as the drive roller 12 rotates. When a color image is formed, the toner image formed by the development process in each photoconductor 1 is obtained in the nip portion formed by each photoconductor 1 and the transfer roller 13 sandwiching the transfer transfer belt 16. The images are sequentially transferred from 1 to the transfer transfer belt 16. The color image formed by sequentially transferring is transferred to the nip portion formed by the driven roller 17 and the suction roller 20 sandwiching the transfer transport belt 16, transferred to the recording material (paper) 18, and inside the fixing device 21. It is fixed by heating and pressurizing.

The tandem type laser beam printer LBP9660Ci manufactured by Canon Inc. having the configuration as shown in FIG. 1 was modified so that printing can be performed only with a 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. This 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 steps of 10 V, and an entirely white background image (an image having a print ratio of 0%) was printed in each. Then, using the "REFLECTOMETER MODEL TC-6DS" (manufactured by Tokyo Denshoku Co., Ltd.) equipped with an amber filter, the reflectance (%) of the unused paper and the reflectance (%) of the entire white background image are measured. Then, the fog concentration (%) was calculated from the difference between the two reflectances.

The above work was carried out under each of the following environments at the initial stage and after printing 20,000 sheets.
・ Low temperature and low humidity environment (LL environment; temperature 15 ° C, relative humidity 10%)
・ Room 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%)
Although measurement examples are shown in FIGS. 2 and 3, the potential difference between the lower limit value (V) and the upper limit value (V) of the back contrast at which the fog concentration is 2.0% or less is defined as the fog latitude (fog tolerance). .. When the fog latitude is 100 V or more, it is judged that the fog control design is superior. The results are shown in Table 3.

[Fog after standing in a harsh environment]
The LBP9660Ci toner cartridge was filled with 150 g of toner that had been allowed to stand in a harsh environment (temperature 40 ° C./relative humidity 95%) for 168 hours.
Under normal temperature and humidity environment (temperature 23 ° C / relative humidity 50%), 100 images with a print rate of 1% are printed out with horizontal lines, and the reflectance (%) of the non-image part of the 100th image is calculated. The measurement was performed with "REFLECTOMTER MODEL TC-6DS" (manufactured by Tokyo Denshoku Co., Ltd.). A numerical value (%) obtained by subtracting the obtained reflectance (%) from the reflectance (%) of the unused printout paper (plain paper) measured in the same manner was evaluated based on the following criteria. The smaller the value, the more the 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. to 5 ° C. at a process speed of 300 mm / sec.
For the toner 1, a solid image of a square having a length of 5 cm and a width of 5 cm was imaged at the center of the image receiving paper at a position cm from the tip in the paper-passing direction with a toner loading of 0.40 mg / cm ^2. Then, hot offset (a phenomenon in which a part of the fixed image adheres to the surface of the member of the fixing device and is further fixed on the receiving paper in the next round) at the rear end of the image receiving paper after passing through the fixing device in the paper passing direction). Was confirmed. When the hot offset did not occur, the temperature of the surface of the fixing heating part at that time was measured, and the measured temperature was defined as the hot offset end temperature. When the hot offset occurred, the fixing temperature (set value) was lowered by 5 ° C. as described above, and the above-mentioned image formation of the solid image and confirmation of the presence or absence of the hot offset were repeated. When the 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., with a weight of 80 g / m ² ) was used.
The 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 5 ° C. increments at a process speed of 300 mm / sec.
For the toner 1, a solid image having a toner loading amount of 0.40 mg / cm ² was formed on the image receiving paper and heated and pressed without oil 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 imaged were the same as those described in "(1) Hot offset end temperature (hot offset resistance)" above.

As the image receiving paper, businesss 4200 (manufactured by Xerox, with a 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 under a load of 75 g / cm 2} , and lower the temperature at which the rate of decrease in image density before and after rubbing becomes less than 5%. The offset end temperature was used.
To measure the image density, a color reflection densitometer X-RITE 404A (manufactured by X-Rite Co.) was used to measure the relative density of the white background portion with an image density of 0.00 with respect to the printout image, and after rubbing. The rate of decrease in image density was calculated.
The evaluation was carried out in a low temperature and low humidity (temperature 15 ° C./relative humidity 10%) environment.

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

[Heat storage]
5 g of each toner was placed in a 50 cc resin cup and allowed to stand at a temperature of 55 ° C. and a relative humidity of 10% for 3 days, and the presence or absence of agglomerates was examined and evaluated.
(Evaluation criteria)
A: No agglomerates are generated B: Light agglutinates are generated and collapse without touch when pressed lightly with a finger C: Light agglutinates are generated and feel but collapse when pressed lightly with a finger D: Agglutinates are generated Generated and does not collapse even when lightly pressed with a finger E: Completely aggregated and does not collapse even when strongly pressed with a finger In the present invention, C or higher is an acceptable level.

1: Photoreceptor 2: Development roller 3: Toner supply roller 4: Toner, 5: Regulatory blade, 6: Development device, 7: Laser light, 8: Charging device, 9: Cleaning device, 10: Charging for cleaning Equipment, 11: Stirring blade, 12: Drive roller, 13: Transfer roller, 14: Bias power supply, 15: Tension roller, 16: Transfer transfer belt, 17: Driven roller, 18: Paper, 19: Feed roller, 20: Suction roller, 21: Fixing device

Claims (4)

Bundling resin,
Colorant,
Fatty acid metal salts, and
A toner having toner particles containing a binding-crystalline resin,
The crystalline resin is a block polymer having a crystalline polyester moiety and an amorphous vinyl moiety.
The acid value of the crystalline resin is 4.0 mgKOH / g or less, and the acid value is 4.0 mgKOH / g or less.
The hydroxyl value of the crystalline resin is 7.0 mgKOH / g or less, and the hydroxyl value is 7.0 mgKOH / g or less.
The crystalline polyester moiety has an alkyl group having 7 or more carbon atoms at the terminal and has an alkyl group.
The fatty acid constituting the fatty acid metal salt is octanoic acid, nonanoic acid, lauric acid, stearic acid, behenic acid, or montanic acid.
When the carbon number of the alkyl group is C1 and the carbon number of the alkyl portion of the fatty acid constituting the fatty acid metal salt is C2, C1 and C2 satisfy the relationship represented by the following formula (2). toner.
0.75 ≤ C1 / C2 ≤ 1.30 Equation ( 2 ) The toner according to claim 1 the weight average molecular weight before Symbol crystalline resin (Mw) is 15,000 or more 45,000 or less. The toner according to claim 1 or 2, 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 any one of claims 1 to 3 , wherein the fatty acid metal salt contains at least one selected from the group consisting of Al, Ba, Ca, Mg, Zn, Fe, Ti, Co, and Zr. ..

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