JP2019020491A - toner - Google Patents

Abstract

To provide a toner with a wide fixable temperature range that is excellent in resistance against stain on a developing member under a high-temperature and high-humidity environment and achieves both low-temperature fixability and electrostatic offset resistance under a low-temperature and low-humidity environment.SOLUTION: A toner includes toner particles containing a binder resin, a crystalline resin, a polar resin, a mold release agent, and a colorant. The crystalline resin contains a crystalline polyester resin having an alkyl group having 7 or more carbon atoms at the terminal; the polar resin has a partial structure derived from styrene in an amount of 50.00 mass% or more and has a hydroxyl value of 5.0 mgKOH/g or more and an acid value of 10.0 mgKOH/g or more; the mold release agent has an alkyl group having 7 or more carbon atoms.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 lowered, which may cause problems such as fogging.

On the other hand, a toner using a crystalline polyester having a low acid value and hydroxyl value is disclosed (Patent Documents 1 and 2).
With respect to the toners disclosed in Patent Documents 1 and 2, although a decrease in chargeability is suppressed, there remains a problem in the contamination of the developing member in a high temperature and high humidity environment. Further, it has been found by the present inventors that there is a problem of generation of electrostatic offset particularly in fixing in a low temperature and low humidity environment. If electrostatic offset occurs during fixing, the fixable temperature range is narrowed.

Japanese Patent No. 2931899 JP 2002-318471 A

  SUMMARY OF THE INVENTION An object of the present invention is to provide a toner having a wide fixable temperature range, which is excellent in contamination of a developing member in a high temperature and high humidity environment, and has both low temperature fixability and electrostatic offset suppression in a low temperature and low humidity environment. is there.

As a result of intensive studies to solve the above problems, the present inventors have found the following toner. That is, one embodiment of the present invention is a toner having toner particles containing a binder resin, a crystalline resin, a polar resin, a release agent, and a colorant,
The crystalline resin includes a crystalline polyester resin having an alkyl group having 7 or more carbon atoms at its terminal,
The polar resin has a partial structure derived from styrene of 50.00% by mass or more, a hydroxyl value of 5.0 mgKOH / g or more, an acid value of 10.0 mgKOH / g or more,
The release agent is intended to provide a toner having an alkyl group having 7 or more carbon atoms.

  According to the present invention, it is possible to provide a toner having a wide fixable temperature range that is excellent in contamination of a developing member in a high temperature and high humidity environment, and has both low temperature fixability and electrostatic offset suppression in a low temperature and low humidity environment. it can.

Hereinafter, the present invention will be described in detail.
The present invention is a toner having toner particles containing a binder resin, a crystalline resin, a polar resin, a release agent, and a colorant.
The crystalline resin includes a crystalline polyester resin having an alkyl group having 7 or more carbon atoms at the terminal.
The polar resin has a partial structure derived from styrene of 50.00% by mass or more, a hydroxyl value of 5.0 mgKOH / g or more, and an acid value of 10.0 mgKOH / g or more.
The mold release agent has an alkyl group having 7 or more carbon atoms.
By satisfying the above requirements, it is possible to obtain a toner having a wide fixable temperature range that has excellent contamination of the developing member in a high-temperature and high-humidity environment and achieves both low-temperature fixability and electrostatic offset suppression in a low-temperature and low-humidity environment. be able to.

  The toner of the present invention contains a crystalline resin containing a crystalline polyester resin having an alkyl group having 7 or more carbon atoms at the terminal. That is, the crystalline polyester resin is a crystalline polyester resin in which the terminal carboxyl group and terminal hydroxy group of the crystalline polyester resin are decreased, and the acid value and the hydroxyl value are decreased. When a crystalline polyester resin having a low acid value and hydroxyl value is used, development stability such as low-temperature fixability and fogging suppression can be expected, but the developing member is easily contaminated when used in a high-temperature and high-humidity 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.

  At this time, the crystalline polyester resin has an alkyl group having 7 or more carbon atoms at the terminal and the release agent has an alkyl group having 7 or more carbon atoms, so that the developing member is contaminated in a high-temperature and high-humidity environment. The present inventors have found that the property can be suppressed. The reason why the effect of the present invention is obtained is not clear, but is considered as follows. That is, a hydrophobic interaction acts between the alkyl group of the crystalline polyester resin and the alkyl group of the release agent, and the crystalline polyester resin is trapped by the release agent in the toner, and the crystalline polyester resin becomes the toner. This is considered to be because it is easily crystallized.

In addition, when a crystalline polyester resin having a low acid value and hydroxyl value is used, electrostatic offset is likely to occur in fixing in a low temperature and low humidity environment.
The electrostatic offset is a phenomenon in which toner or a toner layer flies or adheres from the image receiving paper to the fixing device side by electrostatic force. If a crystalline polyester resin 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 fixing possible 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 image receiving paper is not sufficiently dissolved and adheres to the surface of the fixing device. Regarding the low temperature offset, since it can be improved by the low temperature fixing effect of the crystalline polyester, the high temperature offset is particularly problematic.
High temperature offset is a phenomenon in which the temperature of the fixing member is high, and a part of the fixed image adheres to the surface of the fixing device member, and is further fixed on the image receiving paper in the next round. Describe.

  At this time, a polar resin having a partial structure derived from styrene of 50.00% by mass or more, a hydroxyl value of 5.0 mgKOH / g or more, and an acid value of 10.0 mgKOH / g or more is used in combination. The present inventors have found that by using such a polar resin in combination, low-temperature fixability and electrostatic offset suppression can be achieved in a low-temperature and low-humidity environment. When the hydroxyl value of the polar resin is 5.0 mgKOH / g or more and the acid value is 10.0 mgKOH / g or more, polar groups such as a carboxy group and a hydroxy group are sufficiently present at the end of the polar resin. Although the mechanism by which the effects of the present invention can be obtained is not clear, it is considered that these polar groups can suppress electrostatic offset even in a low-temperature and low-humidity environment by optimizing the charge density at the fixing nip and suppressing charge-up. ing.

  Moreover, the polar resin of this invention needs to have 50.00 mass% or more of the partial structure derived from styrene. When the polar resin has a partial structure derived from styrene of 50.00% by mass or more, the affinity with a crystalline polyester resin having an alkyl group having 7 or more carbon atoms at the terminal decreases. Furthermore, since a release agent having an alkyl group having 7 or more carbon atoms is used in the present invention, the crystalline polyester resin interacts strongly with the release agent, and the affinity between the crystalline polyester resin and the polar resin further decreases. Conceivable. Thereby, the electrostatic offset suppression effect which the polar resin of this invention has is not inhibited, but it expresses efficiently.

  Further, when the binder resin has an aromatic ring, there is a π-π interaction between the aromatic rings between such a binder resin and a polar resin having a partial structure derived from styrene of 50.00% by mass or more. It is thought to occur. Therefore, the compatibility between the binder resin and the polar resin is improved, and uneven distribution of the polar resin inside the toner is suppressed. As a result, the electrostatic offset suppressing effect at the fixing nip can be efficiently expressed.

  The crystalline polyester resin contained in the toner of the present invention needs to have an alkyl group having 7 or more carbon atoms at the terminal. If the crystalline polyester resin has an aryl group at the terminal, a π-π interaction is likely to occur between the styrene-derived partial structure of the polar resin contained in the toner of the present invention. As a result, the electrostatic offset suppressing effect of the polar resin is hindered, and the hot offset is generated at a lower fixing temperature, so that the fixable temperature region is narrowed.

In addition, when the crystalline polyester resin has an aryl group at the end, the hydrophobic interaction between the crystalline polyester resin and the release agent having an alkyl group having 7 or more carbon atoms does not occur, and the binder resin is aromatic. When it has a ring, the affinity with the binder resin is increased. Therefore, the crystalline polyester resin is difficult to crystallize in the toner and is more likely to bleed. As a result, the developing member is contaminated in a high temperature and high humidity environment. The number of carbon atoms of the alkyl group at the end of the crystalline polyester resin requires 7 or more carbon atoms, more preferably 17 or more carbon atoms, from the viewpoint that excellent affinity with the release agent can be obtained. .
The acid value and hydroxyl value of the crystalline polyester resin are preferably an acid value of 4.0 mgKOH / g or less and a hydroxyl value of 7.0 mgKOH / g or less.

  The polar resin contained in the toner of the present invention needs to have a partial structure derived from styrene of 50.00% by mass or more. If the partial structure derived from styrene of the polar resin is less than 50.00% by mass, the effect of lowering the affinity with the crystalline polyester resin having an alkyl group having 7 or more carbon atoms is reduced. For this reason, the effect of suppressing the electrostatic offset of the polar resin is easily inhibited by the crystalline polyester resin. As a result, hot offset occurs at a lower fixing temperature, and the fixing temperature range is narrowed. The mass ratio of the partial structure derived from styrene of the polar resin is more preferably 80.00% by mass or more.

  In the present invention, it is essential that the polar value of the polar resin is 5.0 mgKOH / g or more and the acid value is 10.0 mgKOH / g or more. If the polar value of the polar resin is less than 5.0 mgKOH / g and the acid value is less than 10.0 mgKOH / g, there are few polar groups such as a carboxy group and a hydroxy group at the end of the polar resin. The effect of optimizing the charge density at the fixing nip hardly occurs. As a result, electrostatic offset cannot be suppressed in a low-temperature and low-humidity environment, hot offset occurs at a lower fixing temperature, and the fixable temperature range becomes narrower. More preferable conditions for the hydroxyl value and acid value of the polar resin are a hydroxyl value of 9.0 mgKOH / g or more and an acid value of 15.0 mgKOH / g or more.

In the toner particles of the present invention,
The content of the crystalline resin with respect to 100 parts by mass of the binder resin is 3.0 parts by mass or more and 20.0 parts by mass or less,
The content of the polar resin with respect to 100 parts by mass of the binder resin is 4.0 parts by mass or more and 20.0 parts by mass or less, which is a further favorable condition for exerting the effect of the present invention.

  When the content of the crystalline resin with respect to 100 parts by mass of the binder resin is 3.0 parts by mass or more, the low temperature fixability is improved by the sharp melt property of the crystalline polyester. In addition, since the content is 20.0 parts by mass or less, the action of the polar resin is not inhibited, and bleeding is suppressed. Improvement is possible.

  When the content of the polar resin with respect to 100 parts by mass of the binder resin is 4.0 parts by mass or more, the terminal polar group works efficiently in the fixing nip, so that the electrostatic offset suppression effect becomes remarkable. Further, it has been found that the low-temperature fixability is improved when the content is 20.0 parts by mass or less.

  In the present invention, the content of the crystalline resin with respect to the content of the release agent in the toner particles is more preferably 100.0% by mass or less. Release of the crystalline resin having an alkyl group having 7 or more carbon atoms having an alkyl group having 7 or more carbon atoms because the content of the crystalline resin with respect to the content of the release agent is 100.0% by mass or less Since it is reliably trapped by the agent, the contamination of the developing member can be further suppressed.

  In the present invention, it is also a preferable condition that the crystalline resin contained in the toner particles is a block polymer having a crystalline polyester portion and an amorphous vinyl portion. When the crystalline resin has a crystalline polyester part and an amorphous vinyl part, the amorphous vinyl part adjusts the compatibility and phase separation of each component in the toner particles, so that it can be stored at low temperature and heat-resistant. Good balance of sex. Further, since the crystalline resin is a block polymer, the low-temperature fixability and heat-resistant storage stability can be highly controlled.

Each component constituting the toner of the exemplary embodiment and a method for producing the toner will be described.
(Crystalline resin)
The crystalline resin contained in the toner of the present invention includes a crystalline polyester resin having an alkyl group having 7 or more carbon atoms at the terminal.
In order to obtain a crystalline polyester resin having an alkyl group having 7 or more carbon atoms at the end, a monovalent alcohol or monovalent acid having an alkyl chain having 7 or more carbon atoms is used, and a carboxy group or hydroxy group at the end of the polymer is used. The method of sealing a group is mentioned. Examples of the monovalent alcohol include octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol and the like. Examples of the monovalent acid include octanoic acid, decanoic acid, dodecanoic acid, stearic acid, and behenic acid.

The crystalline polyester resin can be obtained by the reaction of a divalent or higher polyvalent carboxylic acid and a polyhydric alcohol. From the viewpoint of obtaining an appropriate melting point and crystallinity, a crystalline polyester mainly composed of an aliphatic dicarboxylic acid and an aliphatic diol is preferred.
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.

  The crystalline resin contained in the toner of the present invention is preferably a block polymer having a crystalline polyester portion and an amorphous vinyl portion. 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 easy 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, for example, the following known production methods can be applied. A method of extending the amorphous vinyl moiety by atom transfer radical polymerization after synthesizing the crystalline polyester moiety first, and then synthesizing the crystalline polyester moiety after synthesizing the amorphous vinyl moiety into which the reactive functional group has been introduced. How to stretch. A method in which a crystalline polyester portion and an amorphous vinyl portion are first synthesized separately and then bonded together.

(Polar resin)
The polar resin contained in the toner of the present invention has a partial structure derived from styrene of 50.00% by mass or more, a hydroxyl value of 5.0 mgKOH / g or more, and an acid value of 10.0 mgKOH / g or more. Specific examples include the following. Copolymer of styrene and unsaturated carboxylic acid such as acrylic acid or methacrylic acid, copolymer of styrene and unsaturated carboxylic acid ester, copolymer of styrene and unsaturated dibasic acid or unsaturated dibasic acid anhydride Polymer. Copolymers of polymers such as unsaturated carboxylic acids, unsaturated carboxylic acid esters, unsaturated dibasic acids and unsaturated dibasic acid anhydrides with styrene.

  Among them, the polar resin contained in the toner of the present invention is preferably a styrene acrylic resin prepared using styrene and acrylic acid or methacrylic acid as a copolymerization component. When the polar resin is a styrene acrylic resin, it becomes easy to control the affinity with a crystalline resin containing a crystalline polyester having an alkyl group having 7 or more carbon atoms from the terminal ester bond, and the effects of the present invention are exhibited. Cheap.

  The styrene acrylic resin can be produced by the following method. (1) Solid-phase polymerization method in which monomers are polymerized in a substantially solvent-free state, (2) All monomers to be used for polymerization, all polymerization initiators and solvent are added, and polymerization is performed collectively Solution polymerization method, (3) A dropping polymerization method in which a monomer is added during the polymerization reaction. Moreover, what was manufactured by the normal pressure polymerization method and the pressure polymerization method can be used.

  The following compounds are mentioned as a copolymerization component used for preparation of a styrene acrylic resin. Styrene; α-methyl styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, p-methoxy styrene, and other styrenic monomers; acrylic acid, methacrylic acid; methyl acrylate, ethyl acrylate, acrylic Acrylic acid esters such as n-butyl acid, isobutyl acrylate, n-propyl acrylate; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, 2-methacrylic acid 2- Methacrylic acid esters such as hydroxyethyl; acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile, acrylamide; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether; vinyl Ethyl ketone, vinyl hexyl ketone, such as vinyl ketones of methyl isopropenyl ketone; N- vinyl pyrrole, N- vinyl carbazole, N- vinyl indole, N- vinylpyrrolidone, such as N- vinyl compounds, vinyl naphthalenes.

(Binder resin)
The binder resin type is not particularly limited, and examples thereof include styrene acrylic resin, epoxy resin, polyester, polyurethane resin, polyamide resin, cellulose resin, polyether resin, mixed resin and composite resin thereof. Styrene acrylic resins and polyesters are preferred because they are inexpensive, easily available, and have excellent low-temperature fixability. Furthermore, a styrene acrylic resin is more preferable at the point which is excellent in durable developability.

  Polyester is obtained by selecting and combining suitable ones from polyvalent carboxylic acid, polyol, hydroxycarboxylic acid and the like, for example, by synthesizing using a conventionally known method such as transesterification method or polycondensation method. .

  The polyvalent carboxylic acid is a compound containing two or more carboxyl groups in one molecule. Among these, dicarboxylic acid is a compound containing two carboxyl groups in one molecule and is preferably used. For example, oxalic acid, succinic acid, glutaric acid, maleic acid, adipic acid, β-methyladipic acid, azelain Acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, fumaric acid, citraconic acid, diglycolic acid, cyclohexane-3,5-diene-1,2-carboxylic acid, hexahydroterephthalic acid , Malonic acid, pimelic acid, peric acid, phthalic acid, isophthalic acid, terephthalic acid, tetrachlorophthalic acid, chlorophthalic acid, nitrophthalic acid, p-carboxyphenylacetic acid, p-phenylenediacetic acid, m-phenylenediacetic acid, o- Phenylenediacetic acid, diphenylacetic acid, diphenyl-p, p - dicarboxylic acid, naphthalene-1,4-dicarboxylic acid, naphthalene-1,5-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, anthracene dicarboxylic acid, and cyclohexane dicarboxylic acid.

  Moreover, as polyvalent carboxylic acid other than dicarboxylic acid, the following are mentioned, for example. Trimellitic acid, trimesic acid, pyromellitic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, pyrenetricarboxylic acid, pyrenetetracarboxylic acid, itaconic acid, glutaconic acid, n-dodecyl succinic acid, n-dodecenyl succinic acid, isododecyl succinic acid , Isododecenyl succinic acid, n-octyl succinic acid, n-octenyl succinic acid and the like. These may be used individually by 1 type and may use 2 or more types together.

  A polyol is a compound containing two or more hydroxy groups in one molecule. Among these, diol is a compound containing two hydroxy groups in one molecule, and is preferably used. Specific examples thereof include the following. Ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol 1,18-octadecanediol, 1,14-eicosandecanediol, diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, 1,4-cyclohexane Sundiol, 1,4-cyclohexanedimethanol, 1,4-butenediol, neopentyl glycol, 1,4-cyclohexanediol, polytetramethylene glycol, hydrogenated bisphenol A, bisphenol A, bisphenol F, bisphenol S, the above bisphenol Alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adducts. Among these, preferred are alkylene glycols having 2 to 12 carbon atoms and alkylene oxide adducts of bisphenols, and particularly preferred are alkylene oxide adducts of bisphenols and alkylene glycols having 2 to 12 carbon atoms. It is combined use with.

  Examples of trihydric or higher alcohols include the following. Glycerin, trimethylol ethane, trimethylol propane, pentaerythritol, hexamethylol melamine, hexaethylol melamine, tetramethylol benzoguanamine, tetraethylol benzoguanamine, sorbitol, trisphenol PA, phenol novolak, cresol novolak, polyphenols having three or more valences An alkylene oxide adduct of These may be used individually by 1 type and may use 2 or more types together.

As a styrene acrylic resin, the homopolymer which consists of the following polymerizable monomer, the copolymer obtained by combining these 2 or more types, Furthermore, those mixtures are mentioned.
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 styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene and p-phenyl styrene; methyl Acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, iso-propyl acrylate, iso-propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, iso-butyl acrylate, is o-butyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, n-amyl acrylate, n-amyl methacrylate, n-hexyl acrylate, n-hexyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, n-octyl acrylate, n-octyl methacrylate, n-nonyl acrylate, n-nonyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, benzyl acrylate, benzyl methacrylate, dimethyl phosphate ethyl acrylate, dimethyl phosphate ethyl methacrylate, diethyl phosphate ethyl acrylate, diethyl phosphate ethyl methacrylate , Dibutyl phosphate ethyl Like acrylate, dibutyl phosphate ethyl methacrylate and 2-benzoyloxyethyl acrylate, 2-benzoyloxyethyl methacrylate, acrylonitrile, methacrylonitrile, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, acrylic acid, methacrylic acid, maleic acid Acrylic ethers and methacrylic derivatives; vinyl ether derivatives such as vinyl methyl ether and vinyl isobutyl ether; vinyl ketone derivatives such as vinyl methyl ketone, vinyl ethyl ketone and vinyl isopropenyl ketone; polyolefins such as ethylene, propylene and butadiene.

  As the styrene acrylic resin, a polyfunctional polymerizable monomer can be used as necessary. Examples of the polyfunctional polymerizable monomer include the following. Diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, 1,6-hexanediol diacrylate 1,6-hexanediol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, tripropylene glycol diacrylate, tripropylene glycol dimethacrylate, polypropylene glycol diacrylate, polypropylene glycol dimethacrylate, 2,2'-bis (4- (Acrylo Sidiethoxy) phenyl) propane, 2,2′-bis (4- (methacryloxydiethoxy) phenyl) propane, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, tetramethylolmethane tetraacrylate, tetramethylolmethane tetramethacrylate, divinyl Benzene, divinyl naphthalene and divinyl ether.

In order to control the degree of polymerization, a known chain transfer agent and polymerization inhibitor may be further added.
Examples of the polymerization initiator for obtaining the styrene acrylic resin include organic peroxide polymerization initiators and azo polymerization initiators.

  Examples of the organic peroxide polymerization initiator include benzoyl peroxide, lauroyl peroxide, di-α-cumyl peroxide, 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane, bis (4-t -Butylcyclohexyl) peroxydicarbonate, 1,1-bis (t-butylperoxy) cyclododecane, t-butylperoxymaleic acid, bis (t-butylperoxy) isophthalate, methyl ethyl ketone peroxide, tert-butyl Examples include peroxy-2-ethylhexanoate, diisopropyl peroxycarbonate, cumene hydroperoxide, 2,4-dichlorobenzoyl peroxide, and tert-butyl-peroxypivalate.

  As the azo polymerization initiator, 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexane-1-carbonitrile) ), 2,2′-azobis-4-methoxy-2,4-dimethylvaleronitrile and azobismethylbutyronitrile, 2,2′-azobis- (methyl isobutyrate), and the like.

  A redox polymerization initiator in which an oxidizing substance and a reducing substance are combined can also be used as the polymerization initiator. Examples of the oxidizing substance include hydrogen peroxide, inorganic peroxides of persulfates (sodium salts, potassium salts and ammonium salts) and oxidizing metal salts of tetravalent cerium salts. Reducing substances include reducing metal salts (divalent iron salts, monovalent copper salts and trivalent chromium salts), ammonia, lower amines (amines having 1 to 6 carbon atoms such as methylamine and ethylamine). ), Amino compounds such as hydroxylamine, sodium thiosulfate, sodium hydrosulfite, sodium hydrogen sulfite, sodium sulfite and sodium formaldehyde sulfoxylate and other reducing sulfur compounds, lower alcohols (1 to 6 carbon atoms), ascorbine Examples include acids or salts thereof and lower aldehydes (having 1 to 6 carbon atoms).

  The polymerization initiator is selected with reference to the 10-hour half-life temperature, and is used alone or in combination. The addition amount of the polymerization initiator varies depending on the target degree of polymerization, but generally 0.5 parts by mass or more and 20.0 parts by mass or less are added to 100.0 parts by mass of the polymerizable monomer. The

(Release agent)
The toner of the present invention includes a release agent having an alkyl group having 7 or more carbon atoms. Various known waxes having an alkyl group having 7 or more carbon atoms can be used. Specific examples include the following. Paraffin wax, microcrystalline wax, petroleum wax and its derivatives represented by petrolactam, montan wax and its derivatives, hydrocarbon wax and its derivatives by Fischer-Tropsch method, polyolefin wax and its derivatives represented by polyethylene, carnauba wax Natural waxes typified by candelilla wax and derivatives thereof. Derivatives include oxides, block copolymers with vinyl monomers, and graft modified products. Further, alcohols such as higher aliphatic alcohols; fatty acids such as stearic acid and palmitic acid or acid amides, esters and ketones thereof; hardened castor oil and derivatives thereof, vegetable waxes and animal waxes. These can be used alone or in combination. These waxes may contain an antioxidant within a range that does not affect the chargeability of the toner.

  Among these release agents, the number of carbon atoms of the alkyl group is preferably 14 or more from the viewpoint of heat resistant storage stability and a release effect. Further, these release agents are preferably used in an amount of 1.0 to 30.0 parts by mass with respect to 100.0 parts by mass of the binder resin. The melting point of the release agent is preferably 30 ° C. or higher and 120 ° C. or lower, more preferably 60 ° C. or higher and 100 ° C. or lower. By using a release agent exhibiting the thermal characteristics as described above, the release effect is efficiently expressed and a wider fixing area is secured.

(Coloring agent)
In the toner of the present invention, known pigments and dyes can be used as colorants. As the colorant, a pigment is preferable from the viewpoint of excellent weather resistance.
Examples of cyan colorants include copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds and basic dye lake compounds. Specific examples include the following. C. I. Pigment Blue 1, 7, 15, 15: 1, 15: 2, 15: 3, 15: 4, 60, 62 and 66.

  Examples of the magenta colorant include condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds. 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, 150, 166, 169, 177, 184, 185, 202, 206, 220, 221, 254, and C.I. I. Pigment violet 19.

  Examples of yellow colorants include condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds. Specific examples include the following. C. I. Pigment Yellow 12, 13, 14, 15, 17, 62, 74, 83, 93, 94, 95, 97, 109, 110, 111, 120, 127, 128, 129, 147, 151, 154, 155, 168, 174, 175, 176, 180, 181, 185, 191 and 194.

Examples of the black colorant include carbon black and those that are toned in black using the yellow colorant, the magenta colorant, and the cyan colorant.
These colorants can be used alone or in a mixture, and further in the form of a solid solution. The colorant is preferably used in an amount of 1.0 to 20.0 parts by mass with respect to 100.0 parts by mass of the binder resin.

(Charge control agent, charge control resin)
A charge control agent or charge control resin may be used for the toner of the present invention.
As the charge control agent, a known one can be used, and a charge control agent that has a high frictional charging speed and can stably maintain a constant triboelectric charge amount is particularly preferable. Further, when the toner particles are produced by a suspension polymerization method, a charge control agent having a low polymerization inhibition property and substantially free from a solubilized product in an aqueous medium is particularly preferable.

  As the charge control agent, there are one that controls the toner to negative charge and one that controls the toner to positive charge. Examples of controlling the toner to be negatively charged include the following. Monoazo metal compounds, acetylacetone metal compounds, aromatic oxycarboxylic acids, aromatic dicarboxylic acids, oxycarboxylic acid and dicarboxylic acid metal compounds, aromatic oxycarboxylic acids, aromatic mono- and polycarboxylic acids and their metal salts, anhydrides , Esters, phenol derivatives such as bisphenol, urea derivatives, metal-containing salicylic acid compounds, metal-containing naphthoic acid compounds, boron compounds, quaternary ammonium salts, calixarenes, charge control resins, and the like.

  Examples of controlling the toner to be positively charged include the following. Guanidine compounds; imidazole compounds; quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, tetrabutylammonium tetrafluoroborate, and analogs thereof such as onium salts such as phosphonium salts and These lake pigments; triphenylmethane dyes and these lake pigments (as rake agents, phosphotungstic acid, phosphomolybdic acid, phosphotungsten molybdic acid, tannic acid, lauric acid, gallic acid, ferricyanide, Russian compounds); metal salts of higher fatty acids; charge control resins.

Examples of the charge control resin include a polymer or copolymer having a sulfonic acid group, a sulfonic acid group, or a sulfonic acid ester group. As the polymer having a sulfonic acid group, a sulfonic acid group or a sulfonic acid ester group, a polymer containing a sulfonic acid group-containing acrylamide monomer or a sulfonic acid group-containing methacrylamide monomer in a copolymerization mass ratio of 2% by mass or more. Is preferred. More preferably, it is a polymer containing 5% by mass or more.
These charge control agents or charge control resins may be added alone or in combination of two or more. The addition amount of the charge control agent or charge control resin is preferably 0.01 parts by mass or more and 20.0 parts by mass or less, more preferably 0.5 parts by mass or more with respect to 100.0 parts by mass of the binder resin. 10.0 parts by mass or less.

(External additive)
In order to impart various properties to the toner of the present invention, various organic or inorganic fine particles may be externally added as external additives.
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 particles (eg strontium titanate, cerium oxide, alumina, magnesium oxide, chromium oxide particles), nitride particles (eg silicon nitride particles), carbide particles (eg silicon carbide particles), metal Salt particles (eg calcium sulfate, barium sulfate, calcium carbonate particles).

(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 particles (for example, tin oxide, titanium oxide, zinc oxide, silica, alumina particles), carbon black.

Among these external additives, silica fine particles are preferable. Examples of the silica fine particles include dry silica or fumed silica produced by vapor phase oxidation of silicon halide, and wet silica produced from water glass. As the inorganic fine particles, dry silica having less silanol groups on the surface and inside the silica fine particles and less Na ₂ O and SO ₃ ²⁻ is preferable. The dry silica may be composite fine particles of silica and other metal oxides by using a metal halogen compound such as aluminum chloride, titanium chloride or the like together with a silicon halogen compound in the production process.

  The organic or inorganic fine powder may be subjected to a surface treatment for improving the fluidity of the toner and for uniform charging of the toner particles. By hydrophobicizing the surface of organic or inorganic fine particles with a treatment agent, adjustment of the triboelectric charge amount of toner, improvement of environmental stability, and improvement of fluidity under high temperature and high humidity can be achieved. It is preferable to use organic or inorganic fine particles that have been treated. 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.

  For example, the toner of the present invention can be obtained by externally mixing and mixing inorganic fine particles with toner particles and adhering them to the surface of the toner particles. A known method may be adopted as the external addition method of the inorganic fine particles. For example, the method of performing a mixing process using Mitsui Henschel mixer (made by Mitsui Miike Kako Co., Ltd.) is mentioned.

  The total amount of the organic or inorganic fine particles is preferably 1.00 parts by mass or more and 5.00 parts by mass or less, more preferably 1.00 parts by mass or more and 2.50 parts by mass with respect to 100 parts by mass of the toner particles. Or less. The organic or inorganic fine particles preferably have a particle size of 1/10 or less of the weight average particle size of the toner particles from the viewpoint of toner durability.

(Toner production method)
As a method for producing the toner of the present invention, known production methods such as a melt-kneading pulverization method, an emulsion aggregation method, a dissolution suspension method, and a suspension polymerization method can be applied. In the present invention, the suspension polymerization method which can easily exhibit the electrostatic offset suppressing effect of the polar group is easy to localize on the toner surface because the polar resin having a high acid value and hydroxyl value is the most preferable production method. Details of the suspension polymerization method will be described below.

  As the dispersion stabilizer used when preparing the aqueous medium, a known inorganic compound dispersion stabilizer and organic compound dispersion stabilizer can be used. As dispersion stabilizers for inorganic compounds, tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate , Barium sulfate, bentonite, silica, and alumina. On the other hand, examples of the organic compound dispersion stabilizer include polyvinyl alcohol, gelatin, methylcellulose, methylhydroxypropylcellulose, ethylcellulose, sodium salt of carboxymethylcellulose, polyacrylic acid and salts thereof, and starch. The amount of the dispersion stabilizer used is preferably 0.200 parts by mass or more and 20.0 parts by mass or less with respect to 100 parts by mass of the polymerizable monomer.

  Among these dispersion stabilizers, when a dispersion stabilizer of an inorganic compound is used, a commercially available product may be used as it is. However, in order to obtain a dispersion stabilizer having a finer particle size, the inorganic compound is used in an aqueous medium. It may be generated. For example, tricalcium phosphate can be obtained by mixing an aqueous sodium phosphate solution and an aqueous calcium chloride solution with high stirring.

Hereafter, the measuring method of various physical properties in this invention is demonstrated.
<Measurement method of acid value and hydroxyl value of polar resin and crystalline polyester>
The acid value and hydroxyl value of the polar resin and crystalline polyester are measured by potentiometric titration according to JIS-K0070-1992.

<Method for Measuring Weight Average Particle Size (D4) of Toner Particles>
The weight average particle size (D4) of the toner particles is determined by a precise particle size distribution measuring device “Coulter Counter Multisizer 3” (registered trademark, manufactured by Beckman Coulter, Inc.) equipped with a 100 μm aperture tube. , Measured with 25,000 effective measurement channels using the attached dedicated software “Beckman Coulter Multisizer 3 Version 3.51” (manufactured by Beckman Coulter, Inc.) for measurement condition setting and measurement data analysis Then, the measurement data is analyzed and calculated.

As the electrolytic aqueous solution used for the measurement, a special grade sodium chloride is dissolved in ion-exchanged water so as to have a concentration of about 1% by mass, for example, “ISOTON II” (manufactured by Beckman Coulter, Inc.) can be used. .
Prior to measurement and analysis, the dedicated software is set as follows.

In the “Standard measurement method (SOM) change screen” of the above dedicated software, set the total count in the control mode to 50000 particles, the number of measurements is 1 and the Kd value is “standard particles 10.0 μm” (Beckman Coulter The value obtained using (made by Co., Ltd.) is set. The threshold and noise level are automatically set by pressing the threshold / noise level measurement button. Also, the current is set to 1600 μA, the gain is set to 2, the electrolyte is set to ISOTON II, and the aperture tube flash after measurement is checked.
In the “pulse to particle size conversion setting screen” of the dedicated software, the bin interval is set to logarithmic particle size, the particle size bin is set to 256 particle size bin, and the particle size range is set to 2 μm or more and 60 μm or less.
The specific measurement method is as follows.

(1) About 200 mL of the above electrolytic solution is put in a glass 250 mL round bottom beaker dedicated to Multisizer 3, set on a sample stand, and the stirrer rod is stirred counterclockwise at 24 rpm. Then, dirt and bubbles in the aperture tube are removed by the “aperture flush” function of the analysis software.
(2) About 30 mL of the above electrolytic solution is put into a glass 100 mL flat bottom beaker, and about 0.3 mL of the following diluent is added thereto as a dispersant.
Diluent: “Contaminone N” (Nonionic surfactant, anionic surfactant, 10% by weight aqueous solution of neutral detergent for cleaning precision measuring instruments with pH 7 consisting of organic builder, manufactured by Wako Pure Chemical Industries, Ltd.) Diluted with ion-exchanged water 3 times by mass

(3) Two oscillators with an oscillation frequency of 50 kHz are incorporated with the phase shifted by 180 degrees, and a predetermined amount of ion-exchanged water is placed in the water tank of the ultrasonic disperser described below. About 2 mL.
Ultrasonic Disperser: Electrical output 120 W, “Ultrasonic Dispersion System Tetora 150” (manufactured by Nikka Ki Bios Co., Ltd.)
(4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. And the height position of a beaker is adjusted so that the resonance state of the liquid level of the electrolyte solution in a beaker may become the maximum.

(5) In a state where the electrolytic aqueous solution in the beaker of (4) is irradiated with ultrasonic waves, about 10 mg of toner particles are added to the electrolytic aqueous solution little by little and dispersed. Then, the ultrasonic dispersion process is continued for another 60 seconds. In ultrasonic dispersion, the temperature of the water tank is appropriately adjusted so as to be 10 ° C. or higher and 40 ° C. or lower.
(6) To the round bottom beaker (1) installed in the sample stand, the electrolytic solution (5) in which the toner particles are dispersed is dropped using a pipette, and the measurement concentration is adjusted to about 5%. To do. Measurement is performed until the number of measured particles reaches 50,000.
(7) The measurement data is analyzed with the dedicated software attached to the apparatus, and the weight average particle diameter (D4) is calculated. The “average diameter” on the analysis / volume statistics (arithmetic average) screen when the graph / volume% is set with the dedicated software is the weight average particle diameter (D4).

<Measurement method of weight average molecular weight (Mw)>
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.

Device: High-speed GPC device "HLC-8220GPC" (manufactured by Tosoh Corporation)
Column: 2 series 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.

  Hereinafter, the present invention will be described more specifically with reference to examples. The present invention is not limited by the following examples.

<Production Example of Crystalline Polyester A>
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.
-95.1 parts by mass of the vinyl polymer obtained above-120.0 parts by mass of xylene as the organic solvent-78.6 parts by mass of 1,12-dodecanediol-0.500 parts of titanium (IV) isopropoxide as the esterification catalyst Thereafter, 65.5 parts by mass of sebacic acid was added and reacted at 150 ° C. for 3 hours.
Furthermore, 9.5 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, and the crystalline polyester 1 was obtained. The physical properties are shown in Table 1.

<Production example of crystalline polyesters B and E>
Crystalline polyesters B and E were obtained in the same manner as in the production example of crystalline polyester A, except that the types and addition amounts of the monomers were partially changed in accordance with the formulation described in Table 1. The physical properties are shown in Table 1.

<Production example of crystalline polyester C>
In a reaction vessel equipped with a stirrer, a thermometer, a nitrogen inlet tube, and a decompressor, 80.0 parts by mass of xylene was heated while being purged with nitrogen, and refluxed at a liquid temperature of 140 ° C. A mixture obtained by stirring and mixing 72.6 parts by mass of styrene, 5.80 parts by mass of dicumyl peroxide, and 4.60 parts by mass of acrylic acid was dropped therein over 3 hours, and after completion of the addition, a solution was obtained. Was stirred for 3 hours. Subsequently, the following materials were added and reacted at 150 ° C. for 4 hours.
-91.5 parts by mass of 1,12-dodecanediol-0.600 parts by mass of titanium (IV) isopropoxide as an esterification catalyst Then, 85.0 parts by mass of sebacic acid was added and reacted at 150 ° C for 3 hours.
Further, 9.84 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, and the crystalline polyester C was obtained. The physical properties are shown in Table 1.

<Production Example of Crystalline Polyester D>
The following materials were added to a reaction vessel equipped with a stirrer, a thermometer, a nitrogen introduction tube, and a decompression device, and reacted at 150 ° C. for 4 hours.
-105 parts by weight of 1,12-dodecanediol-95.0 parts by weight of sebacic acid-17.5 parts by weight of stearic acid-0.600 parts by weight of titanium (IV) isopropoxide as an esterification catalyst Thereafter, 180 ° C for 4 hours Crystalline polyester D was obtained by further reacting at 180 ° C. and 1 hPa until the desired acid value and hydroxyl value were obtained. The physical properties are shown in Table 1.

<Production example of polar resin a>
In an autoclave equipped with a stirrer, a thermometer, a nitrogen introduction tube, a decompression device, and a dehydration tube, 300 parts by mass of xylene was charged, heated while purging with nitrogen, and refluxed at a liquid temperature of 140 ° C. A mixture of the following materials was added thereto, and polymerization was carried out for 5 hours at a polymerization temperature of 160 ° C. and a reaction pressure of 0.150 MPa.
・ 91.50 parts by mass of styrene,
・ Butyl acrylate 1.00 parts by mass,
・ Methyl methacrylate 2.50 parts by mass,
-2.50 parts by weight of methacrylic acid-2.50 parts by weight of 2-hydroxyethyl methacrylate,
-Polymerization initiator (di-tert-butyl peroxide) 2.00 parts by mass Thereafter, the solvent removal step was performed under reduced pressure for 3 hours to remove xylene and pulverization to obtain polar resin a. The physical properties are shown in Table 2.

<Production example of polar resins b, c, d, f, g>
Polar resins b, c, d, f, and g were obtained in the same manner as in the production example of the polar resin a except that the type and amount of each material were changed in accordance with the formulation shown in Table 2. The physical properties are shown in Table 2.

<Production example of polar resin e>
After putting the following materials into a reaction vessel equipped with a stirrer, thermometer, nitrogen introduction tube, and dehydration tube, 1.5 parts by mass of dibutyltin was added as a catalyst, and the mixture was then stirred under a nitrogen atmosphere. The temperature was raised to 160 ° C.
-Bisphenol A-propylene oxide 2 mol adduct 29.6 parts by mass-Bisphenol A-ethylene oxide 2 mol adduct 16.0 parts by mass-Terephthalic acid 32.0 parts by mass-Trimellitic acid 2.4 parts by mass

Subsequently, what mixed the following material was prepared and it was dripped in the reaction tank over 4 hours from the dropping funnel.
-Styrene 18.0 parts by mass-1.0 part by weight of methacrylic acid-1.0 part by weight of 2-hydroxyethyl methacrylate-0.40 part by weight of benzoyl peroxide as a polymerization initiator After the completion of dropping, react at 160 ° C for 4 hours I let you. Thereafter, the pressure of the reaction system was reduced while raising the temperature to 230 ° C., and a polycondensation reaction was performed. The polycondensation time after the start of the pressure reduction was set so that the softening point of the polar resin e was about 120 ° C. to obtain the polar resin e. The physical properties are shown in Table 2.

<Production Example of Toner 1>
The following materials were added to a four-necked vessel equipped with a reflux tube, a stirrer, a thermometer, and a nitrogen introduction tube, and a high-speed stirring device T.A. K. The temperature was maintained at 60 ° C. while stirring at 12,000 rpm using a homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.).
・ Ion-exchanged water 700 parts by mass ・ 0.1 mol / L Na ₃ PO ₄ aqueous solution 1000 parts by mass ・ 1.0 mol / L HCl aqueous solution 24.0 parts by mass Here 1.0 mol / L CaCl ₂ aqueous solution 85 parts by mass were gradually added to prepare an aqueous dispersion medium containing a fine hardly water-soluble dispersion stabilizer Ca ₃ (PO ₄ ) ₂ .

Styrene monomer 75.5 parts by mass n-butyl acrylate 24.5 parts by mass Crystalline Polyester A 7.0 parts by mass Polar resin a 10.0 parts by mass Release agent (behenyl behenate) 10.0 Parts by mass, copper phthalocyanine pigment (CI Pigment Blue 15: 3) 6.5 parts by mass, charge control agent (Bontron E-88, manufactured by Orient Chemical Industry Co., Ltd., 3,5-di-tert-butylsalicylic acid Aluminum 3: 1 type compound) 0.7 parts by mass

  The polymerizable monomer composition 1 obtained by dispersing the above material with an attritor (manufactured by Mitsui Miike Chemical Co., Ltd.) for 3 hours was held at a temperature of 60 ° C. for 20 minutes. Thereafter, the polymerizable monomer composition 1 obtained by adding 10.0 parts by mass of t-butyl peroxypivalate which is a polymerization initiator (70% toluene solution) to the polymerizable monomer composition 1 is placed in an aqueous medium. The mixture was granulated for 10 minutes while maintaining the rotation speed of the high-speed stirring device at 12,000 rpm. Thereafter, the high-speed stirrer was changed to a propeller stirrer, the internal temperature was raised to 70 ° C., and the reaction was allowed to proceed for 5 hours with slow stirring. At this time, the pH of the aqueous medium was 5.1. Next, the temperature in the container was raised to 85 ° C. and maintained for 5 hours. Thereafter, the reflux tube was removed, a distillation apparatus was attached, and distillation at a temperature of 100 ° C. in the container was performed for 5 hours. After cooling to 30 ° C., 10% hydrochloric acid was added to remove the dispersion stabilizer. Further, the toner particles 1 having a weight average particle diameter (D4) of 6.4 μm were obtained by filtration, washing and drying.

100 parts by mass of toner particles 1 and 1.6 parts by mass of a hydrophobic silica fine powder having a BET value of 300 m ² / g and a primary particle number average particle size of 8 nm were added to a Mitsui Henschel mixer (Mitsui Miike Chemical Industries, Ltd.). And toner 1 was obtained. The formulation and physical properties of Toner 1 are shown in Table 3.

<Production Example of Toners 2 to 16>
According to the formulation shown in Table 3, toners 2 to 16 were obtained in the same manner as toner 1 except that the type and amount of resin and the amount of release agent were changed. Table 3 shows the physical properties of Toners 2 to 16.

<Production Example of Toner 17>
Styrene acrylic resin 100.0 parts by mass (styrene / n-butyl acrylate = 75.5 parts by mass / 24.5 parts by mass, Mw = 60,000)
Crystalline polyester A 7.0 parts by mass Polar resin a 10.0 parts by mass Paraffin wax (HNP-5, manufactured by Nippon Seiwa Co., Ltd.) 10.0 parts by mass Copper phthalocyanine pigment (CI pigment) Blue 15: 3) 6.5 parts by mass / charge control agent (Bontron E-88, manufactured by Orient Chemical Co., Ltd.) 0.7 parts by mass

The said material was melt | dissolved in 400 mass parts of toluene, and the solution was obtained.
The following materials are added to a four-necked vessel equipped with a Liebig reflux tube, K. The temperature was maintained at 60 ° C. while stirring at 12,000 rpm using a homomixer.
・ Ion-exchanged water 700 parts by mass ・ 0.1 mol / L Na ₃ PO ₄ aqueous solution 1000 parts by mass ・ 1.0 mol / L HCl aqueous solution 24.0 parts by mass Here 1.0 mol / L CaCl ₂ aqueous solution 85 parts by mass were gradually added to prepare an aqueous dispersion medium containing a fine hardly water-soluble dispersion stabilizer Ca ₃ (PO ₄ ) ₂ .

Next, 100 parts by mass of the solution was added to T.W. K. While stirring at 12,000 rpm with a homomixer, the mixture was added and stirred for 10 minutes. The reflux tube was then removed and a distillation apparatus was attached. Next, distillation at a temperature in the vessel of 100 ° C. was performed for 5 hours. After cooling to 30 ° C., 10% hydrochloric acid was added to remove the dispersion stabilizer. Further, filtration, washing, and drying were performed to obtain toner particles 17 having a weight average particle diameter of 6.2 μm.
100 parts by mass of toner particles 17 and 1.6 parts by mass of hydrophobic silica fine powder having a BET value of 300 m ² / g and a primary particle number average particle size of 8 nm were added to Mitsui Henschel mixer (Mitsui Miike Chemical Co., Ltd. ) To obtain toner 17. The physical properties of Toner 17 are shown in Table 3.

<Production Example of Toner 18>
"Synthesis of polyester resin (1)"
・ Bisphenol A ethylene oxide 2mol adduct 10mol%
・ Bisphenol A propylene oxide 2 mol adduct 94 mol%
・ Terephthalic acid 50mol%
・ Fumaric acid 30mol%
・ Dodecenyl succinic acid 25mol%

The above monomer was put into a flask equipped with a stirrer, a nitrogen introducing tube, a temperature sensor, and a rectifying column, and the temperature was raised to 195 ° C. over 1 hour, and it was confirmed that the inside of the reaction system was uniformly stirred. 0.8% by mass of tin distearate was added with respect to the total mass of these monomers. Further, while distilling off the generated water, the temperature was raised from 195 ° C. to 250 ° C. over 5 hours, and a dehydration condensation reaction was carried out at 250 ° C. for another 2 hours.
As a result, the glass transition temperature was 60.1 ° C., the acid value was 14.0 mgKOH / g, the hydroxyl value was 26.2 mgKOH / g, the weight average molecular weight was 15,900, the number average molecular weight was 4,400, and the softening point was 114 ° C. Polyester resin (1) was obtained.

"Synthesis of polyester resin (2)"
・ Bisphenol A ethylene oxide 2mol adduct 50mol%
(Both ends equivalent 2 mol adduct)
・ Bisphenol A propylene oxide 2mol adduct 50mol%
(Both ends equivalent 2 mol adduct)
・ Terephthalic acid 65mol%
・ Dodecenyl succinic acid 30mol%

The above monomer was put into a flask equipped with a stirrer, a nitrogen introducing tube, a temperature sensor, and a rectifying column, and the temperature was raised to 195 ° C. over 1 hour, and it was confirmed that the inside of the reaction system was uniformly stirred. 0.7% by mass of tin distearate was added relative to the total mass of these monomers. Further, while distilling off the generated water, the temperature was increased from 195 ° C. to 240 ° C. over 5 hours, and a dehydration condensation reaction was carried out at 240 ° C. for another 2 hours.
Next, the temperature was lowered to 190 ° C., 6 mol% of trimellitic anhydride was gradually added, and the reaction was continued at 190 ° C. for 1 hour.
As a result, the glass transition temperature was 53.5 ° C., the acid value was 12.1 mg KOH / g, the hydroxyl value was 25.2 mg KOH / g, the weight average molecular weight was 51,000, the number average molecular weight was 6,200, and the softening point was 109 ° C. Polyester resin (2) was obtained.

“Preparation of resin particle dispersion 1”
-Polyester resin (1) 100.0 parts by mass-Methyl ethyl ketone 200.0 parts by mass The above materials were added to a container and completely dissolved to obtain a polyester resin (1) solution. The container containing the polyester resin (1) solution is set at a temperature of 40 ° C., and while stirring, a 10% aqueous ammonia solution is gradually added dropwise to a total of 5 parts by mass, and further 300 parts by mass of ion-exchanged water. Was gradually added dropwise at a rate of 10 mL / min to effect phase inversion emulsification. Further, the solvent was removed under reduced pressure using an evaporator to obtain a resin particle dispersion 1 of polyester resin (1). The resin particles had a volume average particle size of 130 nm. The solid content of the resin particles was adjusted to 20% with ion exchange water.

“Preparation of resin particle dispersion 2”
-Polyester resin (2) 100.0 parts by mass-Methyl ethyl ketone 200.0 parts by mass The above materials were added to a container and completely dissolved to obtain a polyester resin (2) solution. The container containing the polyester resin (2) solution is set at a temperature of 40 ° C., and a 10% aqueous ammonia solution is gradually added dropwise to a total of 3.5 parts by mass with stirring. A part by mass was gradually added dropwise at a rate of 10 mL / min for phase inversion emulsification. Further, the solvent was removed under reduced pressure to obtain a resin particle dispersion 2 of polyester resin (2). The resin particles had a volume average particle size of 150 nm. The solid content of the resin particles was adjusted to 20% with ion exchange water.

“Preparation of resin particle dispersion 3”
-Polar resin a 70.0 mass parts-Methyl ethyl ketone 100.0 mass parts-Isopropyl alcohol 40.0 mass parts The said material was added to the container, it was made to melt | dissolve completely, and polar resin a solution was obtained. The container containing the polar resin a solution was set at a temperature of 40 ° C., and a 10% aqueous ammonia solution was gradually added dropwise to a total of 5 parts by mass with stirring, and 300 parts by mass of ion-exchanged water was further added at 10 mL / The solution was gradually added dropwise at a rate of minutes to effect phase inversion emulsification. Further, the solvent was removed under reduced pressure using an evaporator to obtain a resin particle dispersion 3 of polar resin a. The resin particles had a volume average particle size of 150 nm. The solid content of the resin particles was adjusted to 20% with ion exchange water.

“Preparation of resin particle dispersion 4”
Crystalline polyester A 60.0 parts by mass Anionic surfactant Neogen RK (Daiichi Kogyo Seiyaku Co., Ltd.) 2.0 parts by mass Ion-exchanged water 240.0 parts by mass The above materials are mixed and the temperature is 100 ° C. And then fully dispersed with IKA Ultra Turrax T50, then heated to 115 ° C. with a pressure discharge type gorin homogenizer and dispersed for 1 hour, a resin having a volume average particle size of 140 nm and a solid content of 20%. A particle dispersion 4 was obtained.

"Preparation of colorant particle dispersion"
Copper phthalocyanine (CI Pigment Blue 15: 3) 45.0 parts by mass Anionic surfactant Neogen RK (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 5.0 parts by mass Ion-exchanged water 190.0 parts by mass After mixing the above materials and dispersing for 10 minutes with a homogenizer (IKA Ultra Tarrax), a dispersion process is performed for 20 minutes at a pressure of 250 MPa using an optimizer (counter-impact type wet crusher: manufactured by Sugino Machine Co., Ltd.). It was. Then, a colorant particle dispersion having a volume average particle diameter of 120 nm and a solid content of 20% was obtained.

"Preparation of release agent particle dispersion"
Paraffin wax (HNP-5, manufactured by Nippon Seiwa Co., Ltd.) 60.0 parts by mass Anionic surfactant Neogen RK (Daiichi Kogyo Seiyaku Co., Ltd.) 2.0 parts by mass Ion-exchanged water 240.0 Part by mass The above materials are mixed, heated to a temperature of 100 ° C., sufficiently dispersed with IKA Ultra Turrax T50, heated to 115 ° C. with a pressure discharge type gorin homogenizer, and subjected to a dispersion treatment for 1 hour. A release agent particle dispersion having an average particle size of 160 nm and a solid content of 20% was obtained.

“Preparation of Toner Particles 18”
Resin particle dispersion 1 285.0 parts by weight Resin particle dispersion 2 190.0 parts by weight Resin particle dispersion 3 118.5 parts by weight Resin particle dispersion 4 128.0 parts by weight Colorant particle dispersion 32.5 parts by mass, release agent particle dispersion 48.0 parts by mass After adding 2.2 parts by mass of the anionic surfactant Neogen RK to the flask, the above materials were stirred.

Subsequently, 1 mol / L nitric acid aqueous solution was dropped to pH 3.7, 0.35 parts by mass of aluminum polysulfate was added thereto, and the mixture was dispersed with IKA Ultra Turrax. The flask was heated to 50 ° C. with stirring in an oil bath for heating. After holding at 50 ° C. for 40 minutes, it was heated to 90 ° C. and held at 90 ° C. for 5 hours. Thereafter, cooling, filtration and drying were performed to obtain toner particles 18.
100 parts by mass of toner particles 18 and 1.6 parts by mass of hydrophobic silica fine powder having a BET value of 300 m ² / g and a primary particle number average particle size of 8 nm were added to Mitsui Henschel mixer (Mitsui Miike Chemical Co., Ltd. The toner 18 having a weight average particle diameter of 6.1 μm was obtained. The physical properties of Toner 18 are shown in Table 3.
<Production Example of Toner 19>
Toner 1 was prepared in the same manner as in Toner 1 except that behenyl behenate was changed to myristyl myristylate and the type of resin, amount, release agent, etc. were changed according to the formulation shown in Table 3. 19 was obtained. The physical properties of Toner 19 are shown in Table 3.

<Production example of comparative toners 1 to 4>
Comparative toners 1 to 4 were obtained in the same manner as toner 1 except that the type of resin was changed according to the formulation shown in Table 3. Table 3 shows the physical properties of Comparative Toners 1 to 4.

[Example 1]
The toner 1 was evaluated for a fixable temperature margin, contamination of the developing member, and heat-resistant storage stability. The results are shown in Table 4.

<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, a hot offset (a part of the fixed image adheres to the surface of the fixing device member and is fixed on the image receiving paper in the next round at the rear end of the image receiving paper after passing through the fixing device. It was confirmed whether the phenomenon occurred. 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.

<Contamination of developing member>
A laser beam printer LBP9600C manufactured by Canon Inc. was modified to enable printing only at the cyan station. This LBP9600C toner cartridge was charged with 300 g of toner 1 and allowed to stand for 24 hours in a high temperature and high humidity (temperature 32.5 ° C./relative humidity 90%) environment. Thereafter, a toner cartridge was attached to the LBP 9600C, and an image having a printing ratio of 1.0% was printed out on 30,000 sheets of A4 color laser copier paper in the horizontal direction, and then the developing roller was removed and the toner was blown off with air. Thereafter, the developing member was taped with a mending tape (manufactured by 3M Japan Co., Ltd.), the contaminants on the surface of the developing member were peeled off, and this tape was stuck on A4 color laser copier paper. In addition, an unused mending tape was pasted on the same paper. About each tape, reflection density (%) was measured using the color reflection densitometer X-RITE 404A, and the numerical value (%) of the difference was evaluated based on the following reference | standard.

(Evaluation criteria)
A: Less than 0.020% B: 0.020% or more and less than 0.050% C: 0.050% or more and less than 0.080% D: 0.080% or more and less than 0.100% E: 0.100% or more In the present invention, C or higher is an acceptable level.

<Heat resistant storage stability>
5 g of Toner 1 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.

[Examples 2 to 19, Comparative Examples 1 to 4]
Each toner shown in Table 3 was evaluated in the same manner as in Example 1 for the fixable temperature margin, the developing member contamination, and the heat resistant storage stability. The results are shown in Table 4.

Claims (4)

A toner having toner particles containing a binder resin, a crystalline resin, a polar resin, a release agent and a colorant,
The crystalline resin includes a crystalline polyester resin having an alkyl group having 7 or more carbon atoms at its terminal,
The polar resin has a partial structure derived from styrene of 50.00% by mass or more, a hydroxyl value of 5.0 mgKOH / g or more, an acid value of 10.0 mgKOH / g or more,
The toner according to claim 1, wherein the release agent has an alkyl group having 7 or more carbon atoms. In the toner particles,
The content of the crystalline resin with respect to 100 parts by mass of the binder resin is 3.0 parts by mass or more and 20.0 parts by mass or less,
The toner according to claim 1, wherein the content of the polar resin with respect to 100 parts by mass of the binder resin is 4.0 parts by mass or more and 20.0 parts by mass or less.   The toner according to claim 1, wherein in the toner particles, the content of the crystalline resin with respect to the content of the release agent is 100.0% by mass or less. The toner according to claim 1, wherein the crystalline resin is a block polymer having a crystalline polyester portion and an amorphous vinyl portion.