JP2010151899A - Toner for developing electrostatic charge image - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide toner having wide non-offset temperature width. <P>SOLUTION: The toner for developing electrostatic charge image includes: binder resin (A) containing at least alicyclic olefinic resin or polyester resin; α-olefinic copolymer resin (B) to which ionic bond between molecules is performed by metal ions; and a coloring agent. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an electrostatic charge image developing toner used in electrophotography, electrostatic recording method and the like.

  Conventionally, styrene-acrylic resins and polyester resins are generally used as the binder resin, which is the main component of the toner for developing electrostatic images. Recently, many examples in which an alicyclic olefin resin (cycloolefin resin) typified by a cyclic olefin copolymer (COC) is used as a binder resin different from these (for example, Patent Document 1). ). These alicyclic olefin-based resins have high transparency, excellent low-temperature fixability, sharp molecular weight distribution, good grindability, and low water absorption. Therefore, it is expected to be used as an excellent binder resin. However, since commercially available alicyclic olefin-based resins generally have a narrow molecular weight distribution, there is a problem that an offset phenomenon is likely to occur during toner fixing.

As a means for obtaining a wide non-offset temperature range, generally, (1) the molecular weight distribution of the binder resin is set to two peaks of a low molecular weight component and a high molecular weight component, and (2) a crosslinking component is added to the binder resin. It is known to introduce (3) a large amount of a release agent wax. When an alicyclic olefin-based resin is used as the binder resin, (a) the molecular weight distribution of the binder resin is divided into two peaks of a low molecular weight component and a high molecular weight component (Patent Document 2), (b) the binder resin. (Patent Document 3), (c) A carboxyl group is introduced into the binder resin, a metal is added and melt-kneaded to form a crosslinked structure by ionomer (Patent Document 3), (d) Release It is known to add a large amount of agent wax.
JP 2003-35971 A Japanese Patent Laid-Open No. 9-101631 JP 2000-284528 A

  In the method (1), the low molecular weight component ratio must be increased, and the high temperature offset property and the toner durability are deteriorated. Regarding (2), it is difficult to fix at low temperature while maintaining the crosslinking component, and the crosslinking component has poor transparency and pigment dispersibility and has a problem in color reproducibility. Regarding (3), wax is generally poorly compatible with the binder resin, and it is difficult to uniformly disperse it in large quantities, and poorly dispersed wax deteriorates the fluidity of the toner and is fused to the member. Adversely affects image quality. As for (a), even if the low molecular weight component ratio is increased, the toner durability is sufficient, but the high temperature offset property is deteriorated. As for (b), it is difficult to fix at low temperature while maintaining the crosslinking component, and the crosslinking component has poor transparency and pigment dispersibility and has a problem in color reproducibility. As for (c), it is difficult to introduce a large amount of the carboxyl group only in the terminal by the melt air oxidation method, and the carboxylic acid anhydride is reacted in the presence of the peroxide. In the method, it is difficult to control the reaction, and there is a problem that the odor due to the unreacted carboxylic acid anhydride and the resin is yellowed by excessive reaction. Regarding (d), since the polyolefin resin having a cyclic structure has very good compatibility with the wax, if the resin is added in a large amount, the resin is plasticized and the toner becomes sticky. Accordingly, an object of the present invention is to provide a toner having a wide non-offset temperature range.

  The present invention (1) includes a binder resin (A) containing at least an alicyclic olefin resin or a polyester resin, an α-olefin copolymer resin (B) that is intermolecularly ion-bonded by metal ions, and coloring. And a toner for developing an electrostatic charge image.

  The invention (2) is the toner according to the invention (1), wherein the α-olefin copolymer resin is an ethylene / unsaturated carboxylic acid copolymer.

  The invention (3) is the toner according to the invention (2), wherein the ethylene / unsaturated carboxylic acid copolymer is a copolymer of ethylene and methacrylic acid or a copolymer of ethylene and acrylic acid. is there.

  The present invention (4) is the toner according to any one of the inventions (1) to (3), wherein the metal ions are sodium ions or zinc ions.

  In the invention (5), the softening temperature of the α-olefin copolymer resin (B) intermolecularly ion-bonded by the metal ions is 60 ° C. or more. ) One of the toners.

  The present invention (6) is characterized in that the ratio of the α-olefin copolymer resin (B) ion-bonded between the molecules by metal ions in the toner resin is 1 to 50% by mass. ) To (5).

  Here, the meaning of various terms used in this specification will be described. “Toner resin” means an α-olefin copolymer resin (B) which is ionically bonded between molecules by a binder resin (A) and metal ions, and is a wax (oil), an electrostatic control agent, and a colorant. , External additives and other additives shall not be included. In addition, “α-olefin copolymer resin (B) in which intermolecular ionic bonds are formed by metal ions” may be abbreviated as “resin (B)” for the sake of simplicity.

Here, a method for measuring various parameters in this specification will be described.
In the specification, in order to measure the average molecular weight by the molecular weight distribution of the polymer, it may be measured by gel permeation chromatography (hereinafter abbreviated as “GPC”) using appropriate conditions. Examples of conditions are shown below.
1 Measurement conditions Temperature: 40 ° C., solvent: tetrahydrofuran, flow rate: 1.0 ml / min
2 As a column to be used, a combination of a plurality of commercially available silica gel columns is used. For example, Shodex made by Showa Denko
GPC column
A combination of two KF-806L is suitable.
3 Use standard polystyrene to create the calibration curve. As standard polystyrene, for example, Pressure
Chemical Co. Manufactured by Toyo Soda Industry Co., Ltd. and having molecular weights of 6 × 102, 2.1 × 103, 4 × 103, 1.75 × 104, 5.1 × 104, 1.1 × 105, 3.9 × 105, It is appropriate to use 8.6 × 105, 2 × 106, 4.48 × 106, and use at least about 10 standard polystyrene.
4 As the detector, an RI (refractive index) detector such as SE-31 manufactured by Showa Denko KK is used.

The flow softening point means the temperature at the 50% outflow point measured under the following measurement conditions by an elevated flow tester (“CFT-5000” manufactured by Shimadzu Corporation).
Measurement conditions plunger; 1cm ²
・ Die diameter: 1mm
・ Die length: 1mm
・ Load: 20kgf
-Preheating temperature: 50-80 ° C
・ Preheating time: 300 sec
・ Temperature increase rate: 6 ℃ / min

  The glass transition temperature (Tg) in this specification shall mean the temperature of the shoulder part of the endothermic peak in DSC (differential scanning calorimeter). The acid value refers to the number of mg of potassium hydroxide required to neutralize 1 g of resin.

  According to the present invention (1), it is possible to provide a toner having a wide non-offset temperature range.

  According to the present invention (2), since the compatibility between the resin (B) and the alicyclic olefin resin as the binder resin is improved, the binder resin is chemically modified or a compatibilizer is added. In this case, it is possible to obtain a homogeneous toner that is difficult to phase-separate.

  According to the present invention (3), the compatibility between the resin (B) and the polyester resin as the binder resin is improved, so that the binder resin is not chemically modified or a compatibilizing agent is not added. Thus, it is difficult to separate the phases, and a homogeneous toner can be obtained.

  According to the present invention (4), there is an effect that an intermolecular ionic bond is easily formed and a toner having a wider non-offset temperature range can be provided.

  According to this invention (5), there exists an effect that a moldability improves.

  According to the present invention (6), it is possible to improve the pulverization property at the time of toner production and to prevent high temperature offset at the time of toner fixing.

<Electrostatic charge developing toner>
The electrostatic charge developing toner according to the best mode is an α-olefin copolymer resin (ionomer) in which an intermolecular ionic bond is formed between an alicyclic olefin resin or a polyester resin as a binder resin (A) and a metal ion. (B) and a coloring agent are contained. Further, the toner may contain wax, charge control agent, magnetic powder, and other various additives and external additives as optional components. Next, each component will be described in order.

Binder resin (A)
The binder resin (A) includes at least an alicyclic olefin-based resin or a polyester resin. The binder resin may be a mixture of the two kinds of resins, or may contain other resins. Examples of other resins include styrene resins, (meth) acrylic resins, styrene- (meth) acrylic copolymer resins, olefin resins (for example, α-olefin resins such as polyethylene and polypropylene), vinyl, and the like. Resin (for example, polyvinyl chloride, polyvinylidene chloride, etc.), polyamide resin, polyether resin, urethane resin, epoxy resin, polyphenylene oxide resin, terpene phenol resin, polylactic acid resin, hydrogenated rosin, ring Rubber, thermoplastic polyimide and the like. The addition amount of these resin can be suitably selected from the range of 30% by mass or less with respect to 100% by mass of the binder resin.

(Alicyclic olefin resin)
The alicyclic olefin-based resin is not particularly limited as long as it is a polymer using at least one cyclic olefin as one raw material monomer, and examples thereof include the following polymers (a), (b), and (c). . (A) a homopolymer composed of one type of cyclic olefin, (b) a copolymer composed of two or more types of cyclic olefin, and (c) a cyclic olefin and an acyclic unsaturated monomer A copolymer composed of

  Examples of the cyclic olefin include monocyclic cyclic olefins such as cyclobutene, cyclopentene, cyclohexene, cycloheptene, and cyclooctene, or derivatives thereof, and cyclic conjugated dienes such as cyclopentadiene, cyclohexadiene, cycloheptadiene, cyclooctadiene, or derivatives thereof. Polycyclic olefins such as norbornene, dicyclopentadiene, tricyclodecene, tetracyclododecene, hexacycloheptadecene or derivatives thereof, vinylcyclobutane, vinylcyclobutene, vinylcyclopentane, vinylcyclopentene, vinylcyclohexane, vinylcyclohexene, Vinyl alicyclic hydrocarbons such as vinylcycloheptane, vinylcycloheptene, vinylcyclooctane, vinylcyclooctene, or derivatives thereof; Hydrides or derivatives thereof of an aromatic ring portion of the vinyl aromatic monomer Ren etc., etc., cyclic and / or polycyclic olefinic compounds having at least one double bond can be exemplified. These cyclic olefins can be used alone or in combination of two or more. Examples of the derivatives include alkyl-substituted products, alkylidene-substituted products, alkoxy-substituted products, acyl-substituted products, halogen-substituted products, and carboxyl-substituted products. The number of carbon atoms constituting the alicyclic structure is usually about 4 to 30, preferably about 5 to 20, and more preferably about 5 to 15 from the viewpoints of moldability and transparency.

  The acyclic unsaturated monomer is not particularly limited as long as it is an acyclic unsaturated monomer copolymerizable with a cyclic olefin. For example, an olefin monomer; a (meth) acrylic acid monomer Bodies; for example, (meth) acrylic acid ester monomers such as (meth) acrylic acid C1-6 alkyl esters such as methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylate; Vinyl ester monomers such as vinyl acetate and vinyl propionate; vinyl cyanide monomers such as (meth) acrylonitrile; diene monomers such as butadiene, 1,4-pentadiene and isoprene, Etc. can be exemplified. These acyclic unsaturated monomers may be used alone or in combination of two or more. The acyclic unsaturated monomer is preferably an olefin monomer from the viewpoint of imparting flexibility to the toner. Examples of the olefin monomer include α-C2-10 olefins (preferably α-C2-6 olefins) such as ethylene, propylene, 1-butylene, 1-pentene, 1-hexene, 1-heptene and 1-octene. And more preferably α-C2-4 olefin), branched olefins such as isobutene and isoprene. These olefins may be used alone or in combination of two or more. Of these olefins, ethylene and propylene are particularly preferable.

  Here, the preferred alicyclic olefin-based resin has no unsaturated double bond, is colorless and transparent and has high light transmittance. Among the alicyclic olefin-based resins (a) to (c) described above, (c) is preferable in terms of pulverization properties, processability, mechanical properties, and the like. Among (c), a particularly preferred alicyclic olefin-based resin is ethylene or a copolymer of propylene and norbornene (such as an ethylene-norbornene copolymer or a propylene-norbornene copolymer). In addition, the usage-amount of an acyclic unsaturated monomer can be selected from the range of about 0-100 mol with respect to 100 mol of cyclic olefins, Preferably it is 5-90 mol, More preferably, it is about 10-80 mol.

  The alicyclic olefin resin according to the best mode uses, for example, a metallocene catalyst, a Ziegler catalyst, and a metathesis polymerization, that is, a catalyst for double bond opening and ring opening polymerization reaction. It is preferable that the polymer is obtained by a conventional polymerization method (Japanese Patent Laid-Open No. 5-339327, Japanese Patent Laid-Open No. 5-9223, Japanese Patent Laid-Open No. 6-271628, European Patent Application Publication (A) No. 203799). No. 407870, No. 283164, and No. 156464). Among these, it is preferable to use a metallocene catalyst or a Ziegler catalyst from the viewpoint of synthesizing the resin having no unsaturated double bond.

  According to these, the alicyclic olefin-based resin may be one or more monomers of the cyclic olefin, optionally with one or more of the acyclic olefin-monomer, at -78 to 150 ° C, preferably at 20 to 80 ° C. It is obtained by polymerizing at a pressure of 0.01 to 64 bar in the presence of a cocatalyst such as aluminoxane and a catalyst composed of at least one metallocene such as zirconium or hafnium. Other useful polymers are described in European Patent Application (A) 317262, and hydrogenated polymers and copolymers of styrene and dicyclopentadiene can also be used.

  In the present invention, the alicyclic olefin-based resin preferably has at least two peaks in the molecular weight distribution measured by gel permeation chromatography (hereinafter abbreviated as “GPC”). . Such an alicyclic olefin-based resin may be a mixture of a low molecular weight fraction and a high molecular weight fraction, or the low molecular weight fraction and the high molecular weight fraction each have a peak in the molecular weight distribution by GPC during synthesis. It may be produced under such control. The number average molecular weight (hereinafter abbreviated as “Mn”) of the low molecular weight fraction is less than 7,500, the Mn of the high molecular weight fraction is 7,500 or more, and the ratio of the high molecular weight fraction is In the resin, it is preferably 50% by mass to 5% by mass, and more preferably 30% by mass to 5% by mass. When the proportion of the high molecular weight fraction is more than 50% by mass, the uniform kneading property is extremely lowered to impair the toner performance, and sufficient fixing strength cannot be obtained in low temperature fixing. On the other hand, if it is less than 5% by mass, a sufficient non-offset temperature range cannot be obtained.

  The glass transition temperature of the alicyclic olefin-based resin is determined by the composition ratio of the cyclic olefin and the acyclic unsaturated monomer, and is usually about 50 to 200 ° C., and can be appropriately selected depending on the application and molding temperature. . For toner, it is 50 to 80 ° C, preferably 50 to 70 ° C, more preferably about 50 ° C to 65 ° C. If the glass transition temperature of the alicyclic olefin-based resin is higher than 80 ° C., the fixing properties are deteriorated, and the rigidity and impact resistance are increased, so that the moldability of the toner is not sufficient. In addition, the fixing characteristics are deteriorated, and the anti-fusing property may be lowered.

  In the alicyclic olefin-based resin, a carboxyl group, a hydroxyl group, an amino group, or the like may be introduced by a known method. Furthermore, a crosslinked structure may be introduced into the alicyclic olefin-based resin having a carboxyl group introduced by adding a metal such as zinc, copper, or calcium. By introducing an appropriate amount of these substituents or metal cross-linked structures, the fixing characteristics are improved and the miscibility with other resins such as thermoplastic elastomers and colorants is improved during toner production. Can be expected to improve. However, it should be noted that toner performance may be deteriorated due to uneven introduction and unreacted residual substances.

  Here, the addition amount of the alicyclic olefin-based resin in the toner according to the best mode is preferably 20 to 95% by mass and 30 to 90% by mass based on the total toner mass. More preferred.

(Polyester resin)
The polyester resin blended in the electrostatic image developing toner of the present invention is generally a resin obtained by performing a polycondensation reaction containing at least one diol and at least one dicarboxylic acid as main components. Furthermore, several polyester resins can be used in combination for the purpose of adjusting the molecular weight distribution, glass transition temperature, and the like. The temperature at which the polycondensation reaction is performed is generally 150 to 300 ° C, preferably 180 ° C to 270 ° C, and more preferably 180 ° C to 250 ° C. When the reaction temperature is less than 150 ° C, the reaction time becomes long, which is not preferable. When the reaction temperature exceeds 300 ° C, decomposition occurs, which is not preferable.

  Examples of the diol used as a raw material for the polyester resin include ethylene glycol, 1,2-propanediol (commonly known as propylene glycol), 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 2 , 3-butanediol, diethylene glycol, triethylene glycol, dipropylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, hydrogenated bisphenol A, Examples thereof include an ethylene oxide adduct of bisphenol A and a propylene oxide adduct of bisphenol A. Among these, hydrogenated bisphenol A, bisphenol A ethylene oxide adduct, and bisphenol A propylene oxide adduct are preferably used.

  Dicarboxylic acids used as the other raw material for polyester resins include aliphatic saturated dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, and sebacic acid, maleic acid, fumaric acid, and citraconic acid. , Aliphatic unsaturated dicarboxylic acids such as itaconic acid, aromatic dicarboxylic acids such as phthalic acid, terephthalic acid and isophthalic acid, and anhydrides of the various dicarboxylic acids (for example, succinic anhydride, maleic anhydride, phthalic anhydride, etc.) And lower alkyl esters having 1 to 6 carbon atoms (for example, dimethyl succinate, diethyl maleate, dihexyl phthalate, etc.). Among these, adipic acid, terephthalic acid, and isophthalic acid are preferable, and terephthalic acid is more preferably used.

  Furthermore, as a raw material for the polyester resin, if necessary, trihydric or higher polyhydric alcohols such as glycerin, 2-methylpropanetriol, trimethylolpropane, trimethylolethane, sorbit, sorbitan, octanoic acid, decanoic acid, dodecanoic acid, myristic acid , Aliphatic monocarboxylic acids such as palmitic acid and stearic acid, aliphatic monocarboxylic acids having branched or unsaturated groups, aliphatic monoalcohols such as octanol, decanol, dodecanol, myristyl alcohol, palmityl alcohol, stearyl alcohol, benzoic acid Aromatic monocarboxylic acids such as acids and naphthalenecarboxylic acids, trivalent or higher polyvalent carboxylic acids such as trimellitic acid and pyromellitic acid, and acid anhydrides thereof can be used. Among these, glycerin, trimethylolpropane, stearic acid, trimellitic acid, and benzoic acid are preferable, and benzoic acid is more preferably used.

Further, the number average molecular weight (Mn) of the polyester resin is preferably 1000 to 14000 in the molecular weight distribution measured by GPC. More preferably, it is 1000-7000. When the number average molecular weight is less than 1000, there are cases where it is not preferable in terms of offset resistance and durability, and when it exceeds 14,000, it is not preferable in terms of fixability at low temperatures.
The weight average molecular weight (Mw) is preferably 5,000 to 20,000. More preferably, it is 5000-15000. If the weight average molecular weight is less than 5,000, it may be unfavorable in terms of offset resistance and durability, and if it exceeds 20000, it is not preferable in terms of fixability at low temperatures.
Moreover, it is preferable that the molecule | numerator of molecular weight less than 1000 is less than 10 mass%. More preferably, it is less than 9 mass%. When the number of molecules having a molecular weight of less than 1000 is 10% by mass or more, it may cause fusion to a photoreceptor or a developing roller, which is not preferable.

Further, the glass transition temperature (Tg) of the polyester resin is preferably 30 ° C to 80 ° C. More preferably, it is 40 degreeC-70 degreeC. When the temperature is lower than 30 ° C., blocking resistance (storability) may be deteriorated. When the temperature is higher than 80 ° C., low-temperature fixability may be deteriorated.
The flow softening point of the polyester resin is preferably 105 ° C to 145 ° C. More preferably, it is 105 degreeC-140 degreeC. When it is lower than 105 ° C., blocking resistance (storability) may be deteriorated, and when it is higher than 140 ° C., low-temperature fixability may be deteriorated.

  Moreover, the acid value of the polyester resin applied to the present invention is preferably 30 mgKOH / g or less, more preferably 20 mgKOH / g or less, and still more preferably 10 mgKOH / g or less. When the acid value is larger than 30 mgKOH / g, the blocking resistance (preservability) may be deteriorated, which is not preferable.

  Examples of the polyester resin applied to the present invention include a resin (number average molecular weight (Mn) 2150, weight average molecular weight (Mw) 9340) manufactured by Mitsui Chemicals, Inc., and a resin (number average molecular weight (Mn) 2330) manufactured by the same company. Examples of the resin having a weight average molecular weight (Mw) of 6930) and the like that are used by removing components having a molecular weight of 1000 or less to less than 10% by mass.

Α-Olefin Copolymer Resin (B) Bonded Intermolecularly with Metal Ions
Here, the α-olefin copolymer resin (ionomer) in which intermolecular ionic bonds are formed by metal ions is not particularly limited. For example, the α-olefin copolymer resin is preferably composed of an α-olefin / unsaturated carboxylic acid copolymer. It is. The α-olefin can be represented by the composition formula C _n H _2n , but in the present invention, n is an integer of 2 to 6, that is, ethylene, propylene, 1-butene, 1-pentene and 1-hexene are preferable. In particular, ethylene and propylene are preferred. When n is 7 or more, an alkyl group that becomes a side chain when a copolymer is formed, for example, when n = 7, -C ₅ H ₁₁ (pentyl group) is too long and bulky, and intermolecular ionic bonding is caused by metal ions. May be disturbed. If n is 2 or 3, it is suitable without inhibiting the ionic bond. Here, by using ethylene as the α-olefin, the compatibility of the resin (B) with the alicyclic olefin-based resin is improved, so that the phase separation is difficult and a homogeneous toner can be obtained. Here, the α-olefin / unsaturated carboxylic acid copolymer is not only a copolymer consisting of only an α-olefin and an unsaturated carboxylic acid, but also a multi-component copolymer in which other copolymerization components are optionally copolymerized. It may be a coalescence. The constituent unit content (unsaturated carboxylic acid component content) derived from the unsaturated carboxylic acid component is preferably 0.01 to 35% by mass, more preferably 0.1 to 30% by mass, and 1 to 29% by mass. % Is more preferred.

  Here, the unsaturated carboxylic acid is not particularly limited, and examples thereof include acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid, monomethyl maleate, monoethyl maleate, maleic anhydride, and itaconic anhydride. It is done. Among these, acrylic acid or methacrylic acid is preferable. Among these unsaturated carboxylic acids, by using methacrylic acid or acrylic acid, the compatibility of the resin (B) with the polyester resin is improved, so that it is difficult to separate the phases and a homogeneous toner can be obtained. In addition, since the resin (B) has a carboxyl group for each structural unit of the polymer, the intermolecular ionic bond derived from the interaction between the carboxyl group and the metal ion can be uniformly dispersed in the toner. This also contributes to obtaining a homogeneous toner.

  Specific examples of other copolymer components constituting the resin component of the resin (B) include methyl acrylate, ethyl acrylate, isobutyl acrylate, n-butyl acrylate, isooctyl acrylate, methacrylic acid. Examples thereof include unsaturated carboxylic acid esters such as methyl acid, isobutyl methacrylate, dimethyl maleate and diethyl maleate; vinyl esters such as vinyl acetate and vinyl propionate; and carbon monoxide. When such a multi-component copolymer is used, a soft α-olefin copolymer resin tends to be obtained. As the component of the resin (B), an optional copolymer component is an unsaturated carboxylic acid ester, In particular, multi-component copolymers which are esters of acrylic acid or methacrylic acid are preferred. The copolymerization ratio of such an arbitrary copolymerization component naturally varies depending on the properties of the target composition, but is preferably 40% by mass or less, and more preferably 30% by mass or less. Although a minimum is not specifically limited, For example, it is 5 mass% or more.

  The α-olefin-unsaturated carboxylic acid copolymer can be synthesized by a conventional method and is not particularly limited, but can be obtained, for example, by radical copolymerization. Resin (B) can be obtained by ionizing such an α-olefin-unsaturated carboxylic acid copolymer by a conventional method. The α-olefin-unsaturated carboxylic acid copolymer that can be used for ionization has, for example, a melt flow rate (MFR; JIS K 6760, 190 ° C., 2160 g load) of about 0.1 to 1000 g / 10 minutes, Preferably, it is about 0.5 to 300 g / 10 minutes. Resin (B) can also be obtained by saponification of an α-olefin-unsaturated carboxylic acid ester copolymer.

  Examples of the metal ions contained in the resin (B) include monovalent metals such as lithium, sodium and potassium, and polyvalent metals such as zinc, magnesium, calcium, copper, lead, nickel, cobalt and aluminum. Of the monovalent metals, sodium is preferred. In particular, it is preferable that at least a part is a divalent metal ion. As the divalent metal, zinc and magnesium are preferable, and zinc is most preferable.

  Two or more kinds of resin components of the resin (B) may be used, and an α-olefin-unsaturated carboxylic acid copolymer is used together with an α-olefin copolymer intermolecularly ion-bonded by metal ions. When used in combination, the α-olefin-unsaturated carboxylic acid copolymer may be ionized by melt mixing. Although the neutralization degree of resin (B) is not specifically limited, For example, 5-100% is suitable and 10-90% is suitable.

  The melt flow rate (JIS K 6760, 190 ° C., 2160 g load) of the resin (B) used in the best mode is preferably 0.1 to 300 g / 10 minutes, more preferably 0.2 to 250 g / 10 minutes. It is preferable, and 0.3 to 200 g / 10 min is more preferable.

  The softening temperature of the resin (B) used in the best mode is preferably 60 ° C. or higher, more preferably 65 ° C. or higher, and further preferably 70 ° C. or higher. Although an upper limit is not specifically limited, For example, it is 120 degrees C or less. When the softening temperature is lower than 60 ° C., the moldability is poor because the softening temperature is low, and there is a risk that roll adhesion is likely to occur during melt kneading, particularly in the production stage of the pulverized toner. Here, the softening temperature is measured according to JIS K-7206. Further, the ratio of the resin (B) in the toner according to the best mode is preferably 1 to 50% by mass, more preferably 3 to 40% by mass, and further preferably 5 to 30% by mass in the toner resin. It is. By making it within the range, the pulverization property at the time of toner production is improved, and the effect of preventing the high temperature offset at the time of toner fixing is exhibited. If the proportion of the resin (B) in the toner resin exceeds 50% by mass, the high elasticity of the resin (B) will appear strongly in the properties of the toner resin, and the pulverizability during toner production may deteriorate. There is. If it is less than 1% by mass, the elasticity imparted to the toner resin by the resin (B) becomes insufficient, and the toner viscosity near the fixing temperature tends to be low. Is likely to occur.

Colorant As the colorant used in the toner of the present best mode, a black pigment for black toner, a magenta pigment, a cyan pigment, and a yellow pigment for color toner can be used.

  As the black pigment, usually carbon black can be used. Carbon black can be used without being limited by the number average particle diameter, oil absorption, PH, etc., and the following are commercially available products. For example, product name: Legal (REGAL) 400, 660, 330, 300, SRF-S, STERLING SO, V, NS, R, manufactured by Columbia Carbon Japan Co., Ltd. Product name: Raven (Raven) H20, MT-P, 410, 420, 430, 450, 500, 760, 780, 1000, 1035, 1060, 1080, manufactured by Mitsubishi Chemical Corporation Product names: # 5B, # 10B, # 40, # 2400B, MA-100 Etc. can be used. These carbon blacks can be used alone or in combination of two or more.

  The addition amount of carbon black in the toner of the best mode is preferably in the range of 0.1 to 20% by mass, more preferably 1 to 10% by mass, and still more preferably based on the total toner mass. 1-5 mass% (1-3 mass% is especially preferable). If the ratio of carbon black is too small, the image density is lowered, and if it is too much, the image quality is liable to be lowered and the toner moldability is also lowered. As the black pigment, carbon black and black magnetic powder such as iron oxide and ferrite can be used.

  Examples of the magenta pigment include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48, 49, 50, 51, 52, 53, 54, 55, 57, 58, 60, 63, 64, 68, 81, 83, 87, 88, 89, 90, 112, 114, 122, 123, 163, 202, 206, 207, 209; I. Pigment violet 19; C.I. I. Butlet 1, 2, 10, 13, 15, 23, 29, 35, etc. can be used. These magenta pigments can be used alone or in combination of two or more.

  Examples of cyan pigments include C.I. I. Pigment Bull-2, 3, 15, 16, 17; I. Bat Bull-6; I. Acid Bull-45 etc. can be used. These cyan pigments can be used alone or in combination of two or more.

  Examples of yellow pigments include C.I. I. Pigment Yellow-1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 65, 73, 74, 83, 93, 94, 97, 155 180, etc. can be used. These yellow pigments can be used alone or in combination of two or more.

  As a color pigment for full color, magenta pigment is C.I. from the viewpoint of color mixing and color reproducibility. I. Pigment Red 57 and 122 are cyan pigments such as C.I. I. Pigment Blue 15 is yellow pigment, C.I. I. Pigment Yellow 17, 93, 155, and 180 can be preferably used.

  The addition amount of the color pigment is preferably in the range of 1 to 20% by mass, more preferably 3 to 10% by mass, still more preferably 4 to 9% by mass (particularly 4%) based on the total toner mass. 0.5 to 8% by mass is preferable). If the ratio of these pigments is too small than the above range, the image density is lowered, and if it is too much, the charging stability is deteriorated and the image quality is liable to be lowered. It is also disadvantageous in terms of cost.

  Further, as the color pigment, a so-called master batch that is dispersed in a high concentration in a resin that can be a binder resin in advance may be used.

Waxes will now be described wax according to the present invention. As waxes, polyolefin waxes such as polyethylene wax, polypropylene wax, polybutene wax and modified polyethylene wax, synthetic waxes such as Fischer-Tropsch wax, paraffin waxes such as natural paraffin, microwax and synthetic paraffin, and petroleum-based waxes such as microcrystalline wax Wax, carnauba wax, candelilla wax, rice wax, hardened castor oil, acidic olefin wax, maleic acid ethyl ester, maleic acid butyl ester, stearic acid methyl ester, stearic acid butyl ester, palmitic acid cetyl ester, montanic acid ethylene glycol ester Ester waxes, stearamides, and oleins composed of fatty acid esters such as Amide, palmitic acid amide, lauric acid amide, behenic acid amide, methylene bis stearamide, amide waxes such as ethylene bis stearamide and the like. Among these waxes, Fischer-Tropsch wax, acidic olefin wax, and ester wax are suitable, and Fischer-Tropsch wax is particularly suitable. These waxes can be used alone or in combination of two or more. Waxes having different softening points (melting points) may be mixed.

  The wax content is preferably in the range of 0.1 to 10% by mass, preferably 0.5 to 7% by mass, more preferably 1 to 5% by mass, based on the total toner mass. is there. If the wax content is less than 0.1% by mass, the toner release function is insufficient, and the toner tends to adhere to the heat fixing roller, causing image offset and copying paper wrapping. As a result, the image fixing strength may be weakened. On the other hand, if it exceeds 10% by mass, the wax may be detached from the toner and adhere to various members inside the copying machine, which may cause a decrease in printing quality and a malfunction of the copying machine.

  Suitable waxes used in the present invention are compounds having a relatively low softening point or low melting point, specifically those having a softening point (melting point) of 50 to 170 ° C, more preferably 80 to 160 ° C. When the softening point is lower than 50 ° C., the blocking resistance and storage stability of the toner are insufficient, and when it exceeds 170 ° C., the fixing start temperature increases, which is not preferable. Note that raw material waxes having different softening points (melting points) may be mixed and used.

Other optional components As other optional components, a charge control agent, magnetic powder, additives and the like can be added. Hereinafter, each component will be described.

  First, examples of the charge control agent include a positive charge control agent and a negative charge control agent. Examples of positively chargeable charge control agents include modified products of nigrosine and fatty acid metal salts, quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, tetrabutylammonium tetrafluoroborate, Diorganotin oxide such as dibutyltin oxide, dioctyltin oxide, dicyclohexyltin oxide, diorganotin borate such as dibutyltin borate, dioctyltin borate, dicyclohexyltin borate, pyridium salt, azine, triphenylmethane compounds and cationic functional groups And low molecular weight polymers. These positively chargeable charge control agents may be used alone or in combination of two or more. As these positively chargeable charge control agents, nigrosine compounds and quaternary ammonium salts are preferably used. Examples of negatively chargeable charge control agents include acetylacetone metal complexes, monoazo metal complexes, naphthoic acid or salicylic acid metal complexes or salts, organometallic compounds, chelate compounds, low molecular weight polymers having an anionic functional group, and the like. It is done. These negatively chargeable charge control agents can be used alone or in combination of two or more. As these negatively chargeable charge control agents, salicylic acid metal complexes and monoazo metal complexes are preferably used.

  The addition amount of the charge control agent can usually be selected in the range of 0.1 to 5% by mass, preferably 0.5 to 4% by mass, and more preferably 1 to 4% by mass with respect to the toner. The charge control agent is preferably colorless or light color for color toners.

  Next, examples of magnetic powder include metals such as cobalt, iron, nickel, aluminum, copper, iron, nickel, magnesium, tin, zinc, gold, silver, selenium, titanium, tungsten, zirconium, and other metal alloys. Metal oxides such as aluminum oxide, iron oxide and nickel oxide, ferrite, magnetite and the like can be used. The addition amount of the magnetic powder is usually 1 to 70% by mass, preferably 5 to 50% by mass, and more preferably 10 to 40% by mass with respect to the toner. A magnetic powder having an average particle diameter of 0.01 to 3 μm can be suitably used.

  Next, as additives, for example, stabilizers (for example, UV absorbers, antioxidants, heat stabilizers, etc.), flame retardants, antifogging agents, dispersants, nucleating agents, plasticizers (phthalate esters, fatty acids) A plasticizer, a phosphate plasticizer, etc.), a polymer antistatic agent, a low molecular antistatic agent, a compatibilizing agent, a conductive agent, a filler, and a fluidity improver may be added.

External additive The toner of this best mode preferably has inorganic fine particles attached to the surface from the viewpoint of imparting fluidity. Examples of the inorganic fine particles include silica, alumina, talc, clay, calcium carbonate, magnesium carbonate, titanium oxide, carbon black powder, and magnetic powder. These inorganic fine particles may be used alone or in combination of two or more. Of these inorganic fine particles, silica can be particularly preferably used. Silica is not particularly limited in terms of average particle diameter, BET specific surface area, surface treatment, and the like, and can be appropriately selected according to the application, but the BET specific surface area is preferably in the range of 50 to 400 m ² / g, and the surface-treated hydrophobic Silica is preferred.

  In addition to the inorganic fine particles, a fine resin powder such as polytetrafluoroethylene resin powder or polyvinylidene fluoride resin powder may be further adhered to the toner of the best mode. The ratio of adding these inorganic fine particles and resin fine powder to the toner can be appropriately selected from the range of 0.01 to 8 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the toner. More preferably, it is 0.1-4 weight part (especially 0.3-3 weight part). When the ratio of addition is out of the above range, the fluidity and charging stability of the toner are lowered, and it is difficult to form a uniform image.

  The toner of the best mode is not limited to the developing method, and can be used for a non-magnetic one-component developing method, a magnetic one-component developing method, a two-component developing method, and other developing methods. The magnetic one-component developing system toner is used as a magnetic toner by mixing the magnetic powder with a binder resin, and the two-component developing system toner is used by mixing with a carrier. From the viewpoint of simplicity of the apparatus and cost, it is preferably used as a toner for a non-magnetic one-component development system.

  As the carrier in the two-component development system, for example, nickel, cobalt, iron oxide, ferrite, iron, glass beads and the like can be used. These carriers may be used alone or in combination of two or more. The average particle size of the carrier is preferably 20 to 150 μm. Further, the surface of the carrier may be coated with a coating agent such as a fluorine resin, an acrylic resin, or a silicone resin.

  The toner of the best mode may be a monochrome toner or a full color toner. In the monochrome toner, as the colorant, the above-described carbon black can be used as the non-magnetic toner, and the above-described carbon black as the magnetic toner can be used as the magnetic toner. In the full-color toner, the above-described color pigment can be used as a colorant.

"Production method"
The toner for developing an electrostatic charge image according to the best mode is not particularly limited, but is preferably a pulverized toner. For example, an α-olefin copolymer having an intermolecular ionic bond with a binder resin or a metal ion is preferable. By a method comprising a mixing step of mixing a coalesced resin (B), a colorant, and other additives, a hot-melt kneading step in which the mixture is heated and kneaded, and a pulverizing step in which the kneaded product is pulverized. Can be manufactured. Further, a classification step and a step of adding an external additive to the pulverized toner may be included.

  As a mixing method in the mixing step, a method using a stirrer such as a Henschel mixer, a super mixer, or a ribbon mixer can be used.

  Subsequently, various methods such as a method using a twin screw extruder, a method using a Banbury mixer, a method using a pressure roller, and a method using a pressure kneader can be used as the hot melt kneading method. As the hot melt kneading method, a method using a twin screw extruder is preferable from the viewpoint of moldability and versatility. The melt-kneaded product is obtained by melt-kneading with a twin-screw extruder and extruding from a die (die) at the tip of the twin-screw extruder. The kneading temperature of the twin screw extruder is 50 to 220 ° C, preferably 70 to 200 ° C, more preferably about 80 to 180 ° C.

  Examples of the pulverization method in the pulverization step include a pulverization method using a pulverizer such as a hammer mill, a cutter mill, or a jet mill. As the classification method, an airflow classifier such as a dry centrifugal classifier can be usually used. The volume average particle diameter of the toner thus obtained is usually about 6 to 10 μm, preferably 6 to 9 μm, more preferably 6 to 8 μm. The volume average particle diameter is a 50% volume diameter measured using a particle size distribution measuring apparatus (Multisizer II, manufactured by Beckman Coulter, Inc.).

  Further, the inorganic fine particles and the resin fine powder may be adhered to the toner surface as external additives by stirring using a stirrer such as a turbine stirrer, a Henschel mixer, or a super mixer.

<Binder resin>
Product name TOPAS TB (ethylene-norbornene copolymer cycloaliphatic olefin resin, weight average molecular weight Mw = 200,000, number average molecular weight Mn = 5,000, double molecular weight distribution, glass transition temperature Tg = 60 ° C)
Product name TOPAS TM (ethylene-norbornene copolymer alicyclic olefin resin, weight average molecular weight Mw = 11,000, number average molecular weight Mn = 4,800, single peak molecular weight distribution, glass transition temperature Tg = 60 ° C)
Product name FC-1565 manufactured by Mitsubishi Rayon Co., Ltd. (polyester resin, glass transition temperature Tg = 62 ° C., flow softening point 123 ° C., acid value 6 mgKOH / g)
<Α-Olefin Copolymer Resin (B) Bonded Intermolecularly with Metal Ions>
B-1: Made by Mitsui DuPont Polychemical Co., Ltd., trade name Himiran 1555 (ethylene-methacrylic acid copolymer intermolecularly ion-bonded by sodium ion, softening temperature = 72 ° C. (JISK-7206), MFR = 10 g / 10 minutes (JIS K7210)
B-2: Made by Mitsui DuPont Polychemical Co., Ltd., trade name Himiran 1706 (ethylene-methacrylic acid copolymer intermolecularly ion-bonded by zinc ions, softening temperature = 65 ° C. (JISK-7206), MFR = 5 g / 10 minutes (JIS K7210)
B-3: Made by Mitsui DuPont Polychemical Co., Ltd., trade name Himiran 1855 (ethylene-methacrylic acid copolymer intermolecularly ion-bonded with zinc ions, softening temperature = 56 ° C. (JISK-7206), MFR = 1 g / 10 minutes (JIS K7210)
<Colorant>
Made by Cabot, carbon black, trade name MOGUL-L
<Charge control agent>
Hodogaya Chemical Co., Ltd., azo-based chromium complex, trade name T-95
<Wax>
Sanyo Chemical Industries, Polypropylene, trade name biscol 660P

The raw materials of Examples 1 to 5 and Comparative Examples 1 to 3 were melt kneaded with an open roll type kneader. Subsequently, the melt-kneaded product was pulverized by a jet mill and classified by an airflow classifier to obtain toner particles having a deposition average particle size of 9 μm. Next, with respect to the obtained toner, 0.4% by mass of hydrophobic silica (trade name NA50H, manufactured by Nippon Aerosil Co., Ltd.) and 0.8% by mass of hydrophobic silica (product name, H3004, manufactured by Clariant). The toner of Examples 1 to 3 and 5 and Comparative Examples 1 and 2 was obtained by adding and stirring and mixing with a Henschel mixer for 5 minutes.
The fixability and moldability of the obtained toner were evaluated, and the results are shown in the table.

<Method for evaluating fixing characteristics>
The obtained toner and magnetite carrier were mixed at a mass ratio of 5:95 to prepare a two-component developer. Next, using the obtained two-component developer, a strip-shaped unfixed image having a length of 3 cm and a width of 6 cm was formed on A4 transfer paper by a commercially available copying machine (AR-280, manufactured by Sharp Corporation).
Next, a heating roll type fixing machine in which a heating roll whose surface layer is formed of polytetrafluoroethylene and a pressure roll whose surface layer is formed of silicone rubber is rotated in a pair is rotated at a roll speed of 200 mm / sec. The surface temperature of the heating roll is lowered stepwise at intervals of 5 ° C. between 130 ° C. and 200 ° C., and the toner image on the transfer paper having the unfixed image is fixed at each surface temperature. Went.
At the time of fixing, it was observed whether or not toner contamination occurred in the margin of the transfer paper, and a temperature region where no contamination occurred was defined as a non-offset temperature range.

<Moldability>
In the present invention, “molding” refers to a shape in which the raw material of the toner is kneaded and dispersed (kneaded) in the melt-kneading step of the melt-kneaded and pulverized toner, and the melt-kneaded material of the raw material can be pulverized. It means taking out as the shape immediately before the pulverization step. As an evaluation of “formability”, whether or not it is easy to continuously recover the melt-kneaded material from the kneader, specifically, the melt-kneaded material in contact with the open roll of the kneader is It was evaluated whether or not it could be continuously collected by being peeled off from the roll by a special blade installed so as to slide.
If the melt-kneaded product has poor formability, the melt-kneaded product will not adhere to the roll and peel off, and cannot be recovered by being deposited on the roll surface one after another. There is a problem that continuous molding cannot be performed, that is, continuous production of toner cannot be performed because an operation of removing and recovering by applying an impact such as hitting an object is required.

<Evaluation results>
The toners of Examples 1 to 4 according to the present invention are excellent in non-offset temperature range and formability, and have no practical problems. In the toner of Example 5, although the softening temperature of the α-olefin copolymer resin (B) ion-bonded between the molecules by metal ions is low, roll adhesion occurs during melt kneading, and there is a problem in moldability. Excellent non-offset temperature range.
On the other hand, the toners of Comparative Examples 1 and 3 do not contain the α-olefin copolymer resin (B) ion-bonded between the molecules by the metal ions of the present invention, so that the elasticity is insufficient and high temperature offset is caused. There is a problem with sex.
The toner of Comparative Example 2 does not contain the α-olefin copolymer resin (B) that is intermolecularly ion-bonded with the metal ion of the present invention, but only contains TOPAS TB containing a large amount of high molecular weight fraction as a binder resin. Although it compensates for elasticity, it is excellent in high temperature offset property, but there is a problem in low temperature offset property.
As can be seen from the above results, according to the present invention, the non-offset temperature at the time of fixing in the electrostatic image developing toner containing the binder resin (A) containing an alicyclic olefin resin or polyester resin as a constituent element. Since the width can be widened, the degree of freedom in setting the temperature of a heat roller type fixing device such as a copying machine can be expanded, or a highly versatile electrostatic image developing toner that can be used in various copying machines. Can be provided.

Claims (6)

  Containing a binder resin (A) containing at least an alicyclic olefin-based resin or a polyester resin, an α-olefin copolymer resin (B) ionically intermolecularly bonded by metal ions, and a colorant. A toner for developing an electrostatic charge image.   The toner according to claim 1, wherein the α-olefin copolymer resin is an ethylene / unsaturated carboxylic acid copolymer.   The toner according to claim 2, wherein the ethylene / unsaturated carboxylic acid copolymer is a copolymer of ethylene and methacrylic acid or a copolymer of ethylene and acrylic acid.   The toner according to claim 1, wherein the metal ion is a sodium ion or a zinc ion.   The toner according to claim 1, wherein a softening temperature of the α-olefin copolymer resin (B) in which intermolecular ionic bonds are formed by the metal ions is 60 ° C. or more.   6. The ratio of the α-olefin copolymer resin (B) that is intermolecularly ion-bonded by metal ions in the toner resin is 1 to 50% by mass. 6. Toner.