JP2014126703A - Toner for electrostatic charge image development - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner for electrostatic charge image development that contains a polyester resin including a unit derived from 1,2-propanediol as a binder resin, and suppresses the generation of uncomfortable odor.SOLUTION: A toner for electrostatic charge image development contains a polyester resin including a unit derived from 1,2-propanediol as a binder resin, and is blended with zirconium hydroxide particles. The zirconium hydroxide particles preferably have the volume average particle diameter of 50 nm or more and 100 nm or less. The zirconium hydroxide particles may be internally added or externally added to toner, and preferably externally added to the toner.

Description

  The present invention relates to a toner for developing an electrostatic image.

    In general, in electrophotography, the surface of an electrostatic latent image carrier is charged using corona discharge or the like, and then exposed using a laser or the like to form an electrostatic latent image. A toner image is formed by developing with toner, and the toner image is further transferred to a recording medium to obtain a high-quality image. Usually, toner applied to such an electrophotographic method is kneaded, pulverized and classified by mixing components such as a colorant, a charge control agent, a release agent and a magnetic material in a binder resin such as a thermoplastic resin. To obtain toner particles having an average particle diameter of 5 μm or more and 10 μm or less. Such a method for producing a toner including kneading of materials contained in the toner, pulverization of the kneaded material, and classification of the pulverized material is referred to as a “pulverization method”. An inorganic fine powder such as silica or titanium oxide is externally added to the toner for the purpose of imparting fluidity to the toner, controlling charging of the toner, or improving cleaning properties.

  With respect to such a toner, from the viewpoint of energy saving and downsizing of the apparatus, a toner excellent in low temperature fixability that can be fixed satisfactorily without heating the fixing roller as much as possible is desired. When preparing a toner excellent in low-temperature fixability, a polyester resin is widely used as a binder resin.

  In addition, as a polyester resin for toner, a resin synthesized using a monomer that can be obtained from biomass in consideration of carbon neutral has been attracting attention in consideration of the environment. Among the monomers for polyester that can be obtained from biomass, 1,2-propanediol (propylene glycol) is known as a suitable monomer.

  A toner containing a polyester resin containing a unit derived from 1,2-propanediol as a binder resin is obtained by condensation polymerization of an alcohol component containing 70 mol% or more of an aliphatic polyhydric alcohol and a carboxylic acid component. A binder resin that is a polyester resin and a charge control agent, the alcohol component that is a raw material of the binder resin contains 1,2-propanediol as an aliphatic alcohol, and the charge control agent is a metal of a specific azo compound A toner that is a complex has been proposed (see Patent Document 1).

JP 2012-215857 A

  However, as described in Patent Document 1, a toner containing a polyester resin containing a unit derived from 1,2-propanediol as a binder resin has a problem of unpleasant odor derived from the toner. This unpleasant odor problem is particularly noticeable when a toner image on a recording medium is heated and fixed. Such an unpleasant odor of the toner is caused by 1,2-propanediol, which is slightly contained in the binder resin or slightly generated as the polyester resin is decomposed due to heating during fixing. Conceivable.

  The present invention has been made in view of such circumstances, and contains a polyester resin containing a unit derived from 1,2-propanediol as a binder resin, and is an electrostatic charge developing toner that hardly causes unpleasant odor. The purpose is to provide.

The present invention comprises a binder resin containing a polyester resin containing units derived from 1,2-propanediol,
The present invention relates to an electrostatic charge image developing toner containing zirconium hydroxide particles.

  According to the present invention, it is possible to provide a toner for developing an electrostatic charge that contains a polyester resin containing a unit derived from 1,2-propanediol as a binder resin and hardly generates an unpleasant odor.

It is a figure explaining the measuring method of the softening point using a Koka flow tester.

  Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments, and can be implemented with appropriate modifications within the scope of the object of the present invention. . In addition, although description may be abbreviate | omitted suitably about the location where description overlaps, the summary of invention is not limited.

[Binder resin]
The electrostatic image developing toner according to the present invention includes a binder resin containing a polyester resin containing a unit derived from 1,2-propanediol, and zirconium hydroxide particles. The toner of the present invention may contain components such as a colorant, a charge control agent, a release agent, and magnetic powder in the binder resin, if necessary. Further, the toner of the present invention may have its surface treated with an external additive as necessary. Further, the toner of the present invention is mixed with a desired carrier to form a two-component developer. It can also be used as

  The essential or optional components constituting the electrostatic image developing toner are binder resin, zirconium hydroxide particles, colorant, charge control agent, release agent, magnetic powder, and external additive. A method for producing a charge image developing toner and a carrier used when the toner of the present invention is used as a two-component developer will be described in order.

  The toner of the present invention essentially contains a polyester resin as a binder resin. The polyester resin is a copolymer of a divalent or trivalent or higher alcohol component containing 1,2-propanediol and a divalent or trivalent or higher carboxylic acid component. Hereinafter, regarding the binder resin, the alcohol component, the carboxylic acid component, and the method for producing the binder resin will be described in order.

(Alcohol component)
In the present invention, the dihydric or trihydric or higher alcohol component used as a monomer of the polyester resin used as the binder resin contains at least 1,2-propanediol. The amount of 1,2-propanediol in the alcohol component is not particularly limited as long as the object of the present invention is not impaired. Typically, it is preferably 60% by mass or more, more preferably 75% by mass or more, and 100% by mass. % Is particularly preferred.

  The production method of 1,2-propanediol is not particularly limited, and is produced using a method such as chemical synthesis, fermentation method, or a combination of these methods. As a specific method, vegetable oils and fats are hydrolyzed, glycerin is purified from the obtained reaction product, and the obtained glycerin and hydrogen are reacted in the presence of a hydrocracking catalyst to obtain 1,2- Examples thereof include a method for obtaining propanediol (see JP 2010-111618).

  The alcohol component may contain other divalent or trivalent or higher alcohol components in addition to 1,2-propanediol as long as the object of the present invention is not impaired. Specific examples of other dihydric or trihydric or higher alcohol components other than 1,2-propanediol include 1,3-propanediol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3- Propylene glycol, 1,4-butanediol, neopentyl glycol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, ethylene glycol, dipropylene glycol, Diols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol; bisphenols such as bisphenol A, hydrogenated bisphenol A, polyoxyethylenated bisphenol A, polyoxypropylenated bisphenol A; Bitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, di Trihydric or higher alcohols such as glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene, glycerin Is mentioned. It is particularly preferable to use 1,3-propanediol and glycerin as other divalent or trivalent or higher alcohol components other than these 1,2-propanediol.

(Carboxylic acid component)
Examples of the divalent or trivalent or higher carboxylic acid component used as the monomer of the polyester resin used as the binder resin include the following. Specific examples of the divalent or trivalent or higher carboxylic acid component include maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, phthalic acid, isophthalic acid, terephthalic acid, cyclohexanedicarboxylic acid, succinic acid, adipic acid, Sebacic acid, azelaic acid, malonic acid, or n-butyl succinic acid, n-butenyl succinic acid, isobutyl succinic acid, isobutenyl succinic acid, n-octyl succinic acid, n-octenyl succinic acid, n-dodecyl succinic acid, n-dodecenyl succinic acid Divalent carboxylic acids such as acids, isododecyl succinic acid, alkyl such as isododecenyl succinic acid or alkenyl succinic acid; 1,2,4-benzenetricarboxylic acid (trimellitic acid), 1,2,5- Benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4- Phthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylenecarboxypropane, 1,2,4-cyclohexanetricarboxylic acid Examples thereof include trivalent or higher carboxylic acids such as acid, tetra (methylenecarboxyl) methane, 1,2,7,8-octanetetracarboxylic acid, pyromellitic acid, and empole trimer acid. These divalent or trivalent or higher carboxylic acid components may be used as ester-forming derivatives such as acid halides, acid anhydrides, and lower alkyl esters. Here, “lower alkyl” means an alkyl group having 1 to 6 carbon atoms.

(Binder resin production method)
The method for producing the polyester resin used as the binder resin is not particularly limited, and can be appropriately selected from known polyester resin production methods. As a method for producing a polyester resin, for example, the alcohol component and the carboxylic acid component described above are put in a reaction vessel, and in the presence of a catalyst, a volatile component by-produced at 200 ° C. to 250 ° C. is removed while being removed. The method of performing a condensation reaction is mentioned. During the polycondensation reaction, the reaction vessel can be depressurized for the purpose of removing volatile components and promoting the polycondensation reaction. Examples of the catalyst include metals such as tin, titanium, antimony, manganese, nickel, zinc, lead, iron, magnesium, calcium, and germanium, and these metal-containing compounds.

  From the viewpoint of carbon neutral, the binder resin contained in the toner preferably contains a polyester resin synthesized using biomass-derived 1,2-propanediol. The kind of biomass is not particularly limited, and may be plant biomass or animal biomass. Among the biomass-derived materials, plant biomass-derived materials are more preferred because they are readily available in large quantities and are inexpensive. Specific examples of methods for producing 1,2-propanediol from biomass include chemical hydrolysis using vegetable oils or animal fats acids or bases, or biological hydrolysis using enzymes or microorganisms. Is mentioned. Glycerin can also be produced using a fermentation method from a substrate containing a saccharide such as glucose. Moreover, when the alcohol component which is a monomer of the polyester resin contains 1,3-propanediol or glycerin in addition to 1,2-propanediol, these are also preferably derived from biomass.

Among the CO ₂ present in the atmosphere, the concentration of CO ₂ containing radioactive carbon ( ¹⁴ C) is kept constant in the atmosphere. On the other hand, a plant takes in CO ₂ containing ¹⁴ C in the atmosphere in the process of photosynthesis, so that the concentration of ¹⁴ C in carbon in its organic component is the same as the concentration of CO ₂ containing ¹⁴ C in the atmosphere. The concentration is 107.5 pMC (percent Modern Carbon). Moreover, since carbon in animals is derived from carbon contained in plants, the concentration of ¹⁴ C in carbon in the organic components of animals is the same as that in plants.

Here, when the concentration of ¹⁴ C contained in the toner is XpMC, the proportion of carbon derived from biomass in the carbon in the toner can be obtained according to the following formula (1).
<Formula (1)>
Ratio of carbon derived from biomass (%) = (X / 107.5) × 100 (1)

In addition, as a particularly preferable plastic product from the viewpoint of carbon neutrality, a biomass product (Japan Bioplastics Association certification) is given to a plastic product in which the proportion of carbon derived from biomass in the carbon contained in the product is 25% or more. . Then, when the concentration X of ¹⁴ C in the toner in which the proportion of carbon derived from biomass in the carbon contained in the toner is 25% or more is obtained from the above formula (1), it is 26.9 pMC or more. Accordingly, it is preferable to prepare the polyester so that the concentration of the carbon radioactive carbon isotope ¹⁴ C contained in the toner is 26.9 pMC or more. The concentration of ¹⁴ C in the carbon element of the petrochemical product can be measured according to ASTM-D6866.

  Although the acid value of a polyester resin is not specifically limited, 3 mgKOH / g or more and 30 mgKOH / g or less are preferable. When the acid value of the polyester resin is too high, various performances of the toner are easily affected by humidity under high humidity conditions.

  Although the softening point of a polyester resin is not specifically limited, 80 degreeC or more and 140 degrees C or less are preferable. By using a polyester resin having a softening point in such a range as a binder resin for the toner, it is easy to obtain a toner that has excellent low-temperature fixability and is less likely to cause an offset during fixing at a high temperature. The softening point of the polyester resin can be measured according to the following method.

<Softening point measurement method>
The softening point of the polyester resin is measured using a Koka flow tester (CFT-500D (manufactured by Shimadzu Corporation)). Specifically, the softening point of the polyester resin is measured as follows. A polyester resin 1.5 g is used as a sample, and a die having a height of 1.0 mm and a diameter of 1.0 mm is used. Then, the measurement is performed under the conditions of a heating rate of 4 ° C./min, a preheating time of 300 seconds, a load of 5 kg, and a measurement temperature range of 60 ° C. to 200 ° C. The softening point is read using an S-curve relating to temperature (° C.) and stroke (mm) obtained from measurement of a polyester resin flow tester.

How to read the softening point will be described with reference to FIG. The maximum value of the stroke and S1, the stroke value of the low-temperature side of the base line and S _2. In the S-shaped curve, the temperature at which the stroke value becomes (S ₁ + S ₂ ) / 2 is defined as the softening point of the polyester resin.

  Although the glass transition point (Tg) of a polyester resin is not specifically limited, 60 degreeC or more and 70 degrees C or less are preferable. By using a polyester resin having a glass transition point in such a range as a binder resin for the toner, it is easy to obtain a toner that has excellent low-temperature fixability and is less likely to cause an offset during fixing at a high temperature.

  The glass transition point of the polyester resin can be determined from the change point of the specific heat of the polyester resin using a differential scanning calorimeter (DSC) according to JIS K7121. A more specific measuring method is as follows. It can obtain | require by measuring the endothermic curve of a polyester resin using the differential scanning calorimeter DSC-6200 by Seiko Instruments Inc. as a measuring apparatus. 10 mg of a measurement sample is put in an aluminum pan, and an empty aluminum pan is used as a reference. The glass transition point of the polyester resin can be determined from the endothermic curve of the polyester resin obtained by measurement at a measurement temperature range of 25 ° C. or more and 200 ° C. or less, a temperature increase rate of 10 ° C./min, and normal temperature and humidity.

  The number average molecular weight (Mn) of the polyester resin is not particularly limited as long as the object of the present invention is not impaired, but is preferably 1,800 or more and 2,000 or less. When the number average molecular weight (Mn) of the polyester resin is in such a range, a toner that can be satisfactorily fixed on a paper in a wide temperature range can be obtained. Further, the molecular weight distribution (Mw / Mn) represented by the ratio of the number average molecular weight (Mn) to the mass average molecular weight (Mw) is preferably 15 or more and 16 or less. When the molecular weight distribution of the polyester resin is within such a range, it is easy to obtain a toner having excellent low-temperature fixability. The number average molecular weight (Mn) and the mass average molecular weight (Mw) of the polyester resin can be measured using gel permeation chromatography.

  The binder resin may contain other thermoplastic resins of polyester resin as long as the object of the present invention is not impaired. When the binder resin includes a combination of a polyester resin and another thermoplastic resin of the polyester resin, the other thermoplastic resin of the polyester resin is appropriately selected from the thermoplastic resins conventionally used as the binder resin for toner. You can select and use.

  The content of the polyester resin in the binder resin is not particularly limited as long as the object of the present invention is not impaired. The content of the polyester resin in the binder resin is preferably 70% by mass or more, more preferably 80% by mass or more, particularly preferably 90% by mass or more, and most preferably 100%.

[Zirconium hydroxide particles]
The toner of the present invention essentially contains zirconium hydroxide particles. Since the toner of the present invention essentially contains a binder resin containing a polyester resin containing a unit derived from 1,2-propanediol, there is a potential problem of odor derived from 1,2-propanediol. However, the inclusion of zirconium hydroxide particles reduces the problem of odor derived from 1,2-propanediol.

The particle diameter of the zirconium hydroxide particles is not particularly limited as long as the desired odor suppressing effect is obtained. Typically, the volume average particle diameter of the zirconium hydroxide particles is preferably 500 nm or less, more preferably 10 nm to 300 nm, and particularly preferably 50 nm to 100 nm. When zirconium hydroxide particles in such a range are used, it is easy to obtain a toner that has good fluidity and reduces the odor derived from 1,2-propanediol to a desired extent. The volume average particle diameter (D ₅₀ ) of the zirconium hydroxide particles can be measured using an apparatus such as LA-950 (manufactured by Horiba, Ltd.).

  As an example of a commercial item of zirconium hydroxide particles, nano zirconium hydroxide powder (VK-RH60) manufactured by Ai Xuancheng New Materials Co., Ltd. can be mentioned.

  Zirconium hydroxide particles may be added to the inside of the toner particles or may be externally added to the surface of the toner particles. Zirconium hydroxide particles are preferably externally added from the viewpoint of obtaining a high odor suppressing effect with a small amount.

  The amount of zirconium hydroxide particles used is not particularly limited as long as the object of the present invention is not impaired. Typically, the amount of zirconium hydroxide particles used is preferably 1 part by mass or more and 10 parts by mass or less, and more preferably 1 part by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the binder resin.

[Colorant]
The toner of the present invention may contain a colorant as necessary. The toner can be appropriately selected from known pigments and dyes according to the desired color of the toner particles. Specific examples of suitable colorants to be added to the toner include black pigments such as carbon black, acetylene black, lamp black and aniline black; yellow lead, zinc yellow, cadmium yellow, yellow iron oxide, mineral fast yellow, nickel titanium Yellow, Naples Yellow, Naphthol Yellow S, Hansa Yellow G, Hansa Yellow 10G, Benzidine Yellow G, Benzidine Yellow GR, Quinoline Yellow Lake, Permanent Yellow NCG, Tartrazine Lake, yellow pigments; Orange pigments such as Permanent Orange GTR, Pyrazolone Orange, Vulcan Orange, Indanthrene Brilliant Orange GK; Bengala, Cadmium Red, Lead Red, Mercury Cadmium Sulfide, Permanent Red Red pigments such as 4R, Resol Red, Pyrazolone Red, Watching Red Calcium Salt, Lake Red D, Brilliant Carmine 6B, Eosin Lake, Rhodamine Lake B, Alizarin Lake, Brilliant Carmine 3B; Manganese Purple, Fast Violet B, Methyl Violet Purple pigments such as lakes; blue pigments such as bitumen, cobalt blue, alkali blue lakes, Victoria blue partial chlorinated products, first sky blue, indanthrene blue BC; chrome green, chromium oxide, pigment green B, malachite green lake, Green pigments such as final yellow green G; white pigments such as zinc white, titanium oxide, antimony white, zinc sulfide; barite powder, barium carbonate, clay, silica, white carbon , Talc, extender pigments such as alumina white. These colorants can be used in combination of two or more for the purpose of adjusting the hue of the toner to a desired hue.

  The amount of the colorant used is not particularly limited as long as the object of the present invention is not impaired. Specifically, the amount is preferably 1 part by mass or more and 10 parts by mass or less, and more preferably 3 parts by mass or more and 7 parts by mass or less with respect to 100 parts by mass of the binder resin.

(Charge control agent)
The toner of the present invention may contain a charge control agent as necessary. The charge control agent improves the stability of the charge level of the toner and the charge rise characteristic that is an indicator of whether the toner can be charged to a predetermined charge level in a short time. Used for gaining purposes. When developing with positively charged toner, a positively chargeable charge control agent is used. When developing with negatively charged toner, a negatively chargeable charge control agent is used.

  The type of the charge control agent is not particularly limited as long as the object of the present invention is not impaired, and can be appropriately selected from charge control agents conventionally used in toners. Specific examples of the positively chargeable charge control agent include pyridazine, pyrimidine, pyrazine, orthooxazine, metaoxazine, paraoxazine, orthothiazine, metathiazine, parathiazine, 1,2,3-triazine, 1,2,4-triazine, 1,3,5-triazine, 1,2,4-oxadiazine, 1,3,4-oxadiazine, 1,2,6-oxadiazine, 1,3,4-thiadiazine, 1,3,5-thiadiazine, 1, 2,3,4-tetrazine, 1,2,4,5-tetrazine, 1,2,3,5-tetrazine, 1,2,4,6-oxatriazine, 1,3,4,5-oxatriazine, Azine compounds such as phthalazine, quinazoline and quinoxaline; Azin Fast Red FC, Azin Fast Red 12BK, Azine Violet BO, Azine Direct dyes composed of azine compounds such as N-Brown 3G, Azin Light Brown GR, Azin Dark Green BH / C, Azin Deep Black EW, and Azin Deep Black 3RL; Nigrosine such as Nigrosine, Nigrosine Salt, Nigrosine Derivative Compounds; Acid dyes consisting of nigrosine compounds such as nigrosine BK, nigrosine NB, nigrosine Z; metal salts of naphthenic acid or higher fatty acids; alkoxylated amines; alkylamides; 4 such as benzylmethylhexyldecylammonium and decyltrimethylammonium chloride A class ammonium salt is mentioned. Among these positively chargeable charge control agents, a nigrosine compound is particularly preferable in that a more rapid start-up property can be obtained. These positively chargeable charge control agents can be used in combination of two or more.

  A resin having a quaternary ammonium salt, carboxylate, or carboxyl group as a functional group can also be used as a positively chargeable charge control agent. More specifically, a styrene resin having a quaternary ammonium salt, an acrylic resin having a quaternary ammonium salt, a styrene acrylic resin having a quaternary ammonium salt, a polyester resin having a quaternary ammonium salt, and a carboxylate Styrene resin having carboxylate, acrylic resin having carboxylate, styrene acrylic resin having carboxylate, polyester resin having carboxylate, styrene resin having carboxyl group, acrylic resin having carboxyl group, carboxyl group Styrene acrylic resin having a carboxyl group and polyester resin having a carboxyl group. The molecular weight of these resins is not particularly limited as long as the object of the present invention is not impaired, and may be an oligomer or a polymer.

  Among the resins that can be used as positively chargeable charge control agents, styrene acrylic resins having a quaternary ammonium salt as a functional group are more preferable because the charge amount can be easily adjusted to a value within a desired range. preferable. Specific examples of preferred acrylic comonomers that are copolymerized with styrene units in styrene acrylic resins having a quaternary ammonium salt as a functional group include methyl acrylate, ethyl acrylate, n-propyl acrylate, and iso-propyl acrylate. (Meth) acrylic acid, such as n-butyl acrylate, iso-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate Examples include alkyl esters.

  As the quaternary ammonium salt, a unit derived from a dialkylaminoalkyl (meth) acrylate, dialkylamino (meth) acrylamide, or dialkylaminoalkyl (meth) acrylamide through a quaternization step is used. Specific examples of the dialkylaminoalkyl (meth) acrylate include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dipropylaminoethyl (meth) acrylate, and dibutylaminoethyl (meth) acrylate. A specific example of dialkyl (meth) acrylamide is dimethylmethacrylamide. Specific examples of the dialkylaminoalkyl (meth) acrylamide include dimethylaminopropyl methacrylamide. Further, a hydroxy group-containing polymerizable monomer such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, or N-methylol (meth) acrylamide can be used in combination during polymerization.

  Specific examples of the negatively chargeable charge control agent include organometallic complexes and chelate compounds. Examples of organometallic complexes and chelate compounds include acetylacetone metal complexes such as aluminum acetylacetonate and iron (II) acetylacetonate, and salicylic acid metal complexes such as chromium 3,5-di-tert-butylsalicylate. A salicylic acid metal salt is preferable, and a salicylic acid metal complex or a salicylic acid metal salt is more preferable. These negatively chargeable charge control agents can be used in combination of two or more.

  The amount of the positively or negatively chargeable charge control agent used is not particularly limited as long as the object of the present invention is not impaired. Typically, the amount of the positively or negatively chargeable charge control agent used is preferably 0.5 parts by mass or more and 15 parts by mass or less, and 1.0 part by mass when the total amount of toner is 100 parts by mass. The amount is more preferably 8.0 parts by mass or less, and particularly preferably 3.0 parts by mass or more and 7.0 parts by mass or less. When the amount of charge control agent used is too small, it is difficult to stably charge the toner to a predetermined polarity, so that the image density of the formed image falls below a desired value, or it is difficult to maintain the image density over a long period of time. There are things to do. In such a case, the charge control agent is difficult to uniformly disperse in the toner, so that the formed image is likely to be fogged or the latent image carrier is easily contaminated due to adhesion of the toner component. When the amount of the charge control agent used is excessive, the latent image carrier is caused by image defects in the formed image due to poor charging under high temperature and high humidity due to deterioration of environmental resistance, or due to adhesion of toner components. Contamination is likely to occur.

〔Release agent〕
The toner of the present invention may contain a release agent for the purpose of improving the toner fixability and offset resistance. The type of release agent is not particularly limited as long as it is conventionally used as a release agent for toner.

  Suitable mold release agents include low molecular weight polyethylene, low molecular weight polypropylene, polyolefin copolymers, polyolefin waxes, microcrystalline waxes, paraffin waxes, and aliphatic hydrocarbon waxes such as Fischer-Tropsch wax; oxidized polyethylene waxes, and Oxides of aliphatic hydrocarbon waxes such as block copolymers of oxidized polyethylene waxes; plant waxes such as candelilla wax, carnauba wax, wood wax, jojoba wax, and rice wax; beeswax, lanolin, and whale Animal waxes such as waxes; mineral waxes such as ozokerite, ceresin, and vetrolactam; waxes based on fatty acid esters such as montanate ester wax and castor wax; Some fatty acid esters such as acid carnauba wax, or wax deoxidizing the like all.

  Suitable release agents further include saturated linear fatty acids such as palmitic acid, stearic acid, montanic acid, and long-chain alkyl carboxylic acids having a long-chain alkyl group; brassic acid, eleostearic acid And unsaturated fatty acids such as valinalic acid; saturated alcohols such as stearyl alcohol, eicosyl alcohol, behenyl alcohol, carnauvyl alcohol, seryl alcohol, melyl alcohol, and long chain alkyl alcohols having long chain alkyl groups Polyhydric alcohols such as sorbitol; fatty acid amides such as linoleic acid amide, oleic acid amide, and lauric acid amide; methylene bis stearic acid amide, ethylene biscapric acid amide, ethylene bis lauric acid amide, and hexamethylene vinyl Saturated fatty acid bisamides such as stearic acid amides; Unsaturated fatty acids such as ethylene bisoleic acid amides, hexamethylene bisoleic acid amides, N, N′-dioleyl adipic acid amides, N, N′-dioleyl sebacic acid amides Aromatic bisamides such as amides, m-xylene bis-stearic amide, and N, N′-distearylisophthalic amide; fatty acid metal salts such as calcium stearate, calcium laurate, zinc stearate, and magnesium stearate A wax obtained by grafting a vinyl monomer such as styrene or acrylic acid onto an aliphatic hydrocarbon wax; a partially esterified product of a fatty acid such as behenic acid monoglyceride and a polyhydric alcohol; hydrogenating vegetable oils and fats; Has the resulting hydroxyl group Methyl ester compounds that.

  The amount of the release agent used is not particularly limited as long as the object of the present invention is not impaired. Specifically, the amount of the release agent used is preferably 3% by mass or more and 20% by mass or less, and more preferably 5% by mass or more and 15% by mass or less with respect to the mass of the toner. When the amount of the release agent used is too small, a desired effect may not be obtained with respect to suppression of occurrence of offset and image smearing in the formed image. On the other hand, when the amount of the release agent used is excessive, the heat resistant storage stability of the toner may be reduced due to the fusion between the toners.

[Magnetic powder]
The toner of the present invention can be blended with magnetic powder as necessary. The kind of magnetic powder is not particularly limited as long as the object of the present invention is not impaired. Examples of suitable magnetic powders include irons such as ferrite and magnetite; ferromagnetic metals such as cobalt and nickel; alloys containing iron and / or ferromagnetic metals; compounds containing iron and / or ferromagnetic metals A ferromagnetic alloy subjected to a ferromagnetization treatment such as heat treatment; chromium dioxide.

  The particle size of the magnetic powder is not limited as long as the object of the present invention is not impaired. Specifically, the particle size of the magnetic powder is preferably 0.1 μm or more and 1.0 μm, and more preferably 0.1 μm or more and 0.5 μm or less. When magnetic powder having a particle diameter in such a range is used, it is easy to uniformly disperse the magnetic powder in the binder resin.

  For the purpose of improving the dispersibility of the magnetic powder in the toner, a magnetic powder surface-treated with a surface treatment agent such as a titanium coupling agent or a silane coupling agent can be used.

  The usage-amount of magnetic powder is not specifically limited in the range which does not inhibit the objective of this invention. The specific amount of magnetic powder used is preferably 35 parts by weight or more and 60 parts by weight or less, and 40 parts by weight or more and 60 parts by weight or less when the toner is used as a one-component developer and the total amount of toner is 100 parts by weight. The following is more preferable. If the amount of magnetic powder used is excessive, it may be difficult to maintain the image density at a desired value over a long period of time, or the toner fixability may be extremely reduced. If the amount of magnetic powder used is too small, fog may easily occur in the formed image, or it may be difficult to form an image having a desired image density over a long period of time. When the toner is used as a two-component developer, the amount of magnetic powder used is preferably 20% by mass or less and more preferably 15% by mass or less when the total amount of toner is 100 parts by mass.

(External additive)
The surface of the toner of the present invention may be treated with an external additive as necessary. In the specification of the present application, particles treated with an external additive are referred to as “toner mother particles”. The type of external additive is not particularly limited as long as it does not impair the object of the present invention, and can be appropriately selected from external additives conventionally used for toners. Specific examples of suitable external additives include silica and metal oxides such as alumina, titanium oxide, magnesium oxide, zinc oxide, strontium titanate, and barium titanate. These external additives can be used in combination of two or more. Further, these external additives can be used after being hydrophobized using a hydrophobizing agent such as an aminosilane coupling agent or silicone oil. In the case of using a hydrophobized external additive, it is easy to suppress a decrease in charge amount of the toner under high temperature and high humidity, and it is easy to obtain a toner excellent in fluidity.

  The particle diameter of the external additive is not particularly limited as long as it does not impair the object of the present invention, and typically 0.01 μm or more and 1.0 μm or less is preferable.

  The amount of the external additive used is not particularly limited as long as the object of the present invention is not impaired. Typically, the amount of the external additive used is preferably 0.1 parts by mass or more and 10 parts by mass or less, and more preferably 0.2 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the toner base particles.

[Method for producing toner for developing electrostatic image]
The toner of the present invention is obtained by blending a binder resin containing the above-described specific polyester resin with components such as a colorant, a charge control agent, and a release agent, if necessary. Further, when the toner of the present invention is produced, zirconium hydroxide particles are added internally or externally.

  As a specific method for producing a toner, after mixing a binder resin and components such as a colorant, a charge control agent, and a release agent, the resulting mixture is melt-kneaded, and the melt-kneaded product is pulverized and classified. "Crushing method" is mentioned. The pulverization method is preferable in that a toner having a desired particle diameter can be easily prepared.

  In addition, fine particles of components such as a binder resin, a colorant, a charge control agent, and a release agent are aggregated in a liquid medium such as an aqueous medium to form aggregated particles, and the aggregated particles are heated, An “aggregation method” in which the components contained in the aggregated particles are united is also preferable as a toner production method. In the aggregation method, it is easy to prepare a toner having a uniform shape and a narrow particle size distribution width.

  The average particle diameter of the toner is not particularly limited as long as it does not impair the object of the present invention, but generally it is preferably 5 μm or more and 10 μm or less.

  The surface of the toner thus obtained may be treated with an external additive as necessary. The method for treating the toner using an external additive is not particularly limited, and a conventionally known external additive is used. The processing method using can be selected as appropriate. Specifically, the processing conditions are adjusted so that the particles of the external additive are not embedded in the toner base particles, and the processing using the external additive is performed using a mixer such as a Henschel mixer or a Nauter mixer. .

[Career]
The toner of the present invention can be mixed with a desired carrier and used as a two-component developer. When preparing a two-component developer, it is preferable to use a magnetic carrier.

  Suitable carriers when the toner of the present invention is used as a two-component developer include those in which a carrier core material is coated with a resin. Specific examples of the carrier core material include particles such as iron, oxidized iron, reduced iron, magnetite, copper, silicon steel, ferrite, nickel, and cobalt, and particles of alloys of these materials with manganese, zinc, and aluminum. , Particles like iron-nickel alloy, iron-cobalt alloy, titanium oxide, aluminum oxide, copper oxide, magnesium oxide, lead oxide, zirconium oxide, silicon carbide, magnesium titanate, barium titanate, lithium titanate, titanate Ceramic particles such as lead, lead zirconate and lithium niobate, particles of high dielectric constant materials such as ammonium dihydrogen phosphate, potassium dihydrogen phosphate and Rochelle salt, and the above magnetic particles dispersed in resin A resin carrier is mentioned.

  Specific examples of the resin covering the carrier core material include (meth) acrylic polymer, styrene polymer, styrene- (meth) acrylic copolymer, olefin polymer (polyethylene, chlorinated polyethylene, polypropylene). , Polyvinyl chloride, polyvinyl acetate, polycarbonate, cellulose resin, polyester resin, unsaturated polyester resin, polyamide resin, polyurethane resin, epoxy resin, silicone resin, fluororesin (polytetrafluoroethylene, polychlorotrifluoroethylene, polyfluoride) Vinylidene), phenol resin, xylene resin, diallyl phthalate resin, polyacetal resin, and amino resin. These resins can be used in combination of two or more.

  The particle size of the carrier is not particularly limited as long as the object of the present invention is not impaired, but the particle size measured using an electron microscope is preferably 20 μm or more and 120 μm or less, and more preferably 25 μm or more and 80 μm or less.

  When the toner of the present invention is used as a two-component developer, the content of the toner in the two-component developer is preferably 3% by mass or more and 20% by mass or less, and preferably 5% by mass or more with respect to the mass of the two-component developer. 15 mass% or less is more preferable. By setting the toner content in the two-component developer within such a range, it is easy to maintain the image density of the formed image at an appropriate level, and image formation caused by suppression of toner scattering from the developing device Contamination inside the apparatus and toner adhesion to transfer paper can be suppressed.

  The toner for developing an electrostatic charge image according to the present invention described above hardly generates an unpleasant odor even though it contains a polyester resin containing a unit derived from 1,2-propanediol as a binder resin. Therefore, the electrostatic charge developing toner of the present invention is suitably used in various image forming layers.

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

[Synthesis Example 1]
[Production of 1,2-propanediol]
Vegetable oil was hydrolyzed to obtain glycerin. Specifically, the vegetable oil was completely saponified under heating by adding 10% aqueous sodium hydroxide solution twice the amount necessary to completely saponify the vegetable oil. An aqueous solution of glycerin was separated from the reaction solution after saponification, and the aqueous solution of glycerin was distilled and purified. Distilled glycerin was treated with activated carbon to obtain purified glycerin.

1,2-propanediol was produced from glycerin obtained according to the above method.
First, ethylene glycol (200 g) and cupric nitrate trihydrate (76 g) were added to a reactor having a reflux condenser, and after stirring with heating at 80 ° C. for 2 hours, tetraethoxysilane (52 g) was added dropwise. The mixture was stirred with heating at ° C for 2 hours. Thereafter, water (18 g) was added dropwise, and the mixture was heated and stirred at 80 ° C. for 3 hours to obtain a precipitate. The produced precipitate was dried at about 120 ° C. and calcined in air at 400 ° C. for 2 hours to obtain a copper / silica catalyst (copper content 50%). An aqueous solution of tetraammineplatinum (II) nitrate [Pt (NH3) 4 (NO3) 2] (29.8 mg) was added to the obtained copper / silica catalyst (3 g), and dried and dried on a rotary evaporator. The obtained solid was dried at 120 ° C., calcined in air at 400 ° C. for 2 hours, and copper-platinum / silica catalyst (Cu / Pt / Si = 50 / 0.5 / 17) (copper content 50% )
Next, 2 g of a copper-platinum / silica catalyst and 200 g of glycerin were added to a 500 mL iron autoclave equipped with a stirrer and replaced with hydrogen. Thereafter, hydrogen was introduced into an autoclave at 230 ° C. at 5 L / min (25 ° C., H ₂ ), and reacted at a pressure of 2 MPa for 7 hours to obtain a reaction solution. The resulting reaction solution was purified according to a conventional method to obtain 1,2-propanediol.

[Synthesis Example 2]
1142 g of 1,2-propanediol obtained in Synthesis Example 1, 1992 g of terephthalic acid, and 4 g of tin (II) dioctanoate which is an esterification catalyst, a nitrogen introducing tube, a dehydrating tube, a rectifying device, a stirrer, and A 5-L four-necked flask equipped with a thermocouple was charged. The contents of the flask were heated to 230 ° C. under a nitrogen atmosphere. Next, the contents of the flask were stirred at the same temperature for 15 hours, and then the pressure in the flask was reduced to 8.0 kPa. After decompression, the contents of the flask were stirred at 230 ° C. for 8 hours. Thereafter, the temperature of the contents of the flask was lowered to 180 ° C., and 576 g of trimellitic anhydride was added to the flask at the same temperature. After heating the contents of the flask to 210 ° C. over 2 hours, the polymerization reaction was continued under the same temperature and a pressure condition of 10 kPa until the polyester resin in the flask reached the desired softening point. After stopping the polymerization reaction, the contents in the flask were recovered to obtain a polyester resin A.

[Synthesis Example 3]
1960 g of propylene oxide adduct of bisphenol A, 780 g of ethylene oxide adduct of bisphenol A, 257 g of dodecenyl succinic anhydride, 770 g of terephthalic acid, 4 g of dibutyltin oxide as an esterification catalyst, a nitrogen introduction tube, a dehydration tube , A 5-L four-necked flask equipped with a rectifier, a stirrer, and a thermocouple. The contents of the flask were heated to 235 ° C. under a nitrogen atmosphere. Next, the contents of the flask were stirred at the same temperature for 8 hours, and then the pressure in the flask was reduced to 8.3 kPa. After decompression, the contents of the flask were stirred at 235 ° C. for 1 hour. Thereafter, the temperature of the contents of the flask was lowered to 180 ° C., and an amount of trimellitic anhydride was added into the flask at the same temperature so that the oxidation of the polyester resin was a desired amount. After heating the contents of the flask to 210 ° C. over 3 hours, the polymerization reaction was continued at the same temperature and a pressure condition of 10 kPa until the polyester resin in the flask reached the desired softening point. After stopping the polymerization reaction, the contents in the flask were recovered to obtain a polyester resin B.

[Example 1]
100 parts by mass of polyester A (binder resin) obtained in Synthesis Example 1, 7 parts by mass of wax (release agent, WEP-3 (manufactured by NOF Corporation)), and quaternary ammonium salt (charge control agent, Bontron P-51 (manufactured by Orient Chemical Co., Ltd.)) 1.5 parts by mass and carbon black (colorant, MA-100 (manufactured by Mitsubishi Chemical Corporation)) 7 parts by mass were mixed with a stirrer (Henschel mixer 10B ( Nippon Coke Kogyo Co., Ltd.)). The obtained mixture was melt-kneaded using a melt-kneader (PCM-30 (manufactured by Ikegai Co., Ltd.)) to obtain a melt-kneaded product. The obtained melt-kneaded product was coarsely pulverized with a pulverizer (Rotoplex 16/8 type (manufactured by Toa Machinery Co., Ltd.)) and then finely pulverized with a pulverizer (Turbo Mill RS (manufactured by Turbo Industry Co., Ltd.)). The finely pulverized product was classified with an elbow jet (EJ-LABO model EJ-L-3 (manufactured by Nippon Steel Mining Co., Ltd.)) to obtain toner base particles having a volume average particle diameter of 7 μm.

  With respect to 100 parts by mass of the obtained toner base particles, 1.2 parts by mass of hydrophobic silica fine particles (RA-200H (manufactured by Nippon Aerosil Co., Ltd.)) and titanium oxide (EC-100 (titanium) are used as external additives. Industrial Co., Ltd.)) and 0.8 parts by mass of nano-zirconium oxide powder (volume average particle diameter 60 nm, manufactured by Xuancheng Xingxin Materials Co., Ltd.), and a stirrer (Henschel mixer 10B Nippon Coke Kogyo Co., Ltd.)) was mixed for 2 minutes at a rotational speed of 3000 rpm and a jacket control temperature of 20 ° C. to obtain an externally-treated toner.

[Comparative Example 1]
A toner of Comparative Example 1 was obtained in the same manner as in Example 1 except that the nano-zirconium oxide powder was not used during the external addition treatment.

[Comparative Example 2]
60 parts by mass of the toner of Comparative Example 1 and coconut shell activated carbon (particle diameter of about 2 mm, specific surface area of 1000 m ² / g or more) were mixed in a cloth bag in which the toner powder did not leak and had sufficient air permeability. After mixing, a toner that was allowed to stand with activated carbon overnight in a cloth bag was obtained as a toner of Comparative Example 2.

[Reference Example 1]
A toner of Reference Example 1 was obtained in the same manner as Example 1 except that the polyester B obtained in Synthesis Example 2 was used instead of the polyester A obtained in Synthesis Example 1.

  Using the toners of Example 1, Comparative Example 1, Comparative Example 2, and Reference Example 1, the odor generated by the toner was tested according to the following method.

<Odor test in container>
100 g of a toner sample was sealed in a polyethylene bag (I-4) manufactured by Production Japan Co., Ltd. After leaving the bag containing the toner sample for about 120 minutes, the polyethylene bag was opened, and the presence or absence of an unpleasant odor generated from the opening of the polyethylene bag was confirmed. The odor was confirmed by 10 skilled panelists. Table 1 shows the number of uncomfortable odors among the 10 panelists.

<Odor test during fixing>
Using a multi-functional machine (two-component development system TASKalfa 5550ci (manufactured by Kyocera Document Solutions Co., Ltd.)) with the exhaust filter removed, using a two-component developer prepared by the following method and a toner sample, After continuously printing 100 images with an image area of 20%, it was confirmed whether or not an unpleasant odor was generated from the multifunction machine. The odor was confirmed by 10 skilled panelists. Table 1 shows the number of uncomfortable odors among the 10 panelists.

(Two-component developer preparation method)
A carrier for developer (carrier for TASKalfa 5550ci) and 10% by mass of toner with respect to the mass of the carrier were mixed using a ball mill for 30 minutes at room temperature and normal humidity to obtain a two-component developer. .

  According to Reference Example 1, it can be seen that there is almost no problem with odor in the first place if the toner contains a polyester resin that does not contain a unit derived from 1,2-propanediol as a binder resin. On the other hand, according to Comparative Example 1, it can be seen that a toner having a polyester resin containing a unit derived from 1,2-propanediol as a binder resin has a significant problem with an unpleasant odor.

On the other hand, according to a comparison between Example 1 and Comparative Example 2, the activated carbon widely used as an effective deodorizer removes the odor of the toner derived from 1,2-propanediol slightly. However, it can be seen that if the zirconium hydroxide powder is used as a deodorizer, the odor of the toner derived from 1,2-propanediol can be remarkably suppressed.

Claims (2)

A binder resin containing a polyester resin containing units derived from 1,2-propanediol;
An electrostatic charge image developing toner comprising zirconium hydroxide particles.   The electrostatic charge image developing toner according to claim 1, wherein the zirconium hydroxide particles have a volume average particle diameter of 50 nm or more and 100 nm or less.

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