JP2004295046A - Wax masterbatch and electrostatic charge image developing toner - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrostatic charge image developing toner which can ensure a sufficiently wide fixing temperature range in which no offset phenomenon occur (anti-offset region) even when applied to an oilless fixing system, and prevents filming and sticking of a released wax on a photoreceptor and a developing member in a developing device over a prolonged period of time. <P>SOLUTION: This wax masterbatch is prepared by incorporating 25-75 wt.% wax into a low molecular weight resin. This electrostatic charge image developing toner contains fine wax masterbatch particles, as constituent particles, having an average particle diameter of ≤1 μm prepared by incorporating 25-75 wt.% wax into a low molecular weight resin, and the toner is manufactured using the wax masterbatch prepared by incorporating 25-75 wt.% wax into a low molecular weight resin. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

【０１０９】
比較例１〜５のトナーは非オフセット領域はあるが充分とはいえない。
【０１１０】
（耐久性）
耐久性の評価は、カラープリンタ［ｍａｇｉｃｏｌｏｒ ２３００ＤＬ（ミノルタ（株））］を用いてトナーカートリッジに実施例及び比較例のトナーを詰め替えて非オフセット領域の定着温度に固定して評価した。評価は、現像装置内の現像ローラおよび規制ブレードならびに感光体（以下、部材という）、および得られた画像を目視観察することによって以下の基準に基づいて行った。
○：部材に固着およびフィルミングは発生しておらず、画像上にもノイズは発生していなかった；
△：部材に固着または／およびフィルミングは発生していたが、画像上にはノイズは発生していなかった（実用上問題とならないレベル）；
×：部材に固着または／およびフィルミングが発生し、画像上に縦スジ状の画像濃度ムラが発生し、実用上問題があった。
【０１１１】
【表２】

【０１１２】
分散液中の樹脂微粒子またはマスターバッチの平均粒径はワックスマスターバッチ中のワックス粒子の測定方法と同様の方法でＴＥＭ観察により測定した。
【０１１３】
【発明の効果】
本発明のトナーは、オイルレス定着システムに適用されても、オフセット現象が発生しない定着温度範囲（非オフセット領域）を十分に広く確保でき、かつ現像装置内の現像部材や感光体への遊離ワックスの固着やフィルミングを長期にわたって防止できる。
【図面の簡単な説明】
【図１】実施例１で得られたトナー粒子断面のＴＥＭ写真である。
【図２】比較例１で得られたトナー粒子断面のＴＥＭ写真である。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a wax masterbatch, a toner for developing an electrostatic image, and a method for producing the toner.
[0002]
[Prior art]
As a toner fixing method in an image forming apparatus, a heating roll method is widely used. In the heating roll method, the powder toner image on the recording sheet is brought into pressure contact with the surface of the heating roll, heated and melted, and fixed. For this reason, a part of the toner image adheres to the surface of the heating roll and transfers, so that the next recording sheet is stained. In particular, the occurrence of the offset phenomenon was remarkable in a full-color toner that forms a full-color image by superimposing a plurality of powder toner images.
[0003]
In order to prevent the offset phenomenon, a method of including a wax such as polypropylene or polyethylene in toner particles and a method of applying oil to the surface of a heating roll are known. However, when the oil is applied to the surface of the heating roll, the oil permeates the recording sheet and repels the ink on the recording sheet, so that there is a problem that writing with a pen cannot be performed. Therefore, in order to achieve both oilless fixing and prevention of the offset phenomenon, it was necessary to make the toner particles contain a relatively large amount of wax.
[0004]
Known methods for producing toner particles include a pulverization method, a suspension polymerization method, and an emulsion polymerization aggregation method.
In the pulverization method, a binder resin, a colorant, a wax, and the like are melted and kneaded, and the obtained kneaded material is pulverized to obtain toner particles.
In the suspension polymerization method, a polymer composition containing a polymerizable monomer, a colorant, a wax, a polymerization initiator and the like is suspended in an aqueous medium and polymerized to obtain toner particles.
Emulsion polymerization coagulation method is a method of emulsifying a polymer composition containing a polymerizable monomer or the like in an aqueous medium containing a polymerization initiator or the like and polymerizing to obtain resin fine particles. And at least a colorant in an emulsified state by aggregation, fusion and fusion to obtain toner particles. The wax may be added to the polymerization composition by the emulsion polymerization aggregation method, or may be aggregated with the resin fine particles together with the colorant (for example, Patent Document 1).
In any of the above methods, the wax is generally used as it is.
[0005]
However, when a relatively large amount of wax was used in the above-mentioned method of producing toner particles, the wax was difficult to disperse satisfactorily in the toner particles, and the dispersed particle size of the wax became large. For this reason, there is a problem that the wax particles are separated from the toner particles at the time of production or printing. If the wax is released, not only can the offset phenomenon not be sufficiently prevented, but the released wax can also cause sticking and filming on the surface of the developing member such as the regulating blade, the developing roller, the supply roller, and the lower seal material in the developing device, and the photosensitive member. Provoked. As a result, noise such as streak-like density unevenness occurred on the image. Such a problem was particularly remarkable during printing.
[0006]
Thus, a technique has been reported in which a polyolefin wax alone is wet-pulverized in advance in a polymerizable monomer, and then a colorant is added to carry out suspension polymerization (Patent Document 2). However, when a relatively large amount of wax is used, the dispersed particle size of the wax particles in the obtained toner particles is still large, and the above problem cannot be solved.
[0007]
On the other hand, a technique has been reported in which a petroleum resin is added as a grinding aid during the production of toner by a grinding method (Patent Document 3).
[0008]
[Patent Document 1]
Japanese Patent Application Laid-Open No. H11-125931 (Claim 1 on page 2 and pages 6 to 0069)
[Patent Document 2]
JP-A-6-273977 (Claim 1 on page 2)
[Patent Document 3]
Japanese Patent Application Laid-Open No. 11-72965 (Claim 1 on page 2 and 0024 at page 5)
[0009]
[Problems to be solved by the invention]
INDUSTRIAL APPLICABILITY The present invention can secure a sufficiently wide fixing temperature range (non-offset region) where an offset phenomenon does not occur even when applied to an oilless fixing system, and fix free wax to a developing member or a photoconductor in a developing device. It is an object of the present invention to provide a toner for developing an electrostatic image, which prevents filming and filming for a long time.
[0010]
[Means for Solving the Problems]
The present invention relates to a wax masterbatch containing 25 to 75% by weight of a wax in a low molecular weight resin.
[0011]
The present invention relates to a toner for developing an electrostatic charge image, which comprises, as constituent particles, wax masterbatch fine particles having an average particle diameter of 1 μm or less in which 25 to 75% by weight of wax is contained in a low molecular weight resin.
[0012]
The present invention also relates to a toner for developing an electrostatic charge image, which is manufactured by using a wax masterbatch containing 25 to 75% by weight of a wax in a low molecular weight resin.
[0013]
BEST MODE FOR CARRYING OUT THE INVENTION
The toner for developing an electrostatic image of the present invention is manufactured using wax in the form of a wax masterbatch.
[0014]
(Wax masterbatch)
The wax masterbatch used in the present invention contains a wax alone in a low molecular weight resin, and the wax is finely dispersed uniformly in the low molecular weight resin. In the present invention, the wax is used in such a state that it is finely dispersed in the low-molecular-weight resin in advance, and the unification (integration) of the wax particles is effectively prevented by the low-molecular-weight resin in the process of producing the toner particles. Even if a relatively large amount of wax (ie, a wax masterbatch) is used, fine dispersion of the wax particles in the toner particles can be maintained. As a result, it is considered that high filling of the toner particles with the wax is effectively achieved while suppressing generation of free wax, and the object of the present invention can be achieved.
[0015]
The low molecular weight resin used in the present invention has a number average molecular weight (Mn) of 400 to 2,000, preferably 500 to 1800, in which the wax can be effectively finely dispersed. When Mn is less than 400, the heat resistance storage stability of the obtained toner tends to decrease. If Mn exceeds 2,000, there is a problem in the fixability of the toner. The softening point of the low molecular weight resin is preferably from 90 to 140 ° C., particularly preferably from 100 to 130 ° C., from the viewpoints of heat resistance storage stability and fixing property of the toner.
[0016]
Among such low molecular weight resins, petroleum resins, terpene resins and rosin resins are preferred from the viewpoint of wax dispersibility and availability of the resins, and petroleum resins are particularly preferred from the viewpoint of toner production costs. .
[0017]
Petroleum resin is a thermoplastic resin obtained by directly polymerizing cracked petroleum fraction (unsaturated hydrocarbon) generated by cracking of petroleum, and using unsaturated hydrocarbon generated by cracking of naphtha etc. as a catalyst. Those obtained by polymerization using are preferred.
[0018]
Specific examples of the petroleum resin, for example, isopropylene, piperylene, 2-methylbutene, so-called C ₅ petroleum resins composed mainly of cyclopentadiene, as a main component, vinyltoluene, alpha-methyl styrene, indene and the like so-called C ₉ petroleum resin and; like their hydrogenated petroleum resins and partially hydrogenated petroleum resins. The petroleum resin may be composed of a single unsaturated hydrocarbon or may be composed of two or more unsaturated hydrocarbons.
[0019]
Such petroleum resins include, for example, commercially available Imarv series (Idemitsu Petrochemical Co., Ltd.), Alcon series (Arakawa Chemical Co., Ltd.), neopolymer (Nisseki Chemical Co., Ltd.), Petrotac series ( It is available as Tosoh Corporation, Petcol (Tosoh Corporation), FTR series (Mitsui Chemicals), Quinton series (Zeon Corporation), Rigalight (Hercules Corporation) and the like.
[0020]
The terpene resin is a thermoplastic resin obtained by polymerizing at least one terpene compound.
Specific examples of the terpene resin, for example, α-pinene, β-pinene, dipentene, homopolymers and copolymers from terpene compounds such as limonene as a raw material, and copolymers of terpene compounds and other monomers No. Examples of the other monomers include aromatics such as phenols and styrenes.
[0021]
Such terpene resins can be obtained, for example, as commercially available CLEARON (Yasuhara Chemical Co., Ltd.) and YS resin (Yasuhara Chemical Co., Ltd.).
[0022]
Rosin resin is one of natural resins and has thermoplasticity.
Specific examples of the rosin resin include, for example, gum rosin, tall oil rosin, and modified products thereof. As the modified rosin, ester gum (glycerin ester of rosin), hydrogenated rosin, and maleated rosin (maleic acid adduct of rosin) can be used.
[0023]
Such rosin resins are commercially available, for example, as the KR series (Arakawa Chemical Industries, Ltd.) and the KE series (Arakawa Chemical Industries, Ltd.).
These low molecular weight resins may be used alone or in combination of two or more.
[0024]
The wax used in the present invention is not particularly limited, and waxes known in the field of toner for developing electrostatic images can be used. Specific examples of waxes include, for example, vegetable waxes such as candelilla wax, carnauba wax, rice wax, wood wax, jojoba oil wax; animal waxes such as beeswax and whale wax; mineral waxes such as montan wax; Petroleum waxes such as wax and microcrystalline wax; Fischer-Tropsch wax; polyolefin waxes such as low molecular weight polyethylene wax and low molecular weight polypropylene wax; oxidized polyolefin waxes such as oxidized polyethylene wax and oxidized polypropylene wax; higher fatty acids Wax; higher fatty acid ester wax; and the like. One type of these waxes may be used, or two or more types may be used in combination.
[0025]
The softening point of the wax is not particularly limited, but is preferably from 60 to 160 ° C, particularly preferably from 65 to 150 ° C, from the viewpoint of effectively preventing the offset phenomenon.
[0026]
From the viewpoint of easily achieving fine dispersion of the wax in the masterbatch, it is preferable to employ a combination of the following low-molecular-weight resin and wax in combination.
When a petroleum resin is used as the low molecular weight resin, it is preferable to use a non-polar wax such as a polyolefin wax, a paraffin wax, a Fischer-Tropsch wax, particularly a polyolefin wax or a paraffin wax as the wax. In this case, from the viewpoint of more effectively achieving the fine dispersion of the wax in the toner particles, a styrene-based resin or a styrene-acryl-based resin having few polar groups is preferable as the binder resin of the toner.
[0027]
When terpene resin and / or rosin resin is used as the low molecular weight resin, oxidized polyolefin wax, montan wax, carnauba wax, jojoba oil wax, higher fatty acid ester wax, higher fatty acid wax, etc. It is preferable to use a polar wax having an acidic group or the like, particularly an oxidized polyolefin wax. In this case, from the viewpoint of more effectively achieving the fine dispersion of the wax in the toner particles, a polyester resin having an acidic group and / or a hydroxyl group is preferable as the binder resin of the toner. The acidic group is a group capable of releasing hydrogen ions in water, and is, for example, a carboxyl group, a sulfonic acid group, or the like.
[0028]
The content of the wax is 25 to 75% by weight, preferably 30 to 70% by weight, particularly 40 to 70% by weight based on the total amount of the wax and the low molecular weight resin. If the wax content is less than 25% by weight, a sufficient non-offset region cannot be secured. On the other hand, if it exceeds 75% by weight, the wax is released and adheres to the developing roller, the regulating blade, the supply roller, the lower seal, the photosensitive member, etc., and density unevenness appears on the image. When two or more kinds of waxes are used, the total amount thereof may be within the above range.
[0029]
The wax masterbatch uniformly melts and mixes the low molecular weight resin and the wax as described above at a temperature equal to or higher than the softening point of the substance having the highest softening point among the low molecular weight resins and the wax, for example, at 150 to 200 ° C., and then cooled. Can be obtained by:
[0030]
After cooling, the wax masterbatch is usually ground and used for the production of toner.
The particle size of the wax masterbatch suitable for the production of the toner may be selected according to the method for producing the toner to be employed, and generally has an average particle size of 10 nm to 5 mm.
[0031]
The pulverizing means is not particularly limited as long as the desired wax masterbatch particle size is achieved, and usually may be appropriately selected depending on the desired wax masterbatch particle size. In particular, when it is desired to achieve a relatively small particle size of about 1 μm or less, wet grinding may be performed after once performing dry grinding with a known grinding machine such as a jet grinding machine to achieve a relatively large particle size.
[0032]
Wet pulverization is a method in which pulverization is carried out in a liquid, and is a well-known pulverization method suitably employed for efficiently pulverizing fine substances. For example, a high-speed bead mill [Dynomill DL-PILOT (Shinmaru Enterprise Co., Ltd.)] is supplied with ion-exchanged water, wax masterbatch particles having a particle size of about 0.1 to 5 mm, and a pulverizing medium having a diameter of about 0.5 to 3 mm (eg, zirconia). Ball) and drive at a disk peripheral speed of about 1 to 30 m / sec.
[0033]
In the wax masterbatch as described above, the wax particles are finely dispersed with a relatively small particle size, and the particle sizes of the individual wax particles are relatively uniform. That is, the average particle size of the wax particles in the wax master batch is 10 to 100 nm, particularly 10 to 80 nm.
[0034]
The method for measuring the average particle size of the wax particles is as follows.
After the masterbatch particles were cut to a thickness of about 80 nm by an ultra-thin section method, a staining treatment (3 minutes) with ruthenic acid (2% aqueous solution) was performed to clarify the presence of the Wax component, and the cross section of the sample was observed with a TEM. Observed and determined.
-TEM: Hitachi, H-800; acceleration voltage 100 kV
[0035]
The toner particles produced using such a wax masterbatch maintain a fine dispersion of the wax particles in the wax masterbatch, no matter what method is used to produce the toner particles. More specifically, in the toner particles, the wax particles are dispersed with a relatively small particle size in units of individual particles without being united (integrated) with each other, and the particle sizes of the individual particles are relatively uniform. I have. That is, the average particle size and particle size distribution of the wax particles in the toner particles are the same as the average particle size and particle size distribution of the wax particles in the wax masterbatch, respectively.
[0036]
For example, FIG. 1 shows a TEM photograph of a cross section of toner particles manufactured by a pulverization method described later using a wax masterbatch, and a TEM photograph of a cross section of toner particles manufactured by a conventional pulverization method using wax as it is. It is shown in FIG. According to these figures, when the wax is used in the form of a wax masterbatch, the wax is dispersed in a semi-compatible state, and the wax particles are smaller in the toner particles than in the case where the wax is used as it is. It is evident that the particles are finely dispersed. An electronic copy of the photograph shown in FIGS. 1 and 2 will be submitted as a reference photograph at the same time as the present application.
[0037]
(Toner manufacturing method)
The toner of the present invention may be produced by any method as long as the above-mentioned wax masterbatch is used. The method for producing the toner is not particularly limited, and examples thereof include an emulsion polymerization aggregation method, a suspension polymerization method, a pulverization aggregation method, a pulverization method, a spray drying method, and dissolution and dispersion of a toner composition in an organic solvent, and suspension in an aqueous medium. A granulation method (so-called emulsification dispersion method) in which the organic solvent is removed by turbidity or emulsification can be adopted. Hereinafter, the method for producing the toner of the present invention will be described in detail with reference to some examples, but the present invention is not limited to the following method.
[0038]
<Emulsion polymerization aggregation method>
In the emulsion polymerization agglomeration method, a polymer composition containing a polymerizable monomer is dispersed in an aqueous medium containing a polymerization initiator, and a resin for a binder having an average particle size of 50 to 500 nm, particularly 80 to 400 nm is obtained by emulsion polymerization. After obtaining fine particles (hereinafter sometimes referred to simply as resin fine particles), at least the resin fine particles are aggregated, fused and fused to obtain toner particles having an average particle diameter of 2 to 10 μm, particularly 3 to 8 μm. The masterbatch is coagulated, fused and fused with the fine resin particles, or is previously contained in an aqueous medium or a polymerization composition. Preferably, the wax masterbatch is coagulated, fused and fused together with the fine resin particles. The colorant may be agglomerated, fused and fused with the fine resin particles, or may be previously contained in the aqueous medium or the polymer composition, and is preferably agglomerated, fused and fused with the fine resin particles.
[0039]
Specifically, the polymerization composition usually comprises a polymerizable monomer and a chain transfer agent, and may further contain a wax masterbatch.
When the wax masterbatch is previously contained in the polymerization composition, the low-molecular weight resin in the wax masterbatch is dissolved in the polymerization composition (particularly, the polymerizable monomer). It is not limited, and usually one having a diameter of 0.1 to 3 mm is used. In this case, the amount of the wax masterbatch used is preferably 5 to 50 parts by weight, particularly preferably 10 to 35 parts by weight, based on 100 parts by weight of the polymer composition before dissolution. In this case, even if the low-molecular-weight resin of the wax masterbatch is dissolved, the low-molecular-weight resin acts like a dispersing agent for the wax particles. Does not occur. As a result, fine dispersion of the wax particles in the toner particles is achieved.
The dissolution of the low-molecular-weight resin in the polymerization composition may be achieved by first adding the wax masterbatch to a polymerizable monomer, particularly a styrene-based monomer described below, followed by stirring.
[0040]
Examples of the polymerizable monomer include styrene monomers such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, ethylstyrene, dimethylstyrene, butylstyrene, hexylstyrene, and chlorostyrene; and methyl acrylate. , Ethyl acrylate, propyl acrylate, n-butyl acrylate, iso-butyl acrylate, octyl acrylate, dodecyl acrylate, stearyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate, phenyl acrylate, methyl methacrylate , Ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, methacryl Alkyl (meth) acrylate monomers such as stearyl, phenyl methacrylate, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, acrylic acid, methacrylic acid, maleic acid, Examples include acid monomers such as fumaric acid and itaconic acid, and polyfunctional monomers such as divinylbenzene and divinylnaphthalene, and ethylene glycol dimethacrylate. Of the above monomers, it is preferable to use a combination of at least a styrene monomer and an alkyl (meth) acrylate monomer.
[0041]
Examples of the chain transfer agent include mercaptans such as t-dodecyl mercaptan, n-dodecyl mercaptan, and n-octyl mercaptan; and halogenated hydrocarbons such as carbon tetrachloride and carbon tetrabromide.
These chain transfer agents are preferably used in an amount of 0.1 to 15 parts by weight, more preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the polymerizable monomer.
[0042]
The aqueous medium is generally one in which a polymerization initiator and a dispersant are added to water, and may further contain and disperse a wax masterbatch.
When the wax masterbatch is previously contained and dispersed in an aqueous medium, the wax masterbatch usually has an average particle size of 50 to 500 nm. In this case, the amount of the wax masterbatch used is preferably 5 to 50 parts by weight, particularly preferably 10 to 35 parts by weight, per 100 parts by weight of the polymer composition dispersed in the aqueous medium.
[0043]
As the polymerization initiator, a water-soluble one is used. As specific examples, for example, persulfates such as potassium persulfurized, sodium persulfate and ammonium persulfate, 2,2-azobis (2-amidinopropane) dihydrochloride, 4,4- (4-cyanovaleric acid), 2,2-azobis [2- (2-imidazolin-2-yl) propane] disulfate dihydrate, 2,2-azobisisobutylamide dihydrate, 2,2-azobis (2,4- Dimethylvaleronitrile), 2,2-azobisisobutyronitrile, 2,2-azobis (2-methylbutyronitrile), 2,2-azobis (2,4-dimethylvaleronitrile), 2,2-azobis Azo compounds such as (4-methoxy-2,4-dimethylvaleronitrile), dimethyl 2,2-azobisisobutyrate, 2,2- (2,4,4-trimethylpentane), benzoyl peroxide, methyl Ethyl ketone peroxide, and peroxide such as lauryl peroxide.
The polymerization initiator is preferably used in an amount of 0.1 to 20 parts by weight, more preferably 0.5 to 15 parts by weight, based on 100 parts by weight of the polymerizable monomer.
[0044]
As the dispersant, a nonionic surfactant, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and a poorly water-soluble metal compound are used.
Specific examples of the nonionic surfactant include, for example, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene nonylphenol ether, sorbitan monolaurate, polyoxyethylene monolaurate, oleic acid monoglyceride, and stearic acid monoglyceride. And the like.
Specific examples of the anionic surfactant include, for example, sodium stearate, sodium oleate, sodium laurate, sodium dodecylbenzenesulfonate, sodium laurin sulfate, sodium monooctylsulfosuccinate, sodium polyoxyethylene lauryl ether sulfate, and the like. be able to.
[0045]
Specific examples of the cationic surfactant include, for example, laurylaminoacetate, lauryltrimethylammonium chloride, and polyoxyethylalkylamine.
Examples of the amphoteric activator include lauryl betaine.
Examples of poorly water-soluble metal compounds include barium sulfate, calcium sulfate, barium carbonate, magnesium carbonate, calcium phosphate, aluminum oxide, titanium oxide, aluminum hydroxide, magnesium hydroxide, and ferric hydroxide. .
These dispersants can be used alone or in combination of two or more. These dispersants are used in 0.1 to 15 parts by weight, preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the polymerizable monomer.
[0046]
The aqueous medium may further contain a water-soluble polymer as a dispersion stabilizer and a charge control agent or magnetic powder as a toner component. In particular, a charge control agent and a magnetic powder may be contained in the polymerization composition.
Examples of the water-soluble polymer include polyvinyl alcohol, methyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, polyvinyl pyrrolidone, sodium polyacrylate, gelatin, gum arabic and the like. The dispersion stabilizer is used in an amount of 0.1 to 20 parts by weight, preferably 0.5 to 15 parts by weight, based on 100 parts by weight of the polymerizable monomer.
[0047]
Examples of the positive or negative charge control agent include nigrosine-based EX, quaternary ammonium salts, azo-based metal complexes, boron compounds, calixarene-based compounds, alkylsalicylate metal complexes, and fluorinated quaternary ammonium salts. It is possible.
As the magnetic powder, for example, iron, magnetite, cobalt, nickel, ferrite, hematite and the like can be used.
[0048]
When a wax masterbatch, a charge control agent, a magnetic powder, or the like is added to and dispersed in an aqueous medium, the emulsion polymerization is performed by using those additives as seeds.
[0049]
Emulsion polymerization and seed emulsion polymerization may be performed in multiple stages to form resin fine particles for a binder. That is, the polymerization composition is subjected to emulsion polymerization in an aqueous medium, in the presence or absence of a seed, and after mixing the obtained fine resin fine particle dispersion and an separately prepared aqueous medium, further separately prepared polymerization is performed. The composition is mixed and stirred to perform seed emulsion polymerization. Such an operation may be further repeated.
[0050]
Emulsion polymerization and seed emulsion polymerization may be carried out at any temperature higher than the decomposition temperature of the polymerization initiator in the dispersion in which the polymerization composition is dispersed, and usually 40 to 150 ° C is suitable.
[0051]
In aggregating, fusing and fusing the obtained resin particles for a binder, it is preferable to use a wax masterbatch and a coloring agent.
When the wax masterbatch is coagulated, fused and fused together with fine resin particles, the wax masterbatch usually has an average particle size of 1 μm or less, preferably 50 to 700 nm, particularly 80 to 500 nm. In this case, the use amount of the wax masterbatch is preferably 5 to 50 parts by weight, particularly preferably 10 to 35 parts by weight based on 100 parts by weight of the resin fine particles.
[0052]
The colorant used in the present invention is not particularly limited, and a colorant known in the field of toner for developing an electrostatic image can be used.
Specifically, carbon black, phthalocyanine blue, fast sky blue, C.I. I. Basic Blue 5, Modern Blue 7, Cobalt Blue, Pigment Green B, C.I. I. Direct Green 6, Navel Yellow, Naphthol Yellow S, Mineral First Yellow Permanent Yellow NCG, Bendicine Yellow, Cadmium Yellow, Quinacridone, Rhodamine Lake, Methyl Violet Lake, Fast Violet B, Permanent Red 4R, C.I. I. Dyes and pigments such as Basic Red 1 and Modern Red 30 are exemplified.
The colorant may be used in such an amount that the content of the colorant in the toner particles is 1 to 20 parts by weight, preferably 2 to 15 parts by weight, based on 100 parts by weight of the binder resin. When the colorant is used for aggregating with the binder resin fine particles and the like as described above, the amount of the colorant to be used is usually 2 to 15% by weight, preferably 3 to 12% by weight based on the binder resin fine particles. It is. The coloring agent may be previously contained in the polymer composition or the aqueous medium.
[0053]
When coagulating, fusing and fusing the resin fine particles for the binder together with the wax masterbatch and the colorant,
Method (1): Mixing and stirring the obtained dispersion liquid of resin fine particles for a binder and one or more dispersion liquids in which at least a wax masterbatch and a coloring agent (charge control agent, magnetic powder, etc., as necessary) are dispersed. After heat is applied and fused to form fused particles of at least resin fine particles, a wax masterbatch and a colorant (aggregation / fusion step), the entire dispersion is further heated and fused. Fused particles may be fused to form toner particles (fusion step), or method (2); one or more dispersions of the resin fine particle dispersion and at least a wax masterbatch and a colorant dispersed therein. The liquid is mixed and stirred to form an aggregate, and at least aggregated particles of fine resin particles, a wax master batch and a colorant are formed (aggregation step), and then the entire dispersion is heated. Te may be formed toner particles by performing fusion-fusion of the aggregated particles (fusion-fusion step).
In the present invention, it is preferable to employ the method (1) from the viewpoint of more easily obtaining toner particles having a narrower particle size distribution width.
[0054]
In the present specification, the term "aggregation" is used in a concept that the resin fine particles for a binder (and, if desired, a wax masterbatch and a coloring agent) are simply adhered to each other. By the “aggregation”, so-called heteroaggregated particles (group) are formed in which the constituent particles are in contact with each other, but the bonding of the resin fine particles and the wax masterbatch fine particles is not formed by melting. A group of particles formed by such “aggregation” is simply referred to as “agglomerated particles”. By controlling “aggregation”, the particle size distribution of the toner particles can be controlled.
The term “fusion” is used in a concept intended to form a bond by melting of resin fine particles, wax masterbatch fine particles, and the like at a part of the interface between the individual constituent particles in the aggregated particles. The group of particles subjected to such “fusion” is referred to as “fusion particles”.
“Fusion” is used in the concept that the constituent particles of the fused particles are integrated by melting of resin fine particles, wax master batch fine particles, and the like, and become one particle as a unit for use and handling. The integration may be achieved by melting the resin fine particles or the wax master batch fine particles, etc., to the extent that the gaps (pores) between the constituent particles on the appearance surface of the toner particles are eliminated, or the individual toner particles May be achieved to the extent that it is spherical, but it is preferable to achieve the former degree. A group of particles that have undergone such “fusion” are referred to as “fusion particles”.
[0055]
The aggregation in the “aggregation / fusion step” and “aggregation step” in the methods (1) and (2) is usually started by adding an aggregating agent for the purpose of stabilizing the aggregated particles and controlling the particle size distribution of the toner particles. Is done.
Examples of the coagulant include alkali metal salts and alkaline earth metal salts. Specifically, examples of the alkali metal atom of the alkali metal salt and the alkaline earth metal salt include metal atoms such as lithium, potassium, and sodium, and examples of the alkaline earth metal atom include metal atoms such as magnesium, calcium, strontium, and barium. Is mentioned. Among them, metal atoms such as potassium, sodium, magnesium, calcium, and barium are preferred. In addition, examples of the constituents of the alkali metal salt and the alkaline earth metal salt include chloride, bromide, iodine, carbonate, and sulfate.
[0056]
Agglomeration is usually terminated by adding a terminator to stop particle growth. As the terminating agent, a nonionic surfactant, an anionic surfactant or a metal salt of an inorganic acid having an antagonistic effect between metal ions such as a sodium salt when a magnesium salt of an inorganic acid is used as a flocculant is used. Can be
[0057]
The heating temperature in the “aggregation / fusion step” in the method (1) is a temperature at which aggregation and fusion are simultaneously performed, and is usually performed at a temperature equal to or higher than the glass transition temperature of the resin fine particles, for example, 60 to 85 ° C. On the other hand, the heating temperature in the “aggregation step” in the method (2) is a temperature at which only aggregation is achieved, and is usually a temperature lower than the glass transition temperature of the resin fine particles, for example, 40 to 70 ° C.
[0058]
In the “fusion step” of the method (1), it is necessary to raise the temperature of the dispersion system to a temperature equal to or higher than the “aggregation / fusion step”. Heat to ~ 110 ° C and hold if desired.
In the “fusing / fusing step” of the method (2), the dispersion is heated to a temperature equal to or higher than the glass transition temperature of the resin fine particles and equal to or lower than the melting temperature, for example, the same temperature as the above “fusing step”, and if desired, Hold.
[0059]
In particular, in the method (1), a method may be used in which an organic solvent which is infinitely soluble in water is added, and the glass transition temperature of the resin fine particles is substantially lowered to effectively perform fusion and fusion. Examples of the organic solvent infinitely soluble in water include methanol, ethanol, 1-propanol, 2-propanol, ethylene glycol, glycerin, acetone and the like, and preferably methanol, ethanol, 1-propanol having 3 or less carbon atoms, Alcohols of 2-propanol, more preferably 2-propanol.
[0060]
After the formation of the toner particles (fused particles), the toner particles are usually taken out of the toner particle dispersion liquid to remove impurities mixed during production in the washing step, and then dried.
[0061]
In the washing step, acidic and, in some cases, basic water is added to the toner particles in an amount several times the amount of the toner particles, followed by stirring, followed by filtration to obtain a solid content. After adding pure water several times to the solid content and stirring, filtration is performed. This operation is repeated several times, and the process is completed when the pH of the filtrate after filtration reaches about 7, to obtain toner particles.
[0062]
In the drying step, the toner particles obtained in the washing step are dried at a temperature equal to or lower than the glass transition temperature. At this time, it is preferable to adopt a method of circulating dry air or heating under vacuum conditions according to the required temperature. In the drying step, any method such as a normal vibration-type fluidized drying method, a spray drying method, a freeze drying method, a flash jet method and the like can be adopted.
[0063]
The toner of the present invention may have a post-treatment agent on the surface of the toner particles.
Examples of the post-treatment agent include dry-processed silica, wet-processed silica, titanium oxide, alumina, zinc oxide, and strontium titanate. These post-treatment agents may be used after being subjected to a hydrophobic treatment with a silane coupling agent, a titanium coupling agent, silicone oil, or the like. As the post-treatment agent, for example, vinylidene fluoride fine powder, polytetrafluoroethylene fine powder, styrene fine powder, acrylic fine powder, zinc stearate, calcium stearate and the like may be used.
The post-treatment agent is added in an amount of 0.1 to 3 parts by weight, preferably 0.3 to 2 parts by weight, based on 100 parts by weight of the toner particles.
[0064]
In the emulsion polymerization aggregation method, the toner particles obtained when the wax master batch is aggregated, fused and fused together with the resin fine particles have a configuration containing the wax master batch fine particles as constituent particles. That is, the toner particles obtained in this case are obtained by agglomerating resin binder fine particles and wax master batch fine particles and the like. Therefore, in the toner particles, the portion corresponding to the wax master batch fine particles and the portion corresponding to the resin fine particles can be distinguished to the extent that the interface of the wax master batch fine particles before fusion and fusion can be predicted, and the wax master batch fine particles are included as constituent particles. You can see that it is. This is clear from the appearance of the obtained toner particles (TEM photograph). Therefore, in the toner particles obtained in this case, the wax particles are not finely dispersed uniformly throughout the toner particles, but are locally finely dispersed in the toner particles. That is, in the portion corresponding to the wax masterbatch fine particles before fusion and fusion in the toner particles, the dispersion of the wax particles in a semi-compatible state is recognized, but in the portion corresponding to the binder resin fine particles, the dispersion of the wax particles is recognized. I can't.
[0065]
In the above-mentioned emulsion polymerization aggregation method, in the toner particles obtained when the wax masterbatch is previously contained in the aqueous medium or the polymerization composition, the wax particles are uniformly finely dispersed throughout the toner particles.
[0066]
<Suspension polymerization method>
In the suspension polymerization method, a polymer composition containing a polymerizable monomer and a polymerization initiator is dispersed in an aqueous medium and subjected to suspension polymerization to obtain toner particles having an average particle size of 2 to 10 μm, particularly 3 to 8 μm. At this time, the wax masterbatch is previously contained in the aqueous medium or the polymerization composition. Preferably, a wax masterbatch is included in the polymerization composition in advance. The colorant and the charge control agent may be independently contained in advance in the aqueous medium or the polymerization composition, and preferably are previously contained in the polymerization composition.
[0067]
The description of the suspension polymerization method is the same as that of the above-mentioned emulsion polymerization aggregation method except for the following matters, and thus the detailed description of the suspension polymerization method is omitted.
After the polymerization, toner particles can be obtained without going through a process such as aggregation, and washing, drying and post-treatment may be performed.
The wax masterbatch and the colorant are each independently contained in advance in the aqueous medium or the polymerization composition.
-The polymerization initiator is added to the polymerization composition. Therefore, a water-insoluble polymerization initiator is used. The water-insoluble polymerization initiator is not particularly limited as long as it has been conventionally used as a polymerization initiator in a suspension polymerization method. In the suspension polymerization, the temperature of the dispersion in which the polymerization composition is dispersed may be set to an arbitrary temperature equal to or higher than the decomposition temperature of the polymerization initiator.
-When using a charge control agent and a magnetic powder, these additives must be added to the polymerization composition.
[0068]
In particular, when the wax masterbatch is previously contained in the polymerization composition or the aqueous medium, the particle size and amount of the wax masterbatch are the same as those in the above-mentioned emulsion polymerization aggregation method.
Dissolution of the low molecular weight resin in the polymerization composition when the wax masterbatch is previously contained in the polymerization composition, as in the case of the emulsion polymerization coagulation method, the wax masterbatch is first polymerized monomer, especially What is necessary is just to achieve by adding to a styrene type monomer and stirring. In this case, as in the emulsion polymerization aggregation method, since the low molecular weight resin acts like a dispersant for the wax particles, coalescence (unification) of the wax particles does not occur.
[0069]
In the above suspension polymerization method, in the toner particles obtained when the wax masterbatch is previously contained in the aqueous medium or the polymerization composition, the wax particles are uniformly finely dispersed throughout the toner particles.
[0070]
<Pulverization aggregation method>
In the pulverization-aggregation method, at least a binder resin is melted, kneaded, cooled, and pulverized to obtain binder resin fine particles having an average particle diameter of 0.1 to 2 μm, particularly 0.2 to 1 μm. When the toner particles having an average particle size of 2 to 10 μm, particularly 3 to 8 μm are obtained by aggregation, fusion and fusion, the wax masterbatch is melted and kneaded with the binder resin, or is aggregated and fused with the resin fine particles. And fuse. Preferably, the wax masterbatch is melted and kneaded together with the binder resin. The colorant and the charge control agent may be independently melted and kneaded with the binder resin, or may be coagulated, fused and fused together with the resin fine particles.
[0071]
Specifically, first, after preliminarily mixing a binder resin and, if desired, a wax masterbatch, a coloring agent, a charge control agent, a magnetic powder, and the like by a known mixer such as a Henschel mixer, a twin-screw kneader (PCM-30; ) A known kneading machine such as Ikegai) uniformly melts and kneads at a temperature equal to or higher than the melting point of the binder resin and cools.
[0072]
After cooling, the kneaded material is pulverized. The pulverization method is not particularly limited as long as resin fine particles for a binder having the above particle size can be obtained. Usually, pulverization is performed in several stages. For example, after coarse pulverization, an average particle size of about 5 to 100 μm is once achieved by a known pulverizer such as a jet pulverizer (Type I2; Nippon Pneumatic Co., Ltd.), and thereafter, the wet type Grinding may be performed.
[0073]
The binder resin is not particularly limited as long as it is a thermoplastic resin conventionally used in the production of a toner, and examples thereof include a polyester resin, a styrene resin, a styrene-acrylic resin, and an epoxy resin. As the styrene-based resin, a resin composed of the above-mentioned styrene-based monomer can be used. As the styrene-acrylic resin, a resin containing the aforementioned styrene monomer and alkyl (meth) acrylate monomer as constituent monomers can be used.
[0074]
When the wax masterbatch is melted and kneaded together with the binder resin, the wax masterbatch is melted together with the binder resin. Therefore, the particle size of the wax masterbatch is not particularly limited, and usually a wax masterbatch having a particle size of 0.1 to 5 mm is used. . In this case, the amount of the wax master batch used is preferably 5 to 50 parts by weight, particularly preferably 10 to 35 parts by weight based on 100 parts by weight of the binder resin.
As the colorant, the charge control agent and the magnetic powder, the same as described above can be used.
[0075]
After forming the resin fine particles for the binder, aggregation, fusion and fusion of the resin fine particles, and washing, drying and post-treatment may be performed in the same manner as in the emulsion polymerization aggregation method. At this time, aggregation of the resin fine particles for the binder may be performed together with the wax masterbatch or the colorant, or without using the wax masterbatch, only the resin fine particles, or the resin fine particles and the colorant and the charge control agent, etc. Aggregation or the like may be performed.
[0076]
The toner particles obtained when the wax masterbatch is coagulated, fused and fused with the resin fine particles in the above-mentioned pulverization / aggregation method are obtained by coagulating, fusing and fusing the wax masterbatch with the resin fine particles in the emulsion polymerization / aggregation method. As in the case of the toner particles obtained in (1), it has a configuration containing wax master batch fine particles as constituent particles. Therefore, the wax particles are locally finely dispersed in the toner particles.
[0077]
In the pulverization-aggregation method, the wax particles are uniformly finely dispersed throughout the toner particles in the toner particles obtained when the wax master batch is melted and kneaded together with the binder resin.
[0078]
<Pulverization method>
In the pulverization method, at least a binder resin, a wax masterbatch, and a colorant are melted, kneaded, cooled, and pulverized to obtain toner particles having an average particle diameter of 2 to 8 μm, particularly 3 to 6 μm.
[0079]
The description of the pulverizing method is the same as the description of the pulverizing and aggregating method except for the following matters, and thus the detailed description of the pulverizing method is omitted.
-The wax masterbatch and the colorant are added together with the binder resin so as to be melted and kneaded.
After cooling, pulverization is performed so that the above-mentioned particle size of the toner particles is achieved, and toner particles can be obtained without going through a process such as aggregation. After obtaining the toner particles, the same post-treatment as in the emulsion polymerization aggregation method is usually performed.
-Preferably, after pulverization, classification is performed by a known classifier such as Elbow Jet (Nissin Engineering Co., Ltd.).
-When using a charge control agent and magnetic powder, these additives should be added so as to be melted and kneaded together with the binder resin.
[0080]
In the toner particles obtained by the pulverization method, the wax particles are uniformly finely dispersed throughout the toner particles.
[0081]
<Carrier>
The toner for developing an electrostatic image of the present invention obtained as described above may be used in the form of either a two-component developer or a non-magnetic or magnetic one-component developer.
When used as a two-component developer, as a carrier, iron, magnetite, ferrite and magnetite powder, ferrite powder are dispersed in a resin, and a crushed binder type carrier or a carrier coated with a resin on the surface of the carrier is used. Is done.
[0082]
<Measurement method>
In the present invention, the softening temperature conforms to JIS K-2207 and uses a value measured by a ring and ball method. However, the measurement is not necessarily performed by the above method, and may be measured by any method that can be measured according to the same principle as the above method.
In the present invention, the number average molecular weight and the weight average molecular weight are values measured based on polystyrene conversion by gel permeation chromatography (GPC). However, the measurement is not necessarily performed by the above method, and may be measured by any method that can be measured according to the same principle as the above method.
In the present invention, the average particle size of the toner and the wax masterbatch uses a value measured by Coulter Counter Multisizer II. However, it does not have to be measured by the above-mentioned device, but may be measured by any device that can be measured according to the same principle as the above-mentioned device.
[0083]
【Example】
(Production Example 1)
・ Petroleum resin [Alcon P100 (Arakawa Chemical Industries, Ltd.)] 30 parts by weight (softening point: 100 ° C., molecular weight: 610)
-Hydrogenated petroleum resin [I-MARV P-140 (Idemitsu Petrochemical Co., Ltd.)] 20 parts by weight (softening point: 140 ° C, molecular weight: 930)
・ 15 parts by weight of Fischer-Tropsch wax [Paraflint C105 (Kato Yoko Co., Ltd.)] (softening point: 105 ° C)
・ 25 parts by weight of polyethylene wax [High Wax 400P (Mitsui Chemicals)] (Softening point: 136 ° C)
・ Polypropylene wax [Viscol 550P (Sanyo Chemical Industries, Ltd.)] 10 parts by weight (softening point: 152 ° C.)
The above composition was placed in a 1-L two-necked container equipped with a thermometer and a stirrer, uniformly melt-mixed at 170 ° C. while stirring with a mantle heater, and then transferred to a stainless steel vat and allowed to cool. Next, the resulting mixture was pulverized to an average particle size of 2 mm to obtain master batch particles (1) in which wax was uniformly dispersed.
[0084]
(Production Example 2)
・ Hydrogenated petroleum resin [I-MARB P-125 (Idemitsu Petrochemical Co., Ltd.)] 30 parts by weight (softening point: 125 ° C., molecular weight: 880)
・ 15 parts by weight of aliphatic ester wax [Elector WEP-5RF (Nippon Oil & Fats Co., Ltd.)] (softening point: 82 ° C.)
・ 40 parts by weight of polyethylene wax [Neowax LS (Yasuhara Chemical Co., Ltd.)] (softening point: 110 ° C.)
・ 15 parts by weight of polypropylene wax [Viscol 660P (Sanyo Chemical Co., Ltd.)] (softening point: 145 ° C.)
Masterbatch particles (2) were obtained in the same manner as in Production Example 1, except that the above composition was used.
[0085]
(Production Example 3)
・ Petroleum resin [FTR-8120 (Mitsui Chemicals)] 40 parts by weight (softening point: 120 ° C., molecular weight: 920)
・ Polyethylene wax [High Wax 1160H (Mitsui Chemicals)] 25 parts by weight (softening point: 105 ° C)
・ 25 parts by weight of polyethylene wax [Neowax LS (Yasuhara Chemical Co., Ltd.)] (softening point: 110 ° C.)
・ Polyethylene wax [High Wax 800P (Mitsui Chemicals)] 10 parts by weight (softening point: 140 ° C)
Master batch particles (3) were obtained in the same manner as in Production Example 1, except that the above composition was used.
[0086]
(Production Example 4)
-70 parts by weight of cyclopentadiene resin [Quinton A-100 (Zeon Corporation)] (softening point: 100 ° C, molecular weight: 1350)
・ Polyethylene wax [High Wax 4202 (Mitsui Chemicals)] 20 parts by weight (softening point: 108 ° C)
・ Polypropylene wax 10 parts by weight [UMEX 100TS (Sanyo Chemical Co., Ltd.)] (Softening point: 145 ° C)
Masterbatch particles (4) were obtained in the same manner as in Production Example 1 except that the above composition was used.
[0087]
(Production Example 5)
・ Rosin ester [KE311 (Arakawa Chemical Co., Ltd.)] 50 parts by weight (softening point: 100 ° C., molecular weight: 1300)
・ 20 parts by weight of polyethylene wax [Neowax LS (Yasuhara Chemical Co., Ltd.)] (softening point: 110 ° C.)
・ 15 parts by weight of aliphatic ester wax [Elector WEP-5RF (Nippon Oil & Fats Co., Ltd.)] (softening point: 82 ° C.)
-15 parts by weight of polyethylene wax [Sunwax LEL-400P (Sanyo Chemical Co., Ltd.)] (softening point: 128 ° C)
Master batch particles (5) were obtained in the same manner as in Production Example 1 except that the above composition was used.
[0088]
(Production Example 6)
・ Terpen resin [Clearon K-110 (Yasuhara Chemical Co., Ltd.)] 60 parts by weight (softening point: 110 ° C., molecular weight: 700)
-30 parts by weight of polyethylene wax [Neowax LS (Yasuhara Chemical Co., Ltd.)] (softening point: 110 ° C)
-10 parts by weight of polyethylene wax [Polywax TM3000 (Toyo Peterlight Co., Ltd.)] (softening point: 129 ° C)
Master batch particles (6) were obtained in the same manner as in Production Example 1 except that the above composition was used.
[0089]
(Production Example 7)
-Hydrogenated petroleum resin [I-MARB P-100 (Idemitsu Petrochemical Co., Ltd.)] 80 parts by weight (softening point: 100 ° C, molecular weight: 650)
・ 10 parts by weight of polyethylene wax [High Wax 100P (Mitsui Chemicals)] (Softening point: 121 ° C)
・ Polypropylene wax [Viscol 660P (Sanyo Chemical Industries, Ltd.)] 10 parts by weight (softening point: 145 ° C.)
Master batch particles (7) were obtained in the same manner as in Production Example 1 except that the above composition was used.
[0090]
(Production Example 8)
・ Hydrogenated oil resin [Alcon P-125 (Arakawa Chemical Industry Co., Ltd.)] 20 parts by weight (softening point: 125 ° C., molecular weight: 750)
・ Polyethylene wax 50 parts by weight [Neowax LS (Yashara Chemical Co., Ltd.)] (Softening point: 110 ° C.)
20 parts by weight of polyethylene wax [High Wax 100P (Mitsui Chemicals)] (Softening point: 121 ° C)
・ Polypropylene wax [Viscol 550P (Sanyo Chemical Industries, Ltd.)] 10 parts by weight (softening point: 152 ° C.)
Masterbatch particles (8) were obtained in the same manner as in Production Example 1, except that the above composition was used.
[0091]
(Production Example 9)
-Hydrogenated petroleum resin [I-MARV P-140 (Idemitsu Petrochemical Co., Ltd.)] 60 parts by weight (softening point: 140 ° C, molecular weight: 930)
・ Polyethylene wax [High Wax 720P (Mitsui Chemicals)] 10 parts by weight (softening point: 118 ° C)
・ Polyethylene wax [High Wax 200P (Mitsui Chemicals)] 20 parts by weight (softening point: 130 ° C)
・ Polypropylene wax [Viscol 550P (Sanyo Chemical Industries, Ltd.)] 10 parts by weight (softening point: 152 ° C.)
Master batch particles (9) were obtained in the same manner as in Production Example 1 except that the above composition was used.
[0092]
(Production Example 10)
・ Hydrogenated petroleum resin [Imarb P-90 (Idemitsu Petrochemical Co., Ltd.)] 65 parts by weight (softening point: 90 ° C., molecular weight: 590)
-Hydrogenated jojoba oil [M-1 (Mitsuba Trading Co., Ltd.)] (softening point: 68 ° C) 10 parts by weight-Polyethylene wax 15 parts by weight [Polywax 655 (Toyo Peterlight Co., Ltd.)] (softening point: 99 ° C)
・ Polyethylene wax [High Wax 100P (Mitsui Chemicals)] 10 parts by weight (softening point: 121 ° C)
Master batch particles (10) were obtained in the same manner as in Production Example 1 except that the above composition was used.
[0093]
(Example 1)
-Styrene-acrylic resin [Hymer M8005C (Sanyo Chemical Industries, Ltd.)] 75 parts by weight (softening point: 135 ° C, molecular weight: Mn = 9300, Mw = 186000)
-25 parts by weight of the masterbatch particles (1) of Production Example 1-4 parts by weight of a colorant magenta [SANYO Pigment Red 3090 (Sanyo Pigment Co., Ltd.)]-Charge control agent [Bontron E-84 (Orient Chemical Co., Ltd.)] 2 parts by weight The above composition was placed in a Henschel mixer FM10B (Mitsui Miike Kako Co., Ltd.), mixed at a rotation speed of 2,000 rpm for 5 minutes, and kneaded with a twin-screw kneader PCM-30 (Ikegai Co., Ltd.). After pulverization, the mixture was pulverized with a pulverizer jet pulverizer I-2 (Nippon Pneumatic Industries, Ltd.). After this was classified by a classifier Elbow Jet (Nissin Engineering Co., Ltd.), 0.5% by weight of hydrophobic silica [R-974 (Nippon Aerosil Co., Ltd.)] and hydrophobic titanium oxide were added to 100 parts by weight. 1.2 wt% [STT-30A (Titanium Industry Co., Ltd.)] was mixed with a Henschel mixer at 1500 rpm for 3 minutes and shaken with a 140 mesh screen to obtain a toner having an average particle diameter of 6 μm. FIG. 1 shows a TEM photograph of a cross section of the toner particles obtained in Example 1.
[0094]
(Example 2)
・ Polyester resin [R-3990 (Mitsui Chemicals)] 70 parts by weight (softening point: 124 ° C., molecular weight: Mn = 3400, Mw = 77500)
-30 parts by weight of the master batch particles (4) of Production Example 4-4 parts by weight of a colorant magenta [SANYO Pigment Red 3090 (Sanyo Pigment Co., Ltd.)]-Charge control agent [Bontron E-81 (Orient Chemical Co., Ltd.)] A toner having an average particle size of 5.2 μm was obtained in the same manner as in Example 1, except that 1.5 parts by weight of the above composition was used.
[0095]
(Example 3)
An aqueous solution in which 12 parts by weight of magnesium chloride was dissolved in 300 parts by weight of ion-exchanged water was gradually dropped with stirring while an aqueous solution in which 14 parts by weight of sodium hydroxide was dissolved in 100 parts by weight of ion-exchanged water. The liquid was adjusted.
80 parts by weight of styrene monomer (15% by weight of master batch particles (3) of Production Example 3 are dissolved in styrene monomer)
20 parts by weight of n-butyl methacrylate 0.8 parts by weight of a chain transfer agent (t-dodecyl mercaptan) 1.5 parts by weight of a polymerization initiator (lauryl peroxide) 1.5 parts by weight of a coloring agent [SANYO cyanine Blue KRO (Sanyo Color Co., Ltd.) ))] 6 parts by weight of the magnesium hydroxide colloidal dispersion in a 1-L tall beaker, and the above composition was put in a TK homomixer [HV-M type (Tokusai Kika Kogyo Co., Ltd.)] at 5000 rpm. Droplets of the composition mixture were granulated by number.
Next, the mixture was placed in a 1 L four-necked flask equipped with a cooling tube, a thermometer, a nitrogen inlet tube, and a thermometer, reacted at 60 ° C. for 5 hours at a rotation speed of 200 rpm, further heated to 80 ° C., and reacted for 3 hours. Was. After cooling, the pH was adjusted to 4 or less with sulfuric acid, and acid washing (20 ° C., 15 minutes) was performed. Filtration, washing with ion-exchanged water was repeated three times, and drying was performed at 40 ° C. for 72 hours in a dryer.
0.3% by weight of hydrophobic silica [TS-500 (Cabot Corporation)] and 1.0% by weight of hydrophobic titanium oxide [T-805 (Nippon Aerosil Co., Ltd.)] based on the obtained toner particles. Was mixed with a Henschel mixer at 1500 rpm for 3 minutes and shaken with a 140-mesh screen to obtain a toner having an average particle diameter of 6.5 μm.
[0096]
(Example 4)
225 parts by weight of styrene monomer 45 parts by weight of n-butyl methacrylate 0.8 parts by weight of chain transfer agent (t-dodecyl mercaptan) 700 parts by weight of ion-exchanged water in a 2 L tall beaker, and sodium dodecylbenzene sulfonate 5 as a dispersant 0.5 parts by weight and 7.5 parts by weight of ammonium persulfate as a polymerization initiator were added, and the above composition was added thereto, followed by emulsification with a TK homomixer at a rotation speed of 12000 rpm for 2 minutes. Next, the emulsion was placed in a 3 L four-necked flask equipped with a cooling tube, a thermometer, a nitrogen inlet tube and a stirrer, and reacted at 60 ° C. for 5 hours at a rotation speed of 200 rpm. After further reacting at 80 ° C. for 1 hour, the mixture was cooled to obtain an emulsion polymerization liquid A. The average particle size of the resin fine particles in the emulsion polymerization liquid A was 350 nm.
[0097]
<Preparation of colorant dispersion>
3.5 parts by weight of sodium dodecylbenzenesulfonate was dissolved in 25.5 parts by weight of a colorant cyano [SANYO Cyanine Blue KRO (Sanyo Dyeing Co., Ltd.)] and 300 parts by weight of ion-exchanged water, and Ultra Disperser LK22 type (YAMATO) A colorant dispersion liquid dispersed at 15,000 rpm for 5 minutes by Kagaku Corporation was obtained.
[0098]
<Preparation of emulsion liquid B>
450 parts by weight of ion-exchanged water, 150 parts by weight of the master batch particles (2) of Preparation Example 2 and zirconia balls of 2 mm were put into a high-speed bead mill [DYNO-MILL Type KDL (Shinmaru Enterprases Co., Ltd.)]. Emulsion liquid B was obtained by performing wet pulverization at a speed of 10 m / sec. The average particle size of the master batch fine particles in this emulsion was 500 nm.
[0099]
<Aggregation step>
170 parts by weight of the emulsion polymerization solution A and 30 parts by weight of the emulsion solution B are put into a 3 L four-necked vessel equipped with a cooling pipe, a thermometer, a nitrogen inlet pipe and a stirrer, and adjusted to pH 11 at a rotation speed of 80 rpm, and 80 parts by weight of the dispersion was added and the pH was adjusted to 11. Next, while maintaining the temperature at 60 ° C., 350 parts by weight of a 3% aqueous solution of magnesium sulfate was added dropwise over 30 minutes to cause coagulation and fusion. The system was further heated to 80 ° C. and held for 60 minutes for fusing. This was filtered, washed three times with ion-exchanged water, dried in a drier at 40 ° C. for 72 hours, and crushed to obtain toner particles. 0.8 wt% of hydrophobic silica [TS-500 (Cabot Corp.)] is mixed with 100 parts by weight of toner particles at 2000 rpm for 3 minutes using a Henschel mixer, and shaken with a 140 mesh sieve to give an average particle size of 6%. .2 μm was obtained.
[0100]
(Example 5)
In Example 4, an emulsion liquid C was prepared by replacing the master batch particles (2) of Production Example 2 with the master batch particles (6) of Production Example 6. The average particle size of the master batch fine particles in this emulsion was 50 nm. A toner having an average particle diameter of 6.0 μm was obtained in the same manner as in Example 4 except that this emulsion was used.
[0101]
(Example 6)
70 parts by weight of styrene-acrylic resin [Hymer M8005C (Sanyo Chemical Co., Ltd.)] 30 parts by weight of master batch particles (5) of Production Example 5 Colorant carbon black [Mogal L (Cabot Corporation)] 8 2 parts by weight of a charge control agent [Bontron S-34 (Orient Chemical Co., Ltd.)] A toner having an average particle diameter of 6.2 μm was obtained in the same manner as in Example 1 except that the above composition was used.
[0102]
(Example 7)
In Example 1, a toner having an average particle size of 5.9 μm was obtained in the same manner as in Example 1, except that the master batch particles (9) of Production Example 9 were used.
(Example 8)
A toner having an average particle size of 6 μm was obtained in the same manner as in Example 1 except that the master batch particles (10) of Production Example 10 were used.
[0103]
(Comparative Example 1)
・ 75 parts by weight of styrene-acrylic copolymer resin [Aromatex PA-762M (Mitsui Chemicals)]
・ Hydrogenated petroleum resin [I-MARB P-100 (Idemitsu Petrochemical Co., Ltd.)] 15 parts by weight (softening point: 100 ° C., average molecular weight: 650)
・ Polyethylene wax [High Wax 100P (Mitsui Chemicals)] 5 parts by weight (softening point: 121 ° C)
5 parts by weight of polypropylene wax [Viscol 660P (Sanyo Chemical Co., Ltd.)] (softening point: 145 ° C)
4 parts by weight of coloring agent [SANYO Pigment Red 3090 (Sanyo Pigment Co., Ltd.)] 3 parts by weight of charge control agent [Bontron S-34 (Orient Chemical Co., Ltd.)] Example 1 except that the above composition was used. A toner having an average particle size of 5.7 μm was obtained in the same manner as described above. FIG. 2 shows a TEM photograph of a cross section of the toner particles obtained in Comparative Example 1.
[0104]
(Comparative Example 2)
Styrene monomer 80 parts by weight [Polypropylene wax (Viscol 660P: Sanyo Chemical Co., Ltd.) is added at 10% by weight to the styrene monomer, and the mixture is put into a high-speed bead mill: Dynomill DL-PIOT type together with 2 mm zirconia balls. Wet pulverized. ]
20 parts by weight of n-butyl methacrylate 0.8 parts by weight of a chain transfer agent (t-dodecyl mercaptan) 1.5 parts by weight of a polymerization initiator (lauryl peroxide) 1.5 parts by weight of a coloring agent cyano cyanine blue KRO (Sanyo Dye ( Co., Ltd.)] 6 parts by weight A toner having an average particle size of 7.3 μm was obtained in the same manner as in Example 3 except that the above composition was used.
[0105]
(Comparative Example 3)
High-speed bead mill: Dynomill DL-PIOT type, 2 mm zirconia balls, 600 parts by weight of ion-exchanged water and 10 parts by weight of polyethylene wax [Neowax L (Yasuhara Chemical Co., Ltd.)], wet pulverization, and dispersant dodecylbenzenesulfone 3.5 parts by weight of sodium acid were dissolved to obtain an emulsion of polyethylene wax.
-160 parts by weight of the emulsion polymerization liquid of Example 4-40 parts by weight of the above-mentioned polyethylene wax emulsion liquid The same procedure as in Example 4 was repeated except that the above composition was used. 0.5 μm toner was obtained.
[0106]
(Comparative Example 4)
A toner having an average particle size of 6 μm was obtained in the same manner as in Example 1 except that the master batch particles (7) of Production Example 7 were used instead of the master batch particles (1) of Production Example 1. Was.
(Comparative Example 5)
A toner having an average particle size of 5.3 μm in the same manner as in Example 4 except that the master batch particles (8) of Production Example 8 were used instead of the master batch particles (2) of Production Example 2 Got.
[0107]
(Evaluation)
(Fixing)
The fixability was evaluated by modifying a color printer [magiccolor 2300DL (Minolta Co., Ltd.)] so that the fixing temperature could be changed, and refilling the toner in a toner cartridge. Evaluation was performed based on the following criteria by visually observing the obtained image.
：: no offset phenomenon occurred;
Δ: Offset phenomenon was slightly generated, but there was no practical problem;
X: The offset phenomenon occurred, and there was a problem in practical use.
[0108]
[Table 1]

[0109]
The toners of Comparative Examples 1 to 5 have a non-offset area but are not sufficient.
[0110]
(durability)
The durability was evaluated by using a color printer [magicol 2300DL (Minolta Co., Ltd.)] to refill the toners of the examples and comparative examples in the toner cartridge and fixing the toner at the fixing temperature in the non-offset area. The evaluation was performed based on the following criteria by visually observing a developing roller, a regulating blade, a photoconductor (hereinafter, referred to as a member) in the developing device, and an obtained image.
：: No sticking or filming occurred on the member, and no noise occurred on the image;
C: Sticking or / and filming occurred on the member, but no noise was generated on the image (a level that does not pose a problem in practical use);
×: Image sticking or / and filming occurred on the member, and image density unevenness in the form of vertical stripes occurred on the image, which had a practical problem.
[0111]
[Table 2]

[0112]
The average particle size of the resin fine particles or the masterbatch in the dispersion was measured by TEM observation in the same manner as the measurement method of the wax particles in the wax masterbatch.
[0113]
【The invention's effect】
The toner of the present invention can secure a sufficiently wide fixing temperature range (non-offset region) in which an offset phenomenon does not occur even when applied to an oilless fixing system, and can release wax to a developing member or a photoconductor in a developing device. Adhesion and filming can be prevented for a long period of time.
[Brief description of the drawings]
FIG. 1 is a TEM photograph of a cross section of a toner particle obtained in Example 1.
FIG. 2 is a TEM photograph of a cross section of the toner particles obtained in Comparative Example 1.

Claims (5)

Wax masterbatch containing 25 to 75% by weight of wax in low molecular weight resin. A toner for developing an electrostatic charge image, comprising, as constituent particles, wax masterbatch fine particles having an average particle size of 1 μm or less in which a wax is contained in a low molecular weight resin in an amount of 25 to 75% by weight. A toner for developing an electrostatic charge image, which is manufactured by using a wax masterbatch containing 25 to 75% by weight of a wax in a low molecular weight resin. The electrostatic image developing toner according to claim 3, which is produced by a method of any one of the following (A) to (D) using a wax master batch;
(A) A polymer composition containing a polymerizable monomer is dispersed in an aqueous medium containing a polymerization initiator, and emulsion polymerization is carried out to obtain resin fine particles for a binder. Then, at least the resin fine particles are aggregated and fused. And an emulsion polymerization aggregation method for obtaining toner particles by fusing, wherein the wax masterbatch is coagulated, fused and fused together with the resin fine particles, or is previously contained in an aqueous medium or a polymerization composition. ;
(B) A suspension polymerization method for obtaining toner particles by dispersing a polymerization composition containing a polymerizable monomer and a polymerization initiator in an aqueous medium and performing suspension polymerization, wherein the wax masterbatch is dispersed in an aqueous medium or A method characterized by being previously contained in a polymerization composition;
(C) a pulverization-aggregation method in which at least a binder resin is melted, kneaded, cooled and pulverized to obtain binder resin fine particles, and at least the resin fine particles are aggregated, fused and fused to obtain toner particles. Melting or kneading the wax masterbatch with the binder resin, or coagulating, fusing and fusing with the resin fine particles; or (D) melting at least the binder resin, the wax masterbatch and the colorant. A pulverization method in which toner particles are obtained by kneading, cooling, and pulverizing. The electrostatic image development according to any one of claims 2 to 4, wherein the low molecular weight resin is one or more resins selected from the group consisting of a petroleum resin having a number average molecular weight of 400 to 2,000, a terpene resin, and a rosin resin. For toner.

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