JPH09134027A - Noncontact thermal fixing toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To reproduce an image showing excellent anti-smear property, high image density and excellent image quality such as reproducibility of fine lines and gradation by dispersing lots of acicular crystals of a polyolefin wax in a toner. SOLUTION: The toner contains dispersion of lots of acicular crystals of a polyolefin wax 102 in a binder resin 101. The acicular polyolefin wax 102 has 0.5 to 8μm average major diameter, 0.005 to 0.5μm average minor diameter and 5 to 40 aspect ratio. Further, a toner having 2-8μm wt. average particle size is used to obtain a high-quality image. More preferably, such a toner is used that the proportion of particles having >=2 times size as the wt. average particle size is <=2wt.% and that the proportion of particles having <=1/3 size of the wt. average particle size is <=5% in number. In this way, an image showing excellent anti-smear property, as well as excellent resolution, reproducibility of fine lines and halftone reproducibility can be obtd.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a toner for developing an electrostatic latent image in an image forming method such as electrophotography and electrostatic recording, and more particularly to non-contact heating such as flash fixing method or oven fixing method. The present invention relates to toner used in a fixing system.

[0002]

2. Description of the Related Art Conventionally, in an image forming method such as an electrophotographic method, a toner image transferred on a transfer paper is fixed by
Various methods such as a pressure fixing method without heat, a contact heat fixing method such as a heat roll fixing method, and a non-contact heat fixing method such as a flash fixing method and an oven fixing method are used.

Since the characteristics required of the toner differ depending on the fixing methods, toners having characteristics suitable for the respective fixing methods are required. In consideration of realization, the pressure fixing method is not suitable due to restrictions on the toner and the like, and attention is focused on the heat roller fixing method, the flash fixing method, and the like.

In the heat roll fixing method, since the toner image is fixed by passing the transfer paper carrying the toner image through the heated roller pair, an offset phenomenon occurs in which the toner on the transfer paper adheres to the heat roller. To do. Therefore, apply silicone oil, which is a release agent, to the heat roller,
It is necessary to include an offset preventive agent in the toner. On the other hand, the flash fixing method is a method of irradiating a toner image carried on a transfer paper with flash light of a discharge tube such as a xenon flash to soften and melt the toner and fix the toner on the transfer paper. Since the non-contact heat fixing method such as the flash fixing method is a method of fusing and fixing the toner image on the transfer paper in a non-contact manner, the offset phenomenon does not occur unlike the heat roll fixing method.

Further, in recent years, with the widespread use of image forming apparatuses such as copying machines, the applications thereof have been widespread and the demands on the image quality thereof have become strict. Requirements for image quality include high image density, fine line reproducibility, gradation, image texture, and fidelity reproducibility to generation copy. Especially, fine line reproducibility and excellent fine line reproducibility associated with digitalization of image forming apparatuses Gradation is required. Among these required items, fine line reproducibility, gradation, image texture, and faithful reproducibility with respect to generation copy are properties that depend on the particle size of the toner, and therefore have an average particle size of 10 μm or less. The use of small particle size toners has been proposed.
However, when such a small particle size toner is used in a non-contact heat fixing method, as the toner particle size becomes smaller, the fixing strength and the smearing property on paper due to rubbing of images (hereinafter referred to as smearing property) decrease. Problem occurs. In particular, when the smear property of the toner is bad, when an image such as a bar code pattern is formed, image quality is deteriorated due to rubbing and the like, and bar code verification performance is deteriorated. Further, in recent years, there has been a tendency to increase the amount of addition of a coloring agent such as carbon black in order to reduce the toner consumption amount and achieve high hiding property, which tends to deteriorate the smearing property.

[0006]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object thereof is to provide a toner excellent in smearing property in a non-contact heat fixing system.

Another object of the present invention is to provide a non-contact heat fixing toner which has a high image density and is capable of reproducing image quality excellent in fine line reproducibility and gradation.

[0008]

SUMMARY OF THE INVENTION The present invention is a non-contact heating method comprising at least a binder resin, a colorant and a polyolefin wax, wherein a plurality of the above-mentioned polyolefin wax are dispersed as needles in a toner. The present invention relates to fixing toner.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, a toner having a weight average particle diameter of 2 to 8 μm, preferably 3 to 7 μm is used for the purpose of obtaining a high quality image. More preferably, the content of particles having a weight average particle diameter of 2 times or more is 2% by weight or less, and the content of particles having a weight average particle diameter of 1/3 or less has a particle size distribution of 5% by number or less. Use toner.

The toner having the above-mentioned average particle size and particle size distribution can faithfully reproduce even the fine lines of the latent image formed on the photoconductor and is excellent in reproducing the dot latent image in the digital image. Provides an image with excellent gradation and resolution. Further, even when copying or printing is continued, a stable and good image can be obtained with a toner consumption amount smaller than that of the conventional toner, and the economical efficiency is improved. This is because the toner shown in the present invention can reduce the amount of toner required to obtain the same image density as compared with the conventional toner due to the effect of the particle size.

On the other hand, it is generally known that as the particle size of the toner is reduced, the image quality is improved and the verification rate of the bar code pattern and the like is improved. Since the smearing property of the image on the paper decreases, it is impossible to secure a stable verification rate. In this way, stable image quality cannot be obtained only by reducing the toner particle size.

Therefore, in the present invention, a plurality of polyolefin waxes are dispersed in the toner in the form of needles to improve the smearing property and the fixing property of the non-contact heat fixing toner having a small particle size. .

FIG. 1A shows a schematic sectional view of the non-contact heat fixing toner of the present invention, and FIG. 1B shows a schematic sectional view of a conventional toner. In the toner of the present invention shown in FIG. 1 (A), a plurality of polyolefin waxes (102) are dispersed as acicular bodies in a binder resin (101), and the toner shown in FIG. 1 (B) is bound. It is understood that the polyolefin wax (102) is dispersed in the resin (101) in a particle shape (domain shape).

In the present invention, the polyolefin wax needle-like material has a length-to-short ratio of 5 to 40, preferably 8 to 3.
0, and more preferably 10 to 25. The length-to-shortness ratio of the needle-shaped body indicates the average value of the ratio between the maximum length (major axis) of the needle-shaped body and the maximum value (minor diameter) of the width of the needle-shaped body. The short diameter of the needle-shaped body is defined by the maximum value of the width because a needle-shaped body having a shape in which the central portion is slightly swollen in the length direction compared to the tip portion is seen.

The acicular polyolefin wax has an average major axis of 0.5 to 8 μm, preferably 1.0 to
The average minor axis of the needle-shaped bodies is 0.005 to 0.005 μm.
The thickness is 0.5 μm, preferably 0.05 to 0.3 μm.
The long-short ratio, the average long diameter, and the average short diameter of the needle-shaped body were measured from an enlarged photograph of a cross section obtained by cutting toner particles with a microtome and observing the cross section with a transmission electron microscope (TEM).

The reason why the effect of improving the smearing property can be obtained by dispersing the needle-shaped body of the polyolefin wax as in the present invention has not been clarified yet, but it is considered as follows.

First, when a polyolefin wax is added, the wax in the toner is partially eluted on the surface when melted and fixed, and the slippery property of the wax makes it difficult to cause friction with the paper. The wax that does not elute and is present in the toner does not have compatibility with the binder resin that forms the toner, and therefore has an interface with the binder resin, and when the area of the interface becomes large. It is considered that when the toner image and the paper are rubbed, they are sheared from the interface between the wax and the resin and stains on the paper, that is, smear occurs. Therefore, if the wax is present in the toner in the form of particles (domain shape), the area of the interface with the binder resin becomes large and the smearing property deteriorates. Even if the wax is finely dispersed, the central portion of the toner It is considered that the wax existing in the above does not contribute to the improvement of smearing property because it is difficult to elute on the surface.

Based on the above findings, the present invention has found that the effect of improving smearing can be obtained by dispersing a needle-shaped body of a polyolefin wax in a toner. Since the wax elutes from the part of the body close to the toner surface, good slipperiness can be secured, and the area of the interface between the wax and the wax that does not elute on the surface and remains in the toner is small. Therefore, shearing is less likely to occur, and as a result, good smearing property is considered to be obtained.

Polyethylene wax, polypropylene wax and the like are used as the polyolefin wax used in the present invention, and polyethylene wax is particularly preferable from the viewpoint of improving smearing property. It is considered that this is due to the excellent slipperiness of the polyethylene wax. Especially, the softening point (JIS K2207) is 80-
150 ° C., preferably 90 to 140 ° C., more preferably 100 to 130 ° C., molecular weight by the viscosity method is 800 to
It is preferable to use one having a number of 10,000, preferably 1,000 to 5,000.

When the softening point is lower than 80 ° C. or the molecular weight is 8
If it is less than 00, the toner tends to be blocked and the heat-resistant storability tends to deteriorate, and if the softening point is higher than 150 ° C or the molecular weight is higher than 10,000, the effect of improving smearing tends to decrease. It is not preferable because it is present.

Specific examples of the polyolefin wax having such characteristics are Mitsui High Wax 100P,
200P, 400P, 800P (all manufactured by Mitsui Petrochemical Co., Ltd.), Sun Wax LEL-250, LEL-800,
Polyethylene wax such as LEL-400P (above Sanyo Chemical Industry Co., Ltd.), Viscole 330P, 550P, 60
Examples include polypropylene waxes such as 0P, 660P, 100TS, TS200 (all manufactured by Sanyo Chemical Industries, Ltd.).

Further, in order to improve the dispersibility of the wax in the toner, it is preferable to use a graft modified polyolefin wax. The graft-modified polyolefin wax is a polyolefin wax obtained by graft-polymerizing a polymerizable monomer. The graft-modified polyolefin wax used may or may not have a functional group. In particular, it is preferable to use the polyolefin wax and the graft modified polyolefin wax together. It is particularly preferable to use a graft-modified polyethylene wax as the graft-modified polyolefin wax in order to achieve the effects of the present invention. Examples of such graft-modified polyolefin wax include Mitsui High Wax 1120H, 1140H, 1160H, and 2235H.
(The above are Mitsui Petrochemical Industry Co., Ltd.) and other styrene-modified polyethylene waxes, and Mitsui High Wax 3010R (Mitsui Petrochemical Industry Co., Ltd.) and other styrene-acryl-modified polyethylene waxes. When a styrene resin is used as the binder resin, for example, a styrene graft-modified polyolefin wax is used.
It is preferable from the viewpoint of improving the dispersibility of the wax.

In the present invention, the wax is contained in an amount of 0.5 to 5 parts by weight, preferably 1 to 4 parts by weight, based on 100 parts by weight of the binder resin. If the amount is too small, the sufficient effect cannot be obtained. If the amount is too large, not only a suitable effect cannot be obtained, but also the fluidity is deteriorated, the charging property is deteriorated, and filming and other contaminations are adversely affected.

As the toner of the present invention, it is sufficient that the polyolefin wax is dispersed in the above-mentioned state, and a toner prepared by a known method can be used. From the viewpoint, it is preferable to use a toner prepared by a wet granulation method such as a suspension polymerization method or an emulsion dispersion method, instead of a toner prepared by a kneading and pulverizing method.

In the suspension polymerization method, at least the polymerizable monomer and the colorant are dispersed in a dispersion medium such as an aqueous medium in which the monomer and the resin obtained by polymerizing the monomer are insoluble to form particles. Is formed and the monomer in the particles is polymerized to form the colorant-containing resin particles, and then the dispersion medium is removed and the particles are dried to produce the toner particles.

The emulsification dispersion method is at least a thermoplastic resin,
To disperse a colorant and a solvent capable of dissolving this resin in a dispersion medium such as an aqueous medium in which this resin is insoluble and incompatible with the solvent to form particles, and to remove the solvent in the particles. After forming the colorant-containing resin particles by, the dispersion medium is removed and the particles are dried to produce toner particles.

The method of producing the toner of the present invention will be described in detail below by taking the production of the toner by the suspension polymerization method as an example.

First, a polymerizable monomer and a polyolefin wax are mixed in a predetermined amount ratio, heated to dissolve the polyolefin wax in the polymerizable monomer, and then rapidly cooled under high stirring conditions. To deposit the wax as needles. The heating temperature (T
₁ ) is Tm−30 ° C. ≦ T ₁ ≦ Tm, preferably Tm−2, with respect to the softening point (Tm) of the polyolefin wax.
5 ° C ≤ T ₁ ≤ Tm-5 ° C, more preferably Tm-20 ° C
It is preferable that ≦ T ₁ ≦ Tm−10 ° C.

The temperature (T ₂ ) for quenching the polymerizable monomer composition in which the polyolefin wax is dissolved is Tm-based on the softening point (Tm) of the polyolefin wax.
150 ° C ≤ T ₂ ≤ Tm-80 ° C, preferably Tm-15
0 ° C. ≦ T ₂ ≦ Tm-90 ° C., more preferably Tm-15
It is preferable that 0 ° C. ≦ T ₂ ≦ Tm−100 ° C.

A colorant is added to the polymerizable monomer in which the acicular polyolefin wax is dispersed, and the polymerizable monomer composition is suspended and dispersed in an aqueous medium to form particles. After forming the resin particles by polymerizing the monomer, the dispersion medium is removed and the particles are dried to obtain the toner of the present invention.

Further, as described in JP-A-5-333597, the needle wax and the colorant-dispersed resin particles obtained in an aqueous medium are agglomerated by heating in an aqueous medium, The aggregated particles may be dried and then crushed to obtain amorphous toner particles.

The binder resin used in the present invention is not particularly limited as long as it is generally known as a binder resin for toner, and examples thereof include polystyrene resin, poly (meth) acrylic resin, and polyolefin resin. Thermoplastic resins such as resins, polyamide resins, polycarbonate resins, polyether resins, polysulfone resins, polyester resins, epoxy resins, etc., or copolymers, block polymers, graft polymers and the like of these. A polymer blend or the like is used. The binder resin used in the toner of the present invention is not only in a completely polymer state as in a thermoplastic resin, but also contains an oligomer or a prepolymer and a crosslinking agent as in a thermosetting resin. The thing etc. can also be used.

As the colorant, organic and inorganic dyes and pigments can be used, and examples thereof include carbon black, disazo yellow pigment, insoluble azo pigment, copper phthalocyanine pigment, basic dye and oil-soluble dye. Specifically, for the black toner, it is preferable to use carbon black, and it is particularly preferable to use a carbon black graft polymer from the viewpoint of dispersibility. Also,
For color toner, see C.I. I. Pigment Yellow 12, C.I. I. Pigment Yellow 13, C.I. I. Pigment Yellow 14, C.I. I. Pigment Yellow 1
5, C.I. I. Pigment Yellow 17, C.I. I. Pigment Red 2, C.I. I. Pigment Red 3, C.I. I.
Pigment Red 6, C.I. I. Pigment Red 7,
C. I. Pigment Blue 15, C.I. I. Pigment Blue 16 and the like, C.I. I. Solvent Red 49,
C. I. Solvent Red 52, C.I. I. Solvent Red 109, C.I. I. Basic Red 12, C.I. I.
Examples include dyes such as Basic Red 1.

Further, in the toner of the present invention, resin fine particles having an average particle size of 0.05 to 1.0 μm are fixed or mechanically impacted on the surface of the toner particles for the purpose of improving the heat resistance or cleaning property of the toner. It may be coated. Examples of such resin fine particles include styrene-based particles which have been granulated by a wet polymerization method such as an emulsion polymerization method, a soap-free emulsion polymerization method, a non-aqueous dispersion polymerization method or a gas phase method, (meth)
Acrylic-based, styrene- (meth) acrylic-based, olefin-based, fluorine-containing, nitrogen-containing (meth) acrylic-based, silicon-based, benzoguanamine-based, melamine-based resin fine particles can be used, and particularly soap-free emulsion polymerization method. It is preferable to use the resin fine particles obtained by. As a processing device for fixing the resin fine particles to the toner particle surface by utilizing the action of mechanical impact force, a hybridization system (manufactured by Nara Machinery Co., Ltd.), an atomizer (manufactured by Nara Machinery Co., Ltd.), a kryptron ( Kawasaki Heavy Industries Ltd.) can be used.

If desired, a charge control agent, magnetic fine particles, a post-treatment agent, etc. may be added to the toner of the present invention.

As the charge control agent, those generally known in the field of electrophotography can be used, and examples thereof include salicylic acid metal complexes, naphthenic acid metal complexes, metal-containing complex type azo dyes, organic boron complexes and calixes. Negative charge control agents such as allene compounds, bisphenol S compounds, bisphenol A compounds, fluorine-containing quaternary ammonium salt compounds, nigrosine dyes, imidazole compounds,
Examples thereof include positive charge control agents such as quaternary ammonium salt compounds. Examples of magnetic fine particles include magnetite, γ-hematite, and various ferrites. The charge control agent may be contained in the toner particles, or may be fixed on the surface of the toner particles using mechanical impact force or the like.

As the post-treatment agent, a fluidizing agent, a cleaning aid, etc. can be used. As the fluidizing agent, for example, inorganic fine particles such as silica, titania, alumina and tin oxide are used alone or in combination. It is possible, and it is preferable that these inorganic fine particles are hydrophobized with a hydrophobizing agent such as a silane coupling agent, a titanate coupling agent, an aluminum coupling agent, or silicone oil. Further, in order to adjust the chargeability of the inorganic fine particles, a fluorine-containing silane coupling agent, a fluorine-containing silicone oil, an aminosilane coupling agent, an aminosilicone oil or the like may be used together with the hydrophobizing agent.
The fluidizing agent is preferably externally added and mixed with the toner in an amount of 0.01 to 3% by weight, preferably 0.1 to 1% by weight.

Further, as a cleaning aid, a styrene-based compound which is granulated by a wet polymerization method such as an emulsion polymerization method, a soap-free emulsion polymerization method or a non-aqueous dispersion polymerization method, or a gas phase method,
(Meth) acrylic, styrene- (meth) acrylic,
Various fine resin particles of olefin type, fluorine-containing type, nitrogen-containing (meth) acrylic type, silicon type, benzoguanamine type, melamine type, etc., having an average particle size of 0.05 to 1 μm,
It may be externally added to the toner together with the fluidizing agent.

The toner of the present invention is used in combination with a magnetic carrier.
Used as a component developer. As a magnetic carrier,
Magnetic particle carrier such as iron, magnetite, ferrite,
A resin-coated carrier having these magnetic particles as core particles and a surface coated with a resin, a resin dispersion type carrier in which magnetic particle fine powder is dispersed in a resin, and the like can be used. As the resin for coating, for example, polystyrene resin, poly (meth) acrylic resin, polyolefin resin, polyamide resin, polycarbonate resin, polyether resin, polysulfin resin, polyester resin, epoxy resin , Polybutyral resin, urea resin, urethane resin, urea resin, silicone resin, Teflon resin and other thermoplastic resins and thermosetting resins, and mixtures thereof, copolymers of these resins, blocks Polymers, graft polymers and polymer blends are used. Further, a resin having various polar groups may be used to adjust the charging property. Among these resins, it is preferable to use a thermosetting silicone resin, and it is more preferable to use a thermosetting acrylic silicone resin. Further, as the resin used for the resin dispersion type carrier, the above-mentioned resins can be used, but it is particularly preferable to use a polyester resin or a styrene-acrylic resin. The weight average particle size of the magnetic carrier is 20 to 80 μ.
m, preferably 30-60 μm.

[0040]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below with reference to embodiments.

(Production Example 1 of Toner) A flask equipped with a stirrer, an inert gas introduction tube, a reflux condenser and a thermometer was used.
Deionized water in which 0.1 part by weight of vinyl alcohol is dissolved 2
00 parts by weight, and then a mixture of 8 parts by weight of benzoyl peroxide in a polymerizable monomer consisting of 98 parts by weight of styrene and 2 parts by weight of isopropenyloxazoline was added thereto, and the mixture was stirred at high speed. A uniform suspension was prepared. Then, while introducing nitrogen gas, the temperature was raised to 80 ° C., the polymerization reaction was carried out while stirring for 5 hours, and then cooled to obtain a polymer suspension, which was further filtered and washed, and then dried. A polymer having an oxazoline group as a reactive group was obtained. The polymer obtained here: 40 parts by weight and 20 parts by weight of carbon black (MA-100S: manufactured by Mitsubishi Chemical Co., Ltd.) were kneaded at 170 ° C. using a triple roll. After cooling the kneaded product, it was pulverized with a feather mill to obtain a carbon black graft polymer A.

150 parts by weight of styrene, low molecular weight polyethylene (Mitsui High Wax 200P: molecular weight 2000, softening point 130 ° C., density 0.97: manufactured by Mitsui Petrochemical Industry Co., Ltd.)
9 parts by weight, graft modified wax (Mitsui High Wax 1
140H: molecular weight 2100, softening point 103 ° C, density 0.
97: Mitsui Petrochemical Industry Co., Ltd.) 1 part by weight is put into an autoclave substituted with nitrogen, heated to 120 ° C. with stirring, the wax component is dissolved in styrene, and then rapidly cooled to 40 ° C. to wax in styrene. A mixed solution A in which the components were precipitated was obtained.

Deionized water containing 0.5% by weight of sodium dodecylbenzenesulfonate as an anionic surfactant was added to a reaction kettle equipped with an inert gas introduction tube, a reflux condenser and a thermometer, and further, in this reactor. To the above mixture A160
1 part by weight, 60 parts by weight of n-butyl acrylate, 90 parts by weight of carbon black graft polymer A and 3 parts by weight of 2-2'azobisisobutyronitrile were charged, and T. K. After mixing and stirring with an auto homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) to form a uniform suspension, the mixture was heated to 65 ° C. while blowing nitrogen gas, and the suspension polymerization was continued by stirring at this temperature for 5 hours. After performing the reaction, another 7
The polymerization reaction was completed by heating to 5 ° C. Separately, 2 parts by weight of hydrophobic silica (R974: BET specific surface area 170 m ² / g, primary particle size 12 mμ: manufactured by Nippon Aerosil Co., Ltd.) and 2 parts by weight of silane coupling agent (TSL8311: manufactured by Toshiba Silicone Co.) were used as methyl alcohol. And then added to the above suspension and mixed, and then heated at 60 ° C. for 8 hours using a hot air dryer.
After leaving for 5 hours under the condition of 0% RH, further 50 ° C,
Drying was performed for 5 hours under the condition of 50% RH. The charge control agent (E
-84: particle size 0.2 μm: manufactured by Orient Chemical Industry Co., Ltd. and hydrophobic silica (H2000: BET specific surface area 140)
m ² / g, primary particle size 14 mμ: manufactured by Wacker Co., Ltd. with a Henschel mixer (manufactured by Mitsui Miike Kakoki Co., Ltd.) at 2000 r
After mixing for 1 minute at pm, the suspension polymerization agglomerate is crushed by the Kryptron Cosmos System KTM-0 type (manufactured by Kawasaki Heavy Industries Ltd.) with the inlet temperature set at 0 ° C, and the charge on the crushed particle surface is controlled. The agent and hydrophobic silica were fixed. Then, air classification was performed to obtain colored particles A. Hydrophobic silica H is added to 100 parts by weight of the colored particles A obtained here.
Add 0.2 parts by weight of 2000 (manufactured by Wacker) and use a Henschel mixer (manufactured by Mitsui Miike Kakoki Co., Ltd.) to prepare 200
Toner A was obtained by processing at 0 rpm for 1 minute.

(Toner Production Example 2) Deionized water containing 0.1% by weight of polyvinyl alcohol was placed in a reaction vessel equipped with a stirrer, an inert gas introduction tube, a reflux condenser and a thermometer. Glycidyl methacrylate 10 in
Parts by weight, 60 parts by weight of styrene, butyl methacrylate 3
0 parts by weight and 5 parts by weight of benzoyl peroxide were added and stirred at high speed to form a uniform suspension. Then, the mixture was heated to 80 ° C. while blowing nitrogen gas, and stirring was continued for 5 hours at this temperature to carry out a polymerization reaction, and then water was removed to obtain a polymer having an epoxy group as a reactive group. 100 parts by weight of a polymer having an epoxy group as a reactive group and 40 parts by weight of carbon black MA-100 (manufactured by Mitsubishi Chemical Co., Ltd.) were mixed until sufficiently uniform, and then 1 using a pressure kneader.
After kneading and reacting under the condition of 60 ° C., the mixture was rapidly cooled to 40 ° C. and then pulverized with a feather mill to obtain a carbon black graft polymer B.

150 parts by weight of styrene, low molecular weight polyethylene (Mitsui High Wax 400P: molecular weight 4000, softening point 136 ° C., density 0.98: manufactured by Mitsui Petrochemical Industry Co., Ltd.)
8 parts by weight, graft modified wax (Mitsui High Wax 3
010R: molecular weight 3100, softening point 128 ° C., density 0.
(98: manufactured by Mitsui Petrochemical Co., Ltd.) 0.5 part by weight is put into a nitrogen-substituted autoclave and heated to 125 ° C. with stirring to dissolve a wax component in styrene, and then 40 ° C.
By rapidly cooling to, a mixed solution B in which a wax component was precipitated in styrene was obtained.

Deionized water containing 0.5% by weight of sodium dodecylbenzenesulfonate as an anionic surfactant was charged into a reaction kettle equipped with an inert gas introduction tube, a reflux condenser and a thermometer. To the above mixed solution B15
A mixture prepared by adding 8.5 parts by weight, 20 parts by weight of n-butyl acrylate, 70 parts by weight of carbon black graft polymer B and 3 parts by weight of 2-2'azobisisobutyronitrile was charged, and T.I. K. After mixing and stirring with an auto homomixer (made by Tokushu Kika Kogyo Co., Ltd.) to form a uniform suspension,
Then, the mixture was heated to 65 ° C. while blowing nitrogen gas, and the suspension polymerization reaction was carried out by continuing stirring at this temperature for 5 hours, and then further heated to 75 ° C. to complete the polymerization reaction. Separately, 1 part by weight of hydrophobic silica (H2000: manufactured by Wacker), 1 part by weight of charge control agent (E-84: manufactured by Orient Chemical Industry), 2 parts by weight of silane coupling agent (TSL8311: manufactured by Toshiba Silicone Co., Ltd.) After part of the mixture was dispersed in methyl alcohol, the suspension was added and mixed, and then filtration and washing with water were repeated, followed by drying and air classification to obtain colored particles B. Based on 100 parts by weight of the colored particles B obtained here,
Add 0.1 parts by weight of hydrophobic silica (H2000: manufactured by Wacker) and 0.2 parts by weight of hydrophobic titanium oxide (T-805: BET specific surface area 30 m ² / g, primary particle size 30 mμ: manufactured by Nippon Aerosil Co., Ltd.). Then, a toner B was obtained by processing with a Henschel mixer (Mitsui Miike Kakoki Co., Ltd.) at 2000 rpm for 2 minutes.

(Toner Production Example 3) Inert gas introduction tube,
A reaction kettle equipped with a reflux condenser and a thermometer was charged with deionized water containing 0.5% by weight of sodium dodecylbenzenesulfonate as an anionic surfactant, and 150 parts by weight of styrene and n of acrylic acid were further added thereto. A mixture of 20 parts by weight of butyl, 70 parts by weight of the carbon black graft polymer B obtained in Production Example 2 of toner and 3 parts by weight of 2-2′azobisisobutyronitrile, and
T. K. After mixing and stirring with an auto homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) to form a uniform suspension, the mixture was heated to 65 ° C. while blowing nitrogen gas, and the suspension polymerization was continued by stirring at this temperature for 5 hours. After the reaction, the temperature was further raised to 75 ° C. to complete the polymerization reaction. Separately from this, 1 part by weight of hydrophobic silica (H2000: manufactured by Wacker), 1 part by weight of a charge control agent (E-84: manufactured by Orient Chemical Co., Ltd.), a silane coupling agent (TSL8311: manufactured by Toshiba Silicone Co.) 2 Part by weight was dispersed in methyl alcohol, and after adding and mixing to the above suspension, filtration and washing with water were repeated, followed by drying and air classification to obtain colored particles C. 0.1 part by weight of hydrophobic silica (H2000: manufactured by Wacker Co.) and hydrophobic titanium oxide (T-805: manufactured by Nippon Aerosil Co., Ltd.) per 100 parts by weight of the colored particles C obtained here.
Toner C was obtained by adding 2 parts by weight and treating with a Henschel mixer (manufactured by Mitsui Miike Kakoki Co., Ltd.) at 2000 rpm for 2 minutes.

(Production Example 4 of toner) Inert gas introducing pipe,
A reaction kettle equipped with a reflux condenser and a thermometer was charged with deionized water containing 0.5% by weight of sodium dodecylbenzenesulfonate as an anionic surfactant, and 80 parts by weight of styrene and n of acrylic acid were further added thereto. -Butyl 20 parts by weight, carbon black MA-100 (manufactured by Mitsubishi Chemical Corporation) 1
0 parts by weight, low molecular weight polypropylene wax (Viscole 660P: molecular weight 3000, softening point 145 ° C., density 0.89: manufactured by Sanyo Chemical Industry Co., Ltd.) 3 parts by weight and 2-2 ′
A mixture containing 3 parts by weight of azobisisobutyronitrile was charged, and T. K. After mixing and stirring with an auto homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) to form a uniform suspension, the mixture was heated to 65 ° C. while blowing nitrogen gas, and the suspension polymerization was continued by stirring at this temperature for 5 hours. After the reaction, the temperature was further raised to 75 ° C. to complete the polymerization reaction. Separately from this, 1 part by weight of hydrophobic silica (H2000: manufactured by Wacker), 1 part by weight of a charge control agent (E-84: manufactured by Orient Chemical Co., Ltd.), a silane coupling agent (TSL8311: manufactured by Toshiba Silicone Co.) 2 Part by weight was dispersed in methyl alcohol, and the mixture was added to and mixed with the above suspension, followed by repeating filtration and washing with water, followed by drying and air classification to obtain colored particles D. With respect to 100 parts by weight of the colored particles D obtained here,
0.1 parts by weight of hydrophobic silica (H2000: manufactured by Wacker Co., Ltd.) and 0.2 parts by weight of hydrophobic titanium oxide (T-805: manufactured by Nippon Aerosil Co., Ltd.) were added and a Henschel mixer (manufactured by Mitsui Miike Kakoki Co., Ltd.) was used. Toner D was obtained by processing at 2000 rpm for 2 minutes.

(Toner Production Examples 5 to 7) 3 parts by weight of a low molecular weight polypropylene wax (Viscole 660P: manufactured by Sanyo Chemical Industry Co., Ltd.) was added to 100 parts by weight of the colored particles C obtained in Example 3 of the toner production. (Mitsui Miike Kakoki Co., Ltd.) after mixing for 1 minute at 1000 rpm,
The mixture was kneaded by a twin-screw extruder heated to a maximum temperature of 140 ° C and an outlet temperature of 100 ° C. After the kneaded product is left to cool, it is coarsely pulverized to a diameter of 1 mm or less by a feather mill, and a jet mill (MDS2 type: manufactured by Nippon Pneumatic Mfg. Co., Ltd.)
Finely pulverizing and coarse powder cutting with a classifier (Teeplex 50ATP), and changing the fine pulverizing and classifying conditions to obtain colored particles E to G having different average particle diameters and particle size distributions. It was Hydrophobic silica (H2000: manufactured by Wacker) 0.1 to 100 parts by weight of each of the colored particles E to G obtained here.
Toners E to G are added by adding 0.2 parts by weight of hydrophobic titanium oxide (T-805: manufactured by Nippon Aerosil Co., Ltd.) with a Henschel mixer (manufactured by Mitsui Miike Kakoki Co., Ltd.) at 2000 rpm for 2 minutes. Obtained.

(Toner Production Example 8) Colored particles H were obtained in the same manner as in Toner Production Example 5 except that the wax used was changed to low molecular weight polyethylene (Mitsui High Wax 200P: manufactured by Mitsui Petrochemical Industries, Ltd.). The colored particles H were subjected to the same post-treatment as in Toner Production Example 5 to obtain Toner H.

(Toner Production Example 9) 100 parts by weight of a polyester resin (NE-382: manufactured by Kao) and 4 parts by weight of a cyan pigment (CI Pigment Blue 15-3: manufactured by Toyo Ink Manufacturing) were ball milled. After mixing well, 140
The mixture was kneaded on a triple roll heated to ℃, left to cool, and coarsely pulverized using a feather mill. 2 parts by weight of low-molecular-weight polyethylene (Mitsui High Wax 200P: manufactured by Mitsui Petrochemical Industry Co., Ltd.) per 100 parts by weight of the coarsely pulverized product obtained here,
Graft modified wax (Mitsui High Wax 1160H:
(Molecular weight 1500, softening point 105 ° C., density 1.00: manufactured by Mitsui Petrochemical Industry Co., Ltd.) 0.5 parts by weight are thoroughly mixed with a ball mill, and then 500 parts by weight of toluene are added, and the mixture is heated to 80 ° C. with stirring to obtain toluene. The wax component was completely dissolved therein. Separately, methyl cellulose (Methocel K35LV: manufactured by Dow Chemical Co.) 4% as a dispersion stabilizer
Solution 60 parts by weight, dioctyl sulfosuccinate soda (Nikkor OTP75: Nikko Chemical Co., Ltd.) 1% solution 5 parts by weight, sodium hexametaphosphate (manufactured by Wako Pure Chemical Industries, Ltd.)
After preparing an aqueous solution in which 0.5 part by weight was dissolved in 1000 parts by weight of ion-exchanged water, this was kept at 5 ° C. A solution obtained by dissolving and dispersing the toner component in the hot toluene obtained above is put into this aqueous solution with a TK Auto Homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) with strong stirring to uniformly disperse the solution. Then, it is stabilized at a temperature of 60 ° C., and the particle diameter of the suspended particles is 3 to
The rotation speed was adjusted to 10 μm and the suspension was suspended in water. In this suspension, a calixarene compound (E-8) previously dispersed in methanol so as to form a fine particle state sufficiently.
9: particle size 0.2 μm: manufactured by Orient Chemical Industry Co., Ltd.) 0.5
Parts by weight and 0.5 parts by weight of hydrophobic silica (R-974: manufactured by Nippon Aerosil Co., Ltd.) were added and mixed with 100 parts by weight of the colored resin. This mixed dispersion was vigorously stirred together with an ultrasonic oscillator. After that, after repeating filtration / washing with water, the particles were dried by a slurry dryer (Dispercoat: manufactured by Nisshin Engineering Co., Ltd.) and further classified by wind to obtain colored particles I. Further, with respect to 100 parts by weight of the colored particles I obtained here, hydrophobic silica (H2000:
0.3 parts by weight of Wacker Co., Ltd. and 0.5 parts by weight of hydrophobic titanium oxide (T-805: Nippon Aerosil Co., Ltd.) were added, and the mixture was mixed with a Henschel mixer (Mitsui Miike Kakoki Co., Ltd.).
Toner I was obtained by processing at 000 rpm for 2 minutes.

(Production Example of Carrier) 20 parts by weight of acrylic modified silicone resin KR9706 (manufactured by Shin-Etsu Chemical Co., Ltd.) was dissolved in 400 ml of methyl ethyl ketone to prepare a coating solution. Using a Spiracoater (manufactured by Okada Seiko Co., Ltd.), this coating solution was Cu-having an average particle size of 50 μm.
Spray on Zn-based ferrite particles, coat with resin,
Then, the coating resin was heated at 180 ° C. to cure for 30 minutes to prepare an acrylic-modified silicone resin-coated carrier. The carrier obtained here is crushed with a crusher to obtain 90
After classification with a sieve of μm, magnetic separation was performed to remove low magnetic components, and a resin-coated ferrite carrier having an average particle diameter of 50 μm was prepared.

(Evaluation) (1) Particle size measurement The particle size and particle size distribution of the toner were measured with a Coulter Multisizer (manufactured by Coulter Co.) with an aperture of 50 μm, and the results are shown in Table 1.

The average particle size of the carrier was measured using a laser diffraction particle size distribution analyzer SALD-1100 (manufactured by Shimadzu Corporation).

The long-short ratio, average long diameter, and short diameter of the needle-shaped wax are determined by observing the cross section of the toner particles with a transmission electron microscope (T.
Observed by EM) and measured from the enlarged photograph, the results are shown in Table 1.
It was shown to.

[0056]

[Table 1]

(2) Evaluation of Actual Machine As an evaluation machine, the flash fixing type continuous paper printer shown in FIG. 1 was used. In the figure, a photosensitive drum (1), which is an electrostatic latent image carrier, is installed in the upper right portion. This drum is rotationally driven in the direction of the arrow in the figure by a driving means (not shown). A corona charger (2), a developing device (3), a transfer device (4), a cleaning device (5), and an eraser (6) are sequentially arranged around the photosensitive drum (1). An optical system (7) is arranged below the photosensitive drum. This optical system includes a semiconductor laser generator, a polygon mirror, a toroidal lens, and a housing (71).
A half mirror, a spherical mirror, a folding mirror, a reflection mirror, etc. are arranged, and an exposure slit is formed in a portion of the housing (71) facing the photoconductor, from which the charger (2) and the developing device ( The photosensitive drum (1) can be exposed through the space 3). A paper feed tray (91) is provided in the lower part of the drawing, and a continuous paper (10) with perforations for cutting is folded and stored. Further, a fixing flash (8), a paper discharge roller pair (92), and a paper discharge roller pair (93) are sequentially arranged along the paper conveyance path (9), and the paper discharge roller pair (93). The discharge tray (94) faces the front.

According to this printer, the surface of the photosensitive drum (1) is uniformly charged to a predetermined potential by the charger (2), and the charged area is exposed by the optical system (7) to form an electrostatic latent image. To be done. The exposure of the photosensitive drum is performed based on the image information from the controller (100). The formed electrostatic latent image is stored in the developing device (3),
The toner image is reversely developed by the toner frictionally charged with the same polarity as the photosensitive drum to form a toner image, and the toner image is transferred to the transfer area facing the transfer device (4). On the other hand, holes are continuously provided in both ends of the continuous paper (10) stored in the paper feed tray (91) along the transport direction. Sprocket device (9
In step 0), this hole is hooked and the continuous paper is automatically stepwise fed in a predetermined direction by a stepping motor. The continuous paper is sent to the transfer area along the transport path. In the transfer area, the transfer device (4) transfers an electrostatic charge having a polarity opposite to the charging polarity of the toner from the back surface of the paper to transfer the toner image on the photoconductor drum (1) onto the paper, and a fixing flash. After being fixed by (8), it is discharged to the discharge tray (94) by the pair of discharge rollers (93). After the toner image is transferred to the paper, the toner remaining on the photosensitive drum (1) is cleaned by the cleaning device (5), and the residual charge is erased by the eraser (6).
This completes a series of image forming operations.

An image was formed on the above continuous paper printer under the following image forming conditions. -Photoconductor drum peripheral speed: 100 mm / sec-Photoconductor drum surface potential: -650 V-Development bias: -400 V-Continuous paper thickness: 8 mil-Developer used: Toners A to I and the above carrier, respectively A developer prepared to have a toner concentration of 4% by weight.

(A) Evaluation of Fixing Strength The fixing strength is determined by rubbing the fixed image sample with a sand eraser loaded with 1 kg and measuring the image density before and after rubbing with the sand eraser using a Sakura Densitometer PDA65. [(Image density after rubbing / image density before rubbing) × 10
0] was calculated and the results are shown in Table 2.

(B) Smearability evaluation Smearability was determined by using a cherry densitometer PDA65 and superimposing a sheet of paper on which an image having an image density of 1.2 in a solid area was formed and a blank sheet of paper and superposing 50 g / cm. ^The evaluation was performed by visually observing the degree of toner transfer to the white paper portion when the papers were rubbed together under the load of ² . The case where toner transfer to the white paper part is not recognized is evaluated as ○, the case where toner transfer is slightly recognized is △, and the case where transfer to the white paper part has occurred and apparently color transfer has occurred is judged as ×. The results are shown in Table 2.

(C) Evaluation of image quality (dot reproducibility) A print pattern of 1on1off is printed, and one dot on / off can be reproduced at equal intervals.
One dot can be recognized, but one dot is on / of
The results are shown in Table 2 when the variation of the interval of f is Δ, and when the dots are attached to each other and the reproducibility of dots is poor, the result is x.

(D) Evaluation of Fogging on Image The toner fogging on a white background image was evaluated using a 20 times magnifying glass, and those with no toner fogging were evaluated as ◯, and those with some toner fogging that were practically usable. Δ, the toner fogging is large and there is a problem in practical use was evaluated as ×, and the results are shown in Table 2.

[0064]

[Table 2]

[0065]

According to the toner of the present invention, an image excellent in smear resistance can be obtained in a non-contact heat fixing system such as a flash fixing system or an oven fixing system.
Further, according to the toner of the present invention, resolution, fine line reproducibility,
Images with excellent halftone reproducibility can be obtained.

[Brief description of the drawings]

FIG. 1A is a schematic diagram showing a wax dispersion state of a non-contact heat fixing toner of the present invention, and FIG. 1B is a schematic diagram showing a conventional toner wax dispersion state.

FIG. 2 is a schematic configuration diagram of a flash fixing type continuous paper printer.

[Explanation of symbols]

1: photoconductor drum, 2: charger, 3: developing device, 4: transfer device, 5: cleaning device, 6: eraser, 7:
Optical system, 8: Flash fixing device, 9: Conveying path, 10: Continuous paper, 90: Sprocket device, 91: Paper feed tray, 9
2: Paper ejection roller pair, 93: Paper ejection roller pair, 94: Ejection tray, 101: Binder resin, 102: Wax.

Claims (6)

[Claims] 1. A non-contact heat fixing toner comprising at least a binder resin, a colorant and a polyolefin wax, wherein a plurality of the polyolefin wax are dispersed as needles in the toner. . 2. The non-contact heat fixing toner according to claim 1, wherein the length-to-width ratio of the needle-shaped body is 5 to 40. 3. The average minor axis of the needle-shaped body is 0.005.
The non-contact heat fixing toner according to claim 2, wherein the toner has an average major axis of 0.5 to 8 μm. 4. The toner has a weight average particle diameter of 2 to 8 μm.
The toner for non-contact heat fixing according to claim 1, wherein 5. The toner contains 2% by weight or less of particles having a weight average particle diameter of 2 times or more, and 5% by number or less of particles having a weight average particle diameter of 1/3 or less. 5. The non-contact heat fixing toner according to claim 4, having a particle size distribution of. 6. The non-contact heat fixing toner according to claim 1, wherein the toner is produced by a wet granulation method.