JPS60254154A - Toner for development of electrostatic charge image - Google Patents

Abstract

PURPOSE:To decrease the min. fixing temp. of a toner and to improve the fluidity thereof by incorporating a polyester resin having an aliphat. hydrocarbon group of 3-22C at the side chain and a release agent consisting of specifically composed wax and alkylene bis-fatty acid amide into said toner. CONSTITUTION:The polyester resin which is the non-linear copolymer obtainable from monomer components contg. monomers such as an etherified bisphenol monomer, dicarboxylic acid monomer and tri- or higher hydric alcohol monomer and has the aliphat. hydrocarbon group of 3-22C at the side chain is prepd. The wax contg. >=20wt% ester component and having <=4 penetration and the compd. expressed by formula I [R1, R2 denote a satd. or unsatd. aliphat. group of >=10C, R3, R4 denote a hydrogen atom, -OCR5 (R5 is a satd. or unsatd. aliphat. hydrocarbon grup)] are incorporated as the release agent into such resin. The toner development of an electrostatic charge image is thus prepd.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a toner for developing electrostatic images formed in electrophotography, electrostatic printing, electrostatic recording, and the like.

[Prior art]

For example, in electrophotography, an electrostatic latent image is usually formed by charging and exposing an electrostatic image support such as a photoconductive photoreceptor, and then this electrostatic latent image is transferred to fine particles such as a binder resin. The toner image is developed using a toner containing a colorant and the like, and the resulting toner image is transferred to a support such as transfer paper and then fixed by heating, pressure, etc. to form a visible image.

It is of course preferable to form a visible image via such an electrostatic charge image at high speed, and from this point of view conventionally, thermal roller fixing has been used in the fixing process, which has high thermal efficiency and is advantageous compared to other methods. The method has been widely adopted.

However, in recent years, there has been a strong demand for even higher speeds, and in order to achieve this, it is essential to increase the speed of toner image fixing.

Therefore, in order to fix toner images at high speed in the thermal lawn fixing method, the toner used for development is required to have good low-temperature fixability. Need to lower the score. However, if the softening point of the binder resin of the toner is lowered, a part of the toner forming the image will be transferred to the surface of the heat roller during fixing, and this will be transferred again to the next transfer paper, etc., and the image will be imaged. There is a tendency for the so-called offset phenomenon to occur, which stains the surface.

Furthermore, in the heat roller fixing method, in addition to the above-described offset phenomenon, there is a problem in that a so-called wrapping phenomenon occurs in which the transfer paper or the like is adhered to the surface of the heat roller and wrapped around it. This winding phenomenon occurs particularly when the temperature of the heat roller is too low.

In order to prevent the occurrence of the offset phenomenon and the winding phenomenon described above, various proposals have been made and some have been put into practical use. One method is to apply release oil such as silicone oil to the surface of a heated roller while fixing.
Others impart releasability to the toner itself to provide anti-offset performance. The latter method is superior in that the structure of the fixing device is simple because a silicone oil application mechanism and the like are not required, and maintenance such as replenishment of silicone oil is not required. Known methods for imparting anti-offset properties to the toner itself include (a) a method of using a high molecular weight polymer as a binder resin in the toner, and (b) a method of incorporating a release agent into the toner. ing.

However, in the above method (a) using a high molecular weight polymer, although the non-offset property of the toner is improved,
At the same time, the increase in the softening point makes it difficult to achieve low temperature fixing.

By the way, polyester resins are attracting attention as binder resins with low softening points. Since polyester resin can be relatively easily obtained in the form of a low molecular weight, it can be used as a binder to obtain a toner with a low softening point. Compared to toner as a binder,
When melted, it "wets" well to a support such as transfer paper, and compared to toners made of vinyl polymers, which have approximately the same softening point, sufficient fixation can be achieved at a much lower temperature. has advantages.

On the other hand, as a method of incorporating the above-mentioned release agent into a toner, Japanese Patent Publication No. 52-3304 and Japanese Patent Publication No. 52
As disclosed in Japanese Patent No. 3305, a method has been proposed in which a polyolefin wax such as polypropylene wax or polyethylene wax is used as a mold release agent. Although it is effective to use such a mold release agent,
In order to obtain a toner with high non-offset and non-wrapping properties and a sufficiently wide practical fixing temperature range, it is necessary to apply toner VC of the release agent. −
There is no such thing as IA'.

However, as the content of the release agent in the toner increases, the fluidity of the toner as a powder decreases, and as a result, even if the fixing performance is satisfied, good development becomes difficult. Generally, high image density cannot be obtained.

In addition, when using a toner containing a polyethylene wax, an electrostatic charge image support such as a photoconductive photoreceptor that supports the electrostatic charge image to be developed, a developing sleeve of a developing device, a two-component developer, etc. When used as a carrier, the characteristics of the carrier etc. deteriorate relatively quickly, making it impossible to obtain a long useful life. This is because the wax component in the toner adheres to the so-called filmink phenomenon, and the reason for this is that in order to reliably obtain the effect of adding wax, it is necessary to increase the content of the wax considerably. This is thought to be because the wax exists in a so-called phase-separated state in the toner particles due to the low dispersibility of the wax in the binder resin of the toner and the large wax domains in the toner.

[Purpose of the invention]

The present invention has been made against the above-mentioned background, and its objects are to have sufficient non-offset properties, a low minimum fixing temperature, high fluidity and non-agglomeration properties, and a long service life. It is an object of the present invention to provide an electrostatic image developing toner that can consistently form good visible images over a period of time and is suitable for high-speed fixing.

[Structure of the invention]

The above objectives are (a) etherified bisphenol monomer,
A non-linear copolymer obtained from a monomer component containing a dicarboxylic acid monomer, a trivalent or higher polyhydric alcohol monomer, and/or a trivalent or higher polyvalent carboxylic acid monomer, 20% by weight of a polyester resin having an aliphatic hydrocarbon group having 3 to 22 carbon atoms in its side chain and a Φ) ester component.
This is achieved by a toner for developing an electrostatic image, which is characterized by containing a wax containing the above and having a penetration degree of 4 or less, and a release agent consisting of an alkylene bis fatty acid amide compound represented by the following general formula.

General formula [In the formula, R□ and bird each represent a saturated or unsaturated aliphatic hydrocarbon group having 10 or more carbon atoms, which are the same or different from each other; 0CR, a group (wherein Rs represents a saturated or unsaturated aliphatic hydrocarbon group), and n represents a positive integer. ] Hereinafter, the present invention will be explained in detail.

The toner for developing electrostatic images of the present invention uses a polyester resin having hydrogen groups in an ester structure of etherified bisphenol and dicarboxylic acid as a binder resin, and contains toner particles containing a colorant and other additives as necessary. Together with the ingredients, the wax contains an ester component of 20% by weight or more, has a penetration of 4 or less, preferably has a melting point of 60 to 110°C, and an alkylene bis fatty acid amide compound represented by the following general formula. Contains a mold release agent.

General formula [wherein R1 and avian are each the same or different from each other and represent saturated or unsaturated aliphatic hydrocarbon groups having 10 or more carbon atoms, and R3 and R are each the same or different hydrogen atoms or 10CR , a group (wherein Rs represents a saturated or unsaturated aliphatic hydrocarbon group), and n represents a positive integer. ] In the above, the wax penetration is J I 5K223
5-1980. That is, the sample wax is heated and melted and placed in a sample container9. After being allowed to cool, the temperature is maintained at a constant temperature of 25°C in a constant temperature water bath, and a needle with a total mass of 'tioog is vertically inserted into the sample wax for 5 seconds. The depth of penetration of the needle is measured to the nearest 0.1 inch, and the value obtained by multiplying this by 10 is defined as the degree of penetration.

Further, the melting point is determined by differential scanning calorimetry (DSC). In other words, several samples were heated at a constant heating rate (10°C/
The melting point is the melting peak value when heated at -).

The monomer components used in the synthesis of the polyester resin (non-linear copolymer) constituting the binder in the present invention are mainly composed of (a) etherified bisphenol as a component constituting the basic skeleton of the copolymer; Dihydric alcohol monomer and divalent carboxylic acid monomer/trihydric or higher polyhydric alcohol monomer involved in nonlinearization, that is, branching or network formation of the (I:I) copolymer. 74 or polycarboxylic acid monomer with a valence of 3 or more; In order to introduce a saturated or unsaturated aliphatic hydrocarbon group in 22, 2 having the hydrocarbon group (alcohol monomer in 1 and/or a divalent or higher carboxylic acid monomer having the hydrocarbon group) The monomer is often polyacidic and may contain other monomers if necessary.

The etherified bisphenol in (a) above includes polyoxypropylene (2,2)-2,2-bis(←hydroxyphenyl)propane, polyoxyethylene (2)
-2,2-bis(4-hydroxyphenyl)propane,
Polyoxypropylene (6)-2,2-bis(4-hydroxyphenyl)propane, polyoxypropylene (1
, 3)-2,2-bis(4-hydroxyphenyl)propane, and the like. Other divalent alcohol monomers include ethylene glycol, diethylene glycol, triethylene glycol, 1.2-propylene glycol, 1.3-propylene glycol%1
, 4-butanediol, neointyl glycol, 1.
Diols such as 4-butynediol, 1,4-bis(hydroxymethyl)cyclohexane, and bispheno-k
Examples include hydrogenated bisphenol A and hydrogenated bisphenol A.

In addition, as divalent carboxylic acid monomers, maleic acid,
fumaric acid, mesaconic acid, citraconic acid, itaconic acid,
Glutaconic acid, phthalic acid, inphthalic acid, terephthalic acid, cyclohexanedicarboxylic acid, succinic acid, adipic acid, sepacic acid, malonic acid, anhydrides of these acids, dimers of lower alkyl esters and dileic acid, other divalent acids Examples include organic acid monomers. The amount of these divalent carboxylic acid monomers used is 10% of the total acid component.
~90 mol, or 20 to 60 mol.

The trivalent or higher polyhydric alcohol monomers mentioned above are as follows:
For example, lupitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, sucrose, 1,2,4-butanetriol, 1,2,5-pentane triol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3.5-)lyhydroxymethylbenzene, and others. can be mentioned. The amount of these polyhydric alcohols used is 5 to 50 mol or 10 to 40 mol based on the entire alcohol component. Usage amount is 5
If it exceeds 0 mole, the fixing performance of the toner will be insufficient.
If it is less than molty, the copolymer will not be rendered non-linear and the non-offset properties will be insufficient.

In addition, examples of trivalent or higher polyvalent carboxylic acid monomers include 1,2,4-benzene) IJ carboxylic acid, i.

2.5-benzenetricarboxylic acid, 1,2.4-cyclohexanetricarboxylic acid, 2,5.7-naphthalenetricarboxylic acid, 1,2.4-naphthalenetricarboxylic acid,
1.2.4-butanetricarboxylic acid, 1.2.5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylenecarboxylpropane, tetra(methylenecarboxyl)methane, 1,2,7° Examples include 8-octane tetracarboxylic acid, empol trimer acid, acid anhydrides thereof, and others. The amount of these polyhydric carboxylic acid monomers used is 5 to 50% of the total acid component.
The amount is 50 moles, preferably 10 to 40 moles. If the amount used exceeds 50 moles, the fixing properties of the toner will be insufficient, and if the amount used is less than 5 moles, the non-linearity of the copolymer will be insufficient, resulting in insufficient non-offset properties of the toner.

The above-mentioned (c) divalent or higher alcohol monomers and divalent or higher carboxylic acid monomers having a saturated or unsaturated hydrocarbon substituent having 3 to 22 carbon atoms include the above-mentioned (
A) and (B) can be used, especially n-dodecenylsuccinic acid, isododecenylsuccinic acid,
n-dodecylsuccinic acid, iso-octylsuccinic acid, n-
Suitable examples include octylsuccinic acid and n-butylsuccinic acid. The total amount of these divalent or higher alcohol monomers and divalent or higher carboxylic acid monomers having a hydrocarbon substituent is 1 to 50 mol or 10 to 30 mol based on the entire monomer component. Molch and mole. If the amount used exceeds 50 mole, the non-cohesive property of the toner will be insufficient, and if the amount used is less than 1 mole, the low temperature fixing property of the toner will become insufficient.

The wax contained in the toner of the present invention contains an ester as one component, and the content ratio thereof is 20% by weight or more, and can be considered as another component. Specific examples of such wax include: Those listed in Table 1 can be mentioned.

The release agent such as an alkylene bis fatty acid amide compound represented by the above general formula contained in the toner of the present invention includes:
For example, those represented by the following structural formulas can be cited as representative examples.

1, CI l]H21co-NH-(CH2) 5-
NH-OCC10H212, C11H23CO-NH-
(CHz) 4-NH-OCC11H233, C13
H27CO-NH-(CH2) 2-NH-OCC13
H274-C1o H21Co NH-(CH2) 3
- NHQCC14H2g5, C□5H31CO-N
H-(CH2)2-NH-OCCl, H316, C17
H35CO-NH-CH2-NH-OCC15H3□7
, C17Hss C0-NH-(CH2) 2-NH
-OCC□5H3□8, CzaH47CONH-CH
2NH0CC15Hs□12, C2IH41C0-N
H-CHz -NH-OCC21H4114, C17H
35CONH-(CH2)2 NH0CC17H31 Examples of the commercially available mold release agent made of the alkylene bis fatty acid amide compound represented by the above general formula include the following.

"Bisamide" (manufactured by Nippon Hydrogen Industries Co., Ltd.) "Plastflow" (manufactured by Nitto Kagaku Co., Ltd.) "Diamid 200 Bis" (manufactured by Nippon Hydrogen Industries Co., Ltd.) "Lubloon EJ (manufactured by Nippon Hydrogen Industries Co., Ltd.) "Alflow V-60J" (manufactured by NOF Corporation) "Amide-6L" (manufactured by Youbin Fine Chemical Co., Ltd.) "Amide-78" (manufactured by Yobin Fine Chemical Co., Ltd.) "Amide-6H" (manufactured by Yobin Fine Chemical Co., Ltd.) [Armowax-EBSJ (manufactured by Lion Armor Co., Ltd.) "Hoechst Wax C" (manufactured by Hoechst Japan Co., Ltd.) "Nobukowax-22DSJ (manufactured by Nobuko Chemical Co., Ltd.) "Advawax-280J (manufactured by Advance Co., Ltd.) "Kaohwax-EB" (Kao (manufactured by Soap Co., Ltd.) "Varisin-28"
5J (Paker Castor Oil Co., Ltd.) Generally, the release agent such as the alkylene bis fatty acid amide compound represented by the above general formula becomes softer as the number of carbon atoms in the aliphatic hydrocarbon group and the length of the alkylene chain increase. However, from the viewpoint of reducing the heating temperature or fixing temperature during toner production, it is desirable to have a softening point of IOO to 180°C, preferably 130 to 160°C.

Therefore, the alkylene chain preferably has a length such that the number of carbon atoms is 5 or less.

The content of the release agent made of the above wax and alkylene bis fatty acid amide compound is in the range of 1 to 20% by weight, preferably in the range of 1 to 10% by weight, based on the binder resin. If this ratio is less than 1 weight, the effect as a release agent is not exhibited, so the non-offset property of the toner is not improved, and the effect of lowering the minimum fixing temperature cannot be obtained. On the other hand, if it exceeds 20% by weight,
The fluidity of the toner decreases, and as a result, the developability and transferability decrease, making it impossible to form a good visible image, and the release agent adheres to the developing sleeve or electrostatic image support, causing a film. , and its function becomes obstructed. Also, wax and alkylene bis fatty acid amide compounds are
The alkylene bis fatty acid amide compound is used in a proportion of 0.5 to 10 parts by weight, preferably 0.5 to 5 parts by weight, per 1 part by weight of wax.

The toner of the present invention contains the colorant and the release agent described above in the binder described above, and further contains a property improver added as necessary. At the same time, or in addition to the colorant, a magnetic substance may be contained.

As a coloring agent, carbon black, nigrosine dye (
C,1,m50415B), aniline flu (C,I,
Floor 50405), Calco Oil Blue (C, I.

N [Lazoec Blue 3), chrome yellow + (c, r, m14090), ultramarine blue (
c, r, floor 77103), DuPont Oil Red (C,
1, Sou 26105), quinoline yellow (C, I, N
l147005), methylene blue chloride (c, r
, Kan 52015), Phthalocyanine Blue (C, 1, N
[L74160), Magicite Green Oxalate (
C, 1, N142000), lamp black (C, Ll
@77266), Rose Bengal (C, 1, Nu454
35), mixtures thereof, and others. These colorants need to be contained in a sufficient proportion to form a visible image of sufficient density, and are usually added in an amount of 1 to 20 parts by weight per 100 parts by weight of the binder. Ru.

The magnetic material may be a ferromagnetic metal or alloy such as ferrite, magnetite, iron, cobalt, or nickel, or a compound containing these elements, or a material that does not contain a ferromagnetic element but is subjected to appropriate heat treatment. Alloys 1 that exhibit ferromagnetism by, for example, manganese-copper-
Aluminum, a type of alloy called Heusler alloy containing manganese and copper such as manganese-copper-tin, chromium dioxide, and others can be mentioned. These magnetic materials are uniformly dispersed in the binder in the form of fine powder with an average particle size of o, t-t microns. And its content is
The amount is 920 to 70 parts by weight, preferably 40 to 70 parts by weight, per 100 parts by weight of toner.

The property improver improves the toner's fluidity, non-filming property, that is, the property that filming does not occur when a part of the toner adheres to the surface of the carrier or electrostatic image, pulverizability, charging property, etc. It is included for the purpose of improvement, and this includes resin. Preferably used resins are, for example, uncrosslinked polymers that do not contain chloroform-insoluble matter, such as styrenes such as styrene and parachlorostyrene, vinylnaphthalene, vinyl chloride, vinyl bromide, and vinyl fluoride. , vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate, vinyl butyrate, such as methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, dodecyl acrylate, n-octyl acrylate,
2-chloroethyl acrylate, phenyl acrylate, α
- Methylene aliphatic carboxylic acid esters such as methyl chloroacrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, acrylonitrile, methacrylonitrile, acrylamide, such as vinyl methyl ether, vinyl isobutyl ether, vinyl ethyl ether, etc. vinyl ethers, particularly vinyl ketones such as vinyl methyl ketone and vinyl hexyl ketone, such as N-vinylvirol, N-vinylcarbasol, N-
Homopolymers obtained by polymerizing N-vinyl compounds such as vinyl indole and N-vinylpyrrolidone, and other monomers; copolymers obtained by copolymerizing two or more of these monomers; and or non-vinyl resins such as non-vinyl thermoplastic resins such as rosin-modified phenol-formalin resins, oil-modified epoxy resins, polyurethane resins, cellulose resins, polyether resins, or mixtures thereof with the above-mentioned vinyl resins. Mixtures may be mentioned.

These resins can be contained in a content ratio of 30% by weight or less of the binder, as long as the effects of the present invention are not impaired.

〔Effect of the invention〕

The toner for developing electrostatic images of the present invention uses a polyester resin having a specific structure as a binder, and further contains a release agent such as a wax having specific properties and an alkylene bis fatty acid amide compound having a specific structure. The synergistic effects of the two have the following effects.

(1) It has excellent low-temperature fixing properties, non-offset properties, and non-wrapping properties, and has a wide practical fixing temperature range.

Possible reasons for this are as follows.

(b) The binder resin is composed of a non-linear copolymer with an ester structure of etherified bisphenol and dicarboxylic acid as its backbone, and contains a specific aliphatic hydrocarbon group in the side chain and has a low softening point. have ) A polyester resin that itself has non-offset properties and can be fixed at low temperatures.

←) If the mold release agent is a specific wax or alkylene bis fatty acid amide compound, this will give the toner excellent mold release properties and provide sufficient non-offset and non-wrapping properties. In addition, the amide compound has a low softening point and greatly contributes to low-temperature fixing of the toner.

Excellent fluidity.

The reason for this is that the binder resin is a polar polyester resin with an etherified bisphenol skeleton, and the release agent is a wax containing an ester component and an alkylene bis fatty acid amide compound. Since the molding agent is a polar substance that has a high affinity for the binder resin, the dispersibility of the molding agent in the binder resin is good.As a result, the domain of the molding agent in the toner is small and the molding agent is in a state of phase separation. It is considered that the deterioration of the fluidity of the toner due to the release agent is suppressed compared to the case where only polyolefin wax is used as the release agent.

Since the toner of the present invention has excellent fluidity as described above, it is unnecessary or necessary to add a fluidity improver such as hydrophobic silica fine powder to obtain the necessary fluidity. Even in cases where the amount of hydrophobic silica fine powder added is small, it is sufficient to avoid the harmful effects of adding a large amount of hydrophobic silica fine powder, such as damage to the electrostatic image support due to the highly hard fine silica powder. Problems such as cleaning blade wear can be completely avoided.

Moreover, since the wax is hard with a penetration rate of 4 or less, it is highly durable and does not deteriorate in properties such as a decrease in fluidity even when used in a recycling system.

(3) Has high non-filming properties.

That is, in the toner of the present invention, the dispersibility of the release agent is higher than that described above, and the waxy component does not exist in a phase-separated state. It is prevented from adhering to a developing sleeve of a developing device, a carrier when used as a two-component developer, and the like.

As described above, since the toner of the present invention has high fluidity, it is possible to achieve good development, and
Because it has excellent low-temperature fixing properties, non-offset properties, and non-wrapping properties, it is possible to achieve good high-speed fixing by hot roller fixing, and as a result, it is possible to consistently produce excellent visible images with high single image density. Moreover, it can be formed at high speed.

In addition, since the toner of the present invention has a low minimum fixing temperature, it is possible to avoid exposing the paper serving as the toner image support to high temperatures during fixing, and as a result, the occurrence of wrinkles is suppressed. It becomes practically possible to form a visible image using toner.

〔Example〕

Examples of the present invention will be described below, but the present invention is not limited thereto. Note that "parts" represent parts by weight.

Production of binder resin■) Binder resin A Polyoxypropylene (2,2) -2,2-bis(4
-Hydroxyphenyl)furopane 700g Fluoric acid
150g n-dodecenylsuccinic anhydride 55.4g hydroquinone 0.1g The above substances were mixed with a thermometer, a stainless steel stirrer,
Capacity l with glass nitrogen gas inlet tube and flow-down condenser! Place the flask in a mantle heater, introduce nitrogen gas through the nitrogen gas inlet tube, and raise the temperature to 250°C while keeping the inside of the flask in an inert atmosphere. The reaction was carried out in When the water produced by the reaction stopped flowing out, the acid value was measured to be 1.5.

The polyester thus obtained Ring and ball method for resin (JISK25
31=1960 method. The same applies below. ) The softening point was 120°C.

This polyester resin will be referred to as "binder resin A."

2) Binder resin B Polyoxyethylene (21-2,2-bis(4-hydroxyphenyl)furopane 650 g fumaric acid 120 g isododecenyl succinic anhydride 55.4 g or more of the substance was added using the same equipment as in the case of resin A. The reaction was carried out at a temperature of 220° C. When the water produced by the reaction stopped flowing out, the acid value was measured and found to be 1.5.

Furthermore, 79 g't'' of l,2,4-benzenetricarboxylic acid anhydride was added and reacted at a temperature of 200°C.
The reaction was terminated when the softening point measured by the ring and ball method reached 120°C. The polyester resin thus obtained is referred to as "binder resin B."

3) Binder resin C (for comparison) Polyoxypropylene (2,2)-2,2-bis(4-
Hydroxyphenylfuronokun 211 g Terephthalic acid 299 g Pentaerythritol 82 g The above substances were heated using the same equipment as in the case of resin A, and further dibutyltin oxide 0.05 g K' was added and reacted at a temperature of 200 ° C. The reaction was terminated when the softening point determined by the ring and ball method reached t3i°C. The polyester resin obtained in this way is called "binder resin C".
shall be.

Mold release agent l) Wax al Fatty acid ester wax "Karnara/Gu Wax" (manufactured by Noda Wax Co., Ltd., ester content 80-85% by weight, penetration less than 1, melting point 83°C) 2) Wax a2 Fatty acid ester wax "Gan" Delilah Wax" (manufactured by Noda Wax Co., Ltd., ester content 24-30% by weight, penetration 2, melting point 64°C) 3) Amide compound bl Alkylene bis fatty acid amide "Hoechstwax CJ (
(Manufactured by Hoechst Japan) 4) Amide compound b2 Alkylene bis fatty acid amide “Armowax EBSJ
(Manufactured by Lion Armor Co., Ltd.) 5) Wax C (for comparison) Polypropylene wax "Viscol 660Pj (manufactured by Sanyo Chemical Co., Ltd., needle penetration [1,5, melting point 142°C)] In each example and comparative example, A toner powder consisting of 9 particles with an average particle size of 11 μm was obtained by mixing the materials in an extruder, cooling, pulverizing, and classifying the materials.
To this, 0.8% by weight of hydrophobic silica fine powder was added to produce a toner.

Example 1 Binder resin A 100 parts Wax al Z part Amide compound bl 2 parts Carbon black "Mogul LJ (manufactured by Cabot)
10 parts Example 2 Binder resin A Too part Wax al Z part Amide compound bl 6 parts Carbon black "Mogul LJ 10 parts Example 3 Binder resin A Too part Wax al Z part Amide compound b2 2 parts Carbon black [Mogul: [, 410 parts Example 4 Binder resin A Too part Wax a2 2 parts Amide compound b1 2 parts Carbon black "Mogul L" (manufactured by Cabot)
tcm Example 5 Binder resin A 100 parts Wax a2 2 parts Amide compound 1) 2 2 parts (33) Carbon black [Mogul LJ) 10! Example 6 Binder resin B 100 parts Wax al Z part Amide compound bl 2 parts Carbon black [Mogul LJ lo part Example 7 Binder resin A 48 parts Wax al Z part Amide compound b1 2 parts Magnetic fine powder 1'-BL- 100J (manufactured by Titan Kogyo Co., Ltd.)
52 parts Nigrosine dye "Nigrosine Paste EXj (manufactured by Orient Kogyo Co., Ltd.) 1 part Comparative Example 1 Binder resin A 100 parts Wax al 4 parts Carbon black "Mogal LJ To part Comparative Example 2 Binder resin A Too part Wax a2 4 parts Carbon black [ Mogul LJ 10 parts Comparative Example 3 Binder resin A too parts Amide compound bl 4 parts Carbon black [Mogul I, J 10 parts Comparative example 4 Binder resin A 100 parts Amide compound B 4 parts Carbon black [Mogul I, J 10 parts Comparative example 5 Binder resin A 100 parts Wax C 4 parts Carbon black [Mogul I, J 10 parts Comparative example 6 Binder resin 0 100 parts Wax al Z part Amide compound 1) 1 2 parts Carbon black "Mogul LJ 10 parts Comparative example 7 Binder resin A 100 parts Carbon black [Mogul LJ 10 parts or more of the toners obtained in Examples 1 to 7 were each referred to as "Toner L".
~ "Toner 7" and the toners obtained in Comparative Examples 1 to 7 were designated as "Comparative Toner I" to "Comparative Toner 7", respectively, and the fluidity of each of these toners was examined. That is, taking advantage of the fact that the highly fluid powder and granular material has a low degree of compression, it is poured from above into a container with a diameter of 28M and a volume of too much.

The sample was loosely packed through a mesh sieve, and the weight was measured to determine the static bulk density.

In addition, a developer having a toner concentration of 2% by weight was prepared by mixing each of the above toners other than Toner 7 with a carrier made of resin-coated iron powder, and each of the toners was used to create a toner recycling system. An electrophotographic copying machine [U-Bi
x 4500J (manufactured by Konishiroku Photo Industry Co., Ltd.), we conducted a live-photography test over 60,000 times using the steps of developing an electrostatic image, transferring the toner image to transfer paper, and fixing the toner image with a heat roller fixing device. The initial image density of the resulting copied image and the image density after 60,000 copies were measured. The static bulk density of each toner after 60,000 copies was also measured. After 60,000 copies, the degree of toner contamination (filming) on the surface of the carrier, the surface of the photosensitive drum, and the surface of the developing sleeve was examined.

Furthermore, the minimum fixing temperature, offset occurrence temperature, and curling occurrence temperature were determined for each of all toners.

Regarding the minimum fixing temperature, the surface layer is made of Teflon (polytetrafluoroethylene L/7 manufactured by DuPont) and the surface layer is made of silicone rubber rKE-1300RT.
The operation of fixing the toner image of the sample toner transferred onto a 64 g/d transfer paper at a linear speed of 200+ u/sec using a fixing device consisting of a pressure roller and Yoshi made of VJ (manufactured by Shin-Etsu Chemical Co., Ltd.) is performed using a heat roller. Set temperature to 100℃9
Kimwipe rubbing is applied to the formed fixed image repeatedly at each temperature raised stepwise by 5 degrees Celsius, and the lowest setting temperature for a fixed image that exhibits sufficient rubbing resistance is determined as the minimum fixing temperature. did. Note that the fixing device used here does not have a silicone oil supply mechanism.

In addition, to measure the offset occurrence temperature, the toner image is transferred and fixed by the above-mentioned fixing device, and then a blank transfer paper is sent to the fixing device under the same conditions. The operation of observing whether or not toner stains occur is repeated by successively increasing the set temperature of the heat roller of the fixing unit, and then the lowest set temperature at which toner stains occur. The offset generation temperature was taken as the offset occurrence temperature.

To measure the winding temperature, use a so-called flat black original and set the heat roller of the fixing device to fix the toner on almost the entire surface of the transfer paper, in accordance with the measurement of the offset temperature described above. The test was repeated while the temperature was gradually lowered, and the highest temperature at which the wrapping phenomenon occurred was defined as the wrapping occurrence temperature.

The above results are shown in Table 2.

As is clear from the results in Table 2, according to the toner of the present invention, good results were obtained in all evaluation items, but in the comparative examples, insufficient results were obtained in any of the evaluation items. Ta. That is, since Comparative Toner 1 and Comparative Toner 2 do not contain an alkylene bis fatty acid amide compound, they have a low bulk density and poor fluidity, and in particular, the image density after 60,000 copies is low. Comparative Toner 3 and Comparative Toner 4 do not contain wax, and thus have a high minimum fixing temperature and a high wrapping temperature. Comparative Toner 5 uses polypropylene wax as a release agent, so it is insufficient in all evaluation items, and particularly poor in fluidity and image density. In Comparative Toner 6, the minimum fixing temperature is high because the binder resin is a polyester resin that does not have a specific hydrocarbon group in the side chain. Since Comparative Toner 7 does not contain a release agent, it has a high minimum fixing temperature and a high curling temperature, a low offset occurrence temperature, and a narrow practical fixing temperature range. In addition, contamination with toner was observed on the lower fixing roller.

As described above, the toner according to the present invention has excellent non-offset and non-wrapping properties, and has a very low minimum fixing temperature, and has a practical fixing temperature range compared to toners containing conventional release agents. In addition, it has high fluidity, excellent developability and transferability, and can always form stable and good visible images, making it suitable for high-speed fixing using a heat roller.

Claims (1)

[Claims] 1) (a) Contains an etherified bisphenol monomer, a dicarphonic acid monomer, and a trivalent or higher polyhydric alcohol monomer and/or a trivalent or higher polyvalent carboxylic acid monomer A non-linear copolymer obtained from a monomer component, comprising a polyester resin having an aliphatic hydrocarbon group having 3 to 22 carbon atoms in its side chain; and (b) containing 20% by weight or more of an ester component. 1. A toner for developing an electrostatic image, comprising a wax having a penetration degree of 4 or less and a release agent such as an alkylene bis fatty acid amide compound represented by the following general formula. General formula [wherein and 8 are the same or different from each other, each represents a saturated or unsaturated aliphatic hydrocarbon group having 10 or more carbon atoms, and R3 and R4 are each the same or different hydrogen atoms or 10CR, 5 groups (wherein R5 represents a saturated or unsaturated aliphatic hydrocarbon group), and n represents a positive integer. ]