JPS60254149A - Toner for developing electrostatic charge image - Google Patents

Abstract

PURPOSE:To form a good visible image by incorporating a specific polyester resin having an aliphat. hydrocarbon group of 3-22C at the side chain, polyolefin wax and specific copolymerized polyolefin wax into a toner. CONSTITUTION:The 1st wax consisting of polyolefin and the 2nd wax composed of the polyolefin block-copolymerized or graft-copolymerized with alpha-methylene aliphat. monocarboxylate monomer are incorporated into the polyester resin which is the non-linear copolymer obtainable from monomer components contg. an etherified bisphenol monomer, dicarboxylic acid monomer, tri- or higher hydric alcohol monomer and tri- or higher hydric carboxylic acid monomer and has the aliphat. hydrocarbon group of 3-22C at the side chain. The toner for developing 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 made of 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.

Formation of a visible image via such an electrostatic charge image is of course preferably achieved at high speed, and from this point of view conventionally, in the fixing process, thermal roller fixing, which has high thermal efficiency and is advantageous compared to other methods, has been used. 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 hot roller fixing method, the toner used for development is required to have good low-temperature fixability, and for this purpose, the binder resin that makes up the toner needs to be softened. 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 transfer paper etc. that is sent next, forming the image. There is a tendency for the so-called offset phenomenon to occur easily.

In order to prevent the occurrence of the above offset phenomenon, various proposals have been made in the past, and some of them have been put into practical use.

One is to apply release oil such as silicone oil to the surface of a heated roller while fixing, while the other is to impart release properties to the toner itself to provide anti-offset performance. be. The latter method requires no silicone oil application mechanism, so the structure of the fixing device is simple;
It is superior in that it does not require maintenance such as replenishing silicone oil. As a means for imparting anti-offset properties to the toner itself, there are (a) a method of using a high molecular weight polymer as a binder resin of the toner;
←) A method is known in which a wax having releasability is contained in the toner.

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

By the way, polyester resin is attracting attention as a binder resin with a low softening point. 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 for the method of incorporating the wax in toner as described in ←), Japanese Patent Publication No. 52-3304 and Japanese Patent Publication No. 5
As disclosed in Japanese Patent No. 2-3305, a method has been proposed in which a polyolefin wax such as polypropylene wax or polyethylene wax is used as the wax. Using such wax is effective and F
However, in order to obtain a toner with high non-offset properties and a sufficiently wide practical fixing temperature range, the content ratio of the wax in the toner must be considerably increased.

However, as the content of wax 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 Toku containing polyolefin wax is used, it can be used as an electrostatic image support such as a photoconductive photoreceptor that supports an electrostatic image to be developed, a developing sleeve of a developing device, and a two-component developer. The disadvantage is that the properties of the carrier etc. deteriorate relatively quickly when used, making it impossible to obtain a long useful life. This is because the wax component in the toner adheres to the so-called filming 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 ratio of the wax. This is considered to be because the wax has a low dispersibility in the binder resin of the toner and the wax domain in the toner is large, so that the wax exists in a so-called phase-separated state in the toner particles.

[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 long-term durability. It is an object of the present invention to provide an electrostatic image support toner which can consistently form good visible images over a period of time and is suitable for high-speed fixing.

[Structure of the invention]

The above purpose is to obtain monomers containing (,) etherified bisphenol monomers, dicarboxylic acid monomers, and trihydric or higher polyhydric alcohol monomers and/or trivalent or higher polyhydric carboxylic acid monomers. a nonlinear copolymer obtained from the components, a polyester resin having an aliphatic hydrocarbon group having 3 to 22 carbon atoms in its side chain, (b) a first wax composed of a polyolefin, and α- a second wax composed of a polyolefin diblock copolymerized or graft copolymerized with a methylene aliphatic monocarboxylic acid ester monomer and/or a polyolefin diblock copolymerized or graft copolymerized with an aromatic vinyl monomer; This is achieved by an electrostatic image developing toner characterized by containing:

The present invention will be explained in detail below.

The toner for developing electrostatic images of the present invention is a non-linear copolymer having an ester structure of etherified bisphenol and dicarboxylic acid as a basic skeleton, and has a saturated or unsaturated side chain having 3 to 22 carbon atoms. A polyester resin having an aliphatic hydrocarbon group is used as a binder resin, and a coloring agent and others are added to the particles as necessary. It contains the following wax (1) and wax (2) together with the toner components.

Wax (1) The first wax composed of polyolefin (hereinafter referred to as "unmodified wax") Wax (No α-
A polymer obtained by block copolymerizing a methylene aliphatic monocarboxylic acid ester monomer (hereinafter referred to as "acrylate monomer") or an aromatic vinyl monomer and a polyolefin, or a polymer obtained by block copolymerizing a polyolefin with a methylene aliphatic monocarboxylic acid ester monomer (hereinafter referred to as "acrylate monomer"), or a polymer obtained by block copolymerizing a polyolefin with a polyolefin as a chain backbone and an acrylate monomer or aromatic A second wax composed of a polyolefin modified with a vinyl monomer (hereinafter referred to as "modified polyolefin") or a mixture thereof (hereinafter referred to as "modified wax") In the above, the amounts of unmodified wax and modified wax used are as follows: , the total content of both is within the range of 1 to 20% by weight based on the pinter resin, preferably 1. to 10% by weight.
The weight is within the range of -. If this proportion is less than 1% by weight,
The effect of the wax as a release agent is not exhibited, and therefore the non-offset property of the toner is not improved;
If it exceeds this, the fluidity of the toner will decrease.
As a result, developability and transferability deteriorate, making it impossible to form a good visible image, and the wax adheres to the developing sleeve or electrostatic image support to form a film, impeding its performance. .

The ratio of the unmodified wax to the modified wax is 1 part by weight of the former and 0.5 to 10 parts by weight, preferably 0.5 to 5 parts by weight. When the latter ratio is too small, the fluidity of the toner becomes insufficient, and on the other hand, when the former ratio is too small, the offset generation temperature becomes low.

The monomer components used in the synthesis of the polyester resin (non-linear copolymer) constituting the binder in the present invention are: (a) as the component constituting the basic skeleton of the copolymer;
Divalent alcohol molecules and divalent carboxylic acid monomers mainly composed of etherified bisphenols, ←) Trivalent or higher polyvalents that participate in nonlinearization of the copolymer, that is, branching or network formation. an alkyl monomer and/or a polycarboxylic acid monomer having a valence of 3 or more; It is composed of up to 22 saturated or unsaturated aliphatic hydrocarbons, and can contain other monomers if necessary.

The above etherified bisphenols include 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-hydro-1i-diphenyl)propane, and the like. Other divalent alcohol monomers include ethylene glycol, diethylene glycol, triethylene glycol, 1.2
- Diols such as propylene glycol, 1,3-propylene glycol, 1.47" tanediol, neointyl glycol, 1,4-butynediol, 1,4-bis(hydroxymethyl)cyclohexane, and bisphenol A, Examples include hydrogenated bisphenol A and the like.

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

The trivalent or higher polyhydric alcohol monomers mentioned above are as follows:
For example, nlubitol, 1,2,3.6-hexanetetrol, 1,4-sorbitan, pentaerythritol, digentaerythritol, triintererythritol, sucrose, 'l, 2.4-butanetriol, 1,2.5 −
Mention may be made of hentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3.5-trihydroxymethylbenzene, and others. . The amount of these polyhydric alcohols to be used is 5 to 50 moles, preferably 10 to 40 moles, based on the entire alcohol component. Usage amount is 5
If it exceeds 0 molt, the toner fixing performance 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.

Examples of trivalent or higher polyvalent carboxylic acid monomers include 1.2.4-benzenetricarboxylic acid, 1°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, detra(methylenecarboxyl)methane, 1,2,7°8-octanetetracarboxylic acid, engine trimer acid, acid anhydrides thereof, and others. The amount of these polycarboxylic acid monomers used is 5 to 50 mol, preferably 10 to 40 mol, based on the entire acid component. Usage amount is 50
If the amount exceeds 5 molt, the fixing properties of the toner will be insufficient, and if the amount used is less than 5 molt, the non-linearity of the copolymer will be insufficient, resulting in insufficient non-offset properties of the toner.

The divalent or higher alcohol monomers and the divalent or higher carboxylic acid monomers having the above e number of saturated or unsaturated hydrocarbon substituents having 3 to 22 carbon atoms include the above-mentioned (a) and (cut). can be used, especially n
-dodecenylsuccinic acid, iso-dodecenylsuccinic 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 mole, preferably 10 to 30 mole, based on the entire monomer component. It is a mole article. If the amount used exceeds 50 molty, the non-cohesive property of the toner will be insufficient, and if the amount used is less than 1 molty, the low temperature fixing property of the toner will be insufficient.

The polyolefin constituting the unmodified wax contained in the toner of the present invention is a homopolymer type obtained from a single olefin monomer, or a copolymer type obtained by copolymerizing the olefin monomer with another monomer copolymerizable with it. It may be of any type.

The olefin monomers include, for example, ethylene propylene/, butene-1, pentene-1, hexene-11, butene-1, octene-1, nonene-dodecene-1, and isomers thereof having different positions of unsaturated bonds. , and those having a branched chain consisting of 9 alkyl groups, such as 3-methyl-1-butene, 3-methyl-2-pentene, 3-propyl-5-methyl-2-hexene, and other vectors. Contains olefin monomers.

Other monomers copolymerizable with the olefin monomer include other olefin monomers, such as vinyl methyl ether, vinyl-n-phthyl ether, vinyl phenyl ether, etc., such as vinyl acetate, vinyl butyrate, etc. vinyl esters such as vinyl fluoride, vinylidene fluoride, tetrafluoroethylene, vinyl chloride, vinylidene chloride, haloolefins such as tetrachloroethylene, such as methyl acrylate, ethyl acrylate, n-butyl acrylate,
Methyl methacrylate, ethyl methacrylate, n
-butyl methacrylate, sugearyl methacrylate, N,N-dimethylaminoethyl methacrylate,
Acrylic acid esters or methacrylic acid esters such as t-butylaminoethyl methacrylate, such as acrylonitrile, acrylic acid derivatives such as N,N-dimethylacrylamide, such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, itacon Various organic acids such as acids, diethyl fumarate, β-binene, etc. can be mentioned. Therefore, when the polyolefin component is made into a copolymer type, at least two or more of the above olefin monomers are used. Olefin copolymer types obtained by copolymerization, e.g.

For example, ethylene-propylene copolymers, ethylene-butene copolymers, ethylene-pentene copolymers, propylene-butene copolymers, propylene-pentene copolymers, ethylene-3-methyl-1-butene copolymers, A copolymer type such as an ethylene-propylene-butene copolymer, or an olefin copolymer obtained by copolymerizing at least one of the above-mentioned olefin monomers and at least one monomer other than the above-mentioned olefin monomers. type, such as ethylene-vinyl acetate copolymer, ethylene-vinyl methyl ether copolymer,
Ethylene-vinyl chloride copolymer, ethylene-methyl acrylate copolymer, ethylene-methyl methacrylate copolymer, ethylene-acrylic JLa copolymer, globylene-vinyl acetate copolymer, glopyrene-vinylethyl ether copolymer Polymer, propylene-ethyl acrylate copolymer, propylene-methacrylic acid copolymer, butene-vinyl methyl ether copolymer, butene-methyl methacrylate copolymer, pentene-vinyl acetate copolymer, hexene-vinyl ether copolymer It can be of the copolymer type, such as a rate copolymer, an ethylene-propylene-vinyl acetate copolymer, and an ethylene-vinyl acetate-hinyl methyl ether copolymer.

When a copolymer type is used using a monomer other than an olefin monomer, it is preferable to use a copolymer type in which the ratio of the olefin moiety to the olefin monomer in the polyolefin component is, for example, 50 mole or more.

This is because if the proportion of the olefin portion is too small, the effect of improving the fixing properties of the toner will not be sufficiently exhibited.

The modified polyolefin constituting the modified wax is one obtained by blocking or grafting a polyolefin component with a modifying component, and the above-mentioned polyolefins are used as the polyolefin component.

Furthermore, acrylate monomers and aromatic vinyl monomers are used as modifying components.

Specific examples of acrylate monomers include methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, and n-acrylate.
-Octyl, dodecyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, methyl α-chloroacrylate, methyl methacrylate, ethyl methacrylate, methacrylate propyl acid, n-butyl methacrylate, isobutyl methacrylate,
n-octyl methacrylate, dodecyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylamine ethyl methacrylate, diethylamino 1,000 methacrylate, and others. can be mentioned.

Specific examples of aromatic vinyl monomers include 1-phenylpropene, styrene, 0-methylstyrene, m-
Methylstyrene, p-methylstyrene, α-methylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, p-n-butylstyrene, p-tert-butylstyrene, p-n-hexylstyrene, p-n- Octylstyrene, p-n-nonylstyrene J p'-11
'-7 silstyrene, p-n-1'' decylstyrene, p
-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene, and the like.

By using the above-mentioned acrylate monomer or aromatic vinyl monomer and the polyolefin described above, Zoroku copolymerization or graft copolymerization is carried out according to conventional methods and conditions.

A modified wax made of modified polyolefin can be obtained. For example, for block copolymerization, a method using a living polymer or a method in which a block copolymer is obtained by reacting radicals generated by mechanochemically splitting a wax with a hexamer, etc. can be used. For graft copolymerization, a method of reacting a monomer with an ozonated polyolefin (polymer initiator method), a method of grafting using radiation, etc. can be used.

Here, the proportion of the modified component in the modified polyolefin is 0.
．． It is preferably within the range of 1 to 50 tonne weight and 1 to 40 weight. If this ratio is too small, the fluidity of the toner will be significantly reduced, and if it is too large, the minimum fixing temperature of the toner will become high.

Further, it is desirable that such modified polyolefin itself has a low softening point, for example, JIS K2
531-1960, the softening point is 80 to 180°C, preferably 90 to 16°C.
The temperature is preferably 0°C.

The toner of the present invention is a granular material comprising the above-mentioned unmodified wax and modified wax dispersed in the above-mentioned binder resin together with a colorant, a magnetic substance, a property improver, and other necessary additives. Yes, the average particle size is usually 5~
In the range of 30 microns.

As a coloring agent, carbon black, nigrosine dye (
C, 1, Na50415B), Anilimple Moan (C, I
, Zui 50405), Calco Oil Blue (C, I, Zui aZOee Blue 3), Chrome Yeo- (C
, 1, N114090), ultramarine blue (C,
1, 77103), DuPont Oil Red (C, 1,
Sui 26105), Quinoline Yellow (C, 1, Magic 47)
005), methylene blue chloride (C, 1, Sou 52
015), lid (C0I, N174160), malachite green off-salate (C, 1, 42000), lamp black (C.

1, m77266), Rose Bengal (C, 1, N11
45435).

Mixtures of these and others can be mentioned.

These colorants need to be contained in a sufficient proportion to form a visible image with sufficient concentration, and are usually 1 to 20 parts by weight per 100 parts by weight of the binder. .

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 can be made by subjecting it to appropriate heat treatment. Alloys that become ferromagnetic, such as 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 substances are uniformly dispersed in the binder in the form of fine powder with an average particle size of 0.1 to 1 micron. 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 components, such as styrene, styrenes such as norachlorostyrene, vinylnaphthalene, vinyl chloride, vinyl bromide, fluorocarbons, etc. Vinyl chloride, Hinyl acetate,
Vinyl esters such as vinyl propionate, vinyl benzoate, vinyl butyrate, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, dodecyl acrylate, n-octyl acrylate, 2-acrylate Chlorethyl, acrylic acid 7 =
methylene aliphatic carboxylic acid esters such as methyl α-chloroacrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, acrylonitrile,
Methacrylonitrile, acrylamide, vinyl ethers such as vinyl methyl ether, vinyl isobutyl ether, vinyl ethyl ether, vinyl ketones such as vinyl methyl ketone and vinyl hexyl ketone, such as N-vinylpyrrole, N-vinylcarbazole, Homopolymers obtained by polymerizing N-vinylindole, N-vinyl compounds such as N-vinylpyrrolidone, and other monomers, or copolymers obtained by copolymerizing a combination of two or more of these monomers. or mixtures thereof, products, 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, and polyether resins, or their combinations with the above-mentioned vinyls. Examples include mixtures with other resins.

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 electrostatic image developing toner of the present invention uses a polyester resin having a specific structure as a binder, and does not contain specific unmodified wax or modified wax.
Due to the synergistic effect of the two, the minimum fixing temperature is low, sufficient mold release properties are obtained, and excellent non-offset properties are obtained, as well as good fluidity and high durability. It is possible to stably form a high-density and excellent visible image at a low fixing temperature without causing an offset phenomenon, and at high speed and over a large number of times. Even when subjected to a development process using a recycling system, it has excellent durability and can stably obtain the above characteristics, and contamination of the carrier, electrostatic image support, and developer sleeve by toner is greatly reduced. .

Although the reason why the toner of the present invention has such excellent properties as described above has not been strictly elucidated, it is believed that the following is a part of the reason.

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

(b) Since the wax component consists of both unmodified wax and modified wax, which have different properties, there are disadvantages when using each of these substances alone, i.e., the unmodified wax alone is required for the toner. The decrease in fluidity that occurs when releasability is obtained and the decrease in releasability that occurs when the low-temperature fixability required for the toner 5 is obtained only with modified wax are alleviated, and each of unmodified wax and modified wax is The advantages of this method are fully exhibited, and excellent low-temperature fixing properties, non-offset properties, and fluidity can be obtained.

Furthermore, the binder resin is a polar polyester resin with an ether bisphenol skeleton.
The modified wax that makes up the wax component has a high affinity for this resin and has excellent dispersibility, so the fluidity that appears when a large amount of unmodified wax that has a low affinity for the binder resin is used. It is possible to effectively suppress a decrease in properties and non-aggregation properties.

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 is added is very small, it is sufficient to prevent 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 silica fine powder. There is no invitation.

〔Example〕

Examples of the present invention will be described below, but the present invention is not limited thereto. In addition, "c" represents parts by weight.

Production of binder resin 1) Binder resin A Polyoxypropylene (2,2)-2,2-bis(4-
Hydroxyphenyl)propane 700g fumaric acid 15
0 g n-dodecenylsuccinic anhydride 55.4 g Hydroquinone 0.1 g The above substances were mixed with a thermometer, a stainless steel stirrer,
Place it in a round bottom flask with a capacity of 1mm equipped with a glass nitrogen gas inlet tube and a flow-down condenser, set this flask on a mantle heater, and introduce nitrogen gas through the nitrogen gas inlet tube to inert the inside of the flask. The temperature was raised to 250° C. while maintaining the atmosphere, and the reaction was carried out under stirring. When the water produced by the reaction stopped flowing out, the acid value was measured and was 1.5, indicating β.

Furthermore, 65.4 g of 1,2,4-benzenetricarboxylic acid anhydride was added and reacted for about 8 hours, and the reaction was terminated when the acid value reached 20. The polyester resin thus obtained was The ring and ball method (JISI (253
1-1960 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 (2) = 2.2-bis(4-hydroxyphenyl)furopane 650g fumaric acid 120g indodecenyl anhydride <acid 5s, 4g or more of the substance,
The reaction was carried out at a temperature of 220° C. using the same equipment as in the case of Resin A. When the water produced by the reaction stopped flowing out, the acid value was measured and found to be 1.5.

Further, 79 g of 1,2,4-benzenetricarboxylic acid anhydride was added, and the mixture was allowed to react 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 was used as the binder tree IJ'r1. I'll call it BJ.

3) Binder resin C (for comparison) Polyoxypropylene (2,2) -2,2-bis(4
-Hydroxyphenyl)propane 211 g Terephthalic acid 299 g Pentaerythritol 82 g The above substances were heated using the same apparatus as in the case of Tree@A, and digyl oxides o and ost were added to react at a temperature of 200°C, The reaction was terminated when the softening point measured by the ring and ball method reached 131°C. The polyester resin barreled in this way is
It is assumed to be 1cJ.

Wax 1) Modified wax a Polyethylene wax obtained by Zigzift copolymerization with 1-phenylpropene (1-phenylpropene content 2)
0% by weight, softening point 115°C) 2) Modified wax b Polyethylene wax diblock copolymerized and shrunken with 1-phenylpropene (1-phenylpropene content 2)
0% by weight, softening point 118°C) 3) Modified wax C Polyethylene wax digraft copolymerized with methyl methacrylate (methyl methacrylate content: 2)
0% by weight, softening point 120°C) 4) Unmodified wax d Poly-O propylene wax [Viscol 660 pJ (manufactured by Sanyo Chemical Co., Ltd.) In each example and comparative example, materials of the indicated formulation were melted, kneaded, and cooled. A toner consisting of 9 particles having an average particle size of 10 .mu.m was prepared in a conventional manner by steps of grinding, grinding and classification.

Example 1 Binder resin A 100 parts Modified wax, Tux a 3 parts Unmodified wax d 1 part Carbon black "Mogul L" (manufactured by Cabot) 10 parts Example 2 Binder resin N 100 parts Modified wax B 3 parts Unmodified wax d 1 Part carbon black "Mogul L" 10 parts Example 3 Binder resin A 100 parts Modified wax C 3 parts Unmodified wax d 1 part Carbon black [Mogul LJ iog Example 4 Binder resin B 100 parts Modified straw 2 F 83 parts Unmodified 722,761 parts Carbon Black [Mogul LJ io part Example 5 Binder resin B 100 parts Modified wax b 3 parts Unmodified wax d 1 part Carbon black "Mogul L4 10 parts Example 6 Binder resin B 100 parts Modified wax C 3 parts Unmodified wax d 1 part carbon Black "Mogull LJ io part Example 7 Binder resin A 48 parts Modified wax a 3 parts Unmodified wax d 1 Magnetic fine powder 1'-BL-100J (manufactured by Titan Kogyo Co., Ltd.) 52 parts Nigrosine dye [Nigrosine paste EXJ ( Orient Chemical Co., Ltd.) 1 part Comparative Example 1 Binder resin A 100 parts Modified wax a 3 parts Carbon black [Mogul LJ 10 parts Comparative example 2 Binder resin A 100 parts Unmodified wax d 3 parts Carbon black "Mogul L" 10 parts Comparison Example 3 Binder resin CI 00 parts Modified wax a 3 parts Unmodified wax Hi 1 part Carbon black "Mogul L4" 10 parts Comparative example 4 Binder resin A 100 parts Carbon black "Mogul L" 10 parts or more obtained in Examples 1 to 7 Each of the toners that were
~ "Toner 7" and the toners obtained in Comparative Examples 1 to 4 were designated as "Comparative Toner 1" to "Comparative Toner 4", respectively, and the fluidity of each of these toners was examined. That is, the degree of compaction was measured using a powder compaction tester "Tapdenser" (manufactured by Seishin Enterprise Co., Ltd.), taking advantage of the fact that the degree of compaction of a powder with high fluidity is small. Specifically, the diameter is 28
First, the sample was loosely packed into a container with a volume of 100rnt from above through a 100 mesh sieve, the weight was measured to determine the static bulk density A, and then the container was covered with a lid of the same diameter and an upper tapping device was used to reduce the drop height to 5. The volume of the sample when tapped 600 times under my conditions was determined, and the previously determined weight was divided by this volume value to determine the bulk density P, and the degree of compression C was calculated using the following formula.

In addition, by mixing each of the 10 types of toners other than Toner 7 with a carrier made of resin-coated iron powder, the toner concentration is 2% by weight and the toner charge amount is 20 ± 1 microton/g. Develop the electrostatic charge image, transfer the toner image onto transfer paper, and transfer the toner image using an electrophotographic copying machine rU-Bix4500 (manufactured by Konishiroku Photo Industries Co., Ltd.). Fixing was carried out using a heated roller fixing device, and the amount of toner primarily adhered to the light surface of the photosensitive drum, the transfer rate to transfer paper, and the image density of the resulting copied image were measured.

Here, the primary adhesion amount of toner is the so-called solid black potential of 8.
This is the toner adhesion amount per unit area at the location 00■.

Furthermore, all toners were evaluated for their minimum fixing temperature, offset generation temperature, and storage stability.

Regarding the minimum fixing temperature, a fixing roller consisting of a heat roller whose surface layer is made of Teflon (polytetrafluoroethylene manufactured by DuPont) and a pressure roller whose surface layer is formed of silicone rubber rKE-j300RTVJ (manufactured by Shin-Etsu Chemical Co., Ltd.) is used. The toner image of the sample toner was transferred onto a transfer paper of 64 g/- in a device and fixed at a linear speed of 200 m/s by increasing the set temperature of the heat roller in steps of 5°C from 100°C. Kimwipe rubbing was repeatedly applied to the formed fixed image at each temperature, and the lowest set temperature for a fixed image that showed sufficient rubbing resistance was defined as the lowest fixing temperature. 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 to the above-mentioned fixing device, and then a blank transfer sheet is sent to the fixing device under the same conditions. The operation of observing whether or not toner stains occur is repeated while the set temperature of the heat roller of the fixing unit is successively increased, and the lowest set temperature at which toner stains occur is determined. The offset generation temperature was defined as the offset occurrence temperature.As for storage stability, each sample was left for 48 hours at a temperature of 55° C. and a relative humidity of 40%, and the presence or absence of aggregation and its degree were evaluated.

The above results are shown in Table 1.

As is clear from the results in Table 1, with 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 does not contain unmodified wax, the offset generation temperature is low. Since Comparative Toner 2 does not contain modified wax, it is insufficient in all evaluation items, has low reediness, particularly low fluidity, and is inferior in primary toner adhesion amount, transfer rate, and image density. In Comparative Toner 3, the binder resin is a polyester resin that does not have a specific hydrocarbon group in the side chain, and the minimum fixing temperature is high.

Since Comparative Toner 4 does not contain a wax component, the minimum fixing temperature is high and the offset generation temperature is low, so that the practical fixing temperature range is extremely narrow.

In addition, each of Toner 1 to Toner 6 of Nyo Shimiko photocopying machine [
When we conducted a continuous copying test 600 times using "U-Bi: Ta.

As is clear from the above results, the toner according to the present invention has
It has excellent non-offset properties, has a very low minimum fixing temperature, has a wider practical fixing temperature range than toners containing only conventional polyolefin wax, and has high fluidity and contains a fluidity improver. Even if it is not used, it can be put to practical use, and has excellent developability and transferability.
It can always form stable and good visible images, and is suitable for high-speed fixing using a heat roller.

Claims (1)

[Scope of Claims] 1) ip) Monomers containing etherified bisphenol monomers, dicarboxylic acid monomers, and trivalent or higher polyhydric alcohol monomers and/or trivalent or higher polyhydric carboxylic acid monomers. A first resin comprising a polyester resin having a nonlinear coaliphatic hydrocarbon group obtained from a polymer component, and Φ) a polyolefin.
and a polyolefin obtained by diblock copolymerization or graft copolymerization with an α-methylene aliphatic monocarboxylic acid ester monomer and/or a polyolefin obtained by diblock copolymerization or kraft copolymerization with an aromatic vinyl monomer. A toner for developing an electrostatic image, comprising a second wax. 2) Toner-8 for developing electrostatic images according to claim 1, wherein the total content of the first wax and the second wax is 1 to 20% by weight.