JPS60456A - Toner for developing electrostatic charge image - Google Patents

Abstract

PURPOSE:To obtain a toner having excellent offsetting property by incorporating a binder resin contg. a polymer polymerized with a polymerizable monomer in the presence of a reactive prepolymer and polyolefin wax which is block- or graft-coplymerized with an arom. vinyl monomer into the toner. CONSTITUTION:A binder resin contg. a polymer (an unreacted prepolymer may remain) obtd. by bringing a polymerizable monomer having a functional group that can react with functional groups in the presence of a prepolymer having the reactive groups such as -COOH, ethylene oxide, etc. at the main chain and 1 or side chain is manufactured. On the other hand, the modified wax formed by graft- or block-polymerizing a styrene monomer with polyolefin wax is manufactured. A toner in which the wax is incorporated at 10-20wt% in the mixture composed of the above-described resin and the wax is manufactured. The toner having a low fixing temp., a high offset generating temp., good fluidity and is hardly flocculate is thus obtd.

Description

Detailed Description of the Invention The present invention is applicable to electrophotography, electrostatic printing, electrostatic recording, etc.
This relates to a toner for developing an electrostatic image formed in step 2. ◎ The developing process for an electrostatic image consists of toner that is attracted to charged fine particles by electrostatic attraction to the surface of the electrostatic image support. This is the step of making the electrostatic charge image visible.

The specific method for carrying out such a developing process is as follows:
A wet development method using a liquid developer in which pigments or dyes are finely dispersed in an insulating organic liquid, and a powder consisting of a toner in which a coloring agent such as carbon black is dispersed in a binder made of a natural or synthetic resin. using a developer,
There are dry developing methods such as the cascade method, bristle brush method, magnetic brush method, impression method, and powder cloud method.

The l1iII image visualized in the developing process is sometimes fixed on the support as it is, but usually it is transferred to another support such as transfer paper and then served. In addition to the subsequent steps, that is, the transfer step and the fixing step, the toner has not only good aggressiveness, but also good transferability and fixing. Among these conditions, the conditions related to fixing properties are the most unfavorable, and a large number of papers have been published regarding the improvement of the fixed properties of this toner and the results thereof11. ◇The toner image formed in the developing process or the transferred image! ! It is generally advantageous to use a heating fixing method for fixing the L image, and this heating fixing method includes a non-contact heating fixing method such as oven fixing, and a contact heating fixing method such as a heated roller fixing method. The contact heating fixing method has high thermal efficiency, etc., and is capable of high-speed fixing, making it the standard for high-speed copying machines (Niyoshi Tsuji).Also, it is possible to use a relatively low-temperature Tsubame source. , This method ■ 2 requires less power consumption, making it possible to downsize the copying machine and reduce the energy consumption by M1 The contact heating fixed stone method is preferable from various points of view, such as there is no danger of the toner forming the second image (part of the toner constituting the second image is heated). This is a phenomenon in which the image is transferred to the surface of the roller and transferred again to the next transferred transfer paper, staining the image.To prevent this offset phenomenon, C.
Although there have been no various proposals in the past, some have been put into practical use◎
One method is to perform fixing while applying release oil such as silicone oil to the surface of a heated roller, and the other method is to make the toner itself have the same anti-offset performance. The structure of the fixing device is simplified because there is no need for a V9 oil application mechanism, etc.

It is superior in that it does not require maintenance such as replenishing silicone oil.The offset phenomenon occurs when the temperature of the heat roller reaches a certain level, so the minimum temperature at which the offset phenomenon occurs (below) The higher the offset generation temperature (referred to as "offset generation temperature"), the better the non-offset properties of the toner.However, in order for the toner to become stable, it is necessary to directly heat the toner to a temperature above its softening point. Therefore, in the actual heat roller setting tool C2, the temperature of the heat roller is set to a specific temperature within the setting temperature range, which is above the softening point of the toner and lower than the offset generation temperature.

However, in reality, it is not possible to maintain the temperature of the heat roller perfectly (=uniformly) at the set temperature, and since there is an intermediate dip that must be taken into account in terms of temperature, the temperature range that can be set is wide. However, it is preferable to use a toner that does not overcome the advantages of the contact heat fixing method.

In order to reduce the temperature at which the offset occurs in the toner, it is effective to make the toner binder resin (containing a dipolymer ambiguous component), , since the resin has a high softening point, the minimum temperature [I (lower than 12, referred to as the "minimum joseki temperature") required for ≦ Jutner's joseki becomes high, and the advantage of the contact heating joseki method is lost. Naturally, it is desirable that this minimum standard temperature be low, and in order to achieve the formation of visible images on both sides of a sheet of transfer paper, which has recently become a high demand. (Secondly, the toner used for development must be able to be fixed at a low temperature.

From the above background, by incorporating a low softening point wax consisting of a release agent such as polypropylene wax or polyethylene wax into the toner particles,
A means of lowering the minimum joseki temperature has been developed. However, in this method C2, since the fluidity of the powdered toner is reduced, the developability and transferability are reduced, a good visible image cannot be formed, and there is a tendency for the toner to become cohesive. Moreover, in order to obtain the effect of adding wax (2), the content ratio (2) of the wax must be increased, and as a result, the wax component may not adhere to the developing sleeve or electrostatic image support 62. It has the disadvantage of forming a film and inhibiting its function.

In order to improve the fluidity of the toner, it is effective to add C2 to a toner powder, which is a fluidity improver made of fine hydrophobic silica powder. In order to obtain sufficient fluidity, it is necessary to add a large amount of hydrophobic liquid imitation powder.
As a result, the surface of the electrostatic image support is likely to be damaged by the highly hard hydrophobic silica fine powder, and when the support is a photoconductive photoreceptor, C2 becomes a major problem. , surface cleaning of the electrostatic image support is performed using a rubber blade (
(2) Image formation with a recycling system in which toner that has been subjected to development but has not participated in the formation of a toner image is returned to the developing device for reuse. In the apparatus, the surface part C of the toner particles is embedded with fine particles of two-line aqueous silica, and the fluidity of the toner is reduced, resulting in a visible image formed of low image quality.

The present invention has been developed to overcome the above-mentioned circumstances (2), and its objectives are to have sufficient non-offset properties, a low minimum fixing temperature, high fluidity and non-cohesiveness, and a constant carbon
The purpose of C2 and above is to provide a toner for developing an electrostatic image that can form a clearly visible image. A toner for developing an electrostatic image, characterized in that it contains a binder resin made of a polymer obtained by polymerizing the above, and a wax made of a polyolefin obtained by block copolymerization or graft copolymerization with an aromatic vinyl heptamine. achieved by.

Hereinafter, the present invention will be specifically explained in terms of two conditions: In the present invention, in the presence of a reactive pre-polymer (in the presence of a polymerizable monomer M is combined in the second step, the resulting polymer is used as a binder resin, In the particles, together with C1 colorant, charge control agent and other necessary toner components, a polymer or polyolefin obtained by block copolymerizing an aromatic monomer and a polyolefin is used as a chain trunk, and an aromatic vinyl A polymer obtained by monomer graft copolymerization, that is, a polyolefin modified with an aromatic vinyl monomer (hereinafter referred to as "modified polyolefin")
A toner for developing an electrostatic image is prepared by containing a wax consisting of: Here, the content ratio of the wax is within the range of 1 to 20 degrees, preferably within the range of 1 to 10 degrees.

If this proportion is less than 1% by weight, the sock will not be effective as a release agent and the non-offset property of the toner will not be improved, while if it exceeds 20% by weight, the fluidity of the toner will decrease. As a result, the developability and transferability deteriorate, making it impossible to form a good visible image, and the wax adheres to the developing tube or electrostatic image support to form a film, impairing its functionality. It becomes a hindrance.

In the toner of the present invention, the binder resin is composed of a polymer obtained by polymerizing a polymerizable monomer in the presence of a reactive prepolymer.
Since the offset generation temperature is high and the non-offset properties are obtained, C2 contains a wax made of modified polyolefin as mentioned above, and as will be clear from the description of the examples below (C2). Although the offset generation temperature is high, the minimum fixing temperature is low and it is suitable for fast fixing using a hot roller fixing device. Also, the degree of decrease in fluidity due to the addition of wax is small. In order to obtain the necessary fluidity, it is no longer necessary to add a fluidity improver such as two-line aqueous silica fine powder, or even if it is necessary to add it, it is sufficient to add only a small amount of it, and therefore the hydrophobic By adding multi-value C2 silica fine powder, it is possible to avoid the adverse effects caused by C2. Furthermore, the toner of the present invention has high non-aggregation properties and vague storage stability. Therefore, according to the toner of the present invention, high fluidity and Due to its non-cohesive properties, it is possible to achieve good development, and it is also possible to fix at low temperatures and high speeds, and as a result, it is possible to consistently form excellent visible images with high image density. In addition, since the toner of the present invention has a low minimum fixing temperature, it is possible to avoid exposing the paper, which is the toner image support, to high temperatures during the fixing process, and therefore, the generation of wrinkles is suppressed. It is practically possible to form homoscopic images using toner on both sides of the image.

Although the exact reason why the toner of the present invention has the above-mentioned ambiguous characteristics has not been elucidated, the reason is that the polymerization of the polymerizable monomer to obtain the binder resin is carried out in the presence of a reactive prepolymer. Therefore, during the reaction process, the polymerization intermediate partially reacts with the reactive prepolymer, and as a result, a large portion of molecular wind is generated in the resulting polymer, which has a higher non-offset property than C2. The obtained and unreacted prepolymer and the relatively small part C2 which did not react with the reactive prepolymer have a fixability, that is, a fixability at a lower temperature (2), and are made of a polyolefin. Because the wax is contained, the minimum fixing temperature is lower while the offset generation temperature is high.The polyolefin is a modified polyolefin and has a large temperature difference compared to a binder made of a polymer polymerized in the presence of a reactive prepolymer. It has a modifying component with affinity in its molecular structure, and therefore has high compatibility with its own binder resin. It is thought that part of the reason is that their gender is large.

What is the binder resin and polymer used in the toner of the present invention? :
To explain specific examples of polymerizable monomers to be obtained, examples of vinyl monomers include styrene, 0-methylstyrene, m-methylstyrene, p-methylstyrene, and α-methylstyrene.
Methylnutyrene, p-ethylstyrene, 2,4-dimethylstyrene, p-n-butylstyrene, p-tert-
Butylstyrene, pn-hexylnutylene, pn-
Octylstyrene, pn-nonylstyrene, pn-
Preferred examples include styrene monomers such as decylstyrene sp''-dodecylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, and 3,4-dichlorostyrene.
For example, ethylenically unsaturated monoolefins such as ethylene, propylene, butylene, and isobutylene; vinyl halides such as vinyl chloride, vinylidene chloride, vinyl bromide, and vinyl fluoride; vinyl acetate, vinyl propionate, vinyl benzoate, and vinyl butyrate. Vinyl esters such as; methyl acrylate, ethyl acrylate, loobyl acrylate,
Inbutyl acrylate, propyl acrylate, n-octyl acrylate, dodecyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, methyl α-chloroacrylate, meth Methyl acrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate acetate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate,
α-methylene aliphatic monocarboxylic acid esters such as diethylaminoethyl methacrylate; acrylonitrile;
Acrylic acid or methacrylic acid derivatives such as methacrylonitrile and acrylamide; Vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, and vinyl isophthyl ether; Vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, and methyl isopropenyl ketone; N- N such as vinylpyrrole, N-vinylcarbazole, N-vinylindole, N-vinylpyrrolidone, etc.
-Vinyl compounds; examples include vinylnaphthalenes and others. These monomers can be used alone or in combination, or can be polymerized to form a copolymer.

In addition to the above-mentioned vinyl monomers, the following polymerizable monomers can also be used. Terephthalic acid is a tribasic acid used as a polymerizable monomer to obtain a polyester resin. , isophthalic acid, adipic acid, maleic acid, succinic acid, cepatic acid, thiodiglycolic acid, diglycolic acid, etc. Glycols include ethylene glycol, diethylene glycol%1
14-bis(2-hydroxyethyl)benzene, 1°4
- Examples include cyclohexane dimetatool, propylene glycol, etc. Polymerizable monomers for obtaining polyamide resin include caprolactam, and tribasic acids include terephthalic acid, isophthalic acid, adipic acid, maleic acid, and succinic acid. Examples of diamines include ethylene diamine, diaminoethyl ether, 1,4-diaminobenzene, 1,4-diaminobutane, etc.0 Polyurethane resins Examples of the polymerizable monomer to be obtained include diincyanates such as p-phenylene diisocyanate, p-xylylene diisocyanate, and 1,4-tetramethylene diisocyanate, and examples of glycols include ethylene glycol and diethylene glycol. , propylene glycol, polyethylene glycol, and the like.

As a polymerizable simple substance for obtaining a polyurea resin, examples of diisocyanates include p-phenylene diisocyanate and p-
Xylylene diisocyanate, 1°4-tetramethylene diisocyanate, etc. can be mentioned, and diamines include ethylenediamine, diaminoethyl ether,
．． Examples include 4-diaminobenzene and 1,4-diaminobutane.

As polymerizable monomers for obtaining epoxy resins, examples of amines include ethylamine, butylamine, ethylenediamine, 1,4-diaminobenzene, 1゜4-diaminobutane, monoethanolamine, etc., and examples of jepoxies include , diglycidyl ether, ethylene glycol diglycidyl ether, bisphenol A diglycidyl ether, hydroquinone diglycidyl ether, and the like.

The polymerization of the polymerizable monomers as described above is carried out in the presence of a reactive prepolymer. Here, the prepolymer includes any prepolymer commonly used by those skilled in the art as a prepolymer. This reactive prepolymer is a reactive prepolymer that can react with the main chain and/or side chain mini-polymerizable monomer of the polymer. It is a prepolymer having a reactive group (or atom); these reactive groups include calxoxy group (-COOH), sulfo group (-80, H), alkyl group such as ethyleneimino group)], incyanate Group (OCN-
), a double bond group (-CH=CH-), an acid anhydride halogen atom, etc. are representative examples.

The reaction between the reactive group of the Cilebo 9mer described above and the polymerizable monomer ranges from those that react simply by mixing them, to those that react in the presence of a catalyst such as an intermediate initiator, and those that react with light irradiation such as the cinnamoyl group. (Includes various types of tubes that react with each other.)

The molecular weight of these prepolymers can be any arbitrary molecular weight, but is usually between i,000 and 500.
000. Preferably 1,000 to 50,000 0 or less C2 Typical examples of these prepolymers are listed below. As for those that have an isocyanate group,] 181 [As those that have a two-point group,] (9) (C0CR= Cl-1cOOc)12CH20+n(
101 1'(-OCHt-CH+.

CHz()CMzCH=CHsi [For those with acid anhydride &] α4+CHzCHzCH-CHJ n1+ CHzCt(-
CHCHz CH n2■ [For those with a carboxy group,] a % C) i, -CH+n OOH [For those with a sulfo group,] (lli1 80, H Cnt:n+=60:40) Decoy +CJ- 12-CH+.

80, H [As a vehicle cross-linked by light] H2 In addition to the above, poly-1,2-butadiene, α, ω-
Butadiene-based prepolymers such as polyphtadiene glycol, maleated polybutadiene, and acrylic-terminated polybutadiene can also be used.

Among the above-mentioned blood-combining monomers, vinyl monomers are particularly preferred, and as the reactive prepolymer to be combined with this vinyl yarn monomer, butadiene-based prepolymers or unsaturated polyesters are preferred.◎ Butadiene-based monomers Preferred specific examples of the prepolymer include butadiene polymer, α,ω-polybutadiene homopolymer, α,ω-polybutadiene glycol, α,ω-
Suitable examples include polybutadiene prepolymers such as polybutadiene dicarbonate, maleated polybutadiene, terminal acrylic polybutadiene, terminal semi-Nisdel modified polybutadiene, and these can be used alone or in appropriate combinations. 0 Also, preferred as the unsaturated polyester are at least one dihydric alcohol selected from the group not shown below as a monomer unit, and at least one dibasic acid selected from group B shown below. The dibasic acids selected from Group B contain a small amount of unsaturated carboxylic acid (for example, fumaric acid, maleic acid, itaconic acid, etc.).

Group A diethylene glycol, triethylene glycol,
1.2-propylene glycol, 1゜3-propylene glycol, 1.4-butynediol, neopentyl glycol, 1.4-butynediol, 1,4-bis(hydroxymethyl)cyclohexane, bisphenol A, hydrogenated bisphenol A , polyoxyethylated bisphenol AC.

Group 8: maleic acid, fumaric acid, mesaconic acid, citraconic acid, itaconic acid, glutaconic acid, phthalic acid, isophthalic acid, terephthalic acid, cyclohexanedicarboxylic acid, succinic acid, adipic acid, sebetic acid, malonic acid, or these acids. Esters with anhydrides or lower alcohols 0 Also, the above-mentioned unsaturated polyester Mikie combination moiety (2 may contain at least II!J or more of trihydric or higher alcohols or carboxylic acids shown in Group C below as a monomer component) .

Group 0: Glycerin, trimethylolpropane, pentaerythritol, trimellidic acid, biromellitic acid The above reactive prepolymers have a weight ratio of 0.1 to 40, preferably 1 to 2 polymerizable monomers C. ~20 weight-
It is sufficient if it is contained in the polymer composition within the range of (2).

In the process of polymerizing the above-mentioned blood-forming monomers in the presence of the above prepolymer, when polymerizing through cross-linking reaction, addition reaction, grafting reaction, etc., part of the composition of the blood-forming monomers It is preferable that a polymerizable monomer having a functional group that reacts directly with the functional group of the prepolymer or a polymerizable monomer having a functional group that can react via a crosslinking agent be co-present.

When the functional group of the prepolymer is an epoxy group or an ethyleneimino group, the polymerizable monomer having a functional group that can react with the functional group of the prepolymer is an epoxy group or an ethyleneimino group. A bundling monomer with a functional group [e.g. amino group, carboxy group] that can react with a group such as 2-aminoethyl methacrylate hydrochloride, N-(2-aminoether)acrylamide salt # , methacrylic acid, and acrylic acid; when the functional group of the prepolymer is an isocyanate group or an acid anhydride group, the blood-forming monomer is a functional group that can react with the isocyanate group or acid anhydride primary crystal. Carbodies having a group [e.g. amino group, carboxime hydroxyl group], specifically 2-aminoethyl methacrylate hydrochloride, N-(2-aminoethel)acrylamide a hydrochloride, methacrylic acid, acrylic acid, 2 -Hydroxyethyl methacrylate and p-hydroxystyrene can be mentioned; when the functional group of the prepolymer is a carboxy group or a sulfo group, examples of the blood-forming monomer include.

Blood-forming monomers having a functional group (for example, an epoxy group or an ethyleneimino group) that can react with a carboxy group or a sulfo group, specific examples include acrylic acid, methacrylic [, N-vinylsulfonyl aziridine, and glycidyl methacrylate] and when there is no direct reaction between the functional groups of the prepolymer and the blood-forming monomer, a cross-linking agent may be used to link the reaction between the functional groups of the prepolymer and those of the blood-forming monomer; The crosslinking agent may have two or more functional groups, at least one of which reacts with the functional group of the prepolymer, and the other reacts with the functional group of the blood-forming monomer; specific examples include: The following compounds may be mentioned: 0HOc)12cH2(Ji-1,1-1be>OH,l-
Trap H2-■)-CH,-01()l)cI-1,ci-
i, octt, CH, α1Hf3CH2CHzOH, H
8(112(II2SH.

) f) C) l, C) iIC α 屓, H α 5, α phantom H, H (
Jl, C) f, 5C) 12Cωh.

HxNCHzCHzNHx, 'NklxCHxCH
z Group CH2CH2 Sat.

As a method for producing the toner of the present invention, general methods for synthesizing the calculus resin of the toner, such as the secondary method, the emulsion polymerization method, the block method, or the solution vehicle method, are widely used.

The polyolefin component of the modified polyolefin used as the wax contained in the toner of the present invention is either a homopolymer type obtained from a single olefin monomer or an olefin type obtained by copolymerizing the olefin monomer with another monomer that can be copolymerized with this process. Examples of Ca11 olefin monomers which may be of any number of copolymer types include ethylene, propylene, phten-I, pentene-I, etc.
, hexene-1, heftene-1, octene-1, / #
-1, decene-1, and their isomers with different positions of the unsaturated bond, as well as (2) such as 3-methyl-1-butene, 3-methyl-2-pentene, 3-propyl-5-
Includes all other olefin monomers, such as methyl-2-hexene (those with branched chains consisting of -alkyl groups).

In addition to other olefin monomers, examples of other polymers that can be copolymerized with olefin monomers include vinyl ethers such as vinyl methyl ether, vinyl-n-butyl ether, and vinyl phenyl ether; ), vinyl esters such as vinyl butyrate, vinyl fluoride, vinylidene fluoride, tetrafluoroethylene, vinyl chloride, vinylidene chloride, haloolefins such as tetrachloroethylene, such as methyl acrylate, ethyl acrylate, n-butyl acrylate, methyl Acrylic esters or methacrylic esters such as methacrylate, ether methacrylate, n-butyl methacrylate, stearyl methacrylate, N,N-dimethylaminoethyl methacrylate, t-butylaminoether methacrylate, etc. acrylic acid derivatives such as acrylonitrile, N,N-dimethylacrylamide, organic acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, diethyl fumarate, β-pinene, etc. Therefore, when the polyolefin component is a copolymer type, an olefin copolymer type obtained by copolymerizing at least two or more of the above olefin monomers, such as ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-pentene copolymer, propylene-
Copolymer types such as butene copolymer, propylene-pentene copolymer, ethylene-3-methyl-1-butene copolymer, ethylene-propylene-butene copolymer, etc.
Or an olefin copolymer type obtained by copolymerizing at least one of the above olefin monomers and at least one monomer other than the above olefin monomers, such as ethylene-vinyl acetate copolymer, ethylene -vinyl methylenitel co-arashi polymer, ethylene-vinyl chloride copolymer, ethylene-methyl acrylate copolymer, ethylene-methyl methacrylate copolymer, ethylene-acrylic acid copolymer, propylene-vinyl acetate copolymer, Propylene-vinylethyl ether copolymer, propylene-ethyl acrylate copolymer, propylene-methacrylic acid copolymer, butene-vinyl methyl ether copolymer, pudene-methyl methacrylate copolymer, pentene-vinyl acetate copolymer It can be a copolymer type such as a co-71 polymer, an ethylene-propylene-vinyl acetate copolymer, and an ethylene-vinyl acetate-vinyl methyl ether copolymer.

When making a copolymer type using a monomer other than an olefin monomer (=, it is possible to make a copolymer type in which the proportion of the olefin moiety by the olefin monomer in one portion of the polyolefin is, for example, 50 mol or more). Preferable: When the ratio of the olefin portion is high, the effect of improving the fixing properties of the toner is fully exhibited.
((t(rukara.

The modified polyolefin is composed of a polyolefin component and a modifying component as described above, and the polyolefin component is a di-blocked or grafted component.

Aromatic vinyl monomers are used as the modifying component, and specific examples thereof include 1-phenylpropene,
Nuterene, o-1 methylstyrene, m-methylstyrene,
p-methylstyrene, α-methylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, p-n-butylstyrene, p-te, rt-1-methylstyrene, p-n-
hexylstyrene, p-n-octylstyrene, p-n
-nonylstyrene, pn-decylstyrene, pn-
)' Using zero or more aromatic vinyl monomers such as decylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,4-dimethylstyrene, etc., and the above-mentioned polyolefin. For example, by carrying out block copolymerization or granoid copolymerization, waxes consisting of injected polyolefins can be obtained by conventional methods and conditions (2). A method of reacting wax with a mechanochemical polymer to obtain a block copolymer can be used, and 62 is a method of reacting ozonated polyethylene (a method of reacting with a diaromatic vinyl monomer) for granoid copolymerization. A polymer initiator method) or a method of grafting using radiation can be used.
．． It is preferable that the ratio be within the range of 1 to 15 ff, especially (2) 1 to 10 ff. If this ratio is too small, the fluidity of the toner will be severely reduced, and if it is too large, the minimum standard temperature of the toner will be high. Become.

In addition, 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 υ, preferably 90 to 160
It is desirable that the temperature is ℃.

The toner of the present invention is a granular material made by dispersing the above-mentioned modified polyolefin wax in the above-mentioned binder resin together with a coloring agent, a magnetic substance, a property improver, and other necessary additives. The average particle size is usually between 5 and 30 microns.

As a coloring agent, carbon black, nigrosine dye (
(:', 1. 5υ415B), Aniline Blue (C
, 1, A30405), Calco Oil Blue (C, I.

A azoec Elue 3), Kromui, Z a
-(C,1,A14090), Ultramarine Blue (
C, 1, A77103), DuPont Oil Red (C.
1. A26105), quinoline yellow (C,l, 47005), methylene blue chloride (C,I, 52015), phthalocyanine blue (C,1,A7)
4160), malachite green oxalay 1-(C,
1, J2 42000), lamp black (C, 1, A7
7266), Rose Bengal (C6■, 45435)
, mixtures of these, and other colorants, which can be used to form a visible image of sufficient density (
It is necessary to contain it in a sufficient proportion, and usually the proportion is about 1 to 20 parts by weight per 100 parts by weight of the binder resin. The magnetic materials include ferrite, magnetite, etc. Ferromagnetic gold such as iron, cobalt, and nickel indicates gold I.
or alloys or compounds containing these elements, or C2 alloys that do not contain ferromagnetic elements but exhibit ferromagnetism by applying appropriate heat treatment, such as manganese-copper-aluminum, manganese-copper-tin, etc. Mention may be made of a type of alloy called Heusler alloy containing manganese and copper, or chromium dioxide, among others. 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
) 20 to 70 parts by weight, preferably 40 to 70 parts by weight per part by weight of t-toj.

Examples of the property improving agent include a charge control agent, an anti-offset agent, a lubricant for improving fluidity, and others.

The toner of the present invention is mixed with a carrier made of iron powder, glass beads, etc. to form a two-component developer, but when it contains a magnetic material, it can be used as a single-component developer for developing electrostatic images. Ru.

Examples of the present invention will be described below, but the present invention is not limited by these C2. It is the following.

[Binder resin]

1) Binder resin A Polymerizable monomer: Styrene 85 parts n-butyl acrylate 15 parts Reactive prepolymer: Obtained by reacting etherified bisphenol A with fumaric acid and terephthalic acid in a ratio of 1:1. softening point 11'2
Resin with a softening point of 130°C obtained by polymerizing 3 parts or more of unsaturated polyester of υ using benzoyl peroxide as an initiator 2) Binder resin B Fastening monomer: Styrene 85 parts n-butyl acrylate 15 parts reactive prepolymer: α,ω-polyphtadiene glycol [Nl8SO-PB
-G-3000J (manufactured by Nihon Shisokusha, molecular weight: 4ooo
) was obtained by polymerizing 5 parts or more of the material using benzoyl peroxide as an initiator. Resin with a softening point of 132°C 3) Binder resin C
(For comparison) Polymerizable monomer: 85 parts of styrene 15 parts or more of n-butyl acrylate Resin [wax] with a softening point of 120°C obtained by polymerizing 15 parts or more of n-butyl acrylate using benzoyl peroxide as an initiator 1) Wax a Polyethylene wax made by block copolymerization of styrene≦2 (styrene component content: 4, softening point: 11)
2υ) 2) Wax b Polyethylene wax made by ↓riblock copolymerization with 1-phenylpropene (1-phenylpropene content 4)
3) Wax C Polyethylene wax block copolymerized with styrene C (styrene content 8 11%, softening point 116)
℃) 4) Wax d Polyethylene wax graft copolymerized with 1-phenylpropene (l-phenylzo; Lopene content 4% by weight, softening point 112°C) 5) Wax e (for comparison) Unmodified polypropylene wax "Viscol 660PJ
(manufactured by Kochu Kasei Co., Ltd.). 6) Wax f (for comparison) Unmodified polyethylene wax “Hiwax 220PJ
(Softening point 113°C, manufactured by Mikata Petrochemical Co., Ltd.) 7) Wax g (for comparison) Oxidized polyethylene wax Rohiwax 4202J
(Conversion point: 108°C, manufactured by Mikata Petrochemical Co., Ltd.) In each of the Examples and Comparative Examples, the materials with the indicated formulations were subjected to the usual methods of melting, mixing, cooling, crushing, and classifying. Example 1 Binder resin A 100 parts Wax a 3 parts Carbon black [Mogul LJ 10 parts (manufactured by Capot Co., Ltd.) Processing Example 2 Binder resin A 100 parts Wax b 3 parts Carbon black "Mogal L" 10 parts Example 3 Binder resin A 100 parts Wax 0 3 parts Carbon black "Mogal L" 10 parts Fu Example 4 Binder resin A 100 parts Wax d 3 parts Carbon black "Mogal Shi" 10 parts Further Example 5 Binder resin A 100 parts Wax 8 6 parts Carbon black "Mogul L" 10 parts Example 6 Binder 1st fat B 100 parts Wax 3 3 parts Carbon blank "Mogul LJ 10 parts Example 7 Binder level 1 fat B 100 parts Wax b 3 parts Carbon black "Mogal L" 10 parts Example 8 Binder resin B 100 parts Wax 0 3 parts Carbon black "Mocal LJ 10 parts Example 9 Binder resin B 100 parts Wax a 6 parts Carbon black [Mogal LJ loo Example 10 Binder resin A 48 parts Wax 3 3 parts Magnetic fine powder BL-100J 52 parts Comparative example 1 Binder resin A 100 parts Wax e 3 parts Carbon black Mogul LJ 10 parts Comparative example 2 Binder resin A 100 Part wax f 3 parts Carbon black "Mogul L" 10 parts Comparative example 3 Binder resin A 100 parts Wax g 3 parts Carbon black "Mogul L" 10 parts Comparative example 4 Binder resin 0 100 parts Wax 8 3 parts Carbon black [Mogul LJ loo Comparative Example 5 Binder Resin A 100 parts Carbon black [Mogul LJ Lo Part Above The toners obtained in Examples 1 to 10 were
The toners obtained in Comparative Examples 1 to 5 were respectively designated as "Comparative Toner 1" to "Comparative Toner 5", and the fluidity of each of these toners was determined to be 0-immediate. 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 the powder and granules is small. Concrete (Secondly, the sample is loosely packed into a container with a diameter of 28111I and a volume of 100+nl from above through a 100 mesh sieve, the weight is measured and the static bulk density is measured, and then the container is covered with a lid of the same diameter and a top tapping device is used. 60 under the condition of falling height 5 fins from C2
Calculate the volume of the sample when tapping 0 times, divide the previously determined M amount by this volume value to determine the solidified bulk density P, and calculate the degree of compression C using the following formula. A visual agent that mixes each of the 14 toners in total with a resin-coated carrier that is stronger than iron powder so that the toner concentration is 2% by weight and the toner charge is 20±1 microcoulomb/9. and by each of them,
An electrophotographic copying machine [U-Bix 3000J (manufactured by Konishi Roku Photo Industries Co., Ltd.) was used to develop the electrostatic charge image, transfer the toner image onto transfer paper, and fix the toner image using a heat roller fixing device. The primary adhesion amount of toner to the surface, the transfer rate to the transfer paper, and the image density of the obtained copy image were measured. Here, the toner primary adhesion MN is per unit area at a point where the so-called solid black potential is 800 0, which is the toner adhesion amount of 0.Furthermore, for each of all toners, the minimum fixing temperature and offset occurrence temperature were evaluated, and the storage stability was evaluated. The heat roller is made of silicone rubber [KE-130O] and the surface layer is made of silicone rubber [KE-130O].
The sample toner was transferred onto a 6411/m" transfer paper using a fixing device consisting of a pressure roller formed with "RT■" (manufactured by Shin-Etsu Chemical Co., Ltd.).
The operation of fixing at 20fi/sec was performed by increasing the heat roller's set temperature tn- by 100υ and increasing it stepwise by 5υ at each temperature f! Repeatedly at L+2, the formed fixed image C2 was subjected to Kimwibe rubbing, and the fixed image C2 showing sufficient rubbing resistance was defined as the lowest setting temperature. The matching fuser has a silicone oil supply mechanism.

In addition, to measure the offset occurrence temperature, the toner image is transferred and fixed using 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 were generated was repeated while the set temperature of the heat roller of the fixing device was successively increased to determine the offset photogenic temperature. Regarding toner 10 (=), the electrophotographic copying machine "U-Bi"
xTJ (manufactured by Konishi Rokushakoshi Kogyo Co., Ltd.) was used to develop the electrostatic charge image and transfer the toner image onto transfer paper, and a fixing test was conducted.

Regarding storage stability, Table 1≦2 shows the results of evaluating the presence or absence of aggregation and its degree when each sample was left for 48 hours at a temperature of 55υ and a relative humidity of 40%.

In addition, each of Toner 1 to Toner 9 (20,000 times (=
When we conducted a continuous copying test, we found that no matter how many 2'L of toner was used, the copies were clear and good all the way to the end +1!
An IJ image was formed.

As is clear from the above results, the toner according to the present invention has
It has vague non-offset properties, has a very low minimum fixing temperature, has a wider fixing temperature range than toners containing conventional unmodified polyolefin wax, and has poor fluidity. It can be put to practical use even without the addition of an improving agent, has excellent developability and transferability, and can always form stable and good visible images.

Claims (1)

[Scope of Claims] 1) Block copolymerization or graft copolymerization of an aromatic vinyl monomer with a binder resin consisting of a polymer obtained by polymerizing a blood-forming monomer in the presence of a reactive prepolymer. A toner for developing an electrostatic image characterized by containing a wax made of polyolefin 02) The content ratio of the socks is 1 to 20 *jt%
The toner for developing an electrostatic image according to claim 1. 3) The toner for electrostatic image visualization according to claim 1, wherein the reactive prepolymer is a butadiene thread prepolymer. 4) The toner port for developing an electrostatic image according to claim 1, wherein the reactive prepolymer is an unsaturated polyester.