JPH09211896A - Electric charge controlling agent composition, toner binder composition and toner for developing electrostatic charge image - Google Patents

Abstract

PROBLEM TO BE SOLVED: To ensure a superior color tone and to improve safety and dispersibility by using a salt of an org. acid and an org. compd. having an arom. ring substd. by a specified electron withdrawing group as essential components. SOLUTION: This electric charge controlling agent compsn. contains a salt of an org. acid and an org. compd. having an arom. ring substd. by one or more kinds of electron withdrawing groups selected from among halogen, nitro and cyano groups as essential constituent components. The salt is, e.g. a sulfonate preferably having a perfluoroalkyl group. The org. compd. is, e.g. a polymer contg. a polymerizable monomer having an arom. ring substd. by such electron withdrawing groups as constituent units. This compsn. is excellent in safety because a heavy metal is not contained, ensures a superior color tone for a color toner, has high dispersibility and gives a toner having sharp distribution of the quantity of electric charges.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a charge control agent composition,
The present invention relates to a toner binder composition containing the same and a toner for developing an electrostatic charge image. More specifically, it relates to a negatively chargeable charge control agent composition, a toner binder composition containing the same, and an electrostatic charge image developing toner.

[0002]

2. Description of the Related Art Conventionally, a charge control agent has been added in order to control the charge of an electrostatic image developing toner used in electrophotography, electrostatic recording, electrostatic printing and the like. Among the charge control agents known today, examples of charge control agents for negative charging include azo dye-based compounds and salicylic acid metal complexes. However, these compounds are originally colored (for example, azo dye compounds), and in addition, they contain heavy metals such as chromium, cobalt, and zinc, which is becoming a problem from the viewpoint of safety in recent years. Further, since these compounds are low-molecular crystals, it is difficult to finely disperse them in the toner, and there is a problem that the charge amount distribution is widened when the toner is used.

To solve the above problems, a styrene / sodium vinylbenzenesulfonate copolymer (JP-A-63-88564), a perfluoroalkylethyl acrylate polymer and styrene / methyl acrylate / t-butyl are used. Polymer compounds such as a combination of acrylamide sulfonic acid copolymer (JP-A-6-230609) and methyl methacrylate / methacrylic acid block copolymer (US Pat. No. 4,925,765) have been proposed. .

[0004]

However, although the polymer compounds disclosed in (1) to (3) have been solved in terms of coloring and safety, the charge amount and the rise of charge are insufficient, so that a large amount is added to the toner. There is a need. Therefore, it is not economical and adversely affects other toner properties (low temperature fixing property, hot offset resistance, etc.). Further, these compounds have a problem that the charge amount changes greatly with humidity (environmental stability is insufficient).

[0005]

The present inventors have found that the present invention is substantially colorless and does not contain heavy metals, and a small amount of addition provides a sufficient charge amount.
The present invention has been earnestly studied in order to develop a charge control agent capable of obtaining a rise in charge and excellent in environmental stability, and arrived at the present invention.
That is, the present invention is constituted by the following [1] to [3]. [1] Organic acid salt (α) and at least one electron withdrawing group X selected from the group consisting of halogen atoms, nitro groups, and cyano groups
A charge control agent composition containing an organic compound (β) having an aromatic ring substituted by ## STR1 ## as an essential component [2] containing a toner binder and the charge control agent composition according to [1] In the toner for developing an electrostatic image containing a toner binder, a coloring material and a charge control agent, the charge control agent is
[1] A toner for developing an electrostatic charge image, comprising the charge control agent composition

In the present invention, as the organic acid salt (α), there are sulfonate (α1), carboxylate (α2), sulfamate (α3), sulfate (α4) and phosphate (α).
5) and the like, and more preferable one is an organic acid salt (α-a) having a perfluoroalkyl group in the molecule, that is, a perfluoroalkyl group-containing sulfonate (α1-a).
a), perfluoroalkyl group-containing carboxylate (α2-
a), perfluoroalkyl group-containing sulfamate (α3-a), perfluoroalkyl group-containing sulfate (α4-
a) and perfluoroalkyl group-containing phosphate (α5-
a) and the like.

Examples of (α1) include salts of sulfonic acid and a cation component. As the sulfonic acid, perfluoroalkyl group-containing sulfonic acid [perfluoroalkanesulfonic acid (trifluoromethanesulfonic acid,
Perfluorohexanesulfonic acid, perfluorooctanesulfonic acid, etc.), Perfluoroalkylethanesulfonic acid (perfluorooctylethanesulfonic acid, perfluorodecylethanesulfonic acid, etc.), Perfluoroalkenyloxybenzenesulfonic acid (perfluorononenyloxy) Benzene sulfonic acid etc.)], alkyl sulfonic acid (hexane sulfonic acid, octane sulfonic acid etc.), aryl sulfonic acid (octyl benzene sulfonic acid, toluene sulfonic acid etc.) and the like.
Among these, preferred are perfluoroalkyl group-containing sulfonic acids, more preferred are perfluoroalkane sulfonic acids, and particularly preferred are perfluorooctane sulfonic acids. As the cation component, alkali metal (lithium, sodium, potassium, etc.) salt, alkaline earth metal (magnesium, calcium, barium, etc.) salt, amine (triethylamine,
(Tributylamine, dimethylbenzylamine, etc.) salts and quaternary ammonium salts (tributylbenzylammonium salt, tetraethylammonium salt, tetrabutylammonium salt, etc.) and the like.

As (α2), carboxylic acid and the above (α
Examples thereof include salts with the same cation component as in 1). Examples of the carboxylic acid include a perfluoroalkyl group-containing carboxylic acid [perfluoroalkanoic acid (perfluorohexanoic acid, perfluorooctanoic acid, etc.), perfluoroalkenyloxybenzoic acid (perfluorononenyloxybenzoic acid, etc.)], alkyl Examples thereof include carboxylic acids (lauric acid, stearic acid, etc.), arylcarboxylic acids (benzoic acid, etc.), and the like.

Examples of (α3) include salts of sulfamic acid and the same cation component as in (α1) above. Examples of sulfamic acid include perfluoroalkyl group-containing sulfamic acid [perfluoroalkylethanesulfamic acid (perfluorooctylethanesulfamic acid, perfluorodecylethanesulfamic acid, etc.)], alkylsulfamic acid (octylsulfamic acid, decylsulfamic acid, etc.) ) Is mentioned.

Examples of (α4) include salts of sulfuric acid with a cation component similar to the above (α1). As sulfuric acid, monosulfuric acid ester of perfluoroalkyl group-containing alcohol [perfluoroalkylethanol (perfluorooctylethanol, perfluorodecylethanol, etc.), perfluoroalkylmethanol (perfluorohexylmethanol, etc.)], alcohol (octanol, Decanol etc.) and the like monosulfate ester and the like.

Examples of (α5) include salts of phosphoric acid and the same cation component as in (α1) above. Examples of phosphoric acid include phosphoric acid containing a perfluoroalkyl group (such as mono- or bis-phosphoric acid ester of perfluoroalkyl-containing alcohol) and mono- or bis-phosphoric acid ester of alcohol.

Among these (α), preferred are perfluoroalkyl group-containing organic acid salts (α-a) and sulfonates (α1), and more preferred are perfluoroalkyl group-containing organic acid salts. (Α-a), particularly preferred are perfluoroalkyl group-containing sulfonates (α1-a), and more preferred are alkali metal, alkaline earth metal and perfluoroalkyl group-containing sulfonates. It is an amine salt. Heavy metal (nickel,
Salts of copper, zinc, mercury, chromium, etc. are not preferable in terms of safety.

In the present invention, the electron-withdrawing group X is
Examples thereof include halogen atoms (chlorine atom, bromine atom, iodine atom, fluorine atom), nitro group and cyano group. Among these, a halogen atom and a nitro group are preferable, and a chlorine atom and a nitro group are particularly preferable. The organic compound (β) having an aromatic ring substituted by the electron-withdrawing group X is a polymer containing a polymerizable monomer (A) having an aromatic ring substituted by the electron-withdrawing group X as a constituent unit. (A), a low molecular weight compound having an aromatic ring substituted with an electron-withdrawing group X can be mentioned. Of these, preferred is (A).

The electron-withdrawing group X constituting the polymer (A)
Examples of the polymerizable monomer (a) having an aromatic ring substituted by styrene include styrene substitution products (chlorostyrene, dichlorostyrene, bromostyrene, fluorostyrene, nitrostyrene, cyanostyrene, etc.), phenyl (meth) acrylate substitution products. [Chlorophenyl (meth) acrylate, bromophenyl (meth) acrylate, nitrophenyl (meth) acrylate, chlorophenyloxyethyl (meth)
Acrylate, bromophenyloxyethyl (meth) acrylate, nitrophenyloxyethyl (meth) acrylate, etc.], phenyl (meth) acrylamide substitution product [chlorophenyl (meth) acrylamide, bromophenyl
(Meth) acrylamide, nitrophenyl (meth) acrylamide, etc.], phenylmaleimide substitution product (chlorophenylmaleimide, dichlorophenylmaleimide, nitrophenylmaleimide, nitrochlorophenylmaleimide, etc.), phenylitaconimide substitution product (chlorophenylitaconimide, dichlorophenylitaconimide,
Nitrophenylitaconimide, nitrochlorophenylitaconimide, etc.), phenyl vinyl ether substitution products (chlorophenyl vinyl ether, nitrophenyl vinyl ether, etc.) and the like. Of these, preferred are phenylmaleimide-substituted products and phenylitaconimide-substituted products.

In the present invention, the polymer (A) may be a homopolymer of the polymerizable monomer (A) having an aromatic ring substituted by the electron-withdrawing group X, but can be copolymerized with (A). It is also possible to use a copolymer with one or more other monomers. Examples of the other monomer copolymerizable with (a) include a perfluoroalkyl group- or silicone group-containing polymerizable monomer (a) and a sulfo group-containing polymerizable monomer (c). Copolymerization with (a) is preferable in that a toner with a high charge amount can be obtained with a small amount of addition and the environmental stability is improved. Further, copolymerization with (c) is preferable in that the rise of charging is further improved.

As the perfluoroalkyl group- and / or silicone group-containing polymerizable monomer (a), perfluoroalkyl group-containing polymerizable monomer (a-1) and silicone group-containing polymerizable monomer (a- 2) is mentioned. As the perfluoroalkyl group-containing polymerizable monomer (a-1), perfluoroalkylethyl (meth) acrylate, mono
(Perfluoroalkylethyl) maleate and mono
(Perfluoroalkylethyl) itaconate, perfluoroalkylethylene and the like can be mentioned. Examples of the silicone group-containing polymerizable monomer (a-2) include a terminal hydroxyl group-modified silicone oil and an ester of (meth) acrylic acid or maleic acid. Among these, preferred is (a-1), and particularly preferred is (a-1) in which the perfluoroalkyl group has 8 to 16 carbon atoms.

The sulfo group-containing polymerizable monomer (c) is a sulfonic acid group-containing polymerizable monomer (styrenesulfonic acid, sulfophenylmaleimide, sulfophenylitaconimide, vinylsulfonic acid, 2-acrylamido-2-). Methyl propane sulfonic acid, methacryloyloxypropyl sulfonic acid, etc.), sulfonic acid group-containing polymerizable monomers (alkali metal salts of the above sulfonic acid, etc.) and the like. Among these (c), preferable are sulfonate group-containing polymerizable monomers.

Other monomers (d) other than (a) and (c) copolymerizable with (a) include olefins (ethylene,
Propylene, 1-butene, isobutylene, dodecene, etc.), vinyl ether (methyl vinyl ether, butyl vinyl ether, stearyl vinyl ether, etc.), aromatic vinyl hydrocarbon (styrene, α-methylstyrene, p-
Cumylstyrene, etc.), (meth) acrylic acid, (meth)
Acrylic ester {methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate,
Stearyl (meth) acrylate}, dienes (butadiene, isoprene, etc.), unsaturated dicarboxylic acids (maleic acid, itaconic acid, etc.), and acid anhydrides thereof, and the like.

The proportion of each structural unit in the polymer (A) is as follows. (A) is usually 10% by weight or more, preferably 10% by weight.
˜99% by weight, more preferably 20 to 90% by weight. (A) is usually 0 to 90% by weight, preferably 1 to 9
It is 0% by weight, more preferably 10 to 80% by weight.
(C) is usually 0 to 20% by weight, preferably 0 to 10% by weight, more preferably 1 to 10% by weight. (A)
If the ratio is less than 10% by weight, the charge amount will be insufficient.

The weight average molecular weight of the polymer (A) is usually 1,000 to 500,000, preferably 2,000.
It is 0 to 200,000. If it is less than 1,000, it is compatible with the toner binder and the charge amount becomes insufficient, and the fluidity of the toner is adversely affected. On the other hand, when it exceeds 500,000, it becomes difficult to disperse it in the toner.

Part or all of the polymer (A) is
A styrene-based polymer portion (b1) and a polyester-based polymer portion (b) are added to the polymer portion (a) having the same structure as (A).
It is also possible to replace it with a charge control agent composed of a copolymer (AB) in which the polymer portion (b) selected from 2) is bonded in a graft or block form. By changing (A) to (AB), (a) is preferable in that the particle size of the discontinuous domains formed in the toner can be easily reduced, and the charge amount distribution can be sharpened. In order to exhibit this effect, it is more preferable that (b) has a structure similar to that of the toner binder. That is, when a styrene-based polymer is used as the toner binder,
1) is more preferable, and when the toner binder is a polyester polymer, (b2) is more preferable as (b). In the case of the charge control agent composed of (AB), in order to reduce the dispersed particle size in the toner, the total amount of (A) is (AB)
It is not necessary that the number be (AB). That is, you may contain (A) with (AB). Further, in addition to (AB) and (A), it may contain a polymer (B) selected from a styrene-based polymer (B1) and a polyester-based polymer (B2) which are not bonded to (a). .

Among (A) which constitutes (a), the preferable one is the same as the above description regarding (A).

The styrene polymer portion (b1) may be a homopolymer of styrene or a copolymer of another monomer (e) copolymerizable with styrene. Examples of other copolymerizable monomers (e) include aromatic vinyl hydrocarbons other than styrene, (meth) acrylic monomers, nitrile monomers and other vinyl monomers. As aromatic vinyl hydrocarbons other than styrene, alkyl-substituted styrenes (α-methylstyrene, p-methylstyrene, p-
Cumyl styrene etc.), acetoxy styrene, hydroxy styrene and the like. Examples of (meth) acrylic monomers include alkyl (meth) acrylate [methyl (meth) acrylate
Acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, etc.]; hydroxyl group-containing (meth) acrylate [hydroxyethyl (meth) acrylate Etc.]; Epoxy group-containing (meth) acrylate [glycidyl (meth) acrylate and the like]; Isocyanate group-containing (meth) acrylate [methacryloyl isocyanate and the like] and the like. Examples of the nitrile-based monomer include acrylonitrile and methacrylonitrile. Other vinyl monomers include vinyl ester (vinyl acetate,
Vinyl propionate, etc .; Diene monomers (butadiene, isoprene, etc.); α, β-unsaturated mono- or polycarboxylic acids [(meth) acrylic acid, crotonic acid, sorbic acid, maleic acid, itaconic acid, cinnamon bark Acid etc.]; their anhydrides (maleic anhydride etc.); their partial esters (maleic acid monomethyl ester etc.) and the like. Among those exemplified as the styrene-based polymer portion (b1), preferred are a styrene homopolymer, a copolymer of styrene and a (meth) acrylic monomer, a copolymer of styrene and a nitrile monomer, It is a copolymer of styrene and a diene-based monomer and a copolymer of these with a small amount of another copolymerizable monomer. When (b1) is a styrene-based copolymer, the copolymerization ratio of styrene and the other monomer (e) is usually 40 mol% or more, and preferably 60 mol% or more.

In the present invention, examples of the polyester polymer portion (b2) include polycondensates of polyol (f) and polycarboxylic acid (ki). Examples of the polyol (f) include a diol (f-1) and a polyol (f-2) having a valence of 3 or more, (f-1) alone or (f).
A mixture of (-1) and a small amount of (F-2) is preferable. As the diol (f-1), alkylene glycol (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, etc.); alkylene ether glycol (diethylene glycol) , Triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, etc.); alicyclic diols (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); bisphenols (bisphenol A, bisphenol F, etc.) , Bisphenol S, etc.); alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adducts of the above bisphenols, and the like. Among these, preferred are alkylene glycols having 2 to 12 carbon atoms and alkylene oxide adducts of bisphenols, and particularly preferred are alkylene oxide adducts of bisphenols, and alkylene oxide adducts having 2 to 2 carbon atoms.
12 together with alkylene glycol. Examples of trihydric or higher polyols (C-2) include aliphatic polyhydric alcohols (glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, etc.); trihydric and higher phenols (trisphenol P).
A, phenol novolac, cresol novolac, etc.); and alkylene oxide adducts of the above trivalent or more polyphenols. Examples of the polycarboxylic acid (ki) include dicarboxylic acid (ki-1) and polycarboxylic acid having a valence of 3 or more (ki-2), and (ki-1) and (ki-1) in a small amount (ki-). The mixture of 2) is preferred. Dicarboxylic acids (ki-1) include alkylenedicarboxylic acids (succinic acid, adipic acid, sebacic acid, etc.); alkenylene dicarboxylic acids (maleic acid, fumaric acid, etc.); aromatic dicarboxylic acids (phthalic acid, isophthalic acid, terephthalic acid) , Naphthalene dicarboxylic acid, etc.) and the like.
Of these, preferred are alkenylene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms. Examples of the trivalent or higher polycarboxylic acid (ki-2) include aromatic polycarboxylic acids having 9 to 20 carbon atoms (such as trimellitic acid and pyromellitic acid).
The molar ratio of (f) and (ki) constituting the polyester polymer part (b2) is usually 1: 2 to 2: 1, preferably 1: 1.5 to 1.5: 1. The molar ratio of (f-1) to (f-2) in (f) is usually 100: 0 to 80:20, preferably 100: 0 to 90:10. The preferable molar ratio of (ki-1) and (ki-2) in (ki) is also the same as the molar ratio of (f-1) and (f-2). Further, preferred as (B1) and (B2) are (b1) and (b
Same as 2).

The weight ratio of (AB), (A) and (B) in the charge control agent in the case of being bound in the form of graft or block is usually such that (AB) is 1 to 100% by weight and (A). Is 0 to 99% by weight, (B) is 0 to 90%, preferably (AB) is 10 to 100% by weight, (A) is 0 to 90% by weight, and (B) is 0 to 50%. . If the weight ratio of (AB) is less than 1% by weight, the effect of binding in a graft or block form will not be exhibited, and if the content of (B) exceeds 90% by weight, a large amount of charge control agent for obtaining a sufficient charge amount. Is necessary and not economical. The ratio (Wa) of the total weight of (a) and (A) in the charge control agent is usually 10 to 99% by weight, preferably 20 to 90% by weight. When (Wa) is less than 10%, a large amount of charge control agent is required to obtain a sufficient charge amount, which is not economical, and when it exceeds 99%, the effect of binding in a graft or block form is not exhibited.

Examples of the method of bonding the copolymer (AB) in which (a) and (b) are bonded in a graft form and / or a block form are as follows. Graft copolymer obtained by grafting the branch polymer of (b) onto the trunk polymer of (a) Graft copolymer obtained by grafting the branch polymer of (a) onto the trunk polymer of (b) Block copolymer of (a) and (b) Polymer

The weight average molecular weights of (a) and (b) constituting (AB) are usually 1,000 to 500, for (a).
000 and (b) are 1,000 to 500,000, preferably (a) is 2,000 to 200,000 and (b) is 3,000 to 100,000. (A) or (b)
Less than 1,000 adversely affects the fluidity of the toner,
When (a) or (b) exceeds 500,000, it becomes difficult to disperse it in the toner.

Specific examples of the polymer (A) include the followings. The ratio in parentheses indicates the weight ratio. (1) Nitrophenyl maleimide / perfluoroalkyl (mixture of C8 to C12) ethyl methacrylate (55
/ 45) Copolymer (2) Chlorophenyl maleimide / perfluoroalkyl (mixture of C8 to C12) ethyl acrylate (55 /
45) Copolymer (3) Dichlorophenylmaleimide polymer (4) Dichlorophenylmaleimide / perfluoroalkyl (mixture of C8 to C12) Ethyl methacrylate (4
8/52) Copolymer (5) Dichlorophenylitaconimide / perfluoroalkyl (mixture of C8 to C12) Ethyl acrylate (49/51) Copolymer (6) Dichlorophenyl maleimide / monoperfluoroalkyl (mixture of C8 to C12) ) Ethyl maleate / methyl vinyl ether (34/42/14) copolymer (7) Dichlorophenyl maleimide / perfluoroalkyl (mixture of C8 to C12) ethyl methacrylate / styrene sulfonic acid sodium salt (46/50/4) copolymer Coalescing

Specific examples of the copolymer (AB) include a portion having the same structure as that exemplified as the above (A) and the following graft copolymer (b). (1 ′) Styrene homopolymer part (2 ′) Styrene / butyl acrylate (95/5) copolymer part (3 ′) Styrene / butyl acrylate (87/13) copolymer part (4 ′) Styrene / Butyl methacrylate (75/25) copolymer part (5 ') styrene / acrylonitrile (85/15) copolymer part (6') styrene / butadiene (90/10) copolymer part (7 ') bisphenol A propylene oxide 2 mol adduct / isophthalic acid polycondensate part (8 ') Bisphenol A propylene oxide 2 mol adduct / terephthalic acid polycondensate part (9') Bisphenol A ethylene oxide 2 mol adduct / maleic acid polycondensate Product part (10 ') Bisphenol A propylene oxide 3 mol adduct / maleic acid polycondensate part (11') Bisphenol A ethylene oxide 3 mol adduct / telef Le acid polycondensate part

As an example of the method for producing the polymer (A), the monomers required for obtaining the desired structure from the beginning may be copolymerized according to a known method, or the desired (A) can be derived. After copolymerizing a monomer having a functional group, it may be further reacted to obtain the target copolymer (A). For example,
Dichlorophenylitaconimide may be polymerized with azobisisobutyronitrile as an initiator, or it may be obtained by polymerizing itaconic anhydride and then reacting with dichloroaniline. Examples of the method for producing the copolymer (AB) include the following methods. Styrene-based or polyester-based polymer portion (b) having a polymerizable functional group (for example, an allyl group) at the terminal thereof, and a monomer constituting (a) before becoming copolymer portion (a) Macromer method of obtaining a graft copolymer by copolymerizing a polymer. A styrene-based or polyester-based polymer portion (b) having a functional group (for example, an amino group or a hydroxyl group) capable of reacting with the copolymer portion (a) at the terminal, and a side of the copolymer portion (a). A polymer reaction method in which a copolymer is obtained by reacting with a functional group of a chain (for example, a carboxyl group or an acid anhydride group). A styrene-based or polyester-based polymer portion (b) having a polymerization initiating group (for example, a peroxide group) in a side chain thereof and a monomer constituting (a) before forming a copolymer portion (a). By reacting a monomer having a polymerization initiating group on the side chain of the copolymer part (a) with styrene and other copolymerizable monomers as required. A main chain initiation polymerization method for obtaining a graft copolymer.

The manufacturing method of (a) is basically the same as the above (A).
It is the same as the manufacturing method. For example, as a method of introducing a functional group capable of reacting with a terminal functional group of (b) such as an acid anhydride group into the side chain of (a), a method of polymerizing a monomer constituting (a) is used. It can be obtained by copolymerizing the acid anhydride group-containing monomer in the same manner as in the production method of (A). Examples of the method of providing a side chain of (a) with a polymerization initiation group include a method of reacting (a) having the acid anhydride group with hydroperoxide. The styrene-based polymer part (b1) having the reactive functional group at the terminal or side chain can be synthesized by a known method. For example, a compound having a hydroxyl group at the terminal of (b1) is obtained by radically copolymerizing styrene and another monomer (5) copolymerizable therewith in the presence of a chain transfer agent containing a hydroxyl group (such as mercaptoethanol). Can be obtained at. Polyester polymer part (b
The compound having the above-mentioned reactive functional group at the terminal of 2) can be synthesized according to a known method. For example, (b
The compound having a hydroxyl group at the terminal of 2) can be obtained by using an excessive amount of the polyol (f) when polycondensing the polyol (f) and the polycarboxylic acid (ki) constituting (b2). In addition, (b2) having a methacryloyl group at the terminal can be obtained by reacting (b2) having a hydroxyl group at the terminal with methacryloyl isocyanate.

Further, (b2) does not necessarily require polycondensation of the polyol (f) and the polycarboxylic acid (ki) itself, and a derivative of (f) [lower monocarboxylic acid (acetic acid etc.) ester, alcoholate etc.] And the derivative of (g) [lower alcohol (eg, methanol) ester, acid anhydride, acid halide, etc.] may be polycondensed to form the target polyester polymer portion (b2).

In the charge control agent composition of the present invention, an aromatic ring substituted with an organic acid salt (α) and at least one electron-withdrawing group X selected from the group consisting of a halogen atom, a nitro group and a cyano group. The weight ratio with the organic compound (β) having is usually (α) is 1 to 80% by weight and (β) is 20 to 9
9% by weight, preferably 1 to 50% by weight (α), (β)
Is 50 to 99% by weight, more preferably (α) is 2 to 3
0% by weight and (β) are 70 to 98% by weight. If (α) is less than 1% by weight, the rise of charging is insufficient, and if it exceeds 80% by weight, the saturated charge amount is insufficient and the environmental stability is deteriorated.

The charge control agent composition of the present invention can be used as the toner binder composition of the present invention having a charge control ability by premixing with the toner binder before forming a toner. Examples of the toner binder include styrene-based polymers, polyester-based polymers, epoxy-based polymers, polyolefin-based polymers, polyurethane-based polymers, and mixtures thereof, and examples thereof include those known as toner binders. Styrene-based polymers include copolymers of styrene and (meth) acrylic acid ester, copolymers of styrene and diene-based monomers (butadiene, isoprene, etc.), styrene and nitrile-based monomers (acrylonitrile, methacrylonitrile). Etc.), and copolymers of other monomers copolymerizable therewith. As a polyester polymer,
Examples thereof include polycondensates of aromatic dicarboxylic acids and alkylene oxide adducts of bisphenols. Examples of the epoxy polymer include a reaction product of an aromatic diol and epichlorohydrin, and a modified product thereof.
Examples of the polyolefin-based polymer include polyethylene, polypropylene, and a copolymer of ethylene or propylene with another copolymerizable monomer. Examples of the polyurethane polymer include a polyadduct of an aromatic diisocyanate and an alkylene oxide adduct of an aromatic diol.

Examples of the method for producing the toner binder composition of the present invention include the following methods. A method of polymerizing a monomer capable of obtaining each of the toner binders exemplified above in the presence of the charge control agent composition. The toner binder and the charge control agent composition are mixed with a solvent (toluene, xylene or the like aromatic carbonization). Hydrogen; chloroform,
Halides such as ethylene dichloride; acetone,
A method of solution mixing using a ketone such as methyl ethyl ketone; an amide such as dimethylformamide, etc. A method of heat-melting and mixing a toner binder and the charge control agent composition

The charge control agent composition of the present invention can be mixed with a toner binder and a coloring material and used as the electrostatic image developing toner of the present invention. Examples of the toner binder include the same ones as described above. Known pigments and dyes can be used as the coloring material.
Specifically, carbon black, iron black, Sudan black SM, first yellow-G, benzidine yellow,
Pigment Yellow, India First Orange, Irgasin Red, Balanitoaniline Red, Toluidine Red, Carmine FB, Pigment Orange R, Lake Red 2G, Rhodamine FB, Rhodamine B Lake, Methyl Violet B Lake, Phthalocyanine Blue, Pigment Blue, Priliant. Examples include Green, Phthalocyanine Green, Oil Yellow GG, Kayaset YG, Orazol Brown B, and Oil Pink OP.

In the toner binder composition and the toner for developing an electrostatic charge image of the present invention, the weight content of the charge control agent composition relative to the toner binder is usually 0.1 to 2.
It is 0% by weight, preferably 0.3 to 10% by weight. When the weight ratio of the charge control agent composition is less than 0.1% by weight, the amount of charge when used as a toner is low, and when it exceeds 20% by weight, environmental stability when used as a toner is deteriorated. The composition ratio of the toner for developing an electrostatic image of the present invention is based on the weight of the toner, and
The charge control agent composition is 0.1 to 20% by weight, the toner binder is 30 to 95% by weight, the coloring material is 0 to 15% by weight, and if necessary, magnetic powder (ferromagnetic metal such as iron, cobalt and nickel). Powder or a compound such as magnetite, hematite, or ferrite) may also be contained in an amount of 60% by weight or less, which also functions as a coloring material. Further, various additives such as lubricants (polytetrafluoroethylene, low molecular weight polyolefins, fatty acids, and their metal salts or amides) and other charge control agents (metal-containing azo dyes, salicylic acid metal salts, etc.) should be included. You can Further, hydrophobic colloidal silica fine powder or the like can be used to improve the fluidity of the toner. The amount of these additives is usually 10% by weight or less based on the weight of the toner.

The method for obtaining the toner for developing an electrostatic charge image of the present invention is not particularly limited, but it can be obtained by the following method. Kneading / Pulverizing Method After dry-blending the components constituting the toner, they are melt-kneaded, then coarsely pulverized, and finally pulverized using a jet pulverizer or the like. Further classification is performed to obtain fine particles having a particle size of usually 5 to 20 μm to obtain a toner. External Addition Method After dry blending the charge control agent of the present invention with the toner binder, the coloring material and, if necessary, the base particles having a particle size of 5 to 20 μm, which are composed of the lubricant and the magnetic powder, and then strongly mixing with a mixer while heating if necessary. By doing so, the toner adheres to the base particles to obtain the toner. Polymerization method The charge control agent, the coloring material and the like of the present invention are dispersed and dissolved in the monomer of the toner binder raw material, and then the suspension polymerization is carried out in water and then dried to obtain fine particles having a particle size of usually 5 to 20 μm. Get toner.

The toner for developing an electrostatic charge image of the present invention contains iron powder, glass beads, nickel powder, ferrite, and
It is used as a developer for an electric latent image by being mixed with magnetite and carrier particles such as ferrite whose surface is coated with a resin (acrylic resin, silicone resin, etc.). In addition, instead of the carrier particles, friction with a member such as a charging blade can be performed to form an electric latent image. The electrostatic image developing toner of the present invention is fixed on a support (paper, polyester film, or the like) by a copying machine, a printer, or the like to form a recording material. As a method for fixing to a support, a known hot roll fixing method, flash fixing method, or the like can be applied.

The charge control agent of the present invention can also be used in wet toners, powder coatings and the like.

[0041]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be further described with reference to the following examples, but the present invention is not limited thereto. Hereinafter, parts are parts by weight.

[0042]

【Example】

Example A1 552 parts of m-nitrophenylmaleimide and perfluoroalkylethylmethacrylate {cheminox FA
MAC-C8: manufactured by Nippon Mektron Co., Ltd.} 448 parts were copolymerized in dimethylformamide (DMF) at a boiling point for 8 hours using ditertiary butyl peroxide as an initiator. Then, 100 parts of sodium perfluorooctanesulfonate was added and dissolved, and then DMF was distilled off by a reduced pressure dryer to obtain a charge control agent composition (A1) of the present invention.

Example A2 476 parts of 3,4-dichlorophenylmaleimide and 524 parts of perfluoroalkylethyl methacrylate were copolymerized in the same manner as in Example A1. Then, 200 parts of sodium perfluorooctanesulfonate was added and dissolved and desolvated in the same manner as in Example A1 to obtain the charge control agent composition (A
2) was obtained.

Example A3 In the presence of 500 parts of the charge control agent composition (A2), 500 parts of styrene was graft-polymerized in DMF at 180 ° C. for 4 hours using ditertiary butyl peroxide as an initiator, and then DMF was dried under reduced pressure. Was distilled off to obtain a charge control agent composition (A3) of the present invention.

Example A4 1,000 parts of 3,4-dichlorophenylmaleimide were polymerized in the same manner as in Example A1 and then 200 parts of barium perfluorooctanesulfonate was added to dissolve and desolvate in the same manner as in Example A1 to prepare the present invention. A charge control agent composition (A4) was obtained.

Example A5 Perfluoroalkylethyl acrylate {FLUOW
ET AC 812: Hoechst Industry Co., Ltd.} 5
11 parts and 223 parts of itaconic anhydride were copolymerized in methyl ethyl ketone (MEK) with 50 parts of azobisvaleronitrile as an initiator for 4 hours to give a weight average molecular weight of 18,000.
0 copolymer (1) was obtained. MEK was added to 1000 parts of styrene in the presence of 734 parts of the copolymer (1) in an autoclave.
Graft polymerization was carried out at 180 ° C. in the presence of ditertiarybutyl peroxide for 4 hours, and MEK was then distilled off in a vacuum dryer to obtain a graft polymer (1). Next, 299 parts of 3,4-dichloroaniline was added to 1734 parts of the graft polymer (1), and an imidization reaction was carried out in DMF at a boiling point for 8 hours. Then, 150 parts of sodium perfluorooctanesulfonate was added and dissolved, and DMF was distilled off to obtain a charge control agent composition (A5) of the present invention.

Example A6 Bisphenol A Propylene oxide 2 mol adduct 7
23 parts and 348 parts of terephthalic acid were polycondensed at 230 ° C. using 2 parts of dibutyltin oxide as a catalyst to obtain a polyester polymer (1) having a weight average molecular weight of 6,000 and a hydroxyl value of 20 mgKOH / g. 734 parts of the copolymer (1) obtained in Example A5 and 1000 of the polyester polymer (1)
A part was esterified in MEK at 160 ° C., and MEK was then distilled off under reduced pressure to obtain a graft polymer (2).
Then, 1734 parts of the graft polymer (2) and 299 parts of 3,4-dichloroaniline were reacted in the same manner as in Example A5. Then, 150 parts of sodium perfluorooctanesulfonate was added and dissolved and desolvated in the same manner as in Example A5 to obtain a charge control agent composition (A6) of the present invention.

Example A7 Methyl vinyl ether / maleic anhydride alternating copolymer {VEMA-A101: manufactured by Daicel Chemical Industries Ltd.} 36
To 9 parts of 413 parts of perfluoroalkyl ethanol {Chemox FA-M: manufactured by Nippon Mektron Co., Ltd.} was esterified in MEK at 160 ° C. to obtain a copolymer (2). Copolymer (2) (782 parts) was mixed with styrene 1000 in the same manner as in Example A5.
A part was grafted to obtain a graft polymer (3). Then
1782 parts of the graft polymer (3) was reacted with 244 parts of 3,4-dichloroaniline in the same manner as in Example A5. Thereafter, 200 parts of calcium perfluorooctanesulfonate was added and dissolved and desolvated in the same manner as in Example A5 to obtain the charge control agent composition (A7) of the present invention.

Example A8 782 parts of the copolymer (2) obtained in Example A7 and 1000 parts of the polyester polymer (1) were reacted in the same manner as in Example A6 to obtain a graft polymer (4). . Then, 1782 parts of the graft polymer (4) was reacted with 244 parts of 3,4-dichloroaniline in the same manner as in Example A5. Thereafter, 200 parts of calcium perfluorooctane sulfonate was added and dissolved and desolvated in the same manner as in Example A5 to obtain the charge control agent composition (A
8) was obtained.

Example A9 460 parts of dichlorophenylmaleimide, 500 parts of perfluoroalkylethyl methacrylate and 40 parts of sodium styrenesulfonate were copolymerized in the same manner as in Example A1 to obtain a DMF solution (A9 ') of the copolymer. Then, 75 parts of sodium perfluorooctane sulfonate was added and dissolved and desolvated in the same manner as in Example A1 to obtain the charge control agent composition (A9) of the present invention.

Example A10 DMF solution (A9 ') of the copolymer obtained in Example A9
Sodium trifluoromethanesulfonate (30 parts) was added thereto, and the mixture was dissolved and desolvated in the same manner as in Example A1 to obtain the charge control agent composition (A10) of the present invention.

Example A11 DMF solution (A9 ') of the copolymer obtained in Example A9
50 parts of sodium octylbenzenesulfonate was added to and dissolved and desolvated in the same manner as in Example A1 to obtain the charge control agent composition (A11) of the present invention.

Comparative Example CA1 A comparative charge control agent (CA1) was obtained in the same manner as in Example A1 except that 100 parts of sodium perfluorooctanesulfonate was not added.

Comparative Example CA2 Sodium perfluorooctane sulfonate is used as a comparative charge control agent (CA2).

Comparative Example CA3 Perfluoroalkylethylmethacrylate {Chemox FAMAC-C8: Nippon Mektron Co., Ltd.} 100
0 part was polymerized in toluene under boiling point using azobisisobutyronitrile as an initiator to obtain a comparative charge control agent (CA3).

Comparative Example CA4 920 parts of styrene and 80 parts of 2-acrylamido-2-methylpropanesulfonic acid were copolymerized in a mixed solvent of toluene / methanol with azobisisobutyronitrile as an initiator for 8 hours, and then dried under reduced pressure to remove the solvent. Was distilled off to obtain a comparative charge control agent (CA4).

Comparative Example CA5 912 parts of styrene and 88 parts of sodium styrenesulfonate were copolymerized in DMF at a boiling point for 4 hours by using azobisisobutyronitrile as an initiator, and then DMF was distilled off by a vacuum dryer to give a comparative charge. A control agent (CA5) was obtained.

Example B1 20 parts of the charge control agent composition (A3) and 1000 parts of a styrene-based toner binder {HYMER UNI-3000: manufactured by Sanyo Chemical Industry Co., Ltd.} were dissolved and mixed in DMF, and DMF was distilled off. A toner binder composition (B1) of the invention was obtained.

Examples T1 to T10 and Comparative Examples CT1 to
CT8 A charge control agent composition having the composition shown in Table 1 and a styrene-based toner binder {Haimer UNI-3000, Sanyo Chemical Industry Co., Ltd.
1000 parts, carbon black {MA-100, manufactured by Mitsubishi Kasei Co., Ltd.} 80 parts and low molecular weight polypropylene {Viscole 660P, manufactured by Sanyo Chemical Co., Ltd.} 40 parts were made into toner by the following method. First, a Henschel mixer {FM10B, manufactured by Mitsui Miike Kakoki Co., Ltd.} was premixed, and then kneaded by a biaxial kneader {PCM-30, manufactured by Ikegai Co., Ltd.}. Then, after finely pulverizing using a supersonic jet crusher Labo Jet {manufactured by Nippon Pneumatic Mfg. Co., Ltd.}, an air stream classifier {MDS-I, Nippon Pneumatic Mfg. Co., Ltd.
Co., Ltd.} to obtain powder having a particle size of 5 to 20 μm,
Toners (T1) to (T10) of the present invention and comparative toners (CT1) to (CT8) were obtained. Table 1 shows the evaluation results.

Example T11 The toner of the present invention (toner of the present invention was prepared in the same manner as in Example T1 except that 1020 parts of the toner binder composition (B1) of the present invention was used in place of Hymer UNI-3000 and no charge control agent was added. T11) was obtained. Table 1 shows the evaluation results.

[0061]

[Table 1] Evaluation results ------------------------------------------ Toner name Charge control agent Saturation charge amount Standing environment Charge Amount Copy No No. of added parts (μC / g) Increase Dependency distribution test −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− (T1 ) (A1) 10 parts -22 B A B A (T2) (A2) 10 parts -19 A A B A (T3) (A3) 10 parts -16 B A A B (T4) (A3) 20 parts -20 A A A A (T5) (A4) 10 parts -19 A A B B (T6) (A5) 20 parts -20 A A A A A (T7) (A7) 30 parts -19 A A A A A (T8) ( A9) 10 parts −19 A A A A A (T9) (A10) 10 parts −18 A B A A A (T10) (A11) 10 parts −20 B B A B −−−−−−− −−−−−−−−−−−−−−−−−−−−− (T11) (B1) 1020 parts −19 A A A A −−−−−−−−−−−−−−−− −−−−−−−−−−−−−−−−−− (CT1) not added −9 D C B D D (CT2) (CA1) 10 parts −25 C A B C (CT3) (CA2) 10 Part -11 AC BD (CT4) (CA3) 10 parts -10 C B B D (CT5) (CA4) 20 parts -13 D C A D (CT6) (CA4) 50 parts -18 C C AC ( CT7) (CA3) 10 parts combined use (CA4) 50 parts -17 C CC B C (CT8) (CA5) 10 parts -11 C C B D ------------------. Note: (CT7) is a combination of (CA3) and (CA4) as charge control agents.

(Evaluation Method) Preparation of Developer 1 part of toner and 24 parts of silicone resin-coated ferrite carrier for developing electrostatic image {FL961-150, manufactured by Powder Tech Co., Ltd.} are mixed to prepare a developer. did. Measurement of Saturated Charge Amount (Charge Amount) H. After adjusting the humidity for 8 hours or more, use a tumbler shaker mixer at 50 rpm.
× 1, 3, 7, 20, 60 and 120 minutes of friction stirring, and the charge amount was measured at each time. The charge amount during the friction time when the increase in the charge amount was stopped was defined as the saturation charge amount. Measuring device: Blow-off charge amount measuring device @ Toshiba Chemical
Evaluation standard for rising (rising) of charging The following criteria were used for evaluation based on the results of measuring the amount of charging. A: Friction time to reach a charge amount of 80% of saturated charge amount is less than 7 minutes B: Friction time to reach a charge amount of 80% of saturated charge amount is 7 to 20 minutes (usable level) C: 20 to 60 minutes of friction time to reach 80% of the saturated charge amount D: 60 to 60 minutes of friction time to reach 80% of the saturated charge amount Environmental stability measurement The charge amount of the developer was measured after the humidity was adjusted at high temperature and high humidity and low temperature and low humidity for 8 hours or more. Low temperature and low humidity: 10 ° C, 40% R. H. High temperature and high humidity: 35 ° C, 85% R. H. Evaluation Criteria A: Small changes in charge amount at low temperature and low humidity and high temperature and high humidity B: Medium changes in charge amount at low temperature and low humidity and high temperature and high humidity (usable level) C: Low temperature and low humidity Change in charge amount at high temperature and high humidity Measurement of charge amount distribution H. After adjusting the humidity for 8 hours or more, use a tumbler shaker mixer at 50 rpm.
The mixture was friction-stirred for 20 minutes, and the charge amount distribution was measured. Device: Particle charge distribution measuring device {EST-1, manufactured by Hosokawa Micron Co., Ltd.} Evaluation criteria A: Charge distribution is particularly narrow B: Charge distribution is medium (usable level) C: Charge distribution Wide range Copy test A continuous copy test was carried out on the above developer using a copying machine for evaluation. Evaluator: Electrophotographic copying machine for toner using negative charge toner using selenium photoconductor Continuous copying number: 20,000 Evaluation criteria A: 20,000 sheets Good image after continuous copying B: 20,000 sheets after continuous copying, Image quality is slightly degraded C: Image quality degradation is clearly seen after continuous copying of 20,000 sheets D: Image defect from the beginning of copying

Examples T12 to T15 (Synthesis of Toner Binder) 751 parts of bisphenol A propylene oxide 2 mol adduct, terephthalic acid 10
4 parts and 167 parts of trimellitic anhydride are polycondensed using 2 parts of dibutyltin oxide as a catalyst, and have a softening point of 127 ° C.
A polyester-based toner binder (2) was obtained. (Preparation and Evaluation of Toners) Toners (T12) to (T15) of the present invention were prepared by converting the toners into the toners of Table 2 in the same manner as in Example T1 except that the toner binder was changed to the polyester toner binder (2). Obtained. Table 2 shows the evaluation results.

[0064]

[Table 2] Evaluation results --------------------------------------- Toner name Charge control agent Saturation charge amount Standing environment Charge Amount Copy No No. of added parts (μC / g) Increase Dependence distribution test −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− (T12 ) (A2) 10 parts -18 A A B A (T13) (A5) 20 parts -20 A A BB B (T14) (A6) 20 parts -21 A A A A (T15) (A8) 30 parts -19 A A A A A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A A A A A A A A A A A A A A A A -----

[0065]

The charge control agent composition, toner binder composition and toner for developing an electrostatic image of the present invention have the following effects. 1. Excellent safety because it does not contain heavy metals. 2. Since the charge control agent composition is weakly colored, the color tone of the color toner is excellent. 3. The charge control agent composition has high dispersibility and a toner having a sharp charge amount distribution can be obtained. 4. The charge control agent composition has a high charge amount, and a toner having an appropriate charge amount can be obtained by using a small amount of the charge control agent. 5. It is possible to obtain a toner which is excellent in charge rising and reaches a fixed charge amount by short-time friction. 6. It is possible to obtain a toner which is excellent in environmental dependency and has a small change in the charge amount even under various environments. 7. A toner that stably retains a clear image with little fog even after long continuous copying is obtained. 8. When used as a powder coating material, a coating material having excellent chargeability and excellent color tone can be obtained as in the case of the toners 2 to 7.

Front page continuation (72) Inventor Toru Ohama 1-11, Hitotsubashi-honmachi, Higashiyama-ku, Kyoto Sanyo Kasei Kogyo Co., Ltd.

Claims (13)

[Claims] 1. An organic acid salt (α) and an organic compound (β) having an aromatic ring substituted with at least one electron-withdrawing group X selected from the group consisting of a halogen atom, a nitro group and a cyano group. A charge control agent composition comprising as an essential constituent. 2. A polymerizable monomer (a) wherein (β) has an aromatic ring substituted with at least one electron-withdrawing group X selected from the group consisting of halogen atom, nitro group and cyano group.
A polymer (A) containing as a constituent unit.
The charge control agent composition described. 3. The charge control agent composition according to claim 2, wherein (a) is a phenylmaleimide substituent or an phenylitaconimide substituent in which an aromatic ring is substituted with an electron-withdrawing group X. 4. (A) is a polymerizable monomer (a) further containing a perfluoroalkyl group and / or a silicone group.
The charge control agent composition according to claim 2 or 3, which is a copolymer containing as a constituent unit. 5. The polymerizable monomer selected from the group consisting of (a) perfluoroalkyl group-containing (meth) acrylate, perfluoroalkyl group-containing maleate, and perfluoroalkyl group-containing itaconate as set forth in (4). The charge control agent composition of. 6. The composition according to claim 2, wherein (A) is a copolymer containing the monomer (A) and the sulfo group-containing polymerizable monomer (C) as constituent units. Charge control agent composition. 7. (A) constitutes the monomer (a), a perfluoroalkyl group- and / or silicone group-containing polymerizable monomer (a) and a sulfo group-containing polymerizable monomer (c). The charge control agent composition according to any one of claims 2 to 6, which is a copolymer contained as a unit. 8. A styrene-based polymer portion (b1) and a polyester-based polymer portion (b2) are added to the polymer portion (a) having the same constitution as that of the copolymer (A) according to any one of claims 2 to 7. A copolymer (AB) in which a polymer portion (b) selected from the group consisting of
(Β), and an organic acid salt (α) as essential constituents. 9. The charge control agent composition according to claim 1, wherein (α) is a perfluoroalkyl group-containing organic acid salt. 10. The charge control agent composition according to claim 1, wherein (α) is a sulfonate containing a perfluoroalkyl group. 11. The weight ratio of (α) / (β) is 1/99.
The charge control agent composition according to any one of claims 1 to 10, wherein the charge control agent composition is -80/20. 12. A toner binder composition comprising a toner binder and the charge control agent composition according to any one of claims 1 to 11. 13. An electrostatic charge image developing toner containing a toner binder, a coloring material and a charge control agent, which comprises the charge control agent composition according to any one of claims 1 to 12. Toner for image development.