JPH09171271A - Electric charge controlling agent, toner binder composition and toner for developing electrostatic charge image - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a colorless electric charge controlling agent contg. no heavymetal, ensuring a sufficiently large quantity of electric charges and rapid kick-off of electrostatic charge even in the case of a small amt. and excellent also in environmental stability by using a copolymer contg. a specified polymerizable monomer and a polymerizable monomer having a sulfo group as constituent units. SOLUTION: This electric charge controlling agent is made of a copolymer contg. a polymerizable monomer having an arom. ring substd. by one or more kinds of electron withdrawing groups selected from among halogen, nitro, cyano and perfluoroalkyl and a polymerizable monomer having a sulfa group as constituent units or a copolymer obtd. by bonding a styrene or polyester polymer part to a polymer part having the same structure as the above-mentioned copolymer by graft or block bonding. The objective toner binder compsn. contains a toner binder and the electric charge controlling agent is obtd.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a charge control agent, a toner binder composition containing the same, and a toner for developing an electrostatic image. More specifically, it relates to a negatively chargeable charge control agent, 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. Combined use of acrylamide sulfonic acid copolymer (JP-A-6-230609), methyl methacrylate / methacrylic acid block copolymer (USP)
No. 4,925,765).

[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 characteristics (low temperature fixing property, hot offset resistance) and the like. Furthermore, these compounds have large changes in the temperature and humidity of the charge amount, and have insufficient environmental stability.

[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] A polymerizable monomer (1) 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, a cyano group and a perfluoroalkyl group, and a sulfo group A charge control agent comprising a copolymer (A) containing a polymerizable monomer (2) as a constituent unit. [1 ′] From the group consisting of a styrene-based polymer portion (b1) and a polyester-based polymer portion (b2) in the polymer portion (a) having the same constitution as the copolymer (A) described in [1] above. A charge control agent comprising a copolymer (AB) in which a selected polymer portion (b) is bonded in a graft or block form. [2] A toner binder composition comprising a toner binder and the charge control agent according to [1] or [1 ′]. [3] In a toner for developing an electrostatic image containing a toner binder, a coloring material and a charge control agent, the charge control agent is
A toner for developing an electrostatic charge image, which is the charge control agent as described in [1] or [1 '].

In the present invention, the electron withdrawing group X is a halogen atom (chlorine atom, bromine atom, iodine atom, fluorine atom), nitro group, cyano group, perfluoroalkyl group (trifluoromethyl group, pentafluoroethyl group, C
3 to C14 perfluoroalkyl group). Among these, preferred are a halogen atom and a nitro group, a cyano group and a trifluoromethyl group, more preferred are a halogen atom, a nitro group and a cyano group, and further preferred are a halogen atom and a nitro group. And particularly preferred are chlorine atom and nitro group. Examples of the polymerizable monomer (1) having an aromatic ring substituted with an electron-withdrawing group X include styrene substitution products (chlorostyrene, dichlorostyrene, bromostyrene, fluorostyrene, nitrostyrene, cyanostyrene, trifluoromethylstyrene, etc. ), Phenyl (meth) acrylate substitution product [chlorophenyl (meth) acrylate, bromophenyl (meth) acrylate, nitrophenyl (meth) acrylate, chlorophenyloxyethyl (meth) acrylate, bromophenyloxyethyl (meth) acrylate, nitrophenyloxy Ethyl (meth) acrylate, etc., phenyl (meth) acrylamide substitution product [chlorophenyl (meth) acrylamide, bromophenyl (meth) acrylamide, nitrophenyl (meth) acrylamide, etc. , Phenylmaleimide substitution products (chlorophenylmaleimide, dichlorophenylmaleimide, nitrophenylmaleimide, nitrochlorophenylmaleimide, trifluoromethylphenylmaleimide, etc.), phenylitaconimide substitution products (chlorophenylitaconimide, dichlorophenylitaconimide, nitrophenylitaconimide, nitrochlorophenylitacone) Imide, trifluoromethylphenylitaconimide, etc.), phenyl vinyl ether substitution products (chlorophenyl vinyl ether, nitrophenyl vinyl ether, etc.) and the like. Of these, preferred are styrene-substituted products, acrylamide-substituted products, phenylmaleimide-substituted products and phenylitaconimide-substituted products, and particularly preferred are phenylmaleimide-substituted products and phenylitaconimide-substituted products.

Examples of the sulfo group-containing polymerizable monomer (2) include a sulfonic acid group-containing polymerizable monomer (2-1) and a sulfonate group-containing polymerizable monomer (2-2).
Examples of (2-1) include an aromatic sulfonic acid group-containing polymerizable monomer (2-1a) and an aliphatic sulfonic acid group-containing polymerizable monomer (2-1b). Examples of (2-1a) include styrenesulfonic acid, sulfophenylacrylamide, sulfophenylmaleimide and sulfophenylitaconimide. Examples of (2-1b) include vinyl sulfonic acid, allyl sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid and methacryloyloxyethyl sulfonic acid. Examples of (2-2) include an aromatic sulfonate group-containing polymerizable monomer (2-2a) and an aliphatic sulfonate group-containing polymerizable monomer (2-2b). (2-2a) includes alkali metal (lithium, sodium, potassium, etc.) salts of (2-1a), alkaline earth metal (magnesium, calcium, barium, etc.)
Examples thereof include salts, amines (triethylamine, tributylamine, dimethylbenzylamine, etc.) salts and quaternary ammonium salts (tributylbenzylammonium salt, tetraethylammonium salt, tetrabutylammonium salt, etc.). Examples of (2-2b) include salts similar to the above (2-2a) of (2-1b). Among these (2), the preferable one is (2-2), the more preferable one is (2-2a), and the particularly preferable one is the alkali metal of the aromatic sulfonic acid group-containing polymerizable monomer. , Alkaline earth metal and amine salts. Heavy metal (nickel,
Salts of copper, zinc, mercury, chromium, etc. are not preferable in terms of safety.

In the present invention, the polymer (A) is a copolymer of the polymerizable monomer (1) having an aromatic ring substituted by the electron withdrawing group X and the sulfo group-containing polymerizable monomer (2). Although it may be a combination, it may be a copolymer with a perfluoroalkyl group- and / or silicone group-containing polymerizable monomer (3). Further, it may be a copolymer with at least one other monomer (4) copolymerizable therewith.
Copolymerization of (3) is particularly preferable because a toner having a high charge amount and a quick rise can be obtained with a small amount of addition, and the environmental stability is improved.

The perfluoroalkyl group- and / or silicone group-containing polymerizable monomer (3) includes perfluoroalkyl group-containing monomer (3-1) and silicone group-containing monomer (3-2). Can be mentioned. Examples of the perfluoroalkyl group-containing monomer (3-1) include perfluoroalkylethylene, perfluoroalkylethyl (meth) acrylate, mono (perfluoroalkylethyl) maleate and mono (perfluoroalkylethyl) itaconate. To be Silicone group-containing monomer (3
Examples of -2) include silicone oils modified with terminal hydroxyl groups and esters of (meth) acrylic acid or maleic acid. Preferred among these (3) are (3-1)
And a particularly preferable one is (3-1) in which the perfluoroalkyl group has 8 to 16 carbon atoms.

Other monomers (4) include olefins (ethylene, propylene, 1-butene, isobutylene, dodecene, etc.), vinyl ethers (methyl vinyl ether,
Butyl vinyl ether, stearyl vinyl ether, etc.), aromatic vinyl hydrocarbons (styrene, α-methylstyrene, p-cumylstyrene, etc.), (meth) acrylic acid, (meth) acrylic acid ester (methyl (meth) acrylate, (meth)) Examples thereof include ethyl acrylate, butyl (meth) acrylate, stearyl (meth) acrylate, etc., dienes (butadiene, isoprene, etc.), unsaturated dicarboxylic acids (maleic acid, itaconic acid, etc.), and acid anhydrides thereof.

The proportion of each structural unit in the polymer (A) is as follows: (1) is usually 10% by weight or more, preferably 10% by weight.
˜99% by weight, more preferably 20 to 70% by weight. (2) is usually 0.1 to 20% by weight, preferably 1
10 to 10% by weight. (3) is usually 0 to 90% by weight,
Preferably 1 to 90% by weight, more preferably 10 to 7
0% by weight. (4) is usually 0 to 95% by weight, preferably 0 to 50% by weight, more preferably 0 to 30% by weight. If the ratio of (1) is less than 10% by weight, the charge amount will be insufficient. Further, if the proportion of (2) is less than 0.1% by weight, the rise of charging becomes poor, and if it exceeds 20% by weight, the environmental stability becomes poor.

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-based polymer portion (b1) may be a homopolymer of styrene or a copolymer with another monomer (5) copolymerizable with styrene. Other copolymerizable monomers (5) include aromatic vinyl hydrocarbons other than styrene, (meth) acrylic monomers, nitrile monomers and other vinyl monomers. Examples of aromatic vinyl hydrocarbons other than styrene include alkyl-substituted styrenes (α-methylstyrene, p-methylstyrene, p-cumylstyrene, etc.), acetoxystyrene, hydroxystyrene and the like. Examples of the (meth) acrylic monomer include alkyl (meth) acrylate [methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth).
Acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate and the like]; hydroxyl group-containing (meth) acrylate [hydroxyethyl (meth) acrylate and the like]; epoxy group-containing (meth) acrylate [glycidyl (meth) acrylate and the like]; isocyanate Group-containing (meth) acrylates [methacryloyl isocyanate, etc.] and the like can be mentioned. Examples of the nitrile-based monomer include acrylonitrile and methacrylonitrile. Other vinyl monomers include vinyl esters (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, cinnamic 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 (5) is usually 40 mol% or more, preferably 60 mol% or more.

In the present invention, examples of the polyester polymer portion (b2) include polycondensates of polyol (6) and polycarboxylic acid (7). Examples of the polyol (6) include a diol (6-1) and a polyol (6-2) having 3 or more valences, (6-1) alone or (6)
A mixture of -1) and a small amount of (6-2) is preferred. Diol
Examples of (6-1) include alkylene glycols (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, etc.); alkylene ether glycols (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, 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 the trihydric or higher polyol (6-2) 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. Polycarboxylic acid (7)
Examples thereof include dicarboxylic acid (7-1) and tricarboxylic or higher polycarboxylic acid (7-2), and a mixture of (7-1) and (7-1) with a small amount of (7-2) is preferable. . Examples of the dicarboxylic acid (7-1) include alkylenedicarboxylic acid (succinic acid, adipic acid, sebacic acid, etc.); alkenylene dicarboxylic acid (maleic acid, fumaric acid, etc.); aromatic dicarboxylic acid (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. 3
As the polycarboxylic acid having a valence of 7 or more, the carbon number is 9 to 2
Examples thereof include aromatic polycarboxylic acids of 0 (trimellitic acid, pyromellitic acid, etc.). The molar ratio of (6) and (7) 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 (6-1) and (6-2) in (6) is usually 100:
It is 0 to 80:20, preferably 100: 0 to 90:10. The preferable molar ratio of (7-1) and (7-2) in (7) is also
It is the same as the molar ratio of (6-1) and (6-2). Also, (B1)
And preferred as (B2) are the same as (b1) and (b2).

The weight ratio of (AB), (A) and (B) in the charge control agent when they are combined in a graft or block form is usually such that (AB) is 1 to 100% by weight, (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.

The method of bonding the copolymer (AB) in which (a) and (b) are bonded in a graft form and / or a block form is 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 following. (1) Nitrophenylmaleimide / perfluoroalkyl (mixture of C8 to C12) ethyl methacrylate / 2
-Acrylamido-2-methylpropanesulfonic acid
(51/41/8) Copolymer (2) Chlorophenylmaleimide / perfluoroalkyl (mixture of C8 to C12) ethyl acrylate / sodium styrenesulfonate (50/45/5) copolymer
Body (3) Dichlorophenyl maleimide / styrene sulfonic acid sodium salt (96/4) copolymer (4) Dichlorophenyl maleimide / perfluoroalkyl (mixture of C8 to C12) ethyl methacrylate /
Styrene sulfonic acid sodium salt (46/50/4) copolymer (5) dichlorophenyl maleimide / perfluoroalkyl (mixture of C8 to C12) ethyl methacrylate /
Styrene sulfonic acid tributylamine salt (45/50 /
5) Copolymer (6) Dichlorophenylitaconimide / perfluoroalkyl (mixture of C8 to C12) ethyl acrylate / styrene sulfonic acid magnesium salt (65/30 /
5) Copolymer (7) Dichlorophenylitaconimide / perfluoroalkyl (mixture of C8 to C12) ethyl acrylate / sulfophenyl maleimide sodium salt (56/40)
/ 4) Copolymer (8) Dichlorophenyl maleimide / monoperfluoroalkyl (mixture of C8 to C12) ethyl maleate /
Sulfophenyl maleimide sodium salt / methyl vinyl ether (39/42/5/14) copolymer

Specific examples of the copolymer (AB) include a portion having the same constitution 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 polycondensation (8) Bisphenol A propylene oxide 2 mol adduct / terephthalic acid polycondensate part (9) Bisphenol A ethylene oxide 2 mol adduct / maleic acid polycondensate part (10) Bisphenol A propylene oxide 3 mol adduct / Maleic acid polycondensate part (11) Bisphenol A ethylene oxide 3 mol adduct / terephthalic 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,
(1) and (2) may be copolymerized with azobisisobutyronitrile as an initiator, or it may be obtained by copolymerizing itaconic anhydride and (2) and then reacting with aniline substituted by X. To be 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 (2) having a hydroxyl group at the terminal can be obtained by excessively using the polyol (7) when polycondensing the polyol (7) constituting the component (b2) with the polycarboxylic acid (8). 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) is not necessarily a polyol.
It is not necessary to polycondense (7) and polycarboxylic acid (8) itself, and the derivative of (7) [lower monocarboxylic acid (acetic acid, etc.)
Ester, alcoholate, etc.] and the derivative (8) [lower alcohol (methanol, etc.) ester, acid anhydride, acid halide, etc.] may be polycondensed to obtain the target polyester polymer portion (b2).

The charge control agent of the present invention can be mixed with a toner binder in advance before forming a toner and used as the toner binder composition of the present invention having a charge control ability. Styrene-based polymer as toner binder,
Known examples of toner binders include polyester-based polymers, epoxy-based polymers, polyolefin-based polymers, polyurethane-based polymers, and mixtures thereof. 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. Examples of the polyester-based polymer include a polycondensate of an aromatic dicarboxylic acid and an alkylene oxide adduct of a bisphenol. 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. A toner (toluene,
Solution mixing using aromatic hydrocarbons such as xylene, halides such as chloroform and ethylene dichloride, ketones such as acetone and methyl ethyl ketone, and amides such as dimethylformamide). Melting and mixing the toner binder and the charge control agent. Method

The charge control agent of the present invention is a toner binder,
It can be mixed with a coloring material and used as the toner for developing an electrostatic image 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 S
M, First Yellow-G, Benzidine Yellow, Pigment Yellow, India First Orange, Irgasine 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 green, phthalocyanine green, oil yellow GG, Kayaset YG, orazole brown B, oil pink OP and the like can be mentioned.

In the electrostatic image developing toner of the present invention, it is preferable that at least a part of the toner binder forms a continuous phase and at least a part of the charge control agent forms a discontinuous domain. . Compared with the case where the charge control agent is completely compatible in the toner binder without forming discontinuous domains, the added charge control agent is more likely to be exposed on the toner surface, and the effect is exhibited by adding a small amount.
The dispersed particle size of the domain is preferably 0.01 to
It is 4 μm, and more preferably 0.05 to 2 μm. When it exceeds 4 μm, the dispersibility is insufficient and the problem that the charge amount distribution becomes wide occurs. Further, in the case of being used for a color toner, it is preferable that the dispersed particle diameter is smaller from the viewpoint of transparency, and the dispersed particle diameter is preferably 0.01 to 1 μm. When the dispersed particle size is less than 0.01 μm, it is similar to the case where the particles are completely compatible with each other in the toner binder without forming discontinuous domains, and it is necessary to add a large amount of the charge control agent. The fact that at least a part of the charge control agent forms a discontinuous domain and the dispersed particle size thereof can be confirmed by observing a section of the toner with a transmission electron microscope or the like. In order to observe the interface clearly, it is also effective to observe the interface with an electron microscope after dyeing the toner section with ruthenium tetroxide, osmium tetroxide, or the like.

In the toner binder composition and the toner for developing an electrostatic image of the present invention, the weight ratio of the toner binder to the charge control agent is usually 0.1 to 20% by weight, preferably 0.3 to 10% by weight. is there. When the weight ratio of the charge control agent is less than 0.1% by weight, the charge amount when used as a toner is low, and when it exceeds 20% by weight, the environmental stability when used as a toner is deteriorated. The composition ratio of the toner for developing an electrostatic charge image of the present invention is based on the weight of the toner.
1 to 20% by weight, toner binder 30 to 95% by weight, coloring material 0 to 15% by weight, magnetic powder (ferromagnetic metal powder such as iron, cobalt, nickel or magnetite, hematite, ferrite, etc.) as required. 60% by weight or less may also be included, which also functions as a coloring material. In addition, various additives such as lubricants (polytetrafluoroethylene, low molecular weight polyolefins, fatty acids, or 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 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. After further classification, the toner is obtained as fine particles having a particle size of usually 5 to 20 microns. External Addition Method After dry-blending the charge control agent of the present invention with particles having a particle size of 5 to 20 microns comprising a toner binder, a coloring material, and, if necessary, a lubricant and a magnetic powder, the mixture is intensively mixed with a mixer while heating as necessary. As a result, a toner can be obtained by external addition. Polymerization method The charge control agent and the coloring material of the present invention are dispersed and dissolved in the monomer of the toner binder raw material, then suspended and polymerized in water, and then dried. Is obtained.

The electrostatic image developing toner of the present invention comprises carrier particles such as iron powder, glass beads, nickel powder, ferrite, magnetite, and ferrite whose surface is coated with a resin (acrylic resin, silicone resin, etc.) as required. And is used as a developer for an electric latent image. 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.

[0033]

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.

[0034]

【Example】

Example A1 508 parts of m-nitrophenylmaleimide, perfluoroalkylethylmethacrylate {cheminox FAMA
C-C8: Nippon Mektron KK} 412 parts and 2-acrylamido-2-methylpropanesulfonic acid 80 parts,
Copolymerization was carried out for 8 hours using ditertiary butyl peroxide as an initiator in DMF at a boiling point, and then DMF was distilled off by a vacuum dryer to obtain a charge control agent (A1) of the present invention.

Example A2 3,4-dichlorophenylmaleimide (457 parts), perfluoroalkylethyl methacrylate (503 parts) and sodium styrenesulfonate (40 parts) were copolymerized in the same manner as in Example A1 to give the charge control agent (A2) of the present invention. Obtained.

Example A3 500 styrene in the presence of 500 parts of charge control agent (A2)
Parts were graft-polymerized in DMF at 180 ° C. for 4 hours with ditert-butyl peroxide as an initiator, and then D
MF was distilled off by a vacuum dryer to obtain the charge control agent (A3) of the present invention.

Example A4 960 parts of 3,4-dichlorophenylmaleimide and 40 parts of sodium styrenesulfonate were copolymerized in the same manner as in Example A1 to obtain a charge control agent (A4) of the present invention.

Example A5 Perfluoroalkylethyl acrylate {FLUOW
ET AC 812: Hoechst Industry Co., Ltd.} 5
11 parts and 223 parts of itaconic anhydride were copolymerized in MEK with 50 parts of azobisvaleronitrile as an initiator for 4 hours to obtain a copolymer (1) having a weight average molecular weight of 18,000.
In the presence of 734 parts of the copolymer (1) in an autoclave,
1000 parts of styrene was graft-polymerized in MEK at 180 ° C. for 4 hours by using ditertiary butyl peroxide as an initiator, and then MEK was distilled off by a vacuum dryer to obtain a graft polymer (1). Then, graft polymer (1) 173
To 4 parts, 262 parts of 3,4-dichloroaniline and 37 parts of sodium p-aminobenzenesulfonate were added, and DMF was added.
Imidization reaction was carried out at a medium boiling point for 8 hours, and then DMF was distilled off to obtain a charge control agent (A5) of the present invention.

Example A6 457 parts of 3,4-dichlorophenylmaleimide, perfluoroalkylethyl methacrylate {cheminox FA
MAC-C8: Nippon Mektron KK} 503 parts and 2-acrylamido-2-methylpropanesulfonic acid 36
Parts were copolymerized with ditertiary butyl peroxide as an initiator in DMF at a boiling point for 8 hours, and then 7 parts of sodium hydroxide was added for neutralization, and then DMF was distilled off by a reduced pressure drier to obtain the charge of the present invention. A control agent (A6) was obtained.

Example A7 Bisphenol A Propylene Oxide 2 Mole 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 copolymer (1) and 1000 parts of polyester polymer (1) in MEK at 160 ° C
Was esterified, and then MEK was distilled off with a vacuum dryer to obtain a graft polymer (2). Then graft polymer
(2) 1734 parts, 3,4-dichloroaniline (262 parts) and sodium p-aminobenzenesulfonate (37 parts) were reacted in the same manner as in Example A5 to give the charge control agent (A7) of the present invention.
I got

Example A8 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 graft polymer (3), 214 parts of 3,4-dichloroaniline and 30 parts of sodium p-aminobenzenesulfonate were reacted in the same manner as in Example A5 to obtain the charge control agent (A7) of the present invention.

Example A9 782 parts of the copolymer (2) and 100 of the polyester polymer (1)
0 part was reacted in the same manner as in Example A7 to give the graft polymer (4)
I got Then, graft polymer (4) 1782 parts, 3,4
214 parts of -dichloroaniline and 30 parts of sodium p-aminobenzenesulfonate were reacted in the same manner as in Example A5 to obtain the charge control agent (A9) of the present invention.

Comparative Example CA1 Copolymerization was carried out in the same manner as in Example A3 except that sodium styrenesulfonate was not added to obtain a comparative charge control agent (CA1).

Comparative Example CA2 Perfluoroalkylethyl Methacrylate {Chemox FAMAC-C8: Nippon Mektron Co., Ltd.} 912
Parts and 88 parts of sodium styrenesulfonate were copolymerized in the same manner as in Example A1 to obtain a comparative charge control agent (CA2).

Comparative Example CA3 Perfluoroalkylethyl methacrylate {Chemox FAMAC-C8: manufactured by 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 obtain a comparative charge. A control agent (CA5) was obtained.

Example B1 20 parts of the charge control agent (A3) and a styrene-based toner binder {Heimer UNI-3000: Sanyo Chemical Industry Co., Ltd.
After manufacturing and mixing 1000 parts in DMF, DMF is distilled off,
A toner binder composition (B1) of the present invention was obtained. When a thin piece of the toner binder composition (B1) was dyed with RuO4 and then observed with a transmission electron microscope (TEM) {H-7100: manufactured by Hitachi, Ltd.}, dispersed particles having a particle diameter of about 1 µm were observed. Similarly, Hymer UNI-3000 was observed, but no dispersed particles were present.

Example B2 Bisphenol A Propylene Oxide 2 Mol Adduct 4
Polyester toner binder (1) having a weight average molecular weight of 8,000, 17 parts, 341 parts of bisphenol A ethylene oxide 2 mol adduct and 310 parts of terephthalic acid were polycondensed with 2 parts of dibutyltin oxide as a catalyst.
I got 10 parts of the charge control agent (A2) and 1000 parts of the toner binder (1) were mixed in the same manner as in Example B1 to obtain the toner binder composition (B2) of the present invention. When TEM observation was performed in the same manner as in Example B1, dispersed particles having a particle diameter of about 2 μm were observed.

Examples T1 to T8 and Comparative Examples CT1 to C
T8 A charge control agent having the composition shown in Table 1 and a styrene-based toner binder {Heimer UNI-3000, manufactured by Sanyo Chemical Industry Co., Ltd.} 1
000 parts, carbon black @ MA-100, Mitsubishi Kasei
Toner of 80 parts of low molecular weight polypropylene {Viscole 660P, manufactured by Sanyo Kasei Kogyo Co., Ltd.} was produced by the following method. First, Henschel mixer FM10
B, after premixing using Mitsui Miike Kakoki Co., Ltd.
The mixture was kneaded with a twin-screw kneader {PCM-30, Ikegai Co., Ltd.}.
Then, after finely pulverizing using a supersonic jet crusher Lab Jet {made by Nippon Pneumatic Mfg. Co., Ltd.}, it was classified by an air stream classifier {MDS-I, made by Japan Pneumatic Mfg. Co., Ltd.} to 5-20 μm. To obtain a powder having a particle size of, and the toners (T1) to (T8) of the present invention and the comparative toner (CT1) to
(CT8) was obtained. Table 1 shows the evaluation results.

Example T9 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. T9) was obtained. Table 1 shows the evaluation results.

[0052]

[Table 1] Evaluation results ------------------------------------------ Name of toner Charge control agent Charge amount Standing environment Charge amount Copy No. No. of added parts (μC / g) Increase Dependency distribution test ---------------------------------------------- (T1) (A1) 10 parts −24 B B B B A (T2) (A2) 10 parts −21 A A B B A (T3) (A3) 10 parts −15 B A A B (T4) (A3) 20 parts −22 A A A A (T5) (A4) 10 parts −18 B A B A (T6) (A5) 20 parts −22 A A A A (T7) (A6) 10 parts −21 A A B A (T8) (A8) ) 30 parts -21 A A A A A (T9) (B1) 1020 parts -21 A A A A A -------------------------. − −−−− (CT1) not added −9 D C B D (CT2) (CA1) 10 parts −24 C A B B (CT3) (CA2) 10 parts −17 A B B B A (CT4) (CA3) 10 Part -10 CB BD (CT5) (CA4) 20 parts -13 D C AD (CT6) (CA4) 50 parts -18 C C AC (CT7) (CA3) 10 parts combined (CA4) 50 parts- 17 C C B C (CT8) (CA5) 10 parts −11 C C B D −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− --- Note) (CT7) uses both (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 the saturated charge amount is less than 7 minutes B: Friction time to reach a charge amount of 80% of the saturated charge amount is 7 to 20 minutes C: Saturation charge amount D: A friction time to reach a charge amount of 80% of the saturated charge amount of 20 to 60 minutes D: A friction time to reach a charge amount of 80% of the saturation charge amount exceeds 60 minutes Measurement of environmental stability The charge amount of the sample conditioned at high temperature and high humidity and low temperature and low humidity for 8 hours or more was measured. Low temperature and low humidity: 10 ° C, 40% R. H. High temperature and high humidity: 35 ° C, 85% R. H. Evaluation criteria A: Small change in charge amount at low temperature and low humidity and high temperature and high humidity B: Medium change in charge amount at low temperature and low humidity and high temperature and high humidity C: Charge amount at low temperature and low humidity and high temperature and high humidity Change in charge amount is measured. 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. apparatus:
Particle charge distribution measuring device {EST-1, manufactured by Hosokawa Micron Co., Ltd.} Evaluation Criteria A: Narrow charge distribution B: Medium charge distribution C: Wide charge distribution Copy test Developer Was subjected to a continuous copying test using an evaluation copying machine. 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 is clearly degraded after continuous copying of 20,000 sheets D: Image is defective from the beginning of copying

Examples T10 to T13 (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 Toner) The toners (T10) to (T13) of the present invention were prepared in the same manner as in Example T1 except that the toner binder was changed to the polyester toner binder (2) in the same manner as in Example 2. Obtained. Table 2 shows the evaluation results.

[0055]

[Table 2] Evaluation results --------------------------------------------- toner name charge control agent charge amount standing environment charge amount Copy No. No. of added parts (μC / g) Increase Dependence distribution test ----------------------------------------------- (T10) (A2) 10 parts -20 A A B A B (T11) (A5) 20 parts -21 A A A A A (T12) (A7) 20 parts -23 A A A A (T13) (A9) 30 parts -22 A A A A −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− (Evaluation method) Evaluation was performed in the same manner as in Example T1.

Examples T14 and T15 A polyester toner binder (1) (1000 parts), a colorant (Fastgen Magenta R-11, manufactured by Dainippon Ink and Chemicals, Inc.) 50 parts, and a charge control agent having the composition shown in Table 3 were used. A toner was obtained in the same manner as in Example T1 to obtain toners (T14) and (T15) of the present invention. Table 3 shows the evaluation results.

Example T16 A toner binder composition (B2) was used in place of the toner binder (1), and the charge control agent was not added.
Toner of the present invention (T16) was obtained by converting to toner in the same manner as in Example T13. Table 3 shows the evaluation results.

[0058]

[Table 3] Evaluation results -------------------------------------------- Toner name Charge control agent Charge amount Standing environment Charge amount Transparency No No. of added parts (μC / g) Increase Dependence distribution --------------------------------------------------- (T14) (A5) 20 parts -22 A A A B (T15) (A7) 20 parts -21 A A A A A (T16) (B2) 1020 parts -20 A A A A A --------------- About --------------------------- (Evaluation method)-, it evaluated similarly to Example T1. Evaluation of Transparency Only the toner binder and the charge control agent were kneaded without adding a colorant, and then the kneaded product was molded into a cylinder of about 5 mm using a melt indexer, and its transparency was visually judged. Evaluation criteria A: transparent B: slightly turbid C: cloudy

[0059]

The charge control agent, 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 coloring of the charge control agent is weak, the color tone of a color toner is excellent. 3. The toner has high transparency and excellent color tone when used as a color toner. 4. A toner having a high dispersibility of the charge control agent and a sharp charge amount distribution can be obtained. 5. The charge amount of the charge control agent is high, and a toner having an appropriate charge amount can be obtained by using a small amount of the charge control agent. 6. It is possible to obtain a toner which is excellent in charge rising and reaches a fixed charge amount by short-time friction. 7. 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. 8. A toner that stably retains a clear image with little fog even after long continuous copying is obtained. 9. 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.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Toru Ohama Inventor 1-11, Hitotsubashi-honcho, Higashiyama-ku, Kyoto Sanyo Chemical Industry Co., Ltd.

Claims (11)

[Claims] 1. A polymerizable monomer (1) 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, a cyano group and a perfluoroalkyl group, and sulfo. A charge control agent comprising a copolymer (A) containing a group-containing polymerizable monomer (2) as a constituent unit. 2. (A) has 10 as the constitutional unit of (1)
-99% by weight, 0.1 to 20% by weight of (2) as a constitutional unit, and 1 to 90% by weight of a perfluoroalkyl group- and / or silicone group-containing polymerizable monomer (3) as a constitutional unit. % Of the charge control agent according to claim 1, which is a copolymer. 3. The charge control agent according to claim 1, wherein (1) is a phenylmaleimide-substituted product in which an aromatic ring is substituted with X or a phenylitaconimide-substituted product. 4. The charge control agent according to claim 1, wherein (2) is a sulfonate group-containing monomer. 5. The charge control agent according to claim 1, wherein (2) is an aromatic sulfonate group-containing monomer. 6. The polymerizable monomer (3) is selected from the group consisting of perfluoroalkyl group-containing (meth) acrylate, perfluoroalkyl group-containing maleate and perfluoroalkyl group-containing itaconate.
5. The charge control agent according to any one of 5 to 5. 7. 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 1 to 6. A copolymer (AB) in which a polymer portion (b) selected from the group consisting of
A charge control agent consisting of. 8. A toner binder composition comprising a toner binder and the charge control agent according to claim 1. 9. An electrostatic charge image developing toner containing a toner binder, a coloring material and a charge control agent, which comprises the charge control agent according to any one of claims 1 to 7. For toner. 10. The electrostatic image development according to claim 9, wherein at least a part of the toner binder forms a continuous phase in the toner, and at least a part of the charge control agent forms a discontinuous domain. For toner. 11. A toner for developing an electrostatic image, wherein at least a part of the toner binder forms a continuous phase and at least a part of the charge control agent forms a discontinuous domain. The charge control agent for toner according to any one of 1.