JPS62255958A - Electric charge controlling agent having improved dispersibility and its production - Google Patents

Abstract

PURPOSE:To improve the dispersibility of an electric charge controlling agent and to obtain a good image by polymerizing an unsatd. monomer in the presence of a specific metallic complex to obtain the charge controlling agent. CONSTITUTION:The metallic complex expressed by the formula is used. In the formula, R1, R2, R3 denote H, NO2, halogen, alkyl group of 1-9C, sulfonamide group, SO2CH3, R4 denotes H, alkyl group of 1-9C, COOH, OH, M denotes Cr, Fe, A denotes H, Na, K, NH4, quaternary ammonium salt. The unsatd. monomer is polymerized in the presence of the metallic complex. A styrene, butyl acrylate, glycidyl methacrylate, etc., are used as the unsatd. monomer. The charge controlling agent is obtd. from the polymer. Since the metallic complex is used for the constituting component, the dispersibility of the charge controlling agent is improved and the quantity of electric charge is sharply distributed. The generation of fogging is thus eliminated even by the use of a small amt. and the sharp image is formed.

Description

Detailed Description of the Invention [Industrial Application Field 1] The present invention is used for developing electrostatic images formed in electrophotography, electrostatic printing, electrostatic recording, etc. The present invention relates to a charge control agent for preparing toner.

1. Prior Art 1 Generally, an electrostatic image is developed into a toner image by using a colored powder toner, and this toner image is fixed as it is or after being transferred to a transfer paper or the like.

However, the toner is usually composed of a composition mainly consisting of a polymer as a binder component, a coloring agent such as carbon black, and a specific dye as a charge control agent. A method of melt-mixing under heating at a ratio of 1. By polymerizing a polymerizable unsaturated monomer in the coexistence of a dye as a colorant and a charge control agent, the binder production and toner preparation are carried out at the same time. Methods are known.

Among the above methods, method (■) has advantages in terms of simplifying the toner manufacturing process, but it is difficult to obtain a product with consistent quality, and it also causes bronzing and abnormal odors, and the toner has poor charging properties. The actual situation is that it is difficult to improve and practical application cannot be expected even if the amount of the original charge control reduction is increased, so method (2) is usually implemented.

[Problem to be Solved by the Invention 1] However, the toner obtained by this method is too large to have sufficient chargeability! Since it is necessary to mix an amount of charge control agent, the handling of the control agent is mainly difficult in terms of handling, environmental pollution, and uniform dispersion of the toner. There are many restrictions from

Therefore, it is necessary to improve the dispersibility of the control agent to enhance the charge control effect and sharpen the distribution of charge amount, in other words, to improve the charge control effect. It is extremely useful in practice to reduce the usage rate of B3'l.

Such improvements bring about the effect that clear images can be obtained without fogging or unevenness on the image surface even if copying or printing is continued for a long period of time, and the coloring of the charge control agent is the final purpose of the toner. Since there is no possibility of adversely affecting color difference, it has the advantage that it can be applied to a wide variety of colored toners.

[Means for Solving the Problems 1] As a result of extensive research in order to solve these problems, the inventors of the present invention found that the general formula [However, P, , R2, and R are 1. No.2. ) 10 den, an alkyl group having 1 to 9 carbon atoms, and a sulfonamide group which may have a substituent.

SO, CH,, R4 is H9 an alkyl group having 1 to 9 carbon atoms,
C0() g1. ○ H, M are Cr, Fe, Co,
A (Sat) 1 A charge control agent consisting of a metal complex represented by 1 representing lNa, NH, quaternary ammonium salt, etc. and a vinyl polymer can meet the purpose, and that such a control agent can meet the above-mentioned requirements. The present invention has been completed based on the discovery of the novel fact that unsaturated monomers can be advantageously produced in the coexistence of metal complexes, particularly when three-component polymerization is carried out.

Although the metal complex itself used in the present invention is well known, the combination of this metal complex and a vinyl polymer has a Vf characteristic.

Examples of the metal complex constituting the charge control agent of the present invention are as follows.

Examples of commercially available metal complexes include C, I, and S.
ovenj B 1ack 1, 2, 6, 15,
22, 27, 2829, 34.36° 37.38.40
．． 41,42,45,47.43°C, r, So
lvenL B rown 28, 34, 35.37
+42.43.44+49+52+58° On the other hand, another component constituting the charge control agent of the present invention is a vinyl polymer.

The above polymer is used by homopolymerizing or copolymerizing an ethylenically unsaturated monomer.

Unsaturated that can be used in the present invention! Examples of L-mers include styrene, O-ethylstyrene, m-ethylstyrene, p-methylstyrene, α-7thylstyrene, p-
-ethylstyrene, 2,4-tmethyl or styrene, p-(
n-butyl)styrene, p-(tert-)ethyl)tyrene, p-(n-hexyl)styrene, p-(n-dodecyl)styrene, p-methkinstyrene, 0-7enylstyrene, p-chlor Styrene monomers such as styrene and 3,4-nochlorostyrene, unsaturated monoolefins such as ethylene, propylene, butylene, and isobutylene, and vinyl halides such as vinyl chloride, vinylidene chloride, vinyl bromide, and vinyl fluoride. , vinyl esters such as vinyl acetate, vinyl propionate, vinyl fragrant, vinyl butyrate, methyl (meth)acrylate, ethyl (meth)acrylate, isobutyl (meth)acrylate, (meth)propyl acrylate, (meth)octinoacrylate, (meth)dodecyl acrylate, (meth)acrylate lauryl, (meth)acrylate 2-ethylhexyl, (meth)acrylate 2-chloroethyl, (meth)acrylate ) phenyl acrylate, a-chloro(meth)methyl acrylate, nomethylaminonityl (meth)acrylate, ethylaminoethyl (meth)acrylate,
Carboxylic acid esters such as (anhydrous) maleic acid ester, 7-malic acid ester, crotonic ester, itaconic ester, etc., (meth)acrylic acid, carboxylic acid such as (anhydrous) maleic acid, crotonic acid, itaconic acid, 7-malic acid, etc. , (meth)acrylonitrile, (meth)acrylamide, alkyl vinyl ether, alkyl vinyl kene, N-vinylvirol, N-vinylcarbazole, N-vinylindole, N-vinylpyrrolidone, and the like. These monomers may be used alone or in combination.

Preferred monomers are styrene and (meth)acrylic acid ester, which may be used alone or in combination.

To produce the charge control agent of the present invention, the unsaturated monomer is polymerized in the coexistence of the metal complex described above. As the polymerization method, any method such as solution polymerization, suspension polymerization, bulk polymerization, or emulsion polymerization can be adopted, but solution polymerization is most advantageous in terms of the performance of the charge control agent.6 In the case of solution polymerization, the solvent is Metal complex and unsaturation used
Although it varies depending on the type of h-mer, usually alcohols such as methanol, (iso)propanol, (iso)butanol, toluene, methyl ethyl ketone, acetone, methyl isobutyl ketone, ethyl acetate, butyl acetate, and trimethylformamide are used. , trimethyl sulfoxide, N
-Methylpyrrolidone, γ-butyrolactone, tetrahydro-7rane, nooxane, etc. are used.

In the case of suspension polymerization, the medium is water, but known protective colloids such as polyvinyl alcohols, celluloses, starch, gelatin, and sodium polyacrylate, or barium sulfate, calcium sulfate, and carbonate are used as suspension dispersion stabilizers. Dispersion aids such as barium, calcium carbonate, clay, diatomaceous earth, and surfactants are used.

The initiator used during the polymerization may be any initiator such as an azo initiator or a peroxide initiator, but it is advantageous to use an azo initiator.

Examples of azo initiators include 2.2'-azobisisobutyroni)linob, 2+2'-7zobis-2,4-dimethylvaleronitrile, 2.2'-7zobis-2-cyclopropylbropionitrile, 2 , 2'-7zobis-2-methylbutyronide IJ, 2,2'-7zobis-2,3-methylbutyronide IJ, 2,2'-7zobis-2-methylvaleronitrile, 2-( butyl)azo-2-cyano-4-methoxy-4-methylpentane, 2-t-butylazo-2-cyanopropane, 2-(t-butyl)azo-2-cyano-4-methylpentane, 2- (t-butyl)azo-2-cyanobutane, 1-(t-butyl)azo-1-cyanocyclohexane, 2゜2'-7sol:'su4-methoxy2,4-nomethylvalero=)lyl, 1
, 1'-7zobiscyclohexane-1-carbonitrile, 4,4'-7zobis-4-cyanovalerinoquacid, dimethyl-2-7zobis-in butyrate, and the like.

The reaction can be carried out by polymerizing unsaturated monomers in the coexistence of a metal donor and an initiator, and such raw materials can be charged all at once, in parts, or
It is supplied into the system by any method such as continuous feeding.

The amount of each raw material to be used varies depending on the performance of the target charge control agent, so it cannot be absolutely specified, but usually the metal complex is 5 to 200% by weight, preferably 1% by weight, based on the unsaturated monomer.
0 to 150% by weight, the initiator is 2 to 150% by weight based on the unsaturated monomer.
It is used in a proportion of 20% by weight.

In the finally obtained charge control agent, the ratio of the metal complex to the vinyl polymer is 5 to 200% by weight, preferably 10 to 150% by weight, particularly preferably 10 to 50% by weight.
It is desirable to adjust so that

The polymerization temperature varies slightly depending on the polymerization method, but is usually 40
-130°C, and the practical polymerization time is about 5 to 25 hours.

After the polymerization is completed, the unreacted unsaturated monomer and solvent are removed according to a conventional method to obtain the desired charge control agent in the form of powder, granules, or blocks.

To prepare a toner using the above control agent, it may be mixed with a suitable pigment such as carbon black, a dye, and a polymer as a binder component. The appropriate amount of the control agent mixed in the toner is 0.01 to 1% by weight, preferably 0.1 to 2% by weight, based on the metal complex content. The amount of kneading is far smaller than the amount of charge control agent used in conventional toner production, which indicates that the control agent of the present invention has a superior charge control effect. I can say that there is.

Colorants include carbon black, lamp black,
Iron black, nigrosine dye, aniline black, pennon yellow, Hansa yellow, chrome yellow, rhocumin 6G lake, quinacridone, rose bengal, phthalocyanine dye/pigment, ultramarine blue, triallylmethane dye/pigment, anthraquinone dye, monoazo dye・Diazo Kento・Pigments and other conventionally known dyes and pigments can be used alone or in combination.

As the binder, the above-mentioned monomers and copolymers of unsaturated monomers can be used as appropriate. Furthermore, it is also possible to use wax, polyester resin, epoxy resin, silicone resin, resin, polyurethane (3), etc. When preparing the toner, predistribution, external effects 1, for example charge control other than the present invention. (adequately mix the agents, etc.).

1 work 1 The charge control agent of the present invention is useful for toner preparation.

[Example 1] The charge control agent of the present invention will be explained in more detail with reference to the following example. "Parts" or "%" are by weight unless otherwise specified.

(Left below) Gold 41 wood metal complex used [11 Metal complex ([1 Metal complex [11 Metal tube [V]] Example 1 72 parts of styrene, 13 parts of butyl acrylate, Metal complex 1
1] Polymerization was carried out at 70 to 80°C for 16 hours in a pressure flask equipped with a reflux condenser. After the reaction was completed, the mixture was dried by heating under reduced pressure to obtain a charge control agent. The initial tribocharge amount of the dried product was -46 μC/g.

Example 2 72 parts of styrene, 18 parts of butyl acrylate, metal complex [
1]] 10-6 parts, dimethylformamide 135 parts, and 6 parts of azobisisobutyronitrile were polymerized in a pressurized flask equipped with a reflux condenser at 70 to 80'C for 16 hours. After the reaction was completed, the mixture was dried by heating under reduced pressure to obtain a charge control agent. The initial tribocharge amount of the dried product was -50 μC/8.

Example 3 72 parts of styrene, 18 parts of butyl acrylate, metal complex [
1110 parts of dimethylformamide, 135 parts of dimethylformamide, and 6 parts of azobisisobutyronitrile were placed in a three-neck flask with a reflux-cooled III tube and polymerized at 9.70 to 80°C for 16 hours. After the reaction was completed, the mixture was dried by heating under reduced pressure to obtain a charge control agent. The initial charge amount of the dried bird was -39 ttC/g.

Example 1V 70 parts of styrene, 20 parts of grindyl methacrylate, metal complex [! llo part, trimethylformamide I'13S part,
6 parts of azobisisobutyronitrile was placed in a pressure flask equipped with a reflux condenser and polymerized at 70-80'C for 16 hours. After the reaction was completed, the mixture was dried by heating under reduced pressure to obtain a charge control agent. The initial tribocharge amount of the dried product was -45 μC/g.

Example 5 72 parts of styrene, 18 parts of butyl acrylate, metal complex [
1.0 part of methyl ethyl ketone, 135 parts of methyl ethyl ketone, and 6 parts of azobisisobutyrodifuryl were polymerized in the same flask as in Example 1 at 70 to 80'C for 16 hours. After the reaction, the charge control agent was obtained by heating and drying under reduced pressure. The initial tribocharge amount of the dried product was -49 μC/g.

Measurement tests 1 to 5 of toner physical properties using a charge control agent Styrene/n-butyl methacrylate copolymer (heavy Hm
Composition ratio 6 S/35, average molecule H4oooo, Tg62'
C) 100 parts of carbon black, 5 parts of carbon black, and 5 parts of the charge control agent of Example 1 were uniformly premixed in an X" type blender for 1 hour, and then melted and kneaded for 130 minutes with a kneader-1 trowel of 150'C. The mixture was cooled, crushed in a vibrating mill, finely crushed in an air mill, and then classified to obtain a powder toner having an average particle size of 15 μm.

() The proportion of charge control agent in Qi is as a metal complex (), 5%) Three parts of this toner and iron powder carrier (manufactured by Nippon Tetsuko Co., Ltd., TEFV 200) 97B were mixed to prepare an original image agent. Na.

The initial tribocharge amount of the toner was -31 μC/g.

In addition, when an image was formed using a copying machine equipped with a selenium drum that had been modified so that the collected toner after drum cleaning was automatically circulated to the toner supply section, the initial image was foggy. It is clear with no density unevenness, and the image after SO000 sheets remains as clear as ever. There was no evidence of any contamination of the copying machine due to the Yner flyover.

Furthermore, similar tests were conducted on the charge control agents obtained in Examples 2 to 5.

The proportion of the charge control agent in the toner is 0.5% of the metal complex.
Regardless of %i, the initial triboelectric charge amount is -
28μC/g, -29μC/g, -28μC/g, -3
At 0 μC/g') S OQ The image after 0 sheets remained clear and unchanged.

In addition, as a control test 1, 90 parts of a copolymer solution consisting of 72 parts of styrene and 18 parts of butyl acrylate (produced by polymerizing in the same manner as in Example 1 except that the use of the metal complex was omitted) and the metal complex [ When 1,110 parts of the toner was dissolved and sufficiently stirred, the resulting composition was heated and dried under reduced pressure as a charge control agent and the same test as in Example 1 was conducted, the initial tribocharge amount of the toner was only 15 μC/H. It was nothing more than

Furthermore, as a control test 2, a copolymer consisting of 72 parts of styrene and 18 parts of butyl acrylate (manufactured by polymerization in the same manner as in Example 1 except that the use of the metal complex was omitted)
When the same test was conducted using a charge control agent obtained by melt-blending 90 parts of metal complex [N1t) and part of metal complex [N1t], the initial tribocharge amount of the toner was only 17 μC/g. It was. The initial image was unclear with a lot of fog.

Examples 6 to 11 Experiments were conducted according to Example 1 using the drugs shown in the following table. The results are shown in Table 1.

[Effect of the invention 1] The charge control agent of the present invention has improved dispersibility and a sharp charge distribution, so even when used in a small amount, it can produce clear images without fogging or density unevenness on the image surface. This makes it possible to prepare toners that

Patent applicant Nippon Gosei Kagaku Kogyo Co., Ltd. Orient Chemical Kogyo Co., Ltd.

Claims (1)

[Claims] 1. A charge control agent with improved dispersibility, comprising a metal complex represented by the following general formula and a vinyl polymer. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [However, R_1, R_2, R_3 are H, NO_2, halogen, an alkyl group having 1 to 9 carbon atoms, a sulfonamide group that may have a substituent, SO_2CH_3, R_4 are H ,
Alkyl group having 1 to 9 carbon atoms, COOH, OH, M is Cr
, Fe, Co, A represents H, Na, K, NH_4, quaternary ammonium salt, etc.] 2. Characterized by polymerizing an unsaturated monomer in the coexistence of a metal complex represented by the following general formula. A method for producing a charge control agent with improved dispersibility. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [However, R_1, R_2, R_3 are H, NO_2, halogen, an alkyl group having 1 to 9 carbon atoms, a sulfonamide group that may have a substituent, SO_2CH_3, R_4 are H ,
Alkyl group having 1 to 9 carbon atoms, COOH, OH, M is Cr
, Fe, Co, A represents H, Na, K, NH_4, quaternary ammonium salt, etc.]