JPH05188634A - Additive for developer - Google Patents

Abstract

PURPOSE:To provide an additive for a developer showing an excellent chargeability when an electrostatic charging developer is used, especially, scarcely showing a deterioration of an electrostatic chargeability even under an environment of high temp. and high humidity. CONSTITUTION:The additive is formed by ion exchange processing for vinyl monomer having quaternary nitrogen in which halogen ion is a anion component after existing a polymer which is a component of a copolymer on an org. or inorg. fine particles to form the additive by converting the halogen ion existing on the surface to another anion.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a developer additive to be added to an electrophotographic developer.

[0002]

In the electrophotographic recording method and the like, an electrostatic image formed on a photoconductor is usually developed with an electrophotographic developer containing a pigment or the like, and the obtained visible image is transferred onto a transfer paper, Fixing is performed with a heat roller or the like. At that time, in order for the electrophotographic developer to be used to be excellent in compatibility, it is necessary to be excellent in fluidity, caking resistance, fixing property, charging property, cleaning property and the like. .. Above all, it is important to enhance the fluidity and the cleaning property in order to carry out the development smoothly.

Conventionally, in order to improve the fluidity and cleaning property of the developer, for example, Japanese Patent Publication No. 54-1621.
As disclosed in Japanese Patent Publication No. 9, as a constituent material of a developer for electrophotography, hydrophobized silicon dioxide or resin powder (for example, polymethylmethacrylate powder)
Is being added. However, when these powders are added to the positively chargeable developer, there is a drawback that the amount of reverse polarity toner increases and the background fog occurs on the copy. In order to improve this defect, it has been proposed to use a metal oxide whose surface is treated with an aminosilane compound (Japanese Patent Publication No. 53-24447), but since the chargeability under high humidity conditions is poor, If a large amount of this is used as an additive for a developer, there is a problem that the chargeability is deteriorated. In particular, in the case of a one-component developer, it is necessary to add a large amount from the viewpoint of improving developability and fluidity, but as a result, there is a disadvantage that the chargeability is extremely deteriorated.

[0004]

SUMMARY OF THE INVENTION The present invention has been made for the purpose of overcoming the above-mentioned problems of the prior art. That is, an object of the present invention is to provide an additive for a developer that imparts excellent charging characteristics to a positively chargeable developer, and in particular, electrophotography in which a decrease in chargeability does not occur in a high temperature and high humidity environment. It is to provide an additive for a developer for obtaining a developer.

[0005]

Means for Solving the Problems The present inventors have focused on a polymer constituting the surface of organic or inorganic fine particles, and as the polymer, a vinyl monomer having a quaternary nitrogen containing an anion other than halogen is used. It was found that the above object can be achieved by using a copolymer component, and the present invention has been completed. That is, the developer additive of the present invention is obtained by allowing a polymer having a vinyl monomer having a quaternary nitrogen having a halogen ion as an anion component to be a component of a copolymer to be present on the surface of organic or inorganic fine particles. It is produced by performing an ion exchange treatment, and is characterized in that the halogen ion is converted into another anion.

The present invention will be described in detail below. The organic or inorganic fine particles constituting the present invention are metal oxides or resin powders. Specifically, as the metal oxide,
Examples thereof include various metal oxides such as silicon dioxide, alumina, titanium dioxide, iron oxide, chromium oxide, cerium oxide, magnesium oxide and zinc oxide.

Further, as the resin powder, for example, acrylic resin beads (polymethylmethacrylate powder), silicon resin beads, polyamide beads, polyurea beads,
Melamine resin beads, urea resin beads and the like can be used.

In the present invention, a polymer containing a vinyl monomer having a quaternary nitrogen having a halogen ion as an anion component as one component of the copolymer is present on the surface of these organic or inorganic fine particles. May exist in a state of being chemically bound to the surface of the organic or inorganic fine particles or in a state of being physically attached thereto.

At least one component of the above-mentioned polymer is formed by using a vinyl monomer having a quaternary nitrogen having a halogen ion as an anion component as a constituent component.
The vinyl monomer having a quaternary nitrogen having a halogen ion as an anion component used in the present invention,
For example, acryloyloxyethyltrimethylammonium chloride, acryloyloxyethyltriethylammonium chloride, methacryloyloxyethyltrimethylammonium chloride, methacryloyloxyethyltriethylammonium chloride, methacryloyloxyethylbenzylammonium chloride (meth) acrylate ammonium salt monomer, acrylamide (Meth) acrylamide ammonium salt monomers such as trimethylpropylammonium chloride, acrylamidotriethylpropylammonium chloride, methacrylamidotrimethylpropylammonium chloride and methacrylamidobenzylpropylammonium chloride, vinylbenzylethylammonium chloride Id, vinylbenzyl ammonium salt monomers such as vinylbenzyltrimethylammonium chloride, N-butylvinylpyridinium bromide, vinylpyridinium salt monomers such as N-cetylvinylpyridinium chloride, N-vinyl-2-methylimidazolinium chloride, N- Examples thereof include vinyl imidazolinium salt monomers such as vinyl-2,3-dimethyl imidazolinium chloride.

Examples of the other monomer copolymerizable with the vinyl monomer having a quaternary nitrogen containing the halogen ion as an anion component include, for example, methyl methacrylate, ethylene glycol dimethacrylate, ethyl methacrylate and n-butyl. Methacrylic acid ester such as methacrylate, iso-butyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, methyl acrylate, ethyl acrylate,
Any water-soluble monomer such as acrylic acid ester such as n-butyl acrylate, iso-butyl acrylate, hydroxypropyl acrylate, and hydroxybutyl acrylate, and a monomer having a vinyl group soluble in the water-soluble monomer can be used. Examples thereof include styrene, divinylbenzene, and various acrylic acid esters.

Further, when the above polymer is physically attached to the surface of the organic or inorganic fine particles to be present, another polymer may be mixed with the above polymer. Other polymers that can be mixed with the above polymers include, for example, vinylidene chloride,
Vinylidene polymer such as vinylidene fluoride, olefin polymer such as polyethylene and polypropylene, polyester, polycarbonate, polyurethane, epoxy resin,
Examples include phenolic resins and polyether resins. However, it is desirable that the above-mentioned polymer is mixed in a ratio of about 1/2 to 1/100 with respect to the monomer copolymerizable with the vinyl monomer having a quaternary nitrogen having a halogen ion as an anion component.

In the present invention, the above halogen ions are finally converted into other anions by ion exchange treatment, and various other anion components can be used. Specific examples include, for example, acetate ion,
Carboxylic acid ions such as butyrate ion, caprylate ion, laurate ion, stearate ion, benzoate ion, naphthalenecarboxylate ion, naphthylacetate ion, p-toluenesulfonate ion, p-styrenesulfonate ion, naphthalenesulfone Examples thereof include acid ion, 4-hydroxynaphthalene sulfonate ion, lauryl benzene sulfonate ion, dodecyl benzene sulfonate ion, naphthoquinone sulfonate ion, and other sulfonate ions, and lauryl sulfate ion, dodecyl sulfate ion, and other sulfate ions. Further, examples include those derived from acid dyes such as acid yellow, acid red, acid violet and acid blue. In the ion exchange treatment, these anions may be used by dissolving them in deionized water in the form of sodium salt or potassium salt as shown below.

The above-described additive for a developer of the present invention is prepared by preliminarily pretreating the surface of organic or inorganic fine particles to introduce a substituent capable of reacting with a vinyl monomer having a quaternary nitrogen, and then adding the organic or inorganic fine particle. A polymer obtained by treating the surface of fine particles with a vinyl monomer having a quaternary nitrogen having a halogen ion as an anion component, and using a vinyl monomer having a quaternary nitrogen having a halogen ion as an anion component as one component of the copolymer It is produced by allowing it to exist and then performing an ion exchange treatment to convert the halogen ion into another anion.

The developer additive of the present invention is a polymer containing, as a component of a copolymer, a vinyl monomer having a quaternary nitrogen having a halogen ion as an anion component on the surface of organic or inorganic fine particles. By coating a mixture of the polymer with another polymer by a method such as spray drying, coacervation, or interfacial precipitation, an ion exchange treatment is carried out to convert the halogen ion into another anion. It can be manufactured.

In the above method, the pretreatment is, for example,
When the organic or inorganic fine particles are silicon dioxide, by treating as vinyltrimethylsilane,
In the case of polymethylmethacrylate, it is carried out by treating with ethylene glycol dimethacrylate. This pretreatment is preferably performed by appropriately changing the pretreatment agent depending on the type of organic or inorganic fine particles.

The conversion of a halogen ion into another anion is carried out by dissolving the sodium salt or potassium salt of the corresponding anion in deionized water and adding organic or inorganic fine particles to this aqueous solution, or adding organic or inorganic salt to the aqueous solution. It is performed by adding or removing inorganic fine particles and then washing with water.

Any sodium or potassium anion salt can be used as long as it is water-soluble and can exchange ions with halogen ions. Specific examples include, for example, carboxylic acid salts such as sodium acetate, potassium acetate, sodium butyrate, sodium caprylate, sodium laurate, sodium stearate, sodium benzoate, sodium naphthalenecarboxylate, potassium naphthylacetate, and p-toluene sulfone. Sodium salt, sodium p-styrenesulfonate,
Examples thereof include sodium naphthalene sulfonate, sodium 4-hydroxynaphthalene sulfonate, sodium lauryl benzene sulfonate, sodium dodecyl benzene sulfonate, sodium naphthoquinone sulfonate, and the like, and sulfates such as sodium lauryl sulfate and sodium dodecyl sulfate. Acid dyes such as acid yellow, acid red, acid violet and acid blue can also be used.

[0018]

【Example】

Example 1 As fine particles, 50 g of silicon dioxide powder (130: Nippon Aerosil Co., Ltd.) was taken and 5 g of vinyltrimethoxysilane (SZ6300: Toray Silicone Co., Ltd.) while stirring in a high-speed stirrer (Henschel mixer). It was added to a solution dissolved in 1 liter of toluene, stirred for 1 hour while heating at 110 ° C., and detoluene was carried out to introduce a CH ₂ ═CHSi—O— group on the surface of silicon dioxide. The treated fine particles are suspended in 250 g of ion-exchanged water, and 0.4 g of potassium persulfate and 0.2 g of N- while rotating at 200 rpm with a propeller-type stirrer (Three One Motor: Shinto Scientific Co., Ltd.). Cetyl vinylpyridinium chloride and 2.0 g of methyl methacrylate, 0.16
g of sodium bisulfite was sequentially added, and the reaction was carried out at 25 ° C. for 3 hours. After completion of the reaction, the mixture was poured into 2 kg of ion-exchanged water, sufficiently stirred, and allowed to stand. After the fine particles had settled, the supernatant was removed. This operation was repeated 4 times to wash the fine particles. Next, 2 g of a 5% aqueous solution of sodium 1-naphthalenesulfonate was added to this fine particle suspension, and the mixture was stirred at room temperature for 30 minutes to carry out an ion exchange reaction. After the reaction,
The capsule particles were washed 5 times with 1 liter of ion-exchanged water to obtain the developer additive of the present invention.

Next, 35 parts by weight of magnetic powder (EPT-1000: Toda Kogyo Co., Ltd.), 1 part by weight of cetylpyridinium chloride, styrene-acrylic resin (SAN MI-2).
D: 100 weight of Sanyo Kasei Co., Ltd. was kneaded with a Banbury mixer (Kobe Steel Co., Ltd.), pulverized with Jutshell (Nippon Pneumatic), and classified by a dispersion separator (Nippon Pneumatic) to give 5 ~
Toner A having an average volume diameter of 15 μm was prepared. To 1000 g of this toner A is added 10 g of the above-mentioned additive for developer.
In addition, a toner B was prepared by stirring for 2 minutes while rotating a 10 m / sec blade with a Henschel mixer.

As a comparative example, 1000 g of toner A
Aminosilane-treated silicon dioxide powder (RA-20
OH: Nippon Aerosil Co., Ltd. (10 g) was added and stirred for 2 minutes while rotating a 10 m / sec blade with a Henschel mixer to prepare a toner C.

The above three toners A, B and C were put in a 5014 copying machine manufactured by Fuji Xerox Co., Ltd., and high temperature and high humidity (30 ° C.,
85% RH), normal temperature and normal humidity (22 ° C., 55% RH), low temperature and low humidity (10 ° C., 15% RH), and the results of checking the chargeability of the developer and the printed image (see Table 1). It was found that the toner B containing the developer additive of the present invention is very good.

[0022]

[Table 1]

Example 2 As a fine particle, 50 g of alumina powder (AOC: Nippon Aerosil Co., Ltd.) was used to prepare an additive for a developer in the same manner as in Example 1, and the toner A used in Example 1 was 2 wt%.
When added, a good developer free of background fog was obtained under high temperature and high humidity. In addition, the addition amount is 0.3 to 5.0 wt%
Good results were obtained even when the range was changed.

Example 3 Toner D prepared by removing N-cetylvinylpyridinium chloride from Toner A prepared in Example 1 was prepared, and 2 parts of the developer additive of the present invention prepared in Example 1 was prepared. Add 0.0 wt% and use Henschel mixer for 15m /
Toner E was prepared by stirring for 10 minutes and was tested. As a result, even after 20,000 copies, generation of background fog and reduction in density were not observed at high temperature and high humidity.

Example 4 As fine particles, polymethylmethacrylate powder (Mp-1
00: Soken Chemical Co., Ltd.) 50 g, deionized water 1
Add 25g, 200 rpm with a stirrer (three-one motor manufactured by Shinto Kagaku Co., Ltd.) equipped with a propeller type stirring blade.
Stir in minutes. After adding 5 g of IN nitric acid and 4 g of a 10% cerium sulfate aqueous solution, 0.5 g of ethylene glycol dimethacrylate was added, and the reaction was carried out at 15 ° C. for 3 hours. After completion of the reaction, the mixture was poured into 1 liter of ion-exchanged water, sufficiently stirred and allowed to stand. After the fine particles had settled, the supernatant was removed. This operation was repeated twice more to wash the fine particles. In this way, fine particles in which ethylene glycol dimethacrylate was graft-polymerized on the surface of the fine particles were obtained.
This was resuspended in ion-exchanged water again and stirred at 200 rpm with a stirrer (three one motor: manufactured by Shinto Kagaku Co., Ltd.) equipped with a propeller-type stirring blade. Next, 0.4 g of potassium persulfate, 0.2 g of N-cetylvinylpyridinium chloride, 2.0 g of methyl methacrylate, and 0.16 g of sodium hydrogen sulfite were sequentially added to this, and reacted at 25 ° C. for 3 hours. I went. 2 after the reaction
It was poured into 1 liter of ion-exchanged water, thoroughly stirred and filtered.
After filtering the fine particles, 2 liters of ion-exchanged water was further added, and this operation was repeated 4 times to wash the fine particles. Next, 2 g of a 5% aqueous solution of sodium 1-naphthalenesulfonate was added to this fine particle suspension and stirred at room temperature for 30 minutes to carry out an ion exchange reaction. After completion of the reaction, the fine particles were washed with 1 liter of ion-exchanged water 5 times while filtering to obtain the developer additive of the present invention. The obtained fine particle suspension was opened in a stainless steel vat, dried at 60 ° C. for 10 hours with a dryer (made by Yamato Scientific Co., Ltd.), then placed in a Henschel mixer and stirred to disperse the fine particles to develop the developer of the present invention. An additive powder was obtained.

To the toner A prepared in Example 1, 0.3 wt% of 2 wt% of a fluid finishing agent (R-972: Nippon Aerosil Co., Ltd.) was added, and a blade was applied with a Henschel mixer at 10 m / sec. The developer F was prepared by rotating and stirring for 10 seconds. When this developer was tested in the same manner as in Example 1, it was confirmed to be very good. (See Table 2)

[0027]

[Table 2]

Further, this toner F has a good cleaning property, and toner B, toner C, toners E and F are used.
Compared to the x5014 toner, no contamination of the photoconductor drum was observed even after 20,000 copy operations. Therefore, this developer additive improves the charging stability as well as the cleaning property. I found out. As described above, the additive for a developer of the present invention exhibited a sufficient effect even when used in combination with the conventional fluid finishing agent.

The mixing ratio of the additive for a developer of the present invention (Example (4)) and the fluid finishing agent (R-972: Nippon Aerosil Co., Ltd.) is in the range of 10 / 0.1 to 10/5. It was found that the effect was not changed at all.

Example 5 50 g of urea resin beads (manufactured by Nippon Kasei) as fine particles
Then, the same treatment as in Example 4 was carried out to obtain an additive for a developer of the present invention. As a result of being added to Toner A and tested in the same manner as in Example 4, both the charging property and the cleaning property were good.

Example 6 The same procedure as in Example 4 was repeated except that 0.4 g of methacryloyloxyethyltrimethylammonium chloride was used in place of 0.2 g of N-cetylvinylpyridinium chloride used in Example 4, and the result was tested. Both the chargeability and the cleaning property were good, and a clear copy image was obtained even after performing 20,000 copies.

Example 7 5% of sodium 1-naphthalene sulfonate in Example 4
The same treatment was performed using 1 g of a 10% aqueous solution of sodium acetate instead of 2 g of the aqueous solution. As a result of testing this, chargeability,
The cleaning property was good, and a clear copy image was obtained even after performing 20,000 copies.

[0033]

The developer additive of the present invention imparts excellent chargeability to a positively chargeable developer, which shows no decrease in chargeability under a high temperature and high humidity environment. Therefore, the electrophotographic developer obtained by using the developer additive of the present invention shows no background fog and no decrease in density under high temperature and high humidity. Further, there is an effect that the cleaning property is also good.

[Procedure amendment]

[Submission date] May 16, 1991

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be amended] Detailed explanation of the invention

[Correction method] Change

[Correction content]

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a developer additive to be added to an electrophotographic developer.

[0002]

In the electrophotographic recording method and the like, an electrostatic image formed on a photoconductor is usually developed with an electrophotographic developer containing a pigment or the like, and the obtained visible image is transferred onto a transfer paper, Fixing is performed with a heat roller or the like. At that time, in order for the electrophotographic developer to be used to be excellent in compatibility, it is necessary to be excellent in fluidity, caking resistance, fixing property, charging property, cleaning property and the like. .. Above all, it is important to enhance the fluidity and the cleaning property in order to carry out the development smoothly.

Conventionally, in order to improve the fluidity and cleaning property of the developer, for example, Japanese Patent Publication No. 54-1621.
As disclosed in Japanese Patent Publication No. 9, as a constituent material of a developer for electrophotography, hydrophobized silicon dioxide or resin powder (for example, polymethylmethacrylate powder)
Is being added. However, when these powders are added to the positively chargeable developer, there is a drawback that the amount of reverse polarity toner increases and the background fog occurs on the copy. In order to improve this defect, it has been proposed to use a metal oxide whose surface is treated with an aminosilane compound (Japanese Patent Publication No. 53-24447), but since the chargeability under high humidity conditions is poor, If a large amount of this is used as an additive for a developer, there is a problem that the chargeability is deteriorated. In particular, in the case of a one-component developer, it is necessary to add a large amount from the viewpoint of improving developability and fluidity, but as a result, there is a disadvantage that the chargeability is extremely deteriorated.

[0004]

SUMMARY OF THE INVENTION The present invention has been made for the purpose of overcoming the above-mentioned problems of the prior art. That is, an object of the present invention is to provide an additive for a developer that imparts excellent charging characteristics to a positively chargeable developer, and in particular, electrophotography in which a decrease in chargeability does not occur in a high temperature and high humidity environment. It is to provide an additive for a developer for obtaining a developer.

[0005]

Means for Solving the Problems The present inventors have focused on a polymer constituting the surface of organic or inorganic fine particles, and as the polymer, a vinyl monomer having a quaternary nitrogen containing an anion other than halogen is used. It was found that the above object can be achieved by using a copolymer component, and the present invention has been completed. That is, the developer additive of the present invention is obtained by allowing a polymer having a vinyl monomer having a quaternary nitrogen having a halogen ion as an anion component to be a component of a copolymer to be present on the surface of organic or inorganic fine particles. It is produced by performing an ion exchange treatment, and is characterized in that the halogen ion is converted into another anion.

The present invention will be described in detail below. The organic or inorganic fine particles constituting the present invention are metal oxides or resin powders. Specifically, as the metal oxide,
Examples thereof include various metal oxides such as silicon dioxide, alumina, titanium dioxide, iron oxide, chromium oxide, cerium oxide, magnesium oxide and zinc oxide.

Further, as the resin powder, for example, acrylic resin beads (polymethylmethacrylate powder), silicon resin beads, polyamide beads, polyurea beads,
Melamine resin beads, urea resin beads and the like can be used.

In the present invention, a polymer containing a vinyl monomer having a quaternary nitrogen having a halogen ion as an anion component as one component of the copolymer is present on the surface of these organic or inorganic fine particles. May exist in a state of being chemically bound to the surface of the organic or inorganic fine particles or in a state of being physically attached thereto.

At least one component of the above-mentioned polymer is formed by using a vinyl monomer having a quaternary nitrogen having a halogen ion as an anion component as a constituent component.
The vinyl monomer having a quaternary nitrogen having a halogen ion as an anion component used in the present invention,
For example, acryloyloxyethyltrimethylammonium chloride, acryloyloxyethyltriethylammonium chloride, methacryloyloxyethyltrimethylammonium chloride, methacryloyloxyethyltriethylammonium chloride, methacryloyloxyethylbenzylammonium chloride (meth) acrylate ammonium salt monomer, acrylamide (Meth) acrylamide ammonium salt monomers such as trimethylpropylammonium chloride, acrylamidotriethylpropylammonium chloride, methacrylamidotrimethylpropylammonium chloride and methacrylamidobenzylpropylammonium chloride, vinylbenzylethylammonium chloride Id, vinylbenzyl ammonium salt monomers such as vinylbenzyltrimethylammonium chloride, N-butylvinylpyridinium bromide, vinylpyridinium salt monomers such as N-cetylvinylpyridinium chloride, N-vinyl-2-methylimidazolinium chloride, N- Examples thereof include vinyl imidazolinium salt monomers such as vinyl-2,3-dimethyl imidazolinium chloride.

Examples of the other monomer copolymerizable with the vinyl monomer having a quaternary nitrogen containing the halogen ion as an anion component include, for example, methyl methacrylate, ethylene glycol dimethacrylate, ethyl methacrylate and n-butyl. Methacrylic acid ester such as methacrylate, iso-butyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, methyl acrylate, ethyl acrylate,
Any water-soluble monomer such as acrylic acid ester such as n-butyl acrylate, iso-butyl acrylate, hydroxypropyl acrylate, and hydroxybutyl acrylate, and a monomer having a vinyl group soluble in the water-soluble monomer can be used. Examples thereof include styrene, divinylbenzene, and various acrylic acid esters.

In the present invention, the above halogen ion is finally converted into another anion by the ion exchange treatment, and various other anion components can be used. Specific examples include, for example, acetate ion,
Carboxylic acid ions such as butyrate ion, caprylate ion, laurate ion, stearate ion, benzoate ion, naphthalenecarboxylate ion, naphthylacetate ion, p-toluenesulfonate ion, p-styrenesulfonate ion, naphthalenesulfone Examples thereof include acid ion, 4-hydroxynaphthalene sulfonate ion, lauryl benzene sulfonate ion, dodecyl benzene sulfonate ion, naphthoquinone sulfonate ion, and other sulfonate ions, and lauryl sulfate ion, dodecyl sulfate ion, and other sulfate ions. Further, examples include those derived from acid dyes such as acid yellow, acid red, acid violet and acid blue. In the ion exchange treatment, these anions may be used by dissolving them in deionized water in the form of sodium salt or potassium salt as shown below.

The above-mentioned additive for a developer of the present invention is prepared by preliminarily pretreating the surface of organic or inorganic fine particles to introduce a substituent capable of reacting with a vinyl monomer having a quaternary nitrogen, and then adding the organic or inorganic fine particle. A polymer obtained by treating the surface of fine particles with a vinyl monomer having a quaternary nitrogen having a halogen ion as an anion component, and using a vinyl monomer having a quaternary nitrogen having a halogen ion as an anion component as one component of the copolymer It is produced by allowing it to exist and then performing an ion exchange treatment to convert the halogen ion into another anion.

The developer additive of the present invention is a polymer containing a vinyl monomer having a quaternary nitrogen having a halogen ion as an anion component as a component of a copolymer on the surface of organic or inorganic fine particles. By coating a mixture of the polymer with another polymer by a method such as spray drying, coacervation, or interfacial precipitation, an ion exchange treatment is carried out to convert the halogen ion into another anion. It can be manufactured.

In the above method, the pretreatment is, for example,
When the organic or inorganic fine particles are silicon dioxide, by treating as vinyltrimethylsilane,
In the case of polymethylmethacrylate, it is carried out by treating with ethylene glycol dimethacrylate. This pretreatment is preferably performed by appropriately changing the pretreatment agent depending on the type of organic or inorganic fine particles.

The conversion of the halogen ion into another anion is carried out by dissolving the sodium salt or potassium salt of the corresponding anion in deionized water and adding organic or inorganic fine particles to this aqueous solution, or adding organic or inorganic salt to the aqueous solution. It is performed by adding or removing inorganic fine particles and then washing with water.

Any sodium or potassium anion salt can be used as long as it is water-soluble and can exchange ions with halogen ions. Specific examples include, for example, carboxylic acid salts such as sodium acetate, potassium acetate, sodium butyrate, sodium caprylate, sodium laurate, sodium stearate, sodium benzoate, sodium naphthalenecarboxylate, potassium naphthylacetate, and p-toluene sulfone. Sodium salt, sodium p-styrenesulfonate,
Examples thereof include sodium naphthalene sulfonate, sodium 4-hydroxynaphthalene sulfonate, sodium lauryl benzene sulfonate, sodium dodecyl benzene sulfonate, sodium naphthoquinone sulfonate, and the like, and sulfates such as sodium lauryl sulfate and sodium dodecyl sulfate. Acid dyes such as acid yellow, acid red, acid violet and acid blue can also be used.

Further , other polymer powder is mixed with the above additives.
You may match. A polymer powder that can be mixed with the above additives
For example, vinylidene chloride, vinylidene fluoride, etc.
Vinylidene polymer, polyethylene, polypropylene, etc.
Olefin polymer, polyester, polycarbonate
Resin, polyurethane, epoxy resin, phenol resin,
An example is a polyether resin. As the particle size of the powder,
It is preferably about 0.1 to 2 μm. But above
Polymer powder is about 1/2 to 1/100 of the additive
It is desirable to mix them at a ratio of.

[0018]

Example 1 As fine particles, 50 g of silicon dioxide powder (130: Nippon Aerosil Co., Ltd.) was taken, and vinyltrimethoxysilane (SZ6300: Toray Silicone Co., Ltd.) was stirred with stirring in a high-speed stirrer (Henschel mixer). )) Add 5 g into a solution dissolved in 10 liters of toluene and add 110 ° C.
The mixture was stirred for 1 hour while heating to 0 ° C., and toluene was removed to introduce CH ₂ ═CHSi—O— groups onto the surface of silicon dioxide.
The treated fine particles are suspended in 250 g of ion-exchanged water, and a propeller type agitator (Three One Motor: Shinto Kagaku Co., Ltd.)
While rotating at 200 rpm, 0.4 g of potassium persulfate, 0.2 g of N-cetylvinylpyridinium chloride and 2.0 g of methyl methacrylate, 0.1
Add 6 g of sodium bisulfite sequentially and add 3 at 25 ° C.
A time reaction was performed. After the reaction is complete , open it in the filtration bottle
After filtration, it was washed with 2 kg of ion-exchanged water. This operation was repeated 4 times to thoroughly wash the fine particles . next,
A suspension of these fine particles dispersed in 10 liters of ion-exchanged water.
Add 5% water of sodium 1-naphthalene sulfonate to the suspension.
Add 2 g of solution and stir at room temperature for 30 minutes to remove ion exchange reaction.
I responded. After completion of the reaction, the fine particles were washed 5 times with 1 liter of ion-exchanged water in the same manner as above to obtain the developer additive of the present invention.

Next, 35 parts by weight of magnetic powder (EPT-1000: Toda Kogyo Co., Ltd.), 1 part by weight of cetylpyridinium chloride, styrene-acrylic resin (SAN MI-2).
D: 100 weight of Sanyo Kasei Co., Ltd. was kneaded with a Banbury mixer (Kobe Steel Co., Ltd.), pulverized with Jutshell (Nippon Pneumatic), and classified by a dispersion separator (Nippon Pneumatic) to give 5 ~
Toner A having an average volume diameter of 15 μm was prepared. To 1000 g of this toner A is added 10 g of the above-mentioned additive for developer.
In addition, a toner B was prepared by stirring for 2 minutes while rotating a 10 m / sec blade with a Henschel mixer.

As a comparative example, 1000 g of toner A
Aminosilane-treated silicon dioxide powder (RA-20
OH: Nippon Aerosil Co., Ltd. (10 g) was added and stirred for 2 minutes while rotating a 10 m / sec blade with a Henschel mixer to prepare a toner C.

The above three toners A, B and C were put in a 5014 copying machine manufactured by Fuji Xerox Co., Ltd., and high temperature and high humidity (30 ° C.,
85% RH), normal temperature and normal humidity (22 ° C., 55% RH), low temperature and low humidity (10 ° C., 15% RH), and the results of checking the chargeability of the developer and the printed image (see Table 1). It was found that the toner B containing the developer additive of the present invention is very good.

[0022]

[Table 1]

Example 2 As a fine particle, 50 g of alumina powder (AOC: Nippon Aerosil Co., Ltd.) was used to prepare an additive for a developer in the same manner as in Example 1, and the toner A used in Example 1 was 2 wt%.
When added, a good developer free of background fog was obtained under high temperature and high humidity. In addition, the addition amount is 0.3 to 5.0 wt%
Good results were obtained even when the range was changed.

Example 3 Toner D prepared by removing N-cetylvinylpyridinium chloride from Toner A prepared in Example 1 was prepared, and 2 parts of the developer additive of the present invention prepared in Example 1 was prepared. Add 0.0 wt% and use Henschel mixer for 15m /
Toner E was prepared by stirring for 10 minutes and was tested. As a result, even after 20,000 copies, generation of background fog and reduction in density were not observed at high temperature and high humidity.

Example 4 As fine particles, polymethylmethacrylate powder (Mp-1
00: Soken Chemical Co., Ltd.) 50 g, deionized water 1
Add 25g, 200 rpm with a stirrer (three-one motor manufactured by Shinto Kagaku Co., Ltd.) equipped with a propeller type stirring blade.
Stir in minutes. After adding 5 g of IN nitric acid and 4 g of a 10% cerium sulfate aqueous solution, 0.5 g of ethylene glycol dimethacrylate was added, and the reaction was carried out at 15 ° C. for 3 hours. After completion of the reaction, the mixture was poured into 1 liter of ion-exchanged water, sufficiently stirred and allowed to stand. After the fine particles had settled, the supernatant was removed. This operation was repeated twice more to wash the fine particles. In this way, fine particles in which ethylene glycol dimethacrylate was graft-polymerized on the surface of the fine particles were obtained.
This was resuspended in ion-exchanged water again and stirred at 200 rpm with a stirrer (three one motor: manufactured by Shinto Kagaku Co., Ltd.) equipped with a propeller-type stirring blade. Next, 0.4 g of potassium persulfate, 0.2 g of N-cetylvinylpyridinium chloride, 2.0 g of methyl methacrylate, and 0.16 g of sodium hydrogen sulfite were sequentially added to this, and reacted at 25 ° C. for 3 hours. I went. 2 after the reaction
It was poured into 1 liter of ion-exchanged water, thoroughly stirred and filtered.
After filtering the fine particles, 2 liters of ion-exchanged water was further added, and this operation was repeated 4 times to wash the fine particles. Next, 2 g of a 5% aqueous solution of sodium 1-naphthalenesulfonate was added to this fine particle suspension and stirred at room temperature for 30 minutes to carry out an ion exchange reaction. After completion of the reaction, the fine particles were washed with 1 liter of ion-exchanged water 5 times while filtering to obtain the developer additive of the present invention. The obtained fine particle suspension was opened in a stainless steel vat, dried at 60 ° C. for 10 hours with a dryer (made by Yamato Scientific Co., Ltd.), then placed in a Henschel mixer and stirred to disperse the fine particles to develop the developer of the present invention. An additive powder was obtained.

To the toner A prepared in Example 1, 2 wt% and a fluidity improver (R-972: Nippon Aerosil Co., Ltd. 0.3 wt%) were added, and a blade was applied with a Henschel mixer at 10 m / sec. The developer F was prepared by rotating and stirring for 10 seconds. When this developer was tested in the same manner as in Example 1, it was confirmed to be very good. (See Table 2)

[0027]

[Table 2]

Further, this toner F has a good cleaning property, and is superior to the toners B, C, and E in comparison.
As a result , no contamination of the photosensitive drum was observed even after 20,000 copy operations. Therefore, this developer additive not only provides stable chargeability but also good cleaning performance. all right. As described above, the developer additive of the present invention exhibited a sufficient effect even when used in combination with the conventional fluidity improver .

The developer additive of the present invention (Example (4) and
It was found that the mixing ratio with the fluidity improver (R-972: Nippon Aerosil Co., Ltd.) showed no effect in the range of 10 / 0.1 to 10/5.

Example 5 50 g of urea resin beads (manufactured by Nippon Kasei) as fine particles
Then, the same treatment as in Example 4 was carried out to obtain an additive for a developer of the present invention. As a result of being added to Toner A and tested in the same manner as in Example 4, both the charging property and the cleaning property were good.

Example 6 The same procedure as in Example 4 was repeated except that 0.4 g of methacryloyloxyethyltrimethylammonium chloride was used in place of 0.2 g of N-cetylvinylpyridinium chloride used in Example 4, and the result was tested. Both the chargeability and the cleaning property were good, and a clear copy image was obtained even after performing 20,000 copies.

Example 7 5% of sodium 1-naphthalene sulfonate in Example 4
The same treatment was performed using 1 g of a 10% aqueous solution of sodium acetate instead of 2 g of the aqueous solution. As a result of testing this, chargeability,
The cleaning property was good, and a clear copy image was obtained even after performing 20,000 copies.

[0033]

The developer additive of the present invention imparts excellent chargeability to a positively chargeable developer, which shows no decrease in chargeability under a high temperature and high humidity environment. Therefore, the electrophotographic developer obtained by using the developer additive of the present invention shows no background fog and no decrease in density under high temperature and high humidity. Further, there is an effect that the cleaning property is also good.

Claims (1)

[Claims] 1. An ion exchange treatment is carried out after a polymer containing a vinyl monomer having a quaternary nitrogen having a halogen ion as an anion component is present as a component of a copolymer on the surface of organic or inorganic fine particles. An additive for developers, characterized in that the halogen ion is converted into another anion.