JP2002123034A - Toner for developing electrostatic images - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrostatic image developing toner suitable for a heat roll fixing system, which shows good fixing / offset characteristics in a wide temperature range. In addition, excellent color reproducibility and transparency,
In addition, the present invention provides a toner for developing an electrostatic image for color, which exhibits a stable charging behavior even during continuous printing, and provides a good high-quality image. A toner containing a binder resin, a colorant, a release agent, and a charge control agent, wherein the release agent is a wax containing a higher fatty acid ester compound and / or an aliphatic alcohol compound as a main component. In addition, a toner for developing an electrostatic image, in which the charge control agent is a complex or a salt represented by the following general formula 1, is used. <General formula 1>

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a toner for developing an electrostatic image used in an electrophotographic method, an electrostatic recording method, or an electrostatic printing method.

[0002]

2. Description of the Related Art In a two-component developing method in electrophotography, a carrier shares functions such as agitating, transporting, and charging a developer, and the function separation between the carrier and the toner is clear. For this reason, the two-component developing method is widely used because it is relatively easy to control the charge of the toner and can cope with high speed operation.

Recently, a color toner in which a cyan pigment, a magenta pigment, a yellow pigment or other chromatic pigments are dispersed in a binder has been used, and full-color or mono-color copying using these color toners has been used. Machines and printers have been developed.

[0004] Such a color toner does not cause color turbidity by exhibiting vivid coloration of an image after printing and exhibiting excellent transparency in color superposition in multicolor printing. Having clear color reproducibility, or projecting a color image obtained by transferring and fixing on an overhead projector (hereinafter referred to as OHP) sheet and projecting it on a screen to produce clear colors without turbidity. Color reproduction characteristics are required.

As a method for fixing a toner image, a heat roll fixing method is widely and generally used. In this case, good fixing property and anti-offset property are also important characteristics required for a color toner. is there. In recent color copying machines or printers, the processing speed has been increased, so that the fixing temperature has become lower and the fixing time has become shorter. Furthermore, in order to simplify the machine structure and facilitate maintenance, an oil-less fixing system was developed, in which oil for preventing offset was not applied to the fixing heat roll, and the demand for suitable color toners increased. I have.

Various studies have been made on the color toner used in the two-component developing method in order to satisfy these required characteristics. In particular, the selection of the charge control agent and the release agent is important, and it is necessary to select a molecular design and a material according to the characteristics of the carrier used together with the toner. As the charge control agent, various skeleton charge control agents such as various salicylic acid metal complexes, quaternary ammonium salts, trimethylethane dyes, and metal complex salt azo dyes have been studied. Further, as the release agent, low molecular weight polypropylene or polyethylene wax has been mainly studied. For example, republished patent WO99 / 28729 proposes a toner using a novel salicylic acid-based zirconium complex or salt as a charge control agent. Further, in an example of the publication, a black toner using the charge control agent, a low molecular weight polypropylene wax, and carbon black is reported.

However, the toner sufficiently satisfies the fixing performance and the anti-offset performance in a wide temperature range from a low temperature range to a high temperature range, has good compatibility with a carrier, and reaches a target charge amount immediately after mixing, and No color toner capable of maintaining the charge level has been found. In particular, recently, copiers and printers for high-speed color printing utilizing the features of the two-component developing system have been developed, and no toner for high-speed color printing suitable for such machines has been found.

SUMMARY OF THE INVENTION It is an object of the present invention to provide a toner for developing an electrostatic image suitable for a heat roll fixing system, which shows good fixing / offset characteristics in a wide temperature range.

Another object of the present invention is to provide a color electrostatic image which is excellent in color reproducibility and transparency, exhibits a stable charging behavior even in continuous printing, and provides a good high-quality image. An object of the present invention is to provide a developing toner.

[0009]

Means for Solving the Problems The present inventors have made intensive studies to solve the above problems, and as a result, have reached the present invention.

That is, in order to solve the above-mentioned problems, the present invention provides a toner containing a binder resin, a colorant, a release agent and a charge control agent, wherein the release agent is a higher fatty acid ester compound and / or Or a wax containing an aliphatic alcohol compound as a main component, wherein the charge control agent is a zirconium complex or salt represented by the following general formula 1. is there. <General formula 1>

Embedded image Wherein R ₁ is a quaternary carbon, methine, methylene,
N may include a heteroatom of N, S, O, or P; Y represents a cyclic structure connected by a saturated bond or an unsaturated bond;
₂ and R ₃ are each independently an alkyl group, an alkenyl group, an alkoxy group, an aryl group or an aryloxy group which may have a substituent, an aralkyl group or an aralkyloxy group, a halogen group, hydrogen, a hydroxyl group, a substituent Which may have an amino group, a carboxyl group, a carbonyl group, a nitro group,
R ₄ represents hydrogen or an alkyl group; t is an integer of 0 to 1 to 12; m is an integer of 1 to 20; n is an integer of 0 to 1 to 20; Is an integer from 0 to 1 to 4, p is an integer from 0 to 1 to 4, q is an integer from 0 to 1 to 3, r is an integer from 1 to 20, and s is 0 or an integer from 1 to 20. )

The binder resin used in the present invention can be used without any particular limitation as long as it is generally used as a binder resin in toner. For example, polystyrene, styrene- (meth- A) acrylate copolymer, olefin resin, polyester resin,
Examples include amide resins, carbonate resins, epoxy resins, and their graft polymers and mixtures thereof.

Among them, in consideration of charge stability, storage stability, fixing characteristics, and color reproducibility when used as a resin for a color toner containing a chromatic organic pigment or the like, polyester resin, styrene- ) Acrylic ester copolymer resins can be suitably used.

The polyester resin used in the present invention comprises:
For example, it is obtained by dehydrating and condensing a dicarboxylic acid and a diol by a usual method. As dicarboxylic acids, for example, phthalic anhydride, terephthalic acid, isophthalic acid, orthophthalic acid,
Naphthalenedicarboxylic acid, adipic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid,
Examples thereof include dicarboxylic acids such as hexahydrophthalic anhydride, tetrahydrophthalic anhydride, cyclohexanedicarboxylic acid, succinic acid, malonic acid, glutaric acid, azelaic acid, and sebacic acid, and derivatives thereof.

Examples of the diol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, butanediol, pentanediol, hexanediol, cyclohexanedimethanol, bisphenol A, polyoxyethylene- (2.0 ) -2,2-bis (4-hydroxyphenyl) propane and its derivatives,
Polyoxypropylene- (2.0) -2,2-bis (4
-Hydroxyphenyl) propane, polyoxypropylene- (2.2) -polyoxyethylene- (2.0)-
2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene- (6) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene-
(2.2) -2,2-bis (4-hydroxyphenyl)
Propane, polyoxypropylene- (2.4) -2,2
-Bis (4-hydroxyphenyl) propane, polyoxypropylene- (3.3) -2,2-bis (4-hydroxyphenyl) propane and derivatives thereof.

Further, for example, polyethylene glycol,
Diols such as polypropylene glycol, ethylene oxide-propylene oxide random copolymer diol, ethylene oxide-propylene oxide block copolymer diol, ethylene oxide-tetrahydrofuran copolymer diol, and polycaprolactone diol can also be used.

Further, if necessary, for example, a trifunctional or higher functional aromatic carboxylic acid such as trimellitic acid, trimellitic anhydride, pyromellitic acid, pyromellitic anhydride or a derivative thereof, or sorbitol, 1,2,3 , 6-hexanetetraol, 1,4-sorbitan, pentaerythritol, 1,2,4-butanetriol,
Trifunctional or higher alcohols such as 5-pentanetriol, glycerin, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trimethylolbenzene Or ethylene glycol diglycidyl ether, hydroquinone diglycidyl ether, N, N-diglycidyl aniline, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, trimethylolethane triglycidyl ether, pentaerythritol tetraglycidyl ether, bisphenol A Epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin,
Cresol novolak type epoxy resin, phenol novolak type epoxy resin, polymer or copolymer of vinyl compound having epoxy group, epoxidized resorcinol-acetone condensate, partially epoxidized polybutadiene, semi-dry or dry fatty acid ester epoxy compound A trifunctional or higher polyfunctional epoxy compound such as those described above can be used in combination.

The polyester resin for the color toner is preferably a linear polyester, and the resin preferably has a weight average molecular weight of 2 × 10 ³ to 1 × 10 ⁵ , and more preferably 4 × 10 ³ to 5 × 10 ³ . It is 3 × 10 ⁴ . The linear polyester has excellent melting properties at the time of fixing and is excellent in transparency, so it has excellent color development at the time of color superposition, and OHP.
The projected image of the sheet becomes clear.

When a branched or crosslinked polyester resin is used in combination with a trivalent or higher polyhydric carboxylic acid or polyhydric alcohol, the offset resistance at high temperatures is improved, and as a color toner of an oilless heat roll fixing system, or Suitable as a binder resin for black toner.

Further, when a linear polyester resin is used in combination with a branched or crosslinked polyester resin,
A toner having further excellent low-temperature fixability and high-temperature offset resistance can be obtained. The mixing ratio of the linear polyester and the branched or crosslinked polyester is preferably from 10/90 to 90/10, and more preferably from 30/70 to 70/30.

The polyester resin used in the present invention can be obtained by performing a dehydration condensation reaction or a transesterification reaction using the above-mentioned raw material components in the presence of a catalyst.
The reaction temperature and reaction time at this time are not particularly limited, but are usually 150 to 300 ° C. and 2 to 24 hours.

As a catalyst for carrying out the above reaction, for example, tetrabutyl titanate, zinc oxide, stannous oxide, dibutyltin oxide, dibutyltin dilaurate and the like can be appropriately used.

The polyester resin may have a glass transition point and a melt viscosity characteristic suitable for a two-component developing toner, and the temperature at which the viscosity becomes 1 × 10 ⁵ poise is 95 ° C. or higher. Is preferable because of its good fixability, and among them, those having a viscosity of 1 × 10 ⁵ poise and a temperature of 95 to 170 ° C. are more preferable because the fixability at low temperature is also good, and the viscosity is 1 × 10 ⁵ poise. Those having a temperature of from 95 to 160 ° C. are particularly preferred.

The glass transition temperature (Tg) is preferably 40 ° C. or higher, and particularly preferably the glass transition temperature (Tg) is 45 to 85 ° C.

Further, the acid value is 1 to 30 mg KO.
H / g, more preferably 1 to 20 mgKOH / g
It is. The hydroxyl value is 10 to 100 mg KO.
H / g, more preferably 10 to 60 mgKOH /
g is preferable in that the moisture resistance of the toner is improved.

The styrene monomer used in the styrene- (meth) acrylate copolymer resin used in the present invention includes, for example, styrene, α-methylstyrene, vinyltoluene, p-sulfonestyrene, dimethylaminomethyl There are styrene and the like.

Examples of the (meth) acrylate monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) acrylate. Alkyl (meth) acrylates such as meth) acrylate, tertiary butyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, and stearyl (meth) acrylate; cyclohexyl (meth) acrylate Alicyclic (meth) acrylates such as methacrylate; aromatic (meth) acrylates such as benzyl (meth) acrylate; hydroxyl-containing (meth) acrylates such as hydroxyethyl (meth) acrylate; Phosphoric acid group-containing (meth) acrylates such as riloxyethyl phosphate; halogen atoms such as 2-chloroethyl (meth) acrylate, 2-hydroxy-3-chloropropyl (meth) acrylate and 2,3-dibromopropyl (meth) acrylate (Meth) acrylates; epoxy group-containing (meth) acrylates such as glycidyl (meth) acrylate; ether group-containing (meth) acrylates such as 2-methoxyethyl (meth) acrylate and 2-ethoxyethyl (meth) acrylate;
(Meth) acrylates containing a basic nitrogen atom or an amide group, such as dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate;

Unsaturated compounds copolymerizable therewith can be used if necessary. For example, carboxyl group-containing vinyl monomers such as (meth) acrylic acid, itaconic acid, crotonic acid, maleic acid, and fumaric acid; sulfo group-containing vinyl monomers such as sulfoethylacrylamide; nitrile group-containing vinyl monomers such as (meth) acrylonitrile; Vinyl monomers containing a ketone group such as vinyl methyl ketone and vinyl isopropenyl ketone; basic groups such as N-vinyl imidazole, 1-vinyl pyrrole, 2-vinyl quinoline, 4-vinyl pyridine, N-vinyl 2-pyrrolidone and N-vinyl piperidone For example, a vinyl monomer containing a nitrogen atom or an amide group can be used.

The crosslinking agent may be used in the range of 0.1 to 2% by weight based on the vinyl monomer. As the crosslinking agent, for example, divinylbenzene, divinylnaphthalene,
Divinyl ether, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate,
Polyethylene glycol di (meth) acrylate, 1,3-
Butylene glycol di (meth) acrylate, 1,6-hexane glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polypropylene glycol di ( (Meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethylolmethanetetra (meth) acrylate, and the like.

Alternatively, in the case of a resin using a styrene- (meth) acrylate copolymer obtained by copolymerizing the carboxyl group-containing vinyl monomer, a crosslinked resin may be formed by using a metal salt. A as metal salt
l, Ba, Ca, Cd, Co, Cr, Cu, Fe, Hg, Mg, Mn, Ni, P
b, Sn, Sr, halide such as Zn, hydroxide, oxide,
There are carbonates, carboxylate salts, alkoxylates, chelate compounds and the like. The crosslinking reaction can be carried out by heating and stirring in the presence of a solvent.

As the method for producing the styrene- (meth) acrylic acid ester copolymer, a usual polymerization method can be adopted, and the polymerization reaction is carried out in the presence of a polymerization catalyst such as solution polymerization, suspension polymerization, or bulk polymerization. Is performed.

Examples of the polymerization catalyst include 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, and 1,1′-azobis (cyclohexane-1-yl).
(Carbonitrile), benzoyl peroxide, dibutyl peroxide, butyl peroxybenzoate, and the like, and the amount used is 0.1 to 10.
0% by weight is preferred.

The styrene- (meth) acrylate copolymer resin used in the present invention only needs to have appropriate glass transition point and melt viscosity characteristics as a toner for two-component development. Those having a temperature of 1 × 10 ⁵ poise at 95 ° C. or higher are preferable because of good fixability, and among them, the temperature at which the viscosity becomes 1 × 10 ⁵ poise is 95 ° C.
Those having a viscosity of 1 to 10 ⁵ poise are more preferable because the fixability at low temperatures is good.

On the other hand, the glass transition temperature (Tg) of the styrene- (meth) acrylate copolymer resin is 40 ° C.
Those described above are preferred, and among them, those having a Tg of 45 to 85 ° C are particularly preferred. The acid value is desirably 30 or less, particularly desirably 20 or less. If the acid value is too high, the charge amount will decrease, and the desired charge amount cannot be obtained.

In the present invention, in order to produce a color toner using a chromatic colorant, it is desirable to use a polyester resin from the viewpoint of excellent color development and transparency of a color image. Polyester resin is more tough and more resistant to stress in a developing device than styrene acrylic resin, and has a low melting point and is suitable as a resin for color toner.

As the coloring agent that can be used in the present invention, well-known coloring agents can be mentioned. Examples of the black colorant include carbon black such as furnace black, channel black, acetylene black, thermal black, and lamp black classified according to the production method.

As an example of a chromatic colorant, a phthalocyanine C.I. I. Pigme
nt Blue 15-3, an indanthrone C.I. I.
Pigment Blue 60 and the like are quinacridone-based C.I. I. Pigment Red
122, azo C.I. I. Pigment Red 2
2, C.I. I. Pigment Red 48: 1, C.I.
I. Pigment Red 48: 3, C.I. I. Pig
Ment Red 57: 1, etc., and an azo-based C.I. I. Pigment Yellow 12,
C. I. Pigment Yellow 13, C.I. I.
Pigment Yellow 14, C.I. I. Pigm
ent Yellow 17, C.I. I. Pigment
Yellow 97, C.I. I. Pigment Yellow
ow 155, isoindolinone-based C.I. I. Pigm
ent Yellow 110, a benzimidazolone C.I. I. Pigment Yellow 151, C.I.
I. Pigment Yellow 154, C.I. I. P
and the like.

The content of the coloring agent is determined by the binder resin 100
It is preferably in the range of 1 part by weight to 20 parts by weight based on parts by weight. These colorants can be used alone or in combination of two or more.

The release agent used in the present invention is a wax containing a higher fatty acid ester compound and / or an aliphatic alcohol compound as a main component. Such a release agent is preferable because it has good dispersibility in the polyester resin of the present invention, and has good release properties and slidability. When these waxes are added to the toner, better hot offset resistance and fixing strength can be obtained as compared with the same amount of polyolefin wax such as polypropylene wax and polyethylene wax.

Further, a wax containing a higher fatty acid ester compound and / or an aliphatic alcohol compound as a main component acts as a release agent for preventing an offset phenomenon at the time of heat roll fixing, and also has a large number of sheets for a long time. Also in printing, for example, when used as a two-component developer toner, it gives a stable charge to the toner without adhering to the carrier surface and enables printing of high-quality and high-definition images without generation of scattering toner etc. And Further, when a color toner is used together with a chromatic colorant, a color toner having excellent transparency as compared with a hydrocarbon wax such as a polypropylene wax can be obtained. The color toner having such characteristics is used for printing on an OHP sheet, which is required to have a transparent and vivid projected image, and for printing an intermediate color having good color reproducibility by printing two or more colors in an overlapping manner. Are suitable.

The wax mainly containing a higher fatty acid ester compound and / or an aliphatic alcohol compound is carnauba wax, montan ester wax, rice wax, scale insect wax, lanolin wax or a compound represented by the following general formulas 2 to 6: There is. <General formula 2>

Embedded image (R1 and R2 are a hydrocarbon group having 1 to 40 carbon atoms,
At least one of them represents a chain hydrocarbon group having 12 or more carbon atoms. )

<General formula 3>

Embedded image (R1, R2 and R3 are a hydrocarbon group having 1 to 40 carbon atoms, and at least one of them represents a chain hydrocarbon group having 12 or more carbon atoms.)

<General formula 4>

Embedded image (R1, R2 and R3 are a hydrocarbon group having 1 to 40 carbon atoms, and at least one of them represents a chain hydrocarbon group having 12 or more carbon atoms.)

<General formula 5>

Embedded image (R1 is a hydrocarbon group having 12 to 40 carbon atoms. R2 is a hydrocarbon group having 1 to 40 carbon atoms. A + b = 4, a represents an integer of 1 to 4, and b represents an integer of 0 to 3. Represents.)

<General formula 6>

Embedded image (R1, R2 and R3 are hydrocarbon groups having 1 to 40 carbon atoms, at least one of which is a chain hydrocarbon group having 12 or more carbon atoms, and a and c are integers of 0 to 2,
a + c = 2. b is an integer from 1 to 4, and d is 1
Or 2. Furthermore, e = d-1. )

The following compounds are specific examples of the wax represented by the above general formula.

<Wax 1>: Specific example of general formula 2

Embedded image

<Wax 2>: Specific example of general formula 3

Embedded image

<Wax 3>: Specific example of general formula 4

Embedded image

<Wax 4>: Specific example of general formula 5

Embedded image

<Wax 5>: Specific example of general formula 6

Embedded image

<Wax 6>: Specific example of general formula 6

Embedded image

As the carnauba wax, it is preferable to use a carbauba wax that has been freed from fatty acids and whose free fatty acids have been removed by purification. The acid value of the free fatty acid type carnauba wax is preferably 8 or less, more preferably 5 or less. The free fatty acid-type carnauba wax becomes finer crystals than the conventional carnauba wax, and the dispersibility in the polyester resin is improved. The montan ester wax is refined from a mineral, and becomes fine crystals like the carnauba wax by refining, so that the dispersibility in the polyester resin is improved.

The acid value of the montan ester wax is particularly preferably 30 or less. Rice wax is obtained by refining rice bran wax, and has an acid value of 13
The following is preferred.

The scale insect wax can be obtained by dissolving the waxy component secreted by the larva of the scale insect (also known as lobster) in, for example, boiling water, separating the upper layer, cooling and solidifying, or repeating this. The scale insect wax purified by such a means is white in a solid state, has an extremely sharp melting point, and is suitable as a toner wax in the present invention. The acid value is reduced to 10 or less due to purification, and is preferably 5 or less for toner.

The lanolin wax is obtained by purifying and dehydrating a waxy substance adhering to wool's wool, and preferably has an acid value of 8 or less, more preferably 5 or less.

Examples of the release agent mainly containing an aliphatic alcohol compound include those mainly containing a higher alcohol obtained by an oxidation reaction of paraffin, olefin or the like. Examples of the release agent containing an aliphatic alcohol as a main component include “Unilin 425”, “Unilin 550” (both by Petrolite), “NPS-9210”,
“PARACOL 5070” (Nippon Seiro Co., Ltd.) and the like.

Of the above specific examples, carnauba wax having an acid value of 8 or less, <i> the wax </ i>, and <wax 4>, which is a tetrabehenic acid ester of pentaerythritol, are the most preferred waxes that can be used in the present invention.

The wax of the present invention has a melting point of 65.
Those in the range of ゜ C to 130 ° C. have a large contribution to the offset resistance and are particularly preferable.

The wax may be used alone or in combination, and good fixing offset performance can be obtained by adding 0.3 to 15 parts by weight, preferably 1 to 5 parts by weight, to the binder resin. If the amount is less than 0.3 parts by weight, the offset resistance is impaired. If the amount is more than 15 parts by weight, the fluidity of the toner is deteriorated. This adversely affects the charging characteristics of the toner.

Incidentally, synthetic waxes such as polyamide wax, graft polymerization wax, modified polyolefin wax, polypropylene wax and polyethylene wax can be used in combination with the wax in the present invention.

In the present invention, a compound represented by the following general formula 1 is used as a charge control agent. <General formula 1>

Embedded image <General formula 1> Wherein R ₁ is a quaternary carbon, methine, methylene,
N may include a heteroatom of N, S, O, or P; Y represents a cyclic structure connected by a saturated bond or an unsaturated bond;
₂ and R ₃ are each independently an alkyl group, an alkenyl group, an alkoxy group, an aryl group or an aryloxy group which may have a substituent, an aralkyl group or an aralkyloxy group, a halogen group, hydrogen, a hydroxyl group, a substituent Which may have an amino group, a carboxyl group, a carbonyl group, a nitro group,
R ₄ represents hydrogen or an alkyl group; t is an integer of 0 to 1 to 12; m is an integer of 1 to 20; n is an integer of 0 to 1 to 20; Is an integer from 0 to 1 to 4, p is an integer from 0 to 1 to 4, q is an integer from 0 to 1 to 3, r is an integer from 1 to 20, and s is 0 or an integer from 1 to 20. As the charge control agent of the present invention, compounds having various structures can be suitably used without departing from the general formula 1. However, the compounds having the following structures have higher charge-giving ability, charge stability, and transparency. It can be suitably used.

<Charge Control Agent 1>

Embedded image

<Charge Control Agent 2>

Embedded image

<Charge control agent 3>

Embedded image

The amount of the compound to be used is in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of the binder resin, and within this range, sufficient charging performance can be obtained without a decrease in toner resistance.

As the charge control agent that can be used in combination with the compound of the general formula 1, a conventionally known charge control agent can be used. For example, a nigrosine dye, a triphenylmethane dye, a quaternary ammonium salt, a resin containing a quaternary ammonium group and / or an amino group as a positive charge control agent, a trimethylethane dye, a metal of salicylic acid as a negative charge control agent Complex salts, metal complex salts of benzylic acid, copper phthalocyanine, perylene, quinacridone, azo pigments, metal complex salt azo dyes, acid dyes containing heavy metals such as azochrome complexes, calixarene-type phenolic condensates, cyclic polysaccharides, carboxyl groups And / or a resin containing a sulfonyl group, and the like, if necessary.

In particular, when the toner of the present invention is used as a color toner, it is preferable to use a colorless compound as the charge control agent to be used in combination. Examples of the colorless negatively chargeable charge control agent include “Bontron E-8” manufactured by Orient Chemical Co., Ltd. as a metal (Zn) complex compound of salicylic acid.
"4" is a metal complex compound of benzylic acid such as "LR-147" or "LR-297" manufactured by Nippon Carlit.
As colorless positive charge control agents, TP-302, TP-415, and TP-610 having a quaternary ammonium salt structure;
(Hodogaya Chemical), Bontron P-51; (Orient Chemical), Copy Charge PSY (Clariant Japan), and the like. Since the charge control agent of the general formula 1 used in the present invention is a negative charge control agent, it is preferably a negative charge control agent when other charge control agents are used in combination.

In the present invention, various additives (referred to as external additives) can be used for modifying the surface of the toner such as improving the fluidity of the toner and improving the charging characteristics. Examples of the external additive that can be used in the present invention include silicon dioxide, titanium oxide, aluminum oxide, cerium oxide, zinc oxide, tin oxide,
Inorganic fine powders such as zirconium oxide and those obtained by surface-treating them with a hydrophobic agent such as silicone oil or silane coupling agent, polystyrene, acrylic, styrene acrylic, polyester, polyolefin, cellulose, polyurethane, benzoguanamine, melamine, nylon, Resin fine powders such as silicon, phenol, vinylidene fluoride, and Teflon (registered trademark) are used.

Among them, silicon dioxide (silica) whose surface is hydrophobized with various polyorganosiloxanes or silane coupling agents can be particularly preferably used. As such a product, for example, there is a product commercially available under the following trade names.

AEROSIL R972, R974, R202, R805, R812, RX200, RY200, R809, RX50, RA200HS, RA200H (Nippon Aerosil Co., Ltd.) WACKER HDK H2000, H2050EP HDK H3050EP, HVK2150 (Wacker Chemicals East Asia) Nipsil SS-10, SS-15, SS-20, SS-50, SS-60, SS-100, SS-50B, SS-50F, SS-10F, SS-40, SS-70, SS-72F, ( Nippon Silica Industry Co., Ltd.) CABOSIL TG820F (Cabot Specialty Chemicals, Inc.)

The particle diameter of the external additive is desirably 1/3 or less of the diameter of the toner, particularly preferably 1/10 or less. In addition, these external additives have different average particle diameters.
More than one species may be used in combination. The ratio of the external additive used is toner 1.
The amount is 0.05 to 5% by weight, preferably 0.1 to 3% by weight, based on 00 parts by weight.

In the toner of the present invention, other additives other than those described above may be contained in the toner particles. As an example, a lubricant such as metal soap and zinc stearate can be used, and as an abrasive, for example, cerium oxide and silicon carbide can be used.

When a part or all of the colorant is replaced with magnetic powder, it can be used as a magnetic one-component developing toner. As the magnetic powder, a ferromagnetic metal such as iron, cobalt, and nickel, or an alloy or compound powder such as magnetite, hematite, or ferrite is used. As these magnetic powders, those subjected to a hydrophobic treatment with an organic silicon or a titanium compound or the like, if necessary, are preferably used. The content of the magnetic powder is 15 to
70% by weight is good.

The toner composition of the present invention can be obtained by an extremely general manufacturing method irrespective of a specific manufacturing method. For example, a resin, a colorant, and a charge controlling agent are mixed with the melting point (softening) of the resin. Point) After melt-kneading as described above, it can be obtained by pulverizing and classifying. Specifically, for example, the resin and the colorant are mixed by a kneading means such as a two-roll, three-roll, pressure kneader, or a twin-screw extruder.
At this time, the colorant or the like may be uniformly dispersed in the resin,
The conditions of the melt-kneading are not particularly limited,
It is usually 30 seconds to 2 hours at 80 to 180 ° C. The coloring agent may be previously subjected to a flushing treatment so as to be uniformly dispersed in the resin, or a master batch melt-kneaded with the resin at a high concentration. Then, after cooling, it is pulverized finely by a pulverizer such as a jet mill and classified by an air classifier or the like.

The average particle size of the particles constituting the toner is not particularly limited, but is usually adjusted to be 5 to 15 μm. Usually, fine particles (hereinafter, referred to as an external additive) having a smaller particle size than the toner base are mixed with the toner base obtained in this manner using a mixer such as a Henschel mixer.

The toner of the present invention can be used as a two-component developer by mixing with a magnetic carrier. In this case, the surface of the magnetic carrier is desirably coated with a resin. By coating the surface with the resin, the charge of the developer is stabilized.

As a carrier for preparing a two-component developer using the toner of the present invention, an iron powder carrier, a magnetite carrier and a ferrite carrier used in a usual two-component developing system can be used. A ferrite or a magnetite carrier having high resistance, excellent environmental stability, and easy to form into a sphere and having good fluidity is preferably used. The shape of the carrier can be used without any particular problem, such as a spherical shape and an irregular shape. The average particle size is generally 10
The thickness is preferably from 500 to 500 μm, but is preferably from 30 to 80 μm for printing a high-resolution image.

Further, coated carriers obtained by coating these carriers with a resin can also be suitably used, and examples of the coated resin include polyethylene, polypropylene, polystyrene, polyacrylonitrile, polyvinyl acetate, and the like.
Polyvinyl alcohol, polyvinyl butyral, polyvinyl chloride, polyvinyl carbazole, polyvinyl ether polyvinyl ketone, vinyl chloride / vinyl acetate copolymer, styrene / acrylic copolymer, straight silicone resin comprising organosiloxane bond or its modified product, fluororesin, (Meth) acrylic resin, polyester, polyurethane, polycarbonate, phenol resin, amino resin, melamine resin, benzoguanamine resin, urea resin, amide resin, epoxy resin and the like can be used. Among these, silicone resin, fluororesin, and (meth) acrylic resin are particularly excellent in charge stability and coating strength, and can be more preferably used. That is, in the present invention, the magnetic carrier is preferably a resin-coated magnetic carrier coated with at least one resin selected from a silicone resin, a fluororesin, and a (meth) acrylic resin.

The method of coating the surface of the carrier core material with the resin is not particularly limited. However, a dipping method of dipping in a solution of the coating resin, a spray method of spraying the coating resin solution on the surface of the carrier core material, or a carrier method is used. Fluidized bed method in which the carrier is sprayed while being floated by flowing air, a kneader coater method in which a carrier core material and a coating resin solution are mixed in a kneader coater, and a solvent is removed. The solvent used in the coating resin solution is not particularly limited as long as it dissolves the coating resin. For example, toluene, xylene, acetone, methyl ethyl ketone, tetrahydrofuran, dioxane and the like can be used. The thickness of the coating layer on the carrier surface is usually 0.1 to 3.0 μm.

The weight ratio between the toner of the present invention and the magnetic carrier is not particularly limited.
The amount of the toner is 0.5 to 10 parts by weight per 00 parts by weight.

The thus-obtained toner for developing an electrostatic image of the present invention and the developer using the same are developed and fixed on a recording medium by a known and usual method. It is preferable to adopt a method. As the heat roll, a roll in which the surface of a cylindrical body that can be heated to a temperature at which the toner can be melted and fixed is coated with a coating resin having both releasability and heat resistance such as a silicone resin or a fluororesin is used. In the heat-roll fixing method, the toner is fixed by the printing medium passing between two rolls having at least one heat roll and pressed at an appropriate pressure as described above. The remarkable technical effect of the toner for developing an electrostatic image according to the present invention is exhibited in a developing / fixing device in which development is performed at a higher speed and heat roll fixing is performed.

As the recording medium in the present invention, any of those known and used can be used.
Examples include papers such as resin-coated paper, synthetic resin films and sheets such as PET films and OHP sheets.

[0083]

EXAMPLES Next, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples. In addition,
In the following, the numerical values in the composition table represent "parts by weight".
An example of the synthesis of the binder resin used in preparing the toner first is shown below.

(Synthesis Example 1) 415 parts by weight of terephthalic acid 415 parts by weight of isophthalic acid 1650 parts by weight of polyoxyethylene- (2.0) -2,2-bis (4-hydroxyphenyl) propane

The above monomers were stirred with a stirrer, a condenser,
The mixture was placed in a four-necked flask equipped with a thermometer, and 6 parts by weight of tetrabutyl titanate was added to all the acid components under a stream of nitrogen gas. Allowed to react for hours. The molecular weight of the obtained linear polyester was Mw: 11,000, Mn: 41.
The temperature at which the apparent melt viscosity became 1 × 10 ⁵ poise was 105 ° C., and the acid value was 10. Tg is 62
° C.

The apparent melt viscosity was measured using a flow tester CFT-500C manufactured by Shimadzu Corporation with a sample toner amount of 1.0.
g, weight 10kg, die hole diameter 1.0mm × 1.0m
m, the preheating time was 300 seconds at a measurement start temperature of 60 ° C., and the measurement was performed at a temperature rising rate of 6.0 ° C./min.

(Synthesis Example 2) 320 parts by weight of styrene 80 parts by weight of butyl acrylate 4 parts by weight of azobisisobutyronitrile 600 parts by weight of xylene

The above monomers were charged into a round bottom flask,
After reacting at 80 ° C for about 10 hours in a nitrogen gas atmosphere,
The polymerization was completed by heating to 130 ° C. Thereafter, the mixture was heated to 180 ° C. and deaerated under reduced pressure to 0.5 mmHg with a vacuum pump to remove the solvent.

When the apparent melt viscosity of the obtained styrene acrylic resin was 1 × 10 ⁵ poise, the temperature was 115 ° C.
Tg was 61 ° C.

Example 1 <Manufacture of Toner> 93 parts by weight of resin of Synthesis Example 1 4 parts by weight of Fastgen Super Magenta R manufactured by Dainippon Ink and Chemicals 1 part by weight of charge control agent 1 1 part by weight of purified carnauba wax No. 12 parts by weight (acid value 5, manufactured by Ceralica NODA) are mixed with a Henschel mixer and kneaded with a twin-screw kneader. The kneaded material thus obtained was pulverized and classified to obtain “toner material A” having a volume average particle diameter of 7.5 μm.

100 parts by weight of the above-mentioned "Toner raw material A" 1 part by weight of silica "R-812" manufactured by Nippon Aerosil Co., Ltd. was mixed with a Henschel mixer and then sieved.
"Toner A" was obtained.

<Adjustment of Developer> 4 parts of toner A and a carrier “Ferrite Carrier F-150” 9 manufactured by Powder Tech Co., Ltd.
The developer A was prepared by friction-mixing 6 parts.

Thereafter, toners were prepared according to the formulations shown in Table 1 in the same manner as in Example 1, and the developer A (Example 1) to the developer E (Example 5) and the developer F (Comparative Example 1) to Developer H (Comparative Example 3) was produced.

[0094]

[Table 1]

The indications in the table are as follows. Magenta R; Fastogen Super Magenta R manufactured by Dainippon Ink and Chemicals, Inc. TYHG; Toner Yellow HG VP2155 manufactured by Clariant Japan KET B.111; KET Blue 111 manufactured by Dainippon Ink and Chemicals Inc. Carnauba WAX; Carnauba wax no. 1 (acid value 5) manufactured by Cera Rica NODA Co., Ltd. 1 (acid value 2) manufactured by Cera Rica NODA Co., Ltd. ・ PP WAX; polypropylene wax manufactured by Viscol 550P “Sanyo Kasei” ・ Wax 4; tetrabehenate ester of pentaerythritol ・ E-84; zinc disalicylate complex “Orient Chemical”

<Fixing Offset Test by Heat Roll Fixing> An unfixed image sample of A-4 paper size was prepared using a test machine modified from a commercially available two-component developing type copying machine, and a heat roll fixing unit having the following specifications was installed. The fixing start temperature and the presence or absence of an offset phenomenon were confirmed under the following test conditions. In order to measure the fixing start temperature, an image density remaining ratio calculated by the following equation was obtained.

Image density residual ratio = image density after fastness test / image density before left test * Image density was measured by Macbeth image densitometer RD-918. * The image density after fastness test is the image density after rubbing the fixed image using a Gakushin type friction fastness tester (load: 200 g, rubbing operation: 5 strokes). Image density remaining ratio
At 80% or more, there was no practical problem, and the lowest temperature was the fixing start temperature.

The offset start temperature was a temperature at which the offset phenomenon was visually observed when the fixed image sample was observed. The results are shown in Table-2.

<Print Durability Test> Using a commercially available copying machine, the density of the image area and the density of the background stain in 50,000 continuous prints were measured, and the charge amount of the developer was measured. Image density and background dirt are measured by Macbeth densitometer RD-918.
Was measured. The background stain was obtained by subtracting the density of the white paper before printing from the density of the white background after printing. When the difference was less than 0.01, it was evaluated as ○, when it was less than 0.01 to 0.03, it was evaluated as Δ, and when it was 0.03 or more, it was evaluated as ×.

The charge amount was measured by using a blow-off charge amount measuring device by collecting toner from the inside of the developing device for each number of printed sheets. The results are shown in Table-2.

<Evaluation of OHP Sharpness> An unfixed image was formed on an OHP sheet using a commercially available copying machine, and the unfixed image was fixed using a separately prepared fixing tester. As a fixing tester, a heat roll fixing machine with a built-in temperature sensor was used at a roll temperature of 140 ° C. The heat roll (upper) is made of Teflon (registered trademark of DuPont), the lower roll is made of HTV silicon, and the load is 7 kg / 350 m.
m, the nip width was 4 mm, and the fixing speed was 50 mm / sec.

The OHP sheet prepared according to the above procedure was projected on a white screen by an overhead projector, and the sharpness was evaluated. The evaluation was made by visual observation, and a clear and transparent good projected image was evaluated as ○, and a turbid blackish projected image was evaluated as ×. Table 2 shows the results.
It was shown to.

[0103]

[Table 2]

The indications in the table are as follows. * "Charge amount"; [mu] C / g * "Background dirt evaluation" ○: less than 0.01, Δ: 0.01 to less than 0.03,
La: 0.03 or more

From the above results, it can be seen that the toners of Comparative Examples 1 and 3 are inferior in OHP permeability and have a higher fixing start temperature than the toners of Examples 1 to 4 using the same polyester resin. Further, in the developer using the toners of Comparative Examples 1 to 3, in the printing durability test, the image density and the charge amount at the initial stage of printing and at the time of printing 50,000 sheets were changed, and an increase in background smear was confirmed. Further, in Comparative Examples 1 and 3, toner binder component or wax component adhered to the carrier surface after printing 50KP (50,000 sheets), and generation of spent carrier was observed. Inside the machine, dirt due to toner scattering was observed around the photosensitive member and the peripheral portion of the developing device. Further, when the toner particles were sliced and the cross section thereof was observed with a microscope, it was recognized that polypropylene wax was dispersed as large particles in the binder resin. On the other hand, the toners of the examples were excellent in OHP transparency, low-temperature fixability, and offset resistance, had a constant charge amount even when printing at 50 KP, and were able to perform printing with a uniform image density. No toner scattering was observed around the developing device. further,
When the toner particles were sliced and observed with a microscope, it was observed that the wax was finely and uniformly dispersed in the toner particles.

[0106]

According to the present invention, a long-life static image having excellent fixability and anti-offset properties, showing stable charging behavior even during continuous printing, and obtaining a good image without fluctuation in image density. A charge image developing toner can be obtained.

Further, the toner of the present invention is excellent in transparency and shows good fixing / offset characteristics in a wide temperature range, so that it shows excellent characteristics as a color toner of an oilless heat roll fixing system.

Continuation of the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) // C07C 65/05 G03G 9/08 344 65/21 361 9/10 351 352 354 (72) Inventor Masanobu Nakamura Saitama 1-17-30 Chuo Warabi 1-709 Rene Warabi 1-709 F term (reference) 2H005 AA01 AA06 AA21 BA06 CA02 CA03 CA04 CA08 CA11 CA12 CA14 CA21 CA25 DA01 4H006 AA03 AB78 AB91 BJ50 BN30 BP30

Claims (6)

[Claims] 1. A toner comprising a binder resin, a colorant, a release agent and a charge control agent, wherein the release agent is a wax containing a higher fatty acid ester compound and / or an aliphatic alcohol compound as a main component. Wherein the charge control agent is a zirconium complex or salt represented by the following general formula 1. <General formula 1> Wherein R ₁ is a quaternary carbon, methine, methylene,
N may contain a heteroatom of N, S, O, or P; Y represents a cyclic structure connected by a saturated bond or an unsaturated bond;
₂ and R ₃ are each independently an alkyl group, an alkenyl group, an alkoxy group, an aryl group or an aryloxy group which may have a substituent, an aralkyl group or an aralkyloxy group, a halogen group, hydrogen, a hydroxyl group, a substituent Which may have an amino group, a carboxyl group, a carbonyl group, a nitro group,
R ₄ represents hydrogen or an alkyl group; t is an integer of 0 to 1 to 12; m is an integer of 1 to 20; n is an integer of 0 to 1 to 20; Is an integer of 0 to 1 to 4, p is an integer of 0 to 1 to 4, q is an integer of 0 to 1 to 3, r is an integer of 1 to 20, s is 0 or an integer of 1 to 20. ) 2. The binder resin according to claim 1, wherein the binder resin is a single polymer comprising at least one monomer selected from styrene monomers, acrylic acid and acrylate monomers, methacrylic acid and methacrylate monomers. 2. The toner for developing an electrostatic image according to claim 1, wherein the toner is a united or copolymer. 3. The electrostatic image developing toner according to claim 1, wherein the binder resin is a polyester resin. 4. The electrostatic image developing toner according to claim 1, wherein the colorant is a chromatic organic pigment. 5. The release agent is at least one selected from carnauba wax, montan ester wax, rice wax, scale insect wax, lanolin wax, and compounds represented by the following general formulas 2 to 6. The toner for developing an electrostatic image according to claim 1, 2, 3, or 4. <General formula 2> (R1 and R2 are a hydrocarbon group having 1 to 40 carbon atoms,
At least one of them represents a chain hydrocarbon group having 12 or more carbon atoms. <General formula 3> (R1, R2 and R3 are a hydrocarbon group having 1 to 40 carbon atoms, and at least one of them represents a chain hydrocarbon group having 12 or more carbon atoms.) <General formula 4> (R1, R2 and R3 are a hydrocarbon group having 1 to 40 carbon atoms, and at least one of them represents a chain hydrocarbon group having 12 or more carbon atoms.) <General formula 5> (R1 is a hydrocarbon group having 12 to 40 carbon atoms. R2 is a hydrocarbon group having 1 to 40 carbon atoms. A + b = 4, a represents an integer of 1 to 4, and b represents an integer of 0 to 3. <General formula 6> (R1, R2 and R3 are hydrocarbon groups having 1 to 40 carbon atoms, at least one of which is a chain hydrocarbon group having 12 or more carbon atoms, and a and c are integers of 0 to 2,
a + c = 2. b is an integer from 1 to 4, and d is 1
Or 2. Furthermore, e = d-1. ) 6. A resin-coated magnetic carrier coated with at least one resin selected from the group consisting of silicone resin, fluororesin, and (meth) acrylic resin. 6. The toner for developing an electrostatic image according to 5.