JP2003035969A - Nonmagnetic monocomponent developing toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a nonmagnetic monocomponent developing toner which exhibits stable electrostatic charge behavior even in continuous printing and has a long printing life and to provide a nonmagnetic monocomponent developing toner which causes a small density change in continuous printing and ensures good color reproducibility even in overprinting with color toners. SOLUTION: Each of the nonmagnetic monocomponent developing toners comprises toner particles containing at least a binder resin and a colorant, and the toner particles have been surface-treated with a silicone oil.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a non-magnetic one-component developing toner for developing an electrostatic charge image in electrophotography, electrostatic recording, electrostatic printing and the like. More specifically, it relates to a non-magnetic one-component developing toner having improved printing durability and printing stability.

[0002]

2. Description of the Related Art As a toner composition used in electrophotography, electrostatic recording, electrostatic printing, etc., generally, a dispersion of a black colorant such as carbon black in a binder resin is often used. . Recently, cyan pigment,
A color toner in which a magenta pigment or a yellow pigment is dispersed in a binder resin has also come into wide use. A multi-color image forming apparatus such as a color copying machine or a color printer using these color toners is installed in an office or the like, and is used for producing various kinds of report documents, presentation materials such as catalogs and pamphlets.

Generally, in the developing devices of these multicolor image forming apparatuses, a two-component developing system using toner and carrier is used. However, the two-component developing method requires a toner replenishing device, a device for mixing and agitating a developer consisting of toner and carrier, and the like. Furthermore, in the case of a multi-color image forming apparatus that performs color printing that reproduces colors of a photograph without impairing the color, a developing device that forms an image of four colors of cyan, magenta, yellow, and black is required, and the entire apparatus is The reality is that it must be enlarged.

Therefore, recently, in order to avoid such inconvenience, a color printer using a non-magnetic one-component developing system has been devised. This method can prevent the carrier surface from being contaminated by the components in the toner generated in the two-component developing method, and the deterioration of the image quality due to the change of the triboelectrification property due to the change of the mixing ratio of the toner and the carrier. The developing device is compact, the entire device can be downsized, and further, maintenance is easy and cost reduction can be achieved.

In the non-magnetic one-component developing system, the toner charge imparting mechanism is important, but generally, the toner is passed through between the developing sleeve and the charging member pressed against the developing sleeve and the toner is transferred. The method of triboelectrification is adopted. In that case, it is necessary to give sufficient consideration to the selection of materials for the developing sleeve and the charging member so that the toner is highly charged. For that purpose, it is necessary that the charging member be pressed against the developing sleeve with a certain strong pressure. is there.

However, under such conditions, the toner heats up due to friction and is fused to the charging member, or is over-pulverized to generate a state in which the toner is easily made into fine particles. When these phenomena occur, the image density is lowered, the conveyance of the toner onto the developing sleeve is obstructed, and various undesirable image troubles such as occurrence of white spots during development are caused.

Under such circumstances, in order for the toner to withstand the pressure between the developing sleeve and the charging member and form a stable image for a long period of time so that printing can be performed, for example, JP-A-8-314268 is used. As described in the publication, a polyester cross-linked with a carboxylic acid or alcohol having a valence of 3 or more is used as a resin component of the toner, or a high-molecular weight linear polyester resin is used to improve the durability of the toner. It is normal to give. Also, Japanese Patent No. 2754
As described in Japanese Patent No. 539, it is also known that by using an external additive having a different particle diameter in combination, embedding of an external additive having a small particle diameter is suppressed and durability is provided.

By the way, in the color toner, the sharpness of the printed image is required. To achieve this, there are various factors, but it is important that the toner fixed on the paper forms a highly transparent and uniform layer. For that purpose, it is necessary that the toner particles are melted at a relatively low temperature during fixing, and after fixing, the graininess is completely lost to form a film. This makes it possible to obtain clear secondary colors and tertiary colors when toners of different colors overlap in multicolor printing. In particular, in printing on an OHP sheet, high transparency is required, and if bubbles, spots, graininess, etc. remain in the fixed image, light is scattered, so a vivid projected image cannot be obtained. Therefore, in the non-magnetic one-component color toner, in order to fix the toner at a relatively low temperature and to obtain color development and transparency, the binder resin does not have a crosslinking component, is linear, and has a relatively low molecular weight. It was necessary to select the binder resin of.

Further, in the non-magnetic one-component developing method, a phenomenon called "selective development" in which particles having a high charge amount are selectively adhered to a developing roll and toner having a low charge amount remains without being developed. There is. When this selective development occurs, the charge amount of the toner decreases with the printing, the toner consumption increases in the latter half of the printing life, the image density increases, and the printing life shortens.
Such a variation in image density due to printing is a problem in the case of a color toner in which toner images of different colors are superposed and developed, because the color reproducibility of the developed image deteriorates.

In order to solve such a problem, Japanese Patent No. 26
Japanese Patent No. 94571 discloses a non-magnetic toner having a specific bulk density and containing fine silica powder treated with a silane coupling agent or silicone oil, and in Japanese Patent Application Laid-Open No. 07-036217, a polyester resin is disclosed. It has been proposed that a non-magnetic toner having a specific particle diameter is added with a fluidizing agent composed of inorganic fine particles having a specific particle diameter and having a specific viscosity, which has been treated with silicone oil. However, these are non-magnetic one-component toners that have sufficient durability and the density fluctuation during printing is extremely small because the silica fine powder is released or embedded in the toner particles as they are printed. It was difficult to get.

SUMMARY OF THE INVENTION An object of the present invention is to provide a non-magnetic one-component developing toner which exhibits stable charging behavior even during continuous printing and has a long printing life. Also,
It is another object of the present invention to provide a non-magnetic one-component developing toner which has a small density fluctuation during continuous printing and can obtain good color reproducibility even when overprinting with color toners.

[0011]

As a result of intensive studies to solve the above problems, the present inventors have found that a toner obtained by treating the surface of toner particles with silicone oil solves the above problems. The invention was completed.

That is, the present invention is a non-magnetic one-component developing toner comprising toner particles containing at least a binder resin and a colorant, wherein the toner particles are surface-treated with silicone oil. The present invention provides a non-magnetic one-component developing toner.

The toner surface-treated with the silicone oil of the present invention can withstand a strong shearing force that occurs when passing between the charging member and the developing sleeve of the non-magnetic one-component developing device, and is fused to the charging member. It is suitable as a non-magnetic one-component developing toner having excellent durability such that it has high chargeability and exhibits stable charging characteristics even during printing for a long time. Therefore, not only when using a relatively high molecular weight crosslinked resin as a binder resin,
Even if a linear, relatively low molecular weight resin is used as the binder resin, it can withstand the market share in the developing device.
A toner having excellent low-temperature fixability, color reproducibility, transparency, and durability can be obtained. The toner of the present invention is also most suitable as a color toner for non-magnetic one-component development.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. The binder resin of the toner used in the present invention can be used without particular limitation as long as it is a binder resin used in the toner, and examples thereof include polystyrene and styrene- (meth) acrylic acid. Examples thereof include ester copolymers, styrene-butadiene resins, olefin resins, polyester resins, amide resins, polycarbonate resins, epoxy resins, and graft polymers thereof and mixtures thereof.

Among them, polyester resin, styrene (meth) are taken into consideration in consideration of charge stability, storage stability, fixing property, and color reproducibility when used as a resin for color toner containing chromatic organic pigments. Acrylic ester copolymer resin and epoxy resin can be preferably used. Among them, polyester resin can be particularly preferably used.

The polyester resin used in the present invention is
For example, it can be obtained by reacting a polybasic acid compound selected from a dibasic or higher polybasic acid and / or an acid anhydride and / or a lower alkyl ester thereof with a divalent or higher polyhydric alcohol by a usual method. Examples of the polybasic acid compound used in the present invention, which is selected from dibasic or higher polybasic acids and / or acid anhydrides and / or lower alkyl esters thereof, include phthalic anhydride, terephthalic acid, isophthalic acid and orthophthalic acid. , Naphthalenedicarboxylic acid, adipic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, cyclohexanedicarboxylic acid, succinic acid,
Dicarboxylic acid such as malonic acid, glutaric acid, azelaic acid, sebacic acid or its derivative or its esterified product,
Further, for example, a trifunctional or higher polyvalent carboxylic acid such as trimellitic acid, trimellitic anhydride, pyromellitic acid, pyromellitic anhydride, or a derivative thereof or an esterified product thereof can be mentioned.

Examples of the dihydric or higher polyhydric alcohol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol,
Tripropylene glycol, butanediol, pentanediol, hexanediol, 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 its derivatives, and the like.

Further, for example, polyethylene glycol,
It is also possible to use 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 polycaprocactone diol.

Also, sorbitol, 1,2,3,6-hexanetetraol, 1,4-sorbitan, pentaerythritol, 1,2,4-butanetriol, 1,2,2.
Trifunctional or higher functional compounds such as 5-pentanetriol, glycerin, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trimethylolbenzene, etc. Examples include polyhydric alcohols.

Further, epoxy compounds such as neopentyl glycol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, trimethylolethane triglycidyl ether, pentaerythritol tetraglycidyl ether and the like can be used.

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

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

The glass transition temperature (T
g) is preferably 50 ° C. or higher, but among them, T
It is particularly preferable that g is 55 ° C. or higher. If the Tg is 50 ° C. or less, a blocking phenomenon (thermal aggregation) is likely to occur when the toner is stored, transported, or exposed to a high temperature inside the developing device of the machine.

The softening point of the polyester resin is preferably 90 ° C. or higher, and more preferably 90 ° C. to 180 ° C. More preferably, it is in the range of 95 ° C to 160 ° C. When the softening point is lower than 90 ° C., the toner is apt to cause an agglomeration phenomenon and tends to cause troubles during storage and printing, and when the softening point is higher than 180 ° C., fixability is often deteriorated.

When the toner of the present invention is used as a black toner or a monocolor toner such as a business color for which transparency is not required so much, it is crosslinked with a polyvalent carboxylic acid having a valence of 3 or more or a polyhydric alcohol having a valence of 3 or more. It is desirable to contain the above polyester resin as a binder resin. The softening point of such a crosslinked resin is 90
It is preferably in the range of 90 ° C to 180 ° C, and more preferably in the range of 130 ° C to 180 ° C.

Further, when the color toner is required to have color reproducibility during color superposition and transparency when fixed on an OHP sheet, the softening point of the polyester resin is 90 ° C. to 130 ° C. It is preferably in the range of ° C. More preferably, it is in the range of 95 ° C to 120 ° C.

The acid value of the polyester resin is 20 m
It is preferably gKOH / g or less from the viewpoint that the moisture resistance of the toner is good.

When the toner of the present invention is used as a color toner, the polyester resin used as the binder resin is one selected from the group consisting of 1) divalent carboxylic acid, its acid anhydride and lower alkyl ester thereof. It is preferable to use a linear polyester resin obtained by reacting the above compound with 2) a dihydric alcohol or a derivative thereof.

The non-magnetic one-component developing toner containing the polyester resin has excellent durability and strength as a non-magnetic one-component toner, melts at a relatively low temperature during fixing, and forms a uniform layer after fixing. It is advantageous in obtaining a good image having excellent fixing property and anti-offset property, and having little fluctuation in image density during continuous printing.

Examples of the polyester resin include polystyrene, styrene- (meth) acrylic acid ester copolymer,
An olefin resin, an amide resin, a polycarbonate resin, an epoxy resin, and a graft polymer thereof can be used in combination, but the total amount of the polyester resin is 50 to 100% by weight of the whole binder resin,
It is particularly preferably 70 to 100% by weight.

Particularly in the present invention, it is preferable to produce a color toner by using two kinds of polyester resins having different softening points. The difference in the softening point is 2 to 20 ° C.
Is preferred. Further, it is more preferably 2 to 15 ° C, and particularly preferably 2 ° C or more and less than 10 ° C. With a non-magnetic one-component developing toner containing a polyester resin having a difference in softening point of 2 to 20 ° C., the image density is sufficiently secured and stable, there are no image defects and scumming, and the printing life is long and good. Quality prints are obtained. Also, O
Good sharpness is also obtained when used for HP. When the difference in softening point exceeds 20 ° C., the image density is low, and there is no gloss,
Also, when used for OHP, the definition is poor. Further, the difference in softening point is less than 2 ° C., and when one type of polyester resin is used, background stains and toner spillage occur, and solid uniformity and printing durability deteriorate.

The weight ratio of the two polyester resins having different softening points is 1: 9 to 9: 1, and particularly 2: 8 to 8 :.
2 is preferred. A non-magnetic one-component developing toner containing two kinds of polyester resins having different softening points in a ratio of 1: 9 to 9: 1 is a non-magnetic one-component developing toner while maintaining the excellent characteristics of the non-magnetic one-component developing toner. It has extremely excellent durability and strength as a one-component toner, melts at a relatively low temperature during fixing, forms a uniform layer after fixing, has excellent fixability and offset resistance, and produces images even during continuous printing. A good image having no density fluctuation can be obtained, which is highly clear and has excellent transparency.

The polyester resin having a difference in softening point of 2 ° C. to 20 ° C. can be obtained by appropriately adjusting the molecular weight and the constituent monomers. Further, polystyrene, styrene- (meth) acrylic acid ester copolymer,
An olefin resin, an amide resin, a polycarbonate resin, an epoxy resin, and a graft polymer thereof can be used in combination, but the total amount of the two kinds of polyester resins having different softening points is the same as that of the entire binder resin. 50-100% by weight, especially 70-100% by weight
Is preferred.

Here, the softening point of the polyester resin means the melt viscosity of the polyester resin, which is an overhead flow tester "CF" which is a constant load extrusion type capillary rheometer.
T-500 "(manufactured by Shimadzu Corporation) is used to define the melting temperature T1 / 2 measured by the following method. The constant load extruded capillary rheometer measures the viscous resistance of a melt as it passes through the capillary.

The structure of the cylinder portion of the elevated flow tester is shown in FIG. The measurement by the temperature raising method using this device is conducted while raising the temperature at a constant rate as the test time elapses, so that the sample reaches from the solid region to the transition region, the rubber-like elastic region, and the flow region. The process can be measured continuously. With this device, the shear rate and viscosity at each temperature in the flow region can be easily measured.

FIG. 2 shows a flow curve obtained by the heating method. A
A region B (softening curve) shows a stage in which the sample is deformed under the compression load and the internal voids are gradually reduced. Point B is the temperature at which internal voids disappear and become a single transparent body or phase with a uniform appearance while maintaining a non-uniform stress distribution, which is the inflection point from the solid region to the transition region. The softening temperature T
Define as s. The area of BC (stop curve) shows the area where there is no clear change in the position of the piston within a finite time and the sample starts to flow out from the die.

Point C shows the temperature at which the sample begins to flow out from the die due to the decrease in viscosity, and this temperature is the outflow start temperature Tf.
b. The CDE area (outflow curve) shows the area where the sample flows out from the die, and irreversible viscous flow is mainly performed. The point E indicates the temperature at which the outflow of the sample is completed, and this temperature is the outflow end temperature Tend. Melting temperature T1 / 2
Shows the temperature at the midpoint of the stroke between Tfb and Tend in the outflow curve.

The measurement conditions of T1 / 2 in the present invention are as follows: load 10 kg / cm ² , die hole diameter 1.0 mm × 1.0 m
m, measurement start temperature 60 ° C., preheating time 300 seconds, temperature rising rate 6.0 ° C./min, sample amount 1 cm ³ (about 1.2 g).

Examples of the styrene monomer used in the styrene- (meth) acrylic acid ester copolymer resin used in the present invention include styrene, α-methylstyrene, vinyltoluene, p-sulfonestyrene and dimethylaminomethyl. There are styrene, etc.

Examples of the (meth) acrylic acid ester monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate and isobutyl ( (Meth) acrylate, tertiary butyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth)
Alkyl (meth) acrylates such as acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate; Alicyclic (meth) acrylates such as cyclohexyl (meth) acrylate; Aromatic (meth) acrylates such as benzyl (meth) acrylate; Hydroxyl group-containing (meth) such as hydroxyethyl (meth) acrylate
Acrylate; phosphoric acid group-containing (meth) acrylate such as (meth) acryloxyethyl phosphate; 2-chloroethyl (meth) acrylate, 2-hydroxy-3-chloropropyl (meth) acrylate, 2,3-dibromopropyl (meth) acrylate Halogen atom-containing (meth) acrylate such as; Epoxy group-containing (meth) acrylate such as glycidyl (meth) acrylate; Ether group-containing (meth) such as 2-methoxyethyl (meth) acrylate and 2-ethoxyethyl (meth) acrylate Acrylate; basic nitrogen atom- or amide group-containing (meth) acrylate such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate; and the like.

Further, an unsaturated compound 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; Ketone group-containing vinyl monomers such as vinyl methyl ketone and vinyl isopropenyl ketone; N-vinyl imidazole, 1-vinyl pyrrole, 2-
A vinyl monomer containing a basic nitrogen atom or an amide group such as vinylquinoline, 4-vinylpyridine, N-vinyl-2-pyrrolidone and N-vinylpiperidone can be used.

Further, the crosslinking agent may be used in the range of 0.1 to 2% by weight based on the vinyl monomer. Examples of the cross-linking agent include 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 , Tetramethylolmethane tetra (meth) acrylate and the like.

Alternatively, in the resin using a styrene- (meth) acrylic acid ester copolymer obtained by copolymerizing the above-mentioned carboxyl group-containing vinyl monomer, a metal salt may be used to form a crosslinked resin. A as a metal salt
l, Ba, Ca, Cd, Co, Cr, Cu, Fe, Hg, Mg, Mn, Ni, P
b, Sn, Sr, Zn and other halides, hydroxides, oxides,
There are carbonates, carboxylates, alkoxylates, chelate compounds and the like. The crosslinking reaction can be carried out by heating and stirring in the presence of a solvent.

As a method for producing the styrene- (meth) acrylic acid ester copolymer, an ordinary polymerization method can be adopted. The polymerization reaction is carried out in the presence of a polymerization catalyst, such as solution polymerization, suspension polymerization or bulk polymerization. The method of doing is mentioned.

Examples of the polymerization catalyst include 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 1,1'-azobis (cyclohexane-1-carbonitrile). Nitrile), benzoyl peroxide,
Dibutyl peroxide, butyl peroxybenzoate, etc. can be mentioned, and the amount used is 0.
1 to 10.0% by weight is preferable.

The softening point of the styrene- (meth) acrylic acid ester copolymer resin is 90 ° C. or higher, preferably 90 ° C. to 180 ° C., more preferably 95 ° C. to 160 ° C. It is in the range of ° C. If the softening point is less than 90 ° C., the toner tends to cause an aggregation phenomenon,
Problems often occur during storage and printing, and when the temperature exceeds 180 ° C., the fixability often deteriorates.

Further, as a color toner, especially when color reproducibility at the time of color superimposition and transparency when fixed on an OHP sheet are required, a styrene- (meth) acrylic acid ester copolymer is used. The softening point of the resin is 90 ° C
It is preferably in the range of 130 ° C., more preferably 9
It is in the range of 5 ° C to 120 ° C.

On the other hand, the glass transition temperature (Tg) of the styrene- (meth) acrylic acid ester copolymer resin is 40 ° C.
The above are preferable, and those having a Tg of 45 to 85 ° C. are particularly preferable. Further, the acid value is preferably 30 or less, and particularly preferably 15 or less. If the acid value is too high, the charge amount is lowered and the desired charge amount cannot be obtained.

As the epoxy resin which can be used in the present invention, commercially available products such as "Epiclon 3050" (softening point 94-1 by Dainippon Ink and Chemicals, Inc.) are commercially available.
02 ° C), "Epiclon 4050" (softening point 96 to 10)
4 ° C.), “Epiclone 7050” (softening point 122 to 13
1 ° C.), “Epicoat 1” manufactured by Yuka Shell Epoxy Co.
002 "(softening point 83 ° C)," Epicoat 1003 "
(Softening point 89 ° C), "Epicoat 1004" (Softening point 9
8 ° C), "Epicoat 1007" (softening point 128 ° C),
"Epicoat 1009" (softening point 148 ° C), "Araldide 7072" (softening point 7 manufactured by Ciba-Geigy Co., Ltd.)
5 to 85 ° C), "Araldite 7072" (softening point 75
~ 85 ° C), "Araldite 6084" (softening point 96-
104 ° C), "Araldite 7097" (softening point 115
Up to 125 ° C.) and the like. Among them, aromatic epoxy resins such as epoxy resins obtained from bisphenol A and epihalohydrin are preferable. These binding resins are
A plurality of them may be mixed and used, or may be mixed and used with a small amount of another epoxy resin.

When the non-magnetic one-component developing toner of the present invention is used as a black toner or a mono-color toner such as a business color for which transparency is not required so much, the softening point of the toner is in the range of 90 ° C to 180 ° C. Is preferred,
It is more preferably in the range of 130 ° C to 170 ° C. When used as a color toner, the softening point is 90
The temperature is preferably ˜130 ° C., more preferably 90 to 125 ° C., and particularly preferably 95 to 120 ° C. A non-magnetic one-component developing toner having a softening point of 90 to 130 ° C. has sufficient durability as a non-magnetic one-component toner while maintaining the excellent properties of the non-magnetic one-component developing toner as a color toner. It has high strength, melts at a relatively low temperature during fixing, forms a uniform layer after fixing, has excellent fixability and offset resistance, and gives good images with no fluctuation in image density during continuous printing. Therefore, it becomes clear and highly transparent. The softening point of the non-magnetic one-component developing toner can be measured by the same method as the above-mentioned measuring method of the softening point.

As an example of the silicone oil used in the present invention, dimethyl silicone oil is suitable, but so-called modified silicone oil modified with various functional groups depending on the charging property can also be used. Examples of modified silicone oils include alkyl modified silicone oils, methylstyrene or olefin modified silicone oils,
Polyether modified silicone oil, alcohol modified silicone oil, fluorine modified silicone oil, chlorophenyl silicone oil, mercapto modified silicone oil, epoxy modified silicone oil, carboxyl modified silicone oil, higher fatty acid modified silicone oil, carnauba modified silicone oil, amide modified silicone oil Etc.

In addition to the above silicone oil, methylphenyl silicone oil can be preferably used. Therefore, dimethyl silicone oil or methylphenyl silicone oil is suitable as the silicone oil used in the present invention. These may be used alone or in combination.

These silicone oils can be used alone, but in order to adjust the toner characteristics such as electric characteristics and fluidity of the toner to desired levels, a mixture of two or more kinds may be used depending on the case. It is possible. The silicone oil used in the present invention preferably has a viscosity at 25 ° C. of 1 to 10,000 centistokes. Further, it is more preferably 10 to 6000 centistokes, and particularly preferably 30 to 3000 centistokes. The viscosity of silicone oil is 1
If it exceeds 0000 centistokes, uneven distribution tends to occur when directly added to the toner, which is not preferable.

In the present invention, the amount of silicone oil adhered to the surface of the toner particles is preferably 0.001 to 0.5 parts by weight with respect to 100 parts by weight of the toner particles. Further, it is more preferably 0.001 to 0.2 part by weight, and particularly preferably 0.001 to 0.1 part by weight. If the amount of silicone oil is less than 0.001 part by weight, the effect of the present invention cannot be obtained, and if it exceeds 0.5 part by weight, the fluidity is deteriorated, which is not preferable.

Examples of the colorant that can be used in the present invention include carbon blacks such as furnace black, channel black, acetylene black, thermal black and lamp black, which are classified by the manufacturing method as black colorants. C. I. Pigment B
rack 11 iron oxide pigments, C.I. I. Pigme
nt Black 12 iron-titanium oxide-based pigments, phthalocyanine-based cyanine black BX, and the like. It is also possible to use a plurality of pigments other than black to create a black color.

As the blue colorant, phthalocyanine type C.I. I. Pigment Blue 1, 2, 15:
1,15: 2,15: 3,15: 4,15: 6,15,
16,17: 1,27,28,29,56,60,63
Etc. As a blue colorant, preferably
C. I. Pigment Blue 15: 3 (generic name phthalocyanine blue G), 15 (phthalocyanine blue R), 16 (metal-free phthalocyanine blue), 60
(Indanthrone blue), most preferably C.I. I. Pigment Blue 15: 3,6
0 is mentioned.

As the yellow colorant, for example,
C. I. Pigment Yellow 1, 3, 4,
5, 6, 12, 13, 14, 15, 16, 17, 18,
24, 55, 65, 73, 74, 81, 83, 87, 9
3,94,95,97,98,100,101,10
4,108,109,110,113,116,11
7,120,123,128,129,133,13
8,139,147,151,153,154,15
5,156,168,169,170,171,17
2,173,180,185 etc. are mentioned. Preferably, C.I. I. Pigment Yellow 12 (generic name disazo yellow AAA), 13 (disazo yellow AAMX), 17 (disazo yellow AAO)
A), 97 (Fast Yellow FGL), 110 (Isoindolinone Yellow 3RLT), and 155.
(Sandrin Yellow 4G), 180 (benzimidazolone), most preferably C.I. I. Pigm
ent Yellow 17, 155, 180.

Further, as the red colorant, for example,
C. I. Pigment Red 1, 2, 3, 4, 5,
6,7,8,9,10,12,14,15,17,1
8, 22, 23, 31, 37, 38, 41, 42, 4
8: 1, 48: 2, 48: 3, 48: 4, 49: 1,4
9: 2, 50: 1, 52: 1, 52: 2, 53: 1, 5
4,57: 1,58: 4,60: 1,63: 1,63:
2, 64: 1, 65, 66, 67, 68, 81, 83,
88, 90, 90: 1, 112, 114, 115, 12
2,123,133,144,146,147,14
9,150,151,166,168,170,17
1,172,174,175,176,177,17
8,179,185,187,188,189,19
0,193,194,202,208,209,21
4,216,220,221,224,242,24
3, 243: 1, 245, 246, 247 and the like. Preferably, C.I. I. Pigment Red 4
8: 1 (generic name barium red), 48: 2 (calcium red), 48: 3 (strontium red), 4
8: 4 (manganese red), 53: 1 (lake red), 57: 1 (brilliant carmine 6B), 122
(Quinacridone magenta 122) and 209 (dichloroquinacridone red), most preferably C.I. I. Pigment Red 57: 1, 122 and 209.

The content of these colorants is preferably 1 to 20% by weight based on the whole toner. Above all 2
It is more preferably ˜15% by weight, particularly preferably 2 to 10% by weight. These colorants may be used either individually or in combination of two or more.

In the present invention, a charge control agent can be used if necessary. For example, as a positive charge control agent, a nigrosine dye, a triphenylmethane dye, a quaternary ammonium salt, a resin containing a quaternary ammonium group and / or an amino group, or the like is used as a negative charge control agent, a trimethylethane dye, or a metal of salicylic acid. Complex salts, metal complex salts of benzylic acid, copper phthalocyanine, perylene, quinacridone, azo pigments, metal complex salts azo dyes, acid dyes containing heavy metals such as azochrome complexes, calixarene type phenolic condensates, cyclic polysaccharides, carboxyl groups And / or resins containing sulfonyl groups.

In particular, in the present invention, when a black colorant is not used, it is desirable to use a colorless charge control agent, and a negative charge control agent is a metal complex compound of salicylic acid, which is a product of "Bontron" manufactured by Orient Chemical Company. E-84 "
However, as a colorless positive charge control agent, TP-302, TP-415 and TP-61 having a quaternary ammonium salt structure are also used.
0; (manufactured by Hodogaya Kagaku), Bontron P-51; (manufactured by Orient Kagaku), and Copy Charge PSY (Clariant Japan) are preferably used. Examples of positively chargeable resin type charge control agents containing a quaternary ammonium group and / or amino group include "FCA-201-PS" (Fujikura Kasei Co., Ltd.) and the like.

Among them, the charge control agents that can be particularly preferably used in the present invention include the compounds of the following <general formula 1> and the compounds of <general formula 2>. <General formula 1>

[0063]

[Chemical 1] (In the formula, R ₁ is quaternary carbon, methine, methylene,
N, S, O, P may contain a hetero atom, Y represents a cyclic structure connected by a saturated bond or an unsaturated bond, and R
₂ , R ₃ are each independently an alkyl group, an alkenyl group, an alkoxy group, an aryl group which may have a substituent, an aryloxy group, an aralkyl group or an aralkyloxy group, a halogen group, hydrogen, a hydroxyl group, a substituent May have an amino group, a carboxyl group, a carbonyl group, a nitro group,
Represents a nitroso group, a sulfonyl group, a cyano 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, k 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, and s is 0 or an integer of 1 to 20. )

<General formula 2>

[0065]

[Chemical 2] (In the formula, R ₁ and R ₄ represent a hydrogen atom, an alkyl group, a substituted or unsubstituted aromatic ring (including a condensed ring), and R ₂ and R ₃ represent a substituted or unsubstituted aromatic ring (including a condensed ring). ), And M is one kind of 3 selected from B, Al, Fe, Ti, Co and Cr.
Represents a valent metal, and X ⁺ represents a cation)

Specific examples of the compound of the general formula 1 include the following <charge control agent 1> to <charge control agent 3>.

<Charge Control Agent 1>

[0068]

[Chemical 3]

<Charge control agent 2>

[0070]

[Chemical 4]

<Charge Control Agent 3>

[0072]

[Chemical 5]

As specific examples of the compound of <general formula 2>, <charge control agent 4> and <charge control agent 5> below are given.
There is.

<Charge Control Agent 4>

[0075]

[Chemical 6]

<Charge Control Agent 5>

[0077]

[Chemical 7]

The above charge control agents may be used alone or in combination, and are added in an amount of 0.3 to 0.3 with respect to the binder resin.
By containing 15 parts by weight, preferably 0.5 to 5 parts by weight, good charging performance can be obtained.

In the toner of the present invention, various known waxes such as polypropylene wax, polyethylene wax, polyamide wax, Fischer-Tropsch wax, carnauba wax and ester wax may be appropriately used as a releasing agent. it can.

The above waxes may be used alone or in combination, and are used in an amount of 0.3 to 15 relative to the binder resin.
Good fixing offset performance can be obtained by containing 1 part by weight, preferably 1 to 5 parts by weight. If it is less than 0.3 parts by weight, the anti-offset property is impaired, and if it is more than 15 parts by weight, the fluidity of the toner deteriorates. Doing so hinders the charging of the toner and causes image defects.

The manufacturing method for obtaining the toner of the present invention is as follows:
It can be obtained by any known and commonly used means, for example, by melting and kneading a resin and a colorant and, if necessary, various additives near the melting point (softening point) of the resin, pulverizing and classifying You can get it. When using a colorant,
It is also possible to use a masterbatch which is previously subjected to a flushing treatment so as to be uniformly dispersed in the resin, or which is melt-kneaded with the resin at a high concentration.

Specifically, for example, the above-mentioned resin and colorant are mixed as essential components by a kneading means such as a two-roll, three-roll, pressure kneader, or twin-screw extruder. At this time, the colorant may be uniformly dispersed in the resin,
The conditions of the melt-kneading are not particularly limited,
It is usually at 80 to 180 ° C. for 10 minutes to 2 hours.

Further, if necessary, coarse pulverization is carried out for the purpose of reducing the load in the fine pulverization process and improving the pulverization efficiency. The apparatus and conditions used for coarse pulverization are not particularly limited, but it is common to coarsely pulverize to a particle size of 3 mm mesh pass or less by a rotoplex, palpelizer or the like.

Next, a method of finely pulverizing with an air type pulverizer such as a mechanical pulverizer such as a turbo mill and a kryptron, a spiral jet mill, a counter jet mill, a collision plate type jet mill and the like, and classifying with a wind classifier and the like. Can be mentioned. Equipment for fine pulverization and classification, conditions are desired particle size,
The particle size distribution and particle shape may be selected and set.

In the present invention, as a method for adhering the silicone oil to the toner particles, it may be added directly using a powder mixer such as a Henschel mixer, or may be added by spraying during stirring. May be.

In the present invention, various kinds of additives (referred to as external additives) are added to the surface of the toner particles after the silicone oil is attached to the surface of the toner particles to improve the fluidity of the toner and the charging characteristics. Is preferably used.

As the external additive used in the present invention, for example, inorganic fine powders of silica, titanium oxide, aluminum oxide, cerium oxide, zinc oxide, tin oxide, zirconium oxide and the like and silicone oils, silane coupling agents thereof and the like are used. Those surface-treated with the above hydrophobic treatment agent can be preferably used. If necessary, resin fine powder such as polystyrene, acryl, styrene acryl, polyester, polyolefin, cellulose, polyurethane, benzoguanamine, melamine, nylon, silicon, phenol and vinylidene fluoride can be used.

Concretely, there are some commercially available under the following trade names. AEROSIL; R972, R974, R202, R8
05, R812, RX200, NAX50, RX20
0, RY50, RY200, R809, RX50, R
A200HS, RA200H [Japan Aerosil Co., Ltd.] WACKER; HDK H2000, H2050, H3
050, HVK2150 [Wacker Chemicals Co., Ltd.], HDK H13TM, HDK H13TD, H
DK H13TX [Clariant Japan] Nipsil; SS-10, SS-15, SS-20,
SS-50, SS-60, SS-100, SS-50
B, SS-50F, SS-10F, SS-40, SS-
70, SS-72F, [Nippon Silica Industry Co., Ltd.], CA
BOSIL; TS-500, TS-530, TS-61
0, TS-720, TG-308F, TG-709F,
TG-810G, TG-811F, TG820F [Cabot Specialty Chemicals, Inc.], and the like.

The titanium oxide may be a hydrophilic grade or a hydrophobic grade surface-treated with octylsilane or the like. For example, there are commercially available products with the following trade names. Titanium oxide T
805 [Degussa Co., Ltd.], titanium oxide P25 [Japan Aerosil Co., Ltd.] and the like.

Examples of alumina include aluminum oxide C [Degussa Co., Ltd.] and the like.

The particle diameter of these external additives is preferably 1/3 or less of the diameter of the toner particles, and particularly preferably 1
/ 10 or less. Further, in the present invention, it is preferable to use two or more kinds of external additives having different average particle sizes as external additives in combination. In other words, fine powder with a small average particle size (hereinafter,
It is preferable to use a combination of the first fine powder) and the fine powder having a large average particle diameter (hereinafter referred to as the second fine powder).

The average primary particle diameter of the first fine powder in the present invention is preferably less than 30 nm, 1 nm or more, and more preferably 25 nm to 5 nm.
Furthermore, it is particularly preferable that the thickness is 20 nm to 5 nm.
As the first fine powder, it is possible to use the above-mentioned various materials conventionally used as a fluidity improver.
For example, silica, alumina, titanium dioxide, zinc oxide,
Magnesium oxide and the like can be used alone or in combination of two or more. A particularly preferred first fine powder is silica. Among them, colloidal silica surface-treated with a hydrophobizing agent is preferable. The surface treatment with such a hydrophobizing agent is for preventing the change of the toner charge amount due to the influence of humidity, and the degree of hydrophobization is preferably 80% or more.

As the hydrophobizing agent, conventionally used hydrophobizing agents such as silane coupling agents, titanate coupling agents, silicone oils and the like are used. A silane coupling agent is preferably used. More preferably, silicone oil is used. More preferably,
Both silane coupling agent and silicone oil are used. Examples of the silane coupling agent include trimethylsilane, trimethylchlorosilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, benzyldimethylchlorosilane, methyltrimethoxysilane, methyltriethoxysilane, and isobutyltrimethoxysilane. , N-hexyltrimethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, trimethylmethoxysilane, hydroxypropyltrimethoxysilane, hexamethyldisilazane, hexaethyldisilazane, diethyltetraethyldisilazane, hexaphenyldisilazane, hexatolyldisilane Silazane etc. can be used. As the silicone oil, for example, dimethylpolysiloxane, methylhydrogenpolysiloxane, methylphenylpolysiloxane, etc. can be used. The hydrophobizing agent may be treated by a conventionally known method in an amount used so that the degree of hydrophobization of 80% or more can be achieved.

In the present invention, when the average primary particle size of the first fine powder is 30 nm or more, the effect as a fluidity improver is reduced, and a large amount of fine powder is required to obtain desired fluidity. . In the present invention, the content of the first fine powder is preferably 0.1 to 3 parts by weight, and more preferably 0.3 to 1.5 parts by weight, based on 100 parts by weight of the toner particles. When the content is less than 0.1 part by weight,
The desired fluidity cannot be obtained, and printing unevenness and fog occur, which is not preferable. If the amount exceeds 3 parts by weight, the loosened fine powder adheres to the toner layer regulating member and the like, which tends to induce toner sticking and toner scattering, which is not preferable.

In the present invention, the first fine powder is used in order to improve the fluidity of the toner and the developing durability, to prevent the toner from sticking to the blade of the developing machine and to prevent fog, and to stabilize the charging during running. In addition, it is preferable to use a second fine powder having a large average primary particle size in combination, and the second fine powder preferably has an average primary particle size of 30 nm to 100 nm. The average primary particle size is 30 nm to 80 nm.
nm is more preferable, and 30 nm to 70 nm is particularly preferable.

As the second fine powder, it is possible to use the above-mentioned various materials conventionally used as a fluidity improver. For example, titania, alumina, silica, barium titanate, zinc oxide and the like can be used, but silica is particularly preferable. The second fine powder in the present invention has a function of preventing the first fine powder from being embedded and embedded in the toner particles when the toner is repeatedly subjected to shear in the developing device. As the second fine powder in the present invention, it is preferable to use the second fine powder which has been surface-treated with the above-mentioned hydrophobizing agent, like the above-mentioned first fine powder.

In the present invention, the content of the second fine powder is
It is desirable that the content of the toner is 0.3 to 2.0 parts by weight, more preferably 0.3 to 1.5 parts by weight, based on 100 parts by weight of the toner particles. When the content of the second fine powder is 0.3 parts by weight or less, the function of preventing the first fine powder from being embedded in the toner particles is not sufficiently exhibited, and the printing durability is shortened, which is not preferable. Further, when it exceeds 2.0 parts by weight, the liberated substances and aggregates adhere to the toner layer regulating member as described above,
This may adversely affect the image such as streaks occurring during printing.

The fine powder may be externally added to the toner particles by using, for example, an ordinary powder mixer such as a Henschel mixer or a so-called surface modifier such as a hybridizer.

As a developing method using the toner of the present invention as a non-magnetic one-component developing toner, the toner of the present invention is carried on a developing sleeve without being mixed with a carrier, and an electrostatic latent image is formed on the developing sleeve. There is a contact-type non-magnetic one-component developing method of developing by contacting with a photosensitive drum.

When the toner of the present invention is used as a non-magnetic one-component developing toner, the toner passes between the developing sleeve and the charging member pressed against the toner, thereby being triboelectrically charged, and then on the surface of the photoreceptor. It can be particularly effectively used for a contact type non-magnetic one-component developing device for developing the formed electrostatic latent image.

When the toner of the present invention is used as a non-magnetic one-component developing toner, the material for the charge imparting member of the developing device is not particularly limited as long as it is used under normal conditions. For example, aluminum, stainless steel, urethane rubber,
A developing sleeve made of silicon rubber, aluminum, stainless steel, duralumin, copper, or a layer thickness regulating member in which urethane rubber or silicon rubber is attached to them can be preferably used.

The developing method suitable for the toner of the present invention to exert its effect is a case where either one of the developing sleeve and the charging member is a metal such as aluminum or stainless steel, and the most effective combination (developing The sleeve / charging member is (1) a combination of a developing sleeve made of urethane rubber or silicon rubber and a charging member made of stainless steel, or (2) a developing sleeve made of stainless steel and charging made of urethane rubber or silicon rubber. A combination of members, or (3) a combination of a developing sleeve made of aluminum and a charging member made of urethane rubber or silicon rubber.

[0103]

EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples. In the following, the numerical values in the composition table represent "parts by weight". An example of synthesizing the binder resin used for preparing the toner is shown below.

[0104] (Resin synthesis example 1)       Terephthalic acid 166 parts by weight       Isophthalic acid 415 parts by weight       Trimellitic acid 96 parts by weight       Polyoxyethylene- (2.0) -2,2       -Bis (4-hydroxyphenyl) propane 1300 parts by weight       75 parts by weight of ethylene glycol

The mixture was placed in a four-necked flask equipped with a stirrer, a condenser and a thermometer, and 0.07% by weight of dibutyltin oxide was added to the total acid component under a nitrogen gas stream to produce dehydration condensation. 230 while removing water
The reaction was carried out at ℃ for 15 hours. The polyester resin thus obtained has a softening point T1 / 2 of 155 ° C. and a Tg of 6 by the DSC method.
The acid value was 10 at 2 ° C.

Resin Synthesis Example 2 terephthalic acid 415 parts by weight isophthalic acid 415 parts by weight polyoxyethylene- (2.0) -2,2-bis (4-hydroxyphenyl) propane 1690 parts by weight was added to a four-necked flask. , A stirrer, a condenser and a thermometer were set, nitrogen gas was blown in, 0.7 parts by weight of dibutyltin oxide as a catalyst was added to all the acid components, and dehydration condensation was performed at 220 ° C. The reaction was carried out for 10 hours while removing water. After that, the pressure is sequentially reduced to 5 mmH
The reaction was continued at g. The reaction was followed by the softening point according to ASTM E28-517, and the reaction was terminated when the softening point reached 103 ° C. The linear polyester resin thus obtained had an acid value of 12 and a hydroxyl value of 27. Also,
The softening point T1 / 2 was 105 ° C and the Tg was 62 ° C. The molecular weight is Mw: 9500, Mn: 3600.
Met. Tg was measured by DSC.

(Synthesis Example 3 of Resin) 415 parts by weight of terephthalic acid 415 parts by weight of isophthalic acid 1800 parts by weight of polyoxypropylene- (2.2) -2,2-bis (4-hydroxyphenyl) propane were used as a resin. The reaction proceeds in the same manner as in Synthesis Example 1, and AST
The reaction was terminated when the softening point according to ME28-517 reached 105 ° C. The acid value of the obtained linear polyester resin was 11, and the hydroxyl value was 25. Also,
The softening point T1 / 2 was 108 ° C and the Tg was 62 ° C. The molecular weight is Mw: 10500, Mn: 400.
It was 0. Tg was measured by DSC.

[0108] (Resin synthesis example 4)       Styrene 380 parts by weight       Butyl methacrylate 120 parts by weight       Divinylbenzene 5 parts by weight       Benzoyl peroxide 5 parts by weight

A 2-volume four-necked round-bottomed flask equipped with a thermometer, a glass airflow introduction tube, a stirring rod equipped with a vacuum-proof sealing device, and a water-cooled Dimroth condenser was used. Was thrown in. Nitrogen gas was introduced from a glass air flow introducing pipe to replace the inside of the reactor with an inert atmosphere, and then the contents were gradually heated by a mantle heater equipped with a slider and heated to 75 ° C.
The reaction was carried out while maintaining the temperature at 75 ° C to 80 ° C, and after 10 to 12 hours, the temperature was raised to 130 ° C to complete the reaction and the polymerization was completed. Next, the water-cooled condenser and the glass air flow introducing tube were removed from the flask, and instead, a capillary for vacuum distillation and a Claisen fractionating tube were attached. A thermometer and a water-cooled Leibitz condenser were connected to the Claisen distillation tube, and the outlet of the condenser was connected to an eggplant-shaped flask via a suction adapter. The suction adapter and the vacuum pump were connected with a rubber tube for pressure reduction through a manometer and a trap, and preparation for vacuum distillation was completed. When the mantle heater was heated and the contents were sufficiently stirred and the vacuum pump was operated to reduce the pressure to 20 mmHg, xylene or possibly unreacted monomer started to distill at a liquid temperature of 75 ° C and a distilling temperature of 38 ° C. Finally, the solvent was completely removed by reducing the pressure to 0.5 mmHg at a liquid temperature of 180 ° C. The obtained polymer was opened in a stainless pan while being in a high-temperature molten state, cooled to room temperature, and then crushed.

The softening point T1 / 2 of the obtained polymer is 145.
C., Tg was 55.degree.

Example 1 <Production of Toner> Polyester Resin 2 92 parts by weight Pigment Fastgen Super Magenta R “Dainippon Ink and Chemicals” 5 parts by weight Wax Viscole 550P “Sanyo Kasei Co., Ltd.” 2 parts by weight After mixing 1 part by weight of the charge control agent 4 in a Henschel mixer, the mixture was melt-kneaded by a biaxial extrusion kneader. The kneaded product is cooled to room temperature, roughly crushed with a hammer mill, finely crushed with a jet mill, and then classified with an air classifier to obtain "toner particles (1)" having a volume 50% diameter: 7.5 microns. It was

Next, toner particles (1) 100 parts by weight Dimethyl silicone oil (KF-96-50CS) (Shin-Etsu Chemical Co., Ltd., viscosity 50 centistokes) 0.005 parts by weight Hydrophobic silica NAX50 1.0 parts by weight Parts (average particle size of primary particles of silica manufactured by Nippon Aerosil Co., Ltd .; 30 nm) RX200 0.5 part by weight (average particle size of primary particles of silica manufactured by Nippon Aerosil Co., Ltd .; 12 nm) The above "toner particles (1)" and dimethyl silicone oil KF -96-50CS was mixed at the above mixing ratio, and then hydrophobic silica was added at the above mixing ratio to perform uniform mixing. Then, it was sieved to obtain "Non-magnetic one-component developing toner A".

Example 2 In Example 1, dimethyl silicone oil was replaced by K instead of KF-96-50CS.
A toner was prepared in the same manner except that F-96-300CS (viscosity: 300 centistokes) was used to obtain "non-magnetic one-component developing toner B".

(Example 3) Polyester resin 2 46 parts by weight Polyester resin 3 46 parts by weight Pigment Fastgen Super Magenta R "Dainippon Ink and Chemicals" 5 parts by weight Wax Viscole 550P "Sanyo Kasei Co., Ltd." 2 parts by weight Parts 1 part by weight of the charge control agent 4 was mixed by a Henschel mixer in the same manner as in Example 1, and then melt-kneaded by a biaxial extrusion kneader. After cooling the kneaded material to room temperature, it is roughly crushed with a hammer mill, finely pulverized with a jet mill, and then classified with an air classifier to obtain a volume of 50%.
"Toner particles (2)" having a diameter of 7.5 microns were obtained.

Toner particles (2) 100 parts by weight Dimethyl silicone oil (KF-96-100CS) (Shin-Etsu Chemical Co., Ltd., viscosity 100 centistokes) 0.005 parts by weight Hydrophobic silica NAX50 1.0 parts by weight Parts (average particle size of primary particles of silica manufactured by Nippon Aerosil Co., Ltd .; 30 nm) RX200 0.5 part by weight (average particle size of primary particles of silica manufactured by Nippon Aerosil Co., Ltd .; 12 nm) The above "toner particles (2)" and dimethyl silicone oil ( KF-96-100CS) was mixed at the above blending ratio using a Henschel mixer, and then hydrophobic silica was added at the above blending ratio to carry out uniform mixing. Then, it was sieved to obtain "Non-magnetic one-component developing toner C". The difference in softening point between the two polyester resins was 3 ° C. The softening point of the non-magnetic one-component developing toner B is 106 ° C.
Met.

Example 4 Toner Particles (2) of Example 3 100 parts by weight Dimethyl silicone oil (KF-96-100CS) (Shin-Etsu Chemical Co., Ltd., viscosity 100 centistokes) 0.005 parts by weight Hydrophobic silica RY50 1.0 part by weight (average particle size of primary particles of silica manufactured by Nippon Aerosil Co., Ltd .; 30 nm) RX200 0.5 part by weight (average particle size of primary particles of silica manufactured by Nippon Aerosil Co., Ltd .; 12 nm) 2) ”and dimethyl silicone oil KF-96-100CS were mixed in the above mixing ratio, and then hydrophobic silica was added in the above mixing ratio to perform uniform mixing. After that, sieving was performed to obtain "non-magnetic one-component developing toner D".

Comparative Example 1 A toner was prepared in the same manner as in Example 1 except that dimethyl silicone oil (KF-96-50CS; manufactured by Shin-Etsu Chemical Co., Ltd., viscosity: 50 centistokes) was not used in Example 1. Was produced to obtain "Comparative Toner 1".

Comparative Example 2 A toner was prepared in the same manner as in Example 3 except that dimethyl silicone oil (KF-96-100CS; manufactured by Shin-Etsu Chemical Co., Ltd., viscosity: 100 centistokes) was not used in Example 3. Was produced to obtain “Comparative Toner 2”.

The following tests were conducted using the toners produced in Examples 1 to 4 and Comparative Example. (1) Printing Durability Test A cartridge that was washed by removing the special toner from the cartridge of a commercially available non-magnetic one-component developing type color printer (having a developing device composed of an aluminum developing sleeve and a urethane rubber charging member). 200 g of non-magnetic one-component developing toner A was filled in, and continuous printing with an image density of 5% was performed, and a solid image was printed every 1000 sheets. Printing was terminated when the remaining toner in the cartridge became 50 g or less. The number of printed sheets at this time was defined as the print life.

At this time, a state where toner is spilled around the developing device or the toner is not scattered inside the printer is ◯, a case where toner is spilled or scattered is Δ, a large amount of toner spilled or scattered, When the area around the developing device was heavily contaminated, it was judged as x.

The image density and background stain of the printed matter were measured with a Macbeth densitometer RD-918. Further, the image density at the start of printing and the image density at the end of printing were measured, and the image density at the start of printing was subtracted from the image density at the end of printing to evaluate the density fluctuation at the time of printing. The evaluation of a solid image is based on how much the density uniformity (solid followability) is secured,
The case where the density was uniform up to 4000 sheets or more was marked with ◯, and the case where the density was less than 4000 sheets was marked with x.

The evaluation results are shown in Table 1.

[Table 1]

(Example 5) Polyester resin 1 92 parts by weight Carbon black (Elftex 8: made by Cabot) 5 parts by weight Wax Viscole 550P "Sanyo Kasei Co., Ltd." 2 parts by weight Charge control agent S-34 "Orient" 1 part by weight manufactured by Kagaku Kogyo Co., Ltd. was mixed with a Henschel mixer and then melt-kneaded with a biaxial extrusion kneader. The kneaded product was cooled to room temperature, coarsely crushed with a hammer mill, finely pulverized with a jet mill, and then classified with an air classifier to obtain "toner particles (3)" having a volume ratio of 50%: 9.0 μm. .

Next, the toner particles (3) 100 parts by weight Dimethyl silicone oil (KF96-100CS) (Shin-Etsu Chemical Co., Ltd., viscosity 100 centistokes) 0.01 parts by weight Hydrophobic silica HDK H13TM 1.0 parts by weight (Clariant Co., Ltd. silane coupling agent-treated silica primary particle diameter 20 nm) NAX50 1.0 part by weight (Nippon Aerosil Co., Ltd. silica primary particle average particle diameter; 30 nm) The “toner particles (3)” and dimethyl silicone oil (KF). -96-100CS) was mixed with a Henschel mixer at the above blending ratio, and then hydrophobic silica was added at the above blending ratio to perform uniform mixing. After that, it was sieved to obtain "Non-magnetic one-component developing toner E".

Example 6 Instead of HDK13TM as the hydrophobic silica in Example 5, HDK H13TD (Silica oil treated silica primary particle size 2 manufactured by Clariant Co., Ltd.) was used.
(Toner F for non-magnetic one-component development) was obtained in the same manner as in Example 5 except that 1.0 part by weight (0 nm) was used.

Example 7 Instead of HDK H13TM as the hydrophobic silica in Example 5, HDK H13TX was used.
A toner was prepared in the same manner as in Example 5 except that (a silane coupling agent / silica oil-treated silica primary particle diameter of 20 nm manufactured by Clariant Co., Ltd.) was used to obtain a “non-magnetic one-component developing toner G”.

(Example 8) A toner was prepared in the same manner as in Example 7 except that the styrene-acrylic resin of Resin Synthesis Example 4 was used in place of the polyester resin 1 of Example 7, and the "non-magnetic one-component development was performed. Toner H ”was obtained.

(Example 9) Instead of the polyester resin 1 in Example 7, "Epiclon 4050" (softening point T1
/ 2 = 100 ° C., a toner was prepared in the same manner as in Example 7 except that an epoxy resin manufactured by Dainippon Ink and Chemicals, Inc. was used to obtain “non-magnetic one-component developing toner I”.

Comparative Example 3 A toner was prepared in the same manner as in Example 5 except that the dimethyl silicone oil KF96-100CS (produced by Shin-Etsu Chemical Co., Ltd., viscosity: 100 centistokes) was not used. Got

Comparative Example 4 A toner was prepared in the same manner as in Example 6 except that the dimethyl silicone oil KF96-100CS (produced by Shin-Etsu Chemical Co., Ltd., viscosity: 100 centistokes) was not used. Got

Comparative Example 5 A toner was prepared in the same manner as in Example 6 except that the dimethyl silicone oil KF96-100CS (produced by Shin-Etsu Chemical Co., Ltd., viscosity: 100 centistokes) was not used. Got

The toners obtained in Examples 5 to 9 and Comparative Examples 3 to 5 were subjected to a printing test by using a commercially available monochrome printer having a developing device composed of a urethane rubber developing sleeve and a stainless charging blade. The print life was evaluated based on the number of prints in which the printed image was blurred. The evaluation results are shown in Table 2.

[0133]

[Table 2]

Example 10 Instead of KF-96-50CS, the dimethyl silicone oil in Example 1 was replaced by methylphenyl silicone oil KF-50-100CS.
A toner was manufactured in the same manner as in Example 1 except that (Shin-Etsu Chemical Co., Ltd., viscosity: 100 centistokes) was used to obtain "non-magnetic one-component developing toner J".

(Example 11) The dimethyl silicone oil in Example 4 was replaced by methylphenyl silicone oil KF-50-300C instead of KF-96-100CS.
A toner was prepared in the same manner as in Example 4 except that S (manufactured by Shin-Etsu Chemical Co., Ltd., viscosity: 300 centistokes) was used to obtain "non-magnetic one-component developing toner K".

A printing durability test was conducted on Examples 10 and 11 as in Examples 1 to 4 and Comparative Examples 1 and 2. The results are shown in Table 3.

[0137]

[Table 3]

(Example 12) The dimethyl silicone oil used in Example 5 was replaced by methylphenyl silicone oil KF-50-100C instead of KF-96-100CS.
A toner was prepared in the same manner as in Example 5 except that S (manufactured by Shin-Etsu Chemical Co., Ltd., viscosity: 100 centistokes) was used to obtain "non-magnetic one-component developing toner L".

(Example 13) The dimethyl silicone oil in Example 8 was replaced by methylphenyl silicone oil KF-50-100C instead of KF-96-100CS.
A toner was prepared in the same manner as in Example 8 except that S (manufactured by Shin-Etsu Chemical Co., Ltd., viscosity: 100 centistokes) was used to obtain "non-magnetic one-component developing toner M".

(Example 14) The dimethyl silicone oil used in Example 9 was replaced by methylphenyl silicone oil KF-50-100C instead of KF-96-100CS.
A toner was prepared in the same manner as in Example 9 except that S (manufactured by Shin-Etsu Chemical Co., Ltd., viscosity: 100 centistokes) was used to obtain "non-magnetic one-component developing toner N".

A printing test was conducted on Examples 12 to 14 as in Examples 5 to 9 and Comparative Examples 3 to 5. The results are shown in Table 4.

[0142]

[Table 4]

[0143]

According to the toner of the present invention, it is possible to provide a non-magnetic one-component developing toner which exhibits stable charging behavior even during continuous printing and has a long printing life. Further, it is possible to provide a non-magnetic one-component developing toner which has a small density fluctuation during continuous printing and can obtain good color reproducibility even in overlapping printing with color toners.

[Brief description of drawings]

FIG. 1 is a schematic view showing a structure of a cylinder portion of a constant load extrusion type thin tube rheometer.

FIG. 2 is an example of a flow curve obtained by a heating method.

[Explanation of symbols]

1 piston 2 cylinders 3 heater 4 die 5 die presser 6 samples

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Shinji Amaya             1-4-1-604 Minami Urawa, Saitama City, Saitama Prefecture F-term (reference) 2H005 AA01 AA08 AB09 CA08 CA12                       CA17 CB13 EA03 EA05 EA10                       FA07

Claims (8)

[Claims] 1. A non-magnetic one-component developing toner comprising toner particles containing at least a binder resin and a colorant, wherein the toner particles are surface-treated with silicone oil. Toner for component development. 2. The non-magnetic one-component developing toner according to claim 1, wherein the binder resin contains a polyester resin. 3. The binder resin contains a crosslinked polyester resin, and the softening point of the non-magnetic one-component developing toner containing the crosslinked polyester resin is 90 ° C. to 180 ° C.
The non-magnetic one-component developing toner according to claim 1, 4. The non-magnetic one-component developing toner containing the polyester resin, wherein the binder resin is composed of two kinds of polyester resins having different softening points, the difference in softening point is 2 to 20 ° C. The non-magnetic one-component developing toner according to claim 1, which has a softening point of 90 to 130 ° C. 5. The two types of polyester resins are:
(1) one or more compounds selected from the group consisting of a divalent carboxylic acid, an acid anhydride thereof and a lower alkyl ester thereof, and (2) a divalent alcohol or a derivative thereof,
The non-magnetic one-component developing toner according to claim 4, which is a linear polyester resin obtained by reacting with. 6. The non-magnetic one-component developing toner according to claim 1, wherein two or more kinds of fine powders having different average primary particle diameters are attached to the surface of the toner particles. 7. The viscosity of the silicone oil is 25 ° C.
The toner for non-magnetic one-component development according to claim 1, which has a viscosity of 1 to 10000 centistokes. 8. The non-magnetic one-component developing toner according to claim 1, wherein the silicone oil is dimethyl silicone oil and / or methylphenyl silicone oil.