JPH11352720A - Toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner containing a wax uniformly dispersed in a binder resin, and having good grindability, excellent fixing property, offset resistance, blocking resistance and durability for printing of lots of sheets. SOLUTION: This toner contains at least a binder resin, coloring agent and wax. In this toner, the binder resin is prepared from a mixture containing at least a component (1) of aromatic vinyl monomers, (meth)acrylate monomers and vinyl monomer having carboxyl groups to produce vinyl copolymers, a component (ii) of an acid component and alcohol component to produce a polyester resin, and a component (iii) of a wax. First, the monomers of the component (i) of the mixture are polymerized to produce a vinylic copolymer (A), and then the acid component and alcohol component of the component (ii) are polymerized and condensed in the presence of the wax and the vinylic copolymer (A) above described. Further, the binder resin contains a reaction product (C) of the vinylic copolymer and the polyester resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

[0002]

2. Description of the Related Art An electrophotographic method is disclosed in U.S. Pat.
Numerous methods are known as described in Japanese Patent Publication No. 7,691, Japanese Patent Publication No. 42-23910 and Japanese Patent Publication No. 43-24748. Generally, a photoconductive substance is used to form an electrostatic charge image on a photoreceptor by various means,
Then, the electrostatic image is developed using toner, and if necessary, a toner image is transferred to a transfer material such as paper, and then fixed by heating, pressure, heat and pressure, or solvent vapor to obtain a toner image. is there.

Various methods and apparatuses have been developed for fixing the toner image onto a sheet such as paper, which is the above-mentioned final step. The most common method at present is a fixed heat generation through a heat roller or a heat-resistant film. This is a compression heating method using a heater.

In the pressure heating method using a heating roller, the toner image is fixed by passing the surface of the heat roller having a releasing property to the toner and the toner image surface of the sheet to be fixed while pressing the sheet under pressure. Is performed. In this method, since the surface of the heat roller and the toner image on the sheet to be fixed come into contact with each other under pressure, the thermal efficiency at the time of fusing the toner image onto the sheet to be fixed is extremely good, and the fixing can be performed quickly. Can be.

[0005] Since the surface of the heating roller and the toner image come into contact with each other in a molten state and under pressure, a part of the toner image adheres to the surface of the fixing roller and is transferred. The offset phenomenon, which stains the sheet, is greatly affected by the fixing speed and the fixing temperature. Generally, when the fixing speed is low, the surface temperature of the heating roller is set relatively low, and when the fixing speed is high, the surface temperature of the heating roller is set relatively high. This is because the amount of heat applied from the heating roller to the toner to fix the toner is made substantially constant regardless of the fixing speed.

Since the toner on the sheet to be fixed forms several toner layers, particularly in a system in which the fixing speed is high and the surface temperature of the heating roller is high, the toner layer in contact with the heating roller includes: When the surface temperature of the heating roller is high because the temperature difference between the lowermost toner layer in contact with the fixing sheet and the lowermost toner layer is large, the toner in the uppermost layer is likely to cause an offset phenomenon, and When the surface temperature is low, the toner in the lowermost layer is not sufficiently melted, so that the toner is not fixed on the sheet to be fixed and a phenomenon of low-temperature offset is likely to occur.

As a method for solving this problem, when the fixing speed is high, a method of increasing the pressure at the time of fixing and anchoring the toner to the sheet to be fixed is usually used. According to this method, the temperature of the heating roller can be reduced to some extent, and the high-temperature offset phenomenon of the uppermost toner layer can be prevented. However, since the shearing force applied to the toner becomes very large, the sheet to be fixed winds around the fixing roller, and a winding offset occurs, or after the separation claw for separating the sheet to be fixed from the fixing roller is separated. Easily appear in the fixed image. Furthermore, because the pressure is high, the line image is crushed or the toner is scattered at the time of fixing, and the image quality of the fixed image tends to deteriorate.

Conventionally, vinyl resins such as polyester resins and styrene resins have been mainly used as toner resins. Polyester resin has excellent low-temperature fixability, but it is said that it has the disadvantage that offset phenomenon easily occurs at high temperature.To compensate for this defect, the molecular weight of the polyester resin is increased to increase the viscosity. Attempts have been made to improve the elastic properties, but there is a tendency that the pulverizability during the production of the toner tends to be deteriorated, and an improvement has been demanded for application to finer toner particles.

Further, vinyl copolymers such as styrene resins are excellent in pulverizability at the time of toner production and high in high molecular weight, so they are excellent in high-temperature offset resistance, but in order to improve low-temperature fixability. However, when the molecular weight is lowered or the glass transition temperature is lowered, there is a problem that the blocking resistance and the developability deteriorate.

[0010] In order to make effective use of the advantages of these two types of resins and to compensate for the drawbacks, some methods of mixing and using these resins have been studied.

For example, Japanese Patent Application Laid-Open No. Sho 54-114245 discloses a toner containing a resin obtained by mixing a polyester resin and a vinyl copolymer.

JP-A-56-116043 and JP-A-58-159546 disclose toners characterized by containing a polymer obtained by polymerizing a monomer in the presence of a polyester resin. Have been.

[0013] Also, Japanese Patent Application Laid-Open No. 58-102246,
JP-A-1-156759 discloses a toner containing a polymer obtained by polymerizing a vinyl copolymer in the presence of an unsaturated polyester.

However, the compatibility between polyester resin and vinyl copolymer is so poor that the chemical structure is so different that the polyester resin and vinyl copolymer satisfy all of low-temperature fixing property, high-temperature offset resistance and blocking resistance. difficult.

In addition, it is difficult to uniformly disperse various additives, particularly wax, added during the production of the toner, so that not only the fixing performance of the toner, but also the developability tends to be problematic. This problem is significant for certain toners.

JP-A-2-881 discloses a binder resin for a toner having a phase-separated sea-island structure containing a polyester resin, a styrenic resin and a block polymer obtained by esterifying both of them.

In the above-mentioned binder resin, it is stated that the phase separation state of the polyester resin and the styrene resin is stabilized by containing the block polymer. However, the existence of the block polymer is not directly confirmed. In addition, wax is added during the production of a binder resin or a toner. However, the properties in the vicinity of the wax differ greatly due to the phase-separated binder resin, and it is difficult to control both the dispersed particle size and the particle size distribution of the wax. When such a binder resin is used for a toner, there remains a problem to be improved not only in the fixing property but also in the developing property.

Japanese Patent Application Laid-Open No. 7-98518 discloses two polymerization-based starting monomers each having an independent reaction path,
A binder resin produced by preliminarily mixing a compound capable of reacting with any of these and a carboxylic acid having a valency of 3 or more and polymerizing in parallel in one reaction vessel is disclosed.

However, in the above-mentioned binder resin, addition of a wax which serves as an anti-offset agent for the toner is not considered. In addition, there is no evidence that a compound capable of reacting with any of the two raw material monomers of the polymerization system actually reacts,
Since a compound which is presumed to give a branched or cross-linked structure to the polymer is used only for the production of one kind of polymer, a large difference occurs in the molecular weight distribution between the two. Therefore, the composition of the two polymers is likely to be non-uniform, and it is difficult to control the particle size and distribution of the dispersion even if wax is added in the toner manufacturing process. The crushed particle size tends to be broad, and there is still a problem to be improved.

JP-A-7-28725 discloses a binder resin having a specific molecular weight distribution, which is composed of a blend of polyester and vinyl resin, and has a melting point of 110 to 17.
A toner in which a wax at 0 ° C. is dispersed to a size of 2 μm or less is disclosed.

However, in the above-mentioned toner, since the binder resin is a simple blend of polyester and vinyl resin, the dispersion state of the wax is easily affected by the composition ratio of the surrounding resin in which the wax is present, and the uniformity of the wax is ensured. It is difficult to disperse in the particle size, and there is still a problem to be improved.

For both copiers and printers, it is required to improve the resolution and sharpness of the image. For this purpose, it is effective to reduce the particle size of the toner, but the fixability of the halftone portion tends to deteriorate. According to the study of the present inventor, this is due to the small amount of the toner applied in the halftone portion, and the compression heating method using a high-speed machine using a heat roll fixing device and a fixed heating heater via a heat-resistant film. This is remarkable in medium to low speed machines that use.

[0023]

SUMMARY OF THE INVENTION The present invention provides a toner which has solved the above-mentioned problems.

That is, an object of the present invention is to provide a toner in which wax is uniformly dispersed in a binder resin.

An object of the present invention is to provide a toner which is uniformly dispersed in a binder resin even if the wax contained in the toner is a plurality of polyethylene waxes and hydrocarbon waxes having different melting points and compatibility. Things.

An object of the present invention is to provide a binder resin for toner which has excellent pulverizability and a sharp pulverized particle size.

Another object of the present invention is to provide a good halftone fixing property even when used in a binder resin of a toner having a reduced particle diameter and an increased content of a coloring agent (particularly a magnetic substance). This is to provide a toner.

Another object of the present invention is to provide good low-temperature fixability even in a high-speed machine using a hot roll fixing device and a medium to low-speed machine using a press-fit heating method using a fixed heating heater via a heat-resistant film. The present invention is to provide a toner which exhibits a wide fixing temperature range in which offset does not occur even at high temperatures.

[0029]

According to the present invention, there is provided a toner containing at least a binder resin, a colorant and a wax, wherein the binder resin comprises a component (i): an aromatic compound for forming a vinyl copolymer. Component (ii): Acid component and alcohol component for forming polyester resin Component (iii): Wax A mixture containing at least a group III vinyl monomer, a (meth) acrylate monomer, and a vinyl monomer having a carboxyl group. Polymerizing the monomer of component (i) in the mixture to form a vinyl copolymer (A), and then, in the presence of wax and the vinyl copolymer component, an acid component of component (ii) and A resin component prepared by polycondensation of an alcohol component to produce a polyester component (B), and a vinyl copolymer and a polyester Reaction products of Le resin by containing (C) a toner according to claim.

[0030]

DESCRIPTION OF THE PREFERRED EMBODIMENTS According to the study of the present inventor, a toner having a small particle size and an increased content of a coloring agent (particularly a magnetic substance) is suitable for a halftone image irrespective of the fixing system heating method. In order to obtain a toner that exhibits high low-temperature fixability, a high offset generation temperature, and no offset, not only the wax contained in the binder resin of the toner is dispersed into fine particles but also has an appropriate particle size distribution. This is very important.

According to the study of the present inventors, wax can achieve a good dispersion particle size and a good particle size distribution relatively easily with a vinyl copolymer, but with a polyester resin. It is difficult to achieve good dispersion.

In a conventionally known toner using a binder resin, which is a blend of a polyester resin and a vinyl copolymer or a resin composition presumed to be a blend,
No wax is added, or a wax having a specific melting point or a wax mainly composed of natural products having a specific oxidation is added.

When these waxes are used, it is possible to disperse them to a very small particle size. However, since the vinyl copolymer and polyester resin, which are the main components of the binder resin, are not uniformly mixed, the binder resin composition in the vicinity of the wax is not always uniform, and the dispersed wax Was easy to become broad in particle size distribution. Therefore, although the toner fixability is improved to some extent, not only the toner fixability but also the developability can be greatly affected. Was not.

According to the study of the present inventor, not only the dispersed particle size of wax but also the toner having a binder resin containing a vinyl copolymer and a polyester resin as main components,
In order to control the particle size distribution, the conventionally known method of adding wax in the kneading process of toner is insufficient. Since the vinyl copolymer and the polyester resin as the components are not uniformly mixed, the dispersion of the wax is not always sufficient for the above-described reason.

In order to further improve the dispersion state of the wax, it is necessary to add not only the wax in the binder resin production process but also the reaction between the vinyl copolymer having a specific chemical structure and the polyester resin in the binder resin. It is important that the product be contained in a certain amount. It is not clear why the mixing of the vinyl copolymer and the polyester resin is promoted by the inclusion of the reaction product of the vinyl copolymer and the polyester resin, but they are concentrated at the interface between the two. It is inferred that

In the toner of the present invention, the reaction product of the vinyl copolymer and the polyester resin may be formed as a by-product in the binder resin production process, but the content of the binder resin is controlled. For this purpose, it is preferable to use a monomer obtained by an esterification reaction between a vinyl monomer having a carboxyl group and an alcohol used as an alcohol component of the polyester resin.

The aromatic vinyl monomer for forming the vinyl copolymer of the present invention includes, for example, styrene,
o-methylstyrene, m-methylstyrene, p-methylstyrene, p-phenylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, pn- Hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, p-methoxystyrene, p-chlorostyrene, 3,4-dichlorostyrene and the like can be mentioned.

The vinyl monomer having a carboxyl group for forming the vinyl copolymer of the present invention includes:
Examples include acrylic acid, methacrylic acid, maleic acid, maleic acid monoester, fumaric acid, and fumaric acid monoester.

The reaction product of the vinyl copolymer and the polyester resin in the toner of the present invention is produced using the following esterified product of a vinyl monomer as a raw material. (A) Acrylic ester (b) Methacrylic ester (c) Monoester or diester of fumaric acid (d) Monoester or diester of maleic acid

Specific vinyl monomers (a) to (d)
Are exemplified.

[0041]

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[0042]

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[0043]

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[0044]

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In the toner of the present invention, the vinyl copolymer contains 50 to 90% by weight, preferably 60 to 85% by weight of an aromatic vinyl monomer, and 8 to 8% by weight of a (meth) acrylate monomer. 40% by weight,
The content is preferably 10 to 30% by weight, and the content is 2 to 20% by weight, preferably 5 to 15% by weight of a vinyl monomer having a carboxyl group.

When the content of the aromatic vinyl monomer is more than 90% by weight, the low-temperature fixability of the toner can be obtained irrespective of the composition of the copolymerized (meth) acrylate monomer and the vinyl monomer having a carboxyl group. May be impaired, which is not preferred. Further, when the content of the aromatic vinyl monomer is less than 50% by weight, the blocking resistance of the toner is not affected by the composition of the copolymerized (meth) acrylate monomer and the vinyl monomer having a carboxyl group. It is not preferable because it may be damaged.

In the toner of the present invention, the vinyl copolymer has a weight average molecular weight (Mw) of 2,000 to 2,000.
0, ratio of weight average molecular weight to number average molecular weight (Mw / Mn)
Is 1.5 to 50 and the peak molecular weight (Mp) is 1500 to 15000, and preferably, Mw is 300.
0 to 15000, Mw / Mn is 2 to 40, Mp is 2
It is a case where it is 500 to 12000, more preferably a case where Mw is 4000 to 12000, Mw / Mn is 3 to 35, and Mp is 4500 to 10000.

Mw is less than 2000, Mw / Mn is 1.5
If it is less than 1, or if Mp is less than 1500, the offset resistance of the toner may deteriorate, which is not preferable. When Mw exceeds 20,000, Mw / Mn exceeds 50, and Mp exceeds 15000, the compatibility with the polyester resin may be significantly impaired, which is not preferable.

In the toner of the present invention, the vinyl copolymer has a glass transition temperature (Tg) of from 50 to 80 ° C., preferably from 52 to 75 ° C., and more preferably from 55 to 75 ° C. In this case, the temperature becomes 70 ° C.
When the Tg is lower than 50 ° C., the blocking resistance of the toner may be impaired, which is not preferable. Also, T
If g exceeds 80 ° C., the low-temperature fixability of the toner may be impaired, which is not preferable.

In the toner of the present invention, the vinyl copolymer may have an acid value (Av) of from 5 to 35 KOH mg / g, preferably from 7 to 30 KOH mg / g, and more preferably from 7 to 30 KOH mg / g. Av is 10 to 25K
OH mg / g. Av is 5KOHmg /
If it is less than g, the compatibility with the polyester resin is impaired, which is not preferable. In addition, Av is 35 KOHmg /
If it exceeds g, the dispersibility of the wax may be impaired, which is not preferred.

In the toner of the present invention, the content of the vinyl copolymer (A), the polyester resin (B) and the reaction product (C) of the vinyl copolymer and the polyester resin contained in the binder resin is as follows. A: B: C = (50
To 300): (100 to 500): (3 to 50)
A: B: C = (80 to 2)
50): (150 to 400): (5 to 40), more preferably A: B: C = (120 to 200): (200 to 350): (10 to 30) is there.

When the content of the reaction product (C) between the vinyl copolymer and the polyester resin is less than 3 by weight, a uniform product is obtained regardless of the contents of the vinyl copolymer and the polyester resin. A compatible state cannot be maintained, which may adversely affect the dispersion and developability of the wax, which is not preferable. When the content of the reaction product (C) of the vinyl copolymer and the polyester resin is more than 50 by weight, the vinyl copolymer is not affected by the content of the vinyl copolymer and the polyester resin. Each of the polymer, the polyester resin, and the reaction product may be in a phase separated state, which is not preferable.

In the toner of the present invention, the binder resin contained in the toner preferably contains a component insoluble in tetrahydrofuran (THF) in an amount of 5 to 60% by weight, more preferably 10 to 60% by weight, based on the binder resin. 55% by weight, more preferably 15 to 50% by weight.
It is the case where it contains. If it is less than 5% by weight, the offset resistance of the toner may be impaired, which is not preferable. If the content exceeds 60% by weight, the low-temperature fixability of the toner is impaired, and at the same time, the pulverizability in the production of the toner is deteriorated.

In the toner of the present invention, the binder resin contained in the toner is a component soluble in tetrahydrofuran (THF), and the weight average molecular weight (Mw) is 20,000 to 15
00000, the ratio of the weight average molecular weight to the number average molecular weight (Mw
/ Mn) is 10 to 200, and the peak molecular weight (Mp) is 2
2,000 to 25,000, preferably M
w is 30,000 to 1,000,000, Mw / Mn is 15
To 150 and Mp of 3,000 to 20,000, more preferably Mw of 40,000 to 800.
000, Mw / Mn is 20 to 120, and Mp is 5
000 to 15000.

Mw is less than 20,000, Mw / Mn is 10
If it is less than 2,000 or Mp is less than 2,000, the offset resistance of the toner may deteriorate, which is not preferable. M
w is more than 1500000, Mw / Mn is more than 200 or Mp
If it exceeds 25,000, the pulverizability in the production of the toner may be significantly impaired, which is not preferable.

In the toner of the present invention, the binder resin may have a glass transition temperature (Tg) of 50 to 75 ° C.
The temperature is preferably 52 to 72 ° C, and more preferably 55 to 70 ° C. Tg is 50 ° C
If it is less than the above range, the blocking resistance of the toner may be impaired, which is not preferable. If the Tg exceeds 75 ° C., the low-temperature fixability of the toner may be impaired, which is not preferable.

In the toner of the present invention, the acid value (Av) of the binder resin may be from 10 to 40 KOH mg / g, preferably from 12 to 35 KOH mg / g, and more preferably from Av to 12 KOH mg / g. 15 to 30 KO
Hmg / g. Av is 10 KOHmg /
If it is less than g, the developing property of the toner may be impaired, which is not preferable. In addition, Av is 40 KOHmg /
When the value exceeds g, the developability of the toner may be impaired, which is not preferable.

Examples of the (meth) acrylic acid monomer for forming the vinyl copolymer of the present invention include methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, and methacrylic acid. N-octyl acid, n-dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, n acrylate −
Octyl, n-dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, phenyl acrylate and the like can be mentioned.

If necessary, the polymer may be crosslinked with a crosslinking monomer as exemplified below.

Examples of aromatic divinyl compounds include divinylbenzene and divinylnaphthalene; examples of diacrylate compounds linked by an alkyl chain include:
Ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6 hexanediol diacrylate, neopentyl glycol diacrylate and the above compounds Examples of the acrylate include methacrylates; diacrylate compounds linked by an alkyl chain containing an ether bond include, for example, diethylene glycol diacrylate, triethylene glycol diacrylate,
Tetraethylene glycol diacrylate, polyethylene glycol # 400 diacrylate, polyethylene glycol # 600 diacrylate, dipropylene glycol diacrylate and the above compounds in which the acrylate is replaced with methacrylate; including an aromatic group and an ether bond Examples of chain-linked diacrylate compounds include polyoxyethylene (2) -2,2
-Bis (4-hydroxyphenyl) propane diacrylate, polyoxyethylene (4) -2,2-bis (4-
(Hydroxyphenyl) propane diacrylate and those obtained by replacing the acrylates of the above compounds with methacrylates; polyester-type diacrylates include, for example, the trade name MANDA (Nippon Kayaku).

Of these crosslinkable monomers, those which are preferably used from the viewpoint of fixing property and offset resistance to the resin for toner include an aromatic divinyl compound (particularly divinylbenzene), an aromatic group and one ether bond. And diacrylate compounds linked by a chain.

In the present invention, the polymerization initiator used for producing the vinyl copolymer includes, for example,
2,2'-azobisisobutyronitrile, 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis (-2,4-dimethylvaleronitrile), 2 , 2'-Azobis (-2methylbutyronitrile), dimethyl-2,2'-azobisisobutyrate, 1,1'-azobis (1-cyclohexanecarbonitrile), 2- (carbamoylazo) -isobutyro Nitrile, 2,2'-azobis (2,4,4-trimethylpentane), 2-phenylazo-2,4-dimethyl-4-
Ketone peroxides such as methoxyvaleronitrile, 2,2′-azobis (2-methyl-propane), methyl ethyl ketone peroxide, acetylacetone peroxide and cyclohexanone peroxide;
2-bis (t-butylperoxy) butane, t-butyl hydroperoxide, cumene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, di-t-butyl peroxide, t-butyl Cumyl peroxide, di-cumyl peroxide,
α, α'-bis (t-butylperoxyisopropyl)
Benzene, isobutyl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, m-trioil peroxide, di-isopropylperoxydicarbonate , Di-2-ethylhexylperoxydicarbonate, di-n-propylperoxydicarbonate, di-2-ethoxyethylperoxycarbonate,
Di-methoxyisopropyl peroxydicarbonate,
Di (3-methyl-3-methoxybutyl) peroxycarbonate, acetylcyclohexylsulfonyl peroxide, t-butylperoxyacetate, t-butylperoxyisobutyrate, t-butylperoxyneodecanoate, t-butyl Peroxy 2-ethylhexanoate, t-butyl peroxy laurate, t-butyl peroxy benzoate, t-butyl peroxy isopropyl carbonate, di-t-butyl peroxy isophthalate, t-butyl peroxy allyl carbonate , T-amyl peroxy 2-ethylhexanoate,
Examples thereof include di-t-butylperoxyhexahydroterephthalate and di-t-butylperoxyazelate.

The acid component for forming the polyester resin of the present invention includes benzenedicarboxylic acid such as phthalic acid, isophthalic acid and terephthalic acid or an acid anhydride thereof; succinic acid, adipic acid, sebacic acid, azelaic acid and the like. Alkyl carboxylic acids or anhydrides thereof;
Examples include succinic acid substituted with an alkyl group having 6 to 20 carbon atoms or an acid anhydride thereof.

As alcohol components for forming the polyester resin of the present invention, ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-
Butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, hydrogenated bisphenol A, A bisphenol derivative represented by the following formula;

[0065]

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Diols represented by the following formula;

[0067]

Embedded image And the like.

The wax preferably used in the present invention is:
Consisting of a hydrocarbon having a long-chain alkyl group,
Preferably, it is a wax having, as a main chain or a side chain, a hydrocarbon compound comprising a long-chain alkyl group having few branches, and the wax in which the hydrocarbon compound forms a main chain is, for example, radical polymerization of alkylene under high pressure. Alternatively, a low-molecular-weight alkylene polymer polymerized with a Ziegler catalyst under a low pressure, an alkylene polymer obtained by thermally decomposing a high-molecular-weight alkylene polymer, and a residue obtained by distillation of a hydrocarbon obtained from a mixed gas composed of carbon monoxide and hydrogen by the Age method Or a synthetic hydrocarbon obtained by hydrogenating them. The wax having a hydrocarbon compound as a side chain is obtained by copolymerizing a long-chain alkene and a vinyl monomer such as ethylene, and may contain a component having a substituent such as a hydroxyl group or a carboxyl group.

The wax used in the present invention may be a mixture of a low melting point wax component having a relatively low melting point and a high melting point wax component having a relatively high melting point, and the amount of each wax added to 100 parts by weight of the binder resin component. May be 3 to 20 parts by weight, preferably 4 to 15 parts by weight, and more preferably 5 to 10 parts by weight. If the total amount of the wax is less than 3 parts by weight, the low-temperature fixability and the hot offset resistance of the toner may be adversely affected, which is not preferable. If the total amount of the wax exceeds 20 parts by weight, In this case, it is difficult to keep the dispersion of the wax in a good state, which may adversely affect the developing property of the toner, which is not preferable.

When two or more waxes are used in the toner of the present invention, the melting point and the amount added satisfy the following relational expression (1).

[0071]

(Equation 2) (Wherein, Lv, Hv each low melting wax, represents the amount of the binder resin having a high melting point waxes, L _M, H _M represents each low melting wax, the melting point of the high melting point waxes.)

The relational expression represented by the expression (1) is preferably 7
The case is 5 to 125, and the more preferable case is 80 to 120. If the relational expression represented by the expression (1) is less than 70, the blocking resistance and the hot offset resistance of the toner may be adversely affected, which is not preferable. The relational expression represented by the expression (1) is more than 130. In such a case, the low-temperature fixability of the toner may be adversely affected, which is not preferable.

The low-melting wax component preferably used in the present invention has a weight average molecular weight (Mw) of 600 to 950, more preferably 650 to 900, and Mw / Mn of 2.8 or less when it is composed of a hydrocarbon compound. ,
More preferably, it is 2.3 or less.

When the low-melting-point wax component has a linear hydrocarbon compound having few branches as a side chain,
Mw is from 1000 to 3000, more preferably 1200
To 2500, and Mw / Mn is 8.0 or less, more preferably 3 to 7.5.

The high melting point wax component preferably used in the present invention, when it is composed of a hydrocarbon compound, has a Mw of
Is 1000 to 15000, preferably 1200 to 1
0000, more preferably 1500 to 9000, and Mw / Mn of 3.0 or less, more preferably 2.5 or less.

When the high-melting-point wax component has a straight-chain hydrocarbon compound with few branches as a side chain, the Mw is 2,000 to 50,000, more preferably 3,000 to 35,000, and Mw / Mn is 50. Less than,
More preferably, it is 5 to 30.

In the present invention, a method for adding a plurality of different waxes to the toner will be described below.

[1] When all the waxes are added during the production of the binder resin Combination of a low melting point hydrocarbon wax component and a high melting point hydrocarbon wax component: The low melting point hydrocarbon wax has a long-chain alkyl group with few branches. Has a melting point of 70 to 90 ° C.,
It is preferable that Mw is 600 to 950 and Mw / Mn is 1.5 to 2.5. When the low-melting wax has a branched structure having a long-chain alkyl group with few branches as a side chain, it is preferable that Mw is 2,000 to 7000 and Mw / Mn is 5.0 to 15.
The high-melting-point wax component preferably has a long-chain alkyl group with few branches, a melting point of 95 to 130 ° C., and a Mw of 800 to 2500.

[2] When Only Low Melting Point Wax is Added at the Time of Binder Resin Production The low melting point hydrocarbon wax component used is the same as the low melting point hydrocarbon wax shown in the above [1]. The high-melting-point wax component may be the same as the high-melting-point hydrocarbon wax shown in the above [1]. However, the high-melting-point wax component has a substituent other than a hydrogen atom at the terminal or in a part of the molecule. As a hydroxyl group and / or a carboxyl group,
It is preferable that the alkyl component having a substituent is contained in an amount of 50% by weight or more of the total wax. Further, the high melting point substituted alkyl wax component has a melting point of 95 to 130 ° C.,
Mw is 800 to 5000, and Mw / Mn is 2 to 3.5.

[3] When only high-melting-point wax is added during the production of the binder resin The high-melting-point hydrocarbon wax used is the same as the high-melting-point hydrocarbon wax shown in the above [1]. The low-melting-point wax component may be the same as the low-melting-point hydrocarbon wax shown in the above [1]. However, the low-melting-point wax component has a substituent other than a hydrogen atom at the terminal or in a part of the molecule. As a hydroxyl group and / or a carboxyl group,
It is preferable that the alkyl component having a substituent is contained in an amount of 50% by weight or more of the total wax. Further, the low melting point substituted alkyl wax component has a melting point of 70 to 90 ° C.
w is 400 to 700, and Mw / Mn is 1.5 to 3.

In the toner of the present invention, a charge control agent may be used as needed in order to further stabilize the chargeability. The charge control agent is 0.1 to 100 parts by weight of the binder resin.
It is preferred to use 10 parts by weight, preferably 0.2 to 5 parts by weight.

Examples of the charge control agent include the following.

For example, an organic metal complex, a chelate compound and an organic metal salt can be mentioned. Specific examples include a monoazo metal complex; a metal complex or a metal salt of an aromatic hydroxycarboxylic acid or an aromatic dicarboxylic acid compound. Other examples include aromatic hydroxycarboxylic acids, aromatic mono- and polycarboxylic acids and their anhydrides and esters, and phenol derivatives of bisphenol.

When the toner of the present invention is used as a magnetic toner, the magnetic material contained in the magnetic toner includes iron oxides such as magnetite, maghemite and ferrite, and iron oxides containing other metal oxides; Fe, Co, Ni Or a metal such as Al, Co, Cu,
Pb, Mg, Ni, Sn, Zn, Sb, Be, Bi, C
Alloys with metals such as d, Ca, Mn, Se, Ti, W, and V, and mixtures thereof, and the like.

Specifically, examples of the magnetic material include iron trioxide (Fe ₃ O ₄ ), iron sesquioxide (γ-Fe ₂ O ₃ ), zinc iron oxide (ZnFe ₂ O ₄ ), yttrium iron oxide ( Y ₃ Fe ₅
O ₁₂ ), iron cadmium oxide (CdFe ₂ O ₄ ), iron gadolinium oxide (Gd ₃ Fe ₅ —O ₁₂ ), iron oxide copper (CuFe)
₂ O ₄ ), lead iron oxide (PbFe ₁₂ —O ₁₉ ), nickel iron oxide (NiFe ₂ O ₄ ), and neodymium iron oxide (NdFe
₂ O ₃ ), barium iron oxide (BaFe ₁₂ O ₁₉ ), iron magnesium oxide (MgFe ₂ O ₄ ), iron manganese oxide (MnF
e ₂ O ₄ ), iron lanthanum oxide (LaFeO ₃ ), iron powder (F
e), cobalt powder (Co), nickel powder (Ni) and the like. The above-mentioned magnetic materials are used alone or in combination of two or more. Particularly preferred magnetic materials are fine powders of triiron tetroxide or gamma-iron sesquioxide.

These ferromagnetic materials have an average particle size of 0.1 to 2
μm (more preferably 0.1 to 0.5 μm) and 10K
The magnetic properties upon application of the Oersted are coercive force of 20 to 150 Oersted, saturation magnetization of 50 to 200 emu / g (preferably 50 to 100 emu / g), and residual magnetization of 2 to 20 em.
u / g is preferred.

The magnetic material 1 was added to 100 parts by weight of the binder resin.
It is preferable to use 0 to 200 parts by weight, preferably 20 to 150 parts by weight.

In addition to the magnetic substance, carbon black, titanium white and other pigments and / or dyes can be used as the coloring agent. For example, when using the toner of the present invention as a magnetic color toner, as the dye,
C. I. Direct Red 1, C.I. I. Direct Red 4, C.I. I. Acid Red 1, C.I. I. Basic Red 1, C.I. I. Modant Red 30, C.I. I. Direct Blue 1, C.I. I. Direct Blue 2, C.I.
I. Acid Blue 9, C.I. I. Acid blue 15,
C. I. Basic Blue 3, C.I. I. Basic Blue 5, C.I. I. Modant Blue 7, C.I. I. Direct Green 6, C.I. I. Basic Green 4, C.I.
I. Basic Green 6 and the like. Pigments include mineral fast yellow, navel yellow, naphthol yellow S, Hanza yellow G, permanent yellow NCG, tartrazine lake, molybdenum orange,
Permanent Orange GTR, Pyrazolone Orange, Benzidine Orange G, Cadmium Red, Permanent Red 4R, Watching Red Calcium Salt, Eosin Lake, Brilliant Carmine 3B, Manganese Purple, Fast Violet B, Methyl Violet Lake, Cobalt Blue, Alkaline Blue Lake, Victoria Blue Lake, Phthalocyanine Blue, First Sky Blue, Indanthrene Blue BC, Pigment Green B, Malachite Green Lake, Final Yellow Green G and the like.

When the toner of the present invention is used as a two-component full-color toner, the following colorants may be used. Examples of the magenta coloring pigment include C.I.
I. Pigment Red 1, 2, 3, 4, 5, 6, 7,
8, 9, 10, 11, 12, 13, 14, 15, 16,
17, 18, 19, 21, 22, 23, 30, 31, 3
2,37,38,39,40,41,48,49,5
0, 51, 52, 53, 54, 55, 57, 58, 6
0, 63, 64, 68, 81, 83, 87, 88, 8
9, 90, 112, 114, 122, 123, 163,
202, 206, 207, 209, C.I. I. Pigment Violet 19, C.I. I. Butt Red 1,2,1
0, 13, 15, 23, 29, 35 and the like.

Although the above pigments may be used alone,
It is more preferable to improve the sharpness by using a dye and a pigment in combination from the viewpoint of the image quality of a full-color image. Magenta dyes include C.I. I. Solvent Red 1,3,8,2
3,24,25,27,30,49,81,82,8
3,84,100,109,121, C.I. I. Disperse Red 9, C.I. I. Solvent Violet 8,1
3, 14, 21, 27, C.I. I. Oil-soluble dyes such as Disperse Violet 1, C.I. I. Basic Red 1,
2, 9, 12, 13, 14, 15, 17, 18, 22,
23, 24, 27, 29, 32, 34, 35, 36, 3
7, 38, 39, 40, C.I. I. Basic violet 1,3,7,10,14,15,21,25,26,
And basic dyes such as 27 and 28.

Examples of the cyan coloring pigment include C.I. I. Pigment Blue 2, 3, 15, 16, 17, C.I. I. Bat Blue 6, C.I. I. Acid Blue 45 or a copper phthalocyanine pigment in which 1 to 5 phthalimidomethyl groups are substituted on a phthalocyanine skeleton having a structure represented by the following formula.

[0092]

Embedded image

Examples of yellow color pigments include C.I. I. Pigment Yellow 1,2,3,4,5,6,7,10,
11, 12, 13, 14, 15, 16, 17, 23, 6
5, 73, 83, C.I. I. Bat Yellow 1,3,20
And the like.

The amount of the nonmagnetic colorant used is 100
0.1 to 60 parts by weight, preferably 0.5 part by weight,
５０50 parts by weight.

A fluidity improver may be added to the toner of the present invention. The fluidity improver can be added to the toner to increase the fluidity before and after the addition. For example, fluororesin powders such as vinylidene fluoride fine powder and polytetrafluoroethylene fine powder; fine powder silica such as wet-process silica and dry-process silica, fine powder titanium oxide, fine powder alumina, a silane coupling agent thereof, There are treated silica, treated titanium oxide, and treated alumina that have been surface-treated with a titanium coupling agent and silicone oil.

Preferred fluidity improvers are fine powders produced by vapor phase oxidation of silicon halides, and are so-called dry silica or fumed silica. For example, it utilizes the thermal decomposition oxidation reaction of silicon tetrachloride gas in an oxyhydrogen flame, and the basic reaction formula is as follows.

SiCl ₂ + 2H ₂ + O ₂ → SiO ₂ + 4HC
l

In this production process, it is possible to obtain a composite fine powder of silica and another metal oxide by using another metal halide such as aluminum chloride or titanium chloride together with the silicon halide. They are also included. The particle size is preferably in the range of 0.001 to 2 μm as an average primary particle size, and particularly preferably, fine silica powder in the range of 0.002 to 0.2 μm is used. .

Commercially available silica fine powder produced by the vapor phase oxidation of a silicon halide compound includes, for example, those commercially available under the following trade names.

AEROSIL (Aerosil Japan) 130 200 300 380 TT600 MOX170 MOX80 COK84 Ca-O-SiL (CABOT Co.) M-5 MS-7 MS-75 HS-5 EH-5 Wacker HDK N20 V15 WAC -CHEMIE GMBH) N20E T30 T40 DC Fine Silica (Dow Corning Co.) Fransol (Fransil)

Further, a treated silica fine powder obtained by subjecting a silica fine powder produced by the gas phase oxidation of the silicon halide compound to a hydrophobic treatment is more preferable. It is particularly preferable that the treated silica fine powder is obtained by treating the silica fine powder such that the degree of hydrophobicity measured by a methanol titration test shows a value in the range of 30 to 80.

The method of imparting hydrophobicity is provided by chemically treating with an organic silicon compound or the like which reacts with or physically adsorbs silica fine powder. As a preferred method, silica fine powder produced by vapor phase oxidation of a silicon halide is treated with an organosilicon compound.

Examples of the organosilicon compound include hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane, benzyldimethylchlorosilane, Bromomethyldimethylchlorosilane,
α-chloroethyltrichlorosilane, ρ-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilylmercaptan, trimethylsilylmercaptan, triorganosilyl acrylate, vinyldimethylacetoxysilane, dimethylethoxysilane, dimethyldimethoxysilane, diphenyldiethoxysilane , Hexamethyldisiloxane, 1,3-divinyltetramethyldisiloxane, 1,3-diphenyltetramethyldisiloxane and 2 to 12 siloxane units per molecule, each having one to each of the terminal units. Examples include dimethylpolysiloxane containing a hydroxyl group bonded to Si. Further, a silicone oil such as dimethyl silicone oil may be used. These are used alone or as a mixture of two or more.

The fluidity improver has a specific surface area by nitrogen adsorption measured by the BET method of 30 m ² / g or more, preferably 5 m ² / g or more.
Those with 0 m ² / g or more give good results. Toner 1
0.01 to 8 parts by weight of the fluidity improver based on 00 parts by weight,
Preferably, 0.1 to 4 parts by weight is used.

To produce the toner of the present invention, a binder resin,
A colorant and / or a magnetic substance, a charge control agent or other additives are sufficiently mixed by a mixer such as a Henschel mixer or a ball mill, and are melted, kneaded and kneaded using a hot kneader such as a kneader or an extruder. Then, the resins are mutually dissolved, and the melt-kneaded product is cooled and solidified, and then the solidified product is pulverized, and the pulverized product is classified to obtain the toner of the present invention.

The toner of the present invention preferably has a weight average particle diameter of 3 to 9 μm (more preferably, 3 to 8 μm) in terms of resolution and image density. And heat and pressure.

Further, in the present invention, when the volume average particle diameter (D _V ) of the toner is 2.5 μm or more, a decrease in image density hardly occurs, and a sufficient image density is obtained.
When the particle size is 0 μm or less, the volume average particle diameter (D _V ) of the toner is preferably 2.5 to 6.0 μm since the gradation of a halftone image is particularly improved.

Further, the fluidity improver and the toner are sufficiently mixed by a mixer such as a Henschel mixer to obtain a toner having a fluidity improver on the surface of toner particles.

The methods for quantifying the solvent-soluble components of the toner of the present invention and measuring other physical properties are described below.

(1) Measurement of THF-insoluble content The THF-insoluble content referred to in the present application is the “polymer component insoluble in the THF solvent in the toner (substantially crosslinked polymer) calculated by the Soxhlet extraction method. )). That is, 2.0 g of the toner sample was precisely weighed (W ₁ g), and a cylindrical filter paper (for example, No. 86 manufactured by Toyo Filter Paper) was used.
R: Dimensions: 28 mm outside diameter x 100 mm height), put it through a Soxhlet extractor, and use THF 200 ml as a solvent.
8 using an oil bath temperature-controlled to 120 ° C using
After the time extraction, the amount of the soluble resin component extracted by the solvent is weighed (W ₂ g).

When measuring the THF insoluble content of the toner,
Pigments, colorants, waxes, etc. are considered insoluble in solvents. That is, the weight of the solvent-insoluble component other than the resin is (W ₃
In the case of g), the THF-insoluble matter is obtained by the following equation.

[0112]

(Equation 3)

(2) Measurement of melting point of wax ASTM D3418-8 using a differential scanning calorimeter (DSC measuring apparatus) and DSC-7 (manufactured by PerkinElmer).
Measure according to 2.

The measurement sample is 2 to 10 mg, preferably 5 m
Weigh g precisely.

This was put in an aluminum pan, and an empty aluminum pan was used as a reference.
The measurement is performed at a temperature rising rate of 10 ° C./min and at normal temperature and normal humidity between 0 ° C.

In this heating process, an endothermic peak of the main peak of the DSC curve in the temperature range of 30 to 200 ° C. is obtained.

The temperature of the endothermic main peak is defined as the melting point of the wax.

(3) Measurement of DSC Curve of Toner A DSC curve in the process of raising the temperature of the toner is measured in the same manner as in the measurement of the melting point of the wax.

(4) Glass transition temperature (Tg) of binder resin
ASTM D3418-8 using a differential scanning calorimeter (DSC measuring device) and DSC-7 (manufactured by PerkinElmer).
Measure according to 2.

The measurement sample is 5 to 20 mg, preferably 10
Weigh the mg precisely.

This was put in an aluminum pan, and an empty aluminum pan was used as a reference.
The measurement is performed at a temperature rising rate of 10 ° C./min and at normal temperature and normal humidity between 0 ° C.

During the heating process, an endothermic peak of the main peak in the temperature range of 40 to 100 ° C. is obtained.

At this time, the intersection between the line of the midpoint of the baseline before and after the endothermic peak appears and the differential heat curve is defined as the glass transition temperature Tg in the present invention.

(5) Measurement of wax molecular weight distribution Gel permeation chromatography (GPC) measuring apparatus: GPC-150C (Waters) Column: GMH-HT 30 cm double (manufactured by Tosoh Corporation) Temperature: 135 ° C. Solvent: o-dichlorobenzene (0.1% ionol added) Flow rate: 1.0 ml / min Sample: 0.4 ml of 0.15% sample injected

Measurement is performed under the above conditions, and the molecular weight of the sample is calculated using a molecular weight calibration curve prepared from a monodisperse polystyrene standard sample. In addition, Mark-Hou
It is calculated by converting to polyethylene using a conversion formula derived from the wink viscosity formula.

(6) Measurement of Molecular Weight Distribution of Binder Resin Raw Material or Binder Resin of Toner The molecular weight of a chromatogram by GPC is measured under the following conditions.

The column is stabilized in a heat chamber at 40 ° C., and tetrahydrofuran (THF) is passed through the column at this temperature as a solvent at a flow rate of 1 ml per minute.
When the sample is a binder resin material, a material obtained by passing the binder resin material through a roll mill (130 ° C., 15 minutes) is used. If the sample is a toner, dissolve the toner in THF
m, and the filtrate is used as a sample.
The measurement is performed by injecting 50 to 200 μl of a THF sample solution of a resin adjusted to a sample concentration of 0.05 to 0.6% by weight. In measuring the molecular weight of a sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of a calibration curve prepared from several types of monodisperse polystyrene standard samples and the count number. As standard polystyrene samples for creating calibration curves,
For example, Pressure Chemical Co.
Or Toyo Soda Kogyo Co., Ltd. has a molecular weight of 6 × 1
0 ² , 2.1 × 10 ³ , 4 × 10 ³ , 1.75 × 1
0 ⁴ , 5.1 × 10 ⁴ , 1.1 × 10 ⁵ , 3.9 × 10
⁵ , 8.6 × 10 ⁵ , 2 × 10 ⁶ , 4.48 × 10 ⁶ , and it is appropriate to use at least about 10 standard polystyrene samples. An RI (refractive index) detector is used as the detector.

In order to accurately measure the molecular weight region of 10 ³ to 2 × 10 ^6, a plurality of commercially available polystyrene gel columns may be used in combination.
rs Co., Ltd. μ-styragel 500, 10 ³ , 1
0 ⁴ 10 ⁵ of combinations and, shodex of Showa Denko Co., Ltd.
KA-801, 802, 803, 804, 805, 8
06,807 are preferred.

The particle size distribution of the toner of the present invention is measured using a Coulter Counter TA-II or a Coulter Multisizer (manufactured by Coulter). The electrolyte is 1
A 1% NaCl aqueous solution is prepared using graded sodium chloride. For example, ISOTON-II (manufactured by Coulter Scientific Japan) can be used. As a measurement method, 0.1 to 5 ml of a surfactant, preferably an alkylbenzene sulfonate, is added as a dispersant to 100 to 150 ml of the electrolytic aqueous solution, and a measurement sample is further added to 2-2.
Add 0 mg. The electrolytic solution in which the sample was suspended was subjected to dispersion treatment for about 1 to 3 minutes using an ultrasonic disperser, and the volume and the number of toner particles having a size of 2 μm or more were measured using the measuring device with a 100 μm aperture as the aperture. The distribution and number distribution were calculated.

Then, the weight-based weight average particle diameter (D ₄ ) and volume average particle diameter (D _V ) obtained from the volume distribution according to the present invention (each median value of each channel is a representative value for each channel) I asked.

Next, an example of an image forming apparatus to which the toner of the present invention can be applied will be described with reference to FIGS. The surface of the electrostatic image carrier (photoconductor) 1 is charged to a negative polarity or a positive polarity by the primary charger 2 and an electrostatic image (for example, a digital latent image by image scanning) is formed by analog exposure or exposure 5 by laser light. Then, the electrostatic charge image is reverse developed or developed by the magnetic toner 13 of the developing device 9 including the magnetic blade 11 and the developing sleeve 4 including the magnet 23 having the magnetic poles N ₁ , N ₂ , S ₁ and S _2. Develop by regular development. In the developing section, between the conductive substrate 16 of the photoreceptor 1 and the developing sleeve 4, an alternating bias, a pulse bias and / or a DC bias are applied by the bias applying means 12. The magnetic toner image is transferred to a transfer material with or without an intermediate transfer member. When the transfer paper P is conveyed and reaches the transfer section, the transfer paper P is transferred by the transfer charger 3.
The negatively charged or positively charged magnetic toner image on the surface of the photoreceptor is electrostatically transferred onto the transfer paper P by charging the surface of the photoreceptor with a positive or negative polarity from the back side (opposite side to the photoreceptor side). You. After the charge is removed by the charge removing means 22, the transfer paper P separated from the photoreceptor 1 is heated and pressed and fixed on the toner image on the transfer paper P by the heating and pressing roller fixing device 7 including the heater 21.

The magnetic toner remaining on the photoreceptor 1 after the transfer step is removed by a cleaning means having a cleaning blade 8. After the cleaning, the photosensitive member 1 is neutralized by the erase exposure 6, and the process starting from the charging process by the primary charger 2 is repeated again.

An electrostatic image carrier (for example, a photosensitive drum) 1 has a photosensitive layer 15 and a conductive substrate 16 and moves in the direction of the arrow. Non-magnetic cylindrical developing sleeve 4 which is developing sleeve 4
Rotates so as to advance in the same direction as the surface of the electrostatic image carrier 1 in the developing section. Inside the non-magnetic cylindrical developing sleeve 4, a multi-pole permanent magnet (magnet roll) 23 as a magnetic field generating means is arranged so as not to rotate. The magnetic toner 13 in the developing device 9 is applied to the developing sleeve 4,
In addition, triboelectric charges are given to the magnetic toner particles by friction between the surface of the developing sleeve 4 and the magnetic toner particles. Further, a magnetic doctor blade 17 made of iron is placed close to the surface of the cylindrical developing sleeve 4 (at an interval of 50 μm to 500 μm).
m), the thickness of the magnetic toner layer is reduced (from 30 μm to
The magnetic toner layer is formed to have a thickness equal to or smaller than the gap between the photoconductor 1 and the developing sleeve 4 in the developing section while being regulated uniformly. By adjusting the rotation speed of the developing sleeve 4, the surface speed of the developing sleeve can be reduced.
The speed is substantially the same as or close to the speed of the surface of the substrate. The opposed magnetic poles may be formed by using permanent magnets instead of iron as the magnetic doctor blades 17. In the developing section, an AC bias or a pulse bias may be applied to the developing sleeve 4 by the bias unit 12. This AC bias is f 200-4,000H
z, V _pp may if 500~3,000V.

At the time of transfer of the magnetic toner particles in the developing section, the magnetic toner particles move to the electrostatic image side due to the electrostatic force of the photoreceptor surface and the action of an AC bias or a pulse bias.

Instead of the magnetic blade 11, an elastic blade made of an elastic material such as silicone rubber may be used to regulate the thickness of the magnetic toner layer by pressing to apply the magnetic toner on the developing sleeve.

[0136]

Hereinafter, the present invention will be described with reference to Examples.
The present invention is not limited to these examples.

<Production Example> [1-A] Production of reaction product (A) of vinyl copolymer and polyester resin: 85 parts by weight of styrene 15 parts by weight of butyl acrylate Exemplified monomer (a-2) 5 parts by weight ・ Lauroyl peroxide 3 parts by weight

The above vinyl monomer mixture was treated with xylene 30
Together with 0 parts by weight into an autoclave equipped with a thermometer, a nitrogen inlet tube, a decompression device, and a stirring device.
Solution polymerization was performed at 0 ° C. to obtain an intermediate (a). The intermediate (a) has a weight average molecular weight (Mw) of 16800 and Mw /
It was a polymer having an Mn of 2.9 and a glass transition temperature (Tg) of 65.2 ° C.

Next, in the xylene solution containing the above intermediate (a), 30 parts by weight of 100 parts by weight of the intermediate (a) were used as a raw material for the following polyester resin such as alcohol, carboxylic acid and esterified ester. A catalyst was added, and an esterification reaction was performed according to a conventional method. By distilling off xylene, a weight average molecular weight (Mw) of 18300, Mw / M
A reaction product (A) of a vinyl copolymer and a polyester resin having n = 3.7 and a glass transition temperature (Tg) of 63.2 ° C. was obtained. -PO-BPA 3.0 mol-EO-BPA 2.0 mol-Terephthalic acid 5.0 mol-Trimellitic anhydride 1.5 mol

[1-B] to [1-D] Production of reaction products (B) to (D) of vinyl copolymer and polyester resin: Except for using the exemplified monomers shown in Table 1, the procedure was the same. Reaction products (B) to (D) of the vinyl copolymer and the polyester resin were obtained.

[2-A] Production of binder resin (1): 75 parts by weight of styrene 12 parts by weight of butyl acrylate 5 parts by weight of acrylic acid 8 parts by weight of reaction product (A) 8 lauroyl peroxide 3 Parts by weight Wax H-1 (see Table 3) 12 parts by weight PO-BPA 7.0 mol EO-BPA 2.0 mol Terephthalic acid 5.0 mol Trimellitic anhydride 2.0 mol

A vinyl monomer for forming the vinyl copolymer, a mixture of a carboxylic acid, an alcohol and a wax for forming a polyester resin were mixed with 200 parts by weight of toluene together with a thermometer, a nitrogen inlet tube, a pressure reducing device, It was charged into an autoclave equipped with a stirrer. In order to form a vinyl copolymer, radical polymerization was performed at about 110 ° C. for 5 hours in a nitrogen atmosphere.

Next, an esterification reaction was carried out while heating the temperature to about 150 ° C. and distilling off water produced together with toluene. After the distillation of water and toluene was no longer observed, the temperature of the autoclave was further increased to about 220 ° C. to carry out the esterification reaction, thereby obtaining the binder resin (1) of the present invention.

[2-B] to [2-G] Binder Resin (2) to
Production of (8): The binder resins (2) to (8) of the present invention were prepared in the same manner except that the reaction product of the vinyl copolymer and the polyester resin shown in Table 2 and the wax shown in Table 3 were used. Obtained.

<Comparative Production Example 1> Production of comparative polyester resin: 10 mol of terephthalic acid 5 mol of PO-BPA

The mixture of the above alcohol and carboxylic acid is subjected to an esterification reaction at a temperature of 230 ° C. according to a conventional method to give an acid value of 3.2 KOH mg / mg and a hydroxyl value of 3 KOH.
4KOHmg / mg, Mw = 5800, Tg = 60.8
A comparative polyester resin having a temperature of ° C was obtained. Production of vinyl copolymer for comparison: 76 parts by weight of styrene 24 parts by weight of butyl acrylate 2 parts by weight of divinylbenzene 4 parts by weight of wax H-5

The above vinyl monomer mixture was treated with dioxane 2
A solution prepared by dissolving 1 part by weight of 4,4-azobis (4-cyanopentanoic acid) as a polymerization initiator in 40 parts by weight of dioxane was added to 00 parts by weight and refluxed.
A vinyl copolymer was produced by a solution polymerization method by dividing and adding intermittently. The obtained vinyl copolymer had an Mw of 236000 and an acid value of 3.6 KOH mg / mg.

The dioxane solution 2 of the above vinyl copolymer
After adding and dissolving 100 parts by weight of the comparative polyester resin to 00 parts by weight, dioxane was distilled off under reduced pressure. After completion of the distillation, esterification was carried out by heating to 180 ° C., acid value 1.6 KOH mg / mg, Mw = 19200
0, Mw / Mn = 4.7, although not clear, Tg about 5
A comparative binder resin (1) measured as a mixture of polymers at 8.2 ° C and 72.1 ° C was obtained.

<Comparative Production Example 2>
A comparative binder resin (2) was obtained in the same manner except that lauroyl peroxide was used as the polymerization initiator.

[0150]

[Table 1]

[0151]

[Table 2]

[0152]

[Table 3]

[Example 1]-104 parts by weight of binder resin (1) of the present invention-2 parts by weight of azo-based iron complex compound-100 parts by weight of magnetic iron oxide

The above mixture was melt-kneaded with a twin-screw extruder heated to 130 ° C., and the cooled mixture was roughly pulverized with a hammer mill. The coarsely pulverized product is finely pulverized by a jet mill, and the obtained finely pulverized product is subjected to air classification to have a weight average diameter of 7.
A magnetic toner of 5 μm was obtained.

To 100 parts by weight of the magnetic toner, 1.0 part by weight of hydrophobic dry silica (BET specific surface area = 200 m ² / g) was externally added using a Henschel mixer to obtain a toner. Using this toner, a Canon copier NP-67
When the image characteristics were evaluated at 50, good results were obtained as shown in Table 4.

[Examples 2 to 11] Toners (2) to (11) of the present invention were obtained in the same manner as in Example 1 except that the binder resin and the wax were changed to those shown in Table 4. The toner was evaluated in the same manner as in Example 1.

[Comparative Examples 1-4] Comparative binder resins (1)-
Comparative toners (1) to (4) were produced and evaluated in the same manner as in Example 1 except that (2) was used.

An evaluation method will be described below.

Fixing Property The toner image is fixed on plain paper at a pressure roller temperature of 150 ° C. The fixing property is determined by applying a load of 50 g / cm ² to the fixed image and using a silk cleaning paper [lens cleaning paper].
“Dasper (R)” (Ozu Paper C
o. , Ltd. ) Was rubbed 10 times, and the density reduction rate after rubbing was measured.

In the case of a solid black (D = 1.2) image Rank 5: Density reduction rate 0 to 10% Rank 4: Density reduction rate 11 to 20% Rank 3: Density reduction rate 21 to 30% Rank 2: Density reduction Rate 31 to 40% Rank 1 ... Density reduction rate 41% or more For halftone (D = 0.8) images Rank 5 ... Density reduction rate 0 to 15% Rank 4 ... Density reduction rate 16 to 30% Rank 3 ... Density Decrease rate 31-40% Rank 2 ... Decrease rate 41-50% Rank 1 ... Decrease rate 51% or more

Hot offset resistance At a surface temperature of the heating roller of 230 ° C., the toner image is fixed on plain paper, and then the plain paper is passed through a fixing device to determine whether toner has transferred from the heating roller surface to the plain paper surface. Was evaluated. Rank 5: Toner does not transfer. Rank 4: Transfer of very slight toner. Rank 3: Transfer of slight toner. Rank 2: Clear transfer of toner. Rank 1: Paper sticks to heating roller.

・ Preservation property of toner About 20 g of magnetic toner is put in a 100 ml polycup,
After standing at 50 ° C. for 10 days, it was judged visually. Rank 5: No change Rank 4: Agglomerates, but loosen immediately Rank 3: Difficult to loosen Rank 2: No fluidity Rank 1: Clear caking

Image Density Solid black image density (maximum image density in a portion having no edge effect) Measured by Macbeth RD918 (Macbeth).

Evaluation of Wax Dispersibility in Toner The toner was observed at a low magnification (for example, 30 to 100 times) using an optical microscope equipped with a polarizing plate, and the toner was released from the toner per 500 toner particles. The number of bright spots indicating the presence of wax particles was measured. Rank 5: No bright spot through polarizing plate Rank 4: 1 to 10 bright spots Rank 3: 11 to 20 bright spots Rank 2: 21 to 30 bright spots Rank 1: 31 or more bright spots

Evaluation of Pulverizability A relative evaluation was made based on the weight of the kneaded material of the toner raw material of Comparative Example 1 which was pulverized to a weight average diameter of 7.5 μm per unit time. Rank 5: Pulverizable 1.2 times or more, and weight average diameter 10
20 to 30% of particles having a particle size of μm or more Rank 4: 1.2 times or more can be pulverized, and the weight average
Rank 3: Equal to Comparative Example 1 Rank 2: 10 to 20% less than Comparative Example 1 can be crushed Rank 3: Only 21% less than Comparative Example 1 can be crushed

[0166]

[Table 4]

[0167]

According to the toner of the present invention, the wax is uniformly dispersed in the binder resin, the pulverizability is good, the fixability,
It is excellent in offset resistance, blocking resistance, durability of many sheets, and the like.

[Brief description of the drawings]

FIG. 1 is an explanatory diagram illustrating an example of an image forming apparatus to which the toner of the present invention can be applied.

FIG. 2 is an enlarged view of a developing unit of the image forming apparatus shown in FIG.

 ──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Yuichi Mizoo 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc.

Claims (10)

[Claims] 1. A toner containing at least a binder resin, a colorant and a wax, wherein the binder resin comprises: Component (i): an aromatic vinyl monomer for forming a vinyl copolymer, and (meth) acrylic An acid ester monomer, a vinyl monomer having a carboxyl group Component (ii): An acid component and an alcohol component for forming a polyester resin Component (iii): A mixture containing at least a wax is used, and the component (i) in the mixture is used. ) Is polymerized to produce a vinyl copolymer (A), and then an acid component and an alcohol component of the component (ii) are polycondensed in the presence of the wax and the vinyl copolymer component to obtain a polyester. A resin component prepared by producing the component (B), and a reaction product of a vinyl copolymer and a polyester resin (C ). 2. The content of the vinyl copolymer (A), the polyester resin (B), and the reaction product (C) of the vinyl copolymer and the polyester resin contained in the binder resin is as follows:
A: B: C = (50-300) :( 100-50
0): (3 to 50). The toner according to claim 1, wherein 3. The ratio A: B: C is (80 to 250):
3. The toner according to claim 1, wherein (150 to 400): (5 to 40). 4. The ratio A: B: C is (120 to 20)
The toner according to claim 1, wherein 0): (200 to 350): (10 to 30). 5. A DSC curve of the wax measured by a differential scanning calorimeter, wherein the wax has a temperature of 60 to 150 when heated.
The toner according to any one of claims 1 to 4, wherein the toner has an endothermic peak temperature in a region of ° C. 6. A DSC curve of a wax contained in a toner, which is measured by a differential scanning calorimeter, has a plurality of endothermic peak temperatures in a temperature range of 70 to 140 ° C. when the temperature is raised, and the waxes are different from each other. 4. The method according to claim 1, wherein the wax is composed of two or more kinds of waxes having an endothermic peak temperature, and a relation of the following formula (1) is established with respect to a main endothermic peak temperature when the endothermic peak temperature is a melting point of the wax. 5. The toner according to any one of 5. (Equation 1) (Wherein, Lv, Hv each low melting wax, represents the amount of the binder resin having a high melting point waxes, L _M, H _M represents each low melting wax, the melting point of the high melting point waxes.) 7. The ratio (L _M × L _V + H _M × H _V ) / (Lv + H
7. The toner according to claim 1, wherein v) is 75 to 125. 8. The ratio (L _M × L _V + H _M × H _V ) / (Lv + H
7. The toner according to claim 1, wherein v) is 80 to 120. 9. The wax according to claim 1, wherein the wax is a hydrocarbon wax comprising a long-chain alkyl group.
The toner according to any one of the above. 10. The toner according to claim 1, wherein the wax is a wax having, as a main chain or a side chain, a hydrocarbon compound comprising a long-chain alkyl group having few branches.