JP2008102391A - toner - Google Patents

Abstract

An object of the present invention is to provide a toner that is excellent in low-temperature fixability and high-temperature offset resistance, has good storage stability, exhibits stable chargeability, and provides a high-quality image.
A toner having toner particles containing a binder resin and a colorant,
The binder resin contains 50 to 95% by mass of the polyester resin component with respect to the total amount of the binder resin, and contains a hybrid resin in which the polyester resin component and the vinyl resin component are chemically bonded. And
The toner contains 3 to 50% by mass of the THF-insoluble matter derived from the binder resin. The THF-insoluble matter contains the hybrid resin, hydrolyzes the tetrahydrofuran-insoluble matter, and then is filtered and filtered. The THF soluble component has a main peak in the molecular weight range of 10,000 to 1,000,000,
The polyester resin component is obtained by reacting (A) an acid component containing a polybasic acid compound having an unsaturated double bond and (B) an alcohol component containing 70 mol% or more of a polyhydric alcohol in the alcohol component. It is obtained by the above.
[Selection figure] None

Description

  The present invention relates to a toner used for electrophotography, an image forming method for developing an electrostatic image, and a toner used for a toner jet.

  Various methods and apparatuses have been developed for the process of fixing a toner image to a sheet such as paper in an image forming method for developing an electrophotographic or electrostatic image, such as a pressure heating method using a heat roller or a film. There has been proposed a heating and fixing method in which a heating member is brought into close contact with a heating body via a pressure member.

  In the heating method using a heating roller or a film, fixing is performed by allowing the toner image surface of the fixing sheet to pass through the surface of the heating roller or film formed with a material having releasability with respect to the toner. Is. In this method, since the surface of the heat roller or film and the toner image of the fixing sheet are in contact with each other, the thermal efficiency when fusing the toner image on the fixing sheet is very good, and the fixing can be performed quickly. And is very good in electrophotographic copying machines or printers.

  However, in the above method, since the heat roller or film surface and the toner image are in contact with each other in a molten state, a part of the toner image adheres to and is transferred to the fixing roller or film surface, which is transferred again to the next fixing sheet. An offset phenomenon may occur, and the fixing sheet may be stained. One of the important conditions of the heat fixing method is to prevent the toner from adhering to the heat fixing roller and the film surface. Therefore, it is necessary to further improve the toner fixing property and offset resistance. Therefore, further improvement of the toner binder resin is awaited.

  In response to such a further requirement, a polyester-based resin containing an aliphatic alcohol or an alicyclic polyhydric alcohol as a main component has been proposed as a binder resin (Patent Document 1). These polyester resins can lower the softening point and have a good anchoring effect and excellent fixability. However, compared with a polyester resin having an aromatic component as a main component of an alcohol component such as bisphenol A polyester having an equivalent melt viscosity, blade fusion occurs because the glass transition point of the resin is low, or toner There was a tendency that the storage stability and the blocking resistance were likely to deteriorate.

  On the other hand, with regard to the chargeability of the toner, increasing the proportion of the aliphatic alcohol of the polyester resin in the alcohol component is superior in charging stability in a low-temperature and low-humidity environment as compared with the polyester resin using a bisphenol diol. Such characteristics are considered. In recent years, devices such as laser printers are increasingly used in various environments, and toners that can cope with more severe environments have been demanded. A toner using a polyester resin mainly composed of an aliphatic polyhydric alcohol as a binder resin does not cause an excessive increase in the toner charge amount, that is, a so-called toner charge-up phenomenon even if there is an environmental change. It is thought that the chargeability of the is stable. However, the polyester resin having a high proportion of the aliphatic alcohol in the alcohol component as described above needs to be improved in performance such as durability under high temperature and high humidity and resistance to high temperature offset.

  Therefore, in order to solve these problems, a hybrid resin in which a vinyl polymer and a polyester resin, which are easily increased in molecular weight and excellent in preservability and high-temperature offset resistance, are chemically combined is a problem as described above. Has been proposed as a solution. For example, Patent Document 2 proposes a hybrid resin obtained by addition polymerization of a vinyl monomer to an unsaturated polyester resin composed of an aliphatic carboxylic acid and an aromatic carboxylic acid, and is excellent in both high-temperature offset resistance and low-temperature fixability. Toner has been reported. However, in developing systems that require recent miniaturization, the environment for toner storage stability has become severe, such as fewer heat exhaust mechanisms, while the performance required for low-temperature fixability and high-temperature offset resistance has become increasingly sophisticated. In order to satisfy various performances, there were points to be improved.

JP 05-134454 A JP 2005-099428 A

  An object of the present invention is to provide a toner that is excellent in low-temperature fixability and high-temperature offset resistance, has good storage stability, exhibits stable chargeability, and provides a high-quality image.

The present invention is a toner having toner particles containing at least a binder resin and a colorant,
The binder resin contains 50 to 95% by mass of the polyester resin component with respect to the total amount of the binder resin, and contains a hybrid resin in which the polyester resin component and the vinyl resin component are chemically bonded. And
The toner contains 3 to 50% by mass of a tetrahydrofuran (THF) insoluble component derived from a binder resin, the THF insoluble component contains a hybrid resin, the tetrahydrofuran insoluble component is hydrolyzed, and then filtered and filtered. The THF soluble component of the component to be separated has a main peak in the molecular weight range of 10,000 to 1,000,000 in the molecular weight distribution measured by GPC.
The polyester-based resin component comprises (A) an acid component containing at least one polybasic acid compound having an unsaturated double bond and (B) an aliphatic polyhydric alcohol or an alicyclic polyhydric alcohol as an alcohol component. The present invention relates to a toner characterized by being a polyester resin component obtained by reacting with an alcohol component contained in an amount of 70 mol% or more.

  According to the toner of the present invention, it is possible to provide a toner excellent in fixability, high temperature offset resistance, developability and blocking resistance. In addition, it is possible to provide a toner that exhibits stable charging stability regardless of the environment and can obtain a high-quality image without causing curling or wrinkling of the recording medium.

  Further, the toner of the present invention is excellent in fixability particularly in a low-temperature and low-humidity environment, and has such an effect that the toner hardly peels off from the recording medium.

  The binder resin used in the toner of the present invention needs to contain at least 50% by mass of a polyester resin component in order to ensure good fixability. When the content of the polyester resin unit is less than 50% by mass, it is difficult to obtain sufficient fixability. The content of the polyester-based resin unit in the present invention is a combination of a component present as a polyester resin and a component present as a polyester-based resin component in a hybrid resin or the like.

  One vinyl-based resin component is contained in the binder resin at 50% by mass or less, and preferably 10 to 50% by mass is preferable in that good offset resistance can be obtained. .

  In the toner of the present invention, the tetrahydrofuran-insoluble content (gel component) derived from the binder resin is 3 to 50% by mass (preferably 5 to 40% by mass, more preferably 5 to 30% by mass, particularly preferably 10 to 30%). (Mass%) is preferably contained, and it is further preferred that such a gel component contains a hybrid resin. When the tetrahydrofuran-insoluble content is less than 3% by mass, it is difficult to obtain good high-temperature offset resistance. When the tetrahydrofuran-insoluble content is more than 50% by mass, it is difficult to uniformly disperse a material such as a colorant in the toner, the chargeability of the toner is deteriorated, and fog and image density are liable to occur. In addition, by including a hybrid resin in the tetrahydrofuran-insoluble component (gel component), a colorant such as a wax component or a magnetic substance is likely to be present in the vicinity of the gel component in the toner, or enters the gel component. It becomes. By having an appropriate amount of gel, the soft resin component can be allowed to act only when the gel component retains them even when the polyester resin component has a low softening point and is fixed during heat and pressure. It is considered that problems such as high temperature offset can be suppressed. Further, such an action is an effect obtained by bulk polymerizing a vinyl monomer in the presence of a polyester resin component in the binder resin. In the bulk polymerization method, it is possible to increase the main peak molecular weight of the vinyl resin component contained in the gel component by controlling the molecular weight distribution of the vinyl resin component contained in the tetrahydrofuran insoluble matter (gel component). Since the molecular weight of the vinyl resin component in the gel component can be increased, the molecular weight between the crosslinking points of the network structure of the gel component can be increased, and a large amount of the polyester resin component can be taken into the gel component.

  The bulk polymerization method of the hybrid resin performed in the present invention is a method of polymerizing a vinyl monomer in the presence of an unsaturated polyester resin component without using a solvent or the like. After the vinyl resin and the polyester resin are produced, a hybrid resin may be produced by adding a vinyl monomer and / or a polyester monomer (alcohol, carboxylic acid) in the presence of these polymer components. It may be a method for producing a hybrid resin having a polyester resin component and a vinyl resin component by mixing an addition monomer and a polyester monomer (alcohol, carboxylic acid, etc.) and continuously performing an addition polymerization and a condensation polymerization reaction. . However, due to the ease of polymerization control such as polymerization temperature and stirring, after the production of the polyester resin, a vinyl resin component is produced in the presence and reacted to produce a hybrid resin having the polyester resin component and the vinyl resin component. Is preferred. Bulk polymerization is easier to obtain a pure polymer than solution polymerization or suspension polymerization, and is also suitable for continuous polymerization. Moreover, it is possible to increase the molecular weight of the hybrid resin component, which is suitable as a method for obtaining a resin having desired physical properties of the present invention. In solution polymerization, a step of removing the solvent and recovering the polymer is required. When the solvent remains, there is a concern about the influence on performance, such as the possibility that unreacted monomers may deteriorate the storage stability of the toner. In suspension polymerization, consideration must be given to the removal of impurities such as dispersants.

  In the present invention, the polyester resin component used for the polymerization of the hybrid resin includes (A) an acid component containing at least one polybasic acid compound having an unsaturated double bond, and (B) an aliphatic polyhydric alcohol. Or a polyester resin component obtained by reacting an alicyclic polyhydric alcohol with an alcohol component containing 70 mol% or more of the alcohol component.

  (A) As the polybasic acid compound having an unsaturated double bond, unsaturated dicarboxylic acids such as fumaric acid, maleic acid, citraconic acid and itaconic acid or anhydrides thereof, lower alkyl esters and the like are preferably used. These unsaturated dicarboxylic acids are preferably used in a proportion of 0.1 to 10 mol% (preferably 0.3 to 5 mol%, more preferably 0.5 to 3 mol%) with respect to the total acid component of the polyester monomer. . When an unsaturated dicarboxylic acid is added within this range, the unsaturated bond concentration in the low molecular weight polyester molecule becomes appropriate, and the polyester resin and the vinyl resin are hybridized with an appropriate distance between the crosslinking points. . Other acid components include phthalic anhydride, terephthalic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, adipic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, hexahydrophthalic anhydride, tetrahydrophthalic anhydride Dicarboxylic acids such as acid, cyclohexanedicarboxylic acid, succinic acid, malonic acid, glutaric acid, azelaic acid, naphthalenedicarboxylic acid, sebacic acid, or derivatives thereof, or their derivatives, such as trimellitic acid, trimellitic anhydride, pyro Trifunctional or higher polyvalent carboxylic acids such as merit acid and pyromellitic anhydride, derivatives thereof or esterified products thereof may be mentioned. In the present invention, one or more of these can be used, but it is preferable to use trivalent or higher polyvalent components in the smallest possible range. Since trivalent or higher polyvalent components form a crosslinked structure in the polyester resin component, it is considered that a gel component is generated in part. Since the gel component of the present invention is preferably composed mainly of a hybrid resin component capable of increasing the distance between cross-linking points, it is preferable to use a trivalent or higher polyvalent component as much as possible. If a large amount of gel component is produced by the polyester resin component, the low-temperature fixability is deteriorated. Moreover, it is preferable that aliphatic dicarboxylic acid or alicyclic dicarboxylic acid is an acid component which contains 50 mol% or more in all the acid components. Aromatic dicarboxylic acid compounds of terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, and / or acid anhydrides thereof, and / or lower alkyl esters thereof may be used, but less than 50 mol% in the total acid component. It is preferable to use it. When the ratio of the aromatic dicarboxylic acid compound is increased, the wax dispersion tends to be deteriorated, so that it is preferably used within the above range. As the acid component (B) used in the present invention, an aliphatic dicarboxylic acid, an alicyclic dicarboxylic acid, or a derivative thereof is preferably used. It seems that a toner having a flexible molecular chain that is well-suited to paper can be obtained by using a large amount of highly linear monomers. Specifically, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid and other aliphatic dicarboxylic acids, cyclohexanedicarboxylic acid and other alicyclic dicarboxylic acids, and An anhydride, an alkyl ester, etc. are mentioned.

  Examples of the component of (B) aliphatic alcohol or alicyclic polyhydric alcohol include 1,4-cyclohexanedimethanol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, and tripropylene glycol. , Butanediol, pentanediol, hexanediol, polyethylene glycol, polypropylene glycol, ethylene oxide-propylene oxide random copolymer diol, ethylene oxide-propylene oxide block copolymer diol, ethylene oxide-tetrahydrofuran copolymer diol, polycarbonate Diols such as procactonediol are preferably used. Also, sorbitol, 1,2,3,6-hexanetetraol, 1,4-sorbitan, pentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerin, 2-methylpropanetriol , Trifunctional or higher polyhydric alcohols such as 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trimethylolbenzene, and the like. In addition to the above, epoxy compounds such as neopentyl glycol diglycidyl ether, glycerin triglycidyl ether, trimethylol propane triglycidyl ether, trimethylol ethane triglycidyl ether, pentaerythritol tetraglycidyl ether may be used as the alcohol component. it can.

  The aliphatic polyhydric alcohol or alicyclic polyhydric alcohol needs to be contained in an amount of 70 mol% or more in the alcohol component. Preferably it is 100 mol%. Among these, the alicyclic polyhydric alcohol containing a cyclohexane ring structure is effective for increasing the glass transition point of the resin appropriately, and is preferably contained in an amount of 10 mol% or more. When aliphatic polyhydric alcohols or alicyclic polyhydric alcohols are used as the main component of the alcohol component, the reason for this is not clear, but a flexible linear molecular chain is added to the polyester structure. It is considered that the cohesive force can be reduced and the fixing strength is increased because of the excellent throwing effect on the paper at the time of fixing. When the aliphatic polyhydric alcohol or alicyclic polyhydric alcohol is 70 mol% or less in the alcohol component, the above effect cannot be obtained, and the toner fixed on the recording medium such as paper after fixing may be broken. When a strong force is applied, a problem such as peeling may occur depending on the amount of toner. Further, aromatic diols such as catechol, resorcinol and hydroquinone may be contained as long as they are 30 mol% or less, but they are used as little as possible in consideration of improving low-temperature fixability and suppressing charge-up. It is good. In the case where the toner charge-up phenomenon occurs and the amount of applied toner increases, a problem of paper curl such that the paper after fixing is rounded in addition to the deterioration of fog is likely to occur.

  Moreover, bisphenol A type epoxy resin, bisphenol bisphenol A, polyoxyethylene- (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene- (2.0) -2,2-bis (4-hydroxyphenyl) propane, 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 Although it is possible to use polyoxypropylene- (3.3) -2,2-bis (4-hydroxyphenyl) propane and derivatives thereof, the aromatic alcohol increases the softening point of the binder resin. Therefore, it should be used in as small a quantity as possible without departing from the spirit of the present invention. The amount of the aromatic diol used is desirably 30% by mole or less, more preferably 10% by mole or less in order to keep the raw material monomers inexpensive relative to the total alcohol components.

  Moreover, it is preferable to use two or more types of aliphatic polyhydric alcohols or alicyclic polyhydric alcohols. When there is only one kind of aliphatic polyhydric alcohol or alicyclic polyhydric alcohol in the monomer composition, it is often difficult to control the reaction during polyester synthesis. There exists a tendency for pulverizability to worsen and for manufacturing efficiency to fall. The alcohol component preferably contains 2 to 5 types, more preferably 3 to 4 types of alcohol components. By containing alcohol monomers having different molecular chain lengths, the polymer can maintain a flexible structure and is considered to be excellent in affinity with paper.

  The trivalent or higher polyvalent component is preferably 0.1 to 60 mol% (more preferably 0.1 to 20 mol%) of all components. If the polyester-based resin component contains a large amount of a crosslinked structure, the fixing strength may be low, such as low-temperature fixability and easy peeling from the recording medium. Is preferred.

  The polyester-based resin is usually obtained by a generally known condensation polymerization. The polymerization reaction of the polyester resin is carried out in the presence of a catalyst at a temperature of about 150 to 300 ° C., preferably about 170 to 280 ° C. The reaction can be performed under normal pressure, reduced pressure, or increased pressure, but after reaching a predetermined reaction rate (for example, about 30 to 90%), the reaction system is 200 mmHg or less, preferably 25 mmHg or less, more preferably It is desirable to carry out the reaction by reducing the pressure to 10 mmHg or less.

  Examples of the catalyst include catalysts usually used for polyesterification, for example, metals such as tin, titanium, antimony, manganese, nickel, zinc, lead, iron, magnesium, calcium, germanium; and these metal-containing compounds (dibutyltin oxide, orthodibutyl). Titanate, tetrabutyl titanate, tetraisopropyl titanate, zinc acetate, lead acetate, cobalt acetate, sodium acetate, antimony trioxide, etc.).

  In the present invention, a titanium compound is preferably used because of easy control of the polymerization reaction and high reactivity with the vinyl monomer, and tetraisopropyl titanate, dipotassium oxalate titanate, terephthalic acid titanate are particularly preferable. Potassium. Further, polymerization is performed in the presence of at least one selected from magnesium or calcium acetate, carbonate, sulfate, nitrate, alkoxide, halide such as chloride, acetylacetonate, and oxide as a reaction accelerator. It is more preferable. At this time, it is also preferable to add an antioxidant (particularly a phosphorus-based antioxidant) as an anti-coloring agent for the binder resin.

  The polyester of the present invention is stopped by stopping the reaction when the properties of the reactant (for example, acid value, softening point, etc.) reach a predetermined value, or when the stirring torque or stirring power of the reactor reaches a predetermined value. System resin can be obtained.

  The vinyl resin component of the hybrid resin of the present invention means a vinyl homopolymer or vinyl copolymer.

  Examples of the monomer for obtaining the vinyl resin include the following.

  For example, styrene; o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene, p-ethylstyrene, 2,4- Dimethyl styrene, pn-butyl styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl Styrene derivatives such as styrene; Ethylene unsaturated monoolefins such as ethylene, propylene, butylene and isobutylene; Unsaturated polyenes such as butadiene and isoprene; Vinyl halides such as vinyl chloride, vinyl bromide and vinyl fluoride; Acetic acid Vinyl esthetics such as vinyl, vinyl propionate and vinyl benzoate Class: methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, methacryl Α-methylene aliphatic monocarboxylic acid esters such as dimethylaminoethyl acid, diethylaminoethyl methacrylate; methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, n-octyl acrylate, Acrylic esters such as dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate; vinyl methyl ether, vinyl ethyl ether Ter, vinyl ethers such as vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, methyl isopropenyl ketone; N- such as N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole, N-vinyl pyrrolidone. Vinyl compounds; vinyl naphthalenes; and acrylic acid derivatives or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile, and acrylamide. These vinyl monomers are used alone or in admixture of two or more monomers.

  Among these, a combination of monomers that becomes a styrene copolymer or a styrene acrylic copolymer is preferable.

  Furthermore, as a monomer for adjusting the acid value of the binder resin, for example, acrylic acid such as acrylic acid, methacrylic acid, α-ethylacrylic acid, crotonic acid, and α- or β-alkyl derivatives thereof, fumaric acid, maleic acid, There are unsaturated dicarboxylic acids such as citraconic acid and their monoester derivatives or maleic anhydride, and such monomers are used alone or mixed to copolymerize with other monomers to produce the desired binder resin. Can do. Among these, it is particularly preferable to use a monoester derivative of an unsaturated dicarboxylic acid in order to control the acid value.

  More specifically, for example, monomethyl maleate, monoethyl maleate, monobutyl maleate, monooctyl maleate, monoallyl maleate, monophenyl maleate, monomethyl fumarate, monoethyl fumarate, monobutyl fumarate, monophenyl fumarate Monoesters of α, β-unsaturated dicarboxylic acids such as: monobutyl n-butenyl succinate, monomethyl n-octenyl succinate, monoethyl n-butenylmalonate, monomethyl n-dodecenyl glutarate, monobutyl n-butenyl adipate Monoesters of alkenyl dicarboxylic acids such as, and the like; monoesters of aromatic dicarboxylic acids such as phthalic acid monomethyl ester, phthalic acid monoethyl ester, phthalic acid monobutyl ester, and the like.

  At least one acid monomer selected from maleic acid, fumaric acid, phthalic acid, or a derivative thereof as described above is used in an amount of 0.1 to less than 1.5% by mass with respect to all monomers in the vinyl resin component. It is preferable. Such an acid anhydride monomer is considered to form an ester bond between the hydroxyl group in the polyester resin component and the vinyl resin component in the hybrid resin, and is considered to be able to control the distance between the crosslinking points of the gel network structure. . When the content is too large, the distance between the crosslinking points of the gel network is shortened, and the molecular chain is subjected to a shearing force during the melt kneading in the toner, which may have an influence on the high temperature offset resistance.

  Since the vinyl resin component contained in the gel component of the present invention preferably has a high linearity, it preferably contains no crosslinkable monomer, but in order to achieve the object of the present invention, the following examples are given. It is also possible to add such a crosslinkable monomer.

  As the crosslinkable monomer, a monomer having two or more polymerizable double bonds is mainly used. Aromatic divinyl compounds (eg, divinylbenzene, divinylnaphthalene, etc.); diacrylate compounds linked by alkyl chains (eg, ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate) , 1,5-pentanediol acrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, and acrylates of the above compounds replaced with methacrylate); di-linked by an alkyl chain containing an ether bond Acrylate compounds (eg, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 400 diacrylate, polyethylene glycol # 600 diacrylate, dipropylene glycol diacrylate, and acrylates of the above compounds replaced with methacrylate); diacrylate compounds linked by a chain containing an aromatic group and an ether bond (eg, polyoxyethylene (2 ) -2,2-bis (4-hydroxyphenyl) propane diacrylate, polyoxyethylene (4) -2,2-bis (4-hydroxyphenyl) propane diacrylate, and acrylates of the above compounds are replaced with methacrylate. Polyester type diacrylate compounds (for example, trade name MANDA (Nippon Kayaku)). As polyfunctional crosslinking agents, pentaerythritol acrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate, tetramethylol propane triacrylate, tetramethylol methane tetraacrylate, oligoester acrylate, and acrylates of the above compounds are replaced with methacrylate. Triallyl cyanurate, triallyl trimellitate and the like.

  These crosslinking agents are preferably used in an amount of 0.001 to 1 part by mass, more preferably 0.001 to 0.05 part by mass with respect to 100 parts by mass of the other vinyl monomer components.

  The vinyl resin is preferably produced by using a polyfunctional polymerization initiator as exemplified below alone or in combination of a polyfunctional polymerization initiator and a monofunctional polymerization initiator.

  Specific examples of the polyfunctional polymerization initiator having a polyfunctional structure include 1,1-di-t-butylperoxy-3,3,5-trimethylcyclohexane, 1,1-di-t-hexylperoxy- 3,3,5-trimethylcyclohexane, 1,1-di-t-amylperoxy-3,3,5-trimethylcyclohexane, 1,1-di-t-butylperoxy-2-methylcyclohexane, 1,3 -Bis- (t-butylperoxyisopropyl) benzene, 1,3-bis- (neodecanolperoxyisopropyl) benzene, 2,5-dimethyl-2,5-di- (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di- (t-butylperoxy) hexyne-3, 2,5-dimethyl-2,5-di- (2-ethylhexanolperoxy) hexane, 2, 5-dimethyl-2,5-di- (m-toluolperoxy) hexane, 2,5-dimethyl-2,5-di- (benzoylperoxy) hexane, tris- (t-butylperoxy) triazine, 1,1-di-t-butylperoxycyclohexane, 1,1-di-t-hexylperoxycyclohexane, 1,1-di-t-amylperoxycyclohexane, 1,1-di-t-butylperoxycyclohexane Cyclododecane, 2,2-di-t-butylperoxybutane, 4,4-di-t-butylperoxyvaleric acid-n-butyl ester, di-t-butylperoxyhexahydroterephthalate, di-t -Butylperoxyhexahydroisophthalate, di-t-butylperoxyazelate, tert-butylperoxytrimethyladipate , 2,2-bis- (4,4-di-t-butylperoxycyclohexyl) propane, 2,2-t-butylperoxyoctane and various polymer oxides, and two or more peroxide groups in one molecule A polyfunctional polymerization initiator having a functional group having a polymerization initiation function such as diallyl peroxydicarbonate, t-butylperoxymaleic acid, t-butylperoxyallylcarbonate, t-butylperoxyisopropyl fumarate, etc. The polyfunctional polymerization initiator which has both the functional group which has polymerization initiation functions, such as a peroxide group, and a polymerizable unsaturated group in 1 molecule of these is mentioned.

  Of these, more preferred are 1,3-bis- (t-butylperoxyisopropyl) benzene, 2,5-dimethyl-2,5-di- (t-butylperoxy) hexane, 2,5- Dimethyl-2,5-di- (t-butylperoxy) hexyne-3 and 2,2-bis- (4,4-di-t-butylperoxycyclohexyl) propane.

  These polyfunctional polymerization initiators are preferably used in an amount of 0.01 to 10 parts by mass with respect to 100 parts by mass of the monomer from the viewpoint of efficiency.

  Furthermore, when these polyfunctional polymerization initiators are used in combination with a monofunctional polymerization initiator, the temperature at which the half-life is 10 hours (10-hour half-life temperature) is lower than that of the polyfunctional polymerization initiator. It is preferable to use in combination with a monofunctional polymerization initiator.

  Specifically, benzoyl peroxide, n-butyl-4,4-di (t-butylperoxy) valerate, dicumyl peroxide, α, α′-bis (t-butylperoxydiisopropyl) benzene, t- Examples thereof include organic peroxides such as butyl peroxycumene and di-t-butyl peroxide, and azo and diazo compounds such as azobisisobutyronitrile and diazoaminoazobenzene.

  These monofunctional polymerization initiators may be added to the monomer at the same time as the polyfunctional polymerization initiator. However, in order to keep the efficiency of the polyfunctional polymerization initiator properly, vinyl in the polymerization step is used. It is preferable to add after the polymerization addition rate of the monomer reaches 50% or more.

  As the polymerization initiator, one having a 10-hour half-life temperature of 100 to 150 ° C. is used, and a temperature 30 ° C. lower than the 10-hour half-life temperature of the polymerization initiator is 10 ° C. higher than the 10-hour half-life temperature. Within the range, it is preferable to carry out the polymerization reaction until the polymerization conversion rate of the vinyl monomer reaches 60%, preferably 80%, and to increase the molecular weight of the vinyl resin component produced by bulk polymerization. Furthermore, after the polymerization conversion rate reaches 60% (preferably 80%), it is preferable to carry out the polymerization reaction at a temperature higher by 10 ° C. or more than the 10-hour half-life temperature to terminate the reaction. Furthermore, it is more preferable to carry out the vacuum distillation step in a temperature range that is 20 ° C. or more higher than the 10-hour half-life temperature after completion of the reaction. By performing the vacuum distillation step, an esterification reaction of the acid group in the vinyl resin component and the hydroxyl group of the polyester resin component occurs. It is considered that a cross-linked structure having a large molecular weight between cross-linking points is formed by causing such an esterification reaction after the completion of the polymerization reaction. The high molecular weight component formed by bonding large molecular chains together is a gel component having a regular and large network structure. The gel with a large mesh structure improves the dispersibility of the gel in the toner by incorporating a part of the low molecular weight component into the gel even when using a polyester resin component with high linearity by melt kneading at the time of toner formation. To do.

  The toner of the present invention hydrolyzes tetrahydrofuran-insoluble components derived from the resin component, and then filters the components that are filtered and filtered (hereinafter sometimes referred to as “residue”). However, the molecular weight distribution measured by GPC has a main peak in the molecular weight range of 10,000 to 1,000,000 (preferably 20,000 to 500,000, more preferably 50,000 to 200,000). Furthermore, when hydrolyzing tetrahydrofuran-insoluble matter derived from a resin component, the weight average molecular weight of which is preferably in the range of 10,000 to 5,000,000 (preferably 10,000 to 1,000,000, more preferably 30,000 to 500,000). The component to be decomposed is a polyester resin unit polymerized by an ester bond, and the vinyl resin component remains in a polymer state without being decomposed. Therefore, the residue after hydrolysis is mainly composed of a vinyl resin component, and the tetrahydrofuran soluble content of the residue is the tetrahydrofuran soluble content of the vinyl resin component.

  Further, when a binder resin is produced by simply mixing a polyester resin and a vinyl resin having a main peak at a molecular weight of 10,000 to 1,000,000, such a vinyl resin becomes soluble in tetrahydrofuran. Therefore, it is not included in the tetrahydrofuran insoluble matter in the first stage, and does not satisfy the constitution of the present invention. In addition, when a binder resin is produced by simply mixing a polyester resin and a vinyl resin containing a tetrahydrofuran-insoluble component, the vinyl-based resin remains in the tetrahydrofuran-insoluble component, but after the hydrolysis, the tetrahydrofuran-insoluble component is retained. Therefore, the configuration of the present invention is not satisfied.

  The resin component that satisfies the configuration of the present invention becomes, for example, a tetrahydrofuran-insoluble component by hybridizing a polyester-based resin and a vinyl-based resin having a main peak in the molecular weight range of 10,000 to 1,000,000. This is what you get.

  Therefore, the tetrahydrofuran-soluble component of the residue having a main peak at a molecular weight of 10,000 to 1,000,000 means that the vinyl resin component having a large molecular weight (that is, having a main peak in the region of a molecular weight of 10,000 to 1,000,000) This means that the polyester resin component is hybridized.

  That is, a binder resin in which tetrahydrofuran-insoluble matter derived from the resin component is hydrolyzed and the residual tetrahydrofuran-soluble matter has a main peak at a molecular weight of 10,000 to 1,000,000 in the molecular weight distribution measured by GPC is The gel structure has a large molecular weight and a large molecular weight between cross-linking points. Therefore, when it is used as a binder resin for toner, even when the toner is manufactured through melt kneading or the like, the gel is hardly cut and the gel is newly generated (for example, metal crosslinking). Even if it does not give, it is easy to obtain the intended effect of the present invention.

  A toner containing such a tetrahydrofuran-insoluble component makes the tetrahydrofuran-insoluble component, which is a gel component, easy to move even with a small amount of heat at the time of fixing, and is bound compared to a case where a gel component having a low molecular weight between crosslinks is contained. Since the resin is easily softened by heat, fixability is improved. Furthermore, such a gel component can maintain a high viscosity even at a high temperature, and can improve high-temperature offset resistance. Further, since high temperature offset resistance can be maintained even with a small amount of gel component, a large amount of low molecular weight components can be contained, and the fixability can be further improved. Even if it is a polyester-based resin component having an aliphatic polyhydric alcohol or an alicyclic polyhydric alcohol as a main component in the alcohol component as in the present invention, the blocking resistance and the high temperature offset resistance are likely to deteriorate. In addition, since a part of the polyester-based resin component can be taken into the gel network structure, it is considered that the fixing strength, the low-temperature fixability, and the high-temperature offset resistance can be satisfied while preventing the above-described problems.

  When the tetrahydrofuran-insoluble content is hydrolyzed and the main peak molecular weight of the tetrahydrofuran-soluble content of the residue is less than 10,000, the gel component tends to be hard and the fixability is lowered. In addition, since the molecular weight between cross-linking points is small, the gel component becomes inflexible, the gel component is easily cut by the shearing force at the time of kneading into toner, and high temperature offset resistance is lowered. Further, it may be difficult to incorporate a low molecular weight polyester resin component or wax into the gel component, and the storage stability may be lowered. When the main peak molecular weight is larger than 1,000,000, it is difficult to uniformly disperse the gel component in the toner. As a result, the uniform dispersibility of other components contained in the toner is inhibited, and the chargeability as a toner is reduced. descend. The polyester resin component contained in the tetrahydrofuran-insoluble matter is hydrolyzed, and the molecular weight distribution of the tetrahydrofuran-soluble matter in the residue can be measured by the following procedure.

  First, the tetrahydrofuran insoluble matter derived from the binder resin is taken out of the toner, and this tetrahydrofuran insoluble matter is heated in an alkaline aqueous solution to hydrolyze and remove the polyester resin unit. Since the vinyl resin component remains as a resin component without being hydrolyzed, the residue is extracted and the molecular weight distribution is measured by GPC. A specific GPC measurement method will be described later.

  The glass transition temperature (Tg) of the binder resin used in the present invention is preferably 50 to 75 ° C. When the glass transition temperature of the binder resin is less than 50 ° C., the storage stability of the toner may be insufficient, and when it is higher than 75 ° C., the toner fixability may be insufficient.

  The toner of the present invention may contain a wax as a release agent.

  The waxes used in the present invention include the following. For example, low molecular weight polyethylene, low molecular weight polypropylene, polyolefin copolymer, polyolefin wax, microcrystalline wax, paraffin wax, aliphatic hydrocarbon wax such as Fischer-Tropsch wax; oxide of aliphatic hydrocarbon wax such as oxidized polyethylene wax Or block copolymers thereof; plant waxes such as candelilla wax, carnauba wax, wax wax, jojoba wax; animal waxes such as beeswax, lanolin, spermaceti; mineral waxes such as ozokerite, ceresin, petrolatum; Waxes based on aliphatic esters such as montanic acid ester wax and caster wax; those obtained by partially or fully deoxidizing aliphatic esters such as deoxidized carnauba waxFurther, saturated linear fatty acids such as palmitic acid, stearic acid, montanic acid, or long-chain alkyl carboxylic acids having a long-chain alkyl group; unsaturated fatty acids such as brassic acid, eleostearic acid, and valinal acid; stearyl alcohol Saturated alcohol such as eicosyl alcohol, behenyl alcohol, cannavir alcohol, seryl alcohol, melyl alcohol, or alkyl alcohol having a long chain alkyl group; polyhydric alcohol such as sorbitol; linoleic acid amide, oleic acid amide, lauric acid Aliphatic amides such as acid amides; saturated aliphatic bisamides such as methylene bisstearic acid amide, ethylene biscapric acid amides, ethylene bislauric acid amides, hexamethylene bisstearic acid amides; Unsaturated fatty acid amides such as inamide, hexamethylenebisoleic acid amide, N, N′-dioleyl adipic acid amide, N, N′-dioleyl sebacic acid amide; m-xylene bisstearic acid amide, N, Aromatic bisamides such as N'-distearylisophthalamide; aliphatic metal salts such as calcium stearate, calcium laurate, zinc stearate and magnesium stearate (commonly referred to as metal soap); aliphatic hydrocarbons Wax grafted with a vinyl monomer such as styrene or acrylic acid; Partial esterified product of fatty acid and polyhydric alcohol such as behenic acid monoglyceride; Hydroxyl group obtained by hydrogenating vegetable oil Methyl ester compounds It is.

  In addition, these waxes have a sharp molecular weight distribution using a press sweating method, a solvent method, a recrystallization method, a vacuum distillation method, a supercritical gas extraction method or a melt liquid crystal deposition method, a low molecular weight solid fatty acid, a low molecular weight A solid alcohol, a low molecular weight solid compound, and other impurities are preferably used.

  Specific examples of the wax include Biscol (registered trademark) 330-P, 550-P, 660-P, TS-200 (Sanyo Chemical Industries), high wax 400P, 200P, 100P, 410P, 420P, 320P, 220P, 210P, 110P (Mitsui Chemicals), Sazol H1, H2, C80, C105, C77 (Schumann Sazol), HNP-1, HNP-3, HNP-9, HNP-10, HNP-11, HNP- 12 (Nippon Seiki Co., Ltd.), Unilin (registered trademark) 350, 425, 550, 700, Unicid (registered trademark), Unicid (registered trademark) 350, 425, 550, 700 (Toyo Petrolite Co., Ltd.), Kirou, Beeswax, rice wax, candelilla wax, carnauba wax (available at Celerica NODA Inc.) And the like. It is also a preferred form that these waxes are added as necessary when the resin is produced, and further the dispersibility is improved.

  The toner of the present invention may further contain a magnetic material and be used as a magnetic toner. In this case, the magnetic material can also serve as a colorant.

  In the present invention, the magnetic material contained in the magnetic toner includes iron oxides such as magnetite, maghemite and ferrite; metals such as iron, cobalt and nickel or these metals and aluminum, cobalt, copper, lead and magnesium. And alloys of metals such as tin, zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, vanadium, and mixtures thereof.

  These magnetic materials have a number average particle size of 2.0 μm or less, preferably 0.05 to 0.5 μm. The amount contained in the toner is preferably 20 to 200 parts by mass with respect to 100 parts by mass of the binder resin, and particularly preferably 40 to 150 parts by mass with respect to 100 parts by mass of the resin component.

  As the colorant used in the present invention, a black colorant that is black-toned using carbon black, grafted carbon or the following yellow / magenta / cyan colorant can be used.

  As the yellow colorant, compounds represented by condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, allylamide compounds, and the like are used.

  As the magenta colorant, condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, perylene compounds, and the like are used.

  As the cyan colorant, copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, basic dye lake compounds, and the like can be used. These colorants can be used alone or in combination and further in the form of a solid solution.

  The colorant of the present invention is selected from the viewpoints of hue angle, saturation, brightness, weather resistance, OHP transparency, and dispersibility in the toner. The colorant is added in an amount of 1 to 20 parts by mass with respect to 100 parts by mass of the binder resin.

  The toner of the present invention preferably contains a charge control agent. The following substances are used for controlling the toner to be negatively charged.

  For example, an organic metal compound and a chelate compound are effective, and there are a monoazo metal compound, an acetylacetone metal compound, an aromatic hydroxycarboxylic acid, and an aromatic dicarboxylic acid metal compound. In the present invention, a polymer having a sulfonic acid group, a sulfonic acid group or a sulfonic acid ester group, or a copolymer with an aromatic monomer such as styrene can be used as the resin charge control agent. The resin charge control agent is preferable from the viewpoints of dispersibility with the binder resin and miscibility with other raw materials such as wax. In particular, when a polyester resin component having high linearity is used as in the present invention, the reason is not clear, but the mixing with the resin charge control agent is good, and the chargeability of toner such as fog is related. The problem is suppressed. Other examples include aromatic hydroxycarboxylic acids, aromatic mono- and polycarboxylic acids and their metal salts, anhydrides, esters, and phenol derivatives such as bisphenol.

  The negatively chargeable charge control agent may be an azo metal compound represented by the following general formula (1) or an oxycarboxylic acid metal compound represented by the general formula (2).

〔式中、Ｍは配位中心金属を表し、Ｓｃ、Ｔｉ、Ｖ、Ｃｒ、Ｃｏ、Ｎｉ、Ｍｎ、Ｆｅ等があげられる。Ａｒはアリール基であり、フェニレン基、ナフチレン基などがあげられ、置換基を有してもよい。この場合の置換基としては、ニトロ基、ハロゲン原子、カルボキシル基、アニリド基および炭素数１〜１８のアルキル基、アルコキシ基などがある。Ｘ，Ｘ’、Ｙ，Ｙ’は−Ｏ−、−ＣＯ−、−ＮＨ−、−ＮＲ−（Ｒは炭素数１〜４のアルキル基）である。Ａ＋は水素イオン、ナトリウムイオン、カリウムイオン、アンモニウムイオン、脂肪族アンモニウムイオン、それらの混合物を表すが、Ａ＋は存在しない場合もある。〕

[Wherein M represents a coordination center metal, and examples thereof include Sc, Ti, V, Cr, Co, Ni, Mn, and Fe. Ar is an aryl group, such as a phenylene group or a naphthylene group, and may have a substituent. Examples of the substituent in this case include a nitro group, a halogen atom, a carboxyl group, an anilide group, an alkyl group having 1 to 18 carbon atoms, and an alkoxy group. X, X ′, Y, and Y ′ are —O—, —CO—, —NH—, and —NR— (R represents an alkyl group having 1 to 4 carbon atoms). A + represents a hydrogen ion, a sodium ion, a potassium ion, an ammonium ion, an aliphatic ammonium ion, or a mixture thereof, but A + may not exist. ]

  In particular, the central metal is preferably Fe or Cr, and the substituent is preferably a halogen atom, an alkyl group, or an anilide group.

  In particular, Fe, Cr, Si, Zn, Zr, and Al are preferable as the central metal, alkyl groups, anilide groups, aryl groups, and halogens are preferable as substituents, and counter ions are hydrogen ions, ammonium ions, aliphatic ammonium ions. Is preferred.

  Among them, the azo metal compound represented by the formula (1) is more preferable, and the azo iron compound represented by the following formula (3) is most preferable.

  Next, specific examples of the compound will be shown.

  Examples of the positive charge control agent include the following substances. Modified products with nigrosine and fatty acid metal salts, etc .; quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, tetrabutylammonium tetrafluoroborate, and analogs such as oniums such as phosphonium salts Salts and their lake pigments, triphenylmethane dyes and their lake pigments (the rake agents include phosphotungstic acid, phosphomolybdic acid, phosphotungsten molybdic acid, tannic acid, lauric acid, gallic acid, ferricyanide, Russian compounds, metal salts of higher fatty acids; diorganotin oxides such as dibutyltin oxide, dioctyltin oxide, dicyclohexyltin oxide; dibutyltin borate, dioctyltin borate, dicyclohexyl Diorgano tin borate such as Suzuboreto; guanidine compounds, imidazole compounds. These can be used alone or in combination of two or more. Among these, triphenylmethane compounds and quaternary ammonium salts whose counter ions are not halogen are preferably used.

  Further, the general formula (4)

〔式中、Ｒ₁はＨ又はＣＨ₃を示し、Ｒ₂及びＲ₃は置換または未置換のアルキル基（好ましくは、Ｃ₁〜Ｃ₄）を示す〕
で表されるモノマーの単重合体；前述したスチレン、アクリル酸エステル、メタクリル酸エステルの如き重合性モノマーとの共重合体を正荷電性制御剤として用いることができる。この場合これらの荷電制御剤は、結着樹脂（の全部または一部）としての作用をも有する。

[Wherein, R ₁ represents H or CH ₃ , and R ₂ and R ₃ represent a substituted or unsubstituted alkyl group (preferably C _{1 to} C ₄ )]
A copolymer with a polymerizable monomer such as styrene, acrylic acid ester or methacrylic acid ester described above can be used as a positive charge control agent. In this case, these charge control agents also have an action as a binder resin (all or a part thereof).

  In particular, a compound represented by the following general formula (5) is preferable in the configuration of the present invention.

〔式中、Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄、Ｒ₅及びＲ₆は、各々互いに同一でも異なっていてもよい水素原子、置換もしくは未置換のアルキル基または、置換もしくは未置換のアリール基を表し、Ｒ₇、Ｒ₈及びＲ₉は、各々互いに同一でも異なっていてもよい水素原子、ハロゲン原子、アルキル基、アルコキシ基を表し、Ａ^-は、硫酸イオン、硝酸イオン、ほう酸イオン、りん酸イオン、水酸イオン、有機硫酸イオン、有機スルホン酸イオン、有機りん酸イオン、カルボン酸イオン、有機ほう酸イオン又はテトラフルオロボレートから選択される陰イオンを示す。〕

[Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are the same or different from each other, a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl, R ₇ , R ₈ and R ₉ each represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group, which may be the same or different from each other, and A ⁻ represents a sulfate ion, a nitrate ion, a borate ion, An anion selected from phosphate ion, hydroxide ion, organic sulfate ion, organic sulfonate ion, organic phosphate ion, carboxylate ion, organic borate ion or tetrafluoroborate. ]

  Preferred for negative charging are Spiron Black TRH, T-77, T-95 (Hodogaya Chemical Co., Ltd.), BONTRON (registered trademark) S-34, S-44, S-54, E-84, E-88, E-89 (Orient Chemical Industry Co., Ltd.). Preferred for positive charging are TP-302, TP-415 (Hodogaya Chemical Co., Ltd.), BONTRON (registered trademark) N-01, N-04, N-07, P-51 (Orient Chemical) Kogyo Co., Ltd.) and Copy Blue PR (Clariant).

  As a method of incorporating a charge control agent into the toner, there are a method of adding it inside the toner and a method of adding it externally. The amount of use of these charge control agents is determined by the toner production method including the type of binder resin, the presence or absence of other additives, and the dispersion method, and is not uniquely limited. Preferably, it is used in the range of 0.1 to 10 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the binder resin.

  A fluidity improver may be added to the toner of the present invention. The fluidity improver can be added to the toner particles to increase the fluidity before and after the addition. Examples of such fluidity improvers include fluorine resin powders such as fine vinylidene fluoride powder and polytetrafluoroethylene fine powder; fine powder silica such as wet process silica and dry process silica, and fine powder titanium oxide. , Fine powder alumina, fine powder treated with silane compound, titanium coupling agent, silicone oil; oxides such as zinc oxide and tin oxide; strontium titanate, barium titanate, calcium titanate, zircon Examples thereof include double oxides such as strontium acid and calcium zirconate; calcium carbonate and carbonate compounds such as magnesium carbonate.

A preferred fluidity improver is a fine powder produced by vapor phase oxidation of a silicon halogen compound, and is referred to as so-called dry process silica or fumed silica. For example, a thermal decomposition oxidation reaction of silicon tetrachloride gas in an oxyhydrogen flame is used, and the basic reaction formula is as follows.
SiCl ₄ + 2H ₂ + O ₂ → SiO ₂ + 4HCl

  In this production process, it is also possible to obtain composite fine powders of silica and other metal oxides by using other metal halogen compounds such as aluminum chloride or titanium chloride together with silicon halogen compounds. To do. The particle size is preferably within the range of 0.001 to 2 μm as the average primary particle size, and particularly silica fine powder within the range of 0.002 to 0.2 μm is preferably used.

  Examples of commercially available silica fine powders produced by vapor phase oxidation of silicon halogen compounds include AEROSIL (Nippon Aerosil Co., Ltd.) 130, 200, 300, 380, TT600, MOX170, MOX80, COK84, Ca—O—SiL (CABOT CoL). Company) M-5, MS-7, MS-75, HS-5, EH-5, Wacker HDK N 20 (WACKER-CHEMIE GMBH) V15, N20E, T30, T40, DC Fine Silica (Dow Corning) Co.) and Fransol (Fransil) are commercially available, and these can also be used favorably in the present invention.

  Furthermore, as the fluidity improver used in the present invention, a treated silica fine powder obtained by hydrophobizing a silica fine powder produced by vapor phase oxidation of the silicon halogen compound is more preferable. Among the treated silica fine powders, those obtained by treating the silica fine powder so that the degree of hydrophobicity measured by a methanol titration test is in the range of 30 to 80 are particularly preferable.

  Examples of the hydrophobizing treatment include a chemical treatment with an organosilicon compound that reacts or physically adsorbs with silica fine powder. As a preferred method, silica fine powder produced by vapor phase oxidation of a silicon halogen compound is treated with an organosilicon compound.

  Examples of the organosilicon compound include hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane, benzyldimethylchlorosilane, bromomethridimethylchlorosilane, α- Chloroethyltrichlorosilane, β-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilyl mercaptan, trimethylsilyl mercaptan, triorganosilyl acrylate, vinyldimethylacetoxysilane, dimethylethoxysilane, dimethyldimethoxysilane, diphenyldiethoxysilane, hexamethyl Disiloxane, 1,3-divinyltetramethyldisiloxane, 1, Examples include 3-diphenyltetramethyldisiloxane, and dimethylpolysiloxane having 2 to 12 siloxane units per molecule and containing hydroxyl groups bonded to one Si at each terminal unit. Furthermore, silicone oils such as dimethyl silicone oil can be mentioned. These may be used alone or as a mixture of two or more.

The fluidity improver preferably has a specific surface area by nitrogen adsorption measured by the BET method of 30 m ² / g or more, preferably 50 m ² / g or more. The flowability improver is used in a total amount of 0.01 to 8 parts by weight, preferably 0.1 to 4 parts by weight, based on 100 parts by weight of the toner particles before external addition.

  In addition to the fluidity improver, the toner of the present invention can be used by adding other external additives (for example, a charge control agent) as required.

  The toner of the present invention can be used as a one-component developer or a two-component developer in combination with a carrier. As the carrier for use in the two-component developer, all conventionally known carriers can be used. Specifically, surface oxidized or unoxidized iron, nickel, cobalt, manganese, chromium, rare earth, etc. Particles with an average particle size of 20 to 300 μm, such as metals and their alloys or oxides, are preferably used.

  Further, those obtained by adhering or coating a resin such as a styrene resin, an acrylic resin, a silicone resin, a fluorine resin, or a polyester resin on the surface of the carrier particles are preferably used.

  To produce the toner of the present invention, a binder resin and a colorant, and if necessary, a magnetic material, wax, a charge control agent, other additives, and the like are sufficiently mixed by a mixer such as a Henschel mixer or a ball mill. Then, melt, knead, and knead using a heat kneader such as a roll, kneader, or extruder to disperse the wax or magnetic material in the binder resin, cool and solidify, and then pulverize and classify to obtain a toner be able to.

  The toner of the present invention can be manufactured using a known manufacturing apparatus. For example, the following manufacturing apparatus can be used.

  As a toner production apparatus, for example, as a mixer, a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.); a super mixer (manufactured by Kawata Corporation); a ribocorn (manufactured by Okawara Seisakusho Co., Ltd.); a nauter mixer, a turbulizer, and a cyclomix (Hosokawa Micron Corporation) A spiral pin mixer (manufactured by Taiheiyo Kiko Co., Ltd.); a radige mixer (manufactured by Matsubo).

  As a kneading machine, for example, KRC kneader (manufactured by Kurimoto Iron Works); Bus co-kneader (manufactured by Buss); TEM type extruder (manufactured by Toshiba Machine); TEX twin-screw kneader (manufactured by Nippon Steel Works) PCM kneading machine (Ikegai Iron Works); Three roll mill, mixing roll mill, kneader (Inoue Seisakusho); Needex (Mitsui Mining); MS pressure kneader, Nider Ruder (Moriyama Seisakusho) A Banbury mixer (manufactured by Kobe Steel).

  Examples of the pulverizer include counter jet mill, micron jet, inomizer (manufactured by Hosokawa Micron); IDS type mill, PJM jet pulverizer (manufactured by Nippon Pneumatic Industrial Co., Ltd.); cross jet mill (manufactured by Kurimoto Iron Works Co., Ltd.); (Nisso Engineering Co., Ltd.); SK Jet Oh Mill (Seishin Enterprise Co., Ltd.); Kryptron (Kawasaki Heavy Industries Co., Ltd.); Turbo Mill (Turbo Industry Co., Ltd.); Super Rotor (Nisshin Engineering Co., Ltd.) It is done.

  Classifiers include, for example, a class seal, a micron classifier, a speck classifier (manufactured by Seishin Enterprise); a turbo classifier (manufactured by Nisshin Engineering); a micron separator, a turboplex (ATP), a TSP separator (manufactured by Hosokawa Micron) ); Elbow Jet (manufactured by Nippon Steel & Mining Co., Ltd.), Dispersion Separator (manufactured by Nippon Pneumatic Industrial Co., Ltd.);

  Examples of sieving devices used to screen coarse particles include Ultrasonic (manufactured by Sakae Sangyo Co., Ltd.); Resonator Sheave, Gyroshifter (Tokuju Kosakusha Co., Ltd.); Vibrasonic System (Dalton Co., Ltd.); Examples include a turbo screener (manufactured by Turbo Industry Co., Ltd.), a micro shifter (manufactured by Kanno Sangyo Co., Ltd.), and a circular vibrating sieve.

  The measurement of various physical properties relating to the toner of the present invention will be described below. In the present invention, the molecular weight distribution of the THF soluble part and the content of the tetrahydrofuran insoluble part of the toner and the binder resin can be measured by the following methods.

(1) Measurement of molecular weight of THF-soluble matter The molecular weight of a chromatogram by gel permeation chromatography (GPC) is measured under the following conditions.

  The column is stabilized in a heat chamber at 40 ° C., and tetrahydrofuran (THF) as a solvent is allowed to flow through the column at this temperature at a flow rate of 1 ml / min. As a column, in order to accurately measure a molecular weight region of 103 to 2 × 10 6, it is preferable to combine a plurality of commercially available polystyrene gel columns. For example, shodex GPC KF-801, 802, 803, and 804 manufactured by Showa Denko KK , 805, 806, 807, 800P, Tosoh Corporation TSKgel G1000H (HXL), G2000H (HXL), G3000H (HXL), G4000H (HXL), G5000H (HXL), G6000H (HXL), G7000H The combination of (HXL) and TSK gauge column can be mentioned, and the combination of seven columns of shodex KF-801, 802, 803, 804, 805, 806, 807 manufactured by Showa Denko KK is particularly preferable.

  On the other hand, the polyester resin component contained in the toner, resin or toner insoluble in tetrahydrofuran is hydrolyzed, the vinyl resin component obtained as a residue is dispersed in tetrahydrofuran and dissolved, and then allowed to stand for 24 hours. The mixture is filtered through a treatment filter (pore size of about 0.5 μm, for example, Mysori Disc H-25-2 (manufactured by Tosoh Corporation), etc.), and the filtrate is used as a sample. About 100 μl of a THF solution of toner adjusted so that the resin concentration of the sample component is about 5 mg / ml is injected and measured. An RI (refractive index) detector is used as the detector.

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 number of counts. As a standard polystyrene sample for preparing a calibration curve, for example, Pressure Chemical Co. Manufactured by Toyo Soda Kogyo Co., Ltd. and having molecular weights of 6.0 × 10 ² , 2.1 × 10 ³ , 4 × 10 ³ , 1.75 × 10 ⁴ , 5.1 × 10 ⁴ , 1.1 × 10 ⁵ It is appropriate to use 3.9 × 10 ⁵ , 8.6 × 10 ⁵ , 2.0 × 10 ⁶ , 4.48 × 10 ⁶ , and use at least about 10 standard polystyrene samples.

(2) Amount of tetrahydrofuran-insoluble matter A binder resin or toner is weighed and placed in a cylindrical filter paper (for example, No. 86R size 28 mm × 10 mm, manufactured by Toyo Filter Paper Co., Ltd.) and applied to a Soxhlet extractor. Extraction is performed for 16 hours using 200 ml of tetrahydrofuran as a solvent. At this time, extraction is performed at a reflux rate such that the tetrahydrofuran extraction cycle is about once every 5 minutes. After the extraction is completed, the cylindrical filter paper is taken out and weighed to obtain an insoluble content of the binder resin or toner.

When the toner contains a tetrahydrofuran-insoluble component other than the resin component (eg, magnetic substance, pigment, wax, charge control agent), the weight of the toner placed in the cylindrical filter paper is W1 g, and the extracted THF-soluble resin component Is W2g, and the content of the tetrahydrofuran-insoluble component other than the resin component contained in the toner is W3g, the content of the tetrahydrofuran-insoluble component of the resin component in the toner can be obtained from the following formula.
Tetrahydrofuran insoluble (mass%) = [{W1- (W3 + W2)} / (W1-W3)]
× 100

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the examples.

[Binder resin production example]
(Polyester resin production example 1)
The polyester monomer is mixed in the following ratio.
・ Cyclohexanedicarboxylic acid: 0.650 mol
・ Hexane diacid: 0.200 mol
・ Adipic acid: 0.100 mol
・ Dodecenyl succinic anhydride: 0.050 mol
・ Fumaric acid: 0.008 mol
・ Cyclohexanedimethanol: 0.690 mol
Propylene glycol: 0.300 mol
・ Ethylene glycol: 0.090 mol

  To the above material, 0.1% by mass of tetrabutyl titanate as a catalyst and 0.01% by mass of magnesium acetate as a co-catalyst were added and subjected to condensation polymerization at 240 ° C. to obtain unsaturated polyester resin P-1 (Tg = 53 ° C., main Peak molecular weight = 5800) was obtained.

(Polyester resin production example 2)
The polyester monomer is mixed in the following ratio.
・ Cyclohexanedicarboxylic acid: 0.650 mol
・ Adipic acid: 0.100 mol
・ Terephthalic acid: 0.250 mol
・ Fumaric acid: 0.008 mol
・ Cyclohexanedimethanol: 0.690 mol
Propylene glycol: 0.300 mol
・ Ethylene glycol: 0.090 mol

  To the above material, 0.1% by mass of tetrabutyl titanate as a catalyst and 0.01% by mass of magnesium acetate as a co-catalyst were added and subjected to condensation polymerization at 240 ° C. to obtain unsaturated polyester resin P-2 (Tg = 52 ° C., main Peak molecular weight = 6000) was obtained.

(Polyester resin production example 3)
The polyester monomer is mixed in the following ratio.
・ Naphthalenedicarboxylic acid: 0.100 mol
・ Cyclohexanedicarboxylic acid: 0.350 mol
・ Terephthalic acid: 0.550 mol
・ Fumaric acid: 0.008 mol
・ Cyclohexanedimethanol: 0.690 mol
Propylene glycol: 0.300 mol
・ Ethylene glycol: 0.090 mol

  To the above material, 0.1% by mass of tetrabutyl titanate as a catalyst and 0.01% by mass of magnesium acetate as a cocatalyst were added and subjected to condensation polymerization at 240 ° C. to obtain unsaturated polyester resin P-3 (Tg = 55 ° C., main Peak molecular weight = 6300) was obtained.

(Polyester resin production example 4)
The polyester monomer is mixed in the following ratio.
・ Naphthalenedicarboxylic acid: 0.375 mol
・ Terephthalic acid: 0.625 mol
・ Fumaric acid: 0.008 mol
・ Cyclohexanedimethanol: 0.690 mol
Propylene glycol: 0.300 mol
・ Ethylene glycol: 0.090 mol

  To the above material, 0.1% by mass of tetrabutyl titanate as a catalyst and 0.01% by mass of magnesium acetate as a cocatalyst were added and subjected to condensation polymerization at 240 ° C. to obtain unsaturated polyester resin P-4 (Tg = 57 ° C., main Peak molecular weight = 6900) was obtained.

(Polyester resin production example 5)
An unsaturated polyester resin P-5 (Tg = 60 ° C., main peak molecular weight = 5800) was obtained in the same manner as in the polyester resin production example 1 except that the polyester monomer was mixed at the following ratio.
・ Naphthalenedicarboxylic acid: 0.305 mol
・ Terephthalic acid: 0.625 mol
・ Fumaric acid: 0.008 mol
・ Trimellitic acid: 0.070 mol
・ Cyclohexanedimethanol: 0.690 mol
Propylene glycol: 0.300 mol
・ Ethylene glycol: 0.090 mol

(Polyester resin production example 6)
An unsaturated polyester resin P-6 (Tg = 62 ° C., main peak molecular weight = 7000) was obtained in the same manner as in the polyester resin production example 1 except that the polyester monomer was mixed at the following ratio.
・ Terephthalic acid: 0.900 mol
・ Fumaric acid: 0.008 mol
・ Trimellitic acid: 0.070 mol
・ Cyclohexanedimethanol: 0.690 mol
Propylene glycol: 0.300 mol
・ Ethylene glycol: 0.090 mol

(Polyester resin production example 7)
An unsaturated polyester resin P-7 (Tg = 60 ° C., main peak molecular weight = 8500) was obtained in the same manner as in the polyester resin production example 1 except that the polyester monomer was mixed at the following ratio.
・ Terephthalic acid: 0.900 mol
・ Fumaric acid: 0.008 mol
・ Dodecenyl succinic anhydride: 0.100 mol
・ Neopentyl glycol: 0.300 mol
・ Propylene glycol: 0.250 mol
・ Ethylene glycol: 0.080 mol

(Polyester resin production example 8)
An unsaturated polyester resin P-8 (Tg = 63 ° C., main peak molecular weight = 9000) was obtained in the same manner as in the polyester resin production example 1 except that the polyester monomer was mixed at the following ratio.
・ Terephthalic acid: 1.000 mol
・ Fumaric acid: 0.008 mol
-Bisphenol A propylene oxide adduct (average number of moles added: 2.2 moles):
0.200 mol
・ Cyclohexanedimethanol: 0.400 mol
・ Neopentyl glycol: 0.400 mol

(Polyester resin production example 9)
Saturated polyester resin P-9 (Tg = 68 ° C., main peak molecular weight = 9300) was obtained in the same manner as in polyester resin production example 1 except that the polyester monomer was mixed in the following ratio and no cocatalyst was used.
・ Terephthalic acid: 0.500 mol
・ Isophthalic acid: 0.300 mol
・ Trimellitic acid: 0.200 mol
・ Propylene oxide adduct of bisphenol A (average addition mole number: 2.2 mol):
1.000 mol

(Polyester resin production example 10)
Saturated polyester resin P-10 (Tg = 53 ° C., main peak molecular weight = 9900) was obtained in the same manner as in polyester resin production example 1 except that the polyester monomer was mixed in the following ratio and no cocatalyst was used.
・ Terephthalic acid: 0.520 mol
・ Trimellitic acid: 0.200 mol
・ Dodecenyl succinic anhydride 0.250 mol
・ Neopentyl glycol: 0.500 mol
・ Ethylene glycol: 0.280 mol
・ 1,4-Butanediol: 0.220 mol

(Hybrid resin production example 1)
Unsaturated polyester resin P-1: 75 parts by mass and, as a vinyl monomer, styrene: 18 parts by mass, n-butyl acrylate: 6.5 parts by mass, mono n-butyl maleate: 0.5 parts by mass, paraffin Wax (Mn450, Mw520, main peak molecular weight 500, DSC peak temperature 75.0 ° C.): 2 parts by mass, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3 as initiator 10 hours half-life temperature 128 ° C.): 0.08 parts by mass were mixed. After this vinyl monomer / polyester resin mixture was polymerized at 120 ° C. over 20 hours until the polymerization conversion of the vinyl monomer reached 98%, the temperature was further raised to 150 ° C. and held for 5 hours to leave unreacted vinyl Monomers were polymerized to obtain a hybrid resin. This is designated as binder resin 1.

  The obtained binder resin 1 had a main peak molecular weight of 6000 in the molecular weight distribution measured by GPC with respect to the tetrahydrofuran-soluble content, and contained 50 mass% of the tetrahydrofuran-insoluble content. The tetrahydrofuran-insoluble matter was hydrolyzed, filtered, and analyzed for the tetrahydrofuran-soluble matter of the component to be filtered out. As a result, it contained a vinyl resin. Generally, when a hybrid resin is not contained, a tetrahydrofuran-soluble component does not occur even when hydrolyzed. From this, it was confirmed that the hybrid resin was contained in the tetrahydrofuran insoluble matter.

(Hybrid resin production example 2)
A hybrid resin was obtained in the same manner as in Hybrid resin production example 1 except that unsaturated polyester resin P-2 was used as the polyester resin component. This is designated as binder resin 2. The obtained binder resin 2 had a main peak molecular weight of 6200 in the molecular weight distribution measured by GPC with respect to the tetrahydrofuran-soluble component, and contained 45 mass% of the tetrahydrofuran-insoluble component.

(Hybrid resin production example 3)
A hybrid resin was obtained in the same manner as in Hybrid resin production example 1 except that unsaturated polyester resin P-3 was used as the polyester resin component. This is designated as binder resin 3. The obtained binder resin 3 had a main peak molecular weight of 6700 in the molecular weight distribution measured by GPC with respect to the tetrahydrofuran-soluble content, and contained 49 mass% of the tetrahydrofuran-insoluble content.

(Hybrid resin production example 4)
A hybrid resin was obtained in the same manner as in Hybrid resin production example 1 except that unsaturated polyester resin P-4 was used as the polyester resin component. This is designated as binder resin 4. The obtained binder resin 4 had a main peak molecular weight of 6900 in the molecular weight distribution measured by GPC with respect to the tetrahydrofuran-soluble content, and contained 40 mass% of the tetrahydrofuran-insoluble content.

(Hybrid resin production example 5)
A hybrid resin was obtained in the same manner as in Hybrid resin production example 1 except that unsaturated polyester resin P-5 was used as the polyester resin component. This is designated as binder resin 5. The obtained binder resin 5 had a main peak molecular weight of 6000 in the molecular weight distribution measured by GPC with respect to the tetrahydrofuran-soluble content, and contained 30% by mass of the tetrahydrofuran-insoluble content.

(Hybrid resin production example 6)
A hybrid resin was obtained in the same manner as in Hybrid resin production example 1 except that unsaturated polyester resin P-6 was used as the polyester resin component. This is designated as binder resin 6. The obtained binder resin 6 had a main peak molecular weight of 6000 in the molecular weight distribution measured by GPC with respect to the tetrahydrofuran-soluble content, and contained 55% by mass of the tetrahydrofuran-insoluble content.

(Hybrid resin production example 7)
A hybrid resin was obtained in the same manner as in Hybrid resin production example 1 except that unsaturated polyester resin P-7 was used as the polyester resin component. This is designated as binder resin 7. The obtained binder resin 7 had a main peak molecular weight of 6000 in the molecular weight distribution measured by GPC with respect to the tetrahydrofuran-soluble content, and contained 25 mass% of the tetrahydrofuran-insoluble content.

(Hybrid resin production example 8)
Polyester resin component, unsaturated polyester resin P-8: 75 parts by mass, and vinyl monomer, styrene: 18 parts by mass, n-butyl acrylate: 4.0 parts by mass, mono-n-butyl maleate: 3. A hybrid resin was obtained in the same manner as in Hybrid resin production example 1 except that the amount was 0 parts by mass. This is designated as binder resin 8. The obtained binder resin 8 had a main peak molecular weight of 6000 in the molecular weight distribution measured by GPC with respect to the tetrahydrofuran-soluble content, and contained 47 mass% of the tetrahydrofuran-insoluble content.

(Hybrid resin production example 9)
Unsaturated polyester resin P-8: 75 parts by mass was mixed with xylene 300 and dissolved. Next, as a vinyl monomer, styrene: 18 parts by mass, n-butyl acrylate: 6.5 parts by mass, mono n-butyl maleate: 0.5 parts by mass, paraffin wax (Mn450, Mw520, main peak molecular weight 500) DSC peak temperature 75.0 ° C.): 2 parts by mass, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3 (10-hour half-life temperature 128 ° C.) as an initiator: 0 0.08 part by mass was added, and the vinyl monomer / polyester resin mixture was heated to reflux temperature while introducing nitrogen, and polymerized, and then the solvent was distilled off under reduced pressure to obtain a hybrid resin. This is designated as binder resin 9. The obtained binder resin 9 had a main peak molecular weight of 8000 in the molecular weight distribution measured by GPC with respect to the tetrahydrofuran-soluble content, and contained 38 mass% of the tetrahydrofuran-insoluble content.

(Hybrid resin production example 10)
Polyester resin component, unsaturated polyester resin P-9: 75 parts by mass, and vinyl monomers, styrene: 18 parts by mass, n-butyl acrylate: 4.0 parts by mass, mono-n-butyl maleate: 3. A hybrid resin was obtained in the same manner as in Hybrid resin production example 1 except that the amount was 0 parts by mass. This is designated as binder resin 10. The obtained binder resin 10 had a main peak molecular weight of 8800 in the molecular weight distribution measured by GPC with respect to the tetrahydrofuran-soluble component, and contained 55 mass% of the tetrahydrofuran-insoluble component.

(Example 1)
Binder resin 1 102 parts by mass Magnetite (number average particle size 0.18 μm) 95 parts by mass Styrene: 2-acrylamido-2-methyl-1-propanesulfonic acid copolymer (copolymerization ratio = 95: 5) , Mw of polymer = 3,000, glass transition point (Tg) = 60 ° C.)
2 parts by mass After the above raw materials were premixed with a Henschel mixer, they were kneaded by a twin-screw kneading extruder (PCM-30: manufactured by Ikekai Iron Works Co., Ltd.) set at 130 ° C. and 200 rpm. The obtained kneaded product is cooled and coarsely pulverized with a cutter mill, and then the obtained coarsely pulverized product is finely pulverized using a turbo mill T-250 (manufactured by Turbo Kogyo Co., Ltd.), and a multi-division classifier utilizing the Coanda effect. Was used to obtain negatively chargeable toner particles having a weight average particle diameter (D4) of 7.0 μm. Toner 100 was obtained by adding 1.0 part by mass of negatively chargeable hydrophobic silica (BET specific surface area 120 m ^{2 /} g) treated with hexamethyldisilazane to 100 parts by mass of the toner particles with a Henschel mixer. Table 1 shows the physical properties of Toner 1.

  This toner was evaluated for the following items. The evaluation results are shown in Table 2.

[Fixing test]
Laser beam printer manufactured by Hewlett-Packard Company: LaserJet 4350 fixing device was taken out, and an external fixing device was used so that the fixing temperature of the fixing device could be arbitrarily set and the process speed was 360 mm / sec. This external fixing device is temperature-regulated every 5 ° C. in the range of 140 to 220 ° C., using plain paper (75 g / m ² ), passed through 5 solid white sheets, and then developed solid black (toner development amount on paper) Is set to 0.6 mg / cm ² ) The unfixed image is fixed, and the obtained image is rubbed 5 times with sylbon paper applied with a load of 4.9 kPa, and the density reduction rate of the image density before and after rubbing The fixing temperature was defined as the point at which 10% or less. The lower this temperature, the better the toner at low temperature fixability (Evaluation 1).

Regarding the high temperature offset resistance, the process speed was set to 100 mm / sec, the temperature was adjusted to 240 ° C., the unfixed image was fixed, and the stain due to the offset phenomenon on the image was visually confirmed. The paper used was an office planner 68 g / m ² (Evaluation 2).

Offset resistance rank A: Not generated at all B: Slight offset generated, but acceptable in practice C: Offset generation easily discernable by visual inspection D: Significant offset generation E: Paper wraps around a roller

[Developability]
Using a commercially available LBP printer (Laser Jet 4300, manufactured by HP) in a low-temperature, low-humidity environment (15 ° C / 10%), the A4 size image area ratio is 2%, and the A4 size is 75 g / m2. Image transfer tests were performed using transfer paper, and solid black image density and fogging were measured when 1,000 sheets and 20,000 sheets were passed. The image density was measured by measuring the reflection density using a SPI filter with a Macbeth densitometer (manufactured by Macbeth Co.), and the five-point average was calculated. The smaller the difference in density between the 1,000th sheet and the 20,000th sheet, the better the toner is in image density stability (Evaluation 3).

  The fog was calculated by comparing the whiteness of the transfer paper measured with a reflectometer (manufactured by Tokyo Denshoku Co., Ltd.) and the whiteness of the transfer paper after printing solid white. The smaller this value, the better the durability and stability of the toner (evaluation 4).

[curl]
In a low-temperature and low-humidity environment (15 ° C./10%), using a commercially available LBP printer (Laser Jet 4300, manufactured by HP), using thin paper (50 g / m ² ), solid black (toner development amount on paper is 0 (Set to 8 mg / cm ² ) and the curl occurrence rank of the paper after fixing was evaluated.

The degree of curling of the transfer material during single-sided fixing was evaluated by the following three stages by visual observation.
A: There is almost no curling, and no problem occurs in the transportability of plain paper.
B: Some curling occurs, but there is no practical problem with the transportability of plain paper.
C: Curling occurs, and a problem may occur when an image is formed on the back side of plain paper.

[Fixing strength]
The image used for the paper curl test was folded 180 ° at the center of the paper, and the fixing strength at the crease portion was visually confirmed.
A: The toner is not peeled off and the fixing strength is good. B: The toner is partly peeled off and a solid black portion is thinned, but there is no problem in practical use.
C: The toner is severely peeled off, which causes a practical problem.

[Crushability test]
The coarsely pulverized product was supplied at a rate of 30 kg / h to a pulverizer (Turbomill T-250; manufactured by Turbo Kogyo Co., Ltd.) and finely pulverized while adjusting the air temperature so that the exhaust temperature was 45 ° C. The peripheral speed of the pulverization rotor was adjusted so that the weight average particle diameter (D4) of the finely pulverized product was 5.5 μm, and the pulverization properties of the toners of the examples were judged based on the following criteria based on the peripheral speed of the pulverization rotor at that time. . As the weight average particle diameter (D4) of the finely pulverized product becomes 5.5 μm at a lower peripheral speed, the pulverizability is better.
A: Grinding rotor peripheral speed 91.7 m / s or less B: Grinding rotor peripheral speed 91.7 m / s or more and less than 104.8 m / s C: Grinding rotor peripheral speed 104.8 m / s or more and less than 117.9 m / s D: Grinding rotor circumferential speed 117.9 m / s or more and less than 131.0 m / s E: Grinding rotor circumferential speed 131.0 m / s or more

[Preservation test]
10 g of toner was weighed into a polypropylene cup and allowed to stand at 50 ° C. for 5 days to evaluate the toner blocking state (Evaluation 5).
A: When the cup is tilted, the toner flows smoothly.
B: When the cup is rotated, the toner surface starts to collapse little by little and becomes a smooth powder.
C: When force is applied from the outside while turning the cup, the toner surface collapses and gradually begins to flow.
D: A blocking sphere is generated. It collapses when you prick it with a pointed object.
E: Blocking spheres are generated. Even if it sticks, it is hard to collapse.

(Examples 2 to 8)
2 to 8 were obtained in the same manner as in Example 1 except that the binder resins 2 to 8 were used in place of the binder resin 1. Table 1 shows the physical properties of Toners 2-8. Further, an evaluation test was conducted in the same manner as in Example 1, and the results are shown in Table 2.

(Comparative Examples 1 and 2)
Binder resins 6 and 7 instead of binder resin 1 and azo type iron complex compound (1) instead of styrene: 2-acrylamido-2-methyl-1-propanesulfonic acid copolymer used in Example 1 Toners 9 and 10 were obtained in the same manner as in Example 1 except that (the counter ion was NH ₄ ⁺ ) was used. Table 1 shows the physical properties of Toner 9 and 10. Further, an evaluation test was conducted in the same manner as in Example 1, and the results are shown in Table 2.

(Comparative Example 3)
Toner 11 was obtained in the same manner as in Comparative Examples 1 and 2 except that saturated polyester resin P-6 was used as the binder resin. Table 1 shows the physical properties of Toner 11. Further, an evaluation test was conducted in the same manner as in Example 1, and the results are shown in Table 2.

Claims (4)

A toner having toner particles containing at least a binder resin and a colorant,
The binder resin contains 50 to 95% by mass of the polyester resin component with respect to the total amount of the binder resin, and contains a hybrid resin in which the polyester resin component and the vinyl resin component are chemically bonded. And
The toner contains 3 to 50% by mass of a tetrahydrofuran (THF) insoluble component derived from a binder resin, the THF insoluble component contains a hybrid resin, the tetrahydrofuran insoluble component is hydrolyzed, and then filtered and filtered. The THF soluble component of the component to be separated has a main peak in the molecular weight range of 10,000 to 1,000,000 in the molecular weight distribution measured by GPC.
The polyester-based resin component comprises (A) an acid component containing at least one polybasic acid compound having an unsaturated double bond and (B) an aliphatic polyhydric alcohol or an alicyclic polyhydric alcohol as an alcohol component. A toner comprising a polyester resin component obtained by reacting with an alcohol component contained in an amount of 70 mol% or more.   The toner according to claim 1, wherein the binder resin is obtained by bulk polymerization of a vinyl monomer in the presence of an unsaturated polyester resin.   The polyester resin component (A) is an acid component containing 50 mol% or more of an aliphatic dicarboxylic acid or an alicyclic dicarboxylic acid in the total acid components. Toner.   In the vinyl resin component, at least one acid monomer selected from maleic acid, fumaric acid, phthalic acid, or a derivative thereof is reacted at 0.1 to 2% by mass with respect to all monomers in the vinyl resin component. The toner according to claim 1, wherein the toner is a toner.