JP5106137B2 - Resin composition for toner and toner - Google Patents

Description

  The present invention relates to a toner for developing an electrostatic charge image in an image forming method such as electrophotography or electrostatic printing, or a toner for forming a toner image in a toner jet type image forming method. In particular, the present invention relates to a toner that is used in a fixing method in which a toner image formed of toner is fixed on a print sheet such as a transfer material by heating and pressing.

  2. Description of the Related Art Conventionally, in an image forming method using electrophotography, electrostatic printing, or the like, a copy is generally obtained by a process of fixing a toner image transferred onto a print sheet by heat or pressure. As a process for fixing a toner image, a heat-pressing heating method (hereinafter referred to as a heat roller fixing method) or a heat-fixing method (hereinafter referred to as a heat fixing method) in which a fixing sheet is fixed to a heating body through a fixing film. The film fixing method) has been developed.

  In the heat roll or film fixing method, fixing is performed by allowing a toner image on a fixing sheet to pass through the surface of a heat roller or a fixing film while being contacted under pressure by a pressure member that abuts. In this fixing method, the surface of the heat roller or fixing film and the toner image of the fixing sheet are in contact with each other under pressure, so that the thermal efficiency when fusing the toner image on the sheet is extremely high, and quick and good fixing is achieved. It can be carried out.

  In recent years, there have been various demands for electrophotographic apparatuses such as high image quality, small size and light weight, high speed and high productivity, energy saving, high reliability, low price, and maintenance-free. Particularly in the fixing process, the development of systems and materials that can achieve further higher image quality, higher speed, energy saving, higher reliability, etc. is an important technical issue. However, in order to solve these problems using a heat roller or a film fixing method, it is essential to significantly improve the fixing performance of toner, which is a material.

The fixing performance specifically required for the toner with respect to high image quality, high speed, energy saving, and high reliability is as follows.
-Performance that can be sufficiently fixed on a fixing sheet at a lower temperature (hereinafter referred to as low temperature fixing performance)
-Smoothness or glossiness of the fixed toner image area (hereinafter referred to as gloss performance)
・ Performance capable of stable fixing in a wider temperature range (hereinafter referred to as fixing temperature range)

  In general, these performances appear as phenomena during fixing. In the low temperature region, the toners are not sufficiently fused with each other and partially unfixed, or the adhesion to the fixing sheet is insufficient, causing a low temperature offset in which the toner adheres to and transfers on the heating roller or film surface. As the fixing temperature increases, the melting and fusing of the toner is promoted, and the toner image portion increases in smoothness and the gloss increases. On the other hand, in the high temperature region, excessively melted toner soaks into the fixing sheet and the gloss decreases, and toner on the heating roller or film surface is excessively melted, so that the toner is heated on the heating roller or film surface. Causes a high temperature offset to fuse and transition.

  These fixing phenomena are strongly related to the physical properties of the toner. The phenomenon in the low temperature region is related to the glass transition temperature Tg and softening temperature of the binder resin, the melting point of the wax, and the like, and often trades off with the storage stability and fluidity of the toner. In addition, the phenomenon in the high temperature region is related to the viscoelastic properties of the toner, and is often a trade-off with gloss performance. For this reason, many studies have been made on the types of wax and the molecular weight distribution control technology of the binder resin. However, it has not been possible to obtain a toner that can achieve a sufficient fixing temperature region while having excellent low-temperature fixing performance and gloss performance in response to further higher image quality, higher speed, energy saving, and higher reliability in recent years. It was.

  As a toner having improved fixing performance as described above, studies have been made to use a low Tg vinyl resin as a high molecular weight component of a binder resin (see Patent Documents 1 to 3). According to these toners, offset resistance, low-temperature fixability, and blocking resistance can be improved. However, the gloss performance is not described at all, and it is not satisfactory for high image quality.

  On the other hand, a toner that uses a hybrid cross-linked resin of vinyl resin and polyester resin (or polyamide resin) under specific conditions (see Patent Documents 4 to 9), or a toner that uses a cross-linked vinyl resin using a cross-linking agent (patent) Document 10) is known to exhibit good low-temperature fixability and offset resistance. However, in these toners, it is difficult to control the degree of crosslinking and the amount of gel component (or the amount of polymer component), and the trade-off between gloss performance and high-temperature offset resistance performance has not been sufficiently solved.

  Further, studies have been made to impart an anti-offset effect to the toner without disturbing the low-temperature fixability by incorporating the binder resin into the crosslinked network of the crosslinked polyester resin (or crosslinked polyurethane resin) (Patent Document 11). Thru 13). However, as a result of investigations by the present inventors, it is difficult to control the network structure and the amount of gel component (or the amount of polymer component) even in these toners. The trade-off has not been fully resolved.

JP-A-8-30020 Japanese Patent Laid-Open No. 7-230187 JP 7-295288 A Japanese Patent No. 2928370 Japanese Patent No. 3044595 Japanese Patent No. 3214779 Japanese Patent No. 3534578 JP-A-7-239579 JP-A-8-54753 JP 10-39543 A Japanese Patent No. 2982110 Japanese Patent No. 3643401 Japanese Patent No. 3635125

  The present invention has been made in view of the above problems. That is, an object of the present invention is to provide a toner having better fixability in order to satisfy the demands for higher image quality, higher speed, and energy saving, has low-temperature fixing performance, and is excellent. To provide a toner having high gloss performance and a wide fixing temperature range.

As a result of intensive studies, the inventors have improved the toner fixing performance by adopting a specific cross-linked structure in the hybrid resin composition, having low temperature fixing performance and high gloss performance, and having a fixing temperature range. A toner resin capable of realizing a wide range of toners has been found and the present invention has been completed. That is, the present invention relates to the following resin for toner and toner over.
(1) at least styrene monomer, an acrylate monomer (or methacrylate monomer), and the active hydrogen group-containing monomers over a copolymerizing styrenesulfonate A, an isocyanate group at both ends having a polyether structure or polyester structure A resin composition for a toner obtained by crosslinking reaction with the prepolymer B having a weight average molecular weight Mw calculated by GPC of the copolymer A of 3000 to 35000, and the prepolymer B for the toner The constituent ratio in the resin composition is 12 to 49% by mass, the main peak molecular weight Mp of the tetrahydrofuran-soluble component calculated by GPC of the resin composition for toner is 10,000 to 50,000, and the tetrahydrofuran-insoluble component is 3.0. A resin composition for toner, which is less than mass%.
(2) at least styrene monomer, an acrylate monomer (or methacrylate monomer), and those obtained by modifying a copolymer C obtained by copolymerizing an active hydrogen group-containing monomer over at diisocyanate compound, a polyether structure or a polyester structure A resin composition for a toner obtained by crosslinking reaction with a prepolymer D having a hydroxyl group at both ends, having a weight average molecular weight Mw calculated by GPC of the copolymer C of 3000 to 35000, The constituent ratio of the polymer B in the resin composition for toner is 12 to 49% by mass, the main peak molecular weight Mp of the tetrahydrofuran-soluble component calculated by GPC of the resin composition for toner is 10,000 to 50,000, Insoluble content is less than 3.0% by mass Resin composition for toner.
(3) A toner comprising 5.0 to 45.0 parts by mass of the resin composition for toner according to any one of (1) to (2) with respect to 100 parts by mass of the binder resin.

  By using the toner containing the resin for toner characterized by the present invention described below, high gloss performance and a wide fixing temperature range can be obtained while maintaining low temperature fixing performance, and high image quality, high speed, and energy saving. In contrast, a toner having stable fixing performance can be obtained.

  As a result of intensive studies on the toner fixing performance, the present inventors have found that an excellent toner can be provided by using the resin composition for toner described below.

  The most characteristic point of the resin composition for toner of the present invention is that the copolymer A or C obtained by copolymerizing a styrene monomer, an acrylate monomer (or a methacrylate monomer) and an active hydrogen group-containing monomer, It has the network structure bridge | crosslinked by the both terminal of the prepolymer B or D which has a polyether structure or a polyester structure. By providing this structure, when it is contained in the binder resin, rubber elasticity is imparted due to physical entanglement between the network structure and the main binder resin. The copolymer A or C and the prepolymer B or D are cross-linked by the reaction of an active hydrogen group and an isocyanate group, and form a urethane bond or a urea bond depending on the type of the active hydrogen group. By these bonds, a network structure can be formed while maintaining the flexible properties of the polymer having a polyether or polyol structure. This makes it possible to control the gloss performance and the fixing temperature region that cannot be obtained with conventional crosslinking components.

  In order to form a network structure that draws such characteristics, it is necessary that the constituent ratio of the prepolymer B or D to the resin composition for toner is 12 to 49% by mass. When the amount is less than this range, the portion having a network structure is too small to provide rubber elasticity, that is, the high temperature offset resistance cannot be improved. On the other hand, if the amount is too large, the interval between the cross-linking points is too narrow to physically entangle with the main binder resin, and the cross-linking reaction is difficult to control, and only one end reacts first to become a graft. Otherwise, if the number of cross-linking points increases too much, it will gel.

  In addition, the toner resin composition needs to have a main peak molecular weight Mp calculated from GPC of 10,000 to 50,000 and a tetrahydrofuran insoluble content of less than 3.0% by mass calculated by GPC. When the peak molecular weight Mp is lower than 10,000, it means that the crosslinking / network structure is too small or the network structure is too small, and rubber elasticity cannot be imparted. On the other hand, when Mp is larger than 50000, not only the elasticity is imparted, but also the melt viscosity is increased, and the gloss performance is lowered. Similarly, the binder resin itself entangled in the presence of the gel component also behaves in the same manner as the gel component, causing further reduction in gloss performance. For these reasons, it is necessary that the content of insoluble tetrahydrofuran is less than 3% by mass.

  Further, the toner resin composition needs to have a weight average molecular weight Mw calculated by GPC of the copolymer A or C of 3000 to 35000. When the weight average molecular weight Mw of the copolymer A or C is smaller than 3000, the physical entanglement with the main binder resin cannot be performed because the interval between the crosslinking points is too narrow. On the other hand, if the molecular weight is larger than 35,000, the molecular weight of the resin composition after the crosslinking reaction becomes too large, and the gloss performance is lowered.

  In the resin composition, the active hydrogen group of the copolymer A or C is not particularly limited, but is selected at least depending on the reactivity with the isocyanate group. Specific examples of preferred active hydrogen groups include hydroxyl groups, primary amines, secondary amines, and carboxyl groups. Among these, considering the reactivity with the isocyanate group and the stability of the bond formed, the hydroxyl group is most preferred.

  The copolymer A or C is obtained by copolymerizing the above-mentioned monomer having an active hydrogen group with a styrene monomer or acrylate monomer (or methacrylate monomer). In this copolymerization ratio, the content of active hydrogen groups can be controlled, whereby the number and interval of cross-linking points in the resin composition can be controlled. When the number of crosslinking points is smaller than the number of both ends of the prepolymer B or D, the graft type structure reacted only at one end increases, making it difficult to take a network structure, Polymer B or D remains. On the other hand, if the number of crosslinking points is too large, unreacted active hydrogen groups remain, which may adversely affect the compatibility with the main binder resin. Moreover, when the distance between the crosslinking points is too narrow, it means that the size of the network structure is reduced, which is not preferable. On the contrary, if the distance between the cross-linking points is too wide, it means that the size of the network structure becomes large, and rubber elasticity may not be imparted. For these reasons, the preferred active hydrogen group content of the copolymer A or C is in the range of 0.25 mmol / g to 1.20 mmol / g. The copolymerization ratio of the styrene monomer and the acrylate monomer (or methacrylate monomer) is not particularly limited, and is determined according to the desired glass transition temperature Tg and compatibility with the main binder resin. .

The active hydrogen group-containing monomer that can be used in the copolymer A or C is not particularly limited as long as it is a vinyl monomer having an active hydrogen group, and specifically includes the following.
Monomers having a hydroxyl group: 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxy-3-phenoxypropyl Acrylate, 2-acryloyloxyethyl-2-hydroxyethyl phthalate, hydroxycinnamic acid, cinnamyl alcohol, etc.-Amine-containing monomers: acrylamide, methacrylamide, allylamine, N-methylallylamine, N-ethylallylamine, N-propyl Allylamine, N-butylallylamine, aminostyrene, 2-aminoethyl methacrylate, 2-aminoethyl acrylate, etc. · Has a carboxyl group Monomers: Acrylic acid, methacrylic acid, maleic acid, vinyl acetate, etc.

  Specific examples of styrenic monomers that can be used in the copolymer A or C include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-phenylstyrene, and p-chloro. Styrene, 3,4-dichlorostyrene, p-ethylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, pn-hexylstyrene, pn-octylstyrene, Examples thereof include styrene such as pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, and derivatives thereof. In particular, styrene is most preferably used.

  Furthermore, the type of acrylate monomer (or methacrylate monomer) that can be used for the copolymer A or C is not particularly limited, and is determined according to the desired glass transition temperature Tg and compatibility with the main binder resin. It is. Specific examples include methyl methacrylate, ethyl methacrylate, propyl methacrylate, methacrylate-n-butyl, methacrylate-n-octyl, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate. , Dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, methyl acrylate, ethyl acrylate, -n-butyl acrylate, isobutyl acrylate, propyl acrylate, n-octyl acrylate, dodecyl acrylate, acrylic acid-2 -Ethylhexyl, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate and the like.

  In the case where the active hydrogen group-containing monomer is an acrylate monomer (or methacrylate monomer), another acrylate monomer (or methacrylate) can be used as long as the desired glass transition temperature Tg and compatibility with the main binder resin can be obtained. System monomer) may not be copolymerized.

  In the toner resin composition, the molecular weight of the prepolymer B or D having a polyether structure or a polyester structure is not particularly limited. However, as a preferable range, the number average molecular weight obtained from the number of both ends (NCO value or OH value) is 1000 to 12000. When the number average molecular weight is less than 1000, the size of the network structure may be too small, which may hinder entanglement with the main binder resin. On the other hand, if it is larger than 12,000, the size of the network structure is too large, and the rubber elasticity imparting ability may be reduced. For these reasons, a more preferable range is 1500 to 6000.

  The molecular weight of the toner resin composition needs to have a main peak molecular weight Mp of 10,000 to 50,000 as described above. At this time, the weight average molecular weight Mw is more preferably in the range of 10,000 to 100,000 for the same reason.

  The glass transition temperature Tg of the resin composition is not particularly limited, but it is not preferable from the viewpoint of low-temperature fixability when it is higher than the main binder resin. Further, as a result of intensive studies by the present inventors, it was found that the low-temperature fixing performance of the toner can be improved when the glass transition temperature Tg of the resin composition is less than 35 ° C. The reason for this is considered to be that the resin composition is already in a molten state at a temperature at which the main binder resin starts to melt, thereby promoting the macro flow of molecular chains that are physically entangled. ing.

  The method for forming the resin composition of the present invention described above is a crosslinking reaction utilizing an isocyanate group, but can be divided into two methods. One is a method of reacting the active hydrogen group of the copolymer A with the isocyanate groups present at both ends of the prepolymer B. The other is a method in which the active hydrogen group of the copolymer C is modified with a diisocyanate compound, and the provided isocyanate group reacts with the hydroxyl groups present at both ends of the prepolymer D.

  The crosslinking reaction by an isocyanate group and an active hydrogen group easily proceeds by heating in an organic solvent. The conditions for the crosslinking reaction are not particularly limited, but the degree of the crosslinking reaction can be controlled by the amount of solvent (solid-liquid ratio), reaction temperature, and reaction time, and must be selected according to the desired molecular weight and network structure. The organic solvent that can be used for the reaction is not particularly limited, but it must be capable of dissolving or uniformly dispersing the copolymer A or C and the prepolymer B or D. In addition, it is better to avoid solvents that react with isocyanates (for example, alcohol solvents). The reaction temperature is generally 50 ° C. to 150 ° C. Although it is necessary to adjust the reaction time according to the degree of crosslinking, the reaction must be stopped if necessary. As a method of stopping the reaction, there is a method of quenching, but a method of inactivating unreacted isocyanate groups is preferable. As a method for deactivating an isocyanate group, a compound having one active hydrogen group capable of reacting with an isocyanate group (for example, methanol) may be added.

  The prepolymer B or D has at least a polyether structure or a polyester structure. As the prepolymer D, polyether diols, polyester diols, polyether polyester diols, and the like used in the production of general polyurethane foams and urethane elastomers can be used. As the prepolymer B, one obtained by modifying such a diol compound with an organic diisocyanate compound can be used.

  Examples of the polyether diol include known polyether diols, that is, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 2,3- Butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10- Dihydroxy compounds such as decanediol, diethylene glycol, triethylene glycol, dipropylene glycol 1,4-cyclohexanedimethanol, bisphenol A, hydrogenated bisphenol A, ethylenediamine, hexamethylenediamine, isophoronediamine, 2,4-toluenediamine, 2, 6 torr Diamino compounds such as diamine, 2,2′-diaminodiphenylmethane, 2,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, 4,4′-diaminodicyclohexylmethane, 1,4-diaminocyclohexane, etc. Polyether diol and polyoxypolytetramethylene diol obtained by adding ethylene oxide and / or propylene oxide as an initiator.

  Examples of polyester diols include the known polyester diols: oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, fumaric acid, maleic acid, phthalic acid, isophthalic acid. Acids, terephthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, dicarboxylic acids such as 1,5-naphthalenedicarboxylic acid or their anhydrides, alkyl esters, ethylene glycol, 1,2-propanediol, 1,3- Propanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 1,6- Hexanediol, 1,8-octanediol, 1,9- Polyhydroxy compounds with dihydroxy compounds such as nandiol, 1,10-decanediol, diethylene glycol, triethylene glycol, dipropylene glycol, 1,4-cyclohexanedimethanol, and diols obtained by adding 2 moles of ethylene oxide and propylene oxide to bisphenol A Polyester diol obtained by dehydration and dealcoholization reaction in any combination of the above, or polyester diol obtained by ring-opening polymerization of cyclic ester (lactone) monomers such as ε-caprolactone, δ-valerolactone, alkyl-substituted δ-valerolactone It is.

  Examples of organic diisocyanate compounds that can be used in the preparation of Prepolymer B include 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, 2,2 ′. -Aromatic diisocyanates such as diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, 1,4-phenylene diisocyanate, 4,4'-diphenyl ether diisocyanate, 1,4-xylene diisocyanate, 1,3-xylene diisocyanate, 1,6-hexa Aliphatic diisocyanates such as methylene diisocyanate and lysine diisocyanate, isophorone diisocyanate, 1,4-cyclohexane diisocyanate, 4,4′-dicyclohexane Cycloaliphatic diisocyanates such as Le diisocyanate or dimeric modified products of these polyisocyanates, trimers modified products, biuret modified products, carbodiimide-modified products, and the like. These can be used alone or in a mixture of two or more.

  As the diisocyanate compound for modifying the active hydrogen group of the copolymer C, the above organic diisocyanate compound can be used.

  The copolymer A or C may be copolymerized with other monomers as constituents in consideration of solubility in a solvent, compatibility with the main binder resin, compatibility with waxes, and the like. . Monomers that may be copolymerized can be arbitrarily selected from known ones. Specific examples include ethylene unsaturated monoolefins such as ethylene, propylene, butylene, and isobutylene; unsaturated polyenes such as butadiene and isoprene, Vinyl esters such as vinyl acetate, vinyl propionate and vinyl benzoate; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and methyl isopropenyl ketone; vinyl Naphthalenes; acrylic acid derivatives such as acrylonitrile and methacrylonitrile.

  As a polymerization initiator that can be used when copolymerizing the monomer component of the copolymer A or C, various substances such as a peroxide polymerization initiator and an azo polymerization initiator can be used.

  Examples of the peroxide polymerization initiator that can be used include peroxyesters, peroxydicarbonates, dialkyl peroxides, peroxyketals, ketone peroxides, hydroperoxides, diacyl peroxides, and inorganic ones. Examples of the system include persulfate and hydrogen peroxide. Specifically, t-butyl peroxyacetate, t-butyl peroxylaurate, t-butyl peroxypivalate, t-butyl peroxy- 2-ethylhexanoate, t-butylperoxyisobutyrate, t-butylperoxyneodecanoate, t-hexylperoxyacetate, t-hexylperoxylaurate, t-hexylperoxypivalate, t -Hexylperoxy-2-ethylhexanoate, t- Xylperoxyisobutyrate, t-hexylperoxyneodecanoate, t-butylperoxybenzoate, α, α'-bis (neodecanoylperoxy) diisopropylbenzene, cumylperoxyneodecanoate, 1, 1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, 1-cyclohexyl-1-methylethylperoxyneodecanoate Ate, 2,5-dimethyl-2,5-bis (2-ethylhexanoylperoxy) hexane, 1-cyclohexyl-1-methylethylperoxy-2-ethylhexanoate, t-hexylperoxyisopropyl monocarbonate , T-butyl peroxyisopropyl monocarbonate, t-butyl -Oxy-2-ethylhexyl monocarbonate, t-hexylperoxybenzoate, 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane, t-butylperoxy-m-toluoylbenzoate, bis (t-butylperoxy) Oxy) isophthalate, t-butylperoxymaleic acid, t-butylperoxy-3,5,5-trimethylhexanoate, 2,5-dimethyl-2,5-bis (m-toluoylperoxy) Peroxyesters such as hexane; diacyl peroxides such as benzoyl peroxide, lauroyl peroxide, and isobutyryl peroxide; peroxydicarbons such as diisopropyl peroxydicarbonate and bis (4-t-butylcyclohexyl) peroxydicarbonate Ne 1,1-di-t-butylperoxycyclohexane, 1,1-di-t-hexylperoxycyclohexane, 1,1-di-t-butylperoxy-3,3,5-trimethylcyclohexane, , 2-di-t-butylperoxybutane and other peroxyketals; di-t-butyl peroxide, dicumyl peroxide and t-butylcumyl peroxide and other dialkyl peroxides; A monocarbonate etc. are mentioned. Examples of the azo polymerization initiator that can be used include 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexane- 1-carbonitrile), 2,2′-azobis-4-methoxy-2,4-dimethylvaleronitrile, azobisisobutyronitrile and the like.

  If necessary, two or more of these polymerization initiators can be used simultaneously.

  The amount of the polymerization initiator used at this time is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the monomer.

  As the polymerization method, any method such as solution polymerization, suspension polymerization, emulsion polymerization, dispersion polymerization, precipitation polymerization, bulk polymerization and the like can be used, and it is not particularly limited.

  Measurement of molecular weight by GPC may be performed as follows.

A solution obtained by adding the copolymer to THF (tetrahydrofuran) and allowing to stand at room temperature for 24 hours is filtered through a solvent-resistant membrane filter having a pore diameter of 0.2 μm to obtain a sample solution, which is measured under the following conditions. In addition, sample preparation adjusts the quantity of THF so that the density | concentration of a copolymer may be 0.4 to 0.6 mass%.
Apparatus: High-speed GPC HLC8120 GPC (manufactured by Tosoh Corporation)
Column: Shodex KF-801, 802, 803, 804,
Seven series of 805, 806, 807 (made by Showa Denko KK)
Eluent: Tetrahydrofuran Flow rate: 1.0 ml / min
Oven temperature: 40.0 ° C
Sample injection volume: 0.10 ml

  In calculating the molecular weight of the sample, standard polystyrene resin (TSO standard polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F- manufactured by Tosoh Corporation) was used. 10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500).

  In addition, the measurement of the glass transition point Tg by DSC can be measured, for example using a differential scanning calorimetry (DSC) apparatus (made by M-DSC TA Instruments). As a measuring method, about 6 mg of a sample is precisely weighed on an aluminum pan, an empty aluminum pan is used as a reference pan, and measurement is performed in a nitrogen atmosphere with a modulation amplitude of ± 0.6 ° C. and a frequency of 1 / min. The glass transition point is determined by the midpoint method from the reversing heat flow curve during temperature rise.

  The acid value / hydroxyl value in the present invention is determined by the following method.

  Basic operation is based on JIS K-0070.

<Measurement of acid value>
1) Weigh accurately 0.5 to 2.0 g of the pulverized sample. The mass at this time is defined as W (g).
2) Put the sample in a 300 ml beaker, and add 150 ml of a toluene / ethanol (4/1) mixture to dissolve.
3) Perform titration using a 0.1 mol / l ethanol solution of KOH using a potentiometric titrator (for example, a potentiometric titrator AT-400 (winworkstation) manufactured by Kyoto Electronics Co., Ltd.) and an ABP-410 electric burette. Automatic titration using can be used.)
4) The amount of KOH solution used at this time is S (ml). At the same time, a blank is measured, and the amount of KOH used at this time is defined as B (ml).
5) Calculate the acid value according to the following formula. f is a factor of KOH.
Acid value (mgKOH / g) = {(SB) × f × 5.61} / W

<Measurement of hydroxyl value>
・ Reagent Acetylation reagent (25 g of acetic anhydride is added to a 100-ml volumetric flask, pyridine is added to make a total volume of 100 ml, and shaken well.)
Phenolphthalein solution 0.5 kmol / m ³ potassium hydroxide ethanol solution / Measurement method (a) 0.5 g of a sample is precisely weighed into a 200 ml flat bottom flask, and 5 ml of acetylating reagent is added to the whole using a pipette.
(B) Place a small funnel at the mouth of the flask and immerse the bottom of about 1 cm in a glycerin bath at a temperature of 95-100 ° C. and heat. In order to prevent the temperature of the neck of the flask from rising due to the heat of the glycerin bath, a cardboard disc with a round hole in it is put on the base of the neck of the flask.
(C) After 1 hour, the flask is removed from the glycerin bath, allowed to cool, 1 ml of water is added from the funnel and shaken to decompose acetic anhydride.
(D) Further, in order to complete the decomposition, the flask is heated again in a glycerin bath for 10 minutes, and after cooling, the funnel and the wall of the flask are washed with 5 ml of ethanol.
(E) A few drops of phenolphthalein solution is added as an indicator, and titrated with 0.5 kmol / m ³ potassium hydroxide ethanol solution, and the end point is when the indicator is light red for about 30 seconds.
(F) In the blank test, (a) to (e) are performed without putting a sample.
(G) If the sample is difficult to dissolve, add a small amount of pyridine, or add xylene or toluene to dissolve.
(H) The hydroxyl value is calculated by the following formula.
Hydroxyl value (mgKOH / g) = [{(BC) × 28.05 × f} / S] + D
However,
B: Amount (ml) of 0.5 kmol / m3 potassium hydroxide ethanol solution used for the blank test
C: Amount of 0.5 kmol / m3 potassium hydroxide ethanol solution used for titration (ml)
f: Factor S of 0.5 kmol / m ³ potassium hydroxide ethanol solution: Mass of sample (g)
D: Acid value (mgKOH / g)
28.05: Formula weight of potassium hydroxide 56.11 × 1/2

  In the present invention, the unit of hydroxyl value is mmol / g, and the value of hydroxyl value obtained by the above formula may be divided by 56.11.

  In addition, the NCO value in this invention is calculated | required with the following method.

  Basic operations are based on JIS K-7301.

<Measurement of isocyanate content>
-Reagents Bromocresol green indicator: Add 0.1 ml of 0.1 mol / l sodium hydroxide solution to 0.10 g of bromocresol green, dissolve well and add water to make a total volume of 100 ml.
Dry toluene: Toluene is treated with metallic sodium or a suitable desiccant, then distilled and dissolved. Use one having a water content of 50 ppm or less.
Di-n-butylamine solution: 130 g of di-n-butylamine is dissolved in dry toluene to make 1000 ml.
Measurement method (a) A predetermined amount of sample (note) is accurately weighed to 0.1 mg into a conical flask (300 ml) with a stopper, and 25 ml of dry toluene is added and dissolved.
(Note: The sample collection amount is based on the mass (g) calculated by dividing 20 g by the value of the estimated isocyanate group content (%).)
(B) Next, accurately add 10 ml of di-n-butylamine solution with a whole pipette (10 ml), shake and homogenize, and let stand for about 15 minutes.
(C) Add 100 ml of 2-propanol and 5 to 10 bromocresol green indicators and titrate with 0.5 mol / l hydrochloric acid standard solution while shaking. In particular, near the end point, 0.5 mol / l hydrochloric acid standard solution is added drop by drop, and titration is continued while vigorously shaking the solution each time.
(D) The end point is the point where the liquid color disappears blue or bluish purple and yellow continues for at least 15 seconds.
(E) In the blank test, (a) to (d) are performed without inserting a sample.
(F) The isocyanate group content is calculated by the following formula.
Isocyanate content (%) = [{42.02 × 0.5 × (PQ) × f} / {S × 1000}] × 100
However,
P: Amount of 0.5 mol / l hydrochloric acid standard solution required for titration of sample (ml)
Q: Amount of 0.5 mol / l hydrochloric acid standard solution required for the blank test (ml)
f: Factor of 0.5 mol / l hydrochloric acid standard solution S: Sample collection amount (g)
42.02: Chemical amount of isocyanate group (g / mol)
0.5: molar concentration of hydrochloric acid standard solution (mol / l)

  In the present invention, the unit of NCO value is mmol / g, and the value of isocyanate content (%) obtained by the above formula may be divided by 4.202.

  The toner of the present invention exhibits the effect by containing the toner resin composition, and the content thereof is 5.0 to 45.0 parts by mass with respect to 100 parts by mass of the binder resin. When the amount is less than this range, the effect of the resin composition for toner is so small that almost no influence on the fixability is observed. On the other hand, when the amount is too large, the storage stability and fluidity of the toner are affected, or the gloss performance is lowered.

  In the toner of the present invention, it is preferable that the toner resin composition and the main binder resin are mixed well in order to bring out the effect of the toner resin composition more remarkably. This is because the network structure of the toner resin composition and the main binder resin are more easily entangled. As a method for this purpose, the toner resin composition and the main binder resin are dissolved in an organic medium and mixed. This is because entanglement at the molecular level is promoted by dissolution.

  The main binder resin used in the present invention is not particularly limited. For example, styrene resin, acrylic resin, styrene-acrylic resin, polyethylene resin, polyethylene-vinyl acetate resin, vinyl acetate resin, polybutadiene resin, phenol resin, polyurethane resin, polybutyral resin, polyester resin, and the like can be given. Among these, styrenic resins, acrylic resins, styrene-acrylic resins, polyester resins, and the like are desirable in terms of toner characteristics.

  The peak molecular weight calculated by GPC of the resin component soluble in THF of the toner of the present invention is preferably in the range of 3000 to 50000. If it is smaller than 3000, there may be a problem in chargeability. If it is larger than 50000, it is difficult to obtain high gloss performance. The method for measuring the peak molecular weight is the same as the method for measuring the molecular weight of the toner resin composition described above.

  The toner of the present invention preferably contains a wax. By including wax in the toner, a toner excellent in low-temperature fixing performance and low-temperature offset resistance can be easily obtained.

  When the wax is contained in the toner, the melted wax acts as a release agent between the transfer material and the fixing member due to the surface tension, and not only significantly improves the low temperature offset resistance. The low-temperature fixing performance can also be improved by accelerating the melting of the toner during fixing. In order to effectively exhibit such a wax action in the toner, the melting point of the wax is very important. That is, in the toner having excellent fixability, the melting peak temperature seen at the time of temperature rise is important in the toner DSC curve measured by the differential scanning calorimeter. When the temperature of the melting peak is too high, the releasing action at low temperatures is not exhibited, and not only low-temperature offset resistance is obtained, but also low-temperature fixing performance cannot be expected. On the other hand, if it is too low, the melt viscosity of the toner becomes too low, so that the releasing action on the high temperature side does not appear, sufficient low-temperature offset resistance cannot be obtained, and the winding around the fixing member It is also caused to phenomena such as sticking. For the above reasons, in the DSC curve of the preferred toner, the temperature range of the melting peak observed at the time of temperature rise is 45 ° C. to 130 ° C., more preferably 50 ° C. to 110 ° C., further preferably 50 ° C. to 90 ° C.

  The wax used in the toner of the present invention preferably has a content in the range of 0.5 to 30 parts by mass with respect to 100 parts by mass of the binder resin. If the content is less than 0.5 parts by mass, the effect of improving the offset resistance described above is not sufficient, and if it exceeds 30 parts by mass, the long-term storage stability is lowered and the dispersibility of other toner materials is poor. In addition, the amount of wax present in the vicinity of the toner surface increases, which may lead to a case where the charging characteristics which are the characteristics of the present invention are hindered, a decrease in toner fluidity, and a decrease in image characteristics.

  The wax that can be used in the toner of the present invention is not particularly limited as long as it is selected from those having a melting peak in the above-mentioned range. Specifically, paraffin wax, microcrystalline wax, Petroleum and other petroleum waxes and derivatives thereof, montan wax and derivatives thereof, hydrocarbon waxes and derivatives thereof by Fischer-Tropsch method, polyolefin waxes and derivatives thereof typified by polyethylene, natural waxes and derivatives thereof such as carnauba wax and candelilla wax Derivatives include oxides, block copolymers with vinyl monomers, and graft modified products. Furthermore, fatty acids such as higher aliphatic alcohols, stearic acid and palmitic acid, or compounds thereof, acid amide waxes, ester waxes, ketones, hydrogenated castor oil and derivatives thereof, plant waxes, animal waxes and the like can be mentioned.

  As described above, when a toner having excellent fixing properties is used, it is preferable to control the glass transition point of the toner. That is, when the glass transition point of the toner is too high, low temperature fixing performance cannot be obtained. However, although the melting temperature is lowered by lowering the glass transition point of the toner, if the temperature is too low, not only the storage stability of the toner may be deteriorated and a blocking phenomenon may be caused. As a result, the toner is fused in the developing unit, the toners are fused, and the fluidity is lowered. Further, as a result, the charging performance is lowered, and thus toner scattering and fogging are generated during development. For these reasons, the glass transition point obtained from the DSC curve of the toner is preferably in the range of 40 to 70 ° C, more preferably in the range of 45 to 65 ° C.

  In the present invention, the melting peak of the wax, the softening point temperature of the toner, and the glass transition point are measured in the same manner as the DSC measurement of the resin composition for toner. The melting peak of the wax is obtained from the heat flow curve obtained by the DSC measurement.

  In the toner of the present invention, a charge control agent may be contained in order to assist the frictional charging characteristics. Specifically, as the charge control agent that can be contained, as the negative control agent, salicylic acid, alkyl salicylic acid, dialkyl salicylic acid, naphthoic acid, dicarboxylic acid and the like and metal complex salts thereof; sulfonic acid (or salt), Resin compositions having a sulfonic acid ester or carboxylic acid (or salt) in the side chain; boron compounds; urea compounds; silicon compounds; Examples of the positive control agent include a quaternary ammonium salt, a resin composition having the quaternary ammonium salt in the side chain, a guanidine compound, and an imidazole compound.

  The toner of the present invention generally contains a colorant. As the black colorant, carbon black, a magnetic material, and a color toned to black using a yellow / magenta / cyan colorant shown below are used.

  As the yellow colorant, compounds represented by condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complex methine compounds, and allylamide compounds are used as pigments. Specifically, C.I. I. Pigment Yellow 3, 7, 10, 12, 13, 14, 15, 17, 23, 24, 60, 62, 74, 75, 83, 93, 94, 95, 99, 100, 101, 104, 108, 109, 110 111,117,123,128,129,138,139,147,148,150,166,168,169,177,179,180,181,183,185,191: 1,191,192,193,199 Are preferably used. Examples of the dye system include C.I. l. solvent Yellow 33, 56, 79, 82, 93, 112, 162, 163, C.I. I. disperse Yellow 42.64.2011.211.

  As the magenta colorant, condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds are used. Specifically, C.I. I. Pigment Red 2, 3, 5, 6, 7, 23, 48: 2, 48: 3, 48: 4, 57: 1, 81: 1, 122, 146, 166, 169, 177, 184, 185, 202, 206, 220, 221, 254, C.I. I. Pigment Bio Red 19 is particularly preferable.

  As the cyan colorant, copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, basic dye lake compounds, and the like can be used. Specifically, C.I. I. Pigment Blue 1, 7, 15, 15: 1, 15: 2, 15: 3, 15: 4, 60, 62, and 66 are particularly preferably 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 coloring agent is used in an amount of 1 to 20 parts by mass with respect to 100 parts by mass of the binder resin.

  Furthermore, the toner of the present invention contains a magnetic material and can 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 includes iron oxides such as magnetite, hematite, and ferrite; metals such as iron, cobalt, and nickel, or these metals and aluminum, cobalt, copper, lead, magnesium, tin, zinc, antimony, and beryllium. , Bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, alloys with metals such as vanadium, and mixtures thereof.

  The magnetic material used in the present invention is more preferably a surface-modified magnetic material, and when used in a polymerization method toner produced by a production method such as a polymer dissolution suspension method or suspension polymerization method, Those subjected to a hydrophobizing treatment with a surface modifier, which is a substance without inhibition, are preferred. Examples of such surface modifiers include silane coupling agents and titanium coupling agents.

  These magnetic materials preferably have an average particle size of 2 μm or less, preferably about 0.1 to 0.5 μm. The amount to be contained in the toner is 20 to 200 parts by mass, particularly preferably 40 to 150 parts by mass with respect to 100 parts by mass of the binder resin.

The magnetic characteristics when applied with 796 kA / m (10 k Oersted) are coercive force (Hc) of 1.59 to 23.9 kA / m (20 to 300 Oersted), saturation magnetization (σs) of 50 to 200 Am ² / kg, residual magnetization (σr) ) A magnetic body of ^{2 to} 20 Am ² / kg is preferable.

  In the toner of the present invention, the toner preferably has a weight average particle diameter of 3.0 to 9.0 μm in order to faithfully develop finer latent image dots in order to improve image quality. It is more preferable that the thickness is 6.5 μm. In a toner having a weight average particle diameter of less than 3.0 μm, the transfer residual toner on the photoconductor increases due to a decrease in transfer efficiency, and it becomes difficult to suppress photoconductor scraping and toner fusion. Furthermore, in addition to an increase in the surface area of the entire toner, the fluidity and agitation as a powder decrease, so there is a tendency for fogging and transferability to decrease. Etc. are likely to occur. Further, when the weight average particle diameter of the toner exceeds 9.0 μm, the characters and the line image are likely to be scattered, and it becomes difficult to obtain a high resolution, and the dot reproducibility tends to be lowered.

  The weight average particle diameter (D4) of the toner is determined based on the precise particle size distribution measuring apparatus “Coulter Counter Multisizer 3” (registered trademark, manufactured by Beckman Coulter, Inc.) having a 100 μm aperture tube. Using the attached dedicated software “Beckman Coulter Multisizer 3 Version 3.51” (manufactured by Beckman Coulter, Inc.) for setting and analyzing the measurement data, the measurement data is measured with 25,000 effective channels. Analysis was performed and calculated.

  As the electrolytic aqueous solution used for the measurement, special grade sodium chloride is dissolved in ion-exchanged water so as to have a concentration of about 1% by mass, for example, “ISOTON II” (manufactured by Beckman Coulter, Inc.) can be used.

  Prior to measurement and analysis, dedicated software was set up as follows.

  In the “Standard Measurement Method (SOM) Change Screen” of the dedicated software, set the total count in the control mode to 50000 particles, set the number of measurements once, and set the Kd value to “standard particles 10.0 μm” (Beckman Coulter, Inc.) Set the value obtained using The threshold and noise level are automatically set by pressing the threshold / noise level measurement button. Also, the current is set to 1600 μA, the gain is set to 2, the electrolyte is set to ISOTON II, and the aperture tube flash after measurement is checked.

  In the “pulse to particle size conversion setting screen” of the dedicated software, the bin interval is set to logarithmic particle size, the particle size bin is set to 256 particle size bin, and the particle size range is set to 2 μm to 60 μm.

The specific measurement method is as follows.
(1) About 200 ml of the electrolytic aqueous solution is put in a glass 250 ml round bottom beaker exclusively for Multisizer 3, set on a sample stand, and the stirrer rod is stirred counterclockwise at 24 rotations / second. Then, dirt and bubbles in the aperture tube are removed by the “aperture flush” function of the analysis software.
(2) About 30 ml of the electrolytic aqueous solution is put in a glass 100 ml flat bottom beaker, and "Contaminone N" (nonionic surfactant, anionic surfactant, organic builder pH 7 precision measurement is used as a dispersant therein. About 0.3 ml of a diluted solution obtained by diluting a 10% by weight aqueous solution of a neutral detergent for washing a vessel (made by Wako Pure Chemical Industries, Ltd.) 3 times with ion-exchanged water is added.
(3) Two oscillators with an oscillation frequency of 50 kHz are incorporated in a state where the phase is shifted by 180 degrees, and placed in a water tank of an ultrasonic dispersion device “Ultrasonic Disposition System Tetora 150” (manufactured by Nikka Ki Bios Co., Ltd.) having an electrical output of 120 W. A fixed amount of ion-exchanged water is added, and about 2 ml of the above-mentioned Contaminone N is added to this water tank.
(4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. And the height position of a beaker is adjusted so that the resonance state of the liquid level of the electrolyte solution in a beaker may become the maximum.
(5) In a state where the electrolytic aqueous solution in the beaker of (4) is irradiated with ultrasonic waves, about 10 mg of toner is added to the electrolytic aqueous solution little by little and dispersed. Then, the ultrasonic dispersion process is continued for another 60 seconds. In the ultrasonic dispersion, the temperature of the water tank is appropriately adjusted so as to be 10 ° C. or higher and 40 ° C. or lower.
(6) To the round bottom beaker of (1) installed in the sample stand, the electrolyte solution of (5) in which the toner is dispersed is dropped using a pipette, and the measurement concentration is adjusted to about 5%. . The measurement is performed until the number of measured particles reaches 50,000.
(7) The measurement data is analyzed with the dedicated software attached to the apparatus, and the weight average particle diameter (D4) is calculated. The “average diameter” on the analysis / volume statistics (arithmetic average) screen when the graph / volume% is set with the dedicated software is the weight average particle diameter (D4).

  The method for producing the toner of the present invention is not particularly limited, and a known production method is used. Specifically, a method for directly producing toner particles using the suspension polymerization method described in JP-B-36-10231, JP-A-59-53856, and JP-A-59-61842. A method of producing toner particles by an interfacial polymerization method such as a microcapsule production method; toner formation by a coacervation method; as disclosed in JP-A-62-106473 and JP-A-63-186253 A method of obtaining toner particles by an associative polymerization method in which at least one kind of fine particles are aggregated to obtain particles having a desired particle size; a method of producing toner particles by a dispersion polymerization method characterized by monodispersion; a water-insoluble organic solvent Polymer dissolution (melting) suspension method in which necessary resins are dissolved and then converted into toner in water; method of obtaining toner particles by emulsion dispersion method; and pressure kneader and extruder The toner component is kneaded and uniformly dispersed using a printer or a media disperser, and then cooled, and the kneaded product is collided with a target under a mechanical or jet stream to finely pulverize to a desired toner particle size. Further, a pulverization method in which the particle size distribution is sharpened through a classification step to produce toner particles; a method in which the toner obtained by the pulverization method is spheroidized by heating or the like in a solvent to obtain toner particles.

  However, the effect of the present invention appears more remarkably in the polymer dissolution suspension method or suspension polymerization method. This is because the toner particles can be granulated while the toner resin composition and the main binder resin are mixed in an organic medium (or monomer component). In particular, granulation is possible even if the Tg of the resin composition for toner is not more than room temperature or if the content is relatively large (the kneading and pulverizing method may impair the pulverizability). Each suspension method will be described below.

  In the method for producing toner particles by the polymer dissolution (melting) suspension method, first, the main binder resin, the toner resin composition and the colorant are dissolved and mixed or dispersed in an organic medium. Furthermore, together with wax and other additives as required, the mixture is uniformly dissolved and mixed or dispersed by a stirrer or the like to prepare a liquid mixture for toner formation. In that case, you may add what knead | mixed the colorant, wax, and another additive beforehand. The liquid mixture thus obtained is added to a dispersion medium (preferably an aqueous medium) containing a dispersion stabilizer, and a toner is prepared using a high-speed disperser such as a high-speed stirrer or an ultrasonic disperser as a stirrer. Disperse and suspend to the particle size (granulation step). Then, the organic solvent is removed by heating or reduced pressure, and further, a solvent such as methanol, ethanol, 1-propanol, t-butyl alcohol, and acetone is added to completely remove the organic solvent to obtain toner particles. it can.

  In the method for producing toner particles by the suspension polymerization method, first, a colorant is uniformly dissolved and mixed or dispersed in the polymerizable monomer constituting the main binder resin by a stirrer or the like. In particular, when the colorant is a pigment, it is preferably treated with a disperser to obtain a pigment dispersion paste. The monomer composition is uniformly dissolved and mixed or dispersed with a stirrer or the like together with the polymerizable monomer, the toner resin composition and the polymerization initiator, and other additives as required. Make it. The monomer composition thus obtained is added to a dispersion medium (preferably an aqueous medium) containing a dispersion stabilizer, and a high-speed disperser such as a high-speed stirrer or an ultrasonic disperser is used as a stirrer. Then, it is finely dispersed to the toner particle diameter (granulation step). Then, the monomer composition finely dispersed in the polymerization step is polymerized by light or heat to obtain toner particles.

  The organic medium that can be used in the polymer dissolution suspension method is determined according to the toner binder and is not particularly limited. Specifically, ether alcohols such as methyl cellosolve, cellosolve, isopropyl cellosolve, butyl cellosolve, diethylene glycol, monobutyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone; ethyl acetate, butyl acetate, ethyl propionate, cellosolve acetate, etc. Esters; hydrocarbons such as hexane, octane, petroleum ether, cyclohexane, benzene, toluene, xylene; halogenated hydrocarbons such as trichloroethylene, dichloromethane, chloroform; ethers such as ethyl ether, dimethyl glycol, trioxane tetrahydrofuran; Acetals such as methylal and diethyl acetal; containing sulfur and nitrogen such as nitropropene, nitrobenzene and dimethyl sulfoxide Selected from compounds, and the like.

  As a method of dispersing the pigment composition in the organic medium, a known method can be used. For example, if necessary, a resin and a pigment dispersant are dissolved in an organic medium, and the pigment powder is gradually added while being stirred, so that the solvent is sufficiently blended. Further, by applying mechanical shearing force with a dispersing machine such as a ball mill, paint shaker, dissolver, attritor, sand mill, or high speed mill, the pigment can be stably finely dispersed, that is, dispersed into uniform fine particles.

  The polymerizable monomer that can be suitably used in the suspension polymerization method is an addition polymerization monomer or a condensation polymerization monomer. Preferably, it is an addition polymerization monomer. Specifically, styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene, p-ethylstyrene, 2 , 4-dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, p- Styrene such as n-dodecylstyrene and derivatives thereof; Ethylene unsaturated monoolefins such as ethylene, propylene, butylene and isobutylene; Unsaturated polyenes such as butadiene and isoprene; Vinyl chloride, vinylidene chloride, vinyl bromide and vinyl iodide Vinyl halides such as vinyl acetate, vinyl propionate, benzoic acid Vinyl esters such as Nyl; methyl methacrylate, ethyl methacrylate, propyl methacrylate, -n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate Α-methylene fatty acid monocarboxylic acid esters such as diethylaminoethyl methacrylate; methyl acrylate, ethyl acrylate, acrylic acid-n-butyl, acrylic acid isobutyl, propyl acrylate, acrylic acid-n-octyl, dodecyl acrylate Acrylates such as 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, etc .; vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl Examples thereof include vinyl ethers such as tilether; N-vinyl compounds such as vinyl methyl ketone, vinyl hexyl ketone, and methyl isopropenyl ketone; vinyl naphthalenes; acrylic acid derivatives such as acrylonitrile, methacrylonitrile, and acrylamide.

  The dispersion medium that can be used in the above production method is determined based on the solubility of the binder resin, organic medium, monomer and copolymer in the dispersion medium, but is preferably an aqueous medium. Examples of the aqueous dispersion medium include water; methyl alcohol, ethyl alcohol, modified ethyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, tert-butyl alcohol, sec-butyl alcohol, tert-amyl alcohol, and 3-pentanol. , Alcohols such as octyl alcohol, benzyl alcohol, cyclohexanol; ether alcohols such as methyl cellosolve, cellosolve, isopropyl cellosolve, butyl cellosolve, diethylene glycol monobutyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone; ethyl acetate, butyl acetate , Esters such as ethyl propionate and cellosolve acetate; ethers such as ethyl ether and ethylene glycol Acetals such as methylal and diethyl acetal; acids such as formic acid, acetic acid and propionic acid; sulfur, nitrogen-containing organic compounds such as nitropropene, nitrobenzene, dimethylamine, monoethanolamine, pyridine, dimethylsulfoxide and dimethylformamide However, water or alcohols is particularly preferable. Two or more of these solvents can be mixed and used. The concentration of the liquid mixture or the monomer composition with respect to the dispersion medium is preferably 1 to 80% by mass, more preferably 10 to 65% by mass with respect to the dispersion medium.

  As a dispersion stabilizer that can be used when an aqueous dispersion medium is used, known ones can be used. Specific examples include inorganic compounds such as calcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate. , Bentonite, silica, alumina and the like. As the organic compound, polyvinyl alcohol, gelatin, methyl cellulose, methyl hydroxypropyl cellulose, ethyl cellulose, sodium salt of carboxymethyl cellulose, polyacrylic acid and its salt, starch and the like can be dispersed in an aqueous phase. The concentration of the dispersion stabilizer is preferably 0.2 to 20 parts by mass with respect to 100 parts by mass of the liquid mixture or the monomer composition.

  Examples of the polymerization initiator used in the toner of the present invention using the suspension polymerization method include known polymerization initiators. Specifically, those enumerated in the method for producing the copolymer are used.

  Further, examples of the chain transfer agent used when the toner is produced by the suspension polymerization method include known chain transfer agents.

  The toner of the present invention preferably has an inorganic fine powder on the surface of toner particles.

  The inorganic fine powder is added to and mixed with toner particles to improve the fluidity of the toner and make the charge uniform, and the added inorganic fine powder exists in a state of being uniformly attached to the surface of the toner particles.

  The inorganic fine powder in the present invention preferably has a number average primary particle size of 4 to 80 nm. When the number average primary particle size of the inorganic fine powder is larger than 80 nm, or when the inorganic fine powder of 80 nm or less is not added, good toner fluidity cannot be obtained, and charging is imparted to the toner particles. Are likely to be non-uniform, and problems such as increased fog, decreased image density, and toner scattering may be unavoidable. When the number average primary particle size of the inorganic fine powder is smaller than 4 nm, the agglomeration of the inorganic fine powder is strengthened, and the aggregate is not a primary particle but an aggregate with a wide particle size distribution having a strong agglomeration property that is difficult to break even by crushing treatment. And image defects due to development of the aggregate, damage to the image carrier or development carrier, and the like. In order to make the charge distribution of the toner particles more uniform, the number average primary particle size of the inorganic fine powder is more preferably 6 to 35 nm.

  In the present invention, the number average primary particle size of the inorganic fine powder is measured by a photograph of the toner magnified by a scanning electron microscope, and further by an elemental analysis means such as XMA attached to the scanning electron microscope. Measure 100 or more primary particles of inorganic fine powder adhering to or releasing from the toner particle surface while comparing the photograph of the toner mapped with the elements contained in the body, and obtain the number average particle size. Can be obtained.

As the inorganic fine powder used in the present invention, an inorganic fine powder selected from silica, alumina, titania or a double oxide thereof can be used. Examples of the double oxide include aluminum silicate fine powder and strontium titanate fine powder. Further, as the silicic acid fine powder, both a so-called dry method produced by vapor phase oxidation of silicon halide or dry silica called fumed silica, and so-called wet silica produced from water glass or the like can be used. is there. Dry silica is preferred because it has few silanol groups on the surface and inside of the silicate fine powder and little production residue such as Na ₂ O, SO ₃ ^2- . In dry silica, 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 and titanium chloride together with silicon halogen compounds in the production process. They are also included.

  The addition amount of the inorganic fine powder having a number average primary particle size of 4 to 80 nm is preferably 0.1 to 5.0 parts by mass with respect to 100 parts by mass of the toner particles. If the addition amount is less than 0.1 parts by mass, the effect is not sufficient, and if it is 5.0 parts by mass or more, the fixability may be deteriorated.

  The inorganic fine powder in the present invention is added to improve the fluidity of the toner and to make the charge of the toner particles uniform. The adjustment of the charge amount of the toner and the environmental stability by a treatment such as a hydrophobic treatment of the inorganic fine powder. It is also a preferable form to provide a function such as improvement.

  When the inorganic fine powder added to the toner absorbs moisture, the charge amount of the toner particles is remarkably reduced, and the toner is easily scattered.

  Hydrophobic treatments for hydrophobizing inorganic fine powder include silicone varnish, various modified silicone varnishes, silicone oil, various modified silicone oils, silane compounds, silane coupling agents, other organosilicon compounds, and organic titanium compounds. You may process an agent individually or in combination.

  Among them, those treated with the above silicone oil are preferable, and more preferably, when the inorganic fine powder is treated with the silicone oil at the same time or after the hydrophobic treatment, the magnetic toner particles are used even in a high humidity environment. It is sufficient to keep the charge amount of the toner particles high and prevent toner scattering.

The toner of the present invention has a primary particle size of more than 30 nm (preferably a specific surface area of less than 50 m ² / g), more preferably a primary particle size of 50 nm or more (preferably a specific surface area) for the purpose of improving cleaning properties. It is also a preferable form to add inorganic particles or organic particles close to a sphere having a particle size of less than 30 m ² / g). Specifically, for example, spherical silica particles, spherical polymethylsilsesquioxane particles, spherical resin particles and the like are preferably used.

  Further, the toner used in the present invention may further contain other additives, for example, a lubricant powder such as Teflon (registered trademark) powder, zinc stearate powder, polyvinylidene fluoride powder, or the like within a range that does not substantially adversely affect the toner. Development of abrasives such as cerium oxide powder, silicon carbide powder, strontium titanate powder, fluidity-imparting agents such as titanium oxide powder and aluminum oxide powder, anti-caking agent, and organic and / or inorganic fine particles of opposite polarity A small amount can be used as a property improver. These additives can also be used after hydrophobizing the surface.

  In addition, the toner of the present invention can be mixed with a carrier and used as a two-component developer, or can be used as a one-component developer composed only of toner.

  When the toner of the present invention is used for a two-component developer, the toner is used by mixing with a magnetic carrier. Examples of magnetic carriers include surface oxidized or unoxidized iron, lithium, calcium, magnesium, nickel, copper, zinc, cobalt, manganese, chromium, rare earth metal particles, alloy particles thereof, oxide particles, ferrite and the like. Although fine particles can be used, the charging characteristics of the present invention can be more preferably achieved by using a magnetic fine particle dispersed resin carrier in which magnetic fine particles are dispersed in a resin.

  The coated carrier obtained by coating the surface of the magnetic carrier particles with a resin is particularly preferable in a developing method in which an AC bias is applied to the developing sleeve. Coating methods include a method in which a coating solution prepared by dissolving or suspending a coating material such as a resin in a solvent is adhered to the surface of the magnetic carrier core particles, and a method in which the magnetic carrier core particles and the coating material are mixed with powder. A conventionally known method can be applied.

  Examples of the coating material on the surface of the magnetic carrier core particles include silicone resin, polyester resin, styrene resin, acrylic resin, polyamide, polyvinyl butyral, and aminoacrylate resin. These are used alone or in plural. The treatment amount of the coating material is preferably 0.1 to 30% by mass (preferably 0.5 to 20% by mass) with respect to the carrier core particles. The average particle size of these carriers is preferably 10 to 100 μm, more preferably 20 to 70 μm.

  When a two-component developer is prepared by mixing the toner of the present invention and a magnetic carrier, the mixing ratio is usually 2 to 15% by mass, preferably 4 to 13% by mass as the toner concentration in the developer. Good results are obtained. If the toner concentration is less than 2% by mass, the image density tends to decrease, and if it exceeds 15% by mass, fogging or in-machine scattering tends to occur.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. All parts used in the examples indicate parts by mass.

Production Examples of Copolymers A and C Synthesis of active hydrogen group-containing copolymers A1 to A6 and C1 was performed by the following method.

<Manufacture of copolymer A1>
A reaction vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube was charged with 100 parts of tetrahydrofuran and refluxed under a nitrogen stream.

  Next, the following monomers were mixed to prepare a monomer mixture.

[Monomer composition, mixing ratio]
・ Styrene 45.0 parts ・ Acrylic acid-n-butyl 44.0 parts ・ 2-hydroxyethyl methacrylate 11.0 parts ・ Perbutyl PV purity 70% (manufactured by NOF Corporation) The mixture was added dropwise to the vessel with stirring, and refluxed for 12 hours after the completion of the addition. Thereafter, distillation was performed to distill off the solvent, followed by drying at 50 ° C. under reduced pressure. The obtained solid was pulverized to obtain a copolymer A1.

<Production of copolymer A2>
A reaction vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube was charged with 100 parts of tetrahydrofuran and refluxed under a nitrogen stream.

  Next, the following monomers were mixed to prepare a monomer mixture.

[Monomer composition, mixing ratio]
・ Styrene 45.0 parts ・ Acrylic acid-n-butyl 47.0 parts ・ 2-hydroxyethyl methacrylate 8.0 parts ・ Perbutyl PV purity 70% (manufactured by NOF Corporation) The mixture was added dropwise to the vessel with stirring, and refluxed for 12 hours after the completion of the addition. Thereafter, distillation was performed to distill off the solvent, followed by drying at 50 ° C. under reduced pressure. The obtained solid was pulverized to obtain a copolymer A2.

<Production of copolymer A3>
A reaction vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube was charged with 100 parts of tetrahydrofuran and refluxed under a nitrogen stream.

  Next, the following monomers were mixed to prepare a monomer mixture.

[Monomer composition, mixing ratio]
-Styrene 88.0 parts-2-hydroxyethyl methacrylate 12.0 parts-Perbutyl PV purity 70% (made by NOF Corporation) 4.0 parts is mixed, and it is dripped at the said reaction container, stirring, After completion | finish of dripping Refluxed for 12 hours. Thereafter, distillation was performed to distill off the solvent, followed by drying at 50 ° C. under reduced pressure. The obtained solid was pulverized to obtain a copolymer A3.

<Production of copolymer A4>
A reaction vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube was charged with 100 parts of tetrahydrofuran and refluxed under a nitrogen stream.

  Next, the following monomers were mixed to prepare a monomer mixture.

[Monomer composition, mixing ratio]
・ Styrene 75.0 parts ・ Methyl methacrylate 20.0 parts ・ P-aminostyrene 5.0 parts ・ Perbutyl PV purity 70% (manufactured by Nippon Oil & Fats Co., Ltd.) 8.0 parts are mixed and stirred in the reaction vessel. The solution was added dropwise while refluxing for 12 hours after the completion of the addition. Thereafter, distillation was performed to distill off the solvent, followed by drying at 50 ° C. under reduced pressure. The obtained solid was pulverized to obtain a copolymer A4.

<Production of copolymer A5>
A reaction vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube was charged with 100 parts of tetrahydrofuran and refluxed under a nitrogen stream.

  Next, the following monomers were mixed to prepare a monomer mixture.

[Monomer composition, mixing ratio]
・ Styrene 52.5 parts ・ Acrylic acid-n-butyl 45.0 parts ・ 2-hydroxyethyl methacrylate 2.5 parts ・ Perbutyl PV purity 70% (manufactured by NOF CORPORATION) The mixture was added dropwise to the vessel with stirring, and refluxed for 12 hours after the completion of the addition. Thereafter, distillation was performed to distill off the solvent, followed by drying at 50 ° C. under reduced pressure. The obtained solid was pulverized to obtain a copolymer A5.

<Production of copolymer A6>
A reaction vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube was charged with 100 parts of tetrahydrofuran and refluxed under a nitrogen stream.

  Next, the following monomers were mixed to prepare a monomer mixture.

[Monomer composition, mixing ratio]
-Styrene 42.0 parts-Acrylic acid-n-butyl 40.0 parts-2-hydroxyethyl methacrylate 18.0 parts-Perbutyl PV purity 70% (made by NOF Corporation) 4.0 parts is mixed, and the said reaction The mixture was added dropwise to the vessel with stirring, and refluxed for 12 hours after the completion of the addition. Thereafter, distillation was performed to distill off the solvent, followed by drying at 50 ° C. under reduced pressure. The obtained solid was pulverized to obtain a copolymer A6.

<Production of copolymer C1>
In a reaction vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube, 60 parts of toluene was charged and refluxed under a nitrogen stream.

  Next, the following monomers were mixed to prepare a monomer mixture.

[Monomer composition, mixing ratio]
-51.0 parts of styrene-44.0 parts of acrylate-n-butyl-5.0 parts of 2-hydroxyethyl methacrylate-Perbutyl I Purity 75% (manufactured by NOF Corporation) The mixture was added dropwise to the vessel with stirring, and refluxed for 8 hours after the completion of the addition. Thereafter, distillation was performed to distill off the solvent, followed by drying at 50 ° C. under reduced pressure. The obtained solid was pulverized to obtain a copolymer C1.

<Modification of copolymer C1 with diisocyanate compound>
In a reaction vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube, 80.0 parts of dry toluene and 91.3 parts of copolymer C1 were charged, dissolved, and heated to 80 ° C. under a nitrogen stream.

  Next, a mixture of 8.7 parts of 4,4-diphenylmethane diisocyanate (Millionate MT, manufactured by Nippon Polyurethane Co., Ltd.) and 20.0 parts of dry toluene was prepared and added to the reaction vessel. After reacting at 80 ° C. for 2 hours, the reaction solution was cooled to room temperature to obtain a toluene solution of an NCO-modified product of copolymer C1.

  Copolymers A7 and A8 for comparative examples were synthesized by the method shown below.

<Production of copolymer A7>
A reaction vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube was charged with 100 parts of xylene and refluxed under a nitrogen stream.

  Next, the following monomers were mixed to prepare a monomer mixture.

[Monomer composition, mixing ratio]
・ Styrene 45.0 parts ・ Acrylic acid-n-butyl 44.0 parts ・ 2-hydroxyethyl methacrylate 11.0 parts ・ Perbutyl I purity 75% (manufactured by NOF Corporation) The mixture was added dropwise to the vessel with stirring, and refluxed for 8 hours after the completion of the addition. Thereafter, distillation was performed to distill off the solvent, followed by drying at 50 ° C. under reduced pressure. The obtained solid was pulverized to obtain a copolymer A7.

<Production of copolymer A8>
A reaction vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube was charged with 100 parts of tetrahydrofuran and refluxed under a nitrogen stream.

  Next, the following monomers were mixed to prepare a monomer mixture.

[Monomer composition, mixing ratio]
・ Styrene 45.0 parts ・ Acrylic acid-n-butyl 44.0 parts ・ 2-hydroxyethyl methacrylate 11.0 parts ・ Perbutyl PV purity 70% (manufactured by NOF Corporation) 1.5 parts are mixed, and the reaction The mixture was added dropwise to the vessel with stirring, and refluxed for 12 hours after the completion of the addition. Thereafter, distillation was performed to distill off the solvent, followed by drying at 50 ° C. under reduced pressure. The obtained solid was pulverized to obtain a copolymer A8.

Production Example of Prepolymer B Prepolymers B1 to B4 having a polyether structure or a polyester structure were synthesized by the method shown below.

<Production of prepolymer B1>
A reaction vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube was charged with 40.0 parts of dry toluene and 20.0 parts of 4,4-diphenylmethane diisocyanate (Millionate MT, manufactured by Nippon Polyurethane Industry Co., Ltd.) while stirring. It was dissolved and heated to 80 ° C. under a nitrogen stream. A solution prepared by dissolving 100.0 parts of polytetramethylene ether glycol (PTG-2000SN, manufactured by Hodogaya Chemical Co., Ltd.) in 80.0 parts of dry toluene was added dropwise thereto over 60 minutes. After dropping, the mixture was reacted at 80 ° C. for 90 minutes and then cooled to room temperature to obtain a toluene solution of prepolymer B1.

<Production of prepolymer B2>
A reaction vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube was charged with 40.0 parts of dry toluene and 14.3 parts of 4,4-diphenylmethane diisocyanate (Millionate MT, manufactured by Nippon Polyurethane Industry Co., Ltd.) while stirring. It was dissolved and heated to 80 ° C. under a nitrogen stream. A solution prepared by dissolving 100.0 parts of polyoxy (ethylene / propylene) diol (PF-732, manufactured by Asahi Glass Co., Ltd.) in 74.3 parts of dry toluene was prepared and added dropwise over 60 minutes. After dropping, the mixture was reacted at 80 ° C. for 90 minutes and then cooled to room temperature to obtain a toluene solution of prepolymer B2.

<Production of prepolymer B3>
A reaction vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube was charged with 40.0 parts of dry toluene and 25.0 parts of 4,4-diphenylmethane diisocyanate (Millionate MT, manufactured by Nippon Polyurethane Industry Co., Ltd.) while stirring. It was dissolved and heated to 80 ° C. under a nitrogen stream. A solution prepared by dissolving 100.0 parts of ethylene adipate (Nipporan 4040, manufactured by Nippon Polyurethane Industry Co., Ltd.) in 85.0 parts of dry toluene was added dropwise thereto over 60 minutes. After dropping, the mixture was reacted at 80 ° C. for 90 minutes and then cooled to room temperature to obtain a toluene solution of prepolymer B3.

<Production of prepolymer B4>
A reaction vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube was charged with 40.0 parts of dry toluene and 11.0 parts of 4,4-diphenylmethane diisocyanate (Millionate MT, manufactured by Nippon Polyurethane Industry Co., Ltd.) while stirring. It was dissolved and heated to 80 ° C. under a nitrogen stream. A solution prepared by dissolving 100.0 parts of polycaprolactone diol (Placcel 240CPB, manufactured by Daicel Chemical Industries) in 71.0 parts of dry toluene was added dropwise thereto over 60 minutes. After dropping, the mixture was reacted at 80 ° C. for 90 minutes and then cooled to room temperature to obtain a toluene solution of prepolymer B4.

  For the analysis of the prepolymers B1 to B4, a part of the toluene solution was taken out and the isocyanate value was measured using the toluene distilled off.

  Prepolymers D1 to D3 were prepared as follows.

<Prepolymer D1>
100 parts of butylene adipate (Nipporan 3027, manufactured by Nippon Polyurethane Industry Co., Ltd.) was dissolved in 100 parts of dry toluene under a nitrogen stream to obtain a toluene solution of prepolymer D1.

<Prepolymer D2>
100 parts of polyoxypropylene diol (PF-753, manufactured by Asahi Glass Co., Ltd.) was dissolved in 100 parts of dry toluene under a nitrogen stream to obtain a toluene solution of prepolymer D2.

<Prepolymer D3>
100 parts of polyoxypropylenediol (PF-751, manufactured by Asahi Glass Co., Ltd.) was dissolved in 100 parts of dry toluene under a nitrogen stream to obtain a toluene solution of prepolymer D3.

Production Examples of Toner Resin Compositions Toner resin compositions 1 to 9 were synthesized by the following method.

<Production of Resin Composition 1 for Toner>
In a reaction vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube, 200 parts of dry toluene and 45.0 parts of copolymer A1 were charged, dissolved, and heated to reflux. To this, 45.0 parts of a prepolymer B1 toluene solution was added and allowed to react under reflux conditions with stirring. 30 minutes after the reaction, the temperature was set to 78 ° C., 15.0 parts of methanol was added, and the mixture was refluxed for 40 minutes. Thereafter, the solvent was distilled off to obtain a resin composition 1 for toner.

<Production of Resin Composition 2 for Toner>
In a reaction vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube, 200 parts of dry toluene and 45.0 parts of copolymer A2 were charged, dissolved, and heated to reflux. To this, 45.0 parts of a toluene solution of prepolymer B2 was added and allowed to react under reflux conditions with stirring. 30 minutes after the reaction, the temperature was set to 78 ° C., 15.0 parts of methanol was added, and the mixture was refluxed for 40 minutes. Thereafter, the solvent was distilled off to obtain a resin composition 2 for toner.

<Production of Resin Composition 3 for Toner>
In a reaction vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube, 200 parts of dry toluene and 45.0 parts of copolymer A3 were charged, dissolved, and heated to reflux. To this, 45.0 parts of a toluene solution of prepolymer B3 was added and reacted under reflux conditions with stirring. 30 minutes after the reaction, the temperature was set to 78 ° C., 15.0 parts of methanol was added, and the mixture was refluxed for 40 minutes. Thereafter, the solvent was distilled off to obtain a resin composition 3 for toner.

<Production of Toner Resin Composition 4>
In a reaction vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube, 150 parts of dry toluene and 50.6 parts of copolymer A4 were charged, dissolved, and heated to reflux. To this was added 16.9 parts of a prepolymer B4 toluene solution, and the mixture was reacted under reflux conditions with stirring. 30 minutes after the reaction, the temperature was set to 78 ° C., 15.0 parts of methanol was added, and the mixture was refluxed for 40 minutes. Thereafter, the solvent was distilled off to obtain a resin composition 4 for toner.

<Production of Resin Composition 5 for Toner>
In a reaction vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube, 100 parts of dry toluene and 57.4 parts of copolymer A5 were charged, dissolved, and heated to reflux. To this was added 10.0 parts of a prepolymer B1 toluene solution, and the mixture was reacted under reflux conditions with stirring. 30 minutes after the reaction, the temperature was set to 78 ° C., 15.0 parts of methanol was added, and the mixture was refluxed for 40 minutes. Thereafter, the solvent was distilled off to obtain a resin composition 5 for toner.

<Production of Resin Composition 6 for Toner>
In a reaction vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube, 200 parts of dry toluene and 45.0 parts of copolymer A6 were charged, dissolved, and heated to reflux. To this, 45.0 parts of a prepolymer B1 toluene solution was added and allowed to react under reflux conditions with stirring. 30 minutes after the reaction, the temperature was set to 78 ° C., 15.0 parts of methanol was added, and the mixture was refluxed for 40 minutes. Thereafter, the solvent was distilled off to obtain a resin composition 6 for toner.

<Production of Resin Composition 7 for Toner>
In a reaction vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube, 150 parts of dry toluene and 108.0 parts of a toluene solution of copolymer C1 were charged and heated to reflux. To this, 27.0 parts of a toluene solution of prepolymer D1 was added and allowed to react under reflux conditions with stirring. 30 minutes after the reaction, the temperature was set to 78 ° C., 15.0 parts of methanol was added, and the mixture was refluxed for 40 minutes. Thereafter, the solvent was distilled off to obtain a resin composition 7 for toner.

<Production of Resin Composition 8 for Toner>
In a reaction vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube, 150 parts of dry toluene and 108.0 parts of a toluene solution of copolymer C1 were charged and heated to reflux. To this, 27.0 parts of a toluene solution of prepolymer D2 was added and reacted under reflux conditions with stirring. 30 minutes after the reaction, the temperature was set to 78 ° C., 15.0 parts of methanol was added, and the mixture was refluxed for 40 minutes. Thereafter, the solvent was distilled off to obtain a resin composition 8 for toner.

<Production of Toner Resin Composition 9>
In a reaction vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube, 50 parts of dry toluene and 117.4 parts of a toluene solution of copolymer C1 were charged and heated to reflux. To this was added 17.6 parts of a prepolymer D3 toluene solution, and the mixture was reacted under reflux conditions with stirring. 30 minutes after the reaction, the temperature was set to 78 ° C., 15.0 parts of methanol was added, and the mixture was refluxed for 40 minutes. Thereafter, the solvent was distilled off to obtain a resin composition 9 for toner.

  Comparative toner resin compositions 10 to 16 were synthesized by the following method.

<Production of Resin Composition 10 for Toner>
In a reaction vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube, 200 parts of dry toluene and 45.0 parts of copolymer A1 were charged, dissolved, and heated to reflux. To this, 45.0 parts of a prepolymer B1 toluene solution was added and allowed to react under reflux conditions with stirring. 80 minutes after the reaction, the temperature was set to 78 ° C., 15.0 parts of methanol was added, and the mixture was refluxed for 40 minutes. The gel-like product was added to 1000 parts of hexane and precipitated while being crushed well. The supernatant was discarded by decantation, transferred to a pallet and dried at 50 ° C. under reduced pressure. The mixture was cooled to −10 ° C. and further crushed with a hammer to obtain a resin composition 10 for toner.

<Production of Resin Composition 11 for Toner>
In a reaction vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube, 160 parts of dry toluene and 54.0 parts of copolymer A1 were charged, dissolved, and heated to reflux. To this was added 12.0 parts of a prepolymer B1 toluene solution, and the mixture was reacted under reflux conditions with stirring. 30 minutes after the reaction, the temperature was set to 78 ° C., 15.0 parts of methanol was added, and the mixture was refluxed for 40 minutes. Thereafter, the solvent was distilled off to obtain a resin composition 11 for toner.

<Production of Toner Resin Composition 12>
In a reaction vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube, 160 parts of dry toluene and 27.0 parts of copolymer A1 were charged, dissolved, and heated to reflux. To this, 66.0 parts of a prepolymer B1 toluene solution was added and allowed to react under reflux conditions with stirring. 30 minutes after the reaction, the temperature was set to 78 ° C., 15.0 parts of methanol was added, and the mixture was refluxed for 40 minutes. Thereafter, the solvent was distilled off to obtain a resin composition 12 for toner.

<Production of Resin Composition 13 for Toner>
In a reaction vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube, 200 parts of dry toluene and 45.0 parts of copolymer A7 were charged, dissolved, and heated to reflux. To this, 45.0 parts of a prepolymer B1 toluene solution was added and allowed to react under reflux conditions with stirring. 30 minutes after the reaction, the temperature was set to 78 ° C., 15.0 parts of methanol was added, and the mixture was refluxed for 40 minutes. Thereafter, the solvent was distilled off to obtain a resin composition 13 for toner.

<Manufacture of Resin Composition 14 for Toner>
In a reaction vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube, 200 parts of dry toluene and 45.0 parts of copolymer A8 were charged, dissolved, and heated to reflux. To this, 45.0 parts of a prepolymer B1 toluene solution was added and allowed to react under reflux conditions with stirring. 30 minutes after the reaction, the temperature was set to 78 ° C., 15.0 parts of methanol was added, and the mixture was refluxed for 40 minutes. Thereafter, the solvent was distilled off to obtain a resin composition 14 for toner.

<Manufacture of Resin Composition 15 for Toner>
In a reaction vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube, 150 parts of dry toluene and 108.0 parts of a toluene solution of copolymer C1 were charged and heated to reflux. To this, 13.0 parts of polyoxypropylene monool (XS-601, manufactured by Asahi Glass Co., Ltd.) dissolved in dry toluene 13.0 was added and reacted under stirring under reflux conditions. 30 minutes after the reaction, the temperature was set to 78 ° C., 15.0 parts of methanol was added, and the mixture was refluxed for 40 minutes. Thereafter, the solvent was distilled off to obtain a resin composition 15 for toner.

<Production of Resin Composition 16 for Toner>
A reaction vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube was charged with 100 parts of ethyl acetate and refluxed under a nitrogen stream.

  Next, the following monomers were mixed to prepare a monomer mixture.

[Monomer composition, mixing ratio]
・ Styrene 45.0 parts ・ Acrylic acid-n-butyl 40.0 parts ・ Polyethylene glycol dimethacrylate (light ester 14EG, manufactured by Kyoeisha Chemical Co., Ltd.) 1 5.0 parts ・ Perbutyl PV purity 70% (manufactured by NOF Corporation) 11.0 parts was mixed and added dropwise to the reaction vessel with stirring, and the mixture was refluxed for 2 hours after completion of the addition. The gel-like product was added to 1000 parts of hexane and precipitated while being crushed well. The supernatant was discarded by decantation, transferred to a pallet and dried at 50 ° C. under reduced pressure. The mixture was cooled to −10 ° C. and further crushed with a hammer to obtain a resin composition 16 for toner.

  Table 1 shows the composition and analysis values of each raw material for the toner resin compositions 1 to 16 produced above. Table 2 shows the results of measuring the peak molecular weight Mp, the weight average molecular weight Mw, the THF insoluble fraction, and the glass transition temperature Tg of the toner resin composition measured by the method described above.

Toner Production Examples Toners 1 to 9 were produced by the following method.

<Production Example of Toner 1>
Preparation of pigment dispersion paste:
・ Styrene monomer 80 parts ・ Cu phthalocyanine (Pigment Blue 15: 3) 13 parts After pre-mixing the above materials well in a container, disperse the mixture in a bead mill for about 4 hours while keeping it at 20 ° C. or lower. Produced.

Preparation of toner particles:
Into a separable flask, 1150 parts of ion-exchanged water and 390 parts of a 0.1 mol / liter-Na ₃ PO ₄ aqueous solution were added, heated to 60 ° C., and then adjusted to 12000 rpm using CLEARMIX (M Technique). And stirred. To this, 58 parts of 1.0 mol / liter-CaCl ₂ aqueous solution was added to obtain an aqueous dispersion medium containing Ca ₃ (PO ₄ ) ₂ .

-46.5 parts of the above pigment dispersion paste-35.0 parts of styrene monomer-25.0 parts of n-butyl acrylate-9.0 parts of polyolefin wax (Mw 1850, Mw / Mn 1.27, melting point 78.6 ° C)
Saturated polyester resin 5.0 parts (terephthalic acid-propylene oxide modified bisphenol A copolymer, acid value 15 mg KOH / g, Mw 18000)
E-88 (manufactured by Orient Chemical Co., Ltd.) 1.0 part. Toner resin composition 1 15.0 parts. These were heated to 60.degree. C., dissolved and dispersed to obtain a monomer mixture. Further, while maintaining the temperature at 60 ° C., 10.7 parts of perbutyl PV purity 70% (manufactured by NOF Corporation) was added and dissolved as a polymerization initiator to prepare a monomer composition. The monomer composition was charged into the prepared aqueous dispersion medium. The monomer composition was granulated by stirring at 15000 rpm for 10 minutes at 60 ° C. using CLEARMIX. Thereafter, the mixture was transferred to an oil bath at 90 ° C. and reacted for 8 hours at an internal temperature of 85 to 87 ° C. while stirring with a paddle stirring blade to complete the polymerization. After cooling to room temperature, hydrochloric acid was added to dissolve Ca ₃ (PO ₄ ) 2 and filtered, washed with water, and dried to obtain toner particles. Further, the obtained toner particles were classified, and 2 to 10 μm was selected to prepare toner particles.

Toner preparation:
Hydrophobic silica fine powder 1 having a number average primary particle size of 9 nm and a BET specific surface area of 180 m ² / g treated with silicone oil after treating the surface with 100 parts of the obtained toner particles with hexamethyldisilazane. Parts were mixed and externally added with a Henschel mixer (Mitsui Miike Chemical Co., Ltd.) to obtain toner 1.

<Production Example of Toner 2>
Toner 2 was obtained in the same manner as in the production example of toner 1, except that toner resin composition 2 was used instead of toner resin composition 1.

<Production Example of Toner 3>
Toner 3 was obtained in the same manner as in the production example of toner 1 except that toner resin composition 3 was used instead of toner resin composition 1.

<Production Example of Toner 4>
Toner 4 was obtained in the same manner as in the production example of toner 1, except that toner resin composition 4 was used instead of toner resin composition 1.

<Production Example of Toner 5>
Preparation of toner composition mixture:
-Copolycondensation polyester resin of 1,3-propanediol / 1,2-propanediol / terephthalic acid derivative (Tg 50 ° C., Mp 4400, Mw 4600)
100.0 parts Cu phthalocyanine (Pigment Blue 15: 3) 5.0 parts Aliphatic wax 8.0 parts (Mw 1850, Mw / Mn 1.27, melting point 78.6 ° C.)
-E-88 (manufactured by Orient Chemical Co., Ltd.) 1.0 part-Resin composition 5 for toner 15.0 parts-Ethyl acetate 120.0 parts While being held, it was dispersed for about 4 hours by a bead mill to prepare a toner composition mixed solution.

Preparation of toner particles:
In a separable flask, 240 parts of ion-exchanged water and 78 parts of a 0.1 mol / liter Na3PO4 aqueous solution were added, heated to 60 ° C., and then at 11,000 rpm using CLEARMIX (M Technique). Stir. To this, 12 parts of a 1.0 mol / liter-CaCl2 aqueous solution was added to obtain a dispersion medium containing Ca3 (PO4) 2. Furthermore, 1.0 part of carboxymethylcellulose (trade name: Cellogen BS-H, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was added and stirred for 10 minutes.

While the dispersion medium prepared in the flask is adjusted to 30 ° C. and stirred, 180 parts of the toner composition mixed solution adjusted to 30 ° C. is added, and after stirring for 1 minute, the toner composition is stopped. A dispersion suspension was obtained. The obtained toner composition dispersion suspension was stirred at a constant temperature of 40 ° C., and the gas phase on the suspension surface was forcibly renewed by a local exhaust device and kept for 17 hours to remove the solvent. After cooling to room temperature, hydrochloric acid was added to dissolve Ca ₃ (PO ₄ ) ₂ and filtered, washed with water, and dried to obtain toner particles. Further, the obtained toner particles were classified, and 2 to 10 μm was selected to prepare toner particles. Further, in the same manner as in the production example of the toner 1, the toner 5 was obtained by externally adding hydrophobic silica fine powder to the toner particles.

<Production Example of Toner 6>
Toner 6 was obtained in the same manner as in the production example of toner 5, except that 40.0 parts of resin composition 6 for toner was used instead of 15.0 parts of resin composition 5 for toner.

<Production Example of Toner 7>
A reaction vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube was charged with 100 parts of tetrahydrofuran and refluxed under a nitrogen stream.

Next, the following were mixed to prepare a monomer mixture.
-Styrene 75.0 parts-Acrylic acid-n-butyl 25.0 parts-Toner resin composition 7 15.0 parts-Perbutyl PV purity 70% (manufactured by Nippon Oil & Fats Co., Ltd.) 8.0 parts The mixture was added dropwise to the reaction vessel with stirring, and refluxed for 12 hours after the completion of the addition. Thereafter, distillation was performed to distill off the solvent, followed by drying at 50 ° C. under reduced pressure. The obtained solid was pulverized to obtain a resin composition.

-100.0 parts of the above resin composition-5.0 parts of Cu phthalocyanine (Pigment Blue 15: 3)-5.0 parts of polymethine wax (Mw: 1850, Mw / Mn: 1.27, melting point: 78.6 ° C) )
E-88 (manufactured by Orient Chemical Co., Ltd.) 0.5 part 2 After the mixture of the above materials was thoroughly mixed with a Henschel mixer (FM-75 type, manufactured by Mitsui Miike Chemical Co., Ltd.), the temperature was set to 130 ° C. 2 It knead | mixed with the axis | shaft kneader (PCM-30 type | mold, Ikegai Iron Works Co., Ltd. product).

  The obtained kneaded material was cooled, coarsely pulverized to 1 mm or less with a hammer mill, and then finely pulverized with an air jet type pulverizer. The resulting finely pulverized product was classified to obtain toner particles. Further, the toner 7 was obtained by externally adding hydrophobic silica fine powder to the toner particles in the same manner as in the toner 1 production example.

<Production Example of Toner 8>
100 parts of a 1,3-propanediol / 1,2-propanediol / terephthalic acid derivative copolycondensation polyester resin (Tg 50 ° C., Mp4400, Mw4600) and 15.0 parts of the toner resin composition 8 were mixed with 100 parts of ethyl acetate. The mixture was dissolved in a part and stirred and mixed at 60 ° C. Thereafter, distillation was performed to distill off the solvent, followed by drying at 50 ° C. under reduced pressure. The obtained solid was pulverized to obtain a resin composition.

-100.0 parts of the above resin composition-5.0 parts of Cu phthalocyanine (Pigment Blue 15: 3)-5.0 parts of polymethine wax (Mw: 1850, Mw / Mn: 1.27, melting point: 78.6 ° C) )
E-88 (manufactured by Orient Chemical Co., Ltd.) 0.5 part 2 After the mixture of the above materials was thoroughly mixed with a Henschel mixer (FM-75 type, manufactured by Mitsui Miike Chemical Co., Ltd.), the temperature was set to 130 ° C. 2 It knead | mixed with the axis | shaft kneader (PCM-30 type | mold, Ikegai Iron Works Co., Ltd. product).

  The obtained kneaded material was cooled, coarsely pulverized to 1 mm or less with a hammer mill, and then finely pulverized with an air jet type pulverizer. The resulting finely pulverized product was classified to obtain toner particles. Further, in the same manner as in the toner 1 production example, the toner 8 was obtained by externally adding hydrophobic silica fine powder to the toner particles.

<Production Example of Toner 9>
-Copolycondensation polyester resin of 1,3-propanediol / 1,2-propanediol / terephthalic acid derivative (Tg 50 ° C., Mp 4400, Mw 4600)
100.0 parts-Resin composition for toner 9 6.0 parts-Cu phthalocyanine (Pigment Blue 15: 3) 5.0 parts-Polymethine wax 5.0 parts (Mw: 1850, Mw / Mn: 1.27, melting point) : 78.6 ° C)
E-88 (manufactured by Orient Chemical Co., Ltd.) 0.5 part 2 After the mixture of the above materials was thoroughly mixed with a Henschel mixer (FM-75 type, manufactured by Mitsui Miike Chemical Co., Ltd.), the temperature was set to 130 ° C. 2 It knead | mixed with the axis | shaft kneader (PCM-30 type | mold, Ikegai Iron Works Co., Ltd. product).

  The obtained kneaded material was cooled, coarsely pulverized to 1 mm or less with a hammer mill, and then finely pulverized with an air jet type pulverizer. The resulting finely pulverized product was classified to obtain toner particles. Further, in the same manner as in the toner 1 production example, the toner 9 was obtained by externally adding hydrophobic silica fine powder to the toner particles.

  Toners 10 to 16 for comparative examples were produced by the following method.

<Production Example of Toner 10>
Toner 10 was obtained in the same manner as in the production example of toner 1 except that toner resin composition 10 was used instead of toner resin composition 1.

<Production Example of Toner 11>
Toner 11 was obtained in the same manner as in the production example of toner 1 except that toner resin composition 11 was used instead of toner resin composition 1.

<Production Example of Toner 12>
Toner 12 was obtained in the same manner as in the production example of toner 1 except that toner resin composition 12 was used instead of toner resin composition 1.

<Production Example of Toner 13>
Toner 13 was obtained in the same manner as in the production example of toner 1 except that toner resin composition 13 was used instead of toner resin composition 1.

<Production Example of Toner 14>
Toner 14 was obtained in the same manner as in the production example of toner 1 except that toner resin composition 14 was used instead of toner resin composition 1.

<Production Example of Toner 15>
Toner 15 was obtained in the same manner as in the production example of toner 1 except that toner resin composition 15 was used instead of toner resin composition 1.

<Production Example of Toner 16>
Toner 16 was obtained in the same manner as in the production example of toner 1 except that 10 parts of resin composition 16 for toner was used instead of 15 parts of resin composition 1 for toner.

  For the toners 1 to 16, the weight average particle diameter (D4), the peak molecular weight Mp, the weight average molecular weight Mw, and the glass transition temperature Tg were measured by the above-described methods. The results are shown in Table 3.

  Further, a two-component developer was prepared for the toners 1 to 16 as described below, an unfixed image was prepared, and a fixability test evaluation was performed. The results are shown in Table 4.

Fixability test method Each toner and a ferrite carrier surface-coated with a silicone resin (weight average particle size 42 μm) were mixed to a toner concentration of 6% by mass to prepare a two-component developer. An unfixed toner image (0.6 mg / cm ² ) was formed on a transfer paper (80 g / m ² ) by using a commercially available full-color digital copying machine (CLC700, manufactured by Canon).

  A fixing unit removed from a commercially available full-color laser beam printer (LBP-5400, manufactured by Canon) was remodeled so that the fixing temperature could be adjusted, and a fixing test of an unfixed image was performed using the fixing unit. Under normal temperature and humidity (23.5 ° C., 60% RH), the process speed is set to 180 mm / s, and the toner image is changed at each temperature while changing the set temperature every 5 ° C. in the range of 110 ° C. to 210 ° C. Was fixed. The fixing temperature at which no low temperature offset was observed was taken as the fixing start temperature. On the other hand, the temperature at which high temperature offset occurred was defined as the fixing end temperature. At this time, the difference between the low temperature side start point and the high temperature side end point was defined as a fixing temperature region. Further, the gloss value at each fixing temperature was measured, and the temperature at which the gloss value reached the maximum was taken as the gloss peak temperature.

  The gloss of the fixed image was measured using PG-3D (manufactured by Nippon Denshoku; incident angle 75 degrees). The measurement was performed at 5 points and the average value was used.

  As is apparent from the results shown in Table 4, with respect to toners 1 to 9 according to the present invention, the fixing temperature region was relatively wide and the gloss value was sufficiently high. Further, when toners 1 and 3 were compared, a difference in low-temperature fixing performance was observed. This is considered to be largely due to the difference in Tg of the toner resin composition used. On the contrary, in the toner of the comparative example, although the toners 10, 14 and 16 have a wide fixing temperature range, the gloss is low. In addition, toners 11, 12, 13, and 15 had high gloss values, but the fixing temperature region was insufficient.

Claims (14)

At least the following (a), (b), (c)
(A) a styrenic monomer ;
(B) an acrylate monomer or a methacrylate monomer ;
(C) an active hydrogen group-containing monomer ;
Is a resin composition for toner obtained by crosslinking reaction of copolymer A obtained by copolymerization with prepolymer B having an isocyanate group at both ends having a polyether structure or a polyester structure,
The weight average molecular weight Mw calculated by GPC of the copolymer A is 3000 to 35000, and the constituent ratio of the prepolymer B in the resin composition for toner is 12 to 49% by mass,
A toner resin composition, wherein a main peak molecular weight Mp of a tetrahydrofuran-soluble component calculated by GPC of the toner resin composition is 10,000 to 50,000, and a tetrahydrofuran-insoluble component is less than 3.0% by mass.   2. The toner resin composition according to claim 1, wherein the active hydrogen group of the copolymer A is a hydroxyl group.   The resin composition for toner according to claim 1 or 2, wherein the copolymer A has an active hydrogen group content of 0.25 mmol / g to 1.20 mmol / g. The prepolymer B is at both ends number toner resin composition according to any one of claims 1 to 3 The number average molecular weight determined from (NCO number) is characterized in that it is a 1000 to 12000. The toner resin composition, resin composition for toners according to any one of claims 1 to 4, wherein the weight average molecular weight Mw of tetrahydrofuran-soluble matter was calculated by GPC is 10000 to 100,000 . Toner resin composition according to any one of claims 1 to 5 glass transition temperature Tg calculated by DSC of the toner resin composition and less than 35 ° C.. A toner comprising 5.0 to 45.0 parts by mass of the resin composition for toner according to any one of claims 1 to 6 with respect to 100 parts by mass of a binder resin. At least the following (d), (e), (f)
(D) a styrenic monomer ;
(E) an acrylate monomer or a methacrylate monomer ;
(F) an active hydrogen group-containing monomer ;
A resin composition for a toner obtained by cross-linking a copolymer C obtained by copolymerizing a diisocyanate compound with a prepolymer D having a polyether structure or a polyester structure and having hydroxyl groups at both ends. Yes,
The weight average molecular weight Mw calculated by GPC of the copolymer C is 3000 to 35000, and the constituent ratio of the prepolymer B in the resin composition for toner is 12 to 49% by mass,
A toner resin composition, wherein a main peak molecular weight Mp of a tetrahydrofuran-soluble component calculated by GPC of the toner resin composition is 10,000 to 50,000, and a tetrahydrofuran-insoluble component is less than 3.0% by mass. The resin composition for toner according to claim 8 , wherein the active hydrogen group of the copolymer C is a hydroxyl group. Toner resin composition according to claim 8 or 9 active hydrogen group content of the copolymer C is characterized by a 0.25 mmol / g to 1.20 mmol / g. The prepolymer D is toner resin composition according to any one of claims 8 to 10 number average molecular weight determined from both ends number (OH number) is characterized in that it is a 1000 to 12000. The toner resin composition according to any one of claims 8 to 11 , wherein the toner resin composition has a weight average molecular weight Mw calculated from GPC of 10,000 to 100,000. . Toner resin composition according to any one of claims 8 to 12 glass transition temperature Tg calculated by DSC of the toner resin composition and less than 35 ° C.. A toner comprising 5.0 to 45.0 parts by mass of the resin composition for toner according to any one of claims 8 to 13 with respect to 100 parts by mass of the binder resin.