JP7295696B2 - toner binder - Google Patents

Description

The present invention relates to toner binders.

Toner binders for thermal fixation systems, which are generally used as image fixation systems in copiers, printers, etc., are required to have both low-temperature fixability, hot offset resistance, storage stability, and the like. Therefore, the toner binder has a high storage elastic modulus at a temperature lower than the fixing temperature, a low storage elastic modulus in a short time at the temperature at which fixing starts, and a constant storage elastic modulus up to a high temperature. It is required that the storage elastic modulus changes to an appropriate value around the fixing temperature.
In order to achieve the appropriate change in storage modulus described above, conventional toner binders use polyester as a main component (see, for example, Patent Documents 1 and 2).
However, a toner binder containing polyester as a main component and a toner composition using the same have poor charging characteristics due to a decrease in volume resistivity due to moisture absorption, as compared with polymers of monomers having ethylenically unsaturated bonds. There is a problem of deterioration of In the case of producing a chemical toner using a toner binder containing polyester as a main component, a dissolution suspension method other than emulsion polymerization or suspension polymerization using a monomer having an ethylenically unsaturated bond (for example, 3) or an emulsion aggregation method (see, for example, Patent Document 4), which requires a special granulation technique, resulting in a problem of high production costs.
On the other hand, toner binders that use conventional polymerized monomers with ethylenically unsaturated bonds as the main component instead of polyester have lower intermolecular cohesion than polyester, resulting in low-temperature fixability and hot resistance. It is difficult to achieve both offset property.
In order to solve this problem, a technique of using both low-molecular-weight and high-molecular-weight components (see, for example, Patent Document 5), a technique of using a site with high cohesion as a structural unit (see, for example, Patent Document 6), etc. However, all of them have the problem that the low-temperature fixability is insufficient as the storage elastic modulus increases in the fixing temperature range.
Therefore, it is believed that low-temperature fixability can be improved by using a crystalline acrylate resin or a copolymer of a crystalline acrylate resin and other copolymerizable monomer among polymers of monomers having an ethylenically unsaturated bond. Techniques (Patent Documents 7, 8, etc.) have been proposed.
However, these techniques have the problem of deterioration of storage stability due to deterioration of hygroscopicity due to the introduction of an acid value into the crystalline acrylate resin and the use of a copolymer with a copolymerizable monomer having a hydroxyl group. be.
The above techniques are insufficient to achieve both low-temperature fixability, hot offset resistance, storage stability and charging stability.

Japanese Patent No. 4493080 Japanese Patent No. 2105762 Japanese Patent No. 3596104 Japanese Patent No. 3492748 JP-A-11-327210 Japanese Patent No. 3212860 Japanese Patent No. 4677909 JP-A-2004-163956

An object of the present invention is to provide a polymer having, as a main component, a monomer having an ethylenically unsaturated bond, and to improve low temperature fixability, hot offset resistance, storage stability and charge stability. To provide a toner binder excellent in

The present inventors arrived at the present invention as a result of intensive studies to solve these problems.
That is, the present invention provides a vinyl resin (A) having a monomer (a) as an essential constituent monomer and an amorphous polyester having an alcohol component (x) and a carboxylic acid component (y) as essential constituent monomers. A toner binder containing a resin (B) , wherein the monomer (a) is a (meth)acrylate having 21 to 40 carbon atoms having a chain hydrocarbon group and/or a carbon number having a chain hydrocarbon group 21 to 40 vinyl ester, the melting point of the vinyl resin (A) by DSC measurement is 40 to 80 ° C., the relative dielectric constant ε' of the vinyl resin (A) is 2.5 to 4.0, and the vinyl The water content of the resin (A) is 500 to 10000 ppm, the acid value of the vinyl resin (A) is 19.9 mgKOH/g or less, and the polymerization ratio of the vinyl resin (A) is based on the weight of the toner binder. 21 to 99% by weight, and the polymerization ratio of the monomer (a) is 15 to 90% by weight based on the total weight of the monomers constituting the vinyl resin (A). be.

The present invention can provide a toner binder excellent in low temperature fixability, hot offset resistance, storage stability and charge stability.

The present invention will be described in detail below.
The toner binder of the present invention is a toner binder containing vinyl resin (A) having monomer (a) as an essential constituent monomer, wherein monomer (a) has a chain hydrocarbon group. It is a (meth)acrylate having 21 to 40 carbon atoms and/or a vinyl ester having 21 to 40 carbon atoms having a chain hydrocarbon group, and the vinyl resin (A) has a melting point measured by DSC of 40 to 80°C. The resin (A) has a dielectric constant ε′ of 2.5 to 4.0, a moisture content of the vinyl resin (A) of 500 to 10000 ppm, and the weight of the vinyl resin (A) based on the weight of the toner binder. is 21 to 99% by weight, and the polymerization ratio of the monomer (a) is 15 to 90% by weight based on the total weight of the monomers constituting the vinyl resin (A). It is a toner binder that

In the present invention, "(meth)acrylic" means methacrylic acid or acrylic acid.
In the present invention, "(meth)acrylate" means methacrylate or acrylate.

The toner binder of the present invention contains vinyl resin (A) having monomer (a) as an essential constituent monomer.
The above monomer (a) is a (meth)acrylate having 21 to 40 carbon atoms having a chain hydrocarbon group and/or a vinyl ester having 21 to 40 carbon atoms having a chain hydrocarbon group.
Examples of (meth)acrylates having 21 to 40 carbon atoms having a chain hydrocarbon group include (meth)acrylates having a linear alkyl group having 18 to 36 carbon atoms [octadecyl (meth)acrylate, nonadecyl (meth)acrylate, eicosyl (meth)acrylate, heneicosanyl (meth)acrylate, behenyl (meth)acrylate, lignoceryl (meth)acrylate, ceryl (meth)acrylate, montanyl (meth)acrylate, myricyl (meth)acrylate, dotriaconta (meth)acrylate, etc.] and (Meth)acrylates having a branched alkyl group having 18 to 36 carbon atoms [2-decyltetradecyl (meth)acrylate, etc.].
Examples of vinyl esters having 21 to 40 carbon atoms having a chain hydrocarbon group include vinyl esters having a linear alkyl group having 18 to 36 carbon atoms [for example, vinyl stearate, vinyl behenate, vinyl triacontanoate and hexa vinyl triacontanoate] and vinyl esters having a branched alkyl group having 18 to 36 carbon atoms.
Among these, from the viewpoint of storage stability of the toner, (meth)acrylates having a linear alkyl group of 18 to 36 carbon atoms and vinyl esters having a linear alkyl group of 18 to 36 carbon atoms are preferable. More preferred are (meth)acrylates having a straight-chain alkyl group of 18 to 34 carbon atoms and vinyl esters having a straight-chain alkyl group of 18 to 34 carbon atoms, particularly preferably straight-chain of 18 to 30 carbon atoms. (meth)acrylates having an alkyl group of and vinyl esters having a linear alkyl group having 18 to 30 carbon atoms, most preferably octadecyl (meth)acrylate, myricyl (meth)acrylate, and behenyl (meth)acrylate. .
Monomer (a) may be used alone or in combination of two or more

The weight ratio of the monomer (a) is 15 to 90% by weight, preferably 18 to 80% by weight, more preferably 20%, based on the total weight of the monomers constituting the vinyl resin (A). to 70% by weight, particularly preferably 25 to 65% by weight.
When the weight ratio of the monomer (a) is less than 15% by weight, the low-temperature fixability deteriorates, and when it exceeds 90% by weight, the hot offset resistance deteriorates.

The vinyl resin (A) of the present invention may further contain a monomer (b) other than the monomer (a) as a constituent monomer. The monomer (b) is a monomer other than the monomer (a), and the hydrogen bond term (dH) of the Hansen solubility parameter (HSP) is preferably 5.0 or more and 15.0 or less, more preferably 6 Any monomer may be used as long as it is 11 or less.
When the hydrogen bond term (dH) of the monomer (b) exceeds 15.0, the charging stability and storage stability deteriorate, and when it is less than 5.0, the storage stability deteriorates.

The Hansen solubility parameter is the solubility parameter introduced by Hildebrand (dD), the dispersion term (dD), the polar term (dP), the hydrogen bonding term (dH) divided into three components, expressed in three-dimensional space It is a thing. The dispersion term (dD) indicates the effect of the dispersion force, the polar term (dP) indicates the effect of the dipole force, and the hydrogen bond term (dH) indicates the effect of the hydrogen bond force.

The definition and calculation of the Hansen Solubility Parameter is provided by Charles M. et al. Hansen, Hansen Solubility Parameters; A Users Handbook (CRC Press, 2007). Moreover, by using the computer software "HSPiP4.1.0", it is possible to estimate the Hansen solubility parameters from the chemical structure of monomers for which parameter values are not described in the literature. In the present invention, for monomers for which parameter values are described in literature, those values are used, and for monomers for which parameter values are not described in literature, parameter values estimated using HSPiP are used.

Examples of the monomer (b) include (meth)acrylate (b1) having a hydrocarbon group having 1 to 3 carbon atoms, vinyl ester (b2) having a hydrocarbon group having 1 to 3 carbon atoms, amine and (meth) ) Amide with acrylic acid (b3), compound (b4) having a nitrile group and a vinyl group, compound (b5) having a lactam ring and a vinyl group, compound (b6) having a carboxyl group and a vinyl group, hydroxyl group and a (meth)acrylate (b7) having a and an aldehyde group (b8).

As the (meth)acrylate (b1) having a chain hydrocarbon group having 1 to 3 carbon atoms, methyl acrylate (the value of the hydrogen bond term (dH) of the Hansen solubility parameter (HSP) is 9.4, and the following The same applies in parentheses), ethyl acrylate (6.5), propyl acrylate (6.5) and methyl methacrylate (5.4).

Vinyl esters (b2) having a hydrocarbon group of 1 to 3 carbon atoms include, for example, vinyl acetate (6.8), vinylbutyric acid (6.2) and isopropenyl acetate (6.2).

Examples of the amide (b3) of amine and (meth)acrylic acid include monomers obtained by reacting ammonia or amines having 1 to 8 carbon atoms with acrylic acid or methacrylic acid by a known method.
Specific examples include acrylamide (12.8), methacrylamide (11.6), N-methylacrylamide (9.7) and N-ethylacrylamide (8.7).

Examples of the compound (b4) having a nitrile group and a vinyl group include compounds having a nitrile group having 1 to 5 carbon atoms and a vinyl group (for example, acrylonitrile (6.8), methacrylonitrile (8.5), 4- pentenenitrile (5.7), 5-hexenenitrile (5.2) and α-chloroacrylonitrile (5.2).

Examples of the compound (b5) having a lactam ring and a vinyl group include compounds having a lactam ring having 4 to 8 carbon atoms and a vinyl group (eg, vinylpyrrolidone (5.9), N-vinylpyrrolidone (6.3) , N-vinyl-3-methylpyrrolidone (5.7), N-vinylpiperidone (5.7), N-vinyl-4-methylpiperidone (5.5), N-vinyl-caprolactam (5.5) and N- and vinyl-2-pyridone (6.8).
Vinyl esters (b2) having a hydrocarbon group of 1 to 3 carbon atoms include, for example, vinyl formate, vinyl acetate, vinylpropionic acid and isopropenyl acetate.

Examples of the compound (b6) having a carboxyl group and a vinyl group include compounds having a carboxyl group having 1 to 9 carbon atoms and a vinyl group [for example, methacrylic acid (13.4), crotonic acid (14.4), cinnamic acid (10.9), maleic acid monomethyl ester (12.7), fumaric acid monomethyl ester (12.7), itaconic acid monomethyl ester (13.7), citraconic acid monoethyl ester (13.9), 3-butene acid (14.1), 4-pentenoic acid (12.7), 5-hexenoic acid (11.6), 6-heptenoic acid (10.4), 7-octenoic acid (9.9), 8-nonene acid (9.2), 9-decenoic acid (8.6), 10-undecenoic acid (7.9) and 11-tridecenoic acid (7.8)].
In this specification, the number of carbon atoms in the compounds and structures having a carboxyl group does not include the number of carbon atoms contained in the carboxyl group portion.

As the (meth)acrylate (b7) having a hydroxyl group, any of hydroxyethyl methacrylate (13.4), hydroxypropyl acrylate (13.7) (2-hydroxypropyl ester, 2-hydroxy-1-methylethyl ester) or mixtures thereof), hydroxypropyl methacrylate (12.2) (2-hydroxypropyl ester, 2-hydroxy-1-methylethyl ester or mixtures thereof), hydroxybutyl acrylate (13.0) and methacryl acid hydroxybutyl (11.7) and the like.

(Meth)acrylates (b8) having an aldehyde group include acrolein (7.0) and methacrylolein (5.8).

Monomer (b) may be used alone or in combination of two or more.
Among the above monomers (b), from the viewpoint of achieving both low-temperature fixability and storage stability, (meth)acrylates having a hydrocarbon group having 1 to 3 carbon atoms, and hydrocarbon groups having 1 to 3 carbon atoms are preferable. , an amide of an amine having 1 to 8 carbon atoms and (meth)acrylic acid, a compound having a nitrile group having 1 to 5 carbon atoms and a vinyl group, a lactam ring having 4 to 8 carbon atoms and a vinyl group , a compound having a carboxyl group having 1 to 9 carbon atoms and a vinyl group, and a (meth)acrylate having a hydroxyl group.
More preferably, (meth)acrylic acid, methyl methacrylate, vinyl acetate, vinylpropion, (meth)acrylamide, acrylonitrile, methacrylonitrile, vinylpyrrolidone, (anhydrous) maleic acid, hydroxyethyl (meth)acrylate and (meth) and hydroxypropyl acrylate.

When the vinyl resin (A) contains the monomer (b), the weight ratio of the monomer (b) in the monomers constituting the vinyl resin (A) is determined from the viewpoint of low temperature fixability and hot offset resistance. Therefore, it is preferably 10 to 85% by weight, more preferably 15 to 80% by weight, and particularly preferably 18 to 75% by weight, based on the total weight of the monomers constituting the vinyl resin (A). be.

The weight ratio {(a):(b)} of the monomer (a) and the monomer (b) constituting the vinyl resin (A) is preferably 98:2 from the viewpoint of low-temperature fixability and storage stability. to 15:85, more preferably 70:30 to 15:85.

The vinyl resin (A) is a constituent monomer other than (a) and may contain a monomer (c) other than (b). Monomer (c) may be used individually by 1 type, or may use 2 or more types together.
The monomer (c) is not particularly limited as long as it is a monomer other than the monomer (a) and a monomer other than the monomer (b). to 3 alkylstyrenes (such as α-methylstyrene and p-methylstyrene), ethyl methacrylate, propyl methacrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, vinyl butyrate and vinyl isobutyrate, and the like. be done. Of these, styrene is preferred from the viewpoint of storage stability when used as a toner.

When the monomers constituting the vinyl resin (A) contain the monomer (c), the weight ratio of the monomer (c) should be adjusted to the amount of the monomers constituting the vinyl resin (A) from the viewpoint of storage stability. Based on the total weight of the body, preferably 0-40% by weight, more preferably 0-35% by weight, particularly preferably 0-30% by weight, most preferably 0-25% by weight .

The vinyl resin (A) in the present invention is a known monomer composition containing the monomer (a), optionally used monomer (b) and/or optionally used monomer (c). It can be produced by polymerization by a method (eg, radical polymerization, anionic polymerization, cationic polymerization, living radical polymerization, living anionic polymerization, living cationic polymerization, etc.). For example, the method described in JP-A-5-117330 (method of synthesizing by a solution polymerization method by reacting the monomer with a radical initiator (such as azobisisobutyronitrile) in a solvent (such as toluene)), and a method of polymerizing by the method described in JP-A-10-326026.

The weight average molecular weight of the vinyl resin (A) in the present invention is preferably 10,000 to 3,000,000, more preferably 50,000 to 1,000, from the viewpoints of low-temperature fixability and hot offset resistance of the toner. ,000, particularly preferably 50,000 to 500,000. The weight average molecular weight of polymer (A) can be adjusted by polymerization temperature, amount of radical polymerization initiator, chain transfer agent and the like.

The weight average molecular weight of the vinyl resin (A) is measured using gel permeation chromatography (hereinafter abbreviated as GPC) under the following conditions.
Apparatus (one example): HLC-8120 [manufactured by Tosoh Corporation]
Column (one example): 2 TSK GEL GMH6 [manufactured by Tosoh Corporation]
Measurement temperature: 40°C
Sample solution: 0.25% by weight tetrahydrofuran solution (undissolved matter was filtered through a PTFE filter with an aperture of 1 μm)
Mobile phase: Tetrahydrofuran (without polymerization inhibitor)
Solution injection volume: 100 μl
Detection device: Refractive index detector Reference substance: TSK standard POLYSTYRENE 12 points (weight average molecular weight: 500 1050 2800 5970 9100 18100 37900 96400 190000 355000 1090000 2890000) So Co., Ltd.]

In the present invention, the vinyl resin (A) has a melting point measured by DSC of 40 to 80°C, preferably 45 to 80°C, more preferably 55 to 70°C.
When the melting peak temperature Tm is less than 40°C, the storage stability deteriorates, and when it exceeds 80°C, the low-temperature fixability deteriorates.

The melting point of the vinyl resin (A) as measured by DSC can be adjusted by the type, composition ratio, weight average molecular weight, etc. of the monomers constituting the vinyl resin (A). Specifically, the number of carbon atoms in the monomer (a) that constitutes the vinyl resin (A) is increased, the weight ratio of the number of carbon atoms in the monomer (a) that constitutes the vinyl resin (A) is increased, and the vinyl resin The melting point can be raised by a method such as increasing the weight average molecular weight of the number of carbon atoms in (A). For example, when the number of carbon atoms of the monomer (a) is 22 and the ratio of the monomer (a) is 40% by weight, the weight average molecular weight is set to 5000 or more to achieve the above range.

The DSC measurement in the present invention is a value measured under the following conditions using a differential scanning calorimeter (manufactured by Seiko Instruments Inc., DSC210, etc.).
<Measurement conditions>
(1) Hold at 30°C for 10 minutes (2) Heat up to 150°C at 10°C/min (3) Hold at 150°C for 10 minutes (4) Cool down to 0°C at 10°C/min (5) Hold at 0°C for 10 minutes (6) Heating up to 150°C at 10°C/min The above operations (1) to (6) are successively performed, and each endothermic peak of the differential scanning calorimetry curve measured in the process of (6). to parse

The vinyl resin (A) has a dielectric constant ε' of 2.5 to 4.0, preferably 2.7 to 3.9, more preferably 3.0 to 3.9. As a result, the charged toner particles can be transferred more efficiently during image formation.

The dielectric constant ε' of the vinyl resin (A) can be adjusted by the type, composition ratio, and acid value of the monomers constituting the vinyl resin (A). Specifically, the number of carbon atoms in the monomer (a) that constitutes the vinyl resin (A) is increased, the weight ratio of the number of carbon atoms in the monomer (a) that constitutes the vinyl resin (A) is increased, and the vinyl resin The dielectric constant can be increased by increasing the acid value of (A). For example, when the weight ratio of the monomer (a) is 15%, the specific permittivity falls within the above range by setting the acid value to 0 or more.

The volume resistivity and dielectric constant of the vinyl resin (A) were measured under the following conditions.
Device: TR-1100 type dielectric loss automatic measurement device manufactured by Ando Electric Co., Ltd.
Ando Electric Co., Ltd. TO-198 type constant temperature bath solid electrode: SE-70 type solid electrode Measurement environment: 23 ° C., 50% RH
Put 1.5 g of vinyl resin (A) in a molding ring (made of PVC, φ25 mm, height 5 mm) and press with a press machine at 98 kN for 10 seconds to form a cylinder with a thickness of about 2.3 mm and a diameter of 25 mm. bottom. The molded article was allowed to stand at 23° C. and 50% RH for 30 minutes or more, removed from the molding ring, and the thickness of the molded article was measured with a micrometer (D, unit: μm). Measurements were taken at 1 kHz across the main and counter electrodes, and the CONDUCTANCE (Gx, in nS) and capacitance (Cx, in pF) were recorded. By substituting the obtained numerical values into the following formula (1) or (2), the volume resistivity and dielectric constant were calculated.
Volume resistivity = 3.14 x (0.9) ² / (Gx x D x 10 ^-13 ) (1)
Permittivity=(14.39×Cx×D)/32400 (2)
The dielectric constant of the vinyl resin (A) is determined by the ratio of the calculated dielectric constant to the dielectric constant of air, 1.000585.

The water content of the vinyl resin (A) is 500-10000 ppm, preferably 600-6000 ppm, more preferably 750-3000 ppm. If it is less than 500 ppm, the charging stability will deteriorate, and if it exceeds 10000 ppm, the storage stability will deteriorate.

The amount of water contained in the vinyl resin (A) can be adjusted by the type, composition ratio and acid value of the monomers constituting the vinyl resin (A). Specifically, using a (meth)acrylate (b7) having a hydroxyl group as a monomer constituting the vinyl resin (A), increasing the weight ratio of the monomer (b7) constituting the vinyl resin (A), The amount of water contained in the vinyl resin (A) can be increased by a method such as increasing the acid value of the vinyl resin (A). For example, when hydroxyethyl methacrylate is used as the monomer (b7) constituting the vinyl resin (A) and the weight ratio of the monomer (b7) is 4%, the acid value of the vinyl resin (A) is 19. By setting the content to 9 mgKOH/g or less, the water content of the vinyl resin (A) falls within the above range.
The water content of the vinyl resin (A) is measured by a Karl Fischer moisture measuring device combined with a water vaporizer [eg, trade name: VA-100 (Mitsubishi Chemical Analytic Tech) (vaporization temperature: 190° C.)].

The weight ratio of the vinyl resin (A) is 21 to 99% by weight, preferably 40 to 95% by weight, more preferably 70 to 90% by weight, based on the weight of the toner binder. If the weight ratio of the vinyl resin (A) is less than 21% by weight, the low-temperature fixability is deteriorated, and if the weight ratio of the vinyl resin (A) is over 99% by weight, the charging stability is deteriorated.

The acid value of the vinyl resin (A) is preferably 19.9 mgKOH/g or less, more preferably 0 to 15 mgKOH/g, particularly preferably 0 to 10 mgKOH/g. When the acid value of the vinyl resin (A) is 19.9 mgKOH/g or less, the storage stability is good because the hygroscopicity is small.

The acid value of the vinyl resin (A) can be adjusted by adjusting the acid value of the monomer and the content of the monomer having the acid value. The acid value of vinyl resin (A) is measured by the method described in JIS K 0070.

The toner binder of the present invention may contain an amorphous polyester resin (B) containing an alcohol component (x) and a carboxylic acid component (y) as essential constituent monomers. The amorphous polyester resin in the present invention is a polyester resin that does not have an endothermic peak top temperature when the transition temperature of the sample is measured using a differential scanning calorimeter.

The alcohol component (x) of the amorphous polyester resin (B) includes an aliphatic diol having 2 to 4 carbon atoms (x1), an alkylene oxide adduct of bisphenol A (x2), and other than (x1) and (x2). Diols (x3), trivalent or higher polyols (x4), monools (x5), and the like.

Examples of the aliphatic diol (x1) having 2 to 4 carbon atoms include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol and diethylene glycol.

Examples of the alkylene oxide adduct of bisphenol A (x2) include alkylene oxide adducts of bisphenol A (the average number of added moles is preferably 2 to 30).
The alkylene oxide to be added to bisphenol A is preferably an alkylene oxide having 2 to 4 carbon atoms, specifically ethylene oxide, propylene oxide, 1,2-, 2,3-, 1,3- or iso- butylene oxide, tetrahydrofuran, and the like.

Examples of diols (x3) other than (x1) and (x2) include alkylene glycols having 5 to 36 carbon atoms, alkylene ether glycols having 4 to 36 carbon atoms, alicyclic diols having 6 to 36 carbon atoms, and 6 to 6 carbon atoms. 36 alkylene oxide adducts of alicyclic diols and dihydric phenols.
Alkylene glycols having 5 to 36 carbon atoms include neopentyl glycol, 1,6-hexanediol, 1,9-nonanediol, 1,10-decanediol and 1,12-dodecanediol.
Alkylene ether glycols having 4 to 36 carbon atoms include diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol and polytetramethylene ether glycol.
Alicyclic diols having 6 to 36 carbon atoms include 1,4-cyclohexanedimethanol and hydrogenated bisphenol A.
Examples of the alkylene oxide adducts of alicyclic diols having 6 to 36 carbon atoms include alkylene oxide adducts of alicyclic diols having 6 to 36 carbon atoms (the average number of added moles is preferably 2 to 4).
Examples of dihydric phenols include monocyclic dihydric phenols (eg, hydroquinone) and alkylene oxide adducts of bisphenol compounds other than bisphenol A (preferably having an average number of added moles of 2 to 30).

An alkylene oxide adduct of a bisphenol compound is obtained by adding an alkylene oxide (hereinafter, "alkylene oxide" may be abbreviated as AO) to a bisphenol compound. Examples of the bisphenol compound include those represented by the following general formula (2).

HO-Ar-X-Ar-OH (2)
[In the formula, X represents an alkylene group having 1 to 3 carbon atoms, —SO ₂ —, —O—, —S—, or a direct bond. Ar represents a phenylene group in which a hydrogen atom may be substituted with a halogen atom or an alkyl group having 1 to 30 carbon atoms. ]

Bisphenol compounds include, for example, bisphenol F, bisphenol B, bisphenol AD, bisphenol S, trichlorobisphenol A, tetrachlorobisphenol A, dibromobisphenol F, 2-methylbisphenol A, 2,6-dimethylbisphenol A and 2,2'- diethylbisphenol F and the like.

Trihydric or higher polyols (x4) include trihydric or higher aliphatic polyhydric alcohols having 3 to 36 carbon atoms (alkane polyols and their intramolecular or intermolecular dehydrates such as glycerin, trimethylolethane, trimethylolpropane, Pentaerythritol, sorbitol, sorbitan, polyglycerin and dipentaerythritol), sugars and their derivatives (eg sucrose and methylglucoside), AO adducts of the above aliphatic polyhydric alcohols (average addition mole number is preferably 1 to 30) , AO adducts of trisphenols (trisphenol PA, etc.) (average number of added moles is preferably 2 to 30) and novolak resins (phenol novolak and cresol novolak, etc., and the average degree of polymerization is preferably 3 to 60 ) (average number of added moles is preferably 2 to 30) and the like.

Examples of the monool (x5) include alkanols having 1 to 30 carbon atoms (methanol, ethanol, isopropanol, dodecyl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, etc.).

The alcohol component (x) of the amorphous polyester resin (B) may be used singly or in combination of two or more.
Of these alcohol components (x), aliphatic diols having 2 to 4 carbon atoms and alkylene oxide adducts of bisphenol A are preferred from the viewpoint of low-temperature fixability, and 1,2-propylene glycol and bisphenol A are more preferred. and the propylene oxide adduct of bisphenol A.

Examples of the carboxylic acid component (y) of the amorphous polyester resin (B) include monocarboxylic acid (y1) and polycarboxylic acid (y2).

Monocarboxylic acids (y1) include aliphatic (including alicyclic) monocarboxylic acids and aromatic monocarboxylic acids.
Aliphatic (including alicyclic) monocarboxylic acids include alkane monocarboxylic acids having 1 to 30 carbon atoms (formic acid, acetic acid, propionic acid, butanoic acid, isobutanoic acid, caprylic acid, capric acid, lauric acid, myristic acid, , palmitic acid, stearic acid, behenic acid, cerotic acid, monitoric acid, melissic acid, etc.) and alkene monocarboxylic acids having 3 to 24 carbon atoms (acrylic acid, methacrylic acid, oleic acid, linoleic acid, etc.).
Examples of aromatic monocarboxylic acids include aromatic monocarboxylic acids having 7 to 36 carbon atoms (benzoic acid, methylbenzoic acid, pt-butylbenzoic acid, phenylpropionic acid, naphthoic acid, etc.).

The polycarboxylic acid (y2) includes dicarboxylic acid (y21) and/or tricarboxylic or higher polycarboxylic acid (y22).

The dicarboxylic acid (y21) includes alkanedicarboxylic acids having 4 to 36 carbon atoms (eg succinic acid, adipic acid and sebacic acid), alicyclic dicarboxylic acids having 6 to 40 carbon atoms [eg dimer acid (dimerized linoleic acid), ], C4-36 alkenedicarboxylic acids (e.g. alkenylsuccinic acids such as dodecenylsuccinic acid, maleic acid, fumaric acid, citraconic acid and mesaconic acid), C8-36 aromatic dicarboxylic acids (e.g. phthalic acid, isophthalic acid, terephthalic acid and naphthalene dicarboxylic acid) and their ester-forming derivatives [lower alkyl (alkyl group with 1 to 4 carbon atoms: methyl, ethyl, n-propyl, etc.) esters and acid anhydrides, the following ester-forming The same goes for derivatives. ] etc. are mentioned.

Examples of trivalent or higher polycarboxylic acids (y22) include aromatic polycarboxylic acids having 9 to 20 carbon atoms (trimellitic acid, pyromellitic acid, etc.), aliphatic polycarboxylic acids having 6 to 36 carbon atoms (hexanetricarboxylic acid etc.) and their ester-forming derivatives (acid anhydrides, esters with lower alcohols, etc.), and the like.

The carboxylic acid component (y) of the amorphous polyester resin (B) may be used alone or in combination of two or more.
Among these carboxylic acid components (y), from the viewpoint of low-temperature fixability and hot offset resistance, alkanedicarboxylic acids having 4 to 36 carbon atoms, alkenedicarboxylic acids having 4 to 36 carbon atoms, and aromatic compounds having 8 to 36 carbon atoms are preferred. dicarboxylic acids and aromatic polycarboxylic acids having 9 to 20 carbon atoms, more preferably adipic acid, fumaric acid, terephthalic acid and trimellitic acid.

The reaction ratio between the alcohol component (x) and the carboxylic acid component (y) is preferably 2/1 to 1/2, more preferably 1.5, as the equivalent ratio [OH]/[COOH] between the hydroxyl group and the carboxyl group. /1 to 1/1.3, particularly preferably 1.3/1 to 1/1.2.

In the present invention, the polycondensation of alcohol component (x) and carboxylic acid component (y) can be carried out using a known esterification reaction. As a general method, for example, in an inert gas (nitrogen gas etc.) atmosphere, in the presence of a polymerization catalyst, the reaction temperature is preferably 150 to 280°C, more preferably 180 to 270°C, and particularly preferably 200 to 260°C. It can be carried out by reacting at °C. The reaction time is preferably 30 minutes or more, particularly 2 to 40 hours, from the viewpoint of ensuring the polycondensation reaction.
It is also effective to reduce the pressure in order to improve the reaction rate in the final stage of the reaction.

As the polymerization catalyst, from the viewpoint of reactivity and environmental protection, it is preferable to use a polymerization catalyst containing one or more metals selected from titanium, antimony, zirconium, nickel and aluminum, more preferably a titanium-containing catalyst. .
Titanium-containing catalysts include titanium alkoxide, potassium oxalic acid titanate, titanium terephthalate, catalysts described in JP-A-2006-243715 [titanium dihydroxybis (triethanolamine), titanium monohydroxytris (triethanolamine ), and intramolecular polycondensates thereof, etc.] and catalysts described in JP-A-2007-11307 (titanium tributoxyterephthalate, titanium triisopropoxyterephthalate, titanium diisopropoxyditerephthalate, etc.).
Examples of antimony-containing catalysts include antimony trioxide.
Zirconium-containing catalysts include zirconyl acetate and the like.
Nickel-containing catalysts include nickel acetylacetonate and the like.
Aluminum-containing catalysts include aluminum hydroxide and aluminum triisopropoxide.

It is desirable to appropriately determine the amount of the catalyst to be added so as to maximize the reaction rate. The amount added is preferably 10 ppm to 1.9% by weight, more preferably 100 ppm to 1.7% by weight, based on the total raw materials. An addition amount of 10 ppm or more is preferable in that the reaction rate increases.

The glass transition point of the amorphous polyester resin (B) is preferably 45-80°C, more preferably 50-80°C. The glass transition point of the amorphous polyester resin (B) can be adjusted by the weight average molecular weight, the structure of the alcohol component (x) and the carboxylic acid component (y), the composition ratio, etc. A generally known method can be used for the adjustment factor.
When the glass transition point of the amorphous polyester resin (B) is 45°C or higher, the storage stability is good, and when it is 80°C or lower, the low-temperature fixability is good.

The glass transition point of the amorphous polyester resin (B) is measured by the method (DSC method) specified in ASTM D3418-82 using DSC20, SSC/580 manufactured by Seiko Instruments Inc.
Specifically, 5 mg of the sample was heated at 20°C per minute to a temperature about 30°C higher than the end of the glass transition, cooled at 60°C per minute to a temperature about 50°C lower than the glass transition temperature, and Heat at 20°C per minute to about 30°C higher.
From the data obtained from the above measurements, draw a graph with the vertical axis representing the amount of heat absorption and heat, and the horizontal axis representing the temperature. The glass transition temperature is the temperature at the intersection with the tangent line drawn at the point where the slope of the curve is maximum.

The weight-average molecular weight of the amorphous polyester resin (B) in the present invention is preferably 3,000 to 15,000, more preferably 4,000 to 12,000, especially from the viewpoint of low-temperature fixability and storage stability. It is preferably 4,500 to 10,000. The weight average molecular weight of the amorphous polyester resin (B) in the present invention can be adjusted by adjusting the charging ratio of the alcohol component (x) and the carboxylic acid component (y). The weight average molecular weight of the amorphous polyester resin (B) can be measured in the same manner as the weight average molecular weight of the vinyl resin (A).

The acid value of the amorphous polyester resin (B) is preferably 1 to 30 mgKOH/g, more preferably 1 to 25 mgKOH/g, particularly preferably 1 to 20 mgKOH/g. When the acid value of the amorphous polyester resin (B) is 1 mgKOH/g or more, the charge stability is good, and when it is 30 mgKOH/g or less, the storage stability is good.

The acid value of the amorphous polyester resin (B) can be adjusted by adjusting the acid value of the monomer and the content of the monomer having the acid value. The acid value of the amorphous polyester resin (B) is measured by a method such as JIS K 0070, for example.

The softening point of the amorphous polyester resin (B) is preferably 90 to 144°C, more preferably 95 to 130°C, still more preferably 95 to 120°C, from the viewpoint of storage stability.

The softening point of the amorphous polyester resin (B) in the invention is measured under the following conditions.
Using a flow tester {for example, CFT-500D manufactured by Shimadzu Corporation}, while heating 1 g of a measurement sample at a temperature increase rate of 6 ° C./min, a load of 1.96 MPa is applied by a plunger, and a diameter of 1 mm , extruded from a nozzle with a length of 1 mm, drew a graph of "plunger descent amount (flow value)" and "temperature", and read the temperature corresponding to 1/2 of the maximum plunger descent amount from the graph , this value (the temperature when half of the sample to be measured flows out) is taken as the softening point.

When the amorphous polyester resin (B) is included, the weight ratio of the vinyl resin (A) and the amorphous polyester resin (B) is preferably 99/1 to 21/79, more preferably 95/5 to 40/60. If it is 99/1 or more, charging stability deteriorates, and if it is 21/79 or less, low-temperature fixability deteriorates.

The toner binder of the present invention is obtained by uniformly mixing the vinyl resin (A), the amorphous polyester resin (B), etc., by simply using a known mechanical mixing method (for example, a method using a mechanical stirrer or a magnetic stirrer). or by dissolving the vinyl resin (A) and the amorphous polyester resin (B) in a solvent at the same time for homogenization and then removing the solvent.
When using a mechanical mixing method, the temperature during mixing is preferably 50 to 200°C. Further, the mixing time is preferably 0.5 to 24 hours.
In the case of using a method of dissolving in a solvent, the solvent is not particularly limited as long as it can dissolve all the polymers constituting the toner binder. Examples include toluene and acetone.
The temperature for removing the solvent is preferably 50 to 200° C., and the removal of the solvent can be accelerated by reducing the pressure or ventilating as necessary.

When the toner binder of the present invention is used as a toner, it may contain a colorant, release agent, charge control agent, fluidizing agent, and the like, if necessary.

As the colorant, all dyes, pigments, etc. used as colorants for toners can be used. For example, carbon black, iron black, Sudan black SM, fast yellow G, benzidine yellow, pigment yellow, India first orange, pigment red, irgasin red, paranitroaniline red, toluidine red, carmine FB, pigment orange R, lake red. 2G, Rhodamine FB, Rhodamine B Lake, Methyl Violet B Lake, Phthalocyanine Blue, Pigment Blue, Brilliant Green, Phthalocyanine Green, Pigment Yellow, Oil Yellow GG, Kayaset YG, Orazol Brown B and Oil Pink OP. can be used alone or in combination of two or more. In addition, magnetic powder (powder of ferromagnetic metal such as iron, cobalt, nickel, etc., or compounds such as magnetite, hematite, ferrite, etc.) can be incorporated as required, also functioning as a coloring agent.
The content of the colorant is preferably 1-40 parts, more preferably 3-10 parts, per 100 parts of the toner binder of the present invention. When magnetic powder is used, the amount is preferably 20-150 parts, more preferably 40-120 parts.
Above and below, parts mean parts by weight.

The release agent preferably has a softening point of 50 to 170° C., and includes aliphatic hydrocarbon waxes such as polyolefin wax, microcrystalline wax, paraffin wax, Fischer-Tropsch wax, oxides thereof, carnauba wax, and montan wax. , Sasol waxes and their deacidified waxes, ester waxes such as fatty acid ester waxes, fatty acid amides, fatty acids, higher alcohols, fatty acid metal salts and the like.
The softening point of the releasing agent is measured under the same conditions as the softening point of the amorphous polyester resin (B).

Polyolefin waxes include (co)polymers of olefins (ethylene, propylene, 1-butene, isobutylene, 1-hexene, 1-dodecene, 1-octadecene, mixtures thereof, etc.) [those obtained by (co)polymerization and (e.g. low molecular weight polypropylene, low molecular weight polyethylene, low molecular weight polypropylene polyethylene copolymers), oxides of olefin (co)polymers with oxygen and/or ozone, olefin (co)polymers Combined modified maleic acid [maleic acid and its derivatives (maleic anhydride, monomethyl maleate, monobutyl maleate, dimethyl maleate, etc.) modified products], olefins and unsaturated carboxylic acids [(meth)acrylic acid, itaconic acid and maleic anhydride, etc.] and/or unsaturated carboxylic acid alkyl esters [(meth)acrylic acid alkyl esters (alkyl having 1 to 18 carbon atoms) and maleic acid alkyl esters (alkyl having 1 to 18 carbon atoms)], etc. and Sasol wax.

Among the above, microcrystalline wax, paraffin wax, Fischer-Tropsch wax, carnauba wax, ester wax, and amide wax are preferred from the viewpoint of low-temperature fixability and hot offset resistance.

The charge control agent may contain either a positively chargeable charge control agent or a negatively chargeable charge control agent. Salts, polyamines, imidazole derivatives, polymers containing quaternary ammonium groups, metal-containing azo dyes, copper phthalocyanine dyes, metal salicylates, boron complexes of benzylic acid, polymers containing sulfonic acid groups, fluorine-containing polymers and halogen-substituted aromatics A ring-containing polymer and the like can be mentioned.

Examples of fluidizing agents include silica, titania, alumina, calcium carbonate, fatty acid metal salts, silicone resin particles and fluororesin particles, and two or more of them may be used in combination. Silica is preferable from the viewpoint of charging property of the toner. Silica is preferably hydrophobic silica from the viewpoint of toner transferability.

When the toner binder of the present invention is used as a toner, the composition ratio of the toner is preferably 30 to 97% by weight, more preferably 40 to 95% by weight, particularly preferably 40 to 95% by weight, based on the weight of the toner binder of the present invention. 45 to 92% by weight.
The colorant is preferably 0.05 to 60% by weight, more preferably 0.1 to 55% by weight, particularly preferably 0.5 to 50% by weight, based on the weight of the toner.
The amount of the releasing agent is preferably 0 to 30% by weight, more preferably 0.5 to 20% by weight, particularly preferably 1 to 10% by weight, based on the weight of the toner.
The amount of the charge control agent is preferably 0-20% by weight, more preferably 0.1-10% by weight, particularly preferably 0.5-7.5% by weight, based on the weight of the toner.
The fluidizing agent is preferably 0-10% by weight, more preferably 0-5% by weight, particularly preferably 0.1-4% by weight, based on the weight of the toner.
The total content of additives is preferably 3-70% by weight, more preferably 4-58% by weight, particularly preferably 5-50% by weight, based on the weight of the toner.
When the composition ratio of the toner is within the above range, it is possible to easily obtain a toner having good chargeability.

When the toner binder of the present invention is used as a toner, the method for producing the toner is not particularly limited, and may be any of a kneading pulverization method, an emulsion phase inversion method, an emulsion polymerization method, a suspension polymerization method, a dissolution suspension method, an emulsion aggregation method, and the like. It may be obtained by the method of.
Among these production methods, the kneading pulverization method and the dissolution suspension method are preferred from the viewpoint of productivity, low-temperature fixability and storage stability.

For example, when a toner is obtained by a kneading pulverization method, the components constituting the toner except the fluidizing agent are dry-blended with a Henschel mixer, a Nauta mixer, a Banbury mixer, or the like, followed by a twin-screw kneader, an extruder, a continuous kneader and It is melted and kneaded with a continuous mixing device such as a three-roll mill, then coarsely pulverized with a mill or the like, finally pulverized using an air flow pulverizer or the like, and then the particle size distribution is determined with a classification device such as an elbow jet. By adjusting the volume average particle diameter (D50) to preferably 5 to 20 μm, fine particles can be mixed with a fluidizing agent for production. The volume average particle diameter (D50) is measured using a Coulter counter [eg, trade name: Multisizer III (manufactured by Coulter)].
Specifically, 0.1 to 5 mL of a surfactant (alkylbenzenesulfonate) as a dispersant is added to 100 to 150 mL of ISOTON-II (manufactured by Beckman Coulter, Inc.), which is an electrolytic aqueous solution. Further, 2 to 20 mg of a sample to be measured is added, and the electrolytic solution in which the sample is suspended is subjected to dispersion treatment for about 1 to 3 minutes with an ultrasonic disperser. , the number is measured, and the volume distribution and the number distribution are calculated. From the obtained distribution, the volume average particle diameter (D50) (μm), number average particle diameter (μm), and particle size distribution (volume average particle diameter/number average particle diameter) of the toner particles are determined.

When the toner is obtained by the emulsification phase inversion method, it can be manufactured by dissolving or dispersing the components constituting the toner, excluding the fluidizing agent, in an organic solvent, emulsifying the emulsion by adding water or the like, and then separating and classifying the emulsion. The volume average particle diameter of the toner is preferably 3 to 15 μm.

Known methods [methods described in JP-B-36-10231, JP-B-47-518305, JP-B-51-14895, etc.] can be used for emulsion polymerization and suspension polymerization.

Known methods [methods described in Japanese Patent No. 3596104, Japanese Patent No. 3492748, etc.] can be used as the dissolution suspension method and the emulsion aggregation method.

The toner used in the toner binder of the present invention is carrier particles such as iron powder, glass beads, nickel powder, ferrite, magnetite, and ferrite whose surface is coated with resin (acrylic polymer, silicone polymer, etc.), if necessary. used as a developer for latent electrical images. The weight ratio of toner to carrier particles is from 1/99 to 100/0. It is also possible to form an electric latent image by friction with a member such as a charging blade instead of carrier particles.

The toner binder of the present invention is used as a recording material by being fixed on a support (paper, polyester film, etc.) by a copying machine, a printer, etc., as an electrophotographic toner. As a method for fixing onto the support, a known hot roll fixing method, flash fixing method, and the like can be applied.

EXAMPLES The present invention will be further described below with reference to Examples and Comparative Examples, but the present invention is not limited to these. Hereinafter, parts are by weight unless otherwise specified.

<Production Example 1>
An autoclave was charged with 30 parts of toluene, purged with nitrogen, and heated to 170°C. Then, at the same temperature, 64 parts of behenyl acrylate as monomer (a), 18 parts of styrene as monomer (c), 18 parts of acrylonitrile as monomer (b), and 0 parts of di-t-butyl peroxide A mixed solution of 7 parts and 10 parts of toluene was added dropwise at the same temperature over 3 hours, and the temperature was maintained at the same temperature for 1 hour to obtain a toluene solution of vinyl resin (A1). Next, in the obtained toluene solution, toluene is removed at 1 kPa or less, and after confirming that the toluene in the resin is 100 ppm or less by gas chromatography, it is taken out. A vinyl resin (A1) was obtained by conditioning the humidity for 48 hours.
The hydrogen bond term (dH) of the Hansen solubility parameter (HSP) of the monomer (b) used, the weight average molecular weight, melting point, dielectric constant, water content and acid value of the vinyl resin (A1) are shown in Table 1. .

<Production Examples 2 to 10>
Vinyl resins (A2) to (A10) were obtained in the same manner as in Production Example 1 except that the weight parts of the monomers and other raw materials shown in Table 1 were specified. The physical properties are shown in Table 1, respectively.

<Production Example 11>
2040 parts behenic acid, 2067 parts vinyl acetate, 0.044 parts palladium chloride, 0.10 parts lithium bromide, and 0.984 parts trisodium phosphate are placed in a four-necked flask equipped with stirring and reflux condenser and thermometer. After charging and reacting at 70° C. for 40 hours while stirring, 1527 parts of vinyl behenate was obtained by distillation under reduced pressure.

<Production Example 12>
An autoclave was charged with 30 parts of toluene, purged with nitrogen, and heated to 170°C. Then, at the same temperature, 68 parts of the vinyl behenate obtained in Production Example 11 as the monomer (a), 18 parts of styrene as the monomer (c), 18 parts of acrylonitrile as the monomer (b), A mixed solution of 1.1 parts of t-butyl peroxide and 10 parts of toluene was added dropwise at the same temperature over 3 hours, and the mixture was maintained at the same temperature for 1 hour to obtain a toluene solution of vinyl resin (A11). . Next, in the obtained toluene solution, toluene is removed at 1 kPa or less, and after confirming that the toluene in the resin is 100 ppm or less by gas chromatography, it is taken out. A vinyl resin (A11) was obtained by conditioning the humidity for 48 hours.
The hydrogen bond term (dH) of the Hansen solubility parameter (HSP) of the monomer (b) used, the weight average molecular weight, melting point, dielectric constant, water content and acid value of the vinyl resin (A11) are shown in Table 1. .

<Production Example 13>
An autoclave equipped with a stirrer was charged with 100 parts of xylene, 100 parts of behenyl acrylate as monomer (a), and 1.5 parts of thioglycolic acid. . 0.80 parts of di-t-butyl peroxide [Azo V65, Fuji Film Wako Pure Chemical Industries, Ltd.; did After that, the temperature was further raised to 105°C, stirred at 105°C for 1 hour, and then cooled to 30°C. After cooling, 2.5 parts of hydroxyethyl methacrylate (manufactured by Tokyo Kasei Kogyo Co., Ltd.), which is the monomer (b), was added to the reaction vessel and heated to 55°C. Co., Ltd.) 4 parts, 4-methylaminopyridine (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.1 part, t-Bu hydroquinone (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.1 part dissolved in 20 parts of chloroform The resulting mixture was added dropwise over 1 hour. After that, the mixture was further stirred at 55°C for 5 hours. After that, the solution was cooled to 35° C. and the solid matter was removed, and the dissolved matter was purified by methanol precipitation. The obtained solid content was dried under reduced pressure to obtain a white solid monomer. The white solid monomer had a weight average molecular weight of 6,000 and a melting point of 65°C. The weight average molecular weight and melting point were measured in the same manner as the vinyl resin (A).
Next, another autoclave was charged with 30 parts of toluene, purged with nitrogen, and heated to 170°C. Then, at the same temperature, 64 parts of a white solid monomer, 18 parts of styrene as the monomer (c), 18 parts of acrylonitrile as the monomer (b), 0.7 parts of di-t-butyl peroxide and 10 parts of toluene was added dropwise over 3 hours at the same temperature, and further maintained at the same temperature for 1 hour to obtain a xylene solution of vinyl resin (A12). Next, in the obtained toluene solution, toluene is removed at 1 kPa or less, and after confirming that the toluene in the resin is 100 ppm or less by gas chromatography, it is taken out. A vinyl resin (A12) was obtained by conditioning the humidity for 48 hours.
The hydrogen bond term (dH) of the Hansen solubility parameter (HSP) of the monomer (b) used, the weight average molecular weight, melting point, dielectric constant, water content and acid value of the vinyl resin (A12) are shown in Table 1. .

<Production Example 14>
An autoclave equipped with a stirrer was charged with 100 parts of xylene, 100 parts of acrylonitrile as the monomer (b), and 1.8 parts of thioglycolic acid. After purging with nitrogen, the autoclave was heated to 85° C. under stirring and sealed. 1.05 parts of di-t-butyl peroxide [Azo V65, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., the same shall apply hereinafter] was charged, and the temperature inside the autoclave was maintained at 85° C. while controlling the same temperature for 3 hours to polymerize. did After that, the temperature was further raised to 105°C, stirred at 105°C for 1 hour, and then cooled to 30°C. After cooling, 1.9 parts of hydroxyethyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), which is the monomer (b), is added to the reaction vessel and heated to 55 ° C., then cyclohexylcarbodiimide (Tokyo Chemical Industry Co., Ltd. Co., Ltd.) 3.1 parts, 0.1 part of 4-methylaminopyridine (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.1 part of t-Bu hydroquinone (manufactured by Tokyo Chemical Industry Co., Ltd.) 20 parts of chloroform was added dropwise over 1 hour. After that, the mixture was further stirred at 55°C for 5 hours. After that, it was cooled to 35° C. and purified by a methanol precipitation method. The obtained solid content was dried under reduced pressure to obtain a white solid monomer. The white solid monomer had a weight average molecular weight of 9,300 and a glass transition point of 55°C. The weight average molecular weight and melting point were measured in the same manner as for the vinyl resin.
Further, another autoclave was charged with 30 parts of toluene, purged with nitrogen, and heated to 170°C. Then, at the same temperature, 64 parts of behenyl acrylate, 18 parts of styrene as monomer (c), 18 parts of white solid monomer as monomer (b), 0.7 parts of di-t-butyl peroxide and 10 parts of toluene were added. Part of the mixed solution was added dropwise at the same temperature over 3 hours, and further held at the same temperature for 1 hour to obtain a xylene solution of the vinyl resin (A13). Next, in the obtained toluene solution, toluene is removed at 1 kPa or less, and after confirming that the toluene in the resin is 100 ppm or less by gas chromatography, it is taken out. A vinyl resin (A13) was obtained by conditioning the humidity for 48 hours.
The hydrogen bond term (dH) of the Hansen solubility parameter (HSP) of the monomer (b) used, the weight average molecular weight, melting point, dielectric constant, water content and acid value of the vinyl resin (A13) are shown in Table 1. .

In Table 1, the value of the hydrogen bond term (dH) of the Hansen solubility parameter (HSP) of the monomer (b) is shown in parentheses following the compound name of the monomer (b).
In addition, the (dH) of the monomer (b) constituting the vinyl resin (A) described in the physical properties column is When there are two or more monomers (b), the average value of (dH) of the monomers (b) used is calculated based on the weight ratio of the monomers (b).

<Comparative Production Examples 1 to 5>
Vinyl resins (A'1) to (A'5) were obtained in the same manner as in Production Example 1, except that the weight parts of the monomers and other raw materials shown in Table 2 were specified. The physical properties are shown in Table 2, respectively.

<Production Example 15>
In a reaction vessel equipped with a condenser, stirrer and nitrogen inlet, 365 parts of EO2 molar adduct of bisphenol A, 339 parts of PO2 molar adduct of bisphenol A, 266 parts of terephthalic acid, 8 parts of adipic acid, trimellitic anhydride. Add 29 parts of an acid and 2.5 parts of titanium diisopropoxybistriethanolamine as a condensation catalyst, and react at 230° C. under a stream of nitrogen for 4 hours while distilling off the water produced at 0.5 to 2.5 kPa. After reacting for 5 hours under reduced pressure of , the mixture was taken out to obtain an amorphous polyester resin (B1). Physical properties are shown in Table 3.

<Production Example 16>
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen inlet, 752 parts of PO2 molar adduct of bisphenol A, 313 parts of terephthalic acid, 1 part of fumaric acid, 1 part of trimellitic anhydride, and titanium diiso as a condensation catalyst. Add 2.5 parts of propoxybistriethanolamine, react at 230° C. under a nitrogen stream for 4 hours while distilling off the generated water, and react for 5 hours under reduced pressure of 0.5 to 2.5 kPa. It was taken out to obtain an amorphous polyester resin (B2). Physical properties are shown in Table 3.

<Example 1> [Preparation of toner (T-1)]
80 parts of a vinyl resin (A1) as a toner binder, 9 parts of an amorphous polyester resin (B1), 6 parts of carbon black [manufactured by Mitsubishi Chemical Corporation, MA-100] as a colorant, and carnauba wax as a release agent [ Carnauba wax manufactured by Nippon Wax Co., Ltd.] and 4 parts of Eizenspirone Black [T-77 manufactured by Hodogaya Chemical Co., Ltd.] as a charge control agent were added to obtain a toner by the following method. First, the mixture was premixed using a Henschel mixer [FM10B manufactured by Nippon Coke Kogyo Co., Ltd.], and then kneaded with a twin-screw kneader [PCM-30 manufactured by Ikegai Co., Ltd.]. Then, after pulverizing using an air stream type fine pulverizer [KJ-25 manufactured by Kurimoto, Ltd.], it is classified with an elbow jet classifier [EJ-L-3 (LABO) type manufactured by Matsubo Co., Ltd.], Toner particles having a volume average particle diameter (D50) of 8 μm were obtained.
Then, 1 part of hydrophobic silica [Aerosil R972, manufactured by Nippon Aerosil Co., Ltd.] as a fluidizing agent was mixed with 99 parts of the toner particles using a sample mill to obtain toner (T-1) of the present invention.

<Examples 2 to 19>
[Preparation of Toners (T-2) to (T-19)]
Toners (T-2) to (T-19) were obtained in the same manner as in Example 1 except that the vinyl resin (A) and the amorphous polyester resin (B) shown in Table 4 were used in the specified parts by weight. rice field.

<Comparative Examples 1 to 7>
[Preparation of toner (T'-1) to (T'-7)]
Toners (T'-1) to (T'-7) were prepared in the same manner as in Example 1 except that the vinyl resin (A) and the amorphous polyester resin (B) shown in Table 5 were used in the specified parts by weight. got

[Performance evaluation]
The low-temperature fixability, storage stability, hot offset resistance, and charging stability of the obtained toner were measured, evaluated, and determined by the following methods. The results are shown in Tables 4 and 5.

<Low temperature fixability>
The toner is evenly placed on the surface of the paper so as to be 0.8 mg/cm ² . At this time, the method of placing the powder on the paper surface uses a printer without a heat fixing device. Other methods may be used as long as the powder can be uniformly placed at the above weight density.
This paper was passed through a pressure roller at a fixing speed (heating roller peripheral speed) of 213 mm/sec and a fixing pressure (pressure roller pressure) of 10 kg/cm ² , and the temperature at which cold offset occurred (MFT) was measured.
The lower the temperature at which cold offset occurs, the better the low-temperature fixability. This evaluation condition generally requires a temperature of 125°C or less

<Storage stability>
The toner was allowed to stand for 15 hours in a dryer controlled to a temperature of 50° C. and a humidity of 80%.
[criterion]
○: Blocking does not occur ×: Blocking occurs

<Hot offset resistance>
The toner is evenly placed on the surface of the paper so as to be 0.6 mg/cm ² . At this time, a printer without a heat fixing device was used as a method of placing the toner on the paper surface. The hot offset temperature was measured when this paper was passed through a pressure roller under the conditions of a fixing speed (heating roller circumferential speed) of 213 mm/sec and a fixing pressure (pressure roller pressure) of 5 kg/cm ² .
This evaluation condition generally requires a temperature of 180° C. or higher.

<Electrification stability>
0.5 g of toner and 20 g of ferrite carrier (F-150, manufactured by Powdertech Co., Ltd.) are placed in a 50 ml glass bottle and conditioned at relative humidity (1) 50% and (2) 85% for 8 hours or more.
The mixture was friction-stirred at 50 rpm for 10 and 60 minutes using a Turbula shaker mixer, and the charge amount was measured at each time. A blow-off charge amount measuring device [manufactured by Toshiba Chemical Co., Ltd.] was used for the measurement. The charge amount obtained when the relative humidity was 50% and the friction time was 10 minutes was defined as the saturated charge amount. In addition, "charge amount at 85% relative humidity for 60 minutes of friction/charge amount at 50% relative humidity for 60 minutes" was calculated and used as an index of charging stability.
This evaluation condition generally requires a numerical value of 0.40 or more.

As is clear from the evaluation results in Tables 4 and 5, the toners using the toner binder of the present invention (Examples 1 to 19) have better low-temperature fixability than the comparative toners (Comparative Examples 1 to 7). A result was obtained in which both the storage stability and the hot offset resistance and the charging stability were remarkably good.

A toner using the toner binder of the present invention is excellent in low-temperature fixability, hot offset resistance, and storage stability, and is therefore useful as a toner for developing electrostatic images used in electrophotography, electrostatic recording, electrostatic printing, and the like. .

Claims (3)

A vinyl resin (A) having a monomer (a) as an essential constituent monomer and an amorphous polyester resin (B) having an alcohol component (x) and a carboxylic acid component (y) as essential constituent monomers In the toner binder containing, the monomer (a) is a (meth)acrylate having 21 to 40 carbon atoms having a chain hydrocarbon group and/or a vinyl having 21 to 40 carbon atoms having a chain hydrocarbon group is an ester,
The vinyl resin (A) has a melting point measured by DSC of 40 to 80°C,
The vinyl resin (A) has a dielectric constant ε' of 2.5 to 4.0,
The amount of water contained in the vinyl resin (A) is 500 to 10000 ppm,
The vinyl resin (A) has an acid value of 19.9 mgKOH/g or less,
The polymerization ratio of the vinyl resin (A) is 21 to 99% by weight based on the weight of the toner binder,
A toner binder characterized in that the polymerization ratio of the monomer (a) is 15 to 90% by weight based on the total weight of the monomers constituting the vinyl resin (A). The vinyl resin (A) has a monomer (b) other than the monomer (a) as a constituent monomer, and the hydrogen bond term (dH) of the Hansen solubility parameter (HSP) of the monomer (b) is 2. The toner binder according to claim 1, which is 5.0 or more and 15.0 or less. 3. The toner binder according to claim 1, wherein the amorphous polyester resin (B) has a softening point of 90 to 144.degree.