JP7256679B2 - 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.
It is known that using a crystalline resin in a conventional toner binder in order to achieve the appropriate change in storage modulus described above improves the low-temperature fixability and glossiness of the toner due to the melting characteristics of the crystalline resin. It is
However, if the content of the crystalline resin is increased relative to the amorphous resin used in conventional toner binders, the strength of the resin may decrease. The melting point and/or glass transition point of the toner is lowered due to the compatibility of the amorphous resin with the amorphous resin, which causes a problem in achieving compatibility between low-temperature fixability, hot offset resistance, and storage stability.

On the other hand, a method of reproducing the crystallinity of a crystalline resin by performing a heat treatment after the melt-kneading process (Patent Document 1) achieves both low-temperature fixability and hot offset resistance by hybridizing and cross-linking a polyester resin and a vinyl resin. A method (Patent Document 2) has been proposed.
However, polyester resin-based toner binders often sacrifice glossiness in order to achieve both low-temperature fixability and hot-offset resistance. Measures such as increasing the nip pressure at the time of fixing are required, and it is difficult to satisfy the original low temperature fixability and hot offset resistance.

JP 2005-308995 A JP 2012-002976 A

SUMMARY OF THE INVENTION An object of the present invention is to provide a toner binder that is excellent in low temperature fixability, hot offset resistance, storage stability and glossiness.

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 toner binder containing a vinyl resin (A) having the monomer (a) as an essential constituent monomer, wherein the monomer (a) is a chain hydrocarbon having 18 to 36 carbon atoms. and a vinyl group, the melting peak temperature Tm of the vinyl resin (A) measured by DSC is 40 to 100° C., and the polymerization ratio of the vinyl resin (A) is 21 to 99% by weight based on the weight of the toner binder. %, 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), and the acid value of the vinyl resin (A) is 19.0%. 9 mg KOH / g or less, the loss tangent tan δ (Tm-10) of the vinyl resin (A) at (Tm-10) ° C. is 0.01 to 2.0, and the vinyl resin (A) at (Tm + 20) ° C. The toner binder is characterized by having a loss tangent tan δ (Tm+20) of 0.5 to 30.0.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a toner binder used for a toner excellent in low temperature fixability, hot offset resistance, storage stability and glossiness.

The present invention will be described in detail below.
The toner binder of the present invention is a toner binder containing a vinyl resin (A) having the monomer (a) as an essential constituent monomer, wherein the monomer (a) is a chain having 18 to 36 carbon atoms. It has a hydrocarbon group and a vinyl group, the melting peak temperature Tm of the vinyl resin (A) measured by DSC is 40 to 100° C., and the weight ratio of the vinyl resin (A) is 21 to 21 to the weight of the toner binder. 99% by weight, 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), and the acid value of the vinyl resin (A) is 19.9 mg KOH / g or less, the loss tangent tan δ (Tm-10) at (Tm-10) ° C. of the vinyl resin (A) is 0.01 to 2.0, and the vinyl resin (A) (Tm + 20) The loss tangent tan δ (Tm+20) at °C is 0.5 to 30.0.

The monomer (a) is a monomer having a chain hydrocarbon group having 18 to 36 carbon atoms and a vinyl group. Examples of the monomer having a chain hydrocarbon group having 18 to 36 carbon atoms and a vinyl group include (meth)acrylate having a chain hydrocarbon group having 18 to 36 carbon atoms and chain carbonization having 18 to 36 carbon atoms. Examples include vinyl esters having a hydrogen group. In the present invention, "(meth)acrylate" means "acrylate" and/or "methacrylate".
Examples of (meth)acrylates having a chain hydrocarbon group having 18 to 36 carbon atoms include (meth)acrylates having a linear alkyl group having 18 to 36 carbon atoms [e.g., octadecyl (meth)acrylate, nonadecyl (meth)acrylate , arachidyl (meth)acrylate, heneicosanyl (meth)acrylate, behenyl (meth)acrylate, lignoceryl (meth)acrylate, ceryl (meth)acrylate, montanyl (meth)acrylate, myricyl (meth)acrylate and dotriaconta (meth)acrylate, etc.] and (meth)acrylates having a branched alkyl group having 18 to 36 carbon atoms [2-decyltetradecyl (meth)acrylate, etc.].
Vinyl esters having a chain hydrocarbon group of 18 to 36 carbon atoms include vinyl esters having a linear alkyl group of 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, (A) from the viewpoint of low-temperature fixability and storage stability of the toner is preferably a (meth)acrylate having a linear alkyl group having 18 to 36 carbon atoms, more preferably 18 to 30 carbon atoms. A (meth)acrylate having a linear alkyl group of , more preferably a (meth)acrylate having a linear alkyl group of 18 to 24, particularly preferably a linear alkyl group of 20 to 24 are (meth)acrylates with the most preferred being arachidyl acrylate, behenyl acrylate and lignoceryl acrylate.
Monomer (a) may be used alone or in combination of two or more.

The weight ratio of the monomer (a) in the monomers constituting the vinyl resin (A) is based on the total weight of the monomers constituting the vinyl resin (A), and the low-temperature fixability and hot offset resistance are from the viewpoint of 15 to 90% by weight. It is preferably 18 to 80% by weight, more preferably 20 to 70% by weight, still more preferably 23 to 60% by weight, and particularly preferably 25 to 50% 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.

As a constituent monomer, the vinyl resin (A) further contains at least one selected from the group consisting of an ester group, a carboxyl group, a nitrile group, a urethane group, a urea group, and an amide group, from the viewpoint of hot offset resistance of the toner. It is preferable to include a monomer (b) other than the monomer (a), which is a monomer having a functional group and an ethylenically unsaturated bond.

The functional group possessed by the monomer (b) is a functional group with a high degree of aggregation or a functional group with a high polarity. By raising the temperature Tm to improve the storage stability, or by raising the high-temperature elasticity, the fixation width of the toner and the hot offset resistance can be improved.

Examples of the monomer (b) include a monomer having an ester group (b1), a monomer having a carboxyl group (b2), a monomer having a nitrile group (b3), and a monomer having a urethane group. (b4), a monomer (b5) having a urea group, and a monomer (b6) having an amide group. Monomer (b) may be used alone or in combination of two or more.

Examples of the ester group-containing monomer (b1) include methyl acrylate, ethyl acrylate, propyl acrylate, methyl methacrylate, vinyl acetate, vinyl propionate, hydroxyethyl (meth)acrylate, and hydroxy(meth)acrylate. Propyl (2-hydroxypropyl ester and 2-hydroxy-1-methylethyl ester and the like can be mentioned.

Examples of the monomer (b2) having a carboxyl group include (meth)acrylic acid, crotonic acid, cinnamic acid, (anhydrous) maleic acid, fumaric acid, itaconic acid, citraconic acid, monoalkyl maleate, and monoalkyl fumarate. esters, itaconic acid monoalkyl esters and citraconic acid monoalkyl esters, 2-propenoic acid, 3-butenoic acid, 4-pentenoic acid, 5-hexenoic acid, 6-heptenoic acid, 7-octenoic acid, 8-nonenoic acid, 9 -decenoic acid, 10-undecenoic acid and 11-tridecenoic acid.

Examples of the nitrile group-containing monomer (b3) include acrylonitrile and methacrylonitrile.

As the monomer (b4) having a urethane group, an alcohol having an ethylenically unsaturated bond and a monomer obtained by reacting an isocyanate by a known method, and an alcohol and an isocyanate having an ethylenically unsaturated bond. is a monomer obtained by reacting with a known method, and examples thereof include reaction products of methanol and 2-isocyanatoethyl methacrylate.

As the urea group-containing monomer (b5), a monomer obtained by reacting an amine having an ethylenically unsaturated bond with an isocyanate by a known method, and an amine and an isocyanate having an ethylenically unsaturated bond. is a monomer obtained by reacting with a known method, and examples thereof include reaction products of dibutylamine and 2-isocyanatoethyl methacrylate.

Examples of the amide group-containing monomer (b6) include monomers obtained by reacting ammonia or an amine having 1 to 8 carbon atoms with acrylic acid or methacrylic acid by a known method.

Among the above monomers (b), from the viewpoint of compatibility between low-temperature fixability and storage stability, methyl acrylate, acrylonitrile, methacrylonitrile, vinyl acetate, hydroxyethyl (meth)acrylate, and hydroxy(meth)acrylate Propyl, (meth)acrylic acid, maleic anhydride, vinyl propionate, a reaction product of methanol and 2-isocyanatoethyl methacrylate, and (meth)acrylamide, more preferably methyl acrylate, acrylonitrile, methacrylonitrile, and vinyl acetate , hydroxypropyl (meth)acrylate, (meth)acrylic acid, maleic anhydride, vinyl propionate, reaction products of methanol and 2-isocyanatoethyl methacrylate, and (meth)acrylamide.

The weight ratio of the monomer (b) in the monomers composing the vinyl resin (A) is the total weight of the monomers composing the vinyl resin (A) from the viewpoint of low-temperature fixability and hot offset resistance. based on, preferably 10 to 85% by weight, more preferably 20 to 78% by weight, still more preferably 30 to 75% by weight, particularly preferably 40 to 72% by weight, most preferably 50 to 70% by weight.

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 60:40 to 15:85, still more preferably 40:60 to 15:85.

The vinyl resin (A) may contain a monomer (c) other than the monomers (a) and (b) as constituent monomers in addition to the monomers (a) and (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 monomers (a) and (b). (eg α-methylstyrene and p-methylstyrene) and the like. 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. It is preferably not more than 5% by weight, based on the total weight of the body.

The vinyl resin (A) in the present invention is a known monomer composition containing a monomer (a), optionally a monomer (b), and optionally a monomer (c). It can be produced by polymerization by a method (such as the method described in JP-A-5-117330). For example, a solution in which the monomer is reacted with a radical initiator (di-t-butyl peroxide, t-butylperoxy-2-ethylhexanoate, azobisisobutyronitrile, etc.) in a solvent (toluene, etc.) It can be synthesized by a polymerization method.

The acid value of the vinyl resin (A) in the present invention is 19.9 mgKOH/g or less. If the acid value is more than 19.9 mgKOH/g, the storage stability is deteriorated due to increased hygroscopicity. The acid value of the vinyl resin (A) is preferably 0-15 mgKOH/g, more preferably 0-10 mgKOH/g.

The acid value of the vinyl resin (A) can be adjusted by the content of the monomer (b2) having a carboxyl group. The acid value of (A) is measured by a method such as JIS K 0070, for example.

In the present invention, the melting peak temperature (Tm) of the vinyl resin (A) measured by DSC is preferably 40 to 100° C., more preferably 40 to 100° C., from the viewpoint of crystallinity, low-temperature fixability, and storage stability when used as a toner. is 45-85°C, more preferably 50-70. When the melting peak temperature is 40° C. or higher, the crystallinity and storage stability are good, and when it is 100° C. or lower, the low-temperature fixability is good.
Tm is determined by adjusting the type and composition ratio of the monomers constituting (A) (for example, adjusting the number of carbon atoms in the monomer (a) constituting the vinyl resin (A) and the monomer constituting (A) The weight ratio of (a) can be adjusted, etc.), the weight average molecular weight (for example, the weight average molecular weight of the vinyl resin (A) can be adjusted to 10,000 to 1,000,000, etc.). For example, Tm can be increased by increasing the number of carbon atoms in (a), increasing the weight ratio of (a), or the like.

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 Hold for minutes (6) Heat up to 150°C at 10°C/min (7) Analyze each endothermic peak of the differential scanning calorimetry curve measured in the process of (6).

The weight-average molecular weight of the vinyl resin (A) in the present invention is preferably from 10,000 to 1,000,000, more preferably from 101,000 to 800,000, from the viewpoint of low temperature fixability and hot offset resistance of the toner. is. The weight average molecular weight of the vinyl resin (A) can be adjusted by the polymerization temperature, amount of radical polymerization initiator, chain transfer agent and the like.

The number average molecular weight of the vinyl resin (A) in the present invention is preferably 1,000 to 500,000, more preferably 3,000 to 400,000, most preferably 3,000 to 400,000, and most Preferably it is 4,500 to 85,000. The weight average molecular weight of the vinyl resin (A) can be adjusted by the polymerization temperature, amount of radical polymerization initiator, chain transfer agent and the like.

The ratio [Mw/Mn] of the number average molecular weight to the weight average molecular weight of the vinyl resin (A) in the present invention is preferably 2.2 or more, more preferably 2.2 or more, from the viewpoint of low temperature fixability and hot offset resistance of the toner. 2.2 to 40.0, most preferably 2.6 to 32.3. [Mw/Mn] can be adjusted by increasing or decreasing the molecular weight between cross-linking points by using a cross-linking agent.

The weight average molecular weight and number average molecular weight of the vinyl resin (A) are 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 material: 12 standard polystyrene (TSK standard POLYSTYRENE) (weight average molecular weight: 500 1050 2800 5970 9100 18100 37900 96400 190000 355000 1090000 2890000) [manufactured by Tosoh Corporation]

The vinyl resin (A) has a loss tangent tan δ (Tm-10) at (Tm-10)°C of 0.01 to 2.0, preferably 0.05 to 2.0.

The vinyl resin (A) has a loss tangent tan δ (Tm+20) at (Tm+20)° C. of 0.5 to 30.0, preferably 0.8 to 20.0.

Here, the loss tangent tan δ is a physical property indicated by the ratio (G''/G') of the loss modulus (G'') to the storage modulus (G').
In general, the storage elastic modulus (G') (unit: Pa) represents elasticity, and is an index of the force that is stored to return when deformed by an external force. On the other hand, the loss elastic modulus (G'') (unit: Pa) represents the viscosity, and is an index of the force that follows the force applied and loses heat when deformed by the force applied from the outside. Therefore, it can be said that the loss tangent tan δ is an index representing the balance between viscosity and elasticity.

When the vinyl resin (A) has a loss tangent tan δ (Tm-10) of 0.01 to 2.0, the toner has good low-temperature fixability and storage stability. If it is less than 0.01, the elasticity is too high for the viscosity, so deformation by a roller during heating is difficult to occur, resulting in poor low-temperature fixability. For example, the degree of crystallinity of the vinyl resin (A) is increased by increasing the molecular weight of the vinyl resin (A), the degree of crystallinity of the vinyl resin (A) is increased by a method such as annealing, the monomer (b) The loss tangent tan δ (Tm-10) can be lowered by a method such as using together or increasing the weight ratio of the monomer (b).

When the loss tangent tan δ (Tm+20) of the vinyl resin (A) is 0.5 to 30.0, the smoothness (glossiness) and hot offset resistance of the toner-fixed image are well balanced between viscosity and elasticity. represent.
If the loss tangent tan δ (Tm+20) is less than 0.5, the elasticity with respect to viscosity is too high, resulting in poor glossiness. Offset performance deteriorates. For example, the loss tangent tan δ (Tm+20) can be lowered by increasing the molecular weight of the vinyl resin (A), increasing the molecular weight distribution, increasing the ratio of the monomer (a), or the like.

In the present invention, the vinyl resin (A) preferably satisfies the relational expression (1) from the viewpoint of storage stability and low-temperature fixability when used as a toner.
Relational expression (1): 1.6 ≤ ln (G' _Tm-10 ) / ln (G' _{Tm + 30} ) ≤ 3.4
However, the calculated value shall be obtained by rounding off to the second decimal place.
More preferably, it satisfies the relational expression (1-1), and more preferably satisfies the relational expression (1-2).
Relational expression (1-1): 1.6 ≤ ln (G' _Tm-10 ) / ln (G' _{Tm + 30} ) ≤ 3.0
Relational expression (1-2): 1.6 ≤ ln (G' _Tm-10 ) / ln (G' _{Tm + 30} ) ≤ 2.7

In relational expressions (1), (1-1), and (1-2), G' _Tm-10 is the storage elasticity of (A) when the temperature of the vinyl resin (A) is (Tm-10) ° C. is the modulus (Pa) and G' _Tm+30 is the storage modulus (Pa) of (A) when the temperature of (A) is (Tm+30)°C. ln(G' _Tm-10 )/ln(G' _Tm+30 ) can be adjusted by the weight average molecular weight of (A) and the types or amounts of monomers (a), (b) and (c). For example, ln( _G'Tm-10 )/ln( _G'Tm+30 ) by reducing the weight average molecular weight of (A), increasing the amount of (a), or reducing the amount of (b) or (c) can be raised.

The loss tangent tan δ, storage elastic modulus G′ and loss elastic modulus G″ of the vinyl resin (A) in the present invention, and the storage elastic modulus G′ and loss elastic modulus G″ of the toner binder to be described later, were measured using the following viscoelasticity measuring apparatus. It is a value measured under the following conditions using
Apparatus: ARES-24A (manufactured by Rheometric Co.)
Jig: 25mm parallel plate Frequency: 1Hz
Distortion rate: 5%
Heating rate: 5°C/min

From the viewpoint of storage stability, the toner binder of the present invention preferably contains an amorphous polyester resin (B) as a toner binder polymer other than the vinyl resin (A). The amorphous polyester resin (B) is preferably an amorphous polyester resin containing an alcohol component (x) and a carboxylic acid component (y) as essential components. The composition of the resin is not particularly limited. In the present invention, the term "amorphous" means that there is no melting peak temperature when the transition temperature of the sample is measured using a differential scanning calorimeter under the same conditions as in the case of the vinyl resin (A). means.

Examples of the alcohol component (x) include diols and trivalent or higher polyols. (x) may be used alone or in combination of two or more.

Diols include alkylene glycols having 2 to 36 carbon atoms (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, 1, 9-nonanediol, 1,10-decanediol, and 1,12-dodecanediol), alkylene ether glycols having 4 to 36 carbon atoms (diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol and polytetra methylene ether glycol, etc.), alicyclic diols having 6 to 36 carbon atoms (1,4-cyclohexanedimethanol and hydrogenated bisphenol A, etc.), (poly)alkylene oxide adducts of the above alicyclic diols (preferably addition molar Numbers 1 to 30), and alkylene oxide adducts of aromatic diols [monocyclic dihydric phenol (eg, hydroquinone) and bisphenols].

An alkylene oxide adduct having a bisphenol structure is obtained by adding an alkylene oxide (hereinafter sometimes abbreviated as AO) to a bisphenol. Bisphenols include those represented by the following general formula (1).
HO-Ar-P-Ar-OH (1)
[In the formula, P represents an alkylene group having 1 to 3 carbon atoms, —SO ₂ —, —O—, —S—, or a direct bond, and Ar is a hydrogen atom having a halogen or an alkyl group having 1 to 30 carbon atoms. represents a phenylene group optionally substituted with ]

Bisphenols include, for example, bisphenol A, bisphenol F, bisphenol B, bisphenol AD, bisphenol S, trichlorobisphenol A, tetrachlorobisphenol A, dibromobisphenol F, 2-methylbisphenol A, 2,6-dimethylbisphenol A, 2 , and 2′-diethylbisphenol F, and two or more of these can be used in combination.
The alkylene oxide to be added to these bisphenols is preferably an alkylene oxide having 2 to 4 carbon atoms, and specifically, ethylene oxide (hereinafter, "ethylene oxide" may be abbreviated as EO.), propylene oxide. (hereinafter, "propylene oxide" may be abbreviated as PO), 1,2-, 2,3-, 1,3- or iso-butylene oxide, tetrahydrofuran (hereinafter abbreviated as THF), and two of these Combinations of more than one species are included.

From the viewpoint of heat-resistant storage stability and low-temperature fixability, AO constituting the AO adduct of bisphenols is preferably EO and/or PO. The number of moles of AO to be added is preferably 2 to 30 mol, more preferably 2 to 10 mol, from the viewpoint of heat-resistant storage stability and low-temperature fixability.

Among the alkylene oxide adducts of bisphenols, EO and/or PO adducts of bisphenol A (the number of moles added is preferably 2 to 4, more preferably 2 to 3) is preferable from the viewpoint of toner fixability. be.

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

Of the alcohol components (x), preferred from the viewpoint of achieving both low-temperature fixability and hot offset resistance are alkylene glycols having 2 to 12 carbon atoms, AO adducts of bisphenols (addition mole number is preferably 2 to 30 ), trihydric or higher aliphatic polyhydric alcohols having 3 to 36 carbon atoms and novolac resins (including phenol novolacs and cresol novolaks, the average degree of polymerization is preferably 3 to 60) AO adducts (the number of moles added is 2 to 30), and more preferable from the viewpoint of storage stability are alkylene glycols having 2 to 10 carbon atoms, AO adducts of bisphenols (addition mole number is preferably 2 to 5), 3 to 4 AO adduct (addition mole number is preferably 2 to 30) of a polyhydric aliphatic polyhydric alcohol and novolac resin (including phenol novolak and cresol novolac, etc., preferably 3 to 60 as an average degree of polymerization), and further Preferred are alkylene glycols having 2 to 6 carbon atoms and AO adducts of bisphenol A (addition mole number is preferably 2 to 5), and particularly preferred are ethylene glycol, propylene glycol and AO adducts of bisphenol A (addition The number of moles is preferably 2-3).

From the viewpoint of durability and image quality stability, the amorphous polyester resin (B) in the present invention contains an AO adduct of a bisphenol in the alcohol component (x), preferably 70 moles based on the number of moles of (x). % or more, more preferably 90 mol % or more.

Examples of the carboxylic acid component (y) include dicarboxylic acids and polycarboxylic acids having a valence of 3 or higher. (y) may be used alone or in combination of two or more.
Examples of dicarboxylic acids include alkanedicarboxylic acids having 2 to 50 carbon atoms (oxalic acid, malonic acid, succinic acid, adipic acid, reparginic acid, sebacic acid, etc.), alkene dicarboxylic acids having 4 to 50 carbon atoms (alkenyl acids such as dodecenyl succinic acid). succinic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, glutaconic acid, etc.), aromatic dicarboxylic acids having 8 to 36 carbon atoms (phthalic acid, isophthalic acid, terephthalic acid, naphthalene dicarboxylic acid, etc.), vinyl polymer of saturated carboxylic acid [number average molecular weight (hereinafter referred to as Mn, according to gel permeation chromatography (GPC)): 450 to 10,000] (α-olefin/maleic acid copolymer, etc.); .
Examples of trivalent or higher polycarboxylic acids include aromatic polycarboxylic acids having 9 to 20 carbon atoms (trimellitic acid, pyromellitic acid, etc.), aliphatic tricarboxylic acids having 6 to 36 carbon atoms (hexanetricarboxylic acid, etc.), vinyl polymers of saturated carboxylic acid [Mn: 450 to 10,000] (styrene/maleic acid copolymer, styrene/acrylic acid copolymer, styrene/fumaric acid copolymer, etc.);
(y) may be an anhydride of (y), a lower alkyl (1 to 4 carbon atoms) ester (methyl ester, ethyl ester, isopropyl ester, etc.), or these carboxylic acids may be used in combination. good.

Of the carboxylic acid components (y), preferred from the viewpoint of achieving both low-temperature fixability and hot offset resistance are alkanedicarboxylic acids having 2 to 50 carbon atoms, alkenedicarboxylic acids having 4 to 50 carbon atoms, and 8 to 8 carbon atoms. 20 aromatic dicarboxylic acids and aromatic polycarboxylic acids having 9 to 20 carbon atoms, and more preferable from the viewpoint of storage stability are adipic acid, alkenyl succinic acids having 16 to 50 carbon atoms, terephthalic acid, and isophthalic acid. , maleic acid, fumaric acid, trimellitic acid, pyromellitic acid and combinations thereof, more preferably adipic acid, terephthalic acid, isophthalic acid, trimellitic acid and combinations thereof. Anhydrides and lower alkyl esters of these acids are also preferred.

The amorphous polyester resin (B) in the present invention preferably contains an aromatic dicarboxylic acid and an aromatic polycarboxylic acid in the polycarboxylic acid component (y). The content of the aromatic dicarboxylic acid is preferably 70 to 100 mol %, more preferably 80 to 100 mol % based on the number of moles of (y) from the viewpoint of low-temperature fixability when used as a toner.

The softening point of the amorphous polyester resin (B) used in the present invention is 90 to 144° C., preferably 90 to 130° C., from the viewpoint of achieving both hot offset resistance and low-temperature fixability when used as a toner. More preferably, it is 90 to 120°C.
The softening point in the invention can be measured by the following method.
<Method for measuring softening point>
Using a Koka flow tester {for example, CFT-500D manufactured by Shimadzu Corporation}, a load of 1.96 MPa is applied with a plunger while heating 1 g of a measurement sample at a temperature increase rate of 6 ° C./min. , extrude from a nozzle with a diameter of 1 mm and a length of 1 mm, draw a graph of "plunger descent amount (flow value)" and "temperature", and calculate the temperature corresponding to 1/2 of the maximum plunger descent amount Read from the graph and use this value (the temperature when half of the sample to be measured flows out) as the softening point.

The amorphous polyester resin (B) in the present invention preferably has a total acid value and hydroxyl value of 10 mgKOH/g or more and 80 mgKOH/g or less, more preferably 15 mgKOH/g or more and 75 mgKOH/g or less. When the total of the acid value and the hydroxyl value is 10 mgKOH/g or more, the hot offset resistance when used as a toner is good, and when it is 80 mgKOH/g or less, the low-temperature fixability when used as a toner is good. becomes.

The acid value of the amorphous polyester resin (B) is preferably 5 to 70 mgKOH/g, more preferably 6 to 45 mgKOH/g from the viewpoint of charging stability and heat-resistant storage stability when used as a toner.

The hydroxyl value of the amorphous polyester resin (B) is preferably 0 to 70 mgKOH/g, more preferably 0 to 50 mgKOH/g, from the viewpoint of charging stability and heat-resistant storage stability when used as a toner. .

The acid value and hydroxyl value in the present invention are measured by the method specified in JIS K0070 (1992 edition).

The glass transition temperature (Tg) of the amorphous polyester resin (B) is preferably 45-80°C, more preferably 50-80°C. When the glass transition temperature of (A) is 80° C. or lower, low-temperature fixability when used as a toner is improved, and when it is 45° C. or higher, hot offset resistance is improved.
The glass transition temperature of the present invention can be measured by the method (DSC method) specified in ASTM D3418-82 using DSC20, SSC/580 manufactured by Seiko Instruments Inc.

The weight average molecular weight of the amorphous polyester resin (B) is preferably 3,500 to 18,000, more preferably 3,700 to 15,000, and further preferably It is preferably 4,000 to 12,000.
The weight average molecular weight of the amorphous polyester resin (B) can be measured using GPC, and the GPC measurement can be performed under the same conditions as for the vinyl resin (A).

The number average molecular weight of the amorphous polyester resin (B) is preferably 1,500 to 9,000, more preferably 1,800 to 7,500, and further preferably It is preferably 2,000 to 6,000.
The number average molecular weight of the amorphous polyester resin (B) can be measured using GPC, and the GPC measurement can be performed under the same conditions as for the vinyl resin (A).

The peak top molecular weight of the THF-soluble portion of the amorphous polyester resin (B) is preferably from 3,500 to 18,000, more preferably from 3,700 to 3,700, from the viewpoint of achieving both toner durability and low-temperature fixability. 15,000, more preferably 4,000 to 12,000.
The peak top molecular weight of the amorphous polyester resin (B) can be measured using GPC, and the GPC measurement can be performed under the same conditions as for the vinyl resin (A). In addition, Mp means the molecular weight which shows the maximum peak height on the obtained chromatogram.

In the present invention, the amorphous polyester resin (B) can be produced in the same manner as known polyesters.
For example, in an inert gas (nitrogen gas, etc.) atmosphere, the reaction temperature is preferably 150 to 280°C, more preferably 160 to 250°C, and still more preferably 170 to 235°C. can. The reaction time is preferably 30 minutes or more, more preferably 2 to 40 hours, from the viewpoint of ensuring the polycondensation reaction.

At this time, an esterification catalyst can be used as needed. Examples of esterification catalysts include tin-containing catalysts (such as dibutyltin oxide), antimony trioxide, titanium-containing catalysts (such as titanium alkoxides (tetraisopropoxytitanate and tetrabutoxytitanate), potassium oxalate titanate, titanium terephthalate, etc.). , titanium terephthalate alkoxide, the catalyst described in JP-A-2006-243715 {titanium diisopropoxybis (triethanolamine), titanium dihydroxybis (triethanolamine), titanium monohydroxy tris (triethanolamine) , titanyl bis(triethanolamine) and intramolecular polycondensates thereof, etc.} and catalysts described in JP-A-2007-11307 (titanium tributoxy terephthalate, titanium triisopropoxy terephthalate, titanium diisopropoxy diterephthalate, etc.) etc.], zirconium-containing catalysts (eg, zirconyl acetate, etc.) and zinc acetate. Among these, titanium-containing catalysts are preferred. It is also effective to reduce the pressure in order to improve the reaction rate in the final stage of the reaction.

In the toner binder of the present invention, from the viewpoint of low-temperature fixability, the weight ratio of the vinyl resin (A) is 21 to 99% by weight based on the total weight of the toner binder. It is preferably 30 to 99% by weight, more preferably 45 to 99% by weight, still more preferably 80 to 99% by weight.

From the viewpoint of low-temperature fixability, the toner binder of the present invention preferably has a weight ratio of the amorphous polyester resin (B) of 1 to 79% by weight, more preferably 1 to 79% by weight, based on the total weight of the toner binder. 70% by weight, more preferably 1 to 55% by weight, particularly preferably 1 to 20% by weight.

In the present invention, the softening point (Tsp) of the toner binder is preferably 45 to 110° C., more preferably 45 to 100° C., still more preferably 50, from the viewpoint of low-temperature fixability and storage stability of the toner. ~90°C. When the softening point Tsp is 40° C. or higher, the crystallinity and storage stability are good, and when it is 110° C. or lower, the low-temperature fixability is good.

The softening point (Tsp) of the toner binder depends on the weight ratio of (A) in the toner binder, the type and composition ratio of the monomers constituting (A) (for example, the monomer (a ) and the weight ratio of the monomer (a) constituting (A)), the weight average molecular weight, and the like. For example, Tsp can be increased by reducing the weight ratio of (A), increasing the number of carbon atoms in (a), reducing the weight ratio of (a), and increasing the weight average molecular weight of (A).

The softening point (Tsp) of the toner binder in the present invention is measured under the same conditions as the softening point of the amorphous polyester resin (B).

The melting peak temperature Tm of the toner binder measured by DSC is preferably 40 to 100.degree. C., more preferably 45 to 85.degree. C., still more preferably 50 to 75.degree.
At 40° C. or higher, the storage stability of the toner becomes good. On the other hand, if the temperature is 100° C. or less, the low-temperature fixability will be good.
The melting peak temperature Tm of the toner binder can be measured by the same method as described in the explanation of the melting peak temperature Tm of the vinyl resin (A).
The melting peak temperature Tm of the toner binder is determined by adjusting the number of carbon atoms in the monomer (a) that constitutes the vinyl resin (A) and by adjusting the weight ratio of the monomer (a) that constitutes (A). can be adjusted to the above preferred range. For example, Tm can be increased by increasing the number of carbon atoms in (a), increasing the weight ratio of (a), or increasing the weight average molecular weight of (A). Also, when the content of (A) is small, the Tm can be maintained without lowering by increasing the |ΔSP value| with the other resin (B).
The SP value of the resin is obtained by using the Polymers estimation method attached to the computer software "HSPiP4.1.0".

The toner binder preferably satisfies the relational expression (2) from the viewpoint of storage stability and low-temperature fixability when the toner is used.
Relational expression (2): 1.6 ≤ ln (G' _Tm-10 ) / ln (G' _{Tm + 30} ) ≤ 3.4
However, the calculated value shall be obtained by rounding off to the second decimal place.

More preferably, it satisfies the relational expression (2-1), and even more preferably, it satisfies the relational expression (2-2).
Relational expression (2-1): 1.6 ≤ ln (G' _Tm-10 ) / ln (G' _{Tm + 30} ) ≤ 3.1
Relational expression (2-2): 1.7 ≤ ln (G' _Tm-10 ) / ln (G' _{Tm + 30} ) ≤ 2.7

In relational expressions (2), (2-1) and (2-2), G' _Tm-10 is the storage elastic modulus (Pa) of the toner binder when the temperature of the toner binder is (Tm-10)°C. and G' _Tm+30 is the storage modulus (Pa) of the toner binder when the temperature of the toner binder is (Tm+30)°C.
ln(G' _Tm-10 )/ln(G' _Tm+30 ) can be adjusted by the weight average molecular weight of vinyl resin (A) and the type and amount of monomer (b) or monomer (c). . For example, by reducing the weight average molecular weight of the vinyl resin (A), increasing the amount of (a), or decreasing the amount of (b), ln(G'Tm _-10 )/ln( _G'Tm+30 ) can be raised.
The storage elastic modulus G' and the loss elastic modulus G'' of the toner binder can be measured using the viscoelasticity measuring apparatus described above in the same manner as the method described in the explanation of the vinyl resin (A).

A method for producing the toner binder of the present invention will be described.
The toner binder of the present invention is produced by homogeneously mixing the vinyl resin (A) and the amorphous polyester resin (B) or the like simply by using a known mechanical mixing method; The amorphous polyester resin (B) and the like are simultaneously dissolved in a solvent for homogenization, and then the solvent is removed.
In the mechanical mixing method, the mixing device for powder mixing includes a Henschel mixer, Nauta mixer and Banbury mixer, and the mixing device for melt mixing includes a batch type mixing device and a continuous mixing device. is mentioned. Examples of a continuous mixing device such as a reactor using a mechanical stirrer or a magnetic stirrer include a twin-screw kneader, a static mixer, an extruder, a continuous kneader, and three rolls.
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.
When a method of dissolving in a solvent is used, the solvent is not particularly limited as long as it can dissolve all the resins constituting the toner binder (tetrahydrofuran, toluene, acetone, etc.).
The temperature at which the solvent is removed is preferably 50 to 200° C., and the removal of the solvent can be accelerated by reducing the pressure or exhausting air as necessary.

The post-evaporation solid content of the toner binder and vinyl resin (A) of the present invention is determined by the following method.
About 2.00 g of a toner binder sample is weighed and dried at 130° C. and a reduced pressure of 5 kPa or less for 1 hour. The sample after drying is taken out and the weight is measured to the second decimal place, and the solid content after evaporation is calculated from (weight of sample after drying/weight of sample before drying)×100.

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. 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, etc., and these alone 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 using magnetic powder, the amount is preferably 20 to 150 parts, more preferably 40 to 120 parts. Above and below, parts mean parts by weight.

The release agent preferably has a softening point Tsp of 50 to 170° C., and includes polyolefin waxes, microcrystalline waxes, paraffin waxes, aliphatic hydrocarbon waxes such as Fischer-Tropsch waxes, oxides thereof, carnauba wax, and montan. Waxes, deacidified waxes thereof, 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 Tsp of the release agent is measured under the same conditions as the softening point Tsp of the vinyl resin (A).

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 (including those obtained by further thermal degradation thereof], (e.g., low molecular weight polypropylene, low molecular weight polyethylene, low molecular weight polypropylene polyethylene copolymer), oxides of olefin (co)polymers by oxygen and/or ozone , maleic acid-modified olefin (co)polymers [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] and/or unsaturated carboxylic acid alkyl esters [(meth)acrylic acid alkyl esters (alkyl having 1 to 18 carbon atoms) and alkyl maleates (alkyl having 1 to 18) esters, etc.], and Sasol wax.

As the paraffin wax, for example, Paraffin WAX-155, Paraffin WAX-150, Paraffin WAX-145, Paraffin WAX-140, Paraffin WAX-135, HNP-3, HNP-5, HNP- manufactured by Nippon Seiro Co., Ltd. 9, HNP-10, HNP-11, HNP-12, HNP-51 and the like.

Higher alcohols include aliphatic alcohols having 30 to 50 carbon atoms, such as triacontanol. Fatty acids include fatty acids having 30 to 50 carbon atoms, such as triacontane carboxylic acid.

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 positive charge control agent or a negative charge control agent. Nigrosine dyes, triphenylmethane dyes containing tertiary amines as side chains, quaternary ammonium 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 aromatic rings containing polymer and the like.

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.

The content of the toner binder in the toner is preferably 30-97% by weight, more preferably 40-95% by weight, still more preferably 45-92% by weight, based on the weight of the toner. The content of the colorant is preferably 0.05 to 60% by weight, more preferably 0.1 to 55% by weight, still more preferably 0.5 to 50% by weight, based on the weight of the toner. The content of the releasing agent is preferably 0 to 30% by weight, more preferably 0.5 to 20% by weight, still more preferably 1 to 10% by weight, based on the weight of the toner. The content of the charge control agent is preferably 0 to 20% by weight, more preferably 0.1 to 10% by weight, still more preferably 0.5 to 7.5% by weight, based on the weight of the toner. The fluidizing agent content is preferably 0-10% by weight, more preferably 0-5% by weight, and even more preferably 0.1-4% by weight, based on the weight of the toner. The total content of the colorant, release agent, charge control agent and fluidizing agent is preferably 3 to 70% by weight, more preferably 4 to 58% by weight, still more preferably 5 to 50% by weight, based on the weight of the toner. %. By setting the composition ratio of the toner within the above range, a toner having good chargeability can be easily obtained.

When the toner binder of the present invention is used as a toner, the method for producing the toner is not particularly limited, and known methods such as a kneading pulverization method, an emulsion phase inversion method, an emulsion polymerization method, a suspension polymerization method, a dissolution suspension method and an emulsion aggregation method are known. It may be obtained by any method.
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 Melt and knead with a continuous mixing device such as three rolls, then coarsely pulverize with a mill or the like, and finally pulverize using an air flow pulverizer (e.g., supersonic jet pulverizer, etc.), etc. By adjusting the particle size distribution with a classifier such as an air classifier, toner particles [preferably particles having a volume average particle diameter (D50) of 5 to 20 μm] are prepared, and then mixed with a fluidizing agent. can. The volume average particle diameter (D50) is measured using a Coulter counter [eg, trade name: Multisizer III (manufactured by Beckman Coulter, Inc.)].

When the toner is obtained by the emulsification phase inversion method, it is possible to dissolve or disperse the components constituting the toner, excluding the fluidizing agent, in an organic solvent, emulsify the emulsion by adding water or the like, and then separate and classify the emulsion. can. 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 containing 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, or the like 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.

The toner prepared using the toner binder of the present invention is used for developing electrostatic charge images or magnetic latent images in electrophotography, electrostatic recording, electrostatic printing, and the like.

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 105° C. while stirring and sealed. Behenyl acrylate [manufactured by NOF Corporation, the same applies hereinafter] 30 parts, vinyl acetate [manufactured by Nacalai Techs Co., Ltd., the same applies hereinafter] 69 parts, methacrylic acid [manufactured by Nacalai Techs Co., Ltd., the same applies hereinafter] 1 part, t- A mixed solution of 0.35 parts of butyl peroxy-2-ethylhexanoate [PERBUTYL O, NOF Corporation, the same applies hereinafter] and 10 parts of toluene was heated for 1 hour while controlling the temperature inside the autoclave at 105 ° C. was added dropwise to carry out polymerization. Further, after the polymerization was completed at the same temperature for 4 hours, the solvent was removed at 130° C. and taken out when the solid content reached 99.90% or more after evaporation to obtain a vinyl resin (A1).
Table 1 shows the composition and physical properties.

<Production Examples 2 to 18, 21 to 23>
Vinyl resins (A2 to A18, A21 to A23) were obtained in the same manner as in Production Example 1 except that the monomers and other raw materials shown in Tables 1 and 2 were used in designated parts by weight. The physical properties are shown in Tables 1 and 2, respectively.

<Production Example 19>
Synthesis of reaction product of 2-isocyanatoethyl methacrylate and methanol 83 parts of 2-isocyanatoethyl methacrylate [Karenzu MOI, manufactured by Showa Denko K.K. Same below] 17 parts, catalyst [Neostan U-600, Nitto Kasei Kogyo Co., Ltd., same below] 0.5 parts, charged with 100 parts of dehydrated toluene, replaced with nitrogen, and then sealed at 90 ° C. under stirring for 12 hours. A reaction product of 2-isocyanatoethyl methacrylate and methanol was obtained by reacting for a period of time. The solids content after evaporation was 50%.
-Synthesis of vinyl resin (A19) An autoclave was charged with 30 parts of toluene, purged with nitrogen, and heated to 105°C in a sealed state while stirring. 30 parts of behenyl acrylate, 30.6 parts of styrene, 35 parts of vinyl acetate, 0.35 parts of t-butylperoxy-2-ethylhexanoate, 6.8 parts of the above reaction product of 2-isocyanatoethyl methacrylate and methanol, and 6.6 parts of toluene was added dropwise over 1 hour to carry out polymerization while controlling the internal temperature of the autoclave at 105°C. Furthermore, the same temperature was maintained for 4 hours to complete the polymerization. After that, the solvent was removed at 130° C., and when the solid content after evaporation reached 99.90% or more, it was taken out to obtain a vinyl resin (A19). Physical properties are shown in Table 2.

<Production Example 20>
Synthesis of reaction product of 2-isocyanatoethyl methacrylate and dibutylamine A three-necked flask was charged with 68 parts of 2-isocyanatoethyl methacrylate and 100 parts of dehydrated toluene, purged with nitrogen, and cooled in an ice bath. 32 parts of dibutylamine [manufactured by Nacalai Techs Co., Ltd., the same shall apply hereinafter] was added dropwise while the temperature was maintained at 50° C. or lower under stirring with nitrogen gas flow to obtain a reaction product of 2-isocyanatoethyl methacrylate and dibutylamine. The solids content after evaporation was 50%.
-Synthesis of vinyl resin (A20) Vinyl resin (A20) was synthesized in the same manner as vinyl resin synthesis in Production Example 19, except that each monomer was used as a designated weight part based on the monomer composition shown in Table 2. ). Physical properties are shown in Table 2.

<Comparative Production Examples 1 to 8>
In Comparative Production Examples 1 to 8, vinyl resins (A'1 to A'8) 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 3 were specified. . The physical properties are shown in Table 3, respectively.

<Production Example 24>
Into a reactor, 697 parts of a 2 mol propylene oxide adduct of bisphenol A, 297 parts of terephthalic acid, and 0.5 parts of tetrabutoxy titanate as a condensation catalyst are placed and reacted at 220° C. under a reduced pressure of 0.5 to 2.5 kPa. The mixture was allowed to react for 10 hours while distilling off the generated water, and after the acid value became 1 mgKOH/g or less, the mixture was cooled to 180°C. After adding 10 parts of trimellitic anhydride and reacting for 1 hour, a steel belt cooler was used to obtain an amorphous polyester resin (B1).

Table 4 shows the physical properties of the amorphous polyester resin (B1).

<Examples 1 to 25 and Comparative Examples 1 to 8>
Vinyl resins (A1) to (A23), (A'1) to (A'8) and polyester resin (B1) obtained in Production Examples 1 to 24 and Comparative Production Examples 1 to 8 are shown in Tables 5 to 7. was mixed with tetrahydrofuran at a composition ratio of , to obtain a uniform solution having a solid content of 50% after evaporation. Subsequently, the solvent is removed at 80° C. to obtain a resin mixture having a solid content of 99.90% or more after evaporation. ), toners (Ts1 to Ts25, Tf1, Ts'1 to Ts'8) were obtained by the method described below. Tables 5 to 7 show the melting peak temperature (Tm), softening point (Tsp) and viscoelasticity evaluation of the toner binder.

<Production of Toner (Ts1) by Dissolution Suspension Method>
[Production of Fine Particle Dispersion Liquid 1]
In a reaction vessel equipped with a stirring rod and a thermometer, 683 parts of water, sodium salt of methacrylic acid ethylene oxide adduct sulfate ester [Eleminol RS-30, manufactured by Sanyo Chemical Industries] 11 parts, vinyl benzene 139 parts, methacrylic acid 138 Parts, 184 parts of butyl acrylate and 1 part of ammonium persulfate were charged and stirred at 400 rpm for 15 minutes to obtain a white emulsion. The system temperature was raised to 75° C. by heating, and the reaction was carried out for 5 hours. Further, 30 parts of a 1% ammonium persulfate aqueous solution was added, and the mixture was aged at 75° C. for 5 hours to produce a vinyl polymer (copolymer of vinylbenzene-methacrylic acid-butyl acrylate-sodium salt of ethylene oxide methacrylate adduct sulfate ester). An aqueous dispersion [fine particle dispersion 1] was obtained. The volume average particle diameter of [fine particle dispersion 1] measured by a laser diffraction/scattering particle size distribution analyzer [LA-920, manufactured by HORIBA, Ltd.] was 0.15 μm.
[Production of Wax Dispersion 1]
15 parts of carnauba wax and 85 parts of ethyl acetate were added to a reaction vessel equipped with a cooling tube, a thermometer and a stirrer, heated to 80°C to dissolve, cooled to 30°C over 1 hour, and carnauba was added. Wax was crystallized in the form of fine particles, and further wet pulverized with "Ultra Viscomil" (manufactured by Imex) to prepare [Wax Dispersion 1].
[Production of Pigment Masterbatch]
1200 parts of water, 40 parts of carbon black (Regal 400R manufactured by Cabot Corporation), and 20 parts of the vinyl resin (A18) manufactured in Production Example 18 were mixed in a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.), and the mixture was mixed using three rolls. After kneading at 90° C. for 30 minutes, the mixture was cooled by rolling and pulverized by a pulperizer to obtain a pigment masterbatch [MB1].
[Production of aqueous phase s1]
955 parts of water, 15 parts of [fine particle dispersion liquid 1], and 30 parts of sodium dodecyl diphenyl ether disulfonate aqueous solution (Eleminol MON7, manufactured by Sanyo Chemical Industries) were added to a container equipped with a stirring rod to form a milky white liquid [aqueous phase s1]. got

[Production of Toner (Ts1)]
Particleization 191 parts of toner binder (D1), 25 parts of pigment masterbatch [MB1], 67 parts of [wax dispersion liquid 1], and 124 parts of ethyl acetate are put into a beaker, dissolved and mixed uniformly, and [oil phase s1 ] was obtained. Add 600 parts of [aqueous phase s1] to this [oil phase s1], use a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), perform a dispersion operation at a rotation speed of 12000 rpm at 25 ° C. for 1 minute, and further film The solvent was removed with an evaporator under the conditions of -0.05 MPa (gauge pressure), temperature of 40°C, and number of revolutions of 100 rpm for 30 minutes to obtain an aqueous colored polymer dispersion (X1).
Classification (X1) After centrifuging 100 parts, adding 60 parts of water and centrifuging to separate solid and liquid, the process is repeated twice, dried at 35 ° C. for 1 hour, and then elbow jet classification as a classifier. With a machine [Matsubo Co., Ltd., EJ-L-3 (LABO) model], fine powder is finely powdered so that fine powder of 3.17 μm or less is 12% by number or less, and coarse powder of 8.0 μm or more is 3% by volume or less. and coarse particles were removed to obtain colored polymer particles [Cs1].
External addition treatment Next, 1 part of hydrophobic silica [Aerosil R972, manufactured by Nippon Aerosil Co., Ltd.] is added to 100 parts of the colored polymer particles [Cs1] of the obtained colored powder, and the peripheral speed is 15 m. /sec, 5 cycles of mixing for 30 seconds and resting for 1 minute were performed to obtain a toner (Ts1).

<Production of Toners (Ts2) to (Ts25) and (Ts'1) to (Ts'8) by Dissolution Suspension Method>
[oil phase s2] to [oil phase s2] to [oil phase s2] to [oil phase s2] to [oil Phase s25] was obtained, and toners (Ts2) to (Ts25) and (Ts'1) to (Ts'8) having the compositions shown in Tables 8 to 10 were obtained.

<Example 26: Production of toner (Tf1) by kneading pulverization method>
・ Kneading Binder resin (D1) 85 parts, pigment carbon black MA-100 [manufactured by Mitsubishi Chemical Corporation] 6 parts, release agent carnauba wax 4 parts, charge control agent [T-77, Hodogaya Chemical Industry Co., Ltd.] was made into a toner by the following method. First, each raw material 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.].
・Pulverization and classification Next, after finely pulverizing using a supersonic jet grinder Labjet [LJ type manufactured by Nippon Pneumatic Industry Co., Ltd.], it is classified by an air classifier [MDS-I manufactured by Nippon Pneumatic Industry Co., Ltd.]. to obtain colored resin particles (FP1).
External addition treatment Next, 1 part of hydrophobic silica [Aerosil R972, manufactured by Nippon Aerosil Co., Ltd.] as a fluidizing agent is mixed with 100 parts of colored resin particles (FP1) in a sample mill to obtain toner (Tf1). rice field.

For the toners (Ts1) to (Ts25) and (Tf1) obtained in Examples 1 to 26 and the comparative toners (Ts'1) to (Ts'8) obtained in Comparative Examples 1 to 8, the particle size, Low temperature fixability (MFT), hot offset resistance (hot offset temperature) and storage stability test (blocking test) were evaluated by the following methods. The results are shown in Tables 8-10.

<Particle size>
The particle size of the toner was measured by the following method.
About 0.1 g of a toner sample is weighed in a beaker, 2 mL of DRYWELL (manufactured by FUJIFILM Corporation) and 4 mL of ion-exchanged water are added as a dispersing agent, dispersed for 3 minutes with an ultrasonic dispersing machine of 20 W or higher, and then isoton. After adding 10 to 30 mL of II and dispersing again for 3 minutes with an ultrasonic disperser of 20 W or more, immediately using a particle size measuring machine (manufactured by Beckman Coulter, trade name: Multisizer III), the aperture diameter; Volume average particle diameter (Dv50) and particle size distribution (Dv50/Dn50) were measured under conditions of 100 μm, medium: electrolyte (Isoton II), number of measured particles: 100,000. (μm) and particle size distribution.

<Low Temperature Fixability and 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 the method of placing the powder on the paper surface. The minimum fixing temperature (MFT) and hot offset temperature were 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/ ^cm2 . bottom. A lower MFT means better low-temperature fixability. Further, in Table 10, the MFT or hot offset temperature "not fixed" means that the MFT or hot offset temperature could not be measured.

<Storage stability (blocking test)>
・Blocking test 1
The particulate toner was allowed to stand for 15 hours in a dryer controlled to 50° C. and 50% humidity, and the presence or absence of blocking was visually determined and evaluated according to the following criteria.
1-◎: No blocking occurs and no change in fluidity by visual observation 1-○: Blocking occurs, but when the container is shaken, aggregation unravels and flows 1-×: Blocking occurs・Blocking test 2
The particulate toner was allowed to stand for 15 hours in a dryer controlled to 50° C. and 80% humidity, and the presence or absence of blocking was visually determined to evaluate the heat resistant storage stability according to the following criteria.
2-◎: No blocking occurred and no visual change in fluidity 2-○: Blocking occurred, but when the container was shaken, aggregation unraveled and flowed 2-x: Blocking occurred The storage stability was evaluated from the combination of the results of Blocking Tests 1 and 2 according to the following criteria in 6 grades.
1:1-x and 2-x
2: 1-○ and 2-x
3: 1-◎ and 2-x
4: 1-○ and 2-○
5: 1-◎ and 2-○
6: 1-◎ and 2-◎

<Gloss>
Fixability is evaluated in the same manner as the low-temperature fixability.
A white cardboard is laid under the image, and the glossiness (%) of the printed image is measured at an incident angle of 60 degrees using a gloss meter (manufactured by Horiba, Ltd., "IG-330"). The degree of gloss in °C was taken as the gloss value.
A higher gloss value means more excellent gloss. This evaluation criteria generally requires a score of 5 or higher

As is clear from the evaluation results in Tables 8 to 10, the toners (Ts1) to (Ts25) and (Tf1) containing the toner binder of the present invention have good low-temperature fixability, hot offset resistance, and storage stability. is.
On the other hand, toners (Ts'1) to (Ts'8) containing toner binders for comparison have at least The evaluation result was inferior with one.

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 (4)

A toner binder containing a vinyl resin (A) having a monomer (a) as an essential constituent monomer,
the monomer (a) has a chain hydrocarbon group having 18 to 36 carbon atoms and a vinyl group,
The vinyl resin (A) has a melting peak temperature Tm of 40 to 100° C. as measured by DSC,
The vinyl resin (A) has a weight ratio of 21 to 99% by weight based on the weight of the toner binder,
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 an acid value of 19.9 mgKOH/g or less,
The vinyl resin (A) has a loss tangent tan δ (Tm-10) at (Tm-10)°C of 0.01 to 2.0,
The vinyl resin (A) has a loss tangent tan δ (Tm+20) at (Tm+20)°C of 0.5 to 30.0,
A toner binder , wherein the vinyl resin (A) satisfies the relational expression (1) .
Relational expression (1): 1.6 ≤ ln (G' _Tm-10 ) / ln (G' _{Tm + 30} ) ≤ 3.4
[In the relational expression (1), G′ _Tm-10 is the storage modulus (Pa) of the vinyl resin (A) when the temperature of the vinyl resin (A) is (Tm-10)° C., and G′ _Tm+30 is the storage modulus (Pa) of the vinyl resin (A) when the temperature of the vinyl resin (A) is (Tm+30)°C. ] 2. The vinyl resin (A) according to claim 1 , wherein the vinyl resin (A) has a weight average molecular weight of 10,000 to 1,000,000 and a ratio [Mw/Mn] between the number average molecular weight and the weight average molecular weight of 2.2 or more. toner binder. The toner binder contains an amorphous polyester resin (B) having an alcohol component (x) and a carboxylic acid component (y) as essential constituent monomers, and the softening point of the amorphous polyester resin (B) is 90 to 90. 3. The toner binder of claim 1 or 2, wherein the temperature is 144[deg.]C. The vinyl resin (A) further contains a monomer (b) other than the monomer (a) as a constituent monomer, and the monomer (b) is an ester group, a carboxyl group, a nitrile group, a urethane group, or a urea group. 4. The toner binder according to any one of claims 1 to 3 , which is a monomer having at least one functional group selected from the group consisting of an amide group and an ethylenically unsaturated bond.