JP6965296B2 - Toner binder - Google Patents

Description

The present invention relates to a toner binder.

Toner binders for the heat fixing method, which are generally used as an image fixing method in copiers, printers, etc., are required to have both low temperature fixing property, 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 a temperature at which fixing starts, and maintains a constant storage elastic modulus up to a high temperature. It is required that the storage elastic modulus changes to an appropriate value before and after the fixing temperature.
In order to achieve the above-mentioned appropriate change in storage elastic modulus, polyester is used as a main component in the conventional toner binder (see, for example, Patent Documents 1 and 2).
However, a toner binder containing polyester as a main component and a toner using the same have deteriorated charging characteristics due to a decrease in volume specific resistance value due to moisture absorption, as compared with a polymer of a monomer having an ethylene unsaturated bond. There is a problem of doing.
On the other hand, a toner binder using a conventional polymer of a monomer having an ethylenically unsaturated bond as a main component instead of polyester has a smaller intermolecular cohesive force than polyester, so that it has low temperature fixability and hot resistance. It is difficult to achieve both offset properties.
In order to solve this problem, a technique of using low molecular weight and high molecular weight components in combination (see, for example, Patent Document 3), a technique of using a site having a high cohesive force as a constituent unit (for example, see Patent Document 4), and the like. However, all of them have a problem that the low-temperature fixability is insufficient as the storage elastic modulus increases in the fixing temperature range.
Therefore, a technique (Patent Documents 5 to 9 and the like) has been proposed in which low-temperature fixability can be improved by using a crystalline acrylate resin among polymers of monomers having an ethylene unsaturated bond.
In Patent Document 5, since the crystalline acrylate resin is used as an additive in the chemical toner, it is controlled in a relatively low molecular weight region in order to secure compatibility with the amorphous resin which is the main binder, and an emulsion dispersion method is used. In order to impart hydrophilicity to the toner particles for granulation by the above, it is an essential condition to introduce an acid value into the crystalline acrylate resin. Further, when a crystalline acrylate resin is used as the main binder, there is a problem that the introduction of an excessive acid value deteriorates the heat-resistant storage property due to the deterioration of hygroscopicity.
Patent Documents 6 and 7 show toners using a crystalline acrylate resin alone or a copolymer with styrene. Crystalline acrylate resin alone can achieve storage stability due to high melting point and low temperature fixability due to sharp melt property, but due to lack of high temperature elasticity, hot offset resistance is achieved in fixing machines with high nip pressure such as high-speed monochrome machines. There was a problem of shortage.
Patent Documents 8 and 9 try to solve the above-mentioned hot offset resistance by combining a crystalline acrylate resin and a cross-linking agent, but the generation of insoluble components makes it difficult to disperse the resin in an aqueous medium, and a chemical toner. It is difficult to apply to, and in addition to being applied only to crushed toner, the low temperature viscosity due to cross-linking increases. Therefore, it is not possible to meet the demand for low temperature fixability, which has been increasingly required in recent years.
In Patent Document 10, by using a crystalline acrylate resin, it is applied to suppress unevenness in texture due to wax of clear toner, but it is possible to achieve both low temperature fixability and hot offset resistance required as a toner binder. Can not.

Japanese Patent No. 4493080 Japanese Patent No. 2105762 Japanese Unexamined Patent Publication No. 11-327210 Japanese Patent No. 321260 Japanese Patent No. 4677909 Japanese Unexamined Patent Publication No. 11-44967 Japanese Unexamined Patent Publication No. 6-175394 Japanese Patent No. 3458165 Japanese Unexamined Patent Publication No. 2000-352839 Japanese Unexamined Patent Publication No. 2011-09527

An object of the present invention is to provide a toner binder used for a toner having excellent low temperature fixability, hot offset resistance and storage stability.

The present inventors have arrived at the present invention as a result of diligent studies to solve these problems.
That is, the present invention is a toner binder containing the polymer (A), wherein the polymer (A) is a polymer containing the monomer (a) and the monomer (b) as essential constituent monomers. The polymer (a) has a chain hydrocarbon group having 18 to 36 carbon atoms and a vinyl group, and the monomer (b) is a monomer other than the monomer (a) and has Hansen solubility. The polarity term (dP) and hydrogen bond term (dH) of the parameter (HSP) are monomers satisfying the following relational expression (1), and the monomer (a) is a linear polymer having 20 to 24 carbon atoms. It is a (meth) acrylate having an alkyl group, the weight ratio of the polymer (A) is 21 to 100% by weight based on the weight of the toner binder, and the total weight of the monomers constituting the polymer (A) is used as a reference. The toner binder is characterized in that the weight ratio of the monomer (a) is 15 to 90% by weight and the acid value of the polymer (A) is less than 19.9 mgKOH / g.
Relational expression (1): {(dP) ² + (dH) ² } ^0.5 ≧ 8.3

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

Hereinafter, the present invention will be described in detail.
The toner binder of the present invention is a toner binder containing a polymer (A). The polymer (A) is a polymer containing the monomer (a) and the monomer (b) as essential constituent monomers, and the monomer (a) is a chain hydrocarbon having 18 to 36 carbon atoms. It has a group and a vinyl group, and the monomer (b) is a monomer other than the monomer (a), and the polar term (dP) and the hydrogen bond term (dH) of the Hansen solubility parameter (HSP). Is a monomer that satisfies the above relational expression (1). Further, the weight ratio of the polymer (A) is 21 to 100% by weight based on the weight of the toner binder, and the weight ratio of the monomer (a) is based on the total weight of the monomers constituting the polymer (A). Is 15 to 90% by weight, and the acid value of the polymer (A) is less than 19.9 mgKOH / g.

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 carbon dioxide having 18 to 36 carbon atoms. Vinyl esters having a hydrogen group can be mentioned. In the present invention, "(meth) acrylate" means "acrylate" and / or "methacrylate".
Examples of the (meth) acrylate having a chain hydrocarbon group having 18 to 36 carbon atoms include a (meth) acrylate having a linear alkyl group having 18 to 36 carbon atoms [for example, octadecyl (meth) acrylate and nonadecil (meth) acrylate. , Arakidyl (meth) acrylate, heneicosanyl (meth) acrylate, behenyl (meth) acrylate, lignoceryl (meth) acrylate, ceryl (meth) acrylate, montanyl (meth) acrylate, myricyl (meth) acrylate and dotriacenta (meth) acrylate, etc.] And (meth) acrylate having a branched alkyl group having 18 to 36 carbon atoms [2-decyltetradecyl (meth) acrylate or the like] and the like can be mentioned.
Examples of the vinyl ester having a chain hydrocarbon group having 18 to 36 carbon atoms include a vinyl ester having a linear alkyl group having 18 to 36 carbon atoms [for example, vinyl stearate, vinyl behenate, vinyl triacanthate, and hexagon. [Vinyl triacanthate, etc.] and vinyl esters having a branched alkyl group having 18 to 36 carbon atoms can be mentioned.
Of these, (A) is preferably a (meth) acrylate having a linear alkyl group having 18 to 36 carbon atoms from the viewpoint of low temperature fixability and storage stability of the toner, and more preferably 18 to 30 carbon atoms. A (meth) acrylate having a linear alkyl group of, more preferably a (meth) acrylate having an 18 to 24 linear alkyl group, and particularly preferably a 20 to 24 linear alkyl group. It has (meth) acrylates, most preferably arachidyl acrylates, behenyl acrylates and lignoceryl acrylates.
As the monomer (a), one type may be used alone, or two or more types may be used in combination.

The weight ratio of the monomer (a) in the monomer constituting the polymer (A) is based on the total weight of the monomers constituting the polymer (A) from the viewpoint of low temperature fixability and hot offset resistance. From 15 to 90% by weight. It is preferably 18 to 80% by weight, more preferably 20 to 70% by weight, particularly preferably 23 to 60% by weight, and most preferably 25 to 50% by weight. If the weight ratio of the monomer (a) is less than 15% by weight, the low temperature fixability deteriorates, and if it exceeds 90% by weight, the hot offset resistance deteriorates.

The monomer (b) is a monomer other than the monomer (a), and the polar term (dP) and the hydrogen bond term (dH) of the Hansen solubility parameter (HSP) satisfy the relational expression (1). It is a monomer. Any monomer may be used as long as it is a compound other than the monomer (a) and satisfies the relational expression (1). For example, it has a hydrocarbon group having 1 to 3 carbon atoms (1). Meta) acrylates that satisfy the above relational formula (1) (b1), vinyl esters having a hydrocarbon group having 1 to 3 carbon atoms that satisfy the above relational formula (1) (b2), amines and (meth) acrylates. ) Amids with acrylic acid that satisfy the above relational formula (1) (b3), compounds having a polymerizable double bond with a nitrile group that satisfy the above relational formula (1) (b4), and polymerized with lactam. Among compounds having a sex double bond, those satisfying the above relational formula (1) (b5), and among compounds having a polymerizable double bond with a heterocyclic amine, those satisfying the above relational formula (1) (b6). Among compounds having a carboxyl group and a polymerizable double bond, those satisfying the above relational expression (1) (b7), and among compounds having a hydroxyl group and a polymerizable double bond, those satisfying the above relational formula (1) (b8). ), Compounds having a polymerizable double bond with an aldehyde group satisfying the relational expression (1) (b9), and compounds having a polymerizable double bond with a urethane group satisfying the relational expression (1). (B10), a compound having a polymerizable double bond with a urea group (b11) satisfying the relational expression (1), and a compound having a polymerizable double bond with an ether group, the relational expression (1). Those satisfying (b12) and the like can be mentioned. As the monomer (b), one type may be used alone, or two or more types may be used in combination.

As the (meth) acrylate (b1) having a chain hydrocarbon group having 1 to 3 carbon atoms, the calculated value of methyl acrylate [relational formula (1) is 15.4 (hereinafter, similarly, the relational expression in []). (1) calculated value)], ethyl acrylate [9.0], propyl acrylate [8.3], methyl methacrylate [8.5] and the like.

Examples of the vinyl ester (b2) having a hydrocarbon group having 1 to 3 carbon atoms include vinyl acetate [9.9] and vinyl propionate [9.3].

Examples of the amide (b3) of the amine and the (meth) acrylic acid include a monomer obtained by reacting ammonia or an amine having 1 to 8 carbon atoms with acrylic acid or methacrylic acid by a known method.

Examples of the compound (b4) having a polymerizable double bond with a nitrile group include acrylonitrile [14.5], methacrylonitrile [12.8], 4-pentenenitrile [12.2], and 5-hexenenitrile [11. 3] and α-chloroacrylonitrile [14.2] and the like.

Examples of the compound (b5) having a polymerizable double bond with lactam include N-vinylpyrrolidone [10.2], N-vinyl-3-methylpyrrolidone [9.9], and N-vinyl-5-methylpyrrolidone [17]. .7], N-vinylpiperidone [9.7], N-vinyl-4-methylpiperidone [9.2], N-vinyl-caprolactam [9.0], N-vinyl-2-pyrrolidone [11.8], etc. Can be mentioned.

Examples of the compound (b6) having a polymerizable double bond with the heterocyclic amine include N-vinylmorpholine [8.3] and the like.

Examples of the compound (b7) having a carboxyl group and a polymerizable double bond include (meth) acrylic acid [17.9 (12.3)], crotonic acid [16.0], and (anhydrous) maleic acid [17.9]. ], 2-Propenic acid [11.9], 3-butenoic acid [15.8], 4-pentenoic acid [14.3], 5-hexenoic acid [13.2], 6-heptenoic acid [12.2] ], 7-octenoic acid [11.1], 8-nonenoic acid [10.2], 9-decenoic acid [9.8], 10-undecenoic acid [8.9] and the like.
In the present specification, the carbon number in the compound having a carboxyl group and the structure does not include the carbon number contained in the carboxyl group portion.

Examples of the compound (b8) having a hydroxyl group and a polymerizable double bond include hydroxyethyl (meth) acrylate [18.8 (15.4)] and -2-hydroxypropyl (meth) acrylate [15.9 (meth). 13.6)] and the like.

Examples of the (meth) acrylate (b9) having an aldehyde group include acrolein [13.7] and the like.

Examples of the compound (b10) having a polymerizable double bond with a urethane group include a monomer obtained by reacting an alcohol having an ethylenically unsaturated bond with an isocyanate by a known method, and an alcohol having an ethylenically unsaturated bond. It is a monomer obtained by reacting an isocyanate having the above with a known method, and examples thereof include a reaction product of methanol and 2-isocyanatoethyl methacrylate [13.0].

Examples of the compound (b11) having a polymerizable double bond with a urea group include a monomer obtained by reacting an amine having an ethylenically unsaturated bond with an isocyanate by a known method, and an amine and an ethylenically unsaturated bond. It is a monomer obtained by reacting an isocyanate having the above with a known method, and examples thereof include a reaction product of dibutylamine and 2-isocyanatoethyl methacrylate [11.0].

Examples of the (meth) acrylate (b12) having an ether group include glycidyl methacrylate [10.3].

Of the above-mentioned monomers (b), methyl acrylate [15.4], acrylonitrile [14.5], methacrylonitrile [12.8], vinyl acetate are preferable from the viewpoint of achieving both low-temperature fixability and storage stability. [9.9], hydroxyethyl (meth) acrylate [18.8 (15.4)], -2-hydroxypropyl (meth) acrylate [15.9 (13.6)], (meth) acrylic acid [17.9 (12.3)], maleic anhydride [17.9], vinyl propionate [9.3], N-vinylmorpholine [8.3], a reaction product of methanol and 2-isocyanatoethyl methacrylate [13.0], (meth) acrylamide [17.6], N-vinylpyrrolidone [10.2], acryloline [13.7] and glycidyl methacrylate [10.3], more preferably methyl acrylate. [15.4], acrylonitrile [14.5], methacrylonitrile [12.8], vinyl acetate [9.9], -2-hydroxypropyl (meth) acrylate [15.9 (13.6)] , (Meta) acrylic acid [17.9 (12.3)], maleic anhydride [17.9], vinyl propionate [9.3], N-vinylmorpholine [8.3], methanol and 2-isosia Reactants of natoethyl methacrylate [13.0], (meth) acrylamide [17.6], N-vinylpyrrolidone [10.2], acryloline [13.7] and glycidyl methacrylate [10.3].

The weight ratio of the monomer (b) in the monomer constituting the polymer (A) is based on the total weight of the monomers constituting the polymer (A) from the viewpoint of low temperature fixability and hot offset resistance. It is preferably 10 to 80% by weight, more preferably 20 to 78% by weight, further preferably 30 to 75% by weight, particularly preferably 40 to 72% by weight, and most preferably 50 to 50% by weight. It is 70% by weight.

The weight ratio of the monomer (a) constituting the polymer (A) to the monomer (b) {(a): (b)} is preferably 98: 2 to 98: 2 from the viewpoint of low temperature fixability and storage stability. It is 15:85, more preferably 60:40 to 15:85, and even more preferably 40:60 to 15:85.

The monomer (b) is a monomer other than the monomer (a), and has a polar term (dP) and a hydrogen bond term (dH) of the Hansen solubility parameter (HSP) from the viewpoint of low temperature fixability and storage stability. ) Is a monomer that satisfies the following relational expression (1).
Relational expression (1): {(dP) ² + (dH) ² } ^0.5 ≧ 8.3

It preferably satisfies the relational expression (1-2), and particularly preferably satisfies the relational expression (1-3).
Relational expression (1-2): 18.8 ≧ {(dP) ² + (dH) ² } ^0.5 ≧ 8.5
Relational expression (1-3): 18.8 ≧ {(dP) ² + (dH) ² } ^0.5 ≧ 9.5

The definition and calculation of the Hansen solubility parameter are described by Charles M. et al. It is described in "Hansen Solubility Parameter; A Users Handbook (CRC Press, 2007)" by Hansen. Further, by using the computer software "HSPiP 4.1.0", the Hansen solubility parameter can be estimated from the chemical structure of the monomer whose parameter value is not described in the literature. In the present invention, the values are used for the monomers whose parameter values are described in the literature, and the numerical values in the list attached to "HSPiP 4.1.0" are used for the monomers whose parameter values are not described in the literature. For items not listed, use the parameter values estimated using the Y-BM estimation method.

Examples of the method for adjusting the Hansen solubility parameter include changing the functional group. A monomer (b) containing a functional group having a high dipole moment such as a nitrile group or an ester group, or a monomer (b) containing a functional group having hydrogen bonding properties such as an amide group, a hydroxyl group or a carboxyl group. By selecting, the parameters of dP and dH can be increased.

The polymer (A) may contain a monomer (c) other than the monomers (a) and (b) as a constituent monomer in addition to the monomers (a) and the monomer (b). As the monomer (c), one type may be used alone, or two or more types may be used in combination.
The monomer (c) is not particularly limited as long as it is a monomer other than the monomer (a) and the monomer (b), but styrene and alkylstyrene having an alkyl group having 1 to 3 carbon atoms are not particularly limited. (For example, α-methylstyrene and p-methylstyrene, etc.), ethyl methacrylate, propyl methacrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, vinyl butyrate, vinyl isobutyrate and the like can be mentioned. Of these, styrene is preferable from the viewpoint of storage stability when used as a toner.

When the monomer (c) is contained in the monomer constituting the polymer (A), the weight ratio of the monomer (c) is the weight ratio of the monomer constituting the polymer (A) from the viewpoint of storage stability. It is preferably 0 to 5% by weight based on the total weight.

The acid value of the polymer (A) in the present invention is 19.9 mgKOH / g or less. If the acid value is larger than 19.9 mgKOH / g, the hygroscopicity is increased and the storage stability is deteriorated. The acid value of the polymer (A) is more preferably 0 to 15 mgKOH / g, and particularly preferably 0 to 10 mgKOH / g.
The acid value of the polymer (A) can be adjusted by adjusting the acid value of the monomer and the content of a monomer such as a carboxyl group-containing vinyl monomer having an acid value. The acid value of (A) is measured by a method such as JIS K0070.

In the present invention, the melting peak temperature (Tm) of the polymer (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. It is 45 to 85 ° C., particularly preferably 50 to 70. When the melting peak temperature is 40 ° C. or higher, the crystallinity and storage stability are good, and when the melting peak temperature is 100 ° C. or lower, the low temperature fixability is good.
Tm is the type and composition ratio of the monomer constituting (A) (for example, adjusting the carbon number of the monomer (a) constituting the polymer (A) and the monomer constituting (A) (for example). It can be adjusted by adjusting the weight ratio of a), weight average molecular weight, and the like. For example, Tm can be increased by increasing the number of carbon atoms in (a), increasing the weight ratio of (a), increasing the weight average molecular weight 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 Co., Ltd., DSC210, etc.}.
<Measurement conditions>
(1) Hold at 30 ° C for 10 minutes (2) Raise to 150 ° C at 10 ° C / min (3) Hold at 150 ° C for 10 minutes (4) Cool to 0 ° C at 10 ° C / min (5) 10 at 0 ° C Hold for minutes (6) Raise to 150 ° C at 10 ° C / min (7) Analyze each endothermic peak of the differential scanning calorimetry measured in the process of (6).

The weight average molecular weight of the polymer (A) in the present invention is preferably 5,000 to 3,000,000, more preferably 10,000 to 200,000 from the viewpoint of low temperature fixability and hot offset resistance of the toner. be. The weight average molecular weight of the polymer (A) can be adjusted by adjusting the polymerization temperature, the amount of the radical polymerization initiator, the chain transfer agent, and the like.

The weight average molecular weight of the polymer (A) is measured by gel permeation chromatography (hereinafter abbreviated as GPC) under the following conditions.
Equipment (example): HLC-8120 [manufactured by Tosoh Corporation]
Column (example): 2 TSK GEL GMH6 [manufactured by Tosoh Corporation]
Measurement temperature: 40 ° C
Sample solution: 0.25 wt% tetrahydrofuran solution (use the insoluble matter filtered through a 1 μm PTFE filter)
Mobile phase: Tetrahydrofuran (does not contain polymerization inhibitors)
Solution injection volume: 100 μl
Detection device: Refractive index detector Reference material: Standard polystyrene (TSK standard POLYSTYRENE) 12 points (weight average molecular weight: 500 1050 280 5970 9100 18100 37900 96400 1900000 355000 1090000 2890000) [manufactured by Tosoh Corporation]

In the present invention, the softening point (Tsp) of the polymer (A) is preferably 110 ° C. or lower, more preferably 45 to 100 ° C., from the viewpoint of crystallinity, low-temperature fixability and storage stability when used as a toner. Particularly preferably, it is 50 to 90. When the softening point Tsp is 40 ° C. or higher, the crystallinity and storage stability are good, and when the softening point Tsp is 110 ° C. or lower, the low temperature fixability is good.
Further, the softening point Tsp can be controlled by the same method as the above-mentioned melting peak temperature Tm.

The softening point (Tsp) of the polymer (A) in the present invention is a value measured under the following conditions.
Using a flow tester {for example, CFT-500D manufactured by Shimadzu Corporation}, while heating 1 g of the measurement sample at a temperature rise rate of 6 ° C./min, a load of 1.96 MPa was applied by a plunger, and the diameter was 1 mm. , Extrude from a nozzle with a length of 1 mm, draw a graph of "plunger drop amount (flow value)" and "temperature", and read the temperature corresponding to 1/2 of the maximum value of the plunger drop amount from the graph. , This value (the temperature at which half of the measurement sample flows out) is defined as the softening point (Tsp).

In the present invention, the polymer (A) preferably satisfies the relational expression (2) from the viewpoint of storage stability and low-temperature fixability when made into a toner.
Relational expression (2): 1.6 ≤ ln ( _G'Tm-10 ) / ln ( _{G'Tm + 30} ) ≤ 3.4
However, the calculated value shall be calculated by rounding off the second decimal place.

It preferably satisfies the relational expression (2-1), more preferably satisfies the relational expression (2-2), and further preferably satisfies the relational expression (2-3).
Relational expression (2-1): 1.6 ≤ ln ( _G'Tm-10 ) / ln ( _{G'Tm + 30} ) ≤ 3.0
Relational expression (2-2): 1.6 ≤ ln ( _G'Tm-10 ) / ln ( _{G'Tm + 30} ) ≤ 2.6
Relational expression (2-3): 1.6 ≤ ln ( _G'Tm-10 ) / ln ( _{G'Tm + 30} ) ≤ 2.5

In the relational expressions (2), (2-1), (2-2) and (2-3), _G'Tm-10 is (Tm-10) ° C. when the temperature of the polymer (A) is (Tm-10) ° C. It is the storage elastic modulus (Pa) of A), and _{G'Tm + 30} is the storage elastic modulus (Pa) of (A) when the temperature of (A) is (Tm + 30) ° C. The ln ( _G'Tm-10 ) / ln ( _{G'Tm + 30} ) can be adjusted by the weight average molecular weight of (A) and the type or amount of the monomers (a), (b) and (c). For example, the weight average molecular weight of (A) is reduced, the amount of (a) is increased, the Hansen solubility parameter of (b) and (c) is increased, and the amount of (b) and (c) is decreased. ( _G'Tm-10 ) / ln ( _{G'Tm + 30} ) can be increased.

The storage elastic modulus G'and the loss elastic modulus G'of the polymer (A) in the present invention and the storage elastic modulus G'and the loss elastic modulus G'of the toner binder described later are described below using the following viscoelasticity measuring device. It is a value measured under the condition of.
Equipment: ARES-24A (manufactured by Leometric)
Jig: 25mm parallel plate Frequency: 1Hz
Distortion rate: 5%
Temperature rise rate: 5 ° C / min

The polymer (A) in the present invention is a method known for a monomer composition containing a monomer (a), a monomer (b) and, if necessary, a monomer (c) (Japanese Patent Laid-Open No. 5-). It can be produced by polymerizing by the method described in Japanese Patent Application Laid-Open No. 117330, etc.). For example, it can be synthesized by a solution polymerization method in which the monomer is reacted with a radical initiator (di-t-butyl peroxide, azobisisobutyronitrile, etc.) in a solvent (toluene or the like).

The toner binder of the present invention is described in other resins (B) known as polymers for toner binders other than the polymer (A) (Patent No. 4493080, Japanese Patent No. 2105762, and Japanese Patent Application Laid-Open No. 06-194876. , Etc.) may be contained.
In addition, the toner binder of the present invention may contain the compound used during the polymerization of the polymer (A) and its residue as long as the effects of the present invention are not impaired.

Examples of the other resin (B) include polyester resin (B1) and vinyl resin (B2) excluding (A).
These may be one kind alone or a combination of two or more kinds.

The composition of the polyester resin (B1) is not particularly limited as long as it is a polymer resin which is a polycondensate of an alcohol component (x) and a carboxylic acid component (y), and the vinyl resin (B2) is, for example, A polymer of styrene alone, a copolymer of styrene and (meth) acrylic acid, a resin in which a polymer of styrene alone and a polyester resin (B1) are bonded, a copolymer of styrene and (meth) acrylic acid and a polyester resin ( Examples thereof include a resin bonded to B1).

Examples of the alcohol component (x) of the polyester resin (B1) include monoalcohols, diols, and polyols having a valence of trivalent or higher.
These may be one kind alone or a combination of two or more kinds.

Examples of the monoalcohol include linear or branched alkyl alcohols having 1 to 30 carbon atoms (methanol, ethanol, isopropanol, 1-decanol, dodecyl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, araxyl alcohol, behenyl alcohol, lignoceryl alcohol and the like. ) Etc. can be mentioned.

Examples of the diol include alkylene glycols having 2 to 12 carbon atoms (ethylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, and 1,12-dodecanediol. , 1,2-propylene glycol, 1,2-butanediol, 1,2-pentanediol, 1,2-hexanediol, 1,2-heptandiol, 1,2-octanediol, 1,2-nonanediol, 1,2-decanediol), alkylene ether glycol having 4 to 36 carbon atoms (for example, diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.), fat having 4 to 36 carbon atoms Cyclic diols (eg, 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.), alkylene oxides of the alicyclic diols (hereinafter, "alkylene oxide" is abbreviated as AO) [ethylene oxide (hereinafter, "ethylene oxide") Is abbreviated as EO), propylene oxide (hereinafter, "propylene oxide" is abbreviated as PO), butylene oxide (hereinafter, "butylene oxide" is abbreviated as BO), etc.] Additives (number of moles added 1 to 30) ), AO (EO, PO, BO, etc.) adducts of bisphenols (bisphenol A, bisphenol F, bisphenol S, etc.), polylactone diols (polyε-caprolactone diol, etc.) and polybutadiene diols. And so on.

Polyols having a valence of trivalent or higher include alkane polyols and their intramolecular or intermolecular dehydrations (for example, glycerin, trimethylolethane, trimethylrolpropane, pentaerythritol, sorbitol, sorbitan and polyglycerin, etc.), saccharides and derivatives thereof. (For example, sucrose and methyl glucoside, etc.), AO adducts of trisphenols (trisphenol PA, etc.) (preferably 2 to 30 as the number of AO units), AO adducts of novolak resin (phenol novolak, cresol novolak, etc.) (Preferably 2 to 30 as the number of AO units) and acrylic polyol [copolymer of hydroxyethyl (meth) acrylate and other vinyl monomer] and the like.

Of (x), from the viewpoint of low temperature fixability, hot offset resistance and storage stability, preferably AO adducts of bisphenols (2 to 3 moles added), ethylene glycol, 1,2-propylene glycol and 1, It is 4-butanediol.

The carboxylic acid component (y) of the polyester resin (B1) includes monocarboxylic acid, dicarboxylic acid, trivalent or higher valence polycarboxylic acid, and anhydrides and lower alkyl (carbon number 1 to 4) esters of these acids. Methyl ester, ethyl ester, isopropyl ester, etc.) and the like.
These may be one kind alone or a combination of two or more kinds.

Examples of the monocarboxylic acid include aromatic monocarboxylic acids having 7 to 37 carbon atoms (including carbon of carbonyl group) (benzoic acid, toluic acid, 4-ethylbenzoic acid, 4-propylbenzoic acid, etc.) and 2 to 2 carbon atoms. 50 aliphatic monocarboxylic acids (acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, capric acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, behenic acid , (Meta) acrylic acid [“(meth) acrylic” means acrylic or methacryl), crotonic acid, isocrotonic acid, cinnamic acid, etc.) and the like.

Examples of the dicarboxylic acid include alcandicarboxylic acids having 2 to 50 carbon atoms {alcandicarboxylic acids having carboxyl groups at both ends of chain saturated hydrocarbon groups (succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, 1 , 18-Octadecanediocarboxylic acid, etc.), Arcandicarboxylic acid (decylsuccinic acid, etc.) having a carboxyl group other than the terminal of the chain saturated hydrocarbon group}, Arcendicarboxylic acid with 4 to 50 carbon atoms (dodecenylsuccinic acid, pentadecenyl acid, etc.) Alkenyl succinic acid such as succinic acid and octadecenyl succinic acid, maleic acid, fumaric acid and citraconic acid), alicyclic dicarboxylic acid having 6 to 40 carbon atoms [dimeric acid (dimerized linoleic acid), etc.], carbon Examples thereof include aromatic dicarboxylic acids (phthalic acid, isophthalic acid, terephthalic acid, t-butylisophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, etc.) of numbers 8 to 36.

Examples of the tricarboxylic acid having a valence of 3 or more include an aromatic polycarboxylic acid having 9 to 20 carbon atoms (trimertic acid, pyromellitic acid, etc.) and an aliphatic tricarboxylic acid having 6 to 36 carbon atoms (hexane tricarboxylic acid). Vinyl polymers of (acids, etc.) and unsaturated carboxylic acids [number average molecular weight (Mn): 450 to 10,000] (styrene / maleic acid copolymer, styrene / acrylic acid copolymer, and styrene / fumaric acid common weight) Coalescence, etc.) and the like.

Of (y), aromatic carboxylic acids (benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, t-butylisophthalic acid) having 8 to 36 carbon atoms are preferable from the viewpoint of low temperature fixability, hot offset resistance and heat storage stability. Acids, 2,6-naphthalenedicarboxylic acids and 4,4'-biphenyldicarboxylic acids, etc.), 2 to 50 alcandicarboxylic acids (adiponic acids, etc.), aromatic polycarboxylic acids with 9 to 20 carbon atoms (trimeritic acids and (Pyromellitic acid, etc.) and combinations thereof. Further, it may be an anhydride or a lower alkyl ester of these acids.

The acid value of the polyester resin (B1) is preferably 30 mgKOH / g or less from the viewpoint of storage stability.
The acid value of the polyester resin (B1) is measured under the same conditions as the acid value of the polymer (A).

The weight average molecular weight of the polyester resin (B1) is preferably 4,000 to 100,000 from the viewpoint of low temperature fixability and hot offset resistance.
The weight average molecular weight of the polyester resin (B1) is measured under the same conditions as that of the polymer (A).

The softening point (Tsp) of the polyester resin (B1) is preferably 45 to 150 ° C. from the viewpoint of low-temperature fixability and storage stability when used as a toner.
The softening point (Tsp) of the polyester resin (B1) is measured under the same conditions as the softening point Tsp of the polymer (A).

The polyester resin (B1) can be produced in the same manner as known polyesters.
For example, the reaction can be carried out by reacting the components at a reaction temperature of preferably 150 to 280 ° C., more preferably 160 to 250 ° C., still more preferably 170 to 235 ° C. in an atmosphere of an inert gas (nitrogen gas or the like). can. The reaction time is preferably 30 minutes or more, more preferably 2 to 40 hours, from the viewpoint of reliably performing the polycondensation reaction.

At this time, an esterification catalyst can be used if necessary. Examples of esterification catalysts include tin-containing catalysts (eg dibutyltin oxide, etc.), antimony trioxides, titanium-containing catalysts [eg titanium alkoxide, potassium titanate oxalate, titanium terephthalate, titanium terephthalate alkoxide, JP-A-2006-243715. The catalysts described in Japanese Patent Publication No. {Titanium dihydroxybis (triethanolaminate), titanium monohydroxytris (triethanolaminete), titanylbis (triethanolaminete) and their intramolecular polycondensates, etc.} and JP-A-2007- Examples thereof include catalysts described in No. 11307 (titanium tributoxyterephthalate, titanium triisopropoxyterephthalate, titanium diisopropoxyditerephthalate, etc.)], zirconium-containing catalysts (for example, zirconyl acetate, etc.), zinc acetate, and the like. Of these, a titanium-containing catalyst is preferable. It is also effective to reduce the pressure to improve the reaction rate at the end of the reaction.

The charging ratio of the alcohol component (x) and the carboxylic acid component (y) is preferably 2/1 to 1/2, more preferably 1.5 / 1, as the equivalent ratio [OH] / [COOH] of the hydroxyl group to the carboxyl group. It is 1-1 / 1.3, more preferably 1.4 / 1-1 / 1.2. The hydroxyl group is a hydroxyl group derived from the alcohol component (y), and the carboxyl group is the total of the carboxyl groups derived from the carboxylic acid component (z).

From the viewpoint of low temperature fixability and chargeability, the toner binder of the present invention has a weight ratio of the polymer (A) of 21 to 100% by weight based on the total weight of the toner binder. From the viewpoint of low-temperature fixability, the lower limit is preferably 30% by weight or more, more preferably 45% by weight or more, and further preferably 80% by weight or more. From the viewpoint of chargeability, the upper limit is preferably 98% by weight or less.
The weight ratio [(A): (B)] of the polymer (A) to the other resin (B) when the other resin (B) is contained is preferably 21:79 to 95: 5.

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 when the toner is used. ~ 90 ° C. When the softening point Tsp is 40 ° C. or higher, the crystallinity and storage stability are good, and when the softening point Tsp is 110 ° C. or lower, the low temperature fixability is good.

The softening point (Tsp) of the toner binder is the weight ratio of (A) in the toner binder, the type and composition ratio of the monomers constituting (A) (for example, the monomer (a) constituting the polymer (A)). The carbon number of the above can be adjusted, the weight ratio of the monomer (a) constituting (A) can be adjusted, etc.), and the weight average molecular weight can be adjusted. For example, Tsp can be increased by a method such as reducing the weight ratio of (A), increasing the number of carbon atoms of (a), reducing the weight ratio of (a), or 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 Tsp of the polymer (A).

The melting peak temperature Tm measured by DSC of the toner binder is preferably 40 to 100 ° C., more preferably 45 to 85 ° C., and even more preferably 50 to 75 ° C.
At 40 ° C. or higher, the storage stability of the toner is good. On the other hand, when the temperature is 100 ° C. or lower, the low temperature fixability becomes good.
The melting peak temperature Tm of the toner binder can be measured by the same method as described in the description of the melting peak temperature Tm of the polymer (A).
The melting peak temperature Tm of the toner binder is determined by adjusting the carbon number of the monomer (a) constituting the polymer (A) and adjusting the weight ratio of the monomer (a) constituting the polymer (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), increasing the weight average molecular weight of (A), or the like. When the content of (A) is small, it can be maintained without lowering Tm 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 "HSPiP 4.1.0".

The toner binder preferably satisfies the relational expression (2-4) from the viewpoint of storage stability and low temperature fixability when it is made into toner.
Relational expression (2-4): 1.5 ≤ ln ( _G'Tm-10 ) / ln ( _{G'Tm + 30} ) ≤ 3.4
However, the calculated value shall be calculated by rounding off the second decimal place.

It more preferably satisfies the relational expression (2-5), and more preferably satisfies the relational expression (2-6).
Relational expression (2-5): 1.5 ≤ ln ( _G'Tm-10 ) / ln ( _{G'Tm + 30} ) ≤ 2.6
Relational expression (2-6): 1.6 ≤ ln ( _G'Tm-10 ) / ln ( _{G'Tm + 30} ) ≤ 2.5

In the relational expressions (2-4), (2-5) and (2-6), _G'Tm-10 is the storage elastic modulus of the toner binder when the temperature of the toner binder is (Tm-10) ° C. Pa), and _{G'Tm + 30} is the storage elastic modulus (Pa) of the toner binder when the temperature of the toner binder is (Tm + 30) ° C.
The ln ( _G'Tm-10 ) / ln ( _{G'Tm + 30} ) can be adjusted by the weight average molecular weight of the polymer (A) and the type and amount of the monomer (b) or the monomer (c). For example, ln (G) can be reduced by reducing the weight average molecular weight of the polymer (A), increasing the Hansen solubility parameter of (b) or (c), increasing the amount of (a), decreasing the amount of (b), or the like. ' _Tm-10 ) / ln (G' _{Tm + 30} ) can be increased.
The storage elastic modulus G'and the loss elastic modulus G'of the toner binder can be measured by the same method as described in the description of the polymer (A) using the above-mentioned viscoelasticity measuring device.

The method for producing the toner binder of the present invention will be described.
In the toner binder of the present invention, the polymer (A) may be used as it is, and when the above-mentioned other resin (B) or the like is used, the polymer (A) and the above-mentioned other resin (B) or the like are simply used. A method of producing by uniformly mixing by using a known mechanical mixing method, and (A) and the above-mentioned other resin (B) and the like are simultaneously dissolved and homogenized in a solvent, and then the solvent is removed. It can be obtained by a manufacturing method or the like.
In the mechanical mixing method, examples of a mixing device for powder mixing include a Henschel mixer, a Nauter mixer, and a Banbury mixer, and examples of a mixing device for melt mixing include a reaction using a mechanical stirrer or a magnetic stirrer. Examples include a batch type mixer such as a tank and a continuous mixer. Examples of the continuous mixing device include a twin-screw kneader, a static mixer, an extruder, a continuous sneaker, a three-roll and the like.
When the mechanical mixing method is used, the temperature at the time of mixing is preferably 50 to 200 ° C. The mixing time is preferably 0.5 to 24 hours.
When the method of dissolving in a solvent is used, the solvent is not particularly limited as long as it dissolves all the polymers constituting the toner binder in a suitable manner (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 promoted by reducing the pressure or exhausting air as necessary.

The solid content after evaporation of the toner binder and the polymer (A) of the present invention was determined by the following method.
Approximately 2.00 g of a sample such as a toner binder is weighed and dried at 130 ° C. at a reduced pressure of 5 kPa or less for 1 hour. The sample after drying is taken out, 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, a mold release agent, a charge control agent, a fluidizing agent, and the like, if necessary.

As the colorant, all of the dyes, pigments and the like used as the colorant for toner can be used. Carbon Black, Iron Black, Sudan Black SM, First Yellow G, Benzidine Yellow, Pigment Yellow, India First Orange, Pigment Red, Irgasin Red, Paranitroaniline Red, Toluidine Red, Carmin FB, Pigment Orange R, Lake Red 2G, Rhodamin FB, Rhodamin B Lake, Methyl Violet B Lake, Phtalocyanin Blue, Pigment Blue, Brilliant Green, Phtalocyanin Green, Pigment Yellow, Oil Yellow GG, Kayaset YG, Orazole Brown B and Oil Pink OP, etc. Or a mixture of two or more. Further, if necessary, a magnetic powder (powder of a ferromagnetic metal such as iron, cobalt or nickel or a compound such as magnetite, hematite or ferrite) can be contained also as a colorant.
The content of the colorant is preferably 1 to 40 parts, more preferably 3 to 10 parts, based on 100 parts of the toner binder of the present invention. When magnetic powder is used, it is preferably 20 to 150 parts, more preferably 40 to 120 parts. In the above and below, parts mean parts by weight.

The release agent preferably has a softening point Tsp of 50 to 170 ° C., and is an aliphatic hydrocarbon wax such as polyolefin wax, microcrystallin wax, paraffin wax, and Fishertropsh wax, and their oxides, carnauba wax, and montane. Examples thereof include waxes, their deoxidizing 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 Tsp of the release agent is measured under the same conditions as the softening point Tsp of the polymer (A).

As the polyolefin wax, those obtained by (co) polymerization of olefins (ethylene, propylene, 1-butene, isobutylene, 1-hexene, 1-dodecene, 1-octadecene and mixtures thereof, etc.) and those obtained by (co) polymerization. Including heat-reduced polyolefins], (eg low molecular weight polypropylene, low molecular weight polyethylene, low molecular weight polypropylene polyethylene copolymers), oxides of olefin (co) polymers due to oxygen and / or ozone, olefin (co) weight Copolymerized maleic acid modified products [maleic acid and its derivatives (maleic anhydride, monomethyl maleate, monobutyl maleate, dimethyl maleate, etc.) modified products, etc.], olefins and unsaturated carboxylic acids [(meth) acrylic acid, itaconic acid, etc.] And maleic anhydride, etc.] and / or unsaturated carboxylic acid alkyl ester [(meth) alkyl acrylate (1-18 carbon atoms of alkyl) ester and alkyl maleate (alkyl carbon number 1-18) ester, etc.] and the like. Examples thereof include copolymers of Sazole wax and the like.

Examples of the paraffin wax include Paraffin WAX-155, Paraffin WAX-150, Paraffin WAX-145, Paraffin WAX-140, Paraffin WAX-135, HNP-3, HNP-5, and HNP-manufactured by Nippon Seiwa Co., Ltd. 9, HNP-10, HNP-11, HNP-12, HNP-51 and the like.

Examples of the higher alcohol include aliphatic alcohols having 30 to 50 carbon atoms, and examples thereof include triacontanol. Examples of the fatty acid include fatty acids having 30 to 50 carbon atoms, and examples thereof include triacontane carboxylic acid.

Among the above, microcrystalline wax, paraffin wax, Fishertroph wax, carnauba wax and ester wax, and amide wax are preferable 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, and is a triphenylmethane dye containing a niglosin dye or a tertiary amine as a side chain, or a quaternary ammonium. Salts, polyamines, imidazole derivatives, quaternary ammonium base-containing polymers, metal azo dyes, copper phthalocyanine dyes, salicylate metal salts, boron complexes of benzylic acid, sulfonic acid group-containing polymers, fluorine-containing polymers and halogen-substituted aromatics. Examples include ring-containing polymers.

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

The content of the toner binder in the toner is preferably 30 to 97% by weight, more preferably 40 to 95% by weight, still more preferably 45 to 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 toner weight. The content of the release 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 toner weight. 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 toner weight. The content of the fluidizing agent is preferably 0 to 10% by weight, more preferably 0 to 5% by weight, still more preferably 0.1 to 4% by weight, based on the weight of the toner. The total content of the release agent, the charge control agent and the 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 toner weight. .. By setting the composition ratio of the toner in 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 known methods such as a kneading and pulverizing method, an emulsification phase inversion method, an emulsification polymerization method, a suspension polymerization method, a dissolution suspension method and an emulsion aggregation method are known. It may be obtained by any of the above methods.
Of these production methods, the kneading and pulverizing method and the dissolution-suspension method are preferable from the viewpoints of productivity, low-temperature fixability and storage stability.

For example, when the toner is obtained by the kneading and pulverizing method, the components constituting the toner excluding the fluidizing agent are dry-blended with a Henschel mixer, a Nauter mixer, a Banbury mixer or the like, and then a twin-screw kneader, an extruder, a continuous sneaker and the like. It is melt-kneaded with a continuous mixing device such as a 3-roll, then roughly pulverized with a mill or the like, and finally finely divided using an air flow type pulverizer (for example, a supersonic jet pulverizer or the like), and further. By adjusting the particle size distribution with a classifier such as an air flow classifier, toner particles [preferably particles having a volume average particle size (D50) of 5 to 20 μm] can be produced by mixing with a fluidizing agent. can. The volume average particle size (D50) is measured using a Coulter counter [for example, trade name: Multisizer III (manufactured by Beckman Coulter, Inc.)].

When toner is obtained by the emulsification phase inversion method, the components constituting the toner excluding the fluidizing agent may be dissolved or dispersed in an organic solvent, then emulsified by adding water or the like, and then separated and classified for production. can. The volume average particle size of the toner is preferably 3 to 15 μm.

As the emulsification polymerization method and the suspension polymerization method, known methods [methods described in Japanese Patent Publication No. 36-10231, Japanese Patent Publication No. 47-518305, Japanese Patent Publication No. 51-14895, etc.] can be used.

As the dissolution suspension method and the emulsification / aggregation method, known methods [methods described in Japanese Patent No. 3596104, Japanese Patent No. 3492748, etc.] can be used.

The toner used in the toner binder of the present invention is a carrier particle such as ferrite whose surface is coated with iron powder, glass beads, nickel powder, ferrite, magnetite and a resin (acrylic polymer, silicone polymer, etc.), if necessary. Is mixed with and used as a developer for electrically latent images. The weight ratio of the toner to the carrier particles is 1/99 to 100/0. Further, instead of the carrier particles, it can be rubbed with a member such as a charging blade to form an electrical latent image.

The toner containing the toner binder of the present invention is fixed to a support (paper, polyester film, etc.) as an electrophotographic toner by a copying machine, a printer, or the like to be used as a recording material. As a method of fixing to the support, a known heat roll fixing method, flash fixing method, or the like can be applied.

The toner produced by using the toner binder of the present invention is used for developing an electrostatically charged image or a magnetic latent image in an electrophotographic method, an electrostatic recording method, an electrostatic printing method, or the like.

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples. In the following, the part represents the weight part. In addition, Example 4 is read as Reference Example 4.

<Manufacturing example 1>
After charging 17 parts of toluene into an autoclave and replacing it with nitrogen, the temperature was raised to 140 ° C. in a sealed state with stirring. Behenyl acrylate [manufactured by NOF CORPORATION, same below] 35 parts, styrene [made by Idemitsu Kosan Co., Ltd., same below] 30 parts, acrylonitrile [manufactured by Nacalai Tesque Co., Ltd., same below] 35 parts, di-t- A mixed solution of 0.150 parts of butyl peroxide [Perbutyl D, NOF CORPORATION, the same applies hereinafter] and 20 parts of toluene was added dropwise over 5 hours while controlling the temperature inside the autoclave to 140 ° C. for polymerization. rice field. Further, the polymerization was completed by keeping at the same temperature for 22 hours. After that, the temperature is raised to 170 ° C., the solvent is removed under a reduced pressure of 0.5 to 2.5 kPa while controlling the temperature to 170 ° C., and when the solid content becomes 99.90% or more after evaporation, the polymer (A1) is taken out. ) Was obtained.
The composition and physical characteristics are shown in Tables 1 and 2.

<Manufacturing Examples 2 to 30>
Polymers (A2 to A30) were obtained in the same manner as in Production Example 1 except that each monomer was designated by weight based on the composition of the monomers shown in Tables 1 and 2. The analytical values were as shown in Table 1 and Table 2, respectively.

<Manufacturing example 31>
-Synthesis of reaction product of 2-isocyanatoethyl methacrylate and methanol In an autoclave, 80 parts of 2-isocyanatoethyl methacrylate [Karens MOI, manufactured by Showa Denko KK, the same applies hereinafter], 20 parts of methanol, and a catalyst [Neostan U- 600, Nitto Kasei Kogyo Co., Ltd., the same applies hereinafter] 0.5 parts, 100 parts of dehydrated toluene were charged, replaced with nitrogen, and then reacted at 90 ° C. for 12 hours in a sealed state with stirring to 2-isocyanatoethyl methacrylate. And a reaction product of methanol was obtained. The solid content after evaporation was 50%.
-Synthesis of polymer (A31) 17 parts of toluene was charged into an autoclave, replaced with nitrogen, and then the temperature was raised to 140 ° C. in a sealed state with stirring. 35 parts of behenyl acrylate, 26.6 parts of styrene, 35 parts of acrylonitrile, 0.150 parts of di-t-butyl peroxide, 6.8 parts of the above solution of 2-isocyanatoethyl methacrylate and methanol, and 16 parts of toluene. The mixed solution was added dropwise over 5 hours while controlling the temperature inside the autoclave to 140 ° C. for polymerization. Further, the polymerization was completed by keeping at the same temperature for 22 hours. After that, the temperature is raised to 170 ° C., the solvent is removed under a reduced pressure of 0.5 to 2.5 kPa while controlling the temperature to 170 ° C., and when the solid content becomes 99.90% or more after evaporation, the polymer (A31) is taken out. ) Was obtained.

<Manufacturing example 32>
After charging 17 parts of toluene into an autoclave and replacing it with nitrogen, the temperature was raised to 140 ° C. in a sealed state with stirring. 35 parts of behenyl acrylate, glycidyl methacrylate [manufactured by Tokyo Chemical Industry Co., Ltd., the same applies hereinafter] 35 parts, butyl methacrylate [manufactured by Tokyo Chemical Industry Co., Ltd., the same applies hereinafter] 30 parts, di-t-butyl peroxide 0. A mixed solution of 150 parts and 16 parts of toluene was added dropwise over 5 hours while controlling the temperature inside the autoclave to 140 ° C. for polymerization. Further, the polymerization was completed by keeping at the same temperature for 22 hours. After that, the temperature is raised to 170 ° C., the solvent is removed under a reduced pressure of 0.5 to 2.5 kPa while controlling the temperature to 170 ° C., and when the solid content becomes 99.90% or more after evaporation, the polymer (A32) is taken out. ) Was obtained.

<Production Example 33> [Synthesis of polyester resin (B1)]
40 parts of bisphenol A propylene oxide 2 mol adduct, 30 parts of bisphenol A ethylene oxide 2 mol adduct, 27 parts terephthalic acid, 0.3 dibutyltin oxide in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube. The part was put in and reacted at 230 ° C. under a nitrogen stream, and the reaction was carried out for 10 hours while distilling off the generated water. Next, after reacting under a reduced pressure of 0.5 to 2.5 kPa for 5 hours, when the acid value reached 1.0, the temperature was lowered to 220 ° C., 3 parts of trimellitic anhydride was added, and 1 part was added. After holding for a long time, it was taken out from the reaction vessel to obtain a polyester resin (B1). The acid value of the polyester resin (B1) was 16 mgKOH / g, the weight average molecular weight was 8,000, and the softening point (Tsp) was 100 ° C.

<Comparative Manufacturing Examples 1 to 6>
Comparative Production Examples 1 to 6 are the same as in Production Examples 1 except that each monomer is designated by weight based on the composition of the monomers shown in Table 2, and the polymers (A'1) to (A). '6) was obtained. The analytical values were as shown in Table 2.

<Examples 1 to 36 and Comparative Examples 1 to 8>
Comparative Production Examples 1 to 2 and Comparison The polymers (A1) to (A32), (A'1) to (A'6) and polyester resin (B1) obtained in Production Examples 1 to 6 are shown in Tables 3 and 4. It was mixed with tetrahydrofuran in a composition ratio to obtain a uniform solution having a solid content of 50% after evaporation. Subsequently, the solvent was removed at 80 ° C. to obtain a resin mixture having a solid content of 99.90% or more after evaporation, which was used as an electrophotographic toner binder (D1) to (D36) and (D'1) to (D'1) to (D). As '8), toners (Ts1) to (Ts36), (Tf1) and (Ts'1) to (Ts'8) were obtained by the method described below. The results of evaluating the melting peak temperature (Tm), softening point (Tsp), and viscoelasticity of the toner binder are as shown in Tables 3 and 4.

<Manufacturing of toner (Ts1) by dissolution suspension method>
[Manufacturing of fine particle dispersion liquid 1]
In a reaction vessel with a stirring rod and a thermometer set, 683 parts of water, 11 parts of sodium salt of ethylene methacrylate oxide sulfate ester [Eleminol RS-30, manufactured by Sanyo Kasei Kogyo Co., Ltd.], 139 parts of vinylbenzene, 138 parts of methacrylic acid. A white emulsion was obtained when 184 parts of butyl acrylate and 1 part of ammonium persulfate were charged and stirred at 400 rpm for 15 minutes. The mixture was heated to a temperature inside the system of 75 ° C. and reacted for 5 hours. Further, 30 parts of a 1% ammonium persulfate aqueous solution is added and aged at 75 ° C. for 5 hours to obtain a vinyl polymer (copolymer of a sodium salt of vinylbenzene-methacrylic acid-butyl acrylate-ethylene 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 measuring device [LA-920, manufactured by Horiba Seisakusho Co., Ltd.] was 0.15 μm.
[Manufacturing of wax dispersion liquid 1]
15 parts of carnauba wax and 85 parts of ethyl acetate were put into 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. The wax was crystallized into fine particles and further wet-ground with "Ultra Viscomil" (manufactured by IMEX) to prepare [wax dispersion 1].
[Manufacturing of pigment masterbatch]
1200 parts of water, 40 parts of carbon black (manufactured by Cabot, Legal 400R), and 20 parts of the polymer (A18) manufactured in Production Example 18 are mixed with a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.), and the mixture is mixed using 3 rolls. After kneading at 90 ° C. for 30 minutes, the mixture was rolled and cooled and pulverized with a pulperizer to obtain a pigment masterbatch [MB1].
[Manufacturing of aqueous phase s1]
955 parts of water, 15 parts of [fine particle dispersion liquid 1], and 30 parts of an aqueous solution of sodium dodecyldiphenyl ether disulfonate (eleminol MON7, manufactured by Sanyo Kasei Kogyo) were put into a container in which a stirring rod was set, and a milky white liquid [aqueous phase s1] was added. Got

[Manufacturing of toner (Ts1)]
・ 191 parts of toner binder (D1), 25 parts of pigment masterbatch [MB1], 67 parts of [wax dispersion 1], and 124 parts of ethyl acetate were put into a particle beaker to dissolve and homogenize the mixture, and [oil phase s1]. ] Was obtained. 600 parts of [Aquatic phase s1] is added to this [Oil phase s1], and a TK homomixer (manufactured by Tokushu Kagaku Kogyo Co., Ltd.) is used to perform a dispersion operation at 25 ° C. for 1 minute at a rotation speed of 12000 rpm, and further, a film. The solvent was removed with an evaporator under the conditions of a reduced pressure of −0.05 MPa (gauge pressure), a temperature of 40 ° C., and a rotation speed of 100 rpm for 30 minutes to obtain an aqueous colored polymer dispersion (X1).
-Classification (X1) 100 parts are centrifuged, 60 parts of water is added, and the steps of centrifugation and solid-liquid separation are repeated twice, and after drying at 35 ° C. for 1 hour, elbow jet classification is performed as a classifier. In the machine [manufactured by Matsubo Co., Ltd., EJ-L-3 (LABO) type], fine powder of 3.17 μm or less is 12% by volume or less, and coarse powder of 8.0 μm or more is 3% by volume or less. And the coarse powder was removed to obtain colored polymer particles [Cs1].
-External treatment Next, 1 part of hydrophobic silica [Aerosil R972, manufactured by Nippon Aerosil Co., Ltd.] was added to 100 parts of the colored polymer particles [Cs1] of the obtained colored powder, and the peripheral speed was 15 m. Mixing for 30 seconds at / sec was performed for 5 cycles of rest for 1 minute to obtain toner (Ts1).

<Production of Toners (Ts2) to (Ts36) and (Ts'1) to (Ts'8) by Dissolution Suspension Method (D2) to (D36) and (D'1) to Toner Binder (D1) [Oil phase s2] to [Oil phase s36] are obtained in the same procedure as in Example 1 except that (D'8) is used, and the toners (Ts2) to (Ts2) to (Ts2) to (2) to the compositions shown in Tables 5 and 6 are obtained. Ts36) and (Ts'1) to (Ts'8) were obtained.

<Example 37: Production of toner (Tf1) by kneading and pulverizing method>
・ 85 parts of kneading binder resin (D31), 6 parts of carbon black [MA-100, manufactured by Mitsubishi Chemical Corporation] as a colorant, 4 parts of carnauba wax as a release agent, charge control agent [T-77, Hodoya Chemical Industry Co., Ltd.] 4 parts were made into toner by the following method. First, each raw material was premixed using a Henschel mixer [FM10B manufactured by Nippon Coke Industries Co., Ltd.] and then kneaded with a twin-screw kneader [PCM-30 manufactured by Ikekai Co., Ltd.].
・ After crushing and classification, finely crushed using a supersonic jet crusher Lab Jet [LJ type manufactured by Nippon Pneumatic Industries Co., Ltd.], and then classified by an airflow classifying machine [MDS-I manufactured by Nippon Pneumatic Industries Co., Ltd.]. Then, colored polymer particles (Cf1) were obtained.
-External treatment Next, 100 parts of colored polymer particles (Cf1) were mixed with 1 part of hydrophobic silica [Aerosil R972, manufactured by Nippon Aerosil Co., Ltd.] as a fluidizing agent with a sample mill to obtain toner (Tf1). rice field.

Regarding the toners (Ts1) to (Ts36) and (Tf1) obtained in Examples 1 to 37 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), storage stability test (blocking test), chargeability and glossiness were evaluated by the following methods. The results are shown in Tables 5 and 6.

<Particle size>
The particle size of the toner was measured by the following method.
Approximately 0.1 g of a toner sample is weighed in a beaker, 2 mL of dry well (manufactured by Fujifilm) and 4 mL of ion-exchanged water are added as dispersants, dispersed for 3 minutes with an ultrasonic disperser of 20 W or more, and then isoton. Add 10 to 30 mL of II, disperse again with an ultrasonic disperser of 20 W or more for 3 minutes, and then immediately use a particle size measuring machine (Beckman Coulter, trade name: Multisizer III) to measure the aperture diameter; The volume average particle size (Dv50) was measured under the conditions of 100 μm, medium; electrolytic solution (isoton II), number of particles to be measured: 100,000, and this value was taken as the particle size (μm) of the toner.

<Low temperature fixability and hot offset resistance>
The toner is evenly placed on the paper surface so as to be 0.6 mg / cm ^2. At this time, as a method of placing the powder on the paper surface, a printer with the heat fixing machine removed was used. Measure the minimum fixing temperature (MFT) and hot offset temperature when this paper is passed through a pressure roller under the conditions of fixing speed (heating roller peripheral speed) 213 mm / sec and fixing pressure (pressurized roller pressure) 5 kg / cm ^2. bottom. The lower the MFT, the better the low temperature fixability. Further, in Tables 5 and 6, when the MFT and the hot offset temperature are "not fixed", it means that the MFT and the hot offset temperature could not be measured.

<Storage stability (blocking test)>
・ Blocking test 1
The particulate toner was allowed to stand in a dryer whose temperature and humidity were controlled to 50% and 50% for 15 hours, and the presence or absence of blocking was visually judged and evaluated according to the following criteria.
1- ◎: No blocking has occurred and there is no change in visual fluidity 1- ○: Blocking has occurred, but when the container is shaken, the agglutination is unraveled and the fluid flows 1- ×: Blocking has occurred・ Blocking test 2
The particulate toner was allowed to stand in a dryer whose temperature and humidity were controlled to 50 ° C. and 80% humidity for 15 hours, and the presence or absence of blocking was visually judged, and the heat-resistant storage stability was evaluated according to the following criteria.
2- ◎: No blocking has occurred and there is no change in visual fluidity 2- ○: Blocking has occurred, but when the container is shaken, the agglutination is unraveled and the fluid flows 2- ×: Blocking has occurred Storage stability was evaluated on a 6-point scale based on the combination of the results of blocking tests 1 and 2 according to the following criteria.
1: 1- × and 2- ×
2: 1- ○ and 2- ×
3: 1- ◎ and 2- ×
4: 1- ○ and 2- ○
5: 1- ◎ and 2- ○
6: 1- ◎ and 2- ◎

<Charability>
(1) 0.5 g of toner and 20 g of ferrite carrier (F-150 manufactured by Powdertech Co., Ltd.) were placed in a 50 mL glass bottle, and the humidity was adjusted at 23 ° C. and 50% relative humidity for 8 hours or more. (2) Friction stir welding was performed at 50 rpm for 10 minutes and 60 minutes with a tubler shaker mixer, and the amount of charge at each time was measured.
A blow-off charge measuring device [manufactured by Toshiba Chemical Co., Ltd.] was used for the measurement.
"Charge amount of friction time 60 minutes / charge amount of friction time 10 minutes" was calculated and used as an index of chargeability.
[criterion]
⊚: 0.8 or more ○: 0.7 or more and less than 0.8 Δ: 0.6 or more and less than 0.7 ×: less than 0.6

<Glossy>
Toner was placed on a paper surface and fixed by the same method as described in the above low temperature fixability.
Next, a white thick paper is laid under the paper surface on which the toner is fixed, and the glossiness of the printed image ("IG-330" manufactured by Horiba Seisakusho Co., Ltd.) is used at an incident angle of 60 degrees. %) Is measured every 5 ° C. from the temperature above the cold offset generation temperature (MFT) to the temperature at which the hot offset occurs, and the highest glossiness (maximum glossiness) (%) in that range is the toner gloss. Use as an index of sex.
For example, if it is 10% at 120 ° C., 15% at 125 ° C., 20% at 130 ° C., and 18% at 135 ° C., 20% at 130 ° C. is the highest value, so 20% is adopted.
The higher the glossiness, the better the glossiness. Under this evaluation condition, 10% or more is preferable.

As is clear from the evaluation results in Tables 5 and 6, the toners (Ts1) to (Ts36) and (Tf1) containing the toner binder of the present invention have low temperature fixability, hot offset resistance, storage stability, and charging. Good properties and gloss.
On the other hand, the toners (Ts'1) to (Ts'8) containing a toner binder for comparison have low temperature fixability (MFT), hot offset resistance (hot offset temperature), storage stability, chargeability and chargeability. The evaluation result was inferior in at least one of the glossiness.

The 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 static charge image development used in electrophotographic, electrostatic recording, electrostatic printing, and the like. ..

Claims (2)

A toner binder containing the polymer (A), wherein the polymer (A) is a polymer containing the monomer (a) and the monomer (b) as essential constituent monomers.
The monomer (a) has a chain hydrocarbon group having 18 to 36 carbon atoms and a vinyl group.
The monomer (b) is a monomer other than the monomer (a), and the polar term (dP) and the hydrogen bond term (dH) of the Hansen solubility parameter (HSP) are related to the following relational expression (1). It is a monomer that satisfies
The monomer (a) is a (meth) acrylate having a linear alkyl group having 20 to 24 carbon atoms.
The weight ratio of the polymer (A) is 21 to 100% by weight based on the weight of the toner binder.
The weight ratio of the monomer (a) is 15 to 90% by weight based on the total weight of the monomers constituting the polymer (A), and the acid value of the polymer (A) is 19.9 mgKOH / g or less. A toner binder characterized by that.
Relational expression (1): {(dP) ² + (dH) ² } ^0.5 ≧ 8.3 The first aspect of the present invention, wherein the weight ratio {(a): (b)} of the monomer (a) constituting the polymer (A) to the monomer (b) is in the range of 98: 2 to 15:85. Toner binder.