JP2019219656A - Toner binder - Google Patents

Abstract

To provide a toner binder that is used for a toner excellent in low-temperature fixability, hot offset resistance, storage stability, charge stability, and durability.SOLUTION: A toner binder is used, which contains a vinyl resin (A); the vinyl resin (A) is a polymer having a monomer (a) as an essential constituent monomer; the monomer (a) has a chain hydrocarbon group and is (meth)acrylate having 16 to 36 carbon atoms of the chain hydrocarbon group; based on the total weight of the monomer constituting the vinyl resin (A), the weight ratio of (meth)acrylate (a1) having 18 carbon atoms of the chain hydrocarbon group is 30 to 98.5 wt.%, the weight ratio of (meth)acrylate (a2) having 16 carbon atoms of the chain hydrocarbon group is 0.1 to 20 wt.%, and the weight ratio of (meth)acrylate (a3) having 20 carbon atoms of the chain hydrocarbon group is 0.1 to 1 wt.%.SELECTED DRAWING: None

Description

  The present invention relates to a toner binder.

A toner binder for a heat fixing method, which is generally used as an image fixing method in a copying machine, a printer, and the like, is required to have both low-temperature fixing property, hot offset resistance, storage stability, and the like. For this reason, 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 is started, and maintains a constant storage elastic modulus up to a high temperature. It is required that the storage modulus changes to an appropriate value before and after the temperature.
In order to achieve the above-mentioned appropriate change in storage modulus, a conventional toner binder uses polyester as a main component (for example, see Patent Documents 1 and 2).
However, compared to the addition polymer of a monomer having an ethylenically unsaturated bond, the toner binder containing a polyester as a main component and the toner using the same have lower volume resistivity due to moisture absorption, and thus have a higher charge stability. Is worse. In the case of producing a chemical toner using a toner binder containing a polyester as a main component, a solution suspension method other than emulsion polymerization or suspension polymerization using a monomer having an ethylenically unsaturated bond (for example, Patent Document 1) 3) and a special particle-forming technique such as an emulsion aggregation method (for example, see Patent Document 4), which causes a problem that the production cost is increased.
On the other hand, a toner binder using a conventional addition polymer of a monomer having an ethylenically unsaturated bond instead of polyester as a main component has a lower intermolecular cohesion than polyester, so that the low-temperature fixability and the resistance to toner are low. It is difficult to achieve both hot offset properties.
In order to solve this problem, a technique using a combination of low and high molecular weight components (for example, see Patent Document 5), a technique using a site having high cohesion as a constituent unit (for example, see Patent Document 6), and the like However, there is a problem that the low-temperature fixability is insufficient with an increase in storage modulus in the fixing temperature range.
In view of this, there have been proposed techniques (for example, Patent Documents 7 to 10) in which low-temperature fixability can be improved by using a crystalline acrylate resin among addition polymers of monomers having an ethylenically unsaturated bond.
Patent Document 7 discloses a toner 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 meltability, but lacks high-temperature elasticity, so hot-offset resistance is high for fixing machines with high nip pressure such as high-speed monochrome machines. There is a problem of shortage.
Patent Documents 8 and 9 attempt to solve the above hot offset resistance by combining a crystalline acrylate resin and a cross-linking agent. However, the generation of insoluble components makes it difficult to disperse the resin in an aqueous medium. In addition to the application to pulverized toner, low temperature viscosity due to crosslinking increases. Therefore, it cannot meet the demand for low-temperature fixability which has been increasingly required in recent years.
In Patent Document 10, a crystalline acrylate resin is used to suppress unevenness in texture due to wax of a clear toner. However, both low-temperature fixability and hot offset resistance required as a normal toner binder are compatible. I can't.

Japanese Patent No. 4493080 Japanese Patent No. 2105762 Japanese Patent No. 3596104 Japanese Patent No. 3492748 JP-A-11-327210 Japanese Patent No. 321860 JP-A-11-44967 Japanese Patent No. 3458165 JP 2000-352839 A JP 2011-095727 A

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

As a result of intensive studies to solve these problems, the present invention has been reached.
That is, the present invention relates to a toner binder containing a vinyl resin (A), wherein the vinyl resin (A) is a polymer containing the monomer (a) as an essential constituent monomer, and the monomer (a) Is a (meth) acrylate having a chain hydrocarbon group, wherein the chain hydrocarbon group has 16 to 36 carbon atoms, and the chain is based on the total weight of the monomers constituting the vinyl resin (A). The weight ratio of the (meth) acrylate (a1) having 18 carbon atoms in the chain hydrocarbon group is 30 to 98.5% by weight, and the (meth) acrylate (a2) having 16 carbon atoms in the chain hydrocarbon group. A toner binder having a weight ratio of 0.1 to 20% by weight and a weight ratio of a (meth) acrylate (a3) having 20 carbon atoms in a chain hydrocarbon group of 0.1 to 1% by weight.

  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, storage stability, charge stability, and durability.

  The toner binder of the present invention is a toner binder containing a vinyl resin (A), wherein the vinyl resin (A) is a polymer having the monomer (a) as an essential constituent monomer, a) is a (meth) acrylate having a chain hydrocarbon group and having 16 to 36 carbon atoms in the chain hydrocarbon group, based on the total weight of the monomers constituting the vinyl resin (A). The weight ratio of the (meth) acrylate (a1) having 18 carbon atoms in the chain hydrocarbon group is 30 to 98.5% by weight, and the (meth) acrylate (a2) having 16 carbon atoms in the chain hydrocarbon group. ) Is 0.1 to 20% by weight, and the weight ratio of (meth) acrylate (a3) having 20 carbon atoms in the chain hydrocarbon group is 0.1 to 1% by weight. .

The monomer (a) is a (meth) acrylate having a chain hydrocarbon group and having 16 to 36 carbon atoms. In the present invention, “(meth) acrylate” means “acrylate” and / or “methacrylate”.
As the (meth) acrylate having 16 to 36 carbon atoms in the chain hydrocarbon group, a (meth) acrylate having a linear alkyl group having 16 to 36 carbon atoms [for example, palmityl (meth) acrylate, heptadecyl (meth) acrylate) , Stearyl (meth) acrylate, nonadecyl (meth) acrylate, arachidyl (meth) acrylate, heneicosanyl (meth) acrylate, behenyl (meth) acrylate, lignoceryl (meth) acrylate, seryl (meth) acrylate, montanyl (meth) acrylate, myricyl (Meth) acrylate and dotriacontyl (meth) acrylate) and a (meth) acrylate having a branched alkyl group having 16 to 36 carbon atoms [2-decyltetradecyl (meth) acrylate and the like].
Among these, from the viewpoint of the crystallinity of (A) and the storage stability of the toner, a (meth) acrylate having a linear alkyl group having 16 to 36 carbon atoms is preferable, and a (meth) acrylate having 16 to 30 carbon atoms is more preferable. (Meth) acrylate having a linear alkyl group, particularly preferably palmityl (meth) acrylate, stearyl (meth) acrylate, arachidyl (meth) acrylate, behenyl (meth) acrylate and lignoceryl (meth) acrylate, Preferred are palmityl acrylate, stearyl acrylate and arachidyl acrylate.
At least three types of the monomer (a) are used in combination, and four or more types may be used in combination.

  The monomer (a), which is an essential constituent monomer of the vinyl resin (A), has 18 carbon atoms in the chain hydrocarbon group based on the total weight of the monomers constituting the vinyl resin (A). The weight ratio of (meth) acrylate (a1) is 30 to 98.5% by weight, and the weight ratio of (meth) acrylate (a2) having 16 carbon atoms in the chain hydrocarbon group is 0.1 to 20% by weight. And the weight ratio of (meth) acrylate (a3) having 20 carbon atoms in the chain hydrocarbon group is 0.1 to 1% by weight, which will be described in detail below.

  The (meth) acrylate (a1) having a chain hydrocarbon group having 18 carbon atoms is preferably stearyl acrylate from the viewpoint of the crystallinity of (A), the storage stability of the toner, the charging stability, and the durability. Further, based on the total weight of the monomers constituting the vinyl resin (A), the weight ratio of (a1) is 30 to 98.5% by weight from the viewpoint of the crystallinity of (A), and is preferably. It is 35 to 97% by weight, more preferably 40 to 95% by weight, particularly preferably 45 to 93% by weight, most preferably 48 to 90% by weight.

  The (meth) acrylate (a2) having a chain hydrocarbon group having 16 carbon atoms is preferably palmityl acrylate from the viewpoint of the crystallinity of (A), the storage stability of the toner, the charging stability, and the durability. Further, based on the total weight of the monomers constituting the vinyl resin (A), the weight ratio of (a2) is preferably from 0.1 to 20% by weight from the viewpoint of charging stability and durability of the toner. Is 0.1 to 17% by weight, more preferably 0.1 to 15% by weight, particularly preferably 0.2 to 13% by weight, and most preferably 0.5 to 10% by weight.

  The (meth) acrylate (a3) having a chain hydrocarbon group having 20 carbon atoms is preferably arachidyl acrylate from the viewpoints of storage stability, charging stability and durability of the toner. Further, based on the total weight of the monomers constituting the vinyl resin (A), the weight ratio of (a3) is 0.1 to 1% by weight from the viewpoint of the storage stability and charging stability of the toner. Preferably 0.1-0.9% by weight, more preferably 0.1-0.8% by weight, particularly preferably 0.2-0.7% by weight, most preferably 0.2-0.6% by weight It is.

  In the present invention, the content of the monomer (a) in the monomer constituting the vinyl resin (A) is determined based on the total weight of the monomers constituting the vinyl resin (A), from the viewpoint of low-temperature fixability. From 30.6 to 99.1% by weight, more preferably 39.0 to 98.0% by weight, particularly preferably 44.0 to 95.8% by weight, and most preferably 50.0 to 95.8% by weight. 0 to 91.2% by weight.

  In addition to the monomer (a) as a constituent monomer, the vinyl resin (A) further includes a nitrile group, a urethane group, a urea group, an amide group, an imide group, an allophanate group, from the viewpoint of hot offset resistance of the toner. It may include a monomer (b) having at least one functional group selected from the group consisting of an isocyanurate group and a burette group and an ethylenically unsaturated bond.

  Examples of the monomer (b) include a monomer (b1) having a nitrile group, a monomer (b2) having a urethane group, a monomer (b3) having a urea group, and a monomer having an amide group. (B4), a monomer having an imide group (b5), a monomer having an allophanate group (b6), a monomer having an isocyanurate group (b7), and a monomer having a buret group (b8) And the like.

  The functional group of the monomer (b) is a functional group having a high degree of aggregation and a highly polar functional group. Therefore, by using the monomer (b), the melting peak temperature of the vinyl resin (A) can be improved. Tm can be increased.

  Examples of the monomer (b1) having a nitrile group include acrylonitrile and methacrylonitrile.

Examples of the monomer (b2) having a urethane group include an alcohol having an ethylenically unsaturated bond and having 2 to 22 carbon atoms (such as hydroxylethyl (meth) acrylate and vinyl alcohol) and an isocyanate having 1 to 30 carbon atoms. Examples include monomers reacted by a known method, and monomers obtained by reacting an alcohol having 1 to 26 carbon atoms and an isocyanate having 1 to 30 carbon atoms having an ethylenically unsaturated bond by a known method. Can be
Examples of the isocyanate having 1 to 30 carbon atoms include monoisocyanate compounds (benzenesulfonyl isocyanate, tosyl isocyanate, phenyl isocyanate, p-chlorophenyl isocyanate, butyl isocyanate, hexyl isocyanate, t-butyl isocyanate, cyclohexyl isocyanate, octyl isocyanate, 2-ethylhexyl isocyanate) , Dodecyl isocyanate, adamantyl isocyanate, 2,6-dimethylphenyl isocyanate, 3,5-dimethylphenyl isocyanate, 2,6-dipropylphenyl isocyanate, etc.), aliphatic diisocyanate compounds (trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate) , Pentamethylenediiso Anate, 1,2-propylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, etc.), alicyclic diisocyanate compound (1,3-cyclopentene diisocyanate, 1,3- Cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated tetramethyl xylylene diisocyanate, etc.) and aromatic diisocyanate compounds (phenylene diisocyanate, 2,4-tolylene diisosonate, 2,6-tolylene diisocyanate, 2,2′-diphenylmethyl Diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-toluidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalenediisocyanate, xylylene diisocyanate, and the like). Can be
Examples of the alcohol having 1 to 26 carbon atoms include methanol, ethanol, propanol, isopropyl alcohol, butanol, t-butyl alcohol, pentanol, heptanol, octanol, 2-ethylhexanol, nonanol, decanol, undecyl alcohol, lauryl alcohol, and dodecyl. Alcohol, myristyl alcohol, pentadecyl alcohol, cetanol, heptadecanol, stearyl alcohol, isostearyl alcohol, elaidyl alcohol, oleyl alcohol, linoleyl alcohol, linolenyl alcohol, nonadecyl alcohol, heneicosanol, behenyl alcohol and ell Silalcohol and the like.
Examples of the isocyanate having an ethylenically unsaturated bond and having 1 to 30 carbon atoms include 2-isocyanatoethyl (meth) acrylate and 2- [0- (1′-methylpropylideneamino) carboxyamino] ethyl (meth) acrylate And 2-[(3,5-dimethylpyrazolyl) carbonylamino] ethyl (meth) acrylate and 1,1- (bis (meth) acryloyloxymethyl) ethyl isocyanate.
In the present specification, the number of carbon atoms in the compound having an isocyanate group and the structure does not include the number of carbon atoms contained in the isocyanate group (—NCO).

  Examples of the monomer (b3) having a urea group include amines having 3 to 22 carbon atoms [for example, primary amines (such as normal butylamine, t-butylamine, propylamine and isopropylamine), and secondary amines (diethylamine, dinormal Propylamine, dinormal butylamine, etc.), aniline, cyclohexylamine, etc.] and an isocyanate having 2 to 30 carbon atoms having an ethylenically unsaturated bond by a known method.

As the monomer (b4) having an amide group, an amine having 3 to 22 carbon atoms and a carboxylic acid having 2 to 30 carbon atoms having an ethylenically unsaturated bond (such as acrylic acid and methacrylic acid) are reacted by a known method. And the like.
In the present specification, the number of carbon atoms in the compound having a carboxyl group and the structure does not include the number of carbon atoms contained in the carboxyl group portion.

As the monomer (b5) having an imide group, ammonia and a carboxylic anhydride having 2 to 10 carbon atoms having an ethylenically unsaturated bond (maleic anhydride, diacrylic anhydride, etc.) were reacted by a known method. Examples of the monomer include a monomer obtained by reacting a primary amine having 1 to 30 carbon atoms with a carboxylic anhydride having 2 to 10 carbon atoms having an ethylenically unsaturated bond by a known method.
In the present specification, the number of carbon atoms in the monomer having a carboxylic anhydride structure does not include the number of carbon atoms (two) derived from the carboxyl group.

  Examples of the monomer (b6) having an allophanate group include a monomer obtained by reacting a monomer (b2) having a urethane group with an isocyanate having 1 to 30 carbon atoms by a known method.

  Examples of the monomer (b7) having an isocyanurate group include tris (2-acryloyloxyethyl) isocyanurate and tris- (2-acryloxyethyl) isocyanurate modified with ε-caprolactone.

  Examples of the monomer (b8) having a buret group include a monomer obtained by reacting a monomer (b3) having a urea group with an isocyanate having 1 to 30 carbon atoms by a known method.

The method for introducing at least one functional group selected from the group consisting of a urethane group, a urea group, an amide group, an imide group, an allophanate group, and a burette group into the vinyl resin (A) is as described above. In addition to the method using the bodies (b2) to (b8), the following method can also be used.
First, of the two compounds (the compound having an ethylenically unsaturated bond and the other compound) for obtaining the monomers (b2) to (b8), the compound having an ethylenically unsaturated bond is converted into a monomer (a ). Subsequently, the other compound is reacted with the polymer of the compound having an ethylenically unsaturated bond and the monomer (a). By the above procedure, the "polymer of the compound having an ethylenically unsaturated bond and the monomer (a)" and the "other compound" are bonded to obtain the vinyl resin (A). At the time of this reaction, the "polymer of the compound having an ethylenically unsaturated bond and the monomer (a)" and the "other compound" are converted into a urethane group, a urea group, an amide group, an imide group, an allophanate group. Alternatively, at least one functional group selected from the group consisting of a urethane group, a urea group, an amide group, an imide group, an allophanate group, and a burette group is introduced into the vinyl resin (A) because of being bonded by a burette group. can do.
In the case of the above method, the monomers (b2) to (b8) are not used as the monomers constituting the vinyl resin (A), but since the obtained compounds are the same, the monomers are used for convenience. It is expressed that (b2) to (b8) are used.

Among these monomers (b), a monomer (b1) having a nitrile group, a monomer (b1) having a urethane group, and a monomer (b1) having a urethane group are preferable from the viewpoint of a balance between storage elastic modulus and loss elastic modulus when formed into a toner. b2), a monomer having a urea group (b3) and a monomer having an amide group (b4), more preferably a monomer having a nitrile group (b1), and a monomer having a urea group ( b3) and a monomer (b4) having an amide group.
As the monomer (b), one type may be used alone, or two or more types may be used in combination.

  When the monomer constituting the vinyl resin (A) contains the monomer (b), the weight ratio of the monomer (b) is determined from the viewpoints of low-temperature fixability, hot offset resistance and charging stability. It is preferably 0.5 to 34.7% by weight, more preferably 1.0 to 31.0% by weight, and particularly preferably 2 to 3% by weight, based on the total weight of the monomers constituting the resin (A). 0.5 to 28.0% by weight, most preferably 5.0 to 25.0% by weight.

  The molecular weight of the monomer (b) is determined by the total number of nitrile groups, urethane groups, urea groups, amide groups, imide groups, allophanate groups, isocyanurate groups, and burette groups in one molecule of the monomer (b). (Also referred to as a functional group equivalent) is preferably 800 or less, more preferably 500 or less, from the viewpoint of the loss elastic modulus of the toner.

The vinyl resin (A) may contain a monomer (c) other than (a) and (b) as a constituent monomer in addition to the monomers (a) and (b).
Examples of the monomer (c) include styrene, an alkyl styrene having an alkyl group having 1 to 3 carbon atoms (for example, α-methylstyrene and p-methyl styrene), and an alkyl having an alkyl group having 1 to 15 carbon atoms (meth ) Acrylates (e.g., methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and lauryl (meth) acrylate) and C2-C2 having an ethylenically unsaturated bond 22 alcohols (eg, hydroxylethyl (meth) acrylate and vinyl alcohol) and alkylamino group-containing (meth) acrylates having 1 to 15 carbon atoms in the alkyl group (eg, dimethylaminoethyl (meth) acrylate and diethylaminoethyl ( Meth) acrylate, etc.) It is.
Examples of the carboxyl group-containing vinyl monomer include monocarboxylic acids [for example, include (meth) acrylic acid, crotonic acid, and cinnamic acid, preferably monocarboxylic acids having 2 to 15 carbon atoms], dicarboxylic acids [for example, maleic anhydride). Acids, fumaric acid, itaconic acid, citraconic acid, etc., preferably dicarboxylic acids having 2 to 15 carbon atoms] and dicarboxylic acid monoesters (monoalkyl esters of the above dicarboxylic acids (for example, monoalkyl maleate, monofumarate) Alkyl ester, itaconic acid monoalkyl ester, citraconic acid monoalkyl ester and the like, and preferably a C1 to C17 monoalkyl group).
Examples of the vinyl ester monomer include aliphatic vinyl esters (for example, vinyl acetate, vinyl propionate, and isopropenyl acetate, etc., preferably having 4 to 15 carbon atoms), and unsaturated carboxylic acid polyhydric alcohol esters. [For example, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, 1,6-hexanediol diacrylate and polyethylene glycol di (meth) A) an acrylate or the like, preferably an unsaturated carboxylic acid polyhydric alcohol ester having 8 to 200 carbon atoms] and an aromatic vinyl ester (e.g., methyl-4-vinylbenzoate, etc .; 15 aromatic vinyl ester), and the like of.
Examples of the aliphatic hydrocarbon-based vinyl monomer include olefins (eg, ethylene, propylene, butene, octene, and the like, preferably olefins having 2 to 10 carbon atoms) and dienes (eg, butadiene, isoprene, 1,6-hexadiene, and the like). And preferably a diene having 4 to 10 carbon atoms).
Among these, from the viewpoints of hot offset resistance, storage stability, and charging stability, preferably, styrene, an alkyl styrene having an alkyl group having 1 to 3 carbon atoms, and an alkyl (meth) having an alkyl group having 1 to 15 carbon atoms. An acrylate and a carboxyl group-containing vinyl monomer are particularly preferable, and styrene, methyl (meth) acrylate and (meth) acrylic acid are particularly preferable. Further, two or more of these may be mixed.

  When the monomer (c) is included in the monomers constituting the vinyl resin (A), the weight ratio of the monomer (c) is determined from the viewpoint of storage stability, charge stability and durability from the viewpoint of the vinyl resin ( It is preferably 0.4 to 34.7% by weight, more preferably 1.0 to 30.0% by weight, and particularly preferably 2.5 to 3% by weight, based on the total weight of the monomers constituting A). ~ 28.0% by weight, most preferably 5.0-25.0% by weight.

  The weight average molecular weight of the vinyl resin (A) in the present invention is preferably from 10,000 to 3,000,000, more preferably from 20,000 to 2,000, from the viewpoint of hot offset resistance and charge stability of the toner. 000, particularly preferably 30,000 to 1,500,000, most preferably 50,000 to 1,000,000. The weight average molecular weight of the vinyl resin (A) can be adjusted by a polymerization temperature, a radical polymerization initiator amount, a chain transfer agent and the like.

The weight average molecular weight of the vinyl resin (A) is measured using gel permeation chromatography (hereinafter abbreviated as GPC) under the following conditions.
Apparatus (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 of tetrahydrofuran solution (use insoluble matter filtered through a 1 μm aperture PTFE filter)
Mobile phase: tetrahydrofuran (does not include polymerization inhibitor)
Solution injection volume: 100 μl
Detector: Refractive index detector Reference substance: 12 points of 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 melting peak temperature Tm (° C.) obtained by DSC measurement (differential scanning calorimetry) of the vinyl resin (A) and the toner binder described below is preferably 35 to 35 from the viewpoint of storage stability when used as a toner. It is 80 degreeC, More preferably, it is 38-77 degreeC, Especially preferably, it is 40-75 degreeC, Most preferably, it is 45-73 degreeC.
Tm is the kind and composition ratio of the monomer constituting (A) (for example, adjusting the number of carbon atoms of the monomer (a) constituting the vinyl resin (A), and controlling the monomer constituting the (A) (E.g., adjusting the weight ratio of (a)) and the weight average molecular weight. Generally, 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).

The DSC measurement in the present invention is a value measured under the following conditions using a differential scanning calorimeter {DSA Q20, etc., manufactured by TA Instruments Co., Ltd.}.
<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) 10 ° C. at 10 ° C. (6) Heat up to 150 ° C. at 10 ° C./min. (7) Analyze each endothermic peak of the differential scanning calorimetric curve measured in the process of (6).

The vinyl resin (A) preferably satisfies the relational expression (1-1) from the viewpoints of storage stability and low-temperature fixability when formed into a toner.
Relational expression (1-1): 1.2 ≦ ln (G ′ _Tm−10 ) / ln (G ′ _{Tm + 30} ) ≦ 2.6
However, the calculated value shall be obtained by rounding off the second decimal place.

More preferably, it satisfies the relational expression (1-2), and particularly preferably satisfies the relational expression (1-3).
Relational expression (1-2): 1.6 ≦ ln (G ′ _Tm−10 ) / ln (G ′ _{Tm + 30} ) ≦ 2.6
Relational expression (1-3): 1.7 ≦ ln ( _G′Tm−10 ) / ln ( _{G′Tm + 30} ) ≦ 2.5

In the relational expressions (1-1), (1-2), and (1-3), G ′ _Tm-10 is the value of (A) when the temperature of the vinyl resin (A) is (Tm-10) ° C. G ′ _{Tm + 30} is the storage modulus (Pa) of (A) when the temperature of (A) is (Tm + 30) ° C.
In ( _G'Tm-10 ) / ln ( _{G'Tm + 30} ) can be adjusted by the weight average molecular weight of (A) and the type and amount of monomer (b) or monomer (c). For example, the weight average molecular weight of (A) is reduced, the polarity of (b) and (c) is reduced, the amount of (b) is reduced, and the amount of (c) is increased by a method such as ln (G ' _Tm-10). ) / Ln (G ′ _{Tm + 30} ).

In the present invention, the storage elastic modulus G ′ of the vinyl resin (A) and the storage elastic modulus G ′ and the loss elastic modulus G ″ of the toner binder described below are measured using the following viscoelasticity measuring device under the following conditions. Value.
Apparatus: ARES-24A (Rheometrics)
Jig: 25mm parallel plate Frequency: 1Hz
Distortion rate: 5%
Heating rate: 5 ° C / min

The acid value of the vinyl resin (A) in the present invention is preferably 40 mgKOH / g or less. When the acid value is 40 mgKOH / g or less, the storage stability is improved by increasing the melting peak temperature Tm and decreasing the hygroscopicity. The acid value of the vinyl resin (A) is more preferably 1 to 30 mgKOH / g, and particularly preferably 2 to 25 mgKOH / g.
The acid value of the vinyl resin (A) can be adjusted by the acid value of the monomer and the content of the monomer having the acid value. The acid value of (A) is measured by, for example, a method such as JIS K 0070.

  The vinyl resin (A) in the present invention can be obtained by subjecting a monomer composition containing the monomer (a) and, if necessary, the monomer (b) and / or the monomer (c) to a known method ( It can be produced by polymerization according to the method described in JP-A-5-117330. For example, it can be synthesized by a solution polymerization method in which the above monomer is reacted with a radical initiator (such as di-t-butyl peroxide, azobisisobutyronitrile) in a solvent (such as toluene).

  The radical reaction initiator is not particularly limited, and examples thereof include an inorganic peroxide, an organic peroxide, and an azo compound. Further, these radical reaction initiators may be used in combination.

  Examples of the inorganic peroxide include, but are not particularly limited to, hydrogen peroxide, ammonium persulfate, potassium persulfate, and sodium persulfate.

  The organic peroxide is not particularly limited. For example, benzoyl peroxide, di-t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, α, α-bis (t-butylperoxy) Diisopropylbenzene, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, di-t-hexyl peroxide, 2,5-dimethyl-2,5-di-t-butylperoxy Hexin-3, acetyl peroxide, isobutyryl peroxide, octanolol peroxide, decanolyl peroxide, lauroyl peroxide, 3,3,5-trimethylhexanoyl peroxide, m-toluyl peroxide, t-butyl peroxide Oxyisobutyrate, t-butyl peroxy neodecanoate, cumyl peroxy neodecano Ethate, t-butylperoxy-2-ethylhexanoate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, t-butylperoxybenzoate, t-butyl Examples include peroxyisopropyl monocarbonate and t-butyl peroxyacetate.

  The azo compound is not particularly limited. For example, 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexane- 1-carbonitrile), 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile and azobisisobutyronitrile.

  Among these, organic peroxides are preferred because they have high initiator efficiency and do not produce toxic by-products such as cyanide. Further, since the crosslinking reaction proceeds efficiently and the amount used is small, a reaction initiator having a high hydrogen abstraction ability is more preferable, and benzoyl peroxide, di-t-butyl peroxide, t-butyl cumyl peroxide, Dicumyl peroxide, α, α-bis (t-butylperoxy) diisopropylbenzene, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane and di-t-hexyl peroxide A radical reaction initiator having high hydrogen abstraction ability is particularly preferable.

The toner binder of the present invention is a resin (B) known as a polymer for toner binders other than the vinyl resin (A) (Japanese Patent No. 4493080, Japanese Patent No. 2105762 and Japanese Patent Application Laid-Open No. 06-194876). Described polymer etc.).
Further, the toner binder of the present invention may contain the compound used at the time of polymerization of the vinyl resin (A) and a residue thereof as long as the effects of the present invention are not impaired.

  Examples of the other resin (B) include a polyester resin (B1) and a vinyl resin (B2) excluding (A).

Examples of the polyester resin (B1) include a linear polyester resin and a non-linear polyester resin. From the viewpoint of storage stability, hot offset resistance, charging stability and durability, a non-linear polyester resin is preferable. Here, the “non-linear” polyester resin (B1) is a polyester resin having a branch (crosslinking point) in the main chain.
The polyester resin (B1) may be a resin having a structure in which the polyester (B11) is cross-linked by a carbon-carbon bond. Here, the crosslink by the carbon-carbon bond is formed by directly bonding at least one of the carbon atoms contained in the polyester (B11) molecule and another carbon atom contained in the polyester (B11) molecule. Is done. The polyester (B11) referred to here is not particularly limited, and may be any polyester as long as it can be crosslinked by a carbon-carbon bond. Among them, polyester (B111) having a carbon-carbon double bond is preferable from the viewpoint of easily forming a crosslinked structure.
In the polyester resin (B1), a hydrogen atom bonded to a carbon atom contained in the polyester resin (B11) is extracted by a hydrogen abstraction reaction by heating or the like in addition to the method of reacting the carbon-carbon double bond of the polyester (B111). It can also be obtained by a crosslinking method (also called a hydrogen atom abstraction reaction) or the like.

Further, the polyester (B111) having a carbon-carbon double bond contains, for example, an unsaturated carboxylic acid component and / or an unsaturated alcohol component, and contains any one of the unsaturated carboxylic acid component and the unsaturated alcohol component. It is preferably a polyester resin obtained by polycondensation.
Further, the polyester (B111) having a carbon-carbon double bond may contain a saturated alcohol component or a saturated carboxylic acid component as a component in addition to the unsaturated carboxylic acid component and the unsaturated alcohol component.
The polyester (B111) may be obtained by polycondensation using each of these components one by one, or may be obtained by polycondensation using a plurality of types as each component.
In the present specification, an unsaturated carboxylic acid is a carboxylic acid having an unsaturated bond between carbon atoms (excluding those included in aromatic hydrocarbons). An alcohol having an interatomic unsaturated bond (excluding those contained in aromatic hydrocarbons).

Examples of the unsaturated alcohol component include an unsaturated monool and an unsaturated diol.
These may be used alone or in a combination of two or more.

  Examples of the unsaturated monool include unsaturated monools having 2 to 30 carbon atoms. Preferred examples thereof include 2-propen-1-ol, palmitoleyl alcohol, elaidyl alcohol, oleyl alcohol, ersyl alcohol, and methacryl. 2-hydroxyethyl acid and the like.

  The unsaturated diol includes an unsaturated diol having 2 to 30 carbon atoms, and a preferred example is ricinoleyl alcohol.

  The unsaturated alcohol component is preferably an unsaturated monool having 2 to 30 carbon atoms, more preferably 2-propen-1-ol, palmitoleyl alcohol, elaidyl alcohol, oleyl alcohol, and ell from the viewpoint of heat-resistant storage stability. Silyl alcohol and 2-hydroxyethyl methacrylate.

  Examples of the saturated alcohol component include a saturated monool (x1), a saturated diol (x2), and a polyol having a valence of 3 or more (x3).

Examples of the saturated monool (x1) include linear or branched alkyl alcohols having 1 to 30 carbon atoms (methanol, ethanol, isopropanol, dodecyl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, and the like).
Among these saturated monols, from the viewpoint of storage stability, preferred are straight-chain alkyl alcohols having 8 to 24 carbon atoms, more preferably dodecyl alcohol, myristyl alcohol, stearyl alcohol, behenyl alcohol, and combinations thereof.

Examples of the saturated diol (x2) include alkylene glycols having 2 to 36 carbon atoms (ethylene glycol, 1,2-propylene glycol (propylene glycol), 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, 3 -Methyl-1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecane Diols and 1,12-dodecanediol) (x21), alkylene ether glycols having 4 to 36 carbon atoms (diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.) (X22), an alicyclic diol having 6 to 36 carbon atoms (e.g., 1,4-cyclohexanedimethanol and hydrogenated bisphenol A) (x23), an alkylene oxide adduct of the alicyclic diol (preferably an addition mole number of 1) To 30) (x24), aromatic diols (monocyclic dihydric phenols (for example, hydroquinone, etc.) and alkylene oxide adducts of bisphenols (preferably 2 to 30 moles added)) (x25).
Among these saturated diols (x2), alkylene glycols (x21) having 2 to 36 carbon atoms and aromatic diols (x25) are preferable from the viewpoints of low-temperature fixability and heat-resistant storage stability, and alkylene oxide adducts of bisphenols are preferable. More preferred. In the alkylene oxide, the carbon number of the alkylene group is preferably 2 to 4, and as the alkylene oxide, ethylene oxide, 1,2- or 1,3-propylene oxide, 1,2-, 2,3-, 1, 3- or iso-butylene oxide and tetrahydrofuran are preferred.

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

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

  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, and 2 , 2'-diethylbisphenol F, and the like, and two or more of these can be used in combination.

  As the alkylene oxide to be added to these bisphenols, an alkylene oxide having 2 to 4 carbon atoms is preferable, for example, ethylene oxide (hereinafter, "ethylene oxide" may be abbreviated as EO), 1,2- or 1,3-propylene oxide ("1,2-propylene oxide" may be abbreviated as PO), 1,2-, 2,3-, 1,3- or iso-butylene oxide, tetrahydrofuran, and these Two or more of them may be used in combination.

AO constituting the AO adduct of bisphenols is preferably EO and / or PO from the viewpoints of heat storage stability and low-temperature fixability. The number of moles of AO added is preferably 2 to 30 mol, and more preferably 2 to 10 mol.
Among the alkylene oxide adducts of bisphenols, those which are preferable from the viewpoints of fixability, pulverizability and heat-resistant storage stability of the toner are EO adducts of bisphenol A (the average addition mole number is preferably 2 to 4, more preferably 2 To 3) and / or a PO adduct (the average number of moles of addition is preferably 2 to 4, more preferably 2 to 3).

  Examples of the trivalent or higher valent polyol (x3) include trivalent or higher valent aliphatic polyhydric alcohols having 3 to 36 carbon atoms, saccharides and derivatives thereof, and AO adducts of aliphatic polyhydric alcohols (addition moles). Number is preferably 1 to 30), AO adducts of trisphenols (such as trisphenol PA) (additional mole number is preferably 2 to 30), and novolak resins (phenol novolak and cresol novolak). As the AO adduct (preferably 3 to 60), the number of moles added is preferably 2 to 30.

  Examples of the aliphatic polyhydric alcohol having a valence of 3 or more and having 3 to 36 carbon atoms include alkane polyols and intramolecular or intermolecular dehydrates thereof, for example, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, Sorbitol, sorbitan, polyglycerin, dipentaerythritol and the like.

  Examples of saccharides and derivatives thereof include sucrose and methyl glucoside.

  Among the trivalent or higher valent polyols (x3), from the viewpoint of achieving both low-temperature fixability and hot offset resistance, an aliphatic polyhydric alcohol having 3 to 36 carbon atoms and a valence of 3 or higher and a novolak resin are preferable. (Phenol novolak, cresol novolak, and the like are included, and the average degree of polymerization is preferably 3 to 60).

  Among the saturated alcohol components, those preferable from the viewpoint of compatibility between low-temperature fixability, hot offset resistance and heat-resistant storage stability include alkylene glycols having 2 to 36 carbon atoms and AO adducts of bisphenols (addition mole is preferably 2 AO addition of an aliphatic polyhydric alcohol having a valence of 3 to 36 or more and a novolak resin (including phenol novolak and cresol novolak, preferably having an average degree of polymerization of 3 to 60). (The number of moles to be added is preferably 2 to 30).

As the saturated alcohol component, those more preferable from the viewpoint of storage stability include alkylene glycols having 2 to 10 carbon atoms, AO adducts of bisphenols (addition mole number is preferably 2 to 5), and 3 to 3 carbon atoms. AO adducts (total number of moles is preferably 2 to 30) of 8-valent aliphatic polyhydric alcohol and novolak resin (including phenol novolak and cresol novolak, preferably having an average degree of polymerization of 3 to 60) is there.
Particularly preferred are an alkylene glycol having 2 to 6 carbon atoms, an AO adduct of bisphenol A (the addition mole number is preferably 2 to 5) and a trivalent aliphatic polyhydric alcohol having 3 to 36 carbon atoms, and most preferred. Are ethylene glycol, propylene glycol, an AO adduct of bisphenol A (the number of moles added is preferably 2 to 3), and trimethylolpropane.

Examples of the unsaturated carboxylic acid component include unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, and anhydrides and lower alkyl esters of these acids.
These may be used alone or in a combination of two or more.

  Examples of the unsaturated monocarboxylic acid include unsaturated monocarboxylic acids having 2 to 30 carbon atoms, such as acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, 3-butenoic acid, angelic acid, tiglic acid, and 4-pentene. Acid, 2-ethyl-2-butenoic acid, 10-undecenoic acid, 2,4-hexadienoic acid, myristolic acid, palmitoleic acid, sapienic acid, oleic acid, elaidic acid, vaccenic acid, gadolinic acid, eicosenoic acid, erucic acid And nervonic acid.

  Examples of unsaturated dicarboxylic acids include alkenedicarboxylic acids having 2 to 50 carbon atoms, such as alkenyl succinic acids such as dodecenyl succinic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid and glutaconic acid. .

Among these unsaturated carboxylic acid components, from the viewpoint of compatibility between low-temperature fixability and hot offset resistance, preferably an unsaturated monocarboxylic acid having 2 to 10 carbon atoms and an alkenedicarboxylic acid having 2 to 18 carbon atoms, More preferred are alkenyl succinic acids such as acrylic acid, methacrylic acid and dodecenyl succinic acid, maleic acid and fumaric acid.
Particularly preferred are acrylic acid, methacrylic acid, maleic acid, fumaric acid and combinations thereof. Further, anhydrides and lower alkyl esters of these acids are also preferable.

  Examples of the saturated carboxylic acid component include an aromatic carboxylic acid and an aliphatic carboxylic acid. One type of the saturated carboxylic acid component may be used, or two or more types may be used in combination.

Examples of the aromatic carboxylic acid include aromatic monocarboxylic acids having 7 to 37 carbon atoms (such as benzoic acid, toluic acid, 4-ethylbenzoic acid, and 4-propylbenzoic acid), and aromatic dicarboxylic acids having 8 to 36 carbon atoms. Acids (phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid and the like), and trivalent or higher aromatic polycarboxylic acids having 9 to 20 carbon atoms (such as trimellitic acid and pyromellitic acid) are exemplified.
Examples of the aliphatic carboxylic acid include aliphatic monocarboxylic acids having 2 to 50 carbon atoms (acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristine) Acids, palmitic acid, margaric acid, stearic acid, behenic acid, etc.), aliphatic dicarboxylic acids having 2 to 50 carbon atoms (oxalic acid, malonic acid, succinic acid, adipic acid, reparginic acid, sebacic acid, etc.), carbon number 6 To 36 aliphatic tricarboxylic acids (such as hexanetricarboxylic acid).
As the saturated carboxylic acid component, anhydrides of these carboxylic acids, lower alkyl (1 to 4 carbon atoms) esters (eg, methyl ester, ethyl ester and isopropyl ester) may be used. You may use together.

Among these saturated carboxylic acid components, those preferable from the viewpoint of compatibility between low-temperature fixability, hot offset resistance and heat-resistant storage stability include aromatic monocarboxylic acids having 7 to 37 carbon atoms and aliphatics having 0 to 50 carbon atoms. A dicarboxylic acid, an aromatic dicarboxylic acid having 8 to 20 carbon atoms, and a trivalent or higher aromatic polycarboxylic acid having 9 to 20 carbon atoms.
From the viewpoints of storage stability and charging stability, benzoic acid, adipic acid, alkylsuccinic acid, terephthalic acid, isophthalic acid, trimellitic acid, pyromellitic acid and combinations thereof are more preferred. Particularly preferred are adipic acid, terephthalic acid, trimellitic acid and combinations thereof. Further, anhydrides or lower alkyl esters of these acids may be used.

  In the present invention, the polyester resin (B1) containing the polyester (B111) can be produced in the same manner as a known polyester. For example, the reaction is carried out in an inert gas (nitrogen gas or the like) atmosphere at a reaction temperature of preferably 150 to 280 ° C, more preferably 160 to 250 ° C, particularly preferably 170 to 235 ° C. it 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. It is also effective to reduce the pressure in order to improve the reaction rate at the end of the reaction.

  At this time, an esterification catalyst can be used if necessary. Examples of the esterification catalyst include tin-containing catalysts (eg, dibutyltin oxide), antimony trioxide, and titanium-containing catalysts (eg, titanium alkoxide, potassium oxalate, titanium terephthalate, titanium terephthalate alkoxide, JP-A-2006-243715). Patent Nos. 4,028,098; 5,898,086; and 4,887,098. Titanium dihydroxybis (triethanolaminate), titanium diisopropoxybis (triethanolaminate), titanium monohydroxytris (triethanolaminate), titanylbis (triethanolaminate) and the like Intramolecular polycondensate etc.} and catalysts described in JP-A-2007-11307 (titanium tributoxy terephthalate, titanium triisopropoxy terephthalate, titanium diisopropoxy diterephthalate, etc.) ], Zirconium-containing catalysts (e.g. zirconyl acetate, etc.), and zinc acetate, and the like. Among these, a titanium-containing catalyst is preferred.

  Further, a stabilizer may be added for the purpose of obtaining polyester polymerization stability. Examples of the stabilizer include phenol compounds (for example, hydroquinone, methylhydroquinone, 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl- 4-ethylphenol, 2,6-di-tert-butyl-4-isopropylphenol, 2,4,6-tri-tert-butylphenol, tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone, 4- Methoxyphenol, 2-tert-butyl-4-methoxyphenol and 2,6-di-tert-butyl-4-methoxyphenol and 4-tert-butylcatechol and the like.

Preferred methods for producing the polyester resin (B1) include the following methods.
First, a polyester having a carbon-carbon double bond in the molecule by subjecting at least one of an unsaturated carboxylic acid component and an unsaturated alcohol component to a condensation reaction with a saturated carboxylic acid component and / or a saturated alcohol component as necessary as a constituent component (B111) is obtained. Next, a radical reaction initiator is allowed to act on the polyester (B111), and the radical generated from the radical reaction initiator is used to cause the unsaturated carboxylic acid component and / or unsaturated alcohol component in the polyester (B111). Carbon-carbon double bonds are bonded by a crosslinking reaction. Thereby, a non-linear polyester resin can be manufactured. This method is a preferable method because the crosslinking reaction can be made uniform in a short time.

  The radical reaction initiator used for the crosslinking reaction of the polyester (B111) is not particularly limited, and includes the aforementioned inorganic peroxides, organic peroxides, and azo compounds. These radical reaction initiators may be used alone or in combination of two or more.

The amount of the radical reaction initiator used is not particularly limited, but is 0.1 to 50% by weight based on the total weight of the unsaturated carboxylic acid component and the unsaturated alcohol component used in the polymerization reaction for obtaining the polyester (B111). Parts are preferred.
When the amount of the radical reaction initiator used is 0.1 part by weight or more, the crosslinking reaction tends to proceed easily, and when the amount is 50 parts by weight or less, the odor tends to be good. This amount is more preferably at most 30 parts by weight, particularly preferably at most 20 parts by weight, most preferably at most 10 parts by weight.

  When the polyester resin (B1) is produced by using the above-mentioned type of radical reaction initiator in the above-mentioned usage amount, a cross-linking reaction between carbon-carbon double bonds in the polyester (B111) suitably occurs, and the resistance of the toner is improved. It is preferable because the hot offset property, heat storage stability, and image strength are improved.

The acid value of the polyester resin (B1) is preferably from 0 to 30 mgKOH / g, more preferably from 0 to 25 mgKOH / g, particularly preferably from 0 to 10 mgKOH / g, most preferably from the viewpoint of charge stability. Is 0.1 to 10 mgKOH / g.
The acid value of the polyester resin (B1) can be measured by a method specified in JIS K0070 (1992 version).

  The weight ratio of the vinyl resin (A) in the toner binder is from 5 to 100% by weight based on the weight of the toner binder from the viewpoint of the balance between storage elasticity and loss elasticity and the charge stability and durability of the toner. Preferably, it is 10 to 100% by weight, more preferably 20 to 100% by weight, most preferably 30 to 95% by weight.

Regarding the viscoelasticity of the toner binder, particularly, the loss elastic modulus at 80 ° C. [low temperature loss elastic modulus G ″ (80 ° C.)] is preferably 6.0E + 02 Pa to 3.0E + 05 Pa, more preferably, from the viewpoint of fixing property of the toner. Is 6.0E + 02Pa to 1.0E + 05Pa.
If it is 6.0E + 02 Pa or more, the fixing becomes good. On the other hand, if the pressure is 3.0E + 05Pa or less, adhesion to paper at the time of fixing is sufficient.
Regarding the viscoelasticity of the toner binder, the storage elastic modulus at 110 ° C. [high-temperature storage elastic modulus G ′ (110 ° C.)] is preferably 6.0E + 02 Pa or more, more preferably 1.0E + 04 Pa, from the viewpoint of hot offset resistance. That is all.
In addition, in the present specification, in the case of displaying by E + number, E + 02 means multiplying by a number with zero added to the number, such as 100 times, and E + 05 is 100,000 times.
The loss modulus and the storage modulus of the toner binder can be measured by the same method as described in the description of the storage modulus G ′ of the vinyl resin (A).
The storage elastic modulus and the loss elastic modulus of the toner binder can be adjusted to the above preferred ranges by the weight average molecular weight of the vinyl resin (A) and the composition of the constituent monomers. For example, the storage elastic modulus and the loss elastic modulus of the toner binder can be increased by increasing the weight average molecular weight of (A), increasing the polarity of the monomer composition, or the like.

The melting peak temperature Tm of the toner binder measured by DSC is preferably from 35 to 80 ° C, more preferably from 38 to 77 ° C, and particularly preferably from 40 to 75 ° C.
At 35 ° C. or higher, the storage stability of the toner becomes good. On the other hand, when the temperature is 80 ° 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 vinyl resin (A).
The melting peak temperature Tm of the toner binder is adjusted by adjusting the carbon number of the monomer (a) constituting the vinyl resin (A) and adjusting the weight ratio of the monomer (a) constituting the (A). Can be adjusted to the above preferable range. For example, Tm can be increased by a method such as increasing the number of carbon atoms in (a), increasing the weight ratio of (a), or increasing the weight average molecular weight of (A). When the content of (A) is small, Tm can be maintained without lowering by increasing the | ΔSP value | with respect to the other resin (B).
The SP value of the resin is determined by the method of Fedors [Polym. Eng. Sci. 14 (2) 152, (1974)].

It is preferable that the toner binder satisfies the relational expression (1) from the viewpoints of storage stability and low-temperature fixability when formed into a toner.
Relational expression (1): 1.2 ≦ ln ( _G′Tm−10 ) / ln ( _{G′Tm + 30} ) ≦ 2.6
However, the calculated value shall be obtained by rounding off the second decimal place.

More preferably, it satisfies the relational expression (2), and particularly preferably satisfies the relational expression (3).
Relational expression (2): 1.6 ≦ ln (G ′ _Tm−10 ) / ln (G ′ _{Tm + 30} ) ≦ 2.6
Relational expression (3): 1.7 ≦ ln (G ′ _Tm−10 ) / ln (G ′ _{Tm + 30} ) ≦ 2.5

In the relational expressions (1), (2) and (3), G ′ _Tm−10 is the storage elastic modulus (Pa) of the toner binder when the temperature of the toner binder is (Tm−10) ° C. ' _{Tm + 30} is the storage elastic modulus (Pa) of the toner binder when the temperature of the toner binder is (Tm + 30) ° C.
In (G ′ _Tm−10 ) / ln (G ′ _{Tm + 30} ) can be adjusted by the weight average molecular weight of the vinyl resin (A) and the type and amount of the monomer (b) or the monomer (c). . For example, reducing the weight average molecular weight of the vinyl resin (A), (b) and lowering the polarity of the (c), reduce the amount of (b), the method than ln (G _'Tm such increase the amount of (c) ₋₁₀ ) / ln (G ′ _{Tm + 30} ).
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 vinyl resin (A) using the viscoelasticity measuring device.

The method for producing the toner binder will be described.
The toner binder is not particularly limited as long as it contains the vinyl resin (A). For example, a known method for mixing the vinyl resin (A) and other resins (B) and additives used as needed is a known method. As the mixing method, powder mixing, melt mixing, solvent mixing and the like can be mentioned. Further, (A) and (B) and additives used as necessary may be mixed at the same time when the toner is produced. Among these methods, a melt-mixing method that mixes uniformly and does not require solvent removal is preferred.

Examples of a mixing device for mixing powder include a Henschel mixer, a Nauter mixer, and a Banbury mixer. Preferably, it is a Henschel mixer.
Examples of the mixing device in the case of melt mixing include a batch type mixing device such as a reaction tank and a continuous type mixing device. In order to mix uniformly at an appropriate temperature in a short time, a continuous mixing apparatus is preferable. Examples of the continuous mixing device include a static mixer, an extruder, a continuous kneader, and a three-roll mixer.
The temperature during mixing is preferably from 50 to 200 ° C. 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, and any solvent may be used as long as it can suitably dissolve all the polymers constituting the toner binder (toluene, acetone, and the like).
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.

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

As the colorant, any of dyes, pigments and the like used as colorants for toner can be used. For example, carbon black, iron black, Sudan Black SM, Fast Yellow G, Benzidine Yellow, Pigment Yellow, India First Orange, Pigment Red, Irgasin Red, Paranitroaniline Red, Toluidine Red, Carmine FB, Pigment Orange R, Lake Red 2G, Rhodamine FB, Rhodamine B lake, Methyl Violet B lake, Phthalocyanine blue, Pigment blue, Brilliant green, Phthalocyanine green, Pigment yellow, Oil yellow GG, Kayaset YG, Orazol brown B, Oil pink OP, and the like. Can be used alone or in combination of two or more. If necessary, a magnetic powder (a powder of a ferromagnetic metal such as iron, cobalt, and nickel or a compound such as magnetite, hematite, and ferrite) can be contained 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 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.

As the release agent, those having a flow softening point [T _1/2 ] of 50 to 170 ° C. described below are preferable, and aliphatic hydrocarbon waxes such as polyolefin wax, microcrystalline wax, paraffin wax, and Fischer-Tropsch wax. And their oxides, carnauba wax, montan wax and their deoxidized waxes, ester waxes, fatty acid amides, fatty acids, higher alcohols, fatty acid metal salts and the like.
<Flow softening point [T _1/2 ]>
Using a descending flow tester {for example, CFT-500D, manufactured by Shimadzu Corporation), applying a load of 1.96 MPa with a plunger while heating 1 g of the measurement sample at a heating 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 (flow value)" and "Temperature", and graph the temperature corresponding to 1/2 of the maximum value of the plunger descent. And this value (the temperature at which half of the measured sample flows out) is defined as the flow softening point [T _1/2 ].

  Examples of the polyolefin wax include (co) polymers of olefins (ethylene, propylene, 1-butene, isobutylene, 1-hexene, 1-dodecene, 1-octadecene, and mixtures thereof), and those obtained by (co) polymerization. Including those obtained by further thermal degradation] (eg, low molecular weight polypropylene, low molecular weight polyethylene, low molecular weight polypropylene polyethylene copolymer), oxides of (co) polymers of olefins with oxygen and / or ozone Maleic acid-modified olefin (co) polymer [maleic acid and its derivatives (maleic anhydride, monomethyl maleate, monobutyl maleate and dimethyl maleate) and the like], olefins and unsaturated carboxylic acids [( Meth) acrylic acid, itaconic acid, maleic anhydride, etc.] and / or Copolymer of an unsaturated carboxylic acid alkyl ester [(meth) acrylic acid alkyl (C1-18 alkyl) esters and maleic acid alkyl (C1-18 alkyl) esters, etc.] and the like.

  Examples of the microcrystalline wax include Hi-Mic-2095, Hi-Mic-1090, Hi-Mic-1080, Hi-Mic-1070, Hi-Mic-2065, and Hi-Mic- manufactured by Nippon Seiro Co., Ltd. 1045, Hi-Mic-2045 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-5 manufactured by Nippon Seiro Co., Ltd. 9, HNP-10, HNP-11, HNP-12, HNP-51 and the like.

  Examples of the Fischer-Tropsch wax include Sasolwax C80 manufactured by Sasol.

  Examples of carnauba wax include refined carnauba wax No. 1 manufactured by Kato Yoko Co., Ltd.

  Examples of the ester wax include fatty acid ester waxes (for example, Nissan Elector WEP-2, WEP-3, WEP-4, WEP-5, and WEP-8 manufactured by NOF Corporation).

  Examples of the higher alcohol 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 triacontancarboxylic acid.

  Examples of the fatty acid amide include Diamid Y and Diamid 200 manufactured by Mitsubishi Chemical Corporation.

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

  As the charge control agent, any of a positive charge control agent and a negative charge control agent may be contained, and a nigrosine dye, a triphenylmethane dye containing a tertiary amine as a side chain, and a quaternary ammonium Salt, polyamine, imidazole derivative, quaternary ammonium base-containing polymer, metal-containing azo dye, copper phthalocyanine dye, salicylic acid metal salt, boron complex of benzylic acid, sulfonic acid group-containing polymer, fluorine-containing polymer, and halogen-substituted fragrance Ring-containing polymers and the like can be mentioned.

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

  The content of the toner binder in the toner is preferably 30 to 97% by weight, more preferably 40 to 95% by weight, and particularly 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, and particularly preferably 0.5 to 50% by weight based on the weight of the toner. The content of the release agent is preferably 0 to 30% by weight, more preferably 0.5 to 20% by weight, and particularly 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, and particularly preferably 0.5 to 7.5% by weight based on the weight of the toner. The content of the fluidizing agent is preferably 0 to 10% by weight, more preferably 0 to 5% by weight, particularly preferably 0.1 to 4% by weight based on the weight of the toner. Further, the total content of the colorant, 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, and particularly preferably 5 to 50% by weight. When the composition ratio of the toner is in the above range, a toner having good chargeability can be easily obtained.

  The method for producing the toner when the toner binder of the present invention is used as a toner is not particularly limited, and known methods such as a kneading and pulverizing method, an emulsion inversion method, an emulsion polymerization method, a suspension polymerization method, a solution suspension method, and an emulsion aggregation method are known. May be obtained by any of the above methods.

  For example, when the toner is obtained by a kneading and pulverizing method, the components constituting the toner excluding the fluidizing agent are dry-blended, melt-kneaded, then coarsely pulverized, and finally finely divided using a jet mill pulverizer or the like. By further classifying the mixture, fine particles having a volume average particle size (D50) of preferably 5 to 20 μm can be produced by mixing with a fluidizing agent. The volume average particle size (D50) is measured using a Coulter counter [for example, trade name: Multisizer III (manufactured by Coulter)].

  When the toner is obtained by the emulsification phase inversion method, it is possible to dissolve or disperse the components constituting the toner except for the fluidizing agent in an organic solvent, emulsify by adding water, and then separate and classify the toner. it can. The volume average particle diameter of the toner is preferably 3 to 15 μm.

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

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

  When the toner binder of the present invention is used as a toner, the toner may include, as necessary, iron powder, glass beads, nickel powder, ferrite, magnetite, and ferrite whose surface is coated with a resin (such as an acrylic polymer or a silicone polymer). And used as a developer for an electric latent image. The weight ratio between the toner and the carrier particles is from 1/99 to 100/0. Further, instead of the carrier particles, friction with a member such as a charging blade can be performed to form an electric latent image.

The toner binder of the present invention can be prepared by a chemical method using a monomer having an ethylenically unsaturated bond, such as emulsion polymerization or suspension polymerization, in addition to a method that requires a special particle forming technique such as a solution suspension method or an emulsion aggregation method. Also suitable for toner production.
When the toner binder of the present invention is used as a toner, the toner is fixed on a support (paper, polyester film, or the like) by a copying machine, a printer, or the like to form a recording material. As a method for fixing to a support, a known hot roll fixing method, flash fixing method, and the like can be applied.

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

<Production Example 1> [Synthesis of palmityl acrylate (a2)]
A reaction vessel equipped with a stirrer, a heating / cooling device, a thermometer, an air inlet tube, a pressure reducing device, and a water reducing device was charged with 50 parts of palmityl alcohol, 50 parts of toluene, 22 parts of acrylic acid, and 0.05 part of hydroquinone, Stir to homogenize. Thereafter, 2 parts of paratoluenesulfonic acid was added, and the mixture was stirred for 30 minutes, and reacted for 5 hours while removing water generated at 100 ° C. while blowing air at a flow rate of 30 ml / min. Thereafter, the pressure in the reaction vessel was adjusted to 40 kPa, and the reaction was further performed for 3 hours while removing generated water. After the reaction solution was cooled to room temperature, 30 parts of a 10% by weight aqueous sodium hydroxide solution was added thereto, and the mixture was stirred for 1 hour and allowed to stand still to separate an organic phase and an aqueous phase. The organic phase was collected by liquid separation and centrifugation, and 0.01 part of hydroquinone was added. The solvent was removed under reduced pressure while blowing air to obtain palmityl acrylate (a2).

<Production Example 2> [Synthesis of arachidyl acrylate (a3)]
A reaction vessel equipped with a stirrer, a heating / cooling device, a thermometer, an air introduction tube, a decompression device, and a water reduction device, was charged with 50 parts of arachidyl alcohol, 50 parts of toluene, 18 parts of acrylic acid, and 0.05 part of hydroquinone, Stir to homogenize. Thereafter, 2 parts of paratoluenesulfonic acid was added, and the mixture was stirred for 30 minutes, and reacted for 5 hours while removing water generated at 100 ° C. while blowing air at a flow rate of 30 ml / min. Thereafter, the pressure in the reaction vessel was adjusted to 40 kPa, and the reaction was further performed for 3 hours while removing generated water. After the reaction solution was cooled to room temperature, 30 parts of a 10% by weight aqueous sodium hydroxide solution was added thereto, and the mixture was stirred for 1 hour and allowed to stand still to separate an organic phase and an aqueous phase. The organic phase was collected by liquid separation and centrifugation, and 0.01 part of hydroquinone was added. The solvent was removed under reduced pressure while blowing air to obtain arachidyl acrylate (a3).

<Production Example 3> [Synthesis of vinyl resin (A-1)]
After charging 46 parts of toluene in an autoclave and purging with nitrogen, the temperature was raised to 105 ° C. in a sealed state with stirring. 59.3 parts of stearyl acrylate [manufactured by NOF CORPORATION, the same applies hereinafter], 0.6 parts of palmityl acrylate obtained in Production Example 1, 0.1 part of arachidyl acrylate obtained in Production Example 2, styrene [Idemitsu Kosan 20.0 parts, acrylonitrile [manufactured by Nakarai-Tex Co., Ltd., the same applies hereinafter] 20.0 parts, Karenz MOI [2-isocyanatoethyl methacrylate, manufactured by Showa Denko KK, the same applies hereinafter] A mixed solution of 1.9 parts, perbutyl O [t-butyl peroxy-2-ethylhexanoate, NOF CORPORATION, the same applies hereinafter] 0.36 part, and 23 parts of toluene was heated to an autoclave temperature of 105 ° C. While controlling, polymerization was carried out by dropping over 2 hours. After the polymerization was completed at the same temperature for 4 hours to complete the polymerization, 0.6 part of methanol and 0.5 part of Neostan U-600 (Nitto Kasei Kogyo Co., Ltd .; the same applies hereinafter) were added, and the reaction was carried out at 90 ° C. for 6 hours. went. Thereafter, the solvent was removed at 100 ° C. to obtain a vinyl resin (A-1).

<Production Example 4> [Synthesis of vinyl resin (A-2)]
After charging 46 parts of toluene in an autoclave and purging with nitrogen, the temperature was raised to 105 ° C. in a sealed state with stirring. 49.0 parts of stearyl acrylate, 10.0 parts of palmityl acrylate, 1.0 part of arachidyl acrylate, 20.0 parts of styrene, 20.0 parts of acrylonitrile, 1.9 parts of Karenz MOI, 0.36 part of perbutyl O, and toluene 23 A part of the mixed solution was added dropwise over 2 hours while the temperature inside the autoclave was controlled at 105 ° C., and polymerization was carried out. After keeping the polymerization at the same temperature for 4 hours to complete the polymerization, 0.6 part of methanol and 0.5 part of Neostan U-600 were added, and the mixture was reacted at 90 ° C. for 6 hours. Thereafter, the solvent was removed at 100 ° C. to obtain a vinyl resin (A-2).

<Production Example 5> [Synthesis of vinyl resin (A-3)]
After charging 46 parts of toluene in an autoclave and purging with nitrogen, the temperature was raised to 105 ° C. in a sealed state with stirring. 75.0 parts of stearyl acrylate, 4.5 parts of palmityl acrylate, 0.5 part of arachidyl acrylate, 10.0 parts of styrene, 10.0 parts of acrylonitrile, 1.9 parts of Karenz MOI, 0.36 part of perbutyl O, and toluene 23 A part of the mixed solution was added dropwise over 2 hours while the temperature inside the autoclave was controlled at 105 ° C., and polymerization was carried out. After keeping the polymerization at the same temperature for 4 hours to complete the polymerization, 0.6 part of methanol and 0.5 part of Neostan U-600 were added, and the mixture was reacted at 90 ° C. for 6 hours. Thereafter, the solvent was removed at 100 ° C. to obtain a vinyl resin (A-3).

<Production Example 6> [Synthesis of vinyl resin (A-4)]
After charging 46 parts of toluene in an autoclave and purging with nitrogen, the temperature was raised to 105 ° C. in a sealed state with stirring. A mixed solution of 66.0 parts of stearyl acrylate, 3.8 parts of palmityl acrylate, 0.2 part of arachidyl acrylate, 15.0 parts of styrene, 15.0 parts of acrylonitrile, 0.36 part of perbutyl O, and 23 parts of toluene, While controlling the temperature in the autoclave at 105 ° C., polymerization was carried out by dropping over 2 hours. After the polymerization was completed at the same temperature for 4 hours to complete the polymerization, the solvent was removed at 100 ° C. to obtain a vinyl resin (A-4).

<Production Example 7> [Synthesis of vinyl resin (A-5)]
After charging 46 parts of toluene in an autoclave and purging with nitrogen, the temperature was raised to 105 ° C. in a sealed state with stirring. 32.0 parts of stearyl acrylate, 20.0 parts of palmityl acrylate, 1.0 part of arachidyl acrylate, 10.0 parts of styrene, 37.0 parts of acrylonitrile, 1.9 parts of Karenz MOI, 0.36 parts of perbutyl O, and toluene 23 A part of the mixed solution was added dropwise over 2 hours while the temperature inside the autoclave was controlled at 105 ° C., and polymerization was carried out. After keeping the polymerization at the same temperature for 4 hours to complete the polymerization, 0.6 part of methanol and 0.5 part of Neostan U-600 were added, and the mixture was reacted at 90 ° C. for 6 hours. Thereafter, the solvent was removed at 100 ° C. to obtain a vinyl resin (A-5).

<Production Example 8> [Synthesis of vinyl resin (A-6)]
After charging 46 parts of toluene in an autoclave and purging with nitrogen, the temperature was raised to 105 ° C. in a sealed state with stirring. 93.0 parts of stearyl acrylate, 0.8 parts of palmityl acrylate, 0.2 parts of arachidyl acrylate, 3.0 parts of styrene, 3.0 parts of acrylonitrile, 1.9 parts of Karenz MOI, 0.36 parts of perbutyl O, and toluene 23 A part of the mixed solution was added dropwise over 2 hours while the temperature inside the autoclave was controlled at 105 ° C., and polymerization was carried out. After keeping the polymerization at the same temperature for 4 hours to complete the polymerization, 0.6 part of methanol and 0.5 part of Neostan U-600 were added, and the mixture was reacted at 90 ° C. for 6 hours. Thereafter, the solvent was removed at 100 ° C. to obtain a vinyl resin (A-6).

<Production Example 9> [Synthesis of vinyl resin (A-7)]
An autoclave was charged with 30.0 parts of stearyl acrylate, 0.1 part of palmityl acrylate, 0.1 part of arachidyl acrylate, 29.8 parts of behenyl acrylate, and 53.0 parts of toluene. To 60 ° C. A mixed solution of 13 parts of styrene, 20.0 parts of methacrylonitrile, 7.0 parts of acrylic acid, 2.0 parts of 2,2′-azobis (2,4-dimethylvaleronitrile), and 43.0 parts of toluene, The polymerization was carried out dropwise over 2 hours while controlling the temperature in the autoclave at 60 ° C. After the dropping, the dropping line was washed with 4.0 parts of toluene. Further, the temperature was maintained at the same temperature for 4 hours, the temperature was raised to 80 ° C. over 1 hour, and the temperature was maintained at 80 ° C. for 1 hour. Further, 1.0 part of 2,2′-azobis (2,4-dimethylvaleronitrile) was added, and the mixture was reacted at 80 ° C. for 2 hours. The solvent was removed under reduced pressure of 0.5 to 2.5 kPa at 120 ° C. for 6 hours to obtain a vinyl resin (A-7).

<Production Example 10> [Synthesis of vinyl resin (A-8)]
An autoclave was charged with 39.8 parts of stearyl acrylate, 0.1 part of palmityl acrylate, 0.1 part of arachidyl acrylate, 30.0 parts of behenyl acrylate, and 35.0 parts of ethyl acetate. In this state, the temperature was raised to 60 ° C. A mixture of 10.0 parts of styrene, 15.0 parts of methacrylonitrile, 5.0 parts of methacrylic acid, 1.0 part of 2,2′-azobis (2,4-dimethylvaleronitrile), and 28.5 parts of ethyl acetate. The solution was added dropwise over 2 hours while the temperature in the autoclave was controlled at 60 ° C., and polymerization was carried out. After the addition, the addition line was washed with 3.0 parts of ethyl acetate. Further, the temperature was maintained at the same temperature for 4 hours, the temperature was raised to 80 ° C. over 1 hour, and the temperature was maintained at 80 ° C. for 1 hour. Further, 0.5 part of 2,2′-azobis (2,4-dimethylvaleronitrile) was added thereto and reacted at 80 ° C. for 2 hours. The solvent was removed under reduced pressure of 0.5 to 2.5 kPa at 120 ° C. for 6 hours to obtain a vinyl resin (A-8).

<Production Example 11> [Synthesis of palmityl methacrylate (a2-2)]
A reaction vessel equipped with a stirrer, a heating / cooling device, a thermometer, an air introduction pipe, a decompression device, and a water reduction device, was charged with 50 parts of palmityl alcohol, 50 parts of toluene, 26 parts of methacrylic acid, and 0.05 part of hydroquinone, Stir to homogenize. Thereafter, 2 parts of paratoluenesulfonic acid was added, and the mixture was stirred for 30 minutes, and reacted for 5 hours while removing water generated at 100 ° C. while blowing air at a flow rate of 30 ml / min. Thereafter, the pressure in the reaction vessel was adjusted to 40 kPa, and the reaction was further performed for 3 hours while removing generated water. After cooling the reaction solution to room temperature, 30 parts of a 10% by weight aqueous sodium hydroxide solution was added thereto, and the mixture was stirred for 1 hour, and then allowed to stand to separate an organic phase and an aqueous phase. The organic phase was collected by liquid separation, 0.01 part of hydroquinone was charged, and the solvent was removed under reduced pressure while blowing air into the solution to obtain palmityl methacrylate (a2-2).

<Production Example 12> [Synthesis of arachidyl methacrylate (a3-2)]
Into a reaction vessel equipped with a stirrer, a heating / cooling device, a thermometer, an air introduction pipe, a decompression device, and a water reduction device, were charged 50 parts of arachidyl alcohol, 50 parts of toluene, 22 parts of methacrylic acid, and 0.05 part of hydroquinone, Stir to homogenize. Thereafter, 2 parts of paratoluenesulfonic acid was added, and the mixture was stirred for 30 minutes, and reacted for 5 hours while removing water generated at 100 ° C. while blowing air at a flow rate of 30 ml / min. Thereafter, the pressure in the reaction vessel was adjusted to 40 kPa, and the reaction was further performed for 3 hours while removing generated water. After cooling the reaction solution to room temperature, 30 parts of a 10% by weight aqueous sodium hydroxide solution was added thereto, and the mixture was stirred for 1 hour, and then allowed to stand to separate an organic phase and an aqueous phase. The organic phase was collected by liquid separation, 0.01 parts of hydroquinone was charged, and the solvent was removed under reduced pressure while blowing air to obtain arachidyl methacrylate (a3-2).

<Production Example 13> [Synthesis of vinyl resin (A-9)]
An autoclave was charged with 49.0 parts of stearyl methacrylate, 0.1 part of palmityl methacrylate, 0.9 part of arachidyl methacrylate, and 35.0 parts of ethyl acetate. After the atmosphere was replaced with nitrogen, the temperature was raised to 60 ° C in a sealed state with stirring. did. A mixture of 20.0 parts of styrene, 26.5 parts of methacrylonitrile, 3.5 parts of acrylic acid, 0.8 parts of 2,2′-azobis (2,4-dimethylvaleronitrile), and 28.5 parts of ethyl acetate. The solution was added dropwise over 2 hours while the temperature in the autoclave was controlled at 60 ° C., and polymerization was carried out. After the addition, the addition line was washed with 3.0 parts of ethyl acetate. Further, the temperature was maintained at the same temperature for 4 hours, the temperature was raised to 80 ° C. over 1 hour, and the temperature was maintained at 80 ° C. for 1 hour. Further, 0.5 part of 2,2′-azobis (2,4-dimethylvaleronitrile) was added thereto and reacted at 80 ° C. for 2 hours. The solvent was removed at 120 ° C. for 6 hours under a reduced pressure of 0.5 to 2.5 kPa to obtain a vinyl resin (A-9).

<Production Example 14> [Production of polyester (B111-1)]
In a reactor equipped with a cooling pipe, a stirrer and a nitrogen introducing pipe, 741 parts of bisphenol A / EO 2 mol adduct, 118 parts of terephthalic acid, 118 parts of adipic acid, 13 parts of trimethylolpropane, titanium diisopropoxy as a condensation catalyst 2.5 parts of bistriethanolamate was added and reacted at 230 ° C. for 2 hours under a nitrogen stream while distilling off generated water. Next, after reacting for 5 hours under reduced pressure of 0.5 to 2.5 kPa, the temperature was lowered to 180 ° C. One part of tert-butyl catechol was added as a polymerization inhibitor, and 86 parts of fumaric acid was further added. The mixture was reacted under a reduced pressure of 0.5 to 2.5 kPa for 8 hours and taken out to obtain a polyester (B111-1). The glass transition temperature of the polyester (B111-1) was 37 ° C., the weight average molecular weight was 23,000, and the acid value was 2.

<Comparative Production Example 1> [Synthesis of vinyl resin (A'-1)]
After charging 46 parts of toluene in an autoclave and purging with nitrogen, the temperature was raised to 105 ° C. in a sealed state with stirring. A mixed solution of 39.4 parts of stearyl acrylate, 0.6 parts of palmityl acrylate, 30.0 parts of styrene, 30.0 parts of acrylonitrile, 1.9 parts of Karenz MOI, 0.36 parts of perbutyl O, and 23 parts of toluene was placed in an autoclave. While controlling the temperature at 105 ° C., polymerization was carried out by dropping over 2 hours. After keeping the polymerization at the same temperature for 4 hours to complete the polymerization, 0.6 part of methanol and 0.5 part of Neostan U-600 were added, and the mixture was reacted at 90 ° C. for 6 hours. Thereafter, the solvent was removed at 100 ° C. to obtain a vinyl resin (A′-1).

<Comparative Production Example 2> [Synthesis of vinyl resin (A'-2)]
After charging 46 parts of toluene in an autoclave and purging with nitrogen, the temperature was raised to 105 ° C. in a sealed state with stirring. A mixed solution of 58.0 parts of stearyl acrylate, 2.0 parts of arachidyl acrylate, 20.0 parts of styrene, 20.0 parts of acrylonitrile, 1.9 parts of Karenz MOI, 0.36 parts of perbutyl O, and 23 parts of toluene was placed in an autoclave. While controlling the temperature at 105 ° C., polymerization was carried out by dropping over 2 hours. After keeping the polymerization at the same temperature for 4 hours to complete the polymerization, 0.6 part of methanol and 0.5 part of Neostan U-600 were added, and the mixture was reacted at 90 ° C. for 6 hours. Thereafter, the solvent was removed at 100 ° C. to obtain a vinyl resin (A′-2).

<Comparative Production Example 3> [Synthesis of vinyl resin (A'-3)]
After charging 46 parts of toluene in an autoclave and purging with nitrogen, the temperature was raised to 105 ° C. in a sealed state with stirring. 69.0 parts of stearyl acrylate, 20.6 parts of palmityl acrylate, 0.4 parts of arachidyl acrylate, 5.0 parts of styrene, 5.0 parts of acrylonitrile, 1.9 parts of Karenz MOI, 0.36 parts of perbutyl O, and toluene 23 A part of the mixed solution was added dropwise over 2 hours while the temperature inside the autoclave was controlled at 105 ° C., and polymerization was carried out. After keeping the polymerization at the same temperature for 4 hours to complete the polymerization, 0.6 part of methanol and 0.5 part of Neostan U-600 were added, and the mixture was reacted at 90 ° C. for 6 hours. Thereafter, the solvent was removed at 100 ° C. to obtain a vinyl resin (A′-3).

<Comparative Production Example 4> [Synthesis of vinyl resin (A'-4)]
After charging 46 parts of toluene in an autoclave and purging with nitrogen, the temperature was raised to 105 ° C. in a sealed state with stirring. Stearyl acrylate 30.0 parts, palmityl acrylate 4.0 parts, arachidyl acrylate 1.0 parts, styrene 30.0 parts, acrylonitrile 35.0 parts, Karenz MOI 1.9 parts, perbutyl O 0.36 parts, and toluene 23 A part of the mixed solution was added dropwise over 2 hours while the temperature inside the autoclave was controlled at 105 ° C., and polymerization was carried out. After keeping the polymerization at the same temperature for 4 hours to complete the polymerization, 0.6 part of methanol and 0.5 part of Neostan U-600 were added, and the mixture was reacted at 90 ° C. for 6 hours. Thereafter, the solvent was removed at 100 ° C. to obtain a vinyl resin (A′-4).

<Comparative Production Example 5> [Synthesis of vinyl resin (A'-5)]
After charging 46 parts of toluene in an autoclave and purging with nitrogen, the temperature was raised to 105 ° C. in a sealed state with stirring. A mixed solution of 98.6 parts of stearyl acrylate, 0.6 part of palmityl acrylate, 0.1 part of arachidyl acrylate, 0.7 part of styrene, 0.2 part of perbutyl O, and 23 parts of toluene was heated at an autoclave temperature of 105 ° C. Was added dropwise over 2 hours to carry out polymerization. After the polymerization was completed at the same temperature for 4 hours to complete the polymerization, the solvent was removed at 100 ° C. to obtain a vinyl resin (A′-5).

  Vinyl resins (A-1) to (A-9) obtained in Production Examples 3 to 10 and 13, and comparative vinyl resins (A'-1) to (A'-5) obtained in Comparative Production Examples 1 to 5. ) Was evaluated for weight average molecular weight and melting peak temperature Tm (° C.) by the following methods. The results are shown in Table 1.

  The weight average molecular weights of the vinyl resins (A) and (A ') were measured using GPC under the above conditions.

The melting peak temperatures Tm (° C.) of the vinyl resins (A) and (A ′) were measured under the following conditions using a differential scanning calorimeter {manufactured by TA Instruments, DSC Q20, 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) 10 ° C. at 10 ° C. (6) Heat up to 150 ° C. at 10 ° C./min. (7) Analyze each endothermic peak capable of forming a differential scanning calorimetric curve measured in the process of (6).

<Examples 1-3, 5, 6 and Comparative Examples 1-5>
The vinyl resins (A-1) to (A-3), (A-5), and (A-6) obtained in Production Examples 1 to 3, 5, and 6 were used as toner binders, and were obtained in Comparative Production Examples 1 to 5. Using the vinyl resins (A′-1) to (A′-5) as comparative toner binders, the toners (T-1) to (T-3), (T-5), T-6) and (T'-1) to (T'-5). In addition, carbon black [MA-100 manufactured by Mitsubishi Chemical Corporation] as a colorant, polyolefin wax [Viscol 550P manufactured by Sanyo Chemical Industries, Ltd.] as a release agent, and Aizen Spiron Black [Hodogaya] as a charge control agent T-77 manufactured by Chemical Co., Ltd.], and hydrophobic silica [Aerosil R972 manufactured by Nippon Aerosil Co., Ltd.] was used as a fluidizing agent.
First, a vinyl resin (A), a colorant, a release agent, and a charge control agent were added so as to have the compounding ratio shown in Table 2, and preliminarily mixed using a Henschel mixer [FM10B manufactured by Nippon Coke Industry Co., Ltd.]. The mixture was kneaded with a shaft kneader [PCM-30 manufactured by Ikegai Co., Ltd.]. Then, after finely pulverizing using a supersonic jet pulverizer LabJet [manufactured by Nippon Pneumatic Industries, Ltd.], the mixture was classified using an airflow classifier [MDS-I, manufactured by Nippon Pneumatic Industries, Ltd.] to obtain a volume average particle size. (D50) was obtained having a particle size of 7 μm. Next, hydrophobic silica was mixed with 100 parts by weight of the toner particles in a sample mill so as to have a compounding ratio shown in Table 2, to obtain a toner.

<Example 4>
30 parts by weight of polyester (B111-1) and 70 parts by weight of vinyl resin (A-4) are mixed and supplied to a twin-screw kneader (S5KRC kneader, manufactured by Kurimoto Tekkosho) at a rate of 52 kg / hour, and at the same time, t-butyl. 2.0 parts by weight of peroxyisopropyl monocarbonate was supplied at a rate of 1.04 kg / hour, kneaded and extruded at 160 ° C. for 7 minutes at 90 rpm to carry out a crosslinking reaction, and the organic solvent was removed by reducing the pressure at 10 kPa from the vent port. While mixing. The toner binder of the present invention was obtained by cooling the mixture obtained by mixing.
In the same manner as in Example 1 except that the obtained toner binder was used in place of the vinyl resin (A-1), a toner particle (D-4) having a volume average particle diameter (D50) of 7 μm and a toner (T-4) were obtained. Was.

<Examples 7 to 9>
The vinyl resin (A) and the polyester (B111) in the parts by weight shown in Table 2 were mixed and supplied to a twin-screw kneader, and at the same time, t-butylperoxyisopropyl monocarbonate was supplied. The crosslinking reaction and the removal of the organic solvent were performed to obtain the toner binder of the present invention.
Example 1 was repeated except that the toner binder obtained in place of the vinyl resin (A-1) was used. The toner particles having a volume average particle diameter (D50) of 7 μm and the toners (T-7) to (T-7) T-9) was obtained.

G ′ _Tm−10 (Pa) and G ′ _{Tm + 30} (Pa) of the toner binder were measured using the following viscoelasticity measuring device under the following conditions.
Apparatus: ARES-24A (Rheometrics)
Jig: 25mm parallel plate Frequency: 1Hz
Distortion rate: 5%
Heating rate: 5 ° C / min

  The melting peak temperature Tm (° C.) of the toner binder was measured in the same manner as the melting peak temperature Tm (° C.) of the vinyl resin (A).

[Evaluation method]
For the toners (T-1) to (T-9) and the comparative toners (T'-1) to (T'-5), low-temperature fixability, hot offset resistance, storage stability, and charge stability were determined by the following methods. The properties and durability were evaluated. Table 2 shows the results.

<Low temperature fixability>
The toner was uniformly placed on the paper surface at 0.6 mg / cm ² . At this time, the method of placing the powder on the paper used a printer without the heat fixing machine. Other methods may be used as long as the powder can be uniformly placed at the above weight density.
The low-temperature fixing temperature, which is the temperature at which cold offset occurs when the paper is passed through a pressure roller at a fixing speed (heating roller peripheral speed) of 213 mm / sec and a fixing pressure (pressure roller pressure) of 10 kg / cm ² , is measured. did.
The lower the low-temperature fixing temperature, the better the low-temperature fixing property.

<Hot offset resistance (hot offset generation temperature)>
The fixing was evaluated in the same manner as in the low-temperature fixing property, and the presence or absence of hot offset to the fixed image was visually evaluated.
The temperature at which hot offset occurred after passing through the pressure roller was defined as hot offset resistance (° C.).

<Storage stability test (blocking test)>
The particulate toner was allowed to stand in a dryer adjusted to a temperature of 40 ° C. for 15 hours, and the presence or absence of blocking was visually determined, and the heat-resistant storage stability was evaluated according to the following criteria.
[Judgment criteria]
：: Blocking has not occurred ×: Blocking has occurred

<Charging stability>
(1) 0.5 g of a toner and 20 g of a ferrite carrier (F-150, manufactured by Powder Tech) were placed in a 50 mL glass bottle, and the humidity was adjusted at 23 ° C. and a relative humidity of 50% for 8 hours or more.
(2) Friction stirring was performed at 50 rpm for 10 minutes and for 60 minutes using a Turbuler shaker mixer, and the charge amount at each time was measured.
A blow-off charge amount measuring device [manufactured by Toshiba Chemical Corporation] was used for the measurement.
"Electric charge amount for friction time of 60 minutes / electric charge amount for friction time of 10 minutes" was calculated and used as an index of electrification stability.
[Judgment criteria]
◎: 0.8 or more ○: 0.7 or more and less than 0.8 △: 0.6 or more and less than 0.7 ×: less than 0.6

<Durability>
Continuous copying was performed using a commercially available monochrome copying machine [AR5030, manufactured by Sharp Corporation] using the toner as a two-component developer, and the durability was evaluated according to the following criteria.
[Judgment criteria]
A: There is no change in image quality even after copying 10,000 sheets, and no fogging occurs.
○: Fogging has occurred after 10,000 copies.
Δ: Fog occurred after 6,000 copies.
×: Fog occurred after 2,000 sheets were copied.

  As is clear from the evaluation results in Table 2, the toners containing the toner binder of the present invention of Examples 1 to 9 obtained excellent results in any of the performance evaluation items. On the other hand, the toner of Comparative Example 1 using a toner binder containing a vinyl resin (A′-1) containing no (meth) acrylate (a3) having 20 carbon atoms in the chain hydrocarbon group has a low-temperature fixing property. Contains vinyl resin (A'-2) which is poor in hot offset resistance, storage stability and charging stability and does not use (meth) acrylate (a2) having a chain hydrocarbon group of 16 carbon atoms. The toner of Comparative Example 2 using a toner binder having poor charge stability and having a content of (meth) acrylate (a2) having a chain hydrocarbon group of 16 carbon atoms of more than 20% by weight The toner of Comparative Example 3 using the toner binder containing (A′-3) had poor charging stability and durability, and had a chain hydrocarbon group having 18 carbon atoms (meth) acrylate (a1). Content of 30 The toner of Comparative Example 4 using a toner binder containing a vinyl resin (A′-4) in an amount of less than 5% by weight has poor low-temperature fixability, hot offset resistance, storage stability and charging stability, and has a chain-like shape. The toner of Comparative Example 5 using a toner binder containing a vinyl resin (A′-5) containing a (meth) acrylate (a1) having 18 carbon atoms in the hydrocarbon group and having a content of more than 98.5% by weight is as follows: Hot offset resistance, charging stability and durability were poor.

The toner binder of the present invention is excellent in low-temperature fixing property, hot offset resistance, storage stability, charging stability and durability, and therefore, as a toner for developing an electrostatic image used in electrophotography, electrostatic recording and electrostatic printing. Useful.

Claims (3)

  A toner binder containing a vinyl resin (A), wherein the vinyl resin (A) is a polymer having the monomer (a) as an essential constituent monomer, and the monomer (a) is a chain carbonized resin. It is a (meth) acrylate having a hydrogen group and a chain hydrocarbon group having 16 to 36 carbon atoms, and based on the total weight of the monomers constituting the vinyl resin (A), The weight ratio of the (meth) acrylate (a1) having 18 carbon atoms is 30 to 98.5% by weight, and the weight ratio of the (meth) acrylate (a2) having 16 carbon atoms in the chain hydrocarbon group is 0.1%. 1 to 20% by weight, wherein the weight ratio of (meth) acrylate (a3) having 20 carbon atoms in the chain hydrocarbon group is 0.1 to 1% by weight.   The (meth) acrylate (a1) having 18 carbon atoms in the chain hydrocarbon group is stearyl acrylate, and the (meth) acrylate (a2) having 16 carbon atoms in the chain hydrocarbon group is palmityl acrylate. 2. The toner binder according to claim 1, wherein the (meth) acrylate (a3) having a carbon number of 20 in the form of a hydrocarbon is arachidyl acrylate. The toner binder according to claim 1, wherein a melting peak temperature Tm of the toner binder measured by DSC is 35 to 80 ° C., and the relational expression (1) is satisfied.
Relational expression (1): 1.2 ≦ ln ( _G′Tm−10 ) / ln ( _{G′Tm + 30} ) ≦ 2.6
[In the relational expression (1), 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 The storage elastic modulus (Pa) of the toner binder when the temperature is (Tm + 30) ° C. ]