JP5019259B2 - Toner additive, toner binder resin, and electrophotographic toner - Google Patents

Description

  The present invention relates to a toner additive, a toner binder resin, and an electrophotographic toner using the same.

Conventionally, an electrostatic image formed on a photoreceptor by electrophotography is developed by developing a latent image with a developer to form a toner image, and then the toner image is transferred and fixed on paper or the like. For fixing a toner image, a heat roller fixing method that has high thermal efficiency and enables high-speed fixing is widely used. In order to achieve energy saving by this method, low temperature fixability of the toner is required. Conventional toner binder resins have adopted techniques for lowering the softening point of the resin, but these techniques are accompanied by a decrease in the glass transition point, resulting in poor blocking resistance. Then, what has the polyol resin part which has heat resistance and fluidity | liquidity in the composition of binder resin is examined. For example, polyether polyol resin (for example, refer patent document 1), acid addition type polyether polyol resin (for example, refer patent document 2), and urethane-modified polyol resin (for example, refer patent document 3) are mentioned.
JP 2001-206945 A JP 2000-119370 A JP 2004-020575 A

  In Patent Document 1, a binder resin having an epoxy resin part and a polyester resin part has been studied. However, since the softening point is high, the low-temperature fixability is insufficient.

  In Patent Document 2, an acid addition type is used in order to make it negatively charged. However, since the acid addition type polyether polyol resin obtained has a high softening point, its low-temperature fixability is insufficient.

  In Patent Document 3, the urethane-modified polyol resin is studied in order to improve the high temperature offset resistance, but this does not improve the low temperature fixability.

On the other hand, fatty acid amides that do not react with epoxy resins (fatty acid amides that do not have active hydrogen) have been used for toner applications, limited to use as waxes (see, for example, Patent Document 4). In the present invention, a resin obtained by reacting an epoxy resin with a fatty acid amide having active hydrogen can be used as a toner binder resin having excellent wax dispersibility.
JP 2006-188467 A

  An object of the present invention is to provide a toner additive that improves low-temperature fixability and is excellent in wax dispersibility and blocking resistance, and an electrophotographic toner using the same. Another object is to provide an additive for toner having a wax function.

  As a result of intensive studies, the present inventors have found that a toner additive obtained by reacting at least an epoxy resin and a fatty acid amide and a toner using the additive have good low-temperature fixability, wax dispersibility, blocking resistance and It has been found that it has a wax function, and has led to the present invention.

That is, the present invention
(1) A toner additive comprising at least a resin obtained by reacting at least the following compound (A) with the following compound (B).
(A) Epoxy resin (B) Fatty acid amide which is a condensate of polyalkylene polyamines and fatty acids and has active hydrogen which reacts with an epoxy group (2) Compound (A) of (1) and (1 A toner additive comprising at least a resin obtained by reacting at least the compound (B) and the following compound (C):
(C) Monocarboxylic acids (3) The additive for toner according to (1) or (2) having a wax function.
(4) A toner binder resin containing the toner additives of (1) to (3).
(5) An electrophotographic toner containing at least the toner additive of (1) to (3) or the binder resin for toner of (4) and a colorant.
It is.

  The additive for toner, the binder resin for toner, and the electrophotographic toner using the toner additive of the present invention can have good low-temperature fixability, wax dispersibility, and blocking resistance.

  The compound (A), that is, the epoxy resin used in the present invention is a condensate of bisphenol A and epichlorohydrin, a condensate of bisphenol F and epichlorohydrin, a condensate of bisphenol AD and epichlorohydrin, bisphenol Condensate of C and epichlorohydrin, condensate of bisphenol S and epichlorohydrin, condensate of bisphenol E and epichlorohydrin, bisphenol type which is a condensate of bisphenol B and epichlorohydrin An epoxy resin, a cresol novolak type epoxy resin, a phenol novolak type epoxy resin, a dicyclopentadiene type epoxy resin, a naphthalene type epoxy resin, and the like can be mentioned, and a dicyclopentadiene type epoxy resin and a bisphenol type epoxy resin are preferable. These may be used alone or in combination of two or more different physical properties. Moreover, 200-5000 are preferable for an epoxy equivalent, and 1000-30000 are preferable for a weight average molecular weight. The bisphenol type epoxy resin is manufactured for industrial use, and is manufactured by a one-step method in which bisphenols and epichlorohydrin are reacted in the presence of an alkali metal hydroxide, or by this one-step method. It is obtained by a two-stage method in which bisphenols are further added to an epoxy resin.

  The fatty acid amide (B), which is a compound (B), that is, a condensate of polyalkylene polyamines and fatty acids and has active hydrogen that reacts with an epoxy group, includes fatty acids having 6 to 24 carbon atoms and polyalkylene polyamines. Examples include amino group-containing amide compounds obtained by reaction with aldehydes.

Examples of fatty acids having 6 to 24 carbon atoms include soybean oil fatty acid, linseed oil fatty acid, castor oil fatty acid, lauric acid, palmitic acid, myristic acid, stearic acid, behenic acid, oleic acid, linoleic acid, linolenic acid, and the like. Any of fatty acids and branched fatty acids such as 2-ethylhexylic acid and isostearic acid and derivatives of these fatty acids such as methyl ester, ethyl ester and glycerin ester may be used. These fatty acids and fatty acid derivatives may be used alone or in combination of two or more, but fatty acids having a long-chain alkyl group having 18 to 22 carbon atoms are preferred, oleic acid, stearic acid, More preferred is behenic acid.

  Examples of polyalkylene polyamines include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, dipropylenetriamine, tripropylenetetramine, hexamethylenediamine, aminoethylpiperazine, and the like. May be used in combination, or two or more may be used in combination. Among these, diethylenetriamine, triethylenetetramine, and tetraethylenepentamine are preferable.

  The compound (B) used in the present invention is obtained by reacting the above fatty acids with polyalkylene polyamines. The charging ratio of fatty acids and polyalkylene polyamines is not particularly limited, but the number of moles of carboxylic acid groups of fatty acids is (a) and the total number of moles of primary and secondary amino groups of polyalkylene polyamines is In the case of (b), a relationship of 3.5 ≧ [b / a]> 1 is preferable, and a relationship of 2.1 ≧ [b / a]> 1 is more preferable.

  The compound (B) used in the present invention is obtained by a reaction between fatty acids and polyalkylene polyamines, and the reaction conditions are carried out while heating to 100 to 230 ° C. and removing the generated water. The reaction time is usually 1 to 10 hours, and benzenesulfonic acid, paratoluenesulfonic acid, etc. can be used as a catalyst, and water generated using a solvent such as toluene or xylene is removed by azeotropic distillation. However, it is possible to adopt a method for promoting the reaction.

  Monocarboxylic acids (C) used in the present invention are aromatic monocarboxylic acids such as benzoic acid, 4-butylbenzoic acid, naphthalenecarboxylic acid, salicylic acid, 4-methylbenzoic acid, 3-methylbenzoic acid, hexanoic acid, Examples include octanoic acid, decanoic acid, dodecanoic acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid and other aliphatic monocarboxylic acids, rosin, and methyl esters and ethyl esters of these monocarboxylic acids. Aliphatic monocarboxylic acids and rosins are preferred.

  The resin of the present invention is obtained by reacting the compound (A) with the compound (B) (and the monocarboxylic acid (C)). The reaction between the compound (A) and the compound (B) proceeds by a ring-opening reaction between the epoxy group of the compound (A) and the amino group of the compound (B). The reaction between the compound (A) and the monocarboxylic acid (C) proceeds by a ring-opening reaction between the epoxy group of the compound (A) and the carboxyl group of the monocarboxylic acid (C). The resin is obtained by charging the above-described raw materials into a heatable flask equipped with a cooling pipe, a stirrer, an inert gas introduction pipe, a thermometer, and the like and heating and melting them. The reaction temperature is preferably a temperature that is equal to or higher than the melting points of these components and can be uniformly mixed, and is preferably in the range of 60 to 200 ° C. In the reaction, a catalyst for promoting the ring-opening reaction of the epoxy group may be added. Examples of the catalyst that can be used in this case include amines such as trialkylamine and alkylimidazole, quaternary ammonium salts such as butyltrialkylammonium chloride, and triphenylphosphine.

  In producing the resin of the present invention, the charge ratio of the compound (A) and the compound (B) (and the monocarboxylic acid (C)) is not particularly limited, but the number of moles of amino groups in the compound (B). (C), where the molar number of the epoxy group in the compound (A) is (d) and the molar number of the carboxylic acid group in the monocarboxylic acid (C) is (e), 4.0 ≧ [d / (C + e)] ≧ 0.4 is preferable, and 2.5 ≧ [d / (c + e)] ≧ 0.5 is more preferable. The charging ratio of e / c is preferably 1.60 ≧ e / c ≧ 0.03.

  When the toner additive used in the present invention is used as a toner binder resin, it may be used alone or in combination with other resins. Any other resin can be used as long as it can be used as a binder for an electrophotographic toner. Typical examples include styrene-acrylic copolymers, polyester resins, epoxy resins, urethane resins, and resins obtained by combining styrene-acrylic copolymers and polyester resins. When these resins are used in combination, they can be used to such an extent that the performance as a toner binder resin is not impaired. The additive for toner in the present invention is preferably contained in 70% to 3% in the binder resin for all toners, and more preferably 50% to 5%.

(Physical properties test of toner additive and toner binder resin)
Softening point When the softening point (hereinafter sometimes abbreviated as Tm) is less than 80 ° C, the low-temperature fixability is good, but the high-temperature offset resistance deteriorates. When the Tm is 170 ° C or higher, the high-temperature offset resistance However, Tm is preferably 80 ° C. or higher and lower than 170 ° C.
The softening point in the present invention is 0.5 MPa using a plunger while heating a 1 g sample at a heating rate of 4 ° C./min using a Koka flow tester (manufactured by Shimadzu Corporation: CFT-500D). When a nozzle with a diameter of 1 mm and a length of 1 mm is pushed out, a plunger drop amount of the flow tester (flow value) -temperature curve is created, and the height of the S-shaped curve is h The temperature corresponding to h / 2 (the temperature at which half of the resin flows out) is defined as the softening point.

Glass transition temperature When the glass transition temperature (hereinafter sometimes abbreviated as Tg) is less than 40 ° C., blocking resistance may be deteriorated, and when Tg is 80 ° C. or more, low-temperature fixability may be deteriorated. Is preferably 40 ° C. or higher and lower than 80 ° C.
The glass transition temperature in the present invention was raised to 120 ° C. using a differential scanning calorimeter (SII NanoTechnology Co., Ltd .: DSC-22), allowed to stand at that temperature for 10 minutes, and then cooled down by 10 After cooling to 10 ° C. at 10 ° C./min and leaving at that temperature for 10 minutes, when measured at a heating rate of 10 ° C./min, the peak apex from the extension line of the baseline below the glass transition temperature and the peak rising portion The temperature at the point of intersection with the tangent that indicates the maximum slope until is the glass transition temperature (Tg).

Maximum endothermic peak temperature and onset temperature at the start point of the endothermic peak The onset temperature at the start point of the endothermic peak is preferably 50 ° C. or higher. If it is less than 50 degreeC, blocking resistance will deteriorate easily. The maximum endothermic peak temperature is preferably 60 ° C. or higher and lower than 120 ° C.
The glass transition temperature in the present invention was raised to 120 ° C. using a differential scanning calorimeter (SII NanoTechnology Co., Ltd .: DSC-22), allowed to stand at that temperature for 10 minutes, and then cooled down by 10 After cooling to 10 ° C at 10 ° C / min and leaving at that temperature for 10 minutes, in the DSC curve obtained when measured at a heating rate of 10 ° C / min, the peak top temperature of the peak showing the maximum endothermic peak is the maximum endotherm Use peak temperature. In addition, the temperature at the intersection of the tangent of the curve and the base line at the point where the differential point of the DSC curve first becomes the maximum is the onset temperature of the end point of the endothermic peak.

It is preferable that an acid value acid value exists in the range of 0.5-50 mgKOH / g. If the acid value is less than 0.5 mgKOH / g, the dispersibility of the colorant such as a pigment may decrease. On the other hand, if it exceeds 50 mgKOH / g, the negative charge increases and the temperature dependence of the charge increases. The environmental stability may be poor.
The acid value in the present invention is determined by dissolving 2 g of a sample in 50 ml of tetrahydrofuran (hereinafter sometimes abbreviated as THF), adding a few drops of a phenolphthalein / ethanol solution as an indicator, and then a 1/10 N normal aqueous KOH solution. Titration was performed at It is assumed that the end point is the time when the color of the sample solution is purple, and the acid value (KOHmg / g) is calculated from this titration amount and the sample mass.

THF-insoluble content The THF-insoluble content is preferably in the range of 0.1 to 45%. When the THF insoluble content is less than 0.1%, the low temperature fixability is good, but the high temperature offset resistance is deteriorated. When the THF insoluble content exceeds 45%, the high temperature offset resistance is good, but the low temperature fixability is deteriorated. Because it will do.
In the present invention, the THF-insoluble content of the resin is measured by weighing about 1 g of the resin (W1), putting it in a cylindrical filter paper (for example, No. 86R manufactured by Toyo Roshi), applying it to a Soxhlet extractor, and using 100 g of THF as a solvent. Extraction was performed for 8 hours, and the soluble component extracted with the THF solvent was evaporated, followed by drying at 150 ° C. for 30 minutes, and the weight (W2) of the THF-soluble resin component was weighed. It is calculated.
THF insoluble matter (% by weight) = 100 × (W1-W2) / W1

  The electrophotographic toner of the present invention may contain at least the toner additive of the present invention and a colorant, and may include a toner binder resin containing the toner additive and a colorant, and if necessary, a release agent. In addition, various additives such as a charge control agent and a surface treatment agent can be contained.

  The colorant constituting the electrophotographic toner of the present invention is not particularly limited, and examples thereof include conventionally known dyes and pigments. Specifically, Carbon Black, Sudan Black SM, First Yellow-G, Benzidine Yellow, Pigment Yellow, Indian First Orange, Irgasin Red, Varanitoaniline Red, Toluidine Red, Carmine, Pig FB Mention Orange R, Lake Red 2G , Rhodamine FB, rhodamine B lake, methyl violet B lake, phthalocyanine blue, pigment blue, brilliant green, phthalocyanine green, oil yellow GG, Kayaset YG, orazole brown B, oil pink OP, magnetite, iron black and the like. The content of the colorant is preferably 0.5 to 15% with respect to the solid content weight of the toner binder resin when a dye or a pigment is used. In the case of magnetic toner, since magnetic fine powder is used, the content of the colorant is preferably 20 to 150% with respect to the solid content weight of the binder resin for toner.

  The release agent is not particularly limited. For example, polyolefin resins [polypropylene, polyethylene, ethylene-α olefin (carbon number 3 to 8) copolymer, etc.], paraffins (n-paraffin, isoparaffin, etc.), ester wax Examples (carnauba wax, montan wax, rice wax, etc.), aliphatic alcohols having 30 or more carbon atoms, fatty acids having 30 or more carbon atoms, and mixtures thereof may be used, or one or more of them may be used. The content of the release agent in the toner is preferably 0 to 30% with respect to the solid content weight of the binder resin for toner.

  The charge control agent is not particularly limited. For example, nigrosine dye, quaternary ammonium salt compound, metal-containing azo dye, salicylic acid metal salt, quaternary ammonium base-containing polymer, fluorine-containing polymer, sulfonic acid group-containing polymer and halogen-substituted An aromatic ring containing polymer is mentioned. The content of the charge control agent in the toner is preferably 0 to 10% with respect to the solid weight of the binder resin for toner.

  The surface treatment agent is not particularly limited, and examples thereof include fine powders such as colloidal silica, alumina, titanium oxide, polytetrafluoroethylene, polyvinylidene chloride, polymethyl methacrylate, polystyrene ultrafine particles, and silicone. The content of the surface treatment agent in the toner is preferably 0.1 to 20% with respect to the solid content weight of the binder resin for toner.

  As a method for producing the electrophotographic toner of the present invention containing these materials, a powder mixer is used to mix the toner additive of the present invention, the toner binder resin, the colorant, and optionally other additives by a kneading pulverization method. Then, the mixture is melted at a temperature of 100 to 200 ° C. using a kneader such as a heating roll, an extruder or a kneader, and kneaded to sufficiently mix each component. After cooling this, pulverization and classification are performed to collect particles of 8 to 20 μm, and a surface treating agent is mixed by a powder mixing method to obtain an electrophotographic toner.

  The electrophotographic toner of the present invention is a magnetic one-component developing toner alone when containing a magnetic fine powder, and a non-magnetic one-component developing toner or two-component developing toner when not containing a magnetic fine powder. Alternatively, the two-component developer mixed with a carrier is not particularly limited and can be used in any developing method.

  The electrophotographic toner obtained by the present invention can be used in various fixing methods such as oilless or oil-coated heat roll method, flash method, oven method, pressure fixing method and the like.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated further more concretely, these Examples do not limit this invention. In the examples and comparative examples, “parts” and “%” mean parts by weight and% by weight unless otherwise specified.

Synthesis Example of Resin (Toner Additive) P Consisting of at least Compound (A) and Compound (B) <Synthesis Example 1>
A reaction vessel equipped with a thermometer, a Liebig condenser, a stirrer, and a nitrogen introduction tube was charged with 510.9 parts of behenic acid as a fatty acid and 94.7 parts of tetraethylenepentamine as a polyalkylene polyamine. The reaction was carried out at 170 ° C. under atmospheric pressure for 8 hours to obtain compound (B). After cooling this to 110 ° C, 525.8 parts of epoxy resin A1 (YD-011, manufactured by Toto Kasei, epoxy equivalent 478) was added and reacted for 9 hours while gradually raising the temperature to 190 ° C under a normal pressure in a nitrogen atmosphere. . Furthermore, it was made to react at 190 degreeC under pressure reduction of 10 hPa for 0.5 hour, and resin (P-1) was obtained. The weight average molecular weight of the obtained resin was 6900. The acid value was 1.3 mgKOH / g.

<Synthesis Example 2>
In a reaction vessel equipped with a thermometer, a Liebig condenser, a stirrer, and a nitrogen introduction tube, 546.2 parts of stearic acid as a fatty acid and 113.6 parts of tetraethylenepentamine as a polyalkylene polyamine are charged. The reaction was carried out at 170 ° C. under atmospheric pressure for 8 hours to obtain compound (B). After cooling this to 110 ° C., 516.2 parts of epoxy resin A1 (YD-011 manufactured by Tohto Kasei Co., Ltd., epoxy equivalent 478) was added and reacted for 9 hours while gradually raising the temperature to 190 ° C. under normal pressure in a nitrogen atmosphere. . Furthermore, it was made to react at 190 degreeC under pressure reduction of 10 hPa for 0.5 hour, and resin (P-2) was obtained. The weight average molecular weight of the obtained resin was 9900. The acid value was 1.1 mgKOH / g.

<Synthesis Example 3>
In a reaction vessel equipped with a thermometer, a Liebig condenser, a stirrer, and a nitrogen introduction tube, 256.1 parts of stearic acid as a fatty acid and 46.4 parts of diethylenetriamine as a polyalkylene polyamine were charged in a nitrogen atmosphere. Reaction was performed at 180 ° C. under normal pressure for 6 hours to obtain a compound (B). After cooling this to 110 ° C., 215.1 parts of epoxy resin A1 (YD-011 manufactured by Tohto Kasei, epoxy equivalent 478) was added and reacted for 9 hours while gradually raising the temperature to 190 ° C. in a nitrogen atmosphere. . Furthermore, it was made to react at 190 degreeC under pressure reduction of 10 hPa for 0.5 hour, and resin (P-3) was obtained. The weight average molecular weight of the obtained resin was 3940. The acid value was 2.0 mgKOH / g.

<Synthesis Example 4>
In a reaction vessel equipped with a thermometer, a Liebig condenser, a stirrer and a nitrogen inlet tube, 416.2 parts of stearic acid as fatty acids, 21.8 parts of oleic acid and 79.5 parts of diethylenetriamine as polyalkylene polyamines Was reacted in a nitrogen atmosphere at 180 ° C. for 6 hours to obtain a compound (B). After cooling this to 110 ° C, 404.9 parts of epoxy resin A1 (YD-011, epoxy equivalent 478 manufactured by Tohto Kasei) was added and reacted for 9 hours while gradually raising the temperature to 190 ° C under normal pressure in a nitrogen atmosphere. . Furthermore, it was made to react at 190 degreeC under pressure reduction of 10 hPa for 0.5 hour, and resin (P-4) was obtained. The weight average molecular weight of the obtained resin was 2600. The acid value was 1.8 mgKOH / g.

<Synthesis Example 5>
A reaction vessel equipped with a thermometer, a Liebig condenser, a stirrer, and a nitrogen inlet tube was charged with 694.8 parts of behenic acid, which is a fatty acid, and 99.4 parts, triethylenetetramine, which is a polyalkylenepolyamine, and a nitrogen atmosphere. The mixture was reacted at 180 ° C. for 6 hours under normal pressure to obtain compound (B). After cooling to 110 ° C., 325.0 parts of epoxy resin A1 (YD-011, epoxy equivalent 478, manufactured by Tohto Kasei) was added and reacted for 9 hours while gradually raising the temperature to 190 ° C. under normal pressure in a nitrogen atmosphere. . Furthermore, it was made to react at 190 degreeC under pressure reduction of 10 hPa for 0.5 hour, and resin (P-5) was obtained. The weight average molecular weight of the obtained resin was 3700. The acid value was 3.1 mgKOH / g.

<Synthesis Example 6>
In a reaction vessel equipped with a thermometer, a Liebig condenser, a stirrer, and a nitrogen introduction tube, 508.5 parts of oleic acid as a fatty acid and 103.2 parts of diethylenetriamine as a polyalkylene polyamine were charged in a nitrogen atmosphere. Reaction was performed at 180 ° C. under normal pressure for 6 hours to obtain a compound (B). After this was cooled to 110 ° C., 1067.0 parts of epoxy resin A2 (YD-014 manufactured by Tohto Kasei Co., Ltd., epoxy equivalent 970) was added and reacted for 9 hours while gradually raising the temperature to 190 ° C. under normal pressure in a nitrogen atmosphere. . Furthermore, it was made to react at 190 degreeC under pressure reduction of 10 hPa for 0.5 hour, and resin (P-6) was obtained. The weight average molecular weight of the obtained resin was 9300. The acid value was 0.8 mgKOH / g.

<Synthesis Example 7>
A reaction vessel equipped with a thermometer, a Liebig condenser, a stirrer, and a nitrogen inlet tube was charged with 479.6 parts of behenic acid, which is a fatty acid, and 83.3 parts, tetraethylenepentamine, which is a polyalkylenepolyamine. The reaction was carried out at 180 ° C. under atmospheric pressure for 8 hours to obtain compound (B). After cooling this to 100 ° C., 799.2 parts of epoxy resin A1 (YD-011 manufactured by Tohto Kasei Co., Ltd., epoxy equivalent 478) and 269.3 parts of rosin, which is a monocarboxylic acid, were added, and the reaction was performed in a nitrogen atmosphere under normal pressure. The reaction was carried out for 9 hours while gradually raising the temperature from 0C to 190C. Furthermore, it was made to react at 190 degreeC under pressure reduction of 10 hPa for 0.5 hour, and resin (P-7) was obtained. The weight average molecular weight of the obtained resin was 4350. The acid value was 0.3 mgKOH / g.

<Synthesis Example 8>
In a reaction vessel equipped with a thermometer, a Liebig condenser, a stirrer, and a nitrogen introduction tube, 338.0 parts of stearic acid as a fatty acid and 68.1 parts of diethylenetriamine as a polyalkylene polyamine were charged in a nitrogen atmosphere. Reaction was performed at 180 ° C. under normal pressure for 8 hours to obtain a compound (B). After cooling this to 100 ° C., 441.7 parts of epoxy resin A1 (YD-011, epoxy equivalent 478 manufactured by Tohto Kasei) and 37.6 parts of stearic acid, which is a monocarboxylic acid, were added, and a nitrogen atmosphere was applied under normal pressure. The reaction was performed for 9 hours while gradually raising the temperature from 100 ° C to 190 ° C. Furthermore, it was made to react at 190 degreeC under pressure reduction of 10 hPa for 0.5 hour, and resin (P-8) was obtained. The weight average molecular weight of the obtained resin was 4100. The acid value was 2.7 mgKOH / g.

<Synthesis Example 9>
A reaction vessel equipped with a thermometer, a Liebig condenser, a stirrer, and a nitrogen introduction tube was charged with 519.4 parts of behenic acid as a fatty acid and 89.2 parts of triethylenetetramine as a polyalkylene polyamine, and a nitrogen atmosphere. The mixture was reacted at 180 ° C. for 8 hours under normal pressure to obtain compound (B). After cooling to 100 ° C., 495.7 parts of epoxy resin A1 (YD-011 manufactured by Tohto Kasei Co., Ltd., epoxy equivalent 478) and 41.6 parts of behenic acid, which is a monocarboxylic acid, were added, and a nitrogen atmosphere was applied under normal pressure. The reaction was performed for 9 hours while gradually raising the temperature from 100 ° C to 190 ° C. Furthermore, it was made to react at 190 degreeC under pressure reduction of 10 hPa for 0.5 hour, and resin (P-9) was obtained. The weight average molecular weight of the obtained resin was 4300. The acid value was 2.5 mgKOH / g.

(Binder resin for toner)
<Example 1>
30 parts of the resin (P-1) and 70 parts of the polyester resin were mixed with a blender, and melt-kneaded with a heated biaxial extruder to obtain a binder resin for toner (BR-1) of the example.

<Examples 2 to 8>
Except for blending according to the composition shown in Table 1, toner binder resins (BR-2 to 8) were obtained in the same manner as in Example 1.

<Comparative Examples 1 and 2>
Except for blending according to the composition shown in Table 2, toner binder resins (CR-1, 2) were obtained in the same manner as in Example 1.

Explanation of Table 1 "-" in the table indicates that the component was not used.
Polyester resin (weight average molecular weight 231,000, acid value 5 mg KOH / g, THF insoluble content 3%),
Styrene acrylic resin (weight average molecular weight 281,000, acid value 20 mgKOH / g, THF insoluble content 2%)

Explanation of Table 2 "-" in the table indicates that the component was not used.
Polyester resin (weight average molecular weight 231,000, acid value 5 mg KOH / g, THF insoluble content 3%),
Epoxy resin (YD-014 manufactured by Tohto Kasei, epoxy equivalent 970)

(Toner preparation)
<Example 9>
A biaxial extruder in which 100 parts of resin (BR-1), 5 parts of carnauba wax, 7 parts of carbon black and 1 part of charge control agent TN-105 (made by Hodogaya Chemical) were mixed in a blender and heated to 130 ° C. Melt kneaded. The cooled kneaded product was coarsely pulverized with a speed mill and then finely pulverized with a jet mill. The obtained finely pulverized product was strictly classified with a classifier to obtain toner particles having a weight average particle diameter of 8 μm. Next, 0.5 parts of colloidal silica (Aerosil R972, manufactured by Nippon Aerosil Co., Ltd.) was mixed with 100 parts of the obtained toner particles with a mixer to obtain a toner (T-1) of Example. The obtained toner was evaluated according to the following method. The evaluation results are shown in Table 3.

<Examples 10 to 16>
Toners (T-2 to 8) were obtained in the same manner as in Example 9 except that they were blended according to the composition shown in Table 3. The evaluation results are shown in Table 3.

<Comparative Examples 3 and 4>
Toners (CT-1 and 2) were obtained in the same manner as in Example 9 except that they were blended according to the composition shown in Table 4. The evaluation results are shown in Table 4.

<Evaluation method>
1. Low-temperature fixability Printing was carried out using a fixing device having a fixing roller not coated with silicone oil and capable of changing the temperature set at a roller speed of 100 mm / second, and the low-temperature fixability was evaluated. Further, when the toner was fixed on the paper, the lowest temperature when the toner started to be fixed on the paper was defined as the fixing temperature, and the determination was made according to the following criteria.
○ (Good): Fixing temperature is less than 130 ° C. Δ (Available): Fixing temperature is 130 ° C. or more and less than 160 ° C. x (Inferior): Fixing temperature is 160 ° C. or more

2. High temperature offset resistance The maximum temperature at which the toner moves to the fixing roller during fixing under the same conditions as in the low temperature fixability evaluation method was determined as the offset generation temperature, and the high temperature offset resistance was judged using the following criteria.
○ (Good): Offset generation temperature is 220 ° C or higher Δ (can be used): Offset generation temperature is 200 ° C or higher and lower than 220 ° C x (Inferior): Offset generation temperature is lower than 200 ° C

3. Blocking resistance The degree of aggregation of the toner powder after standing at a temperature of 50 ° C. for 3 days was judged visually.
○: Not blocking (practical level)
Δ: Partially blocked ×: Bad blocking

4). Wax dispersibility A thin piece of the melt-kneaded product was formed and observed under a microscope, and the wax aggregate was visually determined.
○: Aggregates of 2 μm or more are not observed ×: Aggregates of 2 μm or more are observed

  From these results, the toners T-1 to T-8 of the examples using the binder resin for toner of the present invention were excellent in low-temperature fixability, blocking resistance, and wax dispersibility.

  On the other hand, as is apparent from Tables 3 and 4, the comparative toners CT-1 and 2 using the toner binder resin that is not the toner binder resin of the present invention have low temperature fixability, blocking resistance, and wax dispersibility. It was inferior.

  By using the binder resin for toner of the present invention, the toner can be made excellent in both low-temperature fixability and anti-blocking property, and further in wax dispersibility.

<Synthesis Example 10>
A reaction vessel equipped with a thermometer, a Liebig condenser, a stirrer and a nitrogen introduction tube was charged with 545 parts of behenic acid, which is a fatty acid, and 82.6 parts, diethylenetriamine, which is a polyalkylenepolyamine, in a nitrogen atmosphere under normal pressure. Reaction was performed at 170 ° C. for 8 hours to obtain a compound (B). After cooling this to 110 ° C., 390 parts of epoxy resin A1 (YD-011 manufactured by Tohto Kasei, epoxy equivalent 478) was added, and the mixture was reacted for 9 hours while gradually raising the temperature to 190 ° C. in a nitrogen atmosphere. Furthermore, it was made to react at 190 degreeC under pressure reduction of 10 hPa for 0.5 hour, and resin (P-10) was obtained. The weight average molecular weight (Mw) of the obtained resin was 4900, and the molecular weight distribution (Mw / Mn) was 1.8. The maximum endothermic peak temperature and the onset temperature at the beginning of the endothermic peak were 75.2 and 52.2 ° C. The acid value was 1.1 mgKOH / g.

<Synthesis Example 11>
A reaction vessel equipped with a thermometer, a Liebig condenser, a stirrer, and a nitrogen inlet tube was charged with 681.9 parts of behenic acid as a fatty acid and 112.6 parts of triethylenetetramine as a polyalkylene polyamine, and a nitrogen atmosphere. The mixture was reacted at 180 ° C. for 8 hours under normal pressure to obtain compound (B). After cooling this to 100 ° C., 368.1 parts of epoxy resin A1 (YD-011 manufactured by Tohto Kasei Co., Ltd., epoxy equivalent 478) and 104.9 parts of behenic acid, which is a monocarboxylic acid, were added, and in a nitrogen atmosphere under normal pressure. The reaction was performed for 9 hours while gradually raising the temperature from 100 ° C to 190 ° C. Furthermore, it was made to react at 190 degreeC under pressure reduction of 10 hPa for 0.5 hour, and resin (P-11) was obtained. The weight average molecular weight (Mw) of the obtained resin was 4300, and the molecular weight distribution (Mw / Mn) was 2.1. The maximum endothermic peak temperature and the onset temperature at the start of the endothermic peak were 75.2 and 51.9 ° C. The acid value was 2.5 mgKOH / g.

<Synthesis Example 12>
A reaction vessel equipped with a thermometer, a Liebig condenser, a stirrer, and a nitrogen inlet tube was charged with 613.1 parts of behenic acid, which is a fatty acid, and 85.2 parts, tetraethylenepentamine, which is a polyalkylene polyamine, The reaction was carried out at 170 ° C. under atmospheric pressure for 8 hours to obtain compound (B). After cooling this to 110 ° C., 432.1 parts of epoxy resin A1 (YD-014 manufactured by Tohto Kasei, epoxy equivalent 970) was added and reacted for 9 hours while gradually raising the temperature to 190 ° C. under normal pressure in a nitrogen atmosphere. . Furthermore, it was made to react at 190 degreeC under pressure reduction of 10 hPa for 0.5 hour, and resin (P-12) was obtained. The weight average molecular weight (Mw) of the obtained resin was 5900, and the molecular weight distribution (Mw / Mn) was 1.9. The maximum endothermic peak temperature and the onset temperature at the start of the endothermic peak were 81.9 and 52.7 ° C. The acid value was 1.8 mgKOH / g.

<Synthesis Example 13>
A reaction vessel equipped with a thermometer, a Liebig condenser, a stirrer, and a nitrogen introduction tube was charged with 438.1 parts of stearic acid as a fatty acid and 79.5 parts of diethylenetriamine as a polyalkylene polyamine, in a nitrogen atmosphere. Reaction was performed at 170 ° C. under normal pressure for 8 hours to obtain a compound (B). After cooling this to 110 ° C., 368.1 parts of epoxy resin A1 (YD-011 manufactured by Tohto Kasei, epoxy equivalent 478) was added and reacted for 9 hours while gradually raising the temperature to 190 ° C. under normal pressure in a nitrogen atmosphere. . Furthermore, it was made to react at 190 degreeC under pressure reduction of 10 hPa for 0.5 hour, and resin (P-13) was obtained. The weight average molecular weight (Mw) of the obtained resin was 4000, and the molecular weight distribution (Mw / Mn) was 1.9. The maximum endothermic peak temperature and the onset temperature at the start of the endothermic peak were 64.2 and 49.3 ° C. The acid value was 2.8 mgKOH / g.

<Synthesis Example 14>
In a reaction vessel equipped with a thermometer, a Liebig condenser, a stirrer and a nitrogen introduction tube, 463.2 parts of behenic acid which is a fatty acid and 70.2 parts of diethylenetriamine which is a polyalkylene polyamine are charged in a nitrogen atmosphere. Reaction was performed at 170 ° C. under normal pressure for 8 hours to obtain a compound (B). After cooling this to 110 ° C., 656.1 parts of epoxy resin A3 (YDF-2004 manufactured by Tohto Kasei, epoxy equivalent 975) was added and reacted for 9 hours while gradually raising the temperature to 190 ° C. in a nitrogen atmosphere. . Furthermore, it was made to react at 190 degreeC under pressure reduction of 10 hPa for 0.5 hour, and resin (P-14) was obtained. The weight average molecular weight (Mw) of the obtained resin was 6900, and the molecular weight distribution (Mw / Mn) was 2.4. The maximum endothermic peak temperature and the onset temperature at the start of the endothermic peak were 73.7 and 51.5 ° C. The acid value was 1.3 mgKOH / g.

<Synthesis Example 15>
In a reaction vessel equipped with a thermometer, a Liebig condenser, a stirrer and a nitrogen introduction tube, 1021.8 parts of behenic acid, which is a fatty acid, and 189.3 parts, tetraethylenepentamine, which is a polyalkylene polyamine, are charged. The reaction was carried out at 170 ° C. under atmospheric pressure for 8 hours to obtain compound (B). After this was cooled to 110 ° C., 960.8 parts of epoxy resin A1 (YD-011 manufactured by Tohto Kasei, epoxy equivalent 478) was added and reacted for 9 hours while gradually raising the temperature to 190 ° C. under normal pressure in a nitrogen atmosphere. . Furthermore, it was made to react at 190 degreeC under pressure reduction of 10 hPa for 0.5 hour, and resin (P-15) was obtained. The weight average molecular weight (Mw) of the obtained resin was 5600, and the molecular weight distribution (Mw / Mn) was 1.9. The maximum endothermic peak temperature and the onset temperature at the start of the endothermic peak were 73.9 and 52.9 ° C. The acid value was 0.8 mgKOH / g.

<Synthesis Example 16>
In a reaction vessel equipped with a thermometer, a Liebig condenser, a stirrer, and a nitrogen introduction tube, 313 parts of fatty acid stearic acid and 45.4 parts of polyalkylene polyamine diethylenetriamine were charged under nitrogen at normal pressure. Reaction was performed at 170 ° C. for 8 hours to obtain a compound (B). After cooling this to 110 ° C., 107.3 parts of epoxy resin A1 (YD-011, epoxy equivalent 478 manufactured by Tohto Kasei) was added and reacted for 9 hours while gradually raising the temperature to 190 ° C. under normal pressure in a nitrogen atmosphere. . Furthermore, it was made to react at 190 degreeC under pressure reduction of 10 hPa for 0.5 hour, and resin (P-16) was obtained. The weight average molecular weight (Mw) of the obtained resin was 3100, and the molecular weight distribution (Mw / Mn) was 1.6. The maximum endothermic peak temperature and the onset temperature at the start of the endothermic peak were 72.8 and 64.7 ° C. The acid value was 1.2 mgKOH / g.

(Toner preparation)
<Example 17>
Binder resin for toner (polyester resin; weight average molecular weight 275,000, acid value 5 mg KOH / g, THF insoluble content 7%) 100 parts, P-10 7 parts, carbon black 7 parts and charge control agent TN-105 (Hodogaya) 1 part of Chemical) was mixed with a blender and melt-kneaded with a biaxial extruder heated to 130 degrees. The cooled kneaded product was coarsely pulverized with a speed mill and then finely pulverized with a jet mill. The obtained finely pulverized product was strictly classified with a classifier to obtain toner particles having a weight average particle diameter of 8 μm. Next, 100 parts of the obtained toner particles were mixed with 0.5 part of colloidal silica (Aerosil R972, manufactured by Nippon Aerosil Co., Ltd.) using a mixer to obtain Example Toner (T-9). The obtained toner was evaluated according to the following method. The evaluation results are shown in Table 5.

<Examples 18 to 25>
Toners (T-10 to 17) were obtained in the same manner as in Example 17 except for blending according to the composition shown in Table 5. The evaluation results are shown in Table 5.

<Comparative Examples 5-7>
Toners (CT-3 to 5) were obtained in the same manner as in Example 17 except for blending according to the composition shown in Table 6. The evaluation results are shown in Table 6.

<Evaluation method>
1. Low-temperature fixability Printing was carried out using a fixing device having a fixing roller not coated with silicone oil and capable of changing the temperature set at a roller speed of 100 mm / second, and the low-temperature fixability was evaluated. Further, when the toner was fixed on the paper, the lowest temperature when the toner started to be fixed on the paper was defined as the fixing temperature, and the determination was made according to the following criteria.
○ (Good): Fixing temperature is less than 130 ° C. Δ (Available): Fixing temperature is 130 ° C. or more and less than 160 ° C. x (Inferior): Fixing temperature is 160 ° C. or more

2. High temperature offset resistance The maximum temperature at which the toner moves to the fixing roller during fixing under the same conditions as in the low temperature fixability evaluation method was determined as the offset generation temperature, and the high temperature offset resistance was judged using the following criteria.
○ (Good): Offset generation temperature is 220 ° C or higher Δ (can be used): Offset generation temperature is 200 ° C or higher and lower than 220 ° C x (Inferior): Offset generation temperature is lower than 200 ° C

3. Blocking resistance The degree of aggregation of the toner powder after standing at a temperature of 50 ° C. for 3 days was judged visually.
○: Not blocking (practical level)
Δ: Partially blocked ×: Bad blocking

“-” In the explanatory tables of Tables 5 and 6 indicates that the component was not used.
PARAFLINT C-80; Sasol wax Fischer-Tropsch wax HNP-9; Nippon Seiki paraffin wax

From these results, the toners T-9 to 17 of the examples using the toner additive of the present invention retain the blocking resistance as compared with the comparative example CT-3 which does not use the toner additive of the present invention. However, it was excellent in low-temperature fixability and high-temperature offset resistance.

  On the other hand, as is clear from Table 6, the toners CT-4 and 5 of Comparative Example using wax without using the toner additive of the present invention deteriorated in blocking resistance, and the high-temperature offset resistance was equivalent or less. Met.

  As described above, by using the toner additive of the present invention, it is possible to obtain a toner having excellent low-temperature fixability and high-temperature offset resistance while maintaining the toner blocking resistance.

Since the toners T-9 to 17 of Examples using the toner additive of the present invention have excellent high temperature offset resistance, the toner additive of the present invention also functions as a wax.

Claims (5)

A toner additive comprising at least a resin obtained by reacting at least the following compound (A) with the following compound (B).
(A) Epoxy resin (B) Fatty acid amide which is a condensate of polyalkylene polyamines and fatty acids and has active hydrogen which reacts with epoxy groups A toner additive comprising at least a resin obtained by reacting at least the compound (A) according to claim 1, the compound (B) according to claim 1, and the following compound (C).
(C) Monocarboxylic acids 3. The toner additive according to claim 1, wherein the toner additive has a wax function. A toner binder resin according to any one of claims 1 to 3, comprising a toner binder resin.   An electrophotographic toner comprising at least the toner additive according to claim 1 or the toner binder resin according to claim 4 and a colorant.