JP7051530B2 - Toner additive - Google Patents

Description

The present invention relates to an additive for toner.

As a conventional technique for producing toner, there is a production method in which resin particles are dispersed in an aqueous medium (see, for example, Patent Documents 1 and 2). However, since the toner obtained by the above-mentioned manufacturing method imparts hydrophilicity to the raw material of the resin particles in order to impart dispersibility in an aqueous medium, it induces blocking under high temperature and high humidity and has heat-resistant storage stability. There was a drawback that it was bad.
In order to eliminate the above-mentioned drawbacks, a technique for producing toner using a compressible fluid (liquid carbon dioxide or the like) is known (see, for example, Patent Documents 3 to 7).
Further, a technique of adding wax to the toner is known in order to lower the fixing temperature of the toner, prevent contamination on the surface of the heat fixing roller, prevent contamination on the carrier or the developing roller, adjust the glossiness of the printed surface, and improve the image strength. ing.
However, when a toner containing wax is produced in a compressible fluid, additives used for the toner such as a wax dispersant are extracted from the toner binder resin into the compressed fluid during the production process, and the wax in the toner is produced. As a result of the deterioration of the dispersibility of the toner, there is a problem that the performance (charge stability, heat-resistant storage property, etc.) of the obtained toner is also deteriorated.

Japanese Unexamined Patent Publication No. 2009-215414 Japanese Unexamined Patent Publication No. 2010-047752 Japanese Unexamined Patent Publication No. 2004-302323 Japanese Unexamined Patent Publication No. 2006-321830 Japanese Unexamined Patent Publication No. 2008-287088 Japanese Unexamined Patent Publication No. 2009-030002 Japanese Unexamined Patent Publication No. 2010-128114

An object of the present invention is to provide an additive for toner that improves the dispersibility of the wax used for the toner.

The present inventors have arrived at the present invention as a result of diligent studies to solve the above problems.
That is, the present invention is an additive for a toner containing an ester (E), and (E) is a chain with a polyester polyol (C) which is a condensed polymer of a polyol (A) and a polycarboxylic acid (B). It is an ester with a monocarboxylic acid (D) having 18 to 24 carbon atoms having a state alkyl group, the acid value of the ester (E) is less than 1 mgKOH / g, and the hydroxyl value of the ester (E) is 10 to 10 to. Additive for fatty acid having a glass transition point of the ester (E) of −35 to 5 ° C. at 60 mgKOH / g; the additive for the toner, the toner binder resin (R), the colorant (g) and the ester wax. , A toner containing at least one wax (w) selected from the group consisting of a polyolefin wax, an aliphatic alcohol having 30 to 50 carbon atoms and a fatty acid having 30 to 50 carbon atoms.

The toner produced by using the toner additive of the present invention has excellent wax dispersibility. Therefore, the obtained toner is excellent in charge stability and heat storage stability.

FIG. 1 is a flowchart of an experimental device used for producing toner.

The additive for toner in the present invention is an additive for toner containing an ester (E), and the polyester polyol (C) in which (E) is a condensed polymer of the polyol (A) and the polycarboxylic acid (B). ) And a monocarboxylic acid (D) having 18 to 24 carbon atoms having a chain alkyl group, and the acid value of the ester (E) is less than 1 mgKOH / g, and the ester (E) is described. The hydroxyl value of the ester (E) is 10 to 60 mgKOH / g, and the glass transition point of the ester (E) is −35 to 40 ° C.

The polyol (A) in the present invention includes a chain aliphatic polyol having 2 to 20 carbon atoms, an alicyclic polyol having 3 to 20 carbon atoms, an aromatic polyol having 6 to 20 carbon atoms, and novolak (phenol novolak and cresol novolak). Etc., average polymerization degree 3 to 60), and alkylene oxides having 2 to 12 carbon atoms (ethylene oxide, 1,2- or 1,3-propylene oxide, 1,2-, 1,) in these compounds or water. Examples thereof include 3-, 1,4- or 2,3-butylene oxide, styrene oxide, epichlorohydrin and laurylene oxide) adducts.

As the chain aliphatic polyol having 2 to 20 carbon atoms, the chain aliphatic diol having 1 to 20 carbon atoms (ethylene glycol, 1,2- or 1,3-propylene glycol, 1,3- or 1,4- Butanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, neopentyl glycol and 2,2-diethyl-1, 3-Propylene diol, etc.), chain aliphatic triols with 2 to 20 carbon atoms (glycerin, decantriol, trimethylolpropane, etc.) and chain aliphatic 4 to 8-valent alcohols with 2 to 20 carbon atoms (pentaerythritol, sorbitol, etc.) , Mannitol, diglycerin, dipentaerythritol, etc.) and the like.
Examples of the alicyclic polyol having 3 to 20 carbon atoms include alicyclic diols having 3 to 20 carbon atoms [1,3-cyclopentanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,4. -Cycloheptane diol, 2,2-bis (4-hydroxycyclohexyl) propane], alicyclic triol with 3 to 20 carbon atoms (1,3,5-cyclohexanetriol, etc.), alicyclic triol with 3 to 20 carbon atoms Examples thereof include 4- and octahydric alcohols (sorbitane and the like) and saccharides (sucrose, glucose, mannose, fructose, methyl glucoside and derivatives thereof, etc.).
Examples of the aromatic polyol having 6 to 20 carbon atoms include aromatic diols having 6 to 20 carbon atoms (1,4-benzenediethanol, hydroquinone, resorcinol, catechol, dihydroxynaphthalene, bisphenol A, bisphenol F, bisphenol B, bisphenol AD, etc. Bisphenol S, trichlorobisphenol A, tetrachlorobisphenol A, dibromobisphenol F, 2-methylbisphenol A, 2,6-dimethylbisphenol A and 2,2'-diethylbisphenol F, etc.), aromatic triol with 6 to 20 carbon atoms (Fluoroglucin, pyrogallol, etc.) and aromatic 4-8-valent alcohols having 6 to 20 carbon atoms (1,3,6,8-tetrahydroxynaphthalene, 1,4,5,8-tetrahydroxyanthracene, etc.) and the like can be mentioned. ..

The above-mentioned polyol (A) may be used alone or in combination of two or more.
Among these polyols (A), alkylene oxides having 2 to 12 carbon atoms of a chain aliphatic polyol having 2 to 20 carbon atoms and an aromatic polyol having 6 to 20 carbon atoms are preferable from the viewpoint of heat storage stability. More preferably, it is a chain aliphatic triol having 2 to 20 carbon atoms and an alkylene oxide adduct having 2 to 12 carbon atoms of an aromatic diol having 6 to 20 carbon atoms.

The polycarboxylic acid (B) in the present invention includes a chain aliphatic polycarboxylic acid having 2 to 20 carbon atoms, an alicyclic polycarboxylic acid having 5 to 20 carbon atoms, and an aromatic polycarboxylic acid having 8 to 20 carbon atoms. And vinyl polymers of unsaturated carboxylic acids [number average molecular weight: 450-10,000] (α-olefin / maleic acid copolymer, styrene / maleic acid copolymer, styrene / acrylic acid copolymer and styrene / fumal Acid copolymers, etc.) and the like.

Examples of the chain aliphatic polycarboxylic acid having 2 to 20 carbon atoms include chain aliphatic dicarboxylic acids having 2 to 20 carbon atoms (such as oxalic acid, malonic acid, dipropylmalonic acid, succinic acid, and 2,2-dimethylsuccinic acid). , Glutaric acid, 2-methylglutaric acid, 2,2-dimethylglutaric acid, 2,4-dimethylglutaric acid, 3-methylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, Adipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethylpimeric acid, lepargic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, pentadecanedioic acid, tetradecanedioic acid, heptadecanedi Acid, octadecanedioic acid, nonadecandioic acid, eicosandioic acid, alkenyl succinic acid having 16 to 20 carbon atoms (dodecenyl succinic acid, etc.), maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, glutaconic acid, etc.) and carbon Examples thereof include chain aliphatic 3 to 6-valent carboxylic acids (hexanetricarboxylic acid and the like) having a number of 4 to 20.
As the alicyclic polycarboxylic acid having 5 to 20 carbon atoms, the alicyclic dicarboxylic acid having 5 to 20 carbon atoms (cyclopropanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, cyclohexene dicarboxylic acid, dicyclohexyl-4,4' -Dicarboxylic acid and gypsum acid, etc.) and alicyclic 3 to 6-valent carboxylic acid having 6 to 20 carbon atoms (cyclohexanetricarboxylic acid, etc.) and the like can be mentioned.
Examples of the aromatic polycarboxylic acid having 8 to 20 carbon atoms include aromatic dicarboxylic acids having 8 to 20 carbon atoms (phthalic acid, terephthalic acid, isophthalic acid, 2-methylterephthalic acid, 4,4-stylbenzicarboxylic acid, and naphthalenedicarboxylic acid). Acids, 4,4-biphenyldicarboxylic acids, diphenoxyetanedicarboxylic acids, diphenyletherdicarboxylic acids, diphenylsulfonedicarboxylic acids, etc.) and aromatic 3-6-valent carboxylic acids with 9 to 20 carbon atoms (trimellitic acid, pyromellitic acid, etc.) ) Etc. can be mentioned.

The above-mentioned polycarboxylic acid (B) may be used alone or in combination of two or more.
Among these polycarboxylic acids (B), a chain aliphatic polycarboxylic acid having 2 to 20 carbon atoms and an aromatic poly having 8 to 20 carbon atoms are preferable from the viewpoint of achieving both low temperature fixability and hot offset resistance. It is a carboxylic acid, more preferably a chain aliphatic dicarboxylic acid having 2 to 20 carbon atoms, an aromatic dicarboxylic acid having 8 to 20 carbon atoms, and an aromatic 3 to 6-valent carboxylic acid having 9 to 20 carbon atoms. It is preferably an aromatic dicarboxylic acid having 8 to 20 carbon atoms.
From the viewpoint of heat-resistant storage, adipic acid, alkenylsuccinic acid having 16 to 20 carbon atoms, terephthalic acid, isophthalic acid, maleic acid, fumaric acid, trimellitic acid and pyromellitic acid are more preferable, and adipic acid is particularly preferable. , Terephthalic acid and trimellitic acid, most preferably terephthalic acid and trimellitic acid.

The polyester polyol (C), which is a polypolymer of the polyol (A) and the polycarboxylic acid (B) in the present invention, may be used alone or in combination of two or more.
Of these, alkylene oxide adducts (additional moles 2 to 5) of the aromatic diol having 6 to 20 carbon atoms are preferable as (A) from the viewpoint of low temperature fixability, hot offset resistance and heat storage stability. ), And as (B), at least one acid selected from the group consisting of adipic acid, terephthalic acid and trimellitic acid (more preferably terephthalic acid and / or trimellitic acid) was used (C).

The polyester polyol (C) can be produced by subjecting a known polypolymer reaction (condensation reaction described in JP-A-2016-133713) using the polyol (A) and the polycarboxylic acid (B). can.
For example, in an atmosphere of an inert gas (nitrogen gas or the like), the reaction temperature is preferably 150 to 280 ° C., more preferably 160 to 250 ° C., particularly preferably 170 to 235 ° C., and the polyol (A) and the polycarboxylic acid ( It can be carried out by subjecting B) to a polycondensation reaction. The reaction time is preferably 30 minutes or more, more preferably 2 to 40 hours, from the viewpoint of the reaction rate of the polycondensation reaction.
In the above production method, instead of the polycarboxylic acid (B), the anhydride of the polycarboxylic acid (B) and / or the lower alkyl (carbon number 1 to 4) ester (methyl ester) of the polycarboxylic acid (B). , Ethyl ester, isopropyl ester, etc.), or these may be used in combination with the polycarboxylic acid (B).

At this time, if necessary, an esterification catalyst [organic titanium compound (tetrabutoxytitanate, tetrapropioxytitanate, titanium diisopropoxybistriethanolaminate, etc.), organotin compound (butyltin dilaurate, dibutyltin oxide), and other organic lead Compounds, sulfuric acid, etc.] can be used.
Further, a stabilizer may be added for the purpose of obtaining polyester polymerization stability. Examples of the stabilizer include hydroquinone, methylhydroquinone, hindered phenol compounds and the like.

The ratio of the polyol (A) to the polycarboxylic acid (B) used in the above polycondensation reaction is the molar equivalent ratio [OH] / of the hydroxyl group of the polyol (A) to the carboxy group of the polycarboxylic acid (B). The ratio of [COOH] is preferably 2/1 to 1/2, more preferably 1.5 / 1 to 1 / 1.3, and particularly preferably 1.4 / 1 to 1 / 1.2. be.

Preferred monocarboxylic acids (D) having a chain alkyl group and having 18 to 24 carbon atoms in the present invention include stearate, nonadecylic acid, aragidic acid, henicosyl acid, bechenic acid, tricosylic acid, lignoceric acid and the like. Will be.
The monocarboxylic acid (D) may be used alone or in combination of two or more.

The group derived from the monocarboxylic acid (D) in the ester (E), which will be described in detail later, acts as a functional group (also referred to as a parent wax group) having a high affinity for the wax in the toner, and is therefore used for the toner. Depending on the wax, the one with the optimum carbon number can be selected. For example, when an ester wax synthesized from an alcohol having 18 carbon atoms having a chain alkyl group and a fatty acid having 18 carbon atoms having a chain alkyl group, such as stearyl stearate, is used, the monocarboxylic acid (D) is used. By selecting stearic acid, which is a monocarboxylic acid having 18 carbon atoms and having a chain alkyl group, the affinity of the ester (E) for the wax can be improved, and the ester (E) and the wax are contained. The dispersion of wax in the toner is also good.
The wax used for the toner, which will be described in detail later, is preferably 22 from the viewpoint of low temperature fixability and heat storage stability, in that the carbon number of the group derived from the carboxylic acid and the carbon number of the group derived from the alcohol constituting the ester wax are 22, respectively. It is an ester wax, and when this ester wax is used as the toner, it is preferable to use behenic acid having 22 carbon atoms as the monocarboxylic acid (D).

In the toner additive of the present invention, the ester (E), which is a condensate of the polyester polyol (C) and the monocarboxylic acid (D), may be used alone or in combination of two or more. It may be used together.
Among the esters (E), the alkylene oxide adduct (number of moles added) of the aromatic diol having 6 to 20 carbon atoms is preferable as (A) from the viewpoint of low temperature fixability, charge stability and image intensity. 2-5) were used, adipic acid, terephthalic acid and / or trimellitic acid (more preferably terephthalic acid and / or trimellitic acid) was used as (B), and behenic acid was used as (D) (E). Is.

The hydroxyl value of the ester (E) is 10 to 60 mgKOH / g.
If the hydroxyl value of the ester (E) is less than 10, it is not preferable from the viewpoint of fluidity, and if it exceeds 60, it is not preferable from the viewpoint of heat storage stability.
The hydroxyl value of the ester (E) is preferably 10 to 35 mgKOH / g, more preferably 15 to 25 mgKOH / g, from the viewpoint of affinity with the wax used for the toner and the residual amount of the low molecular weight component.
The hydroxyl value of the ester (E) can be calculated from the value obtained by subtracting the number of carboxyl groups of the monocarboxylic acid (D) from the number of terminal hydroxyl groups of the polyester polyol (C), and the polyester polyol (C) constituting the ester (E) can be calculated. ) And the monocarboxylic acid (D) can be adjusted.

The acid value of the ester (E) is less than 1 mgKOH / g.
When the acid value of the ester (E) is 1 or more, it is not preferable from the viewpoint of hot offset resistance.

In the present invention, the hydroxyl value of the ester (E) is measured by the same potentiometric titration method specified in JIS K0070 (1992 edition) except that a sample dissolved in pyridine is used, and the acid value is JIS K0070 (1992 version). It is measured by the potential difference measuring method specified in (1992 edition).

The glass transition point of the ester (E) is −35 to 40 ° C. The glass transition point of the ester (E) can be adjusted by the glass transition point of the polyester polyol (C), and the adjusting factors such as the ester group concentration and the aromatic ring concentration can be adjusted by a generally known method. can.
If the glass transition point of the ester (E) is less than −35 ° C., it is not preferable from the viewpoint of heat-resistant storage, and if it exceeds 40 ° C., it is not preferable from the viewpoint of low-temperature fixability.
The glass transition point of the ester (E) is preferably −35 to 5 ° C. from the viewpoint of affinity with the wax used for the toner.

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

The number average molecular weight (hereinafter abbreviated as Mn) of the ester (E) is preferably 1,500 from the viewpoint of solubility in the solvent (F) used in the production method described in detail later, image strength and heat storage stability. It is ~ 4,500, more preferably 1,500 to 4,000, and most preferably 1,500 to 3,000.
Further, the weight average molecular weight (hereinafter abbreviated as Mw) of the ester (E) is 4,000 from the viewpoint of solubility in the solvent (F) used in the production method described in detail later, image strength and heat storage stability. It is preferably 20,000 to 20,000, more preferably 4,000 to 10,000.

In the present invention, Mn and Mw of the ester (E) are measured by gel permeation chromatography (GPC) under the following conditions.
Equipment (example): HLC-8120 manufactured by Tosoh Corporation
Column (example): 2 TSK GEL GMH6 [manufactured by Tosoh Corporation]
Measurement temperature: 40 ° C
Sample solution: 0.25 wt% THF (tetrahydrofuran) solution Injection amount: 100 μl
Detection device: Refractive index detector Reference material: Tosoh standard polystyrene (TSKstandard POLYSTYRENE) 12 points (molecular weight 500 1050 2800 5970 9100 18100 37900 96400 1900000 355000 1090000 2890000)

The ester (E) is produced by subjecting the polyester polyol (C) and the monocarboxylic acid (D) to a known condensation reaction (condensation reaction described in JP-A-2016-133713). can do.

Further, the toner additive of the present invention contains a compound used for the polycondensation reaction of the polyester polyol (C) and a compound used for the condensation reaction of the ester (E) as long as the effect of the invention is not impaired. It may be contained.

The weight ratio of the ester (E) contained in the toner additive of the present invention is preferably 50 to 100% by weight with respect to the weight of the wax from the viewpoint of low temperature fixability and fluidity.

Since the toner additive of the present invention is difficult to be extracted from the toner binder resin into the carbon dioxide phase during the production of toner using carbon dioxide, which will be described in detail later, a sufficient amount of toner can be produced. It contains an additive for toner, and its effect can be fully exhibited.
Since the toner additive of the present invention is particularly effective as a wax dispersant, the toner produced by using the toner additive of the present invention is excellent in wax dispersibility. Therefore, the obtained toner is excellent in charge stability and heat storage stability.

The toner of the present invention contains the toner additive of the present invention, the toner binder resin (R), the colorant (g) and the wax (w).

As the toner binder resin (R), a known toner binder resin (the toner binder resin described in JP-A-2016-133713, JP-A-2016-157119, International Publication No. 2016/136652, etc.) is used. Possible and preferred are at least one polyol selected from the group consisting of alkylene oxide adducts of ethylene glycol, propylene glycol and bisphenol A, polyester which is a polycondensate of terephthalic acid and trimellitic anhydride. Examples include ester.
As the toner binder resin (R), one type may be used alone, or two or more types may be used in combination.

The toner binder resin (R) in the present invention preferably has a glass transition point of 50 to 65 ° C. and a flow softening temperature of 100 to 120 ° C. from the viewpoint of low temperature fixability.
In the present invention, the flow softening temperature can be measured by the following method.
<Measurement method of flow softening temperature>
Using a descent type flow tester [CFT-500D manufactured by Shimadzu Corporation], a load of 1.96 MPa is applied by a plunger while heating 1 g of the measurement sample at a temperature rise rate of 6 ° C./min, and the diameter is 1 mm. , Extrude from a nozzle with a length of 1 mm, draw a graph of "plunger drop amount (flow value)" and "temperature", and read the temperature corresponding to 1/2 of the maximum value of the plunger drop amount from the graph. , This value (the temperature when half of the measurement sample flowed out) was taken as the softening point.

As the colorant (g), all of the known dyes and pigments used as colorants for toner can be used.
Specific examples of the colorant (g) include carbon black, iron black, Sudan black SM, first yellow G, benzidine yellow, pigment yellow, India first orange, irgasin red, paranitroaniline red, toluisin red, and carmine FB. Pigment Orange R, Lake Red 2G, Rhodamin FB, Rhodamin B Lake, Methyl Violet B Lake, Phtalocyanin Blue, Pigment Blue, Brilliant Green, Phtalussinin Green, Oil Yellow GG, Kayaset YG, Orazole Brown B and Oil Pink OP. Be done.
The above-mentioned colorant (g) may be used alone or in combination of two or more.
Further, if necessary, a magnetic powder (powder of a ferromagnetic metal such as iron, cobalt and nickel and a compound such as magnetite, hematite and ferrite) can be contained also as a colorant.

The wax (w) is at least one selected from the group consisting of ester waxes, polyolefin waxes, fatty alcohols having 30 to 50 carbon atoms and fatty acids having 30 to 50 carbon atoms.

Examples of the ester wax include known ester waxes (ester waxes described in JP-A-2013-15673 and the like).
The ester wax is preferably an ester of a carboxylic acid and an alcohol, wherein at least one of the carboxylic acid or the alcohol has a long-chain alkyl group.

Examples of the carboxylic acid having a long-chain alkyl group (preferably 14 to 24 carbon atoms) used in the synthesis of the ester wax include myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid and lignoceric acid.
Examples of other carboxylic acids used in the synthesis of ester wax include polyvalent carboxylic acids (such as oxalic acid, malonic acid, succinic acid, glutaric acid, fumaric acid and aconitic acid).

Examples of alcohols having a long-chain alkyl group (preferably 8 to 24 carbon atoms) used in the synthesis of ester wax include capryl alcohol, capric alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, arathidyl alcohol, behenyl alcohol and the like. Lignoceryl alcohol and the like can be mentioned.
Other alcohols used in the synthesis of ester wax include polyhydric alcohols [ethylene glycol, propylene glycol, trimethylolpropane, sugar alcohols, saccharides (pentaerytritor, triose, tetrose, pentose, hexose, and disaccharides of these saccharides). And oligosaccharides, etc.] and the like.
Further, the carbon number of the carboxylic acid-derived group and the alcohol-derived group constituting the ester wax are preferably 22 or less from the viewpoint of low-temperature fixability, and the carbon number is 21 from the viewpoint of heat-resistant storage. The above is preferable, and the carbon number is 22 more preferably from the viewpoint of low temperature fixing property and heat storage property.
Examples of the ester wax having 22 carbon atoms in the carboxylic acid-derived group and 22 carbon atoms in the alcohol-derived group constituting the ester wax include monoesters of behenic acid and behenic alcohol.

As the polyolefin wax, a (co) polymer of an olefin (ethylene, propylene, 1-butene, isobutylene, 1-hexene, 1-dodecene, 1-octadecene and a mixture thereof, etc.) [and one obtained by (co) polymerization. Including heat-reduced polyolefin], oxide of olefin (co) polymer with oxygen and / or ozone, maleic acid modified product of olefin (co) polymer [maleic acid and its derivatives (maleic anhydride, maleic acid) (Monomethyl, monobutyl maleate, dimethyl maleate, etc.) modified products], olefins and unsaturated carboxylic acids [(meth) acrylic acid, itaconic acid, maleic anhydride, etc.] and / or unsaturated carboxylic acid alkyl esters [(meth) acrylic Examples thereof include a copolymer with an alkyl acid (1 to 18 carbon atoms of an alkyl) ester and an alkyl maleic anhydride (1 to 18 carbon atoms of an alkyl) ester, etc.] and sazole wax.
The polyolefin wax can also be obtained from a natural product such as paraffin wax.
Examples of the aliphatic alcohol having 30 to 50 carbon atoms include triacontanol and the like.
Examples of the fatty acid having 30 to 50 carbon atoms include triacontane carboxylic acid and the like.

The above wax (w) may be used alone or in combination of two or more.
Of these, ester wax is preferable, and behenic acid and behenic alcohol are more preferably monoesters, from the viewpoint of low-temperature fixing property and heat-resistant storage property.

The wax (w) in the present invention preferably has a flow tester softening temperature of 50 to 170 ° C.

The toner of the present invention is, if necessary, a fluidizing agent, a solvent (F) and organic fine particles (H) in addition to the toner additive, the toner binder resin (R), the colorant (g) and the wax (w) of the present invention. ) Etc. may be contained.

Examples of the fluidizing agent include colloidal silica, alumina powder, titanium oxide powder, calcium carbonate powder and the like.

Examples of the solvent (F) include a ketone solvent (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl amylketone, etc.) and an ester solvent (ethyl acetate, butyl acetate, ethyl pyruvate, 2-hydroxyisobutyric acid ester, lactic acid ester and propylene). Glycol monomethyl ether acetate, etc.), alcohol solvents (methanol, ethanol, 2-propanol, isopropyl alcohol, sec-butyl alcohol, t-butyl alcohol, ethylene glycol, etc.), aromatic hydrocarbon solvents (toluene, benzene, chlorobenzene, xylene, etc.) ), aliphatic hydrocarbon solvents (hexane and cyclohexane, etc.), heterocyclic aromatic amines (pyridine and N-methylpyrrolidone, etc.), N, N-dimethylformamide, dimethylsulfoxide, water, and mixtures thereof.
Of these, a ketone solvent, an ester solvent and an alcohol solvent are preferable from the viewpoint of handling, and acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, ethyl acetate and t-butyl alcohol are more preferable.

As the organic fine particles (H), the fine particles (A) described in International Publication No. 2011/152008 and the like, that is, fine particles containing a crystalline resin and / or an amorphous resin can be used.
When the toner of the present invention contains organic fine particles (H), the organic fine particles (H) are adhered to the surface of the particles containing the toner binder resin (R), the colorant (g) and the wax (w). It may be one in which a film derived from organic fine particles (H) is formed, or one in which a part of organic fine particles (H) is formed into a film.
"The organic fine particles (H) are fixed to the surface of the above particles" does not include the case where the organic fine particles (H) simply adhere to the surface of the resin particles (Y) and are easily detached. And.
The surface state and shape of the toner can be observed, for example, by using a scanning electron microscope (SEM) and taking a photograph of the surface of the resin particles magnified 10,000 times or 30,000 times.

The weight ratio of the toner additive of the present invention contained in the toner of the present invention may be 30 to 100% by weight based on the weight of the wax (w) from the viewpoint of low temperature fixability and fluidity. preferable.
The weight ratio of the toner binder resin (R) contained in the toner of the present invention is preferably 75 to 90% by weight based on the weight of the toner from the viewpoint of low temperature fixability.
The content of the colorant (g) contained in the toner of the present invention is preferably 1 to 11 parts by weight, more preferably 3 to 10 parts by weight, based on 100 parts by weight of the toner binder resin from the viewpoint of low temperature fixability. Is.
The weight ratio of the wax (w) contained in the toner of the present invention is preferably 0.001 to 10% by weight, more preferably 0.5 to 10% by weight, and particularly preferably 1 to 10% by weight, based on the weight of the toner. %.
When the toner of the present invention contains a fluidizing agent, the weight ratio of the fluidizing agent is preferably 0.001 to 10% by weight, more preferably 0.01 to 5% by weight, particularly preferably, based on the weight of the toner. Is 0.1 to 4% by weight.
When the toner of the present invention contains the solvent (F), the weight ratio of the solvent (F) is preferably 0.01 to 10% by weight, more preferably 0.01 to 5%, based on the weight of the toner. % By weight.
When the toner of the present invention contains organic fine particles (H), the weight ratio of the organic fine particles (H) is preferably 5 to 15% by weight based on the weight of the toner.
When the composition ratio of the toner is in the above range, the charge stability is improved.

The volume average particle size of the toner of the present invention is preferably 1 to 12 μm, more preferably 2 to 10 μm, and particularly preferably 3 to 8 μm. When it is 1 μm or more, the handleability as a powder is improved. When it is 12 μm or less, the melting characteristics are improved.

The ratio [Dv / Dn] of the volume average particle diameter Dv and the number average particle diameter Dn of the toner of the present invention is preferably 1.0 to 1.5, more preferably 1.0 to 1.4, and particularly. It is preferably 1.0 to 1.3. When it is 1.5 or less, the handleability as a powder and the melting characteristics are remarkably improved.

The volume average particle diameter of the toner of the present invention and the ratio [Dv / Dn] of the volume average particle diameter Dv to the number average particle diameter Dn are determined by the solvent (F) in the method for producing the toner of the present invention, which will be described in detail later. The resin (R) and the organic fine particles (H) dissolved in the resin (R) can be adjusted by the stirring speed when dispersed in the carbon dioxide (X) and the ratio of the organic fine particles (H) to the resin (R).
Increasing the stirring speed reduces the volume average particle size, and increasing the ratio of the organic fine particles (H) to the resin (R) reduces the volume average particle size.
The same applies to Dv / Dn. If the stirring speed is increased, Dv / Dn becomes smaller, and if the ratio of the organic fine particles (H) to the resin (R) is increased, Dv / Dn becomes smaller.
If necessary, the toner of the present invention can be classified using a wind classifier, a sieve, or the like, and the volume average particle diameter and the ratio of the volume average particle diameter to the number average particle diameter can be further adjusted.

Examples of the method for producing the toner of the present invention include a pulverization method (method described in JP-A-2016-133713 and International Publication No. 2016/136652), and a toner having good heat-resistant storage stability can be obtained. From the viewpoint of being able to do so, the manufacturing method using the compressible fluid described in detail below is preferable.
Hereinafter, a method for producing using carbon dioxide as a compressible fluid will be described.

The toner of the present invention is a wax dispersion liquid (L) containing a colorant dispersion liquid (G), a toner binder resin (R) solution (L), and a toner additive of the present invention in carbon dioxide (X). By dispersing W) and growing the dispersed resin (R) as particles, it contains an additive for toner, a toner binder resin (R), a colorant (g), a solvent (F) and a wax (w). Toner resin particles (Y1) are formed.
Further, if necessary, by using a dispersion (X0) in which organic fine particles (H) are dispersed in carbon dioxide (X) instead of carbon dioxide (X), the surface of the resin particles (Y1) can be used. Resin particles (Z1) to which organic fine particles (H) are adhered can be formed.
The above resin particles (Y1) and (Z1) correspond to the toner of the present invention.
Hereinafter, the dispersion (Q) in which (Y1) and / or (Z1) are dispersed in a dispersion medium containing (X) and (F) is referred to as a dispersion (Q).

The colorant dispersion liquid (G) is obtained by dispersing the colorant (g) in the solvent (F).
The colorant dispersion liquid (G) preferably further contains a pigment dispersant.
As the pigment dispersant, a known pigment dispersant (pigment dispersant described in JP-A-2016-14826, etc.) can be used.
The colorant dispersion (G) can be produced in the solvent (F) by a method of pulverizing the colorant (g) with a bead mill or the like.

The solution (L) of the toner binder resin (R) is obtained by dissolving the toner binder resin (R) in the solvent (F).

The wax dispersion liquid (W) containing the toner additive of the present invention is obtained by dispersing the toner additive of the present invention in a solvent (F) containing the wax (w).
The wax dispersion liquid (W) can be produced by a method of pulverizing the toner additive of the present invention in a solvent (F) containing the wax (w) with a bead mill or the like.

As a method for producing a dispersion (X0) in which organic fine particles (H) are dispersed in carbon dioxide (X), for example, a dispersion liquid in which organic fine particles (H) are dispersed in a solvent (F) is prepared. , A method of dispersing this dispersion in carbon dioxide (X) can be mentioned.

Any method may be used to disperse the toner binder resin (R) solution (L), the colorant dispersion (G) and the wax dispersion (W) into carbon dioxide (X) or the dispersion (X0). May be good.
Specific examples of the dispersion method include the following (1) to (4).
(1) A mixture of a colorant dispersion (G), a solution (L) and a wax dispersion (W) is dispersed in carbon dioxide (X) or a dispersion (X0) with a stirrer, a disperser or the like. Method.
(2) A mixed solution of the colorant dispersion (G), the solution (L) and the wax dispersion (W) is sprayed into carbon dioxide (X) or the dispersion (X0) through a spray nozzle. A method of forming droplets, making the resin in the droplets hypersaturated, and precipitating resin particles (ASES: Aerosol Solvent Operation System).
(3) From a coaxial multiplex tube (double tube, triple tube, etc.), a mixed solution of a colorant dispersion liquid (G), a solution (L), and a wax dispersion liquid (W) and carbon dioxide (X) or dispersion. As a method (SEDS: Solution Enhanced Dispersion by Liquid Liquids) in which a body (X0) is simultaneously ejected from different tubes together with a high-pressure gas and an entrainer to apply external stress to the droplets to promote splitting. Are known).
(4) A mixed solution of a colorant dispersion (G), a solution (L) and a wax dispersion (W) is ejected into carbon dioxide (X) or a dispersion (X0) into droplets obtained. A method of irradiating ultrasonic waves.

The dispersion (Q) is preferably a single phase. That is, it is not preferable that the solvent (F) phase is separated from the phase containing carbon dioxide (X) in which (Y1) and / or (Z1) are dispersed. Therefore, it is preferable to set the amount of the solution (L) of (R) with respect to carbon dioxide (X) so that the solvent phase does not separate.
From the above viewpoint, the weight ratio of the solution (L) of (R) is preferably 90% by weight or less, more preferably 5 to 80% by weight, and particularly preferably 10 to 70% by weight based on the weight of (X). Is.
The weight ratio of the solvent (F) is the total weight of the resin particles (Y1) and (Z1) obtained by manufacturing [additive for toner to be added, toner binder resin (R), colorant (g), wax. Calculated from the weight of (w) and the organic fine particles (H)], preferably 10 to 90% by weight, more preferably 20 to 70% by weight.
The weight ratio of the resin (R) to the carbon dioxide (X) [resin (R): carbon dioxide (X)] is preferably 1: (0.1 to 100), more preferably 1: (. 0.5 to 50), particularly preferably 1: (1 to 20).

When the organic fine particles (H) are used, the ratio of the total weight of the crystalline resin and the amorphous resin constituting the organic fine particles (H) to the weight of the resin (R) constituting the resin particles (Y1) [crystallinity]. The total weight of the resin and the amorphous resin: the weight of the resin (R)] is preferably (0.1: 99.9) to (30:70), and more preferably (0.2: 99. 8)-(20:80). When the weight ratio is within this range, both low-temperature fixing property and heat-resistant storage property are both preferable.
The weight ratio of the organic fine particles (H) to the resin particles (Y1) is not particularly limited, but the weight ratio of (H) is 5 to 20% by weight based on the weight of the resin particles (Y1). It is preferable, and more preferably 5 to 15% by weight. Within this range, the dispersibility of the resin particles (Z1) is improved.

In the method for producing a toner of the present invention, the formed resin particles (Y1) and / or the resin particles (Z1) are treated with carbon dioxide (X) during dispersion, and then carbon dioxide (X) is added. By removing it, the target resin particles (Y1) and / or the resin particles (Z1) can be obtained. Here, the treatment means that the resin particles (Y1) and / or the resin particles (Z1) are dispersed in (X) and contacted with (X) for a certain period of time to swell (Y1) and / or (Z1). Say that.
The above-mentioned fixed time [including the time required for the resin particles (Y1) and / or the resin particles (Z1) to be formed. ] Is preferably 10 seconds to 180 minutes, more preferably 30 seconds to 60 minutes.
The swelling is performed by contacting the resin particles (Y1) and / or the resin particles (Z1) with carbon dioxide (X) for a certain period of time so that the carbon dioxide (X) becomes the resin particles (Y1) and / or the resin particles (Z1). ) It happens by penetrating into. Therefore, the degree of swelling can be adjusted by the contact time with (X), the pressure of (X), and the temperature.

In the production method of the present invention, when treating with carbon dioxide (X), it is preferable to carry out at the temperature described below. That is, in order to prevent the phase transition of carbon dioxide to a solid in the pipe during depressurization and blocking the flow path, the temperature is preferably 30 ° C. or higher, and resin particles (Y1), resin particles (Z1) and organic fine particles (Z1) ( In order to prevent thermal deterioration of H), the temperature is preferably 200 ° C. or lower. Further, 30 to 150 ° C. is preferable, particularly preferably 34 to 130 ° C., particularly preferably 35 to 100 ° C., and most preferably 40 ° C. to 80 ° C.
The same applies to the temperatures of the dispersion (X0) and the dispersion (Q).
When the organic fine particles (H) are used, the treatment with carbon dioxide (X) can be performed at a temperature above or below the Tg or melting point of the organic fine particles (H), but at a temperature below Tg or melting point. Is preferable.

When treating with carbon dioxide (X), it is preferable to carry out at the pressure described below. That is, it is preferably 3 MPa or more in order to satisfactorily disperse the resin particles (Y1) and the resin particles (Z1) in (X), and preferably 40 MPa or less from the viewpoint of equipment cost and operating cost. It is more preferably 3.5 to 35 MPa, particularly preferably 4 to 30 MPa, particularly preferably 4.5 to 25 MPa, and most preferably 5 to 20 MPa. The same applies to the pressure in the container forming the dispersion (X0) and the dispersion (Q).

As for the temperature and pressure when treating in carbon dioxide (X), the resin particles (Y1) and the resin particles (Z1) are not dissolved in (X), and the carbon dioxide (X) is (Y1) and (Z1). ) Is preferably set within a range that allows permeation. In general, the lower the temperature or low pressure, the more likely it is that (Y1) and (Z1) do not dissolve in (X), and the higher the temperature or high pressure, the easier it is for (X) to permeate (Y1) and (Z1). It becomes.
Further, the carbon dioxide (X) at the time of treatment is preferably adjusted to the above-mentioned preferable temperature and pressure to be in a liquid, subcritical state or supercritical state.

In the method for producing a toner of the present invention, the resin particles (Y1) and / or the resin particles (Z1) form a dispersion (Q) dispersed in a dispersion medium containing (X) and (F). After the treatment, the solvent (F) needs to be removed or reduced.
As a method of removing or reducing the solvent (F), there is a method of reducing the pressure of the container as it is, but the solvent dissolved in (Y1) is condensed and the resin particles (Y1) are redissolved or the resin particles (Y1) are redissolved. ) And / or when collecting the resin particles (Z1), there may be a problem that the resin particles (Y1) and / or the resin particles (Z1) are united with each other.
Therefore, as a preferred method, for example, by further mixing carbon dioxide (X) with the dispersion (Q), the solvent (F) is extracted from the dispersion (Q) into the phase of carbon dioxide (X). Next, a method of substituting carbon dioxide (X) containing a solvent (F) with carbon dioxide (X) not containing a solvent (F) and then reducing the pressure may be mentioned.

In the method of mixing carbon dioxide (X), carbon dioxide (X) having a pressure higher than that of the dispersion (Q) may be added, and the dispersion (Q) may be added to carbon dioxide (X) having a pressure lower than that of the dispersion (X). Although it may be added, the latter is preferable from the viewpoint of ease of continuous operation. The amount of carbon dioxide (X) mixed with the dispersion (Q) is preferably 1 to 50 times the volume of the dispersion (Q) from the viewpoint of preventing coalescence of the resin particles (Y1) and the resin particles (Z1). It is more preferably 1 to 40 times, and particularly preferably 1 to 30 times. By removing or reducing the solvent contained in the resin particles (Y1) and (Z1) as described above, and then removing the vaporized carbon dioxide (X), the resin particles (Y1) and / or the resin particles It is possible to prevent (Z1) from uniting with each other.

As a method of replacing carbon dioxide (X) containing a solvent (F) with carbon dioxide (X) not containing a solvent (F), the resin particles (Y1) and the resin particles (Z1) are once supplemented with a filter or a cyclone. After that, a method of circulating carbon dioxide (X) until the solvent (F) is completely removed while maintaining the pressure can be mentioned. The amount of carbon dioxide (X) to be distributed is preferably 1 to 100 times, more preferably 1 to 70 times the volume of the dispersion (Q) from the viewpoint of removing the solvent from the dispersion (Q). It is double, particularly preferably 1 to 50 times.

Carbon dioxide (X) and solvent (F) are removed from the dispersion (Q) in which the resin particles (Y1) and / or the resin particles (Z1) are dispersed by reducing the pressure, and the resin particles (Y1) which is the toner of the present invention are removed. ) And / or obtain resin particles (Z1). At that time, the pressure may be reduced stepwise by providing the containers whose pressure is independently controlled in multiple stages, or the pressure may be reduced to normal temperature and pressure at once.
The method for collecting the resin particles (Y1) and the resin particles (Z1) is not particularly limited, and examples thereof include a method of filtering with a filter and a method of centrifuging with a cyclone or the like.
The resin particles (Y1) and the resin particles (Z1) may be collected after depressurization, or may be collected in high pressure before depressurization and then depressurized. As a method of taking out the resin particles (Y1) and the resin particles (Z1) from the high pressure when the pressure is reduced after collecting under high pressure, the collection container may be depressurized by a batch operation, or the rotary valve may be used. It may be used to perform a continuous retrieval operation.

The step of removing the solvent (F) from the dispersion (Q) preferably includes a step of cooling the dispersion (Q) from the viewpoint of solvent removal efficiency.
By cooling the dispersion (Q), the solubility of the resin (R) in the solvent (F) is lowered, and the solvent (F) in the resin particles (Y1) and the resin particles (Z1) is released from the inside of the resin particles. By being discharged to the dispersion medium phase containing carbon dioxide (X) and the solvent (F), the solvent (F) content in the resin particles (Y1) and the resin particles (Z1) is suppressed from coalescing the particles. From the viewpoint, it can be efficiently reduced to 10% by weight or less, which is preferable. Any method that includes this cooling step may be used in combination with other solvent removal methods.

The cooling temperature is determined by the temperature Ta [° C.] at which the viscosity of the solution (L) becomes 10,000 Pa · s or more, and it is necessary to cool to Ta [° C.] or lower. When the cooling temperature is higher than Ta [° C.], precipitation of the resin (R) does not occur, and the solvent (F) content in the resin particles (Y1) and the resin particles (Z1) may be reduced to 10% by weight or less. Have difficulty.

The cooling method may be any method as long as it can be Ta [° C.] or lower, but it is already (Ta-10) [° C.] or lower [more preferably (Ta-20) to (Ta-60). A method of adding liquid carbon dioxide (X1) cooled to [° C.]] into the dispersion (Q) is preferable. By adding liquid carbon dioxide (X1) cooled to (Ta-10) [° C.] or lower, the process time can be significantly shortened.
The amount of liquid carbon dioxide (X1) added for cooling is preferably 0.5 times or more, more preferably 1 to 10 times the weight of the dispersion (Q). When the weight of (X1) is 0.5 times or more, the temperature of (Q) easily becomes Ta [° C.] or less.

Therefore, in the step of removing the solvent (F) from the dispersion (Q), the temperature of the dispersion (Q) is cooled to Ta [° C.] or lower, and the solvent (Z1) is removed from the resin particles (Y1) and the resin particles (Z1). After removing the solvent from F), the dispersion medium containing liquid carbon dioxide (X1) and the solvent (F) is solid-liquid separated from the resin particles (Y1) and the resin particles (Z1), and the resin particles (Y1) are separated. ) And the resin particles (Z) are preferably collected.
In this case, the method for collecting the resin particles (Y1) and the resin particles (Z1) is not particularly limited, and a method for filtering the dispersion (Q) after cooling to Ta [° C.] or less with a filter, a cyclone, or the like is used. Examples thereof include a method of centrifuging. The resin particles (Y1) and the resin particles (Z1) may be collected after depressurization, or may be collected in high pressure before depressurization and then depressurized. As a method of taking out the resin particles (Y1) and the resin particles (Z1) from the high pressure when the pressure is reduced after collecting under high pressure, the collection container may be depressurized by a batch operation, or the rotary valve may be used. It may be used to perform a continuous retrieval operation.
Among the above methods, the preferred collection method is a method in which the dispersion (Q) cooled to Ta [° C.] or lower is filtered through a filter and then collected under reduced pressure. After depressurization, the liquid carbon dioxide (X1) is preferably 2 with respect to the total weight of the solid content of the resin particles (Y1) and the resin particles (Z1) [weight excluding (F) and (X)]. . By adding 5 to 5 times the weight and performing an operation of further extracting the solvent (F) from the resin particles (Y1) and the resin particles (Z1), the resin particles (Y1) and the resin particles (Z1) can be further extracted. It is possible to further suppress coalescence.

In the resin particles (Z1), when the organic fine particles (H) contain a crystalline resin, after forming the resin particles (Z1), if necessary, as a further step, the crystalline resin, preferably the melting point, is used. By heating to -50 ° C or higher, more preferably -10 ° C or higher, and particularly preferably -10 ° C or higher, the organic fine particles (H) adhering to the surface of the resin particles (Y1) are melted and the organic fine particles (H) are melted. ) Can be fixed to the surface of the resin particles (Y1), or a film derived from the organic fine particles (H) can be formed to form the resin particles. From the viewpoint of suppressing the aggregation of the resin particles, the heating time is preferably 0.01 to 1 hour, more preferably 0.05 to 0.7 hours.

In the resin particles (Z1) obtained by the above production method, the organic fine particles (H) are once fixed to the surface of the resin particles (Y1). For example, when (H) contains a crystalline resin, the crystalline resin is used. Depending on the composition of the resin (R) and the type of the solvent (F), the organic fine particles (H) are filmed during the manufacturing process, and the organic fine particles (H) are filmed on the surface of the resin particles (Y1). A film may be formed.

The resin particles (Y1) and the resin particles (Z1), which are the toners of the present invention obtained by the above production method, are crystallized by treatment with carbon dioxide (X) which has become liquid or supercritical under the above conditions. The degree of crystallization is improved and the heat-resistant storage stability is improved.

The toner of the present invention is electrically mixed with carrier particles such as iron powder, glass beads, nickel powder, ferrite, magnetite, and ferrite whose surface is coated with a resin (acrylic resin, silicone resin, etc.), if necessary. It is used as a developer for latent images. The weight ratio of the toner to the carrier particles is preferably 1/99 to 100/0.
Further, even when the toner of the present invention does not use carrier particles, it is possible to form an electrically latent image by rubbing it with a member such as a charging blade.

The toner of the present invention can be used as a recording material to be fixed to a support (paper, polyester film, etc.) by a copying machine, a printer, or the like. As a method for fixing the toner of the present invention to the support, known thermal roll fixing methods, flash fixing methods and the like can be applied.

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples.
In the following, the part represents the weight part.
Further, in the following, Examples 2, 4, 10 and 12 mean Reference Examples 1 to 4.

<Examples 1 to 8, 19 to 21 and Comparative Example 1>
Toner additives (J-1) to (J-8), (J-19) to (J-21) of the present invention and toner additives (J'-1) for comparison can be obtained by the following methods. Manufactured.

<Example 1><Synthesis of toner additive (J-1)>
In a reaction vessel equipped with a cooling tube, a thermometer, a stirrer and a nitrogen introduction tube, 2 mol of bisphenol A propylene oxide adduct [New Pole BP-2P, manufactured by Sanyo Kasei Kogyo Co., Ltd.] 303.7 parts (24. 0 mol%), bisphenol A propylene oxide 3 mol adduct [New Pole BP-3P, manufactured by Sanyo Kasei Kogyo Co., Ltd.] 334.6 parts (23.6 mol%), terephthalic acid 226.8 parts (37.6) (Mole%) and 2 parts of titanium diisopropoxybistriethanol aminate as a condensation catalyst were added, and the reaction was carried out at 220 ° C. under a nitrogen stream for 4 hours while distilling off the generated water. Further, the reaction was carried out at 220 ° C. for 10 hours under a reduced pressure of 0.5 to 2.5 kPa. When the acid value became less than 1, 181.7 parts (14.7 mol%) of behenic acid was added, and the reaction was carried out at 180 ° C. under a nitrogen stream for 2 hours while distilling off the generated water. Further, the reaction was carried out at 180 ° C. for 1 hour under a reduced pressure of 0.5 to 2.5 kPa. When the acid value became less than 1, the reaction product was taken out from the reaction vessel to obtain an ester compound (E-1).
The acid value of the ester compound (E-1) was 0.4 mgKOH / g, the hydroxyl value was 15 mgKOH / g, the glass transition point (Tg) was −25 ° C., Mn was 2,700, and Mw was 6,100.
The ester compound (E-1) obtained above was used as an additive for toner (J-1).

<Example 2><Synthesis of toner additive (J-2)>
In a reaction vessel equipped with a cooling tube, a thermometer, a stirrer and a nitrogen introduction tube, 2 mol of bisphenol A propylene oxide adduct [New Pole BP-2P, manufactured by Sanyo Kasei Kogyo Co., Ltd.] 721.6 parts (53. 1 mol%), 274.9 parts of terephthalic acid (42.4 mol%) and 2 parts of titanium diisopropoxybistriethanol aminate as a condensation catalyst were added, and the water produced was retained at 220 ° C. under a nitrogen stream. It was allowed to react for 4 hours while leaving. Further, the reaction was carried out at 220 ° C. for 10 hours under a reduced pressure of 0.5 to 2.5 kPa. When the acid value became less than 1, 60.6 parts (4.6 mol%) of behenic acid was added, and the reaction was carried out at 180 ° C. under a nitrogen stream for 2 hours while distilling off the generated water. Further, the reaction was carried out at 180 ° C. for 1 hour under a reduced pressure of 0.5 to 2.5 kPa. When the acid value became less than 1, it was taken out from the reaction vessel to obtain an ester compound (E-2).
The acid value of the ester compound (E-2) was 0.3 mgKOH / g, the hydroxyl value was 40 mgKOH / g, the glass transition point (Tg) was 40 ° C., Mn was 2,600, and Mw was 6,200.
The ester compound (E-2) obtained above was used as a toner additive (J-2).

<Example 3><Synthesis of toner additive (J-3)>
In a reaction vessel equipped with a cooling tube, a thermometer, a stirrer and a nitrogen introduction tube, 2 mol of bisphenol A propylene oxide adduct [New Pole BP-2P, manufactured by Sanyo Kasei Kogyo Co., Ltd.] 581.7 parts (45. 0 mol%), 221.6 parts (35.9 mol%) of terephthalic acid and 2 parts of titanium diisopropoxybistriethanol aminated as a condensation catalyst, and the water produced was retained at 220 ° C. under a nitrogen stream. It was allowed to react for 4 hours while leaving. Further, the reaction was carried out at 220 ° C. for 10 hours under a reduced pressure of 0.5 to 2.5 kPa. When the acid value became less than 1, 242.2 parts (19.1 mol%) of behenic acid was added, and the reaction was carried out at 180 ° C. under a nitrogen stream for 2 hours while distilling off the generated water. Further, the reaction was carried out at 180 ° C. for 1 hour under a reduced pressure of 0.5 to 2.5 kPa. When the acid value became less than 1, it was taken out from the reaction vessel to obtain an ester compound (E-3).
The acid value of the ester compound (E-3) was 0.4 mgKOH / g, the hydroxyl value was 10 mgKOH / g, the glass transition point (Tg) was −33 ° C., Mn was 2,600, and Mw was 6,400.
The ester compound (E-3) obtained above was used as an additive for toner (J-3).

<Example 4><Synthesis of toner additive (J-4)>
In a reaction vessel equipped with a cooling tube, a thermometer, a stirrer and a nitrogen introduction tube, a bisphenol A propylene oxide 2 mol adduct [New Pole BP-2P, manufactured by Sanyo Kasei Kogyo Co., Ltd.] 356.3 parts (28. 0 mol%), 392.5 parts (27.6 mol%) of bisphenol A propylene oxide 3 mol adduct, 240.2 parts (39.6 mol%) of terephthalic acid and titanium diisopropoxybistriethanol aminate as a condensation catalyst. Two parts were charged and reacted at 220 ° C. under a nitrogen stream for 4 hours while distilling off the generated water. Further, the reaction was carried out at 220 ° C. for 10 hours under a reduced pressure of 0.5 to 2.5 kPa. When the acid value became less than 1, 60.6 parts (4.9 mol%) of behenic acid was added, and the reaction was carried out at 180 ° C. under a nitrogen stream for 2 hours while distilling off the generated water. Further, the reaction was carried out at 180 ° C. for 1 hour under a reduced pressure of 0.5 to 2.5 kPa. When the acid value became less than 1, it was taken out from the reaction vessel to obtain an ester compound (E-4).
The acid value of the ester compound (E-4) was 0.2 mgKOH / g, the hydroxyl value was 60 mgKOH / g, the glass transition point (Tg) was 20 ° C., Mn was 1,500, and Mw was 4,100.
The ester compound (E-4) obtained above was used as an additive for toner (J-4).

<Example 5><Synthesis of toner additive (J-5)>
In a reaction vessel equipped with a cooling tube, a thermometer, a stirrer and a nitrogen introduction tube, 2 mol of bisphenol A propylene oxide adduct [New Pole BP-2P, manufactured by Sanyo Kasei Kogyo Co., Ltd.] 314.8 parts (24. 2 mol%), bisphenol A propylene oxide 3 mol adduct [New Pole BP-3P, manufactured by Sanyo Kasei Kogyo Co., Ltd.] 346.8 parts (23.8 mol%), terephthalic acid 235.1 parts (37.8) (Mole%) and 2 parts of titanium diisopropoxybistriethanol aminate as a condensation catalyst were added, and the reaction was carried out at 220 ° C. under a nitrogen stream for 4 hours while distilling off the generated water. Further, the reaction was carried out at 220 ° C. for 10 hours under a reduced pressure of 0.5 to 2.5 kPa. When the acid value became less than 1, 151.7 parts (14.2 mol%) of stearic acid was added, and the mixture was reacted at 180 ° C. under a nitrogen stream for 2 hours while distilling off the generated water. Further, the reaction was carried out at 180 ° C. for 1 hour under a reduced pressure of 0.5 to 2.5 kPa. When the acid value became less than 1, it was taken out from the reaction vessel to obtain an ester compound (E-5).
The acid value of the ester compound (E-5) was 0.3 mgKOH / g, the hydroxyl value was 15 mgKOH / g, the glass transition point (Tg) was 5 ° C., Mn was 2,600, and Mw was 6,000.
The ester compound (E-5) obtained above was used as an additive for toner (J-5).

<Example 6><Synthesis of toner additive (J-6)>
In a reaction vessel equipped with a cooling tube, a thermometer, a stirrer and a nitrogen introduction tube, 2 mol of bisphenol A propylene oxide adduct [New Pole BP-2P, manufactured by Sanyo Kasei Kogyo Co., Ltd.] 290.6 parts (22. 2 mol%), 3 mol adduct of bisphenol A propylene oxide [New Pole BP-3P, manufactured by Sanyo Kasei Kogyo Co., Ltd.] 320.5 parts (21.9 mol%), 14.7 parts of trimethylolpropane (2. 9 mol%), 242.3 parts of terephthalic acid (38.8 mol%) and 2 parts of titanium diisopropoxybistriethanol aminate as a condensation catalyst were added, and the water produced was retained at 220 ° C. under a nitrogen stream. It was allowed to react for 4 hours while leaving. Further, the reaction was carried out at 220 ° C. for 10 hours under a reduced pressure of 0.5 to 2.5 kPa. When the acid value became less than 1, 181.7 parts (14.2 mol%) of behenic acid was added, and the mixture was reacted at 180 ° C. under a nitrogen stream for 2 hours while distilling off the generated water. Further, the reaction was carried out at 180 ° C. for 1 hour under a reduced pressure of 0.5 to 2.5 kPa. When the acid value became less than 1, it was taken out from the reaction vessel to obtain an ester compound (E-6).
The acid value of the ester compound (E-6) was 0.2 mgKOH / g, the hydroxyl value was 20 mgKOH / g, the glass transition point (Tg) was −25 ° C., Mn was 2,900, and Mw was 9,100.
The ester compound (E-6) obtained above was used as an additive for toner (J-6).

<Example 7><Synthesis of toner additive (J-7)>
In a reaction vessel equipped with a cooling tube, a thermometer, a stirrer and a nitrogen introduction tube, a bisphenol A propylene oxide 2 mol adduct [New Pole BP-2P, manufactured by Sanyo Kasei Kogyo Co., Ltd.] 305.4 parts (24. 5 mol%), bisphenol A propylene oxide 3 mol adduct [New Pole BP-3P, manufactured by Sanyo Kasei Kogyo Co., Ltd.] 336.4 parts (24.1 mol%), terephthalic acid 196.8 parts (33.0) Mol%), 24.6 parts (3.6 mol%) of trimellitic anhydride and 2 parts of titanium diisopropoxybistriethanol aminate as a condensation catalyst were added, and the water produced was generated at 220 ° C. under a nitrogen stream. The reaction was carried out for 4 hours while distilling off. Further, the reaction was carried out at 220 ° C. for 10 hours under a reduced pressure of 0.5 to 2.5 kPa. When the acid value became less than 1, 181.7 parts (14.9 mol%) of behenic acid was added, and the mixture was reacted at 180 ° C. under a nitrogen stream for 2 hours while distilling off the generated water. Further, the reaction was carried out at 180 ° C. for 1 hour under a reduced pressure of 0.5 to 2.5 kPa. When the acid value became less than 1, it was taken out from the reaction vessel to obtain an ester compound (E-7).
The acid value of the ester compound (E-7) was 0.3 mgKOH / g, the hydroxyl value was 20 mgKOH / g, the glass transition point (Tg) was -23 ° C, Mn was 3,000, and Mw was 9,500. The ester compound (E-7) obtained above was used as an additive for toner (J-7).

<Example 8><Synthesis of toner additive (J-8)>
In a reaction vessel equipped with a cooling tube, a thermometer, a stirrer and a nitrogen introduction tube, 2 mol of bisphenol A ethylene oxide adduct [New Pole BPE-20, manufactured by Sanyo Kasei Kogyo Co., Ltd.] 617.6 parts (47. 8 mol%), 253.6 parts of terephthalic acid (38.6 mol%) and 2 parts of titanium diisopropoxybistriethanol amine as a condensation catalyst were added, and the water produced was retained at 220 ° C. under a nitrogen stream. It was allowed to react for 4 hours while leaving. Further, the reaction was carried out at 220 ° C. for 10 hours under a reduced pressure of 0.5 to 2.5 kPa. When the acid value became less than 1, 181.7 parts (13.5 mol%) of behenic acid was added, and the reaction was carried out at 180 ° C. under a nitrogen stream for 2 hours while distilling off the generated water. Further, the reaction was carried out at 180 ° C. for 1 hour under a reduced pressure of 0.5 to 2.5 kPa. When the acid value became less than 1, it was taken out from the reaction vessel to obtain an ester compound (E-8).
The acid value of the ester compound (E-8) was 0.4 mgKOH / g, the hydroxyl value was 20 mgKOH / g, the glass transition point (Tg) was -23 ° C, Mn was 2,500, and Mw was 5,500.
The ester compound (E-8) obtained above was used as an additive for toner (J-8).

<Example 19><Synthesis of toner additive (J-19)>
In a reaction vessel equipped with a cooling tube, a thermometer, a stirrer and a nitrogen introduction tube, a bisphenol A propylene oxide 2 mol adduct [New Pole BP-2P, manufactured by Sanyo Kasei Kogyo Co., Ltd.] 304.6 parts (23. 1 mol%), bisphenol A propylene oxide 3 mol adduct [New Pole BP-3P, manufactured by Sanyo Kasei Kogyo Co., Ltd.] 324.4 parts (21.2 mol%), glycerin [manufactured by Sigma Aldrich] 10.5 2 parts (3.0 mol%), 246.2 parts (39.2 mol%) of terephthalic acid and 2 parts of titanium diisopropoxybistriethanol aminate as a condensation catalyst were added and produced at 220 ° C. under a nitrogen stream. The reaction was carried out for 4 hours while distilling off the water. Further, the reaction was carried out at 220 ° C. for 10 hours under a reduced pressure of 0.5 to 2.5 kPa. When the acid value became less than 1, 157.2 parts (12.2 mol%) of behenic acid was added, and the mixture was reacted at 180 ° C. under a nitrogen stream for 2 hours while distilling off the generated water. Further, the reaction was carried out at 180 ° C. for 1 hour under a reduced pressure of 0.5 to 2.5 kPa. When the acid value became less than 1, it was taken out from the reaction vessel to obtain an ester compound (E-19).
The acid value of the ester compound (E-19) was 0.2 mgKOH / g, the hydroxyl value was 19 mgKOH / g, the glass transition point (Tg) was −26 ° C., Mn was 2,300, and Mw was 3,400.
The ester compound (E-19) obtained above was used as an additive for toner (J-19).

<Example 20><Synthesis of toner additive (J-20)>
In a reaction vessel equipped with a cooling tube, a thermometer, a stirrer and a nitrogen introduction tube, 2 mol of bisphenol A propylene oxide adduct [New Pole BP-2P, manufactured by Sanyo Kasei Kogyo Co., Ltd.] 283.4 parts (21. 4 mol%), bisphenol A propylene oxide 3 mol adduct [New Pole BP-3P, manufactured by Sanyo Kasei Kogyo Co., Ltd.] 324.4 parts (21.2 mol%), decantriol [manufactured by Sigma Aldrich] 39. 1 part (5.4 mol%), 251.4 parts (39.8 mol%) of terephthalic acid and 2 parts of titanium diisopropoxybistriethanol aminate as a condensation catalyst were added, and the temperature was 220 ° C. under a nitrogen stream. The reaction was carried out for 4 hours while distilling off the generated water. Further, the reaction was carried out at 220 ° C. for 10 hours under a reduced pressure of 0.5 to 2.5 kPa. When the acid value became less than 1, 163.3 parts (12.6 mol%) of behenic acid was added, and the mixture was reacted at 180 ° C. under a nitrogen stream for 2 hours while distilling off the generated water. Further, the reaction was carried out at 180 ° C. for 1 hour under a reduced pressure of 0.5 to 2.5 kPa. When the acid value became less than 1, it was taken out from the reaction vessel to obtain an ester compound (E-20).
The acid value of the ester compound (E-20) was 0.4 mgKOH / g, the hydroxyl value was 21 mgKOH / g, the glass transition point (Tg) was −16 ° C., Mn was 2,200, and Mw was 4,800.
The ester compound (E-20) obtained above was used as an additive for toner (J-20).

<Example 21><Synthesis of toner additive (J-21)>
In a reaction vessel equipped with a cooling tube, a thermometer, a stirrer and a nitrogen introduction tube, 2 mol of bisphenol A propylene oxide [New Pole BP-2P, manufactured by Sanyo Kasei Kogyo Co., Ltd.] 338.8 parts (26. 4 mol%), bisphenol A propylene oxide 3 mol additive [New Pole BP-3P, manufactured by Sanyo Kasei Kogyo Co., Ltd.] 364.6 parts (24.6 mol%), 1,3-bis (p-carboxyphenoxy) ) Propane [manufactured by Sigma Aldrich] 17.5 parts (1.5 mol%), terephthalic acid 247.9 parts (40.5 mol%) and 2 parts of titanium diisopropoxybistriethanol aminate as a condensation catalyst. The reaction was carried out at 220 ° C. under a nitrogen stream for 4 hours while distilling off the generated water. Further, the reaction was carried out at 220 ° C. for 10 hours under a reduced pressure of 0.5 to 2.5 kPa. When the acid value became less than 1, 89.2 parts (7.1 mol%) of behenic acid was added, and the reaction was carried out at 180 ° C. under a nitrogen stream for 2 hours while distilling off the generated water. Further, the reaction was carried out at 180 ° C. for 1 hour under a reduced pressure of 0.5 to 2.5 kPa. When the acid value became less than 1, it was taken out from the reaction vessel to obtain an ester compound (E-21).
The acid value of the ester compound (E-21) was 0.1 mgKOH / g, the hydroxyl value was 20 mgKOH / g, the glass transition point (Tg) was −26 ° C., Mn was 3,000, and Mw was 8,700.
The ester compound (E-21) obtained above was used as an additive for toner (J-21).

<Comparative Example 1><Synthesis of Toner Additive for Comparison (J'-1) (Conventional Wax Dispersant)>
454 parts of xylene and 150 parts of low molecular weight polyethylene [Sunwax LEL-400, softening point: 128 ° C.] manufactured by Sanyo Kasei Kogyo Co., Ltd. were put into a pressure resistant reaction vessel set with a stirring rod and a thermometer, and after nitrogen substitution. The temperature was raised to 170 ° C. to sufficiently dissolve the mixture, and a mixed solution of 716 parts of styrene, 46 parts of butyl acrylate, 88 parts of acrylonitrile, 34 parts of dit-butylperoxyhexahydroterephthalate and 119 parts of xylene was added over 3 hours. After dropping, the mixture was polymerized at 170 ° C. and further held at 170 ° C. for 30 minutes. Then, the solvent was removed to obtain a wax dispersant (E'-1). The Mw of the wax dispersant (E'-1) was 5200.
The wax dispersant (E'-1) obtained above was used as a toner additive (J'-1) for comparison.

Acid values, hydroxyl values, and glass transition points of the toner additives (J-1) to (J-8) and (J-19) to (J-21) produced in Examples 1 to 8 and 19 to 21. Mn and Mw were measured by the following methods.
The results are summarized in Table 1.

<Acid value and hydroxyl value>
The acid value and the hydroxyl value were measured by the method specified in JIS K0070 (1992 edition).

<Glass transition point>
The glass transition point was measured by the method specified in ASTM D3418-82 (DSC method) using DSC20 and SSC / 580 manufactured by Seiko Instruments.
Specifically, 5 mg of the sample is heated at 20 ° C. per minute to a temperature about 30 ° C. higher than the end of the glass transition, cooled to a temperature about 50 ° C. lower than the glass transition temperature at 60 ° C. It was heated at 20 ° C. per minute to a temperature as high as about 30 ° C.
From the data obtained by the above measurement, draw a graph with the vertical axis as the amount of heat absorption and heat absorption and the horizontal axis as the temperature. The temperature at the intersection with the tangent line drawn at the point where the slope of the curve is maximized was defined as the glass transition temperature.

<Mn and Mw>
Mn and Mw were measured using GPC under the following conditions.
Equipment: HLC-8120 manufactured by Tosoh Corporation
Column: 2 TSK GEL GMH6 [manufactured by Tosoh Corporation]
Measurement temperature: 40 ° C
Sample solution: 0.25 wt% THF (tetrahydrofuran) solution Injection amount: 100 μl
Detection device: Refractive index detector Reference material: Tosoh standard polystyrene (TSKstandard POLYSTYRENE) 12 points (molecular weight 500 1050 2800 5970 9100 18100 37900 96400 1900000 355000 1090000 2890000)

Further, the toner additives (J-1) to (J-8), (J-19) to (J-21) produced in Examples 1 to 8 and 19 to 21 and the toner additives for comparison (J-1) For J'-1), the difficulty of extraction from the toner binder resin to the carbon dioxide phase was evaluated by the following method.
The toner obtained by the above-mentioned method for producing a toner using carbon dioxide contains a sufficient amount of the toner additive so that the toner additive of the present invention is difficult to be extracted from the toner binder resin into the carbon dioxide phase. , The effect of the toner additive of the present invention is exhibited more efficiently.
<Model evaluation of difficulty in extraction into the carbon dioxide phase>
By adding a certain amount of hexane to the mixture of the toner binder resin (R) solution (L) and the wax dispersion liquid (W) as in the following evaluation examples 1 to 11 and comparative evaluation examples 1 to 2. After separating into a liquid upper layer and a viscous lower layer, the upper layer was collected. The weight and solid content concentration of the collected upper layer were measured, and the ratio of the solid content extracted to the upper layer (the solid content contained in the upper layer to the total weight of the solid content contained in the solution (L) and the wax dispersion (W)). Weight ratio) was calculated.
Hexane, which has a relatively low polarity, is considered as a model solvent for carbon dioxide, and the ratio of the amount of solid content extracted into the medium containing hexane as the main component is determined by the above calculation method. Since the low molecular weight component of the toner binder is constant among the extracted solids, it is possible to estimate the difficulty of extraction into carbon dioxide from the ratio of the solids.
That is, the smaller the amount of solid content extracted in the upper layer, the more difficult it is for the toner additive to separate from the toner binder resin even if carbon dioxide having a low polarity is used.

<Evaluation Example 1><Evaluation of Toner Additive (J-1)>
26.3 parts of the amorphous polyester toner binder solution (L-1) obtained in the following Production Example 2 and 13.6 parts of the wax dispersion liquid (W-1) obtained in the following Production Example 9 are put into the beaker. Then, using a disper (manufactured by Primix), the mixture was dispersed at a rotation speed of 3000 rpm for 2 minutes. 60.0 parts of hexane was added to the dispersion, and the mixture was further dispersed at a rotation speed of 3000 rpm for 2 minutes using Disper (manufactured by Primix) and then allowed to stand. After separating into a liquid upper layer and a viscous lower layer, only the upper layer was decanted, and the weight and solid content concentration of the upper layer were measured. The ratio of the solid content extracted to the upper layer was 8.0%.

<Evaluation Examples 2 to 11 and Comparative Evaluation Example 1><Toner Additives (J-2) to (J-8), (J-19) to (J-21) and Comparative Toner Additives (J) '-1) Evaluation>
In Example 1, the wax dispersion liquid (W) shown in Table 2 produced in Production Examples 10 to 19 below was used in place of the wax dispersion liquid (W-1), except that the wax dispersion liquid (W) was used in the same manner as in Example 1. carried out.
The results of each evaluation example are shown in Table 2.

<Comparative evaluation example 2><Comparative evaluation without using toner additives>
34.6 parts of the amorphous polyester toner binder solution (L-1) obtained in Production Example 2 and 5.4 parts of acetone were put into a beaker, and a dispersion (manufactured by Primix Corporation) was used for 2 minutes at a rotation speed of 3000 rpm. Distributed. 60.0 parts of hexane was added to the dispersion, and the mixture was further dispersed at a rotation speed of 3000 rpm for 2 minutes using Disper (manufactured by Primix) and then allowed to stand. After separating into a liquid upper layer and a viscous lower layer, only the upper layer was decanted, and the weight and solid content concentration of the upper layer were measured. The ratio of the solid content extracted to the upper layer was 4.0%.

<Examples 9-18, 22-24>
The toners (T-1) to (T-13) of the present invention and the toners (T'-1) to (T'-2) for comparison were prepared by the following methods.

<Manufacturing Examples 1 to 5>
Toner binder resins (R-1) to (R-2), crystalline polyesters (P-1) and their solutions (L-1) to (L-2) used for producing the toner of the present invention by the following methods. It was created.

<Manufacturing Example 1><Synthesis of Amorphous Polyester Toner Binder Resin (R-1)>
In a reaction vessel equipped with a cooling tube, a thermometer, a stirrer and a nitrogen introduction tube, 2 mol of bisphenol A propylene oxide adduct [New Pole BP-2P, manufactured by Sanyo Kasei Kogyo Co., Ltd.] 197.2 parts (14. 2 mol%), 3 mol adduct of bisphenol A propylene oxide [New Pole BP-3P, manufactured by Sanyo Kasei Kogyo Co., Ltd.] 515.1 parts (33.1 mol%), 15.7 parts of trimethylol propane (2. 9 mol%), 300.5 parts of terephthalic acid (45.3 mol%) and 2 parts of titanium diisopropoxybistriethanol aminate as a condensation catalyst were added, and the water produced was retained at 220 ° C. under a nitrogen stream. It was allowed to react for 4 hours while leaving. Further, the reaction was carried out at 220 ° C. for 10 hours under a reduced pressure of 0.5 to 2.5 kPa. When the acid value becomes less than 1, 34.1 parts (4.5 mol%) of anhydrous trimellitic acid is added, and the reaction is carried out at 180 ° C. under a nitrogen stream for 2 hours, and then the reaction product is removed from the reaction vessel. It was taken out to obtain an amorphous polyester toner binder resin (R-1).
The acid value of the amorphous polyester toner binder resin (R-1) is 20 mgKOH / g, the hydroxyl value is 20 mgKOH / g, the glass transition point (Tg) is 58 ° C., Mn is 4,000, Mw is 20,000, and the flow. The softening temperature T _1/2 was 110 ° C.

<Production Example 2><Synthesis of Amorphous Polyester Toner Binder Solution (L-1)>
77.7 parts of the amorphous polyester toner binder (R-1) prepared in Production Example 1 and 162.5 parts of acetone were put into a pressure resistant reaction vessel equipped with a thermometer and a stirrer, and the temperature was 60 ° C. for 2 hours. The mixture was stirred to obtain an amorphous polyester toner binder solution (L-1).

<Production Example 3><Synthesis of crystalline polyester (P-1)>
249.3 parts (35.3 mol%) of 1,6-hexanediol and 441.9 parts of 1,12-dodecanedicarboxylic acid in a reaction vessel equipped with a condenser, a thermometer, a stirrer and a nitrogen introduction tube. 32.6 mol%) and 2 parts of titanium diisopropoxybistriethanol aminate as a condensation catalyst were added, and the reaction was carried out at 210 ° C. under a nitrogen stream for 4 hours while distilling off the generated water. Further, the reaction was carried out at 210 ° C. for 10 hours under a reduced pressure of 0.5 to 2.5 kPa. When the acid value became less than 1, the reaction product was taken out from the reaction vessel to obtain a crystalline polyester (P-1).
The acid value of the crystalline polyester (P-1) was 0.4 mgKOH / g, the hydroxyl value was 32 mgKOH / g, the melting point (Tm) was 72 ° C., Mn was 4,000, and Mw was 11,000.

<Manufacturing Example 4><Synthesis of Crystalline Polyester Toner Binder Resin (R-2)>
500 parts of methyl ethyl ketone and 691.2 parts of the crystalline polyester (P-1) obtained in Production Example 3 are put into a reaction vessel equipped with a cooling tube, a thermometer, a stirrer and a nitrogen introduction tube, and dissolved at 80 ° C. This gave a crystalline polyester solution.
Next, in a reaction vessel equipped with another cooling tube, thermometer, stirrer and nitrogen introduction tube, 500 parts of methyl ethyl ketone, 130.0 parts of 1,4-cyclohexanedimethanol (14.5 mol%), and toluene diisocyanate. 183.9 parts (17.7 mol%) was added, the reaction was carried out at 80 ° C. for 5 hours, and when the isocyanate content reached 2.0%, the above crystalline polyester solution was added. The reaction was subsequently carried out at 80 ° C. for 3 hours, and when the isocyanate content became less than 0.05%, the reaction was taken out from the reaction vessel. The removed resin solution was subjected to solvent removal at 80 ° C. under a reduced pressure of 0.5 to 2.5 kPa for 3 hours to obtain a crystalline polyester toner binder resin (R-2).
The acid value of the crystalline polyester toner binder resin (R-2) is 0.4 mgKOH / g, the hydroxyl value is 12 mgKOH / g, the melting point (Tm) is 63 ° C., Mn is 13,000, Mw is 43,000, and the flow is softened. The temperature T _1/2 was 115 ° C.
The isocyanate content was measured by the method described in JIS K 6806 (the same applies hereinafter).

<Production Example 5><Synthesis of crystalline polyester toner binder solution (L-2)>
77.7 parts of the crystalline polyester toner binder (R-2) and 162.5 parts of acetone prepared in Production Example 4 were put into a pressure resistant reaction vessel equipped with a thermometer and a stirrer, and stirred at 60 ° C. for 2 hours. The mixture was allowed to obtain a crystalline polyester toner binder solution (L-2).

Acid value, hydroxyl value, glass transition point, Mn, Mw, flow softening temperature and of the toner binder resins (R-1) to (R-2) and the crystalline polyester (P-1) produced in Production Examples 1 to 5. The melting point was measured by the following method.

<Acid value, hydroxyl value, glass transition point, Mn and Mw>
The measurement was carried out in the same manner as the above-mentioned toner additive.

<Measurement method of flow softening temperature>
Using a descent type flow tester [CFT-500D, manufactured by Shimadzu Corporation], a load of 1.96 MPa is applied by a plunger while heating 1 g of the measurement sample at a temperature rise rate of 6 ° C./min, and the diameter is 1 mm. , Extrude from a nozzle with a length of 1 mm, draw a graph of "plunger drop amount (flow value)" and "temperature", and read the temperature corresponding to 1/2 of the maximum value of the plunger drop amount from the graph. , This value (the temperature when half of the measurement sample flowed out) was taken as the softening point.

<Measuring method of melting point>
A sample (5 mg) is collected, placed in an aluminum pan, and endothermic peak due to crystal melting at a heating rate of 10 ° C. per minute by DSC (differential scanning calorimetry) [DSC20, SSC / 580 manufactured by Seiko Instruments Co., Ltd.]. The temperature (° C) of was determined.

<Manufacturing Examples 6 to 7>
A dispersion liquid (S-1) of organic fine particles (H-1) used for producing the toner of the present invention was prepared by the following method.

<Production Example 6><Synthesis of macromonomer (mm-1)>
400 parts of THF and 229 parts of tolylene diisocyanate were put into a container equipped with a stirrer, and the air in the reaction vessel was replaced with nitrogen and then heated to 40 ° C. Next, 171 parts of hydroxyethyl methacrylate was added dropwise in 1 hour, 0.1 part of a bismuth catalyst [Neostan U-600, manufactured by Nitto Kasei Co., Ltd.] was added, and the reaction was carried out at 40 ° C. for 1 hour. A vinyl monomer solution with was obtained. Next, 398 parts of THF and 398 parts of the crystalline polyester (P-1) obtained in Production Example 3 were put into a container equipped with a stirrer, the air in the reaction container was replaced with nitrogen, and then heated to 70. Crystalline polyester (P-1) was uniformly dissolved at ° C. 56 parts of a vinyl monomer solution was added dropwise thereto in 1 hour, 0.1 part of a bismuth catalyst [Neostan U-600, manufactured by Nitto Kasei Co., Ltd.] was added, and a reaction was carried out at 70 ° C. for 3 hours to carry out a reaction of macromonomer (mm-1). A solution was obtained. The isocyanate content of the macromonomer (mm-1) solution was 0.0%.

<Production Example 7><Preparation of Organic Fine Particle Dispersion Liquid (S-1)>
500 parts of THF was charged in a reaction vessel equipped with a stirrer, the air in the reaction vessel was replaced with nitrogen, and then heated to the reflux temperature. Next, 160 parts of behenyl acrylate, 60 parts of methacrylic acid, 200 parts of the macromonomer (mm-1) solution obtained in Production Example 6, methacrylic-modified silicone [manufactured by Shin-Etsu Chemical Co., Ltd., X22-2426, Mw: 12]. 000] A mixture of 80 parts and 1.5 parts of azobisisobutyronitrile was placed in a reaction vessel for 2 hours, and then aged at a reflux temperature for 6 hours to obtain a dispersion of organic fine particles (H-1). S-1) was obtained. The volume average particle size of the organic fine particle dispersion (S-1) measured by a laser particle size distribution measuring device [LA-920, manufactured by HORIBA, Ltd.] was 0.15 μm.

A colorant dispersion (G-1) used for producing the toner of the present invention was prepared by the following method.
<Production Example 8><Preparation of colorant dispersion (G-1)>
A colorant dispersion (G-1) used for producing the toner of the present invention was prepared by the following method.
After mixing 800 parts of acetone, 152.5 parts of phthalocyanine pigment [Chromofine Blue, manufactured by Dainichi Seika Kogyo Co., Ltd.], and 47.5 parts of pigment dispersant [SOLSPERSE26000, manufactured by Nippon Lubrizol Co., Ltd.], a bead mill [ Dynomill Multilab, manufactured by Symmal Enterprises Co., Ltd.] was used for pulverization using zirconia beads having a particle size of 0.3 mm, and then the zirconia beads were filtered off to obtain a pigment dispersion. The volume average particle size of this dispersion measured by a laser particle size distribution measuring device [LA-920, manufactured by HORIBA, Ltd.] was 0.25 μm.

<Production Examples 9 to 19 and Comparative Production Example 1>
The wax dispersions (W-1) to (W-8), (W-19) to (W-21) used for producing the toner of the present invention and the wax dispersions for comparison (W'-) by the following methods. 1) was created.

<Manufacturing Example 9><Adjustment of Wax Dispersion Liquid (W-1)>
800 parts of acetone, ester wax [Unistar M-2222SL (behenic acid behenic acid), manufactured by NOF CORPORATION] 133.3 parts, 66.7 parts of the toner additive (J-1) obtained in Example 1. After mixing, crushing was performed using zirconia beads having a particle size of 0.3 mm using a bead mill [Dynomill Multilab, manufactured by Symmal Acetone Co., Ltd.], and then the zirconia beads were filtered off to disperse wax. Liquid (W-1) was obtained. The volume average particle size of this dispersion measured by a laser particle size distribution measuring device [LA-920, manufactured by HORIBA, Ltd.] was 0.35 μm.

<Manufacturing Example 10><Adjustment of wax dispersion liquid (W-2)>
After mixing 800 parts of acetone, 133.3 parts of ester wax [Unistar M-2222SL, manufactured by NOF CORPORATION], and 66.7 parts of the toner additive (J-2) obtained in Example 2, a bead mill. (Dynomill Multilab: manufactured by Symmal Acetone) is pulverized using zirconia beads having a particle size of 0.3 mm, and then the zirconia beads are filtered off to obtain a wax dispersion (W-2). rice field. The volume average particle size of this dispersion measured by a laser particle size distribution measuring device (LA-920: manufactured by HORIBA, Ltd.) was 0.35 μm.

<Manufacturing Example 11><Adjustment of wax dispersion liquid (W-3)>
After mixing 800 parts of acetone, 133.3 parts of ester wax [Unistar M-2222SL, manufactured by NOF CORPORATION], and 66.7 parts of the toner additive (J-3) obtained in Example 3, a bead mill. (Dynomill Multilab: manufactured by Symmal Acetone) is pulverized using zirconia beads having a particle size of 0.3 mm, and then the zirconia beads are filtered off to obtain a wax dispersion (W-3). rice field. The volume average particle size of this dispersion measured by a laser particle size distribution measuring device (LA-920: manufactured by HORIBA, Ltd.) was 0.35 μm.

<Manufacturing Example 12><Adjustment of wax dispersion liquid (W-4)>
After mixing 800 parts of acetone, 133.3 parts of ester wax [Unistar M-2222SL, manufactured by NOF CORPORATION], and 66.7 parts of the toner additive (J-4) obtained in Example 4, a bead mill. (Dynomill Multilab: manufactured by Symmal Acetone) is pulverized using zirconia beads having a particle size of 0.3 mm, and then the zirconia beads are filtered off to obtain a wax dispersion (W-4). rice field. The volume average particle size of this dispersion measured by a laser particle size distribution measuring device (LA-920: manufactured by HORIBA, Ltd.) was 0.35 μm.

<Manufacturing Example 13><Adjustment of Wax Dispersion Liquid (W-5)>
After mixing 800 parts of acetone, 133.3 parts of ester wax [Unistar M-2222SL, manufactured by NOF CORPORATION], and 66.7 parts of the toner additive (J-5) obtained in Example 5, a bead mill. (Dynomill Multilab: manufactured by Symmal Acetone) is pulverized using zirconia beads having a particle size of 0.3 mm, and then the zirconia beads are filtered off to obtain a wax dispersion (W-5). rice field. The volume average particle size of this dispersion measured by a laser particle size distribution measuring device (LA-920: manufactured by HORIBA, Ltd.) was 0.35 μm.

<Manufacturing Example 14><Adjustment of Wax Dispersion Liquid (W-6)>
After mixing 800 parts of acetone, 133.3 parts of ester wax [Unistar M-2222SL, manufactured by NOF CORPORATION], and 66.7 parts of the toner additive (J-6) obtained in Example 6, a bead mill. (Dynomill Multilab: manufactured by Symmal Acetone) is pulverized using zirconia beads having a particle size of 0.3 mm, and then the zirconia beads are filtered off to obtain a wax dispersion (W-6). rice field. The volume average particle size of this dispersion measured by a laser particle size distribution measuring device (LA-920: manufactured by HORIBA, Ltd.) was 0.35 μm.

<Manufacturing Example 15><Adjustment of wax dispersion liquid (W-7)>
After mixing 800 parts of acetone, 133.3 parts of ester wax [Unistar M-2222SL, manufactured by NOF CORPORATION], and 66.7 parts of the toner additive (J-7) obtained in Example 7, a bead mill. (Dynomill Multilab: manufactured by Symmal Acetone) is pulverized using zirconia beads having a particle size of 0.3 mm, and then the zirconia beads are filtered off to obtain a wax dispersion (W-7). rice field. The volume average particle size of this dispersion measured by a laser particle size distribution measuring device (LA-920: manufactured by HORIBA, Ltd.) was 0.35 μm.

<Manufacturing Example 16><Adjustment of wax dispersion liquid (W-8)>
After mixing 800 parts of acetone, 133.3 parts of ester wax [Unistar M-2222SL, manufactured by NOF CORPORATION], and 66.7 parts of the toner additive (J-8) obtained in Example 8, a bead mill. (Dynomill Multilab: manufactured by Symmal Acetone) is pulverized using zirconia beads having a particle size of 0.3 mm, and then the zirconia beads are filtered off to obtain a wax dispersion (W-8). rice field. The volume average particle size of this dispersion measured by a laser particle size distribution measuring device (LA-920: manufactured by HORIBA, Ltd.) was 0.35 μm.

<Manufacturing Example 17><Adjustment of Wax Dispersion Liquid (W-19)>
After mixing 800 parts of acetone, 133.3 parts of ester wax [Unistar M-2222SL, manufactured by NOF CORPORATION], and 66.7 parts of the toner additive (J-19) obtained in Example 19, a bead mill. (Dynomill Multilab: manufactured by Symmal Acetone) is pulverized using zirconia beads having a particle size of 0.3 mm, and then the zirconia beads are filtered off to obtain a wax dispersion (W-19). rice field. The volume average particle size of this dispersion measured by a laser particle size distribution measuring device (LA-920: manufactured by HORIBA, Ltd.) was 0.35 μm.

<Manufacturing Example 18><Adjustment of Wax Dispersion Liquid (W-20)>
After mixing 800 parts of acetone, 133.3 parts of ester wax [Unistar M-2222SL, manufactured by NOF CORPORATION], and 66.7 parts of the toner additive (J-20) obtained in Example 20, a bead mill. (Dynomill Multilab: manufactured by Symmal Acetone) is pulverized using zirconia beads having a particle size of 0.3 mm, and then the zirconia beads are filtered off to obtain a wax dispersion (W-20). rice field. The volume average particle size of this dispersion measured by a laser particle size distribution measuring device (LA-920: manufactured by HORIBA, Ltd.) was 0.35 μm.

<Manufacturing Example 19><Adjustment of wax dispersion liquid (W-21)>
After mixing 800 parts of acetone, 133.3 parts of ester wax [Unistar M-222SL, manufactured by NOF CORPORATION], and 66.7 parts of the toner additive (J-21) obtained in Example 21, a bead mill. (Dynomill Multilab: manufactured by Symmal Acetone) is pulverized using zirconia beads having a particle size of 0.3 mm, and then the zirconia beads are filtered off to obtain a wax dispersion (W-21). rice field. The volume average particle size of this dispersion measured by a laser particle size distribution measuring device (LA-920: manufactured by HORIBA, Ltd.) was 0.35 μm.

<Comparative Manufacturing Example 1><Preparation of Wax Dispersion Liquid (W'-1) for Comparison>
800 parts of acetone, 133.3 parts of ester wax [Unistar M-2222SL, manufactured by NOF CORPORATION], and 66.7 parts of the comparative toner additive (J'-1) obtained in Comparative Example 1 are mixed. After that, pulverize with a bead mill (Dynomill Multilab: manufactured by Symmal Acetone) using zirconia beads having a particle size of 0.3 mm, and then filter out the zirconia beads to obtain a wax dispersion (W'. -1) was obtained. The volume average particle size of this dispersion measured by a laser particle size distribution measuring device (LA-920: manufactured by HORIBA, Ltd.) was 0.35 μm.

<Example 9><Manufacturing of toner (T-1)>
Amorphous polyester toner binder solution (L-1) obtained in Production Example 2 in a beaker.
240.2 parts, 29.5 parts of the colorant dispersion liquid (G-1) obtained in Production Example 8, and 27.0 parts of the wax dispersion liquid (W-1) obtained in Production Example 9 were added. A dispersed phase (DP-1) was obtained by dispersing for 2 minutes at a rotation speed of 10000 rpm using a homomixer [manufactured by Primix Corporation].
In the experimental apparatus of FIG. 1, first, the valves V1 and V2 were closed, carbon dioxide (purity 99.99% by weight) was introduced into the particle recovery tank T4 from the cylinder B2 and the pump P4, and the temperature was adjusted to 14 MPa and 40 ° C. Further, the dispersed phase (DP-1) was charged into the resin solution tank T1, and the organic fine particle dispersion liquid (S-1) obtained in Production Example 7 was charged into the fine particle dispersion tank T2. Next, carbon dioxide was introduced into the dispersion tank T3 from the cylinder B1 and the pump P3, adjusted to 9 MPa and 40 ° C., and further, the organic fine particle dispersion liquid (S-1) was introduced from the tank T2 and the pump P2. Next, the dispersed phase (DP-1) was introduced into the dispersion tank T3 from the tank T1 and the pump P1 while stirring the inside of the dispersion tank T3 at 2000 rpm. After the introduction, the pressure inside T3 became 14 MPa.
The weight ratio of the composition charged in the dispersion tank T3 is as follows.
Distributed phase (DP-1) 296.7 parts Organic fine particle dispersion (S-1) 25.0 parts Carbon dioxide 550.0 parts The weight of carbon dioxide introduced is the temperature (40 ° C) and pressure of carbon dioxide (40 ° C). The density of carbon dioxide was calculated from 15 MPa) from the state formula described in Document 1 below, and this was calculated by multiplying this by the volume of the dispersion tank T3.
Reference 1: Journal of Physical and Chemical Reference data, vol. 25, P.I. 1509 to 1596
After introducing the dispersed phase (DP-1), the mixture was stirred for 1 minute to obtain a dispersion (Q). After opening the valve V1 and introducing carbon dioxide into T4 from P3, the dispersion (Q) was introduced into T4, and the opening degree of V2 was adjusted so that the pressure was kept constant during this period. This operation was performed for 30 seconds, and V1 was closed. By this operation, the solvent was extracted from the resin solution introduced into T4. Further, T4 was heated to 60 ° C. and held for 15 minutes. By this operation, the organic fine particle dispersion liquid (S-1) was fixed to the surface of the resin particles formed from the dispersed phase (DP-1) to generate toner intermediate particles (TM-1). Next, carbon dioxide containing the extracted solvent is discharged to the solvent trap tank T5 by holding the pressure at 14 MPa by the pressure adjustment valve V2 while introducing carbon dioxide into the particle recovery tank T4 from the pressure cylinder B2 and the pump P4. At the same time, the toner intermediate particles (TM-1) were captured by the filter F1. The operation of introducing carbon dioxide into the particle recovery tank T4 from the pressure cylinder B2 and the pump P4 is such that the introduction of carbon dioxide is performed when 5 times the weight of carbon dioxide introduced in the above dispersion tank T3 is introduced into the particle recovery tank T4. It stopped. At the time of this stop, the operation of substituting the solvent-containing carbon dioxide with the solvent-free carbon dioxide and capturing the toner intermediate particles (TM-1) in the filter F1 was completed. Further, the pressure adjusting valve V2 was opened little by little to reduce the pressure in the particle recovery tank to atmospheric pressure to obtain toner intermediate particles (TM-1) having a volume average particle size D50 of 6 μm, which was captured by the filter F1. ..
99 parts of the toner intermediate particles (TM-1) and 1 part of colloidal silica (Aerosil R972: manufactured by Nippon Aerosil) were mixed by a sample mill to obtain the toner (T-1) of the present invention.

<Examples 10 to 16, 22 to 24><Manufacturing of toners (T-2) to (T-8), (T11) to (T13)>
In Example 9, the toner intermediate particles (TM) were carried out in the same manner as in Example 9 except that the wax dispersant (W) shown in Table 3 was used instead of the wax dispersion liquid (W-1). -2)-(TM-8), (TM-11)-(TM-13) and the toners (T-2)-(T-8), (T11)-(T13) of the present invention were obtained.

<Example 17><Manufacturing of toner (T-9)>
In Example 9, the same procedure as in Example 9 was carried out except that the crystalline polyester toner binder solution (L-2) was used instead of the amorphous polyester toner binder solution (L-1), and the toner was intermediate. Body particles (TM-9) and toner (T-9) were obtained.

<Example 18><Manufacturing of toner (T-10)>
For 86.4 parts of the amorphous polyester toner binder (R-1) obtained in Production Example 1, 5.0 parts of a phthalocyanine pigment [Chromofine Blue, manufactured by Dainichi Seika Kogyo Co., Ltd.], ester wax [ UNISTER M-2222SL, manufactured by NOF CORPORATION] 4.0 parts and 2.0 parts of the toner additive (J-1) obtained in Example 1 were added to make a toner by the following method.
First, a mixture of the above compounds was premixed using a Henschel mixer [FM10B manufactured by Mitsui Miike Machinery Co., Ltd.] and then kneaded with a twin-screw kneader [PCM-30 manufactured by Ikekai Co., Ltd.]. Then, after finely pulverizing using a supersonic jet crusher Lab Jet [manufactured by Nippon Pneumatic Industries, Ltd.], the particles are classified by an air flow classifier [MDS-I manufactured by Nippon Pneumatic Industries, Ltd.], and the volume average particle size is increased. Toner intermediate particles (TM-10) having a D50 of 8 μm were obtained.
Then, 100 parts of toner particles and 1 part of colloidal silica (Aerosil R972: manufactured by Nippon Aerosil) were mixed with a sample mill to obtain the toner (T-10) of the present invention.

<Comparative Example 2><Manufacturing of toner (T'-1)>
In Example 9, the toner intermediate particles (TM'-) were carried out in the same manner as in Example 9 except that the wax dispersion liquid (W'-1) was used instead of the wax dispersion liquid (W-1). 1) and toner (T'-1) were obtained.

<Comparative Example 3><Manufacturing of toner (T'-2)>
In Comparative Example 2, the same procedure as in Comparative Example 2 was carried out except that the crystalline polyester toner binder solution (L-2) was used instead of the amorphous polyester toner binder solution (L-1), and the toner was intermediate. Body particles (TM'-2) and toner (T'-2) were obtained.

[Evaluation methods]
The volume average particle diameters of the toner intermediate particles obtained in Examples 9 to 18, 22 to 24 and Comparative Examples 2 to 3 were measured by the following methods.
Further, the toners (T-1) to (T-13) obtained in Examples 9 to 18 and 22 to 24 and the comparative toners obtained in Comparative Examples 2 to 3 have low temperature fixability and hot offset resistance. The fluidity, heat storage stability, charge stability, image strength and document offset property were evaluated by the following methods.
The results are shown in Table 3.

<Measuring method of volume average particle size>
The toner intermediate particles were dispersed in an aqueous solution of sodium dodecylbenzene sulfonate (concentration 0.1% by weight), and the volume average particle size was measured with a Coulter counter [Multisizer III (manufactured by Beckman Coulter)].

<Low temperature fixability>
Place the toner evenly on the paper surface at 0.85 mg / cm ² . At this time, as a method of placing the powder on the paper surface, a printer with the heat fixing machine removed is used. Other methods may be used as long as the powder can be uniformly placed at the above weight density.
A fixing test was carried out in which this paper was passed through a pressure roller under the conditions of a fixing speed (heating roller peripheral speed) of 213 mm / sec and a fixing pressure (pressurized roller pressure) of 10 kg / cm ² . The presence or absence of cold offset in the fixed image was visually evaluated, and the minimum temperature (MFT) (° C.) that could be fixed without cold offset was measured.
The lower the MFT, the better the low temperature fixability.

<Hot offset resistance (hot offset generation temperature)>
The fixing test was carried out at various fixing temperatures as well as the low temperature fixing property. The presence or absence of hot offset on the fixed image was visually evaluated, and the maximum temperature (° C) at which fixing was possible without hot offset was measured.
The higher the maximum temperature that can be fixed without hot offset, the better the hot offset resistance.

<Liquidity>
The bulk density (g / 100 ml) of the toner was measured with a powder tester manufactured by Hosokawa Micron, and the fluidity was judged according to the following criteria.

[criterion]
⊚: 33 or more ○: 28 or more and less than 33 Δ: 25 or more and less than 28 ×: less than 25

<Heat-resistant storage>
The toner was allowed to stand in an atmosphere of 50 ° C. for 24 hours, the degree of blocking was visually judged, and the heat-resistant storage stability was evaluated according to the following judgment criteria.

[criterion]
⊚: No blocking has occurred.
◯: Blocking has occurred slightly.
Δ: Blocking has occurred in a part.
X: Blocking has occurred in the whole.

<Charging stability>
(1) 0.5 g of toner and 20 g of ferrite carrier (F-150, manufactured by Powdertech) are placed in a 50 ml glass bottle, and the humidity is adjusted at 23 ° C. and 50% relative humidity for 8 hours or more. (2) The mixture of the toner and the ferrite carrier whose humidity was adjusted in (1) was rubbed and stirred with a turbar shaker mixer under the condition of 50 rpm, and the charge amount at the time of friction stirring for 10 minutes and the charge at the time of friction stirring for 60 minutes. The amount was measured.
A blow-off charge measuring device [manufactured by Toshiba Chemical Co., Ltd.] was used for the measurement.
"Charge amount at the time of friction stir for 60 minutes / charge amount at the time of friction stirring for 10 minutes" was calculated and used as an index of charge stability.

[criterion]
⊚: 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

<Image strength>
In the evaluation of low temperature fixability, the image obtained by fixing at the lowest temperature that can be fixed is subjected to a scratch test by applying a load of 10 g from directly above the pencil fixed at an angle of 45 degrees according to JIS K5600. The hardness of the hardest pencil that did not stick was evaluated. The higher the hardness of the hardest pencil that does not scratch, the better the image strength.

[criterion]
◎: H or higher ○: HB to F
Δ: B to HB
×: 2B or less

<Document offset property>
In the evaluation of hot offset resistance, two sheets of A4 paper on which the image obtained by fixing at the maximum temperature that can be fixed was fixed were overlapped with each other on the fixed surfaces, and a load of 420 g (0.68 g / cm ² ) was applied. Sprinkle and let stand at 60 ° C for 60 minutes.
The document offset property was evaluated according to the following criteria for the state when the overlapped papers were pulled apart.

[criterion]
◎: No resistance ○: There is some resistance when pulling apart △: There is a crisp sound, but the image does not peel off from the paper surface ×: The image peels off from the paper surface

As is clear from the evaluation results in Table 3, the toners (T-1) to (T-10) using the toner additive of the present invention used the conventional wax dispersant in all the evaluation items. Results equal to or better than those of the comparative toners (T'-1) to (T'-2) were obtained.
It is considered that this is because the additive for toner of the present invention improved the dispersibility of the wax in the toner.

Since the toner produced by using the toner additive of the present invention has excellent wax dispersibility, the obtained toner has excellent charge stability and heat storage stability. Therefore, the present invention is useful as an additive for toner, and particularly useful as a wax dispersant for toner.

T1: Solution tank T2: Solution tank T3: Dispersion tank (maximum operating pressure 20 MPa, maximum operating temperature 200 ° C, with stirrer)
T4: Particle recovery tank (maximum operating pressure 20 MPa, maximum operating temperature 100 ° C)
T5: Solvent trap F1: Ceramic filter (mesh: 0.5 μm)
B1, B2: Carbon dioxide cylinder P1, P2: Solution pump P3, P4: Carbon dioxide pump V1: Valve V2: Pressure adjustment valve

Claims (5)

An additive for toner containing an ester (E), wherein (E) has a polyester polyol (C) which is a condensed polymer of a polyol (A) and a polycarboxylic acid (B), and a chain alkyl group. It is an ester with a monocarboxylic acid (D) having 18 to 24 carbon atoms, the acid value of the ester (E) is less than 1 mgKOH / g, and the hydroxyl value of the ester (E) is 10 to 60 mgKOH / g. , Additive for toner having a glass transition point of the ester (E) of −35 to 5 ° C. The first aspect of claim 1, wherein the monocarboxylic acid (D) is at least one monocarboxylic acid selected from the group consisting of stearic acid, nonadesyl acid, aragidic acid, henicosyl acid, bechenic acid, tricosylic acid and lignoseric acid. Additive for toner. Claim 1 in which the polyol (A) is one or more compounds selected from the group consisting of an alkylene oxide adduct of a chain aliphatic polyol having 2 to 20 carbon atoms and an aromatic polyol having 6 to 20 carbon atoms. Or the additive for toner according to 2. The toner additive according to any one of claims 1 to 3, wherein the polycarboxylic acid (B) is an aromatic polycarboxylic acid having 8 to 20 carbon atoms. The wax (w) of at least one selected from the group consisting of an ester wax, a polyolefin wax, an aliphatic alcohol having 30 to 50 carbon atoms and a fatty acid having 30 to 50 carbon atoms, according to any one of claims 1 to 4. Toner containing an additive for toner, a toner binder resin (R), and a colorant (g).

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