JP2022176092A - Polyester for toner and resin particles, and production method of polyester for toner - Google Patents

Abstract

To provide a polyester for toner and resin particles which have excellent hot off-set resistance, particle size distribution and charging property.SOLUTION: Provided are: a polyester for toner, which is an addition reaction product of a polyester having a hydroxyl group and an acid anhydride (Z) having a polymerizable unsaturated group, where an amount of the polymerizable unsaturated group is 2×10-6 to 4×10-3 mol/g; and resin particles including a crosslinking reaction product of the polyester for toner.SELECTED DRAWING: None

Description

The present invention relates to a polyester for toner, resin particles, and a method for producing the polyester for toner.

2. Description of the Related Art In recent years, with the development of electrophotographic systems, the demand for electrophotographic apparatuses such as copiers and laser printers has increased rapidly, and demands for their performance have also become more sophisticated.
In electrophotography, conventionally, a latent image based on color image information is formed on a latent image carrier such as an electrophotographic photosensitive member, the latent image is developed with a toner of a corresponding color, and the toner image is transferred onto a transfer material. 2. Description of the Related Art There is known a method and an apparatus for obtaining a multicolor image by heating and fixing a toner image on a transfer material after repeating an image forming process such as transferring the image onto the transfer material.
In order to pass through these processes without problems, the toner must first retain a stable amount of charge (charging property), and it must be able to fix with the toner even if the temperature of the hot roll is low (low-temperature fixability). It is required that the toner does not fuse to the heat roll even at a high fixing temperature (hot offset resistance).
A polyester-based toner binder is used to develop low-temperature fixability, and a toner binder capable of improving low-temperature fixability by incorporating crystalline polyester therein has been proposed (Patent Document 1). However, such a toner tends to cause a problem (hot offset) that the toner is fused to the heat roll.
In addition, for hot offset resistance, (1) polyester partially crosslinked with a polyfunctional monomer is used as a toner binder (Patent Document 2); and a modified polyester prepolymer having a reactive functional group at the end (Patent Document 3), (3) introducing an unsaturated group into a polyester resin with an unsaturated carboxylic acid and dispersing it in an aqueous solvent. Among them, a toner using a modified resin obtained by a cross-linking reaction between carbon-carbon double bonds has been proposed (Patent Document 4).
However, in (1), these toners have poor solubility in the oil phase and poor emulsifiability, resulting in poor particle size distribution. In (3), some of the double bonds react with the reaction temperature during the synthesis of the polyester, making it impossible to achieve both hot offset resistance and particle size distribution.

JP-A-2002-287426 JP-A-57-109825 Japanese Patent Application Laid-Open No. 2008-233360 JP 2018-87320 A

An object of the present invention is to provide a polyester for toner and resin particles which are excellent in hot offset resistance, particle size distribution and chargeability.

The present inventor has arrived at the present invention as a result of intensive studies. That is, the present invention is an addition reaction product of a polyester having a hydroxyl group and an acid anhydride (Z) having a polymerizable unsaturated group, and the amount of the polymerizable unsaturated group is 2×10 ⁻⁶ to 4×10 ⁻³ mol/ The polyester for toner, which is g, is a resin particle containing a cross-linking reaction product of the polyester for toner.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a polyester and resin particles for toner which are excellent in hot offset resistance, particle size distribution and chargeability.

The polyester for toner of the present invention is an addition reaction product of a polyester having a hydroxyl group and an acid anhydride (Z) having a polymerizable unsaturated group. By conducting an addition reaction between a polyester having a hydroxyl group and an acid anhydride (Z) having a polymerizable unsaturated group, the reaction is carried out under milder conditions than in the case of condensation reaction of a carboxylic acid having a polymerizable unsaturated group. It is possible to easily introduce a highly reactive polymerizable unsaturated group at the end of the polyester while suppressing the reaction of the polymerizable unsaturated group. It is possible to obtain a toner polyester having excellent offset properties and charging properties. It should be noted that the toner polyester is preferably a polyester that does not contain a urethane bond and a urea bond from the standpoint of chargeability.

The polyester having a hydroxyl group in the present invention is not particularly limited as long as it is a polyester having a hydroxyl group, and examples thereof include condensation-type polyester polyols and polylactone polyols. Polyesters having a hydroxyl group may be used alone or in combination of two or more.

Condensation-type polyester polyols are not particularly limited, but examples thereof include polycondensates of polyols and polycarboxylic acids.

Examples of polyols include diols (g) and trivalent or higher polyols (h).

Examples of the diol (g) include alkylene glycols having 2 to 36 carbon atoms, alkylene ether glycols having 4 to 36 carbon atoms, alicyclic diols having 4 to 36 carbon atoms, and aromatic diols.

Specific examples of alkylene glycols having 2 to 36 carbon atoms include ethylene glycol, 1,2-propanediol (propylene glycol), 1,3-propanediol, 1,4-butanediol, 3-methyl-1, 5-pentanediol, 1,6-hexanediol, octanediol, decanediol, dodecanediol, tetradecanediol, neopentyl glycol and 2,2-diethyl-1,3-propanediol.

Specific examples of alkylene ether glycols having 4 to 36 carbon atoms include diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol and polytetramethylene ether glycol.

Specific examples of alicyclic diols having 4 to 36 carbon atoms include 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,1-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 5- norbornene-2,3-dimethanol, hydrogenated bisphenol A, spiroglycol, isosorbide, and alkylene oxide of the above alicyclic diols (hereinafter, "alkylene oxide" may be abbreviated as AO) adducts, and the like. .

Examples of the alkylene oxide adduct of the alicyclic diol include ethylene oxide (hereinafter, "ethylene oxide" may be abbreviated as EO) adduct of the alicyclic diol, propylene oxide (hereinafter, "propylene oxide"), may be abbreviated as PO.) adducts and butylene oxide (hereinafter, "butylene oxide" may be abbreviated as BO) adducts. The average number of added moles of the alkylene oxide is preferably 1-15, more preferably 2-5.

Examples of aromatic diols include 1,3-benzenedimethanol, 1,4-benzenedimethanol, bisphenol A, bisphenol F, bisphenol B, bisphenol AD, bisphenol S, trichlorobisphenol A, tetrachlorobisphenol A, dibromobisphenol F, 2-Methylbisphenol A, 2,6-dimethylbisphenol A and 2,2'-diethylbisphenol F, and alkylene oxide adducts of the above aromatic diols.

Examples of the alkylene oxide adducts of the above aromatic diols include EO adducts, PO adducts and BO adducts of the above aromatic diols. The average number of added moles of the alkylene oxide is preferably 1-15, more preferably 2-5.

As the diol (g), diols (g1) having other functional groups may be used in addition to the above diols having no functional groups other than hydroxyl groups.
(g1) includes a diol having a carboxyl group, a diol having a sulfonic acid group or a sulfamic acid group, and salts thereof.
Diols having a carboxyl group include dialkylolalkanoic acids. Examples of dialkylolalkanoic acids include those having 6 to 24 carbon atoms, specifically 2,2-dimethylolpropionic acid (DMPA), 2,2-dimethylolbutanoic acid, 2,2-di Examples include methylolheptanoic acid and 2,2-dimethyloloctanoic acid.
Diols having a sulfonic acid group or a sulfamic acid group include 3-(2,3-dihydroxypropoxy)-1-propanesulfonic acid, sulfoisophthalic acid di(ethylene glycol) ester, sulfamic acid diol and bis(2-hydroxyethyl ) phosphate and the like.

Preferred diols (g) are alkylene glycols having 2 to 36 carbon atoms, aromatic diols and diols (g1) having other functional groups, more preferably alkylene glycols having 2 to 12 carbon atoms and carboxyl groups. AO adduct of bisphenol A, more preferably alkylene glycol having 2 to 12 carbon atoms and AO adduct of bisphenol A, and a combination thereof.

Examples of the trihydric or higher polyol (h) include trihydric or higher polyhydric aliphatic alcohols having 3 to 36 carbon atoms, AO adducts of polyhydric aliphatic alcohols (addition mole number 2 to 120), trisphenol (trisphenol PA, etc.) AO adduct (addition mole number 2-30), novolac resin (phenol novolac, cresol novolac, etc.) AO adduct (addition mole number 2-30), acrylic polyol [hydroxyethyl (meth) acrylate and others etc.] and the like.
Examples of trihydric or higher polyhydric aliphatic alcohols having 3 to 36 carbon atoms include alkane polyols and their intramolecular or intermolecular dehydrates, sugars (sucrose etc.) and their methyl glucosides, and the like.
Specific examples of alkane polyols and their intramolecular or intermolecular dehydrates include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, sorbitan and polyglycerin.

Preferred as the trihydric or higher polyol (h) are trihydric or higher polyhydric aliphatic alcohols having 3 to 36 carbon atoms and AO adducts of novolac resins, and more preferred are trihydric polyols having 3 to 36 carbon atoms. It is the above polyhydric aliphatic alcohol.

Examples of polycarboxylic acids include dicarboxylic acids (i), tricarboxylic or higher polycarboxylic acids (j), and the like.

Examples of the dicarboxylic acid (i) include alkanedicarboxylic acids having 4 to 36 carbon atoms, alicyclic dicarboxylic acids having 6 to 40 carbon atoms and aromatic dicarboxylic acids having 8 to 36 carbon atoms.
Examples of alkanedicarboxylic acids having 4 to 36 carbon atoms include succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanedicarboxylic acid, octadecanedicarboxylic acid and decylsuccinic acid.
Examples of alicyclic dicarboxylic acids having 6 to 40 carbon atoms include dimer acid (dimerized linoleic acid) and the like.
Examples of aromatic dicarboxylic acids having 8 to 36 carbon atoms include phthalic acid, isophthalic acid, terephthalic acid and naphthalenedicarboxylic acid.
Preferred among these are alkanedicarboxylic acids having 4 to 36 carbon atoms, aromatic dicarboxylic acids having 8 to 36 carbon atoms, and combinations thereof.

Trivalent or higher polycarboxylic acids (j) include aromatic polycarboxylic acids having 9 to 20 carbon atoms (trimellitic acid, pyromellitic acid, etc.), anhydrides of these carboxylic acids, lower alkyls (having 1 to 4) Esters (methyl ester, ethyl ester, isopropyl ester, etc.) and the like.

The reaction ratio of polyol and polycarboxylic acid is preferably 2/1 to 1.01/1, more preferably 1.5, as the molar ratio [OH]/[COOH] of hydroxyl group [OH] and carboxyl group [COOH]. /1 to 1.01/1, particularly preferably 1.2/1 to 1.01/1.

Examples of polylactone polyols include, but are not particularly limited to, polyadducts of lactones with diol (g).

Lactones include lactones having 4 to 12 carbon atoms (eg, γ-butyrolactone, γ-valerolactone and ε-caprolactone). Specific examples of polylactone polyols include polycaprolactone diol, polyvalerolactone diol and polycaprolactone triol.

A polyester having a hydroxyl group can be produced by a known production method.
For example, it can be carried out by reacting a polyol and a polycarboxylic acid in an inert gas (nitrogen gas, etc.) atmosphere. The reaction temperature is preferably 150-280° C., and the reaction time is preferably 30 minutes or longer. It is also effective to reduce the pressure in order to improve the reaction rate in the final stage of the reaction.
At this time, an esterification catalyst can be used as needed.
Esterification catalysts include tin-containing catalysts, antimony trioxide, titanium-containing catalysts, zirconium-containing catalysts and zinc acetate.
Specific examples of tin-containing catalysts include dibutyltin oxide and the like.
Titanium-containing catalysts include titanium alkoxide, potassium oxalate titanate, titanium terephthalate, catalysts described in JP-A-2006-243715 (titanium dihydroxybis(triethanolamine), titanium diisopropoxybistriethanolamine, titanium monohydroxy tris (triethanolamine), and their intramolecular polycondensates, etc.) and the catalysts described in JP-A-2007-11307 (titanium tributoxy terephthalate, titanium triisopropoxy terephthalate, and titanium diisopropoxy diterephthalate, etc.).
Zirconium-containing catalysts include zirconyl acetate.

Among the esterification catalysts, titanium-containing catalysts are preferred from the viewpoint of charging properties, and the catalysts described in JP-A-2006-243715 and JP-A-2007-11307 are more preferred.

Acid anhydride (Z) having a polymerizable unsaturated group in the present invention is not particularly limited as long as it is an anhydride of an acid having a polymerizable unsaturated group, one may be used alone, two or more may be used together.
The polymerizable unsaturated group contained in the acid anhydride (Z) is not particularly limited as long as it is an unsaturated group exhibiting polymerizability in a general radical polymerization method. , isopropenyl group, 1-propenyl group, dodecenyl group), acryloyl group and methacryloyl group. An acryloyl group and a methacryloyl group are preferred because they exhibit good polymerizability in a radical polymerization method.

Specific examples of the acid anhydride (Z) having a polymerizable unsaturated group include acrylic anhydride, methacrylic anhydride, crotonic anhydride, tiglic anhydride, pentadecenylsuccinic anhydride, hexade senylsuccinic anhydride, octadecenylsuccinic anhydride, dodecenylsuccinic anhydride, citraconic anhydride, 1,2,3,6-tetrahydrophthalic anhydride and the like.

Among these, from the viewpoint of hot offset property, the acid anhydride (Z) having a polymerizable unsaturated group is selected from the group consisting of acrylic anhydride, methacrylic anhydride, crotonic anhydride, and tiglic anhydride. It is preferably one or more compounds that are

The amount of polymerizable unsaturated groups in the polyester for toner of the present invention is 2×10 ⁻⁶ to 4×10 ⁻³ mol/g. By using the polyester for toner within the above range, a toner excellent in hot offset resistance and chargeability can be obtained.
The amount of polymerizable unsaturated groups is preferably 5×10 ⁻⁶ to 4×10 ⁻³ mol/g, more preferably 2×10 ⁻⁵ to 2×10 ⁻³ mol/g.
The amount of polymerizable unsaturated groups can be obtained by measuring the iodine value and using the following formula.
<Method for measuring iodine value>
Accurately weigh 1 g of sample in an Erlenmeyer flask, add 10 mL of chloroform to dissolve, add 25 mL of Wiiss solution (0.10 mol/L iodine chloride solution), place in a dark place at 20-30°C for 1 hour, and shake occasionally. . 20 mL of 10% by weight potassium iodide solution and 100 mL of water are added and shaken. Next, titrate with 0.1 mol/L sodium thiosulfate standard solution, add about 1 mL of starch indicator when the solution turns slightly yellow, and shake the Erlenmeyer flask well while 0.1 mol/L sodium thiosulfate standard solution. The end point is when the blue color of the starch disappears with iodine. Perform the above operations on the sample and perform a blank test.
The iodine value (IV) is obtained from the following formula.
IV = ((B-A) x f x 1.269)/S
A: mL number of 0.1 mol/L sodium thiosulfate standard solution required for the main test, B: mL number of 0.1 mol/L sodium thiosulfate standard solution required for blank test, f: 0.1 mol/L thio Potency of sodium sulfate standard solution, S: sample volume (g)
<Polymerizable unsaturated group amount>
The amount of polymerizable unsaturated groups can be obtained from the following formula.
Polymerizable unsaturated group amount = IV/25400

The glass transition temperature (Tg) of the polyester for toner is preferably -70 to 80°C, more preferably -70 to 50°C, still more preferably -65 to 45°C.
The Tg in the present invention can be measured by the method (DSC) specified in ASTM D3418-82 using "DSC20, SSC/580" [manufactured by Seiko Electronics Industry Co., Ltd.].

The polyester for toner preferably has a number average molecular weight (Mn) of 1,000 to 500,000, more preferably 1,500 to 50,000.

The weight average molecular weight (Mw) of the toner polyester is preferably 2,000 to 1,000,000, more preferably 3,000 to 120,000.

Mn and Mw in the present invention can be measured using gel permeation chromatography (GPC) under the following conditions.
Apparatus: "HLC-8120" [manufactured by Tosoh Corporation]
Column: 2 "TSK GEL GMH6" [manufactured by Tosoh Corporation] Measurement temperature: 40 ° C.
Sample solution: 0.25% by weight tetrahydrofuran solution (undissolved matter was filtered through a glass filter)
Solution injection volume: 100 μl
Detection device: refractive index detector Reference material: 12 standard polystyrene (TSK standard POLYSTYRENE) (molecular weight: 500, 1,050, 2,800, 5,970, 9,100, 18,100, 37,900, 96,400 , 190,000, 355,000, 1,090,000, 2,890,000) [manufactured by Tosoh Corporation]

The total chlorine content of the toner polyester is preferably 1000 ppm or less from the viewpoint of hot offset properties. The total chlorine content can be measured by ion chromatography, in which a sample is combusted in a mixture of argon gas and oxygen gas, and chlorine ions produced are quantified by ion chromatography.

The tetrahydrofuran (hereinafter sometimes abbreviated as THF) insoluble content of polyester for toner is preferably 1% by weight or less, more preferably 0.1% by weight, from the viewpoint of hot offset resistance and particle size distribution. It is below.
The THF-insoluble portion of the polyester for toner can easily achieve the above range by setting the temperature of the addition reaction step to 110 to 150° C., for example.
The THF-insoluble content was obtained by the following method.
50 ml of THF is added to 0.5 g of sample, and the mixture is stirred and refluxed for 3 hours. After cooling, the insoluble matter is filtered off with a glass filter, and the resin content on the glass filter is dried under reduced pressure at 80° C. for 3 hours. The weight of the resin portion dried on the glass filter is defined as the weight of the THF-insoluble portion, and the weight ratio of the THF-insoluble portion to the weight of the sample is defined as the THF-insoluble portion.

The polyester for toner of the present invention is obtained by an addition reaction between a polyester having a hydroxyl group and an acid anhydride (Z) having a polymerizable unsaturated group.
Therefore, the method for producing a polyester for toner has an addition reaction step between a polyester having a hydroxyl group and an acid anhydride (Z) having a polymerizable unsaturated group.

As shown in the production method described above, by subjecting a polyester having a hydroxyl group to an acid anhydride (Z) having a polymerizable unsaturated group to undergo an addition reaction, while suppressing the reaction of the polymerizable unsaturated group, the end of the polyester is made reactive. Since a polymerizable unsaturated group having a high molecular weight can be easily introduced, it is possible to obtain a polyester for toner that is highly soluble in an organic solvent or the like and has excellent hot offset resistance and charging characteristics.

In the above addition reaction step, a polymerization inhibitor such as tert-butylcatechol may be used, if necessary.

The weight ratio of the polyester having a hydroxyl group used in the addition reaction step is based on the total weight of the polyester having a hydroxyl group and the acid anhydride (Z) having a polymerizable unsaturated group, from the viewpoint of particle size distribution and hot offset resistance. , preferably 50 to 99% by weight, more preferably 75 to 98% by weight.

From the viewpoint of particle size distribution and hot offset resistance, the weight ratio of the acid anhydride (Z) having a polymerizable unsaturated group to be used in the addition reaction step is the polyester having a hydroxyl group and the acid anhydride having a polymerizable unsaturated group It is preferably 1 to 50% by weight, more preferably 2 to 25% by weight, based on the total weight of the substance (Z).

The hydroxyl value of the hydroxyl-containing polyester used in the addition reaction step is preferably 0.75 mgKOH/g or more, more preferably 4.4 to 75 mgKOH/g, from the viewpoint of reactivity. Incidentally, the hydroxyl value can be measured by the method specified in JIS K0070.

The acid value of the hydroxyl-containing polyester used in the addition reaction step is preferably 5 mgKOH/g or less, more preferably 1 mgKOH/g or less, from the viewpoint of reactivity. The acid value can be measured by the method specified in JIS K0070.

The temperature in the addition reaction step is preferably 100 to 180°C, more preferably 110 to 150°C, from the viewpoints of reactivity and solubility in organic solvents and the like.

The pressure in the addition reaction step is preferably 100 to 110 kPa, more preferably atmospheric pressure (101.33 kPa) from the viewpoint of reactivity and solubility in organic solvents and the like.

The time for the addition reaction step is preferably 1 to 3.5 hours, more preferably 2 to 3 hours, from the viewpoints of reactivity and solubility in organic solvents and the like.

In addition to the above addition reaction step, if necessary, a step of removing unreacted unsaturated carboxylic acid produced during the addition reaction by a method such as depressurization may be included.

The resin particles of the present invention are resin particles containing a crosslinking reaction product of a polyester for toner. The cross-linking reaction product of the polyester for toner is a modified resin obtained by a cross-linking reaction of carbon-carbon double bonds derived from the polymerizable unsaturated groups in the polyester for toner. A modified resin in which a cross-linking reaction occurs between carbon-carbon double bonds derived from the polymerizable unsaturated groups in the polyester for toner using radicals generated from the radical reaction initiator (c) to chemically bond. be.
In addition to the cross-linking reaction product of the polyester for toner, other resins can be used in combination with the resin particles. Any known resin can be used as the other resin, and specific examples thereof include polyester resins other than the polyester for toner, vinyl resins, polyurethane resins, epoxy resins, polyamide resins, polyimide resins, Silicone resins, phenolic resins, melamine resins, urea resins, aniline resins, ionomer resins, polycarbonate resins and the like can be used.
Preferable other resins are polyester resins other than the toner polyester, vinyl resins, polyurethane resins, epoxy resins, and combinations thereof. More preferably, polyester resins other than the toner polyester and vinyl resins are used in combination. .

When the other resin is a polyester resin other than the polyester for the toner of the present invention, the polyester resin may be either a crystalline polyester resin or an amorphous polyester resin, and is the same as the polyols and polycarboxylic acids exemplified for the condensation type polyester polyols. A polycondensate using the above can be used, and preferred polyols and polycarboxylic acids are the same as those of the condensation-type polyester polyols.
In the present invention, the term "crystallinity" means that the DSC curve has a maximum and an endothermic peak in the temperature rising process of the differential scanning calorimetry curve obtained by differential scanning calorimetry (also referred to as DSC measurement). . On the other hand, "amorphous" means having no endothermic peak in the DSC curve.

When the other resin is a vinyl resin, the vinyl resin is a polymer obtained by homopolymerizing or copolymerizing vinyl monomers. Examples of vinyl monomers include the following (1) to (10).
(1) Vinyl Hydrocarbon Vinyl hydrocarbons include (1-1) aliphatic vinyl hydrocarbons, (1-2) alicyclic vinyl hydrocarbons and (1-3) aromatic vinyl hydrocarbons.
(1-1) Aliphatic Vinyl Hydrocarbon Examples of the aliphatic vinyl hydrocarbon include alkenes and alkadienes.
Specific examples of alkenes include ethylene, propylene and α-olefins.
Specific examples of alkadienes include butadiene, isoprene, 1,4-pentadiene, 1,6-hexadiene and 1,7-octadiene.
(1-2) Alicyclic Vinyl Hydrocarbons The alicyclic vinyl hydrocarbons include mono- or di-cycloalkenes and alkadienes, and specific examples include (di)cyclopentadiene and terpenes. .
(1-3) Aromatic vinyl hydrocarbon Examples of the aromatic vinyl hydrocarbon include styrene and hydrocarbyl (alkyl, cycloalkyl, aralkyl and/or alkenyl)-substituted products thereof, and specifically α-methyl Styrene, 2,4-dimethylstyrene, vinylnaphthalene, and the like.

(2) Carboxyl Group-Containing Vinyl Monomers and Their Salts Carboxyl group-containing vinyl monomers and their salts include unsaturated monocarboxylic acids (salts) having 3 to 30 carbon atoms, unsaturated dicarboxylic acids (salts) and their anhydrides (salts). ) and its monoalkyl (having 1 to 24 carbon atoms) esters or salts thereof.
Specifically, (meth) acrylic acid, (anhydrous) maleic acid, maleic acid monoalkyl ester, fumaric acid, fumaric acid monoalkyl ester, crotonic acid, itaconic acid, itaconic acid monoalkyl ester, itaconic acid glycol monoether, Examples include carboxyl group-containing vinyl monomers such as citraconic acid, citraconic acid monoalkyl esters, cinnamic acid, and metal salts thereof.

In the present invention, "(salt)" means an acid or a salt thereof.
For example, an unsaturated monocarboxylic acid (salt) having 3 to 30 carbon atoms means an unsaturated monocarboxylic acid or a salt thereof.

In the present invention, "(meth)acrylic" means methacrylic acid or acrylic acid.
In the present invention, "(meth)acryloyl" means methacryloyl or acryloyl.
In the present invention, "(meth)acrylate" means methacrylate or acrylate.

(3) Sulfone Group-Containing Vinyl Monomers, Vinyl Sulfate Monoesters and Their Salts Sulfone group-containing vinyl monomers, vinyl sulfate monoesters and their salts include alkene sulfonic acids (salts) having 2 to 14 carbon atoms, carbon Alkylsulfonic acids (salts) of numbers 2 to 24, sulfo(hydroxy)alkyl-(meth)acrylates (salts) or (meth)acrylamides (salts), and alkylarylsulfosuccinic acids (salts).
Specifically, examples of alkenesulfonic acids having 2 to 14 carbon atoms include vinylsulfonic acid (salts), and examples of alkylsulfonic acids (salts) having 2 to 24 carbon atoms are α-methylstyrenesulfonic acid (salts). etc., and sulfo(hydroxy)alkyl-(meth)acrylate (salt) or (meth)acrylamide (salt) includes sulfopropyl (meth)acrylate (salt), sulfate ester (salt) or sulfonic acid group-containing vinyl monomer (salt) and the like.

(4) Phosphate group-containing vinyl monomer and salt thereof:
Examples of phosphate group-containing vinyl monomers and salts thereof include (meth)acryloyloxyalkyl (C1 to C24) phosphoric acid monoesters (salts) and (meth)acryloyloxyalkyl (C1 to C24) phosphonic acid (salts). be done.
Specific examples of (meth)acryloyloxyalkyl (C1-C24) phosphoric acid monoesters (salts) include 2-hydroxyethyl (meth)acryloyl phosphate (salts) and phenyl-2-acryloyloxyethyl phosphate (salts). mentioned.
Specific examples of the (meth)acryloyloxyalkyl (C1-24) phosphonic acid (salt) include 2-acryloyloxyethylphosphonic acid (salt) and the like.

Examples of the salts (2) to (4) above include alkali metal salts (sodium salts, potassium salts, etc.), alkaline earth metal salts (calcium salts, magnesium salts, etc.), ammonium salts, amine salts and quaternary ammonium salts. is mentioned.

(5) Hydroxyl Group-Containing Vinyl Monomers Examples of hydroxyl group-containing vinyl monomers include hydroxystyrene, N-methylol(meth)acrylamide, hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate, polyethylene glycol mono(meth)acrylate, ( meth)allyl alcohol, crotyl alcohol, isocrotyl alcohol, 1-buten-3-ol, 2-buten-1-ol, 2-butene-1,4-diol, propargyl alcohol, 2-hydroxyethyl propenyl ether and Sucrose allyl ether etc. are mentioned.

(6) Nitrogen-Containing Vinyl Monomer Nitrogen-containing vinyl monomers include (6-1) amino group-containing vinyl monomer, (6-2) amide group-containing vinyl monomer, (6-3) nitrile group-containing vinyl monomer, (6- 4) quaternary ammonium cationic group-containing vinyl monomers and (6-5) nitro group-containing vinyl monomers.
(6-1) Examples of amino group-containing vinyl monomers include aminoethyl (meth)acrylate.
(6-2) Amide group-containing vinyl monomers include (meth)acrylamide and N-methyl(meth)acrylamide.
(6-3) Nitrile group-containing vinyl monomers include (meth)acrylonitrile, cyanostyrene and cyanoacrylate.
(6-4) Examples of quaternary ammonium cationic group-containing vinyl monomers include dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylamide, diethylaminoethyl (meth)acrylamide and diallylamine. Examples include quaternized products of vinyl monomers containing a class amine group (those obtained by quaternizing using a quaternizing agent such as methyl chloride, dimethyl sulfate, benzyl chloride, and dimethyl carbonate).
(6-5) The nitro group-containing vinyl monomer includes nitrostyrene and the like.

(7) Epoxy Group-Containing Vinyl Monomer Examples of epoxy group-containing vinyl monomers include glycidyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate and p-vinylphenylphenyl oxide.

(8) Halogen element-containing vinyl monomer Examples of halogen element-containing vinyl monomers include vinyl chloride, vinyl bromide, vinylidene chloride, allyl chloride, chlorostyrene, bromostyrene, dichlorostyrene, chloromethylstyrene, tetrafluorostyrene and chloroprene. mentioned.

(9) Vinyl esters, vinyl (thio) ethers, vinyl ketones Examples of (9-1) vinyl esters include vinyl acetate, vinyl butyrate, vinyl propionate, vinyl butyrate, diallyl phthalate, diallyl adipate, isopropenyl acetate, vinyl methacrylate. , methyl 4-vinyl benzoate, cyclohexyl methacrylate, benzyl methacrylate, phenyl (meth) acrylate, vinyl methoxy acetate, vinyl benzoate, ethyl α-ethoxy acrylate, alkyl (meth) acrylate having an alkyl group having 1 to 50 carbon atoms [methyl ( meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, hexadecyl (meth)acrylate, heptadecyl (meth)acrylate, octadecyl ( meth)acrylate, eicosyl (meth)acrylate, behenyl (meth)acrylate, etc.)], dialkyl fumarate (wherein the two alkyl groups are linear, branched or alicyclic groups having 2 to 8 carbon atoms) ), dialkyl maleates (wherein the two alkyl groups are linear, branched or alicyclic groups having 2 to 8 carbon atoms), poly(meth)allyloxyalkanes [dialyloxyethane, Triaryloxyethane, tetraallyloxyethane, tetraallyloxypropane, tetraallyloxybutane, tetramethallyloxyethane, etc.], vinyl monomers having a polyalkylene glycol chain [polyethylene glycol (molecular weight 300) mono(meth)acrylate, polypropylene glycol (molecular weight 500) monoacrylate, methyl alcohol ethylene oxide 10 mol adduct (meth)acrylate, lauryl alcohol ethylene oxide 30 mol adduct (meth)acrylate, etc.], poly(meth)acrylate [polyhydric alcohol poly(meth) ) acrylate: ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, polyethylene glycol di(meth)acrylate, etc.] .
(9-2) Vinyl (thio) ether includes, for example, vinyl methyl ether.
(9-3) Vinyl ketone includes, for example, vinyl methyl ketone.

(10) Other Vinyl Monomers Other vinyl monomers include tetrafluoroethylene, fluoroacrylate, isocyanatoethyl (meth)acrylate and m-isopropenyl-α,α-dimethylbenzyl isocyanate.

In synthesizing the vinyl resin, one of the above vinyl monomers (1) to (10) may be used alone or in combination of two or more.
The vinyl resin is preferably a styrene-(meth)acrylic acid ester copolymer and a (meth)acrylic acid ester copolymer, more preferably a styrene-(meth)acrylic acid ester, from the viewpoint of particle size distribution and chargeability. It is a copolymer.

The resin particles of the present invention may contain various known additives such as colorants, release agents, charge control agents, and fluidizing agents, if necessary.

As the colorant, it is preferable to contain one or more selected from the group consisting of a black colorant, a blue colorant, a red colorant and a yellow colorant. As the colorant, all dyes, pigments, etc. used as colorants for toners can be used.
Specifically, carbon black, iron black, Sudan black SM, fast yellow G, benzidine yellow, solvent yellow (21, 77 and 114 etc.), pigment yellow (12, 14, 17 and 83 etc.), India first orange, Irgasin Red, Paranithoaniline Red, Toluidine Red, Solvent Red (17, 49, 128, 5, 13, 22 and 48.2, etc.), Disperse Red, Carmine FB, Pigment Orange R, Lake Red 2G, Rhodamine FB, Rhodamine B Lake, Methyl Violet B Lake, Phthalocyanine Blue, Solvent Blue (25, 94, 60 and 15.3, etc.), Pigment Blue, Brilliant Green, Phthalocyanine Green, Oil Yellow GG, Kayaset YG, Orazol Brown B and Oil Pink OP etc. are mentioned. If necessary, magnetic powders (powder of ferromagnetic metals such as iron, cobalt and nickel, compounds such as magnetite, hematite and ferrite) can be incorporated as a coloring agent.
The content of the colorant is preferably 1 to 40 parts by weight, more preferably 2 to 15 parts by weight, based on 100 parts by weight of the polyester of the present invention and other resins in total. When magnetic powder is used, the content of magnetic powder is preferably 20 to 150 parts by weight, more preferably 30 to 120 parts by weight, based on 100 parts by weight of the polyester of the present invention and other resins combined. be.

Release agents include natural waxes (beeswax, carnauba wax, montan wax, etc.), petroleum waxes (paraffin wax, microcrystalline wax, petrolatum, etc.), synthetic waxes (Fischer-Tropsch wax, polyethylene wax, polypropylene wax, polyethylene oxide, etc.). waxes, oxidized polypropylene waxes, etc.), and synthetic ester waxes (fatty acid esters synthesized from fatty acids having 10 to 30 carbon atoms and alcohols having 10 to 30 carbon atoms, etc.). It is preferable to contain one or more selected types. The content of the release agent is preferably 0 to 30% by weight, more preferably 0.5 to 20% by weight, still more preferably 1 to 10% by weight, based on the total 100 parts by weight of the polyester of the present invention and other resins. % by weight.

If necessary, modified wax may be used in combination with the release agent. Modified waxes are release agents grafted with vinyl polymer chains. Examples of the release agent used for the modified wax include the same release agents as those described above, and preferred ones are also the same. Examples of the vinyl monomer that constitutes the vinyl polymer chain of the modified wax include styrene and methacrylic acid ester. The vinyl polymer chain may be a homopolymer or a copolymer of vinyl monomers. The content of the modified wax is preferably 0 to 15% by weight, more preferably 0.5 to 10% by weight, still more preferably 1 to 5% by weight, based on the total 100 parts by weight of the polyester of the present invention and other resins. % by weight.

The charge control agent may contain either a positively chargeable charge control agent or a negatively chargeable charge control agent. ammonium salts, polyamine resins, imidazole derivatives, polymers containing quaternary ammonium groups, metal-containing azo dyes, copper phthalocyanine dyes, metal salicylates, boron complexes of benzylic acid, polymers containing sulfonic acid groups, fluorine-containing polymers, halogen-substituted aromatics ring-containing polymers and the like. The content of the charge control agent may be 0 to 20% by weight, preferably 0.1 to 10% by weight, more preferably 0.1 to 10% by weight, based on 100 parts by weight of the total polyester of the present invention and other resins. 5 to 7.5% by weight.

Examples of fluidizing agents include silica, titania, alumina, fatty acid metal salts, silicone resin particles and fluororesin particles, and two or more of them may be used in combination. Silica is preferable from the viewpoint of charging property of the toner. Silica is preferably hydrophobic silica from the viewpoint of toner transferability. The fluidizing agent content may be 0-10% by weight, preferably 0-5% by weight, more preferably 0.1-4% by weight, based on 100 parts by weight of the total resin particles of the present invention. is.

In addition, the total weight of additives such as colorants, release agents, charge control agents, and fluidizing agents may be 3 to 70% by weight, preferably 4 to 58% by weight, more preferably 4 to 58% by weight, based on the weight of the resin particles. It is preferably 5 to 50% by weight.

The volume average particle size (D50) of the resin particles is preferably 1 to 15 μm, more preferably 2 to 10 μm, particularly preferably 3 to 7 μm. The number average particle size is preferably 1 to 15 μm, more preferably 2 to 10 μm, particularly preferably 3 to 7 μm. A spherical shape is preferable from the viewpoint of fluidity.

The method for producing resin particles is not particularly limited, and known kneading pulverization methods, suspensions described in JP-B-36-10231, JP-A-59-53856 and JP-A-59-61842 are used. polymerization methods, emulsion polymerization methods represented by soap-free polymerization methods in which monomers are directly polymerized in the presence of water-soluble polymerization initiators to form toners, interfacial polymerization methods such as microcapsule manufacturing methods, In-site polymerization method, coacervation method, as disclosed in JP-A-62-106473 and JP-A-63-186253, at least one kind of fine particles are agglomerated to obtain a desired particle size. Those obtained by the emulsion aggregation method, the dispersion polymerization method characterized by monodispersion, the dissolution suspension method in which the necessary resins are dissolved in a water-insoluble organic solvent and then formed into resin particles in water, and the ester extension polymerization method. or may be produced by a method of dispersing in carbon dioxide in a supercritical state.
From the viewpoint of compatibility between hot offset resistance, particle size distribution, and chargeability, a method for producing resin particles includes dispersing a polyester for toner or a solvent solution thereof in an aqueous medium to obtain carbon derived from a polymerizable unsaturated group in the polyester. - It is preferable to include a step of obtaining a modified resin by cross-linking between carbon double bonds, and using fine particles of the resin, the polyester for toner or its solvent solution is dispersed in an aqueous solvent containing the fine particles of the resin. It is more preferable to include a step of cross-linking the carbon-carbon double bonds derived from the polymerizable unsaturated groups in the polyester to obtain a modified resin.

The method of producing a modified resin by cross-linking the carbon-carbon double bonds derived from the polymerizable unsaturated groups in the polyester for toner of the present invention in an aqueous medium is a dispersion containing the polyester for toner of the present invention. Second, a method for producing a modified resin formed by cross-linking carbon-carbon double bonds derived from polymerizable unsaturated groups in the polyester using radical polymerization, if necessary.

As the aqueous solvent in the present invention, any liquid containing water as an essential component can be used without limitation. Aqueous solutions, mixtures thereof, and the like can be used.
Examples of a method for stably forming a dispersion containing the polyester for toner of the present invention in an aqueous solvent include a method in which the polyester is added to the aqueous solvent and dispersed by shearing force.
When other resins are used, the polyester and other resins can be mixed in advance and dispersed in an aqueous medium. Furthermore, by cross-linking the carbon-carbon double bonds derived from the polymerizable unsaturated groups in the polyester, the polyester can be cross-linked in the presence of other resins.
When other resins are used as the fine particles, the fine particles of the resin are not particularly limited as long as they can form fine particles in an aqueous solvent and are adsorbed to the polyester for toner of the present invention.

The method for making resin fine particles into a dispersion is not particularly limited, but the following [1] to [2] can be mentioned.
[1] In the case of a vinyl resin, a method of directly producing a fine particle dispersion of a resin by polymerization reactions such as suspension polymerization, emulsion polymerization, seed polymerization and dispersion polymerization using a monomer as a starting material.
[2] In the case of polyaddition or condensation resins such as polyester resins, polyurethane resins and epoxy resins, precursors (monomers, oligomers, etc.) or solvent solutions thereof are dispersed in a medium in the presence of a suitable dispersant, and then A method of producing a resin fine particle dispersion by heating or adding a curing agent to cure.

In the method [1] or [2], known surfactants (s), water-soluble polymers (t), and the like described below can be used as emulsifiers or dispersants used in combination. In addition, an organic solvent or the like described later can be used together as an emulsifying or dispersing aid.

Furthermore, when using materials other than the polyester for toner of the present invention and other resins (colorants, release agents, modified waxes, charge control agents, etc.), the polyesters and other resins are mixed with other materials in advance. and can be dispersed in an aqueous medium. Furthermore, by cross-linking the carbon-carbon double bonds derived from the polymerizable unsaturated groups in the polyester, the polyester or other resin can be cross-linked in a state in which other raw materials are mixed in advance. Mixing other toner raw materials into the resin in advance and cross-linking the other raw materials facilitates dispersing and fixing the other raw materials in the resin, which is preferable from the viewpoint of particle size distribution and chargeability.
In addition, in the present invention, other raw materials such as a colorant, a release agent, a modified wax and a charge control agent do not necessarily have to be mixed when forming particles in an aqueous solvent. can be added later. For example, after forming particles containing no colorant, a colorant can be added by a known dyeing method.

The dispersion method is not particularly limited, but known equipment such as low-speed shearing, high-speed shearing, friction, high-pressure jet, and ultrasonic waves can be applied. A high shear method is preferred in order to achieve a dispersion particle size of 2-20 μm. When a high-speed shearing disperser is used, the rotation speed is not particularly limited, but is generally 1000 to 30000 rpm, preferably 5000 to 20000 rpm. The dispersion time is not particularly limited, but is generally 0.1 to 5 minutes in the batch method.
Dispersing devices include, for example, a homogenizer (manufactured by IKA), a polytron (manufactured by Kinematica), a batch-type emulsifier such as TK Auto Homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), and an Ebara Milder (manufactured by Ebara Corporation). ], TK Filmix, TK Pipeline Homomixer [manufactured by Tokushu Kika Kogyo Co., Ltd.], Colloid Mill [manufactured by Shinko Pantech Co., Ltd.], Ultra Visco Mill (manufactured by Aimex), Thrasher, Trigonal Wet Pulverizer [ Mitsui Miike Kakoki Co., Ltd.], Capitron (manufactured by Eurotech), Fine Flow Mill [manufactured by Taiheiyo Kiko Co., Ltd.] and other continuous emulsifiers, Microfluidizer [manufactured by Mizuho Kogyo Co., Ltd.], Nanomizer (manufactured by Mizuho Kogyo Co., Ltd.) Nanomizer), high-pressure emulsifiers such as APV Gaurin (manufactured by Gaurin), membrane emulsifiers such as membrane emulsifiers [manufactured by Reika Kogyo Co., Ltd.], vibromixers [manufactured by Reika Kogyo Co., Ltd.], etc. and an ultrasonic emulsifier such as an ultrasonic homogenizer (manufactured by Branson). Among these, APV Gaulin, Homogenizer, TK Auto Homomixer, Ebara Milder, TK Filmix and TK Pipeline Homomixer are preferred from the viewpoint of uniformity of particle size.

Radical polymerization can be carried out by a known method, and the polymerization temperature is selected according to the polymerization initiator used and the molecular weight of the polyester for toner of the present invention. It is preferably from 5 to 200°C, more preferably from 10 to 100°C, still more preferably from 15 to 60°C. The polymerization time is preferably 1 to 48 hours, more preferably 2 to 24 hours. Polymerization is generally carried out by heating after dispersion, but may be partially allowed to proceed before dispersion.

The radical reaction initiator (c) used for the cross-linking reaction of the polyester for toner of the present invention is not particularly limited. etc. Moreover, you may use together 2 or more types.

Examples of the inorganic peroxide (c1) include, but are not particularly limited to, hydrogen peroxide, ammonium persulfate, potassium persulfate and sodium persulfate.

Examples of the organic peroxide (c2) include, but are not limited to, benzoyl peroxide, di-t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, α,α-bis(t-butyl peroxy)diisopropylbenzene, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane, di-t-hexyl peroxide, 2,5-dimethyl-2,5-di-t- Butylperoxyhexyne-3, acetyl peroxide, isobutyryl peroxide, octaninol peroxide, decanolyl peroxide, lauroyl peroxide, 3,3,5-trimethylhexanoyl peroxide, m-toluyl peroxide, t -butyl peroxyisobutyrate, t-butyl peroxyneodecanoate, cumyl peroxyneodecanoate, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxy-3,5,5 -trimethylhexanoate, t-butylperoxylaurate, t-butylperoxybenzoate, t-butylperoxyisopropylmonocarbonate and t-butylperoxyacetate.

Examples of the azo compound (c3) include, but are not limited to, 2,2'-azobis-(2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 1,1'-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile, 2,2'-azobis(2-methylbutyronitrile) and azobisisobutyronitrile, etc. is mentioned.

In the cross-linking reaction of the polyester for toner of the present invention, a reducing agent may be used, and it is preferable to combine the radical reaction initiator (c) and the reducing agent.
The reducing agent is not particularly limited as long as it is a known reducing agent, and reducing organic compounds such as ascorbic acid, tartaric acid, citric acid, glucose and formaldehyde sulfoxylate metal salts, sodium thiosulfate, sodium sulfite, sodium bisulfite. , sodium metabisulfite, ferric chloride, ferric sulfate (iron (II) sulfate heptahydrate, etc.), and reducing inorganic compounds such as diphosphates.

When the polyester, etc. for toner of the present invention is dispersed in an aqueous solvent, the polyester, etc. is preferably liquid. When the polyester or the like is solid at room temperature, it may be dispersed in a liquid state at a temperature higher than its melting point, or an organic solvent solution of the polyester or the like may be used. It is preferable to use an organic solvent because the particle size distribution becomes sharp.

Examples of organic solvents include aromatic hydrocarbon solvents, aliphatic or alicyclic hydrocarbon solvents, halogen solvents, ester or ester ether solvents, ether solvents, ketone solvents, alcohol solvents, amide solvents, sulfoxide solvents, heterocyclic Compound solvents, mixed solvents of two or more thereof, and the like are included.
Specific examples of organic solvents include aromatic hydrocarbon solvents (toluene, xylene, ethylbenzene, tetralin, etc.); aliphatic or alicyclic hydrocarbon solvents (n-hexane, n-heptane, mineral spirits, cyclohexane, etc.); Halogen solvents such as methyl, methyl bromide, methyl iodide, methylene dichloride, carbon tetrachloride, trichlorethylene and perchlorethylene; esters or ester ethers such as ethyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate and ethyl cellosolve acetate. Solvent; ether solvents such as diethyl ether, tetrahydrofuran, dioxane, ethyl cellosolve, butyl cellosolve and propylene glycol monomethyl ether; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, di-n-butyl ketone and cyclohexanone; methanol, ethanol, n-propanol , isopropanol, n-butanol, isobutanol, t-butanol, 2-ethylhexyl alcohol and benzyl alcohol; amide solvents such as dimethylformamide and dimethylacetamide; sulfoxide solvents such as dimethylsulfoxide; complex solvents such as N-methylpyrrolidone; Examples include cyclic compound solvents and mixed solvents of two or more thereof. Among the above organic solvents, volatile ones having a boiling point of less than 100°C are preferred. Preferred organic solvents include ethyl acetate, acetone and methyl ethyl ketone.

A known surfactant (s) can be used as an emulsifier or dispersant used in combination when the polyester for toner of the present invention is dispersed in an aqueous solvent. The use of the surfactant (s) is preferable because the volume average particle size of the resin particles can be easily reduced.

The surfactant (s) is not particularly limited, and includes an anionic surfactant (s-1), a cationic surfactant (s-2), an amphoteric surfactant (s-3) and a nonionic surfactant ( s-4) and the like. The surfactant (s) may be a combination of two or more surfactants.

Examples of the anionic surfactant (s-1) include carboxylic acids or salts thereof, sulfate ester salts, carboxymethylated salts, sulfonates and phosphate ester salts.
Cationic surfactants (s-2) include quaternary ammonium salt surfactants and amine salt surfactants.
Examples of amphoteric surfactants (s-3) include carboxylate type amphoteric surfactants, sulfate type amphoteric surfactants, sulfonate type amphoteric surfactants and phosphate type amphoteric surfactants. mentioned.
Nonionic surfactants (s-4) include AO addition type nonionic surfactants and polyhydric alcohol type nonionic surfactants.
Specific examples of these surfactants (s) include those described in JP-A-2002-284881.

The amount of the surfactant (s) used is preferably 0 to 300 parts by weight, more preferably 0.001 to 10 parts by weight, and particularly preferably 0.01 to 5 parts by weight based on 100 parts by weight of water as the aqueous solvent. be.

A known water-soluble polymer (t) can be used as an emulsifier or dispersant used in combination when the polyester for toner of the present invention is dispersed in an aqueous solvent. The use of the water-soluble polymer (t) is preferable because the volume average particle size of the resin particles is reduced and the particle size distribution (volume average particle size/number average particle size) tends to be small.

Examples of the water-soluble polymer (t) include cellulose compounds (e.g., methylcellulose, ethylcellulose, hydroxyethylcellulose, ethylhydroxyethylcellulose, carboxymethylcellulose, hydroxypropylcellulose, and saponified products thereof), gelatin, starch, dextrin, gum arabic, chitin, and chitosan. , polyvinyl alcohol, polyvinylpyrrolidone, polyethylene glycol, polyethyleneimine, polyacrylamide, polymers containing acrylic acid (salts) (sodium polyacrylate, potassium polyacrylate, ammonium polyacrylate, sodium hydroxide partially neutralized polyacrylic acid) and sodium acrylate-acrylate copolymer, etc.), sodium hydroxide (partially) neutralized product of styrene-maleic anhydride copolymer, reaction of water-soluble polyurethane (polyethylene glycol, polycaprolactone diol, etc.) with polyisocyanate products, etc.).

The amount of the water-soluble polymer (t) to be used is preferably 0 to 5 parts by weight per 100 parts by weight of water as the aqueous solvent.

The polyester and resin particles for toner of the present invention are raw materials for toner that are fixed on a support (paper, polyester film, etc.) by a copying machine, printer, or the like to form a recording material. As a method for fixing onto the support, a known hot roll fixing method, flash fixing method, or the like can be applied.

The resin particles of the present invention are used as a toner for developing electrostatic charge images or magnetic latent images in electrophotography, electrostatic recording, electrostatic printing, and the like. More particularly, it relates to a toner used for developing electrostatic charge images or magnetic latent images suitable for full-color applications.

EXAMPLES The present invention will be described in detail below with reference to Examples, but the present invention is not limited to these. Moreover, a part means a weight part below.

<Example 1> [Production of toner polyester (A-1)]
446 parts of bisphenol A/PO2 molar adduct, 335 parts of bisphenol A/PO3 molar adduct, 198 parts of terephthalic acid, 83 parts of adipic acid as a condensation catalyst were placed in a reactor equipped with a condenser, stirrer and nitrogen inlet tube. 0.6 part of titanium diisopropoxybistriethanolamine was added and reacted for 10 hours under reduced pressure of 0.5 to 2.5 kPa while gradually raising the temperature to 230°C. An acid value of less than 1 mgKOH/g was confirmed, and a polyester having hydroxyl groups was obtained. Then, 114 parts of methacrylic anhydride was added and reacted at 150° C. for 3 hours, after which the by-product was distilled off under reduced pressure of 0.5 to 2.5 kPa to obtain polyester for toner (A-1). .

<Examples 2 to 11> [Production of toner polyesters (A-2) to (A-11)]
A reactor equipped with a condenser, a stirrer, and a nitrogen inlet tube was charged with the polyols, polycarboxylic acids, and acid anhydrides shown in Table 1. Other than that, the reaction was carried out in the same manner as in Example 1 to produce polyester for toner. (A-2) to (A-11) were obtained.

<Example 12> [Production of toner polyester (A-12)]
508 parts of 3-methyl-1,5-pentanediol, 283 parts of terephthalic acid, 249 parts of adipic acid, and titanium diisopropoxybistriethanol as a condensation catalyst are placed in a reactor equipped with a condenser, stirrer and nitrogen inlet tube. 0.6 part of an amine was added and reacted for 10 hours under a reduced pressure of 0.5 to 2.5 kPa while gradually raising the temperature to 230.degree. An acid value of less than 1 mgKOH/g was confirmed, and a polyester having hydroxyl groups was obtained. Thereafter, 81 parts of methacrylic anhydride was added and reacted at 150° C. for 3 hours to obtain polyester for toner (A-12).

<Comparative Example 1> [Production of toner polyester (A'-1)]
517 parts of bisphenol A/PO2 mol adduct, 261 parts of bisphenol A/EO 2 mol adduct, 131 parts of terephthalic acid, 24 parts of trimellitic anhydride, fumaric 145 parts of an acid and 0.6 parts of titanium diisopropoxybistriethanolamine as a condensation catalyst were added, and the temperature was gradually raised to 180° C., and the reaction was carried out for 4 hours while distilling off the water generated in the nitrogen stream. Furthermore, the mixture was reacted under a reduced pressure of 0.5 to 2.5 kPa for 10 hours to obtain polyester for toner (A'-1).

<Comparative Example 2> [Production of toner polyester (A'-2)]
508 parts of 3-methyl-1,5-pentanediol, 283 parts of terephthalic acid, 249 parts of adipic acid and titanium diisopropoxybistriethanolamine as a condensation catalyst were placed in a reactor equipped with a condenser, stirrer and nitrogen inlet tube. Then, the temperature was gradually raised to 220°C, and the reaction was carried out at 220°C for 4 hours under a nitrogen stream while distilling off the generated water. Furthermore, the reaction was carried out for 10 hours under a reduced pressure of 0.5 to 2.5 kPa. When the acid value became less than 1 mgKOH/g, it was taken out to obtain polyester (a'-2). Further, 1000 parts of polyester (a′-2), 2.7 parts of trimethylolpropane, 116.3 parts of isophorone diisocyanate (IPDI) and 746 parts of ethyl acetate are put into an autoclave and reacted at 80° C. for 10 hours in a closed state. , to obtain a solution of toner polyester (A'-2) containing an isocyanate group at the molecular end.

<Comparative Example 3> [Production of toner polyester (A'-3)]
739 parts of bisphenol A/EO 2 mol adduct, 19 parts of trimethylolpropane, 225 parts of terephthalic acid, 33 parts of adipic acid, 73 parts of acrylic acid, and a condensation catalyst were placed in a reactor equipped with a condenser, stirrer and nitrogen inlet tube. 0.6 part of titanium diisopropoxy bistriethanolamine was added as a solvent, and the temperature was gradually raised to 180° C., and the reaction was carried out for 4 hours while distilling off the water generated in the nitrogen stream. Furthermore, the mixture was reacted under a reduced pressure of 0.5 to 2.5 kPa for 10 hours to obtain polyester for toner (A'-3).

Table 1 shows the composition, glass transition temperature (Tg), weight average molecular weight (Mw), and polymerizability of toner polyesters (A-1) to (A-12) and (A'-1) to (A'-3). The amount of unsaturated groups and the THF-insoluble content are described.

<Production Example 1> [Production of polyester (B-1)]
260 parts of 2 mol bisphenol A.PO adduct, 195 parts of 3 mol. 10 parts, 255 parts of terephthalic acid, 45 parts of adipic acid, 0.6 parts of titanium diisopropoxybistriethanolamine as a condensation catalyst, and an acid value of 20 mgKOH/g while distilling off the water generated under a nitrogen stream at 220°C. After the reaction was carried out until the temperature reached the following, the reaction was carried out for 10 hours under a reduced pressure of 0.5 to 2.5 kPa. Then, 30 parts by weight of trimellitic anhydride was added and the mixture was kept at 175° C. for 1 hour to obtain an amorphous polyester (B-1).

<Production Example 2> [Production of fine particle dispersion]
In a reaction vessel set with a stirring rod and a thermometer, 690.0 parts of water, sodium salt of polyoxyethylene monomethacrylate sulfate ester "Eleminol RS-30" [manufactured by Sanyo Chemical Industries Co., Ltd.] 9.0 parts, styrene 90 0 part, 90.0 parts of methacrylic acid, 110.0 parts of butyl acrylate and 1.0 parts of ammonium persulfate were added and stirred at 350 rpm for 15 minutes to give a white emulsion. Then, the temperature was raised to 75° C. and the reaction was carried out at the same temperature for 5 hours. Further, 30 parts of a 1% by weight ammonium persulfate aqueous solution was added, and the mixture was aged at 75° C. for 5 hours to produce a vinyl resin (copolymer of sodium salt of styrene-methacrylic acid-butyl acrylate-ethylene oxide methacrylate adduct sulfate ester). A fine particle dispersion was obtained.
The volume average particle diameter of the particles dispersed in the fine particle dispersion was measured using a laser diffraction/scattering particle size distribution measuring device "LA-920" [manufactured by Horiba, Ltd.] and was found to be 0.1 μm. there were.

<Production Example 3> [Production of colorant dispersion]
557 parts of propylene glycol, 569 parts of terephthalic acid dimethyl ester, 184 parts of adipic acid, and 3 parts of tetrabutoxytitanate as a condensation catalyst are introduced into a reaction vessel equipped with a stirrer, a heating/cooling device, a thermometer, a condenser, and a nitrogen inlet tube. The mixture was reacted at 180° C. under a nitrogen stream for 8 hours while distilling off the generated methanol. Then, while gradually raising the temperature to 230° C., the mixture was reacted for 4 hours under a nitrogen stream while distilling off the propylene glycol and water produced, and further reacted for 1 hour under a reduced pressure of 0.007 to 0.026 MPa. 175 parts of propylene glycol were recovered. Next, the temperature is cooled to 180°C, 121 parts of trimellitic anhydride are added, and after reacting for 2 hours under normal pressure, the reaction is allowed to proceed at 220°C under normal pressure until the softening point reaches 180°C. ). Into a beaker, 20 parts of copper phthalocyanine, 4 parts by weight of a colorant dispersant "Solspers 28000" [manufactured by Avecia Co., Ltd.], 20 parts of the obtained polyester and 56 parts of ethyl acetate are added and stirred to uniformly disperse. A colorant dispersion was obtained by finely dispersing copper phthalocyanine using a bead mill.

<Production Example 4> [Production of modified wax]
454 parts of xylene, low-molecular-weight polyethylene wax “Sanwax LEL-400” [softening point: 128° C., manufactured by Sanyo Chemical Industries, Ltd.] are placed in a pressure-resistant reaction vessel equipped with a stirring device, a heating and cooling device, a thermometer, and a dropping cylinder. After purging with nitrogen, the temperature was raised to 170° C. with stirring, and at the same temperature, a mixed solution of 595 parts of styrene, 255 parts of methyl methacrylate, 34 parts of di-t-butylperoxyhexahydroterephthalate and 119 parts of xylene. was added dropwise over 3 hours, and the temperature was maintained for 30 minutes. Next, xylene was distilled off under a reduced pressure of 0.039 MPa to obtain a modified wax.

<Production Example 5> [Production of Release Agent Dispersion]
10 parts of paraffin wax "HNP-9" [maximum heat of fusion peak temperature: 73 ° C., manufactured by Nippon Seiro Co., Ltd.], Production Example 4 1 part of the modified wax obtained in 1. and 33 parts of ethyl acetate are added, the temperature is raised to 78° C. with stirring, and after stirring at the same temperature for 30 minutes, the paraffin wax is finely divided into fine particles by cooling to 30° C. over 1 hour. The mixture was crystallized and further wet pulverized with an Ultraviscomil (manufactured by Imex) to obtain a release agent dispersion.

<Production Example 6> [Production of polyester mixed solution (AB-1)]
6.8 parts of polyester (A-1) for toner, 53.2 parts of polyester (B-1), and 40 parts of ethyl acetate were added to a reaction vessel equipped with a stirring device, and dissolved by stirring to give a polyester mixed solution. (AB-1) was obtained.

<Production Examples 7 to 17> [Production of polyester mixed solutions (AB-2) to (AB-12)]
Polyester mixed solutions (AB-2) to (AB-12) were prepared in the same manner as in Production Example 6, except that toner polyester (A-1) was changed to toner polyester (A-2) to (A-12). Obtained.

<Comparative Production Example 1> [Production of polyester mixed solution (A'B-1)]
A polyester mixture solution (A'B-1) was obtained in the same manner as in Production Example 6 except that the toner polyester (A-1) was changed to the toner polyester (A'-1).

<Comparative Production Example 2> [Production of polyester mixed solution (A'B-2)]
11.2 parts of a solution of polyester (A'-2) for toner, 53.2 parts of polyester (B-1), and 35.5 parts of ethyl acetate were charged into a reactor equipped with a stirrer and stirred under a nitrogen stream. They were dissolved by stirring to obtain a mixed polyester solution (A'B-2).

<Comparative Production Example 3> [Production of polyester mixed solution ~ (A'B-3)]
A mixed polyester solution (A'B-3) was obtained in the same manner as in Production Example 6 except that the toner polyester (A-1) was changed to the toner polyester (A'-3).

<Example 13> [Production of resin particles (D-1)]
In a beaker, 135 parts of ion-exchanged water, 0.5 parts of [fine particle dispersion], 5 parts by weight of sodium carboxymethylcellulose, 48.5% by weight aqueous solution of sodium dodecyldiphenyl ether disulfonate "Eleminol MON-7" [Sanyo Chemical Industries, Ltd. )] and 15 parts of ethyl acetate were added and stirred to dissolve uniformly.
Next, 67 parts of polyester mixed solution (AB-1), 20 parts of [colorant dispersion], 20 parts of [releasing agent dispersion] and 5 parts of ethyl acetate were added, and the mixture was stirred at 10,000 rpm with a TK Auto Homomixer. Stir for 2 minutes. Next, 1 part of a 30% aqueous solution of hydrogen peroxide, 1.5 parts of ascorbic acid and 0.1 part of iron (II) sulfate heptahydrate were added and stirred at 40° C. for 3 hours. Next, this mixed solution is transferred to a reaction vessel equipped with a stirrer and a thermometer, and ethyl acetate is distilled off at 50° C. until the concentration becomes 0.5% by weight or less to obtain an aqueous resin dispersion of resin particles. , washing, filtration, and drying at 40° C. for 18 hours to reduce the volatile content to 0.5% by weight or less to obtain resin particles (D-1) of the present invention.

<Examples 14 to 24> [Production of resin particles (D-2) to (D-12)]
In Example 13, resin particles (D-2) to (D -12) was obtained.

<Comparative Example 4> [Production of resin particles (D'-1)]
In a beaker, 135 parts of ion-exchanged water, 0.5 parts of [fine particle dispersion], 5 parts by weight of sodium carboxymethylcellulose, 48.5% by weight aqueous solution of sodium dodecyldiphenyl ether disulfonate "Eleminol MON-7" [Sanyo Chemical Industries, Ltd. )] and 15 parts of ethyl acetate were added and stirred to dissolve uniformly.
Then, 67 parts of polyester solution (A'B-1), 20 parts of [colorant dispersion], 20 parts of [releasing agent dispersion] and 5 parts of ethyl acetate, 2,2'-azobis-(2,4- 1 part of dimethylvaleronitrile) was added and stirred for 2 minutes at 10,000 rpm with a TK auto homomixer. Next, this mixed solution is transferred to a reaction vessel equipped with a stirrer and a thermometer, and ethyl acetate is distilled off at 65° C. until the concentration becomes 0.5% by weight or less to obtain an aqueous resin dispersion of resin particles. , washed, separated by filtration, and dried at 40° C. for 18 hours to reduce the volatile content to 0.5% by weight or less to obtain resin particles (D′-1).

<Comparative Example 5> [Production of resin particles (D'-2)]
In a beaker, 135 parts of ion-exchanged water, 0.5 parts of [fine particle dispersion], 5 parts of sodium carboxymethyl cellulose, 48.5% by weight aqueous solution of sodium dodecyldiphenyl ether disulfonate "Eleminol MON-7" [Sanyo Chemical Industries Co., Ltd. )] and 15 parts of ethyl acetate were added and stirred to dissolve uniformly.
Next, 67 parts of the polyester solution (A'B-2), 20 parts of [colorant dispersion], 20 parts of [releasing agent dispersion], 5 parts of ethyl acetate, and 0.13 parts of isophoronediamine are added, and TK The mixture was stirred for 2 minutes at 10,000 rpm with an auto homomixer. Next, this mixed solution is transferred to a reaction vessel equipped with a stirrer and a thermometer, and ethyl acetate is distilled off at 50° C. until the concentration becomes 0.5% by weight or less to obtain an aqueous resin dispersion of resin particles. , washing, filtration, and drying at 40° C. for 18 hours to reduce the volatile content to 0.5% by weight or less to obtain resin particles (D'-2).

<Comparative Example 6> [Production of resin particles (D'-3)]
In a beaker, 135 parts of ion-exchanged water, 0.5 parts of [fine particle dispersion], 5 parts by weight of sodium carboxymethylcellulose, 48.5% by weight aqueous solution of sodium dodecyldiphenyl ether disulfonate "Eleminol MON-7" [Sanyo Chemical Industries, Ltd. )] and 15 parts of ethyl acetate were added and stirred to dissolve uniformly.
Then, 67 parts of polyester solution (A'B-3), 20 parts of [colorant dispersion], 20 parts of [releasing agent dispersion] and 5 parts of ethyl acetate, 2,2'-azobis-(2,4- 1 part of dimethylvaleronitrile) was added and stirred for 2 minutes at 10,000 rpm with a TK auto homomixer. Next, this mixed solution is transferred to a reaction vessel equipped with a stirrer and a thermometer, and ethyl acetate is distilled off at 65° C. until the concentration becomes 0.5% by weight or less to obtain an aqueous resin dispersion of resin particles. , washed, separated by filtration, and dried at 40° C. for 18 hours to reduce the volatile content to 0.5% by weight or less to obtain resin particles (D'-3).

To 100 parts of resin particles (D-1) to (D-12) and (D'-1) to (D'-3), 1 part of hydrophobic silica "Aerosil R972" [manufactured by Nippon Aerosil] was added as a fluidizing agent. After mixing in a mill, granulation properties, low-temperature fixability, heat-resistant storage stability, and charging properties were evaluated by the following methods. Table 2 shows the evaluation results.

[Evaluation method]
Methods for measuring and evaluating hot-offset resistance, particle size distribution, and chargeability, including judgment criteria, will be described below.

<Hot offset resistance (hot offset generation temperature)>
The resin particles after the external addition treatment are evenly placed on the surface of paper so as to be 0.8 mg/cm ² . At this time, the method of placing the powder on the paper surface uses a printer without a heat fixing device. Other methods may be used as long as the powder can be uniformly placed at the above weight density.
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 (pressure roller pressure) of 10 kg/cm ² , and the temperature at which hot offset occurred was measured. evaluated the sex.
Generally, it is said that 170° C. or higher is preferable under this evaluation condition.
○: hot offset temperature is 170°C or higher ×: hot offset temperature is lower than 170°C

<Particle size distribution>
Granulation properties were evaluated by dispersing each of the resin particles after the external addition treatment in water and measuring the volume average particle size and particle size distribution with a Coulter counter "Multisizer III" (manufactured by Beckman Coulter, Inc.).
Regarding granulation, it is preferred that the particle size distribution is 1.20 or less when the volume average particle size is 5.0 to 5.9 μm.
○: Particle size distribution is 1.20 or less ×: Particle size distribution is greater than 1.20

<Chargeability>
0.5 g of the resin particles after the external addition treatment and 10 g of ferrite carrier (F-150, manufactured by Powdertech Co., Ltd.) were placed in a 50 ml glass bottle, and this was conditioned at 23° C. and a relative humidity of 50% for 8 hours or more. The mixture was friction-stirred at 90 rpm for 2 minutes with a Blur shaker mixer. After stirring, 0.2 g of the mixed powder was loaded into a blow-off powder charge amount measuring device equipped with a stainless wire mesh with an opening of 20 μm, and the charge amount of the residual ferrite carrier was measured under the conditions of a blow pressure of 10 KPa and a suction pressure of 5 KPa. , the charge amount (μC/g) of the resin particles was calculated by a standard method. For toner, the higher the amount of negative charge, the better the charging characteristics.
A blow-off charge amount measuring device [manufactured by Toshiba Chemica Corporation] was used for the measurement.
[criterion]
○: Less than -20 △: -20 or more and less than -15 ×: -15 or more

The resin particles of Examples 13 to 24 of the present invention exhibited excellent hot offset resistance, particle size distribution and chargeability.
On the other hand, the resin particles (D'-1) using the polyester for toner (A'-1) not using the acid anhydride (Z) having a polymerizable unsaturated group is the polyester for toner (A'- Although 1) had a polymerizable unsaturated group, the reactivity of the polymerizable unsaturated group was low, and although the particle size distribution and chargeability were good, the hot offset resistance was poor. Also, the resin particles (D'-2) using the toner polyester (A'-2) containing an isocyanate group at the molecular end had good hot offset property and particle size distribution, but poor chargeability. . Furthermore, the resin particles (D'-3) using the polyester for toner (A'-3) not using the acid anhydride (Z) having a polymerizable unsaturated group is the polyester for toner (A'-3 ) had a polymerizable unsaturated group, but had a large amount of insoluble matter due to a side reaction, and although the hot offset property and charging property were good, the particle size distribution was poor.

The polyester and resin particles for toner of the present invention are excellent in hot offset property, particle size distribution and charging property, and therefore are extremely useful as a toner material for electrostatic charge image development used in electrophotography, electrostatic recording, electrostatic printing and the like. be.

Claims (6)

A toner which is an addition reaction product of a polyester having a hydroxyl group and an acid anhydride (Z) having a polymerizable unsaturated group and has a polymerizable unsaturated group amount of 2×10 ⁻⁶ to 4×10 ⁻³ mol/g. for polyester. 2. The polyester for toner according to claim 1, wherein the polyester for toner has a tetrahydrofuran insoluble content of 1% by weight or less. The acid anhydride (Z) having a polymerizable unsaturated group is one or more compounds selected from the group consisting of acrylic anhydride, methacrylic anhydride, crotonic anhydride, and tiglic anhydride. The polyester for toner described in . 4. Resin particles comprising a crosslinked reaction product of the polyester for toner according to any one of claims 1 to 3. A toner having a polymerizable unsaturated group amount of 2×10 ⁻⁶ to 4×10 ⁻³ mol/g, which has an addition reaction step between a polyester having a hydroxyl group and an acid anhydride (Z) having a polymerizable unsaturated group. Process for producing polyester for use. 5. The acid anhydride having a polymerizable unsaturated group (Z) is one or more compounds selected from the group consisting of acrylic anhydride, methacrylic anhydride, crotonic anhydride, and tiglic anhydride. 3. The method for producing the polyester for toner according to .