JP7679271B2 - Method for producing resin particles - Google Patents

Description

The present invention relates to a method for producing resin particles.

2. Description of the Related Art In recent years, with the development of electrophotographic systems, the demand for electrophotographic apparatuses such as copying machines and laser printers has increased rapidly, and the requirements for their performance have also become more sophisticated.
Conventionally, in electrophotography, there have been known methods and apparatuses in which 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 then the toner image is transferred onto a transfer material. After repeating such image forming steps, the toner image on the transfer material is heated and fixed to obtain a multi-color image.
To pass through these processes without any problems, the toner must first be able to maintain a stable charge (chargeability), and must also satisfy the following functions: the toner must be able to fix even when the heat roll temperature is low (low-temperature fixability), and the toner must not fuse to the heat roll even when the fixation temperature is high (hot offset resistance).
Polyester-based toner binders are used to achieve low-temperature fixability, and a toner binder that can improve low-temperature fixability by incorporating a crystalline polyester has been proposed (Patent Document 1). However, such toners are prone to the problem of the toner fusing to a heated roll (hot offset).
In addition, in order to improve hot offset resistance, (1) a toner binder made of a polyester partially crosslinked with a polyfunctional monomer (Patent Document 2) and (2) a toner using a modified polyester resin having a crosslinked polyester resin skeleton and further having a reactive functional group at the end (Patent Document 3) have been proposed.
However, these toners have problems in that (1) the particle size distribution deteriorates due to low solubility in the oil phase and poor emulsification (formability), and (2) the charging characteristics deteriorate due to the positive charging properties of the urethane and urea groups induced.

JP 2002-287426 A Japanese Unexamined Patent Publication No. 57-109825 JP 2008-233360 A

The present invention aims to provide resin particles that have excellent hot offset resistance, granulation properties, and charging properties.

［一般式（１）中、Ｒ^１は、水素原子又はアルキル基を表し、Ｒ^２はそれぞれ独立にアルキレン基又はオキシアルキレン基を表す。］ The present inventors have conducted extensive research and have arrived at the present invention, which relates to a method for producing resin particles, comprising a step of bonding, in an aqueous medium, the chemical structural moiety of general formula (1) or (2) of a polyester resin having a number average molecular weight of 1,000 to 10,000 and a chemical structural moiety represented by the following general formula (1) or (2):

[In general formula (1), R ¹ represents a hydrogen atom or an alkyl group, and R ² each independently represents an alkylene group or an oxyalkylene group.]

The present invention makes it possible to provide resin particles that are excellent in hot offset resistance, granulation properties, and charging properties.

The method for producing resin particles of the present invention includes a step of bonding, in an aqueous medium, the chemical structural moieties of general formula (1) and/or (2) of a polyester resin having a number average molecular weight of 1,000 to 10,000 and having the chemical structural moieties represented by general formula (1) and/or (2).
The method for producing the resin particles of the present invention will be described below in detail.

The resin particles obtained by the present invention are resin particles containing a reaction product of the chemical structural portion of general formula (1) and/or (2) of a polyester resin having the chemical structural portion represented by general formula (1) and/or (2) and a metal compound. The reaction product is a resin composition obtained by the coordination bond between the chemical structural portion represented by general formula (1) and/or (2) and a metal compound.

The polyester resin in the present invention is a polyester resin characterized by having a number average molecular weight of 1000 to 10000 and having a chemical structural portion represented by the following general formula (1) and/or (2). By having the polyester resin have a structural portion represented by general formula (1) or (2), it is possible to obtain a polyester resin for toners that has excellent chargeability and hot offset properties. Note that, from the viewpoint of chargeability, the polyester resin in the present invention is preferably a polyester resin that does not contain urethane bonds or urea bonds.

ここで、一般式（１）中、Ｒ^１は、水素原子又はアルキル基を表し、Ｒ^２はそれぞれ独立にアルキレン基又はオキシアルキレン基を表す。
アルキル基としては、炭素数１～１８の直鎖又は分岐のアルキル基が挙げられ、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、ペンチル基、ヘキシル基、オクチル基、ノニル基、デシル基等が挙げられる。
アルキレン基としては、炭素数１～１８のアルキレン基が挙げられ、例えば、メチレン基、エチレン基、プロピレン基、ブチレン基、２－メチルプロピレン基、へキシレン基、オクチレン基、ドデシレン基、オクタデシレン基が挙げられる。
オキシアルキレン基としては、炭素数２～１０のオキシアルキレン基が挙げられ、例えば、オキシエチレン基、オキシ－ｎ－プロピレン基、オキシイソプロピレン基、オキシイソプロピリデン基、オキシ－ｎ－ブチレン基、オキシイソブチレン基、オキシ－ｎ－ペンチレン基、オキシイソペンチレン基、オキシ－ｎ－ヘキシレン基、オキシイソヘキシレン基、オキシ－ｎ－ヘプチレン基、オキシイソヘプチレン基、オキシ－ｎ－オクチレン基、オキシイソオクチレン基、オキシ－２－エチルヘキシレン基、オキシ－ｎ－ノニレン基、オキシイソノニレン基、オキシ－ｎ－デシレン基、オキシイソデシレン基等が挙げられる。
耐ホットオフセット性の観点から、Ｒ^１は、アルキル基であることが好ましく、炭素数１～１８の直鎖又は分岐のアルキル基であることが好ましい。
また、耐ホットオフセット性及び造粒性の観点から、Ｒ^２はオキシアルキレン基であることが好ましく、炭素数２～１０のオキシアルキレン基であることがより好ましく、炭素数２～６のオキシアルキレン基であることがさらに好ましい。

In the general formula (1), R ¹ represents a hydrogen atom or an alkyl group, and R ² each independently represents an alkylene group or an oxyalkylene group.
The alkyl group may be a straight-chain or branched alkyl group having 1 to 18 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, a nonyl group, or a decyl group.
The alkylene group includes alkylene groups having 1 to 18 carbon atoms, such as a methylene group, an ethylene group, a propylene group, a butylene group, a 2-methylpropylene group, a hexylene group, an octylene group, a dodecylene group, and an octadecylene group.
The oxyalkylene group includes an oxyalkylene group having 2 to 10 carbon atoms, such as an oxyethylene group, an oxy-n-propylene group, an oxyisopropylene group, an oxyisopropylidene group, an oxy-n-butylene group, an oxyisobutylene group, an oxy-n-pentylene group, an oxyisopentylene group, an oxy-n-hexylene group, an oxyisohexylene group, an oxy-n-heptylene group, an oxyisoheptylene group, an oxy-n-octylene group, an oxyisooctylene group, an oxy-2-ethylhexylene group, an oxy-n-nonylene group, an oxyisononylene group, an oxy-n-decylene group, and an oxyisodecylene group.
From the viewpoint of hot offset resistance, R ¹ is preferably an alkyl group, and more preferably a linear or branched alkyl group having 1 to 18 carbon atoms.
From the viewpoints of hot offset resistance and granulation properties, ^R2 is preferably an oxyalkylene group, more preferably an oxyalkylene group having 2 to 10 carbon atoms, and even more preferably an oxyalkylene group having 2 to 6 carbon atoms.

The polyester resin in the present invention is not particularly limited as long as it has an average molecular weight of 1,000 to 10,000 and has a chemical structure represented by general formula (1) and/or (2). For example, it may be a reaction product of a polyester resin having a hydroxyl group and a compound having a chemical structure represented by general formula (1) and/or (2).

Examples of polyester resins having hydroxyl groups include condensation type polyester polyols and polylactone polyols. One type of polyester having hydroxyl groups may be used alone, or two or more types may be used in combination.

The condensation type polyester polyol is not particularly limited, but examples thereof include polycondensates of polyols and polycarboxylic acids.

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

Examples of diols (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-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 (hereinafter, "alkylene oxide" may be abbreviated as AO) adducts of the above alicyclic diols.

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

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 their alkylene oxide adducts.

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

As the diol (g), in addition to the above diols having no functional groups other than hydroxyl groups, diols (g1) having other functional groups may be used.
Examples of (g1) include diols having a carboxyl group, diols having a sulfonic acid group or a sulfamic acid group, and salts thereof.
The diol having a carboxyl group may be a dialkylolalkanoic acid having 6 to 24 carbon atoms, specifically 2,2-dimethylolpropionic acid (DMPA), 2,2-dimethylolbutanoic acid, 2,2-dimethylolheptanoic acid, 2,2-dimethyloloctanoic acid, etc.
Examples of 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.

Preferred diols (g) are alkylene glycols having 2 to 36 carbon atoms, aromatic diols, and diols having other functional groups (g1), more preferably alkylene glycols having 2 to 12 carbon atoms, diols having a carboxyl group, and AO adducts of bisphenol A, and even more preferably alkylene glycols having 2 to 12 carbon atoms, AO adducts of bisphenol A, and combinations of these.

Examples of the tri- or higher hydric polyol (h) include tri- or higher hydric polyhydric aliphatic alcohols having 3 to 36 carbon atoms, AO adducts of polyhydric aliphatic alcohols (number of moles added: 2 to 120), AO adducts of trisphenols (e.g., trisphenol PA) (number of moles added: 2 to 30), AO adducts of novolak resins (e.g., phenol novolak, cresol novolak) (number of moles added: 2 to 30), and acrylic polyols [e.g., copolymers of hydroxyethyl (meth)acrylate and other vinyl monomers].
Examples of the polyhydric aliphatic alcohol having 3 to 36 carbon atoms and having a valence of 3 or more include alkane polyols and their intramolecular or intermolecular dehydration products, as well as sugars (such as sucrose) and their methyl glucosides.
Specific examples of alkane polyols and their intramolecular or intermolecular dehydration products 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 or higher polyhydric aliphatic alcohols having 3 to 36 carbon atoms.

Examples of polycarboxylic acids include dicarboxylic acids (i) and trivalent or higher polycarboxylic acids (j).

Examples of the dicarboxylic acid (i) include alkane dicarboxylic acids having 4 to 36 carbon atoms, alkene dicarboxylic acids having 4 to 36 carbon atoms, alicyclic dicarboxylic acids having 6 to 40 carbon atoms, aromatic dicarboxylic acids having 8 to 36 carbon atoms, and anhydrides and lower alkyl (having 1 to 4 carbon atoms) esters (methyl esters, ethyl esters, isopropyl esters, etc.) of these carboxylic acids.
Examples of the alkanedicarboxylic acid having 4 to 36 carbon atoms include succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanedicarboxylic acid, octadecanedicarboxylic acid, and decylsuccinic acid.
Examples of the alkene dicarboxylic acid having 4 to 36 carbon atoms include alkenylsuccinic acids such as dodecenylsuccinic acid, maleic acid, fumaric acid, citraconic acid, and mesaconic acid.
Examples of the alicyclic dicarboxylic acid having 6 to 40 carbon atoms include dimer acid (dimerized linoleic acid).
Examples of the aromatic dicarboxylic acid having 8 to 36 carbon atoms include phthalic acid, isophthalic acid, terephthalic acid, and naphthalenedicarboxylic acid.
Among these, preferred are alkane dicarboxylic acids having 4 to 36 carbon atoms, alkene dicarboxylic acids having 4 to 36 carbon atoms, aromatic dicarboxylic acids having 8 to 36 carbon atoms, and combinations of these. When an α,β-unsaturated carbonyl group is to be introduced into the molecule of a polyester resin, preferred are maleic acid, fumaric acid, and anhydrides and lower alkyl (having 1 to 4 carbon atoms) esters (methyl ester, ethyl ester, isopropyl ester, etc.) of these carboxylic acids.

Examples of trivalent or higher polycarboxylic acids (j) include aromatic polycarboxylic acids having 9 to 20 carbon atoms (e.g., trimellitic acid, pyromellitic acid), anhydrides of these carboxylic acids, and lower alkyl (having 1 to 4 carbon atoms) esters (e.g., methyl esters, ethyl esters, and isopropyl esters).

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

The polylactone polyol is not particularly limited, but examples thereof include polyaddition products of lactones with diols (g).

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

The polyester having a hydroxyl group can be produced by a known production method.
For example, the reaction can be carried out by reacting a polyol with a polycarboxylic acid in an inert gas (such as nitrogen gas) atmosphere. The reaction temperature is preferably 150 to 280° C., and the reaction time is preferably 30 minutes or more. It is also effective to reduce the pressure in order to improve the reaction rate at the end of the reaction.
In this case, an esterification catalyst can be used as necessary.
Esterification catalysts include tin-containing catalysts, antimony trioxide, titanium-containing catalysts, zirconium-containing catalysts, zinc acetate, and the like.
Specifically, the tin-containing catalyst may be dibutyltin oxide.
Examples of the titanium-containing catalyst include titanium alkoxides, potassium oxalate titanate, titanium terephthalate, the catalysts described in JP-A-2006-243715 (titanium dihydroxybis(triethanolaminate), titanium diisopropoxybistriethanolaminate, titanium monohydroxytris(triethanolaminate), and intramolecular polycondensates thereof, etc.), and the catalysts described in JP-A-2007-11307 (titanium tributoxyterephthalate, titanium triisopropoxyterephthalate, titanium diisopropoxyditerephthalate, etc.).
Zirconium-containing catalysts include zirconyl acetate.

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

Compounds having a chemical structure represented by general formula (1) and/or (2) include β-ketoester compounds and β-diester compounds, and one type may be used alone or two or more types may be used in combination.

Examples of β-ketoester compounds include ethyl acetoacetate, methyl acetoacetate, allyl acetoacetate, butyl acetoacetate, isopropyl acetoacetate, hexyl acetoacetate, octyl acetoacetate, decyl acetoacetate, and ethyl butyrylacetate.

Examples of β-diester compounds include dimethyl malonate, diethyl malonate, dibutyl malonate, dihexyl malonate, dioctyl malonate, diundecyl malonate, dihexadecyl malonate, di-9-octadecyl malonate, di-9,12-octadecadienyl malonate, and di-9,11,13-octadecatrienyl malonate.

Of the above, β-diester compounds are preferred from the standpoint of hot offset resistance and anti-static properties.

The weight percentage of the polyester resin used in the manufacturing process of the resin particles of the present invention is not particularly limited, but is preferably 5 to 30% by weight, and more preferably 6 to 20% by weight, based on the weight of the resin particles.

The polyester resin in the present invention preferably has a total of 0.10 mmol/g or more based on the weight of the polyester resin, the chemical structure portion represented by the general formula (1) and the chemical structure portion represented by the general formula (2). By using the above polyester resin, a toner having excellent hot offset resistance and chargeability can be obtained.
In addition, in the polyester resin of the present invention, the total amount of the chemical structural portion represented by the above general formula (1) and the chemical structural portion represented by the general formula (2) is more preferably 0.10 to 10 mmol/g, and even more preferably 0.2 to 5 mmol/g.
The total number (N) mmol/g of the chemical structural portion represented by the above general formula (1) and the chemical structural portion represented by the general formula (2) of the polyester resin can be calculated by the following formula.
N=number of moles (mol) of compound having a chemical structure represented by general formula (1) or (2)/weight (g) of all raw materials for polyester resin×1000

From the viewpoint of hot offset resistance and electrostatic chargeability, it is preferable that the polyester resin in the present invention satisfies the relationship of the following mathematical formula (1).
Number average molecular weight of polyester resin × number of moles (mol) of compound having a chemical structure represented by general formula (1) or (2) / weight (g) of all raw materials for polyester resin ≧ 0.5 (1)
The left side of the above formula (1) is the average number of the chemical structure portion of the polyester resin represented by the general formula (1) or (2) per molecule, and the higher this value, the more reactive points with the metal compound are. When the number of reactive points with the metal compound is increased, the molecular weight and crosslinking points of the reaction product between the polyester resin having the chemical structure portion represented by the general formula (1) and/or (2) and the metal compound are increased, so that the hot offset resistance is improved. In addition, it is more preferable to satisfy the relationship of formula (2), and it is even more preferable to satisfy the relationship of formula (3).
10≧number average molecular weight of polyester resin×number of moles (mol) of compound having a chemical structure represented by general formula (1) or (2)/weight (g) of all raw materials for polyester resin≧0.5 (2)
10≧number average molecular weight of polyester resin×number of moles (mol) of compound having a chemical structure represented by general formula (1) or (2)/weight (g) of all raw materials for polyester resin≧1 (3)
The average number of the chemical structure moieties represented by general formula (1) or (2) per molecule can be increased by increasing the amount of the raw material having the structure of (1) or (2) charged or by increasing the molecular weight, and can be decreased by decreasing the amount of the raw material having the structure of (1) or (2) charged or by decreasing the molecular weight.

In the present invention, the number average molecular weight (Mn) and the weight average molecular weight (Mw) can be measured by 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 removed by filtration using a glass filter)
Solution injection volume: 100μl
Detector: Refractive index detector Reference material: 12 types of standard polystyrene (TSKstandard 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 number average molecular weight (Mn) of the polyester resin is 1,000 to 10,000, preferably 1,500 to 8,000.

The weight average molecular weight (Mw) of the polyester resin is preferably 2,000 to 50,000, and more preferably 3,000 to 30,000.

The hydroxyl value of the polyester resin is preferably 20 to 80 mgKOH/g. The hydroxyl value can be measured according to the method specified in JIS K0070.

The glass transition temperature (Tg) of the polyester resin is preferably from -70 to 80°C, more preferably from -70 to 60°C, and further preferably from -50 to 50°C.
In the present invention, Tg can be measured by the method (DSC) specified in ASTM D3418-82 using "DSC20, SSC/580" [manufactured by Seiko Denshi Kogyo Co., Ltd.].

The polyester resin in the present invention can be obtained, for example, by reacting a polyester resin having a hydroxyl group with a compound having a chemical structure represented by general formula (1) and/or (2). The reaction method is not particularly limited, and examples of the reaction include an addition reaction, a condensation reaction, and an ester exchange reaction.

The metal compound in the present invention refers to a metal atom and its compound, and examples thereof include alkaline earth metals such as calcium and magnesium, transition metals such as titanium, chromium, cobalt, nickel, copper and zinc, and aluminum and their compounds. From the viewpoint of ease of coordination bonding with the polyester resin, the metal compound is preferably at least one selected from the group consisting of magnesium compounds, aluminum compounds, calcium compounds, titanium compounds, vanadium compounds, chromium compounds, manganese compounds, iron compounds, cobalt compounds, nickel compounds, copper compounds, zinc compounds and zirconium compounds, more preferably at least one selected from the group consisting of magnesium compounds, aluminum compounds, calcium compounds and zirconium compounds, even more preferably magnesium compounds and/or aluminum compounds, and particularly preferably at least one selected from the group consisting of magnesium chloride, magnesium sulfate, aluminum chloride, aluminum sulfate, polyaluminum chloride and polyaluminum hydroxide.

The weight ratio of the metal compound used in the manufacturing process of the resin particles of the present invention is not particularly limited, but is preferably 0.05 to 10% by weight, and more preferably 0.1 to 5% by weight, based on the weight of the resin particles.

In the method for producing resin particles of the present invention, the molar ratio [(S)/(T)] of the chemical structure portion (S) represented by general formula (1) and/or (2) of the polyester resin to the metal compound (T) is preferably 0.5 to 10 from the viewpoint of hot offset resistance.

In the method for producing resin particles of the present invention, other resins can be used in combination with the above polyester resins, metal compounds, etc. Any known resins can be used as the other resins, and specific examples thereof include polyester resins other than the above polyester resins, vinyl resins, polyurethane resins, epoxy resins, polyamide resins, polyimide resins, silicon resins, phenol resins, melamine resins, urea resins, aniline resins, ionomer resins, polycarbonate resins, etc.
Preferable examples of the other resins include polyester resins other than the above polyester resins, vinyl resins, polyurethane resins, epoxy resins, and combinations of these resins, and more preferably, combinations of polyester resins other than the above polyester resins and vinyl resins.

When the other resin is a polyester resin other than the above polyester resin, examples of the resin include amorphous polyester resin and crystalline polyester resin. A polycondensation product using the same polyol and polycarboxylic acid as those exemplified in the condensation type polyester polyol can be used, and the preferred polyol and polycarboxylic acid are the same as those in the condensation type polyester polyol. In the present invention, "amorphous" means that there is no peak top temperature of the endothermic peak when the transition temperature of the sample is measured using a differential scanning calorimeter.

When the other resin is a vinyl resin, the vinyl resin is a polymer obtained by homopolymerizing or copolymerizing a vinyl monomer. Examples of the vinyl monomer include the following (1) to (10).
(1) Vinyl Hydrocarbons Examples of the vinyl hydrocarbons include (1-1) aliphatic vinyl hydrocarbons, (1-2) alicyclic vinyl hydrocarbons, and (1-3) aromatic vinyl hydrocarbons.
(1-1) Aliphatic Vinyl Hydrocarbons Examples of the aliphatic vinyl hydrocarbons 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 Alicyclic vinyl hydrocarbons include mono- or di-cycloalkenes and alkadienes, and specific examples thereof include (di)cyclopentadiene and terpene.
(1-3) Aromatic Vinyl Hydrocarbons Examples of aromatic vinyl hydrocarbons include styrene and its hydrocarbyl (alkyl, cycloalkyl, aralkyl and/or alkenyl) substituted products, and specific examples thereof include α-methylstyrene, 2,4-dimethylstyrene, and vinylnaphthalene.

(2) Carboxylic Group-Containing Vinyl Monomer and Salts Thereof Examples of the carboxyl group-containing vinyl monomer and salts thereof include unsaturated monocarboxylic acids (salts), unsaturated dicarboxylic acids (salts), and anhydrides (salts), and monoalkyl (C1-24) esters or salts thereof, each having 3 to 30 carbon atoms.
Specific examples thereof include carboxyl group-containing vinyl monomers such as (meth)acrylic acid, (anhydride) maleic acid, maleic acid monoalkyl esters, fumaric acid, fumaric acid monoalkyl esters, crotonic acid, itaconic acid, itaconic acid monoalkyl esters, itaconic acid glycol monoether, citraconic acid, citraconic acid monoalkyl esters, and cinnamic acid, and metal salts thereof.

In the present invention, the term "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 Salts Thereof Examples of the sulfone group-containing vinyl monomers, vinyl sulfate monoesters, and salts thereof include alkene sulfonic acids (salts) having 2 to 14 carbon atoms, alkyl sulfonic acids (salts) having 2 to 24 carbon atoms, sulfo(hydroxy)alkyl-(meth)acrylates (salts) or (meth)acrylamides (salts), and alkylarylsulfosuccinic acids (salts).
Specifically, an example of an alkene sulfonic acid having 2 to 14 carbon atoms is vinyl sulfonic acid (salt), etc., an example of an alkyl sulfonic acid (salt) having 2 to 24 carbon atoms is α-methylstyrene sulfonic acid (salt), etc., and an example of a sulfo(hydroxy)alkyl-(meth)acrylate (salt) or (meth)acrylamide (salt) is sulfopropyl(meth)acrylate (salt), sulfuric acid ester (salt), or a sulfonic acid group-containing vinyl monomer (salt), etc.

(4) Phosphate-containing vinyl monomers and their salts:
Examples of the phosphoric acid group-containing vinyl monomer and its salt include (meth)acryloyloxyalkyl (C1 to C24) phosphoric acid monoester (salt) and (meth)acryloyloxyalkyl (C1 to C24) phosphonic acid (salt).
Specific examples of the (meth)acryloyloxyalkyl (C1 to C24) phosphate monoester (salt) include 2-hydroxyethyl (meth)acryloyl phosphate (salt) and phenyl-2-acryloyloxyethyl phosphate (salt).
Specific examples of the (meth)acryloyloxyalkyl (C1 to C24)phosphonic acid (salt) include 2-acryloyloxyethylphosphonic acid (salt).

Examples of the salts of (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.

(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.

(6) Nitrogen-Containing Vinyl Monomers Examples of the nitrogen-containing vinyl monomers include (6-1) amino group-containing vinyl monomers, (6-2) amide group-containing vinyl monomers, (6-3) nitrile group-containing vinyl monomers, (6-4) quaternary ammonium cation 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) Examples of the amide group-containing vinyl monomer include (meth)acrylamide and N-methyl(meth)acrylamide.
(6-3) Examples of nitrile group-containing vinyl monomers include (meth)acrylonitrile, cyanostyrene, and cyanoacrylate.
(6-4) Examples of the quaternary ammonium cation group-containing vinyl monomer include quaternized products of tertiary amine group-containing vinyl monomers such as dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylamide, diethylaminoethyl (meth)acrylamide, and diallylamine (which are quaternized with a quaternizing agent such as methyl chloride, dimethyl sulfate, benzyl chloride, or dimethyl carbonate).
(6-5) Nitro group-containing vinyl monomers include nitrostyrene and the like.

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

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

(9) Vinyl esters, vinyl (thio)ethers, vinyl ketones (9-1) Examples of 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 methoxyacetate, vinyl benzoate, ethyl α-ethoxyacrylate, and alkyl groups having 1 to 50 carbon atoms. alkyl(meth)acrylates having the formula (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 have 2 to 8 carbon atoms and may be linear, branched or dialkyl maleates (wherein the two alkyl groups are straight, branched or alicyclic groups having 2 to 8 carbon atoms); poly(meth)allyloxyalkanes (diallyloxyethane, triallyloxyethane, tetraallyloxyethane, tetraallyloxypropane, tetraallyloxybutane, tetramethallyloxyethane, etc.); vinyl monomers having polyalkylene glycol chains (polyethylene glycol (molecular weight 300) mono(meth)acrylate, polypropylene glycol (molecular weight 500) monoacrylate, etc.); acrylate, methyl alcohol ethylene oxide 10 mol adduct (meth)acrylate, lauryl alcohol ethylene oxide 30 mol adduct (meth)acrylate, etc.], poly(meth)acrylates [poly(meth)acrylates of polyhydric alcohols: 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) Examples of vinyl (thio)ethers include vinyl methyl ether.
(9-3) Examples of vinyl ketones include vinyl methyl ketone.

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

In the synthesis of the vinyl resin, the above vinyl monomers (1) to (10) may be used alone or in combination of two or more.
As the vinyl resin, from the viewpoints of particle size distribution and chargeability, styrene-(meth)acrylic acid ester copolymers and (meth)acrylic acid ester copolymers are preferred, and styrene-(meth)acrylic acid ester copolymers are more preferred.

In the method for producing resin particles of the present invention, the mixing ratio of the other resin is not particularly limited, but may be 0.01 to 80% by weight, and preferably 0.05 to 75% by weight, based on the weight of the resin particles. When the other resin is a polyester resin, it is preferably 50 to 80% by weight, and more preferably 60 to 75% by weight, based on the weight of the resin particles. When the other resin is a vinyl resin, it is preferably 0.01 to 10% by weight, and more preferably 0.05 to 2% by weight, based on the weight of the resin particles.

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

The colorant preferably contains at least one selected from the group consisting of a black colorant, a blue colorant, a red colorant and a yellow colorant. As the colorant, any dye, pigment or the like that is used as a toner colorant can be used.
Specific examples thereof include carbon black, iron black, Sudan Black SM, Fast Yellow G, Benzidine Yellow, Solvent Yellow (21, 77, 114, etc.), Pigment Yellow (12, 14, 17, 83, etc.), India Fast Orange, Irgasin Red, Paranitoaniline Red, Toluidine Red, Solvent Red (17, 49, 128, 5, 13, 22, 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, 15.3, etc.), Pigment Blue, Brilliant Green, Phthalocyanine Green, Oil Yellow GG, Kayaset YG, Orasol Brown B, and Oil Pink OP. If necessary, magnetic powder (powders of ferromagnetic metals such as iron, cobalt and nickel, and compounds such as magnetite, hematite and ferrite) may be contained to function as a colorant.
The content of the colorant is preferably 1 to 40 parts by weight, more preferably 2 to 15 parts by weight, per 100 parts by weight of the total of the polyester resin and other resins. When magnetic powder is used, the content of the magnetic powder is preferably 20 to 150 parts by weight, more preferably 30 to 120 parts by weight, per 100 parts by weight of the total of the polyester resin and other resins.

Examples of 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, oxidized polyethylene wax, oxidized polypropylene wax, 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.), and it is preferable to contain one or more types selected from the group consisting of these release agents. The content of the release agent is preferably 0 to 30% by weight, more preferably 0.5 to 20% by weight, and even more preferably 1 to 10% by weight, based on 100 parts by weight of the total of the polyester resin and other resins.

When using the above-mentioned release agent, modified wax may be used in combination if necessary. The modified wax is a release agent to which a vinyl polymer chain has been grafted. The release agents used in the modified wax include the same as those described above, and the preferred ones are also the same. Examples of the vinyl monomers constituting the vinyl polymer chain of the modified wax include styrene and methacrylic acid esters. The vinyl polymer chain may be a homopolymer or copolymer of a vinyl monomer. The content of the modified wax is preferably 0 to 15% by weight, more preferably 0.5 to 10% by weight, and even more preferably 1 to 5% by weight, based on 100 parts by weight of the polyester resin and other resins combined.

The charge control agent may contain either a positively charged charge control agent or a negatively charged charge control agent, and examples thereof include nigrosine dyes, triphenylmethane dyes containing a tertiary amine as a side chain, quaternary ammonium salts, polyamine resins, imidazole derivatives, polymers containing a quaternary ammonium base, metal-containing azo dyes, copper phthalocyanine dyes, metal salicylic acid salts, boron complexes of benzilic acid, polymers containing sulfonic acid groups, fluorine-containing polymers, and halogen-substituted aromatic ring-containing polymers. The content of the charge control agent may be 0 to 20% by weight, preferably 0.1 to 10% by weight, and more preferably 0.5 to 7.5% by weight, based on 100 parts by weight of the total of the polyester resin and other resins.

Examples of the fluidizing agent 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. From the viewpoint of the chargeability of the toner, silica is preferred. From the viewpoint of the transferability of the toner, the silica is preferably hydrophobic. The content of the fluidizing agent may be 0 to 10% by weight, preferably 0 to 5% by weight, and more preferably 0.1 to 4% by weight, based on 100 parts by weight of the total of the resin particles of the present invention.

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

As the aqueous medium in the present invention, any liquid containing water as an essential component can be used without limitation, and examples of the aqueous medium that can be used include water, an aqueous solution of an organic solvent, an aqueous solution of a surfactant (s), an aqueous solution of a water-soluble polymer (t), and mixtures thereof, as described below.
As a method for stably forming a dispersion containing a polyester resin in an aqueous medium, there may be mentioned a method in which the polyester resin is added to an aqueous medium and dispersed by shear force.
When the other resin is used, the polyester resin or the like and the other resin can be mixed in advance and dispersed in an aqueous medium, whereby the chemical structure portion represented by the general formula (1) and/or (2) in the polyester resin can be bonded to the metal compound in the presence of the other resin.
When other resins are used as fine particles, the fine particles of the resin are not particularly limited as long as they can form fine particles in an aqueous medium and can be adsorbed to the polyester resin.

The method for producing resin fine particles is not particularly limited, but includes the following methods [1] and [2].
[1] In the case of vinyl resins, a method of directly producing a dispersion of fine resin particles by a polymerization reaction such as suspension polymerization, emulsion polymerization, seed polymerization or 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, a precursor (monomer, oligomer, etc.) or a solvent solution thereof is dispersed in a medium in the presence of a suitable dispersant, and then heated or a curing agent is added to harden the precursor, thereby producing a fine particle dispersion of the resin.

In the above method [1] or [2], the emulsifier or dispersant used in combination may be a known surfactant (s) or a water-soluble polymer (t) as described below. In addition, an organic solvent or the like as described below may be used in combination as an emulsifying or dispersing aid.

Furthermore, when using the polyester resin of the present invention and other raw materials other than the metal compound and other resins (colorant, release agent, modified wax, charge control agent, etc.), the polyester resin, etc., other resin, and other raw materials can be mixed in advance and dispersed in an aqueous medium. In addition, in a state in which other raw materials are mixed in advance with the polyester resin or other resin, the metal compound can be bonded to the chemical structure portion represented by general formula (1) and/or (2) in the polyester resin. Mixing other toner raw materials in the resin in advance and bonding them makes it easier to disperse and fix the other raw materials in the resin, which is preferable from the viewpoint of particle size distribution and chargeability.
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 need to be mixed when forming particles in an aqueous medium, and may be added after forming the particles. For example, after forming particles not containing a colorant, a colorant may be added by a known dyeing method.

The dispersion method is not particularly limited, but known equipment such as low-speed shear type, high-speed shear type, friction type, high-pressure jet type, and ultrasonic type can be applied. A high-speed shear type is preferred in order to make the particle size of the dispersion 2 to 20 μm. When a high-speed shear type 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 in the case of a batch method, it is generally 0.1 to 5 minutes.
Examples of the dispersion device include batch-type emulsifiers such as Homogenizer (manufactured by IKA Corporation), Polytron (manufactured by Kinematica Corporation), and TK Auto Homo Mixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), Ebara Milder (manufactured by Ebara Corporation), TK Filmix, TK Pipeline Homo Mixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), colloid mills (manufactured by Kobe Steel Pantech Co., Ltd.), Ultra Visco Mill (manufactured by Imex Co., Ltd.), Slasher, and Trigonal wet fine grinding mills (manufactured by Mitsui Miike Kakoki Co., Ltd.), and the like. Examples of such emulsifiers include continuous emulsifiers such as Ebara Microfluidizer (manufactured by Ebara Microfluidizer Co., Ltd.), Capitron (manufactured by Eurotech Co., Ltd.), Fine Flow Mill (manufactured by Pacific Machinery Co., Ltd.), high pressure emulsifiers such as Microfluidizer (manufactured by Mizuho Kogyo Co., Ltd.), Nanomizer (manufactured by Nanomizer Co., Ltd.), APV Gaulin (manufactured by Gaulin Co., Ltd.), membrane emulsifiers such as Membrane Emulsifier (manufactured by Reika Kogyo Co., Ltd.), vibration type emulsifiers such as Vibro Mixer (manufactured by Reika Kogyo Co., Ltd.), ultrasonic emulsifiers such as Ultrasonic Homogenizer (manufactured by Branson Co., Ltd.), etc. Among these, from the viewpoint of particle size uniformity, APV Gaulin, homogenizer, TK Auto Homo Mixer, Ebara Milder, TK Filmix and TK Pipeline Homo Mixer are preferred.

The bonding of the chemical structural portion represented by general formula (1) and/or (2) in the polyester resin with the metal compound can be carried out by any known method as long as it includes a step of bonding in an aqueous medium, but a preferred method is to disperse the polyester resin in an aqueous medium, and after the formation of polyester resin particles, dissolve the metal compound in the aqueous medium to bond. From the viewpoint of hot offset resistance, the reaction temperature is preferably 5 to 200°C, more preferably 10 to 100°C, and even more preferably 15 to 60°C. The reaction time is preferably 1 to 48 hours, and even more preferably 2 to 24 hours. The reaction is carried out by heating after dispersion, but may be allowed to proceed partially before dispersion.

When dispersing the polyester resin of the present invention in an aqueous medium, the polyester resin is preferably liquid. If the polyester resin is solid at room temperature, it may be dispersed in a liquid state at a high temperature equal to or higher than the melting point, or an organic solvent solution of the polyester resin may be used. Using an organic solvent is preferable in that the particle size distribution is sharper.

Examples of the organic solvent include aromatic hydrocarbon solvents, aliphatic or alicyclic hydrocarbon solvents, halogenated solvents, ester or ester ether solvents, ether solvents, ketone solvents, alcohol solvents, amide solvents, sulfoxide solvents, heterocyclic compound solvents, and mixed solvents of two or more of these.
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.); halogenated solvents such as methyl chloride, methyl bromide, methyl iodide, methylene dichloride, carbon tetrachloride, trichloroethylene, and perchloroethylene; ester or ester ether solvents such as ethyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate, and ethyl cellosolve acetate; diethyl ether, tetrahydrofuran, dioxane, ethyl cellosolve, butyl ether ... Examples of the organic solvent include ether solvents such as Rosolve and propylene glycol monomethyl ether; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, di-n-butyl ketone and cyclohexanone; alcohol solvents such as 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, heterocyclic compound solvents such as N-methylpyrrolidone, and mixed solvents of two or more of these. 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.

When dispersing the polyester resin or the like in the present invention in an aqueous medium, a known surfactant (s) can be used as the emulsifier or dispersant used in combination. The use of a surfactant (s) is preferred in that it tends to reduce the volume average particle size of the resin particles.

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

Examples of the anionic surfactant (s-1) include carboxylic acids or their salts, sulfate salts, carboxymethyl salts, sulfonates, and phosphate salts.
Examples of the cationic surfactant (s-2) include quaternary ammonium salt type surfactants and amine salt type surfactants.
Examples of the amphoteric surfactant (s-3) include carboxylate-type amphoteric surfactants, sulfate-type amphoteric surfactants, sulfonate-type amphoteric surfactants, and phosphate-type amphoteric surfactants.
Examples of the nonionic surfactant (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 surfactant (s) used per 100 parts by weight of water as the aqueous medium 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.

When dispersing the polyester resin or the like in the present invention in an aqueous medium, a known water-soluble polymer (t) can be used as an emulsifier or dispersant to be used in combination. The use of a water-soluble polymer (t) is preferable in that the volume average particle size of the resin particles becomes smaller and the particle size distribution (volume average particle size/number average particle size) tends to become smaller.

Examples of the water-soluble polymer (t) include cellulose compounds (e.g., methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, ethylhydroxyethyl cellulose, carboxymethyl cellulose, hydroxypropyl cellulose, and saponified products thereof, etc.), gelatin, starch, dextrin, gum arabic, chitin, chitosan, polyvinyl alcohol, polyvinylpyrrolidone, polyethylene glycol, polyethyleneimine, polyacrylamide, acrylic acid (salt)-containing polymers (sodium polyacrylate, potassium polyacrylate, ammonium polyacrylate, partially neutralized polyacrylic acid with sodium hydroxide, and sodium acrylate-acrylic acid ester copolymers, etc.), partially neutralized styrene-maleic anhydride copolymers with sodium hydroxide, and water-soluble polyurethanes (polyethylene glycol, and reaction products of polycaprolactone diol, etc., with polyisocyanates, etc.).

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

The resin particles obtained by the manufacturing method of the present invention are a raw material for toner that is fixed to a support (paper, polyester film, etc.) by a copier, printer, etc. to become a recording material. As a method for fixing to a support, a known heat roll fixing method, flash fixing method, etc. can be used.

The resin particles obtained by the manufacturing method of the present invention are used in toner for developing electrostatic images or magnetic latent images in electrophotography, electrostatic recording, electrostatic printing, etc. More specifically, the present invention relates to a toner used for developing electrostatic images or magnetic latent images that is particularly suitable for full color.

The present invention will be described in detail below with reference to examples, but the present invention is not limited to these. In the following, parts refer to parts by weight.

<Production Example 1> [Production of Polyester Resin (A-1)]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen inlet tube, 439 parts of bisphenol A PO 2 mole adduct, 329 parts of bisphenol A PO 3 mole adduct, 56 parts of terephthalic acid, 90 parts of adipic acid, and 0.6 parts of titanium diisopropoxy bistriethanolamine as a condensation catalyst were placed, and the mixture was reacted for 10 hours under a reduced pressure of 0.5 to 2.5 kPa while gradually increasing the temperature to 230°C. It was confirmed that the acid value was less than 1 mgKOH/g, and a polyester having a hydroxyl group was obtained. Then, 100 parts of diethyl malonate was added, and the mixture was reacted at 150°C for 3 hours, and then the by-products were distilled off under a reduced pressure of 0.5 to 2.5 kPa to obtain a polyester resin (A-1).

<Production Examples 2 to 7> [Production of Polyester Resins (A-2) to (A-7)]
Into a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen inlet tube, the alcohol component, the carboxylic acid component, and the compound having a structure of general formula (1) or (2) shown in Table 1 were charged, and the reaction was carried out in the same manner as in Production Example 1, thereby obtaining polyester resins (A-2) to (A-7).

Comparative Production Example 1 Production of Polyester Resin (A'-1)
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen inlet tube, 884 parts of bisphenol A·PO 2 mole adduct, 196 parts of terephthalic acid and 0.6 parts of titanium diisopropoxy bistriethanolamine as a condensation catalyst were placed, and the mixture was reacted for 10 hours under a reduced pressure of 0.5 to 2.5 kPa while gradually increasing the temperature to 230°C. It was confirmed that the acid value was less than 1 mgKOH/g, and a polyester having a hydroxyl group was obtained. Then, 250 parts of ethyl acetoacetate was added, and the mixture was reacted at 150°C for 3 hours, and then the by-products were distilled off under a reduced pressure of 0.5 to 2.5 kPa to obtain polyester resin (A'-1).

Comparative Production Example 2 Production of Polyester Resin (A'-2)
In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen inlet tube, the alcohol component, the carboxylic acid component, and the compound having the structure of general formula (1) or (2) shown in Table 1 were charged, and the reaction was carried out in the same manner as in Comparative Production Example 1, to obtain a polyester resin (A'-2).

Comparative Production Example 3 Production of Polyester Resin (A'-3)
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen inlet tube, 508 parts of 3-methyl-1,5-pentanediol, 283 parts of terephthalic acid, 249 parts of adipic acid, and 0.6 parts of titanium diisopropoxy bistriethanolamine as a condensation catalyst were placed, and the mixture was reacted for 10 hours under a reduced pressure of 0.5 to 2.5 kPa while gradually increasing the temperature to 230°C. It was confirmed that the acid value was less than 1 mgKOH/g, and a polyester having a hydroxyl group was obtained. 1000 parts of the obtained polyester, 116 parts of isophorone diisocyanate (IPDI) and 884 parts of ethyl acetate were placed in an autoclave, and the reaction was carried out at 80°C for 10 hours in a sealed state, to obtain a solution of polyester resin (A'-3) containing an isocyanate group at the molecular end.

Table 1 shows the compositions of polyester resins (A-1) to (A-7) and (A'-1) to (A'-3), as well as the glass transition temperatures (Tg), number average molecular weights (Mn), and the left side of formula (1).

<Production Example 8> [Production of fine particle dispersion]
In a reaction vessel equipped with a stirring rod and a thermometer, 690.0 parts by weight of water, 9.0 parts by weight of sodium salt of polyoxyethylene monomethacrylate sulfate "Eleminol RS-30" [manufactured by Sanyo Chemical Industries, Ltd.], 90.0 parts by weight of styrene, 90.0 parts by weight of methacrylic acid, 110.0 parts by weight of butyl acrylate, and 1.0 parts by weight of ammonium persulfate were added and stirred at 350 rpm for 15 minutes, resulting in a white emulsion. The mixture was then heated to 75°C and reacted at the same temperature for 5 hours. Further, 30 parts by weight of a 1% by weight aqueous solution of ammonium persulfate was added, and the mixture was aged at 75°C for 5 hours to obtain a fine particle dispersion of a vinyl resin (a copolymer of styrene-methacrylic acid-butyl acrylate-sodium salt of ethylene oxide adduct sulfate ester).
The volume average particle size of the particles dispersed in the fine particle dispersion was measured using a laser diffraction/scattering type particle size distribution measuring device "LA-920" (manufactured by Horiba, Ltd.) and was found to be 0.1 μm.

<Production Example 9> [Production of colorant dispersion]
A reaction vessel equipped with a stirrer, a heating/cooling device, a thermometer, a cooling tube, and a nitrogen inlet tube was charged with 557 parts of propylene glycol, 569 parts of dimethyl terephthalate, 184 parts of adipic acid, and 3 parts of tetrabutoxy titanate as a condensation catalyst, and reacted for 8 hours under a nitrogen stream at 180 ° C. while distilling off the methanol produced. Then, while gradually increasing the temperature to 230 ° C., the reaction was carried out 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. The amount of propylene glycol recovered was 175 parts. Then, the mixture was cooled to 180 ° C., 121 parts of trimellitic anhydride was added, and the mixture was reacted for 2 hours under a sealed normal pressure, and then reacted at 220 ° C. and normal pressure until the softening point reached 180 ° C. to obtain a polyester (Mn = 8,500). 20 parts of copper phthalocyanine, 4 parts by weight of a colorant dispersant "Solsperse 28000" [manufactured by Avecia Corporation], 20 parts of the obtained polyester, and 56 parts of ethyl acetate were charged into a beaker and stirred to uniformly disperse the mixture. The copper phthalocyanine was then finely dispersed using a bead mill to obtain a colorant dispersion.

<Production Example 10> [Production of modified wax]
Into a pressure-resistant reaction vessel equipped with a stirrer, a heating/cooling device, a thermometer, and a dropping cylinder, 454 parts of xylene and 150 parts of low molecular weight polyethylene wax "Sanwax LEL-400" [softening point: 128°C, manufactured by Sanyo Chemical Industries, Ltd.] were charged, and after nitrogen replacement, the temperature was raised to 170°C with stirring, and 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 dropped at the same temperature over 3 hours, and the mixture was further maintained at the same temperature for 30 minutes. Next, xylene was distilled off under a reduced pressure of 0.039 MPa to obtain a modified wax.

<Production Example 11> [Production of release agent dispersion]
Into a reaction vessel equipped with a stirrer, a heating/cooling device, a cooling tube, and a thermometer, 10 parts of paraffin wax "HNP-9" [maximum peak temperature of heat of fusion: 73°C, manufactured by Nippon Seiro Co., Ltd.], 1 part of the modified wax obtained in Production Example 10, and 33 parts of ethyl acetate were charged, and the temperature was raised to 78°C while stirring. After stirring at the same temperature for 30 minutes, the mixture was cooled to 30°C over one hour to crystallize the paraffin wax into fine particles. The mixture was then wet-pulverized with Ultraviscomill (manufactured by Imex) to obtain a release agent dispersion.

<Production Example 12> [Production of amorphous polyester resin]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen inlet tube, 260 parts of bisphenol A·PO 2-mol adduct, 195 parts of bisphenol A·PO 3-mol adduct, 260 parts of bisphenol A·EO 2-mol adduct, 10 parts of trimethylolpropane, 255 parts of terephthalic acid, 45 parts of adipic acid, 0.6 parts of titanium diisopropoxy bistriethanolamine as a condensation catalyst, and reacted at 220° C. under a nitrogen stream while distilling off the water generated until the acid value was 20 or less, and then reacted for 10 hours under a reduced pressure of 0.5 to 2.5 kPa. Next, 30 parts by weight of trimellitic anhydride was added and held at 175° C. for 1 hour to obtain an amorphous polyester resin.

Example 1: Production of resin particles (D-1)
Into a beaker, 135 parts of ion-exchanged water, 0.5 parts of the [fine particle dispersion], 5 parts by weight of sodium carboxymethylcellulose, 34 parts of a 48.5 wt % aqueous solution of sodium dodecyl diphenyl ether disulfonate “Eleminol MON-7” [manufactured by Sanyo Chemical Industries, Ltd.], and 15 parts of ethyl acetate were placed, and the mixture was stirred to dissolve uniformly.
Next, 9 parts of polyester resin (A-1), 40 parts of [colorant dispersion], 40 parts of [release agent dispersion], 71 parts of [amorphous polyester resin], and 54 parts of ethyl acetate were added and stirred for 2 minutes at 10,000 rpm with a TK auto homomixer. Then, this mixed liquid was transferred to a reaction vessel equipped with a stirrer and a thermometer, and ethyl acetate was distilled off until the concentration was 0.5% by weight or less at 50 ° C., to obtain an aqueous resin dispersion of resin particles. Next, 0.5 parts of aluminum sulfate was added to the obtained aqueous dispersion, and the mixture was stirred at room temperature for 3 hours to react, then washed, filtered, 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) of the present invention.

<Examples 2 to 9> [Resin particles (D-2) to (D-9)]
Resin particles (D-2) were obtained in the same manner as in Example 1, except that the polyester resin (A-1) in Example 1 was changed to each of the polyester resins (A) shown in Table 2 and aluminum sulfate was changed to each of the metal compounds.

Comparative Example 1 Production of Resin Particles (D'-1)
Resin particles (D'-1) were obtained in the same manner as in Example 1, except that the polyester resin (A-1) was changed to (A'-1).

Comparative Example 2 Production of Resin Particles (D'-2)
Resin particles (D'-2) were obtained in the same manner as in Example 1, except that the polyester resin (A-1) in Example 1 was changed to the polyester resin (A'-2).

Comparative Example 3 Production of Resin Particles (D'-3)
Into a beaker, 135 parts of ion-exchanged water, 0.5 parts of the [fine particle dispersion], 5 parts by weight of sodium carboxymethylcellulose, 34 parts of a 48.5 wt % aqueous solution of sodium dodecyl diphenyl ether disulfonate “Eleminol MON-7” [manufactured by Sanyo Chemical Industries, Ltd.], and 15 parts of ethyl acetate were placed, and the mixture was stirred to dissolve uniformly.
Next, 18 parts of the polyester resin (A'-3) solution, 40 parts of the colorant dispersion, 40 parts of the release agent dispersion, 71 parts of the amorphous resin, 45 parts of ethyl acetate, and 0.13 parts of isophorone diamine were added and stirred for 2 minutes at 10,000 rpm with a TK auto homomixer. Then, this mixture was transferred to a reaction vessel equipped with a stirrer and a thermometer, and ethyl acetate was distilled off at 50°C until the concentration was 0.5% by weight or less, to obtain an aqueous resin dispersion of resin particles. The obtained aqueous dispersion was then washed, filtered, 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) of the present invention.

100 parts of resin particles (D-1) to (D-9) and (D'-1) to (D'-3) were mixed with 1 part of hydrophobic silica "Aerosil R972" [manufactured by Nippon Aerosil] as a flow agent in a sample mill, and the hot offset resistance, granulation properties, and charge properties were evaluated using the following methods. The evaluation results are shown in Table 2.

[Evaluation method]
The methods for measuring and evaluating the hot offset resistance, granulation property and electrostatic charge property will be described below, including the criteria for evaluation.

<Hot offset resistance (hot offset occurrence temperature)>
The resin particles after the external additive treatment are uniformly placed on the paper surface to a ^density of 0.8 mg/cm2. The method for placing the powder on the paper surface at this time is to use a printer without a heat fixing device. Other methods may be used as long as they can uniformly place the powder at the above weight density.
The temperature at which hot offset occurred was measured when this paper was passed through a pressure roller under conditions of a fixing speed (heat roller peripheral speed) of 213 mm/sec and a fixing pressure (pressure roller pressure) of 10 kg/cm ² .
Generally, a temperature of 170° C. or higher is considered to be preferable under these evaluation conditions.
◯: 170℃ or higher ×: Less than 170℃

<Granulation>
The resin particles after the external additive treatment were each dispersed in water, and the volume average particle size and particle size distribution were measured using a Coulter counter "Multisizer III" (manufactured by Beckman Coulter, Inc.) to evaluate the granulation properties.
Regarding the granulation property, it is considered preferable 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

<Electrostatic property>
0.5 g of the resin particles after the external additive treatment and 10 g of ferrite carrier (F-150, manufactured by Powder Tech Co., Ltd.) were placed in a 50 ml glass bottle, and the bottle was conditioned at 23°C and 50% relative humidity for 8 hours or more, and then friction-stirred with a Turbula shaker mixer at 90 rpm for 2 minutes. 0.2 g of the mixed powder after stirring was loaded into a blow-off powder charge amount measuring device equipped with a stainless steel wire mesh with a mesh size of 20 μm, and the charge amount of the remaining ferrite carrier was measured under conditions of a blow pressure of 10 KPa and a suction pressure of 5 KPa, and the charge amount (μC/g) of the resin particles was calculated by a standard method. Note that for toner, the higher the negative charge amount, the better the charging characteristics.
For the measurement, a blow-off charge amount measuring device (manufactured by Toshiba Chemica Co., Ltd.) was used.

[Judgment criteria]
◎: Less than -20 〇: Between -20 and -15 ×: Between -15 and -15

The resin particles of Examples 1 to 9 of the present invention exhibited excellent performance in all of hot offset resistance, particle size distribution and electrostatic chargeability.
On the other hand, resin particles (D'-1) using polyester resin (A'-1) having a number average molecular weight of less than 1000 exhibited poor offset resistance. Resin particles (D'-2) using polyester resin (A'-2) having a number average molecular weight of more than 10000 exhibited poor granulation properties. Resin particles (D'-3) using polyester resin (A'-3) not having a chemical structure represented by the above general formula (1) or (2) exhibited poor charging properties.

The polyester and resin particles of the present invention have excellent hot offset properties, granulation properties and chargeability, and are therefore extremely useful as a material for toners for developing electrostatic images used in electrophotography, electrostatic recording, electrostatic printing and the like.

Claims (4)

A method for producing resin particles, comprising a step of bonding, in an aqueous medium, the chemical structural portion of general formula (1) or (2) of a polyester resin having a number average molecular weight of 1,000 to 10,000 and a chemical structural portion represented by the following general formula (1) and/or (2):

[In general formulas (1) and (2), R ¹ represents a hydrogen atom or an alkyl group, and R ² each independently represents an alkylene group or an oxyalkylene group.] The method for producing resin particles according to claim 1, wherein the metal compound is at least one selected from the group consisting of magnesium compounds, aluminum compounds, calcium compounds, titanium compounds, vanadium compounds, chromium compounds, manganese compounds, iron compounds, cobalt compounds, nickel compounds, copper compounds, zinc compounds, and zirconium compounds. The method for producing resin particles according to claim 1 or 2, wherein the polyester resin satisfies the relationship of the following mathematical formula (1):
Number average molecular weight of polyester resin × number of moles (mol) of compound having a chemical structure represented by general formula (1) or (2) / weight (g) of all raw materials for polyester resin ≧ 0.5 (1) The method for producing resin particles according to any one of claims 1 to 3, wherein a molar ratio [(S)/(T)] of the chemical structure portion (S) of the polyester resin represented by the general formula (1) and/or (2) to the metal compound (T) is 0.5 to 10.