Polyester resin for toner and toner

Abstract

To provide: a polyester resin for toner that has low environmental load and is superior in hygrothermal stability during storage and low-temperature fixability; and a toner.SOLUTION: A polyester resin is composed of a polycondensate formed from a carboxylic acid component and an alcohol component. The carboxylic acid component includes a cyclic dicarboxylic acid having at least one selected from a terpene group and a hydrogenated terpene group as a cyclic skeleton, or an anhydride thereof, or an alkyl ester thereof, and the alcohol component includes a diol.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a polyester resin for toner and a toner.

Background Art

[0002] In recent years, from the perspective of environmental protection such as global warming suppression, a shift from conventional petroleum-derived plastics to biomass-derived plastics with less environmental impact has been actively pursued. For example, the Japan BioPlastics Association certifies plastics products with a ratio of biomass-derived components in the biomass plastic composition contained in raw materials and products of 25% by mass or more as "Biomass Plastics" and authorizes the use of the defined certification mark. Also, for toners, those using biomass raw materials are desired, and for the binder resins constituting toners, those using biomass raw materials are desired.

[0003] As a polyester resin with low environmental impact, Patent Document 1 proposes a polyester resin obtained by adding natural wax such as rice wax during polymerization. Also, Patent Document 2 proposes a polyester resin obtained by polycondensing a polyhydric alcohol containing plant-derived 1,3-propanediol and a polyvalent carboxylic acid.

[0004] However, when introducing natural wax into the resin as in Patent Document 1, the glass transition temperature of the resulting polyester resin decreases. Therefore, when further increasing the biomass content and applying it to toners, it is impossible to obtain a toner with sufficient storage stability. Also, when using 1,3-propanediol with a low molecular weight and terephthalic acid as the main components as in Cited Document 2, the ester group concentration and polarity of the resulting polyester resin increase, and under high temperature and high humidity conditions, there is a problem that the storage stability decreases and the dispersibility of the low-polarity wax and crystalline polyester resin contained in the toner deteriorates.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0006] An object of the present invention is to provide a polyester resin for toner and a toner that have a low environmental impact and excellent wet heat storage stability and low temperature fixing properties.

Means for Solving the Problems

[0007] As a result of intensive studies to solve these problems, the present inventor has reached the present invention. That is, the present invention is A polyester resin obtained by polycondensing a carboxylic acid component and an alcohol component, wherein the carboxylic acid component contains at least one selected from a terpene group and a hydrogenated terpene group as a cyclic skeleton, a cyclic dicarboxylic acid or an anhydride thereof or an alkyl ester thereof, and the alcohol component contains a diol, and a toner containing the polyester resin for toner.

Effects of the Invention

[0008] According to the present invention, it is possible to provide a polyester resin for toner and a toner that have a low environmental impact and excellent wet heat storage stability and low temperature fixing properties.

Modes for Carrying Out the Invention

[0009] Hereinafter, the polyester resin for toner and the toner of the present invention will be described. The polyester resin for toner of the present invention is a polyester resin obtained by polycondensing a carboxylic acid component and an alcohol component, wherein the carboxylic acid component contains at least one selected from terpene groups and hydrogenated terpene groups as a cyclic skeleton, in the form of a cyclic dicarboxylic acid or an anhydride thereof or an alkyl ester thereof, and the alcohol component contains a diol.

[0010] As the carboxylic acid component constituting the polyester resin for toner of the present invention, a cyclic dicarboxylic acid having at least one selected from terpene groups and hydrogenated terpene groups as a cyclic skeleton, or an anhydride thereof or an alkyl ester thereof is included. The above cyclic dicarboxylic acid or its anhydride is generally synthesized by a cyclization addition reaction of terpenes with an unsaturated dicarboxylic acid and / or an unsaturated acid anhydride. Also, the alkyl ester of the above cyclic dicarboxylic acid or its anhydride can be synthesized by using an alkyl ester of terpenes and an unsaturated dicarboxylic acid and / or an unsaturated acid anhydride as raw materials for the above cyclization addition reaction. Alternatively, it can also be obtained by an esterification reaction using a cyclic dicarboxylic acid or its anhydride and an alcohol as raw materials and using an appropriate reagent. The terpenes are not particularly limited, but specifically, α-terpinene, d-limonene, felandrene, alloocimene, camphene, terpinolene, terpineol, carvone, etc. (all of which are available as commercially available reagents) can be used. The terpenes may be used alone or in combination of two or more.

[0011] The above unsaturated dicarboxylic acid and / or unsaturated acid anhydride are not particularly limited, but specifically, fumaric acid, maleic anhydride, maleic acid, phthalic anhydride, phthalic acid, etc. (all of which are available as commercially available reagents) can be used. The unsaturated dicarboxylic acid and / or unsaturated acid anhydride may be used alone or in combination of two or more. Specific examples of the above alkyl esters include dimethyl maleate, diethyl maleate, dibutyl maleate, dimethyl fumarate, diethyl fumarate, dibutyl fumarate, etc.

[0012] Regarding the terpene group of the cyclic dicarboxylic acid having a terpene group as a cyclic skeleton, its anhydride, or their alkyl esters obtained by the above cycloaddition reaction, it may be hydrogenated if necessary.

[0013] Further, as the carboxylic acid component, dicarboxylic acids, monocarboxylic acids, and polycarboxylic acids having a valence of 3 or more other than the above may be further contained. Examples of the dicarboxylic acids other than the above include alkanedicarboxylic acids having 2 to 50 carbon atoms (e.g., oxalic acid, malonic acid, succinic acid, adipic acid, pimelic acid, and sebacic acid, etc.), alkenedicarboxylic acids having 4 to 50 carbon atoms (e.g., maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, and glutaconic acid, etc.), and aromatic dicarboxylic acids having 8 to 36 carbon atoms (e.g., phthalic acid, isophthalic acid, terephthalic acid, and naphthalenedicarboxylic acid, etc.). In addition, acid anhydrides and lower alkyl (having 1 to 4 carbon atoms) esters (e.g., methyl ester, ethyl ester, and isopropyl ester, etc.) of these dicarboxylic acids may be used. The dicarboxylic acid may be used alone or in combination of two or more.

[0014] Examples of the monocarboxylic acid include aliphatic monocarboxylic acids and aromatic monocarboxylic acids, etc. The monocarboxylic acid may be used alone or in combination of two or more. Examples of the aliphatic monocarboxylic acid include chain saturated monocarboxylic acids, chain unsaturated monocarboxylic acids, and alicyclic monocarboxylic acids, etc. Examples of the chain saturated monocarboxylic acid include linear or branched chain saturated monocarboxylic acids having 2 to 30 carbon atoms (e.g., acetic acid, propionic acid, butyric acid, valeric acid, 2-ethylhexanoic acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, pentadecylic acid, palmitic acid, margaric acid, stearic acid, tuberculostearic acid, arachidic acid, behenic acid, and lignoceric acid, etc.). Examples of the chain unsaturated monocarboxylic acid include linear or branched chain unsaturated monocarboxylic acids having 3 to 30 carbon atoms (for example, acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, palmitoleic acid, oleic acid, vaccenic acid, linoleic acid, α-linolenic acid, γ-linolenic acid, eleostearic acid, 8,11-eicosadienoic acid, 5,8,11-eicosatrienoic acid, arachidonic acid, stearidonic acid, eicosapentaenoic acid, docosapentaenoic acid, docosahexaenoic acid, dihomo-γ-linolenic acid, elaidic acid, erucic acid, nervonic acid, etc.). Examples of the alicyclic monocarboxylic acid include alicyclic monocarboxylic acids having 4 to 14 carbon atoms (for example, cyclopropanecarboxylic acid, cyclobutanecarboxylic acid, cyclopentanecarboxylic acid, cyclohexanecarboxylic acid, cycloheptanecarboxylic acid, etc.). Examples of the aromatic monocarboxylic acid include aromatic monocarboxylic acids having 7 to 36 carbon atoms, specifically, benzoic acid, vinylbenzoic acid, toluic acid, dimethylbenzoic acid, t-butylbenzoic acid, cumic acid, naphthoic acid, biphenylmonocarboxylic acid, phthalic acid, etc. In addition, acid anhydrides and lower alkyl (having 1 to 4 carbon atoms) esters (for example, methyl ester, ethyl ester, isopropyl ester, etc.) of these monocarboxylic acids may be used.

[0015] Examples of the polycarboxylic acid having a valence of 3 or more include aromatic polycarboxylic acids having 9 to 20 carbon atoms (trimellitic acid, pyromellitic acid, etc.) and aliphatic (including alicyclic) tricarboxylic acids having 6 to 36 carbon atoms (hexanetricarboxylic acid, decanetricarboxylic acid, etc.). In addition, as the polycarboxylic acid having a valence of 3 or more, acid anhydrides and lower alkyl (having 1 to 4 carbon atoms) esters (for example, methyl ester, ethyl ester, isopropyl ester, etc.) of the above-mentioned ones may be used. The polycarboxylic acid having a valence of 3 or more may be used alone or in combination of two or more.

[0016] The alcohol component constituting the polyester resin for toner of the present invention contains a diol. Examples of the diol include aliphatic diols and aromatic diols. The diol may be used alone or in combination of two or more kinds. Examples of the aliphatic diol include chain aliphatic diols and alicyclic aliphatic diols. Examples of the chain aliphatic diol include alkylene glycols having 2 to 30 carbon atoms (e.g., ethylene glycol, 1,2-propanediol (propylene glycol), 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, octanediol, decanediol, dodecanediol, tetradecanediol, neopentyl glycol, 2,2-diethyl-1,3-propanediol, etc.); alkylene ether glycols (e.g., diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.); polylactone diols (e.g., poly-ε-caprolactone diol, etc.); polybutadiene diols; polyester diols; and polycarbonates, polyisoprene polyols, hydrogenated polyisoprene polyols, etc. Examples of the alicyclic aliphatic diol include alicyclic diols having 6 to 24 carbon atoms (e.g., 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); AO adducts (addition mole number: 2 to 100) of the alicyclic diol [e.g., EO 10 mole adduct of 1,4-cyclohexanedimethanol, etc.] Examples of the aromatic diol include AO (EO, PO, BO, etc.) adducts (addition mole number: 2 to 100) of bisphenols (bisphenol A, bisphenol F, bisphenol S, etc.) (e.g., bisphenol A·EO adduct (addition mole number: 2 to 4 moles) and bisphenol A·PO adduct (addition mole number: 2 to 4 moles), etc.).

[0017] Furthermore, as the alcohol component, in addition to the above-mentioned diol, a monoalcohol and a polyol having a valency of 3 or more may be included. Examples of the monoalcohol include aliphatic monoalcohols and aromatic monoalcohols. The monoalcohol may be used alone or in combination of two or more thereof. Examples of the aliphatic monoalcohol include chain saturated monoalcohols and chain unsaturated monoalcohols. Examples of the chain saturated monoalcohol include linear or branched chain saturated monoalcohols having 1 to 30 carbon atoms (for example, methanol, ethanol, 1-propyl alcohol, isopropyl alcohol, butanol, pentanol, 2-methyl-1-butanol, 2,2-dimethyl-1-propanol, hexanol, 4-methyl-1-pentanol, 2,3-dimethyl-2-butanol, heptanol, 3-ethyl-3-pentanol, octanol, 2-ethyl-1-hexanol, nonanol, 2,6-dimethyl-4-heptanol, decanol, undecanol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, etc.), and those obtained by adding an alkylene oxide having 2 to 4 carbon atoms (hereinafter, may be abbreviated as "AO") to the linear or branched chain saturated monoalcohol having 1 to 30 carbon atoms [for example, ethylene oxide (hereinafter, may be abbreviated as "EO"), propylene oxide (hereinafter, may be abbreviated as "PO"), butylene oxide (hereinafter, may be abbreviated as "BO"), etc.] (the addition mole number is 1 to 20 moles), etc. Examples of the chain unsaturated monoalcohol include linear or branched chain unsaturated monoalcohols having 2 to 30 carbon atoms (for example, allyl alcohol, 2-buten-1-ol, 2-penten-1-ol, 2-hexen-1-ol, 2-hepten-1-ol, 2-octen-1-ol, 2-nonen-1-ol, 2-decen-1-ol, 2-dodecenol, palmitoleyl alcohol, oleyl alcohol, linoleyl alcohol, etc.), and those obtained by adding an AO having 2 to 4 carbon atoms (for example, EO, PO, BO, etc.) to the linear or branched chain unsaturated monoalcohol having 2 to 30 carbon atoms (the addition mole number is 1 to 20 moles), etc. Examples of the aromatic monohydric alcohol include aromatic monohydric alcohols having 6 to 30 carbon atoms (such as aromatic aliphatic alcohols (e.g., benzyl alcohol, etc.)), and those obtained by adding AO having 2 to 4 carbon atoms (e.g., EO, PO, and BO, etc.) to the aromatic monohydric alcohol having 6 to 30 carbon atoms (the number of moles of addition being 1 to 20 moles), etc.

[0018] Examples of the polyhydric alcohol having a valence of 3 or more include polyhydric aliphatic alcohols having a valence of 3 or more and 3 to 36 carbon atoms, AO adducts of polyhydric aliphatic alcohols (the number of moles of addition being 2 to 120), AO adducts of tris-phenols (such as tris-phenol PA, etc.) (the number of moles of addition being 2 to 30), AO adducts of novolak resins (such as phenol novolak, cresol novolak, etc.) (the number of moles of addition being 2 to 30), acrylic polyols [such as copolymers of hydroxyethyl (meth)acrylate and other vinyl monomers, etc.], etc. Examples of the polyhydric aliphatic alcohols having a valence of 3 or more and 3 to 36 carbon atoms include alkane polyols and their intramolecular or intermolecular dehydrates, and saccharides (such as sucrose, etc.) and their methyl glucosides, etc. Specific examples of the alkane polyols and their intramolecular or intermolecular dehydrates include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, sorbitan, and polyglycerin, etc.

[0019] The cyclic dicarboxylic acid, or their anhydrides or their alkyl esters are preferably compounds represented by the following formula (1) and / or (2) from the viewpoints of moisture and heat resistance storage stability and low temperature fixing property.

Chemical formula

Chemical formula

[0020] The total weight ratio of the cyclic dicarboxylic acid or its anhydride or their alkyl esters is preferably 10 to 100% by weight based on the total weight of the carboxylic acid component from the viewpoints of moisture and heat resistance storage stability and low-temperature fixability.

[0021] The polyester resin for toner of the present invention contains amorphous polyester, and may further contain crystalline polyester. Note that "amorphous" means that when measuring the transition temperature of a sample using a differential scanning calorimeter, there is no peak top temperature of the endothermic peak.

[0022] The polyester resin for toner of the present invention can be produced in the same manner as the known production method of polyester resin. For example, the alcohol component and the carboxylic acid component can be subjected to polycondensation reaction in an atmosphere of an inert gas (such as nitrogen gas) at a reaction temperature preferably of 150 to 280°C, more preferably 160 to 250°C, and still more preferably 170 to 235°C. The reaction time is preferably 30 minutes or more, more preferably 2 to 40 hours, from the viewpoint of ensuring the polycondensation reaction. It is also effective to reduce the pressure to improve the reaction rate at the end stage of the reaction.

[0023] The polyester resin for toner of the present invention can be produced by subjecting the alcohol component and the carboxylic acid component to condensation polymerization in the presence of a catalyst. Examples of the catalyst include tin-containing catalysts (such as dibutyltin oxide), antimony trioxide, titanium-containing catalysts [such as titanium alkoxides (titanium tetrabutoxide), potassium titanyl oxalate, titanium terephthalate, titanium alkoxide terephthalate, catalysts described in JP-A-2006-243715 {titanium diisopropoxybis(triethanolamineate), titanium dihydroxybis(triethanolamineate), titanium monohydroxytri(triethanolamineate), titanyl bis(triethanolamineate) and their intramolecular polycondensates, etc.} and catalysts described in JP-A-2007-11307 (titanium tributoxyterephthalate, titanium triisopropoxyterephthalate, titanium diisopropoxyditerephthalate, etc.)], zirconium-containing catalysts (such as zirconyl acetate), zinc acetate, and the like. Among these catalysts, titanium-containing catalysts are preferred, and more preferably, the catalysts described in JP-A-2006-243715 and the catalysts described in JP-A-2007-11307.

[0024] The SP value of the polyester resin for toner of the present invention is 10.0 to 11.5 (cal / cm 3 ) 1 / 2 preferably, and more preferably 10.2 to 11.4 (cal / cm 3 ) 1 / 2 . If the SP value is within the above range, the compatibility with the crystalline polyester becomes good, and the low-temperature fixability is excellent. The SP value is the solubility parameter and is calculated by the method described in the following document proposed by Fedors et al. The SP values of the polyester resin for toner (amorphous polyester) and the crystalline polyester of the present invention can be calculated by obtaining the SP value of the structure in which the hydroxyl group is removed from the alcohol component and the hydrogen of the carboxyl group is removed from the carboxylic acid component used, and performing additive averaging based on the molar fraction. "POLYMER ENGINEERING AND SCIENCE, FEBRUARY, 1974, Vol. 14, No. 2, ROBERT F. FEDORS. (pages 147 - 154)" In addition, the SP value of the polyester resin for toner of the present invention and the crystalline polyester described later refers to the SP value of the structure excluding the functional groups at the terminals.

[0025] The glass transition temperature (hereinafter abbreviated as Tg) of the polyester resin for toner of the present invention is preferably 20 to 90°C, more preferably 40 to 80°C. If it is 20°C or higher, it has excellent moisture and heat resistance storage properties, and if it is 90°C or lower, there is little inhibition to low-temperature fixing properties.

[0026] The acid value of the polyester resin for toner of the present invention is preferably 0 to 75 mgKOH / g, more preferably 7 to 24 mgKOH / g.

[0027] The hydroxyl value of the polyester resin for toner of the present invention is preferably 0 to 120 mgKOH / g, more preferably 3 to 70 mgKOH / g.

[0028] The number average molecular weight (hereinafter may be abbreviated as Mn) of the polyester resin for toner of the present invention is preferably 1,000 to 1,000,000, more preferably 2,000 to 8,000.

[0029] The weight average molecular weight (hereinafter may be abbreviated as Mw) of the polyester resin for toner of the present invention is preferably 4,000 to 10,000,000, more preferably 4,000 to 15,000.

[0030] The polyester resin for toner of the present invention can contain a binder resin. Examples of the binder resin include other polyester resins, polyurethane resins, styrene resins, and epoxy resins. As the other polyester resin used as the binder resin, a crystalline polyester obtained by polycondensing a component containing an alcohol component and a carboxylic acid component can be used. "Crystalline" means that in differential scanning calorimetry (also referred to as DSC measurement), the DSC curve has a peak top temperature (melting point) of an endothermic peak. Examples of the alcohol component include diols and polyols having three or more hydroxyl groups, and examples of the carboxylic acid component include dicarboxylic acids and polycarboxylic acids having three or more carboxyl groups.

[0031] Examples of the diol include linear aliphatic diols having 2 to 20 carbon atoms (such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,15-pentadecanediol, 1,18-octadecanediol, 1,19-nonadecanediol, and 1,20-eicosanediol), alicyclic diols having 6 to 36 carbon atoms (such as 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 sometimes abbreviated as "AO") adducts of the above alicyclic diols), and aromatic diols (such as 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, 2,2'-diethylbisphenol F, and alkylene oxide adducts of the above aromatic diols).

[0032] Examples of polyols with a valence of 3 or higher include polyhydric aliphatic alcohols (alkane polyols and their intramolecular or intermolecular dehydration products, such as glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, sorbitan, and polyglycerin, saccharides and their esterified products, such as sucrose, and methyl glucoside, etc.), AO adducts of tris-phenols (such as tris-phenol PA, etc.) (the number of added moles is 2 to 30), AO adducts of novolak resins (such as phenol novolak, cresol novolak, etc.) (the number of added moles is 2 to 30), and acrylic polyols [copolymers of hydroxyethyl (meth)acrylate and other vinyl monomers, etc.].

[0033] Examples of dicarboxylic acids include linear aliphatic dicarboxylic acids having 2 to 50 carbon atoms (such as succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, and 1,18-octadecanedicarboxylic acid, etc.), alicyclic dicarboxylic acids having 8 to 36 carbon atoms (such as 1,4-cyclohexanedicarboxylic acid, etc.), and aromatic dicarboxylic acids having 8 to 36 carbon atoms (such as phthalic acid, isophthalic acid, and terephthalic acid, etc.).

[0034] Examples of polycarboxylic acids with a valence of 3 or higher include aromatic polycarboxylic acids having 9 to 20 carbon atoms (such as trimellitic acid and pyromellitic acid, etc.).

[0035] The reaction ratio between the alcohol component and the carboxylic acid component, expressed as the molar ratio of the hydroxyl group to the carboxyl group {[OH] / [COOH]}, is preferably 1 / 2 to 2 / 1, more preferably 1 / 1.3 to 1.5 / 1, and even more preferably 1 / 1.2 to 1.4 / 1. The above hydroxyl group is the hydroxyl group derived from the alcohol component.

[0036] The crystalline polyester can be produced in the same manner as the known polyester production methods, similar to the toner polyester resin of the present invention.

[0037] The SP value of the crystalline polyester is 10.0 to 11.5 (cal / cm 3 ) 1 / 2is preferably, more preferably 10.0 to 11.2 (cal / cm 3 ) 1 / 2 and even more preferably 10.0 to 11.0 (cal / cm 3 ) 1 / 2 . If the SP value is within the above range, the compatibility with the polyester resin for toner of the present invention is good, and the low-temperature fixability is excellent.

[0038] The melting point (Tm) of the crystalline polyester is 60 to 100 °C, preferably 65 to 95 °C, and more preferably 65 to 85 °C.

[0039] The viscosity of the crystalline polyester at 100 °C is preferably 10 to 10,000 mPa·s, and more preferably 400 to 7,000 mPa·s.

[0040] The heat absorption amount of the crystalline polyester is preferably 5 to 101.5 J / g, and more preferably 40 to 101.2 J / g.

[0041] The acid value of the crystalline polyester is preferably 0 to 75 mgKOH / g, and more preferably 1 to 35 mgKOH / g.

[0042] The hydroxyl value of the crystalline polyester is preferably 0 to 120 mgKOH / g, and more preferably 5 to 21 mgKOH / g.

[0043] The number average molecular weight of the crystalline polyester (hereinafter may be abbreviated as Mn) is preferably 1,000 to 1,000,000, and more preferably 2,000 to 50,000.

[0044] The weight average molecular weight of the crystalline polyester (hereinafter may be abbreviated as Mw) is preferably 8,000 to 10,000,000, and more preferably 6,000 to 15,000.

[0045] The weight ratio of the polyester resin for toner to the crystalline polyester in the present invention [amorphous polyester: crystalline polyester] is preferably from 97:3 to 70:30, more preferably from 95:5 to 85:15.

[0046] The above polyester resin for toner constitutes resin particles. The content of the polyester resin for toner in the resin particles is preferably 30 to 97% by weight, more preferably 42 to 96% by weight, still more preferably 50 to 95% by weight based on the weight of the resin particles.

[0047] If necessary, the resin particles can be mixed with various additives such as known resin fine particles, colorants, release agents, charge control agents, fluidizing agents and the like.

[0048] The resin fine particles are not particularly limited as long as they are resins capable of forming an aqueous dispersion in an aqueous medium, and can be appropriately selected from known resins according to the purpose. They may be thermoplastic resins or thermosetting resins. For example, vinyl resins, polyurethane resins, epoxy resins, polyester resins, polyamide resins, polyimide resins, silicone resins, phenolic resins, melamine resins, urea resins, aniline resins, ionomer resins and polycarbonate resins and the like can be mentioned. These may be used alone or in combination of two or more. Among these, vinyl resins, polyurethane resins, epoxy resins and polyester resins are particularly preferred in that an aqueous dispersion of fine spherical resin particles is easily obtained. The vinyl resin is a polymer obtained by homopolymerizing or copolymerizing vinyl monomers. For example, styrene-(meth)acrylate copolymer, styrene-butadiene copolymer, (meth)acrylic acid-acrylate copolymer, styrene-(meth)acrylate-(meth)acrylic acid copolymer, styrene-acrylonitrile copolymer, styrene-maleic anhydride copolymer, styrene-(meth)acrylic acid copolymer, and styrene-styrene sulfonic acid-(meth)acrylate copolymer and the like can be mentioned. The vinyl resin is preferably a styrene-alkyl (meth)acrylate copolymer, a styrene-alkyl (meth)acrylate-(meth)acrylic acid copolymer, and an alkyl (meth)acrylate copolymer from the viewpoints of low-temperature fixing property, heat-resistant storage stability, and ease of obtaining an aqueous dispersion of fine spherical resin particles. More preferably, it is a styrene-alkyl (meth)acrylate and a styrene-alkyl (meth)acrylate-(meth)acrylic acid copolymer.

[0049] In addition, as the resin fine particles, a copolymer containing a monomer having at least two unsaturated groups as a constituent monomer can also be used. The monomer having at least two unsaturated groups is not particularly limited and can be appropriately selected according to the purpose. Examples thereof include divinylbenzene and 1,6-hexanediol diacrylate. The content of the resin fine particles is preferably 0.1 to 10% by weight based on the weight of the resin particles.

[0050] The resin fine particles are not particularly limited and can be obtained by polymerization according to a known method appropriately selected according to the purpose. However, it is preferable to obtain them as an aqueous dispersion of the resin fine particles. As a method for preparing the aqueous dispersion of the resin fine particles, for example, (1) In the case of the vinyl resin, a method of directly producing an aqueous dispersion of resin fine particles by any polymerization reaction selected from suspension polymerization, emulsion polymerization, seed polymerization, and dispersion polymerization using a vinyl monomer as a starting material. (2) In the case of polyaddition or condensation resins such as the polyester resin, polyurethane resin, and epoxy resin, after dispersing a precursor (monomer, oligomer, etc.) or its solvent solution in an aqueous medium in the presence of a suitable dispersant, heating or adding a curing agent to cure it to produce an aqueous dispersion of resin fine particles. (3) In the case of polyaddition or condensation resins such as the polyester resin, polyurethane resin, and epoxy resin, after dissolving a suitable emulsifier in a precursor (monomer, oligomer, etc.) or its solvent solution (preferably a liquid, which may be liquefied by heating), adding water to perform phase inversion emulsification. (4) A method of obtaining resin fine particles by pulverizing a resin prepared in advance by a polymerization reaction (which may be any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) using a pulverizer such as a mechanical rotation type or jet type, and then classifying, and then dispersing the resin fine particles in water in the presence of a suitable dispersant. (5) A method of obtaining resin fine particles by spraying a resin solution in which a resin prepared in advance by a polymerization reaction (which may be any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) is dissolved in a solvent in a mist form, and then dispersing the resin fine particles in water in the presence of a suitable dispersant. (6) A method of precipitating resin fine particles by adding a poor solvent to a resin solution in which a resin prepared in advance by a polymerization reaction (which may be any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) is dissolved in a solvent, or by cooling a resin solution previously dissolved in a solvent by heating, then removing the solvent to obtain resin particles, and then dispersing the resin particles in water in the presence of a suitable dispersant. (7) A polymerization reaction in advance (any polymerization A method of removing a solvent by heating, reduced pressure, etc. after dispersing a resin solution in which a resin prepared by a reaction mode may be used) in a solvent in an aqueous medium in the presence of a suitable dispersant. (8) A method such as adding water and carrying out phase inversion emulsification after dissolving a suitable emulsifier in a resin solution in which a resin prepared in advance by a polymerization reaction (which may be any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) is dissolved in a solvent is preferably mentioned.

[0051] As the colorant, it is preferably contained 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 (such as 21, 77, and 114), Pigment Yellow (such as 12, 14, 17, and 83), Indanthrene Fast Orange, Irgasin Red, Para Nitroaniline Red, Toluidine Red, Solvent Red (such as 17, 49, 128, 5, 13, 22, and 48:2), Disperse Red, Carmine FB, Pigment Orange R, Lake Red 2G, Rhodamine FB, Rhodamine B Lake, Methyl Violet B Lake, Phthalocyanine Blue, Solvent Blue (such as 25, 94, 60, and 15:3), Pigment Blue, Brilliant Green, Phthalocyanine Green, Oil Yellow GG, Kayaset YG, Orazole Brown B, Oil Pink OP, etc. can be mentioned. Further, if necessary, magnetic powder (powders of ferromagnetic metals such as iron, cobalt, and nickel, compounds such as magnetite, hematite, and ferrite) can be contained having a 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, based on 100 parts by weight in total of the polyester resin for toner of the present invention. When using magnetic powder, the content of the magnetic powder is preferably 20 to 150 parts by weight, more preferably 30 to 120 parts by weight, based on 100 parts by weight in total of the polyester resin for toner.

[0052] Examples of the release agent include natural waxes (such as beeswax, carnauba wax, and montan wax), petroleum waxes (such as paraffin wax, microcrystalline wax, and petrolatum), synthetic waxes (such as Fischer-Tropsch wax, polyethylene wax, polypropylene wax, oxidized polyethylene wax, and oxidized polypropylene wax), and synthetic ester waxes (such as 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 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, still more preferably 1 to 10% by weight, based on 100 parts by weight in total of the polyester resin for toner of the present invention.

[0053] When using the above release agent, a modified wax may be used in combination if necessary. The modified wax is one in which a vinyl polymer chain is grafted onto the release agent. Examples of the release agent used for the modified wax include the same ones as the above release agent, and preferred ones are also the same. Examples of the vinyl monomer constituting 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 the vinyl monomer. The content of the modified wax is preferably 0 to 15% by weight, more preferably 0.5 to 10% by weight, and still more preferably 1 to 5% by weight based on 100 parts by weight in total of the polyester resin for toner of the present invention.

[0054] As the charge control agent, either a positively chargeable charge control agent or a negatively chargeable charge control agent may be contained. For example, nigrosine dyes, triphenylmethane dyes containing a tertiary amine as a side chain, quaternary ammonium salts, polyamine resins, imidazole derivatives, quaternary ammonium um salt-containing polymers, metal-containing azo dyes, copper phthalocyanine dyes, metal salts of salicylic acid, boron complexes of benzoic acid, sulfonic acid group-containing polymers, fluorine-containing polymers, halogen-substituted aromatic ring-containing polymers, etc. may be mentioned. 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 in total of the polyester resin for toner of the present invention.

[0055] 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. Silica is preferred from the viewpoint of the chargeability of the toner. Also, silica is preferably hydrophobic silica from the viewpoint of the transferability of the toner. 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 in total of the polyester resin for toner of the present invention.

[0056] In addition, the total weight of additives such as colorants, release agents, charge control agents, fluidizing agents, etc. may be 3 to 70% by weight, preferably 4 to 58% by weight, more preferably 5 to 50% by weight based on the weight of the resin particles.

[0057] The volume average particle diameter (D50) of the resin particles is preferably 1 to 15 μm, more preferably 2 to 10 μm, and particularly preferably 3 to 7 μm. By setting it within the above range, the low-temperature fixability becomes good.

[0058] There are no particular restrictions on the method for producing the resin particles, and known kneading and pulverizing methods, suspension polymerization methods described in Japanese Patent Publication No. 36-10231, Japanese Patent Laid-Open No. 59-53856, and Japanese Patent Laid-Open No. 59-61842, emulsion polymerization methods typified by soap-free polymerization methods in which monomers are directly polymerized in the presence of a water-soluble polymerization initiator soluble in the monomers to produce toner, interfacial polymerization methods such as microcapsule production methods, in site polymerization methods, coacervation methods, emulsion aggregation methods in which at least one or more fine particles are aggregated as disclosed in Japanese Patent Laid-Open No. 62-106473 and Japanese Patent Laid-Open No. 63-186253 to obtain those with a desired particle size, dispersion polymerization methods characterized by monodispersity, dissolution suspension methods in which resins necessary for a water-insoluble organic solvent are dissolved and then resin particles are formed in water, or ester extension polymerization methods may be used, or they may be produced by a method of dispersing in supercritical carbon dioxide.

Examples

[0059] Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited thereto. Hereinafter, unless otherwise specified, "parts" indicates parts by weight.

[0060] The crystalline polyester resin and amorphous polyester resin contained in the polyester resin for toner, as well as each physical property value of toner, etc. were measured by the following methods.

[0061] [Measurement Method] <Melting Point (Tm)> Using a differential scanning calorimeter (DSC Q20 manufactured by TA Instruments Co., Ltd.), the first heating was performed from 30°C to 180°C at a rate of 10°C / min, followed by cooling from 180°C to 0°C at a rate of 10°C / min, and then the second heating was performed from 0°C to 180°C at a rate of 10°C / min. The temperature at the top of the endothermic peak during the second heating process was defined as the melting point.

[0062] <Endothermic quantity> Under the same measurement conditions as the measurement of the melting point above, for the DSC curve of the second heating process observed, a straight line was drawn connecting the point on the baseline closest to the peak below the endothermic start temperature of the endothermic peak and the point on the baseline closest to the peak above the end temperature of the endothermic peak, and the endothermic quantity at the endothermic peak having the peak top temperature of the endothermic peak was calculated.

[0063] <Acid value and hydroxyl value> Measured by the method specified in JIS K0070. However, the measurement solvent for the acid value was a mixed solvent of acetone, methanol, and toluene (acetone:methanol:toluene = 12.5:12.5:75), and the measurement solvent for the hydroxyl value was THF.

[0064] <Number average molecular weight (Mn) and weight average molecular weight (Mw)> The resin was dissolved in tetrahydrofuran (THF), and this was used as a sample solution. It was measured using gel permeation chromatography (GPC) under the following conditions. Apparatus: HLC-8120 [manufactured by Tosoh Corporation] Column: Two TSK GEL GMH6 [manufactured by Tosoh Corporation] Measurement temperature: 40°C Sample solution: 0.25 wt% THF solution (insoluble matter filtered off with a glass filter) Solution injection volume: 100 μL Detector: Refractive index detector Reference substance: Standard polystyrene (TSKstandard POLYSTYRENE)

[0065] <Glass transition temperature (Tg)> Measurement was performed using a differential scanning calorimeter (DSC Q20 manufactured by TA Instruments Co., Ltd.) according to the method specified in ASTM D3418-82 (DSC method). The measurement conditions for the glass transition temperature are as follows (1) Heating from 30 °C to 150 °C at a rate of 20 °C / min (2) Holding at 150 °C for 10 minutes (3) Cooling from 150 °C to -35 °C at a rate of 20 °C / min (4) Holding at -35 °C for 10 minutes (5) Heating from -35 °C to 150 °C at a rate of 20 °C / min (6) The differential scanning calorimetry curve measured during the process of (5) was analyzed to determine the glass transition temperature.

[0066] <Solid content concentration and volatile content of the dispersion> Taking care not to cause precipitation of resin particles or resin fine particles, 2.00 g of the sample before drying was weighed, dried at 120 °C for 1 hour, the sample after drying was taken out and weighed to the second decimal place, and the solid content concentration (weight %) was calculated from (weight of the sample after drying / weight of the sample before drying) × 100, and the volatile content (weight %) was calculated from {(weight of the sample before drying - weight of the sample after drying) / weight of the sample before drying} × 100.

[0067] <Volume-based median diameter of the resin fine particle dispersion> The volume-based median diameter of the resin fine particles was measured using a dynamic light scattering particle size distribution measuring device "SZ-100" (manufactured by Horiba, Ltd.). The resin fine particle dispersion was diluted 100-fold with ion-exchanged water, the temperature was adjusted to 25 °C, and then filled into a disposable cell (transparent on all four sides). Next, the measurement mode was set to the particle size measurement mode, and the volume-based median diameter was measured.

[0068] <Volume average particle diameter (D50) (μm), number average particle diameter (μm), and particle size distribution (volume average particle diameter / number average particle diameter) of the resin particles> Measurement was performed using a Coulter counter [product name: Multisizer III (manufactured by Beckman Coulter, Inc.)]. First, 0.1 to 5 mL of a surfactant (alkylbenzene sulfonate) as a dispersant was added to 100 to 150 mL of ISOTON-II (manufactured by Beckman Coulter), which is an electrolytic aqueous solution. Further, 2 to 20 mg of the measurement sample was added, and the electrolytic solution in which the sample was suspended was subjected to dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes. Using a 50-μm aperture as an aperture, the volume and number of resin particles were measured with the said measuring device, and the volume distribution and number distribution were calculated. From the obtained distributions, the volume average particle diameter (D50) (μm), number average particle diameter (μm), and particle size distribution (volume average particle diameter / number average particle diameter) of the resin particles were determined.

[0069] <Production Example 1> [Synthesis of Fumarated α-Terpinene] 420 parts of α-terpinene and 286 parts of fumaric acid were charged into a 1-L autoclave equipped with an electromagnetic stirring device, and the temperature was raised while stirring, followed by reaction at 170 to 180 °C for 12 hours. After the reaction, unreacted α-terpinene was distilled off under reduced pressure to obtain 560 parts of fumarated α-terpinene.

[0070] <Production Example 2> [Synthesis of Hydrogenated Fumarated α-Terpinene] 250 parts of the fumarated terpinene obtained above, 493 parts of 2-propanol, and 2.5 parts of a powdery 5% palladium-carbon catalyst were charged into a 1-L autoclave equipped with an electromagnetic stirring device. Then, this was sealed, and after replacing the atmosphere with nitrogen gas, hydrogen gas was introduced while applying a pressure of 15 kg / cm 2 When stirring was started, the internal temperature rose from 27 °C to 32 °C. The reaction was carried out for 4 hours while maintaining the pressure at 15 to 20 kg / cm 2 by supplementing the absorbed hydrogen. Thereafter, the obtained suspension was subjected to suction filtration with a Buchner funnel to filter off the catalyst. Then, the filtrate was concentrated under reduced pressure to obtain 243 parts of hydrogenated fumarated α-terpinene.

[0071] <Production Example 3> [Synthesis of Maleated α-Terpinene Anhydride] In a reaction vessel equipped with a stirrer, a heating and cooling device, and a thermometer, 256 parts by weight of maleic anhydride was charged. After melting at 145°C, 6 parts by weight of p-toluenesulfonic acid was added and homogenized at 300 revolutions per minute. While maintaining the temperature at 145°C, 500 parts by weight of α-pinene was added dropwise over 0.5 hours and then reacted at 145°C for 3 hours. The resulting brown viscous liquid was distilled under reduced pressure (7 mmHg), and the fraction distilling at 225°C was collected to obtain 549 parts of α-terpinene maleic anhydride.

[0072] <Production Example 4> [Synthesis of Amorphous Polyester (L-1)] Into a reaction tank equipped with a condenser, a stirrer, and a nitrogen inlet tube, 246 parts of propylene glycol, 666 parts of fumarated α-terpinene obtained in Production Example 1, 59 parts of succinic acid, and 2.5 parts of titanium dihydroxybis(triethanolamineate) as a condensation catalyst were placed. While heating under a reduced pressure of 0.5 to 2.5 kPa up to 200°C, water generated was distilled off while reacting. When the acid value became less than 2 mg KOH / g, 29 parts of trimellitic anhydride was added, and the reaction was further carried out under a reduced pressure of 0.5 to 2.5 kPa. When the acid value reached 18 mg KOH / g, it was taken out to obtain amorphous polyester (L-1).

[0073] <Production Example 5> [Synthesis of Amorphous Polyester (L-2)] Into a reaction tank equipped with a condenser, a stirrer, and a nitrogen inlet tube, 259 parts of propylene glycol, 652 parts of α-terpinene maleic anhydride obtained in Production Example 3, 62 parts of succinic acid, and 2.5 parts of p-toluenesulfonic acid as a condensation catalyst were placed. While heating under a reduced pressure of 0.5 to 2.5 kPa up to 200°C, water generated was distilled off while reacting. When the acid value became less than 2 mg KOH / g, 27 parts of trimellitic anhydride was added, and the reaction was further carried out under a reduced pressure of 0.5 to 2.5 kPa. When the acid value reached 18 mg KOH / g, it was taken out to obtain amorphous polyester (L-2).

[0074] <Production Example 6> [Synthesis of Amorphous Polyester (L-3)] Into a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen inlet pipe, 245 parts of propylene glycol, 668 parts of hydrogenated fumarated α-terpinene obtained in Production Example 2, 58 parts of succinic acid, and 2.5 parts of titanium dihydroxybis(triethanolamine) as a condensation catalyst were charged. While raising the temperature under a reduced pressure of 0.5 to 2.5 kPa up to 200°C, the reaction was carried out while distilling off the generated water. When the acid value became less than 2 mgKOH / g, 29 parts of trimellitic anhydride were added, and the reaction was further carried out under a reduced pressure of 0.5 to 2.5 kPa. When the acid value reached 18 mgKOH / g, it was taken out to obtain an amorphous polyester (L-3).

[0075] <Production Example 7>[Synthesis of Amorphous Polyester (L-4)] Into a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen inlet pipe, 562 parts of bisphenol A·EO2 molar adduct, 408 parts of fumarated α-terpinene obtained in Production Example 1, and 2.5 parts of titanium dihydroxybis(triethanolamine) as a condensation catalyst were charged. While raising the temperature under a reduced pressure of 0.5 to 2.5 kPa up to 200°C, the reaction was carried out while distilling off the generated water. When the acid value became less than 2 mgKOH / g, 30 parts of trimellitic anhydride were added, and the reaction was further carried out under a reduced pressure of 0.5 to 2.5 kPa. When the acid value reached 18 mgKOH / g, it was taken out to obtain an amorphous polyester (L-4).

[0076] <Production Example 8>[Synthesis of Amorphous Polyester (L-5)] Into a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen inlet pipe, 647 parts of bisphenol A·EO2 molar adduct, 37 parts of fumarated α-terpinene obtained in Production Example 1, 287 parts of terephthalic acid, and 2.5 parts of titanium dihydroxybis(triethanolamine) as a condensation catalyst were charged. While raising the temperature under a reduced pressure of 0.5 to 2.5 kPa up to 200°C, the reaction was carried out while distilling off the generated water. When the acid value became less than 2 mgKOH / g, 29 parts of trimellitic anhydride were added, and the reaction was further carried out under a reduced pressure of 0.5 to 2.5 kPa. When the acid value reached 18 mgKOH / g, it was taken out to obtain an amorphous polyester (L-5).

[0077] <Production Example 9>[Synthesis of Amorphous Polyester (L-6)] Into a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen inlet tube, 596 parts of bisphenol A·EO2 molar adduct, 9 parts of trimethylolpropane, 184 parts of fumarated α-terpinene obtained in Production Example 1, 181 parts of terephthalic acid, and 2.5 parts of titanium dihydroxybis(triethanolamineate) as a condensation catalyst were charged. While raising the temperature under a reduced pressure of 0.5 to 2.5 kPa up to 200 °C, the reaction was carried out while distilling off the generated water. When the acid value became less than 2 mgKOH / g, 29 parts of trimellitic anhydride were added, and the reaction was further carried out under a reduced pressure of 0.5 to 2.5 kPa. When the acid value reached 18 mgKOH / g, it was taken out to obtain amorphous polyester (L-6).

[0078] <Production Example 10>[Synthesis of Amorphous Polyester (L-7)] Into a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen inlet tube, 26 parts of propylene glycol, 506 parts of bisphenol A·EO2 molar adduct, 438 parts of fumarated α-terpinene obtained in Production Example 1, and 2.5 parts of titanium dihydroxybis(triethanolamineate) as a condensation catalyst were charged. While raising the temperature under a reduced pressure of 0.5 to 2.5 kPa up to 200 °C, the reaction was carried out while distilling off the generated water. When the acid value became less than 2 mgKOH / g, 30 parts of trimellitic anhydride were added, and the reaction was further carried out under a reduced pressure of 0.5 to 2.5 kPa. When the acid value reached 18 mgKOH / g, it was taken out to obtain amorphous polyester (L-7).

[0079] <Production Example 11>[Synthesis of Amorphous Polyester (L-8)] Into a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen inlet pipe, 162 parts of ethylene glycol, 120 parts of neopentyl glycol, 9 parts of trimethylolpropane, 325 parts of fumarated α-terpinene obtained in Production Example 1, 356 parts of terephthalic acid, and 2.5 parts of titanium dihydroxybis(triethanolamineate) as a condensation catalyst were charged. While heating under reduced pressure of 0.5 to 2.5 kPa up to 200 °C, the reaction was carried out while distilling off the generated water. When the acid value became less than 2 mgKOH / g, 27 parts of trimellitic anhydride were added, and further, the reaction was carried out under reduced pressure of 0.5 to 2.5 kPa. When the acid value reached 18 mgKOH / g, it was taken out to obtain an amorphous polyester (L-8).

[0080] <Comparative Production Example 1>[Synthesis of Comparative Amorphous Polyester (LR-1)] Into a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen inlet pipe, 381 parts of propylene glycol, 534 parts of terephthalic acid, 61 parts of succinic acid, and 2.5 parts of titanium dihydroxybis(triethanolamineate) as a condensation catalyst were charged. While heating under reduced pressure of 0.5 to 2.5 kPa up to 230 °C, the reaction was carried out while distilling off the generated water. When the acid value became less than 2 mgKOH / g, 25 parts of trimellitic anhydride were added, and further, the reaction was carried out under reduced pressure of 0.5 to 2.5 kPa. When the acid value reached 18 mgKOH / g, it was taken out to obtain an amorphous polyester (LR-1).

[0081] <Comparative Production Example 2>[Synthesis of Comparative Amorphous Polyester (LR-2)] Into a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen inlet pipe, 677 parts of bisphenol A·EO2 molar adduct, 294 parts of terephthalic acid, and 2.5 parts of titanium dihydroxybis(triethanolamineate) as a condensation catalyst were charged. While heating under reduced pressure of 0.5 to 2.5 kPa up to 230 °C, the reaction was carried out while distilling off the generated water. When the acid value became less than 2 mgKOH / g, 29 parts of trimellitic anhydride were added, and further, the reaction was carried out under reduced pressure of 0.5 to 2.5 kPa. When the acid value reached 18 mgKOH / g, it was taken out to obtain an amorphous polyester (LR-2).

[0082] Table 1 shows the compositions and physical properties of the amorphous polyesters (L-1) to (L-8) obtained in Production Examples 4 to 11 and the comparative crystalline polyesters (LR-1) to (LR-2) obtained in Comparative Production Examples 1 to 2.

[0083]

Table 1

[0084] <Production Example 12> [Synthesis of Crystalline Polyester (C-1)] Into a reaction vessel equipped with a stirrer, a heating and cooling device, a thermometer, a condenser, and a nitrogen inlet tube, 434 parts of 1,6 - hexanediol, 686 parts of sebacic acid, and 1.5 parts of titanium diisopropoxybis(triethanolamineate) as a condensation catalyst were charged, and the mixture was reacted at 220 °C for 8 hours while distilling off the water generated under a nitrogen stream. Then, the reaction was carried out while removing water under a reduced pressure of 0.001 to 0.026 MPa to obtain a crystalline polyester (C-1). The Mn of the resin was 4500, Mw was 15000, the melting point (Tm) was 68 °C, the heat absorption amount was 101.1 J / g, the acid value was 1 mgKOH / g, the hydroxyl value was 21 mgKOH / g, and the SP value was 10.0 (cal / cm 3 ) 1 / 2 It was. The SP value in the present invention was calculated by the method by Fedors [Polym. Eng. Sci. 14(2) 152, (1974)].

[0085] <Production Example 13> [Production of Crystalline Polyester Dispersion (CDO-1)] Into a reaction vessel equipped with a condenser, a stirrer, a heating and cooling device, and a thermometer, 10 parts of crystalline polyester (C-1) and 90 parts of ethyl acetate were charged, the temperature was raised to 78 °C, and the mixture was stirred at the same temperature for 3 hours. Then, it was cooled to 30 °C over 1 hour to crystallize the crystalline polyester (C-1) in the form of fine particles, and further wet - ground with an ultraviscomill (manufactured by Imex) to obtain a crystalline polyester dispersion (CDO-1). The volume - based median diameter of the crystalline polyester dispersion (CDO-1) measured by "LA-920" was 0.25 μm.

[0086] <Production Example 14>[Production of Aqueous Dispersion of Resin Fine Particles (OW-1)] Into a reaction vessel equipped with a stirrer, a heating and cooling device, and a thermometer, 790 parts of water and 5 parts of sodium alkyl allyl sulfosuccinate (manufactured by Sanyo Chemical Industries, Ltd., Eminol JS-20) were charged and stirred at 200 revolutions per minute for homogenization. This was heated to raise the temperature of the system to 75 °C, and after adding 5 parts of a 10% aqueous ammonium persulfate solution, a monomer mixture consisting of 89.6 parts of styrene, 49.0 parts of butyl acrylate, and 61.4 parts of methacrylic acid was added dropwise over 2 hours. After the dropwise addition, it was aged at 75 °C for 10 hours to obtain 1000 parts of a fine particle dispersion (OW-1) containing resin fine particles. The median diameter of the fine particles contained in the fine particle dispersion was 0.047 μm on a volume basis. Also, a part of the fine particle dispersion was dried to isolate the resin. The Mn of the resin component was 30900, the Mw was 321000, the Tg was 60 °C, and the acid value was 200 mgKOH / g.

[0087] <Production Example 15>[Production of Modified Wax (WD-1)] Into a pressure-resistant reaction vessel equipped with a stirring device, a heating and cooling device, a thermometer, and a dropping funnel, 454 parts by weight of xylene and 150 parts by weight of low molecular weight polyethylene "Sun Wax LEL-400" [softening point: 128 °C, manufactured by Sanyo Chemical Industries, Ltd.] were charged. After nitrogen substitution, the temperature was raised to 170 °C with stirring, and at the same temperature, a mixed solution of 595 parts by weight of styrene, 255 parts by weight of methyl methacrylate, 34 parts by weight of di-t-butyl peroxyhexahydroterephthalate, and 119 parts by weight of xylene was added dropwise over 3 hours and further held at the same temperature for 30 minutes. Then, xylene was distilled off under a reduced pressure of 0.039 MPa to obtain a modified wax. The SP value of the graft chain of the modified wax was 10.35 (cal / cm 3 ) 1 / 2 , the Mn was 1,900, the Mw was 5,200, and the Tg was 56.9 °C.

[0088] <Production Example 16>[Production of Release Agent Dispersion (WO-1)] Into a reaction vessel equipped with a cooling pipe, a stirrer, a heating and cooling device, and a thermometer, 10 parts of paraffin wax "HNP-9" [maximum heat of fusion peak temperature: 73°C, manufactured by Nippon Seiro Co., Ltd.], 5 parts of the modified wax (WD-1) obtained in Production Example 15, and 85 parts of ethyl acetate were charged. The temperature was raised to 78°C and stirred at the same temperature for 3 hours, then cooled to 30°C over 1 hour to crystallize the release agent in fine particles, and further wet-milled with an ultraviscosity mill (manufactured by Imex) to obtain a release agent dispersion (WO-1). The volume-based median diameter of the release agent dispersion (WO-1) measured with "LA-920" was 0.25 μm.

[0089] <Production Example 17> [Production of Colorant Dispersion (PO-1)] Into a reaction vessel equipped with a stirring device, a heating and cooling device, a cooling pipe, and a thermometer, 20 parts of carbon black "MA100" [manufactured by Mitsubishi Chemical Corporation], 4 parts of a colorant dispersant "Solsperse 28000" [manufactured by Avecia Co., Ltd.], and 56 parts of ethyl acetate were charged. After stirring to uniformly disperse, the pigment was finely dispersed by a bead mill to obtain a colorant dispersion (PO-1). The volume-based median diameter of the colorant dispersion (PO-1) measured with "LA-920" was 0.2 μm.

[0090] <Example 1> [Production of Toner (T-1)] Using the aqueous dispersion (OW-1) obtained in Production Example 14, the amorphous polyester (L-1) obtained in Production Example 4, the colorant dispersion (PO-1) obtained in Production Example 17, the release agent dispersion (WO-1) obtained in Production Example 16, and the crystalline polyester dispersion (CDO-1) obtained in Production Example 13, toner (T-1) was obtained by the following method (dissolution suspension method). 330 parts of ion-exchanged water, 30 parts of an aqueous dispersion of resin fine particles (OW-1), 2 parts of sodium carboxymethyl cellulose, 52 parts of sodium dodecyl diphenyl ether disulfonic acid “Eleminol Mon-7” [manufactured by Sanyo Chemical Industries, Ltd.], and 28 parts of ethyl acetate were put into a beaker, and an aqueous solution was obtained by uniformly mixing them. Next, 90 parts of amorphous polyester (L-1), 32 parts of a colored dispersion (PO-1), 40 parts of a mold release agent dispersion (WO-1), and 100 parts of a crystalline polyester dispersion (CDO-1) were mixed in another beaker to prepare a resin dispersion in which the amorphous polyester was dissolved. The entire amount of this dispersion was added to the aqueous solution prepared above, and the mixture was stirred with a TK autohomomixer for 2 minutes to obtain a mixed solution. Next, this mixed solution was transferred to a reactor equipped with a stirrer and a thermometer, and ethyl acetate was distilled off at 50°C until the concentration became 0.5% by weight or less to perform a complexing step, and an aqueous resin dispersion of resin particles was obtained. Next, the resin particles were filtered and washed with water three times, then filtered off, and dried in a hot air circulation dryer at 40°C for 18 hours to obtain resin particles containing the polyester resin (L-1) for toner of the present invention with a volatile content of 0.5% by weight or less. Then, 100 parts of the resin particles and 1 part of hydrophobic silica “Aerosil R-972” [manufactured by Nippon Aerosil Co., Ltd.] were mixed with a sample mill to obtain the toner (T-1) of the present invention.

[0091] <Example 2> [Manufacture of Toner (T-2)] It was manufactured in the same manner as in Example 1 except that the amorphous polyester was changed to the amorphous polyester (L-2) obtained in Production Example 5, and a toner (T-2) containing the polyester resin (L-2) for toner of the present invention was obtained.

[0092] <Example 3> [Manufacture of Toner (T-3)] It was manufactured in the same manner as in Example 1 except that the amorphous polyester was changed to the amorphous polyester (L-3) obtained in Production Example 6, and a toner (T-3) containing the polyester resin (L-3) for toner of the present invention was obtained.

[0093] <Example 4> [Manufacture of Toner (T-4)] It was produced in the same manner as in Example 1 except that the amorphous polyester was changed to the amorphous polyester (L-4) obtained in Production Example 7, and a toner (T-4) containing the polyester resin (L-4) for toner of the present invention was obtained.

[0094] <Example 5> [Production of Toner (T-5)] It was produced in the same manner as in Example 1 except that the amorphous polyester was changed to the amorphous polyester (L-5) obtained in Production Example 8, and a toner (T-5) containing the polyester resin (L-5) for toner of the present invention was obtained.

[0095] <Example 6> [Production of Toner (T-6)] It was produced in the same manner as in Example 1 except that the amorphous polyester was changed to the amorphous polyester (L-6) obtained in Production Example 9, and a toner (T-6) containing the polyester resin (L-6) for toner of the present invention was obtained.

[0096] <Example 7> [Production of Toner (T-7)] It was produced in the same manner as in Example 1 except that the amorphous polyester was changed to the amorphous polyester (L-7) obtained in Production Example 10, and a toner (T-7) containing the polyester resin (L-7) for toner of the present invention was obtained.

[0097] <Example 8> [Production of Toner (T-8)] It was produced in the same manner as in Example 1 except that the amorphous polyester was changed to the amorphous polyester (L-8) obtained in Production Example 11, and a toner (T-8) containing the polyester resin (L-8) for toner of the present invention was obtained.

[0098] <Comparative Example 1> [Production of Toner (TR-1)] It was produced in the same manner as in Example 1 except that the amorphous polyester was changed to the amorphous polyester (LR-1) obtained in Comparative Production Example 1, and a toner (TR-1) containing the polyester resin (LR-1) for toner of the present invention was obtained.

[0099] <Comparative Example 2> [Production of Toner (TR-2)] The toner polyester resin (LR-2) of the present invention was used to produce a toner (TR-2) in the same manner as in Example 1, except that the amorphous polyester was changed to the amorphous polyester (LR-2) obtained in Comparative Production Example 2.

[0100] The low-temperature fixability and moisture and heat resistance storage stability of the toners (T-1) to (T-8) and (TR-1) to (TR-2) in the examples and comparative examples were evaluated by the following methods. The blending amounts, physical properties, and evaluation results of each toner are shown in Table 2.

[0101]

Table 2

[0102] <Low-temperature fixability> The toner is uniformly placed on the paper surface so that it becomes 0.8 mg / cm. 2 At this time, as long as the powder can be uniformly placed on the paper surface with the above weight density, other methods may be used. The method used is a printer with the heat fixing unit removed. The paper is 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 The occurrence temperature (MFT) of cold offset when passing through was measured. The lower the occurrence temperature of cold offset, the better the low-temperature fixability. Under these evaluation conditions for low-temperature fixability, 115°C or lower is preferably used. ◎: 105°C or lower ○: 106 - 115°C △: 116 - 125°C ×: 126°C or higher

[0103] <Moisture and heat resistance storage stability> The toners (T-1) to (T-8), (TR-1) to (TR-2) were allowed to stand in an atmosphere of 40°C and 80% relative humidity for 20 hours, and the moisture and heat resistance storage stability was evaluated according to the following criteria based on the degree of blocking. [Evaluation criteria] ○: No blocking occurs. △: Blocking occurs, but it easily disperses when force is applied. ×: Blocking occurs and does not disperse even when force is applied.

[0104] The toners (T-1) to (T-8) of Examples 1 to 8 containing the polyester resins (L-1) to (L-8) of the present invention exhibited excellent performance in both low-temperature fixability and heat and humidity resistance storage stability. On the other hand, the toners (TR-1) and (TR-2) using the amorphous polyesters (LR-1) and (LR-2) had poor low-temperature fixability and heat and humidity resistance storage stability.

Industrial Applicability

[0105] The polyester resin for toner of the present invention can achieve both high levels of low-temperature fixability and heat and humidity resistance storage stability, and is extremely useful as a resin for toner for electrostatic charge image development used in electrophotography, electrostatic recording, electrostatic printing, etc.

Claims

Claim 1 A polyester resin obtained by polycondensing a carboxylic acid component and an alcohol component, wherein the carboxylic acid component contains at least one selected from terpene groups and hydrogenated terpene groups as a cyclic skeleton, a cyclic dicarboxylic acid or an anhydride thereof or an alkyl ester thereof, and the alcohol component contains a diol. The cyclic dicarboxylic acid or an anhydride thereof or an alkyl ester thereof is a compound represented by the following formula (1) and / or (2). 【Chemical 1】 【Chemical 2】 [In General Formula (1), R and R' each independently represent a hydrogen atom or an alkyl group. R and R' may be the same or different.] The total weight ratio of the cyclic dicarboxylic acid or an anhydride thereof or an alkyl ester thereof is 10 to 93.59% by weight based on the total weight of the carboxylic acid component. The carboxylic acid component contains trimellitic anhydride. A toner polyester resin in which the total weight ratio of the cyclic dicarboxylic acid or an anhydride thereof or an alkyl ester thereof and the trimellitic anhydride is 18.70 to 100% by weight based on the total weight of the carboxylic acid component. Claim 2 The toner polyester resin according to claim 1, wherein the cyclic dicarboxylic acid or an anhydride thereof or an alkyl ester thereof is fumarated α-terpinene, hydrogenated fumarated α-terpinene, or maleated α-terpinene anhydride. Claim 3 The toner polyester resin according to claim 1 or 2, wherein the total weight ratio of the trimellitic anhydride is 3.64 to 8.22% by weight based on the total weight of the carboxylic acid component. Claim 4 A toner containing the toner polyester resin according to claim 1 or 2. Claim 5 A toner containing the toner polyester resin according to claim 3.

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