JP6352598B2 - Toner binder and toner composition - Google Patents

Description

  The present invention relates to a toner binder and a toner composition.

The toner binder for electrophotography, which is commonly used as an image fixing method in copying machines, printers, etc., does not fuse the toner to the heat roll even at a high fixing temperature (hot offset resistance), fixing. Toners can be fixed even at low temperatures (low temperature fixability) and storage stability is required.
Toner compositions containing a polyester-based toner binder that are excellent in both low-temperature fixability and hot offset resistance are known (see Patent Documents 1 and 2). On the other hand, in order to improve the print image quality, there is an increasing demand for toner chargeability and heat-and-moisture storage stability of fixed images.

JP-A-12-75549 JP 2005-77930 A

  SUMMARY OF THE INVENTION An object of the present invention is to provide a toner binder that can achieve both low-temperature fixability and hot offset resistance, and is excellent in chargeability and heat-and-humidity storage stability of a fixed image.

As a result of intensive studies to solve the above problems, the present inventor has reached the present invention.
That is, the present invention provides a toner binder containing a polyester resin (A) having polycarboxylic acid (x) and polyol (y) as structural units, wherein (y) is 1,2-propylene glycol (PG). ) And (PG) is selected from the group consisting of (a) fatty acids or metal salts thereof, (b) sulfur-containing compounds, (c) nitrogen-containing compounds, and (d) trivalent or higher polyhydric alcohols A toner binder containing the above substances and having a content of 0.001 to 10% by weight based on the weight of (PG).

  The toner binder of the present invention can achieve both low-temperature fixability and hot offset resistance, and is excellent in blocking resistance, chargeability, and wet heat resistance of fixed images.

The present invention is described in detail below.
The polyester resin (A) is a polyester resin having a polycarboxylic acid (x) and a polyol (y) as structural units.

  Examples of the polycarboxylic acid (x) include a dicarboxylic acid (x1), a polycarboxylic acid having 3 to 6 or more valences (x2), and an acid anhydride and a lower alkyl ester (x3) of (x1) or (x2) Is mentioned.

Examples of the dicarboxylic acid (x1) include alkane dicarboxylic acids having 4 to 32 carbon atoms (such as succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanedicarboxylic acid and octadecanedicarboxylic acid); alkenedicarboxylic acids having 4 to 32 carbon atoms. (Eg, maleic acid, fumaric acid, citraconic acid, mesaconic acid, etc.); branched alkene dicarboxylic acids having 8 to 40 carbon atoms [eg, dimer acid, alkenyl succinic acid (dodecenyl succinic acid, pentadecenyl succinic acid, and octadecenyl succinic acid) Branched alkane dicarboxylic acids having 12 to 40 carbon atoms [eg alkyl succinic acid (decyl succinic acid, dodecyl succinic acid and octadecyl succinic acid etc.); aromatic dicarboxylic acids having 8 to 20 carbon atoms (eg phthalic acid, isophthalic acid, etc.) , Terephthalic acid and naphthalenedicarboxylic acid, etc. Etc. The.
Of these, alkene dicarboxylic acids and aromatic dicarboxylic acids are preferred, and aromatic dicarboxylic acids are more preferred.

  Examples of the trivalent to hexavalent or higher polycarboxylic acid (x2) include aromatic polycarboxylic acids having 9 to 20 carbon atoms (for example, trimellitic acid and pyromellitic acid).

Examples of the acid anhydride (x3) of (x1) or (x2) include trimellitic acid anhydride and pyromellitic acid anhydride.
Examples of the lower alkyl ester of (x1) or (x2) include methyl ester, ethyl ester, and isopropyl ester.

The ratio of the dicarboxylic acid (x1) in the polycarboxylic acid (x) is preferably 80 mol% or more, more preferably 83 to 98 mol%, and particularly preferably 85 to 95 mol%.
The ratio of the tri- to hexa-valent or higher polycarboxylic acid (x2) in (x) is preferably 20 mol% or less, more preferably 1 to 15 mol%, particularly preferably 2 to 12 mol%. is there.

  The polyol (y) in the present invention contains 1,2-propylene glycol [hereinafter abbreviated as (PG)]. Examples of (y) other than (PG) include diol (y1) and trivalent to hexavalent or higher polyol (y2).

  Examples of the diol (y1) include alkylene glycols having 2 to 30 carbon atoms excluding (PG) (for example, ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, octanediol, decane) Diol, dodecanediol, tetradecanediol, neopentyl glycol, 2,2-diethyl-1,3-propanediol, etc.); number average molecular weight (hereinafter abbreviated as Mn) = 106 to 10,000 alkylene ether glycol (for example, diethylene glycol) , Triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol and polytetramethylene ether glycol); alicyclic diols having 6 to 24 carbon atoms (for example, 1,4-cyclohexanedimethanol and Bisphenol A or the like); alkylene oxide (hereinafter abbreviated as AO) adduct of Mn = 100 to 10,000 (addition mole number 2 to 100) [for example, 1,4-cyclohexanedimethanol Ethylene oxide (hereinafter abbreviated as EO) 10 mol adduct, etc.]; C13-C30 bisphenols (Bisphenol A, bisphenol F, bisphenol S, etc.) or C12-C24 polyphenols (for example, catechol, hydroquinone and resorcinol) Etc.) AO [EO, propylene oxide (hereinafter abbreviated as PO) and butylene oxide (hereinafter abbreviated as BO), etc.] adducts (addition mole number 2 to 100) (for example, bisphenol A · EO 2 to 4 mol adduct and Bisphenol A / PO 2-4 mol adduct, etc.); heavy Average molecular weight (hereinafter abbreviated as Mw) = 100 to 5,000 polylactone diols (such as poly -ε- caprolactone diol); polybutadiene diol of Mw = 1,000 to 20,000 and the like.

  Examples of the trivalent to hexavalent or higher polyol (y2) include trivalent to hexavalent or higher aliphatic polyhydric alcohols having 3 to 10 carbon atoms (for example, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitan). And AO (2 to 4 carbon atoms) adduct (addition mole number 2 to 100) of trisphenol having 25 to 50 carbon atoms (for example, trisphenol · EO 2 to 4 mol adduct and trisphenol PA · PO 2 −). 4 mol adducts, etc.); AO (carbon number 2-4) adducts (addition mol number 2-100) (phenol novolac PO 2 mol adducts) of 3 to 50 novolak resins (for example, phenol novolak and cresol novolak). And phenol novolac EO 4 mol adduct); polyphenols having 6 to 30 carbon atoms (examples) Pyrogallol, phloroglucinol, 1,2,4-benzenetriol and the like) AO (carbon number 2 to 4) adduct (addition mole number 2 to 100) (pyrogallol EO 4 mol adduct); and polymerization degree 20 to 2 , 1,000 acrylic polyol {copolymer of hydroxyethyl (meth) acrylate and other polymerizable double bond monomer [for example, styrene, (meth) acrylic acid, (meth) acrylic acid ester, etc.]} Etc.

  Among the polyols (y), the diol (y1) is preferable from the viewpoint of compatibility between low-temperature fixability and hot offset resistance and storage stability, and more preferable are alkylene glycols having 2 to 10 carbon atoms and carbon numbers. AO adducts of 15 to 30 bisphenols, particularly preferred are alkylene glycols having 2 to 10 carbon atoms and AO adducts of bisphenol A (addition moles 2 to 30), particularly preferred are ethylene glycol, 1,3-propylene glycol, 1,4-butanediol and polyoxyalkylene ethers of bisphenols (number of AO units 2 to 30), most preferably polyoxyalkylene ethers of ethylene glycol and bisphenols (AO) The number of units is 2 to 30).

  The proportion of (PG) in the polyol (y) (excluding those distilled out of the system during the polycondensation reaction, the same shall apply hereinafter) is preferably 40 mol% or more, more preferably 50 mol% or more. Especially preferably, it is 70 mol% or more. When the ratio of (PG) is 40 mol% or more, the fixing temperature range when used as a toner is widened, and the storage stability is sufficient.

  (PG) in the present invention is one or more selected from the group consisting of (a) a fatty acid or a metal salt thereof, (b) a sulfur-containing compound, (c) a nitrogen-containing compound, and a trihydric or higher polyhydric alcohol (d). And the content thereof is 0.001 to 10% by weight based on the weight of (PG), and preferably 0.002 based on the weight of (PG) from the viewpoint of chargeability and charge retention. -5% by weight, more preferably 0.005-2% by weight.

As a fatty acid in a fatty acid and its metal salt (a), a C2-C30 saturated fatty acid, a C3-C30 unsaturated fatty acid, etc. are mentioned.
Examples of saturated fatty acids having 2 to 30 carbon atoms include 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.
Examples of unsaturated fatty acids having 3 to 30 carbon atoms include acrylic acid, methacrylic acid, palmitoleic acid, oleic acid, vaccenic acid, linoleic acid, α-linolenic acid, γ-linolenic acid, eleostearic acid, and 8,11-eicosadiene. Acid, 5,8,11-eicosatrienoic acid, arachidonic acid, stearidonic acid, eicosapentaenoic acid, docosapentaenoic acid, docosahexaenoic acid, dihomo-γ-linolenic acid, docosapentaenoic acid, elaidic acid, erucic acid and nerbon An acid etc. are mentioned.
Examples of the fatty acid metal salt (a) include alkali metal (such as lithium, sodium and potassium) salts and alkaline earth metal (such as magnesium, calcium and barium) salts of the above fatty acids.

  Examples of the sulfur-containing compound (b) include thioether compounds such as dimethylthioether and methionine, thiol compounds such as ethanethiol and propanethiol, sulfoxide compounds such as alliin, sulfonic acid compounds such as benzenesulfonic acid, p-toluenesulfonic acid, and taurine. Etc.

  As the nitrogen-containing compound (c), ammonia; monomethylamine, monoethylamine, monopropylamine, monobutylamine, monopentylamine, monohexylamine, monoheptylamine, monooctylamine, dimethylamine, methylethylamine, diethylamine, methylpropyl Alkylamines such as amine, ethylpropylamine, dipropylamine, methylbutylamine, ethylbutylamine, propylbutylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine (the alkyl group may be linear or branched) Good); monomethanolamine, monoethanolamine, monopropanolamine, monobutanolamine, monopentanolamine, monohexanolamine, monoheptano Luamine, monooctanolamine, monononanolamine, dimethanolamine, methanolethanolamine, diethanolamine, methanolpropanolamine, ethanolpropanolamine, dipropanolamine, methanolbutanolamine, ethanolbutanolamine, propanolbutanolamine, dibutanolamine, dipen Examples include alkanolamines such as tanolamine, dihexanolamine, diheptanolamine, and dioctanolamine (the alkanol group may be linear or branched).

  Examples of the trivalent or higher polyol (d) include those exemplified as the above trivalent to hexavalent or higher polyol (y2).

The polyester resin (A) may have a monocarboxylic acid (e) and / or a monoalcohol (f) as a structural unit in addition to the polycarboxylic acid (x) and the polyol (y).
Examples of the monocarboxylic acid (e) include an aliphatic monocarboxylic acid (e-1) and an aromatic monocarboxylic acid (e-2).

Examples of the aliphatic monocarboxylic acid (e-1) include a chain saturated monocarboxylic acid, a chain unsaturated monocarboxylic acid, and an alicyclic monocarboxylic acid.
As the chain saturated monocarboxylic acid, a linear or branched chain saturated monocarboxylic acid having 2 to 30 carbon atoms (acetic acid, propionic acid, butyric acid, valeric acid, 2-ethylhexanoic acid, caproic acid, enanthic acid, capryl) 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).
Examples of the chain unsaturated monocarboxylic acid include linear or branched chain unsaturated monocarboxylic acid having 3 to 30 carbon atoms (acrylic acid, methacrylic acid, palmitoleic acid, oleic acid, vaccenic acid, linoleic acid, α-linolenic acid. Acid, γ-linolenic acid, eleostearic acid, 8,11-icosadienoic acid, 5,8,11-icosatrienoic acid, arachidonic acid, stearidonic acid, eicosapentaenoic acid, docosapentaenoic acid, docosahexaenoic acid, dihomo-γ- Linolenic acid, docosapentaenoic acid, elaidic acid, erucic acid, nervonic acid and the like).
Examples of the alicyclic monocarboxylic acid include alicyclic monocarboxylic acids having 4 to 14 carbon atoms (such as cyclopropane carboxylic acid, cyclobutane carboxylic acid, cyclopentane carboxylic acid, cyclohexane carboxylic acid, and cycloheptane carboxylic acid). .
Examples of the aromatic monocarboxylic acid (e-2) include aromatic monocarboxylic acids having 7 to 36 carbon atoms. Specific examples include benzoic acid, vinyl benzoic acid, toluic acid, dimethyl benzoic acid, and t-butyl. Examples include benzoic acid, cumic acid, naphthoic acid, biphenyl monocarboxylic acid, and furic acid.
Of the monocarboxylic acids (e), aromatic monocarboxylic acids (e-2) are preferred from the viewpoint of low-temperature fixability and wet heat storage stability, and more preferred are benzoic acid and t-butylbenzoic acid. Acids and naphthoic acids.

Examples of the monoalcohol (f) include an aliphatic monoalcohol (f-1) and an aromatic monoalcohol (f-2).
Examples of the aliphatic monoalcohol (f-1) include a chain saturated monoalcohol and a chain unsaturated monoalcohol.

  Examples of the chain saturated monoalcohol include linear or branched chain saturated monoalcohol having 1 to 30 carbon atoms (methanol, ethanol, 1-propanol, 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, and stearyl alcohol), and straight-chain or branched-chain saturated monomers having 1 to 30 carbon atoms Alcohol with 2 to 4 carbon atoms (EO, PO and BO) obtained by adding the (addition molar number of 1 to 20 mol), and the like.

  Examples of the chain unsaturated monoalcohol include linear or branched chain unsaturated monoalcohol having 2 to 30 carbon atoms (allyl alcohol, 2-buten-1-ol, 2-penten-1-ol, 2-hexene- 1-ol, 2-hepten-1-ol, 2-octen-1-ol, 2-nonen-1-ol, 2-decen-1-ol, 2-dodecenol, palmitolyl alcohol, oleyl alcohol and linoleyl alcohol Etc.), and those obtained by adding AO (EO, PO, and BO) having 2 to 4 carbon atoms to linear or branched chain-type unsaturated monoalcohol having 1 to 30 carbon atoms (addition mole number 1 to 20 moles), etc. Is mentioned.

  As aromatic monoalcohol (f-2), C6-C30 aromatic monoalcohol (phenol, ethylphenol, isobutylphenol, pentylphenol, octylphenol, dodecylphenol, tetradecylphenol, benzyl alcohol, etc.) and carbon Examples include those obtained by adding AO (EO, PO and BO) having 2 to 4 carbon atoms to aromatic monoalcohol having several to 30 to 30 mol (added mole number 1 to 20 mol).

The polyester resin (A) in the present invention can be produced in the same manner as in an ordinary polyester production method. For example, the reaction temperature of the carboxylic acid component (x) and the polyol component (y) is preferably 150 to 280 ° C., more preferably 170 to 260 ° C., particularly preferably in an inert gas (nitrogen gas or the like) atmosphere. It can carry out by making it react at 190-240 degreeC. The reaction time is preferably 30 minutes or longer, particularly 2 to 40 hours from the viewpoint of reliably performing the polycondensation reaction. It is also effective to reduce the pressure in order to improve the reaction rate at the end of the reaction.
The reaction ratio between the polyol component (y) and the polycarboxylic acid component (x) is preferably 2/1 to 1/2, more preferably 1. as the equivalent ratio [OH] / [COOH] of the hydroxyl group to the carboxyl group. 5/1 to 1 / 1.3, particularly preferably 1.3 / 1 to 1 / 1.2.
At this time, an esterification catalyst can be used as needed. Examples of the esterification catalyst include a tin-containing catalyst (for example, dibutyltin oxide), antimony trioxide, and a titanium-containing catalyst [for example, titanium alkoxide, potassium oxalate titanate, titanium terephthalate, a catalyst described in JP 2006-243715 A [Titanium dihydroxybis (triethanolamate), titanium monohydroxytris (triethanolaminate), and intramolecular polycondensates thereof], and catalysts described in JP-A No. 2007-11307 (titanium tributoxyterephthalate) , Titanium triisopropoxy terephthalate, titanium diisopropoxy diterephthalate, etc.)], zirconium-containing catalyst (for example, zirconyl acetate), zinc acetate and the like. Among these, a titanium-containing catalyst is preferable.

The polyester resin (A) may be a nonlinear polyester resin (A1) or a linear polyester resin (A2). Here, the non-linear polyester resin (A1) is a dicarboxylic acid (x1) and a diol (y1), a tri- or hexavalent polycarboxylic acid (x2), an acid anhydride of (x2) and a lower alkyl. It is a polyester resin having a structural unit of an ester (x3) and / or a tri- or hexavalent or higher polyol (y2).
The linear polyester resin (A2) is a chain polyester resin having a dicarboxylic acid (x1) and a diol (y1) as structural units and having no three-dimensional crosslinked structure. (X1), (y1) In addition to the polycarboxylic acid (x2) having 3 to 6 or more valences, the acid anhydride and lower alkyl ester (x3) of (x2), and / or the polyol (y2) having 3 to 6 or more valences. Even in the case of the unit, the molar ratio of use and reaction conditions are selected, the reaction is substantially carried out as monofunctional or bifunctional, and the remaining functional groups are left unreacted. The linear polyester resin (A2) can be confirmed by a THF-insoluble matter.

The acid value of the non-linear polyester resin (A1) is preferably 0 to 100 (mg KOH / g, the same shall apply hereinafter) from the viewpoint of chargeability, more preferably 0 to 80, and particularly preferably 1 to 60.
The hydroxyl value of (A2) is preferably 0 to 100 (mg KOH / g, the same applies hereinafter), more preferably 0 to 80, and particularly preferably 0 to 50, from the viewpoint of hot offset resistance.

In the present invention, the acid value and hydroxyl value of the polyester resin can be measured by the method specified in JIS K0070 (1992 edition).
When the sample has a solvent-insoluble component accompanying crosslinking, the sample after melt-kneading is used as a sample by the following method.
Kneading device: Labo plast mill MODEL4M150 manufactured by Toyo Seiki Co., Ltd.
Kneading conditions: 130 ° C., 70 rpm, 30 minutes

  The peak top molecular weight (hereinafter abbreviated as Mp) of the tetrahydrofuran (THF) soluble part of the non-linear polyester resin (A1) is preferably 2000 to 20000 from the viewpoint of achieving both heat-resistant storage stability and low-temperature fixability of the toner. More preferably, it is 3000-18000, Most preferably, it is 4000-15000.

In the present invention, the molecular weight [Mp, number average molecular weight (Mn), and weight average molecular weight (Mw)] of the resin is measured using gel permeation chromatography (GPC) under the following conditions.
Device (example): HLC-8120 manufactured by Tosoh Corporation
Column (example): TSK GEL GMH6 2 [Tosoh Corp.]
Measurement temperature: 40 ° C
Sample solution: 0.25 wt% THF (tetrahydrofuran) solution Solution injection amount: 100 μl
Detection apparatus: Refractive index detector Reference material: Tosoh standard polystyrene (TSK standard POLYSYRENE) 12 points (molecular weight 500 1050 2800 5970 9100 18100 37900 96400 190000 355000 1090000 2890000)
The molecular weight showing the maximum peak height on the obtained chromatogram is defined as peak top molecular weight (Mp). The molecular weight is measured by dissolving a polyester resin in THF and filtering out the insoluble matter with a glass filter.

The glass transition temperature (Tg) of the nonlinear polyester resin (A1) in the present invention is preferably 30 to 75 ° C., more preferably 40 to 72 ° C., particularly preferably from the viewpoints of fixability, storage stability and durability. Is 50-70 degreeC.
In addition, in the above and below, Tg is measured by the method (DSC method) prescribed | regulated to ASTM D3418-82 using Seiko Denshi Kogyo Co., Ltd. DSC20 and SSC / 580.

The softening point [Tm] of (A1) is preferably 120 to 170 ° C, more preferably 125 to 168 ° C, and particularly preferably 130 to 165 ° C.
Within this range, the compatibility between hot offset resistance and low-temperature fixability is good. In the present invention, Tm is measured by the following method.
<Softening point [Tm]>
Using a Koka-type flow tester {for example, CFT-500D, manufactured by Shimadzu Corporation), a load of 1.96 MPa was applied by a plunger while heating a 1 g measurement sample at a heating rate of 6 ° C./min. Extrude from a nozzle with a diameter of 1 mm and a length of 1 mm, draw a graph of “plunger descent (flow value)” and “temperature”, and set the temperature corresponding to 1/2 of the maximum plunger descent It reads from a graph and makes this value (temperature when half of a measurement sample flows out) be a softening point [Tm].

The non-linear polyester resin (A1) used in the present invention has a storage elastic modulus at 150 ° C. [in this specification, “G ′ (150)” in some cases, from the viewpoint of hot offset resistance when used as a toner. is there. ] (Pa) is 2000 Pa or more (preferably 3000 Pa or more), and G ′ (150) and storage elastic modulus at 180 ° C. [In this specification, it may be expressed as “G ′ (180)”. (Pa) needs to satisfy the following formula (1), preferably satisfies the formula (1 ′), and more preferably satisfies the formula (1 ″).
[G ′ (150)] / [G ′ (180)] ≦ 15 Formula (1)
[G ′ (150)] / [G ′ (180)] ≦ 14 Formula (1 ′)
[G ′ (150)] / [G ′ (180)] ≦ 13 Formula (1 ″)
When G ′ (150) and G ′ (180) satisfy the formula (1), it is considered that the viscosity is not too low in a practical range even in a high temperature range, and the hot offset resistance when used as a toner is good. .
In order to adjust the storage elastic modulus (G ′) of the non-linear polyester resin (A1), for example, when G ′ (150) / G ′ (180) is decreased, the Tm of the polyester resin (A) is increased. This can be achieved by increasing the ratio of the above components, increasing the number of crosslinking points, increasing the molecular weight, or increasing the Tg.

In the present invention, the storage elastic modulus (G ′) of the non-linear polyester resin (A1) is measured using the following viscoelasticity measuring device.
Apparatus: ARES-24A (Rheometric)
Jig: 25 mm parallel plate Frequency: 1 Hz
Distortion rate: 5%
Temperature increase rate: 5 ° C / min

The nonlinear polyester resin (A1) has a viscosity at Tg + 40 ° C. (referred to as Eta [Tg + 40] in the present specification) (Pa · s) in the following formula from the viewpoint of low-temperature fixability when used as a toner. It is preferable to satisfy (2), more preferably to satisfy formula (2 ′), and most preferably to satisfy formula (2 ″).
Eta [Tg + 40] ≦ 7 × 10 ⁵ ... Formula (2)
Eta [Tg + 40] ≦ 6 × 10 ⁵ Formula (2 ′)
Eta [Tg + 40] ≦ 5 × 10 ⁵ Formula (2 ″)
When Eta [Tg + 40] satisfies the formula (2), the viscosity in the low temperature region is small, and the low temperature fixability when used as a toner is good.
In order to adjust the viscosity Eta of the non-linear polyester resin (A1), for example, when Eta [Tg + 40] is decreased, the Tm of the non-linear polyester resin (A1) is decreased or Mp is decreased.

In the present invention, the viscosity Eta of the polyester resin is measured using the following viscoelasticity measuring apparatus.
Apparatus: ARES-24A (Rheometric)
Jig: 8mm parallel plate Frequency: 1Hz
Distortion rate: 5%
Temperature increase rate: 3 ° C / min

  The acid value of the linear polyester resin (A2) is preferably 0 to 60, more preferably 1 to 55, and particularly preferably 2 to 50. When the acid value is 60 or less, charging characteristics when used as a toner do not deteriorate.

  The hydroxyl value of the linear polyester resin (A2) is preferably 0 to 125, more preferably 1 to 100. When the hydroxyl value is 125 or less, hot offset resistance and storage stability when used as a toner are improved.

  The Mp of gel permeation chromatography of the THF-soluble component of the linear polyester resin (A2) is preferably 1000 to 12000, more preferably 2000 to 11000, and particularly preferably 2500 to 10,000. When Mp is 2000 or more, the resin strength necessary for fixing is obtained, and when it is 12000 or less, the low-temperature fixability when used as a toner is good.

  The softening point [Tm] of the linear polyester resin (A2) is preferably 70 to 120 ° C, more preferably 75 to 118 ° C, particularly preferably 80 to 115 ° C. In this range, the balance between hot offset resistance and low-temperature fixability is good.

  The glass transition temperature [Tg] of the linear polyester resin (A2) used in the present invention is preferably 45 ° C. or higher from the viewpoint of storage stability. Further, when it is 75 ° C. or lower, the low-temperature fixability when used as a toner is good.

  The THF insoluble content in the linear polyester resin (A2) is preferably 5% or less from the viewpoint of low-temperature fixability when used as a toner. More preferably, it is 4% or less, and particularly preferably 3% or less.

The THF-insoluble matter in the present invention is determined by the following method.
Add 50 ml of THF to 0.5 g of the sample and stir to reflux for 3 hours. After cooling, the insoluble content is filtered off with a glass filter, and the resin content on the glass filter is dried under reduced pressure at 80 ° C. for 3 hours. The insoluble matter is calculated from the weight of the dried resin content on the glass filter and the weight ratio of the sample.

The toner binder of the present invention may contain a polyester resin (B) in addition to the polyester resin (A). (B) is a polyester resin having polycarboxylic acid (x) and polyol (y) as structural units, and is a resin different from (A).
Examples of the polyester resin (B) include a nonlinear polyester resin (B1) and a linear polyester resin (B2).

  The toner binder of the present invention has a non-linear polyester resin (A1) and / or a non-linear polyester resin (B1) and a linear polyester resin (A2) and a linear shape from the viewpoint of achieving both hot offset resistance and low-temperature fixability. It is preferable to combine both or one of the polyester resins (B2), and its weight ratio [[(A1) and (B1) or either one]] / [(A2) and (B2) or either On the other hand,]] (the total is 100) is preferably (95-5) / (5-95), more preferably (85-15) / (15-85), and particularly preferably (75-25). ) / (25-70).

The polyester resin (A) in the present invention contains one or more substances selected from the group consisting of (a) fatty acids or metal salts thereof, (b) sulfur-containing compounds, and (c) nitrogen-containing compounds, and The content is 10 to 10000 ppm, preferably 20 to 8000 ppm, particularly preferably 20 to 5000 ppm, based on the weight of (A).
In the above and the following, this content rate is a total value of the weight ratios of the respective components calculated from the molar ratio of protons measured by ¹ H-NMR.

The method for mixing the polyester resins (A) and (B) is not particularly limited, and may be a known method that is usually performed, and may be either powder mixing or melt mixing. Further, it may be mixed at the time of toner formation.
As a mixing apparatus in the case of melt-mixing, a batch type mixing apparatus such as a reaction tank and a continuous mixing apparatus can be mentioned. In order to uniformly mix at an appropriate temperature in a short time, a continuous mixing device is preferable. Examples of the continuous mixing device include an extruder, a continuous kneader, and a three roll.
Examples of the mixing device for powder mixing include a Henschel mixer, a Nauter mixer, and a Banbury mixer. A Henschel mixer is preferable.

  The toner composition of the present invention contains the toner binder of the present invention and a colorant.

As the colorant, all of dyes and pigments used as toner colorants can be used. Specifically, carbon black, iron black, Sudan Black SM, First Yellow G, Benzidine Yellow, Pigment Yellow, Indian First Orange, Irgasin Red, Paranitroaniline Red, Toluidine Red, Carmine FB, Pigment Orange R, Lake Red 2G, Rhodamine FB, Rhodamine B Lake, Methyl Violet B Lake, Phthalocyanine Blue, Pigment Blue, Brilliant Green, Phthalocyanine Green, Oil Yellow GG, Kayaset YG, Orazole Brown B, Oil Pink OP, etc. Or 2 or more types can be mixed and used. Further, if necessary, magnetic powder (a powder of a ferromagnetic metal such as iron, cobalt, nickel, or a compound such as magnetite, hematite, ferrite) can also be included as a colorant.
The content of the colorant is preferably 1 to 40 parts by weight, more preferably 3 to 10 parts by weight with respect to 100 parts by weight of the toner binder of the present invention. In addition, when using magnetic powder, Preferably it is 20-150 weight part, More preferably, it is 40-120 weight part.

The toner composition of the present invention may contain one or more additives selected from a release agent, a charge control agent, a fluidizing agent and the like.
As the release agent, those having a softening point [Tm] of 50 to 170 ° C. by a flow tester are preferable, and polyolefin wax, natural wax, aliphatic alcohol having 30 to 50 carbon atoms, fatty acid having 30 to 50 carbon atoms and the like can be mentioned. It is done.
Polyolefin waxes include (co) polymers [obtained by (co) polymerization] of olefins (for example, ethylene, propylene, 1-butene, isobutylene, 1-hexene, 1-dodecene, 1-octadecene, and mixtures thereof). And olefin (co) polymer oxides by oxygen and / or ozone, maleic acid modifications of olefin (co) polymers [eg maleic acid and its derivatives (maleic anhydride, Modified products such as monomethyl maleate, monobutyl maleate and dimethyl maleate), olefins and unsaturated carboxylic acids [(meth) acrylic acid, itaconic acid and maleic anhydride, etc.] and / or unsaturated carboxylic acid alkyl esters [(meta ) Alkyl acrylate (alkyl of 1 to 18 carbon atoms) ester and Copolymers of maleic acid alkyl (having 1 to 18 carbon atoms in the alkyl) esters, etc.] or the like, and Sasol wax.
Examples of natural waxes include carnauba wax, montan wax, paraffin wax, and rice wax.
Examples of the aliphatic alcohol having 30 to 50 carbon atoms include triacontanol.
Examples of the fatty acid having 30 to 50 carbon atoms include triacontane carboxylic acid.

  As charge control agents, nigrosine dyes, triphenylmethane dyes containing tertiary amines as side chains, quaternary ammonium salts, polyamine resins, imidazole derivatives, quaternary ammonium base-containing polymers, metal-containing azo dyes, copper phthalocyanine dyes , Salicylic acid metal salts, boron complexes of benzylic acid, sulfonic acid group-containing polymers, fluorine-containing polymers, halogen-substituted aromatic ring-containing polymers, and the like.

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

  The composition ratio of the toner composition of the present invention is preferably 30 to 97% by weight, more preferably 40 to 95% by weight, particularly preferably 45 to 92% by weight, based on the toner weight. The agent is preferably 0.05 to 60% by weight, more preferably 0.1 to 55% by weight, particularly preferably 0.5 to 50% by weight; among the additives, the release agent is preferably 0 to 30%. % By weight, more preferably 0.5 to 20% by weight, particularly preferably 1 to 10% by weight; the charge control agent is preferably 0 to 20% by weight, more preferably 0.1 to 10% by weight, particularly preferably 0.5 to 7.5% by weight; The fluidizing agent is preferably 0 to 10% by weight, more preferably 0 to 5% by weight, and particularly preferably 0.1 to 4% by weight. The total content of additives is preferably 3 to 70% by weight, more preferably 4 to 58% by weight, and particularly preferably 5 to 50% by weight. When the composition ratio of the toner composition is within the above range, a toner having good chargeability can be easily obtained.

The toner composition of the present invention may be obtained by any conventionally known method such as a kneading and pulverizing method, an emulsion phase inversion method, or a polymerization method. For example, when a toner is obtained by a kneading and pulverizing method, the components constituting the toner excluding the fluidizing agent are dry blended, and then melt-kneaded, then coarsely pulverized, and finally atomized using a jet mill pulverizer or the like. Further, by further classifying, the volume average particle diameter (D50) is preferably 5 to 20 μm and then mixed with a fluidizing agent. The particle size (D50) is measured using a Coulter counter [for example, trade name: Multisizer III (manufactured by Coulter)].
When the toner is obtained by the emulsion phase inversion method, the components constituting the toner excluding the fluidizing agent are dissolved or dispersed in an organic solvent, and then emulsified by adding water, etc., and then separated and classified for production. it can. The volume average particle diameter of the toner is preferably 3 to 15 μm.

  The toner composition of the present invention is mixed with carrier particles such as iron powder, glass beads, nickel powder, ferrite, magnetite, and ferrite whose surface is coated with a resin (acrylic resin, silicone resin, etc.) as necessary. Used as a developer for a latent image. The weight ratio of toner to carrier particles is usually 1/99 to 100/0. In addition, instead of carrier particles, it can be rubbed with a member such as a charging blade to form an electrical latent image.

  The toner composition of the present invention is fixed on a support (paper, polyester film, etc.) by a copying machine, a printer, or the like to form a recording material. As a method for fixing to the support, a known hot roll fixing method, flash fixing method, or the like can be applied.

  Hereinafter, the present invention will be further described with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

[Purification of (PG) -1]
Crude propylene glycol (PG-1) (propylene glycol purity measured by gas chromatography was 88% by weight) was put into a reaction vessel equipped with a condenser and a stirrer, and distilled under atmospheric pressure. And a fraction having a boiling point of 186 to 190 ° C. was collected to obtain purified propylene glycol (PG-2). The purity of propylene glycol measured by gas chromatography was 97% by weight.

[Purification of (PG) -2]
The above propylene glycol (PG-2) is placed in a reaction vessel equipped with a condenser and a stirrer, and distilled under atmospheric pressure to recover a fraction having a boiling point of 188 to 190 ° C. and purified propylene glycol ( PG-3) was obtained. The purity of propylene glycol measured by gas chromatography was 99% by weight.

<Production Example 1> [Synthesis of polyester resin (A1-1)]
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 631 parts by weight of terephthalic acid, 21 parts by weight of adipic acid, 640 parts by weight of (PG-3), titanium diisopropoxybistriethanolamate 0 as a polymerization catalyst .5 parts by weight was added and reacted for 5 hours while distilling off the water produced at 210 ° C. under a nitrogen stream, and then reacted under reduced pressure of 0.5 to 2.5 kPa for 1 hour. Next, 53 parts by weight of benzoic acid was added, and the mixture was reacted for 3 hours under normal pressure. Further, 94 parts by weight of trimellitic anhydride was added and reacted under normal pressure for 1 hour, followed by reaction under reduced pressure of 2.5 to 5 kPa and taken out at a softening point of 1 ° C. The recovered 1,2-propylene glycol was 274 parts by weight. The obtained resin was cooled to room temperature and then pulverized into particles. This is designated as polyester resin (A1-1).
Mp of (A1-1) was 6000, Tg was 65 ° C., Tm was 160 ° C., the acid value was 16, and the hydroxyl value was 14.

<Production Example 2> [Synthesis of polyester resin (A1-2)]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 608 parts by weight of terephthalic acid, 20 parts by weight of adipic acid, 600 parts by weight of 1,2-propylene glycol (PG-3), titanium diisopropylene as a polymerization catalyst. After adding 0.5 parts by weight of propoxybistriethanolamate and reacting for 5 hours while distilling off the water produced at 210 ° C. under a nitrogen stream, the reaction is carried out for 1 hour under a reduced pressure of 0.5 to 2.5 kPa. It was. Next, 65 parts by weight of benzoic acid was added and reacted under normal pressure for 3 hours. Furthermore, after adding 132 weight part of trimellitic anhydride and making it react under normal pressure for 1 hour, it was made to react under reduced pressure of 2.5-5 kPa, and it took out at the softening point of 160 degreeC. The recovered 1,2-propylene glycol was 257 parts by weight. The obtained resin was cooled to room temperature and then pulverized into particles. This is designated as polyester resin (A1-2).
Mp of (A1-2) was 4500, Tg was 65 ° C., Tm was 160 ° C., acid value was 30, and hydroxyl value was 1.

<Production Example 3> [Synthesis of polyester resin (A1-3)]
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 596 parts by weight of terephthalic acid, 33 parts by weight of phthalic acid, 465 parts by weight of 1,2-propylene glycol (PG-3), 95 parts by weight of ethylene glycol, After adding 0.5 parts by weight of titanium diisopropoxybistriethanolaminate as a polymerization catalyst and reacting for 5 hours while distilling off the water generated under a nitrogen stream at 210 ° C., the pressure is reduced to 0.5 to 2.5 kPa. The reaction was allowed to proceed for 1 hour. Next, 88 parts by weight of benzoic acid was added and reacted under normal pressure for 3 hours. Furthermore, after adding 133 weight part of trimellitic anhydride and making it react for 1 hour under a normal pressure, it was made to react under the reduced pressure of 2.5-5 kPa, and it took out at 164 degreeC of softening points. The recovered 1,2-propylene glycol was 207 parts by weight, and ethylene glycol was 35 parts by weight. The obtained resin was cooled to room temperature and then pulverized into particles. This is designated as polyester resin (A1-3).
Mp of (A1-3) was 4700, Tg was 63 ° C., Tm was 164 ° C., the acid value was 28, the hydroxyl value was 3, and the molar ratio of 1,2-propylene glycol in the alcohol was 80 mol%.

<Production Example 4> [Synthesis of polyester resin (A1-4)]
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 559 parts by weight of terephthalic acid, 49 parts by weight of isophthalic acid, 393 parts by weight of 1,2-propylene glycol (PG-3), 138 parts by weight of ethylene glycol, After adding 0.5 parts by weight of titanium diisopropoxybistriethanolaminate as a polymerization catalyst and reacting for 5 hours while distilling off the water generated under a nitrogen stream at 210 ° C., the pressure is reduced to 0.5 to 2.5 kPa. The reaction was allowed to proceed for 1 hour. Next, 85 parts by weight of benzoic acid was added and reacted under normal pressure for 3 hours. Furthermore, after adding 129 weight part of trimellitic anhydride and making it react under normal pressure for 1 hour, it was made to react under reduced pressure of 2.5-5 kPa, and it took out at 164 degreeC of softening points. The recovered 1,2-propylene glycol was 141 parts by weight, and ethylene glycol was 51 parts by weight. The obtained resin was cooled to room temperature and then pulverized into particles. This is designated as polyester resin (A1-4).
Mp of (A1-4) was 4700, Tg was 61 ° C., Tm was 164 ° C., the acid value was 26, the hydroxyl value was 5, and the molar ratio of 1,2-propylene glycol in the alcohol was 70 mol%.

<Production Example 5> [Synthesis of polyester resin (A1-5)]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 752 parts by weight of terephthalic acid, 73 parts by weight of adipic acid, 17 parts by weight of trimellitic anhydride, 726 weights of 1,2-propylene glycol (PG-3) After adding 0.5 parts by weight of titanium diisopropoxybistriethanolamate as a polymerization catalyst and reacting for 5 hours while distilling off the water generated under a nitrogen stream at 210 ° C., the pressure was reduced to 2.5 to 5 kPa. The reaction was carried out at the bottom and taken out at a softening point of 141 ° C. The recovered 1,2-propylene glycol was 384 parts by weight. The obtained resin was cooled to room temperature and then pulverized into particles. This is designated as polyester resin (A1-5).
Mp of (A1-5) was 18000, Tg was 66 ° C., Tm was 141 ° C., the acid value was 1, and the hydroxyl value was 14.

<Production Example 6> Synthesis of polyester resin (A1-6)]
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 693 parts by weight of terephthalic acid, 68 parts by weight of adipic acid, 28 parts by weight of trimellitic anhydride, 670 parts by weight of 1,2-propylene glycol (PG-3) After adding 0.5 parts by weight of titanium diisopropoxybistriethanolamate as a polymerization catalyst and reacting for 5 hours while distilling off the water generated under a nitrogen stream at 210 ° C., the pressure was reduced to 2.5 to 5 kPa. The reaction was carried out at the bottom and taken out at a softening point of 141 ° C. The recovered 1,2-propylene glycol was 384 parts by weight. The obtained resin was cooled to room temperature and then pulverized into particles. This is designated as polyester resin (A1-6).
Mp of (A1-6) was 14000, Tg was 64 ° C., Tm was 143 ° C., the acid value was 1, and the hydroxyl value was 19.

<Production Example 7> [Synthesis of polyester resin (A1-7)]
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 680 parts by weight of terephthalic acid, 30 parts by weight of adipic acid, 16 parts by weight of trimellitic anhydride, 660 parts by weight of 1,2-propylene glycol (PG-2) After adding 0.5 parts by weight of titanium diisopropoxybistriethanolamate as a polymerization catalyst and reacting for 5 hours while distilling off the water generated under a nitrogen stream at 210 ° C., the pressure was reduced to 2.5 to 5 kPa. The reaction was carried out at the bottom and the softening point was 135 ° C. The recovered 1,2-propylene glycol was 280 parts by weight. The obtained resin was cooled to room temperature and then pulverized into particles. This is designated as polyester resin (A1-7).
Mp of (A1-7) was 5000, Tg was 64 ° C., Tm was 135 ° C., the acid value was 1, and the hydroxyl value was 18.

<Production Example 8> [Synthesis of polyester resin (A1-8)]
In the reaction vessel, 455 parts by weight of terephthalic acid (88.5 mol parts), 44 parts by weight of adipic acid (9.8 mol parts), 383 parts by weight of 1,2-propylene glycol (PG-2) (recovery fraction 235 below) 60.0 mol parts by subtracting parts by weight), 452 parts by weight of bisphenol A / PO2 mol adduct (40.0 mol parts), 0.5 parts by weight of titanium diisopropoxybistriethanolamate, and nitrogen at 210 ° C. After reacting for 5 hours while distilling off the water and ethylene glycol produced under an air stream, 10 parts by weight (1.7 mole parts) of trimellitic anhydride is added and reacted for 1 hour under normal pressure. The reaction was conducted under reduced pressure of 5 to 5 kPa, and the product was taken out at a softening point of 130 ° C. The recovered 1,2-propylene glycol was 235 parts by weight. The obtained resin was cooled to room temperature and then pulverized into particles. This is designated as polyester resin (A1-8).
Tg of (A1-8) was 62 ° C., Tm was 130 ° C., Mp was 13000, the acid value was 1, and the hydroxyl value was 14.

<Production Example 9> [Synthesis of polyester resin (A1-9)]
In the reaction vessel, 455 parts by weight of terephthalic acid (88.5 mol parts), 44 parts by weight of adipic acid (9.8 mol%), 333 parts by weight of 1,2-propylene glycol (PG-2) (recovery fraction 235 below) 40.0 mol parts by subtracting parts by weight), 678 parts by weight (60.0 mol parts) of bisphenol A · PO2 mol adduct, 0.5 parts by weight of titanium diisopropoxybistriethanolamate, and nitrogen at 210 ° C After reacting for 5 hours while distilling off the water and ethylene glycol produced under an air stream, 10 parts by weight (1.7 mole parts) of trimellitic anhydride is added and reacted for 1 hour under normal pressure. The reaction was conducted under reduced pressure of 5 to 5 kPa, and the product was taken out at a softening point of 133 ° C. The recovered 1,2-propylene glycol was 235 parts by weight. The obtained resin was cooled to room temperature and then pulverized into particles. This is designated as polyester resin (A1-9).
Tg of (A1-9) was 63 ° C., Tm was 133 ° C., Mp was 13000, the acid value was 1, and the hydroxyl value was 14.

<Production Example 10> [Synthesis of Amorphous Linear Polyester Resin (A2-1)]
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 776 parts by weight of terephthalic acid, 50 parts by weight of benzoic acid, 710 parts by weight of 1,2-propylene glycol (PG-3), titanium diisosodium as a polymerization catalyst After adding 0.5 parts by weight of propoxybistriethanolaminate and reacting at 210 ° C. for 5 hours while distilling off the water generated in a nitrogen stream, the reaction was carried out under a reduced pressure of 2.5 to 5 kPa. Furthermore, 17 parts by weight of trimellitic anhydride was added, and the mixture was reacted for 1 hour under normal pressure. The recovered 1,2-propylene glycol was 380 parts by weight. The obtained resin was cooled to room temperature and then pulverized into particles. This is designated as polyester resin (A2-1).
Mp of (A2-1) was 4800, Tg was 61 ° C., Tm was 106 ° C., the acid value was 10, the hydroxyl value was 18, and the THF-insoluble matter was 1% by weight.

<Production Example 11> [Synthesis of Amorphous Linear Polyester Resin (A2-2)]
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 703 parts by weight of terephthalic acid, 8 parts by weight of phthalic anhydride, 67 parts by weight of adipic acid, 693 parts by weight of 1,2-propylene glycol (PG-3) Then, 24 parts by weight of ethylene glycol and 0.5 parts by weight of titanium diisopropoxybistriethanolamate as a polymerization catalyst were added and reacted at 210 ° C. for 5 hours while distilling off the water generated under a nitrogen stream. The reaction was carried out under reduced pressure of 5 to 5 kPa. Furthermore, 17 parts by weight of trimellitic anhydride was added, and the mixture was reacted for 1 hour under normal pressure. The recovered 1,2-propylene glycol was 332 parts by weight, and ethylene glycol was 11 parts by weight. The obtained resin was cooled to room temperature and then pulverized into particles. This is designated as polyester resin (A2-2).
Mp of (A2-2) is 10,000, Tg is 62 ° C., Tm is 115 ° C., acid value is 9, hydroxyl value is 20, THF insoluble content is 1% by weight, 1,2-propylene glycol in alcohol component The molar ratio was 96 mol%.

<Production Example 12> [Synthesis of polyester resin (B1-1)]
In the reaction vessel, 41 parts by weight (10.2 mol parts) of bisphenol A · EO 2 mol adduct, 457 parts by weight of bisphenol A · PO 3 mol adduct (89.1 mol parts), phenol novolac (average number of functional groups: 5. 6) PO6 mole adduct 9 parts by weight (0.8 mole part), 166 parts by weight (49.8 moles) terephthalic acid, 93 parts by weight (39.8 moles) fumaric acid, and tetrabutoxy as a condensation catalyst 3 parts by weight of titanate was added, and the reaction was carried out for 5 hours while distilling off the generated water under a nitrogen stream of 230 ° C. Next, the reaction is carried out under a reduced pressure of 0.5 to 2.5 kPa. When the acid value becomes 2 or less, the mixture is cooled to 180 ° C., and 41 parts by weight (10.4 mol parts) of trimellitic anhydride is added. After the reaction for 2 hours in a sealed state, the reaction was further performed at 230 ° C. under reduced pressure of 0.5 to 2.5 kPa, and the product was taken out at a softening point of 135 ° C. The taken-out resin was cooled to room temperature and then pulverized into particles. This is designated as polyester resin (B1-1).
Tg of (B1-1) was 58 ° C., Tm was 135 ° C., Mp was 11300, acid value was 20, and hydroxyl value was 5.

<Production Example 13> [Synthesis of polyester resin (B1-2)]
In the reaction vessel, 486 parts by weight (80.7 moles) of bisphenol A · PO3 mole adduct, 23 parts by weight of PO6 mole adduct of phenol novolak (average functional group number: 5.6) (19.3 moles), 166 parts by weight (82.6 parts by mole) of terephthalic acid and 3 parts by weight of tetrabutoxy titanate as a condensation catalyst were added and reacted at 230 ° C. under a nitrogen stream for 5 hours while distilling off the generated water. Next, the reaction is carried out under a reduced pressure of 0.5 to 2.5 kPa. When the acid value becomes 2 or less, the mixture is cooled to 180 ° C., 40 parts by weight (17.4 moles) of trimellitic anhydride is added, After the reaction for 2 hours in a sealed state, the reaction was performed at 230 ° C. under reduced pressure of 0.5 to 2.5 kPa, and the mixture was taken out at a softening point of 145 ° C. The taken out resin was cooled to room temperature and then pulverized into particles. This is designated as polyester resin (B-2).
(B-2) had a Tg of 57 ° C., a Tm of 145 ° C., an Mp of 8,300, an acid value of 20, and a hydroxyl value of 18.

<Production Example 14> [Synthesis of polyester resin (B2-1)]
In the reaction vessel, 418 parts by weight (55 moles) of a bisphenol A · PO3 mole adduct, 320 parts by weight (45 moles) of a bisphenol A · EO2 mole adduct, 274 parts by weight (100 moles) of terephthalic acid, and a condensation catalyst 3 parts by weight of tetrabutoxy titanate was added and reacted at 230 ° C. in a nitrogen stream for 5 hours while distilling off the generated water. Next, the reaction is carried out under a reduced pressure of 0.5 to 2.5 kPa. When the acid value becomes 2 or less, the mixture is cooled to 180 ° C., 42 parts by weight of trimellitic anhydride is added, and the reaction is carried out for 2 hours under normal pressure sealing. It was. The taken out resin was cooled to room temperature and then pulverized into particles. This is designated as polyester resin (B2-1).
Tg of (B2-1) was 64 ° C., Tm was 110 ° C., Mp was 5200, acid value was 25, and hydroxyl value was 50.

<Comparative Production Example 1> [Synthesis of Polyester Resin (RA1-1)]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 631 parts by weight of terephthalic acid, 21 parts by weight of adipic acid, 640 parts by weight of (PG-1), titanium diisopropoxybistriethanolamate 0 as a polymerization catalyst .5 parts by weight was added and reacted for 5 hours while distilling off the water produced at 210 ° C. under a nitrogen stream, and then reacted under reduced pressure of 0.5 to 2.5 kPa for 1 hour. Next, 53 parts by weight of benzoic acid was added, and the mixture was reacted for 3 hours under normal pressure. Further, 94 parts by weight of trimellitic anhydride was added and reacted under normal pressure for 1 hour, followed by reaction under reduced pressure of 2.5 to 5 kPa and taken out at a softening point of 1 ° C. The recovered 1,2-propylene glycol was 250 parts by weight. The obtained resin was cooled to room temperature and then pulverized into particles. This is designated as polyester resin (RA1-1).
Mp of (RA1-1) was 6100, Tg was 65 ° C., Tm was 158 ° C., the acid value was 15, and the hydroxyl value was 13.

<Comparative Production Example 2> [Synthesis of Amorphous Linear Polyester Resin (RA2-1)]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 776 parts by weight of terephthalic acid, 50 parts by weight of benzoic acid, 710 parts by weight of 1,2-propylene glycol (PG-1), titanium diisosodium as a polymerization catalyst. After adding 0.5 parts by weight of propoxybistriethanolaminate and reacting at 210 ° C. for 5 hours while distilling off the water generated in a nitrogen stream, the reaction was carried out under a reduced pressure of 2.5 to 5 kPa. Furthermore, 17 parts by weight of trimellitic anhydride was added, and the mixture was reacted for 1 hour under normal pressure. The recovered 1,2-propylene glycol was 335 parts by weight. The obtained resin was cooled to room temperature and then pulverized into particles. This is designated as polyester resin (RA2-1).
(RA2-1) had an Mp of 4900, a Tg of 60 ° C., a Tm of 105 ° C., an acid value of 9, a hydroxyl value of 19, and a THF insoluble content of 1% by weight.

The main physical property values of the polyester resin (A), the polyester resin (RA), the crystalline resin (B1), the crystalline resin (RB), and the amorphous linear polyester resin (B2) measured by the above method are shown. 1 and 2. In Tables 1 and 2, the power exponent of 10 is indicated by a number with a ^ instead of a number with a superscript. For example, 10 ³ is represented as 10 ^ 3.

<Examples 1-18>, <Comparative Examples 1-4>
Polyester resins (A1-1) to (A1-9), crystalline resins (B1-1) to (B1-2), amorphous linear polyester resins (B2-1) obtained in the above production examples, and comparison The polyester resins (RA-1) to (RA-2) and (RB-1) obtained in the production examples were blended according to the blending ratio (parts by weight) shown in Table 4, and the toner binder of the present invention and the comparative toner A binder was obtained and converted into a toner by the following method.
First, 8 parts by weight of carbon black MA-100 [Mitsubishi Chemical Co., Ltd.], 5 parts by weight of Carnauba wax, 1 part by weight of charge control agent T-77 [Hodogaya Chemical Co., Ltd.] were added, and Henschel mixer [Mitsui The mixture was premixed using FM10B manufactured by Miike Chemical Industry Co., Ltd. and then kneaded using a biaxial kneader [PCM-30 manufactured by Ikegai Co., Ltd.]. Then, after finely pulverizing using a supersonic jet pulverizer Labo Jet [manufactured by Nippon Pneumatic Industry Co., Ltd.], it is classified by an airflow classifier [MDS-I manufactured by Nippon Pneumatic Industry Co., Ltd.], and a particle size D50 is obtained. 8 μm toner particles were obtained. Next, 100 parts by weight of toner particles were mixed with 0.5 part of colloidal silica (Aerosil R972: manufactured by Nippon Aerosil) using a sample mill, and the toner compositions (T-1) to (T-18) of the present invention, and Comparative toner compositions (RT-1) to (RT-4) were obtained.
Table 3 shows the evaluation results evaluated by the following evaluation methods. In Table 4, a blank indicates that the raw material is not blended.

[Evaluation method]
[1] Low-temperature fixability An unfixed image developed using a commercial copier (AR5030; manufactured by Sharp) using the toner composition described above was evaluated using a commercial copier (AR5030; manufactured by Sharp). did. The lower limit temperature at which the residual ratio of the image density measured with a Macbeth reflection densitometer RD-191 (manufactured by Macbeth) after rubbing the fixed image with a pad was defined as the minimum fixing temperature (MFT). The lower the minimum fixing temperature, the better the low-temperature fixing property.
[2] Hot offset resistance The presence or absence of hot offset on a fixed image was visually evaluated in the same manner as in the low temperature fixability evaluation method described above. The upper limit temperature at which hot offset does not occur after passing through the fixing roll was defined as hot offset generation temperature (HOT). The higher the hot offset generation temperature, the better the hot offset resistance.
[HOT-MFT] is described as the fixing temperature range (° C.).
[3] Blocking resistance The above toner composition was mixed with 50 ° C. and 85% R.D. H. Was conditioned for 48 hours in a high temperature and high humidity environment. Under the same environment, the blocking state of the developer was visually determined, and further, the image quality when copied with a commercial copying machine (AR5030: manufactured by Sharp) was observed, and blocking resistance was evaluated according to the following criteria.
[Criteria]
A: There is no toner blocking, and the image quality after copying 3000 sheets is also good.
○: There is no toner blocking, but a slight disturbance is observed in the image quality after copying 3000 sheets.
X: Toner blocking is visible, and no image is produced by 3000 sheets.
[4] Charging property 1 part by weight of the above toner composition and iron powder for electrophotography (ASR-, manufactured by Powdertech)
10) 24 parts by weight, 23 ° C., 50% R.I. H. After adjusting the humidity for 8 hours or more, the mixture was frictionally stirred at 50 rpm × 1, 3, 7, 20, 60, and 120 minutes with a tumbler shaker mixer, and the charge amount was measured at each time. For the measurement, a blow-off charge measuring device [manufactured by Toshiba Chemical Co., Ltd.] was used. The amount of charge at the friction time when the increase in charge amount ceased was taken as the saturation charge amount.
[5] Humidity and heat storage stability of a fixed image A fixing device of a commercial copying machine (AR5030; manufactured by Sharp) is used to develop an unfixed image developed using the above toner composition using a commercial copying machine (AR5030; manufactured by Sharp). Evaluation was performed using an image fixed by using.
A sheet of white paper was brought into close contact with the fixed image, and a load of 100 g was applied thereto. H. Was conditioned for 48 hours in a high temperature and high humidity environment. Under the same environment, the degree of adhesion of the paper was observed, and the wet heat resistance was evaluated according to the following criteria.
[Criteria]
◎: There is no adhesion between the two sheets of paper. ○: The two sheets of paper are weakly bonded. When peeled off, a small amount of toner can be confirmed on the white paper side. ×: The two sheets of paper are strongly bonded. You can see the image clearly moved to the blank side

The toner composition and toner binder of the present invention are excellent in low-temperature fixability, hot offset resistance, blocking resistance, and chargeability. Therefore, the toner for developing an electrostatic image used in electrophotography, electrostatic recording, electrostatic printing, etc. And useful as a toner binder.

Claims (5)

A toner binder comprising a polyester resin (A) having polycarboxylic acid (x) and polyol (y) as structural units, wherein (y) comprises 1,2-propylene glycol (PG), A) contains one or more substances selected from the group consisting of (a) fatty acids or metal salts thereof, (b) sulfur-containing compounds and (c) nitrogen-containing compounds, and (c) nitrogen- containing compounds are ammonia and alkyl 1 or more nitrogen-containing compounds selected from the group consisting of amines and alkanolamines, and 1 selected from the group consisting of (a) fatty acids or metal salts thereof, (b) sulfur-containing compounds and (c) nitrogen-containing compounds A toner binder in which the content of the species or more is 10 to 10,000 ppm based on the weight of (A). 1,2-propylene glycol (PG) is selected from the group consisting of (a) a fatty acid or a metal salt thereof, (b) a sulfur-containing compound, (c) a nitrogen-containing compound, and (d) a trihydric or higher polyhydric alcohol. 2. The toner binder according to claim 1, wherein the toner binder contains at least one kind of substance, and the content thereof is 0.001 to 10% by weight based on the weight of (PG). The toner binder according to claim 1 or 2 , wherein the polyester resin (A) is a non-linear polyester resin (A1) and / or a linear polyester resin (A2). In addition to the polyester resin (A), the toner binder according to any one of claims 1 to 3 containing (A) other than the polyester resin (B). The toner composition containing a colorant and a toner binder according to any one of claims 1-4.