JP2015092240A - Toner binder and toner composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To develop a toner binder and toner composition that emit less odor while achieving low-temperature fixability and hot offset resistance (wide range of fixing temperature).SOLUTION: There is provided a toner binder containing 30 weight% or more of a polyester resin (A) having a polycarboxylic acid component (x) and a polyol component (y) as constitutional units, where the polyester resin (A) has a softening point of 90 to 160°C, 0 to 30 weight% of THF insolubles, the sum of an acid value and a hydroxyl value of 20 to 70; and in pyrolysis gas chromatography-mass spectrometry at a pyrolysis gas temperature of 180°C, the polyester resin (A) has the peak area of 40% or less, which is attributed to acetaldehyde when the total area of all peaks is 100%, and the total area of peaks of 30% or less, which is attributed to aldehyde having a carbon number of 4 to 12.

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.
A toner composition containing a polyester-based toner binder that is excellent in both low-temperature fixability and hot offset resistance is known (see Patent Document 1). However, since the softening temperature is high, there is a problem that the minimum fixing temperature of the toner cannot be sufficiently lowered and the low-temperature fixability is still insufficient. In addition, there is a problem that a peculiar unpleasant odor occurs when the toner binder and the toner composition are produced.

JP 2007-4149 A

  The present invention has been made to solve the above-described problem, and a toner binder and a toner composition having a low odor while maintaining both low-temperature fixability and hot offset resistance (widening temperature range). Is to provide.

As a result of intensive studies to solve the above problems, the present inventors have found that the odor of the toner binder and the whole toner can be greatly improved by adjusting the content ratio of the aldehyde having a specific carbon number. The present invention has been reached.
That is, the present invention is the following two inventions.
(I) A toner binder containing 30% by weight or more of a polyester resin (A) having a polycarboxylic acid component (x) and a polyol component (y) as structural units, and the softening point of the polyester resin (A) is 90 to 90%. In pyrolysis gas chromatograph-mass spectrometry at 160 ° C., THF insoluble content of 0 to 30% by weight, the sum of acid value and hydroxyl value is 20 to 70, and pyrolysis temperature of 180 ° C., the total area of all peaks A toner binder in which the peak area attributed to acetaldehyde is 40% or less, and the total area of peaks attributed to aldehydes having 4 to 12 carbon atoms is 30% or less, assuming that is 100%.
(II) A toner composition containing the toner binder of the present invention and a colorant.

  According to the present invention, it is possible to provide a toner binder and a toner composition with less odor while maintaining both low-temperature fixability and hot offset resistance (wide fixing temperature range). The toner composition of the present invention also has good blocking resistance.

The present invention is described in detail below.
The polyester resin (A) used in the toner binder of the present invention has a polycarboxylic acid component (x) and a polyol component (y) as structural units, and two or more kinds may be used in combination.

In the polyester resin (A), examples of the polycarboxylic acid component (x) include dicarboxylic acids and trivalent or higher polycarboxylic acids. Examples of the dicarboxylic acid include aromatic dicarboxylic acids having 8 to 36 carbon atoms (for example, phthalic acid, isophthalic acid, terephthalic acid, and naphthalenedicarboxylic acid), alkanedicarboxylic acids having 4 to 36 carbon atoms (for example, succinic acid, adipic acid, and sebacic acid). Acid and dodecanedicarboxylic acid), alicyclic dicarboxylic acid having 6 to 40 carbon atoms [for example, dimer acid (dimerized linoleic acid)], alkene dicarboxylic acid having 4 to 6 carbon atoms (for example, maleic acid, fumaric acid, citracone) Acid, alkenyl succinic acid such as mesaconic acid and dodecenyl succinic acid), and ester-forming derivatives thereof.
Examples of the ester-forming derivatives include acid anhydrides, alkyl (C1-C24, preferably 1-4: methyl, ethyl, butyl, stearyl, etc.) esters, and partial alkyl (same as above) esters. . The same applies to the following ester-forming derivatives.
Among these, preferred are phthalic acid, isophthalic acid, terephthalic acid, succinic acid, adipic acid, sebacic acid, maleic acid, fumaric acid, and ester-forming derivatives thereof.

Examples of the trivalent or higher (preferably 3 to 6) polycarboxylic acid include aromatic polycarboxylic acids having 9 to 20 carbon atoms (for example, trimellitic acid and pyromellitic acid), aliphatic groups having 6 to 36 carbon atoms ( And alicyclic polycarboxylic acids (eg, hexanetricarboxylic acid and decanetricarboxylic acid), and ester-forming derivatives thereof.
Of these, trimellitic acid, pyromellitic acid, and ester-forming derivatives thereof are preferable.
In addition, you may use a small amount of C7-14 aromatic monocarboxylic acid (benzoic acid etc.) in the polycarboxylic acid component (x) if necessary.

  From the viewpoint of storage stability and fixability, the polycarboxylic acid component (x) preferably contains 80 mol% or more of aromatic polycarboxylic acid, more preferably 81 to 99.9 mol%, and particularly preferably 82. ˜99.8 mol%.

In the polyester resin (A), examples of the polyol component (y) include diols, trivalent or higher polyols, and combinations thereof.
Diols include aromatic diols and aliphatic diols.

Specific examples of aromatic diols include alkylene oxide adducts of dihydric phenols [monocyclic dihydric phenols (for example, hydroquinone) and bisphenols (bisphenol A, bisphenol F, bisphenol S, etc.)] -4 (oxyethylene group, oxypropylene group, etc.)] [number 2-30 of oxyalkylene units (hereinafter abbreviated as AO units)];
Of these, preferred are alkylene oxide adducts of bisphenol A, and more preferred are ethylene oxide adducts of bisphenol A and propylene oxide adducts of bisphenol A.

Examples of the aliphatic diol include alkylene glycols having 2 to 36 carbon atoms (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, 1,9-nonanediol, and 1,10-decanediol, 1,12-dodecanediol, etc.); alkylene ether glycol having 4 to 36 carbon atoms (diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, And polytetramethylene ether glycol); alicyclic diols having 6 to 36 carbon atoms (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); (poly) oxyalkylenes of the above alicyclic diols Etc. (1-30 of AO units) ether and the like.
Among these, from the viewpoint of achieving both low-temperature fixability and hot offset resistance, alkylene glycols having 2 to 6 carbon atoms are preferable, and ethylene glycol and 1,2-propylene glycol are more preferable.

Trivalent or higher (preferably 3 to 8) polyols include 3 to 8 or higher aliphatic polyhydric alcohols having 3 to 36 carbon atoms (alkane polyols and intramolecular or intermolecular dehydrates such as glycerin). , Trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, sorbitan, polyglycerin, and dipentaerythritol; sugars and derivatives thereof such as sucrose and methylglucoside); (poly) oxyalkylene ethers of the above aliphatic polyhydric alcohols (Number of AO units 1-30); polyoxyalkylene ether (number of AO units 2-30) of novolak-type resin (phenol novolak, cresol novolak, etc., average polymerization degree 3-60); trisphenols (trisphenol PA) Etc.) Etc. (the number 2 to 30 of AO units) oxyalkylene ether.
Of these, polyoxyalkylene ethers of novolac resins are preferable.

  From the viewpoint of achieving both hot offset resistance and low-temperature fixability, the polyol component (y) is a bisphenol A ethylene oxide adduct (the number of oxyethylene units is 2 to 30) and / or A combination containing ethylene glycol, the total content of which is 50 mol% or more based on (y), and a propylene oxide adduct of bisphenol A (the number of oxypropylene units is 2 to 30) and / or 1,2 -The combination which contains propylene glycol and the total content contains 50 mol% or more based on (y) is preferable, and it is further more preferable to contain 55 mol% or more.

In the polyester resin (A) in the present invention, the reaction temperature of the polycarboxylic acid component (x) and the polyol component (y) is preferably 150 to 280 ° C., more preferably in an inert gas (nitrogen gas or the like) atmosphere. Can be carried out by reacting at 170 to 260 ° C, particularly preferably at 180 to 240 ° C. The reaction time is preferably 30 minutes or more, particularly preferably 2 to 40 hours, from the viewpoint of reliably performing the polycondensation reaction. In order to improve the reaction rate at the end of the reaction, it is also effective to perform a reduced pressure (preferably 0.1 to 10 kPa) reaction after a normal pressure (atmospheric pressure) 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 1.4 / 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 (triethanolaminate), 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 catalysts (for example, zirconyl acetate), zinc acetate, and the like. Among these, a titanium-containing catalyst is preferable.

The softening point [T (1/2)] of the polyester resin (A) is 90 to 160 ° C, preferably 95 to 158 ° C, more preferably 104 to 155 ° C. Within this range, both hot offset resistance and low-temperature fixability are good. In the present invention, T (1/2) is measured by the following method.
<Softening point [T (1/2)]>
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 the half of a measurement sample flows out) be a softening point [T (1/2)].

The THF insoluble matter in the polyester resin (A) used in the present invention is 0 to 30% by weight, preferably 1 to 27% by weight, more preferably from the viewpoint of hot offset resistance when used as a toner. 1 to 25% by weight.
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 sum of the acid value and the hydroxyl value of the polyester resin (A) used in the present invention is 20 to 70, preferably 25 to 65. Within this range, the charging stability of the toner due to environmental changes is excellent.
In the present invention, the acid value and hydroxyl value of the polyester resin are measured by the method defined in JIS K0070 (1992 edition).
In addition, when there exists a solvent insoluble part accompanying bridge | crosslinking in a sample, the thing after melt-kneading is used as a sample by the following method.
Kneading apparatus: Laboplast mill MODEL4M150 manufactured by Toyo Seiki Co., Ltd.
Kneading conditions: 130 ° C., 30 minutes at 70 rpm

The temperature rising pyrolysis gas chromatograph-mass spectrometry of the polyester resin (A) used in the present invention is performed under the following conditions, and the peak area attributed to acetaldehyde is 40% when the total area of all peaks is 100%. It is necessary to be below, and 0 to 38% is preferable.
In addition, the total area of peaks attributed to aldehydes having 4 to 12 carbon atoms needs to be 30% or less, preferably 0 to 28%. If it is within this range, the odor of the toner binder or toner can be considerably reduced.
Examples of the aldehyde having 4 to 12 carbon atoms include crotonaldehyde, valeraldehyde, isovaleraldehyde, 2-methyl-2-butenal, 2-pentenal, capronaldehyde, 2-hexenal, 2-methyl-2-pentenal, 2 -Ethyl-2-butenal, enanthal, 2-heptenal, 2-methyl-2-hexenal, 2,2-dimethyl-3-pentenal, 2,3-dimethyl-2-pentenal, octanal, nonanal, decanal, undecanal, Examples include dodecanal.
Examples of the method for bringing acetaldehyde and an aldehyde having 4 to 12 carbon atoms into the above range include, for example, a method of taking out a liquid polyester resin produced in a reaction vessel into water (preferably a water temperature of 20 to 100 ° C.), and a polyester resin. And a method of devolatilizing at a temperature below the glass transition point. Specific examples of the devolatilization method include a method in which a polyester resin is pulverized and granulated, and then allowed to stand under reduced pressure (for example, 0.5 to 10 kPa), and a method in which an inert gas such as nitrogen is blown. It is done.

<Temperature pyrolysis gas chromatograph-mass spectrometry (pyrolysis GC / MS)>
1. Pyrolysis equipment and conditions Equipment: TurboMatrix 40 manufactured by Perkin Elmer Japan
Thermal decomposition temperature: 180 ° C
Thermal decomposition time: 60 min
2. GC / MS apparatus and conditions apparatus: GCMS QP-2010 manufactured by Shimadzu Corporation
Column: ZB-5 (30 m × 0.25 mm × 1 μm)
Oven temperature: 40 ° C. (3 min) -2 ° C./min (70 ° C.)-5 ° C./min (150 ° C.)-10 ° C./min (300 ° C.)-30 min
Carrier gas: He (pressure 100 kPa)
Interface temperature: 250 ° C
Injection method: Full volume injection Inlet temperature: 200 ° C
Detector (MS): GCMS QP-2010 manufactured by Shimadzu Corporation
MS temperature: ion source 200 ° C.
Scan range: EI (Electron Ionization): m / z (mass / charge of ions) 33-500
3. Sampling conditions Vial size: 20 ml headspace vial Sample volume: 100 mg

  The toner binder of the present invention may contain, in addition to the polyester resin (A), other resins usually used as a toner binder as long as the characteristics are not impaired. Examples of the other resins include polyester resins other than the polyester resin (A), styrene resins having a weight average molecular weight [Mw] of 1,000 to 1,000,000, resins having a structure in which a vinyl resin is grafted on a polyolefin resin, epoxy resins, A polyurethane resin is mentioned. Other resins may be blended with (A) or partially reacted.

The polyester resin other than the polyester resin (A) is a polyester resin having the same composition and physical properties as in (A), and the total area of all peaks in pyrolysis gas chromatograph-mass spectrometry at a pyrolysis temperature of 180 ° C. The peak area attributed to acetaldehyde when the content is 100% exceeds 40%, or the peak area attributed to aldehydes having 4 to 12 carbon atoms exceeds 30%.
The peak area attributed to acetaldehyde in the above analysis of the polyester resin other than (A) is preferably 50% or less, more preferably 45% or less. The total area of peaks attributed to aldehydes having 4 to 12 carbon atoms is preferably 40% or less, more preferably 35% or less.

The content of the polyester resin (A) in the toner binder of the present invention is 30% by weight or more, and preferably 50% by weight or more, more preferably 80% by weight or more, from the viewpoint of reducing the odor of the toner binder or toner composition. Particularly preferably, it is 90% by weight or more.
Further, the total content of the polyester resins other than the polyester resins (A) and (A) is preferably 90% by weight or more, and more preferably 95% by weight or more, from the viewpoint of the wide fixing temperature range.

In the toner binder of the present invention, the mixing method when two or more kinds of resins are used is not particularly limited, and may be a publicly known method, which may be either powder mixing or melt mixing. Further, it may be mixed at the time of toner formation.
Examples of the mixing device in the case of melt mixing include a batch type mixing device such as a reaction tank and a continuous mixing device. 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 Henschel mixer (registered trademark), Nauter mixer (registered trademark), and 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, olazole brown B, and oil pink OP, etc. The above 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, more preferably 3 to 10 parts, with respect to 100 parts of the toner binder of the present invention. In addition, when using magnetic powder, Preferably it is 20-150 parts, More preferably, it is 40-120 parts. Above and below, parts mean parts by weight.

  One or more additives selected from a release agent, a charge control agent, a fluidizing agent, and the like may be added to the toner composition of the present invention.

As the mold release agent, those having a melting point of 50 to 170 ° C. are preferable, and polyolefin wax, natural wax, Fischer-Tropsch wax, aliphatic alcohol having 30 to 50 carbon atoms, fatty acid having 30 to 50 carbon atoms, and a mixture thereof. Can be mentioned.
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 with 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), and olefins and unsaturated carboxylic acids [such as (meth) acrylic acid, itaconic acid and maleic anhydride] and / or unsaturated carboxylic acid alkyl esters [( Alkyl methacrylate (alkyl carbon) 18) copolymers of esters and maleic acid alkyl (C1-18 alkyl) esters, etc.] and the like.

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 triacontanoic acid.
Examples of Fischer-Tropsch wax include petroleum-based Fischer-Tropsch wax (Paraflint H1, Paraflint H1N4, Paraflint C105, etc. manufactured by Schumann-Sazol), natural gas-based Fischer-Tropsch wax (FT100, manufactured by Shell MDS, etc.), and Fischer-Tropsch wax. And purified by a method such as fractional crystallization [Nippon Seiwa Co., Ltd. MDP-7000 and MDP-7010] and the like.
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 triacontanoic 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 based on the toner weight (% in this item is% by weight), and the toner binder of the present invention is preferably 30 to 97%, more preferably 40 to 95%, Particularly preferably 45 to 92%; Colorant, preferably 0.05 to 60%, more preferably 0.1 to 55%, particularly preferably 0.5 to 50%; , Preferably 0 to 30%, more preferably 0.5 to 20%, particularly preferably 1 to 10%; the charge control agent is preferably 0 to 20%, more preferably 0.1 to 10%, particularly preferably 0.5 to 7.5%; The fluidizing agent is preferably 0 to 10%, more preferably 0 to 5%, and particularly preferably 0.1 to 4%. The total content of additives is preferably 3 to 70%, more preferably 4 to 58%, and particularly preferably 5 to 50%. 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 a conventionally known method such as a kneading and pulverizing method. For example, in order to obtain toner by the kneading and pulverizing method, the components constituting the toner excluding the fluidizing agent are dry blended, then melt-kneaded, then coarsely pulverized, and finally atomized using a jet mill pulverizer or the like. By further classifying, the volume-based median 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)].

  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. Hereinafter, unless otherwise specified, “%” represents “% by weight”, and “mol” in () represents mol part.

<Production Example 1> [Synthesis of polyester resin (A-1)]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube (the reaction vessel used in the following production examples is also the same), 349 parts (5.6 mol) of ethylene glycol and 251 parts of neopentyl glycol (2.4 mol) ), 398 parts (2.4 mol) of terephthalic acid, 267 parts (1.6 mol) of isophthalic acid, 1 part (9.6 mmol) of adipic acid, 38 parts (0.31 mol) of benzoic acid and tetrapolymer as a polymerization catalyst. After adding 2 parts of butoxy titanate, the reaction was carried out for 5 hours while distilling off the water and ethylene glycol produced at 210 ° C under a nitrogen stream, and then for 2 hours under reduced pressure of 0.5 to 2.5 kPa. It was. Next, 60 parts (0.31 mol) of trimellitic anhydride was added and reacted for 1 hour under normal pressure, then reacted for 5 hours under a reduced pressure of 0.5 to 2.5 kPa, and further 2.5 to 5 kPa. The reaction was carried out under reduced pressure, and when the softening point reached 145 ° C., it was taken out into water at 25 ° C. The obtained resin was cooled to room temperature and then pulverized into particles. This is designated as polyester resin (A-1).
T (1/2) of polyester resin (A-1) is 145 ° C., THF insoluble matter is 23%, acid value is 15, hydroxyl value is 15 (sum of acid value and hydroxyl value is 30), thermal decomposition temperature In pyrolysis gas chromatograph-mass spectrometry at 180 ° C., the peak area attributed to acetaldehyde when the total area of all peaks is 100% is 28%, and the peak attributed to aldehydes having 4 to 12 carbon atoms The total area was 22%.

<Production Example 2> [Synthesis of polyester resin (A-2)]
In the reaction vessel, 466 parts (7.5 moles) of ethylene glycol, 230 parts (2.2 moles) of neopentyl glycol, 371 parts (2.2 moles) of terephthalic acid, 247 parts (1.5 moles) of isophthalic acid, After adding 1 part (9.6 mmol) of adipic acid, 40 parts (0.35 mol) of benzoic acid and 2 parts of tetrabutoxytitanate as a polymerization catalyst, water and ethylene glycol produced at 210 ° C. in a nitrogen stream were distilled. The reaction was allowed to proceed for 5 hours while leaving, and then allowed to react for 2 hours under a reduced pressure of 5 to 20 mmHg. Next, 120 parts (0.62 mol) of trimellitic anhydride was added, and the mixture was reacted for 1 hour under normal pressure, and then reacted for 2 hours under a reduced pressure of 5 to 20 mmHg to obtain 0.10 parts (5.6 parts of ion-exchanged water (5.6). In addition, when the softening point 134 ° C. was reached, it was taken out into water at 25 ° C. The obtained resin was cooled to room temperature and then pulverized into particles. This is designated as polyester resin (A-2).
T (1/2) of polyester resin (A-2) is 134 ° C., THF-insoluble matter is 16%, acid value is 33, hydroxyl value is 4 (sum of acid value and hydroxyl value is 37), thermal decomposition temperature In pyrolysis gas chromatograph-mass spectrometry at 180 ° C., the peak area attributed to acetaldehyde when the total area of all peaks is 100% is 32%, and the peak attributed to aldehydes having 4 to 12 carbon atoms The total area was 21%.

<Production Example 3> [Synthesis of Polyester Resin (A-3)]
In a reaction vessel, 366 parts (1.1 moles) of a bisphenol A propylene oxide (hereinafter referred to as PO) 2 mole adduct, bisphenol A ethylene oxide (hereinafter referred to as EO) 2 moles adduct 1 part (3 0.2 mmol), 252 parts (4.1 mol) of ethylene glycol, 294 parts (1.8 mol) of terephthalic acid, 126 parts (0.76 mol) of isophthalic acid, 1 part (6.8 mmol) of phthalic anhydride, After adding 36 parts (0.19 mol) of trimellitic anhydride and 2 parts of tetrabutoxytitanate as a polymerization catalyst, a polyesterification reaction was performed at 230 ° C. Next, 67 parts (0.35 mol) of trimellitic anhydride was added and reacted under normal pressure for 1 hour, then reacted under reduced pressure of 0.5 to 2.5 kPa, and reached a softening point of 154 ° C. It was taken out in water at 25 ° C. The obtained resin was cooled to room temperature and then pulverized into particles. This is designated as polyester resin (A-3).
Polyester resin (A-3) has T (1/2) of 154 ° C., THF-insoluble content of 25%, acid value of 17, hydroxyl value of 16 (sum of acid value and hydroxyl value is 33), thermal decomposition temperature In pyrolysis gas chromatograph-mass spectrometry at 180 ° C., the peak area attributed to acetaldehyde when the total area of all peaks is 100% is 31%, and the peak attributed to aldehydes having 4 to 12 carbon atoms The total area was 20%.

<Production Example 4> [Synthesis of polyester resin (A-4)]
In a reaction vessel, 340 parts (0.99 mol) of PO2 mol adduct of bisphenol A, 317 parts (1.0 mol) of EO2 mol adduct of bisphenol A, phenol novolak resin (number of nuclei of about 5.6) 5.6 mol EO adduct 1 part (1.2 mmol), terephthalic acid 300 parts (1.8 mol), fumaric anhydride 1 part (8.6 mmol) and tetrabutoxy titanate 2 parts as polymerization catalyst were added. Thereafter, the polyesterification reaction was carried out at 230 ° C., and when the acid value became 2 or less, the mixture was cooled to 180 ° C., and 22 parts (0.11 mol) of trimellitic anhydride was added and held at 180 ° C. for 1 hour. , Took out. The resin taken out was cooled to room temperature, pulverized and granulated, and devolatilized at 40 ° C. and 3 kPa for 1 hour in a vacuum dryer. This is designated as polyester resin (A-4).
T (1/2) of the polyester resin (A-4) is 107 ° C., THF-insoluble content is 2%, acid value is 20, hydroxyl value is 22 (sum of acid value and hydroxyl value is 42), thermal decomposition temperature In pyrolysis gas chromatograph-mass spectrometry at 180 ° C., the peak area attributed to acetaldehyde when the total area of all peaks is 100% is 28%, and the peak attributed to aldehydes having 4 to 12 carbon atoms The total area was 22%.

<Production Example 5> [Synthesis of polyester resin (A-5)]
In the reaction vessel, 697 parts (2.2 mol) of EO2 mol adduct of bisphenol A, 1 part (2.9 mmol) of PO2 mol adduct of bisphenol A, 314 parts (1.9 mol) of terephthalic acid, fumaric acid After 1 part (8.6 mmol) and 2 parts of tetrabutoxytitanate as a polymerization catalyst were added, a polyesterification reaction was carried out at 230 ° C., and when the acid value became 2 or less, the mixture was cooled to 180 ° C. The merit acid 55 parts (0.29 mol) was prepared, kept at 180 ° C. for 1 hour and taken out. The resin taken out was cooled to room temperature and then pulverized to form particles, and then blown with nitrogen in the resin at room temperature for 2 hours for devolatilization. This is designated as polyester resin (A-5).
Polyester resin (A-5) has T (1/2) of 113 ° C., THF-insoluble content of 1%, acid value of 30, hydroxyl value of 14 (sum of acid value and hydroxyl value is 44), thermal decomposition temperature In pyrolysis gas chromatograph-mass spectrometry at 180 ° C., the peak area attributed to acetaldehyde is 30% when the total area of all peaks is 100%, and the peak attributed to aldehydes having 4 to 12 carbon atoms The total area was 18%.

<Production Example 6> [Synthesis of polyester resin (A-6)]
In a reaction vessel, 805 parts (10.6 mol) of 1,2-propylene glycol, 214 parts (0.65 mol) of an EO2 mol adduct of bisphenol A, 528 parts (3.2 mol) of terephthalic acid, 52 adipic acid 52 1 part (0.36 mol) and 2 parts of tetrabutoxy titanate as a polymerization catalyst were added, and then reacted for 5 hours while distilling off water and 1,2-propylene glycol generated at 210 ° C. under a nitrogen stream. The reaction was carried out under a reduced pressure of 0.5 to 2.5 kPa, and when the softening point of 92 ° C. was reached, the pressure was returned to normal pressure and cooled to 180 ° C. Trimellitic anhydride 26 parts (0.14 mol) was added, and after reaction for 1 hour, it was taken out in water at 25 ° C. The obtained resin was cooled to room temperature and then pulverized into particles. This is designated as polyester resin (A-6).
T (1/2) of polyester resin (A-6) is 95 ° C., THF-insoluble matter is 0%, acid value is 15, hydroxyl value is 50 (the sum of acid value and hydroxyl value is 65), thermal decomposition temperature In pyrolysis gas chromatograph-mass spectrometry at 180 ° C., the peak area attributed to acetaldehyde when the total area of all peaks is 100% is 12%, and the peak attributed to aldehydes having 4 to 12 carbon atoms The total area was 8%.

<Comparative Production Example 1> [Synthesis of Polyester Resin (RA-1)]
Until the take-out step, a polyester resin was synthesized under the same conditions as in Production Example 1 and taken out when the softening point was reached at 145 ° C. The obtained resin was cooled to room temperature and then pulverized into particles. This is designated as polyester resin (RA-1).
T (1/2) of polyester resin (RA-1) is 145 ° C., THF-insoluble matter is 23%, acid value is 15, hydroxyl value is 16 (sum of acid value and hydroxyl value is 31), thermal decomposition temperature In pyrolysis gas chromatograph-mass spectrometry at 180 ° C., the peak area attributed to acetaldehyde when the total area of all peaks is 100% is 43%, and the peak attributed to aldehydes having 4 to 12 carbon atoms The total area was 32%.

<Comparative Production Example 2> [Synthesis of Polyester Resin (RA-2)]
A polyester resin was synthesized under the same conditions as in Production Example 2 until the take-out step, and was taken out when the softening point reached 134 ° C. The obtained resin was cooled to room temperature and then pulverized into particles. This is designated as polyester resin (RA-2).
T (1/2) of polyester resin (RA-2) is 135 ° C., THF-insoluble matter is 23%, acid value is 32, hydroxyl value is 3 (the sum of acid value and hydroxyl value is 35), thermal decomposition temperature In pyrolysis gas chromatograph-mass spectrometry at 180 ° C., the peak area attributed to acetaldehyde when the total area of all peaks is 100% is 42%, and the peak attributed to aldehydes having 4 to 12 carbon atoms The total area was 23%.

<Comparative Production Example 3> [Synthesis of Polyester Resin (RA-3)]
A polyester resin was synthesized under the same conditions as in Production Example 3 until the removal step, and was taken out when the softening point was reached at 154 ° C. The obtained resin was cooled to room temperature and then pulverized into particles. This is designated as polyester resin (RA-3).
T (1/2) of polyester resin (RA-3) is 154 ° C., THF insoluble content is 26%, acid value is 15, hydroxyl value is 15 (the sum of acid value and hydroxyl value is 30), thermal decomposition temperature In pyrolysis gas chromatograph-mass spectrometry at 180 ° C., the peak area attributed to acetaldehyde when the total area of all peaks is 100% is 26%, and the peak attributed to aldehydes having 4 to 12 carbon atoms The total area of was 34%.

<Examples 1-5, Comparative Examples 1-4>
The polyester resins (A-1) to (A-6) obtained in the above production examples and the polyester resins (RA-1) to (RA-3) obtained in the comparative production examples are blended in the ratio shown in Table 1 ( Part) to obtain the toner binder of the present invention consisting of the polyester resin (A) and the comparative toner binder, which were converted into toners by the following method. (Carbon black MA-100 [Mitsubishi Chemical Co., Ltd.], polyolefin wax, charge control agent T-77 [Hodogaya Chemical Co., Ltd.]).
First, after preliminarily mixing using a Henschel mixer [FM10B manufactured by Nippon Coke Industries, Ltd.], the mixture was kneaded at 150 ° C. using a Laboplast mill MODEL4M150 [manufactured by Toyo Seiki Co., Ltd.]. Then, after finely pulverizing using a supersonic jet crusher lab 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 the particle size D50 is 8 μm toner particles were obtained. Next, 100 parts of toner particles are mixed with 0.5 part of colloidal silica (Aerosil R972: manufactured by Nippon Aerosil Co., Ltd.) using a sample mill, and toner compositions (T-1) to (T-5) of the present invention are mixed. And comparative toner compositions (RT-1) to (RT-4) were obtained.
Table 1 shows the results of evaluating these toner compositions by the following evaluation methods.

[Evaluation method]
[1] Minimum fixing temperature (MFT)
Using the toner composition described above, an unfixed image developed with a commercial copying machine (AR5030; manufactured by Sharp Corporation) is converted into a commercial full-color copying machine (LBP-2160, manufactured by Canon Inc.) and a heat roller Fixing was performed at a process speed of 110 mm / sec using a fixing machine with variable temperature. After the fixed image was rubbed with a pad, the minimum fixing temperature (MFT) was defined as the fixing roll temperature at which the residual ratio of the image density measured with a Macbeth reflection densitometer RD-191 (manufactured by Macbeth) was 70% or more. .
[2] Hot offset generation temperature (HOT)
The fixing was evaluated in the same manner as the MFT, and the presence or absence of hot offset on the fixed image was visually evaluated. The temperature at which the hot offset occurred was defined as the hot offset occurrence temperature (HOT).
[3] Blocking Resistance of Toner The above toner composition was conditioned for 48 hours in a high temperature and high humidity environment of 50 ° C. and 85% RH. Under the same environment, the blocking state of the toner composition was visually determined, and further, the image quality when copied with a commercially available copying machine (AR5030: manufactured by Sharp) was observed and 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.
(Triangle | delta): The blocking of toner can be visually observed and disorder is observed in the image quality after 3000 copies.
X: Toner blocking is visible, and no image is produced by 3000 sheets.
[4] Odor test 1.0 g of the toner composition was placed in a glass test tube with a lid (φ15 mm × 150 mm), sealed, and heated at 210 ° C. for 5 minutes. Thereafter, the lid was removed, and 10 monitors confirmed the odor and evaluated it according to the following criteria.
[Criteria]
◎: 1 person responds that it smells or only 1 person smells ○: 2 to 3 persons respond that it smells △: 4 to 6 persons respond that it smells ×: 7 or more persons respond that it smells

The toner composition and toner binder of the present invention are toners and toners for developing electrostatic images that are used for electrostatic printing or the like with little odor while maintaining both low temperature fixability and hot offset resistance (wide fixing temperature range). Useful as a binder.

Claims (5)

  A toner binder containing 30% by weight or more of a polyester resin (A) having a polycarboxylic acid component (x) and a polyol component (y) as structural units, the softening point of the polyester resin (A) is 90 to 160 ° C., In the pyrolysis gas chromatograph-mass spectrometry, the total area of all peaks is 100% in the THF insoluble content of 0 to 30% by weight, the sum of the acid value and the hydroxyl value of 20 to 70, and the thermal decomposition temperature at 180 ° C A toner binder in which the peak area attributed to acetaldehyde is 40% or less and the total area of peaks attributed to aldehydes having 4 to 12 carbon atoms is 30% or less. The polyol component (y) contains bisphenol A ethylene oxide adduct (the number of oxyethylene units is 2 to 30) and / or ethylene glycol, and the total content thereof is 50 mol% or more based on (y). The toner binder according to claim 1. The polyol component (y) contains a propylene oxide adduct of bisphenol A (the number of oxypropylene units is 2 to 30) and / or 1,2-propylene glycol, and the total content is 50 based on (y). The toner binder according to claim 1, which is at least mol%.   The toner binder according to claim 1, wherein the polycarboxylic acid component (x) contains 80 mol% or more of an aromatic polycarboxylic acid. A toner composition comprising the toner binder according to claim 1 and a colorant.