JP5490771B2 - 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.
A toner composition comprising 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 fixing lower limit temperature of the toner cannot be lowered and the low-temperature fixability is not sufficient. Further, since the melt viscosity is high, there is a problem that the glossiness of an image obtained by fixing the toner on the recording medium is not sufficient.

JP-A-12-75549

  The present invention has been made to solve the above-described problems, and is excellent in both low-temperature fixability and hot offset resistance (wide fixing temperature range), glossiness, and storage stability. Toner binder and toner are provided.

The inventors of the present invention have arrived at the present invention as a result of intensive studies to develop a toner binder excellent in all of the fixing temperature width, glossiness, and storage stability.
That is, the present invention is the following two inventions.
(I) A polyester resin (A) having a polycarboxylic acid component (x) and a polyol component (y) as structural units and a polyester resin (B) are contained, and the softening point of the polyester resin (A) is 120 to 150 ° C., The weight average molecular weight is 100,000 to 300,000, the loss tangent [tan δ (140)] at 140 ° C. and the loss tangent [tan δ (190)] at 190 ° C. satisfy the following formula (1), and the softening point of the polyester resin (B) is 90 A toner binder having a loss tangent [tan δ (100)] at 100 ° C. and a loss tangent [tan δ (140)] at 140 ° C. satisfying the following formula (2):
1.0 ≦ [tan δ (190)] / [tan δ (140)] ≦ 5.0 Formula (1)
3.0 ≦ [tan δ (140)] / [tan δ (100)] ≦ 15.0 Formula (2)
(II) A toner composition containing the toner binder, a colorant, and, if necessary, one or more additives selected from a release agent, a charge control agent, and a fluidizing agent.

  According to the present invention, it is possible to provide a toner binder and a toner excellent in both low-temperature fixability and hot offset resistance (wide fixing temperature range), glossiness, and storage stability. .

The present invention is described in detail below.
The toner binder of the present invention contains a polyester resin (A) and a polyester resin (B) having a polycarboxylic acid component (x) and a polyol component (y) as constituent units.

In the polyester resin (A) and the polyester resin (B), 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), alkane dicarboxylic acids having 4 to 8 carbon atoms (for example, succinic acid, and adipic acid). C9-C36 alkane dicarboxylic acid (e.g., sebacic acid and dodecane dicarboxylic acid), C6-C40 alicyclic dicarboxylic acid [e.g., dimer acid (dimerized linoleic acid)], C4-C8 Alkene dicarboxylic acids (for example, maleic acid, fumaric acid, citraconic acid, and mesaconic acid), alkene dicarboxylic acids having 9 to 36 carbon atoms (for example, alkenyl succinic acid such as dodecenyl succinic acid), and ester-forming derivatives thereof Can be mentioned.
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.

The polyester resin (A) and the polyester resin (B) preferably contain 90 mol% or more of an aromatic polycarboxylic acid in the polycarboxylic acid component (x) from the viewpoint of storage stability and fixability. Preferably it is 91-99.9 mol%, Most preferably, it is 92-99.7 mol%.
In addition, at least one of (A) and (B), preferably both, further contains an alkanedicarboxylic acid and / or alkenedicarboxylic acid having 4 to 8 carbon atoms in the polycarboxylic acid component (x) in an amount of 0.1 to 10. It is preferable to contain mol%, Preferably it is 0.2-9 mol%, More preferably, it is 0.3-8 mol%. When the content of the alkene dicarboxylic acid having 4 to 8 carbon atoms is 0.1 mol% or more, the storage stability is better, and when it is 10 mol% or less, the transparency is good when used for a color toner. become.

In the polyester resin (A) and the polyester resin (B), the polyol component (y) includes a diol and a trivalent or higher polyol.
Examples of the diol include aromatic diols and aliphatic diols, and examples of the aromatic diol include polyoxyalkylene ethers of bisphenols. As specific examples, polyoxyalkylenes of dihydric phenols [monocyclic dihydric phenols (for example, hydroquinone) and bisphenols (bisphenol A, bisphenol F, bisphenol S, etc.)] 2 to 4 carbon atoms of an alkylene group (oxyethylene) And the following polyoxyalkylene groups are the same] ether [numbers 2 to 30 of oxyalkylene units (hereinafter abbreviated as AO units)]; and the like.
Among these, bisphenol A polyoxyalkylene ether is preferable, and bisphenol A polyethylene ether and bisphenol A polypropylene ether are more preferable.

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, an unbranched aliphatic diol having a primary hydroxyl group at the molecular end (ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, 1,10-decanediol, etc.) are preferred.
From the viewpoint of storage stability, ethylene glycol, 1,3-propylene glycol, and 1,4-butanediol are more preferable, and ethylene glycol is particularly 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.

The polyester resin (A) and the polyester resin (B) preferably contain a diol and, if necessary, a trivalent or higher polyol in the polyol component (y), from the viewpoint of storage stability, and bisphenols (particularly bisphenol A). And a polyoxyalkylene ether of a novolak type resin as required. From the viewpoint of grindability, it is preferable to contain a polyoxypropylene ether of a bisphenol (particularly bisphenol A) among polyoxyalkylene ethers of bisphenols.
When these are contained, the content of polyoxyalkylene ethers of bisphenols in (y) is preferably 90 mol% or more, more preferably 91 to 99.95 mol%, from the viewpoint of storage stability.
The content of polyoxypropylene ether of bisphenols is preferably 70 mol% or more, more preferably 72 to 99.95 mol%, from the viewpoint of grindability.
Further, the content of the polyoxyalkylene ether of the novolak type resin is preferably 0.02 to 10 mol%, more preferably 0.05 to 8 mol%, from the viewpoint of storage stability.

The polyester resin (A) and the polyester resin (B) 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 polycarboxylic 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. Can be carried out by reacting 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. 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 (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) used in the present invention is 120 to 180 ° C, preferably 123 to 170 ° C, more preferably 125 to 160 ° C. Outside this range, it becomes difficult to achieve both hot offset resistance and low-temperature fixability. 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 weight average molecular weight [Mw] of (A) is from 100,000 to 300,000, preferably from 110000 to 290000, more preferably from 120,000 to 280000, from the viewpoint of achieving both heat-resistant storage stability and low-temperature fixability of the toner.

In the present invention, the weight average molecular weight [Mw] of the polyester resin is measured under the following conditions using gel permeation chromatography (GPC).
Device (example): HLC-8120 manufactured by Tosoh Corporation
Column (example): TSK GEL GMH6 2 [Tosoh Corporation]
Measurement temperature: 40 ° C
Sample solution: 0.25 wt% THF (tetrahydrofuran) 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 is measured by dissolving a polyester resin in THF and filtering out the insoluble matter with a glass filter.

The polyester resin (A) has a loss tangent [tan δ (140)] at 140 ° C. and a loss tangent [tan δ (190)] at 190 ° C. from the standpoint of achieving both offset resistance and gloss. It is necessary to satisfy, it is preferable to satisfy the formula (1 ′), and it is more preferable to satisfy the formula (1 ″).
1.0 ≦ [tan δ (190)] / [tan δ (140)] ≦ 5.0 (1)
1.2 ≦ [tan δ (190)] / [tan δ (140)] ≦ 4.8 Expression (1 ′)
1.3 ≦ [tan δ (190)] / [tan δ (140)] ≦ 4.5 Formula (1 ″)
It is known that the above formula (1), which is excellent in offset resistance when used as a toner, generally tends to be inferior in glossiness, but tan δ (190) and tan δ (140) in (A). The ratio was determined to be an important factor for the balance between the offset resistance and the glossiness, and the optimum range was determined by numerous experiments.
In order to adjust the loss tangent [tan δ] of (A), for example, when reducing [tan δ (190)] / [tan δ (140)], the softening point of the polyester resin (A) [T (1/2) It can be achieved by increasing the ratio of constituents having three or more valences, increasing the number of crosslinking points, increasing the molecular weight, and the like.

In the present invention, the loss tangent [tan δ] of the polyester resin is measured using the following viscoelasticity measuring apparatus.
Apparatus: ARES-24A (Rheometric)
Jig: 25 mm parallel plate Frequency: 1 Hz
Distortion rate: 5%
Temperature increase rate: 5 ° C / min

The acid value of the polyester resin (A) is preferably 10 to 50 (mg KOH / g, the same shall apply hereinafter), more preferably 15 to 35. When the acid value is 50 or less, charging characteristics when used as a toner do not deteriorate.
The hydroxyl value of (A) is preferably 0 to 10 (mg KOH / g, the same shall apply hereinafter), and more preferably 0 to 9. When the hydroxyl value is 10 or less, the environmental stability 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 softening point [T (1/2)] of the polyester resin (B) used in the present invention is 90 ° C. or higher and lower than 120 ° C., preferably 95 to 119 ° C., particularly preferably 100 to 115 ° C. Outside this range, it becomes difficult to achieve both hot offset resistance and low-temperature fixability.

  The weight average molecular weight [Mw] of (B) is 20000 to 40000, preferably 21000 to 39000, and more preferably 22000 to 38000, from the viewpoint of achieving both low-temperature fixability and offset resistance of the toner.

The polyester resin (B) has a loss tangent [tan δ (100)] at 100 ° C. and a loss tangent [tan δ (140)] at 140 ° C. from the viewpoints of both low-temperature fixability and offset resistance and gloss. It is necessary to satisfy the formula (2), it is preferable to satisfy the formula (2 ′), and it is more preferable to satisfy the formula (2 ″).
3.0 ≦ [tan δ (140)] / [tan δ (100)] ≦ 15.0 Formula (2)
3.2 ≦ [tan δ (140)] / [tan δ (100)] ≦ 14.8 Expression (2 ′)
3.5 ≦ [tan δ (140)] / [tan δ (100)] ≦ 14.5 Formula (2 ″)
It is known that the above formula (2) generally has excellent offset resistance when used as a toner, but tends to be inferior in low-temperature fixability and glossiness. The ratio of tan δ (100) was found to be an important factor for the balance between offset resistance, low-temperature fixability and glossiness, and the optimum range was determined by numerous experiments.
In order to adjust the loss tangent [tan δ] of (B), for example, when reducing [tan δ (140)] / [tan δ (100)], the softening point of the polyester resin (B) [T (1/2) It can be achieved by increasing the ratio of constituents having three or more valences, increasing the number of crosslinking points, increasing the molecular weight, and the like.

The acid value of the polyester resin (B) is preferably 5 to 50, more preferably 10 to 35. When the acid value is 50 or less, charging characteristics when used as a toner do not deteriorate.
The hydroxyl value of (B) is preferably 10-40, more preferably 12-30. When the hydroxyl value is 10 or more or 40 or less, the charging characteristics when used as a toner are excellent.

  The weight ratio [(A) / (B)] of the polyester resin (A) and the polyester resin (B) in the toner binder of the present invention when the total of (A) and (B) is 100 is expressed as the toner. From the point of balance between hot offset resistance and low temperature fixability when used, it is preferably 10/90 to 90/10, more preferably 15/85 to 85/15, particularly preferably 20/80 to 80 /. 20.

  The toner binder of the present invention may contain, in addition to the polyester resin (A) and the polyester resin (B), other resins usually used as a toner binder as long as the characteristics are not impaired. Examples of other resins include 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, and polyurethane resins. Other resins may be blended with (A) and (B) or may be partially reacted. The content of other resins is preferably 10% by weight or less, more preferably 5% by weight or less.

In the toner binder of the present invention, the mixing method of two or more resins such as polyester resin (A) and polyester resin (B) is not particularly limited, and may be a commonly known method, such as powder mixing or melt mixing. Either is acceptable. 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 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, a colorant, and, if necessary, one or more additives selected from a release agent, a charge control agent, a fluidizing agent and the like.

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, Orazol Brown B and 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, 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.

As the mold release agent, those having a melting point (Tm) of 50 to 170 ° C. are preferable, polyolefin wax, natural wax, Fischer-Tropsch wax, aliphatic alcohol having 30 to 50 carbon atoms, fatty acid having 30 to 50 carbon atoms, and these A mixture etc. are 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), olefins and unsaturated carboxylic acids [such as (meth) acrylic acid, itaconic acid and maleic anhydride] and / or unsaturated carboxylic acid alkyl esters [(meta ) Alkyl acrylate (C1-C1 of alkyl 8) esters and maleic acid alkyl (C1-18 alkyl) copolymers of an ester, 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 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 is in 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. 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. Hereinafter, unless otherwise specified, “%” represents “% by weight”, and “mol” in () represents a mole part.

Production Example 1
[Synthesis of Polyester Resin (A-1)]
686 parts of propylene oxide of bisphenol A (hereinafter referred to as PO) 686 parts (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). 7 mol), 53 parts (0.15 mol) of PO2 mol adduct of bisphenol A, 1 part (3.1 mmol) of 2 mol adduct of bisphenol A (hereinafter referred to as EO), phenol novolac resin (core) 5.6) EO 5.6 mol adduct (1.2 mmol), 246 parts (1.5 mol) terephthalic acid, 1 part (5.2 mmol) dimethyl terephthalate, maleic anhydride 1 1 part (10 mmol), 6 parts (31 mmol) trimellitic anhydride and 2 parts of tetrabutoxytitanate as a polymerization catalyst were allowed to undergo a polyesterification reaction at 230 ° C. . Subsequently, 73 parts (0.38 mol) of trimellitic anhydride was added and reacted under normal pressure for 1 hour, then reacted under reduced pressure of 5 to 20 mmHg, and taken out when the softening point reached 131 ° 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 the polyester resin (A-1) is 131 ° C., [Mw] is 150,000, the acid value is 23, the hydroxyl value is 3, tan δ (190) is 5.0, and tan δ (140) is 2. 3, [tan δ (190)] / [tan δ (140)] was 2.2.

Production Example 2
[Synthesis of polyester resin (A-2)]
Addition of 733 parts (1.9 moles) of PO3 mole adduct of bisphenol A, 11 parts (0.18 moles) of ethylene glycol, and 5.6 moles of EO of phenol novolac resin (number of nuclei of about 5.6) in the reaction vessel. Product 1 part (1.2 mmol), terephthalic acid 292 parts (1.8 mol), dimethyl terephthalate 1 part (5.2 mmol), maleic anhydride 1 part (10 mmol), trimellitic anhydride 10 parts ( 52 mmol) and 2 parts of dibutyltin oxide as a polymerization catalyst were added, followed by a polyesterification reaction at 230 ° C. Next, 15 parts (78 mmol) of trimellitic anhydride was added and reacted under normal pressure for 1 hour, then reacted under reduced pressure of 5 to 20 mmHg, and taken out when the softening point reached 125 ° 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 the polyester resin (A-2) is 125 ° C., [Mw] is 230000, the acid value is 22, the hydroxyl value is 0, tan δ (190) is 7.2, tan δ (140) is 1. 7, [tan δ (190)] / [tan δ (140)] was 4.2.

Production Example 3
[Synthesis of Polyester Resin (A-3)]
In a reaction vessel, 686 parts (1.7 moles) of a PO3 mole adduct of bisphenol A, 34 parts (42 mmol) of a 5.6 mole EO adduct of phenol novolak resin (number of nuclei of about 5.6), terephthalic acid 232 parts (1.4 mol), 14 parts (0.12 mol) of fumaric anhydride and 2 parts of tetrabutoxy titanate as a polymerization catalyst were added, followed by a polyesterification reaction at 230 ° C. Subsequently, 82 parts (0.44 mol) of trimellitic anhydride was added and reacted under normal pressure for 1 hour, then reacted under reduced pressure of 5 to 20 mmHg, and taken out when the softening point reached 141 ° C. The obtained resin was cooled to room temperature and then pulverized into particles. This is designated as polyester resin (A-3).
In the polyester resin (A-3), T (1/2) is 141 ° C., [Mw] is 130,000, acid value is 23, hydroxyl value is 1, tan δ (190) is 2.1, tan δ (140) is 1. 6, [tan δ (190)] / [tan δ (140)] was 1.3.

Production Example 4
[Synthesis of polyester resin (A-4)]
In a reaction vessel, 73 parts (0.21 moles) of a PO2 mole adduct of bisphenol A, 667 parts (1.7 moles) of a PO3 mole adduct of bisphenol A, and a phenol novolak resin (number of nuclei of about 5.6) 5.6 mol EO adduct 1 part (1.2 mmol), 191 parts terephthalic acid (1.2 mol), 56 parts isophthalic acid (0.35 mol), 24 parts trimellitic anhydride (0.12 mol) After adding 4 parts (34 mmol) of succinic acid and 2 parts of tetrabutoxytitanate as a polymerization catalyst, a polyesterification reaction was carried out at 230 ° C. Subsequently, 68 parts (0.35 mol) of trimellitic anhydride was added and reacted under normal pressure for 1 hour, then reacted under reduced pressure of 5 to 20 mmHg, and taken out when the softening point was reached 130 ° C. The obtained resin was cooled to room temperature and then pulverized into particles. This is designated as polyester resin (A-4).
T (1/2) of the polyester resin (A-4) is 130 ° C., [Mw] is 180,000, the acid value is 24, the hydroxyl value is 1, tan δ (190) is 5.0, and tan δ (140) is 1. 4, [tan δ (190)] / [tan δ (140)] was 3.6.

Production Example 5
[Synthesis of polyester resin (A-5)]
In a reaction vessel, PO3 mol adduct 746 parts (1.9 mol) of bisphenol A, ethylene glycol 1 part (16 mmol), phenol novolac resin (number of cores about 5.6) EO 5.6 mol adduct 1 part (1.2 mmol), 268 parts (1.8 mol) terephthalic acid, 1 part (5.2 mmol) dimethyl terephthalate, 11 parts (56 mmol) trimellitic anhydride and 2 parts dibutyltin oxide as a polymerization catalyst After putting, polyesterification reaction was carried out at 230 ° C. Subsequently, 35 parts (0.18 mol) of trimellitic anhydride was added and reacted under normal pressure for 1 hour, then reacted under reduced pressure of 5 to 20 mmHg, and taken out when the softening point reached 127 ° C. The obtained resin was cooled to room temperature and then pulverized into particles. This is designated as polyester resin (A-5).
In the polyester resin (A-5), T (1/2) is 126 ° C., [Mw] is 210000, acid value is 13, hydroxyl value is 3, tan δ (190) is 6.0, and tan δ (140) is 1. 3, [tan δ (190)] / [tan δ (140)] was 4.6.

Production Example 6
[Synthesis of Polyester Resin (B-1)]
In the reaction vessel, 587 parts (1.5 mol) of PO3 mol adduct of bisphenol A, 164 parts (0.47 mol) of PO2 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), 262 parts (1.6 mol) terephthalic acid, 1 part (5.2 mmol) dimethyl terephthalate, 1 part (10 mmol) maleic anhydride, anhydrous After adding 24 parts (0.13 mol) of trimellitic acid and 2 parts of tetrabutoxytitanate as a polymerization catalyst, a polyesterification reaction was performed at 230 ° C, and when the acid value became 2 or less, the mixture was cooled to 180 ° C. , 21 parts (0.11 mol) of trimellitic anhydride were charged, held at 180 ° C. for 1 hour, and then taken out. The taken out resin was cooled to room temperature and then pulverized into particles. This is designated as polyester resin (B-1).
In the polyester resin (B-1), T (1/2) is 112 ° C., [Mw] is 31000, acid value is 14, hydroxyl value is 22, tan δ (140) is 14.6, tan δ (100) is 1. 9, [tan δ (140)] / [tan δ (100)] was 7.7.

Production Example 7
[Synthesis of Polyester Resin (B-2)]
In the reaction vessel, 586 parts (1.5 mol) of PO3 mol adduct of bisphenol A, 161 parts (0.32 mol) of PO5 mol adduct of bisphenol A, phenol novolac resin (number of nuclei of about 5.6). 5.6 mol EO adduct 1 part (1.2 mmol), 236 parts (1.4 mol) terephthalic acid, 1 part (5.2 mmol) dimethyl terephthalate, 1 part (10 mmol) maleic anhydride, anhydrous After adding 15 parts (78 mmol) of trimellitic acid and 2 parts of tetrabutoxytitanate as a polymerization catalyst, a polyesterification reaction was performed at 230 ° C., and when the acid value became 2 or less, the mixture was cooled to 180 ° C. Trimellitic acid 36 parts (0.19 mol) was charged, held at 180 ° C. for 1 hour, and then taken out. The taken out resin was cooled to room temperature and then pulverized into particles. This is designated as polyester resin (B-2).
In the polyester resin (B-2), T (1/2) is 103 ° C., [Mw] is 22000, acid value is 21, hydroxyl value is 15, tan δ (140) is 22.2, tan δ (100) is 2. 1, [tan δ (140)] / [tan δ (100)] was 10.6.

Production Example 8
[Synthesis of polyester resin (B-3)]
In a reaction vessel, 102 parts (0.30 mol) of an EO2 mol adduct of bisphenol A, 600 parts (1.8 mol) of a PO2 mol adduct of bisphenol A, and a phenol novolac resin (number of nuclei of about 5.6) 1 part (1.2 mmol) of 5.6 mol EO adduct, 269 parts (1.6 mol) terephthalic acid, 20 parts (0.16 mol) fumaric acid and 2 parts tetrabutoxy titanate as a condensation catalyst When the acid value became 2 or less, the mixture was cooled to 180 ° C., charged with 51 parts (0.27 mol) of trimellitic anhydride, held at 180 ° C. for 1 hour, and taken out. . The taken out resin was cooled to room temperature and then pulverized into particles. This is designated as polyester resin (B-3).
In the polyester resin (B-3), T (1/2) is 115 ° C., [Mw] is 32000, acid value is 28, hydroxyl value is 14, tan δ (140) is 8.3, and tan δ (100) is 2. 0, [tan δ (140)] / [tan δ (100)] was 4.2.

Production Example 9
[Synthesis of polyester resin (B-4)]
In a reaction vessel, 29 parts (87 mmol) of an EO2 mol adduct of bisphenol A, 683 parts (1.7 mol) of a PO3 mol adduct of bisphenol A, 9 parts (0.15 mol) of ethylene glycol, phenol novolac resin (nuclear) 5.6 mol EO adduct (1.2 mmol), 264 parts (1.6 mol) terephthalic acid, 1 part (5.2 mmol) dimethyl terephthalate, adipic acid 1 Parts (6.8 mmol), trimellitic anhydride 19 parts (99 mmol) and 2 parts of tetrabutoxy titanate as a condensation catalyst were subjected to a polyesterification reaction at 230 ° C., and when the acid value became 2 or less, The mixture was cooled to 180 ° C., charged with 52 parts (0.27 mol) of trimellitic anhydride, held at 180 ° C. for 1 hour, and taken out. The taken out resin was cooled to room temperature and then pulverized into particles. This is designated as polyester resin (B-4).
Polyester resin (B-4) has T (1/2) of 114 ° C., [Mw] of 30000, acid value of 30, hydroxyl value of 11, tan δ (140) of 23.5, and tan δ (100) of 4. 6. [tan δ (140)] / [tan δ (100)] was 5.1.

Production Example 10
[Synthesis of polyester resin (B-5)]
In a reaction vessel, 118 parts (0.34 mol) of a bisphenol A PO2 mol adduct, 639 parts (1.6 mol) of a PO3 mol adduct of bisphenol A, 1 part (20 mmol) of ethylene glycol, a phenol novolac resin ( 1 part (1.2 mmol) of a 5.6 mol EO adduct having a number of nuclei of about 5.6), 257 parts (1.5 mol) of terephthalic acid, 1 part (5.2 mmol) of dimethyl terephthalate, After adding 16 parts (85 mmol) of merit acid and 2 parts of tetrabutoxytitanate as a polymerization catalyst, a polyesterification reaction was performed at 230 ° C., and when the acid value became 2 or less, the mixture was cooled to 180 ° C. 24 parts (0.12 mol) of merit acid was charged, held at 180 ° C. for 1 hour, and taken out. The taken out resin was cooled to room temperature and then pulverized into particles. This is designated as polyester resin (B-5).
In the polyester resin (B-5), T (1/2) is 103 ° C., [Mw] is 23000, acid value is 14, hydroxyl value is 23, tan δ (140) is 45.2, and tan δ (100) is 4. 8, [tan δ (140)] / [tan δ (100)] was 9.4.

Comparative production example 1
[Synthesis of Polyester Resin (RA-1)]
In a reaction vessel, 236 parts (0.69 moles) of PO2 mole adduct of bisphenol A, 540 parts (1.3 moles) of PO3 mole adduct of bisphenol A, EO5 of phenol novolac (average degree of polymerization about 5.6) 1 part (1.2 mmol) of 6 mol adduct, 120 parts (0.72 mol) of terephthalic acid, 73 parts (0.63 mol) of fumaric acid and 2 parts of dibutyltin oxide as a condensation catalyst, and polyester at 230 ° C. The reaction was allowed to proceed. Subsequently, 87 parts (0.45 mol) of trimellitic anhydride was added and reacted under normal pressure for 1 hour, then reacted under reduced pressure of 5 to 20 mmHg, and taken out when a predetermined softening point was reached. The obtained resin was cooled to room temperature and then pulverized into particles. This is designated as polyester resin (RA-1).
Polyester resin (RA-1) has a T (1/2) of 161 ° C., [Mw] of 110000, an acid value of 29, a hydroxyl value of 9, tan δ (190) of 0.96, and tan δ (140) of 1. 1, [tan δ (190)] / [tan δ (140)] was 0.9.

Comparative production example 2
[Synthesis of Polyester Resin (RB-1)]
In a reaction vessel, 261 parts (0.75 mol) of PO2 mol adduct of bisphenol A, 470 parts (1.2 mol) of PO3 mol adduct of bisphenol A, 25 parts (0.40 mol) of ethylene glycol, phenol novolac EO 5.6 mol adduct (1.2 mmol) with an average degree of polymerization of about 5.6, 275 parts (1.7 mol) terephthalic acid, 69 parts (0.42 mol) isophthalic acid, phthalic anhydride 1 part (8.6 mmol) and 2 parts of tetrabutoxytitanate as a condensation catalyst were added, and a polyesterification reaction was carried out at 230 ° C. When the acid value became 2 or less, the mixture was cooled to 180 ° C and trimellitic anhydride 17 parts (89 mmol) was charged, held at 180 ° C. for 1 hour, and taken out. The taken out resin was cooled to room temperature and then pulverized into particles. This is designated as polyester resin (RB-1).
T (1/2) of the polyester resin (RB-1) is the softening point 111 ° C., [Mw] is 22000, the acid value is 10, the hydroxyl value is 22, tan δ (140) is 40.2, and tan δ (100) is 2.4, [tan δ (140)] / [tan δ (100)] was 16.8.

<Examples 1-6>, <Comparative Examples 1-3>
Polyester resins (A-1) to (A-5), (B-1) to (B-5) obtained in the above production examples, and polyester resins (RA-1) and ( RB-1) was blended according to the blending ratio (parts) in Table 1 to obtain the toner binder of the present invention comprising the polyester resin (A) and the polyester resin (B), and a comparative toner binder, and the following method. Made toner. (Carbon black MA-100 [Mitsubishi Chemical Co., Ltd.], polyolefin wax, charge control agent T-77 [Hodogaya Chemical Co., Ltd.])
First, after premixing using a Henschel mixer [FM10B manufactured by Mitsui Miike Chemical Co., Ltd.], the mixture was kneaded at 140 ° C. using a biaxial kneader [PCM-30 manufactured by Ikegai 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 were mixed with 0.5 part of colloidal silica (Aerosil R972: manufactured by Nippon Aerosil Co., Ltd.) using a sample mill, and the toner compositions (T-1) to (T-6) of the present invention and a comparison were made. Toner compositions (RT-1) to (RT-3) 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 above toner composition, an unfixed image developed with a commercial copying machine (AR5030; manufactured by Sharp) is converted into a fixing machine of a commercial full-color copying machine (LBP-2160, manufactured by Canon Inc.) to change the temperature of the heat roller. Fixing was performed at a process speed of 110 mm / sec using a fixing machine. 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] Toner blocking resistance test The toner composition was tested at 50 ° C. and 85% R.V. H. Was conditioned for 48 hours in a high temperature and high humidity environment. Under the same environment, the blocking state of the toner composition was visually judged, and the image quality when copied with a commercial copying machine (AR5030: manufactured by Sharp) was observed.
Criteria A: There is no toner blocking, and the image quality after copying 3000 sheets is 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] Gloss of Toner Unfixed image developed on J paper (manufactured by Fuji Xerox) with a commercial copying machine (AR-505: manufactured by Sharp) using the above toner composition (printing area: 2 cm × 12 cm, adhesion amount: 0.5 mg / cm ² ) was fixed at 160 ° C. and 400 mm / sec.
White cardboard was laid under the image, and the glossiness of the printed image was measured at an incident angle of 60 degrees using a gloss meter (“IG-330” manufactured by Horiba, Ltd.).
Evaluation criteria ◎: 20 or more ○: 15 or more and less than 20 △: 10 or more and less than 15 ×: Less than 10

  The toner composition and toner binder of the present invention are excellent in both low temperature fixability and hot offset resistance (wide fixing temperature range), glossiness, and blocking resistance (storage stability). It is useful as an electrostatic charge image developing toner and toner binder used for recording, electrostatic printing and the like.

Claims (7)

It contains a polyester resin (A) and a polyester resin (B) having a polycarboxylic acid component (x) and a polyol component (y) as structural units, the softening point of the polyester resin (A) is 120 to 180 ° C., and the weight average molecular weight The loss tangent [tan δ (140)] at 140 ° C. to 100,000 to 300,000 and the loss tangent [tan δ (190)] at 190 ° C. satisfy the following formula (1), and the softening point of the polyester resin (B) is 90 ° C. or higher and 120 ° C. A toner binder having a loss tangent [tan δ (100)] at 100 ° C. and a loss tangent [tan δ (140)] at 140 ° C. satisfying the following formula (2):
1.0 ≦ [tan δ (190)] / [tan δ (140)] ≦ 5.0 Formula (1)
3.0 ≦ [tan δ (140)] / [tan δ (100)] ≦ 15.0 Formula (2)   Polyester resin (A) and polyester resin (B) are 90 mol% or more of aromatic polycarboxylic acid in polycarboxylic acid component (x) and 90 mol of bisphenol polyoxyalkylene ether in polyol component (y). The toner binder according to claim 1, wherein the toner binder is contained in an amount of at least%.   The toner binder according to claim 1 or 2, wherein the polyester resin (A) and the polyester resin (B) contain 70 mol% or more of polyoxypropylene ethers of bisphenols in the polyol component (y).   The polyester resin (A) and / or polyester resin (B) further contains 0.1 to 10 mol% of alkanedicarboxylic acid and / or alkenedicarboxylic acid having 4 to 8 carbon atoms in the polycarboxylic acid component (x). The toner binder according to claim 2.   The toner according to claim 2, wherein the polyester resin (A) and the polyester resin (B) further contain 0.02 to 10 mol% of a polyoxyalkylene ether of a novolak resin in the polyol component (y). binder.   The toner binder according to claim 1, wherein the weight ratio [(A) / (B)] of the polyester resin (A) to the polyester resin (B) is (10 to 90) / (90 to 10). .   A toner composition comprising the toner binder according to any one of claims 1 to 6, a colorant, and, if necessary, one or more additives selected from a release agent, a charge control agent, and a fluidizing agent.