JPH09325518A - Toner binder for color - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a binder good in heat resistance for storage, low in lower limit temp. for fixing and lower limit temp. for color mixing and wide in temp. width with hot offset generating temp. at the time of toner treatment by constituting the binder with a specified linear polyester and satisfying a specified condition. SOLUTION: The binder is composed of the linear polyester made from an alcohol component and an acid component. 20-100mol.% diol having 4-30C alkyl group or alkenyl group at a side chain is incorporated in the alcohol component and/or 20-100mol.% carboxylic acid or acid unhydride having 4-30C alkyl group or alkyl group at the side chain is incorporated in the acid component. A total of the diol and the carboxylic acid incorporated in the total monomer constituting the linear polyester is 20-50mol.%. A glass transition temp. Tg1 of the polyester and weight-average mol.wt. Mw satisfy the formula Tg1>=133-(logMw/0.051).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a color polyester toner binder.

[0002]

2. Description of the Related Art As a color toner binder, a polyester composed of an alkylene oxide of bisphenol A and maleic acid and / or fumaric acid, or a polyester composed of an alkylene oxide of bisphenol A, cyclohexanedimethanol and terephthalic acid (Japanese Patent Application Laid-Open No. Hei 4).
No. 12367 gazette) is proposed.

[0003]

However, the color toner using the above-mentioned polyester as a binder has a narrow temperature range between the fixing lower limit temperature or the color mixture lower limit temperature and the hot offset generation temperature, so that the color toners of recent color copying machines and printers have been narrowed down. It is hard to say that it has sufficiently responded to the trend of demanding lower temperature fixability due to higher speed and the trend of demanding more heat resistant storage stability due to miniaturization. The present invention solves the above problems and provides a toner binder that has good heat-resistant storage stability when formed into a toner, has a low fixing lower limit temperature and a lower color mixture lower limit temperature, and has a wide temperature range with a hot offset occurrence temperature. The purpose is to

[0004]

The inventors of the present invention have selected a toner binder which has good heat-resistant storage stability when formed into a toner, has a low fixing lower limit temperature and a lower color mixture lower limit temperature, and has a wide temperature range with a hot offset occurrence temperature. As a result of intensive studies aimed at obtaining the above, the present invention has been achieved. That is, the present invention comprises a linear polyester (A) composed of an alcohol component (a) and an acid component (b), and has an alkyl or alkenyl group having 4 to 30 carbon atoms in the side chain in the component (a). Diol (a
20 to 100 mol% of 1) and / or a dicarboxylic acid or acid anhydride (b) having a side chain of an alkyl or alkenyl group having 4 to 30 carbon atoms in the component (b).
1) is contained in an amount of 20 to 100 mol%, and the total of the diol (a1) and the dicarboxylic acid (b1) having a side chain of an alkyl or alkenyl group having 4 to 30 carbon atoms contained in all the monomers constituting (A) is 20. It is a color toner binder having a glass transition temperature (Tg1) and a weight average molecular weight (Mw) of the polyester of 50 mol% to 50 mol%. Tg1 ≧ 133− (logMw / 0.051) (1)

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in detail below. The alcohol component (a) of the polyester of the present invention has 4 carbon atoms
Examples of the diol (a1) having an alkyl or alkenyl group of about 30 in its side chain include long-chain olefin glycols (1,2-hexanediol, 1,2-dodecanediol, 1,2-tetradecanediol, etc.). Can be done. If necessary, other dihydric alcohol may be used in combination with the diol (a1). (A
1) is 20 to 100 mol% in (a), preferably 40 to 100 mol%, more preferably 60 to 100 mol%.
mol%. When it is less than 20 mol%, the viscosity of the binder becomes high, and when the toner is used, the lower limit temperature of fixing and the lower limit temperature of color mixing cannot be sufficiently lowered.

Specific examples of other dihydric alcohols include (1) alkylene glycols having 2 to 12 carbon atoms (ethylene glycol, 1,2-propylene glycol,
1,3-propylene glycol, 1,4-butanedio-
, Neopentyl glycol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol, etc.) (2) Alkylene ether glycols (diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, (Polypropylene glycol, polytetramethylene glycol, etc.); (3) C6-C30 alicyclic diol (1,
4-cyclohexanedimethanol, hydrogenated bisphenol A, etc .; and (4) bisphenols (bisphenol A, bisphenol F, bisphenol S, etc.); and (5) alkylene oxides of the above bisphenols [ethylene oxide (abbreviated as EO hereinafter). ), Propylene oxide (hereinafter abbreviated as PO), butylene oxide, etc.] 2 to 8 mol addition product.

The dicarboxylic acid or acid anhydride (b1) having a side chain of an alkyl or alkenyl group having 4 to 30 carbon atoms, which is the acidic component (b) of the polyester of the present invention, includes (1) alkylsuccinic acid or Acid anhydrides (octyl succinic acid, decyl succinic acid, dodecyl succinic acid, tetradecyl succinic acid, hexadecyl succinic acid, octadecyl succinic acid, isooctadecyl succinic acid, etc.);
(2) Alkenyl succinic acid or its acid anhydride (hexenyl succinic acid, octenyl succinic acid, decenyl succinic acid, dodecenyl succinic acid, tetrapropenyl succinic acid,
Tetradecenyl succinic acid, hexadecenyl succinic acid, isooctadecenyl succinic acid, octadecenyl succinic acid,
Nonenylsuccinic acid). If necessary, the carboxylic acid or its acid anhydride (b1)
Besides, other divalent carboxylic acids can be used in combination.
(B1) is 20 to 100 mol%, preferably 40 to 100 mol%, more preferably 60 to 1 in (b).
It is 00 mol%. When it is less than 20 mol%, the viscosity of the binder becomes high, and when the toner is used, the lower limit temperature of fixing and the lower limit temperature of color mixing cannot be sufficiently lowered.

Specific examples of divalent carboxylic acids include:
(1) aliphatic dicarboxylic acids having 2 to 20 carbon atoms (maleic acid, fumaric acid, succinic acid, adipic acid, sebacic acid,
Malonic acid, azelaic acid, mesaconic acid, citraconic acid,
(2) alicyclic dicarboxylic acid having 8 to 20 carbon atoms (cyclohexanedicarboxylic acid, methylmedic acid, etc.); (3) aromatic dicarboxylic acid having 8 to 20 carbon atoms (phthalic acid, isophthalic acid, terephthalic acid) Acid, toluene dicarboxylic acid, naphthalenedicarboxylic acid, etc.); and anhydrides and lower alkyl (methyl, butyl, etc.) esters of these divalent carboxylic acids.

In the present invention, for the purpose of adjusting the molecular weight and controlling the reaction, a monocarboxylic acid, a monoalcohol and the like can be used as necessary together with the alcohol component (a) and the acid component (b). Specific examples thereof include monocarboxylic acids such as benzoic acid, paraoxybenzoic acid, toluenecarboxylic acid, salicylic acid, acetic acid, propionic acid and stearic acid; monoalcohols such as benzyl alcohol, toluene-4-methanol and cyclohexanemethanol. . Alcohol component (a) and acid component (b) constituting the polyester resin (A) of the present invention
The ratio of alcoholic hydroxyl group equivalent / carboxyl group equivalent is usually 0.6 to 1.4, preferably 0.7 to 1.
The ratio may be 3, and more preferably 0.8 to 1.2. If necessary, to adjust the acid value, 3
A carboxylic acid having a valence of 3 or more can be used, and the amount of the carboxylic acid used is 5 mol% in all monomers constituting the linear polyester (A) from the viewpoint of the lower limit temperature of fixing of toner and the lower limit temperature of color mixing.
Or less, preferably 3 mol% or less, more preferably 2
It is below mol%.

As an example of the method for producing the polyester resin (A) of the present invention, a method in which (a) and (b) are put into a reaction vessel all at once to carry out a polyesterification reaction, or a part of raw materials is divided Then, the raw materials other than (b1) are charged into the reaction vessel and subjected to the polyesterification reaction (b
1) is added and esterification is further performed] to obtain the polyester resin of the present invention. The reaction is usually 150 to 300 ° C., preferably 170 to 28 ° C. in the presence of a catalyst.
It is performed under a temperature condition of about 0 ° C. Also, the reaction is under normal pressure,
The reaction can be carried out under reduced pressure or under pressure, but after reaching a predetermined reaction rate (for example, about 30 to 90%), it is desirable to carry out the reaction by reducing the pressure of the reaction system to 200 mmHg or less, preferably 25 mmHg or less.

As the above-mentioned catalyst, a catalyst usually used for polyesterification, for example, tin, titanium, antimony,
Metals such as manganese, nickel, zinc, lead, iron, magnesium, calcium, germanium; and compounds containing these metals (dibutyltin oxide, orthodibutyl titanate, tetrabutyl titanate, zinc acetate, lead acetate, cobalt acetate, sodium acetate, trioxide). Antimony and the like). The polyester of the present invention by stopping the reaction when the properties of the reactant (eg, acid value, softening point, etc.) reach a predetermined value, or when the stirring torque or power of the reactor reaches a predetermined value. The resin (A) can be obtained.

The glass transition temperature (Tg1) and the weight average molecular weight (Mw) of (A) need only satisfy the following mathematical expression (1), but the glass transition temperature (Tg1) of (A) is usually 40.
To 60 ° C., preferably 45 to 60 ° C., and the weight average molecular weight of (A) is usually 5300 to 60,000, preferably 5300 to 25,000, from the viewpoint of the hot offset occurrence temperature and the color mixing lower limit temperature. Tg1 ≧ 133− (logMw / 0.051) (1) The number average molecular weight of (A) is 3000 to 20000,
It is preferably 5000 to 12000. The ratio of the weight average molecular weight to the number average molecular weight is usually 1.5 to 3.0, preferably 1.8 to 2.5. The melt viscosity of (A) measured with a flow tester is such that the temperature at which it becomes 10 ⁶ poise is 60 to 100 ° C, preferably 70 to 90 ° C.
The difference between the temperature showing 0 ³ poise and the temperature showing 10 ⁶ poise is
From the viewpoint of hot offset occurrence temperature and color mixture lower limit temperature,
It is usually 30 to 50 ° C, preferably 35 to 45 ° C.
(A) is usually 0.5 to 30, preferably 1 to 25 mg, from the viewpoint of the amount of charge when the toner is used and its humidity dependency.
From the viewpoint of acid value of KOH / g, fixability at low temperature and humidity dependency of charge amount, usually 5 to 100, preferably 5 to 60.
It has a hydroxyl value of mgKOH / g.

The waxes (B) used in the present invention are not particularly limited, but specific examples include the following. (B1-1) Hydrocarbon wax; paraffin wax, microcrystalline wax, sazol wax, polyethylene wax, polypropylene wax, chlorinated polyethylene wax, fluorocarbon wax and the like. (B1-2) Higher fatty acid wax: stearic acid, behenic acid, coconut oil fatty acid, hydroxy fatty acid and the like. (B1-3) Higher fatty acid amide wax; higher fatty acid monoamide (stearic acid amide, N-stearyl erucic acid amide, etc.), higher fatty acid bisamide (N, N-ethylene bisoleic acid amide, etc.). (B1-4) higher fatty acid ester wax; glycerin fatty acid ester (stearic acid triglyceride, etc.), glycol fatty acid ester (ethylene glycol dioleate, etc.), sorbitan fatty acid ester, partial ester of fatty acid and polyhydric alcohol (pentaerythritol tetra) Stearates, trimethylolpropane tribehenate, etc.), partial esters of fatty acids with polyalkylene glycols, polyglycerol (Panasate R218 manufactured by NOF CORPORATION, etc.). (B1-5) Alcohol wax; higher aliphatic alcohol (stearyl alcohol, behenyl alcohol, etc.), polyhydric alcohol (mannitol, glycerin, sorbitol, pentaerythritol, etc.). (B1-6) Urethane wax; monovalent or polyvalent isocyanate compound [monoisocyanate compound (phenyl isocyanate etc.), diisocyanate compound (isophorone diisocyanate, tolylene diisocyanate etc.), or Polyisocyanate compounds (Sumijour N, Coronate AP made by Nippon Polyurethane, etc.)] and mono- or polyhydric alcohols [higher aliphatic alcohols, mannitol, glycerin, sorbitol, trimethylolpropane, pentaerythritol, polyalkylene glycol, Wax-like compound obtained by urethanization reaction with polyester glycol and the like]. (B1-7) Animal and plant waxes; candelilla wax, carnauba wax, rice wax, beeswax, wood wax and the like. (B1-8) mineral wax; montan wax, etc.
And these oxidized wax etc. In addition, the above wax may be grafted with a vinyl monomer [(meth) acrylonitrile, (meth) acrylic acid, hydroxyalkyl (meth) acrylate, lower alkyl ester of (meth) acrylic acid, etc., or a mixture thereof], or maleic Various modifications such as acid modification can be used. In addition, the following oligomers described in Oligomer Handbook (published by Kagaku Kogyo Nippo) can be used. (B2-1) Olefin-based oligomers; α-olefin oligomers and the like. (B2-2) diene-based oligomer; polybutadiene-based,
Cyclic oligomers, etc. (B2-3) Ring-opening polymerization type oligomer; polyethylene glycol type and the like. (B2-4) Vinyl polymerization type oligomer; polystyrene oligomer type, polystyrene / acrylic copolymer oligomer type and the like. (B2-5) Polycondensation, polyaddition type oligomer; polyester type oligomer (unsaturated polyester resin etc.), polyamide type oligomer (dimer acid / ethylenediamine condensate etc.), polyurethane type oligomer (toluene diisocyanate / 1, 4-butanediol condensate etc.). (B2-6) Addition-condensation type oligomer; phenol resin type, amino resin type, xylene resin type, ketone resin type and the like. (B2-7) Petroleum resin; C5 petroleum resin, C9 petroleum resin, dicyclopentadiene petroleum resin and the like. (B2-8) Silicone type, fluorine type oligomer and the like. These can be used alone or as a mixture of plural kinds of waxes and oligomers. Of these, waxes (B1) are preferable from the viewpoint of melt viscosity, and more preferable are higher fatty acid waxes (B1).
-2), higher fatty acid amide wax (B1-3), higher fatty acid ester wax (C1-4), alcohol wax (B1-5) and urethane wax (B)
1-6).

The melting point of (B) is usually 20 to 120 from the viewpoint of the fixability at low temperature and the heat-resistant storage stability of the toner.
C., preferably 50 to 110.degree.

The amount of (B) contained in (A) is (B)
The glass transition temperature (Tg2) of the composition lowered by containing the compound (A) may be the amount satisfying the weight average molecular weight (Mw) of (A) and the following mathematical formula (2), but usually 30% by weight or less. , Preferably 5 to 20% by weight. Tg2 ≧ 177− (logMw / 0.031) (2) When the content of (B) exceeds 30% by weight, the powder fluidity of the toner is adversely affected.

An example of a method for producing an electrophotographic toner, which is an application of the binder of the present invention, will be described. The toner binder is usually 45 to 95% by weight based on the weight of the toner, and a known coloring agent (carbon black, nigrosine dye, aniline blue). , Red iron oxide, acetylene black, monoazo dye, diazo dye, quinacridone, anthraquinone dye, chalcooil blue, copper phthalocyanine, induslen blue, benzidine yellow, chrome yellow, ultramarine yellow, duPont oil red, induslen blue, permanent Brown FG, Bryanto Farnest Scarlet, Malachite Green Oxalate,
Pigments or dyes such as Lamp Black, Rose Bengal, Pigment Green B, Rhodamine B and Solvent-35, and JP-A-1-277253 and JP-A-1.
Pigments or dyes other than the above described in JP-A-159759) are usually used in an amount of 3 to 15% by weight, and magnetic powders (compounds such as iron, cobalt, nickel, hematite and ferrite) are usually used in an amount of 0.1 to 50% by weight. I can give you something. In addition, various additives [charge control agents (metal complexes, nigrosine, etc.), lubricants (polytetrafluoroethylene,
Low molecular weight polyolefin, fatty acid, or metal salt or amide thereof, etc.)]. The amount of these additives is usually 0 to 10% by weight based on the weight of the toner. The toner for electrophotography is dry-blended with the above components, melt-kneaded, then coarsely pulverized, and finally finely pulverized using a jet pulverizer or the like to have a particle size of 5 to 20 μm.
It is obtained as fine particles of. The electrophotographic toner is mixed with carrier particles such as iron powder, glass beads, nickel powder, and ferrite, if necessary, and used as a developer for an electric latent image. Further, hydrophobic colloidal silica fine powder can be used to improve the fluidity of the powder. The electrophotographic toner is used by being fixed on a support (paper, polyester film, etc.).

[0017]

The present invention will be further described with reference to the following examples, but the present invention is not limited to these examples. Hereinafter, parts are parts by weight.

The methods for measuring the properties of the polyester resins obtained in Synthesis Examples, Examples and Comparative Examples are shown below. 1. Acid value and hydroxyl value The method specified in JIS K0070. However, when the sample does not dissolve, a solvent such as dioxane or tetrahydrofuran is used as the solvent. 2. Glass transition temperature (Tg) Method prescribed in ASTM D3418-82 (DSC
Law). 3. Melt viscosity Measured with a flow tester. The conditions for measuring the melt viscosity with a flow tester are as follows. Equipment: Shimadzu CFT-500 type die: 1.0 mmφ × 1.0 mm load: 10 kg heating rate: 5 ° C./min 4. Molecular weight Gel permeation chromatography (GP
Measured in C). The conditions for measuring the molecular weight by GPC are as follows. Equipment: Toyo Soda HLC-802A column: Column TSK gel GMH62
Book (manufactured by Toyo Soda Co., Ltd.) Measurement temperature: 25 ° C. Sample solution: 0.5 wt% THF solution Injection amount: 200 μl Detector: Refractive index detector The molecular weight calibration curve was prepared using standard polystyrene.

Example 1 A PO adduct of bisphenol A (hydroxyl value: 32) was placed in a reaction vessel equipped with a thermometer, a stirrer, a condenser and a nitrogen inlet tube.
0) 64 parts, EO adduct of bisphenol A (hydroxyl number 343) 544 parts, terephthalic acid 123 parts and dibutyltin oxide 4 parts were added, reacted at 230 ° C. under normal pressure for 3 hours, then cooled to 180 ° C. and dried. 296 parts of dodecenylsuccinic acid was added, and the mixture was further reacted under reduced pressure of 10 to 15 mmHg until the acid value became 2 mgKOH / g or less. Then, add 20 parts of trimellitic anhydride and keep it at 180 ℃ under normal pressure.
After reacting for 2 hours, the toner was taken out from the reaction tank to obtain the toner binder (TB-1) of the present invention. Tg of (TB-1) is 4
8 ° C, number average molecular weight 9000, weight average molecular weight 220
00, the temperature at which the melt viscosity reaches 10 ⁶ poise is 73 ° C, 1
The difference between the temperature at which it becomes 0 ⁶ poise and the temperature at which it becomes 10 ³ poise is 3
7 ℃, acid value 10mgKOH / g, hydroxyl value 17mg
KOH / g.

Example 2 A reactor similar to that of Example 1 was charged with 636 parts of a PO adduct of bisphenol A (hydroxyl value 320) and 19 terephthalic acid.
Add 1 part and 4 parts of dibutyltin oxide, react at atmospheric pressure at 230 ° C. for 3 hours, cool to 180 ° C., add 205 parts of dodecenylsuccinic anhydride, and further add 10 to 15
The reaction was performed under reduced pressure of mmHg until the acid value became 2 mgKOH / g or less. Then add 20 parts trimellitic anhydride,
The reaction was carried out at 180 ° C. for 2 hours under normal pressure, and the product was taken out from the reaction tank to obtain the toner binder (TB-2) of the present invention. (TB-
Tg of 55 ° C. for 2), a number average molecular weight of 5,000, a weight average quantity is 10000, the temperature is 83 ° C. to be 10 ⁶ poise at a melt viscosity, the difference between the temperature at which the temperature of 10 ³ poise to 10 ⁶ poise 35 C., the acid value was 11 mgKOH / g, and the hydroxyl value was 16 mgKOH / g.

Example 3 In the same reaction apparatus as in Example 1, 444 parts of PO adduct of bisphenol A (hydroxyl value 320) and 40 terephthalic acid were used.
7 parts, 1,2-dodecanediol and 4 parts of dibutyltin oxide were added, and the mixture was reacted at 230 ° C. for 8 hours under normal pressure,
Furthermore, the acid value is 2 mgKOH at a reduced pressure of 10-15 mmHg.
/ G or less, and reacted from the reaction tank to obtain the toner binder (TB-3) of the present invention. (TB-3)
Has a Tg of 48 ° C., a number average molecular weight of 9200, a weight average molecular weight of 22000, and a melt viscosity of 10 ⁶ poise at a temperature of 7580 ° C., a difference between a temperature of 10 ⁶ poise and a temperature of 10 ³ poise is 39 ° C., The acid value was 2 mgKOH / g and the hydroxyl value was 5 mgKOH / g.

Example 4 A reactor similar to that used in Example 1 was charged with 604 parts of a PO adduct of bisphenol A (hydroxyl value 320) and 18 terephthalic acid.
1 part and 4 parts of dibutyltin oxide were added, reacted at 230 ° C. under normal pressure for 3 hours, cooled to 180 ° C., added with 195 parts of dodecenylsuccinic anhydride, and further added to 10 to 15
The reaction was performed under reduced pressure of mmHg until the acid value became 2 mgKOH / g or less. Then add 20 parts trimellitic anhydride,
After reacting for 2 hours at 180 ° C. under normal pressure, 50 parts of behenic acid was added, and after stirring for 1 hour at 180 ° C. for normal pressure, the toner was taken out from the reaction tank to obtain a toner binder (TB-4) of the present invention. Tg of polyester resin before adding behenic acid is 62
C., Tg of (TB-4) is 53.degree. C., number average molecular weight is 60
00, the weight average amount is 13000, the temperature at which the melt viscosity becomes 10 ⁶ poise is 80 ° C., and the temperature at which the melt viscosity becomes 10 ⁶ poise is 1
The difference in the temperature to reach 0 ³ poise is 35 ° C, and the acid value is 10 mgK
The OH / g and the hydroxyl value were 17 mgKOH / g.

Example 5 300 parts of bisphenol A PO adduct (hydroxyl value 320) and bisphenol A were added to the same reactor as in Example 1.
282 parts of EO adduct (hydroxyl value 343), 115 parts of terephthalic acid and 4 parts of dibutyltin oxide were added, reacted at 230 ° C. under normal pressure for 3 hours, cooled to 180 ° C., and added with 276 parts of dodecenylsuccinic anhydride. Furthermore, the reaction was performed under a reduced pressure of 10 to 15 mmHg until the acid value became 2 mgKOH / g or less. Then trimellitic anhydride 20
After adding 2 parts and reacting under normal pressure at 180 ℃ for 2 hours, behenic acid 5
After adding 0 part and further stirring at normal pressure 180 ° C. for 1 hour,
The toner binder of the present invention (TB-
5) was obtained. Tg of polyester resin before adding behenic acid
Is 50 ° C., Tg of (TB-5) is 40 ° C., number average molecular weight is 9000, weight average molecular weight is 22000, and melt viscosity is 1
The difference between the temperature at which 0 ⁶ poise is 68 ° C and the temperature at which 10 ⁶ poise is 10 ³ poise is 40 ° C, and the acid value is 10 m.
The gKOH / g and the hydroxyl value were 17 mgKOH / g.

Comparative Example 1 A reactor similar to that of Example 1 was charged with 695 parts of a PO adduct of bisphenol A (hydroxyl value 320) and 1 maleic anhydride.
Add 96 parts and 4 parts of dibutyltin oxide, react at atmospheric pressure at 230 ° C. for 8 hours, and further 10 to 15 mmHg
Under reduced pressure until the acid value becomes 5 mgKOH / g, the toner binder of the present invention (TB-1
1) was obtained. (TB-11) has a Tg of 60 ° C., a number average molecular weight of 5100, a weight average molecular weight of 12,000, and a melt viscosity of 10 ⁶ poise at 85 ° C., 10 ⁶ poise and 10 ³ poise. The difference is 40 ℃, the acid value is 5
The mgKOH / g and the hydroxyl value were 12 mgKOH / g.

Comparative Example 2 695 parts of a PO adduct of bisphenol A (hydroxyl value 320) and 1 maleic anhydride were placed in the same reactor as in Example 1.
Add 96 parts and 4 parts of dibutyltin oxide, react at atmospheric pressure at 230 ° C. for 8 hours, and further 10 to 15 mmHg
Under reduced pressure until the acid value reaches 10 mgKOH / g,
The toner binder of the present invention (TB-
12) was obtained. (TB-12) has a Tg of 40 ° C., a number average molecular weight of 2100, a weight average molecular weight of 4000, and a melt viscosity of 10 ⁶ poise at 65 ° C., 10 ⁶ poise and 10 ³ poise. The difference is 30 ℃, the acid value is 1
The hydroxyl value was 0 mgKOH / g, and the hydroxyl value was 17 mgKOH / g.

Comparative Example 3 261 parts of a bisphenol A PO adduct (hydroxyl value 320) and 11 parts of terephthalic acid were placed in the same reactor as in Example 1.
Add 8 parts and 4 parts of dibutyltin oxide, react at atmospheric pressure at 230 ° C. for 3 hours, cool to 180 ° C., add 286 parts of dodecenylsuccinic anhydride, and further add 10 to 15
The reaction was performed under reduced pressure of mmHg until the acid value became 2 mgKOH / g or less. Then add 20 parts trimellitic anhydride,
After reacting at 180 ° C. under normal pressure for 2 hours, the reaction product was taken out from the reaction tank to obtain a toner binder (TB-13) of the present invention. (TB
-13) has a Tg of 50 ° C., a number average molecular weight of 4,500, a weight average molecular weight of 9,100, and a melt viscosity of 10 ⁶ poise at a temperature of 80 ° C. The difference between the temperature of 10 ⁶ poise and the temperature of 10 ³ poise is At 35 ° C, the acid value was 10 mgKOH / g and the hydroxyl value was 17 mgKOH / g.

Comparative Example 4 340 parts of a PO adduct of bisphenol A (hydroxyl value 320) and bisphenol A were placed in the same reactor as in Example 1.
282 parts of EO adduct (hydroxyl value 343), 115 parts of terephthalic acid and 4 parts of dibutyltin oxide were added, reacted at 230 ° C. under normal pressure for 3 hours, cooled to 180 ° C., and added with 276 parts of dodecenylsuccinic anhydride. Furthermore, the reaction was performed under a reduced pressure of 10 to 15 mmHg until the acid value became 2 mgKOH / g or less. Then trimellitic anhydride 20
After adding 2 parts and reacting under normal pressure at 180 ℃ for 2 hours, behenic acid 1
00 parts was added, and the mixture was further stirred at a normal pressure of 180 ° C. for 1 hour, then taken out of the reaction tank, and the toner binder (T
B-14) was obtained. The Tg of the polyester resin before the addition of behenic acid is 50 ° C, the Tg of (TB-14) is 33 ° C, the number average molecular weight is 9,000, the weight average amount is 22,000, and the temperature at which the melt viscosity is 10 ⁶ poise is 60 ° C. The difference between the temperature of ⁶ poise and the temperature of 10 ³ poise is 40 ° C, the acid value is 10 mgKOH / g, and the hydroxyl value is 17 mgKOH / g.
Met.

Use Example 1 Using the toner binder obtained in Example 1, 100 parts of the toner binder, 5 parts of the pigment and the charge control agent (3.
5-di-butylsalicylic acid chromium complex compound) in an amount of 1 part by weight of the pigment. I. Pigment Yellow
17, C.I. I. Pigment Red 122,
C. I. Pigment Blue 15 and carbon black, respectively, and then kneaded with a twin-screw extruder, the cooled product is finely pulverized with a jet mill, and classified with a dispersion separator to obtain a yellow toner (a having an average particle size of 10 μm).
1), magenta toner (a2), cyan toner (a3) and black toner toner (a4) were obtained.

Use Example 2 and Comparative Use Example Using the toner binders of the present invention of Examples 2 to 5 and the toner binders of Comparative Examples 1 to 4 in the same manner as in Use Example 1, (b1 to 4) to (i1). ~ 4) toner was obtained. Test Example 1 Ferrite carrier (F-100 manufactured by Powder Tech Co., Ltd.) 97 was added to 3 parts of each of toners (a1 to 4) to (i1 to 4).
Parts are mixed uniformly, and a commercial copying machine (Canon CLC-1)
The lower limit temperature of fixing, the lower limit temperature of color mixture, and the hot offset generation temperature were measured by using the modified machine. The test results are shown in Table 1.
As shown in.

As for the minimum lower limit temperature, the solid image portion was rubbed by the Gakshin-type fastness tester (rubbing portion = paper) with 5 reciprocations, and the image density of the solid portion after rubbing was 70% or more. The temperature of the heat roll when the copy was obtained was read. For the lower limit temperature of color mixture, the gloss value (glossiness) of the solid image portion is measured by a commercially available gloss meter (MURAKAMI COLOR RE).
SEARCH LABORATORY GMX-20
260 type) and the heat roll temperature when a copy having a gloss value of more than 10% was obtained was read. The hot offset generation temperature was obtained by visually confirming the hot offset generation and reading the heat roll temperature when a copy in which the generation of the hot offset was recognized was obtained.

Test Example 2 Toners (1 to 4) to (i1 to 4) each containing 10 g of 2 toner
Put in a 0cc screw tube and 4 at 40 ° C x 40% RH.
After standing for 8 hours, the heat-resistant storage stability was evaluated in four ranks according to the degree of toner aggregation. Table 1 shows the test results. Rank A: No aggregation at all. Rank B: Slightly aggregated, but redispersed when a light impact is applied to the screw tube C rank: About 1/4 of the toner is aggregated and does not redisperse even when a slight impact is applied to the screw tube. Rank D: The degree of agglomeration is remarkable and does not redisperse even when a strong impact is applied to the screw tube.

[0032]

[Table 1]

All of the toners using the binders TB-1 to TB-5 of the present invention have lower lower-limit fixing temperature and lower-limit color mixing temperature as compared with the toner using the comparative binder TB-11, which deteriorates heat-resistant storage stability. The fixability at low temperatures is improved without. Further, the binder TB- of the present invention
All of the toners using 1 to TB-5 have improved heat resistant storage stability as compared with the toners using the comparative binders TB-12 to TB-14. Examples of Table 1 (a1-4),
The toners of (e1 to 4) were continuously copied on 10,000 sheets. The image quality after copying 10,000 sheets was the same as the initial image quality. It can be seen that the toner using the toner binder of the present invention does not change even after long-term friction with the carrier and has excellent durability.

[0034]

The toner using the toner binder of the present invention has a low minimum fixing temperature and a minimum mixing temperature, and is excellent in heat-resistant storage stability. Further, the hot offset generation temperature is high and the durability is good. As described above, the toner using the toner binder of the present invention has not only fixability (low temperature fixability, low temperature color mixing property and anti-offset property) but also heat-resistant storage property, durability and other practically necessary performances. Therefore, it is useful for color copying machines of various speeds (especially high speed copying machines) and color printers.

Claims (2)

[Claims] 1. A diol comprising a linear polyester (A) composed of an alcohol component (a) and an acid component (b), and having a side chain of an alkyl or alkenyl group having 4 to 30 carbon atoms in the component (a). 20 to 100 mol% of (a1), and / or 20 to 100 mol% of a dicarboxylic acid or acid anhydride (b1) having a C4 to C30 alkyl or alkenyl group in its side chain in the component (b),
The total of (a1) and (b1) contained in all the monomers constituting (A) is 20 to 50 mol%, and the glass transition temperature (Tg1) and the weight average molecular weight (Mw) of the polyester are represented by the following formula (1). ) Color toner binder that satisfies the above. Tg1 ≧ 133− (logMw / 0.051) (1) 2. A composition comprising a wax (B), wherein the glass transition temperature (Tg2) of the composition and the weight average molecular weight (Mw) of the linear polyester (A) are represented by the following formula (2). The toner binder for color according to claim 1, which satisfies the above condition. Tg2 ≧ 177- (logMw / 0.031) (2)