JPH10239903A - Toner binder for developing electrostatic charge image - Google Patents

Abstract

PROBLEM TO BE SOLVED: To suppress the reduction of the glass transition temp. of a resin and to obtain a toner binder having satisfactory electrostatic charge kick-off property by using polyester resin consisting of polycarboxylic acid, polyol and oxyalkylene ether of monool contg. an arom. ring. SOLUTION: This toner binder is polyester resin consisting of polycarboxylic acid, polyol and oxyalkylene ether of monool contg. an arom. ring. The polycarboxylic acid has bivalent or more COOH groups. The polyol has bivalent or more OH groups. The monool is, e.g. phenol, alkyl substd. phenol, aralkyl alcohol or alkyl substd. aralkyl alcohol.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a toner binder for developing a black and white and color electrostatic image used in electrophotography, electrostatic recording, electrostatic printing and the like.

[0002]

2. Description of the Related Art Conventionally, as a method of developing an electrostatic image using toner in electrophotography, electrostatic recording, electrostatic printing, etc., an electrostatic latent image is formed on a photoreceptor by a conventional method, After development, the toner image is transferred onto copy paper, and then heat-fixed (usually using a heat roller) to obtain a copy. Hitherto, it has been proposed to use a polyester resin as a toner binder, which is a component of the toner. US Pat. No. 3,681,106 discloses an alkylene oxide addition of a trihydric or higher polyhydric alcohol (such as trimethylolpropane). Proposal of polyester using things. Also, in US Pat. No. 5,294,682,
A polyester resin using an oxyalkylene ether of a novolak type phenol resin has been proposed.

[0003]

However, conventional polyester resins have insufficient charging characteristics such as charge amount, charge rise, environmental stability, and the like. US Patent Specification 5,2
As described in JP-A-94,682, monoalcohols can be used for the purpose of controlling the molecular weight as a conventional technique.
g (glass transition temperature) is too large to achieve the heat-resistant storage stability of the toner, and the boiling point of benzyl alcohol is lower than or close to the polyesterification reaction temperature. There is a problem that the chemical reaction cannot be performed.

[0004]

Means for Solving the Problems The present inventor has proposed that the resin Tg
The present inventors have conducted intensive studies with the aim of obtaining a toner binder having a good charge rising property while suppressing the reduction, and as a result, have reached the present invention. That is, the present invention provides an electrostatic image development, which is a polyester resin comprising a polycarboxylic acid (A), a polyol (B), and an oxyalkylene ether (C) of a monol (c) containing an aromatic ring. Toner binder.

[0005]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. In the present invention, the polycarboxylic acids (A) include divalent carboxylic acids (A1) and trivalent or higher carboxylic acids (A2). Specific examples of the divalent carboxylic acids (A1) 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) an alicyclic dicarboxylic acid having 8 to 20 carbon atoms (such as cyclohexanedicarboxylic acid and methylmedic acid); and (3) an aromatic dicarboxylic acid having 8 to 20 carbon atoms (phthalic acid, isophthalic acid, and terephthalic acid). Acid, toluenedicarboxylic acid, naphthalenedicarboxylic acid, etc.);
(4) Alkyl or alkenyl (anhydride) succinic acid having a hydrocarbon group having 4 to 35 carbon atoms in a side chain {dodecenyl (anhydride) succinic acid, pentadodecenyl (anhydride) succinic acid, etc.}; Examples include anhydrides and lower alkyl (methyl, butyl, etc.) esters. Among them, the above-mentioned (1), (3), (4) and anhydrides and lower alkyl esters of these dicarboxylic acids are preferable, and (anhydride) maleic acid, fumaric acid, isophthalic acid, terephthalic acid, dimethyl terephthalate, dodecenyl ( Succinic anhydride) is more preferred. (Anhydride) maleic acid and fumaric acid are preferred in terms of high reactivity, and isophthalic acid and terephthalic acid are preferred in terms of increasing the glass transition temperature of the polyester.

Specific examples of the trivalent or higher carboxylic acids (A2) include (1) aliphatic polycarboxylic acids having 7 to 20 carbon atoms (1,2,4-butanetricarboxylic acid, 1,2,5-
Hexanetricarboxylic acid, 1,3-dicarboxyl-2
-Methyl-2-methylenecarboxypropane, tetra (methylenecarboxyl) methane, 1,2,7,8-octanetetracarboxylic acid and the like); (2) C9 to C20.
Alicyclic polycarboxylic acids (e.g., 1,2,4-cyclohexanetricarboxylic acid); (3) aromatic polycarboxylic acids having 9 to 20 carbon atoms (1,2,4-benzenetricarboxylic acid, 1,2,5 -Benzenetricarboxylic acid, 2,5,7
-Naphthalenetricarboxylic acid and 1,2,4-naphthalenetricarboxylic acid, pyromellitic acid, benzophenonetetracarboxylic acid, etc.); and anhydrides and lower alkyl (methyl, butyl, etc.) esters thereof. When (A2) is used, among these, (3) and its anhydrides and lower alkyl esters are preferred, and in particular, 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid and their anhydrides And lower alkyl esters are preferred in terms of cost and imparting toner with offset resistance.

In the polycarboxylic acids (A) of the present invention, the divalent carboxylic acids (A1) may be used alone or in combination with the trivalent or higher carboxylic acids (A2).
In particular, for black and white, the combination of (A1) and (A2) is preferred.

[0008] The polyols (B) in the present invention comprise 2
The polyhydric alcohols (B1) and the trihydric or higher alcohols (B2) are exemplified. Specific examples of the dihydric alcohols (B1) include (1) alkylene glycols having 2 to 12 carbon atoms (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 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) (3) alicyclic diols having 6 to 30 carbon atoms (such as 1,4-cyclohexanedimethanol and hydrogenated bisphenol A); and (4) bisphenols (bisphenol A, bisphenol F, Screw And (5) alkylene oxides of bisphenols such as ethylene oxide (hereinafter abbreviated as EO), propylene oxide (hereinafter abbreviated as PO), butylene oxide and the like, and 2 to 8 mol adducts. . Of these, (1) and (5) are preferred, and (5) is more preferred. In the above (1), ethylene glycol increases the reaction rate, and 1,2-propylene glycol and neopentyl glycol are preferred from the viewpoint of low-temperature fixability. Further, among the above (5), an adduct of bisphenol A with 2 to 4 moles of EO and / or PO is particularly preferred in that it gives the toner good offset resistance.

Specific examples of the trihydric or higher alcohols (B2) include (1) aliphatic polyhydric alcohols having 3 to 20 carbon atoms (sorbitol, 1,2,3,6-hexanetetraol, 1,4 -Sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol,
1,2,4-butanetriol, 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, etc.);
(2) C6-C20 aromatic polyhydric alcohol (1,
3,5-trihydroxylmethylbenzene, etc.); and their alkylene oxide adducts; (3) oxyalkylene ethers of novolak-type phenol resins;
(4) Oxyalkylene ethers of heterocyclic compounds having two or more active hydrogens in the molecule such as isocyanuric acid and the like. The oxyalkylene ether of the novolak phenol resin (3) is an alkylene oxide (b2) adduct of the novolak phenol resin (b1), and (b1) is a phenol (phenol or a hydrocarbon group having 1 to 35 carbon atoms). And / or a substituted phenol having at least one halogen group as a substituent, and a mixture thereof, preferably produced by polycondensation of phenol, cresol, or t-butylphenol) with an aldehyde (formalin, paraformaldehyde, trioxane, etc.). Specific examples of (b2) include ethylene oxide (EO), 1,2-propylene oxide (PO), 1,2-butylene oxide,
3-butylene oxide and the like, and (b)
The average number of moles of (b) added to one phenolic hydroxyl group in 1) is usually 0.1 to 10 mol, preferably 0.2 to 10 mol.
４4 mol, more preferably 0.3-2 mol. Of these, the compounds (1), (3) and (4) are preferred, and (1) and (3) are more preferred.

In the polyols (B) of the present invention, 2
The polyhydric alcohols (B1) may be used alone or in combination with a trihydric or higher polyols (B2). Particularly for black and white, it is preferable to use both (B1) and (B2).

The oxyalkylene ether (C) of the monol (c) containing an aromatic ring in the present invention is a compound containing a phenol or an aromatic ring in the molecule or adding an alkylene oxide or a (poly) alkylene glycol to a monoalcohol. It has a chemical structure represented by the following general formula. Ar-O- (AO) n-H (wherein, Ar is an optionally substituted hydrocarbon group containing an aromatic ring, AO is an oxyalkylene group, and n is 1 to 10
Represents an integer. Examples of the monool (c) include phenols (c1) such as phenol, alkyl-substituted phenol and alkoxy-substituted phenol, and aralkyl alcohols (c2) such as aralkyl alcohol, alkyl-substituted aralkyl alcohol and alkoxy-substituted aralkyl alcohol. )
And the like. Specific examples of the phenols (c1) include phenol; alkyl-substituted phenols (cresol, ethylphenol, t-butylphenol, nonylphenol, dodecylphenol, etc.); and alkoxy-substituted phenols (ethyloxyphenol, t-butyloxyphenol, hexyl). Oxyphenol, decyloxyphenol, etc.). Of these, alkyl-substituted phenols are preferred, especially those having 4 carbon atoms.
Alkyl-substituted phenols having the above-mentioned alkyl groups as substituents are preferred from the viewpoint of reactivity in the polyesterification reaction. Specific examples of the aralkyl alcohols (c2) include benzyl alcohol, 2-phenylmethanol; 4-methylbenzyl alcohol, 4-ethylbenzyl alcohol; 4-methoxybenzyl alcohol and the like. Specific examples of the alkylene oxide include:
Ethylene oxide (EO), 1,2-propylene oxide (PO), 1,2-butylene oxide, 2,3
-Butylene oxide and the like, and (c)
The average number of moles of the alkylene oxide added to one hydroxyl group is usually 1 to 10 mol, preferably 1 to 4 mol,
More preferably, it is 1 to 2 mol. When the number of added moles exceeds 10 moles, the Tg decrease in the case of polyesterification is large. The unadded monool (c) may partially remain within a range that does not affect the esterification reaction. The boiling point of the oxyalkylene ether (C) in the present invention is usually 220 ° C. or higher at normal pressure, preferably 240 ° C.
° C or higher, more preferably 260 ° C or higher. 22
If the temperature is lower than 0 ° C., distillation easily occurs during the ester reaction,
As a result, the charge amount and the rise of the charge are likely to be adversely affected. The upper limit of the boiling point at normal pressure is not particularly limited.

The polyesterification reaction of the present invention is usually carried out in the presence of a catalyst, usually at 150 to 300 ° C., preferably at 170 to 300 ° C.
It is carried out under a temperature condition of 280 ° C, more preferably 200 ° C to 260 ° C. In addition, it is preferable to carry out at a reaction temperature which is usually 20 or more lower than the boiling point of the oxyalkylene ether (C) at normal pressure. The reaction can be performed under normal pressure, reduced pressure, or increased pressure, but after reaching a predetermined polyester conversion rate (for example, 30 to 90%), the pressure of the reaction system is reduced to 200 mmHg or less, preferably 50 mmHg or less. It is desirable to carry out a polyesterification reaction.

The ratio of the polycarboxylic acid (A) to the alcohol (polyols (B) and oxyalkylene ether (C)) constituting the polyester resin of the present invention is such that the ratio of alcoholic hydroxyl group equivalent / carboxyl group equivalent is:
The ratio may be generally 0.6 to 1.5, preferably 0.7 to 1.4, and more preferably 0.8 to 1.3. Oxyalkylene ether (C) is usually 0.1 to
It is 35% by weight, preferably 0.1 to 25% by weight, more preferably 0.1 to 20% by weight. When the oxyalkylene ether (C) exceeds 35% by weight, the molecular weight decreases,
The crushing strength of the toner decreases. When a tri- or higher-valent carboxylic acid and a tri- or higher-valent alcohol are used in combination as required, the amount is usually 35% by weight or less, preferably 25% by weight or less. If the content of the trivalent or higher carboxylic acid and / or the trivalent or higher valent alcohol exceeds 35% by weight, the low-temperature fixability of the toner is insufficient.

As an example of a method for producing the polyester resin of the present invention, the polycarboxylic acid (A), the polyols (B) and the oxyalkylene ether (C) are mixed at a predetermined ratio, and a polyesterification reaction is carried out. Is obtained. (A), (B),
Part of (C) may be added to the reaction system during the polyesterification reaction. Examples of the catalyst include catalysts generally used for polyesterification, for example, metals such as tin, titanium, antimony, manganese, nickel, zinc, lead, iron, magnesium, calcium, and germanium; and compounds containing these metals (dibutyltin oxide, ortho Dibutyl titanate, tetrabutyl titanate, zinc acetate, lead acetate, cobalt acetate, sodium acetate, antimony trioxide, etc.). The polyester of the present invention is obtained by stopping the reaction when the properties of the reactants (eg, acid value, softening point, etc.) reach a predetermined value, or when the stirring torque or stirring power of the reactor reaches a predetermined value. A resin can be obtained.

The polyester resin of the present invention has an acid value of usually 30 or less, preferably 20 or less, and a hydroxyl value of usually 50 or less, preferably 35 or less, more preferably 25 or less. If the acid value exceeds 30, the humidity dependence of the charge amount increases. On the other hand, when the hydroxyl value exceeds 50, the humidity dependency of the charge amount becomes large. The number average molecular weight of the polyester resin of the present invention is usually 1,000 to 12,000, preferably 1500 to 9000, more preferably 20 to 9000.
00 to 7000.

The Tg (glass transition temperature) of the polyester resin of the present invention is usually 40 to 85 ° C., preferably 45 to 80 ° C.
° C, more preferably 50-75 ° C. Tg is 40
If the temperature is lower than 0 ° C., adhesion and aggregation (blocking) of toner particles using the binder of the present invention are likely to occur, and Tg is 8 ° C.
If the temperature exceeds 5 ° C., the low-temperature fixability of the toner deteriorates.

The softening point of the polyester resin of the present invention is usually from 60 to 140 ° C., preferably from 75 to 125 ° C. when used for color, and usually 90 to 125 ° C. when used for black and white.
C. or higher, preferably 100 ° C. or higher.

The binder of the present invention comprises the polyester resin of the present invention, but may further contain other toner binder resins if necessary. Other resins for toner binder include polystyrene resin, styrene-acryl copolymer resin, styrene-butadiene copolymer resin, styrene-acrylonitrile copolymer resin, styrene-acryl-acrylonitrile copolymer resin, polyurethane resin, polyamide Resins, epoxy resins, polyester resins other than the present invention, and the like.

As an example of the method for producing a toner for developing an electrostatic image, which is used as the binder of the present invention, the toner binder is usually 45 to 95% by weight based on the weight of the toner, and a known coloring agent (carbon black, iron black, Sudan Black S
M, Fast Yellow-G, Benzidine Yellow, Pigment Yellow, India First Orange, Irgasin Red, Balanitoaniline 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, oil pink OP, etc.). Compounds such as cobalt, nickel, hematite, and ferrite) are usually used in an amount of 0 to 50% by weight. Furthermore, various additives [charge adjusting agent (Nigrosine dye, triphenylmethane derivative, quaternary ammonium salt compound, polymer containing polymerizable unit having quaternary ammonium base as a constituent unit, azo dye compound, salicylic acid metal complex , A copolymer containing, as constituent units, a polymerizable monomer having an aromatic ring substituted with an electron-withdrawing group (such as a nitro group or a perfluoroalkyl group) and a polymerizable monomer having a sulfo group, and a lubricant. (Such as polytetrafluoroethylene, low molecular weight polyolefin, fatty acid, or a metal salt or amide thereof). The amount of these additives is usually 0 based on the weight of the toner.
-10% by weight. The toner for developing a positive charge image is dry-blended, melt-kneaded, then coarsely pulverized, and finally finely pulverized using a jet pulverizer or the like to obtain fine particles having a particle size of 5 to 20 μm.

The toner for developing an electrostatic image 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. A fluidity improver (hydrophobic colloidal silica fine powder or the like) can also be used to improve the fluidity of the powder. In addition, instead of the carrier particles, friction with a member such as a charging blade can be performed to form an electric latent image. The electrostatic image developing toner of the present invention is fixed on a support (paper, polyester film, or the like) by a copying machine, a printer, or the like to form a recording material. As a method for fixing to a support, a known hot roll fixing method, flash fixing method, or the like can be applied.

[0021]

The present invention will be further described with reference to the following examples, but the present invention is not limited to these examples. Hereinafter, "part" indicates "part by weight". The methods for measuring the properties of the polyester resins obtained in Examples and Comparative Examples are described below. (Measurement method) Acid value and hydroxyl value Method specified in JISK0070. However, when the sample does not dissolve, a solvent such as dioxane or tetrahydrofuran is used as the solvent. Glass transition temperature (Tg) Method specified in ASTM D3418-82 (DSC
Law). Molecular weight Gel permeation chromatography (GP
Measured in C). (A1) is Labo Plastmill (Toyo Seiki Seisakusho)
And kneaded at 120 ° C. for 30 minutes. In addition,
The conditions for measuring the molecular weight by GPC are as follows. Apparatus: HLC-802A manufactured by Toyo Soda Column: Column TSK gel GMH6 2 pieces (manufactured by Toyo Soda) Measurement temperature: 25 ° C Sample solution: 0.5% by weight THF solution Solution injection amount: 200 μl Detector: Refractive index detector A molecular weight calibration curve was created using standard polystyrene. With a softening point flow tester (CFT-500, manufactured by Shimadzu Corporation)
Using a nozzle of 1.0mmφ × 1.0mm, load 10K
g at a heating rate of 5 ° C./min to determine the temperature at which 1/2 of the 1.5 g sample has flowed out.

Example 1 PO2 of bisphenol A was placed in a reaction vessel equipped with a thermometer, a stirrer equipped with a torque detector, a cooler and a nitrogen inlet tube.
2 parts by adding 144 parts of a molar adduct, 63 parts of an EO2 molar adduct of bisphenol A, 43 parts of neopentyl glycol, 165 parts of terephthalic acid, 20 parts of a 1 molar adduct of t-butylphenol and 2 parts of dibutyltin oxide.
The polyesterification reaction was performed at 10 ° C. The polyester reaction was proceeded under reduced pressure from the time when the reaction product became transparent. The reaction was stopped when the acid value was 3, and the reaction product was taken out to obtain the polyester resin (TB-1) of the present invention. (TB-
The Tg of 1) was 61 ° C., the number average molecular weight was 4,600, the hydroxyl value was 8, and the softening point was 100 ° C.

EXAMPLE 2 Bisphenol A PO2 was added to the same reactor as in Production Example 1.
84 parts of a molar adduct, 210 parts of an EO 2 mol adduct of bisphenol A, 45 parts of a 4.5 mol PO adduct of a novolak phenol resin (number of nuclei is about 4.4), 174 parts of isophthalic acid, and 1 mol of EO of nonylphenol 43 parts of the product and 2.5 parts of dibutyltin oxide were added and reacted at 230 ° C. under a nitrogen stream. The polyesterification reaction was proceeded under reduced pressure from the time when the reaction product became transparent. When the viscosity of the reactant gradually increases and the torque of the stirrer reaches a predetermined value, the reaction is stopped, and the polyester resin (T
B-2) was obtained. (TB-2) has a Tg of 62 ° C., a number average molecular weight of 4000, an acid value of 5, a hydroxyl value of 15, and a softening point of 116.
° C.

Example 3 In the same reactor as in Example 1, bisphenol A PO2 was added.
178 parts of a molar adduct, 170 parts of an EO2 molar adduct of bisphenol A, 35 parts of trimellitic anhydride, 125 parts of terephthalic acid, and 1 mol of a nonylphenol PO adduct 30
And 1.5 parts of dibutyltin oxide were reacted in the same manner as in Example 2 to give the polyester resin (TB-
3) was obtained. (TB-3) had a Tg of 61 ° C, a number average molecular weight of 3,900, an acid value of 5, a hydroxyl value of 20, and a softening point of 125 ° C.

Example 4 In the same reactor as in Production Example 1, 50 parts of a 2-mol adduct of bisphenol A PO, 240 parts of a 2-mol adduct of bisphenol A, and a novolak-type phenol resin (the number of nuclei of about 4.
30 parts of the 4.5 mol EO adduct of 4), terephthalic acid 17
0 parts, 50 parts of a 1 mol addition product of EO of nonylphenol and 1 part of dibutyltin oxide were reacted in the same manner as in Example 2 to obtain a polyester resin (TB-4) of the present invention.
(TB-4) had a Tg of 54 ° C., a number average molecular weight of 3,000,
The acid value was 10, the hydroxyl value was 15, and the softening point was 120 ° C.

Example 5 In the same reactor as in Production Example 1, 227 parts of a PO2 mole adduct of bisphenol A, 140 parts of an EO 2 mole adduct of bisphenol A, 153 parts of terephthalic acid, 15 parts of trimellitic anhydride, and 15 parts of t-butylphenol EO 2 mole adduct 2
0 parts and 1 part of dibutyltin oxide were reacted in the same manner as in Example 2 to give the polyester resin (TB-5) of the present invention.
I got (TB-5) had a Tg of 65 ° C. and a number average molecular weight of 4
The acid value was 500, the acid value was 5, the hydroxyl value was 15, and the softening point was 137 ° C.

Example 6 In a similar reactor as in Production Example 1, 60 parts of a 2-mol adduct of bisphenol A, 230 parts of a 2-mol adduct of EO of bisphenol A, 20 parts of trimethylolpropane, 173 parts of terephthalic acid, and 1 mol of EO of nonylphenol were added. Thing 25
And 1.5 parts of dibutyltin oxide were reacted in the same manner as in Example 2 to give the polyester resin (TB-
6) was obtained. The Tg of (TB-6) was 60 ° C, the number average molecular weight was 4,100, the acid value was 5, the hydroxyl value was 5, and the softening point was 117 ° C.

COMPARATIVE EXAMPLE 1 In the same reactor as in Production Example 1, 305 parts of a 2-mol adduct of bisphenol A PO, 95 parts of a 2-mol adduct of bisphenol A, 155 parts of terephthalic acid, and 1.5 parts of dibutyltin oxide were used. And a polyester resin (TR-1) was obtained. (TR-1) has a Tg of 60 ° C., a number average molecular weight of 3,500, an acid value of 3, and a hydroxyl value of 3
0, 103 ° C.

Comparative Example 2 In the same reactor as in Production Example 1, 100 parts of a 2-mol adduct of bisphenol A PO, 259 parts of a 2-mol adduct of bisphenol A, and novolak-type phenol resin (number of nuclei: about 4.4) Polyester resin (TR-2) was reacted with 25 parts of 5 mol PO adduct, 170 parts of terephthalic acid and 1.5 parts of dibutyltin oxide in the same manner as in Example 2.
I got (TR-2) has a Tg of 63 ° C. and a number average molecular weight of 4
100, acid value 3, hydroxyl value 35, and softening point 118 ° C.

Comparative Example 3 In the same reactor as in Production Example 1, 100 parts of a 2-mol adduct of bisphenol A, 259 parts of a 2-mol adduct of bisphenol A, and 259 parts of a novolak type phenol resin (number of nuclei: about 4.4) were used. 25 parts of a 5 mol PO adduct, 170 parts of terephthalic acid, 35 parts of benzyl alcohol and 1.5 parts of dibutyltin oxide were reacted in the same manner as in Example 2 to obtain a polyester resin (TR-3). T of (TR-3)
g was 60 ° C, the number average molecular weight was 4000, the acid value was 3, the hydroxyl value was 33, and the softening point was 116 ° C.

Use Examples 1-4 Pigments were prepared by mixing 100 parts of the polyester resin (TB-1) of Example 1, 5 parts of pigment and 1 part of a charge control agent (chromium complex 3,5-di-butylsalicylate) in 1 part by weight. To C. I.
Pigment Yellow 17, C.I. I. Pig
Ment Red 122, C.I. I. Pigment
After uniformly mixing Blue 15 and carbon black, respectively, kneading with a Labo Plastomill at an internal temperature of 120 ° C.
The cooled product was finely pulverized by a jet mill and classified by a dispersion separator to obtain toner compositions (T1) to (T4) having an average particle size of 12 μm. Table 1 shows the evaluation results.

Use Examples 5 to 9 Polyester resins (TB-2) to (TB) of Examples 2 to 6
-6) in 88 parts each, carbon black (MA100 manufactured by Mitsubishi Kasei Co., Ltd.) 7 parts, low molecular weight polyethylene (Sunwax 151-P, manufactured by Sanyo Chemical Industries, Ltd.) 5
Parts and a charge control agent (Spiron Black TRH manufactured by Hodogaya Chemical Industry Co., Ltd.)
The mixture was kneaded with a Labo Plastomill at ℃, and the cooled product was finely pulverized with a jet mill and classified with a dispersion separator to obtain toner compositions (T5) to (T9) having an average particle size of 12 μm. Table 1 shows the evaluation results.

Comparative Use Example 1 100 parts of the polyester resin (TR-1) of Comparative Example 1, 5 parts of a pigment (CI Pigment Blue 15), and a charge control agent (a chromium complex compound of 3,5-di-butylsalicylate) After uniformly mixing one part, the mixture is kneaded with a Labo Plast mill at an internal temperature of 120 ° C., and the cooled product is finely pulverized with a jet mill and classified with a dispersion separator to obtain an average particle size of 1 part.
A 2 μm toner composition (CT1) was obtained. Table 1 shows the evaluation results.

Comparative Examples 2 and 3 The polyester resins (TR-2) and (TR) of Comparative Examples 2 and 3
-3) in 88 parts each, carbon black (MA100 manufactured by Mitsubishi Kasei Co., Ltd.) 7 parts, low molecular weight polyethylene (Sunwax 151-P, manufactured by Sanyo Chemical Industry Co., Ltd.) 5
Parts and a charge control agent (Spiron Black TRH manufactured by Hodogaya Chemical Industry Co., Ltd.)
The mixture was kneaded with a LaboPlast mill at ℃ and finely pulverized with a jet mill and classified with a dispersion separator to obtain toner compositions (CT2) and (CT3) having an average particle diameter of 12 μm. Table 1 shows the evaluation results.

[0035]

[Table 1] Evaluation results-------------------------------------------------------------------------------- g) Rise Dependency --------------------------------------------------------------------------- (T1) (TB1) -19 AB (T2 ) (TB1) -21 BA (T3) (TB1) -19 AA (T4) (TB1) -20 BA (T5) (TB2) -21 AA (T6) (TB3) -19 AA (T7) ) (TB4) -22 AB (T8) (TB5) -23 A A (T9) (TB6) -19 B A -------------- −−−−−−−−−− (CT1) (TR1) −10 DB (CT2) (TR2) −13 C C (CT3) (TR3) −11 C C −−− -----------------------------

(Evaluation Method) Preparation of Developer One part of toner was mixed with 24 parts of a silicone resin-coated ferrite carrier for developing an electrostatic image (FL961-150, manufactured by Powder-Tech Co., Ltd.) to prepare a developer. did. Measurement of Saturated Charge Amount (Charge Amount) H. After adjusting the humidity for 8 hours or more, use a tumbler shaker mixer at 50 rpm.
× 1, 3, 7, 20, 60 and 120 minutes of friction stirring, and the charge amount was measured at each time. The charge amount during the friction time when the increase in the charge amount was stopped was defined as the saturation charge amount. Measuring device: Blow-off charge amount measuring device @ Toshiba Chemical
Evaluation standard for rising (rising) of charging The following criteria were used for evaluation based on the results of measuring the amount of charging. A: Friction time to reach a charge amount of 80% of the saturated charge amount is less than 7 minutes B: Friction time to reach a charge amount of 80% of the saturated charge amount is 7 to 20 minutes C: Saturation charge amount D: A friction time to reach a charge amount of 80% of the saturated charge amount of 20 to 60 minutes D: A friction time to reach a charge amount of 80% of the saturation charge amount exceeds 60 minutes Measurement of environmental stability The charge amount of the sample conditioned at high temperature and high humidity and low temperature and low humidity for 8 hours or more was measured. Low temperature and low humidity: 10 ° C, 40% R. H. High temperature and high humidity: 35 ° C, 85% R. H. Evaluation Criteria A: Small change in charge amount between low temperature and low humidity and high temperature and high humidity B: Change amount in charge amount between low temperature and low humidity and high temperature and high humidity C: Charge amount at low temperature and low humidity and high temperature and high humidity Those with large changes

[0037]

The toner binder for developing an electrostatic image of the present invention has the following effects. 1. Since the charge amount is high, a toner having an appropriate charge amount can be obtained by using a small amount of the charge control agent. 2. It is possible to obtain a toner which is excellent in charge rising and reaches a fixed charge amount by short-time friction. 3. It is possible to obtain a toner which is excellent in environmental dependency and has a small change in the charge amount even under various environments. 4. It has an alkyl group and an alkoxy group at the terminal, and improves the dispersibility of a lubricant such as a low-molecular-weight polyolefin when formed into a toner. 5. The amount of monoalcohol distilled off during production is small, and the control of the reaction is facilitated. 6. There is little decrease in Tg, and material design becomes easy.

Claims (6)

[Claims] 1. An electrostatic image development comprising a polyester resin comprising a polycarboxylic acid (A), a polyol (B) and an oxyalkylene ether (C) of a monol (c) containing an aromatic ring. Toner binder. 2. The toner binder according to claim 1, wherein the monol (c) is one or more phenols (c1) selected from the group consisting of phenol, phenol substituted with an alkyl group, and phenol substituted with an alkoxy group. 3. The aralkyl alcohol according to claim 1, wherein the monool (c) is at least one aralkyl alcohol selected from the group consisting of aralkyl alcohols, alkyl-substituted aralkyl alcohols and alkoxy-substituted aralkyl alcohols. Toner binder. 4. The polycarboxylic acid (A) wherein at least a part thereof is a divalent or higher carboxylic acid (A2).
4. The toner binder according to any one of items 1 to 3, 5. The polyols (B) wherein at least a part of the polyols (B) are dihydric or higher alcohols (B2).
The toner binder according to any one of the above. 6. The toner binder according to claim 1, wherein the oxyalkylene ether (C) has a boiling point at normal pressure of 220 ° C. or higher.