JP2003096170A - Polyester resin and resin composition containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyester resin used for a binder, a pigment dispersant or an antistatic agent which can realize a color toner for electrostatic image development, a powder coating material and the like. SOLUTION: An alkyl-substituted alicyclic dicarboxylic acid compound (A) wherein a carboxy group or a carboxylic acid derivative group is bonded to each of neighboring two carbon atoms that constitute an alicyclic ring, an alicyclic dihydric alcohol (B) and a chain aliphatic dihydric alcohol (C) are subjected to polycondensation to give a polyester precursor containing no aromatic ring and having a number-average molecular weight of 1,500 to 5,000 and a glass transition temperature of 50 deg.C or higher. This polyester precursor and a polycarboxylic acid having a sulfo group or the like, or a polyhydric alcohol and the like are subjected to polycondensation to give a polyester resin.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyester resin used as a binder, a dispersant or a charge control agent, which can provide a toner for electrophotography, powder coating material and the like.

[0002]

2. Description of the Related Art In recent years, full-color electrophotographic apparatuses, particularly digitized full-color electrophotographic apparatuses, have been attracting attention and are being widely marketed with the progress of OA. As a toner for developing an electrostatic charge image used in an electrophotographic apparatus, a colorant, a charge control agent, etc. are added to a binder, kneaded, pulverized and further classified, and a fluidity modifier etc. is externally added if necessary. The particles produced by the so-called pulverization method are used. As a binder for toner,
Styrene / acrylic copolymer resins have been mainly used, but in recent years, polyester resins, which are excellent in low-temperature fixability and image surface gloss, have tended to be used due to the increase in speed and color.

As the binder resin for toner, there are disclosed in JP-A-56-1952 and JP-A-58-17452, an anhydride of cyclohexene dicarboxylic acid or cyclohexane dicarboxylic acid anhydride, and a polyhydric alcohol having a bisphenol structure. A polyester resin obtained by polycondensing is disclosed. Further, JP-A No. 12-284533 discloses a polyester resin containing hydrogenated bisphenol A and a phenol novolac type epoxy resin as essential components in place of the diols having a bisphenol structure. However, the fluidity that contributes to the low-temperature fixability of the toner and the blocking resistance that contributes to the high-temperature storability have been insufficient. In addition, since the aromatic ring is contained, it is not a sufficient solution to environmental problems. Polyester resin is also used to uniformly disperse the colorant in the toner or to control the charge amount. The resin for dispersion or charge control is used in the above-mentioned pulverization method, and is mixed with a monomer and a colorant to form a monomer composition, which is emulsion-polymerized or suspension-polymerized, and if necessary. It can be used in a method of directly obtaining colored particles by associating with each other. As such a polyester resin, for example,
A polyester resin obtained from an aromatic polycarboxylic acid having a sulfonate group, an ethanediol derivative, and cyclohexanedimethanol is disclosed. (JP-A-5-107807). However, it does not fully solve the environmental problem in that it contains an aromatic ring.

On the other hand, the powder coating material is a coating material which does not contain a volatile component such as an organic solvent and only the coating film forming component is applied to an object to be coated and melted to form a coating film. Compared with conventional solvent-based paints, powder paints 1) can be applied thickly in 1 time, 2)
The powder that did not adhere can be collected and reused.
3) Since it has advantages such as a small amount of waste paint, it is now widely used in various industrial product fields such as automobile parts, vehicles or home appliances from the viewpoint of rationalization of coating and environmental friendliness. As such powder coating materials, epoxy-based, vinyl chloride-based, polyolefin-based, acrylic-based, and polyester-based powder coating materials have been conventionally used. Among them, the polyester powder coating material is widely known as a coating material having a balanced coating film performance. The polyester resin preferably used in the above-mentioned applications has a good affinity with a pigment as a colorant, has a sharp melt property (= melts quickly) at a relatively low temperature, and has a sharp storage property at the time of storage. It is desired not to block. In recent years, bisphenol A, which is regarded as one of environmental hormones, and certain aromatic compounds such as styrene monomer, which is expected to adversely affect the human body, have become a problem as environmental pollutants. There is a growing demand for polyester resins containing no.

As a powder coating composition, Japanese Patent Publication No. 8-512
Japanese Patent No. 078 discloses a product containing an amorphous polyester composed of residues of cyclohexanedicarboxylic acid and alicyclic diol. However, it was not satisfactory as a paint in that the sharp melt property was not sufficient. Polyester resin is also used to uniformly disperse the colorant in the powder coating material. For example, JP-A-6-336557 discloses a polyester resin having an amine value obtained by reacting a mixture of ε-caprolactone, lauric acid and tetrabutyl titanate under a nitrogen atmosphere and then reacting with polyethyleneimine. ing. The dispersibility of the colorant was insufficient.

[0006]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and is low in aromatic components that can be environmental pollutants such as bisphenol A which is an environmental hormone, and is involved in low-temperature fixability. A binder, a dispersant or a binder capable of realizing a color toner for developing an electrostatic charge image, which has excellent fluidity and storage stability, and a powder coating which has excellent appearance (smoothness) and weather resistance and also has good blocking resistance. It is intended to provide a polyester resin used as a charge control agent. As a result of intensive studies, the present inventor has found that an alicyclic divalent carboxylic acid compound such as 4-methyl-hexahydrophthalic anhydride and 2,2-bis (4-hydroxycyclohexyl) -propane (that is, Aliphatic dihydric alcohols such as hydrogenated bisphenol A) and chain aliphatic 2 such as ethylene glycol
Polyester obtained by polycondensing a polyester precursor having a specific glass transition temperature obtained by polycondensation with a polyhydric alcohol, and a polyvalent carboxylic acid containing a sulfonic acid group or an amino group and / or a polyhydric alcohol It was found that the resin has excellent fluidity at low temperature, excellent storability at high temperature, can improve the dispersibility of the pigment, and can control the electrostatic charge amount, and based on this finding, the present invention was completed. I arrived.

[0007]

According to the present invention, the alicyclic divalent carboxylic acid compound (A), the alicyclic dihydric alcohol (B), and the chain aliphatic dihydric alcohol (C) are thus obtained.
Is a polycondensate of 1,500 to 5,0 having a number average molecular weight of 1,500 to 5,0.
Is a polycondensation product of a polyester precursor of No. 00 with a polycarboxylic acid and / or a polyhydric alcohol containing a sulfonic acid group or a salt thereof or an amino group or a salt thereof, and has a number average molecular weight of 5,500 to 30. , A polyester resin of 1,000, or a polycondensation product of an alicyclic divalent carboxylic acid compound (A), an alicyclic dihydric alcohol (B), and a chain aliphatic dihydric alcohol (C), with a number average A polyester precursor having a molecular weight of 1,500 to 5,000, a polyvalent carboxylic acid and / or a polyvalent alcohol containing a sulfonic acid group or a salt thereof, or an amino group or a salt thereof, and a polyvalent carboxylic acid other than the above. And / or a polycondensation product with a polyhydric alcohol having a number average molecular weight of 5,
A polyester resin is provided that is 500 to 30,000. Moreover, according to this invention, the resin composition containing the said polyester resin and a coloring agent is provided.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The polyester resin of the present invention is a polycondensate of a specific polyester precursor with a polyfunctional carboxylic acid and / or polyhydric alcohol having a specific functional group,
And a polycondensation product of a specific polyester precursor, a polyvalent carboxylic acid and / or polyhydric alcohol having a specific functional group, and a polyvalent carboxylic acid and / or polyhydric alcohol other than the above.

The polyester precursor is a polycondensate of a polycarboxylic acid and a polyhydric alcohol. The polycarboxylic acid used for the polyester precursor is an alicyclic divalent carboxylic acid compound (A). The alicyclic divalent carboxylic acid compound is a compound in which a carboxyl group or a carboxylic acid derivative group is bonded to each of two carbon atoms forming an alicycle. As a suitable alicyclic divalent carboxylic acid compound (A), a carboxyl group or a carboxylic acid derivative group (amide group, ester group, acid anhydride group, acid halide) An alicyclic divalent carboxylic acid compound (A) formed by bonding to adjacent carbon atoms; particularly preferably an alicyclic divalent carboxylic acid represented by the general formula (1) or (2) or an anhydride thereof. An alkyl group such as the one bonded to an alicyclic ring as a substituent. The alkyl group preferably has 1 to 8 carbon atoms,
Specific examples thereof include a methyl group, an ethyl group, a propyl group and an isopropyl group.

[0010]

[Chemical 3]

[0011]

[Chemical 4] (R in the formula (1) or (2) is an alkyl group.)

Examples of the alicyclic structure include monocyclic rings such as cyclopentane ring, cyclohexane ring, cycloheptane ring and cyclohexene ring; and polycyclic rings such as norbornane ring and norbornene ring. The alicyclic divalent carboxylic acid anhydride is an acid anhydride group formed by dehydration of two carboxyl groups as shown in formula (1) or (2).

The alicyclic divalent carboxylic acid compound (A) used in the present invention is, for example, butadiene, isoprene,
It can be obtained by reacting a diene compound such as piperylene or cyclopentadiene; and maleic anhydride, and hydrogenating if necessary. Specific examples of the alicyclic divalent carboxylic acid compound (A) include tetrahydroterephthalic acid, 3-alkyltetrahydroterephthalic acid, hexahydroterephthalic acid, 3-alkylhexahydroterephthalic acid, 4-alkyltetrahydroterephthalic acid and 4-alkyltetrahydroterephthalic acid. Alkyl hexahydroterephthalic acid, 3,6-endomethylene-tetrahydroterephthalic acid, 2-alkyl-3,
6-endomethylene-tetrahydroterephthalic acid, 3-
Alkyl-3,6-endomethylene-tetrahydroterephthalic acid, 3,6-Endomethylene-hexahydroterephthalic acid, 2-alkyl-3,6-endmethylene-hexahydroterephthalic acid, 3-alkyl-3,6-endo Methylene-hexahydroterephthalic acid; tetrahydroisophthalic acid, 3-alkyltetrahydroisophthalic acid, hexahydroisophthalic acid, 3-alkylhexahydroisophthalic acid, 4-alkyltetrahydroisophthalic acid, 4-alkylhexahydroisophthalic acid, 3,6
-Endomethylene-tetrahydroisophthalic acid, 2-alkyl-3,6-endomethylene-tetrahydroisophthalic acid, 3-alkyl-3,6-endomethylene-tetrahydroisophthalic acid, 3,6-endomethylene-hexahydroisophthalic acid, 2-alkyl-3,6-endomethylene-hexahydroisophthalic acid, 3-alkyl-
3,6-Endomethylene-hexahydroisophthalic acid;

Tetrahydrophthalic acid, 3-alkyltetrahydrophthalic acid, hexahydrophthalic acid, 3-alkylhexahydrophthalic acid, 4-alkyltetrahydrophthalic acid, 4-alkylhexahydrophthalic acid, 3,6-
Endomethylene-tetrahydrophthalic acid, 2-alkyl-3,6-endomethylene-tetrahydrophthalic acid, 3
-Alkyl-3,6-endomethylene-tetrahydrophthalic acid, 3,6-endomethylene-hexahydrophthalic acid, 2-alkyl-3,6-endomethylene-hexahydrophthalic acid, 3-alkyl-3,6- Endomethylene-hexahydrophthalic acid and their derivatives (anhydrides, esters, halides, amides, etc.) and the like can be mentioned. These may be used alone or in combination of two or more. Among these,
3-Alkyltetrahydrophthalic acid, 3-alkylhexahydrophthalic acid, 4-alkyltetrahydrophthalic acid, 4-alkylhexahydrophthalic acid and their anhydrides are preferred because they give highly flowable resins. The amount of the alicyclic divalent carboxylic acid compound is usually 70 to 100 mol%, particularly 80 to 1 of the total carboxylic acid components constituting the precursor.
It is preferably 00 mol%. If this ratio is low, sufficient fluidity may not be obtained.

If desired, a polyvalent carboxylic acid such as an aliphatic polyvalent carboxylic acid or an aromatic polyvalent carboxylic acid may be copolymerized. The proportion of the aliphatic polycarboxylic acid is preferably 15 mol% or less. When the proportion of the aliphatic polycarboxylic acid is large, the glass transition temperature of the polyester precursor is lowered and the blocking resistance when used as a toner or powder coating is lowered. The proportion of aromatic polycarboxylic acid is also preferably 15 mol% or less. Examples of the copolymerizable polycarboxylic acid include adipic acid, azelaic acid, 1,10-decanedicarboxylic acid, dimer acid; trimellitic acid, pyromellitic acid and trimesic acid.

In the polyester precursor, an alicyclic dihydric alcohol (B) and a chain aliphatic dihydric alcohol (C) are used as the polyhydric alcohol. Examples of the alicyclic dihydric alcohol (B) include 2,2-bis (4-hydroxycyclohexyl) -propane (that is, hydrogenated bisphenol A), 1,4-cyclohexanedimethanol,
2,2,4,4-tetramethyl-1,3-cyclohexanediol, 1,4-cyclohexanediol and the like can be mentioned. Of these, hydrogenated bisphenol A is preferred. As the chain aliphatic dihydric alcohol (C), linear aliphatic glycols such as ethylene glycol, diethylene glycol, 1,4-butanediol, and 1,6-hexanediol; propylene glycol, neopentyl glycol, 2-ethyl- Examples thereof include branched chain aliphatic glycols such as 2-butyl-1,3-propanediol. Of these, ethylene glycol is preferred.

A preferred polyester precursor is a chain aliphatic dihydric alcohol (C) in which 40 to 80 mol% of all polyhydric alcohol components in the precursor are 20 to 60 mol% of an alicyclic group 2.
It is a polyhydric alcohol (B). When the amount of the chain aliphatic dihydric alcohol (C) is small, the molecular weight of the polyester precursor to be synthesized tends to be low. Further, if the amount of the alicyclic dihydric alcohol (B) is too small, the glass transition temperature becomes low, and the effect of improving the blocking resistance tends to decrease. On the contrary, the amount of the alicyclic dihydric alcohol increases. If it is too much, the molecular weight of the polyester precursor tends to be low. Polyhydric alcohol components other than the above, for example, trihydric or higher alcohols such as trimethylolpropane, glycerin, pentaerythritol, and dipentaerythritol can be appropriately used as necessary.

The molecular weight of the polyester precursor used in the present invention is determined by gel permeation chromatography (GP
The polystyrene reduced number average molecular weight measured in C) is 1,
500 to 5,000, preferably 2,000 to 4,000
It is 0. When the molecular weight is within this range, the blocking resistance and processability are excellent, and the coating film strength is high. The glass transition temperature is preferably 50 ° C or higher, particularly preferably 50 to 80 ° C. When the glass transition temperature is 50 ° C. or higher, phenomena such as aggregation and solidification of powdered resin are less likely to occur. The polyester precursor used in the present invention has a hydroxyl value of usually 10 to 100 mgKOH / g, preferably 25 to 70 mgKOH / g. When the hydroxyl value is small, large irregularities are generated on the surface of the coating film, and the smoothness tends to be lowered. On the contrary, when it is large, the water resistance tends to be lowered. This polyester precursor preferably does not contain an aromatic ring.

The polyester precursor used in the present invention can be obtained by a method similar to the known method for producing polyester (that is, polycondensation method). In polycondensing the polyhydric carboxylic acid component and the polyhydric alcohol component, the total hydroxyl value [X] of the alcoholic reactive groups in all monomers obtained by summing the polyhydric carboxylic acid component and the polyhydric alcohol component is Total number of acid values of carboxylic acid reactive groups [Y]
It is preferable to carry out the reaction under the condition of not lowering the molecular weight of the polyester precursor and the hydroxyl value. The ratio of the total number [X] of hydroxyl values of alcoholic reactive groups to the total number [Y] of acid values of carboxylic acid reactive groups is preferably [X] / [Y] equivalent ratio of 1.00 or more. 01-1.5 are more preferable, 1.0
The range of 3 to 1.3 is particularly preferable. Here, the alcoholic reactive group refers to an alcoholic functional group that forms an ester bond, and typically includes a hydroxyl group and the like. The carboxylic acid reactive group refers to a carboxylic acid functional group that forms an ester bond, and usually includes a carboxyl group or a carboxylic acid derivative group.

The polycondensation reaction is carried out, for example, at a reaction temperature of 100 to
It is carried out at 300 ° C., preferably 150 to 280 ° C., particularly preferably in the presence of an inert gas. If necessary, a water-insoluble organic solvent that is azeotropic with water, such as toluene or xylene, may be used. The polycondensation reaction is carried out under reduced pressure (usually 0.1 to 500 mmHg, preferably 0.5 to 500 mmHg).
200 mmHg, more preferably 1 to 50 mmHg). An esterification catalyst is usually used in this polycondensation reaction. Examples of the esterification catalyst include Bronsted acids such as paratoluenesulfonic acid, sulfuric acid, and phosphoric acid; calcium acetate, zinc acetate, manganese acetate, zinc stearate; iron and zinc acetylacetonates; metal alkoxides; alkyltin oxides. , Organoalkyl compounds such as dialkyltin oxide and organotitanium compounds: metal oxides such as tin oxide, antimony oxide, titanium oxide and vanadium oxide: heteropolyacids, etc. Alkoxides, heteropoly acids or iron acetylacetonates are preferred.

The polyvalent carboxylic acid and / or polyhydric alcohol constituting the polyester resin of the present invention is a polycarboxylic acid and / or polyhydric alcohol containing a sulfonic acid group or a salt thereof or an amino group or a salt thereof. , And preferably a polyvalent carboxylic acid and / or a polyhydric alcohol having a ring structure. Examples of the polyvalent carboxylic acid and / or polyhydric alcohol containing a sulfonic acid group or a salt thereof include sulfoterephthalic acid, 5-sulfoisophthalic acid, 5
-Sulfoisophthalic acid methyl ester, 4-sulfophthalic acid, 4-sulfophthalic anhydride, 4-sulfonaphthalene-2,7-dicarboxylic acid, 5- [4-sulfophenoxy] isophthalic acid; 5-sulfohexahydroisophthalic acid, 5-sulfohexahydroisophthalic acid methyl ester, 4-sulfohexahydrophthalic acid, 4-sulfohexahydrophthalic anhydride; 5-sulfotetrahydroisophthalic acid, 5-sulfotetrahydroisophthalic acid methyl ester, 4-sulfotetrahydrophthalic acid , 4-sulfotetrahydrophthalic anhydride; 2,3-bis (hydroxymethyl) benzenesulfonic acid, 3,5-bis (hydroxymethyl) benzenesulfonic acid, 3,4-bis (hydroxymethyl) benzenesulfonic acid, 2 , 5-bis (hydroxymethyl) Such as benzenesulfonic acid and include their sulfonate. As sulfonate, ammonium, Li, Na, K, Mg, Ca, C
Salts such as u and Fe may be mentioned, and particularly when used as a charge control agent, K salt or Na salt is preferable.

Examples of polyvalent carboxylic acids and / or polyhydric alcohols containing an amino group or a salt thereof include aminoterephthalic acid, 5-aminoisophthalic acid, 5-aminoisophthalic acid methyl ester, 4-aminophthalic acid and 4-aminophthalic acid.
Aminophthalic anhydride, 4-aminonaphthalene-2,7
Dicarboxylic acid, 5- [4-aminophenoxy] isophthalic acid; 5-aminohexahydroisophthalic acid, 5-aminohexahydroisophthalic acid methyl ester, 4-aminohexahydrophthalic acid, 4-aminohexahydrophthalic anhydride; 5-aminotetrahydroisophthalic acid, 5
-Aminotetrahydroisophthalic acid methyl ester, 4
-Aminotetrahydrophthalic acid, 4-aminotetrahydrophthalic anhydride; 2-amino-2-methyl-1,3-
Propanediol, diethanolamine, 2-amino-
4-hydroxymethylbenzyl alcohol, 2-amino-3-hydroxymethylbenzyl alcohol, 4-amino-2-hydroxymethylbenzyl alcohol, 5-amino-3-hydroxymethylbenzyl alcohol, 2,
4-bis (hydroxyethyl) -1-aminocyclohexane and the like and ammonium salts thereof can be mentioned. In the present invention, the amount of polyvalent carboxylic acid and / or polyhydric alcohol is usually 0.
It is 2 to 10 mol%, preferably 0.5 to 5 mol%. By containing a polyvalent carboxylic acid and / or a polyhydric alcohol as a polycondensation component, the dispersibility of the pigment in the toner or the paint can be improved, and the electrostatic chargeability of the resin can be controlled. The polyhydric carboxylic acid and / or polyhydric alcohol has a function of connecting the polyester precursors, and by using the polyhydric carboxylic acid and / or polyhydric alcohol, the molecular weight of the polyester resin can be increased.

The polyester resin of the present invention may contain other polyvalent carboxylic acid and / or polyhydric alcohol as a polycondensation component in addition to the polyvalent carboxylic acid and / or polyhydric alcohol. When a polyvalent carboxylic acid and / or a polyhydric alcohol is used, polyester precursors can be joined together to easily obtain a high molecular weight polyester resin. The polyvalent carboxylic acid and / or polyhydric alcohol is not particularly limited as long as it is something other than the polyvalent carboxylic acid and / or polyhydric alcohol, and as described above, an alicyclic dicarboxylic acid, an aliphatic Dicarboxylic acids, aliphatic tricarboxylic acids, aromatic dicarboxylic acids; alicyclic diols, alicyclic triols, aliphatic diols, aliphatic triols, aromatic diols and the like can be mentioned. Suitable examples of polyvalent carboxylic acid and / or polyhydric alcohol include:
A ring structure-containing divalent carboxylic acid compound in which a carboxyl group or a carboxylic acid derivative group is bonded to each of two non-adjacent carbon atoms constituting a ring such as terephthalic acid and hexahydroterephthalic acid; Examples thereof include bis (hydroxyalkyl) terephthalate and bis (hydroxyalkyl) hexahydroterephthalate. The amount of polycarboxylic acid and / or polyhydric alcohol is preferably 10 to 50 parts by weight, and particularly preferably 20 to 40 parts by weight, based on 100 parts by weight of the polyester precursor. When the amount of the polyvalent carboxylic acid and / or the polyhydric alcohol is within the above range, it is possible to increase the molecular weight without impairing the fluidity, which is preferable.

The polycondensation reaction between the polyester precursor, the polyvalent carboxylic acid and / or polyhydric alcohol, and the polyvalent carboxylic acid and / or polyhydric alcohol optionally used is carried out by the above-mentioned precursor. It can be carried out by the same method as that used for production. That is,
In this polycondensation reaction, a polyester precursor, a polyvalent carboxylic acid and / or a polyhydric alcohol, and a polyvalent carboxylic acid and / or a polyhydric alcohol which are used as necessary, are required at the above reaction temperature. The esterification catalyst may be added accordingly, and the reaction may be performed under reduced pressure. In addition, after the polycondensation reaction for synthesizing the polyester precursor is performed, the reaction system is provided with a polyvalent carboxylic acid and / or a polyhydric alcohol, and further, a polyvalent carboxylic acid and / or a polyvalent carboxylic acid optionally used. The polycondensation reaction can be continuously performed by adding a polyhydric alcohol.

The number average molecular weight of the polyester resin of the present invention is 5,500 to 30,000, preferably 7,
It is 500 to 15,000. The number average molecular weight is a polystyrene conversion value measured by gel permeation chromatography (GPC). When the molecular weight is within this range, the blocking resistance and processability are excellent, and the coating film strength is high. The glass transition temperature of the polyester resin of the present invention is preferably 50 ° C. or higher, particularly preferably 5 ° C.
It is 0 to 80 ° C. When the glass transition temperature is 50 ° C. or higher, phenomena such as aggregation and solidification of powdered resin are less likely to occur.

The polyester resin of the present invention can be used as it is as a binder, a dispersant, or a charge control agent for toner or powder coating, or can be used as a mixture with other resins. When mixed with other resins, the polyester resin of the present invention preferably accounts for at least 25% by weight, more preferably at least 33% by weight, particularly preferably at least 40% by weight, most preferably at least 50% by weight of the total resin. Used above. Suitable resins that can be mixed with the polyester resin of the present invention include epoxy resins, styrene-acrylate copolymer resins, acrylate resins, and other polyester resins.

The resin composition of the present invention comprises the polyester resin of the present invention and a colorant.
The colorant used in the resin composition of the present invention is a pigment or dye used for coloring. Dyes are preferable from the viewpoint of spectral transmission characteristics. When using a pigment as a colorant, benzidine-based, azo-based, and isoindoline-based pigments are used for yellow coloring.
For magenta coloring, azo lake type, rhodamine lake type,
Quinacridone pigments, naphthol pigments and diketopyrrolopyrrole pigments are preferably used for cyan coloring, and phthalocyanine pigments and indanthrene pigments are preferably used for cyan coloring. Carbon black is usually used to obtain a black toner. Examples of carbon black include thermal black, acetylene black, channel black, furnace black, lamp black and the like. When a dye is used as a coloring agent, azo-based, nitro-based, quinoline-based, quinophthalone-based, and methine-based dyes are used for yellow coloring, anthraquinone-based, azo-, xanthene-based dyes are used for magenta coloring, and anthraquinone is used for cyan coloring. Based dyes, phthalocyanine dyes and indoaniline dyes are preferably used. The amount of the colorant may be appropriately selected depending on the desired shade, density and the like.

In addition to the hardener, the crosslinking agent, the antioxidant, the antistatic agent, the ultraviolet absorber, the resin composition of the present invention,
It may contain additives such as a light stabilizer, a surfactant, a dispersant, a leveling agent, an emulsifier, a flame retardant, a filler and a plasticizer.

The curing agent used in the resin composition of the present invention is not particularly limited, but an isocyanate curing agent is suitable. As the isocyanate-based curing agent, a blocked isophorone diisocyanate-based curing agent and a blocked hydrogenated diphenylmethane diisocyanate-based curing agent that do not exhibit activity at a certain temperature or lower are preferable, and specific examples include isophorone diisocyanate-based blocked with ε-caprolactam. Hardening agent "Vestagon B1530" manufactured by Hüls, isophorone diisocyanate curing agent "Vestagon BF1540" manufactured by Bayer Co., "TPLS2147", ε-caprolactam, which does not contain a blocking agent and is self-blocking with isocyanate groups. Examples of hydrogenated diphenylmethane diisocyanate-based curing agent blocked by McWHORTER "24-2430" and "24-2431". The amount of curing agent is
0.5 to 1.5 times equivalent, preferably 1.0 times equivalent to the hydroxyl value of the polyester resin is suitable.

The resin composition of the present invention is not particularly limited depending on its production method. For example, it can be prepared by melt-kneading a polyester resin, a colorant, and optionally other additives at 70 to 150 ° C. using a kneader or roll.

[0031]

EXAMPLES Next, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples. Parts and percentages in these examples are by weight unless otherwise stated. The operation or test of the evaluation items was as follows. [Number average molecular weight] The number average molecular weight of the polyester is GP
According to method C, it is calculated as a standard polystyrene equivalent amount. [Hydroxyl Value] The hydroxyl value of polyester is 2,4,9,2-83 of "Standard Oil and Fat Analysis Test Method" (Japan Oil Chemistry Association).
Measure according to the method described in section. The unit is mgKO
H / g. [Glass Transition Temperature] Glass transition temperature of polyester (T
g) is measured according to the DSC method specified in JIS K 7121. The unit is ° C. [Storability] The toner was left in an atmosphere of a temperature of 45 ° C. for 24 hours, taken out, and examined for the presence of aggregates. When there were no aggregates, it was evaluated as ◯, when small aggregates were evaluated as Δ, and when large aggregates were evaluated as x.

[Pigment dispersibility] The toner was melted on a slide glass to form a film. This film-shaped toner was observed with an optical microscope at a magnification of 400 times to visually determine the presence or absence of pigment aggregates. When there were no aggregates, it was evaluated as ◯; when there were a few aggregates, as Δ; when there were many aggregates, it was evaluated as x. [Fixing start temperature & offset start temperature] 5 parts of toner,
95 parts of iron powder carrier (TEFV150 / 250: manufactured by Nippon Iron Powder Co., Ltd.) was mixed with a ball mill to obtain a developer. This developer was filled in a commercially available copying machine from which the fixing unit was removed, and transferred onto a copy paper to form a transferred image. Next, the transferred image on the copy paper was heat-fixed by using a heating roll fixing device made of polytetrafluoroethylene while various roll temperatures were changed, and a fixed image was formed. An adhesive tape was attached to the fixed image, and a peeling test was performed to determine the minimum temperature at which the fixed image did not peel off (= fixing start temperature). Further, the minimum temperature (= offset start temperature) at which the transferred image starts to be fused to the roll was determined. The unit in the table is ° C.

[Synthesis of Polyester Precursor] Synthesis Example 1 545 parts of 4-methyl-hexahydrophthalic anhydride were placed in a three-necked flask equipped with a stirrer, a thermometer, a reflux condenser, a water dividing pipe and a nitrogen gas introducing pipe. , Bis (4-hydroxycyclohexyl) -propane (284 parts) and ethylene glycol (171 parts) were charged. The ratio of total hydroxyl value [X] / acid value [Y] is 1.20. Stirring was carried out while introducing nitrogen gas, and the reaction was carried out at 200 ° C. for 3 hours while removing water produced during the reaction. Next, 0.5 part of tetrabutoxy titanate was added, the reaction temperature was raised to 220 ° C. and the pressure in the flask was gradually decreased to 1.5 mmHg or less after 1.5 hours, and then the reaction was continued for another 3 hours to obtain the polyester precursor. Body A is obtained. The resulting polyester precursor A has a number average molecular weight of 2,050 and a hydroxyl value of 6
8. The glass transition temperature was 62 ° C.

Synthesis Example 2 484 parts of hexahydrophthalic anhydride and 2,2-bis (4-hydroxycyclohexyl) were placed in a three-necked flask equipped with a stirrer, a thermometer, a reflux condenser, a diversion tube and a nitrogen gas inlet tube. ) -Propane 373 parts and ethylene glycol 143 parts were charged. The ratio of total hydroxyl value [X] / acid value [Y] is 1.10. Stirring is carried out while introducing nitrogen gas to remove water generated during the reaction at 200
The reaction was carried out at 0 ° C for 3 hours. Next, 0.3 part of iron acetylacetonate was added, the reaction temperature was raised to 220 ° C., the pressure in the flask was gradually reduced, and 1.5 mmHg after 1.5 hours.
The reaction was continued below for 3.5 hours to obtain a polyester precursor B. The resulting polyester precursor B had a number average molecular weight of 3,440, a hydroxyl value of 53, and a glass transition temperature of 70 ° C.

[Synthesis of bis (β-hydroxyethyl) hexahydroterephthalate] Synthesis Example 3 In a three-necked flask equipped with a stirrer, a thermometer, a reflux condenser, a water dividing pipe and a nitrogen gas introducing pipe, 1,4-cyclohexanedicarboxylic acid was added. Acid 557 parts, and ethylene glycol 44
I prepared three copies. Stir while introducing nitrogen gas,
The reaction was carried out at 180 ° C. for 5 hours while removing water generated during the reaction. The reaction temperature was raised to 200 ° C. and the pressure in the flask was gradually decreased to 1.5 mmHg or less after 1.5 hours, and then the reaction was continued for another 2 hours to obtain bis (β-hydroxyethyl) hexahydroterephthalate. Bis (β-hydroxyethyl) hexahydroterephthalate was a colorless transparent liquid.

Example 1 80 parts of the polyester precursor A obtained in Synthesis Example 1 and 5-sodium sulfoisophthalic acid were placed in a three-necked flask equipped with a stirrer, a thermometer, a reflux condenser, a diversion tube and a nitrogen gas inlet tube. 0.5 parts of methyl ester and 19.5 parts of bis (β-hydroxyethyl) hexahydroterephthalate obtained in Synthesis Example 3 were charged. The mixture was stirred while introducing nitrogen gas, and the reaction was carried out at 200 ° C. for 5 hours while removing water produced during the reaction. 0.3 parts of iron acetylacetonate was added, the reaction temperature was raised to 220 ° C. and the pressure in the flask was gradually reduced, and after 5 hours, 5 mmH
The polyester resin C was obtained by setting the amount to g or less and further continuing the reaction for 5 hours. The obtained polyester resin C has a number average molecular weight of 11,260 and a hydroxyl value of 12 mgKOH /
g, a light yellow transparent solid having a glass transition temperature of 63 ° C. 95 parts of polyester resin C and copper phthalocyanine cyan pigment (Heliogen Blue S7084: BASF
(Manufactured by K.K.) 5 parts by melt-kneading with a twin-screw extruder and then solidifying,
The toner was pulverized using a jet mill, and then classified by wind force to obtain a cyan toner having a number average particle diameter of 10 μm. The evaluation results of this toner are shown in Table 1. The image showed a vivid cyan color.

Example 2 80 parts of the polyester precursor B obtained in Synthesis Example 2 and methyl 5-sodium sulfoisophthalate were placed in a three-necked flask equipped with a stirrer, a thermometer, a reflux condenser, a water dividing tube and a nitrogen gas introducing tube. 3 parts of ester and 17 parts of bis (β-hydroxyethyl) hexahydroterephthalate obtained in Synthesis Example 3 were charged. Stirring is carried out while introducing nitrogen gas, and water generated during the reaction is removed at 200 ° C. for 5 minutes.
Reacted for hours. Titanium isopropoxide (0.5 parts) was added, the reaction temperature was raised to 220 ° C., the pressure in the flask was gradually decreased, 1.5 hours later, the pressure was reduced to 5 mmHg or less, and the reaction was continued for another 5 hours to give polyester resin D. Obtained.
The obtained polyester resin D has a number average molecular weight of 7,8.
It was a light yellow transparent solid having a hydroxyl value of 65, a hydroxyl value of 16 mgKOH / g, and a glass transition temperature of 70 ° C. Using this polyester resin D, a cyan toner was obtained in the same manner as in Example 1. The evaluation results are shown in Table 1. The image showed a vivid cyan color.

Comparative Example 1 A three-necked flask equipped with a stirrer, a thermometer, a reflux condenser, a water dividing pipe and a nitrogen gas introducing pipe was placed in a dimethyl terephthalate flask.
278 parts, dimethyl isophthalate 261 parts, trimellitic acid 5 parts, 5-sodium sulfoisophthalic acid methyl ester 17 parts, ethylene glycol 175 parts, propylene glycol 215 parts, 1,4-cyclohexane dimethano -49 parts and tetrabutoxytitanate 0.3 parts were charged and reacted at about 205 ° C for 2 hours. Then, the temperature was raised to 240 ° C., the pressure was adjusted to 1 to 10 mmHg, and the reaction was continued for 60 minutes to obtain a polyester resin E. The resulting polyester resin E has a number average molecular weight of 5,30.
It was 0, the hydroxyl value was 19 mgKOH / g, and the glass transition temperature was 63 ° C., which was a light yellow transparent solid. Using this polyester resin E, a cyan toner was obtained in the same manner as in Example 1. The evaluation results are shown in Table 1.

[0039]

[Table 1]

As is clear from Table 1, the toner using the polyester resin (Examples 1 and 2) of the present invention as a binder has good pigment dispersibility, a low fixing start temperature, and a high offset start temperature. The phenomenon is unlikely to occur. The image quality is also clear. Furthermore, the storage stability of the toner is good. On the other hand, in the polyester resin in which the alicyclic divalent carboxylic acid is not polycondensed (Comparative Example 1), the pigment dispersibility is insufficient and the fixing start temperature is high. Furthermore, the storage stability is also insufficient.

[0041]

The toner for developing an electrostatic charge image using the polyester resin of the present invention has a fixing start temperature and an offset start temperature in a fixing device in which a heat-resistant film capable of power saving and quick start and a thermal head are combined. Shows a good fixing property and high temperature storability.
Further, even if a releasing agent or the like is not added to the toner, the surface smoothness and transparency of the fixed image are excellent, so that the reproducibility of the color image is excellent. Further, since the pigment dispersibility is excellent, the color development of the image is clear. Further, the charge amount of the toner can be controlled by changing the amount of sulfonic acid groups or the like to be bonded. Further, the binder using the polyester resin of the present invention can be a powder coating having excellent surface properties, weather resistance, matteness and fluidity of the powder coating. As a result, since the powder coating material does not solidify, the efficiency of powder coating is increased, and at the same time, a coating film having excellent appearance (smoothness) and weather resistance can be formed. The powder coating material according to the present invention is used outdoors and can be used for an object to be coated which is required to have a matting property.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 2H005 AA01 AA06 CA08 DA01 EA06                 4J029 AA03 AC04 AD01 AE11 BA02                       BA03 BA05 BA07 BA08 BA10                       BD03C BD06C BD07A BD10                       CB04B CB05B CB06B CB07B                       CD03 DA02 DB02 HA01 HB01                       HB02 HB03A HD01 JB131                       JB151 JF321 JF561 KB02                       KC01 KC05 KE03 KE05 KE15

Claims (8)

[Claims] 1. A polycondensation product of an alicyclic divalent carboxylic acid compound (A), an alicyclic dihydric alcohol (B), and a chain aliphatic dihydric alcohol (C), having a number average molecular weight of 1 , 50
It is a polycondensation product of a polyester precursor of 0 to 5,000 and a polyvalent carboxylic acid and / or a polyhydric alcohol containing a sulfonic acid group or a salt thereof or an amino group or a salt thereof and having a number average molecular weight of 5 , 500-3
A polyester resin that is 10,000. 2. A polycondensation product of an alicyclic divalent carboxylic acid compound (A), an alicyclic dihydric alcohol (B) and a chain aliphatic dihydric alcohol (C), having a number average molecular weight of 1 , 50
Polyester precursor of 0 to 5,000, polyvalent carboxylic acid and / or polyhydric alcohol containing sulfonic acid group or salt thereof or amino group or salt thereof, and polyvalent carboxylic acid and / or polyvalent other than the above It is a polycondensate with alcohol and has a number average molecular weight of 5,500.
A polyester resin that is ˜30,000. 3. The alicyclic divalent carboxylic acid compound (A)
Is a compound in which a carboxyl group or a carboxylic acid derivative group is bonded to each of two adjacent carbon atoms forming an alicycle, and the polyester resin according to claim 1. 4. The alicyclic divalent carboxylic acid compound (A)
Is a compound represented by the general formula (1) or (2) or an anhydride thereof. [Chemical 1] [Chemical 2] (R in the formula (1) or (2) is an alkyl group.) 5. A polyvalent carboxylic acid and / or polyhydric alcohol having a ring structure and having a carboxyl group or a carboxylic acid derivative group bonded to each of two non-adjacent carbon atoms constituting a ring. The polyester resin according to claim 2, wherein a compound is used. 6. A bis (hydroxyalkyl) terephthalate or a bis (hydroxyalkyl) hexahydroterephthalate as the ring structure-containing divalent carboxylic acid compound.
The polyester resin according to claim 2, wherein 7. The alicyclic dihydric alcohol (B) is 2,2
The polyester resin according to claim 1, which is -bis (4-hydroxycyclohexyl) -propane. 8. A resin composition containing the polyester resin according to claim 1 and a colorant.