JP2003082079A - Polyester resin and binder composition containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyester resin almost free from aromatic components which may become environmental pollutants, having excellent fluidity participating in low-temperature fixability, and usable as a static charge image developing color toner having excellent storage stability and a binder resin of a powdered paint having excellent appearance (smoothness), weather resistance and blocking resistance. SOLUTION: An alkyl-substituted alicyclic dicarboxylic compound (A) in which a carboxlic group or a carboxylic acid derivative group is bonded on each of two carbon atoms constituting an alicycle and positioned side by side, an alicyclic dihydric alcohol (B) and a linear aliphatic dihydric alcohol (C) are subjected to polycondensation to obtain a polyester precursor resin having a number-average molecular weight of 1,500-5,000 and a glass transition temperature of >=50 deg.C, and free from aromatic groups. The polyester precursor is subjected to polycondensation with a polycarboxylic acid or a polyhydric alcohol to obtain the 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 resin capable of realizing electrophotographic toner, 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 binder resin, a colorant, a charge control agent, and the like are added and kneaded, and then pulverized and further classified. Particles produced by a so-called pulverization method are used. A styrene / acrylic copolymer resin has been mainly used as a binder resin for toner, but in recent years, a polyester resin excellent in low-temperature fixability and image surface gloss tends to be used due to higher speed and coloration. .

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.

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 coloring material, has a sharp melt property (= melts quickly) at a relatively low temperature, and 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. 8-512078 discloses a composition containing an amorphous polyester composed of cyclohexanedicarboxylic acid and alicyclic diol residues. However, it was not satisfactory as a paint in that the sharp melt property was not sufficient.

[0005]

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. Used as a binder resin that can realize color toner for electrostatic image development that has excellent fluidity and storage stability, and powder coating that has excellent appearance (smoothness) and weather resistance and blocking resistance. It is intended to provide a polyester resin. As a result of intensive studies, the present inventor has found that an alicyclic divalent carboxylic acid compound in which a carboxyl group or a carboxylic acid derivative group is bonded to each of two adjacent alicyclic carbon atoms and 2,2-bis The specific glass transition temperature obtained by polycondensing an alicyclic dihydric alcohol such as (4-hydroxycyclohexyl) -propane (that is, hydrogenated bisphenol A) and a chain aliphatic dihydric alcohol such as ethylene glycol A polyester resin obtained by further polycondensing a polyester precursor having a polycarboxylic acid and / or a polyhydric alcohol such as bis (hydroxyethyl) terephthalate or bis (hydroxyethyl) hexahydroterephthalate at low temperature Based on this finding, we found that it has excellent fluidity at This has led to the completion of the present invention.

[0006]

Thus, according to the present invention, (1) an alicyclic group in which a carboxyl group or a carboxylic acid derivative group is bonded to each of two adjacent carbon atoms forming an alicyclic ring Divalent carboxylic acid compound (A), alicyclic group 2
It is a polycondensation product of a polyhydric alcohol (B) and a chain aliphatic dihydric alcohol (C), and has a number average molecular weight of 1,500 to
It is a polycondensate of a polyester precursor having a glass transition temperature of 5,000 and a glass transition temperature of 50 ° C. or higher, and (2) a polyvalent carboxylic acid and / or a polyhydric alcohol (D), and having a number average molecular weight of 6, A polyester resin having a glass transition temperature of 000 to 30,000 and a glass transition temperature of 50 ° C. or higher is provided. Further, according to the present invention, a binder composition containing the above polyester resin and a curing agent is provided, and according to the present invention, a binder composition containing the above polyester resin and a colorant is provided.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The polyester resin of the present invention is
It is a polycondensate of (1) a specific polyester precursor and (2) a polyvalent carboxylic acid and / or a polyhydric alcohol.

The polyester precursor is a polycondensate of a specific polycarboxylic acid and a polyhydric alcohol. As a polyvalent carboxylic acid used for the polyester precursor, an alicyclic divalent carboxylic acid compound (A) in which a carboxyl group or a carboxylic acid derivative group is bonded to each of two adjacent carbon atoms forming an alicycle , Particularly preferably the general formula (1)
Alternatively, an alicyclic divalent carboxylic acid represented by (2) or an anhydride thereof having an alkyl group bonded to the alicyclic ring as a substituent is used.

[0009]

[Chemical 3]

[0010]

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

In the alicyclic divalent carboxylic acid compound (A) used in the present invention, a carboxyl group or a carboxylic acid derivative group (amide group, ester group, acid anhydride group, acid halide) constitutes an alicycle. , Bonded to each of two adjacent carbon atoms. Examples of the alkyl group include those having 1 to 8 carbon atoms, such as a methyl group, an ethyl group, a propyl group and an isopropyl 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 acid anhydride of the alicyclic divalent carboxylic acid is an acid anhydride group formed by dehydration of two carboxyl groups represented by the 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 with maleic anhydride, and hydrogenating if necessary. Specific examples of the alicyclic divalent carboxylic acid compound (A) include tetrahydrophthalic acid and 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-hexahydro Phthalic acid, 3-alkyl-3,6
-Endomethylene-hexahydrophthalic acid and their derivatives (anhydrides, esters, halides, amides, etc.) and the like. These are each
Alternatively, two or more kinds can be used in combination.
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%, and particularly preferably 80 to 100 mol% of the total carboxylic acid components constituting the precursor. If this ratio is low, sufficient fluidity may not be obtained.

If desired, other polyvalent carboxylic acids such as alicyclic dicarboxylic acids and aliphatic dicarboxylic acids may be copolymerized, but the proportion of the aliphatic dicarboxylic acids is 15 mol%.
The following are preferred. When this proportion 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. As the polyvalent carboxylic acid capable of copolymerization, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid,
1,3-cyclohexene dicarboxylic acid, 1,4-cyclohexene dicarboxylic acid; adipic acid, azelaic acid,
1,10-decanedicarboxylic acid, dimer acid; trimellitic acid, pyromellitic acid, trimesic acid and the like.

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 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 an amount of 40 to 80 mol% of the total polyhydric alcohol component and an alicyclic dihydric alcohol (B) in an amount of 20 to 60 mol%. There is something. 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, when the amount of the alicyclic dihydric alcohol (B) is too small, the glass transition temperature becomes low,
If the amount of the alicyclic dihydric alcohol is too large, 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 2,500 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 50 ° C. or higher, preferably 50 to 80.
℃. 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
It is of 60 mg KOH / 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.

In the polyester resin of the present invention, the polyvalent carboxylic acid and / or the polyhydric alcohol (D) is used for connecting the polyester precursors to each other so as to have a high molecular weight. The polyhydric carboxylic acid and / or polyhydric alcohol (D) used in the present invention is an alicyclic dicarboxylic acid, an aliphatic dicarboxylic acid, an aliphatic tricarboxylic acid, such as those listed for obtaining a polyester precursor; Examples thereof include cyclic diols, alicyclic triols, aliphatic diols and aliphatic triols. Preferable examples of polyvalent carboxylic acid and / or polyhydric alcohol (D) include terephthalic acid and hexahydrophthalic acid, which form a ring and have carboxyl groups or carboxylic acid derivatives at two non-adjacent carbon atoms. A divalent carboxylic acid compound having a ring structure and having a group bonded thereto. Particularly preferred are bis (hydroxyethyl) terephthalate or bis (hydroxyethyl) hexahydroterephthalate.
The amount of polyvalent carboxylic acid and / or polyhydric alcohol (D) used for connecting the polyester precursor is preferably 10 to 5 with respect to 100 parts by weight of the polyester precursor.
0 parts by weight, particularly preferably 20 to 40 parts by weight. When the amount of the polyvalent carboxylic acid and / or the polyhydric alcohol (D) 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 and polyvalent carboxylic acid and / or polyhydric alcohol (D)
It can be carried out by the same method as that used for producing the above precursor. That is, this polycondensation reaction may be carried out under reduced pressure by adding a polyester precursor and a polyvalent carboxylic acid and / or polyhydric alcohol (D) at the reaction temperature, optionally adding an esterification catalyst. Good. In addition, after carrying out a polycondensation reaction for synthesizing a polyester precursor, a polyvalent carboxylic acid and / or a polyhydric alcohol (D) is added to the reaction system to continuously carry out the polycondensation reaction. You can also

The polyester resin of the present invention can be used as it is as a binder resin 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,
The amount of the total resin is preferably 25% by weight or more, more preferably 33% by weight or more, particularly preferably 40% by weight or more, and most preferably 50% by weight or more. 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 binder composition of the present invention comprises the polyester resin of the present invention and a curing agent or colorant. The curing agent used in the binder composition of the present invention is not particularly limited, but an isocyanate curing agent is suitable. As an isocyanate-based curing agent,
A blocked isophorone diisocyanate-based curing agent and a blocked hydrogenated diphenylmethane diisocyanate-based curing agent that do not show activity at a certain temperature or lower are preferable, and specific examples include ε-caprolactam-blocked isophorone diisocyanate-based curing agent manufactured by Huls Ltd. "Vestagon B1530", an isophorone diisocyanate-based curing agent that does not contain a blocking agent and is self-blocking with isocyanate groups, "Vestagon BF1540"
”, Bayer's“ TPLS2147 ”, ε-caprolactam blocked hydrogenated diphenylmethane diisocyanate curing agent, McWHORTER's“ 24-243 ”.
0 ”and“ 24-2431 ”and the like. The amount of the curing agent is 0.5 to the hydroxyl value of the polyester resin.
It is suitable to use 1.5 times equivalent, preferably 1.0 times equivalent.

The colorant used in the binder composition of the present invention is a pigment or dye used for coloring. Dyes are preferable from the viewpoint of spectral transmission characteristics. When a pigment is used as a colorant, benzidine-based, azo-based, and isoindoline-based pigments are used for yellow coloring, and azo-based, rhodamine-based, quinacridone-based, naphthol-based, diketopyrrolopyrrole are used for magenta coloring. A phthalocyanine pigment and an indanthrene pigment are preferably used for cyan coloring. Carbon black is usually used to obtain a black toner. Carbon black includes thermal black, acetylene black, channel black,
Examples include furnace black and lamp black.
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, and anthraquinone-based, azo-based dyes are used for magenta coloring.
Xanthene dyes are preferably used for cyan coloring, and anthraquinone 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.

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

[0025]

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 G
It is calculated as a standard polystyrene conversion amount according to the PC method. [Hydroxyl value]: The hydroxyl value of polyester is 2,4,9,2-8 of "Standard oil and fat analysis test method" (Japan Oil Chemistry Association).
Measure according to the method described in Section 3. The unit in the table is mgKOH / g. [Softening point] & [Flow start temperature]: A Shimadzu flow tester (CFT-500C) was used to perform a temperature rise flow test under the following measurement conditions, and the softening temperature and flow start temperature were determined from the inflection point. The fluidity can be evaluated by the difference between the flow starting temperature and the softening point, and the smaller the difference, the better the fluidity. A material having good fluidity tends to have a low minimum fixing temperature when used as a toner. Die: 1.0 mmφ × 10 mm, heating rate: 6 ° C /
Min, load: 20 kg / cm ² , sample amount: 1.2
g, pellet preheating temperature: 40 ° C. The unit in the table is ° C. [Glass transition temperature]: The glass transition temperature (Tg) of the polyester resin is DSC defined in JISK 7121.
Measure according to the method. The unit in the table is ° C.

[Blocking resistance]: A powder having a height of 4 cm is put into a bottomed glass tube having a diameter of 3 cm and a height of 7 cm.
After leaving it in a constant temperature bath at 40 ° C. for 1 week, the glass tube was turned upside down to take out the powder, and the state of the powder was evaluated according to the following two stages. ◯: Almost no agglomeration of powder and almost no lump. Δ: The powder partially aggregates and there are some small lumps. X: There is a large lump in which powder is aggregated and solidified. [Smoothness]: The smoothness of the coating film was visually observed and evaluated in the following two stages. Good: The coating film has few irregularities and has good smoothness. X: The coating film has large unevenness and has poor smoothness. [Glossiness]: A 60-degree specular glossiness was determined according to JIS K 5400. [Weather resistance]: Using a WEL-6XS-HC-B / EC type sunshine weather meter (manufactured by Suga Test Instruments Co., Ltd.)
After irradiating the coating film with light for 1000 hours, the glossiness was measured. The ratio of the post-irradiation glossiness to the pre-irradiation glossiness was determined. (If this value is 80% or more, it passes.)

[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, 0.3 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 water dividing pipe and a nitrogen gas introducing pipe. ) -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 3 557 parts of hexahydroterephthalic acid was 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. , And 443 parts of ethylene glycol. Stirring was carried out while introducing nitrogen gas, and the reaction was carried out at 180 ° C. for 5 hours while removing water produced 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 A three-necked flask equipped with a stirrer, a thermometer, a reflux condenser, a water diversion tube, and a nitrogen gas inlet tube was used, and 850 parts of the polyester precursor A obtained in Synthesis Example 1 and the synthesis example 3 were obtained. 150 parts of bis (β-hydroxyethyl) hexahydroterephthalate was 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. 0.5 parts of iron acetylacetonate was added, the reaction temperature was raised to 220 ° C., the pressure in the flask was gradually reduced, and after 1.5 hours, the pressure was reduced to 5 mmHg or less, and the reaction was continued for another 5 hours. Got The resulting polyester resin C was a pale yellow transparent solid having the physical properties shown in Table 1.

Example 2 A three-necked flask equipped with a stirrer, a thermometer, a reflux condenser, a water diversion tube and a nitrogen gas inlet tube was used, and 800 parts of the polyester precursor B obtained in Synthesis Example 2 and the synthesis example 3 were obtained. 200 parts of bis (β-hydroxyethyl) hexahydroterephthalate was 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. 0.5 parts of iron acetylacetonate was added, the reaction temperature was raised to 220 ° C. and the pressure in the flask was gradually reduced to 1.5 mmHg or less after 1.5 hours,
The reaction was continued for further 5 hours to obtain polyester resin D. The resulting polyester resin D was a pale yellow transparent solid having the physical properties shown in Table 1.

Comparative Example 1 A 2-necked flask equipped with a stirrer, a thermometer, a reflux condenser, a water dividing pipe and a nitrogen gas introducing pipe was charged with 320 parts of 2,2-bis (4-hydroxycyclohexyl) -propane and 2,2.
-144 parts of dimethyl-1,3-propanediol, 11 parts of trimethylolpropane and 0.8 parts of dibutyltin oxide were charged. Heat to 180 ° C, then 1,
420 parts of 4-cyclohexanedicarboxylic acid were added.
Stir while introducing nitrogen gas, raise from 180 ° C to 230 ° C while removing water generated during the reaction,
The reaction was carried out for 8 hours. Then, 105 parts of 1,4-cyclohexanedicarboxylic acid was further added, and the reaction was continued at 230 ° C. for 6 hours to obtain a polyester resin E1. The polyester resin E1 thus obtained had the physical properties shown in Table 1.

[0033]

[Table 1]

[Preparation of powder coating] Polyester resin C,
In D or E1, a curing agent (“Vestagon B1530” manufactured by Huls), a dioctyltin maleate curing catalyst (“Stann OMF” manufactured by Sansha Machine Gosei Co., Ltd.), a butyl polyacrylate-based leveling agent (“Acronal 4F” manufactured by BASF). ), Benzoin and rutile type titanium dioxide pigment (“Taipec CR-90” manufactured by Ishihara Sangyo Co., Ltd.) were dry blended with a Henschel mixer (FM10B type manufactured by Mitsui Miike Seisakusho Co., Ltd.) according to the formulation shown in Table 2. Then
110 ° C using a kneader (PR-46 type manufactured by Buss)
It was melt-kneaded. After kneading well, cool, crush,
Finally, the powder coating was obtained by classification with a wire mesh having an opening of 106 μm (140 mesh). The obtained powder coating material was electrostatically coated on a zinc phosphate-treated steel plate to a film thickness of 50 to 60 μm, and baked under the conditions of 180 ° C. for 20 minutes. The evaluation results of the powder coating are shown in Table 2.

[0035]

[Table 2]

From the results of Tables 1 and 2, the alicyclic ring is constituted,
A specific polyester precursor obtained by using an alkyl group-substituted alicyclic divalent carboxylic acid compound or the like in which a carboxyl group or a carboxylic acid derivative group is bonded to each of two adjacent carbon atoms, and a polyvalent carboxylic acid And / or the powder coating using the polyester resin C or D obtained by polycondensing the polyhydric alcohol, the appearance (smoothness) of the coating film,
The coating film was excellent in weather resistance and blocking resistance.

[0037]

EFFECTS OF THE INVENTION The binder composition using the polyester resin of the present invention can be made into 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 suitably used for an object to be coated which is required to have a matting property. Especially wipers,
It is suitable for automobile parts such as aluminum wheels, guardrails, road equipment such as road signs, and outdoor building materials such as aluminum sashes. The binder composition using the polyester resin of the present invention can also be used in a toner for developing an electrostatic image, and is the minimum in a fixing device in which a heat-resistant film capable of power saving and quick start and a thermal head are combined. The interval between the fixing temperature and the offset generation temperature is wide, and good fixing characteristics are exhibited. Further, since it is not necessary to add a release agent or the like to the toner, and the surface smoothness and transparency of the fixed image are excellent, the reproducibility of the color image is excellent.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 2H005 AA01 CA06 CA08 CA30 EA03                       EA06                 4J029 AA03 AA07 AB01 AC02 AD01                       AD07 AE11 AE13 BA02 BA03                       BA05 BA07 BA08 BD03A                       BD04A BD07A BD10 CD03                       CD04 GA22 GA23 KC01 KE05                       KE15                 4J038 DD081 DD082 DG301 DG302                       KA03 KA08 LA02 MA02 MA12                       MA13 MA14 NA26

Claims (7)

[Claims] (1) An alicyclic divalent carboxylic acid compound (A), in which a carboxyl group or a carboxylic acid derivative group is bonded to each of two adjacent carbon atoms forming an alicyclic ring, Polyester precursor which is a polycondensation product of a dihydric alcohol (B) and a chain aliphatic dihydric alcohol (C), having a number average molecular weight of 1,500 to 5,000 and a glass transition temperature of 50 ° C. or higher. Body, and (2) polycarboxylic acid and / or polyhydric alcohol (D)
A polyester resin having a number average molecular weight of 6,000 to 30,000 and a glass transition temperature of 50 ° C. or higher. 2. 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.) 3. A polyvalent carboxylic acid and / or polyhydric alcohol (D) 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 1, wherein a carboxylic acid compound is used. 4. The polyester resin according to claim 1, wherein bis (hydroxyalkyl) terephthalate or bis (hydroxyalkyl) hexahydroterephthalate is used as the polycarboxylic acid and / or polyhydric alcohol (D). 5. The alicyclic dihydric alcohol (B) is 2,2
The polyester resin according to claim 1, which is -bis (4-hydroxycyclohexyl) -propane. 6. A binder composition containing the polyester resin according to claim 1 and a curing agent. 7. A binder composition containing the polyester resin according to claim 1 and a colorant.