JP3164161B2 - Resin particles - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention is widely used as a matting agent, an anti-blocking material, a carrier for chromatography, a carrier for medicine, a powder coating, a gap adjusting material, a toner for electrophotography, a cosmetic and the like. The present invention relates to resin particles which have been used, and particularly to polyester resin particles which exhibit good light fastness when colored with a dye.

[0002]

2. Description of the Related Art Conventionally, resin particles produced by the "polymerization granulation method" can be exemplified as resin particles used in such applications. The polymerization granulation method can be roughly classified into an emulsion polymerization method, a suspension polymerization method, a seed polymerization method, and a dispersion polymerization method.

In the emulsion polymerization method, resin particles are obtained by performing polymerization in water in a micelle of a polymerizable monomer stabilized with a surfactant. In the emulsion polymerization method, particles having a sharp particle size distribution can be obtained. However, since the particle size is determined by the size of the micelles that can exist stably, the particle size is limited to a range of about 0.01 to 0.5 μm, and is about 1 μm.
It is impossible to obtain particles having a particle size of m or more. In addition, since a surfactant that is essential for stabilizing micelles remains on the surface of the prepared particles, the range of use of the obtained resin particles is limited.

The suspension polymerization method is a method in which particles are obtained by polymerizing a polymerizable monomer in a suspension system obtained by mechanically stirring water and a polymerizable monomer. In the suspension polymerization method, it is difficult to obtain fine polymer particles having a uniform particle size distribution because the size of the particles depends on mechanical stirring. The particle size range of the particles obtained by the suspension polymerization method is about 10 μm or more.

[0005] In the seed polymerization method, particles obtained by another method are used as seed particles, and the seed particles are swollen with a solvent and a polymerizable monomer. This is a method in which seed particles grow large by polymerization. In the seed polymerization method, in principle, by selecting appropriate seed particles, particles having a sharp particle size distribution can be obtained. -Controllable by the swelling ratio of the polymer particles and the polymerizable monomer. In the seed polymerization method, particles obtained by an emulsion polymerization method, that is, vinyl polymer particles are used for the seed. It is difficult to swell the vinyl polymer particles with the polymerizable monomer. The swelling ratio is determined by the balance between the interaction between the polymer constituting the seed particles and the monomer used for swelling, and the interfacial tension of the swollen particles. It will be a limit.
That is, the swelling ratio cannot be extremely increased, and there is naturally a limit to the particle size range in which the particles can be grown at once. Since increasing the particle diameter by 10 corresponds to increasing the volume by 1000 times, it is necessary to repeat seed polymerization in order to realize this by seed polymerization.

[0006] The two-stage swelling seed polymerization method is a method devised to increase the swelling ratio of seed particles. In the two-step swelling seed polymerization method, first, the seed particles are swelled with an oligomer or a low-molecular weight substance (swelling agent) that is hardly soluble in water, and then swelled with a polymerizable monomer. By this method, the swelling ratio of the seed particles can be increased up to several thousand times. However, since a swelling agent remains in the particles obtained by the two-step swelling seed polymerization method, a step of removing them is essential. Although the seed polymerization method and the two-step swelling seed polymerization method are excellent methods for producing micron-order resin particles having a sharp particle size distribution, the above problems are disadvantageous. This makes it difficult to industrially establish a depolymerization method.

The dispersion polymerization method comprises a polymerizable monomer, an initiator,
This method involves dissolving a stabilizer in an organic solvent and initiating polymerization to grow polymer particles that are insoluble in the organic solvent using the aggregates of the oligomer generated in the initial stage as particle nuclei. The dispersion polymerization method is an excellent method for producing micron-order resin particles having a sharp particle size distribution, but it is difficult to produce a mass product because an organic solvent is used as a medium. It cannot be established as a typical production method.

[0008]

As described above, the resin particles obtained by the emulsion polymerization method and the suspension polymerization method have a limited particle size range and a broad particle size distribution. . The resin particles obtained by the seed polymerization method and the dispersion polymerization method have a sharp particle size distribution, but are very expensive. Further, as described above, the "polymerization granulation method", that is, the resin particles produced by emulsion polymerization, suspension polymerization, seed polymerization, and dispersion polymerization are made of a vinyl polymer as apparent from the production method. Limited to resin particles.

In the case of coloring these vinyl polymer resin particles with a dye, the resin particles are formed by a predetermined operation after dissolving the dye in the vinyl monomer as a raw material. In this case, the dye is attacked by radicals when the vinyl monomer is polymerized, and many dyes cause discoloration. Further, the obtained colored particles are also inferior in light fastness and are liable to undergo discoloration and fading due to exposure to ultraviolet rays or the like. It is not surprising that a method of dyeing resin particles of a vinyl polymer in advance in an aqueous medium can be considered, but in this case, it is not only difficult to obtain resin particles colored at a high concentration, During the dyeing, aggregation and fusion of the particles occur, and it is difficult to obtain colored particles having an initial particle system and particle size distribution.

[0010]

In view of such circumstances, the present inventors have a sharp particle size distribution, have an arbitrary particle size, and are colored with a dye at high concentration and high light fastness. As a result of intensive studies to obtain possible resin particles, the following invention was reached. That is, the present invention relates to a polyester resin mainly obtained from a polyhydric carboxylic acid and a polyhydric alcohol, wherein terephthalic acid and / or its derivative (a) is 40 to 95 mol%, and isophthalic acid and / or its derivative (b) polycarboxylic acids and propylene glycol but containing aromatic polycarboxylic acid and or its derivatives sum is not less than 80 mol% of and a 5 to 60 mol% and its of (a) and (b), and or
2,3-butanediol and / or its derivative (c)
A polyester resin obtained from a polyhydric alcohol containing 20 to 100 mol% and containing an ionic group in a range of 20 to 500 (equivalent / 10 ⁶ g polymer) is used as a main component and has an average particle diameter D of 0.1 to 0.1 mol%. Resin particles having a particle size in the range of 2 to 50 μm and a particle size range of 0.5 D to 2.0 D containing 80% by weight or more of particles.

[0011]

The polycarboxylic acids in the present invention include an acid and an ester-forming derivative thereof, and will be represented by an acid below. The polycarboxylic acids of the present invention mainly consist of dicarboxylic acids. Examples of the dicarboxylic acids include terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6 naphthalenedicarboxylic acid, diphenic acid, diphenyl 4,4′-
Aromatic dicarboxylic acids such as dicarboxylic acids, aromatic carboxylic acids such as p-hydroxybenzoic acid, p- (hydroxyethoxy) benzoic acid, and the like can be used. As the aromatic polycarboxylic acid, 80 mol% or more of the polycarboxylic acid is essential, and more preferably 90 mol% or more should be used. In the present invention, the content of terephthalic acid is further essential in an amount of 40 to 95 mol%, preferably 60 to 90 mol%, and more preferably 70 to 85 mol%. Also, isophthalic acid 5
60 mol% is essential. When the amount of the aromatic polycarboxylic acid is less than the above range, the glass transition temperature of the polyester resin is lowered, which may hinder the storage stability of the resin particles. If the constituent ratio between terephthalic acid and isophthalic acid is not within this range, the polyester resin may be crystallized or amorphous more than necessary, and desired characteristics may not be obtained.

In the present invention, other dicarboxylic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid,
Aliphatic dicarboxylic acids such as dodecane dicarboxylic acid,
Unsaturated aliphatic and alicyclic dicarboxylic acids, such as luic acid, maleic acid, itaconic acid, hexahydrophthalic acid, and tetrahydrophthalic acid, can be used. In the present invention, if necessary, a small amount of tri- and tetracarboxylic acids such as trimellitic acid, trimesic acid, and pyromellitic acid may be contained.

[0014]-flops as polyhydric alcohol ethers in the present invention
Propylene glycol and / or 2,3-butanegio
It is essential that the content is 2 to 100 mol%.
Among them, propylene glycol is most preferred. Propyle
As a glycol component other than ethylene glycol and / or 2,3-butanediol, an aliphatic polyhydric alcohol such as ethylene glycol or an alicyclic polyhydric alcohol is preferably used, and ethylene glycol is more preferable.

Other polyhydric alcohol components include, for example, propylene glycol, 1,3-propanediol-
1,4-butanediol, 1,5-pentanedio-
1,6-hexanediol, neopentyl glyco-
, Diethylene glycol, dipropylene glycol,
2,2,4-trimethyl-1,3-pentaneddiol,
1,4-cyclohexanedimethanol, cyclohexanediol, tricyclodecandiodiol, tricyclodecanedimethanol, spiroglycol, 1,4-phenyleneglycol, paraxyleneglycol, dicyclohexyl 4,4 ′ diol, ethylene oxide adduct of 1,4-phenylene glycol, polyethylene glycol
Diols such as phenol, polypropylene glycol and polytetramethylene glycol, ethylene oxide adducts and propylene oxide adducts of bisphenol A, ethylene oxide adducts and propylene oxide adducts of hydrogenated bisphenol A Diols such as trimethylolethane, trimethylolpropane, glycerin, etc .; tetraols such as pentaerthritol; and lactones such as .epsilon. Lactone-based polyester polyols obtained by ring polymerization can be used.

In the present invention, the polyester resins can be used alone or in combination of two or more as required. Further, in a molten state or a solution state, it can be mixed with an amino resin, an epoxy resin isocyanate compound or the like, and further, it can be partially reacted with these compounds.

The polyester resin according to the present invention is a main component, the average particle diameter D is in the range of 0.2 μm to 50 μm, and the particle diameter range of 0.5D to 2.0D contains 80% by weight or more of the whole particles. As a method of obtaining the resin particles to be obtained, the polyester resin has micro-water dispersibility by previously containing an ionic group in the polyester resin, and the ionic group-containing polyester resin is micro-dispersed stably in an aqueous medium. After the microdispersed particles are plasticized, the amount of ions present on the surface and near the surface of the microdispersed particles is reduced under a uniformly controlled condition, whereby the microdispersed particles are stabilized in a medium. A method of obtaining polyester particles by breaking the state and combining the micro-dispersed particles can be exemplified. The ions present on the surface and near the surface of the micro-dispersed particles have a function of stabilizing the resin fine particles in the aqueous medium by forming an electric double layer near the surface of the micro-dispersed particles.

Means for reducing the amount of ions present on the surface of the micro-dispersed particles and in the vicinity of the surface are as follows: the ionic groups contained in the polyester resin are cut off by photolysis, thermal decomposition, hydrolysis, or the like; Means for controlling the degree of dissociation by scanning temperature, pH, etc .; blocking ionic groups by counter ions; and breaking the electric double layer by adding an electrolyte. In the present invention, a reactive monomer having a counterionic group is added into the system, and the ionic group is blocked using a polyion complex formed by polymerizing the monomer having a counterionic group. A method or a method of releasing an ionic group in combination with a decomposition catalyst or the like can be preferably used.

The ionic group contained in the resin includes a carboxyl group, a sulfonic acid group, a sulfate ester group, a phosphoric acid group, a phosphonic acid group, a phosphinic acid group, or a salt thereof (hydrogen salt, metal salt, ammonium salt). And a cationic group such as a primary to tertiary amine group, preferably a carboxyl group, an ammonium carboxylate group, a sulfonic acid group, or an alkali metal sulfonic acid group. Can be. These ionic groups are preferably contained in a form copolymerized with the resin. Examples of the sulfonic acid metal base-containing compound copolymerizable with the resin include sulfoterephthalic acid, 5-sulfoisophthalic acid, and 4-sulfophthalic acid. , 4-sulfonaphthalene-2,
Metal salts such as 7-dicarboxylic acid and 5 [4-sulfophenoxy] isophthalic acid can be given. In particular, when an ionic group is introduced into a polymer terminal, sulfobenzoic acid and a metal salt thereof can be used. L as a metal salt
Salts such as i, Na, K, Mg, Ca, Cu, Fe and the like can be mentioned, and particularly preferred is Na salt. The content of these ionic groups is 20 to 5 with respect to the polyester resin.
00 equivalent / 10 ⁶ g is essential, 50-200 equivalent / 1
0 ⁶ g is preferable. If the ionic group content is less than the lower limit, it may be difficult to microdisperse the polyester resin in an aqueous medium. If the upper limit is exceeded, the polyester resin may become water-soluble. In the case where the above-described method of removing an ionic group is used, the content of the ionic group in the obtained particles is smaller than the initial content of the polyester resin.

The characteristics of the resin particles of the present invention appear particularly when they are colored with a dye. As dyes that can be used, yellow-colored azo, nitro-based, quinoline-based, quinophthalone-based, and methine-based dyes, magenta-colored anthraquinone-based, azo-, and rhodamine-based dyes, and cyan-colored Is preferably an anthraquinone dye. As the form of the dye, it is preferable to use a disperse dye or an oil-soluble dye. These may be directly used in the form of a commercially available dye as a disperse dye for dyeing textiles, and those which are not available in such a form include a dye base (kink cake), a dispersant, and an aqueous dye. Medium and medium
A mixture obtained by mixing with a mill, a sand mill, a shaker, or the like, and then the cake of the dye is further pulverized and finely dispersed may be used. As the dispersant, a condensate of naphthalene sulfonate, polystyrene sulfonate, a copolymer of styrene sulfonate and acrylic acid, or the like can be used.

As the dye, "a dye insoluble in water at normal temperature"
It is preferable to use These are generally classified as disperse dyes or oil-soluble dyes. More specifically, C.I. I. Disperse Yellow 198 C.I. I. Disperse Yellow 42 C.I. I. Disperse Red 92 C.I. I. Disperse Violet 26 C.I. I. Disperse Violet 35 C.I. I. Disperse Blue 60 C.I. I. At least one dye selected from Disperse Blue 87 is preferably used. They are particularly excellent in light fastness, sublimation fastness, hue and saturation.

Example 1 (Synthesis 1 of polyester resin) In an autoclave equipped with a thermometer and a stirrer, 145.5 parts by weight of dimethyl terephthalate, 38.8 parts of dimethyl isophthalate Parts by weight, 5-sodium sulfoisophthalate methyl ester 4.0 parts by weight, trimellitic anhydride 5.8 parts by weight, ethylene glycol 68.2 parts by weight, propylene glycol 91.2 parts by weight tetrabutoxy 0.1 part by weight of titanate was charged and heated at 180 to 230 ° C. for 120 minutes to perform a transesterification reaction. Then, the temperature of the reaction system was raised to 240 ° C., and the reaction was continued at a system pressure of 1 to 10 mmHg for 60 minutes, thereby obtaining a copolymerized polyester resin (A1). The composition of the obtained copolymerized polyester resin (A1) was determined by NMR.
As a result of analysis, as an acid component, terephthalic acid 75 mol% isophthalic acid 20 mol% 5-sodium sulfoisophthalic acid 2 mol% trimellitic acid 3 mol
%, Ethylene glycol 50 mol% as an alcohol component, and propylene glycol 50 mol%. The glass transition temperature of (A1) was 63 ° C., and the amount of sodium sulfonate group was 84 equivalents / 10 ⁶ g. Hereinafter, polymerization is performed by changing the charge composition in the same manner, and the polyester resin (A
2) to (A4) were obtained. The results are shown in Table 1 below. Shown in

100 parts by weight of the copolymerized polyester resin (A1), 10 parts by weight of tetrahydrofuran, 50 parts by weight of methyl ethyl ketone and 15 parts by weight of isopropyl alcohol are dissolved at 80 ° C., and 200 parts of water at 80 ° C. are added. An aqueous microdispersion of a copolymerized polyester resin having a diameter of about 0.1 μm was obtained. Further, the obtained aqueous microdispersion was placed in a distillation flask and distilled until the fraction temperature reached 100 ° C. After cooling, water was added to adjust the solid content concentration to 30%.

In a four-necked 1-liter separable flask equipped with a thermometer, a condenser, and a stirring blade, 1000 parts by weight of the aqueous dispersion of the copolymerized polyester and 8.0 parts by weight of dimethylaminoethyl methacrylate were placed. Put, 80
C., and the reaction was continued while keeping at 80.degree. C. for 120 minutes. As a result, the copolymer having a submicron order particle size present in the copolymerized polyester aqueous dispersion grows as a united particle, and has an average particle size of 8.4 μm and a diameter of D to 0.5D to 2D. Polyester resin particles having a particle occupancy of 91 wt% were obtained. Water was added to the obtained polyester resin particles to obtain a 25% by weight aqueous dispersion of polyester resin particles (B1).

100 parts by weight of an aqueous dispersion of polyester particles (B1) obtained in a dyeing tester minicolor [Texam Giken], and a disperse dye Sumicalon Turquoise Blue SG
L (CI DISPERSE BLUE 60) [manufactured by Sumitomo Chemical], 10 parts by weight, and 130 ° C. at 3 ° C./min.
After heating at 130 ° C. for 60 minutes, the mixture was cooled with water to room temperature, washed, dehydrated, and vacuum-dried for 48 hours to obtain colored polyester particles (C1).

5 parts by weight of the obtained colored particles and 95 parts by weight of ferrite-based spherical particles F-100 (manufactured by Powder-Tech Co., Ltd.) having a diameter of about 70 μm are placed in a glass bottle and shaken about 200 times at a stroke of 30 cm. did. This operation confirmed that the colored particles were negatively charged by a foil voltage detector. White paper was fixed on an aluminum plate held at an angle of 45 degrees, and a voltage of about +1 kV was applied to the aluminum plate. Next, the mixture of the colored particles and the ferrite particles was sprinkled on white paper from the upper end side of the aluminum plate held diagonally.
The colored particles adhered to the white paper due to their electrostatic charge. Put the paper with the colored particles in a dry oven at 130 ° C.
The colored particles were melted and fixed on the paper by heating for minutes to obtain test pieces. The thickness of the particle layer on the paper was obtained by weight conversion, and the voltage was applied to an aluminum plate to adjust the voltage so that the thickness was standardized to about 10 microns.

The chromaticity coordinates of the obtained test piece were measured using a colorimeter C.
It was measured using R-210 (manufactured by Minolta). The results are shown in Table 2. Shown in It turns out that it has high saturation. Further, the obtained test piece was measured again after an ultraviolet exposure test (fade meter: irradiation of carbon arc lamp for 20 hours, irradiation environment temperature of 63 ° C.) to obtain a color difference ΔE. Table 2 shows the results. Shown in The results are shown by averaging N = 5 by rounding off decimal places. Hereinafter, similarly, the polyester resin (A
2) to (A4) from (A6) to (C2) to (C4) (C
6) and the results of evaluating the chromaticity coordinates and light fastness are shown in Table 2. I will show you.

Example 2 (Synthesis 2 of polyester resin) In an autoclave equipped with a thermometer and a stirrer, 145.5 parts by weight of dimethyl terephthalate, 38.8 parts of dimethyl isophthalate Parts by weight, 68.2 parts by weight of ethylene glycol, 91.2 parts by weight of propylene glycol and 0.1 part by weight of tetrabutoxy titanate, and heated at 150 to 220 ° C. for 180 minutes to carry out the transesterification reaction. went. Then, after heating to 240 ° C.,
The pressure of the system was gradually reduced to 10 mmHg after 30 minutes,
The reaction was continued for 60 minutes. Thereafter, the autoclave was replaced with nitrogen gas to bring the pressure to atmospheric pressure. While maintaining the temperature at 200 ° C., 10 parts by weight of trimellitic anhydride was added and the reaction was carried out for 60 minutes to obtain a copolymerized polyester resin (A5). As a result of NMR analysis of the obtained polyester resin (A5), terephthalic acid was 75 mol%, isophthalic acid was 20 mol%, trimellitic acid was 5 mol%, ethylene glycol was 100 mol%, and propylene glycol was 50 mol%. . The molecular weight of the copolymerized polyester resin (A5) was 4,100, the glass transition temperature was 60 ° C., and the carboxyl group value was 305 equivalents / 10 ⁶ g. 100 parts by weight of the copolymerized polyester resin (A5), 25 parts by weight of tetrahydrofuran, 50 parts by weight of methyl ethyl ketone, and 10 parts by weight of isopropyl alcohol are dissolved at 80 ° C., and 1N is added so as to be equivalent to the acid value of the copolymerized polyester. After stirring at 30 ° C. for 30 minutes at 80 ° C., 200 parts of water at 80 ° C. was added to obtain an aqueous dispersion of a copolymerized polyester. Further, sodium hydroxide was added to 1000 parts of the obtained water dispersion so as to be equivalent to ammonia, distilled until the fraction temperature reached 100 ° C., cooled, and finally the solid content concentration of the solvent removed was 33%. (B5) was obtained.

A part of the obtained aqueous dispersion was dried to measure a carboxyl group value of 3.8 equivalents / 10 ⁶ g. Most of the carboxyl groups were replaced with sodium carboxylate groups. In a four-necked 1-liter separable flask equipped with a thermometer, a condenser, and a stirring blade, 300 parts by weight of the aqueous dispersion of the copolymerized polyester (B5) and 15.0 parts by weight of dimethylaminoethyl methacrylate were placed. Then, the temperature was raised to 80 ° C., and the reaction was continued while keeping the temperature at 80 ° C. for 120 minutes. As a result, the particle diameter of the submicron order present in the polyester aqueous dispersion was united particle growth, and when the average particle diameter D was 9.1 μm and the diameter was D, the particle diameter was in the range of 0.5D to 2D. Polyester resin particles having an occupancy of 92 wt% of particles having the following formula: The obtained particles were washed, filtered, and then re-dispersed in water to obtain a solid content concentration of 25% by weight. Thereafter, the particles were colored in the same manner as in Example 1 to obtain colored polyester particles (C5). Table 2 shows the results of evaluating the chromaticity coordinates and light fastness. Shown in

Comparative Example 1 Condensed powder of disperse dye (CI Disperse Blue 60) containing 1% by weight of 2,2 'azobis (2,4 dimethylvaleronitrile).
Methyl methacrylate monomer-12 dissolved at 4% by weight
0 parts by weight was added to 880 parts by weight of deionized water and stirred for 20 minutes. Then, the temperature was raised to 70 ° C., and suspension polymerization was performed for 3 hours to obtain colored polymethyl methacrylate particles (C7). The obtained colored polymethyl methacrylate particles have an average particle diameter D of 18.7 μm and a diameter of D of 0.5 μm.
The occupancy (weight) of particles having a particle size in the range of D to 2D was 54% by weight. Table 2 below shows the results of evaluating the chromaticity coordinates in the same manner as in Example 1. Shown in The obtained color was low in both chroma and lightness, indicating that the dye had undergone discoloration during polymerization.

Example 3 Using the copolymerized polyester resin (A1) obtained in Example 1 as a dye: Sumicaron Brilliant Blue S-BL (CIDISPERSE BLUE 87) [Sumitomo Chemical] Sumicaron Brilliant・ Red F-BL (CIDISPERSE RED 60) [Mitsui Toatsu Dye] ・ Miketone ・ Polyester Red SE-BL (CIDISPERSE RED 92) [Mitsui Toatsu Dye] ・ Miketone ・ Polyester ・ Red Violet 4
RL (CIDISPERSE VIOLET 35) [Mitsui Toatsu Dye] ・ Sumicaron Bold-SE-BL (CIDISPERSE VIOLET 26) [Sumitomo Chemical] ・ Miketone Fast Yellow-GL (CIDISPERSE YELLOW 33) [Mitsui Toatsu Dye] Using Miketone / Polyester Yellow-5GF (CIDISPERSE YELLOW 198) [manufactured by Mitsui Toatsu Dyes Ltd.], a test piece was prepared in the same manner, and a test piece was prepared and subjected to an ultraviolet exposure test. The results are shown in Table 3 below. Shown in

Comparative Example 2 120 parts by weight of methyl methacrylate monomer in which 1% by weight of 2,2 ′ azobis (2,4 dimethylvaleronitrile) was dissolved was added to 880 parts by weight of deionized water, and the mixture was added for 20 minutes. Stirred. Then, the temperature was raised to 70 ° C. and suspension polymerization was carried out for 3 hours to obtain colored polymethyl methacrylate particles (C8). The obtained colored polymethyl methacrylate particles have an average particle diameter D of 18.6 μm, and when the diameter is D, the occupation ratio (weight) of the particles having a particle diameter in the range of 0.5D to 2D is 52% by weight. Met. Thereafter, a dyeing tester minicolor [Texam Giken] in the same manner as in Example 1.
100 parts by weight of an aqueous dispersion of the particles (C8) obtained in the above method, and a disperse dye Sumicalon Turquoise Blue-S-GL (C.I.
I. DISPERSE BLUE 60) [Sumitomo Chemical Co., Ltd.] 5 parts by weight were charged, the temperature was increased to 130 ° C. at 3 ° C./min, and the temperature was maintained at 130 ° C. for 60 minutes, followed by water cooling to room temperature. The resin particles (C8) were aggregated in the pot and melted and attached to the side wall of the pot, so that colored resin particles could not be obtained.

[0033]

As described above, the resin particles according to the present invention have excellent properties such as having a sharp particle size distribution, being capable of coloring a dye at a high concentration, and having good light fastness. Have

[0034]

[Table 1] Table 1. Medium, TPA is terephthalic acid, IPA is isophthalic acid, TMA is trimellitic acid, SIP is 5-sodium sulfoisophthalic acid, EG is ethylene glycol, PPG is propylene glycol, and BPE is propylene oxide of bisphenol A. Each adduct is shown.

[0035]

[Table 2]

[0036]

[Table 3]

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C08G 63/00-63/91 C08J 3/12-3/16

Claims (1)

(57) [Claims] 1. A polyester resin mainly obtained from a polycarboxylic acid and a polyhydric alcohol, wherein terephthalic acid and / or its derivative (a) is 40 to 95 m
ol%, isophthalic acid and / or its derivative (b)
Polycarboxylic acids and propylene but containing aromatic polycarboxylic acid and or its derivatives sum is not less than 80 mol% of and a 5 to 60 mol% and its of (a) and (b)
Lenglycol and / or 2,3-butanediol and / or a derivative thereof (c) obtained from a polyhydric alcohol containing 20 to 100 mol%,
(Equivalents / 10 ⁶ g polymer) in the range of a polyester resin containing an ionic group as a main component, an average particle diameter D in the range of 0.2 to 50 μm, and a particle diameter range of 0.5 D to 2.0 D. Resin particles containing 80% by weight or more of particles.