JP3149885B2 - 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. 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.

[0006] 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.

[0007]

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. When 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,
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-based polymer previously formed into particles in an aqueous medium is not conceivable, 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.

[0008]

SUMMARY OF THE INVENTION In view of such circumstances, the present inventors have a sharp particle size distribution, have an arbitrary particle size, and have a high concentration of dye and high light fastness. As a result of intensive studies to obtain colorable resin particles, the following invention was reached. That is, the present invention mainly relates to a polyester resin obtained by condensation of a polyvalent alcohol containing an alicyclic diol having a cyclohexane skeleton and a polyvalent carboxylic acid in a range of 0.5 mol% to 90 mol%. As a component, the average particle diameter D is 0.2 μm to 50 μm.
m, and a particle diameter range of 0.5D to 2.0D contains 80% by weight or more of the entirety of the resin particles.

[0009] The polycarboxylic acid in the present invention mainly comprises dicarboxylic acids. As dicarboxylic acids,
For example, terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6 naphthalenedicarboxylic acid, diphenic acid, aromatic dicarboxylic acids such as diphenyl 4,4′-dicarboxylic acid, p-oxybenzoic acid, Aromatic oxycarboxylic acids such as p- (hydroxyethoxy) benzoic acid and the like can be used. The aromatic dicarboxylic acid is preferably used in an amount of at least 60 mol% of the polycarboxylic acid component, more preferably at least 80 mol%. If the content of the aromatic dicarboxylic acid is less than this range, the glass transition temperature of the resin may decrease, which may hinder the storage stability. The dicarboxylic acids preferably used in the present invention are terephthalic acid and isophthalic acid. These are preferably used in an amount of 80 mol% or more of the aromatic dicarboxylic acid. In the present invention, other dicarboxylic acids such as succinic acid, adipic acid, azelaic acid,
Uses aliphatic dicarboxylic acids such as sebacic acid and dodecane dicarboxylic acid, unsaturated aliphatic such as fumaric acid, maleic acid, itaconic acid, hexahydrophthalic acid, tetrahydrophthalic acid, and alicyclic dicarboxylic acids. can do. 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.

In the present invention, an alicyclic diol having a cyclohexane skeleton is used as the polyvalent alcohol component. Examples of the alicyclic diol include: cyclohexanediol, cyclohexanedimethanol, hydrogenated bisphenol A and / or a derivative thereof, and hydrogenated biphenol and / or a derivative thereof. . The alicyclic diol is essential in the range of 0.5 mol% to 90 mol% of the polyhydric alcohol component, preferably in the range of 5 mol% to 70 mol%,
The range is more preferably from 10 mol% to 50 mol%.

Other polyhydric alcohol components include, for example, ethylene glycol, propylene glycol,
3-propanediol, 1,4-butanediol, 2,
3-butanediol, 1,5-pentanediole, 1,6
Hexanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, 2,2,4
Trimethyl-1,3-pentaneditol, spiroglycol, 1,4-phenylene glycol, ethylene oxide adduct of 1,4-phenylene glycol, polyethylene glycol, polypropylene glycol, polytetra Diols such as methylene glycol and the like, bisphenol A ethylene oxide adducts and propylene oxide adducts and the like, and if necessary, trimethylol triethane such as trimethylolethane, trimethylolpropane and glycerin; Lactone-based polyester polyols obtained by ring-opening polymerization of lactones such as ε-caprolactone and the like in addition to tetraols such as pentaerthritol
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 of the present invention is used as a main component, and has an average particle diameter D of 0.2 μm to 50 μm, and a particle diameter of 0.5 D to 2.0 D 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. The average particle diameter and the particle diameter range of the resin particles of the present invention are as described above, and the sphericity (the ratio of the minor axis to the major axis of the particles) is 0.9.
The above particles are 80% by weight or more of all the particles.

Means for reducing the amount of ions present on the surface of the micro-dispersed particles and in the vicinity of the surface include: cutting off ionic groups contained in the polyester resin 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 groups contained in the resin include 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). 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. it can. 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
Examples include salts of i, Na, K, Mg, Ca, Cu, Fe and the like, and particularly preferred is a Na salt. The content of these ionic groups is preferably from 0.005 to 0.2 equivalents / 1000 g, more preferably from 0.01 to 0.15 equivalents / 1000 g, and still more preferably from 0.02 to 0 g, based on the polyester resin. .1 equivalent / 1000 g. 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 colored by 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 dye, "a dye insoluble in water at ordinary temperature" is preferably used. 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. These are particularly excellent in light fastness, sublimation fastness, hue and saturation, and are preferable as three primary colors for process colors. 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. The medium may be mixed with a ball mill, a sand mill, a shaker, or the like, and a condensed cake of the dye may be further finely pulverized and finely dispersed. As the dispersant, a condensate of naphthalene sulfonate, polystyrene sulfonate, a copolymer of styrene sulfonate and acrylic acid, or the like can be used.

[0017]

EXAMPLES Examples 1 to 8 The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto. In an autoclave equipped with a thermometer and a stirrer, 95 parts by weight of dimethyl terephthalate, 95 parts by weight of dimethyl isophthalate, 6 parts by weight of 5-sodium sulfodimethyl isophthalate, ethylene glycol 60 parts by weight of toluene and 0.1 parts by weight of tetrabutoxy titanate were charged and heated at 180 to 230 ° C. for 120 minutes to carry out a transesterification reaction. Then, the temperature of the reaction system was raised to 250 ° C., and the reaction was continued at a system pressure of 1 to 10 mmHg for 60 minutes. As a result, a copolymerized polyester resin (A1) was obtained. The composition and number average molecular weight of the obtained copolymerized polyester resin (A1) are shown in Table 1. Shown in Hereinafter, polymerization was carried out in the same manner by changing the raw materials and the composition. Polyester resin,
Examples (A2) to (A8) were obtained.

After dissolving 100 parts by weight of the copolymerized polyester resin (A1) and 30 parts by weight of butyl cellosolve at 110 ° C., 200 parts of water at 80 ° C. are added, and the particle size is about 0.1 μm.
m was obtained as an aqueous microdispersion of a copolymerized polyester resin. Further, the obtained aqueous microdispersion was placed in a distillation flask, and distilled until the fraction temperature reached 100 ° C., and after cooling, water was added to adjust the solid concentration to 38%. In a four-necked 1-liter separable flask equipped with a thermometer, a condenser, and a stirring blade, an aqueous dispersion of the copolymerized polyester 100 was placed.
0 parts by weight and dimethylaminoethyl methacrylate
8.0 parts by weight, and heated to 80 ° C. Further 60
The reaction was continued while being kept at 80 ° C. for 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 5.2 μm and a diameter of D to 0.5D to 2D. Polyester resin particles having an occupation ratio of 92 wt% of particles having the following particle size were obtained. Water was added to the obtained polyester resin particles to obtain a 25% by weight aqueous dispersion of polyester resin particles (B1). Hereinafter, in the same manner, the copolymerized polyester resins (A2) to (A8) were used in Table 2. (B2) to (B8).

100 parts by weight of an aqueous dispersion of polyester particles (B1) obtained in a dyeing tester minicolor [Texam Giken], disperse dye Sumikaron Turquoise Blue SG
L (CI DISPERSE BLUE 60) [manufactured by Sumitomo Chemical], 10 parts by weight, and 130 at 3 ° C./min.
After raising the temperature to 130 ° C. and maintaining the temperature at 130 ° C. for 60 minutes, the mixture was cooled with water to room temperature, washed, dehydrated, and then dried under vacuum for 48 hours to obtain colored polyester particles (C1). Similarly, the colored particles (C) were obtained from the aqueous dispersions of polyester particles (B2) to (B8) in the same manner.
2) to (C8) were obtained. The average particle diameter D and the particle size distribution of the colored particles did not change significantly before coloring.

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 determined by weight conversion, and the applied voltage to the aluminum plate was adjusted to standardize the thickness to about 5 microns. The chromaticity coordinates (CIELAB) of the obtained test piece were measured using a colorimeter CR-21.
0 [manufactured by Minolta Co., Ltd.], and an ultraviolet exposure test (fade meter: irradiation with carbon arc lamp for 20 hours, irradiation environment temperature of 63 ° C.) was carried out again to obtain a color difference ΔE. The results are shown in Table 3 below. Shown in The results are shown by averaging N = 5 by rounding off to two decimal places.

Similarly, as the dye, Sumicaron Brilliant Blue S-BL (CIDISPERSE BLUE 87) [manufactured by Sumitomo Chemical] Sumicaron Brilliant Red F-BL (CIDISPERSE RED 60) [manufactured by Mitsui Toatsu Dye]・ 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. Table 3 shows the results. Shown in

[0022]

Comparative Example 1 One part by weight of 2,2 ′ azobis (2,4 dimethylvaleronitrile) was used, and the disperse dye Sumicaron Turquoise Blue S-GL Conc Powder (C.I. DIS)
PERSE BLUE 60) [Sumitomo Chemical] 4 parts by weight were dissolved in 50 parts by weight of methyl methacrylate monomer and 50 parts by weight of styrene monomer. 900 parts by weight of deionized water and the obtained mixture 1 were placed in a four-necked 1-liter separable flask equipped with a thermometer, a condenser, and a stirring blade.
Add 100 parts by weight and raise the temperature to 60 ° C while stirring vigorously.
After polymerization for a period of time, the colored polymethyl methacrylate (A
The particles of 9) were obtained. The obtained particles have an average particle diameter D of 11
The occupancy (weight) of the particles having a particle diameter in the range of 0.5D to 2D was 53% by weight. The obtained colored particles were fixed on paper by the same method as in the example, and an ultraviolet exposure test was performed. The results are shown in Table 4 below. Shown in Although the film thickness was normalized to the same film thickness, the color tone became dark and dull in the initial state, and it was presumed that discoloration and fading of the dye occurred during the graining process. The results of the UV exposure test were not good either.

[0023]

Comparative Example 2 Bisphenol A propylene oxide adduct 7 was placed in an autoclave equipped with a thermometer and a stirrer.
0 parts by weight, 19.6 parts by weight of maleic anhydride and 0.2 parts by weight of hydroquinone were charged, nitrogen gas was introduced into the reaction system, and the reaction system was maintained in an inert atmosphere. To give a polyester resin (A10). The obtained polyester resin was finely pulverized with a freezer mill to an average particle size of 8 μm. 38 parts of 100 parts by weight of the obtained resin powder, 10 parts by weight of Tamol-based dispersant Mignol 802 (manufactured by Yatsusha Yushi Kogyo KK), and 0.1 part by weight of sodium rarylbenzenesulfonate
An aqueous dispersion of the resin powder was obtained by putting the mixture in 0 parts by weight of deionized water and using an ultrasonic cleaner and a stirrer together. The aqueous dispersion of the obtained resin particles was dyed in the same manner as in the examples. The resin particles after dyeing re-agglomerated under heating to form a resin mass. The obtained colored resin mass was reground by a freezer mill, applied on white paper in the same manner as in the example, and subjected to an ultraviolet exposure test. The obtained colored particles were fixed on paper in the same manner as in the example, but the color tone was dark and dull even though it was normalized to the same film thickness, and the discoloration of the dye occurred during the dyeing process. It was speculated that

[0024]

As described above, the resin particles according to the present invention have good light fastness when dyed.

[0025]

[Table 1] Table 1. , TPA is terephthalic acid, IPA is isophthalic acid, SIP is 5-sodium sulfoisophthalic acid, EG is ethylene glycol, PPG is propylene glycol, CHD is cyclohexanediol, CHDM
Is cyclohexane dimethanol, HBP is hydrogenated bisphenol A, and DCD is dicyclohexyldiol (4,
4′-) are shown.

[0026]

[Table 2]

[0027]

[Table 3]

[0028]

[Table 4]

──────────────────────────────────────────────────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 obtained by condensation of a polyvalent alcohol containing an alicyclic diol having a cyclohexane skeleton and a polycarboxylic acid in a range of 0.5 mol% or more and 90 mol% or less. As a constituent, the average particle diameter D is in the range of 0.2 μm to 50 μm, and 0.5D
Resin particles characterized by containing particles of not less than 80% by weight in the particle diameter range of from 2.0 to 2.0D.