JP3114814B2 - 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 rate cannot be extremely increased,
There is a natural limit to the particle size range that can be grown at once. To increase the particle diameter by a factor of 10 would require a volume of 1000
Since this corresponds to doubling, it is necessary to repeat the seed polymerization in order to realize this by the seed polymerization. The two-stage swelling seed polymerization method is a method devised to increase the swelling ratio of the seed particles. In the two-stage 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 to several thousand times. However, since a swelling agent remains in the particles obtained by the two-stage swelling seed polymerization method, a step of removing them is essential. The seed polymerization method and the two-step swelling seed polymerization method are the
Although it is an excellent method in the production of micron-order resin particles having a good particle size distribution, the above problems make it difficult to industrially establish a seed polymerization 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 provides 0.5 mol%
The polyester resin obtained by condensation of a polyvalent alcohol containing an alicyclic diol having a tricyclodecane skeleton in the range of 90 mol% or less and a polyvalent carboxylic acid is used as a main component and has an average particle diameter of not less than 90 mol%. The resin particles are characterized in that 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 total particles.

[0009] The polycarboxylic acid in the present invention mainly comprises dicarboxylic acids. As dicarboxylic acids,
For example, aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, and 1,5-naphthalic acid;
And aromatic oxycarboxylic acids such as -oxybenzoic acid and p- (hydroxyethoxy) benzoic acid. Aromatic dicarboxylic acid is a polycarboxylic acid component of 60
Preferably, it is used in an amount of at least 80 mol%, more preferably at least 80 mol%. When the content of the aromatic dicarboxylic acid is less than this range, the glass transition temperature of the resin decreases,
Storage stability may be affected. 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, sebacic acid, aliphatic dicarboxylic acids such as dodecanedicarboxylic acid, fumaric acid, maleic acid,
Unsaturated aliphatic and alicyclic dicarboxylic acids such as 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.

In the present invention, an alicyclic diol having a tricyclodecane skeleton is used as a polyvalent alcohol component. Examples of the alicyclic diol include compounds represented by the following formula 1, and derivatives thereof.

Embedded image Wherein R 1 and R 2 are a hydroxyl group and / or a hydroxyalkylene group having 1 to 8 carbon atoms and / or a group obtained by adding 1 to 10 mol of alkylene oxide to a hydroxyalkylene group having 1 to 4 carbon atoms. In the present invention, it is preferable to use tricyclodecane dimethylol in which R1 and R2 are both methylol groups. The alicyclic diol is essential in the range of 0.5 mol% to 90 mol% of the polyhydric alcohol component, and 5 mol% to 70 mol%.
mol% or less, preferably 10 mol% or more and 50 mol% or less.
% Is more preferable.

Other polyhydric alcohol components include, for example, ethylene glycol, propylene glycol,
3-propanediol, 1,4-butanediol, 1,
5-pentaneddiol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, 2,2,4-trimethyl-1,3-
Pentanediol, 1,4-cyclohexanedimethano-
, Spiroglycol, 1,4-phenylene glyco-
And ethylene oxide adducts of 1,4-phenylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, etc.
And diols such as ethylene oxide adduct and propylene oxide adduct of bisphenol A, ethylene oxide adduct and propylene oxide adduct of hydrogenated bisphenol A, and, if necessary, trimethylolethane and trimethylol. Lactone-based polyester polyols obtained by ring-opening polymerization of triols such as lupropane and glycerin, tetraols such as pentaerthritol, and lactones such as ε-caprolactone.
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, and has an average particle diameter D in the range of 0.2 μm to 50 μm. As a method for obtaining the contained resin particles, 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 stably micro-dispersed in an aqueous medium, Further, after the micro-dispersed particles are plasticized, the amount of ions present on the surface and near the surface of the micro-dispersed particles is reduced under a uniformly controlled condition, so that the micro-dispersed particles in the medium are reduced. An example of a method for obtaining polyester particles by breaking the stable state and uniting 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 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 group contained in the ionic group-containing polyester resin includes a carboxyl group, a sulfonic acid group, a sulfate group, a phosphoric acid group, and a salt thereof (hydrogen salt, metal salt, ammonium salt) and the like. 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. 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 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.

[0017]

Examples 1 to 4 and Comparative Example 1 The present invention will be described in more detail with reference to the following examples, but the present invention is not 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, 40 parts by weight of tricyclodecane dimethylol, 60 parts by weight of ethylene glycol Parts, neopentyl glycol 91 parts by weight, and tetrabutoxy titanate 0.1 part by weight (tricyclodecane dimethylol (TCD-alcoholDM manufactured by Hoechst) used in this example was 3,8-dimethylol and / or 4,9-dimethylol). ) As a main component) 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,
The reaction was continued for 60 minutes at a system pressure of 1 to 10 mmHg, and 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 below. Hereinafter, polymerization was carried out in the same manner by changing the raw materials and the composition, and the
Polyester resin shown in Example 1, Examples (A2) to (A4), Comparative Example 1
(A5) was obtained. In Table 1, TPA refers to terephthalic acid, IPA
Is isophthalic acid, SIP is 5-sodium sulfoisophthalic acid, SA is sebacic acid, MA is maleic acid, TCD is tricyclodecane dimethylol, EG is ethylene glycol, NPG is neopentyl glycol, BPE Represents an ethylene oxide adduct of bisphenol A, and BPP represents a propylene oxide adduct of bisphenol A.

(Production of resin particles) 100 parts by weight of a copolymerized polyester resin (A1) and 30 parts by weight of butyl cellosolve were dissolved at 110 ° C, and 200 parts of water at 80 ° C were added. An aqueous microdispersion of the polymerized polyester resin was obtained. Further, the obtained aqueous microdispersion was placed in a distillation flask, and distilled until the distillate temperature reached 100 ° C. After cooling, water was added to increase the solids concentration to 38%.
And A four-necked 1-liter separable flask equipped with a thermometer, a condenser, and a stirring blade was charged with 1000 parts by weight of the aqueous dispersion of the copolymerized polyester and 8.0 parts by weight of dimethylaminoethyl methacrylate. The temperature was raised to ° C. Next, after dropwise adding 150 parts by weight of an aqueous solution containing 0.2 parts by weight of ammonium persulfate over 60 minutes,
The reaction was continued for another 60 minutes at 80 ° C. As a result, the copolymer having a submicron-order particle size present in the copolymerized polyester aqueous dispersion grew into united particles, and when the average particle size was 5.2 μm and the diameter was D, 0.5% was obtained.
92% by weight of particles having a particle size in the range of D to 2D
To obtain polyester resin particles. Water was added to the obtained polyester resin particles to obtain a 25% by weight aqueous dispersion of polyester resin particles (B1). Hereinafter, polyester particle aqueous dispersions (B2) to (B5) were obtained from the copolymerized polyester resins (A2) to (A5) in the same manner.

(Dyeing) Aqueous dispersion of polyester particles (B1) 1 obtained by Dyeing Tester Minicolor [Texam Giken]
00 parts by weight, disperse dye Sumicaron Turquoise Blue
S-GL (CI DISPERSE BLUE 6
0) [Sumitomo Chemical] 10 parts by weight were charged, the temperature was raised to 130 ° C. at 3 ° C./min, and the temperature was maintained at 130 ° C. for 60 minutes, then water-cooled to room temperature, washed, dehydrated, and then vacuum dried for 48 hours. Then, colored polyester particles (C1) were obtained. Hereinafter, colored particles (C2) to (C5) were obtained from the polyester particle aqueous dispersions (B2) to (B5) in the same manner.

(Evaluation of light fastness) 5 parts by weight of the obtained colored particles and ferrite spherical particles F-
95 parts by weight (100 manufactured by Powder-Tech Co., Ltd.) were placed in a glass bottle and shaken about 200 times with a stroke of 30 cm. 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. The paper to which the colored particles were adhered was placed in a 130 ° C. dry oven and heated for 5 minutes to fuse and fix the colored particles to the paper 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-210 (manufactured by Minolta Co., Ltd.), and an ultraviolet ray exposure test (fade meter: irradiation with carbon arc lamp for 20 hours) After the irradiation environment temperature (63 ° C.), the color difference ΔE was determined by measuring again. The results are shown in Table 2. Shown in The result is N =
The average value of 5 was rounded off to the decimal point and displayed.

[0021]

Comparative Example 2 MA / BPP resin particles (A6) 70 parts by weight of a propylene oxide adduct of bisphenol A and 19.6 parts by weight of maleic anhydride in an autoclave equipped with a thermometer and a stirrer. , 0.2 parts by weight of hydroquinone, nitrogen gas was introduced into the reaction system to maintain an inert atmosphere, 0.05 parts by weight of dibutyltin oxide was added, and the mixture was reacted at 200 ° C. to obtain a polyester resin (A6). . Table 1. Composition and number average molecular weight of polyester resin (A6) Shown in 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 dispersant Mignol 802 [manufactured by Yatsusha Yushi Kogyo Co., Ltd.], and 0.1 part by weight of sodium rarylbenzenesulfonate
The resin powder was put into 0 parts by weight of deionized water, and an aqueous dispersion of a resin powder was obtained by 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. Table 2 shows the results. Shown in

[0022]

Example 5 Using the copolyester 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. Table 3 shows the results. Shown in

[0023]

[Table 1]

[0024]

[Table 2]

[0025]

[Table 3]

[0026]

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

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C08G 63/00-63/91 CA (STN) REGISTRY (STN)

Claims (1)

(57) [Claims] 1. A polyester resin obtained by condensation of a polyvalent alcohol containing an alicyclic diol having a tricyclodecane skeleton in the range of 0.5 mol% to 90 mol% with a polycarboxylic acid. Is a main component, and the average particle diameter D is in the range of 0.2 μm to 50 μm.
Resin particles characterized in that the particle diameter range of 5D to 2.0D contains particles of 80% by weight or more of the whole.