JP5350856B2 - Fluorene-containing polyester resin particles and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide fluorene-containing polyester-based resin particles having nanometer sizes and method for producing the resin particles. <P>SOLUTION: The resin particles includes a fluorene-containing polyester-based resin having a 9,9-bisarylfluorene skeleton and have a number-average particle diameters of a nanometer size. The resin particles can be produced by bringing the resin fluorene-containing polyester-based resin (A) and a resin solution containing a solvent (B) soluble in the resin fluorene-containing polyester-based resin (A) into contact with a solvent (C) which is a poor solvent for the component (A) and is miscible in the solvent (B) to deposit the resin fluorene-containing polyester-based resin (A) in particle form while making the resin solution fine. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to nanometer-sized resin particles composed of a fluorene-containing polyester resin containing a 9,9-bisarylfluorene skeleton and a method for producing the same.

  The resin particles can be used, for example, as various materials or members (for example, additives), and are used in plastic products, rubber products, cosmetics, foods, pharmaceuticals, adhesives, paints (or coating agents), electronic fields, optical fields, etc. Widely used in a wide range of fields to improve product characteristics and value. In particular, in the electronic field and the optical field, miniaturization and homogenization of resin particles (or reduction in particle size variation) are desired as members become more precise and have higher functions, and further, such as heat resistance and transparency. Resin particles having optical properties are desired.

  Methods for producing these resin particles are roughly classified into (1) gas phase method, (2) liquid phase method, and (3) solid phase method. Note that these three methods are further divided into chemical methods and physical methods.

  (1) In the vapor phase method, generally, a method of spraying a resin (or monomer) solution under heating to make it fine is widely used. However, in this method, since the generated particles are at a high temperature, there is a possibility that the particles are deformed or the particles are aggregated (or aggregated), and it is difficult to produce uniform resin particles. In addition, large-scale equipment is required, and manufacturing conditions (such as spraying conditions) must be strictly controlled, resulting in poor productivity.

  (2) Regarding the liquid phase method, for example, JP-A-6-206950 (Patent Document 1) discloses (meth) acrylic acid esters of alcohols having 1 to 14 carbon atoms and 1 to 14 carbon atoms. Latex based on one or more from the group consisting of vinyl esters of saturated aliphatic carboxylic acids, olefins, vinyl aromatics, vinyl halides and / or vinyl ethers is polymerized in the first step and the resulting latex weight Disclosed is a method for producing a graft copolymer latex of core / shell dispersed particles having an improved phase bond between the core and shell in a two-step emulsion polymerization process in which the coalescence is grafted in the second step. In the example of this document, core / shell dispersed particles having an average particle diameter of nanometer size (for example, core / shell dispersed particles having an average particle diameter of 192 nm in Example 2) are obtained. However, the production method described in this document cannot be applied to monomers and polycondensation polymers that exhibit other polymerization forms such as polycondensation because the polymerization reaction is performed in an aqueous solvent and the polymerization proceeds by a radical reaction. Further, the core / shell dispersed particles described in this document are inferior in heat resistance, optical properties (transparency, etc.) and the like.

  Furthermore, the (2) liquid phase method includes a coprecipitation method, a uniform precipitation method, and the like in addition to the method using emulsion polymerization described in Patent Document 1. In such a production method, the particle size of resin particles It is difficult to control the diameter, and the generated resin particles may aggregate (or aggregate). In addition, the surfactant and the flocculant necessary for the polymerization reaction are likely to remain in the resin particles, so that separation and purification are difficult, and use may be restricted depending on the application, which is not practical. Furthermore, the generated fine particles tend to have non-uniform particle diameters and are inferior in surface smoothness.

  (3) Regarding the solid phase method, a typical solid phase method includes a pulverization method. For example, JP-T-2002-506890 (Patent Document 2) discloses a method for removing harmful surface substances from pulverized regenerated polymer particles (polymer particles obtained by pulverizing a polymer to be recycled). Yes. The ground recycled polymer particles described in this document are produced by any suitable grinding operation, and the average particle size of the ground recycled polymer particles is about 1/4 inch to about 3/4 inch, about 3 / 8 inches to about 5/8 inches are described as preferred. However, since the pulverized regenerated polymer particles described in this document have a large particle size, their use in precision members may be limited. Japanese Patent Application Laid-Open No. 2004-130305 (Patent Document 3) discloses a high-speed powder reactor in which the powder is formed into fine particles by rotating a processing container containing a plurality of grinding media balls and powder. And a high-speed powder reactor that pulverizes the powder on the inner wall surface of the processing container to give the powder the kinetic energy of the grinding medium ball to make the powder fine particles. It is disclosed. This document describes that various powders such as organic substances, plastics, inorganic substances, and metals can be used as the powders. For example, in the embodiment, about 40 nm of aluminum (or nickel) powder is applied to the high-speed powder reactor, so that the particle size is about 20 nm.

  However, when the resin particles are produced by a pulverization (mechanical pulverization) method, there is a limit to miniaturization of the particle size, and it is difficult to produce resin particles having a smooth surface and a uniform surface. The pulverization (mechanical pulverization) method generates heat at the time of pulverization, and therefore can be applied relatively easily to resins having a high Tg (glass transition temperature), resins having a crosslinked structure, etc., but having a low Tg. When resin, high molecular weight resin, heat-labile resin, etc. are made into fine particles, the generated fine particles may be agglomerated with each other, or the fine particles may adhere to the pulverizer, so that the practicality is low. .

  As a resin constituting the resin particles, a polyester resin having a fluorene skeleton has been known so far, but the polyester resin is a condensation resin and has a bulky skeleton. In this method, it is difficult to produce nanometer-sized resin particles having a smooth surface and a uniform surface.

JP-A-6-206950 (Claims, Examples) Japanese translation of PCT publication No. 2002-506890 (claims, paragraph [0012]) JP 2004-130305 A (claims, paragraph [0015], examples)

  Accordingly, an object of the present invention is to provide nanometer-sized fluorene-containing polyester resin particles and a method for producing the same.

  Another object of the present invention is to provide a fluorene-containing polyester resin particle having a high refractive index and excellent heat resistance and transparency, and a method for producing the same.

  Still another object of the present invention is to provide a fluorene-containing polyester resin particle having a small variation in particle diameter and a method for producing the same.

  Another object of the present invention is to provide a fluorene-containing polyester resin particle that can be easily produced industrially and can form nanometer-sized particles even with a fluorene-containing polyester resin (condensation resin), and a method for producing the same. There is.

  As a result of intensive investigations to achieve the above-mentioned problems, the present inventors have refined a resin solution containing a specific fluorene-containing polyester resin under specific conditions. As a result, novel nanometer-sized fluorene-containing polyester resin particles are obtained. The present invention has been completed by finding out that it can be obtained.

  That is, the resin particles of the present invention are resin particles composed of a fluorene-containing polyester resin containing a 9,9-bisarylfluorene skeleton, and the number average particle diameter is nanometer size.

The number average particle diameter may be about 1 to 500 nm (for example, 40 to 500 nm), and the coefficient of variation of the number average particle diameter may be 35% or less. In the present invention, in particular, the number average particle diameter may be 50 nm or less (for example, 1 to 30 nm).
The fluorene-containing polyester resin has the following formula (1):

(In the formula, Z ¹ and Z ² are the same or different and each represents an aromatic hydrocarbon group. R ^1a and R ^1b represent the same or different alkylene group, and R ^2a and R ^2b represent the same or different hydrocarbon. Group, alkoxy group, cycloalkoxy group, aryloxy group, aralkyloxy group, acyl group, alkoxycarbonyl group, halogen atom, nitro group, cyano group or substituted amino group, R ^3a and R ^3b are the same or different and carbonized A hydrogen group, an alkoxy group, a halogen atom, a nitro group, a cyano group or a substituted amino group, wherein m and n are the same or different and are 0 or an integer of 1 or more, and h1 and h2 are the same or different and represent 0-4. An integer, j1 and j2 are the same or different and are integers of 0 to 4)
The polyester-type resin which uses the diol component containing the compound represented by these and a dicarboxylic acid component at least as a polymerization component may be sufficient. The weight average molecular weight of the fluorene-containing polyester resin may be about 20,000 to 45,000.

  In the present invention, a resin solution containing a fluorene-containing polyester resin (A) containing a 9,9-bisarylfluorene skeleton, and a solvent (B) capable of dissolving the fluorene-containing polyester resin (A), A resin (C) that is a poor solvent for the fluorene-containing polyester resin (A) and that is miscible with (or compatible with) the solvent (B) is brought into contact with each other to refine the resin solution and produce the resin particles. The method of doing is also included.

  In such a method, the resin solution may be further contacted with a solvent (D) (sometimes referred to as an intermediate solvent or a third solvent) different from the solvent (B) and the solvent (C). Such solvent (D) may be, for example, at least one solvent selected from aliphatic ketones and carboxylic acid alkyl esters. The solvent (D) is often a solvent that exhibits intermediate solubility between the solvent (B) and the solvent (C) with respect to the resin (A). In an embodiment using such a solvent (D), typically, the mixed solution containing the resin solution and the solvent (D) may be brought into contact with the solvent (C). When such a solvent (D) is used, the recovery efficiency of resin particles can be improved efficiently.

  In the method, for example, the resin solution and the solvent (C) are mixed and contacted with stirring (for example, the other of the resin solution and the solvent (C) is dropped into contact with the other). In particular, the solvent (C) may be mixed (for example, dropped) with stirring into the resin solution. When the solvent (C) is mixed with the resin solution, the particle diameter of the resin particles can be further reduced. In addition, in such a method, the said solvent (D) can be used conveniently. For example, in this method, a mixed solution containing a resin solution (a solution containing the resin (A) and the solvent (B)) and the solvent (D) may be used as the resin solution.

  In the method, the solvent (C) may be sprayed (or sprayed) on the resin solution. In particular, the solvent (C) may be sprayed at a spray rate of 100 to 10,000 mL / min with respect to the resin solution flowing at a flow rate of 1 mL / min.

  In the present invention, nanometer-sized resin particles can be formed in spite of using a condensation resin having a bulky skeleton such as fluorene. Moreover, since the said resin fine particle is comprised with specific resin, it is high refractive index, and is excellent also in heat resistance and transparency. Furthermore, the resin fine particles have small particle size variations and good particle size uniformity. Such resin particles can be easily manufactured industrially because the resin solution only needs to be refined under specific conditions.

FIG. 1 is a partially cutaway schematic cross-sectional view showing an example of the resin particle production apparatus of the present invention. FIG. 2 is a photomicrograph of the resin particles obtained in Example 1. FIG. 3 is a photomicrograph of the resin particles obtained in Example 2. FIG. 4 is a micrograph (10,000 times) of the resin particles obtained in Example 3. FIG. 5 is an enlarged photograph (50000 times) of the micrograph of FIG. FIG. 6 is a micrograph (10,000 times) of the resin particles obtained in Example 4. FIG. 7 is an enlarged photograph (50000 times) of the micrograph of FIG.

  Hereinafter, the present invention will be described in detail with reference to the accompanying drawings as necessary.

[Resin particles]
The resin particle of the present invention is composed of a fluorene-containing polyester resin containing a 9,9-bisarylfluorene skeleton. The fluorene-containing polyester resin may be a polyester-based resin having a dicarboxylic acid component containing a 9,9-bis (carboxyaryl) fluorene skeleton and a diol component as polymerization components. The resin is a polyester resin having a diol component containing a 9,9-bis (hydroxyaryl) fluorene skeleton and a dicarboxylic acid component as polymerization components. Such a fluorene-containing polyester-based resin includes, for example, at least a diol component represented by the formula (1) [a diol component containing at least a compound represented by the formula (1) (diol component)], and a dicarboxylic acid A polyester resin having a component as a polymerization component is included.

(Fluorene-containing polyester resin (A))
In Z ¹ and Z ² of the formula (1), examples of the aromatic hydrocarbon group include groups corresponding to C _6-14 aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, biphenyl, and indene. Z ¹ and Z ² are preferably a group corresponding to benzene (for example, a phenylene group).

In the formula (1), the alkylene group represented by R ^1a and R ^1b is a linear or branched C _2-4 alkylene group such as an ethylene group, a propylene group, a trimethylene group, or a tetramethylene group. Can be illustrated. In R ^1a and R ^1b , the types of alkylene groups may be different from each other. Further, the types of the alkylene groups R ^1a and R ^1b may be different depending on the numbers of the coefficients m and n. A preferable alkylene group is a _C2-3 alkylene group (ethylene group, propylene group), and is usually an ethylene group in many cases.

R ^2a and R ^2b are alkyl groups (eg, linear or branched C _1-8 alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and t-butyl groups). (In particular, a C _1-6 alkyl group)), a cycloalkyl group (C _5-10 cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, preferably a C _5-8 cycloalkyl group, more preferably a C _{5- 6} cycloalkyl group), aryl group [eg, phenyl group, alkylphenyl group (methylphenyl group (or tolyl group, 2-methylphenyl group, 3-methylphenyl group, etc.), dimethylphenyl group (xylyl group), etc.) and _{C 6-10} aryl group such as a naphthyl group, an aralkyl group (benzyl group, _{C 6-10} aryl, such as phenethyl group - _1-4 such as an alkyl group) carbon atoms and the like; alkoxy group (e.g., methoxy group, an ethoxy group, a propoxy group, n- butoxy group, isobutoxy group, _{C 1-8} alkoxy (especially C, such as t- butoxy _1-6 alkoxy group)); cycloalkoxy group (C _5-10 cycloalkyloxy group such as cyclohexyloxy group); aryloxy group (C _6-10 aryloxy group such as phenoxy group); aralkyloxy group (For example, C _6-10 aryl-C _1-4 alkyloxy group such as benzyloxy group); acyl group (such as C _1-6 acyl group such as acetyl group); alkoxycarbonyl group (C such as methoxycarbonyl group) _1-4, such as an alkoxycarbonyl group), a halogen atom (fluorine atom, such as chlorine atom); nitro group; shea Group; and the like substituted amino group (such as dialkylamino group).

The substitution numbers h1 and h2 of the substituents R ^2a and R ^2b may generally be an integer of about 0 to 4 (for example, 0 to 2). The substitution positions of the substituents R ^2a and R ^2b are not particularly limited. Preferred substituents R ^2a and R ^2b are C _1-6 alkyl groups (particularly methyl groups), and preferred substitution numbers h1 and h2 are integers of about 0 to 2 (for example, 0 or 1).

Examples of R ^3a and R ^3b include the hydrocarbon groups, alkoxy groups, halogen atoms, nitro groups, cyano groups, and substituted amino groups described above.

The substitution numbers j1 and j2 of the substituents R ^3a and R ^3b may be an integer of generally 0 to 4, preferably 0 to 2 (for example, 0 or 1). The substitution positions of the substituents R ^3a and R ^3b are not particularly limited. Preferred substituents R ^3a and R ^3b are C _1-6 alkyl groups (particularly methyl groups), and preferred substitution numbers j1 and j2 are 0 or 1 (eg, 0).

  The number of repetitions m and n of the oxyalkylene unit is 0 or an integer of 1 or more, and is usually an integer of about 1 to 10, preferably 1 to 7, and more preferably about 1 to 5 (for example, 1 to 3). May be.

Further, the fluorene-containing polyester resin only needs to contain the compound represented by the above formula (1) (diol component) as a diol component. For example, the diol component represented by the above formula (1) and the following: Formula (2)
HO—R ^1c —OH (2)
(In the formula, R ^1c represents an alkylene group.)
The polyester resin which uses as a polymerization component the diol component containing the diol component represented by these, and the below-mentioned dicarboxylic acid component may be sufficient. In the formula (2), examples of the alkylene group represented by R ^1c include linear or branched C _2-10 alkylene groups such as ethylene group, propylene group, trimethylene group and tetramethylene group. A chain or branched C _2-4 alkylene group (for example, ethylene group, tetramethylene group, etc.) is preferred.

  The ratio (molar ratio) between the diol component represented by formula (1) and the diol component represented by formula (2) is the former / the latter = 100/0 to 10/90 (for example, 100/0 to 30 / 70), usually 99/1 to 50/50, preferably 99/1 to 55/45, more preferably 98/2 to 60/40, especially 97/3 to 65/35 (e.g. , 95/5 to 70/30).

  On the other hand, the dicarboxylic acid component may be an aliphatic dicarboxylic acid component, but is an alicyclic dicarboxylic acid component or an aromatic dicarboxylic acid component from the viewpoint of optical properties (for example, refractive index, birefringence, etc.). Is preferred.

Examples of the alicyclic dicarboxylic acid component include cycloalkane dicarboxylic acids (cyclopentane dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid, 1,3-cyclohexane dicarboxylic acid, 1,2-cyclohexane dicarboxylic acid, cycloheptane dicarboxylic acid, etc. _5-10 cycloalkane-dicarboxylic acid), polycyclic alkane dicarboxylic acids (di or tricyclo C _7-10 alkane-dicarboxylic acid such as bornane dicarboxylic acid and norbornane dicarboxylic acid) and the like. Usually, the alicyclic dicarboxylic acid component is C _5-10 cycloalkane-dicarboxylic acid (particularly 1,4-cyclohexanedicarboxylic acid).

Examples of the aromatic dicarboxylic acid component include C _6-14 arene-dicarboxylic acid such as phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, and C _12-14 biphenyl-dicarboxylic acid such as biphenyl-4,4′-dicarboxylic acid. Etc. can be exemplified. Usually, the aromatic dicarboxylic acid component is a C _6-12 arene-dicarboxylic acid (particularly terephthalic acid).

The dicarboxylic acid component may be an acid anhydride, a lower C _1-4 alkyl ester such as dimethyl ester, or a derivative capable of forming an ester such as an acid halide corresponding to the dicarboxylic acid. The dicarboxylic acid component may include one or more substituents such as a hydrocarbon group [for example, an alkyl group (for example, a C _1-4 alkyl group such as a methyl group), a cycloalkyl group (for example, a cyclohexyl group, etc.). C _5-10 cycloalkyl group), aryl group (for example, C _6-10 aryl group such as phenyl group)], haloalkyl group, hydroxyl group, alkoxy group (for example, C _1-10 alkoxy group such as methoxy group) ), Haloalkoxy group, carboxyl group, alkoxycarbonyl group (eg, C _1-10 alkoxy-carbonyl group such as methoxycarbonyl group), acyl group (eg, C _2-5 acyl group such as acetyl group), substituted amino Group, halogen atom, nitro group, cyano group, etc., depending on the type of dicarboxylic acid Yibin can be selected.

  The ratio (use ratio) of the dicarboxylic acid component and the diol component can be selected from the former / the latter (molar ratio) = about 5/1 to 0.1 / 1, and usually the former / the latter = 1.5 / 1. It may be about 0.5 / 1, preferably 1.2 / 1 to 0.8 / 1, more preferably about 1.1 / 1 to 0.9 / 1. By adjusting the ratio (use ratio) between the dicarboxylic acid component and the diol component, the type of terminal group of the fluorene-containing polyester resin to be generated can be adjusted.

Preferred fluorene-containing polyester resins include, for example, (i) in the formula (1), R ^1a and R ^1b are ethylene groups, m and n are 1, and R ^2a and R ^2b are alkyl groups (for example, , A C _1-6 alkyl group such as a methyl group) or an aryl group (for example, a C _6-10 aryl group such as a phenyl group), h1 and h2 are 0 to 2, and j1 and j2 are 0 A copolymer comprising a component and a diol component in which R ^1c is an ethylene group and a dicarboxylic acid component that is terephthalic acid in the formula (2) as a polymerization component, and represented by the following formula (3a) A copolymer having a unit and a unit represented by the following formula (4a), (ii) In the formula (1), R ^1a and R ^1b are ethylene groups, m and n are 1, and R ^2a And R ^2b is a An alkyl group (eg, a C _1-6 alkyl group such as a methyl group) or an aryl group (eg, a C _6-10 aryl group such as a phenyl group), h1 and h2 are 0 to 2, and j1 and j2 are A diol component that is 0, a diol component in which R ^1c is an ethylene group in the above formula (2), and a dicarboxylic acid component that is 1,4-cyclohexanedicarboxylic acid, and the like. . For example, as an example of the copolymer contained in (i), a copolymer having a unit represented by the following formula (3a) and a unit represented by the following formula (4a) As an example of the copolymer contained, a copolymer having a unit represented by the following formula (3b) and a unit represented by the following formula (4b) can be given.

  The ratio of the unit represented by the following formula (3a) and the unit represented by the following formula (4a) is the former / the latter (unit number ratio) = 50/50 to 100/0, preferably 60/40 to 95. / 5, more preferably about 65/35 to 90/10. The ratio of the unit represented by the following formula (3b) to the unit represented by the following formula (4b) is also the former / the latter (unit number ratio) = 50/50 to 100/0, preferably 60/40. It may be about ~ 95/5, more preferably about 65/35 to 90/10.

  The fluorene-containing polyester-based resin may be a commercially available product or a synthesized product synthesized using (or applying) a conventional method. The fluorene-containing polyester resin can be obtained by reacting a corresponding diol component with a dicarboxylic acid component. For a method for producing such a polyester resin, for example, JP-A-2004-315676 can be referred to.

  The weight average molecular weight of the fluorene-containing polyester resin is, for example, 5,000 to 50,000, preferably measured by gel permeation chromatography (solvent: tetrahydrofuran, reference resin: polystyrene) at 40 ° C. May be about 10,000 to 48,000, more preferably about 15,000 to 46,000, particularly about 20,000 to 45,000 (for example, 25,000 to 40,000).

  The shape of the resin particles composed of such a fluorene-containing polyester resin is not particularly limited as long as it is in the form of particles. For example, spherical (or true spherical), irregular shape (elliptical spherical, cylindrical, rod, flat) Or an irregular shape). A preferred shape is spherical. The surface (or outer surface) of the resin particles may be smooth or uneven (or curved).

  Although the resin particles are composed of a fluorene-containing polyester resin having a bulky structure, the particle size (particle diameter) is extremely small and nanometer size. The number average particle diameter (or number-based average particle diameter: Dn) of the resin particles can be selected from a range of about 1 to 1000 nm, for example, 10 to 900 nm, preferably 20 to 800 nm (for example, 30 to 800 nm), Preferably it is about 35 to 600 nm (for example, 40 to 550 nm), particularly about 40 to 500 nm (for example, 50 to 400 nm), and usually about 1 to 500 nm (for example, 2 to 400 nm, preferably 3 to 300 nm). Good. In the present invention, the resin particles have a number average particle diameter (or number-based average particle diameter: Dn) of 50 nm or less (for example, 1 to 40 nm, preferably 1 to 30 nm, more preferably 2 to 20 nm, usually 3 to 3). The particle size can be very small (about 25 nm). The volume average particle diameter (or volume standard average particle diameter: Dv) of the resin particles can be selected from a range of about 2 to 1000 nm, for example, 10 to 1000 nm, preferably 20 to 800 nm, more preferably 30 to 750 nm, particularly It is about 40-700 nm (for example, 50-600 nm), and about 2-600 nm (for example, 2-500 nm, preferably 3-400 nm) may be sufficient. In the present invention, the volume average particle diameter (or volume reference average particle diameter: Dn) of the resin particles is 60 nm or less (for example, 2 to 50 nm, preferably 3 to 40 nm, more preferably about 4 to 30 nm). Small particle size can also be achieved. In addition, the said number average particle diameter and volume average particle diameter respectively show the number average particle diameter and volume average particle diameter calculated | required by converting into spherical shape, when the said resin particle is the said unusual shape.

The resin particles have small variation in particle diameter and high uniformity in particle diameter. That is, the resin particles have a small particle size dispersity (or dispersibility). The ratio (Dv / Dn) between the volume average particle diameter and the number average particle diameter of the resin particles is, for example, 1.0 to 10, preferably 1.01 to 8, more preferably 1.02 to 6, particularly 1. It may be about 0.05 to 5 (for example, 1.07 to 4). Further, the coefficient of variation (CV value) indicating the variation in particle diameter is, for example, 50% or less (for example, about 1 to 45%), preferably 40% or less (for example, about 2 to 40%), and more preferably 35. % Or less (for example, about 3 to 35%), particularly 30% or less (for example, about 5 to 25%). The coefficient of variation (CV value) is expressed by the following formula (1).
Coefficient of variation (%) = (standard deviation of number average particle diameter / number average particle diameter) × 100 (1)
Can be used to calculate.

  Such resin particles (or molded articles thereof) are excellent in heat resistance. The glass transition temperature (Tg) of the resin particles (or a molded product thereof) is 110 ° C. or higher (for example, 110 to 180 ° C.), preferably 115 to 170 ° C., more preferably about 120 to 165 ° C.

  Moreover, the resin particles are excellent in various optical properties. Specifically, the resin particles are excellent in transparency. For example, the light transmittance at a wavelength of 550 nm of the molded body of the resin particles is 80 to 97%, preferably 82 to 96%, more preferably 85 to 95. %. Further, the resin particles (or a molded product thereof) have a high refractive index, for example, 1.56 to 1.75, preferably 1.57 to 1.73, and more preferably about 1.58 to 1.7. is there.

  In addition, the said resin particle may be comprised by the alloy of the said fluorene containing polyester-type resin and other resin, unless the characteristic of this invention is impaired. The resin capable of forming an alloy may be, for example, a thermosetting resin, but is usually a thermoplastic resin [for example, olefin resin, styrene resin, vinyl chloride resin, vinyl acetate resin, polyvinyl alcohol resin. Resin, thermoplastic acrylic resin, polyacetal resin, polyester resin (eg, polyalkylene arylate resin such as polyethylene terephthalate resin), polycarbonate resin, fluorine resin, polyamide resin, polysulfone resin (polysulfone resin) , Polyethersulfone resins, etc.), polyphenylene ether resins, polyphenylene sulfide resins, and the like. The resins may be used alone or in combination of two or more. The proportion of the resin may be selected according to the type, and is, for example, 20 parts by weight or less (for example, 0.01 to 20 parts by weight), preferably 0.05 with respect to 100 parts by weight of the fluorene-containing polyester resin. -15 parts by weight, more preferably about 0.1-10 parts by weight.

  Further, the resin particles may be added with conventional additives such as plasticizers, softeners, colorants, dispersants, mold release agents, stabilizers (hindered phenol antioxidants, phosphorus oxides) as necessary. Antioxidants, antioxidants such as sulfur-based antioxidants, UV absorbers, heat stabilizers, etc.), antistatic agents, flame retardants, anti-blocking agents, crystal nucleus growth agents, fillers (glass fibers, carbon fibers, etc.) Or other fibrous fillers). These additives may be used alone or in combination of two or more. The ratio of the additive may be selected according to the type and is not particularly limited, but can be selected from a range of about 0.01 to 100 parts by weight with respect to 100 parts by weight of the fluorene-containing polyester resin. It is about 1 to 50 parts by weight, preferably about 0.5 to 30 parts by weight.

[Production method of resin particles]
The method for producing the resin particles of the present invention can be produced by various production methods (for example, (1) gas phase method, (2) liquid phase method, (3) solid phase method, etc.) as exemplified in the background section. There may be. In addition, the said resin particle utilizes the method of grind | pulverizing the lump (or lump-like fluorene-containing polyester resin) of the said fluorene containing polyester-type resin, the method of spraying the said lump under heating (or in a molten state), etc. However, it is industrially easy to produce resin particles that are excellent in operability (for example, that they can be produced even under non-heating, easy to adjust viscosity, etc.) and resin particles with a small particle size. It is preferable that the resin and the resin solution containing the solvent capable of dissolving the resin are refined (or made into particles) and manufactured.

  Specifically, the resin particles are produced by refining a resin solution containing the fluorene-containing polyester resin (A) and a solvent (B) capable of dissolving the fluorene-containing polyester resin (A). Also good.

(Resin solution)
The resin solution can be prepared by mixing at least the fluorene-containing polyester resin (A) and a solvent (B) capable of dissolving the resin (A).

(Solvent (B))
The solvent (B) is not particularly limited as long as it can dissolve the fluorene-containing polyester-based resin (A). However, the solvent (B) has a good affinity with the solvent (C) described below in terms of dissolving the resin (A) well. In view of the above, the solvent (B) is usually an aprotic polar solvent [for example, cyclic ethers such as tetrahydrofuran (THF), dioxolane, dioxane, trioxane; diethyl ketone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK). , Ketones such as cyclohexanone; lactones or cyclic monoesters (for example, C _4-10 lactones such as β-propiolactone, β-butyrolactone, γ-butyrolactone, γ-valerolactone, ε-caprolactone); nitrogen-containing solvents [ For example, nitriles (eg, acetonitrile, propionitrily , Benzonitrile, etc.), amides (eg, dimethylformamide, dimethylacetamide, etc.), pyrrolidone-containing solvents (eg, N-methyl-2-pyrrolidone, etc.), hexamethylphosphamide, etc.]; sulfur-containing solvents [eg, dimethyl Sulfoxides such as sulfoxide, sulfolane and the like] are preferably used. The solvent (B) may be a single solvent or a mixed solvent of two or more. Among these solvents (B), it is preferable to use a volatile solvent from the viewpoint that the solvent (B) can be easily removed in the production process (or after production) of the resin particles. Specifically, for example, cyclic ethers such as tetrahydrofuran, dioxolane, dioxane and the like are preferable, and tetrahydrofuran is particularly preferably used. Incidentally, the solubility parameter of the solvent (B) ([delta]), for example, ^{23 MPa 1/2} or less (e.g., 10~23MPa ^1/2), preferably ^{22 MPa 1/2} or less (e.g., 12~22MPa ^1/2) More preferably, it may be about 21 MPa ^1/2 or less (for example, 15 to 21 MPa ^1/2 ).

  The ratio between the fluorene-containing polyester resin (A) and the solvent (B) is the former / the latter (weight ratio) = 1/99 to 50/50, preferably 2/98 to 45/55, more preferably 3/97. May be about 40/60, especially 5/95 to 30/70 (for example, 7/93 to 25/75), and usually 3/97 to 40/60 (for example, 4/96 to 35/65). It may be a degree. As described later, the resin solution containing the fluorene-containing polyester resin (A) at such a ratio is obtained by precipitating the fluorene-containing polyester resin (A) with the solvent (C) while miniaturizing the resin solution. It is effective for producing particles.

  In addition, when forming the resin particle comprised by the alloy of the said resin (A) and other resin, the resin particle containing an additive, the other resin of the said illustration, an additive, etc. are the said resin normally. Often added or mixed during the preparation of the solution.

  The method for refining (or granulating) the resin solution is not particularly limited, but promotes the miniaturization (or particleization) of the resin solution, enhances production efficiency, and aggregates the generated resin particles (or In order to prevent condensation, the resin solution is usually brought into contact with a solvent (C) which is a poor solvent for the resin (A) and is miscible with the solvent (B) to refine the resin solution ( Or particles).

(Solvent (C))
The solvent (C) is not particularly limited as long as it is a poor solvent for the fluorene-containing polyester resin (A) and is a solvent miscible (or compatible) with the solvent (B). Examples of the solvent (C) include water, organic solvents (for example, water-soluble organic solvents) {for example, C _1-7 such as alcohols (for example, methanol, ethanol, 1-propanol, isopropanol, 1-butanol, hexanol and the like). Alkanols; C _2-6 alkanediols such as ethylene glycol, propylene glycol, butylene glycol (or 1,4-butanediol), (poly) alkylene glycol alkyl ethers [for example, cellosolves (methyl cellosolve, ethyl C _1-4 alkyl cellosolves such as cellosolve), carbitols (such as C _1-4 alkyl carbitols such as methyl carbitol and ethyl carbitol), propylene glycol monoalkyl ether (eg, propylene glycol monomethyl) Propylene glycol mono _C1-4 alkyl ether such as ether), dipropylene glycol monoalkyl ether (eg, dipropylene glycol mono _C1-4 alkyl ether such as dipropylene glycol monomethyl ether), etc.], (poly) alkylene glycol mono Alkyl ether acetates [e.g., cellosolve acetates ( _C1-4 alkyl cellosolve acetates such as ethyl cellosolve acetate), propylene glycol monoalkyl ether acetates (e.g., propylene glycol mono _C1-4 alkyl such as propylene glycol monomethyl ether acetate) Ethers) etc.] etc.} (for example, aqueous solvents). Solvent (C) may be a single solvent or a mixed solvent of two or more. Of these solvents (C), water and alcohols are preferable from the viewpoint of easy removal after the production of the resin particles, cost, and safety. Particularly, C ₁ such as water, methanol, ethanol, isopropanol and the like. _-3 alkanols and the like are preferably used. In addition, (poly) alkylene glycol alkyl ethers and (poly) alkylene glycol monoalkyl ether acetates are also preferable in terms of making resin particles finer. Since such a solvent is a solvent that is widely used as a solvent constituting the coating liquid, the resin particles can also be used in the form of a dispersion liquid dispersed in a solvent. The solubility parameter (δ) of the solvent (C) is, for example, 16 MPa ^1/2 or more (eg, 16 to 50 MPa ^1/2 ), preferably 17 MPa ^1/2 or more (eg, 17 to 40 MPa ^1/2 ), Preferably, it may be about 18 MPa ^1/2 or more (for example, 18 to 35 MPa ^1/2 ).

  The ratio of the solvent (C) is 5 to 1000 parts by weight, preferably 10 to 700 parts by weight, and more preferably 30 to 500 parts by weight with respect to 1 part by weight of the fluorene-containing polyester resin (A) contained in the resin solution. Part (for example, about 50 to 400 parts by weight), or usually about 30 to 300 parts by weight. The ratio of the solvent (C) is, for example, 1 to 800 parts by weight, preferably 3 to 500 parts by weight, with respect to 1 part by weight of the resin solution (or the total of the resin (A) and the solvent (B)). More preferably, it may be about 5 to 400 parts by weight (for example, 7 to 300 parts by weight), and usually about 10 to 250 parts by weight.

In miniaturization, in addition to the solvents (B) and (C), a third solvent (D) may be further used. As such a solvent (D), a solvent exhibiting intermediate solubility between a good solvent and a poor solvent (that is, a solvent capable of slightly dissolving the resin (A)) can be selected for the resin (A). . When such a solvent (D) (sometimes referred to as an intermediate solvent) is used, the recovery efficiency of the resin (A) can be efficiently improved because the solvent (D) promotes the precipitation of the resin (A). As such a solvent (D), although it depends on the kind of the resin (A), for example, a linear ketone such as an aliphatic ketone (for example, a di-C _1-4 alkyl ketone such as acetone or ethyl methyl ketone), Examples thereof include esters [for example, carboxylic acid alkyl esters (for example, acetic acid C _1-4 alkyl esters such as methyl acetate and ethyl acetate)] and the like. In addition, the solvent (D) may be a solvent that is usually miscible with the solvent (B) and the solvent (C). The solvent (D) may be used alone or in combination of two or more. The solubility parameter (δ) of the solvent (D) (for example, aliphatic ketone, carboxylic acid alkyl ester, etc.) is, for example, 17 to 25 MPa ^1/2 , preferably 17.5 to 23 MPa ^1/2 , more preferably 18. It may be about ˜22 MPa ^1/2 , especially about 18.5 to 21 MPa ^1/2 .

  The intermediate solvent (D) may be in contact with the resin solution in the process of contacting the resin solution and the solvent (C). For example, (a) a mixed solution of the resin solution and the intermediate solvent (D) And a solvent (C) may be contacted, and (b) a mixed solution of the resin solution and the intermediate solvent (D) and a mixed solution of the intermediate solvent (D) and the poor solvent (C) may be contacted. Also good. In a preferred embodiment, the solvent (C) may be mixed at least in the state where the intermediate solvent (D) is mixed in advance with the resin solution (for example, the above-described embodiment (a)).

  The ratio of the solvent (D) is, for example, 0.5 to 50 parts by weight, preferably 1 to 40 parts by weight, more preferably 2 to 30 parts by weight (1 part by weight based on 1 part by weight of the fluorene-containing polyester resin (A). For example, it may be about 3 to 25 parts by weight, and usually about 5 to 20 parts by weight. Moreover, the ratio of a solvent (D) is 0.05-20 weight part with respect to 1 weight part of solvent (B), Preferably it is 0.1-10 weight part, More preferably, it is 0.2-5 weight. Part (for example, 0.3 to 3 parts by weight) or about 0.1 to 2 parts by weight (for example, 0.2 to 1 part by weight).

  As described above, the resin particles of the present invention may be produced by bringing the resin solution into contact with the solvent (C) to refine the resin solution. Specifically, the resin particles are (1) mixed with the solvent (C) while miniaturizing the resin solution [for example, the resin solution is added (or dropped) to the solvent (C) and stirred. [Mixed by mechanical (or physical) means such as sonication etc.] The fluorene-containing polyester resin (A) is precipitated into particles by the solvent (C) while miniaturizing (specifically, the phase) (2) In order to minimize the particle diameter of the resin particles, the solvent (C) is sprayed (or sprayed) on the resin solution and sprayed. While the liquid is collided with the resin solution and refined, the fluorene-containing polyester resin (A) may be phase-separated and precipitated into particles. In addition, when using an intermediate | middle solvent (D), in any of these methods, a resin solution and an intermediate | middle solvent (D) should just be contacted at an appropriate step as mentioned above. For example, the mixed solution containing the resin solution and the intermediate solvent (D) may be mixed with the solvent (C) while miniaturizing, and the solvent (C) is added to the mixed solution containing the resin solution and the intermediate solvent (D). You may spray.

  Hereinafter, these two methods will be described in detail.

[Method (1)]
In the method (1), the resin solution is refined and mixed with the solvent (C), and the fluorene-containing polyester resin (A) is precipitated in the form of particles by the solvent (C). In such a method (1), the method for refining the resin solution is not particularly limited, but typically, the resin solution and the solvent (C) may be mixed under stirring. .

  Stirring can be performed using stirring means (such as a stirring bar) or ultrasonic waves, or a combination thereof. When using stirring means such as a stirring blade, the stirring speed may be, for example, 10 to 5000 rpm, preferably 30 to 2000 rpm, more preferably about 50 to 1000 rpm, and usually about 20 to 500 rpm.

  The order of mixing is not limited, and the resin solution may be mixed (mixed under stirring) with the solvent (C), or the solvent (C) may be mixed (mixed under stirring) with the resin solution. In particular, when the solvent (C) is mixed (for example, dropped) into the resin solution, the fluorene-containing polyester resin (A) can be further refined. Further, the mixing is preferably carried out little by little from the viewpoint of making the resin solution finer. Typically, the resin solution and the solvent (C) are often mixed by dropping the other (for example, the resin solution) into either one (for example, the solvent (C)).

  When the intermediate solvent (D) is used as described above, the intermediate solvent (D) can be appropriately mixed. For example, the solvent (C) is mixed with the mixed solution containing the resin solution and the solvent (D). (For example, dripping) may be performed, and a mixed solution containing the solvent (C) and the intermediate solvent (D) may be mixed (for example, dripping) in the resin solution.

[Method (2)]
In the method (2) (method of spraying the solvent (C)), the concentration of the resin solution is 0.1 to 50% by weight, preferably 0.5 to 40% by weight, more preferably 1 to 30% by weight. It may be a degree.

  The ratio between the flow rate of the resin solution and the spray amount of the solvent (C) to be sprayed can be appropriately selected according to the desired particle size and the like. For example, the solvent (C C) is sprayed at a spraying amount of, for example, about 100 to 10000 mL / min, preferably 300 to 9000 mL / min, more preferably 500 to 8000 mL / min, particularly 1000 to 7000 mL / min (for example, 1300 to 6000 mL / min). May be. Further, spraying the solvent (C) at a high speed (or high pressure) on the resin solution is effective for minimizing the particle diameter. For example, for the resin solution flowing at a flow rate of 1 m / sec, the solvent (C) is, for example, 200 to 5000 m / sec, preferably 500 to 4000 m / sec, more preferably 700 to 3000 m / sec, particularly 800 to You may spray by the spray speed of about 2500 m / sec (for example, 1000-2000 m / sec). The flow rates (or spray rates) of the resin solution and the solvent (C) may be adjusted (or controlled) using various pumps (for example, a liquid feed pump, a circulation pump, etc.). Further, when the solvent (C) is sprayed on the resin solution at a spray angle (or spray angle) of 60 to 150 °, preferably 75 to 125 °, more preferably about 80 to 110 °, the resin solution and A solvent (C) can be made to contact efficiently.

  In the present invention, the form of the resin solution may be a resin solution flow or a droplet. The size (or diameter) of the resin solution flow in the width direction may be, for example, about 0.1 to 10 mm, preferably about 0.5 to 8 mm, and more preferably about 1 to 5 mm. The droplet size (or droplet diameter) may be, for example, about 0.5 to 5 mm, preferably about 0.6 to 4 mm, more preferably about 0.7 to 3 mm, and particularly about 0.7 to 2 mm. .

  In addition, the said solvent (C) may be sprayed with respect to the said resin solution (or its droplet) fixed to the member (or base material) etc., and the said resin solution (or resin solution) which is flowing. Or the droplets thereof may be sprayed.

  Such a method for producing resin particles can be performed using various apparatuses. FIG. 1 is a partially cutaway schematic cross-sectional view showing an example of the resin particle production apparatus of the present invention. The arrows in the figure indicate the flow of the product mixture.

  The apparatus includes a supply pipe (solvent supply pipe) 4 for supplying (or spraying) the solvent (C), a supply pipe (resin solution supply pipe) 5 for supplying (or dropping) the resin solution, and a supply The precipitation tube (length 0. 0) for bringing the fluorene-containing polyester resin (A) into particles in the solvent (C) while bringing the solvent (C) and resin solution into contact with each other to refine the resin solution. 5 to 3 m, an inner diameter of 20 to 50 mmφ) 2, a receiver 3 for collecting the resin particles generated in the precipitation tube 2, a side wall (or side wall) of the receiver 3, and a solvent ( C) and a pump 6 for guiding (or circulating) the solvent to the solvent supply pipe 4, and the pump 6, the receiver 3, and the solvent supply pipe 4 are respectively the first flow path 7a and the second flow path. They are connected by a flow path 7b.

  The solvent supply pipe (inner diameter of about 5 to 10 mmφ) 4 and the resin solution supply pipe (inner diameter of about 1 to 3 mmφ) 5 lead the solvent (C) and the resin solution into the precipitation tube 2, so that the plug 1 is arranged in parallel. It penetrates and extends into the precipitation tube 2. Further, the resin solution supply pipe 5 has the downstream end portion in the resin solution supply direction bent substantially at right angles to the axial direction of the solvent supply pipe 4 in order to bring the solvent (C) into contact with the resin solution. An opening (or an outlet) (inner diameter of about 0.1 to 1 mmφ) 5b is formed at the tip. The outlet 5b is disposed on an extension line of the axis of the solvent supply pipe 4 with a distance of about 3 to 10 mm from an opening (or spraying opening) 4b on the downstream side of the solvent supply pipe 4. Yes.

  In such an apparatus, for example, the resin solution is supplied from the opening (or supply port) 5a on the upstream side of the resin solution supply pipe 5 toward the outlet 5b, and is 0.5 to 3 mL / from the outlet 5b. It flows out into the precipitation tube 2 in the vertical direction in the form of a resin solution flow or droplets (for example, droplets having a droplet diameter of about 0.5 to 2 mm) at a flow rate of about a minute. The outflowed resin solution is supplied from the supply port 4a on the upstream side of the solvent supply pipe 4 toward the spray port 4b and is sprayed in the vertical direction at a spray rate of about 3000 to 5000 mL / min from the spray port 4b. (C) is contacted (or collided) in the precipitation tube 2 to be refined, and the fluorene-containing polyester resin (A) is precipitated in particles by the solvent (C) to produce resin particles. The produced resin particles are collected in the receiver 3 together with the solvent (B) and the solvent (C). The collected resin particles, the solvent (B) and the solvent (C) are sucked out by the pump 6 and sent again to the solvent supply pipe 4 through the first flow path 7a and the second flow path 7b. Reused.

  In the apparatus, the size (inner diameter, length, etc.) of the precipitation tube, the solvent supply tube, and the resin solution supply tube is not limited to the above-described sizes, and can be selected according to the desired particle size, production amount, and the like. In the apparatus, the solvent supply tube 4 and the resin solution supply tube 5 are hollow cylinders, and the cross section is circular, elliptical, polygonal (for example, triangular, quadrangular, pentagonal, octagonal, etc.). It may be present, but the cross section is preferably circular (or cylindrical). Moreover, although the outflow port 5b is normally arrange | positioned on the extension line | wire of the axial center of the solvent supply pipe | tube 4, the solvent (C) sprayed can contact (or collide) with the resin solution (or its droplet). As long as the above is true, the outlet 5b may be displaced from the axis of the solvent supply pipe 4. Furthermore, the distance between the spray port 4b and the outlet 5b can be selected according to the spray amount of the solvent (C), the spray speed, the flow rate of the resin solution (or its droplets), etc. There is no need to be about 3 to 10 mm, for example, 1 to 30 mm, preferably 2 to 20 mm, more preferably about 3 to 15 mm (for example, 5 to 10 mm), and the solvent (C) and resin to be sprayed Effective contact (or collision) with the solution (or its droplets) makes it possible to produce extremely small resin particles.

  In the present invention, it is sufficient that both the solvent (C) and the resin solution are in contact with each other. For example, both the solvent (C) and the resin solution may be contacted in a liquid state, or both may be contacted (or collided) in a spray liquid state. Furthermore, any one of the solvent (C) and the resin solution may be sprayed on the other to be brought into contact. Specifically, the solvent (C) may be brought into contact with the resin solution stream. Further, the spray solution of the solvent (C) and the spray solution of the resin solution may be contacted (or collided). Furthermore, the resin solution may be sprayed (or jetted) on the solvent (C), and the solvent (C) may be sprayed (or jetted) on the resin solution stream (or droplets thereof).

  Moreover, the outflow (or spraying) direction of both the solvent (C) and the resin solution is not particularly limited as long as both can be contacted. For example, the outflow (particularly spraying) direction of the solvent (C) The outflow direction of the resin solution may be directed, and the outflow (especially spraying) direction of the solvent (C) may intersect with the outflow direction of the resin solution.

  The flow rate of the resin solution and the spray amount of the solvent (C) are not limited to the above examples. For example, the flow rate of the resin solution is not limited to 0.5 to 3 mL / min, and is, for example, 0.1 to 100 mL / min, preferably 0.5 to 50 mL / min, depending on the desired particle size, production amount, and the like. More preferably, it may be about 1 to 30 mL / min. Further, the spray amount of the solvent (C) is not limited to 3000 to 5000 mL / min, and is, for example, 100 to 50000 mL / min (for example, 300 to 20000 mL / min), preferably according to the desired particle diameter, production amount, etc. It may be about 500 to 10000 mL / min (for example, 1000 to 8000 mL / min), more preferably about 2000 to 6000 mL / min (for example, 2500 to 4500 mL / min). As described above, nanometer-sized resin particles can be effectively produced by spraying the solvent (C) at a higher speed than the flow rate (or outflow rate) of the resin solution.

  In the above method, the resin is sprayed with the solvent (C), and the spray solution is brought into contact with (or collided with) the resin solution to refine the resin solution, while the fluorene-containing polyester resin (A) is precipitated. Produce particles. Therefore, the solvent (C) may be continuously supplied (or sprayed) or may be supplied (or sprayed) intermittently while the resin solution flows out from the outlet. However, as described above, from the viewpoint of bringing the solvent (C) into contact with the resin solution, the solvent (C) is continuously supplied (or sprayed) while the resin solution flows out from the outlet 5b. Is preferred. In particular, the solvent (C) and the resin solution are effectively contacted to increase the precipitation efficiency of the fluorene-containing polyester resin (A), and from the viewpoint of obtaining nanometer-sized particles, the solvent (C) is continuously added. And as above-mentioned, it is preferable to supply (or spray) at high speed and to fill the said solvent (C) in a precipitation tube. Even when the solvent (C) is continuously supplied (or sprayed) at a high speed, the solvent (C) is circulated using a pump (circulation pump or the like) as in the above example. By reusing it, the production cost of the resin particles can be significantly reduced.

  In addition, after the production is completed, the resin particles collected in a state of dispersion with the solvent (B) and the solvent (C) in the receiver are collected in, for example, a small amount of polar solvent [for example, conventional polar solvent] (For example, acid such as hydrochloric acid, etc.) is added, and the dispersibility is increased, and the resin particles are precipitated by centrifugation (for example, about 5000 to 12000 rpm), and then drained and isolated (or purified). May be.

  As described above (for example, by the method (1) or (2)), particles of the resin (A) are obtained. Recovery of the resin particles can be performed using a conventional method such as filtration. For the recovery, centrifugation or the like may be used. Further, in the recovery, if necessary, thickeners [for example, cellulose ethers (alkyl cellulose such as methyl cellulose; hydroxyalkyl cellulose such as hydroxyethyl cellulose and hydroxypropyl cellulose; carboxymethyl cellulose, sodium carboxymethyl cellulose, etc.), polycarboxylic acids (Such as sodium polyacrylate)] may be used. These thickeners may be used alone or in combination of two or more. The use ratio of the thickener may be, for example, about 1 to 500 parts by weight, preferably about 2 to 300 parts by weight with respect to 100 parts by weight of the resin (A). The thickener is usually used in a mixture with the mixture after the particles are produced. By using such a thickener, the produced resin particles can be easily precipitated in the mixed solution, and the recovery efficiency can be increased.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. In addition, the symbol of each evaluation method and component in an Example and a comparative example is as follows.

[Evaluation method]
(Flow rate and spray amount)
The flow rate of the solvent (C) and the spray amount of the resin solution were measured and adjusted using a liquid feed pump (manufactured by Yamato Scientific Co., Ltd., “Master Flex Tube Pump”).

(Average particle size)
The number average particle size and the volume average particle size were measured using a particle size distribution measuring device (manufactured by Nikkiso Co., Ltd., “Microtrac UPA 150”).

[Component abbreviations]
FBP: fluorene-containing polyester resin {manufactured by Osaka Gas Chemical Co., Ltd. [in block copolymer having a unit represented by the above formula (3b) and a unit represented by the following formula (4b) (in the formula (3b) , H1 and h2 are 0, a unit represented by formula (3b) / unit represented by formula (4b) (unit number ratio) = 80/20, weight average molecular weight: 33,850 ]]}
Example 1
Resin particles were produced using the apparatus shown in FIG. Specifically, the solvent supply pipe (inner diameter 6.0 mmφ) 4, the resin solution supply pipe (inner diameter 2.15 mmφ, the inner diameter of the opening (or outlet) 0.65 mmφ) 5, and the precipitation pipe (length 1.5 m) , Fluorene-containing polyester resin (FBP) and tetrahydrofuran (THF) using an apparatus including an inner diameter 40 mmφ 2, a receiver 3, and a pump 6 for introducing the solvent (C) to the solvent supply pipe 4. The resin solution [FBP / THF (weight ratio) = 10/90 resin solution] was discharged from the resin solution supply pipe 5 at a flow rate of 2 mL / min. Methanol as the solvent (C) is sprayed from the solvent supply tube 4 at a spray angle of 90 ° from the solvent supply pipe 4 at a spray amount of 4000 mL / min, and the resin particles composed of FBP are brought into contact with the droplets. Manufactured. The obtained resin particles were observed with a scanning electron microscope (SEM) and the number average particle diameter was measured. The number average particle diameter was 253 nm. The micrograph is shown in FIG. The scale bar in the figure indicates 1 μm. Moreover, the coefficient of variation of the number average particle diameter of the obtained resin particles was 14.5%.

(Example 2)
Resin particles were produced in the same manner as in Example 1 except that water was used instead of methanol. The obtained resin particles were observed with a scanning electron microscope (SEM) and the number average particle diameter was measured. The number average particle diameter was 273 nm. The micrograph is shown in FIG. The scale bar in the figure indicates 1 μm. Moreover, the coefficient of variation of the number average particle diameter of the obtained resin particles was 29.9%.

(Example 3)
Resin particles were produced in the same manner as in Example 1 except that cyclohexanone was used instead of THF and water was used instead of methanol. The obtained resin particles were observed with a scanning electron microscope (SEM) and the number average particle diameter was measured. The number average particle diameter was 248 nm. The micrographs are shown in FIGS. 4 and 5 (enlarged view of FIG. 4). The scale bar in FIG. 4 indicates 5 μm, and the scale bar in FIG. 5 indicates 1 μm. Moreover, the coefficient of variation of the number average particle diameter of the obtained resin particles was 12.1%.

Example 4
Resin particles were produced in the same manner as in Example 1 except that cyclohexanone was used instead of THF. The obtained resin particles were observed with a scanning electron microscope (SEM) and the number average particle diameter was measured. As a result, the number average particle diameter was 170 nm. The micrographs are shown in FIGS. 6 and 7 (enlarged view of FIG. 6). The scale bar in FIG. 6 indicates 5 μm, and the scale bar in FIG. 7 indicates 1 μm. Further, the coefficient of variation of the number average particle diameter of the obtained resin particles was 3.2%.

  As is apparent from FIGS. 3 to 7, the resin particles obtained in the examples were nanometer size. Moreover, the variation in particle diameter was small and the uniformity was excellent.

(Comparative Example 1)
Laboplast Mill, which is a dry blend of 30 parts of fluorene-based polyester resin (Ogaso Chemical Co., Ltd., FBP-GX) and 70 parts of water-soluble polyvinyl alcohol (Kuraray Co., Ltd., Expal) and heated to 260 ° C. (Torshin Co., Ltd., TDR100-500X3 type) was added and kneaded at 300 rpm for 10 minutes. Immediately after kneading, the melt began to become turbid, indicating that the fluorene-based polyester resin was dispersed in water-soluble polyvinyl alcohol. After kneading, the mixture is cooled, and the cooled dispersion is pulverized into a lump of about 1 cm using a pulverizer (Osaka Gas Chemical Co., Ltd., Absolute Mill ABS-W). Alcohol was eluted to obtain fluorene-based polyester resin fine particles as a precipitate. Further, the washing with hot water was repeated three times. The average particle size of the fluorene-based polyester resin fine particles was 1.94 μm when measured in a water-dispersed state.

(Example 5)
Into a 100 mL beaker, 20 g of a THF solution containing FBP at a ratio of 10% by weight was added dropwise over 5 minutes while stirring with a magnetic stirrer, and a resin solution (A) containing acetone (mixture) Got.

  400 g of methanol was placed in a 500 mL beaker. Then, while vigorously stirring with a 7 cm-long stir bar, the resin solution (A) is removed from the syringe while the needle of a syringe (10 mL) with an injection needle (φ0.9 mm) is immersed in about 2 cm in methanol. Was poured over 10 minutes to obtain a slurry containing resin particles. The obtained slurry was centrifuged at a rotational speed of 5000 rpm for 15 minutes to recover 1.8 g of resin particles (that is, recovered at a yield of 90%). The obtained resin particles were observed with a scanning electron microscope (SEM) and the number average particle size was measured. The number average particle size was 0.15 μm.

(Example 6)
20 g of a THF solution containing 10% by weight of FBP was placed in a 100 mL beaker, and 12.2 g of acetone was added dropwise over 5 minutes while stirring with a magnetic stirrer to obtain a resin solution (A) containing acetone.

  A 500 mL beaker was charged with 360 g of isopropanol. And like Example 5, after inject | pouring the said resin solution (A) over 10 minutes or more from a syringe, 0.72g of hydroxypropyl cellulose (made by Aldrich) is added, and the slurry containing a resin particle is obtained. It was. From the obtained slurry, 1.80 g of resin particles were recovered in the same manner as in Example 5 (that is, recovered at a yield of 90%). The obtained resin particles were observed with a scanning electron microscope (SEM) and the number average particle size was measured. The number average particle size was 0.2 μm.

(Example 7)
20 g of a THF solution containing 7 wt% of FBP was placed in a 100 mL beaker, and 14.6 g of acetone was added dropwise over 5 minutes while stirring with a magnetic stirrer to obtain a resin solution (A) containing acetone.

  216 g of isopropanol was placed in a 500 mL beaker. And it carried out similarly to Example 5, and inject | poured the said resin solution (A) over 10 minutes or more from the syringe, and obtained the slurry containing a resin particle. From the obtained slurry, 1.22 g of resin particles were recovered in the same manner as in Example 5 (that is, recovered in a yield of 87%). The obtained resin particles were observed with a scanning electron microscope (SEM), and the number average particle diameter was measured. The number average particle diameter was 0.1 μm.

(Example 8)
20 g of a THF solution containing 7 wt% of FBP was placed in a 100 mL beaker, and 12.8 g of acetone was added dropwise over 5 minutes while stirring with a magnetic stirrer to obtain a resin solution (A) containing acetone.

  55.8 g of isopropanol was placed in a 500 mL beaker. And it carried out similarly to Example 5, and inject | poured the said resin solution (A) over 10 minutes or more from the syringe, and obtained the slurry containing a resin particle. From the obtained slurry, 1.19 g of resin particles were recovered in the same manner as in Example 5 (that is, recovered at a yield of 85%). The obtained resin particles were observed with a scanning electron microscope (SEM) and the number average particle size was measured. The number average particle size was 0.2 μm.

Example 9
20 g of a THF solution containing 5% by weight of FBP was placed in a 100 mL beaker and 14.1 g of acetone was added dropwise over 5 minutes while stirring with a magnetic stirrer to obtain a resin solution (A) containing acetone.

  190 g isopropanol was placed in a 500 mL beaker. And it carried out similarly to Example 5, and inject | poured the said resin solution (A) over 10 minutes or more from the syringe, and obtained the slurry containing a resin particle. From the obtained slurry, 0.88 g of resin particles were recovered in the same manner as in Example 5 (that is, recovered with a yield of 88%). The obtained resin particles were observed with a scanning electron microscope (SEM) and the number average particle diameter was measured. The number average particle diameter was 0.09 μm.

(Example 10)
20 g of a THF solution containing 5% by weight of FBP was placed in a 100 mL beaker and 14.1 g of acetone was added dropwise over 5 minutes while stirring with a magnetic stirrer to obtain a resin solution (A) containing acetone.

  190 g isopropanol was placed in a 500 mL beaker. And like Example 5, after inject | pouring the said resin solution (A) from a syringe over 10 minutes or more, hydroxypropylcellulose (made by Aldrich) 0.95g is added, The slurry containing a resin particle is obtained. It was. From the obtained slurry, 0.86 g of resin particles were recovered in the same manner as in Example 5 (that is, recovered with a yield of 86%). The obtained resin particles were observed with a scanning electron microscope (SEM) and the number average particle size was measured. The number average particle size was 0.15 μm.

(Example 11)
20 g of a THF solution containing 5% by weight of FBP was placed in a 100 mL beaker and 14.1 g of acetone was added dropwise over 5 minutes while stirring with a magnetic stirrer to obtain a resin solution (A) containing acetone.

  190 g of water was placed in a 500 mL beaker. And like Example 5, after inject | pouring the said resin solution (A) from a syringe over 10 minutes or more, hydroxypropylcellulose (made by Aldrich) 0.95g is added, The slurry containing a resin particle is obtained. It was. 0.85 g of resin particles were recovered from the resulting slurry in the same manner as in Example 5 (that is, recovered with a yield of 85%). The obtained resin particles were observed with a scanning electron microscope (SEM) and the number average particle size was measured. The number average particle size was 0.15 μm.

(Example 12)
20 g of a dioxane solution containing 10% by weight of FBP was placed in a 100 mL beaker, and 15.1 g of acetone was added dropwise over 5 minutes while stirring with a magnetic stirrer to obtain a resin solution (A) containing acetone.

  360 g of methanol was placed in a 500 mL beaker. And it carried out similarly to Example 5, and inject | poured the said resin solution (A) over 10 minutes or more from the syringe, and obtained the slurry containing a resin particle. From the resulting slurry, 1.8 g of resin particles were recovered in the same manner as in Example 5 (that is, recovered at a yield of 90%). The obtained resin particles were observed with a scanning electron microscope (SEM) and the number average particle size was measured. The number average particle size was 0.2 μm.

(Example 13)
100 g of a THF solution containing 20% by weight of FBP was placed in a 500 mL beaker. Then, while stirring vigorously with a 7 cm stirrer, a syringe (10 mL) attached with a syringe needle (φ0.9 mm) was immersed in the resin solution for about 2 cm in the resin solution, and PGME (propylene glycol monomethyl ether) was passed from the syringe. ) 20 g was poured over 10 minutes to obtain a slurry containing resin particles. Resin particles were collected by centrifuging the obtained slurry at a rotational speed of 5000 rpm for 15 minutes. The obtained resin particles were observed with a scanning electron microscope (SEM) and the number average particle diameter was measured. The number average particle diameter was 6.7 nm.

(Example 14)
100 g of a THF solution containing 20% by weight of FBP was placed in a 500 mL beaker. And PGME12g was inject | poured from the syringe over 10 minutes or more like Example 13, and the slurry containing a resin particle was obtained. Resin particles were collected by centrifuging the obtained slurry at a rotational speed of 5000 rpm for 15 minutes. The obtained resin particles were observed with a scanning electron microscope (SEM) and the number average particle diameter was measured. The number average particle diameter was 11.2 nm.

(Example 15)
100 g of a THF solution containing 20% by weight of FBP was placed in a 500 mL beaker. Then, in the same manner as in Example 13, 20 g of propylene glycol monomethyl ether acetate was injected from a syringe over 10 minutes to obtain a slurry containing resin particles. Resin particles were collected by centrifuging the obtained slurry at a rotational speed of 5000 rpm for 15 minutes. The obtained resin particles were observed with a scanning electron microscope (SEM) and the number average particle diameter was measured. The number average particle diameter was 8.5 nm.

  The resin particles obtained in the examples have a nanometer size, and are useful as various materials or members in the electronic field, the optical field, and the like, where functionalization (or refinement) is rapidly progressing.

  Since the resin particles of the present invention are fine and have small particle size variations, they are widely used in plastic products, rubber products, cosmetics, foods, pharmaceuticals, adhesives, paints (or coating agents), electronic fields, optical fields, and the like. In the field, it is useful as various materials (or members) such as additives. In particular, since the resin particles of the present invention are excellent in heat resistance and various optical properties (for example, transparency, high refractive index, low birefringence, etc.), they are useful for optical applications. Spacers, various additives [additives for coating agents (blocking agents, slip agents, etc.), rheology control agents (for example, rheology control agents for top coats, etc.), light diffusing agents, matting agents, fillers, It is useful as an anti-blocking agent (for example, an anti-blocking agent for films, etc.).

DESCRIPTION OF SYMBOLS 1 ... Plug 2 ... Deposition pipe 3 ... Receiver 4 ... Solvent supply pipe 5 ... Resin solution supply pipe 4a, 5a ... Supply port 4b ... Spraying port 5b ... Outlet 6 ... Pump 7a ... 1st flow path 7b ... 2nd Flow path

Claims (11)

Resin particles composed of a fluorene-containing polyester-based resin containing a 9,9-bisarylfluorene skeleton,
Fluorene-containing polyester resin is represented by the following formula (1)
(In the formula, Z ¹ and Z ² are the same or different and each represents an aromatic hydrocarbon group. R ^1a and R ^1b represent the same or different alkylene group, and R ^2a and R ^2b represent the same or different hydrocarbon. Group, alkoxy group, cycloalkoxy group, aryloxy group, aralkyloxy group, acyl group, alkoxycarbonyl group, halogen atom, nitro group, cyano group or substituted amino group, R ^3a and R ^3b are the same or different and carbonized A hydrogen group, an alkoxy group, a halogen atom, a nitro group, a cyano group or a substituted amino group, wherein m and n are the same or different and are 0 or an integer of 1 or more, and h1 and h2 are the same or different and represent 0-4. An integer, j1 and j2 are the same or different and are integers of 0 to 4)
And a compound represented by the following formula (2)
HO—R ^1c —OH (2)
(In the formula, R ^1c represents an alkylene group.)
A polyester system having a weight average molecular weight of 20,000 to 45,000, comprising at least a polymerization component of a diol component containing a diol component represented by: and a dicarboxylic acid component optionally having one or more substituents. Resin,
The substituent that the dicarboxylic acid component may have is an alkyl group, a cycloalkyl group, an aryl group, a haloalkyl group, an alkoxy group, a haloalkoxy group, an alkoxycarbonyl group, an acyl group, a substituted amino group, a halogen atom, or a nitro group. And at least one selected from a cyano group,
The ratio (molar ratio) between the compound represented by the formula (1) and the diol component represented by the formula (2) is the former / the latter = 95/5 to 65/35,
Resin particles having a number average particle diameter of nanometer size.   The resin particles according to claim 1, wherein the number average particle diameter is 1 to 500 nm, and the coefficient of variation of the number average particle diameter is 35% or less.   The resin particles according to claim 1 or 2, wherein the number average particle diameter is 1 to 30 nm. A resin solution containing a fluorene-containing polyester resin (A) containing a 9,9-bisarylfluorene skeleton, a solvent (B) capable of dissolving the fluorene-containing polyester resin (A), and the fluorene-containing polyester resin The resin particle according to any one of claims 1 to 3 , wherein the resin solution is refined by contacting a solvent (C) that is a poor solvent of (A) and is miscible with the solvent (B). how to. Claims wherein the resin solution is further contacted with at least one solvent (D) selected from aliphatic ketones and carboxylic acid alkyl esters, which is an intermediate solvent (D) different from the solvent (B) and the solvent (C). Item 5. The production method according to Item 4 . The manufacturing method of Claim 5 which makes the liquid mixture containing a resin solution and a solvent (D) and a solvent (C) contact. The manufacturing method according to claim 4 , wherein the other is dropped into contact with one of the resin solution and the solvent (C) under stirring. The production method according to claim 7 , wherein the solvent (C) is added dropwise to the resin solution with stirring. The production method according to claim 7 or 8 , wherein a mixed solution containing the resin solution and the solvent (D) according to claim 5 is used as the resin solution. The manufacturing method of Claim 4 which sprays a solvent (C) with respect to a resin solution. The manufacturing method of Claim 10 which sprays a solvent (C) with the spraying quantity of 100-10000 mL / min with respect to the resin solution which distribute | circulates at the flow volume of 1 mL / min.