JP2009167231A - Fluorene-based polyester resin fine particle and process for preparing same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a process for preparing fluorene-based polyester resin fine particles excellent in both transparency and heat resistance properties. <P>SOLUTION: The fluorene-based polyester resin fine particles are prepared by melt blending a fluorene-based polyester resin with a water-soluble polymer not compatible with the fluorene-based polyester resin, dispersing a dispersed phase consisting of the fluorene-based polyester resin in a continuous phase consisting of the water-soluble polymer, and then eluting the water-soluble polymer. The vinyl alcohol-based resin may be used as the water-soluble polymer. The ratio (weight ratio) of the fluorene-based polyester resin to the water-soluble polymer may be of the order of the former/the latter=1/99-50/50. The water-soluble polymer may be eluted by using the water. Also, in the preparing process, the average particle size of the fine particles may be of the order of 0.1-5 μm. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to fluorene-based polyester resin fine particles excellent in both properties of transparency and heat resistance, a method for producing the same, a composite material using the resin fine particles, and a method for producing the same.

  Known methods for producing polymer fine particles include physical methods such as a gas phase method and a pulverization method, and chemical methods such as a liquid phase method.

  In the gas phase method, a method of spraying a polymer solution under heating is mainly performed. However, a large-scale facility is required, and very strict control is required for manufacturing conditions. In addition, in the gas phase method, in addition to the poor surface smoothness of the polymer fine particles, the particle size distribution is large, and aggregation of the polymer fine particles is unavoidable.

  In addition, as a pulverization method, for example, Japanese Patent Application Laid-Open No. 2004-130305 (Patent Document 1) discloses a high-speed method for finely pulverizing powder by rotating a processing container containing a plurality of pulverization medium balls and powder. In the powder reaction apparatus, at least one guide vane that changes a movement direction of the grinding media ball based on rotation of the processing container is disposed in the processing container, and the movement direction is changed by the guide vane. A high-speed powder reaction apparatus is disclosed in which a powdered grinding medium ball collides with the powder on the wall surface in the processing container to make the powder fine particles. However, in such a method, the particles cannot be made smaller than a certain size, the surface smoothness is inferior, and the particle size distribution is wide. Further, in this method, the particles are easily condensed due to heat of pulverization.

  Examples of the liquid phase method include a coprecipitation method using a difference in solubility, a uniform precipitation method, and a polymerization method using a monomer suspension or a monomer emulsion. For example, JP-A-6-206950 (Patent Document 2) includes (meth) acrylic acid ester of alcohol, vinyl ester of saturated aliphatic carboxylic acid, olefin, vinyl aromatic compound, vinyl halide and / or vinyl ether. A latex based on at least one or more selected is polymerized in the first step, where a free radical initiator is added to the polymer latex, and in the second step, the mixture is brought to a temperature at which free radicals are decomposed. Core / shell dispersion in a two-step emulsion polymerization process, wherein the latex polymer is grafted after the addition of a grafted monomer phase containing monomers that are heated to and / or added and / or form a homopolymer A method for producing a fine-grain graft copolymer latex is disclosed. However, in such a method, it is difficult to separate and purify the polymer fine particles, and the surfactant and the flocculant remain in the polymer fine particles. Depending on the use, the surfactant and the flocculant have an adverse effect on the fine particles. . In particular, this method requires the use of a radically polymerizable monomer and cannot be applied to a condensation-polymerized resin (such as a polyester resin).

In order to solve these problems, for example, Japanese Patent Laid-Open No. 9-165457 (Patent Document 3) describes a mixture weight ratio (A) of a water-soluble polymer (A) and a thermoplastic resin (B) that can be melt-molded. ) / (B) = 99/1 to 30/70 to obtain a melt-molded product, which is then contacted with water to remove the water-soluble polymer (A) to produce resin fine particles. A method is disclosed. This document describes polyvinyl alcohol resins, modified starches, polyethylene oxides and the like as water-soluble polymers. Further, it is described that the thermoplastic resin (B) is preferably a polyolefin resin, a polyester resin, a polyamide resin, or a saponified ethylene-vinyl acetate copolymer. This document describes that as the polyester resin, polyethylene terephthalate, polybutylene adipate, poly (ethylene-2,6-naphthalate), polyethylene terephthalate-polyethylene adipate copolymer, and the like are used. However, since this method uses a crystalline polyalkylene arylate resin or an aliphatic polyester, it is difficult to achieve both transparency and heat resistance of the resin fine particles. In addition, this document describes that resin fine particles can be used for fillers, but does not describe a combination of resin fine particles and inorganic fine particles. Furthermore, a large amount of inorganic fine particles cannot be contained in the resin.
JP 2004-130305 A (Claim 2) JP-A-6-206950 (Claim 1) JP-A-9-165457 (Claim 1, paragraph numbers [0006] [0013] and [0015])

  Accordingly, an object of the present invention is to provide a fluorene-based polyester resin fine particle excellent in both properties of transparency and heat resistance, a method for producing the same, a composite material using the fluorene-based polyester resin fine particles, and a method for producing the same. It is in.

  Another object of the present invention is to provide a fluorene-based polyester resin fine particle having a small particle size and excellent surface smoothness, a method for producing the same, a composite material using the fluorene-based polyester resin fine particles, and a method for producing the same. It is in.

  Still another object of the present invention is to provide fluorene-based polyester resin fine particles having a narrow particle size distribution, a method for producing the same, a composite material using the fluorene-based polyester resin fine particles, and a method for producing the same.

  Another object of the present invention is to provide a composite material uniformly mixed even if the content of inorganic fine particles is large, and a method for producing the same.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors dispersed a dispersed phase composed of a fluorene-based polyester resin in a continuous phase composed of a water-soluble polymer, and then dispersed the water-soluble polymer. As a result, it was found that fluorene-based polyester resin fine particles excellent in both transparency and heat resistance could be produced, and the present invention was completed.

  That is, in the present invention, a fluorene-based polyester resin and a water-soluble polymer that is incompatible with the fluorene-based polyester resin are melt-kneaded and the fluorene-based polyester is contained in a continuous phase composed of the water-soluble polymer. After the dispersed phase composed of the polyester resin is dispersed, the water-soluble polymer is eluted to produce fluorene-based polyester resin fine particles. As the water-soluble polymer, a vinyl alcohol resin may be used. The ratio (weight ratio) between the fluorene-based polyester resin and the water-soluble polymer may be about the former / the latter = 1/99 to 50/50. In the production method, the water-soluble polymer may be eluted using water. Moreover, in the said manufacturing method, about 0.1-5 micrometers may be sufficient as the average particle diameter of microparticles | fine-particles.

  The present invention also includes fluorene-based polyester resin fine particles obtained by the above production method.

  The present invention also includes a method for producing a composite material by pressing and / or thermoforming a powder composition composed of the fine particles and inorganic fine particles. In the manufacturing method, the average particle size of the inorganic fine particles may be smaller than the average particle size of the fluorene-based polyester resin fine particles. When such a powder composition is used, even if the content of the inorganic fine particles is large, it can be easily and uniformly mixed with the fluorene-based polyester resin. In the production method, the ratio (weight ratio) between the fluorene-based polyester resin fine particles and the inorganic fine particles may be about the former / the latter = 99/1 to 50/50. Further, the present invention includes a composite material obtained by the manufacturing method.

  In the present invention, in order to elute the water-soluble polymer after dispersing the dispersed phase composed of the fluorene-based polyester resin in the continuous phase composed of the water-soluble polymer, both transparency and heat resistance are achieved. Fluorene-based polyester resin fine particles having excellent characteristics can be produced. Furthermore, fluorene-based polyester resin fine particles having a small particle size and excellent surface smoothness can be produced. Furthermore, fluorene-based polyester resin fine particles having a narrow particle size distribution can be produced. In addition, since the powder composition composed of the fluorene-based polyester resin fine particles and the inorganic fine particles is pressed and / or thermoformed, the powder composition is uniformly mixed with the fluorene-based polyester resin even if the content of the inorganic fine particles is large. be able to.

The fluorene-based polyester resin fine particles of the present invention include a step of melt-kneading a fluorene-based polyester resin and a water-soluble polymer that is incompatible with the fluorene-based polyester resin, and a step of eluting the water-soluble polymer. It can manufacture by going through.
(Fluorene polyester resin)
The fluorene-based polyester resin is an esterification reaction between a diol component composed of at least a diol having a fluorene skeleton (a diol component composed of a diol having a 9,9-bis (hydroxyaryl) fluorene skeleton) and a dicarboxylic acid component. The polyester resin obtained by is included. Such a fluorene-based polyester resin usually has at least a repeating unit represented by the following formula (1).

(In the formula, A represents an aliphatic hydrocarbon residue, an alicyclic hydrocarbon residue or an aromatic hydrocarbon residue, and Z ¹ and Z ² are the same or different and represent an aromatic hydrocarbon residue. ⁴ represents a halogen atom or an alkyl group, R ^1a and R ^1b are the same or different and each represents an alkylene group, R ^2a , R ^2b , R ^3a and R ^3b are the same or different and represent an alkyl group, an alkoxy group, an aryl group A group, a cycloalkyl group, an aralkyl group, a nitro group or a cyano group, and m and n are the same or different and are an integer of 0 or 1. h1 and h2 are the same or different and are an integer of 0 to 6, j1 and j2 are the same or different and are integers of 0 to 4, and k is an integer of 0 or more.)
In A, the aliphatic hydrocarbon residue corresponds to a linear or branched C _1-10 aliphatic saturated hydrocarbon such as methane, ethane, propane, butane, isobutane, n-heptane, and n-octane. Groups (divalent groups) corresponding to linear or branched C _1-10 aliphatic unsaturated hydrocarbons such as ethylene, propylene, trimethylene, isobutene, etc. , A group corresponding to a linear or branched C _1-10 aliphatic saturated hydrocarbon (divalent group). In A, the alicyclic hydrocarbon residue includes a group corresponding to a C _5-10 cycloalkane ring such as cyclopentane, cyclohexane, cycloheptane, cyclooctane (divalent group), cyclopentene, cyclohexene, cyclooctene, etc. Corresponding to a group corresponding to a C _5-10 cycloalkene ring (divalent group), polycyclic saturated hydrocarbon ring such as bornane, norbornane, adamantane (for example, bicyclic or tricyclic C _7-10 hydrocarbon ring) Groups corresponding to polycyclic unsaturated hydrocarbon rings such as bornene and norbornene (for example, bicyclic or tricyclic C _7-10 unsaturated hydrocarbon rings) (bivalent groups), etc. Can be illustrated. Usually, the alicyclic hydrocarbon residue is a group (divalent group) corresponding to a C _5-10 cycloalkane ring. In A, examples of the aromatic hydrocarbon residue include groups (divalent groups) corresponding to C _6-14 aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, biphenyl, and indene. A represents the alicyclic hydrocarbon residue or the aromatic hydrocarbon residue (for example, a divalent group corresponding to a C _5-10 cycloalkane ring or a divalent group corresponding to a C _6-10 aromatic hydrocarbon ring. In particular, a phenylene group is preferable.

  In A, the position of the bond of the hydrocarbon residue corresponding to A is not particularly limited, and may be an asymmetric position or a symmetric position. For example, when A is a cyclohexane ring, the hydrocarbon residue corresponding to A may be a 1,2-cyclohexane-diyl group, a 1,3-cyclohexane-diyl group, or a 1,4-cyclohexane-diyl group. It may be a group.

As the substituent R ⁴ , a linear or branched C _1-6 such as a halogen atom (bromine atom, chlorine atom, fluorine atom, etc.), an alkyl group (methyl group, ethyl group, butyl group, t-butyl group, etc.) Alkyl group) and the like. R ⁴ is usually often inert to the esterification reaction. The substitution number k of the substituent R ⁴ can be selected in the range of an integer of 0 or more according to the carbon number of A and the like, and may generally be an integer of about 0 to 8 (for example, 0 to 2). The substitution position of the substituent R ⁴ is not particularly limited and can be selected according to the type of A.

In Z ¹ and Z ² , examples of the aromatic hydrocarbon residue include a group (divalent group) corresponding to a C _6-14 aromatic hydrocarbon ring such as benzene, naphthalene, and anthracene. Z ¹ and Z ² are preferably a phenylene group or a naphthylene group (for example, a phenylene group).

Examples of the alkylene group represented by R ^1a and R ^1b include linear or branched C _2-4 alkylene groups such as an ethylene group, a propylene group, a trimethylene group, and a tetramethylene group. 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 R ^2a , R ^2b , R ^3a and R ^3b , the alkyl group may be a linear or branched C chain such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, or a t-butyl group. _{A 1-5} alkyl group (especially _C1-4 alkyl group) can be illustrated. In R ^2a , R ^2b , R ^3a and R ^3b , examples of the alkoxy group include C _1-4 alkoxy groups such as methoxy group, ethoxy group, propoxy group and butoxy group (particularly C _1-3 alkoxy group). In R ^2a , R ^2b , R ^3a and R ^3b , examples of the aryl group include C _6-12 aryl groups such as a phenyl group and a naphthyl group. In R ^2a , R ^2b , R ^3a and R ^3b , cycloalkyl Examples of the group include C _5-10 cycloalkyl groups such as a cyclopentyl group and a cyclohexyl group. In R ^2a , R ^2b , R ^3a and R ^3b , examples of the aralkyl group include C _6-12 aryl-C _1-4 alkyl groups such as a benzyl group.

The substitution numbers h1 and h2 of the substituents R ^2a and R ^2b may generally be an integer of about 0 to 3 (for example, 0 to 2, particularly 0). The substitution positions of the substituents R ^2a and R ^2b are not particularly limited, and can be selected according to the type of Z ¹ and Z ² . Preferred substituents R ^2a and R ^2b are C _1-4 alkyl groups (particularly methyl groups), and preferred substitution numbers h 1 and h 2 are integers of about 0 to 2 (eg, 0 or 1).

The substitution numbers j1 and j2 of the substituents R ^3a and R ^3b may generally be an integer of about 0 to 2 (eg, 0 or 1). Substitution position of the substituent ^{R 3a} and ^{R 3b} is not particularly limited, preferred substituents ^{R 3a} and ^{R 3b} _{are C 1-4} alkyl group (particularly methyl group), the preferred substituents which j1 and j2 0 or 1 (For example, 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). .

  The fluorene-based polyester resin may be a homopolyester or a copolyester. Such a fluorene-based polyester resin may have, for example, at least a repeating unit represented by the above formula (1) and a repeating unit represented by the following formula (2).

(In the formula, A, R ⁴ and k are the same as above. R ^1c represents an alkylene group, and q is an integer of 1 or more.)
^Examples of the alkylene group represented by R ^1c include linear or branched C _2-10 alkylene groups such as an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, a hexamethylene group, and an octamethylene group. A preferred alkylene group is a linear or branched C _2-4 alkylene group (for example, ethylene group, tetramethylene group, etc.). In particular, when q ≧ 2, examples of the alkylene group represented by R ^1c include C _2-4 alkylene groups such as an ethylene group, a propylene group, and a butylene group, and q is 2 to 10, preferably 2 -7, More preferably, it may be an integer of about 2-5 (for example, 2-4). In the formula (2), the coefficient q is usually an integer of about 1 to 5, preferably about 1 to 3 (particularly 1).

  Such a fluorene-based polyester resin may or may not contain a unit represented by the formula (2). The ratio between the unit represented by the formula (1) and the unit represented by the formula (2) is the former / the latter (molar ratio) = 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 97/3 to 60/40, especially 95/5 to 65/35 (e.g. 90/10 to 65/35).

  Preferred fluorene-based polyester resins include (i) a repeating unit represented by the following formula (1a) and a repeating unit represented by the following formula (2a) in which the dicarboxylic acid component is a benzenedicarboxylic acid (particularly terephthalic acid) component. A fluorene-based polyester resin having (ii) a repeating unit represented by the following formula (1b) in which the dicarboxylic acid component is a cyclohexanedicarboxylic acid component, and a fluorene-based polyester resin having a repeating unit represented by the following formula (2b) Is included.

(Wherein, R ^1a and R ^1b are the same or different and each represents a C _2-4 alkylene group, R ^1c represents a C _2-4 alkylene group, R ^2a and R ^2b are the same or different, and C _{1- 4 represents} an alkyl group, m and n are integers of 1 to 3, and h1 and h2 are integers of 0 to 2.)

The weight average molecular weight of the fluorene-based polyester resin is, for example, 0.5 × 10 ^{4 to} 100 × 10 ⁴ , preferably 1 × 10 ⁴ to 50 × 10 ⁴ , and more preferably 1 × 10 ^{4 to} 25 × 10 ⁴ (for example, 1 × 10 ⁴ to 10 × 10 ⁴ ).

  Such a fluorene-based polyester resin is excellent in various properties such as high transparency, heat resistance, hydrophobicity, refractive index and the like, and a small increase in birefringence accompanying molding.

  The refractive index of the fluorene-based polyester resin is, for example, 1.55 or more (for example, about 1.59 to 1.7), preferably 1.60 or more (for example, about 1.60 to 1.65), more preferably. May be 1.605 or more (for example, about 1.605 to 1.63).

The photoelastic coefficient of the fluorene-based polyester resin is, for example, 7 × 10 ⁻¹² cm ² / dyn or less (for example, about 0.1 × 10 ^{−12 to} 6.5 × 10 ⁻¹² cm ² / dyn), Preferably it is 6 × 10 ⁻¹² cm ² / dyn or less (for example, about 1 × 10 ^{−12 to} 5.5 × 10 ⁻¹² cm ² / dyn), more preferably 5 × 10 ⁻¹² cm ² / dyn or less (for example, 2 × 10 ^{−12 to} 4.5 × 10 ⁻¹² cm ² / dyn).

  The fluorene-based polyester resin is usually a diol component composed of at least a diol represented by the following formula (3) (a diol having a 9,9-bis (hydroxyaryl) fluorene skeleton), and at least the following formula (5). It can obtain by making the dicarboxylic acid component containing these, and the dicarboxylic acid component containing these reactive derivatives react. Furthermore, as described above, each of the diol component and the dicarboxylic acid component may be a single component, and the diol component and / or the dicarboxylic acid component may include a copolymer component. For example, the diol component may be configured by combining a diol represented by the formula (3) and a diol represented by the following formula (4).

(In the formula, A, Z ¹ , Z ² , R ^1a , R ^1b , R ^2a , R ^2b , R ^3a , R ^3b , R ⁴ , m, n, h1, h2, j1, j2, and k are the above-mentioned compounds. The same as 1. R ^1c and q are the same as those in Chemical Formula 2)
The diol represented by the formula (3) includes 9,9-bis (hydroxyaryl) fluorenes and 9,9-bis (hydroxy (poly) alkoxyaryl) fluorenes.

As 9,9-bis (hydroxyaryl) fluorenes, 9,9-bis (4-hydroxyphenyl) fluorene (bisphenolfluorene, BPF); biscresol fluorene (BCF, for example, 9,9-bis (4-hydroxy) 9,9-bis (C _1-4 alkylhydroxyphenyl) fluorene, such as 3-methylphenyl) fluorene, 9,9-bis (3-hydroxy-4-methylphenyl) fluorene, etc .; 9,9-bis (diC _1-4 alkylhydroxyphenyl) fluorene such as 4-hydroxy-3,5-dimethylphenyl) fluorene, and 9,9-bis [2- (6-hydroxy) naphthyl] fluorene; 9 9,9-bis (2,9-bis [2- (6-hydroxy-5-methyl) naphthyl] fluorene, etc. Roh or di _{C 1-4} alkyl hydroxy naphthyl) fluorene; corresponding to these compounds, the substituents ^{R 2a} and ^{R 2b} is like _{C 5-10} cycloalkyl group or a _{C 6-12} aryl group bis (hydroxyaryl) Fluorenes are mentioned.

Moreover, as 9,9-bis (hydroxy (poly) alkoxyaryl) fluorenes, 1 to 10 moles of C _2-4 alkylene oxide (preferably 1 to 1 mole) with respect to 1 mole of hydroxyl groups of bis (hydroxyaryl) fluorenes. 5 mol, especially 1 to 3 mol) or a compound to which about 1 to 5 mol (preferably 1 to 3 mol, particularly 1 mol) of C _2-8 haloalkanol such as 3-chloropropanol is added. Typical 9,9-bis (hydroxy (poly) alkoxyaryl) fluorenes include 9,9-bis such as 9,9-bis (4-hydroxyethoxyphenyl) fluorene (bisphenoxyethanol fluorene, BPEF). [4- (hydroxy _{C 2-3} alkoxy) phenyl] fluorene; 9,9-bis (4-hydroxyethoxy-3-methylphenyl) fluorene (biscresol ethanol fluorene, BCEF), 9,9- bis (4-hydroxy 9,9-bis (alkylhydroxy C _2-3 alkoxyphenyl) fluorene such as isopropoxy-3-methylphenyl) fluorene; 9 such as 9,9-bis (4-hydroxyethoxy-3,5-dimethylphenyl) fluorene , 9-bis (di-hydroxy _{C 2-3} Turkey hydroxyphenyl) fluorene; 9,9-bis (4-hydroxyethoxy-3-phenyl) 9,9-bis fluorene (cycloalkyl hydroxy _{C 2-3} alkoxyphenyl) fluorene; 9,9-bis (4 9 such as 9,9-bis (arylhydroxy C _2-3 alkoxyphenyl) fluorene such as -hydroxyethoxy- _3- phenylphenyl) fluorene and 9,9-bis [2- (6-hydroxyethoxy) naphthyl] fluorene 9,9-bis (mono or dialkylhydroxy C ₂ ) such as 9,9-bis (hydroxyC _2-3 alkoxynaphthyl) fluorene; 9,9-bis [2- (6-hydroxyethoxy-5-methyl) naphthyl] fluorene _-3 alkoxynaphthyl) fluorene and the like.

Among these compounds, as 9,9-bis (hydroxyaryl) fluorenes, for example, 9,9-bis (4-hydroxyphenyl) fluorene (for example, BPF), 9,9-bis (C _1-4 ). Alkylhydroxyphenyl) fluorene (eg BCF) is preferred. The 9,9-bis (hydroxy (poly) alkoxyaryl) fluorenes, for example, 9,9-bis [4- (hydroxy _{C 2-3} alkoxy) phenyl] fluorene (e.g., BPEF), 9,9-bis (Alkylhydroxy C _2-3 alkoxyphenyl) fluorene (for example, BCEF) and the like are preferable. As the diol component represented by the above formula (3), 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene is often used. These compounds may be used alone or in combination of two or more.

  The diol represented by the above formula (3) {for example, 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene} has heat resistance due to having a rigid fluorene ring and two aromatic rings. In addition to improving the transparency, the planes of these three aromatic rings are non-crystalline due to the conformation in which the planes of the three aromatic rings are orthogonal to each other, so that the transparency can also be improved.

The diol represented by the formula (4) can be used as a copolymerization component and is not always necessary. Examples of the diol represented by the formula (4) include alkylene glycol (for example, ethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, tetramethylene glycol, hexanediol, neopentyl glycol, octanediol, decanediol. Linear or branched C _2-12 alkylene glycols, etc.), (poly) oxyalkylene glycols (eg, di to tetra C _2-4 alkylene glycols such as diethylene glycol, triethylene glycol, dipropylene glycol, etc.). It can be illustrated. These diols can be used alone or in combination of two or more. Preferred diols are linear or branched C _2-10 alkylene glycols, especially C _2-6 alkylene glycols (eg, linear or branched C 2 C such as ethylene glycol, propylene glycol, 1,4-butanediol). _2-4 alkylene glycol). As the diol, at least ethylene glycol is often used.

  The diol represented by the above formula (4) (for example, ethylene glycol) is useful as a copolymer component for enhancing polymerization reactivity and imparting flexibility to the resin. In addition, since a refractive index, heat resistance, etc. may fall by introduction | transduction of a copolymerization component, generally it seems that the one where a copolymerization ratio is as small as possible is good.

  The ratio (molar ratio) between the diol represented by the formula (3) and the diol represented by the formula (4) is the former / the latter = 100/0 to 10/90 (for example, 100/0 to 30/70). Can be selected from a range of degrees, usually 99/1 to 50/50, preferably 99/1 to 60/40, more preferably 99/1 to 70/30, especially 97/3 to 75/25 (e.g. 95/5 to 80/20).

  If necessary, the diols represented by the above formulas (3) and (4) may be added to alicyclic diols (for example, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 2,2-bis). Bis (hydroxycycloalkyl) alkanes such as (4-hydroxycyclohexyl) propane, bis ((hydroxyalkoxy) cycloalkyl) alkanes such as 2,2-bis (4- (2-hydroxyethoxy) cyclohexyl) propane), Aromatic diols (for example, biphenol, bis (hydroxyaryl) alkanes such as 2,2-bis (4-hydroxyphenyl) propane, bis (2,2-bis (4- (2-hydroxyethoxy) phenyl) propane, etc. (Hydroxyalkoxy) aryl) alkane, xylylene glycol, etc.) It may be used in conjunction look. These diols may be used alone or in combination of two or more. Furthermore, you may use together polyols, such as glycerol, a trimethylol propane, a trimethylol ethane, a pentaerythritol, as needed.

Among the dicarboxylic acid components containing the dicarboxylic acid represented by the formula (5) and their reactive derivatives, the aliphatic dicarboxylic acid component includes aliphatic saturated dicarboxylic acids (for example, malonic acid, succinic acid, glutaric acid, adipine acid, pimelic acid, suberic acid, azelaic acid, C _1-10 alkane such as sebacic acid - such as dicarboxylic acid), aliphatic unsaturated dicarboxylic acids (e.g., maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid and the like C _2-10 alkene-dicarboxylic acid, etc.), their reactive derivatives (acid anhydrides such as succinic anhydride, lower C _1-4 alkyl esters such as dimethyl ester and diethyl ester, acid halides corresponding to dicarboxylic acid, etc. And derivatives capable of forming esters). Usually, the aliphatic dicarboxylic acid component is a C _2-8 alkane-dicarboxylic acid or a reactive derivative thereof.

Among the dicarboxylic acid components including the dicarboxylic acid represented by the formula (5) and their reactive derivatives, the alicyclic dicarboxylic acid component includes cycloalkanedicarboxylic acids (cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid). _{C5- 10} cycloalkane-dicarboxylic acid such as 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, cycloheptanedicarboxylic acid), cycloalkene dicarboxylic acids (C _5-10 cycloalkene such as tetrahydrophthalic acid) - dicarboxylic acid), polycyclic alkane dicarboxylic acids (Bol nonanedicarboxylic acid, norbornane carboxylic acid, di-or tricyclic C _7-10 alkanes such as adamantane dicarboxylic acid - dicarboxylic acid), polycyclic alkene dicarboxylic acids (Bol annual carboxylic acid Di- or tricyclic C _7-10 alkene such as norbornene dicarboxylic acid - dicarboxylic acid), acid anhydrides such as those reactive derivatives (hexahydrophthalic anhydride, dimethyl ester, lower C _1-4 alkyl esters such as diethyl ester, dicarboxylic Examples thereof include derivatives capable of forming an ester such as acid halides corresponding to acids. Usually, the alicyclic dicarboxylic acid component is C _5-10 cycloalkane-dicarboxylic acid or a reactive derivative thereof.

Among the dicarboxylic acid components including the dicarboxylic acid represented by the formula (5) and their reactive derivatives, the aromatic dicarboxylic acid component includes C _6-14 such as phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, and the like. C _12-14 biphenyl-dicarboxylic acid such as arene-dicarboxylic acid, biphenyl-4,4′-dicarboxylic acid or reactive derivatives thereof (acid anhydride such as phthalic anhydride, lower C ₁ such as dimethyl ester, diethyl ester, etc. _-4 alkyl esters, derivatives capable of forming esters such as acid halides corresponding to dicarboxylic acids), and the like. Usually, the aromatic dicarboxylic acid component is C _6-12 arene-dicarboxylic acid or a reactive derivative thereof.

  These dicarboxylic acid components can be used alone or in combination of two or more. The ratio (molar ratio) between the alicyclic dicarboxylic acid or aromatic dicarboxylic acid and the aliphatic dicarboxylic acid is the former / the latter = 100/0 to 50/50, preferably 95/5 to 70/30, more preferably 90. It may be about / 10 to 80/20. Furthermore, if necessary, a branched structure may be introduced into the fluorene-based polyester resin by using a polycarboxylic acid such as tricarboxylic acid or tetracarboxylic acid in combination. Of these dicarboxylic acid components, 1,4-cyclohexanedicarboxylic acid or reactive derivatives thereof (such as dimethyl 1,4-cyclohexanedicarboxylate) and terephthalic acid or reactive derivatives thereof (such as dimethyl terephthalate) are often used. .

  Various properties such as refractive index, transparency, mechanical strength and moldability of the resulting fluorene polyester resin can be adjusted by the dicarboxylic acid component, so the type of dicarboxylic acid component should be selected according to the purpose. Can do.

  The ratio (molar ratio) between the dicarboxylic acid component and the diol component is usually the former / the latter = 1.5 / 1 to 0.7 / 1, preferably 1.2 / 1 to 0.8 / 1 (especially 1 About 1/1 to 0.9 / 1).

  JP, 2004-315676, A can be referred to for the manufacturing method of fluorene polyester resin. The production method of the fluorene-based polyester resin is not particularly limited. Conventional methods such as transesterification, melt polymerization (direct polymerization, etc.), solution polymerization in an organic solvent, and interface using acid halide Examples thereof include a polymerization method. When a dicarboxylic acid and bis (hydroxyaryl) fluorenes and, if necessary, a copolymer component (such as alkylene glycol) are reacted directly by a polymerization method, the esterification reaction proceeds smoothly even under extremely mild conditions.

Although the reaction can be carried out in the absence of a catalyst, it is preferable to use a catalyst in order to prevent the resin from being colored and to obtain a resin having a predetermined polymerization degree under milder conditions. As the catalyst, various catalysts used for the production of fluorene-based polyester resins, for example, metal catalysts can be used. As the metal catalyst, for example, a metal compound containing an alkali metal (such as sodium), an alkaline earth metal (such as magnesium or barium), or a transition metal (such as zinc, cadmium, lead, or cobalt) is used. Examples of the metal compound include alkoxide, organic acid salt (acetate, propionate, etc.), inorganic acid salt (borate, carbonate, etc.), metal oxide and the like. These catalysts can be used alone or in combination of two or more. The amount of the catalyst used is, for example, about 0.01 × 10 ^{−4 to} 100 × 10 ⁻⁴ mol, preferably about 0.1 × 10 ⁻⁴ to 10 × 10 ⁻⁴ mol, with respect to the dicarboxylic acid component. Also good.

The reaction can usually be performed in an inert gas (nitrogen, helium, etc.) atmosphere. The reaction may be carried out under normal pressure or under reduced pressure (for example, 1 to 100 torr (about 1 × 10 ² to 1 × 10 ⁴ Pa)). The reaction temperature can be about 150-270 degreeC (preferably 180-260 degreeC, More preferably, it is 200-250 degreeC) grade, for example. After completion of the reaction, the resin may be purified by a conventional method if necessary.

  When an aliphatic dicarboxylic acid is used as the dicarboxylic acid represented by the formula (5), the resulting fluorene-based polyester resin has easy moldability.

  Moreover, when alicyclic dicarboxylic acid is used as dicarboxylic acid represented by Formula (5), the obtained fluorene-type polyester resin has very high transparency. In addition, since the molding fluidity is excellent, a small amount of a copolymer component such as alkylene glycol (ethylene glycol or the like) may be used, and the original physical properties (for example, refractive index, heat resistance, etc.) of the resin can be maintained.

  Furthermore, when an aromatic dicarboxylic acid is used as the dicarboxylic acid represented by the formula (5), the mechanical strength and refractive index of the resulting fluorene-based polyester resin are improved. In addition, although molding fluidity is lowered and transparency may be generally lowered due to stress strain or molecular orientation, diol (bis (hydroxyaryl) fluorenes) having a fluorene skeleton and aromatic dicarboxylic acid are polymerized. By doing so, a fluorene-based polyester resin having high transparency can be obtained. Further, when alkylene glycol (ethylene glycol or the like) is used as a copolymer component of the diol component, the fluidity can be improved and a resin suitable for molding can be obtained.

(Water-soluble polymer)
The water-soluble polymer is not particularly limited as long as it is incompatible with the fluorene-based polyester resin, and examples thereof include vinyl alcohol resins (for example, polyvinyl alcohol, vinyl alcohol-ethylene sulfonic acid copolymer, vinyl alcohol). -Maleic acid copolymer, etc.), vinyl ether resins (polyvinyl methyl ether, polyvinyl ethyl ether, vinyl alkyl ether-vinyl alkyl ethers such as maleic acid copolymers or copolymers), vinyl pyrrolidone resins (polyvinyl) Pyrrolidone; copolymer of vinyl pyrrolidone and vinyl acetate), polyalkylene glycol (polyethylene glycol, polyoxyethylene-polyoxypropylene copolymer, etc.), acrylamide resin (polyacrylamide, etc.), water Sex polyamide water-soluble synthetic resin, such as (poly etc. oxyethylene units polyoxy C _2-3 polyether polyamide having an alkylene unit, etc.); (such as methyl) cellulose resins [alkylcelluloses, hydroxyalkylcelluloses (hydroxyethylcellulose (HEC ), Hydroxypropylcellulose (such as HPC)), hydroxyalkylalkylcellulose (such as hydroxypropylmethylcellulose), carboxyalkylcellulose (such as carboxymethylcellulose (CMC)), alkyl-carboxyalkylcellulose (such as methylcarboxymethylcellulose)] and the like Derivatives [CMC salts such as sodium carboxymethyl cellulose (such as alkali metal salts)] and the like It is. These water-soluble polymers can be used alone or in combination of two or more. Of these water-soluble polymers, vinyl alcohol resins such as polyvinyl alcohol are often used.

  The water-soluble polymer is usually often miscible with the fluorene-based polyester resin.

  The ratio (weight ratio) between the fluorene-based polyester resin and the water-soluble polymer is the former / the latter = 1/99 to 50/50 (for example, 5/95 to 45/55), preferably 10/90 to 43. / 57, more preferably about 15/85 to 40/60.

  In the production method of the present invention, additives may be used as necessary. The additive may be previously contained in the fluorene-based polyester resin and / or the water-soluble polymer, and is added to the resin composition containing the fluorene-based polyester resin and the water-soluble polymer in the process of melt kneading described later. May be.

  Examples of the additive include plasticizers (esters, phthalic acid compounds, epoxy compounds, sulfonamides, etc.), flame retardants (inorganic flame retardants, organic flame retardants, colloid flame retardants, etc.), stabilizers, and the like. (Antioxidants, UV absorbers, heat stabilizers, etc.), antistatic agents, antifoaming agents, lubricants, mold release agents (natural waxes, synthetic waxes, linear fatty acids or their metal salts, acid amides, etc.) Etc. Moreover, in order to improve refractive index and heat resistance, a sulfur compound, polysilane, etc. may be included in the range which does not impair transparency. These additives may be used alone or in combination of two or more.

  The ratio of the additive is 0.1 to 30 parts by weight, preferably 0.3 to 20 parts by weight, and more preferably 0 to 100 parts by weight of the total amount of the fluorene polyester resin and the water-soluble polymer. It may be about 5 to 10 parts by weight.

  The melt-kneading of the fluorene-based polyester resin and the water-soluble polymer is not particularly limited as long as the dispersed phase composed of the fluorene-based polyester resin can be dispersed in the continuous phase composed of the water-soluble polymer. It can be performed using a melt kneader, for example, a single or vented twin screw extruder, a Banbury mixer, a kneader, a mixing roll, and the like. Prior to melt-kneading, for example, using a mixer (tumbler, V-type blender, Henschel mixer, Nauta mixer, ribbon mixer, mechanochemical device, etc.), etc., fluorene-based polyester resin, water-soluble polymer and necessary May be premixed with additives and the like.

  The melt kneading temperature may be, for example, about 150 to 300 ° C, preferably 160 to 280 ° C, and more preferably about 170 to 260 ° C. Further, it may be cooled after completion of melt kneading, or may be cooled in a state where the dispersed phase is deformed by melt kneading.

  By such a method, a dispersion in which a continuous phase (sea or matrix) and a dispersed phase (island) are formed can be obtained. The shape of the dispersed phase is not particularly limited, and may be, for example, a rod shape, an ellipsoid shape (football type shape or a spheroid shape), a spherical shape, etc., and is usually a spherical shape in many cases. Further, the dispersed phase may be flat.

  In order to efficiently dissolve the water-soluble polymer, the dispersion may be pulverized using, for example, a conventional pulverizer (hammer mill, cutter mill, pelletizer, etc.).

  By eluting the water-soluble polymer constituting the continuous phase in the dispersion, fluorene-based polyester resin fine particles can be obtained. For elution of the water-soluble polymer, water, a mixed solvent of water and a water-soluble organic solvent, or the like can be used. Usually, water (for example, warm water) is often used.

Examples of the water-soluble organic solvent include alcohols (such as C _1-4 alkanols such as methanol, ethanol, propanol, isopropanol, and butanol), ketones (such as acetone), ethers (such as dioxane and tetrahydrofuran), and organic carboxyls. Acids (such as acetic acid), cellosolves (such as _C1-4 alkyl cellosolves such as methyl cellosolve and ethyl cellosolve), cellosolve acetates ( _C1-4 alkyl cellosolve acetates such as ethyl cellosolve acetate), carbitols (methyl) And C _1-4 alkyl carbitols such as carbitol and ethyl carbitol). These water-soluble organic solvents can be used alone or in combination of two or more.

  In the mixed solvent of water and the water-soluble organic solvent, the ratio (weight ratio) of the water-soluble organic solvent is not limited as long as the water-soluble polymer can be eluted and the fluorene-based polyester resin fine particles are not eluted, For example, with respect to 100 parts by weight of water, 20 parts by weight or less (for example, 0.01 to 15 parts by weight), 10 parts by weight or less (for example, 0.03 to 5 parts by weight), more preferably 3 parts by weight or less ( For example, it may be about 0.05 to 1 part by weight.

  Examples of the method for eluting the water-soluble polymer include a method in which water and a water-soluble polymer are brought into contact. For example, a method in which the dispersion is immersed in water, a method in which the dispersion is washed with water, and the like. Can be mentioned.

  The elution temperature may be about 0 to 100 ° C, preferably 10 to 90 ° C, more preferably about 20 to 85 ° C (particularly 30 to 80 ° C).

  The fluorene-based polyester resin fine particles thus obtained have a small particle size and excellent surface smoothness. Furthermore, the fluorene-based polyester resin fine particles have a narrow particle size distribution.

  Examples of the shape of the fluorene-based polyester resin fine particles include those exemplified in the section of the shape of the dispersed phase, and it is particularly preferable that the shape is particularly spherical. As described above, when cooled after melt-kneading, the shape of the fluorene-based polyester resin fine particles can be formed into a spherical shape, and when cooled with the dispersed phase deformed by melt-kneading, it can be formed into a rod shape, an ellipsoidal shape, or the like. . The fluorene-based polyester resin has high hydrophobicity, so that the dispersed phase is easily dispersed in a spherical shape in the continuous phase, and fine particles having a small particle diameter are obtained.

  The average particle size of the fluorene-based polyester resin fine particles is 0.1 to 30 μm (for example, 0.3 to 20 μm), preferably 0.5 to 10 μm, more preferably 1 to 5 μm (particularly 1.5 to 3 μm). However, it is often about 0.1 to 5 μm. The aspect ratio of the fluorene-based polyester resin fine particles can be selected from about 1 to 10, preferably about 1.1 to 5, more preferably about 1.2 to 3 (for example, 1.3 to 2). Usually, it is often about 1 to 3.

  Such fluorene-based polyester resin fine particles are excellent in both characteristics of transparency and heat resistance. Furthermore, the particle size is small and the surface smoothness is excellent. Furthermore, it has high affinity with various additives, and a composite material can be easily produced.

  A composite material can be produced by pressurizing and / or thermoforming a powder composition composed of the fluorene-based polyester resin fine particles and inorganic fine particles.

  The powder composition can be obtained by mixing fluorene polyester resin fine particles and inorganic fine particles. For mixing, for example, the mixer exemplified in the section of preliminary kneading in the melt kneading can be used.

  The molding pressure may be, for example, about 1 to 100 MPa, preferably 3 to 80 MPa, more preferably about 5 to 50 MPa (for example, 8 to 30 MPa). The molding temperature may be, for example, about 150 to 300 ° C, preferably about 180 to 280 ° C, and more preferably about 200 to 270 ° C.

  The molding time may be, for example, 1 minute to 1 hour, preferably 3 to 30 minutes, and more preferably about 5 to 20 minutes.

  Since the fluorene-based polyester resin fine particles are used, even if the content of the inorganic fine particles is large, they can be uniformly mixed.

  Examples of the inorganic fine particles include fine particle inorganic fillers [silicates such as carbon black, graphite, kaolin, talc, and clay; metal oxides such as iron oxide, titanium oxide, zinc oxide, antimony oxide, and alumina; calcium Metal carbonates and sulfates such as magnesium and zinc; metal carbides such as silicon carbide, metal nitrides such as silicon nitride and boron nitride, etc.]. Of these inorganic fine particles, metal oxides such as titanium oxide are often used. The inorganic fine particles may be used alone or in combination of two or more.

  Examples of the shape of the inorganic fine particles include the shapes exemplified in the section of the shape of the dispersed phase.

  The average particle size of the inorganic fine particles is 10 nm to 80 μm (for example, 10 nm to 50 μm), preferably 15 nm to 10 μm (for example, 15 nm to 1 μm), more preferably 20 to 100 nm (for example, 20 to 80 nm, particularly 25 to 25 nm). About 60 nm). The average particle size of the inorganic fine particles may be larger or smaller than the average particle size of the fluorene-based polyester resin fine particles. When the average particle diameter of the inorganic fine particles is smaller than the average particle diameter of the fluorene-based polyester resin fine particles, even if the content of the inorganic fine particles is large, the inorganic fine particles can be efficiently and uniformly mixed with the fluorene-based polyester resin.

  The aspect ratio of the inorganic fine particles can be selected from the same range as the aspect ratio of the fluorene-based polyester resin fine particles.

  The ratio of the average particle size (B) of the inorganic fine particles to the average particle size (A) of the fluorene-based polyester resin fine particles (particle size ratio (B / A)) is 0.5 to 20, preferably 1 to 15 ( For example, it may be about 1.5 to 12), more preferably about 2 to 10 (particularly 3 to 8).

  The ratio (weight ratio) between the fluorene-based polyester resin fine particles and the inorganic fine particles is the former / the latter = 99/1 to 50/50, preferably 90/10 to 55/45, more preferably about 80/20 to 60/40. Usually, it is often about 95/5 to 50/50.

  The composite material thus obtained is uniformly mixed with the fluorene-based polyester resin even if the content of the inorganic fine particles is large.

  Fluorene-based polyester resin fine particles include optical spacers, various additives [additives to be added to coating agents (blocking agents, slip agents, etc.), rheology control agents (for example, rheology control agents for top coats), light diffusion Agent, matting agent, filler, anti-blocking agent (for example, anti-blocking agent for film, etc.)] and the like.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

  The characteristics of the obtained fluorene polyester resin fine particles were evaluated by the following methods.

[transparency]
For the transparency, light transmittance at a wavelength of 550 nm was measured using a UV-Vis spectrophotometer UV3600 manufactured by Shimadzu Corporation.

[Glossiness]
The glossiness was measured using a gloss meter (Gloss Checker) IG-330 manufactured by Horiba, Ltd.

[Glass-transition temperature]
The glass transition temperature was measured using a differential scanning calorimeter (manufactured by Shimadzu Corporation, “DSC-60”) under a nitrogen flow of 50 mL / min and a temperature rising condition of 10 ° C./min.

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 using a particle size distribution analyzer (manufactured by Nikkiso Co., Ltd., Microtrac UPA). was gotten. FIG. 1 shows a scanning electron micrograph of fluorene-based polyester resin fine particles, and FIG. 2 shows the particle size distribution of the fluorene-based polyester resin fine particles.

(Example 2)
The fluorene-based polyester resin fine particles obtained in Example 1 and titanium oxide (Ishihara Sangyo Co., Ltd., TTO-55D, particle size 30 to 50 nm) are premixed in a powder state at a ratio shown in Table 1. did. Next, the mixed powder composition was filled in a Teflon (registered trademark) ring having an inner diameter of 20 mm and a height of 20 mm to a height (thickness) of about 5 mm, and was heated between the hot presses heated to the temperatures shown in Table 1. The composite sheet was obtained by holding and pressing with a cylinder inscribed in a Teflon (registered trademark) ring for 10 minutes under a pressure of 10 MPa.

  The obtained composite sheet was a glossy white sheet and was sufficiently flexible. The transparency, glossiness, and glass transition temperature of the composite sheet were measured, and the cross section of the composite sheet was observed with a scanning electron microscope (manufactured by JEOL Ltd., field emission scanning electron microscope (FE-SEM)). The results are shown in Table 1 and FIG.

  As is clear from Table 1 and FIGS. 1 and 2, fluorene-based polyester resin fine particles having a smaller particle size and a narrow particle size distribution were obtained in the Examples as compared with Comparative Examples. Furthermore, it was found that the fluorene-based polyester resin fine particles have high transparency and gloss. Further, as is clear from FIG. 3, the composite sheet was uniformly mixed without agglomeration in the fluorene-based polyester resin even when the content of titanium oxide was large.

1 is a scanning electron micrograph of 50,000 times the fluorene-based polyester resin fine particles obtained in Example 1. FIG. The scale in the figure indicates 10 μm. FIG. 2 shows a particle size distribution curve in terms of the number of fluorene-based polyester resin fine particles obtained in Example 1. FIG. 3 is a scanning electron micrograph of 50,000 times the cross section of the composite sheet obtained in Example 2. The scale in the figure indicates 10 μm.

Claims (10)

  A fluorene-based polyester resin and a water-soluble polymer that is incompatible with the fluorene-based polyester resin are melt-kneaded, and the continuous phase composed of the water-soluble polymer is composed of the fluorene-based polyester resin. A method of producing fluorene-based polyester resin fine particles by dispersing a dispersed phase and then eluting a water-soluble polymer.   The production method according to claim 1, wherein a vinyl alcohol resin is used as the water-soluble polymer.   The method according to claim 1 or 2, wherein the ratio (weight ratio) between the fluorene-based polyester resin and the water-soluble polymer is the former / the latter = 1/99 to 50/50.   The manufacturing method in any one of Claims 1-3 which elute a water-soluble polymer using water.   The production method according to claim 1, wherein the fine particles have an average particle size of 0.1 to 5 μm.   Fluorene-based polyester resin fine particles obtained by the production method according to claim 1.   A method for producing a composite material by pressurizing and / or thermoforming a powder composition comprising the fluorene-based polyester resin fine particles and inorganic fine particles according to claim 6.   The production method according to claim 7, wherein the average particle size of the inorganic fine particles is smaller than the average particle size of the fluorene-based polyester resin fine particles.   The production method according to claim 7 or 8, wherein the ratio (weight ratio) between the fluorene-based polyester resin fine particles and the inorganic fine particles is the former / the latter = 99/1 to 50/50.   The composite material obtained by the manufacturing method in any one of Claims 7-9.