JPH05186538A - Spherical particle and its production - Google Patents

Abstract

PURPOSE:To obtain the title particle excellent in hardness, compressive strength, heat resistance and solvent resistance by using a specified polymer. CONSTITUTION:The title particle is made from a cross-linked phosphazene polymer desirably obtained by the emulsion polymerization or suspension polymerization of a curable phosphazene compound [e.g. 1,1,3,3,5,5-hexa(methacryloylethylenedioxy)cyclotriphosphazene] in the presence (absence) of a comonomer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to spherical particles and a method for producing the same, and more particularly to spherical particles made of a crosslinked phosphazene polymer having excellent hardness, compressive strength, heat resistance and solvent resistance, and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, fine particles of synthetic resin have been used in a wide variety of fields such as pigment dispersants, toner additives, powder molding binders, paper treating agents, and resin-reinforced fillers. There is. As such a fine particle polymer, for example, a polymer made of crosslinked polymethylmethacrylate, a benzoguanamine-based resin, a melamine-based resin, or the like has been used. However, although the above-mentioned resin products have their respective merits depending on the material, they have not yet fully met the demands in accordance with the expansion of fields of application. That is, there is a problem that hardness, compressive strength and heat resistance are low, and solvent resistance is insufficient.
Therefore, the present inventor has conducted diligent research to solve the above problems.

[0003]

As a result, it was found that the above problems can be solved by using spherical particles made of a crosslinked phosphazene polymer. The present invention is
It was completed based on this knowledge. That is,
The present invention provides spherical particles composed of a cross-linked phosphazene polymer, and the above cross-linking is carried out by emulsion-polymerizing or suspension-polymerizing a curable phosphazene compound in the presence or absence of a monomer for copolymerization. The present invention provides a method for producing spherical particles composed of a phosphazene polymer.

The spherical particles made of the crosslinked phosphazene polymer of the present invention are produced from various curable phosphazene compounds. As this curable phosphazene compound,
For example, the general formula (I)

[0005]

[Chemical 1]

(In the formula, A represents a polymerization-curable group, B represents a non-polymerization-curable group, and a and b are 0 <a and 0 ≦ b.
And a real number that satisfies a + b = 2. ) And a phosphazene compound having a repeating unit represented by), and there are various compounds depending on the type of each substituent. In the formula, A
Represents a polymerization-curable group, and the polymerization-curable group means a functional group that is cured by reaction with irradiation of ultraviolet rays, visible rays or electron beams, use of a chemical curing agent or heating, and is usually It is a group having a reactive double bond. There are various groups having this reactive double bond, and examples thereof include functional groups containing an acryloyl group, a methacryloyl group, a vinyl group or an allyl group. The functional group containing an acryloyl group or a functional group containing a methacryloyl group is an acryloyloxy group or a methacryloyloxy group,
Furthermore, the general formula (II)

[0007]

[Chemical 2]

(In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ² represents an alkylene group having 1 to 12 (preferably 1 to 5) carbon atoms (including a branched alkylene group)). It is something.

Specific examples of the group represented by the general formula (II) include 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, 6-hydroxy-3-methylhexyl methacrylate, 5-hydroxyhexyl methacrylate, 3-hydroxy-2-t-butylpropyl methacrylate, 3-hydroxy-2,2-dimethylhexyl Removal of hydrogen atom from hydroxyl groups in methacrylates such as methacrylate, 3-hydroxy-2-methyl-2-ethylpropyl methacrylate and 12-hydroxydodecyl methacrylate. Residues, and 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 3-hydroxybutyl acrylate, 4-hydroxybutyl acrylate, 5-hydroxypentyl acrylate, 6-hydroxy -3-Methylhexyl acrylate, 5-hydroxyhexyl acrylate, 3-hydroxy-2-t-butylpropyl acrylate, 3-hydroxy-2,2-dimethylhexyl acrylate, 3-hydroxy-2-methyl-2-
Examples thereof include a residue obtained by removing a hydrogen atom from a hydroxyl group in acrylates such as ethylpropyl acrylate and 12-hydroxydodecyl acrylate. Particularly preferred groups are 2-hydroxyethyl methacrylate residue and 2-hydroxyethyl acrylate residue.
Further, the functional group containing an acryloyl group or a methacryloyl group can be a compound represented by the general formula (I
II)

[0010]

[Chemical 3]

(Wherein R ¹ and R ² are the same as above), that is, a residue obtained by removing a hydrogen atom from a hydroxyl group of hydroxyalkyl-substituted (meth) acrylamide, and further represented by the general formula ( IV)

[0012]

[Chemical 4]

(In the formula, R ¹ is the same as the above.), That is, a residue obtained by removing one hydrogen atom from the amino group of acrylamide or methacrylamide may be mentioned. Furthermore, as the functional group containing an allyl group, in addition to the allyl group itself, for example, an allyloxy group (CH ₂
═CH—CH ₂ O—), but not limited to this allyloxy group, and widely represented by the general formulas (V) to (VII).

[0014]

[Chemical 5]

(Wherein R ¹ , R ³ and R ⁴ are the same as above), that is, a residue obtained by removing a hydrogen atom from a hydroxyl group of an allyl compound having one hydroxyl group. You can Specific examples of the functional groups represented by the general formulas (V) to (VII) include:

[0016]

[Chemical 6]

There is a residue obtained by removing a hydrogen atom from a hydroxyl group in an allyl compound such as. On the other hand, B in the general formula (I) is
As described above, the general formulas (VIII), (IX)

[0018]

[Chemical 7]

(In the formula, M is an oxygen atom, a sulfur atom or
Represents a mino group, R^FiveIs an alkyl group having 1 to 18 carbon atoms
Or represents a halogenated alkyl group having 1 to 18 carbon atoms. Well
R ⁶~ R^TenAre independently hydrogen atom and halogen atom
Child, alkyl group having 1 to 4 carbon atoms or ha having 1 to 4 carbon atoms
A rogenated alkyl group is shown. ) Represents a group represented by. one
Specific examples of general formula (VIII) include methoxy group and ethoxy group.
Group, propoxy group, butoxy group, pentyloxy group,
Xyloxy group, heptyloxy group, octyloxy group
Alkoxy groups such as, halogen (eg fluorine, chlorine,
A similar alkoxy group substituted with bromine, etc., methyl
O group, ethylthio group, propylthio group, butylthio group,
Pentylthio group, heptylthio group, octylthio group, etc.
Alkylthio group, halogen (eg fluorine, chlorine, odor
A similar alkylthio group substituted with
Mino group, ethylimino group, propylimino group, butyrui
Mino group, pentylimino group, hexyluimino group, hepti
Alkylimino such as ruimino group and octylimino group
Substitute with groups or halogens (eg fluorine, chlorine, bromine, etc.)
The similar alkylimino group etc.
It The group of formula (IX) is specifically a phenoxy group or a thiol group.
Phenyl group, halogenated phenoxy group (2, 4, 6-to
Libromophenoxy group, 4-bromophenoxy group, 2-
Chlorophenoxy group, 2,4-dichlorophenoxy group
And halogenated thiophenyl group (4-chlorophene)
Nylthio group) or aniline and halogenated
Aniline (2-chloroaniline, 2,4-dichloroani
Amino of phosphorus, 2,4,6-tribromoaniline, etc.
It is possible to name residues such as those in which a hydrogen atom has been removed from a group.
Wear.

Regarding a and b in the above-mentioned general formula (I), 0 <a ≦ 2, 0 ≦ b <2, and a + b =
It may be any real number that satisfies 2, but preferably 0.6 ≦ a ≦
2,0 ≦ b ≦ 1.4. The substituent A is a group that exerts a crosslinking action when the phosphazene compound of the general formula (I) is polymerized (crosslinked), and the substituent B controls the physical properties of the polymer and has a high polymerization performance. Is a group having an effect of regulating the. Therefore, by properly selecting a and b, various physical properties of the spherical particles of the present invention will be defined. However, since those with a = 0 have no curability, such phosphazene compounds are excluded from the scope of the present invention. However, a = 2, b = 0, that is,

[0021]

[Chemical 8]

The phosphazene compound having a repeating unit represented by the formula (A is the same as above) can be used as a raw material for the crosslinked phosphazene polymer of the present invention. The phosphazene compound used in the present invention is preferably one having a repeating unit of the above-mentioned general formula (I), but the degree of polymerization thereof is 3 or more, preferably 3 to 10,
The range is 000, more preferably 3 to 18, and most preferably 3 or 4 or a mixture thereof. Further, the repeating unit of the general formula (I) may be linked (polymerized) in a chain, but is preferably linked (polymerized) in a cyclic form. Specific examples of such a phosphazene compound are as follows.

[0023]

[Chemical 9]

Such a phosphazene compound can be produced by various methods and is not particularly limited. For example, when it is desired to introduce a group represented by the general formula (II) as the substituent A, a hydroxyalkyl (meth) acrylate corresponding to the general formula (II), that is, a general formula

[0025]

[Chemical 10]

(In the formula, R ¹ and R ² are the same as above.)
When a hydroxyalkyl (meth) acrylate represented by the formula (3) is used and a group represented by the general formula (III) is desired to be introduced as the substituent A, the corresponding general formula

[0027]

[Chemical 11]

(In the formula, R ¹ and R ² are the same as above.)
When using a hydroxyalkyl (meth) acrylamide represented by the formula (1) and introducing a group represented by the general formula (IV) as the substituent A, the corresponding general formula

[0029]

[Chemical 12]

When (meth) acrylamide represented by the formula (wherein R ¹ is the same as the above) is used, or when it is desired to introduce the groups represented by the general formulas (V) to (VIII) as the substituent A. , The corresponding general formula

[0031]

[Chemical 13]

(In the formula, R ¹ , R ³ and R ⁴ are the same as above.) Allyl alcohol, allylphenol, allyl ester of hydroxybenzoic acid or its derivative is used. On the other hand, in the group represented by the general formula (VIII) introduced as the substituent B, when M is an oxygen atom, an alkanol represented by R ⁵ OH (wherein R ⁵ is the same as the above),
Using halogenated alkanol or its derivative, M
Is a sulfur atom, an alkylmercaptan represented by R ⁵ SH (wherein R ⁵ is the same as above), a halogenated alkylmercaptan or a derivative thereof is used, and when M is an imido group, R ⁵ NH ₂ R ⁵ is the same as the above), and an alkylamine, a halogenated alkylamine or a derivative thereof is used. In the group represented by the general formula (IX) introduced as the substituent B, when M is an oxygen atom, the general formula

[0033]

[Chemical 14]

(Wherein, R ^{6 to} R ¹⁰ are the same as above), and when M is a sulfur atom, a general formula is used.

[0035]

[Chemical 15]

(Wherein R ^{6 to} R ¹⁰ are the same as above), and when M is an imide group, a general formula is used.

[0037]

[Chemical 16]

An aniline represented by the formula (wherein R ^{6 to} R ¹⁰ are the same as above) or a derivative thereof is used. The compound forming the substituent A and the compound forming the substituent B are mixed with chlorophosphazene (a cyclic compound represented by the formula (NPCl ₂ ) _n or a compound represented by the formula Cl ₄ P. (NPCl ₂ ) _n- 1.N.
By reacting with a chain compound represented by PCl ₃ (n is an integer of 3 or more, preferably 3 to 18), the desired phosphazene compound of the general formula (I) can be obtained. When the compound forming the substituent B is alcohol, mercaptan, phenol or thiophenol,
Alkalates, phenolates, mercaptides, and thiophenolates may be prepared by previously reacting an alkali metal such as sodium metal or potassium. Also,
In the reaction of the compound forming each of the substituents A and B with chlorophosphazene, it is preferable to use a dehydrohalogenating agent such as a tertiary amine. Examples of the tertiary amine include trimethylamine, triethylamine, triisopropylamine, tri-n-propylamine, tri-n-butylamine, pyridine, and the like. Of these, pyridine is preferable. Furthermore, this reaction is usually performed in an organic solvent. Examples of the organic solvent used include benzene, toluene, xylene, chloroform, cyclohexane, methylene chloride, tetrahydrofuran and 1,4-dioxane. These can be used alone or in combination. In the curable phosphazene compound obtained by the above reaction, it is preferable that all the chlorine atoms of chlorophosphazene which is a raw material are substituted with the above-mentioned substituents, but some chlorine may remain. By the reaction as described above, a curable phosphazene compound which is a main raw material of the crosslinked phosphazene polymer is obtained.

To form a crosslinked phosphazene-based polymer, the above-mentioned phosphazene compound or, if necessary, a monofunctional monomer and / or a polyfunctional monomer copolymerizable with the phosphazene compound and a conventional monomer are used. Emulsion polymerization or suspension polymerization may be carried out by adding additives. Monomers copolymerizable with phosphazene compounds (monomers for copolymerization)
Examples include silicone-modified curable compounds, polymerizable prepolymers, acryloyl groups, methacryloyl groups,
Examples thereof include a compound having a reactive double bond, such as a polymerizable monomer having a vinyl group or an allyl group. Here, the silicone-modified curable compound is not particularly limited as long as it is a compound having a silicone (silane) group and preferably a (meth) acrylate group in one molecule.

Specific examples of the silicone-modified curable compound include silicone-modified urethane acrylate and (meth)
Examples thereof include an acryloxysilane compound and a (meth) acrylate-modified polysiloxane. Also,
As the (meth) acryloxysilane compound, for example, γ-
Methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane and the like can be mentioned. As the (meth) acrylate-modified polysiloxane, there is a compound containing a silicone (silane) group and a (meth) acrylate group in one molecule. The mixing ratio of the curable phosphazene compound and the silicone-modified curable compound is not particularly limited and may be appropriately selected depending on the type of the silicone-modified curable compound. Usually, the curable phosphazene compound is 20 to 99.5 parts by weight, and the silicone-modified curable compound is 0.5 to 80 parts by weight. Preferably, the curable phosphazene compound is 40 to 99 parts by weight and the silicone-modified curable compound is 1 to 60 parts by weight.

Specific examples of the polymerizable monomer having an acryloyl group, a methacryloyl group and the like include methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate and 2-hydroxy. Monofunctional groups such as propyl (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, ethylene glycol di (Meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate , Bifunctional functional groups such as hydroxybivalic acid ester neopentyl glycol di (meth) acrylate, trifunctional functional groups such as trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate Mention may be made of polyfunctional compounds having groups or more.

On the other hand, examples of the polymerizable prepolymer include polyester (meth) acrylate, polyurethane (meth) acrylate, epoxy (meth) acrylate, polyether (meth) acrylate, melamine (meth) acrylate, oligo (meth) acrylate. , Alkyd (meth) acrylates, polyol (meth) acrylates, silicon (meth) acrylates, and other prepolymers having at least one (meth) acryloyl group. A particularly preferred prepolymer is polyester,
Epoxy and polyurethane (meth) acrylates. As the polyester (meth) acrylate,
For example, ethylene glycol, 1,4-butadiol,
Polyhydric alcohols such as 1,6-hexanediol, diethylene glycol trimethylolpropane, dipropylene glycol, polyethylene glycol, polypropylene glycol, pentaerythritol, dipentaerythritol and phthalic acid, adipic acid, maleic acid, trimellitic acid, itaconic acid A polyester obtained from a polybasic acid such as succinic acid, terephthalic acid, or alkenylsuccinic acid, and then (meth) acrylated is used. As the above-mentioned (meth) acrylated,
Examples of polyester (meth) acrylates such as adipic acid / 1,6-hexanediol / (meth) acrylic acid type, phthalic anhydride / propylene oxide / (meth) acrylic acid type, trimellitic acid / diethylene glycol / acrylic acid type You can Epoxy (meth) acrylate is obtained by esterifying an epoxy group of an epoxy resin with (meth) acrylic acid to make a functional group a (meth) acryloyl group. Specific examples thereof include bisphenol A-epichlorohydrin type epoxy resin / (meth) acrylic acid type, phenol novolak-epichlorohydrin type epoxy resin / (meth) acrylic acid type, and alicyclic epoxy resin / (meth) acrylic acid type. Epoxy (meth) acrylate is mentioned. The polyurethane (meth) acrylate can be obtained, for example, by reacting an isocyanate compound such as tolylene diisocyanate with a (meth) acrylate having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate. In this case, the central part of the molecule has a polyester structure, with isocyanate groups at both ends (meta).
Often acrylated. Examples of urethane compounds include oil-modified polyurethane resin systems, moisture-curable polyurethane resin systems, block-type polyurethane resin systems, and catalyst-curable polyurethane resin systems. Examples of the epoxy compound include those obtained by adding an appropriate curing agent to epoxy resin, those obtained by esterification by the reaction of epoxy resin and fatty acid, and those obtained by using epoxy resin and alkyd resin together. Examples of the silicone compound include an initial condensate obtained by mixing a small amount of dimethyldichlorosilane and diethyldichlorosilane with monomethyl or monoethyltrichlorosilane and reacting them. The obtained initial condensate is usually
It is dissolved in an appropriate solvent and, if necessary, a curing accelerator such as a soluble fatty acid salt or zinc octinate is added for use.

When a heat curing method or a room temperature curing method is used in carrying out the above-mentioned polymerization or copolymerization, a peroxide compound or an azo compound may be used alone or in combination as a polymerization initiator, if necessary. Preferably. In the case of suspension polymerization, peroxide compounds are usually used alone or in combination as a polymerization initiator.
Examples of peroxide compounds include benzoyl peroxide; p-chlorobenzoyl peroxide; 2,4
-Dichlorobenzoyl peroxide; t-butyl hydroperoxide; di-t-butyl peroxide; dicumyl peroxide; t-butyl peroxyacetate; t-butyl peroxybenzoate and the like. In this case, the amount of the peroxide-based compound used is usually 0.1 to 5 with respect to 100 parts by weight of the curable compound.
It is selected in the range of 0 parts by weight. In the case of emulsion polymerization, it is usually preferable to use a peroxide (persulfate, redox type) and an azo compound as the polymerization initiator, alone or in combination. Ammonium persulfate, potassium persulfate and the like are used as the persulfate, and hydrogen peroxide-metal salt, organic peroxide-metal salt, organic peroxide-aliphatic or alicyclic polyamine compound, organic peroxide are used as the redox type. Examples of azo compounds such as oxide-dimethylaniline and potassium dichromate-metal oxide include aromatic diazoamino compounds, aromatic diazothioethers, aromatic diazooxy compounds, and aliphatic diazo compounds.
In this case, the amount of the polymerization initiator used is the curable compound 100.
It is usually selected in the range of 0.1 to 5.0 parts by weight with respect to parts by weight.

When the above-mentioned polymerization or copolymerization is carried out by emulsion polymerization, emulsifiers used include rosin acid salts such as potassium rosinate and sodium rosinate, potassium oleate, sodium oleate, potassium laurate and sodium stearate stearate. Acids Sodium and potassium salts of fatty acids such as potassium stearate, sulfate ester salts of aliphatic alcohols such as sodium lauryl sulfate, and alkylallyl sulfonic acids such as sodium dodecylbenzene sulfonate. In the case of carrying out suspension polymerization, the suspension stabilizers used include organic suspension stabilizers such as polyvinyl alcohol, polyvinylpyrrolidone, gelatin, carboxymethyl cellulose and hydroxyalkyl cellulose, and calcium or magnesium salts of phosphoric acid and carbonic acid. Inorganic suspension stabilizers.

The spherical particles made of the crosslinked phosphazene polymer of the present invention are produced by using the above-mentioned curable phosphazene resin, and if necessary, a monomer for copolymerization, a polymerization initiator, an emulsifier and a suspension stabilizer. .. For example, the dispersant used in the suspension polymerization is 0.1 to 1% by weight based on the amount of the normally used monomer, and the suspension stabilizer used in the suspension polymerization is 0.001 in the same manner. .About.0.1 wt%, the polymerization initiator is also 0.1 to 1 wt%, and the amount of water is preferably monomer / water ≧ 1.

The crosslinked polymer spherical particles thus obtained preferably have a size of 10 ^-7 to 10 ^-3 m. In the suspension polymerization, crosslinked polymer spherical particles of 10 ^-5 to 10 ^-3 m are usually obtained, and in emulsion polymerization, particles of 10 ^-7 to 10 ^-5 m are obtained.

Further, various additives may be added within the range not impairing the object of the present invention. Here, examples of the additive include an inorganic filler, an organic filler, and a lubricant. As the inorganic filler, finely powdered silica, alumina, glass, ceramics or the like (solvent-dispersed type) may be used. Examples of the organic filler include finely powdered acrylic resin and the like. The lubricant may be any type of liquid, solid or grease,
Silicone-based, fluorine-based, other synthetic lubricants, Teflon fine particles, molybdenum disulfide, etc. can be used.

[0048]

EXAMPLES The present invention will be described in more detail based on the production examples and examples, but the present invention is not limited thereto. Production Example 1 Production of curable phosphazene compound (A) Hexachlorocyclotriphosphazene (cyclic compound of formula (NPCl ₂ ) ₃ ) 8 was placed in a 2 liter flask equipped with a thermometer, a stirrer, a dropping funnel and a condenser.
6.8 g was dissolved in 338 g of dehydrated benzene. To this benzene solution, 310 g of pyridine and 0.29 g of hydroquinone were added and stirred. Next, 200 ml of 2-hydroxyethyl methacrylate was dissolved in 237 ml of benzene, and this solution was dropped into the above flask and reacted at 60 ° C. for 30 hours. After the reaction, the pyridine hydrochloride was removed by filtration. The filtrate was washed with water, then dried using Glauber's salt, the solvent was removed by distillation under reduced pressure, and the viscous 1,1,3,3,5,5-hexa (methacryloylethylenedioxy) cyclotriphosphazene (cured 200 g of the phosphazene compound (A)) was obtained.

Production Example 2 Production of Curable Phosphazene Compound (B) 300 ml of tetrahydrofuran and 25.5 g of metallic sodium were placed in a 2 liter flask equipped with a thermometer, a stirrer, a dropping funnel and a condenser. 104.3 g (1.11 mol) of phenol was added dropwise to the mixture, and after completion of the addition, the mixture was refluxed for 3 hours to obtain a phenolate. Next, a solution of 193 g (0.555 mol) of hexachlorocyclotriphosphazene dissolved in 400 ml of benzene was added dropwise to the above reaction solution, and the reaction was allowed to proceed for 4 hours under reflux. Then, the temperature of the reaction solution was cooled to room temperature, 352 g (4.45 mol) of pyridine was added, and 381 g (2.45 mol) of 2-hydroxyethyl methacrylate was gradually added dropwise from the dropping funnel. Furthermore, the mixture was heated to 60 ° C. in a hot water bath, reacted for 20 hours while stirring, the precipitated crystals and catalyst were filtered off, the solvent in the obtained filtrate was removed by distillation under reduced pressure, and the residue was sufficiently dried. Thus, 452 g of a yellow liquid material (curable phosphazene compound (B)) was obtained.

Example 1 In a 3-liter flask equipped with a thermometer, a stirrer, a dropping funnel and a condenser, 1000 g of pure water,
5.0 g of tricalcium phosphate, 2.0 g of 1% aqueous solution of sodium dodecylbenzene sulfonate, 3 g of benzoyl peroxide and 1000 g of the curable phosphazene compound (A) obtained in Production Example 1 were added, and the mixture was stirred at 400 rpm to homogenize the mixture. A different dispersion was obtained. This suspension dispersion is stirred for 8 hours.
The temperature was raised to 0 ° C. and kept for 2 hours, then raised over 1 hour and kept at 120 ° C. for 3 hours to complete the polymerization. After the completion of the polymerization, the mixture was cooled, water was separated, and dried to obtain spherical particles (A) of the polymer. The average particle size of the obtained spherical particles is 0.5 m.
It was m.

Example 2 Production Example 2 was used in place of the curable phosphazene compound (A).
Spherical particles (B) were obtained in the same manner as in Example 1 except that the curable phosphazene compound (B) obtained in step 1 was used. The average particle size of the obtained spherical particles was 0.4 mm.

Example 3 1500 g of pure water was placed in a 3 liter flask equipped with a thermometer, a stirrer, a dropping funnel and a condenser.
20 g of calcium rosinate, 3 g of potassium persulfate, and the curable phosphazene compound (A) 1 obtained in Production Example 1
000 g was added and stirred at 400 rpm to obtain a uniform dispersion liquid. This emulsion was stirred under a nitrogen gas atmosphere,
Polymerization was completed by holding at 50 ° C for 5 hours. After completion of the polymerization, the mixture was cooled, water was separated, and dried to obtain polymer spherical particles (C). The average particle size of the obtained spherical particles is 0.8 μm.
Met.

Example 4 Preparation Example 2 was used instead of the curable phosphazene compound (A).
Spherical particles (D) were obtained in the same manner as in Example 3 except that the curable phosphazene compound (B) obtained in step 1 was used. The average particle size of the obtained spherical particles was 0.7 μm.

[0054]

As described above, the spherical particles made of the crosslinked phosphazene polymer of the present invention have high hardness (pencil hardness 9).
H), high compressive strength, and heat resistance (long-term heat resistance, 230 ° C or higher). Therefore, the spherical particles of the present invention can be widely and effectively used as a pigment dispersant, a toner additive, a powder molding binder, a paper treating agent, a resin-reinforced filler, an ink, a coating material, a cosmetic, a miniature bearing and the like. It

Claims (2)

[Claims] 1. Spherical particles comprising a crosslinked phosphazene-based polymer. 2. A spherical shape comprising a crosslinked phosphazene polymer according to claim 1, wherein the curable phosphazene compound is emulsion-polymerized or suspension-polymerized in the presence or absence of a monomer for copolymerization. Method for producing particles.