WO2015111546A1 - Microparticules de résine de poly(sulfure de phénylène), leur procédé de production, et liquide de dispersion - Google Patents

Microparticules de résine de poly(sulfure de phénylène), leur procédé de production, et liquide de dispersion Download PDF

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WO2015111546A1
WO2015111546A1 PCT/JP2015/051247 JP2015051247W WO2015111546A1 WO 2015111546 A1 WO2015111546 A1 WO 2015111546A1 JP 2015051247 W JP2015051247 W JP 2015051247W WO 2015111546 A1 WO2015111546 A1 WO 2015111546A1
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polyphenylene sulfide
sulfide resin
fine particles
pps resin
pps
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PCT/JP2015/051247
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English (en)
Japanese (ja)
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高橋俊也
牧田圭
坂根智博
赤阪寛章
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東レ株式会社
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Priority to JP2015507833A priority Critical patent/JPWO2015111546A1/ja
Publication of WO2015111546A1 publication Critical patent/WO2015111546A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • C08J3/14—Powdering or granulating by precipitation from solutions
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2381/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
    • C08J2381/04—Polysulfides

Definitions

  • the present invention relates to novel polyphenylene sulfide resin fine particles, a production method thereof, and a dispersion.
  • Polyphenylene sulfide (hereinafter sometimes abbreviated as PPS) resin has properties suitable as an engineering plastic such as excellent heat resistance, chemical resistance, organic solvent resistance, and electrical insulation, It is used for various electrical / electronic parts, machine parts, automobile parts, etc. mainly for extrusion molding.
  • PPS resin having such various excellent properties is highly demanded in the fields of paints, adhesive materials, automobiles, and electronic materials where heat resistance is required, and a method for obtaining fine PPS resin particles and a dispersion thereof. The following production method has been reported.
  • Patent Document 1 the PPS resin is dissolved in an organic solvent such as N-methyl-2-pyrrolidinone (hereinafter sometimes abbreviated as NMP) in the presence of an inorganic salt and then cooled, and the resulting PPS resin is A method of obtaining a PPS resin fine particle dispersion by mechanical pulverization with a bead mill or the like is disclosed. This method discloses that a PPS resin fine particle dispersion having an average particle size (hereinafter sometimes simply referred to as an average particle size) of 1 ⁇ m or less by a laser diffraction / scattering method is obtained.
  • NMP N-methyl-2-pyrrolidinone
  • an average particle size of 1 ⁇ m or less is obtained by dissolving a PPS resin in an organic solvent such as NMP in the presence of a surfactant, and then cooling, and mechanically pulverizing the obtained PPS resin with a bead mill or the like.
  • a method for obtaining a fine PPS resin particle dispersion is disclosed.
  • Patent Document 3 after dissolving a PPS resin in an organic solvent such as NMP, fine PPS resin fine particles are obtained by flash crystallization, and the PPS resin fine particles are mechanically pulverized or mechanically dispersed.
  • a method for producing fine PPS resin particles having an average particle size of 1 ⁇ m or less and a method for obtaining a dispersion thereof are described.
  • Patent Document 4 reports a method in which PPS resin is dissolved in a solvent and then precipitated to obtain PPS resin fine particles having a particle size of several ⁇ m.
  • a PPS resin synthesized by a method in which a dihalogen aromatic compound and an alkali metal sulfide are usually used in an N-alkylamide solvent is used as a raw material.
  • a PPS resin having a relatively low molecular weight obtained by the production method described in Japanese Patent Publication No. 45-3368 and a crosslinking agent such as peroxide in an oxygen atmosphere is used.
  • a PPS resin obtained by increasing the degree of polymerization is used.
  • an essentially linear and high molecular weight PPS resin by the production method described in JP-B-52-12240 is used.
  • Patent Document 5 describes a method for producing fine PPS resin particles using a PPS resin oligomer or a PPS resin having a low alkali metal content.
  • the PPS resin fine particles described in Patent Document 5 are non-spherical and have an average particle size of 1.1 ⁇ m to 8.6 ⁇ m, there is a problem that the dispersion stability is not sufficient.
  • the average particle size of the PPS resin fine particles is 1 ⁇ m or less and the particle shape is spherical. Further, in the paint field, adhesive material field, automobile field, and electronic material field, heat-resistant particles having an average particle diameter of 1 ⁇ m or less and excellent in dispersion stability have been demanded in order to reduce the weight and thickness of members.
  • the problem is to obtain fine PPS resin particles that could not be obtained by conventional techniques and have an average particle size of 1 ⁇ m or less and a small amount of gas generation during heating.
  • the fine PPS resin particles obtained according to the present invention can further have a fine average primary particle size and be uniform.
  • the polyphenylene sulfide resin has a dispersity (Mw / Mn) defined by the ratio of the number average molecular weight (Mn) to the weight average molecular weight (Mw) of 2.5 or less, and the average primary particle size of the fine particles comprising the resin is 90 nm.
  • A A process of heating a polyphenylene sulfide resin in an organic solvent to obtain a polyphenylene sulfide resin solution (dissolution process)
  • B A step of precipitating fine particles of polyphenylene sulfide resin by flash crystallization of the solution (precipitation step)
  • ⁇ Wr (W1-W2) / W1 ⁇ 100 (%)
  • ⁇ Wr is a weight reduction rate (%), and when thermogravimetric analysis was performed at a temperature rising rate of 20 ° C./min from 50 ° C. to an arbitrary temperature of 330 ° C.
  • the polyphenylene sulfide resin used as a raw material is a cyclic polyphenylene sulfide represented by the following general formula (I)
  • p is an integer of 4 to 20, and the component (B) may be a mixture of plural kinds of cyclic polyphenylene sulfides having different m.
  • a polyphenylene sulfide resin obtained by heating a polyphenylene sulfide prepolymer having a weight average molecular weight of less than 10,000 and converting it to a high degree of polymerization having a weight average molecular weight of 10,000 or more.
  • (V) A method for producing a polyphenylene sulfide resin fine particle dispersion in which polyphenylene sulfide resin fine particles obtained by the method for producing polyphenylene sulfide resin fine particles according to (III) are dispersed in a dispersion medium.
  • the average particle size is 1 ⁇ m or less, the shape is spherical, the dispersion stability is excellent, the polyphenylene sulfide resin has a dispersity of 2.5 or less, and contains an alkali metal.
  • Polyphenylene sulfide resin fine particles having an amount of less than 100 ppm can be easily obtained, and the amount of gas generated during heating is small, which can be a widely industrially useful material.
  • the PPS resin used as a raw material of the present invention contains a repeating unit of the formula, — (Ar—S) —, as a main constituent unit, and preferably contains 80 mol% or more of the repeating unit. Homopolymer or copolymer.
  • Ar includes units represented by the following formulas (a) to (k), among which the formula (a) is particularly preferable.
  • R1 and R2 are substituents selected from hydrogen, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an arylene group having 6 to 24 carbon atoms, and a halogen group. May be the same or different
  • this repeating unit can contain a small amount of branching units or crosslinking units represented by the following formulas (l) to (n).
  • the copolymerization amount of these branched units or cross-linked units is preferably in the range of 0 to 1 mol% with respect to 1 mol of — (Ar—S) — units.
  • the PPS resin used as the raw material of the present invention may be any of a random copolymer, a block copolymer and a mixture thereof containing the above repeating unit.
  • Typical examples of these include polyphenylene sulfide, polyphenylene sulfide sulfone, polyphenylene sulfide ketone, random copolymers thereof, block copolymers, and mixtures thereof.
  • PPS resin p-phenylene sulfide unit as the main structural unit of the polymer
  • PPS resin containing 80 mol% or more, particularly 90 mol% or more PPS resin containing 80 mol% or more, particularly 90 mol% or more.
  • the lower limit value of the molecular weight (weight average molecular weight) of the PPS resin is selected in the range of 10,000 or more, preferably 15,000 or more, more preferably 18,000 or more.
  • the upper limit value of the molecular weight (weight average molecular weight) of the PPS resin is selected within a range of 100,000 or less, preferably 50,000 or less, and more preferably 30,000 or less.
  • the lower limit value of the weight average molecular weight of the PPS resin is less than 10,000, properties of the obtained fine particles such as an increase in the amount of gas generated during heating are impaired.
  • the upper limit of the weight average molecular weight exceeds 100,000 there is a possibility that the solubility in an organic solvent is lowered.
  • fine-particles from which the one where the weight average molecular weight of PPS resin is smaller can be expected.
  • the dispersity (Mw / Mn) represented by the ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) (weight average molecular weight / number average molecular weight) is 2.5 or less.
  • 2.3 or less is more preferable, 2.1 or less is more preferable, and 2.0 or less is even more preferable.
  • the lower limit of the degree of dispersion is theoretically 1 and is usually 1.5 or more. When the degree of dispersion is 2.5 or less, the amount of low molecular components contained in the PPS resin tends to decrease.
  • the resulting PPS resin fine particles tend to have a favorable tendency such as a decrease in the amount of gas generated when heated and a decrease in the amount of the eluted component when in contact with the solvent.
  • the said weight average molecular weight and number average molecular weight can be calculated
  • melt viscosity of the PPS resin a range in which the melt viscosity is usually 5 to 10,000 Pa ⁇ s (300 ° C., shear rate 1,000 / second) can be exemplified as a preferable range.
  • the resulting fine particles tend to be excellent in processability.
  • the alkali metal content which is an impurity contained in the PPS resin, is not particularly limited, but the alkali metal content is preferably less than 700 ppm by weight from the viewpoint of developing the resulting fine particles for use in semiconductor members that require electrical insulation. It can be illustrated as a range. It is preferable for the alkali metal content to be less than 700 ppm because it is possible to prevent a decrease in electrical insulation due to metal impurities. From the viewpoint of lowering electrical insulation, the alkali metal content of the PPS resin is more preferably less than 500 ppm by weight, more preferably less than 200 ppm, and particularly preferably less than 100 ppm.
  • the alkali metal content of the PPS resin used as the raw material of the present invention is a value calculated from the amount of alkali metal in the ash, which is a residue obtained by firing the PPS resin using an electric furnace, for example, For example, it can be quantified by analyzing by ion chromatography or atomic absorption.
  • the alkali metal refers to lithium, sodium, potassium, rubidium, cesium, and francium belonging to Group IA of the periodic table, but the PPS resin that is a raw material of the present invention may not contain an alkali metal other than sodium. preferable.
  • an alkali metal other than sodium is included, the electric characteristics and thermal characteristics of the obtained PPS resin fine particles tend to be adversely affected.
  • the amount of eluted metal when the obtained fine PPS resin particles come into contact with various solvents increases, and this tendency becomes strong particularly when the PPS resin contains lithium.
  • alkali metals tend to have a strong influence on the electrical properties, thermal properties, and metal elution amount of PPS resins. It is in. Therefore, it is estimated that the quality of the PPS resin fine particles obtained can be improved by setting the alkali metal content within the above range among various metal species.
  • a major feature of the PPS resin used as the raw material of the present invention is that the weight reduction rate upon heating satisfies the following formula (1).
  • ⁇ Wr (W1-W2) /W1 ⁇ 100 ⁇ 0.18 (%) (1)
  • ⁇ Wr is a weight reduction rate (%), and when thermogravimetric analysis was performed at a temperature increase rate of 20 ° C./min from 50 ° C. to an arbitrary temperature of 330 ° C. or higher in a non-oxidizing atmosphere at normal pressure. The value obtained from the sample weight (W2) when reaching 330 ° C. with reference to the sample weight (W1) when reaching 100 ° C.
  • the weight reduction rate ⁇ Wr of the PPS resin used as a raw material is 0.18% or less, preferably 0.12% or less, more preferably 0.10% or less, and 0.085% or less. Even more preferred. ⁇ Wr is preferably as small as possible, but the usual lower limit is 0.001%. When ⁇ Wr exceeds the above range, for example, there is a tendency that a problem that the amount of generated gas is large when processing the obtained PPS resin fine particles is large.
  • the conventional PPS resin obtained by a known production method has a ⁇ Wr of more than 0.18%. However, unlike the conventional PPS resin, the PPS resin used as a raw material of the present invention has a narrow molecular weight distribution and extremely low impurity content. Since it is small, it is estimated that the value of ⁇ Wr is remarkably lowered.
  • ⁇ Wr can be obtained by a general thermogravimetric analysis, and an atmospheric pressure non-oxidizing atmosphere is used as the atmosphere in this analysis.
  • the non-oxidizing atmosphere is an atmosphere in which the oxygen concentration in the gas phase in contact with the sample is 5% by volume or less, preferably 2% by volume or less, and more preferably an oxygen-free atmosphere, that is, inert such as nitrogen, helium, argon, etc. Indicates a gas atmosphere. Among these, a nitrogen atmosphere is particularly preferable from the viewpoint of economy.
  • the normal pressure is a pressure in the vicinity of the standard state of the atmosphere, and is an atmospheric pressure condition in which the temperature is about 25 ° C. and the absolute pressure is about 101.3 kPa.
  • the PPS resin may be oxidized during the measurement, or may not be measured in accordance with the actual use conditions of the PPS resin, such as being significantly different from the atmosphere used in the actual processing of the PPS resin. A possibility arises.
  • the thermogravimetric analysis is performed by increasing the temperature from 50 ° C. to an arbitrary temperature of 330 ° C. or more at a temperature increase rate of 20 ° C./min. Preferably, after holding at 50 ° C. for 1 minute, the temperature is increased at a rate of temperature increase of 20 ° C./min to perform thermogravimetric analysis.
  • This temperature range is a temperature region frequently used when the PPS resin is actually used, and is also a temperature region frequently used when the solid PPS resin is melted and then molded into an arbitrary shape.
  • the weight reduction rate in the actual use temperature region is related to the amount of gas generated from the PPS resin during actual use, the amount of components adhering to the die or mold during molding, and the like. Therefore, it can be said that a PPS resin having a lower weight loss rate in such a temperature range is an excellent PPS resin having a higher quality. It is desirable to measure ⁇ Wr with a sample amount of about 10 mg, and the shape of the sample is desirably a fine particle of about 2 mm or less.
  • the PPS resin having the characteristic of the above formula (1) includes a polyphenylene sulfide prepolymer (hereinafter referred to as PPS prepolymer) containing cyclic polyphenylene sulfide (hereinafter sometimes abbreviated as cyclic PPS) as described later. (Which may be omitted) is preferably produced by heating to a high degree of polymerization. Although the conversion to a high polymerization degree will be described in detail later, the weight fraction of the cyclic PPS contained in the PPS resin obtained after the operation of converting the PPS prepolymer to the high polymerization degree is 40% by weight.
  • % Or less preferably 25% by weight or less, more preferably 15% by weight or less, is preferable because the above-described ⁇ Wr value is particularly small.
  • the value of the weight fraction of cyclic PPS exceeds the above range, the value of ⁇ Wr tends to increase. Although the cause of this is not clear at present, it is assumed that the cyclic PPS contained in the PPS resin is partially volatilized during heating.
  • the conditions selected from the weight average molecular weight, the degree of dispersion, and the alkali metal content of the PPS resin are as follows: It is not necessarily within the above-mentioned range. As described above, the PPS resin containing a certain amount of cyclic PPS can satisfy the thermogravimetric characteristic of the formula (1). However, when the conditions selected from the weight average molecular weight, the degree of dispersion, and the alkali metal content of the PPS resin are within the above-described ranges, it is desirable because the weight loss upon heating tends to be particularly small.
  • the PPS resin used as a raw material of the present invention has an excellent feature that the weight reduction rate ⁇ Wr at the time of heating accompanied by a temperature rise is small, but when holding the PPS resin at any certain constant temperature, There exists a tendency to have the outstanding characteristic that there is also little reduction rate (heating loss) of the weight compared before and after a heating.
  • the PPS resin used as the raw material of the present invention is obtained by heating a PPS prepolymer containing at least 50% by weight of cyclic PPS and having a weight average molecular weight of less than 10,000.
  • An example is a method of production by converting to a high degree of polymerization having an average molecular weight of 10,000 or more. According to this method, it is possible to easily obtain a PPS resin having the above-described characteristics.
  • cyclic PPS a cyclic PPS represented by the following general formula (I) can be used.
  • p is an integer of 4 to 20
  • the cyclic PPS used may be a mixture of plural kinds of cyclic PPS having different p.
  • the cyclic PPS may be either a single compound having a single repeating number or a mixture of cyclic PPS having different repeating numbers.
  • a mixture of cyclic PPS having a different number of repetitions tends to have a lower melting temperature than a single compound having a single number of repetitions, and the use of a mixture of cyclic PPS having a different number of repetitions will be described later. This is preferable because the temperature during the conversion to a high degree of polymerization can be further reduced.
  • the PPS prepolymer containing the above cyclic PPS is heated to be converted into a high degree of polymerization.
  • the PPS prepolymer used here contains at least 50% by weight of cyclic PPS, preferably 70% by weight or more, more preferably 80% by weight or more, and still more preferably 90% by weight or more. .
  • the higher the weight ratio of cyclic PPS in the PPS prepolymer the higher the degree of polymerization and the melt viscosity of the PPS resin obtained after heating. That is, in the method for producing the PPS resin used as the raw material of the present invention, it is possible to easily adjust the polymerization degree and the melt viscosity of the obtained PPS resin by adjusting the abundance ratio of the cyclic PPS in the PPS prepolymer. It is.
  • the weight ratio of cyclic PPS in the PPS prepolymer exceeds the above-described upper limit value, the melt dissolution temperature of the PPS prepolymer tends to increase, so the weight ratio of cyclic PPS in the PPS prepolymer is within the above range. It is preferable to do so because the temperature at which the PPS prepolymer is converted into a high degree of polymerization can be lowered.
  • the component other than cyclic PPS in the PPS prepolymer is particularly preferably a linear polyphenylene sulfide oligomer (hereinafter sometimes abbreviated as PPS oligomer).
  • the linear PPS oligomer is a homo-oligomer or co-oligomer having a repeating unit of the formula, — (Ar—S) —, as a main constituent unit, and preferably containing 80 mol% or more of the repeating unit.
  • Ar includes units represented by the above-described formulas (a) to (k), among which the formula (a) is particularly preferable.
  • the linear PPS oligomer can contain a small amount of branching units or crosslinking units represented by the above formulas (l) to (n) as long as these repeating units are the main constituent units.
  • the copolymerization amount of these branched units or cross-linked units is preferably in the range of 0 to 1 mol% with respect to 1 mol of — (Ar—S) — units.
  • the linear PPS oligomer may be any of a random copolymer, a block copolymer and a mixture thereof containing the above repeating unit.
  • Typical examples of components other than cyclic PPS include polyphenylene sulfide oligomers, polyphenylene sulfide sulfone oligomers, polyphenylene sulfide ketone oligomers, random copolymers, block copolymers, and mixtures thereof.
  • Particularly preferred linear PPS oligomers include linear PPS oligomers containing 80 mol% or more, particularly preferably 90 mol% or more of p-phenylene sulfide units as the main structural unit of the polymer.
  • the amount of linear polyphenylene sulfide (hereinafter sometimes abbreviated as linear PPS) contained in the PPS prepolymer is particularly preferably smaller than the cyclic PPS contained in the PPS prepolymer. That is, the weight ratio of cyclic PPS to linear PPS (cyclic PPS / linear PPS) in the PPS prepolymer is preferably 1 or more, more preferably 2.3 or more, still more preferably 4 or more, and 9 The above is even more preferable. By using such a PPS prepolymer, a PPS resin having a weight average molecular weight of 10,000 or more can be easily obtained.
  • the weight average molecular weight of the PPS resin obtained by the preferred production method of the PPS resin used as the raw material of the present invention tends to increase. . Therefore, although there is no particular upper limit to this weight ratio, in order to obtain a PPS prepolymer having a weight ratio exceeding 100, it is necessary to significantly reduce the linear PPS content in the PPS prepolymer. It takes effort. According to a preferred method for producing a PPS resin used as a raw material of the present invention, a sufficiently high molecular weight PPS resin can be easily obtained even if a PPS prepolymer having a weight ratio of 100 or less is used.
  • the upper limit of the molecular weight of the PPS prepolymer is less than 10,000 in terms of weight average molecular weight, preferably 5,000 or less, and more preferably 3,000 or less.
  • the lower limit is preferably 300 or more, preferably 400 or more, and more preferably 500 or more in terms of weight average molecular weight.
  • the PPS resin is characterized by high purity, and the PPS prepolymer used for production is also preferably high purity. Therefore, in the PPS prepolymer, the content of alkali metal as an impurity is preferably less than 700 ppm by weight, more preferably less than 500 ppm, still more preferably less than 200 ppm, and particularly preferably less than 100 ppm.
  • the alkali metal content of the obtained PPS resin usually depends on the alkali metal content of the PPS prepolymer.
  • the alkali metal content of the PPS prepolymer exceeds the above range, the alkali metal content of the obtained PPS resin may exceed the range of the alkali metal content of the PPS resin used as the raw material of the present invention.
  • the amount of alkali metal in the reaction system is less than 700 ppm by weight, preferably 500 ppm or less, more preferably 300 ppm or less, more preferably 100 ppm or less. It is desirable to carry out under the following conditions.
  • the disulfide weight relative to the total sulfur weight in the reaction system is less than 1% by weight, preferably less than 0.5% by weight, more preferably less than 0. It is preferable to carry out under the condition of less than 3% by weight, more preferably less than 0.1% by weight.
  • an ionic compound containing an alkali metal and / or other metal component or a compound having radical generating ability as a catalyst component.
  • examples of the ionic compound include sodium salt of thiophenol and alkali metal salt of sulfur.
  • examples of the compound having a radical generating ability include a compound that generates a sulfur radical by heating, and more specifically, a compound containing a disulfide bond.
  • the weight loss increase upon heating of the obtained PPS resin is different from the case where an ionic compound or a compound having radical generating ability is used as a catalyst component. It tends to be suppressed. From this, when using a catalyst component for the purpose of accelerating the reaction for conversion to a high degree of polymerization, it is desirable to use a zero-valent transition metal compound.
  • Examples of the method for obtaining the PPS prepolymer include the following methods. (1) A granular PPS resin separated by an 80 mesh sieve (aperture 0.125 mm) by polymerizing PPS by heating a mixture containing at least a polyhalogenated aromatic compound, a sulfidizing agent and an organic solvent, A PPS component produced by polymerization and containing a PPS component other than the granular PPS resin (referred to as a PPS oligomer), an organic solvent, water, and an alkali metal halide salt is prepared.
  • the PPS oligomer contained in this mixture is separated and recovered and subjected to a purification operation to obtain a PPS prepolymer.
  • a method of recovering the PPS prepolymer by refining the obtained PPS using a poor solvent by obtaining a PPS containing the PPS prepolymer by purifying this by a known method.
  • the PPS resin is preferably produced by a method in which the PPS prepolymer is heated to be converted into a high degree of polymerization.
  • the heating temperature is preferably a temperature at which the PPS prepolymer melts, and there is no particular limitation as long as it is such a temperature condition. When the heating temperature is lower than the melting temperature of the PPS prepolymer, a long time tends to be required to obtain a high degree of polymerization of the PPS resin.
  • the temperature at which the PPS prepolymer melts varies depending on the composition and molecular weight of the PPS prepolymer and the environment during heating, it cannot be uniquely indicated.
  • the PPS prepolymer is a differential scanning calorimeter. It is possible to grasp the melting solution temperature by analyzing with. However, if the temperature at the time of heating is too high, it is not preferable represented by a crosslinking reaction or a decomposition reaction between PPS prepolymers, between high degree of polymerization produced by heating, between a high degree of polymerization and a PPS prepolymer, or the like. Side reactions tend to occur, and the properties of the resulting PPS resin may be deteriorated. Therefore, it is desirable to avoid a temperature at which such an undesirable side reaction is remarkably generated. As heating temperature, 180 degreeC or more can be illustrated, Preferably it is 200 degreeC or more, More preferably, it is 250 degreeC or more. Moreover, 400 degrees C or less can be illustrated as heating temperature, Preferably it is 380 degrees C or less, More preferably, it is 360 degrees C or less.
  • the time for performing the heating differs depending on the characteristics such as the content of cyclic PPS in the PPS prepolymer used, the p number, the molecular weight, and the conditions such as the heating temperature, it cannot be uniformly defined, but is not preferable as described above. It is preferable to set so that the side reaction does not occur as much as possible.
  • the heating time include 0.05 hours or more, preferably 0.1 hours or more.
  • 100 hours or less can be illustrated, 20 hours or less are preferable and 10 hours or less are more preferable.
  • the heating time is less than 0.05 hours, the conversion of the PPS prepolymer to a high degree of polymerization tends to be insufficient.
  • the heating time exceeds 100 hours there is a tendency that an adverse effect on the properties of the PPS resin becomes obvious due to an undesirable side reaction.
  • the conversion of the PPS prepolymer to a high degree of polymerization by heating is usually performed in the absence of a solvent, but can also be performed in the presence of a solvent.
  • the solvent is not particularly limited as long as it does not substantially cause undesirable side reactions such as inhibition of conversion of the PPS prepolymer to a high degree of polymerization by heating and decomposition or crosslinking of the produced high degree of polymerization.
  • the solvent examples include NMP, dimethylformamide, polar solvents such as dimethylacetamide, dimethylsulfoxide, and dimethylsulfone, ketone solvents such as acetone, methyl ethyl ketone, diethyl ketone, and acetophenone, and ethers such as dimethyl ether, dipropyl ether, and tetrahydrofuran.
  • polar solvents such as dimethylacetamide, dimethylsulfoxide, and dimethylsulfone
  • ketone solvents such as acetone, methyl ethyl ketone, diethyl ketone, and acetophenone
  • ethers such as dimethyl ether, dipropyl ether, and tetrahydrofuran.
  • Solvents chloroform, methylene chloride, trichloroethylene, ethylene chloride, dichloroethane, tetrachloroethane, halogen solvents such as chlorobenzene, methanol, ethanol, propanol, butanol, pentanol, ethylene glycol, propylene glycol, polyethylene glycol, etc.
  • Alcohol solvents phenol solvents such as phenol and cresol, benzene, toluene, and And aromatic hydrocarbon solvents such as xylene. These solvents can be used as one kind or a mixture of two or more kinds.
  • the conversion of the PPS prepolymer to a high degree of polymerization by heating may be performed in a mold for producing a molded product, as well as by a method using a normal polymerization reaction apparatus, an extruder or a melt. Any apparatus equipped with a heating mechanism, such as a kneader, can be used without particular limitation, and known methods such as a batch method and a continuous method can be employed.
  • the atmosphere during the conversion of the PPS prepolymer to a high degree of polymerization by heating is preferably a non-oxidizing atmosphere, and is preferably performed under reduced pressure. Moreover, when it carries out under pressure reduction conditions, it is preferable to make it the pressure reduction conditions after making the atmosphere in a reaction system once non-oxidizing atmosphere.
  • the reduced pressure condition means that the pressure in the reaction system is lower than atmospheric pressure, and the upper limit is preferably 50 kPa or less, more preferably 20 kPa or less, and even more preferably 10 kPa or less.
  • An example of the lower limit of the pressure in the system is 0.1 kPa or more.
  • PPS resin fine particles in the present invention can be produced through the steps including the following steps (a) and (b).
  • a process of heating a PPS resin in an organic solvent to form a PPS resin solution (dissolution process)
  • (B) A step of precipitating PPS resin fine particles by flash crystallization of the solution (precipitation step).
  • a PPS resin fine particle dispersion can be produced through the following step (c).
  • the dispersion medium may contain a surfactant, and it is preferable to mechanically disperse a suspension in which the PPS resin fine particles are dispersed in the dispersion medium.
  • the PPS resin is dissolved by heating in an organic solvent.
  • organic solvent any organic solvent can be used as long as it is a solvent in which the PPS resin dissolves.
  • alkyl halides such as chloroform, aromatic halides such as o-dichlorobenzene and 1-chloronaphthalene, N-alkylpyrrolidinones such as NMP, and N-alkylcaprolactams such as N-methyl- ⁇ -caprolactam 1,3-dimethyl-2-imidazolidinone, N, N-dimethylacetamide, N, N-dimethylformamide (hereinafter sometimes abbreviated as DMF), hexamethylphosphoric triamide, dimethyl sulfoxide (hereinafter DMSO) And a solvent selected from at least one of polar solvents such as dimethyl sulfone and tetramethylene sulfone.
  • NMP is particularly preferable because of the solubility
  • the upper limit charge concentration of the PPS resin with respect to the organic solvent is such that, when undissolved PPS resin or molten PPS resin is present at a predetermined temperature, after flash crystallization, it becomes a coarse particle or a lump and becomes a flash crystallized liquid.
  • the PPS resin concentration is 20 parts by weight or less, preferably 15 parts by weight or less, more preferably 10 parts by weight or less with respect to 100 parts by weight of the total of the organic solvent and the PPS resin.
  • the PPS resin concentration increases, the average primary particle size increases, but when the PPS resin concentration is too high, the particles tend to fuse.
  • the PPS resin particles When the PPS resin particles are used under extreme conditions such as strong acid, strong base, and high temperature, the PPS resin may be decomposed, so that the specific surface area of the particles is preferably small in order to make the decomposition difficult. Therefore, particles having a large particle size are preferred.
  • (i) increase the concentration of the PPS resin (ii) increase the NMP / water ratio of the receiving tank in the precipitation process, and (iii) set the temperature of the receiving tank in the precipitation process. It is preferable to raise. Under such conditions, spherical fine particles having an average primary particle diameter of 150 nm to 300 nm, which will be described later, and a sphericity of 0.85 or more are obtained.
  • the PPS resin solution is flash-crystallized in a precipitation solvent in another container in which PPS resin fine particles are precipitated in the precipitation step described later.
  • the atmosphere of the tank in the dissolution process is preferably a non-oxidizing atmosphere in order to suppress the decomposition and deterioration of the PPS resin and further to proceed safely.
  • the non-oxidizing atmosphere is an atmosphere in which the oxygen concentration in the gas phase is 5% by volume or less, preferably 2% by volume or less, and more preferably contains substantially no oxygen, that is, an inert gas atmosphere such as nitrogen, helium, and argon. Of these, a nitrogen atmosphere is particularly preferable from the viewpoint of economy.
  • the dissolution method is not particularly limited, PPS resin and an organic solvent are placed in a predetermined container and heated while stirring.
  • a method in which the PPS resin is completely dissolved in a solvent and then flash-crystallized and precipitated is preferable.
  • the solubility of the PPS resin in the organic solvent is small, so that the boiling point of the solvent is higher than the boiling point of the solvent and less than the decomposition point of the PPS resin.
  • a method of dissolving by heating is preferred.
  • the dissolution temperature varies depending on the type of solvent used and the concentration of the PPS resin, but is usually 200 ° C. to 400 ° C., preferably 220 ° C. to 320 ° C.
  • the temperature is high, the PPS resin is decomposed. Moreover, if it is less than 200 degreeC, in order to melt
  • the dissolution time varies depending on the type of solvent, the concentration of the PPS resin charged, and the dissolution temperature, but is usually 10 minutes to 10 hours, preferably 20 minutes to 8 hours, more preferably 30 minutes to 5 hours.
  • the PPS resin can be dissolved by the above operation.
  • a pressure vessel such as an autoclave
  • the fine particles deposited in the precipitation step are different from the PPS resin before dissolution in shape and particle size, the result is determined by the dissolution / precipitation of the present invention.
  • the shape and particle size change due to this dissolution / precipitation is judged from the change in average particle size using a particle size distribution meter and the shape change by SEM.
  • the PPS resin solution dissolved in the dissolution step is flash-crystallized in a precipitation solvent in another container (hereinafter sometimes referred to as a receiving tank) in which PPS resin fine particles are precipitated to precipitate PPS resin fine particles.
  • flash crystallization refers to the solution under heating / pressurization, the temperature and pressure being below the boiling point of the organic solvent used in the dissolving step (or under cooling), below the pressure being applied.
  • a method of rapidly cooling using a cooling effect due to a pressure difference or a cooling effect due to latent heat by ejecting and transferring liquid through a nozzle into a solvent for precipitation in a receiving tank controlled under reduced pressure. Point to.
  • the degree of cooling can be adjusted by heating the receiving tank, and the particle size of the PPS resin fine particles can be controlled.
  • a solution of PPS resin from a container held under heating and pressurization into a receiving tank under atmospheric pressure (may be under reduced pressure).
  • a receiving tank under atmospheric pressure may be under reduced pressure.
  • the melting step when the melting is performed in a pressure-resistant container such as an autoclave, the inside of the container is pressurized by a self-made pressure by heating. By releasing the pressure from this state and releasing it into a receiving tank under atmospheric pressure, it can be carried out more easily.
  • the solvent for precipitating the PPS resin fine particles is not particularly limited, but from the viewpoint of uniformly dispersing the precipitated PPS resin fine particles and the solvent of the PPS resin solution in the precipitating solvent, an organic solvent used in the dissolving step. It is preferable that the solvent is uniformly mixed with the solvent.
  • uniform mixing means that when two or more solvents are mixed, the interface does not appear even if the mixture is allowed to stand for one day, and is mixed uniformly.
  • uniform mixing means that when two or more solvents are mixed, the interface does not appear even if the mixture is allowed to stand for one day, and is mixed uniformly.
  • water NMP, DMF, acetone, DMSO, tetrahydrofuran, methanol, ethanol and the like can be mentioned as a solvent in which they are uniformly mixed.
  • a solvent for dissolving the PPS resin can also be used as a solvent for precipitation.
  • the solvent for precipitation is a solvent that is uniformly mixed with the solvent used in the dissolution step, and a poor solvent for the PPS resin is used. It is preferable to include.
  • NMP is selected as the solvent for the dissolution step
  • NMP alcohols, acetones, water, etc.
  • the solvent for precipitation can select the solvent to precipitate according to the objective.
  • the precipitation solvent for precipitating the PPS resin fine particles may be a single solvent or a mixture of two or more solvents as long as it is uniformly mixed with the organic solvent used in the dissolution step. Good.
  • the precipitation solvent it is preferable to use water or a mixed solvent of NMP and water from the viewpoints of safety and economy.
  • a mixed solvent of NMP and water it is preferable that water is 10 to 0.1 parts by weight with respect to 1 part by weight of NMP.
  • the amount of the precipitating solvent for precipitating the PPS resin fine particles is not particularly limited, but the range of 100 to 0.1 parts by weight with respect to 1 part by weight of the solvent in the dissolving step can be exemplified, and preferably 50 to 0.00. 1 part by weight, more preferably 15 to 0.1 part by weight.
  • the flash crystallization method is not particularly limited, but usually the flash crystallization is performed in a single stage in a receiving tank under a pressure of 200 ° C. to 400 ° C., preferably 220 ° C. to 320 ° C. or lower, or under reduced pressure.
  • a method or a method of flash cooling in multiple stages in a container having a lower pressure than the inside of the tank containing the solution can be employed.
  • the melting step when the melting is performed in a pressure-resistant container such as an autoclave, the inside of the container is pressurized by a self-made pressure by heating.
  • the pressurized solution is flushed in an atmospheric pressure receiving tank containing a precipitation solvent for precipitating PPS resin fine particles, or is flushed in a receiving tank under reduced pressure.
  • the pressure (gauge pressure) of the solution for flash crystallization is preferably 0.2 to 4 MPa. From this environment, it is preferable to perform flash crystallization, preferably flash crystallization in a receiving tank under atmospheric pressure, more preferably under atmospheric pressure.
  • the temperature of the receiving tank varies depending on the precipitating solvent for precipitating PPS resin fine particles to be put into the receiving tank, but the temperature at which the solvent for precipitating the PPS resin fine particles does not solidify.
  • the temperature immediately before flash crystallization is preferably 0 to 100 ° C.
  • the dissolution temperature is 270 ° C.
  • the temperature of the water in the receiving tank is 100 ° C.
  • the temperature of the flash solution immediately after flash crystallization rises to 100 ° C. or higher.
  • the particle size of the PPS resin fine particles becomes large. Therefore, when it is desired to increase the average primary particle size, it is preferable to increase the receiving tank temperature.
  • the receiving tank temperature immediately before flash crystallization can be adjusted to 100 ° C. or higher, and a larger particle diameter can be obtained by using a mixed solvent of NMP and water. Particles can be obtained.
  • the flash crystallization method for precipitation of PPS resin fine particles in the solvent for precipitation is the same as that in which the outlet of the connecting tube from the dissolution tank is placed in the precipitation solvent of the receiving tank and the PPS resin solution is directly flash crystallization.
  • PPS resin fine particles can be obtained, which is preferable.
  • a liquid in which fine PPS resin particles obtained by flash crystallization of a PPS resin solution in a precipitation solvent is referred to as a flash solution.
  • the flash liquid obtained in the above precipitation step may be used as it is or after adding a surfactant to perform mechanical dispersion to form a PPS resin fine particle dispersion, but after replacing with a new dispersion medium, mechanical dispersion is performed. Also good.
  • a method for isolating the PPS resin fine particles it can be performed by a conventionally known solid-liquid separation method such as filtration, centrifugation, centrifugal filtration, etc. In order to efficiently isolate the PPS resin fine particles by a solid-liquid separation operation.
  • a method for increasing the particle size by agglomeration a natural agglomeration method that agglomerates with time, an agglomeration method by heating, an agglomeration method by removing an organic solvent while heating, an agglomeration method by salting-out, etc.
  • aggregates having a large particle size suitable for industrial solid-liquid separation methods can be obtained.
  • the average particle size of the aggregates at this time is 5 to 150 ⁇ m (particle size according to the measurement method described later), preferably 20 to 100 ⁇ m.
  • the flash solution is heated to 50 ° C. to 100 ° C. by allowing it to stand for 1 day or longer, and the flash solution is further heated to the boiling point of the organic solvent (normal pressure, reduced pressure).
  • the aggregation time can be shortened by removing the organic solvent while heating.
  • an aggregate having a large particle size can be obtained by adding about 0.5 to 500 parts by weight.
  • salting-out agents inorganic metal salts such as sodium chloride, magnesium chloride, calcium chloride, lithium chloride, potassium chloride, sodium acetate, magnesium acetate, calcium acetate, sodium oxalate, magnesium oxalate, calcium oxalate, sodium citrate And organic metal salts such as magnesium citrate and calcium citrate.
  • a solvent for dissolving the salting-out agent water is preferable.
  • the inorganic salt may be dissolved in advance in a solvent for precipitating the PPS resin fine particles in the receiving tank when flash crystallization is performed.
  • the solvent for precipitating the PPS resin fine particles at this time is preferably water.
  • the amount of the inorganic salt to be added is preferably 0.1 parts by weight or more with respect to 1 part by weight of the PPS resin fine particles and less than or equal to the saturated dissolution amount in the solvent in which the PPS resin fine particles are precipitated.
  • the PPS resin fine particles obtained by flash crystallization as in the present invention are easily agglomerated by such a method to facilitate solid-liquid separation.
  • Examples of the solid-liquid separation method for the PPS resin particles obtained by the aggregation include methods such as filtration and centrifugation.
  • a membrane filter filtration or a filter cloth (filtration, centrifugation) can be used.
  • the opening of the filter is appropriately determined according to the particle size of the PPS resin fine particles to be obtained.
  • the air permeability is usually about 0.1 to 50 ⁇ m, and in the case of a filter cloth, the air permeability is 124.5 Pa. 5 cm 3 / cm 2 ⁇ sec or less can be used.
  • the solvent in the wet cake is reslurried with the dispersion medium used in the dispersion process, or the dispersion medium used in the dispersion process. Just wash and wash.
  • the PPS resin fine particles obtained in the filtration / isolation step are redispersed by ultrasonic dispersion to obtain a PPS resin fine particle dispersion.
  • the PPS resin fine particles used in the dispersion step contain a dispersion medium. It is necessary to keep it in a state.
  • the PPS resin fine particles used in the dispersion step are preferably in a state containing 50% by weight or more of a dispersion medium.
  • Examples of the medium that can be a dispersion medium include aliphatic hydrocarbon solvents such as pentane, hexane, heptane, octane, cyclohexane, cyclopentane, decane, dodecane, tridecane, and tetradecane, benzene, toluene, xylene, 2-methylnaphthalene, and the like.
  • Aromatic hydrocarbon solvents such as ethyl acetate, methyl acetate, butyl acetate, butyl propionate, butyl butyrate, chloroform, bromoform, methylene chloride, 1,2-dichloroethane, 1,1,1-trichloroethane, Halogen solvents such as chlorobenzene, o-dichlorobenzene, p-dichlorobenzene, 2,6-dichlorotoluene, 1-chloronaphthalene and hexafluoroisopropanol, and ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and methyl butyl ketone.
  • ester solvents such as ethyl acetate, methyl acetate, butyl acetate, butyl propionate, butyl butyrate, chloroform, bromoform, methylene chloride, 1,2-dichlor
  • Ton solvents alcohol solvents such as methanol, ethanol, isopropanol, n-propanol, N-alkylpyrrolidinone solvents such as NMP, N-ethyl-2-pyrrolidinone, N-methyl- ⁇ -caprolactam, N-ethyl- ⁇ -N-alkylcaprolactam solvents such as caprolactam, polar solvents such as 1,3-dimethyl-2-imidazolidinone, N, N-dimethylacetamide, DMF, hexamethylphosphate triamide, DMSO, dimethylsulfone, tetramethylenesulfone , Diethyl ether, tetrahydrofuran, diisopropyl ether, dioxane, diglyme, dimethoxyethane and the like, and at least one solvent selected from water can be exemplified, but water is most preferable from the environmental and safety viewpoints.
  • a surfactant and a dispersion medium are added to the fine PPS resin particles obtained by solid-liquid separation operation or the like, and the resultant is subjected to a dispersion step.
  • a surfactant is added.
  • the addition timing of the surfactant may be either before or after ultrasonic dispersion, but in order to prevent aggregation of fine particles during ultrasonic dispersion, addition before dispersion or an addition method using both addition before dispersion and addition during dispersion is preferable. .
  • the surfactant examples include a cationic surfactant, an anionic surfactant, an amphoteric surfactant, a nonionic surfactant, and a polymer surfactant.
  • Anionic surfactants include fatty acid sodium, fatty acid potassium, sodium alkylbenzene sulfonate, sodium alkylnaphthalene sulfonate, sodium alkyl sulfate, sodium alkyl sulfonate, sodium alkyl ether sulfate, monoalkyl phosphate, polyoxyethylene
  • Examples include sodium alkyl ether phosphate, sodium fatty acid ester sulfonate, sodium fatty acid ester sulfate, sodium fatty acid alkylose amide sulfate, sodium fatty acid amide sulfonate, and the like.
  • cationic surfactants include alkylmethylammonium chloride, alkyltrimethylammonium chloride, dialkyldimethylammonium chloride, alkyldimethylbenzylammonium chloride, and alkylpyridinium chloride.
  • zwitterionic surfactants include alkylaminocarboxylates, carboxybetaines, alkylbetaines, sulfobetaines, and phosphobetaines.
  • Nonionic surfactants include sucrose fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene lanolin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene glycol mono fatty acid ester, polyoxyethylene alkylphenyl ether, polyoxyethylene Oxyethylene monobenzyl phenyl ether, polyoxyethylene dibenzyl phenyl ether, polyoxyethylene tribenzyl phenyl ether, polyoxyethylene monostyryl phenyl ether, polyoxyethylene distyryl phenyl ether, polyoxyethylene tristyryl phenyl ether, polyoxyethylene Biphenyl ether, polyoxyethylene phenoxyphenyl ether, polyoxyethylene cumylphenyl Ether, polyoxyethylene alkyl ethers, fatty acid alkanolamides, fatty acid monoethanolamide, fatty acid diethanolamide, fatty acid triethanol amide, polyoxyethylene fatty acid amides, isopropanol
  • alkyl here is illustrated, a C1-C30 linear saturated hydrocarbon group or a branched saturated hydrocarbon group will be mentioned.
  • a linear unsaturated hydrocarbon group or a branched unsaturated hydrocarbon group may be used instead of alkyl.
  • Polymeric surfactants include polyvinylpyrrolidone (PVP), polypyrrole, polythiophene, (meth) acrylic acid copolymer, maleic acid copolymer, polystyrene sulfonate, vinylpyridine copolymer, polyethyleneimine, polyvinyl alcohol, Synthetic polymer surfactants such as polyvinyl ether and polyacrylamide, and semisynthetic polymer surfactants such as carboxymethylcellulose, methylcellulose, ethylcellulose, hydroxyethyl sesulose, and hydroxypropylmethylcellulose are used.
  • PVP polyvinylpyrrolidone
  • polypyrrole polypyrrole
  • polythiophene polythiophene
  • acrylic acid copolymer maleic acid copolymer
  • polystyrene sulfonate vinylpyridine copolymer
  • vinylpyridine copolymer polyethyleneimine
  • polyvinyl alcohol Synthetic polymer surfactants such as polyviny
  • the polymeric surfactant is a non-ionic surfactant, an anionic surfactant, and other general surfactants with a structure having a pair of hydrophilic groups and lipophilic groups in the molecule.
  • the surfactant has a complicated structure having a large number of hydrophilic groups and lipophilic groups, and has a large molecular weight.
  • general surfactants and polymer surfactants are greatly different both in structure and molecular weight.
  • the polymer surfactant used in the present invention is preferably a polymer surfactant having a number average molecular weight of 1,000 or more (GPC measurement, styrene conversion), and more preferably 5,000 or more.
  • GPC measurement, styrene conversion preferably 5,000 or more.
  • the amount of the surfactant used is 0.01 to 2 parts by weight, preferably 0.01 to 1 part by weight based on 1 part by weight of the PPS resin.
  • the amount of these surfactants added is in the range of 0.01 to 100 parts by weight, preferably in the range of 0.5 to 100 parts by weight, more preferably 1 to 100 parts by weight of the PPS resin fine particles.
  • the range is from 100 parts by weight.
  • the mixing ratio of the PPS resin fine particles and the dispersion medium used in the dispersion step is preferably in the range of 1 to 50 parts by weight, particularly preferably 1 to 30 parts by weight with respect to 100 parts by weight of the dispersion medium.
  • the PPS resin fine particles obtained in the above filtration / isolation step are ultrasonically dispersed so that the average particle size is reduced as much as possible with an ultrasonic output of 90 w to 120 W.
  • the PPS resin fine particle dispersion may also contain coarse particles and precipitates in some cases. In that case, coarse particles or precipitates may be separated from the dispersed portion. When only the dispersion liquid is obtained, the coarse particles and precipitates may be separated from the dispersion portion. For that purpose, decantation, filtration, centrifugation, etc. may be performed to remove the coarse particles and precipitate portions.
  • the dispersion refers to a state in which the interface between the fine PPS resin particles and the dispersion medium does not appear even after being allowed to stand at room temperature (25 ° C.) for 24 hours.
  • PPS resin fine particles The PPS resin fine particles obtained by the production method of the present invention are produced using the above-described PPS resin as a raw material by a production method including steps (a) and (b), whereby the dispersity of the PPS resin is obtained.
  • Spherical PPS resin fine particles having an average primary particle size of 90 nm to 300 nm and a sphericity of 0.85 or more can be obtained.
  • PPS resin fine particles having a coefficient of variation in average primary particle diameter of 20 to 45% can be used. For spacer applications and applications where a constant film thickness is required, it is required to have the same particle size, so a smaller coefficient of variation is preferred.
  • spherical PPS resin fine particles having a sphericity of 0.85 or more.
  • the dispersity and alkali metal content of the fine PPS resin particles depend on the dispersity and alkali metal content of the PPS resin used as a raw material, and the measurement method and preferred range are also the same.
  • the average primary particle size of the PPS resin fine particles is determined by selecting an arbitrary 100 particles from an image obtained by a scanning electron microscope, measuring the particle size using the maximum length as the particle size, and calculating the average value as the average primary particle size. The particle size.
  • the coefficient of variation (CV) of the average primary particle size is expressed by the following equation (2) using the value of the particle size distribution obtained by measuring arbitrary 100 particle sizes from an image obtained with a scanning electron microscope. ) To formula (4).
  • the average particle size of the PPS resin fine particles is that of Nikkiso Laser Diffraction / Scattering Particle Size Distribution Measuring Device MT3300EXII. Measurement was performed using a 0.5 wt% aqueous solution. Specifically, the cumulative curve is obtained by setting the total volume of fine particles obtained by analyzing the scattered light of the laser by the microtrack method to 100%, and the particle diameter (median diameter: d50) at which the cumulative curve becomes 50% is obtained. The average particle size of the fine particles was used.
  • the average primary particle size in the present invention is an arbitrary value obtained by selecting arbitrary 100 particles from an image obtained with a scanning electron microscope JEOL JMS-6700F manufactured by JEOL and measuring the maximum length as the particle size. was the average primary particle size.
  • the coefficient of variation (CV) of the average primary particle size in the present invention is a value of the particle size distribution obtained by measuring arbitrary 100 particle sizes from an image obtained with a scanning electron microscope JEOL JMS-6700F manufactured by JEOL. Was obtained by the following formulas (2) to (4).
  • sphericity of primary particles For the sphericity in the present invention, arbitrary 30 particles are selected from an image (magnification 30,000 times) obtained with a scanning electron microscope JEOL JMS-6700F manufactured by JEOL, and the shortest and longest diameters are selected as a short diameter and a long diameter, respectively. The average value of the ratio (minor axis / major axis) was defined as the sphericity of the primary particles.
  • Ultrasonic dispersion is an ultrasonic homogenizer manufactured by Nippon Seiki, US-300T (ultrasonic oscillator: rated output 300 W, oscillation frequency 19.5 KHz ⁇ 1 KHz (automatic frequency tracking type), ultrasonic transducer: ⁇ 26 mm PZT (bolt clamped strain type)
  • the ultrasonic oscillation chip was adjusted to have a predetermined output using a vibrating element, and was contacted in a PPS resin fine particle dispersion (suspension) liquid.
  • the temperature was raised from room temperature to 200 ° C. over 25 minutes while stirring at 400 rpm. Next, the temperature was raised to 250 ° C. over 35 minutes, and the reaction was performed at 250 ° C. for 2 hours. Next, the extraction valve was gradually opened while maintaining the internal temperature at 250 ° C., and 26.6 kg of the solvent was distilled off over 40 minutes. After completion of the solvent distillation, the autoclave was cooled to near room temperature and the contents were collected.
  • the obtained dried solid was charged into a glass test tube equipped with a distilling tube and a stirring blade, and then decompression and nitrogen substitution in the test tube were repeated three times. While maintaining the inside of the test tube at about 0.1 kPa, the temperature was adjusted to 340 ° C. and heated for 120 minutes, and then cooled to room temperature to obtain a polymer. Based on the infrared spectrum, the product obtained was found to be a PPS resin. Further, GPC measurement showed that the obtained product had a weight average molecular weight of 50,000 and a dispersity of 2.35. As a result of measuring the weight loss rate during heating of the obtained product, ⁇ Wr was 0.055%. Furthermore, as a result of quantifying the alkali metal content of the obtained product, the Na content was 70 ppm by weight, and no other alkali metals were detected.
  • the residual water content in the system per 1 mol of the alkali metal sulfide charged was 1.06 mol including the water consumed for the hydrolysis of NMP.
  • the amount of hydrogen sulfide scattered was 0.02 mole per mole of charged alkali metal sulfide.
  • the content was diluted with about 35 liters of NMP, stirred as a slurry at 85 ° C. for 30 minutes, and then filtered through an 80 mesh wire mesh (aperture 0.175 mm) to obtain a solid.
  • the obtained solid was similarly washed and filtered with about 35 liters of NMP.
  • the obtained solid was added to 70 liters of ion exchange water, stirred at 70 ° C. for 30 minutes, and then filtered through an 80 mesh wire net to collect the solids three times in total.
  • the obtained solid and 32 g of acetic acid were added to 70 liters of ion exchange water, stirred at 70 ° C. for 30 minutes, and then filtered through an 80 mesh wire net.
  • the obtained solid was further added to 70 liters of ion exchange water, stirred at 70 ° C. for 30 minutes, and then filtered through an 80 mesh wire net to collect the solid.
  • the solid material thus obtained was dried at 120 ° C. under a nitrogen stream to obtain a powdered PPS resin.
  • the weight average molecular weight was 50,000, and the degree of dispersion was 2.66.
  • the weight loss rate during heating of the PPS resin was ⁇ Wr of 0.23%, and the alkali metal content was quantified.
  • the Na content was 120 ppm by weight, and other alkali metals were detected. There wasn't.
  • Example 1 [Dissolution process] A 1 L autoclave (dissolution tank) was opened and closed, and a connecting pipe was mounted so that the end of the pipe was positioned in the tank. Further, as a receiving tank for flash crystallization, a 1 L pressure tank was equipped with a stirrer, a condenser, and a gas vent pipe, and the other end of the connecting pipe of the dissolution tank was placed in the tank. 12 g of PPS resin of Reference Example 1 and 388 g of NMP were placed in the dissolution tank, and the valve of the internal connection pipe was sealed and replaced with nitrogen, and then the internal temperature was raised to 270 ° C. with stirring. The internal pressure (gauge pressure) at this time was 0.4 MPa.
  • the solid content was suspended in 200 g of ion-exchanged water, and then filtered with a centrifugal dehydrator. The same operation was performed twice to obtain a wet PPS resin fine particle wet cake (solid content concentration: 21.3 wt%).
  • the average primary particle diameter of the PPS resin fine particles was 98.6 nm, the coefficient of variation was 23.0%, and the sphericity was 0.961. Further, the degree of dispersion was 2.47, and the Na content was 71 ppm by weight.
  • Example 2 The same procedure as in Example 1 was performed except that 20 g of PPS resin and 380 g of NMP in the dissolution tank were used. PPS resin fine particles having an average primary particle size of 121.0 nm, a coefficient of variation of 43.1%, and a sphericity of 0.956 were obtained. Obtained. Further, the degree of dispersion was 2.44, and the Na content was 72 ppm by weight.
  • Example 3 The same procedure as in Example 1 was performed except that 36 g of PPS resin and 364 g of NMP in the dissolution tank were used. PPS resin fine particles having an average primary particle size of 151.4 nm, a coefficient of variation of 44.4%, and a sphericity of 0.966 were obtained. Obtained. Further, the degree of dispersion was 2.49, and the Na content was 72 ppm by weight.
  • Example 4 The same procedure as in Example 1 was carried out except that 32 g of PPS resin, 368 g of NMP in the dissolution tank, 60 ° C. of the receiving tank temperature, NMP 266 g of the receiving tank solvent, and 133 g of ion-exchanged water were used, and the average primary particle size was 179.5 nm. PPS resin fine particles having a coefficient of 30.5% and a sphericity of 0.919 were obtained. Further, the degree of dispersion was 2.49, and the Na content was 73 ppm by weight.
  • Example 5 The same procedure as in Example 1 was performed except that 32 g of PPS resin, 368 g of NMP in the dissolution tank, 60 ° C. of the receiving tank temperature, 320 g of NMP and 80 g of ion-exchanged water were used as the receiving solvent, and the average primary particle size was 184.2 nm. PPS resin fine particles having a coefficient of 31.9% and a sphericity of 0.921 were obtained. Further, the degree of dispersion was 2.40, and the Na content was 72 ppm by weight.
  • Example 6 The same procedure as in Example 1 was carried out except that 32 g of PPS resin, 368 g of NMP in the dissolution tank, 100 ° C. of the receiving tank temperature, NMP 266 g of the receiving tank solvent, and 133 g of ion-exchanged water were used, and the average primary particle size was 184.0 nm. PPS resin fine particles having a coefficient of 29.2% and a sphericity of 0.936 were obtained. The degree of dispersion was 2.37, and the Na content was 68 ppm by weight.
  • Example 7 Flash crystallization was carried out in the same manner as in Example 1 except that 32 g of PPS resin, 368 g of NMP in the dissolution tank, 110 ° C. of the receiving tank, 266 g of NMP and 134 g of ion-exchanged water were used as the receiving solvent.
  • the flash solution was heated at 80 ° C. for 4 hours and allowed to stand at room temperature for 1 hour.
  • the aggregated liquid was subjected to solid-liquid separation with a centrifugal dehydrator, and the solid content was collected by filtration.
  • the solid content was suspended in 200 g of ion-exchanged water, and then filtered with a centrifugal dehydrator.
  • the same operation was performed twice to obtain a hydrous PPS resin fine particle wet cake (solid content concentration: 22.3% by weight).
  • the average primary particle size of the fine PPS resin particles was 205 nm, the coefficient of variation was 33.7%, and the sphericity was 0.900. Further, the degree of dispersion was 2.36, and the Na content was 75 ppm by weight.
  • Example 8 Flash crystallization was performed in the same manner as in Example 1 except that 32 g of PPS resin, 368 g of NMP in the dissolution tank, 117 ° C. of the receiving tank, 266 g of NMP and 133 g of ion-exchanged water were used as the receiving solvent. Flush liquid aggregation and cake washing were carried out in the same manner as in Example 7 to obtain PPS resin fine particles having an average primary particle size of 227.6 nm, a coefficient of variation of 51.4%, and a sphericity of 0.894. Further, the degree of dispersion was 2.47, and the Na content was 70 ppm by weight.
  • Example 9 The same procedure as in Example 1 was carried out except that 36 g of PPS resin, 364 g of NMP in the dissolution tank, the temperature of the receiving tank was 60 ° C., the solvent of the receiving tank was 200 g of NMP, and 200 g of ion-exchanged water. PPS resin fine particles having a coefficient of 40.3% and a sphericity of 0.942 were obtained. The degree of dispersion was 2.38, and the Na content was 78 ppm by weight.
  • Example 10 Flash crystallization was performed in the same manner as in Example 1 except that 36 g of PPS resin, 364 g of NMP in the dissolution tank, 60 ° C. of the receiving tank, 266 g of NMP and 133 g of ion-exchanged water were used as the receiving solvent. Flush liquid aggregation and cake washing were carried out in the same manner as in Example 7. PPS resin fine particles having an average primary particle size of 199.2 nm, a coefficient of variation of 35.3%, and a sphericity of 0.901 were obtained. Further, the degree of dispersion was 2.42, and the Na content was 75 ppm by weight.
  • Comparative Example 1 The same operation as in Example 1 was performed except that the PPS resin of Reference Example 2 was used.
  • the average primary particle size of the fine PPS resin particles was 99.0 nm, the coefficient of variation was 26.1%, and the sphericity was 0.960.
  • the dispersity was 2.71, and the Na content was 125 ppm by weight.
  • Comparative Example 2 In a 1 L pressure vessel, 10 g of the PPS resin obtained in Reference Example 1 and 1000 g of 1-chloronaphthalene (manufactured by Kanto Chemical Co., Inc.) were added. After sealing under nitrogen, the temperature was raised to 230 ° C. and stirred for 20 minutes. After cooling the pressure vessel to near room temperature with ice water, the PPS resin particle suspension was filtered to remove coarse particles, the filtrate was centrifuged at 6,000 rpm, and the supernatant was collected. The average particle size of the supernatant was 1.92 ⁇ m.
  • the generated particles are non-spherical particles, the sphericity cannot be measured, and the agglomerated particle size and the primary particle size (particle size of individual particles) cannot be distinguished, so the particle size distribution is measured by the laser diffraction / scattering method, The average particle size was determined.
  • the degree of dispersion is 2.5 or less
  • the average primary particle size is 90 nm to 300 nm
  • the sphericity is 0.85 or more
  • the alkali metal ions are less than 100 ppm
  • the amount of gas generated during molding is small.
  • Spherical PPS resin fine particles can be easily obtained.
  • the PPS resin fine particles obtained in this way and the dispersion thereof have heat resistance, they are widely used for adhesives, paints and printing inks, electrical / electronic materials, etc. that require heat resistance. Can be used

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)

Abstract

La présente invention concerne : des microparticules de résine de poly(sulfure de phénylène) générant peu de gaz une fois chauffée, leur procédé de production, et un liquide de dispersion associé. Le procédé de production comprend les étapes (a) et (b) et utilise comme matière première associée de la résine de poly(sulfure de phénylène) représentée par la formule (1) et présentant une réduction du poids (ΔＷｒ) une fois chauffée inférieure à 0,18 %. (a) une étape (étape de dissolution) dans laquelle de la résine de poly(sulfure de phénylène) est dissoute dans une solution de solvant organique. (b) une étape (étape de dépôt) dans laquelle est mise en œuvre une cristallisation éclair et des microparticules de résine de poly(sulfure de phénylène) sont déposées. (1) ΔＷｒ = (W1 - W2) / W1 × 100 (%) (une valeur obtenue pour un poids (W2) d'échantillon lorsque la température atteint 330 °C, sur la base d'un poids (W1) d'échantillon lorsque la température atteint 100 °C, lors d'une analyse thermogravimétrique à une vitesse d'augmentation de température de 20 °C/min à partir de 50 °C jusqu'à une température quelconque supérieure ou égale à 330 °C, sous atmosphère non oxydante, à pression normale).
PCT/JP2015/051247 2014-01-24 2015-01-19 Microparticules de résine de poly(sulfure de phénylène), leur procédé de production, et liquide de dispersion WO2015111546A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017061607A (ja) * 2015-09-25 2017-03-30 国立大学法人東京農工大学 ポリフェニレンサルファイド微粒子
CN117843997A (zh) * 2024-01-04 2024-04-09 浙江新和成特种材料有限公司 聚苯硫醚树脂微粒及其制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007034800A1 (fr) * 2005-09-22 2007-03-29 Toray Industries, Inc. Poly(sulfure d’arylène) et son procédé de production
JP2008231250A (ja) * 2007-03-20 2008-10-02 Toray Ind Inc ポリフェニレンスルフィド微粒子、その製造方法および分散液
WO2009119466A1 (fr) * 2008-03-28 2009-10-01 東レ株式会社 Procédé de fabrication de fines particules de résine de polysulfure de phénylène, fines particules de résine de polysulfure de phénylène et dispersion de celles-ci

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007034800A1 (fr) * 2005-09-22 2007-03-29 Toray Industries, Inc. Poly(sulfure d’arylène) et son procédé de production
JP2008231250A (ja) * 2007-03-20 2008-10-02 Toray Ind Inc ポリフェニレンスルフィド微粒子、その製造方法および分散液
WO2009119466A1 (fr) * 2008-03-28 2009-10-01 東レ株式会社 Procédé de fabrication de fines particules de résine de polysulfure de phénylène, fines particules de résine de polysulfure de phénylène et dispersion de celles-ci

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017061607A (ja) * 2015-09-25 2017-03-30 国立大学法人東京農工大学 ポリフェニレンサルファイド微粒子
CN117843997A (zh) * 2024-01-04 2024-04-09 浙江新和成特种材料有限公司 聚苯硫醚树脂微粒及其制备方法

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JPWO2015111546A1 (ja) 2017-03-23

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