WO2006082880A1 - Composition composite de résine thermoplastique, procédé servant à produire celle-ci et utilisation de celle-ci - Google Patents

Composition composite de résine thermoplastique, procédé servant à produire celle-ci et utilisation de celle-ci Download PDF

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Publication number
WO2006082880A1
WO2006082880A1 PCT/JP2006/301748 JP2006301748W WO2006082880A1 WO 2006082880 A1 WO2006082880 A1 WO 2006082880A1 JP 2006301748 W JP2006301748 W JP 2006301748W WO 2006082880 A1 WO2006082880 A1 WO 2006082880A1
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Prior art keywords
inorganic fine
thermoplastic resin
fine particles
composite composition
resin composite
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PCT/JP2006/301748
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English (en)
Japanese (ja)
Inventor
Jeong Chang Lee
Kunihiko Takeda
Mitsuru Tanahashi
Naoki Kanayama
Narihiro Matsuda
Masaki Hirose
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Du Pont-Mitsui Fluorochemicals Co., Ltd.
National University Corporation Nagoya University
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Application filed by Du Pont-Mitsui Fluorochemicals Co., Ltd., National University Corporation Nagoya University filed Critical Du Pont-Mitsui Fluorochemicals Co., Ltd.
Publication of WO2006082880A1 publication Critical patent/WO2006082880A1/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
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/201—Pre-melted polymers
    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/10—Reinforcing macromolecular compounds with loose or coherent fibrous material characterised by the additives used in the polymer mixture

Definitions

  • Thermoplastic resin composite composition production method and use thereof
  • the present invention relates to a thermoplastic resin composite composition in which inorganic fine particles are dispersed at a primary particle level and a method for producing the same. More specifically, it is obtained by melt-mixing a low-strength inorganic fine particle aggregate formed by the cohesive force between inorganic fine particles and a thermoplastic resin. The inorganic fine particles are dispersed in the resin at the level of the original inorganic fine particles.
  • the present invention relates to a thermoplastic resin composite composition that can be said to be a thermoplastic resin nanocomposite and a method for producing the same.
  • Japanese Patent Application Laid-Open No. 2001-152030 discloses an inorganic porous material having an average particle diameter of 100 nm to 1000 nm obtained by firing an inorganic material such as porous glass or acid silicate (hereinafter sometimes referred to as silicic force).
  • An additive selected from metals, metal salts, and inorganic compounds or a flame retardant is preliminarily supported on the material, and the inorganic porous material is crushed by melting and mixing with the resin, and the average particle size is 10 ⁇ m
  • a resin composite composition characterized in that particles carrying the additive or flame retardant of ⁇ 100 nm are dispersed in the resin, and a method for producing the same is described.
  • the structure of the porous glass described in the above publication is a covalent bond between silicon and oxygen, and crushing and dispersing the porous glass is equivalent to breaking the covalent bond, which is large. Therefore, it is extremely difficult to crush and disperse the porous glass by melt mixing with the resin.
  • an aggregate of inorganic fine particles such as silica fine particles having an average primary particle diameter of 12 nm is 600 ° C to
  • the lOOOnm inorganic porous material is solidified into a skeleton that has solid bonds due to the surface melting of silica particles (or aggregates of silica particles) that are slightly melted and fused together by firing.
  • S and the inorganic porous material after melt mixing have a wide average particle size of 290 nm, particle size distribution of 40 nm to 100, 0 OOnm (100 m), and the original primary particles have not been successfully crushed.
  • the 13th Symposium on Polymer Materials, P10, 2003 the mechanical properties are markedly deteriorated due to the presence of many non-crushed inorganic fine particle aggregated sintered bodies having a particle size of 10 m or more in polystyrene resin.
  • the dispersion state of the inorganic fine particles or the inorganic nanoparticles greatly changes depending on the type of the fine particles to be dispersed and the hydrophobicity / hydrophilicity as well as the kind of the inorganic fine particles or the inorganic nanoparticles and the surface property alone.
  • Patent Document 1 Japanese Patent Laid-Open No. 2001-152030
  • Non-Patent Document 1 Proceedings of 13th Symposium on Polymer Materials, P10, 2003
  • the present inventor has found that the strength formed by the cohesive force between the inorganic fine particles is low, and the inorganic fine particle aggregate and the thermoplastic resin are melt-mixed, whereby the inorganic stress is generated by the shear stress generated in the melt mixing apparatus.
  • Fine particle aggregates are uniformly crushed and dispersed to the original inorganic fine particles (hereinafter sometimes referred to as primary particles), and mechanical properties are maintained while maintaining a certain degree of elongation and melt moldability of thermoplastic resin.
  • primary particles original inorganic fine particles
  • the present invention provides a thermoplastic resin composite composition excellent in mechanical properties, dimensional stability, etc., in which inorganic fine particles are dispersed to the level of primary particles.
  • the present invention relates to a thermoplastic resin in which inorganic fine particles are obtained by melt-mixing a low-strength inorganic fine particle aggregate formed by the cohesive force between inorganic fine particles and a thermoplastic resin, and the inorganic fine particles are nano-leveled.
  • a composite composition is provided.
  • the present invention also provides a method for producing a thermoplastic resin composite composition, which can be called a resin nanocomposite, in which inorganic fine particles are dispersed to the level of primary particles.
  • the present invention provides an inorganic fine particle aggregate obtained by drying a mixed liquid of inorganic fine particles and an inorganic salt to obtain a solidified product, removing the inorganic salt from the solidified product using a solvent, and drying.
  • the inorganic fine particle aggregate formed by the cohesive force between the inorganic fine particles obtained by performing the drying at a temperature at which surface fusion between the inorganic fine particles does not substantially occur and the thermoplastic resin are melted.
  • a thermoplastic resin composite composition in which inorganic fine particles having an average particle size of 1 ⁇ m or less obtained by mixing are dispersed in / in a resin.
  • thermoplastic resin composite composition described above in which the crushing strength of the inorganic fine particle aggregate is 1.5 MPa or less is a preferred embodiment of the present invention.
  • thermoplastic resin composite composition described above in which the average primary particle size of the inorganic fine particles is 1 m or less, is a preferred embodiment of the present invention.
  • thermoplastic resin composite composition in which the compression load of the inorganic fine particle aggregate is 40 mN or less is a preferred embodiment of the present invention.
  • thermoplastic rosin composite composition described above having a force particle diameter of not less than 80% of the number of inorganic fine particles dispersed in the rosin and not more than 600 nm is a preferred embodiment of the present invention.
  • thermoplastic resin in which the inorganic fine particles are at least one selected from the group consisting of acid carbonate, titanium oxide, acid aluminum, and zinc oxide and antimony pentaoxide.
  • the fat composite composition is a preferred embodiment of the present invention.
  • the inorganic salt is at least one selected from the group consisting of hydrohalic acid, phosphoric acid, sulfuric acid, nitric acid, and molybdic acid, lithium metal salt, alkaline earth metal salt, and ammonium salt power.
  • a plastic rosin composite composition is a preferred embodiment of the present invention.
  • the inorganic salt is at least one selected from potassium bromide, potassium chloride, ammonium molybdate, sodium hydrogen phosphate, calcium chloride, and ammonium bromide force.
  • the above-described thermoplastic resin composite composition is a preferred embodiment of the present invention.
  • thermoplastic resin composite composition performed at / T) of 0.23 or less is a preferred embodiment of the present invention.
  • the thermoplastic resin is polyethylene (PE), polypropylene (PP), polysalt resin (PV C), polystyrene (PS), polymethacrylic resin (PMMA), polyethylene butyl alcohol copolymer (EVOH), acrylic butadiene styrene resin (ABS), polyacetal (POM), polyamide (PA), polycarbonate (PC), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyphenylene ether (PPE), polyphenol- Renoxide (PPO), Polyphenylene-sulfite (PPS), Polysulfone (PSE), Polyimide resin (PI), Polyimide amide resin (PAI), Fully aromatic polyester (Liquid crystal polymer), Polyoxybenzylene (POB) , Polymethylpentene (TPX), Polyethersulfone (PESF), Polyetherimide (PEI), Polyarylate (PAR), Polyetheretherketo The above-mentioned thermoplastic resin composite composition
  • the present invention also prepares a solidified product by drying a mixed solution of inorganic fine particles and inorganic salt, removes the inorganic salt from the solidified product using a solvent, and dries, and then the drying is performed between the inorganic fine particles.
  • the above-described thermoplastic resin composite composition is obtained by melt-mixing an inorganic fine particle aggregate formed by the cohesive force between inorganic fine particles obtained by performing the temperature at which no surface fusion occurs, and a thermoplastic resin. A method of manufacturing an object is provided.
  • thermoplastic resin composite composition in which inorganic fine particles are dispersed up to the primary particle level in a thermoplastic resin.
  • the present invention makes it possible to provide a thermoplastic resin composite composition in which inorganic fine particles are uniformly dispersed at a nano level in thermoplastic resin.
  • inorganic fine particles can be dispersed in thermoplastic resin to the level of primary particles.
  • a method for producing a thermoplastic rosin composite composition is also provided.
  • thermoplastic resin and the inorganic fine particle aggregate having low strength are melt-mixed to disperse the inorganic fine particles to the nano level, so that the thermoplastic resin can be easily nanocomposited. it can.
  • thermoplastic resin composite composition of the present invention can be applied to all fields where particles can be expected to be dispersed at the nano level.
  • thermoplastic resin composite composition excellent in mechanical properties and dimensional stability and a method for producing the same are provided.
  • the present invention provides an inorganic fine particle aggregate formed by the cohesive force of inorganic fine particles and a thermoplastic coagulant obtained by melting and mixing the inorganic fine particles with an average particle size of 1 ⁇ m or less.
  • a thermoplastic resin composite composition that disperses!
  • the inorganic fine particle aggregate formed by the cohesive force between the inorganic fine particles in the present invention means that the inorganic fine particle is formed by the cohesive force between the inorganic fine particles without substantially fusing on the surface. Aggregates.
  • thermoplastic resin used in the present invention is not limited to its kind or chemical structure such as hydrophilic 'hydrophobic', rubber, thermoplastic elastomer, general-purpose resin, engineering ring. Any thermoplastic resin such as plastic can be used.
  • Examples of the rubber include natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), styrene butadiene rubber (SBR), chloroprene rubber (CR), -tolyl rubber (NBR), and butyl rubber (IIR). , Ethylene 'propylene rubber (EPDM), chlorosulfonated polyethylene (CSM), attalinole rubber (ACM, ANM), epichlorohydrin rubber (ECO), silicon rubber (VMQ, FVMQ), fluoro rubber (FKM), urethane rubber, etc. Can be mentioned.
  • Thermoplastic elastomers include styrene (SBC), olefin (TPO), vinyl chloride (TPVC), urethane (TPU), ester (TPEE), and amide (TPAE). I can list them.
  • SBC styrene
  • TPO vinyl chloride
  • TPVC vinyl chloride
  • TPU urethane
  • TPEE ester
  • TPAE amide
  • the general-purpose resin a general-purpose resin used in general melt molding can be preferably used.
  • PE polyethylene
  • PP polypropylene
  • PVC polychlorinated butyl
  • PS polystyrene
  • polymethacrylic resin examples thereof include resin (PMMA), polyethylene butyl alcohol copolymer (EV OH), and acrylic butadiene styrene resin (ABS).
  • Engineering plastics include polyacetanol (POM), polyamide (PA), polycarbonate (PC), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyphenylene ether (PPE), polyphenol lenoxide (PPO). ), Polyphenylene sulfite (PPS), polysulfone (PSE), polyimide resin (PI), polyimide amide resin (PAI), wholly aromatic polyester (liquid crystal polymer), polyoxybenzylene (POB), polymethyl Examples include rupentene (TPX), polyethersulfone (PESF), polyetherimide (PEI), polyarylate (PAR), polyetheretherketone (PEEK), and polyetherketoneketone (PEKK).
  • POM polyacetanol
  • PA polyamide
  • PC polycarbonate
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • PPE polyphenylene ether
  • PPO polyphenol lenoxide
  • the inorganic fine particles used in the preparation of the inorganic fine particle aggregate in the present invention include silicon oxide, titanium oxide, zeolite, acid zirconium, alumina, pentoxide antimony, silicon carbide, aluminum nitride, and nitride.
  • Dispersions of inorganic fine particles such as silicon, barium titanate, aluminum borate, boron nitrite, lead oxide, zinc oxide, tin oxide, cerium oxide, magnesium oxide, cerium zincate, calcium silicate, zirconium silicate
  • sol (Hereinafter sometimes referred to as sol).
  • sol These inorganic fine particles can be used alone or in combination of two or more.
  • the inorganic fine particle aggregate of the present invention a sol of inorganic fine particles and an inorganic salt are mixed, and the mixed solution is dried to produce a solidified product of the inorganic fine particles and the inorganic salt, and the solvent is removed from the solidified product. And agglomerates of inorganic fine particles obtained by elution and removal of inorganic salts and drying by drying.
  • the inorganic fine particle aggregate of the present invention is formed by a cohesive force between the inorganic fine particles, and a temperature at which surface fusion between the inorganic fine particles does not substantially occur, preferably a temperature at which the neck formation described later does not occur. Agglomerates of inorganic fine particles dried at
  • the temperature at which surface fusion between the inorganic fine particles does not substantially occur is preferably different depending on the type of inorganic fine particles used. Its temperature The inorganic fine particles can be selected by confirming the above.
  • the thus obtained aggregate of inorganic fine particles is an aggregate formed only by the cohesive force between the inorganic fine particles, so that the inorganic fine particles described in JP-A-2001-152030 are used.
  • the mixture of the fine particles and the inorganic salt is fired at a high temperature to form an aggregate of inorganic fine particles having a lower strength than the aggregate of inorganic fine particles prepared by fusing the inorganic fine particles.
  • the inorganic fine particle aggregate obtained by removing the inorganic salt with a solvent and drying in the present invention usually gives a coarse particle or agglomerate having a large particle diameter. It may be pulverized and classified. From the viewpoint of biting in the hopper of the extruder, the average particle size of the aggregate of inorganic fine particles of the present invention is in the range of 50 ⁇ m to 400 ⁇ m, preferably 70 0 ⁇ to 300 / ⁇ ⁇ . A range is preferred. In the case of pulverizing and classifying the aggregate, it is preferable that the average particle diameter is within the above range.
  • the solvent for eluting the inorganic salt from the solidified product of the inorganic fine particles and the inorganic salt may be the same as or different from the solvent used for the mixed liquid of the inorganic fine particles and the inorganic salt. Preferably it is active.
  • a solvent can be appropriately selected from polar solvents, which are poor solvents for inorganic fine particles and good solvents for inorganic salts. Water is one suitable example of such a solvent. Since the inorganic salt is eluted and removed using a solvent that elutes the inorganic salt from the solidified product, it acts as a kind of pore-forming agent for the resulting aggregate.
  • the inorganic fine particle aggregate of the present invention is preferably obtained by using at least one kind selected from silica sol, titanium oxide sol, alumina sol, zeolite sol, a composite oxide of zinc oxide and antimony pentoxide as the inorganic fine particles.
  • Water is used as a solvent, and a water-soluble inorganic salt is used as a pore forming agent.
  • water-soluble inorganic salt examples include hydrohalic acid, phosphoric acid, sulfuric acid, nitric acid, molybdate alkali metal salt, alkaline earth metal salt, ammonium salt, etc., preferably potassium nitrate, potassium iodide, ammonium molybdate. -Um, sodium phosphate-sodium hydrogen, potassium bromide, odor Ammonium chloride, potassium chloride, calcium chloride, copper chloride, calcium nitrate and the like.
  • These inorganic salts can be used alone or in combination of two or more.
  • a form using silica sol as the inorganic fine particles is more preferable.
  • An inorganic fine particle aggregate having a high purity can be obtained as an inorganic fine particle aggregate obtained by using a solvent having a high purity as the solvent. For example, when the residual inorganic salt is eluted repeatedly using pure water, inorganic fine particle aggregates with extremely high purity can be obtained.
  • a high-purity agglomerate having a silica particle force can be obtained by applying this method.
  • the thermoplastic resin composition obtained by melt-mixing the high-purity agglomerate and the thermoplastic resin obtained in this way can be suitably used even for parts that require purity used in semiconductor manufacturing equipment and the like.
  • the inorganic fine particle aggregate is obtained by a method described in Japanese Patent No. 3369193, wherein a fired body produced using silica sol or alumina sol, an alkali metal halide and a substitute agent as raw materials is used. It also has a metal power that has a lower ionization tendency than the metal in the substitution agent. It is immersed in an aqueous solution of the additive or its metal compound to remove the alkali metal halide, and replaces the metal of the additive with the substitution agent and carries it. Silica aggregates may be used. Note that when the firing described in the above patent is performed, the good dispersion expected in the present invention cannot be obtained.
  • Examples of the additive for the composite inorganic fine particles include inorganic substances such as hydroxide-magnesium, hydroxide-aluminum, and trimonate-antimony, which have a catalytic action, palladium, copper, magnesium, iron, aluminum, Metals such as tin, nickel, conoret, titanium, white gold, gold and silver are used.
  • inorganic fine particle aggregates supporting an additive selected from metals, metal salts, and inorganic compounds in the resin By dispersing inorganic fine particle aggregates supporting an additive selected from metals, metal salts, and inorganic compounds in the resin to the nano level, effects such as reduction of the amount added can be obtained.
  • the strength formed by the agglomeration force between the inorganic fine particles obtained in the present invention is low, and the strength of the inorganic fine particle aggregate is the kind and particle size of the inorganic fine particle sol, the pH of the inorganic fine particle sol, the inorganic salt These conditions vary depending on the type, content, drying temperature, etc. By selecting, the strength of the inorganic fine particle aggregate can be controlled.
  • the inorganic fine particle aggregate of the present invention is melt-mixed with the thermoplastic resin to disperse the inorganic fine particles in the resin
  • the type of the thermoplastic resin to be melt-mixed and the melt-mixing device used Depending on the structure (screw structure and combination), melt mixing conditions (temperature and screw rotation speed), etc., the average particle size and dispersion state of the inorganic fine particle aggregates dispersed in the thermoplastic resin change. Therefore, the inorganic fine particle agglomerates and thermoplastics used in order to uniformly crush and disperse the thermoplastic agglomerates and inorganic fine particle agglomerates to the nano level of the original primary particles physically in the hot melt fat. It is necessary to select the conditions for melt mixing according to the type of the resin.
  • thermoplastic resin composite composition can be obtained by controlling both the preparation of inorganic fine particle aggregates and the melt mixing conditions.
  • the strength is the sum of the interparticle adhesion forces acting at the contact points between a large number of primary silica particles forming the porous material. It depends on the next particle size (Chemie Ingenieurtechnik, vol 42, p538, 1970).
  • the average primary particle size is 50 nm or more, preferably 90 nm or more, more preferably llOnm or more and 1 m or less.
  • the agglomerate strength is inversely proportional to the primary particle size, and the average primary particle size force increases, and the agglomerate strength increases and the crushing process becomes difficult during the melt mixing process. Tend.
  • the inorganic fine particle aggregates are uniformly crushed and dispersed in the thermoplastic resin when melt-mixed with a stronger shear stress. .
  • the inorganic salt used in the present invention functions as a kind of pore-forming agent for the aggregate of inorganic fine particles, the strength of the inorganic fine particle aggregate is greatly changed depending on the content of the inorganic salt. . As the content of the inorganic salt with respect to the inorganic fine particles increases, the strength of the inorganic fine particle aggregate decreases. However, if the content of inorganic salt is too high, the inorganic fine particle aggregates are easily crushed by a measuring process and returned to primary particles. Therefore, the content of inorganic salt in the inorganic fine particle aggregate is 1 to 90% by volume, preferably 50 to 85% by volume, more preferably 60 to 80% by volume. %.
  • the mixed liquid After mixing the water-dispersed inorganic fine particle sol and the inorganic salt, the mixed liquid is dried to prepare a solidified product of the inorganic fine particles and the inorganic salt, and the solidification of the inorganic fine particles and the inorganic salt.
  • the temperature at which the inorganic salt is removed and dried by using a solvent that elutes the inorganic salt from the product is a temperature at which surface fusion between the inorganic fine particles does not substantially occur as described above, preferably the formation of a neck Doesn't happen, temperature is desired.
  • the melting point on the surface of the inorganic fine particles is lower than the melting point inside (bulk state)
  • the drying temperature is increased, a part of the surface of the inorganic fine particles is melted, and the aggregate of the inorganic fine particles is formed by the fusion of adjacent inorganic fine particles.
  • the strength of is increased.
  • inorganic fine particles generally have crystal structure defects on the surface of the particles when they are formed. All of these defects are thermally unstable, so they rapidly recover or move when heated.
  • a bonding portion (neck) is formed at the contact portion between adjacent inorganic fine particles. The formation of this neck also increases the strength of the aggregate of inorganic fine particles.
  • the main cause of neck formation is thought to be surface fusion between adjacent inorganic fine particles. Neck formation starts when the ratio (T / T) of the drying temperature (T) expressed in absolute temperature to the melting point (T) of the inorganic fine particles is 0.23.
  • the ratio of the drying temperature shown in absolute temperature to the melting point of the inorganic fine particles is preferably 0.23 or less.
  • the drying be performed at a temperature of 150 ° C or lower, preferably 120 ° C or lower! /.
  • the strength of the inorganic fine particle aggregate of the present invention depends on the type of the resin to be melt-mixed, the structure of the melt-mixing apparatus to be used (screw structure and combination), the melt-mixing conditions (temperature and screw rotation speed), etc. Force due to Compressive Load, measured when the particle size is about 150 m, 0 mN or less, preferably 35 mN or less.
  • the crushing strength S of the inorganic fine particle aggregate of the present invention is 1.50 MPa or less, preferably 1.40 MPa or less. As will be described later, the crushing strength is a strength corrected for the effect of the difference in particle size.
  • the mixing ratio of the inorganic fine particle aggregate to the thermoplastic resin is a force depending on the use of the thermoplastic resin composite composition 0.3 to 70% by weight, more preferably 0.5 to 50% by weight. Most preferably, it is 1 to 30% by weight.
  • Inorganic fine particles are dispersed to the nano level in rosin
  • the interfacial area between the nanoparticle and the rosin matrix is significantly higher in the nano-fax composite mixture or the so-called polymer nano-composite than in the conventional wafer composite mixture in which the filler is dispersed at the micron level. Therefore, there is an advantage that improvement of physical properties can be expected even if a smaller amount of the inorganic fine particle aggregate is added than the conventional resin composite mixture.
  • thermoplastic resin composite composition obtained by the present invention is obtained by melting and mixing the inorganic fine particle aggregate and the thermoplastic resin, and the inorganic fine particles in the resin are 1 ⁇ m (lOOOnm) or less.
  • the thermoplastic thermoplastic resin composite composition is preferably dispersed below 600 nm or less, more preferably 400 nm or less.
  • thermoplastic resin composite composition in which almost all fine particles are dispersed at the nano level.
  • the state in which the inorganic fine particles are dispersed in the thermoplastic resin can be observed with an electron micrograph of the resulting thermoplastic resin composite composition. Using an electron microscope, it is not possible to observe particles of different sizes up to an aggregate of inorganic fine particles with an average particle size of about 12 nm and inorganic fine particles with an average particle size of about 50, OOOnm (50 ⁇ m).
  • Plastic resin composite composition After cooling the sample in liquid nitrogen, the fractured surface obtained by folding is arbitrarily selected from three locations for each sample using an electron microscope, and crushed inorganic fine particle aggregates or primary particles
  • the distribution of the particle size and the number of particles was prepared (the particle size on the horizontal axis is a logarithmic scale), and the particle size with the largest proportion of inorganic fine particles was taken as the average particle. Therefore, when most of the inorganic fine particle aggregates are crushed and dispersed to primary particles, most of the particles counted from the electron micrograph are primary particles, so the average particle size formed inorganic fine particle aggregates. This is the primary particle size.
  • the primary particle when the strength of the inorganic fine particle aggregate is high, the primary particle is not crushed and dispersed, so the average particle size is several hundred times as large as the particle size of the primary particle.
  • the number of inorganic fine particles that can be confirmed by microscopic observation is 80% or more, preferably 90% or more, more preferably 95% or more, force 600 nm or less, more preferably 400 nm or less.
  • a thermoplastic rosin composite composition is a preferred embodiment of the present invention.
  • inorganic fine particles having a lower strength than an inorganic porous material obtained by firing a conventional inorganic material such as porous glass or silica are prepared in advance, and the aggregate and thermoplastic resin are melt-mixed.
  • the strength is low due to shear stress.
  • Manufactures so-called polymer nanocomposites, in which inorganic fine particles are uniformly crushed and dispersed to the nanoscale regardless of the type of thermoplastic resin, hydrophilicity, hydrophobicity, etc. can do.
  • the type of thermoplastic resin used and the melt viscosity are used.
  • the temperature of the resin increases due to internal heat generation, the melt viscosity decreases, and the shear applied to the resin is sheared. Since the stress is low, it is better to set it in consideration of the increase in the resin temperature due to internal heat generation. However, a temperature that does not exceed 50 ° C above the melting point is preferable. In the case of rubber or non-crystalline polymer, it is preferable to lower the mixing temperature as much as possible while suppressing internal heat generation so that large shear stress is applied to the resin.
  • a solidified product is obtained by liquid mixture drying of inorganic fine particles and inorganic salt, and the inorganic salt is removed by using the solidified product solvent, followed by drying.
  • the method of melt-mixing the inorganic fine particle aggregates formed by the cohesive force between the inorganic fine particles, which is obtained by carrying out at a temperature at which no surface fusion occurs, with the thermoplastic resin is the thermoplastic resin of the present invention.
  • a preferred method for producing the composite composition is the thermoplastic resin of the present invention.
  • any kind of particles that can be expected by uniformly dispersing at the nano-level are available. It can be applied to the field and is not particularly limited by the present invention.
  • tubes, sheets, rods, fibers, packings, linings, wire coatings and the like that can be obtained by compression molding, extrusion molding, blow molding, injection molding.
  • the particles are uniformly dispersed in the thermoplastic resin at the nano level, the zero shear viscosity is much higher when the shear rate is low than when the particles are not nano-dispersed.
  • silica when used as the inorganic fine particles, the silica particles increased by nano-dispersion. It can also be used in applications where an improvement in adhesion can be expected due to the interaction between the hydroxyl group bonded to the surface and the metal or substrate.
  • each physical property was measured by the following method.
  • micro-compression tester MCT-W500, manufactured by Shimadzu Corporation
  • spray about lOOmg of sample on a high-rigidity stage measure the particle size D of each sample, and apply a load.
  • the measured experimental force P (Compressive Load) and compression displacement were measured, and the crushing strength S (or breaking strength) of the data was calculated using the following formula (Japan Mining Association, vol. 81, p24, 1965).
  • the experimental force P measured at a compression speed of 103 mNZsec was taken as the compression load.
  • the crushing strength was measured five times for each sample, and the average value was used as the crushing strength (MPa).
  • the inorganic fine particle aggregate of the present invention was selected to have a particle size of about 150 m and the crushing strength was measured.
  • the average particle size of commercially available silica used as a comparative example is smaller than that of the sample of the present invention, the value of the experimental force P is small, but the crushing strength S corrected for the effect of the particle size difference S
  • the fracture surface obtained by folding is arbitrarily selected at three locations for each sample with an electron microscope, and the size of silica particles crushed by the following method The distribution of the silica particle size and its number was prepared (the particle size on the horizontal axis is a logarithmic scale), and the particle size with the largest proportion of silica particles was taken as the average particle.
  • Silica aggregates of 5 m to 20 m The number of silica particles having a particle diameter of 5 ⁇ m to 20 ⁇ m and the particle diameter thereof were measured from the observation result at 500 times (field of view: 180 m ⁇ 180 m). In addition, the number of silica particles corresponding to each particle size counted was multiplied by 6.25 and converted to the result of the area observed at 200 times.
  • silica particles having a particle diameter of 1 ⁇ m to 5 ⁇ m and the particle diameter thereof were measured from the results of observation at 1 to 5 m silica aggregate: 2000 times (field: 45 m ⁇ 45 m). In addition, the number of silica particles corresponding to each particle size counted was multiplied by 100 and converted to the result of the area observed at 200 times.
  • the number of silica particles corresponding to each counted particle size was multiplied by 625 and converted to a result of the area observed at 200 times.
  • the particle size was measured in nm and rounded down to the nearest 100 (eg, 650 nm is 600 nm).
  • the particle size of the silica primary particles was the same as the measured value.
  • Silica aggregate or silica primary particle of 200 nm to 500 nm From the result of observation at 10,000 times (field of view: 9 m X 9 ⁇ m), particle size 200 ⁇ The number of silica aggregates or silica primary particles of ⁇ 500 nm and their particle sizes were measured by the same method as in d), and converted to the result of the area to be observed at 200 times f) Silica aggregates or silica primary of 200 nm or less Particles: From the result of observation at 20000 times (field of view: 4.5 ⁇ ⁇ ⁇ 4.5 ⁇ m), the number of silica aggregates or silica primary particles with a particle size of 200 nm or less and the particle size is the same as d) Measured and converted to the result of the area observed at 200 times. (3) Silica dispersion state
  • thermoplastic resin composite composition sample prepared in liquid nitrogen was observed at three locations for each sample with an electron microscope, and the crushed and dispersed state of the inorganic fine particle aggregates was evaluated according to the following criteria.
  • A Most of the inorganic fine particle aggregates having a particle size of about 150 ⁇ m are crushed and dispersed to the primary silica particles by melt mixing! ⁇ : A few inorganic fine particle aggregates are left without being completely crushed with a size of about 1 m to 20 m.
  • Snowtex MP2040 (silica average primary particle size: 190nm),
  • Snowtex MP1040 (silica average l order particle size: 110nm),
  • Snowtex 30 (silica average primary particle size: 12nm)
  • Solid lOOg and pure water 2.5L were put into a beaker and stirred at 200rpm for 30 minutes while heating at 80 ° C, and then allowed to stand to precipitate the solidified product, and the supernatant containing the eluted KBr was removed. . After removing the supernatant, test for about 10 hours in a 120 ° C dryer. The material is dried and further vacuum dried at 120 ° C for 3 hours to remove KBr, and the SiO skeleton.
  • Fig. 1 shows an electron micrograph of the S4 sample. From FIG. 1, it can be seen that the primary particles of silica form a skeleton three-dimensionally only by physical cohesion.
  • the mixture was pulverized and classified with a sieve having openings of 300 ⁇ m and 75 ⁇ m to obtain a solidified product having an average particle size of 75 ⁇ m to 300 ⁇ m.
  • the obtained solidified product was placed on a baking dish and baked at a temperature of 600 ° C. shown in Table 1 for 2 hours in a fully automatic open / close tubular furnace (manufactured by ISUZU, EKRO-23). 100g of solidified product after baking and 2.5L of pure water were placed in a beaker, stirred while heating at 80 ° C, and allowed to stand to settle the solidified product, and the supernatant liquid containing the eluted KBr was removed. .
  • Figure 2 shows an electron micrograph of the sample. It can be seen from FIG. 2 that the calcined silica fine particle agglomerates form a three-dimensional framework by melting and fusing the silica primary particles. Also, the crush strength of the obtained sample and the commercially available porous silica Table 1 shows the measurement results of the crushing strength of (R1) and commercially available fused silica (R2).
  • the silica fine particle aggregates S1 to S2 (Examples 1 and 2) prepared above and a copolymer (ethylene butyl alcohol, hereinafter referred to as EVOH), which is a polar thermoplastic resin, have the compositions shown in Table 2.
  • EVOH ethylene butyl alcohol
  • Example 1 since the crushing strength of the silica fine particle aggregate used was weaker than that of Comparative Example 1, most of the silica fine particle aggregates were crushed to primary particles by melt mixing, but about 1 to 20 m. A few inorganic fine particle agglomerates remained without being completely crushed.
  • Example 2 a silica fine particle aggregate having the weakest crushing strength was used. Agglomerates of silica particles with a size of approximately 150 m were crushed and dispersed up to the primary silica particles (particle size 190 nm) by melt mixing (Fig. 3). Therefore, the aggregate of silica fine particles having a primary particle force with a large primary particle size has a lower crushing strength, and it is easy to crush and disperse to the silica primary particles by melt mixing.
  • Example 3 using the silica fine particle aggregate (S1) with the weakest crushing strength, the silica fine particle aggregate was completely crushed and dispersed until the silica primary particle (particle size 190 nm) in the melt mixing process. ( Figure 4). In Example 4 where the content was increased to 10% by weight, the silica fine particle aggregates were completely crushed and dispersed by the silica primary particles (Fig. 5).
  • silica fine particle aggregate (S5) having the strongest crushing strength force produced by firing was used.
  • Silica fine particle aggregates cannot be crushed during the melt mixing process, and many silica fine particle aggregates remain as very large uncrushed silica fine particle aggregates with a particle size of about 50 m.
  • Figure 6 This is because the silica fine particle aggregate of the present invention forms the skeleton three-dimensionally only by the physical cohesive force between the silica primary particles (FIG. 1), but the fired silica fine particle aggregate (S5) Due to the melting of the surface of the silica primary particles, the surface layers melt and adhere to each other, or the neck is formed and a skeleton having a strong bond is formed in three dimensions, resulting in high crushing strength. (Fig. 2).
  • the inorganic fine particle aggregate formed by the cohesive force between the inorganic fine particles and the relatively weak adjacent particles is melt-mixed with the inorganic fine particle aggregate and the thermoplastic resin.
  • inorganic fine particle aggregates with low strength can be physically crushed and dispersed by shear stress, so that inorganic fine particles can reach nanoscale regardless of the type of thermoplastic resin or hydrophilicity / hydrophobicity. It can be seen that it is possible to produce a so-called high-molecular nanocomposite that is uniformly crushed and dispersed in a uniform manner.
  • FIG. 7 shows a concept for explaining the preparation procedure of the silica fine particle aggregate used in the present invention and the dispersion state of the silica particles crushed and dispersed in the melt mixing process.
  • thermoplastic resin composite composition in which inorganic fine particles are uniformly dispersed at a nano level in a thermoplastic resin.
  • the present invention provides a method for producing a thermoplastic resin composite composition in which inorganic fine particles are dispersed in a thermoplastic resin to the primary particle level.
  • thermoplastic resin nanocomposite is provided by melt-mixing a thermoplastic resin and an inorganic fine particle aggregate having low strength to disperse the inorganic particles to the nano level.
  • thermoplastic resin composite composition of the present invention can be applied to all fields where particles can be expected to be dispersed at the nano level.
  • a thermoplastic resin composite composition that can be applied to all fields that can be expected by uniformly dispersing particles at a nano level.
  • the zero shear viscosity becomes very high when the shear rate is low compared to when the particles are not nano-dispersed.
  • silica when used as the inorganic fine particles, it can be used for applications in which an improvement in adhesive force can be expected due to the interaction between the hydroxyl group bonded to the silica particle surface increased by nano-dispersion and the metal or the base material.
  • Fig. 1 is an electron micrograph of a silica fine particle aggregate (without firing) used in the present invention.
  • FIG. 2 is an electron micrograph of the silica fine particle aggregate fired at 600 ° C. used in Comparative Example 1.
  • FIG. 3 is an electron micrograph of a fracture surface of a thermoplastic resin mixture composition sample used in Example 2.
  • FIG. 4 is an electron micrograph of a fracture surface of a thermoplastic resin mixture composition sample used in Example 3.
  • FIG. 5 is an electron micrograph of a fracture surface of a thermoplastic resin mixture composition sample used in Example 4.
  • FIG. 6 is an electron micrograph of a fracture surface of the thermoplastic resin mixture composition sample used in Comparative Example 1.
  • FIG. 7 is a conceptual diagram illustrating the procedure for preparing the silica fine particle aggregate used in the present invention and the dispersion state of the silica particles crushed and dispersed in the melt mixing process.

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  • Chemical Kinetics & Catalysis (AREA)
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Abstract

Composition composite de résine thermoplastique laquelle contient de fines particules inorganiques dispersées au niveau des particules primaires et laquelle est excellente en termes de propriétés mécaniques, de stabilité des dimensions, etc. ; et utilisation de la composition. La composition composite de résine thermoplastique est obtenue en mélangeant à l'état fondu une résine thermoplastique avec des agrégats de fines particules inorganiques obtenus en séchant un liquide contenant un mélange constitué de fines particules inorganiques et d'un sel inorganique pour obtenir un solide, en enlevant le sel inorganique du solide avec un solvant et en séchant le solide résultant à une température à laquelle ne survient pas une agglomération des fines particules inorganiques les unes avec autres par fusion en surface, les agrégats étant formés sur la base de la force de cohésion entre les fines particules inorganiques. Dans la composition composite de résine thermoplastique, les fines particules inorganiques ayant un diamètre moyen des particules inférieur ou égal à 1 µm sont dispersées dans la résine. Des articles moulés tels que des tubes, des feuilles, des barres, des fibres, des garnitures, des revêtements et des revêtements de fil électrique constituent des utilisations préférables de la composition composite de résine thermoplastique.
PCT/JP2006/301748 2005-02-04 2006-02-02 Composition composite de résine thermoplastique, procédé servant à produire celle-ci et utilisation de celle-ci WO2006082880A1 (fr)

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CN104723572A (zh) * 2015-03-31 2015-06-24 鹰领航空高端装备技术秦皇岛有限公司 耐高温、透微波的高硅氧耐火纤维-聚苯硫醚-聚醚砜复合材料的制备方法
CN107722404A (zh) * 2017-11-06 2018-02-23 安徽蓝德集团股份有限公司 一种热电偶测温线路保护管

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JP2008013610A (ja) * 2006-07-03 2008-01-24 Du Pont Mitsui Fluorochem Co Ltd フッ素樹脂複合体組成物からなる成形品
JP2010111760A (ja) * 2008-11-06 2010-05-20 Hitachi Cable Ltd ノンハロゲン樹脂組成物、ノンハロゲン絶縁電線、及びノンハロゲンケーブル
JP5874357B2 (ja) * 2011-12-05 2016-03-02 住友ベークライト株式会社 樹脂組成物、樹脂混練物及び成形体
JP6544194B2 (ja) * 2015-10-23 2019-07-17 三菱ケミカル株式会社 （メタ）アクリル樹脂複合体組成物の製造方法

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CN104723572A (zh) * 2015-03-31 2015-06-24 鹰领航空高端装备技术秦皇岛有限公司 耐高温、透微波的高硅氧耐火纤维-聚苯硫醚-聚醚砜复合材料的制备方法
CN107722404A (zh) * 2017-11-06 2018-02-23 安徽蓝德集团股份有限公司 一种热电偶测温线路保护管

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