WO2008146400A1 - Composition de résine - Google Patents

Composition de résine Download PDF

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Publication number
WO2008146400A1
WO2008146400A1 PCT/JP2007/061145 JP2007061145W WO2008146400A1 WO 2008146400 A1 WO2008146400 A1 WO 2008146400A1 JP 2007061145 W JP2007061145 W JP 2007061145W WO 2008146400 A1 WO2008146400 A1 WO 2008146400A1
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WIPO (PCT)
Prior art keywords
group
carbon atoms
resin composition
boron nitride
weight
Prior art date
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PCT/JP2007/061145
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English (en)
Japanese (ja)
Inventor
Hiroaki Kuwahara
Susumu Honda
Yoshio Bando
Chunyi Zhi
Chengchun Tang
Dmitri Golberg
Original Assignee
Teijin Limited
National Institute For Materials Science
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Application filed by Teijin Limited, National Institute For Materials Science filed Critical Teijin Limited
Priority to PCT/JP2007/061145 priority Critical patent/WO2008146400A1/fr
Priority to CN2007800531051A priority patent/CN101707914B/zh
Priority to JP2009516136A priority patent/JPWO2008146400A1/ja
Priority to KR1020097024360A priority patent/KR101422315B1/ko
Publication of WO2008146400A1 publication Critical patent/WO2008146400A1/fr
Priority to HK10108077.7A priority patent/HK1141821A1/xx

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • 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
    • C08J5/005—Reinforced macromolecular compounds with nanosized materials, e.g. nanoparticles, nanofibres, nanotubes, nanowires, nanorods or nanolayered materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such 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
    • C08J2300/00—Characterised by the use of unspecified 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
    • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such 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
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such 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
    • C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/38—Boron-containing compounds

Definitions

  • the present invention relates to a resin composition in which boron nitride nanotubes are dispersed in a thermoplastic resin, a production method thereof, and a molded body thereof.
  • carbon nanotubes have unprecedented mechanical properties, electrical properties, thermal properties, etc., they have been attracting attention as the leading material of nanotechnology, and their potential for application in a wide range of fields has been studied. Has been.
  • Patent Document 1 there has been a report that the mechanical properties of poly force-ponay can be improved by using force-bonded nanotubes whose surface is modified with chemical bonds.
  • Patent Document 2 there is a report that coating of bonbon nanotubes with a conjugated polymer makes the dispersibility of carbon nanotubes extremely high and gives high conductivity to the matrix resin with a small amount of carbon nanotubes.
  • a single-layer single-tube nanotube can be obtained by coating single-layer single-tube nanotubes with a conjugated polymer.
  • boron nitride nanotubes having structural similarities to carbon nanotubes are also attracting attention as materials having unprecedented properties (Patent Document 5).
  • Boron nitride nanotubes not only have excellent mechanical and thermal properties comparable to carbon nanotubes, but are also chemically stable and superior to carbon nanotubes. It is known to have high oxidation resistance. Moreover, since it is insulative, it can also be expected as an insulating heat dissipation material.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 2004-323738
  • Patent Document 2 Japanese Patent Application Laid-Open No. 2004-2621
  • Patent Document 3 Japanese Unexamined Patent Application Publication No. 2004-244490
  • Patent Document 4 Japanese Unexamined Patent Publication No. 2003-268246
  • Patent Document 5 JP 2000-109306 A Disclosure of Invention
  • the objective of this invention is providing the resin composition used as the molded object excellent in thermal conductivity.
  • the objective of this invention is providing the molded object excellent in thermal conductivity.
  • An object of the present invention is to provide a method for producing the resin composition.
  • inorganic oxide particles such as silica and alumina are often added to the resin. These inorganic particles have a large particle size and need to be used in large amounts to improve thermal conductivity. If it is used in a large amount, the original mechanical strength of the resin is impaired.
  • the present inventor studied a method for improving the thermal conductivity while maintaining the mechanical strength inherent in the resin, focusing on the dispersibility of the nitrogen boron nanotubes in the resin.
  • polyamide effectively disperses nitrogen boron nanotubes, and a resin composition with excellent mechanical strength and heat resistance can be obtained, but the improvement in thermal conductivity was not as effective as expected. .
  • thermoplastic resin having a predetermined solubility parameter ( ⁇ ) such as polycarbonate, polyester, acrylic resin, and the like has a power inferior to polyamide in terms of dispersibility of nitrogen boron nanotubes, and significantly improves thermal conductivity.
  • ⁇ solubility parameter
  • the present invention has been completed.
  • the resin composition in which nitrogen boron nanotubes are dispersed in these thermoplastic resins is excellent in mechanical strength and dimensional stability. I found it.
  • the present invention provides a resin composition comprising 100 parts by weight of a thermoplastic resin having a solubility parameter ( ⁇ 5) of 9 to 12 and 0.01 to 10 parts by weight of boron nitride nanotubes; It is a thing.
  • the present invention is also a method for producing a resin composition comprising mixing boron nitride nanotubes and a thermoplastic resin having a solubility parameter (5) of 9 to 12.
  • this invention is a molded object which consists of the said resin composition.
  • the boron nitride nanotube is a tube-shaped material made of boron nitride.
  • the hexagonal mesh surface forms a tube parallel to the tube axis, and becomes a single tube or multiple tube. It is what.
  • the average diameter of the boron nitride nanotubes is preferably 0.4 nm to 1 m, more preferably 0.6 to 500 nm, and even more preferably 0.8 to 200 nm.
  • the average diameter here means the average outer diameter in the case of a single pipe, and the average outer diameter of the outermost pipe in the case of multiple pipes.
  • the average length is preferably 10 ⁇ m or less, more preferably 5 im or less.
  • the aspect ratio is the average length Z average diameter.
  • the average aspect ratio is preferably 5 or more, more preferably 10 or more.
  • the upper limit of the aspect ratio is not limited as long as the average length is 10 m or less, but the upper limit is substantially 25,00. Therefore, the boron nitride nanotubes preferably have an average diameter of 0.4 nm to l ⁇ m and an average aspect ratio of 5 or more.
  • the average diameter and average aspect ratio of boron nitride nanotubes can be determined from observation with an electron microscope.
  • TEM Transmission Electron Microscope
  • the form of boron nitride nanotubes in the composition is measured by, for example, TEM (transmission electron microscope) measurement of the fiber cross section cut parallel to the fiber axis. I can grasp it.
  • the average diameter and the average length were determined by arbitrary 50 arithmetic averages in an electron microscope image.
  • Boron nitride nanotubes are known to be synthesized using arc discharge, laser heating, and chemical vapor deposition.
  • a method of synthesizing borazine as a raw material using nickel boride as a catalyst is also known.
  • a method of synthesizing boron oxide and nitrogen by using a carbon nanotube as a vertical shape has been proposed.
  • the boron nitride nanotubes used in the present invention are not limited to those produced by these methods.
  • boron nitride nanotubes For boron nitride nanotubes, boron nitride nanotubes with strong acid treatment or chemical modification can be used.
  • the boron nitride nanotubes are preferably coated with a conjugated polymer.
  • the conjugated polymer that coats the boron nitride nanotube is preferably one that has a strong interaction with the boron nitride nanotube and a strong interaction with the thermoplastic resin as the matrix resin.
  • conjugated polymers examples include polyphenylene vinylene polymers, polythiophene polymers, polyphenylene polymers, polypyrrole polymers, polyaniline polymers, and polyacetylene polymers. It is done. Of these, polyphenylene vinylene polymers and polythiophene polymers are preferred.
  • the resin composition of the present invention contains 0.001 to 100 parts by weight of boron nitride nanotubes with respect to 100 parts by weight of the thermoplastic resin. By setting it within this range, the boron nitride nanotubes can be uniformly dispersed in the thermoplastic resin. If the boron nitride nanotubes are excessively large, it is difficult to obtain a uniform resin composition.
  • the lower limit of the boron nitride nanotube content is preferably 0.05 parts by weight, more preferably 0.1 parts by weight, and even more preferably 5 parts by weight with respect to 100 parts by weight of the thermoplastic resin.
  • the resin composition of the present invention preferably contains 5 to 100 parts by weight of boron nitride nanotubes with respect to 100 parts by weight of the thermoplastic resin.
  • the upper limit of the content of boron nitride nanotubes is thermoplastic resin 1 0 0
  • the amount is preferably 20 parts by weight, more preferably 15 parts by weight with respect to parts by weight.
  • the resin composition of the present invention may contain boron nitride flakes derived from boron nitride nanotubes, catalytic metals, and the like.
  • thermoplastic resin (Thermoplastic resin)
  • the thermoplastic resin used in the present invention has a solubility parameter ( ⁇ ) of 9 to 12, preferably 9.5 to 11.5.
  • the solubility parameter ⁇ 5 is calculated from the following formula based on “Polymer One Blend”, Saburo Akiyama, Takashi Inoue, Toshio Nishi, and CMC Co., Ltd.
  • the thermoplastic resin is preferably at least one resin selected from the group consisting of polycarbonate, polyester and acrylic resin.
  • the poly force monoponate used in the present invention is preferably an aromatic poly force monoponate or an alicyclic poly force monoponate.
  • the polycarbonate sheet may be a mixture of two or more kinds of polycarbonates.
  • the aromatic polystrength Ponate mainly contains a repeating unit represented by the following formula (A).
  • the content of the repeating unit represented by the following formula (A) is preferably 80 to 100 mol%, more preferably 90 to 100 mol%.
  • the other units are cyclic units derived from alicyclic dihydroxy compounds and aliphatic dihydroxy compounds.
  • R 1 and R 2 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or 6 to 20 carbon atoms.
  • a cycloalkyl group, a C6-C20 cycloalkoxy group, a C6-C10 aryl group, a C7-C20 aralkyl group, a C6-C10 aryloxy group and a C7-C7 represents a group selected from the group consisting of 20 aralkyloxy groups, and when there are a plurality of R 1 and R 2 s , they may be the same or different.
  • Examples of the halogen atom for R 1 and R 2 include a fluorine atom, a chlorine atom, and a bromine atom.
  • Examples of the alkyl group having 1 to 10 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group and the like S.
  • Examples of the alkoxy group having 1 to 10 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.
  • Examples of the cycloalkyl group having 6 to 20 carbon atoms include a cyclohexyl group and a cyclooctyl group.
  • Examples of the C6-C20 cycloalkoxy group include a cyclohexyloxy group, a cyclooctoxy group, and the like.
  • Examples of the aryl group having 6 to 10 carbon atoms include a phenyl group and a naphthyl group.
  • Examples of the aralkyl group having 7 to 20 carbon atoms include benzyl group and phenethyl group.
  • Examples of the aryloxy group having 6 to 10 carbon atoms include a phenoxy group. Carbon number? Examples of the aralkyloxy group of ⁇ 20 include a benzyloxy group.
  • n are each independently an integer of 1 to 4.
  • W is one of the structural units represented by (A-1).
  • R 3 and R 4 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms.
  • the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group.
  • the alkoxy group having 1 to 10 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.
  • R 5 and R 6 each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and when there are a plurality of R 5 and R G s , they may be the same or different from each other.
  • the alkyl group include a methyl group, an ethyl group, and a propyl group.
  • p represents an integer of 4 to 12.
  • R 7 and R 8 each independently represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 3 carbon atoms.
  • the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.
  • the alkyl group having 1 to 3 carbon atoms include a methyl group, an ethyl group, and a propyl group.
  • the repeating unit represented by the formula (A) is 2,2-bis (4-hydroxyphenyl) propane (bisphenol A;), 1,1-bis (4-hydroxyphenyl) -3,3,5- It is a repeating unit derived from at least one selected from trimethylcyclohexane, 4,4 ′-(m-phenyldiisopropylidene) diphenol and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene. .
  • the repeating unit represented by the formula (A) is preferably a repeating unit represented by the following formula (A-2).
  • Aromatic polystrength can be obtained by reacting a dihydroxy compound and a carbonate precursor.
  • the dihydroxy compound include 2,2-bis (4-hydroxyphenyl) propane, 1,1 bis (4-hydroxyphenyl) cyclohexane, 1,1 bis (4-hydroxyphenyl) 3, 3, 5— Trimethylcyclohexane, bis (4-hydroxyphenyl) methane, 1 1 1 bis (4-hydroxyphenyl) ethane, 2 2-bis (4-hydroxyphenyl) butane, 1, 1 1 bis (4-hydroxyphenyl) Enyl) 11-phenylphenyl, bis (4-hydroxyphenyl) diphenylmethane, 2, 2-bis (4-hydroxy 3-methylphenyl) propane, 2, 2-bis (3-phenyl-4-hydroxyphenyl) propane, 2 , 2-bis (4-hydroxy-3-tert-butylphenyl) propane, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene
  • dihydroxy compound S Preferable S
  • dihydroxy compounds may be used alone or in combination of two or more It may be used as a copolymer polycarbonate. It can also be used as a polyester polyester that partially contains terephthalic acid and Z or isophthalic acid components.
  • carbonate precursor carbonyl halide, carbonic acid diester, haloformate or the like is used, and specifically, phosgene, diphenyl carbonate, dihaloformate of dihydroxy compound, or the like can be used.
  • the alicyclic polycarbonate mainly contains a repeating unit represented by the following formula (B).
  • the content of the repeating unit represented by the following formula (B) is preferably 40 100 mol%, more preferably 60 100 mol%, and even more preferably.
  • R 9 to R 12 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, or an aryl group having 6 to 10 carbon atoms. It is.
  • Examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, a propyl group, a propyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group.
  • Examples of the cycloalkyl group having 6 to 20 carbon atoms include a cyclohexyl group and a cyclooctyl group.
  • Examples of the aryl group having 6 to 10 carbon atoms include a phenyl group and a naphthyl group. '
  • the alicyclic polycarbonate can be obtained by reacting a dihydroxy compound and a carbonate precursor.
  • the alicyclic polycarbonate can be produced using a dihydroxy compound represented by the following formula (B-1).
  • R 9 to R 12 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, or 6 to 10 carbon atoms. It ’s the Ariele group.
  • the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, a propyl group, a propyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group.
  • Examples of the cycloalkyl group having 6 to 20 carbon atoms include cyclohexyl group, cyclooctyl group and the like S.
  • Examples of aryl groups having 6 to 10 carbon atoms include phenyl groups and naphthyl groups.
  • Specific examples of the compound represented by the formula (B-1) include isomannide of the following formula (B-2), isoidide of the following formula (B-3), and isosorbide force S of the following formula (B-4) S .
  • ether diols are substances that can also be obtained from natural biomass and are called renewable resources.
  • Isosorbide (B-4) is obtained by hydrogenating D-glucose obtained from starch and then dehydrating it.
  • Other ether diols can be obtained by the same reaction except for the starting materials.
  • the ether diol is preferably a polystreptonate containing an isosorbide residue.
  • Isosorbide can be easily made from starch etc. It is an etherdiol and can be obtained in abundant resources, and it is also superior in ease of manufacture compared to isomannide (B-2) and isoidide (B-3).
  • the method for purifying ether diol used in the present invention is not particularly limited. Preferably, it may be purified by simple distillation, rectification or recrystallization, or a combination of these techniques.
  • carbonate precursor strong sulfonyl halide, carbonic acid diester, or hachiguchi formate is used, and specifically, phosgene, diphenyl carbonate, dihaloformate of dihydroxy compound, or the like can be used.
  • the alicyclic poly force is a compound represented by the following formula (B-5)
  • the repeating unit represented by these may be contained.
  • R 13 is an aliphatic group having 2 to 12 carbon atoms.
  • the aliphatic group having 2 to 12 carbon atoms an alkyl group having 1 to 10 carbon atoms and a cycloalkyl group having 6 to 20 carbon atoms are preferable.
  • the alkyl group having 1 to 10 carbon atoms include methyl group, ethyl group, .propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group and the like.
  • the cycloalkyl group having 6 to 20 carbon atoms include a cyclohexyl group and a cyclooctyl group.
  • the content of the repeating unit represented by the formula (B-5) is preferably 0 to 60 mol%, more preferably 0 to 40 mol%, still more preferably 0 to 20 mol%.
  • the repeating unit represented by the formula (B-5) can be introduced using a dihydroxy compound represented by the following formula (B-6) as a dihydroxy compound.
  • R 13 is the same as defined in formula (B-5) above.
  • Examples of the dihydroxy compound represented by the formula (B-6) include ethylene glycol, 1,3-propanediol, 1,4-monobutanediol, 1,5-pentanediol. , 1,6-hexane diol, 1,4-cyclohexane diol, 1,4-six hexane dimethanol and the like.
  • 1,3-propanediol, 1,4-butanediol, 1,6-hexane is preferred in that the degree of polymerization tends to increase in the synthesis of the polymer, and also shows a high glass transition point in the physical properties of the polymer.
  • Diols are preferred. Further, at least two kinds of these diol components may be combined.
  • the diol component may contain other diol components.
  • Other diol components include cyclohexanediol, cyclohexanedimethanol and other alicyclic alkylenediols, dimethanolbenzene, diethanolbenzene and other aromatic diols, and bisphenols. Can do.
  • a polystrength Ponate can be obtained by reacting a dihydroxy compound with a carbonate precursor.
  • the reaction method include an interfacial polymerization method, a melt transesterification method, a solid-phase transesterification method of force-pone prepreg, and a ring-opening polymerization method of a cyclic carbonate compound.
  • Polystrength Ponate is a branched polycarbonate obtained by copolymerizing polyfunctional aromatic compounds of three or more functions, and polyester strength obtained by copolymerizing aromatic or aliphatic (including alicyclic) difunctional carboxylic acids.
  • Trifunctional or higher polyfunctional aromatic compounds include 1, 1, 1-tris (4-hydroxyphenyl) ethane, 1, 1, 1-tris (3, 5-dimethyl-4-hydroxyphenyl) ether, etc. it can.
  • the ratio is from 0.001 to 1 mol%, preferably from 0.005 to 1 mol% based on the total amount of the aromatic polycarbonate. 0.9 mol%, particularly preferably 0.1 to 0.8 mol%.
  • a branched structure may be generated as a side reaction.
  • the amount of such a branched structure is preferably from 0.001 to 1 mol% in the total amount of aromatic polyphenol. Or 0.05 to 0.9 mol%, particularly preferably 0.01 to 0.8 mol%.
  • Such a ratio can be calculated by 1 H-NMR measurement.
  • the aliphatic bifunctional carboxylic acid is preferably ⁇ , ⁇ -dicarboxylic acid.
  • the aliphatic bifunctional carboxylic acid include sebacic acid (decanedioic acid), dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid, linear saturated aliphatic dicarboxylic acid such as icosanedioic acid, and Preferable examples include alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid.
  • the bifunctional alcohol an alicyclic diol is more preferable, and examples thereof include cyclohexane dimethanol, cyclohexane diol, and tricyclodecane dimethanol.
  • polycarbonate-polyorganosiloxane copolymer obtained by copolymerizing polyorganosiloxane units can be used.
  • the reaction by the interfacial polymerization method is usually a reaction between a dihydroxy compound and phosgene, and is performed in the presence of an acid binder and an organic solvent.
  • the acid binder include alkali metal hydroxides such as sodium hydroxide hydroxide and pyridine, and pyridine.
  • the organic solvent include halogenated hydrocarbons such as methylene chloride and black benzene.
  • a catalyst such as tertiary amine or quaternary ammonium salt can be used, and molecular weight regulators such as phenol, ⁇ -tert-butylphenol, p-cumylphenol, etc.
  • Monofunctional phenols are preferably used. Examples of monofunctional phenols include decyl phenol, dodecyl phenol, teradecyl phenol, hexadecyl phenol, octadecyl phenol, eicosyl phenol, docosyl phenol, and triacontyl phenol. it can. These monofunctional phenols having relatively long-chain alkyl groups are effective when fluidity is required to improve hydrolysis resistance. is there.
  • the reaction temperature is usually 0 to 40 ° C.
  • the reaction time is several minutes to 5 hours
  • the pH during the reaction is usually preferably maintained at 10 or more.
  • the reaction by the melting method is usually an ester exchange reaction between a dihydroxy compound and a carbonic acid diester.
  • the dihydroxy compound and the carbonic acid diester are mixed in the presence of an inert gas, and usually under reduced pressure, usually 1 220 to 3500 ° C. React with.
  • the degree of vacuum is changed in stages, and finally the phenols generated at 1 3 3 Pa or less are removed from the system.
  • the reaction time is usually about 1 to 4 hours.
  • Examples of the carbonic acid diester include diphenyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate, jetyl carbonate and dibutyl carbonate. Among them, diphenyl carbonate is preferable.
  • a polymerization catalyst can be used to increase the polymerization rate.
  • the polymerization catalyst include alkali metal such as sodium hydroxide and hydroxy hydroxide, hydroxide of alkaline metal, boron, Aluminum hydroxide, alkali metal salt, alkaline earth metal salt, quaternary ammonium salt, alkali metal or alkaline earth metal alkoxide, alkali metal or alkaline earth metal organic acid salt, zinc compound, boron compound Catalysts usually used in esterification reactions and transesterification reactions such as silicon compounds, germanium compounds, organotin compounds, lead compounds, antimony compounds, manganese compounds, titanium compounds, and zirconium compounds.
  • the catalyst may be used alone or in combination of two or more.
  • the amount of the polymerization catalyst, the raw material dihydroxy compound per mol preferably 1 X 1 0 - 8 ⁇ 1 X 1 0 one 3 equivalents, more preferably 1 X 1 0- 7 ⁇ 5 X 1 0 one It is selected in the range of 4 equivalents.
  • 2-chlorophenyl phenyl carbonate, 2-methoxycarbonyl phenyl carbonate and 2-ethoxycarbonyl phenol are used at the later stage or after the completion of the polymerization reaction.
  • Compounds such as enyl phenyl carbonate can be added.
  • the melt transesterification method it is preferable to use a deactivator that neutralizes the activity of the catalyst.
  • the amount of the deactivator is 0.5 to 50 per 1 mol of the remaining catalyst.
  • the molar ratio is preferably used.
  • the aromatic polycarbonate after polymerization for the aromatic polycarbonate after polymerization,
  • the quenching agent includes phosphonium salts such as tetrabutylphosphonium salt of dodecylbenzenesulfonate, and ammonium salts such as tetraethylammonium dodecylpentyl sulfate.
  • the viscosity average molecular weight of the polycarbonate is preferably from 8, 00 to 100, 00. If the viscosity average molecular weight is less than 8,00, the molded product from the resin composition becomes very brittle, which is not preferable. On the other hand, if it exceeds 100, 00, the melt fluidity is deteriorated and it becomes difficult to obtain a good molded product. More preferably, it is the range of 1 0, 0 0 0 to 5 0, 0 0 0.
  • the viscosity average molecular weight is calculated by substituting the intrinsic viscosity obtained in a methylene chloride solution of polycarbonate into the “Mark Ichiho Ink” Sakurada equation. The various coefficients in this case are described, for example, on pages 7 to 23 of Polymer Handbook 3rd Ed. Willey, 1989, 3rd revised edition of Polymer Handbook.
  • Polyester has an aromatic dicarboxylic acid as a main dicarboxylic acid component, and an aliphatic diol having 2 to 10 carbon atoms, an alicyclic diol having 6 to 10 carbon atoms, or an aromatic diol having 6 to 12 carbon atoms. It is a polyester used as the main diol component.
  • the content of the aromatic dicarboxylic acid component is preferably 80 mol% or more, more preferably 90 mol% or more.
  • the content of the aliphatic diol component having 2 to 10 carbon atoms is preferably 80 mol% or more, more preferably 90 mol% or more.
  • Aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalene dicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-biphenyldicarponic acid, 4,4, -bifu Enyl ether dicarboxylic acid, 4, 4, -Biphenylmethanedicarboxylic acid, 4,4, -biphenylsulfonedicarboxylic acid, 4,4'-biphenylisopropylidenedicarboxylic acid, 1,2-bis (phenoxy) ethane 4,4'-dicarboxylic acid, 2,5 — Anthracene dicarboxylic acid, 2, 6-anthracene dicarboxylic acid, 4, 4 ′ p-even diene dicarboxylic acid, 2,5-pyridinedicarboxylic acid, and other aromatic dicarboxylic acids are preferably used. Acid, 2,6-naphthal
  • Aromatic dicarboxylic acids may be used as a mixture of two or more. In addition, if the amount is small, it is possible to use a mixture of one or more aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid and dodecanediic acid, and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid together with the dicarboxylic acid. It is.
  • Diols include ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, neopentyl glycol, pentamethylene glycol, hexamethylene glycol, decamethylene glycol, 2-methyl-1,3-propanediol, diethylene glycol, triethylene glycol Aliphatic diols such as 1,4-cyclohexanedimethanol and other alicyclic diols, 2,2-bis (-hydroxyethoxyphenyl) propane-containing diols containing aromatic rings, and the like And mixtures thereof.
  • one or more kinds of long-chain diols having a molecular weight of 400 to 6,000 such as polyethylene dallicol, poly 1,3-propylene glycol, and polytetramethylene glycol may be copolymerized.
  • the aromatic polyester of the present invention can be branched by introducing a small amount of a branching agent.
  • a branching agent Trimesic acid, a trimellitic acid, a trimethylol ethane, a trimethylol propane, a pen erythritol 1 ⁇ l etc. are mentioned.
  • Polyesters include polyethylene terephthalate (PET), polypropylene terephthalate, polybutylene terephthalate (PBT), polyhexylene terephthalate, polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), Polyethylene 1,2-bis (phenoxy) chain 4,4,1 dicarboxylate. Examples thereof include copolymer polyesters such as polyethylene isophthalate / terephthalate, polybutylene terephthalate / isophthalate, and the like.
  • the terminal group structure of the obtained aromatic polyester is not particularly limited, and may be a case where the ratio of one of the hydroxyl groups and the force lpoxyl group in the terminal group is large, except when the ratio is almost the same. .
  • those terminal groups may be blocked by reacting a compound having reactivity with such terminal groups. According to a conventional method, such an aromatic polyester polymerizes a dicarboxylic acid component and a diol component while heating in the presence of a polymerization catalyst containing titanium, germanium, antimony, etc.
  • germanium-based polymerization catalysts include germanium oxides, hydroxides, halides, alcoholates, phenolates, etc. More specifically, germanium oxide, germanium hydroxide, germanium tetrachloride, Examples thereof include tetramethoxygermanium.
  • Preferred examples of the polymerization catalyst for the organic titanium compound include titanium teraboxide, titanium isopropoxide, titanium oxalate, titanium acetate, titanium benzoate, trimellitic acid titanate, tetrabutyl titanate and trimellitic anhydride.
  • a reaction product can be mentioned.
  • the amount of the organic titanium compound used is preferably such that the titanium atom has a concentration of 3 to 12 17 ⁇ atomic% with respect to the acid component constituting the polybutylene terephthalate.
  • compounds such as manganese, zinc, calcium, magnesium, etc., used in the transesterification reaction, which is the former stage of the conventionally known polycondensation can also be used together, and phosphoric acid or phosphorous after completion of the transesterification reaction. It is also possible to deactivate the catalyst and perform polycondensation with an acid compound or the like.
  • the production method of the aromatic polyester can be either batch type or continuous polymerization type.
  • the molecular weight of the aromatic polyester is not particularly limited, but the reduced viscosity measured at 35 using o-chlorophenol as a solvent is 0.6 to 3.0, preferably 0.6 5 to 2.5, More preferably, it is 0.7 to 2.0.
  • acrylic resins include methacrylic acid, acrylic acid, and methyl methacrylate.
  • the acrylic resin used in the present invention includes 5 to 100% by weight of methyl methacrylate, and 0 to 49% by weight of one or more comonomers containing an unsaturated bond copolymerizable with methyl methacrylate. % Copolymerized methacrylic copolymer is preferred.
  • polymethyl methacrylate poly (methyl methacrylate / methacrylic acid), poly (methyl methacrylate Z acrylic acid), poly (methyl methacrylate acrylate / ethyl methacrylate), poly (methyl methacrylate / ethyl acrylate), poly ( Methyl methacrylate / n-propyl methacrylate), poly (methyl methacrylate / n-propyl methacrylate), poly (methyl methacrylate Z t-butyl methacrylate), poly (methyl methacrylate / t-butyl methacrylate), Poly (methyl methacrylate n-hexyl methacrylate), Poly (methyl methacrylate / n-hexyl acrylate), Poly (methyl methacrylate ⁇ Z cyclohexyl methacrylate), Poly (methyl methacrylate) Tonoxycyclohexyl acrylate), poly (methyl methacrylate chloromethyl methacrylate), poly (methyl me
  • polymethyl methacrylate which is a polymer of methyl methacrylate
  • poly (methyl methacrylate-maleic anhydride) which is a copolymer containing a ring structure in the main chain
  • poly (methyl methacrylate ⁇ maleimide) dartaric acid
  • Acrylic resin containing an anhydride unit intramolecular cyclization reaction product of poly (methyl methacrylate) / methacrylic acid
  • acrylic resins can be used alone or in combination of two or more.
  • the weight average molecular weight of the acryl resin is preferably from 5, 0 0 to 2, 0 0 0, 0 0 0. If the weight average molecular weight is smaller than 5, 00 0, the molded product from the resin composition becomes very brittle, which is not preferable. On the other hand, if it exceeds 2, 0 0 0, 0 0 0, the melt fluidity will deteriorate and it will be difficult to obtain a good molded product. More preferably, it is in the range of 1 0, 0 0 0 to 1, 5 0 0, 0 0 0. Manufacturing method of resin composition>
  • the resin composition of the present invention can be produced by mixing nitrogen nitride boron nanotubes and a thermoplastic resin. Mixing can be done by melt mixing or solution mixing.
  • the resin composition of the present invention can be produced by melt-mixing boron nitride nanotubes with a thermoplastic resin (Method a).
  • the method of melt mixing is not particularly limited, but can be mixed using a single or twin screw extruder, a kneader, a lab plast mill, or the like.
  • the resin composition of the present invention can be produced by mixing a solution containing boron nitride nanotubes and a solvent and a thermoplastic resin, and then removing the solvent (Method b).
  • the solvent is preferably a solvent that can dissolve the thermoplastic resin.
  • a solvent that can dissolve the thermoplastic resin include dichloromethane, black mouth form, tetrahydrofuran, methanol, ethanol, butanol, toluene, xylene, acetone, ethyl acetate, dimethylformamide, N-methyl-2-pyrrolidone, dimethylacetamide, and the like.
  • the dispersibility of the boron nitride nanotubes can be improved by subjecting the boron nitride nanotubes to bead milling in a solvent, ultrasonic treatment, or strong shearing treatment.
  • the resin composition thus prepared may be melt-kneaded for the purpose of further improving dispersibility.
  • the kneading method is not particularly specified, but can be carried out using a single screw rudder, a twin screw rudder and a kneader.
  • the melt kneading temperature is 5 to 100 ° C. higher than the temperature at which the resin component melts. If the temperature is too high, decomposition of the resin or abnormal reaction is undesirable.
  • the kneading time is at least 0.5 to 15 minutes, preferably 1 to 10 minutes.
  • a boron nitride nanotube coated with a conjugated polymer may be used as the boron nitride nanotube. Coating does not use solvent, boron nitride nanotubes Can be added to the molten conjugated polymer and mixed (Method 1). The coating can be performed by dispersing and mixing boron nitride nanotubes and a conjugated polymer in a solvent that dissolves the conjugated polymer (Method 2).
  • ultrasonic waves and various stirring methods can be used as a method for dispersing boron nitride nanotubes.
  • a stirring frame method a high-speed stirring method such as a homogenizer or a stirring method such as a pole mill can be used.
  • the solvent is preferably a solvent that dissolves the conjugated polymer. Specific examples include dichloromethane, black mouth form, tetrahydrofuran, methanol, ethanol, butanol, toluene, xylene, acetone, ethyl acetate, dimethylformamide, N-methyl-2-pyrrolidone, dimethylacetamide, and the like. .
  • the resin composition of the present invention is preferably in the form of pellets.
  • the pellet may take a general shape such as a cylinder, a prism, and a sphere, but is more preferably a cylinder.
  • the diameter of such a cylinder is preferably 1 to 5 mm, more preferably 1.5 to 4 mm, and even more preferably 2 to 3.3 mm.
  • the length of the cylinder is preferably 1 to 30 mm, more preferably 2 to 5 mm, and still more preferably 2.5 to 3.5 mm.
  • the resin composition of the present invention contains other resins, elastomers, inorganic fillers, flame retardants, stabilizers, antioxidants, UV inhibitors, light stabilizers, bluing agents, dyes, pigments, and the like. It may be.
  • the resin composition of the present invention may contain other resins and elastomers.
  • other resins include polyamide, polyimide, polyetherimide, polyurethane, silicone, polyphenylene ether, polyphenylene sulfide, polysulfone, polyethylene, polypropylene and other polyolefins, polystyrene, acrylonitrile / styrene copolymer ( AS resin), acrylonitrile Z-brene / styrene copolymer (ABS resin), phenol, epoxy and other resins.
  • AS resin acrylonitrile / styrene copolymer
  • ABS resin acrylonitrile Z-brene / styrene copolymer
  • phenol epoxy and other resins.
  • elastomers examples include isobutylene isoprene rubber, styrene z butadiene rubber, ethylene z propylene rubber, acrylic elastomer, polymer Examples include re-ester elastomers, polyamide elastomers, MBS (methyl methacrylate Z styrene / butadiene) rubber and MA s (methyl methacrylate z acrylonitrile / styrene) rubber, which are core-shell type elastomers.
  • resins and elastomers are preferably used in an amount of not more than 50 parts by weight, more preferably not more than 40 parts by weight, still more preferably not more than 30 parts by weight with respect to 100 parts by weight of the thermoplastic resin. .
  • the lower limit is preferably 1 part by weight.
  • the resin composition of the present invention can contain an inorganic filler.
  • the inorganic filler include glass filler power S such as glass fiber, glass milled fiber, glass peas, glass flake, and glass powder.
  • the glass composition such as E glass, especially, if the T I_ ⁇ 2, Z r 2 ⁇ , B E_ ⁇ , C E_ ⁇ 2, SO 3 and P 2 0 5 etc. may be contained.
  • E glass non-alkali glass
  • the glass fiber is obtained by rapidly cooling molten glass while drawing it by various methods to obtain a predetermined fiber shape. In such a case, the quenching and stretching conditions are not particularly limited.
  • the cross-sectional shape may be various irregular cross-sectional shapes typified by superimposing perfect circular fibers in parallel. Further, it may be a glass fiber having a perfect circular shape and a modified cross-sectional shape.
  • the glass fiber has an average fiber diameter of 1 to 25 m, preferably 5 to 17 m. If glass fibers with an average fiber diameter of less than 1 im are used, the moldability will be impaired, and if glass fibers with an average fiber diameter of more than 25 are used, the appearance will be impaired and the reinforcing effect will be sufficient. is not.
  • Inorganic fillers include hexagonal boron nitride particles, potassium titanate whisker, aluminum borate whisker, carbonized whisker, nitrided whisker, etc., calcium carbonate, magnesium carbonate, dolomite, silica, diatom Soil, Alumina, Iron oxide, Zinc oxide, Magnesium oxide, Calcium sulfate, Ma sulfate Five
  • the resin composition of the present invention may contain hexagonal boron nitride particles in addition to boron nitride nanotubes.
  • the content of the hexagonal boron nitride particles is preferably 0.01 to 20 parts by weight with respect to 100 parts by weight of the thermoplastic resin.
  • Such an inorganic filler is preferably surface-treated with a silane coupling agent, a titanate coupling agent, an luminescent coupling agent or the like.
  • silane coupling agents are preferred.
  • the resin composition of the present invention can contain a flame retardant.
  • flame retardants include halogenated bisphenol A polycarbonate flame retardants, organic salt flame retardants, halogenated aromatic phosphate ester flame retardants, and aromatic phosphate ester flame retardants. One or more of these can be used.
  • polycarbonate-type flame retardant for halogenated bisphenol A examples include a polycarbonate-type flame retardant for tetrabromobisphenol A, and a copolymer polycarbonate-type flame retardant for tetrabromobisphenol A and bisphenol A. .
  • Halogenated aromatic phosphate-type flame retardants include tris (2, 4, 6-tribromophenyl) phosphate, tris (2, 4-dibromophenyl) phosphate, tris (4 monobromophenyl) phosphate Etc.
  • the content of the halogenated aromatic phosphate ester type flame retardant and the aromatic phosphate ester type flame retardant is preferably from 0.1 to 25 parts by weight, more preferably from 1 to 25 parts by weight per 100 parts by weight of the thermoplastic resin. It is 20 parts by weight, more preferably 2 to 18 parts by weight.
  • the resin composition of the present invention can contain a stabilizer.
  • the stabilizer include those already known as thermal stabilizers for thermoplastic resins such as phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid and esters thereof.
  • phosphite compounds include triphenyl phosphite, tris (nonyl phenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite , Diisopropyl monophenyl phosphite, monoptyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite , Tris (Jetylphenyl) Phosphite, Tris (di-iso-propylphenyl) Phosphite, Tris (
  • phosphite compounds that react with dihydroxy compounds and have a cyclic structure
  • 2, 2'-methylenebis (4,6-ditert-butylphenyl) (2,4-ditert-butylphenyl) phosphate 2,2'-methylenebis (4,6-ditert-butylphenyl) (2-tert -Butyl-4 monomethylphenyl) phosphite
  • 2, 2 'ethylidenebis (4-methyl-6-tert-butylphenyl) (2-tert-butyl-tetramethylphenyl) Phosphite and the like can be mentioned.
  • Examples of the phosphate compound include tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorphenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorxenyl phosphate, tri Examples include butoxytyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, and the like, and triphenyl phosphate and trimethyl phosphate are preferred.
  • Phosphonite compounds include tetrakis (2,4-di-tert-butyl). ) -4,4, -biphenyl di-range phosphonai ⁇ , tetrakis (2,4-di-tert-butylphenyl) 1-4,3'-biphenyl di-range phosphonite, terakis (2,4-di-tert-) Butylphenyl) 1, 3, 3, —biphenyl dirange phosphate, tetrakis (2, 6-di tert-butyl phenyl) 1, 4, 4'-biphenyl diphosphonate, tetrakis (2, 6-di tert-butyl phenyl) 1 , 3, -Phiphenyl dirange phosphonite, tetrakis (2,6-di-tert-butyl phenyl) 1,3,3'-bi-di-range phosphonite, bis (2,4-di
  • Examples of the phosphonate compound include dimethyl benzenephosphonate, jetyl benzenephosphonate, and dipropyl benzene phosphonate.
  • the phosphorus stabilizers can be used alone or in combination of two or more.
  • phosphite compounds or phosphonite compounds are preferred.
  • One-phenyl leuphenyl phosphonite is preferred.
  • a combination of these with a phosphite monosaccharide compound is also a preferred embodiment. Five
  • the resin composition of the present invention can contain an antioxidant.
  • the antioxidant include hindered phenolic antioxidants.
  • hindered phenolic antioxidants 0! -Tocopherol, butyl hydroxytoluene, sinapyral alcohol, vitamin E, n-octyldecyl and j8- (4, monohydroxyl 3 ', 5, and -di-tert-butylfel ) Propionate, 2-tert-butyl-6- (3'-tert-butyl-5'-methyl-2-hydroxybenzyl) 1-4-methylphenyl acrylate, 2,6-di-tert-butyl-4- (N, N — Dimethylaminomethyl) phenol, 3,5-di-tert-butyl-1-4-hydroxybenzylphosphonate jetyl ester, 2,2, -methylenebis (4-methyl-6-tert-butylphenol), 2,2, -methylenebis ( 4-ethyl-6-tert-butylphenol), 4,4,
  • the content of the antioxidant is preferably 0.001 to 0.5 parts by weight, more preferably 0.005 to 0.3 parts by weight, and still more preferably 0.01 to 100 parts by weight of the thermoplastic resin. ⁇ 0.2 parts by weight.
  • the resin composition of the present invention can contain an ultraviolet absorber.
  • the ultraviolet absorber include benzophenone-based, benzotriazole-based, hydroxyphenyltriazine-based, and cyclic iminoester-based ultraviolet absorbers.
  • Benzotriazole-based UV absorbers include 2-1- (2-hydroxy-5-methylphenyl) benzotriazol, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-3 , 5-Dicumylphenyl) Phenylbenzotriazole, 2- (2-Hydroxy-3-tert-butyl-5-methylphenyl) One 5-Clobenbenzotriazole, 2, 2, 2-Methylenebis [4 (1, 1, 3, 3— Tetramethylbutyl) -6- (2 H-benzotriazol 2-yl) phenol], 2- (2-hydroxy-3,5-di-tert-butylphenyl) benzotriazole, 2- (2-hydroxy 3 , 5-di-tert-butylphenyl) 1 5-clobenzobenzoyl, 2- (2-hydroxy-3,5-di-tert-amylphenyl) benzotriazol 2— (2-hydroxy-5-tert-octyl
  • Hydroxyphenyltriazine-based UV absorbers include 2- (4,6-diphenyl-1,3,5-triazine-1,2- ⁇ ⁇ l) -1,5-hexyloxyphenol, 2- (4,6-diphenyl) 2-ru 1, 3, 5-triazine 2-yl) 5-methyloxyphenol, 2- (4, 6-diphenyl 1, 3, 5, 5-triazine 2-yl) 1 delta 1 Xiphenol, 2- (4,6-Diphenyl 1,3,5-triazine 2-yl) 5-Propoxyphenol, and 2- (4,6-Diphenyl 1,3,5-triazine (1-2-yl) 1-butyloxyphenol and the like. Further, 2- (4,6-bis (2,4-dimethylphenyl) 1,1,3,5-triazine-2-yl) 15-hexyloxyphenol, etc. Examples are compounds with 4-dimethylphenyl groups.
  • Cyclic imino ester-based UV absorbers include 2, 2, 1 ⁇ -phenylene bis (3, 1 benzoxazine 4-one), 2, 2 '— m-phenylene bis (3, 1 benzoxazine 1 4 one-on), and 2, 2 'one p, p' diphenylenbis (3,4 one-benzoxazine one-one).
  • the ultraviolet absorber may be used alone or in a mixture of two or more.
  • the content of the UV absorber is preferably 0.0005 to 3 parts by weight, more preferably 0.01 to 2 parts by weight, and still more preferably 0.02 to 1 part by weight with respect to 100 parts by weight of the thermoplastic resin. is there.
  • the resin composition of the present invention can contain a light stabilizer.
  • a light stabilizer there is a hindered amine type light stabilizer.
  • a hindered amine light stabilizer bis (2, 2, 6, 6-tetramethyl-4-piperidyl) sebacate, bis (1, 2, 2, 6, 6-Penyumethyl-4-piperidyl) Sepakate, Tetrax (2, 2, 6, 6-Tetramethyl-4-piperidyl)-1, 2, 3, 4-Bitatietracar Poxylate, Tetrakis (1, 2, 2, 6, 6-Penyumethyl-4-piperidyl) 1, 1, 2, 3, 4-Butante Lacarpoxylate, Poly ⁇ [6- (1, 1, 3, 3— Tetramethylbutyl) amino-1,3,5-triazine-1,2,4-diyl] [(2, 2, 6, 6-tetramethylpiperidyl) imino] hexamethylene [(2, 2, 6, 6-tetra Methylpiperidyl) imino] ⁇ , and polymethylpropyl 3-
  • the light stabilizer may be used alone or in a mixture of two or more.
  • the amount of the light stabilizer used is preferably from 0.0005 to 3 parts by weight, more preferably from 0.01 to 2 parts by weight, still more preferably from 0.02 to 1 part by weight, based on 100 parts by weight of the thermoplastic resin. 05 to 0.5 parts by weight are particularly preferred.
  • the resin composition of the present invention can contain a bluing agent.
  • the blooming agent is preferably used in the resin composition in an amount of 0.05 to 3 ppm (weight ratio).
  • the bluing agent is effective for eliminating the yellowishness of the molded product.
  • a certain amount of UV absorber is used, so the molded product tends to be yellowish due to the action and color of the UV absorber, giving the molded product a natural transparency. In order to do so, the use of a blowing agent is effective.
  • the bluing agent refers to a colorant that exhibits a blue or purple color by absorbing orange or yellow light, and a dye is particularly preferred.
  • the content of the bluing agent is in the range of 0.5 to 2.5 ppm, more preferably 0.5 to 2 ppm in the resin composition. Examples include Chlorex Blue RR, Sand's Terrasol Blue I RLS, and Arimoto Chemical Industry's Plast Blue 8580.
  • the resin composition of the present invention can contain a dye and a pigment as long as the object of the present invention is not impaired.
  • Preferred dyes include perylene dyes, coumarin dyes, thioindigo dyes, anthraquinone dyes, thixanthone dyes, bitumen cyanides, perinone dyes, quinoline dyes, quinacridone dyes, dioxazine dyes And isoindolinone dyes and phthalocyanine dyes.
  • the amount of these dyes used is preferably from 0.001 to 1 part by weight, more preferably from 0.05 to 0.5 part by weight, per 100 parts by weight of the thermoplastic resin. (Other additives)
  • the resin composition of the present invention contains a lubricant, a release agent, a foaming agent, a crosslinking agent, a colorant, a flow modifier, an antibacterial agent, a photocatalytic antifouling agent, a photochromic agent, and the like, depending on the purpose as appropriate. be able to. Molded body>
  • This invention includes the molded object which consists of the said resin composition.
  • the molded body include a film and a sheet.
  • the molded body can be manufactured by molding the resin composition.
  • Molding methods include extrusion molding, injection molding, and inflation molding. Extrusion molding can be performed by extruding a molten resin composition from a die. In addition, a film containing a resin composition and a solvent can be cast on a support and cast to a specific thickness, and then the solvent can be removed to produce a film or sheet.
  • Extrusion molding can be performed by extruding a molten resin composition from a die.
  • a film containing a resin composition and a solvent can be cast on a support and cast to a specific thickness, and then the solvent can be removed to produce a film or sheet.
  • Thermal conductivity is measured quickly by the probe method (unsteady hot wire method).
  • KEMTHERM QTM-D3 type manufactured by Kyoto Electronics Industry Co., Ltd.
  • the apparent thermal conductivity is plotted against the thermal conductivity (logarithm) of the reference sample using the following formula, and the deviation is 0
  • the thermal conductivity of the sample was derived by interpolation, and the thermal conductivity of the sample was derived.
  • Deviation ⁇ (apparent thermal conductivity with unknown sample)-(thermal conductivity of reference sample) ⁇ / (thermal conductivity of reference sample)
  • the solubility parameter ⁇ is calculated from the following formula based on the conventional method (“Polymer blend”, Saburo Akiyama, Takashi Inoue, Toshio Nishi, and CMC Co., Ltd.).
  • o is the density of the polymer
  • M is the molecular weight of the repeating unit structure of the polymer
  • ⁇ F i is the molar attractive force constant, which is specific to each substructure
  • the boron nitride nanotubes and resins used in the examples and comparative examples are as follows.
  • the boron nitride nanotubes prepared in Reference Example 1 were used.
  • Hexagonal boron nitride particles made by Aldrich and having a particle size of 1 z ⁇ m were used.
  • PET Polyethylene terephthalate
  • a boron nitride crucible was charged with boron and magnesium oxide at a molar ratio of 1: 1, and the crucible was heated to 1,300 ° C. in a high frequency induction heating furnace. And boron oxide Maguneshiu arm reacts, magnesium vapor is generated with gaseous boron oxide (B 2 ⁇ 2). This product was transferred to the reaction chamber with argon gas, and the temperature was maintained at 1,100 ° C. to introduce ammonia gas. Boron oxide and ammonia reacted to form boron nitride. 1. When 55 g of the mixture was fully heated and the by-products were evaporated, 31 Omg of white solid was obtained from the reaction chamber walls.
  • boron nitride nanotube was a tube with an average diameter of 27.6 nm and an average length of 2,460 nm. .
  • Isosorbide purified by simple distillation in advance (Rocket, Na, Fe, Ca content: 0.6 p pm) 25.0 kg (17 lmo 1), and diphenyl carbonate (Na, Fe, Ca) Content: 0.4 ppm) 36.7 k (1 71 mo 1) was placed in a S US 316 raw material dissolution tank equipped with a stirrer and dissolved at a jacket temperature of 150 ° C. in a nitrogen atmosphere.
  • the raw material melt is sent to a first reactor of S US 316 equipped with a distillation column, a stirrer and a condenser, and 2, 2-bis (4-hydroxyphenyl) propan disodium salt is used as a polymerization catalyst. . 6mg (4.
  • Phenol / 1, 1, 2, 2-tetrachloromethane mixed solution The reduced viscosity measured at a temperature of 35 and a concentration of 1.2 gZd l using a medium (weight ratio 6/4) as a solvent was 1.05. ⁇ was 10.7.
  • the resulting dope is cast on a glass substrate using an 800 m doctor blade, 50 to 1 hour, 80. It was dried for 1 hour. Subsequently, the dried sheet was put into ion-exchanged water, peeled off from the glass substrate, and washed for 1 hour. The obtained sheet was fixed to a metal frame and dried under reduced pressure at 30 mmHg for 1 hour at 80, 100 hours for 1 hour, and then press molded at 150 ° C and 50 kg ⁇ for 5 minutes. A 121 m specimen was obtained. The measured thermal conductivity of the test piece was 2.5 WZmK.
  • the obtained dope was cast on a glass substrate using an 800 // m doctor blade and then dried at 50 ° C. for 1 hour and 80 ° C. for 1 hour. Subsequently, the dried sheet was put into ion-exchanged water, the film was peeled off from the glass substrate, and washed for 1 hour. The obtained sheet was fixed to a metal frame and 30 mmHg at 80 ° C for 1 hour. 3
  • Drying under reduced pressure was carried out at 100 ° C. for 1 hour, and press molding was further performed at 20 ° and 50 kgf for 5 minutes to obtain a test piece having a thickness of 125 mm.
  • the measured thermal conductivity of the specimen was 2.9 WZmK.
  • the obtained dope was cast on a glass substrate using an 80 / xm document blade, and then dried at 50 ° C. for 1 hour and at 80 ° C. for 1 hour. Subsequently, the dried sheet was poured into ion-exchanged water, peeled off from the glass substrate, and washed for 1 hour. The obtained sheet was fixed to a metal frame and dried under reduced pressure at 30 mmHg at 80 for 1 hour and at 100 for 1 hour, and further at 200 and 5 kg at 5 kg for 5 minutes. A test piece having a thickness of 1 2 2 m was obtained by press molding. The thermal conductivity of the test piece was measured and found to be 2.8 WZmK.
  • the obtained sheet was fixed to a metal frame, dried under reduced pressure at 3 OmmHg at 80 ° C for 1 hour and at 100 ° C for 1 hour, and then press molded at 150 at 50 kgf for 5 minutes. A specimen having a thickness of 119 was obtained. The measured thermal conductivity of the test piece was 2.3 WZmK.
  • the obtained dope was cast on a glass substrate using an 800 _tm doctor blade, and then dried at 50 ° C. for 1 hour and at 80 ° C. for 1 hour. Subsequently, the dried sheet was put into ion-exchanged water, peeled off from the glass substrate, and washed for 1 hour. The obtained sheet was fixed to a metal frame and dried under reduced pressure at 3 OmmHg for 1 hour at 80 ° C, 1 hour at 100 ° C, and press-molded at 200 ° C and 50 kgf for 5 minutes. A 121 xm specimen was obtained. The measured thermal conductivity of the test piece was 2.6 WZmK.
  • the specimen thickness was 125 ⁇ m.
  • the measured thermal conductivity of the specimen was 0.18 WZmK.
  • the thickness of the specimen was 121.
  • the thermal conductivity of the test piece was measured and found to be 0.19 W / mK.
  • Hexagonal boron nitride particles in the same manner as in Example 1 except that 2 parts by weight of commercially available hexagonal nitrogen nitride particles (Aldrich, particle size 1 / im) were used instead of 2 parts by weight of boron nitride nanotubes.
  • Hexagonal boron nitride particles in the same manner as in Example 2 except that 2 parts by weight of commercially available hexagonal boron nitride particles (made by Aldrich, particle size 1 xm) were used instead of 2 parts by weight of the nitrogen nitride boron nanotubes.
  • Example 3 Contains hexagonal boron nitride particles in the same manner as in Example 3 except that 2 parts by weight of commercially available hexagonal boron nitride particles (Aldrich, particle size: 1 zm) were used instead of 2 parts by weight of boron nitride nanotubes.
  • a test piece of alicyclic polycarbonate ( ⁇ 11.5) was prepared. The specimen thickness was 11. The thermal conductivity of the test piece was measured and found to be 0.85 WZmK.
  • PET Polyethylene terephthalate
  • B NNT boron nitride nanotubes
  • B NNT is dispersed in the polyamide at the nano level, and there is little aggregation between B NNTs.
  • B NNT is dispersed in a thermoplastic resin having a solubility parameter 1 ( ⁇ 5) of 9 to 12
  • B NNT aggregates in the mesoscopic region. Therefore, it is presumed that a resin composition having excellent thermal conductivity can be obtained by using a thermoplastic resin having a predetermined solubility parameter 1 ( ⁇ ) that allows B NNT to moderately aggregate.
  • thermoplastic resins In general, the thermal conductivity of thermoplastic resins is 0.2 W / mK or less, whereas the thermal conductivity of the resin composition of the present invention exceeds 2 W / mK. This shows that the thermal conductivity of the resin composition of the present invention is exceptional.
  • the resin composition of the present invention and the molded body thereof are excellent in thermal conductivity.
  • the molded article of the present invention is excellent in mechanical properties and dimensional stability.
  • the resin composition of the present invention can be molded into a desired shape by any molding method, and can be suitably used for mechanical parts, industrial materials, electrical and electronic applications, and the like.

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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)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Composite Materials (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

L'invention concerne une composition de résine qui donne un article moulé possédant une excellente propriété mécanique, stabilité dimensionnelle et conductivité thermique. L'invention concerne ladite composition de résine contenant 100 parties en poids d'une résine thermoplastique ayant un paramètre de solubilité (δ) de 9 à 12 et de 0,01 à 100 parties en poids d'un nanotube de nitrure de bore, un procédé pour la préparer et un article moulé la contenant.
PCT/JP2007/061145 2007-05-25 2007-05-25 Composition de résine WO2008146400A1 (fr)

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PCT/JP2007/061145 WO2008146400A1 (fr) 2007-05-25 2007-05-25 Composition de résine
CN2007800531051A CN101707914B (zh) 2007-05-25 2007-05-25 树脂组合物
JP2009516136A JPWO2008146400A1 (ja) 2007-05-25 2007-05-25 樹脂組成物
KR1020097024360A KR101422315B1 (ko) 2007-05-25 2007-05-25 수지 조성물
HK10108077.7A HK1141821A1 (en) 2007-05-25 2010-08-24 Resin composition

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PCT/JP2007/061145 WO2008146400A1 (fr) 2007-05-25 2007-05-25 Composition de résine

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012214675A (ja) * 2010-06-25 2012-11-08 Mitsubishi Chemicals Corp ポリカーボネート樹脂組成物および成形品
JP2013032451A (ja) * 2011-08-02 2013-02-14 Kaneka Corp 高熱伝導性熱可塑性樹脂組成物
JP2016160278A (ja) * 2015-02-26 2016-09-05 帝人株式会社 絶縁熱伝導性ポリカーボネート樹脂組成物
JP2016204653A (ja) * 2015-04-20 2016-12-08 三菱化学株式会社 熱伝導性材料
JP2017095292A (ja) * 2015-11-19 2017-06-01 積水化学工業株式会社 窒化ホウ素ナノチューブ及び熱硬化性材料
JP2017095293A (ja) * 2015-11-19 2017-06-01 積水化学工業株式会社 窒化ホウ素ナノチューブ及び熱硬化性材料
JP2017132662A (ja) * 2016-01-28 2017-08-03 積水化学工業株式会社 窒化ホウ素ナノチューブ材料及び熱硬化性材料
JP2018048296A (ja) * 2016-09-21 2018-03-29 ナイール テクノロジーＮＡｉＥＥＬ Ｔｅｃｈｎｏｌｏｇｙ 樹脂組成物、及びそれから製造された物品、並びにその製造方法
EP3378899A4 (fr) * 2015-11-19 2019-06-26 Sekisui Chemical Co., Ltd. Matière thermodurcissable et produit durci
KR20190099117A (ko) * 2017-02-07 2019-08-26 미츠비시 가스 가가쿠 가부시키가이샤 수지 조성물, 프리프레그, 금속박 피복 적층판, 수지 시트 및 프린트 배선판
WO2022013511A1 (fr) * 2020-07-17 2022-01-20 Commissariat A L'energie Atomique Et Aux Energies Alternatives Nanocomposite à matrice polymère et nanotubes de nitrure de bore

Families Citing this family (2)

* Cited by examiner, † Cited by third party
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CN109066316A (zh) * 2018-09-27 2018-12-21 句容市凯特电力电器有限公司 一种高压开关柜触头盒

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003268246A (ja) * 2002-03-18 2003-09-25 Nissan Motor Co Ltd 樹脂組成物およびその製造方法
JP2003342476A (ja) * 2002-05-27 2003-12-03 Bridgestone Corp 導電性樹脂材料
JP2004002621A (ja) * 2002-03-26 2004-01-08 Toray Ind Inc カーボンナノチューブ含有ペースト、カーボンナノチューブ分散コンポジットおよびカーボンナノチューブ分散コンポジットの製造方法
JP2004161561A (ja) * 2002-11-14 2004-06-10 National Institute For Materials Science 窒化ホウ素ナノチューブの製造方法
JP2004244490A (ja) * 2003-02-13 2004-09-02 Toray Ind Inc カーボンナノチューブ含有樹脂コンポジットとその製造方法および高弾性フィルム
JP2005150362A (ja) * 2003-11-14 2005-06-09 Dainippon Printing Co Ltd 高熱伝導性シートおよびその製造方法
JP2007146038A (ja) * 2005-11-29 2007-06-14 Teijin Ltd 樹脂組成物およびその製造方法
JP2007146039A (ja) * 2005-11-29 2007-06-14 Teijin Ltd 樹脂組成物およびその成形体
JP2007146081A (ja) * 2005-11-30 2007-06-14 Teijin Ltd ポリカーボネート系樹脂成形体およびその製造法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2972882B1 (ja) 1998-09-30 1999-11-08 科学技術庁無機材質研究所長 窒化ホウ素ナノチューブの製造方法
JP2004256607A (ja) * 2003-02-25 2004-09-16 Hitachi Metals Ltd 樹脂強化剤、樹脂組成物
WO2004106420A2 (fr) * 2003-05-22 2004-12-09 Zyvex Corporation Nanocomposites et procedes

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003268246A (ja) * 2002-03-18 2003-09-25 Nissan Motor Co Ltd 樹脂組成物およびその製造方法
JP2004002621A (ja) * 2002-03-26 2004-01-08 Toray Ind Inc カーボンナノチューブ含有ペースト、カーボンナノチューブ分散コンポジットおよびカーボンナノチューブ分散コンポジットの製造方法
JP2003342476A (ja) * 2002-05-27 2003-12-03 Bridgestone Corp 導電性樹脂材料
JP2004161561A (ja) * 2002-11-14 2004-06-10 National Institute For Materials Science 窒化ホウ素ナノチューブの製造方法
JP2004244490A (ja) * 2003-02-13 2004-09-02 Toray Ind Inc カーボンナノチューブ含有樹脂コンポジットとその製造方法および高弾性フィルム
JP2005150362A (ja) * 2003-11-14 2005-06-09 Dainippon Printing Co Ltd 高熱伝導性シートおよびその製造方法
JP2007146038A (ja) * 2005-11-29 2007-06-14 Teijin Ltd 樹脂組成物およびその製造方法
JP2007146039A (ja) * 2005-11-29 2007-06-14 Teijin Ltd 樹脂組成物およびその成形体
JP2007146081A (ja) * 2005-11-30 2007-06-14 Teijin Ltd ポリカーボネート系樹脂成形体およびその製造法

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9120910B2 (en) 2010-06-25 2015-09-01 Mitsubishi Chemical Corporation Polycarbonate resin compositions and molded articles
JP2012214675A (ja) * 2010-06-25 2012-11-08 Mitsubishi Chemicals Corp ポリカーボネート樹脂組成物および成形品
JP2013032451A (ja) * 2011-08-02 2013-02-14 Kaneka Corp 高熱伝導性熱可塑性樹脂組成物
JP2016160278A (ja) * 2015-02-26 2016-09-05 帝人株式会社 絶縁熱伝導性ポリカーボネート樹脂組成物
JP2016204653A (ja) * 2015-04-20 2016-12-08 三菱化学株式会社 熱伝導性材料
EP3378899A4 (fr) * 2015-11-19 2019-06-26 Sekisui Chemical Co., Ltd. Matière thermodurcissable et produit durci
JP2017095292A (ja) * 2015-11-19 2017-06-01 積水化学工業株式会社 窒化ホウ素ナノチューブ及び熱硬化性材料
JP2017095293A (ja) * 2015-11-19 2017-06-01 積水化学工業株式会社 窒化ホウ素ナノチューブ及び熱硬化性材料
US11866635B2 (en) 2015-11-19 2024-01-09 Sekisui Chemical Co., Ltd. Thermosetting material and cured product
JP2017132662A (ja) * 2016-01-28 2017-08-03 積水化学工業株式会社 窒化ホウ素ナノチューブ材料及び熱硬化性材料
JP2018048296A (ja) * 2016-09-21 2018-03-29 ナイール テクノロジーＮＡｉＥＥＬ Ｔｅｃｈｎｏｌｏｇｙ 樹脂組成物、及びそれから製造された物品、並びにその製造方法
JP2019123890A (ja) * 2016-09-21 2019-07-25 ナイール テクノロジーＮＡｉＥＥＬ Ｔｅｃｈｎｏｌｏｇｙ 樹脂組成物、及びそれから製造された物品、並びにその製造方法
US10246623B2 (en) 2016-09-21 2019-04-02 NAiEEL Technology Resin composition, article prepared by using the same, and method of preparing the same
KR20190099117A (ko) * 2017-02-07 2019-08-26 미츠비시 가스 가가쿠 가부시키가이샤 수지 조성물, 프리프레그, 금속박 피복 적층판, 수지 시트 및 프린트 배선판
KR102115720B1 (ko) 2017-02-07 2020-05-28 미츠비시 가스 가가쿠 가부시키가이샤 수지 조성물, 프리프레그, 금속박 피복 적층판, 수지 시트 및 프린트 배선판
WO2022013511A1 (fr) * 2020-07-17 2022-01-20 Commissariat A L'energie Atomique Et Aux Energies Alternatives Nanocomposite à matrice polymère et nanotubes de nitrure de bore
FR3112552A1 (fr) * 2020-07-17 2022-01-21 Commissariat A L'energie Atomique Et Aux Energies Alternatives Nanocomposite à matrice polymère et nanotubes de nitrure de bore

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CN101707914B (zh) 2012-12-12
KR20100017269A (ko) 2010-02-16
HK1141821A1 (en) 2010-11-19
CN101707914A (zh) 2010-05-12
JPWO2008146400A1 (ja) 2010-08-19
KR101422315B1 (ko) 2014-07-22

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