WO2006080318A1 - Composition de résine contenant des nanoparticules d'un sulfure de métal et procédé servant à produire ladite composition - Google Patents

Composition de résine contenant des nanoparticules d'un sulfure de métal et procédé servant à produire ladite composition Download PDF

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WO2006080318A1
WO2006080318A1 PCT/JP2006/301069 JP2006301069W WO2006080318A1 WO 2006080318 A1 WO2006080318 A1 WO 2006080318A1 JP 2006301069 W JP2006301069 W JP 2006301069W WO 2006080318 A1 WO2006080318 A1 WO 2006080318A1
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compound
compounds
carboxylate
resin composition
group
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PCT/JP2006/301069
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Japanese (ja)
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Ryotaro Tsuji
Tomokazu Tozawa
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Kaneka Corporation
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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
    • 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
    • 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

Definitions

  • the present invention relates to a resin composition containing metal sulfide nanoparticles and a method for producing the composition.
  • Metal sulfate nanoparticles have been studied for practical use in a wide range of fields such as electronics, optics, optoelectronics, bioscience, and medical fields in order to utilize quantum properties according to their size.
  • solar cells light emitting elements, displays, phosphors, wavelength conversion elements, wavelength cut filters, nonlinear optical materials, semiconductor lasers, optical memories, ultraviolet shielding materials, electromagnetic wave shielding materials, magnetic recording materials, photocatalysts, quantum transistors, biotechnology A marker etc. can be mentioned.
  • the conventional method for synthesizing such metal sulfate nanoparticles is to use a sulfur metal compound such as sodium sulfate as a sulfur source.
  • a sulfur metal compound such as sodium sulfate
  • metal sulfate nanoparticles are highly unstable due to their high surface activity, and are easily agglomerated during or after synthesis, resulting in non-uniform particle size and reduced quantum properties.
  • problems such as reduced transparency.
  • conventional metal sulfate nanoparticles have been difficult to disperse in thermoplastic resins.
  • Patent Document 1 describes a method of producing a compound semiconductor colloid in a polymer solution.
  • this method has limited polymer compounds applicable to the use of protic hydrophilic solvents such as water, and as a result, only materials having poor weather resistance, water resistance, and durability are produced. I could't.
  • protic hydrophilic solvent it is necessary to use a sulfur metal compound as a sulfur source, and contamination of the resin composition by alkali metal ions cannot be prevented, and a material with high purity can be obtained. I could't do it.
  • Non-patent document 1 describes N, N-dimethyl as a method for obtaining metal sulfate nanoparticles with high purity!
  • a process is described in which thiourea is used as a sulfur source in formaldehyde.
  • thioglycerol as a nanoparticle modifier, the long-term stability effect is insufficient, and it is difficult to separate the raw material residue force. It was inferior in compatibility when trying to disperse the resin in the resin, and it was impossible to obtain a thermoplastic resin composition in which the nanoparticles were uniformly dispersed.
  • Non-Patent Document 2 describes the stability of a force modifier using sodium sulfate as a sulfur source and hexadecyl dithiophosphate as a modifier.
  • the wrinkles are incomplete and aggregation of particles is observed in the transmission electron microscope (TEM) photograph.
  • Patent Document 2 discloses a method for producing nanoparticles in the presence of amines
  • Patent Document 3 discloses a method for producing nanoparticles modified with a thiol compound and an amine compound. However, both of them were modified with a low molecular weight compound, so that the stability effect was insufficient, and it was impossible to prevent aggregation.
  • Patent Document 4 describes a method of extracting and purifying nanoparticle hydrosols into an organic phase using a lipophilic surface-modifying molecule.
  • the efficiency of the purification is increased due to mass transfer between the two phases.
  • Patent Document 5 describes a method of depositing a polymer containing nanoparticles by adding a poor solvent to the polymer after the polymer is added to the nanoparticle dispersion liquid. There was a problem that the binding was weak, so that the nanoparticles did not fully settle and the purification efficiency was poor.
  • Patent Document 6 and Patent Document 7 describe a method of modifying nanoparticles using a polymer having an SH group having strong adhesion to nanoparticles to prevent aggregation and improve purification efficiency!
  • a hydrophilic polymer is used as a polymer, it is necessary to use a protic hydrophilic solvent such as water or alcohol as a solvent, and it is synthesized in an aprotic organic solvent such as zinc sulfate. Nanoparticles had a force that could not be applied.
  • the resulting polymer-modified nanoparticles are hydrophilic, when they are used to produce films and molded articles, they only have inferior water resistance.
  • Patent Document 8 Non-Patent Document 3 and Non-Patent Document 4 describe a technique for modifying nanoparticles using a polymer obtained by reversible addition-elimination chain transfer (RA FT) polymerization !, Ru .
  • RA FT reversible addition-elimination chain transfer
  • Ru reversible addition-elimination chain transfer
  • Patent Document 1 Japanese Patent Laid-Open No. 5-93076
  • Patent Document 2 JP-A-5-113586
  • Patent Document 3 Japanese Unexamined Patent Publication No. 2003-89522
  • Patent Document 4 Japanese Patent Laid-Open No. 2003-73126
  • Patent Document 5 JP-A-10-36517
  • Patent Document 6 Japanese Unexamined Patent Application Publication No. 2002-121548
  • Patent Document 7 Japanese Unexamined Patent Application Publication No. 2002-121549
  • Patent Document 8 US Patent Application Publication No. 2003Z0199653
  • Non-Patent Document 1 J. Nanda et al., “Chem. Mater. J, 2000, pp. 1218”
  • Non-Patent Document 2 S. Chen et al., “Langmuir”, 1999, 15 pp. 8100
  • Non-Patent Document 3 A. B. Lowe et al., “J. Am. Chem. Soc.”, 2002, 124th, 1156
  • Non-Patent Document 4 J. Shan et al., “Macromolecules”, 2003, Vol. 36, p. 4526 Disclosure of the Invention
  • a resin composition containing metal sulfide nanoparticles obtained by reacting a metal compound with a thiourea compound in the presence of a thermoplastic resin soluble in the solvent and then removing the solvent (Claim 1). ).
  • a preferred embodiment of the present invention is a thermoplastic resin soluble in an abrotic polar organic solvent.
  • a resin composition containing metal sulfide nanoparticles according to claim 1 (claim 2).
  • a preferred embodiment of the present invention is a thermoplastic resin-containing polymer soluble in an abrotic polar organic solvent. It is a contained rosin composition (Claim 3).
  • the SH group-containing polymer is terminally SH-modified with a treating agent after reversible addition-elimination chain transfer polymerization using a thiothiol compound as a chain transfer agent.
  • the metal sulfide according to claim 4 wherein the treatment agent is one or more compounds selected from the group consisting of a hydrogen-nitrogen bond-containing compound, a basic compound, and a reducing agent power.
  • the treatment agent is one or more compounds selected from the group consisting of a hydrogen-nitrogen bond-containing compound, a basic compound, and a reducing agent power.
  • a nano-particle-containing rosin composition (Claim 5).
  • the metal compound comprises 90 to: LOO mol% of a zinc carboxylate compound, a zinc dithiocarboxylate compound, a zinc dithiocarbamate compound, a xanthogenic acid
  • a zinc compound an acetylylacetonato zinc compound and an alkylzinc compound, wherein 0 to 10 mol% is a manganese carboxylate compound, an acetylyl compound Cetnatomanganese compound, manganese nitrate, manganese halide compound, strength copper rubonic acid compound, silver carboxylate compound, lead carboxylate compound, halogenated aluminum compound, cobalt carboxylate compound, cobalt halide compound, europium carboxylate compound, Erbium carboxylate, yttrium carboxylate, neodymium carboxylate, terbium carboxylate
  • the thiourea compound is thiourea, monoalkylthiourea, monoarylthiourea, dialkylthiourea, diarylthiourea, cyclic thiourea and dithiothiourea. It is one or more compounds selected from the group A resin composition containing metal sulfate nanoparticles according to any one of claims 1 to 6 (claim 7).
  • a preferred embodiment of the present invention is one or more selected from the group consisting of abrotic polar organic solvent power N, N dimethylformamide, N, N dimethylacetamide, dimethyl sulfoxide and hexamethylphosphoric triamide.
  • the metal sulfide nanoparticle-containing resin composition according to any one of claims 1 to 7, wherein the resin composition is a compound of claim 1 (claim 8).
  • a metal compound and a thiourea compound are reacted in an abrotic polar organic solvent in the presence of a thermoplastic resin soluble in the solvent, and then the solvent is removed.
  • a method for producing a metal sulfide nanoparticle-containing resin composition (claim 9).
  • a preferred embodiment of the present invention is a thermoplastic resin that is soluble in an abrotic polar organic solvent.
  • a preferred embodiment of the present invention is a metal sulfate nanoparticle according to claim 9, which is a thermoplastic resin-containing polymer soluble in an abrotic polar organic solvent.
  • a method for producing a particle-containing resin composition (Claim 11).
  • the SH group-containing polymer is terminally SH-modified with a treating agent after reversible addition-elimination chain transfer polymerization using a thiothiol compound as a chain transfer agent.
  • a method for producing a metal sulfide nanoparticle-containing resin composition according to claim 11 (claim 12).
  • the treatment agent is one or more compounds selected from the group consisting of a hydrogen-nitrogen bond-containing compound, a basic compound, and a reducing agent power.
  • This is a method for producing a resin composition containing rosy nanoparticles (Claim 13).
  • the metal compound is 90 to: LOO mol% is a zinc carboxylate compound, a zinc dithiocarboxylate compound, a zinc dithiocarbamate compound, a xanthogenic acid From the group consisting of zinc compounds, acetylylacetonato zinc compounds, alkyl zinc compounds
  • One or more compounds selected, and 0 to 10 mol% is a manganese carboxylate compound, an acetylacetonate manganese compound, a manganese nitrate, a manganese halide compound, a copper carboxylate compound, a silver carboxylate compound, a carboxylic acid Lead compounds, halogenated aluminum compounds, cobalt carboxylate compounds, cobalt halide compounds, europium carboxylates, erbium carboxylates, yttrium carboxylates, carboxylic acid neodymium compounds, terbium carboxylates, cerium carboxylates 14.
  • the thiourea compound is also thiourea, monoalkylthiourea, monoarylthiourea, dialkylthiourea, diarylthiourea, cyclic thiourea, dithiothiourea. 15.
  • a preferred embodiment of the present invention is selected from the group consisting of abrotic polar organic solvent power N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoric triamide 1
  • the method for producing a resin composition containing metal sulfide nanoparticles according to any one of claims 9 to 15, which is a compound of at least one species (claim 16).
  • a preferred embodiment of the present invention is that when a metal compound and a thiourea compound are reacted in an abrotic polar organic solvent in the presence of a thermoplastic resin soluble in the solvent, a temperature of 80 to 300 ° C is used.
  • the method for producing a metal nanoparticle-containing resin composition according to any one of claims 9 to 16, wherein the composition is heated by heating (claim 17).
  • the metal according to any one of claims 9 to 17, wherein the solvent is removed by distillation after reacting the metal compound with the thiourea compound.
  • a method for producing a resin composition containing sulfur nanoparticles (claim 18).
  • thermoplastic resin containing the metal sulfide nanoparticles.
  • a poor solvent for the thermoplastic resin is added to precipitate the thermoplastic resin containing the metal sulfide nanoparticles.
  • the metal sulfate nanoparticle-containing resin composition of the present invention is excellent in weather resistance, water resistance, and durability with high purity.
  • the metal sulfate nanoparticles are uniformly dispersed in the resin without agglomerating, the quantum properties are excellent.
  • it can be manufactured in one stage and one pot, it is highly productive and economical.
  • the particle diameter can be highly controlled by wrapping the nanoparticles in a polymer. Is possible.
  • the resin composition containing metal sulfate nanoparticles can easily precipitate polymer-modified metal sulfate nanoparticles by adding a poor solvent for the polymer after the reaction. Since it can be separated, purification is easy and nanoparticles with high purity can be easily obtained.
  • the metal sulfide nanoparticle-containing resin composition of the present invention reacts a metal compound and a thiourea compound in an abrotic polar organic solvent in the presence of a thermoplastic resin soluble in the solvent, It is then obtained by removing the solvent.
  • the abrotic polar organic solvent used in the present invention is not particularly limited, and N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAC), dimethyl sulfoxide (DMSO) ), Hexamethylphosphoric triamide (HMPA), nitromethane, pyridine, acetonitrile and the like which are generally well known.
  • DMF N-dimethylformamide
  • DMAC N, N-dimethylacetamide
  • DMSO dimethyl sulfoxide
  • HMPA Hexamethylphosphoric triamide
  • nitromethane pyridine
  • acetonitrile acetonitrile and the like
  • DMF, DMAC, DMSO, and HMPA are preferred in terms of solubility, boiling point, and safety.
  • DMF and DMAC are more preferred. These may be used alone or in combination.
  • thermoplastic resin used in the present invention is not particularly limited as long as it is soluble in the above-mentioned abrotic polar organic solvent.
  • thermoplastic rosin As a specific example of such thermoplastic rosin,
  • thermoplastic resins (meth) acrylic ester-based resins, (meth) acrylamide-based resins, styrene-based resins, (metabolites) are excellent in dispersibility and scavenging properties of metal sulfide nanoparticles.
  • thermoplastic rosins are not particularly limited, but they have high heat resistance, and the glass transition temperature is preferably 80 ° C or higher in terms of 100 ° C or higher. Preferably Yes.
  • the molecular weight is preferably 5000 or more, more preferably 10,000 or more.
  • SH group-containing polymer is used as a thermoplastic resin, the reason why it has a high affinity with metal sulfate nanoparticles is not limited to this, and the molecular weight range described below is preferred.
  • the SH group-containing polymer which is one type of thermoplastic resin used in the present invention, can be used as long as it has a SH group in the molecule, and is not particularly limited.
  • a polymer refers to a compound with a structure in which 10 or more monomer units are connected.
  • the SH group may be present at the terminal of the polymer, or may be present as a substituent in the main chain, or may be present in a branched branch.
  • the polymer structure is not limited to a straight chain, a branch, a dendrimer, a no, an iper branch, and the like, but a straight chain polymer is preferable in terms of high efficiency of modifying nanoparticles.
  • the primary structure of the polymer is not particularly limited, and any of a homopolymer, a block polymer, a random polymer, and a gradient polymer can be used.
  • a syndiotactic polymer, an isotactic polymer, and a heterotactic polymer can be used.
  • Stereoregular polymers such as polymers can also be used.
  • addition-polymerizable polymers and condensation-polymerizable polymers can be used as the types of SH group-containing polymers.
  • Addition-polymerizable polymers are preferred in terms of weatherability, water resistance, and durability.
  • More preferable is a beryl polymer obtained by radical polymerization in view of the availability of the polymer.
  • Specific examples of such polymers include polymers obtained by polymerizing vinyl acetate in the presence of thioacetic acid and then hydrolyzing the end groups with Am. Chem. Sco., 2001, No. 123 10411 [Polystyrenes having SH groups such as those described above can be cited.
  • RAFT polymerization As the SH group-containing polymer, reversible addition / desorption using a thiothio compound as a chain transfer agent is possible because the SH group can be easily and reliably introduced and the molecular weight and molecular weight distribution can be controlled. Most preferred are those that have been terminally SH-treated by a treating agent after chain transfer (RAFT) polymerization.
  • RAFT polymerization as described in JP-T-2000-515181, is a method for controlled radical polymerization of a bull monomer using a thiothiol compound as a chain transfer agent.
  • the polymer obtained by RAFT polymerization has the ability to have a dithioester structure or a trithiocarbonate structure at the molecular end or in the main chain. Is used by converting it to an SH group by treating it with a treating agent.
  • the tiocarbonylthio compound used in the present invention is not particularly limited, and examples thereof include those described in JP 2000-515181 A.
  • the following compounds are preferred in terms of properties:
  • the reaction conditions for RAFT polymerization are not particularly limited, but the polymerization temperature is preferably 60 ° C or higher, more preferably 80 ° C or higher in terms of reactivity.
  • the polymerization mode is not limited to bulk polymerization, solution polymerization, emulsion polymerization, suspension polymerization and the like, but bulk polymerization and solution polymerization are preferable because they can be easily converted into SH groups.
  • the solvent to be used is not particularly limited, and an appropriate solvent may be selected according to the monomer or polymer.
  • Specific examples include toluene, xylene, ethyl acetate, butyl acetate, DMF, DMAC, DMSO, methyl ethyl ketone, methyl isobutyl ketone, acetone, and acetonitrile.
  • RAFT polymerization is a force that can be achieved by radical polymerization of a butyl monomer in the presence of the thiocarbothio compound
  • the radical polymerization initiation method is not particularly limited. Examples thereof include a method in which a radical initiator that is thermally decomposed coexists, a method that is initiated by light irradiation, and a method that is initiated by microwave irradiation. Among these, a method of coexisting a radical initiator that thermally decomposes in view of availability, versatility, and controllability is preferable.
  • radical initiators include methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, cyclohexanone peroxide, benzoyl peroxide, tamen hydroperoxide, di-t-butyl peroxide, t -Peroxygen-based initiators such as butyl bisoxyacetate, bis (2-ethylhexyl) peroxydicarbonate, succinic peroxide; dimethyl 2,2'-azobisisobutyrate, 2,2, -azobis (4-Methoxy-1,2,4 dimethylvale-tolyl), 2,2'-azobis (isobutyoxy-tolyl), 1,1,1azobis (cyclohexane-1-1-carbo-tolyl), 2, 2,1 Azobis (2,4 dimethylvale-tolyl), 2,2, -azobis (2-methylbutyoxy-tolyl), 4, 4, azobis (4-cyananovaleric acid) Which azo
  • an azo initiator is preferred in view of availability, safety and reactivity.
  • the amount of the polymerization initiator used is not particularly limited, but 0.5 mol or less is preferable with respect to 1 mol of thiocarbonylthio group in the thiocarbothioi compound in terms of narrowing the molecular weight distribution of the resulting polymer. More preferably, it is 0.25 mol or less.
  • the bull monomers used in the RAFT polymerization are not particularly limited, and those capable of radical polymerization can be used. Specific examples of such bulle monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, (meth) acrylic acid 2 —Hydroxyethyl, (meth) acrylic acid 2-methoxychetyl, (meth) acrylic acid 2-ethylhexyl, (meth) glycidyl acrylate, 2- (meth) acryloyloxypropyltrimethoxysilane, (meth) (Meth) acrylic acid esters such as 2,2,2-trifluoroethyl acrylate and (meth) acrylic acid; (meth) acrylic acid; styrene, ⁇ -methylolstyrene, ⁇ -hydroxystyrene, ⁇ -
  • Aliphatic olefin compounds such as butadiene and isoprene; Halogen-containing bur compounds such as butyl chloride, vinylidene chloride and chloroprene; (meth) acrylamide, ⁇ -methyl (meth) acrylamide, ⁇ , ⁇ -dimethyl (meta ) Acrylamide, (meth) acrylamides such as) -isopropyl (meth) acrylamide; -Tolyl compounds such as (meth) acrylonitrile; Maleimide compounds such as ⁇ -phenolmaleimide; Heterocycles such as 4-burpyridine and ⁇ -bullpyrrolidone Compounds: Examples include but are not limited to butyl ester compounds such as butyl acetate, butyl propionate, benzoate, and maleic anhydride.
  • (meth) acrylic acid ester and styrenic compound are preferred in terms of weather resistance, water resistance, durability, and heat resistance of the resulting polymer.
  • These vinyl monomers can be used alone or in combination.
  • the treating agent used when converting the polymer obtained by RAFT polymerization into an SH group-containing polymer is not particularly limited, but a hydrogen-nitrogen bond-containing compound or basic compound is high in terms of high conversion efficiency. And a compound selected from the group consisting of reducing agent power is preferred.
  • the hydrogen-nitrogen bond-containing compound is not particularly limited, and examples thereof include ammonia, hydrazine, primary amine, secondary amine, hindered amine light stabilizer (HALS) and the like. Can do.
  • Specific examples of the primary amine include methylamine, ethylamine, isopropylamine, n-butylamine, t-butylamine, 2-aminoethanol, ethylene diamine, cyclohexylamine, and arline.
  • Specific examples of the secondary amines include dimethylamine, jetylamine, diisobutylamine, iminodiacetic acid, bis (hydroxyjetyl) amine, di-n-butylamine, di-tert-butylamine, diphenylamine, imidazole, Examples include piperidine.
  • Specific examples of HALS include Adeka Stub LA-77 (Asahi Denki Kogyo Co., Ltd.), Tinuvin 144 (Ciba 'Specialty Chemicals Co., Ltd.), Adeka Stub LA- 67 (Asahi Denka Kogyo Co., Ltd.) ) And the like.
  • examples of basic compounds are not particularly limited, but include sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, sodium methoxide, sodium ethoxy.
  • Examples include sodium carbonate, sodium carbonate, and potassium carbonate.
  • the reducing agent is not particularly limited, and examples thereof include sodium hydride, lithium hydride, calcium hydride, LiAlH, NaBH, LiBEt H, and hydrogen.
  • the above treatment agents may be used alone or in combination. From the viewpoint of conversion efficiency, a primary nitrogen amine having a boiling point of 20 to 100 ° C. is more preferable because a compound containing a hydrogen nitrogen bond having a boiling point of 20 to 200 ° C. and a refinement that favors a reducing agent can be simplified. Such primary amines can be removed by distillation after the treatment reaction.
  • the amount of the treatment agent used is not particularly limited, but is 100 parts by weight of polymer in terms of the balance between conversion efficiency and economy. 0.01-: LOO parts by weight are preferred. 0.1-30 parts by weight are more preferred.
  • the reaction conditions are not particularly limited.
  • the molecular weight of the SH group-containing polymer synthesized by RAFT polymerization is not particularly limited, but the effect of nanoparticle modification is high, and the molecular weight is determined by gel permeation chromatography (GPC) analysis.
  • Number average molecular weight (Mn) force S is in the range of 1000 to 100000, force S is more preferably in the range of 1500 to 50000.
  • the molecular weight distribution is not particularly limited, but the ratio of the weight average molecular weight (Mw) to Mn (MwZMn) obtained by GPC analysis is 1.5 or less in that the particle size of the nanoparticles is uniform. Preferable 1. It is more preferable that it is 3 or less.
  • an SH group-containing polymer is used as the thermoplastic resin of the present invention
  • the SH group can efficiently modify the surface of the metal sulfide nanoparticles
  • nanoparticles protected with the polymer can be obtained.
  • aggregation of the nanoparticles can be prevented, so that the particle size of the metal sulfate nanoparticles in the resin composition becomes uniform, and the quantum characteristics depending on the size become uniform.
  • Such uniformity of quantum characteristics can be confirmed, for example, by analyzing an emission spectrum.
  • the emission spectrum is single and sharp.
  • a resin composition having excellent transparency and ultraviolet absorbing ability can be obtained.
  • the metal compound used in the present invention is not particularly limited, and a compound that reacts with a thiourea compound to form sulfur nanoparticles can be used.
  • metal compounds include zinc compounds, manganese compounds, copper compounds, magnesium compounds, titanium compounds, cobalt compounds, iron compounds, nickel compounds, cadmium compounds, aluminum compounds, gallium compounds, indium compounds, Vanadium compounds, tantalum compounds, chromium compounds, molybdenum compounds, tungsten compounds, germanium compounds, tin compounds, lead compounds, mercury compounds, antimony compounds, bismuth compounds, puffy compounds, erbium compounds, yttrium compounds, neodymium compounds, Examples thereof include terbium compounds and cerium compounds.
  • zinc-rich compound examples include zinc carboxylates such as zinc acetate, zinc benzoate, zinc citrate, zinc formate, zinc laurate, zinc salicylate, etc.
  • manganese compound examples include, but are not limited to, manganese carboxylic acid compounds such as manganese acetate and manganese benzoate; acetyl cetato manganese compounds such as acetyl acetyl sodium; Manganese nitrate; manganese halide compounds such as dichloromanganese and dibromomanganese.
  • the copper compound include, but are not limited to, copper carboxylate compounds such as copper acetate, copper benzoate, copper titanate, and copper phthalate; dithio compounds such as copper dimethyldithiocarbamate Examples thereof include copper rubamate compounds; copper halide compounds such as copper chloride and copper bromide; copper nitrate; copper sulfate.
  • magnesium compound examples include magnesium carboxylates such as magnesium acetate; alkylmagnesium compounds such as jetylmagnesium and di-n-butylmagnesium; chloromethylmagnesium, bromomethylmagnesium, chloroethyl And halogenated magnesium compounds such as nilmagnesium and magnesium iodide.
  • magnesium carboxylates such as magnesium acetate
  • alkylmagnesium compounds such as jetylmagnesium and di-n-butylmagnesium
  • chloromethylmagnesium, bromomethylmagnesium, chloroethyl And halogenated magnesium compounds such as nilmagnesium and magnesium iodide.
  • titanium carboxylic acid compounds such as titanium cresylate; titanium halides such as titanium trichloride, titanium tetrachloride, and titanium tetrabromide.
  • titanium halides such as titanium trichloride, titanium tetrachloride, and titanium tetrabromide.
  • Compounds; acetylacetonate titanate compounds such as titanium oxide (II) acetylcetate.
  • cobalt compound examples include cobalt acetate and benzoic acid.
  • cobalt carboxylate compounds such as cobalt acid cobalt, cobalt citrate, and cobalt oxalate; halogenated cobalt compounds such as cobalt chloride; and acetylacetonato cobalt compounds such as acetylacetonatocobalt.
  • iron compound examples include iron carboxylate compounds such as iron acetate; halogenated iron compounds such as iron dichloride and trisalt iron.
  • nickel compound examples include, but are not limited to, nickel carboxylate compounds such as nickel acetate, formic acid-nickel and nickel lactate; acetylylacetonate nickel such as acetylylacetonate nickel Compound: Nickel dithiocarnomate compound such as bis (dibutyldithiocarnomate) -keke; Halogenated-keke Louis compound such as nickel chloride.
  • cadmium compound examples include, but are not limited to, cadmium acetate, cadmium formate, cadmium stearate, and other carboxylic acid cadmium compounds; salt cadmium, bromide, methyl cadmium chloride, and the like.
  • the aluminum compound are not particularly limited, but alkyl aluminum compounds such as trimethylaluminum, triethylaluminum, tri-n-butylaluminum, trioctylaluminum; aluminum trichloride, dimethylaluminum chloride, chloride Examples thereof include halogenated aluminum compounds such as jetyl aluminum, methyl aluminum dichloride, and ethyl aluminum dichloride.
  • gallium compound examples include, but are not limited to, alkyl gallium compounds such as tri-n-butyl gallium; halogen-gallium compounds such as gallium trichloride, di-n-butyl gallium chloride, and n-butyl gallium dichloride. And so on.
  • indium compound examples include, but are not limited to, indium halide compounds such as trimethylindium indium trichloride, di-n-butylindium chloride, and n-butylindium dichloride.
  • vanadium compound examples are not particularly limited, and examples thereof include halogen vanadium compounds such as vanadium dichloride and tetrasalt vanadium.
  • tantalum compound examples include, but are not particularly limited to, tantalum halide compounds such as pentachloride tantalum and tantalum pentahalide.
  • chromium compound examples include, but are not limited to, chromium carbonate compounds such as chromium acetate; chromium halide compounds such as chromium tribromide and chromium triiodide.
  • molybdenum compound examples include, but are not limited to, molybdenum carboxylate compounds such as molybdenum acetate dimer; halogen-molybdenum compounds such as molybdenum tetrachloride and molybdenum tetrabromide. .
  • tungsten compound examples include halogen tungsten compounds such as tandane tetrachloride and tungsten tetrabromide.
  • germanium compound examples are not particularly limited, and examples thereof include germanium halide compounds such as tetrasalt-germanium and germanium tetrabromide.
  • tin compound examples include, but are not limited to, tin carboxylate compounds such as tin acetate; tin halide compounds such as tin dichloride and tin tetrachloride, and the like.
  • lead compounds include, but are not limited to, lead carboxylate compounds such as lead acetate; and halogen lead compounds such as lead dichloride and lead dibromide. be able to.
  • mercury-containing compound examples include mercury carboxylate compounds such as mercury acetate; halogen-mercury compounds such as disalt mercury.
  • antimony compound examples include, but are not limited to, antimony carboxylic acid compounds such as antimony acetate; alkylantimony compounds such as trimethylantimony and tri-n-butylantimony; antimony trichloride and methylantimony dichloride.
  • antimony carboxylic acid compounds such as antimony acetate
  • alkylantimony compounds such as trimethylantimony and tri-n-butylantimony
  • antimony trichloride such as trimethylantimony and tri-n-butylantimony
  • methylantimony dichloride examples include, but are not limited to, antimony carboxylic acid compounds such as antimony acetate; alkylantimony compounds such as trimethylantimony and tri-n-butylantimony; antimony trichloride and methylantimony dichloride.
  • Halogenated antimony compounds such as
  • bismuth compounds are not particularly limited, but include power bismuth compounds such as bismuth acetate; alkyl bismuth compounds such as trimethyl bismuth and tri-n-butyl bismuth; bismuth trichloride and methyl dichloride.
  • power bismuth compounds such as bismuth acetate
  • alkyl bismuth compounds such as trimethyl bismuth and tri-n-butyl bismuth
  • bismuth trichloride and methyl dichloride bismuth halides such as bismuth And the like.
  • europium compound examples include, but are not limited to, europium acetate, carboxylic acid europium compounds such as europium oxalate; europium halide compounds such as europium chloride; europium nitrate; europium carbonate and the like.
  • erbium compound examples include, but are not limited to, erbium carboxylate compounds such as erbium acetate and erbium oxalate; acetylacetate erbium compounds such as acetylacetonatoerbium; Examples include erbium alkoxide compounds such as propoxide; halogenated rubium compounds such as erbium chloride and erbium fluoride; erbium nitrate; erbium carbonate.
  • erbium carboxylate compounds such as erbium acetate and erbium oxalate
  • acetylacetate erbium compounds such as acetylacetonatoerbium
  • Examples include erbium alkoxide compounds such as propoxide; halogenated rubium compounds such as erbium chloride and erbium fluoride; erbium nitrate; erbium carbonate.
  • yttrium compound examples are not particularly limited, but yttrium carboxylate compounds such as yttrium acetate and yttrium oxalate; yttrium halide compounds such as yttrium chloride and yttrium bromide; yttrium nitrate; yttrium carbonate; Examples include alkoxylated yttrium compounds such as yttrium soproboxide.
  • neodymium compound examples include, but are not limited to, neodymium carboxylic acid compounds such as neodymium acetate and neodymium 2-ethylhexanoate; acetylylacetonate neodymium compounds such as acetylylacetonate neodymium; Examples thereof include neodymium nitrate; neodymium carbonate; halogenated neodymium compounds such as neodymium salt and neodymium bromide; and alkoxy-neodymium compounds such as neodymium isopropoxide.
  • neodymium carboxylic acid compounds such as neodymium acetate and neodymium 2-ethylhexanoate
  • acetylylacetonate neodymium compounds such as acetylylacetonate neodymium
  • Examples thereof include neody
  • terbium carboxylate compounds such as terbium acetate and terbium oxalate
  • acetylylacetonate terbium compounds such as acetylacetonatoterbium; , Terbium bromide, and the like, and rogene terbium compounds
  • terbium carbonate terbium nitrate.
  • cerium carboxylate compounds such as cerium acetate, cerium 2-ethylhexanoate, and cerium oxalate; cerium carbonate; cerium nitrate; cerium sulfate; salt Halium cerium such as cerium and cerium bromide Things can be mentioned.
  • the metal compounds used in the present invention may be used alone or in combination. It may be a hydrate or an anhydride.
  • the number of acid atoms of the metal atom is not particularly limited.
  • LOO mol% of the metal compound is a zinc compound in terms of the quantum characteristics, safety, and environmental load of the obtained nanoparticles.
  • a metal compound other than the zinc compound can be used as 0 to: LO mol% of the metal compound.
  • zinc sulfate nanoparticles doped with metal atoms other than zinc can be produced.
  • Such doving makes it possible to control the emission characteristics, absorption wavelength, and the like of the resulting metal sulfide nanoparticles.
  • metal compounds other than zinc used for doping purposes include manganese carboxylate compounds and acetylenes in terms of availability, reactivity, and quantum properties.
  • the thiourea compound used in the present invention is not particularly limited.
  • thiourea monoalkylthiourea, monoarylthiourea, dialkylthiourea, diallylthiourea, trialkylthiourea, tetraalkylthiourea, carboxyl
  • group-containing thiourea cyclic thiourea, diacid thiothiourea, and the like.
  • thiourea compounds specific examples of monoalkylthiourea are not particularly limited. N-methyl thiourea, N isopropyl thiourea, N allyl thiourea, N—n propyl thiourea, N—n—butyl thiourea, N—n decyl thiourea, N—2 phenyl thiourea, N triphenyl methyl thiourea, etc. Can be mentioned.
  • thiourea compounds specific examples of monoarylthiourea are not particularly limited, but N-phenylthiourea, N—o tolylthiourea, N—p tolylthiourea, N—3 pyridylthiourea, N —P cyanophylthiourea, N—2 pyridylthiourea, N—1-naphthylthiourea, N—p-trifluorothiourea, N—o-methoxyphenolthiourea, N—m fluorothiourea, N—p phenoloxy-thiol And urea, 1, 4 -phenol-bis (thiourea).
  • dialkylthiourea examples are not particularly limited, but N, N, -dimethinoretiourea, N, N, -jetinoretiourea, N, N, oxy n-butylthiourea, N, N, -di-n-octylthiourea, N, N dicyclohexylthiourea, N, N′bis (dimethylaminopropyl) thiourea and the like can be mentioned.
  • diarylthiourea are not particularly limited, but N, N, diphenylthiourea, N, N, di-o-tolylthiourea, N, N, P Tolylthiourea can be mentioned.
  • trialkylthiourea examples include trimethylthiourea, triethylthiourea, and triarylthiourea.
  • thiourea compounds specific examples of tetraalkylthiourea are not particularly limited, and examples thereof include tetramethylthiourea and tetraethylthiourea.
  • carboxyl group-containing thiourea examples include N-acetylthiourea, N-benzoylthiourea, N (benzoylamidino) thiourea, N, N diisobutyl-N'-be And nzoylthiourea.
  • thiourea compounds specific examples of cyclic thiourea are not particularly limited, and examples thereof include ethylene thiourea and propylene thiourea.
  • the thiourea compounds used in the present invention may be used singly or in combination.
  • thiourea, monoalkylthiourea, monoarylthiourea, dialkylthiourea, diarylthiourea, cyclic thiourea, and thiothiourea diacid are preferred in terms of reactivity and availability.
  • N-methylthiourea, N, N′-dimethylthiourea, ethylenethiourea, and thiourea dioxide are more preferable.
  • the amount ratio of these compounds is not particularly limited, but the particle size of the resulting metal sulfide nanoparticle is not limited. In terms of particle size distribution, quantum characteristics, and yield, it is preferable to use 0.2 to 1.2 moles of thiourea compound per mole of metal compound. More preferably, the ratio is used.
  • thermoplastic resin at a ratio of 50 to 50 parts by weight with respect to 100 parts by weight of the metal compound. 100-5 0000 parts by weight is preferred.
  • the metal sulfate nanoparticles can be strongly modified, so in this case, 0.01 to: L 5 mol or 0.05 to 1 mol It is preferable to use in proportion.
  • the amount of the abrotic polar organic solvent to be used is not particularly limited, but 100 to 100000 parts by weight is preferable with respect to 100 parts by weight of the metal compound in terms of reaction efficiency. I like it!
  • the reaction conditions for reacting the metal compound with the thiourea compound in the presence of the thermoplastic resin are not particularly limited, but the reaction temperature is preferably 80 ° C or higher from the viewpoint of reaction efficiency 100 ° C or more is more preferable. If the reaction temperature is too high, decomposition of the thermoplastic oxalate-urine compound occurs. Therefore, 300 ° C or lower is preferable, and 250 ° C or lower is more preferable. Either batch type or fluid type reaction can be applied.
  • the metal sulfate nanoparticle-containing resin composition of the present invention can be obtained by reacting the metal compound with the thiourea compound and then removing the solvent.
  • the method for removing the solvent is not particularly limited. For example, (1) a method of distillation; (2) a method of precipitation by adding a poor solvent for thermoplastic resin to separate from the solvent; (3) lyophilization Do The method etc. can be mentioned. Of these, the methods (1) and (2) are preferable in terms of simple operation, and the method (2) is more preferable in that a resin composition is obtained.
  • the specific means is not particularly limited.
  • the pressure may be normal, it is preferable to reduce pressure in terms of efficiency.
  • the temperature may be room temperature! / Is preferably heated from the viewpoint of efficiency.
  • the distilled solvent is preferably recovered and reused from the viewpoints of safety and environmental burden.
  • the specific means is not particularly limited.
  • an appropriate one may be selected according to the thermoplastic resin to be used, but those which are compatible with the aprotic polar organic solvent used in the reaction are preferred. If an appropriate combination of antisolvents is not found, an appropriate antisolvent may be selected after replacing the aprotic polar organic solvent with another appropriate solvent.
  • thermoplastic rosin examples include aliphatic hydrocarbon solvents such as hexane, pentane, octane and cyclohexane; alcohol solvents such as methanol, ethanol, hexanol and octanol; Fluorinated solvents such as fluoroethanol and HCFC-225 (Asahi Glass Co., Ltd.) can be mentioned.
  • the resin composition containing metal sulfate nanoparticles separated by adding a poor solvent can be used after drying by a general method.
  • the resin composition according to the present invention may be mixed or added with other thermoplastic resins, thermosetting resins, additives and the like according to the purpose.
  • a thermoplastic resin a thermosetting resin can be used generally, and it is preferable to use a resin having compatibility with the resin composition according to the present invention.
  • the additives include pigments and dyes, heat stabilizers, acid / antioxidants, ultraviolet absorbers, light stabilizers, lubricants, plasticizers, flame retardants, and antistatic agents.
  • the metal sulfate nanoparticle-containing resin composition of the present invention can be used as various coating films, films, and molded articles by solution casting, melt molding and the like.
  • Mw and Mn of the polymer were determined by GPC analysis. Waters Sys The column was used by connecting Shodex K-806 and K-805 (manufactured by Showa Denko Co., Ltd.) and using a polystyrene standard sample as an eluent. The monomer reaction rate in polymerizing the polymer was determined by gas chromatography (GC) analysis. GC analysis was performed with gas chromatograph GC-14B (manufactured by Shimadzu Corp.) using the Kyaryari Islamic Ram DB-17 (manufactured by J & W SCIENTIFIC) by dissolving the sampling solution in ethyl acetate.
  • GC gas chromatography
  • the dispersion state and particle size of the metal sulfide nanoparticles were observed using a transmission electron microscope (TEM) JEM-1200EX (manufactured by JEOL Ltd.) at an acceleration voltage of 80 kV.
  • the emission spectrum was measured using a spectrofluorometer FP-6500DS (manufactured by JASCO Corporation) using 300 nm excitation light with respect to the solution or film sample, and the photoluminescence spectrum was measured in the range of 350 to 700 nm. .
  • the obtained PMMA resin composition can form a transparent film on a quartz substrate by a solution casting method (film thickness: 100 ⁇ m), and has a wavelength of 410 nm and 436 nm for 300 nm excitation light.
  • the emission spectrum was shown. Force that seems to be because some of the nanoparticles are agglomerated because the emission spectrum was bimodal.
  • the agglomeration of ZnS nanoparticles was less than 3% and almost uniformly dispersed It was confirmed.
  • the resulting film has a haze of 0.8%.
  • Example 1 PBA (4. Og) (manufactured by Aldrich) (Mw: about 60000, Mn: about 20000, product number: 18, 141-2) was used in place of PMMA. Of a viscous polymer was obtained (yield 3.0 g).
  • the obtained PBA showed emission spectra of 408 nm and 432 nm for excitation light of 300 nm in black mouth form. Since the emission spectrum was bimodal, some ZnS nanoparticles were aggregated, and the power that was considered to be achievable.
  • This PBA containing ZnS nanoparticles was left at room temperature for 1 month, but remained transparent. It was confirmed that further aggregation of ZnS nanoparticles was suppressed. However, when this ZnS nanoparticle-containing PBA was left as a black mouth form, toluene, and DMF solution at room temperature, turbidity occurred and the transparency decreased in one week. It is not considered.
  • Example 1 a similar experiment was performed using PC (Caliber 300-30; manufactured by Sumitomo Dow Co., Ltd.) (2.5 g) instead of PMMA to obtain PC containing ZnS nanoparticles (yield) 2. lg).
  • PC Caliber 300-30; manufactured by Sumitomo Dow Co., Ltd.
  • Yield 2. lg.
  • This The PC containing ZnS nanoparticles was molded as a 0.3 mm thick sheet by hot pressing.
  • This film showed an emission spectrum at 420 nm for an excitation wavelength of 300 nm.
  • the haze of this film was 1.9%.
  • the aggregation of ZnS nanoparticles was less than 4%, and it was confirmed that they were uniformly dispersed.
  • the obtained PMMA resin composition was formed into a film having a thickness of 95 m on a polyethylene terephthalate (PET) film by a solution casting method.
  • PET polyethylene terephthalate
  • the PMMA film obtained by peeling from the PET film showed an emission spectrum of 590 nm for 300 nm excitation light.
  • the aggregation of ZnS: Mn nanoparticles was less than 4%, and it was confirmed that they were uniformly dispersed.
  • the haze of the obtained film was 0.9%.
  • Example 1 the same experiment was performed except that PMMA was not present.
  • the reaction solution of DMF became a white suspension, did not show an emission spectrum, and ZnS nanoparticles could not be obtained. Also, it was impossible to obtain a resin composition and film because of the presence of PMMA.
  • PMMA was obtained at a monomer reaction rate of 42% by heating at 90 ° C for 1 hour. Next, n-butylamine (25 g) was added and the end of PMMA was converted to an SH group by stirring at 80 ° C. for 4 hours. The reaction solution was concentrated to 400 mL and poured into methanol (2 L) to isolate PMMA having an SH group at the end.
  • PMMA (5.9 g) with SH group obtained in Production Example 1 was placed in a 3-roflasco (300 mL) equipped with a reflux condenser with a nitrogen inlet, a magnetic stirrer, and a thermocouple for temperature measurement. (lOOmL) was added and dissolved. Zinc acetate dihydrate (0.966 g) and thiourea (0.237 g) were added and dissolved, and the reaction system was purged with nitrogen. The reaction solution is stirred at 150 ° C for 10 hours and then cooled to room temperature.
  • the PMMA-modified ZnS nanoparticles obtained in this way showed a 410 nm unimodal emission spectrum for excitation light of 300 nm in black mouth form.
  • the PMMA-modified nanoparticles were allowed to stand at room temperature for 6 months as a black mouth form, toluene, and DMF solution, but remained transparent, and there was no change in the UV absorption spectrum or photoluminescence spectrum. From this, it was confirmed that the effect of the modification stability by SH group-containing PMMA is large.
  • PMMA (6. Og) with SH group obtained in Production Example 1 is placed in a 3-roflasco (300 mL) equipped with a reflux condenser with a nitrogen inlet, a magnetic stirrer, and a thermocouple for temperature measurement. (lOOmL) was added and dissolved. Zinc acetate dihydrate (0.973 g), manganese acetate tetrahydrate (0.088 g), and thiourea (0.237 g) were added and dissolved, and the reaction system was purged with nitrogen. The reaction solution is stirred at 150 ° C for 10 hours and then cooled to room temperature.
  • the PMMA-modified ZnS: Mn nanoparticles obtained in this way exhibited a single-peak emission spectrum at 580 nm in a black mouth with excitation at 300 nm. This is attributed to light emission from manganese doped in ZnS crystals.
  • the PMMA-modified nanoparticles were allowed to stand at room temperature for 6 months as a solution of black mouth form, toluene, and DMF. However, they remained transparent, and there was no change in the ultraviolet absorption spectrum or photoluminescence spectrum. From this, it was confirmed that the effect of modification stability by SH group-containing PMMA is significant.
  • Example 6 the same experiment was carried out using PBA (4. Og) having SH groups obtained in Production Example 2 instead of PMMA having SH groups, and PBA-modified ZnS nanoparticles were obtained. (Yield 2.9 g) was obtained.
  • the obtained PBA-modified ZnS nanoparticles showed a single-peak emission spectrum of 408 ⁇ m for excitation light of 300 nm in black mouth form.
  • the PBA-modified nanoparticles were allowed to stand at room temperature for 6 months as a solution of black mouth form, toluene, and DMF, but remained transparent, and no change was observed in the ultraviolet absorption spectrum and photoluminescence spectrum. Based on this, it was confirmed that the effect of modification stability by SH group-containing PBA was significant.
  • the metal sulfide nanoparticle-containing resin composition of the present invention stably exhibits a quantum effect and has a high purity, so that a solar cell, a light emitting device, a display, a phosphor, a wavelength conversion device, It is useful as a material for wavelength cut filters, nonlinear optical materials, semiconductor lasers, optical memories, ultraviolet shielding materials, electromagnetic wave shielding materials, magnetic recording materials, photocatalysts, quantum transistors, biomarkers, and the like.

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Abstract

Composition de résine contenant des nanoparticules d'un sulfure de métal, laquelle est produite en faisant réagir un composé d'un métal et un composé thiourée dans un solvant polaire aprotique en présence d'une résine thermoplastique soluble dans ledit solvant et en enlevant ensuite le solvant ; et procédé servant à produire la composition de résine. Lors de la production d'une composition de résine contenant des nanoparticules d'un sulfure de métal par la réaction ci-dessus, on chauffe de préférence le système de réaction à une température de 80 à 300°C. Comme procédé servant à enlever le solvant, on utilise de préférence la distillation ou la séparation par l'ajout d'un mauvais solvant. La composition de résine contenant un sulfure de métal ci-dessus est excellente en termes de résistance aux intempéries, de résistance à l'eau, de durabilité et de transparence et elle a une pureté élevée, ne coagule pas et présente une dispersion uniforme et elle peut en outre être produite avec une productivité élevée et une bonne rentabilité économique.
PCT/JP2006/301069 2005-01-25 2006-01-24 Composition de résine contenant des nanoparticules d'un sulfure de métal et procédé servant à produire ladite composition WO2006080318A1 (fr)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100584743C (zh) * 2006-12-15 2010-01-27 中国科学院长春应用化学研究所 一种铜配合物纳米纤维的制备方法
US7976733B2 (en) * 2007-11-30 2011-07-12 Xerox Corporation Air stable copper nanoparticle ink and applications therefor
JP2021024966A (ja) * 2019-08-06 2021-02-22 三菱ケミカル株式会社 ポリビニルエステル系重合体の製造方法
JP2023024383A (ja) * 2021-08-05 2023-02-16 臺灣塑膠工業股▲ふん▼有限公司 樹脂組成物の製造方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6191005A (ja) * 1984-10-08 1986-05-09 Ryuichi Yamamoto 金属硫化物溶液とその製造方法
JPS61215661A (ja) * 1985-03-22 1986-09-25 Ryuichi Yamamoto 導電性金属硫化物組成物の製造法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6191005A (ja) * 1984-10-08 1986-05-09 Ryuichi Yamamoto 金属硫化物溶液とその製造方法
JPS61215661A (ja) * 1985-03-22 1986-09-25 Ryuichi Yamamoto 導電性金属硫化物組成物の製造法

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100584743C (zh) * 2006-12-15 2010-01-27 中国科学院长春应用化学研究所 一种铜配合物纳米纤维的制备方法
US7976733B2 (en) * 2007-11-30 2011-07-12 Xerox Corporation Air stable copper nanoparticle ink and applications therefor
JP2021024966A (ja) * 2019-08-06 2021-02-22 三菱ケミカル株式会社 ポリビニルエステル系重合体の製造方法
JP7351133B2 (ja) 2019-08-06 2023-09-27 三菱ケミカル株式会社 ポリビニルエステル系重合体の製造方法
JP2023024383A (ja) * 2021-08-05 2023-02-16 臺灣塑膠工業股▲ふん▼有限公司 樹脂組成物の製造方法
JP7558225B2 (ja) 2021-08-05 2024-09-30 臺灣塑膠工業股▲ふん▼有限公司 樹脂組成物の製造方法

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