JPWO2006080318A1 - Metal sulfide nanoparticle-containing resin composition and method for producing the composition - Google Patents

Abstract

An object of the present invention is to provide a metal sulfide nanoparticle-containing resin composition that is excellent in water resistance, weather resistance, durability, high purity, and uniformly dispersed without agglomeration, and a method for producing the same. The metal sulfide nanoparticle-containing resin composition is 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. When the metal sulfide nanoparticle-containing resin composition is obtained by the above reaction, it is preferably heated at 80 to 300 ° C. As a method for removing the solvent, separation by distillation or addition of a poor solvent is preferable. The resin composition of the present invention is excellent in weather resistance, water resistance, durability, and transparency, has high productivity, and can be produced economically.

Description

  The present invention relates to a metal sulfide nanoparticle-containing resin composition and a method for producing the composition.

  Metal sulfide 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 use quantum properties according to their size. For example, 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, biomarkers, etc. Can be mentioned.

  However, the conventional method for synthesizing such metal sulfide nanoparticles has a problem in that the nanoparticles are contaminated with ions and atoms such as sodium because of the use of a metal sulfide compound such as sodium sulfide as a sulfur source, and purification is difficult. was there. Also, metal sulfide nanoparticles are very unstable due to their high surface activity, and are prone to agglomerate during or after synthesis, resulting in non-uniform particle size, reduced quantum properties, and reduced transparency There were problems such as. Furthermore, it has been difficult to disperse conventional metal sulfide nanoparticles in a thermoplastic resin.

  As a technique for dispersing metal sulfide nanoparticles in a resin, Patent Document 1 describes a method of generating a compound semiconductor colloid in a polymer solution. However, in this method, a high molecular compound applicable to use of a protic hydrophilic solvent such as water is limited, and as a result, only materials having poor weather resistance, water resistance and durability can be produced. It was. In addition, in order to use a protic hydrophilic solvent, it is necessary to use a metal sulfide compound as a sulfur source, and the contamination of the resin composition by alkali metal ions cannot be prevented, and a high-purity material cannot be obtained. .

  As a method for obtaining highly pure metal sulfide nanoparticles, Non-Patent Document 1 describes a method using thiourea as a sulfur source in N, N-dimethylformamide. However, since thioglycerol coexists as a nanoparticle modifier in this method, the long-term stabilization effect is insufficient, it is difficult to separate from the raw material residue, and the nanoparticles are not contained in the resin. The thermoplastic resin composition in which the nanoparticles were uniformly dispersed could not be obtained due to poor compatibility when trying to disperse the polymer.

  Non-Patent Document 2 uses sodium sulfide as the sulfur source and hexadecyldithiophosphate as the modifying agent as a method for preventing the aggregation of nanoparticles, but the stabilization by the modifying agent is incomplete and transmission electron Aggregation of particles is observed in a microscope (TEM) photograph.

  Patent Document 2 describes a method for producing nanoparticles in the presence of amines, and Patent Document 3 describes a method for producing nanoparticles modified with a thiol compound and an amine compound. Because of the modification with a low molecular weight compound, the stabilizing effect was insufficient, and aggregation could not be prevented.

  Further, Patent Document 4 describes a method of purifying nanoparticle hydrosol by extracting it into an organic phase using a fat-soluble surface modifying molecule. However, there is a problem that purification efficiency is low due to mass transfer between two phases. there were. Patent Document 5 describes a method of depositing a polymer containing nanoparticles by adding a polymer to the nanoparticle dispersion and then adding a poor solvent for the polymer, but the bond between the polymer and the nanoparticles is weak. For this reason, there was a problem that nanoparticles were not sufficiently precipitated and purification efficiency was poor.

  In order to prevent aggregation and improve purification efficiency, Patent Document 6 and Patent Document 7 describe a method of modifying nanoparticles using a polymer having an SH group having strong adhesion to the nanoparticles. However, since 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 applicable to nanoparticles synthesized in an aprotic organic solvent such as zinc sulfide. I couldn't. In addition, since the polymer-modified nanoparticles obtained are hydrophilic, when a film or a molded body is produced using this, only those having poor water resistance can be obtained.

Patent Document 8, Non-Patent Document 3 and Non-Patent Document 4 describe techniques for modifying nanoparticles using a polymer obtained by reversible addition-elimination chain transfer (RAFT) polymerization. However, since the methods described in these references apply to nanoparticles synthesized by the reduction method in a protic hydrophilic solvent, producing metal sulfide nanoparticles modified with polymers obtained by RAFT polymerization I couldn't.
JP-A-5-93076 JP-A-5-113586 JP 2003-89522 A JP 2003-73126 A Japanese Patent Laid-Open No. 10-36517 JP 2002-121548 A JP 2002-121549 A US Patent Application Publication No. 2003/0199653 J. et al. Nanda et al., “Chem. Mater.”, 2000, 12: 1018. S. Chen et al., “Langmuir”, 1999, Vol. 15, p. 8100. A. B. Lowe et al., “J. Am. Chem. Soc.”, 2002, 124, 11562. J. et al. Shan et al., “Macromolecules”, 2003, 36, 4526.

  To provide a metal sulfide nanoparticle-containing resin composition that is excellent in water resistance, weather resistance, durability, high purity, and uniformly dispersed without agglomeration, and a method for producing the composition.

  As means for solving the above problems, the following metal sulfide nanoparticle-containing resin composition and a method for producing the composition are proposed.

  The resin composition containing metal sulfide nanoparticles of the present invention reacts a metal compound and a thiourea compound in an aprotic polar organic solvent in the presence of a thermoplastic resin soluble in the solvent, and then removes the solvent. A metal sulfide nanoparticle-containing resin composition (claim 1).

  In a preferred embodiment of the present invention, a thermoplastic resin soluble in an aprotic polar organic solvent is a (meth) acrylic ester resin, (meth) acrylamide resin, styrene resin, (meth) acrylonitrile resin, The metal sulfide nanoparticle-containing resin composition according to claim 1, wherein the resin composition is one or more resins selected from the group consisting of vinyl acetate resins, polycarbonate resins, and polyamide resins (claim 2). ).

  According to a preferred embodiment of the present invention, the metal sulfide nanoparticle-containing resin composition according to claim 1, wherein the thermoplastic resin soluble in the aprotic polar organic solvent is an SH group-containing polymer. Item 3).

  In a preferred embodiment of the present invention, the SH group-containing polymer is terminally SH-modified with a treating agent after reversible addition / elimination chain transfer polymerization using a thiocarbonylthio compound as a chain transfer agent. The metal sulfide nanoparticle-containing resin composition according to (4).

  In a preferred embodiment of the present invention, the metal sulfide nanoparticles 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. It is a containing resin composition (Claim 5).

  In a preferred embodiment of the present invention, 90 to 100 mol% of the metal compound comprises a zinc carboxylate compound, a zinc dithiocarboxylate compound, a zinc dithiocarbamate compound, a zinc xanthate compound, an acetylacetonatozinc compound and an alkylzinc compound. One or more compounds selected from the group, and 0 to 10 mol% is a manganese carboxylate compound, an acetylacetonatomanganese compound, a manganese nitrate, a manganese halide compound, a carboxylate copper compound, a carboxylate silver compound, and a lead carboxylate Compounds, aluminum halide compounds, cobalt carboxylates, cobalt halides, europium carboxylates, erbium carboxylates, yttrium carboxylates, neodymium carboxylates, terbium carboxylates and 6. The metal sulfide nanoparticle-containing resin composition (Claim 6) according to any one of claims 1 to 5, wherein the resin composition is one or more compounds selected from the group consisting of cerium rubonate compounds. .

  In a preferred embodiment of the present invention, the thiourea compound is one or more selected from the group consisting of thiourea, monoalkylthiourea, monoarylthiourea, dialkylthiourea, diarylthiourea, cyclic thiourea and thiourea dioxide. The metal sulfide nanoparticle-containing resin composition according to any one of claims 1 to 6, wherein the compound is a compound of (1).

  In a preferred embodiment of the present invention, the aprotic polar organic solvent is one or more compounds selected from the group consisting of 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 resin composition (claim 8).

  In addition, an embodiment of the present invention provides a metal sulfide nanoparticle in which a metal compound and a thiourea compound are reacted in an aprotic polar organic solvent in the presence of a thermoplastic resin soluble in the solvent, and then the solvent is removed. It is a manufacturing method (Claim 9) of a particle-containing resin composition.

  In a preferred embodiment of the present invention, a thermoplastic resin soluble in an aprotic polar organic solvent is a (meth) acrylic ester resin, (meth) acrylamide resin, styrene resin, (meth) acrylonitrile resin, The method for producing a metal sulfide nanoparticle-containing resin composition according to claim 9, wherein the resin composition is one or more kinds of resins selected from the group consisting of vinyl acetate resins, polycarbonate resins, and polyamide resins (claim 10). is there.

  A preferred embodiment of the present invention is the resin composition containing metal sulfide nanoparticles according to claim 9, wherein the thermoplastic resin soluble in an aprotic polar organic solvent is an SH group-containing polymer. This is a manufacturing method (claim 11).

  The preferred embodiment of the present invention is such that the SH group-containing polymer is terminally SH-treated with a treating agent after reversible addition-elimination chain transfer polymerization using a thiocarbonylthio compound as a chain transfer agent. A process for producing a metal sulfide nanoparticle-containing resin composition according to claim 12 (claim 12).

  In a preferred embodiment of the present invention, the metal sulfide nanoparticles according to claim 12, wherein the treatment agent is at least one compound selected from the group consisting of a hydrogen-nitrogen bond-containing compound, a basic compound, and a reducing agent. It is a manufacturing method (Claim 13) of a containing resin composition.

  In a preferred embodiment of the present invention, 90 to 100 mol% of the metal compound comprises a zinc carboxylate compound, a zinc dithiocarboxylate compound, a zinc dithiocarbamate compound, a zinc xanthate compound, an acetylacetonato zinc compound, and an alkyl zinc compound. One or more compounds selected from the group, and 0 to 10 mol% is a manganese carboxylate compound, an acetylacetonatomanganese compound, a manganese nitrate, a manganese halide compound, a carboxylate copper compound, a carboxylate silver compound, and a lead carboxylate Compound, Aluminum halide compound, Cobalt carboxylate, Cobalt halide, Europium carboxylate, Erbium carboxylate, Yttrium carboxylate, Neodymium carboxylate, Terbium carboxylate, Carboxyl Is at least one compound selected from the group consisting of cerium compound, a method for producing a metal sulfide nanoparticles-containing resin composition according to any of claims 9 13 (claim 14).

  In a preferred embodiment of the present invention, the thiourea compound is one or more selected from the group consisting of thiourea, monoalkylthiourea, monoarylthiourea, dialkylthiourea, diarylthiourea, cyclic thiourea, and thiourea dioxide. It is a manufacturing method (Claim 15) of the metal sulfide nanoparticle containing resin composition in any one of Claims 9-14 which is a compound of these.

  In a preferred embodiment of the present invention, the aprotic polar organic solvent is one or more compounds selected from the group consisting of N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoric triamide. It is a manufacturing method (Claim 16) of the metal sulfide nanoparticle containing resin composition in any one of Claim 9 to 15.

  According to a preferred embodiment of the present invention, when a metal compound and a thiourea compound are reacted in an aprotic polar organic solvent in the presence of a thermoplastic resin soluble in the solvent, heating is performed at 80 to 300 ° C. It is the manufacturing method (Claim 17) of the metal nanoparticle containing resin composition in any one of Claim 9 to 16 characterized by the above-mentioned.

  The metal sulfide nanoparticles according to any one of claims 9 to 17, wherein a preferred embodiment of the present invention comprises reacting a metal compound with a thiourea compound and then removing the solvent by distillation. It is a manufacturing method (claim 18) of a containing resin composition.

  In a preferred embodiment of the present invention, after reacting a metal compound and a thiourea compound, a thermoplastic resin containing metal sulfide nanoparticles is precipitated and separated from the solvent by adding a poor solvent for the thermoplastic resin. A method for producing a metal sulfide nanoparticle-containing resin composition according to any one of claims 9 to 17 (claim 19).

  The metal sulfide nanoparticle-containing resin composition of the present invention has high purity and is excellent in weather resistance, water resistance and durability. Further, since the metal sulfide nanoparticles are uniformly dispersed in the resin without agglomeration, the quantum characteristics are excellent. Moreover, since it can be manufactured in one step and one pot, it is highly productive and economical.

  In addition, since nanoparticle synthesis and modification are performed simultaneously, it is possible to almost completely prevent aggregation of the nanoparticles, and furthermore, the particle diameter can be highly controlled by enclosing the nanoparticles with a polymer. Further, in the production method of the present invention, the metal sulfide nanoparticle-containing resin composition can easily precipitate and separate the polymer-modified metal sulfide nanoparticles by adding a poor solvent for the polymer after the reaction. Purification is easy and nanoparticles with high purity can be obtained easily.

  The resin composition containing metal sulfide nanoparticles of the present invention reacts a metal compound and a thiourea compound in an aprotic polar organic solvent in the presence of a thermoplastic resin soluble in the solvent, and then removes the solvent. Can be obtained.

  The aprotic 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 are generally well known. Among these, DMF, DMAC, DMSO, and HMPA are preferable in terms of solubility, boiling point, and safety, and DMF and DMAC are more preferable. These may be used alone or in combination.

  The thermoplastic resin used in the present invention is not particularly limited as long as it is soluble in the aprotic polar organic solvent. Specific examples of such thermoplastic resins include polymethyl methacrylate, methyl methacrylate / methyl acrylate copolymer, methyl acrylate / styrene / acrylonitrile copolymer (ASA resin), methyl methacrylate / styrene copolymer. (Meth) acrylic ester resins such as coalescence (MS resin) and acrylic modified polyvinyl chloride; (Meth) acrylamide such as poly (N, N-dimethyl (meth) acrylamide) and poly (N-isopropyl (meth) acrylamide) Resin: polystyrene, poly (α-methylstyrene), styrene / acrylonitrile copolymer (SAN resin), styrene / maleic anhydride copolymer, styrene / maleimide copolymer, acrylonitrile / butadiene / styrene copolymer (ABS) Resin), chlorinated polyethylene / acrylic Styrenic resin such as nitrile / styrene copolymer (ACS resin); (Meth) acrylonitrile resin such as poly (meth) acrylonitrile, (meth) acrylonitrile / vinyl chloride copolymer; polyvinyl acetate, ethylene / vinyl acetate copolymer Polymers (EVA resins), ethylene / vinyl acetate / vinyl chloride copolymers, vinyl acetate resins such as polyvinyl acetal and polyvinyl alcohol; polycarbonate resins such as polycarbonate and modified polycarbonate; polyamide 66, polyamide 6, polyamide 46, etc. Polyamide resins; Polyester resins such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), aromatic polyester, polyarylate; thermoplastic polyimide, polyamideimide, polyether Polyimide resins such as polyimide; polyether resins such as polyacetal, polyether ether ketone, polyether ketone, polyether sulfone, polythioether sulfone; polyester thermoplastic elastomer (TPEE), polyvinyl chloride thermoplastic elastomer (TPVC) ), Thermoplastic elastomers such as polyurethane-based thermoplastic elastomers (TPU), polyamide-based thermoplastic elastomers (TPAE), (meth) acrylic ester-based thermoplastic elastomers, and SH group-containing polymers.

  In addition to these, various copolymers and modified polymers can be used. These may be used alone or in combination. Among these thermoplastic resins, (meth) acrylic acid ester resin, (meth) acrylamide resin, styrene resin, (meth) acrylonitrile resin, Vinyl acetate resins, polycarbonate resins, polyamide resins, and SH group-containing polymers are preferred, (meth) acrylic acid ester resins, (meth) acrylamide resins, styrene resins, and SH group-containing polymers are more preferred, and SH groups. The containing polymer is most preferred.

  Although it does not specifically limit as a suitable characteristic of these thermoplastic resins, It is preferable that a glass transition temperature is 80 degreeC or more at a point with high heat resistance, and it is preferable that it is 100 degreeC or more. In terms of mechanical strength, the molecular weight is preferably 5000 or more, and more preferably 10,000 or more. However, when an SH group-containing polymer is used as the thermoplastic resin, it is not limited to this because of its high affinity with the metal sulfide nanoparticles, and the molecular weight range described below is preferable.

  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. Here, the polymer refers to a compound having a structure in which 10 or more monomer units are connected. The SH group may be present at the end of the polymer, may be present as a substituent in the main chain, or may be present in a branch branched from the main chain. The polymer structure is not limited to a straight chain, a branch, a dendrimer, a hyperbranch and the like, but a linear polymer is preferable in terms of high efficiency for modifying the nanoparticles. In addition, the primary structure of the polymer is not particularly limited, and any of a homopolymer, a block polymer, a random polymer, a gradient polymer, and the like can be used, such as a syndiotactic polymer, an isotactic polymer, a heterotactic polymer, etc. Stereoregular polymers can also be used.

  As the kind of the SH group-containing polymer, either an addition polymerization type polymer or a condensation polymerization type polymer can be used, but an addition polymerization type polymer is preferable in terms of weather resistance, water resistance, and durability, and a vinyl polymer is more preferable. In view of availability, a vinyl polymer obtained by radical polymerization is more preferable. Specific examples of such a polymer include polymers obtained by polymerizing vinyl acetate in the presence of thioacetic acid and then hydrolyzing the end groups. Am. Chem. Sco. 2001, Vol. 123, p. 10411, and the like.

  As an SH group-containing polymer, a reversible addition / desorption chain transfer (RAFT) using a thiocarbonylthio compound as a chain transfer agent in that an SH group can be easily and reliably introduced and the molecular weight and molecular weight distribution can be controlled. ) After polymerization, most preferably terminally SH-treated with a treating agent. RAFT polymerization is a method for controlled radical polymerization of a vinyl monomer using a thiocarbonylthio compound as a chain transfer agent, as described in JP-T-2000-515181. The polymer obtained by RAFT polymerization has a dithioester structure or a trithiocarbonate structure at the molecular end or in the main chain. In the present invention, it is converted into an SH group by treatment with a treating agent.

  The thiocarbonylthio compound used in the present invention is not particularly limited, and examples thereof include those described in JP 2000-515181 A. However, the following compounds are preferable in view of availability and reactivity. ;

(In the formula, Me represents a methyl group, Et represents an ethyl group, and Ph represents a phenyl group). Of these, compounds having a trithiocarbonate structure are preferred in terms of reactivity. When a polyfunctional thiocarbonylthio compound is used, a polymer having SH groups at a plurality of terminals in one molecule can be obtained. When polymer-modified metal sulfide nanoparticles are produced by the method of the present invention using such a polymer, a material having a structure in which the nanoparticles are crosslinked with each other can be obtained. In RAFT polymerization, since the molecular weight is kept uniform, it is possible to produce a strong coating film or film in which the distance between the nanoparticles is kept constant.

  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. In the case of solution polymerization, 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, acetonitrile, and the like.

  RAFT polymerization is achieved by radical polymerization of a vinyl monomer in the presence of the thiocarbonylthio compound, but 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 of starting by light irradiation, a method of starting by microwave irradiation, and the like. Among these, a method in which a radical initiator that thermally decomposes is present in view of availability, versatility, and controllability is preferable.

  Examples of such radical initiators include methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, cyclohexanone peroxide, benzoyl peroxide, cumene hydroperoxide, di-t-butyl peroxide, t-butyl peroxyacetate, bis ( 2-ethylhexyl) peroxide initiators such as peroxydicarbonate and succinic peroxide; dimethyl 2,2′-azobisisobutyrate, 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) 2,2′-azobis (isobutyronitrile), 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′- Azobis (2-methylbutyronitrile), 4,4 -Azo initiators such as azobis (4-cyanovaleric acid); inorganic peroxides such as potassium persulfate and sodium persulfate; vinyl monomers that generate radical species thermally such as styrene; benzoin A compound that generates radical species by light, such as a derivative or benzophenone; a redox-type initiator that combines a reducing agent and an oxidizing agent can be given, but is not limited thereto.

  In the present invention, an azo initiator is preferred from the viewpoint of availability, safety and reactivity. The amount of the polymerization initiator used is not particularly limited, but is preferably 0.5 mol or less with respect to 1 mol of the thiocarbonylthio group in the thiocarbonylthio compound in that the molecular weight distribution of the obtained polymer is narrow. 25 mol or less is more preferable.

  It does not specifically limit as a vinyl-type monomer used for the said RAFT polymerization, What can be radically polymerized can be used. Specific examples of such vinyl monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, (meth) acrylic acid 2 -Hydroxyethyl, 2-methoxyethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, glycidyl (meth) acrylate, 2- (meth) acryloyloxypropyltrimethoxysilane, (meth) acrylic acid 2,2 , 2-trifluoroethyl, (meth) acrylic acid esters such as allyl (meth) acrylate; (meth) acrylic acid; styrene, α-methylstyrene, p-hydroxystyrene, p-methoxystyrene, p-vinylbenzenesulfone Styrenes such as acid, sodium p-vinylbenzenesulfonate, divinylbenzene Compound; aliphatic olefin compound such as butadiene and isoprene; halogen-containing vinyl compound such as vinyl chloride, vinylidene chloride and chloroprene; (meth) acrylamide, N-methyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, (Meth) acrylamides such as N-isopropyl (meth) acrylamide; nitrile compounds such as (meth) acrylonitrile; maleimide compounds such as N-phenylmaleimide; heterocyclic compounds such as 4-vinylpyridine and N-vinylpyrrolidone; vinyl acetate; Examples include vinyl ester compounds such as vinyl propionate, vinyl benzoate, and maleic anhydride, but are not limited thereto.

  In the present invention, (meth) acrylic acid ester and styrenic compound are preferable from the viewpoint of weather resistance, water resistance, durability, and heat resistance of the polymer obtained, methyl (meth) acrylate, ethyl (meth) acrylate, ( More preferred are n-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, styrene, and α-methylstyrene. These vinyl monomers may be used alone or in combination.

  Although it does not specifically limit as a processing agent used when converting the polymer obtained by RAFT polymerization into an SH group containing polymer, It consists of a hydrogen-nitrogen bond containing compound, a basic compound, and a reducing agent at the point with high conversion efficiency. A compound selected from the group is preferred.

  Although it does not specifically limit as a hydrogen-nitrogen bond containing compound among the said processing agents, Ammonia, hydrazine, a primary amine, a secondary amine, a hindered amine light stabilizer (HALS) etc. can be mentioned. Specific examples of the primary amine include methylamine, ethylamine, isopropylamine, n-butylamine, t-butylamine, 2-aminoethanol, ethylenediamine, cyclohexylamine, and aniline.

  Specific examples of the secondary amine include dimethylamine, diethylamine, diisobutylamine, iminodiacetic acid, bis (hydroxydiethyl) amine, di-n-butylamine, di-t-butylamine, diphenylamine, imidazole, and piperidine. . Specific examples of the HALS include ADK STAB LA-77 (Asahi Denka Kogyo Co., Ltd.), Tinuvin 144 (Ciba Specialty Chemicals), ADK STAB LA-67 (Asahi Denka Kogyo Co., Ltd.), and the like. be able to.

  Among the above-mentioned treatment agents, examples of basic compounds are not particularly limited, but sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, sodium methoxide, sodium ethoxide, sodium carbonate, potassium carbonate And so on.

No particular limitation is imposed on the reducing agent of the treatment agent include sodium hydride, lithium hydride, calcium _{hydride, LiAlH 4, NaBH 4, LiBEt} 3 H, hydrogen and the like.

  The said processing agent may be used independently and may be used in combination of multiple. A hydrogen-nitrogen bond-containing compound having a boiling point of 20 to 200 ° C. and a reducing agent are preferable in terms of conversion efficiency, and a primary amine having a boiling point of 20 to 100 ° C. is more preferable in that purification can be simplified. Such primary amines can be removed by distillation after the treatment reaction. Although the usage-amount of the said processing agent is not specifically limited, 0.01-100 weight part is preferable with respect to 100 weight part of polymers with respect to conversion efficiency and economical efficiency, and 0.1-30 weight part is more preferable. The reaction conditions are not particularly limited.

  The molecular weight of the SH group-containing polymer synthesized by RAFT polymerization in the present invention is not particularly limited, but the number average molecular weight (Mn) determined by gel permeation chromatography (GPC) analysis is 1000 to 1000 in that the effect of nanoparticle modification is high. It is preferably in the range of 100,000, 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 (Mw / Mn) obtained by GPC analysis in that the particle diameter of the nanoparticles becomes uniform is 1.5 or less. Preferably, it is 1.3 or less.

  When the SH group-containing polymer is used as the thermoplastic resin of the present invention, since the SH group can efficiently modify the surface of the metal sulfide nanoparticle, nanoparticles protected with the polymer can be obtained. Thereby, aggregation of nanoparticles can be prevented, so that the particle size of the metal sulfide 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. In the case of nanoparticles with uniform quantum characteristics, the emission spectrum is single and sharp. In the metal sulfide nanoparticle-containing resin composition having a uniform particle diameter and quantum characteristics, for example, a resin composition having excellent transparency and ultraviolet absorbing ability is obtained.

  The metal compound used in the present invention is not particularly limited, and a compound that reacts with a thiourea compound to form sulfide nanoparticles can be used. Examples of such 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, and tantalum compounds. Chrome compounds, molybdenum compounds, tungsten compounds, germanium compounds, tin compounds, lead compounds, mercury compounds, antimony compounds, bismuth compounds, europium compounds, erbium compounds, yttrium compounds, neodymium compounds, terbium compounds, cerium compounds, etc. it can.

  Specific examples of the zinc compound are not particularly limited, but include zinc acetate, zinc benzoate, zinc citrate, zinc formate, zinc laurate, zinc salicylate, etc .; zinc dithioacetate, zinc dithiobenzoate, etc. Zinc dithiocarboxylate; zinc dithiocarbamate such as zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, zinc dibutyldithiocarbamate, zinc N-ethyl-N-phenyldithiocarbamate, zinc N-pentamethylenedithiocarbamate, zinc dibenzyldithiocarbamate Compound: zinc ethyl xanthate, zinc butyl xanthate, zinc xanthate zinc such as isopropyl xanthate; acetylacetonato zinc compound such as acetylacetonato zinc; dimethyl zinc, di Chill zinc, alkyl zinc compounds, such as diisopropyl zinc; dichloro zinc, dibromo zinc, chloromethyl zinc, zinc halide compounds such as bromomethyl zinc; and zinc nitrate may be mentioned.

  Although it does not specifically limit as a specific example of the said manganese compound, Carboxylic acid manganese compounds, such as manganese acetate and manganese benzoate; Acetyl acetonato manganese compounds, such as acetylacetonato manganese; Manganese nitrate; Halogenation, such as dichloro manganese and dibromo manganese Mention may be made of manganese compounds.

  Although it does not specifically limit as a specific example of the said copper compound, Carboxylic acid copper compounds, such as copper acetate, copper benzoate, copper citrate, and copper phthalate; Dithiocarbamate copper compounds, such as copper dimethyldithiocarbamate; Copper chloride, Bromide Examples include copper halide compounds such as copper; copper nitrate; copper sulfate.

  Specific examples of the magnesium compound include, but are not limited to, magnesium carboxylate compounds such as magnesium acetate; alkyl magnesium compounds such as diethyl magnesium and di-n-butyl magnesium; chloromethyl magnesium, bromomethyl magnesium, chloroethynyl magnesium, iodine And magnesium halide compounds such as magnesium halide.

  Although it does not specifically limit as a specific example of the said titanium compound, Titanium carboxylate compounds, such as titanium cresylate; Titanium halide compounds, such as titanium trichloride, titanium tetrachloride, titanium tetrabromide; Titanium oxide (II) acetylacetonate An acetylacetonato titanium compound such as

  Although it does not specifically limit as a specific example of the said cobalt compound, Carboxylic acid cobalt compounds, such as cobalt acetate, cobalt benzoate, cobalt citrate, and cobalt oxalate; Cobalt halide compounds, such as cobalt chloride; Acetyl, such as acetylacetonato cobalt Examples thereof include acetonatocobalt compounds.

  Specific examples of the iron compound are not particularly limited, and examples thereof include iron carboxylate compounds such as iron acetate; iron halide compounds such as iron dichloride and iron trichloride.

  Specific examples of the nickel compound are not particularly limited, but nickel carboxylate compounds such as nickel acetate, nickel formate and nickel lactate; acetylacetonatonickel compounds such as acetylacetonatonickel; dithiocarbamines such as bis (dibutyldithiocarbamate) nickel Examples thereof include nickel acid compounds; nickel halide compounds such as nickel chloride.

  Specific examples of the cadmium compound include, but are not limited to, cadmium acetate, cadmium formate, cadmium carboxylate such as cadmium stearate; cadmium chloride compounds such as cadmium chloride, cadmium bromide, methyl cadmium chloride; dimethyl cadmium, diethyl Examples thereof include alkyl cadmium compounds such as cadmium.

  Although it does not specifically limit as a specific example of the said aluminum compound, Alkyl aluminum compounds, such as trimethylaluminum, triethylaluminum, tri-n-butylaluminum, and trioctylaluminum; Aluminum trichloride, dimethylaluminum chloride, diethylaluminum chloride, methyl dichloride Examples thereof include aluminum halide compounds such as aluminum and ethylaluminum dichloride.

  Specific examples of the gallium compound include, but are not limited to, alkyl gallium compounds such as tri-n-butyl gallium; gallium halide compounds such as gallium trichloride, di-n-butyl gallium chloride, and n-butyl gallium dichloride. Can be mentioned.

  Specific examples of the indium compound include, but are not limited to, alkyl indium compounds such as trimethylindium, triethylindium, and tri-n-butylindium; indium trichloride, di-n-butylindium chloride, n-butylindium dichloride, and the like And an indium halide compound.

  Specific examples of the vanadium compound are not particularly limited, and examples thereof include vanadium halide compounds such as vanadium dichloride and vanadium tetrachloride.

  Specific examples of the tantalum compound include, but are not limited to, tantalum halide compounds such as tantalum pentachloride and tantalum pentabromide.

  Specific examples of the chromium compound include, but are not limited to, chromium carboxylate compounds such as chromium acetate; chromium halide compounds such as chromium tribromide and chromium triiodide.

  Specific examples of the molybdenum compound include, but are not limited to, molybdenum carboxylate compounds such as molybdenum acetate dimer; molybdenum halide compounds such as molybdenum tetrachloride and molybdenum tetrabromide.

  Specific examples of the tungsten compound include, but are not limited to, tungsten halide compounds such as tungsten tetrachloride and tungsten tetrabromide.

  Specific examples of the germanium compound are not particularly limited, and examples thereof include germanium halide compounds such as germanium tetrachloride and germanium tetrabromide.

  Although it does not specifically limit as a specific example of the said tin compound, Carboxylic acid compounds, such as a tin acetate; Tin halide compounds, such as a tin dichloride and a tin tetrachloride, etc. can be mentioned.

  Specific examples of the lead compound include, but are not limited to, lead carboxylate compounds such as lead acetate; lead halide compounds such as lead dichloride and lead dibromide.

  Although it does not specifically limit as a specific example of the said mercury compound, Carboxylic acid mercury compounds, such as mercury acetate; Halogenated mercury compounds, such as mercury dichloride, etc. can be mentioned.

  Specific examples of the antimony compound include, but are not limited to, antimony carboxylate compounds such as antimony acetate; alkylantimony compounds such as trimethylantimony and tri-n-butylantimony; antimony halides such as antimony trichloride and methylantimony dichloride. A compound etc. can be mentioned.

  Specific examples of the bismuth compound are not particularly limited, but carboxylic acid bismuth compounds such as bismuth acetate; alkylated bismuth compounds such as trimethyl bismuth and tri-n-butyl bismuth; halogenated compounds such as bismuth trichloride and methyl bismuth dichloride. Examples thereof include bismuth compounds.

  Although it does not specifically limit as a specific example of the said europium compound, Carboxylic acid europium compounds, such as europium acetate and an oxalate europium; Halogenated europium compounds, such as europium chloride; Europium nitrate; Europium carbonate etc. can be mentioned.

  Specific examples of the erbium compound include, but are not limited to, erbium carboxylate compounds such as erbium acetate and erbium oxalate; acetylacetonatoerbium compounds such as acetylacetonatoerbium; alkoxylated erbium compounds such as erbium isopropoxide; Erbium halide compounds such as erbium and erbium fluoride; erbium nitrate; erbium carbonate and the like.

  Specific examples of the yttrium compound include, but are not limited to, yttrium carboxylate compounds such as yttrium acetate and yttrium oxalate; yttrium halide compounds such as yttrium chloride and yttrium bromide; yttrium nitrate; yttrium carbonate; yttrium isopropoxide and the like And the alkoxylated yttrium compound.

  Specific examples of the neodymium compound include, but are not limited to, neodymium carboxylic acid compounds such as neodymium acetate and neodymium 2-ethylhexanoate; acetylacetonatoneodymium compounds such as acetylacetonatoneodymium; neodymium nitrate; neodymium carbonate; neodymium chloride; And halogenated neodymium compounds such as neodymium bromide; alkoxylated neodymium compounds such as neodymium isopropoxide.

  Specific examples of the terbium compound include, but are not limited to, terbium carboxylate compounds such as terbium acetate and terbium oxalate; acetylacetonatoterbium compounds such as acetylacetonatoterbium; terbium halide compounds such as terbium chloride and terbium bromide Terbium carbonate; terbium nitrate and the like.

  Although it does not specifically limit as a specific example of the said cerium compound, Carboxylic acid cerium compounds, such as cerium acetate, cerium 2-ethylhexanoate, and cerium oxalate; Cerium carbonate; Cerium nitrate; Cerium sulfate; Cerium chloride, Cerium bromide Examples include cerium halide compounds; acetylacetonatocerium compounds such as trifluoroacetylacetonatocerium.

  The said metal compound used by this invention may be used independently, and may be used in combination of multiple. Further, it may be a hydrate or an anhydride. The oxidation number of the metal atom is not particularly limited.

  As said metal compound used by this invention, it is preferable that 90-100 mol% of a metal compound is a zinc compound at the point of the quantum characteristic of the nanoparticle obtained, safety | security, and an environmental load, Availability, reactivity In this respect, 90 to 100 mol% of the metal compound is more preferably a zinc carboxylate compound, a zinc dithiocarboxylate compound, a zinc dithiocarbamate compound, a zinc xanthate compound, an acetylacetonatozinc compound, or an alkylzinc compound.

  In a preferred embodiment of the present invention, a metal compound other than the zinc compound can be used as 0 to 10 mol% of the metal compound. This makes it possible to produce zinc sulfide nanoparticles doped with metal atoms other than zinc. Such doping makes it possible to control the light emission characteristics, absorption wavelength, and the like of the obtained metal sulfide nanoparticles.

  In a preferred embodiment of the present invention, the metal compound other than zinc used for doping purposes includes manganese carboxylate compound, acetylacetonatomanganese compound, manganese nitrate, manganese halide compound in terms of availability, reactivity, and quantum characteristics. , Copper carboxylate compound, silver carboxylate compound, lead carboxylate compound, aluminum halide compound, cobalt carboxylate compound, cobalt halide compound, europium carboxylate, erbium carboxylate, yttrium carboxylate, neodymium carboxylate A terbium carboxylate compound and a cerium carboxylate compound are preferred.

  The thiourea compound used in the present invention is not particularly limited. For example, thiourea, monoalkylthiourea, monoarylthiourea, dialkylthiourea, diarylthiourea, trialkylthiourea, tetraalkylthiourea, carboxyl group-containing thiourea, Examples thereof include cyclic thiourea and thiourea dioxide.

  Of the above thiourea compounds, specific examples of monoalkylthiourea are not particularly limited, but N-methylthiourea, N-isopropylthiourea, N-allylthiourea, Nn-propylthiourea, Nn-butylthiourea, N -N-decylthiourea, N-2-phenylethylthiourea, N-triphenylmethylthiourea and the like can be mentioned.

  Although it does not specifically limit as a specific example of monoaryl thiourea among the said thiourea compounds, N-phenyl thiourea, No-tolyl thiourea, Np-tolyl thiourea, N-3-pyridyl thiourea, Np- Cyanophenylthiourea, N-2-pyridylthiourea, N-1-naphthylthiourea, Np-nitrophenylthiourea, No-methoxyphenylthiourea, Nm-fluorothiourea, Np-phenoxyphenyl Examples thereof include thiourea and 1,4-phenylenebis (thiourea).

  Among the thiourea compounds, specific examples of dialkylthiourea are not particularly limited, but N, N′-dimethylthiourea, N, N′-diethylthiourea, N, N′-di-n-butylthiourea, N, N Examples thereof include '-di-n-octylthiourea, N, N-dicyclohexylthiourea, N, N′-bis (dimethylaminopropyl) thiourea and the like.

  Among the above thiourea compounds, specific examples of diarylthiourea are not particularly limited, but N, N′-diphenylthiourea, N, N′-di-o-tolylthiourea, N, N′-di-p-tolylthio are used. Examples include urea.

  Specific examples of the trialkylthiourea among the thiourea compounds are not particularly limited, and examples thereof include trimethylthiourea, triethylthiourea, and triallylthiourea.

  Specific examples of tetraalkylthiourea among the thiourea compounds are not particularly limited, and examples thereof include tetramethylthiourea and tetraethylthiourea.

  Among the thiourea compounds, specific examples of carboxyl group-containing thiourea are not particularly limited, but N-acetylthiourea, N-benzoylthiourea, N- (benzoylamidino) thiourea, N, N-diisobutyl-N′— Examples include benzoylthiourea.

  Specific examples of the cyclic thiourea among the thiourea compounds are not particularly limited, and examples thereof include ethylene thiourea and propylene thiourea.

  The thiourea compounds used in the present invention may be used alone or in combination. Of the above thiourea compounds, thiourea, monoalkylthiourea, monoarylthiourea, dialkylthiourea, diarylthiourea, cyclic thiourea, and thiourea dioxide are preferred in terms of reactivity and availability, and thiourea, N- More preferred are methylthiourea, N, N′-dimethylthiourea, ethylenethiourea, and thiourea dioxide.

  When reacting a metal compound and a thiourea compound in the presence of a thermoplastic resin, the amount ratio of these compounds is not particularly limited, but the particle size, particle size distribution, and quantum characteristics of the resulting metal sulfide nanoparticles From the viewpoint of yield, it is preferable to use the thiourea compound in a proportion of 0.2 to 1.2 mol, more preferably 0.5 to 1 mol, relative to 1 mol of the metal compound. .

  Moreover, it is preferable to use a thermoplastic resin in the ratio of 50-100000 weight part with respect to 100 weight part of metal compounds at the point of transparency of the resin composition obtained, and an optical characteristic, and the ratio of 100-50000 weight part. More preferably it is used. However, in the case of an SH group-containing polymer, the metal sulfide nanoparticles can be strongly modified, so that it is not limited to this, and a ratio of 0.01 to 1.5 mol, or even 0.05 mol to 1 mol, relative to 1 mol of the metal compound Is preferably used.

  The amount of the aprotic polar organic solvent to be used is not particularly limited, but is preferably 100 to 100,000 parts by weight and more preferably 500 to 50,000 parts by weight with respect to 100 parts by weight of the metal compound in terms of reaction efficiency.

  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, more preferably 100 ° C. or higher in terms of reaction efficiency. Further, when the reaction temperature is too high, decomposition of the thermoplastic resin or thiourea compound occurs, so that it is preferably 300 ° C. or lower, and more preferably 250 ° C. or lower. Either batch type or fluid type reaction can be applied.

  The metal sulfide nanoparticle-containing resin composition of the present invention can be obtained by reacting the metal compound with a thiourea compound and then removing the solvent. The method for removing the solvent is not particularly limited. For example, (1) a method for distillation; (2) a method for precipitation by adding a poor solvent for a thermoplastic resin to separate from the solvent; (3) a method for freeze-drying, etc. Can be mentioned. Among these, the methods (1) and (2) are preferable in that the operation is simple, and the method (2) is more preferable in that a highly pure resin composition can be obtained.

  In the above (1) distillation method, the specific means is not particularly limited. The pressure may be normal pressure, but is preferably reduced in terms of efficiency. The temperature may be room temperature, but it is preferable to heat from the viewpoint of efficiency. The distilled solvent is preferably recovered and reused from the viewpoint of safety and environmental load.

  In the method of (2) precipitation by adding a poor solvent for the thermoplastic resin and separating from the solvent, the specific means is not particularly limited. Although the said poor solvent should just select an appropriate thing according to the thermoplastic resin to be used, what is compatible with the aprotic polar organic solvent used at the time of reaction is preferable. In addition, when an appropriate poor solvent combination cannot be found, an appropriate poor solvent may be selected after once replacing the aprotic polar organic solvent with another appropriate solvent.

  Examples of poor solvents for thermoplastic resins include aliphatic hydrocarbon solvents such as hexane, pentane, octane, and cyclohexane; alcohol solvents such as methanol, ethanol, hexanol, and octanol; trifluoroethanol, HCFC-225 (Asahi Glass Co., Ltd.) )) And other fluorine-based solvents. The metal sulfide nanoparticle-containing resin composition separated by adding a poor solvent can be used after being dried 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. As the thermoplastic resin or the thermosetting resin, a general one can be used, and it is preferable to use one having compatibility with the resin composition according to the present invention. Examples of the additive include pigments and dyes, heat stabilizers, antioxidants, ultraviolet absorbers, light stabilizers, lubricants, plasticizers, flame retardants, and antistatic agents.

  The metal sulfide 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.

  Examples of the present invention are shown below, but are not limited thereto.

  In the present invention, the polymer Mw and Mn were determined by GPC analysis. A Waters system was used, and the column was analyzed by using Shodex K-806 and K-805 (Showa Denko Co., Ltd.) connected together, chloroform as an eluent, and a polystyrene standard sample. The monomer reaction rate in polymerizing the polymer was determined by gas chromatography (GC) analysis. The GC analysis was performed with a gas chromatograph GC-14B (manufactured by Shimadzu Corporation) using a capillary column DB-17 (manufactured by J & W SCIENTIFIC) by dissolving the sampling solution in ethyl acetate.

  The dispersion state and particle size of the metal sulfide nanoparticles were observed at an accelerating voltage of 80 kV using a transmission electron microscope (TEM) JEM-1200EX (manufactured by JEOL Ltd.). The emission spectrum was measured using a spectrofluorometer FP-6500DS (manufactured by JASCO Corporation) with 300 nm excitation light for a solution or film sample, and a photoluminescence spectrum was measured in the range of 350 to 700 nm.

  The thiocarbonylthio compound used as the chain transfer agent is disclosed in JP 2000-515181 A, J. Am. Chem. Research (S), 1995, p. 478, J.A. Chem. It was synthesized by applying the methods described in Research (S), 1998, page 454, and Macromolecules, 2002, 35, 5417. The haze measurement of the film was performed using COH300A (made by Nippon Denshoku Industries Co., Ltd.).

(Example 1)
Synthesis of poly (methyl methacrylate) (PMMA) containing zinc sulfide (ZnS) nanoparticles In a three-necked flask (300 mL) equipped with a reflux condenser with a nitrogen introduction tube, a magnetic stirrer, and a thermocouple for temperature measurement, PMMA (SUMIPEX LG- 21, Sumitomo Chemical Co., Ltd.) (6.0 g) was added, and DMF (100 mL) 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 solid obtained by distilling off DMF under reduced pressure is dissolved in toluene (20 mL), and a small amount of insoluble matter is removed by centrifugation (6000 rpm / 15 minutes). did. The supernatant was concentrated to 10 mL and poured into methanol (100 mL) to precipitate and separate ZnS nanoparticle-containing PMMA and dried under reduced pressure (yield 5.12 g).

  The obtained PMMA resin composition was able to form a transparent film on a quartz substrate by a solution casting method (film thickness 100 μm), and showed emission spectra of 410 nm and 436 nm with respect to 300 nm excitation light. Although some of the nanoparticles are considered to be aggregated because the emission spectrum was bimodal, as a result of TEM observation, the aggregation of ZnS nanoparticles was less than 3% and was almost uniformly dispersed. It was confirmed. The haze of the obtained film was 0.8%.

(Example 2)
Synthesis of ZnS nanoparticle-containing poly (n-butyl acrylate) (PBA) In Example 1, instead of PMMA, PBA (4.0 g) (Aldrich) (Mw: about 60000, Mn: about 20000, product number: 18,141-2) The same experiment was carried out using) to obtain a colorless and transparent viscous polymer (yield: 3.0 g).

  The obtained PBA showed emission spectra of 408 nm and 432 nm for excitation light of 300 nm in chloroform. Since the emission spectrum was bimodal, it is considered that some ZnS nanoparticles were aggregated, but this PBA containing ZnS nanoparticles was allowed to stand 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 allowed to stand as a chloroform, toluene, and DMF solution at room temperature, turbidity occurred in one week and the transparency was lowered, so that the nanoparticle stabilization effect by commercially available PBA is considered to be incomplete. .

(Example 3)
Synthesis of ZnS nanoparticle-containing methyl methacrylate-styrene copolymer (MS resin) In Example 1, MS resin (Cebian-MAS10; manufactured by Daicel Polymer Co., Ltd.) (5.5 g) was used instead of PMMA. Experiments were carried out to obtain ZnS nanoparticle-containing MS resin (yield 5.0 g). This ZnS nanoparticle-containing MS resin was formed into a film having a thickness of 100 μm by a solution casting method. This film showed an emission spectrum at 417 nm with respect to an excitation wavelength of 300 nm. The haze of this film was 1.0%. As a result of TEM observation, the aggregation of ZnS nanoparticles was less than 3%, and it was confirmed that they were uniformly dispersed.

Example 4
Synthesis of ZnS nanoparticle-containing polycarbonate (PC) In Example 1, a similar experiment was performed using PC (Caliber 300-30; manufactured by Sumitomo Dow Co., Ltd.) (2.5 g) instead of PMMA. ZnS nanoparticles PC containing was obtained (yield 2.1 g). This ZnS nanoparticle-containing PC was molded as a sheet having a thickness of 0.3 mm by hot pressing. This film showed an emission spectrum at 420 nm with respect to an excitation wavelength of 300 nm. The haze of this film was 1.9%. As a result of TEM observation, the aggregation of ZnS nanoparticles was less than 4%, and it was confirmed that they were uniformly dispersed.

(Example 5)
Synthesis of Manganese-Doped Zinc Sulfide (ZnS: Mn) Nanoparticle-Containing PMMA A three-necked flask (300 mL) equipped with a reflux condenser with a nitrogen introduction tube, a magnetic stirrer, and a thermocouple for temperature measurement was combined with PMMA (SUMIPEX LG-21, Sumitomo Chemical Co., Ltd.) (6.1 g) was added, and DMF (100 mL) was added and dissolved. Zinc acetate dihydrate (0.972 g), manganese acetate tetrahydrate (0.083 g) and thiourea (0.245 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 solid obtained by distilling off DMF under reduced pressure is dissolved in toluene (20 mL), and a small amount of insoluble matter is removed by centrifugation (6000 rpm / 15 minutes). did. The supernatant was concentrated to 10 mL, poured into methanol (100 mL) to precipitate and separate ZnS: Mn nanoparticle-containing PMMA, and dried under reduced pressure (yield 5.52 g).

  The obtained PMMA resin composition was formed into a film with a thickness of 95 μm on a polyethylene terephthalate (PET) film by a solution casting method. The PMMA film obtained by peeling from the PET film showed an emission spectrum of 590 nm with respect to 300 nm excitation light. As a result of TEM observation, 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%.

(Comparative Example 1)
In Example 1, an experiment was performed in exactly the same manner 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. Moreover, since PMMA was not allowed to coexist, a resin composition and a film could not be obtained.

(Production Example 1)
Synthesis of polymethyl methacrylate (PMMA) having an SH group at its terminal A 4-necked flask (1000 mL) equipped with a reflux condenser with a nitrogen introduction tube, a magnetic stirrer, and a thermocouple for temperature measurement was added to 2- (2-phenylpropyl). ) Dithiobenzoate (8.0 g), methyl methacrylate (501 g), toluene (260 g) and 2,2′-azobis (isobutyronitrile) (1.1 g) were added, and the inside of the reactor was purged with nitrogen.

  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. The molecular weight and molecular weight distribution of the obtained PMMA were Mw = 13500, Mn = 11300, and Mw / Mn = 1.19.

(Production Example 2)
Synthesis of poly (n-butyl acrylate) having an SH group at its end (PBA) A 4-necked flask (100 mL) equipped with a reflux condenser with a nitrogen introduction tube, a magnetic stirrer, and a thermocouple for temperature measurement was combined with n-butyl acrylate ( 49.8 g) and dibenzyltrithiocarbonate (0.504 g) 2,2′-azobis (isobutyronitrile) (0.072 g) were added, and the inside of the reactor was purged with nitrogen. By stirring this reaction solution at 90 ° C. for 1 hour, PBA was obtained at a reaction rate of 65%. Unreacted n-butyl acrylate was distilled off under reduced pressure to isolate PBA. This PBA was dissolved in ethyl acetate (30 mL), n-butylamine (4 g) was added in a nitrogen atmosphere, and the mixture was stirred at 50 ° C. for 6 hours to modify the end of PBA to an SH group. PBA having SH groups was isolated by pouring this solution into methanol (200 mL). The molecular weight and molecular weight distribution of the obtained PBA having an SH group were Mw = 8100, Mn = 7000, and Mw / Mn = 1.16.

(Example 6)
Synthesis of PMMA-modified ZnS nanoparticles In a three-necked flask (300 mL) equipped with a reflux condenser with a nitrogen introduction tube, a magnetic stirrer, and a thermocouple for temperature measurement, PMMA having SH groups obtained in Production Example 1 (5. 9 g) was added and dissolved by adding DMF (100 mL). 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 solid obtained by distilling off DMF under reduced pressure is dissolved in toluene (20 mL), and a small amount of insoluble matter is removed by centrifugation (6000 rpm / 15 minutes). did. The supernatant was concentrated to 10 mL, poured into methanol (100 mL) to precipitate and separate PMMA-modified ZnS nanoparticles, and dried under reduced pressure (yield 4.40 g).

  The PMMA-modified ZnS nanoparticles thus obtained showed a unimodal emission spectrum of 410 nm for excitation light of 300 nm in chloroform. As a result of TEM observation of the PMMA-modified ZnS nanoparticles, it was confirmed that the ZnS nanoparticles were present without being aggregated. The PMMA-modified nanoparticles were left as a chloroform, toluene, and DMF solution at room temperature for 6 months, but remained transparent, and no change was observed in the ultraviolet absorption spectrum or photoluminescence spectrum. From this, it was confirmed that the effect of stabilizing the modification by the SH group-containing PMMA is large.

(Example 7)
Synthesis of PMMA-modified ZnS: Mn nanoparticles PMMA having an SH group obtained in Production Example 1 was added to a three-necked flask (300 mL) equipped with a reflux condenser with a nitrogen introduction tube, a magnetic stirrer, and a thermocouple for temperature measurement. 6.0 g) was added and dissolved by adding DMF (100 mL). 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 solid obtained by distilling off DMF under reduced pressure is dissolved in toluene (20 mL), and a small amount of insoluble matter is removed by centrifugation (6000 rpm / 15 minutes). did. The supernatant was concentrated to 10 mL and poured into methanol (100 mL) to precipitate and separate PMMA-modified ZnS: Mn nanoparticles and dried under reduced pressure (yield 4.70 g).

  The PMMA-modified ZnS: Mn nanoparticles thus obtained showed a single-peak emission spectrum of 580 nm in chloroform with excitation at 300 nm. This is attributed to light emission from manganese doped in the ZnS crystal. As a result of TEM observation of the PMMA-modified ZnS: Mn nanoparticles, it was confirmed that the ZnS: Mn nanoparticles existed without being aggregated. The PMMA-modified nanoparticles were left as a chloroform, toluene, and DMF solution at room temperature for 6 months, but remained transparent, and no change was observed in the ultraviolet absorption spectrum or photoluminescence spectrum. From this, it was confirmed that the effect of stabilizing the modification by the SH group-containing PMMA is large.

(Example 8)
Synthesis of PBA-modified ZnS nanoparticles Using PBA (4.0 g) having an SH group obtained in Production Example 2 instead of PMMA having an SH group in Example 6, the same experiment was carried out to modify the PBA. ZnS nanoparticles were obtained (yield 2.9 g).

  The resulting PBA-modified ZnS nanoparticles exhibited a 408 nm monomodal emission spectrum for 300 nm excitation light in chloroform. The PBA-modified nanoparticles were left as a chloroform, toluene, and DMF solution at room temperature for 6 months, but remained transparent, and no change was observed in the ultraviolet absorption spectrum or photoluminescence spectrum. From this, it was confirmed that the effect of stabilizing the modification by SH group-containing PBA was great.

  Since the metal sulfide nanoparticle-containing resin composition of the present invention stably exhibits a quantum effect and has a high purity, the solar cell, light-emitting element, display, phosphor, wavelength conversion element, wavelength cut filter, nonlinearity It is useful as a material for optical materials, semiconductor lasers, optical memories, ultraviolet shielding materials, electromagnetic shielding materials, magnetic recording materials, photocatalysts, quantum transistors, biomarkers, and the like.

Claims (19)

  Metal sulfide nanoparticle-containing resin composition obtained by reacting a metal compound with a thiourea compound in the presence of a thermoplastic resin soluble in the aprotic polar organic solvent and then removing the solvent .   Thermoplastic resins soluble in aprotic polar organic solvents are (meth) acrylic ester resins, (meth) acrylamide resins, styrene resins, (meth) acrylonitrile resins, vinyl acetate resins, polycarbonate resins, The metal sulfide nanoparticle-containing resin composition according to claim 1, wherein the resin composition is at least one resin selected from the group consisting of polyamide-based resins.   The metal sulfide nanoparticle-containing resin composition according to claim 1, wherein the thermoplastic resin soluble in an aprotic polar organic solvent is an SH group-containing polymer.   The metal sulfide nanoparticle-containing polymer according to claim 3, wherein the SH group-containing polymer is terminally SH-modified by a treating agent after reversible addition / elimination chain transfer polymerization using a thiocarbonylthio compound as a chain transfer agent. Resin composition.   The metal sulfide nanoparticle-containing resin composition according to claim 4, wherein the treating 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.   One or more compounds in which 90 to 100 mol% of the metal compound is selected from the group consisting of a zinc carboxylate compound, a zinc dithiocarboxylate compound, a zinc dithiocarbamate compound, a zinc xanthate compound, an acetylacetonato zinc compound, and an alkyl zinc compound 0-10 mol% is a manganese carboxylate compound, an acetylacetonatomanganese compound, manganese nitrate, a manganese halide compound, a carboxylate copper compound, a carboxylate silver compound, a lead carboxylate compound, an aluminum halide compound, a carboxylic acid Group consisting of cobalt compound, cobalt halide compound, europium carboxylate, erbium carboxylate, yttrium carboxylate, neodymium carboxylate, terbium carboxylate, cerium carboxylate Ri is one or more compounds selected, metal sulfide nanoparticles-containing resin composition according to any one of claims 1 to 5.   The thiourea compound is one or more compounds selected from the group consisting of thiourea, monoalkylthiourea, monoarylthiourea, dialkylthiourea, diarylthiourea, cyclic thiourea, and thiourea dioxide. 7. The metal sulfide nanoparticle-containing resin composition according to any one of 6 above.   The aprotic polar organic solvent is one or more compounds selected from the group consisting of N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, and hexamethylphosphoric triamide. The metal sulfide nanoparticle-containing resin composition according to any one of the above.   A method for producing a metal sulfide nanoparticle-containing resin composition, comprising reacting a metal compound and a thiourea compound in an aprotic polar organic solvent in the presence of a thermoplastic resin soluble in the solvent, and then removing the solvent.   Thermoplastic resins soluble in aprotic polar organic solvents are (meth) acrylic ester resins, (meth) acrylamide resins, styrene resins, (meth) acrylonitrile resins, vinyl acetate resins, polycarbonate resins, The manufacturing method of the metal sulfide nanoparticle containing resin composition of Claim 9 which is 1 or more types of resin chosen from the group which consists of a polyamide-type resin.   The method for producing a metal sulfide nanoparticle-containing resin composition according to claim 9, wherein the thermoplastic resin soluble in an aprotic polar organic solvent is an SH group-containing polymer.   12. The metal sulfide nanoparticle-containing polymer according to claim 11, wherein the SH group-containing polymer is terminally SH-modified with a treating agent after reversible addition / desorption chain transfer polymerization using a thiocarbonylthio compound as a chain transfer agent. A method for producing a resin composition.   The method for producing a metal sulfide nanoparticle-containing resin composition according to claim 12, wherein the treating agent is at least one compound selected from the group consisting of a hydrogen-nitrogen bond-containing compound, a basic compound, and a reducing agent.   One or more compounds in which 90 to 100 mol% of the metal compound is selected from the group consisting of a zinc carboxylate compound, a zinc dithiocarboxylate compound, a zinc dithiocarbamate compound, a zinc xanthate compound, an acetylacetonato zinc compound, and an alkyl zinc compound 0-10 mol% is a manganese carboxylate compound, an acetylacetonatomanganese compound, manganese nitrate, a manganese halide compound, a carboxylate copper compound, a carboxylate silver compound, a lead carboxylate compound, an aluminum halide compound, a carboxylic acid Group consisting of cobalt compound, cobalt halide compound, europium carboxylate, erbium carboxylate, yttrium carboxylate, neodymium carboxylate, terbium carboxylate, cerium carboxylate Ri is one or more compounds selected method of metal sulfide nanoparticles-containing resin composition according to any of claims 9 13.   The thiourea compound is one or more compounds selected from the group consisting of thiourea, monoalkylthiourea, monoarylthiourea, dialkylthiourea, diarylthiourea, cyclic thiourea, and thiourea dioxide. 14. A method for producing a metal sulfide nanoparticle-containing resin composition according to any one of 14 above.   The aprotic polar organic solvent is at least one compound selected from the group consisting of N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, and hexamethylphosphoric triamide. The manufacturing method of the metal sulfide nanoparticle containing resin composition in any one.   The aprotic polar organic solvent is heated at 80 to 300 ° C when the metal compound and the thiourea compound are reacted in the presence of a thermoplastic resin soluble in the solvent. The manufacturing method of the metal nanoparticle containing resin composition in any one of these.   The method for producing a metal sulfide nanoparticle-containing resin composition according to any one of claims 9 to 17, wherein the solvent is removed by distillation after reacting the metal compound and the thiourea compound.   The thermoplastic resin containing metal sulfide nanoparticles is precipitated and separated from the solvent by adding a poor solvent for the thermoplastic resin after reacting the metal compound and the thiourea compound. 18. The method for producing a metal sulfide nanoparticle-containing resin composition according to any one of 1 to 17.