WO2022181293A1 - 酸化ビスマスナノ粒子、その分散体、樹脂複合体および製造方法 - Google Patents
酸化ビスマスナノ粒子、その分散体、樹脂複合体および製造方法 Download PDFInfo
- Publication number
- WO2022181293A1 WO2022181293A1 PCT/JP2022/004404 JP2022004404W WO2022181293A1 WO 2022181293 A1 WO2022181293 A1 WO 2022181293A1 JP 2022004404 W JP2022004404 W JP 2022004404W WO 2022181293 A1 WO2022181293 A1 WO 2022181293A1
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- WO
- WIPO (PCT)
- Prior art keywords
- bismuth oxide
- oxide nanoparticles
- carboxylic acid
- hydroxyl
- acid
- Prior art date
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- 229910000416 bismuth oxide Inorganic materials 0.000 title claims abstract description 89
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 title claims abstract description 89
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Classifications
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- C—CHEMISTRY; METALLURGY
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- C08K9/04—Ingredients treated with organic substances
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G29/00—Compounds of bismuth
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/60—Compounds characterised by their crystallite size
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- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
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Definitions
- the present invention relates to bismuth oxide nanoparticles, a dispersion thereof, a resin composite obtained by dispersing it in a resin, and a method for producing the same.
- metal oxide nanoparticles have been attracting attention as a material that contributes to the improvement of the functionality and performance of various materials such as optical materials, electronic component materials, magnetic recording materials, catalyst materials, and ultraviolet and near-infrared absorbing materials. ing.
- Patent Document 2 introduces a resin composition containing bismuth oxide nanoparticles as an energy-curable resin composition with a high refractive index suitable for optical lenses.
- Patent Document 2 does not describe an example using bismuth oxide nanoparticles, so its dispersibility and degree of aggregation are unknown, but the commercially available bismuth oxide nanoparticles used in Patent Document 1 are aggregated. Therefore, diffusion treatment using three rolls is required.
- the present invention is to provide bismuth oxide nanoparticles that hardly aggregate and are excellent in dispersibility in organic solvents, monomers, resins, etc., their dispersions and resin composites, and a method for producing the bismuth oxide nanoparticles. Make it an issue.
- the present inventors have found that the surface is treated with a carboxylic acid having no hydroxyl group (hereinafter referred to as a hydroxyl-free carboxylic acid) and a carboxylic acid having a hydroxyl group (hereinafter referred to as a hydroxyl-containing carboxylic acid).
- a carboxylic acid having no hydroxyl group hereinafter referred to as a hydroxyl-free carboxylic acid
- a carboxylic acid having a hydroxyl group hereinafter referred to as a hydroxyl-containing carboxylic acid
- the present invention is as follows. (1) Bismuth oxide nanoparticles surface-treated with a hydroxyl-free carboxylic acid (a) and a hydroxyl-containing carboxylic acid (b). (2) The bismuth oxide nanoparticles according to (1), wherein the hydroxyl-free carboxylic acid (a) is an aliphatic monocarboxylic acid or an aromatic monocarboxylic acid. (3) The bismuth oxide nanoparticles according to (1) or (2), wherein the hydroxyl-free carboxylic acid (a) has 3 or more and 22 or less carbon atoms.
- a method for producing bismuth oxide nanoparticles which comprises mixing and heating a hydroxyl-free carboxylic acid (a), a hydroxyl-containing carboxylic acid (b) and triphenylbismuthine (c).
- a hydroxyl-free carboxylic acid (a) is an aliphatic monocarboxylic acid or an aromatic monocarboxylic acid.
- the triphenylbismuthine (c) is 40 to 100 parts by mass with respect to the total amount of 100 parts by mass of the hydroxyl-free carboxylic acid (a) and the hydroxyl-containing carboxylic acid (b).
- the bismuth oxide nanoparticles of the present invention hardly aggregate and have excellent dispersibility in organic solvents, monomers, polymerizable oligomers, resins, and the like. Therefore, it can be applied to optical materials by dispersing it in a monomer or polymerizable oligomer and polymerizing it. It can also be dispersed in resins to add functions to those resins or to improve optical or mechanical properties.
- FIG. 2 shows the XRD of Example 2 (top) and the XRD from the crystal structure database (bottom).
- FIG. 10 is a diagram showing an FT-IR spectrum of Example 2;
- the bismuth oxide nanoparticles of this embodiment are surface-treated with a hydroxyl-free carboxylic acid (a) and a hydroxyl-containing carboxylic acid (b).
- the hydroxyl-free carboxylic acid (a) is a compound having one or more carboxylic acids in the molecule but no hydroxyl group.
- Examples of the hydroxyl-free carboxylic acid (a) include aliphatic and aromatic monocarboxylic acids. Specifically, when the hydroxyl-free carboxylic acid (a) is aliphatic, it may have 3 to 22 carbon atoms which may be branched or may have an aromatic substituent such as a phenyl group, regardless of whether it is saturated or unsaturated. of monocarboxylic acids. Of these, aliphatic monocarboxylic acids are preferred in consideration of their dispersibility in organic solvents, monomers, and the like.
- propionic acid butyric acid, valeric acid, caproic acid, caprylic acid (octanoic acid), octylic acid, pelargonic acid, capric acid, neodecanoic acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid , palmitic acid, heptadecanoic acid, stearic acid, nonadecanic acid, eicosanoic acid, heneicosanoic acid, and saturated monocarboxylic acids such as docosanoic acid; Unsaturated fatty acids and their geometric isomers are exemplified.
- aliphatic monocarboxylic acids having 3 to 22 carbon atoms are preferable, aliphatic monocarboxylic acids having 4 to 15 carbon atoms are more preferable, and aliphatic monocarboxylic acids having 6 to 10 carbon atoms are even more preferable.
- a hydroxyl-containing carboxylic acid (b) is a compound having one or more carboxylic acids and one or more hydroxyl groups in the molecule.
- the hydroxyl group-containing carboxylic acid (b) include carboxylic acids that may be branched or have an aromatic substituent such as a phenyl group, regardless of whether they are saturated or unsaturated.
- hydroxyl group-containing aliphatic monocarboxylic acids having 6 to 22 carbon atoms are preferable, and monohydroxyaliphatic carboxylic acids are more preferable.
- Specific examples include 2-hydroxydecanoic acid, 3-hydroxyhexanoic acid, 2-hydroxystearic acid, 12-hydroxystearic acid, and ricinoleic acid.
- the hydroxyl-free carboxylic acid (a) imparts hydrophobicity to the surface of the bismuth oxide nanoparticles and contributes to their dispersion stability in organic solvents and the like.
- the hydroxyl group-containing carboxylic acid (b) contributes to the stability of the dispersion through hydrogen bonding with the carbonyl group, particularly when the dispersion medium is an organic solvent, monomer or polymerizable oligomer having a carbonyl group.
- the surface treatment means forming a hydrophobic group on the surface of the bismuth oxide particles to impart hydrophobicity to the bismuth oxide particles, and forming a hydroxyl group on the surface of the bismuth oxide particles to improve the dispersion stability of the bismuth oxide particles.
- the bismuth oxide particles of the present embodiment are surface-treated with a hydroxyl-free carboxylic acid (a) and a hydroxyl-containing carboxylic acid (b) can be confirmed, for example, by IR measurement of the bismuth oxide particles and the CH stretching of alkanes. and the peak of COO - stretching of the carboxylate anion.
- the method for producing bismuth oxide nanoparticles of the present embodiment includes a step of mixing and heating a hydroxyl-free carboxylic acid (a), a hydroxyl-containing carboxylic acid (b) and triphenylbismuthine (c).
- a hydroxyl-free carboxylic acid (a) and a hydroxyl-containing carboxylic acid (b) are mixed, triphenylbismuthine (c) is added thereto, the mixture is heated and stirred, and the bismuth oxide nano-particles are purified by a conventional method. particles can be obtained.
- the purification method includes, for example, a method of adding a poor solvent to the obtained reaction solution to cause reprecipitation, filtering the obtained precipitate, and drying it.
- the heating temperature is not particularly limited, but is preferably 80 to 200°C, more preferably 90 to 150°C. By setting the heating temperature within the above range, the surfaces of the bismuth oxide particles can be satisfactorily treated with the hydroxyl-free carboxylic acid (a) and the hydroxyl-containing carboxylic acid (b).
- the heating time is adjusted as appropriate, and is preferably 1 to 10 hours, more preferably 2 to 8 hours, and even more preferably 3 to 7 hours, for example.
- the bismuth oxide nanoparticles thus obtained are monodispersed with a particle size of several nanometers to several tens of nanometers. 10 nm is more preferred.
- the average particle size of the bismuth oxide nanoparticles is equivalent to the crystallite size obtained from the powder X-ray diffraction data (XRD) by the Scherrer formula. That is, the crystallite size calculated from the diffraction peak width of the powder X-ray diffraction data can be used as the average particle size.
- the surfaces of the bismuth oxide nanoparticles of the present embodiment are treated with a hydroxyl-free carboxylic acid (a) and a hydroxyl-containing carboxylic acid (b), they are excellent in dispersibility in organic solvents, monomers, resins, and the like. .
- the amount of surface treatment with these carboxylic acids is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 20% by mass or more, and even more preferably It is 30% by mass or more.
- the amount of surface treatment with carboxylic acid is preferably 50% by mass or less, more preferably 47% by mass or less, relative to the obtained bismuth oxide nanoparticles.
- the amount of carboxylic acid surface treatment of the bismuth oxide nanoparticles of the present embodiment is the mass reduction rate ( mass %). That is, since the carboxylic acid on the surface of the bismuth oxide nanoparticles is removed by the high-temperature treatment, the amount of carboxylic acid surface treatment can be specified by measuring the amount of mass reduction of the particles.
- the bismuth oxide nanoparticles of the present embodiment have a hydrophobic surface and are less likely to aggregate, so they are excellent in dispersibility in organic solvents, monomers, resins, and the like. Therefore, for example, by using an ultrasonic homogenizer, not only can it be easily and uniformly dispersed in an organic solvent, but also bismuth oxide nanoparticles can be dispersed in a monomer or polymerizable oligomer and then polymerized, or dispersed in a resin. A resin composite in which the particles are finely dispersed in the resin can be obtained.
- the bismuth oxide dispersion and the resin composite of the present embodiment may contain antioxidants, release agents, polymerization initiators, dyes and pigments, dispersants, and the like, depending on the purpose.
- organic solvent examples include alcohols such as ethanol, 2-propanol, butanol, octanol and cyclohexanol, ethyl acetate, butyl acetate, ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ⁇ - Esters such as butyrolactone, diethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, ethers such as dioxane, acetone, methyl ethyl ketone, methyl isobutyl ketone , acetylacetone and cyclohexanone, aromatic hydrocarbons such as benzene, toluene, xylene and ethyl
- radical polymerizable, polycondensation polymerizable, ring-opening polymerizable and the like can be used as the above-mentioned monomers and polymerizable oligomers.
- radically polymerizable monomers include (meth)acrylic monomers such as methyl acrylate and methyl methacrylate, (meth)acrylic monomers having reactive functional groups such as glycidyl groups, isocyanate groups, and vinyl ether groups, and styrene.
- polycondensation-polymerizable monomers include monomers forming polyamides and polyesters, combinations of polyisocyanates with polyols and polythiols, and ring-opening-polymerizable monomers such as epoxy-based monomers.
- a urethane acrylate oligomer, an epoxy acrylate oligomer, an acrylate oligomer, or the like can be preferably used.
- (Meth)acrylate is used to indicate both acrylate and methacrylate.
- the bismuth oxide nanoparticles of the present embodiment can be dispersed in a monomer or polymerizable oligomer and then polymerized, or dispersed in a resin to obtain a resin composite. It is suitably used for applications such as improving mechanical properties.
- thermoplastic resins for example, polyolefins such as polyethylene and polypropylene, polyesters such as polylactic acid and polyethylene terephthalate, polyamides, poly(meth)acrylates, polyphenylene ethers, One or more selected from polyurethane, polystyrene, cyclic polyolefin, polycarbonate and the like is preferably used.
- % in Examples and Comparative Examples means % by mass.
- the Scherrer constant K is 0.9 and the wavelength ⁇ of the X-ray tube is 1.54059.
- Example 1 40.5 g of triphenylbismuthine was added to a mixed solution of 29.7 g of octanoic acid and 29.7 g of ricinoleic acid, and the resulting mixture was stirred at 100° C. for 5 hours under a nitrogen atmosphere to obtain a clear solution. After the resulting clear solution was cooled to room temperature, it was added to 3 L of acetone and filtered through a 0.2 ⁇ m pore size filter. The white matter obtained by filtration was vacuum-dried at 60° C. for one day to obtain 37.6 g of carboxylic acid-treated bismuth oxide powder.
- the surface treatment amount of carboxylic acid in the bismuth oxide powder was 45.69% from the mass reduction rate when the temperature was raised to 800°C at a rate of 40°C/min in a nitrogen atmosphere using a PerkinElmer thermal mass measurement device TGA8000. .
- the crystallite size of the bismuth oxide powder was 4.5 nm by XRD.
- Example 2 46.3 g of triphenylbismuthine was added to a mixed solution of 26.9 g of propionic acid and 26.9 g of ricinoleic acid, and the resulting mixture was stirred at 100° C. for 5 hours under a nitrogen atmosphere to obtain a clear solution. After the resulting clear solution was cooled to room temperature, it was added to 3 L of acetone and filtered through a 0.2 ⁇ m pore size filter. The white matter obtained by filtration was vacuum-dried at 60° C. overnight to obtain 33.6 g of carboxylic acid-treated bismuth oxide powder.
- the surface treatment amount of carboxylic acid in the bismuth oxide powder was 35.48% from the mass reduction rate when the temperature was raised to 800°C at a rate of 40°C/min in a nitrogen atmosphere using a PerkinElmer thermal mass measurement device TGA8000. .
- the crystallite diameter of the bismuth oxide powder was 5.4 nm by XRD.
- the upper part of FIG. 1 shows the X-ray diffraction curve (XRD) of the bismuth oxide nanoparticles of Example 2, and the lower part of FIG. 1 is diffraction data from the crystal structure database of bismuth oxide Bi 2 O 3 .
- the bismuth oxide powder surface-treated with carboxylic acid obtained in Example 2 was measured using FT-IR (Bruker infrared spectrometer VERTEX70), and the results are shown in FIG. From the FT-IR spectrum of FIG. 2, peaks of CH stretching of alkane and COO 2 - stretching of carboxylate anion could be confirmed. Therefore, it was confirmed that the carboxylic acid reacted with the surface of the bismuth oxide particles to form a chemical bond in the state of carboxylate. It was shown to be surface treated with acid (b). Further, for reference, FIG. 2 also shows the FT-IR spectrum of the bismuth (III) oxide powder (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) which is not surface-treated in Comparative Example 1 described later.
- FT-IR Brunauer-IR
- Table 1 shows the dispersibility in organic solvents of Examples 1 and 2 and Comparative Example 1. It was found that all of the examples had better dispersibility in organic solvents, monomers, etc. than the comparative examples.
- Example 3 Production of bismuth oxide resin composite 4.3 parts of bismuth oxide nanoparticles of Example 2, 8.6 parts of vinyl toluene monomer, 0.5 parts of 3-phenoxybenzyl acrylate and 0.5 parts of 2-acryloyloxyethyl succinate It was added to a vial, ultrasonically dispersed, and mixed until it became transparent to obtain a mixed liquid. After that, 0.08 part of 2,2′-azobis(2,4-dimethylvaleronitrile) was further added to the mixed solution, and left in an oven at 65° C. for 24 hours under a nitrogen atmosphere to remove 18.97 parts of bismuth oxide. % of transparent bismuth oxide-containing resin, that is, a bismuth oxide resin composite was obtained.
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Abstract
Description
(1) 水酸基不含有カルボン酸(a)および水酸基含有カルボン酸(b)で表面処理されている、酸化ビスマスナノ粒子。
(2) 前記水酸基不含有カルボン酸(a)が脂肪族モノカルボン酸または芳香族モノカルボン酸である、(1)記載の酸化ビスマスナノ粒子。
(3) 前記水酸基不含有カルボン酸(a)の炭素数が3以上22以下である、(1)または(2)記載の酸化ビスマスナノ粒子。
(4) 前記水酸基含有カルボン酸(b)が水酸基含有脂肪族モノカルボン酸である、(1)から(3)のいずれかに記載の酸化ビスマスナノ粒子。
(5) 前記水酸基含有脂肪族モノカルボン酸がモノヒドロキシ脂肪族モノカルボン酸である、(4)記載の酸化ビスマスナノ粒子。
(6) 前記水酸基含有カルボン酸(b)の炭素数が6以上22以下である、(1)から(5)のいずれかに記載の酸化ビスマスナノ粒子。
(7) 当該酸化ビスマスナノ粒子の平均粒子径が1~20nmである、(1)から(6)のいずれかに記載の酸化ビスマスナノ粒子。
(8) 表面処理量が当該酸化ビスマスナノ粒子全量に対して5~50質量%である、(1)から(7)のいずれかに記載の酸化ビスマスナノ粒子。
(9) (1)から(8)のいずれかに記載の酸化ビスマスナノ粒子を、有機溶媒、モノマーおよび重合性オリゴマーから選ばれた少なくとも一つを含有する分散媒中に分散してなる、酸化ビスマスナノ粒子分散体。
(10) (1)から(8)のいずれかに記載の酸化ビスマスナノ粒子を、樹脂中に分散してなる樹脂複合体。
(11) 水酸基不含有カルボン酸(a)、水酸基含有カルボン酸(b)およびトリフェニルビスムチン(c)を混合し加熱する工程を含む、酸化ビスマスナノ粒子の製造方法。
(12) 前記水酸基不含有カルボン酸(a)が脂肪族モノカルボン酸または芳香族モノカルボン酸である、(11)記載の酸化ビスマスナノ粒子の製造方法。
(13) 前記水酸基含有カルボン酸(b)が水酸基含有脂肪族モノカルボン酸である、(11)または12記載の酸化ビスマスナノ粒子の製造方法。
(14) 前記水酸基含有脂肪族モノカルボン酸がモノヒドロキシ脂肪族モノカルボン酸である、(13)記載の酸化ビスマスナノ粒子の製造方法。
(15) 前記混合し加熱する前記工程において、前記水酸基不含有カルボン酸(a)と前記水酸基含有カルボン酸(b)の合計量100質量部に対し、前記トリフェニルビスムチン(c)が40~100質量部である、(11)から(14)のいずれかに記載の酸化ビスマスナノ粒子の製造方法。
前記水酸基不含有カルボン酸(a)としては、脂肪族および芳香族のモノカルボン酸が挙げられる。具体的には、水酸基不含有カルボン酸(a)が脂肪族である場合、飽和、不飽和を問わず、枝分かれまたはフェニル基等の芳香族置換基を有してもよい炭素数が3から22のモノカルボン酸が挙げられる。なかでも、有機溶媒、およびモノマー等への分散性を考慮すると脂肪族モノカルボン酸が好ましい。より具体的には、プロピオン酸、酪酸、吉草酸、カプロン酸、カプリル酸(オクタン酸)、オクチル酸、ペラルゴン酸、カプリン酸、ネオデカン酸、ウンデカン酸、ラウリン酸、トリデカン酸、ミリスチン酸、ペンタデカン酸、パルミチン酸、ヘプタデカン酸、ステアリン酸、ノナデカン酸、エイコサン酸、ヘネイコサン酸、およびドコサン酸等の飽和モノカルボン酸;オレイン酸、リノール酸、リノレイン酸、および魚油を鹸化分解して得られる脂肪酸等の不飽和脂肪酸ならびにそれらの幾何異性体が例示される。なかでも、炭素数が3から22の脂肪族モノカルボン酸が好ましく、炭素数が4から15の脂肪族モノカルボン酸がより好ましく、炭素数が6から10の脂肪族モノカルボン酸がさらに好ましい。
前記水酸基含有カルボン酸(b)としては、飽和、不飽和を問わず、枝分かれまたはフェニル基等の芳香族置換基を有してもよいカルボン酸が挙げられる。なかでも、炭素数が6から22の水酸基含有脂肪族モノカルボン酸が好ましく、モノヒドロキシ脂肪族カルボン酸がより好ましい。具体的には、2-ヒドロキシデカン酸、3-ヒドロキシヘキサン酸、2-ヒドロキシステアリン酸、12-ヒドロキシステアリン酸、およびリシノール酸等が例示される。
なお、本実施形態において表面処理とは、酸化ビスマス粒子表面に疎水基を形成して酸化ビスマス粒子に疎水性を付与しつつ、酸化ビスマス粒子表面に水酸基を形成して酸化ビスマス粒子に分散安定性を付与することを意図する。また、本実施形態の酸化ビスマス粒子が水酸基不含有カルボン酸(a)および水酸基含有カルボン酸(b)で表面処理されていることは、例えば、酸化ビスマス粒子のIR測定を行い、アルカンのCH伸縮とカルボキシレートアニオンのCOO-伸縮のピークが見られることにより確認できる。
水酸基不含有カルボン酸(a)と水酸基含有カルボン酸(b)との混合比(質量比)は、(a):(b)=1:9~9:1が好ましく、(a):(b)=3:7~7:3がより好ましく、(a):(b)=4:6~6:4がさらに好ましく、(a):(b)=4.5:5.5~5.5:4.5がことさらに好ましい。
また、水酸基不含有カルボン酸(a)と水酸基含有カルボン酸(b)の合計量100質量部に対するトリフェニルビスムチン(c)の添加量は、40~100質量部が好ましく、50~80質量部がより好ましく、60~75質量部がさらに好ましい。
また、加熱温度は、特に限定されないが、80~200℃が好ましく、90~150℃がより好ましい。加熱温度を上記範囲内とすることで、酸化ビスマス粒子の表面を水酸基不含有カルボン酸(a)および水酸基含有カルボン酸(b)によって良好に処理することができる。また、加熱時間は、適宜調整されるが、例えば、1~10時間が好ましく、2~8時間がより好ましく、3~7時間がさらに好ましい。
カルボン酸による表面処理量を上記下限値以上とすることにより、有機溶媒、モノマー等への分散性を良好にできる。一方、カルボン酸による表面処理量を上記下限値以上とすることにより、酸化ビスマス自身が一定量保持され、酸化ビスマスによる機能が得られやすくなる。
ここで、本実施形態の酸化ビスマスナノ粒子のカルボン酸の表面処理量は、酸化ビスマスナノ粒子を窒素雰囲気下40℃/分の速度で800℃まで昇温処理した前後における酸化ビスマスナノ粒子の質量減少率(質量%)とする。すなわち、高温処理により、酸化ビスマスナノ粒子の表面にあるカルボン酸が除去されることとなるため、当該粒子の質量減少量を測定することで、カルボン酸の表面処理量を特定することができる。
なお、本実施形態の酸化ビスマス分散体および樹脂複合体は、その目的に応じて酸化防止剤、離型剤、重合開始剤、染顔料、および分散剤等を含有してもよい。
なお、(メタ)アクリレートはアクリレートとメタクリレートの両者を示すものとして使用される。
以下の実施例および比較例で得られた酸化ビスマスナノ粒子の平均粒子径は、X線回折装置(株式会社リガク製、全自動多目的X線回折装置 SmartLab)を用い、測定条件を、X線管電圧40kV、X線管電電流30mA、走査範囲2θは10.0-65.0°とし、X線回折測定の2θ=32.67°付近の(200)面による回折強度からその半価幅βを求め、以下の数1のScherrer式において、Scherrer定数Kを0.9、X線管球の波長λを1.54059として結晶子径Dを求め、その値とした。
D=K・λ/(β・cosθ)
以下の実施例および比較例で得られた酸化ビスマス粉末について、分散性を評価した。有機溶媒またはモノマー中での分散性は、具体的には、実施例および比較例で得られた各酸化ビスマスナノ粒子に10%濃度になるように、表1に示す各溶媒(種々の有機溶媒またはモノマー)を添加し、超音波洗浄器(アズワン株式会社製単周波超音波洗浄器 MCS-6)による数分の処理後、目視により観察し、透明なものを○、白濁または沈降が見られたものを×として、分散性を評価し、結果を表1に示した。
オクタン酸29.7g、リシノール酸29.7gの混合溶液にトリフェニルビスムチン40.5gを添加し、得られた混合物を窒素雰囲気下で100℃、5時間撹拌し、透明溶液を得た。得られた透明溶液を室温まで冷却後、3Lのアセトンに添加し、ポアサイズ0.2μmフィルタで濾過した。濾過により得られた白色物を60℃で一昼夜真空乾燥を行うことにより、37.6gのカルボン酸で表面処理された酸化ビスマス粉末を得た。
酸化ビスマス粉末のカルボン酸の表面処理量は、PerkinElmer社製の熱質量測定装置TGA8000により、窒素雰囲気下40℃/分の速度で800℃まで昇温した質量減少率から45.69%であった。また酸化ビスマス粉末の結晶子径はXRDより4.5nmであった。
プロピオン酸26.9g、リシノール酸26.9gの混合溶液にトリフェニルビスムチン46.3gを添加し、得られた混合物を窒素雰囲気下で100℃、5時間の撹拌し、透明溶液を得た。得られた透明溶液を室温まで冷却後、3Lのアセトンに添加し、ポアサイズ0.2μmフィルタで濾過した。濾過により得られた白色物を60℃で一昼夜真空乾燥を行うことにより、33.6gのカルボン酸で表面処理された酸化ビスマス粉末を得た。
酸化ビスマス粉末のカルボン酸の表面処理量は、PerkinElmer社製の熱質量測定装置TGA8000により、窒素雰囲気下40℃/分の速度で800℃まで昇温した質量減少率から35.48%であった。また、酸化ビスマス粉末の結晶子径はXRDより5.4nmであった。
なお、図1の上部は、実施例2の酸化ビスマスナノ粒子のX線回折曲線(XRD)を示し、図1の下部は、酸化ビスマスBi2O3の結晶構造データベースからの回折データである。
図2のFT-IRスペクトルより、アルカンのCH伸縮とカルボキシレートアニオンのCOO-伸縮のピークが確認できた。したがって、酸化ビスマス粒子の表面にはカルボン酸が反応して、カルボキシレートの状態で化学結合が形成されていることが確認され、酸化ビスマス粒子は、水酸基不含有カルボン酸(a)および水酸基含有カルボン酸(b)で表面処理されていることが示された。
さらに、参考のため、後述の比較例1の表面処理されていない酸化ビスマス(III)粉末(富士フイルム和光純薬製)についてのFT-IRスペクトルも図2に示した。
市販の表面処理されていない酸化ビスマス(III)粉末(富士フイルム和光純薬株式会社製)を用いた。
・酸化ビスマス樹脂複合体の製造
実施例2の酸化ビスマスナノ粒子4.3部、ビニルトルエンモノマー8.6部、3-フェノキシベンジルアクリレート0.5部および2-アクリロイルオキシエチルサクシネート0.5部をバイアルに添加、超音波分散させ、透明になるまで混合し、混合液をえた。その後、この混合液に2,2’-アゾビス(2,4-ジメチルバレロニトリル)0.08部をさらに加え、窒素雰囲気下、65℃のオーブンに24時間静置し、酸化ビスマスを18.97%含有する透明な酸化ビスマス含有樹脂、すなわち酸化ビスマス樹脂複合体を得た。
Claims (15)
- 水酸基不含有カルボン酸(a)および水酸基含有カルボン酸(b)で表面処理されている、酸化ビスマスナノ粒子。
- 前記水酸基不含有カルボン酸(a)が脂肪族モノカルボン酸または芳香族モノカルボン酸である、請求項1記載の酸化ビスマスナノ粒子。
- 前記水酸基不含有カルボン酸(a)の炭素数が3以上22以下である、請求項1または2記載の酸化ビスマスナノ粒子。
- 前記水酸基含有カルボン酸(b)が水酸基含有脂肪族モノカルボン酸である、請求項1から3のいずれかに記載の酸化ビスマスナノ粒子。
- 前記水酸基含有脂肪族モノカルボン酸がモノヒドロキシ脂肪族モノカルボン酸である、請求項4記載の酸化ビスマスナノ粒子。
- 前記水酸基含有カルボン酸(b)の炭素数が6以上22以下である、請求項1から5のいずれかに記載の酸化ビスマスナノ粒子。
- 当該酸化ビスマスナノ粒子の平均粒子径が1~20nmである、請求項1から6のいずれかに記載の酸化ビスマスナノ粒子。
- 表面処理量が当該酸化ビスマスナノ粒子全量に対して5~50質量%である、請求項1から7のいずれかに記載の酸化ビスマスナノ粒子。
- 請求項1から8のいずれかに記載の酸化ビスマスナノ粒子を、有機溶媒、モノマーおよび重合性オリゴマーから選ばれた少なくとも一つを含有する分散媒中に分散してなる、酸化ビスマスナノ粒子分散体。
- 請求項1から8のいずれかに記載の酸化ビスマスナノ粒子を、樹脂中に分散してなる樹脂複合体。
- 水酸基不含有カルボン酸(a)、水酸基含有カルボン酸(b)およびトリフェニルビスムチン(c)を混合し加熱する工程を含む、酸化ビスマスナノ粒子の製造方法。
- 前記水酸基不含有カルボン酸(a)が脂肪族モノカルボン酸または芳香族モノカルボン酸である、請求項11記載の酸化ビスマスナノ粒子の製造方法。
- 前記水酸基含有カルボン酸(b)が水酸基含有脂肪族モノカルボン酸である、請求項11または12記載の酸化ビスマスナノ粒子の製造方法。
- 前記水酸基含有脂肪族モノカルボン酸がモノヒドロキシ脂肪族モノカルボン酸である、請求項13記載の酸化ビスマスナノ粒子の製造方法。
- 前記混合し加熱する前記工程において、前記水酸基不含有カルボン酸(a)と前記水酸基含有カルボン酸(b)の合計量100質量部に対し、前記トリフェニルビスムチン(c)が40~100質量部である、請求項11から14のいずれかに記載の酸化ビスマスナノ粒子の製造方法。
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