WO2017163610A1 - 酸化ジルコニウムナノ粒子 - Google Patents
酸化ジルコニウムナノ粒子 Download PDFInfo
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- WO2017163610A1 WO2017163610A1 PCT/JP2017/003168 JP2017003168W WO2017163610A1 WO 2017163610 A1 WO2017163610 A1 WO 2017163610A1 JP 2017003168 W JP2017003168 W JP 2017003168W WO 2017163610 A1 WO2017163610 A1 WO 2017163610A1
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- zirconium oxide
- oxide nanoparticles
- acid
- mpa
- zirconium
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Definitions
- the present invention relates to zirconium oxide nanoparticles.
- metal oxide nanoparticles have the potential to develop various functions in optical materials, electronic component materials, and the like, and are attracting attention in the field of various functional materials.
- metal oxides alone are often agglomerated due to insufficient dispersibility in an organic medium, causing problems such as a decrease in transparency and a decrease in mechanical strength.
- a method of chemically bonding an organic group to a metal oxide has been proposed.
- Patent Document 1 is coated with two or more coating agents, and at least one of the coating agents is represented by the formula R-COOH (R is a hydrocarbon group having 6 or more carbon atoms).
- R-COOH R is a hydrocarbon group having 6 or more carbon atoms.
- Zirconium oxide nanoparticles are disclosed, and it is described that such zirconium oxide nanoparticles can improve dispersibility in a nonpolar solvent or the like.
- zirconium oxide nanoparticle dispersion since there are various examples of the use of the zirconium oxide nanoparticle dispersion, non-polar solvents having erosive properties such as methyl ethyl ketone are not preferred when using polycarbonate as the resin substrate, and polarities such as water and ethanol are used. A dispersion using a solvent as a dispersion medium is required. In addition, with the transition of required physical properties of optical materials, electronic component materials, etc., monomers of optical materials having a higher polarity than before are being used, and zirconium oxide nanoparticles themselves are required to be dispersed in polar solvents. .
- Patent Document 1 does not include an example using methanol, which is a typical polar solvent, and the dispersibility of zirconium oxide nanoparticles in a more polar solvent such as water and ethanol is not sufficient. Furthermore, even if these zirconium oxide nanoparticles can be dispersed in a nonpolar solvent, there is an upper limit to the metal oxide concentration (core concentration; concentration calculated by the formula (A)) in the dispersion, and the zirconium oxide nanoparticles are dispersed at a higher concentration. There is a need for possible zirconium oxide nanoparticles.
- An object of the present invention is to provide zirconium oxide nanoparticles that are excellent in dispersibility in a polar solvent and that can increase the core concentration in the dispersion.
- R 1 includes one or more elements selected from the group consisting of an oxygen atom, a nitrogen atom, and a sulfur atom and a carbon atom, and the total number of carbon atoms, oxygen atoms, nitrogen atoms, and sulfur atoms in R 1 is 8
- the following groups are represented.
- R 4 represents a halogen atom or —OR 2
- R 2 represents a hydrogen atom or an alkyl group.
- n represents 1 or 2
- m represents an integer of 1 to 3.
- the ratio of the sum of oxygen, nitrogen and sulfur atoms to the number of carbon atoms is 1/7 or more and 1/1 or less.
- [6] The zirconium oxide nanostructure according to any one of [1] to [5], wherein the Hansen solubility parameter (HSP) distance of R 1 to ethanol is 0 (MPa) 1/2 or more and 20 (MPa) 1/2 or less. particle.
- [7] The zirconium oxide nanostructure according to any one of [1] to [5], wherein the Hansen solubility parameter (HSP) distance of R 1 in water is 20 (MPa) 1/2 or more and 41 (MPa) 1/2 or less. particle.
- [8] A dispersion containing the zirconium oxide nanoparticles according to any one of [1] to [7].
- a resin composition comprising the zirconium oxide nanoparticles according to any one of [1] to [7].
- the resin composition according to [10] or [11] comprising a solvent having a Hansen solubility parameter (HSP) distance in water of 0 (MPa) 1/2 or more and 40 (MPa) 1/2 or less.
- a molding material comprising the zirconium oxide nanoparticles according to any one of [1] to [7].
- a method for producing a ceramic material comprising firing the zirconium oxide nanoparticles according to any one of [1] to [7] at 500 ° C. or higher.
- a method for producing a ceramic material comprising firing the composition containing the zirconium oxide nanoparticles according to any one of [1] to [7] at 500 ° C. or higher.
- the zirconium oxide nanoparticles are coated with the specific group R 1 , the dispersibility in polar solvents such as water and alcohol is excellent, and the core concentration in the dispersion can be increased. Zirconium oxide nanoparticles can be obtained.
- Zirconium oxide nanoparticles of the present invention comprise R 1 —COOH having a group R 1 , (R 1 O) 3-n —P (O) — (OH) n , (R 1 ) 3-n —P (O) -(OH) n , (R 1 O) -S (O) (O)-(OH), R 1 -S (O) (O)-(OH), (R 1 ) 4-m -Si (R 4 ) Since it is coated with a compound selected from the group consisting of m (hereinafter sometimes simply referred to as “compound (1)”), the dispersibility in polar solvents such as water and alcohol is increased, and the laminated film Can be formed in accordance with the polarity of the solvent. In addition, the core concentration in the dispersion can be increased, and the range of selection of the solvent used for film formation can be expanded.
- the molecular weight of the compound (1) can be reduced.
- the proportion (mass%) of the zirconium oxide component in the particles can be made relatively high.
- the performance of the zirconium oxide nanoparticles can be exerted more strongly.
- a coating film having a higher refractive index can be produced from the resin composition containing the zirconium oxide nanoparticles of the present invention. .
- the lower limit of the total number of carbon atoms, oxygen atoms, nitrogen atoms and sulfur atoms contained in R 1 is 2 or more, more preferably 7 or less, still more preferably 5 or less, still more preferably 4 or less, particularly preferably. Is 3 or less.
- the total number of carbon atoms, oxygen atoms, nitrogen atoms and sulfur atoms contained in R 1 is smaller.
- the characteristics of R 1 can also be evaluated by the Hansen solubility parameter (HSP).
- HSP Hansen solubility parameter
- the Hansen solubility parameter (HSP) is a value used for predicting the solubility of a substance.
- HSP is composed of three parameters: energy (D) due to intermolecular dispersion force, energy (P) due to dipolar interaction between molecules, and energy (H) due to hydrogen bonds between molecules. These three parameters can be regarded as coordinates in a three-dimensional space. And when HSP of two substances (substance 1 and substance 2) is placed in a three-dimensional space, the closer the distance is, the easier it is to dissolve each other.
- the HSP distance of R 1 with respect to ethanol is preferably 0 (MPa) 1/2 or more, more preferably 5 (MPa) 1/2 or more, still more preferably 10 (MPa) 1/2 or more, preferably 20 ( MPa) 1/2 or less, more preferably 18 (MPa) 1/2 or less, still more preferably 17 (MPa) 1/2 or less.
- the HSP distance of R 1 with respect to water is preferably 20 (MPa) 1/2 or more, more preferably 25 (MPa) 1/2 or more, still more preferably 30 (MPa) 1/2 or more, and preferably 41 ( MPa) 1/2 or less, more preferably 39 (MPa) 1/2 or less, still more preferably 38 (MPa) 1/2 or less.
- the ratio of the sum of oxygen, nitrogen and sulfur atoms to the number of carbon atoms in R 1 is: Preferably it is 1/7 or more, more preferably 1/5 or more, still more preferably 1/3 or more, preferably 1/1 or less, more preferably 1 / 1.3 or less, still more preferably 1 / 1.6. It is as follows.
- the ratio of the number of oxygen atoms to the number of carbon atoms is preferably 1/7 or more, more preferably 1/5 or more, and even more preferably 1/3 or more. Preferably, it is 1/1 or less, more preferably 1 / 1.3 or less, and still more preferably 1 / 1.6 or less. Since the hydrophilicity of R 1 is increased, the presence of oxygen atoms in a certain ratio or more with respect to the carbon atoms in R 1 contributes to enhancing the dispersibility of the zirconium oxide nanoparticles in the polar solvent.
- R 1 is, for example, a hydrocarbon group in which a part of the elements constituting the hydrocarbon group is substituted with one or more elements selected from the group consisting of an oxygen atom, a nitrogen atom and a sulfur atom.
- substituent of the element contained in the hydrocarbon group include a group that substitutes a carbon atom such as an ether bond, a carbonyl group, a thioketone group, a sulfide bond, a sulfoxide group, a carbamoyl group, a> NH group, and a> N-group.
- a group that replaces a hydrogen atom such as a hydroxy group, a thiol group, a —NH 2 group, a carboxyl group, a cyano group, a ureido group, or an isocyanate group; and preferably an ether bond, a hydroxy group or a —NH 2 group More preferably an ether bond.
- Examples of the hydrocarbon group for R 1 include a chain hydrocarbon group and a cyclic hydrocarbon group, and a chain hydrocarbon group is preferred.
- the chain hydrocarbon group is preferably saturated or unsaturated, more preferably saturated.
- the chain hydrocarbon group is preferably linear or branched, and more preferably linear.
- the chain hydrocarbon group is preferably a saturated chain hydrocarbon group, more preferably a linear saturated chain hydrocarbon group.
- the cyclic hydrocarbon group is preferably saturated or unsaturated.
- R 1 preferably contains an oxygen atom, more preferably a group consisting of a hydrogen atom, a carbon atom and an oxygen atom.
- the compound (1) is, R 1 -C, R 1 -O , R 1 -P, has a R 1 -S and R 1 either partial structure of -Si, the R 1 - R in Part
- the bond end of 1 is preferably a carbon atom.
- the carbon atom that is the bond terminal of R 1 is preferably represented by formula (A-1) to formula (A-4) (wherein the single bond corresponds to the bond of the R 1 -moiety), More preferred is formula (A-1).
- one single bond and one double bond may be a bond as one embodiment of a resonance structure. Therefore, one single bond and double bond in Formula (A-4) includes a case where it is part of an aromatic ring.
- the ratio of the number of oxygen atoms to the number of carbon atoms is preferably more than 1/6, more preferably 1/2 or more, still more preferably 1 / 1.4. It is above, Preferably it is 1 / 0.2 or less, More preferably, it is 1 / 0.8 or less, More preferably, it is 1 / 0.9 or less.
- the presence of oxygen atoms at a certain ratio or more with respect to the carbon atoms in the compound (1) contributes to increasing the content of zirconium oxide nanoparticles in the polar solvent.
- R 1 -COOH includes methoxyacetic acid, ethoxyacetic acid, 3-ethoxypropionic acid, 2-methoxyethoxyacetic acid and other ether bond-containing carboxylic acids; glyoxylic acid, pyruvic acid, levulinic acid, 2-oxovaleric acid, asparagine, glutamine , Carbonyl group-containing carboxylic acids such as ⁇ -methyllevulinic acid and ⁇ -methyllevulinic acid; sulfide-containing carboxylic acids such as methionine; glycolic acid, DL-lactic acid, 2-hydroxyisobutyric acid, dimethylolpropionic acid, hydroxypival Acid, 3-hydroxypropionic acid, DL-2-hydroxybutyric acid, DL-3-hydroxybutyric acid, 2-hydroxy-2-methylbutyric acid, ⁇ -hydroxyisovaleric acid, 2,2-bis (hydroxymethyl) butyric acid, serine , Threonine, 4-hydroxycyclohexanecarbo Acid
- (R 1 O) 3-n -P (O)-(OH) n or (R 1 ) 3-n -P (O)-(OH) n includes methoxymethyl phosphate, di (methoxymethyl phosphate) ), DL-glyceraldehyde-3-phosphate, glycerin phosphate and the like.
- R 1 O) -S (O) (O)-(OH) or R 1 -S (O) (O)-(OH) include methoxymethyl sulfate, L-serine-O-sulfate potassium salt and the like. Illustrated.
- R 4 is preferably a chlorine atom, a methoxy methyltrichlorosilane, methoxyethyl trichlorosilane, (3-aminopropyl) Trichlorosilane, (3-mercaptopropyl) trichlorosilane, 2-cyanoethyltrichlorosilane, [3- (N, N-dimethylamino) propyl] trichlorosilane, 3- (methylamino) propyltrichlorosilane, 3-cyanopropyltrichlorosilane , (3-ureidopropyl) trichlorosilane, (3-isocyanatopropyl) trichlorosilane, 3- (2-aminoethylamino) propyltrichlorosilane, methyl [3- (trichlorosily
- R 1 4-m -Si (R 4) of m, R 4 is OR 2
- R 2 is a hydrogen atom or an alkyl group
- R 2 represents a hydrogen atom or a C 1-6 (especially carbon It is preferably an alkyl group having 1 to 4)
- R 2 is more preferably an alkyl group having 1 to 4 carbon atoms (particularly a methyl group or an ethyl group).
- R 2 is an alkyl group
- (R 1 ) 4-m -Si (OR 2 ) m includes methoxymethyltrimethoxysilane, methoxyethyltriethoxysilane, (3-aminopropyl) trimethoxysilane, (3 -Mercaptopropyl) trimethoxysilane, 2-cyanoethyltriethoxysilane, [3- (N, N-dimethylamino) propyl] trimethoxysilane, 3- (methylamino) propyltrimethoxysilane, 3-cyanopropyltrimethoxysilane , (3-ureidopropyl) trimethoxysilane, (3-isocyanatopropyl) triethoxysilane, 3- (2-aminoethylamino) propyltrimethoxysilane, methyl [3- (trimethoxysilyl) propyl] carbamate, etc.
- (R 1 ) 4-m -Si (OR 2 ) m includes methoxymethyltrihydroxysilane, methoxyethyltrihydroxysilane, (3-aminopropyl) trihydroxysilane, (3 -Mercaptopropyl) trihydroxysilane, 2-cyanoethyltrihydroxysilane, [3- (N, N-dimethylamino) propyl] trihydroxysilane, 3- (methylamino) propyltrihydroxysilane, 3-cyanopropyltrihydroxysilane , (3-ureidopropyl) trihydroxysilane, (3-isocyanatopropyl) trihydroxysilane, 3- (2-aminoethylamino) propyltrihydroxysilane, methyl [3- (trihydroxysilyl) propyl] carbamate, etc.
- the compound represented by (R 1 ) 4-m —Si (R 4 ) m is preferably not tetraethoxysilane, more preferably not tetraalkoxysilane.
- the compound that coats the zirconium oxide nanoparticles is preferably R 1 —COOH, more preferably an ether bond-containing carboxylic acid, still more preferably methoxyacetic acid, ethoxyacetic acid, 3-ethoxypropionic acid or 2-methoxyethoxyacetic acid. Particularly preferred is methoxyacetic acid or ethoxyacetic acid.
- the amount of the compound (1) is 5 to 35% by mass in the zirconium oxide nanoparticles (preferably 8% by mass or more, more preferably 10% by mass or more, preferably 33% by mass or less, more preferably 30% by mass or less). It is.
- the fact that the zirconium oxide nanoparticles are coated with the compound (1) means that the compound (1) includes both a chemically bonded state and a physically bonded state to the zirconium oxide nanoparticles.
- the compound (1) is a carboxylic acid, it means that the compound (1) and / or the carboxylate derived from the compound (1) are coated.
- Zirconium oxide nanoparticles may be coated with a second compound other than compound (1).
- the second compound include carboxylic acids that can be mixed into the raw material of the compound (1) (except for the compound (1); hereinafter, sometimes referred to as “carboxylic acid (2)”).
- the second compound may be contained in the zirconium oxide particles to such an extent that the coating effect of the compound (1) is not hindered.
- the amount of the second compound is preferably 30% by mass or less, More preferably, it is 10 mass% or less, More preferably, it is 5 mass% or less.
- the carboxylic acid (2) is preferably a carboxylic acid having 3 to 22 (preferably 4 to 20) carbon atoms.
- the carboxylic acid (2) includes any of primary carboxylic acid, secondary carboxylic acid and tertiary carboxylic acid. Is included.
- As the primary carboxylic acid a linear primary carboxylic acid having 4 to 20 carbon atoms and a branched primary carboxylic acid having 4 to 20 carbon atoms (that is, a carboxylic acid in which a carbon atom other than the ⁇ -position is branched) are preferable. .
- the linear carboxylic acid is preferably a linear saturated aliphatic carboxylic acid, specifically, butyric acid, valeric acid, hexanoic acid, heptanoic acid, caprylic acid, nonanoic acid, decanoic acid, lauric acid, tetradecanoic acid , Stearic acid, oleic acid, ricinoleic acid and the like.
- Examples of the branched primary carboxylic acid include isovaleric acid, 3,3-dimethylbutyric acid, 3-methylvaleric acid, isononanoic acid, 4-methylvaleric acid, 4-methyl-n-octanoic acid, naphthenic acid, and the like. .
- the secondary carboxylic acid is preferably a secondary carboxylic acid having 4 to 20 carbon atoms, specifically isobutyric acid, 2-methylbutyric acid, 2-ethylbutyric acid, 2-ethylhexanoic acid, 2-methylvaleric acid, 2 -Methylhexanoic acid, 2-methylheptanoic acid, 2-propylbutyric acid, 2-hexylvaleric acid, 2-hexyldecanoic acid, 2-heptylundecanoic acid, 2-methylhexadecanoic acid, 4-methylcyclohexanecarboxylic acid, etc.
- 2-ethylhexanoic acid and 2-hexyldecanoic acid are preferred, and 2-ethylhexanoic acid is particularly preferred.
- the tertiary carboxylic acid is preferably a tertiary carboxylic acid having 5 to 20 carbon atoms.
- pivalic acid, 2,2-dimethylbutyric acid, 2,2-dimethylvaleric acid, 2,2-dimethylhexanoic acid examples include 2,2-dimethylheptanoic acid and neodecanoic acid.
- the zirconium oxide nanoparticles are mainly composed of zirconium, but may further contain at least one selected from Al and rare earth elements in order to stabilize the crystal structure of the zirconium oxide crystal.
- Zirconium oxide nanoparticles containing these metals have a high ratio of tetragonal crystals and / or cubic crystals in the particles, and can suppress reduction of tetragonal crystals when the zirconium oxide nanoparticles are fired. The ratio of can be increased.
- the rare earth elements include Sc (scandium), Y (yttrium), and lanthanoid elements having atomic number 57 (La) to atomic number 71 (Lu).
- Al and rare earth elements it is preferably at least one selected from Al, Y, La, Yb, Sc, Ce and Er, more preferably at least one selected from Al, Y, Sc and Er.
- Al and a rare earth element When Al and a rare earth element are contained, it is preferably 0 to 20% by mass, more preferably 3 to 20% by mass, and still more preferably, of zirconium in zirconium oxide and a total of 100% by mass of Al and the rare earth element. It is desirable to contain 5 to 20% by mass.
- the zirconium oxide nanoparticles may contain metal elements other than zirconium, Al, and rare earth elements, but the content of zirconium contained in the nanoparticles of the present invention is the total metal elements contained in the zirconium nanoparticles. Among these, preferably 60% by mass or more, more preferably 70% by mass or more, and further preferably 80% by mass or more. Further, the content of metal elements other than these is preferably as small as possible, and the content of metal elements excluding hafnium, which is usually included as impurities of zirconium, Al, rare earth elements and zirconium, is preferably among all metal elements contained in the nanoparticles. It is 3 mass% or less, More preferably, it is 1 mass% or less, and 0 mass% may be sufficient.
- the crystal structure of the zirconium oxide nanoparticles is preferably cubic, tetragonal, or monoclinic, and the sum of tetragonal and cubic is preferably 60% or more of the entire crystal structure.
- the total ratio of tetragonal crystals and cubic crystals is preferably 70% or more, more preferably 80% or more.
- the zirconium oxide nanoparticles contain Al or a rare earth element, tetragonal crystals and / or cubic crystals are stabilized, and the ratio of tetragonal crystals and / or cubic crystals in the nanoparticles tends to increase.
- the zirconium oxide nanoparticles contain Al or rare earth elements, it becomes easy to maintain tetragonal crystals and / or cubic crystals even after firing.
- Examples of the shape of the zirconium oxide nanoparticles include a spherical shape, a granular shape, an elliptical spherical shape, a cubic shape, a rectangular parallelepiped shape, a pyramid shape, a needle shape, a columnar shape, a rod shape, a cylindrical shape, a flake shape, a plate shape, and a flake shape.
- the shape is preferably spherical, granular or columnar.
- the crystallite diameter of the tetragonal crystal and / or cubic crystal of the zirconium oxide nanoparticles calculated by X-ray diffraction analysis is preferably 30 nm or less, and more preferably 20 nm or less. By doing in this way, the transparency of the composition containing a zirconium oxide nanoparticle can be improved.
- the crystallite diameter is more preferably 20 nm or less, and further preferably 15 nm or less.
- the lower limit of the crystallite diameter is usually about 1 nm.
- the particle diameter of the zirconium oxide nanoparticles can be evaluated by the average particle diameter obtained by processing images obtained by various electron microscopes, and the average particle diameter (average primary particle diameter) is preferably 100 nm or less, more preferably Is 50 nm or less, more preferably 30 nm or less, and the lower limit is not particularly limited, but is usually 1 nm.
- the average particle size was randomly increased by expanding the zirconium oxide nanoparticles with a transmission electron microscope (TEM), a field emission transmission electron microscope (FE-TEM), a field emission scanning electron microscope (FE-SEM), etc. It can be determined by selecting 100 particles, measuring the length in the major axis direction, and calculating the arithmetic average thereof.
- Zirconium oxide nanoparticles are produced by bringing zirconia-containing particles into contact with compound (1).
- the contact temperature is preferably 0 to 120 ° C, more preferably 10 to 100 ° C, still more preferably 20 to 80 ° C.
- grains may be disperse
- the zirconia-containing particles are produced by hydrothermal reaction of a zirconium component, a carboxylic acid (2), and an Al or rare earth element component used as necessary.
- a zirconium component there can be used a zirconium raw material which is composed (preferably combined) of carboxylic acid (2) and zirconium or a zirconium-containing compound.
- it when synthesizing nanoparticles containing Al or a rare earth element component, it is composed of carboxylic acid (2) and at least one of Al, rare earth element, Al-containing compound and rare earth element-containing compound (preferably bonded) Al) or a rare earth element source material can be used.
- zirconium raw material examples include (i) a salt of carboxylic acid (2) and a zirconium oxide precursor, (ii) a zirconium salt of carboxylic acid (2), and (iii) carboxylic acid (2) and oxidation. Examples thereof include at least one selected from zirconium precursors.
- zirconium oxide precursor examples include zirconium hydroxide, chloride, oxychloride, acetate, oxyacetate, oxynitrate, sulfate, carbonate, alkoxide and the like. That is, zirconium alkoxides such as zirconium hydroxide, zirconium chloride, zirconium oxychloride, zirconium acetate, zirconium oxyacetate, zirconium oxynitrate, zirconium sulfate, zirconium carbonate, and tetrabutoxyzirconium.
- the salt is not only a single compound composed of a stoichiometric ratio of the carboxylic acid (2) and the zirconium oxide precursor, but also a complex salt, an unreacted carboxylic acid (2) or a zirconium oxide precursor. May be present in the composition.
- the salt of the carboxylic acid (2) and the zirconium oxide precursor was adjusted to have a degree of neutralization of 0.1 to 0.8 (more preferably 0.2 to 0.7). It is preferably a salt of carboxylic acid (2) and zirconium obtained by a reaction between a carboxylate-containing composition derived from carboxylic acid (2) and a zirconium oxide precursor. If the degree of neutralization is less than 0.1, the solubility of the carboxylic acid (2) compound is low, so that the salt may not be formed sufficiently, and if it exceeds 0.8, it is presumed to be a hydroxide of zirconium. In some cases, a large amount of white precipitate is generated and the yield of the coated zirconium oxide particles decreases.
- the degree of neutralization is preferably adjusted with an alkali metal and / or an alkaline earth metal, and alkali metals that form a highly water-soluble salt, particularly sodium and potassium, are preferred.
- the ratio of the carboxylate-containing composition to the zirconium oxide precursor is preferably 1 to 20 moles of carboxyl groups, more preferably 1.2 to 18 moles per mole of zirconium oxide precursor. 1.5 to 15 mol is more preferable.
- the reaction temperature is not particularly limited as long as the aqueous solution can be maintained, but is preferably from room temperature to 100 ° C, more preferably from 40 ° C to 80 ° C.
- the salt obtained by reacting the carboxylate-containing composition with the zirconium oxide precursor may be subjected to a hydrothermal reaction as it is, but insoluble by-products are removed by filtration, liquid separation, or the like. Is preferred.
- a zirconium salt of the carboxylic acid (2) prepared in advance is used.
- a hydrothermal reaction without going through the complicated steps as described above.
- the compounds that can be easily obtained are limited, the target zirconium oxide particles coated with an organic group may not be obtained.
- zirconium salt examples include zirconium octoate, zirconium 2-ethylhexanoate, zirconium stearate, zirconium laurate, zirconium naphthenate, zirconium oleate, zirconium ricinoleate and the like. I can do it. When the purity of the zirconium salt is low, it may be used after purification, but a commercially available product or a salt prepared in advance can be directly subjected to a hydrothermal reaction.
- the zirconium oxide precursor that can be used in (iii) is the same as the zirconium oxide precursor described above.
- the zirconium oxide precursor is preferably zirconium carbonate.
- the ratio of the carboxylic acid (2) to the zirconium oxide precursor is preferably 0.5 mol to 10 mol of the carboxylic acid (2) with respect to 1 mol of the zirconium oxide precursor. More preferably, it is 1.2 mol-5 mol.
- the carboxylic acid (2) and the zirconium oxide precursor may be subjected to a hydrothermal reaction as they are, or may be reacted in advance before the hydrothermal reaction.
- reaction can be carried out by lowering the reaction pressure to lower the boiling point of water.
- Al or rare earth element raw material (i) a salt of a carboxylic acid (2) and a precursor such as a rare earth oxide, (ii) a salt of a carboxylic acid (2) such as a rare earth element, and ( iii) At least one selected from carboxylic acids (2) and precursors such as rare earth oxides.
- Preferred embodiments (i) to (iii) are the same as the preferred embodiments (i) to (iii) in the zirconium raw material.
- At least one of the above (i) to (iii) and at least one of the above (i) to (iii) are preferably mixed in the presence of water when Al or a rare earth element component is added.
- low boiling point compounds contained in the zirconium oxide precursor such as ammonia and acetic acid can be driven out of the system, and the pressure increase in the hydrothermal reaction in the next step is suppressed. Therefore, it is preferable.
- the hydrothermal reaction will be described.
- the zirconium component when at least one of (i) to (iii) and Al or a rare earth element component are added, oxidation is performed by subjecting at least one of (i) to (iii) to a hydrothermal reaction. A zirconium nanoparticle composition is obtained.
- an organic solvent exhibiting good solubility in the above (i) to (iii) may be added. .
- zirconium oxide nanoparticles it is preferable to use a zirconium salt of carboxylic acid (2), a salt of rare earth element of carboxylic acid (2), etc., respectively, as the zirconium component, Al or rare earth element component.
- organic solvent hydrocarbons, ketones, ethers, alcohols and the like can be used. Since there is a possibility that the reaction does not proceed sufficiently with a solvent that is vaporized during a hydrothermal reaction, an organic solvent having a boiling point of 120 ° C. or higher under normal pressure is preferable, 140 ° C. or higher is more preferable, and 150 ° C. or higher is even more preferable.
- Examples include diol, 2,3-butanediol, hexanediol, glycerin, methanetrimethylol, toluene, xylene, trimethylbenzene, dimethylformamide (DMF), dimethylsulfoxide (DMSO) and the like, and mineral oil, dodecane, tetradecane, and trimethylbenzene preferable.
- a surfactant or the like When separated into two layers by adding the organic solvent, a surfactant or the like may be added to obtain a homogeneous phase state or a suspension emulsified state, but usually the two layers are subjected to a hydrothermal reaction. I can do it.
- the composition may contain a sufficient amount of water derived from the raw material, but if there is no or little water contained in the raw material, add water before subjecting it to a hydrothermal reaction. There is a need.
- the amount of water present in the hydrothermal reaction system is the number of moles of water relative to the number of moles of zirconium oxide precursor or a salt containing zirconium (hereinafter referred to as zirconium oxide precursor) present in the system (number of moles of water /
- the number of moles of zirconium oxide precursor and the like is preferably 4/1 to 100/1, more preferably 8/1 to 50/1. If it is less than 4/1, the hydrothermal reaction may take a long time, and the obtained zirconium oxide particles may have a large particle size. On the other hand, if it exceeds 100/1, there is no particular problem except that productivity is lowered because there are few zirconium oxide precursors and the like present in the system.
- the hydrothermal reaction is preferably performed at a pressure of 2 MPaG (gauge pressure) or less. Although the reaction proceeds even above 2 MPaG, the reaction apparatus becomes expensive, which is not industrially preferable. On the other hand, if the pressure is too low, the reaction progresses slowly, and the particle size of the nanoparticles may increase due to the long-time reaction or the zirconium oxide may have a plurality of crystal systems. It is preferable to carry out under the above pressure, and it is more preferable to carry out at 0.2 MPaG or more.
- the hydrothermal reaction time is, for example, about 2 to 24 hours.
- Zirconium oxide nanoparticles have good dispersibility in various media and can be added to various solvents, monomers (monofunctional monomers and / or crosslinkable monomers), oligomers, polymers, etc., or combinations thereof.
- the present invention also includes compositions containing zirconium oxide nanoparticles.
- the composition includes a dispersion containing zirconium oxide nanoparticles and a solvent, and a resin composition containing at least one resin component selected from zirconium oxide nanoparticles, monomers, oligomers, and polymers.
- the resin composition includes a polymer (polymer or the like) and zirconium oxide nanoparticles; a mixture of a dicarboxylic acid and a diamine, an unsaturated carboxylic acid such as acrylic acid or methacrylic acid, or an ester compound thereof. And a composition comprising a monomer having a property and zirconium oxide nanoparticles; a composition comprising the polymer, the monomer having a polymerizability, and zirconium oxide nanoparticles; and the like.
- the resin component may be a molding resin used for a molding material such as an optical film.
- the resin composition may further contain a solvent (coating material).
- the solvent used in the composition has an HSP distance to water of preferably 40 (MPa) 1/2 or less, more preferably 35 (MPa) 1/2 or less, More preferably, it is 30 (MPa) 1/2 or less, and although a minimum is not specifically limited, Usually, it is 0 (MPa) 1/2 or more.
- alcohols such as methanol, ethanol, n-propanol, isopropanol, and ethylene glycol
- ketones such as methyl
- Hydrocarbons Halogenated hydrocarbons such as dichloromethane and chloroform; Dimethylforma De, N, N- dimethylacetamide, amides such as N- methylpyrrolidone; water; mineral oils, vegetable oils, waxes oils include oils such as silicone oil. These may be used alone or in combination of two or more. Since the zirconium oxide nanoparticles have particularly good dispersibility in polar solvents, preferred organic solvents are water, alcohols, esters or amides, more preferably water, alcohols or esters, and still more preferably. Water or alcohols, particularly preferably water, methanol or ethanol.
- the zirconium oxide nanoparticles of the present invention have good dispersibility in organic solvents, a dispersion having a high core concentration can also be produced.
- the total amount (core concentration) of oxides of metal elements (zirconium, aluminum, transition metal, etc.) contained in the nanoparticles of the present invention in the dispersion is preferably 100% by mass or more, more preferably 45% by mass or more.
- the upper limit is not limited, but is, for example, 80% by mass or less, more preferably 70% by mass or less.
- the total amount (core concentration) of oxides of metal elements (zirconium, aluminum, transition metal, etc.) contained in the nanoparticles of the present invention in the dispersion can be calculated based on the formula (A).
- Core concentration total weight of metal oxides contained in the nanoparticles according to the present invention in the dispersion / dispersion weight (A)
- the monofunctional monomer may be a compound having only one polymerizable carbon-carbon double bond, and is a (meth) acrylic acid ester; styrene, p-tert-butylstyrene, ⁇ -methylstyrene, m-methylstyrene. , Styrene monomers such as p-methylstyrene, p-chlorostyrene and p-chloromethylstyrene; carboxyl group-containing monomers such as (meth) acrylic acid; hydroxyl group-containing monomers such as hydroxyethyl (meth) acrylate Examples include the body.
- (meth) acrylic acid ester examples include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth).
- (Meth) acrylic acid alkyl esters such as acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate; (meth) acrylic such as cyclohexyl (meth) acrylate and isobornyl (meth) acrylate Acid cycloalkyl ester; (meth) acrylic acid aralkyl ester such as benzyl (meth) acrylate; (meth) acrylic acid ester having a glycidyl group such as glycidyl (meth) acrylate. These exemplified monofunctional monomers may be used alone, or two or more kinds may be appropriately mixed and used.
- the crosslinkable monomer may be a compound containing a plurality of carbon-carbon double bonds copolymerizable with the carbon-carbon double bond of the monomer.
- Specific examples of the crosslinkable monomer include alkylene glycol poly (ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate) and the like.
- (Meth) acrylate neopentyl glycol poly (meth) acrylate such as neopentyl glycol di (meth) acrylate and dineopentyl glycol di (meth) acrylate; trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) Trimethylolpropane poly (meth) acrylate such as acrylate; pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipenta Polyfunctional (meth) acrylates such as pentaerythritol poly (meth) acrylate such as lithitol hexa (meth) acrylate; polyfunctional styrene monomers such as divinylbenzene; diallyl phthalate, diallyl isophthalate, triallyl cyanurate, tri And polyfunctional allyl ester
- the composition containing the monomer corresponds to a curable composition.
- the curable composition constitutes a resin composition after curing, and such a curable composition is also included in the resin composition of the present invention.
- the composition of the present invention may be a resin composition containing the polymer (resin).
- the polymer that is a medium is, for example, polyamides such as 6-nylon, 66-nylon, and 12-nylon; polyimides; polyurethanes; polyolefins such as polyethylene and polypropylene, PET, PBT, Polyesters such as PEN; polyvinyl chlorides; polyvinylidene chlorides; polyvinyl acetates; polyvinyl alcohols; polystyrenes; (meth) acrylic resin-based polymers; ABS resins; fluororesins; phenol-formalin resins, cresol-formalins Phenol resins such as resins; epoxy resins; amino resins such as urea resins, melamine resins and guanamine resins; polyvinyl butyral resins, polyurethane resins, ethylene-vinyl acetate copolymer resins, ethylene- (meth) acrylic acid esters Or the like can be mentioned a soft resin and a hard resin
- polyimides, polyurethanes, polyesters, polyvinyl alcohols, (meth) acrylic resin polymers, phenol resins, amino resins, and epoxy resins are more preferable, and polyvinyl alcohols or (meth) acrylic resin polymers are preferred. Further preferred. These may be used alone or in combination of two or more.
- the concentration of the zirconium oxide nanoparticles in the composition can be appropriately set according to the use. However, when the composition is uncured or contains a polymer (resin), all components of the composition are usually used. It is 90% by mass or less with respect to 100% by mass (total of all of zirconium oxide nanoparticles, solvent, monomer, oligomer, polymer, polymer precursor described later, etc. used). If it exceeds 90% by mass, it may be difficult to uniformly disperse and the uncured composition may become cloudy.
- the lower limit is not particularly limited, but is, for example, 1% by mass or more in consideration of the solvent cost. More preferably, they are 5 mass% or more and 85 mass% or less, More preferably, they are 10 mass% or more and 80 mass% or less.
- the composition has good transparency even in a high concentration composition (dispersion).
- a composition in which zirconium oxide nanoparticles are dispersed at a high concentration is advantageous, for example, in improving the refractive index, and the refractive index can be adjusted according to various applications.
- the amount of zirconium oxide nanoparticles in the composition is preferably 25% by mass or more, more preferably 30% by mass or more, and still more preferably Is 60% by mass or more.
- the upper limit is not particularly limited, the amount of zirconium oxide nanoparticles in the composition is preferably 90% by mass or less.
- the resin composition may contain zirconium oxide nanoparticles and other additive components of the resin.
- the additive component include a curing agent, a curing accelerator, a colorant, a release agent, a reactive diluent, a plasticizer, a stabilizer, a flame retardant aid, and a crosslinking agent.
- the shape of the resin composition is not particularly limited, and may be a molding material such as a plate, a sheet, a film, or a fiber.
- Zirconium oxide nanoparticles have good dispersibility, such as antireflection films, hard coat films, brightness enhancement films, prism films, lenticular sheets, microlens sheets, and other optical films (or sheets), optical refractive index adjusters, Optical adhesive, optical waveguide, lens, catalyst, CMP polishing composition, electrode, capacitor, inkjet recording method, piezoelectric element, LED / OLED / organic EL light extraction improver, antibacterial agent, dental adhesive, etc.
- the denture material In addition to being used favorably for light concentrating structures used in solar cell panels, the denture material, SOFC (solid oxide form), since the change in crystal structure before and after firing is suppressed in addition to good dispersibility It can also be suitably used for ceramic materials such as (fuel cell) materials and crucibles.
- the zirconium oxide nanoparticles are coated with the compound (1) having the group R 1 , the dispersibility in a solvent (particularly a highly polar solvent) is good, and the composition containing the zirconium oxide nanoparticles is fired.
- the obtained ceramic material has good ceramic properties such as translucency, toughness and strength.
- the ceramic material obtained from zirconium oxide nanoparticles can be obtained by firing zirconium oxide nanoparticles alone.
- zirconium oxide nanoparticles can be obtained by firing a composition containing additives such as alumina, spinel, YAG, mullite, and an aluminum borate compound.
- the composition which consists of a zirconium oxide nanoparticle and a binder can also be obtained by baking.
- the firing temperature at this time may be about 500 to 1600 ° C.
- Firing can be performed by a known method. Pressure may be applied to promote sintering during firing. Further, it may be fired in air, an oxygen atmosphere, a mixed atmosphere of oxygen and air, or may be fired in an inert atmosphere such as nitrogen or argon. Each can be appropriately selected according to the use after firing.
- the average primary particle diameter of coated zirconium oxide particles was measured by observing with an ultra-high resolution field emission scanning electron microscope (S-4800, manufactured by Hitachi High-Technologies Corporation). did. The coated zirconium oxide particles were observed at a magnification of 150,000 times, the length of each particle in the major axis direction was measured for any 100 particles, and the average value was taken as the average primary particle size.
- Comparative Example 1 Zirconium oxide coated with 2-ethylhexanoic acid (R 1 Hansen solubility parameter (HSP) distance to ethanol is 21 (MPa) 1/2 ) and / or carboxylate derived from 2-ethylhexanoic acid Production of nanoparticles> Pure water (15.5 g) was mixed with zirconium 2-ethylhexanoate mineral spirit solution (90.4 g, zirconium 2-ethylhexanoate content 44 mass%, manufactured by Daiichi Rare Element Chemical Co., Ltd.), and 200 mL of water The thermosynthetic vessel was charged. The vessel was heated to 190 ° C. and kept at that temperature for 16 hours for reaction.
- HSP Hansen solubility parameter
- the pressure during hydrothermal synthesis was 1.3 MPaG (gauge pressure). After the reaction, water was separated and removed from the hydrothermal synthesis reaction solution. When the crystal structure of the zirconium oxide nanoparticles obtained by removing the organic solvent by heating the upper layer of the hydrothermal synthesis reaction solution after removing water was confirmed at 180 ° C., it was attributed to tetragonal and monoclinic crystals. From the diffraction line intensity, the ratio of tetragonal to monoclinic crystal was 74/26, and the particle diameter (tetragonal and / or cubic crystallite diameter) was 5 nm. The measurement result of the average primary particle diameter by an electron microscope was 11 nm.
- decrease rate of the zirconium oxide nanoparticle was 14 mass%. Therefore, it was found that the coating amount of 2-ethylhexanoic acid and / or carboxylate derived from 2-ethylhexanoic acid was 14% by mass of the entire zirconium oxide nanoparticles.
- ethanol 0.5 g, Hansen solubility parameter (HSP) distance in water is 24 (MPa) 1/2
- Example 1 Production of zirconium oxide nanoparticles coated with methoxyacetic acid> 50 g of the upper layer of the hydrothermal synthesis reaction liquid after removing water of Comparative Example 1 and 5 g of methoxyacetic acid (R 1 Hansen solubility parameter (HSP) distance to ethanol is 14 (MPa) 1/2 ) for 30 minutes at 60 ° C. Mixed. The aggregated particles were then separated by filtration after adding n-hexane. Thereafter, the separated aggregated particles are added to n-hexane, and after stirring for 10 minutes, the aggregated particles are separated by filtration, and the obtained particles are vacuum-dried at room temperature, so that the zirconium oxide nanoparticle coated with methoxyacetic acid is obtained.
- R 1 Hansen solubility parameter (HSP) distance to ethanol is 14 (MPa) 1/2
- Example 2 Production of inorganic oxide fine particle-containing solution 1>
- the inorganic oxide fine particle containing solution 1 was obtained by mix
- Example 2 Production of yttria-stabilized zirconium oxide nanoparticles coated with 2-ethylhexanoic acid and / or carboxylate derived from 2-ethylhexanoic acid>
- the zirconium 2-ethylhexanoate mineral spirit solution of Example 1 (zirconium 2-ethylhexanoate content 44 mass%, manufactured by Daiichi Rare Element Chemical Co., Ltd.) was changed to 86.7 g, and Nikka octyl strium (containing yttrium) was obtained. This was synthesized in the same manner as in Example 1 except that the amount was changed to 10.1 g.
- the coating amount of 2-ethylhexanoic acid and / or carboxylate derived from 2-ethylhexanoic acid was 25% by mass of the total yttria-stabilized zirconium oxide nanoparticles.
- Yttria-stabilized zirconium oxide nanoparticles (1 g) obtained by removing the organic solvent and ethanol (0.5 g) were mixed and stirred, but the white powder was not dispersed.
- Example 3 Production of coated yttria-stabilized zirconium oxide nanoparticles coated with methoxyacetic acid> Synthesis was performed in the same manner as in Example 1 except that the upper layer of the hydrothermal synthesis reaction solution after removing the used water was synthesized in Comparative Example 2. The weight (mass) reduction rate of the yttria-stabilized zirconium oxide nanoparticles was 15% by mass. Therefore, the mass of 2-ethylhexanoic acid, carboxylate derived from 2-ethylhexanoic acid and methoxyacetic acid to be coated was found to be 15% by mass of the total yttria-stabilized zirconium oxide nanoparticles.
- Example 4 Production of inorganic oxide fine particle-containing solution 2>
- the yttria-stabilized zirconium oxide nanoparticles (1 g) obtained in Example 3 and ethanol (0.5 g) were blended and stirred until uniform to obtain inorganic oxide fine particle-containing solution 2.
- Example 5 Production of inorganic oxide fine particle-containing resin composition 1> By blending 1 g of zirconium oxide nanoparticles obtained in Example 1, 1 g of 2-hydroxyethyl acrylate (manufactured by Nippon Shokubai) and 4 g of methanol, and stirring at room temperature for 1 hour, uniform inorganic oxide fine particle-containing resin Composition 1 was obtained.
- Example 6 Production of resin composition 2 containing fine inorganic oxide particles> By mixing 1 g of zirconium oxide nanoparticles obtained in Example 1, 1 g of pentaerythritol triacrylate (“SR444 NS” manufactured by SARTOMER), and 4 g of methanol, the mixture is stirred at room temperature for 1 hour to obtain uniform inorganic oxide fine particles. A contained resin composition 2 was obtained.
- SR444 NS pentaerythritol triacrylate
- Example 7 Production of resin composition 3 containing fine inorganic oxide particles> By mixing 1 g of the zirconium oxide nanoparticles obtained in Example 1, 1 g of dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku “KAYARAD DPHA”), and 4 g of methanol, the mixture is uniformly stirred by heating at 80 ° C. for 1 hour. An inorganic oxide fine particle-containing resin composition 3 was obtained.
- Example 8 Production of resin composition 4 containing fine inorganic oxide particles> By mixing 1 g of the zirconium oxide nanoparticles obtained in Example 1, 1 g of polyvinyl alcohol (“CP-1210” manufactured by Kuraray) and 4 g of ion-exchanged water, and heating and stirring at 80 ° C. for 1 hour, uniform inorganic oxidation A fine particle-containing resin composition 4 was obtained.
- CP-1210 polyvinyl alcohol
- the zirconium oxide nanoparticles of the present invention are useful because they are excellent in dispersibility in polar solvents such as alcohol, can increase the core concentration in the dispersion, and can be widely used in optical materials and electronic component materials. is there.
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Abstract
Description
[1]R1-COOH、(R1O)3-n-P(O)-(OH)n、(R1)3-n-P(O)-(OH)n、(R1O)-S(O)(O)-(OH)、R1-S(O)(O)-(OH)、(R1)4-m-Si(R4)mからなる群より選択される1以上の化合物で被覆されていることを特徴とする酸化ジルコニウムナノ粒子。
〔式中、
R1は、酸素原子、窒素原子および硫黄原子からなる群より選ばれる1以上の元素と炭素原子とを含み、R1中の炭素原子、酸素原子、窒素原子および硫黄原子の総原子数が8以下の基を表す。
R4はハロゲン原子又は-OR2であり、R2は水素原子又はアルキル基を表す。
nは1または2を示し、mは1~3の整数を示す。〕
[2]R1中、炭素原子数に対する酸素原子、窒素原子及び硫黄原子の和の比(酸素原子、窒素原子及び硫黄原子の和/炭素原子数)が1/7以上1/1以下である[1]に記載の酸化ジルコニウムナノ粒子。
[3]前記化合物中、炭素原子数に対する酸素原子数の比(酸素原子数/炭素原子数)が1/6超1/0.2以下である[1]または[2]に記載の酸化ジルコニウムナノ粒子。
[4]正方晶及び立方晶の合計が結晶構造全体の60%以上である[1]~[3]のいずれかに記載の酸化ジルコニウムナノ粒子。
[5]平均粒子径が1~100nmである[1]~[4]のいずれかに記載の酸化ジルコニウムナノ粒子。
[6]エタノールに対するR1のハンセン溶解度パラメータ(HSP)距離が0(MPa)1/2以上20(MPa)1/2以下である[1]~[5]のいずれかに記載の酸化ジルコニウムナノ粒子。
[7]水に対するR1のハンセン溶解度パラメータ(HSP)距離が20(MPa)1/2以上41(MPa)1/2以下である[1]~[5]のいずれかに記載の酸化ジルコニウムナノ粒子。
[8][1]~[7]のいずれかに記載の酸化ジルコニウムナノ粒子を含む分散液。
[9]水に対するハンセン溶解度パラメータ(HSP)距離が0(MPa)1/2以上40(MPa)1/2以下である溶媒を含む[8]に記載の分散液。
[10][1]~[7]のいずれかに記載の酸化ジルコニウムナノ粒子を含む樹脂組成物。
[11]モノマー、オリゴマー及びポリマーから選択される少なくとも1種以上の樹脂成分を含む[10]に記載の樹脂組成物。
[12]水に対するハンセン溶解度パラメータ(HSP)距離が0(MPa)1/2以上40(MPa)1/2以下である溶媒を含む[10]または[11]に記載の樹脂組成物。
[13][1]~[7]のいずれかに記載の酸化ジルコニウムナノ粒子を含む成型材料。
[14][1]~[7]のいずれかに記載の酸化ジルコニウムナノ粒子から得られるセラミックス材料。
[15][1]~[7]のいずれかに記載の酸化ジルコニウムナノ粒子を500℃以上で焼成することを特徴とするセラミックス材料の製造方法。
[16][1]~[7]のいずれかに記載の酸化ジルコニウムナノ粒子を含む組成物を500℃以上で焼成することを特徴とするセラミックス材料の製造方法。
(R3)2=4*(D1-D2)2+(P1-P2)2+(H1-H2)2
〔式中、D1、P1、H1は物質1のHSPパラメータであり、D2、P2、H2は物質2のHSPパラメータである。〕
鎖式炭化水素基は、飽和または不飽和のいずれも好ましく、より好ましくは飽和である。また鎖式炭化水素基は、直鎖状または分岐状のいずれも好ましく、より好ましくは直鎖状である。鎖式炭化水素基は、好ましくは飽和鎖式炭化水素基であり、より好ましくは直鎖状の飽和鎖式炭化水素基である。
環式炭化水素基は、飽和または不飽和のいずれも好ましい。
mは、2または3が好ましく、3がより好ましい。R2が水素原子である場合、(R1)4-m-Si(OR2)mとしては、メトキシメチルトリヒドロキシシラン、メトキシエチルトリヒドロキシシラン、(3-アミノプロピル)トリヒドロキシシラン、(3-メルカプトプロピル)トリヒドロキシシラン、2-シアノエチルトリヒドロキシシラン、[3-(N,N-ジメチルアミノ)プロピル]トリヒドロキシシラン、3-(メチルアミノ)プロピルトリヒドロキシシラン、3-シアノプロピルトリヒドロキシシラン、(3-ウレイドプロピル)トリヒドロキシシラン、(3-イソシアナトプロピル)トリヒドロキシシラン、3-(2-アミノエチルアミノ)プロピルトリヒドロキシシラン、[3-(トリヒドロキシシリル)プロピル]カルバミン酸メチルなどが例示される。
1級カルボン酸としては、炭素数4~20の直鎖状1級カルボン酸、炭素数4~20の分岐状1級カルボン酸(すなわち、α位以外の炭素原子が枝分かれしたカルボン酸)が好ましい。直鎖状カルボン酸は、好ましくは直鎖状飽和脂肪族カルボン酸であり、具体的には、酪酸、吉草酸、ヘキサン酸、ヘプタン酸、カプリル酸、ノナン酸、デカン酸、ラウリン酸、テトラデカン酸、ステアリン酸、オレイン酸、リシノール酸などを含む。分岐状1級カルボン酸としては、イソ吉草酸、3,3-ジメチル酪酸、3-メチル吉草酸、イソノナン酸、4-メチル吉草酸、4-メチル-n-オクタン酸、ナフテン酸などが挙げられる。
2級カルボン酸としては、炭素数4~20の2級カルボン酸が好ましく、具体的にはイソ酪酸、2-メチル酪酸、2-エチル酪酸、2-エチルヘキサン酸、2-メチル吉草酸、2-メチルヘキサン酸、2-メチルヘプタン酸、2-プロピル酪酸、2-ヘキシル吉草酸、2-ヘキシルデカン酸、2-ヘプチルウンデカン酸、2-メチルヘキサデカン酸、4-メチルシクロヘキサンカルボン酸などが挙げられ、2-エチルヘキサン酸、2-ヘキシルデカン酸の1種以上が好ましく、2-エチルヘキサン酸が特に好ましい。
3級カルボン酸としては、炭素数5~20の3級カルボン酸が好ましく、具体的にはピバル酸、2,2-ジメチル酪酸、2,2-ジメチル吉草酸、2,2-ジメチルヘキサン酸、2,2-ジメチルヘプタン酸、ネオデカン酸などが挙げられる。
Al及び希土類元素のうち、好ましくはAl、Y、La、Yb、Sc、Ce及びErから選ばれる少なくとも一種以上であり、より好ましくはAl、Y、Sc及びErから選ばれる少なくとも一種以上である。
前記平均粒子径は、酸化ジルコニウムナノ粒子を透過型電子顕微鏡(TEM)、電界放射型透過電子顕微鏡(FE-TEM)、電界放射型走査電子顕微鏡(FE-SEM)などで拡大し、無作為に100個の粒子を選択してその長軸方向の長さを測定し、その算術平均を求めることで決定できる。
前記カルボン酸塩含有組成物と前記酸化ジルコニウム前駆体とを反応させるには、水溶液同士又は水溶液と有機溶媒を混合させるのが好ましい。反応温度は水溶液を保持できる温度であれば特に問わないが、室温から100℃が好ましく、40℃~80℃がより好ましい。
(ii)の実施形態では、事前に調製したカルボン酸(2)のジルコニウム塩を用いるものである。上記の様な煩雑な工程を経ることなく、水熱反応に供することが出来る利点がある。但し、容易に入手できる化合物が限られているため、目的とする有機基で被覆された酸化ジルコニウム粒子が得られないことがある。
ジルコニウム成分について前記(i)~(iii)の少なくとも1種と、Al又は希土類元素成分を入れる場合には、前記(i)~(iii)の少なくとも1種とを水熱反応に供することで酸化ジルコニウムナノ粒子組成物が得られる。前記(i)~(iii)だけでは、粘度が高く水熱反応が効率的に進行しない場合には、該(i)~(iii)に対して良好な溶解性を示す有機溶媒を添加するとよい。酸化ジルコニウムナノ粒子を得るためには、特にジルコニウム成分、Al又は希土類元素成分として、それぞれカルボン酸(2)のジルコニウム塩、カルボン酸(2)の希土類元素等の塩を用いることが好ましい。
酸化ジルコニウムナノ粒子は、特に極性溶媒に対する分散性が良好なため、好ましい有機溶媒は水、アルコール類、エステル類またはアミド類であり、より好ましくは水、アルコール類またはエステル類であり、更に好ましくは水またはアルコール類であり、特に好ましくは水、メタノール又はエタノールである。
なお分散液中、本発明のナノ粒子に含まれる金属元素(ジルコニウム、アルミニウム、遷移金属など)の酸化物の総量(コア濃度)は、式(A)に基づいて計算できる。
コア濃度=分散液中の本発明に係るナノ粒子に含まれる金属酸化物の総重量/分散液重量 …(A)
酸化ジルコニウムナノ粒子の結晶構造は、X線回折装置(リガク社製、RINT-TTRIII)を用いて解析した。測定条件は以下の通りである。
X線源:CuKα(0.154nm)
X線出力設定:50kV、300mA
サンプリング幅:0.0200°
スキャンスピード:10.0000°/min
測定範囲:10~75°
測定温度:25℃
X線回折装置(リガク社製、RINT-TTRIII)を用いて算出される値を元に、計算ソフト(リガク社製、PDXL)を用いて参照強度比法(RIP法)により定量した(ピークの帰属も計算ソフトの指定に従った)。
酸化ジルコニウムナノ粒子の結晶子径は、X線回折装置(リガク社製、RINT-TTRIII)によって解析及び算出される30°のピークの半値幅を元に、計算ソフト(リガク社製、PDXL)を用いて算出した。
なお、X線回折測定では酸化ジルコニウムナノ粒子の立方晶と正方晶を区別することが難しく、立方晶が存在する場合でもその割合は正方晶の割合としてカウントされる。
TG-DTA(熱重量-示差熱分析)装置により、空気雰囲気下、室温から800℃まで10℃/分で酸化ジルコニウムナノ粒子を昇温し、該粒子の重量(質量)減少率を測定した。この重量(質量)減少率により、酸化ジルコニウムナノ粒子を被覆している被覆剤の割合を知ることができる。
被覆型酸化ジルコニウム粒子の平均一次粒子径は、超高分解能電界放出型走査電子顕微鏡(日立ハイテクノロジーズ社製、S-4800)で観察することによって測定した。倍率15万倍で被覆型酸化ジルコニウム粒子を観察し、任意の100個の粒子について、各粒子の長軸方向の長さを測定し、その平均値を平均一次粒子径とした。
コア濃度は、式(A)に基づいて算出した。なお実施例では、「分散液中のナノ粒子に含まれる金属酸化物の総重量」を、「(配合したナノ粒子重量×(1-(4)で測定された重量減少率))」として計算を行った。
コア濃度=分散液中のナノ粒子に含まれる金属酸化物の総重量/分散液重量 …(A)
2-エチルヘキサン酸ジルコニウムミネラルスピリット溶液(90.4g、2-エチルヘキサン酸ジルコニウム含有率44質量%、第一稀元素化学工業社製)に純水(15.5g)を混合し、200mLの水熱合成容器に仕込んだ。この容器を190℃まで加熱し、該温度で16時間保持して反応させた。水熱合成の際の圧力は、1.3MPaG(ゲージ圧)であった。反応後、水熱合成反応溶液から水を分液して取り除いた。
水を除去した後の水熱合成反応液上層を、180℃で加熱して有機溶媒を除去して得られた酸化ジルコニウムナノ粒子の結晶構造を確認したところ、正方晶と単斜晶に帰属される回折線が検出され、回折線の強度から、正方晶と単斜晶の割合は74/26で、その粒子径(正方晶及び/又は立方晶の結晶子径)は5nmであった。電子顕微鏡による平均一次粒子径の測定結果は11nmであった。また酸化ジルコニウムナノ粒子の重量(質量)減少率は、14質量%であった。従って、被覆する2-エチルヘキサン酸及び/又は2-エチルヘキサン酸由来のカルボキシレートは、酸化ジルコニウムナノ粒子全体の14質量%であることが分かった。
この有機溶媒を除去して得られた粒子(1g)にエタノール(0.5g、水に対するハンセン溶解度パラメータ(HSP)距離は24(MPa)1/2)を添加したところ、白濁が生じて粒子を分散させることはできなかった。
比較例1の水を除去した後の水熱合成反応液上層50gとメトキシ酢酸(エタノールに対するR1のハンセン溶解度パラメータ(HSP)距離は14(MPa)1/2)5gを60℃で30分撹拌混合した。次いで、n-ヘキサンを添加した後に凝集粒子を濾過により分離した。その後、分離した凝集粒子をn-ヘキサン中に添加、10分撹拌後、凝集粒子を濾過により分離し、得られた粒子を室温にて真空乾燥することで、メトキシ酢酸で被覆された酸化ジルコニウムナノ粒子を得た。
この粒子の結晶構造を確認したところ、正方晶と単斜晶に帰属される回折線が検出され、回折線の強度から、正方晶と単斜晶の割合は74/26で、その粒子径(正方晶及び/又は立方晶の結晶子径)は5nmであった。また酸化ジルコニウムナノ粒子の重量(質量)減少率は、11質量%であった。従って、被覆する2-エチルヘキサン酸、2-エチルヘキサン酸由来のカルボキシレート及びメトキシ酢酸の質量は、酸化ジルコニウムナノ粒子全体の11質量%であることが分かった。
実施例1で得られた酸化ジルコニウムナノ粒子(1g)及びエタノール(0.5g)を配合し、均一になるまで撹拌することで、無機酸化物微粒子含有溶液1を得た。なお分散液中、得られたナノ粒子に含まれる金属酸化物の濃度(コア濃度)は59%(=(1g×(1-0.11))/(1g+0.5g))であった。
実施例1の2-エチルヘキサン酸ジルコニウムミネラルスピリット溶液(2-エチルヘキサン酸ジルコニウム含有率44質量%、第一稀元素化学工業社製)を86.7gに変更し、ニッカオクチックスイットリウム(イットリウム含有量6.2%、日本化学産業社製)を10.1gに変更した以外は、実施例1と同様に合成した。
得られたイットリア安定化酸化ジルコニウムナノ粒子の結晶構造を確認したところ、正方晶と単斜晶に帰属される回折線が検出され、回折線の強度から、正方晶と単斜晶の割合は97/3で、その粒子径(正方晶及び/又は立方晶の結晶子径)は4nmであった。電子顕微鏡による平均一次粒子径の測定結果は6nmであった。またイットリア安定化酸化ジルコニウムナノ粒子の重量(質量)減少率は、25質量%であった。従って、被覆する2-エチルヘキサン酸及び/又は2-エチルヘキサン酸由来のカルボキシレートは、イットリア安定化酸化ジルコニウムナノ粒子全体の25質量%であることが分かった。有機溶媒を除去して得られたイットリア安定化酸化ジルコニウムナノ粒子(1g)及びエタノール(0.5g)を混合撹拌したが、白色粉体が分散することはなかった。
使用した水を除去した後の水熱合成反応液上層を比較例2で合成したものとした以外は、実施例1と同様に合成した。イットリア安定化酸化ジルコニウムナノ粒子の重量(質量)減少率は、15質量%であった。従って、被覆する2-エチルヘキサン酸、2-エチルヘキサン酸由来のカルボキシレート及びメトキシ酢酸の質量は、イットリア安定化酸化ジルコニウムナノ粒子全体の15質量%であることが分かった。
実施例3で得られたイットリア安定化酸化ジルコニウムナノ粒子(1g)及びエタノール(0.5g)を配合し、均一になるまで撹拌することで、無機酸化物微粒子含有溶液2を得た。なお分散液中、得られたナノ粒子に含まれる金属酸化物の濃度(コア濃度)は57%(=(1g×(1-0.15))/(1g+0.5g))であった。
実施例1で得られた酸化ジルコニウムナノ粒子1g、アクリル酸2-ヒドロキシエチル(日本触媒製)1g、及びメタノール4gを配合し、室温で1時間撹拌することで、均一な無機酸化物微粒子含有樹脂組成物1を得た。
実施例1で得られた酸化ジルコニウムナノ粒子1g、ペンタエリスリトールトリアクリレート(SARTOMER社製「SR444 NS」)1g、及びメタノール4gを配合し、室温で1時間撹拌することで、均一な無機酸化物微粒子含有樹脂組成物2を得た。
実施例1で得られた酸化ジルコニウムナノ粒子1g、ジペンタエリスリトールヘキサアクリレート(日本化薬製「KAYARAD DPHA」)1g、及びメタノール4gを配合し、80℃で1時間加熱撹拌することで、均一な無機酸化物微粒子含有樹脂組成物3を得た。
実施例1で得られた酸化ジルコニウムナノ粒子1g、ポリビニルアルコール(クラレ製「CP-1210」)1g、及びイオン交換水4gを配合し、80℃で1時間加熱撹拌することで、均一な無機酸化物微粒子含有樹脂組成物4を得た。
Claims (16)
- R1-COOH、(R1O)3-n-P(O)-(OH)n、(R1)3-n-P(O)-(OH)n、(R1O)-S(O)(O)-(OH)、R1-S(O)(O)-(OH)、(R1)4-m-Si(R4)mからなる群より選択される1以上の化合物で被覆されていることを特徴とする酸化ジルコニウムナノ粒子。
〔式中、
R1は、酸素原子、窒素原子および硫黄原子からなる群より選ばれる1以上の元素と炭素原子とを含み、R1中の炭素原子、酸素原子、窒素原子および硫黄原子の総原子数が8以下の基を表す。
R4はハロゲン原子又は-OR2であり、R2は水素原子又はアルキル基を表す。
nは1または2を示し、mは1~3の整数を示す。〕 - R1中、炭素原子数に対する酸素原子、窒素原子及び硫黄原子の和の比(酸素原子、窒素原子及び硫黄原子の和/炭素原子数)が1/7以上1/1以下である請求項1に記載の酸化ジルコニウムナノ粒子。
- 前記化合物中、炭素原子数に対する酸素原子数の比(酸素原子数/炭素原子数)が1/6超1/0.2以下である請求項1または2に記載の酸化ジルコニウムナノ粒子。
- 正方晶及び立方晶の合計が結晶構造全体の60%以上である請求項1~3のいずれかに記載の酸化ジルコニウムナノ粒子。
- 平均粒子径が1~100nmである請求項1~4のいずれかに記載の酸化ジルコニウムナノ粒子。
- エタノールに対するR1のハンセン溶解度パラメータ(HSP)距離が0(MPa)1/2以上20(MPa)1/2以下である請求項1~5のいずれかに記載の酸化ジルコニウムナノ粒子。
- 水に対するR1のハンセン溶解度パラメータ(HSP)距離が20(MPa)1/2以上41(MPa)1/2以下である請求項1~5のいずれかに記載の酸化ジルコニウムナノ粒子。
- 請求項1~7のいずれかに記載の酸化ジルコニウムナノ粒子を含む分散液。
- 水に対するハンセン溶解度パラメータ(HSP)距離が0(MPa)1/2以上40(MPa)1/2以下である溶媒を含む請求項8に記載の分散液。
- 請求項1~7のいずれかに記載の酸化ジルコニウムナノ粒子を含む樹脂組成物。
- モノマー、オリゴマー及びポリマーから選択される少なくとも1種以上の樹脂成分を含む請求項10に記載の樹脂組成物。
- 水に対するハンセン溶解度パラメータ(HSP)距離が0(MPa)1/2以上40(MPa)1/2以下である溶媒を含む請求項10または11に記載の樹脂組成物。
- 請求項1~7のいずれかに記載の酸化ジルコニウムナノ粒子を含む成型材料。
- 請求項1~7のいずれかに記載の酸化ジルコニウムナノ粒子から得られるセラミックス材料。
- 請求項1~7のいずれかに記載の酸化ジルコニウムナノ粒子を500℃以上で焼成することを特徴とするセラミックス材料の製造方法。
- 請求項1~7のいずれかに記載の酸化ジルコニウムナノ粒子を含む組成物を500℃以上で焼成することを特徴とするセラミックス材料の製造方法。
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