CN105085561B - Metal oxide particle and application thereof - Google Patents

Metal oxide particle and application thereof Download PDF

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Publication number
CN105085561B
CN105085561B CN201510408770.4A CN201510408770A CN105085561B CN 105085561 B CN105085561 B CN 105085561B CN 201510408770 A CN201510408770 A CN 201510408770A CN 105085561 B CN105085561 B CN 105085561B
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acid
metal oxide
compound
particle
carboxylic acid
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CN105085561A (en
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高桥邦夫
广田幸逸
冈田笃
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Nippon Shokubai Co Ltd
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Nippon Shokubai Co Ltd
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Priority claimed from JP2011270198A external-priority patent/JP2013122643A/en
Priority claimed from JP2012085681A external-priority patent/JP6030844B2/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C53/00—Saturated compounds having only one carboxyl group bound to an acyclic carbon atom or hydrogen
    • C07C53/126—Acids containing more than four carbon atoms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G1/00—Methods of preparing compounds of metals not covered by subclasses C01B, C01C, C01D, or C01F, in general
    • C01G1/02—Oxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/04—Oxides; Hydroxides
    • C01G23/047—Titanium dioxide
    • C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G25/00—Compounds of zirconium
    • C01G25/02—Oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/056—Forming hydrophilic coatings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
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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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/36—Compounds of titanium
    • C09C1/3607—Titanium dioxide
    • C09C1/3669—Treatment with low-molecular organic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/36—Compounds of titanium
    • C09C1/3692—Combinations of treatments provided for in groups C09C1/3615 - C09C1/3684
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/006—Combinations of treatments provided for in groups C09C3/04 - C09C3/12
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2433/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2244—Oxides; Hydroxides of metals of zirconium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets

Abstract

The present invention provides a kind of metal oxide particle and application thereof covered by carboxylate.Metal oxide particle provided by the invention is covered by least two kinds of carboxylic acid compounds with the carboxylic acid compound other than the carboxylic acid of 1 or more substituent group or first carboxylic acid compound and the first carboxylic acid compound of (methyl) acrylic acid in the group as composed by ester group, ether, amide groups, thioester substrate, thioether group, carbonate group, urethane groups and urea base.Metal oxide particle of the invention, due to being covered with carboxylate compound, favorable dispersibility in solvent and resin, and heat resistance is also excellent.

Description

Metal oxide particle and application thereof
Related application
It is December 10, entitled " chemical combination in 2012 that the application, which is application No. is the 201280060430.1, applying date, The divisional application of the Chinese invention patent application of object, metal oxide particle and its preparation method and application ".
Technical field
The present invention relates to a kind of metal oxide particles and application thereof.
Background technique
It has widely popularized using liquid crystal display as the thin display of representative, in addition to previous television applications, has calculated Machine purposes is also rapidly popularized towards portable applications, mobile phone purposes, mobile terminal purposes etc..Thin display be with The layered body of the material or film of various functions, plate, but in order to improve function and lighting, resin film is used mostly, it is another Aspect uses inorganic material in electrode, is formed as the structure that multiple material is laminated.
On the other hand, the touch panel of the input unit one-piece type as display, due to its good use feeling by Widely utilize.There are many kinds of the modes of the touch panel, it is known that have optical profile type, ultrasonic wave mode, resistive film mode, capacitor Coupled modes etc..Wherein, consider from pure of its structure etc., resistive film mode is widely used, the resistive film side The touch panel of formula is formed as 2 transparent conductive films and substrate via the opposite structure of partition, to be pressed by finger or pen etc. Pressure contacts opposite conductive film and the structure of mode that is inputted (for example, referring to patent document 1).
In addition, the touch panel of capacitive coupling, for by proximity sensors such as the fingers of people, detection is applied with voltage Sensor static capacity variation come the structure of the mode inputted, by the way that electrode is configured with special pattern, It can further improve detection position precision (for example, referring to patent document 2).The capacitive coupling compared with resistive film mode, Due to not having mechanicalness drive part, it is considered can provide the touch panel of long-life and high reliablity.
But the laminated material of glass or transparent electrode, resin film etc. has intrinsic refractive index, in the refraction of interlayer In the biggish situation of rate difference, the situation of depicting pattern is reduced or recognized there are light transmittance.Especially in touch surface display In, ito film is mainly used as transparent conductive film, but the refractive index of the ito film is 2.0 or so, it is relatively high, therefore, touch-control The reflectivity of the Sensor section of panel is got higher, and identity is deteriorated.In addition, in the ITO base for configuring ITO electrode using setting pattern In the contact panel sensor of plate, since ITO electrode part and the reflectivity of the part of not electrode are significantly different, thus electricity The depicting pattern of pole reflects, and there is a problem of identity difference.
In addition, metal oxide particle due to optical material, electronic component material, magnetic recording material, catalyst material, The multifunction of the various material such as ultraviolet absorption material and high performance are made contributions, and by gazing at, wherein known oxygen Change zirconium particle and shows very high refractive index.In order to realize multifunction or high property brought by such metal oxide particle Energyization, it is desirable that metal oxide particle can be well dispersed within substrate.
For example, disclosing one kind in various solvents in the invention documented by the applied patent document 3 of the present inventor Improve the Zirconia particles of dispersibility.It is covered specifically, disclosing by coverture of more than two kinds, coverture is extremely Few a kind is R1-COOH(R1The alkyl for being 6 or more for carbon number) zirconium oxide nano-particle.In patent document 3, in order to obtain R1The zirconium oxide nano-particle of-COOH covering, makes zirconium oxychloride and R1Water occurs for COONa reaction, the mixing water in the reactant Thermal response (also referred to as hydrothermal synthesis).
In addition, the preparation side as other examples, as the nanoparticle containing Zirconia particles covered by carboxylic acid Method, it is also known that the method including following process: synthesizing, which reacts organic carboxyl acid and metallic compound at a specific ratio, obtains Metal salt of organic carboxylic acid process；The metal salt of organic carboxylic acid and zirconium compounds is set to react synthesis of carboxylic acid-zirconium composite work Sequence；And the compound is supplied to the process (patent document 4) of hydrothermal synthesis.
Citation
Patent document
Patent document 1: Japanese Unexamined Patent Publication 10-48625 bulletin
Patent document 2: Japanese Unexamined Patent Publication 2002-326301 bulletin
Patent document 3: special open 2008-44835 bulletin
Patent document 4: special open 2009-096681 bulletin
Summary of the invention
The purpose of the present invention is to provide a kind of covered in preparation by carboxylate it is useful in metal oxide particle New compound (intermediate compound), and the novel metal oxide particle covered by carboxylate and its new preparation side Method.
The compound of the present invention, for the metal or oxygen alloy category for being bonded with carboxylate, which is characterized in that have specific Ligancy.In addition, metal oxide particle of the invention, which is characterized in that have carboxylate compound as covering ingredient.
That is, the present invention is a kind of compound, which is characterized in that the compound is the compound that following formula (1) indicates,
Mm(-OCO-R)n (1)
In formula (1), M is metal or oxygen alloy category；
R is that carbon number is 1 or more, 20 hereinafter, can have halogen and/or heteroatomic linear chain structure, branched structure, alicyclic ring knot The alkyl of structure or aromatic ring structure；
The integer that m is 1 or more；
When M is metal, its valence mumber is indicated with a valence, when M belongs to as oxygen alloy, the valence for the metal that oxygen alloy belongs to will be constituted When number is indicated with (a+2) valence, the chain length for (i) constituting the methene chain of R is up to 2, and the quantity of the methene chain of chain a length of 2 is When 0 or 1, n is the integer for meeting m≤n≤a × m relationship；(ii) in addition to the chain length for meeting the methene chain of composition R is up to 2 and constitute R chain a length of 2 methene chain quantity be 0 or 1 two essential condition the case where other than, n be meet m≤ The integer of n < a × m relationship.
The M is preferably selected from least one kind of in the group as composed by Ti, Al, Zr, Zn, Sn, oxygen titanium, oxygen zirconium and oxygen tin Metal or oxygen alloy category.In addition, the invention also includes the metal oxide particles obtained by the compound.
The invention also includes had selected from by ester group, ether, amide groups, thioester substrate, thioether group, carbonate group, urethane First carboxylic acid compound of the carboxylic acid of 1 or more substituent group in group composed by base and urea base or (methyl) acrylic acid, And the metal oxide particle that at least two kinds of carboxylic acid compounds of the first carboxylic acid compound other than carboxylic acid compound are covered. The preferred pKa of the first carboxylic acid compound for capped metal oxide particle of the invention is 4.8 hereinafter, first is Carboxylation Closing object or the second carboxylic acid compound has polymeric double bond.
In addition, when understanding the present invention from another side, for the metal of the carboxylate compound covering indicated by following formula (2) Oxide particle.
-OCO-R’ (2)
(wherein, in formula, R ' is saturated hydrocarbyl, and the chain length for constituting the methene chain of the saturated hydrocarbyl is up to 2, and chain length Quantity for 2 methene chain is 0 or 1.)
The preparation method of metal oxide particle of the invention, which is characterized in that in presence of water, heats metalized conjunction Object or oxygen alloy category compound；It is preferred that: (i) reacts in the presence of aromatic hydrocarbon；(ii) relative to 1 mole of metallic compound, instead The amount of seasonable water is 17 moles or less；(iii) it is reacted in the presence of alkali compounds；Deng.
The preparation method of metal oxide particle of the invention, when understanding from another point of view, which is characterized in that in depositing for water Under, the mixture of carbonate and carboxylic acid that the carbonate of metal or oxygen alloy belong to is heated；It is preferred that: (i) is deposited aromatic hydrocarbon In lower reaction；(ii) relative to 1 mole of metallic compound or oxygen alloy category compound, the amount of water when reaction be 17 moles with Under；(iii) it is reacted in the presence of alkali compounds；Deng.
Prepare the compound of the present invention method, which is characterized in that by the carbonate (M is same as described above) of M with have The mixture of the carboxylic acid (R is same as described above) of RCOO base heats；It is preferred that: (i) in the presence of aromatic hydrocarbon, make the carbonate of M with Carboxylic acid reaction with RCOO base；(ii) in the presence of alkali compounds, keep the carbonate of M and the carboxylic acid with RCOO base anti- It answers；Deng.
The present invention, further preferably in the solution of metal salt containing third carboxylic acid etc. and halide, containing not with institute The tetracarboxylic acid bronsted lowry acids and bases bronsted lowry that metal forms compound is stated, by reacting the tetracarboxylic acid bronsted lowry acids and bases bronsted lowry with the halide, to remove halogen Compound.In the preparation method, the solution, containing the latest after the reaction of halide soluble compound it is organic molten Agent, and the second solvent mutually separated with the organic solvent, after so that the reactant of the halide is dissolved in the second solvent, to organic Solvent and the second solvent are separated.
It further include being related to the composition containing the compound and containing the metal oxide particle in addition, of the invention Composition invention.
Further, of the invention, it further include the resin combination for display with transparent planar formed body, feature exists In containing the metal oxide particle.It is described to be used for resin combination of the display with transparent planar formed body, preferred resin The metal oxide particle in composition is 10 mass %-90 mass % in composition.
In addition, the invention also includes be formed by for display with the resin combination of transparent planar formed body by described Planar formed body.Further, the invention also includes layered product and the planar formed bodies made of planar formed body lamination Touch control panel device made of lamination.
The compound of the present invention is the metal or oxygen alloy category for being bonded with carboxylate, due to specific ligancy, It can be used conveniently to prepare metal oxide particle.
In addition, metal oxide particle of the invention, due to being covered by the first carboxylic acid and the second carboxylic acid, thus in various Jie Dispersibility in matter is extremely good, can be applied to various uses.Especially forming the subtle knot of precision using resist as representative It is significant useful during the purposes of structure, dispersion unevenness or development residue can be improved.
Further, metal oxide particle of the invention, due to being covered with carboxylate compound, in solvent and resin Favorable dispersibility, and heat resistance is also excellent, and which passes through by the carboxylate compound covering with above-mentioned formula (2) structure Metal oxide particle is further played.Therefore, metal oxide particle of the invention will not agglomerate in the composition, Its characteristic (high refractive index etc.) can be played, and will not be changed colour even when exposed in high temperature, it is industrially extremely useful.
Detailed description of the invention
Fig. 1 is will be containing the substitution cover type ZrO in aftermentioned embodiment (embodiment 2-1)2The embodiment 2-3 of particle 1 Hardening resin composition 1 (anti-corrosion agent composition) be exposed solidification and develop after test pattern laser microscope shine Piece.
Fig. 2 is will be containing the substitution cover type ZrO in aftermentioned preparation example (preparation example 2-2)2The embodiment 2-8 of particle 5 Hardening resin composition 4 (anti-corrosion agent composition) be exposed solidification and develop after test pattern laser microscope shine Piece.
Fig. 3 is by the hardening resin composition 2 in aftermentioned embodiment (embodiment 2-4) according to " (16) forming characteristic " Evaluation procedure solidify after pyramid array pattern scanning electron microscope (SEM) photo.
Specific embodiment
Metal oxide particle of the invention, can by by metallic compound or oxygen alloy category compound in presence of water Heating is to prepare.Metal oxide particle of the invention, for example, can by by metallic compound or oxygen alloy category compound (with Under, sometimes referred to as metal oxide precursor.) and carboxylate compound or carboxylic acid heat in presence of water to prepare.? It, can be via various compounds (intermediate compound of metal oxide particle) in the preparation process in the present invention.That is, this hair Bright various metal oxide particles can be obtained by each compound described below or each preparation method.Obtained metal Oxide particle, which is characterized in that covered by the carboxylate compound with RCOO base identical with the RCOO base in compound.
In addition, so-called " covering " includes two states in the present invention, i.e., by carboxylate (carboxylic acid compound) or organic compound The state of object and metal oxide particle chemical bonding；And carboxylate (carboxylic acid compound) or the physical attachment of organic compound In the state of metal oxide particle.
Metal oxide particle of the invention can be prepared by following 4 kinds of methods.About each method, details are as follows.
1. first invention (first method)
The metal oxide particle of first invention preparation, which is characterized in that average grain diameter be 1nm or more and be 100nm with Under, the surface of metal oxide particle is covered by organic compound.
The refractive index of metal oxide particle is preferably 1.5 or more, and more preferably 1.55 or more, further preferably 1.6 More than, further preferably 1.65 or more, most preferably 1.7 or more.It can make the combination containing the metal oxide particle as a result, The refractive index of object improves, and can inhibit light from adjacent material to total reflection when the composition incidence.Forming refractive index is 1.7 The metal of above oxide is, for example, Al, Ti, Zr, In, Zn, Sn, La, Y, Ce etc., preferably Al, Ti, Zr, Zn, Sn, Ce (more preferably Al, Ti, Zr, Zn, Sn), particularly preferably Ti, Zr.These metals are used alone or make the ratio of composite oxides It is bigger, refractive index can be made higher.
Organic compound used in covering, as long as can surface coordination in metal oxide particle and/or bonding Organic compound, there is no particular limitation, organic carboxylic acid compounds can be lifted, silane based compound, metal coupling agent, contain epoxy The compound of base, the compound containing hydroxyl, the compound containing amido, compound containing mercapto etc..It is preferably organic Carboxylic acid compound, silane based compound, metal coupling agent, the compound containing epoxy group, more preferably organic carboxylic acid compounds. When the organic compound is organic carboxylic acid compounds, silane based compound, metal coupling agent, compound containing epoxy group, It easy method can be used to be covered on metal oxide particle, and can inexpensively prepare.The total carbon of the organic compound Number, preferably 3 or more.By making total 3 or more carbon number, dispersion of the metal oxide particle in solvent or resin can be improved Property.From the viewpoint of dispersibility, total carbon number of the organic compound is preferably more, and lower limit value is more preferably 4, into one Step preferably 5.On the other hand, total carbon number of the organic compound is preferably 20 or less.It can be improved as a result, and organic compound The yield of the metal oxide particle of coordination and/or bonding.The upper limit of total carbon number of the organic compound is more preferably 18, into One step is preferably 16, and particularly preferably 10.In addition, the organic compound can also have halogen and/or hetero atom, it can also be straight Chain structure, branched structure, alicyclic structure or aromatic ring structure.It is also excellent when the organic compound is organic carboxylic acid compounds Choosing has branch, can inhibit metal oxide particle cohesion as a result,.
Above-mentioned organic carboxylic acid compounds, for example, can enumerate acrylic acid, methacrylic acid, maleic acid, fumaric acid, valeric acid, oneself Acid, enanthic acid, 2 ethyl hexanoic acid, octanoic acid, 2- methyl enanthic acid, 4- methyloctanoic acid, n-nonanoic acid, capric acid, neodecanoic acid, dodecyl acid, ten Tetraalkyl acid, lauric acid, myristic acid, palmitinic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, lactic acid, malic acid, citric acid, Benzoic acid, phthalic acid, M-phthalic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pyruvic acid, butyric acid, Neopentanoic acid, 2,2-dimethylbutyric acid, 3,3- acid dimethyl, 2,2- dimethyl valeric acid, 2,2- diethyl butyric acid, 3,3- diethyl Butyric acid, aphthenic acids, cyclohexane dicarboxylic acid, 2- acryloyl-oxyethyl succinic acid, 2- methacryloxyethyl succinic acid, 2- Acryloyl-oxyethyl hexahydrophthalic acid, 2- methacryloxyethyl hexahydrophthalic acid, 2- acryloxy Ethyl phthalic acid, 2- methacryloxyethyl phthalic acid etc..Wherein, preferably neopentanoic acid, 2,2- dimethyl Butyric acid, 3,3- acid dimethyl, acrylic acid, methacrylic acid, 2 ethyl hexanoic acid, neodecanoic acid, more preferably 2,2- dimethyl butyrate Acid, 3,3- acid dimethyl.Organic carboxylic acid compounds can be used only a kind, can also combine two or more use.
Above-mentioned silane based compound, such as have vinyltrimethoxysilane, vinyltriethoxysilane, 3- methyl-prop Alkene acryloxypropylethoxysilane triethoxysilane, 3- acryloyloxypropyltrimethoxysilane, N- (2- amido ethyl) -3- amido third Base trimethoxy silane, to styryltrimethoxysilane, phenyltrimethoxysila,e, silane based compound can be used only 1 kind, two or more use can also be combined.
Above-mentioned metal coupling agent, for example, have aluminium methoxide, aluminium ethoxide, aluminium isopropoxide, three n-butoxy aluminium, The aluminum alkoxide of tri sec-butoxy aluminum, three tert-butoxy aluminium etc.；Aluminium ethylacetoacetate diisopropoxide, acetoacetate alkyl ester Base diisopropoxy aluminium, monomethacrylates base diisopropoxy aluminium, ketostearic acid aluminium trimer, aluminum isopropoxide acetyl The aluminium system coupling agent of acetic acid alkyl ester list (dioctyl phosphate) etc.；Titanium n-butoxide, four tert-butoxy titaniums, four sec-butoxy titaniums, Purity titanium tetraethoxide, four isobutoxy titaniums, titanium tetramethoxide, four (methoxy propoxy) titaniums, four (methoxyphenoxy) titaniums etc. Alkoxytitanium；Three isostearoyl base titanate esters of isopropyl, three caprylyl titanate esters of isopropyl, four octyls are bis-, and (two-tridecyls are sub- Phosphate) titanate esters, bis- (dioctylphyrophosphoric acid ester) titanate esters of tetra isopropyl, isopropyl three (dioctylphyrophosphoric acid acyloxy) titanium Acid esters, bis- (dioctylphyrophosphoric acid acyloxy) oxygen acetyl titanate esters, bis- (dioctylphyrophosphoric acid acyloxy) ethylene titanate esters etc. Titanium system coupling agent；Four n-propoxyzirconiums, four tert-butoxy zirconiums, four (2- ethyl hexyl oxy) zirconiums, four isobutoxy zirconiums, tetraethoxy The zirconium alkoxide of zirconium, zirconium tetraisopropoxide, four n-propoxyzirconiums, four (2- methyl 2- butoxy) zirconiums etc.；Two n-butoxies (double- 2,4- pentanedione) zirconium, three n-butoxy pentanedione zirconiums, dimethacrylate dibutoxy zirconium etc. zirconium compounds；Metal coupling Agent can be used only a kind, can also combine two or more use.
The above-mentioned compound containing epoxy group, such as 3,4- epoxycyclohexyethylSiOi enylmethyl -3 ', 4 '-epoxy groups can be enumerated Cyclohexenyl group carboxylate, bis- (3,4- expoxycyclohexyl) adipate esters, A Hydrogenated Bisphenol A type epoxy resin, hydrogenation phenolic epoxy The modified dilute ylmethyl -3 ' of 3,4- epoxycyclohexyethylSiOi of resin, cyclohexanedimethanodiglycidyl diglycidyl ether, 6-caprolactone, 4 '-epoxy groups Cyclohexenyl group carboxylate etc., the compound containing epoxy group can be used only a kind, can also combine two or more use.
The above-mentioned compound containing hydroxyl, such as cyclohexanol, n-butyl alcohol, 2- butanol, methyl cyclohexanol, ethylene glycol can be enumerated Single ether, ethylene glycol mono-n-butyl ether, glycol monoethyl ether, 2- hydroxyethylmethacry,ate, 2- hydroxyethyl methacrylate, 2- acrylate, 2- hydroxy propyl methacrylate, 3- acrylate, 3- hydroxypropylmethyl third Olefin(e) acid ester, 2- hydroxybutyl acrylate, 2- hydroxybutyl methacrylate, 3- hydroxybutyl acrylate, 3- hydroxyl fourth Methyl acrylate, 4- hydroxybutyl acrylate, 4- hydroxybutyl methacrylate, polymer containing hydroxyl etc., Compound containing hydroxyl can be used only a kind, can also combine two or more use.
In addition, in first invention, above-mentioned organic carboxylic acid compounds, metal coupling agent, contain epoxy group at silane based compound Compound or other covering metal oxide particle surface organic compound, a kind can be used only, 2 can also be combined Kind is used above.
Metal oxide particle can cover metal oxide particle table by selection for the dispersibility of monomer or polymer The organic compound in face adjusts, but by using the group for showing compatibility to the monomer for constituting medium, can improve particle pair The dispersibility of monomer or the polymer formed by the monomer.For example, with the tool of (methyl) acrylic acid or (methyl) acrylate etc. When having the organic compound covering particle of vinyl, particle can be improved to same (methyl) acrylic acid or (first with vinyl Base) acrylate etc. monomer dispersibility.In addition, can be improved when covering particle with the organic compound with phenyl to benzene The dispersibility of the polymer of the monomer or styrene resin of ethylene etc. or phenolic resin etc., the monomer with phenyl or polymer.
The overlay capacity of organic compound of the invention, it is excellent relative to the metal oxide particle covered with organic compound It is selected as 0.1 mass % or more.Metal oxide particle can be improved as a result, to the dispersibility of resin medium or solvent etc..The key Resultant is more preferably 0.5 mass % or more, further preferably 2 mass % or more.When bonded amount is more, due to being included in per unit The quantitative change of the metal oxide particle of volume is few, is unable to give full play the effect of refractive index raising, thus not preferred.Therefore, institute Stating bonded amount is usually 30 mass % hereinafter, preferably 25 mass % are hereinafter, more preferably 20 mass % or less.
As formed metal oxide particle metal oxide, can be single metal oxide, can for 2 kinds with On oxide solid solution, or may be composite oxides.Single metal oxide, including such as aluminium oxide (Al2O3), titanium oxide (TiO2), zirconium oxide (ZrO2), indium oxide (ln2O3), zinc oxide (ZnO), tin oxide (SnO2), lanthana (La2O3), yttrium oxide (Y2O3), cerium oxide (CeO2), magnesia (MgO), preferably titanium oxide, zirconium oxide, tin oxide.As 2 Kind or more oxide solid solution, ITO, ATO etc. can be enumerated.Composite oxides are, for example, barium titanate (BaTiO3), perovskite (CaTiO3), spinelle (MgAl2O4) etc..
The partial size of metal oxide particle by the calculated crystallization particle diameter of X-ray diffraction analysis and/or can be led to by processing The image that various electron microscope observations obtain is crossed to measure.
Pass through the crystallization particle diameter of the calculated metal oxide particle of X-ray diffraction analysis, preferably 20nm or less.By This, can be improved the transparency of the composition containing the metal oxide particle.The crystallization particle diameter is more preferably 15nm hereinafter, into one Step is preferably 10nm or less.The lower limit of the crystallization particle diameter is usually 1nm or so.
It can be by by metal oxide particle transmission electron microscope by the partial sizes of various electron microscope observations (TEM), electric field radioactive transmission electron microscope (FE-TEM), electric field radioactive scanning electron microscope (FE-SEM) etc. are amplified Observation randomly chooses the length of 100 particle assay its long axis directions, its arithmetic average is asked to determine.
It is preferably in the average grain diameter (average primary particle diameter) of the metal oxide particle of above-mentioned electron microscope observation 100nm or less.The transparency of the composition containing the metal oxide particle can be improved as a result,.Average primary particle diameter is more preferable For 50nm hereinafter, further preferably 30nm is hereinafter, most preferably 20nm or less.The lower limit of average primary particle diameter is usually 1nm Left and right.
The refractive index of metal oxide particle is preferably 1.7 or more.It is can be improved as a result, containing the metal oxide particle The refractive index of composition, and can inhibit light from adjacent material to total reflection when the composition incidence.Formed refractive index 1.7 with On oxide metal, for example, Al, Ti, Zr, In, Zn, Sn, La, Y, Ce etc., preferably Al, Ti, Zr, Zn, Sn, especially Preferably Ti, Zr, Sn.These metals are used alone or the ratio of composite oxides is bigger, and refractive index can be made higher.
The crystalline texture of metal oxide can for example enumerate cubic crystal, regular crystal, monoclinic crystal etc..Particularly preferred crystalline texture The above are regular crystals for whole 70%.When the ratio of regular crystal is big, refractive index can be improved.Tetragonal phase is for monoclinic ratio (the former/the latter) it is 0.8 or more, preferably 1.3 or more, more preferably 2.0 or more.It can also be individually for regular crystal.
As the shape of metal oxide particle, spherical, oval spherical, cubic, rectangular-shape, pyramid can be enumerated Shape, needle-shaped, column, rodlike, tubular, flakey, plate, flake etc..Consider that dispersibility etc. in a solvent, the shape are excellent It is selected as spherical, granular, column etc..
In addition, zirconium oxide has high refractive index when using zirconium oxide as metal oxide, as its crystalline texture, Monoclinic crystal, regular crystal etc. can be enumerated.In the crystalline texture of zirconium oxide, it is known that regular crystal shows highest refractive index, In the case where seeking higher refractive index, the ratio of preferably regular crystal is more.In addition, by adjusting these crystalline textures containing than Example can adjust the refractive index of zirconium oxide.
Metal oxide particle in first invention, in the feature with metal oxide particle described in first invention In range, the feature for the metal oxide particle that can also have aftermentioned second invention described can also have described in third invention Metal oxide particle feature, the feature that can also have the 4th invention described further can also have the group of these features It closes.
Metal component is not particularly limited as long as including the compound for generating metal oxide by hydro-thermal reaction.As Compound containing metal component, can enumerate various metal oxide precursors, for example, the hydroxide of various metals, chloride, Oxychlorination things, sulfate, acetate, acylate, alkoxide etc., further or various metals and the second carboxylic acid Salt.For example, zirconium hydroxide, zirconium chloride, zirconium oxychloride, zirconium oxyacetate, zirconyl nitrate, sulfuric acid can be enumerated using in the example of zirconium Zirconium, zirconium caprylate, 2 ethyl hexanoic acid zirconium, oleic acid oxidation zirconium, acetic acid zirconium, stearic acid zirconium oxide, lauric acid zirconium oxide, tetrabutyl zirconate Deng zirconium alkoxide etc..In addition, using titanium hydroxide, titanium chloride, titanium oxychloride, acetic acid oxygen titanium, nitre using in the example of titanium Sour oxygen titanium, titanium sulfate, sad titanium, oleic acid oxidation titanium, acetic acid titanium, stearic acid titanium oxide, lauric acid titanium oxide, four titanium butoxides It is preferred method whens the alkyl titanium oxide etc. of (such as four titanium n-butoxides) etc..
When using hydro-thermal reaction, the organic solvent containing water can be used.As organic solvent, hydrocarbon, ketone, ether, alcohol can be used Deng.Since the solvent to gasify when hydro-thermal reaction is there is a possibility that reaction is unable to fully carry out, it is therefore preferable that the boiling point under normal pressure is 120 DEG C or more of organic solvent, more preferably 180 DEG C or more, further preferably 210 DEG C or more.Specifically, the last of the ten Heavenly stems can be exemplified Alkane, dodecane, the tetradecane, octanol, decyl alcohol, cyclohexanol, terpinol, ethylene glycol, diethylene glycol, 1,2- propylene glycol, 1,3- the third two Alcohol, 1,4- butanediol, 2,3- butanediol, hexylene glycol, glycerol, Pehanorm, toluene, dimethylbenzene, trimethylbenzene, dimethyl Formamide (DMF), dimethyl sulfoxide (DMSO) etc., preferably dodecane, the tetradecane.
When being separated into 2 layers by adding the organic solvent, can add surfactant etc. formed homogeneous phase state or Suspended emulsified state, usually can be directly with 2 layers of supply hydro-thermal reaction.
Although the case where composition is there is also containing from an adequate amount of water of raw material, does not contain in the feed Moisture or it is seldom when, it is necessary to add moisture in advance before supplying hydro-thermal reaction.
The amount of moisture being present in the system of hydro-thermal reaction, relative to the metal oxide precursor or gold being present in system The molal quantity of the water of the molal quantity of the intermediate compound (hereinafter referred to as metal oxide precursor etc.) of category oxide particle be (water The molal quantity of molal quantity/metal oxide precursor etc.) it is preferably 4/1~100/1, more preferably 8/1~50/1.When less than 4/1, There can be the case where hydro-thermal reaction needs the partial size of long period or obtained particle to become larger.On the other hand, more than 100/ When 1, in addition to the metal oxide precursor being present in system is less, thus other than yield decline, there is no special problems.
The pressure of hydro-thermal reaction, preferably 0.5MPa or more, more preferably 0.6MPa or more.The upper limit of pressure, usually For 3.0MPa hereinafter, preferably 2.0MPa hereinafter, more preferably 1.5MPa hereinafter, particularly preferably 1.0MPa or less.
The reaction temperature of hydro-thermal reaction, preferably 100 DEG C or more, more preferably 140 DEG C or more, further preferably 160 DEG C or more.The upper limit of hydro-thermal process temperature, is not particularly limited, preferably 300 DEG C hereinafter, more preferably 250 DEG C hereinafter, into One step is preferably 220 DEG C or less.Hydrothermal conditions, for example, 5-50 hour, preferably 10-40 hour.When hydro-thermal reaction Atmosphere is not particularly limited, preferably the atmosphere of inert gases of nitrogen, argon gas etc..
The method for making organic compound be coordinated and/or be bonded with metal oxide particle of the invention, in addition to via above-mentioned Metal oxide precursor method other than, such as can also be above-mentioned by being added in the solvent dispersions of metal oxide particle Coverture is heated to prepare.As long as the solvent used has the dispersibility of appropriateness to metal oxide particle, do not have There is special limitation.For example, benzene,toluene,xylene, hexamethylene etc. can be used.As long as the concentration appropriate adjustment of metal oxide is Can, but preferably 0.1-50 mass % or so.As long as the dosage appropriate adjustment of coverture, usually relative to metal oxide Particle is 1-60 mass %.As long as heating temperature appropriate adjustment, usually 30 to 180 DEG C or so, preferably 40-150 DEG C, More preferably 50-130 DEG C.As long as reaction time also appropriate adjustment, usually 0.1-10 hours, preferably 0.3-3 hours Left and right.
The preparation method of metal oxide particle in first invention, it is possible to use it is aftermentioned second, third, the four directions Method can also be synthesized by well known method.For example, the progress under metallic compound and for the coexisting of the organic compound of covering Hydro-thermal reaction is come the method that obtains metal oxide particle；In advance by for covering organic compound and metallic compound synthesize Intermediate compound, the method that metal oxide particle is obtained by the hydro-thermal reaction of the intermediate compound；In the gold modulated in advance Belong to the method etc. covered on oxide microparticle using the organic compound for covering, since these methods can be easily The metal oxide particle covered by organic compound is obtained, thus is preferred synthetic method.
2. the second invention (second method)
Second invention, including compound and metal oxide particle also further comprise their preparation method.
Firstly, to the compound used in the second invention (second method) (intermediate compound of metal oxide particle) It is described in detail.
The compound used in the second invention is preferably the compound with following characteristics: being indicated for following formula (1) Compound,
Mm(-OCO-R)n (1)
In formula (1), M is metal or oxygen alloy category；
R is that carbon number is 1 or more, 20 hereinafter, can have halogen and/or heteroatomic linear chain structure, branched structure, alicyclic ring knot The alkyl of structure or aromatic ring structure；
The integer that m is 1 or more；
When M is metal, its valence mumber is indicated with a valence, when M belongs to as oxygen alloy, the valence for the metal that oxygen alloy belongs to will be constituted When number is indicated with (a+2) valence, the chain length for (i) constituting the methene chain of R is up to 2, and the quantity of the methene chain of chain a length of 2 is When 0 or 1, n is the integer for meeting m≤n≤a × m relationship；(ii) in addition to the chain length for meeting the methene chain of composition R is up to 2 and constitute R chain a length of 2 methene chain quantity be 0 or 1 two essential condition the case where other than, n be meet m≤ The integer of n < a × m relationship.
When for the compound, it is bonded with carboxylate since metal in the compound or oxygen alloy belong to, the compound With specific ligancy, thus it can be used conveniently to prepare metal oxide particle.
M indicates metal or oxygen alloy category, can arbitrarily select these a kind or more.M is preferably selected from transition metal, typical case One or more of metal and their oxygen alloy category (partial oxide), more preferably selected from transition metal and transition metal One or more of oxygen alloy category (partial oxide).Oxygen alloy category (partial oxide) refers to the state of metal oxidation, and metal Coordination and unused oxygen element be saturated, the meaning that can be bonded with carboxylate.
M is preferably selected from least one kind of in the group as composed by Ti, Al, Zr, Zn, Sn, oxygen titanium, oxygen zirconium and oxygen tin.
R is that carbon number is 1 or more, 20 hereinafter, can have halogen and/or heteroatomic linear chain structure, branched structure, alicyclic ring knot The alkyl of structure or aromatic ring structure, preferably linear chain structure, branched structure, alicyclic structure saturated hydrocarbyl.Under the carbon number of R Limit preferably 3 or more, more preferably 4 or more.The upper limit of the carbon number of R is preferably 15 hereinafter, more preferably 12 or less.
The RCOO base (carboxylate) for being bonded to M, the chain length for (i) constituting the methene chain of R are up to 2, and chain length The case where quantity for 2 methene chain is 0 or 1, and the chain length of the methene chain of (ii) in addition to meeting composition R are up to 2, with And constitute R chain a length of 2 methene chain quantity be 0 or 1 two essential condition the case where other than, the n in above-mentioned formula (1) The condition that should meet is different.
(i) chain length for constituting the methene chain of R is up to 2, and the quantity of the methene chain of chain a length of 2 is 0 or 1 (that is, R Methene chain without chain a length of 2, or there is the methene chain of chain a length of 2) the case where.
At this point, indicating its valence mumber with a valence when M is metal, when M is that oxygen alloy belongs to, the metal of oxygen alloy category will be constituted When valence mumber is indicated with (a+2) valence (that is, when the bonding ligancy of M is indicated with a), n is to meet m≤n≤a × m relationship Integer.That is, the coordination of M can be all bonded with carboxylate, there may also be the coordinations for the M not being bonded with carboxylate.Key The compound for having the second invention of such carboxylate is closed, since the R is hydrophobicity, thus especially hydrophobic molten Dispersibility in agent or hydrophobic resin etc. becomes well, operability to can be improved.Further, obtained by the compound Dispersibility of the metal oxide particle in hydrophobic solvent or hydrophobic resin etc. also becomes good.Further, due to R In the chain length of methene chain be up to 2, and the quantity of the methene chain of chain a length of 2 is 0 or 1, thus be can be improved through the change Close the heat resistance of the obtained metal oxide particle of object.
The chain length of methene chain refers to unsubstituted methylene (- CH2) continuous quantity, preferably 1, or 0.
Total carbon number in above-mentioned R, preferably 3 or more.By making 3 or more total carbon number in R, metal oxide can be improved Dispersibility of the particle in solvent or resin.From the viewpoint of dispersibility, total carbon number in R is preferably more, lower limit value More preferably 4, further preferably 5.On the other hand, total carbon number in R is preferably 20 or less.It can increase as a result, through the change Close the metal oxide component of the obtained metal oxide particle covered by carboxylate compound of object.Total carbon number in R The upper limit is more preferably 10, further preferably 6, particularly preferably 5.
In addition, R preferably has branch, the cohesion of metal oxide particle can inhibit as a result,.
In above-mentioned formula (1), it is-R that particularly preferred carboxylate, which is-the R in formula,1-R2-R3-(R4)p-H.Wherein, 0 p Or 1, R1-R4For-CH2-、-CR5R6(wherein ,-CR5R6It does not include-CH2Any one of), and R1-R4In any one For-CR5R6-.In addition, the R5And R6Can for it is identical can also be different, be any one of hydrogen atom, methyl, ethyl, propyl. These R5And R6, preferably without containing the group with three-level hydrogen.Further, R1-R4With multiple-CR5R6When, R5、R6Can because (- CR5R6) unit and it is different.The R5And R6, preferably methyl, ethyl, particularly preferably methyl.In addition, R5、R6Preferably straight chain Shape.
Above-mentioned-R1-R2-R3-(R4)p- H (p=0,1), preferably R1、R2Either one or two of be-CR5R6(especially-C (CH3)2-)。
Above-mentioned-R1-R2-R3-(R4)p- H (p=0,1), particularly preferred R1For-CH2-、-C(CH3)2Any of, R2-R4 For-CH2-、-C(CH3)2、-CH(CH3Any of)-, and R1-R4Either one or two of be-C (CH3)2-。
The carboxylic acid of above-mentioned carboxylate is formed, such as butyric acid, neopentanoic acid, 2,2- acid dimethyl, 3,3- diformazan can be enumerated Base butyric acid, 2,2- dimethyl valeric acid, 2,2- diethyl butyric acid, 3,3- diethyl butyric acid, preferably neopentanoic acid, 2,2- dimethyl butyrate Acid, 3,3- acid dimethyl, more preferably 2,2- acid dimethyl, 3,3- acid dimethyl.
Carboxylate in second invention can be used only a kind, can also combine two or more use.Combine two or more In use, the chain length at least constituting the methene chain of a kind of R is up to 2, and the quantity of the methene chain of chain a length of 2 is for 0 or 1 It can.
The chain length for constituting the methene chain of R is up to 2, and the quantity of the methene chain of chain a length of 2 be 0 or 1 (i) feelings Under condition, especially M be preferably selected from it is at least one kind of in the group as composed by Ti, Al, Zr, Zn, Sn, oxygen titanium, oxygen zirconium and oxygen tin, It is at least one kind of in more preferably Zr and oxygen zirconium.
(ii) in addition to the chain length for meeting the methene chain of composition R is up to 2, the number of the methene chain of the chain a length of 2 of R is constituted Other than the case where two essential condition that amount is 0 or 1
At this point, indicating its valence mumber with a valence when M is metal, when M is that oxygen alloy belongs to, the metal of oxygen alloy category will be constituted When valence mumber is indicated with (a+2) valence, n is the integer for meeting m≤n < a × m relationship.I.e. in the coordination of M, there are not with carboxylate The coordination of base bonding.
It is 1 or more, 20 below to have halogen and/or heteroatomic linear chain structure, branch link that R at this time, which is in carbon number, In the alkyl of structure, alicyclic structure or aromatic ring structure, it is up to 2 in addition to meeting the chain length of methene chain of composition R, constitutes All alkyl other than the case where two essential condition that the quantity of the methene chain of the chain of R a length of 2 is 0 or 1.As such Alkyl, such as valeric acid, caproic acid, 2 ethyl hexanoic acid, octanoic acid, neodecanoic acid, lauric acid, myristic acid, palmitinic acid, tristearin can be enumerated Acid, oleic acid, linoleic acid, linolenic acid, lactic acid, malic acid, citric acid, benzoic acid, phthalic acid, M-phthalic acid, oxalic acid, Malonic acid, succinic acid, glutaric acid, adipic acid, fumaric acid, maleic acid, pyruvic acid etc..
Then, the preparation method of compound involved in the second invention is illustrated, compound according to the present invention Preparation method, be not limited to the following method.
The compound of second invention, can be by making metallic compound or oxygen alloy category compound (for example, the change of the M Close object), it is reacted with carboxylate compound or carboxylic acid (such as carboxylate compound or carboxylic acid of the RCOO base with the R) to make It is standby, preferably heated (hereinafter, also referred to as " being heat-treated ".).It, can as metallic compound or oxygen alloy category compound Carbonate, the metal halide (chloride etc.), oxygen alloy category halide (chlorine belonged to using the carbonate of such as metal, oxygen alloy Compound etc.), metal oxide or metal alkoxide.
For example, metal be zirconium example in, can enumerate zirconium carbonate, zirconyl carbonate, zirconium hydroxide, zirconium chloride, zirconium oxychloride, Zirconium oxyacetate, zirconyl nitrate, zirconium sulfate, zirconium caprylate, oleic acid oxidation zirconium, acetic acid zirconium, stearic acid zirconium oxide, lauric acid zirconium oxide, Zirconium alkoxide compound of tetrabutyl zirconate etc. etc..
Carboxylate compound used in the preparation method of the compound of second invention or carboxylic acid, using with above-mentioned (i) or (ii) respectively as defined in R RCOO compound (carboxylate compound) or RCOOH (carboxylic acid).
The amount of carboxylate compound or carboxylic acid, is not particularly limited, such as relative to metallic compound or oxygen alloy categoryization Closing 1 mole of object can be 3 moles or less.
The carbonate (such as carbonate of the M) and carboxylic acid (example for particularly preferably belonging to the carbonate of metal or oxygen alloy Such as carboxylic acid of the RCOO base with the R) heat treatment, to prepare the compound of the second invention.
The carbonate that the carbonate or oxygen alloy of metal belong to, such as Zr2(CO3)(OH)2O2Or O=Zr (CO3) etc., relative to 1 mole of M (that is, carbonate that the carbonate of metal or oxygen alloy belong to), CO3Ratio be less than a moles, (preferably (a-1) rubs You hereinafter, especially (a-1.5) mole) metal carbonate or oxygen alloy belong to carbonate (wherein, a refers to that M is bonding and matches Digit).In the reaction of carbonate and carboxylic acid that the carbonate or oxygen alloy of metal belong to, acid-base reaction is generated by heat treatment, The CO of the carbonate3A part be replaced as OCOR, generate the metal or oxygen alloy for being bonded with carboxylate of the second invention Belong to.When the carbonate belonged to using metal carbonate or oxygen alloy, can effectively it be obtained by the carboxylic acid fewer than theoretically a moles It is bonded with the metal or oxygen alloy category of carboxylate.
It is used to prepare the heat treatment temperature of the compound of the second invention, preferably 25 DEG C or more, more preferably 50 DEG C or more, Further preferably 70 DEG C or more.Heat treatment time, for example, 30 minutes~4 hours, preferably 1-3 hours.
The atmosphere of heat treatment does not limit, preferably the atmosphere of inert gases of nitrogen, argon gas etc..
Then, the metal oxide particle of the second invention is illustrated.The metal oxide particle of second invention can lead to Crossing heats metallic compound or oxygen alloy category compound in presence of water to prepare.The metal oxide grain of second invention Son, for example, can by by metallic compound or oxygen alloy category compound and carboxylate compound or carboxylic acid, in presence of water into Row heat treatment, can also be via the compound of the present invention in the preparation process to prepare.That is, metal oxide grain of the invention Son can be obtained by the compound of the present invention, can be obtained by having RCOO base identical with the RCOO base in the compound of the present invention The metal oxide particle that is covered of carboxylate compound.
The overlay capacity of carboxylate compound in the metal oxide particle of second invention, covers relative to carboxylate compound The metal oxide particle of lid, preferably 0.1 mass % or more.Metal oxide particle can be improved as a result, in solvent etc. Dispersibility.The overlay capacity, more preferably 0.5 mass % or more, further preferably 2 mass % or more.The overlay capacity compared with When more, the quantitative change of the metal oxide particle itself as contained by per unit volume is few, plays refraction with being unable to fully The improvement effect of rate etc., it is thus not preferred.Therefore, the overlay capacity, for example, 30 mass % hereinafter, preferably 25 mass % with Under, more preferably 20 mass % or less.In addition, by the way that (carboxylate compound covers rubbing for the metal in metal oxide particle That number)/(molal quantity of metallic compound or the metal in oxygen alloy category compound) × 100 metal oxide particles found out Yield is, for example, 50% or more, and preferably 70% or more, more preferably 80% or more.The upper limit of the yield is usually 98% left side It is right.
It is formed by the metal oxide of the obtained metal oxide particle of compound of the second invention, metal oxide Crystalline texture, the partial size of metal oxide particle, crystallization particle diameter, average grain diameter, shape, refractive index can quote above-mentioned first hair Bright explanation.
It, can in presence of water, by metallic compound as the method that the compound via the second invention prepares particle Or the mixture heating of oxygen alloy category compound and carboxylate compound or carboxylic acid, specific step can first make for (i) Metallic compound or oxygen alloy category compound, and carboxylate compound or carboxylic acid reaction, after synthesizing the compound of the present invention, at it The leading synthesis compound type that water is heat-treated is added in reactant, or (ii) is by closing metallic compound or oxygen Metallic compound and carboxylate compound or carboxylic acid and water are heat-treated, while synthesizing the compound of the present invention, synthesis The simultaneously synthesizing type of compound and metal oxide of metal oxide particle.In the present specification, will add in (i) sometimes Add the process that water is heat-treated, and reaction and heat treatment procedure in (ii), referred to as " hydro-thermal process process ".First The step of (i) of row synthesis compound type, with (ii) of compound and the simultaneously synthesizing type of metal oxide the step of compared with, can drop Pressure when low-heat processing.
In second invention, in the process (i) or (ii), water contained in the mixture, relative to metal compound 1 mole of object or oxygen alloy category compound, for example, 5 moles or more, preferably 7 moles or more, more preferably 10 moles or more.Institute Water contained in the mixture is called, refers to the meaning of existing all water in the mixture, not only includes the amount of the water of addition, It further include water contained in the compound of the carbonate of metal or carbonate etc. that oxygen alloy belongs to, or the water as solvent.
Hydro-thermal process temperature, preferably 100 DEG C or more, more preferably 140 DEG C or more, further preferably 160 DEG C or more. The upper limit of hydro-thermal process temperature, is not particularly limited, preferably 300 DEG C hereinafter, more preferably 250 DEG C hereinafter, further preferably It is 220 DEG C or less.Hydrothermal conditions, for example, 5-50 hour, preferably 10-40 hour.
In the preparation method of the metal oxide particle of the second invention, pressure when hydro-thermal process, preferably 0.5MPa More than, more preferably 0.6MPa or more.The upper limit of pressure, usually 3.0MPa hereinafter, preferably 2.0MPa hereinafter, more preferably For 1.5MPa or less (especially 1.0MPa or less).In addition, atmosphere when hydro-thermal process and be not limited, preferably nitrogen, argon gas Deng atmosphere of inert gases.
In second invention, when especially with zirconium carbonate and carboxylic acid prepare compound, by the mixed of zirconium carbonate and carboxylic acid Object (usually containing the water for being 5 moles or more relative to 1 mole of zirconium) heat treatment is closed, adjusts the amount of carboxylic acid, or make the mixing Object further contains aromatic hydrocarbon (that is, in the presence of aromatic hydrocarbon, making the carbonate of M and the carboxylic acid reaction with RCOO base), adjusts The amount (i.e. the amount of the carbonate of M and water when carboxylic acid reaction with RCOO base) of the whole water comprising in the mixture, or in alkali Property compound in the presence of be heat-treated (that is, in the presence of alkali compounds, make the carbonate of M with RCOO base Carboxylic acid reaction) etc., due to can adjust the ratio of the regular crystal in finally obtained cover type Zirconia particles, thus preferably. This is respectively described below.
The carboxylic acid is relative to 1 mole of zirconium of mole, preferably less than 2 moles (essential condition A).The mole of carboxylic acid It is fewer, it more can be improved the ratio of the regular crystal in cover type Zirconia particles.The mole of carboxylic acid, more preferably 1.5 moles Hereinafter, further preferably 1 mole hereinafter, further preferably 0.7 mole or less.The mole of carboxylic acid is preferably 0.2 mole More than.When carboxylic acid amount is very few, the overlay capacity of carboxylate compound can be become inadequate.The mole of carboxylic acid is more preferably 0.3 and rubs More than you, further preferably 0.4 mole or more.
Since carboxylic acid can be improved by making the mixture of the zirconium carbonate and carboxylic acid contain aromatic hydrocarbon (essential condition B) The ratio of regular crystal in the Zirconia particles (cover type Zirconia particles) of ester compounds covering, thus preferably.Aromatic hydrocarbon is excellent It is selected as the alky-substituted aromatic hydrocarbon that total carbon number is 7 or more, more preferably total carbon number is that the alkyl of 8 or more (especially 9 or more) takes For aromatic hydrocarbon, specially toluene, ethylbenzene, dimethylbenzene, diethylbenzene, trimethylbenzene；With dimethylbenzene, trimethylbenzene (especially 1, 2,4- trimethylbenzene).In addition, the aromatic hydrocarbon content in the mixture (mixture of zirconium carbonate and carboxylic acid), relative to zirconium 100 mass parts of carbonate, it is more than preferably 30 mass parts, it is more than more preferably 40 mass parts, further preferably 50 mass Part or more.On the other hand, when the content surplus of aromatic hydrocarbon, the yield of the cover type Zirconia particles finally obtained can decline.Cause This, the content of the aromatic hydrocarbon in the mixture, relative to 100 mass parts of carbonate of zirconium, such as preferably 400 mass parts with Under, more preferably 200 below the mass, and further preferably 100 below the mass.In addition, in compound and metal oxide In the case where the step of (ii) of simultaneously synthesizing type, preferably add (when compound synthesis) in zirconium carbonate and carboxylic acid reaction Add aromatic hydrocarbon.
The amount of water in the mixture of the zirconium carbonate and carboxylic acid is preferably 17 moles or less relative to 1 mole of zirconium (essential condition C).By inhibiting the water in the mixture, the ratio of the regular crystal of cover type Zirconia particles can adjust. Water in the mixture, relative to 1 mole of zirconium, preferably 15 moles hereinafter, more preferably 10 moles or less.
In second invention, the heat treatment (essential condition D) is preferably carried out in the presence of alkali compounds.By in alkalinity It is heat-treated in the presence of compound, not only can adjust the ratio of the regular crystal of cover type Zirconia particles, also can be improved and cover The yield of cap-type Zirconia particles.Relative to 1 mole of zirconium, alkali compounds is preferably 0.1 mole or more, more preferably 0.2 Mole or more, further preferably 0.5 mole or more.The upper limit of alkali compounds amount usually 2 is rubbed relative to 1 mole of zirconium You are hereinafter, preferably 0.8 mole or less.In addition, the case where step of (ii) of reaction and heat treatment simultaneous type, in the carbonic acid of zirconium After salt and carboxylic acid reaction, preferably addition alkali compounds is heat-treated.
The alkali compounds includes the alkali of any definition of the Taide Bu Langsi alkali, lewis base etc., and can be nothing Any one in machine compound, organic compound.Wherein, alkali metal salt, alkali salt and 1~3 grade of amine are preferably selected from In at least one or more alkali compounds, the more preferably hydroxide, organic of the hydroxide of alkali metal, alkaline-earth metal One or more of amine compounds, the particularly preferably hydroxide of alkali metal.As alkali compounds, most preferably hydroxide Sodium.
The essential condition A-D, can satisfy any one essential condition, can also meet two or more simultaneously.
In addition, essential condition A (being related to the essential condition of carboxylic acid amount), essential condition B (are related in above-mentioned essential condition A-D The essential condition of aromatic hydrocarbon) and essential condition D (being related to the essential condition of alkali compounds), preferably satisfy the compound Preparation method.In the preparation method of compound, essential condition A, B and D can satisfy any one essential condition, can also be with Meet two or more simultaneously.
Especially in the metal oxide particle for obtaining being covered by the carboxylate compound containing RCOO base, wherein in R For meet carbon number be 1 or more, 20 hereinafter, can have halogen and/or heteroatomic linear chain structure, branched structure, alicyclic structure or In the alkyl of aromatic ring structure, it is up to 2 in addition to meeting the chain length of methene chain of composition R, and constitute the chain a length of 2 of R Methene chain quantity be 0 or 1 two essential condition alkyl other than (that is, R by the second invention compound (ii) rule Alkyl periodically), it is preferred to use in presence of water, the mixing of carbonate and carboxylic acid that the carbonate of metal or oxygen alloy are belonged to The preparation method that object is heated.
The metal oxide particle of second invention, for the carboxylate compound with carboxylate shown in following formula (2) When the metal oxide particle of covering, as described above, can be via (i) in the compound of the present invention the case where compound, It can not also be via.Metal oxide particle when not via the compound of the present invention (i), such as can enumerate in metal oxide grain On son in a manner of organic synthesis the method for addition carboxylate compound (for example, will have the carboxylic acid of R ' COO structure or silane even Join agent, the method handled by dry method or damp process unmodified metal oxide particle) etc..
-OCO-R’ (2)
(wherein, in formula, R ' is saturated hydrocarbyl, and the chain length for constituting the methene chain of the saturated hydrocarbyl is up to 2, and chain length Quantity for 2 methene chain is 0 or 1.)
It, can be entirely by reference in addition, the R ' in above-mentioned formula (2), identical as R the case where (i) of the compound of the second invention The explanation of the R of the case where (i) of the compound of the present invention.In addition, the M phase for the type of metal, with the compound of the present invention Together.
For the metal oxide particle of the carboxylate compound covering indicated by above-mentioned formula (2), metal oxidation is formed The type of the metal oxide of object particle, the overlay capacity of carboxylate compound, partial size, shape of particle, refractive index, crystalline texture, It is identical as the metal oxide particle (that is, by the obtained metal oxide particle of the compound of the present invention), it can join completely According to their explanation.
Second invention further includes the preparation method of metal oxide particle, which is characterized in that in presence of water, will be golden The mixture heating of the metallic compound or oxygen alloy category compound and carboxylic acid of the carbonate that the carbonate or oxygen alloy of category belong to.This It, can by using the metallic compound or oxygen alloy category compound of the carbonate that the carbonate or oxygen alloy of metal belong in invention Be effectively prepared metal oxide particle.
The metallic compound or oxygen alloy category compound for the carbonate that the carbonate or oxygen alloy of metal belong to, there is no especially Limit, in the case where the refractive index for considering metal oxide particle, for example, Al, Ti, Zr, In, Zn, Sn, La, Y, Ce, these Partial oxide carbonate, preferably Al, Ti, Zr, Zn, Sn, Ce, these partial oxide carbonate, further Preferably Al, Ti, Zr, Zn, Sn, these partial oxide carbonate, the particularly preferably carbon of the partial oxide of Ti, Zr Hydrochlorate.
Carboxylic acid can enumerate in the compound of the present application above-mentioned illustrated by carboxylic acid.
The metal oxide particle can be prepared as with the method for the metal oxide particle of preparation aforementioned present invention. Other essential conditions refer to for example using metal carbonate or oxygen alloy belong to carbonate metallic compound or oxygen close The type and its blend ratio of metallic compound or carboxylic acid, water, the temperature of hydro-thermal process, water when specific steps, hydro-thermal process The pressure condition of heat treatment, the atmosphere of hydro-thermal process, essential condition A-D, can be entirely by reference to these conditions.
Further, the second invention can also be with the first invention, the invention of aftermentioned third, mutual group respectively of the 4th invention It closes.
That is, the method as metal oxide particle documented by the second invention of preparation, can quote first invention portion respectively The preparation side of the preparation method of metal oxide particle documented by point, metal oxide particle documented by third invention section The preparation method of metal oxide particle documented by method, the 4th invention section.
In addition, compound (intermediate compound of metal oxide particle) documented by the second invention and metal oxide grain Son can also have metal oxide particle documented by first invention in the range of having feature documented by the second invention Feature, can also have third invention record compound and metal oxide particle feature, can also have the 4th invention remember The feature of the metal oxide particle of load can also be further combined with these features.
3. third invents (third method)
Third is invented in (third method), maximum to be characterized in that, for covering the carboxylic acid compound of metal oxide For two or more.Further, have by selection selected from by ester group, ether, amide groups, thioester substrate, thioether group, carbonate group, urine The carboxylic acid or (methyl) acrylic acid of 1 or more substituent group in the group of alkyl and urea base composition, as the carboxylic for covering 1 kind of acid compound, realizes the dispersibility in a variety of media.Carboxylic acid compound is bonded with Metal Oxide Chemical, or Carboxylic acid is formed together with hydrogen atom or cationic atom or its salt is attached to metal oxide.Next coming in order are illustrated.
The metal oxide particle of third invention, the dispersibility in various media is extremely good, can be applied to various use On the way.Especially exceedingly useful on the way as the accurate microstructural use of the formation of representative using resist, can improve dispersion it is uneven or Development residue.
Firstly, being illustrated to the first carboxylic acid compound used in third invention.In third invention, for covering gold In the carboxylic acid compound for belonging to oxide, it is selected from using having by ester group, ether, amide groups, thioester substrate, thioether group, carbonic ester The carboxylic acid of 1 or more substituent group (hereinafter, sometimes referred to as specified substituent) in group composed by base, urethane groups and urea base or (methyl) acrylic acid (hereinafter referred to as the first carboxylic acid compound).By using these compounds, object particle can be oxidized metal Hydrophobicity and hydrophilic balance improve, and are remarkably improved in hydrophilic solvent, hydrophobic solvent, monomer, oligomer, polymerization Dispersibility in the various media of object etc..First carboxylic acid compound is (methyl) acrylic acid, or takes with a kind or more specific Dai Ji can also have multiple identical or different specified substituents, can also be further with taking other than specified substituent Dai Ji.Specified substituent, from obtain it is ease from the viewpoint of, preferably ester group, ether, amide groups, further preferably ester Base, ether.There is 1 or more specified substituent in 1 molecule, although the upper limit is not particularly limited, from preparation gold Operability consideration when category oxide particle, preferably 20 or less.More preferably 10 hereinafter, further preferably 5 with Under.
Commercially available product also can be used in first carboxylic acid compound, can also be synthesized by well known synthetic method.For example, can generation It exemplifies to table: the method that ester compounds are obtained by various alcoholic compounds and binary acid or anhydride reaction；Pass through epoxidation Close the method for reacting to obtain ester compounds of object or glycidyl compound and binary acid；Pass through reacting for alcohol or water and cyclic ethers To the method for ether compound；By amine compounds and binary acid or acid anhydrides react amide to compound method；Pass through sulphur The method for reacting to obtain thioester compound of alcoholic compound and binary acid or acid anhydrides；Thioether chemical combination is obtained by the desulfurization of two mercaptan The method etc. of object.
The α carbon of the carboxyl of first carboxylic acid compound can be any one of secondary carbon, tertiary carbon, quaternary carbon or aromatic series carbon.This Outside, the carboxyl of the first carboxylic acid compound can be one or more, in order to avoid particle occurs when preparing metal oxide particle Between be crosslinked, preferably 3 hereinafter, more preferably 2, most preferably 1.
From with aftermentioned second carboxylic acid exchange easiness from the viewpoint of, the pKa of the first carboxylic acid compound is preferably 4.8 Hereinafter, more preferably 4.7 hereinafter, further preferably 4.6 or less.The pKa of carboxylic acid compound is using soft by calculating chemistry The calculated value of part ACD/pKa version 10.01 (Advanced Chemistry Development.Ince society system) institute.
The covering metal oxide particle that third is invented is admixed in solidification compound, it is excellent when being used for various uses Select the first carboxylic acid compound that there is polymeric double bond.By having polymerism double on the covering ingredient of metal oxide particle Key can blend ingredient copolymerization with others, thus the problem of agglomerating or oozing out will not occur in solidification, even if in solidfied material It can also maintain good dispersity.In addition, can have polymeric double bond in the first carboxylic acid compound, aftermentioned second is Carboxylation Polymeric double bond can also be had by closing in object.In addition, when using first or second carboxylic acid compound of more than two kinds, at least 1 in them Kind has polymeric double bond.
As the concrete example of the first carboxylic acid compound, acrylic acid, methacrylic acid 2- acryloyl-oxyethyl amber can be enumerated Amber acid, 2- methacryloxyethyl succinic acid, 2- acryloyl-oxyethyl hexahydrophthalic acid, 2- methacryloxypropyl Base ethyl hexahydrophthalic acid, 2- acryloyl-oxyethyl phthalic acid, 2- methacryloxyethyl O-phthalic Acid etc..Wherein, it is preferable to use acrylic acid, 2- acryloyl-oxyethyl succinic acid, 2- acryloyl-oxyethyl hexahydro O-phthalic Acid, 2- acryloyl-oxyethyl phthalic acid.
First carboxylic acid compound can be used only a kind, can also combine two or more use.Cover metal oxide grain The ratio of first carboxylic acid compound of son, relative to 100 mass parts of metal oxide particle after covering, the first carboxylic acid compound It is more than preferably 0.1 mass parts.Dispersion of the metal oxide particle in solvent etc. when can be improved preparation as a result, or in product Property.The amount of first carboxylic acid compound, more than more preferably 0.5 mass parts, more than further preferably 2 mass parts.Overlay capacity compared with When more, the quantitative change of the metal oxide particle contained by per unit volume is few, thus not preferred.Therefore, the first carboxylic acid compound Amount, usually 30 below the mass, and preferably 25 below the mass, and more preferably 20 below the mass.
Then, the second carboxylic acid compound is illustrated.As long as the second carboxylic acid is the carboxylic acid other than first carboxylic acid, It is not particularly limited, from the viewpoint of aftermentioned preparation section, it is preferred to use straight-chain carboxylic acid that total carbon number is 3 or more, branch Chain carboxylic acid, cyclic carboxylic acids or aromatic carboxylic acid.Wherein, particularly preferred branched carboxylic acid.By using branched carboxylic acid, can have Effect ground inhibits the cohesion of metal oxide particle.
Second carboxylic acid compound can be used only a kind, can also combine two or more use.Metal oxide particle With the ratio for the second carboxylic acid compound for covering the metal oxide particle, relative to 100 mass parts of metal oxide particle, the Dicarboxylic acid compound is preferably 0.1 mass parts or more.Metal oxide particle when can be improved preparation as a result, or in product is molten Dispersibility in agent etc..The amount of second carboxylic acid compound, it is more than preferably 0.5 mass parts, further preferably 2 mass parts with On.When overlay capacity is more, the quantitative change of the metal oxide particle contained by per unit volume is few, thus not preferred.Therefore, second The amount of carboxylic acid compound, usually 30 below the mass, and preferably 25 below the mass, and more preferably 20 below the mass.
In addition, total overlay capacity of first carboxylic acid compound and the second carboxylic acid compound, relative to 100 mass parts, It is more than preferably 0.2 mass parts, it is more than more preferably 1 mass parts, it is more than further preferably 2 mass parts, be 40 mass parts with Under, preferably 35 below the mass, and more preferably 30 below the mass.
The mass ratio of the overlay capacity of first carboxylic acid and the second carboxylic acid, in terms of the first carboxylic acid/second carboxylic acid, preferably 100/1 ~1/100, more preferably 50/1~1/50, further preferably 30/1~1/30.It, can by adjusting overlay capacity in the range The compatibility for improving gained a variety of media such as metal oxide particle and hydrophily, hydrophobicity, can be improved dispersibility.
For the metal oxide of third invention, the metal oxide of metal oxide particle, metal oxide are formed Crystalline texture, the partial size of metal oxide particle, crystallization particle diameter, average grain diameter, shape, refractive index, can quote described first The explanation of invention.
Hereinafter, being illustrated to the representative preparation method of the metal oxide particle of third invention, but each process can It suitably changes.Furthermore, it is contemplated that sometimes the metal oxide particle that third is invented is known as taking below when the feature of preparation method For cover type particle.The particle (replacing cover type particle) of third invention can be prepared by following steps: firstly, modulation quilt The particle (hereinafter, sometimes referred to as cover type particle) of second carboxylic acid compound covering then can be by the cover type particle surface Second carboxylic acid is replaced with the first carboxylic acid compound.
Firstly, being illustrated to the modulation of cover type particle.Cover type particle is by presence of water, making metal component Hydro-thermal reaction is carried out with the second carboxylic acid compound and is obtained.Illustrating for hydro-thermal reaction can quote saying for aforementioned first invention Bright, the second invention explanation.
In third invention, by making metal component and the second carboxylic acid compound carry out hydro-thermal reaction, it can prepare by the second carboxylic The cover type particle of acid compound covering preferably makes at least one or more in (i), (ii) and (iii) carry out hydro-thermal anti- It answers.That is, (i) salt of the second carboxylic acid compound and metal oxide precursor, the metal salt of (ii) second carboxylic acid compound, (iii) Second carboxylic acid compound and metal oxide precursor.
Hereinafter, being described in detail for using the chloride of the oxychlorination things of various metals etc. as the metal oxide precursor Or the high metal oxide precursor of water solubility and corrosivity of nitrate of oxygen nitric acid object etc. etc. as raw material when, it is preferably described (i) the case where.
Further, so-called salt, the not only single type chemical combination that is constituted with stoichiometric ratio of carboxylic acid and metal oxide precursor Object, or complex salt or there are unreacted carboxylic acid or the compositions of metal oxide precursor.
In (i), the salt of so-called second carboxylic acid compound and metal oxide precursor, preferably by alkali metal and/ Or alkaline-earth metal is neutralized into degree of neutralization in the composition containing the carboxylate from the second carboxylic acid compound of the range of 0.1-0.8 The salt of second carboxylic acid compound and metal obtained from being reacted with metal oxide precursor.
The composition containing carboxylate of the range in 0.1-0.8 that is neutralized into degree of neutralization refers to relative to constituting the 1 mole of whole carboxyls of dicarboxylic acid compound, the shape that the carboxyl for being 0.1-0.8 moles is neutralized by alkali metal and/or alkaline-earth metal The composition containing organic carboxylate of state, the hydroxide etc. in addition to suitable alkali metal is added in the second carboxylic acid compound And other than obtaining, unneutralized second carboxylic acid compound can also be mixed with the carboxylate compounds neutralized completely and/or partially And it obtains.The second carboxylic acid compound that the unneutralized, complete neutralization or part neutralize can also can be different from each other to be identical, into One step may be the unneutralized of the composition as composed by different carboxylic acids, complete neutralization or part corrective.
The degree of neutralization is preferably 0.1-0.8, more preferably 0.2-0.7.When less than 0.1, due to the second carboxylic acid compound Solubility it is low, thus exist and be unable to fully the case where forming the salt, in addition, when more than 0.8, generate and a large amount of is speculated as metal Hydroxide white precipitate, thus exist reduce metal oxide particle yield the case where.
Alkali and alkaline earth metal ions for obtaining the composition containing carboxylate can be any one, preferably Form the metal of the carboxylate of high water solubility, preferably alkali metal, particularly preferably sodium and potassium.
The ratio of the composition containing carboxylate and the metal oxide precursor, relative to metal oxide precursor 1 mole, carboxyl is preferably 1 mole -20 moles, more preferably 1.2-18 moles, further preferably 1.5-15 moles.
It is preferably that aqueous solution is mutually mixed when reacting the composition containing carboxylate and the metal oxide precursor It closes.As long as the temperature that reaction temperature is able to maintain as aqueous solution is preferably room temperature to 100 DEG C with regard to not special problem, more excellent It is selected as 40 DEG C -80 DEG C.
The salt obtained from reacting the composition containing carboxylic acid with the metal oxide precursor, although can be with Hydro-thermal reaction is directly fed, but preferably in advance removes insoluble by-product by filtering etc..
Then, the case where (ii), is described in detail.
In the embodiment of (ii), the metal salt for the second carboxylic acid compound modulated in advance is used.With without Loaded down with trivial details process as described above, that is, the advantages of can be supplied to hydro-thermal reaction.But due to can handy compound it is limited, Sometimes the case where being unable to get the metal oxide particle covered by objective carboxylic acid ester group.Metal is not particularly limited, preferably Containing at least one kind of selected from Ti, Al, Zr, Zn, Sn and Ce.
As the metal salt for the embodiment that can be used for (ii), 2 ethyl hexanoic acid titanium, 3,3- acid dimethyl can be exemplified Titanium, sad titanium, oleic acid oxidation titanium, stearic acid titanium oxide, lauric acid titanium oxide, aluminium octoate, zirconium caprylate, 2 ethyl hexanoic acid zirconium, oil Acid oxidase zirconium, stearic acid zirconium oxide, lauric acid zirconium oxide, zinc octoate, tin octoate, cerium octoate etc..
When the purity of metal salt is lower, it is possible to implement used after purification, the salt that can also be directly modulated by commercially available product or in advance Supply hydro-thermal reaction.
Then, the case where (iii), is described in detail.
In (iii), as the metal oxide precursor, for example, the hydroxide of various metals, chlorination can be enumerated Object, oxychlorination things, sulfate, acetate, acylate, metal alkoxides etc..For example, using hydrogen-oxygen using in the example of zirconium Change zirconium, zirconium chloride, zirconium oxychloride, zirconium oxyacetate, zirconyl nitrate, zirconium sulfate, zirconium caprylate, oleic acid oxidation zirconium, acetic acid zirconium, stearic acid It is preferred method whens the zirconium alkoxide etc. of zirconium oxide, lauric acid zirconium oxide, tetrabutyl zirconate etc..In addition, using the example of titanium , it is preferable to use titanium hydroxide, titanium chloride, titanium oxychloride, acetic acid oxygen titanium, titanyl nitrate, titanium sulfate, sad titanium, oleic acid oxygen in son Change the titanium alcoxyl of titanium, acetic acid titanium, stearic acid titanium oxide, lauric acid titanium oxide, four titanium butoxides (such as four titanium n-butoxides) etc. It is preferred method whens compound etc..
It is identical as above-mentioned (i) for second carboxylic acid compound.
It is preferred that in presence of water, the metal oxide precursor and second carboxylic acid compound are mixed.At this point, logical It crosses heating or carries out under reduced pressure, low-boiling compound contained in the metal oxide precursor by ammonia or acetic acid etc. is driven out of Outside system, the rising of pressure can inhibit in the hydro-thermal reaction of subsequent processing, thus preferably.Alternatively, it is also possible to aftermentioned in addition Organic solvent after solution in carry out the reaction.
Then, hydro-thermal reaction is illustrated.
By any one supply hydro-thermal reaction in by described in (i)-(iii), metal oxide particle combination can be obtained Object.Only by (i)-(iii), in the case where viscosity is high hydro-thermal reaction is effectively performed, to (i)-(iii) The organic solvent of addition display good solubility.
Pressure, reaction temperature, the concrete condition in reaction time when organic solvent, amount of moisture, reaction, can quote the first hair The explanation of bright explanation, the second invention.
By the hydro-thermal reaction, in general, metal oxide particle (the cover type grain covered by the second carboxylic acid compound Son) generation can be precipitated in container bottom.Cover type particle is implementable for removing the by-product of hydro-thermal reaction carbon generated etc. Or the purification of condensation product of cover type particle etc..For example, it will be dissolved in toluene equal solvent after product filtering will be precipitated, it will be insoluble Toluene equal solvent is removed to obtain cover type particle by reduced pressure etc. again after object filtering.
, it is preferable to use alkali compounds when the hydro-thermal reaction.As long as alkali compounds shows alkalinity when being dissolved in water Compound, no matter the form of the Taide Bu Langsi alkali or lewis base etc., inorganic compound, organic compound are equal It can.Wherein, it is preferably selected from the alkali compounds of at least one or more in alkali metal salt, alkali salt and 1-3 grade amine, more Preferably alkali metal salt, the organic amine compound of the hydroxide, carboxylic acid of alkali or alkaline earth metal, particularly preferably alkali metal Hydroxide, organic amine compound.By the way that there are alkali compounds, the yield of the cover type particle of generation can be improved.Into one Step, using broad category of carboxylic acid as raw material, obtains being covered by carboxylate for the type for being difficult to prepare by previous methods The cover type particle of lid.
The amount of the alkali compounds, the metal oxide precursor used in this process relative to 1 mole, preferably 0.03 mole or more and be 1.5 moles or less.By adding the alkali compounds of the range, cover type grain can further improve The yield of son.
Then, the substitution process of cover type particle is illustrated.By by the obtained cover type of the hydro-thermal reaction The first carboxylic acid compound of second carboxylic acid compound of particle replaces substitution cover type particle (the metal oxidation for obtaining third invention Object particle).Specifically, mixture of the substitution by stirring containing cover type particle and the first carboxylic acid compound is (especially mixed Close liquid) Lai Jinhang.The mass ratio of first carboxylic acid compound and cover type particle, is not particularly limited, as the first carboxylic acid chemical combination Object/cover type particle, preferably 5/100~200/100.When fewer than 5/100, the import volume of the first carboxylic acid compound becomes sometimes Must be insufficient, dispersibility becomes inadequate, and when more than 200/100, becomes replacing the import volume saturation in cover type particle It is non-effective.More preferably 10/100~150/100.
The solvent used when modulating the mixed liquor, can be used directly the solvent when hydro-thermal reaction, it is possible to use Other solvents.It is preferable to use with for aftermentioned composition (solidification compound etc.) identical solvent, (composition is with molten Agent).When modulation replaces cover type particle in such solvent, obtained substitution cover type particle can further improve in group The compatibility in object is closed, further can highly prevent dispersion uneven.
Whipping temp is preferably 0-100 DEG C, more preferably 10-70 DEG C, further preferably 20-50 DEG C, in mixed liquor The concentration of cover type particle is preferably 5-80 mass %, more preferably 10-60 mass %.Furthermore, it is possible to use ball mill etc. into Solvent-free or higher concentration the processing of row.Reaction time is preferably 10 minutes~5 hours, more preferably 20 minutes~2 hours.
When modulation replaces cover type particle in composition solvent, cover type particle is replaced to be preferably dissolved in composition molten In agent.At this point, can make to replace cover type grain by the way that Weak solvent (for example, aliphatic hydrocarbon series solvent of hexane etc.) appropriate is added Son is precipitated.Precipitate can be separated by solid-liquid isolation method appropriate (filtration method, centrifugal separation etc.) with solvent.On the other hand, When cover type particle being replaced to dissolve in a solvent, it can also be separated by concentration etc. with solvent.
By the covering metal oxide particle of the obtained third invention of the above method, preferably carry out clean.By washing Only, by-product or unreacted first carboxylic acid compound or substituted second carboxylic acid compound can be removed from composition, When for aftermentioned various uses, adverse effect not will cause.It as clean solvent, is not particularly limited, preferably uses third Ketone, hexane, heptane, octane, methanol, ethyl alcohol.
Further, third invention can also be combined with each other respectively with first invention, the second invention, the 4th invention.
That is, the method for the metal oxide particle described as preparation third invention, can quote first invention part respectively The preparation method of metal oxide particle described in the preparation method of the metal oxide particle, the second invention section, The preparation method of metal oxide particle described in four invention sections.
In addition, cover type particle and substitution cover type particle that third invention is described, in the spy described with third invention In the range of sign, it is possible to have compound described in first invention (intermediate compounds of metal oxide particles) and metal oxidation The feature of object particle, it is possible to have the feature of the second invention compound and metal oxide particle, it is possible to have The feature of the 4th invention metal oxide particle can also further be combined with these features.
4. the 4th invention (fourth method)
However, there is the case where containing impurity such as halide in the raw material (metal oxide precursor) of metal oxide particle, The present invention also provides the preparation methods for the metal oxide particle for effectively reducing these impurity.
According to the 4th invention, by with the carboxylic acid that is used to cover (hereinafter, being referred to as the third carboxylic acid and metal oxygen of third carboxylic acid The intermediate compound of the salt of compound precursor or the metal oxide particle being bonded with third carboxylic acid is referred to as the " metal of third carboxylic acid Salt etc. ".) different carboxylic acids (hereinafter referred to as tetrabasic carboxylic acid) with alkali whens being used together to handle metal salt of third carboxylic acid etc., halogen The fluidity of compound changes, with the metal salt of third carboxylic acid etc. or metal oxide particle (cover type metal oxide particle) Become different, removing can be isolated.More it is especially surprising that specifying the halogenation for removing trace impurity according to the 4th invention Object can effectively improve the ratio of the regular crystal of finally obtained metal oxide particle.
According to the 4th invention, the metal salt etc. of third carboxylic acid is handled due to being used together tetracarboxylic acid bronsted lowry acids and bases bronsted lowry, it can Reduce the halogen concentration of chlorine etc., metal salt of the third carboxylic acid refined etc. (purifying metal salt etc.).Further, using the essence Whens metal salt processed etc., halogen concentration can be not only reduced, the ratio that also can be obtained regular crystal is higher, i.e. the higher metal of refractive index Oxide particle.
That is, for the metal salt etc. for the third carboxylic acid that will be modulated from carboxylic acid as the coverture of raw material and metal oxide precursor Contained in halide remove technology.The metal salt etc. of third carboxylic acid becomes metal oxide particle by hydro-thermal reaction.? In third invention, it is important that until completing the preparation of metal oxide particle in the modulation of metal salt from third carboxylic acid etc. Series of processes any moment, make in the solution of metal salt containing third carboxylic acid etc. containing metal oxide will not be covered The alkali of carboxylic acid (not forming the carboxylic acid of compound with metal) (tetrabasic carboxylic acid) and specified amount of precursor, it is anti-with impurity (halide) It answers.Make tetrabasic carboxylic acid, alkali and halide reaction as a result, the fluidity of halide can be changing into separately by a kind of (such as oil-soluble) A kind of (such as water-soluble), can remove from metal salt of third carboxylic acid etc. (such as oil-soluble).
The amount of alkali is not particularly limited, and is preferably 1 equivalent or less relative to tetrabasic carboxylic acid.By the selection of alkali, relative to When the amount of tetrabasic carboxylic acid is more than 1 equivalent, metal salt of alkali and third carboxylic acid etc. forms white precipitate and forms gel, sometimes without Method is separated off halide.Relative to tetrabasic carboxylic acid, the amount of alkali be preferably 0.7 equivalent hereinafter, more preferably 0.5 equivalent hereinafter, Lower limit is not particularly limited, more than for example, 0.1 equivalent.
In 4th invention, it is most important that make the solution for containing the metal salt of third carboxylic acid of halide as impurity etc. In, the alkali containing tetrabasic carboxylic acid and specified amount.It is not limited at the time of the alkali for making it contain tetrabasic carboxylic acid and specified amount, Ke Yi A series of preparation section after the modulation of the metal salt of third carboxylic acid etc. until preparing metal oxide particle is (that is, by During metal salt etc. of tricarboxylic acids and metal oxide precursor modulation third carboxylic acid to before terminating hydro-thermal reaction process) Any stage implements, and particularly preferably makes containing third carboxylic acid existing at the end of the modulating process such as the metal salt of third carboxylic acid In the solution of metal salt etc., the alkali containing tetrabasic carboxylic acid and specified amount.By making it contain together with halide at the moment Tetracarboxylic acid bronsted lowry acids and bases bronsted lowry can remove effectively halide.So that it is contained the method for carboxylic bronsted lowry acids and bases bronsted lowry, can be any one in following 1-3 Kind.
1. in advance reacting carboxylic bronsted lowry acids and bases bronsted lowry, it is added after forming salt.
2. carboxylic bronsted lowry acids and bases bronsted lowry is added simultaneously.
3. after carboxylic acid is added, alkali is added.
Pass through removing for the reactant of halide caused by tetracarboxylic acid bronsted lowry acids and bases bronsted lowry (changing halide hereinafter also referred to as fluidity) Method is gone, as long as utilizing the method different from the fluidity of the metal salt of third carboxylic acid etc., there is no particular limitation, can be used and wash Only, method well known to crystallization etc., it is easier because cleaning removing, thus recommend.In order to remove halide by cleaning, in advance by the The metal salt etc. of tricarboxylic acids is dissolved in a kind of solvent (such as oil-based solvent) of fluidity, by the molten of another fluidity of the solution Agent (such as aqueous solvent) is cleaned.In addition, these a kind of and another fluidity solvents, it can be after the reaction of halide It is added, preferably a part by constituting the solution of metal salt containing third carboxylic acid etc. before reacting.In addition, by reacting preceding i.e. structure At the solution of the metal salt containing third carboxylic acid etc. a part when, the fluidity, halide reaction after determine.That is, containing The solution of metal salt of third carboxylic acid etc. and halide, the latest after the reaction of halide, the gold containing dissolvable third carboxylic acid Belong to a kind of organic solvent (fluidity solvent (the first solvent), such as oil-based solvent) of salt etc., and mutually separated with the organic solvent Second solvent (another fluidity solvent, such as aqueous solvent), preferably makes the reactant of the halide be dissolved in the second solvent Organic solvent and the second solvent are separated again afterwards.It can be dissolved in metal salt of third carboxylic acid of same solvent etc. and halogen as a result, Compound is separated to the organic solvent mutually separated and the second solvent respectively.It, can be by the metal salt containing third carboxylic acid etc. after liquid separation Solution is further cleaned with the second solvent, furthermore can also be crystallized.
Organic solvent (oil-based solvent), as long as can dissolve the metal salt etc. of third carboxylic acid, there is no particular limitation, can make With the aromatic hydrocarbon solvent of such as benzene,toluene,xylene etc.；Di Iso Propyl Ether, t-butyl methyl ether, dibutyl ethers, diethylene glycol (DEG) two The ether series solvent of methyl ether etc.；The modification ethers of propylene glycol monomethyl ether acetate etc.；The ketone system of methyl ethyl ketone, methylisobutylketone etc. Solvent；The ester series solvent of ethyl acetate, butyl acetate etc.；The halogen-based solvent of chloroform, two chloroforms etc.；Hexamethylene, methyl cyclohexane The cyclic hydrocarbon solvents of alkane, ethyl cyclohexane etc.；The chain hydrocarbon solvent of pentane, hexane, heptane, octane, isooctane, Permethyl 99A etc. Deng.
In addition, the mixed solvent etc. of water, water and water-miscible organic solvent can be enumerated as the second solvent (aqueous solvent). As water-miscible organic solvent, the alcohols of methanol, ethyl alcohol etc. can be illustrated；The ether of ethylene glycol, dimethoxy-ethane, tetrahydrofuran etc. Class；The ketone of acetone, dioxane etc.；The nitrile etc. of acetonitrile etc..
The amount of first solvent, relative to metal oxide precursor, preferably 0.25-4.0 mass times, more preferably 0.5- 2.0 mass times.In addition, the amount of the second solvent, relative to the first solvent, preferably 0.2-10 mass times, more preferably 0.5-5 matter Amount times.
Reaction temperature when reacting tetracarboxylic acid bronsted lowry acids and bases bronsted lowry with the halide, preferably 40-150 DEG C.By being adjusted to Such temperature range can efficiently generate the reactant of halide, remove halogen.The lower limit of the reaction temperature, preferably 50 DEG C or more, further preferably 70 DEG C or more, the upper limit of the reaction temperature, more preferably 130 DEG C are hereinafter, further preferably It is 100 DEG C or less.Reaction time is not particularly limited, and (preferably 30 minutes~1 hour) for example, 15 minutes~3 hours left It is right.
Third carboxylic acid covers metal oxide particle, has and improves the dispersibility in the medium of solvent or resin etc. Effect.As third carboxylic acid, carboxylic acid described in first invention can be used.
Third carboxylic acid, relative at 1 mole of metal of metal oxide precursor, preferably 1-5 moles, more preferably 2-4 Mole.Especially in the modulation of the metal salt of third carboxylic acid etc., the excessive third carboxylic that is not reacted with metal oxide precursor Acid residual, using the excessive third carboxylic acid as tetrabasic carboxylic acid in use, the lower limit of third carboxylic acid amount, relative to metal oxide 1 mole of metal in precursor, preferably 1.3 moles or more, more preferably 1.5 moles or more.In addition, using with third carboxylic acid not With tetrabasic carboxylic acid when, the upper limit of third carboxylic acid amount, as long as finally obtained metal oxide particle can be improved in the medium Dispersibility degree, for example, 3 moles hereinafter, more preferably 1.5 moles or less.
As metal oxide precursor, the carbonate, metal halide and oxygen alloy category halogenation for selecting free metal can be used One or more of group composed by object.As constitute metal oxide precursor metal, such as can enumerate Ti, Al, Zr, In, Zn, Sn, La, Y, Ce, Mg, Ba, Ca etc..It is excellent from the viewpoint of the refractive index that finally obtained metal oxide can be improved It is selected as at least one kind of (especially Zr) in the group as composed by Ti, Al, Zr, Zn and Sn.
Temperature 50-100 whens third carboxylic acid being made to react the metal salt etc. for generating third carboxylic acid with metal oxide precursor DEG C (preferably 70-90 DEG C) left and right, time are (preferably 2-4 hours) 1-5 hours Zuo You.
Tetrabasic carboxylic acid is not particularly limited, such as in the same manner as third carboxylic acid, and carboxylic acid described in first invention can be used.The Tetrabasic carboxylic acid can be different from third carboxylic acid, can also be identical.When especially identical, in the tune of the metal salt of the third carboxylic acid etc. In system, make not react excessive carboxylic acid remained with the metal oxide precursor, it is also preferred that use the excessive carboxylic acid as Tetrabasic carboxylic acid.Tetrabasic carboxylic acid can be used only a kind, can also combine two or more use.
The amount of tetrabasic carboxylic acid, it is for example, 0.3 mole or more, more excellent relative to 1 mole of metal in metal oxide precursor It is selected as 0.5 mole or more.The upper limit of tetrabasic carboxylic acid amount is not particularly limited, and rubs relative to the metal 1 in metal oxide precursor You, for example, 4 moles hereinafter, preferably 3 moles or less.
Alkali is not particularly limited, no matter highly basic, weak base.Alkali metal for example including sodium hydroxide or potassium hydroxide etc. Hydroxide；The alkaline earth metal hydroxide of magnesium hydroxide etc.；The alkali etc. containing N of ammonia, triethylamine, pyridine etc..Preferably ammonia.
As described above, halide can be removed when containing carboxylic bronsted lowry acids and bases bronsted lowry together with halide, can be obtained halogen concentration relative to The purified compound of the metal of metal oxide precursor, for example, 10 mass ppm or less (preferably 5 mass ppm or less).More Surprisingly, specifying will be used as halide existing for impurity to remove in metal oxide precursor, can effectively improve final The ratio of the regular crystal of obtained metal oxide particle.
That is, by (fine golds such as the metal salts of third carboxylic acid reduced by the obtained halogen concentration of above-mentioned preparation method Belong to salt etc.) the obtained metal oxide particle of hydro-thermal reaction (cover type metal oxide particle) is carried out to reduce halogen dense While spending, the ratio of the regular crystal in crystallization is higher.More specifically, halogen is 10 relative to the ratio of metal oxide particle Quality ppm is hereinafter, and tetragonal phase is 70% or more for total ratio of whole systems of crystallization in crystallization.The halogen Ratio, preferably 7 mass ppm or less (more preferably 5 mass ppm or less), the ratio of the regular crystal is preferably 75% or more.
In addition, above-mentioned metal oxide particle, the covering of the carboxylate compound shown in following formula (3).
- OC (=O)-R " (3)
R " is saturated hydrocarbyl.It is preferable to use the carboxylate compounds that total carbon number in R " is 3 or more.It is total in R " by making Carbon number is 3 or more, and dispersibility of the finally obtained metal oxide particle in the medium of solvent or resin etc. can be improved.From From the viewpoint of dispersibility, total carbon number in preferably R " is more, lower limit value, more preferably 4, further preferably 5.Another party The upper limit in face, total carbon number in R is not particularly limited, for example, being 20 or less.
Using the hydro-thermal reaction of purified compound, explanation, the second invention and the third hair of the first invention can be quoted Bright explanation.
Further, the 4th invention can also be combined with each other respectively with first invention, the second invention, third invention.
That is, the method for the metal oxide particle described as the 4th invention of preparation, can also quote first invention respectively The preparation side of metal oxide particle described in the preparation method of metal oxide particle described in part, the second invention section The preparation method of metal oxide particle described in method, third invention section.
In addition, compound and metal oxide particle that the 4th invention is described, with the feature described in the 4th invention In range, it is possible to have compound described in first invention (intermediate compound of metal oxide particle) and metal oxide The feature of particle, it is possible to have the second invention cover type particle and the feature for replacing cover type particle can also have The feature for the metal oxide particle for having third invention described can also further be combined with these features.
5. composition
The invention also includes the compositions containing above-mentioned each compound or each metal oxide particle.As group of the invention Object is closed, the dispersion of compound or metal oxide particle dispersion in a solvent can be exemplified；It is aoxidized containing compound or metal The resin combination for the transparent planar formed body of display of object particle (hereinafter, sometimes referred to simply as " resin combination ") Deng.Above-mentioned metal oxide particle, can be used alone, and can also use with other substances together as composition.
Covering metal oxide particle of the invention can be added to due to having significant dispersibility to various media In multi-solvents, monomer (monofunctional monomer and/or cross-linkable monomer), oligomer, polymer etc. or in their combination.
For the solvent of dispersion of the invention, as long as the compound of the present invention or metal oxide particle show compared with The solvent of high dispersibility.Such as the alcohols that methanol, ethyl alcohol, normal propyl alcohol, isopropanol, ethylene glycol can be enumerated etc.；Methyl second The ketone of base ketone, methyl iso-butyl ketone (MIBK), cyclohexanone etc.；The ester of ethyl acetate, propyl acetate, propylene glycol monomethyl ether acetate etc. Class；The ethers of glycol monoethyl ether, diethylene glycol monobutyl ether etc.；The modification ethers of propylene glycol monomethyl ether acetate etc. is (preferably For ether modification and/or ester modified ethers, further preferably ether modification and/or ester modified alkane glycols)；Benzene, toluene, diformazan The hydro carbons of benzene, ethylo benzene, trimethylbenzene, hexane, hexamethylene, hexahydrotoluene, ethyl cyclohexane, mineral spirits etc.；Two chloroforms, The halogenated hydrocarbons of chloroform etc.；The amides of dimethylformamide, DMAC N,N' dimethyl acetamide, N-Methyl pyrrolidone etc.；Water；Mine The oils of object oil, vegetable oil, wax oil, silicone oil etc..It may be selected that two or more also may be selected and is used in mixed way using a kind in these. From the aspect of operability, the boiling point preferably under normal pressure be 40 DEG C or more and be 250 DEG C or less Zuo You solvent.It is aftermentioned anti- It loses agent to use on the way, preferably ketone, modified ethers etc..
It in the dispersion according to the invention, can be using the polymerizable compound of monofunctional monomer, cross-linkable monomer etc. as Jie Matter, as long as the compound of the present invention or metal oxide particle show the medium of higher dispersibility.
As long as monofunctional monomer only with the compound of 1 polymerizable carbon-to-carbon double bond, can enumerate (methyl) Acrylate；Styrene, p-tert-butylstyrene, α-methylstyrene, o-methyl styrene, p-methylstyrene, to chlorobenzene The styrenic monomers of ethylene, p-chloromethyl styrene etc.；The monomer containing carboxyl of (methyl) acrylic acid etc.；Ethoxy (first Base) acrylate etc. the monomer etc. containing hydroxyl.As above-mentioned (methyl) acrylate, such as (methyl) can be specifically enumerated Methyl acrylate, (methyl) ethyl acrylate, (methyl) n-propyl, (methyl) n-butyl acrylate, (methyl) propylene (the first of sour isobutyl ester, (methyl) tert-butyl acrylate, (methyl) 2-EHA, (methyl) lauryl acrylate etc. Base) alkyl acrylate；(methyl) acrylate base of (methyl) cyclohexyl acrylate, (methyl) isobornyl acrylate etc. Ester；(methyl) acrylic acid aralkyl ester of (methyl) benzyl acrylate etc.；(methyl) glycidyl acrylate etc. has contracting Glyceryl (methyl) acrylate of water etc., preferably (methyl) methyl acrylate.These monofunctional monomers illustrated, can be with Be used alone, can also properly mix two kinds it is used above.
As long as cross-linkable monomer contains multiple carbon-to-carbons that can be copolymerized with carbon-to-carbon double bond possessed by monofunctional monomer The compound of double bond.As the cross-linkable monomer, such as ethylene glycol two (methyl) acrylate, diethyl can be specifically enumerated The alkylene of glycol two (methyl) acrylate, propylene glycol two (methyl) acrylate, dipropylene glycol two (methyl) acrylate etc. Poly- (methyl) acrylate of base glycol；Neopentyl glycol two (methyl) acrylate, two neopentyl glycol two (methyl) acrylates etc. Poly- (methyl) acrylate of neopentyl glycol；Trimethylolpropane tris (methyl) acrylate, two (trimethylolpropane) four (first Base) acrylate etc. poly- (methyl) acrylate of trimethylolpropane；Pentaerythrite four (methyl) acrylate, two Ji Wusi Polyfunctionality (methyl) acrylate of poly- (methyl) acrylate of the pentaerythrite of alcohol six (methyl) acrylate etc. etc.；Diethyl The polyfunctionality styrenic monomers of alkenyl benzene etc.；Diallyl phthalate, diallyl isophthalate, triallyl Polyfunctionality allyl ester system monomer of cyanurate, triallyl isocyanate etc. etc..
The concentration of compound or metal oxide particle in dispersions, can suitably set depending on the application, in general, relative to The dispersion is 90 mass % hereinafter, becoming difficult to be uniformly dispersed when more than 90 mass %, gonorrhoea occurs in dispersion.Another party Face, lower limit value are not particularly limited, it is contemplated that the cost of solvent, for example, 1 mass % or more, preferably 5 mass % or more and For 80 mass % hereinafter, further preferably 10 mass % or more and be 70 mass % or less.
It is used in the resin of resin combination, is not particularly limited as long as the resin used as ordinary resin, example Thermoplastic resin, heat-curing resin, light-cured resin can such as be enumerated.
Composition containing above-mentioned monomer is equivalent to solidification compound.Resin group is constituted after solidification compound solidification Close object.In addition, composition of the invention, or the resin combination containing above-mentioned polymer (resin).Constitute the present invention Resin combination when, the resin as medium (matrix) can use thermoplastic resin, heat-curing resin, photo-curable tree Any one in rouge.
As thermoplastic resin, the polyamide-based of 6- nylon, 66- nylon, 12- nylon etc. can be specifically exemplified；Polyamides is sub- Amine；Polyurethanes；The polyalkenes of polyethylene, polypropylene etc.；The polyesters of PET, PBT, PEN etc.；Polyether sulfone, polyether ethersulfone, The aromatic system polyethers of polyether-ketone, polyether-ether-ketone etc.；Polyvinyl chloride；Vingon class；Polyvinyl acetate；Polyphenyl Vinyl；(methyl) acrylic resin based polymer；ABS resin；Fluororesin；Acid imide silane resin etc..In addition, can also enumerate Polyvinyl butyral system resin, polyurethane series resin, ethylene-vinyl acetate copolymer system resin, ethylene-(methyl) propylene Soft resin or hard resin of acid ester copolymer system resin etc. etc..When using thermoplastic resin as medium, it can be used well known Mixed method, such as can be suitably using the mixing using extruder or the mixing using solution.
As heat-curing resin, can enumerate as condensation be heat reactive resin phenol formaline resin, cresols The phenolic resin of formaline resin etc.；The amine resin etc. of urea resin, melamine resin, guanamine resin etc., using phenol It when aldehyde system resin, and is excellent with compound, guanamine derivatives, cyanuric acid derivative or isocyanuric acid derivatives with triazine ring The embodiment of choosing.
As heat or the resin of photocuring, can be used has cationic polymerizable group and/or radically polymerizable group group Resin.Epoxy resin can specifically be enumerated；Urethane (methyl) acrylate；Epoxy group (methyl) acrylate；Polyester (first Base) acrylate；Unsaturated polyester (UP)；The phenylethylene resin series of divinylbenzene etc.；Diallyl phthalate, isophthalic diformazan The allyl ester system resin of diallyl phthalate, triallyl cyanurate, triallyl isocyanate etc.；Ethylene glycol two (methyl) propylene Acid esters, 1,6-hexylene glycols two (methyl) acrylate, 1,9- nonanediol two (methyl) acrylate, neopentyl glycol two (methyl) third Olefin(e) acid ester, 3- methyl-1,5- pentanediol two (methyl) acrylate, 2-butyl-2-ethyl-1,3-propanediol two (methyl) propylene Acid esters, dihydroxymethyl tristane two (methyl) acrylate, pentacyclopentadecandimethanol glycol two (methyl) acrylate, bisphenol-A two Two (methyl) acrylic acid adducts, cyclohexanedimethanol two (methyl) acrylate, norbornane dimethanol of glycidol ether Two (methyl) acrylate, to terpane -1,8- glycol two (methyl) acrylate, to terpane -2,8- glycol two (methyl) Acrylate, to terpane -3,8- glycol two (methyl) acrylate, bicyclic [2.2.2]-octane -1- methyl -4- isopropyl - 2 degrees of functionality (methyl) acrylate compounds of 5,6- dihydroxymethyl two (methyl) acrylate etc.；Trimethylolpropane tris (first Base) acrylate, trimethylolethane trimethacrylate (methyl) acrylate, glycerol three (methyl) acrylate, four (first of pentaerythrite Base) acrylate, dipentaerythritol six (methyl) acrylate, poly- (methyl) acrylate of tripentaerythritol, tetrapentaerythritol (methyl) acroleic acid esterifications more than 3 degrees of functionality of poly- (methyl) acrylate of poly- (methyl) acrylate, five pentaerythrites etc. Close (methyl) acrylic of object etc.；(methyl) acrylic acid -2- ethylene acyl-oxygen ethyl ester, (methyl) acrylic acid -2- (2- second Alkene acyloxyethyl) ethyl ester, diethylene glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, tetraethylene glycol two The ethylene oxy of (methyl) acrylate, three (methyl) acrylate of the ethylene oxide addition product of trimethylolpropane, bisphenol-A (methyl) propylene derivative with ether structure of two (methyl) acrylate of compound addition product etc.；Glycol divinyl The vinyl ethers based compound of base ether, cyclohexanedimethanol divinyl base ether etc.；Trimethylolpropane allyl ether, Ji Wusi The allyl ether of alcohol triallyl ether etc., glycerol diallyl ether adipate ester etc. allyl ether based compound；Contain side The polymer of chain double bond；With polymerizable functional group and the isocyanate compound containing silicon group etc..
When using the resin of heat or photocuring, preferred embodiment is and uses polymerizable monomer or polymerization initiator, heat Polymerization accelerant, light sensitizer, photopolymerization promoter etc..It as polymerizable monomer, is not particularly limited, can specifically enumerate example Such as styrene, 4- t-butyl styrene, α-methylstyrene, 4- chlorostyrene, 4- methyl styrene, 4- 1-chloro-4-methyl-benzene Styrenic monomers；(methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) propylene Acid butyl ester, (methyl) acrylic acid-2-ethyl caproite, (methyl) cyclohexyl acrylate, (methyl) isobornyl acrylate, (methyl) Acrylic acid -1- Buddha's warrior attendant alkyl ester, (methyl) acrylic acid tetrahydrofurfuryl alcohol ester, (methyl) acrylic acid -2- hydroxyl ethyl ester, (methyl) acrylic acid 2- Hydroxypropyl acrylate, (methyl) glycidyl acrylate, (methyl) acrylic acid trifluoro ethyl ester, (methyl) perfluoroethyl octyl ethyl ester etc. (methyl) acrylic acid be derivative；The vinyl ether monomer of hydroxy butyl vinyl ether, dodecyl vinyl etc.；Allyl Base glycidol ether, the allyl ether of melamine methylol, the adipate ester of glycerol diallyl ether, allyl acetal, hydroxyl The allyl ether system monomer of the allyl ether of methyl-prop keto-aldehyde ureine etc.；The maleic acid of diethyl maleate, dibutyl maleate etc. Rouge system monomer；The fumarate system monomer of dibutyl fumarate, dioctyl fumarate etc.；4- (methyl) acryloyloxymethyl- 2- methyl -2- ethyl -1,3- dioxolanes, 4- (methyl) acryloyloxymethyl -2- methyl -2- isobutyl group -1,3- dioxy penta Ring, 4- (methyl) acryloyloxymethyl -2- cyclohexyl -1,3- dioxolanes, 4- (methyl) acryloyloxymethyl -2,2- two The 1,3- dioxolanes system monomer of penta ring of methyl-1,3-dioxy etc.；(methyl) acryloyl morpholine；N- vinyl formamide；N- Vinyl pyrrolidone etc..These polymerizable monomers, can be used alone, and can also be used in combination of two or more.These polymerizable monomers In, preferably (methyl) acrylic acid series ester compounds.
Among above-mentioned, more preferably polyimide, polyurethanes, polyesters, (methyl) acrylic resin based polymer, Phenolic resin, amine resin, epoxy resin.They can be used alone, and can also mix two or more use.
The concentration of metal oxide particle of the invention in above-mentioned composition, can suitably set depending on the application, the combination It is (metal oxide particle, solvent, monomer, oligomeric usually relative to the whole components of the uncured composition when object is uncured The whole of ingredient used in object, polymer and aftermentioned polymer precursor etc. is total) 100 mass % are 90 mass % Below.When more than 90 mass %, it becomes difficult to which evenly dispersed, uncured composition is possible to gonorrhoea occur.On the other hand, lower limit Value is not particularly limited, but considers solvent cost, for example, 1 mass % or more.More preferably 5 mass % or more and be 80 matter Measure % hereinafter, further preferably 10 mass % or more and be 70 mass % or less.
In addition, in resin combination of the invention, not only above-mentioned high-molecular compound (polymer) and of the invention The composition of compound or metal oxide particle further includes constituting the monomer (polymer precursor) of above-mentioned polymer, such as two Unsaturated carboxylic acid or its ester compounds of the mixture of carboxylic acid and diamines, acrylic or methacrylic acid etc. etc. and of the invention The composition of compound or metal oxide particle.In addition, resin combination of the invention, or including polymer and list The composition of the two of body.
In above-mentioned polymer, the good polymer of heat resistance is particularly preferably used.By using the good polymerization of heat resistance Object can fully play the heat resistance improvement effect of metal oxide particle of the invention.And specifically, it is preferable to polyimide, (methyl) acrylic resin based polymer, phenolic resin, epoxy resin etc..
The blended amount of metal oxide particle as resin combination of the invention, 1 matter preferably in composition In the range of amount %-90 mass %.When above-mentioned blended amount is less than 1 mass %, the planar formed body that formed by resin combination or The refractive index of optical article is possible to be lower.On the other hand, when above-mentioned blended amount is more than 90 mass %, the viscosity of composition is sometimes It can get higher, workability reduces.The upper limit value of the blended amount of metal oxide particle, more preferably 85 mass %, most preferably 80 Quality %.In addition, the lower limit value of the blended amount, more preferably 10 mass %, further preferably 15 mass %, most preferably 20 mass %.
Resin combination of the invention, in addition to above-mentioned solvent, monomer, oligomer, polymer, in order to further increase dispersion Property, dispersing aid can also be added.Dispersing aid, as long as the substance that metal oxide particle of the invention can be made to disperse, just It is not particularly limited, it is representative to enumerate surfactant etc..
As surfactant, anionic surfactant, cationic surface active agent, amphoteric ion table can be enumerated Face activating agent, nonionic surface active agent.As anionic surfactant, enuatrol, odium stearate, laurel can be used The sodium soap of sour sodium etc.；The fatty acid type surfactant of fatty acid potassium, aliphatic ester sodium sulfonate etc.；Alkyl phosphate sodium etc. Phosphatic type surfactant；The olefin type surfactant of α oleic acid sodium sulfonate etc.；The alcohol type surface-active of sodium alkyl sulfate etc. Agent；Alkyl benzene surfactant etc..As cationic surface active agent, chlorination alkyl methyl ammonium, chlorination alkyl can be used Dimethyl ammonium, alkyl trimethylammonium chloride, alkyldimethyl benzylammonium chloride etc..As zwitterionic surfactant, can make With the carboxylic acid type surfactant of alkyl amine group carboxylate etc.；The phosphate-type surfactant etc. of phosphate glycine betaine etc..Make For nonionic surface active agent, polyethylene glycol oxide lanolin alcohol aliphatic ester, polyoxyethylene sorbitol fatty acid can be used The fatty acid type surfactant of ester etc.；Polyethylene glycol oxide alkyl phenyl ether；Fatty acid alkanol amides etc..
In addition, preferably, can enumerate by adding 2- acryloyl-oxyethyl succinic acid, 2- acryloyl-oxy Base ethyl hexahydrophthalic acid, 2- acryloyl-oxyethyl phthalic acid, 2- methacryloxyethyl succinic acid, 2- Methacryloxyethyl hexahydrophthalic acid, 2- methacryloxyethyl phthalic acid improve dispersibility.
Resin combination (including the solidification compound after solidifying) of the invention, can also blend the compound of the present invention or Adding ingredient other than metal oxide particle (substituted type cover type particle) and resin.As the adding ingredient, such as can lift Curing agent, curing accelerator, colorant, internal mold release, coupling agent, reactive diluent, plasticiser, stabilization agent, resistance out Combustion auxiliary agent, low-shrinkage mixture, polymerization terminator, antioxidant, ultraviolet absorbing agent, defoaming agent, smooth agent, shakes variation at crosslinking agent Agent, tackifier etc..
Resin combination (including the solidification compound after solidifying) of the invention, equably due to metal oxide particle Dispersion, thus the transparency is high.Specifically, the light transmittance of the light of wavelength 400nm can be 70% or more on 100 μm of thickness, excellent It is selected as 75% or more, more preferably 80% or more.
Resin combination (including the solidification compound after solidifying) of the invention, due to the metal oxidation containing specified amount Object particle, thus refractive index is also higher.Specifically, for the refractive index of the light of 589nm can for 1.5 or more, preferably 1.6 with On.The upper limit of refractive index, such as can be 1.8 or so.
The shape of resin combination (including the solidification compound after solidifying) of the invention, is not particularly limited, such as It can be the formed body of film, plate, thin slice, film, fiber etc..
The resin combination (resin combination) for the transparent planar formed body of display, is particularly preferably configured to Planar.Planar formed body of the invention refers to the whole circumstances with face including film, plate, thin slice, film etc., is not rely on Thickness or film thickness.In addition it is also possible to be rectangular, rectangle, circle, ellipse, triangle, polygon, abnormity or roll fashion, layer Any shape of pressure mode etc..By being configured to planar, so that the lamination in aftermentioned display or touch control panel device becomes It must be easy.
Obtained planar formed body through the invention due to being easily adjusted refractive index, thus can be prevented due to having The reflection and scattering of the light of the refringence of the interlayer of the display device of multilayered structure.Further, due to by blending the present invention Metal oxide particle, can be improved dielectric constant, thus be suitable for insulating film.
Especially in touch surface display, the high-index material of IT0 film etc. is used to describe as transparent conductive film There is electrode pattern clamping insulating layer to describe figuratum first layer in X-direction and describe the figuratum second layer in the Y direction Three-decker.Resin combination for transparent planar formed body of the invention can prevent from seeing depicting pattern, improve identification Property, thus can be suitable for the layer of insulating layer or protective film etc. contacted with electrode layer.Further, it can be also suitably used for liquid crystal display Thin film transistor (TFT) (TFT) the substrate planarization film of element or organic EL display element etc., semiconductor element interlayer dielectric, The core or clad material of solid photographic element planarization film or microlens array pattern or optical waveguide.
Resin combination of the invention, due to containing metal oxide particle, thus the refraction of adjustable tree oil/fat composition Rate.Further, since the average grain diameter of metal oxide particle is 1nm or more and is 100nm hereinafter, resin group thus can be maintained Close the transparency of object.Since the surface of metal oxide particle of the invention is by the organic compound institute that can be coordinated and/or be bonded Covering, thus the favorable dispersibility in resin, and heat resistance, ultra-violet resistance are also excellent.Therefore, metal oxygen of the invention Compound particle will not agglomerate in the composition, can play its characteristic (high refractive index etc.), and if exposed to high temperature or purple It will not change colour in outer light, suitable for the resin layer or resin thin film layer in display.In addition, metal oxide of the invention The surface of particle is covered by the organic compound that can be coordinated and/or be bonded, and compared with unlapped particle, can make particle surface For hydrophobicity, thus while forming solidfied material, can make water-fast physical property, electrical characteristics (insulating properties) excellent.
6. preferable use
Obtained metal oxide particle (cover type Zirconia particles) according to the present invention, suitable for optical lens, Optical thin film sticker, optical thin film bonding agent, nano impression resin, microlens array, for the anti-of transparent electrode Reflecting layer, antireflective film or antireflection agent, the surface covering of optical lens, organic EL light-extraction layer etc. optical material.
Particularly, using the curability group of the metal oxide particle (replacing cover type particle) prepared by the second invention Object is closed, due to the metal oxide particle (replace cover type particle) containing good dispersion, thus excellent flowability and curability Also excellent.Therefore, in nanometer embossing, the excellent transferability of mold.
Metal oxide particle of the invention can be unfolded in a variety of applications where due to its significant dispersibility.As requiring The purposes of polymolecularity, can enumerate resist purposes, optical applications, coating applications, adhesion purposes, suitable for optical lens, Optical thin film sticker, optical thin film bonding agent, nano impression resin combination, microlens array, be used in it is transparent Anti-reflection layer, antireflective film or the antireflection agent of electrode, the surface covering of optical lens, organic EL light-extraction layer, various The various protective films of hard coat material, TFT planarization film, colored filter sealer, antireflective film etc., and Optical light filter, touch sensing insulating film, TFT insulating film, colored filter light clapboard, touch panel guarantor's peritonaeum Deng optical material.Metal oxide particle of the invention is in addition to significant dispersibility, due to also having high refractive index, height hard Degree, high stability, thus passed particularly preferred for optical lens, the surface covering of optical lens, various hard coat materials, touch-control Sensor insulating film, TFT insulating film, touch panel protective film.
Further, metal oxide particle of the invention efficiently uses its high dielectric constant other than optical applications, It can be suitable for the gate insulating film of semiconductor or the memory electricity container insulating film of DRAM etc..As obtaining, dielectric high in this way is normal The method of several insulating films, it is known to pass through CVD (Chemical Vapor Deposition: chemistry using Organometallic precursor Vapour deposition process) method or ALD (Atomic Layer Deposition: atomic layer deposition method) method etc. chemical vapour deposition vapor deposition Afterwards, the method for oxidation processes is carried out.The metal oxide of desired high dielectric constant needs 600 DEG C or more of height in order to obtain The phenomenon that temperature is handled, but since it is influenced, and can cause the job insecurity of the semiconductor layer headed by anchoring phenomenon.The present invention Metal oxide particle, be not necessarily to high-temperature process, dielectric constant with higher when generation, for the single particle of several nm, So that the lamination that can correspond to the imperceptibility of semiconductor from now on is possibly realized, simultaneously as it is not necessarily to high-temperature process, it can also The semiconductor preparation being used on plastic base.
Hereinafter, the resist purposes as representative purposes is described in detail.Utilize the element of resist method, example Production can be such as proceed as follows.
1) modulation contains the solidification compound (curable resin) of metal oxide particle of the invention.Typically adjust System is containing metal oxide particle of the invention, the polymer with acidic group or has acidic group, radically polymerizable group group or ring The polymer of oxygroup, the compound with free-radical polymerised double bond or the compound with epoxy group, optical free radical producing agent Or photoacid generator, solvent as needed, colorant, filling material, dyestuff, pigment, defoaming agent, coupling agent, smooth agent, increasing sense Agent, release agent, lubrication prescription, plasticiser, antioxidant, ultraviolet absorbing agent, fire retardant, polymerization inhibitor, tackifier, dispersing agent etc. Well known additive anti-corrosion agent composition.Well known combination of materials, well known blend ratio may be selected in various composition.
2) prepare above-mentioned solidification compound (the curable resin combination containing metal oxide particle of the invention Object) it is deposited to the substrate on the transparent substrate of glass, transparent plastic etc. or transparent electrode.As transparent electrode, it is representative can Illustrate ITO, IZO, AZO, ZnO2, tin metaantimmonic acid etc..On the glass substrate formed transparent electrode thin film when, can by vacuum evaporation, The previous methods such as the physical method or chemical vapour deposition technique of sputter, ion plating, ion beam vapor deposition etc. carry out.
On the substrate, it by method well known to method of spin coating, spray coating method etc., will be aoxidized containing metal of the invention The solidification compound of object particle is coated with, dry, makes film.As coating method, it is preferable to use method of spin coating.As dry Dry condition is the temperature of room temperature~120 DEG C, and preferably 60 DEG C -100 DEG C of temperature is -60 minutes 10 seconds, and preferably 30 seconds extremely 10 minutes, method preferably dry in normal pressure or heating under vacuum.
3) then, as expected pattern form is provided with to the light shield (pattern formation film) of opening portion, with contact State or contactless state are positioned on above-mentioned film, irradiation light, make its solidification.Here, so-called light, refers not only to visible light, also Refer to the radioactive ray of ultraviolet light, X-ray, electric wire etc., most preferably ultraviolet light.As ultraviolet source, height usually can be suitably used Medium pressure mercury lamp.
4) after light irradiation, developed with solvent, water, alkaline aqueous solution etc..In them, since alkaline aqueous solution is to environment Load it is less and the development of high sensitivity can be carried out, thus preferably.As alkaline components, preferably potassium hydroxide, sodium hydroxide, Sodium carbonate etc..The concentration of alkali, preferably 0.01-5 mass %, further preferably 0.05-3 mass %, most preferably 0.1-1 matter Measure %.When alkali concentration is lower than above range, the dissolubility of the curable resin is insufficient sometimes, on the contrary, when excessively high, it is sometimes molten Xie Li is excessively high, and developability is deteriorated.Further, surfactant can also be added in alkaline aqueous solution.
5) (rear baking) further progress solidification is preferably heated after alkaline development, and when there is dissolvent residual by it It completely removes.Temperature when as rear baking, preferably 120-300 DEG C, further preferably 150-250 DEG C, most preferably 180-230℃.Afterwards baking temperature than it is above-mentioned high when, element is possible to colour or damage because of thermal decomposition the flatness of film, phase Instead, when too low, cured progress is less, and coating strength is likely to decrease.After toast, can be after the development during each component is formed It carries out, can also be carried out after forming all components.The element is preferred for display device, as specific example, can enumerate Liquid crystal display device, but not limited to this, for example, it is also possible to use the display device etc. of organic EL.In addition, being also suitble to use In the article of touch panel etc..
Hereinafter, being described in detail to the case where being used for lens application.Usual optical lens, refractive index more high-performance more Height, metal oxide particle of the invention have nanoscale dispersibility, and from the refractive index of metal oxide, can be big The earth improves the refractive index of solidfied material, thus is suitble to use.Such as production can be proceeded as follows.
1) it by the monomer or oligomer of metal oxide particle and resin of the invention, is mixed with blender, production has The resin combination of mobility.
2) by the resin combination, it is configured to defined shape using metal die, glass mold, resin die etc., is made Make to form the forming of small convex lens portions on the surface (surface of side) of the substrate formed by flat resin combination Body.
3) formed body is heated, or imposes the irradiation of ultraviolet light or infrared ray etc. to formed body, solidify the formed body, Form optical lens.
The monomer or oligomer of resin, when having reactive carbon double bond (C=C), even if only mixing, Ji Kejin Row polymerization and resinification.In particular, the resin combination as ultraviolet light (UV) curable resin made containing allyl resin etc. Cured method has various methods, representative to have the free radical polymerization for using and causing by heating or light irradiation anti- Moulding method, transfer forming process for answering etc..As the Raolical polymerizable, the polymerization reaction (hot polymerization using heat can be enumerated Close), using ultraviolet light etc. light polymerization reaction (photopolymerization), using gamma-ray polymerization reaction, or by they a variety of groups The method etc. of conjunction.
As described above, optical lens according to the present embodiment is distributed to using metal oxide particle of the invention Transparent complex in resin forms small on the surface of the flat transparent substrate formed by the transparent complex Convex lens portions, thus light transmittance, refractive index, thermal stability, hardness and weatherability can be improved.
Therefore, it is possible to provide high transparency, high refractive index, high thermal stability, high rigidity and the excellent optical lens of weatherability. The microlens array, due to for high transparency, high refractive index, high thermal stability, high rigidity and the excellent lens array of weatherability Column, thus be suitable for requiring OA machine of duplicator, printer of high-resolution and high reliability etc. etc..
Further, it instantiates the method for lenticule excipient among the above in tabular component, it is saturating spherical surface can also to be used for well Mirror, non-spherical lens, cylindrical lens etc..
Hereinafter, to for being described in detail by the case where coating applications of representative of hard conating purposes.Gold of the invention Belonging to oxide particle has nanoscale polymolecularity, and the hardness of metal oxide is high, excellent abrasion, thus beneficial In the high rigidityization and imparting marresistance of substrate.Such as it can be according to production of such as getting off.
1) coating composition can also be as needed other than metal oxide particle of the invention, blends polymerism Monomer, polymerization initiator, thermal polymerization promotor, light sensitizer, photopolymerization promoter etc. further blend organic solvent, polymerization Object, various additives, and mix, stir to obtain.Coating composition can pass through irradiation when not blending polymerization initiator Electric wire, blend thermal polymerization when, can by heating, in addition, blend Photoepolymerizationinitiater initiater when, can by irradiate it is ultraviolet Line makes its solidification.
2) previous known by the hand painting of brush smearing etc. or spraying coating, infusion process etc. by the coating composition Method be coated on substrate.As coating weight, preferably 0.2-100g/m2In the range of, more preferably 0.5-70g/m2Model In enclosing.In addition, as coating thickness, in the range of preferably 1-500 μm, in the range of more preferably 2-200 μm.As being used for The substrate of layered product, such as polyethylene (PE), polypropylene (PP), polymethyl methacrylate (PMMA), polyacrylic acid can be enumerated Ester, polyvinyl alcohol (PVA), polystyrene (PS), polyethylene terephthalate (PET), polybutylene terephthalate (PBT) (PBT), ethylene-vinyl acetate copolymer (EVA), acrylonitrile-butadiene-styrene copolymer (ABS), Triafol T (TAC), cyclic olefin polymer (COP), polycarbonate (PC), polyether-ketone (PEEK), polyamidoimide (PAI), polyimides (PI), the resin forming article and film of polyetheramides (PEI), nylon (NY), polyvinyl chloride (PVC), Vingon etc.；Poly- second The stationery of coated paper, the non-coated paper of ene coatings paper, polyethylene terephthalate coated paper etc. etc.；Timber；Glass；It is stainless Metal class of steel, iron, aluminium, copper, alloy etc. etc..
3) then, make the coating composition for being coated on substrate, pass through heating or UV radiation curing, production solidification Film.For example, using infrared ray, far infrared, hot wind, high-frequency heating etc. when using the solidification of heating.Heating temperature, It can suitably be adjusted, be not particularly limited, preferably 80-200 DEG C, more preferably 90-180 DEG C according to type of substrate etc., into One step is preferably in the range of 100-170 DEG C.Heating time can suitably adjust according to spreading area etc., be not particularly limited, In the range of preferably 1 minute~24 hours, more preferably 10 minutes~12 hours, further preferably 30 minutes~6 hours.
For example, being using the light source containing the light in the range of wavelength 150-450nm when using the solidification of ultraviolet light It can.As such light source, such as sunray, Cooper-Hewitt lamp, high-pressure mercury-vapor lamp, extra-high-pressure mercury vapour lamp, metal can be enumerated Halide lamp, gallium lamp, xenon lamp, carbon arc lamp etc..It can also be together with these light sources, and with infrared ray, far infrared, hot wind, high frequency The heat of heating etc..Irradiate accumulated light, preferably 0.1-10J/cm2, more preferably 0.15-8J/cm2, further preferably 0.2- 5J/cm2In the range of.
For example, it is preferably 10-500kV that acceleration voltage, which can be used, more preferably 20- when using the solidification of electric wire Electric wire in the range of 300kV, further preferably 30-200kV.In addition, exposure is preferably 2-500kGy, it is more excellent It is selected as 3-300kGy, in the range of further preferably 4-200 is kGy.It can also be together with electric wire, and with infrared ray, remote The heat of infrared ray, hot wind, high-frequency heating etc..
In addition, coating composition can also be used forming while band method.This method, at least by film and layer will be banded Banding for being constituted is put into injection molding metal die with film, and after mode locking, shaping resin is projected to die cavity, is being shaped The surface of resin forming product after resin solidification makes to band with thin slice integration and be bonded, obtains shaping while banding formed products.
Hard conating material of the invention, suitable for the communicating machine of OA machine, mobile phone etc., household electronic products, vapour Automobile-used interior exterior part, furniture exterior member, plastic lens, cosmetics containers, beverage-container, organic el display etc. The purposes field of touch panel, sink, commode and the show window of display, household appliances etc., window-glass etc..
In addition, the present invention is based on Japanese patent application No. 2011-270198,2011 filed on December 9th, 2011 Japanese patent application filed in Japanese patent application filed in December 16 the 2011-275765th, on March 16th, 2,012 Japanese patent application 2012-85681 CLAIM OF PRIORITY interests filed in No. 2012-61186 and on April 4th, 2012.
Day filed in Japanese patent application filed on December 9th, 2011 the 2011-270198th, on December 16th, 2011 Japanese patent application the 2012-61186th filed in present patent application the 2011-275765th, on March 16th, 2012 and The full content of the specification of Japanese patent application filed on April 4th, 2012 the 2012-85681st can introduce the application use In reference.
Embodiment
Hereinafter, further illustrating the present invention by enumerating embodiment.The present invention is not limited by the examples below, when It can so implement being suitble to the range of aforementioned and aftermentioned objective to be subject to change appropriate, these are included in technology of the invention In range.
Physical property and characteristic disclosed in embodiment, are measured by the following method.
The physical property of 1.1 metal oxides (zirconium oxide, titanium oxide) particle
(1) parsing of crystalline texture
The crystalline texture of metal oxide particle is solved using X-ray diffraction device (リ ガ Network society system, RINT-TTRIII) Analysis.Determination condition is as described below.
X-ray source: CuK α (0.154nm)
X-ray output setting: 50kV, 300mA
Sampling width: 0.0200 °
Scanning speed: 10.0000 °/min
Measurement range: 10-75 °
Measuring temperature: 25 DEG C
(2) regular crystal, monoclinic crystal ratio quantify
Based on using the calculated value of X-ray diffraction device (リ ガ Network society system, RINT-TTRIII) institute, calculating is used Than method (RIP method), quantitatively (ownership of wave crest is also according to the finger of software for calculation by referring to intensity for software (リ ガ Network society system, PDXL) It is fixed).
(3) it is calculated using the crystallization particle diameter of X-ray diffraction analysis
Crystallization particle diameter is gone out by using X-ray diffraction device (リ ガ Network society system, RINT-TTRIII) analytical Calculation, by 2 θ= Crystallization particle diameter of the partial size of 30 ° of wave crest as Zirconia particles, using the partial size of the wave crest of 2 θ=25 ° as Titanium particles Crystallization particle diameter.In addition, crystallization particle diameter, to use X-ray diffraction device (リ ガ Network society system, RINT-TTRIII) 30 ° calculated Wave crest and 25 ° of wave crest halfwidth based on, using software for calculation (リ ガ Network society system, PDXL), with following Scherrers (Scherrer) formula calculates crystallization particle diameter (L).
L=K λ/β cos θ
K: constant
λ: the wavelength of X-ray tube is used
β: halfwidth
2 θ: angle of diffraction
(4) it is measured using the average grain diameter of electron microscope
The average primary particle diameter of Zirconia particles, by utilizing ultrahigh resolution field emission scanning electron microscope (day Vertical Ha イ テ Network ノ ロ ジ ー ズ system, S-4800) it observes to measure.With 150,000 times of observation Zirconia particles of multiplying power, to any 100 A particle measures the length of the long axis direction of each particle, using its average value as average primary particle diameter.
(5) measurement of weight (quality) loss late
By TG-DTA (TG-DTA analysis) device, under air atmosphere, with 10 DEG C/minute by metal oxide particle By room temperature to 800 DEG C, weight (quality) loss late of the particle is measured.By weight (quality) loss late, it is known that covering The ratio of the carboxylate compound of metal oxide particle and the ratio of metal oxide.
(6) particle heat-resistance test
By metal oxide particle, under air atmosphere, after being placed 24 hours at 180 DEG C, visually to observe color change Change.Not changing colour is qualification, and it is unqualified for having discoloration.
(7) measurement of carbon content
By J-Science society JM10, the measurement of carbon content is carried out.
(8)1The measurement of H-NMR
Covering metal oxide particle is dispersed in deuterated chloroform as measurement sample, Variann society is used " Unity Plus " (resonant frequency: 400MHz, integral number of times: 16 times) is measured.Based on following chemical shift (tetramethylsilanes Alkyl is quasi-) wave crest integral ratio, determine the molar ratio of each compound.
I) 2 ethyl hexanoic acid (1.0-0.5ppm:6H)
Ii) from the carboxylate of 2 ethyl hexanoic acid (1.0-0.5ppm:6H)
Iii) 2- acryloyl-oxyethyl succinic acid (6.7-5.7ppm:3H)
Iv) 2- acryloyl-oxyethyl hexahydrophthalic acid (6.8-5.6ppm:3H)
V) 2- acryloyl-oxyethyl phthalic acid (6.8-5.2ppm:3H)
Vi) 3,3- acid dimethyl (1.0-0.5ppm:9H)
Vii the carboxylate (1.0-0.5ppm:9H)) from 3,3- acid dimethyl
(9) measurement of Zr, Si content
Using fluorescent x-ray analyzer (ZSX PrimusII リ ガ Network society system), the Zr measured in Zirconia particles contains Amount, Si content.
(10) measurement of the chlorinity in Zirconia particles
Chlorinity uses ion chromatograph (DIONEX society ICS-2000), is parsed according to determination condition below. Zirconia particles and zirconium dimethyl butyric acid compound are measured with combustion method.
Column: IonPac AS11HC
Eluent: potassium hydroxide 23mmol/L
The characteristic of 1.2 polymer
(11) weight average molecular weight
Using gel permeation chromatography measurement device (" Shodex GPC System-21H " Showa electrician system), by polymer Weight average molecular weight be scaled polystyrene and be measured.
(12) polymer concentration in polymer solution
Solution made of acetone 4g dissolution will be added in polymer solution 1g, spontaneously dry, further exist at normal temperature It is cooling in drying box after being dried under reduced pressure (160 DEG C/5mmHg) at 100 DEG C 5 hours, and quality measurement.Then, to be dried under reduced pressure Weight afterwards is as polymer weight, by it divided by polymer solution 1g, as polymer concentration.
(13) acid value
Acetone 80ml and water 10ml is added in polymer solution 0.5-1g and stirs makes its uniform dissolution, by 0.1mol/L KOH aqueous solution as titrating solution, titrated using automatic titration device (" COM-555 " flat natural pond industry system), measure solution Acid value.Then, it is assumed that acid all is from polymer, by the acid value and polymer concentration of solution, calculates the acid value of polymer.
The characteristic of 1.3 hardening resin compositions
(14) transparency evaluation in second method
By the light transmittance (optical wavelength: 400nm) of the thickness direction of no glass slide for carrying out any coating, extinction light is used Degree meter (Shimadzu Seisakusho Ltd.'s spectrophotometer " UV-3100 ") is measured, its light transmittance is set to T1%.Then, glass is being carried Hardening resin composition rod coater #10 is coated with, heats at 80 DEG C after five minutes, with high-pressure mercury light irradiation by piece 50mJ/cm2Ultraviolet light make its solidification, obtain cured coating film.The formation of production is had to the thickness side of the glass slide of cured coating film To light transmittance (optical wavelength: 400nm), be measured using spectrophotometer " UV-3100 ", its light transmittance be set to T2%. Light transmittance T is calculated by following formula by these values.
T (%)=100+T2 (%)-T1 (%)
(15) transparency evaluation in fourth method
On glass slide, it is coated film thickness as 100 μm of mode with coating machine aftermentioned composition, in nitrogen Under atmosphere, by with high-pressure mercury light irradiation 1000mJ/cm2Ultraviolet light make its solidification, obtain solidfied material.Use spectrophotometric Count (society, Shimadzu Seisakusho Ltd. spectrophotometer UV-3100), when measuring to the light of the solidfied material illumination wavelength 400nm of production The light transmittance of thickness direction.
(16) developability is evaluated
On the glass substrate by hardening resin composition rotary coating, 3 minutes dry at 100 DEG C, forming film thickness is 2.0 μm of film.It is 30 μm via line width with UV exposure device (Topcon society system, trade name: TME-150RNS) by film Line and interval light shield, use 50mJ/cm2UV light exposure, use spin developer (ア Network テ ス society system, trade name: ADE- 3000S), development 20 seconds is carried out with 0.05% potassium hydroxide aqueous solution, carries out the evaluation of developability.
(17) detecting refractive index is tested
On glass slide, it is coated film thickness as 100 μm of mode with coating machine hardening resin composition, Under nitrogen atmosphere, with high-pressure mercury light irradiation 1000mJ/cm2Ultraviolet light make its solidification, obtain solidfied material.Use index meter (ア タ go society system, DR-M2), at 20 DEG C, the refractive index of light of the measurement gained solidfied material at wavelength 589nm.
(18) dielectric constant is evaluated
On copper foil, film thickness is set to carry out coating as 50 μm of mode with rod coater aftermentioned composition, in nitrogen Under atmosphere, with high-pressure mercury light irradiation 1000mJ/cm2Ultraviolet light make its solidification, obtain solidfied material.Further, it is steamed on surface It is gold-plated, it is produced on the sample for evaluation that electrode is formed on two sides.Using impedance analyzer (ヒ ュ ー レ ッ ト パ ッ カ ー De society system, Trade name " 4294A ") sample is measured in the dielectric constant of 1MHz.
(19) pencil hardness
According to 5400 8.4.1 of JIS K (testing machine method), pencil scraping experiment is carried out, it will be when being damaged on film Pencil hardness as hardness.
(20) forming characteristic
(a) production of the pyramid array mold of PDMS
On the Si wafer in the four directions 10mm, being processed into depth using cutting mechanics is 25 μm, and spacing is 50 μm, and apex angle is 90 ° of V-type ditch is similarly machined, it is 25 μ that production side length, which is 50 μm of height, by the way that the direction of substrate to be rotated by 90 ° The master mold for the pyramid array mold that the Pyramid (quadrangular pyramid) of m is regularly arranged.
On the surface of the master mold, using spin coater by release agent (Off ロ ロ テ Network ノ ロ ジ ー society system, " Off ロ ロ サ ー Off " (registered trademark) FG5020 ") coating film (application conditions: slope 5sec → 1500rpm 30sec) after, It is 5 minutes dry in 80 DEG C of heating plate.
Using the mold of above-mentioned obtained demoulding processing as master mold, the mould of dimethyl silicone polymer (PDMS) system is made Tool.Specifically, for by dimethyl silicone polymer (シ リ コ ー Application society, SHIN-ETSU HANTOTAI system, " KE-1310ST ") and catalyst (SHIN-ETSU HANTOTAI's シ リ U ー Application society system, " CAT-1310S ") with 10:1 (mass ratio) mixing, and carry out deaeration.The mixture is poured on the master mold, By the support substrate (quartz plate) of upper setting casting.Directly after being placed at room temperature for 24 hours, keep 3 small at 80 DEG C in baking oven When.Then, master mold is demoulded, makes the pyramid array mold (the regularly arranged mold of recessed quadrangular pyramid) of PDMS.Also, by The mold for the PDMS that " KE-1310ST " and " CAT-1310S " is formed, glass transition temperature is -140~-120 DEG C, at 23 DEG C Modulus of elasticity is 6.0MPa.
(b) it shapes
On Si wafer, hardening resin composition is added dropwise, the pyramid array mold of PDMS is set, uses simple pressure Printing equipment is set, and is squeezed with loading 0.1MPa.With the state of extrusion die, high-pressure mercury light irradiation 1000mJ/cm is used2It is ultraviolet Line solidifies resin combination, then removes UV pyramid array mold.By the zirconia nanopowder containing figuration on Si wafer The structural body of particle is shot with scanning electron microscope (SEM), evaluates shape.
Embodiment 1
By alkaline carbonic acid zirconium 100g (Zr2(CO3)(OH)2O2, it is ZrO2The wet feed product of content 43%, water content are rubbed relative to 1 Your zirconium is 7 moles, Japanese light metal society system), 2,2- acid dimethyl 83g (Tokyo chemical conversion industry society system), dimethylbenzene 50g with And the mixed liquor of deionized water 59g, it is warming up to 80 DEG C under open system, stirs 1 hour.Organic layer 5g after taking out reaction, It is added in acetone 50g, white precipitate is precipitated.The white precipitate of precipitation is filtered and is taken out, is done under vacuum at room temperature Dry 12 hours, obtain ZrO (OH) (CO3)1/2(1-n)(OCOC5H11)n.Gained compound according to " the survey of (5) rate of weight loss The rate of weight loss measured calmly " is 53%, therefore ZrO contained in resulting compound2Weight ratio be 47%, by The weight ratio of Zr atom known to this is 35%.In addition, being obtained according to the result that " measurement of (7) carbon content " is measured The carbon content of compound is 30%, it is known that C5H11The content ratio of COO unit is 48%.It can be seen from this result that Zr atom and C5H11The molar ratio of COO unit is 1/1, n=1 in above-mentioned formula.
Embodiment 2
Under stiring, in 40 DEG C of pure water 210.6g, addition sodium hydroxide 30g (キ シ ダ chemistry society system, superfine) is obtained To sodium hydrate aqueous solution.Then, under stiring, in the sodium hydrate aqueous solution, 2,2- acid dimethyl is added 100.0g (Tokyo chemical conversion industry society system) modulates 2,2- dimethyl butyrate acid sodium aqueous solution.
Then, it in 2, the 2- dimethyl butyrate acid sodium aqueous solution, is added dimethylbenzene 432.8g (northern Hong Kongnization society system), adds Heat is to 80 DEG C, under stiring, by zirconium oxychloride 221.8g (ZrOCl2·8H2O, the first rare element chemistry industry society system, Zircosol ZC-20) spend 20 minutes investments.Then, it is persistently stirred at 80 DEG C 1 hour, after removing water phase, by that will have Machine layer is sufficiently washed, and 2,2- acid dimethyl zirconium xylene solution 490g is obtained.Then, by 2,2- acid dimethyl zirconium dimethylbenzene Solution is concentrated into 120g with reduced pressure machine, and methanol 360g (northern Hong Kongnization society system) is added wherein, and by the white of precipitation The filtering of 2,2- acid dimethyl zirconiums is taken out, and is dried under vacuum at room temperature 12 hours.According to " measurement of (5) rate of weight loss " The rate of weight loss of 2,2- acid dimethyl zirconium after the drying measured is 65%, 2, the 2- acid dimethyl zirconium after drying Yield is 100g.
Above-mentioned 2,2-dimethylbutyric acid zirconium is according to the rate of weight loss that " measurement of (5) rate of weight loss " is measured 65%, therefore ZrO contained in gained compound2Weight ratio be 35%, it can thus be appreciated that the weight ratio of Zr atom is 26%.In addition, be 41% according to the carbon content that the result that " measurement of (7) carbon content " is measured is obtained compound, by C known to this5H11The content ratio of COO unit is 66%.Zr atom and C are confirmed by the result5H11The molar ratio of COO unit is 1/ 2, structure is ZrO (OCOC5H11)2。
Embodiment 3
By alkaline carbonic acid zirconium 100g (composition formula: Zr2(CO3)(OH)2O2, ZrO2The wet feed product of content 43%, Japanese light metal Society's system), 2,2-dimethylbutyric acid 83g (being 2 moles relative to 1 mole of zirconium), dimethylbenzene 50g and deionized water 59g it is (opposite In 1 mole of zirconium be 9 moles) mixed liquor be added high-pressure reactor, the atmosphere in the high-pressure reactor is replaced with nitrogen.So Afterwards, mixed liquor is heated to 190 DEG C, is kept for 22 hours (pressure in high-pressure reactor is 2.5MPa).It is molten after taking out reaction The sediment for being deposited on bottom is filtered, is cleaned with 200g toluene by liquid.By obtaining the cover type of white for the drying of clean object Zirconia particles 40g.
Embodiment 4
Other than using 2,2- acid dimethyl 63g (being 1.5 moles relative to 1 mole of zirconium), similarly to Example 3 Ground obtains the cover type Zirconia particles 29g of white.
Embodiment 5
By alkaline carbonic acid zirconium 100g (Zr2(CO3)(OH)2O2, ZrO2The wet feed product of content 43%, Japanese light metal society system), High-pressure reactor is added in the mixed liquor of 2,2- acid dimethyl 83g, 1,2,4- trimethylbenzene 50g and deionized water 59g, by this The atmosphere of high-pressure reactor is replaced with nitrogen.Then, mixed liquor is heated to 190 DEG C, holding 22 hours (in high-pressure reactor Pressure is 2.5MPa).The sediment for being deposited on bottom is filtered, is cleaned with 200g toluene by the solution after taking out reaction.Passing through will Object drying is cleaned, the cover type Zirconia particles 37g of white is obtained.
Embodiment 6
Other than using 2,2- acid dimethyl 63g, the cover type zirconium oxide grain of white is obtained similarly to Example 5 Sub- 36g.
Embodiment 7
By alkaline carbonic acid zirconium 100g (Zr2(CO3)(OH)2O2, ZrO2The wet feed product of content 43%, Japanese light metal society system), (zirconium relative to 1 mole is by 2,2-dimethylbutyric acid 63g, 1,2,4- trimethylbenzene 50g and deionized water 59g, NaOH 3g 0.2 mole) mixed liquor be added high-pressure reactor, the atmosphere of the high-pressure reactor is replaced with nitrogen.Then, by mixed liquor plus Heat is kept for 22 hours (pressure in high-pressure reactor is 2.6MPa) to 190 DEG C.Solution after taking out reaction, will be deposited on bottom The sediment in portion filters, and is cleaned with 200g toluene.By obtaining the cover type Zirconia particles 46g of white for the drying of clean object.
Embodiment 8
Other than using 2,2- acid dimethyl 42g (being 1 mole relative to 1 mole of zirconium), similarly to Example 7 Obtain the cover type Zirconia particles 44g of white.
Embodiment 9
By alkaline carbonic acid zirconium 100g (Zr2(CO3)(OH)2O2, ZrO2The wet feed product of content 43%, Japanese light metal society system), The mixed liquor addition high-pressure reactor of 2,2- acid dimethyl 42g, 1,2,4- trimethylbenzene 100g and NaOH 3g, by the height The atmosphere of pressure reactor is replaced with nitrogen.Then, mixed liquor is heated to 190 DEG C, keeps 22 hours (pressures in high-pressure reactor Power is 2.4MPa).The sediment for being deposited on bottom is filtered, is cleaned with 200g toluene by the solution after taking out reaction.By that will wash Net object is dry, obtains the cover type Zirconia particles 35g of white.
Embodiment 10
In addition to using 2,2- acid dimethyl 21g (being 0.5 mole relative to 1 mole of zirconium), make in high-pressure reactor Pressure is to obtain the cover type Zirconia particles 26g of white similarly to Example 9 other than 2.6MPa.
Embodiment 11
In addition to using 1,2,4- trimethylbenzene 50g, make other than the pressure 2.6MPa in high-pressure reactor, with embodiment 9 Get similarly the cover type Zirconia particles 43g of white.
Embodiment 12
By alkaline carbonic acid zirconium 100g (Zr2(CO3)(OH)2O2, ZrO2The wet feed product of content 43%, Japanese light metal society system), The mixed liquor addition high-pressure reactor of 2,2- acid dimethyl 63g, deionized water 59g and NaOH 3g, by the high-pressure reactor Atmosphere replaced with nitrogen.Then, mixed liquor is heated to 190 DEG C, being kept for 22 hours, (pressure in high-pressure reactor is 2.6MPa).The sediment for being deposited on bottom is filtered, is cleaned with 200g toluene by the solution after taking out reaction.By by clean object It is dry, obtain the cover type Zirconia particles 47g of white.
Embodiment 13
By alkaline carbonic acid zirconium 100g (Zr2(CO3)(OH)2O2, ZrO2The wet feed product of content 43%, Japanese light metal society system), (zirconium relative to 1 mole is by 2,2-dimethylbutyric acid 83g, 1,2,4- trimethylbenzene 50g, deionized water 59g and NaOH9g 0.6 mole) mixed liquor be added high-pressure reactor, the atmosphere of the high-pressure reactor is replaced with nitrogen.Then, by mixed liquor plus Heat is kept for 22 hours (pressure in high-pressure reactor is 2.1MPa) to 170 DEG C.Solution after taking out reaction, will be deposited on bottom The sediment in portion filters, and is cleaned with 200g toluene.By obtaining the cover type Zirconia particles 41g of white for the drying of clean object.
Embodiment 14
By alkaline carbonic acid zirconium 100g (Zr2(CO3)(OH)2O2, ZrO2The wet feed product of content 43%, Japanese light metal society system), The mixed liquor of 2,2- acid dimethyl 83g, 1,2,4- trimethylbenzene 50g and deionized water 59g, are warming up under open system It 80 DEG C, stirs 1 hour.Then, NaOH 9g is added, and is added in high-pressure reactor, by the atmosphere nitrogen of the high-pressure reactor Gas displacement.Then, mixed liquor is heated to 170 DEG C, is kept for 22 hours (pressure in high-pressure reactor is 0.8MPa).It takes out anti- The sediment for being deposited on bottom is filtered, is cleaned with 200g toluene by the solution after answering.By obtaining white for the drying of clean object Cover type Zirconia particles 38g.
Embodiment 15
By alkaline carbonic acid zirconium 100g (Zr2(CO3)(OH)2O2, ZrO2The wet feed product of content 43%, Japanese light metal society system), The mixed liquor of 2,2- acid dimethyl 83g, dimethylbenzene 50g and deionized water 59g, 80 DEG C are warming up under open system, is stirred It mixes 1 hour.Then, high-pressure reactor is added in mixed liquor, the atmosphere of the high-pressure reactor is replaced with nitrogen.Then, it will mix It closes liquid and is heated to 190 DEG C, kept for 22 hours (pressure in high-pressure reactor is 1.4MPa).Solution after taking out reaction, will sink Sediment of the product in bottom filters, and is cleaned with 200g toluene.By obtaining the cover type zirconium oxide grain of white for the drying of clean object Sub- 41g.
Zirconia particles obtained for embodiment 3-15 carry out the ratio of regular crystal by the method for above-mentioned (1)-(6) The confirmation of example, rate of weight loss, average grain diameter, heat resistance.It the results are shown in table 1, in table 2.
[table 1]
The molal quantity relative to 1 mole of zirconium is indicated in ※ table, in ().
[table 2]
The molal quantity relative to 1 mole of zirconium is indicated in ※ table, in ().
Embodiment 16
In obtained 2, the 2- acid dimethyl zirconium 270g of embodiment 2, mixed xylenes 338g and pure water 288g are obtained Mixed liquor.The mixed liquor is added in the high-pressure reactor with blender, the atmosphere of the high-pressure reactor is set with nitrogen It changes.Then, mixed liquor is heated to 190 DEG C, after being kept for react it within 16 hours (pressure in high-pressure reactor is 1.4MPa), It is taken out from high-pressure reactor, the sediment for being deposited on bottom is filtered, is cleaned with 210g toluene.By the way that clean object is dry, Obtain the cover type Zirconia particles 103g of white.
The crystalline texture of obtained Zirconia particles is confirmed, detects to belong to regular crystal and monoclinic diffraction Line, by the intensity of diffracted ray it is found that regular crystal and monoclinic ratio are 27/73, partial size (crystallization particle diameter) is 8nm.
Average grain diameter (average primary particle diameter) by the obtained Zirconia particles of determination of electron microscopy is 11nm.This Outside, by obtained Zirconia particles, with infrared absorption spectrum analysis, as a result confirm from C-H absorption and from The absorption of COOH.The absorption, it is believed that it is due to be covered on 2, the 2- acid dimethyl of Zirconia particles and/or from 2, The carboxylate of 2- acid dimethyl.
Further, the rate of weight loss of the Zirconia particles measured according to above-mentioned " measurement of (5) rate of weight loss " is 12 mass %.It may thus be appreciated that the 2,2-dimethylbutyric acid of covering Zirconia particles and the carboxylate from 2,2-dimethylbutyric acid Total amount, be cover type Zirconia particles entirety 12 mass %.
In addition, heat-resistance test as a result, Zirconia particles keep white and it is unchanged.
Embodiment 17 uses the example of 3,3- acid dimethyl
Under stiring, in 40 DEG C of pure water 421g, addition sodium hydroxide 60g (キ シ ダ chemistry society system, superfine) is obtained Sodium hydrate aqueous solution.Then, under stiring, in the sodium hydrate aqueous solution, 3,3- acid dimethyl 200.0g is added (Tokyo chemical conversion industry society system) modulates 3,3- dimethyl butyrate acid sodium aqueous solution.
Then, in 3, the 3- dimethyl butyrate acid sodium aqueous solution, ethyl cyclohexane 649g (Wan Shan petrochemistry society is added System), 80 DEG C are heated to, under stiring, by zirconium oxychloride 444g (ZrOCl2·8H2O, the first rare element chemistry industry society system, Zircosol ZC-20) spend 20 minutes investments.Then, it is persistently stirred at 80 DEG C 1 hour, it is abundant with water after removing water phase Organic layer is cleaned, 3,3- acid dimethyl zirconium ethyl cyclohexane solution 830g is obtained, then, by 3,3- acid dimethyl zirconium ethyl Cyclohexane solution is concentrated into 270g with reduced pressure machine, and white is precipitated in methanol 810g (northern Hong Kongnization society system) 3 are added wherein, 3- acid dimethyl zirconium, filtering are taken out 3, the 3- acid dimethyl zirconium of white, are dried under vacuum at room temperature 12 hours.According to The rate of weight loss of 3,3- acid dimethyl zirconium after the drying that " measurement of (5) rate of weight loss " is measured is 63%, dry The yield of 3,3- acid dimethyl zirconium afterwards is 190g.
In 3, the 3- acid dimethyl zirconium 270g obtained in this way, 1,2,4- trimethylbenzene 338g (ア Le De リ ッ チ is mixed Society's system), sodium hydroxide 37g (キ シ ダ chemistry society system, superfine) and pure water 288g obtain mixed liquor.The mixed liquor is added to In high-pressure reactor with blender, the atmosphere of the high-pressure reactor is replaced with nitrogen.Then, mixed liquor is heated to 190 DEG C, after keeping react it at such a temperature within 16 hours (pressure in high-pressure reactor is 1.4MPa), by high-pressure reactor It takes out, the sediment for being deposited on bottom is filtered, is cleaned with 210g toluene.By obtaining the covering of white for the drying of clean object Type Zirconia particles 51g.
The crystalline texture of obtained Zirconia particles is confirmed, detects to belong to regular crystal and monoclinic diffraction Line, by the intensity of diffracted ray it is found that regular crystal and monoclinic ratio are 5/95, partial size (crystallization particle diameter) is 8nm.
Average grain diameter (average primary particle diameter) by the obtained Zirconia particles of determination of electron microscopy is 11nm.This Outside, by obtained Zirconia particles, with infrared absorption spectrum analysis, as a result confirm from C-H absorption and from The absorption of COOH.The absorption, it is believed that be due to be covered on 3, the 3- acid dimethyl of Zirconia particles and/or from 3,3- The carboxylate of acid dimethyl.
Further, the rate of weight loss of the Zirconia particles measured according to above-mentioned " measurement of (5) rate of weight loss " is 12 mass %.It may thus be appreciated that the 3,3- acid dimethyl of covering Zirconia particles and the carboxylate from 3,3- acid dimethyl Total amount, be cover type Zirconia particles entirety 12 mass %.
In addition, heat-resistance test as a result, Zirconia particles keep white and it is unchanged.
Embodiment 18
Under stiring, in 40 DEG C of pure water 11.5g, addition sodium hydroxide 2.6g (キ シ ダ chemistry society system, superfine) is obtained To sodium hydrate aqueous solution.Then, under stiring, in the sodium hydrate aqueous solution, addition neopentanoic acid 7.5g (Tokyo chemical conversion Industrial society's system), neopentanoic acid sodium water solution is modulated, is heated to 80 DEG C.
Then, under stiring, in the neopentanoic acid sodium water solution, by zirconium oxychloride 18.9g (ZrOCl2·8H2O, first Rare element chemistry industry society system, Zircosol ZC-20) 20 minutes investments are spent, the neopentanoic acid zirconium of white is precipitated.This is new The filtering of valeric acid zirconium is taken out, and after methanol cleaning, is dried under vacuum at room temperature 12 hours.According to " the survey of (5) rate of weight loss The rate of weight loss of neopentanoic acid zirconium after the drying measured calmly " is 60%, and the yield of the neopentanoic acid zirconium after drying is 8.5g.
In gained neopentanoic acid zirconium 1.06g, mixed xylenes 1.22g, pure water 1.13g and sodium hydroxide 0.13g (キ シ ダ chemistry society system, superfine) obtain mixed liquor.The mixed liquor is added in the high-pressure reactor with blender, by the high pressure The atmosphere of reactor is replaced with nitrogen.Then, mixed liquor is heated to 190 DEG C, keeps 16 hours (reaction under high pressures at such a temperature It after pressure in device reacts it for 1.4MPa), is taken out by high-pressure reactor, the sediment that will be deposited on bottom filters, and uses 10g Toluene is cleaned.By obtaining the cover type Zirconia particles 0.17g of white for the drying of clean object.
The crystalline texture of obtained Zirconia particles is confirmed, detects to belong to regular crystal and monoclinic diffraction Line, by the intensity of diffracted ray it is found that regular crystal and monoclinic ratio are 69/31, partial size (crystallization particle diameter) is 4nm.
In addition, by obtained Zirconia particles, with infrared absorption spectrum analysis, confirm from C-H absorption and From the absorption of COOH.The absorption, it is believed that be due to be covered on the neopentanoic acid of Zirconia particles and/or from neopentanoic acid Carboxylate.
Further, the rate of weight loss of the Zirconia particles measured according to " measurement of (5) rate of weight loss " is 17 matter Measure %.Therefore, the neopentanoic acid of Zirconia particles and the total amount of the carboxylate from neopentanoic acid are covered, is cover type zirconium oxide 17 mass % of particle entirety.
In addition, heat-resistance test as a result, Zirconia particles keep white and it is unchanged.
Embodiment 19
By mixing the obtained Zirconia particles 1.0g of embodiment 17, stearic acid 1.0g and toluene 18.0g, 50 Heating obtains Zirconia particles transparent dispersion at DEG C.
Embodiment 20
By mixing the obtained Zirconia particles 1g of embodiment 15, acetic acid 4.5g, deionized water 4.5g, aoxidized Zirconium dispersion liquid.By mixing PLACCEL FM-10.5g (methacrylic acid monomer containing hydroxyl, ダ イ in the dispersion liquid セ Le chemistry society system) and DAROCUR1173 (free radical type Photoepolymerizationinitiater initiater, BASF society system) obtain zirconia dispersion. 0.1g is added dropwise with dropper in the dispersion on a glass, is heated 30 minutes at 150 DEG C.Then, with high-pressure mercury light irradiation 8J/cm2Ultraviolet light make its solidification, obtain transparent coating.Gained film is touched with finger, fingerprint is not had, confirms and fill Divide solidification.
Embodiment 3-13 to mix zirconium carbonate, carboxylic acid and other compounds, and carries out the example of hydro-thermal process Son.Embodiment 14 and 15, to be reacted in the presence of other compounds other than NaOH by zirconium carbonate and carboxylic acid, For embodiment 14, the example of hydro-thermal process is carried out for addition NaOH thereafter.The either case of embodiment 3-15 can be obtained by carboxylic The Zirconia particles of ester compound covering.
Embodiment 3 and 4,5 and 6,7 and 8,9 and 10 are compared respectively, it is known that by keeping the quantitative change of carboxylic acid few, can mention The ratio of high regular crystal.
Embodiment 7 and 12 is compared, it is known that by using fragrant hydrocarbon system solvent, the ratio of regular crystal can be improved.
Embodiment 9 and 11 is compared, it is known that the quantitative change of fragrant hydrocarbon system solvent is more, and the ratio of regular crystal can be made to become larger.
Embodiment 6 and 7 is compared, it is known that the ratio of regular crystal can be improved by using NaOH.
Embodiment 8 and 11 is compared, it is known that by adjusting the amount of water, can adjust the ratio of regular crystal.
Embodiment 3 and 15,13 and 14 are compared respectively, it is known that carry out water again after first making zirconium carbonate and carboxylic acid reaction Heat treatment can make reaction pressure when hydro-thermal process lower compared with the case where carrying out the reaction and hydro-thermal process simultaneously.
In embodiment 18, to use zirconium oxychloride as oxygen alloy category compound, use neopentanoic acid sodium as Carboxylation Object is closed, they are carried out to the example of hydro-thermal process, the oxidation covered by carboxylate compound also can be obtained by such method Zirconium particle.
Preparation example 2-1
By 2 ethyl hexanoic acid and/or the carboxylate from 2 ethyl hexanoic acid covering zirconium oxide nano-particle (cover type ZrO2Particle) preparation
In 2 ethyl hexanoic acid zirconium mineral spirits solution (782g, 44 mass % of 2 ethyl hexanoic acid zirconium content, the first rare element Chemical industry corporation system) (pKa=4.82 of 2 ethyl hexanoic acid) middle mixing pure water (268g).Gained mixed liquor is added to have and is stirred It mixes in the high-pressure reactor of machine, the atmosphere of the high-pressure reactor is replaced with nitrogen.Then mixed liquor is heated to 180 DEG C, It keeps 16 hours (pressure in high-pressure reactor is 0.94MPa) making its reaction at this temperature, generates Zirconia particles.Then, Mixed liquor after taking out reaction filters the sediment for being deposited on bottom, dry after being cleaned with acetone.It will be described heavy after drying Starch (100g) is distributed in toluene (800mL), forms gonorrhoea solution.Then, as refining step, with quantitative filter paper (ア De Society, バ ンテック Japan system, No.5C) it filters again, remove the oversize grain etc. in sediment.Further, filtrate decompression is dense Contracting removes toluene, recycles Zirconia particles (the cover type ZrO of white2Particle).
To obtained cover type ZrO2The crystalline texture of particle confirmed, detects to belong to regular crystal and monoclinic Diffracted ray, by the intensity of diffracted ray it is found that regular crystal and monoclinic ratio are 54/46, partial size (crystallization particle diameter) is 5nm.
Pass through the obtained cover type ZrO of determination of electron microscopy2The average grain diameter (average primary particle diameter) of particle is 12nm.In addition, by obtained cover type ZrO2Particle, with infrared absorption spectrum analysis, confirm from C-H absorption and From the absorption of COOH.The absorption, it is believed that be due to be covered on the 2 ethyl hexanoic acid of Zirconia particles and/or from The carboxylate of 2 ethyl hexanoic acid.
Further, the cover type ZrO measured according to above-mentioned " measurement of (5) mass loss rate "2The mass loss of particle Rate is 12 mass %.It may thus be appreciated that the 2 ethyl hexanoic acid of covering Zirconia particles and/or the carboxylate from 2 ethyl hexanoic acid, For 12 mass % of Zirconia particles entirety.
Embodiment 2-1
By 2 ethyl hexanoic acid and/or the carboxylate from 2 ethyl hexanoic acid and 2- acryloyl-oxyethyl succinic acid covering Zirconium oxide nano-particle (replaces cover type ZrO2Particle 1) preparation
By the obtained cover type ZrO of preparation example 2-12Particle (10g), 2- acryloyl-oxyethyl succinic acid (2g) (pKa =4.35) it is stirred in propylene glycol monomethyl ether acetate (12g, hereinafter referred to as " PGMEA ") to evenly dispersed.Then, lead to Crossing addition n-hexane (36g) makes dispersed particle agglomerate and solution is made gonorrhoea occur, separates aggregated particle from gonorrhoea solution with filter paper. Then, isolated aggregated particle is added in n-hexane (36g), after ten minutes, aggregated particle is separated with filter paper for stirring, is led to It crosses and obtained particle is dried under vacuum at room temperature, modulate by 2 ethyl hexanoic acid and/or from the carboxylic of 2 ethyl hexanoic acid Acid esters and the Zirconia particles of 2- acryloyl-oxyethyl succinic acid surface treatment (replace cover type ZrO2Particle 1).
By obtained substitution cover type ZrO2Particle 1 is distributed to deuterated chloroform as measurement sample, carries out1H-NMR's Analysis.As a result, knowing 2 ethyl hexanoic acid and/or carboxylate from 2 ethyl hexanoic acid and 2- acryloyl-oxyethyl succinic acid It is 10:90 there are molar ratio.
Further, the substitution cover type ZrO measured according to above-mentioned " measurement of (5) mass loss rate "2The quality of particle 1 Loss late is 20 mass %.It may thus be appreciated that the 2 ethyl hexanoic acid of covering Zirconia particles and/or the carboxylic acid from 2 ethyl hexanoic acid Ester and acrylyl oxy-ethyl succinic acid are 20 mass % of Zirconia particles entirety.
Embodiment 2-2
By 2 ethyl hexanoic acid and/or the carboxylate from 2 ethyl hexanoic acid and 2- acryloyl-oxyethyl succinic acid covering Zirconium oxide nano-particle (replaces cover type ZrO2Particle 2) preparation
By the obtained cover type ZrO of preparation example 2-12Particle (10g), 2- acryloyl-oxyethyl succinic acid (1g) exist It is stirred in PGMEA (12g) to evenly dispersed.Then, dispersed particle cohesion is made to make solution by adding n-hexane (36g) There is gonorrhoea, separates aggregated particle from gonorrhoea solution with filter paper.Then, isolated aggregated particle is added to n-hexane (36g) In, after ten minutes, aggregated particle is separated with filter paper for stirring, by the way that obtained particle is dried under vacuum at room temperature, Modulation by 2 ethyl hexanoic acid and/or the carboxylate from 2 ethyl hexanoic acid and 2- acryloyl-oxyethyl succinic acid surface treatment Zirconia particles (replace cover type ZrO2Particle 2).
Gained is replaced into cover type ZrO2Particle 2 is dispersed in deuterated chloroform as measurement sample, carries out1Point of H-NMR Analysis.As a result, knowing depositing for 2 ethyl hexanoic acid and/or carboxylate from 2 ethyl hexanoic acid and 2- acryloyl-oxyethyl succinic acid It is 30:70 in molar ratio.
Further, the substitution cover type ZrO measured according to above-mentioned " measurement of (5) mass loss rate "2The quality of particle 2 Loss late is 20 mass %.It may thus be appreciated that the 2 ethyl hexanoic acid of covering Zirconia particles and/or the carboxylic acid from 2 ethyl hexanoic acid Ester and acrylyl oxy-ethyl succinic acid are 20 mass % of Zirconia particles entirety.
Synthesis example 2-1
Prepare the detachable flask with condenser pipe as reactive tank, is stirred in addition, making adequate preparation in monomer dropping slot Mix mixing dimethyl -2,2 '-[oxygen is bis- (methylene)] double -2- acrylate (20g, hereinafter referred to as " MD "), methacrylic acid (50g, hereinafter referred to as " MAA "), methacrylic acid methyl (80g, hereinafter referred to as " MMA "), cyclohexyl methacrylate (50g, with Down referred to as " CHMA "), tert-butyl peroxide -2 ethyl hexanoic acid ester (4g, " the PERBUTYL O " of Japanese grease society；Hereinafter, claiming For the mixture of " PBO "), PGMEA (75g), make adequate preparation in chain-transferring agent dropwise adding tank be mixed β-mercaptopropionic acid (6g, Hereinafter referred to as " β-MPA "), the mixture of PGMEA (5g).
PGMEA (234g) is added in reactive tank, after being replaced with nitrogen, stirring oil bath heating in side heats up reactive tank To 90 DEG C.Content is added dropwise after 90 DEG C are stablized in the temperature of reactive tank by monomer dropping slot and chain-transferring agent dropwise adding tank respectively Object.90 DEG C of temperature is kept when being added dropwise, and is spent 135 minutes respectively and is carried out.Completion of dropwise addition starts after sixty minutes by reactive tank It is warming up to 110 DEG C.It maintains at 110 DEG C after 3 hours, loads onto gas introduction tube in detachable flask, start with oxygen/nitrogen =5/95 (v/v) mixed gas is bubbled.Then, in reactive tank, and addition glycidyl methacrylate (50g, hereinafter referred to as " GMA "), 2,2 '-di-2-ethylhexylphosphine oxides (4- methyl-6-tert butyl phenol) (0.4g, hereinafter referred to as " MBMTB ") triethylamine (0.8g, with It is known as " TEA " down), it is reacted 12 hours directly at 110 DEG C.Then PGMEA (75g) is added and is cooled to room temperature, obtains concentration For the polymer solution of 40 mass %.The weight average molecular weight of polymer is 9000, and the acid value of polymer solution is 72mgKOH/g.
Embodiment 2-3
By the obtained substitution cover type ZrO of embodiment 2-12Particle 1 (5.0g) and the obtained polymer of synthesis example 1 are molten Liquid (resin solution, 5.0g), dipentaerythritol hexaacrylate (3.0g), PGMEA (18.7g) mixing.In obtained dispersion In liquid, mixing IRGACURE (registered trademark) 907 (0.2g, チ バ ジ ャ パ Application society system) is used as Photoepolymerizationinitiater initiater, consolidate The property changed resin combination 1.
Light transmittance according to the cured coating film of above-mentioned " (14) transparency evaluation " measurement hardening resin composition 1 is 99%.In addition, implementing the evaluation of the developability of hardening resin composition 1 according to " evaluation of (15) developability ", as shown in Figure 1 simultaneously The residue in unexposed portion is not confirmed, developability is good.
Embodiment 2-4
The obtained substitution cover type ZrO of embodiment 2-1 is added in dark brown vial2Particle 1 (6.0g), FA-BZA (1.5g, benzyl acrylate, chemical conversion industry society, Hitachi system), LIGHT ACRYLATE TMP-A (0.5g, trimethylolpropane tris Acrylate, chemistry society, common prosperity society system), DAROCUR1173 (0.4g, optical free radical polymerization initiator, チ バ ジ ャ パ Application society System), it is stirred to uniform, obtains hardening resin composition 2.Obtained hardening resin composition 2, has at 25 DEG C There is mobility.Using obtained hardening resin composition 2, it is measured according to above-mentioned " test of (17) detecting refractive index ", As a result the refractive index of obtained solidfied material is 1.64.
" (20) forming characteristic " is evaluated using hardening resin composition.With scanning electron microscope (SEM) shooting at The structural body containing zirconium oxide nano-particle after shape.The SEM image is indicated in Fig. 3.As shown in figure 3, transferability is good.
Embodiment 2-5
In the obtained substitution cover type ZrO of dark brown vial mix embodiment 2-12Particle 1 (6.0g), LIGHT ACRYLATE TMP-A (6.0g), methyl ethyl ketone (28g, hereinafter referred to as " MEK ").In obtained dispersion liquid, mixing IRGACURE (registered trademark) 907 (0.24g, チ バ ジ ャ パ Application society system) is used as Photoepolymerizationinitiater initiater, obtains curable resin Composition 3.By obtained hardening resin composition 3, being coated on PET film with rod coater #10, (A4300, film spin in Japan Thick 100 μm, pencil hardness 2H) on, it is 3 minutes dry at 80 DEG C, under air atmosphere, with high-pressure mercury light irradiation 1000mJ/ cm2Ultraviolet light make its solidification, obtain solidfied material.Measure pencil hardness as a result, its hardness be 3H.
Embodiment 2-6
By 2 ethyl hexanoic acid and/or the carboxylate from 2 ethyl hexanoic acid and 2- acryloyl-oxyethyl hexahydro O-phthalic The zirconium oxide nano-particle of acid covering (replaces cover type ZrO2Particle 3) preparation
By the obtained cover type ZrO of preparation example 2-12Particle (10g) and 2- acryloyl-oxyethyl hexahydro O-phthalic Sour (4g) (pKa=3.33) is stirred in MEK (10g) to uniform.Then, make dispersible granule by adding n-hexane (36g) Son agglomerates and solution is made gonorrhoea occur, is separated aggregated particle from gonorrhoea solution with filter paper.Then, isolated aggregated particle is added It is added in n-hexane (36g), stirring separates aggregated particle after ten minutes, with filter paper, by obtained particle at room temperature true The lower drying of sky, modulation by 2 ethyl hexanoic acid and/or the carboxylate from 2 ethyl hexanoic acid and 2- acryloyl-oxyethyl hexahydro it is adjacent The Zirconia particles of phthalic acid surface treatment (replace cover type ZrO2Particle 3).
By obtained substitution cover type ZrO2Particle 3 is dispersed in deuterated chloroform as measurement sample, is carried out1H-NMR's Analysis.As a result, knowing 2 ethyl hexanoic acid and/or carboxylate and 2- acryloyl-oxyethyl hexahydro neighbour's benzene from 2 ethyl hexanoic acid Dioctyl phthalate is 25:75 there are molar ratio.
Further, the mass loss rate of the Zirconia particles measured according to above-mentioned " measurement of (5) mass loss rate " is 19 mass %.It may thus be appreciated that the 2 ethyl hexanoic acid of covering Zirconia particles and/or carboxylate and 2- third from 2 ethyl hexanoic acid Alkene trimethylammonium hexahydrophthalic acid is 19 mass % of Zirconia particles entirety.
Embodiment 2-7
By 2 ethyl hexanoic acid and/or the carboxylate from 2 ethyl hexanoic acid and 2- acryloyl-oxyethyl phthalic acid cover The zirconium oxide nano-particle of lid (replaces cover type ZrO2Particle 4) preparation
By the obtained particle cover type ZrO of preparation example 2-12Particle (10g) and 2- acryloyl-oxyethyl O-phthalic Sour (4g) (pKa=4.35) is stirred in MEK (10g) to evenly dispersed.Then, made point by adding n-hexane (36g) It dissipates particle coacervation and solution is made gonorrhoea occur, separated aggregated particle from gonorrhoea solution with filter paper.Then, by isolated cohesion grain Son is added in n-hexane (36g), and stirring separates aggregated particle after ten minutes, with filter paper, by gained particle at room temperature true Sky lower drying, modulation 2 ethyl hexanoic acid and/or carboxylate and 2- acryloyl-oxyethyl neighbour benzene two from 2 ethyl hexanoic acid The Zirconia particles of formic acid surface treatment (replace cover type ZrO2Particle 4).
By obtained substitution cover type ZrO2Particle 4 is dispersed in deuterated chloroform as measurement sample, is carried out1H-NMR's Analysis.As a result, knowing 2 ethyl hexanoic acid and/or carboxylate and 2- acryloyl-oxyethyl O-phthalic from 2 ethyl hexanoic acid Acid is 6:94 there are molar ratio.
Further, the mass loss rate of the Zirconia particles measured according to above-mentioned " measurement of (5) mass loss rate " is 24 mass %.It may thus be appreciated that the 2 ethyl hexanoic acid of covering Zirconia particles and/or carboxylate and 2- third from 2 ethyl hexanoic acid Alkene trimethylammonium hexahydrophthalic acid is 24 mass % of Zirconia particles entirety.
Preparation example 2-2
By 2 ethyl hexanoic acid and/or carboxylate and 3- acryloyloxypropyltrimethoxysilane from 2 ethyl hexanoic acid The preparation of the zirconium oxide nano-particle of covering
By the obtained cover type ZrO of above-mentioned preparation example 2-12It is transparent molten that particle (10g) is distributed to modulation in toluene (90g) Liquid.In the solution, 3- acryloyloxypropyltrimethoxysilane (1.5g, chemical industry society system, KBM- are added 5103) it is used as surface treating agent, is heated to reflux at 90 DEG C 1 hour.Then, by adding in the solution after reflow treatment N-hexane (300g) makes dispersed particle agglomerate and solution is made gonorrhoea occur.Aggregated particle is separated from gonorrhoea solution with filter paper, Heat drying at room temperature, modulation 2 ethyl hexanoic acid and/or carboxylate and 3- acryloxypropyl from 2 ethyl hexanoic acid The zirconium oxide nano-particle of trimethoxy silane surface treatment (replaces cover type ZrO2Particle 5).
To obtained substitution cover type ZrO2The crystalline texture of particle 5 is confirmed, detects to belong to regular crystal and list Tiltedly brilliant diffracted ray, by the intensity of diffracted ray it is found that regular crystal and monoclinic ratio are 54/46, partial size (crystallization particle diameter) For 5nm.
Average grain diameter (average primary particle diameter) by the obtained Zirconia particles of determination of electron microscopy is 12nm.This Outside, by obtained Zirconia particles, with infrared absorption spectrum analysis, confirm in addition to from C-H absorption and from Other than the absorption of COOH, the absorption from Si-O-C is further acknowledged.These are absorbed, it is believed that are come from and be covered on zirconium oxide The 2 ethyl hexanoic acid of nanoparticle and/or carboxylate and 3- acryloxypropyl trimethoxy silicon from 2 ethyl hexanoic acid Alkane.Further, the mass loss rate of the Zirconia particles measured according to above-mentioned " measurement of (5) mass loss rate " is 17 matter Measure %.It may thus be appreciated that the 2 ethyl hexanoic acid of covering zirconium oxide nano-particle and/or carboxylate and 3- third from 2 ethyl hexanoic acid Alkene acryloxypropylethoxysilane trimethoxy silane is 17 mass % of particle entirety.
In addition, measuring the content of Si by analyzing the nanoparticle according to " (9) Zr, Si assay ", covering 3- acryloyloxypropyltrimethoxysilane in cap rock is quantitative.Further, nanometer is measured according to " measurement of (7) carbon content " Whole carbon contents in particle calculate 2- by subtracting the carbon amounts from 3- acryloyloxypropyltrimethoxysilane The carbon amounts of thylhexoic acid and/or the carboxylate from 2 ethyl hexanoic acid acquires the 2 ethyl hexanoic acid in coating and/or comes from 2- The amount of the carboxylate of thylhexoic acid.As a result, relative to the 2 ethyl hexanoic acid in coating and/or from the carboxylic acid of 2 ethyl hexanoic acid Ester, 3- acryloyloxypropyltrimethoxysilane there are ratio, with molar ratio computing for 1.5.
Embodiment 2-8
In addition to replacing replacing cover type ZrO2Particle 1 uses substitution cover type ZrO synthesized by preparation example 2-22Particle 5 with Outside, same method obtains hardening resin composition 4 with embodiment 2-3 (hardening resin composition 1).
Light transmittance according to the cured coating film of the hardening resin composition 4 of above-mentioned " (14) transparency evaluation " measurement is 98%.In addition, implement the evaluation of the developability of curable resin composition 4 according to " evaluation of (16) developability ", it as a result can by Fig. 2 Know, confirm the residue in unexposed portion, developability is bad.
Embodiment 2-9
In addition to replacing replacing cover type ZrO2Particle 1 uses substitution cover type ZrO synthesized by preparation example 2-22Particle 5 with Outside, same method obtains hardening resin composition 5 with embodiment 2-4 (hardening resin composition 2).Gained curability tree Oil/fat composition 5 does not have mobility at 25 DEG C.
Want that forming object 5 to curable resin evaluates " (20) forming characteristic ", but curability tree can not be added dropwise on Si wafer Oil/fat composition 5 is unable to get the structural body containing zirconium oxide nano-particle.
Comparative example 2-1
LIGHT ACRYLATE TMP-A (6.0g), methyl ethyl ketone (14g) are mixed in dark brown vial.By In obtained dispersion liquid, mixing IRGACURE (registered trademark) 907 (0.12g, チ バ ジ ャ パ Application society system) is used as photopolymerization Initiator obtains comparing hardening resin composition 1.By obtained relatively hardening resin composition 1, with rod coater # 10 are coated on PET film (A4300,100 μM of film thickness, pencil hardness 2H spin in Japan), 3 minutes dry at 80 DEG C, in air Under atmosphere, with high-pressure mercury light irradiation 1000mJ/cm2Ultraviolet light, film maintain liquid, be unable to get solidfied material.
Embodiment 2-10
By the obtained cover type ZrO of preparation example 2-12Particle (10g) is stirred in PGMEA (12g), is maintained white It is turbid, uniform solution can not be formed.
Embodiment 3-1
By alkaline carbonic acid zirconium 432g (Japanese light metal society system, composition formula: Zr2(CO3)(OH)2)O2, moisture content 46% it is wet Item.Contain the chlorine of 3400 mass ppm relative to zirconium.Zirconium 1.52mol), 2,2-dimethylbutyric acid 354g (3.04mol) and two The mixed liquor of toluene 216g reacts 2 hours at 80 DEG C in the detachable flask of glass system.At this point, not with zirconium formationization The theoretical value for closing the excessive 2,2-dimethylbutyric acid of object is 1.52mol.It adds and is adjusted in obtained solution The ammonium hydroxide 1150g (ammonia: 0.38mol) of 0.033mol%, is stirred 30 minutes at 80 DEG C.Water layer is removed after being cooled to room temperature, and is obtained To the xylene solution of acid dimethyl zirconium compounds.
A part of the xylene solution of obtained acid dimethyl zirconium compounds is taken out, is evaporated at reduced pressure conditions Dimethylbenzene measures chlorinity by ion chromatograph, chlorine is not detected.
On the other hand, it by the chlorinity of the water layer of removing, is measured with ion chromatograph, detects that the zirconium relative to addition is The chlorine of 3400 mass ppm.
Embodiment 3-2
It is added in the obtained oil reservoir of embodiment 3-1 deionized water 448g (being 16 moles relative to 1 mole of zirconium), and It is added in high-pressure reactor, the atmosphere of the high-pressure reactor is replaced with nitrogen.Then mixed liquor is heated to 190 DEG C (instead Answer pressure: 1.4MPa), it is kept for 16 hours.Solution after taking out reaction filters the sediment for being deposited on bottom, with 800g first Benzene is cleaned.By obtaining the cover type Zirconia particles 156g of white for the drying of clean object.
The crystalline texture of obtained cover type Zirconia particles is confirmed, detects to belong to regular crystal and monoclinic crystal Diffracted ray, by the intensity of diffracted ray it is found that regular crystal and monoclinic ratio are 78/22.In addition, crystallization particle diameter is 4nm.
In addition, the average grain diameter (average primary particle diameter) for passing through the obtained Zirconia particles of determination of electron microscopy is 9nm, shape are granular.
Further, the mass loss rate of the Zirconia particles measured according to above-mentioned " measurement of (5) mass loss rate " is 13%.
For obtained cover type Zirconia particles, chlorinity is measured with ion chromatograph, chlorine is not detected.
Embodiment 3-3
It is same with embodiment 3-1 in addition to 2, the 2- acid dimethyl of embodiment 3-1 to be changed to other than 177g (1.52mol) Carry out to sample the synthesis of acid dimethyl zirconium compounds.As a result, generating gonorrhoea when investment ammonium hydroxide, gel is formed, can not be carried out The separation of organic layer (oil reservoir) and water layer.
Embodiment 3-4
In addition to replacing the ammonium hydroxide of embodiment 3-1 to be carried out similarly dimethyl with embodiment 3-1 other than deionized water The synthesis of butyric acid zirconium compounds.
A part of the xylene solution of obtained acid dimethyl zirconium compounds is taken out, is evaporated at reduced pressure conditions Dimethylbenzene measures chlorinity by ion chromatograph, detects the chlorine that the zirconium relative to addition is 3380 mass ppm.
It by the chlorinity of the water layer of removing, is measured with ion chromatograph, detects that the zirconium relative to addition is 20 mass ppm Chlorine.
Embodiment 3-5
It using the obtained xylene solution of embodiment 3-4, is similarly operated with embodiment 3-2, carries out cover type oxidation The synthesis of zirconium particle.As a result, obtaining the cover type Zirconia particles 175g of white.
The crystalline texture of obtained cover type Zirconia particles is confirmed, detects to belong to regular crystal and monoclinic crystal Diffracted ray, from the peak strength of diffracted ray it is found that regular crystal and monoclinic ratio are 45/55.In addition, crystallization particle diameter is 7nm。
In addition, the average grain diameter (average primary particle diameter) for passing through the obtained Zirconia particles of determination of electron microscopy is 10nm。
Further, the mass loss rate of the Zirconia particles measured according to above-mentioned " measurement of (5) mass loss rate " is 12%.
By obtained cover type Zirconia particles, chlorinity is measured by ion chromatograph, is detected relative to particle In zirconium be 730 mass ppm chlorine.
The preparation for the zirconium oxide nano-particle that preparation example 4-1 is covered by 2 ethyl hexanoic acid
By 2 ethyl hexanoic acid zirconium mineral spirits solution (782g, the first rare element chemistry industry society system) and pure water (268g) Mixing.Gained mixed liquor is added in the high-pressure reactor with blender, the atmosphere of the high-pressure reactor is replaced with nitrogen. Then, mixed liquor is heated to 180 DEG C, keeps 16 hours (pressure in high-pressure reactor is 0.94MPa), makes at such a temperature It is reacted, and generates Zirconia particles.Then, the mixed liquor after reaction is taken out, the sediment for being deposited on bottom is filtered, acetone is used It is dry after cleaning.The sediment (100g) after drying is dispersed in toluene (800mL), gonorrhoea solution is formed.Then, It as refining step, is filtered, is removed thick in sediment again with quantitative filter paper (society, ア De バ ンテック Japan system, No.5C) Big particle etc..Further, filtrate decompression is concentrated to the Zirconia particles for removing toluene recovery white.
The crystalline texture of obtained Zirconia particles is confirmed, detects to belong to regular crystal and monoclinic diffraction Line, by the intensity of diffracted ray it is found that regular crystal and monoclinic ratio are 54/46, partial size (crystallization particle diameter) is 5nm.
Average grain diameter (average primary particle diameter) by the obtained Zirconia particles of determination of electron microscopy is 12nm.This Outside, obtained Zirconia particles are confirmed with infrared absorption spectrum analysis from the absorption of C-H and from COOH Absorption.The absorption, it is believed that be due to be covered on the 2 ethyl hexanoic acid of Zirconia particles and/or from 2 ethyl hexanoic acid Carboxylate.
Further, the mass loss rate of the Zirconia particles measured according to above-mentioned " measurement of (5) mass loss rate " is 12 mass %.It may thus be appreciated that the 2 ethyl hexanoic acid of covering Zirconia particles and/or the carboxylate from 2 ethyl hexanoic acid, for oxidation 12 mass % of zirconium particle entirety.
The zirconia nanopowder grain that preparation example 4-2 is covered by 2 ethyl hexanoic acid and 3- acryloyloxypropyltrimethoxysilane The preparation of son
It is transparent molten that the obtained zirconium oxide nano-particle of preparation example 4-1 (10g) is distributed to modulation in toluene (90g) Liquid.3- acryloyloxypropyltrimethoxysilane (1.5g, chemical industry society system, KBM-5103) is added in the solution As surface treating agent, it is heated to reflux at 90 DEG C 1 hour.Then, by adding n-hexane in the solution after reflow treatment Dispersed particle is set to agglomerate and solution is made gonorrhoea occur.Aggregated particle is separated from gonorrhoea solution with filter paper, heating is dry at room temperature It is dry, the zirconium oxide nano-particle of modulation 2 ethyl hexanoic acid and the surface treatment of 3- acryloyloxypropyltrimethoxysilane.
The crystalline texture of obtained cover type Zirconia particles is confirmed, detects to belong to regular crystal and monoclinic crystal Diffracted ray, by the intensity of diffracted ray it is found that regular crystal and monoclinic ratio are 54/46, partial size (crystallization particle diameter) is 5nm。
Average grain diameter (average primary particle diameter) by the obtained Zirconia particles of determination of electron microscopy is 12nm.This Outside, it with infrared absorption spectrum analysis, confirms in addition to the absorption from C-H and the absorption from COOH, further acknowledges arrival From in the absorption of Si-O-C.These are absorbed, it is believed that come from the 2 ethyl hexanoic acid and 3- for being covered on zirconium oxide nano-particle Acryloyloxypropyltrimethoxysilane.Further, the zirconium oxide measured according to above-mentioned " measurement of (5) mass loss rate " The mass loss rate of particle is 17 mass %.It may thus be appreciated that the 2 ethyl hexanoic acid and 3- acryloyl-oxy of covering zirconium oxide nano-particle Base propyl trimethoxy silicane is 17 mass % of particle entirety.
In addition, the content of Si is measured, in coating by analyzing the nanoparticle with fluorescent x-ray analyzer 3- acryloyloxypropyltrimethoxysilane quantified.Further, nanoparticle is measured with CHNcoder analytical equipment In whole carbon contents, by subtract from 3- acryloyloxypropyltrimethoxysilane C meter calculate from 2- The C amount of thylhexoic acid, acquires the amount of the 2 ethyl hexanoic acid in coating.As a result, relative to the 2 ethyl hexanoic acid in coating, 3- Acryloyloxypropyltrimethoxysilane there are ratio, with molar ratio computing for 1.5.
Embodiment 4-1
The zirconium oxide nano-particle containing acrylic synthesized by preparation example 4-2 is added in dark brown vial 7.5g, LIGHT ACRYLATE IBX-A (isobornyl acrylate, chemistry society, common prosperity society system) 10.0g, LIGHT ACRYLATE (optical free radical polymerization causes TMP-A (trimethylolpropane trimethacrylate, chemistry society, common prosperity society system) 2.5g, DAROCUR1173 Agent, チ バ ジ ャ パ Application society system) 0.4g, methyl ethyl ketone 10.0g, it is stirred to uniform, obtains micro- containing inorganic oxide The composition of particle.
Embodiment 4-2
Other than carrying out according to mix proportions shown in table 3, method same as embodiment 4-1 obtains composition.
Comparative example 4-1
Other than carrying out according to mix proportions shown in table 3, method same as embodiment 4-1 obtains composition.
Mix proportions and obtained embodiment 4-1,4-2 of measurement are indicated in table 3 contains inorganic oxide particle The light transmittance of the composition of the composition and comparative example 4-1 of son, refractive index, the result of dielectric constant.
[table 3]
Abbreviation in table 3 is as described below.
IBX-A:LIGHT ACRYLATE IB-XA (isobornyl acrylate, chemistry society, common prosperity society system)
TMP-A:LIGHT ACRYLATE TMP-A (trimethylolpropane trimethacrylate, chemistry society, common prosperity society system)
DAROCUR1173:2- hydroxy-2-methyl -1- phenyl-propan -1- ketone (チ バ ジ ャ パ Application society system)
<using the example of titanium>
Preparation example 5-1
By 2 ethyl hexanoic acid and/or the carboxylate from 2 ethyl hexanoic acid covering titanium oxide nanoparticles (cover type TiO2Son) preparation
Make four titanium n-butoxides (170g, 0.5mol, Japanese Cao Da society system " B-1 ") and 2 ethyl hexanoic acid (345g, Mixed liquor 2.4mol) reacts 3 hours at 80 DEG C in the detachable flask of glass system.Add in obtained solution Enter deionized water (65g is 7 moles relative to 1 mole of titanium), and be added in high-pressure reactor, by the atmosphere of the high-pressure reactor It encloses and is replaced with nitrogen.Then, mixed liquor is heated to 190 DEG C, is kept for 16 hours.Solution after taking out reaction, will be deposited on bottom The sediment in portion filters, and is cleaned with methanol (500g).By obtaining the cover type Titanium particles of yellow for the drying of clean object (cover type TiO2Particle) 33g.
The crystalline texture of obtained Titanium particles is confirmed, detects the diffracted ray for belonging to anatase.In addition, Crystallization particle diameter is 6nm.
Further, the cover type Titanium particles (cover type measured according to above-mentioned " measurement of (5) mass loss rate " TiO2Particle) mass loss rate be 13 mass %.It may thus be appreciated that covering the 2 ethyl hexanoic acid of Titanium particles and/or coming from 2- The carboxylate of thylhexoic acid is 13 mass % of Titanium particles entirety.
Embodiment 5-1
By 2 ethyl hexanoic acid and/or the carboxylate from 2 ethyl hexanoic acid and 2- acryloyl-oxyethyl succinic acid cover oxygen Change titanium nanoparticle and (replaces cover type TiO2Particle) preparation
By the obtained cover type TiO of preparation example 5-12Particle (30g), 2- acryloyl-oxyethyl succinic acid (6g) (pKa =4.35) 100ml flask is added, at room temperature, with 1200rpm in, the zirconia ball 270g of PGMEA (30g), diameter 0.03mm It carries out decentralized processing 2 hours.Then, zirconia ball is removed by filtration, obtains by 2 ethyl hexanoic acid and/or from 2- ethyl hexyl The Titanium particles of carboxylate and 2- acryloyl-oxyethyl the succinic acid covering of acid (replace cover type TiO2Particle) dispersion Liquid.Then, by add n-hexane (36g) make dispersed particle cohesion so that solution gonorrhoea is occurred, with filter paper by aggregated particle from The separation of gonorrhoea solution.Then, isolated aggregated particle is added in n-hexane (36g), stirring after ten minutes, is separated with filter paper Obtained particle is dried under vacuum aggregated particle at room temperature, and modulation is by 2 ethyl hexanoic acid and/or comes from 2- ethyl hexyl The Titanium particles of carboxylate and 2- acryloyl-oxyethyl the succinic acid surface treatment of acid (replace cover type TiO2Particle).
By obtained substitution cover type TiO2Particle is dispersed in deuterated chloroform as measurement sample, is carried out1H-NMR's Analysis.As a result, knowing 2 ethyl hexanoic acid and/or carboxylate from 2 ethyl hexanoic acid and 2- acryloyl-oxyethyl succinic acid It is 10:90 there are molar ratio.
Further, the substitution cover type TiO measured according to above-mentioned " measurement of (5) mass loss rate "2The quality of particle Loss late is 20 mass %.It may thus be appreciated that the 2 ethyl hexanoic acid of covering Titanium particles and/or the carboxylic acid from 2 ethyl hexanoic acid Ester and 2- acryloyl-oxyethyl succinic acid are 20 mass % of Titanium particles entirety.
Embodiment 5-2
By 3,3- acid dimethyl and/or the carboxylate from 3,3- acid dimethyl covering titanium oxide nanoparticles (cover type TiO2Particle) preparation
Make four titanium n-butoxides (170g, 0.5mol, Japanese Cao Da society system " B-1 "), 3,3- acid dimethyl (280g, Mixed liquor 2.4mol) reacts 3 hours at 80 DEG C in the detachable flask of glass system.Add in obtained solution Enter deionized water (65g is 7 moles relative to 1 mole of zirconium oxide), and be added in high-pressure reactor, by the high-pressure reactor Atmosphere replaced with nitrogen.Then, mixed liquor is heated to 190 DEG C, is kept for 16 hours.Solution after taking out reaction, will deposit Sediment in bottom filters, and is cleaned with methanol (500g).By obtaining the cover type titanium oxide grain of yellow for the drying of clean object Son (cover type TiO2Particle) 62g.
The crystalline texture of obtained Titanium particles is confirmed, detects the diffracted ray for belonging to anatase.In addition, Crystallization particle diameter is 6nm.
Further, the cover type Titanium particles (cover type measured according to above-mentioned " measurement of (5) mass loss rate " TiO2Particle) mass loss rate be 10%.It may thus be appreciated that covering Titanium particles 3,3- acid dimethyl and/or come from 3, The carboxylate of 3- acid dimethyl is 10 mass % of Titanium particles entirety.
In addition, heat-resistance test as a result, Titanium particles keep yellow and unchanged.
Embodiment 5-3
By 3,3- acid dimethyl and/or the carboxylate from 3,3- acid dimethyl and 2- acryloyl-oxyethyl amber The titanium oxide nanoparticles of acid covering (replace cover type TiO2Particle) preparation
By the obtained cover type TiO of embodiment 5-22Particle (30g), 2- acryloyl-oxyethyl succinic acid (6g) (pKa =4.35), the zirconia ball 270g of PGMEA (30g), diameter 0.03mm is added in 100ml flask, at room temperature, with 1200rpm is carried out decentralized processing 2 hours.Then, zirconia ball is removed by filtration, obtain by 3,3- acid dimethyl and/or The Titanium particles of carboxylate and the covering of 2- acryloyl-oxyethyl succinic acid from 3,3- acid dimethyl (replace cover type TiO2Particle) dispersion liquid.Then, n-hexane (36g) is added in obtained dispersion liquid 24g makes dispersed particle agglomerate and make There is gonorrhoea in solution, is separated aggregated particle from gonorrhoea solution with filter paper.Then, isolated aggregated particle is added to n-hexane In (36g), stirring separates aggregated particle after ten minutes, with filter paper, and gained particle is dried under vacuum at room temperature, modulates quilt 3,3- acid dimethyl and/or the surface treatment of carboxylate from 3,3- acid dimethyl and 2- acryloyl-oxyethyl succinic acid Titanium particles (replace cover type TiO2Particle).
Gained is replaced into cover type TiO2Particle is dispersed in deuterated chloroform as measurement sample, is carried out1The analysis of H-NMR. As a result, know 3,3- acid dimethyl and/or the carboxylate and 2- acryloyl-oxyethyl amber for coming from 3,3- acid dimethyl Acid is 15:85 there are molar ratio.
Further, the substitution cover type TiO measured according to above-mentioned " measurement of (5) mass loss rate "2The quality of particle Loss late is 19 mass %.Therefore the 3,3- acid dimethyl of Titanium particles is covered and/or from 3,3- acid dimethyl Carboxylate and 2- acryloyl-oxyethyl succinic acid are 19 mass % of Titanium particles entirety.

Claims (9)

1. a kind of metal oxide particle, which is characterized in that the metal oxide particle is had selected from by ester group, ether, acyl 1 or more substituent group in group composed by amido, thioester substrate, thioether group, carbonate group, urethane groups and urea base simultaneously has First carboxylic acid compound of the carboxylic acid of polymeric double bond and the carboxylic acid compound other than the first carboxylic acid compound it is at least two kinds of Carboxylic acid compound is covered.
2. capped metal oxide particle according to claim 1, wherein the pKa of first carboxylic acid compound It is 4.8 or less.
3. a kind of composition, which is characterized in that the composition contains metal oxide particle of any of claims 1 or 2.
4. a kind of for the display resin combination of transparent planar formed body, which is characterized in that the resin combination contains Metal oxide particle of any of claims 1 or 2.
5. the resin combination according to claim 4 for the transparent planar formed body of display, wherein the resin Metal oxide particle of any of claims 1 or 2 in composition is 10 mass %-90 mass % in composition.
6. a kind of planar formed body, which is characterized in that the planar formed body by it is as claimed in claim 4 for display with transparent The resin combination of planar formed body is formed.
7. a kind of planar formed body, which is characterized in that the planar formed body is as described in claim 5 for display with transparent The resin combination of planar formed body is formed.
8. a kind of layered product, which is characterized in that the layered product is that planar formed body described in claim 6 or 7 is laminated.
9. a kind of touch control panel device, which is characterized in that the touch control panel device is the forming of planar described in claim 6 or 7 Body is laminated.
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