CN105085561A - Metal oxide particle and applications thereof - Google Patents

Metal oxide particle and applications thereof Download PDF

Info

Publication number
CN105085561A
CN105085561A CN201510408770.4A CN201510408770A CN105085561A CN 105085561 A CN105085561 A CN 105085561A CN 201510408770 A CN201510408770 A CN 201510408770A CN 105085561 A CN105085561 A CN 105085561A
Authority
CN
China
Prior art keywords
acid
metal oxide
particle
carboxylic acid
oxide particle
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201510408770.4A
Other languages
Chinese (zh)
Other versions
CN105085561B (en
Inventor
高桥邦夫
广田幸逸
冈田笃
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Shokubai Co Ltd
Original Assignee
Nippon Shokubai Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2011270198A external-priority patent/JP2013122643A/en
Priority claimed from JP2012085681A external-priority patent/JP6030844B2/en
Application filed by Nippon Shokubai Co Ltd filed Critical Nippon Shokubai Co Ltd
Publication of CN105085561A publication Critical patent/CN105085561A/en
Application granted granted Critical
Publication of CN105085561B publication Critical patent/CN105085561B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • 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
    • 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
    • C08K9/06—Ingredients treated with organic substances with silicon-containing 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
    • 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
    • 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
    • C09C3/006—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 invention provides a metal oxide particle covered by a carboxylic ester group and applications thereof. The provided metal oxide particle is covered by at least two carboxylic acid compounds of carboxylic acid having at least one of the following groups: free ester group, ether group, amido, thioester group, thioether group, carbonic ester group, urethane group, and urea group, a first (meth)carboxylic acid compound and other carboxylic acid compounds other than the first carboxylic acid compound. The provided metal oxide particles can be well dispersed in solvents and resins, because the metal oxide particle is covered by carboxylate compounds, and moreover, the heatproof performance of the metal oxide particle is very good too.

Description

Metal oxide particle and uses thereof
Related application
The divisional application that the application is application number is 201280060430.1, the applying date is on December 10th, 2012, denomination of invention is the Chinese invention patent application of " compound, metal oxide particle and its production and use ".
Technical field
The present invention relates to a kind of metal oxide particle and uses thereof.
Background technology
Be that the thin display of representative is popularized widely with liquid-crystal display, except television applications in the past, in computer purposes, also popularize rapidly towards portable applications, mobile telephone purposes, mobile terminal purposes etc.Thin display is the polylayer forest with the material of various function or film, plate, but in order to improve function and lighting, mostly uses resin film, on the other hand, uses inorganic materials, be formed as the structure of multiple material institute lamination at electrode.
On the other hand, as the contact panel of the one-piece type input unit of indicating meter, the use sense good due to it and being widely utilized.The mode of this contact panel has a variety of, and known has optical profile type, ultrasonic wave mode, resistive film mode, capacitive coupling etc.Wherein, consider from the pure etc. of its structure, resistive film mode is widely used, the contact panel of this resistive film mode, be formed as 2 nesa coatings and substrate via the relative structure of dividing plate, carry out the structure (for example, referring to patent documentation 1) of the mode inputted for making relative conducting film contact by finger or the pressing such as pen.
In addition, the contact panel of capacitive coupling, for proximity transducers such as the fingers by people, detect the structure that the mode inputted is carried out in the change being applied with the electrostatic capacity of the sensor of voltage, by electrode is configured with particular pattern, can further improve and detect positional precision (for example, referring to patent documentation 2).This capacitive coupling, compared with resistive film mode, owing to not having mechanicalness drive part, is therefore considered to provide the long lifetime and the high contact panel of reliability.
But the laminating material of glass or transparency electrode, resin film etc. has intrinsic specific refractory power, when the refringence of interlayer is larger, there is the situation that transmittance reduces or recognizes depicting pattern.Particularly in touch surface indicating meter, mainly use ito film as nesa coating, but the specific refractory power of this ito film is about 2.0, relatively high, therefore, the reflectivity of the Sensor section of contact panel uprises, and identity is deteriorated.In addition, use arrange in the contact panel sensor of the ito substrate of pattern arrangement ITO electrode, due to ITO electrode part from do not have the reflectivity of the part of electrode different significantly, thus the depicting pattern of electrode reflects, and there is the problem of identity difference.
In addition, metal oxide particle is owing to making contributions to the multifunction of the various material such as optical material, electronic component material, magnetic recording material, catalystic material, ultraviolet absorption material and high performance, and extensively gazed at, wherein, known Zirconia particles demonstrates very high specific refractory power.In order to realize multifunction that such metal oxide particle brings or high performance, metal oxide particle can be scattered in substrate by requirement well.
Such as, in the invention described in the patent documentation 3 that the present inventor applies for, disclose a kind of Zirconia particles that improve dispersiveness in all kinds of SOLVENTS.Specifically, disclose and covered by insulating covering agent of more than two kinds, at least a kind of insulating covering agent is R 1-COOH (R 1for carbon number is the alkyl of more than 6) zirconium oxide nano-particle.In patent documentation 3, in order to obtain R 1the zirconium oxide nano-particle that-COOH covers, makes zirconium oxychloride and R 1cOONa reacts, mixing water in this reactant, and hydro-thermal reaction (also referred to as Hydrothermal Synthesis) occurs.
In addition, as other example, as the preparation method of the nanoparticle containing Zirconia particles covered by carboxylic acid, the also known method comprising following operation: the operation of the metal salt of organic carboxylic acid that synthesis makes organic carboxyl acid and metallic compound obtain with specific ratio reaction; Make the operation of this metal salt of organic carboxylic acid and zirconium compounds Reactive Synthesis carboxylic acid-zirconium composite; And, by the operation (patent documentation 4) of this mixture supply Hydrothermal Synthesis.
At first technical literature
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 10-48625 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2002-326301 publication
Patent documentation 3: JP 2008-44835 publication
Patent documentation 4: JP 2009-096681 publication
Summary of the invention
The object of the present invention is to provide a kind of in preparation is by carboxylic acid ester groups institute covering metal oxide particle useful novel cpd (intermediate compound), and the novel metal oxide particle that covers by carboxylic acid ester groups and new preparation method thereof.
Compound of the present invention, for being bonded with metal or the oxygenate metal of carboxylic acid ester groups, is characterized in that having specific ligancy.In addition, metal oxide particle of the present invention, is characterized in that, has carbonate as covering composition.
That is, the present invention is a kind of compound, it is characterized in that, this compound is the compound that following formula (1) represents,
M m(-OCO-R) n(1)
In formula (1), M is metal or oxygenate metal;
R is carbon number is more than 1, less than 20, can have the alkyl of halogen and/or heteroatomic linear chain structure, branched structure, alicyclic structure or aromatic ring structure;
M is the integer of more than 1;
When M is metal, its valence mumber is represented with a valency, when M is as oxygenate metal, when the valence mumber of the metal forming oxygenate metal is represented with (a+2) valency, i chain length that () forms the methene chain of R is 2 to the maximum, and the quantity that chain length is the methene chain of 2 is when being 0 or 1, n is for meeting the integer of the relation of m≤n≤a × m; (ii) except the chain length of methene chain of satisfied formation R be to the maximum 2 and the chain length that forms R be the quantity of the methene chain of 2 be except the situation of two underlying conditions of 0 or 1, n is for meeting the integer of the relation of m≤n<a × m.
Described M is preferably selected from least a kind of metal in the group be made up of Ti, Al, Zr, Zn, Sn, oxygen titanium, oxygen zirconium and oxygen tin or oxygenate metal.In addition, the present invention also comprises the metal oxide particle obtained by this compound.
The present invention also comprise by have be selected from by ester group, ether, amide group, thioester substrate, thioether group, carbonate group, urethane groups and Urea-based the carboxylic acid cpd beyond the substituent carboxylic acid of more than 1 in the group that forms or (methyl) acrylic acid first carboxylic acid cpd and the first carboxylic acid cpd at least 2 kinds of carboxylic acid cpds the metal oxide particle that covers.The preferred pKa of the first carboxylic acid cpd for capped metal oxide particle of the present invention is that the less than 4.8, first carboxylic acid cpd or the second carboxylic acid cpd have polymerizability double bond.
In addition, when understanding of the present invention from another side, be the metal oxide particle that the carbonate represented by following formula (2) covers.
-OCO-R’(2)
(wherein, in formula, R ' is saturated hydrocarbyl, and the chain length forming the methene chain of this saturated hydrocarbyl is 2 to the maximum, and the quantity that chain length is the methene chain of 2 is 0 or 1.)
The preparation method of metal oxide particle of the present invention, is characterized in that, in presence of water, and heating of metal compound or oxygenate metallic compound; Preferred: (i) reacts under the existence of aromatic hydrocarbon; (ii) relative to metallic compound 1 mole, the amount of water during reaction is less than 17 moles; (iii) react under the existence of basic cpd; Deng.
The preparation method of metal oxide particle of the present invention, when understanding from another point of view, is characterized in that, in presence of water, the carbonate of metal or the carbonate of oxygenate metal and the mixture of carboxylic acid is heated; Preferred: (i) reacts under the existence of aromatic hydrocarbon; (ii) relative to metallic compound or oxygenate metallic compound 1 mole, the amount of water during reaction is less than 17 moles; (iii) react under the existence of basic cpd; Deng.
Prepare the method for compound of the present invention, it is characterized in that, the mixture of the carbonate (M is same as described above) of M with the carboxylic acid (R is same as described above) with RCOO base is heated; Preferred: (i), under the existence of aromatic hydrocarbon, makes the carbonate of M and the carboxylic acid reaction with RCOO base; (ii) under the existence of basic cpd, the carbonate of M and the carboxylic acid reaction with RCOO base is made; Deng.
The present invention, further preferred containing tricarboxylic metal-salt etc. with in halid solution, containing not forming the tetracarboxylic acid bronsted lowry acids and bases bronsted lowry of compound with described metal, by making this tetracarboxylic acid bronsted lowry acids and bases bronsted lowry and described halide reaction, remove halogenide.In described preparation method, described solution, containing the organic solvent of soluble compound after halid reaction the latest, and the second solvent be separated with this organic solvent, make described halid reactants dissolved after the second solvent, organic solvent is separated with the second solvent.
In addition, the present invention, also comprises the invention of the composition related to containing described compound and the composition containing described metal oxide particle.
Further, the present invention, also comprises for the resin combination of indicating meter with transparent planar molding, it is characterized in that, containing described metal oxide particle.Described for the resin combination of indicating meter with transparent planar molding, the described metal oxide particle in preferred resin composition is 10 quality %-90 quality % in composition.
In addition, the present invention also comprises by the described planar molding formed with the resin combination of transparent planar molding for indicating meter.Further, the present invention also comprises the layered product of described planar molding lamination and the touch control panel device of described planar molding lamination.
Compound of the present invention is the metal or the oxygenate metal that are bonded with carboxylic acid ester groups, owing to having specific ligancy, is applicable to and prepares metal oxide particle.
In addition, metal oxide particle of the present invention, owing to being covered by the first carboxylic acid and the second carboxylic acid, the dispersiveness thus in various medium is extremely good, can be applicable to various uses.Particularly significantly useful in the purposes process forming with resist the precision thin microstructure being representative, dispersion inequality or development residue can be improved.
Further, metal oxide particle of the present invention, owing to being coated with carbonate, favorable dispersity in solvent and resin, and thermotolerance is also excellent, this effect is played further by the metal oxide particle covered by the carbonate with above-mentioned formula (2) structure.Therefore, metal oxide particle of the present invention, can not condense in the composition, can play its characteristic (high refractive index etc.), even and if be exposed in high temperature also can not variable color, and industrially extremely useful.
Accompanying drawing explanation
Fig. 1 is will containing the replacement cover type ZrO in embodiment described later (embodiment 2-1) 2the curable resin composition 1 (anti-corrosion agent composition) of the embodiment 2-3 of particle 1 carries out exposure curing and the laser microscope photo of test pattern after development.
Fig. 2 is will containing the replacement cover type ZrO in preparation example described later (preparation example 2-2) 2the curable resin composition 4 (anti-corrosion agent composition) of the embodiment 2-8 of particle 5 carries out exposure curing and the laser microscope photo of test pattern after development.
Fig. 3 is by scanning electronic microscope (SEM) photo of the curable resin composition 2 in embodiment described later (embodiment 2-4) according to the pyramid array pattern after the evaluation procedure solidification of " (16) forming characteristic ".
Embodiment
Metal oxide particle of the present invention, prepares by metallic compound or oxygenate metallic compound being heated in presence of water.Metal oxide particle of the present invention, such as, by metallic compound or oxygenate metallic compound (below, are sometimes referred to as metal oxide precursor.) and carbonate or carboxylic acid in presence of water heat treated prepare.In the present invention, can via various compounds (intermediate compound of metal oxide particle) in this preparation process.That is, various metal oxide particle of the present invention, obtains by each compound of following explanation or each preparation method.The metal oxide particle obtained, is characterized in that, is covered by the carbonate with the RCOO base identical with the RCOO base in compound.
In addition, in the present invention, so-called " covering " comprises two states, by the state of carboxylicesters (carboxylic acid cpd) or organic compound and metal oxide particle chemical bonding; And carboxylicesters (carboxylic acid cpd) or organic compound physical property are attached to the state of metal oxide particle.
Metal oxide particle of the present invention, by following 4 kinds of methods preparation.About each method, details are as follows.
1. the first invention (the first method)
The metal oxide particle of the first invention preparation, is characterized in that, median size is more than 1nm and for below 100nm, the surface of metal oxide particle cover by organic compound.
The specific refractory power of metal oxide particle is preferably more than 1.5, is more preferably more than 1.55, and more preferably more than 1.6, more preferably more than 1.65, most preferably be more than 1.7.Thus, the specific refractory power of the composition containing this metal oxide particle can be made to improve, total reflection when light can be suppressed incident to said composition by adjacent material.Formation specific refractory power is the metal of the oxide compound of more than 1.7 is such as Al, Ti, Zr, In, Zn, Sn, La, Y, Ce etc., is preferably Al, Ti, Zr, Zn, Sn, Ce (being more preferably Al, Ti, Zr, Zn, Sn), is particularly preferably Ti, Zr.Be used alone these metals or make the ratio of composite oxides larger, specific refractory power can be made higher.
Cover the organic compound used, as long as can at the organic compound of the surface coordination of metal oxide particle and/or bonding, just be not particularly limited, organic carboxylic acid compounds, silane based compound, metal coupling agent, the compound containing epoxy group(ing), the compound containing hydroxyl, the compound containing amido, the compound etc. containing thiol group can be lifted.Be preferably organic carboxylic acid compounds, silane based compound, metal coupling agent, compound containing epoxy group(ing), be more preferably organic carboxylic acid compounds.When described organic compound is organic carboxylic acid compounds, silane based compound, metal coupling agent, compound containing epoxy group(ing), method easy to use can covers on metal oxide particle, and can prepare at an easy rate.Total carbon number of described organic compound, is preferably more than 3.By making total carbon number be more than 3, the dispersiveness of metal oxide particle in solvent or resin can be improved.From the viewpoint of dispersiveness, total carbon number of described organic compound is preferably more, and its lower value is more preferably 4, and more preferably 5.On the other hand, total carbon number of described organic compound is preferably less than 20.Thus, the productive rate with the metal oxide particle of organic compound coordination and/or bonding can be improved.The upper limit of total carbon number of described organic compound is more preferably 18, and more preferably 16, be particularly preferably 10.In addition, described organic compound also can have halogen and/or heteroatoms, also can be linear chain structure, branched structure, alicyclic structure or aromatic ring structure.When described organic compound is organic carboxylic acid compounds, also preferably there is side chain, thus, metal oxide particle can be suppressed to condense.
Above-mentioned organic carboxylic acid compounds, such as, can enumerate vinylformic acid, methacrylic acid, toxilic acid, fumaric acid, valeric acid, caproic acid, enanthic acid, 2 ethyl hexanoic acid, sad, 2-methyl enanthic acid, 4-methyloctanoic acid, n-nonanoic acid, capric acid, neodecanoic acid, dodecyl acid, tetradecyl acid, lauric acid, tetradecanoic acid, palmitinic acid, stearic acid, oleic acid, linolic acid, linolenic acid, lactic acid, oxysuccinic acid, citric acid, M-nitro benzoic acid, phthalic acid, m-phthalic acid, oxalic acid, propanedioic acid, succsinic acid, pentanedioic acid, hexanodioic acid, pyruvic acid, butyric acid, PIVALIC ACID CRUDE (25), 2,2-acid dimethyl, 3,3-acid dimethyl, 2,2-dimethyl valeric acid, 2,2-diethyl butyric acid, 3,3-diethyl butyric acid, naphthenic acid, cyclohexane dicarboxylic acid, 2-acryloyl-oxyethyl succsinic acid, 2-methacryloxyethyl succsinic acid, 2-acryloyl-oxyethyl hexahydrophthalic acid, 2-methacryloxyethyl hexahydrophthalic acid, 2-acryloyl-oxyethyl phthalic acid, 2-methacryloxyethyl phthalic acid etc.Wherein, be preferably PIVALIC ACID CRUDE (25), 2,2-acid dimethyls, 3,3-acid dimethyls, vinylformic acid, methacrylic acid, 2 ethyl hexanoic acid, neodecanoic acid, be more preferably 2,2-acid dimethyl, 3,3-acid dimethyls.Organic carboxylic acid compounds can only use a kind, also can combine two or more and use.
Above-mentioned silane based compound, such as there are vinyltrimethoxy silane, vinyltriethoxysilane, 3-methacryloxypropyl, 3-acryloxypropyl Trimethoxy silane, N-(2-amido ethyl)-3-aminocarbonyl propyl Trimethoxy silane, to styryl Trimethoxy silane, phenyltrimethoxysila,e, silane based compound can only use a kind, also can combine two or more and use.
Above-mentioned metal coupling agent, such as, have the aluminum alkoxide of aluminum methylate, aluminum ethylate, aluminium isopropoxide, three n-butoxy aluminium, tri sec-butoxy aluminum, three tert.-butoxy aluminium etc.; The aluminium system coupling agent of aluminium ethylacetoacetate diisopropoxide, etheric acid carbalkoxy diisopropoxy aluminium, monomethacrylates base diisopropoxy aluminium, ketostearic acid aluminium trimer, aluminum isopropoxide etheric acid alkane ester list (dioctyl phosphoric acid ester) etc.; The titan-alkoxide of titanium n-butoxide, four tert.-butoxy titaniums, four sec-butoxy titaniums, purity titanium tetraethoxide, four isobutoxy titaniums, tetramethoxy titanium, four (methoxy propoxy) titanium, four (methoxyphenoxy) titanium etc.; The titanium system coupling agent of two (two-tridecyl phosphite) titanic acid ester of sec.-propyl three isostearoyl base titanic acid ester, sec.-propyl three capryloyl titanic acid ester, four octyl groups, tetra isopropyl two (dioctylphyrophosphoric acid ester) titanic acid ester, sec.-propyl three (dioctylphyrophosphoric acid acyloxy) titanic acid ester, two (dioctylphyrophosphoric acid acyloxy) oxygen acetyl titanic acid ester, two (dioctylphyrophosphoric acid acyloxy) ethylene titanic acid ester etc.; The zirconium alkoxide of four n-propoxyzirconium, four tert.-butoxy zirconiums, four (2-ethyl hexyl oxy) zirconium, four isobutoxy zirconiums, tetraethoxy zirconium, zirconium tetraisopropoxide, four n-propoxyzirconium, four (2-methyl 2-butoxy) zirconium etc.; The zirconium compounds of two n-butoxies (two-2,4-diacetylmethanes) zirconium, three n-butoxy diacetylmethane zirconiums, dimethacrylate dibutoxy zirconium etc.; Metal coupling agent can only use a kind, also can combine two or more and use.
The above-mentioned compound containing epoxy group(ing), such as can enumerate 3,4-epoxycyclohexyethylSiOi enylmethyl-3 ', 4 '-epoxycyclohexyethylSiOi alkenyl carboxylate, two (3,4-expoxycyclohexyl) adipic acid ester, A Hydrogenated Bisphenol A type epoxy resin, hydrogenation phenol aldehyde type epoxy resin, cyclohexanedimethanodiglycidyl diglycidyl ether, 6-caprolactone modification 3, the rare ylmethyl-3 of 4-epoxycyclohexyethylSiOi ', 4 '-epoxycyclohexyethylSiOi alkenyl carboxylate etc., compound containing epoxy group(ing) can only use a kind, also can combine two or more and use.
The above-mentioned compound containing hydroxyl, such as hexalin can be enumerated, n-butyl alcohol, 2-butanols, methyl-cyclohexanol, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol monomethyl ether, 2-hydroxyethylmethacry,ate, 2-HEMA, 2-acrylate, 2-hydroxy propyl methacrylate, 3-acrylate, 3-hydroxy propyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, polymkeric substance etc. containing hydroxyl, compound containing hydroxyl can only use a kind, also can combine two or more to use.
In addition, in first invention, the organic compound on above-mentioned organic carboxylic acid compounds, silane based compound, metal coupling agent, compound containing epoxy group(ing) or other covering metal oxide particle surface, can only use a kind, also can combine two or more and use.
Metal oxide particle is for the dispersiveness of monomer or polymkeric substance, adjust by selecting the organic compound on covering metal oxide particle surface, but by using the group to the monomer display affinity forming medium, particle can be improved to monomer or the dispersiveness of polymkeric substance that formed by this monomer.Such as, when covering particle with the organic compound with vinyl of (methyl) vinylformic acid or (methyl) acrylate etc., particle can be improved to the dispersiveness of monomer equally with (methyl) vinylformic acid of vinyl or (methyl) acrylate etc.In addition, when covering particle with the organic compound with phenyl, the polymkeric substance to the monomer of vinylbenzene etc. or styrene resin or resol etc. can be improved, there is the monomer of phenyl or the dispersiveness of polymkeric substance.
The overlay capacity of organic compound of the present invention, relative to the metal oxide particle covered with organic compound, is preferably more than 0.1 quality %.Thus, the dispersiveness of metal oxide particle to resin medium or solvent etc. can be improved.Described bonded amount is more preferably more than 0.5 quality %, more preferably more than 2 quality %.When bonded amount is many, because the quantitative change of the metal oxide particle being included in per unit volume is few, the effect that specific refractory power improves cannot be given full play to, thus not preferred.Therefore, described bonded amount is generally below 30 quality %, is preferably below 25 quality %, is more preferably below 20 quality %.
As the metal oxide forming metal oxide particle, can be the oxide compound of single metal, can be the sosoloid of oxide compound of more than two kinds, or also can be composite oxides.Single metal oxide, comprises such as aluminum oxide (Al 2o 3), titanium oxide (TiO 2), zirconium white (ZrO 2), Indium sesquioxide (ln 2o 3), zinc oxide (ZnO), stannic oxide (SnO 2), lanthanum trioxide (La 2o 3), yttrium oxide (Y 2o 3), cerium oxide (CeO 2), magnesium oxide (MgO), be preferably titanium oxide, zirconium white, stannic oxide.As the sosoloid of oxide compound of more than two kinds, ITO, ATO etc. can be enumerated.Composite oxides are such as barium titanate (BaTiO 3), perovskite (CaTiO 3), spinel (MgAl 2o 4) etc.
The particle diameter of metal oxide particle, by processing the crystallization particle diameter that calculated by X-ray diffraction analysis and/or being measured by the image that various electron microscope observation obtains.
The crystallization particle diameter of the metal oxide particle calculated by X-ray diffraction analysis, is preferably below 20nm.Thus, the transparency of the composition containing this metal oxide particle can be improved.This crystallization particle diameter is more preferably below 15nm, more preferably below 10nm.The lower limit of this crystallization particle diameter is generally about 1nm.
By the particle diameter of various electron microscope observation by by amplifying observations such as metal oxide particle transmission electron microscope (TEM), electric field radioactive transmission electron microscope (FE-TEM), electric field radioactive scanning electronic microscope (FE-SEM), the length of Stochastic choice 100 its long axis directions of particle assay, asks its arithmetical mean to determine.
Below 100nm is preferably in the median size (average primary particle diameter) of the metal oxide particle of above-mentioned electron microscope observation.Thus, the transparency of the composition containing this metal oxide particle can be improved.Average primary particle diameter is more preferably below 50nm, more preferably below 30nm, most preferably is below 20nm.The lower limit of average primary particle diameter is generally about 1nm.
The specific refractory power of metal oxide particle is preferably more than 1.7.Thus, the specific refractory power of the composition containing this metal oxide particle can be improved, and total reflection when light can be suppressed incident to said composition by adjacent material.Forming the metal of the oxide compound of specific refractory power more than 1.7, such as, is Al, Ti, Zr, In, Zn, Sn, La, Y, Ce etc., is preferably Al, Ti, Zr, Zn, Sn, is particularly preferably Ti, Zr, Sn.These metals be used alone or the ratio of composite oxides larger, specific refractory power can be made higher.
The crystalline texture of metal oxide such as can enumerate cubic crystal, regular crystal, oblique crystal etc.What particularly preferably crystalline texture was whole more than 70% is regular crystal.When the ratio of regular crystal is large, specific refractory power can be improved.Tetragonal phase is more than 0.8 for monoclinic ratio (the former/the latter), is preferably more than 1.3, is more preferably more than 2.0.Also can be separately regular crystal.
As the shape of metal oxide particle, spherical, oval spherical, cubic, rectangular-shaped, pyramid shape, needle-like, column, bar-shaped, tubular, flakey, tabular, flake etc. can be enumerated.Consider dispersiveness etc. in a solvent, described shape preferably spherical, granular, column etc.
In addition, when using zirconium white as metal oxide, zirconium white has high specific refractory power, as its crystalline texture, can enumerate oblique crystal, regular crystal etc.In zirconic crystalline texture, known regular crystal demonstrates the highest specific refractory power, when require more high refractive index, the ratio of preferred regular crystal is more.In addition, proportional by adjusting containing of these crystalline textures, the zirconic specific refractory power of adjustable.
Metal oxide particle in first invention, in the scope of feature with the metal oxide particle described in the first invention, also the feature of the metal oxide particle described in the second invention described later can be had, also the feature of the metal oxide particle described in the 3rd invention can be had, also the feature described in the 4th invention can be had, further, the combination of these features can also be had.
Just be not particularly limited by the compound of hydro-thermal reaction generation metal oxide as long as metal ingredient comprises.As the compound containing metal ingredient, various metal oxide precursor can be enumerated, the oxyhydroxide, muriate, oxychlorination thing, vitriol, acetate, organic acid salt, alkoxide etc. of such as various metal also can be the salt of various metal and the second carboxylic acid further.Such as, use in the example of zirconium, the zirconium alkoxide etc. of zirconium hydroxide, zirconium chloride, zirconium oxychloride, zirconyl acetate, Zircosol ZN, zirconium sulfate, zirconium caprylate, 2 ethyl hexanoic acid zirconium, oleic acid oxidation zirconium, acetic acid zirconium, stearic acid zirconium white, lauric acid zirconium white, tetrabutyl zirconate etc. can be enumerated.In addition, using in the example of titanium, is preferred method when using the alkyl titanium oxide etc. of titanium hydroxide, titanium chloride, oxychlorination titanium, acetic acid oxygen titanium, titanyl nitrate, titanium sulfate, sad titanium, oleic acid oxidation titanium, acetic acid titanium, stearic acid titanium oxide, lauric acid titanium oxide, four titanium butoxide (such as four titanium n-butoxide) etc.
When adopting hydro-thermal reaction, the organic solvent containing water can be adopted.As organic solvent, hydrocarbon, ketone, ether, alcohol etc. can be used.Because the solvent gasified during hydro-thermal reaction likely makes reaction fully carry out, therefore, the boiling point under preferred normal pressure is the organic solvent of more than 120 DEG C, is more preferably more than 180 DEG C, more preferably more than 210 DEG C.Particularly, decane, dodecane, the tetradecane, octanol, decyl alcohol, hexalin, Terpineol 350, ethylene glycol, Diethylene Glycol, 1 can be exemplified, 2-propylene glycol, 1, ammediol, 1,4-butyleneglycol, 2,3-butyleneglycol, hexylene glycol, glycerine, Pehanorm, toluene, dimethylbenzene, Three methyl Benzene, dimethyl formamide (DMF), dimethyl sulfoxide (DMSO) (DMSO) etc., be preferably dodecane, the tetradecane.
When being separated into 2 layers by adding described organic solvent, tensio-active agent etc. can being added and form homogeneous phase state or be suspended emulsified state, usually can directly with 2 layers of supply hydro-thermal reaction.
Although described composition also exists the situation of the water containing the substantial amount coming from raw material, time in the feed containing moisture or seldom, be necessary to add moisture in advance before supply hydro-thermal reaction.
Be present in the amount of moisture in the system of hydro-thermal reaction, (following relative to the intermediate compound of the metal oxide precursor be present in system or metal oxide particle, be called metal oxide precursor etc.) mole number water mole number (mole numbers of the mole number/metal oxide precursor of water etc.) be preferably 4/1 ~ 100/1, be more preferably 8/1 ~ 50/1.During less than 4/1, can there is hydro-thermal reaction needs the long period, or the particle diameter of the particle obtained becomes large situation.On the other hand, during more than 100/1, except the metal oxide precursor be present in system is less, beyond thus productive rate declines, not special problem.
The pressure of hydro-thermal reaction, is preferably more than 0.5MPa, is more preferably more than 0.6MPa.This upper limit of pressure, is generally below 3.0MPa, is preferably below 2.0MPa, is more preferably below 1.5MPa, is particularly preferably below 1.0MPa.
The temperature of reaction of hydro-thermal reaction, is preferably more than 100 DEG C, is more preferably more than 140 DEG C, more preferably more than 160 DEG C.The upper limit of hydrothermal treatment consists temperature, is not particularly limited, and is preferably less than 300 DEG C, is more preferably less than 250 DEG C, more preferably less than 220 DEG C.Hydrothermal conditions is such as 5-50 hour, is preferably 10-40 hour.Atmosphere during hydro-thermal reaction, is not particularly limited, the atmosphere of inert gases of preferred nitrogen, argon gas etc.
The method of organifying compound and metal oxide particle coordination of the present invention and/or bonding, except the method via above-mentioned metal oxide precursor, such as, also carry out heat treated to prepare by adding above-mentioned insulating covering agent in the solvent dispersions of metal oxide particle.As long as the solvent used has the dispersiveness of appropriateness to metal oxide particle, be just not particularly limited.Such as, benzene,toluene,xylene, hexanaphthene etc. can be used.As long as the concentration of metal oxide suitably adjusts, but be preferably 0.1-50 about quality %.As long as the consumption of insulating covering agent suitably adjusts, be 1-60 quality % relative to metal oxide particle usually.As long as Heating temperature suitably adjusts, be generally about 30 to 180 DEG C, be preferably 40-150 DEG C, be more preferably 50-130 DEG C.As long as the reaction times also suitably adjusts, be generally 0.1-10 hour, be preferably 0.3-3 hours.
The preparation method of the metal oxide particle in the first invention, also can use described later second, third, the 4th method, also synthesize by known method.Such as, hydro-thermal reaction is carried out to obtain the method for metal oxide particle at metallic compound with under the coexisting of organic compound that cover; In advance by the organic compound for covering and metallic compound synthetic mesophase compound, obtained the method for metal oxide particle by the hydro-thermal reaction of this intermediate compound; Metal oxide microparticle modulated in advance using the organic compound for covering carry out the method etc. covered, because these methods can obtain the metal oxide particle that covered by organic compound easily, is thus preferred synthetic method.
2. the second invention (the second method)
Second invention, comprises compound and metal oxide particle, also comprises their preparation method further.
First, the compound (intermediate compound of metal oxide particle) used in the second invention (the second method) is described in detail.
The compound used in the second invention preferably has the compound of following characteristics: the compound represented for following formula (1),
M m(-OCO-R) n(1)
In formula (1), M is metal or oxygenate metal;
R is carbon number is more than 1, less than 20, can have the alkyl of halogen and/or heteroatomic linear chain structure, branched structure, alicyclic structure or aromatic ring structure;
M is the integer of more than 1;
When M is metal, its valence mumber is represented with a valency, when M is as oxygenate metal, when the valence mumber of the metal forming oxygenate metal is represented with (a+2) valency, i chain length that () forms the methene chain of R is 2 to the maximum, and the quantity that chain length is the methene chain of 2 is when being 0 or 1, n is for meeting the integer of the relation of m≤n≤a × m; (ii) except the chain length of methene chain of satisfied formation R be to the maximum 2 and the chain length that forms R be the quantity of the methene chain of 2 be except the situation of two underlying conditions of 0 or 1, n is for meeting the integer of the relation of m≤n<a × m.
During for described compound, due to metal in this compound or oxygenate metal being bonded with carboxylic acid ester groups, this compound has specific ligancy, is thus applicable to and prepares metal oxide particle.
M represents metal or oxygenate metal, more than a kind that can select arbitrarily these.M is preferably selected from more than a kind in transition metal, typical metal and their oxygenate metal (partial oxide), is more preferably more than a kind that is selected from the oxygenate metal (partial oxide) of transition metal and transition metal.Oxygenate metal (partial oxide) refers to the state of burning, and the coordination of metal does not use oxygen element saturated, can with the meaning of carboxylic acid ester groups bonding.
M is preferably selected from least a kind in the group be made up of Ti, Al, Zr, Zn, Sn, oxygen titanium, oxygen zirconium and oxygen tin.
R is carbon number is more than 1, less than 20, can have the alkyl of halogen and/or heteroatomic linear chain structure, branched structure, alicyclic structure or aromatic ring structure, is preferably the saturated hydrocarbyl of linear chain structure, branched structure, alicyclic structure.The lower limit of the carbon number of R is preferably more than 3, is more preferably more than 4.The upper limit of the carbon number of R is preferably less than 15, is more preferably less than 12.
The described RCOO base (carboxylic acid ester groups) being bonded to M, i chain length that () forms the methene chain of R is 2 to the maximum, and the quantity that chain length is the methene chain of 2 is the situation of 0 or 1, (ii) except the chain length of the methene chain of satisfied formation R is 2 to the maximum, and to form the chain length of R be the quantity of the methene chain of 2 is beyond the situation of two underlying conditions of 0 or 1, the condition difference that the n in above-mentioned formula (1) should meet.
The i chain length of methene chain that () forms R is 2 to the maximum, and the quantity that chain length is the methene chain of 2 be 0 or 1 situation of (that is, R does not have the methene chain that chain length is 2, or there is a chain length be the methene chain of 2).
Now, when M is metal, its valence mumber is represented with a valency, when M is oxygenate metal, when being represented with (a+2) valency by the valence mumber of the metal forming oxygenate metal (that is, when ligancy bonding for M being represented with a), n is for meeting the integer of the relation of m≤n≤a × m.That is, M coordination can all with carboxylic acid ester groups bonding, also can exist not with the coordination of the M of carboxylic acid ester groups bonding.Be bonded with the compound of the second invention of such carboxylic acid ester groups, because described R is hydrophobicity, the dispersiveness thus particularly in hydrophobic solvent or hydrophobic resin etc. becomes good, can improve operability.Further, the dispersiveness of metal oxide particle in hydrophobic solvent or hydrophobic resin etc. obtained by this compound also becomes good.Further, because the chain length of the methene chain in R is 2 to the maximum, and the quantity that chain length is the methene chain of 2 is 0 or 1, thus can improve the thermotolerance of the metal oxide particle obtained by this compound.
The chain length of methene chain, refers to the methylene radical (-CH without replacing 2-) continuous quantity, be preferably 1, also can be 0.
Total carbon number in above-mentioned R, is preferably more than 3.By making the total carbon number in R be more than 3, the dispersiveness of metal oxide particle in solvent or resin can be improved.From the viewpoint of dispersiveness, the total carbon number in R is preferably more, and its lower value is more preferably 4, and more preferably 5.On the other hand, the total carbon number in R is preferably less than 20.Thus, the metal oxide component of the metal oxide particle covered by carbonate obtained by this compound can be increased.The upper limit of the total carbon number in R is more preferably 10, and more preferably 6, be particularly preferably 5.
In addition, R preferably has side chain, thus, can suppress the cohesion of metal oxide particle.
In above-mentioned formula (1), particularly preferred carboxylic acid ester groups, for-the R in formula is-R 1-R 2-R 3-(R 4) p-H.Wherein, p is 0 or 1, R 1-R 4for-CH 2-,-CR 5r 6-(wherein ,-CR 5r 6-do not comprise-CH 2-) in any one, and R 1-R 4in any one be-CR 5r 6-.In addition, described R 5and R 6can be identical also can be different, be any one in hydrogen atom, methyl, ethyl, propyl group.These R 5and R 6, preferably not containing the group with three grades of hydrogen.Further, R 1-R 4there is multiple-CR 5r 6-time, R 5, R 6can because of (-CR 5r 6-) unit and different.Described R 5and R 6, be preferably methyl, ethyl, be particularly preferably methyl.In addition, R 5, R 6be preferably straight-chain.
Above-mentioned-R 1-R 2-R 3-(R 4) p-H (p=0,1), preferred R 1, R 2any one be-CR 5r 6-(particularly-C (CH 3) 2-).
Above-mentioned-R 1-R 2-R 3-(R 4) p-H (p=0,1), particularly preferably R 1for-CH 2-,-C (CH 3) 2-in any one, R 2-R 4for-CH 2-,-C (CH 3) 2,-CH (CH 3)-in any one, and R 1-R 4any one be-C (CH 3) 2-.
Form the carboxylic acid of above-mentioned carboxylic acid ester groups, such as, can enumerate butyric acid, PIVALIC ACID CRUDE (25), 2,2-acid dimethyls, 3,3-acid dimethyl, 2,2-dimethyl valeric acid, 2,2-diethyl butyric acid, 3,3-diethyl butyric acid, be preferably PIVALIC ACID CRUDE (25), 2,2-acid dimethyl, 3,3-acid dimethyls, be more preferably 2,2-acid dimethyl, 3,3-acid dimethyls.
Carboxylic acid ester groups in second invention, can only use a kind, also can combine two or more and use.When combining two or more use, the chain length at least forming the methene chain of a kind of R is 2 to the maximum, and the quantity that chain length is the methene chain of 2 is 0 or 1.
The chain length forming the methene chain of R is 2 to the maximum, and the quantity that chain length is the methene chain of 2 is when being (i) of 0 or 1, particularly M is preferably selected from least a kind in the group be made up of Ti, Al, Zr, Zn, Sn, oxygen titanium, oxygen zirconium and oxygen tin, is more preferably at least a kind in Zr and oxygen zirconium.
(ii) except the chain length of methene chain of satisfied formation R is 2 to the maximum, the chain length forming R is the quantity of the methene chain of 2 is beyond the situation of two underlying conditions of 0 or 1
Now, when M is metal, represented by its valence mumber with a valency, when M is oxygenate metal, when being represented with (a+2) valency by the valence mumber of the metal forming oxygenate metal, n is for meeting the integer of the relation of m≤n<a × m.In the coordination of i.e. M, have not with the coordination of carboxylic acid ester groups bonding.
R be now carbon number be more than 1, less than 20 had halogen and/or heteroatomic linear chain structure, branched structure, alicyclic structure or aromatic ring structure alkyl in, except the chain length of methene chain of satisfied formation R is 2 to the maximum, all alkyl beyond the situation of the chain length forming R to be the quantity of the methene chain of 2 be two underlying conditions of 0 or 1.As such alkyl, such as, can enumerate valeric acid, caproic acid, 2 ethyl hexanoic acid, sad, neodecanoic acid, lauric acid, tetradecanoic acid, palmitinic acid, stearic acid, oleic acid, linolic acid, linolenic acid, lactic acid, oxysuccinic acid, citric acid, M-nitro benzoic acid, phthalic acid, m-phthalic acid, oxalic acid, propanedioic acid, succsinic acid, pentanedioic acid, hexanodioic acid, fumaric acid, toxilic acid, pyruvic acid etc.
Then, the preparation method of the compound involved by the second invention is described, the preparation method of compound involved in the present invention, is not limited to following method.
The compound of the second invention, by making metallic compound or oxygenate metallic compound (such as, the compound of described M), react to prepare with carbonate or carboxylic acid (such as there is carbonate or the carboxylic acid of the RCOO base of described R), preferably carry out heat treated (below, also referred to as " thermal treatment ".)。As metallic compound or oxygenate metallic compound, the carbonate of the carbonate of such as metal, oxygenate metal, metal halide (muriate etc.), oxygenate metal halide (muriate etc.), metal oxide or metal alkoxide can be used.
Such as, metal is in the example of zirconium, can enumerate the zirconium alkoxy compound etc. of zirconium carbonate, zirconyl carbonate, zirconium hydroxide, zirconium chloride, zirconium oxychloride, zirconyl acetate, Zircosol ZN, zirconium sulfate, zirconium caprylate, oleic acid oxidation zirconium, acetic acid zirconium, stearic acid zirconium white, lauric acid zirconium white, tetrabutyl zirconate etc.
The carbonate used in the preparation method of the compound of the second invention or carboxylic acid, use the RCOO compound (carbonate) or RCOOH (carboxylic acid) with the R that above-mentioned (i) or (ii) specifies separately.
The amount of carbonate or carboxylic acid, is not particularly limited, such as, can be less than 3 moles relative to metallic compound or oxygenate metallic compound 1 mole.
Particularly preferably by the carbonate (such as the carbonate of described M) of the carbonate of metal or oxygenate metal, and carboxylic acid (such as there is the carboxylic acid of the RCOO base of described R) heat treated, prepare the compound of the second invention.
The carbonate of metal or the carbonate of oxygenate metal, such as Zr 2(CO 3) (OH) 2o 2or O=Zr (CO 3) etc., relative to M (that is, the carbonate of metal or the carbonate of oxygenate metal) 1 mole, CO 3ratio be the carbonate (wherein, a refers to the ligancy that M is bonding) of metal carbonate or the oxygenate metal (be preferably below (a-1) mole, particularly (a-1.5) mole) less than a mole.In the carbonate of metal or the carbonate of oxygenate metal and the reaction of carboxylic acid, produce acid-base reaction by thermal treatment, the CO of described carbonate 3a part be replaced as OCOR, generate the metal being bonded with carboxylic acid ester groups of the second invention or oxygenate metal.When using the carbonate of metal carbonate or oxygenate metal, by effectively obtaining than a mole of few carboxylic acid in theory the metal or the oxygenate metal that are bonded with carboxylic acid ester groups.
For the preparation of the thermal treatment temp of the compound of the second invention, be preferably more than 25 DEG C, be more preferably more than 50 DEG C, more preferably more than 70 DEG C.Heat treatment time is such as 30 minutes ~ 4 hours, is preferably 1-3 hour.
Heat treated atmosphere does not limit, and is preferably the atmosphere of inert gases of nitrogen, argon gas etc.
Then, the metal oxide particle of the second invention is described.The metal oxide particle of the second invention, prepares by making metallic compound or oxygenate metallic compound heat in presence of water.The metal oxide particle of the second invention, such as, by by metallic compound or oxygenate metallic compound and carbonate or carboxylic acid, carries out heat treated to prepare in presence of water, also can via compound of the present invention in this preparation process.That is, metal oxide particle of the present invention, can be obtained by compound of the present invention, can obtain the metal oxide particle covered by the carbonate with the RCOO base identical with the RCOO base in compound of the present invention.
The overlay capacity of the carbonate in the metal oxide particle of the second invention, relative to the metal oxide particle that carbonate covers, is preferably more than 0.1 quality %.Thus, the dispersiveness of metal oxide particle in solvent etc. can be improved.Described overlay capacity, is more preferably more than 0.5 quality %, more preferably more than 2 quality %.When described overlay capacity is more, the quantitative change of the metal oxide particle contained by per unit volume self is few, therefore cannot play the raising effect of specific refractory power etc. fully, thus not preferred.Therefore, described overlay capacity is such as below 30 quality %, is preferably below 25 quality %, is more preferably below 20 quality %.In addition, be such as more than 50% by the productive rate of (mole number of the metal in carbonate covering metal oxide particle)/(mole number of the metal in metallic compound or oxygenate metallic compound) × 100 metal oxide particles obtained, be preferably more than 70%, be more preferably more than 80%.The upper limit of this productive rate is generally about 98%.
Form metal oxide, the crystalline texture of metal oxide, the particle diameter of metal oxide particle, crystallization particle diameter, median size, shape, the specific refractory power of the metal oxide particle obtained by the compound of the second invention, the explanation of above-mentioned first invention can be quoted.
The method of particle is prepared as the compound via the second invention, can be in presence of water, by metallic compound or oxygenate metallic compound, heat with the mixture of carbonate or carboxylic acid, concrete step can first make metallic compound or oxygenate metallic compound for (i), with carbonate or carboxylic acid reaction, after synthesizing compound of the present invention, the leading synthetic compound type that water is heat-treated is added in its reactant, also can be (ii) by by metallic compound or oxygenate metallic compound and carbonate or carboxylic acid, heat-treat with water, while synthesis compound of the present invention, the compound of synthesis of metal oxide particle and metal oxide synthesis type simultaneously.In this manual, the operation that water be heat-treated sometimes will be added in described (i), and reaction in described (ii) and heat treatment step, be called " hydrothermal treatment consists operation ".The step of (i) of leading synthetic compound type, as compared to the step of compound with (ii) of synthesis type while of metal oxide, can reduce pressure during thermal treatment.
In second invention, in described operation (i) or (ii), the water yield contained in this mixture, relative to metallic compound or oxygenate metallic compound 1 mole, be such as more than 5 moles, be preferably more than 7 moles, be more preferably more than 10 moles.Water contained in this mixture so-called, refers to the meaning of all water existed in the mixture, not only comprises the amount of the water of interpolation, also comprises water contained in the compound of the carbonate of metal or the carbonate of oxygenate metal etc., or as the water of solvent.
Hydrothermal treatment consists temperature, is preferably more than 100 DEG C, is more preferably more than 140 DEG C, more preferably more than 160 DEG C.The upper limit of hydrothermal treatment consists temperature, is not particularly limited, and is preferably less than 300 DEG C, is more preferably less than 250 DEG C, more preferably less than 220 DEG C.Hydrothermal conditions is such as 5-50 hour, is preferably 10-40 hour.
In the preparation method of the metal oxide particle of the second invention, pressure during hydrothermal treatment consists, is preferably more than 0.5MPa, is more preferably more than 0.6MPa.This upper limit of pressure, is generally below 3.0MPa, is preferably below 2.0MPa, is more preferably below 1.5MPa (particularly below 1.0MPa).In addition, atmosphere during hydrothermal treatment consists indefinite, be preferably the atmosphere of inert gases of nitrogen, argon gas etc.
In second invention, when particularly using zirconium carbonate and carboxylic acid to prepare compound, by mixture (usually containing the water relative to zirconium 1 mole being more than the 5 moles) thermal treatment of zirconium carbonate and carboxylic acid, the amount of adjustment carboxylic acid, or make this mixture further containing aromatic hydrocarbon (namely, under the existence of aromatic hydrocarbon, make the carbonate of M and the carboxylic acid reaction with RCOO base), adjustment comprises the amount (i.e. the carbonate of M and the amount of water when having a carboxylic acid reaction of RCOO base) of water in the mixture, or heat-treat (namely under the existence of basic cpd, under the existence of basic cpd, make the carbonate of M and the carboxylic acid reaction with RCOO base) etc., due to the ratio of the regular crystal in final the obtained cover type Zirconia particles of adjustable, thus preferred.This is respectively described below.
Described carboxylic acid, relative to the molar weight of zirconium 1 mole, is preferably less than 2 moles (underlying condition A).The molar weight of carboxylic acid is fewer, more can improve the ratio of the regular crystal in cover type Zirconia particles.The molar weight of carboxylic acid, is more preferably less than 1.5 moles, more preferably less than 1 mole, more preferably less than 0.7 mole.The molar weight of carboxylic acid is preferably more than 0.2 mole.When carboxylic acid amount is very few, the overlay capacity of carbonate can become insufficient.The molar weight of carboxylic acid is more preferably more than 0.3 mole, more preferably more than 0.4 mole.
Due to by making the mixture of described zirconium carbonate and carboxylic acid contain aromatic hydrocarbon (underlying condition B), the ratio of the regular crystal in the Zirconia particles (cover type Zirconia particles) of carbonate covering can be improved, thus preferably.Aromatic hydrocarbon is preferably the alky-substituted aromatic hydrocarbon that total carbon number is more than 7, is more preferably the alky-substituted aromatic hydrocarbon that total carbon number is more than 8 (particularly more than 9), is specially toluene, ethylbenzene, dimethylbenzene, diethylbenzene, Three methyl Benzene; With dimethylbenzene, Three methyl Benzene (particularly 1，2，4-trimethylbenzene).In addition, the aromatic hydrocarbon content in described mixture (mixture of zirconium carbonate and carboxylic acid), relative to carbonate 100 mass parts of zirconium, is preferably more than 30 mass parts, is more preferably more than 40 mass parts, more preferably more than 50 mass parts.On the other hand, when the content of aromatic hydrocarbon is superfluous, the productive rate of the final cover type Zirconia particles obtained can decline.Therefore, the content of the aromatic hydrocarbon in described mixture, relative to carbonate 100 mass parts of zirconium, such as, is preferably below 400 mass parts, is more preferably below 200 mass parts, more preferably below 100 mass parts.In addition, when the step of compound and metal oxide (ii) of synthesis type simultaneously, preferably when zirconium carbonate and carboxylic acid reaction (during compou nd synthesis), interpolation aromatic hydrocarbon.
The zirconium of amount relative to 1 mole of the water in the mixture of described zirconium carbonate and carboxylic acid is preferably less than 17 moles (underlying condition C).By suppressing the water yield in described mixture, the ratio of the regular crystal of adjustable cover type Zirconia particles.The water yield in described mixture, relative to the zirconium of 1 mole, is preferably less than 15 moles, is more preferably less than 10 moles.
In second invention, preferably under basic cpd exists, carry out described thermal treatment (underlying condition D).By heat-treating under the existence of basic cpd, the not only ratio of the regular crystal of adjustable cover type Zirconia particles, also can improve the productive rate of cover type Zirconia particles.Relative to the zirconium of 1 mole, basic cpd is preferably more than 0.1 mole, is more preferably more than 0.2 mole, more preferably more than 0.5 mole.The upper limit of basic cpd amount, relative to the zirconium of 1 mole, is generally less than 2 moles, is preferably less than 0.8 mole.In addition, the situation of the step of (ii) of reaction and thermal treatment simultaneous type, after the carbonate and carboxylic acid reaction of zirconium, preferably adds basic cpd and heat-treats.
Described basic cpd comprises the alkali of arbitrary definition of Bu Langsi Taide alkali, Lewis base etc., and can be any one in mineral compound, organic compound.Wherein, be preferably selected from the basic cpd of more than at least a kind in an alkali metal salt, alkaline earth salt and 1 ~ 3 grade of amine, be more preferably more than a kind in alkali-metal oxyhydroxide, the oxyhydroxide of alkaline-earth metal, organic amine compound, be particularly preferably alkali-metal oxyhydroxide.As basic cpd, most preferably be sodium hydroxide.
Described underlying condition A-D, can meet any one underlying condition, also can meet more than two simultaneously.
In addition, in above-mentioned underlying condition A-D, underlying condition A (relating to the underlying condition of carboxylic acid amount), underlying condition B (relating to the underlying condition of aromatic hydrocarbon) and underlying condition D (relating to the underlying condition of basic cpd), preferably meet the preparation method of described compound.In the preparation method of compound, underlying condition A, B and D, can meet any one underlying condition, also can meet more than two simultaneously.
Particularly when obtaining by the metal oxide particle of the carbonate covering containing RCOO base, wherein, be more than 1 at R for meeting carbon number, less than 20, halogen and/or heteroatomic linear chain structure can be had, branched structure, in the alkyl of alicyclic structure or aromatic ring structure, except the chain length of the methene chain of satisfied formation R is 2 to the maximum, with to form the chain length of R be the quantity of the methene chain of 2 be two underlying conditions of 0 or 1 alkyl beyond (namely, when R is specified by (ii) of the compound of the second invention) alkyl, preferred employing in presence of water, the carbonate of metal or the carbonate of oxygenate metal and the mixture of carboxylic acid are carried out the preparation method heated.
The metal oxide particle of the second invention, for have the carboxylic acid ester groups shown in following formula (2) carbonate cover metal oxide particle time, as mentioned above, can via the compound of the situation of (i) in compound of the present invention, also can not be via.Not via metal oxide particle during compound (i) of the present invention, such as can to enumerate on metal oxide particle with the method for the mode addition carbonate of organic synthesis (such as, carboxylic acid or the silane coupling agent of R ' COO structure will be had, the method that the metal oxide particle to unmodified processes by drying process or damp process) etc.
-OCO-R’(2)
(wherein, in formula, R ' is saturated hydrocarbyl, and the chain length forming the methene chain of this saturated hydrocarbyl is 2 to the maximum, and the quantity that chain length is the methene chain of 2 is 0 or 1.)
In addition, the R ' in above-mentioned formula (2), identical with the R of the situation of (i) of the compound of the second invention, can completely with reference to the explanation of the R of the situation of (i) of compound of the present invention.In addition, for the kind of metal, identical with the M of compound of the present invention.
For the metal oxide particle that the carbonate represented by above-mentioned formula (2) covers, form the kind of the metal oxide of this metal oxide particle, the overlay capacity of carbonate, particle diameter, particle shape, specific refractory power, crystalline texture, with described metal oxide particle (namely, the metal oxide particle obtained by compound of the present invention) identical, can completely with reference to their explanation.
Second invention, also comprises the preparation method of metal oxide particle, it is characterized in that, in presence of water, by the mixture heating of the metallic compound of the carbonate of the carbonate of metal or oxygenate metal or oxygenate metallic compound and carboxylic acid.In the present invention, by using metallic compound or the oxygenate metallic compound of the carbonate of metal or the carbonate of oxygenate metal, effectively can prepare metal oxide particle.
The metallic compound of the carbonate of metal or the carbonate of oxygenate metal or oxygenate metallic compound, be not particularly limited, when considering the specific refractory power of metal oxide particle, be such as Al, Ti, Zr, In, Zn, Sn, La, Y, Ce, these the carbonate of partial oxide, be preferably Al, Ti, Zr, Zn, Sn, Ce, these the carbonate of partial oxide, more preferably Al, Ti, Zr, Zn, Sn, these the carbonate of partial oxide, be particularly preferably the carbonate of the partial oxide of Ti, Zr.
Carboxylic acid can enumerate carboxylic acid illustrated in the compound of aforesaid the present application.
This metal oxide particle, can prepare in the same manner as the method for the metal oxide particle of preparation the invention described above.Other underlying condition refers to the metallic compound of the carbonate of the metal such as used or the carbonate of oxygenate metal or the kind of oxygenate metallic compound or carboxylic acid and blended ratio thereof, the pressure condition of water yield when concrete steps, hydrothermal treatment consists, the temperature of hydrothermal treatment consists, hydrothermal treatment consists, the atmosphere of hydrothermal treatment consists, underlying condition A-D, can completely with reference to these conditions.
Further, the second invention also can be combined with described first invention, the 3rd invention described later, the 4th invention respectively mutually.
Namely, as the method for the described metal oxide particle of preparation second invention, the preparation method of the preparation method of the metal oxide particle described in the first invention part, the preparation method of metal oxide particle described in the 3rd invention part, the metal oxide particle described in the 4th invention part can be quoted respectively.
In addition, compound (intermediate compound of metal oxide particle) described in second invention and metal oxide particle, in the scope with the feature described in the second invention, also the feature of the metal oxide particle described in the first invention can be had, also the compound of the 3rd invention record and the feature of metal oxide particle can be had, also can have the feature of the metal oxide particle that the 4th invention is recorded, also can combine further and there is these features.
3. the 3rd invention (third method)
In 3rd invention (third method), its maximum feature is, the carboxylic acid cpd for covering metal oxide compound is two or more.Further, the substituent carboxylic acid of more than 1 had in the group being selected from and being made up of ester group, ether, amide group, thioester substrate, thioether group, carbonate group, urethane groups and Urea-based by selection or (methyl) vinylformic acid, as a kind of the carboxylic acid cpd for covering, achieve the dispersiveness in medium.Carboxylic acid cpd and Metal Oxide Chemical bonding, or form carboxylic acid or its salt is attached to metal oxide together with hydrogen atom or cationic atom.Next coming in order are described.
The metal oxide particle of the 3rd invention, the dispersiveness in various medium is extremely good, can be applicable to various uses.Particularly exceedingly useful in the accurate microstructural purposes of the formation taking resist as representative, dispersion inequality or development residue can be improved.
First, the first carboxylic acid cpd used in the 3rd invention is described.In 3rd invention, in carboxylic acid cpd for covering metal oxide compound, adopt the substituting group with more than 1 in the group being selected from and being made up of ester group, ether, amide group, thioester substrate, thioether group, carbonate group, urethane groups and Urea-based (following, be sometimes referred to as specified substituent) carboxylic acid or (methyl) vinylformic acid (hereinafter referred to as the first carboxylic acid cpd).By adopting these compounds, the hydrophobicity of metal oxide particle and hydrophilic balance can be made to improve, the dispersiveness in the various media of hydrophilic solvent, hydrophobic solvent, monomer, oligopolymer, polymkeric substance etc. can be significantly improved.First carboxylic acid cpd is (methyl) vinylformic acid, or has the specified substituent of more than a kind, also can have multiple identical or different specified substituent, also can have the substituting group beyond specified substituent further.Specified substituent, ease from the viewpoint of obtaining, be preferably ester group, ether, amide group, more preferably ester group, ether.There is more than 1 specified substituent in 1 molecule, although the upper limit is not particularly limited, considers from operability when preparing metal oxide particle, be preferably less than 20.Be more preferably less than 10, more preferably less than 5.
First carboxylic acid cpd also can use commercially available product, also can be synthesized by known synthetic method.Such as, exemplify: the method being obtained ester cpds by various alkylol cpd and diprotic acid or anhydride reaction representativity; By the method being obtained by reacting ester cpds of epoxy compounds or glycidyl compound and diprotic acid; By the method being obtained by reacting ether compound of alcohol or water and cyclic ethers; By amine compound and diprotic acid or acid anhydrides react acid amides to the method for compound; By the method being obtained by reacting thioester compound of mercaptan compound and diprotic acid or acid anhydrides; The method etc. of sulfide compound is obtained by the desulfurization of two mercaptan.
The α carbon of the carboxyl of the first carboxylic acid cpd can be any one of secondary carbon, tertiary carbon, quaternary carbon or aromatic series carbon.In addition, the carboxyl of the first carboxylic acid cpd can be one or more, crosslinked in order to avoid occurring when preparing metal oxide particle between particle, is preferably less than 3, is more preferably 2, most preferably is 1.
From the viewpoint of the exchange easiness with the second carboxylic acid described later, the pKa of the first carboxylic acid cpd is preferably less than 4.8, is more preferably less than 4.7, and more preferably less than 4.6.The pKa of carboxylic acid cpd is for adopting the value calculated by calculational chemistry software ACD/pKaversion10.01 (AdvancedChemistryDevelopment.Ince society system).
Be admixed in solidification compound by the covering metal oxide particle of the 3rd invention, during for various uses, preferably the first carboxylic acid cpd has polymerizability double bond.By there is polymerizability double bond on the covering composition of metal oxide particle, can with other fusion composition copolymerization, thus can not occur when solidifying to condense or the problem of oozing out, even if also good dispersion state can be maintained in cured article.In addition, in the first carboxylic acid cpd, polymerizability double bond can be had, in the second carboxylic acid cpd described later, also can have polymerizability double bond.In addition, when using of more than two kinds first or the second carboxylic acid cpd, in them, at least a kind has polymerizability double bond.
As the concrete example of the first carboxylic acid cpd, vinylformic acid, methacrylic acid 2-acryloyl-oxyethyl succsinic acid, 2-methacryloxyethyl succsinic acid, 2-acryloyl-oxyethyl hexahydrophthalic acid, 2-methacryloxyethyl hexahydrophthalic acid, 2-acryloyl-oxyethyl phthalic acid, 2-methacryloxyethyl phthalic acid etc. can be enumerated.Wherein, vinylformic acid, 2-acryloyl-oxyethyl succsinic acid, 2-acryloyl-oxyethyl hexahydrophthalic acid, 2-acryloyl-oxyethyl phthalic acid is preferably used.
Described first carboxylic acid cpd, can only use a kind, also two or more use capable of being combined.The ratio of the first carboxylic acid cpd of covering metal oxide particle, relative to metal oxide particle 100 mass parts after covering, the first carboxylic acid cpd is preferably more than 0.1 mass parts.Thus, the dispersiveness of metal oxide particle in solvent etc. when can improve preparation or in product.The amount of the first carboxylic acid cpd, is more preferably more than 0.5 mass parts, more preferably more than 2 mass parts.When overlay capacity is more, the quantitative change of the metal oxide particle contained by per unit volume is few, thus not preferred.Therefore, the amount of the first carboxylic acid cpd, is generally below 30 mass parts, is preferably below 25 mass parts, is more preferably below 20 mass parts.
Then, the second carboxylic acid cpd is described.As long as the second carboxylic acid is the carboxylic acid beyond described first carboxylic acid, be just not particularly limited, from the viewpoint of preparation section described later, total preferably adopt carbon number be more than 3 straight-chain carboxylic acid, branched carboxylic acid, cyclic carboxylic acids or aromatic carboxylic acid.Wherein, particularly preferably branched carboxylic acid.By adopting branched carboxylic acid, the cohesion of metal oxide particle effectively can be suppressed.
Described second carboxylic acid cpd can only use a kind, also can combine two or more and use.The ratio of the second carboxylic acid cpd of metal oxide particle and this metal oxide particle of covering, relative to metal oxide particle 100 mass parts, the second carboxylic acid cpd is preferably more than 0.1 mass parts.Thus, the dispersiveness of metal oxide particle in solvent etc. when can improve preparation or in product.The amount of the second carboxylic acid cpd, is preferably more than 0.5 mass parts, more preferably more than 2 mass parts.When overlay capacity is more, the quantitative change of the metal oxide particle contained by per unit volume is few, thus not preferred.Therefore, the amount of the second carboxylic acid cpd, is generally below 30 mass parts, is preferably below 25 mass parts, is more preferably below 20 mass parts.
In addition, the total overlay capacity of described first carboxylic acid cpd and the second carboxylic acid cpd, relative to 100 mass parts, be preferably more than 0.2 mass parts, being more preferably more than 1 mass parts, more preferably more than 2 mass parts, is below 40 mass parts, be preferably below 35 mass parts, be more preferably below 30 mass parts.
The mass ratio of the overlay capacity of the first carboxylic acid and the second carboxylic acid, in the first carboxylic acid/the second carboxylic acid, is preferably 100/1 ~ 1/100, is more preferably 50/1 ~ 1/50, more preferably 30/1 ~ 1/30.By adjusting overlay capacity within the scope of this, the affinity of gained metal oxide particle and the medium such as wetting ability, hydrophobicity can be improved, can dispersiveness be improved.
For the metal oxide of the 3rd invention, form metal oxide, the crystalline texture of metal oxide, the particle diameter of metal oxide particle, crystallization particle diameter, median size, shape, the specific refractory power of metal oxide particle, the explanation of the invention of described first can be quoted.
Below, the representational preparation method of the metal oxide particle of the 3rd invention is described, but each operation can suitably change.In addition, when considering the feature of preparation method, sometimes the metal oxide particle of the 3rd invention is called below and replaces cover type particle.The particle (replacing cover type particle) of the 3rd invention is prepared by following steps: first, modulate by the particle of the second carboxylic acid cpd covering (following, be sometimes referred to as cover type particle), then, the second carboxylic acid of this cover type particle surface can be replaced with the first carboxylic acid cpd.
First, the modulation of cover type particle is described.Cover type particle, by presence of water, makes metal ingredient and the second carboxylic acid cpd carry out hydro-thermal reaction and obtain.The explanation that the illustrating of hydro-thermal reaction can quote aforementioned first invention, the explanation of the second invention.
In 3rd invention, hydro-thermal reaction is carried out by making metal ingredient and the second carboxylic acid cpd, the cover type particle covered by the second carboxylic acid cpd can be prepared, preferably make more than at least a kind of being selected from (i), (ii) and (iii) carry out hydro-thermal reaction.That is, (i) second salt of carboxylic acid cpd and metal oxide precursor, (ii) second metal-salt of carboxylic acid cpd, (iii) second carboxylic acid cpd and metal oxide precursor.
Below, describe in detail for as described metal oxide precursor, use the water-soluble of the nitrate of the muriate of the oxychlorination thing of various metal etc. or oxygen nitric acid thing etc. etc. and the metal oxide precursor that corrodibility is high as raw material time, the preferably situation of described (i).
Further, so-called salt, is not only carboxylic acid and metal oxide precursor stoichiometrically than the single compounds formed, and can be composite salt or the composition that there is unreacted carboxylic acid or metal oxide precursor yet.
In described (i), the salt of so-called second carboxylic acid cpd and metal oxide precursor, is neutralized into second carboxylic acid cpd that containing composition and metal oxide precursor from the carboxylate salt of second carboxylic acid cpd react and obtain of degree of neutralization in the scope of 0.1-0.8 and the salt of metal preferably by basic metal and/or alkaline-earth metal.
Described be neutralized into degree of neutralization 0.1-0.8 scope containing the composition of carboxylate salt, refer to the whole carboxyls 1 mole relative to formation second carboxylic acid cpd, for the composition containing organic carboxylate of the state that the carboxyl of 0.1-0.8 mole is neutralized by basic metal and/or alkaline-earth metal, except obtaining except adding appropriate alkali-metal oxyhydroxide etc. in the second carboxylic acid cpd, also can by unneutralized second carboxylic acid cpd with completely and/or the carboxylate compounds that neutralizes of part be obtained by mixing.This does not neutralize, the second carboxylic acid cpd of neutralization or part neutralization completely, can be identical, can difference mutually yet, further also can for not the neutralizing of the composition that is made up of different carboxylic acids, neutralize completely or part corrective.
Described degree of neutralization is preferably 0.1-0.8, is more preferably 0.2-0.7.During less than 0.1, because the solubleness of the second carboxylic acid cpd is low, thus there is the situation that fully cannot form described salt, in addition, during more than 0.8, generate the white precipitate being speculated as the oxyhydroxide of metal in a large number, thus there is the situation of the productive rate reducing metal oxide particle.
Can be any one for obtaining the alkali and alkaline earth metal ions of the described composition containing carboxylate salt, preferably forming the metal of water-soluble high carboxylate salt, being preferably basic metal, being particularly preferably sodium and potassium.
Described containing the composition of carboxylate salt and the ratio of described metal oxide precursor, relative to metal oxide precursor 1 mole, carboxyl is preferably 1 mole-20 moles, is more preferably 1.2-18 mole, more preferably 1.5-15 mole.
When the composition containing carboxylate salt described in making and the reaction of described metal oxide precursor, preferably the aqueous solution is mixed mutually.As long as temperature of reaction can remain the temperature of the aqueous solution, just there is no special problem, be preferably room temperature to 100 DEG C, be more preferably 40 DEG C-80 DEG C.
The described salt that composition containing carboxylic acid described in making and described metal oxide precursor are reacted and obtained, although directly can supply hydro-thermal reaction, preferably passes through the removings such as filtration by insoluble by product in advance.
Then, the situation of (ii) is described in detail.
In the embodiment of (ii), use the metal-salt of the second carboxylic acid cpd modulated in advance.Have and through operation loaded down with trivial details as above, need not can supply the advantage of hydro-thermal reaction.But, due to can handy compound limited, sometimes cannot obtain the situation of the metal oxide particle covered by objective carboxylic acid ester group.Metal is not particularly limited, preferably containing being selected from Ti, Al, Zr, Zn, Sn and Ce at least a kind.
As the metal-salt of embodiment that can be used for (ii), 2 ethyl hexanoic acid titanium, 3,3-acid dimethyl titaniums, sad titanium, oleic acid oxidation titanium, stearic acid titanium oxide, lauric acid titanium oxide, aluminium octoate, zirconium caprylate, 2 ethyl hexanoic acid zirconium, oleic acid oxidation zirconium, stearic acid zirconium white, lauric acid zirconium white, zinc octoate, stannous octoate, cerium octoate etc. can be exemplified.
When the purity of metal-salt is lower, refining rear use can be implemented, also can directly by commercially available product or prior salt supply hydro-thermal reaction of modulating.
Then, the situation of described (iii) is described in detail.
In described (iii), as described metal oxide precursor, such as, the oxyhydroxide of various metal, muriate, oxychlorination thing, vitriol, acetate, organic acid salt, metal alkoxides etc. can be enumerated.Such as, using in the example of zirconium, is preferred method when using the zirconium alkoxide etc. of zirconium hydroxide, zirconium chloride, zirconium oxychloride, zirconyl acetate, Zircosol ZN, zirconium sulfate, zirconium caprylate, oleic acid oxidation zirconium, acetic acid zirconium, stearic acid zirconium white, lauric acid zirconium white, tetrabutyl zirconate etc.In addition, using in the example of titanium, is preferred method when preferably using the alkyl titanium oxide etc. of titanium hydroxide, titanium chloride, oxychlorination titanium, acetic acid oxygen titanium, titanyl nitrate, titanium sulfate, sad titanium, oleic acid oxidation titanium, acetic acid titanium, stearic acid titanium oxide, lauric acid titanium oxide, four titanium butoxide (such as four titanium n-butoxide) etc.
For described second carboxylic acid cpd, identical with above-mentioned (i).
Preferably in presence of water, by described metal oxide precursor and described second carboxylic acid cpd mixing.Now, by heating or under reduced pressure carrying out, low-boiling compound contained in the described metal oxide precursor of ammonia or acetic acid etc. is driven out of outside system, the rising of pressure can be suppressed in the hydro-thermal reaction of subsequent processing, thus preferably.In addition, also described reaction can be carried out in the solution after adding organic solvent described later.
Then, hydro-thermal reaction is described.
By by any one supply hydro-thermal reaction in described (i)-(iii), metal oxide particle composition can be obtained.By means of only described (i)-(iii), when viscosity high and effectively cannot carry out hydro-thermal reaction, to this (i)-(iii) add display good solubility organic solvent.
The particular case in pressure when organic solvent, amount of moisture, reaction, temperature of reaction, reaction times, can quote the explanation of the explanation of the first invention, the second invention.
By described hydro-thermal reaction, usually, can be generated in container bottom precipitation by the metal oxide particle (cover type particle) that the second carboxylic acid cpd covers.Cover type particle can implement condensation product etc. refining for the by product or cover type particle removing carbon that hydro-thermal reaction generates etc.Such as, after resultant filtration will be precipitated, be dissolved in toluene equal solvent, after being filtered by insolubles, obtain cover type particle by removing toluene equal solvents such as concentrating under reduced pressure again.
During described hydro-thermal reaction, preferably use basic cpd.As long as basic cpd shows the compound of alkalescence when being dissolved in water, the no matter form of Bu Langsi Taide alkali or Lewis base etc., mineral compound, organic compound.Wherein, preferably be selected from the basic cpd of more than at least a kind in an alkali metal salt, alkaline earth salt and 1-3 level amine, be more preferably the oxyhydroxide of basic metal or alkaline-earth metal, an alkali metal salt of carboxylic acid, organic amine compound, be particularly preferably alkali-metal oxyhydroxide, organic amine compound.By there is basic cpd, the productive rate of the cover type particle of generation can be improved.Further, the carboxylic acid of broad variety can be utilized as raw material, obtain the cover type particle covered by carboxylic acid ester groups being difficult to the kind prepared by previous methods.
The amount of described basic cpd, relative to the metal oxide precursor that 1 mole uses in this operation, is preferably more than 0.03 mole and be less than 1.5 moles.By adding the basic cpd of described scope, can further improve the productive rate of cover type particle.
Then, the replacement operation of cover type particle is described.The replacement cover type particle (metal oxide particle) obtaining the 3rd invention is replaced with the first carboxylic acid cpd by the second carboxylic acid cpd of the cover type particle described hydro-thermal reaction obtained.Particularly, this replacement is undertaken by the mixture (particularly mixed solution) stirred containing cover type particle and the first carboxylic acid cpd.The mass ratio of the first carboxylic acid cpd and cover type particle, is not particularly limited, and as the first carboxylic acid cpd/cover type particle, is preferably 5/100 ~ 200/100.Time fewer than 5/100, the import volume of the first carboxylic acid cpd becomes insufficient sometimes, and dispersiveness becomes insufficient, than more than 200/100 time, replacing, the import volume in cover type particle is saturated and become non-effective.Be more preferably 10/100 ~ 150/100.
The solvent used when modulating described mixed solution, directly can use solvent during described hydro-thermal reaction, also can use other solvent.Preferred use with for the identical solvent (composition solvent) of composition described later (solidification compound etc.).When modulation replaces cover type particle in such solvent, can further improve obtained replacement cover type particle affinity in the composition, can highly prevent dispersion uneven further.
Whipping temp is preferably 0-100 DEG C, is more preferably 10-70 DEG C, more preferably 20-50 DEG C, and the concentration of the cover type particle in mixed solution is preferably 5-80 quality %, is more preferably 10-60 quality %.In addition, ball mill etc. also can be used to carry out process that is solvent-free or greater concn.Reaction times is preferably 10 minutes ~ 5 hours, is more preferably 20 minutes ~ 2 hours.
When modulation replaces cover type particle in composition solvent, replace cover type particle and be preferably dissolved in composition solvent.Now, by adding suitable Weak solvent (such as, the aliphatic hydrocarbon series solvent of hexane etc.), replacement cover type particle is separated out.Precipitate is by suitable solid-liquid isolation method (filtration method, centrifugal separation etc.) and separated from solvent.On the other hand, when replacement cover type particle dissolves in a solvent, also by concentrated grade and separated from solvent.
The covering metal oxide particle of the 3rd invention obtained by aforesaid method, is preferably cleaned.By cleaning, by product or unreacted first carboxylic acid cpd or the second carboxylic acid cpd be substituted can be removed from composition, during for various uses described later, can not detrimentally affect be caused.As clean solvent, be not particularly limited, can preferably use acetone, hexane, heptane, octane, methyl alcohol, ethanol.
Further, the 3rd invention also can be combined with the first invention, the second invention, the 4th invention respectively mutually.
Namely, as the method for the metal oxide particle described in preparation the 3rd invention, the preparation method of the preparation method of the metal oxide particle described in the first invention part, the preparation method of metal oxide particle described in the second invention part, the metal oxide particle described in the 4th invention part can be quoted respectively.
In addition, cover type particle described in 3rd invention and replacement cover type particle, in the scope with the feature described in the 3rd invention, also the feature of compound (intermediate compound of metal oxide particles) described in the first invention and metal oxide particle can be had, also the feature of compound described in the second invention and metal oxide particle can be had, also can have the feature of the metal oxide particle described in the 4th invention, further, also can combine and there is these features.
4. the 4th invention (the 4th method)
But there is the situation containing impurity such as halogenide in the raw material (metal oxide precursor) of metal oxide particle, present invention also offers the preparation method of the metal oxide particle effectively reducing these impurity.
According to the 4th invention, (by with the carboxylic acid being used for covering below, will the salt of tricarboxylic tricarboxylic acid and metal oxide precursor be called or be referred to as " tricarboxylic metal-salt etc. " with the intermediate compound of the metal oxide particle of tricarboxylic acid bonding.) different carboxylic acid is (following, be called tetracarboxylic acid) when making together with alkali for the tricarboxylic metal-salt of process etc., halid fluidity changes, dissimilate with tricarboxylic metal-salt etc. or metal oxide particle (cover type metal oxide particle), can removing be isolated.More it is shocking, specify that according to the 4th invention, the halogenide of removing trace impurity, can improve the ratio of the regular crystal of the metal oxide particle finally obtained effectively.
According to the 4th invention, owing to using tetracarboxylic acid bronsted lowry acids and bases bronsted lowry together to process tricarboxylic metal-salt etc., therefore can reduce the halogen concentration of chlorine etc., obtain (purifying metal salt etc.) such as the tricarboxylic metal-salts refined.Further, when using this purifying metal salt etc., not only can reduce halogen concentration, also can obtain the ratio of regular crystal higher, metal oxide particle that namely specific refractory power is higher.
That is, be the technology using the halogenide removing contained in the tricarboxylic metal-salt etc. of the insulating covering agent of raw material and metal oxide precursor modulation from carboxylic acid.Tricarboxylic metal-salts etc., become metal oxide particle by hydro-thermal reaction.In the 3rd invention, importantly in the modulation from tricarboxylic metal-salt etc. until complete any instant of the series of processes of the preparation of metal oxide particle, to make in the solution containing tricarboxylic metal-salt etc., containing can not the carboxylic acid (namely not forming the carboxylic acid of compound with metal) (tetracarboxylic acid) of covering metal oxide precursor and the alkali of specified amount, to react with impurity (halogenide).Thus, make tetracarboxylic acid, alkali and halide reaction, halid fluidity can be changing into another kind (such as water-soluble) by a kind of (such as oil soluble), can remove from (such as oil solubles) such as tricarboxylic metal-salts.
The amount of alkali is not particularly limited, and is preferably below 1 equivalent relative to tetracarboxylic acid.By the selection of alkali, during relative to the amount of tetracarboxylic acid more than 1 equivalent, alkali and tricarboxylic metal-salt etc. form white precipitate and form gel, sometimes cannot be separated removing halogenide.Relative to tetracarboxylic acid, the amount of alkali is preferably below 0.7 equivalent, and be more preferably below 0.5 equivalent, lower limit is not particularly limited, such as, be more than 0.1 equivalent.
In 4th invention, the most important thing is to make containing in the solution of halogenide as the tricarboxylic metal-salt etc. of impurity, the alkali containing tetracarboxylic acid and specified amount.Its moment containing the alkali of tetracarboxylic acid and specified amount is not limited, can at a series of preparation section of modulation afterwards to preparing metal oxide particle of tricarboxylic metal-salt etc. (namely, modulated by tricarboxylic acid and metal oxide precursor in the process of tricarboxylic metal-salt etc. to before terminating hydro-thermal reaction operation) any stage implement, particularly preferably make in the solution containing the tricarboxylic metal-salt that exists at the end of the modulating process such as tricarboxylic metal-salt etc., the alkali containing tetracarboxylic acid and specified amount.By making it contain tetracarboxylic acid bronsted lowry acids and bases bronsted lowry together with halogenide in this moment, effectively halogenide can be removed.Making it contain the method for carboxylic bronsted lowry acids and bases bronsted lowry, can be any one in following 1-3.
1. make carboxylic acid and alkali reaction in advance, add after forming salt.
2. add carboxylic bronsted lowry acids and bases bronsted lowry simultaneously.
3., after adding carboxylic acid, add alkali.
The halid reactant produced by tetracarboxylic acid bronsted lowry acids and bases bronsted lowry is (following, also referred to as fluidity change halogenide) removing method, as long as utilize the fluidity diverse ways with tricarboxylic metal-salt etc., just be not particularly limited, the known methods such as clean, crystallization can be adopted, easier because cleaning removing, thus recommend.In order to by cleaning removing halogenide, in advance tricarboxylic metal-salt etc. is dissolved in a kind of solvent (such as oil-based solvent) of fluidity, the solvent (such as aqueous solvent) of this solution by another kind of fluidity is cleaned.In addition, these a kind of and alternative fluidity solvents, can add after halid reaction, preferably by the part namely forming the solution containing tricarboxylic metal-salt etc. before reacting.In addition, during by the solution namely formed before reacting containing tricarboxylic metal-salt etc. a part of, described fluidity, determines after halide reaction.Namely, containing tricarboxylic metal-salt etc. and halid solution, the latest after halid reaction, organic solvent (a kind of fluidity solvent (the first solvent) containing the tricarboxylic metal-salt of solubilized etc., such as oil-based solvent), and with the second solvent (another kind of fluidity solvent, such as aqueous solvent) that this organic solvent is separated, preferably make described halid reactants dissolved after the second solvent again by organic solvent and the second separated from solvent.Thus, by being dissolved in tricarboxylic metal-salt of same solvent etc. and halogenide, the organic solvent and the second solvent that are separated can be separated to respectively.After separatory, by the solution containing tricarboxylic metal-salt etc., can clean with the second solvent further, also can carry out crystallization in addition.
Organic solvent (oil-based solvent), as long as the tricarboxylic metal-salt of solubilized etc., is just not particularly limited, can uses the aromatic hydrocarbon solvent of such as benzene,toluene,xylene etc.; The ether series solvent of Di Iso Propyl Ether, t-butyl methyl ether, dibutyl ether, diglyme etc.; The modification ethers of propylene glycol monomethyl ether acetate etc.; The ketone series solvent of methyl ethyl ketone, mibk etc.; The ester series solvent of vinyl acetic monomer, N-BUTYL ACETATE etc.; The halogen series solvent of chloroform, two chloroforms etc.; The cyclic hydrocarbon solvents of hexanaphthene, methylcyclohexane, ethylcyclohexane etc.; The chain hydrocarbon solvent etc. of pentane, hexane, heptane, octane, octane-iso, Permethyl 99A. etc.
In addition, as the second solvent (aqueous solvent), the mixed solvent etc. of water, water and water-miscible organic solvent can be enumerated.As water-miscible organic solvent, the alcohols of methyl alcohol, ethanol etc. can be illustrated; The ethers of ethylene glycol, glycol dimethyl ether, tetrahydrofuran (THF) etc.; The ketone of acetone, dioxane etc.; The nitrile etc. of acetonitrile etc.
The amount of the first solvent, relative to metal oxide precursor, is preferably 0.25-4.0 quality doubly, is more preferably 0.5-2.0 quality doubly.In addition, the amount of the second solvent, relative to the first solvent, is preferably 0.2-10 quality doubly, is more preferably 0.5-5 quality doubly.
Make temperature of reaction when tetracarboxylic acid bronsted lowry acids and bases bronsted lowry and described halide reaction, be preferably 40-150 DEG C.By being adjusted to such temperature range, can effectively generate halid reactant, removing halogen.The lower limit of described temperature of reaction, be preferably more than 50 DEG C, more preferably more than 70 DEG C, the upper limit of described temperature of reaction, is more preferably less than 130 DEG C, more preferably less than 100 DEG C.Reaction times is not particularly limited, such as, be 15 minutes ~ 3 hours (being preferably 30 minutes ~ 1 hour) left and right.
Metal oxide particle covers by tricarboxylic acid, has the effect of the dispersiveness improved in the medium of solvent or resin etc.As tricarboxylic acid, the carboxylic acid described in the first invention can be used.
Tricarboxylic acid, relative to 1 mole, the metal in metal oxide precursor, is preferably 1-5 mole, is more preferably 2-4 mole.Particularly in the modulation of tricarboxylic metal-salt etc., the excessive tricarboxylic acid do not reacted with metal oxide precursor remains, when this excessive tricarboxylic acid is used as tetracarboxylic acid, the lower limit of tricarboxylic acid amount, relative to 1 mole, the metal in metal oxide precursor, be preferably more than 1.3 moles, be more preferably more than 1.5 moles.In addition, when using the tetracarboxylic acid different from tricarboxylic acid, the upper limit of tricarboxylic acid amount, as long as the degree that can improve the metal oxide particle dispersiveness in media as well finally obtained, such as, is less than 3 moles, is more preferably less than 1.5 moles.
As metal oxide precursor, more than a kind in the group selecting the carbonate of free metal, metal halide and oxygenate metal halide to form can be used.As the metal forming metal oxide precursor, such as, Ti, Al, Zr, In, Zn, Sn, La, Y, Ce, Mg, Ba, Ca etc. can be enumerated.From the viewpoint of the specific refractory power that can improve the metal oxide finally obtained, be preferably selected from least a kind (particularly Zr) in the group be made up of Ti, Al, Zr, Zn and Sn.
Temperature when making tricarboxylic acid and metal oxide precursor react the tricarboxylic metal-salt of generation etc. is 50-100 DEG C of (being preferably 70-90 DEG C) left and right, and the time is 1-5 hour (being preferably 2-4 hour) left and right.
Tetracarboxylic acid is not particularly limited, and such as, in the same manner as tricarboxylic acid, can use the carboxylic acid described in the first invention.Tetracarboxylic acid can be different from tricarboxylic acid, also can be identical.Time particularly identical, in the modulation of described tricarboxylic metal-salt etc., what make not react with described metal oxide precursor is excessive carboxylic acid remained, also preferably uses this excessive carboxylic acid as tetracarboxylic acid.Tetracarboxylic acid can only use a kind, also two or more use capable of being combined.
The amount of tetracarboxylic acid, relative to 1 mole, the metal in metal oxide precursor, such as, is more than 0.3 mole, is more preferably more than 0.5 mole.The upper limit of tetracarboxylic acid amount is not particularly limited, and relative to 1 mole, the metal in metal oxide precursor, such as, is less than 4 moles, is preferably less than 3 moles.
Alkali is not particularly limited, no matter highly basic, weak base.Such as comprise the alkali metal hydroxide of sodium hydroxide or potassium hydroxide etc.; The alkaline earth metal hydroxides of magnesium hydroxide etc.; The alkali etc. containing N of ammonia, triethylamine, pyridine etc.Be preferably ammonia.
As mentioned above, time together with halogenide containing carboxylic bronsted lowry acids and bases bronsted lowry, can remove halogenide, can obtain the metal of halogen concentration relative to metal oxide precursor, such as, be the purified compound of below 10 quality ppm (being preferably below 5 quality ppm).More surprisingly, specify that and the halogenide existed as impurity in metal oxide precursor is removed, effectively can improve the ratio of the regular crystal of the metal oxide particle finally obtained.
Namely, the tricarboxylic metal-salt etc. (the purifying metal salt etc.) halogen concentration obtained by above-mentioned preparation method reduced carries out metal oxide particle (cover type metal oxide particle) that hydro-thermal reaction obtains while decreasing halogen concentration, and the ratio of the regular crystal in crystallization is higher.More specifically, halogen is below 10 quality ppm relative to the ratio of metal oxide particle, and tetragonal phase is more than 70% for the ratio of the total of the whole crystal system in crystallization.The ratio of described halogen, be preferably below 7 quality ppm (being more preferably below 5 quality ppm), the ratio of described regular crystal is preferably more than 75%.
In addition, above-mentioned metal oxide particle, is covered by the carbonate shown in following formula (3).
-OC(＝O)-R”(3)
R " be saturated hydrocarbyl.Preferred use R " in total carbon number be the carbonate of more than 3.By making R " in total carbon number be more than 3, the dispersiveness of metal oxide particle in the medium of solvent or resin etc. finally obtained can be improved.From the viewpoint of dispersiveness, preferred R " in total carbon number more, its lower value, is more preferably 4, more preferably 5.On the other hand, the upper limit of the total carbon number in R is not particularly limited, and such as, is less than 20.
Use the hydro-thermal reaction of purified compound, the explanation of the explanation of described first invention, the second invention and the 3rd invention can be quoted.
Further, the 4th invention also can be combined with the first invention, the second invention, the 3rd invention respectively mutually.
Namely, as the method for the metal oxide particle described in preparation the 4th invention, the preparation method of the preparation method of the metal oxide particle described in the first invention part, the preparation method of metal oxide particle described in the second invention part, the metal oxide particle described in the 3rd invention part also can be quoted respectively.
In addition, compound described in 4th invention and metal oxide particle, in the scope with the feature described in the 4th invention, also the feature of compound (intermediate compound of metal oxide particle) described in the first invention and metal oxide particle can be had, also the cover type particle described in the second invention and the feature replacing cover type particle can be had, also can have the feature of the metal oxide particle described in the 3rd invention, further, also can combine and there is these features.
5. composition
The present invention also comprises the composition containing above-mentioned each compound or each metal oxide particle.As composition of the present invention, compound or metal oxide particle dispersion dispersion in a solvent can be exemplified; Containing compound or metal oxide particle for the resin combination (following, sometimes referred to as " resin combination ") etc. of indicating meter with transparent planar molding.Above-mentioned metal oxide particle, can be used alone, and also can use as composition together with other material.
Covering metal oxide particle of the present invention, owing to having significant dispersiveness to various medium, can add in multi-solvents, monomer (monofunctional monomer and/or cross-linkable monomer), oligopolymer, polymkeric substance etc. or in their combination.
For the solvent of dispersion of the present invention, as long as compound of the present invention or metal oxide particle demonstrate the solvent of higher dispersiveness.Such as can enumerate the alcohols of methyl alcohol, ethanol, n-propyl alcohol, Virahol, ethylene glycol etc.; The ketone of methyl ethyl ketone, methyl iso-butyl ketone (MIBK), pimelinketone etc.; The ester class of vinyl acetic monomer, propyl acetate, propylene glycol monomethyl ether acetate etc.; The ethers of ethylene glycol monomethyl ether, diethylene glycol monobutyl ether etc.; The modification ethers (being preferably ether modification and/or ester modified ethers, more preferably ether modification and/or ester modified alkane glycols) of propylene glycol monomethyl ether acetate etc.; The hydro carbons of benzene,toluene,xylene, ethylbenzene, Three methyl Benzene, hexane, hexanaphthene, methylcyclohexane, ethylcyclohexane, mineral spirits etc.; The halogenated hydrocarbons of two chloroforms, chloroform etc.; The amides of dimethyl formamide, N,N-dimethylacetamide, N-Methyl pyrrolidone etc.; Water; The oils of mineral oil, vegetables oil, wax oil, silicone oil etc.Can in these a kind of choice for use, two or more also can be selected used in combination.From the viewpoint of operability, the boiling point under preferred normal pressure is more than 40 DEG C and is the solvent of about less than 250 DEG C.In resist purposes described later, be preferably ketone, modification ethers etc.
In the dispersion according to the invention, can the polymerizable compound of monofunctional monomer, cross-linkable monomer etc. as medium, as long as compound of the present invention or metal oxide particle demonstrate the medium of higher dispersiveness.
As long as monofunctional monomer only has the compound of 1 polymerisable carbon-to-carbon double bond, (methyl) acrylate can be enumerated; Vinylbenzene, p-tert-butylstyrene, alpha-methyl styrene, o-methyl styrene, p-methylstyrene, styrenic monomers to chloro-styrene, p-chloromethyl styrene etc.; The monomer containing carboxyl of (methyl) vinylformic acid etc.; The monomer etc. containing hydroxyl of hydroxyethyl (methyl) acrylate etc.As above-mentioned (methyl) acrylate, (methyl) alkyl acrylate of (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) n-propyl, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) 2-EHA, (methyl) lauryl acrylate etc. can be enumerated such as particularly; (methyl) acrylate base ester of (methyl) cyclohexyl acrylate, (methyl) isobornyl acrylate etc.; (methyl) vinylformic acid aralkyl ester of (methyl) benzyl acrylate etc.; (methyl) acrylate etc. with glycidyl of (methyl) glycidyl acrylate etc., is preferably (methyl) methyl acrylate.These illustrative monofunctional monomer, can be used alone, and also suitably can mix more than two kinds uses.
As long as the compound of the carbon-to-carbon double bond of cross-linkable monomer containing multiple carbon-to-carbon double bond copolymerization that can have with monofunctional monomer.As this cross-linkable monomer, poly-(methyl) acrylate of aklylene glycol of such as ethylene glycol bisthioglycolate (methyl) acrylate, Diethylene Glycol two (methyl) acrylate, propylene glycol two (methyl) acrylate, dipropylene glycol two (methyl) acrylate etc. can be enumerated particularly; Poly-(methyl) acrylate of neopentyl glycol of neopentyl glycol two (methyl) acrylate, two neopentyl glycol two (methyl) acrylate etc.; Poly-(methyl) acrylate of TriMethylolPropane(TMP) of trimethylolpropane tris (methyl) acrylate, two (TriMethylolPropane(TMP)) four (methyl) acrylate etc.; Polyfunctionality (methyl) acrylate of poly-(methyl) acrylate of tetramethylolmethane of tetramethylolmethane four (methyl) acrylate, Dipentaerythritol six (methyl) acrylate etc. etc.; The polyfunctionality styrenic monomers of Vinylstyrene etc.; The polyfunctionality allyl ester system monomer etc. of Phthalic acid, diallyl ester, diallyl isophthalate, triallyl cyanurate, triallyl isocyanate etc.
Compound or metal oxide particle concentration in dispersions, suitably can set according to purposes, usually, is below 90 quality % relative to this dispersion, and be difficult to disperse equably more than becoming during 90 quality %, gonorrhoea appears in dispersion.On the other hand, lower value is not particularly limited, and considers the cost of solvent, such as, be more than 1 quality %, is preferably more than 5 quality % and be below 80 quality %, more preferably more than 10 quality % and be below 70 quality %.
Be used in the resin of resin combination, as long as be just not particularly limited as the resin of ordinary resin use, such as, can enumerate thermoplastic resin, heat-curing resin, light-cured resin.
Composition containing above-mentioned monomer is equivalent to solidification compound.Resin combination is formed after the solidification of this solidification compound.In addition, composition of the present invention, also can for the resin combination containing above-mentioned polymkeric substance (resin).When forming resin combination of the present invention, the resin as medium (matrix) can adopt in thermoplastic resin, heat-curing resin, light-cured resin any one.
As thermoplastic resin, the polyamide-based of 6-nylon, 66-nylon, 12-nylon etc. specifically can be exemplified; Polyimide; Polyurethanes; The polyalkenes of polyethylene, polypropylene etc.; The polyester of PET, PBT, PEN etc.; The fragrant family polyethers of polyethersulfone, polyether ethersulfone, polyetherketone, polyether-ether-ketone etc.; Polyvinyl chloride; Polyvinylidene chloride class; Polyvinyl acetate; Polystyrene type; (methyl) acrylic resin based polymer; ABS resin; Fluoro-resin; Imide silane resin etc.In addition, the soft resin or hard resin etc. of polyvinyl butyral acetal system resin, polyurethane series resin, ethylene-vinyl acetate copolymer system resin, ethene-(methyl) acrylate copolymer system resin etc. can also be enumerated.During using thermoplastic resin as medium, known blending means can be used, such as, suitably can adopt the mixing utilizing forcing machine or the mixing utilizing solution.
As heat-curing resin, the resol of the phenol formaline resin, cresols formaline resin etc. as condensation system heat reactive resin can be enumerated; The amine resin etc. of urea resin, melamine resin, guanamine resin etc. when adopting phenolic aldehyde system resin, and is preferred embodiment with having the compound of triazine ring, guanamine derivatives, cyanuric acid derivative or isocyanuric acid derivatives.
As resin that is hot or photocuring, the resin with cationic polymerizable group and/or free-radical polymerised group can be used.Epoxy resin can be enumerated particularly, urethane (methyl) acrylate, epoxy group(ing) (methyl) acrylate, polyester (methyl) acrylate, unsaturated polyester, the phenylethylene resin series of Vinylstyrene etc., the allyl ester system resin of Phthalic acid, diallyl ester, diallyl isophthalate, triallyl cyanurate, triallyl isocyanate etc., ethylene glycol bisthioglycolate (methyl) acrylate, 1,6-hexylene glycol two (methyl) acrylate, 1,9-nonanediol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, 3-methyl isophthalic acid, 5-pentanediol two (methyl) acrylate, 2-butyl-2-ethyl-1,3-PD two (methyl) acrylate, dihydroxymethyl tristane two (methyl) acrylate, pentacyclopentadecandimethanol glycol two (methyl) acrylate, two (methyl) acrylic acid adduct of bisphenol A diglycidyl ether, cyclohexanedimethanol two (methyl) acrylate, norbornane dimethanol two (methyl) acrylate, to menthane-1,8-glycol two (methyl) acrylate, to menthane-2,8-glycol two (methyl) acrylate, to menthane-3,8-glycol two (methyl) acrylate, 2 functionality (methyl) acrylic compound of dicyclo [2.2.2]-octane-1-methyl-4-sec.-propyl-5,6-dihydroxymethyl two (methyl) acrylate etc., trimethylolpropane tris (methyl) acrylate, trimethylolethane trimethacrylate (methyl) acrylate, glycerine three (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, Dipentaerythritol six (methyl) acrylate, tripentaerythritol gathers (methyl) acrylate, tetrapentaerythritol gathers (methyl) acrylate, (methyl) acrylic of (methyl) acrylic compound more than 3 functionality of poly-(methyl) acrylate of five tetramethylolmethanes etc. etc., (methyl) vinylformic acid-2-ethene acyl-oxygen ethyl ester, (methyl) propylene system derivative with ether structure of two (methyl) acrylate of three (methyl) acrylate of the ethylene oxide affixture of (methyl) vinylformic acid-2-(2-ethene acyloxyethyl) ethyl ester, Diethylene Glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, TEG two (methyl) acrylate, TriMethylolPropane(TMP), the ethylene oxide affixture of dihydroxyphenyl propane etc., the vinyl ether based compound of triethyleneglycol divinylether, cyclohexanedimethanol divinyl base ether etc., the allyl ethers based compound of the allyl ethers of trimethylolpropane allyl ether, pentaerythritol triallyl ether etc., the adipic acid ester of glycerol diallyl ether etc., polymkeric substance containing side chain type double bond, there is polymerizable functional group and the isocyanate compound etc. containing silicon group.
When adopting heat or the resin of photocuring, be preferred embodiment and by polymerizable monomer or polymerization starter, thermopolymerization promotor, light sensitizer, photopolymerization promoter etc.As polymerizable monomer, be not particularly limited, the styrenic monomers of such as vinylbenzene, 4-t-butyl styrene, alpha-methyl styrene, 4-chloro-styrene, 4-vinyl toluene, 4-1-chloro-4-methyl-benzene etc. can be enumerated particularly, (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) ethyl acrylate, (methyl) cyclohexyl acrylate, (methyl) isobornyl acrylate, (methyl) vinylformic acid-1-diamantane ester, (methyl) vinylformic acid tetrahydrofurfuryl alcohol ester, (methyl) vinylformic acid-2-hydroxyl ethyl ester, (methyl) vinylformic acid 2-hydroxypropyl acrylate, (methyl) glycidyl acrylate, (methyl) vinylformic acid trifluoro ethyl ester, (methyl) vinylformic acid of (methyl) perfluoroethyl octyl group ethyl ester etc. is derivative, the vinyl ether system monomer of hydroxy butyl vinyl ether, dodecyl vinyl etc., the allyl ether system monomer of the allyl ether of the allyl ethers of glycidyl allyl ether, melamine methylol, the adipic acid ester of glycerol diallyl ether, allyl group acetal, methylolacetone aldehyde ureine etc., the toxilic acid fat system monomer of ethyl maleate, dibutyl maleinate etc., the fumarate system monomer of dibutyl fumarate, dioctyl fumarate etc., 4-(methyl) acryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane, 4-(methyl) acryloyloxymethyl-2-methyl-2-isobutyl--1,3-dioxolane, 4-(methyl) acryloyloxymethyl-2-cyclohexyl-1,3-dioxolane, 4-(methyl) acryloyloxymethyl-2,2-dimethyl-1, the DOX system monomer of 3-dioxolane etc., (methyl) acryloyl morpholine, N-vinyl formamide, NVP etc.These polymerizable monomers, can be used alone, also can and use two or more.In these polymerizable monomers, be preferably (methyl) acrylic acid series ester cpds.
Among above-mentioned, be more preferably polyimide, polyurethanes, polyester, (methyl) acrylic resin based polymer, resol, amine resin, epoxy resin.They can be used alone, and also can mix two or more and use.
The concentration of metal oxide particle of the present invention in above-mentioned composition, suitably can set according to purposes, when said composition is uncured, usually relative to whole compositions (whole totals of the composition used in metal oxide particle, solvent, monomer, oligopolymer, polymkeric substance and polymer precursor described later etc.) the 100 quality % of this uncured composition, be below 90 quality %.During more than 90 quality %, becoming and be difficult to dispersed, likely there is gonorrhoea in uncured composition.On the other hand, lower value is not particularly limited, but considers solvent cost, such as, be more than 1 quality %.Be more preferably more than 5 quality % and be below 80 quality %, more preferably more than 10 quality % and be below 70 quality %.
In addition, in resin combination of the present invention, be not only above-mentioned macromolecular compound (polymkeric substance) and the composition of compound of the present invention or metal oxide particle, also comprise the monomer (polymer precursor) forming above-mentioned polymkeric substance, the unsaturated carboxylic acid of the mixture, acrylic or methacrylic acid etc. of such as dicarboxylic acid and diamines or its ester cpds etc., and the composition of compound of the present invention or metal oxide particle.In addition, resin combination of the present invention also can be both compositions comprising polymkeric substance and monomer.
In above-mentioned polymkeric substance, particularly preferably use the polymkeric substance that thermotolerance is good.By the polymkeric substance using thermotolerance good, the thermotolerance that can play metal oxide particle of the present invention fully improves effect.Particularly, preferred polyimide, (methyl) acrylic resin based polymer, resol, epoxy resin etc.
As the blended amount of the metal oxide particle of resin combination of the present invention, be preferably in the scope of 1 quality %-90 quality % in composition.When above-mentioned blended amount is less than 1 quality %, the specific refractory power likely step-down of the planar molding formed by resin combination or optical article.On the other hand, when above-mentioned blended amount is more than 90 quality %, the viscosity of composition uprises sometimes, and workability reduces.The higher limit of the blended amount of metal oxide particle, is more preferably 85 quality %, most preferably is 80 quality %.In addition, the lower value of described blended amount, is more preferably 10 quality %, more preferably 15 quality %, most preferably is 20 quality %.
Resin combination of the present invention, except above-mentioned solvent, monomer, oligopolymer, polymkeric substance, in order to improve dispersiveness further, can also add dispersing auxiliary.Dispersing auxiliary, as long as the material that metal oxide particle of the present invention can be made to disperse, is just not particularly limited, and representationally enumerates tensio-active agent etc.
As tensio-active agent, aniorfic surfactant, cationic surfactant, zwitterionics, nonionic surface active agent can be enumerated.As aniorfic surfactant, the sodium soap of sodium oleate, sodium stearate, sodium laurate etc. can be used; The fatty acid type tensio-active agent of lipid acid potassium, fatty acid ester sodium sulfonate etc.; The phosphatic type tensio-active agent of alkyl phosphate sodium etc.; The olefin type tensio-active agent of α oleic acid sodium sulfonate etc.; The alcohol type tensio-active agent of sodium alkyl sulfate etc.; Alkyl benzene surfactant etc.As cationic surfactant, kelene ylmethyl ammonium, chlorination alkyl Dimethyl Ammonium, alkyltrimethylammonium chloride, alkyldimethyl benzylammonium chloride etc. can be used.As zwitterionics, the carboxylic acid type tensio-active agent of alkyl amine group carboxylate salt etc. can be used; The phosphate surfactant etc. of phosphoric acid ester trimethyl-glycine etc.As nonionic surface active agent, the fatty acid type tensio-active agent of polyoxyethylene Wool wax alcohol fatty acid ester, polyoxyethylene sorbitol fatty acid ester etc. can be used; Polyoxyethylene alkyl phenyl ether; Fatty acid alkyl amide etc.
In addition, preferably, can enumerate by adding 2-acryloyl-oxyethyl succsinic acid, 2-acryloyl-oxyethyl hexahydrophthalic acid, 2-acryloyl-oxyethyl phthalic acid, 2-methacryloxyethyl succsinic acid, 2-methacryloxyethyl hexahydrophthalic acid, 2-methacryloxyethyl phthalic acid improve dispersiveness.
Resin combination of the present invention (comprising the solidification compound after solidification), also can added ingredients beyond fusion compound of the present invention or metal oxide particle (substituted type cover type particle) and resin.As this added ingredients, such as can enumerate solidifying agent, curing catalyst, tinting material, internal mold release, coupling agent, reactive diluent, fluidizer, stabilization agent, flame retardant, linking agent, low condensing agent, polymerization terminator, antioxidant, UV light absorber, defoamer, smooth agent, shake change agent, tackifier etc.
Resin combination of the present invention (comprising the solidification compound after solidification) is because metal oxide particle disperses equably, thus transparent high.Particularly, on the thickness of 100 μm, the transmittance of the light of wavelength 400nm can be more than 70%, is preferably more than 75%, is more preferably more than 80%.
Resin combination of the present invention (comprising the solidification compound after solidification), due to the metal oxide particle containing specified amount, thus specific refractory power is also higher.Particularly, the specific refractory power for the light of 589nm can be more than 1.5, is preferably more than 1.6.The upper limit of specific refractory power can be such as about 1.8.
The shape of resin combination of the present invention (comprising the solidification compound after solidification), is not particularly limited, such as, can be the molding of film, plate, thin slice, film, fiber etc.
Described for the resin combination (resin combination) of indicating meter with transparent planar molding, be particularly preferably configured as planar.Planar molding of the present invention refers to the top and bottom with face comprising film, plate, thin slice, film etc., and does not rely on thickness or thickness.In addition, also can be any shape of square, rectangle, circle, ellipse, trilateral, Polygons, abnormity or roll fashion, laminar manner etc.By being configured as planar, the lamination in indicating meter described later or touch control panel device is made to become easy.
The planar molding obtained by the present invention, owing to easily adjusting specific refractory power, thus can prevent from resulting from reflection and the scattering of the light of the refringence of the interlayer of the display unit with multilayered structure.Further, due to by fusion metal oxide particle of the present invention, can specific inductivity be improved, thus be suitable for insulating film.
Particularly in touch surface indicating meter, use the high-index material of IT0 film etc. to describe electrode pattern as nesa coating, there is clamping insulation layer and describe figuratum the first layer in X-direction and describe the three-decker of the figuratum second layer in the Y direction.Resin combination for transparent planar molding of the present invention, can prevent from seeing depicting pattern, improves identity, thus can be suitable for the layer contacted with electrode layer of insulation layer or protective membrane etc.Further, thin film transistor (TFT) the substrate planarization film of liquid crystal display device or organic EL display element etc., the interlayer dielectric of semiconductor element, the core of solid photographic element planarization film or microlens array pattern or optical waveguides or clad material is also suitable for.
Resin combination of the present invention, due to containing metal oxide particle, the thus specific refractory power of adjustable tree oil/fat composition.Further, the median size due to metal oxide particle is more than 1nm and is below 100nm, thus can maintain the transparency of resin combination.Because the surface of metal oxide particle of the present invention is by can the organic compound of coordination and/or bonding cover, the favorable dispersity thus in resin, and thermotolerance, ultraviolet resistance are also excellent.Therefore, metal oxide particle of the present invention, can not condense in the composition, can play its characteristic (high specific refractory power etc.), even and if be exposed in high temperature or UV-light also can not variable color, be suitable for the resin layer in indicating meter or resin thin film layer.In addition, the surface of metal oxide particle of the present invention is by can the organic compound of coordination and/or bonding cover, compared with unlapped particle, particle surface can be made to be hydrophobicity, when thus forming cured article, water-fast physical property, electrical characteristic (insulativity) can be made excellent.
6. preferable use
According to the metal oxide particle (cover type Zirconia particles) that the present invention obtains, be suitable for the optical material of optical lens, optical thin film tackiness agent, optical thin film caking agent, nano impression resin, microlens array, anti-reflection layer for transparency electrode, antireflective film or antireflection agent, the top coat of optical lens, the light-extraction layer of organic EL etc.
Especially, use the solidification compound of the metal oxide particle (replacing cover type particle) by the second invention preparation, due to the metal oxide particle (replace cover type particle) containing good dispersity, thus mobility is excellent and solidified nature is also excellent.Therefore, in nanometer embossing, the excellent transferability of mould.
Metal oxide particle of the present invention, because it is dispersed significantly, can launch in a variety of applications where.As the purposes requiring polymolecularity, resist purposes can be enumerated, optical applications, coating applications, adhesion purposes, be suitable for optical lens, optical thin film tackiness agent, optical thin film caking agent, nano impression resin combination, microlens array, be used in the anti-reflection layer of transparency electrode, antireflective film or antireflection agent, the top coat of optical lens, the light-extraction layer of organic EL, various hard coat material, TFT planarization film, colored filter sealer, the various protective membranes of antireflective film etc., and optical filter, touch sensing insulating film, TFT insulating film, colored filter light clapboard, the contact panel optical material protecting peritonaeum etc.Metal oxide particle of the present invention is except significant dispersiveness; owing to also having high refractive index, high rigidity, high stability, be thus particularly preferred for optical lens, the top coat of optical lens, various hard coat material, touch sensing insulating film, TFT insulating film, contact panel protective membrane.
Further, metal oxide particle of the present invention, except optical applications, effectively utilizes its high-k, can be suitable for the internal memory electricity container insulating film of the gate insulating film or DRAM etc. of semi-conductor.As the method for insulating film obtaining such high-k, there will be a known after using the chemical vapour deposition evaporation of Organometallic precursor by CVD (ChemicalVaporDeposition: chemical Vapor deposition process) method or ALD (AtomicLayerDeposition: atomic layer deposition method) method etc., carry out the method for oxide treatment.In order to the metal oxide obtaining desired high-k needs the pyroprocessing of more than 600 DEG C, but due to its impact, the phenomenon of the job insecurity of the semiconductor layer headed by anchoring phenomenon can be caused.Metal oxide particle of the present invention, without the need to pyroprocessing, during generation, there is higher specific inductivity, for the single particle of several nm, thus the lamination of the granular of the semi-conductor that may correspond to from now on is made to change into as possibility, meanwhile, due to without the need to pyroprocessing, the semi-conductor preparation on plastic base can be also used in.
Below, the resist purposes of representatively purposes is described in detail.Utilize the element of resist method, such as, can make as follows.
1) solidification compound (curable resin) of modulation containing metal oxide particle of the present invention.Modulation is containing metal oxide particle of the present invention typically, there is the polymkeric substance of acidic group or there is acidic group, the polymkeric substance of free-radical polymerised group or epoxy group(ing), there is the compound of free-radical polymerised double bond or there is the compound of epoxy group(ing), optical free radical produces agent or light acid producing agent, solvent as required, tinting material, fill material, dyestuff, pigment, defoamer, coupling agent, smooth agent, sensitizing agent, releasing agent, lubrication prescription, fluidizer, antioxidant, UV light absorber, fire retardant, polymerization retarder, tackifier, the anti-corrosion agent composition of the known additive of dispersion agent etc.Various composition, can select known combination of materials, known blended ratio.
2) prepare the substrate of above-mentioned solidification compound (curable resin composition) evaporation on the transparency carrier or transparency electrode of glass, transparent plastics etc. containing metal oxide particle of the present invention.As transparency electrode, representationally illustrate ITO, IZO, AZO, ZnO 2, tin metaantimmonic acid etc.When forming transparent electrode thin film on the glass substrate, undertaken by the method in the past such as the physical method of vacuum evaporation, sputter, ion plating, ionic fluid evaporation etc. or chemical Vapor deposition process.
On the substrate, by the known method such as method of spin coating, spraying method, by the solidification compound coating containing metal oxide particle of the present invention, dry, make film.As coating process, preferably use method of spin coating.As drying conditions, be the temperature of room temperature ~ 120 DEG C, being preferably the temperature of 60 DEG C-100 DEG C, is 10 seconds-60 minutes, is preferably 30 seconds to 10 minutes, preferably in the method for normal pressure or heating under vacuum drying.
3) then, the light shield (pattern formation film) of opening portion will be provided with according to desired pattern form, be positioned on above-mentioned film with contact condition or contactless state, and irradiate light, make it solidify.At this, so-called light, not only refers to visible light, also refers to the radioactive rays of ultraviolet, X-ray, electric wire etc., most preferably is ultraviolet.As ultraviolet source, usually suitably high pressure mercury vapour lamp can be used.
4), after rayed, develop with solvent, water, alkaline aqueous solution etc.In them, because the load of alkaline aqueous solution to environment is less and can carry out the development of high sensitivity, thus preferably.As alkaline components, be preferably potassium hydroxide, sodium hydroxide, sodium carbonate etc.Paper mill wastewater, is preferably 0.01-5 quality %, more preferably 0.05-3 quality %, most preferably is 0.1-1 quality %.When alkali concentration is lower than above-mentioned scope, the solvability of described curable resin is not enough sometimes, and on the contrary, time too high, solvency power is too high sometimes, and developability is deteriorated.Further, also tensio-active agent can be added in alkaline aqueous solution.
5) after alkaline development, preferably carry out heating (toasting afterwards) to be cured further, and when there being dissolvent residual, it is removed completely.As temperature during rear baking, be preferably 120-300 DEG C, more preferably 150-250 DEG C, most preferably be 180-230 DEG C.Rear storing temperature than above-mentioned high time, element is likely painted or damage the smoothness of film because of thermolysis, and on the contrary, time too low, the progress of solidification is less, and coating strength likely reduces.Rear baking, can carry out after the development in each component is formed, and also can carry out after all components of formation.Described element is preferred for display unit, as object lesson, can enumerate liquid crystal display device, but be not limited thereto, such as, and also can for using the display unit etc. of organic EL.In addition, the article of contact panel etc. are also suitable for.
Below, the situation for lens application is described in detail.Usual optical lens, specific refractory power more high-performance is higher, and metal oxide particle of the present invention has nano level dispersiveness, and comes from the specific refractory power of metal oxide, can improve the specific refractory power of cured article widely, is thus applicable to using.Such as can according to making as follows.
1) by the monomer of metal oxide particle of the present invention and resin or oligopolymer, with stirrer mixing, the resin combination with mobility is made.
2) by this resin combination, use metal die, glass mold, resin die etc. to be configured as the shape of regulation, the surface (surface of side) being produced on the base material formed by flat resin combination forms the molding of small convex lens portions.
3) this molding is heated, or the irradiation of ultraviolet or infrared rays etc. is imposed to molding, this molding is solidified, form optical lens.
The monomer of resin or oligopolymer, have when possessing reactive carbon double bond (C=C), even if only mix, can carry out being polymerized and resinifying.Particularly, as the method for the resin composition of the ultraviolet made containing acrylic resin etc. (UV) curable resin, have various method, representational have the moulding method, transfer moulding method etc. that use the Raolical polymerizable caused by heating or rayed.As this Raolical polymerizable, the polyreaction (thermopolymerization) utilizing heat, the polyreaction (photopolymerization) utilizing the light of ultraviolet etc. can be enumerated, utilize gamma-ray polyreaction, or by the method etc. of their multiple combinations.
As described above, optical lens according to the present embodiment, metal oxide particle of the present invention is used to be distributed to transparent complex in resin, the surface of the flat transparent substrate formed by this transparent complex defines small convex lens portions, thus can improve transmittance, specific refractory power, thermostability, hardness and weathering resistance.
Therefore, the optical lens that high transmission rate, high refractive index, high thermal stability, high rigidity and weathering resistance are excellent can be provided.This microlens array, owing to being the excellent lens arra of high transmission rate, high refractive index, high thermal stability, high rigidity and weathering resistance, is thus suitable for the OA machine etc. of the duplicating machine of requirement high resolving power and high reliability, printer etc.
Further, exemplified with in the method for tabular component by microlens excipient in above-mentioned, also can well for spherical lens, non-spherical lens, cylindrical lens etc.
Below, the situation for the coating applications that is representative with hard coat purposes is described in detail.Metal oxide particle of the present invention has nano level polymolecularity, and the hardness of metal oxide is high, excellent abrasion, is thus of value to the high rigidityization of base material and gives scuff resistance.Such as can according to making as follows.
1) coating composition, except metal oxide particle of the present invention, also can be as required, fusion polymerizable monomer, polymerization starter, thermopolymerization promotor, light sensitizer, photopolymerization promoter etc., further fusion organic solvent, polymkeric substance, various additive, and mix, stir to obtain.Coating composition, when not fusion polymerization starter, by irradiating electric wire, during fusion thermal polymerization, by heating, in addition, during fusion Photoepolymerizationinitiater initiater, by irradiation ultraviolet radiation, makes it solidify.
2) by described coating composition, the hand smeared etc. by brush is coated with or the known method such as spraying coating, pickling process is coated on base material.As glue spread, be preferably 0.2-100g/m 2scope in, be more preferably 0.5-70g/m 2scope in.In addition, as coating thickness, be preferably in the scope of 1-500 μm, be more preferably in the scope of 2-200 μm.As the base material for layered product, such as can enumerate polyethylene (PE), polypropylene (PP), polymethylmethacrylate (PMMA), polyacrylic ester, polyvinyl alcohol (PVA), polystyrene (PS), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), ethylene-vinyl acetate copolymer (EVA), acrylonitrile-butadiene-styrene copolymer (ABS), cellulosetri-acetate (TAC), cyclic olefin polymer (COP), polycarbonate (PC), polyetherketone (PEEK), polyamidoimide (PAI), polyimide (PI), polyetheramides (PEI), nylon (NY), polyvinyl chloride (PVC), the resin forming article of polyvinylidene chloride etc. and film, the stationery of the overlay paper of polyethylene coating paper, polyethylene terephthalate overlay paper etc., non-overlay paper etc., timber, glass, the metal species etc. of stainless steel, iron, aluminium, copper, alloy etc.
3) then, make the coating composition coating base material, by heating or UV radiation curing, make cured film.Such as, when utilizing the solidification of heating, use infrared rays, far infrared rays, hot blast, ratio-frequency heating etc.Heating temperature, suitably can regulate according to the kind of base material etc., be not particularly limited, be preferably 80-200 DEG C, be more preferably 90-180 DEG C, more preferably in the scope of 100-170 DEG C.Heat-up time, suitably can regulate according to surface covered etc., be not particularly limited, be preferably 1 minute ~ 24 hours, be more preferably 10 minutes ~ 12 hours, in the scope of more preferably 30 minutes ~ 6 hours.
Such as, when utilizing ultraviolet solidification, use the light source containing the light in the scope of wavelength 150-450nm.As such light source, such as, can enumerate solar ray, Cooper-Hewitt lamp, high pressure mercury vapour lamp, extra-high-pressure mercury vapour lamp, metal halide lamp, gallium lamp, xenon lamp, carbon arc lamp etc.Also can together with these light sources, and by the heat of infrared rays, far infrared rays, hot blast, ratio-frequency heating etc.Irradiate accumulated light, be preferably 0.1-10J/cm 2, be more preferably 0.15-8J/cm 2, more preferably 0.2-5J/cm 2scope in.
Such as, when the solidification utilizing electric wire, acceleration voltage can be used to be preferably 10-500kV, to be more preferably 20-300kV, the electric wire in the scope of more preferably 30-200kV.In addition, irradiation dose is preferably 2-500kGy, is more preferably 3-300kGy, and more preferably 4-200 is in the scope of kGy.Also can together with electric wire, and by the heat of infrared rays, far infrared rays, hot blast, ratio-frequency heating etc.
In addition, coating composition also can use shaping to band method simultaneously.The method, for by least by film with band banding that layer forms and put into injection molding metal die with film, after locked mode, by shaping resin injection to die cavity, the surface of the resin forming product after shaping resin solidification, make to band and use thin slice integrated and bonding, obtain being shaped and band molding simultaneously.
Hard coat material of the present invention, be suitable for contact panel, tank, the commode of the indicating meter, household appliances etc. of the communicating machine of OA machine, mobile phone etc., household electronic products, the interior exterior part of automobile, furniture exterior member, plastic lens, cosmetics containers, beverage-container, OLED display etc., and the purposes field of show window, window-glass etc.
In addition, the present invention is based on No. 2012-61186th, the Japanese patent application of Japanese patent application application on March 16th, No. 2011-275765 1 and the Japanese patent application 2012-85681 CLAIM OF PRIORITY interests of application on April 4th, 2012 of the Japanese patent application application on December 16th, No. 2011-270198 1 of application on December 9th, 2011.
The full content of No. 2012-61186th, the Japanese patent application of Japanese patent application application on March 16th, No. 2011-275765 1 of the Japanese patent application application on December 16th, No. 2011-270198 1 of application on December 9th, 2011 and the specification sheets of No. 2012-85681st, the Japanese patent application of application on April 4th, 2012, can introduce the application for reference.
Embodiment
Below, the present invention is further illustrated by enumerating embodiment.The present invention is not limited by the examples below, certainly can the scope being applicable to aforementioned and aim described later in addition suitable change implement, these include in technical scope of the present invention.
Physical property disclosed in embodiment and characteristic, measured by following method.
The physical property of 1.1 metal oxides (zirconium white, titanium oxide) particle
(1) parsing of crystalline texture
The crystalline texture of metal oxide particle, uses X-ray diffraction device (リ ガ Network society system, RINT-TTRIII) to resolve.Condition determination is as described below.
X-ray source: CuK α (0.154nm)
X-ray exports setting: 50kV, 300mA
Sampling width: 0.0200 °
Sweep velocity: 10.0000 °/min
Measurement range: 10-75 °
Measure temperature: 25 DEG C
(2) regular crystal, oblique crystal ratio quantitative
To use X-ray diffraction device (リ ガ Network society system, RINT-TTRIII) based on the value calculated, use software for calculation (リ ガ Network society system, PDXL) by referring to strength ratio method (RIP method) quantitatively (ownership of crest is also according to the appointment of software for calculation).
(3) the crystallization particle diameter utilizing X-ray diffraction to analyze calculates
Crystallization particle diameter is by using X-ray diffraction device (リ ガ Network society system, RINT-TTRIII) analytical Calculation goes out, using the crystallization particle diameter of the particle diameter of the crest of 2 θ=30 ° as Zirconia particles, using the crystallization particle diameter of the particle diameter of the crest of 2 θ=25 ° as Titanium particles.In addition, crystallization particle diameter, for using X-ray diffraction device (リ ガ Network society system, based on the halfwidth of the crest of 30 ° that RINT-TTRIII) calculate and the crest of 25 °, use software for calculation (リ ガ Network society system, PDXL), crystallization particle diameter (L) is calculated with the formula of following Scherrer (Scherrer).
L＝Kλ/βcosθ
K: constant
λ: the wavelength using X-ray tube
β: halfwidth
2 θ: angle of diffraction
(4) median size of electron microscope is utilized to measure
The average primary particle diameter of Zirconia particles, observes by utilizing ultrahigh resolution field emission scanning electronic microscope (Hitachi Ha イ テ Network ノ ロ ジ ー ズ system, S-4800) and measures.Observe Zirconia particles with multiplying power 150,000 times, to any 100 particles, measure the length of the long axis direction of each particle, using its mean value as average primary particle diameter.
(5) mensuration of weight (quality) rate of loss
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, measure weight (quality) rate of loss of this particle.By this weight (quality) rate of loss, the ratio of carbonate of known covering metal oxide particle and the ratio of metal oxide.
(6) particle thermal test
By metal oxide particle, under air atmosphere, place at 180 DEG C after 24 hours, with visual observation colour-change.What do not have variable color is qualified, and what have variable color is defective.
(7) mensuration of carbon content
By J-Science society JM10, carry out the mensuration of carbon content.
(8) 1the mensuration of H-NMR
Covering metal oxide particle is dispersed in as working sample in deuterochloroform, uses " UnityPlus " (resonant frequency: 400MHz, integral number of times: 16 times) of Variann society to measure.Based on the integration ratio of the crest of following chemical shift (tetramethylsilane benchmark), determine the mol ratio of each compound.
I) 2 ethyl hexanoic acid (1.0-0.5ppm:6H)
Ii) carboxylicesters (1.0-0.5ppm:6H) of 2 ethyl hexanoic acid is come from
Iii) 2-acryloyl-oxyethyl succsinic 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 dimethyls (1.0-0.5ppm:9H)
Vii) from the carboxylicesters (1.0-0.5ppm:9H) of 3,3-acid dimethyl
(9) mensuration of Zr, Si content
Use fluorescent x-ray analyzer (ZSXPrimusII リ ガ Network society system), measure Zr content, Si content in Zirconia particles.
(10) mensuration of the cl content in Zirconia particles
Cl content uses ion chromatograph (DIONEX society ICS-2000), resolves according to following condition determination.Zirconia particles and zirconium dimethyl butyric acid compound are all measured by combustion method.
Post: IonPacAS11HC
Elutriant: potassium hydroxide 23mmol/L
The characteristic of 1.2 polymkeric substance
(11) weight-average molecular weight
Use gel permeation chromatography determinator (" ShodexGPCSystem-21H " Showa electrician system), the weight-average molecular weight of polymkeric substance is scaled polystyrene and measures.
(12) polymer concentration in polymers soln
To add the solution of acetone 4g dissolving in polymers soln 1g, seasoning at normal temperatures, at 100 DEG C, drying under reduced pressure (160 DEG C/5mmHg), after 5 hours, cools in loft drier further, and quality measurement.Then, using the weight after drying under reduced pressure as polymer weight, by it divided by polymers soln 1g, as polymer concentration.
(13) acid value
In polymers soln 0.5-1g, add acetone 80ml and water 10ml and stir and make its uniform dissolution, using the KOH aqueous solution of 0.1mol/L as titrating solution, use automatic titration device (" COM-555 " flat natural pond industry system) to carry out titration, measure the acid value of solution.Then, suppose that acid is all from polymkeric substance, by acid value and the polymer concentration of solution, calculates the acid value of polymkeric substance.
The characteristic of 1.3 curable resin compositions
Transparency evaluation in (14) second methods
To not carry out the transmittance (optical wavelength: 400nm) of the thickness direction of the slide glass of any coating, and use extinction photometer (Shimadzu Seisakusho Ltd.'s spectrophotometer " UV-3100 ") to measure, its transmittance is decided to be T1%.Then, on slide glass, the excellent coating machine #10 of curable resin composition is coated with, heats after 5 minutes at 80 DEG C, with high-pressure mercury light irradiation 50mJ/cm 2ultraviolet make it solidify, obtain cured coating film.By the transmittance (optical wavelength: 400nm) being formed with the thickness direction of the slide glass of cured coating film made, use spectrophotometer " UV-3100 " to measure, its transmittance is decided to be T2%.Transmittance T is gone out by following formulae discovery by these values.
T(％)＝100+T2(％)-T1(％)
Transparency evaluation in (15) the 4th methods
On slide glass, the mode that composition coating machine described later makes thickness become 100 μm is coated with, under nitrogen atmosphere, by with high-pressure mercury light irradiation 1000mJ/cm 2ultraviolet make it solidify, obtain cured article.Use spectrophotometer (society of Shimadzu Seisakusho Ltd. spectrophotometer UV-3100), measure the transmittance at thickness direction during the light to the cured article illumination wavelength 400nm made.
(16) developability evaluation
By curable resin composition rotary coating on the glass substrate, drying 3 minutes at 100 DEG C, forms the film that thickness is 2.0 μm.By film, with UV exposure apparatus (Topcon society system, trade(brand)name: TME-150RNS), be the line of 30 μm and the light shield at interval via live width, use 50mJ/cm 2uV light exposure, use spin developer (ア Network テ ス society system, trade(brand)name: ADE-3000S), the potassium hydroxide aqueous solution with 0.05% carries out development 20 seconds, carries out the evaluation of developability.
(17) detecting refractive index test
On slide glass, the mode that curable resin composition coating machine makes thickness become 100 μm is coated with, under nitrogen atmosphere, with high-pressure mercury light irradiation 1000mJ/cm 2ultraviolet make it solidify, obtain cured article.Use index meter (ア タ go society system, DR-M2), at 20 DEG C, measure the specific refractory power of the light of gained cured article under wavelength 589nm.
(18) specific inductivity evaluation
On Copper Foil, the composition described later mode that excellent coating machine makes thickness become 50 μm is carried out coating, under nitrogen atmosphere, with high-pressure mercury light irradiation 1000mJ/cm 2ultraviolet make it solidify, obtain cured article.Further, at surperficial gold evaporation, be produced on sample for evaluation two sides being formed electrode.Use impedance analyzer (ヒ ュ ー レ ッ ト パ ッ カ ー De society system, trade(brand)name " 4294A ") measure the specific inductivity of this sample at 1MHz.
(19) pencil hardness
According to JISK54008.4.1 (trier method), carry out pencil scraping experiment, using pencil hardness when damaging on film as hardness.
(20) forming characteristic
The making of the pyramid array mould of (a) PDMS
On the Si wafer in 10mm four directions, using cutting mechanics to be processed into the degree of depth is 25 μm, spacing is 50 μm, drift angle is the V-type ditch of 90 °, by the direction half-twist by substrate, carry out same mechanical workout, the master mold of the pyramid array mould that the Pyramid (quadrangular pyramid) making the length of side to be 50 μm of height be 25 μm arranges regularly.
On the surface of described master mold, use spin coater by releasing agent (Off ロ ロ テ Network ノ ロ ジ ー society system, " Off ロ ロ サ ー Off " (registered trademark) FG5020 ") after coating masking (application conditions: slope5sec → 1500rpm30sec), on the hot-plate of 80 DEG C dry 5 minutes.
Using the mould of above-mentioned obtained demoulding process as master mold, make the mould that polydimethylsiloxane (PDMS) is made.Particularly, for by polydimethylsiloxane (シ リ コ ー Application society of SHIN-ETSU HANTOTAI system, " KE-1310ST ") mix with 10:1 (mass ratio) with catalyzer (シ リ コ ー Application society of SHIN-ETSU HANTOTAI system, " CAT-1310S "), and carry out deaeration.By this mixture, pour on described master mold, the support substrate (quartz plate) of casting is set from above.Directly after room temperature places 24 hours, keep 3 hours at 80 DEG C at baking oven.Then, by the master mold demoulding, make the pyramid array mould (mould that recessed quadrangular pyramid is regularly arranged) of PDMS.Further, the mould of the PDMS formed by " KE-1310ST " and " CAT-1310S ", second-order transition temperature is-140 ~-120 DEG C, is 6.0MPa at the moduluss of elasticity of 23 DEG C.
B () is shaped
On Si wafer, drip curable resin composition, the pyramid array mould of PDMS is set, uses simple and easy imprinting apparatus, extrude with loading 0.1MPa.With the state of extrusion mould, use high-pressure mercury light irradiation 1000mJ/cm 2ultraviolet, make resin composition, then UV pyramid array mould peeled off.By the structure containing the zirconium oxide nano-particle of figuration on Si wafer, with sweep electron microscope (SEM) shooting, evaluate shape.
Embodiment 1
By alkaline carbonic acid zirconium 100g (Zr 2(CO 3) (OH) 2o 2, be ZrO 2the wet feed product of content 43%, the zirconium of water content relative to 1 mole is 7 moles, Japanese light metal society system), 2, the mixed solution of 2-acid dimethyl 83g (Tokyo changes into industrial society system), dimethylbenzene 50g and deionized water 59g, under open system, be warming up to 80 DEG C, stir 1 hour.Take out reacted organic layer 5g, add in acetone 50g, separate out white precipitate.The white precipitate of separating out is filtered and takes out, at room temperature carry out drying 12 hours under vacuo, obtain ZrO (OH) (CO 3) 1/2 (1-n)(OCOC 5h 11) n.The rate of weight loss measured according to " mensuration of (5) rate of weight loss " of gained compound is 53%, ZrO contained in the compound of therefore gained 2part by weight be 47%, it can thus be appreciated that the part by weight of Zr atom is 35%.In addition, the carbon content that the result measured according to " mensuration of (7) carbon content " is obtained compound is 30%, known C 5h 11cOO unit containing proportional be 48%.By the known Zr atom of this result and C 5h 11the mol ratio of COO unit is 1/1, n=1 in above-mentioned formula.
Embodiment 2
Under agitation, in the pure water 210.6g of 40 DEG C, add sodium hydroxide 30g (キ シ ダ chemistry society system, superfine), obtain aqueous sodium hydroxide solution.Then, under agitation, in described aqueous sodium hydroxide solution, 2,2-acid dimethyl 100.0g (Tokyo changes into industrial society system) is added, modulation 2,2-dimethyl butyrate acid sodium aqueous solution.
Then, in described 2,2-dimethyl butyrate acid sodium aqueous solutions, add dimethylbenzene 432.8g (northern Hong Kongnization society system), be heated to 80 DEG C, under agitation, by zirconium oxychloride 221.8g (ZrOCl 28H 2o, the first rare element chemistry industry society system, ZircosolZC-20) spend 20 minutes inputs.Then, Keep agitation 1 hour at 80 DEG C, after removing aqueous phase, by fully being washed by organic layer, obtains 2,2-acid dimethyl zirconium xylene solution 490g.Then, by 2,2-acid dimethyl zirconium xylene solution, be concentrated into 120g with concentrating under reduced pressure machine, add methyl alcohol 360g (northern Hong Kongnization society system) wherein, and by 2 of the white of precipitation, 2-acid dimethyl zirconium filters and takes out, at room temperature under vacuo dry 12 hours.The rate of weight loss of dried 2, the 2-acid dimethyl zirconiums measured according to " mensuration of (5) rate of weight loss " is 65%, and the output of dried 2,2-acid dimethyl zirconiums is 100g.
The rate of weight loss that above-mentioned 2,2-acid dimethyl zirconiums measure according to " mensuration of (5) rate of weight loss " is 65%, therefore contained in gained compound ZrO 2part by weight be 35%, it can thus be appreciated that the part by weight of Zr atom is 26%.In addition, the carbon content that the result measured according to " mensuration of (7) carbon content " is obtained compound is 41%, it can thus be appreciated that C 5h 11cOO unit containing proportional be 66%.By this results verification Zr atom and C 5h 11the mol ratio of COO unit is 1/2, and its structure is ZrO (OCOC 5h 11) 2.
Embodiment 3
By alkaline carbonic acid zirconium 100g (composition formula: Zr 2(CO 3) (OH) 2o 2, ZrO 2the wet feed product of content 43%, Japanese light metal society system), 2, the mixed solution of 2-acid dimethyl 83g (zirconium relative to 1 mole is 2 moles), dimethylbenzene 50g and deionized water 59g (zirconium relative to 1 mole is 9 moles) adds high-pressure reactor, by the atmosphere nitrogen replacement in this high-pressure reactor.Then, mixed solution is heated to 190 DEG C, keeps 22 hours (pressure in high-pressure reactor is 2.5MPa).Take out reacted solution, the throw out being deposited on bottom is filtered, cleans with 200g toluene.Dry by thing will be cleaned, obtain the cover type Zirconia particles 40g of white.
Embodiment 4
Beyond using 2,2-acid dimethyl 63g (zirconium relative to 1 mole is 1.5 moles), obtain the cover type Zirconia particles 29g of white similarly to Example 3.
Embodiment 5
By alkaline carbonic acid zirconium 100g (Zr 2(CO 3) (OH) 2o 2, ZrO 2the wet feed product of content 43%, Japanese light metal society system), the mixed solution of 2,2-acid dimethyl 83g, 1，2，4-trimethylbenzene 50g and deionized water 59g adds high-pressure reactor, by the atmosphere nitrogen replacement of this high-pressure reactor.Then, mixed solution is heated to 190 DEG C, keeps 22 hours (pressure in high-pressure reactor is 2.5MPa).Take out reacted solution, the throw out being deposited on bottom is filtered, cleans with 200g toluene.Dry by thing will be cleaned, obtain the cover type Zirconia particles 37g of white.
Embodiment 6
Beyond using 2,2-acid dimethyl 63g, obtain the cover type Zirconia particles 36g of white similarly to Example 5.
Embodiment 7
By alkaline carbonic acid zirconium 100g (Zr 2(CO 3) (OH) 2o 2, ZrO 2the wet feed product of content 43%, Japanese light metal society system), 2,2-acid dimethyl 63g, 1,2, the mixed solution of 4-Three methyl Benzene 50g and deionized water 59g, NaOH3g (zirconium relative to 1 mole is 0.2 mole) adds high-pressure reactor, by the atmosphere nitrogen replacement of this high-pressure reactor.Then, mixed solution is heated to 190 DEG C, keeps 22 hours (pressure in high-pressure reactor is 2.6MPa).Take out reacted solution, the throw out being deposited on bottom is filtered, cleans with 200g toluene.Dry by thing will be cleaned, obtain the cover type Zirconia particles 46g of white.
Embodiment 8
Beyond using 2,2-acid dimethyl 42g (zirconium relative to 1 mole is 1 mole), obtain the cover type Zirconia particles 44g of white similarly to Example 7.
Embodiment 9
By alkaline carbonic acid zirconium 100g (Zr 2(CO 3) (OH) 2o 2, ZrO 2the wet feed product of content 43%, Japanese light metal society system), the mixed solution of 2,2-acid dimethyl 42g, 1，2，4-trimethylbenzene 100g and NaOH3g adds high-pressure reactor, by the atmosphere nitrogen replacement of this high-pressure reactor.Then, mixed solution is heated to 190 DEG C, keeps 22 hours (pressure in high-pressure reactor is 2.4MPa).Take out reacted solution, the throw out being deposited on bottom is filtered, cleans with 200g toluene.Dry by thing will be cleaned, obtain the cover type Zirconia particles 35g of white.
Embodiment 10
Except using 2,2-acid dimethyl 21g (zirconium relative to 1 mole is 0.5 mole), making the pressure in high-pressure reactor be beyond 2.6MPa, obtaining the cover type Zirconia particles 26g of white similarly to Example 9.
Embodiment 11
Except using 1，2，4-trimethylbenzene 50g, making the pressure in high-pressure reactor be beyond 2.6MPa, obtaining the cover type Zirconia particles 43g of white similarly to Example 9.
Embodiment 12
By alkaline carbonic acid zirconium 100g (Zr 2(CO 3) (OH) 2o 2, ZrO 2the wet feed product of content 43%, Japanese light metal society system), the mixed solution of 2,2-acid dimethyl 63g, deionized water 59g and NaOH3g adds high-pressure reactor, by the atmosphere nitrogen replacement of this high-pressure reactor.Then, mixed solution is heated to 190 DEG C, keeps 22 hours (pressure in high-pressure reactor is 2.6MPa).Take out reacted solution, the throw out being deposited on bottom is filtered, cleans with 200g toluene.Dry by thing will be cleaned, obtain the cover type Zirconia particles 47g of white.
Embodiment 13
By alkaline carbonic acid zirconium 100g (Zr 2(CO 3) (OH) 2o 2, ZrO 2the wet feed product of content 43%, Japanese light metal society system), 2,2-acid dimethyl 83g, 1,2, the mixed solution of 4-Three methyl Benzene 50g, deionized water 59g and NaOH9g (zirconium relative to 1 mole is 0.6 mole) adds high-pressure reactor, by the atmosphere nitrogen replacement of this high-pressure reactor.Then, mixed solution is heated to 170 DEG C, keeps 22 hours (pressure in high-pressure reactor is 2.1MPa).Take out reacted solution, the throw out being deposited on bottom is filtered, cleans with 200g toluene.Dry by thing will be cleaned, obtain the cover type Zirconia particles 41g of white.
Embodiment 14
By alkaline carbonic acid zirconium 100g (Zr 2(CO 3) (OH) 2o 2, ZrO 2the wet feed product of content 43%, Japanese light metal society system), the mixed solution of 2,2-acid dimethyl 83g, 1，2，4-trimethylbenzene 50g and deionized water 59g, under open system, be warming up to 80 DEG C, stir 1 hour.Then, add NaOH9g, and join in high-pressure reactor, by the atmosphere nitrogen replacement of this high-pressure reactor.Then, mixed solution is heated to 170 DEG C, keeps 22 hours (pressure in high-pressure reactor is 0.8MPa).Take out reacted solution, the throw out being deposited on bottom is filtered, cleans with 200g toluene.Dry by thing will be cleaned, obtain the cover type Zirconia particles 38g of white.
Embodiment 15
By alkaline carbonic acid zirconium 100g (Zr 2(CO 3) (OH) 2o 2, ZrO 2the wet feed product of content 43%, Japanese light metal society system), the mixed solution of 2,2-acid dimethyl 83g, dimethylbenzene 50g and deionized water 59g, under open system, be warming up to 80 DEG C, stir 1 hour.Then, mixed solution is added high-pressure reactor, by the atmosphere nitrogen replacement of this high-pressure reactor.Then, mixed solution is heated to 190 DEG C, keeps 22 hours (pressure in high-pressure reactor is 1.4MPa).Take out reacted solution, the throw out being deposited on bottom is filtered, cleans with 200g toluene.Dry by thing will be cleaned, obtain the cover type Zirconia particles 41g of white.
For the Zirconia particles that embodiment 3-15 obtains, by the method for above-mentioned (1)-(6), carry out the confirmation of the ratio of regular crystal, rate of weight loss, median size, thermotolerance.The results are shown in table 1, table 2.
[table 1]
In ※ table, in (), represent the mole number relative to zirconium 1 mole.
[table 2]
In ※ table, in (), represent the mole number relative to zirconium 1 mole.
Embodiment 16
In 2, the 2-acid dimethyl zirconium 270g that embodiment 2 obtains, xylol 338g and pure water 288g obtains mixed solution.Being joined by this mixed solution has in the high-pressure reactor of stirrer, by the atmosphere nitrogen replacement of this high-pressure reactor.Then, mixed solution is heated to 190 DEG C, after keeping 16 hours (pressure in high-pressure reactor is 1.4MPa) to make it react, takes out from high-pressure reactor, the throw out being deposited on bottom is filtered, cleans with 210g toluene.Dry by thing will be cleaned, obtain the cover type Zirconia particles 103g of white.
Confirm the crystalline texture of obtained Zirconia particles, detect and belong to regular crystal and monoclinic diffracted ray, known by the intensity of diffracted ray, regular crystal and monoclinic ratio are 27/73, and its particle diameter (crystallization particle diameter) is 8nm.
The median size (average primary particle diameter) of the Zirconia particles obtained by determination of electron microscopy is 11nm.In addition, by obtained Zirconia particles, with infrared absorption spectrum analysis, results verification is to coming from the absorption of C-H and coming from the absorption of COOH.This absorption, can think to result from cover 2,2-acid dimethyls of Zirconia particles and/or come from the carboxylicesters of 2,2-acid dimethyl.
Further, the rate of weight loss of the Zirconia particles measured according to above-mentioned " mensuration of (5) rate of weight loss " is 12 quality %.Therefore known capping oxidation zirconium particle 2,2-acid dimethyls and come from the total amount of carboxylicesters of 2,2-acid dimethyl, be 12 quality % of cover type Zirconia particles entirety.
In addition, the result of thermal test, Zirconia particles maintenance white is also unchanged.
Embodiment 17 uses the example of 3,3-acid dimethyl
Under agitation, in the pure water 421g of 40 DEG C, add sodium hydroxide 60g (キ シ ダ chemistry society system, superfine), obtain aqueous sodium hydroxide solution.Then, under agitation, in described aqueous sodium hydroxide solution, 3,3-acid dimethyl 200.0g (Tokyo changes into industrial society system) is added, modulation 3,3-dimethyl butyrate acid sodium aqueous solution.
Then, in described 3,3-dimethyl butyrate acid sodium aqueous solutions, add ethylcyclohexane 649g (Wan Shan petroleum chemistry society system), be heated to 80 DEG C, under agitation, by zirconium oxychloride 444g (ZrOCl 28H 2o, the first rare element chemistry industry society system, ZircosolZC-20) spend 20 minutes inputs.Then, Keep agitation 1 hour at 80 DEG C, after removing aqueous phase, fully clean organic layer with water, obtain 3,3-acid dimethyl zirconium ethylcyclohexane solution 830g, then, 3,3-acid dimethyl zirconium ethylcyclohexane solution concentrating under reduced pressure machine is concentrated into 270g, adds 3 of methyl alcohol 810g (northern Hong Kongnization society system) precipitation white wherein, 3-acid dimethyl zirconium, filter 3, the 3-acid dimethyl zirconiums taking out white, at room temperature under vacuo dry 12 hours.The rate of weight loss of dried 3, the 3-acid dimethyl zirconiums measured according to " mensuration of (5) rate of weight loss " is 63%, and the output of dried 3,3-acid dimethyl zirconiums is 190g.
In 3, the 3-acid dimethyl zirconium 270g obtained like this, mixing 1，2，4-trimethylbenzene 338g (ア Le De リ ッ チ society system), sodium hydroxide 37g (キ シ ダ chemistry society system, superfine) and pure water 288g obtain mixed solution.Being joined by this mixed solution has in the high-pressure reactor of stirrer, by the atmosphere nitrogen replacement of this high-pressure reactor.Then, mixed solution is heated to 190 DEG C, after keeping 16 hours (pressure in high-pressure reactor is 1.4MPa) to make it react at such a temperature, is taken out by high-pressure reactor, the throw out being deposited on bottom is filtered, cleans with 210g toluene.Dry by thing will be cleaned, obtain the cover type Zirconia particles 51g of white.
Confirm the crystalline texture of obtained Zirconia particles, detect and belong to regular crystal and monoclinic diffracted ray, known by the intensity of diffracted ray, regular crystal and monoclinic ratio are 5/95, and its particle diameter (crystallization particle diameter) is 8nm.
The median size (average primary particle diameter) of the Zirconia particles obtained by determination of electron microscopy is 11nm.In addition, by obtained Zirconia particles, with infrared absorption spectrum analysis, results verification is to coming from the absorption of C-H and coming from the absorption of COOH.This absorption, can think to result to cover 3,3-acid dimethyls of Zirconia particles and/or the carboxylicesters from 3,3-acid dimethyl.
Further, the rate of weight loss of the Zirconia particles measured according to above-mentioned " mensuration of (5) rate of weight loss " is 12 quality %.Therefore known capping oxidation zirconium particle 3,3-acid dimethyls and come from the total amount of carboxylicesters of 3,3-acid dimethyl, be 12 quality % of cover type Zirconia particles entirety.
In addition, the result of thermal test, Zirconia particles maintenance white is also unchanged.
Embodiment 18
Under agitation, in the pure water 11.5g of 40 DEG C, add sodium hydroxide 2.6g (キ シ ダ chemistry society system, superfine), obtain aqueous sodium hydroxide solution.Then, under agitation, in described aqueous sodium hydroxide solution, add PIVALIC ACID CRUDE (25) 7.5g (Tokyo changes into industrial society system), modulation PIVALIC ACID CRUDE (25) sodium water solution, is heated to 80 DEG C.
Then, under agitation, in described PIVALIC ACID CRUDE (25) sodium water solution, by zirconium oxychloride 18.9g (ZrOCl 28H 2o, the first rare element chemistry industry society system, ZircosolZC-20) spend 20 minutes inputs, separate out the PIVALIC ACID CRUDE (25) zirconium of white.This PIVALIC ACID CRUDE (25) zirconium is filtered and takes out, after methanol cleaning, at room temperature under vacuo dry 12 hours.The rate of weight loss of the dried PIVALIC ACID CRUDE (25) zirconium measured according to " mensuration of (5) rate of weight loss " is 60%, and the output of dried PIVALIC ACID CRUDE (25) zirconium is 8.5g.
In gained PIVALIC ACID CRUDE (25) zirconium 1.06g, xylol 1.22g, pure water 1.13g and sodium hydroxide 0.13g (キ シ ダ chemistry society system, superfine) obtain mixed solution.By this mixed solution, join and have in the high-pressure reactor of stirrer, by the atmosphere nitrogen replacement of this high-pressure reactor.Then, mixed solution is heated to 190 DEG C, after keeping 16 hours (pressure in high-pressure reactor is 1.4MPa) to make it react at such a temperature, is taken out by high-pressure reactor, the throw out being deposited on bottom is filtered, cleans with 10g toluene.Dry by thing will be cleaned, obtain the cover type Zirconia particles 0.17g of white.
Confirm the crystalline texture of obtained Zirconia particles, detect and belong to regular crystal and monoclinic diffracted ray, from the intensity of diffracted ray, regular crystal and monoclinic ratio are 69/31, and its particle diameter (crystallization particle diameter) is 4nm.
In addition, by obtained Zirconia particles, with infrared absorption spectrum analysis, the absorption coming from C-H and the absorption coming from COOH is confirmed.This absorption, the PIVALIC ACID CRUDE (25) can thinking to result to cover Zirconia particles and/or the carboxylicesters from PIVALIC ACID CRUDE (25).
Further, the rate of weight loss of the Zirconia particles measured according to " mensuration of (5) rate of weight loss " is 17 quality %.Therefore, the PIVALIC ACID CRUDE (25) of capping oxidation zirconium particle and come from the total amount of carboxylicesters of PIVALIC ACID CRUDE (25) is 17 quality % of cover type Zirconia particles entirety.
In addition, the result of thermal test, Zirconia particles maintenance white is also unchanged.
Embodiment 19
Mixed by the Zirconia particles 1.0g, stearic acid 1.0g and the toluene 18.0g that embodiment 17 are obtained, at 50 DEG C, heating obtains the transparent dispersion liquid of Zirconia particles.
Embodiment 20
Mixed by Zirconia particles 1g, acetic acid 4.5g that embodiment 15 is obtained, deionized water 4.5g, obtain Zirconium oxide dispersion liquid.By in this dispersion liquid, mixing PLACCELFM-10.5g (the methacrylic acid monomer containing hydroxyl, ダ イ セ Le chemistry society system) and DAROCUR1173 (free radical type Photoepolymerizationinitiater initiater, BASF society system) obtain zirconia dispersion.This dispersion dropper is dripped 0.1g on a glass, heats 30 minutes at 150 DEG C.Then, with high-pressure mercury light irradiation 8J/cm 2ultraviolet make it solidify, obtain transparent coating.With finger touch gained film, do not have fingerprint, confirm abundant solidification.
Embodiment 3-13, for by zirconium carbonate, carboxylic acid and other compound, and carries out the example of hydrothermal treatment consists.Embodiment 14 and 15, for by zirconium carbonate and carboxylic acid, reacting, for embodiment 14, carrying out the example of hydrothermal treatment consists for adding thereafter NaOH under the existence of the compound of other except NaOH.Arbitrary situation of embodiment 3-15, the Zirconia particles that all can be covered by carbonate.
Embodiment 3 and 4,5 and 6,7 and 8,9 and 10 is compared respectively, known by making the quantitative change of carboxylic acid few, the ratio of regular crystal can be improved.
Embodiment 7 and 12 is compared, known by using aromatic hydrocarbon series solvent, the ratio of regular crystal can be improved.
Embodiment 9 and 11 compared, the quantitative change of known aromatic hydrocarbon series solvent is many, and the ratio of regular crystal can be made to become large.
Embodiment 6 and 7 is compared, the known ratio by using NaOH can improve regular crystal.
Embodiment 8 and 11 is compared, the known amount by adjustment water, the ratio of adjustable regular crystal.
Embodiment 3 and 15,13 and 14 is compared respectively, known first make zirconium carbonate and carboxylic acid reaction after carry out hydrothermal treatment consists again, and carry out described reaction simultaneously and compare with the situation of hydrothermal treatment consists, reaction pressure during hydrothermal treatment consists can be made lower.
In embodiment 18, for using zirconium oxychloride as oxygenate metallic compound, using PIVALIC ACID CRUDE (25) sodium as carboxylic acid cpd, they being carried out the example of hydrothermal treatment consists, also can be obtained the Zirconia particles covered by carbonate by such method.
Preparation example 2-1
By 2 ethyl hexanoic acid and/or zirconium oxide nano-particle (the cover type ZrO that covers from the carboxylicesters of 2 ethyl hexanoic acid 2particle) preparation
Mixing pure water (268g) in 2 ethyl hexanoic acid zirconium mineral spirits solution (782g, 2 ethyl hexanoic acid zirconium content 44 quality %, the first rare element chemistry industry society system) (pKa=4.82 of 2 ethyl hexanoic acid).Being joined by gained mixed solution has in the high-pressure reactor of stirrer, by the atmosphere nitrogen replacement of this high-pressure reactor.Then mixed solution is heated to 180 DEG C, keeps 16 hours (pressure in high-pressure reactor is 0.94MPa) to make it react at such a temperature, generate Zirconia particles.Then, take out reacted mixed solution, the throw out being deposited on bottom is filtered, dry after cleaning with acetone.Dried described throw out (100g) is distributed in toluene (800mL), forms gonorrhoea solution.Then, as refining step, again filter, the oversize particle etc. in disgorging with quantitative paper (society of ア De バ ンテック Japan system, No.5C).Further, filtrate reduced in volume is removed toluene, reclaim Zirconia particles (the cover type ZrO of white 2particle).
To obtained cover type ZrO 2the crystalline texture of particle confirms, detects and belongs to regular crystal and monoclinic diffracted ray, and from the intensity of diffracted ray, regular crystal and monoclinic ratio are 54/46, and its particle diameter (crystallization particle diameter) is 5nm.
The cover type ZrO obtained by determination of electron microscopy 2the median size (average primary particle diameter) of particle is 12nm.In addition, by obtained cover type ZrO 2particle, with infrared absorption spectrum analysis, confirms the absorption coming from C-H and the absorption coming from COOH.This absorption, can think to result from the 2 ethyl hexanoic acid covering Zirconia particles and/or the carboxylicesters coming from 2 ethyl hexanoic acid.
Further, according to the cover type ZrO that above-mentioned " mensuration of (5) mass loss rate " measures 2the mass loss rate of particle is 12 quality %.Therefore known capping oxidation zirconium particle 2 ethyl hexanoic acid and/or come from the carboxylicesters of 2 ethyl hexanoic acid, be 12 quality % of Zirconia particles entirety.
Embodiment 2-1
(cover type ZrO is replaced by 2 ethyl hexanoic acid and/or from the zirconium oxide nano-particle that carboxylicesters and the 2-acryloyl-oxyethyl succsinic acid of 2 ethyl hexanoic acid cover 2particle 1) preparation
The cover type ZrO that preparation example 2-1 is obtained 2particle (10g), 2-acryloyl-oxyethyl succsinic acid (2g) (pKa=4.35) are uniformly mixed to dispersed in propylene glycol monomethyl ether acetate (12g, hereinafter referred to as " PGMEA ").Then, solution is made to occur gonorrhoea, with filter paper from gonorrhoea solution separating aggregated particle by adding normal hexane (36g) to make dispersed particle condense.Then, the aggregated particle of separation is added in normal hexane (36g), stir after 10 minutes, aggregated particle filter paper is separated, by obtained particle is at room temperature dry under vacuo, modulate and (replace cover type ZrO by 2 ethyl hexanoic acid and/or from the carboxylicesters of 2 ethyl hexanoic acid and 2-acryloyl-oxyethyl succsinic acid surface-treated Zirconia particles 2particle 1).
By obtained replacement cover type ZrO 2particle 1, is distributed to deuterochloroform as working sample, carries out 1the analysis of H-NMR.As a result, known 2 ethyl hexanoic acid and/or be 10:90 from the carboxylicesters of 2 ethyl hexanoic acid and the molar ratio that exists of 2-acryloyl-oxyethyl succsinic acid.
Further, according to the replacement cover type ZrO that above-mentioned " mensuration of (5) mass loss rate " measures 2the mass loss rate of particle 1 is 20 quality %.Therefore known capping oxidation zirconium particle 2 ethyl hexanoic acid and/or from the carboxylicesters of 2 ethyl hexanoic acid and acrylyl oxy-ethyl succsinic acid, be 20 quality % of Zirconia particles entirety.
Embodiment 2-2
(cover type ZrO is replaced by 2 ethyl hexanoic acid and/or from the zirconium oxide nano-particle that carboxylicesters and the 2-acryloyl-oxyethyl succsinic acid of 2 ethyl hexanoic acid cover 2particle 2) preparation
The cover type ZrO that preparation example 2-1 is obtained 2particle (10g), 2-acryloyl-oxyethyl succsinic acid (1g) are uniformly mixed to dispersed in PGMEA (12g).Then, solution is made to occur gonorrhoea, with filter paper from gonorrhoea solution separating aggregated particle by adding normal hexane (36g) to make dispersed particle condense.Then, the aggregated particle of separation is added in normal hexane (36g), stir after 10 minutes, aggregated particle filter paper is separated, by obtained particle is at room temperature dry under vacuo, modulate and (replace cover type ZrO by 2 ethyl hexanoic acid and/or from the carboxylicesters of 2 ethyl hexanoic acid and 2-acryloyl-oxyethyl succsinic acid surface-treated Zirconia particles 2particle 2).
Gained is replaced cover type ZrO 2particle 2, is dispersed in as working sample in deuterochloroform, carries out 1the analysis of H-NMR.As a result, known 2 ethyl hexanoic acid and/or be 30:70 from the carboxylicesters of 2 ethyl hexanoic acid and the molar ratio that exists of 2-acryloyl-oxyethyl succsinic acid.
Further, according to the replacement cover type ZrO that above-mentioned " mensuration of (5) mass loss rate " measures 2the mass loss rate of particle 2 is 20 quality %.Therefore known capping oxidation zirconium particle 2 ethyl hexanoic acid and/or from the carboxylicesters of 2 ethyl hexanoic acid and acrylyl oxy-ethyl succsinic acid, be 20 quality % of Zirconia particles entirety.
Synthesis example 2-1
Prepare with the detachable flask of prolong as reactive tank, in addition, make adequate preparation in monomer dropping groove and be uniformly mixed dimethyl-2,2 '-[oxygen two (methylene radical)] two-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, hereinafter referred to as " CHMA "), tert-butyl peroxide-2-ethylhexanoate (4g, " PERBUTYLO " of Japanese grease society; Hereinafter referred to as " PBO "), the mixture of PGMEA (75g), the mixture of mix and blend β-mercaptopropionic acid of making adequate preparation in chain-transfer agent dropwise adding tank (6g, hereinafter referred to as " β-MPA "), PGMEA (5g).
In reactive tank, add PGMEA (234g), after nitrogen replacement, limit stirring oil bath is heated, and reactive tank is warming up to 90 DEG C.After the temperature of reactive tank is stable at 90 DEG C, by monomer dropping groove and chain-transfer agent dropwise adding tank, drip content respectively.Dropping limit, limit keeps the temperature of 90 DEG C, and cost is carried out for 135 minutes respectively.After dripping 60 minutes that terminate start reactive tank to be warming up to 110 DEG C.At maintaining 110 DEG C after 3 hours, load onto gas introduction tube at detachable flask, start with oxygen/nitrogen=5/95 (v/v) mixed gas bubbling.Then, in reactive tank, add glycidyl methacrylate (50g, hereinafter referred to as " GMA "), 2,2 '-methylene-bis (4-methyl-6-tert butyl phenol) (0.4g, hereinafter referred to as " MBMTB ") triethylamine (0.8g, hereinafter referred to as " TEA "), directly reacts 12 hours at 110 DEG C.Then add PGMEA (75g) and be cooled to room temperature, obtaining the polymers soln that concentration is 40 quality %.The weight-average molecular weight of polymkeric substance is 9000, and the acid value of polymers soln is 72mgKOH/g.
Embodiment 2-3
The replacement cover type ZrO that embodiment 2-1 is obtained 2the polymers soln (resin solution, 5.0g) that particle 1 (5.0g) and synthesis example 1 obtain, dipentaerythritol acrylate (3.0g), PGMEA (18.7g) mix.In obtained dispersion liquid, mixing IRGACURE (registered trademark) 907 (0.2g, チ バ ジ ャ パ Application society system), as Photoepolymerizationinitiater initiater, obtains curable resin composition 1.
The transmittance measuring the cured coating film of curable resin composition 1 according to above-mentioned " (14) transparency is evaluated " is 99%.In addition, implement the evaluation of the developability of curable resin composition 1 according to " (15) developability evaluation ", do not confirm the residue in unexposed portion as shown in Figure 1, developability is good.
Embodiment 2-4
The replacement cover type ZrO that embodiment 2-1 obtains is added in dark brown vial 2particle 1 (6.0g), FA-BZA (1.5g, benzyl acrylate, Hitachi changes into industrial society system), LIGHTACRYLATETMP-A (0.5g, Viscoat 295, common prosperity society chemistry society system), DAROCUR1173 (0.4g, optical free radical polymerization starter, チ バ ジ ャ パ Application society system), carry out being stirred to evenly, obtain curable resin composition 2.The curable resin composition 2 obtained, has mobility at 25 DEG C.Use the curable resin composition 2 obtained, measure according to above-mentioned " test of (17) detecting refractive index ", the specific refractory power of the cured article that result obtains is 1.64.
Use curable resin composition evaluation " (20) forming characteristic ".The structure containing zirconium oxide nano-particle after being shaped with scanning electron microscope (SEM) shooting.By this SEM graphical representation at Fig. 3.As shown in Figure 3, transferability is good.
Embodiment 2-5
At the replacement cover type ZrO that dark brown vial mix embodiment 2-1 obtains 2particle 1 (6.0g), LIGHTACRYLATETMP-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), as Photoepolymerizationinitiater initiater, obtains curable resin composition 3.By obtained curable resin composition 3, be coated in PET film (A4300, thickness 100 μm, pencil hardness 2H spin in Japan) with excellent coating machine #10, drying 3 minutes at 80 DEG C, under air atmosphere, with high-pressure mercury light irradiation 1000mJ/cm 2ultraviolet make it solidify, obtain cured article.Measure the result of pencil hardness, its hardness is 3H.
Embodiment 2-6
(cover type ZrO is replaced by 2 ethyl hexanoic acid and/or from the zirconium oxide nano-particle that carboxylicesters and the 2-acryloyl-oxyethyl hexahydrophthalic acid of 2 ethyl hexanoic acid cover 2particle 3) preparation
The cover type ZrO that preparation example 2-1 is obtained 2particle (10g) and 2-acryloyl-oxyethyl hexahydrophthalic acid (4g) (pKa=3.33) are uniformly mixed to evenly in MEK (10g).Then, by add normal hexane (36g) make dispersed particle condense and make solution occur gonorrhoea, with filter paper by aggregated particle from gonorrhoea solution separating.Then, the aggregated particle of separation is made an addition in normal hexane (36g), stir after 10 minutes, aggregated particle is separated with filter paper, obtained particle is at room temperature dry under vacuo, modulate and (replace cover type ZrO by 2 ethyl hexanoic acid and/or from the carboxylicesters of 2 ethyl hexanoic acid and 2-acryloyl-oxyethyl hexahydrophthalic acid surface-treated Zirconia particles 2particle 3).
By obtained replacement cover type ZrO 2particle 3 is dispersed in as working sample in deuterochloroform, carries out 1the analysis of H-NMR.As a result, known 2 ethyl hexanoic acid and/or be 25:75 from the carboxylicesters of 2 ethyl hexanoic acid and the molar ratio that exists of 2-acryloyl-oxyethyl hexahydrophthalic acid.
Further, the mass loss rate of the Zirconia particles measured according to above-mentioned " mensuration of (5) mass loss rate " is 19 quality %.Therefore known capping oxidation zirconium particle 2 ethyl hexanoic acid and/or from the carboxylicesters of 2 ethyl hexanoic acid and 2-acryloyl-oxyethyl hexahydrophthalic acid, be 19 quality % of Zirconia particles entirety.
Embodiment 2-7
(cover type ZrO is replaced by 2 ethyl hexanoic acid and/or from the zirconium oxide nano-particle that carboxylicesters and the 2-acryloyl-oxyethyl phthalic acid of 2 ethyl hexanoic acid cover 2particle 4) preparation
The particle cover type ZrO that preparation example 2-1 is obtained 2particle (10g) and 2-acryloyl-oxyethyl phthalic acid (4g) (pKa=4.35) are uniformly mixed to dispersed in MEK (10g).Then, by add normal hexane (36g) make dispersed particle condense and make solution occur gonorrhoea, with filter paper by aggregated particle from gonorrhoea solution separating.Then, the aggregated particle of separation is added in normal hexane (36g), stir after 10 minutes, aggregated particle is separated with filter paper, gained particle is at room temperature dry under vacuo, modulation 2 ethyl hexanoic acid and/or (replace cover type ZrO from the carboxylicesters of 2 ethyl hexanoic acid and 2-acryloyl-oxyethyl phthalic acid surface-treated Zirconia particles 2particle 4).
By obtained replacement cover type ZrO 2particle 4 is dispersed in as working sample in deuterochloroform, carries out 1the analysis of H-NMR.As a result, known 2 ethyl hexanoic acid and/or be 6:94 from the carboxylicesters of 2 ethyl hexanoic acid and the molar ratio that exists of 2-acryloyl-oxyethyl phthalic acid.
Further, the mass loss rate of the Zirconia particles measured according to above-mentioned " mensuration of (5) mass loss rate " is 24 quality %.Therefore known capping oxidation zirconium particle 2 ethyl hexanoic acid and/or from the carboxylicesters of 2 ethyl hexanoic acid and 2-acryloyl-oxyethyl hexahydrophthalic acid, be 24 quality % of Zirconia particles entirety.
Preparation example 2-2
By 2 ethyl hexanoic acid and/or the preparation of zirconium oxide nano-particle that covers from the carboxylicesters of 2 ethyl hexanoic acid and 3-acryloxypropyl Trimethoxy silane
The cover type ZrO that above-mentioned preparation example 2-1 is obtained 2particle (10g) is distributed to modulation clear solution in toluene (90g).In this solution, add 3-acryloxypropyl Trimethoxy silane (1.5g, chemical industry society of SHIN-ETSU HANTOTAI system, KBM-5103) as surface treatment agent, reflux 1 hour at 90 DEG C.Then, by the solution after reflow treatment, add normal hexane (300g) and make dispersed particle condense and make solution occur gonorrhoea.With filter paper by aggregated particle from gonorrhoea solution separating, at room temperature heat drying, modulation 2 ethyl hexanoic acid and/or (replace cover type ZrO from the carboxylicesters of 2 ethyl hexanoic acid and 3-acryloxypropyl Trimethoxy silane surface-treated zirconium oxide nano-particle 2particle 5).
To obtained replacement cover type ZrO 2the crystalline texture of particle 5 confirms, detects and belongs to regular crystal and monoclinic diffracted ray, and from the intensity of diffracted ray, regular crystal and monoclinic ratio are 54/46, and its particle diameter (crystallization particle diameter) is 5nm.
The median size (average primary particle diameter) of the Zirconia particles obtained by determination of electron microscopy is 12nm.In addition, by obtained Zirconia particles, with infrared absorption spectrum analysis, except the absorption confirming the absorption except coming from C-H and come from COOH, the absorption coming from Si-O-C is also confirmed.These absorb, and can think to come from the 2 ethyl hexanoic acid that covers zirconium oxide nano-particle and/or from the carboxylicesters of 2 ethyl hexanoic acid and 3-acryloxypropyl Trimethoxy silane.Further, the mass loss rate of the Zirconia particles measured according to above-mentioned " mensuration of (5) mass loss rate " is 17 quality %.Therefore known capping oxidation zirconium nanoparticle 2 ethyl hexanoic acid and/or from the carboxylicesters of 2 ethyl hexanoic acid and 3-acryloxypropyl Trimethoxy silane, be 17 quality % of particle entirety.
In addition, by being analyzed according to " (9) Zr, Si assay " by this nanoparticle, the content of Si is measured, by quantitative for the 3-acryloxypropyl Trimethoxy silane in tectum.Further, the whole carbon contents in nanoparticle are measured according to " mensuration of (7) carbon content ", by deducting the carbon amounts coming from 3-acryloxypropyl Trimethoxy silane, calculate the carbon amounts of 2 ethyl hexanoic acid and/or the carboxylicesters from 2 ethyl hexanoic acid, try to achieve the amount of the 2 ethyl hexanoic acid in tectum and/or the carboxylicesters from 2 ethyl hexanoic acid.As a result, relative to the 2 ethyl hexanoic acid in tectum and/or the carboxylicesters from 2 ethyl hexanoic acid, 3-acryloxypropyl Trimethoxy silane there is ratio, with molar ratio computing for 1.5.
Embodiment 2-8
Except replacing replacing cover type ZrO 2particle 1 uses the replacement cover type ZrO synthesized by preparation example 2-2 2beyond particle 5, the method same with embodiment 2-3 (curable resin composition 1) obtains curable resin composition 4.
The transmittance of the cured coating film of the curable resin composition 4 measured according to above-mentioned " (14) transparency is evaluated " is 98%.In addition, implement the evaluation of the developability of curable resin composition 4 according to " (16) developability evaluation ", as shown in Figure 2, can confirm the residue in unexposed portion, developability is bad for result.
Embodiment 2-9
Except replacing replacing cover type ZrO 2particle 1 uses the replacement cover type ZrO synthesized by preparation example 2-2 2beyond particle 5, the method same with embodiment 2-4 (curable resin composition 2) obtains curable resin composition 5.Gained curable resin composition 5, does not have mobility at 25 DEG C.
Want that forming thing 5 to curable resin evaluates " (20) forming characteristic ", but curable resin composition 5 cannot be dripped on Si wafer, the structure containing zirconium oxide nano-particle cannot be obtained.
Comparative example 2-1
LIGHTACRYLATETMP-A (6.0g), methyl ethyl ketone (14g) is 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), as Photoepolymerizationinitiater initiater, obtains comparing curable resin composition 1.By obtained comparison curable resin composition 1, be coated in PET film (A4300, thickness 100 μMs, pencil hardness 2H spin in Japan) with excellent coating machine #10, drying 3 minutes at 80 DEG C, under air atmosphere, with high-pressure mercury light irradiation 1000mJ/cm 2ultraviolet, film maintain aqueous, cannot cured article be obtained.
Embodiment 2-10
The cover type ZrO that preparation example 2-1 is obtained 2particle (10g) is uniformly mixed in PGMEA (12g), maintains gonorrhoea, cannot form uniform solution.
Embodiment 3-1
By alkaline carbonic acid zirconium 432g (Japanese light metal society system, composition formula: Zr 2(CO 3) (OH) 2) O 2, the wet feed product of water ratio 46%.The chlorine of 3400 quality ppm is contained relative to zirconium.Zirconium 1.52mol), the mixed solution of 2,2-acid dimethyl 354g (3.04mol) and dimethylbenzene 216g, in the detachable flask of glass, react 2 hours at 80 DEG C.Now, the theoretical value not forming 2, the 2-excessive acid dimethyls of compound with zirconium is 1.52mol.In obtained solution, add the ammoniacal liquor 1150g (ammonia: 0.38mol) being adjusted to 0.033mol%, stir 30 minutes at 80 DEG C.Remove water layer after being cooled to room temperature, obtain the xylene solution of acid dimethyl zirconium compounds.
A part for the xylene solution of obtained acid dimethyl zirconium compounds is taken out, heats up in a steamer removal xylene at reduced pressure conditions, measure cl content by ion chromatograph, chlorine do not detected.
On the other hand, by the cl content of water layer of removing, measure with ion chromatograph, detect relative to the zirconium added to be the chlorine of 3400 quality ppm.
Embodiment 3-2
In the oil reservoir that embodiment 3-1 obtains, add deionized water 448g (zirconium relative to 1 mole is 16 moles), and join in high-pressure reactor, by the atmosphere nitrogen replacement of this high-pressure reactor.Then mixed solution is heated to 190 DEG C (reaction pressures: 1.4MPa), keeps 16 hours.Take out reacted solution, the throw out being deposited on bottom is filtered, cleans with 800g toluene.Dry by thing will be cleaned, obtain the cover type Zirconia particles 156g of white.
Confirm the crystalline texture of obtained cover type Zirconia particles, detect and belong to regular crystal and monoclinic diffracted ray, from the intensity of diffracted ray, regular crystal and monoclinic ratio are 78/22.In addition, crystallization particle diameter is 4nm.
In addition, the median size (average primary particle diameter) of the Zirconia particles obtained by determination of electron microscopy is 9nm, and its shape is granular.
Further, the mass loss rate of the Zirconia particles measured according to above-mentioned " mensuration of (5) mass loss rate " is 13%.
For obtained cover type Zirconia particles, measure cl content with ion chromatograph, chlorine do not detected.
Embodiment 3-3
Except being changed to beyond 177g (1.52mol) by 2, the 2-acid dimethyls of embodiment 3-1, carry out the synthesis of acid dimethyl zirconium compounds in the same manner as embodiment 3-1.As a result, produce gonorrhoea when dropping into ammoniacal liquor, form gel, being separated of organic layer (oil reservoir) and water layer cannot be carried out.
Embodiment 3-4
Except replacing the ammoniacal liquor of embodiment 3-1, using beyond deionized water, carry out the synthesis of acid dimethyl zirconium compounds in the same manner as embodiment 3-1.
A part for the xylene solution of obtained acid dimethyl zirconium compounds is taken out, heats up in a steamer removal xylene at reduced pressure conditions, measure cl content by ion chromatograph, detect relative to the zirconium added to be the chlorine of 3380 quality ppm.
By the cl content of water layer of removing, measure with ion chromatograph, detect relative to the zirconium added to be the chlorine of 20 quality ppm.
Embodiment 3-5
Use the xylene solution that embodiment 3-4 obtains, the operation same with embodiment 3-2, carries out the synthesis of cover type Zirconia particles.As a result, the cover type Zirconia particles 175g of white is obtained.
Confirm the crystalline texture of obtained cover type Zirconia particles, detect and belong to regular crystal and monoclinic diffracted ray, from the peak strength of diffracted ray, regular crystal and monoclinic ratio are 45/55.In addition, crystallization particle diameter is 7nm.
In addition, the median size (average primary particle diameter) of the Zirconia particles obtained by determination of electron microscopy is 10nm.
Further, the mass loss rate of the Zirconia particles measured according to above-mentioned " mensuration of (5) mass loss rate " is 12%.
By obtained cover type Zirconia particles, measure cl content by ion chromatograph, detect relative to the zirconium in particle to be the chlorine of 730 quality ppm.
The preparation of the zirconium oxide nano-particle that preparation example 4-1 is covered by 2 ethyl hexanoic acid
2 ethyl hexanoic acid zirconium mineral spirits solution (782g, the first rare element chemistry industry society system) is mixed with pure water (268g).Being added by gained mixed solution has in the high-pressure reactor of stirrer, by the atmosphere nitrogen replacement of this high-pressure reactor.Then, mixed solution is heated to 180 DEG C, keeps 16 hours (pressure in high-pressure reactor is 0.94MPa) at such a temperature, make it react, generate Zirconia particles.Then, take out reacted mixed solution, the throw out being deposited on bottom is filtered, after cleaning with acetone, dry.Dried described throw out (100g) is dispersed in toluene (800mL), forms gonorrhoea solution.Then, as refining step, again filter, the oversize particle etc. in disgorging with quantitative paper (society of ア De バ ンテック Japan system, No.5C).Further, filtrate reduced in volume is removed the Zirconia particles of toluene recovery white.
Confirm the crystalline texture of obtained Zirconia particles, detect and belong to regular crystal and monoclinic diffracted ray, from the intensity of diffracted ray, regular crystal and monoclinic ratio are 54/46, and its particle diameter (crystallization particle diameter) is 5nm.
The median size (average primary particle diameter) of the Zirconia particles obtained by determination of electron microscopy is 12nm.In addition, by obtained Zirconia particles, with infrared absorption spectrum analysis, the absorption coming from C-H and the absorption coming from COOH is confirmed.This absorption, the 2 ethyl hexanoic acid can thinking to result to cover Zirconia particles and/or the carboxylicesters from 2 ethyl hexanoic acid.
Further, the mass loss rate of the Zirconia particles measured according to above-mentioned " mensuration of (5) mass loss rate " is 12 quality %.Therefore the known 2 ethyl hexanoic acid of capping oxidation zirconium particle and/or the carboxylicesters from 2 ethyl hexanoic acid is 12 quality % of Zirconia particles entirety.
The preparation of the zirconium oxide nano-particle that preparation example 4-2 is covered by 2 ethyl hexanoic acid and 3-acryloxypropyl Trimethoxy silane
The zirconium oxide nano-particle (10g) obtained by described preparation example 4-1 is distributed to modulation clear solution in toluene (90g).3-acryloxypropyl Trimethoxy silane (1.5g, chemical industry society of SHIN-ETSU HANTOTAI system, KBM-5103) is added as surface treatment agent, reflux 1 hour at 90 DEG C in this solution.Then, solution is made to occur gonorrhoea by adding normal hexane to make dispersed particle condense in the solution after reflow treatment.With filter paper by aggregated particle from gonorrhoea solution separating, at room temperature heat drying, modulation 2 ethyl hexanoic acid and 3-acryloxypropyl Trimethoxy silane surface-treated zirconium oxide nano-particle.
Confirm the crystalline texture of obtained cover type Zirconia particles, detect and belong to regular crystal and monoclinic diffracted ray, from the intensity of diffracted ray, regular crystal and monoclinic ratio are 54/46, and its particle diameter (crystallization particle diameter) is 5nm.
The median size (average primary particle diameter) of the Zirconia particles obtained by determination of electron microscopy is 12nm.In addition, with infrared absorption spectrum analysis, confirm except coming from the absorption of C-H and coming from the absorption of COOH, also confirm the absorption coming from Si-O-C.These absorb, and can think to come from the 2 ethyl hexanoic acid and 3-acryloxypropyl Trimethoxy silane that cover zirconium oxide nano-particle.Further, the mass loss rate of the Zirconia particles measured according to above-mentioned " mensuration of (5) mass loss rate " is 17 quality %.Therefore the 2 ethyl hexanoic acid of known capping oxidation zirconium nanoparticle and 3-acryloxypropyl Trimethoxy silane, be 17 quality % of particle entirety.
In addition, by by the fluorescent x-ray analyzer analysis of this nanoparticle, measure the content of Si, the 3-acryloxypropyl Trimethoxy silane in tectum is carried out quantitatively.Further, measure the whole carbon contents in nanoparticle with CHNcoder analytical equipment, calculating by deducting the C gauge coming from 3-acryloxypropyl Trimethoxy silane the C amount coming from 2 ethyl hexanoic acid, trying to achieve the amount of the 2 ethyl hexanoic acid in tectum.As a result, relative to the 2 ethyl hexanoic acid in tectum, 3-acryloxypropyl Trimethoxy silane there is ratio, with molar ratio computing for 1.5.
Embodiment 4-1
Zirconium oxide nano-particle 7.5g, LIGHTACRYLATEIBX-A (isobornyl acrylate containing acrylic synthesized by preparation example 4-2 is added in dark brown vial, chemistry society of common prosperity society system) 10.0g, LIGHTACRYLATETMP-A (Viscoat 295, chemistry society of common prosperity society system) 2.5g, DAROCUR1173 (optical free radical polymerization starter, チ バ ジ ャ パ Application society system) 0.4g, methyl ethyl ketone 10.0g, carry out being stirred to evenly, obtain the composition containing inorganic oxide particle.
Embodiment 4-2
Except carrying out according to mix proportions shown in table 3, the method same with embodiment 4-1 obtains composition.
Comparative example 4-1
Except carrying out according to mix proportions shown in table 3, the method same with embodiment 4-1 obtains composition.
Represent mix proportions in table 3 and measure obtain embodiment 4-1, the transmittance containing the composition of inorganic oxide particle and the composition of comparative example 4-1 of 4-2, specific refractory power, specific inductivity result.
[table 3]
Abbreviation in table 3 is as described below.
IBX-A:LIGHTACRYLATEIB-XA (isobornyl acrylate, chemistry society of common prosperity society system)
TMP-A:LIGHTACRYLATETMP-A (Viscoat 295, chemistry society of common prosperity society system)
DAROCUR1173:2-hydroxy-2-methyl-1-phenyl-propan-1-ketone (チ バ ジ ャ パ Application society system)
< uses the example > of titanium
Preparation example 5-1
By 2 ethyl hexanoic acid and/or TiOx nano particle (the cover type TiO that covers from the carboxylicesters of 2 ethyl hexanoic acid 2son) preparation
Make the mixed solution of four titanium n-butoxide (170g, 0.5mol, Japanese Cao Da society system " B-1 ") and 2 ethyl hexanoic acid (345g, 2.4mol), in the detachable flask of glass, react 3 hours at 80 DEG C.In obtained solution, add deionized water (65g is 7 moles relative to titanium 1 mole), and join in high-pressure reactor, by the atmosphere nitrogen replacement of this high-pressure reactor.Then, mixed solution is heated to 190 DEG C, keeps 16 hours.Take out reacted solution, the throw out being deposited on bottom is filtered, cleans with methyl alcohol (500g).Dry by thing will be cleaned, obtain yellow cover type Titanium particles (cover type TiO 2particle) 33g.
The crystalline texture of obtained Titanium particles is confirmed, detects the diffracted ray belonging to anatase octahedrite.In addition, crystallization particle diameter is 6nm.
Further, according to cover type Titanium particles (the cover type TiO that above-mentioned " mensuration of (5) mass loss rate " measures 2particle) mass loss rate be 13 quality %.Therefore the 2 ethyl hexanoic acid of known capping oxidation titanium particle and/or the carboxylicesters from 2 ethyl hexanoic acid is 13 quality % of Titanium particles entirety.
Embodiment 5-1
(cover type TiO is replaced by 2 ethyl hexanoic acid and/or from the carboxylicesters of 2 ethyl hexanoic acid and 2-acryloyl-oxyethyl succsinic acid capping oxidation titanium nanoparticle 2particle) preparation
The cover type TiO that preparation example 5-1 is obtained 2the zirconia ball 270g of particle (30g), 2-acryloyl-oxyethyl succsinic acid (6g) (pKa=4.35), PGMEA (30g), diameter 0.03mm, add 100ml flask, at room temperature, dispersion treatment is carried out 2 hours with 1200rpm.Then, filtering zirconia ball by crossing, obtaining (replacing cover type TiO by 2 ethyl hexanoic acid and/or from the Titanium particles that carboxylicesters and the 2-acryloyl-oxyethyl succsinic acid of 2 ethyl hexanoic acid cover 2particle) dispersion liquid.Then, by add normal hexane (36g) make dispersed particle condense and make solution occur gonorrhoea, with filter paper by aggregated particle from gonorrhoea solution separating.Then, the aggregated particle of separation is added in normal hexane (36g), stir after 10 minutes, aggregated particle is separated with filter paper, obtained particle is at room temperature dry under vacuo, modulate and (replace cover type TiO by 2 ethyl hexanoic acid and/or from the carboxylicesters of 2 ethyl hexanoic acid and 2-acryloyl-oxyethyl succsinic acid surface-treated Titanium particles 2particle).
By obtained replacement cover type TiO 2particle dispersion as working sample, is carried out in deuterochloroform 1the analysis of H-NMR.As a result, known 2 ethyl hexanoic acid and/or be 10:90 from the carboxylicesters of 2 ethyl hexanoic acid and the molar ratio that exists of 2-acryloyl-oxyethyl succsinic acid.
Further, according to the replacement cover type TiO that above-mentioned " mensuration of (5) mass loss rate " measures 2the mass loss rate of particle is 20 quality %.Therefore known capping oxidation titanium particle 2 ethyl hexanoic acid and/or from the carboxylicesters of 2 ethyl hexanoic acid and 2-acryloyl-oxyethyl succsinic acid, be 20 quality % of Titanium particles entirety.
Embodiment 5-2
By 3,3-acid dimethyl and/or TiOx nano particle (the cover type TiO that covers from the carboxylicesters of 3,3-acid dimethyl 2particle) preparation
Make the mixed solution of four titanium n-butoxide (170g, 0.5mol, Japanese Cao Da society system " B-1 "), 3,3-acid dimethyls (280g, 2.4mol), in the detachable flask of glass, react 3 hours at 80 DEG C.In obtained solution, add deionized water (65g is 7 moles relative to zirconium white 1 mole), and join in high-pressure reactor, by the atmosphere nitrogen replacement of this high-pressure reactor.Then, mixed solution is heated to 190 DEG C, keeps 16 hours.Take out reacted solution, the throw out being deposited on bottom is filtered, cleans with methyl alcohol (500g).Dry by thing will be cleaned, obtain yellow cover type Titanium particles (cover type TiO 2particle) 62g.
The crystalline texture of obtained Titanium particles is confirmed, detects the diffracted ray belonging to anatase octahedrite.In addition, crystallization particle diameter is 6nm.
Further, according to cover type Titanium particles (the cover type TiO that above-mentioned " mensuration of (5) mass loss rate " measures 2particle) mass loss rate be 10%.Therefore 3,3-acid dimethyls of known capping oxidation titanium particle and/or the carboxylicesters from 3,3-acid dimethyl is 10 quality % of Titanium particles entirety.
In addition, the result of thermal test, Titanium particles maintenance is yellow and unchanged.
Embodiment 5-3
(cover type TiO is replaced by 3,3-acid dimethyl and/or from the TiOx nano particle that carboxylicesters and the 2-acryloyl-oxyethyl succsinic acid of 3,3-acid dimethyl cover 2particle) preparation
The cover type TiO that embodiment 5-2 is obtained 2the zirconia ball 270g of particle (30g), 2-acryloyl-oxyethyl succsinic acid (6g) (pKa=4.35), PGMEA (30g), diameter 0.03mm, add in 100ml flask, at room temperature, dispersion treatment is carried out 2 hours with 1200rpm.Then, filtering zirconia ball by crossing, obtaining (replacing cover type TiO by 3,3-acid dimethyl and/or from the Titanium particles that carboxylicesters and the 2-acryloyl-oxyethyl succsinic acid of 3,3-acid dimethyl cover 2particle) dispersion liquid.Then, add in obtained dispersion liquid 24g normal hexane (36g) make dispersed particle condense and make solution occur gonorrhoea, with filter paper by aggregated particle from gonorrhoea solution separating.Then, the aggregated particle of separation is added in normal hexane (36g), stir after 10 minutes, aggregated particle is separated with filter paper, gained particle is at room temperature dry under vacuo, modulate and (replace cover type TiO by 3,3-acid dimethyl and/or from the carboxylicesters of 3,3-acid dimethyl and 2-acryloyl-oxyethyl succsinic acid surface-treated Titanium particles 2particle).
Gained is replaced cover type TiO 2particle dispersion as working sample, is carried out in deuterochloroform 1the analysis of H-NMR.As a result, known 3,3-acid dimethyls and/or be 15:85 from the carboxylicesters of 3,3-acid dimethyl and the molar ratio that exists of 2-acryloyl-oxyethyl succsinic acid.
Further, according to the replacement cover type TiO that above-mentioned " mensuration of (5) mass loss rate " measures 2the mass loss rate of particle is 19 quality %.Therefore capping oxidation titanium particle 3,3-acid dimethyls and/or from the carboxylicesters of 3,3-acid dimethyl and 2-acryloyl-oxyethyl succsinic acid, be 19 quality % of Titanium particles entirety.

Claims (9)

1. a metal oxide particle, it is characterized in that, this metal oxide particle by have be selected from by ester group, ether, amide group, thioester substrate, thioether group, carbonate group, urethane groups and Urea-based the carboxylic acid cpd beyond the substituent carboxylic acid of more than 1 in the group that forms or (methyl) acrylic acid first carboxylic acid cpd and the first carboxylic acid cpd at least 2 kinds of carboxylic acid cpds cover.
2. capped metal oxide particle according to claim 1, wherein, the pKa of described first carboxylic acid cpd is less than 4.8.
3. capped metal oxide particle according to claim 1 and 2, wherein, described first carboxylic acid cpd or the second carboxylic acid cpd have polymerizability double bond.
4. a composition, is characterized in that, said composition contains the metal oxide particle according to any one of claim 1-3.
5., for the resin combination of indicating meter with transparent planar molding, it is characterized in that, this resin combination contains the metal oxide particle according to any one of claim 1-3.
6. according to claim 5 for the resin combination of indicating meter with transparent planar molding, wherein, the metal oxide particle according to any one of the claim 1-3 in described resin combination is 10 quality %-90 quality % in composition.
7. a planar molding, is characterized in that, this planar molding is by being formed for the resin combination of indicating meter with transparent planar molding described in claim 5 or 6.
8. a layered product, is characterized in that, this layered product is that planar molding lamination according to claim 7 forms.
9. a touch control panel device, is characterized in that, this touch control panel device is that planar molding lamination according to claim 7 forms.
CN201510408770.4A 2011-12-09 2012-12-10 Metal oxide particle and application thereof Active CN105085561B (en)

Applications Claiming Priority (9)

Application Number Priority Date Filing Date Title
JP2011270198A JP2013122643A (en) 2011-12-09 2011-12-09 Resin composition and planar molded body
JP2011-270198 2011-12-09
JP2011275765 2011-12-16
JP2011-275765 2011-12-16
JP2012061186 2012-03-16
JP2012-061186 2012-03-16
JP2012085681A JP6030844B2 (en) 2012-04-04 2012-04-04 Method for producing purified metal carboxylic acid compound and method for producing metal oxide particles using the same
JP2012-085681 2012-04-04
CN201280060430.1A CN103987688B (en) 2011-12-09 2012-12-10 Compound, metal oxide particles, and method for producing same and use of same

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
CN201280060430.1A Division CN103987688B (en) 2011-12-09 2012-12-10 Compound, metal oxide particles, and method for producing same and use of same

Publications (2)

Publication Number Publication Date
CN105085561A true CN105085561A (en) 2015-11-25
CN105085561B CN105085561B (en) 2019-05-28

Family

ID=48574411

Family Applications (2)

Application Number Title Priority Date Filing Date
CN201510408770.4A Active CN105085561B (en) 2011-12-09 2012-12-10 Metal oxide particle and application thereof
CN201280060430.1A Active CN103987688B (en) 2011-12-09 2012-12-10 Compound, metal oxide particles, and method for producing same and use of same

Family Applications After (1)

Application Number Title Priority Date Filing Date
CN201280060430.1A Active CN103987688B (en) 2011-12-09 2012-12-10 Compound, metal oxide particles, and method for producing same and use of same

Country Status (4)

Country Link
KR (1) KR101986233B1 (en)
CN (2) CN105085561B (en)
TW (1) TWI554475B (en)
WO (1) WO2013085062A1 (en)

Families Citing this family (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6217296B2 (en) * 2013-01-22 2017-10-25 東洋インキＳｃホールディングス株式会社 Photosensitive resin composition and coating film using the same
JP6278624B2 (en) * 2013-07-12 2018-02-14 株式会社日本触媒 Metal oxide particle-containing composition and optical member
JP6219627B2 (en) * 2013-07-12 2017-10-25 株式会社日本触媒 Metal oxide particles, composition containing metal oxide particles and optical member
WO2015111664A1 (en) * 2014-01-24 2015-07-30 株式会社日本触媒 Dispersion containing metal oxide particles
EP3106495B1 (en) * 2014-06-30 2018-10-17 Sekisui Plastics Co., Ltd. Nanoparticle-containing solution and use thereof
JP6687033B2 (en) * 2015-09-30 2020-04-22 住友金属鉱山株式会社 Conductive substrate
JP6589151B2 (en) * 2015-11-19 2019-10-16 協立化学産業株式会社 Photocurable resin composition and high refractive resin cured body
JP6747324B2 (en) 2017-02-06 2020-08-26 三菱マテリアル株式会社 Method for producing fine metal oxide particles
CN108075013A (en) * 2017-12-07 2018-05-25 苏州阿特斯阳光电力科技有限公司 A kind of preparation method and photovoltaic module of nanoscale photovoltaic welding belt coating
JP6933156B2 (en) 2018-02-14 2021-09-08 三菱マテリアル株式会社 Method for producing metal oxide dispersion
JP7020223B2 (en) * 2018-03-22 2022-02-16 三菱マテリアル株式会社 Metal oxide fine particles and their manufacturing method, dispersion liquid for forming an infrared shielding film and its manufacturing method, a method for forming an infrared shielding film, and a base material with an infrared shielding film.
WO2019220835A1 (en) * 2018-05-14 2019-11-21 Jsr株式会社 Pattern forming method and radiation sensitive composition
WO2020004172A1 (en) * 2018-06-29 2020-01-02 国立研究開発法人産業技術総合研究所 Organically modified metal oxide nanoparticles, production method thereof, euv photoresist material and production method for etching mask
WO2020255830A1 (en) * 2019-06-18 2020-12-24 住友電気工業株式会社 Resin composition, secondary coating material of optical fiber, optical fiber, and method for producing optical fiber
US11934101B2 (en) 2019-11-27 2024-03-19 Taiwan Semiconductor Manufacturing Company, Ltd. Photoresist composition and method of forming photoresist pattern
KR102293495B1 (en) * 2019-12-11 2021-08-26 주식회사 유엔아이 Inorganic Oxide Nanoparticles And Pigment Dispersed Composition And Photoresist Composition for Image Sensor Containing The Same
US20220397823A1 (en) * 2019-12-24 2022-12-15 National Institute Of Advanced Industrial Science And Technology Organically modified metal oxide nanoparticle, method for producing same, euv photoresist material, and method for producing etching mask
US11747724B2 (en) * 2019-12-24 2023-09-05 Tokyo Ohka Kogyo Co., Ltd. Organically modified metal oxide nanoparticles, organically modified metal oxide nanoparticles-containing solution, organically modified metal oxide nanoparticles-containing resist composition, and resist pattern forming method
WO2022043805A1 (en) * 2020-08-27 2022-03-03 3M Innovative Properties Company Surface-modified transition metal oxide nanoparticles, method of making the same, and curable composition and article including the same
KR20220078242A (en) * 2020-12-03 2022-06-10 주식회사 케이씨텍 Dispersion comprising metal oxide

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0246761A1 (en) * 1986-05-14 1987-11-25 Corning Glass Works Preparation of high purity zirconia and zirconia mixtures from zirconium carbonate
WO2008010533A1 (en) * 2006-07-18 2008-01-24 Nippon Shokubai Co., Ltd. Metal oxide nanoparticle and method for producing the same
CN101132989A (en) * 2004-12-30 2008-02-27 3M创新有限公司 Zirconia particles
US20080242745A1 (en) * 2007-03-29 2008-10-02 Fujifilm Corporation Aqueous dispersion of metal oxide fine particles and method for producing the same
CN101296982A (en) * 2005-10-28 2008-10-29 住友大阪水泥股份有限公司 Transparent inorganic-oxide dispersion, resin composition containing inorganic oxide particles, composition for encapsulating luminescent element, luminescent element, hard coat, optical functional fi
JP2009191167A (en) * 2008-02-14 2009-08-27 Sumitomo Osaka Cement Co Ltd Transparent liquid dispersion of metal oxide having high refractive index, transparent resin complex, and optical lens

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1048625A (en) * 1996-08-02 1998-02-20 Sumitomo Chem Co Ltd Touch panel for liquid crystal display
JP4004025B2 (en) * 2001-02-13 2007-11-07 日東電工株式会社 Transparent conductive laminate and touch panel
JP5030694B2 (en) 2006-07-18 2012-09-19 株式会社日本触媒 Zirconium oxide nanoparticles
JP2009096681A (en) 2007-10-18 2009-05-07 Nippon Shokubai Co Ltd Manufacturing process of zirconium oxide nanoparticle, zirconium oxide nanoparticle and composition containing zirconium oxide nanoparticle

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0246761A1 (en) * 1986-05-14 1987-11-25 Corning Glass Works Preparation of high purity zirconia and zirconia mixtures from zirconium carbonate
CN101132989A (en) * 2004-12-30 2008-02-27 3M创新有限公司 Zirconia particles
CN101296982A (en) * 2005-10-28 2008-10-29 住友大阪水泥股份有限公司 Transparent inorganic-oxide dispersion, resin composition containing inorganic oxide particles, composition for encapsulating luminescent element, luminescent element, hard coat, optical functional fi
WO2008010533A1 (en) * 2006-07-18 2008-01-24 Nippon Shokubai Co., Ltd. Metal oxide nanoparticle and method for producing the same
US20080242745A1 (en) * 2007-03-29 2008-10-02 Fujifilm Corporation Aqueous dispersion of metal oxide fine particles and method for producing the same
JP2009191167A (en) * 2008-02-14 2009-08-27 Sumitomo Osaka Cement Co Ltd Transparent liquid dispersion of metal oxide having high refractive index, transparent resin complex, and optical lens

Also Published As

Publication number Publication date
KR20140117352A (en) 2014-10-07
CN105085561B (en) 2019-05-28
KR101986233B1 (en) 2019-06-05
CN103987688A (en) 2014-08-13
CN103987688B (en) 2017-05-24
TW201336786A (en) 2013-09-16
TWI554475B (en) 2016-10-21
WO2013085062A1 (en) 2013-06-13

Similar Documents

Publication Publication Date Title
CN105085561A (en) Metal oxide particle and applications thereof
JP6251478B2 (en) Metal oxide particles, composition and method for producing metal oxide particles
CN103154052B (en) Diolefin series carboxylate anion is with its salt and be polymerized or solidification compound
WO2008010533A1 (en) Metal oxide nanoparticle and method for producing the same
KR102042983B1 (en) Electronic device and manufacturing method thereof
TWI439419B (en) Aggregate of spherical core shell type cerium oxide/polymeric hybrid nano particles and manufacturing method thereof
EP1590100B1 (en) Hybrid organic-inorganic polymer coatings with high refractive indices
JP2008201864A (en) Coating composition and optical film
CN102046522A (en) Method for producing core-shell particle, core-shell particle, method for producing hollow particle, paint composition and article
JP5815304B2 (en) Optical thin film forming paint and optical thin film
Chang et al. Preparation and characterization of TiO 2 hybrid sol for UV-curable high-refractive-index organic–inorganic hybrid thin films
TW201125732A (en) Optical layered product, polarizer and display using the optical layered product
TW201400561A (en) Hard coating composition and composition for forming high refractive index anti-blocking layer
CN105793036A (en) Conductive laminate and touch panel using same
CN105829451B (en) Resin combination, resin sheet and resin laminate
JP6278624B2 (en) Metal oxide particle-containing composition and optical member
JP2008184596A (en) Coating composition and optical film
CN110461589A (en) Polymeric substrate with hard conating
CN103959105B (en) Color tone correction film and transparent conductive film using same
JP3944957B2 (en) Fluorine-containing compound, optical thin film and antireflection article
CN103987781A (en) Resin composition for optical material
TWI606101B (en) Coating composition and method of manufacturing the same
KR20110133209A (en) High refractive index hard coating compositions using roll printing and printing film using it
KR101321414B1 (en) Resin composition for hard coating hanving antiblocking and antistatic property and hard coating film using the same
Park et al. Triethylene glycol–titanium oxide hydrate hybrid films with high refractive index and surface evenness

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant