WO2019225743A1 - Composition - Google Patents

Composition Download PDF

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Publication number
WO2019225743A1
WO2019225743A1 PCT/JP2019/020672 JP2019020672W WO2019225743A1 WO 2019225743 A1 WO2019225743 A1 WO 2019225743A1 JP 2019020672 W JP2019020672 W JP 2019020672W WO 2019225743 A1 WO2019225743 A1 WO 2019225743A1
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Prior art keywords
metal
group
composition
metal alkoxide
alkoxide
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PCT/JP2019/020672
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French (fr)
Japanese (ja)
Inventor
幸宏 牧島
井　宏元
北　弘志
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コニカミノルタ株式会社
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Application filed by コニカミノルタ株式会社 filed Critical コニカミノルタ株式会社
Priority to JP2020520396A priority Critical patent/JPWO2019225743A1/en
Publication of WO2019225743A1 publication Critical patent/WO2019225743A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
    • C08G79/14—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing two or more elements other than carbon, oxygen, nitrogen, sulfur and silicon
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L85/00—Compositions of macromolecular compounds obtained by reactions forming a linkage in the main chain of the macromolecule containing atoms other than silicon, sulfur, nitrogen, oxygen and carbon; Compositions of derivatives of such polymers

Definitions

  • the present invention relates to a composition, and more particularly, to a composition that can form an organic thin film that is stable in the air and can be removed by low-temperature drying.
  • An inorganic oxide containing a plurality of types of metal atoms has a function that does not appear from a single inorganic oxide.
  • barium titanate (BaTiO 3 ) has a specifically high dielectric constant and ferroelectricity and is widely known as an electronic device material such as a capacitor.
  • inorganic oxides containing multiple types of metal atoms are produced by vacuum film formation and can form a dense film.
  • a large apparatus is required, and roll-to-roll Since it is unsuitable for continuous production as described above, the cost burden in manufacturing is high, and the problem is large for mass production at low cost.
  • Patent Document 1 describes the stability of metal alkoxide in water by adding a chelating agent to Ti alkoxide and Si alkoxide. It has been disclosed that polymerization can be suppressed and particle size can be kept small even in the atmosphere. However, when forming a film, it is necessary to remove components such as solvents and additives in order to ensure the physical properties of the metal oxide film, but chelating agents generally have a very high coordinating power. Therefore, there is a problem that the use of the resin on a flexible substrate such as polyethylene terephthalate (PET) or polyethylene naphthalate (PEN) is restricted.
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • the metal alkoxide is excessively stabilized by the high coordinating power of the chelating agent, the reactivity is extremely low even when it is formed into a film, and the function represented by water absorption utilizing chemical adsorption is inhibited. There was a problem of doing.
  • the present invention has been made in view of the above-described problems and situations, and a problem to be solved is to provide a composition that can form an organic thin film that is stable in the air and can be removed by solvent drying at low temperature. .
  • the present inventor has stabilized the metal alkoxide by changing the alkoxy group having a plurality of types of metals to a metal alkoxide having a fluorinated alkoxy group. Further, when the film was further formed, it was found that the solvent could be distilled off by drying at a low temperature, and that a water absorbing function and a water repellent function were exhibited.
  • a composition comprising a metal atom.
  • the plurality of types of metal atoms are Ti—Si, Ti—Ba, Ti—Sr, Ti—Ca, Ti—Mg, Ti—Zr, Ti—Zn, Ti—Cu, Zn—Cu, Zn—Si, Cu—.
  • the monomer of the metal alkoxide or metal carboxylate has a plurality of types of metal alkoxide or metal carboxylate having a structure represented by the following general formula (1), and the metal of the plurality of types of metal alkoxide or metal carboxylate The composition according to item 1 or 2, wherein the species are different from each other.
  • M (OR 1 ) y (OR) xy (In the formula, R represents a hydrogen atom, an alkyl group having 1 or more carbon atoms, an alkenyl group, an aryl group, a cycloalkyl group, an acyl group, or a heterocyclic group. However, R represents a carbon containing a fluorine atom as a substituent.
  • the chain may be a chain
  • M represents a metal atom
  • OR 1 represents a fluorinated alkoxy group
  • x represents the valence of the metal atom
  • y represents any integer between 1 and x.
  • the monodentate ligand which has the ether bond or carbonyl group which can be coordinated to the metal atom in the said metal alkoxide or metal carboxylate is contained, Any one of Claim 1 to 4 characterized by the above-mentioned.
  • composition according to item 5 wherein the monodentate ligand has an ether bond.
  • R 1 —O—R 2 (In the formula, R 1 and R 2 each independently represents an alkyl group having 2 to 4 carbon atoms.)
  • metal alkoxide or metal carboxylate has high reactivity to water.
  • the sol-gel solution comprising a plurality of types of metal alkoxide or metal carboxylate having a fluorinated alkoxy group according to the present invention has a reaction rate with moisture. Since it is relaxed, the progress of the polymerization can be suppressed. Therefore, the particle size can be kept small even in the atmosphere.
  • the fluorinated alcohol since it has no coordination power to the metal alkoxide or the metal carboxylate, it can be removed by low-temperature drying, and use for a flexible substrate using a resin is realized.
  • a film prepared from the above liquid is effective as a functional film having both water absorption and water repellency or hydrophobicity.
  • the reason why the reaction rate between the metal alkoxide or metal carboxylate having a fluorinated alkoxy group and moisture is relaxed is that the fluorine atom present around the central metal exhibits a hydrophobic effect, and the frequency factor of moisture around the central metal is reduced. This is considered to be because it can be reduced. As a result, it is considered that polymerization can be suppressed to some extent even in the atmosphere, and the particle size can be suppressed to a small value.
  • Ti alkoxide having high reactivity with water can suppress the reactivity by using a metal alkoxide or metal carboxylate having a fluorinated alkoxy group, and the metal alkoxide or metal carboxylate other than Ti, for example,
  • Si silicon as a plurality of types, the reaction rate between the metal alkoxide or metal carboxylate and moisture can be controlled.
  • the composition of the present invention is a composition containing a metal alkoxide or a metal carboxylate, wherein the metal alkoxide or metal carboxylate has a fluorinated alkoxy group. It is a combination and contains a plurality of types of metal atoms. This feature is a technical feature common to the following embodiments.
  • the plurality of types of metal atoms are Ti—Si, Ti—Ba, Ti—Sr, Ti—Ca, Ti—Mg, Ti—Zr, Ti. It is liquid stable to be any combination of metal atoms of —Zn, Ti—Cu, Zn—Cu, Zn—Si, Cu—Si, Ca—Bi—Ti, Sr—Bi—Ta or Bi—Fe. From the viewpoint of water absorption.
  • the monomer of the metal alkoxide or metal carboxylate has a plurality of types of metal alkoxides or metal carboxylates having the structure represented by the general formula (1), and the plurality of types of metal alkoxides or metal carboxylates. It is preferable that the metal species are different from each other because an effect that does not appear from a single inorganic oxide is obtained.
  • the number of fluorine atoms contained in the metal alkoxide is preferably in the range of 4 to 16 with respect to one metal atom of each metal alkoxide.
  • a monodentate ligand having an ether bond or a carbonyl group that can be coordinated to a metal atom in the metal alkoxide or metal carboxylate because a liquid stability effect can be obtained.
  • the monodentate ligand preferably has an ether bond, and more preferably a monodentate ligand having an ether bond represented by the general formula (2).
  • ⁇ is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
  • the composition of the present invention is a composition containing a metal alkoxide or a metal carboxylate, wherein the metal alkoxide or metal carboxylate has a fluorinated alkoxy group. It is a combination and contains a plurality of types of metal atoms.
  • Such a configuration makes it possible to realize a composition that can form a film that is stable in the air and that can be removed by solvent drying at low temperature.
  • the metal alkoxide or metal carboxylate according to the present invention is a metal alkoxide or metal carboxylate monomer or polymer having a fluorinated alkoxy group, and contains a plurality of types of metal atoms.
  • the composition of the present invention is a polycondensate of an organic metal oxide or an organic metal oxide obtained by alcohololysis of a metal alkoxide or metal carboxylate in the presence of an excess of fluorinated alcohol to replace the alcohol. At that time, it is preferable to use a long-chain alcohol in which a fluorine atom is substituted at the ⁇ -position of the hydroxy group.
  • a plurality of metal alkoxides or metal carboxylates may be treated separately, or a plurality of metal alkoxides or metal carboxylates may be mixed and treated simultaneously.
  • the organometallic oxide can promote a sol-gel reaction and form a polycondensate by irradiating with sintering or ultraviolet rays.
  • the frequency factor of moisture present around the metal in the metal alkoxide or metal carboxylate is reduced by the water repellent effect or hydrophobic effect of fluorine.
  • the hydrolysis rate is reduced, and by utilizing the phenomenon, a three-dimensional polymerization reaction can be suppressed and a uniform and dense organic thin film containing a desired organometallic oxide can be formed.
  • the organometallic oxide according to the composition of the present invention is shown in the following reaction scheme I or reaction scheme II.
  • the metal alkoxide or metal carboxylate contains a plurality of types of metal atoms. Specifically, it is preferable that a plurality of types of metal alkoxides or metal carboxylates are included and the metal types of the metal alkoxides or metal carboxylates are different.
  • the sintered metal oxide since the metal alkoxide uses a plurality of metal alkoxides having different metal species, the sintered metal oxide includes a plurality of metal species.
  • M 1 or M 2 in the “OM 1 ” or “OM 2 ” part further has a substituent. It is omitted.
  • the organic thin film formed by polycondensation of the organometallic oxide by ultraviolet irradiation is hydrolyzed by moisture (H 2 O) from outside the system according to the following reaction scheme III, and is made of a water repellent or hydrophobic substance. Releases some fluorinated alcohol (R'-OH).
  • composition of the present invention is characterized in that a water-repellent function or a hydrophobic function is added by reaction with moisture because the fluorinated alcohol produced by hydrolysis is water-repellent or hydrophobic.
  • M 1 or M 2 in the “OM 1 ” or “OM 2 ” part further has a substituent, but is omitted.
  • the metal alkoxide or metal carboxylate monomer according to the present invention includes a plurality of metal alkoxides or metal carboxylates having a structure represented by the following general formula (1), and the plurality of types of metal alkoxides or metal carboxylates.
  • the metal species of the rate are preferably different from each other.
  • each of the metal species having a structure represented by the following general formula (3) manufactured from a plurality of metal alkoxides or metal carboxylates having different metal species having a structure represented by the following general formula (1) is different. It is preferable to contain a plurality of metal alkoxides or metal carboxylates as a main component.
  • the “main component” is preferably a total of the metal alkoxide or metal carboxylate in which 70% by mass or more of the total mass of the composition releases water-repellent or hydrophobic substances, and more preferably 80%. It means mass% or more, particularly preferably 90 mass% or more.
  • R represents a hydrogen atom, an alkyl group having 1 or more carbon atoms, an alkenyl group, an aryl group, a cycloalkyl group, an acyl group, or a heterocyclic group. However, R represents a carbon containing a fluorine atom as a substituent.
  • the chain may be a chain
  • M represents a metal atom
  • OR 1 represents a fluorinated alkoxy group
  • x represents the valence of the metal atom
  • y represents any integer between 1 and x.
  • R represents a hydrogen atom, an alkyl group having 1 or more carbon atoms, an alkenyl group, an aryl group, a cycloalkyl group, an acyl group, an alkoxy group, or a heterocyclic group.
  • R represents fluorine as a substituent.
  • the organometallic oxide according to the present invention is not particularly limited as long as it can be produced by using a sol-gel method.
  • a plurality of types of metal alkoxides or metal carboxylates having a structure represented by the general formula (1) are provided, and the metal types of the plurality of types of metal alkoxides or metal carboxylates are different from each other.
  • Multiple kinds of metal atoms are Ti—Si, Ti—Ba, Ti—Sr, Ti—Ca, Ti—Mg, Ti—Zr, Ti—Zn, Ti—Cu, Zn—Cu, Zn—Si, Cu—Si. , Ca—Bi—Ti, Sr—Bi—Ta, or a combination of Bi—Fe is preferable from the viewpoint of liquid stability and water absorption.
  • OR 1 represents a fluorinated alkoxy group.
  • R 1 represents an alkyl group substituted with at least one fluorine atom. Specific examples of each substituent will be described later.
  • the water repellency or hydrophobicity of the film obtained by polycondensation of the composition of the present invention that the number of fluorine atoms contained in the metal alkoxide is in the range of 4 to 16 per one metal atom. Can be increased, which is preferable.
  • R represents a hydrogen atom, an alkyl group having 1 or more carbon atoms, an alkenyl group, an aryl group, a cycloalkyl group, an acyl group, an alkoxy group, or a heterocyclic group. Or what substituted at least one part of the hydrogen atom of each group with the halogen may be used. Moreover, a polymer may be sufficient.
  • Alkyl groups are substituted or unsubstituted, and specific examples include methyl, ethyl, propyl, butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl.
  • the alkenyl group is substituted or unsubstituted, and specific examples include a vinyl group, an allyl group, a butenyl group, a pentenyl group, a hexenyl group, and the like, and preferably those having 8 or more carbon atoms. These oligomers or polymers may also be used.
  • the aryl group is substituted or unsubstituted, and specific examples include phenyl group, tolyl group, 4-cyanophenyl group, biphenyl group, o, m, p-terphenyl group, naphthyl group, anthranyl group, phenanthrenyl group, There are a fluorenyl group, a 9-phenylanthranyl group, a 9,10-diphenylanthranyl group, a pyrenyl group, and the like, preferably those having 8 or more carbon atoms. These oligomers or polymers may also be used.
  • substituted or unsubstituted alkoxy group examples include a methoxy group, an n-butoxy group, a tert-butoxy group, a trichloromethoxy group, and a trifluoromethoxy group, and preferably those having 8 or more carbon atoms. These oligomers and polymers may also be used.
  • substituted or unsubstituted cycloalkyl group examples include a cyclopentyl group, a cyclohexyl group, a norbonane group, an adamantane group, a 4-methylcyclohexyl group, a 4-cyanocyclohexyl group, and preferably those having 8 or more carbon atoms. Good. These oligomers or polymers may also be used.
  • substituted or unsubstituted heterocyclic group examples include pyrrole group, pyrroline group, pyrazole group, pyrazoline group, imidazole group, triazole group, pyridine group, pyridazine group, pyrimidine group, pyrazine group, triazine group, indole group, Benzimidazole group, purine group, quinoline group, isoquinoline group, sinoline group, quinoxaline group, benzoquinoline group, fluorenone group, dicyanofluorenone group, carbazole group, oxazole group, oxadiazole group, thiazole group, thiadiazole group, benzoxazole group Benzothiazole group, benzotriazole group, bisbenzoxazole group, bisbenzothiazole group, bisbenzimidazole group and the like. These oligomers or polymers may also be used.
  • substituted or unsubstituted acyl group examples include formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl, isovaleryl, pivaloyl, lauroyl, myristoyl, palmitoyl, stearoyl, oxalyl Group, malonyl group, succinyl group, glutaryl group, adipoyl group, pimeloyl group, suberoyl group, azelaoil group, sebacoyl group, acryloyl group, propioloyl group, methacryloyl group, crotonoyl group, isocrotonoyl group, oleoyl group, elidoyl group, maleoyl group , Fumaroyl group, citraconoyl group, mesaconoyl group, camphoroyl group, benzoyl group, phthaloyl group, isophthaloyl group, iso
  • Each of the plurality of metal alkoxides and metal carboxylates having different metal species and the fluorinated alcohol (R′-OH) become the organometallic oxide according to the present invention by the following reaction scheme IV.
  • a metal oxide substituted with n fluoroalkoxy groups can be obtained.
  • (R′—OH) is exemplified by the following structures F-1 to F-16.
  • Examples of the metal alkoxide or metal carboxylate according to the present invention include the following compounds represented by M (OR) n or M (OCOR) n, and the organometallic oxide according to the present invention includes the above (R′—OH: F In combination with -1 to F-16), compounds having the structures of the following exemplified compound numbers 1 to 170 (see the exemplified compounds I to IV below) are obtained.
  • the individual metal alkoxide or metal carboxylate according to the present invention is not limited to this. In this invention, it is preferable to have two or more types of the above-mentioned metal alkoxide or metal carboxylate, and the metals in the plurality of types of metal alkoxide or metal carboxylate are different.
  • the metal is 2 to 3 kinds.
  • Each metal alkoxide or metal carboxylate having a different metal species is preferably in the range of 10 to 90 mol% with respect to the total amount of the entire metal alkoxide or metal carboxylate.
  • the method for producing an organometallic oxide for producing the organometallic oxide according to the present invention is preferably produced using a mixed solution of a metal alkoxide or metal carboxylate and a fluorinated alcohol.
  • the organic metal oxide polycondensate forms an organic thin film, which absorbs moisture and releases fluorinated alcohol, which is a water-repellent or hydrophobic substance, according to Reaction Scheme V below.
  • the metal species is represented by Ti, but R′—OH can be similarly released using a plurality of metals.
  • Ti in the “O—Ti” part further has a substituent, but is omitted.
  • the composition of the present invention contains a ligand, and the ligand is monodentate having an ether bond or a carbonyl group capable of coordinating to a metal atom in the metal alkoxide or metal carboxylate according to the present invention. It is characterized by being a rank.
  • a monodentate ligand in this way, the composition of the present invention is stabilized, excessive polymerization is suppressed, and the solvent can be easily removed. Can be expressed.
  • the monodentate chemical species according to the present invention by adding the monodentate chemical species according to the present invention to the fluorine-substituted metal alkoxide or metal carboxylate, the monodentate chemical species is coordinated to the central metal of the metal alkoxide or metal carboxylate. To do. As a result, the metal alkoxide or metal carboxylate is further stabilized and excessive polymerization can be suppressed, and the particle size in the atmosphere can be suppressed small.
  • monodentate species are less coordinating than chelating agents, so they can be distilled off by drying at lower temperatures, and when they are made into membranes, they also exhibit water absorption, water repellency or hydrophobic functions. can do.
  • Such an ether bond or carbonyl group that can be coordinated to a metal atom in a metal alkoxide or metal carboxylate includes dibutyl ether.
  • Such a monodentate ligand is preferably a monodentate ligand having an ether bond represented by the following general formula (2).
  • R 1 —O—R 2 (In the formula, R 1 and R 2 each independently represents an alkyl group having 2 to 4 carbon atoms.)
  • Examples of the monodentate coordination having an ether bond include diethyl ether, dipropyl ether, dibutyl ether, and propylbutyl ether.
  • the monodentate ligand is preferably used in the range of 0.1 to 4 mol, preferably in the range of 1 to 2 mol, relative to 1 mol of the metal alkoxide or metal carboxylate.
  • Organic thin film in which the composition of the present invention is used can be formed by preparing a coating solution containing the composition of the present invention, and forming a film while applying polycondensation by sintering or irradiating ultraviolet rays after coating. it can.
  • organic solvent examples include hydrocarbon solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons, halogenated hydrocarbon solvents, or Ethers such as aliphatic ethers or alicyclic ethers can be used as appropriate.
  • hydrocarbon solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons, halogenated hydrocarbon solvents, or Ethers such as aliphatic ethers or alicyclic ethers can be used as appropriate.
  • the concentration of the organometallic oxide of the present invention in the coating solution varies depending on the target thickness and the pot life of the coating solution, but is preferably about 0.2 to 35% by mass. It is also preferable to add a catalyst for promoting polymerization to the coating solution.
  • the prepared coating liquid can be applied by spray coating, spin coating, blade coating, dip coating, dip coating, casting, roll coating, bar coating, die coating, and other printing methods including inkjet printing.
  • a wet forming method such as a patterning method can be used, and can be used depending on the material.
  • the inkjet printing method is preferable.
  • the ink jet printing method is not particularly limited, and a known method can be adopted.
  • the on-demand method or the continuous method may be used as the method for discharging the coating liquid from the ink jet head by the ink jet printing method.
  • On-demand inkjet heads are available in electro-mechanical conversion methods such as single cavity type, double cavity type, bender type, piston type, shear mode type and shared wall type, or thermal inkjet type and bubble jet (registered trademark). ) Any type of electrical-thermal conversion system or the like may be used.
  • plasma In order to fix the organic thin film after coating, it is preferable to use plasma, ozone, or ultraviolet light that can be polymerized at a low temperature.
  • Examples of means for generating ultraviolet rays in vacuum ultraviolet treatment include metal halide lamps, high-pressure mercury lamps, low-pressure mercury lamps, xenon arc lamps, carbon arc lamps, excimer lamps, and UV light lasers.
  • UV irradiation can be applied to both batch processing and continuous processing, and can be appropriately selected depending on the shape of the substrate used.
  • the base material for forming the organic thin film is in the form of a long film, it can be carried out by continuously irradiating ultraviolet rays in a drying zone equipped with the ultraviolet ray generation source as described above while being conveyed.
  • the time required for ultraviolet irradiation is generally 0.1 seconds to 10 minutes, preferably 0.5 seconds to 3 minutes, although it depends on the base material used and the composition and concentration of the composition-containing coating solution.
  • the energy coated surface receives is preferably 3.0 J / cm 2 or more, more preferably 3.5 J / cm 2 or more, 4.0 J More preferably, it is / cm 2 .
  • it is preferably 14.0J / cm 2 or less, more preferably 12.0J / cm 2 or less, is 10.0J / cm 2 or less More preferably.
  • the oxygen concentration at the time of irradiation with the excimer lamp is preferably 300 to 10,000 ppm by volume (1% by volume), more preferably 500 to 5,000 ppm by volume. By adjusting to such an oxygen concentration range, it is possible to prevent the organic thin film from being excessive in oxygen and to prevent moisture absorption from deteriorating.
  • a dry inert gas as the gas other than oxygen at the time of excimer lamp irradiation, and it is particularly preferable to use a dry nitrogen gas from the viewpoint of cost.
  • the organic thin film formed from the composition of the present invention is preferably an organic material for electronic devices.
  • the electronic device examples include organic EL elements, light emitting diodes (LEDs), liquid crystal elements, solar cells (photoelectric conversion elements), touch panels, liquid crystal display devices, and other color filters.
  • the electronic device is an organic EL element, a solar cell, and a light emitting diode from the viewpoint of manifesting the effect of the present invention.
  • the organic material for electronic devices means the solid component of an organic material, and shall not contain an organic solvent.
  • the organic thin film according to the present invention can be used, for example, as a desiccant that releases water-repellent or hydrophobic substances by reacting with water.
  • composition of the present invention can be used as an ink jet dispenser liquid.
  • Example 1 (Preparation of composition) (Preparation of Composition 1) (A) Titanium tetraisopropoxide (Ti (OiPr) 4 ) 0.1M and (b) barium diisopropoxide (Ba (OiPr) 2 ) in a glove box under a dry nitrogen atmosphere with a moisture concentration of 1 ppm or less Composition 1 was a sol-gel solution prepared by 2 mL of a solution using dehydrated isopropyl alcohol each containing 0.1 M as a solvent.
  • composition 2 (Preparation of composition 2) (A) Titanium tetraisopropoxide (Ti (OiPr) 4 ) 0.1M and (b) barium diisopropoxide (Ba (OiPr) 2 ) in a glove box under a dry nitrogen atmosphere with a moisture concentration of 1 ppm or less 2 mL of a solution was prepared using dehydrated isopropyl alcohol each containing 0.1 M as a solvent, and 40 mL of air at 25 ° C. and humidity 50% RH sealed in a glass syringe was bubbled and immediately returned to the glove box.
  • the sol-gel solution was composition 2.
  • compositions 3 to 10 were obtained.
  • 140 ⁇ L of dibutyl ether as a monodentate ligand was added to prepare a solution, and then the atmosphere was bubbled to prepare the composition.
  • Average particle size The average particle size was measured three times for 100 particles using a Zetasizer Nano ZS90 (Malvern Panallytical), the average value of the obtained particle sizes was confirmed, and the average value of the three measurements was averaged. The particle diameter was taken.
  • compositions 5 and 7 using a fluorinated alcohol with respect to comparative compositions 2 and 3 have a small average particle size and a transparent liquid. Moreover, it turns out that the composition 5 and 6 which used the fluorinated alcohol with respect to the comparative compositions 3 and 4 can suppress particle size small even if it increases bubbling amount, and is more stable in air
  • Example 2 (Production of composition) (Preparation of composition 11) In a glove box under a dry nitrogen atmosphere having a moisture concentration of 1 ppm or less, (a) titanium tetraisopropoxide (Ti (OiPr) 4 ) 0.1M and (b) silicon tetraisopropoxide (Si (OiPr) 4 ) Thickness of 100 nm formed by preparing 2 mL of a solution using dehydrated isopropyl alcohol each containing 0.1 M as a solvent, and drying the solution on a silicon wafer by spin film formation (1000 rpm, 30 seconds), followed by drying at 110 ° C. for 30 minutes. This organic thin film was designated as Composition 11.
  • compositions 12 to 15 were prepared in the same manner as the composition 11 except that the two metal alkoxides and the solvent were replaced with the two metal alkoxides shown in Table II and the dehydrated solvent.
  • 140 ⁇ L of bidentate acetylacetone (a quantity of 2 mol with respect to 1 mol of metal alkoxide) was further added as a ligand, and then this was sealed in a glass syringe at 25 ° C. and humidity of 50%.
  • a liquid obtained by bubbling 40 mL of the RH atmosphere was spin-formed in the same manner as the composition 11 and dried to prepare an organic thin film having a thickness of 100 n ⁇ m.
  • composition 15 a monodentate ligand dibutyl ether 140 ⁇ L (2 mol amount per 1 mol of metal alkoxide) was further added, followed by spin film formation in the same manner as in composition 11, and dried to form an organic thin film having a thickness of 100 nm.
  • a monodentate ligand dibutyl ether 140 ⁇ L (2 mol amount per 1 mol of metal alkoxide) was further added, followed by spin film formation in the same manner as in composition 11, and dried to form an organic thin film having a thickness of 100 nm. was made.
  • ⁇ Formed as a film, and the composition does not adhere to the hand even when touched by the hand.
  • the physical resistance of the film is weak and the composition adheres to the hand when touched by the hand.
  • the film has a sea-island pattern. .
  • the refractive index of the organic thin film produced above was measured at a wavelength of 650 nm using a spectroscopic ellipsometer (UNECS-2000: manufactured by ULVAC, Inc.).
  • composition 14 using the fluorinated alcohol with respect to the composition 13 and further the composition 15 in which dibutyl ether is added as a monodentate ligand have an improved refractive index.
  • a high refractive index indicates that the organic thin film is densified and the volatilization ratio of the solvent or additive is high. It can be confirmed that the solvent evaporation rate is excellent even at low temperatures.
  • Example 3 (Production of composition) (Preparation of composition 21) (A) Titanium tetraisopropoxide (Ti (OiPr) 4 ) 0.1M and (b) strontium diisopropoxide (Sr (OiPr) 2 ) in a glove box under a dry nitrogen atmosphere with a moisture concentration of 1 ppm or less 2 mL of a solution was prepared using dehydrated ethylene glycol each containing 0.1 M as a solvent, and 140 ⁇ L of bidentate ligand acetylacetone (2 mol relative to 1 mol of metal alkoxide) was added as a ligand. After that, a liquid formed by bubbling 40 mL of air at 25 ° C.
  • composition 21 50% humidity RH sealed in a glass syringe on a silicon wafer was spin-deposited on a silicon wafer (1000 rpm, 30 seconds), and then dried at 110 ° C. for 30 minutes to form a thickness A 100 nm organic thin film was used as composition 21.
  • compositions 22 and 23 In the preparation of the composition 21, an organic compound having a thickness of 100 nm was prepared in the same manner as the composition 21 except that the two metal alkoxides, the solvent and the ligand were replaced with the two metal alkoxides shown in Table III, the dehydrated solvent and the ligand. Thin films were prepared as compositions 22 and 23.
  • the water absorption of the organic thin film was measured after the compositions 21 to 23 prepared above were further left in a constant temperature and humidity layer at 60 ° C. and 90% for 1 day.
  • the composition of the present invention is hydrolyzed by moisture from outside the system, and releases fluorinated alcohol (R′—OH), which is a water-repellent or hydrophobic substance. This fluorinated alcohol can impart water repellency or hydrophobicity to the organic thin film.
  • compositions 22 and 23 having a fluorinated alkoxide group have a high water absorption function even after being made into an organic thin film with respect to the comparative composition 21.
  • composition according to the present invention having three kinds of metals, Sr—Bi—Ti.
  • the composition of the present invention can form a film that is stable in the air and can be removed by low-temperature drying.
  • the organic thin film formed from the composition of the present invention is preferably an organic material for electronic devices.
  • an electronic device it can apply to color filters etc., such as an organic EL element, a light emitting diode, a liquid crystal element, a solar cell (photoelectric conversion element), a touch panel, and a liquid crystal display device, for example.
  • color filters etc. such as an organic EL element, a light emitting diode, a liquid crystal element, a solar cell (photoelectric conversion element), a touch panel, and a liquid crystal display device, for example.
  • it can be preferably applied to organic EL elements, solar cells, and light emitting diodes.

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Abstract

The present invention addresses the problem of providing a composition which is stable in the atmosphere and is capable of forming a solvent-removable organic thin film by means of drying at a low temperature. A composition according to the present invention contains a metal alkoxide or a metal carboxylate, and is characterized in that the metal alkoxide or the metal carboxylate contains a plurality of kinds of metal atoms, while being a monomer or polymer of a metal alkoxide or a metal carboxylate, which has a fluorinated alkoxy group.

Description

組成物Composition
　本発明は組成物に関し、より詳しくは、大気中でも安定で、低温乾燥で溶媒除去可能な有機薄膜を形成することのできる組成物に関する。 The present invention relates to a composition, and more particularly, to a composition that can form an organic thin film that is stable in the air and can be removed by low-temperature drying.
　複数種の金属原子を含む無機酸化物は、単独の無機酸化物からでは発現しない機能を有する。例えば、チタン酸バリウム（ＢａＴｉＯ３）は、特異的に高い誘電率や強誘電性を有し、コンデンサ等の電子デバイス材料として広く知られている。一般的に、複数種の金属原子を含む無機酸化物は真空成膜により作製され、緻密な膜を形成することができるが、一方で大型の装置が必要であることや、ロール・ｔｏ・ロールのような連続生産に不向きであることから製造上のコスト負荷が高く、大量かつ安価な生産に対しては問題が大きい。 An inorganic oxide containing a plurality of types of metal atoms has a function that does not appear from a single inorganic oxide. For example, barium titanate (BaTiO 3 ) has a specifically high dielectric constant and ferroelectricity and is widely known as an electronic device material such as a capacitor. In general, inorganic oxides containing multiple types of metal atoms are produced by vacuum film formation and can form a dense film. On the other hand, a large apparatus is required, and roll-to-roll Since it is unsuitable for continuous production as described above, the cost burden in manufacturing is high, and the problem is large for mass production at low cost.
　一方、複数種の金属原子を含む無機酸化物をゾル・ゲル法に代表される液相法によって作製する方法もある。この方式では、大気圧下、安価でかつ大面積の製膜が可能となり、これから到来するＩｏＴ（Ｉｎｔｅｒｎｅｔ　ｏｆ　Ｔｈｉｎｇｓ）時代へ向けて、実際には製造コストのボトルネックとなっていた、安価でかつ効果的な封止加工といった課題が解決される。しかし、ゾル・ゲル法によりＢａＴｉＯ３を作製する際に用いる金属アルコキシドが不安定であり、大気中に放置しておくと水分と反応して三次元的な重合が進み、粒子が生じる。特にアルコキシドとアルコール溶媒の系では、重合を抑制することができず粒子サイズが大きくなり最終的に沈殿物を生じてしまい、安定にＢａＴｉＯ３を生産できないことが問題となっていた。 On the other hand, there is also a method for producing an inorganic oxide containing a plurality of types of metal atoms by a liquid phase method typified by a sol-gel method. In this method, it is possible to form a film with a large area under an atmospheric pressure at a low cost. For the coming IoT (Internet of Things) era, it is an inexpensive and cost-effective bottleneck. The problem of effective sealing processing is solved. However, the metal alkoxide used when producing BaTiO 3 by the sol-gel method is unstable, and if left in the atmosphere, it reacts with moisture to promote three-dimensional polymerization and produce particles. In particular, in the alkoxide and alcohol solvent system, the polymerization cannot be suppressed, the particle size becomes large, and a precipitate is finally produced, which makes it impossible to stably produce BaTiO 3 .
　ゾル・ゲル法により複数種の金属からなる無機酸化物を作る別の手段として、特許文献１には、ＴｉアルコキシドとＳｉアルコキシドにキレート化剤を添加させることで金属アルコキシドの水への安定性を向上させ、重合を抑制することができ、大気中でも粒子サイズを小さく抑えることができることが開示されている。しかし、膜とした際、金属酸化物膜の物性を担保するためには溶媒や添加物等の成分は取り除く必要があるが、キレート化剤は一般的に配位力が非常に高いため、これを取り除くためには高温乾燥が必要となりポリエチレンテレフタレート（ＰＥＴ）やポリエチレンナフタレート（ＰＥＮ）に代表される、樹脂を用いたフレキシブル基材への使用が制限される問題がある。 As another means for producing an inorganic oxide composed of a plurality of kinds of metals by the sol-gel method, Patent Document 1 describes the stability of metal alkoxide in water by adding a chelating agent to Ti alkoxide and Si alkoxide. It has been disclosed that polymerization can be suppressed and particle size can be kept small even in the atmosphere. However, when forming a film, it is necessary to remove components such as solvents and additives in order to ensure the physical properties of the metal oxide film, but chelating agents generally have a very high coordinating power. Therefore, there is a problem that the use of the resin on a flexible substrate such as polyethylene terephthalate (PET) or polyethylene naphthalate (PEN) is restricted.
　また、キレート化剤の高配位力により、金属アルコキシドが過度に安定化されてしまうため、膜にした際も反応性が極端に低く、化学吸着を利用した吸水性に代表される機能を阻害してしまうという問題があった。 In addition, since the metal alkoxide is excessively stabilized by the high coordinating power of the chelating agent, the reactivity is extremely low even when it is formed into a film, and the function represented by water absorption utilizing chemical adsorption is inhibited. There was a problem of doing.
特開２０１０－００６９９７号公報JP 2010-006997 A
　本発明は、上記問題・状況に鑑みてなされたものであり、その解決課題は、大気中でも安定で、低温乾燥で溶媒除去可能な有機薄膜を形成することのできる組成物を提供することである。 The present invention has been made in view of the above-described problems and situations, and a problem to be solved is to provide a composition that can form an organic thin film that is stable in the air and can be removed by solvent drying at low temperature. .
　本発明者は、上記課題を解決すべく、上記問題の原因等について検討した結果、複数種の金属を有するアルコキシ基を、フッ化アルコキシ基を有する金属アルコキシドとすることで、金属アルコキシドが安定化し、さらに膜にした際、溶媒を低温での乾燥で留去ができ吸水機能や撥水機能も発現することを見いだし本発明に至った。 As a result of studying the cause of the above-mentioned problem in order to solve the above problems, the present inventor has stabilized the metal alkoxide by changing the alkoxy group having a plurality of types of metals to a metal alkoxide having a fluorinated alkoxy group. Further, when the film was further formed, it was found that the solvent could be distilled off by drying at a low temperature, and that a water absorbing function and a water repellent function were exhibited.
　すなわち、本発明に係る上記課題は、以下の手段により解決される。 That is, the above-mentioned problem according to the present invention is solved by the following means.
　１．金属アルコキシド又は金属カルボキシレートを含有する組成物であって、前記金属アルコキシド又は金属カルボキシレートが、フッ化アルコキシ基を有する、金属アルコキシド又は金属カルボキシレートの単量体若しくは重合体であり、かつ複数種の金属原子を含むことを特徴とする組成物。 1. A composition containing a metal alkoxide or metal carboxylate, wherein the metal alkoxide or metal carboxylate is a metal alkoxide or metal carboxylate monomer or polymer having a fluorinated alkoxy group, and a plurality of types A composition comprising a metal atom.
　２．前記複数種の金属原子が、Ｔｉ－Ｓｉ、Ｔｉ－Ｂａ、Ｔｉ－Ｓｒ、Ｔｉ－Ｃａ、Ｔｉ－Ｍｇ、Ｔｉ－Ｚｒ、Ｔｉ－Ｚｎ、Ｔｉ－Ｃｕ、Ｚｎ－Ｃｕ、Ｚｎ－Ｓｉ、Ｃｕ－Ｓｉ、Ｃａ－Ｂｉ－Ｔｉ、Ｓｒ－Ｂｉ－Ｔａ又はＢｉ－Ｆｅの金属原子の組み合わせのいずれかであることを特徴とする第１項に記載の組成物。
　３．前記金属アルコキシド又は金属カルボキシレートの単量体が、下記一般式（１）で表される構造を有する金属アルコキシド又は金属カルボキシレートを複数種有し、当該複数種の金属アルコキシド又は金属カルボキシレートの金属種がそれぞれ異なることを特徴とする第１項又は第２項に記載の組成物。 2. The plurality of types of metal atoms are Ti—Si, Ti—Ba, Ti—Sr, Ti—Ca, Ti—Mg, Ti—Zr, Ti—Zn, Ti—Cu, Zn—Cu, Zn—Si, Cu—. 2. The composition according to item 1, wherein the composition is any one of a combination of metal atoms of Si, Ca—Bi—Ti, Sr—Bi—Ta, or Bi—Fe.
3. The monomer of the metal alkoxide or metal carboxylate has a plurality of types of metal alkoxide or metal carboxylate having a structure represented by the following general formula (1), and the metal of the plurality of types of metal alkoxide or metal carboxylate The composition according to item 1 or 2, wherein the species are different from each other.
　　一般式（１）
　　　　　Ｍ（ＯＲ１）ｙ（Ｏ－Ｒ）ｘ－ｙ
　（式中、Ｒは、水素原子、炭素数１個以上のアルキル基、アルケニル基、アリール基、シクロアルキル基、アシル基又は複素環基を表す。ただし、Ｒは置換基としてフッ素原子を含む炭素鎖でもよい。Ｍは、金属原子を表す。ＯＲ１は、フッ化アルコキシ基を表す。ｘは金属原子の価数、ｙは１とｘの間の任意な整数を表す。）
　４．前記金属アルコキシド中に含まれるフッ素原子の数が、それぞれの金属アルコキシドの金属原子１個に対し４～１６の範囲内であることを特徴とする第３項に記載の組成物。 General formula (1)
M (OR 1 ) y (OR) xy
(In the formula, R represents a hydrogen atom, an alkyl group having 1 or more carbon atoms, an alkenyl group, an aryl group, a cycloalkyl group, an acyl group, or a heterocyclic group. However, R represents a carbon containing a fluorine atom as a substituent. The chain may be a chain, M represents a metal atom, OR 1 represents a fluorinated alkoxy group, x represents the valence of the metal atom, and y represents any integer between 1 and x.)
4). 4. The composition according to item 3, wherein the number of fluorine atoms contained in the metal alkoxide is in the range of 4 to 16 with respect to one metal atom of each metal alkoxide.
　５．前記金属アルコキシド又は金属カルボキシレート中の金属原子に配位することのできるエーテル結合又はカルボニル基を有する単座配位子を含有することを特徴とする第１項から第４項までのいずれか一項に記載の組成物。 5. The monodentate ligand which has the ether bond or carbonyl group which can be coordinated to the metal atom in the said metal alkoxide or metal carboxylate is contained, Any one of Claim 1 to 4 characterized by the above-mentioned. A composition according to 1.
　６．前記単座配位子が、エーテル結合を有することを特徴とする第５項に記載の組成物。 6. 6. The composition according to item 5, wherein the monodentate ligand has an ether bond.
　７．前記単座配位子が、下記一般式（２）で表されるエーテル結合を有する単座配位子であることを特徴とする第５項又は第６項に記載の組成物。 7. The composition according to Item 5 or 6, wherein the monodentate ligand is a monodentate ligand having an ether bond represented by the following general formula (2).
　　一般式（２）
　　　　Ｒ１－Ｏ－Ｒ２
　（式中、Ｒ１及びＲ２は、それぞれ独立に炭素数２～４のアルキル基を表す。） General formula (2)
R 1 —O—R 2
(In the formula, R 1 and R 2 each independently represents an alkyl group having 2 to 4 carbon atoms.)
　本発明の上記手段により、大気中でも安定で、低温乾燥で溶媒除去可能な有機薄膜を形成することのできる組成物を提供することができる。 By the above means of the present invention, it is possible to provide a composition that can form an organic thin film that is stable in the air and that can be removed by low temperature drying.
　本発明の効果の発現機構ないし作用機構については、明確にはなっていないが、以下のように推察している。 The expression mechanism or action mechanism of the effect of the present invention is not clear, but is presumed as follows.
　一般に金属アルコキシド又は金属カルボキシレートは、水に対する反応性が高いが、本発明に係るフッ化アルコキシ基を有する複数種の金属アルコキシド又は金属カルボキシレートからなるゾル・ゲル液では、水分との反応速度が緩和されるために、重合の進行を抑制することができる。そのため大気中でも粒子サイズを小さく抑えることができる。さらに、フッ化アルコールは金属アルコキシド又は金属カルボキシレートへの配位力はないため、低温乾燥で取り除くことが可能となり、樹脂を用いるフレキシブル基材への使用が実現される。さらに、上記液から作成した膜は吸水性と撥水性又は疎水性を併せ持つ機能性膜として効果を示す。 In general, metal alkoxide or metal carboxylate has high reactivity to water. However, the sol-gel solution comprising a plurality of types of metal alkoxide or metal carboxylate having a fluorinated alkoxy group according to the present invention has a reaction rate with moisture. Since it is relaxed, the progress of the polymerization can be suppressed. Therefore, the particle size can be kept small even in the atmosphere. Furthermore, since the fluorinated alcohol has no coordination power to the metal alkoxide or the metal carboxylate, it can be removed by low-temperature drying, and use for a flexible substrate using a resin is realized. Furthermore, a film prepared from the above liquid is effective as a functional film having both water absorption and water repellency or hydrophobicity.
　フッ化アルコキシ基を有する、金属アルコキシド又は金属カルボキシレートと水分との反応速度が緩和される理由は、中心金属周りに存在するフッ素原子が疎水効果を示すことで中心金属周りの水分の頻度因子を低減させることができるからであると考えられる。結果として大気中でもある程度重合を抑制することができ、粒子サイズを小さく抑えることができるものと考えられる。例えば、水と反応性が高いＴｉアルコキシドは、フッ化アルコキシ基を有する、金属アルコキシド又は金属カルボキシレートとすることで、反応性を抑えることができ、さらに金属アルコキシド又は金属カルボキシレートをＴｉ以外の例えばＳｉを用い複数種とすることで、金属アルコキシド又は金属カルボキシレートと水分との反応速度をコントロールすることができるものである。 The reason why the reaction rate between the metal alkoxide or metal carboxylate having a fluorinated alkoxy group and moisture is relaxed is that the fluorine atom present around the central metal exhibits a hydrophobic effect, and the frequency factor of moisture around the central metal is reduced. This is considered to be because it can be reduced. As a result, it is considered that polymerization can be suppressed to some extent even in the atmosphere, and the particle size can be suppressed to a small value. For example, Ti alkoxide having high reactivity with water can suppress the reactivity by using a metal alkoxide or metal carboxylate having a fluorinated alkoxy group, and the metal alkoxide or metal carboxylate other than Ti, for example, By using Si as a plurality of types, the reaction rate between the metal alkoxide or metal carboxylate and moisture can be controlled.
　またこのように複数の金属種を有する金属アルコキシド又は金属カルボキシレートを用いることで、単独の金属酸化物からは予想が困難な特異的な性能を有する複数の金属種を有する金属酸化物を容易に得ることができる。 In addition, by using a metal alkoxide or metal carboxylate having a plurality of metal species in this way, a metal oxide having a plurality of metal species having specific performance that is difficult to predict from a single metal oxide can be easily obtained. Can be obtained.
　本発明の組成物は、金属アルコキシド又は金属カルボキシレートを含有する組成物であって、前記金属アルコキシド又は金属カルボキシレートが、フッ化アルコキシ基を有する、金属アルコキシド又は金属カルボキシレートの単量体若しくは重合体であり、かつ複数種の金属原子を含むことを特徴とする。この特徴は、下記各実施態様に共通する技術的特徴である。 The composition of the present invention is a composition containing a metal alkoxide or a metal carboxylate, wherein the metal alkoxide or metal carboxylate has a fluorinated alkoxy group. It is a combination and contains a plurality of types of metal atoms. This feature is a technical feature common to the following embodiments.
　本発明の実施態様としては、本発明の効果発現の観点から、前記複数種の金属原子が、Ｔｉ－Ｓｉ、Ｔｉ－Ｂａ、Ｔｉ－Ｓｒ、Ｔｉ－Ｃａ、Ｔｉ－Ｍｇ、Ｔｉ－Ｚｒ、Ｔｉ－Ｚｎ、Ｔｉ－Ｃｕ、Ｚｎ－Ｃｕ、Ｚｎ－Ｓｉ、Ｃｕ－Ｓｉ、Ｃａ－Ｂｉ－Ｔｉ、Ｓｒ－Ｂｉ－Ｔａ又はＢｉ－Ｆｅの金属原子の組み合わせのいずれかであることが、液安定性と吸水性の観点から好ましい。 In an embodiment of the present invention, from the viewpoint of manifesting the effect of the present invention, the plurality of types of metal atoms are Ti—Si, Ti—Ba, Ti—Sr, Ti—Ca, Ti—Mg, Ti—Zr, Ti. It is liquid stable to be any combination of metal atoms of —Zn, Ti—Cu, Zn—Cu, Zn—Si, Cu—Si, Ca—Bi—Ti, Sr—Bi—Ta or Bi—Fe. From the viewpoint of water absorption.
　また、前記金属アルコキシド又は金属カルボキシレートの単量体が、前記一般式（１）で表される構造を有する金属アルコキシド又は金属カルボキシレートを複数種有し、当該複数種の金属アルコキシド又は金属カルボキシレートの金属種がそれぞれ異なることが、単独の無機酸化物からでは発現しない効果が得られることから、好ましい。 The monomer of the metal alkoxide or metal carboxylate has a plurality of types of metal alkoxides or metal carboxylates having the structure represented by the general formula (1), and the plurality of types of metal alkoxides or metal carboxylates. It is preferable that the metal species are different from each other because an effect that does not appear from a single inorganic oxide is obtained.
　さらに、本発明においては、前記金属アルコキシド中に含まれるフッ素原子の数が、それぞれの金属アルコキシドの金属原子１個に対し４～１６の範囲内であることが好ましい。これにより、組成物を重縮合して得られる膜の撥水性又は疎水性を大きくすることができる。 Furthermore, in the present invention, the number of fluorine atoms contained in the metal alkoxide is preferably in the range of 4 to 16 with respect to one metal atom of each metal alkoxide. Thereby, the water repellency or hydrophobicity of the film obtained by polycondensation of the composition can be increased.
　また、前記金属アルコキシド又は金属カルボキシレート中の金属原子に配位することのできるエーテル結合又はカルボニル基を有する単座配位子を含有することが、液安定性の効果が得られることから、好ましい。 In addition, it is preferable to contain a monodentate ligand having an ether bond or a carbonyl group that can be coordinated to a metal atom in the metal alkoxide or metal carboxylate because a liquid stability effect can be obtained.
　前記単座配位子が、エーテル結合を有することが好ましく、さらに、前記一般式（２）で表されるエーテル結合を有する単座配位子であることが好ましい。 The monodentate ligand preferably has an ether bond, and more preferably a monodentate ligand having an ether bond represented by the general formula (2).
　以下、本発明とその構成要素、及び本発明を実施するための形態・態様について詳細な説明をする。なお、本願において、「～」は、その前後に記載される数値を下限値及び上限値として含む意味で使用する。 Hereinafter, the present invention, its components, and modes and modes for carrying out the present invention will be described in detail. In the present application, “˜” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
　《組成物の概要》
　本発明の組成物は、金属アルコキシド又は金属カルボキシレートを含有する組成物であって、前記金属アルコキシド又は金属カルボキシレートが、フッ化アルコキシ基を有する、金属アルコキシド又は金属カルボキシレートの単量体若しくは重合体であり、かつ複数種の金属原子を含むことを特徴とする。 <Outline of composition>
The composition of the present invention is a composition containing a metal alkoxide or a metal carboxylate, wherein the metal alkoxide or metal carboxylate has a fluorinated alkoxy group. It is a combination and contains a plurality of types of metal atoms.
　このような構成により、大気中でも安定で、低温乾燥で溶媒除去可能な膜を形成することのできる組成物を実現可能にすることができる。 Such a configuration makes it possible to realize a composition that can form a film that is stable in the air and that can be removed by solvent drying at low temperature.
　〔金属アルコキシド又は金属カルボキシレート〕
　本発明に係る金属アルコキシド又は金属カルボキシレートは、フッ化アルコキシ基を有する、金属アルコキシド又は金属カルボキシレートの単量体若しくは重合体であり、かつ複数種の金属原子を含む。 [Metal alkoxide or metal carboxylate]
The metal alkoxide or metal carboxylate according to the present invention is a metal alkoxide or metal carboxylate monomer or polymer having a fluorinated alkoxy group, and contains a plurality of types of metal atoms.
　本発明の組成物は、金属アルコキシド又は金属カルボキシレートを過剰のフッ化アルコール存在下で加アルコール分解して、アルコール置換した有機金属酸化物又は有機金属酸化物の重縮合体である。その際に、ヒドロキシ基のβ位にフッ素原子が置換した長鎖アルコールを用いることが好ましい。加アルコール分解する際、複数の金属アルコキシド又は金属カルボキシレートを別々に処理しても良いし、複数の金属アルコキシド又は金属カルボキシレートを混合して同時に処理しても良い。 The composition of the present invention is a polycondensate of an organic metal oxide or an organic metal oxide obtained by alcohololysis of a metal alkoxide or metal carboxylate in the presence of an excess of fluorinated alcohol to replace the alcohol. At that time, it is preferable to use a long-chain alcohol in which a fluorine atom is substituted at the β-position of the hydroxy group. When the alcoholysis is performed, a plurality of metal alkoxides or metal carboxylates may be treated separately, or a plurality of metal alkoxides or metal carboxylates may be mixed and treated simultaneously.
　一方、前記有機金属酸化物は、焼結や紫外線を照射することで、ゾル・ゲル反応を促進し重縮合体を形成することができる。その際、前記ヒドロキシ基のβ位にフッ素原子が置換した長鎖アルコールを用いると、フッ素の撥水効果又は疎水効果により金属アルコキシド又は金属カルボキシレート中の金属周りに存在する水分の頻度因子を減少させることで、加水分解速度が減少し、当該現象を利用することで３次元の重合反応を抑え、所望の有機金属酸化物を含有する均一で稠密な有機薄膜を形成しうるという特徴がある。 On the other hand, the organometallic oxide can promote a sol-gel reaction and form a polycondensate by irradiating with sintering or ultraviolet rays. In this case, when a long chain alcohol having a fluorine atom substituted at the β-position of the hydroxy group is used, the frequency factor of moisture present around the metal in the metal alkoxide or metal carboxylate is reduced by the water repellent effect or hydrophobic effect of fluorine. Thus, there is a feature that the hydrolysis rate is reduced, and by utilizing the phenomenon, a three-dimensional polymerization reaction can be suppressed and a uniform and dense organic thin film containing a desired organometallic oxide can be formed.
　本発明の組成物に係る有機金属酸化物は、以下の反応スキームＩ又は反応スキームIIに示すものである。本発明においては、金属アルコキシド又は金属カルボキシレートが複数種の金属原子含む。具体的には、金属アルコキシド又は金属カルボキシレートを複数種有し当該金属アルコキシド又は金属カルボキシレートの金属種がそれぞれ異なることが好ましい。以下の反応スキームＩ～IIIでは、金属種が２種の場合であり、Ｍ１及びＭ２は、
それぞれ異なる金属種を表す。本発明では、金属アルコキシドは、金属種がそれぞれ異なる複数の金属アルコキシドを用いるため、焼結後の金属酸化物は複数の金属種を含む。 The organometallic oxide according to the composition of the present invention is shown in the following reaction scheme I or reaction scheme II. In the present invention, the metal alkoxide or metal carboxylate contains a plurality of types of metal atoms. Specifically, it is preferable that a plurality of types of metal alkoxides or metal carboxylates are included and the metal types of the metal alkoxides or metal carboxylates are different. In the following reaction schemes I to III, there are two metal species, and M 1 and M 2 are
Each represents a different metal species. In the present invention, since the metal alkoxide uses a plurality of metal alkoxides having different metal species, the sintered metal oxide includes a plurality of metal species.
　なお、焼結後の有機金属酸化物の重縮合体の構造式において、「Ｏ－Ｍ１」又は「Ｏ－Ｍ２」部のＭ１又はＭ２は、さらに置換基を有しているが、省略してある。 In the structural formula of the polycondensate of organometallic oxide after sintering, M 1 or M 2 in the “OM 1 ” or “OM 2 ” part further has a substituent. It is omitted.
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
　上記有機金属酸化物が、紫外線照射により重縮合して形成された有機薄膜は、以下の反応スキームIIIによって、系外からの水分（Ｈ２Ｏ）によって加水分解し、撥水性又は疎
水性物質であるフッ化アルコール（Ｒ′－ＯＨ）を放出する。 The organic thin film formed by polycondensation of the organometallic oxide by ultraviolet irradiation is hydrolyzed by moisture (H 2 O) from outside the system according to the following reaction scheme III, and is made of a water repellent or hydrophobic substance. Releases some fluorinated alcohol (R'-OH).
　すなわち、本発明の組成物は、加水分解によって生成したフッ化アルコールが撥水性又は疎水性のため、水分との反応により撥水機能又は疎水機能が付加されるという特徴を有する。 That is, the composition of the present invention is characterized in that a water-repellent function or a hydrophobic function is added by reaction with moisture because the fluorinated alcohol produced by hydrolysis is water-repellent or hydrophobic.
　なお、下記構造式において、「Ｏ－Ｍ１」又は「Ｏ－Ｍ２」部のＭ１又はＭ２は、さらに置換基を有しているが、省略してある。 In the structural formula below, M 1 or M 2 in the “OM 1 ” or “OM 2 ” part further has a substituent, but is omitted.
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
　本発明に係る金属アルコキシド又は金属カルボキシレートの単量体は、下記一般式（１）で表される構造を有する金属アルコキシド又は金属カルボキシレートを複数種有し、当該複数種の金属アルコキシド又は金属カルボキシレートの金属種がそれぞれ異なることが好ましい。また、それぞれ、下記一般式（１）で表される構造を有する金属種の異なる複数の金属アルコキシド又は金属カルボキシレートから製造された下記一般式（３）で表される構造を有する金属種の異なる複数の金属アルコキシド又は金属カルボキシレートを主成分として含有することが好ましい。「主成分」とは、前記組成物の全体の質量のうち、７０質量％以上が撥水性又は疎水性物質を放出する前記金属アルコキシド又は金属カルボキシレートの総計であることが好ましく、より好ましくは８０質量％以上、特に好ましくは９０質量％以上であることをいう。 The metal alkoxide or metal carboxylate monomer according to the present invention includes a plurality of metal alkoxides or metal carboxylates having a structure represented by the following general formula (1), and the plurality of types of metal alkoxides or metal carboxylates. The metal species of the rate are preferably different from each other. In addition, each of the metal species having a structure represented by the following general formula (3) manufactured from a plurality of metal alkoxides or metal carboxylates having different metal species having a structure represented by the following general formula (1) is different. It is preferable to contain a plurality of metal alkoxides or metal carboxylates as a main component. The “main component” is preferably a total of the metal alkoxide or metal carboxylate in which 70% by mass or more of the total mass of the composition releases water-repellent or hydrophobic substances, and more preferably 80%. It means mass% or more, particularly preferably 90 mass% or more.
　　一般式（１）
　　　Ｍ（ＯＲ１）ｙ（Ｏ－Ｒ）ｘ－ｙ
　（式中、Ｒは、水素原子、炭素数１個以上のアルキル基、アルケニル基、アリール基、シクロアルキル基、アシル基又は複素環基を表す。ただし、Ｒは置換基としてフッ素原子を含む炭素鎖でもよい。Ｍは、金属原子を表す。ＯＲ１は、フッ化アルコキシ基を表す。ｘは金属原子の価数、ｙは１とｘの間の任意な整数を表す。）
　　一般式（３）
　　　Ｒ－［Ｍ（ＯＲ１）ｙ（Ｏ－）ｘ－ｙ］ｎ－Ｒ
　（式中、Ｒは、水素原子、炭素数１個以上のアルキル基、アルケニル基、アリール基、シクロアルキル基、アシル基、アルコキシ基、又は複素環基を表す。ただし、Ｒは置換基としてフッ素原子を含む炭素鎖でもよい。Ｍは、金属原子を表す。ＯＲ１は、フッ化アルコキシ基を表す。ｘは金属原子の価数、ｙは１とｘの間の任意な整数を表す。ｎは重縮合度をそれぞれ表す。）
　本発明に係る有機金属酸化物は、ゾル・ゲル法を用いて作製できるものであれば特に制限はされず、例えば、「ゾル－ゲル法の科学」（作花済夫著、アグネ承風社）Ｐ１３及びＰ２０に紹介されている金属、リチウム（Ｌｉ）、ナトリウム（Ｎａ）、マグネシウム（Ｍｇ）、銅（Ｃｕ）、カルシウム（Ｃａ）、ストロンチウム（Ｓｒ）、ビスマス（Ｂｉ）、ハフニウム（Ｈｆ）、ニオブ（Ｎｂ）、バリウム（Ｂａ）、亜鉛（Ｚｎ）、ホウ素（Ｂ）、アルミニウム（Ａｌ）、ガリウム（Ｇａ）、イットリウム（Ｙ）、ケイ素（Ｓｉ）、ゲルマニウム（Ｇｅ）、鉛（Ｐｂ）、リン（Ｐ）、アンチモン（Ｓｂ）、バナジウム（Ｖ）、タンタル（Ｔａ）、タングステン（Ｗ）、ランタン（Ｌａ）、ネオジウム（Ｎｄ）、チタン（Ｔｉ）、鉄（Ｆｅ）、ジルコニウム（Ｚｒ）、又は銀（Ａｇ）の金属原子からを目的により、任意に選ぶことができる。 General formula (1)
M (OR 1 ) y (OR) xy
(In the formula, R represents a hydrogen atom, an alkyl group having 1 or more carbon atoms, an alkenyl group, an aryl group, a cycloalkyl group, an acyl group, or a heterocyclic group. However, R represents a carbon containing a fluorine atom as a substituent. The chain may be a chain, M represents a metal atom, OR 1 represents a fluorinated alkoxy group, x represents the valence of the metal atom, and y represents any integer between 1 and x.)
General formula (3)
R— [M (OR 1 ) y (O—) xy ] n —R
(In the formula, R represents a hydrogen atom, an alkyl group having 1 or more carbon atoms, an alkenyl group, an aryl group, a cycloalkyl group, an acyl group, an alkoxy group, or a heterocyclic group. However, R represents fluorine as a substituent. It may be a carbon chain containing atoms, M represents a metal atom, OR 1 represents a fluorinated alkoxy group, x represents a valence of the metal atom, y represents an arbitrary integer between 1 and x, n Represents the degree of polycondensation.)
The organometallic oxide according to the present invention is not particularly limited as long as it can be produced by using a sol-gel method. For example, “Science of Sol-Gel Method” (Sakuo Sakuo, Agne Jofu Co., Ltd.) ) Metals introduced in P13 and P20, lithium (Li), sodium (Na), magnesium (Mg), copper (Cu), calcium (Ca), strontium (Sr), bismuth (Bi), hafnium (Hf) Niobium (Nb), Barium (Ba), Zinc (Zn), Boron (B), Aluminum (Al), Gallium (Ga), Yttrium (Y), Silicon (Si), Germanium (Ge), Lead (Pb) , Phosphorus (P), antimony (Sb), vanadium (V), tantalum (Ta), tungsten (W), lanthanum (La), neodymium (Nd), titanium (Ti), iron (Fe), Rukoniumu (Zr), or the purpose of the metal atoms of silver (Ag), can be chosen arbitrarily.
　本発明では、一般式（１）で表される構造を有する金属アルコキシド又は金属カルボキシレートを複数種有し、当該複数種の金属アルコキシド又は金属カルボキシレートの金属種がそれぞれ異なることが好ましい。複数種の金属原子が、Ｔｉ－Ｓｉ、Ｔｉ－Ｂａ、Ｔｉ－Ｓｒ、Ｔｉ－Ｃａ、Ｔｉ－Ｍｇ、Ｔｉ－Ｚｒ、Ｔｉ－Ｚｎ、Ｔｉ－Ｃｕ、Ｚｎ－Ｃｕ、Ｚｎ－Ｓｉ、Ｃｕ－Ｓｉ、Ｃａ－Ｂｉ－Ｔｉ、Ｓｒ－Ｂｉ－Ｔａ又はＢｉ－Ｆｅの金属原子の組み合わせのいずれかであることが、液安定性と吸水性の観点から好ましい。 In the present invention, it is preferable that a plurality of types of metal alkoxides or metal carboxylates having a structure represented by the general formula (1) are provided, and the metal types of the plurality of types of metal alkoxides or metal carboxylates are different from each other. Multiple kinds of metal atoms are Ti—Si, Ti—Ba, Ti—Sr, Ti—Ca, Ti—Mg, Ti—Zr, Ti—Zn, Ti—Cu, Zn—Cu, Zn—Si, Cu—Si. , Ca—Bi—Ti, Sr—Bi—Ta, or a combination of Bi—Fe is preferable from the viewpoint of liquid stability and water absorption.
　上記一般式（１）及び一般式（３）において、ＯＲ１はフッ化アルコキシ基を表す。 In the above general formula (1) and general formula (3), OR 1 represents a fluorinated alkoxy group.
　Ｒ１は少なくとも一つのフッ素原子が置換したアルキル基を表す。各置換基の具体例は後述する。 R 1 represents an alkyl group substituted with at least one fluorine atom. Specific examples of each substituent will be described later.
　また、金属アルコキシド中に含まれるフッ素原子の数が、前記金属原子１個に対し４～１６の範囲内であることが本発明の組成物を重縮合して得られる膜の撥水性又は疎水性を大きくすることができることから好ましい。 Further, the water repellency or hydrophobicity of the film obtained by polycondensation of the composition of the present invention that the number of fluorine atoms contained in the metal alkoxide is in the range of 4 to 16 per one metal atom. Can be increased, which is preferable.
　Ｒは水素原子、炭素数１個以上のアルキル基、アルケニル基、アリール基、シクロアルキル基、アシル基、アルコキシ基、又は複素環基を表す。又はそれぞれの基の水素原子の少なくとも一部をハロゲンで置換したものでもよい。また、ポリマーでもよい。 R represents a hydrogen atom, an alkyl group having 1 or more carbon atoms, an alkenyl group, an aryl group, a cycloalkyl group, an acyl group, an alkoxy group, or a heterocyclic group. Or what substituted at least one part of the hydrogen atom of each group with the halogen may be used. Moreover, a polymer may be sufficient.
　アルキル基は置換又は未置換のものであるが、具体例としては、メチル基、エチル基、プロピル基、ブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基、トリデシル基、テトラデシル基、ペンタデシル基、ヘキサデシル基、ヘプタデシル基、オクタデシル基、ノナデシル基、イコシル基、ヘンイコシル基、ドコシル等であるが、好ましくは炭素数が８以上のものがよい。またこれらのオリゴマー、ポリマーでもよい。 Alkyl groups are substituted or unsubstituted, and specific examples include methyl, ethyl, propyl, butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl. Group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group, heicosyl group, docosyl, etc., preferably carbon The number of 8 or more is good. These oligomers and polymers may also be used.
　アルケニル基は、置換又は未置換のもので、具体例としては、ビニル基、アリル基、ブテニル基、ペンテニル基、ヘキシセニル基等があり、好ましくは炭素数が８以上のものがよい。またこれらのオリゴマー又はポリマーでもよい。 The alkenyl group is substituted or unsubstituted, and specific examples include a vinyl group, an allyl group, a butenyl group, a pentenyl group, a hexenyl group, and the like, and preferably those having 8 or more carbon atoms. These oligomers or polymers may also be used.
　アリール基は置換又は未置換のもので、具体例としては、フェニル基、トリル基、４－シアノフェニル基、ビフェニル基、ｏ，ｍ，ｐ－テルフェニル基、ナフチル基、アントラニル基、フェナントレニル基、フルオレニル基、９－フェニルアントラニル基、９，１０－ジフェニルアントラニル基、ピレニル基等があり、好ましくは炭素数が８以上のものがよい。また、これらのオリゴマー又はポリマーでもよい。 The aryl group is substituted or unsubstituted, and specific examples include phenyl group, tolyl group, 4-cyanophenyl group, biphenyl group, o, m, p-terphenyl group, naphthyl group, anthranyl group, phenanthrenyl group, There are a fluorenyl group, a 9-phenylanthranyl group, a 9,10-diphenylanthranyl group, a pyrenyl group, and the like, preferably those having 8 or more carbon atoms. These oligomers or polymers may also be used.
　置換又は未置換のアルコキシ基の具体例としては、メトキシ基、ｎ－ブトキシ基、ｔｅｒｔ－ブトキシ基、トリクロロメトキシ基、トリフルオロメトキシ基等でありが好ましくは炭素数が８以上のものがよい。また、これらのオリゴマー、ポリマーでもよい。 Specific examples of the substituted or unsubstituted alkoxy group include a methoxy group, an n-butoxy group, a tert-butoxy group, a trichloromethoxy group, and a trifluoromethoxy group, and preferably those having 8 or more carbon atoms. These oligomers and polymers may also be used.
　置換又は未置換のシクロアルキル基の具体例としては、シクロペンチル基、シクロヘキシル基、ノルボナン基、アダマンタン基、４－メチルシクロヘキシル基、４－シアノシクロヘキシル基等であり好ましくは炭素数が８以上のものがよい。また、これらのオリゴマー又はポリマーでもよい。 Specific examples of the substituted or unsubstituted cycloalkyl group include a cyclopentyl group, a cyclohexyl group, a norbonane group, an adamantane group, a 4-methylcyclohexyl group, a 4-cyanocyclohexyl group, and preferably those having 8 or more carbon atoms. Good. These oligomers or polymers may also be used.
　置換又は未置換の複素環基の具体例としては、ピロール基、ピロリン基、ピラゾール基、ピラゾリン基、イミダゾール基、トリアゾール基、ピリジン基、ピリダジン基、ピリミジン基、ピラジン基、トリアジン基、インドール基、ベンズイミダゾール基、プリン基、キノリン基、イソキノリン基、シノリン基、キノキサリン基、ベンゾキノリン基、フルオレノン基、ジシアノフルオレノン基、カルバゾール基、オキサゾール基、オキサジアゾール基、チアゾール基、チアジアゾール基、ベンゾオキサゾール基、ベンゾチアゾール基、ベンゾトリアゾール基、ビスベンゾオキサゾール基、ビスベンゾチアゾール基、ビスベンゾイミダゾール基等がある。またこれらのオリゴマー又はポリマーでもよい。 Specific examples of the substituted or unsubstituted heterocyclic group include pyrrole group, pyrroline group, pyrazole group, pyrazoline group, imidazole group, triazole group, pyridine group, pyridazine group, pyrimidine group, pyrazine group, triazine group, indole group, Benzimidazole group, purine group, quinoline group, isoquinoline group, sinoline group, quinoxaline group, benzoquinoline group, fluorenone group, dicyanofluorenone group, carbazole group, oxazole group, oxadiazole group, thiazole group, thiadiazole group, benzoxazole group Benzothiazole group, benzotriazole group, bisbenzoxazole group, bisbenzothiazole group, bisbenzimidazole group and the like. These oligomers or polymers may also be used.
　置換又は未置換のアシル基の具体例としては、ホルミル基、アセチル基、プロピオニル基、ブチリル基、イソブチリル基、バレリル基、イソバレリル基、ピバロイル基、ラウロイル基、ミリストイル基、パルミトイル基、ステアロイル基、オキサリル基、マロニル基、スクシニル基、グルタリル基、アジポイル基、ピメロイル基、スベロイル基、アゼラオイル基、セバコイル基、アクリロイル基、プロピオロイル基、メタクリロイル基、クロトノイル基、イソクロトノイル基、オレオイル基、エライドイル基、マレオイル基、フマロイル基、シトラコノイル基、メサコノイル基、カンホロイル基、ベンゾイル基、フタロイル基、イソフタロイル基、テレフタロイル基、ナフトイル基、トルオイル基、ヒドロアトロポイル基、アトロポイル基、シンナモイル基、フロイル基、テノイル基、ニコチノイル基、イソニコチノイル基、グリコロイル基、ラクトイル基、グリセロイル基、タルトロノイル基、マロイル基、タルタロイル基、トロポイル基、ベンジロイル基、サリチロイル基、アニソイル基、バニロイル基、ベラトロイル基、ピペロニロイル基、プロトカテクオイル基、ガロイル基、グリオキシロイル基、ピルボイル基、アセトアセチル基、メソオキサリル基、メソオキサロ基、オキサルアセチル基、オキサルアセト基、レブリノイル基これらのアシル基にフッ素、塩素、臭素、又はヨウ素などが置換してもよい。好ましくは、アシル基の炭素は８以上良い。また、これらのオリゴマー又はポリマーでもよい。 Specific examples of the substituted or unsubstituted acyl group include formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl, isovaleryl, pivaloyl, lauroyl, myristoyl, palmitoyl, stearoyl, oxalyl Group, malonyl group, succinyl group, glutaryl group, adipoyl group, pimeloyl group, suberoyl group, azelaoil group, sebacoyl group, acryloyl group, propioloyl group, methacryloyl group, crotonoyl group, isocrotonoyl group, oleoyl group, elidoyl group, maleoyl group , Fumaroyl group, citraconoyl group, mesaconoyl group, camphoroyl group, benzoyl group, phthaloyl group, isophthaloyl group, terephthaloyl group, naphthoyl group, toluoyl group, hydroatropoyl group, atropoyl group Cinnamoyl group, furoyl group, tenoyl group, nicotinoyl group, isonicotinoyl group, glycoloyl group, lactoyl group, glyceroyl group, tartronoyl group, maloyl group, tartaloyl group, tropoyl group, benzyloyl group, salicyloyl group, anisoyl group, vanilloyl group, veratroyl group , Piperoniloyl group, protocatechuyl group, galloyl group, glyoxyloyl group, pyrvoyl group, acetoacetyl group, mesooxalyl group, mesooxalo group, oxalacetyl group, oxalaceto group, levulinoyl group Fluorine, chlorine, bromine on these acyl groups Or iodine or the like may be substituted. Preferably, the acyl group has 8 or more carbon atoms. These oligomers or polymers may also be used.
　本発明に係る一般式（１）で表される構造を有する有機金属酸化物を形成するための、金属アルコキシド、金属カルボキシレート及びフッ化アルコールの具体的な組み合わせについて、以下に例示する。ただし、本発明は、これに限定されるものではない。 Specific examples of the combination of metal alkoxide, metal carboxylate, and fluorinated alcohol for forming the organometallic oxide having the structure represented by the general formula (1) according to the present invention are illustrated below. However, the present invention is not limited to this.
　前記金属種の異なる複数の金属アルコキシド、金属カルボキシレートのそれぞれとフッ化アルコール（Ｒ′－ＯＨ）は以下の反応スキームIVによって、本発明に係る有機金属酸化物となる。このフッ化アルコールとの反応をさらに繰り返すことにより、ｎ個のフッ化アルコキシ基が置換した金属酸化物とすることができる。ここで、（Ｒ′－ＯＨ）としては、以下のＦ－１～Ｆ－１６の構造が例示される。 Each of the plurality of metal alkoxides and metal carboxylates having different metal species and the fluorinated alcohol (R′-OH) become the organometallic oxide according to the present invention by the following reaction scheme IV. By further repeating the reaction with the fluorinated alcohol, a metal oxide substituted with n fluoroalkoxy groups can be obtained. Here, (R′—OH) is exemplified by the following structures F-1 to F-16.
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
　本発明に係る金属アルコキシド又は金属カルボキシレートは、以下のＭ（ＯＲ）ｎ又はＭ（ＯＣＯＲ）ｎに示す化合物が例示され、本発明に係る有機金属酸化物は、前記（Ｒ′－ＯＨ：Ｆ－１～Ｆ－１６）との組み合わせにより、下記例示化合物番号１～１７０の構造を有する化合物（下記例示化合物Ｉ～IV参照。）となる。本発明に係る個々の金属アルコキシド又は金属カルボキシレートは、これに限定されるものではない。
本発明では、上記した金属アルコキシド又は金属カルボキシレートを複数種有し、当該複数種の金属アルコキシド又は金属カルボキシレート中の金属が異なることが好ましい。 Examples of the metal alkoxide or metal carboxylate according to the present invention include the following compounds represented by M (OR) n or M (OCOR) n, and the organometallic oxide according to the present invention includes the above (R′—OH: F In combination with -1 to F-16), compounds having the structures of the following exemplified compound numbers 1 to 170 (see the exemplified compounds I to IV below) are obtained. The individual metal alkoxide or metal carboxylate according to the present invention is not limited to this.
In this invention, it is preferable to have two or more types of the above-mentioned metal alkoxide or metal carboxylate, and the metals in the plurality of types of metal alkoxide or metal carboxylate are different.
　また、当該金属は、２～３種であることが好ましい。金属種の異なるそれぞれの金属アルコキシド又は金属カルボキシレートは、全体の金属アルコキシド又は金属カルボキシレートの総量に対して、それぞれ１０～９０モル％の範囲内であることが好ましい。 In addition, it is preferable that the metal is 2 to 3 kinds. Each metal alkoxide or metal carboxylate having a different metal species is preferably in the range of 10 to 90 mol% with respect to the total amount of the entire metal alkoxide or metal carboxylate.
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000009
　本発明に係る有機金属酸化物を製造する有機金属酸化物の製造方法は、金属アルコキシド又は金属カルボキシレートとフッ化アルコールの混合液を用いて製造することが好ましい。 The method for producing an organometallic oxide for producing the organometallic oxide according to the present invention is preferably produced using a mixed solution of a metal alkoxide or metal carboxylate and a fluorinated alcohol.
　前記有機金属酸化物の重縮合体が有機薄膜を形成し、以下の反応スキームＶにより、水分を吸収して撥水性又は疎水性物質であるフッ化アルコールを放出する。 The organic metal oxide polycondensate forms an organic thin film, which absorbs moisture and releases fluorinated alcohol, which is a water-repellent or hydrophobic substance, according to Reaction Scheme V below.
　反応スキームＶでは、金属種をＴｉで代表させたが、複数種の金属を用いても同様にＲ′－ＯＨを放出することができる。なお、下記構造式において、「Ｏ－Ｔｉ」部の「Ｔｉ」は、さらに置換基を有しているが、省略してある。
Figure JPOXMLDOC01-appb-C000010
 In Reaction Scheme V, the metal species is represented by Ti, but R′—OH can be similarly released using a plurality of metals. In the structural formula below, “Ti” in the “O—Ti” part further has a substituent, but is omitted.
Figure JPOXMLDOC01-appb-C000010
　〔配位子〕
　本発明の組成物は、配位子を含有し、前記配位子が、本発明に係る金属アルコキシド又は金属カルボキシレート中の金属原子に配位することのできるエーテル結合又はカルボニル基を有する単座配位子であることを特徴とする。このように単座配位子を用いることで、本発明の組成物が安定化し、過度の重合が抑えられ、かつ、溶媒を容易に除去でき、膜にしたとき吸水機能と撥水機能又は疎水機能を発現させることができる。 [Ligand]
The composition of the present invention contains a ligand, and the ligand is monodentate having an ether bond or a carbonyl group capable of coordinating to a metal atom in the metal alkoxide or metal carboxylate according to the present invention. It is characterized by being a rank. By using a monodentate ligand in this way, the composition of the present invention is stabilized, excessive polymerization is suppressed, and the solvent can be easily removed. Can be expressed.
　すなわち、本発明に係る単座配位性の化学種をフッ素置換された金属アルコキシド又は金属カルボキシレートに添加することで、単座配位性の化学種が金属アルコキシド又は金属カルボキシレートの中心金属に配位する。結果的に金属アルコキシド又は金属カルボキシレートがさらに安定化し過度の重合を抑えられ、大気中での粒子サイズを小さく抑えることができる。さらに、単座配位性の化学種はキレート化剤よりも配位能力が低いため、より低温での乾燥で留去ができ、さらに膜にした際に吸水機能と撥水機能又は疎水機能も発現することができる。 That is, by adding the monodentate chemical species according to the present invention to the fluorine-substituted metal alkoxide or metal carboxylate, the monodentate chemical species is coordinated to the central metal of the metal alkoxide or metal carboxylate. To do. As a result, the metal alkoxide or metal carboxylate is further stabilized and excessive polymerization can be suppressed, and the particle size in the atmosphere can be suppressed small. In addition, monodentate species are less coordinating than chelating agents, so they can be distilled off by drying at lower temperatures, and when they are made into membranes, they also exhibit water absorption, water repellency or hydrophobic functions. can do.
　このような、金属アルコキシド又は金属カルボキシレート中の金属原子に配位することのできるエーテル結合又はカルボニル基としては、ジブチルエーテルが挙げられる。 Such an ether bond or carbonyl group that can be coordinated to a metal atom in a metal alkoxide or metal carboxylate includes dibutyl ether.
　このような単座配位子は、下記一般式（２）で表されるエーテル結合を有する単座配位子であることが好ましい。 Such a monodentate ligand is preferably a monodentate ligand having an ether bond represented by the following general formula (2).
　　一般式（２）
　　　　Ｒ１－Ｏ－Ｒ２
　（式中、Ｒ１及びＲ２は、それぞれ独立に炭素数２～４のアルキル基を表す。）
　このようなエーテル結合を有する単座配位としては、ジエチルエーテル、ジプロピルエーテル、ジブチルエーテル及びプロピルブチルエーテルなどを挙げることができる。 General formula (2)
R 1 —O—R 2
(In the formula, R 1 and R 2 each independently represents an alkyl group having 2 to 4 carbon atoms.)
Examples of the monodentate coordination having an ether bond include diethyl ether, dipropyl ether, dibutyl ether, and propylbutyl ether.
　単座配位子は、金属アルコキシド又は金属カルボキシレート１モルに対して０．１～４モルの範囲内、好ましくは１～２モルの範囲内で用いることが好ましい。 The monodentate ligand is preferably used in the range of 0.1 to 4 mol, preferably in the range of 1 to 2 mol, relative to 1 mol of the metal alkoxide or metal carboxylate.
　〔有機薄膜〕
　本発明の組成物が用いられる有機薄膜は、本発明の組成物を含む塗布液を調製し、塗布後、焼結又は紫外線を照射して重縮合させながら皮膜化することで、形成することができる。 [Organic thin film]
The organic thin film in which the composition of the present invention is used can be formed by preparing a coating solution containing the composition of the present invention, and forming a film while applying polycondensation by sintering or irradiating ultraviolet rays after coating. it can.
　塗布液を調製する際に必要であれば用いることのできる有機溶媒としては、例えば、脂肪族炭化水素、脂環式炭化水素、芳香族炭化水素等の炭化水素溶媒、ハロゲン化炭化水素溶媒、又は、脂肪族エーテル又は脂環式エーテル等のエーテル類等が適宜使用できる。 Examples of the organic solvent that can be used when preparing the coating liquid include hydrocarbon solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons, halogenated hydrocarbon solvents, or Ethers such as aliphatic ethers or alicyclic ethers can be used as appropriate.
　塗布液における本発明の有機金属酸化物の濃度は、目的とする厚さや塗布液のポットライフによっても異なるが、０．２～３５質量％程度であることが好ましい。塗布液には重合を促進する触媒を添加することも好ましい。 The concentration of the organometallic oxide of the present invention in the coating solution varies depending on the target thickness and the pot life of the coating solution, but is preferably about 0.2 to 35% by mass. It is also preferable to add a catalyst for promoting polymerization to the coating solution.
　調製した塗布液は、スプレーコート法、スピンコート法、ブレードコート法、ディップコート法、キャスト法、ロールコート法、バーコート法、ダイコート法などの塗布による方法、インクジェットプリント法を含む印刷法などのパターニングによる方法などの湿式形成法が挙げられ、材料に応じて使用できる。これらのうち好ましいのは、インクジェットプリント法である。インクジェットプリント法については、特に限定されるものではなく、公知の方法を採用することができる。 The prepared coating liquid can be applied by spray coating, spin coating, blade coating, dip coating, dip coating, casting, roll coating, bar coating, die coating, and other printing methods including inkjet printing. A wet forming method such as a patterning method can be used, and can be used depending on the material. Of these, the inkjet printing method is preferable. The ink jet printing method is not particularly limited, and a known method can be adopted.
　インクジェットプリント法によるインクジェットヘッドからの塗布液の吐出方式は、オンデマンド方式及びコンティニュアス方式のいずれでもよい。オンデマンド方式のインクジェットヘッドは、シングルキャビティー型、ダブルキャビティー型、ベンダー型、ピストン型、シェアーモード型及びシェアードウォール型等の電気－機械変換方式、又は、サーマルインクジェット型及びバブルジェット（登録商標）型等の電気－熱変換方式等のいずれでもよい。 The on-demand method or the continuous method may be used as the method for discharging the coating liquid from the ink jet head by the ink jet printing method. On-demand inkjet heads are available in electro-mechanical conversion methods such as single cavity type, double cavity type, bender type, piston type, shear mode type and shared wall type, or thermal inkjet type and bubble jet (registered trademark). ) Any type of electrical-thermal conversion system or the like may be used.
　塗布後の有機薄膜を固定化するには、低温で重合反応が可能なプラズマやオゾンや紫外線を使うことが好ましい。 In order to fix the organic thin film after coating, it is preferable to use plasma, ozone, or ultraviolet light that can be polymerized at a low temperature.
　真空紫外線処理における紫外線の発生手段としては、例えば、メタルハライドランプ、高圧水銀ランプ、低圧水銀ランプ、キセノンアークランプ、カーボンアークランプ、エキシマランプ、ＵＶ光レーザー等が挙げられる。 Examples of means for generating ultraviolet rays in vacuum ultraviolet treatment include metal halide lamps, high-pressure mercury lamps, low-pressure mercury lamps, xenon arc lamps, carbon arc lamps, excimer lamps, and UV light lasers.
　紫外線照射は、バッチ処理にも連続処理にも適合可能であり、使用する基材の形状によって適宜選定することができる。有機薄膜を形成する基材が長尺フィルム状である場合には、これを搬送させながら上記のような紫外線発生源を具備した乾燥ゾーンで連続的に紫外線を照射することにより行うことができる。紫外線照射に要する時間は、使用する基材や組成物含有塗布液の組成、濃度にもよるが、一般に０．１秒～１０分間であり、好ましくは０．５秒～３分間である。 UV irradiation can be applied to both batch processing and continuous processing, and can be appropriately selected depending on the shape of the substrate used. When the base material for forming the organic thin film is in the form of a long film, it can be carried out by continuously irradiating ultraviolet rays in a drying zone equipped with the ultraviolet ray generation source as described above while being conveyed. The time required for ultraviolet irradiation is generally 0.1 seconds to 10 minutes, preferably 0.5 seconds to 3 minutes, although it depends on the base material used and the composition and concentration of the composition-containing coating solution.
　塗膜面が受けるエネルギーとしては、均一で堅牢な薄膜を形成する観点から、３．０Ｊ／ｃｍ２以上であることが好ましく、３．５Ｊ／ｃｍ２以上であることがより好ましく、４．０Ｊ／ｃｍ２であることがさらに好ましい。また、同様に、過度な紫外線照射を避ける観点から、１４．０Ｊ／ｃｍ２以下であることが好ましく、１２．０Ｊ／ｃｍ２以下であることがより好ましく、１０．０Ｊ／ｃｍ２以下であることがさらに好ましい。 The energy coated surface receives, from the viewpoint of forming a uniform and robust film, is preferably 3.0 J / cm 2 or more, more preferably 3.5 J / cm 2 or more, 4.0 J More preferably, it is / cm 2 . Similarly, from the viewpoint of avoiding excessive ultraviolet radiation, it is preferably 14.0J / cm 2 or less, more preferably 12.0J / cm 2 or less, is 10.0J / cm 2 or less More preferably.
　また、エキシマランプを照射する際の、酸素濃度は３００～１００００体積ｐｐｍ（１体積％）とすることが好ましく、更に好ましくは、５００～５０００体積ｐｐｍで
ある。このような酸素濃度の範囲に調整することにより、有機薄膜が酸素過多になるの
を防止して、水分吸収の劣化を防止することができる。 Further, the oxygen concentration at the time of irradiation with the excimer lamp is preferably 300 to 10,000 ppm by volume (1% by volume), more preferably 500 to 5,000 ppm by volume. By adjusting to such an oxygen concentration range, it is possible to prevent the organic thin film from being excessive in oxygen and to prevent moisture absorption from deteriorating.
　エキシマランプ照射時にこれら酸素以外のガスとしては乾燥不活性ガスを用いることが好ましく、特にコストの観点から乾燥窒素ガスにすることが好ましい。 It is preferable to use a dry inert gas as the gas other than oxygen at the time of excimer lamp irradiation, and it is particularly preferable to use a dry nitrogen gas from the viewpoint of cost.
　これらのエキシマランプ処理の詳細については、例えば、特開２０１２－０８６３９４号公報の段落００５５～００９１、特開２０１２－００６１５４号公報の段落００４９～００８５、特開２０１１－２５１４６０号公報の段落００４６～００７４等に記載の内容を参照することができる。 Details of these excimer lamp processes are, for example, paragraphs 0055 to 0091 of JP2012-086394A, paragraphs 0049 to 0085 of JP2012-006154A, paragraphs 0046 to 0074 of JP2011-251460A. Etc. can be referred to.
　〔用途〕
　本発明の組成物から形成される有機薄膜は、電子デバイス用有機材料であることが好ましい。 [Use]
The organic thin film formed from the composition of the present invention is preferably an organic material for electronic devices.
　前記電子デバイスとしては、例えば、有機ＥＬ素子、発光ダイオード（Ｌｉｇｈｔ　Ｅｍｉｔｔｉｎｇ　Ｄｉｏｄｅ：ＬＥＤ）、液晶素子、太陽電池（光電変換素子）、タッチパネル、液晶表示装置などのカラーフィルター等が挙げられる。特に、本発明においては、本発明の効果発現の観点から、電子デバイスが有機ＥＬ素子、太陽電池及び発光ダイオードであることが好ましい。 Examples of the electronic device include organic EL elements, light emitting diodes (LEDs), liquid crystal elements, solar cells (photoelectric conversion elements), touch panels, liquid crystal display devices, and other color filters. In particular, in the present invention, it is preferable that the electronic device is an organic EL element, a solar cell, and a light emitting diode from the viewpoint of manifesting the effect of the present invention.
　なお、本発明において、電子デバイス用有機材料とは、有機材料の固形成分のことをいい、有機溶媒を含まないものとする。 In addition, in this invention, the organic material for electronic devices means the solid component of an organic material, and shall not contain an organic solvent.
　本発明に係る有機薄膜は、例えば、水と反応することにより、撥水性又は疎水性物質を放出する乾燥剤等として使用することができる。 The organic thin film according to the present invention can be used, for example, as a desiccant that releases water-repellent or hydrophobic substances by reacting with water.
　さらに、本発明の組成物は、インクジェットディスペンサ液として用いることができる。 Furthermore, the composition of the present invention can be used as an ink jet dispenser liquid.
　以下、実施例を挙げて本発明を具体的に説明するが、本発明はこれらに限定されるものではない。なお、実施例において「部」又は「％」の表示を用いるが、特に断りがない限り「質量部」又は「質量％」を表す。 Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, although the display of "part" or "%" is used in an Example, unless otherwise indicated, "mass part" or "mass%" is represented.
　実施例１
　〔組成物の調製〕
　（組成物１の調製）
　水分濃度１ｐｐｍ以下の乾燥窒素雰囲気下のグローブボックス内で、（ａ）チタニウムテトライソプロポキシド（Ｔｉ（ＯｉＰｒ）４）０．１Ｍと、（ｂ）バリウムジイソプロポキシド（Ｂａ（ＯｉＰｒ）２）０．１Ｍとをそれぞれ含有する脱水したイソプロピルアルコールを溶媒として溶液を２ｍＬ調製したゾル・ゲル液を組成物１とした。 Example 1
(Preparation of composition)
(Preparation of Composition 1)
(A) Titanium tetraisopropoxide (Ti (OiPr) 4 ) 0.1M and (b) barium diisopropoxide (Ba (OiPr) 2 ) in a glove box under a dry nitrogen atmosphere with a moisture concentration of 1 ppm or less Composition 1 was a sol-gel solution prepared by 2 mL of a solution using dehydrated isopropyl alcohol each containing 0.1 M as a solvent.
　（組成物２の調製）
　水分濃度１ｐｐｍ以下の乾燥窒素雰囲気下のグローブボックス内で、（ａ）チタニウムテトライソプロポキシド（Ｔｉ（ＯｉＰｒ）４）０．１Ｍと、（ｂ）バリウムジイソプロポキシド（Ｂａ（ＯｉＰｒ）２）０．１Ｍとをそれぞれ含有する脱水したイソプロピルアルコールを溶媒として溶液を２ｍＬ調製し、ガラスシリンジに封入した２５℃・湿度５０％ＲＨの大気を４０ｍＬバブリングをして、すぐにグローブボックス内に戻したゾル・ゲル液を組成物２とした。 (Preparation of composition 2)
(A) Titanium tetraisopropoxide (Ti (OiPr) 4 ) 0.1M and (b) barium diisopropoxide (Ba (OiPr) 2 ) in a glove box under a dry nitrogen atmosphere with a moisture concentration of 1 ppm or less 2 mL of a solution was prepared using dehydrated isopropyl alcohol each containing 0.1 M as a solvent, and 40 mL of air at 25 ° C. and humidity 50% RH sealed in a glass syringe was bubbled and immediately returned to the glove box. The sol-gel solution was composition 2.
　（組成物３～１０の調製）
　組成物２の調製において、２種の金属アルコキシド（ａ）、（ｂ）及び溶媒を表Ｉに示した脱水した溶媒を用いて溶液を２ｍＬ調製し、組成物２の調製と同様にバブリングをして、組成物３～１０とした。ただし、組成物８の調製に当たっては、溶媒に加えて単座配位子であるジブチルエーテルをさらに１４０μＬ（金属アルコキシド１ｍｏｌに対して２ｍｏｌの量）加えて溶液を調製後、大気をバブリングして組成物を調製した。 (Preparation of compositions 3 to 10)
In the preparation of Composition 2, 2 mL of a solution was prepared using two kinds of metal alkoxides (a) and (b) and a dehydrated solvent shown in Table I, and bubbling was performed in the same manner as in the preparation of Composition 2. Thus, compositions 3 to 10 were obtained. However, in preparing the composition 8, in addition to the solvent, 140 μL of dibutyl ether as a monodentate ligand (addition amount of 2 mol with respect to 1 mol of metal alkoxide) was added to prepare a solution, and then the atmosphere was bubbled to prepare the composition. Was prepared.
　〔評価〕
　上記作製した組成物１～１０について、液状態と平均粒子径を測定した。 [Evaluation]
For the compositions 1 to 10 prepared above, the liquid state and the average particle size were measured.
　（液状態）
　上記作製した組成物１～１０について液状態を目視観察して、白濁しているか透明であるかを観察した。 (Liquid state)
The liquid states of the prepared compositions 1 to 10 were visually observed to observe whether they were cloudy or transparent.
　（平均粒子径）
　平均粒子径は、ゼータサイザーナノＺＳ９０（Ｍａｌｖｅｒｎ　Ｐａｎａｌｙｔｉｃａｌ社製）を用い、１００個の粒子について３回の測定を行い、それぞれ得られる粒径の平均値を確認し、３回測定の平均値を平均粒子径とした。 (Average particle size)
The average particle size was measured three times for 100 particles using a Zetasizer Nano ZS90 (Malvern Panallytical), the average value of the obtained particle sizes was confirmed, and the average value of the three measurements was averaged. The particle diameter was taken.
　以上の結果を表Ｉに示す。なお、なお以下の実施例で以下の略号を用いた。
ＩＰＡ：イソプロピルアルコール
ＢｕＯＨ：ブチルアルコール
ＴＦＰＯ：テトラフルオロプロピルアルコール
ＯＦＰＯ：オクタフルオロペンタノール
ＤＢＥ：ジブチルエーテル
ＥＧ：エチレングリコール
Figure JPOXMLDOC01-appb-T000011
 The results are shown in Table I. In the following examples, the following abbreviations were used.
IPA: isopropyl alcohol BuOH: butyl alcohol TFPO: tetrafluoropropyl alcohol OFPO: octafluoropentanol DBE: dibutyl ether EG: ethylene glycol
Figure JPOXMLDOC01-appb-T000011
　表Ｉから、比較の組成物２及び３に対してフッ化アルコールを用いた組成５及び７は、平均粒子径が小さく液も透明であることが分かる。また、比較の組成３及び４に対してフッ化アルコールを用いた組成５及び６は、バブリング量を増やしても粒子サイズ小さく抑えることができ、大気中でより安定であることが分かる。さらに、Ｔｉ－Ｂａの組み合わせだけでなく、組成物９からＴｉ－Ｓｒの金属を組み合わせても液状態は透明で、平均粒子径も抑えられ大気中で安定であることが分る。 From Table I, it can be seen that compositions 5 and 7 using a fluorinated alcohol with respect to comparative compositions 2 and 3 have a small average particle size and a transparent liquid. Moreover, it turns out that the composition 5 and 6 which used the fluorinated alcohol with respect to the comparative compositions 3 and 4 can suppress particle size small even if it increases bubbling amount, and is more stable in air | atmosphere. Further, it can be seen that not only the combination of Ti—Ba but also the combination of Ti—Sr metal from the composition 9, the liquid state is transparent, the average particle size is suppressed, and it is stable in the atmosphere.
　実施例２
　〔組成物の作製〕
　（組成物１１の作製）
　水分濃度１ｐｐｍ以下の乾燥窒素雰囲気下のグローブボックス内で、（ａ）チタニウムテトライソプロポキシド（Ｔｉ（ＯｉＰｒ）４）０．１Ｍと、（ｂ）シリコンテトライソプロポキシド（Ｓｉ（ＯｉＰｒ）４）０．１Ｍとをそれぞれ含有する脱水したイソプロピルアルコールを溶媒として溶液を２ｍＬ調製し、液をシリコンウェハ上にスピン成膜（１０００ｒｐｍ，３０秒）後、１１０℃３０分乾燥させて形成した厚さ１００ｎｍの有機薄膜を組成物１１とした。 Example 2
(Production of composition)
(Preparation of composition 11)
In a glove box under a dry nitrogen atmosphere having a moisture concentration of 1 ppm or less, (a) titanium tetraisopropoxide (Ti (OiPr) 4 ) 0.1M and (b) silicon tetraisopropoxide (Si (OiPr) 4 ) Thickness of 100 nm formed by preparing 2 mL of a solution using dehydrated isopropyl alcohol each containing 0.1 M as a solvent, and drying the solution on a silicon wafer by spin film formation (1000 rpm, 30 seconds), followed by drying at 110 ° C. for 30 minutes. This organic thin film was designated as Composition 11.
　（組成物１２～１５の作製）
　組成物１１の作製において、金属アルコキシド２種及び溶媒を表IIに示した金属アルコキシド２種及び脱水した溶媒に変えて組成物１１と同様にして組成物１２～１５を作製した。ただし、組成物１３では、配位子として二座配位子であるアセチルアセトン１４０μＬ（金属アルコキシド１ｍｏｌに対して２ｍｏｌの量）をさらに添加した後、これにガラスシリンジに封入した２５℃・湿度５０％ＲＨの大気を４０ｍＬバブリングした液を組成物１１同様にスピン製膜し、乾燥させて厚さ１００ｎμｍの有機薄膜を作製した。また組成物１５では、単座配位子であるジブチルエーテル１４０μＬ（金属アルコキシド１ｍｏｌに対して２ｍｏｌの量）をさらに添加した後組成物１１同様にスピン製膜し、乾燥させて厚さ１００ｎｍの有機薄膜を作製した。 (Preparation of compositions 12 to 15)
In preparing the composition 11, compositions 12 to 15 were prepared in the same manner as the composition 11 except that the two metal alkoxides and the solvent were replaced with the two metal alkoxides shown in Table II and the dehydrated solvent. However, in the composition 13, 140 μL of bidentate acetylacetone (a quantity of 2 mol with respect to 1 mol of metal alkoxide) was further added as a ligand, and then this was sealed in a glass syringe at 25 ° C. and humidity of 50%. A liquid obtained by bubbling 40 mL of the RH atmosphere was spin-formed in the same manner as the composition 11 and dried to prepare an organic thin film having a thickness of 100 nμm. Further, in composition 15, a monodentate ligand dibutyl ether 140 μL (2 mol amount per 1 mol of metal alkoxide) was further added, followed by spin film formation in the same manner as in composition 11, and dried to form an organic thin film having a thickness of 100 nm. Was made.
　〔評価〕
　上記作製した膜状の組成物１１～１５に対して、有機薄膜の性状及び屈折率を測定した。 [Evaluation]
The properties and refractive index of the organic thin film were measured for the film-like compositions 11 to 15 produced above.
　（膜性）
　有機薄膜の性状を膜性として以下の評価基準で評価した。 (Membrane)
The properties of the organic thin film were evaluated as the film properties according to the following evaluation criteria.
　○：膜として形成しており手で触れても手に組成物が付着しない
　△：膜の物理的耐性が弱く手で触れると手に組成物が付着する
　×：膜が海島模様となっている。 ○: Formed as a film, and the composition does not adhere to the hand even when touched by the hand. Δ: The physical resistance of the film is weak and the composition adheres to the hand when touched by the hand. ×: The film has a sea-island pattern. .
　（屈折率の測定）
　上記作製した有機薄膜の屈折率を、分光エリプソメータ（ＵＮＥＣＳ－２０００：株式会社アルバック製）を用いて波長６５０ｎｍでの屈折率を測定した。 (Measurement of refractive index)
The refractive index of the organic thin film produced above was measured at a wavelength of 650 nm using a spectroscopic ellipsometer (UNECS-2000: manufactured by ULVAC, Inc.).
　以上の結果を表IIに示す。 The above results are shown in Table II.
Figure JPOXMLDOC01-appb-T000012
Figure JPOXMLDOC01-appb-T000012
　表IIから、組成物１３に対して、フッ化アルコールを用いた組成物１４、更に単座配位子としてジブチルエーテルを添加した組成物１５は、屈折率が向上していることが分る。屈折率が高いことは、有機薄膜は稠密化しおり、溶媒や添加物の揮発割合が高いことを表している。低温においても、溶媒の留去率が優れていることが確認できる。 From Table II, it can be seen that the composition 14 using the fluorinated alcohol with respect to the composition 13 and further the composition 15 in which dibutyl ether is added as a monodentate ligand have an improved refractive index. A high refractive index indicates that the organic thin film is densified and the volatilization ratio of the solvent or additive is high. It can be confirmed that the solvent evaporation rate is excellent even at low temperatures.
　実施例３
　〔組成物の作製〕
　（組成物２１の作製）
　水分濃度１ｐｐｍ以下の乾燥窒素雰囲気下のグローブボックス内で、（ａ）チタニウムテトライソプロポキシド（Ｔｉ（ＯｉＰｒ）４）０．１Ｍと、（ｂ）ストロンチウムジイソプロポキシド（Ｓｒ（ＯｉＰｒ）２）０．１Ｍとをそれぞれ含有する脱水したエチレングリコールを溶媒として溶液を２ｍＬ調製し、さらに、配位子として二座配位子であるアセチルアセトン１４０μＬ（金属アルコキシド１ｍｏｌに対して２ｍｏｌの量）を添加した後、これにガラスシリンジに封入した２５℃・湿度５０％ＲＨの大気を４０ｍＬバブリングした液をシリコンウェハ上にスピン成膜（１０００ｒｐｍ、３０秒）後、１１０℃３０分乾燥させて形成した厚さ１００ｎｍの有機薄膜を組成物２１とした。 Example 3
(Production of composition)
(Preparation of composition 21)
(A) Titanium tetraisopropoxide (Ti (OiPr) 4 ) 0.1M and (b) strontium diisopropoxide (Sr (OiPr) 2 ) in a glove box under a dry nitrogen atmosphere with a moisture concentration of 1 ppm or less 2 mL of a solution was prepared using dehydrated ethylene glycol each containing 0.1 M as a solvent, and 140 μL of bidentate ligand acetylacetone (2 mol relative to 1 mol of metal alkoxide) was added as a ligand. After that, a liquid formed by bubbling 40 mL of air at 25 ° C. and 50% humidity RH sealed in a glass syringe on a silicon wafer was spin-deposited on a silicon wafer (1000 rpm, 30 seconds), and then dried at 110 ° C. for 30 minutes to form a thickness A 100 nm organic thin film was used as composition 21.
　（組成物２２及び２３の作製）
　組成物２１の作製において、金属アルコキシド２種、溶媒及び配位子を表IIIに示した
金属アルコキシド２種、脱水した溶媒及び配位子に変えて組成物２１と同様にして厚さ１００ｎｍの有機薄膜を作製し組成物２２及び２３とした。 (Preparation of compositions 22 and 23)
In the preparation of the composition 21, an organic compound having a thickness of 100 nm was prepared in the same manner as the composition 21 except that the two metal alkoxides, the solvent and the ligand were replaced with the two metal alkoxides shown in Table III, the dehydrated solvent and the ligand. Thin films were prepared as compositions 22 and 23.
　〔評価〕
　上記作製した組成物２１～２３を、さらに６０℃９０％の恒温恒湿層に１日放置した後の有機薄膜の吸水量を測定した。本発明の組成物は、系外からの水分によって加水分解し、撥水性又は疎水性物質であるフッ化アルコール（Ｒ′－ＯＨ）を放出する。このフッ化アルコールによって、有機薄膜に撥水性又は疎水性を付与することができる。 [Evaluation]
The water absorption of the organic thin film was measured after the compositions 21 to 23 prepared above were further left in a constant temperature and humidity layer at 60 ° C. and 90% for 1 day. The composition of the present invention is hydrolyzed by moisture from outside the system, and releases fluorinated alcohol (R′—OH), which is a water-repellent or hydrophobic substance. This fluorinated alcohol can impart water repellency or hydrophobicity to the organic thin film.
　（吸水量）
　重水（Ｄ２Ｏ）と金属アルコキシドとの反応により、撥水性又は疎水性物質であるフッ化アルコール（Ｒ′－ＯＤ）が生成することから、Ｒ′－ＯＤを検出することにより給水量を測定した。すなわち、Ｄ２Ｏ雰囲気下に３時間放置後のＲ′－ＯＤを検出した。検出は、昇温脱離分析装置ＴＤＳ１２００（電子科学株式会社製）を用いた。 (Water absorption)
The reaction between heavy water (D 2 O) and metal alkoxide produces water-repellent or hydrophobic fluorinated alcohol (R'-OD), so the amount of water supply can be measured by detecting R'-OD did. That is, R′-OD after 3 hours in a D 2 O atmosphere was detected. For detection, a temperature programmed desorption analyzer TDS1200 (manufactured by Electronic Science Co., Ltd.) was used.
　以上の結果を表IIIに示す。 The above results are shown in Table III.
Figure JPOXMLDOC01-appb-T000013
Figure JPOXMLDOC01-appb-T000013
　表IIIから、比較の組成物２１に対して、フッ化アルコキシド基を有する組成物２２及
び２３は有機薄膜にした後でも、高い吸水機能を有することが分る。 From Table III, it can be seen that the compositions 22 and 23 having a fluorinated alkoxide group have a high water absorption function even after being made into an organic thin film with respect to the comparative composition 21.
　また、上記の結果は、Ｓｒ－Ｂｉ－Ｔｉの３種の金属を有する本発明に係る組成物においても得られた。 The above results were also obtained for the composition according to the present invention having three kinds of metals, Sr—Bi—Ti.
　本発明の組成物は、大気中でも安定で、低温乾燥で溶媒除去可能な膜を形成することができる。本発明の組成物から形成される有機薄膜は、電子デバイス用有機材料であることが好ましい。電子デバイスとしては、例えば、有機ＥＬ素子、発光ダイオード、液晶素子、太陽電池（光電変換素子）、タッチパネル、液晶表示装置などのカラーフィルター等に適用できる。特に、有機ＥＬ素子、太陽電池及び発光ダイオードに好ましく適用することができる。 The composition of the present invention can form a film that is stable in the air and can be removed by low-temperature drying. The organic thin film formed from the composition of the present invention is preferably an organic material for electronic devices. As an electronic device, it can apply to color filters etc., such as an organic EL element, a light emitting diode, a liquid crystal element, a solar cell (photoelectric conversion element), a touch panel, and a liquid crystal display device, for example. In particular, it can be preferably applied to organic EL elements, solar cells, and light emitting diodes.

Claims (7)

  1. 　金属アルコキシド又は金属カルボキシレートを含有する組成物であって、前記金属アルコキシド又は金属カルボキシレートが、フッ化アルコキシ基を有する、金属アルコキシド又は金属カルボキシレートの単量体若しくは重合体であり、かつ複数種の金属原子を含むことを特徴とする組成物。 A composition containing a metal alkoxide or metal carboxylate, wherein the metal alkoxide or metal carboxylate is a metal alkoxide or metal carboxylate monomer or polymer having a fluorinated alkoxy group, and a plurality of types A composition comprising a metal atom.
  2. 　前記複数種の金属原子が、Ｔｉ－Ｓｉ、Ｔｉ－Ｂａ、Ｔｉ－Ｓｒ、Ｔｉ－Ｃａ、Ｔｉ－Ｍｇ、Ｔｉ－Ｚｒ、Ｔｉ－Ｚｎ、Ｔｉ－Ｃｕ、Ｚｎ－Ｃｕ、Ｚｎ－Ｓｉ、Ｃｕ－Ｓｉ、Ｃａ－Ｂｉ－Ｔｉ、Ｓｒ－Ｂｉ－Ｔａ又はＢｉ－Ｆｅの金属原子の組み合わせのいずれかであることを特徴とする請求項１に記載の組成物。 The plurality of types of metal atoms are Ti—Si, Ti—Ba, Ti—Sr, Ti—Ca, Ti—Mg, Ti—Zr, Ti—Zn, Ti—Cu, Zn—Cu, Zn—Si, Cu—. The composition according to claim 1, wherein the composition is one of a combination of metal atoms of Si, Ca-Bi-Ti, Sr-Bi-Ta, or Bi-Fe.
  3. 　前記金属アルコキシド又は金属カルボキシレートの単量体が、下記一般式（１）で表される構造を有する金属アルコキシド又は金属カルボキシレートを複数種有し、当該複数種の金属アルコキシド又は金属カルボキシレートの金属種がそれぞれ異なることを特徴とする請求項１又は請求項２に記載の組成物。
    　　一般式（１）
    　　　　　Ｍ（ＯＲ１）ｙ（Ｏ－Ｒ）ｘ－ｙ
    　（式中、Ｒは、水素原子、炭素数１個以上のアルキル基、アルケニル基、アリール基、シクロアルキル基、アシル基又は複素環基を表す。ただし、Ｒは置換基としてフッ素原子を含む炭素鎖でもよい。Ｍは、金属原子を表す。ＯＲ１は、フッ化アルコキシ基を表す。ｘは金属原子の価数、ｙは１とｘの間の任意な整数を表す。）     The monomer of the metal alkoxide or metal carboxylate has a plurality of types of metal alkoxide or metal carboxylate having a structure represented by the following general formula (1), and the metal of the plurality of types of metal alkoxide or metal carboxylate The composition according to claim 1 or 2, wherein the species are different from each other.
    General formula (1)
    M (OR 1 ) y (OR) xy
    (In the formula, R represents a hydrogen atom, an alkyl group having 1 or more carbon atoms, an alkenyl group, an aryl group, a cycloalkyl group, an acyl group, or a heterocyclic group. However, R represents a carbon containing a fluorine atom as a substituent. The chain may be a chain, M represents a metal atom, OR 1 represents a fluorinated alkoxy group, x represents the valence of the metal atom, and y represents any integer between 1 and x.)
  4. 　前記金属アルコキシド中に含まれるフッ素原子の数が、それぞれの金属アルコキシドの金属原子１個に対し４～１６の範囲内であることを特徴とする請求項３に記載の組成物。 The composition according to claim 3, wherein the number of fluorine atoms contained in the metal alkoxide is in the range of 4 to 16 with respect to one metal atom of each metal alkoxide.
  5. 　前記金属アルコキシド又は金属カルボキシレート中の金属原子に配位することのできるエーテル結合又はカルボニル基を有する単座配位子を含有することを特徴とする請求項１から請求項４までのいずれか一項に記載の組成物。 The monodentate ligand which has an ether bond or carbonyl group which can be coordinated to the metal atom in the said metal alkoxide or metal carboxylate is contained, The any one of Claim 1 to 4 characterized by the above-mentioned. A composition according to 1.
  6. 　前記単座配位子が、エーテル結合を有することを特徴とする請求項５に記載の組成物。 The composition according to claim 5, wherein the monodentate ligand has an ether bond.
  7. 　前記単座配位子が、下記一般式（２）で表されるエーテル結合を有する単座配位子であることを特徴とする請求項５又は請求項６に記載の組成物。
    　　一般式（２）
    　　　　Ｒ１－Ｏ－Ｒ２
    　（式中、Ｒ１及びＲ２は、それぞれ独立に炭素数２～４のアルキル基を表す。）     The composition according to claim 5 or 6, wherein the monodentate ligand is a monodentate ligand having an ether bond represented by the following general formula (2).
    General formula (2)
    R 1 —O—R 2
    (In the formula, R 1 and R 2 each independently represents an alkyl group having 2 to 4 carbon atoms.)
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* Cited by examiner, † Cited by third party
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JPH03133990A (en) * 1989-10-18 1991-06-07 Ajinomoto Co Inc Fluorinated carbon chain-containing titanate compound and fluorine-based surface modifier
JPH03255088A (en) * 1989-12-11 1991-11-13 Ajinomoto Co Inc Aluminum-based surface-modifier container fluorinated carbon chain
JPH04232271A (en) * 1990-07-27 1992-08-20 Kali Chem Ag Deposition method of copper-containing layer onto substrate
JPH04362655A (en) * 1991-06-10 1992-12-15 Ajinomoto Co Inc Magnetic powder for magnetic toner
JPH05163482A (en) * 1991-12-13 1993-06-29 Nippon Soda Co Ltd Surface-treating agent of coated surface
JPH06340870A (en) * 1993-06-01 1994-12-13 Nippon Soda Co Ltd Water-and oil-repellent aerosol composition
JPH08104985A (en) * 1994-10-07 1996-04-23 Toyota Motor Corp Formation of water-repellent coating film on ferrous member
JP2015225785A (en) * 2014-05-28 2015-12-14 国立大学法人山形大学 Sealing method for organic electroluminescence element

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03133990A (en) * 1989-10-18 1991-06-07 Ajinomoto Co Inc Fluorinated carbon chain-containing titanate compound and fluorine-based surface modifier
JPH03255088A (en) * 1989-12-11 1991-11-13 Ajinomoto Co Inc Aluminum-based surface-modifier container fluorinated carbon chain
JPH04232271A (en) * 1990-07-27 1992-08-20 Kali Chem Ag Deposition method of copper-containing layer onto substrate
JPH04362655A (en) * 1991-06-10 1992-12-15 Ajinomoto Co Inc Magnetic powder for magnetic toner
JPH05163482A (en) * 1991-12-13 1993-06-29 Nippon Soda Co Ltd Surface-treating agent of coated surface
JPH06340870A (en) * 1993-06-01 1994-12-13 Nippon Soda Co Ltd Water-and oil-repellent aerosol composition
JPH08104985A (en) * 1994-10-07 1996-04-23 Toyota Motor Corp Formation of water-repellent coating film on ferrous member
JP2015225785A (en) * 2014-05-28 2015-12-14 国立大学法人山形大学 Sealing method for organic electroluminescence element

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