WO2002094953A1 - Solution alcoolique colloidale de metal noble ou de cuivre, procede permettant de produire cette solution et composition de revetement - Google Patents

Solution alcoolique colloidale de metal noble ou de cuivre, procede permettant de produire cette solution et composition de revetement Download PDF

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Publication number
WO2002094953A1
WO2002094953A1 PCT/JP2001/004214 JP0104214W WO02094953A1 WO 2002094953 A1 WO2002094953 A1 WO 2002094953A1 JP 0104214 W JP0104214 W JP 0104214W WO 02094953 A1 WO02094953 A1 WO 02094953A1
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Prior art keywords
solution
noble metal
copper
colloid
alcohol
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PCT/JP2001/004214
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English (en)
Japanese (ja)
Inventor
Hideo Ishibashi
Taizou Nanke
Toshikatsu Kobayashi
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Nippon Paint Co., Ltd.
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Application filed by Nippon Paint Co., Ltd. filed Critical Nippon Paint Co., Ltd.
Priority to JP2002592416A priority Critical patent/JPWO2002094953A1/ja
Priority to CN01813038.0A priority patent/CN1443228A/zh
Priority to PCT/JP2001/004214 priority patent/WO2002094953A1/fr
Priority to TW091110472A priority patent/TW570963B/zh
Publication of WO2002094953A1 publication Critical patent/WO2002094953A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/0004—Preparation of sols
    • B01J13/0043—Preparation of sols containing elemental metal
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D17/00—Pigment pastes, e.g. for mixing in paints
    • C09D17/004—Pigment pastes, e.g. for mixing in paints containing an inorganic pigment
    • C09D17/006—Metal

Definitions

  • the present invention relates to an alcohol solution of a noble metal or copper colloid which can be suitably used for a sol-gel method, a method for producing the same, a solution preparation method, a coating composition using the same, an inorganic coating using the same,
  • the present invention relates to a method for forming an inorganic film.
  • Precious metal and copper colloids are very stable chemically and develop a unique color for each colloid.
  • colloidal gold exhibits a color such as blue, bluish violet, or magenta depending on the particle size. Taking advantage of this property, it has been used for coloring Venetian glass and stained glass.
  • Such color development by the noble metal colloid is observed in so-called nanoparticles having a particle size of several nm to several tens nm, and it is advantageous that the colorant is a colloid having a narrow particle size distribution.
  • Japanese Patent Application Laid-Open No. 11-080647 discloses a precious metal or copper colloidal particle having high coloring properties, which includes a precious metal or copper colloidal particle and a high molecular weight pigment dispersant.
  • a copper colloid solution is disclosed. Since this material is not intended for use as an optical material, the necessary saturation may not be obtained in some cases.
  • the sol-gel method for producing glass and ceramics has been known for a long time.
  • an alcohol, water necessary for hydrolysis, an acid or a base as a catalyst are added to a metal alkoxide, and the mixture is subjected to polycondensation to form a sol in which particles of a metal oxide formed are dispersed in a colloidal state.
  • this is further gelled, it is processed into a coating film or the like, and an oxide solid is obtained by heating.
  • the sol-gel method has the advantage of obtaining a thin film gel or glass from a solution as described above.In addition, the thin film obtained by this method has good adhesion to a glass substrate and uniformity of the obtained thin film.
  • the present invention provides a colloidal alcohol solution of a noble metal or copper which has a high concentration, has sufficient coloring properties, and can be suitably used for a sol-gel method, and a method for producing the same, a method for preparing a solution, and It is an object of the present invention to provide a coating composition comprising the alcohol solution of a noble metal or copper colloid or a colloidal solution of a noble metal or copper, and an inorganic coating and an inorganic coating forming method using the same. It is a thing.
  • the present inventors have used an alcohol having 1 to 4 carbon atoms as a dispersion medium of a noble metal or copper colloid, and considered the affinity with the above alcohol as a protective colloid of the noble metal or copper colloid particles.
  • an alcohol solution of a precious metal or copper colloid having a narrow particle size distribution of the colloid particles can be obtained at a high concentration, and it can be suitably used for the sol-gel method.
  • the present invention has been completed.
  • the present invention is an alcohol solution of a noble metal or copper colloid comprising a noble metal or copper colloid particle and a high molecular weight pigment dispersant, wherein the alcohol has 1 to 4 carbon atoms, and the high molecular weight pigment dispersion agent is an alcohol solution of a colloid of a noble metal or copper, characterized in that those that meet the following formula (1) or (2) c
  • a and B are respectively the values of the above-mentioned acetone solution in which 0.5 g of the high molecular weight pigment dispersant is dissolved in 10 ml of acetone and water or hexane is added until the acetone solution becomes cloudy.
  • the alcohol is preferably a monoalcohol having 2 to 4 carbon atoms, and the above formula (1) is preferably the following formula (1 ′).
  • the present invention further provides a noble metal or copper colloid alcohol which is prepared by dissolving a noble metal or copper compound into an alcohol having 1 to 4 carbon atoms, adding a high molecular weight pigment dispersant, and then reducing the compound to a noble metal or copper.
  • a and B are respectively the same as above when water or hexane is added to an acetone solution obtained by dissolving 0.5 g of the polymer i pigment dispersant in 10 ml of acetone until the acetone solution becomes cloudy. The amount (ml) of the water added and the amount (ml) of the hexane added until the aceton solution became cloudy.
  • the present invention is also a colloidal alcohol solution of a noble metal or copper obtained by this method.
  • the present invention is characterized in that, after concentrating an alcohol solution of a colloid of a noble metal or copper obtained by the above-mentioned production method, a solution different from the above-mentioned alcohol is added to a solution obtained by concentrating the solution to dilute the noble metal or copper.
  • This is a method for preparing a colloid solution.
  • the present invention is also a colloidal solution of a noble metal or copper obtained by this preparation method.
  • the present invention is also a coating composition comprising the above alcohol solution of a noble metal or copper colloid and a metal alkoxide.
  • the present invention comprises the above colloidal solution of a noble metal or copper and a metal alkoxide. It is also a coating composition.
  • the present invention is also an inorganic coating obtained using the coating composition.
  • the present invention further provides a method for forming an inorganic film, comprising forming an inorganic film on a substrate using the coating composition.
  • the alcohol solution of the noble metal or copper colloid of the present invention contains noble metal or copper colloid particles and a high molecular weight pigment dispersant, and has a C 1-4 alcohol as a dispersion medium.
  • the alcohol has 1 to 4 carbon atoms, not only can noble metal or copper color particles be dispersed with high concentration and high stability, but also when used as an optical material, In addition, a high chroma can be realized, and a large amount of the colloidal alcohol solution of the noble metal or copper of the present invention can be used in the sol-gel method.
  • the noble metal or copper colloid solution using the alcohol as a solvent has insufficient compatibility with the metal alkoxide solution used in the sol-gel method, and a coating composition may be obtained. It may not be possible.
  • the alcohol used in the present invention is not particularly limited as long as it has 1 to 4 carbon atoms.
  • monoalcohols such as methanol, ethanol, propanol, and ptananol; ethylene glycol, diethylene glycol, and propylene glycol
  • alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl enoate ether, ethylene glycol monoethyl enolate ether, and propylene dalycol monomethynoole ether.
  • the colloidal alcohol solution of the noble metal or copper of the present invention is used in the sol-gel method, it is preferably one having 2 to 4 carbon atoms in consideration of the evaporability, and it does not progress cross-linking between metal alkoxides. Considering this, monoalcohols are preferred. Since ethyl silicate is preferably used as the metal alkoxide in the sol-gel method, the alcohol is more preferably ethanol. In addition, The above alcohols may be used alone or in combination of two or more.
  • a dispersion medium of the noble metal or copper colloid composed of only the alcohol.
  • a small amount of the above alcohol may be used as long as the stability is not impaired when added to the metal alkoxide solution used in the sol-gel method. Water may be added.
  • the noble metal or copper colloid particles are formed of a noble metal or copper compound.
  • the noble metal is not particularly limited, and examples thereof include gold, silver, ruthenium, rhodium, palladium, osmium, iridium, and platinum. Of these, gold, silver, platinum and palladium are preferred.
  • the noble metal or copper compound is preferably a compound which dissolves in the above alcohol having 1 to 4 carbon atoms.
  • examples thereof include tetrachlorobase (III) acid tetrahydrate, silver perchlorate, and hexachlorotoplatinum (IV). Acid hexahydrate, palladium (II) chloride dihydrate, rhodium (III) trichloride trihydrate, copper (II) chloride dihydrate, copper (II) acetate monohydrate and the like be able to.
  • the high molecular weight pigment dispersant is an amphiphilic copolymer in which a functional group having a high affinity for the pigment surface is introduced into the high molecular weight polymer.
  • This is suitable as a dispersant for organic pigments or inorganic pigments because it has sufficient compatibility with resin compositions for coatings, etc., and is usually used as a pigment dispersant in the production of pigment pastes. Is what it is.
  • the high-molecular weight pigment dispersant functions as a protective colloid when the noble metal or copper colloid particles are formed, and by using the same, a very high concentration alcohol solution of the noble metal or copper colloid is obtained.
  • the high molecular weight pigment dispersant satisfies the following formula (1) or (2).
  • (1) A ⁇ 3 m 1 and 3m 1 ⁇ B 4 Om 1
  • the formula (2) can be used as the high molecular weight pigment dispersant if the formula (2) is satisfied.
  • the high molecular weight pigment dispersant is an alcohol having 1 to 4 carbon atoms, which is a dispersion medium of an alcohol solution of a noble metal or copper colloid. As a result, no colloidal particles of noble metal or copper can be obtained.
  • the above formula (1) is preferably the following formula (1 ′).
  • the number average molecular weight of the high molecular weight pigment dispersant used in the present invention is preferably from 1,000 to 100,000. If it is less than 1000, the dispersion stability is not sufficient, and if it exceeds 1,000,000, the viscosity becomes too high to make handling difficult, and the particle size distribution of the colloid particles becomes wide and the chroma decreases. More preferably, it is 2000 to 500,000, and still more preferably 4000 to 500,000.
  • the high molecular weight pigment dispersant is a resin having a structure containing a pigment affinity group and a solvation portion, and examples thereof include those exemplified in JP-A-11-80647.
  • a commercially available pigment dispersant can also be used.
  • examples of the above commercially available products include Solsperse 27,000 and Solsperse 41 090 (above, manufactured by Abyssia), Dispervik 180, Dispervik 181, Dispervik 190, Dispervik 191, Dispervik 192 (above, manufactured by Big Chem), Polymer 450, Polymer 451, Polymer 452, Polymer 453, E FKA-1 501, EFKA-1 502, EFKA-4540, EFKA-4550 (all manufactured by EFKA Chemical), Floren TG-720 Floren_730W, Floren 740W, Floren 1
  • the content of the high molecular weight pigment dispersant is preferably 30 to 1000 parts by weight based on 100 parts by weight of the noble metal or copper.
  • the amount is less than 30 parts by weight, the dispersibility of the noble metal or copper colloid particles is insufficient.
  • the alcohol solution of the noble metal or copper colloid is used for the sol-gel method. In such a case, the physical properties of the obtained thin film may be poor. More preferably, it is 40 to 650 parts by weight.
  • the alcohol solution of a colloid of a noble metal or copper of the present invention is an organosol using the above-mentioned alcohol having 1 to 4 carbon atoms as a solvent, and the concentration of the noble metal or copper can be 1 Ommo 1/1 or more. If it is less than 1 Ommo 1/1, it is not possible to obtain a high-concentration alcohol solution of colloid. More preferably, it is 50 mmolZl or more.
  • the average particle size of the colloid particles is preferably 5 to 50 nm. If it is less than 5 nm, the coloring power is weak, and if it exceeds 50 nm, the saturation becomes low.
  • the solid content of the colloid particles and the polymer dispersant can be arbitrarily set, for example, 1 to 50% by weight. Further, the metal concentration in the solid content is preferably about 10% by weight or more. If it is less than this, the desired effect cannot be obtained because the metal content is too low.
  • the upper limit is not particularly specified, but can be, for example, 98% by weight or less. You.
  • the alcohol solution of a noble metal or copper colloid of the present invention is obtained by dissolving the above noble metal or copper compound in an alcohol having 1 to 4 carbon atoms and reducing the compound to noble metal or copper in the presence of a high molecular weight pigment dispersant. Obtainable.
  • the method for the reduction is not particularly limited, and examples thereof include a method of chemically reducing the compound by adding a reducing compound, a method of irradiating light with a high-pressure mercury lamp, and the like.
  • the addition of the compound in the chemical reduction method may be performed after the addition of the polymer pigment dispersant.
  • the polymer pigment dispersant and the compound may be mixed first, and the mixture may be used. In the form of addition to a solution of a noble metal or copper compound.
  • the reducing compound is preferably an alcohol-soluble compound, for example, an alkali metal borohydride salt such as sodium borohydride which has been conventionally used as a reducing agent; a hydrazine compound; a hydroxylamine compound; Acid salt; a sulfoxylate derivative; formaldehyde; an organic acid having 1 to 6 carbon atoms such as formic acid or a salt thereof, citric acid or a salt thereof, succinic acid or a salt thereof, tartaric acid or a salt thereof, L-ascorbic acid or a salt thereof, or Its salts and the like can be used.
  • an amine can be used in addition to the conventional reducing agent. One or more of these can be used.
  • the above-mentioned amine is not usually used as a reducing agent. However, by adding the amine to the above-mentioned solution of the noble metal or copper compound, stirring and mixing, the noble metal ion or copper ion becomes noble metal at around room temperature. It is reduced to copper.
  • the above-mentioned amine it is not necessary to use a dangerous reducing agent or a highly harmful reducing agent, and without heating or using a special light irradiation device, about 5 to 100 ° C, preferably The noble metal or copper compound can be reduced at a reaction temperature of about 20 to 80 ° C.
  • the above-mentioned amine is not particularly limited, and for example, those exemplified in JP-A-11-8647 can be used.
  • Alicyclic amines such as tilpiperidine, piperazine, pyrrolidine, morpholine and derivatives thereof; aromatic amines such as aniline, 1,izidine, anisidine, phenetidine and derivatives thereof; benzylamine, phenethylamine, xylylenediamine; And aralkylamines such as derivatives thereof.
  • Examples of the above amine include methylaminoethanol, dimethylaminoethanol, methylaminoethanol, triethanolamine, ethanolamine, diethanolamine, methylethanolanolamine, propanolanolamine, 2- (3-aminopropylamino) Alkanolamines such as ethanol, butanolamine, hexanolamine and dimethylaminopropanol can also be mentioned. Of these, alkanolamine is preferred, and 2-dimethylaminoethanol is more preferred.
  • the amount of the amine to be added is preferably 1 to 50 mol per 1 mol of the noble metal or copper compound. If it is less than lmo1, the reduction is not performed sufficiently, and if it exceeds 50mo1, the stability of the generated colloidal particles with respect to aggregation decreases. More preferably, it is 2 to 8 mol.
  • the amount of the sodium borohydride to be added is preferably 1 to 5 Omo 1, more preferably 1.5 to L Omol, per 1 mo 1 of the noble metal or copper compound.
  • citric acid or a salt thereof is used as the reducing agent, noble metal ions, copper ions, and the like can be reduced by heating and refluxing in the presence of an alcohol.
  • the above citric acid or its salt has the advantage that it is very inexpensive and easily available.
  • sodium citrate is preferable.
  • the reduction action is improved when iron (II) sulfate is used in combination, so that the reduction reaction can proceed under milder conditions.
  • iron (II) sulfate when sodium citrate and iron (II) sulfate are mixed, insoluble iron (II) citrate is formed when the stoichiometry of citrate and iron (II) ions is adjusted, and when sedimentation occurs, Trouble occurs.
  • iron (II) sulfate it is necessary to add iron (II) sulfate so that the amount of sodium citrate becomes excessive.
  • the reducing action can be improved by using it together with, for example, a sulfoxylate derivative in addition to citric acid.
  • salts of humic acid, tartaric acid and the like with the above-mentioned amines are also preferable because both the acid and the ammine have a reducing property.
  • the addition amount of the above citric acid or a salt thereof is preferably 1 to 50 mol per 1 mol of the noble metal or copper compound. If it is less than 1 m o 1, the reduction is not sufficiently performed, and if it exceeds 5 m o 1, the stability against aggregation decreases. More preferably, it is 1.5 to 1 Omo1.
  • the method for producing a noble metal or copper colloid alcohol solution of the present invention comprises dissolving the noble metal or copper compound in a solvent containing an alcohol having 1 to 4 carbon atoms to form a solution, and adding a high molecular weight pigment dispersant.
  • a colloidal solution of noble metal or copper with a concentration of 10 times or more higher than that of the conventional colloidal solution of noble metal. Can be manufactured.
  • alkanolamine it can be easily produced under mild conditions of about 20 to 80 ° C.
  • the high molecular weight pigment dispersant used in the method for producing a colloidal solution of a noble metal or copper colloid according to the present invention is the same as that described for the alcohol solution of a noble metal or copper colloid described above.
  • the solution after the reduction is, in addition to the metal colloid particles and the polymer pigment dispersant, miscellaneous ions such as chloride ions derived from the raw material of the noble metal or copper colloid solution, salts generated by reduction, and in some cases, It contains amines, and these miscellaneous ions and chlorides may adversely affect the stability of the resulting colloidal solution of noble metal or copper, so it is desirable to remove them.
  • miscellaneous ions such as chloride ions derived from the raw material of the noble metal or copper colloid solution, salts generated by reduction, and in some cases, It contains amines, and these miscellaneous ions and chlorides may adversely affect the stability of the resulting colloidal solution of noble metal or copper, so it is desirable to remove them.
  • electrodialysis, centrifugation, and ultrafiltration are used for the removal of these components. However, as described later, centrifugation and ultrafiltration are preferably used because concentration is performed.
  • the method of preparing a colloidal solution of a noble metal or copper colloid according to the present invention involves concentrating an alcohol solution of a colloidal noble metal or copper obtained earlier, and then adding the above-mentioned alcohol to the concentrated solution. It is characterized by adding and diluting a solvent different from coal.
  • concentration method centrifugal separation and ultrafiltration are preferable, since various methods can simultaneously remove foreign ions and saltamine.
  • a solvent different from the above alcohol is used, and by repeating this concentration and dilution, the solvent can be substantially replaced.
  • water is preferable from the viewpoint of workability and ease of handling.
  • the aqueous solution of the noble metal or copper colloid obtained in this way has a sharper absorption curve than that produced using water as a solvent.
  • the alcohol solution of the precious metal or copper colloid of the present invention and the precious metal or copper colloid solution obtained by the above solution preparation method can be suitably used for the sol-gel method.
  • the sol-gel method generally, an alcohol, water necessary for hydrolysis, and an acid or base as a catalyst are added to a metal alkoxide, and the mixture is stirred at room temperature to 80 ° C. to undergo hydrolysis and condensation polymerization. It is. By these reactions, a sol in which metal oxide particles are dispersed in a colloidal state is easily obtained.
  • the sol solution can be used as a coating composition.
  • a sol film can be formed on a substrate by a dipping method, a spin coating method, or the like. The coated sol film is dried at room temperature and then heated at an appropriate temperature to obtain a gel thin film or a glass thin film which is an inorganic coating.
  • the coating composition of the present invention comprises the above alcohol solution of a noble metal or copper colloid and a metal alkoxide.
  • Another coating composition of the present invention comprises the above-mentioned colloidal solution of a noble metal or copper and a metal alkoxide.
  • metal alkoxide those usually used in the sol-gel method can be used.
  • M (OR) n M is a metal atom, R is an alkyl group, and n is an acid number of a metal. ) Can be mentioned.
  • Si (OR) 4 is generally used.
  • the genus atoms M those of Zn, Zr, Ti, Al, Fe, Co, and Ni can be used according to the purpose.
  • the alkoxy group in the metal alkoxide include an alkoxy group having 1 to 5 carbon atoms such as methoxy, ethoxy, propoxy, butoxy, pentyloxy and the like. Among these, an ethoxy group is more preferable in that it has good reactivity.
  • tetraethoxysilane is particularly preferable in terms of easy handling.
  • Examples of the solvent for the metal alkoxide solution include those composed of alcohol and water.
  • the number of moles of alcohol per mole of water can be selected depending on the properties of the target thin film, but is usually preferably 1 to 30. If the number of moles of alcohol per mole of water is less than 1, hydrolysis of the metal alkoxide progresses too much and lacks stability.If it exceeds 25, hydrolysis of the metal alkoxide becomes insufficient and is not practical. Not a target.
  • the mole number of the alcohol per 1 mole of the water is more preferably from 10 to 25.
  • the alcohol in the metal alkoxide solution is not particularly limited, and for example, those exemplified as the alcohols contained in the alcohol solution of the noble metal or copper colloid of the present invention and alcohols having 5 carbon atoms can be used.
  • the metal alkoxide solution may contain an acid or a base as a catalyst, but preferably contains an acid when forming an inorganic coating.
  • the acid is not particularly limited, and examples thereof include hydrochloric acid and nitric acid.
  • the metal alkoxide solution may further contain, if necessary, additives such as a drying inhibitor, a colored transition metal compound other than the noble metal or copper, a silane coupling agent, and an organic dye.
  • a drying inhibitor is not particularly limited, and examples thereof include dimethylformamide and dimethylacetamide.
  • the coating composition of the present invention is obtained by adding a noble metal or copper colloidal alcohol solution or a noble metal or copper colloidal solution to the metal alkoxide solution and stirring the mixture.
  • a noble metal or copper colloidal alcohol solution or a noble metal or copper colloidal solution As the ratio of the above-mentioned addition, the above-mentioned noble metal or copper colloidal alcohol solution or the noble metal or copper It is preferable to add the colloidal particles of the noble metal or copper so that the concentration of the colloidal particles of the noble metal or copper in the state where the colloidal solution is added is 0.01 to 70% by weight.
  • a colloidal alcohol solution of a noble metal or copper it is preferable to use a colloidal alcohol solution of a noble metal or copper.
  • the substrate on which the coating composition used in the above sol-gel method is applied is not particularly limited, and examples thereof include metals such as aluminum and stainless steel, glass, and plastics. And / or both surfaces may be subjected to surface processing.
  • the coating method in addition to the above-described methods such as the dip method and the spin coating method, when the substrate is a metal such as aluminum, electrophoresis can be used. By baking the film thus obtained, an inorganic coating can be obtained.
  • the calcination can be preferably performed at 100 to 500 ° C.
  • the calcination can be preferably performed for 5 to 120 minutes.
  • the inorganic coating obtained by forming a film by the sol-gel method using the alcoholic solution of the noble metal or copper colloid of the present invention or the coating composition containing the noble metal or copper colloid solution contains metal. Higher concentrations can have a metallic luster.
  • the metallic luster mentioned here includes a state called a half mirror. Those having this metallic luster can be used not only as an electromagnetic wave shield but also as a design material.
  • inorganic coatings with a high color depth and high saturation can be used as optical materials, for example, optical materials such as heat-resistant optical filters and non-linear optical materials, and coloring materials with high heat resistance and high durability. In addition, it can be used for antibacterial materials and catalysts.
  • the thickness of the inorganic coating can be selected according to the application to be used, but when it is used as an optical material, the dry thickness is preferably 0.05 to 10 / xm. When the film thickness is less than 0.05 / im, coloring power or electromagnetic wave shielding power may be lacked. When the film thickness exceeds ⁇ , peeling or cracking due to heating tends to occur.
  • the thickness is preferably 0.1 to 5 ⁇ .
  • the inorganic coating as an optical material produced by the above method uses the above-mentioned alcohol solution of a noble metal or copper colloid or a solution of a noble metal or copper colloid as a coloring agent, the resulting thin film is vivid. Color is applied and the applied color is chemically stable and does not fade.
  • the optical material is not particularly limited, and examples thereof include an optical filter such as a colored coating on the surface of a CRT of a television.
  • the alcohol solution of the noble metal or copper colloid of the present invention or the solution of the noble metal or copper colloid can be added to the metal alkoxide solution used in the sol-gel method, and a stable coating composition can be obtained. Obtainable.
  • the noble metal or copper colloidal alcohol solution or the noble metal or copper colloidal solution of the present invention has a sharper absorption curve than conventional ones. Higher saturation can be realized.
  • alcohol is used in the production process, so that the molecular weight of the high molecular weight pigment dispersant The effect is small, the degree of freedom of each dispersant molecule is high, the kinetic rate is low, and it is easy to coordinate with each of the noble metal or copper particles to be dispersed, and the particle size of each colloid particle Acts as a protective colloid in a small state, the particle size distribution becomes narrow, and as a result, the absorption curve It is thought that it becomes a loop.
  • FIG. 1 is an absorbance curve showing the particle size distribution of gold colloid particles in an alcohol solution of gold colloid.
  • the solid line is for the toluene solution of gold colloid obtained in Production Example, and the broken line is for the ethanol solution of gold colloid obtained in Example 1.
  • the horizontal axis represents wavelength (nm), and the vertical axis represents absorbance.
  • Dispervik 190 Dispervik 191, Dispervik 192 and Dispervik 184 (all manufactured by Big Chemie), EF KA—450 and EF Place 0.5 g of KA-4450 (all manufactured by EF KA Chemikanole), Solsperse 2400 and Solsperse 2800 (all manufactured by Abyssia) in a container, and place in each container.
  • EF KA—450 and EF Place 0.5 g of KA-4450 all manufactured by EF KA Chemikanole
  • Solsperse 2400 and Solsperse 2800 all manufactured by Abyssia
  • Equation (1) was evaluated as follows. ⁇ : When the expression (1 ′) is satisfied.
  • Equation (2) was evaluated as follows. ⁇ : When equation (2) is satisfied.
  • Dispervik 190, Dispervik 191, Disparvik 192, EFKA-4550, EFKA-4540 are suitable.
  • the Desperbic 190 and the Despervik 191 were preferred.
  • a polymeric pigment dispersant 20 g of EF KA-450 550, 14 g of dimethylaminoethanol and 200 g of ethanol manufactured by EF KA Chemical Co., Ltd. were placed in a reaction vessel, and stirred. The polymer pigment dispersant was completely dissolved. On the other hand, tetrachloroethene mouthpiece (III) acid tetrahydrate (HA u C 1 4 ⁇ 4 H 2 0) was dissolved 1 2 g of ethanol 1 0 0 ml. While stirring the ethanol solution of the polymer pigment dispersant, an ethanol solution of tetraclo mouth (III) acid tetrahydrate was added thereto instantaneously.
  • Example 2 except that 20 g of EF KA-450 manufactured by EF KA Chemical was used instead of EF KA-450 manufactured by EF KA Chemical as a polymer pigment dispersant, the gold colloid was used. 37 g of a solution of gold colloid in ethanol having a solid content of 22% by weight and consisting of particles and a polymer pigment dispersant and exhibiting a bright and dense red color was obtained. As a result of T G—D T A measurement, the content of gold particles in the solid content was 65% by weight. /. Met.
  • the ethanol solution of the palladium colloid thus obtained was used with an ultrafiltration pencil type module AHP-0113 manufactured by Asahi Kasei Corporation. Then, a process of removing residual ions by filtration, adding ethanol to the obtained filtrate, and further filtering the mixture was repeated, and the palladium colloid particles and the polymer pigment dispersant from which the residual ion components were removed were removed. 30 g of a thick brown palladium colloid ethanol solution having a solid content of 40% by weight was obtained. As a result of TG-DTA measurement, the content of palladium particles in the solid content was 58 wt. /. Met.
  • Example 5 Preparation of a silver colloid ethanol solution was attempted according to Example 5 except that 240 g of Solsperse manufactured by Avicia was used as a high molecular weight pigment dispersant. A massive precipitate consisting of silver particles and Solsperse 2400 was formed, and a silver colloid ethanol solution was not obtained.
  • An ethanol solution of silver colloid was prepared in accordance with Example 5 except that 280.10 g of Solsperse manufactured by Avicia was used as a high molecular weight pigment dispersant. However, a massive precipitate composed of silver particles and Solsperse 2800 was formed, and a silver colloid ethanol solution was not obtained.
  • 4 g of Solsperse 280.000 and Aceton (60 g) manufactured by Avicia Co., Ltd. were placed in another container as a polymer pigment dispersant, and the polymer pigment dispersant was dissolved by stirring.
  • This polymer pigment dispersant solution was added to a reaction vessel containing an aqueous solution of tetrachlorobase (III) acid, and 13.0 g of 2-dimethylaminoethanol was added instantaneously with stirring.
  • the ethanol solution of gold colloid obtained in Example 1 was further greatly diluted with ethanol and transferred to a glass cell having a bottom surface of 1 cm X lcm, and a spectrophotometer MCPD—300 manufactured by Otsuka Electronics Co., Ltd. was used.
  • MCPD spectrophotometer
  • the toluene solution of colloidal gold obtained in Production Example was further greatly diluted with toluene, and the absorbance was measured in the same manner as in Example 7.
  • the absorption derived from the plasmon of the gold colloid having a maximum around 535 nm was found. I could observe it.
  • FIG. 1 shows an absorption curve in which the concentration of the gold colloid was adjusted so that the absorbance at the maximum of the absorption peak was 1.5.
  • Example 9 Preparation of Coating Composition Used for Sol-Gel Method
  • the alcohol solution of Examples 2 to 5 was used instead of the ethanol solution of colloidal gold obtained in Example 1 respectively. Except for the same procedure, Each of the compositions for inging was prepared. All of these coating compositions were stable at room temperature for 24 hours.
  • Example 8 a coating composition was prepared in the same procedure except that the toluene solution of colloidal gold obtained in Production Example was used instead of the ethanol solution of colloidal gold obtained in Example 1. However, they did not mix well, and a coating composition could not be obtained.
  • Example 8 The coating composition obtained in Example 8 was applied to a glass plate by spin coating, and then baked at 150 ° C. for 20 minutes to obtain a colored glass gel film having a thickness of 0.2 ⁇ . Was formed on a glass substrate.
  • the colored glass gel film was transparent and colored red. A rubbing test with a detergent was performed to evaluate the water resistance of the colored glass gel film, but no decolorization was observed. When the pencil hardness of the colored glass gel film was measured in accordance with JISK 540, it was 8 mm, and a sufficient hardness was obtained.
  • Example 11 The coating composition obtained in Example 11 was applied to a glass plate by a spin coating method, and then baked at 150 ° C. for 20 minutes to form a coating having a thickness of 0.2 ⁇ m. A colored glass gel film was formed on a glass substrate.
  • This colored glass gel film was transparent and colored yellow. A rubbing test with a detergent was performed to evaluate the water resistance of the colored glass gel film, but no decolorization was observed. When the pencil hardness of the colored glass gel film was measured in accordance with JISK 540, it was 8 mm, and a sufficient hardness was obtained.
  • the ethanol solution of the gold colloid obtained before the ultrafiltration obtained in Example 1 was subjected to the residual ion separation using an ultrafiltration pencil type module manufactured by Asahi Kasei Corporation. Was removed by filtration, and a step of adding water to the obtained filtrate and further performing filtration was repeated. By repeating this operation, the residual ion component is removed. In both cases, the solvent was replaced with water from ethanol to obtain 37 g of an aqueous solution of colloidal gold composed of colloidal gold particles and a polymer pigment dispersant with a solid content of 25% by weight. As a result of TG-DTA measurement, the content of gold particles in the solid content was 56% by weight.
  • Comparative Examples 1 to 3 when a high-molecular-weight pigment dispersant other than the above-described predetermined high-molecular-weight pigment dispersant was used, an alcohol solution of a metal colloid was not obtained. From the results of Comparative Example 5, the toluene solution of gold colloid prepared in the Production Example was not suitable for use in the coating composition used in the sol-gel method. From the results of FIG.
  • the absorption curve derived from the ethanol solution of the colloidal gold of Example 1 was sharper than the absorption curve derived from the toluene solution of the colloidal gold of Production Example, In particular, sharp particles were obtained on the long wavelength side, indicating that the particle size distribution of the colloidal gold particles was narrow.
  • the colloidal alcohol solution of a noble metal or copper of the present invention, and the colloidal solution of a noble metal or copper obtained by the solution preparation method of the present invention have the above-described configuration, and contain a high concentration of noble metal or copper colloid particles. And the absorption curve becomes sharper than before, so that it also has excellent coloring properties. it can. Furthermore, since it can be suitably used for the sol-gel method, the inorganic coating obtained by the sol-gel method can be used for optical materials such as optical filters and non-linear optical materials having excellent heat resistance, coloring materials, antibacterial materials, catalysts, and electromagnetic wave shielding. It can be suitably used for example.

Abstract

L'invention concerne solution alcoolique contenant des particules colloïdales d'un métal noble ou de cuivre et un dispersant de pigments à haute molécularité, et présentant une concentration élevée et un pouvoir colorant adéquat, qui convient pour un procédé sol-gel. Cette solution est caractérisée en ce que l'alcool comprend de un à quatre atomes de carbone et le dispersant de pigments à haute molécularité satisfait à la relation (1) ou (2) suivante : (1) A ≥ 3 ml et 3 ml ≤ B ≤ 40 ml ; (2) 0,25 ≤ A/B ≤ 4,5, dans lesquelles A et B représentent les quantités respectives d'eau et d'hexane nécessaires pour rendre trouble une solution cétonique obtenue par dissolution de 0,5 g de dispersant à haute molécularité dans 10 ml d'acétone.
PCT/JP2001/004214 2001-05-21 2001-05-21 Solution alcoolique colloidale de metal noble ou de cuivre, procede permettant de produire cette solution et composition de revetement WO2002094953A1 (fr)

Priority Applications (4)

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JP2002592416A JPWO2002094953A1 (ja) 2001-05-21 2001-05-21 貴金属又は銅のコロイドのアルコール溶液及びその製造方法並びにコーティング用組成物
CN01813038.0A CN1443228A (zh) 2001-05-21 2001-05-21 贵金属或铜的胶体醇溶液、其制造方法及涂料组合物
PCT/JP2001/004214 WO2002094953A1 (fr) 2001-05-21 2001-05-21 Solution alcoolique colloidale de metal noble ou de cuivre, procede permettant de produire cette solution et composition de revetement
TW091110472A TW570963B (en) 2001-05-21 2002-05-20 Alcohol solution of noble metal or copper colloids, method of producing the same, and coating composition

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PCT/JP2001/004214 WO2002094953A1 (fr) 2001-05-21 2001-05-21 Solution alcoolique colloidale de metal noble ou de cuivre, procede permettant de produire cette solution et composition de revetement

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JP2005060824A (ja) * 2003-07-28 2005-03-10 Mitsuboshi Belting Ltd 合金微粒子の製造方法及び合金薄膜の製造方法
JP2005120074A (ja) * 2003-08-11 2005-05-12 L'oreal Sa 安定化し、場合によっては被覆した金属粒子を含む化粧品組成物
JP2005270957A (ja) * 2004-02-26 2005-10-06 Mitsubishi Materials Corp 金属微粒子の抽出方法等および用途
WO2005092519A1 (fr) * 2004-03-29 2005-10-06 Nippon Paint Co., Ltd. Procédé pour la formation d’une pellicule d’enrobage lumineux et article à enrobage lumineux
JP2005320616A (ja) * 2003-09-05 2005-11-17 Mitsubishi Materials Corp 金属微粒子とその含有組成物等
JP2006089786A (ja) * 2004-09-22 2006-04-06 Mitsuboshi Belting Ltd 極性溶媒に分散した金属ナノ粒子の製造方法

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CN104897726A (zh) * 2015-05-22 2015-09-09 兰州大学 一种利用溶胶-凝胶法制备的高灵敏度气体传感器

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JP2005060824A (ja) * 2003-07-28 2005-03-10 Mitsuboshi Belting Ltd 合金微粒子の製造方法及び合金薄膜の製造方法
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