Colloidal metal solution, process for producing the same, and coating material containing the same

Technical field

0001The present invention relates to a solution, the metal colloid particles therein dispersed, and a method for producing the same, and further a coating material using the metal colloid solution.

Technical background

0002Various transparent substrate materials such as plastics or glass to Use in screens of display devices such as cathode ray tubes, liquid crystal displays and the like, window materials for clean rooms and packaging materials for electronic components or films for use in overhead displays or photographs are usually to insulating materials and therefore tend to electrostatic charging. Therefore, like collecting dust or fine powder to substrate surfaces, the glitches to sometimes of electrical appliances and the like leads. influences of electromagnetic waves of personal computers and television screens are produced on human body are an existing problem.

0003Around antistatic protection or shielding electromagnetic waves provide, it is common Practice, a Beschich processing medium or electrically conductive materials to apply to substrates containing paint or Mixture of substrate materials and electrically conductive materials to form. Metal particles are commonly used as such electrically conductive materials. In particular, metal particles, the average particle sizes of comprise about 1-100 nm, called Kolloidmetallteilchen, the property, to be able to transmit visible light, and they are therefore suitable for use in the transparent substrate materials. They are the most suitable electrically conductive materials for shielding electromagnetic waves, the high electric conductivity require. The colloidal metal particles are usually in a state of colloidal metal solution used, wherein the colloidal metal particles in a dispersion medium are dispersed. However, the colloidal metal particles have due very small particle sizes a size surface energy and aggregating therefore like and are marginally stable in dispersion media, such as water, organic solvents and the like, to disperse. It is known, for the desired stable Dispersion surfaces of colloidal metal with a stabilizing agent identified as a "protective colloid" to protect them from the dispersion.

0004For example discloses M Carey Lea, American Journal of Science, vol 37, p 476-491, 1889, a method for producing a colloidal metal solution by Addition of citric acid or a salt thereof to an aqueous solution a metal salt as a protective colloid, and then a reducing agent, such as iron (II) ions and the like, at this and subsequent desalting and concentrating. The method requires a large amount of the protective colloid to stabilize the dispersion of colloidal Metal particles, which leading to a further problem of reducing electrical conductivity results of colloidal metal. Further, it makes the stabilization of the dispersion by a protective colloid hard to reaggregate the colloidal metal, and removing salts from the metal colloid solution and the concentration of the colloidal need metal Operations, such as centrifugation, ultrafiltration, deionization and the like, so the large-caliber Devices require that mass production is unfavorable.

0005The <patcit><text>JP-A-10-195505</text></patcit> disclosed a process for the preparation of powders of colloidal metal particles with thiolgeschützten surfaces by performing a reduction reaction on a solution containing a metal salt and contains an amine, and subsequent Addition of a thiol to the solution. The method is based on the concentration of a solution containing metal colloid particles contains, in a rotary evaporator to remove the colloidal metal as powder, and thus have been problems, such as desalting, and the Productivity, not yet solved by the method. That is, it is difficult to metal colloid solution produce in a good dispersion state.

Disclosure of the Invention

0006The conventional metal colloid solution had as a result of dispersion stability problem and also a technology problem the concentration on a commercial scale to date only a high concentration colloidal metal particles of 1 wt .-%.

0007task of the present invention is to provide a colloidal Metal solution, The high electrical conductivity and the like can give a clear and dispersion stability over a long can hold period, and further to provide a Paint using the metal colloid solution.

0008A Another object of the present invention is to provide a commercially and economically advantageous process for Producing a colloidal metal solution, wherein the concentration colloidal metal particles can be selected as desired, without a Centrifuge or a rotary evaporator to use.

0009As Result of intensive studies, the inventors of the present invention that a metal colloid solution by using a sulfur compound of low molecular weight on as a protective colloid and adjusting the pH value of the solution the basic side was prepared which contained colloidal Metal is about can hold stably dispersed for a long time, wherein the sulfur compound a low molecular weight a significant protective colloid function has, even if it is used in a small amount, and also easy to thermal decomposition or volatilization can be subjected, ie the time of fixing the colloidal Metal particles can be easily removed to a substrate, resulting in apparent electrical conductivity and the like leads. The present inventors further have found that for producing such a metal colloid solution metal colloid particles with the sulfur compound of low molecular weight to the particle in a solution first be prepared, and then the pH of the solution is adjusted to the acidic side, order to make it easy to aggregate the colloidal metal and the salts and solvents to remove. The aggregated colloidal metal hold Sulfur compounds on the particle surfaces and can therefore, by setting the pH of the solution redispersed to the basic side readily. That is, a metal colloid solution can be obtained with a significant dispersion stability. The present inventors further have found that the colloidal metal particles to the substrate by use of a Two-component paint, which consists of a first fluid comprises at least the colloidal Me talllösung, and a second Liquid, a curable resin component comprises, consists, be fixed and for the case that the dispersion medium the first liquid comprises water as a main component, the coating film formed clear transparency, electrical conductivity and the like, if a non-aqueous solvent a high dielectric constant and a high boiling point is added to the first liquid. The present invention has been further investigation on the Base made of these findings.

0010By the present invention there is provided a colloidal Metal solution, consisting essentially of <ul><li>(I) colloidal metal with a sulfur compound of low molecular weight to the particle as a protective colloid and</li><li>(Ii) a water solvent consists, wherein the sulfur compound is at least one, from the group consisting of mercaptoacetic acid, mercaptopropionic acid, thiodipropionic acid, mercaptosuccinic acid, mercaptoethanol, Thiodiethylene glycol, thiodiglycolic, aminoethyl mercaptan, thiodiethyl, Thiourea, thioformamide and the salts thereof is selected, the Content of the sulfur compound from 0.05 to 1.5 parts by weight, based on one part by weight of colloidal metal particles is, the Metal of the colloidal metal particles is at least one element selected from the group consisting of metals belonging to Group 8 and Group 1B of the periodic table, selected is, and the solution not less than 1 wt .-% contains to the colloidal metal particles and a having pH of 8-14.</li></ul>

0011By The present invention further provides a Process for producing a colloidal metal solution, which <ul><li>(I) a first step of forming colloidal Metal particles with a sulfur compound of low molecular weight on the particle as a protective colloid in a water solvent, wherein: the sulfur compound is at least one selected from the group consisting of mercaptoacetic acid, mercaptopropionic acid, thiodipropionic acid, mercaptosuccinic acid, mercaptoethanol Thiodiethylene glycol, thiodiglycolic, aminoethyl mercaptan, thiodiethyl, Thiourea, thioformamide and the salts thereof is selected, the Content of the sulfur compound from 0.05 to 1.5 parts by weight, based on one part by weight of colloidal metal particles is, the Metal of the colloidal metal particles is at least one element selected from the group of metals that to Group 8 and Group 1B of the periodic table, selected is,</li><li>(Ii) a second step of adjusting the solution to a pH of not more than 5, whereby the colloidal metal particles aggregate, and the recovery of the colloidal metal particles by filtration and</li><li>(Iii) a third step of dispersing the colloidal obtained Metal particles in a water solvent at a pH of 8-14 includes.</li></ul>

0012By The present invention further provides a Paint, at least the colloidal metal and a curable Resin, wherein the coating material is preferably a two-component paints is that a first liquid, at least the colloidal metal solution includes, and a second liquid, the at least one curable includes resin component comprises. Furthermore, carried out by the present invention to provide a process for forming a coating film using the two-component paint and a method for making an article with the coating film thereon.

Best Mode for carrying out the invention

0013The present colloidal metal solution is a solution, the metal colloid particles dispersed therein, and the solution consisting essentially of colloidal metal particles with a sulfur compound a low molecular weight as a protective colloid on the particle surfaces and a water solvent as a dispersion medium. The solution contains not less than 1 wt .-%, preferably 2-50 wt .-%, more preferably 5-50 Wt .-% of the colloidal metal particles and has a pH 8-14, preferably 8-13, more preferably 8-12 at. conventional metal colloid solution contains only 1 wt .-% of colloidal metal particles with maximum concentration due to the dispersion stability problem and technology problem of commercial concentration and therefore suffer compositions that use conventional metal colloid solution, to considerable restrictions in view of the desired Design combinations and properties.

0014metal species for use as components of the colloidal metal particles are not especially limited, but is at least one metal species selected from the group of metals Group 8 of the periodic table (iron, cobalt, nickel, ruthenium, Rhodium, palladium, osmium, iridium and platinum) and metals of the Group 18 (copper, silver and gold) is selected, in many applications used, of which gold, silver, platinum, palladium and copper due to significant electrical conductivity and the like are particularly are preferred. Colloidal metal particles can be made of an alloy of consist of at least two of the above-mentioned metal species or from a mixture of at least two types of colloidal metal particles consist. Colloids metal particles have an average Particle size of about 1-100 nm, and those having an average particle size of 5-50 nm are preferred due to the clear transparency. The dispersion medium is for use in the present colloidal metal solution a water solvent. The metal colloid solution has a pH of 8-14, because the colloidal metal can be stably dispersed at high concentration. If the metal colloid solution has a lower pH than 8, the colloidal metal solution can not have a long period of time are kept in a stable dispersion state. Preferably, the pH value is lower than 13, since a basic substance as a pH control agent hardly any influence on the electrical conductivity exercises.

0015The colloidal metal particles have a sulfur compound of low Molecular weight on the particle surfaces as a protective colloid. The content of the sulfur compound is 0.05-1.5 parts by weight the basis of 1 part by weight of the colloidal metal particles, as a sufficient stabilization effect can be obtained as a protective colloid can. , the sulfur compound of low molecular weight also in a small proportion to good effect as a protective colloid. When used in a thermosetting Composition tends the sulfur compound to decompose or volatilization at a temperature lower than 250 ° C and they can therefore without large heat load of the substrate are removed.

0016The Sulfur compounds of low molecular weight are particularly those having molecular weights of 34-200, preferably 48-180, said mercaptoacetic (Molecular weight: 92, boiling point: 110-112 00), mercaptopropionic acid (molecular weight: 106, boiling point: 111-112 ° C / 2.0 x 10³ Pa), thiodipropionic acid (molecular weight: 178), mercaptosuccinic (Molecular weight: 150), mercaptoethanol (molecular weight: 78, Boiling point: 157 ° C / 99.7 × 10³ Pa), thiodiethylene glycol (molecular weight: 122, boiling point: 164-166 ° C / 2.7 x 10³ Pa), thiodiglycolic acid (molecular weight: 150), Aminoethyl mercaptan (molecular weight: 77), thiodiethyl (molecular weight: 120, boiling point: 231-233 ° C / 101.0 × 10³ Pa), thiourea (molecular weight: 76), Thioformamide (molecular weight: 61) and include their salts. At least one of these sulfur compounds can be used. Especially are swingfelverbindungen thiol-based (ie, compounds with a hydrogen atom of an aliphatic hydrocarbon substituting SH group of the general formula RSH (wherein R is an alkyl group and the like is)) to colloidal due to higher affinity Metal particles and a significant protective colloid function preferably and mercaptoacetic, mercaptopropionic and mercaptoethanol particularly preferred.

0017The present invention further provides a process for preparing a colloidal metal solution ready, the method comprising a first step of forming colloidal Metal particles with a sulfur compound of low molecular weight on the particle in a water solvent, a second step of adjusting the solution to a pH of not more than 5, whereby the aggregated colloidal metal be, and the recovery of the colloidal metal particles by filtration and a third step of dispersing the colloidal obtained Metal particles in a dispersion medium at a pH of 8-14 includes.

0018The first stage is a step of forming colloidal metal particles with a sulfur compound of low molecular weight to the particle in a water solvent. Therefore, a water solvent, which is a compound of a metal, the colloidal metal particles to form capable contains, to a pH value of 8-14 in the presence of a sulfur compound low molecular weight adjusted, whereby such a Metal compound to a reduction reaction is subjected, or the water solvent containing such a metal compound is adjusted to a pH of 8-14 and then the sulfur compound of low molecular weight added thereto, whereby the metal compound a reduction reaction is subjected. When the pH of the solution of low than 8, a part of the metal compound is precipitated, and he not reduced remains. The pH of the metal compound containing solution is in a range of preferably 8-13, more preferably 8-12.

0019The mentioned above sulfur compounds have the Sulfur compound of low molecular weight are used and in particular those having a molecular weight of 34-200 are preferred, and those having a molecular weight of 48-180 even better. Sulfur compounds thiol-based are still cheaper and at least one compound of mercaptoacetic acid, mercaptopropionic acid and Mercaptoethanol is at best used. The sulfur compound is present in a proportion of 0.05-1.5 Parts by weight per 1 part by weight of the colloidal metal particles used. When the reduction reaction of the metal compound in the absence the sulfur compound of low molecular weight is performed, are the colloidal metal particles formed in this way directly precipitated and the surfaces the colloidal metal particles also remain in to allow sulfur compound then not fully protected, making a redispersion of the particles difficult. Therefore, it is necessary, the metal compound of the reduction reaction in the presence of subjecting the sulfur compound.

0020The Metal compound is a compound of a metal, the colloidal may form metal particles by a reduction reaction. For example can Metal chlorides, metal sulfates, metal nitrates, metal carbonates and the like are used as the metal compound. The concentration of the metal compound in the solution is not limited, provided that the metal compound in the solution is soluble and not less than 5 mmol / l is commercially reasonable. Solvents to dissolve the metal compound may be a water solvent or at least one organic solvent, such as an alcohol and the like. To produce a aqueous colloidal metal solution the metal compound is preferably water, but can hardly water-soluble Metal compounds also together with a compound which contains chloride ions, ammonia or the like, the soluble are able to form complexes with the metal component, are used.

0021The may reduction reaction by adding a reducing agent to the solution the metal compound or irradiation can be carried out with light. The reducing agent includes, for example, phosphoric acid, phosphinic acid, citric acid and their salts, sodium borohydride, hydrazine, aldehydes, amines, alcohols and the like, but it is not particularly limited. The Reduction reaction can be performed at any temperature and in the case of the reduction reaction in an aqueous solution is a temperature of 5-90 ° C preferable because the reaction can take place readily. A total of is used to perform the reduction reaction, and the stable dispersion in this way formed colloidal metal, the reducing agent preferably used in a proportion of 0.2-50 mol per 1 mol of the metal compound. the The method of the irradiation with light is absorbed. Light deposition method, the irradiating the metal compound with a light to reduce comprises the metal compound to the metal appropriate wavelength.

0022The second step is a step of adjusting the solution containing colloidal metal particles, the in the first stage was obtained to a pH value of not more than 5, preferably 0-5, by an acidic compound and the like, whereby the colloidal Metal particles are aggregated, and the recovery of the colloidal Metal particles by filtration. The exhibit colloidal metal a sulfur compound of low molecular weight on the particle as a protective colloid, and therefore the colloidal metal can readily accomplished by adjusting the solution to a pH of not more than 5 are aggregated and by a relatively simple won separation process as suction filtration, sedimentation and the like will. The obtained colloidal metal can contribute complete removing soluble Salts by the usual Procedures are washed, leading to preferred properties such as electric conductivity and the like leads.

0023The third step is a step of dispersing the colloidal metal particles, by the second stage including as required washing and the like were obtained in a dispersion medium at a pH-value 8-14, preferably 8-13, more preferably 8-12. The colloidal metal can in a dispersion medium at a pH of 8-14, due to the Presence of the sulfur compound of low molecular weight on the particle redisperse readily. The colloidal metal are usually as wet cake by filtration ge gained and can thereby by stirring redispersed with the addition of a dispersion medium for the wet cake will. A mixer such as a line mill, a colloid mill and the like, can, be used if necessary to re-dispersion. As the dispersion medium to re-dispersion of colloidal metal is a water solvent used. In the present invention, the colloidal metal can be prepared such that they at any desired concentration of the have redispersion. For example, a highly concentrated metal colloid solution, 1-50 wt .-% of colloidal metal contains, without any concentration and the like are obtained.

0024In of the present invention include basic compounds for use at the pH adjustment, hydroxides of alkali metals or alkaline earth metals, such as sodium hydroxide, potassium hydroxide, calcium hydroxide and the like; Ammonium compounds such as ammonia and the like, and amines or . like Acidic compounds include inorganic acids such as Hydrochloric acid, Sulfuric acid, nitric acid and the like, and organic acids such as formic acid, acetic acid, propionic acid, and . like The basic compounds or the acidic compounds are not particularly limited. The present colloidal metal solution is useful as an electrically conductive material and they can also as an antibacterial agent, coloring agent, catalyst and the like be used.

0025The present invention further provides a coating agent which at least the metal colloid solution and a curable includes resin component. The combination of the metal colloid solution a curable Resin component, such as inorganic resins such as alkyl silicate, Alkyl titanate and the like, or organic resins, for example, an acrylic resin, alkyd resin, polyester resin, urethane resin, epoxy resin, Melamine resin and the like, can give a paint which can result in the colloidal metal inherent functions. Any component of the cold curing type, by firing curable Type ultraviolet curing, can be used as the curing resin component used type and the like will. In particular, a low temperature burning is carried curable Type preferably used, since the sulfur compound of low Molecular weight as the protective colloid by heating at such a low Temperature decomposed or volatilized can without stressing the substrate thermally. The mixing ratio the curable Resin component can be appropriately selected. The right choice a dispersion medium for redispersing the colloidal metal can have any paint on the basis of an organic solvent and aqueous Paints result. In the present invention, a highly concentrated colloidal metal solution can be prepared and therefore can produced from such a highly concentrated colloidal metal solution Paints a higher Solids concentration, a clear film-forming ability and the like. Such paints can colloidal Metal particles of ceramics, metals and the like or in particular transparent substrates such as glass, plastics, foils and the like, fix, and therefore as electrically conductive materials, antistatic Materials, materials for shielding against electromagnetic Waves, antibacterial materials, color materials, catalysts and the like.

0026the This paint is preferably a two-component paints, a first liquid, covering at least the metal colloid solution, and a second Liquid, the at least one curable includes resin component comprises. The two-component paints is particularly favorable as the electrically conductive paint, as a particularly high electric conductivity, which is suitable for shielding electromagnetic waves, without Presence of insulating curable Resin component at the interface between the colloidal metal particles and the substrate by applying the first liquid, the ever no content of the curable comprises resin, and then applying the second liquid and then hardening can be obtained. The dispersion medium of the first liquid for a Such a two-component paint is usually water as the main component. When water as the dispersion medium of the first liquid is used, it is favorable, a non-aqueous solvent a high dielectric constant and a high boiling point to admit. The present colloidal metal solution uses a sulfur compound of low molecular weight as a protective colloid, and therefore may be difficult steric Hinderungsaktion occur, and the colloidal metal particles tend to aggregate, when water is evaporated, since the surface tension of water high can be kept until the curing terminated by heating and drying is, however, the addition of non-aqueous solvent a high dielectric constant and a high boiling point, the aggregation of colloidal metal particles suppress what the desired electrical conductivity and transparency leads. It is not cheap, a common Dispersing agents such as a surfactant and the like, to use, although this is desired by the uses depends, as it on the surfaces colloidal metal particles is strongly absorbed, which is sometimes than the electrical conductivity inhibiting factor acts. Further, preferably, the non-aqueous solvent has a lower surface tension because an Marmorierungsverfärbung on the coating film takes place and less significant smoothness, free from wrinkling or shrinking, get on this can be.

0027especially have non-aqueous solvent preferably a dielectric constant of not less than 35, more preferably 35-200, and preferably a boiling point of not lower than 100 ° C, even cheaper 100 ° C-250 ° C. Such non-aqueous solvent include N-methylformamide (dielectric constant: 190, boiling point: 197 ° C), Dimethyl sulfoxide (dielectric constant: 45, Boiling point: 189 ° C), Ethylene glycol (dielectric constant: 38, Boiling point: 226 ° C), 4-butyrolactone (dielectric constant: 39, Boiling point: 204 ° C), Acetamide (dielectric constant: 65, Boiling point: 222 ° C), 1,3-dimethyl-2-imidazolidinone (dielectric constant: 38, boiling point: 226 ° C), Formamide (dielectric constant: 111, boiling point: 210 ° C), N-methylacetamide (dielectric constant: 175, boiling point: 205 ° C), Furfural (dielectric constant: 40, Boiling point: 161 ° C) and the like, at least one of which can be used. Further, the non-aqueous have solvent preferably a surface tension of not more than 50 × 10^-3 N / m, even cheaper 10 × 10^-3-50 × 10^-3 N / m on. Such non-aqueous solvent include N-methyl formamide (surface tension: 38 x 10^-3 N / m), Dimethyl sulfoxide (surface tension: 43 × 10^-3 N / m), Ethylene glycol (surface tension: 48 × 10^-3 N / m), 4-butyrolactone (surface tension: 44 × 10^-3 N / m), Acetamide (surface tension: 39 × 10^-3 N / m), 1,3-dimethyl-2-imidazolidinone (surface tension: 41 x 10^-3 N / m) and . like The content of the non-aqueous solvent is preferably 15-900 parts by weight, more preferably 15-50 parts by weight, based on 100 parts by weight of water in the first liquid is included.

0028The second liquid for the This two-component paints comprising at least one curable resin component. As the curable Resin component can inorganic resins such as alkyl silicate, alkyl titanate and the like; and organic resins such as an acrylic resin, alkyd resin, polyester resin, urethane resin, epoxy resin, Melamine resin and the like are used, and any Component of the cold curing Type curable by firing Type ultraviolet curing, Type and the like can also be used. especially is curable a low temperature by firing Type preferably used, since the sulfur compound of low Molecular weight as the protective colloid by heating at such a can be low temperature decomposed or volatilized without Substrate to charge thermally. The mixing ratio of the curable Resin component can be appropriately selected.

0029The first liquid or the second liquid can a filler, such as colloidal silica, titanium oxide fine particles, fine tin oxide and the like, various additives, different colorant, a Solvents, such as alcohols, ketones, esters, aromatic compounds, aliphatic Compounds and the like, various dispersants and like. The two-component paint may as electric conductivity imparting materials, antistatic materials, materials for shielding electromagnetic waves and the like for substrates use of glass, plastics, films and the like.

0030On Coating film can be made of the present two-component paints by applying the first liquid containing on a substrate, thereby forming a metal colloid particles Layer, then applying the second liquid on the layer and curing the curable Resin component are formed. In particular, by application the first liquid, the colloidal metal particles with a sulfur compound of low Molecular weight on the particle comprises, on a substrate by Spin coating, dip coating, bar coating, spray coating or the like, whereby a layer is formed, the colloid the contains metal particles on the substrate surface, then Applying the second liquid similarly Manner on the layer and curing the curable Resin component by heating, drying or the like, whereby fixes the colloidal metal particles at the substrate surface be formed a coating film on the substrate surface will. The coating film obtained in this manner has significant electric conductivity, antistatic property, the property of shielding electromagnetic Waves and the like, for example, a significant electrical conductivity of preferably not more than 1 × 10³ Ω / square with respect to the surface resistivity, which as a specific Resistance per unit area is indicated on. The film thicknesses of the applied first and second liquids are not particularly limited, However, they are preferably in the range of 0.01-10 microns, respectively in terms on the processability and the distribution property. objects with a coating film containing the colloidal metal particles, on the surfaces can produced by said above application processes will. Various articles can for the Application may be used, such as plastic products, Film products, paper products, glass products, ceramic products and like, in particular display devices such as cathode ray tubes, liquid crystal display devices and the like, window materials for clean rooms, packaging materials for electronic components, Films for use in overhead displays, photographs and the like and so on.

Examples

0031The present invention will be hereinafter detailed with reference to Examples, which do not as the present invention restrictive should be interpreted.

example 1

1. First stage

00323.0 g mercaptoacetic as the sulfur compound of low molecular weight was added to 1000 ml of an aqueous Silver nitrate solution added at a concentration of 50 mmol / l with stirring, after which the aqueous solution containing Ammonia water (26%) was adjusted to a pH of 10.0. 50 ml of aqueous Sodium borohydride with a concentration of 400 mmol / l reducing agent were quickly added to the aqueous solution at room temperature for carrying out where a reduction reaction. Colloids silver particles with mercaptoacetic on the particle were in the solution thereby formed.

2. Second Stage

0033The obtained in the first stage solution was with nitric acid (20%) adjusted to a pH value of 3.0, the colloidal silver particles precipitate and then, the precipitated won colloidal silver particles through a vacuum filter and with washed water until the electrical conductivity of the filtrate became not more than 10.0 ĩS / cm reached, thereby obtaining wet cake of colloidal silver were.

3. Third Stage

0034The wet cake of colloidal silver, the second in the Stage were recovered by filtration, were added to water, to provide a concentration of the colloidal silver particles of 10% to produce, and therein with stirring redispersed while the solution adjusted with ammonia water (26%) to a pH value of 9.0 was, whereby the present colloidal silver solution (Sample A) was obtained.

example 2

0035The present colloidal silver solution (Sample B) was prepared according to Example 1 was obtained, except that in the first stage of Example 1 used as a reducing agent aqueous solution of sodium borohydride by 50 ml of an aqueous hydrazine was replaced with a concentration of 800 mmol / l.

example 3

0036The present colloidal silver solution (Sample C) was prepared according to Example 1 was obtained, except that in the first stage of Example 1 used as the sulfur compound of low molecular weight mercaptoacetic by 3.0 g of 3-mercaptopropionic was replaced.

example 4

0037The present colloidal silver solution (Sample D) was prepared according to Example 1 was obtained, except that in the first stage of Example 1 used as the sulfur compound of low molecular weight mercaptoacetic was replaced by 3.0 g of 2-mercaptoethanol.

example 5

0038The present colloidal silver solution (Example E) was prepared according to Example 1 was obtained, except that the in the third stage of Example 1 Ammonia water used as the basic substance of a pH adjusting agent was replaced by 2-aminoethanol.

example 6

0039The present colloidal silver solution (Example F) was measured according to Example 1 was obtained, except that the in the third stage of Example 1 Ammonia water used as the basic substance of a pH adjusting agent by an aqueous sodium hydroxide (10%) was replaced.

example 7

1. First stage

00403.0 g of 3-mercaptopropionic acid were used as sulfur compound of low molecular weight to 1000 ml of an aqueous Palladium chloride solution under stirring with a concentration of 50 mmol / l and was then the aqueous solution with ammonia water (26%) adjusted to a pH value of 10.0. 50 ml of an aqueous hydrazine were at a concentration of 800 mmol / l reducing agent rapidly to the aqueous solution at room temperature for carrying out where a reduction reaction, whereby colloidal palladium with 3-mercaptopropionic on the particle in the solution were formed. The aqueous Palladium chloride solution was prepared by adding 0.8 parts by weight of sodium chloride per 1 part by weight Palladium chloride and subsequent solution in water.

2. Second Stage

0041The obtained in the first stage solution was with hydrochloric acid (20%) adjusted to a pH value of 3.0 to colloidal palladium precipitate. The colloidal palladium particles were recovered by a vacuum filter and washed with water until the electrical conductivity of the filtrate became not more than 10.0 s / cm reached, thereby forming wet Cake obtained colloidal palladium particles.

3. Third Stage

0042The moist cakes of colloidal palladium particles, the second in the Stage were recovered by filtration, were added to water, to prepare a colloidal palladium concentration of 10%, and in water with stirring redispersed while the aqueous solution adjusted with ammonia water (26%) to a pH value of 9.0 was, whereby the present colloidal palladium solution (sample I) was obtained.

example 8

1. First stage

00431.5 g of 3-mercaptopropionic acid were used as sulfur compound of low molecular weight to 1000 ml of an aqueous Chloroplatinic acid solution optionally a concentration of 25 mmol / l with stirring and then was the aqueous solution with ammonia water (26%) adjusted to a pH value of 10.0. 50 ml of an aqueous hydrazine with a concentration of 1600 mmol / l reducing agent were rapidly to the aqueous solution at room temperature for carrying out where a reduction reaction, whereby colloidal platinum with 3-mercaptopropionic on the particle in the solution were formed.

2. Second Stage

0044The obtained in the first stage solution was with hydrochloric acid (20%) adjusted to a pH value of 3.0 to colloidal platinum precipitate. The colloidal platinum particles were recovered by a vacuum filter and washed with water until the electrical conductivity of the filtrate became not more than 10.0 s / cm reached, thereby forming wet Cake obtained colloidal platinum.

3. Third Stage

0045The wet cake of colloidal platinum particles, the second in the Stage were recovered by filtration, were added to water, to produce a concentration of colloidal particles of platinum of 10%, and in water with stirring redispersed while the aqueous solution adjusted with ammonia water (26%) to a pH value of 9.0 was, whereby the present colloidal platinum solution (Sample J) was obtained.

example 9

1. First stage

00461.5 g of 3-mercaptopropionic acid were used as sulfur compound of low molecular weight to 1000 ml of an aqueous chloroauric acid with optionally a concentration of 25 mmol / l with stirring and then was the aqueous solution with ammonia water (26%) adjusted to a pH value of 10.0. 50 ml of an aqueous hydrazine with a concentration of 1200 mmol / l reducing agent were rapidly to the aqueous solution at room temperature for carrying out where a reduction reaction, whereby colloidal gold particles with 3-mercaptopropionic on the particle in the solution were formed.

2. Second Stage

0047The obtained in the first stage solution was with hydrochloric acid (20%) adjusted to a pH value of 3.0 to colloidal gold particles precipitate and the colloidal gold particles were recovered by a vacuum filter and washed with water until the electrical conductivity of the filtrate became not more than 10.0 s / cm reached, thereby forming wet Cake obtained colloidal gold particles.

3. Third Stage

0048The wet cake of colloidal gold particles in the second stage were recovered by filtration, were added to water to make a produce concentration of colloidal gold particles of 10%, and in Water while stirring redispersed while the aqueous solution adjusted with ammonia water (26%) to a pH value of 9.0 was, whereby the present colloidal gold solution (sample K) was obtained.

example 10

1. First stage

00493.0 g of 3-mercaptoacetic were used as sulfur compound of low molecular weight to 1000 ml of an aqueous copper acetate under stirring with a concentration of 50 mmol / l and was then the aqueous solution with ammonia water (26%) adjusted to a pH value of 10.0. 50 ml of an aqueous sodium borohydride with a concentration of 800 mmol / l as a reducing agent were rapidly to the aqueous solution at room temperature for carrying out where a reduction reaction, whereby colloidal copper with mercaptoacetic on the particle in the solution were formed.

2. Second Stage

0050The obtained in the first stage solution was with nitric acid (20%) adjusted to a pH value of 3.0 to colloidal copper precipitate and the colloidal copper particles were recovered by a vacuum filter and washed with water until the electrical conductivity of the filtrate became not more than 10.0 s / cm reached, thereby forming wet Cake obtained colloidal copper particles.

3. Third Stage

0051The wet cake of colloidal copper particles in the second Stage were recovered by filtration, were added to water, to a concentration of colloidal copper particles of 10 to produce, and in water with stirring redispersed while the aqueous solution adjusted with ammonia water (26%) to a pH value of 9.0 was, whereby the present colloidal copper solution (Sample L) was obtained.

example 11

1. First stage

00523.8 g sodium borohydride as a reducing agent were in 3000 ml of water dissolved and the aqueous solution was (26%) adjusted with ammonia water to a pH value of 11.0, followed by the addition of 2.5 g of mercaptoacetic acid as a sulfur compound a low molecular weight, followed by an aqueous mixed solution from the reducing agent and the sulfur compound of low Molecular weight produce. 20.0 g of silver nitrate were in 2000 dissolved ml water and the aqueous solution was adjusted with ammonia Waser (26%) to a pH value of 11.0 and then the total amount of the mixed aqueous solution was added to the aqueous solution stirring at room temperature Administered 30 min to perform a reduction reaction, whereby colloidal silver particles with mercaptoacetic on the particle in the solution were formed. The molar ratio of the reducing agent to the silver nitrate was 0.85.

2. Second Stage

0053The obtained in the first stage solution was with nitric acid (20%) adjusted to a pH value of 3.0 to colloidal silver precipitate. The colloidal silver particles were recovered by a vacuum filter and washed with water until the electrical conductivity of the filtrate became not more than 10.0 s / cm reached, thereby forming wet Cake obtained colloidal silver.

3. Third Stage

0054The wet cake of colloidal silver, the second in the Stage were recovered by filtration, were added to water, to a concentration of colloidal silver particles of 10 to produce, and in water with stirring redispersed while the aqueous solution adjusted with ammonia water (26%) to a pH value of 9.0 was, whereby the present colloidal silver solution (Sample M) was obtained.

example 12

1. First stage

005512.5 g of hydrazine monohydrate at a concentration of 80% as a reducing agent were dissolved in 3000 ml water and the aqueous solution was (26%) adjusted with ammonia water to a pH value of 10.0, an aqueous solution of make the reducing agent. 20.8 g of palladium chloride and 6.6 g sodium chloride were combined in 3000 ml of water and 2.5 g of 3-Methylmercaptopropionsäure were used as sulfur compound of low molecular weight added. The aqueous formed solution was adjusted to a pH value of 10.0 with Ammonaikwasser (26%) and with the total amount of the aqueous solution of the Reducing agent with stirring at room temperature Mixed for 30 minutes to perform a reduction reaction, whereby colloidal palladium particles with 3-Methylmercaptopropionsäure on the particle in the solution were formed. The molar ratio of the reducing agent to the palladium chloride was 1.70.

2. Second Stage

0056The obtained in the first stage solution was with hydrochloric acid (20%) adjusted to a pH value of 3.0 to colloidal palladium precipitate. The colloidal palladium particles were recovered by a vacuum filter and washed with water until the electrical conductivity of the filtrate became not more than 10.0 s / cm reached, thereby forming wet Cake obtained colloidal palladium particles.

3. Third Stage

0057The moist cakes of colloidal palladium particles, the second in the Stage were recovered by filtration, were added to water, to prepare a colloidal palladium concentration of 10%, and in water with stirring redispersed while the aqueous solution adjusted with ammonia water (26%) to a pH value of 9.0 was, whereby the present colloidal palladium solution (sample N) was obtained.

example 13

0058The present colloidal silver solution (Sample O) was prepared according to Example 1 is obtained, but instead of the addition of sodium borohydride in the first stage of Example 1, irradiation with light for 3 hours with a high pressure mercury lamp of the UV-type SHL-100 (manufactured by Toshiba Corp.) for performing a Reduction reaction was carried out.

example 14

1. First stage

005910.0 g sodium borohydride as a reducing agent were in 1500 ml of water dissolved and the aqueous obtained solution was adjusted with ammonia water (26%) to a pH of 11.0, an aqueous solution of make the reducing agent. 170.0 g of silver nitrate were in 2000 ml, water and 10.8 g of 3-mercaptopropionic acid were used as sulfur compound of low molecular weight added and the aqueous obtained solution was adjusted with ammonia water (26%) to a pH value of 3.0 and then the total amount of the aqueous solution of the reducing agent was to the resulting aqueous solution stirring at room temperature 60 min added to perform a reduction reaction, whereby colloidal silver particles with 3-mercaptopropionic acid on the particle in the solution were formed. The molar ratio of the reducing agent to the silver nitrate was 0.26.

2. Second Stage

0060The obtained in the first stage solution was with hydrochloric acid (20%) adjusted to a pH value of 3.0 to colloidal silver precipitate. The colloidal silver particles were recovered by a vacuum filter and washed with water until the electrical conductivity of the filtrate became not more than 10.0 s / cm reached, thereby forming wet Cake obtained colloidal silver.

3. Third Stage

0061The wet cake of colloidal silver, the second in the Stage were recovered by filtration, were added to water, to a concentration of colloidal silver particles of 10 to produce, and in water with stirring redispersed while the aqueous solution with n-butylamine (26%) was adjusted to a pH value of 9.0, whereby the present colloidal silver solution (Sample P) was obtained.

example 15

1. First stage

006220.0 g sodium borohydride as a reducing agent were in 1500 ml of water dissolved and the aqueous obtained solution was adjusted with ammonia water (26%) to a pH of 11.0, an aqueous solution of make the reducing agent. 177.3 g of palladium chloride were dissolved in 2000 ml of water and 10.6 g of 3-mercaptopropionic acid were used as sulfur compound of low molecular weight added and the aqueous obtained solution was adjusted with ammonia water (26%) to a pH value of 13.0 and then the total amount of the aqueous solution of the reducing agent was to the resulting aqueous solution stirring at room temperature 60 min added to perform a reduction reaction, whereby colloidal palladium particles with 3-mercaptopropionic on the particle in the solution were formed. The molar ratio of the reducing agent to the palladium chloride was 0.53.

2. Second Stage

0063The obtained in the first stage solution was with hydrochloric acid a (20%) to a pH value of 3.0asked to colloidal palladium precipitate. The colloidal palladium particles were recovered by a vacuum filter and washed with water until the electrical conductivity of the filtrate became not more than 10.0 s / cm reached, thereby forming wet Cake obtained colloidal palladium particles.

3. Third Stage

0064The moist cakes of colloidal palladium particles, the second in the Stage were recovered by filtration, were added to water, to prepare a colloidal palladium concentration of 10%, and in water with stirring redispersed while the aqueous solution was adjusted with n-butylamine to a pH value of 9.0, whereby the present colloidal palladium solution (sample Q) was obtained.

example 16

1. First stage

006530.0 g sodium borohydride as a reducing agent were in 1500 ml of water dissolved and the aqueous obtained solution was adjusted with ammonia water (26%) to a pH of 11.0, an aqueous solution of make the reducing agent. 412.0 g chloroauric acid tetrahydrate were dissolved in 2000 ml water and 19.7 g of 3-mercaptoacetic as the sulfur compound of low molecular weight was added and the aqueous obtained solution was adjusted with ammonia water (26%) to a pH value of 13.0 and then the total amount of the aqueous solution of the reducing agent was to the resulting aqueous solution stirring at room temperature 60 min added to perform a reduction reaction, whereby colloidal gold particles with 3-mercaptoacetic on the particle in the solution were formed. The molar ratio the reducing agent to the chloroauric acid was 0.79.

2. Second Stage

0066The obtained in the first stage solution was with hydrochloric acid

0067(20 %) Adjusted to a pH value of 3.0 to colloidal gold particles precipitate. The colloidal gold particles were recovered by a vacuum filter and washed with water until the electrical conductivity of the Filtrate became not more than 10.0 s / cm reached, thereby obtaining wet cake colloidal gold particles were.

3. Third Stage

0068The wet cake of colloidal gold particles in the second stage were recovered by filtration, were added to water to make a produce concentration of colloidal gold particles of 10%, and in Water while stirring redispersed while the aqueous solution was adjusted with n-butylamine to a pH value of 9.0, whereby the present colloidal gold solution (Sample R) was obtained.

example 17

1. First stage

006940.0 g sodium borohydride as a reducing agent were in 1500 ml of water dissolved and the aqueous obtained solution was adjusted with ammonia water (26%) to a pH of 11.0, an aqueous solution of make the reducing agent. 518.0 g chloroplatinic acid were dissolved in 2000 ml water and 19.5 g of 3-mercaptoacetic as the sulfur compound of low molecular weight was added and the aqueous obtained solution was adjusted with ammonia water (26%) to a pH value of 13.0 and then the total amount of the aqueous solution of the reducing agent was to the resulting aqueous solution stirring at room temperature 60 min added to perform a reduction reaction, whereby colloidal platinum with 3-mercaptoacetic on the particle in the solution were formed. The molar ratio the reducing agent to the chloroplatinic acid was 1.06.

2. Second Stage

0070The obtained in the first stage solution was with hydrochloric acid (20%) adjusted to a pH value of 3.0 to colloidal platinum precipitate. The colloidal platinum particles were ge through a vacuum filtergained and washed with water until the electrical conductivity of the filtrate became not more than 10.0 s / cm reached, thereby forming wet Cake obtained colloidal platinum.

3. Third Stage

0071The wet cake of colloidal platinum particles, the second in the Stage were recovered by filtration, were added to water, to produce a concentration of colloidal particles of platinum of 10%, and in water with stirring redispersed while the aqueous solution was adjusted with n-butylamine to a pH value of 9.0, whereby the present colloidal platinum solution (Sample S) was obtained.

Comparative Example 1

0072The Treatment was according to Example 1 was carried out, except that used in the first stage of Example 1 is not mercaptoacetic was used and black precipitates by addition of aqueous sodium borohydride were formed, but no redispersion was carried out. There was no colloidal silver solution receive.

Comparative Example 2

0073The Treatment was according to Example 1 was carried out, but 3.0 g of acetic acid used in place of mercaptoacetic acid used in the first stage of Example 1 were, and black precipitates by addition of aqueous sodium borohydride were formed, but no redispersion was carried out. There was no colloidal silver solution receive.

Comparative Example 3

0074In the first stage of Example 1 were citric acid monohydrate 3.0 h instead of mercaptoacetic used. A colloidal silver solution was prepared by adding the aqueous sodium borohydride condition, but black precipitates were also formed in the solution. rainfall were from the solution separated by filtration and the filtrate was treated with nitric acid (20 %) Adjusted to a pH of 3.0, but there was no Training of colloidal silver particles and they could not be by filtration ge gained.

Comparative Example 4

0075In Comparison Example 3, the amount of added Citronensäuremonohydrats increased to 50 g and it was a colloidal silver solution by addition of aqueous obtained sodium borohydride. The solution was treated with nitric acid (20 %) Adjusted to a pH of 3.0, but was not precipitation of colloidal silver particles and they could not by filtration be won.

Comparative Example 5

0076The Treatment was according to Example 7 is performed, except that used in the first stage of Example 7 is not 3-mercaptopropionic acid has been used. Black precipitates were prepared by adding the aqueous hydrazine formed, but there was no re-dispersion. There was no colloidal palladium solution receive.

Comparative Example 6

0077The Treatment was according to Example 8 performed except that used in the first step of Example 8 is not 3-mercaptopropionic acid has been used. Black precipitates were prepared by adding the aqueous hydrazine formed, but there was no re-dispersion. There was no colloidal platinum solution receive.

Comparative Example 7

0078The Treatment was according to Example 9 carried out, except that used in the first step of Example 9 is not 3-mercaptopropionic acid has been used. Black precipitates were prepared by adding the aqueous hydrazine formed, but there was no re-dispersion. There was no colloidal gold solution receive.

Comparative Example 8

0079The Treatment was according to Example 10 carried out, but the employed in the first step of Example 10 3-mercaptopropionic acid was not used. Black precipitates were prepared by adding the aqueous sodium borohydride formed, but there was no re-dispersion. There was no colloidal copper solution receive.

Comparative Example 9

0080The Treatment was according to Example 1 was carried out, but ammonia water used instead of monoethanolamine was used and the mercaptoacetic acid in the first stage of Example 1 is not has been used. Black precipitates were prepared by adding the aqueous sodium borohydride formed, but there was no re-dispersion. There was no colloidal silver solution receive.

Comparative Example 10

0081The Treatment was according to Example 1 was carried out, except that the pH adjustment in the third stage of Example 1 did not take place. The pH of the solution was 6.5 and it was no Redisperison of colloidal silver. There was no colloidal silver solution receive.

assessment 1

0082The dispersion stability obtained in the examples 1 to 17 colloidal metal solutions (Samples A to S) was evaluated. The evaluation was made by determining the particle sizes of colloidal Metal particles in the colloidal metal solutions at the start and after storage while three months at room temperature by a particle size distribution Micro Track UPA 9340 type (manufactured by Nikkiso Co., Ltd.). The particle sizes were the average particle sizes on Media base indicated. changes appearance and precipitation were also vi Suell considered.

0083The Results are given in Table 1 below. It was found that the present colloidal metal solutions no changes with regard to the state of dispersion of colloidal metal solutions themselves exhibited before and after storage and a significant dispersion stability exhibited. Neither changes the appearance nor precipitation was observed in all samples even after storage during three months observed. TABLE 1 <tables><table frame="all"><tgroup cols="7" colsep="1" rowsep="1"><colspec colname="1" colwidth="1*" /><colspec colname="2" colwidth="1*" /><colspec colname="3" colwidth="1*" /><colspec colname="4" colwidth="1*" /><colspec colname="5" colwidth="1*" /><colspec colname="6" colwidth="1*" /><colspec colname="7" colwidth="1*" /><tbody><row><entry morerows="1" colname="1">Example no.</entry><entry morerows="1" colname="2">Sample no.</entry><entry morerows="1" colname="3">Containing colloidal metal (wt .-%)</entry><entry morerows="1" colname="4">Content of sulfur compound (parts by weight per part by weight of colloidal metal)</entry><entry morerows="1" colname="5">color</entry><entry namest="6" nameend="7">storage stability</entry></row><row><entry colname="6">Particle size at the beginning (Nm)</entry><entry colname="7">particle size after 3 months (nm)</entry></row><row><entry colname="1">1</entry><entry colname="2">A</entry><entry colname="3">10.2</entry><entry colname="4">0.56</entry><entry colname="5">maroon</entry><entry colname="6">10.4</entry><entry colname="7">11.0</entry></row><row><entry colname="1">2</entry><entry colname="2">B</entry><entry colname="3">10.7</entry><entry colname="4">0.56</entry><entry colname="5">maroon</entry><entry colname="6">11.0</entry><entry colname="7">11.1</entry></row><row><entry colname="1">3</entry><entry colname="2">C</entry><entry colname="3">10.5</entry><entry colname="4">0.56</entry><entry colname="5">maroon</entry><entry colname="6">10.4</entry><entry colname="7">10.5</entry></row><row><entry colname="1">4</entry><entry colname="2">D</entry><entry colname="3">9.9</entry><entry colname="4">0.56</entry><entry colname="5">maroon</entry><entry colname="6">20.4</entry><entry colname="7">21.0</entry></row><row><entry colname="1">5</entry><entry colname="2">e</entry><entry colname="3">10.1</entry><entry colname="4">0.56</entry><entry colname="5">maroon</entry><entry colname="6">9.9</entry><entry colname="7">10.4</entry></row><row><entry colname="1">6</entry><entry colname="2">F</entry><entry colname="3">10.1</entry><entry colname="4">0.56</entry><entry colname="5">maroon</entry><entry colname="6">11.2</entry><entry colname="7">12.3</entry></row><row><entry colname="1">7</entry><entry colname="2">I</entry><entry colname="3">11.0</entry><entry colname="4">0.56</entry><entry colname="5">black-brown</entry><entry colname="6">8.9</entry><entry colname="7">9.3</entry></row><row><entry colname="1">8th</entry><entry colname="2">J</entry><entry colname="3">8.9</entry><entry colname="4">0.51</entry><entry colname="5">black-brown</entry><entry colname="6">11.9</entry><entry colname="7">12.2</entry></row><row><entry colname="1">9</entry><entry colname="2">K</entry><entry colname="3">9.4</entry><entry colname="4">0.30</entry><entry colname="5">bordeaux-red</entry><entry colname="6">10.0</entry><entry colname="7">10.1</entry></row><row><entry colname="1">10</entry><entry colname="2">L</entry><entry colname="3">10.1</entry><entry colname="4">0.94</entry><entry colname="5">maroon</entry><entry colname="6">12.5</entry><entry colname="7">12.8</entry></row><row><entry colname="1">11</entry><entry colname="2">M</entry><entry colname="3">10.0</entry><entry colname="4">0.20</entry><entry colname="5">maroon</entry><entry colname="6">9.9</entry><entry colname="7">10.5</entry></row><row><entry colname="1">12</entry><entry colname="2">N</entry><entry colname="3">11.4</entry><entry colname="4">0.20</entry><entry colname="5">black-brown</entry><entry colname="6">9.1</entry><entry colname="7">9.5</entry></row><row><entry colname="1">13</entry><entry colname="2">O</entry><entry colname="3">9.4</entry><entry colname="4">0.56</entry><entry colname="5">maroon</entry><entry colname="6">8.7</entry><entry colname="7">9.2</entry></row><row><entry colname="1">14</entry><entry colname="2">P</entry><entry colname="3">10.2</entry><entry colname="4">0.10</entry><entry colname="5">maroon</entry><entry colname="6">8.8</entry><entry colname="7">8.9</entry></row><row><entry colname="1">15</entry><entry colname="2">Q</entry><entry colname="3">10.1</entry><entry colname="4">0.10</entry><entry colname="5">black-brown</entry><entry colname="6">10.2</entry><entry colname="7">10.5</entry></row><row><entry colname="1">16</entry><entry colname="2">R</entry><entry colname="3">10.2</entry><entry colname="4">0.10</entry><entry colname="5">bordeaux-red</entry><entry colname="6">9.9</entry><entry colname="7">11.3</entry></row><row><entry colname="1">17</entry><entry colname="2">S</entry><entry colname="3">9.9</entry><entry colname="4">0.10</entry><entry colname="5">black-brown</entry><entry colname="6">10.3</entry><entry colname="7">11.0</entry></row></tbody></tgroup></table></tables><ul><li>(Manufacture of electrically conductive two-component paints)</li></ul>

example 18

0084the This electrically conductive two-component paints (Sample a) consisting of a first liquid and a second liquid there was prepared by mixing of P sample of Example 14 and compounds according to the following formulations given by a disperser produced. In the first liquid was the mixing ratio of acetamide 24 parts on the basis of 100 parts by weight of water. First liquid <tables><table frame="none"><tgroup cols="2" colsep="0" rowsep="0"><colspec colname="1" colwidth="1*" /><colspec colname="2" colwidth="1*" /><tbody><row><entry colname="1">sample P</entry><entry colname="2">4.0 G</entry></row><row><entry colname="1">water</entry><entry colname="2">25.0 G</entry></row><row><entry colname="1">ethylene glycol</entry><entry colname="2">5.0 G</entry></row><row><entry colname="1">acetamide</entry><entry colname="2">6.0 G</entry></row></tbody></tgroup></table></tables> Second liquid <tables><table frame="none"><tgroup cols="2" colsep="0" rowsep="0"><colspec colnum="1" colname="1" colwidth="1*" /><colspec colnum="2" colname="2" colwidth="1*" /><tbody><row><entry colname="1">methyl silicate 51 (manufactured by Colcoat Co., Ltd.) </entry><entry colname="2"> 4.6 G</entry></row><row><entry colname="1">ethanol</entry><entry colname="2"> 9.0 G</entry></row><row><entry colname="1">2-propanol</entry><entry colname="2"> 46.8 G</entry></row><row><entry colname="1">1-methoxy-2-propanol</entry><entry colname="2"> 173.0 G</entry></row><row><entry colname="1">water</entry><entry colname="2"> 1.0 G</entry></row><row><entry colname="1">20% hydrochloric acid</entry><entry colname="2"> 0.03 G</entry></row></tbody></tgroup></table></tables>

example 19

0085the This electrically conductive two-component paints (Sample b) according to Example 18 prepared, but the acetamide by dimethyl sulfoxide in Example was replaced 18th

example 20

0086the This electrically conductive two-component paints (Sample c) according to Example 18 prepared, but the acetamide with N-methylformamide in Example was replaced 18th

example 21

0087the This electrically conductive two-component paints (Sample d) according to Example 18 prepared, but the acetamide by ethylene glycol in Example was replaced 18th

example 22

0088the This electrically conductive two-component paints (Sample e) according to Example 18 prepared, but using 2-imidazolidinone 1,3-dimethyl-acetamide by was replaced in Example 18th

example 23

0089the This electrically conductive two-component paints (Sample f) according to Example 18 prepared, but the acetamide with 4-butyrolactone in Example was replaced 18th

example 24

0090the This electrically conductive two-component paints (Sample g) was prepared according to Example 18 prepared, except that the sample P through the sample of Example Q 15 was replaced in Example 18th

example 25

0091the This electrically conductive two-component paints (Sample h) according to Example 18 prepared, except that the sample P through the sample of Example R 16 was replaced in Example 18th

example 26

0092the This electrically conductive two-component paints (Sample i) according to Example 18 prepared, except that the sample P through the sample S of Example 17 was replaced in Example 18th

example 27

0093the This electrically conductive two-component paints (Sample j) according to Example 18 prepared, but the sample by P by a mixture of 3.84 g of sample P and 0.16 g of sample Q replaced in Example 18 has been.

example 28

0094the This electrically conductive two-component paints (Sample k) according to Example 18 prepared, but the sample by P by a mixture of 3.84 g of sample P and 0.16 g of sample R replaced in Example 18 has been.

example 29

0095the This electrically conductive two-component paints (Sample l) according to Example 18 prepared, except that the formulation of the first liquid was replaced by the specified hereinafter in Example eighteenth In the first liquid was the mixing ratio of acetamide 24.5 parts by weight on the Based on 100 parts by weight of water. First liquid <tables><table frame="none"><tgroup cols="2" colsep="0" rowsep="0"><colspec colnum="1" colname="1" colwidth="1*" /><colspec colnum="2" colname="2" colwidth="1*" /><tbody><row><entry colname="1">sample P</entry><entry colname="2">3.2 G</entry></row><row><entry colname="1">water</entry><entry colname="2">25.4 G</entry></row><row><entry colname="1">Snowtex N (20 SiO₂-containing colloidal silica, manufactured by Nissan Chemical Industries, Ltd.)</entry><entry>0.4 g</entry></row><row><entry colname="1">ethylene glycol</entry><entry colname="2">5.0 G</entry></row><row><entry colname="1">acetamide</entry><entry colname="2">6.0 G</entry></row></tbody></tgroup></table></tables>

example 30

0096the This electrically conductive two-component paints (Sample m) was prepared according to Example 18 prepared, except that the formulation of the first liquid was replaced by the specified hereinafter in Example eighteenth In the first liquid was the mixing ratio of acetamide 23.7 parts by weight on the Based on 100 parts by weight of water. First liquid <tables><table frame="none"><tgroup cols="2" colsep="0" rowsep="0"><colspec colnum="1" colname="1" colwidth="1*" /><colspec colnum="2" colname="2" colwidth="1*" /><tbody><row><entry colname="1">sample P</entry><entry colname="2">3.2 G</entry></row><row><entry colname="1">water</entry><entry colname="2">25,33 G</entry></row><row><entry colname="1">SN-100S (aqueous Dispersion of antimony doped tin oxide, manufactured by Ishihara Sangyo Kaisha, Ltd.)</entry><entry>0.47 g</entry></row><row><entry colname="1">ethylene glycol</entry><entry colname="2">5.0 G</entry></row><row><entry colname="1">acetamide</entry><entry colname="2">6.0 G</entry></row></tbody></tgroup></table></tables>

example 31

0097the This electrically conductive two-component paints (Sample n) according to Example 18 prepared, but the acetamide by formamide (surface tension: 57 × 10^-3 N / m) was replaced in Example 18th

Comparative Example 11

0098It has been attempted, an electrically conductive two-component paints according to example 18 to produce, but the acetamide with 1-butanol (dielectric constant: 18; Surface tension: 25 × 10^-3 N / m) was replaced in Example 18, but formed in the first liquid black aggregates and no electrically conductive paint receive.

Overall 2

0099On square glass substrate (75 mm × 75 mm, 3 mm thick) was 50 ° C in the atmosphere mounted on a spin coater, and 1 ml of first liquid the electrically conductive two-component paints (samples a to n), which were prepared in Examples 18 to 31, were individually dripped onto the substrate, whereupon rotation at 120 rpm for 100 s followed by a forming electrically conductive layer thereon. Then, the second liquid under the same conditions as above it, spin-coated, followed by heating in an oven in an atmospheric environment at 120 ° C for 30 min followed by a transparent electrically conductive coating film to form. The coating film obtained in this manner was tested, wherein the surface resistivity by a Oberflächenohmmeter (Loresta GP Type, manufactured by Mitsubishi Chemical Corp.) determined was and turbidity and the permeability by a turbidity measuring device (DH-300 A type, manufactured by Nippon Densyoku Industries Co., Ltd.) were determined. The appearance of the coating surface was on the base of spots or marbling assessed visually.

0100The Evaluation results of surface resistivity, turbidity, transmittance and appearance of a coating film are given in Table 2 below. It has been found that the coating films obtained in this way significant electrical conductivity and high transparency exhibited. The appearance of the coating films was also substantially satisfactory, and in the case of non-aqueous solvent having a surface tension of not more than 50 × 10^-3 N / m could get good appearance with no spots or marbling will. TABLE 2<tables><table frame="all"><tgroup cols="6" colsep="1" rowsep="1"><colspec colname="1" colwidth="1*" /><colspec colname="2" colwidth="1*" /><colspec colname="3" colwidth="1*" /><colspec colname="4" colwidth="1*" /><colspec colname="5" colwidth="1*" /><colspec colname="6" colwidth="1*" /><tbody><row><entry colname="1">example No.</entry><entry colname="2">sample</entry><entry colname="3">Surface resistivity (Ω / square)</entry><entry colname="4">Haze [%]</entry><entry colname="5">Transparent speed [%]</entry><entry colname="6">Appearance</entry></row><row><entry colname="1">18</entry><entry colname="2">a</entry><entry colname="3">5.9 × 10²</entry><entry colname="4">0.3</entry><entry colname="5">78.0</entry><entry colname="6">Good</entry></row><row><entry colname="1">19</entry><entry colname="2">b</entry><entry colname="3">6.1 × 10²</entry><entry colname="4">0.4</entry><entry colname="5">76.1</entry><entry colname="6">Good</entry></row><row><entry colname="1">20</entry><entry colname="2">c</entry><entry colname="3">4.8 × 10²</entry><entry colname="4">0.3</entry><entry colname="5">77.5</entry><entry colname="6">Good</entry></row><row><entry colname="1">21</entry><entry colname="2">d</entry><entry colname="3">4.9 × 10²</entry><entry colname="4">0.4</entry><entry colname="5">74.9</entry><entry colname="6">Good</entry></row><row><entry colname="1">22</entry><entry colname="2">e</entry><entry colname="3">6.0 × 10²</entry><entry colname="4">0.3</entry><entry colname="5">76.8</entry><entry colname="6">Good</entry></row><row><entry colname="1">23</entry><entry colname="2">f</entry><entry colname="3">7.3 × 10²</entry><entry colname="4">0.3</entry><entry colname="5">74.9</entry><entry colname="6">Good</entry></row><row><entry colname="1">24</entry><entry colname="2">G</entry><entry colname="3">8.0 × 10²</entry><entry colname="4">0.2</entry><entry colname="5">76.8</entry><entry colname="6">Good</entry></row><row><entry colname="1">25</entry><entry colname="2">h</entry><entry colname="3">6.9 × 10²</entry><entry colname="4">0.2</entry><entry colname="5">75.5</entry><entry colname="6">Good</entry></row><row><entry colname="1">26</entry><entry colname="2">i</entry><entry colname="3">7.2 × 10²</entry><entry colname="4">0.3</entry><entry colname="5">69.8</entry><entry colname="6">Good</entry></row><row><entry colname="1">27</entry><entry colname="2">j</entry><entry colname="3">5.3 × 10²</entry><entry colname="4">0.2</entry><entry colname="5">71.2</entry><entry colname="6">Good</entry></row><row><entry colname="1">28</entry><entry colname="2">k</entry><entry colname="3">6.0 × 10²</entry><entry colname="4">0.3</entry><entry colname="5">73.4</entry><entry colname="6">Good</entry></row><row><entry colname="1">29</entry><entry colname="2">l</entry><entry colname="3">7.8 × 10²</entry><entry colname="4">0.2</entry><entry colname="5">80.1</entry><entry colname="6">Good</entry></row><row><entry colname="1">30</entry><entry colname="2">m</entry><entry colname="3">4.6 x 10²</entry><entry colname="4">0.3</entry><entry colname="5">74.8</entry><entry colname="6">Good</entry></row><row><entry colname="1">31</entry><entry colname="2">n</entry><entry colname="3">2.9 × 10^8th</entry><entry colname="4">1.2</entry><entry colname="5">49.8</entry><entry colname="6">With stains</entry></row></tbody></tgroup></table></tables>