JP2007128864A - Fluid composition, and electrode, wiring pattern, as well as coating film formed by using it, and decoration goods forming the coating film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a fluid composition for obtaining a rigid coating film with excellent adhesion with a base material even by drying and heating at comparatively low temperature. <P>SOLUTION: The fluid composition contains at least crosslinking agent and solvent, and sulfuric compound having at least a kind of hydrophilic group selected from a carboxyl group, hydroxyl group, amino group, hydrazide group, and amide group, nitrogen compound, or phosphorus compound are chemically bonded on the surface of metal particles. As the crosslinking agent, an oxazoline system crosslinking agent, carbodiimide system crosslinking agent, blocked isocyanate system crosslinking agent, epoxy system crosslinking agent, and melamine system crosslinking agent are mixed. The fluid composition is suited for forming a fine electrode, a circuit wiring pattern or for forming a mirror-face coating film. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a fluid composition containing metal particles, an electrode formed using the fluid composition, a wiring pattern, a coating film, and a decorative article on which the coating film is formed.

  A fluid composition containing metal particles is generally dispersed in a solvent, and further added with additives such as binders, dispersants, viscosity modifiers, etc., generally coating agents, paints, pastes, inks, It is a generic term that includes compositions such as ink, and is used for various purposes such as securing electrical continuity, or providing antistatic properties, electromagnetic wave shielding, or metallic luster by utilizing the properties of the metal particles. It has been. Moreover, in recent years, as colloidal metal particles, metal colloidal particles having an average particle diameter of about 1 to 100 nm have been used, and their uses are expanding in various fields. Specifically, it is applied to electromagnetic wave shielding of transparent members such as cathode ray tubes and liquid crystal displays by utilizing the high conductivity of metal colloid particles. In addition, a technique for forming fine electrodes and circuit wiring patterns using metal colloidal particles, which are nanomaterials, has been proposed. This is because a flowable composition containing metal colloid particles is applied with a pattern of electrodes and circuit wiring on a substrate by a method such as screen printing or ink jet printing, and then heated at a relatively low temperature to melt the metal colloid particles. In particular, it is being applied to the production of printed wiring boards. Furthermore, since metal colloidal particles are easily fused even under mild heating conditions to develop a metallic luster, a simple mirror surface preparation technique is attracting attention in design and decoration applications.

  As such a fluid composition, for example, an organic component such as sodium citrate or potassium citrate is included in the metal colloid particles as a dispersion stabilizer, and a polyurethane resin such as blocked isocyanate, a melamine resin or the like is used as a film-forming aid. There is known a conductive ink used as (see Patent Document 1).

JP 2001-325831 A

  A coating film obtained by applying the conductive ink described in Patent Document 1 to a substrate and heating at a relatively low temperature of about 150 ° C. has low adhesion to the substrate, and the coating film strength is fragile. In addition, surface defects such as cracks and defects such as peeling are likely to occur, which not only impairs commercial value but also deteriorates properties such as conductivity. Specifically, even if circuit wiring or electrodes are formed, troubles such as disconnection or reduction in electrical continuity occur, and the antistatic property and electromagnetic wave shielding property of the formed coating film deteriorate. In addition, the metal particles aggregate while the coating film is dried, so that the smoothness of the coating film tends to be lowered, and there is a problem that the metallic luster is reduced and white turbidity is generated.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a specific compound that chemically bonds more strongly than the sodium citrate, potassium citrate and the like described in Patent Document 1 on the surface of the metal particles. Further, when a fluid composition is prepared by adding a hydrophilic group to the end of the compound, and blending an oxazoline crosslinking agent, a carbodiimide crosslinking agent, a blocked isocyanate crosslinking agent, etc. The present inventors have found that the adhesion of the coating film is improved by heating at a relatively low temperature of about 150 ° C., the coating film has excellent smoothness, and the finished appearance such as metallic luster is improved. Furthermore, as a result of examining the above findings in detail, when the active group present in the crosslinking agent used reacts with the hydrophilic group present in the compound chemically bonded to the surface of the metal particles, the adhesion and the like are further improved. As a result, the present invention has been completed.

  That is, the present invention includes (1) a compound having at least one metal particle, a crosslinking agent, and a solvent, and having at least one element selected from sulfur, nitrogen, and phosphorus and a hydrophilic group on the surface of the metal particle. It is a fluid composition characterized in that it is chemically bonded via an element and the crosslinking agent has an active group capable of reacting with the hydrophilic group of the compound, and (2) metal particles, It contains at least a crosslinking agent and a solvent, and at least one hydrophilic property selected from a carboxyl group, a hydroxyl group, an amino group, a hydrazide group, and an amide group on the surface of the metal particles and at least one element selected from sulfur, nitrogen, and phosphorus. And a compound having a group are chemically bonded through the above-mentioned elements, and the crosslinking agent is an oxazoline-based crosslinking agent, a carbodiimide-based crosslinking agent, a blocked isocyanate-based crosslinking agent, an epoxy-based crosslinking agent, It is a fluid composition characterized in that it is at least one selected from laminar crosslinking agents, and (3) is formed using the fluid composition of (1) and (2) above. (4) A decorative article characterized in that the coating film of (3) is formed.

  The fluid composition of the present invention is a metal film that is superior to conventional ones in that a strong coating film having excellent adhesion to a substrate can be obtained by drying or heating at a relatively low temperature, and also having excellent smoothness. A coating film having a specular surface due to gloss is obtained. For this reason, defective products due to coating surface defects, coating film dropouts, and defects are unlikely to occur, and can be used reliably for materials that ensure electrical continuity, or materials that provide antistatic, electromagnetic shielding, or metallic luster. In particular, it is used for the formation of fine electrodes such as printed circuit boards and circuit wiring patterns utilizing the conductivity of the coating film, and for design and decoration applications utilizing the mirror surface of the coating film.

  The present invention is a fluid composition containing at least metal particles, a crosslinking agent and a solvent, and (1) at least one element selected from sulfur, nitrogen and phosphorus and a hydrophilic group on the surface of the metal particles. A compound having an active group capable of reacting with the hydrophilic group of the compound, wherein the compound has a chemical bond through the element (2) It is important that The hydrophilic compound forms a strong chemical bond with the metal particle through the element of sulfur, nitrogen or phosphorus, and the hydrophilic group is oriented on the outer surface of the metal particle, thereby making the metal particle excellent in hydrophilicity. At the same time, it is considered that the effect of suppressing the aggregation of particles is high. On the other hand, the active group possessed by the cross-linking agent reacts with an externally oriented hydrophilic group and active hydrogen such as a hydroxyl group on the substrate surface under heating conditions, and a metal film and substrate formed by fusion of metal particles It is thought that it bridges the gap. Therefore, it is estimated that the metal film formed from the fluid composition of the present invention also has high adhesion to the substrate. In addition, the hydrophilic compound strongly bonded to the surface of the metal particles relaxes the electron deficiency on the metal surface by electron donation from the hydrophilic compound, and at the same time, keeps the distance between particles constant by steric repulsion. In this fluid composition, the dispersion stability of the metal particles is hardly lowered.

  The fluid composition of the present invention includes a composition generally referred to as a coating agent, paint, paste, ink, ink, etc., and the compounding amount of metal particles, hydrophilic compound, and crosslinking agent in the fluid composition is as follows. It can set suitably according to each use. For example, in order to obtain electrodes and circuit wiring patterns with stable conductivity, it is desirable to form a thick coating with a single coating. It is preferably blended at a concentration, and the blending amount may be 5% by weight or more with respect to the total weight of the fluid composition, more preferably 10% by weight or more, and even more preferably 15% by weight or more. . The upper limit of the amount of metal particles in the electrode material application can be about 90% by weight, preferably 85% by weight, and more preferably 80% by weight. On the other hand, in decorative applications, it is desirable that a coating film having a mirror surface is obtained by using metal particles having a lower concentration from the viewpoint of cost. The blending amount may be 50% by weight or less, and 20% by weight or less. More preferred is 15% by weight or less. The lower limit of the amount of metal particles in the coating application can be about 0.1% by weight, preferably 0.5% by weight, and more preferably 1% by weight. If the hydrophilic compound is present in a range of about 0.01 to 200 parts by weight with respect to 1000 parts by weight of the metal particles, the desired effect can be obtained, and a more preferable range is 0.5 to 100 parts by weight. Degree. Since the desired effect is obtained if the crosslinking agent is in the range of 0.01 to 10 parts by weight with respect to 100 parts by weight of the metal particles, it is not preferred because the effect of the present invention is difficult to obtain if it is too small, If the amount is too large, curing is excessively advanced, and the viscosity of the paint is increased, so that the paintability is inhibited. A more preferable range is about 0.01 to 8 parts by weight, and further preferably about 0.01 to 5 parts by weight.

  In the fluid composition of the present invention, a predetermined amount of metal particles, a hydrophilic compound, a crosslinking agent, and a solvent are mixed by a known method to chemically bond the hydrophilic compound to the surface of the metal particles, Disperse in solvent. Further, as another more preferable method, after preparing a powder of metal particles chemically bonded with a hydrophilic compound and a dispersion in which the metal particles are dispersed in a solvent as described later, when mixed with a crosslinking agent and a solvent, A more uniform dispersion state can be obtained. As a mixing method, for example, a method such as agitation and mixing using a stirrer such as a disper or a wet pulverization and mixing such as a sand mill or a colloid mill can be used. During mixing, other components such as an aqueous binder described later can be added and mixed as necessary. The cross-linking agent may be mixed in advance in the same manner as the other components to prepare a fluid composition. However, when the cross-linking reaction proceeds rapidly, the two-part property of the metal particle solvent dispersion and the cross-linking agent solution is used. As a composition, they can be mixed before use.

Next, each component mix | blended with the fluid composition of this invention is demonstrated.
(1) Metal particles The metal particles used in the present invention are not particularly limited in terms of their constituent components, particle diameter, etc., and can be appropriately selected according to the intended use. The constituent component may be one kind of metal or may be composed of two or more kinds of metals such as an alloy or a laminate. If the metal component is at least one selected from the group consisting of group VIII (iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum) and group IB (copper, silver, gold) as the metal component In particular, silver, gold, platinum, palladium, and copper are more preferable because of their high conductivity. Among them, the balance between conductivity and cost is desirable for use in a fluid composition for forming electrodes and circuit wiring patterns. Particularly preferred is silver or copper. In addition, the metal particles may contain impurities such as oxygen and foreign metals that are unavoidable in the manufacturing method, or in advance, oxygen, metal oxides, and organics may be used in advance to prevent rapid oxidation of the metal particles. A compound etc. may be contained. Since the particle size of the metal particles is easily available, it is preferable to appropriately use metal particles having an average particle size of about 1 nm to 10 μm, more preferably metal particles having an average particle size of about 1 nm to 1 μm, and various uses. Metal colloid particles having an average particle diameter of about 1 to 100 nm are more preferable, and in order to obtain finer electrodes and circuit wiring patterns, metal colloids having an average particle diameter in the range of 5 to 50 nm. More preferably, particles are used. In the present invention, one kind of metal particles may be used, or two or more kinds of metal particles may be mixed and used. For example, two or more kinds of metal particles having different average particle diameters, two or more kinds having different constituent components. These metal particles may be mixed and used.

  The metal particles can be produced using a known method. For example, (1) a method in which a metal is evaporated in a vacuum to condense the metal particles from a gas phase, and (2) a reducing agent is added to the metal compound solution. Can be used to precipitate metal particles from the liquid phase, and the method (2) is more preferable because metal colloidal particles can be obtained at low cost. In the method (2), as the metal compound that is a raw material for producing metal particles, for example, the metal chloride, sulfate, nitrate, carbonate and the like can be used. An organic solvent such as water or alcohol, or a mixed solvent of two or more of these can be used for the medium for dissolving the metal compound. The concentration of the metal compound in the liquid medium is not particularly limited as long as the metal compound can be dissolved, but is preferably 5 mmol / liter or more industrially. If the metal compound is hardly soluble in water, a compound containing chlorine ions, ammonia, or the like that forms a soluble complex with the metal component can be added and used.

  As the reducing agent used in the reaction in the liquid phase, a known reducing agent can be used. For example, (1) hydrazine or a hydrate thereof, (2) hydrazine compounds (for example, hydrazine hydrochloride, hydrazine sulfate, etc.), ( 3) Aldehydes ((a) aliphatic aldehydes (eg, formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, etc.), (b) aromatic aldehydes (eg, benzaldehyde, etc.), (c) heterocyclic Aldehydes), (4) amines ((a) primary amines (eg, butylamine, ethylamine, propylamine, ethylenediamine), (b) secondary amines (eg, dibutylamine, diethylamine, dipropylamine) Etc.), (c) tertiary amines (for example, tributylamine, triethyl) Amine, tripropylamine, etc.), (5) aminoaldehydes (eg, aminoacetaldehyde, etc.), (6) alkanolamines (eg, ethanolamine, diethanolamine, triethanolamine, etc.), (7) reducing sugar ( (E.g., sucrose, treperth, maltose, lactose, etc.), (8) hydrogen compounds (e.g., sodium borohydride, etc.), (9) low-order inorganic oxygen acids (e.g., sulfurous acid, nitrous acid, hyponitrous acid, phosphorous) Acid, hypophosphorous acid, etc.) and hydrates thereof (for example, hydrogen sulfite) or salts thereof (for example, alkali metal salts such as sodium), etc., and these may be used alone or in combination. . The reduction reaction can be carried out at any temperature, and when carried out in an aqueous medium, a temperature in the range of 5 to 90 ° C. is preferred because the reaction can proceed easily. The addition amount of the reducing agent can be appropriately set as long as it can be reduced to a metal, and is preferably 0.2 to 50 mol with respect to 1 mol of the metal compound. If the addition amount is less than 0.2 mol, it is not preferable because the reduction reaction is unlikely to proceed sufficiently.

  It is preferable to adjust the pH of the mixed solution of the metal compound and the reducing agent to a range of 8 to 14 because the metal compound is uniformly dispersed in the medium and a reduction reaction is likely to occur. A more preferable pH range is 8 to 13, and 8 to 12 is more preferable. Specifically, for example, after adjusting the pH of the liquid medium containing the metal compound, the metal compound may be reduced, or after mixing the reducing agent, the pH may be adjusted. For pH adjustment, for example, a basic compound such as an alkali metal or alkaline earth metal hydroxide or carbonate such as sodium hydroxide, potassium hydroxide or calcium hydroxide, an ammonium compound such as ammonia, or an amine is used. be able to. Since the metal particles obtained in this way easily aggregate when the pH of the liquid medium is 5 or less, they can be separated by a relatively simple operation such as suction filtration or sedimentation separation. A more preferable pH range is 0-5. The colloidal metal colloid particles can be washed by a conventional method, and soluble salts and remaining reducing agent can be sufficiently removed. For pH adjustment, for example, an inorganic compound such as hydrochloric acid, sulfuric acid or nitric acid, or an acidic compound such as organic acid such as formic acid, acetic acid or propionic acid can be used.

(2) Hydrophilic compound The hydrophilic compound to be chemically bonded to the surface of the metal particles is a compound having a hydrophilic group and a compound containing at least one element selected from sulfur, nitrogen, and phosphorus. is there. Since each element of sulfur, nitrogen, and phosphorus is coordinated and chemically bonded to the surface of the metal particle, hydrophilic compounds containing the elements of sulfur, nitrogen, and phosphorus are coordinated to the surface of the metal particle through these elements. To do. Among these elements, sulfur is preferable because it has a strong chemical bonding force with metal particles. Sulfur, nitrogen and phosphorus elements may be contained in a functional group different from the hydrophilic group, and if the hydrophilic compound has two or more hydrophilic groups, they are contained in the hydrophilic group. Also good. However, in the present invention, it is not always necessary that all the hydrophilic compounds present on the surface of the metal particles are chemically bonded to the metal particles, and the effect of the present invention can be obtained if at least a portion is chemically bonded. The remaining part may be adsorbed or deposited on the particle surface. The hydrophilic group means a functional group having an affinity for water and is preferably capable of reacting with the active group of the crosslinking agent, and a compound having at least one hydrophilic group is used. Examples of the hydrophilic group include a carboxyl group (—COOH), a hydroxyl group (—OH), an amino group (—NH ₂ ), a hydrazide group (—NH—NH ₂ ), an amide group (—CONH—), and the like. The hydrophilic compound preferably contains one or more of these.

Examples of the sulfur compound having a hydrophilic group include (a) mercaptocarboxylic acids (the hydrophilic group is a carboxyl group: for example, mercaptopropionic acid, mercaptoacetic acid, thiodipropionic acid, mercaptosuccinic acid, dimercaptosuccinic acid, thioacetic acid. Thiothioglycolic acid, etc.), (b) thioglycols (hydrophilic groups are hydroxyl groups: for example, mercaptoethanol, thiodiethylene glycol, etc.), (c) aminothiols (hydrophilic groups are amino groups: aminoethyl mercaptan, thio) Diethylamine, etc.), (d) thioamides (hydrophilic groups are amide groups, such as thioformamide), (e) sulfur-containing amino acids (hydrophilic groups are amino groups and carboxyl groups, such as cysteine, methionine, etc.) Can be mentioned. Among these, at least one selected from mercaptopropionic acid, mercaptoacetic acid, thiodipropionic acid, mercaptosuccinic acid, mercaptoethanol, thiodiethylene glycol, thiodiglycolic acid, aminoethyl mercaptan, and thiodiethylamine is preferable, particularly mercaptopropionic acid, mercapto Acetic acid and mercaptoethanol are more preferred because they are effective in imparting hydrophilicity and dispersion stability to metal particles, particularly metal colloid particles.
Examples of the nitrogen compound having a hydrophilic group include (a) amino acids (the hydrophilic group is a carboxyl group: for example, neutral amino acids such as glycine and alanine, basic amino acids such as histidine and arginine, aspartic acid, Acidic amino acids such as glutamic acid), (b) aminopolycarboxylic acids (the hydrophilic group is a carboxyl group: for example, ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA), iminodiacetic acid (IDA), ethylenediaminediacetic acid (EDDA) , Ethylene glycol diethyl ether diamine tetraacetic acid (GEDA), etc.), (c) alkanolamines (hydrophilic groups are hydroxyl groups: for example, ethanolamine, diethanolamine, triethanolamine, etc.), (d) amines (hydrophilic groups are Amino group: ethylenediamine, diethyl Ntoriamin, triamino triethylamine etc.).
As the phosphorus compounds having a hydrophilic group, an alkyl phosphine (-PR 3: _R is an alkyl group) and the like in which a part of the alkyl group is substituted with a functional group having a hydrophilic group.

  In order to chemically bond the hydrophilic compound to the surface of the metal particles in advance, the hydrophilic compound is added and mixed in a liquid medium in which the metal particles are dispersed, or the metal compound and the reducing agent are mixed in a liquid phase. It can be produced even when a hydrophilic compound is present in the reaction. The latter method is a preferred method because a hydrophilic compound is present during the reduction reaction, so that highly dispersed metal particles can be obtained, and particularly fine metal colloid particles can be obtained. From this, a method of reducing by mixing a reducing agent with a solution in which a metal compound and a hydrophilic compound are dissolved in a medium, a reducing agent is added to a solution in which a metal compound and a hydrophilic compound are dissolved in a medium. The reduction method is a more preferable method.

(3) Cross-linking agent The cross-linking agent blended in the fluid composition has an active group capable of reacting with the hydrophilic group of the hydrophilic compound, and the active group of the cross-linking agent and the hydrophilic property of the hydrophilic compound. A group capable of undergoing a crosslinking reaction, for example, a group which can undergo condensation, addition polymerization or ring-opening polymerization with the above-mentioned carboxyl group, hydroxyl group, amino group, hydrazide group, amide group or the like. Examples of such an active group include an oxazoline group (—CONC ₂ ), a carbodiimide group (—N═C═N—), a blocked isocyanate group, an epoxy group (—COC), and a carbonyl group (—C═O). A crosslinking agent having at least one active group selected from these is preferable, and a crosslinking agent having at least one active group selected from an oxazoline group, a carbodiimide group, and a blocked isocyanate group is more preferable. In the present invention, these active groups may be contained in one type or two or more types in one type of cross-linking agent, and two or more types of cross-linking agents having different active groups may be used, or the same type of active group may be used. Two or more different kinds of cross-linking agents can be used. Moreover, 1 type of compounds chosen from a melamine and a melamine derivative can also be used as a crosslinking agent. Specifically, as the oxazoline-based crosslinking agent, 2,2′-bis (2oxazoline), 2,2′-methylene-bis (2oxazoline), 2,2′-ethylene-bis (4,4′dimethyl) -2oxazoline), 2,2'-phenylene-bis (2oxazoline), bis (2-oxazolinecyclohexanone) sulfide, and the like. Examples of the carbodiimide-based crosslinking agent include condensates of diisocyanate compounds such as xylene diisocyanate, hexamethylene diisocyanate, tolylene diisocyanate, and isophorone diisocyanate. Examples of the blocked isocyanate crosslinking agent include those obtained by blocking the isocyanate group (—N═C═O) of the above-mentioned diisocyanate compound with a blocking agent such as alcohol, phenol, oxime, or acid amide. Examples of the epoxy-based crosslinking agent include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,6-hexanediol glycidyl ether, and glycidyl acrylate. Examples of the carbonyl crosslinking agent include aldehyde compounds such as formaldehyde, glyoxal, and glutaraldehyde, ketone compounds such as diacetone, cyclopentadione, diacetone acrylamide, adipic acid hydrazide, acetoacetoxyethyl methacrylate, and allyl acetoacetate. It is done. Examples of the melamine crosslinking agent include melamine, a methylolated melamine derivative obtained by condensing melamine and formaldehyde, a compound partially or completely etherified by reacting a methylolated melamine with a lower alcohol, and a mixture thereof. .

  In a preferred embodiment of the hydrophilic compound and the cross-linking agent, at least one element selected from sulfur, nitrogen, phosphorus and a carboxyl group, a hydroxyl group, an amino group, a hydrazide group, and an amide group is provided on the surface of the metal particle. A compound having a kind of hydrophilic group is chemically bonded through the above elements, and the crosslinking agent is an oxazoline-based crosslinking agent, a carbodiimide-based crosslinking agent, a blocked isocyanate-based crosslinking agent, an epoxy-based crosslinking agent, or a melamine-based crosslinking agent. Even when the reaction between the hydrophilic group of the hydrophilic compound and the active group of the crosslinking agent cannot be confirmed in the coated product, the effects of the present invention such as excellent adhesion can be obtained. In a more preferred embodiment, a compound having a sulfur element and at least one hydrophilic group selected from a carboxyl group, a hydroxyl group, an amino group, a hydrazide group, and an amide group on the surface of the metal particle is the sulfur element. The crosslinking agent is at least one selected from an oxazoline crosslinking agent, a carbodiimide crosslinking agent, a blocked isocyanate crosslinking agent, an epoxy crosslinking agent, and a melamine crosslinking agent, and is a mercapto as a sulfur compound. More preferably, it is at least one selected from propionic acid, mercaptoacetic acid, thiodipropionic acid, mercaptosuccinic acid, mercaptoethanol, thiodiethylene glycol, thiodiglycolic acid, aminoethyl mercaptan, and thiodiethylamine.

  Furthermore, considering the reactivity of the hydrophilic compound and the crosslinking agent, it is more preferable to select an appropriate combination according to the type of each hydrophilic group and active group. For example, when the hydrophilic group is a carboxyl group, at least one selected from an oxazoline-based crosslinking agent, a carbodiimide-based crosslinking agent, a blocked isocyanate-based crosslinking agent, a melamine-based crosslinking agent, and an epoxy-based crosslinking agent has excellent adhesion, etc. The effect of the present invention can be obtained, and an oxazoline-based crosslinking agent, a carbodiimide-based crosslinking agent, and a blocked isocyanate-based crosslinking agent are more preferable. In addition, if the hydrophilic group is a hydroxyl group, a blocked isocyanate-based crosslinking agent, a melamine-based crosslinking agent, or the like is selected. If an amino group or an amide group, a blocked isocyanate-based crosslinking agent, an epoxy-based crosslinking agent, or the like is selected, and a hydrazide group is selected. In this case, it is more preferable to select a carbonyl-based crosslinking agent.

(4) Solvent The solvent to be blended in the fluid composition may be water or an organic solvent such as alcohols and ketones, and can be set as appropriate according to the use situation. Since the hydrophilic compound is chemically bonded, sufficient dispersion stability can be obtained even with water or an aqueous solvent mainly composed of water, so that it can be suitably used. The content of water in the aqueous solvent can be appropriately set according to the usage scene. For example, in order to form electrodes and circuit wiring patterns, water is preferably contained in an amount of 50% by weight or more, and 80% by weight or more. Is more preferable. On the other hand, in order to form a coating film for decorative use, water is preferably contained in an amount of 1% by weight or more, more preferably 5% by weight or more, more preferably 10% by weight or more, and more preferably 15% by weight or more. preferable. Aqueous solvents include alcohols such as methanol, ethanol, propanol, ethylene glycol, diacetone alcohol, and glycerin, methyl ethyl ketone, methyl isobutyl for the purpose of controlling the volatilization rate of the electrode, wiring pattern, and coating solvent. A hydrophilic organic solvent such as ketones such as ketone, glycol ethers such as ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, and the like can be mixed. Since water has a large surface tension, if necessary, an organic solvent having a relative dielectric constant of 35 or more, preferably 35 to 200, and a boiling point of 100 ° C. or more, preferably 100 to 250 ° C. is added. It is preferable because surface defects such as wrinkles and shrinkage hardly occur in the coated product during heat drying and heat baking, and a uniform and highly dense coated product is easily obtained. Examples of such organic solvents include N-methylformamide (dielectric constant 190, boiling point 197 ° C.), dimethyl sulfoxide (dielectric constant 45, boiling point 189 ° C.), ethylene glycol (relative dielectric constant 38, boiling point 226 ° C.), 4-butyrolactone. (Relative permittivity 39, boiling point 204 ° C.), acetamide (relative permittivity 65, boiling point 222 ° C.), 1,3-dimethyl-2-imidazolidinone (relative permittivity 38, boiling point 226 ° C.), formamide (relative permittivity 111, boiling point 210 ° C.), N-methylacetamide (relative dielectric constant 175, boiling point 205 ° C.), furfural (relative dielectric constant 40, boiling point 161 ° C.) and the like, and one or more selected from these can be used. . Among them, N-methylformamide (surface tension 38 × 10 ⁻³ N / m) having a surface tension of 50 × 10 ⁻³ N / m or less, 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 × 10 ⁻³ N / m) or the like is more effective and preferable. These organic solvents having a high relative dielectric constant and a high boiling point are preferably contained in a solvent other than water in a range of 20 to 100% by weight, and more preferably in a range of 40 to 100% by weight.

(5) Other components It is preferable to add an aqueous binder to the fluid composition of the present invention as necessary, since the adhesion between the coated material and the substrate is further improved. As the aqueous binder, a water-soluble type, an emulsion type, a colloidal dispersion type and the like can be used without limitation, but if it is cured by the cross-linking agent, it is preferable because a coating with high hardness is easily obtained, A water-soluble type is more preferable. Examples of suitable aqueous binders include protein-based polymers, aqueous acrylic resins, aqueous polyester resins, aqueous urethane resins, and aqueous cellulose, and it is preferable to use at least one selected from these. In particular, protein polymers such as gelatin, gum arabic, casein, sodium caseinate, and ammonium caseinate have a strong interaction with metal particles and more efficiently in the reaction with the cross-linking agent. In particular, gelatin is more preferable. As a suitable combination with a crosslinking agent, for example, a protein polymer, an aqueous urethane resin, an aqueous acrylic resin, an aqueous polyester resin and the like are preferable for an oxazoline-based crosslinking agent and a carbodiimide-based crosslinking agent. For the agent, protein-based polymer, aqueous acrylic resin, aqueous polyester resin, aqueous urethane resin, aqueous cellulose and the like are preferable. The amount of the aqueous binder component is preferably in the range of about 0.01 to 10 parts by weight with respect to 100 parts by weight of the metal particles, and more preferably in the range of about 0.01 to 8 parts by weight, and 0.01 to 5 parts by weight. If it is a grade, it is still more preferable.

  In addition to the metal particles, the crosslinking agent, the solvent, and the aqueous binder, the fluid composition of the present invention contains additives such as a surfactant, a dispersant, a thickener, a plasticizer, and an antifungal agent. Further, it can be appropriately blended as necessary. For example, the surfactant is preferable because it has an effect of further improving the dispersion stability of the metal particles and an effect of controlling the rheological properties of the fluid composition and improving the coatability. Specifically, the surfactant is a quaternary ammonium. Known surface activity such as cation type such as salt, anionic type such as carboxylate, sulfonate, sulfate ester salt, phosphate ester salt, nonionic type such as ether type, ether ester type, ester type, nitrogen type An agent can be used and 1 or more types chosen from these can be used. The compounding amount of the surfactant varies depending on the type of metal particles and the like, and is appropriately set according to the coating composition. Generally, it is about 0.01 to 0.5 parts by weight with respect to 100 parts by weight of the metal particles. A range is preferred.

Next, an electrode using the fluid composition of the present invention will be described.
An electrode and a circuit wiring pattern are obtained by applying the fluid composition of the present invention to a substrate by a method such as screen printing or inkjet printing, and then heating and baking the applied material at an appropriate temperature. The coating film is obtained by applying the fluid composition to a substrate and drying it by a method such as spin coating, roll coating, spray coating, or brush coating. Or a coating film can also be formed using printing methods, such as screen printing and inkjet printing, and a transfer method. Since the reaction between the crosslinking agent and the hydrophilic compound contained in the fluid composition or the reaction between the crosslinking agent and the aqueous binder is accelerated by heating, heating is performed at an appropriate temperature even when a coating film is obtained. It is preferable. In addition, since the solvent is volatilized in a short time by heating, wrinkles, wrinkles, dents and the like are hardly generated on the surface of the coating film, and it becomes easier to obtain a good appearance. The heating conditions are appropriately set depending on the combination of the crosslinking agent and the hydrophilic compound or aqueous binder, the type of substrate, etc., but the crosslinking agent is the oxazoline-based crosslinking agent, carbodiimide-based crosslinking agent, or blocked isocyanate-based crosslinking agent. If it exists, the range of 40-300 degreeC is preferable, A desired effect will be acquired when it heats for about 30 minutes to 2 hours at the temperature of the range of 80-200 degreeC more preferably. The coating film produced using the fluid composition of the present invention contains at least metal particles and a curing component, and the surface of the metal particles contains at least one element selected from sulfur, nitrogen and phosphorus and a hydrophilic group. The compound having a chemical bond is formed through the above-described elements, and the curing component can be configured to be crosslinked by the reaction between the hydrophilic group of the compound and the active group of the crosslinking agent.

The decorative article of the present invention is such that the above-mentioned coating film is formed on at least a part of the surface of the substrate, and the metal color and gloss of the metal particles are imparted to the substrate surface. The entire surface of the substrate can be colored to give gloss, and a design, mark, logo mark can be formed on a part of the substrate surface, and other characters, figures and symbols can be formed. . As the base material, use inorganic materials such as metals, glass, ceramics, concrete, organic materials such as rubber, plastic, paper, wood, leather, cloth, and fibers, and materials that use a combination of inorganic materials and organic materials or composite materials. Can do. The base material of those materials can be decorated by forming a coating film on the raw material base material before being processed into an article to be used, or can be decorated on any article after processing the base material. Moreover, decorating the surface of those previously coated on the substrate surface is also included.
Specific examples of articles to be decorated include (1) exterior, interior, bumper, door knob, side mirror, front grill, lamp reflector, display device, etc. of transportation equipment such as automobiles, trucks, and buses,
(2) Exteriors of electrical appliances such as TVs, refrigerators, microwave ovens, personal computers, mobile phones, cameras, remote controls, touch panels, front panels, etc.
(3) Houses, buildings, department stores, stores, shopping malls, pachinko shops, wedding halls, funeral halls, exteriors of buildings such as shrines and temples, window glass, entrances, nameplates, gates, doors, doorknobs, show windows, interiors, etc. ,
(4) Lighting equipment, furniture, furniture, toilet equipment, Buddhist altar tools, Buddhist statues and other home equipment
(5) Fixtures such as hardware and tableware,
(6) Vending machines for drinking water, tobacco, etc.
(7) Containers for synthetic detergents, skin care, soft drinks, alcoholic beverages, confectionery, food, tobacco, pharmaceuticals,
(8) Packing tools such as cover paper and cardboard boxes,
(9) Costumes and accessories such as clothes, shoes, bags, glasses, artificial nails, artificial hair, jewelry,
(10) Sports equipment such as baseball bats and golf clubs, hobby goods such as fishing equipment,
(11) Office supplies such as pencils, colored paper, notebooks, New Year postcards, desks and chairs,
(12) Books covers and covers, dolls, toys such as minicars, cards such as commuter passes, recording media such as CDs and DVDs, and the like. In addition, human nails, skin, eyebrows, hair, and the like can be used as a base material.

  The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Examples 1-6, Comparative Example 1
(Preparation of metal colloidal particles)
50 g of silver nitrate as a metal compound and 1.6 g of 3-mercaptopropionic acid as a hydrophilic compound were dissolved in 220 ml of pure water, and 70 ml of 28% ammonia water was added to adjust the pH to 11.6. On the other hand, 2.1 g of sodium borohydride as a reducing agent was dissolved in 295 ml of pure water to which 4 ml of 28% ammonia water was added. Both were dripped simultaneously in 600 milliliters of pure water over 30 minutes, and silver nitrate was reduced to produce silver colloidal particles having 3-mercaptopropionic acid on the surface in the medium. Next, the medium liquid of the obtained silver colloid particles is adjusted to pH 2.5 with nitric acid (30%), the silver colloid particles are settled, and the silver colloid particles (silver colloid particles are collected by a vacuum filter). 3 parts by weight of mercaptopropionic acid with respect to 1000 parts by weight of the particles.The average particle diameter of the silver colloidal particles is about 10 nm), and after washing with water until the specific conductivity of the filtrate is 10 μS / cm or less, Re-dispersion in water gave an aqueous silver colloid solution (containing 70% by weight of silver colloid particles).

(Preparation of fluid composition)
Using the silver colloid solution, the formulation shown in Table 1 was charged into a screw bottle and subjected to ultrasonic dispersion for 10 minutes to obtain a fluid composition (silver colloid particle concentration: 50% by weight) of the present invention and a comparative object. . Each is designated as samples AG.

（１）オキサゾリン系架橋剤（日本触媒社製）
（２）ブロックイソシアネート系架橋剤（第一工業製薬社製）
（３）カルボジイミド系架橋剤（日清紡社製）
（４）分散剤（有効成分４０重量％：ビックケミー社製）

(1) Oxazoline-based crosslinking agent (manufactured by Nippon Shokubai Co., Ltd.)
(2) Blocked isocyanate crosslinking agent (Daiichi Kogyo Seiyaku Co., Ltd.)
(3) Carbodiimide type crosslinking agent (Nisshinbo Co., Ltd.)
(4) Dispersant (active ingredient 40% by weight: manufactured by Big Chemie)

Comparative Examples 2-8
(Preparation of metal colloidal particles)
60 ml of an aqueous solution obtained by dissolving 39.4 g of silver nitrate as a metal compound in pure water, 262.8 g of trisodium citrate dihydrate as a surface protective agent, and 129.2 g of ferrous sulfate heptahydrate as a reducing agent, The solution was dropped into an aqueous solution dissolved in 800 ml of pure water over 20 minutes while stirring to reduce silver nitrate, and silver colloid particles having trisodium citrate existing on the surface were generated in the medium. Next, the obtained silver colloid particle liquid is centrifuged at 98000 m / s ² for 30 minutes using a centrifuge, and the sediment is recovered and redispersed in 800 ml of pure water. Further, 98000 m Centrifugation was performed at / s ² for 30 minutes to remove sediment, and an aqueous silver colloid solution was obtained. When the specific conductivity of this aqueous silver colloid solution was measured, it was 10 μS / cm or less. 800 ml of acetone is added to the obtained aqueous silver colloid solution, the silver colloid particles are aggregated, and centrifuged again at 29400 m / s ² for 30 minutes to collect a sediment, and a silver colloid particle cake (silver colloid particles Containing 61% by weight).

(Preparation of fluid composition)
Using the silver colloid particle cake, the formulation shown in Table 2 was charged into a screw bottle and subjected to ultrasonic dispersion for 10 minutes to obtain a fluid composition for comparison (silver colloid particle concentration: 20% by weight). Each is designated as samples H to N.

（１）オキサゾリン系架橋剤（日本触媒社製）
（２）ブロックイソシアネート系架橋剤（第一工業製薬社製）
（３）カルボジイミド系架橋剤（日清紡社製）
（４）分散剤（有効成分４０重量％：ビックケミー社製）

(1) Oxazoline-based crosslinking agent (manufactured by Nippon Shokubai Co., Ltd.)
(2) Blocked isocyanate crosslinking agent (Daiichi Kogyo Seiyaku Co., Ltd.)
(3) Carbodiimide type crosslinking agent (Nisshinbo Co., Ltd.)
(4) Dispersant (active ingredient 40% by weight: manufactured by Big Chemie)

Evaluation 1: Evaluation of specific resistance of coating film The fluid compositions (samples A to N) of Examples 1 to 6 and Comparative Examples 1 to 8 were applied on a glass plate with a # 16 bar coater, and the temperature was 150 ° C. And baked for 1 hour. The volume resistivity of the obtained coating film was measured using a Loresta-GP type low resistivity meter (manufactured by Mitsubishi Chemical Corporation). The results are shown in Table 3. It turns out that the electroconductive coating film obtained by the fluid composition of this invention shows the electroconductivity equivalent to the coating film obtained by the conventional method.

Evaluation 2: Evaluation of coating film strength and coating film appearance The fluid compositions (samples A to F and I to N) of Examples 1 to 6 and Comparative Examples 3 to 8 were applied onto a PET film with a # 10 bar coater. And baked at a temperature of 150 ° C. for 1 hour. The obtained coating film was made with 100 cutters having a size of 10 mm × 10 mm, and a cellophane tape was affixed thereon, and then the cellophane tape was peeled off at an angle of 90 °. The number of gobangs remaining on the PET film after peeling was measured. The larger this value, the higher the coating strength. Moreover, after immersing a coating film in water and 70 degreeC warm water overnight, the coating-film intensity | strength was evaluated similarly. Furthermore, the appearance of these coating films was visually observed. In Comparative Examples 1 and 2, since the coating film is not cured, this evaluation is not performed. The results are shown in Table 3. It can be seen that the conductive coating obtained by the fluid composition of the present invention has high coating strength and an excellent appearance. The above is a specific example of silver particles chemically bonded with a hydrophilic sulfur compound, but similar results have been obtained with hydrophilic nitrogen compounds and hydrophilic phosphorus compounds, and also with metal particles other than silver particles. It was confirmed that a result was obtained.

Example 7 and Comparative Example 9
An aqueous silver colloid solution (containing 70% by weight of silver colloid particles) was obtained in the same manner as in Example 1, and then, using this aqueous silver colloid solution, the formulation shown in Table 4 was charged into a screw bottle for 10 minutes. Ultrasonic dispersion was performed to obtain an ink composition (silver colloid particle concentration: 10% by weight) of the present invention and a comparative object. Let them be samples O and P, respectively.

（１）オキサゾリン系架橋剤（日本触媒社製）
（２）分散剤（有効成分４０重量％：ビックケミー社製）

(1) Oxazoline-based crosslinking agent (manufactured by Nippon Shokubai Co., Ltd.)
(2) Dispersant (active ingredient 40% by weight: manufactured by Big Chemie)

  The ink composition (samples O and P) of Example 7 and Comparative Example 9 was applied onto a PET film, glass plate, and acrylic plate with an airbrush (HP-CH manufactured by Anest Iwata Co., Ltd.), which is a type of spray coating machine, and 80 Bake for 1 hour at a temperature of 150 ° C or 150 ° C. The obtained coating film was made with 100 cutters of 10 mm × 10 mm in size by using the method of evaluation 2 above, and after applying cellophane tape on it, the cellophane tape was sharply applied at an angle of 90 °. It peeled. Table 5 shows the results of measuring the number of gobangs remaining on the PET film, glass plate, and acrylic plate after peeling, and evaluating the coating strength and appearance. It was found that the coating film obtained from the fluid composition of the present invention had high coating film strength and had a metallic gloss mirror surface.

  The flowable composition of the present invention is superior in adhesion to the base material than the conventional ones, and has been used in the conventional materials for ensuring electrical continuity, or antistatic, electromagnetic shielding or metallic luster. In addition to being widely used for applications such as materials to be applied, coatings with excellent conductivity and metallic luster can be obtained by heating at relatively low temperatures, so electrodes and circuit wiring that have been actively developed in recent years It can be applied to new uses of nanotechnology such as pattern formation, and it can also be applied to alternative uses of plating technology such as design and decoration by metallic luster.

Claims (17)

It contains at least metal particles, a crosslinking agent, and a solvent, and a compound having at least one element selected from sulfur, nitrogen, and phosphorus and a hydrophilic group is chemically bonded to the surface of the metal particles through the above elements. A fluid composition, wherein the cross-linking agent has an active group capable of reacting with the hydrophilic group of the compound. The fluid composition according to claim 1, wherein the hydrophilic group of the compound chemically bonded to the metal particles is at least one selected from a carboxyl group, a hydroxyl group, an amino group, a hydrazide group, and an amide group. . The fluid according to claim 1, wherein the crosslinking agent is a compound having at least one active group selected from an oxazoline group, a carbodiimide group, a blocked isocyanate group, and an epoxy group, or a melamine and / or a melamine derivative. Sex composition. At least one element selected from a carboxyl group, a hydroxyl group, an amino group, a hydrazide group, and an amide group and at least one element selected from sulfur, nitrogen, and phosphorus on the surface of the metal particle, including at least metal particles, a crosslinking agent, and a solvent The compound having a hydrophilic group is chemically bonded through the above-mentioned elements, and the crosslinking agent is an oxazoline crosslinking agent, a carbodiimide crosslinking agent, a blocked isocyanate crosslinking agent, an epoxy crosslinking agent, or a melamine crosslinking agent. A fluid composition comprising at least one selected. The fluid composition according to claim 1 or 4, wherein the compound chemically bonded to the metal particles is a sulfur compound. The sulfur compound is at least one selected from mercaptopropionic acid, mercaptoacetic acid, thiodipropionic acid, mercaptosuccinic acid, mercaptoethanol, thiodiethylene glycol, thiodiglycolic acid, aminoethyl mercaptan, and thiodiethylamine. Item 6. The fluid composition according to Item 5. The hydrophilic group of the compound chemically bonded to the metal particles is a carboxyl group, and the crosslinking agent is selected from oxazoline crosslinking agents, carbodiimide crosslinking agents, blocked isocyanate crosslinking agents, epoxy crosslinking agents, and melamine crosslinking agents. The fluid composition according to claim 1 or 4, wherein the fluid composition is at least one. The fluid composition according to claim 1 or 4, comprising a crosslinking agent in an amount of 0.01 to 10 parts by weight per 100 parts by weight of the metal particles. The metal constituting the metal particles is at least one selected from the group consisting of iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum, copper, silver, and gold. Or the fluid composition of 4. The fluid composition according to claim 9, wherein the metal particles are silver particles. The fluid composition according to claim 1 or 4, further comprising an aqueous binder. The fluid composition according to claim 11, wherein the aqueous binder is at least one selected from a protein polymer, an aqueous acrylic resin, an aqueous polyester resin, an aqueous urethane resin, and an aqueous cellulose. An electrode formed using the flowable composition according to claim 1. A wiring pattern formed using the fluid composition according to claim 1. A coating film formed using the fluid composition according to claim 1. A metal particle, containing at least a curing component, and a compound having a hydrophilic group and at least one element selected from sulfur, nitrogen, and phosphorus is chemically bonded to the surface of the metal particle via the element, and cured. The component is a coating film obtained by reacting the hydrophilic group of the compound with the active group of the crosslinking agent to cause crosslinking. A decorative article comprising the coating film according to claim 15 or 16 formed on at least a part of a surface of a substrate.