Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B22—CASTING; POWDER METALLURGY
  • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
  • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B22—CASTING; POWDER METALLURGY
  • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
  • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
  • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
  • B22F1/102—Metallic powder coated with organic material
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B22—CASTING; POWDER METALLURGY
  • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
  • B22F9/00—Making metallic powder or suspensions thereof
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
  • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
  • C09C1/62—Metallic pigments or fillers
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
  • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
  • C09C1/66—Copper alloys, e.g. bronze
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
  • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
  • C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D17/00—Pigment pastes, e.g. for mixing in paints
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
  • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
  • H01B1/20—Conductive material dispersed in non-conductive organic material
  • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys

Definitions

• the present invention relates to a metal particle composition.
• metal particles have been used for a variety of purposes, including as raw powder for powder metallurgy, as firing paste for multilayer ceramic capacitors, and as materials for conductive pastes and conductive inks for forming wiring by inkjet printing, etc.
• Patent Document 1 proposes a method of coating the particle surface with fatty acids such as fatty acids and fatty acid alkanolamides in order to suppress aggregation between particles.
• Patent Document 2 proposes a method of modifying the particle surface with an alkylamine.
• Patent Document 3 describes a technology that uses a compound having a specific structure including an unsaturated double bond together with metal particles.
• Patent Document 3 does not consider the dispersion stability of the metal particle composition.
• the present invention was made in consideration of these conventional problems, and aims to provide a metal particle composition that has excellent dispersion stability even in highly polar solvents.
• a metal particle composition with excellent dispersion stability can be obtained by using a compound having a specific structure containing unsaturated double bonds together with metal particles, and by using a solvent in which the polar term ⁇ P and hydrogen bond term ⁇ H of the Hansen solubility parameters are in specific numerical ranges, and thus completed the present invention.
• a metal particle composition comprising:
• R1 and R2 each independently represent a hydrogen atom; an alkyl group having 1 to 6 carbon atoms; an alkoxy group having 1 to 6 carbon atoms; an alkenyl group having 2 to 6 carbon atoms; an aryl group; or an aralkyl group.
• R3 and R4 each independently represent a hydrogen atom; an alkyl group having 1 to 6 carbon atoms; an alkoxy group having 1 to 6 carbon atoms; an alkenyl group having 2 to 6 carbon atoms; an alkenyloxy group having 2 to 6 carbon atoms; an aryl group; or an aralkyl group.
• R5 and R6 each independently represent a hydrogen atom; an alkyl group having 1 to 6 carbon atoms; an alkoxy group having 1 to 6 carbon atoms; an alkenyl group having 2 to 6 carbon atoms; an aryl group; or an aralkyl group.
• R7 and R8 each independently represent a hydrogen atom; an alkyl group having 1 to 6 carbon atoms; an alkoxy group having 1 to 6 carbon atoms; an alkenyl group having 2 to 6 carbon atoms; an alkenyloxy group having 2 to 6 carbon atoms; an aryl group; or an aralkyl group.
• R9 represents a hydrogen atom; a (meth)acrylic group; an alkyl group having 1 to 6 carbon atoms; an alkenyl group having 2 to 6 carbon atoms; an aryl group; or an aralkyl group.
• [5] The metal particle composition according to any one of the items [1] to [4], wherein the solvent (C) contains at least one selected from the group consisting of water, ethylene glycol, dipropylene glycol, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, and ⁇ -terpineol.
• the content of the compound (B) is 0.1 to 10 parts by mass per 100 parts by mass of the metal particles (A).
• a method for producing a metal particle composition comprising metal particles (A), a compound (B) having a structure represented by general formula (I), and a solvent (C) having a Hansen solubility parameter polarity term ⁇ P of 3.0 to 17.0 and a hydrogen bond term ⁇ H of 6.6 to 42.5, A method for producing a metal particle composition, comprising a mixing step of mixing the metal particles (A), the compound (B), and the solvent (C).
• R1 and R2 each independently represent a hydrogen atom; an alkyl group having 1 to 6 carbon atoms; an alkoxy group having 1 to 6 carbon atoms; an alkenyl group having 2 to 6 carbon atoms; an aryl group; or an aralkyl group.
• R3 and R4 each independently represent a hydrogen atom; an alkyl group having 1 to 6 carbon atoms; an alkoxy group having 1 to 6 carbon atoms; an alkenyl group having 2 to 6 carbon atoms; an alkenyloxy group having 2 to 6 carbon atoms; an aryl group; or an aralkyl group.
• the present invention provides a metal particle composition that has excellent dispersion stability even in highly polar solvents.
• this embodiment is an example for embodying the technical concept of the present invention, and the present invention is not limited to the description below.
• a metal particle composition according to an embodiment of the present invention is a metal particle composition comprising metal particles (A), a compound (B) having a structure represented by the following general formula (I), and a solvent (C) having a Hansen solubility parameter polarity term ⁇ P of 3.0 to 17.0 and a hydrogen bond term ⁇ H of 6.6 to 42.5:
• R1 and R2 each independently represent a hydrogen atom; an alkyl group having 1 to 6 carbon atoms; an alkoxy group having 1 to 6 carbon atoms; an alkenyl group having 2 to 6 carbon atoms; an aryl group; or an aralkyl group.
• R3 and R4 each independently represent a hydrogen atom; an alkyl group having 1 to 6 carbon atoms; an alkoxy group having 1 to 6 carbon atoms; an alkenyl group having 2 to 6 carbon atoms; an alkenyloxy group having 2 to 6 carbon atoms; an aryl group; or an aralkyl group.
• the metal particle composition uses a compound having a specific structure including unsaturated double bonds together with metal particles, and uses a solvent in which the polar term ⁇ P and hydrogen bond term ⁇ H of the Hansen solubility parameters are in specific ranges, thereby obtaining a metal particle composition having excellent dispersion stability.
• the reason for this is thought to be, but is not limited to, as follows.
• the compound with an unsaturated double bond interacts with the metal particles, so that the highly polar oxygen atom site is located on the outside of the particle.
• the affinity with highly polar solvents and solvents with high hydrogen bonding properties increases, the aggregation of particles is suppressed, and the dispersion stability is excellent even in highly polar solvents.
• the metal particle composition may be a mixture of the metal particles (A) and the compound (B), or at least a portion of the compound (B) may be attached to the metal particles (A).
• the surface of the metal particles (A) may be coated with the compound (B).
• the metal particle composition may be a mixture of the compound (B) and the metal particles (A), and a portion of the compound (B) may be attached to or coat the surface of the metal particles (A).
• Metal Particles (A) contained in the metal particle composition various types of particles containing a metal can be used without any particular limitation.
• the metal contained in the metal particles (A) include at least one selected from the group consisting of copper, silver, iron, nickel, tin, lead, and titanium.
• the metal may be an alloy as long as it contains any of the above elements.
• the metal particles (A) may contain elements other than metal elements such as hydrogen, oxygen, carbon, nitrogen, and sulfur as long as it contains any of the above elements.
• the metal particles (A) may be mixed particles containing any two or more of copper, silver, iron, nickel, tin, lead, and titanium.
• the metal particles (A) are preferably made of at least one metal selected from the group consisting of silver, copper, and iron, and more preferably made of at least one metal selected from the group consisting of silver and copper. Of these, copper or silver is preferred, and silver is more preferred, from the viewpoint of easily exerting the high performance inherent to metals, such as electrical conductivity.
• the metal particles (A) preferably contain copper or silver, and more preferably contain silver.
• the shape of the metal particles (A) is not particularly limited, but examples include granular, pellet-like, flake-like, spherical, needle-like, stick-like, and disk-like shapes. Among these, the shape is preferably spherical. When the metal particles (A) are spherical, it is easier to improve the fluidity.
• the average particle size of the metal particles (A) is not particularly limited, but is preferably 1 nm to 100 ⁇ m, more preferably 10 nm to 10 ⁇ m, and even more preferably 30 nm to 1 ⁇ m.
• the average particle size of the metal particles (A) is the primary particle size, and the primary particle size can be measured from images obtained by, for example, an electron microscope, an optical microscope, a digital microscope, or the like.
• the average particle size of the metal particles (A) can be calculated in accordance with JIS H 7804: 2005. Specifically, the method described in the Examples can be followed.
• Such metal particles (A) are made by shaping metal into particles, and can be produced by various known manufacturing methods. Commercially available metal particles (A) may also be used.
• the content of the metal particles (A) in the total amount of the metal particles (A) and the compound (B) is preferably 70 to 99.9 mass%, more preferably 80 to 99.8 mass%, and even more preferably 90 to 99.7 mass%.
• the content of the metal particles (A) is equal to or greater than the lower limit, it becomes easier to secure the necessary amount of metal, and also easier to secure the necessary physical properties such as electrical conductivity.
• the content of the metal particles (A) is equal to or less than the upper limit, the content of the compound (B) becomes relatively large, and therefore it becomes easier to improve the dispersion stability of the metal particle composition.
• the content of the metal particles (A) in the metal particle composition is preferably 0.01 to 90% by mass.
• the content of the metal particles (A) in the metal particle composition is more preferably 0.01 to 50% by mass, even more preferably 0.1 to 10% by mass, even more preferably 0.1 to 5% by mass, and even more preferably 0.2 to 3% by mass.
• R 1 and R 2 each independently represent a hydrogen atom; an alkyl group having 1 to 6 carbon atoms; an alkoxy group having 1 to 6 carbon atoms; an alkenyl group having 2 to 6 carbon atoms; an aryl group; or an aralkyl group.
• Examples of the alkyl group having 1 to 6 carbon atoms represented by R1 and R2 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a neopentyl group, an n-hexyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.
• Examples of the alkoxy group having 1 to 6 carbon atoms represented by R 1 and R 2 include a methoxy group, an ethoxy group, an n-propyloxy group, an isopropyloxy group, a butyloxy group, and a hexyloxy group.
• Examples of the alkenyl group having 2 to 6 carbon atoms represented by R 1 and R 2 include a vinyl group, an allyl group, a propenyl group, an isopropenyl group, a butenyl group, an isobutenyl group, a pentenyl group, a prenyl group, a hexenyl group (such as a cis-3-hexenyl group), and a cyclohexenyl group.
• the aryl group represented by R 1 and R 2 is preferably an aryl group having 6 to 18 carbon atoms, such as a phenyl group, a tolyl group, a xylyl group, and a naphthyl group.
• the aralkyl group represented by R 1 and R 2 is preferably an aralkyl group having 7 to 18 carbon atoms, such as a benzyl group, a 2-phenylethyl group, a 2-naphthylethyl group, or a diphenylmethyl group.
• R1 and R2 are each preferably independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkenyl group having 2 to 6 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, even more preferably a hydrogen atom or a methyl group, and still more preferably a methyl group.
• R3 and R4 each independently represent a hydrogen atom; an alkyl group having 1 to 6 carbon atoms; an alkoxy group having 1 to 6 carbon atoms; an alkenyl group having 2 to 6 carbon atoms; an alkenyloxy group having 2 to 6 carbon atoms; an aryl group; or an aralkyl group.
• Examples of the alkenyloxy group having 2 to 6 carbon atoms represented by R3 and R4 include a vinyloxy group, a 1-propenyloxy group, a 2-n-propenyloxy group (allyloxy group), a 1-n-butenyloxy group, and a prenyloxy group.
• alkyl group having 1 to 6 carbon atoms examples include the alkyl group having 1 to 6 carbon atoms, the alkoxy group having 1 to 6 carbon atoms, the alkenyl group having 2 to 6 carbon atoms, the aryl group, and the aralkyl group represented by R3 and R4 are the same as those for R1 and R2 above, and therefore a duplicated explanation will be omitted.
• R 3 and R 4 are each preferably independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkenyl group having 2 or 3 carbon atoms, or an aryl group, more preferably a hydrogen atom or a methyl group, and even more preferably a hydrogen atom.
• R 3 and R 4 are both hydrogen atoms.
• compound (B) containing the structure represented by general formula (I) is a compound containing a structure represented by the following general formula (II).
• R5 and R6 each independently represent a hydrogen atom; an alkyl group having 1 to 6 carbon atoms; an alkoxy group having 1 to 6 carbon atoms; an alkenyl group having 2 to 6 carbon atoms; an aryl group; or an aralkyl group.
• R7 and R8 each independently represent a hydrogen atom; an alkyl group having 1 to 6 carbon atoms; an alkoxy group having 1 to 6 carbon atoms; an alkenyl group having 2 to 6 carbon atoms; an alkenyloxy group having 2 to 6 carbon atoms; an aryl group; or an aralkyl group.
• R9 represents a hydrogen atom; a (meth)acrylic group; an alkyl group having 1 to 6 carbon atoms; an alkenyl group having 2 to 6 carbon atoms; an aryl group; or an aralkyl group.
• examples of the alkyl group having 1 to 6 carbon atoms, the alkoxy group having 1 to 6 carbon atoms, the alkenyl group having 2 to 6 carbon atoms, the aryl group, and the aralkyl group represented by R5 and R6 are the same as those for R1 and R2 above.
• examples of the alkyl group having 1 to 6 carbon atoms, the alkoxy group having 1 to 6 carbon atoms, the alkenyl group having 2 to 6 carbon atoms, the alkenyloxy group having 2 to 6 carbon atoms, the aryl group, and the aralkyl group represented by R7 and R8 are the same as those for R3 and R4 above.
• R 9 is a hydrogen atom.
• Compound (B) is, for example, a compound having a molecular structure represented by at least one of the following general formulas (III) to (VII). From the viewpoint of making it easier to improve the dispersion stability of the metal particle composition, it is preferable that the compound be represented by at least one of the general formulas (III) to (VI), and it is more preferable that the compound be represented by at least one of the general formulas (III), (V), and (VI).
• the compound represented by the general formula (III) has a weight average molecular weight (Mw) in terms of polystyrene of 200 to 50,000.)
• R 10 , R 11 , R 13 and R 14 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aryl group, or an aralkyl group.
• R 12 represents any one of a hydroxyl group, a (meth)acryloyloxy group, a 4-vinylphenoxy group and an alkenyloxy group having 2 to 6 carbon atoms.
• L represents an alkylene group having 1 to 6 carbon atoms and having R 12 as a substituent.
• a and B each independently represent a substituted or unsubstituted alkylene group having 1 to 6 carbon atoms.
• a and b each independently represent an integer of 0 or 1 to 100.
• R 12 is preferably a hydroxyl group or a (meth)acryloyloxy group, more preferably a hydroxyl group.
• the alkenyloxy group having 2 to 6 carbon atoms may be a vinyloxy group having 2 to 6 carbon atoms.
• the (meth)acryloyloxy group refers to an acryloyloxy group or a methacryloyloxy group.
• Examples of the alkenyloxy group represented by R 12 include a vinyloxy group, a 1-propenyloxy group, a 2-n-propenyloxy group (allyloxy group), a 1-n-butenyloxy group, and a prenyloxy group.
• R 15 , R 16 , R 21 and R 22 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aryl group, or an aralkyl group.
• R 17 and R 18 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aryl group, or an aralkyl group.
• R 19 represents a hydrogen atom or a methyl group
• R 20 represents any one of a hydroxyl group, a (meth)acryloyloxy group, a 4-vinylphenoxy group, and an alkenyloxy group having 2 to 6 carbon atoms.
• R 19 is preferably a hydrogen atom.
• R 20 is preferably a hydroxyl group or a (meth)acryloyloxy group, more preferably a hydroxyl group.
• R 15 , R 16 , R 21 , and R 22 in the general formula (VI) are the same as R 1 and R 2 in the general formula (I)
• R 17 and R 18 in the general formula (VI) are the same as R 3 and R 4 in the general formula (I)
• R 20 in the general formula (VI) is the same as R 12 in the general formula (V). The same is true for the examples and preferred ones of these, so a duplicated explanation will be omitted.
• the compounds represented by the above general formulas (III) and (IV) have hydroxyl groups in their molecules, and the compounds represented by the above general formulas (V) and (VI) have R 12 and R 20 , which are functional groups exhibiting electron donating properties, in their molecules. The presence of these groups makes it easier to increase the adsorption of the compound (B) to metal particles while maintaining the stability of the compound.
• the compounds represented by the general formulas (III), (V), and (VI) have relatively high electron donating groups bonded to the double bonds at both ends, making it easier to improve stability.
• R 23 , R 24 , R 27 and R 28 each independently represent an alkyl group having 1 to 6 carbon atoms; an alkoxy group having 1 to 6 carbon atoms; an alkenyl group having 2 to 6 carbon atoms; an aryl group; or an aralkyl group.
• R 25 and R 26 each independently represent a hydrogen atom; an alkyl group having 1 to 6 carbon atoms; an alkoxy group having 1 to 6 carbon atoms; an alkenyl group having 2 to 6 carbon atoms; an aryl group; or an aralkyl group.
• R23 , R24 , R27 and R28 in the general formula (VII) are the same as R1 and R2 in the general formula (I), respectively, and R25 and R26 in the general formula (VII) are the same as R3 and R4 in the general formula (I), respectively. The same is true for the examples and preferred ones of these, so duplicated explanations will be omitted.
• the metal particle composition preferably contains 0.1 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, of compound (B) containing the structure represented by the above general formula (I) relative to 100 parts by mass of metal particles (A).
• the content of compound (B) is 0.1 parts by mass or more, the dispersion stability of the metal particle composition is easily obtained.
• the content of compound (B) is 5 parts by mass or less, the amount of metal particles (A) is relatively large, so that the necessary amount of metal can be secured, and the necessary physical properties such as conductivity can be secured, resulting in a good balance between production costs and the obtained effects.
• the content of compound (B) is preferably 0.1 to 4 parts by mass, more preferably 0.15 to 3 parts by mass, even more preferably 0.2 to 3 parts by mass, and even more preferably 0.2 to 2 parts by mass.
• the solvent (C) is a solvent having a polarity term ⁇ P of 3.0 to 17.0 and a hydrogen bond term ⁇ H of 6.6 to 42.5 in the Hansen solubility parameters.
• the polarity term ⁇ P is preferably 3.0 to 16.0, more preferably 3.0 to 15.0, even more preferably 3.0 to 14.0, even more preferably 3.0 to 10.0, even more preferably 3.5 to 10.0, and even more preferably 6.0 to 9.0.
• the polarity term ⁇ H is preferably 6.6 to 35.0, more preferably 6.6 to 25.0, even more preferably 6.6 to 20.0, even more preferably 7.0 to 20.0, even more preferably 10.0 to 20.0, and even more preferably 14.0 to 17.0.
• the Hansen solubility parameter is a three-dimensional vector obtained by dividing the solubility parameter (SP value) into three parts: dispersion term ⁇ D, polar term ⁇ P, and hydrogen bond term ⁇ H.
• the polar term ⁇ P and hydrogen bond term ⁇ H of the Hansen solubility parameter can be calculated by the following calculation. That is, the calculation was performed using the calculation software "Hansen Solubility Parameters in Practice (HSPiP) Version 5.3.05" (by Steven Abbott, Charles M. Hansen, and Hiroshi Yamamoto). The method of estimating the HSP value in such software is based on "Hansen Solubility Parameters: A Users Handbook (by Charles M. Hansen, CRC Press, 2007)” and the like.
• water, alcohols, ethers, ketones or esters having a polarity parameter ⁇ P of 3.0 to 17.0 and a hydrogen bond parameter ⁇ H of 6.6 to 42.5 are preferred, with water or alcohols being more preferred.
• the alcohol having a polar term ⁇ P of 3.0 to 17.0 and a hydrogen bond term ⁇ H of 6.6 to 42.5 from the viewpoint of improving the dispersion stability of the metal particle composition, a monol or polyol having a polar term ⁇ P of 3.0 to 17.0 and a hydrogen bond term ⁇ H of 6.6 to 42.5 is preferred, a monol or diol having a polar term ⁇ P of 3.0 to 17.0 and a hydrogen bond term ⁇ H of 6.6 to 42.5 is more preferred, and a diol having a polar term ⁇ P of 3.0 to 17.0 and a hydrogen bond term ⁇ H of 6.6 to 42.5 is even more preferred.
• the diol is preferably a diol in which the hydrogen atoms bonded to two carbon atoms in an aliphatic hydrocarbon containing one or more etheric oxygen atoms or not containing one, two or more etheric oxygen atoms are replaced by a hydroxyl group, more preferably a diol in which the hydrogen atoms bonded to two carbon atoms in an aliphatic hydrocarbon containing one or more etheric oxygen atoms are replaced by a hydroxyl group, and even more preferably a diol in which the hydrogen atoms bonded to two carbon atoms in an aliphatic hydrocarbon containing one etheric oxygen atom are replaced by a hydroxyl group.
• the diol contains the etheric oxygen atom, the dispersion stability of the metal particle composition tends to be further improved.
• Solvents (C) include ethylene glycol ( ⁇ P: 13.5, ⁇ H: 27.4), propylene glycol ( ⁇ P: 10.2, ⁇ H: 22.1), propanediol ( ⁇ P: 11.7, ⁇ H: 23.7), dipropylene glycol ( ⁇ P: 8.2, ⁇ H: 15.5), glycerin ( ⁇ P: 12.7, ⁇ H: 27.8), butyl carbitol ( ⁇ P: 6.2, ⁇ H: 10.5), ethylene glycol monobutyl ether ( ⁇ P: 6.3, ⁇ H: 12.3), 3-methyl-1,3-butanediol ( ⁇ P: 11.0, ⁇ H: 22.8), 3-methoxy-3-methyl-1-butanol ( ⁇ P: 6.0, ⁇ H: 9.9), nonanediol ( ⁇ P: 6.5, ⁇ H: 13.8), 2-methyl-1,8-octanediol ( ⁇ P: 6.3, ⁇ H: 13.9), ⁇ -
• Solvent (C) can be used as a mixed solvent if the polar term ⁇ P of the solvent after mixing of two or more solvents is in the range of 3.0 to 17.0 and the hydrogen bond term ⁇ H is in the range of 6.6 to 42.5.
• the polar term ⁇ P and hydrogen bond term ⁇ H of the Hansen solubility parameters in a mixed solvent can be calculated as a weighted average of the polar term ⁇ P and hydrogen bond term ⁇ H of each solvent contained in the mixed solvent and the volume fraction of each solvent contained in the mixed solvent.
• the metal particle composition preferably contains 10 to 100,000 parts by mass of the solvent (C) relative to 100 parts by mass of the total amount of the metal particles (A) and the compound (B).
• the content of the solvent (C) is 10 parts by mass or more, the metal particle composition does not become solid and can maintain a paste state.
• the content of the solvent (C) is 100,000 parts by mass or less, the amount of the metal particles (A) is relatively large, so that the necessary amount of metal can be secured and the necessary physical properties such as conductivity can be secured.
• the content of the solvent (C) is preferably 50 to 80,000 parts by mass, more preferably 100 to 50,000 parts by mass, even more preferably 500 to 20,000 parts by mass, and even more preferably 1,000 to 15,000 parts by mass.
• the content of the solvent (C) is also preferably 10 to 20,000 parts by mass.
• the above metal particle composition may contain a solvent other than solvent (C). From the viewpoint of improving the dispersion stability of the metal particle composition, the content of solvent (C) in the total amount of solvent is preferably 60 to 100 mass%, more preferably 80 to 100 mass%, even more preferably 90 to 100 mass%, and even more preferably 100 mass%.
• the metal particle composition may further contain components other than those described above, such as a diluent, a pigment, a dye, a filler, an ultraviolet absorber, a thickener, a shrinkage reducing agent, an antioxidant, a plasticizer, an aggregate, a flame retardant, a stabilizer, a fiber reinforcement material, an antioxidant, a leveling agent, and an anti-sagging agent.
• a diluent such as a diluent, a pigment, a dye, a filler, an ultraviolet absorber, a thickener, a shrinkage reducing agent, an antioxidant, a plasticizer, an aggregate, a flame retardant, a stabilizer, a fiber reinforcement material, an antioxidant, a leveling agent, and an anti-sagging agent.
• the total amount of the metal particles (A), the compound (B), and the solvent (C) in the metal particle composition is preferably 60 mass % or more, preferably 60 to 100 mass %, more preferably 80 to 100 mass %, even more preferably 90 to 100 mass %, and even more preferably 100 mass %.
• the method for producing a metal particle composition according to an embodiment of the present invention includes a mixing step of mixing metal particles (A), a compound (B), and a solvent (C), thereby producing the metal particle composition.
• the method for producing the metal particle composition may include a step of coating metal particles (A) with a compound (B) containing a structure represented by general formula (I) above, and a dispersion step of mixing the metal particles (A) coated with compound (B) with a solvent (C) having a Hansen solubility parameter polarity term ⁇ P of 3.0 to 17.0 and a hydrogen bond term ⁇ H of 6.6 to 42.5.
• the order in which the components are mixed is not particularly limited. That is, the order in which the metal particles (A), the compound (B), and the solvent (C) are mixed is not particularly limited. All the components may be mixed at once or in order.
• the method for producing the metal particle composition from the viewpoint of making it easy to mix the metal particles (A) and the compound (B) uniformly, it is also preferable to mix the metal particles (A) and the compound (B) in the mixing step, and then mix the solvent (C). From the same viewpoint, it is also preferable to mix the metal particles (A), the compound (B) and the organic solvent in the mixing step, and then mix the solvent (C).
• the metal particles (A), the compound (B) and the organic solvent it is more preferable to mix the metal particles (A), the compound (B) and the organic solvent, remove the organic solvent, and then mix the solvent (C). It is further preferable to include a coated metal particle production step of mixing the metal particles (A), the compound (B) and the organic solvent, and removing the organic solvent to obtain coated metal particles, and a dispersion step of mixing the coated metal particles with the solvent (C) to obtain a dispersion liquid.
• the order of mixing the components is not particularly limited.
• Compound (B) may be mixed into the organic solvent and then metal particles (A) may be added thereto, or metal particles (A) may be mixed into the organic solvent and then compound (B) may be added thereto, or compound (B) and metal particles (A) may be added to the organic solvent at the same time.
• Other components may be mixed with the metal particles (A) and the compound (B) as needed.
• the order in which the other components are added is not particularly limited, and the other components may be added to the organic solvent together with the compound (B), may be added to the organic solvent together with the metal particles (A), or may be added to the organic solvent together with the compound (B) and the metal particles (A).
• the amount of compound (B) added per 100 parts by mass of metal particles (A) is preferably 10 to 500 parts by mass, and more preferably 20 to 200 parts by mass, from the viewpoint of obtaining a metal particle composition having the above-mentioned composition.
• the organic solvent is removed to obtain coated metal particles. More specifically, the organic solvent is removed from the mixture by distilling off the organic solvent using an evaporator or the like, thereby obtaining coated metal particles consisting of metal particles (A) and a compound (B) that coats the metal particles (A). More preferably, the coated metal particles include a coating layer on the surface of the metal particles (A), and the coating layer includes a compound (B). In the coated metal particles, the coating layer may contain a component other than the compound (B) in addition to the compound (B).
• the main component of the coating layer is the compound (B), and it is more preferable that 90 mass% or more of the coating layer is the compound (B), and it is even more preferable that the coating layer is substantially composed of only the compound (B).
• the coating layer does not contain a resin component.
• the coating layer may cover the entire metal particles (A), or may cover only a part of the metal particles (A).
• the compound (B) may be attached to the metal particles (A).
• the organic solvent used in producing the coated metal particles include acetone, methanol, 1-propanol, and tetrahydrofuran.
• the amount of the organic solvent used is not particularly limited, but is, for example, 0.2 to 2.0 L per 10 g of compound (B).
• the above-mentioned metal particles (A) can be used as the metal particles.
• the metal compound metal oxide, etc.
• the metal compound may be converted to a metal in this process.
• a metal oxide is used as the raw material for the metal particles (A)
• a reducing agent such as hydrazine monohydrate may be further added to reduce the metal oxide and convert it to a metal.
• the coated metal particles are mixed with the solvent (C).
• the solvent (C) may be any of those mentioned above.
• the mixing method is not particularly limited, but may be performed by stirring and mixing using an ultrasonic homogenizer, a roll mill, a ball mill, a bead mill, a paint shaker, a kneader, an attritor, a sand mill, or the like.
• the above metal particle composition has excellent oxidation resistance, does not require a transition metal catalyst, and can be applied to existing metal particles, and therefore can be used in a wide range of fields.
• it can be used as a raw material powder for powder metallurgy, a firing paste for multilayer ceramic capacitors, and a material for conductive pastes and conductive inks for forming wiring by inkjet printing, etc.
• the paste according to the embodiment of the present invention includes the metal particle composition described above.
• the metal particle composition has excellent dispersion stability, so that a paste can be obtained that is less likely to cause problems such as increased electrical resistance or decreased thermal conductivity even if the particle size of the metal particles (A) is small.
• the above paste is unlikely to cause problems such as increased electrical resistance and decreased thermal conductivity even if the particle size of the metal particles (A) is small, and can therefore be used, for example, as a conductive paste for forming wiring in electronic components or a firing paste for multilayer ceramic capacitors.
• the paste may further include a binder.
• the binder may be one containing a resin and a solvent. When the paste contains a binder, it can provide the paste with a function of adhering and solidifying the metal particles (A) to an object such as a printed wiring board.
• the resin contained in the binder is preferably a thermosetting resin or an ultraviolet-curing resin. It may also be a resin that is cured by other energy rays such as an electron beam.
• the resin is a thermosetting resin
• the paste can be solidified by heating.
• the resin is an ultraviolet-curing resin
• the paste can be solidified by irradiating the paste with ultraviolet rays.
• Thermosetting resins are not particularly limited, but examples include various modified polyester resins such as polyester resin, urethane-modified polyester resin, epoxy-modified polyester resin, and acrylic-modified polyester resin, polyurethane resin, polyether urethane resin, polycarbonate urethane resin, acrylic urethane resin, vinyl chloride-vinyl acetate copolymer, epoxy resin, modified epoxy resin, phenol resin, acrylic resin, alkyd resin, alkyd phenol resin, butyral resin, polyvinyl butyral resin, ethylene-vinyl acetate copolymer, polyamide-imide, polyimide, polyamide, nitrocellulose, cellulose acetate butyrate, cellulose acetate propionate, and other modified celluloses. These may be used alone or in combination of two or more.
• a thermal polymerization catalyst such as peroxide may be used in combination with the thermosetting resin.
• the ultraviolet-curable resin may be a resin obtained by using a photopolymerizable monomer, that is, the photopolymerizable monomer is polymerized to become the ultraviolet-curable resin.
• the photopolymerizable monomer is not particularly limited, but examples thereof include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polyurethane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, trimethylolpropane ethylene oxide modified tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and
• the solvent contained in the binder has the function of mixing the metal particles (A) with the resin.
• This solvent may be different from the above-mentioned solvent (C), or it may be the same.
• the solvent is volatilized and removed when the paste is adhered to and solidified on an object such as a printed wiring board.
• Such solvents are not particularly limited as long as they are inert, but examples thereof include aromatics such as anisole and diphenyl ether, glycol ethers such as cellosolve, methyl cellosolve, carbitol, methyl carbitol, butyl carbitol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, and tripropylene glycol normal butyl ether, esters such as ethyl acetate, butyl acetate, ethyl butyrate, n-butyl butyrate, and cellosolve acetate, alcohols such as ethanol, propanol, ethylene glycol, propylene glycol, terpineol, and butyl carbitol
• the content of the binder in the paste is preferably 10 to 50 parts by mass, and more preferably 12.5 to 33.3 parts by mass, per 100 parts by mass of metal particles (A).
• the viscosity of the paste at 25°C is preferably 10 to 200,000 mPa ⁇ s, more preferably 1,000 to 100,000 mPa ⁇ s, from the viewpoint of ease of handling.
• the viscosity can be measured, for example, by a cone-plate viscometer.
• the paste When the paste is applied to an object by spraying it from a nozzle such as an inkjet, the paste may be further diluted with an organic solvent or the like.
• the thixotropy ratio of the paste at 25° C. is preferably 1.0 to 4.0, and more preferably 1.5 to 3.5.
• the thixotropy ratio at 25° C. is a value expressed as viscosity at a shear rate of 10 s ⁇ 1 at 25° C./viscosity at a shear rate of 100 s ⁇ 1 at 25° C.
• the shape of the metal particles (A) contained in the paste there is no particular restriction on the shape of the metal particles (A) contained in the paste, and as described above, various shapes may be used, but spherical shapes are particularly preferred.
• the metal particles (A) contained in the paste are spherical, the fluidity is improved. Therefore, when a paste containing spherical metal particles is sprayed onto an object from a nozzle such as an inkjet head, clogging of the nozzle is easily suppressed, which in turn makes it easier to form conductive circuits of a printed wiring board, etc., in the desired position.
• the paste may further contain the various components listed as other components that may be contained in the metal particle composition.
• the paste may contain a conductive organic compound.
• the conductive organic compound include polycyclic aromatic compounds such as pentacene, polyacetylene, poly(p-phenylenevinylene), polypyrrole, polythiophene, polyaniline, poly(p-phenylene sulfide), polyphenylenevinylene, and other conductive polymers, conductive liquid crystals, and the like.
• a conductive liquid crystal is preferred, and a mixture of two or more kinds of conductive liquid crystals is more preferred.
• the conductive liquid crystal is regularly oriented between the metal particles, thereby further improving the electrical conductivity of the paste.
• the method for producing the paste is not particularly limited, and various conventionally known production methods can be used.
• the paste can be produced by mixing the metal particle composition, the binder, and other components used as necessary by a known method.
• the paste is applied to an object such as a printed wiring board, and then heated at, for example, 100° C. or higher to volatilize the solvent in the binder and cure the resin in the binder if it is a thermosetting resin. If the resin in the binder is an ultraviolet curable resin, it is cured by irradiating it with ultraviolet light after or in addition to heating. In this way, when the paste is solidified, the metal particles can be adhered and solidified to a printed wiring board or the like in a uniformly dispersed state while maintaining a state in which adjacent metal particles are in contact with each other or are connected to each other via a conductive organic compound.
• the metal particle compositions obtained in the examples and comparative examples were evaluated as follows. ⁇ Dispersion Stability Evaluation> The vial containing the dispersion of metal particles was left to stand at room temperature, and the degree of sedimentation was observed. The number of days until the interface between the metal particles and the supernatant liquid became half or less of the liquid height was recorded as the "number of days required for sedimentation.”
• TG measurement thermogravimetry
• the TG measurement was carried out under the following measurement conditions.
• Measuring equipment DTG-60H (Shimadzu Corporation) Measurement temperature: The cooling conditions were -5°C/min and holding temperature of 20°C for 100 min. The heating conditions were a heating rate of 5° C./min and a hold temperature of 600° C. for 0 min.
• Sample amount about 10 mg
• Cell Alumina Atmosphere gas: Nitrogen gas Flow rate: 100 ml/min
• Synthesis Example 1 Synthesis of compound (B-1) In a reactor equipped with a stirrer, a thermometer, and a dropping funnel, 61.8 g (0.717 mol, manufactured by Kuraray Co., Ltd.) of 3-methyl-2-buten-1-ol and 36.84 g (0.657 mol) of potassium hydroxide were charged under a nitrogen stream. The internal temperature was kept below 10°C, and 19.34 g (0.209 mol, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) of epichlorohydrin was added dropwise while stirring, and the temperature was raised to 50°C after the end of the dropwise addition. The internal temperature was stirred at 50°C for 6 hours, and then cooled to 25°C.
• reaction solution was neutralized with a 4M aqueous hydrochloric acid solution, and the upper layer was washed with 310 mL of ion-exchanged water.
• the resulting organic layer was purified by distillation to obtain 28.77 g (0.126 mol; yield 60.3%) of 1,3-bis(3-methyl-2-butenoxy)-2-hydroxypropane represented by the following formula (B-1).
• Example 1 A beaker was charged with 500 mg of silver particles (A-1), 500 mg of compound (B-1), and 50 mL of methanol, and ultrasonic irradiation was performed for 10 minutes using an ultrasonic homogenizer. The obtained silver particle dispersion was centrifuged to remove the supernatant, and then washed with methanol and acetone and dried in vacuum to obtain 420 mg of coated silver particles coated with compound (B-1). The amount of coating of compound (B-1) on the coated silver particles was measured from the weight loss amount by TG measurement (sample amount: 13.630 mg) under a nitrogen stream. The blending amounts of each component, and the contents of silver particles (A-1) and compound (B-1) in the obtained coated silver particles are shown in Table 1.
• Coated silver particles were obtained in the same manner as in Production Example 1, except that the amounts of each component were as shown in Table 1.
• the amount of coating of compound (B) or (B') was measured from the amount of weight loss by TG measurement under a nitrogen stream.
• the contents of silver particles (A-1) and compound (B) or (B') in the obtained coated silver particles are shown in Table 1.
• Examples 2 to 8 Comparative Examples 1 to 10> A silver particle dispersion was obtained in the same manner as in Example 1, except that the formulation was changed as shown in Table 2. The obtained dispersion was allowed to stand, and the dispersion stability was evaluated. The contents of each component in the silver particle dispersion and the evaluation results of the dispersion stability are shown in Table 2.
• the metal particle composition of the present invention containing compound (B) has higher dispersion stability than the comparative example not containing compound (B).
• solvents (C) whose Hansen solubility parameters were within a given range showed high dispersion stability, whereas solvents outside the range showed sedimentation within one day and dispersion stability was not maintained.
• Example 11 A copper particle dispersion was obtained in the same manner as in Example 9, except that the compound (B-1) and the solvent (C-1) were used in the proportions shown in Table 4. The obtained dispersion was allowed to stand, and the dispersion stability was evaluated. The contents of each component in the copper particle dispersion and the evaluation results of the dispersion stability are shown in Table 4.

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