WO2016136571A1 - Résine hybride métallique et son procédé de production - Google Patents

Résine hybride métallique et son procédé de production Download PDF

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WO2016136571A1
WO2016136571A1 PCT/JP2016/054660 JP2016054660W WO2016136571A1 WO 2016136571 A1 WO2016136571 A1 WO 2016136571A1 JP 2016054660 W JP2016054660 W JP 2016054660W WO 2016136571 A1 WO2016136571 A1 WO 2016136571A1
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metal
resin
phenol resin
hybrid resin
atom
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PCT/JP2016/054660
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English (en)
Japanese (ja)
Inventor
鎌田　徹
忠明 山岸
崇文 林
友樹 生越
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住友ベークライト株式会社
国立大学法人金沢大学
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Priority to JP2017502307A priority Critical patent/JP6706804B2/ja
Publication of WO2016136571A1 publication Critical patent/WO2016136571A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols

Definitions

  • the present invention relates to a metal hybrid resin and a manufacturing method thereof.
  • Patent Document 1 a printing adhesive layer forming ink containing conductive particles having a primary particle diameter of 1 to 300 nm, a curable resin, a dispersant, and a solvent is prepared, printed on a substrate, and cured.
  • a technique for forming an adhesive layer in a composite layer is disclosed. According to such a technique, it is said that the adhesion between the substrate and the wiring layer can be improved and the connection resistance can be lowered.
  • Patent Document 2 discloses a conductive layer-forming composition containing inorganic particles including a dispersion medium and a metal oxide, a binder material, and conductive particles containing conductive particles having a number average particle diameter of 1 nm to 3000 nm.
  • a composition set comprising an adhesive composition is disclosed, and according to such a conductive adhesive composition, high adhesion between a conductive substrate and a conductor layer formed from a metal-containing particle dispersion is provided on the surface. It is said that the continuity between the conductor layer and the substrate can be secured.
  • the present invention has been made in view of the above problems, and provides a metal resin composite material in which metal particles are uniformly dispersed in a resin and can exhibit high mechanical strength.
  • a phenolic resin (B) A metal hybrid resin comprising metal particles composed of metal atoms coordinated to oxygen atoms in the phenol resin is provided.
  • (A) (A) a step of preparing a phenol resin; (B) (B ′) preparing a metal salt solution; (C) A step of mixing the (A) phenol resin and the (B ′) metal salt solution to coordinate a metal atom to an oxygen atom in the (A) phenol resin to obtain a metal hybrid resin.
  • the present invention is a composite material including a phenol resin and metal particles, wherein a metal atom constituting the metal particle is coordinated to an oxygen atom in the phenol resin.
  • a metal atom constituting the metal particle is coordinated to an oxygen atom in the phenol resin.
  • the metal particles and the resin can be bonded through a chemical bond, the metal particles can be uniformly dispersed in the resin, and high mechanical strength can be expressed.
  • the name of the “metal hybrid resin” is the name of the present inventors and refers to a novel metal resin composite material in which the metal particles and the resin material as described above are bonded through a coordinate bond. Is.
  • FIG. 2 is a chart of an Ag3d narrow scan spectrum measured for the metal resin composite material obtained in Example 1.
  • FIG. It is a chart of Ag3d narrow scan spectrum measured about the sample which cleaned Ag foil with Ar ion. It is a photograph figure which shows the result of having observed the surface with the transmission electron microscope (TEM) about the metal resin composite material obtained by Example 1.
  • TEM transmission electron microscope
  • the metal hybrid resin of this embodiment contains the following components (A) and (B).
  • ((A) Phenolic resin What is necessary is just to select suitably the phenol resin used for the metal hybrid resin of this embodiment from well-known phenol resins in view of a use etc.
  • this phenol resin for example, a novolak type phenol resin, a resol type phenol resin, an aryl alkylene type phenol resin, or the like can be used.
  • the novolac-type phenol resin can be obtained, for example, by reacting phenols and aldehydes under an acidic catalyst.
  • phenols used in producing the novolak type phenol resin include phenol, cresol, xylenol, ethylphenol, p-phenylphenol, p-tert-butylphenol, p-tert-amylphenol, p-octylphenol, p- Nonylphenol, p-cumylphenol, bisphenol A, bisphenol F, resorcinol, 2-hydroxybenzaldehyde, 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde or derivatives thereof may be mentioned.
  • these phenols can also be used individually or in combination of 2 or more types.
  • aldehydes used in the production of novolak type phenol resins include alkyl aldehydes such as formaldehyde, acetaldehyde, propyl aldehyde, and butyraldehyde, aromatic aldehydes such as benzaldehyde, 2-hydroxybenzaldehyde, 3-hydroxybenzaldehyde, 4- And aromatic aldehydes having a hydroxyl phenol such as hydroxybenzaldehyde.
  • the formaldehyde source include formalin (aqueous solution), paraformaldehyde, hemi-formal with alcohols, and trioxane. In addition, you may use these aldehydes individually or in combination of 2 or more types.
  • the reaction molar ratio of phenols to aldehydes is usually 0.3 to 1.7 mol of aldehydes with respect to 1 mol of phenols, preferably 0.5 ⁇ 1.5 moles.
  • Examples of the acidic catalyst used for the production of the novolak type phenol resin include organic carboxylic acids such as oxalic acid and acetic acid, organic sulfonic acids such as benzenesulfonic acid, paratoluenesulfonic acid and methanesulfonic acid, and 1-hydroxyethylidene-1
  • organic phosphonic acids such as 1,1'-diphosphonic acid and 2-phosphonobutane-1,2,4-tricarboxylic acid
  • inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid.
  • the resol type phenol resin can be obtained, for example, by reacting phenols and aldehydes in the presence of a catalyst such as an alkali metal, an amine, or a divalent metal salt.
  • a catalyst such as an alkali metal, an amine, or a divalent metal salt.
  • phenols used for the production of the resol type phenol resin include cresols such as phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, and 2,5-xylenol.
  • Xylenols such as 2,6-xylenol, 3,4-xylenol and 3,5-xylenol, ethylphenols such as o-ethylphenol, m-ethylphenol and p-ethylphenol, isopropylphenol, butylphenol, p- Butylphenols such as tert-butylphenol, p-tert-amylphenol, p-octylphenol, p-nonylphenol, alkylphenols such as p-cumylphenol, fluorophenol, chlorophenol, bromophenol, iodo Halogenated phenols such as enol, monovalent phenol substitutes such as p-phenylphenol, aminophenol, nitrophenol, dinitrophenol and trinitrophenol, and monovalent phenols such as 1-naphthol and 2-naphthol, Resorcin, alkylresorcin, pyr
  • aldehydes used in the production of resol type phenol resins include formaldehyde, paraformaldehyde, trioxane, acetaldehyde, propionaldehyde, polyoxymethylene, chloral, hexamethylenetetramine, furfural, glyoxal, n-butyraldehyde, capro
  • These aldehydes may be used alone or in combination of two or more.
  • formaldehyde and paraformaldehyde are preferably selected and used from the viewpoint of excellent reactivity and low cost.
  • Examples of the catalyst used in the production of the resol type phenolic resin include alkali metal hydroxides such as sodium hydroxide, lithium hydroxide and potassium hydroxide, alkaline earth metal oxides such as calcium, magnesium and barium, and the like. Examples thereof include hydroxides, sodium carbonate, aqueous ammonia, amines such as triethylamine and hexamethylenetetramine, and divalent metal salts such as magnesium acetate and zinc acetate. These catalysts may be used alone or in combination of two or more.
  • the reaction molar ratio of phenols to aldehydes is preferably 0.80 to 2.50 moles of aldehydes per mole of phenols, more preferably Aldehydes are 1.00 to 2.30 mol.
  • An arylalkylene type phenol resin refers to a phenol resin having one or more arylalkylene groups in a repeating unit.
  • Examples of such aryl alkylene type phenol resins include xylylene type phenol resins and biphenyl dimethylene type phenol resins.
  • Such an arylalkylene type phenol resin can be produced according to a known method, and the above-described phenols may be used as a raw material.
  • the metal hybrid resin of this embodiment has a feature that metal atoms constituting metal particles described later are coordinated to oxygen atoms in the phenol resin.
  • the coordinated oxygen atom is not limited to the phenolic hydroxyl group provided in the phenol resin, and may be an oxygen atom derived from a functional group other than this, and thus oxygen atoms derived from various functional groups and By causing the metal particles to interact, the adhesion between the metal particles and the phenol resin can be further increased.
  • the phenol resin includes a phenol resin having an aliphatic alcohol group in the molecule, a phenol resin having an ether group in the molecule, a phenol resin having a ketone group in the molecule, and a phenol having an aldehyde group in the molecule. It is preferable to use a resin, a phenol resin having a carboxyl group in the molecule, a phenol resin having an ester group in the molecule, and a phenol resin having a urethane group in the molecule.
  • a phenol resin having a carbonyl moiety such as a ketone group, an aldehyde group, a carboxyl group, an ester group, or a urethane group in the molecule.
  • carbonyl group such as a ketone group, an aldehyde group, a carboxyl group, an ester group, or a urethane group
  • the metal hybrid resin in the present embodiment is a mixture of a metal salt solution and a phenol resin, and coordinates a metal atom to an oxygen atom in the phenol resin.
  • the aldehyde group brings about a reducing action on the metal cation constituting the metal salt.
  • the metal atom can be easily coordinated to the oxygen atom in the phenol resin.
  • Such a phenol resin having an aldehyde group in the molecule is, for example, a phenol used for producing the phenol resin, for example, hydroxybenzaldehyde such as 2-hydroxybenzaldehyde, 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde, A derivative thereof may be used.
  • a desired phenol resin can be produced by performing a conversion reaction on this phenol according to a known production method of a phenol resin.
  • the number average molecular weight (Mn) of the phenol resin of the present embodiment can be appropriately set according to the application to which the metal hybrid resin is applied, but is, for example, 150 or more, preferably 200 or more, more preferably 250. That's it. Moreover, the number average molecular weight (Mn) of the phenol resin of this embodiment is 1500 or less, for example, Preferably it is 1200 or less, More preferably, it is 1000 or less. By setting to such a range, moderate flexibility as a resin component can be imparted.
  • the weight average molecular weight (Mw) of the phenol resin of this embodiment can be suitably set according to the use which applies a metal hybrid resin, it is 200 or more, for example, Preferably it is 300 or more, More preferably, it is 400. That's it. Moreover, the weight average molecular weight (Mw) of the phenol resin of this embodiment is 2500 or less, for example, Preferably it is 2000 or less, More preferably, it is 1800 or less. By setting to such a range, moderate flexibility as a resin component can be imparted.
  • the ratio (Mw / Mn) of the weight average molecular weight to the number average molecular weight of the phenol resin of the present embodiment can be appropriately set according to the use, for example, 2.5 or less as an upper limit value, Preferably it is 2.2 or less, More preferably, it is 2.0 or less. By setting in this way, it becomes easy to express the properties unique to the metal hybrid resin.
  • the lower limit of the ratio (Mw / Mn) of the weight average molecular weight to the number average molecular weight of the phenol resin of the present embodiment is not particularly limited, but is, for example, 1.05 or more.
  • the phenol resin used as the raw material and the phenol resin contained as the metal hybrid resin may not have the same molecular weight. is there.
  • the molecular weight of the phenol resin used as a raw material should be set so that the phenol resin contained in the metal hybrid resin falls within the above molecular weight range in consideration of the manufacturing conditions. Is a preferred embodiment.
  • the phenol resin of the present embodiment is preferably contained in an amount of 10% by mass or more, more preferably 15% by mass or more, and further preferably 20% by mass or more based on the entire metal hybrid resin. Thereby, moderate flexibility as a composite material can be imparted and workability can be improved. Moreover, it is preferable that the phenol resin of this embodiment contains 99 mass% or less with respect to the whole metal hybrid resin, It is more preferable to contain 95 mass% or less, It is further more preferable to contain 90 mass% or less. By doing in this way, the degree of expression of mechanical strength derived from metal particles can be raised.
  • the metal hybrid resin of this embodiment includes metal particles composed of metal atoms coordinated to oxygen atoms in the phenol resin. That is, since the metal atoms constituting the metal particles are coordinated to the oxygen atoms in the phenol resin, the adhesion between the metal particles and the phenol resin is further increased as compared with the composite materials that existed in the past. be able to.
  • Coordinated to an oxygen atom specifically means that an oxygen atom (referred to herein as “O”) and a metal atom (referred to herein as “M”) are OM bonds. Refers to being chemically linked. More specifically, in the X-ray photoelectron spectroscopy (ESCA (Electron Spectroscopy for Chemical Analysis)), the above-mentioned OM bond is observed when a composite material of metal particles and a resin is analyzed. .
  • ESA Electrodectron spectroscopy for Chemical Analysis
  • the metal atom which comprises the metal particle contained in the metal hybrid resin of this embodiment can be suitably selected according to the use to which this metal hybrid resin is applied. More specifically, silver (Ag), copper (Cu), zinc (Zn), calcium (Ca), iron (Fe), aluminum (Al), magnesium (Mg), titanium (Ti), scandium (Sc) , Vanadium (V), chromium (Cr), manganese (Mn), cobalt (Co), nickel (Ni), gallium (Ga), strontium (Sr), yttrium (Y), niobium (Nb), molybdenum (Mo) , Ruthenium (Ru), palladium (Pd), cadmium (Cd), barium (Ba), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm) Europium (Eu), gadolinium (Gd), terb
  • the metal atoms are silver (Ag), copper (Cu), zinc (Zn), calcium (Ca), iron (Fe) due to the ease of manufacturing the metal hybrid resin and the wide range of application fields. ), Aluminum (Al), magnesium (Mg), and preferably one or more metal atoms.
  • the metal particles contained in the metal hybrid resin of the present embodiment are usually mostly “zero-valent” metal atoms, but some metal ions having a cationic property may be mixed.
  • the mechanical strength can be improved as the interaction between the metal ions and the phenolic resin may be combined.
  • the lower limit value of the average particle diameter of the metal particles according to the present embodiment can be appropriately set according to the application to be used, but is, for example, 1 nm or more, preferably 3 nm or more, more preferably 5 nm or more. . By setting in this way, it becomes easy to express desired mechanical strength.
  • the upper limit value of the average particle diameter of the metal particles according to the present embodiment can be appropriately set according to the application to be used, but is, for example, 1 ⁇ m or less, preferably 600 nm or less, more preferably 300 nm or less. More preferably, it is 150 nm or less, still more preferably 100 nm or less, particularly preferably 50 nm or less.
  • the particle size of the metal particles in the metal hybrid resin can be determined by observing with a transmission electron microscope (TEM), for example. More specifically, the surface of the metal hybrid resin is observed with a transmission electron microscope (TEM), the particle size of 100 arbitrarily selected metal particles is measured, and the average particle size of the metal particles is obtained as the average value. It can be.
  • TEM transmission electron microscope
  • the metal particles of the present embodiment are preferably contained in an amount of 1% by mass or more, more preferably 3% by mass or more, and further preferably 5% by mass or more based on the entire metal hybrid resin. Thereby, the performance specific to the metal particles can be expressed. Moreover, it is preferable that the metal particle of this embodiment contains 85 mass% or less with respect to the whole metal hybrid resin, It is more preferable to contain 75 mass% or less, It is further more preferable to contain 65 mass% or less. By doing in this way, the specific gravity as the whole metal hybrid resin can be suppressed, and the range of application can be expanded.
  • the metal hybrid resin according to the present embodiment can be blended with a known resin material for the purpose of modifying the characteristics of the resin in addition to the above-described phenol resin.
  • various additives used in ordinary metal resin composite materials for example, release agents such as stearic acid, calcium stearate or polyethylene, flame retardants such as calcium hydroxide, and colorants such as carbon black A coupling agent, a solvent, or the like may be blended.
  • the specific gravity of the metal hybrid resin according to the present embodiment can be set as appropriate depending on the intended use.
  • the lower limit of the specific gravity is, for example, 1.25 g / cm 3 or more, and preferably 1.27 g / cm 3. Or more, and more preferably 1.30 g / cm 3 or more.
  • the specific gravity of the metal hybrid resin according to the present embodiment can be appropriately set depending on the application to be used, the upper limit of this specific gravity, for example 16.6 g / cm 3 or less, preferably 16.0 g / cm 3 or less More preferably, it is 15.5 g / cm 3 or less.
  • the manufacturing method of the metal hybrid resin of this embodiment includes the following steps. (A) (A) Step of preparing phenol resin (b) Step of preparing (B ′) metal salt solution (c) Mixing (A) phenol resin and (B ′) metal salt solution, Step of obtaining metal hybrid resin by coordinating metal atom to oxygen atom in (A) phenol resin Each step will be described below.
  • a solution of (B ′) metal salt is prepared.
  • the solution of (B ′) metal salt is formed on the metal atoms constituting “(B) metal particles composed of metal atoms coordinated to oxygen atoms in the phenol resin” described above. It can be prepared using the corresponding salt.
  • silver (Ag), copper (Cu), zinc (Zn), calcium (Ca), iron (Fe), aluminum from the ease of production of metal hybrid resins and the wide range of application fields. It is preferable to use a metal salt corresponding to one or more metal atoms selected from the group consisting of Al) and magnesium (Mg).
  • a metal salt is comprised by the cation (cation) and anion (anion) of said metal atom.
  • anions include halogen ions such as chlorine ion, bromine ion and iodine ion; carboxylate ions such as acetate ion, oxalate ion and fumarate ion; p-toluenesulfonate ion, methanesulfonate ion, butanesulfonate ion, Examples thereof include sulfonate ions such as benzenesulfonate ion; sulfate ion; perchlorate ion; carbonate ion; nitrate ion.
  • the metal particles constituting the metal hybrid resin of the present embodiment are silver, that is, silver particles will be described as an example.
  • a salt is prepared by combining silver ions with the above anions, and a solution is prepared therefrom.
  • nitrate ion it is preferable to use nitrate ion as an anion and to use silver nitrate as a metal salt because of its high solubility in a solvent.
  • an appropriate metal salt may be selected in consideration of the solubility of the metal salt as appropriate.
  • copper copper sulfate, copper nitrate, etc.
  • zinc zinc as a metal atom
  • zinc chloride, zinc sulfate, zinc nitrate when using calcium as a metal atom, calcium chloride, calcium nitrate, iron are used.
  • metal chloride, iron sulfate, iron nitrate when used as a metal atom, aluminum is used as a metal atom, aluminum nitrate can be used, and when magnesium is used as a metal atom, magnesium chloride, magnesium sulfate, magnesium nitrate, or the like can be used.
  • the metal valence of the metal salt may be appropriately selected in consideration of solubility in a solvent, ease of reduction, and the like.
  • a metal salt solution is prepared, and a solvent for dissolving the metal salt may be appropriately selected according to the characteristics of the metal salt.
  • a solvent for dissolving the metal salt may be appropriately selected according to the characteristics of the metal salt.
  • water can be selected as the solvent.
  • organic solvents other than water can be employed as the solvent, for example, alcohol solvents such as methanol, ethanol, propanol, butanol, pentanol, hexanol, and ethylene glycol; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone Solvents: ether solvents such as dimethyl ether, diethyl ether, methyl ethyl ether, dipropyl ether, tetrahydrofuran, etc., cellosolves such as methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate; N-methyl-2-pyrrolidone And amide solvents such as N, N-dimethylformamide; dimethyl carbonate and the like can be used.
  • alcohol solvents such as methanol, ethanol, propanol, butanol
  • organic solvents may be used alone or in combination. Moreover, when these organic solvents are miscible with water, they can be used by appropriately mixing with water. Moreover, the solution of the metal salt of this embodiment can also adjust the pH of a solution for the purpose of improving the solubility of a metal salt.
  • the concentration of the metal salt in the metal salt solution of the present embodiment is, for example, 1% or more, preferably 3% or more, and more preferably 5% or more.
  • the concentration of the metal salt in the metal salt solution is, for example, 20% or less, preferably 15% or less, and more preferably 12% or less. By setting to such a range, it is possible to stably convert from a metal salt to desired metal particles.
  • the concentration of the metal salt is defined as a ratio of the mass of the dissolved metal salt to the mass of the entire solution.
  • Step (c) In this step, a phenol resin and a metal salt solution are mixed, and metal atoms are coordinated to oxygen atoms in the phenol resin to obtain a metal hybrid resin. Specifically, the above-described phenol resin and a metal salt solution are mixed, and a reduction reaction is performed on the metal salt to form metal particles from the metal salt (that is, “zero-valent” metal Precipitate as particles) to obtain a metal hybrid resin.
  • a reduction reaction is performed on the above-described metal salt.
  • This reduction reaction can be performed using a known reducing agent, or can be performed utilizing a reducing functional group resulting from the structure of the phenol resin.
  • a phenol resin having an aldehyde group in the molecule can be employed as the phenol resin.
  • the aldehyde group in the molecule brings about a reducing action on the metal cation constituting the metal salt and can be converted into metal particles.
  • a phenol resin having an aldehyde group in the molecule for example, 0.1 times or more of the phenol resin can be used, preferably 0.5 times the mass of the metal salt contained in the solution.
  • An amount of phenol resin can be used, and more preferably twice as much phenol resin can be used.
  • the upper limit of the amount of phenol resin to be used is not specifically limited, For example, it is 100 times or less.
  • the reducing agent other than the phenol resin having an aldehyde group in the molecule known ones can be employed, for example, sodium hypophosphite, dimethylamine borane, sodium borohydride, potassium borohydride, An inorganic or organic reducing agent such as formaldehyde, hydrazine, or ascorbic acid can be used.
  • the amount of the reducing agent used can be set as appropriate depending on the type of the reducing agent, and it is sufficient to set an amount sufficient to deposit a sufficient amount of metal particles.
  • a reducing adjuvant in order to accelerate
  • amine compounds and alcohols can also be used as reducing aids. More specifically, ammonia, ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, tripropylamine, isopropyldiethylamine, diethanolamine, triethanolamine, morpholine, ethylenediamine, pyridine, or the like is used as a reducing auxiliary agent as an amine compound. Can do. Moreover, as alcohols, ethoxyethanol, ethylene glycol, diethylene glycol, etc. can be used as a reduction aid.
  • this process can also be performed by heating after mixing various raw materials.
  • the lower limit of the temperature condition when performing this heating is, for example, 30 ° C. or higher, preferably 40 ° C. or higher, and more preferably 45 ° C. or higher.
  • the upper limit of temperature conditions is 100 degrees C or less, for example, Preferably it is 90 degrees C or less, More preferably, it is 80 degrees C or less.
  • the reaction time may be appropriately set while observing the degree of change of the mixed raw materials, but the lower limit of the reaction time is, for example, 10 minutes or more, preferably 30 minutes or more, more preferably 1 hour or more. is there. Moreover, the upper limit of reaction time is 24 hours or less, for example, Preferably it is 12 hours or less, More preferably, it is 8 hours or less.
  • the metal hybrid resin according to the present embodiment is expected to be used in a wide range of applications because the metal particles are uniformly dispersed in the resin and can exhibit high mechanical strength.
  • it is expected that it can be used as a conductive material by paying attention to the conductivity, and can also be used as a heat dissipation material, paying attention to thermal conductivity.
  • application as an electronic member in ceramic capacitors, power inductors, etc. application as automotive parts such as tire bead parts, application as friction materials and abrasives, bond magnets, building materials, structural materials, Expected to be used as sports equipment and soundproofing materials.
  • the number average molecular weight (Mn), the weight average molecular weight (Mw), and the ratio of the weight average molecular weight to the number average molecular weight (Mw / Mn) are as follows.
  • the number average molecular weight and the weight average molecular weight are measured by GPC (Gel Permeation Chromatography) using TSK-GEL G1000H, G2000H, G3000H as column types and tetrahydrofuran as a mobile phase. went.
  • monodisperse polystyrene was used as a standard substance.
  • the same operation is repeated to sequentially obtain the phenol resin 1, and a metal resin composite material is produced using this.
  • Example 1 A four-neck 1 L flask equipped with a stirring blade, a thermometer, a dropping funnel, and a condenser was prepared. In this flask, 30.0 g of the phenol resin 1 obtained above and sodium hydroxide 4 with respect to 300 g of water. An aqueous solution of sodium hydroxide in which 0.6 g (0.11 mol) was dissolved, 6.0 g (0.05 mol) of thiodiethanol, and 31.6 g (0.03 mol) of 1N silver nitrate were charged. After stirring and dissolving them uniformly, the temperature was raised until the internal temperature reached 50 ° C., and the reaction was carried out for 2 hours while maintaining the temperature from the time when the internal temperature reached 50 ° C.
  • the obtained solid was dried, and the molecular weight of the portion soluble in tetrahydrofuran was measured by GPC.
  • the number average molecular weight (Mn), the weight average molecular weight (Mw), and the ratio of the weight average molecular weight to the number average molecular weight (Mw / Mn) are as follows.
  • the metal resin composite material obtained in Example 1 was measured with an X-ray photoelectron spectrometer Escalab-220iXL manufactured by Thermo Fisher Scientific Co., Ltd.
  • the measurement conditions are as follows. ⁇ Irradiated X-ray: Monochrome AlK ⁇ ⁇ Detection depth: about 5nm ⁇ X-ray spot diameter: about 1mm
  • FIG. 2 shows a chart of an Ag3d narrow scan spectrum measured for a sample obtained by cleaning an Ag foil with Ar ions.
  • the peak position of the Ag3d narrow scan spectrum is 368.9 eV
  • the peak position is 368.3 eV. Differences were observed.
  • the peak of Ag alone is observed around 368.1 to 368.3 eV, whereas in a compound in which an Ag atom and an O atom interact, such as silver acetate, this peak is 368.3 to Shift to 368.9 eV (Source: Handbook of X-ray Photoelectron Spectroscopy (Physical Electronics)). This confirms that the metal resin composite material obtained in Example 1 has an Ag—O bond in its chemical structure.
  • the surface of the composite material obtained in Example 1 was observed with a transmission electron microscope (TEM). The result is shown in FIG. As shown in FIG. 3, the metal resin composite material obtained in Example 1 uniformly contained silver particles on the order of several tens of nm (average particle diameter: 13 nm).
  • Example 2 A four-neck 1 L flask equipped with a stirring blade, a thermometer, a dropping funnel, and a condenser was prepared. In this flask, 30.0 g of the phenol resin 1 obtained above was hydroxylated with respect to 300.0 g of water. An aqueous sodium hydroxide solution in which 4.6 g (0.11 mol) of sodium was dissolved, 6.0 g (0.05 mol) of thiodiethanol, and 15.8 g (0.015 mol) of 1N silver nitrate were charged. After stirring and dissolving them uniformly, the temperature was raised until the internal temperature reached 50 ° C., and the reaction was carried out for 2 hours while maintaining the temperature from the time when the internal temperature reached 50 ° C.
  • Example 3 A four-neck 1 L flask equipped with a stirring blade, a thermometer, a dropping funnel, and a condenser was prepared. In this flask, 30.0 g of the phenol resin 1 obtained above and sodium hydroxide 4 with respect to 300 g of water. An aqueous solution of sodium hydroxide in which 0.6 g (0.11 mol) was dissolved, 6.0 g (0.05 mol) of thiodiethanol, and 31.6 g (0.03 mol) of 1N silver nitrate were charged. After stirring and dissolving them uniformly, the temperature was raised until the internal temperature reached 30 ° C., and the reaction was carried out for 24 hours while maintaining the temperature from the time when the internal temperature reached 30 ° C.
  • the metal resin composite materials obtained in Examples 1 to 3 and Comparative Examples 1 and 2 were evaluated based on the following.
  • the specific gravity of the metal resin composite material of each example and the metal resin composite material of each comparative example does not differ greatly, it can be said that the content of silver particles in the composite material is almost the same level.
  • the bending strengths of the examples and the comparative examples are compared, a remarkable difference is observed in these strengths.
  • the metal-resin composite material (metal hybrid resin) of the present invention has a metal and a resin bonded through a chemical bond, so that it exhibits appropriate adhesion and can thus achieve high mechanical strength. It is to support.
  • the metal hybrid resin according to the present invention is expected to be used in a wide range of applications because the metal particles are uniformly dispersed in the resin and can exhibit high mechanical strength. In addition, it is expected that it can be used as a conductive material by paying attention to the conductivity, and can also be used as a heat dissipation material, paying attention to thermal conductivity.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Phenolic Resins Or Amino Resins (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Résine hybride métallique contenant : (A) une résine phénolique; et (B) des particules métalliques conçues à partir d'atomes métalliques coordonnés à des atomes d'oxygène de la résine phénolique.
PCT/JP2016/054660 2015-02-27 2016-02-18 Résine hybride métallique et son procédé de production WO2016136571A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5440898A (en) * 1977-09-06 1979-03-31 Mead Corp Preparation of novel metallimproved novolak resin* and application to pressureesensitive paper
JP2006193640A (ja) * 2005-01-14 2006-07-27 Showa Highpolymer Co Ltd フェノール樹脂組成物及びそれを用いた高耐水性フェノール樹脂硬化物
JP2014523468A (ja) * 2011-06-30 2014-09-11 コーネル ユニバーシティ ハイブリッド材料及びナノコンポジット材料、これらを作製する方法、並びにこれらの使用
WO2016009754A1 (fr) * 2014-07-14 2016-01-21 住友ベークライト株式会社 Procédé de fabrication d'une résine électroconductrice, pâte électroconductrice, et élément électronique

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5440898A (en) * 1977-09-06 1979-03-31 Mead Corp Preparation of novel metallimproved novolak resin* and application to pressureesensitive paper
JP2006193640A (ja) * 2005-01-14 2006-07-27 Showa Highpolymer Co Ltd フェノール樹脂組成物及びそれを用いた高耐水性フェノール樹脂硬化物
JP2014523468A (ja) * 2011-06-30 2014-09-11 コーネル ユニバーシティ ハイブリッド材料及びナノコンポジット材料、これらを作製する方法、並びにこれらの使用
WO2016009754A1 (fr) * 2014-07-14 2016-01-21 住友ベークライト株式会社 Procédé de fabrication d'une résine électroconductrice, pâte électroconductrice, et élément électronique

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
ZHI, L. ET AL.: "Preparation of phenolic resin/silver nanocomposites via in situ reduction", SCRIPTA MATERIALIA, vol. 47, 2002, pages 875 - 879, ISSN: 1359-6462 *

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TW201704331A (zh) 2017-02-01
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