TW201704331A - Metal hybrid resin and manufacturing method thereof - Google Patents

Abstract

A metal hybrid resin containing: (A) a phenol resin; and (B) metal particles configured from metal atoms coordinated to oxygen atoms of the phenol resin.

Description

Metal mixed resin and method of producing the same

The present invention relates to a metal mixed resin and a method of producing the same.

Conventionally, it has been attempted to impart a characteristic property of metal particles to a resin material by blending metal particles with a resin material. The properties peculiar to the metal particles include, for example, conductivity or mechanical strength.

As a technique related to this, a technique disclosed in Patent Document 1 or Patent Document 2 is known.

Patent Document 1 discloses a technique of preparing an ink for forming an adhesive layer comprising conductive particles having a primary particle diameter of 1 to 300 nm, a curable resin, a dispersing agent, and a solvent, and printing the same on a substrate and hardening it. Thereby, an adhesive layer in the composite layer is formed. According to this technique, it is considered that the adhesion between the substrate and the wiring layer can be improved, and the connection resistance can be lowered.

Further, Patent Document 2 discloses a composition set including a conductor layer forming composition and a conductive adhesive composition, wherein the conductor layer forming composition contains "containing a dispersion medium and a metal oxide". Inorganic particles; the conductive adhesive composition comprising a binder material and conductive particles having a number average particle diameter of 1 nm to 3000 nm; The electrical adhesive composition can exhibit high adhesion of a substrate having conductivity on the surface and a conductor layer formed of a dispersion containing metal particles, and ensure conduction between the conductor layer and the substrate.

Patent Document 1: Japanese Laid-Open Patent Publication No. 2013-175559

Patent Document 2: International Publication No. 2013/018777

However, the inventors of the present invention conducted research and found that the following problems exist.

In the technique described in Patent Document 1 or Patent Document 2, the metal particles and the resin material are blended, but the properties of the metal particles as the inorganic material and the resin material as the organic material are different from each other. On the other hand, there is a problem in the dispersion of metal particles.

Here, when the dispersibility is insufficient, for example, when a mechanical force is applied from the outside to the composite material of the metal particles and the resin material, cracks are generated from the interface between the metal particles and the resin material.

The present invention has been made in view of the above problems, and provides a metal resin composite material which can uniformly disperse metal particles in a resin and exhibit high mechanical strength.

According to the present invention, there is provided a metal mixed resin comprising the following components: (A) a phenol resin; and (B) a metal particle composed of a metal atom coordinated to an oxygen atom in the above phenol resin.

Further, according to the present invention, there is provided a method for producing a metal mixed resin comprising the steps of: (a) preparing (A) a phenol resin; (b) a step of preparing a solution of the (B') metal salt; and (c) mixing a solution of the above (A) phenol resin and the above (B') metal salt to cause a metal atom and the oxygen in the (A) phenol resin The atom is coordinated to obtain a metal mixed resin step.

The present invention is characterized in that it contains a phenol resin and a composite material with metal particles, and the metal atoms constituting the metal particles are coordinated to the oxygen atoms in the phenol resin.

Thereby, the metal particles and the resin can be bonded via a chemical bond, and the metal particles can be uniformly dispersed in the resin, and the mechanical strength can be exhibited.

In addition, the name "metal hybrid resin" is a name given to the present inventors, and refers to a novel metal resin composite material in which a metal particle and a resin material are bonded via a coordinate bond as described above. .

The above and other objects, features and advantages of the present invention will become more apparent from

Fig. 1 is a graph showing the Ag3d narrow scan spectrum obtained by measuring the metal-resin composite obtained in Example 1.

Fig. 2 is a view showing a narrow scan pattern of Ag3d obtained by measuring a sample in which Ag foil was washed with Ar ions.

Fig. 3 is a photographic view showing the results obtained by observing the surface by a transmission electron microscope (TEM) with respect to the metal-resin composite material obtained in Example 1.

Hereinafter, the present invention will be described in detail based on the embodiments. In the present specification, "~" means from the above to the following unless otherwise specified.

[Metal Mixed Resin]

First, the metal mixed resin of the present embodiment will be described.

The metal mixed resin of the present embodiment contains the following components (A) and (B).

(A) phenolic resin

(B) a metal particle composed of a metal atom coordinated to an oxygen atom in a phenol resin

((A) phenol resin)

The phenol resin used in the metal-mixed resin of the present embodiment may be appropriately selected from known phenol resins for use or the like.

As the 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 a phenol with an aldehyde in an acidic catalyst.

Examples of the phenol used in the production of the novolac type phenol resin include phenol, cresol, xylenol, ethylphenol, p-phenylphenol, p-tert-butylphenol, and p-tert-pentylphenol. , p-octylphenol, p-nonylphenol, p-cumylphenol, bisphenol A, bisphenol F, resorcinol, 2-hydroxybenzaldehyde, 3-hydroxybenzaldehyde, 4- Hydroxybenzaldehyde or such derivatives and the like. In addition, these phenols may be used alone or in combination of two or more.

Further, examples of the aldehyde used for producing the novolac type phenol resin include alkyl aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, and butyraldehyde; aromatic aldehydes such as benzaldehyde; 2-hydroxybenzaldehyde and 3-hydroxyl groups; An aromatic aldehyde having a hydroxyphenol or the like such as benzaldehyde or 4-hydroxybenzaldehyde. As a source of formaldehyde, fumarin (aqueous solution), paraformaldehyde, hemiformal of alcohol, and three Alkane, etc. In addition, these aldehydes may be used alone or in combination of two or more.

In the synthesis of a novolak-type phenol resin, the molar ratio of the reaction between the phenol and the aldehyde is usually from 0.3 to 1.7 mol, preferably from 0.5 to 1.5 mol, based on 1 mol of the phenol.

Further, examples of the acidic catalyst for producing a novolac type phenol resin include organic carboxylic acids such as oxalic acid and acetic acid; organic sulfonic acids such as benzenesulfonic acid, p-toluenesulfonic acid and methanesulfonic acid; and 1-hydroxyethylidene An organic phosphonic acid such as keto-1,1'-diphosphonic acid or 2-phosphonobutane-1,2,4-tricarboxylic acid; an inorganic acid such as hydrochloric acid, sulfuric acid or phosphoric acid. In addition, these acidic catalysts may be used alone or in combination of two or more.

The resol type phenol resin can be obtained, for example, by reacting a phenol with an aldehyde in the presence of a catalyst such as an alkali metal or an amine or a divalent metal salt.

Examples of the phenol used for producing the resol type phenol resin include cresols such as phenol, o-cresol, m-cresol, and p-cresol; 2,3-xylenol and 2,4-dimethyl Dimethylphenols such as phenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol; o-ethylphenol, m-ethylphenol, Ethylphenols such as ethyl phenol; butyl phenols such as isopropyl phenol, butyl phenol, p-tert-butylphenol; p-tert-butylphenol, p-octylphenol, p-nonylphenol, p-isopropyl Alkanols such as phenylphenol; halogenated phenols such as fluorophenol, chlorophenol, bromophenol, iodophenol; monophenolic substitutions such as p-phenylphenol, aminophenol, nitrophenol, dinitrophenol, trinitrophenol Monophenols such as 1-naphthol and 2-naphthol; resorcinol, alkyl resorcinol, gallic phenol, catechol, alkyl catechol, hydroquinone, alkane Polyphenols such as hydroquinone, phloroglucin, bisphenol A, bisphenol F, bisphenol S, dihydroxynaphthalene, etc.; 2-hydroxybenzaldehyde, 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde, etc. Aldehyde-based phenols or derivatives thereof Things and so on. Furthermore, the phenols may also be used. It can be used individually or in mixture of 2 or more types.

Further, examples of the aldehyde used for producing the resol type phenol resin include formaldehyde, paraformaldehyde, and trisole. Alkane, acetaldehyde, propionaldehyde, polyoxymethylene, trichloroacetaldehyde, hexamethylenetetramine, furfural, glyoxal, n-butyraldehyde, hexanal, allyl aldehyde, benzaldehyde, crotonaldehyde, propylene Acrolein, tetraformaldehyde, phenylacetaldehyde, o-tolualdehyde, 2-hydroxybenzaldehyde, 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde, and the like. These aldehydes may be used alone or in combination of two or more. Further, among these aldehydes, formaldehyde and paraformaldehyde are preferably used from the viewpoint of excellent reactivity and low cost.

Further, examples of the catalyst for producing the resol type phenol resin include hydroxides of alkali metals such as sodium hydroxide, lithium hydroxide, and potassium hydroxide; and oxides of alkaline earth metals such as calcium, magnesium, and barium. And hydroxide; amines such as sodium carbonate, ammonia, triethylamine, hexamethylenetetramine; divalent metal salts such as magnesium acetate or zinc acetate. These catalysts may be used alone or in combination of two or more.

Further, when the resol type phenol resin is produced, the molar ratio of the reaction between the phenol and the aldehyde is preferably from 0.80 to 2.50 moles, more preferably from the phenol, to the aldehyde. It is 1.00~2.30 Mo.

The arylalkylene type phenol resin is a phenol resin having one or more arylalkylene groups in a repeating unit. Examples of such an arylalkylene-type phenol resin include a xylyl phenol resin and a biphenyl dimethylene phenol resin.

The method for producing such an arylalkylene type phenol resin can be carried out according to a known method, and a phenol such as the above can be used as a raw material.

The metal mixed resin of the present embodiment is characterized in that it constitutes a metal to be described later. The metal atom of the particle coordinates with the oxygen atom in the phenol resin. Here, the oxygen atom to be coordinated is not limited to the phenolic hydroxyl group of the phenol resin, and may be an oxygen atom derived from a functional group other than the above, and the oxygen atom and the metal particle derived from various functional groups are generated as described above. The interaction can thereby improve the adhesion of the metal particles to the phenol resin.

More specifically, it is preferred to use 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, a phenol resin having an aldehyde group in the molecule, and having intramolecular A phenol resin having a carboxyl group, a phenol resin having an ester group in the molecule, and a phenol resin having an urethane group in the molecule are used as the phenol resin.

Among these, a phenol resin having a carbonyl moiety (carbonyl group) such as a ketone group or an aldehyde group, a carboxyl group, an ester group or an amine ester group in the molecule is preferably used.

By carrying out in the above manner, the metal atom may not only coordinate with the oxygen atom of the phenolic hydroxyl group in the phenol resin, but may also partially coordinate with the oxygen atom of the carbonyl group. Thereby, the adhesion between the metal atom and the phenol resin can be further improved.

In the case of producing a phenol resin having a carbonyl group in the molecule, the phenols listed above may be used as a raw material by using a functional group having a corresponding molecule in the molecule.

Further, in the case of using a phenol resin having an aldehyde group in the molecule, there is also an advantage that "it becomes easy to produce a metal mixed resin".

That is, as described below, in the metal mixed resin of the present embodiment, the solution of the metal salt is mixed with the phenol resin, and the metal atom is coordinated with the oxygen atom in the phenol resin, but the aldehyde group is used in the molecule. In the case where the phenol resin is used as a raw material of the metal mixed resin, the aldehyde group brings a reduction action to the metal cation constituting the metal salt. Further, by adopting this condition, there is an advantage in that it is easy to coordinate the metal atom with the oxygen atom in the phenol resin.

The phenol resin having an aldehyde group in such a molecule, for example, as a phenol used in the production of a phenol resin, for example, hydroxybenzaldehyde such as 2-hydroxybenzaldehyde, 3-hydroxybenzaldehyde or 4-hydroxybenzaldehyde or Its derivatives can be.

The phenol resin can be produced by a conversion reaction of the 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 depending on the application of the metal mixed resin, and is, for example, 150 or more, preferably 200 or more, and more preferably 250 or more.

Further, the number average molecular weight (Mn) of the phenol resin of the present embodiment is, for example, 1,500 or less, preferably 1200 or less, more preferably 1,000 or less.

By setting it as the said range, it can provide moderate flexibility as a resin component.

The weight average molecular weight (Mw) of the phenol resin of the present embodiment can be appropriately set depending on the application of the metal mixed resin, and is, for example, 200 or more, preferably 300 or more, and more preferably 400 or more.

Further, the weight average molecular weight (Mw) of the phenol resin of the present embodiment is, for example, 2,500 or less, preferably 2,000 or less, more preferably 1,800 or less.

By setting it as the said range, it can provide moderate flexibility as a resin component.

Further, 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 depending on the use, and for example, the upper limit is 2.5 or less, preferably 2.2 or less, more preferably It is 2.0 or less. By setting in the above manner, it becomes easy to express the properties inherent to the metal mixed resin.

Further, the weight average molecular weight of the phenol resin of the present embodiment is relative to the number average molecular weight The lower limit of the ratio (Mw/Mn) is not particularly limited, and is, for example, 1.05 or more.

Further, in the present embodiment, in the stage of producing the metal mixed resin, the phenol resin used as the raw material and the phenol resin contained in the metal mixed resin may not necessarily have the same molecular weight and the like due to the chemical reaction.

In other words, in the case of producing a metal mixed resin, it is preferable to set the molecular weight of the phenol resin to be a raw material in such a manner that the phenol resin contained in the metal mixed resin is in the above molecular weight range in consideration of the production conditions.

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 still more preferably 20% by mass or more based on the total amount of the metal mixed resin. Thereby, it is possible to provide an appropriate degree of flexibility or improvement in workability as a composite material.

In addition, the phenol resin of the present embodiment is preferably contained in an amount of 99% by mass or less, more preferably 95% by mass or less, and still more preferably 90% by mass or less based on the total amount of the metal mixed resin. Thereby, the degree of expression of the mechanical strength derived from the metal particles can be improved.

((B) a metal particle composed of a metal atom coordinated to an oxygen atom in a phenol resin)

The metal mixed resin of the present embodiment contains metal particles "consisting of a metal atom coordinated to an oxygen atom in a phenol resin". That is, since the metal atom constituting the metal particle is coordinated to the oxygen atom in the phenol resin, the adhesion between the metal particle and the phenol resin can be increased more than the conventional composite material.

Here, "coordination with an oxygen atom" means, more specifically, an oxygen atom (herein referred to as "O") and a metal atom (herein referred to as "M") chemically linked to an O-M bond.

More specifically, it refers to the following situation: X-ray photoelectron spectroscopy (ESCA (EIectron) In the Spectroscopy for Chemical Analysis)), when the composite material of the metal particles and the resin was analyzed, the above O-M bond was observed.

The metal atom constituting the metal particles contained in the metal mixed resin of the present embodiment can be appropriately selected depending on the use of the metal mixed resin.

More specifically, it may be selected from the group consisting of silver (Ag), copper (Cu), zinc (Zn), calcium (Ca), iron (Fe), aluminum (Al), magnesium (Mg), titanium (Ti), and antimony. (Sc), vanadium (V), chromium (Cr), manganese (Mn), cobalt (Co), nickel (Ni), gallium (Ga), antimony (Sr), antimony (Y), antimony (Nb), molybdenum (Mo), ruthenium (Ru), palladium (Pd), cadmium (Cd), barium (Ba), lanthanum (La), cerium (Ce), cerium (Pr), yttrium (Nd), yttrium (Pm), yttrium (Sm), 铕 (Eu), 釓 (Gd), 鋱 (Tb), 镝 (Dy), 鈥 (Ho), 铒 (Er), 銩 (Tm), 镱 (Yb), 鑥 (Lu), 铪One or more of the group consisting of (Hf), tantalum (Ta), tungsten (W), yttrium (Re), yttrium (Os), yttrium (Ir), platinum (Pt), and gold (Au) The metal atom.

In the above, in terms of ease of production of the metal mixed resin and wide range of applications, the metal atom is preferably selected from the group consisting of silver (Ag), copper (Cu), zinc (Zn), and calcium (Ca). One or more metal atoms of the group consisting of iron (Fe), aluminum (Al), and magnesium (Mg).

The metal particles contained in the metal mixed resin of the present embodiment are usually a "zero-valent" metal atom, but a cationic metal ion may be partially mixed. The interaction between the metal ion and the phenol resin also complements each other, and further improvement in mechanical strength can be achieved.

The lower limit of the average particle diameter of the metal particles of the present embodiment can be appropriately set, for example, 1 nm or more, preferably 3 nm or more, and more preferably 5 nm or more. By setting in the above manner, it becomes easy to express the required mechanical strength.

In addition, the upper limit of the average particle diameter of the metal particles of the present embodiment can be appropriately set, for example, 1 μm or less, preferably 600 nm or less, more preferably 300 nm or less, still more preferably 150 nm or less, and further preferably 150 nm or less. It is preferably 100 nm or less, and particularly preferably 50 nm or less. By setting in the above manner, the dispersibility to the phenol resin can be improved.

Further, the particle diameter of the metal particles in the metal mixed resin can be determined, for example, by observation using a transmission electron microscope (TEM).

More specifically, the surface of the metal mixed resin can be observed by a transmission electron microscope (TEM), and the particle diameter of arbitrarily selected 100 metal particles can be measured, and the average value is defined as the average particle diameter of the metal particles.

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 still more preferably 5% by mass or more based on the total amount of the metal mixed resin. Thereby, the inherent properties of the metal particles can be exhibited.

In addition, the metal particles of the present embodiment are preferably contained in an amount of 85% by mass or less, more preferably 75% by mass or less, and still more preferably 65% by mass or less based on the total amount of the metal mixed resin. Thereby, the specific gravity of the entire metal mixed resin can be suppressed, and the range of application can be expanded.

(other ingredients)

Further, in addition to the above-described phenol resin, the metal mixed resin of the present embodiment may be blended with a known resin material in order to improve the resin properties.

Further, various additives used in a usual metal resin composite material may be blended as needed, such as a release agent such as stearic acid, calcium stearate or polyethylene; a flame retardant such as calcium hydroxide; and coloring such as carbon black Agent; coupling agent; solvent, etc.

The specific gravity of the metal-mixed resin of the present embodiment can be appropriately set depending on the intended use, and the lower limit of the specific gravity is, for example, 1.25 g/cm ³ or more, preferably 1.27 g/cm ³ or more, and more preferably 1.30 g/ Cm ³ or more.

The specific gravity of the metal mixed resin of the present embodiment can be appropriately set depending on the intended use, and the upper limit of the specific gravity is, for example, 16.6 g/cm ³ or less, preferably 16.0 g/cm ³ or less, and more preferably 15.5 g/cm ^{3 .} the following.

[Manufacturing method of metal mixed resin]

Next, a method of producing the metal mixed resin of the present embodiment will be described.

The method for producing a metal mixed resin of the present embodiment includes the following steps.

(a) a step of preparing (A) a phenol resin; (b) a step of preparing a solution of the (B') metal salt; and (c) mixing a solution of the (A) phenol resin and the (B') metal salt, and allowing the metal The step of coordinating an atom with an oxygen atom in the (A) phenol resin to obtain a metal mixed resin.

The following steps are explained.

((a) step)

In this step, a phenol resin is prepared.

As the phenol resin used herein, the above phenol resin may be appropriately selected.

((b) steps)

In this step, a solution of the (B') metal salt is prepared.

Here, in the present embodiment, the solution of the (B') metal salt may be a metal atom corresponding to the "metal particles composed of metal atoms coordinated to the oxygen atoms in the (B) phenol resin". The salt is prepared.

More specifically, the preparation corresponds to "selected from silver (Ag), copper (Cu), zinc (Zn), calcium (Ca), iron (Fe), aluminum (Al), magnesium (Mg), titanium (Ti), strontium (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), ruthenium (Ba), 镧 (La), 铈 (Ce), 鐠 (Pr), 钕 (Nd), 鉕 (Pm), 钐 (Sm), 铕 (Eu), 釓 (Gd), 鋱 (Tb), 镝(Dy), 鈥 (Ho), 铒 (Er), 銩 (Tm), 镱 (Yb), 鑥 (Lu), 铪 (Hf), 钽 (Ta), tungsten (W), 铼 (Re), 锇The metal salt of one or two or more metal atoms of the group consisting of (Os), iridium (Ir), platinum (Pt), and gold (Au) may be used.

Among these, in terms of easiness of production of the metal mixed resin and wide range of applications, it is preferred to use "corresponding to" selected from the group consisting of silver (Ag), copper (Cu), zinc (Zn), and calcium (Ca). A metal salt of one or two or more metal atoms of a group consisting of iron (Fe), aluminum (Al), and magnesium (Mg).

In the present embodiment, the metal salt is composed of a cation and an anion of the above metal atom.

Examples of such an anion include a halide ion such as a chloride ion, a bromide ion, and an iodide ion; a carboxylate ion such as an acetate ion, an oxalate ion, or a fumarate ion; a p-toluenesulfonate ion and a methanesulfonate ion; , sulfonate ion such as butane sulfonate ion, besylate ion; sulfate ion; perchlorate ion; carbonate ion; nitrate ion.

In the case where the metal particles constituting the metal mixed resin of the present embodiment are silver, that is, silver particles, a salt obtained by combining silver ions with the above anions is prepared, and then a solution is prepared.

Further, in the case of using silver, it is preferred to use nitrate ions as an anion in terms of solubility in a solvent to prepare silver nitrate as a metal salt.

Of course, even in the case of using metals other than silver, it is only appropriate to consider The appropriate metal salt may be selected by the solubility of the metal salt or the like.

For example, copper or copper nitrate can be used in the case of using copper as a metal atom; zinc chloride or zinc sulfate or zinc nitrate can be used in the case of using zinc as a metal atom; in the case of using calcium as a metal atom Calcium chloride or calcium nitrate can be used; in the case of using iron as a metal atom, ferric chloride or iron sulfate, iron nitrate can be used; in the case of using aluminum as a metal atom, aluminum nitrate can be used; in the case of using magnesium as a metal atom In the case, magnesium chloride, magnesium sulfate, magnesium nitrate or the like can be used.

Further, the valence of the metal of the metal salt may be appropriately determined in consideration of solubility in a solvent, easiness of reduction, and the like.

In the present step, a solution of a metal salt is prepared, but a solvent for dissolving the metal salt may be appropriately selected depending on the characteristics of the metal salt.

For example, as a solvent, water can be selected. As described above, it becomes helpful to reduce the manufacturing cost by using water.

Further, as the solvent, an organic solvent other than water may be used. For example, an alcohol solvent such as methanol, ethanol, propanol, butanol, pentanol, hexanol or ethylene glycol; acetone, methyl ethyl ketone or methyl group; a ketone solvent such as isobutyl ketone; an ether solvent such as dimethyl ether, diethyl ether, methyl ethyl ether, dipropyl ether or tetrahydrofuran; methyl siatone, ethyl cyanidin, butyl Ceramide, vinyl acetate acesulfame, ethyl acesulfame acetate, etc.; phthalamide solvent such as N-methyl-2-pyrrolidone or N,N-dimethylformamide; Dimethyl carbonate and the like. These organic solvents may be used singly or in combination of several.

Further, when the organic solvent is mixed with water, it may be used by mixing with water as appropriate.

Further, the solution of the metal salt of the present embodiment can adjust the pH of the solution for the purpose of improving the solubility of the metal salt and the like.

The concentration of the metal salt in the solution of the metal salt of the present embodiment is, for example, 1% or more, preferably 3% or more, and more preferably 5% or more. Further, the concentration of the metal salt in the solution of the metal salt is, for example, 20% or less, preferably 15% or less, more preferably 12% or less.

By setting it within the above range, it is possible to stably convert from a metal salt to a desired metal particle.

Further, the concentration of the metal salt is defined as the ratio of the mass of the dissolved metal salt to the overall mass of the solution.

((c) step)

In this step, a solution of a phenol resin and a metal salt is mixed, and a metal atom is coordinated with an oxygen atom in the phenol resin to obtain a metal mixed resin.

Specifically, the phenol resin and the metal salt solution are mixed, and the metal salt is subjected to a reduction reaction, whereby metal particles are formed from the metal salt (that is, precipitated as "zero-valent" metal particles) to obtain a metal. Mixed resin.

When this step is carried out, the above metal salt is subjected to a reduction reaction.

The reduction reaction can be carried out by using a known reducing agent or by using a reducing functional group of a structure of a phenol resin.

That is, as described above, in the present embodiment, a phenol resin having an aldehyde group in a molecule can be used as the phenol resin.

In this case, the aldehyde group in the molecule imparts a reduction to the metal cation constituting the metal salt, and can be converted into a metal particle.

In the case of using a phenol resin having an aldehyde group in the molecule, relative to the solution For the quality of the metal salt to be contained, for example, 0.1 times or more of the phenol resin may be used, preferably 0.5 times the amount of the phenol resin, and more preferably 2 times the amount of the phenol resin.

Moreover, the upper limit of the amount of the phenol resin to be used is not particularly limited, and is, for example, 100 times or less.

Further, as a reducing agent other than the phenol resin having an aldehyde group in the molecule, a known one may be used, and for example, inorganic or sodium hypophosphite, dimethylamine borane, sodium borohydride, potassium borohydride, formaldehyde, hydrazine, ascorbic acid or the like may be used. Organic reducing agent.

The amount of the reducing agent to be used can be appropriately set depending on the type thereof, and it suffices to set only a sufficient amount of metal particles to be precipitated.

Further, in this step, in order to promote the reduction reaction, a reducing aid can be suitably used. For example, in the case of using silver nitrate as a metal salt and mixing a phenol resin having an aldehyde group in the molecule, dimethyl sulfide, diethyl sulfide, dipropyl sulfide, dibutyl sulfide, dipentane sulfide, Dihexyl sulfide, diphenyl sulfide, ethyl phenyl sulfide, thiodiethanol, thiodipropanol, thiodibutanol, 1-(2-hydroxyethylthio)-2-propanol 1-(2-hydroxyethylthio)-2-butanol, 1-(2-hydroxyethylthio)-3-butoxy-1-propanol or the like is used as a reducing aid.

Further, an amine compound or an alcohol may be used as a reducing aid in the same manner.

More specifically, ammonia, ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, tripropylamine, isopropyldiethylamine, which are amine compounds, can be used. Diethanolamine, triethanolamine, morphine, ethylenediamine, pyridine, etc. are used as reducing assistants.

Further, as the alcohol, ethoxyethanol, ethylene glycol, diethylene glycol or the like can be used as the reducing assistant.

Moreover, this step can also be carried out by mixing various raw materials and heating.

The lower limit of the temperature condition at which the heating is performed is, for example, 30 ° C or higher, preferably 40 ° C. Above, more preferably 45 ° C or more. Further, the upper limit of the temperature condition is, for example, 100 ° C or lower, preferably 90 ° C or lower, more preferably 80 ° C or lower.

The reaction time may be appropriately set as long as the degree of change of the mixed raw materials is observed, and the lower limit of the reaction time is, for example, 10 minutes or longer, preferably 30 minutes or longer, more preferably 1 hour or longer. Further, the upper limit of the reaction time is, for example, 24 hours or shorter, preferably 12 hours or shorter, more preferably 8 hours or shorter.

[use]

The metal-mixed resin of the present embodiment exhibits high mechanical strength because the metal particles can be uniformly dispersed in the resin, and thus it is expected to be widely used.

In view of the electrical conductivity of the metal-mixed resin of the present embodiment, it is expected that the metal-mixed resin of the present embodiment can be used as a conductive material, and the thermal conductivity of the metal-mixed resin of the present embodiment is focused on. The metal mixed resin can also be used as a heat dissipating material.

Specifically, the metal mixed resin of the present embodiment is expected to be used as an electronic component in a ceramic capacitor, a power inductor, or the like; as an application for an automobile part such as a bead portion of a tire; as a friction material or an abrasive material; As a combination of magnets, building materials, structural materials, sporting goods, sound insulation materials.

Although the embodiments of the present invention have been described above, these are examples of the present invention, and various configurations other than the above may be employed.

Example

Hereinafter, the present invention will be specifically described by way of examples, but the scope of the invention is not limited to the examples and the like.

[Manufacture of phenol resin 1]

First, a 1 L four-necked flask equipped with a stirring blade, a thermometer, a dropping funnel, and a condenser was prepared, and 24.4 g (0.20 mol) of 4-hydroxybenzaldehyde and 6.5 g (0.20 mol) of 92% paraformaldehyde were charged. 210.0 g of acetic acid of the solvent and 186.0 g of 2-ethoxyethanol were stirred and uniformly dissolved.

Thereafter, 73.4 g of 98% sulfuric acid was added to the dropping funnel, and the temperature was observed so as not to rise to 60 ° C or more in the flask, and the sulfuric acid was added dropwise in small portions.

At the end of the dropwise addition of sulfuric acid, the temperature was raised until the internal temperature became 100 ° C, and the reaction was carried out for 2 hours while the internal temperature was maintained at 100 ° C.

After the reaction, it was confirmed that the internal temperature of the flask was lowered to 30 ° C or lower, and the contents of the flask were poured into 1 L of water, and the solid precipitated at this time (recovered amount (after drying): 22 g) was collected.

The obtained solid was dried and analyzed, and it was confirmed that the solid was a phenol resin having an aldehyde group in the molecule. Further, the ratio of the number average molecular weight (Mn), the weight average molecular weight (Mw), and the weight average molecular weight to the number average molecular weight (Mw/Mn) is as follows.

‧ number average molecular weight (Mn): 334

‧ Weight average molecular weight (Mw): 607

‧ Ratio of weight average molecular weight to number average molecular weight (Mw/Mn): 1.82

Further, in the present embodiment, the measurement of the number average molecular weight and the weight average molecular weight was carried out by using GPC (Gel Permeation Chromatography) using TSK-GEL G1000H, G2000H, and G3000H as a column type, and using tetrahydrofuran as a mobile phase. Also, monodisperse polystyrene was used as a standard substance.

In the examples and comparative examples shown below, the phenol resin 1 was successively obtained by repeating the same operation, and a metal resin composite material was produced using the same.

(Example 1)

A 1 L four-necked flask equipped with a stirring blade, a thermometer, a dropping funnel, and a condenser was prepared, and 10.00.0 g of the phenol resin obtained above was placed in the flask, and 4.6 g (0.11 mol) of sodium hydroxide was dissolved in water 300 g. Aqueous sodium hydroxide solution, thiodiethanol 6.0 g (0.05 mol), 1 N silver nitrate 31.6 g (0.03 mol). After stirring, the mixture was uniformly dissolved, and the temperature was raised until the internal temperature became 50 ° C. The reaction was carried out for 2 hours while the internal temperature was 50 ° C.

After the reaction, it was confirmed that the internal temperature of the flask was lowered to 30 ° C or lower, and 0.5 g of acetic acid was added dropwise from the dropping funnel to make the reaction system neutral to a weak acidity with a pH of 5, thereby precipitating the metal resin composite material. .

Finally, the metal resin composite material precipitated in the flask was recovered (recovered amount (after drying): 33 g).

The obtained solid was dried, and the molecular weight of the fraction soluble in tetrahydrofuran was measured by GPC. The ratio of the number average molecular weight (Mn), the weight average molecular weight (Mw), and the weight average molecular weight to the number average molecular weight (Mw/Mn) is as follows.

‧ number average molecular weight (Mn): 282

‧ Weight average molecular weight (Mw): 478

‧ Ratio of weight average molecular weight to number average molecular weight (Mw/Mn): 1.70

The metal resin composite material obtained in Example 1 was measured by an X-ray photoelectron spectroscopy apparatus Escalab-220iXL manufactured by Thermo Fisher Scientific Co., Ltd.

Further, the measurement conditions are as follows.

‧ Irradiation X-ray: Monochrome AlKα

‧Detection depth: about 5nm

‧X-ray spot diameter: about 1mm

A graph showing the results of measuring the Ag3d narrow scan pattern for the metal resin composite material obtained in Example 1 is shown in Fig. 1. Further, in response to this, a graph of the Ag3d narrow scan pattern measured on the sample in which the Ag foil was cleaned with Ar ions is shown in Fig. 2 .

In the graph shown in Fig. 1, the peak position of the Ag3d narrow scan pattern is 368.9 eV, and on the other hand, in the graph shown in Fig. 2, the peak position is 368.3 eV, and the difference in peak position is observed in these.

Generally, the peak of the Ag component is observed in the vicinity of 368.1 to 368.3 eV. In contrast, for example, in a compound in which an Ag atom such as silver acetate interacts with an O atom, the peak shifts to 368.3 to 368.9 eV ( Source: Handbook of X-ray Photoelectron Spectroscopy (Physical Electronics)).

From the above, it was confirmed that the metal resin composite material obtained in Example 1 had an Ag-O bond in its chemical structure.

Further, the metal resin composite material obtained in Example 1 was observed on the surface of the composite material by a transmission electron microscope (TEM). The result is shown in Fig. 3.

As shown in FIG. 3, the metal-resin composite material obtained in Example 1 uniformly contained silver particles of a tens of nanometer order (average particle diameter: 13 nm).

(Example 2)

A 1 L four-necked flask equipped with a stirring blade, a thermometer, a dropping funnel, and a condenser was prepared, and 10.00.0 g of the phenol resin obtained above was placed in the flask, and 4.6 g (0.11 mol) of sodium hydroxide was dissolved in water 300.0. NaOH aqueous solution, thiodiethanol 6.0g (0.05 m), 1N Silver nitrate 15.8 g (0.015 mol). After stirring, the mixture was uniformly dissolved, and the temperature was raised until the internal temperature became 50 ° C. The reaction was carried out for 2 hours while the internal temperature was 50 ° C.

After the reaction, it was confirmed that the internal temperature of the flask was lowered to 30 ° C or lower, and 0.5 g of acetic acid was added dropwise from the dropping funnel to make the reaction system neutral to a weak acidity with a pH of 5, thereby making the metal resin composite material Precipitate.

Finally, the metal resin composite material precipitated in the flask was recovered (recovered amount (after drying): 31 g).

(Example 3)

A 1 L four-necked flask equipped with a stirring blade, a thermometer, a dropping funnel, and a condenser was prepared, and 10.00.0 g of the phenol resin obtained above was placed in the flask, and 4.6 g (0.11 mol) of sodium hydroxide was dissolved in water 300 g. Aqueous sodium hydroxide solution, thiodiethanol 6.0 g (0.05 mol), 1 N silver nitrate 31.6 g (0.03 mol). After stirring, the mixture was uniformly dissolved, and the temperature was raised until the internal temperature became 30 ° C. The reaction was continued for 24 hours from the time when the internal temperature became 30 ° C.

After the reaction, it was confirmed that the internal temperature of the flask was lowered to 30 ° C or lower, and 0.5 g of acetic acid was added dropwise from the dropping funnel to make the reaction system neutral to a weak acidity with a pH of 5, thereby precipitating the metal resin composite material. .

Finally, the metal resin composite material precipitated in the flask was recovered (recovered amount (after drying): 33 g).

(Comparative Example 1)

Using Laboplastomill, the phenol resin obtained in the above was 95 g, and the average particle diameter was 1 μm. Silver powder (manufactured by DOWA Co., Ltd.) was kneaded for 5 minutes for 5 minutes to obtain a metal resin composite material.

(Comparative Example 2)

Using a Laboplastomill, 90 g of the phenol resin obtained above and 10 g of silver powder (manufactured by DOWA Co., Ltd.) having an average particle diameter of 1 μm were kneaded for 30 minutes to obtain a metal resin composite material.

The metal resin composite materials obtained in Examples 1 to 3 and Comparative Examples 1 and 2 were evaluated based on the following.

(proportion)

The metal resin composite material obtained in each of the examples and the comparative examples was subjected to compression molding under the conditions of a press pressure of 100 MPa and a mold temperature of 175 ° C to prepare 60 × 60 × 2 mm as shown in ISO 294-4. Audition.

For this test piece, the specific gravity was measured in accordance with JIS K 6911. The results are shown in Table 1.

(flexural strength)

Using the metal resin composite material obtained in each of the examples and the comparative examples, a test piece of 80 × 10 × 4 mm shown in ISO 178 was produced by compression molding under the conditions of a press pressure of 100 MPa and a mold temperature of 175 °C. .

Then, for the obtained test piece, the flexural strength was measured in accordance with ISO 178. The results are shown in Table 1.

The metal-resin composite material of each of the examples and the metal-resin composite material of each comparative example have a small difference in specific gravity, so that the content of the silver particles in the composite material is roughly The same level. However, when the flexural strengths of the respective examples and the comparative examples were compared, it was observed that there was a significant difference in the strengths.

It is confirmed that the metal resin composite material (metal mixed resin) of the present invention exhibits moderate adhesion due to bonding of a metal and a resin via a chemical bond, and even achieves high mechanical strength.

Industrial availability

Since the metal mixed resin of the present invention exhibits high mechanical strength because the metal particles can be uniformly dispersed in the resin, it is expected to be spread to a wide range of applications.

Further, focusing on the electrical conductivity of the metal mixed resin of the present invention, it is expected that the metal mixed resin of the present invention can also be used as a conductive material, and attention is paid to the thermal conductivity of the metal mixed resin of the present invention, and the metal mixed resin of the present invention is expected. Can also be used as a heat sink material.

The application is based on the priority of Japanese Patent Application No. 2015-038557, filed on Feb. 27, 2015, the entire disclosure of which is incorporated herein.

Claims (12)

A metal mixed resin comprising: (A) a phenol resin; and (B) a metal particle composed of a metal atom coordinated to an oxygen atom in the phenol resin. The metal mixed resin according to claim 1, wherein the metal atom is selected from the group consisting of silver (Ag), copper (Cu), zinc (Zn), calcium (Ca), iron (Fe), aluminum (Al), One or two or more metal atoms of the group consisting of magnesium (Mg). The metal-mixed resin of the first or second aspect of the invention is contained in an amount of 1% by mass or more and 85% by mass or less based on the total amount of the metal mixed resin. The metal mixed resin according to claim 1 or 2, wherein the phenol resin has an aldehyde group in a molecule. The metal mixed resin according to claim 1 or 2, wherein the metal atom is coordinated to an oxygen atom of a phenolic hydroxyl group or an oxygen atom of a carbonyl group in the phenol resin. The metal mixed resin according to claim 1 or 2, wherein the metal particles have an average particle diameter of 1 nm or more and 600 nm or less. A method for producing a metal mixed resin, comprising the steps of: (a) preparing a step (A) of a phenol resin; (b) preparing a solution of a (B') metal salt; and (c) preparing the above (A) phenol The step of mixing the resin with the solution of the above (B') metal salt and coordinating the metal atom with the oxygen atom in the above (A) phenol resin to obtain a metal mixed resin. The method for producing a metal mixed resin according to claim 7, wherein the metal atom is selected from the group consisting of silver (Ag), copper (Cu), zinc (Zn), calcium (Ca), iron (Fe), and aluminum ( One or two or more metal atoms of the group consisting of Al) and magnesium (Mg). The method for producing a metal mixed resin according to the seventh or eighth aspect of the invention, wherein the metal mixed resin produced contains 1% by mass or more of the metal particles composed of the metal atom as a whole of the metal mixed resin. 85 mass% or less. The method for producing a metal mixed resin according to claim 7 or 8, wherein the phenol resin has an aldehyde group in a molecule. The method for producing a metal mixed resin according to claim 7 or 8, wherein the metal atom is coordinated to an oxygen atom of a phenolic hydroxyl group or an oxygen atom of a carbonyl group in the phenol resin. The method for producing a metal mixed resin according to claim 7 or 8, wherein in the step (c), the solution of the (A) phenol resin and the (B') metal salt is mixed, and The (B') metal salt is subjected to a reduction reaction, and the metal salt composed of the above metal atom is formed from the (B') metal salt.