WO2016136571A1 - Metal hybrid resin and method for producing same - 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 hybrid resin and method for producing the same

The present invention relates to a metal hybrid resin and a manufacturing method thereof.

Conventionally, attempts have been made to impart properties unique to metal particles to resin materials by blending metal particles with resin materials. Examples of the properties unique to the metal particles include conductivity and high mechanical strength.

As techniques relating to this, techniques disclosed in Patent Document 1 and Patent Document 2 are known.
In 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.

JP 2013-175559 A International Publication No. 2013/018777 Pamphlet

However, as a result of studies by the present inventors, it has been found that there are the following problems.
That is, in the techniques described in Patent Document 1 and Patent Document 2, the metal particles and the resin material are blended. In the metal particles that are inorganic materials and the resin material that is organic materials, The properties possessed were different, leaving problems in terms of dispersibility of metal particles.
Here, if the dispersibility is insufficient, for example, when a mechanical force is applied to the composite material of the metal particles and the resin material from the outside, there is a concern that cracks may occur from the interface between the metal particles and the resin material. is there.

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.

According to the present invention,
(A) 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.

Moreover, according to the present invention,
(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. When,
A method for producing a metal hybrid resin containing

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.
As a result, 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.

The above-described object and other objects, features, and advantages will be further clarified by a preferred embodiment described below and the following drawings attached thereto.

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. FIG.

Hereinafter, the present invention will be described in detail based on embodiments. In the present specification, “˜” represents the following from the above unless otherwise specified.

[Metal hybrid resin]
First, the metal hybrid resin according to the present embodiment will be described.
The metal hybrid resin of this embodiment contains the following components (A) and (B).
(A) Phenolic resin (B) Metal particles composed of metal atoms coordinated to oxygen atoms in the phenolic resin

((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.
As 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.

Examples of the 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. In addition, these phenols can also be used individually or in combination of 2 or more types.

Examples of 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. Examples of 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.

When synthesizing a novolac type phenol resin, 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, and inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid. In addition, you may use these acidic catalysts individually or in combination of 2 or more types.

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.

Examples of the 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, pyrogallol, catechol, alkylcatechol, hydroquinone, alkylhydroquinone, phloroglucin, polyphenols such as bisphenol A, bisphenol F, bisphenol S, dihydroxynaphthalene, 2-hydroxybenzaldehyde, 3-hydroxybenzaldehyde, 4-hydroxy Examples thereof include phenols having an aldehyde group such as benzaldehyde or derivatives thereof. In addition, you may use these phenols individually or in mixture of 2 or more types.

Examples of aldehydes used in the production of resol type phenol resins include formaldehyde, paraformaldehyde, trioxane, acetaldehyde, propionaldehyde, polyoxymethylene, chloral, hexamethylenetetramine, furfural, glyoxal, n-butyraldehyde, capro Examples include aldehyde, allyl aldehyde, benzaldehyde, crotonaldehyde, acrolein, tetraoxymethylene, 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. Of these aldehydes, 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.

When producing a resol-type phenol resin, 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. Here, 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.

More specifically, 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.
Among these, it is preferable to use a phenol resin having a carbonyl moiety (carbonyl group) such as a ketone group, an aldehyde group, a carboxyl group, an ester group, or a urethane group in the molecule.
By doing in this way, it becomes possible to coordinate a metal atom not only to the oxygen atom of the phenolic hydroxyl group in the phenol resin but also partially to the oxygen atom of the carbonyl group. Thereby, the adhesiveness of a metal atom and a phenol resin can be improved further.
In addition, when manufacturing the phenol resin which has a carbonyl group in such a molecule | numerator, what has the corresponding functional group in the molecule | numerator about the phenols enumerated above should just be used as a raw material.

In addition, when a phenol resin having an aldehyde group in the molecule is used, there is an advantage that the production of the metal hybrid resin is facilitated.
That is, as will be described later, 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. When a phenol resin having a group is used as a raw material for the metal hybrid resin, the aldehyde group brings about a reducing action on the metal cation constituting the metal salt. In addition, by adopting this condition, there is an advantage that 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.

Although 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.

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 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.
Moreover, 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.

In this embodiment, since a chemical reaction is performed at the stage of manufacturing the metal hybrid resin, 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.
In other words, when manufacturing a metal hybrid resin, 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.

((B) Metal particles composed of metal atoms coordinated to oxygen atoms in phenol resin)
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.

Here, “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. .

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), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), hafnium (Hf), tantalum (Ta), tungsten (W), rhenium (Re), osmium (Os), iridium (Ir), platinum One or more metal atoms selected from the group consisting of (Pt) and gold (Au) can be employed.
Among these, 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.
Further, 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 μm 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. By setting in this way, the dispersibility with respect to a phenol resin can be improved.
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.

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.

(Other ingredients)
Moreover, 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.
Further, as required, 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.

[Production method of metal hybrid resin]
Then, the manufacturing method of the metal hybrid resin which concerns on this embodiment is demonstrated.
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) Process)
In this step, a phenol resin is prepared.
What is necessary is just to select the phenol resin mentioned above suitably as a phenol resin used here.

((B) Process)
In this step, a solution of (B ′) metal salt is prepared.
Here, in the present embodiment, 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.

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), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), hafnium (Hf), tantalum (Ta), tungsten (W), rhenium (Re), osmium (Os), iridium (Ir), platinum A metal salt corresponding to one or more metal atoms selected from the group consisting of (Pt) and gold (Au) may be prepared.
Among these, 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).

In this embodiment, a metal salt is comprised by the cation (cation) and anion (anion) of said metal atom.
Examples of such 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 case where 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.
In addition, when using silver, 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.

Of course, even when a metal other than silver is used, an appropriate metal salt may be selected in consideration of the solubility of the metal salt as appropriate.
For example, when using copper as a metal atom, copper sulfate, copper nitrate, etc.When using 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. When used as a metal atom, iron chloride, iron sulfate, iron nitrate, when 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.
In addition, the metal valence of the metal salt may be appropriately selected in consideration of solubility in a solvent, ease of reduction, and the like.

In this step, 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.
For example, water can be selected as the solvent. Thus, using water contributes to a reduction in manufacturing cost.

Moreover, 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. These 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.

In performing this step, 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.

That is, as described above, in this embodiment, a phenol resin having an aldehyde group in the molecule can be employed as the phenol resin.
In this case, 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.

When such a phenol resin having an aldehyde group in the molecule is used, 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.
Moreover, although the upper limit of the amount of phenol resin to be used is not specifically limited, For example, it is 100 times or less.

In addition, as 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.

Moreover, in this process, in order to accelerate | stimulate a reductive reaction, a reducing adjuvant can be used suitably. For example, when silver nitrate is used as the metal salt and a phenol resin having an aldehyde group in the molecule is mixed, dimethyl sulfide, diethyl sulfide, dipropyl sulfide, dibutyl sulfide, dipentyl sulfide, dihexyl sulfide, diphenyl sulfide, ethylphenyl sulfide Thiodiethanol, thiodipropanol, thiodibutanol, 1- (2-hydroxyethylthio) -2-propanol, 1- (2-hydroxyethylthio) -2-butanol, 1- (2-hydroxyethylthio)- 3-Butoxy-1-propanol or the like can be used as a reduction aid.
Similarly, 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.

Moreover, 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. Moreover, 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.

[Usage]
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.
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.
Specifically, 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.

As mentioned above, although embodiment of this invention was described, these are illustrations of this invention and various structures other than the above are employable.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the scope of the present invention is not limited to these examples.

[Production of phenolic resin 1]
First, a four-neck 1 L 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, 6.5 g of 92% paraformaldehyde (0.20). Mol), 210.0 g of acetic acid and 186.0 g of 2-ethoxyethanol as a solvent were added and stirred to dissolve them uniformly.
Thereafter, 73.4 g of 98% sulfuric acid was charged into the dropping funnel, and this sulfuric acid was added dropwise little by little while observing the temperature so that the temperature in the flask did not exceed 60 ° C.
When the dropping of sulfuric acid was completed, the temperature was raised until the internal temperature reached 100 ° C., and the reaction was carried out for 2 hours while maintaining the temperature from the time when the internal temperature reached 100 ° C.
After the reaction, it was confirmed that the internal temperature of the flask had dropped to 30 ° C. or less, and the contents of the flask were poured into 1 L of water, and the solid precipitated at this time was recovered (recovered amount (after drying): 22 g).

As a result of drying and analyzing the obtained solid, it was confirmed that this solid was a phenol resin having an aldehyde group in the molecule. 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.
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
In this Example section, 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. Moreover, monodisperse polystyrene was used as a standard substance.
In the following examples and comparative examples, 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.
After the reaction, it was confirmed that the internal temperature of the flask had dropped to 30 ° C. or less, and 0.5 g of acetic acid was dropped from the dropping funnel to make the reaction system neutral to weakly acidic with pH = 5 as the limit. A metal resin composite material was deposited.
Finally, the metal resin composite material deposited in the flask was recovered (recovered amount (after drying): 33 g).

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.
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 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 AlKα
・ Detection depth: about 5nm
・ X-ray spot diameter: about 1mm

A chart showing the results of measuring the Ag3d narrow scan spectrum of the metal resin composite material obtained in Example 1 is shown in FIG. In addition, FIG. 2 shows a chart of an Ag3d narrow scan spectrum measured for a sample obtained by cleaning an Ag foil with Ar ions.
In the chart shown in FIG. 1, the peak position of the Ag3d narrow scan spectrum is 368.9 eV, while in the chart shown in FIG. 2, the peak position is 368.3 eV. Differences were observed.
Usually, 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.

Moreover, 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.
After the reaction, it was confirmed that the internal temperature of the flask had dropped to 30 ° C. or less, and 0.5 g of acetic acid was dropped from the dropping funnel to make the reaction system neutral to weakly acidic with pH = 5 as the limit. A metal resin composite material was deposited.
Finally, the metal resin composite material deposited in the flask was collected (recovered amount (after drying): 31 g).

(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.
After the reaction, it was confirmed that the internal temperature of the flask had dropped to 30 ° C. or less, and 0.5 g of acetic acid was dropped from the dropping funnel to make the reaction system neutral to weakly acidic with pH = 5 as the limit. A metal resin composite material was deposited.
Finally, the metal resin composite material deposited in the flask was recovered (recovered amount (after drying): 33 g).

(Comparative Example 1)
95 g of the phenol resin 1 obtained above and 5 g of silver powder (manufactured by DOWA) having an average particle diameter of 1 μm were kneaded for 30 minutes using a lab plast mill to obtain a metal resin composite material.

(Comparative Example 2)
90 g of the phenol resin 1 obtained above and 10 g of silver powder (manufactured by DOWA) having an average particle diameter of 1 μm were kneaded for 30 minutes using a lab plast mill 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.

(specific gravity)
A test piece of 60 × 60 × 2 mm shown in ISO 294-4 was formed by compression molding under the conditions of a press pressure of 100 MPa and a mold temperature of 175 ° C. using the metal resin composite materials obtained in each Example and each Comparative Example. Was made.
About this test piece, specific gravity was measured according to JISK6911. The results are shown in Table 1.

(Bending strength)
Using the metal resin composite materials obtained in each Example and each Comparative Example, a test piece of 80 × 10 × 4 mm shown in ISO 178 was produced by compression molding under conditions of a press pressure of 100 MPa and a mold temperature of 175 ° C. did.
Subsequently, the bending strength of the obtained test piece was measured according to ISO 178. The results are shown in Table 1.

Since 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. However, when the bending strengths of the examples and the comparative examples are compared, a remarkable difference is observed in these strengths.
This is because 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.

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

Claims (12)

(A) a phenolic resin;
(B) A metal hybrid resin comprising metal particles composed of metal atoms coordinated to oxygen atoms in the phenol resin. The metal atom is one or more selected from the group consisting of silver (Ag), copper (Cu), zinc (Zn), calcium (Ca), iron (Fe), aluminum (Al), and magnesium (Mg). The metal hybrid resin according to claim 1, which is a metal atom. The metal hybrid resin according to claim 1 or 2, wherein the metal particles are contained in an amount of 1% by mass to 85% by mass with respect to the entire metal hybrid resin. The metal hybrid resin according to any one of claims 1 to 3, wherein the phenol resin has an aldehyde group in the molecule. 5. The metal hybrid resin according to any one of claims 1 to 4, 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 hybrid resin according to any one of claims 1 to 5, wherein an average particle diameter of the metal particles is 1 nm or more and 600 nm or less. (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. When,
A method for producing a metal hybrid resin containing The metal atom is one or more selected from the group consisting of silver (Ag), copper (Cu), zinc (Zn), calcium (Ca), iron (Fe), aluminum (Al), and magnesium (Mg). The manufacturing method of the metal hybrid resin of Claim 7 which is a metal atom. The manufactured metal hybrid resin contains 1% by mass or more and 85% by mass or less of metal particles composed of the metal atoms with respect to the entire metal hybrid resin. Manufacturing method of metal hybrid resin. The method for producing a metal hybrid resin according to any one of claims 7 to 9, wherein the phenol resin has an aldehyde group in the molecule. The method for producing a metal hybrid resin according to any one of claims 7 to 10, 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. . In the step (c), the (A) phenol resin and the solution of the (B ′) metal salt are mixed, and a reduction reaction is performed on the (B ′) metal salt, whereby the (B ′ The metal hybrid resin production method according to any one of claims 7 to 11, wherein metal particles composed of the metal atoms are formed from a metal salt.

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