JP2635331B2 - Composite material, method for producing the same, and method for depositing metal - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a composite material, in particular, a composite material having a uniform metal layer on a carrier, a fired body thereof, a production method thereof, and a metal deposition method.

That is, the present invention relates to a composite material obtained by treating a carrier with a silicone compound having a Si-H group and then treating with a metal salt solution, particularly a carrier coated with a metal. The carrier coated with a metal obtained according to the present invention can be used as a conductive material.

Furthermore, the present invention also relates to a composite material obtained by performing electroless plating on the metal-coated carrier, which can be applied as a magnetic material, an electromagnetic wave shielding material, and the like.

In the composite material of the present invention, since a small metal colloid is generated on the surface, it interacts with a carrier and can be used as a catalyst.

Depending on the type of metal used, a colored composite material can be obtained.For example, if gold colloid is coated on the surface, red,
Palladium or platinum becomes black and can be used as a coloring material. At this time, if a black metal is coated on a white interference color type pearl agent, the appearance changes from white to an interference color, and it can be used as a colored pearl agent, which can be used for paints, inks, cosmetics, etc. it can. It can also be used as a filler for liquid chromatography.

Furthermore, the present invention also relates to a fired body of each of the above-mentioned composite materials.

[Conventional technology]

As a method of coating a metal film on a certain material,
Vacuum deposition, ion plating or sputtering is known as a dry type, and electrolytic plating, electroless plating and the like are known as a wet type.

Electroplating, which is one of the wet methods, uses a direct current to cover a metal, but has a drawback that the plating thickness is not uniform due to the shape of the object to be plated. On the other hand, electroless plating does not allow current to flow from the outside, so it does not depend on the shape of the object to be plated, the plating thickness is almost uniform, and there is no need to apply current to the object from an external power supply, so plastic And ceramics. However, electroless plating on non-conductors requires two pretreatment steps, sensitizing and activating. For example, when performing electroless plating on plastic, the plastic is immersed in a hydrochloric acid solution of stannous chloride for several minutes as sensitizing. Thereafter, as an activation, the sensitized plastic is immersed in, for example, a hydrochloric acid solution of palladium chloride. Divalent tin ions are adsorbed on the surface of the sensitized plastic, but when immersed in an activation solution, palladium ions are reduced by divalent tin ions and precipitate as metallic palladium on the surface, Conversely, tin ions are oxidized to tetravalent tin ions. When the thus formed palladium metal-precipitated plastic is immersed in an electroless plating solution, electroless plating starts with palladium as a core. What is important in this case is the strength of the adhesion between the plating and the nonconductor.
If the adhesion is weak, plating cannot be performed sufficiently.

[Problems to be solved by the invention]

However, in a conventional dry method such as a vacuum deposition method or a sputtering method, the treatment is performed in a state close to a vacuum, and is not suitable for treating a large amount of powder or the like.

In addition, even in the wet method, a current is required in the electrolytic plating method, and a dedicated device must be used. In addition, the electroless plating method involves sensitizing and activating steps, which is complicated. Further, there is a problem that the catalyst solution is strongly acidic and the carrier is damaged, so that it cannot be used for a substance weak to an acid.

An object of the present invention is to provide a simple and versatile method capable of supporting a wide variety of metals as a uniform layer on a carrier. It is a further object of the present invention to provide a composite material having a uniform metal layer on a carrier.

[Means for solving the problem]

According to the present invention, a carrier supporting a silicone polymer layer having a Si-H portion is treated with a metal salt solution to form a metal layer on the silicone polymer layer. A composite material is provided that carries the metal layers essentially in this order.

According to the invention, also the carrier carrying the silicone polymer layer having Si-H moieties is treated with a solution of a salt of a first metal to deposit the first metal on said silicone polymer layer, A silicone polymer layer and a first metal layer on a surface of a carrier obtained by forming a second metal film on a first metal deposition layer by treating with an electroless plating solution containing a second metal; And a composite material carrying the second metal layer essentially in this order.

Further, the present invention provides a composite, wherein the carrier supporting the silicone polymer layer having a Si-H portion is treated with a metal salt solution to form a metal layer on the silicone polymer layer, followed by firing. A method of making the material is also provided.

Further, the present invention provides a method of treating a carrier carrying a silicone polymer layer having a Si-H moiety with a solution of a salt of a first metal to deposit the first metal on the silicone polymer layer. A method for producing a composite material, comprising forming a film of a second metal on a deposition layer of a first metal by treating with an electroless plating solution containing a second metal, followed by firing. I do.

Furthermore, the present invention also provides a method for precipitating a metal from a metal salt solution, comprising treating a silicone polymer having a Si—H moiety with a metal salt solution.

 Hereinafter, the present invention will be described in detail.

The carrier used in the present invention is not particularly limited as long as it is a solid that is stable under the processing conditions according to the present invention, that is, there is no particular limitation on the material, shape, structure, size, and the like. Therefore, in terms of materials, typical examples are
Metal, metal oxide, silicate mineral, pearlescent material, carbon, plastic, paper, biopolymer, ultramarine, navy blue,
Mica and composite powders are included. These carriers may be treated by one kind or by combining a plurality of kinds.
Furthermore, one or more of these powders can be treated with aggregates, compacts, films or shaped bodies.

The carrier has a μm as long as it is stable under the above conditions.
From orderly powders, they can be of the order of mm or cm or larger. In the present invention, especially a powdery carrier, preferably a particle diameter of 0.001 μm to 2
It is suitable to use a carrier of 00 μm, especially 0.01 μm to 10 μm.

Metal oxides and metal hydroxides that can be used in the present invention are magnesium oxide, magnesium hydroxide, calcium oxide, calcium hydroxide, aluminum oxide,
Aluminum hydroxide, silica, iron oxide (α-Fe ₂ O ₃ −,
γ-Fe ₂ O ₃ , Fe ₃ O ₄ , FeO), yellow iron oxide (particularly rod-shaped), titanium oxide (particularly titanium dioxide having a particle size of 0.001 to 1.0 μm), lower titanium oxide, zirconium oxide, chromium oxide : Composite oxides and hydroxides of chromium hydroxide, manganese oxide, cobalt oxide, nickel oxide, and combinations of two or more of these, such as silica alumina, iron titanate, cobalt titanate, lithium cobalt titanate, and aluminum Cobalt acid is exemplified. Also ultramarine,
Pigments such as navy blue can also be treated. The particle size of these carriers is not particularly limited, but 0.001 μm to 10 m
m, especially 0.001 to 200 μm, preferably 0.01 to 10 μm.

The pearl luster material used as a carrier in the present invention includes titanium mica-based composite material, mica iron oxide-based composite material, bismuth oxychloride, guanine, and a titanium compound containing titanium oxynitride and / or lower titanium oxide. Coated mica and the like. The titanium of the mica-titanium-based composite material may be any of titanium dioxide, low-order titanium oxide, and titanium oxynitride. Further, a mica-titanium-based composite material or bismuth oxychloride may be further mixed with a colored pigment such as iron oxide, navy blue, chromium oxide, carbon black, carmine or ultramarine.

The pearly luster material used in the present invention may be a raw material, but when used as a pearly luster pigment in powder form, the particle size is 0.
Particles having a flatness of 1 to 200 μm, particularly about 1 to 50 μm and having a particle shape as small as possible are preferable because beautiful color tone and pearl luster are easily exhibited.

The silicate minerals used in the present invention are phyllosilicate minerals (eg, kaolin, montmorillonite, clay mica, chlorite, serpentine) and tectosilicate minerals (eg, zeolite), and pyrophyllite. , Talc, chlorite, chrysotile, antigorite, lizadite, kaolinite, deckite, nacrite, halloysite, montmorillonite, nontronite, saponite, sauconite, bentonite and soda zeolite, medium zeolite, scholes zeolite, Thomson zeolite, etc. And zeolite such as mesolite, heavy zeolites, gray zeolites, chabazite and gumelinite, and the like.

These phyllosilicate minerals may contain organic cations between layers, or may be substituted with alkali metal, alkaline earth metal ions, or the like.

In the case of the tectosilicate, the metal ions may enter the pores.

Mica includes muscovite, phlogopite, biotite, sericite, iron mica, phlogopite, lithia mica, chinwald mica, soda mica, and the like.
l ₂ (Al, Si ₃ ) O ₁₀ F ₂ , KMg ₃ (Al, Si ₃ ) O ₁₀ F ₂ , K (Mg Fe ₃ )
(Al, Si ₃ ) O ₁₀ F ₂ ]. These mica may be fired.

The inorganic material used in the present invention is CaCO which is a carbonate mineral.
₃ , MgCO ₃ , FeCO ₃ , MnCO ₃ , ZnCo ₃ , CaMg (CO ₃ ) ₂ , Cu (OH) ₂ CO
₃ , Cu ₃ (OH) ₂ (CO ₃ ) ₂ , BaSO ₄ , a sulfate mineral, SrSO
_{4, PbSO 4, CaSO 4,} CaSO 4 · 2H 2 O, CaSO 4 · 5H 2 O, Cu 4 SO 4 (OH)
₆ , KAl ₃ (OH) ₆ (SO ₄ ) ₂ , KFe ₃ (OH) ₆ (SO ₄ ) ₂ , phosphate minerals YPO ₄ , (Ce, La) PO ₄ , Fe ₃ (SO ₄ ) ₂・ 8H
₂ O, Ca ₅ (SO ₄ ) ₃ F, Ca ₅ (SO ₄ ) ₃ Cl, Ca ₅ (SO ₄ ) ₃ (OH),
Examples include Ca ₅ (SO ₄ , CO ₃ OH) ₃ (F, OH), metal nitrides such as titanium nitride, boron nitride, and chromium nitride.

Activated carbon, carbon black and the like can also be used as inorganic substances.

Biopolymers include keratin such as hair, animal hair, feathers, horns, and hooves, collagen such as silk fibroin, animal skin, tendons, and bones, cellulose, hemicellulose, pectin, chitin,
Examples include chondroitin, nucleic acids (eg, DNA, RNA), peptides, glucan, and the like. These polymers may be in the form of fibers or sheets.

The metals used as carriers include aluminum, iron,
Nickel, cobalt, chromium, gold, silver, copper, platinum,
Zinc, indium, tin, antimony, tungsten,
Zirconium, molybdenum, silicon or titanium.

As synthetic resins, 12 nylon, polyamide, polyethylene, polystyrene, divinylbenzene, benzoguanamine, polyester, acrylic resin, silicone resin,
Fluororesin, cellulosic resin, polyethylene terephthalate and the like can be mentioned.

In the first step of the method for producing a composite according to the invention, the powder is coated with a coating of a silicone polymer having at least one Si-H moiety. In this coating process,
Any silicone compound can be used as long as a silicone polymer film having at least one Si-H moiety can be formed on the powder surface.

In the silicone polymer coating step of the present invention, a silicone compound having at least one Si-H moiety can be used, and is preferably a compound represented by the general formula: (Wherein, R ¹ , R ² and R ³ are each independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms which may be substituted with at least one halogen atom. ,
R ¹ , R ² and R ³ are not simultaneously hydrogen atoms, and R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom or substituted by at least one halogen atom. A hydrocarbon group having 1 to 10 carbon atoms, and a is 0
Or an integer of 1 or more, b is 0 or an integer of 1 or more, and c is 0 or 2, provided that when c is 0, the sum of a and b is an integer of 3 or more. And the maximum value of a + b + c should be 10,000). In the formula (I), the groups R ^{1 to} R ⁶ may be different from each other in each repeating unit.

The silicone compounds of the formula (I) consist of two groups. The first group corresponds to the case where c = 0 in the above formula (I), and has a general formula (R ¹ HSiO) ₂ (R ² R ³ SiO) _b (III) wherein R ¹ , R ² , R ³ , a and b have the same meanings as described above, but preferably R ¹ , R ² and R ³ are each independently a lower alkyl having 1 to 4 carbon atoms which may be substituted with at least one halogen atom. An alkyl group or an aryl group (for example, a phenyl group), and the sum of a and b is 3 or more.]

The second group of the silicone compounds of the formula (I) corresponds to the case where c = 2 in the formula (I), [Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , a and b have the same meanings as above, and c is 2, but preferably R ^{1 to} R ⁶ are mutually Independently a lower alkyl group having 1 to 4 carbon atoms or an aryl group (for example, a phenyl group)].

The silicone polymer coating step according to the present invention can be carried out by various methods (including conventional coating methods).

For example, a silicone compound is converted into an organic solvent (eg, chloroform, hexane, benzene, toluene, acetone)
The carrier is dispersed with a silicone polymer film by dispersing the carrier, particularly powder, in the dispersion solution to prepare a dispersion, heating the dispersion to evaporate the solvent, and forming a film on the surface of the carrier. Can be coated. Further, a film can be formed by drying the above-mentioned dispersion liquid with a spray drier. Alternatively, the carrier is poured by pouring the dispersion into the poor solvent of the high molecular silicone compound, or by pouring the poor solvent into the dispersion and adhering the insolubilized silicone compound onto the carrier surface to form a film thereof. Can be carried out.

The above-mentioned coating treatment can also be carried out by mechanochemically treating a liquid high molecular silicone compound and a carrier or the like with a powder in a ball mill, for example.

Further, the carrier can be encapsulated with a silicone polymer film by polymerizing the silicone compound monomer on the surface of the carrier in the presence of a catalyst, as in an in situ polymerization method.

Alternatively, the step of coating the silicone polymer according to the invention can be carried out using active sites which are widely distributed on substantially the entire surface of the carrier. As used herein, the term “active point” refers to a siloxane bond (Si—O—Si) or
It is a site capable of catalyzing the polymerization of a silicone compound having a Si-H (hydrosyl) group, and means, for example, an acid point, a base point, an oxidation point or a reduction point.

In the coating step utilizing active sites, the silicone compound is brought into contact with the various carriers described above in the form of its own vapor, in the form of a solution dissolved in an appropriate solvent, or in its own liquid form, and It can be polymerized on the surface.

A treatment in which a liquid silicone compound itself is directly contacted with a carrier (hereinafter sometimes referred to as a liquid phase treatment).
Is a suitable mixer such as a rotary ball mill, a vibrating ball mill, a planetary ball mill, a sand mill, an attritor,
The method is carried out by charging a carrier, particularly a powder, into a pug mill, a poni mixer, a planetary mixer, a crusher, or the like, and treating the powder mechanochemically. Care must be taken in this liquid phase treatment because the shape of the carrier may change. Carriers preferably used for this liquid phase treatment, for example, talc,
It is a mixture of mica or spherical resin (for example, nylon, polyethylene, cellulose) and fine powder (for example, pigment). When the mixture is treated with the silicone compound while mixing the talc, mica or spherical resin with the pigment, the talc, mica or spherical resin as a core is coated with the pigment and the silicone resin.

As an alternative to the liquid phase treatment, a solution of the silicone compound and a carrier may be contacted. As a solvent for the silicone compound, an organic solvent such as chloroform or hexane can be used. Preparing a solution containing 1 to 50% by weight of the silicone compound in the solvent,
Dispersing the carrier therein, followed by heating to evaporate the solvent and polymerize the silicone compound on the surface, or
Alternatively, the solution can be sprayed directly onto the carrier, followed by similar heating to evaporate the solvent and polymerize the silicone compound.

The carrier that can be used in the liquid phase treatment is a carrier that can be easily filtered, for example, powder such as talc and mica. Also,
Silicone compounds suitable for the liquid phase treatment are, for example, those wherein a + b + c in the formula (I) is 10,000 or less.

The silicone compound may be brought into contact with the carrier in the form of evaporation (hereinafter, may be referred to as a gas phase treatment).
Specifically, the basic mode of the gas phase treatment is as follows. A carrier and a silicone compound (eg, a cyclic organosiloxane) are put in separate containers in a closed room (eg, at 100 ° C. or lower), and the upper part is opened. Just keep it. In this state, the silicone compound is vaporized by the partial pressure at that temperature and maintains adsorption equilibrium on the carrier. When the treated carrier is removed from the sealed room, if the carrier is not active, the silicone compound will be desorbed and the carrier will return to the original surface, but the carrier with active sites on the surface In the case of (1), the silicone compound is polymerized on the carrier because of the polymerization activity, and the partial pressure of the silicone compound on the carrier surface is reduced, so that the silicone compound is vaporized and supplied from the silicone compound in the container. Since the surface polymerization occurs in such an order, the silicone compound is supplied in a required amount in the system, and there is no waste. Since gas-phase processing is based on such a simple principle, no special equipment is required. For example, any closed room (for example, a closed room that can be kept at a constant temperature) such as a constant temperature bath can be used. In addition, a desiccator can be used for the small amount treatment. However, ideally, a device capable of degassing after treatment is desirable, and a gas sterilization device is preferably used. The carrier in the closed room can be agitated continuously or intermittently to make contact between the carrier and the silicone compound vapor desirable.

According to another embodiment of the gas phase treatment, at 120 ° C. or lower, preferably 1 ° C.
Only the carrier is previously charged in a closed room at a temperature of 00 ° C. or lower, and a silicone compound is vaporized at a predetermined partial pressure in another closed room at a temperature of 120 ° C. or lower, and the room in which the carrier has been charged is vaporized. The vaporized silicone compound can be introduced therein, for example by means of a pipe. Although there is no particular limitation on the pressure of the system, the polymerization is 200 mmHg or less, preferably 100 mmHg.
It is preferably carried out under the following pressure. In either embodiment, the treatment time is from 30 minutes to 150 hours, after which the unpolymerized silicone compound is removed by degassing,
Obtain the desired product.

According to another aspect of the gas phase treatment, the carrier can be treated by contacting the silicone compound in the form of a gas mixture with the carrier gas (for example, by supplying the carrier surface). The mixing of the silicone compound with the carrier gas is accomplished by, for example, heating the silicone compound, if necessary, until the silicone compound has a vapor pressure of at least 1 mmHg, preferably at least 100 mmHg, and then flowing the carrier gas into or at the surface of the silicone compound. It can be implemented by being introduced above. The supply rate of the carrier gas stream can be appropriately determined depending on, for example, the vapor pressure of the silicone compound, the type and amount of the carrier, and the capacity of the processing container. It is preferable to adjust so that the treatment can be performed in 30 minutes to 150 hours.

As the carrier gas, an inert gas such as nitrogen, argon, helium or the like is preferable, but a mixed gas obtained by mixing water or steam, methanol vapor, or ethanol vapor in a gaseous molecular state with air or the inert gas may also be used. it can.

According to the gas phase treatment, the mixed gas containing the silicone compound is brought into contact with the carrier. Since the mixed gas contains the silicone compound as saturated vapor, it is necessary to make the contact / reaction temperature the same as or higher than the temperature of the mixed gas. If the contact / reaction temperature is lower than the temperature of the mixed gas, the silicone compound is condensed and the carrier, especially the powder, is easily treated in an agglomerated form. When a carrier having many active sites on the surface is treated with the mixed gas, the carrier is easily slurried. In this case, it is preferable that the contact / reaction temperature be equal to or higher than the temperature of the supplied mixed gas and that a carrier gas containing no silicone compound is simultaneously supplied to reduce the relative pressure of the silicone compound with respect to the saturated vapor pressure.

The silicone compound and the carrier gas can be separately introduced and mixed in the reaction vessel.

As described above, in the gas phase treatment, by supplying a mixed gas of a silicone compound and a carrier gas to the carrier surface, molecules of the silicone compound are continuously adsorbed to the carrier, and active points on the surface are utilized. Polymerization forms are included.

The above-mentioned gas-phase treatment can be advantageously carried out on all carriers to which the present invention is directed. In particular, powders of ultrafine powders, porous materials, pearl pigments, organic pigments and the like are preferably subjected to a gas phase treatment. When these powders are treated by a gas phase treatment, an ultrathin silicone polymer film is formed, and the ultrafineness, porosity, pearl effect and the like of the powder can be maintained. In addition, a metal carrier that is stable against oxidation can be obtained by subjecting a metal that is easily oxidized to a gas phase treatment immediately after its generation. Silicone compounds suitable for gas phase processing
In the above formula (I), it is a compound of a + b + c = 3 to 10, especially 3 to 7. Particularly preferred silicone compounds are as follows.

The compounds (A), (B) and (C) can be used alone or in any combination thereof.

Examples of the cyclic silicone compound suitable for the gas phase treatment include, for example, dihydrogenhexamethylcyclotetrasiloxane, trihydrogenpentamethylcyclotetrasiloxane, tetrahydrogentetramethylcyclotetrasiloxane, dihydrogenoctamethylcyclopentasiloxane, and trihydrogenoctamethylcyclopentasiloxane. Hydrogen heptamethylcyclopentasiloxane, tetrahydrogenhexamethylcyclopentasiloxane and pentahydrogenpentamethylcyclopentasiloxane can be mentioned. These compounds can be used alone or in any combination.

Specific examples of linear silicone compounds suitable for gas phase treatment include 1,1,1,2,3,4,4,4-octamethyltetrasiloxane, 1,1,1,2,3,4, Mention may be made of 5,5,5-nonamethylpentasiloxane and 1,1,1,2,3,4,5,6,6,6-decamethylhexasiloxane.

Generally, silicone compounds having at least two Si-H moieties in the molecule are preferred. However, the amount of hydrogen atoms becomes so large that it becomes difficult to obtain a silicone compound containing a silicon atom bonded to two hydrogen atoms.

There are two types of structures of the silicone polymer film that covers the surface of the carrier. That is, when the polymerization occurs by a siloxane bond (-Si-O-Si-), the resulting silicone polymer has a linear structure containing -Si-O-Si- units, and preferably has a weight average molecular weight of 200,000 or more. .

On the other hand, the polymerization in the case caused by the dehydrogenation reaction of hydrosilyl bond (Si-H) in the presence of H ₂ O or O ₂ in small or trace amounts, following the polymerization of Si-H moieties: Derived from The silicone polymer will comprise a network with units.

Preferred reticulated polymers are those in which 5-90%, preferably 20-80%, of all silicon atoms are as described above in the polymer coating. It is converted to a unit. The content of this unit can be determined from the infrared absorption spectrum of the methyl group in the polymer film.

The coating amount of the silicone polymer in the silicone polymer coating treatment step varies depending on the type of the carrier and the surface area of the carrier, but is preferably 0.005 to 95% by weight based on the total weight of the carrier after the coating.

Before carrying out the silicone polymer coating according to the invention, the carrier can be subjected to any conventional treatment (eg alkali washing, acid washing, plasma treatment). When the carrier has many acid sites (for example, kaolinite, iron oxide, manganese violet), it is preferable to carry out alkali washing. This is because, according to the present invention, when the silicone compound is subsequently brought into contact with the surface and polymerized, a silicone polymer film having a crosslinked structure is easily formed.

The silicone polymer formed on the carrier in the coating step of the present invention is, for example, a compound represented by the general formula Wherein R ²¹ , R ²³ , R ²⁴ , R ²⁵ and R ²⁶ are each independently a hydrocarbon group, especially a lower alkyl group or an aryl group, and R ²² is a hydrogen atom or a hydrocarbon group, especially an alkyl group or An aryl group, provided that R ²¹ and R ²² can be different for each repeat unit, and x
Is an integer of 1 or more, y and z are 0 or an integer of 1 or more, and x and y are In particular, a molecular weight of 200,000 or more (weight average). The silicone polymer having a molecular weight of 200,000 or more does not elute even when treated with a solvent such as chloroform, and can form a complete coating on a carrier.

In the above formula (II), as the value of 100x / (x + y) increases, the network structure of the silicone polymer increases, and the possibility of release even when entering the solvent system decreases. The ratio between x and y can be calculated from the infrared absorption spectrum.

Representative examples of the silicone polymer of the formula (II) include a compound represented by the formula Wherein R ²¹ and R ²³ are a lower alkyl group such as a methyl group or an ethyl group or an aryl group such as a phenyl group, and x and y have the meanings given in the above formula (II). Or expression Wherein R ²¹ and R ²³ are a lower alkyl group or an aryl group, R ²² is a hydrogen atom, an alkyl group or an aryl group, and x and y have the meanings given in the above formula (II). Can be mentioned.

More specific examples of the silicone polymer of the formula (II) include [CH ₃ SiO _3/2 ] _x [(CH ₃ ) HSiO] _y , [CH ₃ SiO _3/2 ] _x [(C ₂ H ₅ ) HSiO] _y , [CH ₃ SiO _3/2 ] _x [(CH ₃ ) HSiO] _y [(CH ₃ ) ₃ SiO _1/2 ]
_z , [CH ₃ SiO _3/2 ] _x [(C ₂ H ₅ ) HSiO] _y [(CH ₃ ) ₃ Si
O _1/2 ] _z , [CH ₃ SiO _3/2 ] _x [(C ₅ H ₁₁ ) HSiO] _y [(CH ₃ ) ₃ Si
O _1/2 ] _z , [CH ₃ SiO _3/2 ] _x [(C ₈ H ₁₇ ) HSiO] _y [(CH ₃ ) ₃ Si
O _{1/2] z,} [CH ₃ SiO _{3/2] x} [(C ₆ H ₁₁₎ HSiO] _y [(CH _{3) 3} Si
O _1/2 ] _z , and the like.

The composite material according to the present invention can be obtained, for example, by treating a carrier coated with the above-mentioned Si-H moiety-containing silicone polymer with a metal salt solution.

Metals that can be used here are those whose ions are Si
Any metal that can be reduced by the -H moiety may be used. These metals are, for example, ruthenium (Ru), rhodium (Rh), palladium (Pd), osmium (Os), iridium (Ir), platinum (Pt), gold (Au), silver (Ag) and the like.

Treating the polymer-coated support with a metal salt solution containing the metal in cation form. The metal salt is, for example, a salt of the above-mentioned metal with an inorganic acid (eg, hydrochloric acid, nitric acid, sulfuric acid) or an organic acid (eg, acetic acid).

Particularly preferred metal salts are, for example, chloroplatinic acid, palladium chloride, chloroauric acid or silver nitrate.

The solvent is preferably, for example, an alcohol, especially a lower alcohol such as methanol, ethanol or isopropanol, acetone or chloroform, or a mixture of alcohol and water.

The concentration of the metal salt solution is not particularly limited, but 10% or less is sufficient.

The treatment with the metal salt solution can be performed by immersing the silicone polymer-coated carrier in the metal salt solution. Alternatively, when the carrier is relatively small, for example, a powder, it can be carried out by adding a metal salt or a metal salt solution to a dispersion of the silicone polymer-coated carrier.

The amount of the metal salt used can be varied in various ways depending on the desired degree of treatment, but when depositing a uniform metal layer on the carrier, it depends particularly on the surface area of the carrier to be treated.

When performing the above treatment with a metal salt solution, the silicone polymer-coated carrier and the metal salt solution are cooled, at room temperature, or under heating (for example, 0 ° C. to 60 ° C.) without particularly requiring light irradiation. If left for only about 30 minutes to 10 hours, the metal will be deposited in a uniform thickness on the silicone polymer coating layer.

The amount of the metal deposited covers the whole or a part of the silicone polymer coating layer depending on the amount of the metal salt used. The thickness of the deposited layer is 1000 ° or less, preferably 200 ° or less. When the silicone polymer coating layer is present only on a part of the carrier surface, the coating amount is 5.0% or less.

The end of the precipitation treatment with the metal salt solution can be determined, for example, by stopping the generation of hydrogen.

Thus, a composite material according to the invention is formed which carries the silicone polymer layer and the metal layer essentially in this order on the surface of the carrier. Here, "essentially in this order" means that if there is a gap between the silicone polymer layer and the carrier surface, a metal deposition layer may be formed between the two in some cases, Such rare cases are intended to be included in the scope of the present invention.

In many cases, the composite material having a metal precipitate supported on the outermost layer formed in this manner has the same activity as the material to be processed after the sensitizing step and the activation step, which are the pretreatment steps of the electroless plating method. The present inventors have further found that The activity is particularly high when the outermost layer of the composite material is a palladium deposition layer.

Therefore, for a metal that is difficult or impossible to deposit by the metal deposition treatment method using the metal salt solution,
After first treating the silicone polymer-coated support with a solution of a first metal, for example a salt of palladium, the composite material plated with the second metal is further treated with an electroless plating solution containing a second metal. Can be formed. Further, in the electroless plating method utilizing the catalytic action of palladium, the metal layer can be freely controlled, and a thick metal layer can be obtained.

In the above electroless plating treatment according to the present invention, one or more arbitrary known electroless plating solutions can be used in the same manner as the known method. As the second metal, for example, cobalt, nickel, copper, gold,
Silver, palladium and tin can be mentioned. These metals are generally metals whose deposition potential is higher than that of hydrogen.

When the composite material carrying the deposited layer of the first metal is treated with an electroless plating solution containing the second metal, the first metal acts as a catalyst to deposit the second metal. Further, alloy plating of the first metal and the second metal is also possible.

The second metal is reduced by the reducing agent contained in the plating solution, and is uniformly deposited on the polymer by the action of the metal on the silicone polymer layer.

The electroless plating solution contains the second metal in the form of an inorganic salt such as a sulfate, a hydrochloride, a nitrate, and a carbonate. For example, potassium cyanide, nickel sulfate, nickel chloride, nickel acetate, potassium potassium cyanide, copper sulfate and the like can be mentioned.

The above-mentioned electroless plating solution generally contains a reducing agent. As the reducing agent, sodium hypophosphite, sodium hyposulfite, anhydrous sodium sulfite, hydrazine chloride, hydrazine sulfate, hydrazine oxalate, anhydrous sodium sulfite, hydroquinone, hydrosalofide tartrate, formalin,
Sucrose, monosaccharides, gliogizar and the like can be mentioned, and any one or more of these can be used.

Complexing stabilizers are used to stabilize metal salts in the plating solution in the form of complex salts or chelates to prevent spontaneous decomposition of the metal salts and to facilitate the deposition of metals, such as tartrate and citrate. Complexing agents, triethanolamine, EDTA
Any one or more selected from chelating agents such as

As a buffer, organic acids such as acetic acid, tartaric acid, citric acid and gluconic acid and their sodium, potassium and ammonium salts, or sodium carbonate, potassium carbonate, ammonium carbonate, sodium bicarbonate, potassium bicarbonate,
Examples thereof include ammonium bicarbonate and the like, and any one or more of them are used.

Thus, a composite material according to the invention is formed which carries the silicone polymer layer, the first metal layer and the second metal layer essentially in this order on the surface of the carrier. Here, “essentially” has the same meaning as described above.

When each of the composite materials according to the present invention is fired in an oxidizing atmosphere, a variety of composite materials can be formed according to the firing conditions, the type of the carrier, the type of the metal layer, and the like.

When the carrier does not react with or has low reactivity with the metal and metal oxide supported thereon, the calcination described above results in a composite material comprising the carrier having the metal oxide supported on the outermost layer. Is formed.

The silicone polymer forms a composite oxide with silica or a coexisting metal by firing.

When the carrier has high reactivity with the metal or metal oxide carried thereon, various oxidized composite materials are formed by the above-mentioned calcination. For example, when firing a composite material composed of a titanium dioxide carrier supporting a cobalt layer, depending on the firing conditions, the outermost layer was changed to cobalt oxide, some titanium oxide and cobalt reacted with cobalt titanate, and the whole. Is obtained as a solid solution cobalt titanate. In addition, under an oxidizing atmosphere, for example, under a nitrogen atmosphere, a nitride is generated.

The sintering temperature is generally between 500 ° C and 1200 ° C, preferably between 700 ° C and
1000 ° C. The sintering time depends on the sintering temperature.
~ 20 hours. The firing atmosphere may be in the air, in nitrogen, or under reduced pressure of an oil rotary pump.

Various composite materials of the present invention can obtain the desired appearance color, magnetism, and conductivity by controlling the type of metal, pH of electroless plating, reaction temperature, and the like, and can provide paints, cosmetics, plastics, inks, paints, It is useful as a pigment for decorative articles, textiles, ceramics and the like, and a colored pearl luster material, and has applications such as a conductive layer or recording layer of recording paper, a conductive material such as an antistatic material, and an electromagnetic wave shielding material. In addition, a metal colloid obtained by treating a silicone compound having a Si-H group with a metal salt solution becomes a stable colloid by selecting a solvent, and is uniformly mixed with the silicone compound. Coating with a silicone film in which colloids are uniformly dispersed is possible. Electroless plating can be performed using the metal in the silicone film, for example, palladium as a catalyst.

〔Example〕

Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited thereto.

Example 1 100 g of titanium dioxide fine particles (0.025 μm) and 20 g of tetrahydrotetramethylcyclotetrasiloxane were placed in separate containers, and the containers were left at 80 ° C. in a closed container. After 96 hours, the titanium dioxide fine particles were taken out and weighed to obtain 109.30 g of silicone polymer-coated titanium dioxide fine particles, and further left in a drying oven at 90 ° C. for 24 hours to obtain 105.30 g of silicone polymer-coated titanium dioxide fine particles. .

Example 1-1 5.0 g of ethanol and 5.0 g of ion-exchanged water were added to 1.0 g of the silicone polymer-coated titanium dioxide fine particles produced in Example 1.
After adding 0 g, 1.0 g of ethanol containing 20 mg of chloroplatinic acid
Was added and left at room temperature.

Comparative Example 1-1 The same operation as in Example 1-1 was performed using titanium dioxide fine particles not subjected to the silicone polymer coating treatment in Example 1.

Results of Example 1-1 and Comparative Example 1-1 In Example 1-1, after about 2 hours, the supernatant liquid became transparent and yellow disappeared, and titanium dioxide was blackened.
At 1, the supernatant remained yellow and the titanium dioxide remained white. The infrared absorption spectrum of the silicone polymer-coated titanium dioxide of Example 1 was 2170.
Although there is an absorption of Si—H group at cm ⁻¹ , in Example 1-1, 2170
The absorption at cm ^-1 had disappeared.

Example 1-2 10 g of the silicone polymer-coated titanium dioxide fine particles of Example 1 were dispersed in 50 g of ethanol, and 100 m of palladium chloride was dispersed.
g was dissolved in 10 g of water and left at room temperature for 3 hours. The dispersion thus formed was converted to an alkaline side with ammonia water in a cobalt plating bath (0.2 M sodium hypophosphite, 0.5 M ammonium sulfate, 0.5 M sodium tartrate, 0.1 M sodium tartrate).
The mixture was dispersed in 40 ml for 40 minutes, filtered and dried to obtain 10.2 g of cobalt-plated titanium dioxide fine particles. These fine particles were black. When this was measured by X-ray fluorescence, cobalt was detected.

The thus obtained cobalt-plated titanium dioxide fine particles were placed in a crucible and fired in an electric furnace at 800 ° C. for 5 hours to obtain blue-green fine particles of cobalt titanate.

Example 2 Commercially available pearl pigment Flamenco Blue 30 manufactured by Marl, USA
0g of gas sterilizer Kapocalizer CL-30B (Fuji Electric
Co. Ltd.), 50 g of tetrahydrotetramethylcyclotetrasiloxane was placed in another container and coexisted, and the pressure in the system was reduced to 300 mmHg, and the temperature was maintained at 90 ° C. After standing overnight, air was introduced, the pressure was returned to normal pressure, and the mixture was evacuated several times to obtain a silicone polymer-coated pearl.

Example 2-1 The silicone polymer-coated pearlescent agent produced in Example 2
Disperse 10 g in ethanol 50 g, palladium chloride 100 mg
Was dissolved in 10 g of water, and the mixture was allowed to stand at room temperature. The color instantly changed from white to blue, and an interference color type blue pearl agent was obtained.

Example 2-2 Silicone polymer-coated pearlescent agent produced in Example 2
10 g was dispersed in 25 g of ethanol and 25 g of ion-exchanged water, and 5 g of isopropanol containing 200 mg of chloroauric acid was added, whereby a purple interference color type pearl agent was obtained.

Example 3 20 kg of mica was placed in a rotary double-cone type reaction tank having a capacity of 100 (made of stainless steel and equipped with a heat insulation jacket).
Directly connected to this reaction tank with a stainless steel tube, it is connected to a stock solution supply tank (stainless steel, with heat insulation jacket). 400g of silicone compound of
The pressure was reduced to Hg. The heat medium heated to 90 ° C. was supplied from the heat medium heating tank to the heat retaining jacket of the reaction tank and the stock solution supply tank by a circulation pump, and the temperature of the system was maintained at 90 ° C. The rotation of the reaction tank was 3 rotations after standing still for 10 minutes by a timer,
This rotation was repeated for 10 hours. During the repetition of rotation, the mica was mixed and stirred in the reaction vessel, and then N ₂ gas was introduced into the system to return to normal pressure, thereby obtaining 20.83 kg of a silicone polymer-coated mica.

Example 3-1 To 100 g of the silicone polymer-coated mica of Example 3, 200 g of ethanol and 100 g of ion-exchanged water were added, and 10 g of ethanol containing 100 mg of palladium chloride was added, followed by stirring at room temperature to obtain a palladium-coated mica. As a result of measuring this product by fluorescent X-ray, a trace amount of palladium was detected.

Example 3-1-1 20 g of the palladium-coated mica of Example 3-1 was treated with ethanol 6
The dispersion was added to 1.5 g of a cobalt plating bath (0.2 M sodium hypophosphite, 0.5 M ammonium sulfate, 0.5 M sodium tartrate and 0.05 M cobalt sulfate) which was made alkaline with aqueous ammonia. After dispersing for 40 minutes, the mixture was filtered and dried to obtain 20.3 g of metal cobalt-plated mica.
This product was magnetic, and the presence of cobalt was confirmed by X-ray fluorescence.

Example 3-1-2 20 g of the palladium-coated mica of Example 3-1 was treated with ethanol 6
0g, electroless nickel plating bath maintained at 70 ° C [sodium hypophosphite (10g /), sodium citrate (100g /), ammonium chloride (50g /) and nickel chloride (30g /)] After adding 1200 ml of formalin (35%), the mixture was further dispersed for 1 hour.
After filtration, washing with ethanol-water (1: 1) and drying at 80 ° C., 21.5 g of nickel-plated mica was obtained. As a result of measuring this product by fluorescent X-ray, the presence of nickel was confirmed.

Example 3-1-3 20 g of the palladium-coated mica of Example 3-1 was treated with ethanol 6
0g, and electroless copper plating bath [Rossell salt (170g /), sodium hydroxide (50g)
/), Sodium carbonate (30g /), copper sulfate (35g /
)] And dispersed in 1200 ml for 1 hour. Filter and wash with water 100
It was dried at ℃ to obtain 21.1 g of copper-plated mica. As a result of measuring this product by fluorescent X-ray, the presence of copper was confirmed.

Example 3-1-4 20 g of the palladium-coated mica of Example 3-1 was treated with ethanol 6
It was dispersed in 0 g and 140 g of a 5% EDTA solution adjusted to pH 13.0, and the temperature was raised to 80 ° C. Next, 60 g of a 10% potassium potassium cyanide solution and 60 g of a solution consisting of 2% potassium borohydride and 11% sodium hydroxide were gradually added to the above-mentioned suspension with stirring in equal amounts. . After the total amount was added, stirring was continued for 30 minutes while maintaining the liquid temperature at 80 ° C. Next, filter, wash and dry the gold-plated mica
12.6 g was obtained.

Example 4 20 g of talc, 2 g of hydrogen methylpolysiloxane (Shin-Etsu Silicon KF-99) and 30 g of alumina beads (radius 5 mm) were placed in a planetary ball mill and mixed for 2 hours. Then 20 g of ethanol containing 20 mg of palladium chloride
Was added and mixed for an additional 2 hours. Remove the mixture, pH 1
The mixture was dispersed in 100 g of a 1% aqueous potassium cyanide solution adjusted to 3.0, and heated to 85 ° C. Then, 16 g of a 10% solution of potassium silver cyanide and 16 g of an aqueous solution consisting of 3% of potassium borohydride and 16% of sodium hydroxide were added in equal amounts to the above suspension under stirring. After the total amount was added, stirring was continued while maintaining the temperature at 90 ° C. for 30 minutes to obtain 22.6 g of silver-plated talc.

Example 5 A cloth of 5 cm × 5 cm noodles was thoroughly immersed in hydrogen methyl polysiloxane (Shin-Etsu Silicon KF-99). After taking out the cloth, the cloth was placed on paper to remove the polysiloxane. Then, it was immersed in a mixed solution of 20 g of ethanol containing 50 mg of chloroplatinic acid and 5 g of ion-exchanged water, and allowed to stand for 3 hours. The darkened cloth was taken out and dried at room temperature for 24 hours to obtain a platinum-coated cloth.

Example 6 A filter paper of 5 cm × 2 cm was put in a 100 ml sample tube, 50 g of acetone and 0.5 g of tetrahydrotetramethylcyclotetrasiloxane were added, and 5 g of a 0.01% palladium chloride aqueous solution was further added.
The solution was blackened where p was added, and palladium particles precipitated. Take out the paper and keep the copper plating bath (pH 0.25M, 0.25M formalin, 0.06M EDTA, 0.05M copper sulfate, 20g / 2,2'-
Dipyridyl, 50 g / potassium ferrocyanide) 100 ml
Immersion in a mixed solution of
The reaction was carried out at 60 ° C. to obtain a copper-plated paper.

Example 7 Methyl hydrogen polysiloxane in 10 g of acetone
Add 0.5g, then 1m aqueous palladium chloride (0.01%)
When l was added and stirred well, hydrogen was generated from the solution and colloidal black palladium was deposited.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical display location C23C 18/42 C23C 18/42

Claims (5)

(57) [Claims] 1. A carrier carrying a silicone polymer layer having a Si--H portion, which is treated with a metal salt solution to form a metal layer on the silicone polymer layer. A composite material that carries the layers essentially in this order. 2. The method according to claim 1, wherein the carrier supporting the silicone polymer layer having a Si--H moiety is treated with a solution of a salt of a first metal to form a first carrier.
Is deposited on the silicone polymer layer and subsequently treated with an electroless plating solution containing a second metal to form a second metal film on the first metal deposition layer. A composite material having a silicone polymer layer, a first metal layer, and a second metal layer carried on the surface of the carrier in essentially this order. 3. The method according to claim 1, wherein the carrier supporting the silicone polymer layer having a Si—H portion is treated with a metal salt solution to form a metal layer on the silicone polymer layer, and then fired in an oxidizing atmosphere. A method of manufacturing a composite material. 4. The method according to claim 1, wherein the carrier supporting the silicone polymer layer having a Si--H moiety is treated with a solution of a first metal salt to form a first carrier.
Is deposited on the silicone polymer layer and then treated with an electroless plating solution containing a second metal to form a second metal film on the first metal deposition layer, And producing the composite material by firing. 5. A method for precipitating a metal from a metal salt solution, comprising treating the silicone compound having a Si—H moiety with a metal salt solution.