JP2002128926A - Resin composite material and its forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for forming on the surface of a resin substrate a resin composite material having a metal element-containing component or film excellent in adhesion properties and not having a catalyst layer formed in the case of electroless plating by a relatively simple treatment step comprising a plasma treatment and a wet process without polluting working environments and the global environment. SOLUTION: The resin composite material, which has a metal element- containing component on the surface of a resin substrate and is obtained by a wet method, has no catalyst layer and is more excellent in adhesion properties between the resin substrate and the metal element-containing component and in uniformity of the film thickness of the metal element-containing film than conventional resin composite materials obtained by a wet method. As the method for forming the resin composite material dispenses with an etching treatment and an electroless plating treatment indispensable for conventional wet methods, it allows simple manufacture without causing deterioration in working environments and pollution of the global environment and the like which might be caused by such treatments.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a resin composite material having a metal element-containing component on the surface of a resin substrate and a method for forming the resin composite material.

[0002]

2. Description of the Related Art In a plating process for a plastic resin substrate, a plating process for a printed wiring board in a through-hole plating method, a semi-additive method, and the like, a method for forming a conductive film on a nonconductive resin has been used for a long time.
Electroless plating has been performed. In recent years, 3-5
Various compound semiconductors such as group III compound semiconductors and group 2-6 compound semiconductors are being used as electronic device materials and optical device materials. In particular, group 3-5 compound semiconductors have a transition-type energy band structure. Many of them have direct features, and they have excellent points such as high-efficiency electrical and optical exchange, and their use is expected. Further, various alloys, metal oxides, and the like having properties as magnetic films are being used as magnetic memory materials, magnetic head materials, optical disk memory materials, and the like. Generally, in order to form a functional film such as a compound semiconductor or a magnetic film on the surface of a resin substrate, a PVD (physical vapor deposition) method such as a vacuum evaporation method, a sputtering method, and an ion plating method is employed. .

[0003] The electroless plating treatment has a bad working environment for the human body, such as the use of a carcinogenic substance such as formalin, and has the problem of causing environmental pollution due to the waste liquid of the electroless plating treatment. . Further, in general, the electroless plating treatment involves many steps, so that it takes a long time and has a problem that the management of the electroless plating treatment liquid is complicated. Further, in a resin composite material in which a metal film is formed on a resin substrate by electroless plating, the adhesion between the resin substrate and the metal film is generally low. Therefore, usually, as a pretreatment for improving the adhesion, an etching treatment for treating the surface of the resin substrate with a chemical such as chromic acid or permanganic acid to form irregularities on the surface of the resin substrate that provides an anchor effect is performed. Required. However, in some cases, such as polyimide resin, it is difficult to form irregularities that provide an anchor effect even when an etching treatment is performed, and it is difficult to obtain sufficient adhesion. Further, chemicals such as chromic acid and permanganic acid used for the etching process have a problem for the environment and the human body. When a metal film is formed on the surface of the resin substrate by the electroless plating method, first, a catalyst nucleus such as Pd, Ag, or Au is formed on the resin substrate, and then the plating is performed centering on the catalyst nucleus. The metal is deposited, and a metal film is formed. Therefore, in the resin composite material having a metal film on the surface of the resin substrate obtained by the electroless plating method, the catalyst metal exists as a catalyst layer between the metal film and the resin substrate. For this reason, regarding the thickness of the metal film formed by the electroless plating method, the portions where the catalyst nuclei are present are thicker and the portions where the catalyst nuclei are not present are thinner. When the density is low, there is a problem that sufficient uniformity of the film thickness cannot be achieved.

[0004] The above-mentioned plating process for the plastic resin substrate, the through-hole plating method for the printed wiring board,
The non-conductive resin used in the plating process in the semi-additive method or the like is manufactured from an epoxy resin, a polyimide resin, and the like.
Since a substrate made of a resin such as methyl methacrylate, polyethylene, or vinyl chloride is a poor conductor of electricity, it is easily charged by friction or the like. In a charged substrate, the substrate is damaged by discharging static electricity generated by the charging, and dust or the like easily adheres to the substrate due to the static electricity.
For this reason, there is a problem that processing of the resin base becomes difficult, and it is particularly remarkable in the manufacture of precision parts in which fine damage to the base, fine dust, and dust are not allowed. In addition, many processed resin products do not require adhesion of dust and dust due to charging. In order to prevent electrification in the resin substrate, it is best not to cause charge separation, but in the current situation where there are many unknowns in the electrification mechanism,
It is difficult to solve the problem from this viewpoint. Therefore, to reduce the local electric field formed by charge separation, the surface is covered with a substance having a high dielectric constant, or nearby air is ionized for the purpose of increasing the leakage speed of separated charges. In addition, charging is prevented by covering the surface with a substance having a large dielectric constant.

[0005] As the antistatic method, there are a temporary antistatic method and a permanent antistatic method. As the temporary static elimination method, a surface active agent or a substance mainly composed of a surface active agent is applied to the surface of the substrate to apply the same. There is a method of increasing the hygroscopicity, thereby reducing the surface resistance, and an air ionization method, but both have a problem of poor durability. It is used only to eliminate processing difficulties. As a permanent antistatic method, there is a method of introducing a conductive substance such as silver or copper powder into a resin substrate. As one mode of introducing a conductive substance into a resin base, there is a method of mixing a conductive substance into a resin base. In this case,
There is a possibility that the original properties of the resin base, such as the low conductivity, which is the property of the resin base, may be lost. The reason for mixing the metal while maintaining the properties of the resin base is not only the amount of the mixed metal but also the metal. The particle size and distribution of the particles are also important, and it is very difficult to mix these metals while controlling them to obtain a resin substrate having desired properties.

Further, as another mode for introducing a conductive substance into a resin substrate, there is a method of introducing a metal to the surface of the resin substrate. As the method of introducing the metal, a metal vapor deposition method, a casting method, a plating method, or the like is used. Have been. When introducing a metal onto the surface of the resin substrate, the adhesion between the resin substrate and the metal and the amount of the metal introduced are problematic, but these methods do not always allow the metal to be introduced with good adhesion. Although it is sufficient to remove the charge, it is difficult to introduce the metal in such an amount that the low conductivity on the surface of the substrate does not exceed a certain level. For example, when the resin constituting the resin substrate is a polyimide resin, it is difficult to form irregularities that cause an anchor effect, and thus it is more difficult to obtain sufficient adhesion than other resins. In the case of ABS resin, chromic acid
By etching with a mixed solution of sulfuric acid, butadiene particles are preferentially eluted to form round concave marks, thereby producing an anchor effect and improving adhesion, and in the case of an epoxy resin or a polyimide resin. In this method, the adhesion can be improved by etching the epoxy resin with a permanganic acid solution or the like to form irregularities on the surface. However, even after these surfaces are etched as a pre-treatment, even if a metal is introduced by an electroless plating method that has been widely used in the past, the low conductivity does not exceed a certain level and the charging is prevented. It is extremely difficult to introduce as little metal as possible.

[0007]

For this reason, there is a strong demand for a new method of introducing a metal component or forming a metal film on the surface of a resin substrate instead of the electroless plating. In addition, special and large-scale equipment is required for PVD methods such as vacuum evaporation, sputtering, and ion plating, which are used to form functional films such as semiconductors and magnetic films on the surface of resin substrates. It is said. For this reason, a simpler method for forming a semiconductor, a magnetic film and the like on the surface of the resin substrate is desired. Also, without lowering the low conductivity inherently possessed by the resin base to a certain level,
There is a strong demand for a non-chargeable resin composite material in which a trace amount of a metal element-containing component that can prevent charging of the resin substrate is introduced onto the surface of the resin substrate.

The present invention has been made in view of such circumstances, and the present invention has a metal element-containing component or a film having excellent adhesion on a surface of a resin substrate, and is provided with an electroless plating method. Does not have a catalyst layer formed in the case of
The purpose is to provide a resin composite material obtained by a wet method, and further, by using a plasma treatment and a relatively simple processing step by a wet method, to form the resin composite material without polluting the working environment and the global environment. It is also an object to provide a method. Further, in the present invention, a metal-containing component is introduced onto the surface of the resin substrate so that the conductivity of the resin substrate can be prevented without making the low conductivity on the surface of the resin substrate higher than a certain level. An object is to provide a resin composite material.

[0009]

The present invention provides a resin composite material obtained by a wet method, having a metal element-containing component on the surface of a resin substrate, wherein the resin composite material has no catalyst layer. Provide materials. In addition, the present invention provides a method for treating a surface of a resin substrate subjected to plasma treatment with a metal ion-containing liquid to introduce metal ions, and converting the metal ions. A resin composite material having the same is provided. Further, the present invention provides (1) a step of plasma-treating the resin substrate,
(2) a step of treating with a metal ion-containing liquid, and (3)
A method for forming the resin composite material, comprising a step of forming a metal element-containing component on a resin surface by a conversion treatment.

[0010]

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a resin composite material having a metal element-containing component on the surface of a resin substrate and obtained by a wet method, wherein the resin composite material has no catalyst layer. The present invention will be described in detail below.

The resin substrate that can be used in the resin composite material of the present invention is made of any resin, as long as it has appropriate physical properties according to the intended use, such as strength and corrosion resistance. The resin substrate is not particularly limited. The resin substrate usable in the present invention is not limited to a resin molded product, and may be a composite material in which a reinforcing material such as a glass fiber reinforcing material is interposed between resins, or may be a ceramic, glass, metal, or the like. A resin film may be formed on a substrate made of any of the above materials.

Any resin can be used for the resin substrate, for example, polyethylene resins such as high-density polyethylene, medium-density polyethylene, branched low-density polyethylene, linear low-density polyethylene, ultra-high-molecular-weight polyethylene, polypropylene resins, Polybutadiene, boribene resin,
Polyolefin resins such as polybutylene resin and polystyrene resin; halogen-containing resins such as polyvinyl chloride resin, polyvinylidene chloride resin, polyvinylidene chloride-vinyl chloride copolymer resin, chlorinated polyethylene, chlorinated polypropylene, and tetrafluoroethylene; AS resin AB
S resin; MBS resin; polyvinyl alcohol resin; polyacrylate resin such as polymethyl acrylate;
Polymethacrylate resins such as polymethyl methacrylate; methyl methacrylate-styrene copolymer resin; maleic anhydride-styrene copolymer resin; polyvinyl acetate resin; cellulose propionate resin, cellulose acetate resin, etc. Cellulose resin; Epoxy resin; Polyimide resin; Polyamide resin such as nylon; Polyamideimide resin; Polyarylate resin; Polyetherimide resin; Polyetheretherketone resin; Polyethylene oxide resin; Various polyester resins such as PET resin; Resin; polyvinyl ether resin; polyvinyl butyral resin; polyphenylene ether resin such as polyphenylene oxide; polyphenylene sulfide resin; polybutylene terephthalate resin; Rimechirupenten resin; polyacetal resin; PVC - Vinegar Bikoporima; ethylene - acetate Bikoporima; ethylene - salt Bikoporima; and the like and these copolymers and thermoplastic resins such as a blend,
Epoxy resin; xylene resin; guanamine resin; diallyl phthalate resin; vinyl ester resin; phenolic resin; unsaturated polyester resin; furan resin; polyimide resin; polyurethane resin; maleic acid resin; , As well as mixtures thereof. Preferred resins include epoxy resin, polyimide resin, vinyl resin, phenol resin, nylon resin, polyphenylene ether resin, polypropylene resin, fluorine resin, AB
An S resin is mentioned, and an epoxy resin, a polyimide resin, a polyphenylene ether resin, a fluororesin, and an ABS resin are more preferable, and an epoxy resin and a polyimide resin are still more preferable. Further, the resin substrate may be made of a single resin, or may be made of a plurality of resins. Further, the surface to be plasma-treated may be a resin substrate, and may be a composite in which a resin is applied or laminated on another substrate.

The metal element-containing component in the resin composite material of the present invention refers to a component containing a metal or a metal compound.
The metal may be a metal composed of a single metal element,
An alloy composed of two or more metal elements may be used. As the metal, the alloy may be in a state in which a plurality of metal elements form a solid solution, a state in which an amorphous body which is a mixture of component metals composed of the respective metal elements is formed, or a state in which these are combined. May be. Metal compounds are
A compound in which a plurality of types of metal elements form an intermetallic compound,
And a compound comprising at least one kind of metal element and at least one kind of element other than the metal element. The metal compound contained as the metal element-containing component may be one type or a plurality of types. The metal element refers to an element whose element is a metal, for example, Sc, Ti, V, Cr, Mn, F
e, Co, Ni, Cu, Zn, Ga, Ge, As, S
e, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd,
Ag, Cd, In, Sb, Te, Hf, Ta, W, R
e, Os, Ir, Pt, Au, Hg, Tl, Pb, B
i, Po and the like.

If the metal element-containing component is a metal, the metal may be a metal Sc, Ti, V, Cr, Mn, Fe,
Co, Ni, Cu, Zn, Ga, Ge, As, Se,
Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, A
g, Cd, In, Sb, Te, Hf, Ta, W, Re,
A metal selected from the group consisting of Os, Ir, Pt, Au, Hg, Tl, Pb, Bi or Po, and alloys thereof is preferred. More preferably, the metal is metal V, C
r, Mn, Fe, Co, Ni, Cu, Ga, As, S
e, Mo, Ru, Rh, Pd, Ag, Cd, In, S
It is a metal selected from the group consisting of b, Te, Os, Ir, Pt, Au, Hg, Pb or Bi, and alloys thereof. Even more preferably, the metal is a metal V, M
n, Co, Ni, Cu, Ga, As, Se, Mo, P
d, Ag, In, Sb, Te, Pt, Au, Hg or Bi, and a metal selected from the group consisting of alloys thereof. Most preferably, the metal is a metal Co, Ni,
It is a metal selected from the group consisting of Cu, Pd, Ag, Pt or Au, and alloys thereof.

[0015] In the non-chargeable resin composite material of the present invention, the metal element-containing component introduced onto the resin substrate can exist on the substrate in any state. For example, the metal element-containing component may be present separately as fine particles on the substrate surface, may be a film or a network structure, or may be a mixture thereof. In addition, various forms such as the thickness of the coating when forming the coating, such as the distribution state and the particle size of the particles in the case of being in the form of particles, are appropriately set. The state of introduction of the metal element-containing component is as follows: (1) a step of plasma-treating the resin substrate, (2) a step of treating with the metal ion-containing liquid, and (3) a conversion treatment to form the metal element-containing component on the resin surface. When formed by a method including a step of causing
It is possible to adjust appropriately by changing each condition of the steps (1) to (3). The surface of the resin composite material formed by introducing the metal element-containing component onto the resin substrate,
Depending on the types and amounts of the metals and metal compounds contained, and the state of introduction, various useful properties such as conductivity, semiconductor properties, magnetism, and non-charging properties are obtained. Further, when the metal element-containing component forms a film, a conductive film, a compound semiconductor film, a magnetic film, etc., depending on the type of the metal and the metal compound contained therein, and when the metal is an alloy, the state of the alloy. Has various useful properties as a functional film. From the viewpoint of being useful as a magnetic film, the metal film is made of Co-Ni, Co-Cr, Co-V,
Ni-Mo-Fe, Gd-Co, Mn-Bi, Mn-C
It is preferable to include alloys such as u-Bi, Pt-Co, and Co-Cr.

The metal compound is a compound in which a plurality of kinds of metal elements form an intermetallic compound, and a compound composed of one or more kinds of metal elements and one or more kinds of elements other than metal elements. Metal arsenides including GaSb, InSb; metal antimonides including ZnSe, CdSe, HgSe; metal tellurides including CdTe, HgTe; CuS, PdS, CdS, ZnS, A
gS and other metal sulfides; Fe ₂ O ₃ , Fe ₃ O
_{4, CrO, Co-Ni-} O, MnO-ZnO-Fe 2
Metal oxides including O ₃ ; metal hydroxides; metal nitrides; metal silicides; metal borides;
It is not limited to these.

The metal compound is preferably GaAs
arsenic including s, InAs; GaSb, I
metal antimonides including nSb; ZnSe;
Metal selenides such as CdSe and HgSe; C
Metal telluride including dTe, HgTe; Cu
S, PdS, CdS, ZnS, metal sulfides including _{AgS; Fe 2 O 3, Fe} 3 O 4, CrO, Co-N
It is selected from the group consisting of and mixtures thereof; where i-O, metal oxides including _{MnO-ZnO-Fe 2 O 3} . More preferably, GaAs, GaSb, InA
s, InSb, ZnSe, CdSe, CdTe, HgS
e, HgTe, CuS, PdS, CdS, ZnS, Ag
_{S, Fe 2 O 3, Fe} 3 O 4, CrO, Co-Ni-O
And _{MnO-ZnO-Fe 2 O 3} , and is selected from the group consisting of mixtures.

Metal arsenides such as GaAs and InAs; metal antimonides such as GaSb and InSb; metal selenides such as ZnSe, CdSe and HgSe; metal tellurides such as CdTe and HgTe; Coatings containing metal sulfides such as CdS and ZnS are useful as compound semiconductors.
Further, a film containing a metal sulfide such as CuS or PdS is useful as a conductive film. Further, Fe ₂ O ₃ , Fe ₃ O
_{4, CrO, Co-Ni-} O, MnO-ZnO-Fe 2
A metal oxide film such as O ₃ is useful as a magnetic film.

In the present invention, the above-mentioned metal or metal compound in the above-mentioned resin used for the resin substrate and the metal element-containing component can be arbitrarily selected. When the metal element-containing component is a metal, the combination of the resin and the metal is preferably epoxy resin, polyimide resin, vinyl resin, phenol resin, nylon resin, polyphenylene ether resin, polypropylene resin, fluorine resin or ABS. A resin selected from the group consisting of resins and mixtures thereof, wherein the metal is metal V, Mn, Co, N
i, Cu, Ga, As, Se, Mo, Pd, Ag, I
It is a metal selected from the group consisting of n, Sb, Te, Pt, Au, Hg or Bi, and alloys thereof. More preferably, the resin is an epoxy resin, a polyimide resin,
Vinyl resin, phenol resin, nylon resin, polyphenylene ether resin, polypropylene resin or ABS
A resin selected from the group consisting of resins and mixtures thereof, wherein the metal is metal V, Mn, Co, Ni, Cu,
Ga, As, Se, Mo, Pd, Ag, In, Sb, T
e, Pt, Au, Hg or Bi, and a metal selected from the group consisting of alloys thereof. Even more preferably, the resin is a resin selected from the group consisting of an epoxy resin, a polyimide resin, a polyphenylene ether resin or an ABS resin, and a mixture thereof, and the metal is a metal V, Mn, Co, Ni, Cu, Ga, As, Se,
Mo, Pd, Ag, In, Sb, Te, Pt, Au, H
g or Bi, and a metal selected from the group consisting of alloys thereof.

When the metal element-containing component is a metal sulfide, the combination of the resin and the metal sulfide is preferably such that the resin is an epoxy resin, a polyimide resin, a polyphenylene ether resin, a fluorine-based resin or an ABS resin, and a combination thereof. A resin selected from the group consisting of a mixture, wherein the metal sulfide is CuS, CdS, ZnS, PdS, Ag
_{2 S,} is _{As 4 S 4, As 2 S} 3, As 2 S 6, TeS and TeS _3, and metal sulfides selected from the group consisting of mixtures. More preferably, the resin is a resin selected from the group consisting of an epoxy resin, a polyimide resin, a polyphenylene ether resin or an ABS resin, and a mixture thereof, and the metal sulfide is CuS,
A metal sulfide selected from the group consisting of CdS, ZnS, PdS or Ag ₂ S, and mixtures thereof.

When the metal element-containing component is a metal oxide, the combination of the resin and the metal oxide is preferably selected from the group consisting of an epoxy resin, a polyimide resin or a fluorine-based resin, and a mixture thereof. And the metal oxide is a metal oxide selected from the group consisting of FeO, NiO, CoO or MnO, and mixtures thereof. More preferably, the resin is a resin selected from the group consisting of an epoxy resin or a polyimide resin, and a mixture thereof, and the metal oxide is Fe
A metal oxide selected from the group consisting of O, NiO, CoO or MnO, and mixtures thereof.

The metal element-containing component present on the surface of the resin composite material of the present invention is subjected to various treatments according to a usual method. When the metal element-containing component forms a film, for example, a conductive film can be used as a base film for various plating treatments. After forming the film, an electrolytic copper plating process is performed.In the semi-additive method, after forming the conductive film, electroless copper plating process, resist pattern forming process, electrolytic copper plating process, solder plating process, as necessary, Conventionally known processes such as a resist removal process and a solder stripping process are sequentially performed.
If necessary, a known process such as a degreasing process, a washing process, an etching process, and a rust prevention process may be added. Further, the compound semiconductor film can be used as an electronic device material, an optical device material, and the like according to a conventional method. Regarding the magnetic coating,
For example, it can be used as a magnetic memory medium, a magnetic head material, an optical disk memory material, and the like.

In the present specification, the term “wet method” means that a metal element component (any form of a metal-containing substance such as a metal, a metal ion, or a metal compound) is introduced into a resin substrate in a liquid phase. The method of the present invention, which will be described in detail later, is a wet method. Further, the wet method refers to a PVD method such as a vacuum evaporation method, a sputtering method, and an ion plating method.
This is a concept opposite to a dry method in which a metal is introduced into a resin substrate in a gas phase as in the method.

The resin composite material of the present invention is characterized in that no catalyst layer is present. When a metal film is formed on the surface of a resin substrate by an electroless plating method, first, the resin substrate is generally treated with a catalyst made of Pd and Sn or Cu to form Pd and a tin salt or Cu.
Then, a plating metal is deposited around the catalyst nucleus to form a metal film. Here, the catalyst layer refers to a layer of a catalyst formed on a resin substrate, but the catalyst does not necessarily need to be in a layered form, as long as the catalyst is present on the resin. Alternatively, a mode in which catalyst nuclei are scattered on the resin surface may be used. Therefore, the resin composite material having a metal film on the surface of the resin substrate obtained by the electroless plating method has a catalyst core between the metal film and the resin substrate, that is,
The catalyst layer will be present. On the other hand, the resin composite material of the present invention is a resin composite material in which a catalyst layer does not exist between a metal element-containing component and a resin substrate, and is different from a material formed by conventional electroless plating.

In the resin composite material of the present invention, the metal element-containing component introduced on the resin substrate has a more uniform distribution state as compared with the case where it is introduced by conventional electroless plating. Also, it has excellent adhesion to the base resin. Further, when the metal element-containing component forms a film, the film has a more uniform film thickness in the formation of a thin film as compared with a resin composite material having a metal film formed by conventional electroless plating. While not wishing to be bound by theory, it is believed that the above advantages of the present invention result from the fact that the resin composite of the present invention does not have a catalyst layer. That is, in electroless plating, metal is deposited mainly on the catalyst nucleus formed on the resin substrate, so that the thickness of the formed metal film is such that the portion where the catalyst nucleus exists is thick and the portion where the catalyst nucleus does not exist is thick. Become thin.
Therefore, if the distribution of the catalyst nuclei in the electroless plating is non-uniform and the distribution density is low, sufficient uniformity of the film thickness cannot be achieved at a film thickness of 200 nm or less, and the film thickness cannot be controlled. is there. On the other hand, since the resin composite material of the present invention is not formed by depositing a metal around the catalyst core, nonuniformity of the film thickness due to the electroless plating does not occur. In particular, the surface of the resin substrate subjected to plasma treatment is treated with a metal ion-containing liquid to introduce metal ions,
In the metal element-containing film obtained by the method of converting metal ions, a group having an ion exchange ability is densely introduced on the surface of the resin substrate, and the metal ions are ion-exchanged into the group. Are evenly distributed,
It is considered that the film has excellent adhesiveness, and when a film is formed, a uniform film having a thickness of 50 to 200 nm is formed.

In the resin composite material of the present invention, the adhesion between the metal element-containing component and the resin substrate is improved.
When the metal element-containing component forms a film, the adhesion can be determined by the peel strength of the film and a tape peeling test. When the metal element-containing film is a metal film, the peel strength of the film is 3N. / Cm or more, preferably 5 N / c
m or more, more preferably 8 N / cm or more.
When the metal element-containing film is a metal sulfide film or a metal hydroxide film, it is preferable that no peeling is observed when a tape peeling test is performed. In addition, the peel strength of the film and the tape peeling test method will be described later.

In the present invention, “the resin composite material is non-chargeable
Has a surface resistance value that is antistatic.
Means In resin composite materials, the resin substrate is inherently
Antistatic without lowering the high surface resistance below a certain level
It is desirable to have a surface resistance that can be stopped
In view of the above, preferably, the non-chargeable resin composite of the present invention
The material has a surface resistance of 10⁶-10¹¹Ω / □ and more
Preferably, 10⁷-10⁹Ω / □. In addition,
Usually, what is called a conductor has a surface resistance of about 10^{− 6}~ 1
0²Ω / □, and what is called a semiconductor is the surface resistance
Value is about 10 at room temperature ^-2-10⁹With a value of Ω / □
It is. In addition, as non-chargeable resin composite materials, insulating
By adding a small amount of a substance with high electrical conductivity to the body,
It is preferred to achieve charging properties. From this point of view,
The amount of metal element-containing components introduced into the composite material should be
Desirably. In the present invention, "resin composite material
Resistance value of material / resistivity of metal element-containing component "
By setting, the gold existing on the surface of the resin composite material
The amount of the genus element-containing component is limited. This value is preferred
Is 10¹²-10¹⁷(1 / (□ · cm))
More preferably, 10¹³-10^Fifteen(1 / (□ ・ c
m)). Each metal element-containing component has its own resistance
Metal present on the surface of the resin composite material
The weight of the element-containing component is determined by the resistivity of the metal element-containing component.
Will change accordingly. For example, metal element-containing components
When is copper, preferably 0.005 to 5 g / m²
Surface area, preferably 0.01 to 0.3 g / m²table
Area. The “resistivity (Ω · cm)” in the present invention
Is the reciprocal of the electrical conductivity, and the metal element-containing component is
It has a specific value of resistivity. Also, "Surface resistance value
(Ω / □) ”means that the part to be measured has a width of 1 mm and a length of
= 5 mm, and apply the conductive paint.
Resistance value at the area where no is applied (5 mm length)
When R is measured, it is calculated by the following equation. Surface electric resistance (Ω / □) = R (Ω) x width (mm) / length
Sa (mm)

The above-mentioned resin composite material according to the present invention comprises:
It can be manufactured by a method including (1) a step of plasma-treating a resin substrate, (2) a step of treating with a metal ion-containing liquid, and (3) a step of forming a metal element-containing film on the resin surface by a conversion treatment. Hereinafter, each of these steps will be described in detail. Step (1): In the method for forming a resin composite material of the present invention, first, a resin substrate is subjected to plasma treatment. By this plasma treatment, the resin substrate is subjected to surface roughening by etching, elimination of resin constituent elements by high-energy active species (such as extraction of hydrogen), and branch-crosslinking or desaturation. Introduction etc. occur. In the present invention, it is considered that the group having ion exchange ability introduced into the resin ion-exchanges metal ions in step (2).

In the present invention, the group having an ion exchange ability introduced by the plasma treatment may be any of a cation exchange group and an anion exchange group, for example, a carboxyl group, a thiocarboxyl group, a dithiocarboxyl group, Sulfo group, sulfino group, sulfeno group,
Haloformyl group, carbamoyl group, hydrazinocarbonyl group, amidino group, cyano group, nitrilo group, isocyanate group, cyanato group, isocyanato group, thiocyanato group, isothiocyanato group, formyl group, hydroxyl group, carbonyl group, thioformyl group, thioxo group, mercapto group But not limited to, a group, a hydroxypropyl group, an amino group, an imino group, a hydrazino group, a diazo group, an azide group, a nitro group, and a nitroso group. Preferably, the group having ion exchange ability is a carboxyl group, a hydroxyl group, a carbonyl group, an amino group, an imino group, a cyano group, or a nitro group. In the case of a cation exchange group, in step (2), ion exchange is performed with a metal ion that is a cation. In the case of an anion exchange group, in step (2), ion exchange is performed with a metal ion that is an anion.

Examples of the group having ion exchange ability introduced by the plasma treatment include oxygen-containing functional groups such as a carboxyl group, a hydroxyl group and a carbonyl group in the case of oxygen or air plasma. For gas plasma, nitrogen-containing functional groups such as amino group, imino group and cyano group can be mentioned, and for nitrogen gas plasma, functional groups such as nitro group can be mentioned. It is also possible to introduce a group having another type of ion exchange ability by using a gas other than the above-mentioned gases. Since a group having an ion exchange ability is introduced on the resin surface by the plasma treatment, most of the surface of the resin substrate is modified to be hydrophilic.

The plasma treatment can be performed by any method as long as it can appropriately introduce the metal element-containing component into the base resin. Examples of the treatment include a reduced pressure plasma treatment and a normal pressure plasma treatment. Not done. From the viewpoint that a large-sized resin substrate can be processed and continuous processing can be performed, normal pressure plasma (in the atmosphere, normal pressure (about 1 atm)) is preferable. As the apparatus for performing the plasma processing, any apparatus can be used. For example, a reduced-pressure plasma processing apparatus can be used. The processing conditions are appropriately set according to the resin substrate used, the type of the metal element-containing film to be formed, and the like. The processing conditions in the reduced-pressure plasma processing are preferably a discharge current of 30 to 200 mA at 20 kHz, a pressure of 0.1 to 0.3 Pa, a processing time of 1 to 30 minutes, and oxygen, argon, CO ₂ and N ₂ as a modifying reagent. ₂ can be used. More preferably, the discharge current is 20k
The frequency is 50 to 150 mA, the pressure is 0.1 to 0.3 Pa, the processing time is 10 to 20 minutes, and oxygen, argon, CO ₂ and N ₂ can be used as the modifying reagent. The processing conditions in the normal pressure plasma processing are preferably a pulse voltage of 70 to 100 kV, a discharge space of 1 to 3 c.
m, the processing time is 0.5 to 100 minutes, more preferably, the pulse voltage is 80 to 90 kV, the discharge space is 1 to 2 cm,
Processing time is 1 to 30 minutes. Further, the processing temperature in the plasma processing can be appropriately set, but is preferably room temperature (about 20 ° C. to 30 ° C.) from the viewpoint of stability and workability of the resin substrate.
The gases in the atmosphere during the plasma processing include H, N,
There are O, N ₂ , O ₂ , O _3, etc., but in the case of normal pressure, oxygen is preferred.

The method of introducing a group having ion exchange ability onto the surface of the resin substrate by plasma treatment is not particularly limited, and various methods are possible, depending on the type of the resin to be introduced and the type of group to be introduced. Then, an introduction method by a known plasma treatment can be appropriately adopted. Hereinafter, a method of introducing a carboxyl group as an acidic group will be exemplified. After setting the polyimide resin film on the turntable in the microwave low-temperature oxygen plasma processing tank, the vacuum pump was operated to reduce the pressure in the processing tank to 0.13 Pa or less, and then the vacuum pump was operated in the same state. By introducing oxygen gas at a rate of 10 mL / min and irradiating the polyimide resin with a discharge current of 50 (mA) for 5 minutes, a carboxyl group as a cation exchange group can be formed on the resin surface. Also, place the polyimide resin in a narrow space of about 1 cm.
By applying a high pulse voltage of 0 to 100 KV and treating for 1 minute, a carboxyl group as a cation exchange group can be formed on the resin surface.

In step (1) of the present invention, optionally,
Before and after the plasma treatment, the resin substrate can be treated by bringing an ion exchange group-introducing agent into contact therewith. The method and time of the contact, the contact temperature, etc., a group having a desired amount of ion exchange capacity is introduced into the resin substrate,
The conditions are appropriately set so that the resin substrate is not damaged. For example, the contact method includes, but is not limited to, immersion. The treatment with the ion-exchange group-introducing agent may be performed once or may be performed a plurality of times using the same or different introducing agents. The ion-exchange group-introducing agent used in the treatment includes any agent capable of introducing a group having ion-exchange ability into the resin substrate,
Preferably, a Lewis acid or a Lewis base is used, but is not limited thereto. More preferably, the ion exchange group-introducing agent is a sulfonating agent such as sulfuric acid, fuming sulfuric acid, sulfur trioxide, chlorosulfuric acid, and sulfuryl chloride; an acid such as hydrochloric acid, nitric acid, acetic acid, formic acid, citric acid, and lactic acid; Alkalis such as sodium, potassium hydroxide and ammonia; and other aminating agents, nitrating agents, cyanating agents, oxidizing agents and the like. Even more preferably, it is sulfuric acid, potassium hydroxide or sodium hydroxide.

Step (2): Next, step (2) of the method for producing a resin composite material according to the present invention will be described. In step (2), the resin substrate obtained by subjecting the resin substrate to plasma treatment in step (1) is treated with a metal ion-containing liquid.
By this treatment, metal ions are introduced onto the resin substrate surface. It is considered that the group having the ion exchange ability introduced on the surface of the resin substrate in the step (1) performs an ion exchange reaction with the metal ion. As the metal ion-containing liquid, a solution in which a metal component constituting a target metal element-containing component exists as a metal ion may be used. For example, when forming a metal, a solution containing a desired metal ion may be used, and when forming an alloy, a solution containing metal ions of all or some metal components constituting the alloy may be used. It may be used. In the alloy, in step (2),
When a solution containing metal ions of some metal components constituting the alloy is used, it is converted into a desired alloy by treating with a solution containing the remaining metal components in the subsequent step (3). The Rukoto. When a metal compound such as a metal oxide or a metal sulfide is formed, a solution containing a metal ion of a metal component contained in the metal compound may be used.

The metal ion may be a complex ion in the liquid. In this case, the complex ion may be either a complex cation or a complex anion. The metal ion-containing liquid is generally used as an aqueous solution. However, depending on the metal ions used, the medium may be an organic medium such as methanol or an organic solution that is a mixed medium of water and an organic medium. If necessary, a stabilizer for maintaining the pH, a complexing agent for preventing precipitation of metal ions, and the like can be added to the metal ion-containing liquid.

The metal ions contained in the metal ion-containing liquid that can be used in the present invention include the ions of the metal elements exemplified above.

The metal ion is generally mixed with the metal ion-containing liquid as a metal compound or a metal salt. The type of metal compound or metal salt used is not particularly limited, and an appropriate soluble metal compound or metal salt may be used depending on the type of metal. For example, formate, acetate,
Carboxylate such as chloroacetate or oxalate, sulfate, sulfite, thiosulfate, fluoride, chloride, bromide, iodide, nitrate, nitrite, hydrogencarbonate, hydroxide, phosphoric acid Salt, phosphite, pyrophosphate, metaphosphate, selenate, thiocyanate, tetrafluoroborate, trisethylenediamine chloride, cyanide, chlorate, perchlorate, bromate, Examples include, but are not limited to, perbromate, iodate, perbromate, and the like. Preferred are sulfates, chlorides and nitrates, and more preferred are sulfates.

The concentration of metal ions in the metal ion-containing liquid is usually about 0.01 to 1 mol / l, and preferably about 0.03 to 0.1 mol / l. Further, when the target metal element-containing coating is a form containing a plurality of metal components such as a mixture of alloys and metal compounds, the metal ions are formed at a molar ratio corresponding to the molar ratio of the metal components in the final product. A contained solution may be used, and in such a case, the total concentration of the plurality of metal ions may be in the above-described range.

The method of treating the resin substrate with the solution containing metal ions is not particularly limited, but usually, the resin substrate subjected to plasma treatment in step (1) may be immersed in a solution containing metal ions. The processing is, for example, 20 to
At a temperature of about 80 ° C., preferably about 25 to 60 ° C., for example, it may be performed for about 1 to 10 minutes, preferably for about 3 to 5 minutes. Further, after the resin substrate is treated with the metal ion-containing liquid, treatments such as washing with water and drying can be performed as necessary.

In the step (3) performed after the treatment with the metal ion-containing solution, the pH of the metal ion-containing solution is reduced to reduce the pH of the metal ion-containing solution in order to replenish the hydroxide ions. -Neutral, specifically pH 2-6
It is appropriate to adjust to about 3 and preferably about 3 to 4.

Step (3): Next, step (3) of the method for producing a resin composite material according to the present invention will be described. In the step (3), a metal element-containing component is introduced into the surface of the resin substrate by performing a conversion treatment of the metal ions introduced in the step (2). In the present invention, "conversion" refers to changing the bonding state of a metal element to a bonding state different from the original state. In the present invention, it is necessary that the metal element-containing component is formed by the conversion, and the conversion not forming the metal element-containing component is not included in the conversion referred to in the present invention. The conversion treatment of the metal ions is performed depending on the type of the finally desired metal element-containing component.
For example, the conversion treatment in the step (3) is a reduction treatment when the metal element-containing component is a metal, a treatment with a sulfide-containing solution when the metal sulfide is a metal sulfide, and a water treatment when the metal hydroxide is a metal hydroxide. The treatment with the oxide-containing solution is performed, but is not limited thereto.

When the conversion treatment of the metal ions is a reduction treatment, the method of the reduction treatment is not particularly limited, and the metal ions introduced on the surface of the resin substrate by the treatment in the step (2) are reduced to form a metal. Any method can be used as long as the resin substrate can be converted into a resin substrate. Usually, the method is performed by immersing the resin substrate treated in step (2) in a solution containing a reducing agent.

The reducing agent used for reducing the metal ions introduced onto the surface of the resin substrate can be used without any particular limitation as long as the metal ions can be reduced to precipitate the metal. Usually, the solution containing the reducing agent is used as an aqueous solution. Examples of the reducing agent used in this case include sodium borohydride, dimethylamine borane (DMAB), and trimethylamine borane (TMA).
B), hydrazine, formaldehyde, and derivatives of these compounds, sulfites such as sodium sulfite, and hypophosphites such as sodium hypophosphite, but are not limited thereto, and are not limited thereto. Any reducing agent can be used. The concentration of the reducing agent in the aqueous solution is usually
About 0.0025 to 3 mol / l, preferably 0.1 to 3 mol / l.
It may be about 01 to 1.5 mol / liter. The reduction temperature is usually about 20 to 90 ° C, preferably 25 to 90 ° C.
The temperature may be about 80 ° C., and the processing time may be about 1 to 60 minutes, preferably about 20 to 40 minutes.

It is also possible to use antimony (III) chloride, tellurium chloride such as selenium urea or arsenous acid as a reducing agent. When these reducing agents are used, they are chemically adsorbed on acidic groups. At the same time as the reduced metal ions are reduced, the metal component in the reducing agent, that is, Se when selenium urea is used, As when using arsenous acid, and antimony (III) chloride are used. In this case, Sb can be used, and when tellurium chloride is used, Te can form a metal compound with a reduced metal component. The conditions for using the reducing agent such as selenium urea and arsenous acid may be the same as those for each of the above reducing agents, and may be used in combination with each of the above reducing agents. In particular, when selenium urea is used, the coexistence of another reducing agent can improve the stability of selenium urea in the reducing agent solution. Therefore, it is preferable to coexist another reducing agent.

In the above-mentioned reduction treatment using an aqueous solution containing a reducing agent, when sufficient metallization is difficult,
The reduction treatment can be performed using an organic solvent solution containing a reducing agent having a stronger reducing property. Examples of the reducing agent that can be used as such an organic solvent include metal Li,
Na, K, etc. (solvent: liquid ammonia, amines, etc.), trialkylaluminum (solvent: dioxane, toluene, tetrahydrofuran, etc.), tin hydride compounds such as tri-n-butyltin (solvent: ether solvents, benzene, toluene) Etc.). When performing a reduction treatment using an organic solvent solution of these reducing agents,
The concentration of the reducing agent, the reducing conditions, and the like may be appropriately determined so that sufficient metallization is performed according to the type of the metal salt to be reduced.

The reduction treatment can also be performed by irradiating the resin substrate into which the metal ions have been introduced with electromagnetic radiation. The reduction treatment by irradiation with electromagnetic rays is a step of using an excitation energy of the electromagnetic rays for a reduction reaction to precipitate a metal from the introduced metal ions. As the electromagnetic radiation that can be used for the reduction treatment, any electromagnetic radiation can be used as long as it has excitation energy capable of reducing metal ions, but ultraviolet rays are preferable. The power of the electromagnetic radiation can be used in a range of 10 W to 10 kW.
W is preferred. The irradiation time of the electromagnetic radiation is 30 seconds to 1 hour, preferably 1 minute to 10 minutes.

If necessary, a glass mask or the like can be attached to irradiate ultraviolet rays. When a glass mask is mounted, reduction of metal ions can be selectively performed only on necessary portions (circuits). The mask may be any mask as long as it does not transmit ultraviolet rays. Also,
Unreduced metal ions other than those required can be easily removed with a dilute nitric acid solution or the like. As a result, a resin composite material having a patterned metal film directly on the surface of the resin substrate is formed without performing etching or electroless plating.

When forming a metal sulfide, the resin substrate that has been treated with the metal ion-containing solution in step (2) is treated with a sulfide-containing solution. The sulfide contained in the sulfide-containing solution used in this treatment can be used without particular limitation as long as it generates sulfide ions in the solution. Preferred examples of such sulfides include sodium sulfide, potassium sulfide, and ammonium sulfide.

The amount of sulfide in the sulfide-containing solution is generally about 0.05 to 1.2 mol / liter, preferably about 0.1 to 0.5 mol / liter. When the sulfide concentration is less than 0.05 mol / liter, it is difficult to sufficiently precipitate the metal sulfide. On the other hand, even when the sulfide concentration exceeds 1.2 mol / liter, the effect is hardly improved. It is not preferable because it is uneconomical. The sulfide-containing solution may be an aqueous solution or a solution comprising an organic solvent and a mixture of water and an organic solvent.

The pH of the sulfide-containing solution may be weakly acidic to alkaline, and is preferably about pH 4-11.
Particularly preferably, it is adjusted to about 6 to 10. The treatment with the sulfide-containing solution may be usually performed by a method in which the resin substrate into which the metal ions have been introduced in step (2) is immersed in the sulfide-containing solution, and the treatment temperature is generally 20 to 80.
C., preferably about 25 to 60.degree. When the treatment temperature is lower than 20 ° C., formation of metal sulfide tends to be insufficient. On the other hand, when the treatment temperature is higher than 80 ° C., the solution becomes unstable, which is not preferable. The processing time may be usually about 2 to 30 minutes.

In the case of forming a metal hydroxide, the resin substrate that has been treated with the metal ion-containing liquid in step (2) is treated with a hydroxide-containing solution and then heat-treated. A metal hydroxide is formed on the resin substrate.
In this treatment step, any compound can be used as the hydroxide as long as it is a compound capable of forming hydroxide ions in a solution. Such hydroxides include Na
OH, NH ₄ OH, KOH and the like.

The concentration of the hydroxide in the hydroxide-containing liquid is generally about 0.025 to 12 mol / L,
Preferably, the concentration is about 0.1 to 5 mol / liter. If the hydroxide concentration is too low, the hydroxide will not be formed sufficiently. On the other hand, if the hydroxide concentration is too high, the resin may deteriorate, which is not preferable. The hydroxide-containing solution may be an aqueous solution or a solution composed of an organic solvent and a mixture of water and an organic solvent.

The treatment with the hydroxide-containing solution may be usually carried out by a method in which the resin substrate into which the metal ions have been introduced in step (2) is immersed in the hydroxide-containing solution. The processing temperature is generally about 10 to 80 ° C, preferably 20 to 80 ° C.
If the treatment temperature is too low, the formation of metal hydroxide tends to be insufficient. On the other hand, if the treatment temperature is too high, the resin may deteriorate, which is not preferable. . Processing time is usually 2 to 30
Minutes.

In this way, by treating with a hydroxide-containing solution, a metal hydroxide is formed on the surface of the resin substrate, and then subjected to heat treatment and dehydration, whereby the metal oxide is deposited on the resin substrate. It is formed. Although the heat treatment method is related to the heat resistance of the resin, the temperature is preferably set to a high temperature as long as the resin does not deteriorate. For example, in the case of an epoxy resin-based resin substrate, it is preferable to heat at about 80 to 150 ° C., and in the case of a polyimide-based resin substrate,
It is preferable to heat at about 80 to 180 ° C. The heating time may usually be about 30 to 120 minutes. The heating atmosphere is not particularly limited, and heat treatment may be performed in the air. For example, in the case of forming Fe ₃ O ₄ , a heating atmosphere may be used in a reducing atmosphere such as a hydrogen atmosphere so as to prevent excessive oxidation. The heating is preferably performed in accordance with the properties of the target component.

[0055]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Peel Strength Measurement Method After a thin film containing a metal element is formed by the method of the present invention, a copper film of 25 to 30 microns is formed by copper sulfate plating. After annealing at 120 ° C for 1 hour,
Cut the film to a width of 1 cm and use a tensile tester.
It was measured by a vertical peel test (90 ° peel strength) at a speed of mm / min. Tape peel test method According to ASTM D-3359-95a. That is,
Cut the knife horizontally and vertically at 1 mm intervals to make 100 squares of 1 mm square. Nichiban Cellotape 18mm
The width was applied, and the number of squares peeled off at once was counted.

Example 1 (Preparation of Copper Thin Film on Polyimide Resin) A 5 cm × 10 cm polyimide film (Kapton film 200-H manufactured by Du Pont-Toray Co., Ltd.) was placed in a normal pressure plasma apparatus (manufactured by Nippon Paint Co., Ltd.), and the pressure was increased to 80 KV. For 10 minutes at a distance between the electrodes of 2 cm. This sample is
It was immersed in a 5 mol / l aqueous solution of copper sulfate for 5 minutes at room temperature, washed with water, then immersed in a 0.02 mol / l aqueous solution of sodium borohydride at room temperature for 30 minutes, washed with water and dried. The obtained copper thin film was uniform and glossy. Thereafter, copper plating was performed using a commercially available copper sulfate plating bath at 25 μm.
Rinsing, washing with water, and at room temperature with Entec Cu-56 manufactured by Meltex Co. to prevent oxidation of the copper film surface.
Treated for seconds, washed with water and dried. After annealing at 120 ° C. for 1 hour, the peel strength of the obtained film was measured.
N / cm and good adhesion.

[0057]

Example 2 (Preparation of Copper Thin Film on Epoxy Resin) An epoxy resin (manufactured by Matsushita Electric Works) of 5 cm × 10 cm (1 mm in thickness) was put in a normal pressure plasma apparatus, and the interelectrode distance was 2 cm at 80 KV for 10 minutes. Processed. This sample is
It was immersed in a 5 mol / l copper acetate aqueous solution at room temperature for 5 minutes, washed with water, then immersed in a 0.02 mol / l sodium borohydride aqueous solution at room temperature for 20 minutes, washed with water and dried. The obtained copper thin film was uniform and glossy. Thereafter, copper plating was performed using a commercially available copper sulfate plating bath at 25 μm.
Rinsing, washing with water, and at room temperature with Entec Cu-56 manufactured by Meltex Co. to prevent oxidation of the copper film surface.
Treated for seconds, washed with water and dried. Thereafter, after annealing at 120 ° C. for 1 hour, the peel strength of the obtained film was measured and found to be 12 N / cm, indicating that the film had good adhesion.

Example 3 (Preparation of Copper Thin Film on Polyimide Resin) A 5 cm × 10 cm polyimide film (Kapton film 200-H manufactured by Du Pont-Toray Co., Ltd.) was placed on a turntable in a microwave low-temperature oxygen plasma treatment tank. Then, the vacuum pump was operated to reduce the pressure in the processing tank to 0.13 Pa or less. Then, while the vacuum pump was operated, oxygen gas was introduced at a rate of 10 mL / min to discharge the polyimide resin at a discharge current of 150 (mA). ) For 5 minutes to form a carboxyl group as a cation exchange group on the resin surface. This sample was immersed in a 0.05 mol / l aqueous solution of copper sulfate for 5 minutes at room temperature, washed with water, and then washed with 0.03
It was immersed in a mol / liter aqueous sodium borohydride solution at room temperature for 10 minutes, washed with water and dried. The obtained copper thin film was uniform and glossy. Thereafter, copper plating was performed using a commercially available copper sulfate plating bath at 25 μm, washed with water, and treated with Entec Cu-56 manufactured by Meltex Co., Ltd. for 20 seconds at room temperature to prevent oxidation of the copper film surface, and washed with water and dried. . Thereafter, after annealing at 120 ° C. for 1 hour, the peel strength of the obtained film was measured to be 9.8 N
/ Cm, and had good adhesion.

Example 4 (Preparation of Nickel Thin Film) A 5 cm × 10 cm polyimide film (Kapton film 200-H manufactured by Du Pont-Toray Co., Ltd.) was placed on a turntable in a microwave low-temperature oxygen plasma treatment tank, and then a vacuum pump was applied. Is operated to reduce the pressure in the processing tank to 0.13 Pa or less. Then, while the vacuum pump is operated, oxygen gas is introduced at a rate of 10 mL / min, and the polyimide resin is discharged at a discharge current of 100 (mA). By irradiation for one minute, a carboxyl group as a cation exchange group was formed on the resin surface. This sample was immersed in a 0.02 mol / L aqueous solution of nickel sulfate at room temperature for 5 minutes, washed with water,
It was immersed in a 0.02 mol / L sodium borohydride aqueous solution at room temperature for 10 minutes, washed with water and dried. The obtained nickel thin film was uniform and glossy. Thereafter, copper plating was performed using a commercially available copper sulfate plating bath at 25 μm, washed with water, and treated with Entec Cu-56 manufactured by Meltex Co., Ltd. for 20 seconds at room temperature to prevent oxidation of the copper film surface, and washed with water and dried. . Thereafter, after annealing at 120 ° C. for 1 hour, the peel strength of the obtained film was measured and found to be 11 N / cm, indicating that the film had good adhesion.

Example 5 (Preparation of Build-Up Substrate) A 5 cm × 10 cm (thickness: 1.6 mm) substrate (composed of eight layers of glass cloth as a reinforcing agent and made of a compressed epoxy resin) was used as an insulating layer. After applying an epoxy resin (manufactured by Matsushita Electric Works) of 100 μm and curing it at 150 ° C. for 1 hour, a micro via was formed with a carbon dioxide gas laser. After roughening the surface of the sample by desmearing, the sample was processed at 80 KV for 10 minutes at a distance between electrodes of 2 cm using an atmospheric pressure plasma apparatus. 0.05 mol /
The sample was immersed in a 1 L aqueous solution of copper acetate at room temperature for 5 minutes, washed with water, then dipped in a 0.02 mol / L aqueous solution of sodium borohydride at room temperature for 20 minutes, washed with water and dried. The obtained copper thin film was uniform and glossy. Thereafter, copper plating was performed using a commercially available copper sulfate plating bath at 25 μm,
The substrate was washed with water and treated with Entec Cu-56 manufactured by Meltex Co., Ltd. at room temperature for 20 seconds to prevent oxidation of the copper film surface, and washed with water and dried. After that, after annealing at 120 ° C. for 1 hour, the peel strength of the obtained film was measured.
It showed 12 N / cm, and had good adhesion.

Example 6 (Preparation of Iron Oxide Magnetic Film) A sample treated with plasma in Example 2 was added to a 0.05 mol / L ferrous sulfate aqueous solution (maintained at pH 3) at room temperature for 3 hours.
By immersing for 1 minute, iron ions were chemically adsorbed on the carboxyl groups formed on the substrate surface, and washed with water at room temperature for 1 minute. Thereafter, the substrate was immersed in a 1 mol / L aqueous solution of sodium hydroxide at 50 ° C. for 3 minutes to form an iron hydroxide layer.
Heat treatment for 1 minute converted to iron oxide Fe ₃ O ₄ . This film was manufactured by RIKENDENSHI CO, LTD. S.
With the MAGNETOMETER vibrating sample magnetometer,
The hysteresis loop was measured at 0.025 emu on the vertical axis and 5k0e on the horizontal axis, and as a result, the magnetic tape had magnetic properties equivalent to those of iron oxide used in current magnetic tapes.

Example 7 (Preparation of ZnSe Compound Semiconductor) The sample subjected to the plasma treatment in Example 2 was immersed in 0.05 mol / L zinc nitrate (maintained at pH 3) at room temperature for 3 minutes, so that the substrate surface was Zinc ions were chemically adsorbed on the formed carboxyl groups and washed with water at room temperature for 1 minute. Thereafter, the substrate was immersed in a mixed aqueous solution containing 0.5 mol / l of selenium urea and 0.5 mol / l of hydrazine at 60 ° C. for 3 minutes to form a zinc-selenium metal layer. For 1 minute to clean the surface, and heat-treated at 100 ° C. for 5 minutes in a drier in a nitrogen atmosphere. This film is made of Zn which is currently manufactured by a dry method.
It had the same semiconductor properties as the Se film. In the present example, the expression of having the same semiconductor characteristics means that the conductivity was 10 ⁻² to 10 ⁹ Ω / cm, and the surface resistance value in this case was 2 × 10 ^-3
２2 × 10 ⁹ Ω / □. “Surface resistance value (Ω / □)” used in the present invention means that a part to be measured has a width =
When a conductive paint is applied so as to have a length of 1 mm and a length of 5 mm, and a resistance value R is measured at a portion where the conductive paint is not applied (a portion having a length of 5 mm), it is calculated by the following equation. Surface electric resistance (Ω / □) = R (Ω) × width (mm) / length (mm) Hereinafter, in Examples 2 to 10, the surface resistance was measured by the same method.

Example 8 (Preparation of CdSe compound semiconductor) The sample subjected to plasma treatment in Example 2 was immersed in a 0.05 mol / L cadmium nitrate aqueous solution (maintained at pH 3) at room temperature for 3 minutes to obtain a substrate surface. Cadmium ions are chemically adsorbed on the carboxyl groups formed in
Washed with water for 1 minute at room temperature. Thereafter, this substrate was immersed in an aqueous solution containing 0.5 mol / l of selenium urea and 0.5 mol / l of hydrazine in an aqueous solution at 60 ° C. for 3 minutes to form a cadmium-selenium metal layer. For 1 minute to clean the surface, and heat-treated at 100 ° C. for 5 minutes in a drier in a nitrogen atmosphere. This film had semiconductor properties equivalent to the CdSe film currently manufactured by the dry method.

Example 9 (Preparation of CdTe compound semiconductor) The sample subjected to the plasma treatment in Example 2 was immersed in a 0.05 mol / L cadmium nitrate aqueous solution (maintained at pH 3) at room temperature for 3 minutes to obtain a substrate surface. Cadmium ions are chemically adsorbed on the carboxyl groups formed in
Washed with water for 1 minute at room temperature. Thereafter, this substrate was immersed in an aqueous solution containing 0.5 mol / l of tellurium chloride and 0.5 mol / l of hydrazine in an aqueous solution at 60 ° C. for 3 minutes to form a cadmium-tellurium metal layer. For 1 minute to clean the surface, and heat-treated at 100 ° C. for 5 minutes in a drier in a nitrogen atmosphere. This film had the same semiconductor properties as a CdTe film currently manufactured by a dry method.

Example 10 (Preparation of CdS compound semiconductor) The sample subjected to plasma treatment in Example 2 was immersed in a 0.05 mol / L cadmium nitrate aqueous solution (maintained at pH 3) at room temperature for 3 minutes to obtain a substrate surface. Cadmium ions are chemically adsorbed on the carboxyl groups formed in
Washed with water for 1 minute at room temperature. Thereafter, the substrate was immersed in a 0.25 mol / L aqueous solution of sodium sulfide at room temperature for 3 minutes to form a cadmium sulfide layer, washed with water at room temperature for 1 minute, and air-dried at room temperature. This film had the same semiconductor properties as the CdS film currently manufactured by the dry method.

Example 11 (Fabrication of ZnS compound semiconductor) The sample treated in Example 2 was immersed in 0.05 mol / L zinc nitrate (maintained at pH 3) at room temperature for 3 minutes to form a sample on the substrate surface. Zinc ions were chemically adsorbed on the formed carboxyl groups and washed with water at room temperature for 1 minute. Thereafter, the substrate was immersed in a 0.25 mol / L aqueous solution of sodium sulfide at room temperature for 3 minutes to form a cadmium sulfide layer, washed with water at room temperature for 1 minute, and air-dried at room temperature. This film is made of ZnS, which is currently manufactured by a dry method.
It had the same semiconductor properties as the film.

Example 12 (Preparation of InAs compound semiconductor) The sample treated with plasma in Example 2 was immersed in a 0.05 mol / L aqueous solution of indium sulfate (maintained at pH 3) at room temperature for 3 minutes to obtain a substrate surface. Indium ions are chemically adsorbed on the carboxyl groups formed in
Washed with water for 1 minute at room temperature. Thereafter, the substrate was immersed in an aqueous solution containing 0.5 mol / l arsenous acid and 0.5 mol / l hydrazine at 60 ° C. for 3 minutes to form an indium-arsenic metal layer. The surface was cleaned by washing with water for 1 minute at room temperature, and dried in a nitrogen atmosphere dryer for 10 minutes.
Heat treatment was performed at 0 ° C. for 5 minutes. This coating had semiconductor properties equivalent to those of InAs coatings currently manufactured by the dry method.

Example 13 (Preparation of InSb compound semiconductor) The sample subjected to the plasma treatment in Example 2 was immersed in a 0.05 mol / L aqueous solution of indium sulfate (maintained at pH 3) at room temperature for 3 minutes to obtain a substrate. Indium ions are chemically adsorbed on the carboxyl groups formed on the surface,
Washed with water for 1 minute at room temperature. Thereafter, the substrate was immersed in an aqueous solution containing 0.5 mol / l antimony trichloride and 0.5 mol / l hydrazine at 60 ° C. for 3 minutes to form an indium-antimony metal layer. The surface was cleaned by washing with water at room temperature for 1 minute, and heat-treated at 100 ° C. for 5 minutes in a dryer under a nitrogen atmosphere. This film had the same semiconductor properties as the InSb film currently manufactured by the dry method.

Comparative Example 1 (Preparation of Copper Thin Film on Polyimide Resin) A 5 cm × 10 cm polyimide film (Kapton Film 200-H manufactured by Du Pont-Toray Co., Ltd.) was subjected to a general-purpose electroless copper plating treatment to form a conductive thin film of copper. Thereafter, copper plating was performed using a commercially available copper sulfate plating bath at 25 μm, washed with water, and treated with Entec Cu-56 manufactured by Meltex Co., Ltd. at room temperature for 20 seconds to prevent oxidation of the copper film surface, washed with water and dried. Was. After annealing at 120 ° C. for 1 hour, the peel strength of the obtained film was measured.
cm, and good adhesion could not be obtained.

Example 14 An epoxy resin was immersed in a 1 M KOH solution at 25 ° C. for 2 minutes to clean the surface. Then, after washing with water and drying, oxygen plasma is applied at 25 ° C., 1 atm and 60 kW for 1 hour.
Irradiation was performed for 0 second to introduce a carboxyl group as a cation exchanger into the epoxy resin. Next, after immersing in a 0.1 M CuSO ₄ solution at 25 ° C. for 5 minutes, washing with water and drying,
Ultraviolet light was irradiated for 1 hour from a low-pressure mercury lamp power supply of W to reduce copper. The surface after the reduction treatment had a metallic luster. This was plated with copper sulfate at 2 A / dm ^{2 for} 60 minutes, and about 25 μm of copper was plated. This sample was washed with water, dried, cut with a knife to a width of 1 cm, and the peel strength was measured. As a result, a high strength of 9.8 N / cm was obtained, and the sample had good adhesion.

Example 15 A polyimide resin was immersed in a 1M KOH solution at 25 ° C. for 2 minutes to clean the surface. Thereafter, after washing with water and drying, oxygen plasma was irradiated at 25 ° C., 1 atm, and 60 kW for 10 seconds to introduce a carboxyl group as a cation exchanger into the polyimide resin. Next, 0.1M AgNO
After being immersed in the _three solutions at 25 ° C. for 3 minutes, washed with water, dried, and then irradiated with ultraviolet light from a 140 W low-pressure mercury lamp power source for 1 hour through a quartz glass mask pattern to form a silver circuit. Metal ions remaining outside the circuit were eluted and removed with a 1% nitric acid solution. This sample was washed with water, dried and then subjected to a tape peeling test. As a result, no adhesion of the film to the tape side was observed, and the sample had good adhesion.

Embodiment 16 Oxygen plasma was applied to ABS resin at 25 ° C., 1 atm, and 30 kW.
For 5 seconds to introduce a carboxyl group as a cation exchanger. Next, 25 ° C. in a 0.1 M NiSO ₄ solution.
After immersion for 3 minutes, washed with water and dried, UV rays at 25 ℃,
Irradiation was performed at 1 atm and 500 W for 5 minutes. A nickel pattern exhibiting metallic luster was formed on the ABS resin surface after reduction by ultraviolet light. As a result of performing a tape peeling test on this sample, no film was adhered to the tape side, and the sample had good adhesion.

Example 17 A polyimide resin was irradiated with plasma at 25 ° C., 8 Torr and 400 W for 60 seconds in an ammonia gas atmosphere.
Amino groups, which are cation exchangers, were introduced into the polyimide resin. Next, it was immersed in a 0.05M CuSO ₄ solution at 25 ° C. for 5 minutes, washed with water and dried, and then irradiated with ultraviolet rays from a 500 W high-pressure mercury lamp power source for 10 minutes to reduce copper.
The surface after the reduction treatment had a metallic luster. This is plated with copper sulfate at 2 A / dm ^{2 for} 60 minutes,
μm copper plating was performed. After washing this sample with water and drying,
As a result of cutting with a knife to a width of 1 cm and measuring the peel strength, a high strength of 9.8 N / cm was obtained and had good adhesion.

Example 18 A polyimide resin was subjected to plasma treatment in a nitrogen gas atmosphere.
Irradiation was performed at 5 ° C., 8 Torr, and 400 W for 5 minutes to introduce a nitro group as a cation exchanger into the polyimide resin. Next, it was immersed in a 0.1 M CuSO ₄ solution at 25 ° C. for 5 minutes, washed with water and dried, and then irradiated with ultraviolet rays from a 500 W high-pressure mercury lamp power source for 10 minutes to reduce copper. The surface after the reduction treatment had a metallic luster. This was plated with copper sulfate at 2 A / dm ^{2 for} 60 minutes, and about 25 μm of copper was plated. This sample was washed with water, dried, cut with a knife to a width of 1 cm, and the peel strength was measured.
High strength of 9.8 N / cm was obtained and had good adhesion.

Example 19 (Production of non-chargeable resin composite material)
Production) Oxygen plasma on ABS resin at 25 ° C, 1 atm, 30kW
For 10 seconds, and carboxyl as a cation exchange group
A group was introduced. Next, 2 M was added to a 0.1 M nickel sulfate solution.
After immersion at 5 ° C for 3 minutes, washing with water, then washing with water, 0.01
Nickel immersed in M hypophosphorous acid solution for 20 minutes and introduced
Was reduced to metal. At this time, the resistance value on the surface is
1 × 10⁹Ω / □. Nickel resistivity is 6.8
4 × 10 ^-6Ω · cm, so the surface of the resin composite material
Resistance value / resistivity of metal element-containing component = 1.5 × 10¹⁴
(1 / (□ · cm)). Example 20 (Production of Non-Chargeable Resin Composite Material) Oxygen plasma was applied to ABS resin at 25 ° C., 1 atm, and 30 kW.
For 5 seconds, and a carboxyl group which is a cation exchange group
Was introduced. Next, 25 M is added to a 0.1 M nickel sulfate solution.
After immersion in water for 3 minutes, washing with water and drying, a high-pressure mercury lamp
Irradiate with ultraviolet rays at 25 ° C, 1 atm, 500W for 5 minutes
Was. Reduces nickel introduced by ultraviolet light to metal
Was. At this time, the resistance value on the surface is 1 × 10¹⁰Ω /
□. The resistivity of nickel is 6.84 × 10^-6Ω
・ Because of cm, surface resistance value of resin composite material / metal element
Resistivity of element-containing component = 1.5 × 10¹⁴(1 / (□ ・ c
m)). Example 21 (Production of non-chargeable resin composite material) A polyimide resin was added to a 1 M potassium hydroxide solution at 25 ° C.
For 4 minutes. After washing with water and drying,
Irradiated at 25 ° C., 1 atm, 40 kW for 5 seconds.
A carboxyl group, which is an exchange group, was introduced. Next, 0.
1M NiSO₄After immersion in the solution at 25 ° C for 5 minutes, rinse with water
Then, after washing with water, the solution was added to a 0.01 M hypophosphorous acid solution for 20 minutes.
And the introduced nickel was reduced to metal. this
The resistance value on the surface at the time is 5 × 10⁹Ω / □
Was. The resistivity of nickel is 6.84 × 10^-6Ω · cm
Therefore, the surface resistance value of the resin composite material /
Minute resistivity = 7.3 × 10¹⁴(1 / (□ · cm)) and
Become. Example 22 (Production of Non-Chargeable Resin Composite Material) Oxygen plasma was applied to a polyimide resin at 25 ° C., 1 atm, 30
Irradiation at kW for 5 seconds, carboxy as a cation exchange group
A carbonyl group was introduced. Next, after washing with water and drying, 0.1 M
After immersion in a cobalt sulfate solution at 25 ° C for 5 minutes, washing with water and drying
After drying, irradiate UV light with a 140W low-pressure mercury lamp for 1 hour.
Irradiated for a while to reduce the copper. The resistance value on the surface at this time
Is 1 × 10¹⁰Ω / □. The resistivity of cobalt is
6.24 × 10^-6Ω · cm, resin composite material
Resistance value / resistivity of metal element-containing component = 1.6 × 1
0^Fifteen(1 / (□ · cm)).

As is clear from the results of Examples 19 to 22, the resin substrate was treated with plasma, and then treated with a metal ion-containing liquid to introduce metal ions and convert the metal ions. Thus, a resin composite material having a surface resistance value exhibiting non-charging properties was obtained.

[0078]

As described above, the resin composite material of the present invention is excellent in the uniform distribution of the metal element-containing component on the substrate and the uniformity of the film thickness of the metal element-containing film. It is useful in various applications that require uniform distribution and uniformity of the film. Further, since the adhesiveness between the metal element-containing component or the film and the resin substrate is excellent, it is useful in various uses requiring adhesiveness. Further, since the resin composite material of the present invention is formed by a wet method, it can be formed more easily without requiring a special and large-scale apparatus as in the dry method. Further, the resin composite material of the present invention is subjected to an etching treatment during the production thereof,
Since the electroless plating process is not required, the production can be easily performed without causing the deterioration of the working environment and the pollution of the global environment due to these. In addition, the method of the present invention is a plasma treatment method that is relatively simple and capable of continuous operation, and a treatment method using a wet method. Various metal element-containing films having a uniform thickness can be formed. Furthermore, in the method of the present invention, since the reduction can be performed by irradiation with electromagnetic radiation, a patterned metal film can be easily formed. In addition, the resin composite material of the present invention has an extremely small amount of a metal element-containing component that can prevent charging of the resin substrate without making the inherently low conductivity of the resin substrate higher than a certain level, which was conventionally difficult. Can be introduced onto the surface of the resin substrate. As a result, the non-chargeable resin composite material can prevent adverse effects such as damage to the substrate due to static electricity and dust or dust adhesion to the substrate due to charging. In addition, in the non-chargeable resin composite material, since the metal element-containing component present on the surface of the resin base has excellent adhesion to the base, permanent antistatic rather than temporary antistatic is possible. Becomes

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Masaaki Imanari 2-269-4 Yoshino-cho, Omiya-shi, Saitama Japan Rielnal Co., Ltd. Technical Research Institute (72) Inventor Koichi Yogoda 2- Yoshino-cho, Omiya-shi, Saitama 269-4 Nippon Rironal Co., Ltd. Technical Research Institute (72) Inventor Hidemi Naofune 5-38-34 Makamicho, Takatsuki-shi, Osaka F-term (reference) 4F006 AA22 AA34 AA39 AB73 AB74 AB75 BA07 CA08 EA03 4F073 AA01 BA19 BA22 BA31 BB01 CA01 4F100 AA07 AA09 AA09B AA17B AA23 AB01B AB02B AB13B AB14B AB15B AB16B AB17B AB20B AB22B AB23B AB24B AB25B AB31 AK01A AK49 AK53 AK74 BA02 BA07 DH00 EH71 EJ08 J11 EJ54 J06 EJ54 J61 EJ54 J61 EJ54 J61 EJ54 J61 EJ54 J61JBEJB

Claims (15)

[Claims] 1. A resin composite material having a metal element-containing component on a surface of a resin substrate and obtained by a wet method, wherein a catalyst layer is not present. 2. The surface of a resin substrate having a metal element-containing component obtained by treating a surface of a resin substrate subjected to plasma treatment with a metal ion-containing liquid to introduce metal ions and converting the metal ions. Resin composite material. 3. The resin composite material according to claim 1, wherein the metal element-containing component forms a metal element-containing film on the resin substrate. 4. The method according to claim 1, wherein the metal element-containing component is a metal,
The resin composite material according to any one of claims 1 to 3, which is selected from the group consisting of metal antimonides, metal selenides, metal tellurides, metal sulfides, and metal oxides. 5. The resin composite material according to claim 1, wherein the adhesion of the metal element-containing component to the substrate is improved. 6. The resin composite material according to claim 5, wherein the metal element-containing coating is a metal coating, and the peel strength of the coating is 3 N / cm or more. 7. The metal element-containing film is a metal arsenide film, a metal antimonide film, a metal selenide film, a metal telluride film, a metal sulfide film, and a metal oxide film. The resin composite material according to claim 5, which is not provided. 8. The method according to claim 1, wherein the resin composite material is non-chargeable.
The resin composite material according to any one of claims 1 to 5, wherein 9. The resistance value of the surface of the resin composite material is 10 ⁶ or more.
The resin composite material according to claim 8, wherein the resistance is 10 ¹¹ Ω / □. 10. The resin composite material has a surface resistance value of said resin composite material / a resistivity value of said metal element-containing component of 1 or more.
The resin composite material according to claim 8, wherein the ratio is from 0 ¹² to 10 ¹⁷ (1 / (□ · cm)). 11. The metal element is V, Cr, Mn, Fe, C
o, Ni, Cu, Ga, As, Se, Mo, Ru, R
h, Pd, Ag, Cd, In, Sb, Te, Os, I
11. A metal element selected from r, Pt, Au, Hg, Pb or Bi and a mixture thereof.
The resin composite material according to any one of the above. 12. The resin composite material according to claim 1, wherein the conversion is performed by irradiation with electromagnetic radiation, and the metal element-containing component is a metal. 13. The resin composite material according to claim 12, wherein the irradiation with electromagnetic radiation is performed through a mask pattern to form a patterned metal film. 14. A method comprising: (1) a step of plasma-treating a resin substrate; (2) a step of treating with a metal ion-containing liquid; and (3) a step of introducing a metal element-containing component to the resin surface by a conversion treatment. Item 3. The method for forming a resin composite material according to Item 1 or 2. 15. The method according to claim 14, wherein the metal element-containing component is introduced to form a film.