WO2016051667A1 - Electroless plating base agent, method for producing same and plating laminate using electroless plating base agent - Google Patents

Abstract

The present invention provides an electroless plating base agent which exhibits excellent adhesion, while placing little burden on the environment. The present invention relates to an electroless plating base agent which is characterized by containing a catalyst carrier (Y) and a binder polymer (Z), and which is also characterized in that: catalyst metal fine particles supported on the surface of the catalyst carrier (Y) contain palladium fine particles; and the average particle diameter (D50) of the palladium fine particles is from 10 nm to 43 nm (inclusive).

Description

Electroless plating base agent, method for producing the same, and plating laminate using the electroless plating base agent

The present invention relates to an electroless plating base agent, a method for producing the same, and a plating laminate using the electroless plating base agent.

In electroless plating, a film with a uniform thickness can be obtained by simply immersing the substrate in the plating solution, regardless of the type or shape of the substrate. Metal plating films can also be applied to non-conductive materials such as plastic, ceramic, and glass. Therefore, it is widely used in various fields such as decorative applications such as imparting a sense of quality and aesthetics to resin moldings such as automobile parts, and wiring technologies such as electromagnetic shielding, printed circuit boards and large-scale integrated circuits. . A specific example of what is manufactured using such electroless plating is a fixing member of an image forming apparatus such as a copying machine or a printer that employs an electrophotographic system.

As the fixing member, for example, Patent Document 1 discloses a fixing member having an electroless nickel plating layer, an electrolytic copper plating layer, and a silicone rubber layer on a base layer made of polyimide resin.

However, the fixing member disclosed in Patent Document 1 has the following problems.
That is, in order to form a fixing member having the metal plating layer, it is usually an activation in which a precursor of a catalytic metal such as Pd is applied to the surface of a polymer base layer and then the precursor is metallized by reduction. Process. Then, after such a plating pretreatment step for the base layer, an electroless metal plating layer is formed on the surface of the base layer. Furthermore, an electrolytic metal plating layer is formed using this as an electrode.

However, the electroless metal plating layer formed by performing the plating pretreatment has poor adhesion to the base layer. Therefore, the electroless metal plating layer is easily peeled from the base layer. Moreover, if the electroless metal plating layer peels from the base layer, as a result, the electrolytic metal plating layer or the like laminated thereon also peels from the base layer. That is, the fixing member has a problem that the adhesion between the base layer and the metal plating layer is inferior. If the metal plating layer is peeled off from the base layer during use of the fixing member, the temperature rise due to electromagnetic induction heating is reduced. Usually, the fixing member is not premised on periodic replacement, but is used repeatedly, so that it is important to have durability.

Therefore, in order to improve the adhesion, the heating member of Patent Document 2 was proposed. The heating member of Patent Document 2 includes an electroless plating base layer in which a catalyst-carrying carrier carrying a catalyst metal is dispersed on the carrier surface, and the catalyst metal carrier has a portion exposed on the surface on the metal plating side. In the electroless plating base layer, palladium is preferably used as the catalyst metal constituting the carrier for supporting the catalyst because of its excellent catalytic ability and binding property to the electroless metal plating and high versatility.

Not only in Patent Document 2, but also in the production of an electroless plating base layer using palladium, since a catalyst imparting property is excellent, a stannous chloride solution is usually used. Therefore, a waste liquid containing tin is generated, and the remaining Sn ⁴⁺ cannot be removed due to the aggregation of the carrier or insufficient cleaning, and the remaining Sn ⁴⁺ inhibits the electroless plating reaction and causes poor adhesion of the plating. It was.

In addition, when palladium fine particles are included in the electroless plating underlayer, it is considered that an average particle size as small as possible (for example, about 3 nm) is desirable in order to increase the specific surface area in consideration of catalytic activity.

However, in the production of the electroless plating underlayer, it is difficult to control the particle size of the palladium fine particles because it is difficult to control the reaction of palladium.

JP 2009-25565 A JP2013-210406A

An object of the present invention is to provide an electroless plating base material having a low environmental load and excellent adhesion. Moreover, an object of this invention is to provide the plating laminated body which has little environmental impact and is excellent in adhesiveness. Furthermore, an object of the present invention is to provide a method for producing an electroless plating base material in which the particle diameter of palladium fine particles can be easily controlled.

The present invention includes a catalyst-supporting carrier (Y) and a binder polymer (Z), the catalyst metal fine particles supported on the catalyst-supporting carrier (Y) include palladium fine particles, and the average particle diameter (D50) of the palladium fine particles. ) Is 10 nm or more and 43 nm or less.

The present invention also includes a base layer formed of a base layer polymer, the electroless plating base agent, an electroless plating base layer stacked on the base layer, and a base layer formed on the plating base layer. There is provided an electroless metal plating layer formed by electrolytic metal plating, and a plating laminate having a portion on the surface of the electroless metal plating layer where a catalyst-carrying carrier carrying a catalyst metal is exposed on the carrier surface. .

Furthermore, the present invention provides a step (A) of obtaining a catalyst metal fine particle-containing solution (X) by reducing the catalyst metal-containing raw material solution with a reducing agent, the catalyst metal fine particle-containing solution (X) obtained in the step, and a carrier To obtain a catalyst-carrying carrier (Y) carrying catalyst metal fine particles on the surface thereof, and the catalyst-carrying carrier (Y) obtained in the previous step and a binder polymer (Z). A method for producing an electroless plating base material comprising a step (C) of mixing, wherein the catalytic metal fine particles supported on the carrier include fine palladium particles, and the average particle diameter (D50) of the fine palladium particles is 10 nm or more and 43 nm or less. I will provide a.

The electroless plating base material of the present invention does not produce a tin (Sn) waste liquid, can reduce the environmental burden, and has excellent adhesion. Moreover, the plating laminated body which is excellent in adhesiveness can be provided by this invention. Furthermore, the method for producing an electroless plating base material of the present invention can easily control the particle diameter of the target palladium fine particles.

It is the figure which demonstrated typically the microstructure and laminated structure of a plating base layer in the plating laminated body which concerns on one Embodiment of this invention.

The electroless plating base material of the present invention includes a catalyst-supporting carrier (Y) and a binder polymer (Z), and the catalyst metal fine particles supported on the surface of the catalyst-supporting carrier (Y) include fine palladium particles, The average particle diameter (D50) of the palladium fine particles is from 10 nm to 43 nm.

The binder polymer (Z) used in the present invention is not particularly limited as long as the effects of the present invention are not hindered, and various resins or rubbers can be used. These may be used alone or in combination of two or more. Moreover, these can use a commercial item.

Examples of the resin include polyamideimide resin; polyamide resin; polyimide resin; urethane resin; urethane silicone resin; (meth) acrylic resin; (meth) acrylic silicone resin; fluororesin (for example, polytetrafluoroethylene (PTFE), Perfluoroalkoxyalkane (PFA), perfluoroethylene propene copolymer (FEP), ethylene-tetrafluoroethylene copolymer (ETFE), tetrafluoroethylene-perfluorodioxole copolymer (TFE / PDD), polyvinylidene fluoride (PVDF), Polychlorotrifluoroethylene (PCTFE), ethylene-chlorotrifluoroethylene copolymer (ECTFE), polyvinyl fluoride (PVF), etc.); acetal resin; alkyd resin; Ester resins (for example, polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), etc.); polyether resins (for example, poly Etherimide (PEI); Polyethersulfone (PES); Polyetherketone (PEK), Polyetheretherketone (PEEK), Polyetherketoneketone (PEKK), Polyetheretherketoneketone (PEEKK), etc. Aromatic polyether ketone having two or more); carbonate resin (for example, polycarbonate having carbonate skeleton (—O—C (═O) —O—), etc.); polyvinyl alcohol; Cellulosic resins (for example, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, etc.); polyacrylamide; polyethylene oxide; polyethylene glycol; polypropylene glycol; polyvinyl methyl ether; polyamine (for example, diethylenetriamine, triethylenetetramine, tetraethylenepentamine) , Spermidine, spermine, putrescine and the like, aliphatic amines having at least two amino groups bonded thereto; alicyclic polyamines such as isophoronediamine); polyethyleneimine; olefin resins (for example, polyethylene, polypropylene and other olefins) Monomers (eg 1-butene, 2-methyl-1-butene, 3-methyl-1-butene, pentene, hexene, cyclo Copolymer resins such as hexene, 4-methyl-1-pentene, vinylcyclohexane, octene and other aliphatic olefin monomers having 10 or less carbon atoms); polyvinyl chloride resin; polystyrene, acrylonitrile-styrene copolymer resin (SAN), styrene resins such as acrylonitrile-butadiene-styrene copolymer (ABS resin), vinyl chloride-vinyl acetate copolymer resin, polyvinyl acetal resin (for example, polyvinyl butyral resin); polyisobutylene; polytetrahydrofuran; Polyaniline, polydienes (eg, polyisoprene, polybutadiene, etc.); polysiloxanes (eg, dimethylpolysiloxane, etc.); polysulfones (PSF); polyacetic anhydrides; polyureas; polysulfides (eg, diisopropyldisulfane) Aliphatic sulfides such as dimethyltrisulfane); polyphosphazenes; aliphatic polyketones; polyhaloolefins; melamine resins, and derivatives or modified products thereof (modified groups include amino groups, epoxy groups, carboxy groups) Hydroxyl group, polyether group, epoxy alkyl group, epoxy polyether group, alkyl group having 1 to 10 carbon atoms, siloxane group, etc.). Among these, polyamideimide resin; polyamide resin; polyimide resin; urethane resin; urethane silicone resin; (meth) acrylic resin; (meth) acrylic silicone resin; fluororesin; polyester resin; polyvinyl alcohol; One or more selected from the group consisting of olefin resins are preferred.

Examples of the rubber include acrylonitrile-butadiene rubber (NBR), butadiene rubber (BR), styrene-butadiene rubber (SBR), butyl rubber (IIR), chloroprene rubber (CR), hydrin rubber (ECO, CO), isoprene rubber ( IR), urethane rubber (U), silicone rubber (Q), ethylene-propylene-diene rubber (EPDM), natural rubber (NR) and the like.

The carrier constituting the catalyst-supporting carrier (Y) of the present invention is not particularly limited as long as the effects of the present invention are not hindered. For example, various particles such as a spherical shape, a substantially spherical shape, a fibrous shape, a columnar shape, a massive shape, and a substantially tufted shape are used. It can be a shape. The material of the carrier is not particularly limited as long as the effect of the present invention is not hindered. For example, it is easy to ensure the affinity with the binder polymer (Z), and it is easy to contribute to the improvement of adhesion. One or more selected from the group consisting of a metal oxide and silica can be mentioned, and a carbon-based material is more preferable from the viewpoint of affinity with the binder polymer (Z). These may be used alone or in combination of two or more. Moreover, these can use a commercial item.

The carbon-based material is not particularly limited, and examples thereof include carbon black, carbon nanotube, fullerene, and graphite. Although it does not specifically limit as said metal oxide, For example, a titanium oxide, a zinc oxide, aluminum oxide, magnesium oxide etc. are mentioned. Of the above-mentioned supports, carbon black is particularly preferable from the viewpoints of easy loading of the catalyst metal, affinity with the binder polymer (Z), economy, and the like.

The average particle size of the carrier is preferably about 10 nm to 10 μm, preferably 50 nm to 5.mu.m, from the viewpoints of good dispersibility in the binder polymer (Z) and easy to ensure the smoothness of the plating base layer surface. About 0 μm is more preferable, and about 100 nm to 2.0 μm is more preferable. The average particle size of the support is preferably larger than the average particle size of the catalyst metal fine particles supported on the support. The average particle size of the carrier in the present invention can be measured by a dynamic light scattering type particle size distribution analyzer [manufactured by Nikkiso Co., Ltd., “Microtrac UPA-EX150”, etc.].

The catalyst metal constituting the catalyst support (Y) used in the present invention contains at least palladium (Pd). The catalyst metal is not particularly limited as long as the effect of the present invention is not hindered. In addition to palladium, a metal having a catalytic ability necessary to develop an electroless metal plating reaction (in the present invention, “metal” “Alloys” may be used). As the catalytic metal, it is preferable to use only palladium. Examples of the catalyst metal include, besides palladium, Pt group other than Pt and Pt (Ru, Rh, Os, Ir), Ag, Au, and alloys thereof.

Specifically, the catalyst-carrying carrier (Y) can have a structure in which an exposed part where the carrier surface is exposed and a carrier part where a catalyst metal is carried are mixed. In this case, it becomes easy to fix the catalyst-supporting support (Y) to the binder polymer (Z) by utilizing the affinity between the support surface and the binder polymer (Z). Therefore, when it is set as a plating laminated body, it is advantageous for the adhesive improvement between a plating base layer and an electroless metal plating layer. In particular, the carrier constituting the catalyst carrier (Y) is a carbon-based material, and the binder polymer (Z) is a polyamide-imide resin, a modified polyamide-imide resin, a polyimide resin, or a blend of these resins with a polysiloxane compound. In some cases, the effect can be easily obtained. Examples of the modified polyamideimide resin include silane-modified polyamideimide resin; siloxane-modified polyamideimide.

Also, the amount of catalyst metal used can be reduced as compared with the case where the support surface is almost covered with the catalyst metal. Therefore, it can contribute to resource saving and is advantageous in reducing the cost of the plated laminate.

In the catalyst-carrying carrier (Y) of the present invention, the catalytic metal containing palladium is carried on the carrier surface as fine particles. The palladium fine particles supported on the surface of the carrier have an average particle diameter (D50) of 10 nm or more and 43 nm or less, 10, 15, 16, 20, 21, 25, 26, 28, 29, 30, 31, 34, 35, It can be any value of 37, 39, 40, 41 and 43 nm, or a range of two values arbitrarily selected from these values (the values at the end points of the range may be included or excluded), and good 20 nm or more and 40 nm or less is more preferable, and 25 nm or more and 39 nm or less is more preferable.

The average particle diameter (D50) of the catalyst metal fine particles is a circle-equivalent diameter obtained by microscopy, and the particle size distribution of 100 Pd colloidal particles observed with a transmission microscope is obtained. (D50).

In the electroless plating base material of the present invention, it is preferable that the catalyst-carrying carrier (Y) carrying the catalyst metal on the carrier surface is dispersed in the binder polymer (Z). The binder polymer (Z) mainly has a role of holding the catalyst support in a dispersed state and forming a plating underlayer.

The electroless plating base material of the present invention includes, for example, a step (A) of obtaining a catalyst metal fine particle-containing solution (X) by reducing a catalyst metal-containing raw material solution with a reducing agent, and a catalyst metal fine particle-containing solution obtained in the above step (X) and a carrier are brought into contact with each other to obtain a catalyst-carrying carrier (Y) carrying catalyst metal fine particles on the surface (B), and the catalyst-carrying carrier (Y) obtained in the above step, and a binder A production method comprising a step (C) of mixing with a polymer (Z), wherein the catalyst metal fine particles supported on the carrier include palladium fine particles, and the average particle size (D50) of the palladium fine particles is 10 nm to 43 nm. Can be manufactured by.

[Step (A)]
In step (A) (reduction step), the catalyst metal-containing raw material solution is reduced with a reducing agent to obtain catalyst metal fine particle-containing solution (X). By adjusting the reaction conditions in this step, the particle size can be easily controlled. Further, performing this step before the contact between the catalyst metal and the carrier is one factor that makes it easy to control the particle size.

The solvent for the reduction reaction is not particularly limited as long as the effect of the present invention is not hindered. For example, alcohols such as water, methanol, ethanol, n-propanol, isopropanol, and ethylene glycol; halogenated hydrocarbons such as methylene chloride and chloroform And the like; cyclic ethers such as tetrahydrofuran, 2-methyltetrahydrofuran and tetrahydropyran; nitriles such as acetonitrile and butyronitrile; aromatic hydrocarbons such as benzene and toluene; and mixtures of these solvents, and water is preferred. . The catalyst metal-containing raw material solution and the solvent for dissolving the reducing agent may be different, but the same is preferable.

The catalyst metal-containing raw material solution is obtained by dissolving a catalyst metal-containing compound containing at least palladium in the reduction reaction solvent. The catalytic metal-containing compound is not particularly limited as long as it can be dissolved in the reduction reaction solvent. For example, palladium chloride, palladium fluoride, palladium bromide, palladium iodide, palladium nitrate, palladium sulfate, palladium oxide, sulfide Palladium compounds such as palladium; silver compounds such as silver nitrate, silver fluoride, silver oxide and silver acetate; gold cyanide, gold trichloride, gold tribromide, potassium gold chloride, potassium gold cyanide, sodium gold chloride, cyanide Examples thereof include gold compounds such as gold sodium; platinum compounds such as platinum chloride and platinum sulfate; nickel compounds such as nickel chloride and nickel sulfate. These may be used alone or in combination of two or more. The content of the catalyst metal in the catalyst metal-containing raw material solution is not particularly limited, but is preferably 0.001 g / L or more, more preferably 0.01 g / L or more based on the total amount of the catalyst metal-containing raw material solution. The catalyst metal content is preferably 5.0 g / L or less, more preferably 2.0 g / L or less, based on the total amount of the catalyst metal-containing raw material solution.

The pH of the catalyst metal-containing raw material solution is not particularly limited as long as the effect of the present invention is not hindered. For example, 1.0 to 4.5 is preferable, 1.3 to 4.0 is more preferable, and 1.5 to 3.5 is more preferable. The pH can be measured by a known method.

The catalyst metal-containing raw material solution may be heated before the reduction reaction, and is preferably heated after the preparation to the pH range and after the reduction reaction. The heating temperature depends on the solvent and is not particularly limited. However, from the viewpoint of easy control of the particle size, the boiling point of the solvent is preferably −20 ° C. to the boiling point of the solvent + 20 ° C., and the boiling point of the solvent is −10 ° C. A boiling point + 10 ° C. is more preferable. For example, when the solvent is water, the heating temperature is more preferably about 90 to 110 ° C., and the boiling temperature (100 ° C. ± 5 ° C.) is particularly preferable. The heating time is not particularly limited, but is preferably about 5 minutes to 10 hours, and more preferably about 10 minutes to 5 hours.

The reducing agent is not particularly limited as long as the effect of the present invention is not hindered. For example, a metal borohydride such as sodium borohydride or potassium borohydride; lithium aluminum hydride, potassium aluminum hydride, hydrogenation Aluminum hydride salts such as aluminum cesium, aluminum beryllium hydride, magnesium aluminum hydride, calcium aluminum hydride; hydrazine compounds; citric acid and its salts, gallic acid and its salts, formic acid and its salts, acetic acid and its salts, Carboxylic acids such as fumaric acid and its salt, malic acid and its salt, succinic acid and its salt, ascorbic acid and its salt; tannic acid and its salt; primary or secondary such as methanol, ethanol, isopropanol, polyol Alcohols; trimethylamine, triethyl Tertiary amines such as amine, diisopropylethylamine, diethylmethylamine, tetramethylethylenediamine [TMEDA], ethylenediaminetetraacetic acid [EDTA]; hydroxylamine; ketones such as acetone and methylethylketone; ethers such as diethylether; formaldehyde, Aldehydes such as acetaldehyde; esters such as methyl formate, methyl acetate, ethyl acetate; tri-n-propylphosphine, tri-n-butylphosphine, tricyclohexylphosphine, tribenzylphosphine, triphenylphosphine, triethoxyphosphine, 1,2-bis (diphenylphosphino) ethane [DPPE], 1,3-bis (diphenylphosphino) propane [DPPP], 1,1′-bis (diphenylphosphino) Erosen [DPPF], 2,2'-bis (diphenylphosphino) -1,1'-binaphthyl [BINAP] phosphines such as and the like. These may be used alone or in combination of two or more. Although it does not specifically limit as said salt, Alkali metal salt (For example, lithium, sodium, potassium etc.), calcium salt, magnesium salt, ammonium salt etc. are mentioned. Of these, citric acid and its salts (preferably sodium citrate (trisodium citrate)), tannic acid and its salts, gallic acid and its salts, and succinic acid are highly reducible and easy to handle. And ascorbic acid and its salts are preferred.

The amount of the reducing agent used is not particularly limited as long as the effect of the present invention is not hindered. However, the molar ratio of catalyst: reducing agent = 1.0: 0 with respect to the catalyst contained in the catalyst metal fine particle-containing solution (X). About 1 to 1.0: 50 is preferable, about 1.0: 0.5 to 1.0: 30 is more preferable, and about 1.0: 0.8 to 1.0: 10 is more preferable. For example, when the catalyst is palladium chloride (PdCl ₂ ), the molar ratio of palladium chloride (PdCl ₂ ): reducing agent is preferably about 1.0: 0.1 to 1.0: 50, and 1.0: 0. About 5 to 1.0: 30 is more preferable, and about 1.0: 0.8 to 1.0: 10 is more preferable.

The conditions for the reduction reaction are not particularly limited as long as the effects of the present invention are not hindered. For example, the reaction temperature is usually from room temperature (about 20 ° C.) to the vicinity of the boiling point of the solvent (± 10 ° C.). The vicinity of the boiling point of (± 10 ° C.) is preferred. For example, when water is used as the solvent, when the solvent is water, the heating temperature is more preferably about 90 to 110 ° C., and the boiling temperature (100 ° C. ± 5 ° C.) is particularly preferable. The reaction time is not particularly limited, but is preferably about 1 minute to 5 hours, more preferably about 5 minutes to 3 hours.

Refrigerate if heated after the reduction reaction. The temperature after cooling is not particularly limited, but is preferably about room temperature (5 to 35 ° C.). Thereafter, in order to remove impurities from the obtained catalyst metal fine particle-containing solution (X), ion exchange of the catalyst metal fine particle-containing solution (X) is performed with an ion exchange resin. The ion exchange resin is not particularly limited as long as the effect of the present invention is not hindered, and a commercially available product can be used.

In the step (A), a reaction accelerator may be further used. The reaction accelerator is not particularly limited as long as the effect of the present invention is not hindered. For example, alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium hydroxide; sodium carbonate, potassium carbonate, Examples include alkali metal carbonates such as cesium carbonate and lithium carbonate; alkaline earth metal salts such as calcium hydroxide; ammonia and the like. These may be used alone or in combination of two or more.

The amount of the reaction accelerator used is not particularly limited as long as the effect of the present invention is not hindered, but the catalyst: reaction accelerator = 1.0 in terms of molar ratio with respect to the catalyst contained in the catalyst metal fine particle-containing solution (X). Is preferably about 0.01 to 1.0: 10, and more preferably about 1.0: 0.1 to 1.0: 5.0 from the viewpoint of easier control of the particle size. More preferably, it is about 0.5 to 1.0: 3.0. For example, when the catalyst is palladium chloride (PdCl ₂ ), the molar ratio is preferably palladium chloride (PdCl ₂ ): reaction accelerator = 1.0: 0.01 to 1.0: 10, preferably 1.0: 0. About 1 to 1.0: 5.0 is more preferable, and about 1.0: 0.5 to 1.0: 3.0 is more preferable. The amount of the reaction accelerator used is, for example, preferably about reducing agent: reaction accelerator = 1.0: 0.001 to 1.0: 10 in molar ratio with respect to the reducing agent. Is more preferably about 1.0: 0.01 to 1.0: 5.0, and further preferably about 1.0: 0.05 to 1.0: 3.0.

[Step (B)]
In the step (B) (catalyst-supported carrier production step), the catalyst-supported carrier (Y) that supports the catalyst metal fine particles on the surface by bringing the catalyst metal fine particle-containing solution (X) obtained in the above-mentioned step into contact with the carrier. Get. The contact method is not particularly limited as long as the effect of the present invention is not hindered, and examples thereof include a method of adding and mixing a support to the catalyst metal fine particle-containing solution (X).

The carrier used in this step may be subjected to an etching treatment using a surfactant or the like, but an electroless plating base material having sufficient adhesion can be obtained without it.

In step (B), it is preferable to further disperse the catalyst metal fine particle-containing solution (X) and the carrier after contacting them. The method of the dispersion treatment is not particularly limited as long as the effect of the present invention is not hindered, and a generally used method can be adopted. Examples of the dispersion processing method include ultrasonic processing. The conditions for ultrasonic treatment are not particularly limited as long as the effects of the present invention are not hindered, and for example, 20 kHz or more is preferable.

In step (B), the solution obtained after the contact or, if necessary, the solution obtained after dispersion may be subjected to solvent removal and / or drying treatment. The method of solvent removal and / or drying treatment is not particularly limited, and a known method can be adopted. Moreover, you may perform a grinding | pulverization process following the said solvent removal and / or a drying process. The method of pulverization is not particularly limited, and a known method can be adopted.

Furthermore, if necessary, sintering (sintering) treatment may be performed to adjust the particle size of palladium. The sintering conditions can be appropriately adjusted according to the target average particle diameter of palladium, and are not particularly limited as long as the effects of the present invention are not hindered. For example, about 100 to 500 ° C. is preferable, and 120 to 300 is preferable. More preferably, the temperature is about 150 ° C., more preferably about 150 to 250 ° C. The sintering time can be appropriately adjusted according to the target average particle diameter of palladium, and is not particularly limited as long as the effects of the present invention are not hindered. For example, about 10 minutes to 24 hours is preferable, and 30 minutes to About 20 hours is more preferable. Further, the sintering is preferably performed in a vacuum state.

[Step (C)]
In the step (C) (mixing step), the catalyst support (Y) obtained in the step (B) and the binder polymer (Z) are mixed. Thereby, the electroless plating base material of the present invention can be prepared.

The solvent used for the mixing in the step (C) is not particularly limited as long as the effect of the present invention is not hindered. For example, water; alcohols such as isopropanol; organic acids such as acetic acid; benzene, toluene, xylene, ethylbenzene, Aromatic hydrocarbons such as 1,2-dichlorobenzene; ethers such as tetrahydrofuran and diethyl ether; ketones such as acetone, ethyl methyl ketone, isobutyl methyl ketone, and cyclohexanone; chloroform, dichloromethane, 1,2-dichloroethane, and the like Halides; aliphatic hydrocarbons such as n-hexane, n-heptane and cyclohexane; amides such as N, N-dimethylformamide and N, N-dimethylacetamide; N-methyl-2-pyrrolidone and the like can be used. These solvents may be used alone or in combination of two or more.

The conditions at the time of mixing are not particularly limited as long as the effects of the present invention are not hindered. Depending on the type of the binder polymer (Z), if necessary, it may be heated while stirring. The heating temperature is not particularly limited as long as the effect of the present invention is not hindered. The upper limit of the heating temperature may be about the boiling point of the solvent −20 ° C.

Since the method for producing an electroless plating base material of the present invention does not use a binder polymer and a carrier when palladium fine particles are formed, the particle diameter of the target palladium fine particles can be easily controlled.

Further, as another embodiment of the present invention, a plated laminate can be mentioned. The plated laminate of the present invention will be described below.

FIG. 1 shows the microstructure and the laminated structure of the plating underlayer in one embodiment of the plated laminate of the present invention. A plating laminate 4 shown in FIG. 1 is composed of a base layer 1 formed of a base layer polymer, the electroless plating base agent, and an electroless plating base layer 2 stacked on the base layer. An electroless metal plating layer 3 laminated on the base layer and formed by electroless metal plating, and a catalyst support for supporting catalyst metal fine particles 222 on the surface of the carrier 221 on the surface of the electroless metal plating layer 3 side. The carrier 22 has an exposed portion.

In the plating base layer of the plating laminate 4 of the present invention, an embodiment in which the catalyst supporting carrier 22 supporting the catalyst metal fine particles 222 on the surface of the carrier 221 is dispersed in the binder polymer 21 is preferable. In this case, between the base layer 1 and the plating base layer 2, the base layer polymer and the binder polymer (Z), that is, the polymers are in close contact with each other. Therefore, the adhesion between the base layer and the plating base layer can be improved. In the plating underlayer, the method of dispersing the catalyst-supporting carrier 22 in the binder polymer 21 is to bring the above-mentioned electroless plating undercoat that has been subjected to dispersion treatment such as ultrasonic treatment into contact with the base layer (for example, immersion) , Coating and the like) method.

In the plating laminate, the plating underlayer has a portion where the catalyst-supporting carrier is exposed on the surface on the metal plating layer side. And at the time of plating formation of the metal plating layer, since the electroless metal plating is deposited with the catalyst metal of the catalyst carrier (Y) exposed on the surface of the plating base layer as a nucleus, the space between the catalyst metal and the electroless metal plating is , Bonded by a metal bond. Moreover, the part which is not exposed on the surface among the catalyst support | carrier (Y) exposed on the surface of the plating base layer is being fixed to the binder polymer (Z). Therefore, the adhesion between the plating base layer and the metal plating layer can be improved. Even when the second metal plating layer is laminated on the metal plating layer by further applying electrolytic metal plating or electroless metal plating, the plating layers are in close contact with each other. Can be secured.

In the plated laminate, the base layer can be formed in a cylindrical shape, for example. In addition, for example, the base layer can be formed in a roll shape on the outer periphery of the shaft body. The base layer can be composed of one layer or two or more layers. The base layer may be obtained by laminating a base layer polymer on a metal plate such as an aluminum plate, if necessary.

In the case of having a cylindrical base layer, examples of the base layer polymer used for the base layer include polyamide imide resins, modified polyamide imide resins, polyimide resins, modified polyimide resins, polyether sulfone resins, fluorine resins, polycarbonate resins, and the like. Examples include those obtained by blending a polysiloxane compound with a resin. These may be used alone or in combination of two or more. Moreover, these can use a commercial item. The base layer polymer preferably contains at least one selected from the group consisting of a polyamideimide resin, a modified polyamideimide resin, a polyimide resin, a modified polyimide resin, and a blend of these resins with a polysiloxane compound. Is preferred. Examples of the modified polyamideimide resin include silane-modified polyamideimide resin; siloxane-modified polyamideimide. This is because the rigidity of the cylindrical base layer is increased, which is advantageous for improving the durability of the plated laminate.

As the polysiloxane compound, a silicone oil having a repeating structure represented by the following formula (1) can be suitably used. In this case, it is easy to improve the bending durability and toughness of the plated laminate. This is because an island phase made of a polysiloxane compound is micro-dispersed in a sea phase made of a resin such as the polyamide-imide resin, so that a sea-island structure is easily formed. This is thought to be mitigated. The blend amount of the polysiloxane compound is preferably about 0.01 to 10 parts by mass, and more preferably about 0.1 to 5 parts by mass with respect to 100 parts by mass of the resin. This is because the plating laminate has an excellent balance of bending durability and toughness.

(In the formula, R ¹ and R ² are the same or different and each represents a hydrogen atom or an organic group. N represents a positive integer.)

In the formula (1), the organic group represented by R ¹ and R ² is not particularly limited, and examples thereof include alkyl groups having 1 to 15 carbon atoms such as a methyl group and an ethyl group; Examples include alkoxy groups; phenyl groups; amino groups; epoxy groups; carboxyl groups; ether groups. The repeating unit n in the formula 1 is not particularly limited as long as it is a positive integer, but preferably n = 10 to 1,000, and particularly preferably n = 20 to 300. The silicone oil is not particularly limited, but straight silicone oil or the like in which a methyl group, a phenyl group, a hydrogen atom or the like is bonded as a substituent can be suitably used from the viewpoint of cost.

In the cylindrical base layer, additives such as a flame retardant, a filler, a leveling agent, and an antifoaming agent may be included. These may be used alone or in combination of two or more. The thickness of the cylindrical base layer is preferably about 20 to 200 μm, more preferably about 40 to 150 μm, and further preferably about 60 to 100 μm, from the viewpoint of improving durability and ease of manufacture.

On the other hand, in the case of having a roll-shaped base layer, as the base layer polymer used for the base layer, various resins and rubbers (in the present invention, rubber includes an elastomer, hereinafter omitted) can be used. Examples of the resin include polyamideimide resin; polyamide resin; polyimide resin; urethane resin; urethane silicone resin; (meth) acrylic resin; (meth) acrylic silicone resin; fluororesin (for example, polytetrafluoroethylene (PTFE), Perfluoroalkoxyalkane (PFA), perfluoroethylene propene copolymer (FEP), ethylene-tetrafluoroethylene copolymer (ETFE), tetrafluoroethylene-perfluorodioxole copolymer (TFE / PDD), polyvinylidene fluoride (PVDF), Polychlorotrifluoroethylene (PCTFE), ethylene-chlorotrifluoroethylene copolymer (ECTFE), polyvinyl fluoride (PVF), etc.); acetal resin; alkyd resin; Stell resin (eg, polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), etc.); polyether resin (eg, poly Etherimide (PEI); Polyethersulfone (PES); Polyetherketone (PEK), Polyetheretherketone (PEEK), Polyetherketoneketone (PEKK), Polyetheretherketoneketone (PEEKK), etc. Aromatic polyether ketone having two or more); carbonate resin (for example, polycarbonate having carbonate skeleton (—O—C (═O) —O—), etc.); polyvinyl alcohol; polyvinyl pyrrolide Cellulosic resins (eg, carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, etc.); polyacrylamide; polyethylene oxide; polyethylene glycol; polypropylene glycol; polyvinylmethyl ether; polyamines (eg, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, Aliphatic amines having at least two amino groups bonded thereto such as spermidine, spermine, putrescine; alicyclic polyamines such as isophoronediamine; polyethyleneimine; olefin resins (eg, polyethylene, polypropylene and other olefinic monomers) Isomers (eg 1-butene, 2-methyl-1-butene, 3-methyl-1-butene, pentene, hexene, cyclohexane Copolymers such as xene, 4-methyl-1-pentene, vinylcyclohexane, octene and other aliphatic olefin monomers having 10 or less carbon atoms)); polyvinyl chloride resin; polystyrene, acrylonitrile-styrene copolymer resin (SAN), styrene resins such as acrylonitrile-butadiene-styrene copolymer (ABS resin), vinyl chloride-vinyl acetate copolymer resin, polyvinyl acetal resin (for example, polyvinyl butyral resin); polyisobutylene; polytetrahydrofuran; Polyaniline, polydienes (eg, polyisoprene, polybutadiene, etc.); polysiloxanes (eg, dimethylpolysiloxane, etc.); polysulfones (PSF); polyacetic anhydrides; polyureas; polysulfides (eg, diisopropyldisulfane, Aliphatic sulfides such as methyltrisulfane); polyphosphazenes; aliphatic polyketones; polyhaloolefins; melamine resins, and derivatives or modified products thereof (modified groups include amino groups, epoxy groups, carboxy groups) Hydroxyl group, polyether group, epoxy alkyl group, epoxy polyether group, alkyl group having 1 to 6 carbon atoms, siloxane group, etc.). Among these, polyamideimide resin; polyamide resin; polyimide resin; urethane resin; urethane silicone resin; (meth) acrylic resin; (meth) acrylic silicone resin; fluororesin; polyester resin; polyvinyl alcohol; One or more selected from the group consisting of olefin resins are preferred. Examples of the rubber include silicone rubber (Q), acrylonitrile-butadiene rubber (NBR), butadiene rubber (BR), styrene-butadiene rubber (SBR), butyl rubber (IIR), chloroprene rubber (CR), hydrin rubber ( ECO, CO), isoprene rubber (IR), urethane rubber (U), ethylene-propylene-diene rubber (EPDM), natural rubber (NR) and the like. These may be used alone or in combination of two or more. Moreover, these can use a commercial item.

In the roll-shaped base layer, additives such as a flame retardant, a filler, a crosslinking agent, a crosslinking aid, a lubricant, a plasticizer, a softening agent, and an antioxidant may be included. These may be used alone or in combination of two or more. The thickness of the roll-shaped base layer is preferably about 0.5 to 3 mm, more preferably about 1 to 1.5 mm, from the viewpoint of grounding property, cost, and the like.

In the plating laminate, the plating underlayer has an important role for improving the adhesion between the base layer and the electroless metal plating layer. The plating base layer is laminated on the base layer. Specifically, the plating base layer can be formed along the outer peripheral surface of the base layer. The plating base layer is composed of the plating base agent.

The plating base layer has a portion where the catalyst-supporting carrier (Y) is exposed on the surface on the electroless metal plating layer side. This means that the catalyst carrier (Y) dispersed in the plating base layer and the catalyst carrier (Y) exposed on the surface can be mixed without being exposed on the surface. . Therefore, it does not mean that all the catalyst-supporting carriers dispersed in the plating base layer must be exposed.

The amount of the catalyst-supporting carrier exposed on the surface is not particularly limited, but the catalyst-supporting carrier (Y) exposed on the surface is scattered almost uniformly on the surface of the plating underlayer. It is preferable. This is because the electroless metal plating can be uniformly deposited starting from the catalyst metal supported on the catalyst-supporting carrier (Y), so that the adhesion between the plating base layer and the electroless metal plating layer is enhanced. Further, the exposed amount of the catalyst-supporting carrier (Y) exposed on the surface is not particularly limited as long as there is a portion where the catalyst metal supported on the carrier is outside the binder polymer (Z).

In the plating base layer, the content of the catalyst-supporting carrier (Y) ensures the deposition of the electroless metal plating, improves the adhesion between the plating base layer and the electroless metal plating layer, and the like. 30 parts by mass or more is preferable with respect to 100 parts by mass of the binder polymer (Z), and 50 parts by mass or more is more preferable. In addition, the content of the catalyst-supporting carrier (Y) is 300 parts by mass or less with respect to 100 parts by mass of the binder polymer (Z) from the viewpoints of excellent flexibility of the plating base layer, saturation of the additive effect, economy, and the like. Is preferable, and 200 mass parts or less is more preferable.

Further, the thickness of the plating base layer is not particularly limited as long as the effect of the present invention is not hindered. However, it becomes easy to ensure sufficient adhesion between the base layer and the electroless metal plating layer, and it becomes easy to ensure layer formability. From the viewpoint of the above, 1 μm or more is preferable, and 2 μm or more is more preferable. In addition, the thickness of the plating underlayer is preferably 30 μm or less, more preferably 20 μm or less, from the viewpoints of shortening the layer formation time and economy.

The plating laminate is preferably such that the base layer polymer and the binder polymer (Z) contain the same type of polymer. In this case, the affinity between the base layer and the plating base layer is increased, and the adhesion between the base layer and the plating base layer is easily improved. Preferably, the base layer polymer and the binder polymer (Z) may be the same type of polymer. The “same kind” means not only the case where the polymers are exactly the same, but also the case where the polymers have the same basic skeleton. Therefore, for example, it can be said that various resins classified into a certain type of resin (polyamideimide resin or the like) are the same type of polymer. Various rubbers classified into a certain type of rubber (silicone rubber, etc.) can be said to be the same polymer. In addition, unmodified polymer and modified polymer, polymers having different molecular weights, polymers having a common polymerization unit, and the like are also included in the concept of the same type of polymer.

When the same kind of polymer is used, as the base layer polymer, a polyamideimide resin, a modified polyamideimide resin, a polyimide resin, a blend of these resins with the polysiloxane compound, or the like can be suitably used. Examples of the modified polyamideimide resin include silane-modified polyamideimide resin; siloxane-modified polyamideimide. This is because there are advantages such as excellent strength, heat resistance and flexibility in the case of a cylindrical shape (belt shape). On the other hand, as the binder polymer, a polyamide-imide resin, a modified polyamide-imide resin, a polyimide resin, or a blend of these resins with the polysiloxane compound can be suitably used. This is because there are advantages such as affinity with the base layer polymer, affinity with a carrier made of a carbon-based material described later, and excellent heat resistance.

In the plating laminate, the electroless metal plating layer is a layer capable of functioning as a heat generating layer that generates heat by electromagnetic induction heating together with a single metal plating layer or a second metal plating layer described later. Moreover, it is a layer which can be made to function as an electrode at the time of laminating | stacking the 2nd metal plating layer mentioned later. The electroless metal plating layer is laminated on the plating base layer. Specifically, the electroless metal plating layer can be formed along the outer peripheral surface of the plating base layer.

Examples of the metal forming the electroless metal plating layer include Cu, Ni, Ag, Pd, Sn, Au, and alloys thereof. The catalytic activity for the above-described catalytic metal (particularly Pd), the plating underlayer, and the like Ni and Ni alloys are particularly preferable because of their advantages such as excellent adhesion. These may be used alone or in combination of two or more.

The thickness of the electroless metal plating layer is to ensure adhesion with the plating base layer, from the viewpoint of easily functioning as an electrode when forming the second metal plating layer described later by electrolytic metal plating, 0.1 μm or more is preferable, and 0.2 μm or more is more preferable. Moreover, when laminating the 2nd metal plating layer mentioned later, the thickness of an electroless metal plating layer is 2 micrometers or less from viewpoints of crack suppression at the time of a deformation | transformation of a plating laminated body, shortening of layer formation time, etc. 1 μm or less is more preferable. Further, the thickness of the electroless metal plating layer is preferably 30 μm or less, and more preferably 25 μm or less, when a second metal plating layer described later is not laminated.

In the plating laminate, a second metal plating layer formed by electrolytic metal plating or electroless metal plating may be further laminated on the electroless metal plating layer. The second metal plating layer is a layer that can function as a heat generation layer that generates heat mainly by electromagnetic induction heating. Examples of the metal that forms the second metal plating layer include Cu, Ni, Ag, Au, Sn, Zn, and alloys thereof, and the like. Cu and Cu alloys are particularly preferable because they have advantages such as excellent economy. These may be used alone or in combination of two or more.

When it has a 2nd metal plating layer, it becomes easy to select the metal seed | species different from the metal which forms an electroless metal plating layer, or to select thickness different from an electroless metal plating layer. Therefore, the freedom degree of the structure of the metal plating layer in a plating laminated body improves. Therefore, for example, by selecting a metal having a lower electrical resistance than the electroless metal plating layer, there is an advantage that heat is easily generated by electromagnetic induction heating. Further, by forming the second metal plating layer to be thicker than the electroless metal plating layer, there is an advantage that heat is easily generated by electromagnetic induction heating. In addition, since it becomes adhesion | attachment of plating layers between an electroless metal plating layer and a 2nd metal plating layer, favorable adhesiveness is securable. Therefore, if the adhesion between the base layer and the electroless metal plating layer is ensured, the second metal plating layer hardly peels from the base layer.

The second metal plating layer is laminated on the electroless metal plating layer. Specifically, the second metal plating layer can be formed along the outer peripheral surface of the electroless metal plating layer. The second metal plating layer can be composed of one layer or two or more layers. When the second metal plating layer is composed of a plurality of layers, each layer may be formed from either electrolytic metal plating or electroless metal plating. Each layer may be formed from the same metal or may be formed from different metals. Moreover, the thickness of each layer can also be distributed appropriately.

The thickness of the second metal plating layer is preferably 3 μm or more, more preferably 5 μm or more from the viewpoint of easily ensuring the function as the heat generating layer. In addition, the thickness of the second metal plating layer is preferably 30 μm or less, more preferably 20 μm or less, from the viewpoints of flexibility, heat generation in a short time, shortening of the layer formation time, and the like.

The use of the plated laminate is not particularly limited, and can be used to heat various objects to be heated. The plated laminate can be used, for example, as a fixing member in an electrophotographic image forming apparatus. At this time, the electroless metal plating layer or the metal plating layer may be a heat generation layer that generates heat by electromagnetic induction heating. In this case, since the adhesiveness of the heat generating layer is excellent and peeling or the like hardly occurs, the durability of the plated laminate is excellent. Therefore, a good image can be formed over a long period of time even when used in a state of being pressed against a pressure roll or the like. Examples of the image forming apparatus include a copying machine, a printer, a facsimile machine, a multifunction machine, and a POD (Print On Demand) apparatus that employ an electrophotographic system.

In the method for producing a plated laminate of the present invention, for example, a plating base layer forming material containing a binder polymer (Z) and a catalyst-supporting carrier (Y) is applied in a layered manner on the surface of a base layer formed from a base layer polymer. A step of removing the binder polymer (Z) from the surface of the formed coating layer, exposing the catalyst-supporting carrier (Y) to form a plating base layer, and electroless formation on the surface of the formed plating base layer Applying metal plating to form an electroless metal plating layer. Furthermore, if necessary, a step of forming a second metal plating layer by performing electrolytic metal plating or electroless metal plating on the electroless metal plating layer can be added. According to the said manufacturing method, the plating laminated body of the said structure can be obtained. Furthermore, it is not necessary to perform a complicated plating pretreatment process during the production. Therefore, it is possible to contribute to the downsizing of the production line, and the productivity is excellent.

The method for manufacturing the plated laminate will be described more specifically. When the base layer is cylindrical, the base layer forming material (coating agent) is applied to the outer peripheral surface of a cylindrical or columnar mold and dried. If necessary, heat treatment can be performed. Examples of the coating method include a dip coating method, a dispenser coating method (nozzle coating method), a roll coating method, and a ring coating method. On the other hand, when the base layer is in the form of a roll, the base layer forming material (kneaded material) is injected into a roll mold and heat-treated. Alternatively, the base layer forming material (kneaded material) can be extruded. Thus, the base layer formed from the base layer polymer is prepared in consideration of the shape of the base layer and the like.

Next, an electroless plating base material (coating agent) containing the catalyst-supporting carrier (Y) and the binder polymer (Z) is applied to the outer peripheral surface of the base layer and dried. Heat treatment can be performed as necessary. The electroless plating base material can be manufactured by the above-described manufacturing method. The method described above can be applied to the coating method on the base layer. Specifically, a dip coating method can be selected as a coating method from the viewpoint of easy layer formation.

Next, the binder polymer (Z) on the surface of the formed coating layer is removed, and the catalyst support (Y) is exposed. Thereby, a plating underlayer can be formed. When the binder polymer (Z) can be dissolved by various solvents, the binder polymer (Z) is selectively dissolved (etched) using an appropriate solvent. Can be done. In addition, it is possible to use removing means such as blasting and polishing.

After forming the plating base layer, the electroless metal plating layer can be formed by performing electroless metal plating on the plating base layer using a conventionally known method. For example, it can be formed using a commercially available electroless plating solution. Furthermore, if necessary, the second metal plating layer can be formed by performing electrolytic metal plating on the electroless metal plating layer using a conventionally known method. For example, it can be formed using a commercially available electrolytic plating solution. Alternatively, the second metal plating layer can be formed on the electroless metal plating layer by performing electroless metal plating using a conventionally known method. Furthermore, the manufacturing method of the said plating laminated body can add the process of forming a rubber elastic layer on the electroless metal plating layer surface or the 2nd metal plating layer surface as needed. Moreover, the process of forming a surface layer can also be added to the rubber elastic layer surface as needed.

As the binder polymer (Z), for example, when water-soluble ones such as N-methoxymethylated nylon resin are used, the electroless metal plating solution is impregnated when electroless metal plating is performed. Excellent. Therefore, removal of the binder polymer (Z) can be omitted. In this case, the plating base layer is an electroless metal in which the catalyst support (Y) is dispersed in the binder polymer (Z) and is deposited on the electroless metal plating layer side by impregnation with the electroless metal plating solution. It has an impregnation layer containing plating. Therefore, the electroless metal plating contained in this impregnation layer and the electroless metal plating layer outside the impregnation layer are combined. In addition, an anchor effect by electroless metal plating in the impregnated layer is also expected. As a result, the adhesion between the base layer and the electroless metal plating layer can be improved.

The present invention includes embodiments in which the above configurations are combined in various ways within the technical scope of the present invention as long as the effects of the present invention are exhibited.

EXAMPLES Next, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples at all, and many variations are within the technical idea of the present invention. This is possible by those with ordinary knowledge.

[Example 1]
[Preparation of catalyst metal-containing raw material solution]
First, a palladium chloride solution was prepared. After dissolving 1.68 g of palladium chloride (PdCl ₂ ) (powder) in a mixed solution of 20 mL of 3.65 wt% (1 mol / L) hydrochloric acid aqueous solution and 500 mL of pure water, the volume was adjusted to 1 L with pure water. Thus, a palladium chloride solution was obtained. This was used as a 1 g / L palladium raw material solution (1 g / L-Pd raw material).

[Preparation of reducing agent solution]
As the reducing agent, sodium citrate (trisodium citrate) and tannic acid were used. Specifically, a sodium citrate solution in which sodium citrate was diluted to 10 wt% with pure water and a tannic acid solution in which tannic acid was diluted to 1.43 wt% with pure water were used. Potassium carbonate was used as a reaction accelerator. Specifically, a potassium carbonate solution in which potassium carbonate was diluted with pure water to 13.82 wt% (1 mol / L) was used.

[Step (A)]
In a 1 L round bottom flask, 200 g of a 1 g / L palladium raw material solution and 731.61 g of pure water were mixed. At this time, a small amount of 3.65 wt% (1 mol / L) hydrochloric acid solution was added to adjust the pH to 2.3. This was boiled and refluxed for 1 hour. 15 g of the sodium citrate solution, 35 g of the tannic acid solution, and 1.25 g of the potassium carbonate solution were mixed and added thereto. After these solutions were added and boiled and refluxed for 10 minutes, the flask was placed in ice water and cooled to room temperature. Thereafter, a Pd colloid particle dispersion (hereinafter referred to as “Pd colloid solution”) is obtained by ion exchange with 70 g of an ion exchange resin (Amberlite MB-1 (manufactured by Organo Corporation)) in order to remove impurities. X1) was prepared. With respect to the obtained Pd colloidal particles, the particle size distribution of 100 Pd colloidal particles observed with a transmission microscope was obtained, and the position where the volume accumulation was 50% was defined as the average particle size (D50). The average particle size of the Pd colloidal particles of this example was 10 nm.

[Step (B)]
Next, after adding carbon black (trade name: Thermax N990, average particle size: 280 nm, manufactured by cancarb) to the Pd colloid solution (X1), ultrasonic waves of 45 kHz are added. Was irradiated for 90 minutes to obtain a dispersion of fine Pd particles and carbon black. Subsequently, the dispersion was dehydrated and dried with an evaporator and then pulverized with an agate mortar to obtain Pd fine particle-supported carbon black (Y1).

[Step (C)]
Further, 2.4 g of polyamideimide resin varnish (trade name: HPC-5012, manufactured by Hitachi Chemical Co., Ltd.) and 34.9 g of N-methyl-2-pyrrolidone were added to 2.7 g of the above-mentioned Pd fine particle-supported carbon black (Y1). The mixture was stirred well to obtain a Pd-supported carbon-dispersed polyamideimide solution (electroless plating base material).

Next, a plated base layer-formed aluminum plate was obtained as follows. As a plating substrate, an aluminum plate with a thickness of 1 mm cut to a width of 25 mm and a length of 100 mm was prepared and immersed in a polyamideimide resin varnish (trade name: HPC-5012, manufactured by Hitachi Chemical Co., Ltd.) The polyamideimide resin varnish was applied to the aluminum plate by a method of pulling up at a constant speed. Next, the aluminum plate was dried at 200 ° C. to form a plating base layer to obtain a plating base layer-formed aluminum plate.

After immersing the obtained plating base layer-formed aluminum plate in the Pd-supported carbon-dispersed polyamideimide solution, the Pd-supported carbon-dispersed polyamideimide solution was applied to the aluminum plate by a method of pulling up at a constant speed. Next, the aluminum plate was dried at 200 ° C. to form a plating underlayer. The formed plating underlayer was etched by immersing in a 200 g / L NaOH aqueous solution at 40 ° C. for 10 minutes, and washed with pure water for 10 minutes. Then, it dried at 80 degreeC and obtained the aluminum plate in which the plating base layer in which Pd carrying | support carbon precipitated was formed.

For the nickel plating, an electroless plating solution (trade name: Top Piena 650 Nickel, manufactured by Okuno Pharmaceutical Co., Ltd.) was used, and the aluminum plate on which the plating base layer was formed was immersed for 60 minutes to deposit nickel plating. The degree of precipitation of nickel plating was visually confirmed and evaluated according to the following evaluation criteria. The results are shown in Table 1 below.
<Plating quality evaluation criteria>
A: The plating deposition area is 80% or more of the whole B: The plating deposition area is 50% or more and less than 80% of the whole C: The plating deposition area is 30% or more and less than 50% of the whole D: The plating deposition area is 30 %Less than

[Example 2]
In the preparation of the Pd colloid solution, the amount of pure water mixed with the palladium raw material solution was 744.94 g (pH of the solution 2.3), and the amount of sodium citrate solution used during Pd reduction was 10 g. A Pd colloid solution (X2) was prepared by the same production method.
When the average particle size of the Pd colloidal particles was determined in the same manner as in Example 1, the average particle size of the Pd colloidal particles in this example was 20 nm.
A Pd-supported carbon-dispersed polyamideimide solution was obtained in the same manner as in Example 1 except that the Pd colloid solution (X2) was used instead of the Pd colloid solution (X1) of Example 1, and the polyamideimide solution was Using, after forming a plating foundation layer, nickel plating was deposited. About the obtained nickel plating, the degree of precipitation was evaluated by the same evaluation method and standard as Example 1. The results are shown in Table 1 below.

[Example 3]
Example 1 except that the amount of pure water mixed with the palladium raw material solution was 751.75 g (pH of the solution 2.3) and the amount of sodium citrate solution used during Pd reduction was 5 g when preparing the Pd colloidal solution. A Pd colloid solution (X3) was prepared by the same production method.
When the average particle size of the Pd colloidal particles was determined in the same manner as in Example 1, the average particle size of the Pd colloidal particles in this example was 35 nm.
A Pd-supported carbon-dispersed polyamideimide solution was obtained in the same manner as in Example 1 except that the Pd colloid solution (X3) was used instead of the Pd colloid solution (X1) of Example 1, and the polyamideimide solution was Using, after forming a plating foundation layer, nickel plating was deposited. About the obtained nickel plating, the degree of precipitation was evaluated by the same evaluation method and standard as Example 1. The results are shown in Table 1 below.

[Example 4]
When preparing the Pd colloidal solution, the amount of pure water mixed with the palladium raw material solution was set to 733.25 g (solution pH 2.3), and 50 g of 2 wt% gallic acid solution was used instead of sodium citrate as the reducing agent during Pd reduction. Then, a Pd colloid solution (X4) was prepared by the same production method as in Example 1 except that 1.0 g of potassium carbonate solution as a reaction accelerator was used.
When the average particle size of the Pd colloidal particles was determined in the same manner as in Example 1, the average particle size of the Pd colloidal particles in this example was 10 nm.
A Pd-supported carbon-dispersed polyamideimide solution was obtained in the same manner as in Example 1 except that the Pd colloid solution (X4) was used instead of the Pd colloid solution (X1) of Example 1, and the polyamideimide solution was Using, after forming a plating foundation layer, nickel plating was deposited. About the obtained nickel plating, the degree of precipitation was evaluated by the same evaluation method and standard as Example 1. The results are shown in Table 1 below.

[Example 5]
The same manufacturing method as in Example 1 except that the Pd fine particle-supported carbon black of Example 1 was subjected to a heat treatment at 200 ° C. for 12 hours in a vacuum state, and the particle size of Pd was increased by sintering. A Pd colloid solution (X5) was prepared.
When the average particle size of the Pd colloidal particles was determined in the same manner as in Example 1, the average particle size of the Pd colloidal particles in this example was 35 nm.
A Pd-supported carbon-dispersed polyamideimide solution was obtained in the same manner as in Example 1 except that the Pd colloid solution (X5) was used instead of the Pd colloid solution (X1) of Example 1, and the polyamideimide solution was Using, after forming a plating foundation layer, nickel plating was deposited. About the obtained nickel plating, the degree of precipitation was evaluated by the same evaluation method and standard as Example 1. The results are shown in Table 1 below.

[Comparative Example 1]
As a carrier, 30 g of carbon black (trade name: Thermax N990, average particle size: 280 nm, manufactured by cancarb) was prepared as a carrier. This carbon black was immersed in a 60% by mass nitric acid aqueous solution at 50 ° C. for 10 minutes. Thereby, the carbon black surface was etched. Next, this was filtered and washed with water, and then immersed in an aminocarboxylic acid surfactant [Okuno Pharmaceutical Co., Ltd., “Condizer SP”] at 50 ° C. for 10 minutes. Thereby, the surface adjustment of the carbon black surface was performed. Next, this was filtered and washed with water, and then immersed in a Pd—Sn complex colloidal solution [OPC-80 Catalyst, manufactured by Okuno Pharmaceutical Co., Ltd.] at 25 ° C. for 10 minutes. As a result, the Pd—Sn complex was adsorbed on the carbon black surface. Subsequently, after filtering and washing with water, it was immersed in 10 mass% hydrochloric acid aqueous solution at 25 degreeC for 10 minute (s). This produced metal Pd on the surface of carbon black. Next, this was filtered, washed with water, and dried to obtain powdered Pd fine particle-supported carbon black (CY1). The average particle diameter of the Pd particles was determined by the same method as in Example 1. The average particle size of the Pd colloidal particles of this comparative example was 45 nm.

Next, in the same manner as in Example 1, a plating base layer made of polyamideimide resin varnish was formed on an aluminum plate. Moreover, it replaced with Pd fine particle carrying | support carbon black (Y1) of Example 1, and performed the same method as Example 1 except having performed the process (C) using the said powdery Pd fine particle carrying | support carbon black (CY1). A Pd-supported carbon-dispersed polyamideimide solution was obtained. Except that the Pd-supported carbon-dispersed polyamideimide solution was used in place of the Pd-supported carbon-dispersed polyamideimide solution of Example 1, a plating underlayer was formed by the same method as in Example 1, and then nickel plating was deposited. It was. About the obtained nickel plating, the degree of precipitation was evaluated by the same evaluation method and standard as Example 1. The results are shown in Table 1 below.

As described above, the electroless plating base material of the present invention is excellent in plating properties and by extension, in adhesion.

The electroless plating base material of the present invention is excellent in adhesion and hardly causes poor adhesion. In addition, the plating laminate using the electroless plating base material of the present invention does not have Sn ⁴⁺ remaining due to carrier aggregation or insufficient cleaning, and is less likely to cause poor adhesion due to remaining Sn ⁴⁺ . It is excellent in durability and is particularly useful when used for a heating member or the like that does not require regular replacement.

Claims (12)

1. The catalyst-supporting carrier (Y) and the binder polymer (Z) are included. The catalyst metal fine particles supported on the surface of the catalyst-supporting support (Y) include palladium fine particles, and the average particle diameter (D50) of the palladium fine particles is An electroless plating base material having a thickness of 10 nm to 43 nm.
2. The electroless plating base material according to claim 1, wherein the catalyst-supporting carrier (Y) is dispersed in a binder polymer (Z).
3. The electroless plating base material according to claim 1 or 2, wherein the palladium fine particles have an average particle diameter (D50) of 20 nm or more and 40 nm or less.
4. The carrier constituting the catalyst-carrying carrier (Y) is one or more selected from the group consisting of a carbon-based material, a metal oxide, and silica. The electroless plating base material described in 1.
5. A base layer formed of a base layer polymer, the electroless plating base layer according to any one of claims 1 to 4 and laminated on the base layer, and the plating base layer An electroless metal plating layer formed by electroless metal plating, and having a portion on the surface of the electroless metal plating layer where a catalyst-supporting carrier for supporting a catalyst metal is exposed on the surface of the carrier The plating laminated body characterized by the above-mentioned.
6. 6. The plated laminate according to claim 5, wherein a second metal plating layer formed by electrolytic metal plating or electroless metal plating is further laminated on the electroless metal plating layer.
7. The plating laminate according to claim 5 or 6, wherein the metal forming the electroless metal plating layer is one or more selected from Cu, Ni, Ag, and alloys thereof. .
8. Step (A) of reducing the catalyst metal-containing raw material solution with a reducing agent to obtain a catalyst metal fine particle-containing solution (X),
   A step (B) of obtaining a catalyst-carrying carrier (Y) carrying catalyst metal fine particles on its surface by bringing the catalyst metal fine particle-containing solution (X) obtained in the step into contact with a carrier; and
   A step (C) of mixing the catalyst-carrying support (Y) obtained in the step and the binder polymer (Z),
   The catalyst metal fine particles supported on the carrier include palladium fine particles, and the palladium fine particles have an average particle diameter (D50) of 10 nm or more and 43 nm or less. A method for producing an electroless plating base material.
9. The method for producing an electroless plating base agent according to claim 8, wherein the catalyst metal-containing raw material solution has a pH of 1.0 to 4.5.
10. 10. The method for producing an electroless plating base material according to claim 8 or 9, wherein a reaction accelerator is further used in the reduction.
11. The method for producing an electroless plating base agent according to any one of claims 8 to 10, wherein a dispersion treatment is further performed in the step (B).
12. The method for producing an electroless plating base material according to any one of claims 8 to 11, wherein the palladium fine particles have an average particle diameter (D50) of 20 nm or more and 40 nm or less.

Images