JPS61210182A - Electroless plating method of hydraulically hardened body - Google Patents

Abstract

PURPOSE:To subject a dense hydraulically hardened body consisting essentially of a cement material and water to electroless plating by bringing said body into contact with a catalyst liquid for forming a catalytic film to form the catalytic film thereon then dipping the body into an electroless plating liquid. CONSTITUTION:0.5-5wt% water-reducing agent such as formaldehyde condensation product of beta-naphthalene sulfonic acid as well as aggregate and water are kneaded with 60-95pts.wt. cement such as Portland cement and 5-40pts.wt. ultrafine particles such as silica dust or flyash. Or <=30wt% hydrophilic high- polymer compd. such as carboxymethylcellulose and water are kneaded with the cement and the mixture cured to form the hardened body having <=30% voids. The deposits such as fats and oils are removed by acetone and the hardened body is rinsed and dried. The body is then dipped into an aq. soln. of a platinum group metallic salt such as Pd salt to form the film having catalytic activity on the surface. The body is dipped in the electroless plating liquid of Cu, Ni, etc., by which the electroless plating film is formed.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for electroless plating of a hydraulically cured body, and more particularly to a method for electroless plating of a dense hydraulically cured body.

[Technical background]

Plating methods generally include electroplating and electroless plating, and electroless plating is used for nonmetals such as plastics and ceramics.

In general, electroless plating on a substrate involves forming a film made of particles with catalytic properties on the surface of the substrate to impart catalytic activity, and then depositing the metal to be plated on top of the film, and depositing the deposited plating metal. Plating progresses through autocatalytic action.

In this electroless plating, preliminary cleaning to thoroughly clean the nonmetallic surface and remove dirt and unsuitable oxides on the surface is required as a pretreatment as well as imparting catalyst activity.

A common pretreatment method is to immerse the substrate in a hydrochloric acid acidic colloidal solution containing the catalyst liquid stannous chloride and radium chloride, wash it with water, and then immerse it in an aqueous hydrochloric acid solution and wash it with water. is used.

Specifically, for example, in the case of non-metallic plastics, the plastic surface is first etched with a chromic acid-sulfuric acid solution, then washed with water, immersed in an acidic solution of stannous chloride containing stannous chloride and hydrochloric acid, and then etched again. After washing with water, it is immersed in an acidic solution of a salt of a platinum group compound such as radium chloride, which is a catalyst solution. Electroless plating is performed by placing the plastic substrate, which has been made to have catalytic activity through such pretreatment, into an electroless plating bath.

[Prior art]

Conventionally, when applying the commonly used pretreatment method to a hydraulically cured body and directly performing electroless plating, the surface of the hydraulically cured body is immersed in the strong acid of the pretreatment liquid, and the palladium is removed by the catalyst liquid. There was a drawback that a platinum group compound catalyst film such as the above was not formed and electroless plating was not possible. Methods to solve these drawbacks include applying an acid-resistant resin coating to the surface of the hydraulically cured material and further plating the resin coating surface with metal, or applying a reducing agent such as stannous chloride to the hydraulically cured material. Methods such as applying it to the body while it is still uncured are used.

However, these methods also have drawbacks such as the heat resistance and adhesive properties of the resin coating and the need for a complicated process of coating the surface of the uncured hydraulic cured product.

[Problem that the invention seeks to solve]

As a result of extensive research to solve the above problems, the inventors of the present invention have found that the hydraulic hardening material can be made into a dense material.
The present invention was completed based on the knowledge that plating becomes possible.

[Means to solve the problem]

Partly, the present invention provides a method for plating a hydraulically hardened body consisting of a composition mainly composed of cementitious material, ultrafine powder, water reducing agent, aggregate, and water, which contains a platinum group compound that forms a catalyst film for metal deposition. After contacting with catalyst liquid to form a catalyst film,
This is an electroless plating method for a hydraulic hardened body, which is characterized by performing electroless plating.

The present invention will be explained in detail below.

The dense hydraulic hardened body of the present invention is composed of, for example, a cementitious material, an ultrafine powder, a water reducing agent, an aggregate, and water.
Moreover, it is composed of a cementitious material as a main component, a hydrophilic polymer compound (hereinafter simply referred to as a polymer), and water. [The pore volume fraction (hereinafter referred to as total porosity) of a dense hydraulic hardened material is determined by the amount of cementitious material, ultrafine powder, water reducing agent,
When it consists of aggregate and water, it is 30 degrees or less, and when it consists of a cementitious substance as a main component and consists of a polymer and water, it is 10 degrees or less.

Hydraulic hardened bodies with such a small porosity have high strength, high surface hardness, and good surface smoothness, and when electroless plating is performed, the metal plating condition is good and the plated film is Even if the material is thin, smoothness is easily obtained, and a dense metal-plated hydraulic cured product with good adhesive strength can be obtained.

The cementitious materials used in the present invention include various Portland cements such as normal, early strength, super early strength, white, etc., mixed cements containing fly ash, slag, etc., and alumina cements, as well as expandable mixtures. It is also possible to add materials.

The ultrafine powder used in the present invention has an average particle size that is at least one order of magnitude lower than the cementitious material described above;
In particular, those having an average particle size two orders of magnitude lower are preferable from the viewpoint of fluidity characteristics of the kneaded product. The most suitable ultra-fine powder is silica dust (silica fume) and siliceous dust, which are produced as by-products when manufacturing silicon, silicon-containing alloys, zirconia, etc. In addition, calcium carbonate, silica gel, opalescent silica, fly ash, etc. Slag, titanium oxide,
Ultrafine powders such as aluminum oxide can also be used. In particular, the use of ultrafine powder obtained by pulverizing opalescent silica, fly ash, and slag using a jet mill equipped with a classifier is effective in improving hardening shrinkage. The amount of ultrafine powder used is preferably 5 to 40 parts by weight based on 60 to 95 parts by weight of the cementitious material, and more preferably 10 to 35 parts by weight based on 65 to 90 parts by weight of the cementitious material. If it is less than 5 parts by weight, there is no effect of reducing the porosity, and if it exceeds 40 parts by weight, the fluidity of the mixed material will be markedly reduced, resulting in poor workability.

The water reducing agent used in the present invention can be any commonly used one, but it is a condensation agent of β-naphthalene sulfonate which has a large dispersion ability and does not cause too much delay in condensation or excessive air entrainment even when added in a large amount. It is preferable to use high-performance water reducing agents such as melamine sulfonate, condensate of melamine sulfonate, and lignin sulfonate and polycarboxylate, which have a large amount of high molecular weight components among lignin sulfonate.

The amount of the water reducing agent to be used is 0.5 to 5 parts by weight as solids per 100 parts by weight of the cementitious material and ultrafine powder. The water reducing agent is necessary to obtain a kneaded product with a low water-cement ratio, and if it is used in an amount exceeding 5 parts by weight, it will adversely affect the curing reaction. The amount of water reducing agent used reduces the ratio of water to cementitious material and ultrafine powder,
Even if the porosity is set to 30 cm or less, mortar or concrete with workable fluidity can be obtained by a conventional method.

The water used in the present invention will be explained. In the case of a dense hydraulic hardened body consisting of cementitious material, ultrafine powder, water reducing agent, aggregate and water, the amount of water used should be the same as that of cementitious material and ultrafine powder in order to reduce the porosity to 30 or less. 30 weight or less is preferable, and from the viewpoint of fluidity considering workability,
10 to 30% by weight is more preferable, and in the case of a dense hydraulic hardened body consisting of a cementitious material as a main component and a polymer and water, in order to make the porosity 201 or less, 20 weight - or less is preferred.

The polymers used in the present invention include carboxymethyl cellulose, hydroxyethyl cellulose, hydroxyethyl methyl cellulose, hydroxyglobil methyl cellulose, hydroxybutyl methyl cellulose, polyethylene oxide, acrylamide-acrylic acid copolymer e polyacrylamide, styrene- Maleic anhydride copolymer, polyvinyl alcohol, etc. can be used. The amount of polymer used is 30% by weight or less, preferably 3-20% by weight, based on the cementitious material.

The aggregate may be those conventionally used in the preparation of general mortar and concrete, but hard ones are effective in significantly improving strength. For example, silica, emery, pyrite, magnetite, yellow jade, lawsonite, corundum, zenasite autospinel, beryl,
All curb stones, tourmaline, granite, andalusite, cross stone, zircon,
Calcined bauxite, boron carbide, tungsten carbide, ferrosilicon nitride, silicon nitride, fused silica, fused magnesia. Examples include silicon carbide, cubic boron nitride, and the like.

Dense hydraulic cured product of the present invention (hereinafter simply referred to as cured product)
The kneading method for obtaining this is achieved by using mixers that are generally used for kneading mortar and concrete, such as mortar mixers, hand mixers, forced kneading mixers, tiltable mixers, omnimixers, twin-screw mixers, and extruder mixers. Kneader, twin roll, Banbury mixer.

There are no special restrictions on the method of molding the cured product, but in general, casting, injection molding, vacuum or pressure molding, centrifugal molding, instant release molding,
Spraying includes molding, and these various molding methods may be combined, or other methods may also be used. Furthermore, a vibratory compaction method in which vibration is applied to various molding methods for molding is even more preferable.

There are no particular restrictions on the curing method, and water curing, air curing, steam curing, heat curing, pressure curing, autoclave curing, etc. can be used, and it is also possible to use a combination of these.

Next, the plating method of the present invention will be explained.

In the plating method of the present invention, pre-cleaning is performed in which oils and fats adhering to the surface of the cured product are washed out with a solvent (eg, acetone, trichlorethylene, etc.), washed with water, and dried.

Removal of fats and oils is carried out because, for example, fats and oils that adhere during molding of the cured product tend to deteriorate the adhesion of the plating.

Conditions for removing oil and fat must be selected depending on the state of adhesion, the type of solvent, etc.

Next, catalyst activity is imparted. That is, for example, contact is performed to form a film having catalytic activity of a platinum group metal such as palladium on the plated surface of the cured product, and the film is washed with water.

The molding conditions for this film are not particularly limited;
For example, a film imparted with catalytic activity can be formed by contacting for 1 to 5 minutes at room temperature.

The concentration of water-soluble salts of platinum group compounds such as palladium salts is not particularly limited, but is usually 0, OO1 mol/
About 1 to 0.002 mol/1 is used. In addition, in order to stabilize the water-soluble salt of the platinum group compound such as this palladium salt in an aqueous solution, an acid such as hydrochloric acid was added at I x 101 mol/
It is also possible to mix and use it to some extent.

The electroless plating according to the present invention can perform plating of copper, nickel, cobalt, tin, silver, gold, platinum group metals, nickel alloys, cobalt alloys, and other alloys. Plating conditions vary depending on the properties of the plating bath and the plating thickness, and are not particularly specified, but steel plating is usually carried out at room temperature, and nickel plating is carried out at 70 to 100°C.

As described above, the method of the present invention not only etches with a chromic acid-sulfuric acid solution, which is normally required, but also etches in an acidic solution of stannous chloride containing stannous chloride and hydrochloric acid, which is used as a reducing agent for palladium chloride. It has been discovered that electroless plating can be performed by omitting the immersion step and simply immersing the material in a solution of a platinum group compound such as palladium salt to form a platinum group film such as palladium that imparts catalytic activity. Formation of films with catalytic activity of platinum group metals such as palladium is achieved by reducing platinum group compound salts such as palladium salts using stannous chloride as a reducing agent, and forming films by precipitation of platinum group metals such as palladium. When the cured product of the invention is used as a substrate, calcium ions eluted from the surface of the cured product act as a reducing agent and reduce platinum group compound salts such as palladium salts to precipitate platinum group metals such as palladium to form a film.

The metal-plated hardened body of the present invention can be used for various oak moldings, such as compression molding molds for plastics, transfer molding molds, extrusion molding molds, injection molding molds, injection molding molds, blow molding molds, and secondary molding molds. It can be used in various fields such as laminated molds, compression molds for metals, various molds for glass and ceramics, panel boards for electromagnetic shielding, panel boards for building materials, decorative items, and various stands. .

〔Example〕

The present invention will be explained below with reference to Examples.

Example 1 Knead with a mixer using the formulation shown in Table 1, φ2×5
Each specimen was molded under vacuum suction, and one day later, it was cured in pure water at 20° C. for 7 days. After curing, drying was performed at 105°C to create a cured product. This hardened product is made to have a constant weight, and its weight in air (A) is then completely filled with water by boiling, and its weight in water (B) and weight in air (C) are
was measured, and the porosity was determined from the following formula. The results are also listed in Table 1.

Porosity (4) = ((C)-(4))/(B)X100
Table 1 Cement: Ordinary Portland cement) (Kikagaku Kogyo)
(manufactured by Elkem) Water reducing agent: Cellflow R155 (manufactured by Dai-ichi Kogyo Seiyaku ■) Example 2 In the experiment, silica sand was used in the same weight as the cement and ultrafine powder in the formulations of 461 and 10, and the same weight as that of Example 1 was used. A cured product was prepared in the same manner. Electroless plating was performed using this cured body as a substrate using the pretreatment liquid shown in Table 2. The results are also listed in Table 2. The plating metal was nickel, the electroless plating solution was diluted to the standard dilution rate (catalog value) under the trade name "Kanigen Blue Schumer", and electroless plating was performed at 70° C. for 3 hours. In addition, each pretreatment method involved cleaning with trichlorethylene for degreasing, and then immersing it in the following solution.

The liquid used for pretreatment is as follows.

Solution A: 10 f of stannous chloride and 40 g of hydrochloric acid were diluted with water to make 1 t.

B solution: Palladium chloride 0.25? , 2.5-hydrochloric acid was diluted with water to make 1 t.

Liquid C: Palladium chloride commercially available pre-treatment liquid, Nippon Kanigen ■
Red Schemer Juk liquid: commercially available colloidal pre-treatment liquid of stannous chloride and palladium chloride, Hitachi Chemical Hs-10113J standard solution E: Hitachi Chemical commercially available as a cleaning solution. “A.D.
From the results of the p-20113J standard solution, the nickel-plated cured product with good plating conditions by the plating method of the present invention was a good substrate that did not peel off even in the nail polishing test.

Example 3 100 parts by weight of alumina cement (Denka Alumina Cement No. 1 J manufactured by Denki Kagaku Kogyo ■) was mixed with 8 parts by weight of polyvinyl alcohol (Popal B-24SJ manufactured by Kagaku Kogyo ■), and 11 parts by weight of water was added. Add 5 parts and twin roll
Mixed for a minute.

Take out a 2ms sheet and heat it at 120℃ for 10 minutes at 50℃.
After pressing under surprising conditions and curing at 50°C for 7 days, a substrate for electroless plating was obtained. The porosity of the obtained substrate was 0.8%
Met. Using this substrate, electroless plating was performed in the same manner as in Example 2, except that the pretreatment liquid shown in Table 3 was used.

The results are also listed in Table 3.

Table 3 □ From the above results, a dense nickel-plated cured product was obtained which had a good plating condition and did not peel off even in the nail pick test.

Example 4 A cured substrate prepared by adding silica sand to the experimental AIO formulation of Example 2 was immersed in an electroless plating bath for copper plating and plated with copper according to the pretreatment shown in Table 4. The electroless solution for copper plating contains 29 f/l of copper sulfate, 25 f/l of sodium carbonate, and 140 f/l of potassium sodium tartrate.
Electroless plating was performed at 20° C. for 1 hour using a solution of 4 Qf/l of sodium hydroxide and 37 thiformin 150-1. The results are also listed in Table 4.

From the results shown in Table 4, the plating method according to the present invention obtained good results. Furthermore, the copper-plated film on the cured product was a copper-plated layer with adhesive strength that did not peel off even in the nail pick test.

〔Effect of the invention〕

When the plating method of the present invention is used, the only acids that are expected to attack the surface of the cured product are acidic solutions of salts of platinum group compounds such as palladium salts, and etching with chromic acid-sulfuric acid, which attacks the substrate of the cured product, and , the immersion step in an acidic solution of stannous chloride is omitted. In addition, since the acid concentration of the acidic solution of platinum group compound salts such as palladium salts is used in the pretreatment process, the acid concentration is the lowest, and since a film is directly formed on the substrate by palladium precipitation, contact with the acid is also short. It becomes possible to directly metal plate without damaging the surface of the cured product.

In summary, the present invention has the following effects.

1. A hardened body with high compressive strength and high bending strength can be obtained.

2. A cured product with good surface conditions such as smoothness and no unevenness can be obtained.

3. A product with strong surface hardness can be obtained.

4. Good plating is now possible, making it possible to use it for extrusion molding of deaf parts, electromagnetic shielding materials, and other applications not found in conventional concrete products.

Patent Applicant Denki Kagaku Kogyo Co., Ltd. Procedural Amendment June 11, 1985 Commissioner of the Patent Office Michibe Uga 1, Case Description 1985 Patent Application No. 50317 2, Name of Invention No Hydraulic Curing Body Electrolytic plating method 6, relationship with the case of the person making the amendment Patent applicant address: 1-4-1 Yurakucho, Chiyoda-ku, Tokyo 1-4-1, Chiyoda-ku, Tokyo Claims column and detailed description of the invention column 5 of the specification, amendment Whether or not to amend the detailed statement of contents in attached (corrected) statement 9.

However, the name of the invention remains unchanged.

(Correction) Description 1, Name of the invention Electroless plating method for hydraulically hardened body 2, Claims (1) A dense hydraulically hardened body consisting of a mixture whose main components are a cement substance and water, An electroless plating method for a hydraulically hardened material, which involves directly contacting a catalyst solution containing a platinum group metal to form a catalyst film for plating metal deposition, forming a catalyst film, and then performing electroless plating.

3. Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a method for electroless plating of a hydraulically cured body, and more particularly to a method for electroless plating of a dense hydraulically cured body.

[Technical background]

Plating methods generally include electroplating, electroless plating, and plating, but electroless plating is usually used for nonmetals such as plastics and ceramics.

In general, electroless plating on a substrate involves forming a film made of particles with catalytic action on the surface of the substrate, imparting catalytic activity to the metal plating, and then depositing the metal to be plated on top of the film, and depositing the deposited plating. Plating progresses through the autocatalytic action of the metal.

In this electroless plating, pre-cleaning to thoroughly clean the surface of the non-metallic substrate and remove dirt and unsuitable oxides from the surface is required as a pre-treatment as well as imparting catalytic activity.

A general method for imparting catalytic activity is to immerse the substrate in a salt/acid colloid solution containing stannous chloride as a catalytic reducing agent and palladium chloride as a catalyst, wash it with water, and then immerse it in a hydrochloric acid water bath. A method of soaking and washing with water is used.

Specifically, for example, in the case of non-metallic plastics, first chromic acid-sulfur a! Etch the plastic surface with a solution, wash it with water, immerse it in an acidic solution containing tin oxide and hydrochloric acid, wash it again with water, and immerse it in an acidic bath solution of a platinum group metal salt such as palladium chloride. . Electroless plating is performed by immersing a plastic substrate, which has been made catalytically active through such pretreatment, into an electroless plating bath.

[Prior art and its problems]

In the past, when applying commonly used pretreatment methods, especially catalytic activation, to a hydraulically cured body and performing direct thermal plating, the surface of the hydraulically cured body would be attacked by the strong acid of the catalytic reducing agent solution. However, there was a drawback that a platinum group metal catalyst film such as palladium was not formed by the catalyst solution, and electroless plating was not possible. Methods to solve these drawbacks include applying an acid-resistant resin to the surface of the hydraulically cured material and then plating the formed resin film with metal, or adding a catalytic reducing agent such as stannous chloride to the water. Methods such as applying the hard cured product while it is still uncured are used.

However, these methods also have drawbacks such as the heat resistance and adhesive properties of the resin film and the need for a complicated process of coating the surface of the uncured hydraulic cured product.

As a result of various studies in order to solve the above problems, the present inventors found that by making the hydraulic hardened body dense using a specific material and bringing it into direct contact with the catalyst liquid without using a catalyst reducing agent. After obtaining the knowledge that plating becomes possible, the present invention was completed.

[Means to solve the problem]

That is, the present invention provides a method for directly applying a dense hydraulically cured body made of a mixture mainly composed of cement and water to a catalyst solution containing a platinum group metal that forms a catalyst film for depositing plated metals. This is an electroless plating method for a hydraulically cured material, which is characterized in that electroless plating is performed after contacting to form a catalyst film.

The present invention will be explained in detail below.

The dense hydraulic cured body (hereinafter referred to as cured body) of the present invention is
It consists of a mixture (compound) whose main components are cementitious material, ultrafine powder, water reducing agent, aggregate, and water. It consists of a compound (compound) consisting of molecules (referred to as molecules) and water. The pore volume fraction (hereinafter referred to as porosity) of the cured product is 60% or less in the case of Blend I, and 10% or less in the case of Blend I.

In this way, a cured product with a small 9f& ratio has high strength, high surface hardness, and good surface smoothness, and when electroless plating is performed, the metal plating state is good and the plated film is Even if it is thin, smoothness can be easily obtained, and adhesive strength is also good.

The cementitious materials used in the present invention include various Portland cements such as ordinary-early strength, ultra-early strength, and white, mixed cements containing fly ash, blast furnace slag, etc., and alumina cements, as well as expansive admixtures. It is also possible to add materials.

The ultrafine powder used in the present invention has an average particle size that is at least one order of magnitude lower than the average particle diameter of the cementitious material described above. It is preferable from the aspect. As this ultrafine powder, silica dust (silica hume) and silica hawk dust, which are by-produced during the production of silicon, silicon-containing alloys, zirconia, etc., are particularly suitable, and calcium carbonate.

Silica sol, opal negative silica, fly ash.

Ultrafine powders such as blast furnace slag, titanium oxide, and aluminum oxide can also be used. In particular, the use of ultrafine powder obtained by pulverizing opalescent silica, fly ash, or blast furnace slag using a jet mill equipped with a classifier is effective in improving hardening shrinkage.

The amount of ultrafine powder to be used is preferably 5 to 40 parts by weight per 1,460 to 95 parts by weight of the cementitious material. ffli parts, more preferably 65 to 90'N parts of cementitious material,
The amount is 10 to 35 parts by weight, and if it is less than 5 parts by weight, the effect of reducing the porosity will be small, and if it exceeds 40 fE parts, the fluidity of the kneaded product will decrease and the workability will deteriorate.

As the water reducing agent used in the present invention, commonly used ones can be used, but even when added in a large amount, β-naphthalene sulfone #! does not cause excessive delay in setting or excessive sudden entrainment, and has a high dispersion ability. It is preferable to use a high-performance water reducing agent such as a formaldehyde condensate of I salt, a condensate of melamine sulfone #i-hanawa, a lignin sulfonate containing a large amount of high molecular weight components among lignin sulfonates, and a polycarboxylate.

The amount of water reducing agent used is 0 as solid content per 100 parts by weight of the cementitious material and ultrafine powder (hereinafter referred to as powder 5).
．． 5 to 5 parts by weight is preferred. The water reducing agent is necessary to obtain a kneaded product with a low water-cement ratio, and if it is used in an amount exceeding 5 parts by weight, it will adversely affect the curing reaction. As described above, even if the porosity is reduced to 30% or less by using ultrafine powder and a water reducing agent, it is possible to obtain mortar or concrete with operable fluidity by the usual method.

The water used in the present invention will be explained. In the case of formulation I, in order to make the porosity 30% or less, the amount of water used is preferably 30% by weight or less based on the powder, and from the viewpoint of fluidity considering workability, the amount of water used is 10 to 30% by weight. % is more preferred. Further, in the case of a compound seal, in order to make the porosity t-20% or less, it is preferably 20% by weight or less based on the cementitious material.

Examples of polymers used in the present invention include carboxymethyl cellulose and hydroxyethyl cellulose.

Examples include hydroxybutyl methyl cellulose, hydroxypropyl methyl cellulose, hydroxybutyl methyl cellulose, polyethylene oxide, acrylamide-acrylic acid copolymer, polyacrylamide, styrene-maleic anhydride copolymer, and polygenyl alcohol.

The amount of polymer used is 30% by weight based on the cementitious material.
The following is preferable, and 3 to 20 MIk% is more preferable.

The aggregate may be those conventionally used in the preparation of general mortar and comfleet, but harder aggregates are effective in significantly improving the strength of the cured product. For example, silica fist emery, pyrite, magnetite, yellow jade, lawsonite, corundum, fenacite tosvinel,
Beryl, full curb stone, tourmaline, granite, andalusite, cross stone - zircon, calcined bauxite, boron carbide, tungsten carbide, ferrosilicon nitride, silicon snow, fused silica, fused magnesia, silicon carbide and cubic crystals Examples include boron chloride.

The mixing method for obtaining the hardened product of the present invention can be carried out using mixers generally used for mixing mortar and concrete, such as mortar mixers, hand mixers, forced mixers, tilting mixers, omni mixers, and twin-shaft mixers. ,
There are extruders, kneaders, twin rolls, Banbury mixers, etc.

There are no particular restrictions on the method of molding the cured product, but there are general molding methods, injection molding, vacuum or pressure molding, centrifugal molding for adult pigs, molding for spraying, and combinations of these six molding methods. This is also possible, and other methods are also possible. Furthermore, it is even more preferable to use a vibration compaction method in which each material is molded by applying vibration.

There are no particular restrictions on the curing method, and water curing, air curing, steam curing, heat curing, pressure curing, autoclave curing, etc. can be used, and combinations thereof are also possible.

Next, the plating method of the present invention will be explained.

In the plating method of the present invention, as a pretreatment, first, oils and fats adhering to the surface of the cured product are washed out with a solvent (eg, acetone, trichlorethylene, etc.), followed by washing with water and drying.

Removal of fats and oils is carried out because, for example, fats and oils that adhere to the cured product during molding tend to reduce the activation activity of the plating.

Conditions for removing oil and fat must be selected depending on the state of adhesion, type of solvent, etc.

Next, catalytic activity enrichment is performed. That is, for example, the cured product is immersed and/or plated in a water-bathable salt of a platinum group metal such as palladium salt, and then contacted by spraying or the like to impart the catalytic activity of the platinum group metal such as palladium to the plated surface of the cured product. The resulting film is molded and washed with water.

The molding conditions for this film are not particularly limited;
For example, a film imparted with catalytic activity can be formed by contacting for 1 to 5 minutes at room temperature.

The concentration of water-soluble salts of platinum group metals such as palladium salts is not particularly limited, but is usually o, o o i to 0-0.
02 moV1 is used. Further, in order to stabilize the water-soluble salt of the platinum group metal such as the palladium salt in a water bath, it is also possible to mix hydrochloric acid or the like in an amount of about 1 x 10-'rno'l/no.

In the electroless plating according to the present invention, porcelain, nickel, cobalt, tin, silver, gold, platinum group metals, nickel alloys, cobalt alloys, and other alloys can be used.

In addition, A-203, SiO, diamond, and PTF are contained in the matrix of these metals as composite particles.
(Polytetraf1uoroethlene)
It is also possible to carry out total eutectoid analysis. Furthermore, after performing electroless plating, metals such as copper, nickel, chromium, zinc, gold, gold alloys, silver, and tin can be plated using the conductivity of the electroless plating layer. Of course it is also possible. Electroless plating conditions vary depending on the type I of the plating bath and plating thickness, and are not particularly specified, but usually hook plating is at room temperature, and nickel plating is at 70-100°C.
It is done in C.

As described above, the method of the present invention not only eliminates the normally required etching with a chromic acid-sulfuric acid solution, but also eliminates the step of immersing the etching in an acidic solution of stannous chloride and hydrochloric acid, which are used as catalyst reducing agents for palladium chloride. It was discovered that a film of a platinum group metal such as palladium that imparts catalytic activity is formed by simply immersing the plate in a platinum group metal salt bath solution such as a palladium salt, and electroless plating can be performed. The formation of a film with catalytically active gold of a platinum group metal such as palladium is achieved by reducing a platinum group metal salt such as a palladium salt using stannous chloride as a catalytic reducing agent, and forming a film by precipitation of a platinum group metal such as palladium. When the cured product of the present invention is used as a substrate, calcium eluted from the surface of the cured product acts as a reducing agent, reduces platinum group metal salts such as palladium salts, precipitates platinum group metals such as palladium, and forms a film. .

The metal-plated cured body of the present invention can be used in various molding molds, such as plastic press molding molds, transfer molding molds, extrusion molding molds, injection molding molds, cast molding molds, blow molding molds, secondary molding molds, etc. Laminate molds, compression molds for metals, various molds for glass and ceramics, etc.
It can be used in various fields such as panel boards for electromagnetic shielding, panel boards for building materials, decorative items, and various types of stands.

〔Example〕

The present invention will be explained below with reference to Examples.

Example 1 Mix MIAF) in a mixer using the formulation shown in Table 1, and
The specimen of 2 x 5 cm was molded under vacuum suction, and after 1 day 2
It was cured in pure water at 0°C for 7 days. After curing, drying was performed at 105°C to create a cured product. This hardened material has a constant mass,
x-iiiitA)i in the air at this time, then the pores are completely filled with water by the boiling method, and its weight in water (B)
and air mf[(Ole) were measured, and the porosity was determined from the following formula.The results are also listed in Table 1.

Porosity T%)-((Ct)-(A))/(Bl×100
Table 1〈Materials used〉 Cement Nijintsu Portland Cement (“Kikagaku Kogyo-M”) Ultrafine 15’J Nijiri Kahiyum (Elkem Co. Ltd. water reducing agent: “Cellflow R155J (manufactured by Dai-ichi Kogyo Seiyaku ■) =
Example 2 A cured product was prepared in the same manner as in Example 1 using the same weight of silica dust, cement and ultrafine powder in the formulations of Tests 1 and 10. Electroless plating was performed using this cured body as a substrate using the pretreatment liquid shown in Table 2. The results are also listed in Table 2. The plating metal is nickel, and the electroless plating solution is manufactured by Nippon Kanizen (product name: Kazen Prussumer).
2) Dilute the product to the standard dilution ratio (catalog value) and heat at 70°C.
Electroless plating was performed under conditions of , 6 hours. In each pretreatment method, the sample was washed with trichlorethylene for degreasing, and after drying the surface, it was immersed in six pretreatment solutions for 5 minutes.

After immersion in each liquid, all samples underwent a water washing process before being immersed in the next liquid.

Part 2! I The liquid used for pretreatment was as follows.

Liquid: dilute 10 g of stannous chloride and 40 m of hydrochloric acid with water.
It was.

Solution B: 0.25 g of palladium chloride, 2.5 alt hydrochloric acid
- Diluted with water to 1 concentration.

Liquid C: palladium chloride commercially available pretreatment liquid, Nippon Kanigen m
5tr Red Shamer" standard solution: commercially available colloidal pretreatment solution of stannous chloride and palladium chloride, Hitachi Chemical's "Hs-10113J standard solution E solution: Hitachi Chemical's "Ap" commercially available as a cleaning solution.
From the results of the p-20113j standard solution, the nickel-plated cured product with good plating condition by the electroless plating method of the present invention was a good substrate that did not peel off even in the nail scratch test.

Example 3 Polyvinyl alcohol (manufactured by Denki Kagaku Kogyo ■, trade name "Popal B-
24EIJ) were mixed in powder form, 11 parts by weight of water was added, and the mixture was mixed for 5 minutes using twin rolls.

Take out 211111 in sheet form and heat at 120° for 10 minutes.
A substrate for electroless plating was obtained by pressing under the conditions of 50° C.9/2 false and curing at 50° C. for 7 days. The porosity of the obtained substrate was 0.8%. Using this substrate, electroless plating was performed in the same manner as in Example 2, using the pretreatment liquid shown in Table 3, except for the following. The results are also listed in Table 6.

From the results shown in Table 6, a dense nickel-plated cured product was obtained which had a good plating condition and did not peel off even in the nail pick test.

Example 4 A cured substrate prepared by adding silica sand to the mixture of Experiment 10 of Example 2 was immersed in the pretreatment liquid shown in Table 4 and an electroless plating solution for copper plating, and copper plating was performed. . The electroless solution for copper plating contains 29 II/l of steel sulfate, 25 da/l of sodium carbonate, 140 J/l of potassium sodium tartrate, 409/l of sodium hydroxide, and 37% holv+.
) y 150 m, electroless plating was carried out using a liquid at 20° C. for 1 hour. The results are also listed in Table 4.

From the results shown in Table 4, the plating method according to the present invention yielded good results. Further, the cured product was plated with copper, and the copper plating layer had a strong adhesive strength that did not peel off even in the nail scratch test.

Example 5 An AB8 resin injection molded product (a steering wheel horn for a car) was molded into a round shape using ffi, which was plated in various ways on the surface of a cement mold. The composition of the cement mold at that time, the molding conditions of the cement mold,
The molding results of resin molded products are shown in Tables 5, 186, and 7, respectively.

Table 5 (parts by weight) White cement: Silica hume manufactured by Chichibu Cement ■Water reducer manufactured by Japan Heavy and Chemical Industry ■...
"Self 0-110PJ (*- Manufactured by Kogyo Seiyaku ■) Iron powder/
・・"Dowa Iron Powder" (manufactured by Dowa Iron Powder Industry ■) Particle size 150μ~
44μm 1175 parts by weight, particle size 3ml~150μm
751L quantity Steel fiber... Steel fiber by chatter cutting, length 20 (Kobe Foundry Works ■ I [Effect of the invention]) When the plating method of the present invention is used, acids that are expected to attack the surface of the hardened product are Only an acidic solution made of a salt of a platinum group metal such as a palladium salt is used, and the etching process with chromic acid-sulfuric acid, which attacks the most cured substrate, and the step of immersion in an acidic solution of stannous chloride can be omitted.

In addition, since the acid concentration of the acidic solution of palladium-nose platinum group metal salt is used in the pretreatment process, the lowest eI! Since it is an ITs degree and a film is directly formed on the substrate by precipitation of palladium, contact with metal is short and it is possible to directly metal plate without damaging the surface of the cured product.

In summary, the present invention has the following effects.

1. A plated cured body with high compressive strength and high bending strength can be obtained.

Z A cured product with good surface conditions such as smoothness and no unevenness can be obtained.

6. A product with strong surface strength can be obtained.

4. Since good plating is now possible, it can be used as extrusion molds, #1L-wave shielding materials, and other applications not found in conventional concrete products.

Claims (1)

[Claims] (1) A hydraulically hardened material consisting of a composition mainly composed of cementitious material, ultrafine powder, water reducing agent, aggregate, and water is added to a catalyst liquid containing a platinum group compound that forms a catalyst film for depositing plated metal. An electroless plating method for a hydraulically cured material, characterized in that electroless plating is performed after contacting to form a catalyst film.