JPS61210181A - Plating method for hydraulically hardened body - Google Patents

Abstract

PURPOSE:To easily execute a hydraulically hardened body such as cement contg. Ca to electroless plating by bringing said body into contact with an aq. soln. of a metallic salt having a catalytic effect for electroless plating then dipping the body into an electroless plating liquid. CONSTITUTION:The hydraulically hardening material such as hydraulic lime, Roman cement or others contg. Ca is kneaded with water and is hardened by curing to form the hardened body having a desired shape. Fats and oils, etc., as a form stripping agent stick on the surface of such hardened body and are therefore dissolved away by acetone, etc., and are rinsed. Such body is brought into direct contact with a weak acidic soln. of a platinum metallic salt such as PdCl as a catalyst liquid by dipping or blowing, etc., to reduce PdCl, etc., by the Ca eluted from the hardened body, by which the surface film provided with catalytic activity is formed on the surface of the hardened body. The body is dipped in the electroless plating liquid of Cu, Ni, Cn, etc., or is sprayed with said liquid and the electroless plating layer is thus formed.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention is generally used in a plating method for hydraulic hardened bodies that elutes calcium ions, more specifically, in a pretreatment method for electroless plating. In order to form a catalyst film without using a catalytic reducing agent, the hydraulic cured product is brought into contact with a catalyst solution, a catalyst film is formed with the eluted calcium ions, and then electroless plating is applied to the hydraulic cured product. Regarding the plating method.

[Technical background] - Plating methods generally include electroplating and electroless plating, but electroless plating is used for non-metals such as plastics and ceramics.

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

In this electroless plating, the non-metal top surface is thoroughly cleaned to remove surface dirt and inappropriate oxides.
Pre-washing is necessary as a pre-treatment along with catalyst activation. A common pretreatment method is to immerse the substrate in a hydrochloric acid acidic colloid containing catalyst liquids stannous chloride and palladium chloride, wash it with water, and then immerse it in an aqueous hydrochloric acid solution and wash it with water. ing.

[Prior art and problems to be solved by the present invention] Generally, in electroless plating on a substrate, catalytic activity is imparted by first forming a film made of particles having catalytic properties on the surface of the substrate. do. For example, a method for plating plastics is to first etch it with a chromic acid-sulfuric acid mixture, wash it with water, then immerse it in an acidic solution of stannous chloride containing stannous chloride and hydrochloric acid, and after washing with water, catalyze the process. It is immersed in an acidic solution of a noble metal such as palladium chloride. The plastic substrate imparted with catalytic activity in this manner is placed in an electroless plating bath and plated. There is also a method in which the material is immersed in an acidic solution containing stannous chloride and palladium chloride containing hydrochloric acid, then washed with water, further immersed in a solution of hydrochloric acid, washed with water, and then subjected to thermal electrolytic plating. Even on metal substrates such as aluminum,
A similar pretreatment method is used for habo. However, if a commonly used pretreatment method is applied to a hydraulically cured material that elutes calcium ions, for example, the acidity of the etching solution may be too strong, resulting in severe calcium elution from the substrate of the hydraulically cured material, resulting in surface defects. It had drawbacks such as large deterioration. Furthermore, even if the etching treatment is performed by immersion in an acidic solution of stannous chloride without performing an etching treatment with a chromic acid-sulfur mixture, excessive calcium ions are eluted, the substrate interface is severely degraded, and palladium Since no film is formed, electroless plating does not proceed. On the other hand, in order to protect the surface of the substrate from acids, it is necessary to apply a reducing agent such as stannous chloride while the hydraulic cured material is not yet cured, and the operation is very complicated. There is.

Therefore, when performing electroless plating on hydraulic hardened bodies that elute these calcium ions, a protective film, such as a corrosion-resistant film such as plastic, is adhered and electroless plating is performed on the plastic substrate. Disadvantages include that the film is expensive, that the adhesion between the film and the hydraulic hardening material is insufficient, and that the film itself has no heat resistance, so the heat resistance as a plating layer is also insufficient. There is.

On the other hand, ceramics generally require labor to fire and process, and it is extremely difficult to obtain dog-shaped products. Therefore, it would be of great industrial value if electroless plating could be applied to a cured product that can be easily prepared and molded into different shapes, and large molded products can be obtained.

The present inventors conducted various studies on the above-mentioned problems and completed the present invention based on the knowledge that eluted calcium ions reduce palladium salts.

[Means for solving problems]

That is, the present invention involves bringing a hydraulic hardening material that elutes calcium ions into contact with a catalyst solution that forms a catalyst film for plating metal deposition, forming a catalyst film with the eluted calcium ions, and then performing electroless plating. This is a method of plating a hydraulically cured body, which is characterized by:

The present invention will be explained in detail below.

In the present invention, the calcium-containing hydraulic substances used to obtain the hydraulic hardened body that elutes calcium ions include hydraulic lime, Roman cement, natural cement, various types of Portland cement, single cements such as alumina cement, and blast furnace cements. Cement, silica cement, fly
Mixed cements such as ash cement, masonry cement, expansive cement, and colored cement; special cements such as acid-resistant cement and dental cement; and general hydraulic substances containing so-called calcium, such as blast furnace slag and gypsum. .

Further, if necessary, ultrafine powder, aggregates and other optical fillers, water reducing agents, setting retarders, decolorizing agents and other chemical admixtures can also be used.

Mixing methods for obtaining hydraulic hardened materials include mixers generally used for mixing mortar and concrete, such as mortar mixers, hand mixers, forced mixers, tilting mixers, omni mixers, and twin-shaft mixers. Examples include extrusion machines, kneaders, twin rolls, and mixers.

The curing method for obtaining a hydraulically cured product is not particularly limited, and examples include general air-dry curing, underwater curing, steam curing, autoclave curing, and heat curing.

On the other hand, the surface of the obtained cured product is preferably smooth, and the surface may be polished depending on the case. next,
A method of electroless plating on a hydraulic hardened body in which calcium ions obtained by the above operation are eluted will be described. If the surface of the cured product is coated with oils and fats such as formwork stripping agents, clean it with something that dissolves oils and water such as acetone, and then rinse with water, or remove the oils and fats with a lipophilic solvent such as trichlorethylene. Wash out and dry. Next, the cured product is immersed in a weakly acidic solution of a platinum group compound salt such as a palladium salt as a catalyst solution, or is brought into contact with the solution by spraying to form a surface film imparted with catalytic activity on the substrate surface. As platinum group compound salts, PdyRu+Rh, OstIrmPt
The most common example is palladium chloride. The detailed reason for the mechanism by which the catalyst can easily form a film on the surface of the cured product is unknown, but the general idea is as follows. When the cured body is brought into contact with the catalyst solution by immersion or spraying, first, only calcium ions are eluted from the second surface of the cured body. Next, the eluted calcium ions reduce and precipitate platinum group cations in the solution in the hardened body six times, and are themselves oxidized to form a catalyst film on the surface of the hardened body. It is believed that the above mechanism makes it possible to easily form a catalyst film on the substrate surface without using a commonly used catalyst reducing agent. Furthermore, according to this method, since the catalyst film is formed by a direct redox reaction with the substrate, it also has the advantage that the treatment time for immersion in the catalyst liquid can be shortened compared to conventional treatment methods. Further, the hydraulic hardened body containing calcium having catalytic activity obtained by the above operation is brought into contact with a plating solution by immersion or spraying, to form an electroless plating layer on the surface. As a plating counterfeit, it is possible to form steel, nickel, chromium, cobalt, soot, silver, gold, etc. which are generally used in electroless plating.

The present invention eliminates the contact process such as dipping or spraying in a general acidic catalyst reducing solution such as stannous chloride, thereby degrading the surface of the hydraulic hardening material that elutes calcium ions. The effect is found in a simple and economical electroless plating process.

The plating layer obtained by the invention has excellent physical properties such as adhesive strength, and can be used in various molds such as compression molds for plastics, transfer molds, injection molds, and extrusion molds. Molds, laminated molds, injection molds, blow molds, secondary molds and vacuum molds,
It can be used in a variety of molds, including 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〕

This will be explained in detail in Examples below.

Example 1 The surface of the obtained cured product having the composition shown in Table 1 was degreased with acetone, dried, and then electroless nickel plating was performed using each treatment method.

Write the results on the first coat.

Immediately after the electroless treatment, the plating layer was firmly adhered to all cases, but after the heat treatment, only the hydraulic hardened material was firmly adhered, and in the case of resin systems, the plating layer could be easily removed by the nail grip test method. The nickel plating layer obtained by the present invention had an extremely smooth narrow surface and good adhesive strength.

〔Effect of the invention〕

According to the above process, according to the present invention, l) A cured product to which the plating layer is firmly attached is obtained.

2) Since it is a hydraulically hardened material, it is possible to produce products with large mR.

3) A cured product with a smooth surface can be obtained.

Effects such as this can be obtained.

Patent applicant Denki Kagaku Kogyo Co., Ltd. Procedural amendment (voluntary) June 10, 1985 Director of the Patent Office Michibe Uga 1, Indication of the case 1985 Patent application No. 49245 26 Name of the invention Hydraulic hardening body Plating method 6, relationship with the case of the person making the amendment Patent applicant: 1-4-1 Yurakucho, Chiyoda-ku, Tokyo Address: 1-4-1 Yurakucho, Chiyoda-ku, Tokyo Claims column and Detailed explanation of the invention column 5 of the specification, Amendment Contents (corrected) Description 1, Name of the invention Method for plating a hydraulically hardened body 2, Claims (1) A hydraulically hardened body containing calcium is coated with an aqueous solution of a metal salt having a catalytic action for electroless plating. A method of plating a hydraulically hardened material by directly contacting it with gold and then immersing it in a plating solution to perform electroless plating.

6. Detailed Description of the Invention [Field of Industrial Application] The present invention is generally used in a plating method for a hydraulically hardened body containing calcium, more specifically, in a pretreatment process for electroless plating. The present invention relates to a plating method for a hydraulic cured body in which the hydraulic cured body is brought into direct contact with an aqueous solution of a metal salt having a catalytic action for electroless plating without using a catalytic reducing agent, and then subjected to electroless plating.

[Technical background]

Plating methods generally include electroplating and electroless plating, but electroless plating is usually used for non-gold crystals such as plastics and ceramics. Gold GT-plating is applied to the surface of a material like electroplating by applying chemical substitution and reduction of metals without using electrical energy.

It is also called electroless plating or chemical plating. That is, by forming a film made of particles that have a catalytic action for metal plating on the surface of the substrate, catalytic activity for metal plating is imparted, and further, the metal to be plated is deposited on the film, and the deposited plating metal is self-catalyzed. This action advances plating.

In this electroless plating, it is necessary to sufficiently clean the non-metallic substrate surface 111ilr and remove dirt and inappropriate oxides on the surface.Preliminary cleaning is necessary as well as catalytic activation. A common method for catalysis and activation is to immerse the substrate in an acidic colloidal solution of hydrochloric acid containing stannous chloride as a catalyst reducing agent and palladium chloride as a catalyst. Prior Art and Problems to be Solved by the Present Invention] Generally, in electroless plating on a substrate, a catalytic action is first applied to the surface of the substrate. Catalytic activity is imparted by forming a film made of particles having the following properties. For example, one method for plating plastic is to first etch it with a chromic acid-sulfuric acid mixture, wash it with water, then immerse it in an acidic solution of stannous chloride, which is a catalyst base, and hydrochloric acid, and then wash it with water. After that, the YTF plastic substrate is immersed in an acidic solution of a precious metal such as palladium chloride, which is a catalytic solution.The YTF plastic substrate, which has been given catalytic activity in this way, is immersed in an electroless plating bath to perform plating. Also, after immersing in an acidic bath solution containing stannous chloride and palladium chloride acid, it is washed with water.
Furthermore, there is also a method of immersing the material in a solution of 4 acids, rinsing with water, and then performing electroless plating.

Generally, palladium, which is a catalyst, does not show catalytic action in its ionic state, but is said to show catalytic action when it is reduced by stannous chloride, which is a catalyst reducing agent, and takes an atomic state on the substrate surface. Similar catalytic activity has been imparted to gold-14 substrates such as aluminum. However, if the commonly used method of imparting catalytic activity is applied to a hydraulically cured body containing calcium, for example, the etching solution is too acidic, resulting in severe erosion of the substrate of the hydraulically cured body and surface deterioration. There are some drawbacks such as a big friend. Furthermore, even if the etching treatment is performed without etching using a chromic acid-sulfuric acid mixture and by immersion in an acidic solution of stannous chloride, the surface of the substrate is severely degraded and the palladium film of the catalyst is not formed on the surface of the substrate. Similarly to φ, in which electroless plating does not proceed, even if the salts of stannous chloride and palladium chloride are applied from acidic #l' [containing unoxidized acid], the surface of the substrate deteriorates rapidly, and the catalyst does not form on the surface of the nucleus plate. Electroless plating does not proceed because a palladium film is not formed.On the other hand, in order to protect the surface of the substrate from acid, a catalyst such as stannous chloride or the like can be removed while the hydraulically hardened material is not yet cured. ″
The disadvantage is that it requires a coating process and the operation is very complicated. Ninth, when performing electroless plating on these hydraulic hardened bodies containing calcium, a corrosion-resistant film such as a protective film, such as plastic, is attached, and then electroless plating is performed, but the corrosion-resistant film Disadvantages include that the coating is expensive, that the adhesion between the coating and the hydraulic hardening material tends to be insufficient, and that the core coating itself has insufficient heat resistance as a plating layer. Yes.

In addition, ceramics generally require labor to fire and process, and it is extremely difficult to obtain large-sized molded products.Therefore, hydraulic curing, which can be easily prepared, can be molded into different shapes, and can produce large-sized molded products, is used. If electroless plating can be easily performed on the body, industrial 111ir [expansion] would be possible.

The inventors of the present invention have investigated various problems mentioned above, and have found that electroless plating is possible by directly contacting a catalyst liquid to a hydraulic hardening body containing calcium without using a TST base agent. Based on this knowledge, we have completed the present invention.

[Means for solving problems]

That is, in the present invention, a hydraulic hardening body containing calcium is brought into direct contact with an aqueous solution of a metal salt having a catalytic action for electroless plating, and then immersed in a plating solution to perform electroless plating. This is a method of plating a hydraulically cured body, which is characterized by:

The present invention will be explained in detail below.

Hydraulic substances for obtaining the calcium-containing hydraulic hardened body (hereinafter referred to as hardened body) in the present invention include hydraulic lime, a-man cement, natural cement, Rutland cement, alumina cement, etc. Single cement, blast furnace cement, silica cement, fly ash cement, masonry cement, expanded cement and mixed cement such as colored cement, special cement such as acid resistant cement and grade 1 cement, as well as blast furnace slag, Examples include common hydraulic substances containing so-called calcium such as gypsum. Also, if necessary, ultrafine powder, aggregates and other fillers, water reducing agents, setting retarders, antifoaming agents and other chemical admixtures or admixtures may be used. Materials can also be used.

Mixing methods for obtaining a hardened product include mixers generally used for mixing mortar and concrete, such as mortar mixers, hand mixers, forced mixers, I'T mixers, omni mixers, knee mixers, etc., and extrusion. Examples include methods using a machine, kneader, twin meal, Banbury mixer, etc.

The curing method for obtaining a cured product is not particularly limited, and examples include general air-dry curing, underwater curing, steam curing, autoclave curing, and heat curing.

On the other hand, it is preferable that the surface of the obtained cured product is smooth, and surface polishing may be performed depending on the case. Let me explain in detail. If oils such as formwork stripping agents are attached to the surface of the cured product, clean it with oils and fats such as A7Tone or something that dissolves water, and then rinse with water, or use a lipophilic solvent such as trichlorethylene. Dry all pre-wash lines to wash out oil and fat. Next, the cured product is immersed in a weakly acidic solution of a nickel metal salt such as a palladium salt as a catalyst solution, or is brought into contact with the solution by spraying to form a surface film imparted with catalytic activity on the substrate surface.

Examples of platinum metal salts include ruthenium (Ru), rhodium (Rh), palladium (Pd), Osmira A (O
s) *Iridium (rr), platinum (pi), and the most common one is palladium chloride. The detailed reason for the mechanism by which the catalyst can easily form a film on the surface of the cured product is unknown, but the general idea is as follows. When the cured body is brought into contact with the catalyst liquid by immersion or spraying, first, calcium f7) is electrically discharged from the surface of the cured body. This calcium causes 111 tl of platinum ion t- in #1 g to precipitate on the surface of the hardened body, and is oxidized to form a catalyst film on the surface of the hardened body. It is believed that the above mechanism makes it possible to easily form a catalyst film on the substrate surface without using a commonly used catalyst reducing agent. Furthermore, according to this method, since the catalyst film is formed by a direct oxidation modification reaction with the substrate, there is also the advantage that the treatment time for immersion in the catalyst liquid can be shortened compared to conventional treatment methods. Furthermore, the hardened material that has calcium aK that increases the catalytic activity obtained by the above procedure is added to the plating solution. ii! Contact is made by dipping or spraying plating m to form an electroless plating layer on the surface. As the plating metal, it is possible to use steel, nickel, chromium, cobalt, soot, silver, gold, etc., which are commonly used in electroless plating.

In addition, Azao3, SiC, diamond, and PTF'E (Po
1ytetrafluoroethylene) and the like is also an OT function.

Furthermore, after performing these electroless platings, by utilizing the conductivity of the electroless plating layer, the present invention can be used to replace the conventional IR catalyst such as stannous chloride, which is more effective than steel or chives. The effect is found in simple and continuous electroless plating without deteriorating the surface of the hardened material containing calcium, by eliminating all contact processes such as immersion or spraying in the agent. It is.

The plating layer obtained by the present invention has various physical properties such as adhesive strength.
It has excellent properties and is used in various molding fields, such as compression molding molds for plastics, transfer molding molds, injection molding molds, extrusion molding molds, lamination molding molds, cast molding molds, and blow molding. Molds, secondary molding molds and vacuum forming,
We use press molds for metals, various types of molds for glass and ceramics, and various other products such as panel boards for magnetic shielding, panel boards for building materials, decorative items, and various stands. Usable.

〔Example〕

This will be explained in detail in Examples below.

Example 1 The surfaces of the cured products and resin-based cured products obtained with the compositions shown in Table 1!1 were degreased with acetone, dried, and then electroless plated with nickel using each treatment method.

The results are shown in Table 1.

^ A fS
Hane: :'''mM噌-1''l-0 切 田 連 1) As is clear from the table 1), immediately after electroless plating, the plating layer was firmly adhered to A, but there was a feeling of heat ＠ After that, only the cured product remained firmly attached, and the plating layer of the resin-based cured product was easily peeled off by the nail holder test method.

The nickel plating layer obtained according to the present invention had an extremely smooth surface and good contact strength.

Actual INAIP112 Table of ornaments with reserve shape [Fi is plated under the various conditions shown in Table 1!2 The results are also listed in Table @2.

As is clear from Table 2, the plating peeled off immediately after electroless plating on the A and BS@fat hardened products, but on the hardened products, the nickel electroless plating, 81C$I electrolytic plating, and chromium electrolytic plating layers peeled off, regardless of the substrate. Even after the 1g4-interval contact with the substrate, the layer remained firmly in contact with the substrate, no surface peeling was observed, and no peeling was observed even by the nail grip test method.

〔Effect of the invention〕

As described above, according to the present invention, 1) A cured product to which the plating layer is firmly attached can be obtained.

2) Since it is a hydraulically cured product, it can be made into a large @naked product.

3) A cured product with a smooth surface can be obtained.

Effects such as this can be obtained.

Claims (1)

[Claims] (1) Bringing a hydraulic hardening body that elutes calcium ions into contact with a catalyst liquid that forms a catalyst film for depositing plated metal,
After forming a catalyst film with the eluted calcium ions,
A method of plating a hydraulic hardening material, which is characterized by performing electroless plating.