TW200530430A - Conductive electrolessly plated powder and method for making the same - Google Patents

Abstract

Provided is one type of conductive electrolessly plated powder of plated film with capability of improving heat tolerance and method for making the same. A conductive electroless plated powder of this invention includes a nickel film formed by an electroless plating process on the surface of each core particle. Its characteristic lies in that: crystal grain boundaries in the nickel film mentioned above are primarily oriented in the direction of the thickness of the nickel film. An electroless gold plating film may be deposited on the nickel film as the top layer. The nickel film is formed by electroless plating using glycine or ethylenediamine as a complexing agent.

Description

200530430 The original words of the five-square leather precious layer are stable before the invention. Description of the invention (1) The technical field to which the invention belongs The present invention relates to a conductive method; more specifically, a powder for electrolytic coating of a Soviet and its manufacturing film Conductive electroless plating, high-heat-resistant plating blades for high-heat-resistant coatings, and a method for manufacturing the same. Prior art] The applicant first proposed: use a core metal powder of 1 f resin for personal metal capture surface treatment agents. The second metal ion that is subjected to the electroless plating treatment in the liquid is charged into the core material powder to perform the electroless recording session, and is referred to as a so-called bath-building method I in the synthetic resin method (refer to Patent Document 1). Agents, complexing agents, buffering agents, stabilizing layers f require metal salts, and also have the so-called solution for improving the coating for coatings, the method of the method; the heart of this application: the stringent: various layer requirements The performance is qualitatively determined. At the end of 4 years ... In addition to the consistency, it is also required to be at high temperature. Patent Document 1] Japanese Patent Publication No. 6 1-64882 Patent Document 2] Japanese Patent Publication No. 1-242782 [ Ming content]

200530430 V. Description of the invention (2) Therefore, the object of the present invention is to provide a powder for conductive electroless plating having a coating for improving heat resistance and a method for producing the same. The present inventors conducted a thorough review, and as a result, they thought that the structure of the film for forging described in Patent Document 1 can be formed, that is, a structure different from the fine metal particles to a dense and substantial continuous film structure. Films with different structures achieve the stated purpose. The present invention is to provide a powder for conductive electroless plating, and to form a nickel film on the surface of a core material particle by an electroless plating method, characterized in that the grain boundary in the nickel film is based on the nickel film. Mainly oriented in the thickness direction; in order to achieve the aforementioned purpose. _ In addition, the present invention is to provide a powder for conductive electroless plating layer = manufacturing method, which is characterized in that: the aforementioned core which imparts the capturing energy of precious metal ions by ^, energy or surface treatment with precious metal ions, The material powder soil captures precious metal ions, and then reduces this so that the aforementioned precious metal is carried on the surface of the seventh heartwood powder. Then, the core material powder is dispersed and mixed with nickel ions, a reducing agent, and an amine compound. The initial thin film forming solution of the complexing agent reduces nickel ions, and forms an initializing film on the surface of the core material powder, and then, the aqueous suspension containing the core material powder and the complexing agent forming the initial film is suspended in water. Body, separately and simultaneously adding two kinds of liquids containing nickel ion liquid and reducing agent liquid containing the same type of complexing agent to the complexing agent to perform electroless plating reaction; as the aforementioned conductive electroless vessel layer The ideal manufacturing method of powder 'in order to achieve the aforementioned purpose 0 7082-6219-PF (N2); Ahddub.ptd Page 6

200530430 V. Description of the invention (3) [Embodiment] The following is a description of the invention according to the ideal implementation mode of the 5th generation, while referring to the invention. The powder for conductive electroless plating of the present invention (hereinafter, also referred to as a powder for plating) is formed on the surface of the core material powder, and a nickel film is formed by a favorable layer method. The nickel film formed on the surface of the core material powder is the grain boundary in the nickel film, and the nickel film is mainly oriented in the thickness direction. That is, the crystal system in the #film mainly has a columnar structure extending in the thickness direction of the film. The direction of the thickness of nickel 3: 0 ::: Guang Fang toward the film can be obtained visually by observing a scanning electron microscope (hereinafter also referred to as SEM). == 之 = From ㈣ to 10000 (3 times the magnification to look at 2 = in the cross section 'in the observation extended in the direction of the thickness of the film ^ direction. Under the great sadness, it can be said that the crystal grain boundary is mainly oriented In the thick phase of the moon, the surface will show: the powder of the mineral layer of the present invention-the rate is _ 0 times. It is composed of many columnar structures clearly shown in Figure 1. In Figure 1, each column = The ancient sound of the Λ / Λ columnar structure ^, t 酼 is a method of forming the nickel film and is also produced in a high state. In addition, it is also possible: J: I is relatively large in its inverted shape. The other is cut The shape of a large cone or the powder product for electroless nickel plating shown in Figure 2), the section in the thickness direction of the nickel film ^ The magnification is 50 °

boundary. It is clearly shown from FIG. 1 that this series is made of a nickel film of powder for the coating of Gu Yueyue without any gaps and densely, forming a dense and homogeneous continuous film. Many columnar patterns in the direction On the other hand, the nickel powder of the coating powder is homogeneous. It is known from the examples described later that the film-based crystal particles become thicker and become a review: 1 shown in FIG. 1 clearly shows that by the inventors the thermal properties become higher, even in the case of high-temperature bars having a columnar structure. The nickel film is the conductivity of the body. It ’s not easy to lower the powder for plating. Observe the powder for plating with SEM.

The example is the same as above, the order of the coating film is-81 5 (manufactured by Japan Epoxy Resin Co., Ltd.) 丨 ^ Epicure (Epicurea) (Japanese ring Z multiples and Part, limited by the company's dryer) 5 weight X 1 Omm X 2mm sample, into the tester: Harden the part for 1 Omi to bend and crack, and use SEM to feed. Rupture of the membrane used for viewing noise 3

The present inventors performed the X π ice present measurement / invention. The nickel coating of the powder for coating was in addition to the crystalline substance.

There is a part of non-crystalline material, which is usually mixed in the crystal knife = external state. In addition, the crystalline morphology of the nickel film is in the crystal grain boundaries of the present invention, and if it has a columnar structure, the required heat resistance is found regardless of the non-formation or non-crystallinity. The thickness of the nickel film greatly affects its adhesion or heat resistance.

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— _ I I V. Description of the invention (5) When the thickness is too thick, there is a tendency to decrease. Easily = peeling from the core material powder and the conductivity is easy. The required conductivity. It can't be obtained by】 It is best to be ~ 1. The thickness of the diaphragm is in addition to, for example, about .1. The nickel film is calculated from the amount of added ions or chemical analysis. In addition, it is also possible to use a type of a rhenium agent for forming a zinc film by using an electroless plating to produce a state of a rhenium film. For example, the use of nickel; alloys of nickel and other elements, the obtained nickel film is known as a reducing agent, and the film system of this alloy is also; C 'powder for the money layer of the present invention System in; membrane. It is composed of nickel film. However, from the point of view of forming the surface from the above point of view, it is possible to use a conductive gold electric ore layer of powder on the outermost surface layer to focus on the nickel film. Electric key layer. The thickness of the plating layer is generally-〇〇〇〇1〜〇. 5 ,,,, / 'deplating layer formed. Gold electricity can be added by gold ion. The thickness of the gold plating layer forms the core material powder of the nickel film :; and the nose comes out. The use of organic powder and inorganic powder = ^ is not particularly limited, and

In the non-electrolytic ore layer method described above, it is best to use 何 -species. After considering water. Therefore, the 'core material powder system is the best; ^ powder system can be dispersed in 4 does not dissolve or change even for acids or tests: insoluble in water' is more reasonable because it can be usually divided by stirring, etc. = so-called dispersible in water Suspended shellfish dispersed in water

7082-6219-PF (N2); Ahddub.ptd to the extent that it is formed on the surface of the core material powder: Thai II: To be able to nickel skin 200530430 V. Description of the invention (6) Body.

In the shape of the core material powder, the powder system can be powdery, but can be: 1 system. Generally, the core material has a shape other than a fibrous shape, a hollow shape, or a plate. The size of the core material powder is assigned to 2 or 疋. It can also be an indefinite use and choose an appropriate size = 'the specific of the powder for the plating of this meming is used as the electronic circuit connection i; The best powder is :; material left and right = glass, ceramic (also contains alloy), glass with water), aluminosilicate gold 5 genus emulsion (also contains metal nitrides, metal carbonates Genus: salt, metal carbide, metal sulfide, metal acid salt, metal and other metal salts, gold propylene, polyvinyl chloride, etc .; meaning; natural resin, polyethylene glycol, polyester, polyacrylonitrile, poly Acetal, Ion :::: Polyamine, polyacrylic resin, alkyd resin, benzoic acid ;; ::: = thermoplastic grease, melamine resin, xylene ',,, and guanamine Diallyl phthalate resin, etc. Now, ^ tree month, autumn oxygen resin or a mixture of two or more can be used alone early, can also be used as a core material powder system is best The surface modification is performed with the precious metal ion d: c energy or daughter system is preferably an ion of palladium or silver. Household metal ionization refers to the ability to capture precious metal ions and $ = ^ I capture of precious metal ions can become a chelate or salt. For example, in core material, page 10, 7082-6219-PF (N2); Ahddub.ptd 200530430 V. Description of the invention (7) In the state where the surface of the powder has amine, imine, amido, amido, cyano, hydroxyl, nitrile, carboxyl, etc., the core powder On the surface, there is a trapping energy of precious metal ions. In a state where the surface is modified to have a trapping energy of precious metal ions, for example, the method described in Japanese Patent Publication No. 64882 can be used. The following describes the ideal method for manufacturing the powder for coating of the present invention. The method for manufacturing the powder for coating is roughly divided into (丨) a contact treatment process, (2) an initial film formation process, and (3) non-electrolysis. In the process of coating catalyst treatment, the precious metal ions can be captured or removed. 赋予 The precious metal ions are captured by 2 surface treatments ==, then this is reduced, and the aforementioned precious metal is loaded with "material powder, divided into (") " Two thin Λ-shaped two systems " Compound Institute Composition two: ^ mixed with ions, reducing agent, and amine powder in the core material ;: other initial film forming solution, reducing nickel ions, layer process, forming an initial nickel film. In the absence of electrolytic money Aqueous suspension, == the core material powder of the film and the same amine compound of the aforementioned complexing agent are simultaneously added to contain the same kind of the complex; the liquid two kinds of liquid, the nickel-containing ion of the complexing agent The liquid and the reducing agent are described in detail. The electroless ore layer reaction is carried out. In the following, each process (1) is a catalyst treatment process.

In the state of the core material powder itself and the ancient master M, the catalyst is directly catalyzed: in the state of the capture energy of the Berman ions, the modification treatment is performed. Surface modification ;;;; :: in the state of surface, water or organic solution of surface treatment agent 7082-6219-PF (N2); Ahddnb.ptd page Π 200530430 V. Description of the invention (8) Solvent Come to add the core material powder and thoroughly mix and dry the powder. The amount of surface treatment agent-person # After the knife, separate and adjust the surface area of the powder per m2, ^. ~ The type of wood powder, by which one improves the effect. · Achieving uniformity in the range of ~ 100 lIlg Next, the core material powder is dispersed in a thin acidic aqueous solution of, for example, a salt. This will put 1 into the precious gold surface of distant or silver nitrate. The concentration of the noble metal salt is sufficient for the diions to be trapped in the range of 10-7 to 1 X 10-2 Moore. Capture the main 77 people-1 X per lm2 of surface area separated from the system and washed with water. Next, in the core material powder system of 倭 ^ ions, a reducing agent is added here, and the core material powder is suspended in water and is placed on the surface of the core material powder to carry the original treatment of precious gold tincture. . Thereby, for example, sodium hypophosphite, sodium borohydride, etc. As the reducing agent, hydrazine, formaldehyde and the like are used. Boron potassium and dimethylamine borane can be attached to the surface of the powder before the precious metal ions are captured on the surface of the core material, and the ions are adsorbed on the surface of the powder. Therefore, for example, S can be treated. In order to add the tin ion absorber to the stannous chloride aqueous solution, the core material powder having a predetermined 5-to-negative treatment was stirred. (2) The initial film formation process was performed within t of the next day. The initial thin film formation process is due to the uniform precipitation of nickel from the core to the core powder and the surface of the core material powder. The initial thin film formation process is carried out by first carrying the expensive two. Dispersed in water at ground. For dispersion, for example, one core material powder can be used, and the dispersion device can be sufficiently sheared. In dispersing the core material powder, a dispersant such as a surfactant is used instead of colloidal light or a homogenizer. For example, ^^ can be used to suspend the water

Just 7〇82-6219-PF (N2); Ahddub.ptd Page 12 200530430 V. Description of the invention (9) The turbidity substance 'is dispersed and mixed in the initial film-forming liquid containing nickel ion and a complexing agent added thereto. As a result of the initial reaction and the reduction reaction caused by the amine compound, nickel ions begin to form on the surface of the core material powder. As described above, the initial thin film is formed to form an initial nickel film. The purpose of smoothing the surface of the heartwood powder is because the uniform precipitation and formation of the initial nickel film can be performed to a thinner thickness, and therefore the shape. From this point of view, the initial film ^, the range of the surface of the core material powder is ~ 2, and particularly preferably 0.05. I ~ two jaws. The thickness is preferably 0.001. The thickness of the thin film at the initial stage is reduced by the amount of ions added or chemical analysis without consuming the complexing agent. Pound out. In addition, since the concentration of nickel from the initial thickness of the initial thin film forming the film of the aforementioned thickness is best seen from the aspect of e 9 π, the initial thin rise, especially 1.0 × 10-3 ~ 〇 ”Moore / = And ~ 1 · mol / water-soluble ^ such as nickel sulfate or nickel chloride. As a nickel ion source system, the reducing agent for the initial thin film forming solution: 0 mole / liter from the same viewpoint, especially 2 · 〇χ 1〇 ~ 3〜〇 辰 ^ system is preferably 4 X 10- 4 ~ 2 · The agent system can use the same main moire / liter as described above. As the same as reduction. The reduction of shell metal ions is used in the initial / special film-forming solution to contain human ^ This and the nickel-containing ion described later; it is important. A nickel film with a columnar structure can be borrowed. The compounding agent mixes easily to form metal ions and has the function of forming complexes, and the object of plating is the compounding agent, which uses an amine compound, as an example. In the present invention, M 7082-6219-PF (N2) is used as amine, diethylenetriamine, triethylenetetramine, alanine, dipentaethylenehexamethylenetetramine, etc .; Ahddub.ptd 200530430 2. Description of the invention (10) A compound having an amine group. These complexing agents can be used in i or two or more kinds. Among these complexing agents, especially when glycine or ethylenediamine is used, a nickel film having a columnar structure can be formed more easily. Therefore, it becomes reasonable :: agent :; From the viewpoint of the record margin = and the solubility of the blending agent, eight = / special r, and the amount of the blending agent of the night is preferably 〇〇〇〇3 ～ 10mol / liter, especially 0.00 ~ 6 ~ 4 Moore / L. From the viewpoint of the formation of the three-body S Z 222, the formation of the initial film is' the life of the β-material powder of the aqueous suspension and p ^ 0.5 to 300 g / liter. In addition, it is taken to be 0.1 ~ 500g / liter, especially k containing the core material powder, to obtain an aqueous suspension system; the body and the initial stage of mixing are formed into a film. In addition to the electroless money described later in the electroless recorder, it is easy to form an aqueous suspension of Niigata with a columnar structure. From the aspect of the core dihide that can be included in the suspension, Then, the ratio of the volume of the aqueous suspension to the total surface area of the 5 body is 0 · 1 ~ 1 5 m 2 / liter with respect to the water, and the ratio is generally called the load.) It is preferably too high. 'In the back', the description is 1 ~ 10 # / liter. In the reduction of the load changer, it is a non-Domestic non-electrolytic plating process, and the nickel in the liquid phase is adhered to the surface of the core powder, which is in the liquid phase. A large amount of 'this system (3) electroless plating process ^' is not easy to form a uniform nickel film. In the electroless plating process, the material powder and the above-mentioned mistakes are used (a) including the anger of forming an initial film Aqueous suspensions of 30 kinds of liquids containing reducing agent liquid, (b) nickel ion-containing liquids and (c) ° ia) aqueous suspension systems can still be directly

7082-6219-PF (N2); Ahddub.ptd 页 page 200530430 V. Description of the invention () 1) Use of an aqueous suspension with a film shape different from (a) in the initial stage described above: (c) 2 kinds of liquid containing reducing agent. (B) The nickel ion solution containing nickel ion solution and the secondary source of nickel sulphate or nickel chloride is a nickel ion solution which is, for example, an aqueous solution in which nickel can easily form a solder skin with a columnar structure. If it can be considered to be OH.2 = M eighty /, the concentration of nickel ions is liter. , A liter, especially 0 · 5 ~ 1. 0 Moore /

In the case of the ionic liquid containing Xiaodong PI, the same complex system becomes important. It is also known as turbidity: it is widely available in the factory, and it is mixed with turbidity and (b) nickel-containing ion solution, and it is important to suspend in (a). It is possible to change the reason why the compound type containing the same kind of compound is changed. The reason is not clear. U = nickel film with columnar structure. The turbid body and the nickel-containing ion of (b) are stable because of the inclusion of a complexing agent in both the aqueous suspension of (a), Erhai 3 ~, and the sub-liquid, thereby stabilizing the reversion reaction. For the sake of proceeding. The concentration of the complexing agent containing the ionic liquid containing etched ions is also the same as that of (a). The concentration of the mixture of 蟀 1 mixture is used to form the nickel film, which affects: ". In terms of solubility, nickel

& The amount of staggering agent is preferably from 0.06 to 12 mol / liter, particularly from 0. 012 to 8 mol / liter. ^ (c \ the reducing agent-containing liquid system generally becomes an aqueous solution of the reducing agent. As the original agent system, the same as the reduction of the precious metal ions described above can be used = the same. It is particularly preferable to use sodium hypophosphite From the point of view of the impact on the reduction of nickel ions, the concentration of the reducing agent should preferably be adjusted to 0 · 1 ~ 20 Moore / liter, especially 1 ~ 10 Moore / liter.

200530430 V. Scope of invention description (12). In addition, at h, the addition of the suspension composed of the aforementioned amine compound and the nickel-containing ion solution of (b), and the like can be reduced. In addition to this kind of $ complexing agent, other types such as citric acid, acetoacetate, etc. are added as a series of organic acid or its salt, or its metal test salt; or; stone; stone; rhyme: acid, In the state of lactic acid or gluconic acid, it is the same as that of amine ^ :: ^ ° in the same kind of raw suspension in combination with other types of complexing agents and (b): nickel ion;; of: = in (a) aqueous county ， MJ ^ ^ Sub-liquid and (C) containment; 2 solids of the agent liquid simultaneously add ⑻ of nickel-containing ion to the surface of the core material powder, 2 kinds of chain from the liquid; f. Weaving reduction of nickel ions, adding rate of reducing agent-containing liquid; membrane. Contains nickel ion solution and plastic. Therefore, the formation of the nickel film of the recording structure causes the acceleration of the shadow to be controlled by adjusting the addition of two liquids per meter per hour. The nickel precipitation rate is calculated and calculated. Jikoutian 3 dart ionic liquid Tim Likou = During the period of time when a liquid is added to an aqueous suspension, the concentration of the complexing agent of the body is fluctuated — ^ ^ The water-based county turbidity caused by the addition =;: = due to 2 The concentration of the complexing agent included in a liquid = the increase in t and the solubility of the complexing agent considered in a nickel-containing ion solution 2 "5:. In the manufacturer ④ 'the test of the addition of 2 kinds of liquids is also performed. \, = Hair: people It was learned from the review that the traitor in the high 丨 $ * #Private is particularly conducive to keeping the U wave in the aqueous suspension at 0.003 ~ 10 Moore / liter, especially 200530430 V. Explanation of the invention (13) 0 · 0 0 6 ~ 4 Moore / liter range. It can be easier to keep the concentration of the complexing agent in the aqueous suspension during the two kinds of liquid addition process within the aforementioned range, and it is easier. A nickel film with a columnar structure is formed. I keep the wave length of the complexing agent in the aqueous suspension within the aforementioned range. Therefore, the addition rate of the ionic liquid and the reducing agent-containing liquid (the nickel precipitation rate) or The initial concentration of the complexing agent in the waterborne turbidity or the complexing in the nickel-containing ion solution; Concentrations of these values are as described above. ^ While the two liquids are added to the aqueous suspension, it is best to keep the load of the surface within 0] ~ 1W / liter, especially Bu / Liter range. 1 In this way, nickel is uniformly precipitated, and at the same time, a nickel film that is less than the crystal grain boundary is more strongly formed. For the same reason, it is easy to d't *. The load at the point in time when the addition of the liquid completes the reduction of nickel ions is within this range. Carving Chinyu like this, to obtain a nickel coating film for forming a nickel film on the surface of the core powder, and then a nickel film for the coating powder The grain boundary 俜 in the medium is mainly oriented in the thickness direction of the nickel film. 1 series is also based on the type of reducing agent used, but the suppression value of the suspension is maintained at 3 ~ 13, especially 2 From the perspective of the formation of the water-insoluble precipitate of nickel, the word 'becomes ideal. In order to adjust the pH value, for example, ^ can be used in a reducing agent-containing liquid, and can be used for long-term production. The whole agent. It is obtained by adding pH words such as lice sodium oxide into the existing The powder system for coating is separated after repeated washing ’. As an additional process system,

200530430 V. Description of the invention (14) On ___, the formation of the gold plating layer that becomes the uppermost layer can be performed according to the conventionally known electroless plating layer ^ f The aqueous suspension of the plating layer is made of powder for coating, including ^ Jiao- 仃. For example, using sodium and citrate, such as U, ^, ^, ^, ^, ^, tetraacetic acid, and the pH value of the electrolytic shovel screen, one, and adding sodium hydroxide to adjust the image on the nickel film to form a gold power ore layer. The powder system for coatings served by Nong & samples is suitable for using anisotropic conductive films f Α ΓίΜ 弋 舳 玄 私, && for example, to

Electro-membrane CACE) or heat-sealed connector (HS benefit panel electrode to connect to L s 丨 crystal liquid ^ display material, etc.) ^ < the conductivity of the electric substrate is not limited to the foregoing implementation The shape is on the surface of the core material powder, which is 4 :: In the foregoing implementation, however, in order to replace this, the nickel skin is now formed on the surface of the heartwood powder. The surface of the film of the powder of the metal film is formed with a nickel film of ancient 4 u :. Moreover, the plating of the present invention is not limited to the aforementioned method. The method of manufacturing the cargo body is [ [Example] This hair :: an example to explain the present invention in more detail. However, [Example 2 is limited to this type of example. (1) Catalyst process to make the diameter: the spherical shape of the two true specific gravity 2.23 Dioxygen ... 40 milliliters of regulated water, 40 g of Rongxin wood powder, stir and put into 400 knots 231 "). Tune; i (CyPrei (Cyprei) company's "clean tune with fast water solution concentration of 40 ml / liter. Continued 200530430 V. Description of the invention (15) = at the liquid temperature of 60. 'Apply ultrasonic waves' At the same time, stirring for 30 minutes :: the surface modification and dispersion treatment of the powder. According to the aqueous solution, the core material powder washed with water once became 200 ml of paddle. The sub-aqueous solution 20 was gasified. The milliliter is added to the mixture. The concentration of the aqueous solution is = Asian pen liters / liter. Stir for 5 minutes at room temperature, and perform the sensitization treatment of tin ion = the surface of the heartwood powder. Then 'make the core material powder to be 40%, and maintain it at 60 t. And use ultrasound to perform slurry addition and add 0.11 mole / liter of gasified palladium aqueous solution 2:

= Handle. Then, "the aqueous solution was filtered, so that the repolymerized heartwood powder washed with hot water once" became a slurry of 200 ml. Ultrasound was used at the same time, the slurry was stirred, and 20 ml of a mixed aqueous solution of 0.17 mol / liter of dimethylamine and 0.16 mol / liter of boric acid was added thereto. At room temperature, sonication was performed at the same time, and 2 minutes of searching and mixing were performed to perform the treatment of palladium ions. (2) Initial film formation process

The 200 ml of the slurry obtained in the process of (1) was stirred and added to the initial film-forming liquid of (a) shown in Table 1 to become an aqueous suspension. The initial film-forming liquid system was heated at 7 5 C 'and the liquid amount was 1.8 liters. Immediately after the slurry was charged, the generation of hydrogen was observed, and the start of the initial film formation was confirmed. After 1 minute, 0. 06 3 mol of sodium hypophosphite was added, and stirring was continued for 1 minute. The load of the aqueous suspension is 4 · 5 m 2 / liter. (3) Electroless plating process

7082-6219-PF (N2); Ahddub.ptd Page 19 200530430 V. Description of the invention (16) '----- c, 9 To add the ionic liquid containing ⑴ as shown in Table 1 and raise it at 3 = ί; wide night body. The amount of addition is LI 2 respectively. Immediately see the generation of hydrogen, confirm the coating. Until the end of the addition of the two liquids, the water content. At the end of the two liquids, the addition of Λ / chen once straight = held at the concentration shown in Table 1, maintained at a temperature of 75t, and at the same time, the load of the straight foaming stopped after the addition was 2 4m2 / Whisk into the pan and stir. Two kinds of liquid suspensions were subjected to 3 A f for the filtrate. Next, the water-based 9 # ^ 110 coating powder for coating was filtered. The SEM of ^ g large magnification of 50000 times magnification of the powder for coating obtained when the nickel-phosphorus alloy was observed and observed in Figure 1. The grain boundary of the film is mainly oriented in the cross section of the female film. Same time. The thickness of the thin film was calculated from the amount of nickel ions added. The thickness of the coating film is 0.54 [Examples 5 to 8] [Electroless plating for modulation of gold plating layer] Ye 丨 8 series contains 0.02 7 Moore / liter of Yishuo: \ liter. Electroless plating solution ^ fee 4 7 Jie / L of trisodium citrate and 001 苴 G 酉 夂 tetrasodium, 0.038 Mo • Wu _ / gongdou + & sodium hydroxide aqueous solution to adjust the pH to 6 The gold and potassium cyanide are removed by the plating solution, and at the same time, the plating solution is eight. The temperature of the mixing solution was 60 t: no electricity, and 33 g of the powder for the coating was obtained, and 20 / + was added without adding the materials described in Examples 1 to 4. The liquid was filtered, and the filtered substance was subjected to a gold plating treatment. After three times of re-slurry washing,

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It is dried by a vacuum dryer of Η 0, C. Thereby, a powder for a plating layer is obtained in which a gold electroless plating layer is formed on a nickel film. The thickness of the gold plating layer calculated from the amount of gold ions is 0.025 // m. / j 、、 ^ [Example 9] (1) The catalyst treatment process uses a spherical benzoguanine with an average particle size of 14 and a true specific gravity of 1.39 "-melamine-formaldehyde resin [manufactured by Japan Catalysts, Inc., Commodity name = π Ε ρ 〇s 1: ar (also Persian) prime ν '1, into &a; stone% ,, f ^)], as the core material powder. Make the core # r? 之 ， , To become a body of 400 ml, maintained at 60.0 .: 7

Peel, ... Λ Add 0.11 Moore / L of palladium chloride = 2 ^ L of liquid. ㈣, maintain this ㈣ mix ^ the surface of the powder to capture palladium ion ^ walk in the knife 仃 in the heartwood 汸, you, said AT away from the activation treatment. Next, the aqueous solution was filtered and the slurry was re-slapped once. The water was mixed with the heartwood powder which had been washed by Ruta Tianru to make a slurry of 200 ml. Using ultrasound, the same day master, x... »^ 1 door 4, stir the slurry, add 0.017 Moore / ^ 〇Λ ^„ not U · 1 b ^ / liter of mixed water between boric acid You hang the dish and use ultrasonic waves, and at the same time, perform 2 knife agitation to reduce the palladium ion. (2) Initial film formation process

The 200 ml of the slurry obtained in the process of (1) is stirred and added to the initial film-forming liquid of (a) to become an aqueous suspension. The initial 2 formation liquid system was heated at 75t, and the liquid volume was 18 liters. The generation of hydrogen was observed immediately after the slurry 7 was introduced, and it was confirmed that the initial film formation started. After 1 minute, 0.042 moles of sodium hypophosphite was added, and stirring was continued for 1 minute. The load of the aqueous suspension is 4.6mV liters.

200530430 V. Description of the invention (18) (3) The electroless plating process is in the initial thin film formation process. The addition of 1 is not included, and the master is κ. "King's heart basket knife is not listed in Table (C) with reduction sword. The two kinds of liquids ° The nickel ion-containing solution and liters that are not in (b) in Table 1. In # species / night body. The amount of addition is 409 milligrams. After adding the two kinds of liquids, immediately lose the socks + Xuan a ^ pe ^ ^ 1 can see the generation of lice, confirm the start of the plating. Until the end of the addition of the two liquids, the concentration of the amine-based complexing agent of water-based beans is maintained as shown in Table 丨Concentrated: After the addition of the two liquids, the temperature is maintained at 75 ° C until the hydrogen foaming stops, and the temperature is simultaneously and continuously stirred. The load after the addition of the two liquids is 3. 3mV Liter. Next, the resuspended polymer was washed three times with the aqueous suspension, and then dried with a vacuum dryer of 〇t. This resulted in a nickel-phosphorus alloy. Powder of coating for coating. Observation of coating obtained by SEM magnification of 500,000 () times. The cross-section of the coating film for the body is the same as that in Figure 1. The grain boundary of the coating film is mainly / cross-section oriented in the thickness direction of the coating film. The thickness of the coating film is different from the amount of nickel ions added. 26 Am. [Example 1 〇] In addition to using 2i.36g of powder for forging layer obtained in actual ㈣9

The rest is the same as in Example 5 ', and a powder for a plating layer is obtained in which a gold electroless plating layer is formed on a nickel film. It consists of gold ion, sky + β, and thickness of ore layer. + Added! Calculated gold electricity [Example 11], spherical acrylic resin with a true specific gravity of 133, (1) Catalyst processing process Use an average particle # 10 ν

7082.6219-PF (N2); /vhddub.ptd Page 22 200530430 V. Description of the invention (19) As the core material powder. 200 g of the core material powder was made into a polymer of 200 ml '. 2000 ml of an aqueous solution of stannous chloride was put into the slurry. The concentration of this aqueous solution was 5 X 10-3 ml / liter. Stir at room temperature for 5 minutes to perform a sensitization treatment to adsorb tin ions on the surface of the core material powder. Next, the aqueous solution 'was subjected to re-slurry washing once. Then, the powder of the core material was made into a preparation of 400 ml and maintained at 60 i. Then, using a ultrasonic wave, the slurry was blended, and at the same time, 2 ml of a vaporized palladium aqueous solution of 0. 11 mole / liter was added. The stirring state was maintained for 5 minutes, and an activation treatment was performed on the surface of the core powder to capture palladium ions. Next, the aqueous solution was filtered so that the core material powder, which was washed with the hot water once, became 2000 ml of slurry. Then, the slurry was stirred at the same time with ultrasonic waves, and 20 ml of a mixed aqueous solution of 0 · mol · 7 mol / liter of difluorenylamine and 0 · 16 mole / liter of boric acid was added thereto. Simultaneously, ultrasonic waves were used at room temperature for 2 minutes while stirring to perform a reduction treatment of palladium ions. (2) Initial film formation: The 2,000 ml of the slurry obtained in the process of (1) was stirred and added to the initial film-forming solution of (a) shown in Table 1 to form an aqueous suspension. The initial film-forming liquid system was heated at 75 ° C, and the liquid volume was 8 liters. Immediately after the slurry was charged, the generation of hydrogen was seen and the start of the plating reaction was confirmed. One minute later, 0.042 mol of sodium hypophosphite was added, and stirring was continued for 1 minute. The load of the aqueous suspension was 4.5 m2 / liter. (3) Electroless plating process The aqueous suspensions obtained in the initial film formation process are added at the addition rates shown in Table 1 to the nickel-containing ion solution (b) shown in Table 1 and

7082-6219-PF (N2); Ahddub.ptd

Page 23 200530430 V. Description of the invention (20) '~ ----____ (c) 2 kinds of liquid containing reducing agent. Add liters. Immediately after adding the two kinds of liquids, it was seen that the ^^^ system became the beginning of the reaction. Until the two kinds of liquids are generated by hydrogen, it is confirmed that the water solubility of the plating suspension is 4 times as long as the sulfide having an amine group is ended. After the addition of the two liquids, the density of the two liquids shown in Table 1 was maintained. After the addition of the two liquids, one pound and Hori were 3.2 m2 / liter. At the end of the temperature of ° C, at the same time, until the foaming of 拄 -Λ ceases, it is maintained at 75, and the mixture is stirred for ^^^^ to the filter. Next, the water-based suspension vacuum dryer was filtered to clean the slurry, and then the powder was coated with a coating film at 1 ° C and 0 ° C. ^, Stay. In this way, a coating powder having a coating layer of nickel-phosphorus alloy is obtained. The grain boundary of the obtained film is mainly determined by an SEM with a magnification of 50000 times. The section of the film for the layer is the same as the figure. 1. D calculated from the amount of skin added is a cross section in the thickness direction of the film. From nickel ions [Example 12] # The thickness of the film for money layer is 0. 26 // m. Except that it is used, the other two are the same; the powder of the bond layer obtained in Example 11 was 17.0§, and the electroplating layer was used for steam refining example 5 to obtain the thickness of the gold electroless layer formed on the nickel film. Said 〇? Powder. Gold electricity calculated from the amount of gold ions added [Comparative Example 1] 5 & m. In this comparative example, the electroless ore layer construction method has been used until the catalyst production. The deplating liquid system is the same as in Example 1 until the process ^^. As the second sub-disc without electric liters, it contains 0.111 moles / liter of sodium acid, 0.24 moles / liter / liter of sodium acetic acid, 0.26 moles / liter of sodium sodium fruit , 0.8 Mojina and 2 X 1 0-6 Moore / liter lead acetate and pH adjusted-7082-6219-PF (N2); Ahddub.t

Page 24 200530430 V. Description of Invention (21) '"' ~ It becomes five. 6 liters of electroless plating solution was heated to ^ it for Jianluo. In this bath, the core material powder subjected to the catalyst treatment was put into the mixture and dispersed, and the reduction reaction of nickel was started. An automatic pH adjustment device was used to maintain the pH of the liquid in the reduction reaction at 5 by the addition of a 5 mole / liter aqueous solution of tritium oxide. In addition, if the reaction is stopped halfway, a small amount of 2 moles / liter of a sodium hypophosphite aqueous solution is added in small amounts each time, and the reaction is performed continually. If the liquid does not foam even when the sodium hypophosphite aqueous solution is added, stop all the additions, filter the liquid, and after the slurry is washed three times with re-slurry, dry it under vacuum. Machine to dry. Thereby, a powder having a film for nickel-phosphorus alloy plating was obtained. When observing the cross section of the coating film of the coating powder obtained by SEM magnification of 50000 times, the cross section of the coating film was the same as that shown in FIG. Grain boundary. The powder for the ship layer is manufactured by the conventional electroless plating method. Therefore, it is impossible to supply it with practical use because it contains fine nickel decomposition products. [Comparative Example 2] The same core material powder after the catalytic treatment as obtained in Example 1 was made into a 2 (H) liter slurry. Here, (a ), At the beginning of the @phase film forming liquid and became an aqueous suspension. The initial film formation liquid was heated at f 75 ° C, and the liquid volume was 1.8 litres. After the slurry was put in, hydrogen was generated on the horse, and the start of the initial film formation was confirmed. One minute later, 0.063 moles of sodium hypophosphite was added, and stirring was continued for one minute. To this aqueous suspension, the nickel ion-containing liquid (b) and the reducing agent-containing liquid (c) shown in Table 1 were added at the addition rates shown in Table 丨, respectively.

7082-6219-PF (N2); Ahddub.ptd Page 25 200530430 V. Description of the invention (22) 2 kinds of liquids.余 加 | 里 # are 8700 ml. Immediately after the addition of the two liquids, the generation of hydrogen was observed, and the start of the plating reaction was confirmed. After the end of the two liquids, the gas was added ±-until the foaming of hydrogen ceased, kept at a temperature of 750C, and stirring was continued on the same day. Next, the aqueous suspension was filtered, and the filtrate was washed three times with re-slurry, and then 11 () was used. 〇 Dry! And proceed? dry. Thereby, a rice cutter body having nickel-filled alloy ore Η *, was obtained. When observing the cross section of the coating film of the obtained powder for coating layer through an SEM with a magnification of 50000 times, the cross section of the coating film was the same as that shown in FIG. The thickness of the ore layer calculated from the amount of nickel ions was 0.54 / zm. [Comparative Example 3] Except that 3 3 g of the powder for plating layer obtained in Comparative Example 2 was used, the remainder was the same as in Example 5 to obtain a powder for plating layer in which gold electroless plating and a layer were formed on a nickel film. The gold plating reed x thickness calculated from the amount of gold ions added was 0.025 / zm. [Performance evaluation] The powders for plating layers obtained in Examples 1 to 12 and Comparative Examples 1 to 3 were used to measure the volume specific resistance value by the following method and evaluate the heat resistance. These results are shown in Table 2 below. σ [Measurement of volume specific resistance value] In a resin cylinder with an inner diameter of 1 〇_ standing vertically, add 1.0 g of powder for the mineral layer, and measure the resistance between the upper and lower electrodes under a load of 10 kg. The volume inherent resistance value. [Evaluation of Heat Resistance of Film for Bell Layer]

200530430 V. Description of the invention (23) Under the oxidizing atmosphere at 200 ° C, the coating powder is stored for 24 hours, 48 hours, 72 hours, 96 hours, and 120 hours, respectively. For the powder for plating after storage, the volume specific resistance was measured by the method described above, and the resistance was used as a measure of heat resistance. Tomb 1

W (a) Initial film-forming solution (mol / l) (b) Epidemic-containing liquid (mol / l) (b) Reducing agent-containing liquid (mol / l) Adding speed ml / min Concentration of an ammonium-containing modifier mol / l Preferable Example 1 Sodium nickel glycine sulfate hypophosphite 0.27 0.013 0.032 Nickel glycine sulfate 0.54 0.86 Sodium hypophosphite S sodium oxide 2.57 2.6 7 0.27 Example 2 Ethylene diamine nickel sulfate hypophosphite 0.33 0.013 0.032 Ethylene diamine sulfuric acid 0.66 0.86 sodium hypophosphite sodium hydroxide 2.57 2.6 7 0.33 tone example 3 sodium glycine picronate sodium nickel hyposulfite sodium 0.27 0.087 0.013 0.032 Nickel 0.54 0.17 0.86 Sodium hypophosphite sodium hydroxide 2.57 2.6 7 0.27 Expedient Example 4 Glycine sulfuric acid fed sodium hypophosphite 2.0 0.013 0.032 Nickel tellurate glycine 4.0 0.86 Sodium hypophosphite sodium hydroxide 2.57 2.6 7 2.00 Bao Shi Example 9 Nickel Glycine Sulfate Sodium Hypophosphite 0.27 0.0086 0.021 Nickel Glycine Sulfate 0.54 0.86 Sodium Hypophosphite Sodium Oxide Oxide 2.57 2.6 3 0.27 ί 0.30 Mu Example 11 Nickel Glycine Teteophosphite Sodium 0.27 0.0086 0.021 Nickel Glycine Sulfate 0.54 0.86 Phosphorous acid Sodium vapor sodium oxide 3 2.57 2.6 0.27 1 0.30 Comparative Example 2 Nickel sulfate, sodium lin hyposulfurous nickel sulfate 0.013 0.032 0.86 2.57 sodium hypophosphite 7-- #

7082-6219-PF (N2); Ahddub.ptd Page 27 200530430 V. Description of the invention (24) [Table 2] Volume specific resistance 値 (π Ω cm) 24 hours after plating 4 hours after 4 hours 72 hours after 96 hours 120 hours later, Bao Shi 1 24 59 66 95 92 91 Example 2 19 32 50 78 9D 93 Example 3 24 48 63 85 89 98 Example 4 20 50 70 84 90 101 Bao Shi 5 4.5 4.8 4.9 5.2 4.6 6.3 Example 6 3.2 5 5.5 5.5 5.4 5.6 5.9 Example 7 4.2 5.2 5.2 5.3 5.3 6 6 Baoshi Example 8 3.8 4.9 5 5.3 5.9 6.3 Example 9 45 56 58 74 94 110 Example 10 2.2 4.1 5.8 9 10 10 Example 11 42 60 63 88 98 105 Example 12 4.3 4.2 8.8 10 11 10 Comparative Example 1 Unable to measure. Unable to measure. * Unable to measure. * Unable to measure. * Unable to measure. * Unable to measure. Example 3 4.2 1200 23000 Nickel over 10000D and above 100,000 and 1000DG and above. Nickel disintegrated into Micro Putian 1 is unavailable for measurement.

W It is clear from the results shown in Table 2 that the powder for the mineral layer (product of the present invention) of each example has a very low resistance, and even if it is stored at high temperature for a long time, the increase in resistance is small. The financial heat is very high. Contrary to this, it was found that the powder for the plating layer of the comparative example had low resistance, increased resistance due to long-term storage, and low heat resistance.

[Effects of the Invention] As described in detail above, according to the present invention, the heat resistance of the powder for conductive electroless plating is improved, and even if it is stored at high temperature for a long time, the increase in resistance is reduced.

7082-6219-PF (N2); Ahddub.ptd Page 28 200530430 Brief Description of Drawings Figure 1 is a scanning electron microscope showing an example of a section of a coating film for a coating of a powder for conductive electroless plating of the present invention photo. Fig. 2 is a scanning electron microscope photograph showing an example of a cross-section of a coating film for a conventional electroless plating powder. #

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Claims (1)

200530430 VI. Patent application range 1 ·-A kind of powder for conductive electroless plating is formed on the nickel film by electroless plating method. The surface of "" 'is characterized by:' The powder milk in the aforementioned nickel film #, Direction. 1 is mainly based on the nickel film and is oriented in thickness. 2 · As in the scope of the patent application, the towel has m conductive powder for electroless plating on the outermost surface. 3 · A kind of conductive electroless electroless plating layer. The production of powders for deplating and layering; the raw materials are described in item 1 of the patent scope, and the manufacturing process is characterized by: the powder for conductive electroless ore layer Before the capture energy of the precious metal ions with noble metal ions is added + capture or surface treatment and after the application, reduce this, the heart powder to capture the noble metal ion surface, and then, the core material powder 呷? 2 On the surface of the aforementioned core material powder and a made of amine compound, a is formed on the surface of the body containing nickel ions and reduced. 々Γ y, the initial film of nickel is formed, and after the bran, the initial film is formed 3 The core material powder and the complex: The sexual suspensions are added individually and simultaneously to two kinds of liquids containing the same kind of complexing agent: two sub-liquids and a reducing agent-containing liquid, and the electroless plating reaction is added. ^ 4 As described in the method for manufacturing a powder for conductive electroless ore layer in item 3 of the patent application, in #, the aforementioned nickel-containing ion-containing liquid and the aforementioned containing are added to an aqueous suspension containing the aforementioned core material powder. In the process of the reducing agent liquid, adjust the addition amount of the nickel ion-containing liquid and the reducing agent-containing liquid or the aqueous suspension ^ 200530430 6. The initial concentration of the complexing agent in the scope of patent application or the concentration of the complexing agent in the nickel-containing ion solution, so that the concentration of the aforementioned complexing agent in the aqueous suspension is maintained at 0.003 ~ 10 Moore / Range of liters. 5. The method for producing a powder for a conductive electroless bond layer according to item 3 or 4 of the scope of patent application, wherein the aforementioned complexing agent is glycine or ethylenediamine. 6. The method for producing a powder for conductive electroless plating according to any one of claims 3 to 5, wherein the aforementioned nickel ion-containing liquid and the aqueous suspension containing the aforementioned core material powder are added to The ratio of the total surface area of the core material powder contained in the aqueous suspension before the reducing agent-containing liquid to the volume of the aqueous suspension is 0.1 to 15 m 2 / liter. 7082-6219-PF (N2); Ahddub.ptd p. 31