TW574420B - Surface treating films on nickel metal with superior heat resisting adhesivity to resins - Google Patents

Description

574420 V. Description of the invention (l) ------- [Detailed description of the present invention] [Technical field to which the present invention belongs] The present invention relates to a substrate for providing an object, especially a gold resin, Force-to-force force forms a surface treatment film on a metal surface. As described in more detail, it is related to a nickel-based surface treatment film that has excellent adhesion even when the aforementioned metal-resin joint is placed in a high temperature environment of 200 ° C to 300 r. μ, [Known technology] Used in printed circuit boards, standard frames, LS I, and other electronic and electrical parts, metal parts, and joints. In particular, in thermosetting resins or thermoplastic resins such as epoxy resins or polyimide resins used in this field, when these resins are molded, they need to be exposed to high temperatures at high temperatures. . In addition, in order to: = form the wiring layout on the copper berth, it also needs to undergo severe manufacturing processes in contact with organic solvents, acids, and chemicals. Furthermore, although active parts such as semiconductor parts and passive parts such as LCR are used for welding, lead welding has become increasingly unavailable due to recent environmental problems, so the solder reflow temperature is gradually increasing. Under such conditions, the adhesion between the metal substrate and the resin is poor, especially the moisture adsorbed on the metal surface at high temperature or due to the manufacturing process adsorbed on the bonding interface ^ The expansion of the water caused the metal substrate surface and the resin to peel off; swelling, etc. The occurrence of such damage will damage the internal corrosion resistance, depending on the situation, it will cause the resin to crack and the wiring layout to be damaged.

Page 5 V. Description of the invention (2) 2 The adhesion between the metal substrate and the resin is improved, and the metal surface was roughened by machinery before, so-called fixed points are formed, but this machine = poor productivity And often lead to high costs, 'Born again during processing, grain: often damage the nature of electronic and electrical parts: Therefore, in fact, generally implemented on the surface of the metal substrate. In steel materials, dish salt treatment: Cu 2 and copper alloy ‘Je ί Black’ are treated with copper oxide as its representative. The former is a method of dissolving heavy metals with a low solubility in the third phosphoric acid of sub- =, and contacting it with a phosphoric acid aqueous solution; the latter is a method of boiling by immersion in a strong alkaline aqueous solution containing an appropriate oxidant. ,,

The film of Ur number formed by phosphate treatment contains crystal water. At most, "dyeing wide range Λ in the junction 1 will be destroyed, and the heat resistance of the film is not good; poor j: 二 1 = # 左 接 者 的 前 的Although the adhesiveness is good, it is gradually reduced due to the long duration of time. 1 It is also common to maintain the initial adhesiveness for heat treatment. In this regard, in JP-A-9-209167 or JP-A-9 = Medium ', a liter is treated by applying a chromate treatment to the surface of a metal substrate. Furthermore, in Japanese Patent Application Laid-Open No. 2000-1 9235, it is also proposed that a method of forming a large number of minute scales on the surface without using an electrolyte layer is proposed. Any of the special chrome-based Ϊ Ϊ ί ί methods used in flakes can be used in the surface treatment liquid. You can know that the 6-U compound on the surface of the metal substrate is formed. This is for environmental protection. Less desirable. The road to the shell [Problems to be solved by the present invention] V. Explanation of the invention (3) The present invention aims to solve the aforementioned prior art by 'non-use of hexavalent chromium, etc .;', the purpose of the present invention Adhesiveness between metal substrate and resin, the cause of the matter, and an improved surface treatment film. It has excellent performance at the time of temperature recovery. [Methods to solve this problem] In order to solve the above-mentioned technical door 0§, the results are focused on the heat-resistant metal records and formed on the surface. The recorded oxide; 7 = the element with excellent qualitative properties was invented with the resin, and the only film was introduced into the third treatment film. In other words, the present invention relates to a nickel-based surface-treated film which is a surface-treated film formed on a target material, and which is excellent in thermal adhesion. "Symptoms and resistance of resins": dual use: it is a substitute element for phosphorus in the nickel-based surface film of the present invention. Anti-pancreatic acid & some of the aforementioned record-based surface treatment film can also contain elements and friends. Coexistence. The content ratio of nickel, phosphorous, and / or $ of Yaneryi® Shuangliyi is that the content ratio of the upper layer is greater than that of the lower layer, which means that it is ideal to satisfy the relationship described in one household. [(Phosphorus And / or boron) / Ni] the lower layer < [(phosphorus and / or boron) / 0] the upper layer; and the upper layer of the nickel-based surface treatment film contains a columnar structure, the columnar name I is opposite to the nickel-based surface The content ratio of nickel, phosphorus and / or boron of the treated film is higher than that of the upper layer. The ratio is 比 β _ JL. Please listen to the explanation (4) = — ideal. ideal. The surface treatment film forms bamboo shoots on copper or copper alloys and describes the color appearance of the present invention. It is desirable that the A-layer film has gray, gray-black, and black. The following will describe the present invention. The surface of the nickel-coated surface treatment film is made in more detail. The surface of the nickel-based material of the present invention is: 3 films; J is configured to contain metallic nickel and a plate and a layer structure. Is it ashore? The formation of the i material and the two materials is due to the closeness of the material. In the field, it is often necessary; copper or shank;: =, in the field of electronic and electrical parts. The object material is centered on copper: gold and resin The continuity of the recording of the present invention is shown in Figure V. The cross-section scanning electron microscope (hereinafter the recording of the present invention is shown in Figure 2. The symbol 1 in Figure 1 represents oxygen and phosphorus) The symbol of Figure 丨, columnar structure (including nickel, lower layer (including recording, disc ^^ hair / month) is a surface-treated film. The symbol 3 of the invention 丄 f 1 represents a copper substrate. Figure 2). The surface image of the nickel-based surface-treated film (χΐ〇〇〇〇 is shown in Figure 1, this is mixed. And can be observed on the surface of the surface of the columnar fish film treated with columnar structure, observed (Figure 2) There is a slight gap between the non-column openings. Therefore, if the surface level is extremely fine, it can be found that it has irregularities such as several Bnm to several hundred nm, and it can be bonded to the resin. Obtained and huge and effective 574420 V. Description of the invention (5) Substantial surface area. As analyzed by XPS, the upper nickel The oxide state and the thickness is about 50nm. 'The oxide formed on the metal nickel is only a thin film, and it cannot form the maggot-like structure of the present invention. The third element introduced by the present invention' is through a dish. And / or the introduction of collars to obtain the form of the present invention. Empirically, these third elements are preferably in the range of 2% to 50% by weight. When the content is less than 2% by weight, such a form cannot be obtained, exceeding 5 〇Weight% has no hindrance, it is difficult to form a nickel film with such a composition as the content increases. That is to say, it is more disadvantageous in terms of economy. The nickel-based surface treatment film of the present invention has a columnar structure higher than 5 The range of 〇 ~ 3000nm is ideal. If it is less than 50mm, the fine unevenness on the surface will not be fully formed, and the unevenness will become coarser than 300nm. On the other hand, the thickness of the underlying metal nickel layer is the same. There are no special restrictions. However, one part of the surface of the two object materials is filled with eight ~ @ A 里 相 何 衣 曲 的 口 丨 The knife is filled with a knife, and it is lighter than 0.5 5 // m ^ = heart. Also, because Unnecessary thick film The disadvantage is that the film car is sufficient if it has 5 // m. The upper surface of the nickel-based surface treatment film is gray and black. As shown in Figures 1 and 2, it can be recognized as two colors or even columns. The tissue-like tissue absorbs visible light, but this is ideal for electrons with a gap of π. The copper wiring layout passes through the tree, and the field is more surface-treated than the surface of the film. The life of the presenter (the table of the present invention) It is clear that when the optical layout inspection is performed, and the comparison with the layout, the surface treatment film of the recording system of the present invention is formed into a wire layer, and the surface is oxidized, and the method is based on the object material shape.

Formation. 574420 forming metal nickel layer

The method uses a wet surface treatment such as PVD or the like, ore-deposited gold, or the like, and can also be excellent in the properties of the third element in combination with the aforementioned method by using the J'bonding method or without electricity. In order to make phosphorous eutectoid as the third element, ‘the purpose of the gold plating method is described. A well-known case of adding a sub- 'ore to a watt bath, for example, in the case of gold plating, a commercially available phosphorous acid can also be used. Also, in the non-electrolytic type. 〇-Human phosphorous acid is a reducing agent. Secondly, in order to make it the first element; boron co-firing of 3 elements) and other non-electrolytic materials containing rotten reducing agents. ^ ΜΑΒ (dimethylamine shed is also used as reducing agent DMAB) This is the same as the following: Moreover, such as analysis. And any of these are sold. ~ 驮, can make phosphorus and boron co-exist at the same time, by adding to the gold plating solution / or boron, you can make Carbon, nitrogen, sulfur, and M, adding them to phosphorus and meaning, these methods will be more rational, co-evaluation. In the blackening, the introduction of the additives described below will be able to obtain the action t. For example In other words, when co-analyzing nitrogen, aniline can be added and used. Amine, dimethylamine, triethanolamine, triethylamine gallate, diethanolmorpholine, orthomorphine, glycylic acid, and ammonium Melamine, pyridine 4, imidazole, silk amino acid, minus, aspartic acid, B :, alanine, organic matter. When co-analyzing sulfur, you can add Ν, Ν ~ There are thiocyanic acid crystalline base, 1,3-diethyl-2-furnace-ethyl-aminocarboxylic acid, ethylthionine, bladder amino acid, Bottom: Urinary methylthiobutanine, bladder amino acid, glycidyl amino acid, thioglycol, helyl acid, gum amino acid 1 '2' 3-benzotriazole-2: thiazoline-2? Saccharin, bi ° pyridine, Methanol, thiazole, thio

Page 10 574420

V. Description of the invention (7) 碎 r crushed oxoindole acid. —Sulfabenzoic acid, p-Amino acid: tritium, methyl orange, aminobenzoic acid, thiazole, sulphuric acid, thionium thiocyanate. 2 = salinity ^, 2 can be added when leaching, oxidation Lead-based,:%, representative ammonia systems that can be added with ethylene glycol triamino, etc. are: ::: Gongru = and the case of copper alloy Non-electrolytic ore gold is particularly active, so in the bath, 'the copper is replaced by ore gold due to its inconsistency to phosphorous acid; in this case, by electroplating, the behavior of under-throwing is # 1 and palladium is tested. Gold-plated., Or slightly better. After the nickel money of Weiwei, the electroless mineral gold is used to form a predetermined ^^ human texture layer compared to the target material. Here, let it be equal to 与 2 ^ 7 to form a columnar component on the surface. Specifically, the acid contact treatment of the two agents is more effective for the anode and the cathode; the!, ，, and α α of the local battery has been completed as a special feature of the present invention.

P. 11 Agent. Or, it can also be broad: or a single oxidation oxide and the like to form a single treatment; the second anode electrode •. Although the surface morphology of such an invention is introduced into this surface, although the third element, such as phosphorus, is not introduced into the surface, the nickel-based surface treatment film can be transformed and amorphized; by 5 ' The fine crystals of 574420 are described in the fifth invention (8) on the surface of the columnar structure. The analysis of the third element's nickel content ratio, PS, etc., with caution, shows that the upper layer of plutonium is larger than the lower layer by oxidation treatment. That's it. Moreover, the upper layer of the columnar group; the remaining knots of dishes and the like: 'The surface layer has a high content rate, while the lower layer: emulsification treatment is related to the nickel-based surface treatment skin of the present invention.' :: determined for electronic and electrical parts In the field, although there is no particular limitation on the use of the β T tree, "the present invention: a grease, a polyimide resin dot, and a low glass transition temperature." From the so-called view of continuity, .L ^ M will be converted to the temperature when it reaches the temperature. It can draw a tree of 4 people: the difference in expansion rate is better in continuity. ❻ is the tree of H. Because of its low heat resistance, it is excellent. The surface treatment film of the present invention exerts more k in the resin with high glass transition temperature. The experimental group and the comparative group of the present invention are produced to the present invention. Version ^ Brother Ming Experimental Group 1 Use a Watt bath on the surface of a copper plate (JISC1100) of 30 0 χ 200 χ 0.5 mm. After applying a shock of 1 // m, immerse it to prepare a filling content of 9% by weight. Electroless gold plating bath to form a 5 // m non-electrolytic Ni-P alloy layer. In addition, this was immersed in an oxidation treatment solution mixed with 75% phosphoric acid and 67.5% nitric acid at a capacity ratio of 90 ·· 10 at 40 ° C for 3 minutes, and phosphorus was formed on the surface of the Ni ~ p alloy layer on the copper plate, which was concentrated. Of nickel. The surface after oxidation treatment will have a matte 'and beautiful black appearance. Implement deeper points with XPS

574420 V. Description of the invention (9) Analysis, the top layer is 35 Cao Fan ^,% weight ratio. The attached layer (the lower part of the columnar tissue) is 8.8 'with lifting' Figure 1 and Figure 2 show the experimental group 1. Secondly, 'Implement the aforementioned recording adhesive (the table made by Mitsui Chemicals, "surface / mountain bronze plate, so that the thickness of the polyimide resin 5〇_ stick; \ on == both sides followed by a plate") . = ^ 1% under the conditions of a heating temperature of 25 0 t and a heating time of 2 hours ^ / 1? ° 11:11 The test material was cut at an angle of 5011111, in order to promote its degradation to 85 β after being left in a warm and humid environment for 24 hours , Let it float in the bath of 70 C melting and melting, it is not approved for more than 300 seconds. In the following, the electroplating is described in detail. Watt-bath nickel-salt 45 g / L, water-soluble reagent (using the electrode, the cathode current density is adjusted to hypophosphite L, trisodium citrate: 0 ° ' The value of Ph5 is 9 for ionization. In this way, the electroless gold plating is performed. Experiment group 2 is used for the gold plating bath and treatment conditions of experiment group 1. Touch 'that is, to make it nickel sulfate: 3 3 0g / L,' butterfly acid : Concentrations of 38 g / L, each of which is separated from ten special grades), the bath temperature is at 50 ° C, and the nickel plate is applied at 5A / dm. The electroless gold plating bath is composed of: Na · 0.15 mol / L, ammonium sulfate: 0.5 m 0.25 / 2 mol / L, and nickel sulfate: 0.1 lmoi / L of concentrated water to dissolve the reagent, and caustic crystals are added. The alkali-adjusted non-electrolytic Ni-P alloy bath is heated to ㈣ to form the aforementioned Ni-p alloy 澹. The test using no electrolysis is shown below. In other words, electroless 0 · 126mol / L,

Unlike the electroless Ni-P alloy bath described above, the Ni-B alloy bath was performed in the same manner as in Experimental Group 1. The Ni-B alloy bath was made so that the concentration was salted nickel ...

574420 V. Description of the invention (ο) 'DMAB ·· 0 · 〇6mol / L, malonic acid: 0 · 3 78mol / L, TIN03 · · 70 mg / L each dissolve the reagent in deionized water, and, by Ammonia adjusts the value to 6. The electroless plating so adjusted ...-? Alloy bath was heated to 70 and used. The boron content in the obtained Ni _B alloy film was 2. 8 wt%. This was an oxidative treatment in the same manner as in Experimental Group 1 and showed a faint color. And similarly, using copper polyimide resin adhesive as the medium, the copper was dropped. =; =; Afterwards, the heat resistance of the solder was investigated, and the test group 3 was used for the electroplating of Watt L. At a temperature of 4 ° C and a current density of 5A // dm2, a solution of 10 phosphorous acid was added to form a phosphorus content of 10% by weight. 2Ni_p alloy / gold was subjected to oxidation treatment using the same method as that of the experimental group 1. The neodymium film 5 # m. Because it is black. Below, the same test as the experimental group i_ Pro-Wu Guanzhi's solder heat resistance 'no abnormality within 300 seconds and # 彳 贝 之' in comparison group 1 As usual, after the nickel electroplating used in the experimental group 1 had a nickel plating of 3 // m, it was applied in the same way as the experimental group, and the Watt's shape was slightly tarnished, and the appearance was almost white. Chemical treatment, but the same sample is made and evaluated slightly, and it is peeled off from the test layer coating layer from 2 to 3 below. / I expands and connects to the above test groups 1 to 3, after applying the present invention 'By bonding with resin, for example, even if exposed to ==, excellent heat resistance can be obtained. 〉 Dairun mounted soil brother. In contrast, we can see that the image ratio is 574420. 5. Description of the invention αι) Compared with group 1, the surface of the nickel film is oxidized, and good adhesion cannot be obtained. [Effect of the invention] With the nickel-based surface treatment film to which the present invention is applied, when the metal substrate and the resin are adhered, it can impart lubricity resistance and excellent adhesion at high temperatures, which can bring electrical and electronic parts. High reliability. Furthermore, for its additional effect, the surface-treated film of the present invention has a matte black appearance / view, and when it is subjected to optical inspection of electronic and electrical parts, it can be inspected by giving a good comparison. Increased accuracy.

Page 15 574420 Brief description of the drawings [Simplified description of the drawings] [Figure 1] A cross-sectional SEM image (X 3000) showing the nickel-based surface-treated film of the present invention ° [Figure 2] A nickel-based surface treatment of the present invention SEM image of the surface of the film (X 10000). Explanation of symbols 1 The columnar structure (containing nickel, oxygen, and structure) on the nickel-based surface-treated film of the present invention. 2 The lower layer (containing nickel and phosphorus) of the nickel-based surface treatment film of the present invention.

3 copper substrate

Page 16

Claims (1)

574420 said Year 91121277 6. Scope of patent application [Scope of patent application] 1 A nickel-treated film with a two-layer structure formed on its object-based surface material. The lower layer of the material contains nickel and phosphorus, and the upper layer contains nickel and oxygen. And a nickel-based surface-treated film having phosphorus as its characteristic and heat-resistant adhesiveness to resin. 2—A nickel-based surface treatment film having a two-layer structure formed on the target material. The lower surface of the material contains nickel and boron, and the upper layer contains nickel, oxygen, and boron. Nickel-based surface treatment film. 3 — A nickel-based surface treatment film with a two-layer structure formed on the target material. The lower layer of the material contains nickel, phosphorus, and boron, and the upper layer contains nickel, oxygen, and shed. Ni-based surface treatment film. 4. The nickel-based surface-treated film with heat-resistant adhesiveness to the resin according to any of items 1 to 3 of the scope of the patent application, characterized in that the content ratio of nickel, phosphorus, and / or sides to the nickel-based surface-treated film is The content ratio of the upper layer is larger than that of the lower layer, and the following relationship exists. [(Phosphorus and / or boron) / N i] τ layer < [(Phosphorus and / or boron) / 5. The nickel-based surface-treated film having heat-resistant adhesiveness to resin as described in item 4 of the scope of the patent application, characterized in that the upper layer of the nickel-based surface-treated film has a columnar structure and a column of columnar structure. There is a slight gap from the column. 2003.10.02. 017 574420 Case No. 91121277 Exemption -1 Revision 6. Application for patent scope 6 As described in item 4 of the scope of patent application, a nickel-based surface treatment film with heat-resistant adhesiveness to resin, which is based on copper Or copper alloys. 7. A nickel-based surface-treated film having heat-resistant adhesion to resin as described in item 4 of the scope of the patent application, which is characterized by a gray, gray-black, or black appearance. Page 2 2003.10.02.018 1