TW200526817A - Sealing agent, sealing method and printed board treated with said sealing agent - Google Patents

Abstract

The present invention provides a sealing agent which has no problem of environmental pollution, makes the plated film treated therewith has corrosion-resistance equivalent to or better than that treated with previous sealing agent, and does not deteriorate the wettability of solder of the plated film treated therewith; as well as a sealing method using the sealing agent and a printed board treated with the sealing agent. The sealing agent comprises 0.001 to 0.1 wt% in total of one or two or more heterocyclic compounds containing mercapto group or the salts thereof, and 0.01 to 1 wt% of a surfactant, and the pH of the solution is adjusted to 10 or less.

Description

200526817 IX. Description of the invention: [Technical field to which the invention belongs] The present invention is related to sealing treatment or containing zinc zinc-especially 疋 related to having electroplated nickel material: ... a gold or gold alloy with the material as the bottom layer, Printed board / sealing treatment method based on material and treatment with the treatment agent [Prior art] In the high-end industry, gold-plating is used for the contact parts of electronic and computer equipment such as electronic and computer equipment. = In the past years, the ratio of miniaturization and advancement of electronic equipment has been divided into two: pieces (connectors, switches, seals, etc.) ^ After mining, gold is used as the bottom layer of electronics on the copper base material. Most of the machines require economic efficiency. The above-mentioned mined gold comes at a cost. Therefore, Menbei generally reduces the thickness of mined gold in order to reduce the pores. If the pores become thin, the pores will increase logarithmically, such compounds, vapors, etc. ) Intrusive ^ Rotten substances (water, sulfur, this rotten product combined with // :: Guangchi, the bottom layer of the ground and the substrate. Etc.). Θ "Surface precipitation, leading to the deterioration of contact resistance. Method one t J one π + mechanical system and blood mechanical system, etc. Fang Feng Guding, treatment. Sealing treatment has ... Organic systems due to the general use of halogen-based organic solvents 3J67J0 • 200526817 agent as a solvent, from Shaping one of the human body ~ The damage to the environment such as the damage of the lice layer will cause problems with the shouting point. 1 樯 L L, branches are not known to have a chromate method, but in addition to the bag, Due to the influence of the right 丄 in the solution “ the west priest _ environment and other issues. Chromium ㈣ ㈣ human body In response to these problems, HOWA proposes the use of surfactants and water-soluble water-soluble plugging agents emulsified as organic inhibitors. For example, 'Patent Document 1 discloses that one or two or more kinds are selected from &: two: sialosalic compounds, Weicyl benzothiwa compounds, and Sanhum formulations: water compounds, lubricants, and emulsifiers are used as water-based plugging treatment agents to suppress the market. "/ Patent Literature 2 Reveals that it contains one or two or more compounds selected from the group consisting of benzole compounds, mercaptobenzopyrene η ^ ^ ^-a group of chemical compounds made from the Qin compound, a sex agent, and an amine compound as an inhibitor. Sealing treatment agent W < Including the above-mentioned patents, due to the use of contacts in conventional sealing places and connectors, it is necessary to provide pluggability through the characteristics of the coating film + Wenshui 4, ^ The upper X cloth has a lubricating component, and it is ancient. ^, Points = barriers to the rotten components in the atmosphere, which provide resistance to rot. When 〆 ', = a sealing agent is used for the pad portion of the printed circuit board. ^ On, the welding wettability of the connecting part is significant Question of deterioration ^ Xiheli Document 1 · Japanese Patent Publication No. 2804453 Patent Document 2: Japanese Patent Publication No. 2003-1 29257 [Summary of the Invention] 31671〇200526817 There is no environmental pollution problem and the treatment can be equivalent to the conventional one The above-mentioned sealing treatment agent, solder sealing treatment agent, and improved sealing treatment agent and sealing treatment method 1 are intended to solve the above-mentioned problems. ^ And the treatment agent is to solve the above problems. The inventors of the present case have discovered the following sealing treatment agent and use of the treatment: one or two or more of a heterocyclic compound or a salt thereof, one, · Wt%, and a surfactant 0.1 to 1 wt% And the sealing treatment agent which is characterized by adjusting the pfH of the life fluid directly to a range of 10 or less and adjusting the 0 'pH value to a range of 8 to 10. (3) A plugging treatment method characterized by performing a plugging treatment using the plugging treatment agent disclosed by the above-mentioned ⑴ or ⑵. ~ ⑷ Use the printed circuit board at the sealing hole disclosed in ⑴ or ⑴ above. Wang Yifeng will imitate [embodiment] [perform the best form of the present invention] The first necessary component of the sealing agent of the present invention = one or two or more compounds or salts thereof. These compounds are reacted with nickel to form: reaction formation ™: rolling and burying, as a result, the corrosion resistance of gold plating can be improved. 316710 7 -200526817 The thiol group-containing heterocycle used in the present invention has one nitrogen atom and a 5-member heterocycle. : Condensation, preferably at least an aromatic ring. The better is ;,]: '6-membered heterocyclic compounds, and the use of these salts (sodium salt, the compound represented by the formula described in cattle 17). Also, bismuth salt, amine salt, etc. ).

Lwt% ， SH wooden force of these compounds -η ηπι + 0 / j, plus I in the range of 0.001 to o.lwU vortex 〇. OOlwt%, there is no button 丨 忐, if it exceeds 0. lwt% ， | 3] 67] 0: 200526817 Touch resistance has an adverse effect. It is preferably 0.005 to 0.05 wt%. Further, by adding a surfactant to 0.01 to 1 wt%, it was found that the corrosion resistance was increased. It is thought that the surfactant can reduce the surface tension of water and increase the permeability of thiol-containing heterocyclic compounds or their salts to stomata. If the amount of the surfactant added is less than 0.01% by weight, sufficient permeability to the above pores cannot be obtained and sufficient corrosion resistance cannot be obtained. When it exceeds 1 wt%, the cleaning effect of the surfactant becomes strong, and the adsorption of a heterocyclic compound having a mercapto group or a salt thereof is prevented, and a sufficient effect cannot be obtained. As the surfactant, one or two types of anionic surfactants, cationic, nonionic, and amphoteric surfactants that are commercially available can be appropriately selected and used. In particular, when the pH value of the samarium solution is used in the range of 8 to 10, one or two or more anionic, non-ionic, and amphoteric surfactants are appropriately selected. In #, the self-ionic surfactant is nonylbenzene fluorene ethylene oxide addition (6 to 12 moles of ethylene oxide) or intermediate alcohol ethylene oxide with φ adduct (soil milk ethane) The Mohr number is more preferably 6 to 12). The anionic surfactant is preferably a sulfate type or a phosphate type. A sealing treatment agent disclosed in Japanese Patent No. 2804453 has a water-repellent coating due to 3 / lubricant and emulsifier, and provides lubricity and corrosion resistance. In addition, the sealing agent disclosed in Japanese Patent Laid-Open No. 2003-129257 discloses that, by adding an amine compound, the metal surface shows water repellency, thereby improving the corrosion resistance. However, if the metal surface becomes water-repellent, a glaze or solder applied for the purpose of improving the wettability will significantly degrade the solder wettability. 316710 9 200526817 8. Since Ben Γ does not contain the above-mentioned effect of imparting water repellency to the metal surface, Tan Xi's wettability will not be deteriorated. Because of its low water-repellency, it has poor corrosion resistance. The present invention is formed by the penetration of the surfactant into the solution ... in the salt, and it is made of corrosion-resistant pure agent. 6 " Can dry and the previous sealing treatment 2 = The detailed relationship between the two Qiu value and corrosion resistance is unknown, but the pH value is more acidic, and the corrosion resistance is in the range of 8 to 10 when used & liter . It is known that the high corrosion resistance can be imparted at the Qiu value. The following = ΓΡΗ value must be below 1G, but ^ value will be included if it is in the 7th period: agricultural use is better in terms of tree management. Gan e main 1U dry surrounding By injecting liquid into the sealing treatment tank, it is predicted that the pH value of the liquid will change during use and processing. In order to # 留 bianf 丨 昍 μ, it is better to stop the pH change to take a small limit value 'to add p H buffer. In the present invention: Substances having pH buffering energy can be listed as metal test salts of acetic acid, metal test salts of didichroline acid, trimeric owing ... Limb test metal salt, ammonia, ethanolamine, two

… The plugging agent of the present invention has the above-mentioned components, and the material may be selected from water, ethanol, acetone, and n-alkane. However, considering the economical or ignitability = having _] appropriate choice of 51 human nature, water is the most suitable solvent. 3] 67] 〇10 •• 200526817 When the solvent is water, 'heat the temperature of the solution to 4 (TC to say, the ceremonialization of the ingredients in water will become faster, and the processed material will be easy to dry. "The processing method can be Any method of immersing or smelting electrical minerals in the treatment agent, such as: service or painting. However, in the present invention, the shape of the electroplated product is no matter whether it is plate-shaped, strip-shaped, or profiled parts. ". 泉" can be processed in the production line to improve the effect of various functions of sealing treatment. Two = after the product is processed and then processed, the sealing treatment agent of the present invention is used.

Even if it is a metal material that has been subjected to sealing treatment after power ore / the function of cleaning the pressing hole attached to the pressing oil during the subsequent pressing processing = the function is greatly lost. It is effective to perform the sealing process again in this phase. 2 Treatment of fluorene group ::: board with the sealing agent of the present invention will result in degradation of the pure energy equivalent to that in the past. [Examples] —The following is a detailed description of the present invention with examples.丨 Only detailed examples 1 to 9 and comparative examples 1 to 8 For scale yellow bronze substrates for elastic yellow are passed through a watt bath, ... plate (.521〇, 25_ 20_ 〇.4_) Γ, nickel plating, and cyanate In the solution, 0 · 1 // m of gold plating is defended. Fractional r 仃 仃 the gold-plated substrate with the composition of Table 1-rn〇r, 夺, master,, and the sealing treatment agent can not be processed under the conditions of bath, attack 50 ℃, time of 20 seconds A sealing film is formed on the alloy. Also, dry without exchange water during plating. Use of ions as the solvent of the sealing treatment agent The following evaluation was performed on the substrate after the sealing treatment. The results are shown in]] 316710 200526817 Table i. Salt water spray test ^ Fang ... Hai and other substrates were subjected to a 24-hour salt water spray test (based on JISZ2371 two standards) to evaluate corrosion resistance. Evaluation Criteria 〇 · Almost no corrosion △: Dark brown corrosion spots are seen everywhere> X. Green corrosion spots (copper rust) are seen everywhere Solder wettability will help _26, Damura Chemical Research Corporation (Manufactured) = 2 times the amount of propene released) Fully coated, put 5 4 solder balls (super clean ball s, tin_37% H 6 industry (stock) company killing) after 1G minutes, force 4 The Shi Zhengzheng Cup is a worker's clothing, and is heated on a hot plate kept at 15 (TC for 2 minutes (preliminarily and then added on a hot plate maintained at 230 ° C for _ 30 seconds. Soldering, insect evaluation by determination After heating, the wet expansion area of the solder pad is as follows: I: The wet expansion area of the solder ball is used as a reference (n = 5). 谇 Evaluation criteria of solder wettability 〇 • The solder ball is expanded by the wetness * &gt; Go_ χ 〇95 Enriched product> Untreated wet expanded area X · Wet expanded surface of too dry solder ball <Flu χ 〇7, Large area <Untreated wet expanded area again, Japanese patent will be issued Publication No. 2804453 _ Substrate (Comparative Example 7) and Substrate (Comparison with JP 2003-129257) Example 8) As a comparative example, it is reported as a report of 1 Khan estimates. The composition is as described below under 316710 12 200526817. The results of the Khan test results are shown in Table 1. Comparative Example 7 (Japanese Patent No. 2804445) Sealing treatment ^ Inhibitor: Benzotriol. O.Olwt% Lubrication sword: Oleic acid 0.3 wt% Emulsifier: Lauryl acid phosphate monoester 0.3 wt% Specific Example 8 (Japanese Patent Laid-Open 2003-129257 Sealing treatment agent disclosed in the gazette) Inhibitor: Benzotriazole 0.05% by weight Amine compound: Triethanolamine 丨 wt〇 / 〇 Carnic acid _ series surfactant: EN-2P (manufactured by Aoki Oil Industry Co., Ltd.) 0 · 1 wt%

316710 -200526817

[1 丨 1 Test results Solder wettability 0.00000000000000 Salt water spray test 〇000 〇〇〇〇〇〇 Sealing treatment liquid composition f Cold 4 »&gt; LO LO CD LD σί LO ① LO LTD c ^ &gt; LO CT5 LO LO οο CO οο CNI CNI 〇〇〇〇CNI (NJ potassium pyrophosphate potassium pyrophosphate potassium pyrophosphate potassium tetraborate potassium tetraborate potassium tetraside acid if potassium pyrophosphate potassium pyrophosphate potassium pyrophosphate Surfactant and its concentration (wt? 〇LO CD LO cz> LO CD LO CD LO CD LO ◦ LO CD LO 〇LO CZ5 Nonylphenol ethylene oxide 10 moles Nonylphenol ethylene oxide 10 moles Ear Additives Nonyl Stupid Ethylene Oxide 10 Mol Additives Laureth Ethylene Oxide Additives Phosphate Lauryl Ethylene Oxide Etylene Additives Eric Acid Lauryl Alcohol Ethylene Etylene Additives Filler Acid Ester Lauryl Alcohol Ethylene Oxide Sulfate Salt Lauryl Alcohol Ethylene Etylene Sulfate Sulfate Salt Lauryl Alcohol Cyclopentane Ethane Sulfate Salt Sulfate Compound containing myelin or a salt thereof and its concentration (Wt%) ^ ― (〇 &gt; f Η CD ο C3 CD 〇 &gt; r -__ H 〇T-Η 〇 &gt; r Η 〇 &gt; Τ '(CD ◦ 3-fluorenyl-1,2,4-triazole 2-mercaptobenzothiazole sodium 2-fluorenylbenzoxazole 3-fluorenyl-1,2,4-triazole Sodium 2-fluorenylbenzothiazolyl 2-fluorenylbenzothiazolyl 3-fluorenyl-1, 2, 4-triazole 2-fluorenylbenzothiazolyl sodium 2-fluorenylbenzothiazolyl T-fluorene (ΝΙΙ ΓΟ LO CO 〇〇CD 453-] 4 316710 -200526817

[Z 丨 I 婶] Test results Solder I wettability 〇 〇 〇〇〇〇XX salt water spray test &lt; 3 1 &lt; 3 &lt;] &lt; 3 X 〇 &lt; 3 The pH treatment agent is composed of the gift solution and its buffer Concentration (wt%), pH value LO cn &gt; LO LO CT: LO LO CD 1 LO CZ5 1 ..... * CO CN1 CO CO 1 1 1 1 potassium pyrophosphate potassium pyrophosphate potassium pyrophosphate potassium pyrophosphate not added 1 1 1 Surfactant and its concentration (wt%) LO 〇 &gt; LO 〇0.005 CNI LO 〇1 1 1 Sulfate salt of lauryl alcohol ethylene oxide additive Sulfate salt of lauryl alcohol ethylene oxide additive Nonylbenzyl oxirane 1 0 Molar addon Nonylbenzol ethylene oxide 10 Molar addon Lauryl alcohol Ethylene oxide Addition linoleic acid 1 1 1 Heterocyclic compound containing thiol or Its salt and its concentration (wt%) 1_ 0.0005 LO &lt; ZD ψ &lt; CD CD 〇CD CZ5 CD 1 1 1 2-Sodium benzobenzothiazole 2-sodium benzthiathiazole 3-fluorenyl-1, 2,4-triazole 3-Weiji-1,2,4-triazolyl 2-mercaptobenzothiazole sodium is not treated. Japanese Patent Publication No. 2804453, Japanese Patent Publication 2003-129257 — CNJ CO LO CJD. 15 316710 2005268 17 From the above results, it is clear that the sealing treatment agent of the present invention does not contain substances that will pollute the environment, and the electroplating material treated with the sealing treatment agent of the present invention has corrosion resistance equal to or higher than that in the past, and does not cause Degraded solder wettability 0

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Claims (1)

， 200526817 X. The scope of Shenyin's patent: ^ 1 two sealing treatment agent 'has a thiol-containing heterocyclic compound or its salt 〆 2 or more kinds of juice 0.001 to 0 · and surfactant to 1 Wt%, If the pH value of the solution is adjusted to a range of less than 10, 0 2 · If the pH value of the first range of the patent application is adjusted to 8 to item, the sealing solution is in the range of 10. 3. A sealing treatment method, 苴 牯, special, is to use the sealing treatment agent in the scope of the patent application for item 1 or 2 for hole treatment. 4. A printed circuit board characterized in that it has been treated with a sealing agent in the first or second range of the patent scope. 316710 17: 200526817 VII. Designated Representative Map: None (I) The designated representative map in this case is: (). (2) Brief description of the component symbols in this representative figure: _ 8. If there is a chemical formula in this case, please disclose the chemical formula that can best show the characteristics of the invention: There is no representative chemical formula in this case. 4 316710