TW201134982A - Surface treatment agent for metal - Google Patents

Abstract

Provide is a surface treatment agent for metal, which is effective in preventing discoloration of the metal even when it is exposed to heat treatment during the process or a high temperature environment during use, and allows the metal to possess excellent properties during wire bonding and not having reduced reflectance arisen from the surface treatment. The surface treatment agent is characterized in that it is prepared by dissolving or dispersing specific one, two or more compounds selected from the group consisting of benzotriazine compounds represented by general formula (I), mercaptobenzothiazole compounds represent by general formula (2) and triazine compounds represented by general formula (3), and then adjusting the pH of the mixture to fall within the range of 4 to 7.

Description

201134982 VI. Description of the Invention: [Technical Field] The present invention relates to a surface treatment agent for a metal, particularly a silver or a silver alloy. [Prior Art] A connector for an electronic (four) material connection part ((3)nnec t 〇r), a copper or nickel substrate bond is applied to the surface of brass or μ copper, and a material of mineral silver is applied thereto. Since silver is a good conductor of electricity and heat, silver is used as described above for connectors such as connectors or lead frames. However, the silver-recording material is liable to change color in the air, especially in the atmosphere containing sulfur, which is changed to brown or blue-black due to the rot, so that the electrical contact is deteriorated. As one of the methods for solving such a problem, there is a surface treatment method. That is, the treatment liquid is used to treat the silver-plated surface, thereby preventing deterioration of the appearance due to discoloration or an increase in contact resistance. As a conventional surface treatment method of a mineral silver material, for example, as shown in the patent document, a method of treating a silver plating material in a solution containing an inhibitor is used. According to this method, although it is confirmed that the effect caused by the corrosion of silver plating can be prevented, the prevention effect is not complete, and depending on the atmosphere, there is still a problem that some of them may be discolored. Further, Patent Document 2 describes a surface treatment liquid and a surface treatment method capable of preventing discoloration due to corrosion of a silver plating material and imparting lubricity to the plating surface. The surface treatment liquid contains, as an inhibitor, one or more selected from the group consisting of a specific benzotriazine compound, a decyl benzothiazole compound, a 322696 4 201134982, and a triterpenoid compound, and further contains Lubricants, and emulsifiers. The surface treatment is carried out between pH 8.9 and 8.9, as the surface treatment liquid is not subjected to pH adjustment. When used as a connector, it can prevent discoloration while imparting lubricity. However, the effect of preventing discoloration is not sufficient, and it is not sufficient for financial efficiency. On the other hand, a 'light-emitting diode (LED) device circulates a forward current to a pn junction of a semiconductor, and combines electrons and holes in a junction region to illuminate it. The diode is widely used because of its simple structure and ability to directly convert electrical energy into light energy, which has high conversion efficiency and high reliability. In recent years, from the viewpoints of energy saving and environmental protection, the use of white light-emitting diodes as a new light source for new incandescent bulbs or fluorescent lamps and new lighting fixtures has been attracting attention. Such a light-emitting diode device is designed such that the base of the lead frame is processed, and the LED chip is placed at a position surrounded by the reflecting portion, and the LED crystal is efficiently released in the reflecting portion. Further, when necessary, a resin such as an epoxy resin is used to seal the LED wafer. Such a light-emitting diode device has also been put to practical use as a light source, but there are still various problems to be improved. Among them - there is the problem of improving the reflectivity of the reflection (four). A material having excellent light reflectance is known as a material of silver or gold (Patent Documents 3 and 4). The complex and known silver have high gloss and reflectivity, and are the most suitable materials for reflective materials. 322696 5 201134982 However, silver is active, and the surface of silver film will easily change color due to oxidation and affect the light reflectivity of silver film, so as to reduce Its performance. In particular, the discoloration caused by the heat treatment of the manufacturing process of the rib ribs, the deterioration of the light reflectance caused by the discoloration in the high temperature environment at the time of use, becomes a problem. However, there is no effective technology development for improving the light reflection performance of the silver film or the discoloration caused by oxidation, especially the low light reflection performance caused by discoloration in a high temperature environment. In particular, it is expected to have such an improvement by contributing to the promotion of use as a white light source for lighting for vehicles and lighting. In other words, it is expected to develop a heat treatment which is exposed to an LED manufacturing process or the like, or has a high discoloration prevention effect and excellent wire bonding characteristics in a high temperature environment at the time of use, and there is no possibility of surface treatment. A surface treatment agent for a metal that causes deterioration in reflectance. [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. SUMMARY OF THE INVENTION [Problem to be Solved by the Invention] An object of the present invention is to provide a discoloration prevention even in a high-temperature environment in which a heat treatment is performed during exposure to a LED manufacturing process. High effect and excellent weld line characteristics 'There is no surface treatment agent for metal which is deteriorated by the surface treatment caused by the surface treatment. [Means for the problem] The inventors have intensively studied the results to solve the above problems, and finally achieved the invention of the surface treatment agent as follows. That is, the present invention is: (1) A surface treatment agent for a metal characterized by using a benzotriazole-based compound represented by the following general formula (1) as an inhibitor, and the following general formula ( 2) One or two or more compounds of the above-described mercaptobenzothiazole-based compound and the three-tillage compound represented by the following general formula (3) are dissolved or dispersed in water, and the pH is adjusted to 4 to 7 people.

Ri

(1) (wherein Ri represents hydrogen, a substituted or unsubstituted alkyl group, and R2 represents a metal, hydrogen, substituted or unsubstituted alkyl group.) (2) (wherein R3 represents an alkali metal or hydrogen.)

(3) [In the formula, R4 represents an amine group which is not substituted with -SH, an alkyl group, a dilute group or an aryl group, or a thiol group substituted for a miscible group. R5, R6 represents -NH2, -SH or -SM (M indicates metal inspection). (2) The surface treatment agent for a metal according to the above (1), which has a surfactant. (3) The surface treatment agent for a metal according to the above (1) or (2), wherein the metal is silver or a silver alloy. (4) A surface treatment agent for a metal according to any one of the above (1) to (3), which is used for (10) a (4) (5)-type substrate having a metal surface having silver or a silver alloy on the surface, which is characterized by: The surface treatment agent of the metal described in any one of the above (1) to (3). (6) The substrate having a metal surface as described in the above (5), wherein the surface of the metal treated with the surface treatment agent is 2 〇 (rc is subjected to a heat treatment of 1 knives, and then at 12 〇 (C) The substrate having a metal surface as described in the above (5) or (6), wherein the surface of the substrate has silver or silver alloy LED reflection. [Effects of the Invention] The surface of the metal treated with the surface treatment agent of the present invention has a high discoloration prevention effect after heat treatment, and has excellent weld line characteristics, and does not have a change in reflectance due to surface treatment. The surface treatment agent of the present invention is water-soluble, and since it does not contain an organic solvent or a heavy metal, it is excellent in safety, and does not cause uneven appearance or uneven appearance of spots. Further, the contact resistance is low and the freshener [Embodiment of the Invention] [Embodiment of the Invention] The inhibitor contained in the surface treatment agent of the present invention is a compound of the following 322696 201134982, which is selected Any one or two or more of a benzotris-based compound, a thiol-benzoate compound, and a tri-farming compound. These inhibitors are formed by reacting with a metal to form a thin protective film on the metal surface. And the inside of the metal is protected by the film, and as a result, the insect resistance (discoloration resistance) of the metal surface is improved. The stupid ternary compound used in the present invention can be of a general formula ( 1) Table does not R2

(wherein R1 represents hydrogen, a substituted or unsubstituted alkyl group, and 匕 represents an alkali metal, hydrogen, substituted or unsubstituted alkyl group.) R in the general formula (1), a substituted or unsubstituted alkane represented by The alkyl group is preferably an alkyl group having 1 to 24 carbon atoms, and a substituted or unsubstituted alkyl group represented by R2 is preferably an alkyl group having 1 to 24 carbon atoms. Further, the term "substituent" is preferably silk, recorded, reduced or the like. The aforementioned amine group may also be substituted with a carbon group of 1 to 24 carbon atoms. Among the compounds represented by the general formula (1), preferred are benzobisazole (Ri and R2 are both hydrogen) and 14-methylbenzotriazole (Ri is hydrogen and hydrazine is methyl). And tolyltriazole (Rl is methyl, hydrazine is hydrogen), dioctylamine methyl) benzobisazole (r, hydrogen, 1 is N, N-dioctylaminemethyl) and the like. The mercaptobenzoxanthene compound used in the present invention can be represented by the general formula (2) 322696 9 201134982

CS-r3 (2) (wherein R3 represents an alkali metal or hydrogen.) Among the compounds represented by the general formula (2), preferred are exemplified by the sodium salt of bismuth, hydrazine, decyl benzo (tetra), Unsalted salt of sulfhydryl benzene (tetra) hydrazine. In the case of the general-style (2) towel' #r3 secret metal. The compound of the three soils, which can be expressed by the general formula (3) (3)

Re / [wherein R4 represents an amine group substituted with -SH, an alkyl group, an alkenyl group or an aryl group, or a thiol group substituted with a (4)yl group, R5, Re table *_brain, -sh or an alkali metal). The alkyl group and the aryl group are preferably an alkyl group having a carbon number of 1 to 24, preferably a carbon group of 1 to 24, which is preferably an alkyl group of the substituent of the amine group represented by R4 in the formula (3). For the stupid base. The soil can be described below. Preferred among the compounds represented by the general formula (3) can be exemplified as 322696 10 201134982

Alternatively, there are such metal salts as Na or K. In the case of the general formula (3), when R5 and Re are -SM, it is easy to dissolve the water by the three tillage compounds. The inhibitor will be dissolved or decomposed by water. The amount of the inhibitor added is in the range of 11 322696 201134982 0. 001 to 1 wt% by weight, preferably 〇 〇 1 to 〇 · lwt%. When it is below O.OOlwt%, it is difficult to confirm the treatment effect, and if it is more than 1 wt%, the adverse effect on the contact resistance is exhibited. The water, preferably using pure water, and allowing the inhibitor to dissolve or disperse, adjusts the pH to 4 to 7. As the pH adjuster, hydrazine such as phosphoric acid, acetic acid, citric acid, tartaric acid, oxalic acid, malic acid, or citric acid is preferably used. If the pH is low, the discoloration prevention effect will increase, but the liquid is not stable. Also, the solubility of the inhibitor may be poor. On the contrary, although the stability of the liquid will be good, but the effect of discoloration prevention is good, the color prevention effect and the stability of the liquid are considered, Qiu is 4 to the people. Change from

It is 5 to 6. Further, in the surface treatment agent of the present invention, it is preferable to contain a surfactant in the aqueous solution to improve the surface of the metal to dissolve the plaque on the surface of the washing metal. & ^Infiltration, surface treatment agent, the dissolution aids of the present invention for dissolving the inhibitor in an aqueous solution. Further, in the case where a surfactant is contained, it is preferable that the surface of the heart is excellent in surface activity and has little adverse effect on the environment. ^The fraction of the benzene-containing Ethylene Ethylene Additive or the Higher Alcohol 2 or the test which is less biodegradable is suitable for use. Methyl diol, isopropyl glycol diol ether, or diol ether such as mercapto propylene glycol, internal propylene glycol, and butyl urethane are suitable for use as a dissolution aid. . For example, 322696 12 201134982 pH buffering agent can be used to control the adsorbing property of the inhibitor. The pH buffering agent may, for example, be sodium hydrogen phosphate, acetic acid, sodium acetate, citric acid, citric acid, tartaric acid or sodium tartrate. When considering cost and usability, etc., citric acid, sodium acetate, etc. are preferable. The surface treatment agent of the present invention does not contain a lubricant. In the case of a surface treatment agent used for a connector for connecting parts for electronic equipment, it is necessary to impart lubricity to the metal surface to contain a lubricant, but it is not used for a connector, but is used for an LED reflective material or the like. The surface burying agent of the invention does not need to impart lubricity, and may not contain a lubricant because it may adversely affect the characteristics of the wire due to the imparting of lubricity. In the treatment method, the material to be treated is impregnated into the surface treatment agent, or the surface treatment agent is sprayed or coated, and any method may be employed, but it is preferably impregnated. For the impregnation conditions, the temperature is 15 to 60 ° C for 5 seconds or more, for example, for 5 seconds to 1 minute, and then water is washed and dried. As a result of water washing, the appearance defects such as uneven processing or spots are lost. The treatment material is a substrate having a metal on the surface, and the metal may, for example, be silver, silver alloy, copper, brass, bronze, iron or the like. In particular, a surface treatment agent which is easy to discolor silver and a silver alloy is suitable for use. The silver alloy may, for example, be an alloy of silver and gold, tin, copper, lG (Pd), indium (In), tin, zinc, ruthenium (Ru), rhenium (Rh) or silk (Bi). When the surface treating agent of the present invention is used in such a manner to treat a substrate having a metal on the surface, a film formed of a surface treating agent can be formed on the surface of the metal. The surface treatment agent of the present invention is an aqueous solution, and since it does not contain an organic solvent 13 322696 201134982 or a heavy metal, the stability is excellent. χ, using the treatment agent of the present invention, the surface of the film obtained by the treatment of the core surface, such as 'heat treatment at 2, C 1 〇 minutes, at 12: heat treatment, not only discoloration prevention is still different, Lai Electrochemical, deterioration of reflectivity. The surface treatment agent of the metal of the present invention can be suitably used as a surface of a reflective material having an LED having a silver or a silver alloy on its surface, and is not suitable for the treatment of (4). The examples are given to illustrate the invention in detail. (Example 1) As a substrate to be treated, a silver plating having a thickness of 4 μm on a pure copper substrate was used, and 4 (rc was immersed for 3 sec in the surface treatment agent shown below, and then washed with water. It is dried by warm air using a drier to carry out surface treatment. (Composition of surface treatment agent) 〇. 01 wt% 〇· 01 wt% 1 wt% Inhibitor: Triterpenic-2, 4, 6-trithiol surface The active agent: oleyl hydroxyethoxylate 1 wt% adjusted to pH 5. 5. Dissolving aid: butyl propylene glycol pH buffer: sodium hydrogen phosphate as a pH adjuster using phosphoric acid, after surface treatment of Example 1. The substrate was subjected to a hydrogen sulfide gas test (hydrogen sulfide concentration: 3 ppm, temperature: 40 ° C, humidity 80% RH (relative humidity), test time: 4 hours) according to JIS H8502 without heat treatment. Observed with the naked eye. In addition, heat treatment was carried out at 322696 14 201134982 by a hot air circulation dryer at 200 ° C for 10 minutes, followed by heat treatment at 120 ° C for 6 hours, and the heat treatment was performed on the substrate after heat treatment. The same hydrogen sulfide test, and then the appearance of the naked eye (Evaluation Criteria) 〇: According to the naked eye, the discoloration of the electroless plating surface △: According to the naked eye, the electroplated surface is discolored to a light blue X: According to the naked eye, the electroplated surface is discolored to a thick blue black. The results are shown in Table 1. (Examples 2 to 8 and Comparative Examples 1 to 8) The inhibitors and pH buffers of Example 1 were changed to the compounds and concentrations shown in Table 1, and the pH was made using phosphoric acid as shown in Table 1. The surface of the material to be treated was subjected to surface treatment in the same manner as in Example 1 and evaluated in the same manner as in Example 1. The results are shown in Table 1. 15 322696 201134982 [Table 1] Surface treatment Liquid composition test results inhibitor and its concentration (wt%) pH buffer and its concentration (wt%) pH hydrogen sulfide gas after the appearance of heat treatment and hydrogen sulfide gas test appearance Example 1 San Geng-2,4 , 6-trithiol 0.01 phosphoric acid gas 1 5.5 〇〇 Example 2 Sangen-2,4,6-trithiol sodium salt 0.01 Sodium citrate 1 6.0 〇〇 Example 3 2-aniline-based three-ploughing- 4, 6-dithiol 0.01 sodium hydrogen phosphate 1 6.5 〇〇 implementation 4 2-Diethylaminotrim-4,6-dithiol 0.005 Sodium citrate 1 5.5 〇〇 Example 5 Sodium salt of 2-dibutylaminotrimenen-4,6-dithiol 0.01 Sodium acetate 1 6.0 〇〇 Example 6 2-Dihexylaminotrim-4,6-dithiol 0.01 Sodium tartrate 1 5.5 〇〇 Example 7 1-Mercaptobenzotriazole 0.01 Sodium hydrogen phosphate 1 6.5 〇 〇 Example 8 Sodium benzothiazole sodium salt 0.005 Sodium citrate 1 5.5 〇〇 Comparative Example 1 Untreated — — — XX Comparative Example 2 2-Anilinotrid-4,6-dithiol 0.01 — 7.5 Δ Δ Comparative Example 3 2-anilinotriterpene-4,6-dithiol 0.005 — — 7.5 Δ Δ Comparative Example 4 2-Dibutylamine-based three-till-4,6-dithiol 0.01 1 9.0 Δ Δ Comparative Example 5 Sodium salt of 2-dibutylaminotrimethylene-4,6-dithiol 0.005 Citric acid 1 3.0 Δ Δ Comparative Example 6 Sangen-2,4,6-trithiol 0.01 — 7.5 Δ Δ Comparative Example 7 Sodium salt of mercaptobenzothiazole 0.005 — — 7.5 Δ Δ Comparative Example 8 1-Methylbenzotriazole 0.01 Sodium hydroxide 1 9.0 Δ Δ Using Examples 1, 2, 7 and comparison Surface treated sample of Example 1 The material was evaluated for contact resistance, freshness wettability, fresh line characteristics, and reflectance as follows. The results are shown in Table 2. (1) Contact resistance 16 322696 201134982 Contact resistance, measured according to DC 7.4mA, open circuit voltage 20mV, load 2. 5 to 50g. The criterion for determining the contact resistance is as follows. 〇: Contact resistance is 〇. 02Ω or less x: Contact resistance is 0.02Ω or more (2) Solder wettability Solder wettability is 265. (: The tin-silver-copper alloy flux bath is dipped in the sample before and after the heat treatment, and the time required for the buoyancy to become zero is measured. The heat treatment is performed at 20 (after 10 minutes of TC, then at 120 C). 6 hours of implementation. The criteria for determining the wettability of the solder are as follows: 〇: The time required for buoyancy to become zero is less than 0.2 seconds. x The time required for buoyancy to become zero is 〇. 2 seconds or more (3 The characteristic of the fresh wire characteristics of the wire is that after the wire is welded, it is cut at a speed of 5 〇〇 # m/sec, and is evaluated according to the cutting position of the wire. The reference is as follows: 〇. Line breakage X = peeling of the joint surface between the wire and the sample (4) Reflectance reflectance is measured by ultraviolet visible spectrophotometer (ultraviolet visible spectrophotometer) The reflectance at a wavelength of 450 to 900 nm was evaluated. The heat treatment was carried out at 200 ° C for 1 〇 and then at 12 〇. (: 6 hours was carried out. The reflectance was judged as follows. 〇: at 450 All reflections up to 900nm It is 90% 17 322,696,201,134,982

the above. χ: There is a wavelength at which the reflectance becomes 90% or less at a wavelength of 450 to 900 nm. [Table 2] Flux after wettability after contact resistance heat treatment Wet solder wire characteristics after heat treatment Reflectance after heat treatment Reflectance after heat treatment Example 1 〇〇〇〇〇〇 Example 2 〇〇〇〇〇 〇Example 7 〇〇〇〇〇〇Comparative Example 1 〇〇X 〇〇X Since Examples 1, 2, and 7 did not show an increase in contact resistance, deterioration in solder wettability, and deterioration in reflectance. It is understood that there is no adverse effect on contact resistance, flux wettability, and reflectance due to the discoloration prevention treatment. Further, in Examples 1, 2, and 7, the peeling of the bonding surface between the wire and the sample did not occur, and it was found that there was no adverse effect on the wire bonding characteristics due to the discoloration preventing treatment. [Simple diagram description] None [Main component symbol description] None 18 322696

Claims (1)

201134982 VII. Scope of application for patents: Buzheng: a triazole-based compound as an inhibitor, a surface treatment agent of the following general metals, characterized by: benzene represented by the following general formula (1) And a benzoin-based compound represented by the formula (2) and a group of the D-line compound represented by the following general formula (3) or a compound of two or more kinds dissolved or dispersed in water, and Adjust Qiu to 4 to 7, (wherein R! represents hydrogen, a substituted or unsubstituted alkyl group, R2 represents a metal, hydrogen, substituted or unsubstituted alkyl group), (wherein R3 represents an alkali metal or hydrogen), Wherein R4 represents an amine group substituted with -SU, a pyridyl group, a dilute group or an aryl group, or an alkyl group substituted imidazolylalkyl group, and r5, Re represents _2, -SH or -SM (M represents an alkali metal) )]. 2. The surface treatment agent for a metal according to claim 1, wherein a surfactant is further contained. 3. The surface treatment agent of the metal according to claim 1 or 2, wherein the metal is silver or a silver alloy. The surface treatment agent for a metal according to any one of claims 1 to 3, which is used for an LED reflective material having a silver or a silver alloy on its surface. A substrate having a metal surface, which is characterized by being treated with a surface treatment agent for a metal according to any one of claims 1 to 3. 6. The substrate having a metal surface as described in claim 5, wherein the surface of the metal treated with the surface treatment agent is heat treated at 200 ° C for 10 minutes and then at 120 ° C. The discoloration prevention property after the heat treatment for 6 hours was still excellent. 7. The substrate having a metal surface as described in claim 5 or 6, wherein the substrate has a silver or silver alloy LED reflective material. 2 322696 201134982 IV. Designated representative map: There is no schema in this case (1) The representative representative figure of this case is: (). (2) A brief description of the symbol of the representative figure: 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: 3 322696