TW201014829A - Novel imidazole compounds, surface treating agents, print circuit boards and a method of producing the same - Google Patents

Abstract

This invention provides an imidazole compound. Because of precipitation due to pH changes or evaporation of the processing solution is inhibited, and being highly soluble to organic acid aqueous solutions, the compound can be stably and continuously used even if the impurity ions from the processing of the print circuit boards or soft etching are mixed in and is used for surface treating agent. This invention provides a novel imidazole compound represented by the following general formula. R.sub.1 represents a hydrogen, straight- or branched chain alkyl group of 1 to 11 carbon atoms. R.sub2 respectively independently represents a straight- or branched chain alkoxyl group of 1 to 11 carbon atoms. R.sub.3 respectively independently represents a straight- or branched chainalkyl group of 1 to 11 carbon atoms, chlorine or bromine. M is an integer of 1 to 4, n is an integer of 0 to 4.

Description

[Technical Field] The present invention relates to a novel miso compound, a surface treatment agent, a printed circuit board, and a method of manufacturing the same. BACKGROUND OF THE INVENTION The printed circuit board is formed by, for example, forming a pattern of circuit wiring on a steel-clad laminate, and mounting an electronic component thereon to form a substrate of a circuit unit. In many such printed circuit boards, a surface mounting type in which a circuit pattern having a circuit wiring is formed on a surface thereof and an electronic component is mounted on the circuit pattern is used. For example, when an electronic component having a wafer component having electrodes at both ends is mounted, a flux (flUX) is applied onto a printed circuit board, and the wafer component is soldered by a solder wave soldering method or a reflow soldering method. In the soldering of the wafer parts, after forming the circuit pattern of the printed circuit board, that is, the copper foil portion of the copper clad laminate is obtained to obtain the required circuit wiring, the solder chip parts are left in the obtained circuit. The portion (the portion of the so-called solder pad) is then coated with a solder resist film. However, there are also methods of directly soldering wafer parts after soft etching. However, in many cases, the steps up to the coating of the solder resist film and the subsequent soldering steps of the wafer parts are performed independently. For example, the printed circuit board on which the solder resist film has been coated may be stored as a component, and the soldering step of the wafer component may be performed at another time. The printed circuit board may be circulated, and the splicing step may be performed by another manufacturer. In such a case, the copper (four) surface of the welding age is likely to be oxidized by the time of the welding process, and the copper (four) surface of the welding age is easily oxidized; t is more likely to occur in the case of a lot of moisture. The air of the copper box surface of the welded lining is oxidized. Therefore, in order to prevent oxidation of the surface thereof, an operation of forming an oxidation resistant film is performed, and for this purpose, (4) a surface protective agent. 3 Even if the printed circuit board is covered and soldered, the printed circuit board is used in the case of mounting electronic parts on both sides, for example, by using the reflow method f; % on the soldering lining, applying the coating paste The high temperature is heated like this to make the solder powder melt. Therefore, when the surface of the printed circuit board is subjected to the bonding welding process, the other surface is exposed to a high temperature, and since the copper case of the solder pad is oxidized, the treatment for forming the oxidation resistant film is still required in such a case. When the treatment with such a surface protective agent is carried out, or in order to prevent deterioration of heating caused by the one-side welding process of the printed circuit board, and the oxidation resistance is also applied to the other surface of the soldering pad, a so-called pre-use is used. Flux (preflux). Among them, water-soluble preflux which does not use organic solvents, is free from pollution and fire hazard, is suitable for use. In the past, the copper foil of the exposed soldering pad was rust-proofed. In this regard, as described in the patent document 丨 and Patent Document 2, it is known that a surface protecting agent for a water-soluble printing wiring board containing a benzimidazole-based compound is used as a water-soluble preflux. In the patent documents 1 and 2, "the printed circuit board having the copper foil circuit pattern formed on the surface is impregnated into the surface protective agent for a water-soluble printed wiring board containing a benzimidazole compound", whereby the copper in the circuit pattern of the printed circuit board is used. A heat-resistant coating film is formed on the surface of the copper alloy. This coating film has excellent moisture resistance even after exposure to high humidity, and is excellent for the protection of the printed circuit board and the weldability of the 201014829 parts. In addition, in the case of pre-flux containing rosin, the coating is formed in (4) Koche, and after the parts are mounted, high reliability cannot be obtained unless the unnecessary coating film is cleaned. If you use a water-based pre-flux like the ones in the specials, the forest needs to be cleaned and not used. Therefore, it is better at the point of raw materials and materials. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei No. Hei-5- No. Hei. No. Hei. No. Hei. No. 5 (1) (10) 888. In recent years, most of the bonding methods for electronic components of printed wiring boards are surface mount methods, but because of wafer parts. Temporary joining, mounting on both sides of a part device, or mixing of wafer parts and discrete parts, etc., causes the printed wiring board to be exposed to high temperatures, and when the surface of the printed wiring board is treated with an imidazole compound having a long-chain alkyl group at two positions Since the printed wiring board is exposed to high temperatures, the surface-treated copper surface is discolored, which hinders the subsequent soldering, and thus is not suitable for the surface mounting method. Further, in Patent Documents 3 and 4, the surface protective agent for a water-soluble printed wiring board containing a taste of a sitting compound is formed on a surface of copper and a copper alloy of a copper foil circuit pattern, in particular, a heat-resistant coating film, in particular A treatment solution containing a 2,4-diphenylimyl 11-seat compound forms a chemical conversion coating film having good heat resistance on the surface of the copper metal, thereby ensuring good weldability after reflow heating in the surface ampoules step, and treating The liquid does not precipitate an active ingredient in the treatment bath and is stable. However, when the surface treatment of the printed wiring board is carried out using these 2_aromatic miso compounds, a chemical conversion coating having good heat resistance can be formed on the surface of the steel metal. Membrane, but there is still a problem to be solved in practical use. [Patent Document 3] Patent No. 3277025 No. 5 201014829 [Patent Document 4] Patent No. 3376743, that is, because these imidazole compounds have low solubility in an aqueous solution of an organic acid, Therefore, the imidazole compound is liable to be precipitated due to an increase in the pH of the treatment liquid to be adjusted or evaporation of the treatment liquid, and the precipitated solid imidazole compound crystal is greatly crystallized. In the case where the apparatus is not in operation, the above-mentioned problem is remarkable when the storage temperature of the treatment liquid in the tank or during replenishment is lowered. The object of the present invention is to provide a high solubility in an aqueous solution of an organic acid, which is caused by the treatment liquid. The precipitation of the imidazole-based compound such as pH fluctuation or evaporation is suppressed. Even if it is mixed with the printed wiring board or the soft (four) treatment, it is still possible to continue to use the compound which is suitable for use in the table = treatment agent. Further, the subject of the present invention is to use a metal surface treatment agent using the imidazole compound so that the _axis has heat resistance and has a coating film having very good moisture resistance even after exposure to a high-thirsty household. Further, an object of the present invention is to apply such a surface treatment agent to a brush circuit substrate, so that the molten solder can be wetted and diffused well even in the case of a solder pad which is deteriorated by heating at a high temperature. The invention discloses a method for solving a problem. The present invention is a novel microphone represented by a general formula. 29

In the formula, Ri represents hydrogen or a linear or branched chain alkyl group having 1 to 11 carbon atoms. R2 is independent of each other and represents a linear or branched chain alkoxy group having 1 to 11 carbon atoms. R3 is independent of each other and represents a linear or branched chain alkyl group, gas or bromine having a carbon number of 1 to 11. m is an integer of 1 to 4, and η is an integer of 0 to 4. Further, the present invention relates to a metal surface treatment agent characterized by containing the aforementioned imidazole compound. Furthermore, the present invention relates to a printed circuit board characterized by having a rust preventive film formed by applying the surface treating agent. Further, the present invention relates to a metal surface treatment method for a printed circuit board, characterized in that it is attached to a metal film of a printed circuit board, and the surface treatment agent is applied to form an anti-recording film. Advantageous Effects of Invention According to the present invention, it is possible to provide a high solubility in an aqueous solution of an organic acid, and precipitation of an imidazole-based compound due to pH fluctuation or evaporation of the treatment liquid is suppressed, and even if it is faced with a printed wiring board or a soft etching treatment The mixed ions caused by the mixing can still be used stably, and the taste-saling compound suitable for the surface treatment agent. Further, according to the present invention, a metal surface treatment agent using the imidazole compound can be used to form a coating film having heat resistance and having excellent moisture resistance even after exposure to high humidity. Further, according to the present invention, such a surface treatment agent is applied to a printed circuit board of the 2010, 2010,829, and the molten solder can be well wetted and diffused even in a solder pad which is deteriorated by heating at a high temperature. BRIEF DESCRIPTION OF THE DRAWINGS [Fig. 1] shows the temperature distribution diagram of the air reflow furnace in the heat deterioration test. [Embodiment 3] The best mode for carrying out the invention [New imidazole compound] wherein R! represents hydrogen or a linear or branched chain alkyl group having 1 to 11 carbon atoms. More specifically, the alkyl carbon number of R! is preferably from 1 to 7, more preferably from 1 to 4. It is particularly suitable that Ri is hydrogen. R2 is independent of each other and represents a linear or branched chain alkoxy group having a carbon number of 1 to 11. More specifically, the carbon number of R2 is preferably from 1 to 7, more preferably from 1 to 4. Particularly suitable is that R2 is a methoxy group. R3 is independent of each other and represents a linear or branched chain alkyl group, gas or bromine having a carbon number of 1 to 11. More specifically, the carbon number of R3 is preferably from 1 to 7, more preferably from 1 to 4. Particularly suitable is that R3 is a sulfhydryl group. m is an integer of 1 to 4, and particularly preferably 1 to 2. Further, η is an integer of 0 to 4, and 0 to 1 is particularly suitable. [Synthesis of a rice compound] (Method 中 In the rice salt compound of the present invention, when Ri is hydrogen, it can be synthesized as shown, for example, (Process 1). [Chemical 3] 201014829 (Process 1)

Benzoate (salt) wherein R2 is independent of each other 'is a straight or branched chain alkoxy group having 1 to 11 carbon atoms. R3 is independent of each other and represents a linear or branched alkyl group, gas or bromine having a carbon number of 1 to 11. m is an integer of 1 to 4, and η is an integer of 0 to 4. That is, the first stage is the synthesis of an acetophenone derivative (Chemical 2) into an α-bromophenone and an α-phenyl ketone by an evolution agent or a chlorinating agent (Chemical Formula 3). As the brominating agent, a general brominating agent can be used, and examples thereof include bromine, tribromination, 唆, Ν-bromo succinimide, etc., and bromine is preferred. The gasifying agent can use a general gasifying agent such as milk, sulphur sulphide chloride, continuous sputum milk, phosgene (ph〇Sgene), grass-brewed chlorine, phosphorus oxychl〇ride, and pentachlorination. Phosphorus, tri-phosphorus, etc., preferably sulfoxide, sulfonium chloride. As these halogenating agents, commercially available products can usually be used. This (four) reaction can optionally use a Lewis acid or a bronsted acid as a catalyst. The solvent-free or at least one halogenation reaction can be routinely performed. (4) Suitable reactions may be, for example, methanol, ethanol, 1,2-ethanediol, n-propanol, 2-propanol, n-butanol, and the like, 'already burned, n-pentyl, cyclohexan, stupid, An aliphatic or aromatic hydrocarbon such as toluene or xylene; an aromatic hydrogen such as a gas, a gas, a gas, or a milk, a second hydrogen, a tetrahydrogen, a tetrahydrogen, a chelate, or the like. Fat (4) _ or Saki style. In addition, it is also possible to use 9 201014829 organic acids such as formic acid, acetic acid, and propionic acid.

In the second stage, the above-mentioned a-p-benzophenone (Chemical Formula 3) is reacted in the presence of a clump and a base to obtain a desired product. As the benzamidine, a hydrochloride or a sulfate or the like can be used, and a salt formed with the corresponding inorganic acid and/or organic acid can also be used. Particularly suitable solvents for the reaction solvent are, for example, acetates such as ethyl acetate and butyl acetate, such as decyl alcohol, ethanol, 1,2-ethanediol, n-propanol, 2-propanol, n-butanol. Alcohols such as n-hexane, n-pentane, cyclohexane, benzene, toluene, diphenylbenzene, etc., aliphatic or aromatic hydrocarbons, dichloromethane, chloroform, 1,2-dichloroethane Aromatic hydrogen such as gas benzene, aliphatic bond or alicyclic ether such as dimethyst, tetrachloroaphthyl, 2-mercaptotetrazole, or sigma. Further, the reaction temperature and concentration can be arbitrarily set at any stage. (Method 2) In the case of the imidazole compound of the present invention, when acetophenone as a raw material is not commercially available, it can be synthesized, for example, as in Process 2.

[Chemical 4] (Process 2) <In the case of RAH of (1) X-C'H: -COCl or X-C'H: -C: OBr (X is C1 or Br)

10 201014829 wherein R! represents a hydrogen or a linear or branched chain alkyl group R2 having a carbon number of 1 to 11 and is independent of each other, and represents a linear or branched chain alkoxy group having 1 to 11 carbon atoms. R3 is independent of each other and represents a linear or branched chain alkyl group having a carbon number of 1 to 11, gas or moisture. m is an integer of 1 to 4, and η is an integer of 0 to 4. That is, when R! is hydrogen, the first stage is to make substituted benzenes (haloacetic aicd chloride) (X-CH2-COCl: X is chlorine or odor) or haloacetic acid bromide. (X-CH^COBrCl: X is gas or bromine) reacts to synthesize α-halo-acetophenone (Chemical 3). The reaction is suitably carried out by Friedel-Crafts acylation, and the reaction can be carried out in the presence of a general Lewis acid suitable for the reaction, such as aluminum oxide. The acetic acid vaporization may, for example, be a gas acetic acid vapor, a desert acetic acid vapor, or a - acetic acid bromide, for example, a chloroacetic acid bromide or a desert acetic acid bromide, preferably a gas acetic acid vapor. Further, when the intention is a linear or branched chain alkyl group having a carbon number of 1 to 11, the corresponding acid gasification or acid bromide is subjected to the same reaction as described above, and then the same method as the method. In the method, a ketamine derivative (Chemical 3) is prepared with a brominating agent or a gasifying agent. The second stage can also be synthesized in the same manner after benzamidine. In addition, the reaction temperature and concentration can be arbitrarily set at any stage. [Metal Surface Treatment Agent] The surface treatment agent of the present invention is a compound containing a novel imidazole compound. In a suitable embodiment, the imidazole compound of the essential component is used. /. The surface treatment agent is preferably a G() 5f amount% or more, or a 5% by mass or less aqueous solution. By adjusting the content of the imidazole compound to 201014829. The method of "0.1 mass% or more" becomes easy to form a coating film such as a rust preventive film. If the content exceeds 10 mass. /〇, not only the insoluble part is easy to increase, but also not economical. Since the aforementioned miso compound is poorly soluble in neutral water, an organic acid is used to dissolve the water. In addition, a water-soluble organic solvent can also be used at this time. The organic acid to be used at this time may, for example, be formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, caprylic acid, capric acid, capric acid, lauric acid, myristic acid, palmitic acid, hard. Fatty acid, arachidic acid, behenic acid-tetradecanoic acid, alpha-linolenic acid, stearidonic acid, eicosapentene Acid (eic〇sa_ pentaen〇ic acid), docosahexaenoic acid, linoleic acid, γ·Ά linoleic acid, dihomo- γ-linolenic acid, peanut oleic acid ( Arachidonic acid), oleic acid, erucic acid, glycolic acid, lactic acid, 2-hydroxybutyric acid, 3-hydroxybutyric acid, malic acid, tartaric acid, citric acid, isocitric acid, gaseous acetic acid, Di-acetic acid, tri-acetic acid, desert acetic acid, decyloxyacetic acid, acrylic acid, benzoic acid, cis-benzoic acid, para-butyl benzoic acid, p-toluene® acid, picric acid (piric) Acid), meta-toluic acid, saprotic acid, salicylic acid, maleic acid, fumaric acid (f Umaric acid, adipic acid, azelaic acid, 4-levulinic acid, etc., formic acid and acetic acid are particularly suitable. These acids preferably contain 1 to 4 masses. Further, as the water-soluble organic solvent which can be used at this time, for example, a fermentation product such as methanol, ethanol, 1,2-ethanediol, n-propanol, 2-propanol or n-butanol, acetone, hydrazine, hydrazine- Dimercaptomethylamine and the like. The metal treated with the surface treatment agent may, for example, be copper, copper and phosphorus, an alloy of 12 201014829 and brocade, an alloy of m silver ★, and an alloy containing these metals as a main component. In the surface treatment agent of the present invention (preferably as a water-soluble preflux), it may be further added, such as copper formate, gasified steel, vaporized copper, grass _, copper acetate, copper hydroxide, cuprous oxide. , copper oxide, carbon steel, copper acidate, copper sulfate, formic acid, manganese, oxalic acid, sulfuric acid, acetic acid, acetic acid, hydrogenation, gasification, iron, iron oxide, oxidation Iron, bismuth metal compounds such as copper iodide, cuprous bromide, copper bromide, etc., and ethylenediamine, ethylenediaminetetraacetic acid, imine diacetic acid, nitril triacetic acid, gluconic acid, Crown ether, bismuth (four), porphyrin, phenanthroline, etc., other 'cyclic coordinating compounds, as a complex with copper The film-forming auxiliary agent may be used alone or in combination of two or more kinds, and the amount of addition is preferably from 1 to 10% by mass based on the treatment liquid, and preferably from 0.05 to 5% by mass. A metal ion buffer is also suitable, and thus, representative bases can be exemplified Ammonia, diethylamine, diethylamine, diethanolamine, triethanolamine, monoethanolamine, dimercaptoethanolamine, ethylethanolamine, isopropylethanolamine, hydrazine, sodium hydroxide, hydroxide, etc. In the surface treatment agent of the present invention, in order to further improve the welding characteristics, for example, deuteration, bromination, zinc telluride, zinc bromide, hydrazine, money, and propionic acid may be added. Acid bromide), a halide such as propionic acid iodide, and a molybdenum tetramethylate, a deserted methyl group, a methylpyridinium bromide, a heterocyclic compound 13 201014829 or an amine compound tooth The salt may be used in an amount of 0.01 to 10% by mass, preferably 0.05 to 5% by mass based on the treatment liquid. Based on these cases, the d meter represented by the above general formula (1) is preferable. The cerium compound and the 'water-soluble preflux containing an organic acid' may also contain at least one of the above metal compound, a complex compound, and a dentate. The water-soluble flux of the present invention is applied for rust-preventing treatment, and a rust-proof film is formed. Time After being subjected to grinding, degreasing, pickling, and water washing, that is, the surface of the copper layer of the printed circuit board, after the previous treatment step, the printed circuit board is immersed at 10 to 60 ° C for several seconds in the water-soluble preflux. To a few tenths of a clock, it is preferably immersed for 5 seconds to 1 hour at 20 to 50 ° C, preferably for 1 〇 to 10 minutes. Thus treated, the imidazole compound of the present invention adheres to copper. The higher the treatment temperature of the layer, the longer the treatment time. The more the adhesion amount is, the better the ultrasonic wave is used. Further, other coating methods such as spray removal, brush coating, and tube coating can be used. In the case where the obtained anti-recording film is treated in such a manner as to be mounted on both sides, the molten solder can be wetted and diffused well even in the case of a soldering pad which is deteriorated by high-temperature heating.

Further, a thermoplastic resin having good heat resistance formed by a rosin derivative, a terpene phenol resin or the like may be dissolved in a solvent, and uniformly coated on a water-soluble precoat by a roll coater or the like. A printed circuit board in which a rust preventive film is formed by a flux, thereby improving heat resistance. When manufacturing the printed circuit board of the present invention, for example, the following steps are performed. (1) A circuit diagram formed by a predetermined circuit wiring having a solder pad for soldering a wafer component on a substrate formed of a copper clad laminate, and a step of welding the "external welding". (2) Pre-treatment steps of grinding, degreasing, pickling (soft-touching), and washing the copper surface of the circuit pattern. (3) A step of applying a water-soluble pre-flux containing at least one compound of a group consisting of the compounds represented by the above general formula (丨) to a copper surface of a chrome-plated solder pad and drying it. (4) Applying a solder paste (containing solder powder and flux) directly to the solder pad after applying a flux (p〇stflux) to the obtained printed circuit board, or applying the electrode directly to the solder pad Solder by reflow. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS [Embodiment] Embodiments of the present invention will be described by way of the following examples. In addition, "%" means "quality. /0" unless otherwise specified. [1. Synthesis of Novel Miqua Compound] [Production Example 1] Production of (2-phenyl-4-(2-methoxy)benzimidazole) Dissolving o-methoxyacetophenone (3〇〇g) In a solution formed in hydrazine (500 mL), bromine (320 g) was kept at 5 to 10 ° C while stirring, and dripped for 3 hours. Then, water (500 ml) was added at a temperature below 2 ° C, and potassium carbonate (30 〇 g) was added thereto for 1 hour to be neutralized. Thereafter, ethyl acetate (500 ml) and water (500 ml) were added, and the organic layer was extracted. The organic layer was washed twice with saturated brine 15 201014829 (500 ml), and the bromo(2·decyloxy)acetophenone formed was used in the next reaction. The obtained organic layer was mixed with benzoquinone hydrochloride (320 g), potassium carbonate (800 g) and water (600 mL), and stirred at 60 ° C for 6 hours. The reaction solution was cooled while neutralizing with potassium hydroxide, and then the organic layer was extracted with ethyl acetate (1 L). The organic layer was washed three times with saturated brine (1 L) and concentrated to 150 mL with an evaporator. Hexane (1 L) was added, and the resulting crystal was stirred at room temperature, and 15 g of 2-phenyl-4-(3-methoxy)phenyl miso was obtained. Melting point (160 ° C) 'δΙΗ-NMR (400MHz, DMS0-d6) : 3.83 (s), _ 6.80 (d), 7.29 (t), 7.37 (t), 7.45 (m), 7.80 (s), 8.02 (d) [Chemical 5]

[Production Example 2] (Production of 2-phenyl-4-(3-methoxy)benzimidazole) ® m-methoxyacetophenone (250 g) was dissolved in dichloromethane (lkg), and kept while stirring Drain the product (250g) at 0~5°C. While collecting the generated gas, it was continuously dropped for 2 hours, and then stirred at room temperature for 5 hours. The organic layer was washed twice with a 5% aqueous potassium carbonate solution (1 L) and then washed twice with water. The organic layer was concentrated to the remaining half, and the mixture was stirred at room temperature (2 L). After 1 hour, the resulting crystals were filtered under reduced pressure to give 140 g of ?-? Next, α_gas (3-decyloxy)acetophenone (14〇g), 16 201014829 phenylhydrazine hydrochloride (120g), sodium hydrogencarbonate (240g), tetrahydrofuran (1L) and water were mixed. 500 mL), mixing at 60 ° C for 6 hours. The reaction solution was cooled, neutralized with ammonia, and then the organic layer was extracted with ethyl acetate (1L). The organic layer was washed three times with saturated brine (1 L) and then concentrated to EtOAc. Hexane (1 L) was added, and the resulting crystal was stirred at room temperature, and 127 g of 2-phenyl-4-(3-methoxy)benzene B m. Melting point (159. 〇, δΙΗ-NMR (400MHz, DMSO-d6): 3.82 (s), 6.80 (d), 7.29 (t), 7.36 (t), 7.48 (m), 7.79 (s), 8.02 (d ) ❹ 【化6】

[Production Example 3] (Production of 2-phenyl-4-(3-ethoxy)benzimidazole) Substituting o-methoxyacetophenone with m-methoxyacetophenone (10 g), and [ Production Example 1] The same adjustment was carried out to obtain 55 g of 2-phenyl-4-(3-ethoxy)benzimidazole.

Melting point (159°〇, δΙΗ-NMR (400MHz, DMSO-d6): 3.82 (s), 6.80 (d), 7.29 (t), 7.37 (t), 7.48 (m), 7.79 (s), 8.02 (d ) 【化7】

[Production Example 4] (Production of 2-Ricyl-4-(3,4-dimethoxy)benzimidazole) 17 201014829 Using 3,4-dimethoxyacetophenone (100 g), and [Production Example 2] With the same adjustment, 45 g of 2-phenyl-4-(3-ethoxy)phenylimidazole was obtained. Melting point (155 ° C) 41H-NMR (400MHz, CDC13): 3.95 (m), 6.96 (d), 7.02 (d), 7.21 (d), 7.30 (s), 7.39 (t), 7.57 (s), 7.82 (d), 10.84 (m) [Chem. 8]

(Production of 2-Phenyl-4-(3,4-dimethoxy)phenyl-5-methimazole) Mixed with 1,2-dimethoxybenzene (100 g) and anhydrous aluminum oxide (150 g) In the solution formed by the two gas calcination (600 g), propionic acid chloride (70 g) was added dropwise at 5 ° C or lower for 3 hours. Then, while collecting the generated gas, the mixture was stirred at room temperature for 3 hours, and then 5% hydrochloric acid (300 mL) was added and stirred at room temperature for 1 hour. With 5% potassium carbonate aqueous solution (500 mL)

The organic layer was washed twice and then washed twice with water. The G layer was dehydrated and filtered with anhydrous sodium sulfate. Then, the solution was adjusted to (TC, and the sulfonium gas (100 g) was dropped over a period of 3 hours. Thereafter, while the generated gas was collected, it was stirred at room temperature for 5 hours, and was cooled with 2% of hydroxide while cooling. The aqueous solution (QQmL) was washed twice. Then, the organic layer was concentrated to the remaining half, followed by mixing of phenylhydrazine hydrochloride (95 g), sodium hydrogencarbonate (270 g), tetrahydrofuran (6 mL) and water (300 mL). After stirring at 60 ° C for 6 hours, the reaction solution was cooled, neutralized with ammonia, and then the organic layer was extracted with ethyl acetate (500 mL). The organic layer was washed three times with 18 201014829 saturated brine (500 mL) and evaporated. Concentrate to 1 〇〇 mL. Add hexane (300 mL), stir at room temperature and filter the resulting crystals to give 50 g of 2-phenyl-4-(3,4-dimethoxy)phenyl-5曱 曱 imidazole. Melting point (175 ° C), δ ΙΗ-NMR (4 〇〇 MHz, CDC13): 3.92 (s), 6.89 (d), 7.00 (d), 7.25 (m), 7.39 (t), 7.57 ( s), 7.80 (d), 10.82 (m) [Chemistry 9]

[Production Example 6] (Production of 2-phenyl-4-(2-decyloxy-5-methyl)benzene-flavored o-seat) Methyl anisole (30 g) and methotrexate were mixed ( A solution of chloroacetyl chloride (50 g) was added dropwise to trifluoromethanesulfonic acid over 3 hours at 〇~5 °C. Then, the reaction liquid was poured while stirring slowly in ice water (1 L). The mixture was stirred for 3 hours while cooling, and the resulting white crystals were collected by filtration to yield (yield: (2-methoxy-5-fluorenyl) acetophenone (35 g). Next, benzamidine hydrochloride (30 g), sodium hydrogencarbonate (80 g), toluene (100 mL) and water (100 mL) were added and stirred at 50 ° C for 5 hours. While the reaction solution was cooled, it was neutralized with ammonia, and then the organic layer was extracted with ethyl acetate (200 mL). The organic layer was washed three times with saturated brine (200 mL) and concentrated to 50mL with an evaporator. Hexane (100 mL) was added, and the resulting crystal was stirred at room temperature and filtered to give 22 g of 2-phenyl-4-(2-methoxy-5-indolyl)benzimidazole. Melting point (192. 〇, δΙΗ-NMR (400MHz, CDC13): 2·28 (s), 19 201014829 3.86 (s), 6.86 (d), 7.36 (t), 7.44 (t), 7.64 (s), 7.88 (d) [10]

[Production Example 7] (Production of 2-phenyl-4-(2-a-5-nonyloxy)benzimidazole) Aluminum carbonate (34 g) was mixed at 5 ° C to dioxane (150 g) In the middle, a mixture of 4_gas anisole (30 g) and gas oxime (26 g) was kept at 5 ° C or lower and dripped for 3 hours. Then, while collecting the generated gas, it was stirred at room temperature for 3 hours. Thereafter, 5% hydrochloric acid (100 mL) was added and stirred at room temperature for 1 hour. The organic layer was extracted and washed twice with a 2% aqueous potassium hydroxide solution (120 mL), and then washed twice with water. The organic layer was concentrated to the remaining half, followed by the mixture of benzamidine hydrochloride (120 g), sodium bicarbonate (240 g), tetrahydrofuran (500 mL) and water (300 mL), and stirred at 60 ° C for 6 hours. The reaction solution was cooled while neutralizing with ammonia, and then the organic layer was extracted with ethyl acetate (500 mL). The organic layer was washed three times with saturated brine (500 mL) and then concentrated to 100 mL. Hexane (300 mL) was added, and the resulting crystals were stirred at room temperature and filtered to give 18 g of 2-phenyl- 4-(2-ethane-5-methoxy) imidazole. Melting point (162. 〇, δΙΗ-NMR (400MHz, CDC13): 3.87 (s), 6.89 (d), 7.29 (t), 7.34 (t), 7.59 (d), 7.74 (s), 7.87 (d), CDC13 【化11】 201014829

[Production Example 8] (Production of 2-phenyl-4-(2,5-dimethoxy-3-indolyl)benzimidazole) Substituting 2,5-dimethoxytoluene (130 g) for 4-chloro The anisole was adjusted in the same manner as in [Production Example 7] to obtain 45 g of 2-phenyl-4-(2,5-dimethoxy-3-methyl)indole. Melting point (190. 〇, δΙΗ-NMR (400MHz, CDC13): 2.398 (S), 3.883 (s), 6.741 (s), 7.129 (s), 7.336 (t), 7.395 (t), 7.877 (d), 10.172 (m), (CDC13) [Chem. 12]

[Production Example 9] (Production of 2-phenyl-4-(2,3,5-trimethoxy-6-fluorenyl)benzimidazole) Using 2,4,5-trimethoxytoluene (10 (^) In place of 4-chloroanisole, it was adjusted in the same manner as in [Production Example 7], and 38 g of 2-phenyl-4-(2,5-dimethoxy-3-indolyl)benzene β m was obtained. Melting point (190 ° C), δ ΙΗ-NMR (400 MHz, CDC13): 3.733 (s), 3.895 (s), 3.911 (s), 6.641 (s), 7.364 (t), 7.450 (t), 7.880 (d) , 21 201014829 10.242 (m), (CDC13) [Chem. 13]

Mixing and Evaluation of Surface Treatment Agents The following is a sequence in which (1) the novel sodium saliva and the comparative compound of the present invention are mixed as a surface treatment agent (water-soluble preflux), and (2) the surface treatment is completed! (3) The procedure for forming a coating film on the surface of the copper-clad laminate substrate by the surface treatment agent' (4) Heat resistance and humidification deterioration test of the coating film formed by the surface treatment agent as an example Be explained. Qin (1) The procedure of formulating a surface treatment agent (water-soluble preflux) with the novel imidazole of the present invention and a comparative compound - [Example 1] 2-Phenyl-4_(2-methoxyl) of [Production Example 1] ) Benzimid 0.3%, acetic acid 10%, and zinc bromide 0.05% are dissolved, and the pH is adjusted with ammonia water and pure water to prepare a treatment liquid which can be used as a coating film. [Example 2] 2-Phenyl-4-(3-decyloxy)benzimidazole·3% of [Production Example 2], 20% of acetic acid, 0.05% of heptanoic acid, and 峨化〇_〇5% Dissolve, adjust the pH with ammonia water and pure water to make a treatment liquid for forming a coating film. [Example 3] 2-Phenyl-4-(3-ethoxy)benzene oxime. 2%, formic acid 22 201014829 5.00%, acetic acid 10.00%, and ammonium acetate 0.03% were prepared in [Production Example 3]. Ethylenediaminetetraacetic acid was dissolved in 0.05%, and the pH was adjusted with ammonia water and pure water to prepare a treatment liquid capable of forming a coating film. [Example 4] [Production Example 4] 2-phenyl-4-(3,4-diethoxy)benzimidazole 0.25%, acetic acid 10.00%, glycolic acid 1.0%, bromine Ammonium 〇.〇5〇/0, imine diacetic acid 0.05% dissolved 'The pH is adjusted with ammonia water and pure water to prepare a treatment liquid which can form a coating film. • [Example 5] [Production Example 5] 2-phenyl-4-(4-methoxy)benzene-5-methimazole 0.25%, methoxyacetic acid 10.00%, copper acetate 〇.〇50/〇 Dissolve, adjust the pH with ammonia water and pure water to prepare a treatment liquid which can form a coating film. [Example 6] [Production Example 6] 2-phenyl-4-(2-decyloxy-5-mercapto)benzimidazole 0.30%, acetic acid 30.00%, cesium hexanoate·1%, bromine The solution is dissolved in 0.05 〇/〇, and the pH is adjusted with ammonia water and pure water to prepare a treatment liquid which can form a coating film. [Example 7] 2-Phenyl-4-(2-a-5-methoxy)benzidine 0.20% of [Production Example 7], acetic acid 15%, cesium citrate·1% by weight, zinc acetate 〇 30%, triethanolamine 0.10 ° /. The solution was dissolved, and the pH was adjusted with ammonia water and pure water to prepare a treatment liquid capable of forming a coating film. [Example 8] 2-Phenyl-4-(2,5-dimethoxy-3-methyl)phenylidene of [Production Example 8] was placed at 0.20%, acetic acid 20.00%, and malic acid bismuth·1 〇0/. Tetramethylammonium iodide 23 201014829 (tetramethyl ammonium iodide) 0.05%, hydrazine 0.10% dissolved, adjusted pH with ammonia water and pure water to prepare a treatment liquid which can form a coating film. [Example 9] [Production Example 9] 2-phenyl-4-(2,3,5-trimethoxy-6-methyl)benzimidazole 0.20%, formic acid 10.00%, acetic acid 20. /〇, potassium iodide is dissolved in 0.05%, and the pH is adjusted with ammonia water and pure water to prepare a treatment liquid which can form a coating film. [Comparative Example 1] 0.80% of 2-pentyl imidazole, 2.% by weight of acetic acid, and 0.05% of zinc bromide were dissolved, and the pH was adjusted with aqueous ammonia and pure water to prepare a treatment liquid capable of forming a coating film. [Comparative Example 2] 2-Isoimidazole 1. 〇〇%, formic acid! 〇〇%, 丨〇〇% acetate, and zinc bromide 0.05% were dissolved, and the pH was adjusted with ammonia water and pure water to prepare a treatment liquid capable of forming a coating film. [Comparative Example 3] 2,4-one base ° ° ° sitting 0.30%, acetic acid 1 〇 〇〇 %, bromination word 0.05% dissolved, adjusted pH with ammonia water and pure water, can be formed into a coating film Treatment fluid. (2) Stability test of surface treatment agent The stability of the surface treatment agent (water-soluble preflux) of the present invention was carried out in accordance with the following test. (2-1: low-temperature stability) The treatment agent was placed in a 300 cc polypropylene flask and allowed to stand for 7 days. The state of precipitation of crystals or oil after 7 days was observed. The results are shown in Table (2-2: Stirring stability). 201014829 The treatment agent and the stirrer were placed in a 300 cc polypropylene flask, and the mixture was mixed with an electromagnetic repeller to observe crystals or oil precipitates after 7 days. status. The results are shown in Table 1. (2 3. Mixing stability of sulfuric acid and gas ions) Add the treatment agent and 〇·1% (1 OOOppm) of sulfuric acid or hydrochloric acid to a 3〇〇cc polypropylene flask, stir using a stirrer and stir with a magnetic stirrer. Observe the state of precipitation of crystals or oils after 7 曰. The results are shown in Table 1. [Table 1] Static stability and stability Stabilization of sulfuric acid and gas ion mixing stability (25 ° 〇 sulfuric acid ion gas ion Example 1 no crystal, no oil, no crystal, no oil, no crystal, no oil, no crystal, no oil Example 2 No crystal, no oil, no crystal, no oil, no crystal, no oil, no crystal, no oil, Example 3, no crystal, no oil, no crystal, no oil, no crystal, no oil, no crystal, no oil, example 4 Crystallization, no oil, no crystal, no oil, no crystal, no oil, no crystal, no oil. Example 5 No crystal, no oil, no crystal, no oil, no crystal, no oil, no crystal, no oil. Example 6 No crystal, no oil No crystal, no oil, no crystal, no oil, no crystal, no oil. Example 7 No crystal, no oil, no crystal, no oil, no crystal, no oil, no crystal, no oil. Example 8 No crystal, no oil, no crystal. Oil no crystal, no oil, no crystal, no oil. Example 9 No crystal, no oil, no crystal, no oil, no crystal, no oil, no crystal, no oil. Comparative example 1 No crystal, no oil, no crystal. No oil, no crystal. Oil-free, no crystal, no oil, Comparative Example 2, Crystal precipitation, crystal precipitation, no crystal Oil no crystals, no oil, Comparative Example 3, Crystal precipitation, Crystal precipitation, Crystal precipitation, Crystal precipitation (3) Using the surface _ The order of forming a coating film on the surface of the steel-clad laminate substrate (3-1) Evaluation of substrate cleaning. Preparation will be The soft shaft engraving agent (trade name: manufactured by SE-30M TAMURA KAKEN CORPORATION) is used to clean the surface of the copper foil, and the substrate is taken out and washed with water to remove the liquid. 25 201014829 Next, the novel imidazole compound containing the above-mentioned adjusted invention and In the surface treatment agent of the comparative compound, the evaluation substrate was immersed at 4 ° C for 6 sec, and then taken out and washed with water. The test piece formed by the surface treatment agent was applied as follows using the test piece subjected to such treatment. Heat resistance and humidification deterioration test. (4) Heat resistance and moisture deterioration test of coating film formed of surface treatment agent (4-1: Heat deterioration treatment) Heat resistance test of water-soluble preflux coating film In the above, the heat deterioration treatment of the printed circuit board is performed by performing a plurality of reflow treatments using the line return having the temperature distribution shown in Fig. 1 (4-2: humidification deterioration) The humidification degradation test of the water-soluble preflux film was carried out by means of a constant temperature and humidity layer of 4 ° C and 90% RH for 96 hours. (4-3: Solder diffusivity test (1)) A JIS 2-shaped comb-shaped substrate was used as a test substrate, and a product in which a rust-preventing film was formed by the above method was used. Under the above-described reflow conditions, the test substrate on which the coating film was formed was subjected to 〇~3 heat treatment, and then the solder paste was applied. (trade name: RMA 〇1〇NFp TAMURA KAKEN Corporation) The embossing printing was performed using a metal mask having an opening width of 〇 635 _ and a thickness of 200 μm, and a reflow heat treatment was performed to measure the diffusion length of the solder. The longer the length of the solder diffusion at this time, the higher the _ property of the solder. The results of each water-soluble fresh _ evaluation are shown in Table 2. (4-4: Solder diffusibility test 201014829 A JIS 2-shaped comb-shaped substrate was used as a test substrate, and a product having a rust-preventing film was formed by the above method. The test substrate on which the coating film was formed was subjected to humidification degradation treatment, After the heat treatment was carried out for 0 to 3 times under the above-mentioned reflow conditions, a solder paste (trade name: RMA-010NFP TAMURA KAKEN CORPORATION) was used for one-word printing with a metal mask having an opening width of 0.635 mm and a thickness of 200 μm, and reflow heating was performed. The treatment 'measures the diffusion length of the solder. The longer the length of the solder diffusion at this time' indicates the higher the wettability of the solder. The evaluation results of the examples are shown in Table 2. [Table 2] Solder diffusivity test 1 Solder diffusivity Test 2 Number of reflows 0 number of times 1 time 2 times 3 times 0 times 1 time 2 times 3 times Example 1 8mm 7mm 5mm 4mm 6mm 5m 4mm 3mm Example 2 8mm 7mm 4mm 5mm 6mm 5mm 4mm 3mm Example 3 7mm 6mm 5mm 4mm 6mm 5mm 4mm 3mm Example 4 7mm 7mm 6mm 4mm 6mm 5mm 4mm 3mm Example 5 7mm 6mm 5mm 4mm 6mm 5mm 4mm 3mm Example 6 7mm 6mm 5mm 4mm 6mm 5mm 4mm 3mm Example 7 8mm 7mm 6mm 5mm 7mm 6mm 5mm 4mm Example 8 6mm 6mm 6mm 5mm 6mm 5mm 4mm 3mm Example 9 7mm 6mm 6mm 4mm 6mm 5mm 4mm 3mm Comparative Example 1 2mm 1mm lmm lmm lmm lmm lmm lmm Comparative Example 2 2mm lmm lmm lmm 2mm lmm lmm lmm Comparison Example 3 6 mm 5 mm 4 mm 3 mm 5 mm 4 mm 3 mm 2 mm (4-5: Through-hole solder creep test (1)) A substrate having a through-hole of 360 mm having an inner diameter of 0.6 to 1.0 mm was used as a test substrate, and the use was carried out as described above. The method is to form a product of a rustproof film. 27 201014829 The test substrate forming the anti-recording film is subjected to 〇~3 times of heat treatment under the above-mentioned reflow conditions, and then the coating flux is applied (trade name: CiM rain Η_2ατα hall KAKEM Coip〇 Rati〇1^) 'Welding treatment using a reflow soldering device' measures the ratio of the number of vias to the top of the via hole. The evaluation results of each water-soluble preflux are shown in Table 3. (4-6: Pass Hole solder creep test (2)) A substrate having a through hole 36 having an inner diameter of 0.6 to 1. mm was used as a test substrate, and a product of which a rust preventive film was formed by the above method was used. After the test substrate on which the v-coated film was opened was subjected to a humidification-degradation treatment, and then subjected to heat treatment for 0 to 3 times under the above-described reflux conditions, a flux was applied (trade name: CF 1 l〇VH_2A TAMURA KAKEN Corporation) The soldering process was performed using a reflow soldering apparatus, and the ratio of the number of via holes until the solder climbed up to the upper portion of the via hole was measured. The evaluation results of each water-soluble preflux are shown in Table 3. [Table 3] Through-hole solder improveability 1 Through-hole solder improveability 2 Reflow number of reflow times 0 times 1 time 2 times 3 times 0 times 1 time 2 times 3 times Example 1 100% 100% 100% 100% 100% 100 % 100% 100% Example 2 100% 100% 100% 100% 100% 100% 100% 100% Example 3 100% 100% 100% 100% 100% 100% 100% 100% Example 4 100% 100% 100% 100% 100% 100% 100% 100% Example 5 100% 100% 100% 100% 100% 100% 100% 100% Example 6 100% 100% 100% 100% 100% 100% 100% 100% Example 7 100% 100% 100% 100% 100% 100% 100% 100% Example 8 100% 100% 100% 100% 100% 100% 100% 100% Example 9 100% 100% 100% 100% 100 % 100% 100% 100% Comparative Example 1 15% 6% 3% 1% 10% 5% 2% 2% Comparative Example 2 40% 10% 2% 1% 30% 8% 2% 1% Comparative Example 3 100% 100% 100% 100% 100% 100% 100% 100% 28 201014829 It can be seen from Tables 1 to 3 that the metal surface treatment agent containing the novel imidazole compound provided according to the present invention is very stable and has high solubility in an aqueous solution, =: = the processing of the butterfly compound caused by the change or evaporation of the PH, even if it is printed on a printed circuit board or a table The mixing agent of the surface treatment agent can still be used in a stable manner, and the metal surface treatment formed by the same can be used.

It is heat-resistant, and it can save money even after exposure to high humidity. It has a very good resistance to the coating film. 7. Apply to the printed circuit board 'even if it is subjected to high-side = lining 亲' Good wetting diffusion can be formed. [Simple description of the diagram] The distribution map [Fig. 1] shows the temperature of the air reflow furnace in the heating deterioration test. [Main component symbol description] (None) ❹ 29

Claims (1)

201014829 VII. Patent application scope: 1. A novel imidazole compound represented by the following general formula, [Chemical 1] (wherein R! represents hydrogen, a linear or branched chain alkyl group having 1 to 11 carbon atoms; and R2 is independent of each other, and represents a linear or branched chain alkoxy group having 1 to 11 carbon atoms; and R3 is independent of each other; And represents a linear or branched chain alkyl group having a carbon number of 1 to 11, a gas or a bromine; m is an integer of 1 to 4, and η is an integer of 0 to 4). A metal surface treatment agent comprising the imidazole compound as described in claim 1 of the patent application. 3. The surface treatment agent according to claim 2, which contains an organic acid. 4. The surface treatment agent according to the second or third aspect of the invention, wherein the content of the imidazole compound is 0.01 to 10% by mass. 5. The surface treatment agent according to the third or fourth aspect of the invention, wherein the content of the organic acid is from 1 to 40% by mass. 6. A printed circuit board comprising a rust preventive film formed by applying the surface treating agent according to any one of claims 2 to 5. 7. A surface treatment method for a metal of a printed circuit board, which is characterized in that it is formed on a metal film of a printed circuit board, and is formed by applying a surface treatment agent according to any one of claims 2 to 5. Rust film.