CN1964949B - Phenylnaphthylimidazoles for use on copper surfaces during soldering - Google Patents
Phenylnaphthylimidazoles for use on copper surfaces during soldering Download PDFInfo
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Abstract
A surface treating agent containing a novel phenylnaphthylimidazole compound represented by the following formula is brought into contact with the surface of copper or a copper alloy. In the formula, when A1 is a phenyl group, then A2 represents a 1-naphthyl group or a 2-naphthyl group, and when A1 is a 1-naphthyl group or a 2-naphthyl group, then A2 represents a phenyl group; and R represents a hydrogen atom or a methyl group.
Description
Invention field
The present invention relates to by the novel phenyl napthyl imidazolium compounds shown in the following formula (I); The surface treatment agent that in the welding process of the copper of electronic unit etc. and printed-wiring board (PWB) or copper alloy, uses; The surface treatment method of copper or copper alloy; Printed-wiring board (PWB); And welding process.
In the formula, A
1When being phenyl, A so
2Expression 1-naphthyl or 2-naphthyl, and A
1When being 1-naphthyl or 2-naphthyl, A so
2The expression phenyl; Represent hydrogen atom or methyl with R.
Background technology
In recent years, adopted the high density surface field engineering widely.Wherein these surface mounting techniques are divided into following class: the double-sided surface field engineering, and wherein use soldering paste to connect the chip base part; With mix field engineering, it is to use the surface mounting technique of chip base part of soldering paste and the combination of separating component through hole mount technology.In every kind of mounting process, printed-wiring board (PWB) is carried out two or more welding step, and thereby stand to cause the high temperature of serious thermal history.
Because the copper of printed-wiring board (PWB) circuit pack or the surface of copper alloys are formed in heating, have quickened oxide film formation, and therefore the surface of circuit pack can not keep good weldability.
For the not oxidation by air of copper wire part of protection printed-wiring board (PWB), use surface treatment agent on the surface of circuit pack, to form chemical layer usually.Yet, be necessary with protection copper wire part, even after copper wire partly has repeatedly the thermal history circulation, also to be like this by preventing that chemical layer degraded (promptly being degraded) from keeping good weldability.
The tinsel low eutectic solder has been generally used for electronic unit is mounted to printed-wiring board (PWB) etc.Yet, in recent years, have been noted that the lead that contains in the welding alloy influences human body, and therefore need to use unleaded scolder.
Therefore, developing various unleaded scolders.For example, advised using unleaded scolder, one or more metals wherein, as silver, zinc, bismuth, indium, antimony, copper etc. are added in the base metal tin.
Normally used tin-the wettability of plumbous low eutectic solder on substrate surface is fabulous, the surface of copper especially, and therefore adhere to copper securely, obtain high reliability.On the contrary, unleaded scolder at the lip-deep wettability of copper therefore inferior to normally used wiping solder, and because space and other bonding defect map reveal poor weldability and low bond strength.
Therefore, when using unleaded scolder, must select the flux that has the welding alloy of good weldability and be fit to use with lead-free solder.The surface treatment agent that is used to prevent oxidation on copper or the copper alloy surface also needs to have the wettability that improves lead-free solder and the function of weldability.
Many lead-free solders have high-melting-point and are higher than about 20 ℃～about 500 ℃ welding temperature of normally used tin-plumbous low eutectic solder.Therefore, the surface treatment agent that is used for the lead-free solder weldprocedure should have the characteristic that can form the chemical layer with excellent heat resistance.
As the activeconstituents of surface treatment agent, multiple imidazolium compounds has been proposed.For example, patent documentation 1 discloses 2-alkyl imidazole compound, as the 2-undecyl imidazole; Patent documentation 2 discloses 2-Aryimidazole compound, as 2-phenylimidazole and 2-phenyl-4-methylimidazole; Patent documentation 3 discloses 2-alkyl-benzimidazole compound, as 2-nonyl benzoglyoxaline; With patent documentation 4 2-aralkyl benzimidazole compound is disclosed, as 2-(4-Chlorophenylmethyl) benzoglyoxaline.
Yet, containing in use under the situation of surface treatment agent of these imidazolium compoundss, the thermotolerance of the chemical layer that forms on the copper surface still can not be satisfactory.And in welding, the wettability of scolder also is not enough to obtain good weldability.Especially, under the situation of using lead-free solder replacement low eutectic solder to weld, be difficult to above-mentioned surface treatment agent is dropped into practical application.
[patent documentation 1] JP-B-46-17046
[patent documentation 2] JP-A-4-206681
[patent documentation 3] JP-A-5-25407
[patent documentation 4] JP-A-5-186888
Summary of the invention
Consider that the above-mentioned fact finishes the present invention.The purpose of this invention is to provide a kind of novel phenyl napthyl imidazolium compounds, with a kind of surface treatment agent is provided, it uses low eutectic solder or lead-free solder that electronic unit etc. is installed on the printed-wiring board (PWB), on copper that constitutes circuit pack such as printed-wiring board (PWB) or copper alloy surface, form chemical layer with excellent heat resistance, improved wettability simultaneously with scolder, and the weldability that obtains, the present invention also provides a kind of surface treatment method.
Another object of the present invention provides printed-wiring board (PWB), it contacts with above-mentioned surface treatment agent by the surface that makes the copper that constitutes the copper wire part or copper alloy and obtains, and provides the surface by making copper or copper alloy to contact the welding process of using low eutectic solder or lead-free solder to weld then with above-mentioned surface treatment agent.
For addressing the above problem, the present inventor has carried out widely and deep research.As a result, find to contact with the surface of copper or copper alloy, can realize purpose of the present invention by making to contain as the novel phenyl napthyl imidazolium compounds of following formula (I) expression surface treatment agent as activeconstituents, thus realization the present invention.
The surface treatment agent that contains with good grounds novel phenyl napthyl imidazolium compounds of the present invention, can not only on copper that constitutes circuit pack such as printed-wiring board (PWB) or copper alloy surface, form chemical layer with excellent heat resistance, and can improve low eutectic solder and lead-free solder wettability widely, and obtain good weldability to target surface.
Because can use the scolder that does not contain harmful metallic lead according to welding process of the present invention, from the viewpoint of environment protection, this also is useful.
Detailed description of the invention
Below will put down in writing preferred forms of the present invention.
Phenyl napthyl imidazolium compounds of the present invention comprises:
2-phenyl-4-(1-naphthyl) imidazoles,
2-phenyl-4-(2-naphthyl) imidazoles,
2-phenyl-4-(1-naphthyl)-5-Methylimidazole,
2-phenyl-4-(2-naphthyl)-5-Methylimidazole,
2-(1-naphthyl)-4-phenylimidazole,
2-(2-naphthyl)-4-phenylimidazole,
2-(1-naphthyl)-4-phenyl-5-Methylimidazole and
2-(2-naphthyl)-4-phenyl-5-Methylimidazole.
Phenyl napthyl imidazolium compounds of the present invention can be synthetic according to known method.That is to say, in phenyl napthyl imidazolium compounds of the present invention, compound classification is 2-phenyl-4-naphthyl imidazolium compounds, wherein the 2-position of its imidazole ring and 4-position are respectively by phenyl and naphthyl substituted, promptly, 2-phenyl-4-(1-naphthyl) imidazoles, 2-phenyl-(4-(2-naphthyl)-imidazoles, 2-phenyl-4-(1-naphthyl)-5-Methylimidazole, with 2-phenyl-4-(2-naphthyl)-5-Methylimidazole, these materials for example can synthesize by under heating 2-halogenation naphthyl-alkyl ketone compound and benzenyl amidine compound being reacted in organic solvent and in the presence of dehydrohalogenation reagent, shown in following reaction process.
In the formula, X can represent the chlorine atom, bromine atoms or or the iodine atom; Can represent hydrogen atom or methyl with R.
In the reaction shown in above-mentioned reaction process, the amount of used benzenyl amidine compound, based on 2-halogenation naphthyl alkyl ketone compound, preferred molar ratio is 0.8～1.5 times, more preferably 0.9～1.1 times.The amount of used dehydrohalogenation reagent, based on 2-halogenation naphthyl alkyl ketone compound, preferred proportion is 1～10 times of equivalent.
The example of above-mentioned 2-halogenation naphthyl alkyl ketone compound comprises ω-bromo-1-acetonaphthone, ω-bromo-2-acetonaphthone, and 2-bromo-1 '-naphthalene acetone, 2-bromo-2 '-naphthalene acetone, ω-chloro-1-acetonaphthone, ω-iodo-1-acetonaphthone, 2-chloro-1 '-naphthalene acetone and 2-iodo-2 '-naphthalene acetone.
In these 2-halogenation naphthyl alkyl ketone compounds, ω-bromo-2-acetonaphthone can be used as reagent and obtains.In addition, about other compounds except that ω-bromo-2-acetonaphthone, for example can use by at synthetic those of 2-position halogenation naphthyl alkyl ketone compound.For the halogenation of 2-position,, be the simplest with 1 mole of bromination with 1 mole of naphthyl alkyl ketone compound reaction in the 2-position although may be in the chlorination of 2-position with in the iodate of 2-position.
In the naphthyl alkyl ketone compound, the example of acetonaphthone compound comprises 1-acetonaphthone and 2-acetonaphthone, and the both is known and can easily obtains.
In the naphthyl alkyl ketone compound, the example of naphthalene acetonide comprises 1-naphthalene acetone and 2-naphthalene acetone.1-naphthalene acetone for example can be by using 1, and 2-ethylene dichloride etc. make naphthalene and propionyl chloride-aluminium reaction obtain (seeing the Comparative Examples 1 of following record) as solvent.
2-naphthalene acetone for example can be by making reactions such as 2-naphthyl cyanide and ethylmagnesium bromide, and the described reaction mixture of hydrolysis obtains (seeing the Comparative Examples 2 of following record) under strong acid condition.
The example of benzenyl amidine compound comprises benzenyl amidine; The organic acid salt of benzenyl amidine is as the benzenyl amidine acetate; With the inorganic acid salt of benzenyl amidine, as NSC 2020.
Can use compound known ad lib as dehydrohalogenation reagent.The example of these dehydrohalogenation reagents comprises mineral alkali, as sodium hydroxide, and potassium hydroxide, calcium hydroxide, yellow soda ash, salt of wormwood, sodium bicarbonate and saleratus; Organic bases, as triethylamine and 1,8-diazabicyclo [5.4.0]-7-undecylene (DBU); With the alkoxide cpd of metal, as sodium methylate and uncle-butanols potassium.
Can use compound known ad lib, as long as for example 2-halogenation naphthyl alkyl ketone compound and benzenyl amidine compound and do not participate in reaction in wherein to their solubilized as reaction solvent.The example of appropriate solvent comprises alcohol, as ethanol and Virahol; Hydro carbons is as hexane and toluene; Halohydrocarbon is as chloroform and chlorobenzene; Ester is as ethyl acetate; Nitrile is as acetonitrile; Ether is as tetrahydrofuran (THF) and dioxane; Acid amides is as dimethyl formamide (DMF) and N,N-DIMETHYLACETAMIDE (DMAC); In addition, dimethyl sulfoxide (DMSO) (DMSO).
Preferred room temperature～the reflux temperature of temperature of reaction; With the reaction times preferred 1～10 hour.Reaction can be carried out under barometric point usually.
The 2-phenyl that forms under aforesaid reaction conditions-4-naphthyl imidazolium compounds can be isolated by for example following lock out operation.That is, after reaction is finished,, can obtain the coarse fodder that needs, be solid for example by to the reaction mixture that obtains or from the enriched material of reaction mixture distilling off solvent, added big water gaging.Coarse fodder can be by purifying such as recrystallization operations.
In the middle of the phenyl napthyl imidazolium compounds of the present invention, compound classification is 2-naphthyl-4-phenylimidazole compound, wherein the 2-position of imidazole ring and 4-position are replaced by naphthyl and phenyl respectively, the 5-position does not replace, that is, 2-(1-naphthyl)-4-phenylimidazole and 2-(2-naphthyl)-4-phenylimidazole can be for example by making the naphthaldehyde compound at water-miscible organic solvent (in alcohol) under heating, the 2-acetoxy acetophenone, ammonia and venus crystals (II) synthesize by following reaction process reaction.
In the reaction shown in above-mentioned reaction process, the amount of used 2-acetoxy acetophenone, based on the naphthaldehyde compound, 0.8～1.5 times of preferred molar ratio, more preferably mol ratio is 0.9～1.1 times.The amount of used ammonia, based on the naphthaldehyde compound, preferred molar ratio is 10～50 times, more preferably 20～30 times.The amount of used venus crystals (II), based on the naphthaldehyde compound, preferred molar ratio is 1～5 times, more preferably 2～3 times.
For example by making the reaction of 2-chloro-acetophenone and potassium acetate can obtain 2-acetoxy acetophenone (Comparative Examples of stating as follows 3).The naphthaldehyde compound also comprises 1-naphthaldehyde and 2-naphthaldehyde, and these compounds all are known and can easily obtain.
The example of reaction solvent comprises alcohol, as methyl alcohol, and ethanol, propyl alcohol and Virahol, acetonitrile and tetrahydrofuran (THF).
Preferred 50～80 ℃ of temperature of reaction; With the reaction times preferred 1～10 hour.Reaction can be carried out under barometric point usually.
Under aforesaid reaction conditions, the 2-of formation naphthyl-4-phenylimidazole compound for example can be isolated by following lock out operation.That is, after reaction was finished, by filtration collecting precipitation thing, and precipitation was suspended in the methyl alcohol.Then, added this methanol suspension step by step, no longer consumed sodium sulfhydrate up to based on the sodium sulfhydrate of 0.5～0.8 times of mole of naphthaldehyde compound; Leach sedimentary cupric sulfide; Distill out methyl alcohol in a vacuum; The residue water rinse, thus the coarse fodder that needs obtained, be solid.Coarse fodder can be by purifying such as recrystallization operations.
In the phenyl napthyl imidazolium compounds of the present invention, compound classification is 2-naphthyl-4-phenyl-5-Methylimidazole compound, the 2-position of imidazole ring wherein, 4-position and 5-position are respectively by naphthyl, phenyl and methyl substituted, i.e. 2-(1-naphthyl)-4-phenyl-5-Methylimidazole and 2-(2-naphthyl)-4-phenyl-5-Methylimidazole, it can be for example by making the naphthaldehyde compound under heating, 1-phenyl-1,2-propanedione and ammonium acetate are synthetic by following reaction process reaction in acetate.
In the reaction shown in above-mentioned reaction process, used 1-phenyl-1, the amount of 2-propanedione, based on the naphthaldehyde compound, 0.8～1.5 times of preferred molar ratio, more preferably mol ratio is 0.9～1.1 times.The amount of used ammonium acetate, based on the naphthaldehyde compound, preferred molar ratio is 2～10 times, more preferably 4～6 times.
The naphthaldehyde compound that is used for this reaction comprises 1-naphthaldehyde and 2-naphthaldehyde, and these compounds are identical with aforementioned record.
The preferred 80 ℃～reflux temperature of temperature of reaction; With the reaction times preferred 1～10 hour.Reaction can be carried out under barometric point usually.
The 2-naphthyl that forms under aforesaid reaction conditions-4-phenyl-5-Methylimidazole compound for example can separate by following lock out operation.That is, after reaction is finished, will be by distill out reaction mixture or the residue that acetate obtains from reaction mixture, water-soluble with the alkaline reagents (for example, sodium hydroxide, yellow soda ash and ammonia) excessive with respect to acetate wherein, and mix, thereby can precipitate the coarse fodder that needs.Coarse fodder can be by purifying such as recrystallization operations.
The phenyl napthyl imidazolium compounds can be dissolved in appropriate carriers, as water or organic solvent, to form surface treatment agent.
Can contain for example 0.01～10wt% in the surface treatment agent, the phenyl napthyl imidazolium compounds of preferred 0.1～5wt%.The content of imidazolium compounds is less than 0.01wt% the time, and the film thickness of the chemical layer that forms on the copper surface can be too thin, makes to prevent the oxidation on copper surface.On the other hand, when it surpassed 10wt%, the imidazolium compounds in the surface treatment agent may surplusly have undissolved, made to form the uniform aqueous solution.
When dissolving imidazolium compounds (the formation aqueous solution) in water, organic acid or mineral acid can be used as acid, but can use a small amount of organic solvent simultaneously.Used organic acid representative example comprises formic acid, acetate, propionic acid, butyric acid, glyoxylic acid, pyruvic acid, etheric acid, levulinic acid, enanthic acid is sad, capric acid, dodecylic acid, oxyacetic acid, R-Glyceric acid, lactic acid, vinylformic acid, methoxyacetic acid, ethoxyacetic acid, propoxy-acetate, butoxy acetic acid, 2-(2-methoxy ethoxy) acetate, 2-[2-(2-ethoxy ethoxy) oxyethyl group] acetate, 2-{2-[2-(2-ethoxy ethoxy) oxyethyl group] oxyethyl group } acetate, methoxypropionic acid, ethoxy-propionic acid, the propoxy-propionic acid, butoxy propionic acid, phenylformic acid, the p-nitrobenzoic acid, p-toluenesulphonic acids, Whitfield's ointment, picric acid, oxalic acid, Succinic Acid, toxilic acid, fumaric acid, tartrate and hexanodioic acid; The example of described mineral acid comprises hydrochloric acid, phosphoric acid, sulfuric acid and nitric acid.
These acid can be based on the aqueous solution with 0.1～50wt%, and the ratio of preferred 1～30wt% adds.
In addition, representative examples of organic comprises lower alcohol, as methyl alcohol, and ethanol and Virahol, or acetone, N, dinethylformamide and ethylene glycol etc., they can freely mix with water miscibility.
Can add metal-salt to surface treatment agent of the present invention.Copper compound is as under the situation of metal-salt, and it can promote the formation speed of chemical layer on copper or the copper alloy surface.Zn cpds is as under the situation of metal-salt, and it can further improve the thermotolerance of chemical layer.
The example of typical copper compound comprises neutralized verdigris, cuprous chloride, cupric chloride, cuprous bromide, cupric bromide, cupric iodide, copper hydroxide, cupric phosphate, copper sulfate and cupric nitrate; Comprise zinc oxide with the example of typical described zn cpds, zinc formate, zinc acetate, zinc oxalate, zinc lactate, zinc citrate, zinc sulfate, zinc nitrate and zinc phosphate.Metal-salt can use separately or two or more be used in combination with it.Metal-salt in the surface treatment agent can 0.01～10wt%, and the ratio of preferred 0.02～5wt% adds.
Use under the situation of these copper compounds or zn cpds, need come the pH of stabilizing solution by the material that adding has a shock absorption, the material of described shock absorption as except that as described in ammonia, monoethanolamine, diethanolamine and trolamine organic acid or the mineral acid.
For further improving the formation speed of chemical layer and the thermotolerance of film, can in surface treatment agent of the present invention, add halogen compounds.The example of halogen compounds comprises Sodium Fluoride, Potassium monofluoride, Neutral ammonium fluoride, sodium-chlor, Repone K, ammonium chloride, Sodium Bromide, Potassium Bromide, brometo de amonio, sodium iodide, potassiumiodide and ammonium iodide.These halogen compounds can be used separately or two or more be used in combination with it.Halogen compounds in the surface treatment agent can 0.001～1wt%, and the ratio of preferred 0.01～0.1wt% adds.
For using the condition of handling the surface of copper or copper alloy according to surface treatment agent of the present invention, the fluid temperature of surface treatment agent can be for example 10～70 ℃, can be for example 1 second～10 minutes duration of contact.The example of contact method comprise soak, spraying and cladding process.
In addition, carry out after the surface treatment of the present invention,, also can further improve thermotolerance by being formed on the bilayer structure that has thermoplastic resin on the chemical layer.
Promptly, on copper or copper alloy surface, form after the chemical layer, the thermoplastic resin that has an excellent heat resistance by dissolving in solvent (for example, toluene, ethyl acetate and Virahol), and use for example roll coater etc., thickness with for example 1～30 μ m on chemical layer applies described solution equably, form the bilayer structure of chemical layer and thermoplastic resin, wherein said thermoplastic resin for example can comprise, rosin derivative (for example rosin and rosin ester), terpine resin derivative (for example terpine resin and terpene phenolic resin), hydrocarbon resin (for example aromatic hydrocarbon resin and aliphatic hydrocarbon resin) or its mixture.
The example that is suitable for implementing scolder of the present invention not only comprises normally used tinsel low eutectic solder, and comprises lead-free solder, as the Sn-Ag-Cu base, and Sn-Ag-Bi base, Sn-Bi base, Sn-Ag-Bi-In base, Sn-Zn base and Sn-Cu parent metal.
Welding process of the present invention also can be adapted to fluid welding method and reflow welding method.
The fluid welding method is included in mobile printing wiring board in the melt liquid state scolder of weld groove, with welding electronic unit and printed-wiring board (PWB).
On the contrary, the reflow welding method comprises according to line pattern prints the paste scolder in advance on printed-wiring board (PWB), electronic unit is mounted thereto, and heats whole printed-wiring board (PWB) and finish welding with fusion welding.
Embodiment
The synthetic embodiment of reference example 1～8 as described below notebook invention at length phenyl napthyl imidazolium compounds, but the present invention should not be limited to this.Incidentally, it is as follows to be used for the main raw material(s) of synthesis of phenyl naphthyl imidazolium compounds.
(starting material)
NSC 2020 (by Tokyo Kasei Kogyo Co., the reagent that Ltd. makes)
ω-bromo-1-acetonaphthone (by as the described method preparation of JP-A-9-286755)
ω-bromo-2-acetonaphthone (by Tokyo Kasei Kogyo Co., the reagent that Ltd. makes)
1-naphthalene acetone (by as Comparative Examples 1 described method preparation)
2-naphthalene acetone (by as Comparative Examples 2 described method preparations)
2-acetoxyl group acetonaphthone (by as Comparative Examples 3 described method preparations)
1-naphthaldehyde (by Tokyo Kasei Kogyo Co., the reagent that Ltd. makes)
2-naphthaldehyde (by Tokyo Kasei Kogyo Co., the reagent that Ltd. makes)
1-phenyl-1,2-propanedione (by Tokyo Kasei Kogyo Co., the reagent that Ltd. makes)
Comparative Examples 1
(preparation of 1-naphthalene acetone)
Under 5～10 ℃, the aluminum chloride of 143.7g (1.08 moles) is added to step by step by 1 of 92.6g (1.0 moles) propionyl chloride and 320mL in batches, in the solution that the 2-ethylene dichloride is formed, after adding is finished, temperature is raised to room temperature, with 1 of preparation propionyl chloride aluminum chloride complex compound, 2-dichloroethane solution.
In 1 hour, with 1 of above-mentioned propionyl chloride aluminum chloride complex compound, the 2-dichloroethane solution is added drop-wise to by 128.2g (1.0 moles) naphthalene and 300mL 1 under 35～40 ℃, in the solution that the 2-ethylene dichloride is formed.After adding was finished, the mixing liquid that heating obtains under 45～50 ℃ temperature 2 hours was poured in the frozen water behind the cool to room temperature.Further the 200mL concentrated hydrochloric acid is added wherein, stir and mix this mixture.With chloroform and 1, the product that forms in the 2-ethylene dichloride extractive reaction mixture is used dried over mgso, and vacuum concentration.Distill in a vacuum spissated liquid obtain 145.3g 1-naphthalene acetone (productive rate: 79%, 139～142 ℃ of boiling points/4mmHg), be light yellow oil.
Comparative Examples 2
(preparation of 2-naphthalene acetone)
50.8g (0.33 mole) 2-naphthyl cyanide little by little is added to by in the diethyl ether solution of the ethylmagnesium bromide of 164g (0.5 mole) concentration 3M and the solution that the dried benzene of 120mL is formed, stops to begin heating after the heating.Distill out about 100mL overhead product of mainly being made up of diethyl ether, add the benzene of 100mL, heated mixt is 3 hours under refluxing.After heating is finished, the reaction mixture cool to room temperature; The solution that adding is made up of 35g (0.654 mole) ammonium chloride and 140mL water; Remove water layer; The 6N hydrochloric acid that adds 600mL; Heated mixt is 4 hours under refluxing.After the cooling, remove water layer; Wash organic layer with water, use dried over sodium sulfate, evaporate to dryness in a vacuum obtains 57.3g 2-naphthalene acetone (productive rate: 94.2%), be the dark yellow solid then.
Comparative Examples 3
(preparation of 2-acetoxy acetophenone)
In the ethanol at 500mL under refluxing, the potassium acetate of heating 78.5g (0.80 mole), the acetate of 5.0g (0.08 mole), and the 2-chloro-acetophenone of 123.7g (0.80 mole) 6 hours.After heating was finished, the reaction mixture cool to room temperature leached sedimentary Repone K, and vacuum distilling goes out ethanol, obtains light brown oily material.This oily mater is poured in 1 premium on currency, and by filtering the solid of collecting precipitation, recrystallizing methanol obtains 113.1g 2-acetoxy acetophenone (productive rate: 79.3%), be light yellow solid.
Embodiment 1
(synthesizing of 2-phenyl-4-(1-naphthyl) imidazoles)
Under refluxing, heat by 31.3g (0.20 mole) NSC 2020 the suspension that 10.8g (0.20 mole) sodium methylate and 150mL tetrahydrofuran (THF) are formed 1 hour.Be cooled to after 25 ℃, drip the solution of forming by 49.8g (0.2 mole) ω-bromo-1-acetonaphthone and 100mL tetrahydrofuran (THF), make internal temperature be no more than 30 ℃.After adding is finished, add 10.8g (0.20 mole) sodium methylate, heated mixt is 1 hour under refluxing.Then, the reaction mixture cool to room temperature leaches insoluble substance, evaporated in vacuo filtrate.Water and acetonitrile wash residual solid are dry then continuously, obtain thick crystallization, are the material of needs.Thick crystallization acetonitrile recrystallization obtains 18.0g dusty blue crystallization (productive rate: 33.3%).
Gained crystalline fusing point, thin-layer chromatography Rf value and NMR and mass-spectrometric data are as follows.
·m.p.：167～169℃
TLC (silica gel, chloroform/ethyl acetate=9/1), Rf=0.90
·NMR(CD
3OD)：δ7.3～8.4(m)
·MS?m/z(％)：270(M+，100)，167(56)，139(20)，117(5)，104(7)，89(6)
From these mass-spectrometric datas as can be known, the compound that obtains is 2-phenyl-4-(1-naphthyl) imidazoles that is shown below.
Embodiment 2
(synthesizing of 2-phenyl-4-(2-naphthyl) imidazoles }
Under refluxing, heat by 31.3g (0.20mol) NSC 2020 the suspension that 10.8g (0.20 mole) sodium methylate and 150mL tetrahydrofuran (THF) are formed 1 hour.Be cooled to after 20 ℃, drip the solution of forming by 49.8g (0.2 mole) ω-bromo-2-acetonaphthone and 100mL tetrahydrofuran (THF), make internal temperature be no more than 30 ℃.After adding is finished, add 10.8g (0.20 mole) sodium methylate, heated mixt is 1 hour under refluxing.Then, the reaction mixture cool to room temperature leaches insoluble substance, the vacuum-evaporation dried filtrate.The residual solid of water and toluene wash is dry then continuously, obtains thick crystallization, is the material of needs.This thick crystallization acetonitrile recrystallization obtains 32.8g clear crystal (productive rate: 60.7%).
Gained crystalline fusing point, thin-layer chromatography Rf value and NMR and mass-spectrometric data are as follows.
·m.p.：230～233℃
TLC (silica gel, chloroform/ethyl acetate=9/1), Rf=0.33
·NMR(CD
3OD)：δ7.4～8.3(m)
·MS?m/z(％)：270(M+，100)，243(5)，166(11)，139(21)，117(10)，86(6)
From these mass-spectrometric datas as can be known, the compound that obtains is 2-phenyl-4-(2-naphthyl) imidazoles that is shown below.
Embodiment 3
(synthesizing of 2-phenyl-4-(1-naphthyl)-5-Methylimidazole)
Under 50～55 ℃, 53.3g (0.334 mole) bromine is added drop-wise in the solution of being made up of 61.1g (0.332 mole) 1-naphthalene acetone and 180mL ethanol.Add finish after, vacuum distilling goes out ethanol, the enriched material that obtains is dissolved in the 130mL toluene, with the mixed aqueous solution washing (150mL * twice) of sodium bicarbonate and sodium-chlor, uses dried over sodium sulfate then, obtain 2-bromo-1 '-toluene solution of naphthalene acetone.
Heating is by 50.1g (0.32 mole) NSC 2020 under refluxing, the suspension that 133g (0.96 mole) salt of wormwood and 250mL tetrahydrofuran (THF) are formed 1 hour, in 50 minutes, drip above-mentioned 2-bromo-1 '-toluene solution of naphthalene acetone.After adding is finished, reflux 2 hours.Then, the vacuum concentration reaction mixture, the enriched material that obtains 200mL dilution with toluene, described solution pours in the water of 600mL.Stir this mixture with precipitated solid.Collect this solid by filtering, use toluene and water washing continuously, dry then, obtain thick crystallization, be the material of needs.Thick crystallization DMF recrystallization obtains 48.1g white powder (productive rate: 52.9%).
The fusing point of gained powder, thin-layer chromatography Rf value and NMR and mass-spectrometric data are as follows.
·m.p.：280～282℃
TLC (silica gel, acetone), Rf=0.65
·NMR(d
6-DMSO)：δ2.27(s，3H)，7.38～8.27(m，12H)
·MS?m/z(％)：284(M+，100)，269(1)，215(4)，180(23)，166(4)，153(17)，139(10)，127(7)，104(10)，89(6)，77(10)，62(6)
From these mass-spectrometric datas as can be known, the compound that obtains is the 2-phenyl-4-shown in the following formula (1-naphthyl)-5-Methylimidazole.
Embodiment 4
(synthesizing of 2-phenyl-4-(2-naphthyl)-5-Methylimidazole)
Under 50～55 ℃, 46.0g (0.288 mole) bromine is added drop-wise in the solution of being made up of 55.8g (0.303 mole) 2-naphthalene acetone and 250mL ethanol.After adding is finished; Vacuum distilling goes out ethanol; The enriched material that obtains is dissolved in 130mL toluene; Mixed aqueous solution washing (200mL * twice) with sodium bicarbonate and sodium-chlor; Use dried over sodium sulfate then; Obtain 2-bromo-2 '-toluene solution of naphthalene acetone.
Heating is by 45.1g (0.288 mole) NSC 2020 under refluxing, the suspension that 119.4g (0.864 mole) salt of wormwood and 240mL tetrahydrofuran (THF) are formed 1 hour, in 40 minutes, drip above-mentioned 2-bromo-2 '-toluene solution of naphthalene acetone.After adding is finished, continued reflux 2 hours.Then, the vacuum concentration reaction mixture, the enriched material that obtains 200mL dilution with toluene, described solution is poured in the 600mL water.Stir this mixture with precipitated solid.Collect this solid by filtering, use toluene and water washing continuously, dry then, obtain thick crystallization, be the material of needs.This thick crystallization acetonitrile recrystallization obtains 55.0g white powder (productive rate: 67.2%).
The fusing point of gained powder, thin-layer chromatography Rf value and NMR and mass-spectrometric data are as follows.
·m.p.：215～218℃
TLC (silica gel, acetone), Rf=0.69
·NMR(CDCl
3)：δ2.56(s，3H)，7.34～8.03(m，12H)
·MS?m/z(％)：284(M+，100)，243(1)，215(2)，180(14)，153(12)，139(9)，127(4)，104(7)，89(5)，77(7)，63(5)
From these mass-spectrometric datas as can be seen, the compound that obtains is 2-phenyl-4-(2-naphthyl)-5-Methylimidazole.
Embodiment 5 (synthesizing of 2-(1-naphthyl)-4-phenylimidazole)
With under the water cooling, to be added to 1-naphthaldehyde by the drips of solution that 70.3g (0.352 mole) venus crystals (II) monohydrate and 220g (3.2 moles) 25% ammoniacal liquor are formed by 25.6g (0.160 mole), in the solution that (29.4g 0.165 mole) 2-acetoxy acetophenone and 300mL Virahol are formed, subsequently, temperature was raised to 60 ℃ in 1 hour, and further was raised to 78 ℃ in 3 hours.After the reaction mixture cooling,, wash with water by filtering the collecting precipitation thing, dry then.The sap green powder suspension that obtains adds the sodium sulfhydrate of 8.1g (0.10 mole) 70% in methyl alcohol, this mixture of heating is 1 hour under refluxing.Cool off this methanol solution, leach insoluble atrament, the vacuum-evaporation dried filtrate.
Residual solids is dissolved in chloroform, and washes with water, and vacuum distilling goes out chloroform, with acetonitrile recrystallization exsiccant material, obtains 12.1g off-white powder (productive rate: 28%).
The fusing point of gained powder, thin-layer chromatography Rf value and NMR and mass-spectrometric data are as follows.
·m.p.：198～202℃
TLC (silica gel, chloroform/ethyl acetate=9/1), Rf=0.41
·MMR(CD
3OD)：δ7.0～8.4(m)
·MS?m/z(％)：270(M+，100)，241(3)，166(4)，139(10)，135(9)，127(7)，120(3)，116(5)，89(20)，77(4)，63(7)
From these mass-spectrometric datas as can be known, the compound that obtains is the 2-shown in the following formula (1-naphthyl)-4-phenylimidazole.
Embodiment 6
(synthesizing of 2-(2-naphthyl)-4-phenylimidazole)
With under the water cooling, to be added to by the drips of solution that the ammoniacal liquor of 72.4g (0.363 mole) venus crystals (II) monohydrate and 230g (3.38 moles) 25% is formed by 26.1g (0.167 mole) 2-naphthaldehyde, in the solution that (30.0g 0.168 mole) 2-acetoxy acetophenone and 300mL Virahol are formed, subsequently, temperature is raised to 60 ℃ in 1 hour, further is raised to 78 ℃ in 3 hours.After the reaction mixture cooling,, wash with water by filtering the collecting precipitation thing, dry then.The sap green powder suspension that obtains adds the sodium sulfhydrate of 8.5g (0.11 mole) 70% in methyl alcohol, this mixture of heating is 1 hour under refluxing.This methanol solution cool to room temperature leaches insoluble atrament, the vacuum-evaporation dried filtrate.Residual solids washes with water and is dissolved in acetone, adds oxalic acid, by filtering the oxalate of collecting precipitation.Oxalate is suspended in the methyl alcohol, and adds sodium methylate to discharge the material that needs.Vacuum distilling goes out methyl alcohol, washes the enriched material that obtains with water, and uses recrystallizing methanol, obtains the light yellow crystallization of 6.1g (productive rate: 13.5%).
Gained crystalline fusing point, thin-layer chromatography Rf value and NMR and mass-spectrometric data are as follows.
·m.p.：194～198℃
TLC (silica gel, chloroform/ethyl acetate=9/1), Rf=0.57
·NMR(d
6-DMSO)：δ7.22～8.48(m)
·MS?m/z(％)：270(M+，100)，243(6)，215(3)，167(13)，153(6)，139(14)，127(9)，116(6)，89(25)，77(4)，63(9)
From these mass-spectrometric datas as can be known, the compound that obtains is the 2-shown in the following formula (2-naphthyl)-4-phenylimidazole.
Embodiment 7
(synthesizing of 2-(1-naphthyl)-4-phenyl-5-Methylimidazole)
In 250mL acetate, under refluxing, heat the 1-phenyl-1 of 50.2g (0.34 mole), 2-propanedione, the ammonium acetate of the 1-naphthaldehyde of 52.9g (0.34 mole) and 157g (2.04 moles) 3 hours.Vacuum concentration reaction mixture, the ammoniacal liquor of Macrodilution are poured in the enriched material that obtains, and by the solid of filtration collecting precipitation, and wash with water.The solid that obtains is dissolved in acetone, adds oxalic acid, by filtering the oxalate of collecting precipitation.Then, the oxalate of collecting is dissolved in methyl alcohol, add the material that sodium methylate discharges to be needed, and vacuum distilling goes out methyl alcohol.Water and normal hexane wash residual solid obtain 30.8g oyster white crystallization (productive rate: 32%) continuously.
Gained crystalline fusing point, thin-layer chromatography Rf value and NMR and mass-spectrometric data are as follows.
·m.p.：80～85℃
TLC (silica gel, chloroform/ethyl acetate=9/1), Rf=0.50
·NMR(de-DMSO)：δ2.53(s，3H)，7.14～8.02(m，12H)
·MS?m/z(％)：284(M+，100)，268(4)，241(2)，215(1)，180(2)，153(4)，142(6)，130(7)，103(12)，89(5)，77(7)，63(3)
From these mass-spectrometric datas as can be known, the compound that obtains is the 2-shown in the following formula (1-naphthyl)-4-phenyl-5-Methylimidazole.
Embodiment 8
(synthesizing of 2-(2-naphthyl)-4-phenyl-5-Methylimidazole)
In 120mL acetate, under refluxing, heat the 1-phenyl-1 of 24.5g (0.265 mole), 2-propanedione, the ammonium acetate of the 2-naphthaldehyde of 25.8g (0.165 mole) and 76.5g (0.992 mole) 5 hours.Vacuum concentration reaction mixture, the enriched material that obtains pour in a large amount of weak ammonias, and by filtering the solid of collecting precipitation, water and acetonitrile washing continuously obtains 22.7g light yellowish brown powder (productive rate: 48.2%).
The fusing point of gained powder, thin-layer chromatography Rf value and NMR and mass-spectrometric data are as follows.
·m.p.：237～240℃
TLC (silica gel, chloroform/ethyl acetate=9/1), Rf=0.57
·NMR(CD
3OD)：δ2.47(s，3H)，7.33～8.37(m，12H)
·MS?m/z(％)：284(M+，100)，243(3)，215(2)，180(5)，154(7)，142(9)，130(14)，103(13)，89(7)，77(8)，63(4)
From these mass-spectrometric datas as can be known, the compound that obtains is the 2-shown in the following formula (2-naphthyl)-4-phenyl-5-Methylimidazole.
Describe the surface treatment agent that uses the phenyl napthyl imidazolium compounds among the present invention in detail below with reference to embodiment 9～22 and Comparative Examples 1～7, surface treatment method, the example of welding process and printed-wiring board (PWB), but the invention is not restricted to this.Incidentally, welding test is as follows.
(evaluation test of flow of solder material speed ability)
The printed-wiring board (PWB) of being made, being had 300 copper vias of 0.80 millimeter of internal diameter by the glass epoxy resin of millimeter (width) * 1.6,120 millimeters (length) * 150 millimeter (thickness) is used as testpieces.To this testpieces degreasing, carry out soft etching, wash with water then.Thereafter, testpieces is soaked in preset time in the surface treatment agent that remains on the predetermined liquid temperature, washes with water, and is dry then, forms the chemical layer of about 0.10～0.50 μ m of thickness on the copper surface.
Use (the trade name: MULTI-PRO-306 of infrared reflow baking oven, Vetronix Co.Ltd. makes), the surface-treated testpieces is carried out backflow-heating cycle three times, and wherein top temperature is 240 ℃, and welds (line speed: 1.0m/min) with fluid welding equipment subsequently.
Used scolder is tin-plumbous low eutectic solder, and consisting of 63% tin and 37% lead (wt%) (trade name: H63A is made by Senju Metal Industry Co.Ltd.) and the flux that is used to weld is JS-64MSS (by Koki Co., Ltd. makes).Described welding temperature is 240 ℃.
Also can use lead-free solder, with tin-same method of plumbous low eutectic solder, the testpieces surface that welding is as above handled.Used scolder is lead-free solder (trade name: H705 " ECOSOLDER ", by Senju Metal Industry Co., Ltd. makes), consist of 96.5% tin, 3.0% silver medal and 0.5% bronze medal (wt%) and the flux that is used to weld are JS-E-09 (by KokiCo., Ltd. make).The reflux top temperature is 245 ℃, and welding temperature also is 245 ℃.
For the testpieces of welding, measuring result is with the sum (300 holes) with respect to copper vias, and wherein the scolder filling is up to ratio (%) expression of the copper vias number of the copper face (copper land) of copper vias.
Scolder is when the wettability on copper surface is big, and fusion welding is seeped into the inside of each copper vias, thereby fusion welding easily is filled into top (the upper land) of through hole.More particularly, if soldered number of through-holes in plane is big on it, scolder is evaluated as fabulous to the wettability and the weldability of copper so.
(evaluation test of scolder spreadability)
The printed-wiring board (PWB) of being made by the glass epoxy resin of millimeter (width) * 1.2,50 millimeters (length) * 50 millimeter (thickness) is used as testpieces.Printed-wiring board (PWB) has such wiring diagram, wherein forms 10 copper foil circuits with conducting band of 0.80 millimeter of width, 20 millimeters of length at width every 1.0 millimeters.To the testpieces degreasing, carry out soft etching, wash with water then.Thereafter, testpieces is soaked in specific time in the surface treatment agent that remains on the regulation fluid temperature, washes with water, and is dry then, forms the chemical transformation film of about 0.10～0.50 μ m of thickness on the copper surface.
Use infrared reflow baking oven (trade name: MULTI-PRO-306, Vetronix Co.Ltd. makes), the surface-treated testpieces is once refluxed-heating cycle, wherein top temperature is 240 ℃., use the metal hovel of 1.2 millimeter apertures and 150 millimeter thickness, tin-lead solder slurry is printed onto the center of copper wire, under aforesaid welding conditions, carry out reflux thereafter.Tin-lead solder the slurry that uses is low eutectic solder (trade name: OZ-63-330F-40-10, by Senju Metal Industry Co., Ltd. makes), consists of 63% tin and 37% lead (wt%).
Also can use the lead-free solder slurry, with tin-same method of lead solder slurry, the specimen surface that welding is as above handled.The lead-free solder that uses is by 96.5% tin, and 3.0% silver medal and 0.5% bronze medal (wt%) are formed (trade name: M705-221BM5-42-11, by Senju Metal IndustryCo., Ltd. makes).The reflux top temperature that reaches before and after the printing with paste is arranged on 245 ℃.
Measure moistening and sprawl the length (millimeter) of the copper wire of gained testpieces.
When length was longer, the wettability of scolder and weldability were evaluated as fabulous.
Embodiment 9
With synthetic among the embodiment 2 as 2-phenyl-4-(2-naphthyl) imidazoles of phenyl napthyl imidazolium compounds and and just as the lactic acid of acid-enanthic acid is dissolved in deionized water, to have composition as described in Table 1, is 3.2 with ammoniacal liquor with pH regulator, thus the preparation surface treatment agent.
Then, the testpieces of printed-wiring board (PWB) is soaked in and was controlled at 40 ℃ of surface treatment agents under the temperature 240 seconds, washes with water, and is dry then, thereby measures the velocity of flow performance of scolder and the spreadability of scolder.These test-results are as shown in table 1.
Embodiment 10～22
Use phenyl napthyl imidazolium compounds as described in Table 1, acid, metal-salt and halogen compounds so that 9 same method preparations have the surface treatment agent of composition as described in Table 1 with embodiment, and are carried out surface treatment under treatment condition as described in Table 1.For the sample that obtains, measure the velocity of flow performance of scolder and the spreadability of scolder.Test-results is as shown in table 1.
Incidentally, 2-(2-methoxy ethoxy) acetate as acid is the reagent of being made by SIGMA-ALDRICH.In addition, about 2-[2-(2-ethoxy ethoxy) oxyethyl group] acetate and 2-{2-[2-(2-ethoxy ethoxy) oxyethyl group] oxyethyl group acetate, use according to as Yukagaku, Vol.32, p.118 (1983) described synthesis method synthetic those.
Comparative Examples 1～7
Use imidazolium compounds as described in Table 2, acid, metal-salt and halogen compounds so that 9 same method preparations have the surface treatment agent of composition as described in Table 2 with embodiment, and are carried out surface treatment under treatment condition as described in Table 2.For the sample that obtains, measure the velocity of flow performance of scolder and the spreadability of scolder.Test-results is as shown in table 2.
Incidentally, it is as follows to be used for the imidazolium compounds of Comparative Examples.
2-undecyl imidazole (trade name: CllZ is made by Shikoku Chemicals Corporation)
The 2-phenylimidazole (trade name: 2PZ is made by Shikoku Chemicals Corporation }
2-phenyl-4-methylimidazole (trade name: 2P4MZ is made by Shikoku ChemicalsCorporation)
2-nonyl benzoglyoxaline (reagent is made by SIGMA-ALDRICH)
2-(4-Chlorophenylmethyl) benzoglyoxaline (according to Science of Synthesis, Vol.12, the method for 529 (2002) records is synthetic))
According to the test-results shown in table 1 and the table 2, think and contact under the situation that forms chemical layer with the copper surface at surface treatment agent of the present invention, it uses low eutectic solder or lead-free solder to weld then, because last velocity of flow (flow-up rate) performance of scolder and the spreadability of scolder improve significantly, so the scolder wettability of low eutectic solder and lead-free solder is all greatly improved.
The disclosure is based on following file and require its right of priority: the Japanese patent application No.2004-173150 of application on June 10th, 2004, the Japanese patent application No.2004-218230 of application on July 27th, 2004, with the Japanese patent application No.2005-128938 of application on April 27th, 2005, its content is introduced the present invention as a reference.
Claims (16)
1. the surface treatment agent of copper or copper alloy, it comprises carrier and by the phenyl napthyl imidazolium compounds shown in the following formula (I),
Wherein, A
1When being phenyl, A so
2Expression 1-naphthyl or 2-naphthyl, and A
1When being 1-naphthyl or 2-naphthyl, A so
2The expression phenyl; Represent hydrogen atom or methyl with R.
2. the surface treatment agent of copper as claimed in claim 1 or copper alloy, it comprises that carrier and ratio are the phenyl napthyl imidazolium compounds shown in the formula (I) of 0.01～10wt%.
3. surface treatment agent that is used for copper or copper alloy, comprise that carrier, ratio are organic acid or the mineral acid that phenyl napthyl imidazolium compounds shown in the formula (I) described in the claim 1 of 0.01～10wt% and ratio are 0.1～50wt%, wherein said surface treatment agent is the aqueous solution.
4. surface treatment agent as claimed in claim 1, wherein said carrier are water or organic solvent.
5. surface treatment agent as claimed in claim 1 further comprises metal-salt.
6. surface treatment agent as claimed in claim 5, wherein said metal-salt are the copper compounds that is selected from neutralized verdigris, cuprous chloride, cupric chloride, cuprous bromide, cupric bromide, cupric iodide, cupric phosphate, copper sulfate and cupric nitrate.
7. surface treatment agent as claimed in claim 1 further comprises copper hydroxide.
8. surface treatment agent as claimed in claim 5, wherein said metal-salt are the zn cpdss that is selected from zinc formate, zinc acetate, zinc oxalate, zinc lactate, zinc citrate, zinc sulfate, zinc nitrate and zinc phosphate.
9. surface treatment agent as claimed in claim 1 further comprises zinc oxide.
10. surface treatment agent as claimed in claim 5, the ratio that wherein said metal-salt exists is 0.01～10wt%.
11. surface treatment agent as claimed in claim 1 further comprises halogen compounds.
12. as the surface treatment agent of claim 11, wherein halogen compounds is selected from Sodium Fluoride, Potassium monofluoride, Neutral ammonium fluoride, sodium-chlor, Repone K, ammonium chloride, Sodium Bromide, Potassium Bromide, brometo de amonio, sodium iodide, potassiumiodide and ammonium iodide.
13. as the surface treatment agent of claim 11, the ratio that wherein said halogen compounds exists is 0.001～1wt%.
14. the surface treatment method of copper or copper alloy, it comprises the surface that makes described copper or copper alloy and contacts as each surface treatment agent of claim 1～3.
15. a printed-wiring board (PWB), it comprises the copper wire part that copper or copper alloy are formed, and the surface of wherein said copper or copper alloy with as each surface treatment agent of claim 1～3 contacts.
16. a welding process, it comprises the surface that makes described copper or copper alloy and contacts as each surface treatment agent of claim 1～3, welds then.
Applications Claiming Priority (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004173150 | 2004-06-10 | ||
| JP173150/2004 | 2004-06-10 | ||
| JP218230/2004 | 2004-07-27 | ||
| JP2004218230A JP4194984B2 (en) | 2004-07-27 | 2004-07-27 | Phenylnaphthylimidazole compound |
| JP128938/2005 | 2005-04-27 | ||
| JP2005128938A JP4694251B2 (en) | 2004-06-10 | 2005-04-27 | Copper or copper alloy surface treatment agent for lead-free soldering and use thereof |
| PCT/JP2005/010898 WO2005121101A1 (en) | 2004-06-10 | 2005-06-08 | Phenylnaphthylimidazoles for use on copper surfaces during soldering |
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| CN200910151813XA Division CN101624374B (en) | 2004-06-10 | 2005-06-08 | Phenylnaphthylimidazoles for use on copper surfaces during soldering |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO1999001128A1 (en) * | 1997-07-03 | 1999-01-14 | Neurogen Corporation | Certain diarylimidazole derivatives; a new class of npy specific ligands |
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| TW270944B (en) * | 1993-05-10 | 1996-02-21 | Shikoku Kakoki Co Ltd |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999001128A1 (en) * | 1997-07-03 | 1999-01-14 | Neurogen Corporation | Certain diarylimidazole derivatives; a new class of npy specific ligands |
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| Title |
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| JP特开2004－244390A 2004.09.02 |
| JP特开平8－183776A 1996.07.16 |
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