CN102873471A - Combined solution of alkylbenzimidazole derivatives and method for preparing organic solderability preservative (OSP) - Google Patents

Abstract

The invention provides a combined solution of alkylbenzimidazole derivatives and a method for preparing an organic solderability preservative (OSP). The method for preparing the OSP comprises the following steps of: attaching a secondary dry film in a dust-free room to cover a copper surface through which the OSP passes; finishing an electroless nickel immersion gold (ENIG) process; washing the secondary dry film by using NaOH to expose the prepared copper surface; feeding a circuit board into an OSP horizontal production line; soaking in a degreasing tank for 30 seconds; cleaning twice by using spray water, and micro-etching in a micro-etching groove for 30 seconds; cleaning twice by using spray deionized water, and soaking in a pre-immersion tank at room temperature for 30 seconds; soaking in an OSP tank for 90 seconds; and wiping by using a wringing roller, and air-drying by using a horizontal air-drying section. The technical problem that the conductivity of ENIG can be influenced because copper ions in the solution overquickly ascend at the later stage of using the OSP at present is solved, and the solution has the advantages of high selectivity, high-temperature resistance and solderability, long service life and the like.

Description

A kind of combination solution of alkyl Benzimidazoles and the preparation method of organic solderability preservative

Technical field

The invention belongs to organic solderability preservative OSP technology field, be specifically related to a kind of preparation method of combination solution and organic solderability preservative of alkyl Benzimidazoles.

Background technology

Organic solderability preservative OSP(Organic Solderability Preservatives) can form one deck organic protective film at copper face, it can be used for welding electronic part (such as the resistance inductance etc.).Renewal through five generations.State Intellectual Property Office discloses a kind of low-temperature solubilization agent and application process thereof of organic solderability preservative, and its publication number is 101758338A, and the open date is 2010-06-30.Still there are many problems in it on commerce is used.Its bad point mainly contains: need repeatedly to cross Reflow Soldering during heavy industry or when circuit board two sides weldering electronic component, it will cause the scolding tin performance greatly to weaken, even lose the ability of protection copper face.Because a large amount of generations of the equipment such as smart mobile phone, palm PDA, the pad on the wiring board is more and more less, and chemical nickel and gold is stablized good welding condition owing to the particularity that belongs to the displacement gold can't satisfy very little pad (such as BGA).Must select the good surface treatment of a kind of scolding tin to substitute the chemical nickel and gold of those little pads.OSP is with low cost; Scolding tin is good.It is a kind of good substitute.Two kinds of surface-treateds are good in conjunction with obtaining the key zone conduction, and the outstanding circuit board of weldering part district's weld strength.Because saved golden salt, reduce actual production cost simultaneously.But, to need copper ion to assist film forming in process of production in the existing selective OSP technology, aborning the solution copper ion can rise gradually (copper ion is because disproportionated reaction can make the copper dissolution on the wiring board copper face accelerate) too much copper ion and OSP active ingredient under the effect of chemical bond at surface of chemical nickel and gold face formation OSP epithelium, and can more and more thicker (prior art be that 150-180ppm changes groove).And this can hinder the electric conductivity of chemical nickel and gold.Because being necessary to provide a kind of method: it can be at tank liquor initial stage instead of copper ion, and suppresses copper ion stripping from the wiring board in the middle and later periods, thereby increases solution the selective of copper face increased the service life.

Summary of the invention

When using the later stage, can hinder the technical problem of the electric conductivity of chemical nickel and gold in order to solve present organic solderability preservative owing to the too fast rising of copper ion in the solution, the invention provides a kind of preparation method of combination solution and organic solderability preservative of alkyl Benzimidazoles.The defects that exists to overcome prior art.

The invention provides a kind of combination solution of alkyl Benzimidazoles, described in reaction the derivatives active composition of alkyl benzimidazole as follows:

Wherein, R1 is the alkyl of 1-4 carbon; X is for forming the metal that cooperates with it behind the solution.Preferably, make aborning the derivatives active composition of described alkyl benzimidazole as follows:

Wherein, R1 is the alkyl of 1-4 carbon.

Preferably, described R1 is preferably methyl.

A kind of preparation method who prepares the derivative combination solution of alkyl benzimidazole may further comprise the steps:

1) with (0.1mol) 1-phenyl-1 of 14.8g, (0.1mol) 3 of 2-propanedione, 17.5g, 4-dichlorobenzaldehyde and 46.2g (0.6mol) ammonium acetate adds hot reflux 5 hours in 100ml acetic acid;

2) the gained reactant liquor is cooled to room temperature behind the reaction terminating, injects a large amount of weak aqua ammonias, filters and separates out lotion, and is dry after the washing, obtains brown lotion 32g;

3) with described this paste dissolves in the 150ml chloroform, add concentrated hydrochloric acid, the hydrochloride that filtration is separated out after cleaning with acetone, is dissolved in the methyl alcohol, add again methanol solution of sodium methylate, after the desalination acid, heat up in a steamer methyl alcohol under the decompression again, through washing, dry behind the solid content that obtains, obtain the crystallization of 18.5g off-white powder shape;

4) described this crystallization is raw material shown in (A2).

A kind of preparation method of organic solderability preservative: it is characterized in that: may further comprise the steps:

1) sticking the secondary dry film at dust free room covers and wanted the copper face of OSP; Cover chemical nickel and gold technique; With NaOH flush away secondary dry film, expose ready copper face;

2) wiring board is sent into the OSP horizontal production line;

3) 37 ℃ of lower degreasing tank immersions with 10% KOZO 901 configurations 30 seconds;

4) clean the microetch groove microetch of under 27 ℃, preparing with the concentrated sulfuric acid of 80g/L sodium peroxydisulfate and 20ml/L 30 seconds with twice fountain water;

5) clean with twice spray ID water, enter the preimpregnation of preparing with 1% formic acid under the room temperature and soaked 30 seconds; Enter 27 ℃ of lower OSP drill traverse bubbles 90 seconds;

6) extract again by air-dry section of level air-dry with the water squeezing rumble after finishing.

Preferably, described OSP groove is take the alkyl Benzimidazoles as main active ingredient.

The present invention has the following advantages:

1) high selectivity because the adding of zinc has reduced copper ion, does not almost have the OSP epithelium on golden face.

2) high temperature resistant.Because having added the active ingredient heat-resisting ability that contains two phenyl ring in the OSP tank liquor greatly promotes.Can anti-multi-reflow weldering.

3) the solderability ability is good.Comparable other surface treatment is all good.

4) greatly prolong than before service life.

Description of drawings:

Fig. 1 be among the present invention in the scolding tin process circuit board feature weld cross before the Reflow Soldering and cross Reflow Soldering after the structural representation of tin cream melting;

Wherein: (a) be the front structural representation of Reflow Soldering;

(b) be structural representation after the Reflow Soldering.

The specific embodiment

The invention provides a kind of combination solution of alkyl Benzimidazoles, the derivatives active composition of alkyl benzimidazole is as follows:

Wherein, R1 is the alkyl of 1-4 carbon; X is for forming the metal that cooperates with it behind the solution.

Preferably, make aborning the derivatives active composition of described alkyl benzimidazole as follows:

Wherein, R1 is the alkyl of 1-4 carbon.Described R1 is preferably methyl.Wherein (A2) preparation method is as follows: with (0.1mol) 1-phenyl-1 of 14.8g, and (0.1mol) 3 of 2-propanedione, 17.5g, 4-dichlorobenzaldehyde and 46.2g (0.6mo l) ammonium acetate adds hot reflux 5 hours in 100ml acetic acid.The gained reactant liquor is cooled to room temperature behind the reaction terminating, injects a large amount of weak aqua ammonias, filters and separates out lotion, and is dry after the washing, obtains brown lotion 32g.With this paste dissolves in the 150ml chloroform, add concentrated hydrochloric acid, the hydrochloride that filtration is separated out after cleaning with acetone, is dissolved in the methyl alcohol, add methanol solution of sodium methylate, after the desalination acid, under reduced pressure heat up in a steamer methyl alcohol, through washing, dry behind the solid content that obtains, obtain 18.5g off-white powder shape crystallization (yield 61%).This crystallization is raw material shown in (A2).

The production method of selective OSP needs to cross first chemical nickel and gold.Wiring board to be sticked the secondary dry film at dust free room first, cover and wanted the copper face of OSP; Cover chemical nickel and gold technique; With NaOH flush away secondary dry film, expose ready copper face.This wiring board is sent into the OSP horizontal production line.Soaked 30 seconds through the degreasing tank with KOZO 90110% preparation under 37 ℃; Clean with twice sprays city water, enter under 27 ℃ with the microetch groove microetch of the concentrated sulfuric acid preparation of 80g/L sodium peroxydisulfate and 20ml/L 30 seconds; Clean with twice spray ID water, enter the preimpregnation of preparing with 1% formic acid under the room temperature and soaked 30 seconds.

Enter OSP drill traverse bubble 90 seconds.The preferred forms of OSP groove: derivative shown in the selected chemical formula (A1), preferred 1-10g/L; The complex metal that preferably can replace the part copper function: be chosen as zinc, preferred 0.1-5g/L.In solution, form following active ingredient:

It can be substituted in production initial stage required copper ion during solution film forming, suppresses simultaneously the stripping of copper ion, is unlikely to film forming on chemical nickel and gold gold face, thereby prolongs the life-span of OSP groove.Wherein OSP adopts following prescription to realize:

（A2）	1-10g/L
		Zinc formate	0.1-5g/L
Hexylene glycol	0.1-1ml/L
		KBr	0.1-1g/L
Ammonium chloride	0.1-1g/L
		Formic acid (or other acid)	10-200ml/L
Ammoniacal liquor	10-50ml/L

(A2) be OSP groove Main Ingredients and Appearance, it cooperates formation active ingredient (A3) with zinc formate; Zinc formate other metal for adding, the effect that it replaces copper ion to play at solution; Hexylene glycol can help (A2) to dissolve unlikely separating out in solution; KBr is the thickness growing agent; Ammonium chloride is auxiliary thickness growing agent; Ammonium water is auxiliary thickness growing agent and pH adjusting agent; Formic acid is film forming environment and OSP active ingredient lytic agent.The OSP groove adopts horizontal line to process, time 60-90 second.Roll rumble with water squeezing afterwards and suck unnecessary tank liquor on the circuit board in order to avoid there is water stain seal etc. residual.Cold wind dries up the rear circuit board that production is finished and carries out vacuum packaging.

The present invention is described further with the following Examples:

Embodiment 1:

（A2）	1g/L
		Zinc formate	0.2g/L
Hexylene glycol	0.2ml/L
		KBr	0.5g/L
Ammonium chloride	0.5g/L
		Formic acid	13.4ml/L
Ammoniacal liquor	7ml/L

[0046]Embodiment 2:

（A2）	1g/L
		Zinc formate	0.2g/L
Hexylene glycol	0.5ml/L
		KBr	0.7g/L
Ammonium chloride	0.65g/L
		Formic acid	14.6ml/L
Ammoniacal liquor	7.2ml/L

Embodiment 3:

（A2）	1g/L
		Zinc formate	0.2g/L
Hexylene glycol	0.5ml/L
		KBr	0.7g/L
Ammonium chloride	0.65g/L
		Lactic acid	68ml
Ammoniacal liquor	21.2ml/L

The performance test results:

1, thickness contrast.(the 90 seconds time; 27 ℃ of temperature)

	Thickness
		Embodiment 1	0.347um
Embodiment 2	0.375um
		Embodiment 3	0.293um

[0053]Above embodiment all can reach the requirement of the 0.2-0.5um of common customer needs.

2, epithelium density.This epithelium density method of testing is generally done reference with silver nitrate variable color experiment.Method is that the liquor argenti nitratis ophthalmicus with 0.1mol/L drops on the OSP epithelium, and writing time when being dripped place's beginning blackening, the time is more long to illustrate that more epithelium is finer and close.General Requirements 13-15 is more than second.

	The silver nitrate variable color time
		Embodiment 1	24 seconds
Embodiment 2	27 seconds
		Embodiment 3	22 seconds

The above embodiment nitric acid variable color time is all greater than 15 seconds.

3, scolding tin performance test.Be as the criterion with the angle of wetting test.This method of testing is to brush on the OSP epithelium on the test line plate with web plate with unleaded tin cream; Insert reflow machine (IR machine), utilize the tin of high-temperature fusion tin cream liquefy.At high temperature and help under the effect of tin agent tin as mercury, wettingly to melt simultaneously copper fresh under surperficial OSP epithelium and the epithelium and fuse into the gun-metal layer promptly flattening on the OSP epithelium.The tin that cools off liquid state when taking out again when circuit from reflow machine is solid form (this process is exactly scolding tin).At this moment there is an angle of wetting in the copper face of tin and bottom surface.More the bright scolding tin performance of novel is better for the angle of angle of wetting.As seen referring to shown in the Figure of description.

The two sides of considering circuit board in actual production is scolding tin possibly all, every face may heavy industry once.Therefore test also will be crossed Reflow Soldering (I R) 4 times simultaneously repeatedly.

	IR machine 1 time	IR machine 2 times	IR machine 3 times	IR machine 4 times
					Embodiment 1	1.2°	3.2°	5.3°	8.3°
Embodiment 2	1.4°	3.9°	6.3°	7.4°

[0060]

Embodiment 3

1.2°

4.7°

6.2°

8.5°

All can reach obvious wetting effect after above example I R4 time.The scolding tin performance can meet the demands.

Above content is in conjunction with concrete preferred embodiment further description made for the present invention, can not assert that implementation of the present invention is confined to these explanations.For the general technical staff of the technical field of the invention, without departing from the inventive concept of the premise, can also make some simple deduction or replace, all should be considered as belonging to protection scope of the present invention.

Claims (6)

1. the combination solution of an alkyl Benzimidazoles, it is characterized in that: the reactivity composition of the derivative of described alkyl benzimidazole is as follows:

Wherein, R1 is the alkyl of 1-4 carbon; X is for forming the metal that cooperates with it behind the solution.

2. the combination solution of an alkyl Benzimidazoles, it is characterized in that: the derivatives active composition that makes aborning described alkyl benzimidazole is as follows:

Wherein, R1 is the alkyl of 1-4 carbon.

3. the combination solution of alkyl Benzimidazoles according to claim 1 and 2, it is characterized in that: described R1 is preferably methyl.

4. a preparation method who prepares the derivative combination solution of alkyl benzimidazole in the claim 2 may further comprise the steps:

1) with (0.1mol) 1-phenyl-1 of 14.8g, (0.1mol) 3 of 2-propanedione, 17.5g, 4-dichlorobenzaldehyde and 46.2g (0.6mol) ammonium acetate adds hot reflux 5 hours in 100ml acetic acid;

2) the gained reactant liquor is cooled to room temperature behind the reaction terminating, injects a large amount of weak aqua ammonias, filters and separates out lotion, and is dry after the washing, obtains brown lotion 32g;

3) with described this paste dissolves in the 150ml chloroform, add concentrated hydrochloric acid, the hydrochloride that filtration is separated out after cleaning with acetone, is dissolved in the methyl alcohol, add again methanol solution of sodium methylate, after the desalination acid, under reduced pressure heat up in a steamer methyl alcohol, through washing, dry behind the solid content that obtains, obtain the crystallization of 18.5g off-white powder shape;

4) described this crystallization is raw material shown in (A2).

5. preparation method by the organic solderability preservative that comprises the prepared raw material of claim 4: it is characterized in that: may further comprise the steps:

1) sticking the secondary dry film at dust free room covers and wanted the copper face of OSP; Cover chemical nickel and gold technique; With NaOH flush away secondary dry film, expose ready copper face;

2) wiring board is sent into the OSP horizontal production line;

3) 37 ℃ of lower degreasing tank immersions with 10% KOZO 901 configurations 30 seconds;

4) clean with twice fountains water, enter 27 ℃ of lower sodium peroxydisulfate and microetch groove microetches of the concentrated sulfuric acid preparation of 20ml/L 30 seconds with 80g/L;

5) clean with the twice Air washer, enter the preimpregnation of preparing with 1% formic acid under the room temperature and soaked 30 seconds; Enter 27 ℃ of lower OSP drill traverse bubbles 90 seconds;

6) extract again by air-dry section of level air-dry with the water squeezing rumble after finishing.

6. the preparation method of described organic solderability preservative according to claim 5: it is characterized in that: described OSP groove is take the alkyl Benzimidazoles as main active ingredient.

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