CN114106935B

CN114106935B - Water-based scaling powder cleaning agent, preparation method and application thereof

Info

Publication number: CN114106935B
Application number: CN202111296651.6A
Authority: CN
Inventors: 侯军; 任浩楠
Original assignee: Zhejiang Aoshou Material Technology Co ltd
Current assignee: Zhejiang Aoshou Material Technology Co ltd
Priority date: 2021-11-04
Filing date: 2021-11-04
Publication date: 2023-07-25
Anticipated expiration: 2041-11-04
Also published as: CN114106935A

Abstract

The invention provides a water-based scaling powder cleaning agent, a preparation method and application thereof, wherein the water-based scaling powder cleaning agent comprises the following components in parts by weight: alcohol amine 5-30 parts; 10-55 parts of glycol ether compound; 1-25 parts of polar solvent; 0.001-10 parts of chelating surfactant; 0.1-5 parts of pH regulator; 0.1-10 parts of amino acid; 0.001-10 parts of wetting agent; 5-60 parts of deionized water. The invention also discloses a preparation method and application of the water-based scaling powder cleaning agent. The water-based scaling powder cleaning agent has low use concentration and no harm to human bodies and the environment. The water-based scaling powder cleaning agent has excellent scaling powder cleaning capability, can inhibit oxidation and corrosion of a chip substrate, and effectively improves the yield of chips.

Description

Water-based scaling powder cleaning agent, preparation method and application thereof

Technical Field

The invention relates to a cleaning agent technology, in particular to a water-based scaling powder cleaning agent, a preparation method and application thereof.

Background

In the electronic industry, the soldering flux can effectively remove the solder and the oxide of the contained parent metal in the welding process, and can prevent the metal substrate from being further oxidized in the welding process, so that the surface tension of the solder is reduced, and the welding performance is improved, but after welding, the soldering flux inevitably remains on the surface of the welded object, thereby not only affecting the appearance, but also being more afraid of causing the reliability of a chip; particularly, when the electronic product works under high-temperature and humidity conditions for a long time, the residue may cause problems of aging and corrosion of the circuit insulation, so that insulation resistance (SIR) is reduced and electrochemical migration (ECM) occurs. Accordingly, there is a need for a flux cleaner composition that has excellent flux cleaning ability while inhibiting oxidation and corrosion of substrates and metals.

Disclosure of Invention

Aiming at the problem that the reliability of a chip is reduced due to residual soldering flux, the invention provides a water-based soldering flux cleaning agent which is water-based, has low use concentration and does not harm human bodies and environment; the cleaning agent has excellent scaling powder cleaning capability, can inhibit oxidation and corrosion of a chip substrate, and effectively improves the yield of chips.

In order to achieve the above purpose, the invention adopts the following technical scheme: the water-based scaling powder cleaning agent comprises the following components in parts by weight:

further, the alcohol amine is selected from one or more of monoethanolamine, diethanolamine, triethanolamine, diglycolamine, N-methyl monoethanolamine, N-ethyl monoethanolamine, N-dimethyl ethanolamine, N-methyl diethanolamine, isopropanolamine, methylethylethanolamine, 3-amino-1-propanol, isobutolamine, 2-amino-2-ethoxyethanol. Preferably triethanolamine and/or isobutolamine. The content of the alcohol amine is preferably 10 to 20 parts.

Further, the glycol ether compound is selected from one or more of diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol propyl ether, diethylene glycol butyl ether, diethylene glycol hexyl ether, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, dipropylene glycol butyl ether, triethylene glycol ethyl ether, triethylene glycol butyl ether, tripropylene glycol methyl ether, tripropylene glycol butyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol dimethyl ether, diethylene glycol methyl ether. Preferably triethylene glycol butyl ether and/or tripropylene glycol butyl ether. The content of the glycol ether compound is preferably 25 to 50 parts.

Further, the polar solvent is selected from one or more of amide polar solvents, ketone polar solvents, sulfone polar solvents, acetate polar solvents and alcohol polar solvents. The amide polar solvents such as N, N dimethylformamide, ketone polar solvents such as N-methylpyrrolidone, sulfone polar solvents such as dimethyl sulfoxide, acetate polar solvents such as ethylene glycol monoethyl ether acetate, and alcohol polar solvents such as benzyl alcohol. The polar solvent is preferably N, N dimethylformamide and/or benzyl alcohol. The polar solvent content is preferably 10 to 15 parts.

Further, the chelating surfactant is N-amide ethylenediamine triacetic acid, as shown in formula I, wherein x=an integer of 8-18. Preferably lauramide ethylenediamine triacetic acid when x is 12 and/or hard amide ethylenediamine triacetic acid when x is 18. The content of the chelating surfactant is preferably 0.001 to 5 parts.

Further, the pH adjuster is selected from aliphatic hydroxy acids wherein the hydroxy position is at the end of the carbon chain and this carbon chain is a saturated straight chain, as in formula ii, wherein y = an integer from 3 to 15, preferably hydroxy octanoic acid where y is 8 and/or hydroxy dodecanoic acid where y is 12. The content of the pH adjustor is preferably 0.3 to 3 parts.

HOC _y H2 _y+1 COOH

Further, the amino acid is selected from amino acids containing two or more amino groups in the amino acid molecule, and is selected from one or more of histidine, arginine, asparagine, tryptophan, lysine, glutamic acid and pyrrolysine. Asparagine and/or lysine are preferred. The content of the amino acid is preferably 0.1 to 5 parts.

Further, the wetting agent is a fluorine-containing hybridizable surfactant, such as formula iii, wherein n and m are integers from 2 to 6 and 1 to 6, respectively, for example, n and m are each independently 2 (i.e., perfluoroethyl), 3 (i.e., perfluoro-n-propyl), 4 (i.e., perfluoro-n Ding Yiji), 5 (i.e., perfluoro-n-pentyl), 6 (i.e., perfluoro-n-hexyl), preferably when n is 2 and m is 4. The content of the wetting agent is preferably 0.001 to 5 parts.

Further, the content of the deionized water is preferably 5-20 parts;

the invention also discloses a preparation method of the cleaning agent of the water-based soldering flux, which comprises the following steps:

stirring deionized water and amino acid to dissolve for 30-60min to obtain component A;

sequentially adding a glycol ether compound, a polar solvent, alcohol amine, a pH regulator, a chelating surfactant and a wetting agent, and stirring and dissolving for 30-60min to obtain a component B;

and then mixing and stirring the component A and the component B for 30-60min, uniformly mixing, and filtering out insoluble impurities by using a filter element with 0.1-0.5um to obtain the water-based scaling powder cleaning agent.

The invention also discloses application of the water-based scaling powder cleaning agent in the field of chip scaling powder cleaning. The cleaning device is particularly used for cleaning chip scaling powder residues in the welding process.

Further, the method of cleaning the electronic chip with the water-based flux cleaner is cleaning, rinsing and drying, the cleaning and rinsing method is not particularly limited, for example, immersing, swinging, stirring, ultrasonic, air or liquid spraying, wiping, among which spraying and ultrasonic are preferable; the drying stage method comprises spin drying or nitrogen blow drying. Preferably, the ultrasonic cleaning is carried out for 10-30min after the chip is immersed by adopting the water-based scaling powder cleaning agent.

Further, the cleaning temperature of the water-based flux cleaner is 30 to 70 ℃ from the viewpoints of flux cleaning ability, corrosion resistance of metal and wiring materials, safety and handling.

Further, the water-based flux cleaner is applied in a concentration of 5-60% wt solution, preferably 10-40% wt. Because the cleaning agent of the water-based soldering flux is water-based, the cleaning agent still has higher wiring corrosion resistance when the content of the cleaning agent in the water solution is very low, so the soldering flux can be washed by the water solution, and the water solution washing is an economic cleaning method with extremely low environmental load.

Compared with the prior art, the water-based scaling powder cleaning agent, the preparation method and the application thereof have the following advantages:

(1) The main component of the chip scaling powder is rosin resin and its derivative, the most main component is abietic acid, which belongs to unsaturated acid, alcohol amine contained in the water-based scaling powder cleaning agent of the invention can react with abietic acid, and the formed esterified product can be dissolved by solvents such as glycol ether, etc., so as to achieve the removal effect.

(2) The pH regulator contained in the cleaning agent can play a role in regulating the pH of a system on one hand; on the other hand, the pH regulator aliphatic hydroxy acid can effectively remove the metal oxide film generated by welding points of the soldering flux in the use process, thereby preventing the generation of the metal oxide film and increasing the yield. The aliphatic hydroxy acid and the amino acid molecule can generate synergistic effect, hydroxy acid-amino acid salt is generated in the solution, the hydroxy acid-amino acid simultaneously has more than two amino acids, and the structure of a plurality of amino groups can be more effectively adsorbed on the metal surface; the long chain hydroxy acid molecule at the other end can prevent the metal from being attacked and corroded in alkaline and water. In addition, the aliphatic hydroxy acid-amino acid molecule also has the capability of chelating metal ions, and can be deposited on the metal surface to form a protective film.

(3) The chelating surfactant contained in the cleaning agent has strong surface activity and chelating capacity, can effectively reduce the surface tension, and can chelate the metal ions remained in the welding process, thereby preventing the corrosion of the metal ions to the metal of the chip.

(4) The soldering flux can be inevitably remained on the surface of a chip and in the fine seams in the using process, one end of the wetting agent, namely the hybridization type surfactant, selected by the cleaning agent contains a fluorocarbon chain, and the other end of the wetting agent contains a hydrocarbon chain, so that the structural characteristics of the wetting agent endows the surface active agent with good wettability, and the addition of the hybridization type surfactant containing fluorine can improve the permeability of the fine seams, promote the permeation of solvent and organic alkali molecules to the fine seams and effectively clean the soldering flux residues at the gaps.

In a word, the water-based scaling powder cleaning agent can effectively remove various types of scaling powder, has excellent cleaning effect on scaling powder residues in low gaps in high-density chips, is compatible with various sensitive metals and materials on the chips, and has no corrosion and bright welding spots after cleaning.

Drawings

FIG. 1 is a microscopic image at 100-fold magnification of a 1 x 1cm chip cleaned with the cleaning agent of example 15.

FIG. 2 is a microscopic image of a Cu electrode immersed 500 times at normal temperature using the cleaning agent of example 15.

Fig. 3 is a microscopic image after immersing a Cu electrode 500 times at normal temperature using the cleaning agent of comparative example 1.

Fig. 4 is a microscopic image of a 1 x 1cm chip at 100 x magnification after washing with the detergent of comparative example 2.

Fig. 5 is a microscopic image at 100 x magnification of a 1 x 1cm chip cleaned with the cleaning agent of example 15.

FIG. 6 is a microscopic image at 100 times magnification of a 1 x 1cm chip cleaned with the cleaner of comparative example 3.

Detailed Description

The invention is further illustrated by the following examples:

examples 1 to 20

The components and amounts of examples 1-20 are given in Table 1, wherein the chelating surfactant has the formula I, the pH adjustor aliphatic hydroxy acid has the formula II, and the wetting agent has the formula III. The raw materials and reagents used in the invention are all commercially available.

The preparation method of the water-based soldering flux cleaning agent of examples 1-20 is as follows:

1) Stirring deionized water and amino acid to dissolve for 30-60min to obtain component A;

2) Sequentially adding a glycol ether compound, a polar solvent, alcohol amine, a pH regulator, a chelating surfactant and a wetting agent, and stirring and dissolving for 30-60min to obtain a component B;

3) And then mixing and stirring the component A and the component B for 30-60min, uniformly mixing, and filtering by using a filter element with 0.1-0.5um to obtain the water-based scaling powder cleaning agent.

The cleaning methods of the water-based flux cleaners of examples 1-20 were as follows:

1L of 10-60 wt% of scaling powder cleaning agent is added into an ultrasonic cleaning tank with the frequency of 28-80kHz, and the temperature is raised to 30-80 ℃ for standby. Placing the chip to be cleaned into a scaling powder cleaning agent, ultrasonically cleaning for 10-30min, taking out, washing with deionized water for 10min, and using N ₂ Drying.

TABLE 1 Components and content of Water-based flux cleaners of examples 1-20

Comparative examples 1 to 3

Table 2 shows the components and amounts of the flux cleaners of comparative examples 1-3. Wherein the chelating surfactant has a general formula shown in formula I, the pH regulator has a general formula shown in formula II, and the wetting agent has a general formula shown in formula III.

According to the components and the contents thereof listed in Table 2, deionized water and amino acid are sequentially added into a stirring kettle to be stirred and dissolved for 30min to prepare a component A, a glycol ether compound, a polar solvent, alcohol amine, a pH regulator, a chelating surfactant and a wetting agent are sequentially added into the stirring kettle to be dissolved, in the dissolving process, the temperature of the stirring kettle is controlled below 40 ℃, the stirring kettle is stirred for 30min to prepare a component B, then the component A and the component B are mixed and stirred for 30min, and the component A and the component B are uniformly mixed and filtered by a filter element of 0.1um to obtain the scaling powder cleaning agent.

Table 2 the flux cleaner components and amounts of comparative examples 1-3

Performance test I Corrosion test of cleaning fluids on metallic Cu, stainless steel, al and polymeric substrates

According to the 7.9 requirement in SJ/T11639-2016, a specified pure copper sheet, a stainless steel sheet and an aluminum sheet are selected, soaked in 30 wt% water solution at 60+/-2 ℃ for 2 hours+/-5 minutes, taken out and washed clean by deionized water, and a 20-time microscope is used for checking whether the test piece has phenomena of color change, corrosion and the like, and compared with the recorded condition before the test for observation.

According to the 7.10 requirement in SJ/T11639-2016, selecting a specified printed circuit board and a specified rubber test piece, soaking in 40%wt water solution at 23+/-2 ℃ for 24 hours+/-15 minutes, taking out, washing cleanly with deionized water, and checking whether the solder resist of the PCB test piece has the phenomena of color change, foaming, wrinkling, cracking, layering, whether the character ink has color change, handwriting blurring and the like by using a 20-time microscope; whether the silicon rubber test piece has the phenomena of wrinkling, swelling and the like or not is compared with the recorded condition before the test. The results are shown in Table 3.

TABLE 3 Corrosion of examples 1-20 and comparative example 1 on metallic Cu sheets, stainless steel, al sheets, PCBs and Silicone rubbers

Corrosion conditions: little corrosion ∈slightly corrosive ∈moderately corrosive

Performance test II test of the cleaning Effect of the soldering flux

Chips 1 x 1cm of the flux-containing residue were placed in inventive example cleaners 1-20 and comparative example 2 shown in table 1, immersed in 30% wt aqueous solution, shaken at 30-80 ℃ using a constant temperature shaker for 10-30 minutes, then washed with deionized water and dried with high purity nitrogen. The cleaning effect of the flux is shown in table 4.

TABLE 4 cleaning effect on semiconductor wafers of examples 1-20 and comparative example 2

Cleaning: complete removal of small amount of residual x large amount of residual

Fig. 1 is a microscopic image of a 1 x 1cm chip cleaned using the cleaning solution prepared in example 15, magnified 100 times, and it is clear that the surface of the chip is cleaned very cleanly without any contaminants, indicating that the cleaning effect of the cleaning solution is very excellent. Fig. 2 is a microscopic image of the Cu electrode at 500 times after being immersed for 24 hours at normal temperature using the cleaning solution of example 15, it is clear that the cleaning solution of example 15 does not have any corrosion to the Cu electrode. Fig. 3 is a microscopic image of the Cu electrode immersed for 24 hours at normal temperature using the cleaning solution of comparative example 1, which clearly shows that the chip has more serious surface corrosion. Fig. 4 is a microscopic image at 100 x magnification of a 1 x 1cm chip cleaned with the cleaning solution of comparative example 2, and it is clear that a small amount of flux remains in the chip gap. As is clear from comparison of FIG. 1 and FIG. 4, the added fluorine-containing surfactant has high surface activity, one end of the hybridization surfactant contains a fluorocarbon chain, and the other end contains a hydrocarbon chain, so that the structural characteristics endow the surfactant with good wettability, and the addition of the fluorine-containing hybridization surfactant can improve the permeability to fine gaps, promote the permeation of solvent and organic alkali molecules to the fine gaps, and effectively clean flux residues at the gaps.

FIG. 5 is the color of the weld after cleaning using example 15, and it can be clearly seen that the weld surface is glossy. FIG. 6 is a view showing the surface of the weld after cleaning using comparative example 3, which clearly shows that the surface of the weld is dull and matt. It can be seen that the metal oxide film can be effectively removed after the aliphatic hydroxy acid and the amino acid are added, thereby preventing the generation of the metal oxide film and improving the yield of products.

Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.

Claims

1. The water-based scaling powder cleaning agent is characterized by comprising the following components in parts by weight:

the alcohol amine is selected from one or more of monoethanolamine, diethanolamine, triethanolamine, diglycolamine, N-methyl monoethanolamine, N-ethyl monoethanolamine, N-dimethyl ethanolamine, N-methyl diethanolamine, isopropanolamine, methylethylethanolamine, 3-amino-1-propanol, isobutolamine and 2-amino-2-ethoxyethanol;

the glycol ether compound is selected from one or more of diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol propyl ether, diethylene glycol butyl ether, diethylene glycol hexyl ether, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, dipropylene glycol butyl ether, triethylene glycol ethyl ether, triethylene glycol butyl ether, tripropylene glycol methyl ether, tripropylene glycol butyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol dimethyl ether and diethylene glycol methyl ethyl ether;

the polar solvent is selected from one or more of N, N-dimethylformamide, N-methylformamide, N-dimethylacetamide, N-methylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone, 1-octyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, dimethyl sulfoxide, sulfolane, tetrahydrofurfuryl alcohol, benzyl alcohol, ethylene glycol monoethyl ether acetate, ethylene glycol butyl ether acetate, diethylene glycol butyl ether acetate, propylene glycol methyl ether acetate, propylene glycol diacetate and dipropylene glycol methyl ether acetate;

the chelating surfactant is N-amide ethylenediamine triacetic acid;

the pH regulator is selected from aliphatic hydroxy acid, wherein the hydroxyl position is at the end point of a carbon chain, and the carbon chain is a saturated straight chain;

the amino acid is selected from amino acid containing two or more amino groups in the amino acid molecule, and is selected from one or more of histidine, arginine, asparagine, tryptophan, lysine, glutamic acid and pyrrolysine;

the wetting agent is a fluorine-containing hybridization surfactant.

2. A method for preparing the cleaning agent of the water-based soldering flux according to claim 1, which is characterized by comprising the following steps:

and then mixing and stirring the component A and the component B for 30-60min, uniformly mixing, and filtering by using a filter element with 0.1-0.5um to obtain the water-based scaling powder cleaning agent.

3. Use of the water-based flux cleaner of claim 1 in the field of chip flux cleaning.