CN109989069B

CN109989069B - Oil removing agent, preparation method and application thereof

Info

Publication number: CN109989069B
Application number: CN201910288950.1A
Authority: CN
Inventors: 王溯; 蒋闯
Original assignee: Shanghai Xinyang Semiconductor Material Co Ltd
Current assignee: Shanghai Xinyang Semiconductor Material Co Ltd
Priority date: 2019-04-11
Filing date: 2019-04-11
Publication date: 2021-06-01
Anticipated expiration: 2039-04-11
Also published as: CN109989069A

Abstract

The invention discloses an oil removing agent, a preparation method and application thereof. The oil removing agent comprises the following components in percentage by mass: 10 to 40 percent of sulfone organic solvent, 3 to 15 percent of organic amine, 5 to 18 percent of penetrating agent, 0.3 to 4 percent of corrosion inhibitor, 0.1 to 1.5 percent of nonionic surfactant A, 0.3 to 2 percent of nonionic surfactant B and water; the nonionic surfactant A is N, N-dimethyl hexadecyl-N-amine oxide; the nonionic surfactant B is di-n-octyl sulfoxide. The oil removing agent disclosed by the invention can effectively remove oil on the surface of the lead frame, has the characteristics of low foam, low corrosion, small harm to the environment, no toxicity and mild cleaning conditions, and has a wide application prospect.

Description

Oil removing agent, preparation method and application thereof

Technical Field

The invention relates to an oil removing agent, a preparation method and application thereof.

Background

In the packaging process of the integrated circuit, the lead frame is processed by a plurality of procedures such as deoiling, activation, electroplating, cleaning, drying and the like, wherein the deoiling is a pretreatment process of the lead frame electroplating, and the deoiling effect directly influences the plating effect of subsequent electroplating. The efficient oil removal agent needs to achieve the use effects of low foam, low corrosion, no oil residue, small harm to the environment, no toxicity, mild cleaning conditions and the like.

At present, no degreasing agent related to integrated circuit packaging disclosed by the patent is found, but the pretreatment degreasing agent for the lead frame in the current market mostly adopts N-methyl pyrrolidone as a solvent, and the solvent has great harm to the environment.

Therefore, the development of an oil removing agent which has the effects of low foam, low corrosion, no oil residue, small environmental hazard, no toxicity, mild use conditions and the like is needed to meet the industrial application requirements in the field.

Disclosure of Invention

The invention aims to overcome the defect that a solvent in the existing oil removing agent in the field has great harm to the environment, and provides the oil removing agent, and a preparation method and application thereof. The oil removing agent disclosed by the invention can effectively remove oil on the surface of the lead frame, has the characteristics of low foam, low corrosion, small harm to the environment, no toxicity and mild cleaning conditions, and has a wide application prospect.

N-methyl pyrrolidone is the most widely used solvent in the field of oil removal agents at present, the using effect of the N-methyl pyrrolidone is generally many times better than that of sulfone organic solvents, but the N-methyl pyrrolidone has great harm to the environment. The invention uses the sulfone organic solvent to replace N-methyl pyrrolidone, effectively overcomes the defect of poor cleaning effect by adjusting the types and the contents of the components of the oil removing agent, can achieve the effect equivalent to that of using the N-methyl pyrrolidone, and also solves the problem of great harm of the N-methyl pyrrolidone to the environment.

The invention mainly solves the technical problems through the following technical means:

the invention provides an oil removing agent which comprises the following components in percentage by mass: 10 to 40 percent of sulfone organic solvent, 3 to 15 percent of organic amine, 5 to 18 percent of penetrating agent, 0.3 to 4 percent of corrosion inhibitor, 0.1 to 1.5 percent of nonionic surfactant A, 0.3 to 2 percent of nonionic surfactant B and water;

the nonionic surfactant A is N, N-dimethyl hexadecyl-N-amine oxide; the nonionic surfactant B is di-n-octyl sulfoxide.

In the invention, the mass fraction of the sulfone organic solvent is preferably 15-35%, more preferably 20-30%. The organic amine is preferably 5 to 10 mass percent, and more preferably 7 to 9 mass percent. The mass fraction of the penetrating agent is preferably 8% -15%, more preferably 10% -12%. The mass fraction of the corrosion inhibitor is preferably 0.5-3.5%, more preferably 1-3%. The mass fraction of the nonionic surfactant A is preferably 0.3% -1.2%, more preferably 0.5% -1%. The mass fraction of the nonionic surfactant B is preferably 0.5 to 1.5%, more preferably 0.7 to 1.2%.

In the present invention, the sum of the mass fractions of the components is 100%, so the amount of the water is preferably 100% of the sum of the mass fractions of the components.

In the present invention, the sulfone organic solvent is preferably dimethyl sulfoxide.

The organic amine may be an organic amine conventionally used in the art, preferably an alcohol amine compound, more preferably one or more of monoethanolamine, diethanolamine, triethanolamine, isopropanolamine, N-dimethylethanolamine and N-methyldiethanolamine.

The penetrant may be a penetrant conventionally used in the art, and is preferably an ether compound, and more preferably one or more of ethylene glycol monoalkyl ether, diethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, dipropylene glycol monoalkyl ether, and tripropylene glycol monoalkyl ether.

The ethylene glycol monoalkyl ether is preferably one or more of ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol phenyl ether and ethylene glycol monobutyl ether.

The diethylene glycol monoalkyl ether is preferably one or more of diethylene glycol monomethyl ether, diethylene glycol monoethyl ether and diethylene glycol butyl ether.

The propylene glycol monoalkyl ether is preferably one or more of propylene glycol monomethyl ether, propylene glycol monoethyl ether and propylene glycol monobutyl ether.

The dipropylene glycol monoalkyl ether is preferably one or more of dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether and dipropylene glycol monobutyl ether.

The tripropylene glycol monoalkyl ether is preferably tripropylene glycol monomethyl ether.

The corrosion inhibitor can be a corrosion inhibitor conventionally used in the field, and is preferably one or more of phenol compounds, monocarboxylic acid compounds, dicarboxylic acid compounds, tricarboxylic acid compounds, tetracarboxylic acid compounds, triazole compounds, amino acids, ketoxime compounds, lactone compounds, amide compounds and anhydride compounds.

Wherein, the phenol compound is preferably catechol and/or pyrogallol.

The monocarboxylic acid compound is preferably one or more of formic acid, acetic acid, propionic acid, acrylic acid, gluconic acid, glyceric acid, glycolic acid, glyoxylic acid and lactic acid.

The dicarboxylic acid compound is preferably one or more of oxalic acid, malic acid, tartaric acid, succinic acid, maleic acid, malonic acid, glutaric acid, adipic acid, phthalic acid, isophthalic acid, terephthalic acid, iminodiacetic acid, and N-hydroxyethyliminodiacetic acid.

The tricarboxylic acid compound is preferably one or more of citric acid, trimellitic acid, trimesic acid and nitrilotriacetic acid.

The tetrabasic carboxylic acid compound is preferably ethylene diamine tetraacetic acid and/or trans-1, 2-cyclohexanediaminetetraacetic acid.

The triazole compound is preferably one or more of 3-amino-1, 2, 4-triazole, benzotriazole and methylbenzotriazole.

The amino acid is preferably one or more of glycine, alanine, leucine, isoleucine, arginine, aspartic acid, glutamic acid and lysine.

The ketoxime compound is preferably acetone oxime.

The lactone compound is preferably ascorbic acid.

The amide compound is preferably asparagine.

The acid anhydride compound is preferably maleic anhydride.

The water is preferably one or more of deionized water, distilled water, pure water and ultrapure water.

In a preferred embodiment of the present invention, the oil removing agent is composed of the following components in parts by mass: 10 to 40 percent of sulfone organic solvent, 3 to 15 percent of organic amine, 5 to 18 percent of penetrating agent, 0.3 to 4 percent of corrosion inhibitor, 0.1 to 1.5 percent of nonionic surfactant A, 0.3 to 2 percent of nonionic surfactant B and water;

In a preferred embodiment of the present invention, the oil removing agent is composed of the following components in parts by mass: 15 to 35 percent of sulfone organic solvent, 5 to 10 percent of organic amine, 8 to 15 percent of penetrating agent, 0.5 to 3.5 percent of corrosion inhibitor, 0.3 to 1.2 percent of nonionic surfactant A, 0.5 to 1.5 percent of nonionic surfactant B and water;

In a preferred embodiment of the present invention, the oil removing agent is composed of the following components in parts by mass: 20 to 30 percent of sulfone organic solvent, 7 to 9 percent of organic amine, 10 to 12 percent of penetrating agent, 1 to 3 percent of corrosion inhibitor, 0.5 to 1 percent of nonionic surfactant A, 0.7 to 1.2 percent of nonionic surfactant B and water;

The invention also provides a preparation method of the oil removing agent, which comprises the following steps: and mixing the components of the oil removing agent.

The invention also provides application of the oil removing agent in the electroplating pretreatment process of the lead frame.

Said application, preferably, comprises the steps of: and contacting the degreasing agent with the lead frame, cleaning and drying.

The lead frame can be a lead frame conventionally used in the field, and is preferably a copper-based lead frame or an iron-nickel-based lead frame.

The operation and conditions of the contacting may be conventional in the art, and the lead frame is preferably immersed in the degreasing agent. The contact temperature may be 20-70 deg.C, such as room temperature, 35 deg.C, 45 deg.C, 55 deg.C or 65 deg.C. The contact time may be 10-50min, for example 20 min.

The washing operations and conditions may be conventional in the art, preferably with water. Wherein the water can be one or more of deionized water, distilled water, pure water and ultrapure water, and is preferably deionized water.

The drying operation and conditions may be conventional in the art, and preferably nitrogen is used for blowing.

The room temperature in the present invention means 10 to 30 ℃.

In the invention, the mass fraction refers to the mass percentage of each component in the total mass of all the components.

The above preferred conditions can be arbitrarily combined to obtain preferred embodiments of the present invention without departing from the common general knowledge in the art.

The reagents and starting materials used in the present invention are commercially available.

The positive progress effects of the invention are as follows: the degreasing agent is applied to the electroplating pretreatment process of the lead frame, has good cleaning and degreasing effects, ideal degreasing effects in a medium-low temperature range, wide application range, low corrosion rate to the lead frame, no foam basically generated in the cleaning process, convenient use and mild conditions; the selected sulfone organic solvent has small harm to the environment and wide application prospect.

Detailed Description

The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.

In the following examples and comparative examples, the oil removing agent was prepared by the following steps: and mixing the components of the oil removing agent.

In the following examples, to define specific operating temperatures, all refer to operating at room temperature.

Examples 1 to 12 and comparative examples 1 to 17 each contain the water in an amount to make up 100% of the sum of the mass fractions of the components.

Examples 1 to 12

TABLE 1 Components of oil-removing agent

TABLE 2 Mass fractions of the components

Comparative examples 1 to 17

TABLE 3 Components of oil-removing agent

TABLE 4 mass fraction of each component

Among them, comparative examples 1 to 3 have investigated the effect of using a nonionic surfactant other than di-n-octyl sulfoxide as the nonionic surfactant B. Comparative examples 4 to 5 have investigated the effect of using a nonionic surfactant other than N, N-dimethylhexadecyl-N-amine oxide as the nonionic surfactant A. Upper and lower limits for the amounts of each component were explored in comparative examples 6-17.

Effects of the embodiment

And (3) corrosion rate testing:

the same material as the lead frame is 6 × 6cm²The copper base material and the iron-nickel base material are respectively immersed in a degreasing agent with the volume of 100mL for 20 min. Cleaning the substrate with deionized water after soaking, blow-drying the substrate with nitrogen, and measuring the thickness of the substrate before and after soaking by using a Signatone-QuadPro four-point detector; the corrosion rate was calculated as the change in thickness before and after soaking divided by the soaking time.

Testing the foam generation condition:

500mL of a degreaser was stirred at room temperature and used at a size of 15X 4cm²The magnetons are stirred for 30min at the rotating speed of 300r/min, and the foam generation condition in the degreasing agent is observed.

And (3) observation of oil removal effect:

respectively immersing the copper substrate lead frame and the iron-nickel substrate lead frame which are not plated with tin into degreasing agents with the volume of 100mL for 20min at the conditions of room temperature, 35 ℃, 45 ℃, 55 ℃ and 65 ℃. After soaking, the mixture is washed by deionized water and then dried by nitrogen. The oil residue was observed by a metallographic microscope under a magnification of 100.

The results of the various tests are shown in Table 5.

TABLE 5

Oil removal effect

Has no residue	◎
		Slight residue was found	○
Moderate residue	△
		Severe residue of	×

It can be seen from the above embodiment effect examples 1-12 and comparative effect examples 1-17 that the oil removing agent of the present invention has a good oil removing effect compared to the oil removing agent of the comparative example, has an ideal oil removing effect at room temperature, 35 ℃, 45 ℃, 55 ℃ and 65 ℃, has a wide application range, has a low corrosion rate to copper substrates and iron-nickel substrates of the same material as lead frames, and does not substantially generate foam during the cleaning process.

As can be seen from comparative effect examples 1 to 5, the surfactant of the present invention can achieve a good degreasing effect only by using a nonionic surfactant and a specific combination, and when chain lengths or branched chains of the nonionic surfactant a and the nonionic surfactant B change, the cleaning effect of the degreasing agent is affected, which results in oil residues, severe corrosion to copper substrates and iron-nickel substrates, and other defects, wherein the degreasing agent in comparative effect example 3 and comparative effect example 5 is prone to generate foam; as can be seen from comparative effect examples 6 to 7, when the content of the sulfone organic solvent is less than 10%, the cleaning effect is not good, and when the content of the sulfone organic solvent is more than 40%, the cleaning effect is not good, and foams are easily generated; as can be seen from comparative effect examples 8 to 9, when the content of the organic amine is less than 3% and more than 15%, the cleaning effect is not good; as can be seen from comparative effect examples 10 to 11, when the content of the penetrant is less than 5%, the cleaning effect is not good, and when the content of the penetrant is more than 18%, the cleaning effect is not good, and the corrosion to the copper base material and the iron-nickel base material is severe; from comparative effect examples 12 to 13, it can be seen that when the content of the corrosion inhibitor is less than 0.3%, the corrosion on the copper substrate and the iron-nickel substrate is severe, and the cleaning effect is not good, and when the content of the corrosion inhibitor is more than 4%, the cleaning effect is not good; it can be seen from comparative effect examples 14 to 15 that when the content of the nonionic surfactant a is less than 0.1%, the cleaning effect is not good, the corrosion to the copper base material and the iron-nickel base material is severe, and when the content of the nonionic surfactant a is more than 1.5%, the cleaning effect is not good, and the foam is easily generated; it can be seen from comparative effect examples 16 to 17 that when the content of the nonionic surfactant B is less than 0.3%, the cleaning effect is not good, the corrosion to the copper base material and the iron-nickel base material is severe, and when the content of the nonionic surfactant B is more than 2%, the cleaning effect is not good, and the foam is easily generated.

Claims

1. The oil removing agent is characterized by comprising the following components in percentage by mass: 10 to 40 percent of sulfone organic solvent, 3 to 15 percent of organic amine, 5 to 18 percent of penetrating agent, 0.3 to 4 percent of corrosion inhibitor, 0.1 to 1.5 percent of nonionic surfactant A, 0.3 to 2 percent of nonionic surfactant B and water;

the sulfone organic solvent is dimethyl sulfoxide; the nonionic surfactant A is N, N-dimethyl hexadecyl-N-amine oxide; the nonionic surfactant B is di-n-octyl sulfoxide.

2. The oil remover according to claim 1, wherein the mass fraction of the sulfone organic solvent is 15-35%;

and/or the organic amine accounts for 5-10% of the mass fraction;

and/or the mass fraction of the penetrating agent is 8-15%;

and/or the mass fraction of the corrosion inhibitor is 0.5-3.5%;

and/or the mass fraction of the nonionic surfactant A is 0.3-1.2%;

and/or the mass fraction of the nonionic surfactant B is 0.5-1.5%.

3. The oil remover according to claim 2, wherein the mass fraction of the sulfone organic solvent is 20-30%;

and/or the organic amine accounts for 7-9% of the mass fraction;

and/or the mass fraction of the penetrating agent is 10-12%;

and/or the mass fraction of the corrosion inhibitor is 1-3%;

and/or the mass fraction of the nonionic surfactant A is 0.5-1%;

and/or the mass fraction of the nonionic surfactant B is 0.7-1.2%.

4. The oil removing agent according to claim 1,

the organic amine is an alcohol amine compound;

and/or the penetrating agent is an ether compound;

and/or the corrosion inhibitor is one or more of a phenol compound, a monocarboxylic acid compound, a dicarboxylic acid compound, a tricarboxylic acid compound, a tetracarboxylic acid compound, a triazole compound, amino acid, a ketoxime compound, a lactone compound, an amide compound and an anhydride compound;

and/or the water is pure water.

5. The oil remover according to claim 4, wherein the water is one or more of deionized water, distilled water and ultrapure water.

6. The oil remover according to claim 4, wherein the alkanolamine compound is one or more of monoethanolamine, diethanolamine, triethanolamine, isopropanolamine, N-dimethylethanolamine and N-methyldiethanolamine;

and/or the ether compound is one or more of ethylene glycol monoalkyl ether, diethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, dipropylene glycol monoalkyl ether and tripropylene glycol monoalkyl ether;

and/or the phenol compound is catechol and/or pyrogallol;

and/or the monocarboxylic acid compound is one or more of formic acid, acetic acid, propionic acid, acrylic acid, gluconic acid, glyceric acid, glycolic acid, glyoxylic acid and lactic acid;

and/or the dicarboxylic acid compound is one or more of oxalic acid, malic acid, tartaric acid, succinic acid, maleic acid, malonic acid, glutaric acid, adipic acid, phthalic acid, isophthalic acid, terephthalic acid, iminodiacetic acid and N-hydroxyethyliminodiacetic acid;

and/or the tricarboxylic acid compound is one or more of citric acid, trimellitic acid, trimesic acid and nitrilotriacetic acid;

and/or the tetrabasic carboxylic acid compound is ethylene diamine tetraacetic acid and/or trans-1, 2-cyclohexanediamine tetraacetic acid;

and/or the triazole compound is one or more of 3-amino-1, 2, 4-triazole, benzotriazole and methyl benzotriazole;

and/or, the amino acid is one or more of glycine, alanine, leucine, isoleucine, arginine, aspartic acid, glutamic acid and lysine;

and/or, the ketoxime compound is acetone oxime;

and/or the lactone compound is ascorbic acid;

and/or, the amide compound is asparagine;

and/or the acid anhydride compound is maleic anhydride.

7. The oil remover according to claim 6, wherein the ethylene glycol monoalkyl ether in the ether compound is one or more of ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol phenyl ether and ethylene glycol monobutyl ether.

8. The oil remover according to claim 6, wherein in the ether compound, the diethylene glycol monoalkyl ether is one or more of diethylene glycol monomethyl ether, diethylene glycol monoethyl ether and diethylene glycol butyl ether.

9. The oil remover according to claim 6, wherein the propylene glycol monoalkyl ether in the ether compound is one or more of propylene glycol monomethyl ether, propylene glycol monoethyl ether and propylene glycol monobutyl ether.

10. The oil remover according to claim 6, wherein in the ether compound, the dipropylene glycol monoalkyl ether is one or more of dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether and dipropylene glycol monobutyl ether.

11. The oil removing agent according to claim 6, wherein the tripropylene glycol monoalkyl ether in the ether-based compound is tripropylene glycol monomethyl ether.

12. A method of preparing an oil-removing agent as claimed in any one of claims 1 to 11, comprising the steps of: and mixing the components of the oil removing agent.

13. Use of the oil remover according to any one of claims 1-11 in a lead frame pre-plating treatment process.

14. The use of claim 13, comprising the steps of contacting said oil removal agent with said lead frame, cleaning and drying.

15. The use according to claim 14, wherein the lead frame is a copper-based lead frame or an iron-nickel-based lead frame;

and/or, the temperature of the contact is 20-70 ℃;

and/or, the contact time is 10-50 min;

and/or, the cleaning is cleaning with water;

and/or the drying is blow-drying by nitrogen.

16. The use of claim 15, wherein the contacting is at a temperature of room temperature, 35 ℃, 45 ℃, 55 ℃ or 65 ℃;

and/or, the contact time is 20 min;

and/or the cleaning is cleaning with water, and the water is pure water.

17. The use of claim 16, wherein the rinsing is with water, the water being one or more of deionized water, distilled water, and ultrapure water.

18. The use of claim 17, wherein the cleaning is with water and the water is deionized water.