阅读说明：本技术 一种pi膜剥离液及其制备方法和剥离方法 (PI film stripping liquid and preparation method and stripping method thereof ) 是由 王雪刚 凌丽靖 于 2021-08-27 设计创作，主要内容包括：本发明公开了一种PI膜剥离液,按重量百分比计,由以下组分配制而成：10-20％有机醇胺、4-12％季铵碱、45-60％醇类有机溶剂、0.5-2.0％非离子型表面活性剂以及补足余量的纯水。本发明还公开了上述PI膜剥离液的制备方法,以及上述PI膜剥离液使用时的剥离方法。本发明弥补了PI膜剥离液研究的空白,其配方组分常见,配制步骤简单,溶液颗粒物少,可以实现快速剥离PI膜,不会使PI膜过度溶胀破坏金属布线图案,不会腐蚀金属布线图案和金属基板,成本低且环保。(The invention discloses a PI film stripping liquid which is prepared from the following components in percentage by weight: 10-20% of organic alcohol amine, 4-12% of quaternary ammonium base, 45-60% of alcohol organic solvent, 0.5-2.0% of nonionic surfactant and pure water for supplementing the balance. The invention also discloses a preparation method of the PI film stripping liquid and a stripping method when the PI film stripping liquid is used. The method makes up the blank of research on the PI film stripping solution, has common formula components, simple preparation steps and few solution particles, can realize quick stripping of the PI film, does not cause excessive swelling of the PI film to damage a metal wiring pattern, does not corrode the metal wiring pattern and a metal substrate, and is low in cost and environment-friendly.)

1. A PI film stripping liquid is characterized in that: the composition is prepared from the following components in percentage by weight: 10-20% of organic alcohol amine, 4-12% of quaternary ammonium base, 45-60% of alcohol organic solvent, 0.5-2.0% of nonionic surfactant and pure water for supplementing the balance.

2. The PI film stripping solution according to claim 1, wherein: the organic alcohol amine is at least one of monoethanolamine, diethanolamine, triethanolamine and isopropanolamine.

3. The PI film stripping solution according to claim 1, wherein: the quaternary ammonium hydroxide is at least one of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide and diethyldimethylammonium hydroxide.

4. The PI film stripping solution according to claim 1, wherein: the alcohol organic solvent is at least one of ethylene glycol, glycerol, isopropanol and n-butanol.

5. The PI film stripping solution according to claim 1, wherein: the nonionic surfactant is at least one of polyoxyethylene amine, alkylolamide, polyalcohol fatty acid monoester and N-alkyl pyrrolidone.

6. A preparation method of PI film stripping liquid is characterized by comprising the following steps: the PI film stripping solution as claimed in any one of claims 1 to 5, wherein the PI film stripping solution is prepared by sequentially adding an alcohol organic solvent, organic alcohol amine, quaternary ammonium base and a nonionic surfactant according to the weight percentage, supplementing the rest with pure water, and mixing and stirring uniformly.

7. A method for stripping PI film stripping liquid is characterized by comprising the following steps:

firstly, soaking a metal substrate with a PI film and a Cu/Al metal wiring in the PI film stripping solution as defined in any one of claims 1 to 5, wherein the temperature of the PI film stripping solution is 45-65 ℃, and the soaking time is 25-35 min;

and then, flushing the soaked metal substrate with cold water for 3-5 times, flushing for 30s each time, and drying by using nitrogen gas, so that no water stain is left on the surface of the metal substrate.

8. A method for stripping PI film stripping liquid is characterized by comprising the following steps:

firstly, soaking a metal substrate with a PI film and a Cu/Al metal wiring in PI film stripping liquid prepared by the preparation method of the PI film stripping liquid according to claim 6, wherein the temperature of the PI film stripping liquid is 45-65 ℃, and the soaking time is 25-35 min;

and then, flushing the soaked metal substrate with cold water for 3-5 times, flushing for 30s each time, and drying by using nitrogen gas, so that no water stain is left on the surface of the metal substrate.

Technical Field

The invention belongs to the technical field of stripping liquid, and particularly relates to PI film stripping liquid, which relates to a preparation method of the PI film stripping liquid and a stripping method when the PI film stripping liquid is used.

Background

PI films, polyimide films (polyimide films), were produced by dupont in 1961, and their adhesives, coatings, foams, fibers and varnishes were successively present. With the vigorous development of PI films, the modification technology of PI films becomes an important task, and PI films with different functions such as easy molding and curing, small linear expansion coefficient, high temperature resistance, thermoplasticity and the like are developed in order to meet market demands. The PI film has excellent high and low temperature resistance, electric insulation, adhesion, radiation resistance and medium resistance, is a film type insulating material with excellent performance, and is particularly suitable for being used as a flexible printed circuit board and various high-temperature resistant motor and electric appliance insulating materials. In the process of processing the printed circuit board, the PI liquid is coated and baked to form a PI film on a metal substrate. After the printed circuit board is completely manufactured, the excess PI film needs to be peeled off. The PI film on the market is processed and modified, the peeling of the PI film is also a difficult problem, and the PI film is required to be quickly dissolved in the peeling process, and a metal wiring pattern below the PI film is also required not to be damaged. In the existing stripping liquid system, products specially aiming at the PI film do not exist, so that the phenomena of unclean stripping and large residual quantity can occur in quick stripping, and long-term soaking is often adopted for clean stripping, but the PI film can be swelled, and even the metal wiring pattern and the metal substrate are corroded. In addition, the use amount of the organic solvent of the stripping solution is large, a large amount of stripping solution waste liquid is generated to a certain extent, and the selection of the organic solvent with recycling value is beneficial to reducing the environmental load and the cost, and is helpful to protect the environment.

Disclosure of Invention

In order to make up the blank of research on PI film stripping liquid, the invention aims to provide the PI film stripping liquid which has the advantages of common formula components, simple preparation steps, less solution particles, capability of quickly stripping the PI film, no damage to a metal wiring pattern due to excessive swelling of the PI film, no corrosion to the metal wiring pattern and a metal substrate, low cost and environmental protection.

The invention also provides a preparation method of the PI film stripping liquid and a stripping method when the PI film stripping liquid is used.

In order to achieve the purpose, the invention adopts the following technical scheme:

the PI film stripping liquid is prepared from the following components in percentage by weight: 10-20% of organic alcohol amine, 4-12% of quaternary ammonium base, 45-60% of alcohol organic solvent, 0.5-2.0% of nonionic surfactant and pure water for supplementing the balance.

Wherein the organic alcohol amine is at least one of monoethanolamine, diethanolamine, triethanolamine and isopropanolamine.

The quaternary ammonium hydroxide is at least one of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide and diethyldimethylammonium hydroxide.

The alcohol organic solvent is at least one of ethylene glycol, glycerol, isopropanol and n-butanol.

The nonionic surfactant is at least one of polyoxyethylene amine, alkylolamide, polyalcohol fatty acid monoester and N-alkyl pyrrolidone.

A preparation method of PI film stripping liquid comprises the steps of sequentially adding an alcohol organic solvent, organic alcohol amine, quaternary ammonium base and a nonionic surfactant according to the weight percentage, complementing the balance with pure water, and then mixing and stirring uniformly.

A method for stripping PI film stripping liquid comprises the following steps:

firstly, soaking a metal substrate with a PI film and Cu/Al metal wiring in PI film stripping liquid at the temperature of 45-65 ℃ for 25-35 min;

and then, flushing the soaked metal substrate with cold water for 3-5 times, flushing for 30s each time, and drying by using nitrogen gas, so that no water stain is left on the surface of the metal substrate.

After the scheme is adopted, the invention has the beneficial effects that: the invention fills the blank of research of the PI film stripping liquid, the PI film stripping liquid has common formula components, low toxicity and simple preparation steps, greatly reduces the difficulty of laboratory preparation and production line production, effectively reduces the manufacturing cost, selects the compatibility of quaternary ammonium base and a specific alcohol organic solvent in the formula, improves the solubility of the stripping liquid and the stripping property on the PI film, ensures that the quaternary ammonium base has alkalinity, can ensure that the films are fluffy and the bonding force is weakened, simultaneously leads the films to be cracked through the combined action of internal stress and chemical dissolution, has good hydrophilicity by taking the alcohol reagent as the organic solvent, can be mutually dissolved with other organic reagents, reduces the viscosity of the aqueous stripping liquid, and increases the acting force between the stripping liquid and the films. In addition, the stripping solution has few particles and impurities, can avoid the influence of the particles and the impurities on the metal substrate and the metal wiring pattern, ensures that the stripping solution is clearer and has better permeability, can realize that the PI film is stripped without any residue, cannot cause the PI film to excessively swell to damage the metal wiring pattern of the integrated circuit, and cannot corrode the metal wiring pattern and the metal substrate. The organic solvent used by the stripping liquid can be efficiently recovered and reused, so that the cost is reduced.

Detailed Description

The following embodiments are provided for further description of the technical solution of the present invention, but the present invention is not limited to the scope of the embodiments, and all the embodiments and equivalents thereof are within the protection scope of the present invention.

Selection of one, implementation

The formulations of PI film stripping solutions according to the present invention are given in examples 1-8 of the present invention, and the stripping temperatures of the examples are shown in tables 1-1.

Table 1-1 units: wt.%

Referring to the formulations of the present invention, combination formulations different from the present invention are given as comparative examples 1 to 14, and the peeling temperatures of the respective examples are shown in tables 1 to 2. Among them, comparative example 1 lacks the quaternary ammonium hydroxide of the present invention, comparative example 2 lacks the alcoholic organic solvent of the present invention, comparative example 3 lacks the alcoholic organic solvent and the quaternary ammonium hydroxide of the present invention, comparative example 4 and comparative example 12 have a quaternary ammonium hydroxide amount lower or higher than the present invention, comparative examples 5 and 6 use an ether-based organic solvent instead of the alcoholic organic solvent of the present invention, comparative example 7 has a surfactant other than the nonionic surfactant of the present invention, comparative example 8 and comparative example 9 have a peeling temperature lower or higher than the present invention, comparative example 10 and comparative example 11 have a surfactant amount lower or higher than the present invention, comparative example 13 has an organic alcohol amine amount higher than the present invention, and comparative example 14 has an organic solvent amount higher than the present invention.

Table 1-2 units: wt.%

Second, preparation of stripping solution

According to the formulas shown in the tables 1-1 and 1-2, the organic solvent, the organic alcohol amine, the quaternary ammonium base and the surfactant are sequentially added, the balance is complemented with pure water, and then the mixture is mixed and stirred uniformly to obtain the corresponding stripping liquid. The solubility of the stripping solutions of examples 1-8 were observed by themselves and the solution particulates, as shown in Table 2.

TABLE 2

As shown in Table 2, the alcohol organic solvent, the organic alcohol amine, the quaternary ammonium hydroxide and the nonionic surfactant are selected, grinding is not needed, pure water is supplemented, mixing and stirring are carried out until the mixture is uniform, and the obtained stripping liquid is low in metal impurity content and low in particle content.

Thirdly, detecting the performance of the stripping liquid:

(1) swelling residue experiment: the metal substrate with the PI film and the Cu/Al metal wiring is soaked in stripping solutions with different proportions of components in tables 1-1 and 1-2 respectively, the temperature of the stripping solution is shown in tables 1-1 and 1-2, the soaking time is 25-35min, and then the metal substrate is washed clean by cold water and dried by nitrogen gas and observed by a microscope. The effect of the stripping solution is shown in Table 3, and the balance in tables 1-1 and 1-2 is supplemented with pure water.

(2) Metal corrosion test: the metal substrate with the PI film and the Cu/Al metal wiring was immersed in stripping solutions having different proportions of the components shown in tables 1-1 and 1-2, respectively, at the temperatures shown in tables 1-1 and 1-2, for 12 hours, and then cleaned with cold water and dried with nitrogen gas and observed under a microscope. The effect of the stripping solution is shown in Table 3, and the balance in tables 1-1 and 1-2 is supplemented with pure water.

TABLE 3

Examples of the invention	Swelling of PI film	Residual PI film	Corrosion of metal wiring
				Example 1	No swelling	Has no residue	No corrosion
Example 2	No swelling	Has no residue	No corrosion
				Example 3	No swelling	Has no residue	No corrosion
Example 4	No swelling	Has no residue	No corrosion
				Example 5	No swelling	Has no residue	No corrosion
Example 6	No swelling	Has no residue	No corrosion
				Example 7	No swelling	Has no residue	No corrosion
Example 8	No swelling	Has no residue	No corrosion
				Comparative example 1	No swelling	70% residue	No corrosion
Comparative example 2	No swelling	70% residue	Slight corrosion
				Comparative example 3	No swelling	90% residue	Slight corrosion
Comparative example 4	No swelling	60% residue	No corrosion
				Comparative example 5	Slight swelling of the oil	60% residue	No corrosion
Comparative example 6	No swelling	70% residue	No corrosion
				Comparative example 7	No swelling	50% residue	No corrosion
Comparative example 8	No swelling	50% residue	No corrosion
				Comparative example 9	Apparent swelling	Has no residue	Slight corrosion
Comparative example 10	No swelling	50% residue	No corrosion
				Comparative example 11	Severe swelling of	Has no residue	No corrosion
Comparative example 12	No swelling	Has no residue	Severe corrosion of
				Comparative example 13	No swelling	Has no residue	Slight corrosion
Comparative example 14	Severe swelling of	40% residue	No corrosion

As can be seen from Table 3, the content ratio of quaternary ammonium hydroxide and alcohol organic solvent is adjusted, and effective nonionic surfactant is selected, so that the stripping liquid can be used for simply stripping the PI film, the components in the system supplement each other to ensure that no residue is left after the PI film is stripped, no swelling phenomenon occurs, and the metal wiring and the metal substrate are not corroded.

Fourthly, stripping liquid recovery

The stripping treatment is carried out on the metal substrates of the embodiment 1 and the embodiment 2 and the comparative example 5 and the comparative example 6, the metal substrates with the PI film and the Cu/Al metal wiring are respectively soaked in the stripping solution of the embodiment 1 and the embodiment 2 and the comparative example 5 and the comparative example 6, the temperature of the stripping solution is 45-65 ℃, the soaking time is 25-35min, the recovery solution after the stripping treatment is analyzed, the organic solvent is recovered, and the component content and the recovery rate of the recovery solution are shown in the table 4. As can be seen from Table 4, the stripping solution of the present invention can be recovered with high efficiency, is favorable for secondary use, not only reduces material cost, but also is environment-friendly.

Table 4 units: wt.%

The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.