Copper block cleaning agent for semiconductor packaging product and preparation method of copper block cleaning agent

Abstract

The invention discloses a copper block cleaning agent for a semiconductor packaging product and a preparation method, and belongs to the field of semiconductor packaging, the copper block cleaning agent comprises microcapsules and a double-layer carrier, the microcapsules are uniformly distributed between the double-layer carrier, and the carrier is a modified fiber felt; a core material of the microcapsule comprises the following components in parts by weight: a volatile solvent, water, a low molecule-high molecule compound, didecyl adipate, sodium hyaluronate and nano titanium dioxide; the capsule wall of the microcapsule comprises the following components: chitosan, Arabic gum, fish gelatin and a cross-linking agent, the mass ratio of the chitosan to the Arabic gum to the fish gelatin is 1: 2: (2-3), and the dosage of the cross-linking agent is 0.1-0.15% of the total amount of the chitosan, the Arabic gum and the fish gelatin. The problems that existing cleaning objects such as alcohol cotton pieces can be rapidly dried in the natural environment and lose the cleaning capacity in a short time are solved.

Description

TECHNICAL FIELD

[0001] The application belongs to the field of semiconductor packaging and relates to a copper block cleaning agent for semiconductor packaging products and a preparation method. BACKGROUND

[0002] In the process of semiconductor packaging, the cleaning of copper blocks (or copper substrates) is an important link. In modern semiconductor manufacturing and packaging processes, automated and semi-automated cleaning equipment such as vacuum plasma cleaning machines is used to ensure the consistency and efficiency of cleaning.

[0003] However, the packaging process has many procedures, and in the entire packaging process, some copper blocks that have been cleaned will be secondarily contaminated. The surface of the copper blocks is prone to adhere to dust, fibers, fly fibers, oil stains and other contaminants. The area of the secondarily contaminated region is generally small, and is not suitable for cleaning by automated or semi-automated equipment, which will consume a large amount of energy. Therefore, for secondary or multiple contamination, manual cleaning with alcohol cotton swabs and other fast-evaporating cleaning materials is generally used to reduce energy consumption. However, the existing alcohol cotton swabs and other cleaning materials will quickly dry in the natural environment and lose cleaning ability in a short time. When a more thorough cleaning effect is required or a large number of copper blocks need to be cleaned, a large amount of alcohol cotton swabs and other cleaning materials must be consumed, which increases the consumption of materials. SUMMARY

[0004] The application aims to provide a copper block cleaning agent for semiconductor packaging products and a preparation method, which solves the problem that the existing alcohol cotton swabs and other cleaning materials will quickly dry in the natural environment and lose cleaning ability in a short time.

[0005] The technical scheme adopted by the application is as follows.

[0006] A copper block cleaning agent for semiconductor packaging products, comprising microcapsules and double-layer carriers, the microcapsules being uniformly distributed between the double-layer carriers, and the carriers being modified fiber mats.

[0007] The core material of the microcapsules comprises the following components in parts by weight: 60 parts of a volatile solvent, 40 parts of water, 30-32 parts of a low-molecular-high-molecular compound, 8-9 parts of didecyl adipate, 5-6 parts of sodium hyaluronate, and 2-3 parts of nano titanium dioxide. The low-molecular-high-molecular compound comprises a low-molecular substance and a high-molecular polymer. The low-molecular substance comprises lauroylcamosine-gamma-L-glutamyl-L-cysteinyl-glycine polypeptide and acetylenic diol surfactant, and the mass ratio of lauroylcamosine-gamma-L-glutamyl-L-cysteinyl-glycine polypeptide to acetylenic diol surfactant is 3:2. The high-molecular polymer comprises polyethylene glycol and sodium polyacrylate, and the mass ratio of polyethylene glycol to sodium polyacrylate is 3-4:1.

[0008] The capsule wall of the microcapsule comprises the following components: chitosan, gum arabic, fish gelatin, crosslinking agent, and the mass ratio of chitosan, gum arabic and fish gelatin is 1:2:2-3, wherein the amount of the crosslinking agent is 0.1-0.15% of the total amount of chitosan, gum arabic and fish gelatin.

[0009] The lauroyl amino acid-gamma-L-glutamyl-L-cysteinyl-glycine polypeptide and the acetylenic glycol surfactant have good decontamination effect on copper surface after mixing, the lauroyl amino acid-gamma-L-glutamyl-L-cysteinyl-glycine polypeptide surfactant is the main substance, and the lauroyl amino acid-gamma-L-glutamyl-L-cysteinyl-glycine polypeptide surfactant is mild and non-irritating and has corrosion effect on copper plate; however, the lauroyl amino acid-gamma-L-glutamyl-L-cysteinyl-glycine polypeptide surfactant is a polypeptide substance, and the stability is poor, and the acetylenic glycol surfactant is easy to volatilize, so it is difficult to store for a long time after mixing. Therefore, the lauroyl amino acid-gamma-L-glutamyl-L-cysteinyl-glycine polypeptide surfactant, the acetylenic glycol surfactant and the high molecular polymer are mixed to prepare a low molecular-high molecular complex, the high molecular polymer improves the storage stability of the lauroyl amino acid-gamma-L-glutamyl-L-cysteinyl-glycine polypeptide surfactant and simultaneously reduces the volatility of the acetylenic glycol surfactant during storage; meanwhile, the surfactant is wrapped by the microcapsule shell, which further isolates the external air, water and other substances from contacting the lauroyl amino acid-gamma-L-glutamyl-L-cysteinyl-glycine polypeptide surfactant and the acetylenic glycol surfactant, and the lauroyl amino acid-gamma-L-glutamyl-L-cysteinyl-glycine polypeptide surfactant and the acetylenic glycol surfactant have a significant protection effect.

[0010] The microcapsule prepared by the above formula can be broken by hand pressing, and the core material in the microcapsule can be released. The core material prepared by the above formula contains a large amount of surfactant and has a cleaning effect. After the core material is released and infiltrates on the carrier, the low molecular-high molecular complex is separated under the action of pressing, the low molecular material has low viscosity, fast flow speed and small molecular weight, and the low molecular material mixed in the volatile solvent and water can act on the external copper block through the carrier. The low molecular material mainly includes lauroyl amino acid-gamma-L-glutamyl-L-cysteinyl-glycine polypeptide surfactant and acetylenic glycol surfactant, and the low molecular material can clean the copper block. Since the volatile solvent and the acetylenic glycol surfactant are volatile, no marks are left on the copper block, and the surface of the copper block can be quickly dried in the natural environment. The high molecular polymer adheres to the carrier and does not adhere to the surface of the copper block in large amounts, so that the drying speed of the surface of the copper block is slow.

[0011] The core material in the application also contains didecyl adipate, sodium hyaluronate and nano titanium dioxide, the nano titanium dioxide has the effect of resisting ultraviolet, the sodium hyaluronate has the effect of moisturizing on the carrier and can reduce the drying speed of the carrier, and the didecyl adipate has low viscosity and good volatility, and after the didecyl adipate is mixed with the surfactant, the didecyl adipate will not affect the cleaning effect of the surfactant, and will also accelerate the evaporation speed of the cleaning substances remaining on the copper plate.

[0012] Further, the carrier comprises the following components in parts by weight: 25 parts of carboxymethyl modified fiber, 30 parts of amino acid modified fiber, 10 parts of hyperbranched polyester modified fiber, 5 parts of amino silane coupling agent, and 8 parts of water-soluble polymer modified nano bamboo charcoal particles.

[0013] The carrier is prepared by the following method: taking carboxymethyl modified fiber, amino acid modified fiber and hyperbranched polyester modified fiber as main raw materials, mixing and then obtaining fiber felt through wet laying and water jet curing and drying processes; stirring and dispersing the water-soluble polymer modified nano bamboo charcoal particles in the amino silane coupling agent solution to prepare an impregnating solution; immersing the fiber felt in the impregnating solution, deaerating under negative pressure and then drying to obtain modified fiber felt.

[0014] The carrier in the application takes various modified fibers as main materials, and the modified fiber felt prepared by mixing carboxymethyl modified fiber, amino acid modified fiber and hyperbranched polyester modified fiber can be quickly wetted by the core material, has good cleaning effect on the copper block when wiping on the copper block, has good flexibility and high tensile strength, and the water-soluble polymer modified nano bamboo charcoal particles are distributed on the modified fiber felt, so that the modified fiber felt has good moisturizing effect and will not quickly dry in a natural environment.

[0015] Further, the volatile solvent comprises ethanol and isopropyl alcohol, and the mass ratio of ethanol to isopropyl alcohol is 5:2. The volatility of the mixture of ethanol and isopropyl alcohol is enhanced, but the amount of isopropyl alcohol should not be too much, otherwise it will affect the environment.

[0016] Further, the low-molecule-high-molecule complex is prepared by the following method:

[0017] A. The acetylenic diol surfactant is mixed with water in a mixing container to configure a first solution, and lauroylcamosine-gamma-L-glutamyl-L-cysteinyl-glycine polypeptide is slowly added to the first solution under the stirring action of 100 revolutions per minute, and a first intermediate is obtained after uniform stirring;

[0018] B. A polyethylene glycol solution is configured, and the first intermediate is slowly added to the polyethylene glycol solution under the stirring action of 200 revolutions per minute, and a second intermediate is obtained after stirring for 30-40 minutes;

[0019] C. The polyacrylic acid sodium solution is prepared and slowly added into the second intermediate under stirring, and stirred at 20℃ for 4-5 hours to obtain a low-molecule-high-molecule complex.

[0020] Further, the microcapsule is prepared by the following method:

[0021] S1. The chitosan is dissolved in 1% glacial acetic acid solution at 65℃ for 5 hours, and then left for 24 hours. The pH is adjusted to 5.0 to obtain a 3% chitosan solution. The fish gelatin is soaked in cold water for 10 minutes, and then dissolved by heating and stirring in a water bath at 50℃. The pH is adjusted to 4 to obtain a 30% fish gelatin solution with positive charges. The gum arabic is added to deionized water and stirred to obtain a 10% gum arabic solution.

[0022] S2. The volatile solvent is mixed with water to obtain a mixed solvent. The didecyl adipate, sodium hyaluronate, and nano-titanium dioxide are added to the mixed solvent one by one and stirred at 200 rpm until uniform. After uniform stirring, the low-molecule-high-molecule complex is slowly added, and left at 20℃ for 2 hours to obtain the core material of the microcapsule.

[0023] S3. The core material of the microcapsule is dropped into the gum arabic solution, and then the fish gelatin solution with positive charges is added to the gum arabic solution. After 1 hour of reaction, the chitosan solution is added and stirred slowly. The calcium chloride crosslinking agent is added and stirred at 60 rpm for 10 minutes. After 1 hour of reaction, the microcapsule is obtained by filtration and drying.

[0024] Further, the carboxymethyl modified fiber is prepared by the following method: The coniferous wood pulp board is torn into small pieces and mixed with a sodium hydroxide solution. The mixture is introduced into a stirring reaction kettle for defibration and mixing to obtain a pulp slurry. The mass fraction of the coniferous wood pulp board in the pulp slurry is 6wt%. The sodium hydroxide solution is a mixture of sodium hydroxide and alcohol with a mass ratio of 1:20. When the temperature rises to 65℃, a 50% sodium chloroacetate solution is added to the stirring reaction kettle, followed by a small amount of ethanol for reaction. After 30 minutes of reaction, the reaction is terminated by adding water. The carboxymethyl modified fiber is obtained by filtration and washing.

[0025] Further, the amino acid modified fiber is prepared by the following method: hyaluronic acid, glutamic acid, serine and proline are dispersed in distilled water, stirring at room temperature for 10-15h to obtain a mixed system; the mixed system is electrospun by a horizontal electrospinning device equipped with a metal needle injector to obtain an amino acid fiber rich in amino acids; wherein the inner diameter of the metal needle injector is 0.7mm, the electrospinning parameters are: voltage 20-25kV, distance from needle to collector 20-23cm, and feeding rate 0.57-0.95mL / h; the mass ratio between hyaluronic acid, glutamic acid, serine, proline and distilled water is 55:3.5:13:3:50.

[0026] Further, the hyperbranched polyester modified fiber is prepared by the following method: trimethylolpropane and dimethylolpropionic acid are respectively weighed according to a molar ratio of 1:45, placed in a reaction container, and oil bath heated under stirring with the addition of a catalyst p-toluenesulfonic acid, and then nitrogen is introduced, the temperature is raised to 130 DEG C, and constant temperature reaction is carried out for 2h, vacuum is extracted, and reaction is continuously carried out for 2h, and the fourth generation HBP is obtained after reaction is completed; polyethylene terephthalate (PET) chips are mixed with the fourth generation HBP for granulation and spinning, the addition amount of the fourth generation HBP is 2% of the total mass of the polyethylene terephthalate chip and the fourth generation HBP mixture, and the hyperbranched polyester modified fiber is obtained.

[0027] Further, the water-soluble polymer modified nano-bamboo charcoal particle is prepared by the following method: the surface of the nano-bamboo charcoal particle is activated by using the plasma ball milling technology, and the treatment time is 2 hours; polyvinyl alcohol and sodium carboxymethyl cellulose are mixed and dissolved in water to obtain a water-soluble polymer solution, and the mass ratio of polyvinyl alcohol to sodium carboxymethyl cellulose is 2:1; the activated nano-bamboo charcoal particle is mixed with the water-soluble polymer solution according to a mass ratio of 1:10, and stirring reaction is carried out at 80 DEG C for 4 hours, and the water-soluble polymer modified nano-bamboo charcoal particle is obtained by filtration and drying.

[0028] The preparation method of the copper block cleaning agent for a semiconductor packaging product comprises the following steps: microcapsules are dispersed in a water-based polyurethane pressure-sensitive adhesive solution to obtain a mixture, the mixture is uniformly coated on the surface of one of the carriers, and the other carrier is covered on the surface of the carrier coated with the mixture layer, the two carriers are kneaded, the kneading force used for kneading the two carriers is less than the breaking force of the microcapsules, and the final product is obtained after normal temperature drying.

[0029] As described above, due to the adoption of the above technical solutions, the present application has the following beneficial effects:

[0030] 1. The copper block cleaning agent for semiconductor packaging products of the present application uses modified fiber felt as a carrier, and microcapsules with volatile decontamination components wrapped inside as the main cleaning material. On the one hand, it can store volatile and unstable cleaning materials for a long time. On the other hand, after the modified fiber felt soaks the core material, the modified fiber felt and the core material work together to quickly remove the contaminants on the surface of the copper block, and there will be no residue on the surface of the copper block. The copper block surface will quickly dry, and the semiconductor packaging efficiency will not be affected.

[0031] 2. In the present application, after the modified fiber felt soaks the core material, the moisturizing effect is good, and compared with the existing alcohol cotton sheet, the moisturizing time is long and the cleaning effect can be played for a longer time.

[0032] 3. In the present application, the core material has a large amount of volatile substances. After cleaning the copper plate, the surface of the copper plate will dry within a few seconds. BRIEF DESCRIPTION OF DRAWINGS

[0033] In order to more clearly illustrate the technical solutions of the embodiments of the present application, the following will briefly introduce the drawings needed to be used in the embodiments. It should be understood that the following drawings only show some embodiments of the present application, and should not be regarded as a limitation on the scope. For those skilled in the art, other related drawings can also be obtained without creative labor, wherein:

[0034] Figure 1 is a schematic diagram of the microstructure of the microcapsule of the present application;

[0035] Figure 2 is a schematic diagram of the microstructure of the microcapsule adhered to the carrier of the present application. DETAILED DESCRIPTION

[0036] In order to make the purpose, technical solutions and advantages of the present application more clear, the following will further describe the present application in combination with the drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present application, and are not used to limit the present application, that is, the described embodiments are only a part of the embodiments of the present application, but not all the embodiments. The components of the embodiments of the present application described and shown in the drawings herein can be arranged and designed in various different configurations.

[0037] Therefore, the following detailed description of the embodiments of the present application provided in the drawings is not intended to limit the scope of the claimed present application, but only represents selected embodiments of the present application. Based on the embodiments of the present application, all other embodiments obtained by those skilled in the art without creative labor are within the scope of protection of the present application.

[0038] It is to be understood that the terms "first" and "second" and similar relating terms are used merely to distinguish one entity or action from another, and do not necessarily require or imply any such actual relationship or order between such entities or actions. Also, the terms "comprising", "containing", or any other similar words are intended to encompass non-exclusive inclusion, so that a process, method, article, or apparatus including a list of elements does not necessarily include only those elements, but can include other elements not expressly listed, or can include elements inherent in such process, method, article, or apparatus. Without more limitation, the element defined by the phrase "comprising a" does not exclude the presence of additional identical elements in the process, method, article, or apparatus including the element.

[0039] The features and performances of the present application are further described in detail below in conjunction with embodiments.

[0040] Embodiment 1

[0041] The copper block cleaning agent for semiconductor packaging products provided by the preferred embodiment of the present application comprises microcapsules and double-layer carriers, the microcapsules are uniformly distributed between the double-layer carriers, and the carrier is a modified fiber felt.

[0042] The core material of the microcapsule comprises the following components in parts by weight: 60 parts of volatile solvent, 40 parts of water, 30-32 parts of low-molecular-high-molecular complex, 8-9 parts of didecyl adipate, 5-6 parts of sodium hyaluronate, and 2-3 parts of nano titanium dioxide; the low-molecular-high-molecular complex comprises low-molecular substances and high-molecular polymers, wherein the mass ratio of lauroylsarcosine-γ-L-glutamyl-L-cysteinyl-glycine polypeptide to acetylenic diol surfactant is 3:2; and the mass ratio of polyethylene glycol to sodium polyacrylate in the high-molecular polymers is 3-4:1.

[0043] The capsule wall of the microcapsule comprises the following components: chitosan, gum arabic, fish gelatin, and crosslinking agent, and the mass ratio of chitosan, gum arabic, and fish gelatin is 1:2:2, wherein the amount of the crosslinking agent is 0.1% of the total amount of chitosan, gum arabic, and fish gelatin.

[0044] The carrier comprises the following components in parts by weight: 25 parts of carboxymethyl modified fiber, 30 parts of amino acid modified fiber, 10 parts of hyperbranched polyester modified fiber, 5 parts of amino silane coupling agent, and 8 parts of water-soluble polymer modified nano bamboo charcoal particles.

[0045] The carrier is prepared by the following method: taking carboxymethyl modified fiber, amino acid modified fiber, hyperbranched polyester modified fiber as main raw materials, mixing, then obtaining fiber mat through wet laying and water jet curing drying process; adding water-soluble polymer modified nano bamboo charcoal particles into amino silane coupling agent solution to stir and disperse, to obtain impregnating solution; immersing the fiber mat into the impregnating solution, deaerating under negative pressure, and drying to obtain modified fiber mat.

[0046] The volatile solvent includes ethanol and isopropyl alcohol, and the mass ratio of ethanol to isopropyl alcohol is 5:2.

[0047] The low-molecular-high-molecular complex is prepared by the following method:

[0048] A, the acetylene diol surfactant is mixed with water in a mixing container to configure a first solution, the lauroylcamosine-gamma-L-glutamyl-L-cysteinyl-glycine polypeptide is slowly added to the first solution under the stirring of 100 revolutions per minute, and a first intermediate is obtained after uniform stirring;

[0049] B, a polyethylene glycol solution is configured, the first intermediate is slowly added to the polyethylene glycol solution under the stirring of 200 revolutions per minute, and a second intermediate is obtained after stirring for 30-40 minutes;

[0050] C, a sodium polyacrylate solution is configured, the sodium polyacrylate solution is slowly added to the second intermediate under stirring, and the low-molecular-high-molecular complex is obtained after stirring and mixing at 20℃ for 4-5 hours.

[0051] The microcapsule is prepared by the following method:

[0052] S1, chitosan is dissolved in an acetic acid solution with a mass fraction of 1%, and dissolved at 65℃ for 5 hours, then placed for 24 hours, and adjusted to pH 5.0 to obtain a chitosan solution with a mass fraction of 3%; fish gelatin is soaked in cold water for 10 minutes, then dissolved by heating and stirring in a water bath, the water bath heating temperature is 50℃, and adjusted to pH 4 to obtain a fish gelatin solution with a mass fraction of 30% and positive charge; arabic gum is added to deionized water and stirred and dissolved to obtain an arabic gum solution with a mass fraction of 10%;

[0053] S2, a mixed solvent is prepared by mixing a volatile solvent and water, then adipic acid didecyl ester, sodium hyaluronate and nano titanium dioxide are added one by one into the mixed solvent, stirred uniformly at 200 revolutions per minute, then stopped stirring, and finally slowly add the low-molecular-high-molecular complex, and stand for 2 hours at 20℃ to obtain the core material of the microcapsule;

[0054] S3, the core material of the microcapsule is dropped into the gum arabic solution, then the positively charged fish gelatin solution is added into the gum arabic solution, after 1 hour of reaction, the chitosan solution is added, after uniform mixing, the calcium chloride crosslinking agent is slowly dropped, after 10 minutes of stirring at a stirring speed of 60 revolutions per minute, the reaction is allowed to stand for 1 hour, then filtration and drying are performed to obtain the microcapsule.

[0055] The carboxymethyl modified fiber is prepared by the following method: under room temperature conditions, coniferous wood pulp plates are torn into small pieces, mixed with a sodium hydroxide solution, and then added into a stirring reaction kettle for defibration and mixing to obtain a pulp, the mass fraction of the coniferous wood pulp plates in the pulp is 6wt%, the sodium hydroxide solution is a mixture of sodium hydroxide and alcohol with a mass ratio of 1:20, when the temperature rises to 65℃, a sodium chloroacetate solution with a mass fraction of 50% is added into the stirring reaction kettle, followed by the addition of a small amount of ethanol for reaction, after 30 minutes of reaction, water is added to terminate the reaction, then filtration and washing are performed to obtain the carboxymethyl modified fiber.

[0056] The amino acid modified fiber is prepared by the following method: hyaluronic acid, glutamic acid, serine and proline are dispersed in distilled water, and stirring is performed at room temperature for 10-15h to obtain a mixed system; the mixed system is subjected to electrospinning through a horizontal electrospinning device equipped with a metal needle injector to obtain an amino acid fiber rich in amino acids; wherein the inner diameter of the metal needle injector is 0.7mm, the electrospinning parameters are: voltage of 20-25kV, distance from the needle to the collector of 20-23cm, and feeding rate of 0.57-0.95mL / h; the mass ratio between the hyaluronic acid, glutamic acid, serine, proline and distilled water is 55:3.5:13:3:50.

[0057] The hyperbranched polyester modified fiber is prepared by the following method: trimethylolpropane and dihydroxymethyl propionic acid are respectively weighed according to a molar ratio of 1:45, placed in a reaction container, and subjected to oil bath heating under the stirring action of a catalyst p-toluenesulfonic acid, nitrogen is introduced, the temperature is raised to 130℃, constant temperature reaction is performed for 2h, vacuum is applied, and continuous reaction is performed for 2h, after the reaction is completed, the fourth generation HBP is obtained; polyethylene terephthalate (PET) chips are mixed with the fourth generation HBP for granulation and spinning, the addition amount of the fourth generation HBP is 2% of the total mass of the polyethylene terephthalate chip and the fourth generation HBP mixture, and the hyperbranched polyester modified fiber is obtained.

[0058] The water-soluble polymer modified nano-bamboo charcoal particles are prepared by the following method: the surface of nano-bamboo charcoal particles is activated by using plasma ball milling technology, and the treatment time is 2 hours; polyvinyl alcohol and sodium carboxymethyl cellulose are mixed and dissolved in water to obtain a water-soluble polymer solution, and the mass ratio of polyvinyl alcohol to sodium carboxymethyl cellulose is 2:1; the activated nano-bamboo charcoal particles are mixed with the water-soluble polymer solution according to a mass ratio of 1:10, and stirred and reacted at 80 DEG C for 4 hours, and then filtered and dried to obtain the water-soluble polymer modified nano-bamboo charcoal particles.

[0059] The preparation method of the copper block cleaning agent for semiconductor packaging products comprises the following steps: stirring and dispersing microcapsules in a water-based polyurethane pressure-sensitive adhesive solution to obtain a mixture, uniformly coating the mixture on the surface of one layer of carrier, covering another layer of carrier on the surface of the carrier coated with the mixture layer, kneading the two layers of carrier, and using a kneading force less than the breaking force of the microcapsules, and drying at room temperature to obtain the final product: the final product is used by pressing the carrier with hands or other pressing equipment, so that the microcapsules between the two layers of carrier are broken, the core material in the microcapsules is released after the microcapsules are broken, the carrier is wetted by the core material, and after the carrier is wetted by the core material with the decontamination function, the copper block is wiped, the pollutants on the surface of the copper block can be quickly removed, and the surface of the copper block is quickly dried after cleaning, and no marks are left.

[0060] In actual use, generally, 20-25g of microcapsules are coated on a carrier with a size of 20X20cm, and the mass ratio of the microcapsules to the water-based polyurethane pressure-sensitive adhesive solution is 3:1.

[0061] Figure 1 The microcapsule product of the application can be clearly seen from the micrograph of the microcapsule product of the application. Figure 2 As shown in the figure, the microcapsules mixed with the water-based polyurethane pressure-sensitive adhesive in the application can be successfully adhered to the carrier.

[0062] Example 2

[0063] This example is based on example 1, and is different from example 1 in that: the capsule wall of the microcapsule comprises the following components: chitosan, gum arabic, fish gelatin and crosslinking agent, and the mass ratio of chitosan, gum arabic and fish gelatin is 1:2:2.5, wherein the amount of the crosslinking agent is 0.1% of the total amount of chitosan, gum arabic and fish gelatin.

[0064] Example 3

[0065] The embodiment is based on example 1, and different from example 1 is that the capsule wall of the microcapsule comprises the following components: chitosan, gum arabic, fish gelatin, crosslinking agent, the mass ratio of chitosan, gum arabic and fish gelatin is 1:2:3, wherein the amount of crosslinking agent is 0.1% of the total amount of chitosan, gum arabic and fish gelatin.

[0066] Example 4

[0067] The embodiment is based on example 1, and different from example 1 is that the capsule wall of the microcapsule comprises the following components: chitosan, gum arabic, fish gelatin, crosslinking agent, the mass ratio of chitosan, gum arabic and fish gelatin is 1:2:2, wherein the amount of crosslinking agent is 0.13% of the total amount of chitosan, gum arabic and fish gelatin.

[0068] Example 5

[0069] The embodiment is based on example 2, and different from example 2 is that the capsule wall of the microcapsule comprises the following components: chitosan, gum arabic, fish gelatin, crosslinking agent, the mass ratio of chitosan, gum arabic and fish gelatin is 1:2:2, wherein the amount of crosslinking agent is 0.15% of the total amount of chitosan, gum arabic and fish gelatin.

[0070] Example 6

[0071] The embodiment is based on example 2, and different from example 2 is that the capsule wall of the microcapsule comprises the following components: chitosan, gum arabic, fish gelatin, crosslinking agent, the mass ratio of chitosan, gum arabic and fish gelatin is 1:2:2.5, wherein the amount of crosslinking agent is 0.13% of the total amount of chitosan, gum arabic and fish gelatin.

[0072] Example 7

[0073] The embodiment is based on example 2, and different from example 2 is that the capsule wall of the microcapsule comprises the following components: chitosan, gum arabic, fish gelatin, crosslinking agent, the mass ratio of chitosan, gum arabic and fish gelatin is 1:2:2.5, wherein the amount of crosslinking agent is 0.15% of the total amount of chitosan, gum arabic and fish gelatin.

[0074] Example 8

[0075] The embodiment is based on example 3, and different from example 3 is that the capsule wall of the microcapsule comprises the following components: chitosan, gum arabic, fish gelatin, crosslinking agent, the mass ratio of chitosan, gum arabic and fish gelatin is 1:2:3, wherein the amount of crosslinking agent is 0.13% of the total amount of chitosan, gum arabic and fish gelatin.

[0076] Example 9

[0077] The present example is based on example 3, except that the capsule wall of the microcapsule comprises the following components: chitosan, gum arabic, fish gelatin, crosslinking agent, the mass ratio of chitosan, gum arabic and fish gelatin is 1:2:3, wherein the amount of crosslinking agent is 0.15% of the total amount of chitosan, gum arabic and fish gelatin.

[0078] Comparative Example 1

[0079] The present comparative example is based on example 8, except that the core material of the microcapsule in the present comparative example comprises the following components by weight: 70 parts of volatile solvent, 40 parts of water, 30-32 parts of low-molecular-high-molecular complex, 8-9 parts of didecyl adipate, 5-6 parts of sodium hyaluronate, and 2-3 parts of nano titanium dioxide; the low-molecular-high-molecular complex comprises low-molecular substances and high-molecular polymers, wherein the mass ratio of lauroylsarcosine-γ-L-glutamyl-L-cysteinyl-glycine polypeptide to acetylenic diol surfactant is 3:2; and the mass ratio of polyethylene glycol to sodium polyacrylate is 3-4:1.

[0080] Comparative Example 2

[0081] The present comparative example is based on example 8, except that the core material of the microcapsule in the present comparative example comprises the following components by weight: 50 parts of volatile solvent, 40 parts of water, 30-32 parts of low-molecular-high-molecular complex, 8-9 parts of didecyl adipate, 5-6 parts of sodium hyaluronate, and 2-3 parts of nano titanium dioxide; the low-molecular-high-molecular complex comprises low-molecular substances and high-molecular polymers, wherein the mass ratio of lauroylsarcosine-γ-L-glutamyl-L-cysteinyl-glycine polypeptide to acetylenic diol surfactant is 3:2; and the mass ratio of polyethylene glycol to sodium polyacrylate is 3-4:1.

[0082] Comparative Example 3

[0083] The comparative example is based on example 8, and different from example 8 is that the core material of the microcapsule in the comparative example comprises the following components in parts by weight: 60 parts of volatile solvent, 40 parts of water, 30-32 parts of low-molecular-high-molecular complex, 8-9 parts of didecyl adipate, 5-6 parts of sodium hyaluronate, and 2-3 parts of nano titanium dioxide; the low-molecular-high-molecular complex comprises low-molecular substances and high-molecular polymers, wherein the low-molecular substances comprise lauroylcamosine-gamma-L-glutamyl-L-cysteinyl-glycine polypeptide and acetylenic diol surfactant, and the mass ratio of lauroylcamosine-gamma-L-glutamyl-L-cysteinyl-glycine polypeptide to acetylenic diol surfactant is 1:1; wherein the high-molecular polymers comprise polyethylene glycol and sodium polyacrylate, and the mass ratio of polyethylene glycol to sodium polyacrylate is 3-4:1. Compared with example 8, the cleaning efficiency on the copper plate is relatively poor after the proportion of lauroylcamosine-gamma-L-glutamyl-L-cysteinyl-glycine polypeptide is reduced, and the cleaning time of the comparative example 3 is longer when wiping the copper plate for the same type of stains.

[0084] Comparative example 4

[0085] The comparative example is based on example 8, and different from example 8 is that the core material of the microcapsule in the comparative example comprises the following components in parts by weight: 60 parts of volatile solvent, 40 parts of water, 30-32 parts of low-molecular-high-molecular complex, 8-9 parts of didecyl adipate, 5-6 parts of sodium hyaluronate, and 2-3 parts of nano titanium dioxide; the low-molecular-high-molecular complex comprises low-molecular substances and high-molecular polymers, wherein the low-molecular substances comprise lauroylcamosine-gamma-L-glutamyl-L-cysteinyl-glycine polypeptide and acetylenic diol surfactant, and the mass ratio of lauroylcamosine-gamma-L-glutamyl-L-cysteinyl-glycine polypeptide to acetylenic diol surfactant is 2:1; wherein the high-molecular polymers comprise polyethylene glycol and sodium polyacrylate, and the mass ratio of polyethylene glycol to sodium polyacrylate is 3-4:1.

[0086] Comparative example 5

[0087] The comparative example is based on example 8, and different from example 8 is that the core material of the microcapsule in the comparative example comprises the following components in parts by weight: 60 parts of volatile solvent, 40 parts of water, 30-32 parts of low-molecular-high-molecular complex, 8-9 parts of didecyl adipate, 5-6 parts of sodium hyaluronate, and 2-3 parts of nano titanium dioxide; the low-molecular-high-molecular complex comprises low-molecular substances and high-molecular polymers, wherein the low-molecular substances comprise lauroylcamosine-gamma-L-glutamyl-L-cysteinyl-glycine polypeptide and acetylenic diol surfactant, and the mass ratio of lauroylcamosine-gamma-L-glutamyl-L-cysteinyl-glycine polypeptide to acetylenic diol surfactant is 2:1; wherein the high-molecular polymers comprise polyethylene glycol and sodium polyacrylate, and the mass ratio of polyethylene glycol to sodium polyacrylate is 3-4:1.

[0088] Comparative example 6

[0089] The present comparative example is based on Example 8, except that the core material of the microcapsule in the present comparative example comprises the following components in parts by weight: 60 parts of volatile solvent, 40 parts of water, 30-32 parts of low-molecular-macromolecular complex, 8-9 parts of didecyl adipate, 5-6 parts of sodium hyaluronate, 2-3 parts of nano titanium dioxide; the low-molecular-macromolecular complex comprises low-molecular substances and macromolecular polymers, wherein the low-molecular substances do not comprise lauroylcamosine-γ-L-glutamyl-L-cysteinyl-glycine polypeptide, but only comprise acetylenic diol surfactant; and wherein the macromolecular polymers comprise polyethylene glycol and sodium polyacrylate, and the mass ratio of polyethylene glycol to sodium polyacrylate is 3-4:1.

[0090] Comparative Example 7

[0091] The present comparative example is based on Example 1, except that the cleaning agent prepared from 60 parts of volatile solvent, 40 parts of water, 30-32 parts of low-molecular-macromolecular complex, 8-9 parts of didecyl adipate, 5-6 parts of sodium hyaluronate, and 2-3 parts of nano titanium dioxide in the present comparative example directly infiltrates on the carrier, is not formed into microcapsules, and is not wrapped by a capsule wall; the low-molecular-macromolecular complex comprises low-molecular substances and macromolecular polymers, wherein the low-molecular substances comprise lauroylcamosine-γ-L-glutamyl-L-cysteinyl-glycine polypeptide and acetylenic diol surfactant, and the mass ratio of lauroylcamosine-γ-L-glutamyl-L-cysteinyl-glycine polypeptide to acetylenic diol surfactant is 3:2; and wherein the macromolecular polymers comprise polyethylene glycol and sodium polyacrylate, and the mass ratio of polyethylene glycol to sodium polyacrylate is 3-4:1.

[0092] Comparative Example 8

[0093] The present comparative example is based on Example 1, except that the core material of the microcapsule in the present comparative example comprises the following components in parts by weight: 60 parts of volatile solvent, 40 parts of water, 30-32 parts of low-molecular-macromolecular complex, 8-9 parts of didecyl adipate, 5-6 parts of sodium hyaluronate, 2-3 parts of nano titanium dioxide; wherein the low-molecular-macromolecular complex comprises low-molecular substances and macromolecular polymers, wherein the low-molecular substances do not comprise lauroylcamosine-γ-L-glutamyl-L-cysteinyl-glycine polypeptide, but only comprise acetylenic diol surfactant; and wherein the macromolecular polymers comprise polyethylene glycol and sodium polyacrylate, and the mass ratio of polyethylene glycol to sodium polyacrylate is 3-4:1.

[0094] Comparative Example 9

[0095] The comparative example is based on Example 1, except that the carrier in the comparative example does not include the carboxymethyl-modified fiber.

[0096] Comparative Example 10

[0097] The comparative example is based on Example 1, except that the carrier in the comparative example does not include the amino acid-modified fiber.

[0098] Comparative Example 11

[0099] The comparative example is based on Example 1, except that the carrier in the comparative example does not include the hyperbranched polyester-modified fiber.

[0100] Comparative Example 12

[0101] The comparative example is based on Example 1, except that the carrier in the comparative example does not include the water-soluble polymer-modified nano-bamboo charcoal particles.

[0102] Comparative Example 13

[0103] The comparative example is based on Example 1, except that the nano-bamboo charcoal particles in the carrier in the comparative example are not modified by a water-soluble polymer.

[0104] Comparative Example 14

[0105] The comparative example is based on Example 1, except that the volatile solvent in the comparative example does not include isopropyl alcohol.

[0106] Comparative Example 15

[0107] The comparative example is based on Example 1, except that the volatile solvent in the comparative example does not include ethanol. After the volatile solvent is only isopropyl alcohol, the skin will have an uncomfortable feeling.

[0108] Test Example 1

[0109] A carrier with a size of 20X20 cm is coated with 20-25 g of microcapsules, and the mass ratio of the microcapsules to the water-based polyurethane pressure-sensitive adhesive solution is 3:1; the force that causes the microcapsules between the two layers of the carrier to break in Examples 1-9 is detected using a capsule hardness tester, and after the microcapsules break, the carrier quickly shows a wetting phenomenon; the product with the microcapsules adhered between the two layers of the carrier is placed on the detection table of the capsule hardness tester, and when the wetting phenomenon appears on any one layer of the carrier, it indicates that the microcapsules have broken, and the breaking force at this time is recorded, with the unit being N; the results are shown in Table 1.

[0110] Table 1 Microcapsule Breaking Force Test Results

[0111]

[0112] The microcapsules prepared in Example 8 in the present application have a breaking force of 6-7 N, and can be easily broken by hand, and are convenient to use. Moreover, the microcapsules are not prone to breakage or opening during storage, coating, stirring, kneading of the upper carrier, etc. at this breaking force. Therefore, in actual use, the technical scheme of Example 8 in the present application is preferred. When the breaking force of the microcapsules is lower than 3.5 N, the microcapsules are very easy to break, which is not conducive to the adhesion between the double-layer carriers. When the breaking force of the microcapsules is higher than 12 N, it is not convenient to quickly break the microcapsules.

[0113] Test Example 2

[0114] The products prepared in Examples 1-9 and Comparative Examples 1-15 were used to wipe the surface of a copper block of the same material (the carrier had microcapsules, and the carrier needed to be squeezed to break the microcapsules and release the internal core material, so that the carrier was wetted). The drying time of the copper block surface was detected, and the time required for the double-layer carrier to completely dry in a 25℃, 70% humidity environment (moisture retention time) was also detected. The time for the carrier to dry was from the start of squeezing the microcapsules to break them and wet the carrier to the end of the carrier completely drying. Whether the carrier dried was directly perceived by hand squeezing. After hand squeezing the carrier, the hand was kept in the squeezed state for 1-2 seconds, and if there was no wet feeling on the hand, it indicated that the carrier completely dried. The results are shown in Table 2.

[0115] Table 2: Detection results of copper block surface drying time and carrier moisture retention time

[0116]

[0117]

[0118] Test Example 3

[0119] The breaking strength of the carrier in Example 1 and Comparative Examples 9-13 was detected, and the detection method was the prior art. The detection results are shown in Table 3.

[0120] Table 2: Detection results of carrier breaking strength

[0121]

[0122] The carrier of the present application has good tensile properties.

[0123] The above only describes the preferred embodiments of the present application, and is not intended to limit the protection scope of the present application. Any modifications, equivalent replacements and improvements made by those skilled in the art within the spirit and principles of the present application shall be included in the protection scope of the present application.

Claims

1. A copper block cleaning agent for semiconductor packaging products, characterized in that: It includes microcapsules and a double-layer carrier, with the microcapsules evenly distributed between the double-layer carrier, and the carrier being a modified fiber felt; The core material of the microcapsule comprises the following components in parts by weight: 60 parts volatile solvent, 40 parts water, 30-32 parts low-molecular-weight-high-molecular-weight complex, 8-9 parts didecyl adipate, 5-6 parts sodium hyaluronate, and 2-3 parts nano-titanium dioxide; the low-molecular-weight-high-molecular-weight complex comprises low-molecular-weight substances and high-molecular-weight polymers, wherein the low-molecular-weight substances include lauroyl sarcosine-γ-L-glutamyl-L-cysteyl-glycine peptide and acetylation glycol surfactant, with a mass ratio of lauroyl sarcosine-γ-L-glutamyl-L-cysteyl-glycine peptide and acetylation glycol surfactant of 3:2; wherein the high-molecular-weight polymers include polyethylene glycol and sodium polyacrylate, with a mass ratio of polyethylene glycol and sodium polyacrylate of 3-4:

1. The capsule wall comprises the following components: chitosan, gum arabic, fish gelatin, and a crosslinking agent. The mass ratio of chitosan, gum arabic, and fish gelatin is 1:2:2-3, and the amount of crosslinking agent is 0.1-0.15% of the total amount of chitosan, gum arabic, and fish gelatin.

2. The copper block cleaning agent for semiconductor packaging products according to claim 1, characterized in that: The carrier comprises the following components in parts by weight: 25 parts carboxymethyl modified fiber, 30 parts amino acid modified fiber, 10 parts hyperbranched polyester modified fiber, 5 parts aminosilane coupling agent, and 8 parts water-soluble polymer modified nano-bamboo charcoal particles. The carrier is prepared by the following method: using carboxymethyl modified fiber, amino acid modified fiber and hyperbranched polyester modified fiber as the main raw materials, the fiber felt is obtained by mixing and then by wet web forming and hydroentanglement curing and drying process. Water-soluble polymer-modified bamboo charcoal nanoparticles were added to an aminosilane coupling agent solution and stirred to disperse, thus preparing an impregnation solution. The fiber felt is immersed in the impregnation solution, degassed under negative pressure, and then dried to obtain the modified fiber felt.

3. The copper block cleaning agent for semiconductor packaging products according to claim 1, characterized in that: The volatile solvents include ethanol and isopropanol, with a mass ratio of ethanol to isopropanol of 5:

2.

4. The copper block cleaning agent for semiconductor packaging products according to claim 1, characterized in that: The low-molecular-weight-high-molecular-weight complex was prepared by the following method: A. Prepare a first solution by mixing acetylation diol surfactant with water in a mixing container. Slowly add lauroyl sarcosine-γ-L-glutamyl-L-cysteine-glycine polypeptide to the first solution while stirring at 100 rpm. After stirring evenly, obtain the first intermediate. B. Prepare a polyethylene glycol solution, and slowly add the first intermediate to the polyethylene glycol solution while stirring at 200 rpm. After stirring for 30-40 minutes, the second intermediate is obtained. C. Prepare a sodium polyacrylate solution, and slowly add the sodium polyacrylate solution to the second intermediate under stirring. Stir and mix at 20°C for 4-5 hours to obtain a low molecular weight-high molecular weight composite.

5. The copper block cleaning agent for semiconductor packaging products according to claim 1, characterized in that: The microcapsules were prepared by the following method: S1. Chitosan was dissolved in a 1% (w / w) glacial acetic acid solution at 65°C for 5 hours, then allowed to stand for 24 hours. The pH was adjusted to 5.0 to obtain a 3% (w / w) chitosan solution. Fish gelatin was soaked in cold water for 10 minutes, then heated and stirred in a hot water bath at 50°C to dissolve. The pH was adjusted to 4 to obtain a 30% (w / w) positively charged fish gelatin solution. Gum arabic was added to deionized water and stirred to dissolve, resulting in a 10% (w / w) gum arabic solution. S2. A mixed solvent is prepared by mixing a volatile solvent with water. Then, didecyl adipate, sodium hyaluronate, and nano titanium dioxide are added to the mixed solvent one by one and stirred at 200 rpm until homogeneous. After stirring until homogeneous, stirring is stopped. Finally, a low-molecular-weight-high-molecular-weight complex is slowly added and allowed to stand at 20°C for 2 hours to obtain the core material of the microcapsules. S3. After dropping the core material of the microcapsule into the gum arabic solution, add a positively charged fish gelatin solution to the gum arabic solution. After reacting for 1 hour, add the chitosan solution, mix evenly, and then slowly drop in the calcium chloride crosslinking agent. Stir at a stirring speed of 60 rpm for 10 minutes, then let it stand for 1 hour to react. Filter and dry to obtain the microcapsules.

6. The copper block cleaning agent for semiconductor packaging products according to claim 2, characterized in that: The carboxymethyl modified fiber was prepared by the following method: at room temperature, softwood pulp board was torn into small pieces, mixed with sodium hydroxide solution, and then added to a stirred reactor to dissolve and mix to obtain pulp. The mass fraction of softwood pulp board in the pulp was 6 wt%. The sodium hydroxide solution was a mixture of sodium hydroxide and alcohol with a mass ratio of 1:

20. When the temperature rose to 65°C, a 50% sodium chloroacetate solution was added to the stirred reactor, followed by the addition of a small amount of ethanol for reaction. After reacting for 30 minutes, water was added to terminate the reaction. Then, the mixture was filtered and washed to obtain carboxymethyl modified fiber.

7. The copper block cleaning agent for semiconductor packaging products according to claim 2, characterized in that: The amino acid-modified fiber was prepared by the following method: hyaluronic acid, glutamic acid, serine, and proline were dispersed in distilled water and stirred at room temperature for 10-15 hours to obtain a mixed system; the mixed system was electrospun using a horizontal electrospinning device equipped with a metal needle syringe to obtain amino acid-rich fibers; wherein the inner diameter of the metal needle syringe was 0.7 mm, and the electrospinning parameters were: voltage 20-25 kV, distance from needle to collector 20-23 cm, and feed rate 0.57-0.95 mL / h; the mass ratio of hyaluronic acid, glutamic acid, serine, proline, and distilled water was 55:3.5:13:3:

50.

8. The copper block cleaning agent for semiconductor packaging products according to claim 2, characterized in that: The hyperbranched polyester modified fiber was prepared by the following method: Trimethylolpropane and dimethylolpropionic acid were weighed at a molar ratio of 1:45 and placed in a reaction vessel. The catalyst p-toluenesulfonic acid was added under stirring and heated in an oil bath. Nitrogen gas was introduced and the temperature was raised to 130°C. The reaction was kept at a constant temperature for 2 hours. Vacuum was then applied and the reaction was continued for another 2 hours. After the reaction was completed, fourth-generation HBP was obtained. Polyethylene terephthalate chips and fourth-generation HBP were mixed, granulated, and spun. The amount of fourth-generation HBP added was 2% of the total mass of the mixture of polyethylene terephthalate chips and fourth-generation HBP, thus obtaining hyperbranched polyester modified fiber.

9. The copper block cleaning agent for semiconductor packaging products according to claim 2, characterized in that: The water-soluble polymer-modified nano-bamboo charcoal particles were prepared by the following method: the nano-bamboo charcoal particles were surface-activated using plasma ball milling technology for 2 hours; polyvinyl alcohol and sodium carboxymethyl cellulose were mixed and dissolved in water to obtain a water-soluble polymer solution, with a mass ratio of polyvinyl alcohol to sodium carboxymethyl cellulose of 2:1; the activated nano-bamboo charcoal particles and the water-soluble polymer solution were mixed at a mass ratio of 1:10, stirred and reacted at 80°C for 4 hours, and then filtered and dried to obtain the water-soluble polymer-modified nano-bamboo charcoal particles.

10. A method for preparing a copper block cleaning agent for semiconductor packaging products as described in any one of claims 1-9, characterized in that, Includes the following steps: The microcapsules were placed in an aqueous polyurethane pressure-sensitive adhesive solution and stirred to disperse them, thus obtaining a mixture. The mixture was then uniformly coated on the surface of one of the carrier layers. Finally, another carrier layer was placed on top of the carrier layer coated with the mixture. The two carrier layers were kneaded together, and the kneading force used to knead the two carrier layers was less than the breaking force of the microcapsules. After drying at room temperature, the final product was obtained.

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