Cleaning composition and method for removing thermoplastic polymer materials using the same

Abstract

A cleaning agent composition and a method for removing thermoplastic polymers using the cleaning agent composition are disclosed. The cleaning agent composition comprises at least 10 to 90 wt% of a cyclic acetal compound and 10 to 90 wt% of an aprotic solvent, wherein the aprotic solvent comprises an aromatic ether compound and / or an lactone compound. This cleaning agent composition can not only clean residual materials on wafers but also clean coating equipment and pipelines.

Description

Technical Field

[0001] This invention relates to a cleaning agent composition and a method for removing residual thermoplastic polymer bonding materials using the cleaning agent composition on wafer and coating equipment, and more particularly to a cleaning agent composition and material removal method for cleaning thermoplastic polymer materials in packaging, power device, microelectromechanical and compound wafer fabrication processes. Prior Technology

[0002] Applications such as virtual reality, autonomous vehicles, and artificial intelligence require high-speed computing, and the semiconductor industry's focus has shifted from Moore's Law to heterogeneous integration and advanced high-density packaging. Wafer-level packaging (WLP) has evolved to the point where system-level packaging integration is possible. As die area shrinks and the required input / output bandwidth and number of chips continue to increase, innovative and advanced packaging designs are needed to maintain high bandwidth demands.

[0003] In the past, the packaging industry has relied on flip-chip processes to handle most WLP applications. In the past few years, many new WLP technologies have been developed to achieve higher density applications, including various forms of fan-out wafer-level packaging, fan-in wafer-level chip-scale packaging, 3D FOWLP, 2.5D integrated interposer technology, and 3D IC integration using through-silicon vias (TSVs).

[0004] Many WLP technologies require a substrate to support the wafer during the thinning process, and substrate-assisted wafer thinning has proven to be a reliable method. This method uses polymer materials to temporarily bond the wafer to the substrate, controlling the overall stability of the structure during thinning and other processes.

[0005] In the temporary bonding process, a polymer bonding material is used to mount the wafer onto a carrier substrate. The bonding material and the carrier substrate support the wafer during thinning and subsequent back-side processing. Because the bonding material needs to have bonding and debonding properties, as well as a stable structure during the process, its design must consider the matching of thermal expansion coefficients, the ability to withstand the high stress generated by thermal cycling, and ease of separation at the end of the process.

[0006] Temporary bonding technology has been applied in various high-volume production environments for processing ultrathin wafers using standard wafer fabrication processes such as deposition, dry or wet etching, electroplating, and cleaning. This technology is used in packaging, power devices, microelectromechanical systems (MEMS), and III-V wafer fabrication processes to handle ultrathin wafers.

[0007] Advanced packaging technologies have been developed to meet the demands of electronic devices for high performance, low cost, and small size, resulting in fan-out wafer-level packaging technology. The temporary bonding / debonding technology upon which advanced fan-out technology relies is the foundation of device manufacturing processes.

[0008] Before wafer thinning, the wafer and bonding material must be fixed on a carrier substrate to temporarily bond them together before proceeding with subsequent processes. This is to prevent the thinned wafer from becoming too weak and prone to breakage during process handling. To enable compound wafers to withstand the high stress and temperature during wafer thinning and downstream processing, a polymer bonding material system is required.

[0009] Temporary bonding materials need to possess good thermal, mechanical, and chemical stability. As temperature increases, the mechanical stability of temporary bonding materials gradually disappears as the melt viscosity decreases, thus reducing the stability of the temporary bonding material and causing wafer deformation and delamination. Therefore, temporary bonding materials must be heat-resistant, have a wide thermal cycling temperature range (200-400℃), be easily separable, leave no residue, and prevent gas release from the bonding material that could damage the material on the wafer. Thus, in the advantageous RDL-preferred fan-out wafer-level packaging, thermoplastic polymeric temporary bonding materials with high glass transition temperatures (Tg) are required. These materials possess high softening points to achieve mechanical stability, provide thermal stability up to 400℃, and can absorb laser separation energy to prevent direct laser damage to the material on the wafer.

[0010] After the back-side fabrication of the wafer is completed, the wafer needs to be attached to the fixing tape on the stainless steel frame. Finally, the wafer must be separated from the carrier substrate, usually by mechanical separation or laser separation methods. Any residual bonding material on the carrier substrate and the wafer must be completely cleaned before the wafer can continue to the subsequent processes and the carrier substrate can be recycled.

[0011] On the other hand, during long-term use of coating equipment, a large amount of coating crystals or residues may accumulate on the machine after multiple coating processes. Currently available cleaning solutions for removing residual materials from wafers have poor solubility for high-Tg thermoplastic polymers remaining in the coating equipment and pipelines, causing a large accumulation of polymers on the machine and clogging of the drainage pipelines. After a period of time following the coating process, it is necessary to frequently shut down the machine for extended periods to clean the coating equipment with large amounts of cleaning solution, or to use a separate cleaning solution specifically designed for coating equipment, in order to effectively remove residues from the machine and pipelines.

[0012] Given that conventional cleaning agent compositions still have various drawbacks and limitations in their use, there is an urgent need to develop a cleaning agent composition and a method for using this cleaning liquid composition to remove thermoplastic polymer materials. Summary of the Invention

[0013] The purpose of this invention is to provide a cleaning agent composition that can effectively remove residual high Tg thermoplastic polymer materials on substrates and wafers, and the cleaning agent composition can also be used to clean coating equipment and pipelines.

[0014] The present invention provides a cleaning agent composition for removing thermoplastic polymer materials, comprising a cyclic acetal compound and an aprotic solvent, wherein the aprotic solvent comprises an aromatic ether compound and / or an lactone compound.

[0015] In one specific embodiment, the cleaning agent composition comprises, by total weight, 10 to 90 wt% of the cyclic acetal compound and 10 to 90 wt% of the aprotic solvent.

[0016] In one specific embodiment, the cleaning agent composition comprises, by total weight, 20 to 70 wt% of the cyclic acetal compound and 20 to 80 wt% of the aprotic solvent.

[0017] In a specific embodiment, the cyclic acetal compound may be a compound as shown in formula (I) or formula (II):

[0018]

[0019] Among them, R1, R2, R3, R4 and R5 are each independently H, C1-C6 alkyl, C6-C12 aromatic, C1-C6 hydroxyalkyl, hydroxyl or -R8-C(=O)OR9, wherein R8 is C1-C6 alkylene and R9 is C1-C6 alkyl.

[0020] In one specific embodiment, the cyclic acetal compound may comprise at least one of the group consisting of 1,3-dioxolane, 2-methyl-1,3-dioxolane, 4-methyl-1,3-dioxolane, 2,2-dimethyl-1,3-dioxolane, 2,2-diisopropyl-1,3-dioxolane, 2-phenyl-1,3-dioxolane, 4-methyl-2-phenyl-1,3-dioxolane, 1,3-dioxane, 2-methyl-1,3-dioxane, 2,2-dimethyl-1,3-dioxane, 5,5-dimethyl-1,3-dioxane, 2-isopropyl-5,5-dimethyl-1,3-dioxane, glycerol formaldehyde, acetone glycerol, and apple ester.

[0021] In one specific embodiment, the aromatic ether compound may be a compound as shown in R6-O-R7, wherein R6 and R7 are independently selected from C1-C4 alkyl, C1-C4 alkyl substituted with C6-C12 aromatic groups, and C6-C12 aromatic groups that are unsubstituted or substituted with C1-C4 alkyl groups.

[0022] In one specific embodiment, the aromatic ether compound may include at least one of the group consisting of anisole, phenethyl ether, propyl ether, phenylbutyl ether, isopropyl ether, dibenzyl ether, diphenyl ether, o-methyl anisole, m-methyl anisole, p-methyl anisole, benzyl ethyl ether, and phenyl benzyl ether.

[0023] In one specific embodiment, the endoamine compound may be a compound in which the hydrogen atom of the nitrogen atom of 2-pyrrolidone is substituted with a C1-C8 alkyl group.

[0024] In one specific embodiment, the endoamine compound may include at least one selected from the group consisting of N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-n-propyl-2-pyrrolidone, N-isopropyl-2-pyrrolidone, N-n-butyl-2-pyrrolidone, N-isobutyl-2-pyrrolidone, and N-tert-butyl-2-pyrrolidone.

[0025] In one specific embodiment, the cleaning agent composition may include at least one of the group consisting of corrosion inhibitors, oxidants, crosslinking agents, degradation inhibitors, interface modifiers, surfactants, defoamers, chelating agents, thickeners, dispersants, rust inhibitors, antioxidants, antibacterial agents, antifungal agents, polymerization inhibitors, and conductive auxiliaries.

[0026] The present invention further provides a method for removing thermoplastic polymer materials, comprising providing the cleaning agent composition of the present invention; and contacting the cleaning agent composition with residual thermoplastic polymer materials on a substrate, wafer, coating equipment or pipeline of coating equipment at 15 to 35°C to remove the thermoplastic polymer materials.

[0027] In one specific embodiment of the removal method, the thermoplastic polymer material comprises at least one of the group consisting of polyamide resin, polyimide resin, polyurethane resin, polyetherurethane resin, polyolefin resin, polyester resin, polybenzimidazole resin, polyphenylene ether resin, polyphenylene sulfide resin, polyetherketone resin, polyimide resin, polyetheretherketone resin, polyetherimide resin, and mixtures thereof, and / or at least one of the group consisting of cycloaerocarbon resin, epoxy resin, silicone resin, mixtures thereof, and polymers thereof.

[0028] In one specific embodiment of the removal method, the removal method involves contacting the cleaning agent composition with residual thermoplastic polymer materials on the substrate, wafer, coating equipment, or pipeline of the coating equipment, which may be achieved by immersion, soaking, coating, spin coating, spraying, or rinsing.

[0029] In one specific embodiment of the removal method, the removal method involves contacting the cleaning agent composition with residual thermoplastic polymer material on the substrate, wafer, coating equipment, or pipeline of the coating equipment for 3 seconds to 120 minutes.

[0030] The cleaning agent composition developed in this invention has excellent solubility for high Tg thermoplastic polymer materials. In addition to cleaning residual polymer materials on substrates and wafers after mechanical separation and laser separation, it can also clean coating equipment and pipelines at the same time. It can increase production and reduce the cost and manpower of coating equipment maintenance by eliminating the need for frequent machine shutdowns for cleaning equipment and pipelines. Simple Explanation of the Diagram

[0031] Figure 1 shows the residue on the crystal back after spin-coating a high Tg thermoplastic polymer bonding material, using the cleaning agent composition of Example 8.

[0032] Figure 2 shows the residue on the crystal back after spin-coating a high Tg thermoplastic polymer bonding material, using the cleaning agent composition of Comparative Example 1. Implementation

[0033] It is to be understood that any alteration of proportional relations or adjustment of magnitude in this specification, without affecting the efficacy that the invention can produce and the purposes that can be achieved, shall remain within the scope that the technical content disclosed in the invention can cover. Furthermore, all ranges and values ​​in this paper are included and mergeable. Any numerical value or point that falls within the range described herein, such as any integer that can be used as a minimum or maximum value to derive a lower range.

[0034] Where “include” or “include” a composition or step as described herein, other compositions or steps may be included separately and not to exclude such other component or other steps unless otherwise stated. The term “and / or” is shorthand used to narrate the combination of objects and to narrate the object as an alternative form of or. The term “or” is usually used in its meaning including “and / or” unless the context explicitly states otherwise.

[0035] The invention provides a cleaning agent composition comprising a cyclic acetal compound and an aprotic solvent, wherein, the aprotic solvent comprises an aromatic ether compound and / or a lactam compound.

[0036] The cyclic acetal compounds included in the cleaning agent compositions of the present invention may be compounds as shown in Formula (I) or Formula (II):

[0037]

[0038] Among them, R1, R2, R3, R4 and R5 are each independently H, C1-C6 alkyl, C6-C12 aromatic, C1-C6 hydroxyalkyl, hydroxyl, or -R8-C(=O)OR9, where, R8 is C1-C6 sub(ext)alkyl and R9 is C1-C6 alkyl.

[0039] In one specific embodiment, the cyclic acetal compound comprises selected from the 1,3-dioxopenta ring, 2-methyl-1,3-dioxopenta ring, 4-methyl-1,3-dioxopenta ring, 2,2-dimethyl-1,3-dioxopenta ring, 2,2-diisopropyl-1,3-dioxopenta ring, 2-phenyl-1,3-dioxopenta ring Groups composed of -phenyl-1,3-dioxopentane, 1,3-dioxane, 2-methyl-1,3-dioxane, 2,2-dimethyl-1,3-dioxane, 5,5-dimethyl-1,3-dioxane, 2-isopropyl-5,5-dimethyl-1,3-dioxane, glyceryl formaldehyde, acetone glycerides and at least olefins.

[0040] In one specific embodiment, the content of the cyclic acetal compound in the cleaning agent composition, based on the total weight of the composition, is between 10 and 90 wt% (weight percentage). Specifically, the content of the cyclic acetal compound may be 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 5 0, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, or 90 wt%, and any value between the above. In a specific embodiment, the content of the cyclic acetal compound is preferably between 20 and 70 wt%.

[0041] This invention utilizes cyclic acetal compounds to dissolve high-Tg thermoplastic polymers remaining on the back of a wafer after spin coating. Cyclic acetal compounds are cyclic structures formed by the dehydration reaction of aldehydes and ketones with diols under acid catalysis. Because the acetal molecular structure contains two oxygen atoms within the ring, it provides polarity to the compound, effectively dissolving various thermoplastic polymer bonding materials used in wafer fabrication processes. Furthermore, cyclic acetal compounds exhibit better stability than acyclic acetal compounds and are less prone to decomposition under many application conditions. In addition, cyclic acetal compounds are miscible with a variety of solvents, showing excellent miscibility with the aromatic ether compounds and lactones used in this invention.

[0042] The cleaning agent composition of the present invention may contain an aromatic ether compound as an aprotic solvent, which may be a compound as shown in R6-O-R7, wherein R6 and R7 are independently selected from C1-C4 alkyl, C1-C4 alkyl substituted with C6-C12 aromatic group, and C6-C12 aromatic group that is unsubstituted or substituted with C1-C4 alkyl.

[0043] In one specific embodiment, the aromatic ether compound comprises at least one selected from the group consisting of anisole, phenethyl ether, propyl ether, phenylbutyl ether, isopropyl ether, dibenzyl ether, diphenyl ether, o-methyl anisole, m-methyl anisole, p-methyl anisole, benzyl ethyl ether, and phenyl benzyl ether.

[0044] The cleaning agent composition of the present invention may contain an aprotic solvent, which may be an endo-amine compound, wherein the endo-amine compound may be a compound in which the hydrogen atom of the nitrogen atom of 2-pyrrolidone is substituted by a C1-C8 alkyl group.

[0045] In one specific embodiment, the endoamine compound comprises at least one selected from the group consisting of N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-n-propyl-2-pyrrolidone, N-isopropyl-2-pyrrolidone, N-n-butyl-2-pyrrolidone, N-isobutyl-2-pyrrolidone, and N-tert-butyl-2-pyrrolidone.

[0046] In one specific embodiment, the content of the aprotic solvent in the cleaning agent composition, based on the total weight of the cleaning agent composition, is between 10 and 90 wt%. Specifically, the content of the aprotic solvent can be 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77. 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89 or 90 wt%, and any value between the above. In a specific embodiment, the content of the aprotic solvent is preferably between 20 and 80 wt%.

[0047] In one specific embodiment, the content of the aromatic ether compound in the cleaning agent composition, based on the total weight of the cleaning agent composition, is between 10 and 90 wt%. Specifically, the content of the aromatic ether compound may be 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 5 0, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, or 90 wt%, and any value between the above. In a specific embodiment, the content of the aromatic ether compound is preferably between greater than 20 wt% and less than 85 wt%. In a specific embodiment, the content of the aromatic ether compound is preferably between 25 and 80 wt%.

[0048] In one specific embodiment, the content of the endoamine compound in the cleaning agent composition, based on the total weight of the cleaning agent composition, is between 10 and 90 wt%. Specifically, the content of the endoamine compound can be 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 5 0, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, or 90 wt%, and any value between the above. In a specific embodiment, the content of the endorphin compound is preferably between 25 and 70 wt%.

[0049] In specific embodiments of a nonprotic solvent containing both aromatic ether compounds and endoramine compounds, the total content of aromatic ether compounds and endoramine compounds is between 10 and 90 wt%.

[0050] Since commercially available cleaning agents are mostly designed for cleaning the wafer itself, they are not very effective at cleaning residual polymer materials splashed onto the coating machine during coating. This invention adds aromatic ether compounds and / or lactam compounds, which are non-protic solvents, to cyclic acetal compounds, so that the cleaning agent composition can not only dissolve residual polymer materials on the back of the wafer, but also clean the coating equipment and pipelines, preventing the residue and accumulation of polymer materials on the coating equipment.

[0051] The inventors have experimentally verified that, compared to using only cyclic acetal compounds, the cleaning agent composition containing aromatic ether compounds and / or lactamine compounds can improve the removal capacity of high Tg thermoplastic polymers. It has a good cleaning effect on the temporary bonding materials of high Tg thermoplastic polymers remaining on the substrate and wafer after mechanical separation and laser separation, and also has excellent cleaning ability for polymer materials accumulated on the machine and pipeline during the coating process. It does not require stopping the process for large-scale cleaning equipment and consuming a large amount of cleaning agent, nor does it require special replacement with machine-specific cleaning agents.

[0052] Without hindering the purpose of this invention, the cleaning agent composition of this invention may also contain other components as needed, such as components commonly used in cleaning agents, including but not limited to: other solvents, other additives such as corrosion inhibitors, oxidants, crosslinking agents, degradation inhibitors, interface modifiers, surfactants (such as anionic surfactants, cationic surfactants, nonionic surfactants, zwitterionic surfactants), defoamers, chelating agents, thickeners, dispersants, rust inhibitors, antioxidants (such as butylated hydroxyanisole, butylated hydroxytoluene), antibacterial agents, antifungal agents, polymerization inhibitors, conductive additives, etc. In a specific embodiment, the total content of other components in the cleaning agent composition, based on the total weight of the cleaning agent composition, may be from 10 ppm to 5 wt%, but is not limited thereto.

[0053] In this document, the terms "cleaning", "removal" and "washing" are used interchangeably to refer to a method of removing, peeling off, or washing away polymeric materials using the cleaning agent composition of the present invention.

[0054] The present invention further provides a method for removing thermoplastic polymer materials using the cleaning agent composition of the present invention, comprising: preparing the cleaning agent composition of the present invention to provide the cleaning agent composition of the present invention; and contacting the cleaning agent composition with residual thermoplastic polymer materials on a substrate, wafer, coating equipment or pipeline of coating equipment at 15 to 35°C to remove the thermoplastic polymer materials.

[0055] Specifically, a cyclic acetal compound is mixed with an aprotic solvent (aromatic ether compound and / or lactamine compound) in a specific ratio to prepare a cleaning agent composition. The mixing order is not particularly limited; the components can be mixed simultaneously or in any order, meaning all components can be mixed collectively; or a portion of the components can be mixed beforehand, followed by further mixing of the remaining components. Since most components in the cleaning agent composition of this invention are liquids, they can be easily mixed and prepared. In the preparation method of the cleaning agent composition of this invention, the specific ratio of each component can be set to be the same as the preferred content of each component in the cleaning agent composition of this invention described above.

[0056] The cleaning agent composition of this invention exhibits excellent cleaning ability at room temperature and can be used directly without heating after preparation. The unheated cleaning agent composition minimizes damage to the materials on the wafer and does not damage the adhesive tape on the stainless steel frame.

[0057] There are no particular limitations on the method of bringing the cleaning agent composition into contact with the substrate, wafer, coating equipment, or piping of the coating equipment. Methods such as immersion, dipping, coating, spin coating, spraying, or rinsing can be used to bring the cleaning agent composition into contact with residual thermoplastic polymer materials on the substrate, wafer, coating equipment, or piping of the coating equipment. For example, when cleaning wafers, spin coating can be used to remove residual polymer materials using centrifugal force; or nozzle spraying can be used to precisely clean the back and sides of the wafer, avoiding the cleaning agent composition from affecting the front side of the wafer. When cleaning coating equipment and piping, rinsing can be used to allow the cleaning agent composition to contact the machine and piping system over a large area; or, immersion can be used to focus on cleaning specific parts of the coating equipment to ensure sufficient contact time between the cleaning agent and the residual material to be removed, suitable for cleaning parts with complex structures.

[0058] The contact time between the cleaning agent composition of the present invention and the substrate, wafer, coating equipment, or pipeline of the coating equipment is not particularly limited, as long as it can effectively remove residual polymer materials. For example, when cleaning the substrate and wafer, the substrate and wafer can be periodically removed to check the cleaning and residue status of polymer materials. Alternatively, when cleaning the coating equipment and pipeline, the treatment can be intensified at areas with severe polymer material accumulation or blockage to extend the contact time with the cleaning agent composition. Contact time can range from 3 seconds to 120 minutes, such as 3 seconds, 4 seconds, 5 seconds, 10 seconds, 20 seconds, 30 seconds, 40 seconds, 50 seconds, 1 minute, 5 minutes, 10 minutes, 15 minutes, 20 minutes, 25 minutes, 30 minutes, 35 minutes, 40 minutes, 45 minutes, 50 minutes, 55 minutes, 60 minutes, 65 minutes, 70 minutes, 75 minutes, 80 minutes, 85 minutes, 90 minutes, 95 minutes, 100 minutes, 105 minutes, 110 minutes, 115 minutes, or 120 minutes, but is not limited to these.

[0059] The cleaning agent composition of the present invention can be applied to substrate materials such as glass, quartz, alumina, silicon, sapphire, ceramic substrates, silicon carbide, metals, etc., but is not limited thereto. The cleaning agent composition of the present invention can be applied to wafers or materials on wafers such as metals and their oxides, nitrides or silicides (e.g., copper, aluminum, titanium, lead, cadmium, indium, bismuth, nickel, germanium, zinc, tungsten, tantalum, iron, chromium, tin, silver, gold and their alloys), glass, quartz, silicon carbide, single-crystal silicon, polycrystalline silicon, silicon dioxide, silicon nitride, silicon carbide, silicon-germanium, gallium arsenide, aluminum gallium arsenide, aluminum indium gallium phosphide, indium gallium phosphide, gallium nitride, indium phosphide, organic materials, ceramics, prepregs, low-dielectric materials, resins, solder resists, etc., but is not limited thereto.

[0060] The cleaning agent of the present invention comprises thermoplastic polymers that are to be removed, including various materials that provide temporary bonding capabilities, preferably thermoplastic polymers that are resistant to high temperatures, with a Tg of 200°C or higher. The thermoplastic polymers may include at least one selected from the group consisting of polyamide resins, polyimide resins, polyurethane resins, polyetherurethane resins, polyolefin resins, polyester resins, polybenzimidazole resins, polyphenylene ether resins, polyphenylene sulfide resins, polyetherketone resins, polyimide resins, polyetheretherketone resins, polyetherimide resins, and mixtures thereof, and / or at least one selected from the group consisting of cycloaerocarbon resins, epoxy resins, silicone resins, mixtures thereof, and polymers thereof.

[0061] The following specific embodiments illustrate the implementation of the present invention. Those skilled in the art can easily understand the advantages and effects of the present invention from the content disclosed in this specification, and complete the present invention accordingly. The present invention can also be implemented or applied through other different embodiments, and the details in this specification can also be modified and changed based on different viewpoints and applications without departing from the spirit disclosed in the present invention. It should be understood that the following embodiments are merely examples of the content of the present invention, and not limitations on the scope of the present invention.

[0062] The cleaning agent compositions of Examples 1 to 19 and Comparative Examples 1 and 2 were prepared according to the formulations recorded in Tables 1 and 2: the components shown in Tables 1 and 2 were mixed to obtain the cleaning agent compositions; the dried high-Tg thermoplastic polymer solids (polyimide resin with Tg 200 to 400°C) on the coating equipment were collected; 0.5 g of the high-Tg thermoplastic polymer solids were immersed in 20 ml of the cleaning agent composition and allowed to stand at 25°C for 60 minutes; the cleaning solution was filtered, and the filter paper and the high-Tg thermoplastic polymer residue on the filter paper were dried and weighed using an electronic balance (Shimadzu, product number AUX320). The weight of the high-Tg thermoplastic polymer residue was obtained by subtracting the weight of the filter paper. The cleaning effect of the cleaning agent compositions of Examples 1 to 19 and Comparative Examples 1 and 2 was compared based on the high-Tg thermoplastic polymer residue.

[0063] Table 1 shows the composition, cleaning temperature, and cleaning effect on high Tg thermoplastic polymers used in Examples 1 to 19. The contents of cyclic acetal compounds, aromatic ether compounds, and lactam compounds shown in Table 1 are all expressed as weight percentages. The "Cleaning Effect on High Tg Thermoplastic Polymer Solids" column in the table is represented by four levels:

[0064] A: Residual thermoplastic polymer material <10wt%

[0065] B: Residual thermoplastic polymer material 10-50wt%

[0066] C: Residual thermoplastic polymer material 50-90wt%

[0067] D: Residual thermoplastic polymer materials >90wt%

[0068]

[0069] Table 2 shows the composition, cleaning temperature, and cleaning effect on high Tg thermoplastic polymers used in Comparative Examples 1 and 2. The cleaning agent compositions of the comparative examples in Table 2 do not contain aprotic solvents.

[0070]

[0071] The examples in Table 1 demonstrate that cleaning agent compositions using different concentrations and types of cyclic acetal compounds combined with aromatic ether compounds and / or lactamine compounds can achieve good cleaning results on high-Tg thermoplastic polymer solids. Specifically, in the examples where the cyclic acetal compound content is 20 to 70 wt% and the aprotic solvent content is 20 to 80 wt%, the residual amount of thermoplastic polymer is less than 10%, showing excellent cleaning performance.

[0072] Furthermore, Figures 1 and 2 show the appearance of the coating equipment after spin-coating high-Tg thermoplastic polymer bonding materials onto 200 12-inch wafers, cleaned with the cleaning agent compositions of Example 8 and Comparative Example 1, respectively. The coating equipment cleaned with the cleaning agent composition of Example 8 showed no significant thermoplastic polymer residue, and the pipelines were unblocked. In contrast, the coating equipment cleaned with the cleaning agent composition of Comparative Example 1 showed severe thermoplastic polymer residue, and the pipelines were blocked. Therefore, the cleaning agent composition of the present invention has excellent cleaning effects on the thermoplastic polymer residues on the wafers, as well as on the coating equipment and pipelines, without causing damage to the machine surface.

Claims

1. A cleaning agent composition for removing thermoplastic polymers, comprising a cyclic acetal compound and an aprotic solvent, wherein, The aprotic solvent system contains aromatic ether compounds and / or lactamine compounds.

2. The cleaning agent composition as described in claim 1, wherein, The cleaning agent composition comprises, by total weight, 10 to 90 wt% of the cyclic acetal compound and 10 to 90 wt% of the aprotic solvent.

3. The cleaning agent composition as described in claim 1, wherein, The cleaning agent composition comprises, by total weight, 20 to 70 wt% of the cyclic acetal compound and 20 to 80 wt% of the aprotic solvent.

4. The cleaning agent composition as described in claim 1, wherein, The cyclic acetal compound is a compound as shown in formula (I) or formula (II): wherein R1, R2, R3, R4 and R5 are each independently H, C1-C6 alkyl, C6-C12 aromatic, C1-C6 hydroxyalkyl, hydroxyl or -R8-C(=O)OR9, wherein R8 is C1-C6 alkylene and R9 is C1-C6 alkyl.

5. The cleaning agent composition as described in claim 4, wherein, The cyclic acetal compound comprises at least one selected from the group consisting of 1,3-dioxolane, 2-methyl-1,3-dioxolane, 4-methyl-1,3-dioxolane, 2,2-dimethyl-1,3-dioxolane, 2,2-diisopropyl-1,3-dioxolane, 2-phenyl-1,3-dioxolane, 4-methyl-2-phenyl-1,3-dioxolane, 1,3-dioxane, 2-methyl-1,3-dioxane, 2,2-dimethyl-1,3-dioxane, 5,5-dimethyl-1,3-dioxane, 2-isopropyl-5,5-dimethyl-1,3-dioxane, glycerol formaldehyde, acetone glycerol, and apple ester.

6. The cleaning agent composition as described in claim 1, wherein, The aromatic ether compounds are as shown in R6-O-R7, wherein R6 and R7 are independently selected from C1-C4 alkyl, C1-C4 alkyl substituted with C6-C12 aromatic groups, and C6-C12 aromatic groups that are unsubstituted or substituted with C1-C4 alkyl groups.

7. The cleaning agent composition as described in claim 6, wherein, The aromatic ether compound comprises at least one of the group consisting of anisole, phenethyl ether, propyl ether, phenylbutyl ether, isopropyl ether, dibenzyl ether, diphenyl ether, o-methyl anisole, m-methyl anisole, p-methyl anisole, benzyl ethyl ether, and phenyl benzyl ether.

8. The cleaning agent composition as described in claim 1, wherein, This endoamine compound is a compound in which the hydrogen atom of the nitrogen atom of 2-pyrrolidone is substituted with a C1-C8 alkyl group.

9. The cleaning agent composition as described in claim 8, wherein, The endo-amine compound comprises at least one selected from the group consisting of N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-n-propyl-2-pyrrolidone, N-isopropyl-2-pyrrolidone, N-n-butyl-2-pyrrolidone, N-isobutyl-2-pyrrolidone, and N-tert-butyl-2-pyrrolidone.

10. The cleaning agent composition as described in claim 1, wherein, The cleaning agent composition comprises at least one of the group consisting of corrosion inhibitors, oxidants, crosslinking agents, degradation inhibitors, interface modifiers, surfactants, defoamers, chelating agents, thickeners, dispersants, rust inhibitors, antioxidants, antibacterial agents, antifungal agents, polymerization inhibitors, and conductive auxiliaries.

11. A method for removing thermoplastic polymer materials, comprising: providing a cleaning agent composition as described in claim 1; and contacting the cleaning agent composition with residual thermoplastic polymer materials on a substrate, wafer, coating equipment, or pipeline of the coating equipment at a temperature of 15 to 35°C to remove the thermoplastic polymer materials.

12. The removal method as described in claim 11, wherein, The thermoplastic polymer material comprises at least one of the group consisting of polyamide resins, polyimide resins, polyurethane resins, polyetherurethane resins, polyolefin resins, polyester resins, polybenzimidazole resins, polyphenylene ether resins, polyphenylene sulfide resins, polyetherketone resins, polyimide resins, polyetheretherketone resins, polyetherimide resins, and mixtures thereof, and / or at least one of the group consisting of cycloaerobic resins, epoxy resins, silicone resins, mixtures thereof, and polymers thereof.

13. The removal method as described in claim 11, wherein, The cleaning agent composition is brought into contact with residual thermoplastic polymer materials on the substrate, wafer, coating equipment, or pipeline of the coating equipment by means of immersion, soaking, coating, spin coating, spraying, or rinsing.

14. The removal method as described in claim 11, wherein, The cleaning agent composition is brought into contact with residual thermoplastic polymer material on the substrate, wafer, coating equipment, or pipeline of the coating equipment for 3 seconds to 120 minutes.

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