Polyimide precursor, resin composition and polyimide

Abstract

To provide a polyimide precursor for producing polyimide which is usable in a semiconductor device packaging step and is removable by a solvent.SOLUTION: A polyimide precursor contains a reactant of a dianhydride and a diamine compound, wherein the diamine compound contains a first diamine compound and a second diamine compound, when the total molar number of the diamine compound is 100 mol%, the molar number of the first diamine compound with respect to the total molar number of the diamine compound is 20 mol% or more, the first diamine compound has a diamine residue having a structure of formula (III), and the second diamine compound has a diamine residue having a structure of formula (IV).SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a polyimide and a polyimide precursor for forming the polyimide, and more particularly to a polyimide used as a sacrificial protective layer between a semiconductor chip and an encapsulant layer, and a polyimide precursor for forming the polyimide. [Background technology]

[0002] As the demand for electronic components is increasing, they are also being required to be smaller and thinner. To meet this market trend, the integration density of chips packaged in two dimensions (2D) is insufficient, and so three-dimensional (3D) packaging technology is gradually being developed.

[0003] In the two-dimensional or three-dimensional packaging process, the chip surface is generally covered with a liquid molding compound (e.g., epoxy resin), and after the liquid molding compound is cured, the chip surface is scraped off to expose it for the next step of packaging.

[0004] However, since the molding compound before hardening is liquid, the molding compound before hardening is likely to seep into the chip along the wiring of the chip during processing, which may cause mold flash and contaminate the chip.

[0005] To solve this problem, in some packaging processes, the chip is first protected with a protective layer before packaging with molding compound, and then packaged with molding compound to prevent contamination of the chip.

[0006] The materials used for the protective layer are mostly permanent materials that are very difficult to remove, and are often resin compositions with photo- or thermosetting properties, such as epoxy resins, phenolic resins, and polyimide resins (e.g., solvent-resistant polyimides disclosed in Patent Document 1). However, these resins are difficult to remove in wet processes such as solvents after curing. Therefore, although the protective layer can protect the wiring underneath, it occupies a certain amount of space due to its volume, which affects the package size. In addition, polyimide resins are generally used in the packaging process of electrical equipment because they are generally resistant to high temperatures and have high strength, but polyimide resins that can withstand high temperatures during the curing process of molding compounds and are not affected by them are generally permanent materials or difficult to remove in wet processes after the packaging process. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Taiwan Patent Application Publication No. 201623373 Summary of the Invention [Problem to be solved by the invention]

[0008] An object of the present invention is to provide a polyimide that can be used in the packaging process of a semiconductor device and can be removed by a solvent, a polyimide precursor and a resin composition for producing the polyimide, the use of the polyimide in a sacrificial protective layer between a semiconductor chip and an encapsulant layer, and a semiconductor device containing the sacrificial protective layer. [Means for solving the problem]

[0009] In order to achieve the above object, the present invention provides A reaction product of a dianhydride and a diamine compound, the diamine compound includes a first diamine compound and a second diamine compound, and the molar number of the first diamine compound is 20 mol % or more with respect to the total molar number of the diamine compounds, where the total molar number of the diamine compounds is 100 mol %, and Contains repeat units of formula (I) and formula (II),

[0010] [ka]

[0011] In the formula, R1 and R3 are tetravalent tetracarboxylic acid residues, R2 is a divalent diamine residue of the first diamine compound, R4 is a divalent diamine residue of the second diamine compound, The first diamine compound has a structure of formula (III):

[0012] [ka]

[0013] The second diamine compound has a structure of formula (IV):

[0014] [ka]

[0015] In the formula, X1 is a divalent group containing at least one amide group, R5 and R6 are substituents other than hydrogen on the benzene ring; n1 and n2 are the numbers of substituents, each of which is in the range of 0 to 4; Each of R5 and R6 is independently selected from the group consisting of halogen, a C1-C3 alkyl group, and a C1-C3 halogenated alkyl group; X2 is a divalent group other than a single bond, R7 and R8 are substituents other than hydrogen on the benzene ring; m1 and m2 are the numbers of substituents, each ranging from 0 to 4, and the sum of m1 and m2 is at least 1; The present invention provides a polyimide precursor, wherein R7 and R8 are each independently selected from the group consisting of a hydroxy group, a halogen, a C1-C3 alkyl group, and a C1-C3 halogenated alkyl group, and R7 and R8 together have at least one hydroxy group.

[0016] The present invention also provides a method for producing a semiconductor device comprising the steps of: The present invention provides a resin composition comprising the above polyimide precursor and a solvent capable of dissolving the polyimide precursor.

[0017] The present invention also provides a method for producing a semiconductor device comprising the steps of: A dehydration cyclization product of the polyimide precursor according to claim 1, Contains repeating units of formula (X) and formula (Y)

[0018] [ka]

[0019] The present invention provides a polyimide having a structure comprising:

[0020] The present invention also provides a method for producing a semiconductor device comprising the steps of: The above polyimide is provided for use as a sacrificial protective layer between a semiconductor chip and an encapsulant layer.

[0021] The present invention also provides a method for producing a semiconductor device comprising the steps of: A semiconductor chip having wiring; a sacrificial protective layer covering at least a side surface of the wiring; a sealing material layer covering at least a peripheral side surface of the sacrificial protective layer in an annular shape; The sacrificial protective layer is made of the above polyimide. The present invention provides a semiconductor device including a sacrificial protective layer. Effect of the Invention

[0022] As described above, by the structural design of the polyimide precursor of the present invention, the polyimide, which is the dehydration cyclization product of the polyimide precursor, has the properties of a liquid-resistant molding compound and can be at least partially removed under predetermined conditions. Therefore, it can be used as a protective layer for protecting wiring in a chip packaging process and can be removed in a wet process after packaging is completed, making it highly versatile. [Brief description of the drawings]

[0023] [Figure 1] FIG. 1 is a diagram showing a process for using the polyimide of the present invention as a sacrificial protective layer in a packaging process for a semiconductor device. [Diagram 2] FIG. 13 is a diagram showing another removal flow of a sacrificial protective layer using the polyimide of the present invention in a packaging process of a semiconductor device. [Diagram 3] FIG. 2 is a cross-sectional view showing a state in which a portion of the sacrificial protective layer is removed after a packaging process of the semiconductor device. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0024] An object of the present invention is to provide a polyimide that can be used for a sacrificial protective layer between the chip and the molding compound in the packaging process of a semiconductor device.

[0025] The polyimide is a cyclodehydration product obtained by cyclodehydration of a polyimide precursor (polyamic acid), and contains repeating units of the formulae (X) and (Y).

[0026] [ka]

[0027] The polyimide precursor includes a reaction product obtained by reacting a dianhydride with a diamine compound, and may be a polyamic acid or a partially imidized polyamic acid.

[0028] The diamine compound includes a first diamine compound and a second diamine compound, and the molar number of the first diamine compound relative to the total molar number of the diamine compounds is 20 mol % or more, assuming that the total molar number of the diamine compounds is 100 mol %.

[0029] In some embodiments, the molar number of the first diamine compound is 20 mol% to 80 mol% relative to the total molar number of the diamine compounds, assuming that the total molar number of the diamine compounds is 100 mol%, and when used in combination with other diamine compounds, the arrangement of the polymer chains can be appropriately adjusted, making it easy to impart to the polyimide excellent properties of being able to withstand liquid molding compounds (hereinafter, abbreviated as liquid molding compound resistance) and excellent properties of being removable in a wet process (hereinafter, abbreviated as wet removability).

[0030] The molar ratio of the first diamine compound to the second diamine compound is preferably in the range of 0.25 to 5.00, more preferably in the range of 1.6 to 3.0. By keeping it within the above range, it is possible to further improve the wet removability while maintaining excellent liquid resistance of the molding compound.

[0031] The polyimide precursor comprises repeating units of formula (I) and formula (II).

[0032] [ka]

[0033] In the formula, R1 and R3 are tetravalent tetracarboxylic acid residues.

[0034] R2 is a divalent diamine residue from the first diamine compound.

[0035] R4 is a divalent diamine residue from the second diamine compound.

[0036] The tetracarboxylic dianhydride includes at least an aromatic tetracarboxylic dianhydride.

[0037] The molar ratio of the aromatic tetracarboxylic dianhydride to the total molar ratio of the dianhydrides is 30 mol % or more, where the total molar ratio of the dianhydrides is 100 mol %, thereby improving the adhesion of the polyimide to a chip having wiring.

[0038] In some embodiments, the aromatic tetracarboxylic dianhydride is selected from the group consisting of aromatic tetracarboxylic dianhydrides having 1 to 4 aromatic rings, but is not limited thereto.

[0039] Specifically, the aromatic tetracarboxylic dianhydride is 1,2,4,5-Benzenetetracarboxylic dianhydride (PMDA), Hard segment-containing tetracarboxylic dianhydrides such as 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA), 4,4'-oxydiphthalic anhydride (OPDA), Benzophenone-3,3',4,4'-tetracarboxylic dianhydride one-3,3',4,4'-tetracarboxylic dianhydride , B.T.D.A. 4,4'-(hexafluoroisopropylidene)diphthalic anhydride de, 6FDA), Soft segments such as 4,4'-(4,4'-isopropylidenediphenoxy)bis-(phthalic anhydride) [BPADA] The soft segment-containing tetracarboxylic acid dianhydride is preferably selected from the group consisting of tetracarboxylic acid dianhydrides containing a soft segment, tetracarboxylic acid dianhydrides containing a soft segment, and combinations thereof. When a large amount of the soft segment-containing tetracarboxylic acid dianhydride is used, the resulting polyimide has better adhesion to a chip having wiring, so that it is preferable to use a large amount of the soft segment-containing tetracarboxylic acid dianhydride.

[0040] In some embodiments, the dianhydride further comprises a cycloaliphatic tetracarboxylic dianhydride.

[0041] The alicyclic tetracarboxylic dianhydride is, for example, 1,2,3,4-Cyclobutanetetracarboxylic dianhydride (CBDA), The carboxylic acid dianhydride may be selected from the group consisting of, but is not limited to, 1,2,4,5-cyclohexanetetracarboxylic dianhydride (HPMDA), and combinations thereof.

[0042] When the dianhydride for synthesizing the polyimide precursor contains both the aromatic tetracarboxylic dianhydride and the alicyclic tetracarboxylic dianhydride, if the molar ratio of the aromatic tetracarboxylic dianhydride to the alicyclic tetracarboxylic dianhydride is greater than 3 / 7, the polyimide obtained thereby will have better adhesion to a chip having wiring, and therefore it is preferable to set the molar ratio of the aromatic tetracarboxylic dianhydride to the alicyclic tetracarboxylic dianhydride to be greater than 3 / 7.

[0043] The first diamine compound has a structure of formula (III).

[0044] [ka]

[0045] In the formula, X1 is a divalent group containing at least one amide group, R5 and R6 are substituents other than hydrogen on the benzene ring, n1 and n2 are the numbers of substituents, each of which is in the range of 0 to 4, and R5 and R6 are each independently selected from the group consisting of halogen, a C1-C3 alkyl group, and a C1-C3 halogenated alkyl group.

[0046] Preferably, the first diamine compound has a structure of formula (III-1) or formula (III-2).

[0047] [ka]

[0048] In the formula, R9 is a substituent other than hydrogen on the benzene ring, n3 is the number of substituents and ranges from 0 to 4, each R9 is independently selected from the group consisting of halogen, C1-C3 alkyl groups, and C1-C3 halogenated alkyl groups, a1 is in the range of 0 to 3, and a2 is in the range of 1 to 3.

[0049] In some embodiments, R9 is selected from the group consisting of C1-C3 halogenated alkyl groups.

[0050] Specifically, the first diamine compound is, for example, 4,4'-Diaminobenzanilide (DABA), N,N'-(2,2'-bis(trifluoromethyl)-[1,1'-biphenyl]-4,4'-diyl)bis(4-aminobenzamide) ifluoromethyl)-[1,1'-biphenyl]-4,4'-diyl)bis(4-aminobenzamide), AB-TFMB), The compound is selected from the group consisting of, but not limited to, N,N'-bis(4-aminophenyl)benzene-1,4-dicarboxamide (DATA) and combinations thereof.

[0051] In some embodiments, the first diamine compound is preferably selected from a divalent group of monoamide group, X1. In particular, when the benzene ring in the first diamine compound is all hydrogen and there is no other substituent (i.e., n1, n2 and a1 are all 0), it is more preferable that X1 is a divalent group of monoamide group, such as DABA. This type of diamine compound has a smaller steric hindrance, so that when used in combination with the second diamine compound, the distance between molecules can be made appropriate, a regular stack structure can be formed, and hydrogen bonds between amide groups or between amide groups and hydroxyl groups can more easily interact with each other. Therefore, when undergoing high and low temperature changes in the packaging process, the liquid molding compound (e.g., epoxy resin composition) is less likely to penetrate, and at the same time, it has wet removability, so it exhibits excellent liquid molding compound resistance and excellent wet removability.

[0052] The second diamine compound has the structure of formula (IV).

[0053] [ka]

[0054] In the formula, X2 is a divalent group other than a single bond, R7 and R8 are substituents other than hydrogen on the benzene ring, m1 and m2 are the numbers of substituents, each of which is in the range of 0 to 4 and the sum of m1 and m2 is at least 1, R7 and R8 are each independently selected from the group consisting of a hydroxy group, a halogen, a C1-C3 alkyl group, and a C1-C3 halogenated alkyl group, and R7 and R8 together have at least one hydroxy group.

[0055] In some embodiments, each of R7 and R8 has at least one hydroxy group.

[0056] In some embodiments, X2 is a divalent group other than a single bond and not having a benzene ring.

[0057] In some embodiments, X2 is a disubstituted methylene group. The substituent of the disubstituted methylene group may be specifically a halogenated alkyl group or an alkyl group, and is preferably -CH3 or -CF3.

[0058] Specifically, the second diamine compound is, for example, 2,2-Bis(3-amino-4-hydroxyphenyl)hexafluoropropane (BisAPAF), 2,2-Bis(3-amino-4-hydroxylphenyl)propane (BAP), The sulfonyl bis(2-aminophenol) (BAS) and combinations thereof are selected from the group consisting of, but not limited to, 4,4'-sulphonylbis(2-aminophenol) (BAS).

[0059] As long as the effect of the present invention is not adversely affected, the diamine compound may further contain other diamine compounds, among which a third diamine compound may be included.

[0060] The third diamine compound is a diamine compound having a soft segment, and the number of moles of the third diamine compound relative to the total number of moles of the diamine compounds is 30 mol % or less, assuming that the total number of moles of the diamine compounds is 100 mol %.

[0061] The soft segment has one or more segments formed by groups prone to intramolecular rotation in its structure and is represented by formula (V).

[0062] [ka]

[0063] In the formula, Y1 to Y3 are selected from the group consisting of an ether group, a siloxane group, an alkylene group, and an alicyclic group, and b1+b2+b3>0.

[0064] In some embodiments, the soft segment of the third diamine compound is a siloxane-containing divalent group or an ether-containing divalent group, such as a dimethylsiloxane repeat unit, an ethylene oxide repeat unit, or a propylene oxide repeat unit.

[0065] In order to maintain excellent resistance to liquid molding compounds, excellent wet removability and excellent adhesion, the molecular weight of the third diamine compound is preferably 2000 or less.

[0066] Specifically, the third diamine compound is, for example, Poly(propylene glycol) diamine (O,O'-Bis(2-aminopropyl)polypropyleneglycol), 1,3-bis(3-aminopropyl)tetramethyldisiloxane (3,3'-(1,1,3,3-tetramethyldisiloxane-1,3-diyl)bispropylamine), At least one selected from the group consisting of fatty dimer diamines (FDDs) containing linear aliphatic side chains, but is not limited thereto.

[0067] The FDD has the structure of formula (VI).

[0068] [ka]

[0069] In the formula, Y4 can be a divalent hydrocarbon group, a benzene ring, an alicyclic compound, a cycloalkene, or the like; M1 and M2 can be a divalent hydrocarbon group, an ether group, a siloxane group, or the like; b4 to b5 are the number of repeating units and are greater than 0 and not greater than 100; M3 and M4 can be hydrogen, a divalent hydrocarbon group, an ether group, a siloxane group, or the like; and b6 to b7 are the number of repeating units of M3 and M4 selected from the group consisting of divalent hydrocarbon groups, ether groups, siloxane groups, and the like, and are greater than 0 and not greater than 100.

[0070] In some embodiments, the diamine compound may further include other types of diamine compounds.

[0071] The number of moles of the other diamine compounds is 10 mol % or less relative to the total number of moles of the diamine compounds, where the total number of moles of the diamine compounds is 100 mol %.

[0072] Specifically, the other diamine compound is an aromatic diamine compound other than the first diamine compound, the second diamine compound, and the third diamine compound, for example: 4,4'-diaminodiphenyl ether ether, ODA), 4,4'-Diaminodiphenyl sulfone (DDS), 2,2-Bis[4-(4-aminophenoxy)phenyl] hexafluoropropane (HFBAPP), 9,9-Bis(4-aminophenyl)fluorene (FDA), 2-(4-Aminophenyl)benzoxazol-5-amine (2-(4-Amino-P henyl)-Benzooxazol-5-Ylamine, APABO), Bis(4-aminophenyl) terephthalate (ABHQ), 2,2'-Bis(trifluoromethyl)benzidine (TFMB), 1,3-Bis(4-aminophenoxy)benzene (TPE-R), 3,3'-Dihydroxybenzidine (HAB), but is not limited to this.

[0073] More specifically, the synthesis of the polyimide is carried out by first dissolving a selected dianhydride and a diamine compound in a solvent, controlling the molar ratio of the diamine compound and the dianhydride to within the range of about 0.97:1 to 1.03:1, reacting the dianhydride and the diamine compound at a predetermined reaction temperature to form a polyimide precursor, and obtaining a resin composition containing the solvent and a polyimide precursor that can be dissolved in the solvent. After obtaining the resin composition, the polyimide precursor in the resin composition is dehydrated by high-temperature heating or a chemical catalyst method, and the polyimide is obtained by carrying out a dehydration cyclization reaction.

[0074] The solvent may be any organic solvent capable of dissolving the reactants and polymerizable products, and there are no limitations on the specific solvent or combination.

[0075] In some embodiments, the solvent is selected from the group consisting of amide-based solvents, cyclic amide-based solvents, ester-based solvents, ether-based solvents, and combinations thereof.

[0076] Specifically, the solvent is, for example, N,N-Diethylformamide (DEF), N,N-Dimethylformamide (DMF), N,N-Dimethylacetamide (DMAC), N-Methyl-ε-caprolactam, Dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP), γ-butyrolactone (GBL), Propylene glycol methyl ether acetate (PGMEA), Tetramethylurea, Hexamethylphosphoric triamide (HMPA), Pyridine, 1-methoxy-2-propanol, The organic solvent is selected from the group consisting of n-butyl acetate, etc. As long as the reactants and polymers are not precipitated, the above organic solvents can be used alone or in combination of two or more.

[0077] The polyimide of the present invention has excellent resistance to liquid molding compounds and can be removed, so that the polyimide can be used to protect the chip during the packaging process to prevent the chip from being contaminated by the liquid molding compound during the high-temperature packaging process. After the packaging process, the polyimide can be stably present to protect the chip, and can also be used for dry etching, such as O2 plasma or CF4 plasma, or for example, by using an inorganic base (such as sodium hydroxide) or an organic base (such as sodium hydroxide). Tetramethylammonium hydroxide (TMAH), A wet process using a cleaning solution such as monoethanolamine (MEA) can then be partially or completely removed under predetermined conditions to expose the protected chip wiring, allowing greater flexibility and versatility in the design of electrical connections in the downstream wiring of the chip.

[0078] The polyimides of the present invention can also be used as a sacrificial protective layer between the semiconductor chip and the encapsulant layer.

[0079] As a result, the sacrificial protective layer-containing semiconductor device of the present invention includes a semiconductor chip having wiring, a sacrificial protective layer covering at least the side surfaces of the wiring, and a sealing material layer covering at least the side surfaces of the sacrificial protective layer in a ring shape, and the sacrificial protective layer is composed of the polyimide of the present invention.

[0080] FIG. 1 is a diagram showing a process flow in which the polyimide of the present invention is used as a sacrificial protective layer in the packaging process of a semiconductor device.

[0081] FIG. 2 is a diagram showing a flow of another embodiment of removing a sacrificial protective layer using the polyimide of the present invention in a packaging process for a semiconductor device.

[0082] FIG. 3 is a cross-sectional view showing a state in which a part of the sacrificial protective layer has been removed after a packaging process of the semiconductor device.

[0083] Specifically, referring to FIG. 1, the polyimide of the present invention is used as a sacrificial protective layer 200 between the wiring 101 of a semiconductor chip 100 and liquid molding compound in the packaging process of a semiconductor device.

[0084] When the polyimide of the present invention is used as a sacrificial protective layer 200 between the semiconductor chip 100 and the liquid molding compound, before packaging with a known liquid molding compound, a resin composition containing the polyimide precursor of the present invention is first applied to the surface of the semiconductor chip 100 containing the wiring 101, and then a high-temperature reaction is carried out to convert the polyimide precursor in the resin composition into After high temperature cyclodehydration and solvent removal, a sacrificial protective layer 200 of liquid-resistant molding compound is formed on the surface of the semiconductor chip 100, which is made of polyimide resin and completely covers the wiring 101.

[0085] Therefore, the semiconductor chip 100 on which the sacrificial protective layer 200 is formed is then cut into different sizes and transferred to another package substrate 102, and then the semiconductor chip 100 is packaged by covering the surface of the sacrificial protective layer 200 with a liquid molding compound to form an encapsulant layer 300, thereby forming a packaged component. Alternatively, after the sacrificial protective layer 200 is formed, the encapsulant layer 300 is first formed to cover the surface of the sacrificial protective layer 200, and then the encapsulant layer 300 is cut and transferred to another package substrate 102 to form a packaged component. FIG. 1 illustrates an example of a method in which the sacrificial protective layer 200 is formed, cut along a cut line indicated by a dashed line, transferred to another package substrate 102, and then the encapsulant layer 300 is formed.

[0086] The semiconductor chip 100 is protected by the sacrificial protective layer 200, which prevents conventional liquid molding compounds from seeping along the wiring 101 and contaminating the semiconductor chip 100.

[0087] In addition, when further stacking and packaging multiple chips, the encapsulant layer 300 and the sacrificial protective layer 200 covering the surface of the cut and transferred semiconductor chip 100 are scraped off so that a portion of the sacrificial protective layer 200 on the top surface of the wiring 101 remains (as shown in FIG. 1, the encapsulant layer 300 covers the side peripheral surface of the sacrificial protective layer 200 in an annular shape), and then, in a wet (or dry) process, a portion of the sacrificial protective layer 200 on the top surface of the wiring 101 is removed (at that time, the top surface of the encapsulant layer 300 and the top surface of the sacrificial protective layer 200 are substantially flush with each other), or the encapsulant layer 300 and the sacrificial protective layer 200 covering the surface of the semiconductor chip 100 are The top surface of the wiring 101 is removed to be exposed (as shown in FIG. 2, at this time the top surface of the encapsulant layer 300 is substantially flush with the top surface of the sacrificial protective layer 200). Thus, when electrically connecting to the outside, the remaining sacrificial protective layer 200 covering the side surface 1011 of the wiring 101 not only remains stable to protect the wiring 101, but the polyimide of the present invention can also be further removed by wet or dry process. Therefore, if necessary, the remaining sacrificial protective layer 200 covering the side surface 1011 of the wiring 101 can be removed to further expose the side surface 1011 of the wiring 101, thereby further improving the flexibility of designing the electrical connection of the wiring 101.

[0088] 1 and 2 illustrate an example in which the sacrificial protective layer 200 is completely removed after packaging to expose the side surface 1011 of the wiring 101. However, in actual implementation, only a portion of the sacrificial protective layer 200 may be removed as necessary, with reference to FIG. 3. When a portion of the sacrificial protective layer 200 is removed, the top surface of the remaining sacrificial protective layer 200a is lower than the top surface of the encapsulant layer 300.

[0089] The following examples (E1 to E23) and comparative examples (CE1 to CE8) are used to explain the types and proportions of dianhydrides and diamine compounds used in different polyimides, and the properties of the polyimides of the present invention are further explained based on the evaluation results of those polyimides.

[0090] The structural formulas, chemical names (abbreviations), and CAS registry numbers of the dianhydrides and diamine compounds used in these Examples (E1 to E23) and Comparative Examples (CE1 to CE8) are shown in Tables 1 and 2.

[0091] TIFF0007659588000012.tif246170

[0092] TIFF0007659588000013.tif129170

[0093] TIFF0007659588000014.tif117170

[0094] Polyimide manufacturing conditions: In Examples E1 to E23 and Comparative Examples CE1 to CE8, the molar ratio of the diamine compound used to the dianhydride used was all controlled to 0.98:1, and the reaction was carried out under the same reaction conditions. Reaction conditions: A thermometer, nitrogen inlet and stirring device were installed in a 1L reactor. First, 155g of N,N-diethylformamide (hereinafter referred to as "DEF") was added to the reactor and stirred at 200 rpm. Then, diamine compounds with different molar ratios were mixed with 155g of DEF and added to the reactor. After the diamine compounds were completely dissolved, dianhydrides and 80g of DEF were added to the reactor.

[0095] The mixture was stirred at room temperature for 16 hours to react the diamine compound with the dianhydride to form a polyimide precursor (polyamic acid), and then a resin composition containing the polyimide precursor and DEF was formed. DEF was further added to the resin composition to dilute the resin composition to a viscosity (25°C) of 4000cP-6000cP, to obtain 500g of a resin composition with a solid content of 18wt%-23wt%.

[0096] The resin composition was applied to a glass substrate by spin coating to form a coating film on the surface of the glass substrate. The spin coating was performed at a rotation speed sufficient to form a film having a thickness of about 20 μm.

[0097] Finally, the coating film was preheated at 50°C for 5 minutes and at 90°C for 5 minutes, and then cured and heated at 230°C for 60 minutes to cause a dehydration and cyclization reaction of the polyimide precursor, thereby forming a polyimide film (corresponding to the sacrificial protective layer 200 in Figure 1) made of polyimide on the glass substrate.

[0098] The polyimide films obtained in Examples E1 to E23 and Comparative Examples CE1 to CE8 were subjected to a liquid molding compound resistance test simulating a packaging process, a wet removability test, and an adhesion (cross-cut) test. Liquid Molding Compound Resistance Test: Since the encapsulant layer is obtained by applying liquid molding compound and then curing it under high temperature (approximately 120℃ to 180℃) conditions, the liquid molding compound resistance test simulates the resistance of polyimide to liquid molding compound (LMC) at high temperatures. Test method for liquid resistance of molding compounds: Liquid molding compound (LMC) was dropped onto the polyimide film formed on the glass substrate obtained in each Example and Comparative Example, and the output pressure was 10 kgw / cm 2 While pressing the liquid molding compound with a machine, the liquid molding compound was heated to 120°C and held for 10 minutes, then heated to 230°C and held for 1 hour to cure the liquid molding compound (LMC) into an encapsulant layer, thereby completing the test for 120°C liquid molding compound resistance.

[0099] The liquid molding compound used was an epoxy resin-based sealing material (NAGASE CHEMTEX, product name: EPOXY RESIN T693 / R4000). Liquid molding compound resistance rating: After the liquid molding compound resistance test is completed, the glass substrate is observed from the opposite side of the polyimide film for any deterioration. If the polyimide film is mixed with the liquid molding compound or cracks are formed, it is judged as failing (×), and if no abnormality is found, it is judged as passing (◯). Wet Removability Test: Wet removability testing is performed to verify the removability characteristics of the polyimide after packaging. Wet Removability Test Method: Using the samples that had been tested for resistance to 120°C liquid molding compound, the encapsulant layer formed on the surface of the sample was scraped off until the polyimide film was exposed, and the sample was then immersed in a developer (Taiwan Jayray Hi-Tech Co., Ltd., product name: 920) at 50°C to evaluate the wet removability of the polyimide film. Wet Removability Rating: After visually confirming that the polyimide film has been completely removed, the substrate is taken out and the time required for complete removal is recorded.

[0100] ×: Not soluble △: It took more than 10 minutes to remove everything 〇: Time taken to completely remove the material is within 6 to 10 minutes ◎: Time taken to completely remove the material was less than 6 minutes Cross-cut test (checkerboard test): A cross-cut test is carried out to confirm the toughness of the polyimide film surface and its adhesion to the substrate, and to evaluate the operability in the cutting process of the polyimide film. Cross-cut test method: Based on ASTM D3359 Standard Test Method for Measuring Adhesion by Tape Test The polyimide films obtained in each of the Examples and Comparative Examples were measured for toughness of the film surface and adhesion to the substrate.

[0101] Tape used: 3M 610 cross-cut test tape Cross-cut test rating:

[0102] TIFF0007659588000015.tif83170

[0103] In Examples E1 to E23 and Comparative Examples CE1 to CE8, the types and proportions of the diamine compounds and dianhydrides used, and the evaluation results of the polyimide films obtained are shown in Tables 3 to 6.

[0104] In addition, since the molar ratio of the diamine compound and the dianhydride used was 0.98:1, for ease of understanding, the amount of the diamine compound used in Tables 3 to 6 is expressed in moles per 98 moles of the diamine compound, and the amount of the dianhydride used in Tables 3 to 6 is expressed in moles per 100 moles of the dianhydride. For example, when the total amount of the diamine compounds used is 0.98 moles, the amount of the first diamine compound in E1 used is 0.20 moles, and the amount of the dianhydride used is 0.10 moles. For a total dose of 1.00 mole, the amount of ODPA used in E1 is 0.80 mole.

[0105] TIFF0007659588000016.tif117170

[0106] TIFF0007659588000017.tif119170

[0107] According to the results shown in Tables 3 and 4, when the polyimide does not simultaneously have a structure based on the first diamine compound and the second diamine compound in the structure (Table 4, CE2 to CE8), the polyimide cannot simultaneously satisfy the liquid molding compound resistance and wet removability required when used as a sacrificial protective layer for electronic devices.

[0108] According to CE1, even if the polyimide structure contains a structure of a first diamine compound and a structure of a second diamine compound at the same time, when the amount of the first diamine compound used is insufficient, the wet removability is improved, but the liquid molding compound resistance is poor.

[0109] In addition, according to the results shown in Table 3, when the polyimide structure simultaneously contains a structure of a first diamine compound and a structure of a second diamine compound, and the total mole number of the diamine compounds is taken as 100 mol%, and the mole number of the first diamine compound used is 20 mol% or more relative to the total mole number of the diamine compounds, the polyimide simultaneously has excellent resistance to liquid molding compounds and excellent wet removability, and is therefore suitable for a sacrificial protective layer of an electronic device, and can achieve protection of the chip from being affected by the liquid molding compound during the packaging process.

[0110] TIFF0007659588000018.tif120170

[0111] According to the results shown in Table 5, the toughness, adhesion and wet removability of the polyimide film can be appropriately adjusted by adding an alicyclic acid dianhydride. However, when the molar number of the alicyclic acid dianhydride added exceeds 30 mol % relative to the total molar number of the dianhydrides, taking the total molar number of the dianhydrides as 100 mol %, the adhesion of the obtained polyimide to the substrate decreases.

[0112] In addition, according to the results shown in Table 5, when the molar ratio of the first diamine compound is high (70 to 80), the toughness and adhesion of the polyimide can be adjusted by adding other types of diamine compounds or alicyclic acid dianhydrides.

[0113] TIFF0007659588000019.tif146170

[0114] According to the results shown in Table 6, the wet removability of the polyimide of the present invention can be improved by adding a third diamine compound having a soft segment. When the soft segment of the third diamine compound is a plurality of ether groups (polyether groups) or alicyclic groups (E-19 to E-23), in addition to the wet removability, the toughness and adhesion of the polyimide film can also be adjusted, making it more suitable for the packaging process and the cutting process after packaging.

[0115] According to the above description, by the structural design of the polyimide precursor of the present invention, the polyimide of the present invention has a structure of a first diamine compound having an amide group and a structure of a second diamine compound having a hydroxyl group, and the steric hindrance is smaller, so that the distance between molecules can be made appropriate, and a regular stack structure can be formed, and the hydrogen bond interaction between the amide groups or between the amide groups and the hydroxyl groups is easy to occur, so that excellent stack density can be achieved. Therefore, the polyimide of the present invention has excellent liquid molding compound resistance, and at the same time, by combining the ratio of the amide groups and the hydroxyl groups of the polymer, the wet removability of the polyimide can be improved while maintaining excellent liquid molding compound resistance.

[0116] In addition, the combination of an aromatic acid dianhydride and an alicyclic acid dianhydride gives the polyimide not only superior wet removability but also appropriate film toughness and adhesion, which improves adhesion to the chip (substrate) in the packaging process, further enhances resistance to liquid molding compounds, and makes it suitable for the subsequent cutting process.

[0117] Furthermore, since the polyimide of the present invention has wet removability, it can be removed after packaging is completed, and therefore the adjustability in subsequent processes is high, making it more versatile.

[0118] Although the preferred embodiments of the present invention have been described above, the present invention is not limited thereto, but is intended to encompass all modifications and equivalent configurations as various configurations falling within the spirit and scope of the broadest interpretation. The present invention includes the following aspects. [Section 1] A reaction product of a dianhydride and a diamine compound, the diamine compound includes a first diamine compound and a second diamine compound, and the molar number of the first diamine compound is 20 mol % or more with respect to the total molar number of the diamine compounds, where the total molar number of the diamine compounds is 100 mol %, and Contains repeat units of formula (I) and formula (II), [ka] In the formula, R1 and R3 are tetravalent tetracarboxylic acid residues, R2 is a divalent diamine residue of the first diamine compound, R4 is a divalent diamine residue of the second diamine compound, The first diamine compound has a structure of formula (III): [ka] The second diamine compound has a structure of formula (IV): [ka] In the formula, X1 is a divalent group containing at least one amide group, R5 and R6 are substituents other than hydrogen on the benzene ring; n1 and n2 are the numbers of substituents, each of which is in the range of 0 to 4; Each of R5 and R6 is independently selected from the group consisting of halogen, a C1-C3 alkyl group, and a C1-C3 halogenated alkyl group; X2 is a divalent group other than a single bond, R7 and R8 are substituents other than hydrogen on the benzene ring; m1 and m2 are the numbers of substituents, each ranging from 0 to 4, and the sum of m1 and m2 is at least 1; A polyimide precursor, wherein R7 and R8 are each independently selected from the group consisting of a hydroxy group, a halogen, a C1-C3 alkyl group, and a C1-C3 halogenated alkyl group, and R7 and R8 together have at least one hydroxy group. [Section 2] The first diamine compound has a structure represented by formula (III-1) or (III-2): [ka] In the formula, R9 is a substituent other than hydrogen on the benzene ring; n3 is the number of substituents and ranges from 0 to 4; Each R9 is independently selected from the group consisting of halogen, a C1-C3 alkyl group, and a C1-C3 halogenated alkyl group; a1 is in the range of 0 to 3, 2. The polyimide precursor according to item 1, wherein a2 is in the range of 1 to 3. [Section 3] Item 2. The polyimide precursor according to item 1, wherein X2 contains a disubstituted methylene group or a disubstituted sulfonyl group. [Section 4] 2. The polyimide precursor according to item 1, wherein the molar number of the first diamine compound is 20 mol % to 80 mol % relative to the total molar number of the diamine compounds, where the total molar number of the diamine compounds is 100 mol %. [Section 5] The diamine compound further includes a third diamine compound which is a diamine compound having a soft segment, 2. The polyimide precursor according to item 1, wherein the number of moles of the third diamine compound is 30 mol % or less relative to the total number of moles of the diamine compounds, where the total number of moles of the diamine compounds is 100 mol %. [Section 6] 6. The polyimide precursor according to item 5, wherein the soft segment is selected from the group consisting of at least one ether group, at least one siloxane group, and at least one alicyclic group. [Section 7] 2. The polyimide precursor according to item 1, wherein the dianhydride comprises an aromatic tetracarboxylic dianhydride having one to four aromatic rings, and the number of moles of the aromatic tetracarboxylic dianhydride is more than 30 mol % relative to the total number of moles of the dianhydrides, where the total number of moles of the dianhydrides is taken as 100 mol %. [Section 8] Item 8. The polyimide precursor according to item 7, wherein the dianhydride further comprises an alicyclic tetracarboxylic acid dianhydride. [Section 9] Item 2. A resin composition comprising the polyimide precursor according to item 1 and a solvent capable of dissolving the polyimide precursor. [Section 10] 10. The resin composition according to item 9, wherein the solvent is selected from the group consisting of amide solvents, cyclic amide solvents, ester solvents, ether solvents, and combinations thereof. [Section 11] Item 1 is a dehydration cyclization product of the polyimide precursor according to item 1, Contains repeating units of formula (X) and formula (Y) [ka] A polyimide characterized by: [Section 12] Item 12. The polyimide according to item 11, which is used as a sacrificial protective layer between a semiconductor chip and an encapsulant layer. [Section 13] A semiconductor chip having wiring; a sacrificial protective layer covering at least a side surface of the wiring; a sealing material layer covering at least a peripheral side surface of the sacrificial protective layer in an annular shape; Item 12. A sacrificial protective layer-containing semiconductor device, characterized in that the sacrificial protective layer is made of the polyimide described in item 11. [Section 14] the sacrificial protective layer completely covers the wiring; Item 14. The sacrificial protective layer-containing semiconductor device according to item 13, wherein the encapsulant layer covers a surface of the sacrificial protective layer. [Section 15] the sacrificial protective layer covers a side surface of the wiring so that a top surface of the wiring is exposed, and the sealing material layer covers a side surface of the sacrificial protective layer, Item 14. The semiconductor device including a sacrificial protective layer according to item 13, wherein the top surface of the encapsulant layer is lower than or flush with the top surface of the sacrificial protective layer. [Industrial Applicability]

[0119] The polyimide precursors of the present invention can be formed into polyimides of the present invention, which are suitable for use as sacrificial protective layers in packaging processes. [Explanation of symbols]

[0120] 100 Semiconductor Chips 101 Wiring 102 Package Substrate 200, 200a Sacrificial protective layer 300 Encapsulant layer

Claims

1. A reaction product of a dianhydride and a diamine compound, The dianhydride does not include a compound represented by formula (A) and a compound represented by formula (B), 【Chemistry 1】 the molar ratio of the diamine compound to the dianhydride is in the range of 0.97:1 to 1.03:1; the diamine compound includes a first diamine compound and a second diamine compound, and the number of moles of the first diamine compound is 20 mol % or more relative to the total number of moles of the diamine compounds, where the total number of moles of the diamine compounds is 100 mol %, and Contains repeat units of formula (I) and formula (II), 【Chemistry 2】 In the formula, R1 and R3 are tetravalent tetracarboxylic acid residues, R2 is a divalent diamine residue from the first diamine compound, R4 is a divalent diamine residue from the second diamine compound, The first diamine compound has a structure of formula (III): 【Chemistry 3】 The second diamine compound has a structure of formula (IV): 【Chemistry 4】 In the formula, X １ is a divalent group containing at least one amide group, R ５ and R ６ is a substituent other than hydrogen on the benzene ring, n1 and n2 are the number of substituents, each ranging from 0 to 4; R ５ and R ６ Each of the groups is independently a halogen, C １ ~C ３ Alkyl group, C １ ~C ３ is selected from the group consisting of halogenated alkyl groups; X ２ is a divalent group other than a single bond, R ７ and R ８ is a substituent other than hydrogen on the benzene ring, m1 and m2 are the number of substituents, each ranging from 0 to 4, and the sum of m1 and m2 is at least 1; R ７ and R ８ Each of the groups is independently a hydroxy group, a halogen, C １ ~C ３ Alkyl group, C １ ~C ３ halogenated alkyl groups, and R ７ and R ８ A polyimide precursor characterized by having at least one hydroxy group in total.

2. The first diamine compound has a structure represented by formula (III-1) or (III-2): 【Chemistry 5】 In the formula, R ９ is a substituent other than hydrogen on the benzene ring, n3 is the number of substituents, ranging from 0 to 4; R ９ Each of the groups is independently a halogen, C １ ~C ３ Alkyl group, C １ ~C ３ is selected from the group consisting of halogenated alkyl groups; a1 is in the range of 0 to 3; 2. The polyimide precursor according to claim 1, wherein a2 is in the range of 1 to 3.

3. X ２ The polyimide precursor according to claim 1 , wherein the alkyl group is a di-substituted methylene group or a di-substituted sulfonyl group.

4. The polyimide precursor according to claim 1, characterized in that the number of moles of the first diamine compound is 20 mol% to 80 mol% relative to the total number of moles of the diamine compounds, where the total number of moles of the diamine compounds is 100 mol%.

5. The diamine compound further includes a third diamine compound which is a diamine compound having a soft segment, 2. The polyimide precursor according to claim 1, wherein the number of moles of the third diamine compound is 30 mol % or less relative to the total number of moles of the diamine compounds, where the total number of moles of the diamine compounds is 100 mol %.

6. 6. The polyimide precursor according to claim 5, wherein the soft segment is selected from the group consisting of at least one ether group, at least one siloxane group, and at least one alicyclic group.

7. 2. The polyimide precursor according to claim 1, wherein the dianhydride comprises an aromatic tetracarboxylic dianhydride having one to four aromatic rings, and the number of moles of the aromatic tetracarboxylic dianhydride exceeds 30 mol % relative to the total number of moles of the dianhydrides, where the total number of moles of the dianhydrides is taken as 100 mol %.

8. The polyimide precursor according to claim 7 , wherein the dianhydride further comprises an alicyclic tetracarboxylic dianhydride.

9. A resin composition comprising the polyimide precursor according to claim 1 and a solvent capable of dissolving the polyimide precursor.

10. 10. The resin composition according to claim 9, wherein the solvent is selected from the group consisting of amide-based solvents, cyclic amide-based solvents, ester-based solvents, ether-based solvents, and combinations thereof.

11. A dehydration cyclization product of the polyimide precursor according to claim 1, Contains repeating units of formula (X) and formula (Y) 【Chemistry 6】 A polyimide characterized by:

Images