Polyimide resin and adhesive film

Abstract

The purpose of the present invention is to provide a polyimide resin which, when used in an adhesive film for manufacturing a semiconductor or an electronic component, generates little volatile components even at high temperatures, has good adhesiveness at low temperatures, can be laminated at normal temperature, has appropriate adhesive strength after a high-temperature heat treatment step, and can be used as an adhesive film for manufacturing a semiconductor or an electronic component. The adhesive tape can be easily peeled off without residual adhesive at normal temperature, the warping in each process is less, and the overflow of a mold can be prevented. The present invention provides a solvent-soluble polyimide resin having a cyclic imide structure, the polyimide resin having repeating units of a diamine residue containing a polysiloxane-based diamine and a diamine residue having an anilino group and / or a diamine residue having a carboxyl group. In addition, the present invention provides an adhesive film obtained by laminating a resin composition containing the polyimide resin on at least one surface of a heat-resistant film.

Description

Technical Field

[0001] The present invention relates to a polyimide resin suitable for use as a heat-resistant adhesive for semiconductor or electronic component manufacturing. More specifically, it relates to a polyimide resin for use in semiconductor or electronic component manufacturing, which is bonded to a semiconductor element mounting substrate during semiconductor package manufacturing, and a resin composition, adhesive, and adhesive film containing the same. Background Art

[0002] In recent years, as the demand for miniaturization and lightweighting of electronic devices has increased, the electronic components built into them are also required to be miniaturized and mounted at a high density. Therefore, various forms have been developed as semiconductor packages. For example, as an area array mounting type package, there is a CSP (Chip Size Package) that significantly reduces the size of the BGA (Ball Grid Array). Among these CSPs, the QFN (Quad Flat Non-leaded Package) is a package developed for the purpose of miniaturization and low profile of the QFP (Quad Flat Package) using leads, and uses electrode pads instead of leads as connection terminals. Since the QFN has an external lead portion in the package area, there is a problem of mold flash that causes the sealing resin to be drawn in. In order to solve this problem, it is effective to protect the external lead portion of the lead frame with an adhesive film during resin sealing. From this point of view, various adhesive films for semiconductor packages such as QFN have been proposed.

[0003] Such adhesive films are generally manufactured by applying various adhesive layers to a heat-resistant film. Proposed heat-resistant films include polyimide, polyamide, polyamideimide, polyetherimide, polyester, polyphenylene sulfide, polysulfone, and polyethersulfone. Proposed adhesive layer resins include acrylic, silicone, polyamide, and polyimide. The adhesive layer is heated to high temperatures during heating processes such as die attach, wire bonding, and resin sealing, and is subsequently peeled from the leadframe. This requires addressing not only mold flash but also compatibility with various processes, adhesive residue, and warpage. To address this, various adhesive layers have been proposed.

[0004] For example, Patent Document 1 discloses that a polyimide resin having a main amine component composed of a diaminosiloxane compound and 2,2-bis(4-(4-aminophenoxy)phenyl)propane or 1,3-bis(3-aminophenoxy)benzene, which is soluble in an organic solvent and has a glass transition temperature of 100 to 150°C, becomes a film-like adhesive for semiconductor mounting materials.

[0005] Patent Document 2 also discloses a resin composition containing a polyimide resin and a methylol compound, wherein the diamine residues of the polyimide resin are residues of a polysiloxane diamine and residues of an aromatic diamine having a hydroxyl group, as a heat-resistant adhesive suitable for use in the manufacture of electronic devices. Patent Document 2 states that if either the residue of an aromatic diamine having a hydroxyl group in the polyimide resin or the methylol compound is absent in the resin composition, the adhesive strength to the polyimide film as a substrate increases significantly after treatment at 300°C, making it impossible to peel the film at room temperature (paragraph 0098).

[0006] Patent Document 3 discloses an adhesive film having a heat-resistant film and an adhesive layer for use in manufacturing semiconductors or electronic components, wherein the adhesive layer of the adhesive film comprises a polyimide copolymer containing 30 to 100 mol % of a polysiloxane-based diamine residue in all diamine residues.

[0007] In Patent Documents 2 and 3, polyamic acid is synthesized, and a resin composition containing the polyamic acid is applied onto a substrate such as a glass substrate or a polyimide film, followed by heating to 250° C. for complete imidization.

[0008] However, the adhesive films using polyimide resins described in Patent Documents 1 to 3 have a problem in that adhesive residue is generated depending on the conditions when the adhesive layer is peeled off from the lead frame after a heating step at a high temperature.

[0009] Prior art literature

[0010] Patent Literature

[0011] Patent Document 1: Japanese Patent Application Laid-Open No. 2004-277619,

[0012] Patent Document 2: International Publication No. 2014 / 050878,

[0013] Patent document 3: Japanese Patent Application Laid-Open No. 2020-136600. Summary of the Invention

[0014] Problems to be solved by the invention

[0015] As mentioned above, the properties required for the high heat-resistant adhesive resin or adhesive film used in semiconductor manufacturing are heat resistance at high temperatures, low decomposition, lamination at room temperature, re-peelability at room temperature after high-temperature heat treatment, and low warpage in each process. As resins that meet this requirement, various polyimide resins as mentioned above have been studied, but there is no polyimide resin that fully possesses all of these properties. In particular, it is difficult to find a polyimide resin that can solve the problem of residual glue when peeling off the adhesive layer after the heating process at high temperatures. In addition, if a resin composition comprising polyamic acid is applied to a base material such as a glass substrate or a polyimide film and then heated to a high temperature such as 250°C to carry out complete imidization, a syneresis reaction will occur, and therefore there is also the problem of curling of the adhesive film.

[0016] In view of such circumstances, the object of the present invention is to provide a polyimide resin having a cyclic imide structure, a resin composition using the same, an adhesive film, and a method for producing the same. The polyimide resin produces little volatile components due to decomposition, etc. even at high temperatures of 250°C or above, has good adhesion at low temperatures, can be laminated at room temperature, has appropriate adhesion after a high-temperature heat treatment step, can be easily peeled off at room temperature without residual adhesive, has little warping in each step, and can prevent mold flash.

[0017] Means of solving problems

[0018] The present inventors have conducted intensive research to address the above-mentioned issues and have discovered that a solvent-soluble polyimide resin having a cyclic imide structure that provides suitable adhesiveness and removability can be obtained by using a copolymer having a tetracarboxylic dianhydride residue, a diamine residue of a polysiloxane-based diamine, and a diamine residue having an anilide group and / or a diamine residue having a carboxyl group as a polyimide resin having a cyclic imide structure. Furthermore, the present inventors have discovered that the above-mentioned issues can be addressed by using a resin composition containing such a resin, providing an adhesive for semiconductor or electronic component manufacturing that combines the properties of heat resistance at high temperatures, low decomposition, laminatability at room temperature, removability at room temperature after high-temperature heat treatment, and low warpage in various steps, and an adhesive film using the same, thereby completing the present invention.

[0019] That is, the present invention provides a polyimide resin which is a solvent-soluble imide resin having a cyclic imide structure and is characterized by having a repeating unit represented by the following general formula (1):

[0020] [Chemical Formula 1]

[0021]

[0022] In the formula, Z is a tetracarboxylic dianhydride residue, and A is a diamine residue of a polysiloxane-based diamine, a diamine residue having an anilide group, and / or a diamine residue having a carboxyl group.

[0023] Furthermore, there is provided a resin composition characterized by containing the polyimide resin of the present invention and an organic solvent.

[0024] The present invention also provides an adhesive for use in producing semiconductors or electronic components, comprising the polyimide resin of the present invention.

[0025] The present invention also provides an adhesive film for producing semiconductors or electronic components, wherein the resin composition of the present invention is laminated on at least one surface of a heat-resistant film.

[0026] Effects of the Invention

[0027] The present invention provides a polyimide resin, a resin composition containing the same, an adhesive, and an adhesive film. The polyimide resin emits low levels of volatile components, even at temperatures exceeding 250°C due to decomposition, exhibits excellent adhesion at low temperatures, and can be laminated at room temperature. After undergoing a high-temperature heat treatment step, the resin exhibits moderate adhesion and can be easily peeled off at room temperature without residual adhesive. Furthermore, the resin composition, adhesive, and adhesive film containing the same exhibit minimal warping during the various steps, preventing mold flash. Furthermore, the use of a solvent-soluble polyimide resin having a cyclic imide structure eliminates the need for a heating step for imidization during the adhesive film production process, providing a highly productive production process. DETAILED DESCRIPTION

[0028] [Polyimide resin]

[0029] The polyimide resin of the present invention is a solvent-soluble polyimide resin having a repeating unit represented by the following general formula (1) and a cyclic imide structure. In the present invention, "cyclic imide structure" means a structure in which imide groups form a ring. In addition, the term "solvent-soluble" in the present invention is used with respect to the organic polar solvent used in the synthesis of the polyimide and the organic solvent used for diluting the polyimide resin in the resin composition described below, and means that 5g or more of the polyimide resin dissolves in 100g of the solvent.

[0030] [Chemical Formula 2]

[0031]

[0032] In the formula, Z is a tetracarboxylic dianhydride residue, and A is a diamine residue of a polysiloxane-based diamine, a diamine residue having an anilide group, and / or a diamine residue having a carboxyl group.

[0033] The repeating unit represented by the general formula (1) comprises at least a tetracarboxylic dianhydride residue (Z) and a diamine residue (A), wherein the diamine residue (A) is a diamine residue (A1) of a polysiloxane-based diamine and a diamine residue (A2) having an anilide group and / or a diamine residue (A3) having a carboxyl group.

[0034] That is, the polyimide resin of the present invention is characterized in that it is a polymer comprising the following repeating unit (1-1) in which the diamine residue (A) is a diamine residue (A1) of a polysiloxane-based diamine, and the following repeating unit (1-2) in which the diamine residue (A) is a diamine residue (A2) having an anilide group, or the following repeating unit (1-3) in which the diamine residue (A) is a diamine residue (A3) having a carboxyl group.

[0035] [Chemical Formula 3]

[0036]

[0037] In the formula, Z is a tetracarboxylic dianhydride residue, and A1 is a diamine residue of a polysiloxane-based diamine.

[0038] [Chemical Formula 4]

[0039]

[0040] In the formula, Z is a tetracarboxylic dianhydride residue, and A2 is a diamine residue having an anilide group.

[0041] [Chemical Formula 5]

[0042]

[0043] In the formula, Z is a tetracarboxylic dianhydride residue, and A3 is a diamine residue having a carboxyl group.

[0044] The polyimide resin of the present invention may be a random copolymer randomly containing the repeating unit (1-1) and the repeating unit (1-2) and / or the repeating unit (1-3), or a block polymer having a structure in which only a part of the repeating units (1-1) to (1-3) are polymerized in advance.

[0045] As described later, the resin composition comprising the polyimide resin of the present invention can be suitably used as a heat-resistant adhesive for the manufacture of semiconductors or electronic components. By ensuring that the diamine residue (A) constituting the polyimide resin of the present invention has the specific structure described above, the adhesive layer laminated on the heat-resistant film can achieve both adequate adhesive strength and adhesive residue (no adhesive residue) when peeled. Using diamine residues having functional groups other than carboxyl groups and anilide groups makes it difficult to achieve both adequate adhesive strength and adhesive residue when peeled.

[0046] (Tetracarboxylic dianhydride residue)

[0047] As the tetracarboxylic dianhydride residue (Z), it is preferable to include a residue of an aromatic tetracarboxylic dianhydride. Specific examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2'-dimethyl-3,3',4,4'-biphenyltetracarboxylic dianhydride, 5,5'-dimethyl-3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, Acid dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, 2,3,3',4'-diphenyl ether tetracarboxylic dianhydride, 2,2',3,3'-diphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 2,2',3,3'-benzophenone tetracarboxylic dianhydride, 2,3,3',4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride -diphenylsulfone tetracarboxylic dianhydride, 2,3,3',4'-diphenylsulfone tetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfoxide tetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfide tetracarboxylic dianhydride, 3,3',4,4'-diphenylmethylene tetracarboxylic dianhydride, 4,4'-isopropylidene diphthalic anhydride, 4,4'-(hexafluoroisopropylidene) diphthalic anhydride, 3 ,4,9,10-perylenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 3,3",4,4"-p-terphenyltetracarboxylic dianhydride, 3,3",4,4"-m-terphenyltetracarboxylic dianhydride, 2,3,6,7-anthracenetetracarboxylic dianhydride, 1,2,7,8-phenanthrenetetracarboxylic dianhydride, etc. The above-mentioned aromatic tetracarboxylic dianhydrides can be used alone or in combination of two or more. Among them, from the viewpoint of improving heat resistance by increasing the thermal weight loss temperature, monocyclic acid dianhydrides such as pyromellitic dianhydride are preferred.

[0048] (Diamine residue)

[0049] The diamine residue (A) in the general formula (1) is a diamine residue of a polysiloxane-based diamine, a diamine residue having an anilide group, and / or a diamine residue having a carboxyl group.

[0050] The polysiloxane type as the diamine residue constituting the polysiloxane-based diamine is not particularly limited, but a polysiloxane-based diamine represented by the following general formula (2) is preferred.

[0051] [Chemical Formula 6]

[0052]

[0053] In formula (2), n is a natural number, an integer of 1 to 150. n is preferably 5 to 50, more preferably 7 to 15. R1 and R2 are the same or different from each other and represent an alkylene group or a phenylene group having 1 to 40 carbon atoms. R1 and R2 are preferably an alkylene group or a phenylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 2 to 5 carbon atoms. R3 to R6 are the same or different from each other and represent an alkyl group, a phenyl group or a phenoxy group having 1 to 40 carbon atoms. R3 to R6 are preferably an alkyl group or a phenoxy group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms.

[0054] Specific examples of the polysiloxane diamine represented by the general formula (2) include α,ω-bis(3-aminopropyl)polydimethylsiloxane, α,ω-bis(3-aminopropyl)polydiethylsiloxane, α,ω-bis(3-aminopropyl)polydipropylsiloxane, α,ω-bis(3-aminopropyl)polydibutylsiloxane, α,ω-bis(3-aminopropyl)polydiphenoxysiloxane, α,ω-bis(2-aminoethyl)polydimethylsiloxane, α,ω-bis(2-aminoethyl)polydiphenoxysiloxane, α,ω-bis(3-aminopropyl)polydimethylsiloxane, α,ω-bis(2-aminoethyl)polydiphenoxysiloxane, α,ω-bis(3-aminopropyl)polydimethylsiloxane, α,ω-bis(2-aminoethyl)polydiphenoxysiloxane, α,ω-bis(3-aminopropyl)polydimethylsiloxane, α,ω-bis(3-aminopropyl)polydiethylsiloxane, α,ω-bis(3-aminopropyl)polydibutylsiloxane, α,ω-bis(3-aminopropyl)polydiphenoxysiloxane, α,ω-bis(2-aminoethyl)polydiphenoxysiloxane, α,ω-bis(3-aminopropyl)polydimethylsiloxane, α,ω-bis(2-aminoethyl)polydiphenoxysiloxane, α,ω-bis(3-aminopropyl)polydimethylsiloxane, α,ω-bis(3-aminopropyl)polydimethylsiloxane, α,ω-bis(3-aminopropyl)polydiethylsiloxane, α,ω-bis(3-aminopropyl)polydimethylsiloxane, α,ω-bis(3-aminopropyl)polydimethylsiloxane, α,ω-bis(3-aminopropyl)polydimethylsiloxane, α,ω-bis(3-aminopropyl)polydimethylsiloxane, α,ω-bis(3- -bis(4-aminobutyl)polydimethylsiloxane, α,ω-bis(4-aminobutyl)polydiphenoxysiloxane, α,ω-bis(5-aminopentyl)polydimethylsiloxane, α,ω-bis(5-aminopentyl)polydiphenoxysiloxane, α,ω-bis(4-aminophenyl)polydimethylsiloxane, α,ω-bis(4-aminophenyl)polydiphenoxysiloxane, etc. Among them, α,ω-bis(3-aminopropyl)polydimethylsiloxane is preferred from the viewpoint of excellent balance among adhesion, reactivity, and solubility in reaction solvents. The polysiloxane-based diamine represented by general formula (2) may be used alone or in combination of two or more.

[0055] From the perspective of achieving both adequate adhesive strength and residual adhesiveness (no residual adhesive) during peeling, the content of diamine residues in the polysiloxane-based diamine is preferably 60 mol% or more, 65 mol% or more, more preferably 68 mol% or more, and particularly preferably 70 mol% or more, and is preferably 97 mol% or less, 95 mol% or less, more preferably 93 mol% or less, and particularly preferably 90 mol% or less, based on the total diamine residues. If the content of diamine residues in the polysiloxane-based diamine exceeds 97 mol% of the total diamine residues, the adhesive strength tends to increase, and residual adhesive may be generated.

[0056] The diamine residue having a carboxyl group is preferably a residue of a carboxyl group-containing aromatic diamine represented by the following general formula (3).

[0057] [Chemical Formula 7]

[0058]

[0059] In formula (3), X is a single bond, a substituted or unsubstituted alkylene group, a carbonyl group, or an ether group, p is an integer from 0 to 2, m1 is an integer from 0 to 4, and m2 is an integer from 0 to 4. When p is 0, m1 is an integer from 1 to 4. X is preferably a single bond, p is preferably from 0 to 1, and m1 is preferably from 1 to 2.

[0060] Specific examples of the carboxyl group-containing aromatic diamine represented by the general formula (3) include 3,5-diaminobenzoic acid, 3,4-diaminobenzoic acid, 5,5'-methylenebis(2-aminobenzoic acid), 3,5-bis(4-aminophenoxy)benzoic acid, and 4,4'-diaminobiphenyl-3,3'-dicarboxylic acid. Among them, monocyclic carboxyl group-containing aromatic diamines such as 3,5-diaminobenzoic acid and 3,4-diaminobenzoic acid are preferred from the viewpoints of maintaining an appropriate adhesive strength after the adhesive film has passed through a high-temperature heat treatment step and leaving no adhesive residue when the adhesive film is peeled off at room temperature.

[0061] Furthermore, as the diamine residue having a carboxyl group, the residue of a carboxyl group-containing aromatic diamine described below (4) or (5) can also be used.

[0062] [Chemical Formula 8]

[0063]

[0064] [Chemical Formula 9]

[0065]

[0066] In the present invention, from the viewpoint of achieving both appropriate adhesive strength and residual adhesiveness (no residual adhesive) during peeling, the number of carboxyl groups possessed by the carboxyl group-containing aromatic diamine is preferably 1 to 5, more preferably 1 to 3, further preferably 1 to 2, and particularly preferably 1.

[0067] The above-mentioned carboxyl group-containing aromatic diamines may be used alone or in combination of two or more.

[0068] The diamine residue having an anilide group is preferably at least one of the anilide group-containing aromatic diamines represented by the following general formulae (6-1) to (6-3).

[0069] [Chemical Formula 10]

[0070]

[0071] In the formula, R1 to R8 are the same or different and represent an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms. In addition, n1 to n8 each represent an integer of 0 to 4, preferably 0 to 1.

[0072] Specific examples of the anilino group-containing aromatic diamines represented by the general formulas (6-1) to (6-3) include 4,4'-diaminobenzanilide, 3,4'-diaminobenzanilide, 4,3'-diaminobenzanilide, 4,4'-diaminoterephthalanilide, 4,4'-diaminometaphthalanilide, 3,3'-diaminoterephthalanilide, 3,3'-diaminometaphthalanilide, 3,4'-diaminoterephthalanilide, 3,4'-diaminometaphthalanilide, 2-methoxy-4,4'-diaminobenzanilide, 2,2'-dimethoxy-4,4'-diaminobenzanilide, 2,6-dimethoxy-4,4'-diaminobenzanilide, and 2,6'-dimethoxy-4,4'-diaminobenzanilide. Among these, from the viewpoint of maintaining an appropriate adhesive strength after the adhesive film has passed a high-temperature heat treatment step and leaving no adhesive residue when the adhesive film is peeled off at room temperature, a substance having a benzanilide structure is preferred, and an anilide-containing aromatic diamine represented by the above-mentioned general formula (6-1) is preferred. These anilide-containing aromatic diamines may be used alone or in combination of two or more.

[0073] In the present invention, the number of anilide groups in the anilide-containing aromatic diamine is preferably 1 to 3, more preferably 1 to 2, and even more preferably 1, from the viewpoint of achieving both appropriate adhesive strength and residual adhesiveness (no residual adhesive) during peeling.

[0074] The above-mentioned carboxyl group-containing aromatic diamine and anilide group-containing aromatic diamine may be used in combination or either one thereof may be used.

[0075] From the perspective of achieving both adequate adhesive strength and adhesive residue during peeling, the combined content of diamine residues having carboxyl groups and diamine residues having anilide groups is preferably 3 mol% or more, 5 mol% or more, more preferably 7 mol% or more, and particularly preferably 10 mol% or more of the total diamine residues, and is preferably 40 mol% or less, 35 mol% or less, more preferably 32 mol% or less, and particularly preferably 30 mol% or less. If the combined content of diamine residues having carboxyl groups and diamine residues having anilide groups is less than 3 mol%, adhesive residue may be generated, while if it exceeds 40 mol%, adhesive strength may be reduced.

[0076] When the carboxyl group-containing aromatic diamine and the anilide group-containing aromatic diamine are used in combination, the molar ratio of the diamine residue having a carboxyl group to the diamine residue having an anilide group in the polyimide resin is preferably 9-5:1-5, more preferably 8-6:2-4.

[0077] (Synthesis Method of Polyimide Resin)

[0078] The method for synthesizing the solvent-soluble polyimide can be any known method without particular limitation. The solvent-soluble polyimide can be synthesized by using approximately equal amounts of the above-mentioned aromatic tetracarboxylic dianhydride and diamine, reacting them in an organic polar solvent in the presence of a catalyst and a dehydrating agent at 160 to 200° C. for several hours.

[0079] The solvent-soluble polyimide resin in the present invention is a copolymer. When the polyimide is synthesized by a one-stage polymerization reaction, a random copolymer can be obtained. However, a block copolymer can also be synthesized by performing a block copolymerization reaction as needed. For example, it can be produced by a two-stage sequential addition reaction. In the first stage, a polyimide oligomer can be synthesized from the above-mentioned aromatic tetracarboxylic dianhydride and diamine. Then, in the second stage, aromatic tetracarboxylic dianhydride and / or diamine are further added to cause polycondensation to produce a block copolymer polyimide.

[0080] As catalysts for these reactions, a two-component acid-base catalyst utilizing the equilibrium reaction of lactone is used, thereby promoting the dehydration imidization reaction. Specifically, a two-component catalyst (lactone-based catalyst) of γ-valerolactone and pyridine or N-methylmorpholine is used. As shown in the following formula, as the imidization proceeds, water is generated. The generated water participates in the equilibrium of the lactone, acting as an acid-base catalyst and exhibiting a catalytic effect.

[0081] [Chemical Formula 11]

[0082]

[0083] The water generated by the imidization reaction is azeotropically removed from the reaction system by co-existing with a dehydrating agent such as toluene or xylene in the polar solvent. After the reaction is complete, the water in the solution is removed, and the acid-base catalyst is converted to γ-valerolactone and pyridine or N-methylmorpholine, which are then removed from the reaction system. This produces a high-purity polyimide solution.

[0084] The polyimide obtained by the direct imidization reaction using the above-mentioned lactone catalyst system composed of lactone and base can be obtained in the form of a solution dissolved in a polar solvent. Moreover, the concentration of the polyimide can also be set within the preferred range of 10 to 50% by weight of the solid content of the polyimide resin. Therefore, the produced polyimide solution can be preferably used in its original state.

[0085] Other two-component catalysts include oxalic acid or malonic acid and pyridine or N-methylmorpholine. In a reaction solution at 160-200°C, oxalates or malonates act as acid catalysts to promote the imidization reaction. A catalytic amount of oxalic acid or malonic acid remains in the resulting polyimide solvent. After applying this polyimide solution to a substrate and heating it to above 200°C to remove the solvent and form a film, the oxalic acid or malonic acid remaining in the polyimide undergoes thermal decomposition as shown in the following formula and is expelled from the system as a gas. Oxalic acid-pyridine catalysts are more active than valerolactone-pyridine catalysts and can produce high-molecular-weight polyimides in a short period of time.

[0086] [Chemical Formula 12]

[0087]

[0088] As the organic polar solvent used for the synthesis of the solvent-soluble polyimide, glycol ether solvents, amide polar solvents, and ketone solvents are preferably used from the viewpoint of solubility and storage stability of the polyimide copolymer or polyimide resin.

[0089] Specific examples of the glycol ether-based solvents include propylene glycol mono-t-butyl ether, ethylene glycol mono-t-butyl ether, propylene glycol mono-n-butyl ether, propylene glycol monopropyl ether, propylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol monopropyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dipropyl ether, dipropylene glycol di-n-butyl ether, dipropylene glycol di-t-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monopropyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tripropylene glycol dimethyl ether, and tetraethylene glycol dimethyl ether.

[0090] Specific examples of amide-based polar solvents include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, and 1,3-dimethyl-2-imidazoline. Specific examples of ketone-based solvents include cyclohexanone. These organic polar solvents may be used alone or as a mixture of two or more. Among these, glycol ether-based solvents are preferred from the perspective of improving the storage stability of the synthesized polyimide resin solution.

[0091] The above method enables the synthesis of a solvent-soluble polyimide resin having a cyclic imide structure at high purity. Because the resulting polyimide resin has a cyclic imide structure, it does not require heating to high temperatures, such as 250°C, for complete imidization after coating on a substrate, as is required with polyamic acid. This avoids the problem of adhesive film deformation and, by omitting the high-temperature heating step, provides a highly productive process.

[0092] The molecular weight of the obtained solvent-soluble polyimide resin is 10,000 to 200,000 in terms of weight average molecular weight in terms of polystyrene. Polyimide resins within this weight average molecular weight range can achieve good solvent solubility, film properties, and insulation properties.

[0093] [Resin composition]

[0094] A resin composition containing the solvent-soluble polyimide resin produced as described above and an organic solvent can be suitably used as a heat-resistant adhesive for manufacturing semiconductors or electronic components. The resin composition of the present invention is a resin composition in a solution state in which a polyimide resin is dissolved in an organic solvent so that its solid content is, for example, 10 to 50% by weight. As the organic solvent contained in the resin composition, the organic polar solvent used in the synthesis of the above-mentioned solvent-soluble polyimide resin can be used as it is. By using the organic solvent used in the synthesis method of the solvent-soluble polyimide resin as it is as the organic solvent of the resin composition, a resin composition in a solution state in which the polyimide resin is dissolved in the above-mentioned organic polar solvent so that the solid content is 10 to 50% by weight can be easily obtained.

[0095] Among the organic solvents contained in the resin composition, cyclohexanone is preferably used alone or in combination with other organic solvents because the drying temperature during coating can be lowered and the amount of residual solvent in the drying process can be reduced at a relatively low temperature (160 to 180° C.).

[0096] When cyclohexanone is used as an organic solvent, the ratio of cyclohexanone in the organic solvent contained in the resin composition is generally 20 to 60 volume %, preferably 30 to 50 volume s, more preferably 35 to 45 volume s. As other organic solvents in the case of combining cyclohexanone with other organic solvents in the resin composition, glycol ether solvents such as triethylene glycol dimethyl ether are preferred. For example, by using glycol ether solvents such as triethylene glycol dimethyl ether and ketone solvents such as cyclohexanone (volume ratio) in a ratio of 8: 2 to 4: 6, preferably 7: 3 to 5: 5, there is the advantage that the reduction of monomer solubility, drying temperature and stability all become good. It should be noted that, as the organic solvent contained in the resin composition, it is not limited to the above-mentioned organic solvents, and other organic solvents can also be used.

[0097] (Epoxy Compound)

[0098] From the viewpoint of adjusting the bonding strength, the resin composition of the present invention preferably includes an epoxy compound. As the epoxy compound, there is no particular limitation and it can be selected according to the compatibility with the polyimide resin composition. As the epoxy compound, for example, phenol novolac epoxy resin, cresol novolac epoxy resin, bisphenol A novolac epoxy resin, epoxy resin containing a triazine skeleton, epoxy resin containing a fluorene skeleton, naphthalene type epoxy resin, biphenyl type epoxy resin, crystalline epoxy resin, bisphenol A type epoxy resin, etc. can be used, and their high molecular epoxy resins can also be used. Among them, from the viewpoint of reactivity, it is preferred to use a multifunctional epoxy compound, particularly preferably a monocyclic tetrafunctional epoxy compound (N,N,N',N'-tetraglycidyl-1,3-phenylenedi(methylamine)) represented by the following general formula (7).

[0099] [Chemical Formula 13]

[0100]

[0101] The content of the epoxy compound in the resin composition is preferably 1 part by weight (solid content) or more, preferably 2 parts by weight or more, more preferably 3 parts by weight or more, particularly preferably 4 parts by weight or more, and preferably 10 parts by weight or less, 9 parts by weight or less, 8 parts by weight or less, more preferably 7 parts by weight or less, and particularly preferably 6 parts by weight or less, relative to 100 parts by weight (solid content) of the solvent-soluble polyimide.

[0102] (Other additives)

[0103] For the purpose of improving properties such as adhesion, heat resistance, and coating properties, surfactants, silane coupling agents, leveling agents, etc. may be added to the resin composition of the present invention. Depending on the composition of the resin composition, when there is a concern that the resin composition may show a tendency to be slightly repelled during coating, a leveling agent may be added, but the leveling agent is not an essential component in achieving the effects of the present invention. In addition, the resin composition of the present invention may contain inorganic particles. By containing inorganic particles, the heat resistance and dimensional stability of the resin composition can be improved, and the adhesion can be adjusted. Specific examples of inorganic particles include silicon dioxide, aluminum oxide, titanium oxide, quartz powder, magnesium carbonate, potassium carbonate, barium sulfate, mica, talc, etc., among which silicon dioxide is preferred. The content of the inorganic particles in the resin composition is preferably 2 to 70 parts by weight, preferably 5 to 40 parts by weight, and most preferably 7 to 20 parts relative to 100 parts by weight (solid content) of the polyimide resin.

[0104] [Adhesive film]

[0105] The resin composition is laminated as a polyimide adhesive on at least one surface of a heat-resistant film to form an adhesive layer on the surface of the heat-resistant film, thereby forming an adhesive film having the heat-resistant film and the adhesive layer.

[0106] (Heat-resistant film)

[0107] Heat-resistant films are insulating plastic films that can be used in high-temperature processes such as die attach, wire bonding, resin sealing, and reflow heating. Specifically, they include plastic films such as polyimide, polyamide, polyamideimide, polyetherimide, polyester, polyphenylene sulfide, polysulfone, and polyethersulfone. Polyimide films are preferred from the perspective of heat resistance.

[0108] In order to improve the adhesion of the resin composition to the heat-resistant film, the heat-resistant film is preferably subjected to a surface treatment (surface roughening treatment) such as plasma treatment or corona treatment. As the plasma gas used in the plasma treatment, oxygen, nitrogen, water, carbon dioxide, argon or a mixture thereof can be used.

[0109] (Adhesive layer)

[0110] The adhesive film of the present invention can be produced by applying a resin composition directly or via a primer layer onto a heat-resistant film to form an adhesive layer. Examples of methods for applying the resin composition of the present invention onto a heat-resistant film include spin coating, roll coating, comma coating, gravure printing, screen printing, and slot die coating. After applying the resin composition, drying it at 100-150°C and then heat-treating it continuously or intermittently at 160-240°C for 2 minutes to 1 hour can produce an adhesive layer with excellent adhesion and heat resistance.

[0111] In the present invention, the resin composition can be directly applied to a glass substrate and dried to form an adhesive layer. Examples of coating methods on a glass substrate include spin coating, screen printing, gravure coating, slot die coating, and bar coating.

[0112] The weight loss rate of the adhesive layer when heated from 30°C to 300°C is preferably 0.8% or less, more preferably 0.5% or less, and even more preferably 0.3% or less. If the weight loss rate exceeds 0.8%, contamination of the semiconductor device mounting substrate or wire bonding defects may occur during the semiconductor manufacturing process.

[0113] The thickness of the adhesive layer is preferably 2 to 30 μm, more preferably 3 to 20 μm, and even more preferably 4 to 10 μm. If the thickness of the adhesive layer is less than 2 μm, it may be difficult to follow the unevenness of the surface of the semiconductor element mounting substrate. Therefore, it is impossible to fill the gap between the adhesive and, for example, the lead frame, which is the semiconductor element mounting substrate, and mold flash is likely to occur. If the adhesive layer exceeds 30 μm, it may cause poor wire bonding during wire bonding, and the adhesion to the lead frame or sealing resin increases, and the workability during the peeling process may deteriorate.

[0114] The glass transition temperature of the adhesive layer of the present invention is usually above -10°C, above -8°C, above -5°C, above -3°C, preferably below 40°C, more preferably below 30°C, and particularly preferably below 25°C. If the glass transition temperature exceeds 40°C, when a substrate as an adherend is laminated on the adhesive layer formed using the resin composition of the present invention, good adhesion may not be obtained. In addition, the lower limit of the glass transition temperature does not affect the effect of the present invention, but if it is too low, the adhesion may become too high. "Good adhesion" in the present invention refers to an adhesion force that is greater than the degree to which the substrate will not naturally peel off when the above-mentioned adhesive layer film is laminated on the substrate at room temperature. Specifically, when the substrate as the adherend is peeled off at a peeling angle of 90 degrees and 10 mm / min, an adhesion force of more than 5 g / cm is shown. When it is desired to increase the initial peel strength of the adherend, it can also be achieved by increasing the lamination temperature.

[0115] Typically, if the adhesive layer comprising a polyimide-based adhesive undergoes a high-temperature heat treatment process, the bond strength increases. Although the adhesive comprising the polyimide resin of the present invention increases bond strength after an initial heat treatment of about 150°C, the change in bond strength after the subsequent additional high-temperature heat treatment (150°C to 250°C) is small. That is, the polyimide resin of the present invention can impart and maintain appropriate bonding force to the adhesive layer because it contains a diamine residue with a specific structure in the repeating unit. The appropriate bonding strength at this time is generally 5 to 400 g / cm, preferably 8 to 300 g / cm, and more preferably 10 to 200 g / cm. Furthermore, when it is desired to reduce the bond strength to an appropriate value, it can be adjusted by adding an epoxy compound or inorganic particles (filler).

[0116] (Adhesive film)

[0117] The adhesive film of the present invention is suitable as an adhesive film for semiconductor manufacturing. Specifically, since the adhesive film of the present invention has an adhesive layer containing the above-mentioned polyimide resin having a specific diamine residue, it can be attached to the semiconductor element mounting substrate at room temperature (5 to 35°C). In addition, by using the specific polyimide resin of the present invention, the film is less susceptible to decomposition, degradation, and other changes in the thermal process in the chip mounting process, wire bonding process, flip chip process, redistribution layer formation process, and resin sealing process in the semiconductor manufacturing process, and exhibits stable adhesive strength. Furthermore, by using the specific polyimide resin of the present invention, when the film is peeled off from the semiconductor element mounting substrate after sealing, it is difficult to produce residual adhesive on the surface of the semiconductor element mounting substrate.

[0118] Furthermore, the adhesive film of the present invention is less susceptible to decomposition and degradation due to thermal processes and is therefore suitable as an adhesive film for electronic component manufacturing and can be suitably used in electronic component manufacturing processes employing high-temperature processes such as reflow.

[0119] The adhesive film of the present invention may also be pre-laminated with a removable protective film (insulating film) on the surface of the adhesive layer to protect the adhesive layer or prevent adhesion. In this case, the protective film may be any plastic film such as polyethylene, polypropylene, or polyethylene terephthalate, a metal foil such as aluminum foil or copper foil, or a laminate of a plastic film and a metal foil. Furthermore, to facilitate peeling of the protective film, the surface of the protective film may be pre-treated with a release agent such as a silicone or fluorine-based release agent.

[0120] When the adhesive film of the present invention is used as an adhesive transfer film, a release treatment may be applied to one or both sides of the heat-resistant film according to the purpose.

[0121] The adhesive film of the present invention can be used to be attached to a semiconductor element mounting substrate carrying a semiconductor or electronic component. As a semiconductor element mounting substrate, a lead frame, a printed circuit board, a wafer, and a sealing resin substrate for fan-out wafer level packaging (FOWLP) can be listed. Semiconductor elements refer to semiconductors and electronic components. For example, a semiconductor element can be mounted on a lead frame via a die attach film, or mounted on a printed circuit board by flip-chip connection and a subsequent reflow process. In addition, a semiconductor element can be mounted on a sealing resin wafer substrate by attaching a chip to the adhesive film of the present invention, and then resin-sealing the attached chip together, as in a fan-out package. Furthermore, a semiconductor element also includes a wafer having circuits such as a semiconductor element or a comb-shaped electrode formed on the wafer.

[0122] By using the polyimide resin of the present invention, for example, in a fan-out packaging process, there is no residual adhesive on the exposed surface after peeling the adhesive film from the sealing resin wafer substrate, so the process of forming a redistribution layer on the exposed surface or the process of cutting the redistribution layer can be performed.

[0123] Example

[0124] Hereinafter, the present invention will be described in detail based on Examples, but the present invention is not limited to the following Examples.

[0125] 1. Synthesis of solvent-soluble imide resin and resin composition

[0126] (Example 1)

[0127] A separable three-necked glass flask was equipped with a stirrer, a nitrogen inlet tube, and a Dean-Stark apparatus. 304.08 g (0.358 mol) of polysiloxane diamine KF-8010 (functional group equivalent (g / mol) = 425, manufactured by Shin-Etsu Chemical Co., Ltd., a polysiloxane diamine represented by the general formula (2) of the present invention), 86.70 g (0.397 mol) of pyromellitic dianhydride (hereinafter referred to as PMDA), 6.05 g (0.040 mol) of 3,5-diaminobenzoic acid (hereinafter referred to as 3,5-DABA), 1.99 g (0.020 mol) of γ-valerolactone, 3.14 g (0.040 mol) of pyridine, 285 g of triethylene glycol dimethyl ether, 190 g of cyclohexanone, and 70 g of toluene were added, and the mixture was stirred at 180 rpm for 30 minutes at room temperature under a nitrogen atmosphere, and then heated to 180° C. During the reaction, water was removed by azeotropy with toluene. After confirming the distillation of water, the mixture was heated and stirred for 6 hours, then cooled, 1.94 parts by weight of KL-700 (100% by weight leveling agent manufactured by Kyoeisha Chemical Co., Ltd.) was added, and the mixture was further cooled to room temperature to obtain an adhesive resin composition having a solid content of 45% by weight.

[0128] (Example 2)

[0129] An adhesive resin composition having a solid content of 40 wt % was obtained in the same manner as in Example 1 except that the amount of KF-8010 used was 236.13 g (0.278 mol) and the amount of 3,5-DABA used was 18.11 g (0.119 mol).

[0130] (Example 3)

[0131] An adhesive resin composition having a solid content of 45 wt % was obtained in the same manner as in Example 1 except that 8.86 g (0.039 mol) of 4,4′-diaminobenzanilide was used instead of 3,5-DABA.

[0132] (Example 4)

[0133] To the resin composition of Example 1, 5 parts by weight of N,N,N',N'-tetraglycidyl-1,3-phenylenedi(methylamine) was added to 100 parts by weight of the solid content of the polyimide resin, and the mixture was diluted with cyclohexanone to obtain an adhesive resin composition having a solid content of 48 wt%.

[0134] (Example 5)

[0135] To the resin composition of Example 1, 10 parts by weight of spherical silica slurry (50% solid content, SO-C1 (particle size 0.2 to 0.4 μm) N-methyl-2-pyrrolidone (hereinafter referred to as NMP) slurry, SO-C1 (particle size 0.2 to 0.4 μm, manufactured by ADMATECHS CO., LTD.) was added to the solid content of 100 parts by weight of the polyimide resin, and the mixture was diluted with NMP to obtain an adhesive resin composition with a solid content of 45 wt%.

[0136] (Comparative Example 1)

[0137] An adhesive resin composition having a solid content of 45 wt % was obtained in the same manner as in Example 1 except that 11.23 g (0.040 mol) of 4,4′-methylenebis(2-ethyl-6-methylaniline) was used instead of 3,5-DABA.

[0138] (Comparative Example 2)

[0139] A separable glass three-necked flask was equipped with a stirrer, a nitrogen inlet tube, and a Dean-Stark apparatus. 245.01 g (0.288 mol) of KF-8010, 62.87 g (0.288 mol) of PMDA, 1.44 g (0.014 mol) of valerolactone, 2.28 g (0.029 mol) of pyridine, 553 g of NMP, and 70 g of toluene were added. The mixture was stirred at 180 rpm for 30 minutes at room temperature under a nitrogen atmosphere, and then heated to 180°C. Water was removed during the reaction by azeotropic distillation with toluene. After confirming the distillation of water, the mixture was heated and stirred for 6 hours, then cooled, and 1.94 parts by weight of KL-700 (100 wt% leveling agent manufactured by Kyoeisha Chemical Co., Ltd.) was added. The mixture was further cooled to room temperature to obtain an adhesive resin composition with a solid content of 35 wt%.

[0140] (Comparative Example 3)

[0141] An adhesive resin composition having a solid content of 45 wt % was obtained in the same manner as in Example 1 except that 11.62 g (0.040 mol) of 1,3-bis(3-aminophenoxy)benzene was used instead of 3,5-DABA.

[0142] (Comparative Example 4)

[0143] An adhesive resin composition having a solid content of 45 wt % was obtained in the same manner as in Example 1 except that 7.96 g (0.040 mol) of 4,4′-diaminodiphenyl ether was used instead of 3,5-DABA.

[0144] (Comparative Example 5)

[0145] An adhesive resin composition having a solid content of 45 wt % was obtained in the same manner as in Example 1 except that 8.44 g (0.040 mol) of 3,3′-diaminobenzophenone was used instead of 3,5-DABA.

[0146] 2. Evaluation of properties of polyimide resin composition and adhesive film

[0147] The adhesive resin compositions synthesized in Examples 1-5 and Comparative Examples 1-5 were applied to SUS plates using a spin coater to a thickness of 8 μm. The resins in Examples 1-4 and Comparative Examples 1, 3-5 were then dried at 120°C for 10 minutes and then at 180°C for 20 minutes. The resins in Example 5 and Comparative Example 2 were dried at 120°C for 10 minutes and then at 220°C for 20 minutes. These changes in drying conditions were intended to maintain a consistent residual solvent content even when solvents with different boiling points were used in the Examples and Comparative Examples. However, these changes in drying conditions did not affect the properties of the adhesive films.

[0148] (1) Glass transition temperature Tg (℃)

[0149] The resin in the adhesive layer obtained after drying was scraped off with a cutter or the like, and approximately 10 mg was placed in a standard aluminum container. The glass transition temperature (°C) was determined from the inflection point of the resulting DSC curve using a differential scanning calorimeter (DSC). After pre-drying at 80°C for 30 minutes, the measurement was performed at a heating rate of 10°C / minute.

[0150] (2) Thermal weight loss rate (%)

[0151] The resin from the adhesive layer obtained after drying was scraped off using a cutter or other similar device. Approximately 15 mg of the resin was placed in a standard aluminum container and measured using a thermogravimetric analyzer (TG-DTA). The temperature was raised at a rate of 5°C / min to 400°C, and the weight loss (%) was measured from 30°C to 300°C.

[0152] Next, the resin compositions synthesized in Examples 1 to 5 and Comparative Examples 1 to 5 were applied to a 50 μm thick polyimide film using a spin coater to give an 8 μm thick adhesive layer. The resins of Examples 1 to 4 and Comparative Examples 1 and 3 to 5 were then dried at 120°C for 10 minutes and then at 180°C for 20 minutes, while the resins of Example 5 and Comparative Example 2 were dried at 120°C for 10 minutes and then at 220°C for 20 minutes to obtain adhesive films. The resins of Examples 1 to 4 were then dried at 120°C for 10 minutes and then at 180°C for 20 minutes, while the resins of Example 5 and Comparative Examples 1 to 2 were dried at 120°C for 10 minutes and then at 220°C for 20 minutes to obtain adhesive films.

[0153] (3) Adhesion strength

[0154] The obtained adhesive film was then bonded to a 125 μm thick copper plate (C-7025) using a laminator at 25° C. The initial value was measured by peeling the adhesive film from the copper plate at 90° at room temperature.

[0155] After heat treatment at 175°C for 2 hours, at 220°C for 0.5 hours, and further at 175°C for 1 hour, the adhesive film was peeled off from the copper plate at a 90° angle at room temperature to measure the adhesive strength. Because the adhesive strength has some variation, the average of the five measurements (rounded off) was used.

[0156] Furthermore, after the adhesive strength measurement, transfer of the adhesive from the adhesive film to the copper plate (adhesive residue) was confirmed.

[0157] (4) Sealing resin leakage and warping of substrates laminated with adhesive films

[0158] The adhesive film was bonded to a copper lead frame (C-7025, 125 μm thick, size: 65 mm × 250 mm, linear expansion coefficient of 17.6 ppm / °C) at 25°C, heat treated at 175°C for 2.0 hours and at 220°C for 0.5 hours, and then transfer molded using an epoxy-based sealing material (linear expansion coefficient of 12 ppm / °C) at a temperature of 175°C, a pressure of 8 MPa, and a time of 5 minutes.

[0159] After molding, leakage of the molding resin from the outer lead portion to which the adhesive film was applied was visually checked, and the amount of warpage was measured.

[0160] The evaluation results are shown in the following Tables 1 and 2. The weight average molecular weight of the polyimide resin obtained in each of the Examples and Comparative Examples was approximately 25,000.

[0161] [Table 1]

[0162] Table 1

[0163]

[0164]

[0165] [Table 2]

[0166] Table 2

[0167]

[0168]

[0169] Industrial applicability

[0170] The resin composition containing the polyimide resin of the present invention has adhesiveness at room temperature, excellent heat resistance, and excellent re-peelability. Therefore, it can be suitably used in the field of heat-resistant adhesive films used in the process of sealing semiconductors or electronic parts with sealing resins, or in the field of heat-resistant adhesive films used in reflow processes, etc., in semiconductor element mounting substrates such as lead frames, printed circuit boards, wafers, and sealing resin substrates for fan-out wafer-level packaging.

Claims

1. A polyimide resin, which is a solvent-soluble imide resin having a cyclic imide structure, characterized in that It has a repeating unit represented by the following general formula (1): [Chemical Formula 1] In the formula, Z is a tetracarboxylic dianhydride residue, and A is a diamine residue of a polysiloxane-based diamine, a diamine residue having an anilide group, and / or a diamine residue having a carboxyl group.

2. The polyimide resin according to claim 1, wherein the polysiloxane diamine is represented by the following general formula (2), and the diamine residues of the polysiloxane diamine represented by the following general formula (2) are contained in an amount of 60 to 97 mol% among all diamine residues: [Chemical Formula 2] In the formula, n is a natural number, an integer of 1 to 150; R1 and R2 are the same or different from each other and represent an alkylene group or a phenylene group having 1 to 40 carbon atoms; R3 to R6 are the same or different from each other and represent an alkyl group, a phenyl group or a phenoxy group having 1 to 40 carbon atoms. 3 . The polyimide resin according to claim 1 , wherein the total content of the diamine residue having an anilide group and the diamine residue having a carboxyl group is 3 to 40 mol % of all diamine residues.

4. The polyimide resin according to claim 1, wherein the diamine residue having a carboxyl group is a diamine residue of at least one diamine selected from the group consisting of the diamines represented by the following general formulas (3) to (5): [Chemical Formula 3] In the formula, X is a single bond, a substituted or unsubstituted alkylene group, a carbonyl group, or an ether group, p is an integer from 0 to 2, m1 is an integer from 0 to 4, and m2 is an integer from 0 to 4, wherein when p is 0, m1 is an integer from 1 to 4, [Chemical Formula 4] [Chemical Formula 5] 5. The polyimide resin according to claim 1, wherein the diamine residue having an anilide group is a diamine residue of at least one diamine represented by the following general formulas (6-1) to (6-3): [Chemical Formula 6] In the formula, R1 to R8 are the same or different from each other and represent an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, and n1 to n8 each represent an integer of 0 to 4.

6. A resin composition characterized in that Contains the polyimide resin according to claim 1 and an organic solvent. The resin composition according to claim 6 , wherein the resin composition contains an epoxy compound.

8. The resin composition according to claim 7, wherein the epoxy compound is a compound represented by the following formula (7): [Chemical Formula 7] 9 . The resin composition according to claim 6 , wherein the organic solvent comprises cyclohexanone. 10 . The resin composition according to claim 6 , wherein the glass transition temperature of the resin composition after drying is -10 to 40° C.

11. An adhesive for semiconductor or electronic component production, comprising the polyimide resin according to claim 1.

12. An adhesive film for semiconductor or electronic component production, comprising laminating the resin composition according to claim 6 on at least one surface of a heat-resistant film. 13 . The adhesive film according to claim 12 , wherein a surface of the heat-resistant film on which the resin composition is laminated is a surface subjected to a surface roughening treatment. 14 . The adhesive film according to claim 12 , wherein a heat-resistant insulating film subjected to a mold release treatment is further laminated on the surface of the resin composition laminated on at least one surface of the heat-resistant film. 15 . The adhesive film according to claim 12 , wherein the adhesive film is an adhesive film for being attached to a semiconductor element mounting substrate such as a lead frame, a printed circuit board, a wafer, and a sealing resin substrate for fan-out wafer-level packaging.

16. A method for manufacturing a semiconductor or electronic component, characterized in that The method comprises the steps of attaching the adhesive film according to claim 12 to a semiconductor element mounting substrate, and peeling off the adhesive film after heat treatment. 17 . A method for producing the polyimide resin according to claim 1 , comprising reacting tetracarboxylic dianhydride, a polysiloxane-based diamine, a diamine having an anilide group, and / or a diamine having a carboxyl group in the presence of a lactone-based catalyst.

Images