TW202502907A - Polyimide resin and adhesive film - Google Patents

Abstract

An object of the present invention is to provide a polyimide resin which generates little volatile component even at high temperature, has good adherence at low temperature, can be subjected to laminating at ordinary temperature, has proper adhesiveness after being passed through a heat treatment step at high temperature, can be then easily detached at ordinary temperature without adhesive transfer, causes little warping at each step, and can prevent mold flash, when used as an adhesive film for producing a semiconductor or electronic parts. The present invention provides a solvent-soluble polyimide resin having a cyclic imide structure, which polyimide resin has repeating units including a diamine residue of a polysiloxane-type diamine, and a diamine residue having an anilide group and/or a diamine residue having a carboxyl group. The present invention also provides an adhesive film which is produced by laminating a resin composition containing the polyimide resin on at least one side of a heat-resistant film.

Description

Polyimide resin and adhesive film

The present invention relates to a polyimide resin that can be suitably used as a heat-resistant adhesive for manufacturing semiconductor or electronic components. More specifically, it relates to a polyimide resin for manufacturing semiconductor or electronic components that is used to be attached to a semiconductor element mounting substrate when manufacturing a semiconductor package, a resin composition containing the same, an adhesive, and an adhesive film.

In recent years, with the increasing demand for miniaturization and lightness of electronic equipment, the electronic components built into them are also required to be miniaturized and mounted at a high density. Therefore, various forms of semiconductor packages have been developed. For example, as a surface array mounting package, there is a chip size package (CSP) that greatly reduces the size of the ball grid array (BGA). Among the CSPs, the quad flat non-leaded package (QFN) was developed for the purpose of miniaturization and low height of the quad flat package (QFP) using leads. It is a package that uses electrode pads instead of leads as connection terminals. Since QFN has an external lead portion in the sealing area, there is a problem of causing abnormal molding overflow of the sealing resin package. To solve this problem, it is effective to protect the lead portion outside the lead frame by an adhesive film during resin sealing. Based on this viewpoint, various adhesive films useful for semiconductor packaging such as QFN have been proposed.

Such adhesive films are usually produced by providing various adhesive layers on a heat-resistant film. As the heat-resistant film, polyimide, polyamide, polyamide imide, polyether imide, polyester, polyphenylene sulfide, polysulfone, polyether sulfone, etc. are proposed, and as the resin of the adhesive layer, acrylic resin, polysilicone resin, polyamide resin, polyimide resin, etc. are proposed. Since the adhesive layer is peeled off from the lead frame after being heated to a high temperature in the heating steps of die attach, wire bonding, resin sealing, etc., it is required to solve not only the molding flash but also the adaptability to each process, paste residue and warp. For this purpose, various adhesive layers have been proposed.

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

Furthermore, Patent Document 2 discloses that the following resin composition can be used as a heat-resistant adhesive when manufacturing electronic devices. The resin composition contains a polyimide resin and a hydroxymethyl compound, and the diamine residues of the polyimide resin are residues of polysiloxane diamine and residues of aromatic diamine having a hydroxyl group. Patent Document 2 states that when either the residue of aromatic diamine having a hydroxyl group in the polyimide resin or the hydroxymethyl compound in the resin composition is absent, the adhesion to the polyimide film belonging to the substrate is greatly improved after treatment at 300°C, and cannot be peeled off at room temperature (paragraph 0098).

Furthermore, Patent Document 3 discloses that the following adhesive film is used as an adhesive film for manufacturing semiconductors or electronic components, wherein the adhesive film has a heat-resistant film and an adhesive layer, and the adhesive layer contains a polyimide copolymer, and the polyimide copolymer contains 30 to 100 mol % of polysiloxane diamine residues in all diamine residues.

In patent documents 2 and 3, complete imidization is performed by synthesizing polyamide, applying a resin composition containing polyamide on a substrate such as a glass substrate or a polyimide film, and then heating to 250°C. However, adhesive films using polyimide resins described in patent documents 1 to 3 have the following problem, that is, when the adhesive layer is peeled off from the lead frame after the heating step at a high temperature, paste residues are generated due to the conditions. [Prior art document] [Patent document]

[Patent Document 1] Japanese Patent Publication No. 2004-277619 [Patent Document 2] International Publication No. 2014/050878 [Patent Document 3] Japanese Patent Publication No. 2020-136600

(Invent the problem you want to solve)

As mentioned above, the properties required of a high heat-resistant adhesive resin or adhesive film for semiconductor manufacturing are heat resistance at high temperatures, low decomposition, lamination at room temperature, re-peeling at room temperature after high-temperature heat treatment, and low warping in each step. As a resin that meets these requirements, 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 paste residue when peeling off the adhesive layer after the heating step at high temperature. Furthermore, there is a problem that, when a resin composition containing polyamide is coated on a substrate such as a glass substrate or a polyimide film and then heated to a high temperature such as 250° C. for complete imidization, a dehydration and shrinkage reaction occurs, causing the adhesive film to curl.

In view of this situation, the purpose 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 manufacturing the same. The polyimide resin having a cyclic imide structure produces less volatiles due to decomposition even at a high temperature of more than 250°C, has good adhesion at low temperatures, can be laminated at room temperature, has suitable adhesion after a high-temperature heat treatment step, and can be easily re-stripped at room temperature without leaving any paste, and has less warping in each step, which can prevent molding flash. (Technical means to solve the problem)

The inventors of the present invention have conducted intensive research to solve the above-mentioned problems and have found that by using a copolymer having a tetracarboxylic dianhydride residue, a diamine residue of a polysiloxane-based diamine, and a diamine residue having an aniline group and/or a diamine residue having a carboxyl group as a polyimide resin having a cyclic imide structure, a solvent-soluble polyimide resin having a cyclic imide structure that provides suitable adhesion and re-peelability can be obtained. It was also discovered that the above-mentioned problems can be solved by using a resin composition containing such a resin, and an adhesive for semiconductor or electronic component manufacturing that has heat resistance at high temperatures, low decomposition properties, lamination properties at room temperature, re-peelability at room temperature after high-temperature heat treatment, and low warping properties in each step, and an adhesive film using the same can be provided, thereby completing the present invention.

That is, the present invention provides a polyimide resin, which is characterized in that it is a solvent-soluble polyimide resin having a cyclic imide structure and has a repeating unit represented by the following general formula (1).

[Chemistry 1]

(wherein, Z is a tetracarboxylic dianhydride residue, and A is a diamine residue of a polysiloxane-based diamine, a diamine residue having an aniline group, and/or a diamine residue having a carboxyl group)

In addition, the present invention provides a resin composition, which is characterized in that it contains the polyimide resin of the present invention and an organic solvent. In addition, the present invention provides an adhesive for manufacturing semiconductor or electronic components, which contains the polyimide resin of the present invention. Furthermore, the present invention provides an adhesive film for manufacturing semiconductor or electronic components, which is formed by laminating the resin composition of the present invention on at least one side of a heat-resistant film. (Compared with the effect of the prior art)

The present invention provides a polyimide resin, a resin composition containing the same, an adhesive, and an adhesive film. The polyimide resin produces less volatiles due to decomposition even at a high temperature of more than 250°C, has good adhesion at low temperatures, can be laminated at room temperature, has suitable adhesion after a high-temperature heat treatment step, and can be easily re-stripped at room temperature without leaving any paste, and has less warping in each step, which can prevent molding flash. Furthermore, since a solvent-soluble polyimide resin having a cyclic imide structure is used, a heating step for imidization is not required in the manufacturing step of the adhesive film, and a manufacturing process with higher productivity can be provided.

[Polyimide resin] 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" refers to a structure in which imide groups form a ring. In addition, the term "solvent soluble" in the present invention refers to the organic polar solvent used in the synthesis of polyimide and the organic solvent used to dilute the polyimide resin in the resin composition described below, which means that 5 g or more of the polyimide resin is dissolved in 100 g of the solvent.

[Chemistry 2]

(wherein, Z is a tetracarboxylic dianhydride residue, and A is a diamine residue of a polysiloxane-based diamine, a diamine residue having an aniline group, and/or a diamine residue having a carboxyl group)

The repeating unit represented by the general formula (1) has 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 diamine, a diamine residue ( _A2 ) having an anilide group and/or a diamine residue ( _A3 ) having a carboxyl group. That is, the polyimide resin of the present invention is characterized in that it is a polymer comprising the following repeating units (1-1) in which the diamine residue (A) is a diamine residue (A ₁ ) of a polysiloxane-based diamine, and the following repeating units (1-2) in which the diamine residue (A) is a diamine residue (A ₂ ) having an aniline group, or the following repeating units (1-3) in which the diamine residue (A) is a diamine residue (A ₃ ) having a carboxyl group.

[Chemistry 3]

(wherein Z is a tetracarboxylic dianhydride residue, and _A1 is a diamine residue of a polysiloxane-based diamine)

[Chemistry 4]

(wherein Z is a tetracarboxylic dianhydride residue, and _A2 is a diamine residue having an aniline group)

[Chemistry 5]

(wherein Z is a tetracarboxylic dianhydride residue, and _A3 is a diamine residue having a carboxyl group)

The polyimide resin of the present invention may be a random copolymer randomly comprising the above-mentioned repeating unit (1-1), repeating unit (1-2) and/or repeating unit (1-3), or may be a block polymer having a structure obtained by first polymerizing only a part of the above-mentioned repeating units (1-1) to repeating units (1-3).

As described in detail below, the resin composition including the polyimide resin of the present invention can be suitably used as a heat-resistant adhesive for manufacturing semiconductor or electronic components. By setting the diamine residue (A) constituting the polyimide resin of the present invention to the specific structure as described above, the adhesive layer deposited on the heat-resistant film can take into account both appropriate adhesion and paste residue during peeling (no paste residue). When using a diamine residue having a functional group other than a carboxyl group and an aniline group, it is difficult to take into account both appropriate adhesion and paste residue during peeling.

(Tetracarboxylic dianhydride residue) As the tetracarboxylic dianhydride residue (Z), it is preferably a residue containing an aromatic tetracarboxylic dianhydride. Specific examples of aromatic tetracarboxylic dianhydrides 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'- Diphenylsulfone tetracarboxylic dianhydride, 2,3,3',4'-diphenylsulfone tetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfone 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"-para-triphenyltetracarboxylic dianhydride, 3,3",4,4"-isotriphenyltetracarboxylic dianhydride, 2,3,6,7-anthracenetetracarboxylic dianhydride, 1,2,7,8-phenanthrenetetracarboxylic dianhydride, etc. The above aromatic tetracarboxylic dianhydrides can be used alone or in combination of two or more. Among them, monocyclic acid dianhydrides such as pyromellitic dianhydride are preferred because they can improve heat resistance by increasing the heat reduction temperature.

(Diamine residue) The diamine residue (A) in the general formula (1) is a diamine residue of a polysiloxane diamine, a diamine residue having an aniline group and/or a diamine residue having a carboxyl group. The polysiloxane diamine constituting the diamine residue of the polysiloxane diamine is not particularly limited, and preferably is a polysiloxane diamine represented by the following general formula (2).

[Chemistry 6]

In formula (2), n is a natural number and is an integer of 1 to 150. n is preferably 5 to 50, and 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, and 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, and more preferably an alkyl group having 1 to 5 carbon atoms.

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(2-aminoethyl)polydiphenylsiloxane, α,ω-bis(3-aminopropyl)polydibutylsiloxane, α,ω-bis(3-aminopropyl)polydiphenylsiloxane, α,ω-bis(2-aminoethyl)polydiphenylsiloxane, α,ω-bis(3-aminopropyl)polydiphenylsiloxane, α,ω-bis(2-aminopropyl)polydiphenylsiloxane, α,ω-bis(3-aminopropyl)polydiphenylsiloxane, α,ω-bis(2-aminoethyl)polydiphenylsiloxane, α,ω-bis(3 ...2-aminopropyl)polydiphenylsiloxane, α,ω-bis(3-aminopropyl) 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 in terms of excellent balance of adhesion, reactivity and solubility in reaction solvents. The polysiloxane-based diamines represented by the general formula (2) can be used alone or in combination of two or more.

From the viewpoint of both suitable adhesion and paste residue during peeling (no paste residue), the content of diamine residues in the polysiloxane diamine is preferably set to 60 mol% or more, 65 mol% or more, further 68 mol% or more, and especially 70 mol% or more of all diamine residues, and is preferably set to 97 mol% or less, 95 mol% or less, further 93 mol% or less, and especially 90 mol% or less. If the diamine residues in the polysiloxane diamine exceed 97 mol% of all diamine residues, there is a tendency for the adhesion strength to increase, and there is a possibility of generating paste residues.

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).

[Chemistry 7]

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 of 0 to 2, m1 is an integer of 0 to 4, and m2 is an integer of 0 to 4. However, when p is 0, m1 is an integer of 1 to 4. Among them, X is preferably a single bond, p is preferably 0 to 1, and m1 is preferably 1 to 2.

Specific examples of the carboxyl-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, 4,4'-diaminobiphenyl-3,3'-dicarboxylic acid, etc. Among them, monocyclic carboxyl-containing aromatic diamines such as 3,5-diaminobenzoic acid and 3,4-diaminobenzoic acid are preferred in terms of maintaining an appropriate adhesive strength after the adhesive film has been subjected to a high-temperature heat treatment step and leaving no adhesive residue when the adhesive film is peeled off at room temperature.

Furthermore, as the diamine residue having a carboxyl group, the residue of an aromatic diamine containing a carboxyl group shown below (4) or (5) can also be used.

[Chemistry 8]

[Chemistry 9]

In the present invention, from the perspective of both suitable adhesion and paste residue during peeling (no paste residue), the number of carboxyl groups possessed by the carboxyl-containing aromatic diamine is preferably 1 to 5, more preferably 1 to 3, further preferably 1 to 2, and particularly preferably 1. The above-mentioned carboxyl-containing aromatic diamines may be used alone or in combination of two or more.

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

[Chemistry 10]

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 represent an integer of 0 to 4, preferably 0 to 1.

Specific examples of the aromatic diamines containing an aniline group represented by the general formulae (6-1) to (6-3) include 4,4'-diaminobenzanilide, 3,4'-diaminobenzanilide, 4,3'-diaminobenzanilide, 4,4'-diaminoparaphenylenediamine, 4,4'-diaminometaphenylenediamine, 3,3'-diaminoparaphenylenediamine, 3,3'-diaminoparaphenylenediamine, -diamino-m-phenylenediamine, 3,4'-diamino-p-phenylenediamine, 3,4'-diamino-m-phenylenediamine, 2-methoxy-4,4'-diaminobenzanilide, 2,2'-dimethoxy-4,4'-diaminobenzanilide, 2,6-dimethoxy-4,4'-diaminobenzanilide, 2,6'-dimethoxy-4,4'-diaminobenzanilide, etc. Among them, in terms of maintaining the adhesive strength at an appropriate value after the adhesive film passes through the high-temperature heat treatment step, and leaving no paste residue when the adhesive film is peeled off at room temperature, it is preferably a benzoylaniline structure, and preferably an aromatic diamine containing an acylanilide group represented by the above general formula (6-1). The above aromatic diamine containing an acylanilide group can be used alone or in combination of two or more. In the present invention, from the perspective of taking into account both appropriate adhesion and paste residue during peeling (no paste residue), the number of acylanilide groups possessed by the aromatic diamine containing an acylanilide group is preferably 1 to 3, more preferably 1 to 2, and further preferably 1. The above-mentioned carboxyl-containing aromatic diamine and aniline-containing aromatic diamine may be used in combination or either one of them may be used.

From the perspective of both suitable adhesion and paste residue during peeling, the total content of diamine residues having carboxyl groups and diamine residues having anilide groups is preferably set to 3 mol% or more, 5 mol% or more, further 7 mol% or more, and especially 10 mol% or more of all diamine residues, and preferably set to 40 mol% or less, 35 mol% or less, further 32 mol% or less, and especially 30 mol% or less. When the total content of diamine residues having carboxyl groups and diamine residues having anilide groups is less than 3 mol%, there is a possibility of paste residue, and when it exceeds 40 mol%, there is a possibility of reduced adhesion strength. When the above-mentioned carboxyl-containing aromatic diamine and aniline-containing aromatic diamine are used together, the molar ratio of the diamine residues having carboxyl groups to the diamine residues having aniline groups contained in the polyimide resin is preferably set to 9-5:1-5, and more preferably 8-6:2-4.

(Synthesis method of polyimide resin) The synthesis method of solvent-soluble polyimide can be any known method without any particular limitation. Solvent-soluble polyimide can be synthesized by using approximately equal amounts of the above-mentioned aromatic tetracarboxylic dianhydride and diamine in an organic polar solvent, in the presence of a catalyst and a dehydrating agent, at 160 to 200°C for several hours. 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 polyimide resin as 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, the above-mentioned aromatic tetracarboxylic dianhydride and diamine are used to synthesize a polyimide oligomer. Then, in the second stage, aromatic tetracarboxylic dianhydride and/or diamine are further added to perform polycondensation to produce a block copolymer polyimide.

As a catalyst for these reactions, a two-component acid-base catalyst utilizing the equilibrium reaction of lactone can be used to promote the dehydroimidation reaction. Specifically, γ-valerolactone and pyridine or N-methyl The two components of phenoxylate are catalysts (lactone catalysts). As shown in the following formula, water is generated as the imidization proceeds. The generated water participates in the equilibrium with the lactone to become an acid-base catalyst, thus showing a catalytic effect.

[Chemistry 11]

The water generated by the imidization reaction is removed from the system by azeotropy with a dehydrating agent such as toluene or xylene in a polar solvent. When the reaction is completed, the water in the solution is removed and the acid-base catalyst becomes γ-valerolactone and pyridine or N-methylol In this way, a high-purity polyimide solution can be obtained.

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

As other two-component catalysts, oxalic acid or malonic acid, and pyridine or N-methyl In a reaction solution at 160-200°C, oxalate or malonic acid salts act as acid catalysts to promote the imidization reaction. A catalytic amount of oxalic acid or malonic acid remains in the generated polyimide solvent. After the polyimide solution is coated on a substrate, it is heated 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 removed from the system in the form of gas. The activity of oxalic acid-pyridine catalysts is stronger than that of valerolactone-pyridine catalysts, and high molecular weight polyimide can be generated in a short time.

[Chemistry 12]

As the organic polar solvent for synthesizing the solvent-soluble polyimide, from the viewpoint of the solubility and storage stability of the polyimide copolymer or the polyimide resin, it is preferred to use a glycol ether-based solvent, an amide-based polar solvent, or a ketone-based solvent.

Specifically, the glycol ether-based solvent includes propylene glycol mono-t-butyl ether, ethylene glycol mono-t-butyl ether, propylene glycol mono-n-butyl ether, propylene glycol mono-propyl ether, propylene glycol mono-ethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-propyl 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 mono-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol mono-propyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tripropylene glycol dimethyl ether, and tetraethylene glycol dimethyl ether.

As the amide-based polar solvent, specifically, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, 1,3-dimethyl-2-imidazoline can be listed. As the ketone-based solvent, specifically, cyclohexanone can be listed. These organic polar solvents can be used alone or in combination of two or more. Among them, glycol ether-based solvents are preferred because they can improve the storage stability of the synthesized polyimide resin solution.

By the above method, a solvent-soluble polyimide resin having a cyclic imide structure can be synthesized with high purity. Since the obtained polyimide resin has a cyclic imide structure, it does not need to be heated to a high temperature such as 250°C for complete imidization after being coated on the substrate like polyamide, thereby avoiding the problem of deformation of the adhesive film, and since the heating step at a high temperature is omitted, a process with higher productivity can be provided. The molecular weight of the obtained solvent-soluble polyimide resin is 10,000 to 200,000 in terms of weight average molecular weight converted to polystyrene. Polyimide resins within this weight average molecular weight range can achieve good solvent solubility, membrane properties and insulation properties.

[Resin composition] A resin composition containing a solvent-soluble polyimide resin produced in the above manner and an organic solvent can be suitably used as a heat-resistant adhesive for the manufacture of semiconductors or electronic components. The resin composition of the present invention is a resin composition in a solution state obtained by dissolving a polyimide resin in an organic solvent in a manner such that its solid content becomes 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 directly used. By directly using the organic solvent used in the synthesis method of the solvent-soluble polyimide resin as the organic solvent of the resin composition, a resin composition in the form of a solution obtained by dissolving the polyimide resin in the above-mentioned organic polar solvent in a manner such that the solid content is 10 to 50% by weight can be easily obtained.

As an organic solvent contained in the resin composition, if cyclohexanone is used alone or mixed with other organic solvents, the drying temperature during application can be lowered, and the amount of residual solvent in the drying step can be reduced to a certain extent at a low temperature (160-180°C), so it is better. When cyclohexanone is used as an organic solvent, the proportion of cyclohexanone in the organic solvent contained in the resin composition is usually 20-60 volume%, preferably 30-50 volume%, and more preferably 35-45 volume%. When cyclohexanone is combined with other organic solvents in the resin composition, the other organic solvent is preferably a glycol ether solvent such as triethylene glycol dimethyl ether. For example, by using a glycol ether solvent such as triethylene glycol dimethyl ether and a ketone solvent such as cyclohexanone in a ratio of 8:2 to 4:6, preferably 7:3 to 5:5 (volume ratio), there are advantages that monomer solubility, drying temperature reduction and stability are all improved. Furthermore, the organic solvent contained in the resin composition is not limited to the above, and other organic solvents can also be used.

(Epoxy compound) From the viewpoint of adjusting the adhesive strength, the resin composition of the present invention preferably contains an epoxy compound. The epoxy compound is not particularly limited and can be selected based on its compatibility with the polyimide resin composition. As the epoxy compound, for example, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, trisphenol A novolac type epoxy resin, Epoxy resins having a skeleton, epoxy resins containing a fluorene skeleton, naphthalene-type epoxy resins, biphenyl-type epoxy resins, crystalline epoxy resins, bisphenol A-type epoxy resins, etc., and high molecular weight epoxy resins thereof can also be used. Among them, from the viewpoint of reactivity, it is preferred to use a polyfunctional epoxy compound, and in particular, a monocyclic tetrafunctional epoxy compound represented by the following general formula (7) (N,N,N',N'-tetraglycidyl-1,3-phenylenedi(methylamine)) is preferred.

[Chemistry 13]

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, further preferably 3 parts by weight or more, particularly preferably 4 parts by weight or more, and is preferably 10 parts by weight or less, 9 parts by weight or less, 8 parts by weight or less, further preferably 7 parts by weight or less, particularly preferably 6 parts by weight or less, relative to 100 parts by weight (solid content) of the solvent-soluble polyimide.

(Other additives) Surfactants, silane coupling agents, leveling agents, etc. may also be added to the resin composition of the present invention to improve properties such as adhesion, heat resistance, and coating properties. When there is a concern that the resin composition may show a slight repulsive tendency during coating due to its composition, a leveling agent may be added, but the leveling agent is not a necessary component to achieve the effect of the present invention. In addition, the resin composition of the present invention may contain inorganic microparticles. By containing inorganic microparticles, the heat resistance and dimensional stability of the resin composition can be improved, and the adhesion can be adjusted. Specific examples of inorganic microparticles 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 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 by weight relative to 100 parts by weight (solid content) of polyimide resin.

[Adhesive film] The resin composition is laminated as a polyimide adhesive on at least one side of the heat-resistant film, thereby forming an adhesive layer on the surface of the heat-resistant film, and forming an adhesive film having a heat-resistant film and an adhesive layer. (Heat-resistant film) The heat-resistant film is an insulating plastic film that can be used in high-temperature processes such as die bonding, wire bonding, resin sealing, and reflow. Specifically, the plastic films include: polyimide, polyamide, polyamide imide, polyether imide, polyester, polyphenylene sulfide, polysulfone, polyether sulfone, etc. From the perspective of heat resistance, polyimide film is preferred. In order to improve the adhesion of the resin composition to the heat-resistant film, it is preferred to perform surface treatment (roughening treatment) such as plasma treatment or corona treatment on the heat-resistant film. As the plasma gas used for plasma treatment, oxygen, nitrogen, water, carbon dioxide, argon, or a mixture thereof can be used.

(Adhesive layer) The adhesive film of the present invention can be produced by the following method, that is, a resin composition is applied directly or via a base coating layer on a heat-resistant film to form an adhesive layer. As a method for applying the resin composition of the present invention to a heat-resistant film, there can be listed: a rotary coater, a roll coater, a notched wheel coater, gravure printing, screen printing, a slit die coater, etc. After applying the resin composition, it is dried at 100-150°C, and then heat-treated continuously or intermittently at 160-240°C for 2 minutes to 1 hour, thereby obtaining an adhesive layer with good adhesion and heat resistance. In the present invention, the resin composition can be directly applied and dried on a glass substrate to form an adhesive layer. As methods for applying on a glass substrate, there can be listed: rotary coater, screen printing, gravure coater, slit die coater, rod coater and other methods.

The weight loss rate of the adhesive layer when the temperature is increased from 30°C to 300°C is preferably 0.8% or less, more preferably 0.5% or less, and further preferably 0.3% or less. If the weight loss rate is greater than 0.8%, there is a possibility of contamination of the semiconductor component mounting substrate or poor bonding of wire bonding in the semiconductor manufacturing step. The thickness of the adhesive layer is preferably 2 to 30 μm, more preferably 3 to 20 μm, and further preferably 4 to 10 μm. When 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 component mounting substrate. Therefore, it is impossible to fill between the adhesive and, for example, the lead frame belonging to the semiconductor component mounting substrate, and molding flash is likely to occur. When 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 may increase, resulting in the risk of poor workability during the peeling step.

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, and preferably below 40°C, further below 30°C, and especially below 25°C. If the glass transition temperature exceeds 40°C, there is a possibility that good adhesion cannot be obtained when the substrate layer as the adherend is pressed onto the adhesive layer formed using the resin composition of the present invention. In addition, although the lower limit of the glass transition temperature will not affect the effect of the present invention, if it is too low, the adhesion may become too high. "Good adhesion" in the present invention means having a bonding force above the degree to which the substrate will not naturally peel off when the above-mentioned adhesive layer film is pressed onto the substrate at room temperature. Specifically, it means that when the substrate as the adherend is peeled at a peeling angle of 90 degrees and a peeling speed of 10 mm/minute, it has an adhesion force of more than 5 g/cm. When it is desired to increase the initial peeling strength of the adherend, this can also be achieved by increasing the lamination temperature.

Generally, when an adhesive layer containing a polyimide adhesive is subjected to a high-temperature heat treatment step, the adhesive strength increases. However, although the adhesive containing the polyimide resin of the present invention increases its adhesive strength after the initial heat treatment at about 150°C, the change in adhesive 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 adhesion to the adhesive layer because it has a diamine residue with a specific structure in the repeating unit. The appropriate adhesive 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 adhesive strength to an appropriate value, it can be adjusted by adding epoxy compounds or inorganic microparticles (fillers).

(Adhesive film) 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 the above-mentioned adhesive layer containing the 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 thermal history in the die bonding step, wire bonding step, flip chip step, redistribution layer formation step, and resin sealing step in the semiconductor manufacturing step is less subject to changes such as decomposition and degradation, and exhibits stable adhesion. Furthermore, by using the specific polyimide resin of the present invention, it is not easy to generate paste residue on the surface of the semiconductor component mounting substrate when it is peeled off from the semiconductor component mounting substrate after sealing.

In addition, the adhesive film of the present invention is less susceptible to decomposition and degradation due to thermal history, and is therefore suitable for use as an adhesive film for the manufacture of electronic components, and can also be suitably used in the manufacturing steps of electronic components using high-temperature processes such as reflow.

The adhesive film of the present invention may also pre-laminate a peelable 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, polyethylene terephthalate, metal foil such as aluminum foil, copper foil, or a laminated film of plastic film and metal foil. In addition, the surface of the protective film may be pre-treated with a release agent such as a silicone or fluorine-based release agent to facilitate peeling of the protective film.

When the adhesive film of the present invention is used as an adhesive transfer film, a mold release treatment may be performed on one or both sides of the heat-resistant film according to the purpose. As the mold release treatment, it is preferred to coat the film with silicone resin, fluorine resin, etc.

The adhesive film of the present invention can be used to adhere to a semiconductor element mounting substrate that carries semiconductors or electronic components. As semiconductor element mounting substrates, there can be listed: lead frame, printed circuit substrate, wafer, and sealing resin substrate for wafer fan-out wafer level packaging (F0WLP). Semiconductor elements refer to semiconductors and electronic components. For example, semiconductor elements can be mounted on a lead frame via a die adhesive film, or mounted on a printed circuit substrate by flip-chip connection and subsequent reflow process. In addition, with regard to semiconductor elements, as in fan-out packaging, the chip can be attached to the adhesive film of the present invention, and then the attached chip can be resin-sealed at one time, and the semiconductor element can be mounted on a sealing resin wafer substrate. Furthermore, semiconductor devices also include wafers having circuits such as semiconductor devices or comb electrodes formed on the wafer.

By using the polyimide resin of the present invention, for example, in a fan-out packaging process, since there is no paste residue on the exposed surface after the adhesive film is peeled off from the sealing resin wafer substrate, a step of forming a redistribution layer on the exposed surface or a step of cutting the redistribution layer can be performed. [Example]

Hereinafter, the present invention will be described in detail based on embodiments, but the present invention is not limited to the following embodiments.

1. Synthesis of solvent-soluble polyimide resin and resin composition (Example 1) Install a stirrer, a nitrogen inlet tube, and a Dean-Stark apparatus in a separable three-necked flask made of glass. 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 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 in a nitrogen atmosphere, and then the temperature was raised to 180°C. During the reaction, water was removed by azeotropy with toluene. After confirming that the water was removed by distillation, the mixture was heated and stirred for 6 hours and then cooled. 1.94 parts by weight of KL-700 (a 100% by weight leveling agent manufactured by Kyoeisha Chemical Co., Ltd.) was added and then cooled to room temperature to obtain an adhesive resin composition with a solid content of 45 wt%.

(Example 2) In Example 1, the amount of KF-8010 used was set to 236.13 g (0.278 mol), and the amount of 3,5-DABA used was set to 18.11 g (0.119 mol). In addition, an adhesive resin composition with a solid content of 40 wt% was obtained in the same manner as in Example 1.

(Example 3) In Example 1, 8.86 g (0.039 mol) of 4,4'-diaminobenzanilide was used instead of 3,5-DABA. In addition, an adhesive resin composition with a solid content of 45 wt% was obtained in the same manner as in Example 1.

(Example 4) 5 parts by weight of N,N,N',N'-tetraglycidyl-1,3-phenylenedi(methylamine) was added to the resin composition of Example 1 relative 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 with a solid content of 48 wt%.

(Example 5) Spherical silica slurry (SO-C1 (particle size 0.2-0.4 μm) N-methyl-2-pyrrolidone (hereinafter referred to as NMP) slurry, 50% solid content by weight, manufactured by Admatechs Co., Ltd.) was added to the resin composition of Example 1, with a solid content of 100 parts by weight of the polyimide resin, and diluted with NMP to obtain an adhesive resin composition with a solid content of 45 wt%.

(Comparative Example 1) In Example 1, 11.23 g (0.040 mol) of 4,4'-methylenebis(2-ethyl-6-methylaniline) was used instead of 3,5-DABA. In addition, an adhesive resin composition with a solid content of 45 wt% was obtained in the same manner as in Example 1.

(Comparative Example 2) A stirrer, a nitrogen inlet tube, and a Dean-Stark apparatus were installed in a separable three-necked glass flask. KF-8010 245.01 g (0.288 mol), PMDA 62.87 g (0.288 mol), valerolactone 1.44 g (0.014 mol), pyridine 2.28 g (0.029 mol), NMP 553 g, and toluene 70 g were added, and the mixture was stirred at 180 rpm for 30 minutes at room temperature under a nitrogen atmosphere, and then the temperature was raised to 180°C. During the reaction, water was removed by azeotropy with toluene. After confirming that the water was distilled off, the mixture was heated and stirred for 6 hours and then cooled. 1.94 parts by weight of KL-700 (a 100% by weight leveling agent manufactured by Kyoeisha Chemical Co., Ltd.) was added and then cooled to room temperature to obtain an adhesive resin composition with a solid content of 35 wt%.

(Comparative Example 3) In Example 1, 11.62 g (0.040 mol) of 1,3-bis(3-aminophenoxy)benzene was used instead of 3,5-DABA. In addition, an adhesive resin composition with a solid content of 45 wt% was obtained in the same manner as in Example 1.

(Comparative Example 4) In Example 1, 7.96 g (0.040 mol) of 4,4'-diaminodiphenyl ether was used instead of 3,5-DABA. In addition, an adhesive resin composition with a solid content of 45 wt% was obtained in the same manner as in Example 1.

(Comparative Example 5) In Example 1, 8.44 g (0.040 mol) of 3,3'-diaminobenzophenone was used instead of 3,5-DABA. In addition, an adhesive resin composition with a solid content of 45 wt% was obtained in the same manner as in Example 1.

2. Evaluation of the properties of polyimide resin composition and adhesive film The adhesive resin composition synthesized in Examples 1 to 5 and Comparative Examples 1 to 5 was applied to a Japanese stainless steel standard (SUS, Steel Use Stainless) plate by a rotary coater in such a manner that the thickness of the adhesive layer became 8 μm. Thereafter, the resins of Examples 1 to 4 and Comparative Examples 1, 3 to 5 were dried at 120°C for 10 minutes, and then at 180°C for 20 minutes. 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. The reason for changing the drying conditions in this way is that even when solvents with different boiling points are used in the embodiment and the comparative example, the amount of residual solvent is made consistent, and this change in drying conditions will not affect the properties of the adhesive film.

(1) Glass transition temperature Tg (℃) The resin of the adhesive layer obtained after drying is cut by a cutting machine, and about 10 mg is placed in an aluminum standard container. The DSC differential scanning calorimeter is used for measurement. The glass transition temperature (℃) is calculated based on the inflection point of the obtained DSC curve. After pre-drying at 80℃ for 30 minutes, the measurement is performed at a heating rate of 10℃/min.

(2) Thermogravimetric weight loss rate (%) The resin of the adhesive layer obtained after drying is cut by a cutter, and about 15 mg of the resin is placed in an aluminum standard container and measured using a thermogravimetric analyzer TG-DTA. The measurement conditions are to increase the temperature to 400°C at a rate of 5°C/min, and measure the weight loss rate (%) at 30-300°C.

Next, the resin compositions synthesized in Examples 1 to 5 and Comparative Examples 1 to 5 were coated on a polyimide film having a thickness of 50 μm by a rotary coater in such a manner that the thickness of the adhesive layer became 8 μm. Thereafter, the resins of Examples 1 to 4 and Comparative Examples 1, 3 to 5 were dried at 120° C. for 10 minutes and then at 180° C. for 20 minutes, and 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, thereby obtaining adhesive films. For Examples 1 to 4, drying was performed at 120° C. for 10 minutes and then at 180° C. for 20 minutes. For Example 5 and Comparative Examples 1 to 2, drying was performed at 120° C. for 10 minutes and then at 220° C. for 20 minutes to obtain an adhesive film.

(3) Adhesion strength Then, the obtained adhesive film was bonded to a copper plate (C-7025) with a thickness of 125 μm at 25°C using a bonding machine. The initial value was measured by peeling the adhesive film from the copper plate at 90° at room temperature. After that, the film was heat treated at 175°C for 2 hours, at 220°C for 0.5 hours, and at 175°C for 1 hour. The adhesive strength was then measured by peeling the adhesive film from the copper plate at 90° at room temperature. Since the adhesion strength was somewhat uneven, the average value of the values obtained from 5 measurements was taken (rounded off). In addition, the transfer of adhesive from the adhesive film to the copper plate (paste residue) was confirmed after the adhesive strength measurement.

(4) Leakage and warping of sealing resin on substrates laminated with adhesive film The adhesive film was attached to a copper lead frame (C-7025, 125 μm thickness, size: 65 mm×250 mm, linear expansion coefficient 17.6 ppm/℃) at 25℃, heat treated at 175℃ for 2.0 hours and at 220℃ for 0.5 hours, and then transfer molded at 175℃, 8 MPa, and 5 minutes using an epoxy sealing material (linear expansion coefficient 12 ppm/℃). After molding, leakage of the molding resin outside the lead portion where the adhesive film was attached was visually confirmed. In addition, the amount of warping was measured. The evaluation results are shown in Tables 1 and 2 below. In addition, the weight average molecular weight of the polyimide resin obtained in each embodiment and comparative example is about 25,000.

[Table 1] Table 1 Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Adhesive Polyimide resin composition Polysiloxane diamine (mol%) 90 70 90 90 90 Aromatic diamine containing carboxyl group (molar %) 10 30 10 10 Aromatic diamine containing aniline group (molar %) 10 Other diamines (mol%) Additives Epoxide (parts by weight) 0 0 0 5 0 Silicon dioxide (parts by weight) 0 0 0 0 10 Tg(℃) -1 20 0 2 -1 30～300℃Thermogravimetric loss rate (%) 0.22 0.23 0.24 0.20 0.20 (Polyimide substrate) Thickness (μm) Linear expansion coefficient (ppm/℃) Kapton 200EN 50 16 Adhesive thickness (μm) 8 (Semiconductor device mounting substrate) Substrate type Thickness (μm) Size (mm) Linear expansion coefficient (ppm/℃) Copper (C-7025) 125 65×250 17.6 Sealing material linear expansion coefficient (ppm/℃) 12 Adhesion strength (g/cm) initial 25℃ lamination 75 60 78 50 65 After thermal process 25℃ layer pressure＋175℃×2 H ＋220℃×0.5 H ＋175℃×1 H 235 135 245 125 150 Paste residue without without without without without Sealing resin leakage without without without without without Warp of substrate laminated with adhesive film after molding (mm) 0.1 0.2 0.1 0.2 0.0

[Table 2] Table 2 Comparison Example 1 Comparison Example 2 Comparison Example 3 Comparison Example 4 Comparison Example 5 Adhesive Polyimide resin composition Polysiloxane diamine (mol%) 90 100 90 90 90 Aromatic diamine containing carboxyl group (molar %) Aromatic diamine containing aniline group (molar %) Other diamines (mol%) 10 10 10 10 Additives Epoxide (parts by weight) 0 0 0 0 0 Silicon dioxide (parts by weight) 0 0 0 0 0 Tg(℃) 0 -5 2 1 0 30～300℃Thermogravimetric loss rate (%) 0.30 0.29 0.32 0.32 0.30 (Polyimide substrate) Thickness (μm) Linear expansion coefficient (ppm/℃) Kapton 200EN 50 16 Adhesive thickness (μm) 8 (Semiconductor device mounting substrate) Substrate type Thickness (μm) Size (mm) Linear expansion coefficient (ppm/℃) Copper (C-7025) 125 65×250 17.6 Sealing material linear expansion coefficient (ppm/℃) 12 Adhesion strength (g/cm) initial 25℃ lamination 150 180 160 175 175 After thermal process 25℃ layer pressure＋175℃×2 H ＋220℃×0.5 H ＋175℃×1 H 615 800 755 705 650 Paste residue have have have have have Sealing resin leakage without without without without without Warp of substrate laminated with adhesive film after molding (mm) 0.2 0.1 0.2 0.2 0.2 (Industrial Availability)

The resin composition including the polyimide resin of the present invention has good adhesion 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 step of sealing semiconductors or electronic components with sealing resins, or in the field of heat-resistant adhesive films used in reflow steps, etc., in semiconductor component mounting substrates such as lead frames, printed circuit substrates, wafers, and sealing resin substrates for wafer fan-out wafer-level packaging.

Claims (17)

A polyimide resin is characterized in that it is a solvent-soluble polyimide resin having a cyclic imide structure and has repeating units represented by the following general formula (1): (wherein, Z is a tetracarboxylic dianhydride residue, and A is a diamine residue of a polysiloxane-based diamine, a diamine residue having an aniline group, and/or a diamine residue having a carboxyl group). The polyimide resin of 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 2] (wherein, n is a natural number and an integer of 1 to 150; _R1 and _R2 are the same or different and represent an alkylene group or a phenylene group having 1 to 40 carbon atoms; _R3 to _R6 are the same or different and represent an alkylene group, a phenyl group or a phenoxy group having 1 to 40 carbon atoms). The polyimide resin of claim 1, wherein the total content of the diamine residues having an aniline group and the diamine residues having a carboxyl group is 3 to 40 mol% of all diamine residues. The polyimide resin of claim 1, wherein the diamine residue having a carboxyl group is a diamine residue of at least one diamine among the diamines represented by the following general formulas (3) to (5); [Chemical 3] (wherein 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); [Chemistry 4] [Chemistry 5] . The polyimide resin of claim 1, wherein the diamine residue having an aniline group is a diamine residue of at least one diamine represented by the following general formulas (6-1) to (6-3); (In the formula, R ₁ to R ₈ 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 represent integers of 0 to 4, respectively). A resin composition is characterized in that it contains the polyimide resin of claim 1 and an organic solvent. The resin composition of claim 6, wherein the resin composition contains an epoxy compound. The resin composition of claim 7, wherein the epoxy compound is a compound represented by the following formula (7): . The resin composition of claim 6, wherein the organic solvent comprises cyclohexanone. The resin composition of claim 6, wherein the glass transition temperature of the resin composition after drying is -10 to 40°C. An adhesive for semiconductor or electronic component manufacturing, comprising the polyimide resin of claim 1. An adhesive film for manufacturing semiconductor or electronic components, which is formed by laminating the resin composition of claim 6 on at least one side of a heat-resistant film. As in claim 12, the surface of the heat-resistant film on which the resin composition is laminated is a roughened surface. The adhesive film of claim 12 is formed by laminating the resin composition on at least one side of the heat-resistant film, and further laminating a heat-resistant insulating film that has been subjected to mold release treatment. As in claim 12, the adhesive film is an adhesive film used to adhere to a semiconductor element mounting substrate, and the semiconductor element mounting substrate is a lead frame, a printed circuit substrate, a wafer, and a sealing resin substrate for wafer fan-out type wafer-level packaging. A method for manufacturing a semiconductor or electronic component is characterized in that it includes the following steps: attaching the adhesive film of claim 12 to a semiconductor element mounting substrate, and peeling off the adhesive film after heat treatment. A method for producing the polyimide resin of claim 1, wherein the polyimide resin of claim 1 is produced by reacting tetracarboxylic dianhydride, polysiloxane diamine, diamine having an aniline group and/or diamine having a carboxyl group in the presence of a lactone catalyst.