JP5103870B2 - Adhesive composition for semiconductor, semiconductor device using the same, and method for manufacturing semiconductor device - Google Patents

Description

  The present invention relates to a semiconductor substrate such as an IC or LSI obtained by forming a semiconductor adhesive composition on a semiconductor wafer and then dicing the wafer with the semiconductor adhesive composition into a flexible substrate, a glass epoxy substrate, a glass substrate, and a ceramic. The present invention relates to an adhesive composition for a semiconductor when electrically bonded to a circuit board such as a substrate, a semiconductor device using the same, and a method for manufacturing the semiconductor device.

  In recent years, with the miniaturization and high density of semiconductor devices, flip chip mounting (direct chip attach mounting) has attracted attention and rapidly spread as a method for mounting a semiconductor chip on a circuit board. In flip chip mounting, as a method for ensuring the connection reliability of the joining portion, after bonding the bump electrode formed on the semiconductor chip and the pad electrode of the circuit board, liquid is formed in the gap between the semiconductor chip and the circuit board. It is a common method to inject and cure a sealing adhesive. However, since the number of bump electrodes formed on the semiconductor chip and the height of the bump electrodes have been reduced in order to make the semiconductor device lighter, thinner, and smaller, the liquid sealing adhesive has been removed from the gap between the semiconductor chip and the circuit board. In some cases, the conventional method of injecting a sufficient amount to ensure the connection reliability of the joint portion cannot be used. In contrast, a method of bonding a semiconductor chip and a circuit board after applying a liquid adhesive called an underfill material to a circuit board or a semiconductor chip with bump electrodes by a method such as a dispenser or screen printing has come to be used. It was. However, since it is difficult to uniformly apply a liquid adhesive to a minute area, there are problems such as contamination of a circuit board and a semiconductor chip due to protrusion of the liquid adhesive, an increase in mounting area, and the presence of unsealed portions. (See Patent Document 1).

  In order to solve this problem, after laminating a semiconductor adhesive composition of a certain thickness on a semiconductor wafer with bump electrodes, the semiconductor wafer is made into individual semiconductor chips by dicing, and then the semiconductor chip is flip-chip connected to the circuit board. And the method (refer patent document 2) which performs electrical joining and resin sealing simultaneously, and the adhesive film used for it are proposed. According to this method, the bonding area of the semiconductor adhesive composition and the semiconductor chip can be made substantially the same, and the protrusion of the adhesive composition to the semiconductor chip is very small compared to the case where a liquid sealing adhesive is used. (See Patent Documents 3 and 4). However, the adhesive composition for semiconductors used in Patent Documents 3 and 4 is composed of a phenoxy resin having a fluorene skeleton, an epoxy resin, a microencapsulated imidazole derivative epoxy compound and a silica filler, or an organic solvent-soluble polyimide. , An epoxy resin, a phenol resin, and a silica filler. Since these are insulating compositions, it is necessary to directly bond the bump electrode and the circuit board for electrical connection between the bump electrode and the circuit board.

  Furthermore, when the dicing is performed after the liquid sealing adhesive described in Patent Document 1 is coated on the bump electrode surface side of the semiconductor wafer, the problem that the cutting powder tends to adhere to the liquid sealing adhesive, Due to high fluidity, multiple problems are likely to occur, such as the problem of liquid sealing adhesive adhering to the cut wafer end face and clogging of the cutting blade, and the problem of disturbance of the film surface due to the water jet pressure during cutting. . For this reason, it is difficult to industrially use the process of dicing after coating the liquid sealing adhesive described in Patent Document 1 on the bump electrode surface side of the semiconductor wafer. Further, when the semiconductor adhesive composition described in Patent Documents 3 and 4 is laminated on the surface of the semiconductor wafer with the bump electrodes, dicing is performed, the problem that the cutting powder easily adheres to the liquid sealing adhesive, and the liquid from the wafer. There is a problem that the sealing adhesive is peeled off, and the liquid sealing adhesive is chipped and cracked. Chipping and cracking of the liquid sealing adhesive can be improved to some extent by slowing down the cutting speed. However, considering the recent trend toward larger wafer diameters, the reduction in cutting speed is a cause of increased costs. Become. Further, the semiconductor adhesive composition described in Patent Document 3 uses a phenoxy resin having a fluorene skeleton or an organic solvent-soluble polyimide for imparting heat resistance, but it is coated on a semiconductor wafer with bump electrodes. It does not have sufficient heat resistance and insulation properties as an adhesive composition.

  On the other hand, Patent Document 5 discloses a method in which an organic solvent-soluble polyimide is combined with an epoxy resin having excellent compatibility with polyimide. However, since a solid epoxy resin is used for the epoxy resin, it has a very fragile property, and if it is laminated on a semiconductor wafer with a bump electrode and then diced, it will peel off from the wafer and the adhesive layer itself will be chipped. Cracking occurs.

  Further, a technique is known in which a solid epoxy resin that is solid at normal temperature and an epoxy resin that is liquid at normal temperature are mixed to provide flexibility (see Patent Document 6). However, when dicing is performed after forming an adhesive layer made of such resin on a semiconductor wafer with bump electrodes, there is a problem that the adhesive composition for semiconductor is peeled off from the wafer, and the adhesive composition for semiconductor is chipped or cracked. is there.

  Furthermore, an adhesive sheet containing polyimide, a tri- or higher functional epoxy resin, and a liquid epoxy resin is also disclosed (see Patent Document 7). However, when flip chip mounting is performed using an adhesive sheet containing polyimide described in Patent Document 7, the water absorption of this polyimide is high, so that it is stored in the adhesive sheet due to water absorption for heating during mounting. As a result, the adhesive sheet evaporates rapidly, causing the adhesive sheet to foam, resulting in problems such as insufficient adhesion between the semiconductor chip and the circuit board, and low connection reliability.

  As an organic solvent-soluble polyimide, a polyimide having a reactive group such as a phenolic hydroxyl group at the main chain terminal of the polymer (see Patent Document 8) is known.

On the other hand, as a technique for producing an anisotropic conductive film, a technique in which phenoxy resin, epoxy resin, or acrylic resin is filled with conductive particles is known (see Patent Documents 9 and 10). However, when dicing is performed after forming an adhesive layer made of such resin on a semiconductor wafer with bump electrodes, there is a problem that the adhesive composition for semiconductor is peeled off from the wafer, and the adhesive composition for semiconductor is chipped or cracked. is there.
JP 2004-211064 A (Claims) JP 2001-237268 A (Claim 1) JP 2004-315688 A (Claims) JP 2004-319823 A (Claims) JP 2003-192894 A (Claim 1) JP 2004-146495 A (claim 11, paragraph 39) Japanese Patent Laying-Open No. 2004-292281 (Claims, paragraph 73) International Publication No. 04/109403 Pamphlet JP 2006-249342 A (Claims) JP 10-226769 A (Claims)

  In order to solve the above-mentioned problems, the present invention does not cause cracking or peeling even when bent, and can be laminated on the side of a bump electrode of a semiconductor wafer with a bump electrode having a narrow pitch and a high pin count. Disclosed is an adhesive composition for semiconductors that can be cut at high speed without contamination or loss of powder. In addition, the semiconductor chip cut with high precision can be stably bonded to the electrode pad of the circuit board via the bump, and functions as an adhesive that exerts shrinkage stress between the semiconductor chip and the circuit board. By doing this, the adhesive composition for semiconductors which has a function which assists this conduction | electrical_connection and improves the reliability of a connection is provided.

That is, the present invention contains (a) an organic solvent-soluble polyimide, (b) an epoxy compound, (c) a curing accelerator, (d) conductive particles, and (b) 100 parts by weight of the epoxy compound ( a) 15 to 90 parts by weight of an organic solvent-soluble polyimide, (c) 0.1 to 10 parts by weight of a curing accelerator, and (b) an epoxy compound at 25 ° C. and 1.013 × 10 ⁵ N / m ² It contains a liquid compound and a compound that is solid at 25 ° C. and 1.013 × 10 ⁵ N / m ² , and the content of the liquid epoxy compound is 20% by weight or more and 60% by weight or less based on the total epoxy compound. An adhesive composition for a semiconductor.

  According to the composition of the present invention, a semiconductor wafer with a bump electrode can be laminated on the side face of the bump electrode without a gap, and can be cut at high speed without contamination of the cutting powder or loss of the adhesive layer during dicing. Further, by using the composition and the manufacturing method of the present invention, a semiconductor chip cut with high precision can be electrically bonded to an electrode pad of a circuit board through a bump, and stable conduction can be obtained. A semiconductor device that exhibits shrinkage stress between the chip and the circuit board and has excellent reliability can be obtained. Further, according to the manufacturing method of the present invention, the protruding amount of the adhesive used for the connection between the semiconductor chip and the substrate is small, the mounting area can be minimized, and the semiconductor chip can be thinned and mounted on the circuit board. Can be simplified.

The adhesive composition for a semiconductor of the present invention contains (a) an organic solvent-soluble polyimide, (b) an epoxy compound, (c) a curing accelerator, and (d) conductive particles, and (b) 100 weight of the epoxy compound. (A) 15 to 90 parts by weight of an organic solvent-soluble polyimide, (c) 0.1 to 10 parts by weight of a curing accelerator, and (b) an epoxy compound at 25 ° C. and 1.013 × 10 ^5. compounds which are liquid at N / ^{m 2} and 25 ° C., containing a compound which is solid at 1.013 × ¹⁰ 5 N / ^{m 2,} the content of the epoxy compound is a liquid form to all the epoxy compound more than 20% by weight 60% by weight or less.

  The (a) organic solvent-soluble polyimide used in the present invention is not particularly limited as long as it is soluble in an organic solvent. The term “soluble” means that 20% by weight or more dissolves in a solvent selected from the following at 23 ° C. Ketone solvents acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, ether solvents 1,4-dioxane, tetrahydrofuran, diglyme, glycol ether solvents methyl cellosolve, ethyl cellosolve, propylene glycol monomethyl ether, propylene glycol Monoethyl ether, propylene glycol monobutyl ether, diethylene glycol methyl ethyl ether, other benzyl alcohol, N-methylpyrrolidone, γ-butyrolactone, ethyl acetate, and N, N-dimethylformamide.

  Since the adhesive composition for semiconductors of the present invention contains (a) an organic solvent-soluble polyimide having an imide ring, it is excellent in heat resistance and chemical resistance. In particular, by using an organic solvent-soluble polyimide that has at least one functional group capable of reacting with an epoxy group at the side chain and at the end, the epoxy compound ring-opening and addition reaction to the aromatic polyimide are accelerated during heat treatment. Thus, a composition having a network structure with higher density can be obtained. Examples of the functional group capable of reacting with the epoxy group include a phenolic hydroxyl group, a sulfonic acid group, and a thiol group. As a method for synthesizing such an aromatic polyimide, for example, first, an acid dianhydride having a group capable of reacting with an epoxy group and a diamine are reacted to synthesize a polyimide precursor, and then as an end-capping agent. Examples include a method in which terminal modification of this polyimide precursor is performed using a primary monoamine or carboxylic acid derivative having a group capable of reacting with an epoxy group, followed by heat treatment at 150 ° C. or more to perform polyimide ring closure. Alternatively, after reacting primary monoamine as the acid dianhydride and the end-capping agent first, a diamine is added to synthesize a terminal-modified polyimide precursor, and the polyimide ring is closed at a high temperature of 150 ° C. or higher. Obtainable. Alternatively, after reacting a carboxylic acid derivative as a diamine and an end-capping agent first, an acid dianhydride is added to synthesize a terminal-modified polyimide precursor, and the polyimide ring is closed at a high temperature of 150 ° C. or higher. Can be obtained.

In order to make the (a) organic solvent-soluble polyimide used in the present invention soluble in the aforementioned solvent, the main chain of the aliphatic structure, the polyimide containing the aliphatic ring structure or the aromatic polyimide is 1,1,1, It is preferable to have at least one group selected from the group consisting of 3,3,3-hexafluoropropyl group, isopropyl group, ether group, thioether group and SO ₂ group. For such aromatic polyimide, a diamine component or acid dianhydride component having a 1,1,1,3,3,3-hexafluoropropyl group, an isopropyl group, an ether group, a thioether group, or a SO ₂ group should be used. Is obtained. It is preferable that the polyimide having these groups is 80% by weight or more based on the total amount of the polyimide because the solubility can be increased. Moreover, it is preferable that the terminal of the aromatic polyimide is end-capped with an end-capping agent comprising a monoamine and / or a carboxylic acid derivative.

In the present invention, among (a) organic solvent-soluble polyimides, functional groups having a structure represented by any one of the general formulas (2) to (7) and capable of reacting with an epoxy group are present at side chains and terminals. Polymers each having at least one, and those having 2 to 15% by weight of the structure represented by the general formula (1) as R ⁴ in the general formulas (2) to (7) with respect to the total amount of the polymer are preferably used. The total amount of the polymer (polyimide) obtained by the synthesis of the organic solvent-soluble polyimide here means the weight obtained by polymerization of the constituents composed of the primary amine compound, the acid dianhydride and the terminal blocking agent. The primary amine compound, acid dianhydride, and terminal blocker added excessively during the synthesis are not included in the weight of the polyimide.

In the formula, R ¹ represents a divalent hydrocarbon group, and R ² represents a monovalent hydrocarbon group, which may be the same or different. n shows the integer of 1-10. A plurality of R ² need not have the same structure.

In the formula, R ³ is a 4- to 14-valent organic group, R ⁴ is a 2- to 12-valent organic group, and at least one of R ³ and R ⁴ is 1,1,1,3,3, It contains at least one group selected from the group consisting of 3-hexafluoropropyl group, isopropyl group, ether group, thioether group and SO ₂ group. R ⁵ and R ⁶ represent an organic group having at least one group selected from the group consisting of a phenolic hydroxyl group, a sulfonic acid group, and a thiol group, and may be the same or different. X represents a monovalent organic group, Y represents a divalent organic group, and Z represents a monovalent organic group. m shows the range of 8-200. α and β each represent an integer of 0 to 10, and α + β is an integer of 1 to 10.

  The (a) organic solvent-soluble polyimide used in the present invention has a structure represented by the general formula (1), so that the solubility in the above-mentioned solvent is improved, and shrinkage during curing can be suppressed.

In the general formula (1), R ¹ represents a divalent hydrocarbon group, preferably an alkylene group having 1 to 5 carbon atoms or a phenylene group. n shows the integer of 1-10, Preferably it is 1-2. When n is 1 or more, shrinkage during curing can be suppressed, and when it is 10 or less, the imide group content in the polyimide skeleton is not reduced, and the insulation and heat resistance can be improved. R ² represents a monovalent hydrocarbon group, preferably an alkyl group having 1 to 5 carbon atoms or a phenyl group. Further, the plurality of R ² need not have the same structure.

  Content of the compound containing the structure represented by General formula (1) is 2 to 15 weight% in aromatic polyimide. When the content is 2% by weight or more, the above effect can be obtained, and when the content is 15% by weight or less, the rigidity of the polyimide skeleton can be maintained, and heat resistance and insulation can be maintained.

  Examples of the compound including the structure represented by the general formula (1) include diamine components such as bis (3-aminopropyl) tetramethyldisiloxane and bis (p-amino-phenyl) octamethylpentasiloxane.

  The organic solvent-soluble polyimide having (a) at least one functional group capable of reacting with an epoxy group at the side chain and at the terminal used in the present invention has a structure represented by the above general formulas (2) to (7). It is preferable.

In the above general formulas (2) to (7), R ³ represents a structural component of acid dianhydride, which is a tetravalent to tetravalent organic group, particularly an organic group having 5 to 40 carbon atoms. It is preferable. R ⁴ represents a structural component of diamine, which is a divalent to divalent organic group, preferably an organic group having 5 to 40 carbon atoms. At least one of R ³ and R ⁴ is at least one group selected from the group consisting of 1,1,1,3,3,3-hexafluoropropyl group, isopropyl group, ether group, thioether group, and SO ₂ group. Although it contains, it is preferable that both R < ³ > and R < ⁴ > contain. R ⁵ and R ⁶ represent an organic group having at least one group selected from the group consisting of a phenolic hydroxyl group, a sulfonic acid group, and a thiol group, and may be the same or different. X represents a monovalent organic group, Y represents a divalent organic group, and Z represents a monovalent organic group. m shows the range of 8-200. α and β each represent an integer of 0 to 10, and α + β is an integer of 1 to 10.

R ⁵ is an acid dianhydride substituent, and is selected from the group consisting of a phenolic hydroxyl group, a sulfonic acid group, and a thiol group. Specific examples of the acid dianhydride having at least one substituent include aromatic acid dianhydrides having the structures shown below.

R ¹¹ and R ¹² represent a hydrogen atom, a hydroxyl group, a thiol group, or a sulfonic acid group. However, R ¹¹ and R ¹² are not simultaneously hydrogen atoms.

R ³ represents a constituent of acid dianhydride and is selected from the group consisting of 1,1,1,3,3,3-hexafluoropropyl group, isopropyl group, ether group, thioether group and SO ₂ group. . Specific examples of the acid dianhydride having at least one organic group include 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride and 2,2-bis (2,3-di (). Carboxyphenyl) propane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, 2,2-bis (3,4-dicarboxy) Phenyl) hexafluoropropane dianhydride or a compound in which these aromatic rings are substituted with an alkyl group or a halogen atom.

Having at least one group selected from the group consisting of 1,1,1,3,3,3-hexafluoropropyl group, isopropyl group, ether group, thioether group and SO ₂ group, and having a phenolic hydroxyl group and sulfone Specific examples of the acid dianhydride having at least one group selected from the group consisting of an acid group and a thiol group include aromatic acid dianhydrides having the structures shown below.

R ¹⁰ represents C (CF ₃ ) ₂ , C (CH ₃ ) ₂ , SO ₂ , S or O. R ¹¹ and R ¹² represent a hydrogen atom, a hydroxyl group, a thiol group, or a sulfonic acid group. However, R ¹¹ and R ¹² are not simultaneously hydrogen atoms.

R ³ is an organic group other than 1,1,1,3,3,3-hexafluoropropyl group, isopropyl group, ether group, thioether group and SO ₂ group, R ⁵ is a phenolic hydroxyl group, sulfonic acid group, Specific examples of the acid dianhydride in the case of an organic group other than a thiol group include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3 , 3 ′, 4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride 2,2 ′, 3,3′-benzophenonetetracarboxylic dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, 1,1-bis (2,3-dicarboxy) Phenyl) ethane dianhydride, bis (3 , 4-Dicarboxyphenyl) methane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7 -Aromatic tetracarboxylic dianhydrides such as naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride Alternatively, compounds in which these aromatic rings are substituted with an alkyl group or a halogen atom can be mentioned. The acid dianhydride used in the present invention is used alone or in combination of two or more.

R ⁶ is a diamine substituent, and is selected from the group consisting of phenolic hydroxyl groups, sulfonic acid groups, and thiol groups. Specific examples of the diamine having at least one substituent include 3,3′-diamino-4,4′-dihydroxybiphenyl, 2,4-diamino-phenol, 2,5-diaminophenol, 1,4 -Diamino-2,5-dihydroxybenzene, diaminodihydroxypyrimidine, diaminodihydroxypyridine, hydroxydiaminopyrimidine, 9,9-bis (3-amino-4-hydroxyphenyl) fluorene, or alkyl groups or halogens on these aromatic rings Examples thereof include compounds substituted with atoms, and diamines having the structures shown below.

R ^{11 to} R ¹⁴ represent a hydrogen atom, a hydroxyl group, a thiol group, or a sulfonic acid group. However, R ¹¹ and R ¹² are not simultaneously hydrogen atoms.

R ⁴ represents a constituent component of diamine, and is selected from the group consisting of 1,1,1,3,3,3-hexafluoropropyl group, isopropyl group, ether group, thioether group and SO ₂ group. Specific examples of the diamine having at least one organic group include 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl ether, 4,4'- Diaminodiphenyl ether, 3,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, bis (4-aminophenoxyphenyl) sulfone, bis (3-aminophenoxyphenyl) sulfone, bis (4-aminophenoxy) biphenyl, Bis {4- (4-aminophenoxy) phenyl} ether, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 2,2-bis [4- (4 -Aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (4-amino) Phenoxy) phenyl] propane, or compounds substituted with alkyl group or halogen atom in the aromatic ring.

Having at least one group selected from the group consisting of 1,1,1,3,3,3-hexafluoropropyl group, isopropyl group, ether group, thioether group and SO ₂ group, and having a phenolic hydroxyl group and sulfone Specific examples of the diamine having at least one group selected from the group consisting of an acid group and a thiol group include 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 2,2-bis. (3-hydroxy-4-aminophenyl) hexafluoropropane, 2,2-bis (3-amino-4-hydroxyphenyl) propane, 2,2-bis (3-hydroxy-4-aminophenyl) propane, 3, 3′-diamino-4,4′-dihydroxydiphenyl ether, 3,3′-diamino-4,4′-dihydroxydiphenylsulfo , 3,3'-diamino-4,4'-dihydroxydiphenyl sulfone hydrate or compounds or substituted with an alkyl group or a halogen atom in these aromatic rings, and the like diamines having the structure shown below.

R ¹⁰ represents C (CF ₃ ) ₂ , C (CH ₃ ) ₂ , SO ₂ , S or O. R ^{11 to} R ¹² represent a hydrogen atom, a hydroxyl group, a thiol group, or a sulfonic acid group. However, R ¹¹ and R ¹² are not simultaneously hydrogen atoms.

R ⁴ is an organic group other than 1,1,1,3,3,3-hexafluoropropyl group, isopropyl group, ether group, thioether group and SO ₂ group, R ⁶ is a phenolic hydroxyl group, sulfonic acid group, Specific examples of the diamine in the case of an organic group other than a thiol group include 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, benzidine, m-phenylenediamine, p-phenylenediamine, and 1,5. -Naphthalenediamine, 2,6-naphthalenediamine, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-diethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4, 4'-diaminobiphenyl, 3,3'-diethyl-4,4'-diaminobiphenyl, 2,2 ', 3,3'-tetramethyl-4,4'-diaminobiphe Nyl, 3,3 ′, 4,4′-tetramethyl-4,4′-diaminobiphenyl, 2,2′-di (trifluoromethyl) -4,4′-diaminobiphenyl, or aromatic rings thereof Compounds substituted with alkyl groups or halogen atoms, terephthalic acid hydrazide, isophthalic acid hydrazide, phthaloic acid hydrazide, 2,6-naphthalenedicarboxylic acid dihydrazide, 4,4′-bisphenyldicarbonohydrazine, 4,4′-cyclohexanedicarbono Examples thereof include hydrazine and hydrazide compounds in which these aromatic rings are substituted with an alkyl group or a halogen atom. The diamine used in the present invention is used alone or in combination of two or more.

By selecting R ⁵ and R ⁶ in the above general formulas (2) to (7), the crosslinking density of the adhesive composition for semiconductor can be adjusted by adjusting the reaction rate between the aromatic polyimide and the epoxy compound during the heat treatment. . This makes it possible to impart the necessary heat resistance and chemical resistance to the adhesive composition for semiconductors. It is preferable that 20 to 90% of the total of R ⁵ and R ⁶ is a hydroxyl group, a thiol group, or a sulfonic acid group. By making these groups 20% or more of R ⁵ and R ⁶ , chemical resistance and heat resistance can be improved, and by making them 90% or less, the crosslinking density is suppressed to an appropriate range, and the film The elongation and toughness of can be maintained.

  X which is a structural component of the general formula (2) or general formula (3) preferably has at least one functional group capable of reacting with an epoxy group. Examples of such functional groups include phenolic hydroxyl groups, sulfonic acid groups, and thiol groups. X is preferably a structure represented by the following general formula (8), and these are components derived from a primary monoamine which is a terminal blocking agent. Moreover, X which comprises General formula (2) and General formula (3) is any of the end-capping group represented by General formula (8) alone, or 2 or more types of combinations with other terminal-capping groups. It may be.

  Moreover, it is preferable that Y which is a structural component of General formula (4) and General formula (5) has at least one functional group which can react with an epoxy group. Y is preferably a structure represented by the general formula (9) or the general formula (10), and these are components derived from an acid anhydride among the carboxylic acid derivatives which are end-capping agents. In addition, Y constituting the general formula (4) and the general formula (5) is an end-capping group represented by any one of the general formula (9) and the general formula (10), or other end-capping group. Any combination of two or more of these may be used.

  Z, which is a structural component of general formula (6) and general formula (7), preferably has at least one functional group capable of reacting with an epoxy group. Z is preferably a structure represented by the general formula (11) or the general formula (12), and these include a monocarboxylic acid, a monoacid chloride compound, and a monoactive ester among carboxylic acid derivatives that are end-capping agents. A component derived from a compound selected from compounds. Z constituting the general formula (6) and the general formula (7) is a terminal blocking group represented by any one of the general formula (11) and the general formula (12), or other terminal blocking group. And any combination of two or more of them.

R ¹⁷ in the general formula (8), general formula (11), and general formula (12) represents a divalent group selected from —CR ²¹ R ²² —, —CH ₂ O—, —CH ₂ SO ₂ —, R ²¹ and R ²² represent a monovalent group selected from a hydrogen atom, a hydroxyl group, and a hydrocarbon group having 1 to 10 carbon atoms. R ²⁰ in the general formula (11) and the general formula (12) represents a monovalent group selected from hydrocarbon groups having 1 to 10 carbon atoms. Of these, a hydrocarbon group having 1 to 4 carbon atoms is preferable, and a methyl group and a t-butyl group are particularly preferable. R ¹⁸ and R ¹⁹ in the general formula (10) and the general formula (12) are each a monovalent group selected from a hydrogen atom, a hydroxyl group, a carboxyl group, a sulfonic acid group, a thiol group, and a hydrocarbon group having 1 to 4 carbon atoms. Wherein at least one is a hydroxyl group, a carboxyl group, a sulfonic acid group or a thiol group. Also, ^{R 15} and ^{R 16} in formula (8), the general formula (9), the general formula (11) represents a hydrogen atom, a hydroxyl group, a carboxyl group, a sulfonic acid group, a thiol group, a hydrocarbon having 1 to 10 carbon atoms 1 represents a monovalent group selected from a group, at least one of which is a hydroxyl group, a carboxyl group, a sulfonic acid group or a thiol group. A, E, and G in General Formula (8), General Formula (9), and General Formula (11) are carbon atoms or nitrogen atoms, and may be the same or different. o is an integer of 0 to 10, preferably an integer of 0 to 4. l is 0 or 1, preferably 0. p is 0 or 1, preferably 0. q is an integer of 1 to 3, preferably 1 or 2. r, s, and t are 0 or 1.

  Specific examples of the primary monoamine having the structure represented by the general formula (8) include 5-amino-8-hydroxyquinoline, 4-amino-8-hydroxyquinoline, 1-hydroxy-8-aminonaphthalene, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 1-hydroxy-3-aminonaphthalene, 1-hydroxy-2 -Aminonaphthalene, 1-amino-7-hydroxynaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 2-hydroxy-4-aminonaphthalene, 2, -Hydroxy-3-aminonaphthalene, 1-amino-2-hydroxynaphthalene 1-carboxy-8-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 1-carboxy-4-aminonaphthalene, 1-carboxy- 3-aminonaphthalene, 1-carboxy-2-aminonaphthalene, 1-amino-7-carboxynaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-carboxy-4-aminonaphthalene, 2-carboxy-3-aminonaphthalene, 1-amino-2-carboxynaphthalene, 2-aminonicotinic acid, 4-aminonicotinic acid, 5-aminonicotinic acid, 6-aminonicotinic acid 4-aminosalicylic acid, 5-aminosalicylic acid 6-aminosalicylic acid, 3-amino-o-toluic acid, amelide, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4- Aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 5-amino-8-mercaptoquinoline, 4-amino-8-mercaptoquinoline, 1 -Mercapto-8-aminonaphthalene, 1-mercapto-7-aminonaphthalene, 1-mercapto-6-aminonaphthalene, 1-mercapto-5-aminonaphthalene, 1-mercapto-4-aminonaphthalene, 1-mercapto-3- Aminonaphthalene, 1-mercapto-2-aminonaphthalene, 1- Amino-7-mercaptonaphthalene, 2-mercapto-7-aminonaphthalene, 2-mercapto-6-aminonaphthalene, 2-mercapto-5-aminonaphthalene, 2-mercapto-4-aminonaphthalene, 2-mercapto-3-amino Naphthalene, 1-amino-2-mercaptonaphthalene, 3-amino-4,6-dimercaptopyrimidine, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol and the like can be mentioned.

  Of these, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2 -Hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5 Aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4- Aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2- Aminothiophenol, 3-aminothiophenol, 4-aminothiophenol and the like are preferable.

  In particular 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy- 7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2 -Aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, etc. are preferable, and these are used individually or in combination of 2 or more types.

  Specific examples of the acid anhydride having the structure represented by the general formula (9) or the general formula (10) include phthalic anhydride, maleic anhydride, nadic acid, cyclohexanedicarboxylic anhydride, and more preferably , 3-hydroxyphthalic anhydride, 4-hydroxyphthalic anhydride, trimellitic anhydride, and the like.

  Specific examples of the carboxylic acid derivative, monocarboxylic acid, monoacid chloride compound and monoactive ester compound having the structure represented by the general formula (11) or the general formula (12) include 2-carboxyphenol and 3-carboxyphenol. 4-carboxyphenol, 2-carboxythiophenol, 3-carboxythiophenol, 4-carboxythiophenol, 1-hydroxy-8-carboxynaphthalene, 1-hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene 1-hydroxy-5-carboxynaphthalene, 1-hydroxy-4-carboxynaphthalene, 1-hydroxy-3-carboxynaphthalene, 1-hydroxy-2-carboxynaphthalene, 1-mercapto-8-carboxynaphthalene, 1-merca To-7-carboxynaphthalene, 1-mercapto-6-carboxynaphthalene, 1-mercapto-5-carboxynaphthalene, 1-mercapto-4-carboxynaphthalene, 1-mercapto-3-carboxynaphthalene, 1-mercapto-2-carboxy Monocarboxylic acids such as naphthalene, 2-carboxybenzenesulfonic acid, 3-carboxybenzenesulfonic acid, 4-carboxybenzenesulfonic acid, monoacid chloride compounds in which these carboxyl groups are converted to acid chloride, terephthalic acid, phthalic acid, maleic Acid, cyclohexanedicarboxylic acid, 3-hydroxyphthalic acid, 5-norbornene-2,3-dicarboxylic acid, 1,2-dicarboxynaphthalene, 1,3-dicarboxynaphthalene, 1,4-dicarboxynaphthalene, 1,5 - Ruboxynaphthalene, 1,6-dicarboxynaphthalene, 1,7-dicarboxynaphthalene, 1,8-dicarboxynaphthalene, 2,3-dicarboxynaphthalene, 2,6-dicarboxynaphthalene, 2,7-dicarboxy Monoacid chloride compounds in which only the monocarboxyl group of dicarboxylic acids such as naphthalene is acid chloride, monoacid chloride compounds and N-hydroxy-5-norbornene-2,3-dicarboximide, p-nitrophenol, N-hydroxysuccinate Examples include active ester compounds obtained by reaction with imide, N-hydroxyphthalimide, N-hydroxybenzotriazole and the like.

  Among these, from the ease of introduction into the polymer, acid anhydrides such as phthalic anhydride, maleic anhydride, nadic acid, cyclohexanedicarboxylic anhydride, 3-hydroxyphthalic anhydride, 3-carboxyphenol, 4-carboxyphenol, 3-carboxythiophenol, 4-carboxythiophenol, 1-hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, 1-hydroxy-5-carboxynaphthalene, 1-mercapto-7- Monocarboxylic acids such as carboxynaphthalene, 1-mercapto-6-carboxynaphthalene, 1-mercapto-5-carboxynaphthalene, 3-carboxybenzenesulfonic acid and 4-carboxybenzenesulfonic acid are preferably used. These are used alone or in combination of two or more.

  When the introduction ratio of the component represented by the general formula (8) (the X component of the general formula (3)) is converted into the primary monoamine component of the terminal blocking agent which is the original component, The range of 0.1-60 mol% is preferable, Most preferably, it is 5-50 mol%. Components represented by general formula (9) and general formula (10) (Y component of general formula (2) and general formula (5)), and components represented by general formula (11) and general formula (12) The introduction ratio of (general formula (4), general formula (6), general formula (7) Z component) is the base component acid anhydride, monocarboxylic acid, monoacid chloride compound, When converted in terms of the mono-active ester compound component, the range of 0.1 to 60 mol% is preferable with respect to the total diamine component, and particularly preferably 5 to 55 mol%.

  In the general formulas (2) to (7), m represents the number of polymer repetitions, and ranges from 8 to 200. Preferably it is 10-150. When it says with a weight average molecular weight, it is preferable that it is 4000-80000 in polystyrene conversion by gel filtration chromatography, Most preferably, it is 8000-60000. By setting m to 8 or more, the composition viscosity can be increased to enable thick film coating, and by setting m to 200 or less, solubility in a solvent can be improved.

  The (a) organic solvent-soluble polyimide of the present invention may have a structure represented by the general formulas (2) to (7), or may be a copolymer or a mixture having another structure. good. In that case, it is preferable to contain 50 mol% or more of the structures represented by the general formulas (2) to (7). The type and amount of the structure used for copolymerization or mixing are preferably selected within a range that does not impair the heat resistance of the heat resistant resin film obtained by heat treatment.

  The (a) organic solvent-soluble polyimide used in the present invention is obtained by replacing a part of the diamine with an end-capping agent that is a monoamine, or a part of the acid dianhydride is a monocarboxylic acid, an acid anhydride, or a monoacid. It is synthesized using a known method in place of the end capping agent which is a chloride compound or a monoactive ester compound. For example, a method of reacting a tetracarboxylic dianhydride and a diamine compound (partially substituted with a terminal blocking agent that is a monoamine) at a low temperature, a tetracarboxylic dianhydride (a part of an acid anhydride or A method of reacting a diamine compound with a monoacid chloride compound or a mono-active ester compound, and a diamine compound, a diester is obtained by reaction of tetracarboxylic dianhydride and alcohol, and then a diamine (partially with a monoamine) A method of reacting with a certain end-capping agent and the presence of a condensing agent, a diester is obtained by reaction of tetracarboxylic dianhydride and alcohol, and then the remaining dicarboxylic acid is acid chlorided to obtain a diamine (partially A polyimide precursor is obtained using a method such as a method of reacting with a monoamine end-capping agent), and this is then known in the art. It can be synthesized organic solvent-soluble polyimide by utilizing the method of de reaction.

The structure of the general formula (1) introduced into the polymer and the end capping agent used in the present invention can be easily detected and quantified by the following method. For example, a polymer in which the structure of the general formula (1) and the end-capping agent are introduced is dissolved in an acidic solution or a basic solution, and decomposed into a diamine component and an acid anhydride component which are constituent units of the polymer. The structure of the general formula (1) and the end-capping agent used can be easily detected and quantified by gas chromatography (GC) or NMR measurement. Separately from this, the structure of the general formula (1) is also used by directly measuring the pyrolysis gas chromatograph (PGC), infrared spectrum and ¹³ CNMR spectrum of the polyimide into which the end-capping agent is introduced. It is possible to easily detect and quantify the end-capping agent.

  (A) Content of organic solvent soluble polyimide is 15-90 weight part with respect to 100 weight part of (b) epoxy compounds, Preferably it is 30-65 weight part. (A) When the content of the organic solvent-soluble polyimide is less than 15 parts by weight, the semiconductor adhesive composition is easily peeled off from the semiconductor wafer during dicing, or cracks and chips are likely to occur. Such a defect during dicing becomes more prominent as the cutting speed increases. In addition, when the content of (a) the organic solvent-soluble polyimide exceeds 90 parts by weight, the semiconductor adhesive composition is laminated when laminating the semiconductor adhesive composition (adhesive sheet) on the semiconductor wafer with bump electrodes. Does not sufficiently enter between the bump electrodes, bubbles remain, and the adhesive force between the semiconductor chip after flip chip mounting and the circuit board is reduced. In addition to the above, since the semiconductor adhesive composition can easily absorb water, when the semiconductor chip with the semiconductor adhesive composition layer after dicing is flip-chip mounted on the circuit board, the semiconductor is heated by the flip chip mounting. Moisture in the adhesive composition for a liquid evaporates rapidly, and the adhesive composition layer for a semiconductor foams. This decrease in adhesive force and foaming lead to a decrease in connection reliability between the semiconductor chip and the circuit board.

  The adhesive composition for semiconductor of the present invention further contains (b) an epoxy compound. (B) The epoxy compound reacts with the polyimide side chain and terminal phenolic hydroxyl group, sulfonic acid group, and thiol group to form a high-density network structure, so the resulting adhesive composition for semiconductors exhibits resistance to various chemicals. To do. It can be made completely insoluble in various solvents, particularly N-methylpyrrolidone. Moreover, since an epoxy compound generally hardens | cures by the ring-opening reaction which does not accompany shrinkage | contraction, it becomes possible for the adhesive composition for semiconductors of this invention containing (b) epoxy compound to reduce shrinkage | contraction at the time of hardening. Therefore, as the (b) epoxy compound, one having two or more epoxy groups is preferably used, and the epoxy equivalent is preferably 100 to 500. By setting the epoxy equivalent to 100 or more, the toughness of the heat-resistant resin film can be improved, and by setting it to 500 or less, a high-density network structure can be obtained after thermosetting. The resin component can be made highly insulating.

In addition, (b) the epoxy compound has two types, liquid and solid, and the content ratio of the liquid epoxy compound needs to be 20 wt% or more and 60 wt% or less with respect to the total amount of the epoxy compound. Preferably they are 30 weight% or more and 50 weight% or less. By using a liquid epoxy compound within this range, it is possible to impart moderate plasticity and flexibility to the adhesive composition for semiconductors. When a semiconductor adhesive composition is formed into a sheet, a flexible sheet (adhesive sheet) can be obtained. Obtainable. Further, cracking and chipping of the semiconductor adhesive composition during dicing are suppressed. If the liquid epoxy compound is less than 20% by weight, the adhesive composition for a semiconductor is formed on a plastic film and rolled to form a crack or peel from the plastic film, and the adhesive sheet is cracked or chipped during dicing. There arises a problem that the semiconductor adhesive composition is peeled off from the semiconductor wafer. If the content of the liquid epoxy compound exceeds 60% by weight with respect to the total amount of the epoxy compound, the cutting powder during dicing tends to adhere, and the adhesion and electrical conduction reliability between the semiconductor chip and the circuit board after the subsequent flip chip mounting. Sex is reduced. Here, the liquid epoxy compound indicates a viscosity of 150 Pa · s or less at 25 ° C. and 1.013 × 10 ⁵ N / m ² , and the one having a viscosity exceeding 150 Pa · s at 25 ° C. is a solid epoxy compound. Show. If it is such an epoxy compound, it will not specifically limit, As a liquid epoxy compound, for example, Epicoat 828, Epicoat 1002, Epicoat 1750, Epicoat 152, Epicoat 630 (above a brand name, Japan Epoxy Resin Co., Ltd. product), Epicron And HP-4032 (trade name, manufactured by Dainippon Ink and Chemicals, Inc.). Two or more of these may be combined. Further, as the solid epoxy compound, Epicoat 1002, Epicoat 1001, YX4000H, Epicoat 4004P, Epicoat 5050, Epicoat 154, Epicoat 157S70, Epicoat 180S70, YX4000H (trade name, manufactured by Japan Epoxy Resin Co., Ltd.), Tepic S, Tepic G, Tepic P (trade name, manufactured by Nissan Chemical Industries, Ltd.), Epototo YH-434L (trade name, manufactured by Tohto Kasei Co., Ltd.), EPPN502H, NC3000 (all trade names, manufactured by Nippon Kayaku Co., Ltd.) , Epicron N695, Epicron HP-7200 (trade name, manufactured by Dainippon Ink & Chemicals, Inc.) and the like. Two or more of these may be used in combination.

In the adhesive composition for semiconductor of the present invention, (c) a curing accelerator is further used. By combining the epoxy compound and the curing accelerator, curing of the solid epoxy compound and the liquid epoxy compound can be accelerated and cured in a short time. Examples of the curing accelerator include various imidazoles, imidazole silanes, imidazolines and acid anhydrides. As various imidazoles, imidazole, 2-methylimidazole, 2-undecylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-phenylimidazolium tri Examples include meritate. Examples of imidazole silane include IS-1000, IS-1000D, IM-1000, SP-1000, IA-100A, IA-100P, and IA-100F (trade names, manufactured by Nikko Materials Co., Ltd.). Examples of acid anhydrides include hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, Adeka Hardener EH-3326, Adeka Hardner EH-703, Adeka Hardner EH-705A (above, trade name, manufactured by Asahi Denka Kogyo Co., Ltd.) ), Epicron B-570, Epicron B-650 (trade name, manufactured by Dainippon Ink & Chemicals, Inc.), and the like. (C) Content of a hardening accelerator needs to be the range of 0.1-10 weight part with respect to a total of 100 weight part of (b) epoxy compound. (C) Curing of the epoxy compound is effectively accelerated by setting the content of the curing accelerator to 0.1 parts by weight or more, and the insulation and heat resistance of the cured product are improved by setting the content to 10 parts by weight or less. be able to. Further, (c) a curing accelerator is preferably used insoluble in water. Here, the term “insoluble in water” means that the amount dissolved in pure water at 25 ° C. and 1.013 × 10 ⁵ N / m ² is 5% by weight or less. The water-soluble curing accelerator dissolves in cutting water used at the time of dicing, and the film surface of the adhesive composition sheet for a semiconductor may become rough or may cause a decrease in curability or adhesiveness.

  In the adhesive composition for a semiconductor of the present invention, as a thermoplastic resin, for example, phenoxy resin, polyester, polyurethane, polyamide, polypropylene, acrylonitrile-butadiene copolymer (NBR), styrene-butadiene copolymer, (SBR), Acrylonitrile-butadiene-methacrylic acid copolymer, acrylonitrile-butadiene-acrylic acid copolymer and the like can be added as a stress reducing agent for the cured film. Moreover, a well-known hardening | curing agent for epoxy compounds and a filler can be added.

  (D) Examples of conductive particles include particles made of metals such as Ni, Au, Ag, Cu, Pb, Sn, Bi, or alloys and mixtures thereof, and plastics such as polystyrene, polycarbonate, acrylic resin, dienylbenzene, and nylon. Particles whose particle surfaces are coated with a metal such as Ni, Au, Ag, Cu, Pb, Sn, or Bi can be used. When conductive particles are packed in resin at high density, the surface of the conductive particles is made of styrene butadiene styrene rubber, epoxy resin, acrylic resin, polyester, urethane, etc. It may be coated with an insulating resin.

  The particle diameter of the conductive particles is preferably larger than the bump height variation, and is preferably smaller than the gap between adjacent bumps and the gap between the electrodes on the circuit board. Specifically, 1 to 10 μm is preferable. When the particle diameter of the conductive particles is 1 μm or more, the bump height variation that can be absorbed by the deformation of the particles due to the pressure applied during flip chip bonding is sufficiently large when the bump and the circuit board are bonded by flip chip bonding. It is easy to reliably bond all the bumps in the chip. When the particle diameter of the conductive particles is 10 μm or less, it is easy to maintain good insulation between the pumps even at a fine pitch where the gap between adjacent bumps is 20 μm or less. The insulating layer coated on the conductive particles is preferably 1 to 3 μm.

  The semiconductor adhesive composition of the present invention may be coated on a semiconductor wafer with bump electrodes. In order to process the semiconductor adhesive composition of the present invention into a sheet, the uniformly mixed semiconductor adhesive composition is sandwiched between plastic films or the like, and can be produced by press rolling or roll rolling. Moreover, what was mixed with the adhesive composition for semiconductors in the solvent, and was made into the varnish form can be apply | coated on a plastic film, a solvent can be removed, and it can also process into a sheet form. In the present invention, a plastic film and a semiconductor adhesive composition formed on the plastic film are referred to as a semiconductor adhesive sheet material.

  What is necessary is just to select suitably what melt | dissolves the said component as a solvent used here, for example, acetone solvent, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, ether solvent 1,4-dioxane, tetrahydrofuran, Diglyme, glycol ether solvent methyl cellosolve, ethyl cellosolve, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, diethylene glycol methyl ethyl ether, other benzyl alcohol, propanol, N-methylpyrrolidone, γ-butyrolactone, acetic acid Examples include ethyl, N, N-dimethylformamide and the like. In particular, when a material having a boiling point under atmospheric pressure of 120 ° C. or less can be removed at a low temperature in a short time, sheeting is facilitated.

  As the coating machine, a roll coater, a comma roll coater, a gravure coater, a screen coater, a slit die coater, etc. can be used, but the slit die coater is preferably used because the volatility of the solvent during coating is small and the coating property is stable. Is done.

  The thickness of the sheeted semiconductor adhesive composition is preferably equal to or higher than the average height of the bump electrode when the sheeted semiconductor adhesive composition is bonded to a semiconductor wafer with a bump electrode, more preferably The average height of the bump electrode or more and 1.5 times or less the sum of the average height of the bump electrode and the average height of the pad electrode on the circuit board, and even more preferably, the average height of the bump electrode or more And it is below the thickness which added the average height of the bump electrode and the pad electrode average height on the circuit board. The height of the bump electrode is measured using the wafer surface on which the bump electrode is not formed as a reference (0 μm). In addition, the height of the pad electrode on the circuit board is the height of all the electrode pads with the insulating surface of the circuit board (polyimide, glass epoxy, glass, ceramics, etc.) on which the pad electrode is formed as a reference (0 μm). Measure and take the average value. If the thickness of the sheeted adhesive composition for semiconductor is less than the average height of the bump electrode, a gap is formed between the semiconductor chip after flip chip bonding, the adhesive composition for semiconductor and the circuit board, and the adhesive strength is reduced. To do. In addition, it is not only uneconomical if the thickness of the sheeted adhesive composition for semiconductor exceeds 1.5 times the total thickness of the bump electrode average height and the pad electrode average height on the circuit board. The amount of protrusion of the semiconductor adhesive composition under the semiconductor chip increases and the mounting area increases, and the protruding semiconductor adhesive composition wraps around the top of the semiconductor chip and contaminates the heating horn of the flip chip bonding apparatus. Problems such as adhesion between the horn and the semiconductor chip are likely to occur. In addition, when the heating horn is contaminated, the flatness of the horn is impaired, and the heating state of the semiconductor chip during flip chip bonding becomes uneven, which may cause a problem that bonding failure is likely to occur.

  In the adhesive sheet material for semiconductor produced by the above method, the adhesive force between the plastic film and the adhesive composition for semiconductor is preferably 2 N / m or more and 49 N / m or less. By setting it as 2 N / m or more, the adhesive sheet material for semiconductors excellent in the handling in which the unintentional peeling between a plastic film and the adhesive composition for semiconductors does not occur can be obtained. By setting the adhesive force between the plastic film and the semiconductor adhesive composition to be 49 N / m or less, the semiconductor adhesive composition hardly remains on the surface of the plastic film when the plastic film is peeled off.

  Moreover, if necessary, another plastic film may be laminated on the semiconductor adhesive composition to obtain a semiconductor adhesive sheet material sandwiched between the plastic films. At this time, the magnitude of the adhesive force of each surface is not particularly limited, and each surface preferably has an adhesive force of 2 N / m or more and 49 N / m or less. Further, when one plastic film is (e) a plastic film and the other plastic film is (f) a plastic film, (f) the adhesive force between the plastic film and the adhesive composition for a semiconductor, and (e) the plastic film and the semiconductor The difference in adhesive strength between the adhesive compositions is preferably 5 N / m or more. Here, (f) the adhesive force between the plastic film and the semiconductor adhesive composition is greater than (e) the adhesive force between the plastic film and the semiconductor adhesive composition. The difference in the adhesive strength is preferably 47 N / m or less. By setting the difference in adhesive strength to 5 N / m or more, it is possible to prevent peeling or lifting of the adhesive composition for semiconductors when peeling the plastic film, and the difference in adhesive strength is 47 N / m or less. By doing so, it becomes difficult for the adhesive composition for a semiconductor to remain on the surface of the plastic film when the film is peeled off.

  (E) The adhesive force between the plastic film and the adhesive composition for a semiconductor can be measured as follows. First, the adhesive sheet material for semiconductor is cut into a width of 25 mm and a length of 300 mm, and this is fixed to a stainless steel plate having a thickness of 2 mm using a double-sided adhesive tape. At this time, (e) the plastic film surface is adhered to the adhesive surface of the double-sided adhesive tape. Next, (e) the plastic film is peeled from the semiconductor adhesive composition in the direction of 90 degrees at a speed of 200 mm / min, and (e) the adhesive force between the plastic film and the semiconductor adhesive layer (N / m) Measure.

  (F) The adhesive force between the plastic film and the adhesive composition for a semiconductor can be measured as follows. First, the semiconductor adhesive sheet material was cut to a width of 25 mm and a length of 300 mm, (e) after removing the plastic film, and fixed on a 2 mm thick stainless steel plate with a double-sided adhesive tape attached using a double-sided adhesive tape. To do. At this time, the semiconductor adhesive composition surface is adhered to the adhesive surface of the double-sided adhesive tape. (F) The plastic film is peeled off from the semiconductor adhesive composition in the direction of 90 degrees at a speed of 200 mm / min. (F) The adhesive force (N / m) between the plastic film and the semiconductor adhesive composition is measured.

  Examples of the plastic film used here include a polyethylene terephthalate film, a polyethylene naphthalate film, a polyester film, a polyvinyl chloride film, a polycarbonate film, and a polyimide film. Moreover, fluororesin films, such as a polytetrafluoroethylene film, a polyphenylene sulfide film, a polypropylene film, a polyethylene film, etc. are mentioned. The plastic film may be subjected to a release treatment. For example, the release may be performed using a silicone-based, long-chain alkyl-based, fluorine-based, aliphatic amide-based, or the like. The adhesive force between the plastic film and the adhesive composition for semiconductors is determined by selecting the type and thickness of the plastic film, the composition of the adhesive composition for semiconductors such as the amount of liquid epoxy resin and the addition of a tack component that is in a rubbery state at room temperature, It can be controlled by the type of solvent, heat aging of the adhesive sheet material for semiconductors, and the like.

  Further, (f) an adhesive layer may be formed on the surface of the plastic film. (F) When the pressure-sensitive adhesive layer on the surface of the plastic film is formed, (f) the plastic film and the semiconductor adhesive composition are laminated so that the pressure-sensitive adhesive layer surface sticks to the semiconductor adhesive composition. In this case, when (f) the plastic film is peeled from the adhesive composition for semiconductor, the adhesive force between the plastic film and the adhesive layer is (f) so that the adhesive does not remain on the adhesive composition for semiconductor. It is important that the adhesive strength between the pressure-sensitive adhesive layer and the adhesive composition for a semiconductor is larger. As the material for the pressure-sensitive adhesive, acrylic, vinyl, urethane, silicone, polyester, styrene-butadiene, isoprene, natural rubber and the like can be used. An adhesive whose pressure-sensitive adhesive type, pressure-sensitive adhesive type, thermosetting release type, or photo-curing release type can be used. The thickness of the pressure-sensitive adhesive layer is determined optimally depending on the type and usage of the pressure-sensitive adhesive, and can usually be in the range of 1 to 50 μm. As the plastic film provided with such an adhesive layer, commercially available adhesive tapes such as a back grind tape and a dicing tape can also be used. In addition, instead of using the plastic film (f) in which the pressure-sensitive adhesive layer is formed in advance, the pressure-sensitive adhesive is formed on the adhesive composition layer for a semiconductor by pressure-sensitive adhesive layer coating or the like, and (f) the plastic film is laminated by a method such as lamination You may form in the adhesive composition layer for semiconductors by which the layer was laminated | stacked.

  When the semiconductor device of the present invention has a plastic film on both surfaces of the semiconductor adhesive composition, (e) after removing the plastic film, the exposed semiconductor adhesive composition surface is exposed to a semiconductor with a bump electrode. The wafer is temporarily laminated by heating lamination or vacuum heating lamination at 40 to 100 ° C. In this temperature range, the dynamic viscosity of the adhesive composition for a semiconductor is preferably 10 to 100,000 Pa · s, more preferably 1000 to 10,000 Pa · s. If the dynamic viscosity of the adhesive composition for semiconductor is less than 10 Pa · s, handling becomes difficult, and if it exceeds 100,000 Pa · s, the bump electrode is not embedded in the adhesive composition for semiconductor, and lamination at high pressure is required. Thus, problems such as breakage of the wafer are likely to occur. Further, it is not preferable to perform lamination at a high pressure because warpage is likely to occur after lamination.

  Next, back grinding may be performed as described below as necessary. That is, (f) the plastic film obtained by the above process and the (f) plastic film surface of the semiconductor wafer with the adhesive composition for semiconductor are placed on the fixed surface of the back grinding machine, and the wafer surface on which the semiconductor is not formed (back surface) ) Grinding / polishing may be performed. By performing such processing, a thin semiconductor wafer with an adhesive composition for a semiconductor can be obtained. According to this processing process, the process can be simplified as compared with the normal method in which the back grinding process and the semiconductor chip mounting adhesive application are performed separately.

  Next, (f) the plastic film, the semiconductor wafer with the adhesive composition for semiconductor, and the tape frame obtained by the above process are attached to a dicing tape. At this time, (f) the plastic film and the semiconductor wafer with the adhesive composition for semiconductor are made to adhere the surface opposite to the bump electrode to the adhesive surface of the dicing tape. Thereafter, dicing is performed.

  In the dicing process, first, a tape frame in which a semiconductor wafer with a bump electrode to which a plastic film and an adhesive composition for semiconductor are attached was attached with a dicing tape on a cut table was set, and then ( f) The plastic film is peeled off. The alignment mark on the bump electrode or the semiconductor wafer is recognized on the apparatus, and dicing is performed by setting each dicing condition such as a cut size, a cutting speed, a depth, a blade rotation speed, and a cutting water amount to predetermined values. Here, it is preferable that the alignment mark on the semiconductor wafer includes a plurality of square shapes, and using such an alignment mark can reduce alignment errors. The wafer after dicing is desirably dried at 25 to 100 ° C. for 10 seconds to 4 hours. The crack, chipping and peeling from the semiconductor wafer due to dicing of the semiconductor adhesive composition are preferably within a maximum length of 25 μm with the cut end as the reference position of 0 μm. When cracking, chipping, or peeling from the semiconductor wafer of the semiconductor adhesive composition exceeds 25 μm, water tends to be adsorbed and adhered to the semiconductor adhesive composition during and after dicing. The adsorbed water causes voids and voids in the adhesive composition layer during flip chip mounting to be performed later, causing a decrease in adhesive force and a decrease in electrical reliability. The cracking, chipping, and peeling from the semiconductor wafer of the adhesive composition for a semiconductor are likely to occur at a crosscut portion (portion that hits a corner of a semiconductor chip).

  Next, the semiconductor chip with the adhesive composition for semiconductor obtained by dicing is mounted on a circuit board using a normal flip chip bonder. The mounting conditions are not particularly limited as long as the electrical connection between the semiconductor chip and the circuit board can be satisfactorily obtained, and is appropriately determined according to the material of the bump and the electrode of the circuit board. Moreover, when hardening of the adhesive composition for semiconductors is inadequate, a semiconductor chip mounting circuit board may be heated after mounting and hardening of the adhesive composition for semiconductors may be advanced further.

  As another method for manufacturing a semiconductor device, a multilayer substrate and / or a package substrate using the adhesive composition for a semiconductor of the present invention, there are the following methods. The adhesive composition for a semiconductor can be used as an adhesive layer for joining a semiconductor device with a pair of individually formed electrodes, a multilayer substrate and / or a package substrate so that both electrodes are electrically connected. . A plurality of semiconductor devices, multilayer substrates, and / or package substrates are formed on a single wafer or single substrate, and are separated into individual pieces by dicing or the like after bonding using a semiconductor adhesive composition. Production is possible. A multilayer substrate separated into pieces after bonding can be preferably used as a substrate for a package or module. A semiconductor chip, a passive component, or the like may be mounted or formed on a semiconductor device, a multilayer substrate and / or a package substrate in a state before bonding, or may be mounted or formed after being separated into pieces after bonding. . The material of the electrode used for electrical joining is not particularly limited, and Au, Au / Sn, copper, solder, or the like can be used. The shape of the electrode is not particularly limited as long as it is suitable for bonding, and a bump, a ball, a flat pad, or the like can be preferably used.

  Hereinafter, the present invention will be described with reference to examples and the like, but the present invention is not limited to these examples. In addition, evaluation of the adhesive composition for semiconductor in an Example was performed with the following method.

Synthesis Example 1 Synthesis of Organic Solvent-Soluble Polyimide A 24.54 g (0.067 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (hereinafter referred to as BAHF) under a dry nitrogen stream 1.97 g (0.02 mol) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane (hereinafter referred to as SiDA), 3-aminophenol (hereinafter referred to as 3-Aph) as a terminal blocking agent 2.18 g (0.02 mol) was dissolved in 80 g of NMP. Here, 31.02 g (0.1 mol) of bis (3,4-dicarboxyphenyl) ether dianhydride (hereinafter referred to as ODPA) was added together with 20 g of NMP and reacted at 20 ° C. for 1 hour, and then at 50 ° C. Stir for 4 hours. Thereafter, 15 g of xylene was added, and the mixture was stirred at 180 ° C. for 5 hours while water was azeotroped with xylene. After the stirring was completed, the solution was poured into 3 L of water to obtain a white precipitated polymer. The precipitate was collected by filtration, washed with water three times, and then dried at 80 ° C. for 20 hours using a vacuum dryer. When the resulting measuring the infrared absorption spectrum of the polymer solids, 1780 cm around ^-1, absorption peaks of an imide structure caused by a polyimide was detected near 1377 cm ^-1. Thus, an organic solvent-soluble polyimide A having a functional group capable of reacting with an epoxy group and containing 7.4% by weight of the structure represented by the general formula (1) was obtained. 6 g of tetrahydrofuran was added to 4 g of the obtained polymer, and the mixture was stirred at 23 ° C. and dissolved.

Synthesis example 2 Synthesis | combination of organic-solvent soluble polyimide B Under dry nitrogen stream, BAHF18.31g (0.05mol), SiDA 7.46g (0.03mol), 3-Aph 4.37g (0.04) as terminal blocker Mol) was dissolved in 150 g of NMP. To this, 52 g (0.1 mol) of 2,2-bis (4-dicarboxyphenoxy) phenyl) propane dianhydride (hereinafter referred to as BSAA) was added together with 30 g of NMP and reacted at 20 ° C. for 1 hour. Stir at 4 ° C. for 4 hours. Then, it stirred at 180 degreeC for 5 hours. After the stirring was completed, the solution was poured into 3 L of water to obtain a white precipitated polymer. The precipitate was collected by filtration, washed with water three times, and then dried at 80 ° C. for 20 hours using a vacuum dryer. When the resulting measuring the infrared absorption spectrum of the polymer solids, 1780 cm around ^-1, absorption peaks of an imide structure caused by a polyimide was detected near 1377 cm ^-1. Thus, an organic solvent-soluble polyimide B having a functional group capable of reacting with an epoxy group and containing 8.3% by weight of the structure represented by the general formula (1) was obtained. 6 g of tetrahydrofuran was added to 4 g of the obtained polymer, and the mixture was stirred at 23 ° C. and dissolved.

Synthesis Example 3 Synthesis of Organic Solvent-Soluble Polyimide C Under a dry nitrogen stream, 14.65 g (0.04 mol) of BAHF and 9.96 g (0.04 mol) of SiDA were dissolved in 130 g of NMP. 44.42 g (0.1 mol) of 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride (hereinafter referred to as 6FDA) was added thereto together with 20 g of NMP, followed by stirring at 20 ° C. for 1 hour. And then stirred at 50 ° C. for 2 hours. 3-Aph 3.27g (0.04mol) was added here as terminal blocker, and after stirring at 50 degreeC for 2 hours, it stirred at 180 degreeC for 5 hours. After the stirring was completed, the solution was poured into 3 L of water to obtain a white precipitated polymer. The precipitate was collected by filtration, washed with water three times, and then dried at 80 ° C. for 20 hours using a vacuum dryer. When the resulting measuring the infrared absorption spectrum of the polymer solids, 1780 cm around ^-1, absorption peaks of an imide structure caused by a polyimide was detected near 1377 cm ^-1. Thus, an organic solvent-soluble polyimide C having a functional group capable of reacting with an epoxy group and containing 12.4% by weight of the structure represented by the general formula (1) was obtained. 6 g of tetrahydrofuran was added to 4 g of the obtained polymer, and the mixture was stirred at 23 ° C. and dissolved.

Synthesis Example 4 Synthesis of Organic Solvent-Soluble Polyimide D Under a dry nitrogen stream, 29.3 g (0.08 mol) of BAHF and 4.97 g (0.02 mol) of SiDA were dissolved in 130 g of NMP. 28.54 g (0.092 mol) of ODPA was added thereto together with 20 g of NMP, and the mixture was stirred at 20 ° C. for 1 hour, and then stirred at 50 ° C. for 2 hours. 4-hydroxyphthalic anhydride 3.28g (0.02mol) was added here as terminal blocker, and it stirred at 50 degreeC for 2 hours. Thereafter, 15 g of xylene was added, and the mixture was stirred at 180 ° C. for 5 hours while water was azeotroped with xylene. After the stirring was completed, the solution was poured into 3 L of water to obtain a white precipitated polymer. The precipitate was collected by filtration, washed with water three times, and then dried at 80 ° C. for 20 hours using a vacuum dryer. When the resulting measuring the infrared absorption spectrum of the polymer solids, 1780 cm around ^-1, absorption peaks of an imide structure caused by a polyimide was detected near 1377 cm ^-1. Thus, an organic solvent-soluble polyimide D having a functional group capable of reacting with an epoxy group and containing 14% by weight of the structure represented by the general formula (1) was obtained. 6 g of tetrahydrofuran was added to 4 g of the obtained polymer, and the mixture was stirred at 23 ° C. and dissolved.

Synthesis Example 5 Synthesis of Organic Solvent-Soluble Polyimide E Under a dry nitrogen stream, 29.3 g (0.08 mol) of BAHF and 4.97 g (0.02 mol) of SiDA were dissolved in 130 g of NMP. 28.54 g (0.092 mol) of ODPA was added thereto together with 20 g of NMP, and the mixture was stirred at 20 ° C. for 1 hour, and then stirred at 50 ° C. for 2 hours. 4-nitrophenyl salicylic acid 5.18g (0.02mol) was added here as terminal blocker, and it stirred at 50 degreeC for 2 hours. Thereafter, 15 g of xylene was added, and the mixture was stirred at 180 ° C. for 5 hours while water was azeotroped with xylene. After the stirring was completed, the solution was poured into 3 L of water to obtain a white precipitated polymer. The precipitate was collected by filtration, washed with water three times, and then dried at 80 ° C. for 20 hours using a vacuum dryer. When the resulting measuring the infrared absorption spectrum of the polymer solids, 1780 cm around ^-1, absorption peaks of an imide structure caused by a polyimide was detected near 1377 cm ^-1. Thus, an organic solvent-soluble polyimide E having a functional group capable of reacting with an epoxy group and containing 14.2% by weight of the structure represented by the general formula (1) was obtained. 6 g of tetrahydrofuran was added to 4 g of the obtained polymer, and the mixture was stirred at 23 ° C. and dissolved.

Synthesis Example 6 Synthesis of Organic Solvent-soluble Polyimide F 18.3 g (0.05 mol) of BAHF was dissolved in 100 ml of acetone and 17.4 g (0.3 mol) of propylene oxide, and cooled to −15 ° C. A solution prepared by dissolving 20.4 g (0.11 mol) of 4-nitrobenzoyl chloride in 100 ml of acetone was added dropwise thereto. After completion of dropping, the mixture was stirred at −15 ° C. for 4 hours and then returned to room temperature. The precipitated white solid was filtered off and vacuum dried at 50 ° C.

  30 g of the solid was placed in a 300 ml stainless steel autoclave, dispersed in 250 ml of methyl cellosolve, and 2 g of 5% palladium-carbon was added. Hydrogen was introduced here with a balloon and the reduction reaction was carried out at room temperature. After about 2 hours, the reaction was terminated by confirming that the balloons did not squeeze any more. After completion of the reaction, the palladium compound as a catalyst was removed by filtration and concentrated by a rotary evaporator to obtain a hydroxyl group-containing diamine compound (II). The obtained solid was used for the reaction as it was.

Under a dry nitrogen stream, 24.54 g (0.067 mol) of BAHF, 6.04 g (0.01 mol) of a hydroxyl group-containing diamine compound (II), and 2.49 g (0.01 mol) of SiDA were dissolved in 250 g of NMP. Here, 41.03 g (0.1 mol) of 2,2-bis (3,4-dicarboxyphenyl) ethylene dianhydride (hereinafter referred to as TMEG-100), 4-aminothiophenol (terminal blocker) 4.45 g (0.03 mol) (manufactured by Tokyo Chemical Industry Co., Ltd.) was added and stirred at 60 ° C. for 6 hours. Thereafter, 15 g of xylene was added, and the mixture was stirred at 150 ° C. for 5 hours while azeotropically reacting with xylene. After the stirring was completed, the solution was poured into 2 L of water to obtain a white precipitated polymer. The precipitate was collected by filtration, washed with water three times, and then dried at 80 ° C. for 20 hours using a vacuum dryer. When the resulting measuring the infrared absorption spectrum of the polymer solids, 1780 cm around ^-1, absorption peaks of an imide structure caused by a polyimide was detected near 1377 cm ^-1. Thus, an organic solvent-soluble polyimide F having a functional group capable of reacting with an epoxy group and containing 2.9% by weight of the structure represented by the general formula (1) was obtained. 6 g of tetrahydrofuran was added to 4 g of the obtained polymer, and the mixture was stirred at 23 ° C. and dissolved.

Synthesis Example 7 Synthesis of Organic Solvent Soluble Polyimide G Under dry nitrogen flow, 18.3 g (0.05 mol) of BAHF and 34.2 g (0.3 mol) of allyl glycidyl ether were dissolved in 100 g of gamma butyrolactone (GBL), and −15 Cooled to ° C. To this, 22.1 g (0.11 mol) of trimellitic anhydride chloride dissolved in 50 g of GBL was added dropwise so that the temperature of the reaction solution did not exceed 0 ° C. After completion of dropping, the mixture was stirred at 0 ° C. for 4 hours. This solution was concentrated with a rotary evaporator and charged into 1 liter of toluene to obtain a hydroxyl group-containing acid anhydride (I).

Under a dry nitrogen stream, BAHF 30.03 g (0.082 mol), SiDA 3.73 g (0.015 mol), and 4-aminothiophenol (manufactured by Tokyo Chemical Industry Co., Ltd.) 4.45 g (0 0.03 mol) was dissolved in 100 g of NMP. To this, 71.45 g (0.1 mol) of hydroxyl group-containing acid anhydride (I) was added together with 30 g of NMP and reacted at 20 ° C. for 1 hour, and then reacted at 50 ° C. for 4 hours. Then, it stirred at 180 degreeC for 5 hours. After the completion of stirring, the solution was poured into 3 l of water to obtain a white precipitated polymer. The precipitate was collected by filtration, washed three times with water, and then dried at 200 ° C. for 5 hours using a vacuum dryer. When the resulting measuring the infrared absorption spectrum of the polymer solids, 1780 cm around ^-1, absorption peaks of an imide structure caused by a polyimide was detected near 1377 cm ^-1. Thus, an organic solvent-soluble polyimide G having a functional group capable of reacting with an epoxy group and containing 3% by weight of the structure represented by the general formula (1) was obtained. 6 g of tetrahydrofuran was added to 4 g of the obtained polymer, and the mixture was stirred at 23 ° C. and dissolved.

Synthesis Example 8 Synthesis of Organic Solvent-Soluble Polyimide H Under a dry nitrogen stream, BAHF 25.64 g (0.07 mol), SiDA 4.97 g (0.02 mol), and 3-Aph 2.18 g (0.02) as an end-capping agent Mol) was dissolved in 150 g of NMP. To this, 15.51 g (0.05 mol) of ODPA and 14.71 g (0.05 mol) of biphenyltetracarboxylic dianhydride (BPDA) were added together with 30 g of NMP and reacted at 20 ° C. for 1 hour. Reacted for hours. Then, it stirred at 180 degreeC for 5 hours. After the stirring was completed, the solution was poured into 3 L of water to obtain a white precipitated polymer. The precipitate was collected by filtration, washed with water three times, and then dried at 80 ° C. for 20 hours using a vacuum dryer. When the resulting measuring the infrared absorption spectrum of the polymer solids, 1780 cm around ^-1, absorption peaks of an imide structure caused by a polyimide was detected near 1377 cm ^-1. In this way, an organic solvent-soluble polyimide H having a functional group capable of reacting with an epoxy group and containing 7.3% by weight of the structure represented by the general formula (1) was obtained. 6 g of tetrahydrofuran was added to 4 g of the obtained polymer, and the mixture was stirred at 23 ° C. and dissolved.

Synthesis Example 9 Synthesis of Organic Solvent-Soluble Polyimide I Under a dry nitrogen stream, BAHF 14.65 g (0.04 mol), SiDA 12.42 g (0.05 mol), and 3-Aph 2.18 g (0.02) as a terminal blocking agent Mol) was dissolved in 80 g of NMP. To this, 31.02 g (0.1 mol) of ODPA was added together with 20 g of NMP, reacted at 20 ° C. for 1 hour, and then stirred at 50 ° C. for 4 hours. Thereafter, 15 g of xylene was added, and the mixture was stirred at 180 ° C. for 5 hours while water was azeotroped with xylene. After the stirring was completed, the solution was poured into 3 L of water to obtain a white precipitated polymer. The precipitate was collected by filtration, washed with water three times, and then dried at 80 ° C. for 20 hours using a vacuum dryer. When the resulting measuring the infrared absorption spectrum of the polymer solids, 1780 cm around ^-1, absorption peaks of an imide structure caused by a polyimide was detected near 1377 cm ^-1. In this way, an organic solvent-soluble polyimide I having a functional group capable of reacting with an epoxy group and containing 19.1% by weight of the structure represented by the general formula (1) was obtained. 6 g of tetrahydrofuran was added to 4 g of the obtained polymer, and the mixture was stirred at 23 ° C. and dissolved.

Synthesis Example 10 Synthesis of Organic Solvent-Soluble Polyimide J Under a dry nitrogen stream, BAHF 28.2 g (0.077 mol), SiDA 0.75 g (0.003 mol), and 3-Aph 4.37 g (0.04) as an end-capping agent Mol) was dissolved in 80 g of NMP. To this, 31.02 g (0.1 mol) of ODPA was added together with 20 g of NMP, reacted at 20 ° C. for 1 hour, and then stirred at 50 ° C. for 4 hours. Thereafter, 15 g of xylene was added, and the mixture was stirred at 180 ° C. for 5 hours while water was azeotroped with xylene. After the stirring was completed, the solution was poured into 3 L of water to obtain a white precipitated polymer. The precipitate was collected by filtration, washed three times with water, and then dried at 80 ° C. for 20 hours using a vacuum dryer. When the resulting measuring the infrared absorption spectrum of the polymer solids, 1780 cm around ^-1, absorption peaks of an imide structure caused by a polyimide was detected near 1377 cm ^-1. Thus, an organic solvent-soluble polyimide J having a functional group capable of reacting with an epoxy group and containing 1.1% by weight of the structure represented by the general formula (1) was obtained. 6 g of tetrahydrofuran was added to 2 g of the obtained polymer, and the mixture was stirred at 23 ° C. and dissolved.

  In addition, each material used by the Example and the comparative example is as follows.

Solid epoxy compound Epicoat 157S70 (trade name, epoxy equivalent: 210 g / eq, manufactured by Japan Epoxy Resins Co., Ltd.)
Epicoat 154 (trade name, epoxy equivalent: 180 g / eq, manufactured by Japan Epoxy Resins Co., Ltd.)
Epototo YH-434L (trade name, epoxy equivalent: 130 g / eq, manufactured by Toto Kasei Co., Ltd.)
Epicoat 1001 (trade name, epoxy equivalent: 460 g / eq, manufactured by Japan Epoxy Resin Co., Ltd.).

Liquid epoxy compound epicoat 828 (trade name, epoxy equivalent 187 g / eq, manufactured by Japan Epoxy Resins Co., Ltd.)
Epicoat 1750 (trade name, epoxy equivalent 158 g / eq, manufactured by Japan Epoxy Resins Co., Ltd.)
Epicron HP-4032 (trade name, epoxy equivalent 152 g / eq, manufactured by Dainippon Ink & Chemicals, Inc.)
Epicoat 152 (trade name, epoxy equivalent 175 g / eq, manufactured by Japan Epoxy Resin Co., Ltd.).

Curing accelerator 2-phenylimidazole (trade name 2PZ, manufactured by Shikoku Chemicals Co., Ltd., water-insoluble)
2-Ethyl-4-methylimidazole (trade name 2E4MZ, manufactured by Shikoku Kasei Kogyo Co., Ltd., water-soluble)
Carboxylated NBR
PNR-1HC (trade name, manufactured by JSR Corporation)
Solvent: Methyl ethyl ketone Conductive particles Particles obtained by coating the surface of polystyrene particles having an average particle diameter of 5 μm with 0.2 μm thick Ni and 0.2 μm thick Au in this order by plating.

Examples 1-8 and Comparative Examples 1-7
A resin component, a solvent, and a dispersion were mixed using a ball mill so as to obtain a blending ratio shown in Table 1 for each component of Examples 1 to 8 and Comparative Examples 1 to 7 to prepare an adhesive composition varnish for semiconductor.

  The semiconductor adhesive composition varnish produced at the composition ratio shown in Table 1 was applied onto a polyethylene terephthalate film having a thickness of 38 μm that had been subjected to a silicone-based release treatment using a slit die coater (coating machine). Drying was carried out at 4 ° C. for 4 minutes. A polypropylene film having a thickness of 15 μm is laminated as a plastic film on the adhesive composition for semiconductor after drying at a heating roll temperature of 40 ° C. and wound into a paper tube having a diameter of 7.6 cm in a roll shape. An adhesive sheet material for semiconductor having a thickness of 30 μm (a three-layer structure of a polypropylene film, an adhesive composition layer for semiconductor, and a polyethylene terephthalate film) was obtained.

  The adhesion strength of the obtained plastic film and the adhesive composition layer for semiconductor was measured as follows. Adhesive sheet material for semiconductor (3-layer structure of polypropylene film, semiconductor adhesive composition layer, polyethylene terephthalate film) is cut to a width of 25 mm and a length of 300 mm, using a double-sided adhesive tape on a 2 mm thick stainless steel plate, polyethylene terephthalate The film is fixed on the surface, and the above-mentioned polypropylene film (lightly peeled side plastic film) is peeled from the semiconductor adhesive composition layer at an angle of 90 degrees at a speed of 200 mm / min, between the polypropylene film and the semiconductor adhesive composition layer. The adhesive strength (N / m) of was measured. Next, the adhesive sheet material for semiconductor (two-layer structure of polyethylene terephthalate fill and semiconductor adhesive composition layer) after removing the polypropylene film is cut out to a width of 25 mm and a length of 300 mm, and a stainless steel having a thickness of 2 mm using a double-sided adhesive tape. The polyethylene terephthalate film is fixed on the surface of the semiconductor adhesive composition, and the polyethylene terephthalate film (heavy release side plastic film) is peeled off from the semiconductor adhesive composition layer at an angle of 90 degrees at a rate of 200 mm / min. The adhesive force (N / m) between the adhesive composition for semiconductors was measured. The results are shown in Table 2. A universal tester (Orientec Co., Ltd., RTM-100) was used to peel off the polypropylene film and the polyethylene terephthalate film and measure the adhesive strength.

  Using the obtained adhesive sheet material for semiconductor, a semiconductor device was manufactured as follows.

1. Lamination process and evaluation Embedding of the adhesive sheet material for semiconductor wound in a roll shape into the bump electrode was performed using a bonding apparatus (Technology Vision Co., Ltd., model 900S).

  First, the light release side plastic film (for example, polypropylene film in Example 1) was removed from the semiconductor adhesive sheet material to expose the semiconductor adhesive composition surface. At this time, the presence or absence of peeling traces on the surface of the adhesive composition for a semiconductor, and further, the presence or absence of peeling or dropping of the semiconductor adhesive composition from the heavy release side plastic film (for example, polyethylene terephthalate film in Example 1) were observed. In the case of “Yes”, “X” is given when there is, and “O” is given when there is no. Furthermore, when bending with a radius of curvature of 5 mm so that the adhesive composition surface for the semiconductor faces outward, the presence or absence of cracking of the adhesive composition for semiconductor or peeling from the heavy release side plastic film is observed. The flexibility of the adhesive composition for semiconductors was evaluated with x as the case and ◯ as the case without.

  Next, with a bump electrode having an average height of 20 μm (128 bumps / chip, pitch 100 μm, gold-plated bump) fixed on the bonding apparatus stage, a light release side plastic film is applied to the bump electrode of a silicon wafer (diameter 150 mm, thickness 625 μm). The adhesive composition surface for semiconductor of the adhesive sheet material for semiconductor after peeling was laminated at a temperature of 60 ° C. and a bonding speed of 50 cm / min. At this time, the surface and cross section of the adhesive composition for semiconductor were observed with a microscope (20 magnifications) for the presence or absence of voids or voids, and the presence or absence of voids or voids around the bump electrodes and at the interface between the semiconductor adhesive composition and the silicon wafer was observed. In the case where there is a gap, the mark is “X”, and in other cases, “◯” is marked. Excess semiconductor adhesive composition around the semiconductor wafer is cut with a cutter blade to obtain a semiconductor wafer in which bump electrodes equipped with a plastic film (for example, polyethylene terephthalate film in Example 1) are embedded with a semiconductor adhesive. It was.

2. Dicing process and evaluation To fix the semiconductor wafer obtained in step 1 to the tape frame and dicing tape, use a wafer mounter (FM-1146-DF, manufactured by Technovision Co., Ltd.) and dicing the wafer substrate surface opposite to the bump electrode. A tape (D-650, manufactured by Lintec Corporation) was attached. The remaining plastic film was then removed. The tape frame was fixed on the cutting stage of a dicing apparatus (DSCO-6240, DFD-6240) so that the adhesive composition surface for the semiconductor would be on the surface, and dicing was performed.

Dicing was performed under the following cutting conditions.
Dicing machine: DFD-6240 (manufactured by DISCO Corporation)
Semiconductor chip size: 2.5 × 16.5mm
Blade: NBC-ZH 127F-SE 27HCCC
Spindle speed: 25000rpm
Cutting speed: 50 mm / s
Cutting depth: Cut to 20 μm depth of dicing tape Cut: One-pass full cut Cut mode: Down cut Cutting water amount: 3.7 L / min Cutting water and cooling water: Temperature 23 ° C., electric conductivity 0.5 MΩ · cm (extra Carbon dioxide gas is injected into pure water)
For semiconductor chips in which bump electrodes are embedded with a semiconductor adhesive composition into individual chips by dicing (semiconductor chips), the presence or absence of cutting powder on the surface of the semiconductor adhesive composition, the surface of the semiconductor adhesive composition The presence or absence of cracks and chips, and the presence or absence of peeling of the adhesive layer from the wafer were confirmed with a microscope. Regarding the adhesion of the cutting powder, the surface where the cutting powder did not adhere to the surface of the adhesive composition for a semiconductor was marked with ◯, and the surface where the cutting powder was adhered was marked with ×. The results are shown in Table 2 for stain resistance. In addition, with regard to cracking, chipping, and peeling of the semiconductor adhesive composition from the wafer, when the length of the semiconductor adhesive composition cracking, chipping, and peeling from the wafer is 25 μm or less from the cutting edge of the semiconductor adhesive composition ◯, and those exceeding 25 μm were marked with ×. The results are shown in Table 2 for scratch resistance. A schematic diagram of this crack, chipping and peeling from the wafer is shown in FIG. Reference numeral 1 is a part of a semiconductor wafer coated with the composition. Reference numeral 2 indicates a crack / notch portion of the generated adhesive composition, and reference numeral 3 indicates a crack. Further, in order to measure the size of the crack or chip of the adhesive composition, the size of the crack / chip 2 or the crack 3 is expressed as the length of the defective portion indicated by reference numeral 4. Reference numeral 5 indicates a cutting end, and reference numeral 6 indicates the maximum length of the missing portion.

3. Flip chip bonding and evaluation A flip chip bonding apparatus (DB-100, manufactured by Tritech Co., Ltd.) was used for connection of the semiconductor chip in which the bump electrode prepared in Step 1 was embedded with the semiconductor adhesive composition to the circuit board. A substrate on which an ITO (indium-tin oxide) pad electrode having a surface resistance of 10Ω / □ and a thickness of 150 nm was formed on an alkali-free glass plate was used as a circuit board. 2. Flip chip bonding was performed under the conditions of a temperature of 200 ° C., a time of 20 s, and a pressure of 0.4 MPa so that the bump electrodes of the semiconductor chip fabricated in the above and the pad electrodes on the circuit board with pad electrodes overlapped. As a result, a circuit board with a semiconductor having a semiconductor chip mounted on the circuit board was obtained. After bonding is completed, the surface of the adhesive composition for semiconductor and the cross section are observed with a microscope (20 magnifications) through the semiconductor substrate on the side of the circuit board where the semiconductor chip is not mounted. ,confirmed. When there was a void or a void, it was marked as “X”, otherwise it was marked as “◯”. The results are shown in the table connectivity.

  The samples after flip-chip bonding in Examples 1 to 8 were observed with a microscope from a direction perpendicular to the interface between the semiconductor and the circuit board, and the protrusion of the adhesive to the semiconductor chip was evaluated. And it was very small.

4). Conductivity evaluation (after initial continuity and thermal shock test)
3 above. The initial conductivity and the conductivity after the thermal shock test of the circuit board with a semiconductor fabricated in the above were evaluated. The conductivity evaluation was measured using a digital multimeter (manufactured by Advantest Corporation, TR6847). The initial continuity is the same as described in 3. The 20 circuit boards with semiconductor manufactured in the above are evaluated, and if there is a continuity failure (the resistance value is infinite and disconnected) even at one location, it is determined as defective, and the number of defective products per 20 circuit boards with semiconductor is determined. It is shown in Table 2. In the thermal shock test, the non-defective product having the initial conductivity was evaluated. After maintaining the circuit board with a semiconductor at −40 ° C. for 5 minutes and then maintaining at 125 ° C. for 5 minutes as one cycle, the continuity of the circuit board with semiconductor after 1000 cycles was evaluated. Evaluate 20 good products in the initial continuity test, and if there is a continuity failure (resistance value is infinite and disconnected) even at one location, it is considered as defective. The number of defective products per 20 circuit boards with semiconductors It is shown in Table 2.

5. Insulation evaluation The insulation between adjacent electrodes on the circuit board with a semiconductor manufactured in step 1 was evaluated. Resistance values were evaluated using an electrometer / high resistance system 6517A manufactured by Keithley Instruments Co., Ltd. A resistance value of 10 ¹⁰ Ω or more was evaluated as “◯”, and a resistance value of less than 10 ¹⁰ Ω was evaluated as “x”. The results are shown in Table 2.

6). Liquid crystal display test After the thermal shock test evaluation, a circuit board with a semiconductor was incorporated in a liquid crystal panel to produce a semiconductor device, and a display test was performed. The displayed ones were marked with ◯, and the other ones that were not displayed or had noise were marked with ×.

Example 7
Example 1 with the exception that the adhesive composition for semiconductor varnish produced based on the composition ratio in Table 1 was used and the polypropylene film was replaced with a 38 μm-thick polyethylene terephthalate film subjected to silicone release treatment as a plastic film. Similarly, an adhesive sheet material for a semiconductor was obtained.

Example 8
Similar to Example 1 except that a semiconductor adhesive composition varnish produced based on the composition ratio in Table 1 was used, and a 38 μm-thick polyethylene terephthalate film not subjected to mold release treatment was used as the plastic film for coating. Thus, an adhesive sheet material for a semiconductor was obtained.

  The varnish compositions of Examples 1 to 8 and Comparative Examples 1 to 7 are shown in Table 1, and the evaluation results are shown in Table 2.

Example 9
An adhesive composition varnish for semiconductor was prepared in the same manner as in Example 1 with the composition ratio described in Table 3. This adhesive composition varnish for semiconductor is hydrophilized using a slit die coater (coating machine) to an unstretched polypropylene film (trade name, Treffan NO model number ZK-99, manufactured by Toray Industries, Inc.) having a thickness of 80 μm. It apply | coated on the surface which has not been processed, and it dried for 4 minutes at 75 degreeC after that. An untreated surface of a 15 μm-thick biaxially stretched polypropylene film (trade name, Treffan BO Model No. YK57) as a plastic film is laminated on the dried adhesive composition for a semiconductor, laminated at a heating roll temperature of 40 ° C., and a diameter of 7 It was wound up into a roll of 6 cm paper tube to obtain a semiconductor adhesive sheet material having a semiconductor adhesive layer thickness of 30 μm.

  Using the obtained adhesive sheet material for semiconductor, Example 1 except that a silicon wafer with a diameter of 150 mm and a thickness of 550 μm was used as a silicon wafer with bump electrodes having an average height of 20 μm (256 bumps / chip, pitch 65 μm, gold-plated bump, for liquid crystal driver) used in And evaluated. The results are shown in Table 3.

Examples 10-121, Comparative Examples 8-65
Adhesive composition varnishes for semiconductors were produced in the same manner as in Example 1 with the composition ratios described in Tables 4-14. Each obtained adhesive composition varnish for semiconductor was applied to a film in the same manner as in Example 9 to obtain an adhesive sheet material for semiconductor. Evaluation was performed in the same manner as in Example 9, and the obtained results are shown in Tables 4 to 14.

The raw materials used in Examples 9 to 121 and Comparative Examples 8 to 65 are shown below.
Organic solvent soluble polyimide Organic solvent soluble polyimide A (previously synthesized)
Organic solvent soluble polyimide B (previously synthesized)
Organic solvent soluble polyimide C (previously synthesized)
PI-101 (trade name, manufactured by Maruzen Petrochemical Co., Ltd.), 6 g of tetrahydrofuran was added to 4 g of PI-101, and the mixture was stirred at 23 ° C. to dissolve.

Solid epoxy compound Epicoat 157S70 (trade name, epoxy equivalent: 210 g / eq, manufactured by Japan Epoxy Resins Co., Ltd.)
Epicron HP-7200H (trade name, epoxy equivalent: 280 g / eq, manufactured by Dainippon Ink & Chemicals, Inc.).

Liquid epoxy compound epicoat 828 (trade name, epoxy equivalent 187 g / eq, manufactured by Japan Epoxy Resins Co., Ltd.)
Epicoat YX8000 (trade name, epoxy equivalent 205 g / eq, manufactured by Japan Epoxy Resins Co., Ltd.).

Curing accelerator 2PZ (trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd., water-insoluble)
2E4MZ (trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd., water-soluble)
Solvent: methyl ethyl ketone, tetrahydrofuran, n-propyl alcohol.

Examples 122-141, Comparative Examples 66-85
2. Using the adhesive composition for semiconductors produced based on the composition ratios in Tables 15 to 16, Evaluation was performed in the same manner as in Example 9 except that the flip chip bonding time was set to 60 s. The compositions and evaluation results of the adhesive compositions for semiconductors of Examples 122 to 141 and Comparative Examples 66 to 85 are shown in Tables 15 to 16.

  Samples were prepared and evaluated in the same manner except that polyimide A used in Examples 39 to 59, 102 to 141 and Comparative Examples 28 to 33 and 46 to 85 was replaced with organic solvent-soluble polyimide D. The same results as 39-59, 102-141 and Comparative Examples 28-33, 46-85 were obtained.

  When samples were prepared and evaluated in the same manner except that the polyimide A used in Examples 39 to 59, 102 to 141 and Comparative Examples 28 to 33 and 46 to 85 was replaced with the organic solvent-soluble polyimide E, examples were obtained. The same results as 39-59, 102-141 and Comparative Examples 28-33, 46-85 were obtained.

  Samples were prepared and evaluated in the same manner except that the polyimide A used in Examples 39 to 59, 102 to 141 and Comparative Examples 28 to 33 and 46 to 85 was replaced with the organic solvent-soluble polyimide F. The same results as 47-67, 102-141 and Comparative Examples 34-39, 52-71, 72-91 were obtained.

  Samples were prepared and evaluated in the same manner except that the polyimide A used in Examples 39 to 59, 102 to 141 and Comparative Examples 28 to 33 and 46 to 85 was replaced with an organic solvent-soluble polyimide G. The same results as 39-59, 102-141 and Comparative Examples 28-33, 46-85 were obtained.

  Samples were prepared and evaluated in the same manner except that the polyimide A used in Examples 39 to 59, 102 to 141 and Comparative Examples 28 to 33 and 46 to 85 was replaced with an organic solvent-soluble polyimide H. The same results as 39-59, 102-141 and Comparative Examples 28-33, 46-85 were obtained.

Examples 142, 143
A semiconductor adhesive composition was produced in the same manner as in Example 1 with the composition ratio described in Table 17. Each obtained adhesive composition for a semiconductor was applied to a film in the same manner as in Example 9 to obtain an adhesive sheet material for a semiconductor. Evaluation was performed in the same manner as in Example 9, and the results obtained are shown in Table 17.

Examples 144, 145
A semiconductor adhesive composition was produced in the same manner as in Example 1 with the composition ratio described in Table 18. Each obtained adhesive composition for a semiconductor was applied to a film in the same manner as in Example 9 to obtain an adhesive sheet material for a semiconductor. Evaluation was conducted in the same manner as in Example 9, and the results obtained are shown in Table 18.

Example 146
A semiconductor adhesive composition was produced in the same manner as in Example 1 with the composition ratio described in Example 39 of Table 7. This semiconductor adhesive composition is hydrophilized to an unstretched polypropylene film (trade name, Treffan NO model number ZK-99, manufactured by Toray Industries, Inc.) having a thickness of 80 μm using a slit die coater (coating machine). The film was coated on the surface not subjected to the coating, and then dried at 75 ° C. for 4 minutes. A plastic base film (trade name, BGE-124S, manufactured by Toyo Adtec Co., Ltd.) in which a 160 μm-thick pressure-sensitive adhesive layer is formed on the dried adhesive composition for semiconductor, and the pressure-sensitive adhesive layer surface is bonded to semiconductor The film was laminated at a heating roll temperature of 25 ° C. so as to adhere to the composition, and wound into a roll on a paper tube having a diameter of 7.6 cm. As a result, a semiconductor adhesive sheet material having both a back grind tape function and a semiconductor adhesive function in which four layers of a polypropylene film, a semiconductor adhesive composition layer, a pressure-sensitive adhesive layer, and a plastic film were laminated in this order was obtained.

  The adhesion strength between the materials was measured as follows. Adhesive sheet material for semiconductor (4-layer structure of polypropylene film, adhesive composition layer for semiconductor, adhesive layer, base film) is cut to a width of 25 mm and a length of 300 mm, using a double-sided adhesive tape on a 2 mm thick stainless steel plate The polyethylene terephthalate film is fixed on the surface, and the above-mentioned polypropylene film (lightly peeled side plastic film) is peeled off from the semiconductor adhesive composition layer at an angle of 90 degrees at a rate of 200 mm / min. The adhesion between the layers was measured. This adhesive force was 14 N / m. Next, after removing the polypropylene film, the semiconductor adhesive sheet material (three-layer structure of the base film, the pressure-sensitive adhesive layer, and the semiconductor adhesive composition layer) is cut into a width of 25 mm and a length of 300 mm, and the thickness is measured using a double-sided adhesive tape. A semiconductor adhesive composition surface is fixed on a 2 mm stainless steel plate, and the base film with the pressure-sensitive adhesive layer (heavy release side plastic film) is 200 mm / min in the direction of 90 degrees from the semiconductor adhesive composition layer. Then, it peeled off at the interface between the pressure-sensitive adhesive layer and the adhesive composition layer for semiconductor, and the adhesive force between the pressure-sensitive adhesive layer and the adhesive composition for semiconductor was measured. As a result, it was 45 N / m.

  A bonding apparatus (Model 900S, manufactured by Technovision Co., Ltd.) was used for embedding the adhesive sheet material for a semiconductor having both a back grind tape function wound in a roll shape and a semiconductor bonding function into a bump electrode.

  With a bump electrode with an average height of 20 μm fixed on the bonding device stage (256 bumps / chip, pitch 65 μm, gold-plated bump, for liquid crystal driver) on the bump electrode of a silicon wafer (diameter 150 mm, thickness 625 μm), light release side The adhesive composition surface for semiconductor of the adhesive sheet material for semiconductor after peeling the polypropylene film which is a plastic film was laminated at a temperature of 60 ° C. and a bonding speed of 50 cm / min. Excess semiconductor adhesive composition around the semiconductor wafer was cut with a cutter blade. As a result, a semiconductor wafer was obtained in which an electrode in which a pressure-sensitive adhesive layer and a base film were laminated in this order on a semiconductor adhesive was embedded with the semiconductor adhesive.

  Next, the surface of the semiconductor wafer opposite to the bump electrode was ground and polished using a grinding / polishing apparatus (DGP-8760, manufactured by DISCO Corporation) so that the thickness of the semiconductor wafer became 100 μm. Subsequently, the base film with the pressure-sensitive adhesive layer was peeled off from the semiconductor adhesive.

  After that, in Example 1. 2. Dicing process 3. flip chip bonding; 4. Conductivity evaluation, When a liquid crystal display test was conducted, the same results as in Example 39 were obtained.

Schematic of semiconductor wafer with adhesive composition for semiconductor after dicing

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Part of semiconductor wafer to which composition is applied 2 Chip / crack 3 Crack 4 Chip length 5 Cutting edge 6 Maximum chip length

Claims (6)

(A) an organic solvent-soluble polyimide, (b) an epoxy compound, (c) a curing accelerator, (d) conductive particles, and (b) 100 parts by weight of the epoxy compound, (a) soluble in an organic solvent 15 to 90 parts by weight of polyimide, (c) 0.1 to 10 parts by weight of a curing accelerator, and (b) a compound in which the epoxy compound is liquid at 25 ° C. and 1.013 × 10 ⁵ N / m ² An adhesive composition for a semiconductor, which contains a compound that is solid at 25 ° C. and 1.013 × 10 ⁵ N / m ² , and the content of the liquid epoxy compound is 20% by weight or more and 60% by weight or less based on the total epoxy compound object. (A) The organic solvent-soluble polyimide has a structure represented by any one of the general formulas (2) to (7), and has at least one functional group capable of reacting with an epoxy group at each side chain and terminal. 2. The adhesive composition for a semiconductor according to claim 1, which is a polymer and has a structure represented by the general formula (1) as R ⁴ in the general formulas (2) to (7) in an amount of 2 to 15 wt% based on the total amount of the polymer.

(In the formula, R ¹ represents a divalent hydrocarbon group, R ² represents a monovalent hydrocarbon group, and may be the same or different. N represents an integer of 1 to 10.)

(In the formula, R ³ is a 4 to 14 valent organic group, R ⁴ is a 2 to 12 valent organic group, and at least one of R ³ and R ⁴ is 1,1,1,3,3. , 3-hexafluoro-propyl group, an isopropyl group, an ether group, .R ⁵ and R ⁶ at least one contains a group selected from the group consisting of a thioether group and a SO ₂ group, the phenolic hydroxyl group, sulfonic acid group and thiol An organic group having at least one group selected from the group consisting of groups, which may be the same or different, X is a monovalent organic group, Y is a divalent organic group, and Z is a monovalent organic group. M represents a range of 8 to 200. α and β each represents an integer of 0 to 10, and α + β is an integer of 1 to 10.) The cutting state after dicing the adhesive composition for a semiconductor according to claim 1 formed on a semiconductor wafer is a maximum of a defective portion of the adhesive composition for a semiconductor with a cutting edge of the adhesive composition for a semiconductor as a reference position of 0 μm. The adhesive composition for semiconductors whose length is 25 micrometers or less. A semiconductor device having a heat resistant resin obtained from the adhesive composition for a semiconductor according to claim 1. A plastic film having the semiconductor adhesive composition according to any one of claims 1 to 3 is formed on a wafer on which a plurality of semiconductor elements having electrodes formed thereon are mounted. The semiconductor element with the adhesive composition for semiconductor is mounted on the mounting substrate, and the electrodes formed on the semiconductor element and the electrodes on the mounting substrate are mounted. A method for manufacturing a semiconductor element for electrical connection. The semiconductor adhesive composition according to any one of claims 1 to 3, a pressure-sensitive adhesive layer, and a plastic film are formed in this order on a wafer on which a plurality of semiconductor elements having electrodes formed thereon are mounted. After polishing the wafer surface on which no solder is formed, it is separated into individual pieces by dicing, and the separated semiconductor element with an adhesive composition for semiconductor is mounted on a mounting substrate, and the electrodes formed on the semiconductor element are mounted. A method for manufacturing a semiconductor element for electrically connecting electrodes on a substrate.

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