Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
  • C08G73/106—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing silicon
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
  • B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/15—Heterocyclic compounds having oxygen in the ring
  • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
  • C08K5/1515—Three-membered rings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
  • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
  • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
  • C09J11/02—Non-macromolecular additives
  • C09J11/06—Non-macromolecular additives organic
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J179/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09J161/00 - C09J177/00
  • C09J179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
  • C09J179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J7/00—Adhesives in the form of films or foils
  • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
  • C09J7/38—Pressure-sensitive adhesives [PSA]
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W74/00—Encapsulations, e.g. protective coatings
  • H10W74/01—Manufacture or treatment

Definitions

• the present invention relates to a polyimide resin suitable for use as a heat-resistant adhesive for the manufacture of semiconductors or electronic components. More specifically, the present invention relates to a polyimide resin for use in the manufacture of semiconductors or electronic components, which is attached to a semiconductor element mounting substrate when manufacturing a semiconductor package, and to a resin composition, adhesive, and adhesive film containing the polyimide resin.
• Such adhesive films are generally manufactured by providing various adhesive layers on a heat-resistant film.
• Proposed heat-resistant films include polyimide, polyamide, polyamideimide, polyetherimide, polyester, polyphenylene sulfide, polysulfone, polyethersulfone, etc.
• proposed resins for the adhesive layer include acrylic, silicone, polyamide, polyimide, etc. Since the adhesive layer is heated to high temperatures in heating processes such as die attach, wire bonding, and resin sealing, and then peeled off from the lead frame, it is necessary not only to solve the mold flash problem, but also to ensure compatibility with each process and to solve the problems of glue residue and warping, and various adhesive layers have been proposed for this purpose.
• Patent Document 1 discloses that a polyimide resin whose main amine components are a diaminosiloxane compound and 2,2-bis(4-(4-aminophenoxy)phenyl)propane or 1,3-bis(3-aminophenoxy)benzene, which is soluble in organic solvents and has a glass transition temperature of 100 to 150°C, can be used as a film-like adhesive for semiconductor packaging materials.
• Patent Document 2 also discloses that a resin composition containing a polyimide resin and a methylol compound, in which the diamine residues of the polyimide resin are residues of a polysiloxane diamine and residues of an aromatic diamine having a hydroxyl group, serves as a heat-resistant adhesive that can be used in the manufacture of electronic devices.
• Patent Document 2 describes that if there is no residue of an aromatic diamine having a hydroxyl group in the polyimide resin or no methylol compound in the resin composition, the adhesive strength with the polyimide film substrate increases significantly after treatment at 300°C, and peeling at room temperature is not possible (paragraph 0098).
• Patent Document 3 discloses that an adhesive film having a heat-resistant film and an adhesive layer, in which the adhesive layer contains a polyimide copolymer containing 30 to 100 mol % of polysiloxane-based diamine residues in the total diamine residues, can be used as an adhesive film for manufacturing semiconductors or electronic components.
• Patent Documents 2 and 3 polyamic acid is synthesized, and a resin composition containing the polyamic acid is applied onto a substrate such as a glass substrate or a polyimide film, and then heated to 250° C. to perform complete imidization.
• a substrate such as a glass substrate or a polyimide film
• the adhesive films using the polyimide resins described in Patent Documents 1 to 3 had a problem in that when the adhesive layer was peeled off from the lead frame after a high-temperature heating process, adhesive residue was generated depending on the conditions.
• the properties required for a high heat-resistant adhesive resin or adhesive film for semiconductor manufacturing are heat resistance at high temperatures, low decomposition, lamination at room temperature, removability at room temperature after high-temperature heat treatment, and low warpage during each process.
• various polyimide resins as mentioned above have been considered, but no polyimide resins that fully possess all of these properties have yet existed.
• the object of the present invention is to provide a polyimide resin having a cyclic imide structure, which generates little volatile matter due to decomposition even at high temperatures of 250°C or higher, has good adhesion at low temperatures, can be laminated at room temperature, has appropriate adhesive strength after passing through a high-temperature heat treatment process, can be easily peeled off at room temperature without leaving any adhesive residue, has little warping in each process, and can prevent mold flash; a resin composition and an adhesive film using the same; and a method for producing the same.
• the inventors have conducted extensive research to solve the above problems, and have found that by using a copolymer having a tetracarboxylic dianhydride residue, a diamine residue of a polysiloxane-based diamine, and a diamine residue having an anilide group and/or a diamine residue having a carboxyl group as a polyimide resin having a cyclic imide structure, a solvent-soluble polyimide resin having a cyclic imide structure that provides suitable adhesion and removability can be obtained.
• the inventors have also found that the above problems can be solved by using a resin composition containing such a resin, and that it is possible to provide an adhesive for semiconductor or electronic component manufacturing that combines high temperature heat resistance, low decomposition, lamination properties at room temperature, removability at room temperature after high temperature heat treatment, and low warpage in each process, and an adhesive film using the same, and have completed the present invention.
• the present invention provides a solvent-soluble polyimide resin having a cyclic imide structure, characterized in that the polyimide resin has a repeating unit represented by the following general formula (1):
• Z is a tetracarboxylic dianhydride residue
• A is a diamine residue of a polysiloxane-based diamine, as well as a diamine residue having an anilide group and/or a diamine residue having a carboxyl group
• the present invention also provides a resin composition comprising the polyimide resin of the present invention and an organic solvent.
• the present invention also provides a pressure-sensitive adhesive for producing semiconductors or electronic parts, which comprises the polyimide resin of the present invention.
• the present invention further provides an adhesive film for producing semiconductors or electronic parts, which comprises a heat-resistant film and the resin composition of the present invention laminated on at least one surface of the heat-resistant film.
• the present invention can provide a polyimide resin that generates little volatile matter due to decomposition even at high temperatures of 250°C or more, has good adhesion at low temperatures, can be laminated at room temperature, has appropriate adhesive strength after passing through a high-temperature heat treatment process, can be easily peeled off at room temperature without leaving any adhesive residue, has little warping in each process, and can prevent mold flash, as well as a resin composition, adhesive, and adhesive film containing the polyimide resin. Furthermore, because a solvent-soluble polyimide resin with a cyclic imide structure is used, a heating step for imidization is not required in the manufacturing process of the adhesive film, making it possible to provide a highly productive manufacturing process.
• the polyimide resin of the present invention is a solvent-soluble polyimide resin having a repeating unit represented by the following general formula (1) and a cyclic imide structure.
• cyclic imide structure means a structure in which imide groups form a ring.
• solvent-soluble in the present invention is a term used for an organic polar solvent used in synthesizing a polyimide and an organic solvent used to dilute a polyimide resin in a resin composition described below, and means that 5 g or more of the polyimide resin dissolves in 100 g of a solvent.
• Z is a tetracarboxylic dianhydride residue
• A is a diamine residue of a polysiloxane-based diamine, as well as a diamine residue having an anilide group and/or a diamine residue having a carboxyl group
• the repeating unit represented by the above general formula (1) has at least a tetracarboxylic dianhydride residue (Z) and a diamine residue (A), and the diamine residue (A) is a diamine residue (A 1 ) of a polysiloxane-based diamine, as well as a diamine residue (A 2 ) having an anilide group and/or a diamine residue (A 3 ) having a carboxyl group.
• the polyimide resin of the present invention is characterized in that it is a polymer containing the following repeating unit (1-1) in which the diamine residue (A) is a diamine residue (A 1 ) of a polysiloxane-based diamine, and also containing the following repeating unit (1-2) in which the diamine residue (A) is a diamine residue (A 2 ) having an anilide group, or the following repeating unit (1-3) in which the diamine residue (A) is a diamine residue (A 3 ) having a carboxyl group.
• Z is a tetracarboxylic dianhydride residue
• A1 is a diamine residue of a polysiloxane-based diamine.
• Z is a tetracarboxylic dianhydride residue
• A2 is a diamine residue having an anilide group.
• Z is a tetracarboxylic dianhydride residue
• A3 is a diamine residue having a carboxyl group.
• the polyimide resin of the present invention may be a random copolymer containing the repeating unit (1-1) and the repeating unit (1-2) and/or the repeating unit (1-3) in a random arrangement, or may be a block polymer containing a structure in which only a portion of the repeating units (1-1) to (1-3) are polymerized first.
• the resin composition containing the polyimide resin of the present invention can be suitably used as a heat-resistant adhesive for manufacturing semiconductors or electronic components.
• the diamine residue (A) constituting the polyimide resin of the present invention have the specific structure described above, the adhesive layer laminated on the heat-resistant film can achieve both appropriate adhesive strength and adhesive residue upon peeling (no adhesive residue).
• a diamine residue having a functional group other than a carboxyl group or an anilide group is used, it is difficult to achieve both appropriate adhesive strength and adhesive residue upon peeling.
• the tetracarboxylic dianhydride residue (Z) preferably contains a residue of an aromatic tetracarboxylic dianhydride.
• aromatic tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2'dimethyl-3,3',4,4'-biphenyltetracarboxylic dianhydride, 5,5'dimethyl-3,3',4,4'-biphenyltetracarboxylic dianhydride, and 1,2'dimethyl-3,3',4,4'-biphenyltetracarboxylic dianhydride.
• phenyl tetracarboxylic dianhydride 2,3,3',4'-biphenyl tetracarboxylic dianhydride, 2,2',3,3'-biphenyl tetracarboxylic dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, 2,3,3',4'-diphenyl ether tetracarboxylic dianhydride, 2,2',3,3'-diphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 2,2',3,3'-benzophenone tetracarboxylic dianhydride, 2,3,3',4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-diphenyl sulfone tetracarboxylic dianhydride,
• the aromatic tetracarboxylic dianhydrides may be used alone or in combination of two or more.
• monocyclic acid dianhydrides such as pyromellitic acid dianhydride are preferred because they can improve heat resistance by increasing the heat reduction temperature.
• the diamine residue (A) in the general formula (1) is a diamine residue of a polysiloxane-based diamine, as well as a diamine residue having an anilide group and/or a diamine residue having a carboxyl group.
• the polysiloxane diamine constituting the diamine residue of the polysiloxane diamine is not particularly limited, but is preferably a polysiloxane diamine represented by the following general formula (2).
• n is a natural number and is an integer of 1 to 150. n is preferably 5 to 50, and more preferably 7 to 15.
• R 1 and R 2 are the same or different and represent an alkylene group or a phenylene group having 1 to 40 carbon atoms.
• R 1 and R 2 are preferably an alkylene group or a phenylene group having 1 to 10 carbon atoms, and more preferably an alkylene group having 2 to 5 carbon atoms.
• R 3 to R 6 are the same or different and represent an alkyl group, a phenyl group, or a phenoxy group having 1 to 40 carbon atoms.
• R 3 to R 6 are preferably an alkyl group or a phenoxy group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 5 carbon atoms.
• polysiloxane diamines represented by general formula (2) include ⁇ , ⁇ -bis(3-aminopropyl)polydimethylsiloxane, ⁇ , ⁇ -bis(3-aminopropyl)polydiethylsiloxane, ⁇ , ⁇ -bis(3-aminopropyl)polydipropylsiloxane, ⁇ , ⁇ -bis(3-aminopropyl)polydibutylsiloxane, ⁇ , ⁇ -bis(3-aminopropyl)polydiphenoxysiloxane, ⁇ , ⁇ -bis(2-aminoethyl)polydimethylsiloxane, ⁇ , ⁇ -bis(2-aminoethyl)polydiphenoxysiloxane, ⁇ , ⁇ -bis( Examples of suitable diamines include ⁇ , ⁇ -bis(4-aminobutyl)polydimethylsiloxane, ⁇ , ⁇
• ⁇ , ⁇ -bis(3-aminopropyl)polydimethylsiloxane is preferred because it has an excellent balance of adhesion, reactivity, and solubility in reactive solvents.
• the polysiloxane-based diamines represented by the above general formula (2) may be used alone or in combination of two or more kinds.
• the content of diamine residues in the polysiloxane diamine is preferably 60 mol% or more, 65 mol% or more, or even 68 mol% or more, and especially 70 mol% or more of the total diamine residues, and is preferably 97 mol% or less, 95 mol% or less, or even 93 mol% or less, and especially 90 mol% or less. If the diamine residues in the polysiloxane diamine exceed 97 mol% of the total diamine residues, the adhesive strength tends to increase and there is a possibility of adhesive residue being generated.
• the diamine residue having a carboxyl group is preferably a residue of a carboxyl-containing aromatic diamine represented by the following general formula (3):
• X is a single bond, a substituted or unsubstituted alkylene group, a carbonyl group, or an ether group
• p is an integer from 0 to 2
• m1 is an integer from 0 to 4
• m2 is an integer from 0 to 4.
• X is preferably a single bond
• p is preferably 0 to 1
• m1 is preferably 1 to 2.
• carboxyl group-containing aromatic diamines represented by the above general formula (3) include 3,5-diaminobenzoic acid, 3,4-diaminobenzoic acid, 5,5'-methylenebis(2-aminobenzoic acid), 3,5-bis(4-aminophenoxy)benzoic acid, 4,4'-diaminobiphenyl-3,3'-dicarboxylic acid, etc.
• monocyclic carboxyl group-containing aromatic diamines such as 3,5-diaminobenzoic acid and 3,4-diaminobenzoic acid are preferred in that they maintain an appropriate adhesive strength after the adhesive film has passed through a high-temperature heat treatment process and leave no adhesive residue when the adhesive film is peeled off at room temperature.
• residue of a carboxyl-containing aromatic diamine shown below in (4) or (5) may be used as the diamine residue having a carboxyl group.
• the number of carboxyl groups contained in the carboxyl group-containing aromatic diamine is preferably 1 to 5, more preferably 1 to 3, even more preferably 1 or 2, and particularly preferably 1, from the viewpoint of achieving both appropriate adhesive strength and adhesive residue (no adhesive residue) upon peeling.
• the above carboxyl group-containing aromatic diamines may be used alone or in combination of two or more kinds.
• the diamine residue having an anilide group is preferably at least one of the anilide group-containing aromatic diamines represented by the following general formulas (6-1) to (6-3).
• R 1 to R 8 are the same or different and each represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms.
• n1 to n8 each represent an integer of 0 to 4, preferably 0 to 1.
• anilide group-containing aromatic diamines represented by the above general formulas (6-1) to (6-3) include 4,4'-diaminobenzanilide, 3,4'-diaminobenzanilide, 4,3'-diaminobenzanilide, 4,4'-diaminoterephthalanilide, 4,4'-diaminoisophthalanilide, 3,3'-diaminoterephthalanilide, 3,3'-diaminoisophthalanilide, 3,4'-diaminoterephthalanilide, 3,4'-diaminoisophthalanilide, 2-methoxy-4,4'-diaminobenzanilide, 2,2'-dimethoxy-4,4'-diaminobenzanilide, 2,6-dimethoxy-4,4'-diaminobenzanilide, 2,6'-dimethoxy-4,4'-diaminobenzanilide, and the like.
• the anilide group-containing aromatic diamine represented by the above general formula (6-1) is preferred, in that the adhesive strength of the adhesive film is maintained at an appropriate value after the adhesive film has passed through a high-temperature heat treatment process, and no adhesive residue is left when the adhesive film is peeled off at room temperature.
• the above anilide group-containing aromatic diamine may be used alone or in combination of two or more kinds.
• the number of anilide groups contained in the anilide group-containing aromatic diamine is preferably 1 to 3, more preferably 1 or 2, and even more preferably 1, from the viewpoint of achieving both appropriate adhesive strength and adhesive residue (no adhesive residue) upon peeling.
• the above-mentioned carboxyl group-containing aromatic diamine and anilide group-containing aromatic diamine may be used in combination, or either one of them may be used.
• the total content of diamine residues having a carboxyl group and diamine residues having an anilide group is preferably 3 mol% or more, 5 mol% or more, even 7 mol% or more, and particularly 10 mol% or more of the total diamine residues, and is preferably 40 mol% or less, 35 mol% or less, even 32 mol% or less, and particularly 30 mol% or less. If the total content of diamine residues having a carboxyl group and diamine residues having an anilide group is less than 3 mol%, adhesive residue may occur, and if it exceeds 40 mol%, adhesive strength may decrease.
• the molar ratio of the diamine residue having a carboxyl group to the diamine residue having an anilide group contained in the polyimide resin is preferably 9-5:1-5, and more preferably 8-6:2-4.
• the method for synthesizing the solvent-soluble polyimide may be a known method and is not particularly limited.
• the solvent-soluble polyimide can be synthesized by using approximately equal amounts of the aromatic tetracarboxylic dianhydride and diamine described above in an organic polar solvent in the presence of a catalyst and a dehydrating agent at 160 to 200° C. for several hours.
• the solvent-soluble polyimide resin in the present invention is a copolymer, and when the polyimide is synthesized by a one-stage polymerization reaction, a random copolymer is obtained, but if necessary, a block copolymerization reaction can be carried out to synthesize the polyimide resin as a block copolymer.
• polyimide oligomer is synthesized from the aromatic tetracarboxylic dianhydride and diamine described above in the first stage, and then, in the second stage, an aromatic tetracarboxylic dianhydride and/or diamine is further added and polycondensed to obtain a block copolymerized polyimide.
• the dehydration imidization reaction can be accelerated by using a two-component acid-base catalyst that utilizes the lactone equilibrium reaction as a catalyst for these reactions.
• a two-component catalyst lactone catalyst
• ⁇ -valerolactone and pyridine or N-methylmorpholine is used.
• water is generated as the imidization proceeds, and the generated water participates in the lactone equilibrium, becoming an acid-base catalyst and exhibiting catalytic action.
• the water produced by the imidization reaction is removed from the system by azeotropy with a dehydrating agent such as toluene or xylene that coexists in the polar solvent.
• a dehydrating agent such as toluene or xylene that coexists in the polar solvent.
• the reaction is completed, the water in the solution is removed, and the acid-base catalyst becomes ⁇ -valerolactone and pyridine or N-methylmorpholine, which are removed from the system. In this way, a high-purity polyimide solution can be obtained.
• the polyimide obtained by the direct imidization reaction using the lactone catalyst system consisting of the above lactone and base can be obtained in the form of a solution dissolved in a polar solvent, and the polyimide concentration can be set within the preferred range of 10 to 50% by weight of the polyimide resin solids, so the produced polyimide solution can be used as is.
• oxalic acid or malonic acid and pyridine or N-methylmorpholine.
• the oxalate or malonate acts as an acid catalyst to promote the imidization reaction.
• a catalytic amount of oxalic acid or malonic acid remains in the polyimide solvent that is produced.
• This polyimide solution is applied to a substrate and then heated to 200°C or higher.
• the oxalic acid or malonic acid remaining in the polyimide is thermally decomposed as shown in the formula below and removed from the system as a gas.
• Oxalic acid-pyridine catalysts are more active than valerolactone-pyridine catalysts, and can produce high molecular weight polyimide in a short period of time.
• organic polar solvents used in the synthesis of solvent-soluble polyimides it is preferable to use glycol ether-based solvents, amide-based polar solvents, and ketone-based solvents from the viewpoint of the solubility and storage stability of the polyimide copolymer or polyimide resin.
• glycol ether solvents include propylene glycol mono-t-butyl ether, ethylene glycol mono-t-butyl ether, propylene glycol mono-n-butyl ether, propylene glycol monopropyl ether, propylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol monopropyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dipropyl ether, dipropylene glycol di-n-butyl ether, dipropylene glycol di-t-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glyco
• amide-based polar solvents include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, and 1,3-dimethyl-2-imidazoline.
• ketone-based solvents include cyclohexanone. These organic polar solvents can be used alone or in combination of two or more. Among these, glycol ether-based solvents are preferred because they can increase the storage stability of the synthesized polyimide resin solution.
• a solvent-soluble polyimide resin having a cyclic imide structure can be synthesized with high purity. Since the obtained polyimide resin has a cyclic imide structure, it is not necessary to heat the polyimide resin to a high temperature such as 250°C after coating on a substrate, as in the case of polyamic acid, to perform complete imidization. This avoids the problem of deformation of the adhesive film, and makes it possible to provide a highly productive process by omitting the heating step at a high temperature.
• the molecular weight of the obtained solvent-soluble polyimide resin is 10,000 to 200,000 in terms of polystyrene equivalent weight average molecular weight. A polyimide resin in this weight average molecular weight range can achieve good solvent solubility, film properties, and insulating properties.
• the resin composition containing the solvent-soluble polyimide resin and the organic solvent produced as described above can be suitably used as a heat-resistant adhesive for manufacturing semiconductors or electronic components.
• the resin composition of the present invention is a resin composition in a solution state in which the polyimide resin is dissolved in an organic solvent so that the solid content is, for example, 10 to 50% by weight.
• the organic solvent contained in the resin composition the organic polar solvent used in the synthesis of the above-mentioned solvent-soluble polyimide resin can be used as it is.
• the organic solvent used in the synthesis method of the solvent-soluble polyimide resin as it is as the organic solvent of the resin composition, it is possible to easily obtain a resin composition in a solution state in which the polyimide resin is dissolved in the above-mentioned organic polar solvent so that the solid content is 10 to 50% by weight.
• cyclohexanone is preferred, either alone or in combination with other organic solvents, because it allows the drying temperature during coating to be lowered and the amount of residual solvent in the drying process to be reduced at a relatively low temperature (160 to 180°C).
• the ratio of cyclohexanone in the organic solvent contained in the resin composition is usually 20 to 60% by volume, preferably 30 to 50% by volume, and more preferably 35 to 45% by volume.
• glycol ether-based solvents such as triethylene glycol dimethyl ether are preferred as the other organic solvents.
• a glycol ether-based solvent such as triethylene glycol dimethyl ether and a ketone-based solvent such as cyclohexanone in a ratio (volume ratio) of 8:2 to 4:6, preferably 7:3 to 5:5, there is an advantage that all of the monomer solubility, the reduction in drying temperature, and the stability are good.
• the organic solvent contained in the resin composition is not limited to the above, and other organic solvents can also be used.
• the resin composition of the present invention preferably contains an epoxy compound from the viewpoint of adjusting the adhesive strength.
• the epoxy compound is not particularly limited and can be selected based on the compatibility with the polyimide resin composition.
• the epoxy compound for example, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, triazine skeleton-containing epoxy resin, fluorene skeleton-containing epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, crystalline epoxy resin, bisphenol A type epoxy resin, etc. can be used, and these polymer epoxy resins can also be used.
• a multifunctional epoxy compound from the viewpoint of reactivity, and in particular, a monocyclic tetrafunctional epoxy compound (N,N,N',N'-tetraglycidyl-1,3-benzenedi(methanamine)) represented by the following general formula (7) is suitable.
• the content of the epoxy compound in the resin composition is preferably 1 part by weight (solid content) or more, more preferably 2 parts by weight or more, even more preferably 3 parts by weight or more, and particularly preferably 4 parts by weight or more, and is preferably 10 parts by weight or less, 9 parts by weight or less, 8 parts by weight or less, even more preferably 7 parts by weight or less, and particularly preferably 6 parts by weight or less, per 100 parts by weight (solid content) of the solvent-soluble polyimide.
• the resin composition of the present invention can contain inorganic fine particles. By containing inorganic fine particles, the heat resistance and dimensional stability of the resin composition can be improved and the adhesion can be adjusted.
• inorganic fine particles include silica, alumina, titanium oxide, quartz powder, magnesium carbonate, potassium carbonate, barium sulfate, mica, talc, etc., and among them, silica is preferred.
• the content of inorganic particles in the resin composition is preferably 2 to 70 parts by weight, more preferably 5 to 40 parts by weight, and most preferably 7 to 20 parts by weight, based on 100 parts by weight (solid content) of polyimide resin.
• the above resin composition is laminated as a polyimide-based adhesive on at least one side of a heat-resistant film to form an adhesive layer on the surface of the heat-resistant film, thereby forming an adhesive film having a heat-resistant film and an adhesive layer.
• the heat-resistant film is an insulating plastic film that can be used in high-temperature processes such as heating processes such as die attach, wire bonding, resin sealing, reflow, etc.
• Specific examples include plastic films such as polyimide, polyamide, polyamideimide, polyetherimide, polyester, polyphenylene sulfide, polysulfone, and polyethersulfone, and from the viewpoint of heat resistance, a polyimide film is preferred.
• the heat-resistant film In order to improve the adhesion of the resin composition to the heat-resistant film, it is preferable to subject the heat-resistant film to a surface treatment (roughening treatment) such as plasma treatment or corona treatment.
• a surface treatment such as plasma treatment or corona treatment.
• the plasma gas used in the plasma treatment can be oxygen, nitrogen, water, carbon dioxide, argon, or a mixture thereof.
• the adhesive film of the present invention can be produced by applying the resin composition directly or via a primer layer onto a heat-resistant film to form an adhesive layer.
• methods for applying the resin composition of the present invention to a heat-resistant film include a spin coater, a roll coater, a comma coater, gravure printing, screen printing, and a slit die coater. After applying the resin composition, the composition is dried at 100 to 150°C, and then heat-treated continuously or intermittently at 160 to 240°C for 2 minutes to 1 hour to obtain an adhesive layer with good adhesion and heat resistance.
• the pressure-sensitive adhesive layer may be formed by directly applying and drying the resin composition onto a glass substrate, etc. Examples of a method for applying the resin composition onto a glass substrate, etc. include methods using a spin coater, screen printing, a gravure coater, a slit die coater, a bar coater, etc.
• the pressure-sensitive adhesive layer preferably has a weight loss rate of 0.8% or less, more preferably 0.5% or less, and even more preferably 0.3% or less, when heated from 30° C. to 300° C. If the weight loss rate is greater than 0.8%, contamination of a semiconductor element mounting substrate, poor bonding of wire bonding, etc. may occur during the semiconductor manufacturing process.
• the thickness of the adhesive layer is preferably 2 to 30 ⁇ m, more preferably 3 to 20 ⁇ m, and even more preferably 4 to 10 ⁇ m. If the thickness of the adhesive layer is less than 2 ⁇ m, it may be difficult to follow the unevenness of the surface of the semiconductor element mounting substrate.
• the adhesive layer is more than 30 ⁇ m, it may cause wire bonding failure during wire bonding, and the adhesive strength to the lead frame and the sealing resin may increase, which may deteriorate the workability in the re-peeling process.
• the adhesive layer of the present invention usually has a glass transition temperature of -10°C or higher, -8°C or higher, -5°C or higher, or -3°C or higher, and is preferably 40°C or lower, further 30°C or lower, and particularly 25°C or lower. If the glass transition temperature exceeds 40°C, good adhesion may not be obtained when the adhesive layer formed using the resin composition of the present invention is laminated to the substrate to be adhered. In addition, the lower limit of the glass transition temperature does not affect the effect of the present invention, but if it is too low, the adhesion may become excessively high.
• good adhesion means that the adhesive layer film has an adhesive strength of at least such a level that the substrate does not peel off naturally when laminated to the substrate at room temperature. Specifically, it means that the adhesive layer film has an adhesive strength of 5 g/cm or higher when the substrate to be adhered is peeled off at a peel angle of 90 degrees at 10 mm/min. If you want to increase the initial peel strength to the substrate, you can also achieve this by increasing the lamination temperature.
• the adhesive strength of an adhesive layer containing a polyimide-based adhesive increases after a high-temperature heat treatment process, but the adhesive strength of an adhesive containing the polyimide resin of the present invention increases after the first heat treatment at about 150°C, but there is little change in the adhesive strength after the additional high-temperature heat treatment (150°C to 250°C).
• the polyimide resin of the present invention since the polyimide resin of the present invention has a diamine residue with a specific structure as a repeating unit, it can impart and maintain an appropriate adhesive strength to the adhesive layer.
• the appropriate adhesive strength in this case is usually 5 to 400 g/cm, preferably 8 to 300 g/cm, and more preferably 10 to 200 g/cm.
• the adhesive film of the present invention is suitable as an adhesive film for semiconductor manufacturing. Specifically, since the adhesive film of the present invention has an adhesive layer containing the polyimide resin having the specific diamine residue described above, it can be attached to a semiconductor element mounting substrate at room temperature (5 to 35°C). In addition, by using the specific polyimide resin of the present invention, there is little change such as decomposition or deterioration due to heat history in the die attachment process, wire bonding process, flip chip process, rewiring layer formation process, resin sealing process, etc. in the semiconductor manufacturing process, and the adhesive strength is stable. Furthermore, by using the specific polyimide resin of the present invention, adhesive residue is unlikely to occur on the surface of the semiconductor element mounting substrate when peeled off from the semiconductor element mounting substrate after sealing.
• the adhesive film of the present invention is less susceptible to changes such as decomposition and deterioration due to heat history, so it is also suitable as an adhesive film for the manufacture of electronic components, and can be suitably used in the manufacturing process of electronic components that uses high-temperature processes such as reflow.
• the adhesive film of the present invention may have a peelable protective film (insulating film) laminated onto the surface of the adhesive layer to protect the adhesive layer and prevent blocking.
• any protective film may be used, such as plastic films such as polyethylene, polypropylene, and polyethylene terephthalate, metal foils such as aluminum foil and copper foil, and laminated films of plastic films and metal foils.
• the surface of the protective film may be subjected to a release treatment using a silicone-based or fluorine-based release agent.
• the adhesive film of the present invention When the adhesive film of the present invention is used as an adhesive transfer film, one or both sides of the heat-resistant film may be subjected to a release treatment depending on the purpose.
• a release treatment a treatment of coating with silicone resin, fluorine-based resin, etc. is preferable.
• the adhesive film of the present invention can be used to attach to a semiconductor element mounting substrate that mounts a semiconductor or electronic component.
• semiconductor element mounting substrates include lead frames, printed circuit boards, wafers, and sealing resin substrates for fan-out wafer level packages (FOWLPs).
• Semiconductor elements refer to semiconductors and electronic components. Semiconductor elements can be mounted, for example, on a lead frame via a die attach film, or on a printed circuit board by flip-chip connection and a subsequent reflow process. Semiconductor elements can also be mounted on a sealing resin wafer substrate by attaching a chip to the adhesive film of the present invention as in a fan-out package, and then encapsulating the attached chips with resin.
• semiconductor elements also include wafers on which semiconductor elements, comb-shaped electrodes, and other electrical circuits are formed.
• the polyimide resin of the present invention for example, in the fan-out packaging process, no glue remains on the exposed surface after peeling the adhesive film from the sealing resin wafer substrate, so that the process of forming a rewiring layer and the process of dicing the rewiring layer can be carried out on the exposed surface.
• Example 2 A pressure-sensitive adhesive resin composition having a solid content of 40 wt % was obtained in the same manner as in Example 1, except that the amount of KF-8010 used was 236.13 g (0.278 mol) and the amount of 3,5-DABA used was 18.11 g (0.119 mol).
• Example 3 An adhesive resin composition having a solid content of 45 wt % was obtained in the same manner as in Example 1, except that 8.86 g (0.039 mol) of 4,4'-diaminobenzanilide was used instead of 3,5-DABA.
• Example 4 To the resin composition of Example 1, 5 parts by weight of N,N,N',N'-tetraglycidyl-1,3-benzenedi(methanamine) was added per 100 parts by weight of polyimide resin solids, and the mixture was diluted with cyclohexanone to obtain an adhesive resin composition with a solids content of 48 wt %.
• Example 5 To the resin composition of Example 1, 10 parts by weight of a spherical silica slurry (50 wt% solids product, SO-C1 (particle size 0.2 to 0.4 ⁇ m) N-methyl-2-pyrrolidone (hereinafter referred to as NMP) slurry, manufactured by Admatechs Co., Ltd.) was added per 100 parts by weight of the polyimide resin solids, and the mixture was diluted with NMP to obtain an adhesive resin composition with a solids content of 45 wt%.
• NMP N-methyl-2-pyrrolidone
• Thermogravimetric reduction rate (%) The resin of the adhesive layer obtained after the drying was scraped off with a cutter or the like, and about 15 mg of the resin was packed in a standard aluminum container and measured using a thermogravimetric analyzer TG-DTA. The measurement conditions were a temperature rise rate of 5°C/ The temperature was raised to 400°C in 15 minutes, and the weight loss rate (%) from 30 to 300°C was measured.
• the resin compositions synthesized in Examples 1-5 and Comparative Examples 1-5 were applied to a 50 ⁇ m thick polyimide film using a spin coater so that the adhesive layer was 8 ⁇ m thick, and then the resins in Examples 1-4 and Comparative Examples 1 and 3-5 were dried at 120°C for 10 minutes and then at 180°C for 20 minutes, and the resins in Example 5 and Comparative Example 2 were dried at 120°C for 10 minutes and then at 220°C for 20 minutes to obtain adhesive films.
• the resins were dried at 120°C for 10 minutes and then at 180°C for 20 minutes, and for Example 5 and Comparative Examples 1-2, the resins were dried at 120°C for 10 minutes and then at 220°C for 20 minutes to obtain adhesive films.
• Adhesive strength Next, the obtained adhesive film was attached to a 125 ⁇ m thick copper plate (C-7025) using a laminator at 25° C. The initial adhesive strength was measured at room temperature by peeling the adhesive film from the copper plate in a 90° direction. After that, the adhesive film was peeled off from the copper plate in a 90° direction at room temperature after heat treatment for 2 hours at 175°C, 0.5 hours at 220°C, and then another hour at 175°C, and the adhesive strength was measured. Since the adhesive strength varies to some extent, the average value (rounded off) of five measurements was taken. In addition, after measuring the adhesive strength, the transfer of adhesive from the adhesive film to the copper plate (adhesive residue) was confirmed.
• the resin composition containing the polyimide resin of the present invention has adhesiveness at room temperature, excellent heat resistance, and excellent removability, and therefore can be suitably used in the field of heat-resistant adhesive films used in the process of sealing semiconductors or electronic components with sealing resin in semiconductor element mounting substrates such as lead frames, printed circuit boards, and sealing resin substrates for wafers and fan-out wafer-level packages, or in the field of heat-resistant adhesive films used in reflow processes, etc.

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