WO2013183293A1 - Polyimide resin composition, film, adhesive agent and component - Google Patents
Polyimide resin composition, film, adhesive agent and component Download PDFInfo
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- WO2013183293A1 WO2013183293A1 PCT/JP2013/003540 JP2013003540W WO2013183293A1 WO 2013183293 A1 WO2013183293 A1 WO 2013183293A1 JP 2013003540 W JP2013003540 W JP 2013003540W WO 2013183293 A1 WO2013183293 A1 WO 2013183293A1
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- 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
- 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
- C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
-
- 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
- C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
-
- 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
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D179/00—Coating compositions 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 C09D161/00 - C09D177/00
- C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; 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
- 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
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/28—Applying non-metallic protective coatings
- H05K3/282—Applying non-metallic protective coatings for inhibiting the corrosion of the circuit, e.g. for preserving the solderability
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/28—Applying non-metallic protective coatings
- H05K3/285—Permanent coating compositions
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use 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 C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
Definitions
- the present invention relates to a polyimide resin composition containing at least a polar solvent and a polyimide resin. Moreover, it is related with the film formed from the said polyimide resin composition. Moreover, it is related with the components containing the molded object formed from the adhesive agent containing the said polyimide resin composition, and the said polyimide resin composition.
- the main adhesive currently used is an epoxy resin, but the heat resistance of the epoxy resin is not sufficient, and there is a problem that a long time is required for the thermosetting reaction.
- thermoplastic polyimide resin has the advantages of high heat resistance and a relatively short thermosetting reaction.
- a polyamic acid varnish coating film which is a precursor of a polyimide resin, is usually formed and subjected to an imidization step at a high temperature of 300 ° C. or higher, the resin contracts, causing stress or peeling. There was a problem such as. Moreover, there existed a problem that it was not applicable to the thing using the member which is not suitable for high temperature processing, or the use which a high temperature process is unsuitable.
- Patent Documents 1 and 2 a method using a polyimide varnish soluble in a solvent has been proposed (Patent Documents 1 and 2).
- the polyimide varnish soluble in the solvent is not imidized with the polyimide precursor after the coating, but is already imidized at the varnish stage. For this reason, the process of imidizing at high temperature can be cut after a coating film.
- Patent Document 2 discloses ring-closed polyimide (A) and epoxy resin (B) used for the purpose of improving the adhesion between copper foil / polyimide resin (insulating resin layer) without roughening the copper foil.
- a primer layer-containing resin composition has been proposed.
- the solvent-soluble polyimide resin composition does not require a heating step, it is expected to be used in various applications including applications where heat treatment is not possible and applications where the difference in thermal expansion coefficient is a problem. Yes.
- the structure of the polyimide resin is specified in order to be soluble in a solvent, it has been difficult to provide a structure that satisfies various physical properties.
- the present invention has been made in view of such circumstances, and contains a polyimide resin composition excellent in mechanical properties and heat resistance of a molded article obtained while being soluble in a solvent, and the polyimide resin composition. It aims at providing the film
- the polyimide resin composition according to the present invention comprises a composition containing at least a polar solvent and a polyimide resin, and the viscosity average molecular weight ⁇ of the polyimide resin is 0.6 or more and 1.60 or less.
- the viscosity average molecular weight ⁇ of the polyimide resin is 0.6 or more and 1.60 or less.
- 95 mol% or more and 100 mol% or less with respect to all monomers constituting the polyimide resin is an aromatic monomer having no aliphatic chain having 3 or more carbon atoms in the main chain.
- the aromatic monomer is a monomer (A) having at least one of the benzophenone skeletons represented by the chemical formula (1) and the chemical formula (2) in a total content of 5 mol% or more, 30 mol in all monomers constituting the polyimide resin.
- the total monomer constituting the polyimide resin contains 0 mol% or more and less than 45 mol%, and the monomer (B) has at least 3 mol of aromatic rings in the total monomer constituting the polyimide resin.
- the monomer (B-1) is used.
- the viscosity average molecular weight ⁇ of the polyimide resin is in a specific range
- the monomer resin (A) having a benzophenone skeleton is included as a structure of the polyimide resin
- the biphenyl skeleton is further included.
- the monomer (B) having a diphenyl ether skeleton is included in a specific amount
- the monomer (C) having a biphenyl skeleton is less than a specific amount
- the monomer (B) has a structure having three or more aromatic rings. Use the one containing the amount.
- the polyimide resin composition according to the present invention preferably satisfies the following conditions. That is, the polyimide film obtained by coating and drying the composition is (a) a glass transition temperature of 130 ° C. or higher and lower than 260 ° C., (b) a tensile elastic modulus at 25 ° C. of 2.0 GPa or higher, It is preferable that less than 4.0 GPa and (c) 5% thermogravimetric reduction temperature in a nitrogen atmosphere satisfy 500 ° C. or more. It is preferable that the monomer which comprises the terminal group of the said polyimide resin is diamine.
- Preferred examples of the monomer having the benzophenone skeleton include 3,3′-diaminobenzophenone, 3,4′-diaminobenzophenone, 4,4′-diaminobenzophenone, 3,3 ′, 4,4′-benzophenone tetracarboxylic acid dicarboxylate.
- An anhydride and at least one of 2,3 ′, 3,4′-benzophenonetetracarboxylic dianhydride can be mentioned.
- the aromatic ring of the monomer (B-1) is preferably a benzene ring.
- the monomer (C) having a biphenyl skeleton includes 4,4′-bis (3-aminophenoxy) biphenyl, 4,4′-bis (4-aminophenoxy) biphenyl, 3,3′-bis (4- Aminophenoxy) biphenyl, 2,2′-bis (trifluoromethyl) -1,1′-biphenyl-4,4′-diamine, 4,4′-bis (3,4-dicarboxyphenoxy) biphenyl dianhydride 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride and 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride are preferable.
- the monomer (C) which has the said biphenyl skeleton is contained 10 mol% or more in all the monomers which comprise the said polyimide resin.
- the total number of moles of tetracarboxylic dianhydride constituting the polyimide resin is preferably 0.99 to 0.999 with respect to the total number of moles of diamine constituting the polyimide resin.
- the weight average molecular weights of the said polyimide resin are 120,000 or more and 300,000 or less, and Mw / Mn ratio is 10 or more and 12 or less.
- the storage elastic modulus at 300 degreeC of the said polyimide film is 1.0 * 10 ⁇ 5 > Pa or more.
- a filler is mentioned as a preferable aspect of a polyimide resin composition.
- a filler is mentioned as a preferable aspect of a polyimide resin composition.
- 1 or more types of compounds chosen from a bismaleimide compound and a nadiimide compound further as a preferable aspect of a polyimide resin composition is mentioned.
- another resin as a preferable aspect of a polyimide resin composition is mentioned.
- the film which concerns on this invention is formed from the polyimide resin composition of the said aspect.
- a preferred example of the film is a coverlay film.
- the adhesive which concerns on this invention contains the polyimide resin composition of the said aspect.
- Preferable examples of the adhesive include a flexible printed circuit board adhesive, a coverlay film adhesive, or a bonding sheet adhesive.
- the component according to the present invention includes a molded body formed from the polyimide resin composition of the above aspect.
- Preferred examples of the above components include electronic circuit board members, semiconductor devices, lithium ion battery members, solar cell members, fuel cell members, motor windings, engine peripheral members, paints, optical components, heat dissipation materials, electromagnetic shielding materials, and surge components. Dental materials, sliding coats, and electrostatic chucks.
- a polyimide resin composition excellent in mechanical properties and heat resistance of a molded article obtained while being soluble in a solvent, an adhesive containing the polyimide resin composition, and the polyimide resin composition There is an excellent effect that it is possible to provide a part including a molded body formed from the above, and a film formed from the polyimide resin composition.
- the polyimide resin composition according to the present invention includes at least a polar solvent and a polyimide resin.
- the polar solvent is not particularly limited as long as it can dissolve the polyimide resin.
- Preferred examples include N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylformamide, N, N-diethyl.
- Examples include acetamide, N, N-dimethylmethoxyacetamide, dimethyl sulfoxide, hexamethylphosphoramide, N-methyl-2-pyrrolidone, dimethyl sulfone and the like.
- a polar solvent can be used individually or as a 2 or more types of mixed solvent.
- a nonpolar solvent may be mixed as long as the polyimide resin can be dissolved.
- Nonpolar solvents include benzene, toluene, xylene, benzonitrile, dioxane, cyclohexane, mesitylene (1,3,5-trimethylbenzene), 1,2,4-trimethylbenzene, and the like.
- the addition amount of a nonpolar solvent is not specifically limited in the range which does not deviate from the meaning of this invention, For example, it is about 30 mass% or less.
- the concentration of the resin solid content in the polyimide resin composition is not particularly limited, and can be appropriately selected according to the shape and thickness of the molded body. From the viewpoint of improving the coatability, the content is preferably 5 to 50% by mass, and more preferably 10 to 30% by mass.
- the polyimide resin has a structure represented by chemical formula (3).
- a 1 is a tetravalent organic group
- a 2 is a divalent organic group.
- a polyimide resin is obtained by reacting a diamine and a tetracarboxylic dianhydride component to obtain a polyamic acid that is a polyimide precursor, and then polyimidizing it by a dehydration / cyclization reaction.
- the polyimide resin preferably has an imidization ratio of 80% or more with respect to the polyamic acid which is a polyimide precursor. More preferably, it is 85% or more.
- the polyimide resin preferably has only the structure represented by the chemical formula (3), but may include another structure without departing from the gist of the present invention.
- the polyimide resin according to the present invention has a viscosity average molecular weight ⁇ of 0.6 or more and 1.60 or less.
- the viscosity average molecular weight ⁇ referred to in this specification is a value calculated by the following method. That is, a small amount of polyimide varnish to be measured is collected in an Erlenmeyer flask and diluted to 0.5 (g / dL) with N-methylpyrrolidone (NMP). And the fall time is measured by the Uberote tube (made by Shibata Kagaku company) which put the prepared dilution varnish in the 35 degreeC thermostat.
- required from (eta) ln [dilution varnish fall time / NMP fall time] be a viscosity average molecular weight (eta).
- the viscosity average molecular weight ⁇ of the polyimide resin is more preferably 0.7 or more, and further preferably 0.8 or more. From the viewpoint of solubility, the viscosity average molecular weight ⁇ is preferably 1.4 or less.
- the polyimide resin of the present invention is an aromatic monomer having 95 to 100 mol% of the main chain and having no aliphatic chain having 3 or more carbon atoms in the entire monomer constituting the polyimide resin [hereinafter referred to as “aromatics”. Also referred to as “monomer (M)”.
- the main chain is the direction in which the polyimide chain extends, and refers to the structure in which the two terminal reactive groups of the monomer constituting the polyimide are linked, excluding the atoms constituting the side chain.
- the side chain may include one having an aliphatic chain having 3 or more carbon atoms. From the viewpoint of heat resistance, it is preferable that the side chain of the aromatic monomer (M) does not have an aliphatic chain having 3 or more carbon atoms.
- the polyimide resin of the present invention includes a case where all monomers constituting the polyimide resin are aromatic monomers (M) having no aliphatic chain having 3 or more carbon atoms in the main chain. By including 95 mol% or more of the aromatic monomer (M), an effect of increasing heat resistance can be obtained. Monomers that are not classified as aromatic monomers (M) can be used in a range of less than 5 mol%. For example, an aromatic monomer having an aliphatic chain having 3 or more carbon atoms in the main chain, an alicyclic monomer, or an aliphatic monomer may be used in a range of less than 5 mol%. From the viewpoint of heat resistance, it is preferable that all monomers constituting the polyimide resin are aromatic monomers (the aromatic monomer here is not limited to the aromatic monomer (M)).
- the aromatic monomer (M) of the present invention shall satisfy the following conditions (Structure I) to (Structure III).
- the monomer (A) having at least one of the benzophenone skeletons represented by the following chemical formula (1) and the following chemical formula (2) [hereinafter also referred to as “monomer A”] constitutes the polyimide resin. It shall contain 5 mol% or more and 30 mol% or less in all the monomers.
- the chemical formulas (1) and (2) may contain a substituent such as a methyl group, an ethyl group, or a halogen, for example, within a range not departing from the gist of the present invention.
- the monomer (A) is less than 5 mol%, the solubility of the polyimide resin in a polar solvent tends to be reduced. Further, when the monomer (A) exceeds 30 mol%, gelation tends to occur.
- the monomer (A) is preferably 9 mol% or more, particularly preferably 10 mol% or more. Moreover, it is preferable that a monomer (A) is 25 mol% or less, and it is especially preferable that it is 15 mol% or less.
- the monomer (A) is not particularly limited, and suitable examples of the diamine include 3,3′-diaminobenzophenone, 3,4′-diaminobenzophenone, 4,4′-diaminobenzophenone, a compound of the formula (4), 4 , 4′-bis [4- (4-amino- ⁇ , ⁇ -dimethylbenzyl) phenoxy] benzophenone, and the like.
- Preferable examples in the case of applying an acid dianhydride as the monomer (A) include 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 2,3 ′, 3,4′-benzophenone tetracarboxylic Examples thereof include acid dianhydrides and 2,2 ′, 3,3′-benzophenone tetracarboxylic dianhydrides.
- Monomers (A) can be used alone or in combination.
- a monomer (B) having no diphenyl ether skeleton and having a diphenyl ether skeleton [hereinafter also referred to as “monomer (B)”] is 40 mol% or more and 95 mol% or less in all monomers constituting the polyimide resin. Shall be included. Further, the monomer (B) is a monomer (B-1) [hereinafter referred to as “monomer (B-1)” having 3 or more aromatic rings in the total amount of monomers constituting the polyimide resin of 20 mol% or more and 95 mol% or less. Is also expressed as].
- the aromatic ring of monomer (B-1) is preferably a benzene ring.
- the monomer (B) and the monomer (A) may be counted redundantly. That is, a monomer having a benzophenone skeleton and not having a biphenyl skeleton and having a diphenyl ether skeleton is both a monomer (A) and a monomer (B).
- the monomer (B) is 40 mol% or more and 95 mol% or less in all monomers constituting the polyimide resin, and the monomer (B-1) is 20 mol% or more and 95 mol% or less in all monomers constituting the polyimide resin. Thereby, the solubility with respect to the polar solvent of a polyimide resin can be improved. If the monomer (B) is less than 40 mol%, the solubility tends to decrease.
- the monomer (B-1) is preferably 30 mol% or more, and more preferably 40 mol% or more.
- the monomer (B-1) is not particularly limited, and examples thereof include a diamine having the above chemical formula (4) and a diamine having the following chemical formula (5).
- X represents a divalent group of an oxygen atom, a sulfur atom, a sulfone group, a methylene group, an isopropylidene group or a hexafluoroisopropylidene group.
- Suitable examples of the diamine of the monomer (B-1) include bis [4- (3-aminophenoxy) phenyl] sulfide, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-amino).
- Phenoxy) benzene 1,3-bis (3- (3-aminophenoxy) phenoxy) benzene, 1,3-bis (3- (4-aminophenoxy) phenoxy) benzene, 1,3-bis (4- (3 -Aminophenoxy) phenoxy) benzene, 1,3-bis (3- (3-aminophenoxy) phenoxy) -2-methylbenzene, 1,3-bis (3- (4-aminophenoxy) phenoxy) -4-methyl Benzene, 1,3-bis (4- (3-aminophenoxy) phenoxy) -2-ethylbenzene, 1,3-bis (3- (2-aminophenoxy) 5-sec-butylbenzene, 1,3-bis (4- (3-aminophenoxy) phenoxy) -2,5-dimethylbenzene, 1,3-bis (4- (2-amino-6-methylphenoxy) phenoxy ) Benzene, 1,3-bis (2- (2-amino-6-
- Suitable examples of applying acid dianhydride as the monomer (B-1) include 4,4 ′-(4,4′-isopropylidenediphenoxy) bisphthalic anhydride, 1,3-bis (3, 4-dicarboxyphenoxy) benzene dianhydride, 1,4-bis (3,4-dicarboxyphenoxy) benzene dianhydride, and the like.
- Monomers (B-1) can be used alone or in combination.
- the monomer (B) not classified into the monomer (B-1) is not particularly limited, but examples of preferred diamines include 4,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, and the like. Is mentioned.
- a suitable example of applying acid dianhydride as monomer (B) not classified as monomer (B-1) is 4,4′-oxydiphthalic anhydride.
- Monomers (B) can be used alone or in combination.
- a monomer (C) having a biphenyl skeleton [hereinafter also referred to as “monomer (C)”] is contained in an amount of 0 mol% or more and less than 45 mol% in all monomers constituting the polyimide resin.
- the monomer (C) and the monomer (A) may be counted redundantly. That is, a monomer having a benzophenone skeleton and a biphenyl skeleton is both a monomer (A) and a monomer (C).
- the monomer (C) is not particularly limited, and suitable examples of the diamine include 4,4′-bis (3-aminophenoxy) biphenyl, 4,4′-bis (4-aminophenoxy) biphenyl, 3,3 ′.
- -Bis (4-aminophenoxy) biphenyl, 4,4'-bis (4-aminophenoxy) biphenyl, 2,2'-bis (trifluoromethyl) -1,1'-biphenyl-4,4'-diamine Examples include 3,3′-dimethylbenzidine, 3,4′-dimethylbenzidine, and 4,4′-dimethylbenzidine.
- Preferable examples in the case of applying acid dianhydride as the monomer (C) include 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3 ′, 3,4′-biphenyltetracarboxylic Acid dianhydrides, 4,4′-bis (3,4-dicarboxyphenoxy) biphenyl dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, and the like.
- Monomers (C) can be used alone or in combination.
- aromatic monomers (M) preferable monomers other than the monomers (A), monomers (B), and monomers (C) [hereinafter also referred to as “other monomers (D)”] have the following chemical formula ( 6) can be exemplified.
- Y represents a divalent group of a sulfur atom, a sulfone group, a methylene group, an isopropylidene group or a hexafluoroisopropylidene group.
- aromatic monomers (D) are not particularly limited, but specific examples of suitable tetracarboxylic dianhydrides include pyromellitic dianhydride and bis (3,4-dicarboxyphenyl) sulfide dianhydride.
- Bis (3,4-dicarboxyphenyl) sulfone dianhydride bis (3,4-dicarboxyphenyl) methane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl)- 1 1,1,3,3,3-hexafluoropropane dianhydride, bis (2,3-dicarboxyphenyl) sulfide dianhydride, bis (2,3-dicarboxyphenyl) sulfone dianhydride, 1,2 , 5,6
- Suitable diamines for other aromatic monomers (D) include m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, m-aminobenzylamine, p-aminobenzylamine, bis (3-aminophenyl) sulfide Bis (4-aminophenyl) sulfide, bis (3-aminophenyl) sulfoxide, (3-aminophenyl) (4-aminophenyl) sulfoxide, bis (3-aminophenyl) sulfone, (3-aminophenyl) (4 -Aminophenyl) sulfone, bis (4-aminophenyl) sulfone, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, bis (3-aminophenyl
- the monomer other than the aromatic monomer (M) ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1, 7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, poly (tetramethylene oxide) -di-p- Examples thereof include aminobenzoate (14EL; manufactured by Ihara Chemical Co., Ltd.), polyetheramine (XTJ-542, D-2000; manufactured by HUNTSMAN).
- Some or all of the hydrogen atoms on the aromatic ring may be substituted with a group selected from a fluoro group, a methyl group, a methoxy group, a trifluoromethyl group, a trifluoromethoxy group, and the like.
- a bridge selected from an ethynyl group, a benzocyclobuten-4′-yl group, a vinyl group, an allyl group, a cyano group, an isocyanate group, a nitrilo group, and an isopropenyl group, depending on the purpose. You may have the group used as a point. These may be used alone or in combination of two or more.
- the polyimide resin contains a benzophenone skeleton derived from aromatic tetracarboxylic dianhydride or aromatic diamine.
- the terminal group of the polyimide resin is not particularly limited, but is preferably an amine terminal from the viewpoint of heat resistance.
- an amine terminal By using an amine terminal, a carbonyl group derived from a benzophenone skeleton contained in one polyimide molecule and a terminal amino group of another polyimide molecule are hydrogen-bonded, so that high heat resistance is obtained.
- the total number of moles of tetracarboxylic dianhydride can be easily obtained by setting it to 0.9 to 0.999 with respect to the total number of moles of diamine.
- the total number of moles of tetracarboxylic dianhydride is 0.99 to 0.999 with respect to the total number of moles of diamine.
- the polyimide resin may be a random polymer or a block polymer, but a random polymer is preferable because the characteristics of the diamine component are easily obtained.
- the preferred weight average molecular weight of the polyimide resin is 50,000 or more and 1,000,000 or less. By setting the weight average molecular weight to 50,000 or more and 1,000,000 or less, the mechanical strength can be effectively increased.
- the weight average molecular weight is more preferably 100,000 or more, and particularly preferably 120,000 or more.
- the weight average molecular weight is more preferably 500,000 or less, and particularly preferably 300,000 or less. By setting the weight average molecular weight in the range of 120,000 or more and 300,000 or less, the mechanical strength can be increased more effectively.
- the preferable range of Mw / Mn ratio is 5 or more and 100 or less.
- the Mw / Mn ratio is more preferably 10 or more, and particularly preferably 12 or more.
- the Mw / Mn ratio is more preferably 50 or less, and particularly preferably 30 or less.
- the preferable range of the number average molecular weight is 500 to 200,000, particularly preferably 4,000 to 25,000, calculated from the above weight average molecular weight and Mw / Mn.
- the amine equivalent of the polyimide resin is determined by dividing the number average molecular weight by the number of amino groups contained in one molecule. In the case of using a terminal amine, the total number of moles of tetracarboxylic dianhydride can be easily obtained by setting it to 0.9 to 0.999 with respect to the total number of moles of diamine. Therefore, from the number average molecular weight, a preferred range of amine equivalent is 250 to 10,000, and a more preferred range is 2,000 to 125,000.
- the polyimide resin composition can contain various additives without departing from the spirit of the present invention.
- an ultraviolet absorber for example, an ultraviolet absorber, a storage stabilizer, an adhesion aid, a surface modifier, a dispersant, and the like can be added as appropriate.
- other resins than the polyimide resin may be contained within a range that does not affect the heat resistance and flexibility and does not depart from the gist of the present invention.
- Preferable examples include urethane resin, epoxy resin, acrylic resin, PET (polyethylene terephthalate) resin, polyamide resin, polyamideimide resin and the like.
- the polyimide resin composition may contain the following compound.
- Epoxy compounds such as bisphenol A type epoxy compounds and bisphenol F type epoxy compounds; acrylate compounds such as carboxyethyl acrylate, propylene glycol acrylate, ethoxylated phenyl acrylate and aliphatic epoxy acrylate; methylene bisphenyl diisocyanate (MDI), toluene diisocyanate (TDI) ), Isocyanate compounds such as hexamethylene diisocyanate (HDI) and xylene diisocyanate (XDI); 4,4′-diphenylmethane bismaleimide, 4,4′-diphenyloxy bismaleimide, 4,4′-diphenylsulfone bismaleimide, p- Phenylene bismaleimide, m-phenylene bismaleimide, 2,4-tolylene bismaleimide, 2,6-tolylene bismaleimide , Ethylene bismaleimide, he
- alkenyl-substituted nadiimide examples include 4,4 ′-(diphenylmethane) bisnadiimide, phenylene bisnadiimide, 4,4′-biphenylene bisnadiimide, 4,4′-diphenylpropane bisnadiimide, 4,4′-diphenyl ether bisnadiimide and the like.
- a nadiimide compound is mentioned.
- the addition amount of other resin can be suitably selected according to a use.
- the polyimide resin composition may contain a filler.
- a filler Preferred examples include boron nitride, aluminum nitride, alumina, alumina hydrate, silicon oxide, silicon nitride, silicon carbide, diamond, hydroxyapatite, barium titanate, copper, aluminum, silica, magnesia, titania, silicon nitride, silicon carbide.
- a material having thermal conductivity such as is used.
- alumina, boron nitride, and the like are particularly preferable because they are excellent in thermal conductivity and electrical insulation and are chemically stable.
- metal, metal oxide, amorphous carbon powder, graphite, or metal-plated filler can be used as the filler.
- the metal examples include copper, aluminum, nickel, iron, gold, silver, platinum, tungsten, chromium, titanium, tin, lead, and palladium. These may be used alone or in combination of two or more.
- a soft magnetic filler may be used as the filler.
- soft magnetic fillers include magnetic stainless steel (Fe—Cr—Al—Si alloy), sendust (Fe—Si—Al alloy), permalloy (Fe—Ni alloy), silicon copper (Fe—Cu—Si alloy), Fe-Si alloy, Fe-Si-B (-Cu-Nb) alloy, Fe-Ni-Cr-Si alloy, Fe-Si-Cr alloy, Fe-Si-Al-Ni-Cr alloy and the like can be mentioned. Further, ferrite or pure iron particles may be used.
- the ferrite examples include soft ferrite such as Mn—Zn ferrite, Ni—Zn ferrite, Mn—Mg ferrite, Mn ferrite, Cu—Zn ferrite, Cu—Mg—Zn ferrite, and hard ferrite that is a permanent magnet material. It is done.
- the average particle size of the filler is not particularly limited, but is, for example, 0.5 to 100 ⁇ m. The addition amount of a filler can be suitably selected according to a use.
- the polyimide resin composition may contain a flame retardant.
- a flame retardant is not specifically limited, For example, a halogen flame retardant, an inorganic flame retardant, and a phosphorus flame retardant can be used.
- a flame retardant may be used by 1 type and may be used in mixture of 2 or more types.
- the halogen-based flame retardant include an organic compound containing chlorine and a compound containing bromine. Specific examples include pentabromodiphenyl ether, octabromodiphenyl ether, decabromodiphenyl ether, tetrabromobisphenol A, hexabromocyclodecane tetrabromobisphenol A, and the like.
- Examples of inorganic flame retardants include antimony compounds and metal hydroxides.
- Antimony compounds include antimony trioxide and antimony pentoxide.
- Examples of the metal hydroxide include aluminum hydroxide and magnesium hydroxide.
- Examples of the phosphorus flame retardant include phosphazene, phosphine, phosphine oxide, and phosphate ester.
- the addition amount of the flame retardant is not particularly limited, and can be appropriately changed according to the type of the flame retardant used. Generally, it is preferable to use in the range of 5 to 50 parts by mass with respect to 100 parts by mass of the polyimide resin.
- the polyimide resin composition of the present invention contains a polyimide resin that is soluble in a solvent, it can be used as a polyimide varnish. Therefore, after apply
- the polyimide resin composition of the present invention does not require a step of imidization at a high temperature, it is not suitable for a high temperature process or when a polyimide molded body is to be formed on a low heat resistance substrate or member. It can also be applied widely.
- the polyimide resin is excellent in heat resistance, it can also be suitably applied in applications where high temperature treatment is performed. Further, since it is soluble in a solvent, a pattern can be formed using a lift-off method or the like.
- the polyimide resin composition preferably satisfies the following conditions in a polyimide film having a thickness of 30 ⁇ m to 70 ⁇ m after the composition is applied and dried. That is, (a) glass transition temperature of 130 ° C. or higher and lower than 260 ° C., (b) tensile elastic modulus at 25 ° C. of 2.0 GPa or higher and lower than 4.0 GPa, and (c) 5% heat in a nitrogen atmosphere
- the weight reduction temperature preferably satisfies 500 ° C. or higher.
- a polyimide resin composition coating may be applied to a thickness of 300 ⁇ m to 400 ⁇ m.
- the production method of the polyimide film is not particularly limited, but examples include the following method. That is, the polyimide resin composition is applied at a speed of 10 mm / sec on the release-treated PET film. The obtained coating film is dried at 200 ° C. for 30 minutes, the solvent is removed, and after drying, the film part is peeled off from the PET film using tweezers and the like, and the coating film thickness after drying is sufficiently dried.
- An example is a method of producing the film to have a thickness of 30 to 70 ⁇ m.
- the tensile elastic modulus in this specification refers to a value measured by the following method. That is, the polyimide film is cut into a size of 90 mm length ⁇ 10 mm width, the actual measurement length is 50 mm length (both ends are 20 mm portions), and AUTOGRAPH AGS-100D (manufactured by Shimadzu Corporation) at 25 ° C. The initial inclination in the chart when the strip-shaped sample film is pulled at a speed of 50 mm / min is obtained, and this value is defined as “tensile modulus”.
- the 5% thermal weight loss temperature in this specification refers to a value measured by the following method. That is, when a thermogravimetric measuring device (TGA-51, manufactured by Shimadzu Corporation) was used, about 10 mg of polyimide film was placed in a quartz crucible and heated to 800 ° C. at 10 ° C./min from room temperature in a nitrogen atmosphere. Of 5% thermal weight loss temperature.
- TGA-51 thermogravimetric measuring device
- the heat resistance of the polyimide resin can be more effectively exhibited by setting the glass transition temperature to 130 ° C. or higher. Further, by setting the glass transition temperature to less than 260 ° C., for example, when the polyimide resin layer is multilayered, adhesion and flexibility with other layers can be effectively improved.
- the glass transition temperature is more preferably 135 ° C. or higher, and more preferably 255 ° C. or lower.
- the polyimide film having a thickness after drying of 30 ⁇ m to 70 ⁇ m preferably has a tensile elastic modulus at 25 ° C. of 2.1 GPa or more, particularly preferably 2.2 GPa or more. Moreover, it is more preferable that it is 3.8 GPa or less, and it is further more preferable that it is 3.7 GPa or less.
- the 5% thermal weight loss temperature in a nitrogen atmosphere of a polyimide film having a thickness after drying of 30 ⁇ m to 70 ⁇ m is preferably 500 ° C. or higher, more preferably 520 ° C. or higher, and particularly preferably 530 It is above °C. By setting it as 500 degreeC or more, the molded object excellent in heat resistance can be provided.
- the storage elastic modulus E ′ (300 ° C.) of the polyimide film having a thickness after drying of 30 ⁇ m to 70 ⁇ m is preferably 1.0 ⁇ 10 5 Pa or more.
- a polyimide resin that satisfies all the above characteristics (a) to (c) By using a polyimide resin that satisfies all the above characteristics (a) to (c), a polyimide resin that is soluble in a solvent, has excellent mechanical properties, and has high heat resistance can be obtained.
- the ratio at the time of synthesizing the acid precursor of the polyimide precursor and the diamine is not particularly limited, but the total of the diamine component is 47.5 to 52.5 mol% and the acid dianhydride is based on the total of the diamine and the acid anhydride.
- the copolymerization is preferably performed in a range where the total of the anhydride components satisfies 47.5 to 52.5 mol%.
- the total number of moles of tetracarboxylic dianhydride can be easily obtained by setting it to 0.9 to 0.999 with respect to the total number of moles of diamine.
- the amount ratio of the charged monomer used when synthesizing the polyimide resin and the ratio of the monomer in the obtained polymer are almost the same. Therefore, in order to obtain a polymer having a desired structure, the amount of the charged monomer is adjusted. do it.
- Polymerization can be performed in a solid phase system, but is preferably performed in a liquid phase system.
- the polymerization concentration is, for example, about 5 to 50% by mass.
- the reaction solvent is not particularly limited, but preferably has a boiling point of 100 ° C. or higher.
- a solvent used for polymerization of a polyimide precursor can be suitably used.
- it dissolves at least one reactant, preferably both acid anhydrides and diamines.
- Specific examples include N, N-dimethylformamide, N, N-dimethylacetamide, cresol, dimethyl sulfoxide, N-methyl-2-pyrrolidone, tetramethylurea and the like.
- These solvents can be used alone or in combination with other solvents such as 1,3,5-trimethylbenzene, 1,2,4-trimethylbenzene, benzonitrile, dioxane, xylene or toluene.
- a catalyst may be used as appropriate.
- the catalyst is not particularly limited as long as it substantially accelerates the progress of the dehydration polycondensation reaction or inhibits the progress of the side reaction of the crosslinking agent without departing from the spirit of the present invention.
- the amount of the catalyst used may be appropriately adjusted in consideration of the properties of the catalyst itself such as the volatility of the catalyst and the acid strength, and the reaction conditions. There is no particular limitation as long as the reaction can be substantially promoted or the progress of side reactions such as crosslinking can be inhibited.
- the catalyst includes a catalyst that changes to a compound having the above properties by reacting with a flowing gas or a reaction solvent even if the catalyst itself does not have the above properties.
- the catalyst examples include generally known catalysts used for polymerization of polyimide, and acid catalysts such as organic sulfonic acid. More specifically, for example, methanesulfonic acid, ethanesulfonic acid, 1-propanesulfonic acid, 1-butanesulfonic acid, 1-pentanesulfonic acid, 1-hexanesulfonic acid, 1-heptanesulfonic acid, alkanesulfonic acid such as 1-octanesulfonic acid, halogenated substituted alkanesulfonic acid such as trifluoromethanesulfonic acid, benzenesulfone Benzenesulfonic acid derivatives such as acid, p-toluenesulfonic acid, p-xylene-2-sulfonic acid, p-chlorobenzenesulfonic acid, p-nitrobenzenesulfonic acid, naphthalene-1-sulfonic acid, naphthalene-2
- the order and method of charging the raw materials, the solvent, and other catalysts added as necessary are not particularly limited.
- the reaction temperature is not particularly limited as long as a necessary weight average molecular weight (Mw) can be obtained, but is usually 20 ° C. or higher and 100 ° C. or lower when polyamic acid is polymerized as a polyimide precursor.
- the reaction time is not limited to a range that is sufficient to obtain the required degree of polymerization.
- the reaction is preferably performed in an inert gas atmosphere such as nitrogen.
- the solid content concentration in the reaction system (in the reactor) is not particularly limited, but is usually 5% by mass to 50% by mass.
- the reaction apparatus used for the solid phase reaction is not particularly limited, but Super Blend (Sumitomo Heavy Industries, Ltd.), Aiko Chemical Mixer (Aikosha Seisakusho), Planetary Mixer (Inoue Seisakusho), Trimix ( And kneading machines such as those manufactured by Inoue Seisakusho.
- the polyimide resin described in Patent Document 1 has insufficient heat resistance and thermal weight reduction temperature. Further, the polyimide resin described in Patent Document 2 has a low weight average molecular weight Mw, and the heat resistance and mechanical properties of a film obtained therefrom are not sufficient.
- the viscosity average molecular weight of the polyimide resin is in a specific range, the structure of the monomer constituting the polyimide resin (aromatic monomer (M), monomers (A) to (C)), and the content thereof
- aromatic monomer (M) aromatic monomer (M)
- monomers (A) to (C) monomers (A) to (C)
- the content thereof By specifying, it is possible to obtain a polyimide resin composition that is soluble in a solvent and has an excellent molded product and high heat resistance.
- the polyimide resin by using the above-mentioned specific proportion of benzophenone skeleton, diphenyl ether skeleton having no biphenyl skeleton, further using a biphenyl skeleton, and using the above-mentioned specific viscosity average molecular weight ⁇ , High heat resistance with a 5% thermal weight loss temperature of 500 ° C. or higher can be realized. Moreover, the obtained molded object can provide the polyimide resin composition excellent in the mechanical characteristic easily. And the storage stability as a varnish of a polyimide resin composition can be improved by maintaining the balance of solid content in the polyimide resin composition using the polyimide resin mentioned above.
- the polyimide resin composition according to the present invention can be suitably applied as an adhesive or the like.
- the polyimide resin contained in the polyimide resin composition of the present invention is preferably used as a binder resin for a heat dissipation material for cooling semiconductor devices, home appliances, personal computers, motors, portable devices and the like. Silicone, epoxy, acrylic, and the like have been used for conventional binder resins for heat dissipation materials, but there were problems with heat resistance, flexibility, insulation, VOC (volatile organic compounds), and the like. If a resin composition containing 20 to 60% by volume of a heat dissipating filler in the polyimide resin composition of the present invention is used, it has heat resistance, flexibility, high insulation, and low VOC. It becomes possible. Therefore, the polyimide resin composition of this invention is suitable for a heat radiating member use.
- the polyimide resin contained in the polyimide resin composition of the present invention is an electromagnetic wave shielding member that blocks external electromagnetic waves that affect semiconductor devices, home appliances, personal computers, automobiles and other transport devices, portable devices, or internal electromagnetic waves generated therefrom. It is preferably used as a binder resin. Silicone, epoxy, acrylic, and the like are used for conventional electromagnetic wave shielding binder resins, but there are problems with heat resistance, flexibility, VOC, and the like. If a resin composition containing 20 to 90% by volume of a conductive filler or the like in the polyimide resin composition of the present invention is used, it becomes possible to have both heat resistance, flexibility, and low VOC. . Therefore, the polyimide resin composition of the present invention is suitable for use as an electromagnetic shielding member.
- the polyimide resin composition of the present invention is an adhesive for surge parts (surge absorbers) for protecting from abnormal currents and voltages that affect household appliances, personal computers, automobiles and other transportation equipment, portable equipment, power supplies, servers, telephones, etc. Or it is preferably used as a sealing material.
- a welding agent such as silver wax is used for conventional adhesives or sealants for surge parts, but there are problems such as requiring a high temperature process and high material costs.
- the resin adhesive has problems such as withstand voltage, heat resistance, and VOC. If the polyimide resin composition of the present invention is used, it is possible to have low-temperature process, withstand voltage, heat resistance, low VOC, and low cost, which is suitable for this application.
- the polyimide resin composition of the present invention is preferably used as an adhesive for flexible printed circuit boards used in transportation equipment such as personal computers and automobiles and portable equipment.
- a polyamic acid varnish or the like is used as a conventional flexible printed circuit board adhesive, but a high temperature process is required.
- Use of the polyimide resin composition of the present invention makes it possible to achieve both low-temperature process and heat resistance, and is suitable for the adhesive application.
- the polyimide resin composition of the present invention is preferably used as an adhesive for a cover lay film of a flexible printed circuit board used for transportation devices such as personal computers and automobiles, and portable devices.
- Epoxy resins and the like have been used as conventional coverlay film adhesives, but none of them have excellent workability, flexibility, electrical insulation, heat resistance, and adhesiveness. If the polyimide resin composition of this invention is used, it will become possible to satisfy workability, flexibility, electrical insulation, heat resistance, and adhesiveness simultaneously, and it is suitable for the adhesive application.
- the film formed from the polyimide resin composition of the present invention is preferably used as a cover lay film of a flexible printed circuit board used for transportation equipment such as personal computers and automobiles and portable equipment.
- Conventional coverlay film is used as a two-layer film by combining an adhesive such as an epoxy resin with a polyimide film, but as a single-layer film, workability, flexibility, electrical insulation, heat resistance, and adhesiveness are simultaneously There was nothing excellent. If the polyimide resin composition of the present invention is used, it becomes possible to simultaneously satisfy processability, flexibility, electrical insulation, heat resistance, and adhesiveness as a single-layer film, which is suitable for the above film use.
- the polyimide resin composition of the present invention is preferably used as an adhesive for a bonding sheet of a flexible printed circuit board used for transportation devices such as personal computers and automobiles and portable devices.
- Epoxy resins and the like have been used as conventional adhesives for bonding sheets, but none of them have excellent workability, flexibility, electrical insulation, heat resistance, and adhesiveness at the same time. If the polyimide resin composition of the present invention is used, processability, flexibility, electrical insulation, heat resistance, and adhesiveness can be satisfied at the same time, which is suitable for the adhesive application.
- Example 1 Preparation of Polyimide Resin Composition
- 1,3-Bis (3-aminophenoxy) benzene hereinafter referred to as “NMP and mesitylene (1,3,5-trimethylbenzene)” in a solvent prepared at a ratio of 8: 2.
- the obtained mixture was stirred for 4 hours or more in a flask into which dry nitrogen gas could be introduced to obtain a polyamic acid solution having a resin solid content of 18 to 25% by mass. After sufficiently stirring, the reaction system was heated to about 180 ° C. while stirring in a flask equipped with a Dean-Stark tube, and water generated by the dehydration reaction was taken out of the system to obtain a polyimide resin composition.
- the polyimide resin composition was applied at a rate of 10 mm / sec on a PET film that had been subjected to a release treatment.
- the obtained coating film was dried at 200 ° C. for 30 minutes to remove the solvent. After drying, the film part was peeled off from the PET film using tweezers or the like to prepare a polyimide film (film thickness: 50 ⁇ m).
- the prepared polyimide film was cut into a width of 10 mm and a length of 90 mm to obtain a sample film.
- the sample film was pulled in the length direction with AUTOGRAPH AGS-100D (manufactured by Shimadzu Corporation) at 25 ° C. at a speed of 50 mm / min.
- the initial slope in the chart was defined as “tensile modulus”.
- thermogravimetric decrease temperature evaluation of polyimide film A 5% thermogravimetric decrease temperature was calculated using a thermogravimetric apparatus (TGA-51, manufactured by Shimadzu Corporation). Specifically, about 10 mg of the sample film was put in a quartz crucible, and the 5% thermogravimetric reduction temperature when the temperature was raised from room temperature to 800 ° C. at 10 ° C./min in a nitrogen atmosphere was determined.
- GPC Evaluation A polyimide varnish to be measured was diluted with a mobile phase for GPC measurement to prepare a concentration of 0.1%. After leaving overnight, it was filtered using a membrane filter (MILLEX-LH; manufactured by Nihon Millipore), and the filtrate was used for measurement.
- the apparatus used was a 515 pump, 717Plus automatic injection device (manufactured by Nippon Waters) under the following conditions.
- the polyimide resin composition was prepared in the same manner as in Example 1 except for the mixing ratio. And the polyimide film was produced by the method similar to Example 1, and was evaluated.
- the polyimide resin composition was prepared in the same manner as in Example 1 except for the mixing ratio. And the polyimide film was produced by the method similar to Example 1, and was evaluated.
- the polyimide resin composition was prepared in the same manner as in Example 1 except for the mixing ratio. Moreover, the polyimide film was produced by the method similar to Example 1, and evaluated.
- ODA 4,4′-oxydianiline
- Table 1 shows the preparation ratio of the polyimide precursor
- Table 2 shows the physical property values of the sample film obtained from the polyimide resin composition obtained.
- Example 1 the weight average molecular weight Mw determined by GPC was 204,000, and the Mw / Mn ratio was 19. On the other hand, in Comparative Example 5, Mw was 51,900 and Mw / Mn ratio was 5.3.
- the 5% thermal weight loss temperature was 500 ° C. or higher in any polyimide film, and the heat resistance was good. Furthermore, it was found that the tensile modulus was 2.0 GPa or more, and the mechanical properties were excellent. Furthermore, the storage modulus was found to be> 10 5 Pa in all cases. Moreover, when the varnish stability of the polyimide resin composition was examined, it was confirmed that all were good.
- the molded body obtained from the polyimide resin composition according to the present invention has excellent heat resistance and mechanical strength, and also has an excellent 5% thermal weight loss temperature, so that it can be applied to all materials for which these are required. is there.
- electronic circuit board members, semiconductor devices, and lithium ion battery members having structures that are applied, dried, and bonded to metal foils, ceramic substrates, resin films, resin substrates, metal moldings, ceramic moldings, resin moldings, etc.
- binders for lithium ion batteries various battery members such as solar cell members and fuel cell members, various battery peripheral members, motor windings, various engine peripheral members and motor members including automobiles, aerospace applications It can be suitably applied as a member, paint, optical component, heat radiation material, electromagnetic shielding material, surge component, dental material, sliding coating, and electrostatic chuck.
- the polyimide resin composition which concerns on this invention can be applied suitably as an adhesive agent.
- the adhesive include flexible printed circuit board adhesives, coverlay film adhesives, and bonding adhesives.
- the polyimide resin composition according to the present invention is suitable for all films. A suitable example is a coverlay film.
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Abstract
Description
前記ポリイミド樹脂の末端基を構成するモノマーは、ジアミンであることが好ましい。
前記ベンゾフェノン骨格を有するモノマーの好ましい例として、3,3'-ジアミノベンゾフェノン、3,4'-ジアミノベンゾフェノン、4,4'-ジアミノベンゾフェノン、3,3',4,4'-ベンゾフェノンテトラカルボン酸二無水物、及び2,3',3,4'-ベンゾフェノンテトラカルボン酸二無水物の少なくともいずれかを挙げることができる。
また、前記モノマー(B-1)の芳香環は、ベンゼン環であることが好ましい。
また、前記ビフェニル骨格を有するモノマー(C)は、4,4'-ビス(3-アミノフェノキシ)ビフェニル、4,4'-ビス(4-アミノフェノキシ)ビフェニル、3,3'-ビス(4-アミノフェノキシ)ビフェニル、2,2'-ビス(トリフルオロメチル)-1,1'-ビフェニル-4,4'-ジアミン、4,4'-ビス(3,4-ジカルボキシフェノキシ)ビフェニル二無水物、2,2',3,3'-ビフェニルテトラカルボン酸二無水物、3,3',4,4'-ビフェニルテトラカルボン酸二無水物の少なくともいずれかとすることが好ましい。
また、前記ビフェニル骨格を有するモノマー(C)を、前記ポリイミド樹脂を構成する全モノマー中に10モル%以上含むことが好ましい。
また、前記ポリイミド樹脂を構成するテトラカルボン酸二無水物の合計モル数が、前記ポリイミド樹脂を構成するジアミンの合計モル数に対して、0.99~0.999であることが好ましい。
また、前記ポリイミド樹脂の重量平均分子量が、120,000以上、300,000以下であり、Mw/Mn比が10以上、12以下であることが好ましい。
また、前記ポリイミドフィルムの300℃での貯蔵弾性率は、1.0×105Pa以上であることが好ましい。
また、ポリイミド樹脂組成物の好ましい態様として、フィラーを含有するものが挙げられる。
また、ポリイミド樹脂組成物の好ましい態様として、さらに、ビスマレイミド化合物、及びナジイミド化合物より選ばれる1種以上の化合物を含有するものが挙げられる。
また、ポリイミド樹脂組成物の好ましい態様として、他の樹脂を含有するものが挙げられる。 The polyimide resin composition according to the present invention preferably satisfies the following conditions. That is, the polyimide film obtained by coating and drying the composition is (a) a glass transition temperature of 130 ° C. or higher and lower than 260 ° C., (b) a tensile elastic modulus at 25 ° C. of 2.0 GPa or higher, It is preferable that less than 4.0 GPa and (c) 5% thermogravimetric reduction temperature in a nitrogen atmosphere satisfy 500 ° C. or more.
It is preferable that the monomer which comprises the terminal group of the said polyimide resin is diamine.
Preferred examples of the monomer having the benzophenone skeleton include 3,3′-diaminobenzophenone, 3,4′-diaminobenzophenone, 4,4′-diaminobenzophenone, 3,3 ′, 4,4′-benzophenone tetracarboxylic acid dicarboxylate. An anhydride and at least one of 2,3 ′, 3,4′-benzophenonetetracarboxylic dianhydride can be mentioned.
The aromatic ring of the monomer (B-1) is preferably a benzene ring.
The monomer (C) having a biphenyl skeleton includes 4,4′-bis (3-aminophenoxy) biphenyl, 4,4′-bis (4-aminophenoxy) biphenyl, 3,3′-bis (4- Aminophenoxy) biphenyl, 2,2′-bis (trifluoromethyl) -1,1′-biphenyl-4,4′-diamine, 4,4′-bis (3,4-dicarboxyphenoxy) biphenyl dianhydride 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride and 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride are preferable.
Moreover, it is preferable that the monomer (C) which has the said biphenyl skeleton is contained 10 mol% or more in all the monomers which comprise the said polyimide resin.
The total number of moles of tetracarboxylic dianhydride constituting the polyimide resin is preferably 0.99 to 0.999 with respect to the total number of moles of diamine constituting the polyimide resin.
Moreover, it is preferable that the weight average molecular weights of the said polyimide resin are 120,000 or more and 300,000 or less, and Mw / Mn ratio is 10 or more and 12 or less.
Moreover, it is preferable that the storage elastic modulus at 300 degreeC of the said polyimide film is 1.0 * 10 < 5 > Pa or more.
Moreover, what contains a filler is mentioned as a preferable aspect of a polyimide resin composition.
Moreover, what contains 1 or more types of compounds chosen from a bismaleimide compound and a nadiimide compound further as a preferable aspect of a polyimide resin composition is mentioned.
Moreover, what contains another resin as a preferable aspect of a polyimide resin composition is mentioned.
上記フィルムの好ましい例として、カバーレイフィルムが挙げられる。
本発明に係る接着剤は、上記態様のポリイミド樹脂組成物を含有するものである。
上記接着剤の好ましい例として、フレキシブルプリント基板用接着剤、カバーレイフィルム用接着剤、又はボンディングシート用接着剤が挙げられる。 The film which concerns on this invention is formed from the polyimide resin composition of the said aspect.
A preferred example of the film is a coverlay film.
The adhesive which concerns on this invention contains the polyimide resin composition of the said aspect.
Preferable examples of the adhesive include a flexible printed circuit board adhesive, a coverlay film adhesive, or a bonding sheet adhesive.
上記部品の好ましい例として、電子回路基板部材、半導体デバイス、リチウムイオン電池部材、太陽電池部材、燃料電池部材、モーター巻線、エンジン周辺部材、塗料、光学部品、放熱材、電磁波シールド材、サージ部品、歯科材、摺動コート、及び静電チャックが挙げられる。 The component according to the present invention includes a molded body formed from the polyimide resin composition of the above aspect.
Preferred examples of the above components include electronic circuit board members, semiconductor devices, lithium ion battery members, solar cell members, fuel cell members, motor windings, engine peripheral members, paints, optical components, heat dissipation materials, electromagnetic shielding materials, and surge components. Dental materials, sliding coats, and electrostatic chucks.
化学式(3)中のA1は4価の有機基であり、A2は2価の有機基である。ポリイミド樹脂は、ジアミンとテトラカルボン酸二無水物成分とを反応させてポリイミド前駆体であるポリアミド酸を得、その後、脱水・環化反応によりポリイミド化したものである。ポリイミド樹脂は、ポリイミド前駆体であるポリアミド酸に対してイミド化率を80%以上とすることが好ましい。より好ましくは85%以上である。ポリイミド樹脂は、化学式(3)の構造のみからなることが好ましいが、本発明の趣旨を逸脱しない範囲において別の構造が含まれていてもよい。 The polyimide resin has a structure represented by chemical formula (3).
In the chemical formula (3), A 1 is a tetravalent organic group, and A 2 is a divalent organic group. A polyimide resin is obtained by reacting a diamine and a tetracarboxylic dianhydride component to obtain a polyamic acid that is a polyimide precursor, and then polyimidizing it by a dehydration / cyclization reaction. The polyimide resin preferably has an imidization ratio of 80% or more with respect to the polyamic acid which is a polyimide precursor. More preferably, it is 85% or more. The polyimide resin preferably has only the structure represented by the chemical formula (3), but may include another structure without departing from the gist of the present invention.
化学式(5)中、Xは酸素原子、硫黄原子、スルホン基、メチレン基、イソプロピリデン基またはヘキサフルオロイソプロピリデン基の2価の基を示す。 The monomer (B-1) is not particularly limited, and examples thereof include a diamine having the above chemical formula (4) and a diamine having the following chemical formula (5).
In the chemical formula (5), X represents a divalent group of an oxygen atom, a sulfur atom, a sulfone group, a methylene group, an isopropylidene group or a hexafluoroisopropylidene group.
化学式(6)中、Yは硫黄原子、スルホン基、メチレン基、イソプロピリデン基またはヘキサフルオロイソプロピリデン基の2価の基を示す。 Further, among the aromatic monomers (M), preferable monomers other than the monomers (A), monomers (B), and monomers (C) [hereinafter also referred to as “other monomers (D)”] have the following chemical formula ( 6) can be exemplified.
In chemical formula (6), Y represents a divalent group of a sulfur atom, a sulfone group, a methylene group, an isopropylidene group or a hexafluoroisopropylidene group.
ハロゲン系難燃剤としては、塩素を含む有機化合物と臭素を含む化合物が挙げられる。具体的には、ペンタブロモジフェニルエーテル、オクタブロモジフェニルエーテル、デカブロモジフェニルエーテル、テトラブロモビスフェノールA、ヘキサブロモシクロデカンテトラブロモビスフェノールAなどが挙げられる。
無機系難燃剤としては、アンチモン化合物と金属水酸化物などが挙げられる。アンチモン化合物としては三酸化アンチモンと五酸化アンチモンが挙げられる。金属水酸化物としては、水酸化アルミニウム、水酸化マグネシウムなどが挙げられる。
リン系難燃剤としては、ホスファゼン、ホスフィン、ホスフィンオキサイド、リン酸エステルなどが挙げられる。
難燃剤の添加量は、特に限定されず、用いる難燃剤の種類に応じて適宜変更できる。一般的には、ポリイミド樹脂100質量部に対して5質量部から50質量部の範囲で用いることが好ましい。 The polyimide resin composition may contain a flame retardant. Although a flame retardant is not specifically limited, For example, a halogen flame retardant, an inorganic flame retardant, and a phosphorus flame retardant can be used. A flame retardant may be used by 1 type and may be used in mixture of 2 or more types.
Examples of the halogen-based flame retardant include an organic compound containing chlorine and a compound containing bromine. Specific examples include pentabromodiphenyl ether, octabromodiphenyl ether, decabromodiphenyl ether, tetrabromobisphenol A, hexabromocyclodecane tetrabromobisphenol A, and the like.
Examples of inorganic flame retardants include antimony compounds and metal hydroxides. Antimony compounds include antimony trioxide and antimony pentoxide. Examples of the metal hydroxide include aluminum hydroxide and magnesium hydroxide.
Examples of the phosphorus flame retardant include phosphazene, phosphine, phosphine oxide, and phosphate ester.
The addition amount of the flame retardant is not particularly limited, and can be appropriately changed according to the type of the flame retardant used. Generally, it is preferable to use in the range of 5 to 50 parts by mass with respect to 100 parts by mass of the polyimide resin.
以下、本発明を実施例によってより詳細に説明するが、本発明は以下の実施例によって何ら限定されるものではない。 <Example>
EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited at all by the following example.
(ポリイミド樹脂組成物の調製) NMPとメシチレン(1,3,5-トリメチルベンゼン)を8:2の比率で調整した溶媒中に、1,3-ビス(3-アミノフェノキシ)ベンゼン(以下、「APB-N」と称する)と、3,3',4,4'-ビフェニルテトラカルボン酸二無水物(以下、「s-BPDA」と称する)(JFEケミカル社製)、3,3',4,4'-ベンゾフェノンテトラカルボン酸二無水物(以下、「BTDA」と称する)の2種類の酸二無水物とを、APB-N:s-BPDA:BTDA=1.0:0.69:0.3のモル比で配合した。得られた混合物を、乾燥窒素ガスを導入することができるフラスコ内で4時間以上攪拌して、樹脂固形分質量が18~25質量%であるポリアミック酸溶液を得た。十分に攪拌した後、ディーンスターク管が付属したフラスコ内で攪拌しながら、反応系を180℃程度まで加熱し、脱水反応により発生した水を系外に取り出すことでポリイミド樹脂組成物を得た。 Example 1
(Preparation of Polyimide Resin Composition) 1,3-Bis (3-aminophenoxy) benzene (hereinafter referred to as “NMP and mesitylene (1,3,5-trimethylbenzene)” in a solvent prepared at a ratio of 8: 2. APB-N ”), 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (hereinafter referred to as“ s-BPDA ”) (manufactured by JFE Chemical), 3,3 ′, 4 , 4′-benzophenonetetracarboxylic dianhydride (hereinafter referred to as “BTDA”) and APB-N: s-BPDA: BTDA = 1.0: 0.69: 0 .3 molar ratio. The obtained mixture was stirred for 4 hours or more in a flask into which dry nitrogen gas could be introduced to obtain a polyamic acid solution having a resin solid content of 18 to 25% by mass. After sufficiently stirring, the reaction system was heated to about 180 ° C. while stirring in a flask equipped with a Dean-Stark tube, and water generated by the dehydration reaction was taken out of the system to obtain a polyimide resin composition.
ポリイミドフィルムの粘弾性は、300℃での貯蔵弾性率E'の値に基づいて評価した。
○:貯蔵弾性率E'が1.0×105Pa以上
×:貯蔵弾性率E'が1.0×105Pa未満 (Viscoelasticity evaluation of a film) The glass transition temperature of the produced polyimide film was evaluated. The measurement is performed by measuring the storage elastic modulus E ′ and the loss elastic modulus E ″ by temperature dispersion measurement (tensile mode) of solid viscoelasticity, and calculating the glass transition temperature from the peak value of loss tangent tan δ = E ″ / E ′. Derived. As a measuring device, RSA-III manufactured by TA instruments was used, and measurement was performed in a tensile mode and a measurement frequency of 1 Hz.
The viscoelasticity of the polyimide film was evaluated based on the value of the storage elastic modulus E ′ at 300 ° C.
○: Storage elastic modulus E ′ is 1.0 × 10 5 Pa or more ×: Storage elastic modulus E ′ is less than 1.0 × 10 5 Pa
η=ln[希釈ワニス落下時間/NMP落下時間]より、粘度平均分子量ηを算出した。 (Evaluation of viscosity average molecular weight η of polyimide resin composition) A small amount of polyimide varnish to be measured was collected in an Erlenmeyer flask and diluted to 0.5 (g / dL) using NMP. The fall time was measured with the Uberote tube (made by Shibata Kagaku Co., Ltd.) which put the produced dilution varnish in the 35 degreeC thermostat.
The viscosity average molecular weight η was calculated from η = ln [dilution varnish falling time / NMP falling time].
装置は515ポンプ、717Plus 自動注入装置(日本ウォーターズ社製)を用い、以下の条件で行った。カラム温度:60℃、分離カラム:TSKgel Super AWM-H 6.0mm I.D. ×15cm 2本(東ソー社製)、移動相:10mM LiBrを添加したNMP、流速:0.5mL/min、検出器:示差屈折計(Shodex(登録商標)RI-101 昭和電工社製)、注入量:20μL、分子量構成:単分散ポリスチレン(EasiCal PS-1;ポリマーラボラトリーズ社製) (GPC Evaluation) A polyimide varnish to be measured was diluted with a mobile phase for GPC measurement to prepare a concentration of 0.1%. After leaving overnight, it was filtered using a membrane filter (MILLEX-LH; manufactured by Nihon Millipore), and the filtrate was used for measurement.
The apparatus used was a 515 pump, 717Plus automatic injection device (manufactured by Nippon Waters) under the following conditions. Column temperature: 60 ° C., separation column: TSKgel Super AWM-H 6.0 mm ID × 15 cm 2 (manufactured by Tosoh Corporation), mobile phase: NMP added with 10 mM LiBr, flow rate: 0.5 mL / min, detector: differential refractometer (Shodex (registered trademark) RI-101, manufactured by Showa Denko KK), injection amount: 20 μL, molecular weight composition: monodisperse polystyrene (EasiCal PS-1; manufactured by Polymer Laboratories)
○:3ヶ月保管後も、樹脂の析出やゲル化の発生無し
×:3ヶ月以内に、樹脂の析出やゲル化の発生あり (Stability Evaluation of Polyimide Resin Composition) The storage stability of the prepared polyimide resin composition was evaluated. The produced polyimide resin composition was observed in a small bottle, especially in a refrigerator (3 ° C.), and the appearance was changed with time, and whether it was stored for 3 months was checked for resin precipitation or gelation.
○: No resin precipitation or gelation after storage for 3 months ×: Residual precipitation or gelation within 3 months
NMPとメシチレンを8:2の比率で調整した溶媒中に、2,2-ビス〔4-(4-アミノフェノキシ)フェニル〕プロパン(以下、「p-BAPP」と称する)からなるジアミンと、s-BPDA,BTDAの2種類の酸二無水物とを、pBAPP:s-BPDA:BTDA=1.0:0.79:0.2のモル比で配合した。当該配合比を除く条件は、実施例1と同様にしてポリイミド樹脂組成物を調製した。そして、実施例1と同様の方法でポリイミドフィルムを作製し、評価した。 (Example 2)
A diamine composed of 2,2-bis [4- (4-aminophenoxy) phenyl] propane (hereinafter referred to as “p-BAPP”) in a solvent prepared by adjusting NMP and mesitylene in a ratio of 8: 2, and s -BPDA and BTDA, two types of acid dianhydrides were blended at a molar ratio of pBAPP: s-BPDA: BTDA = 1.0: 0.79: 0.2. The polyimide resin composition was prepared in the same manner as in Example 1 except for the mixing ratio. And the polyimide film was produced by the method similar to Example 1, and was evaluated.
NMPとメシチレンを8:2の比率で調整した溶媒中に、APB-Nと、4,4'-ビス(3-アミノフェノキシ)ビフェニル(以下、「mBP」と称する)の2種類のジアミンと、s-BPDA,BTDA,4,4'-オキシジフタル酸無水物(以下、「ODPA」と称する)の3種類の酸二無水物とを、APB-N:mBP:s-BPDA:BTDA:ODPA=0.5:0.5:0.2:0.3:0.49のモル比で配合した。当該配合比を除く条件は、実施例1と同様にしてポリイミド樹脂組成物を調製した。そして、実施例1と同様の方法でポリイミドフィルムを作製し、評価した。 (Example 3)
In a solvent prepared by adjusting NMP and mesitylene at a ratio of 8: 2, two types of diamines, APB-N and 4,4′-bis (3-aminophenoxy) biphenyl (hereinafter referred to as “mBP”), Three types of acid dianhydrides, s-BPDA, BTDA, 4,4′-oxydiphthalic anhydride (hereinafter referred to as “ODPA”), APB-N: mBP: s-BPDA: BTDA: ODPA = 0 .5: 0.5: 0.2: 0.3: 0.49 molar ratio. The polyimide resin composition was prepared in the same manner as in Example 1 except for the mixing ratio. And the polyimide film was produced by the method similar to Example 1, and was evaluated.
NMPとメシチレンを8:2の比率で調整した溶媒中に、1,3-ビス(3-(3-アミノフェノキシ)フェノキシ)ベンゼン(以下、「APB5」と称する)からなる1種類のジアミンと、s-BPDA,BTDAの2種類の酸二無水物とを、APB5:s-BPDA:BTDA=1.0:0.69:0.3のモル比で配合した。当該配合比を除く条件は、実施例1と同様にしてポリイミド樹脂組成物を調製した。また、実施例1と同様の方法によりポリイミドフィルムを作製し、評価した。 (Example 4)
In a solvent prepared by adjusting NMP and mesitylene at a ratio of 8: 2, one kind of diamine composed of 1,3-bis (3- (3-aminophenoxy) phenoxy) benzene (hereinafter referred to as “APB5”); Two types of acid dianhydrides, s-BPDA and BTDA, were blended at a molar ratio of APB5: s-BPDA: BTDA = 1.0: 0.69: 0.3. The polyimide resin composition was prepared in the same manner as in Example 1 except for the mixing ratio. Moreover, the polyimide film was produced by the method similar to Example 1, and evaluated.
NMPとメシチレンを8:2の比率で調整した溶媒中に、APB-N,4,4'-オキシジアニリン(以下、「ODA」と称する)の2種類のジアミンと、s-BPDA,BTDAの2種類の酸二無水物とを、APB-N:ODA:s-BPDA:BTDA=0.7:0.3:0.69:0.3のモル比で配合した。当該配合比以外は、実施例1と同様にポリイミド樹脂組成物を調製し、ポリイミドフィルムを作製して評価した。 (Example 5)
In a solvent in which NMP and mesitylene were adjusted at a ratio of 8: 2, two kinds of diamines, APB-N, 4,4′-oxydianiline (hereinafter referred to as “ODA”), and s-BPDA and BTDA Two types of acid dianhydrides were blended at a molar ratio of APB-N: ODA: s-BPDA: BTDA = 0.7: 0.3: 0.69: 0.3. Except for the blending ratio, a polyimide resin composition was prepared in the same manner as in Example 1, and a polyimide film was prepared and evaluated.
NMPとメシチレンを8:2の比率で調整した溶媒中に、APB-Nの1種類のジアミンと、ODPA、BTDAの2種類の酸二無水物とを、APB-N:ODPA:BTDA=1.0:0.69:0.3のモル比で配合した。当該配合比以外は、実施例1と同様にポリイミド樹脂組成物を調製し、ポリイミドフィルムを作製して評価した。 (Example 6)
In a solvent prepared by adjusting NMP and mesitylene at a ratio of 8: 2, one kind of diamine of APB-N and two kinds of acid dianhydrides of ODPA and BTDA, APB-N: ODPA: BTDA = 1. The molar ratio was 0: 0.69: 0.3. Except for the blending ratio, a polyimide resin composition was prepared in the same manner as in Example 1, and a polyimide film was prepared and evaluated.
NMPとメシチレンを8:2の比率で調整した溶媒中に、APB-Nからなる1種類のジアミンと、s-BPDAからなる1種類の酸二無水物とを、APB-N:s-BPDA=1.0:0.99のモル比で配合した。そして、実施例1と同様にポリイミド樹脂組成物を調製し、ポリイミドフィルムを作製して評価した。 (Comparative Example 1)
In a solvent in which NMP and mesitylene were adjusted at a ratio of 8: 2, one kind of diamine composed of APB-N and one kind of acid dianhydride composed of s-BPDA were added to APB-N: s-BPDA = The molar ratio was 1.0: 0.99. And the polyimide resin composition was prepared similarly to Example 1, and the polyimide film was produced and evaluated.
NMPとメシチレンを8:2の比率で調整した溶媒中に、APB-Nからなる1種類のジアミンと、BTDAからなる1種類の酸二無水物とを、APB-N:BTDA=1.0:0.99のモル比で配合した。そして、実施例1と同様にポリイミド樹脂組成物を調製し、ポリイミドフィルムを作製して評価した。 (Comparative Example 2)
In a solvent in which NMP and mesitylene were adjusted at a ratio of 8: 2, one kind of diamine composed of APB-N and one kind of acid dianhydride composed of BTDA were added to APB-N: BTDA = 1.0: It was blended at a molar ratio of 0.99. And the polyimide resin composition was prepared similarly to Example 1, and the polyimide film was produced and evaluated.
NMPとメシチレンを8:2の比率で調整した溶媒中に、APB-Nからなる1種類のジアミンと、ODPAからなる1種類の酸二無水物とを、APB-N:ODPA=1.0:0.99のモル比で配合したこと以外は、実施例1と同様にポリイミド樹脂組成物を調製し、ポリイミドフィルムを作製して評価した。 (Comparative Example 3)
In a solvent in which NMP and mesitylene were adjusted at a ratio of 8: 2, one kind of diamine composed of APB-N and one kind of acid dianhydride composed of ODPA were added to APB-N: ODPA = 1.0: A polyimide resin composition was prepared in the same manner as in Example 1 except that it was blended at a molar ratio of 0.99, and a polyimide film was prepared and evaluated.
NMPとメシチレンを8:2の比率で調整した溶媒中に、1種類のジアミン(APB-N)と1種類の酸二無水物(ODPA)とを、APB-N:ODPA=1.0:1.02のモル比で配合したこと以外は、実施例1と同様に化学式(7)のポリイミドワニスを調製し、評価した。ワニスの粘度が低すぎて、ポリイミドフィルムを作製は不可能であった。
One type of diamine (APB-N) and one type of acid dianhydride (ODPA) in a solvent prepared by adjusting NMP and mesitylene at a ratio of 8: 2, APB-N: ODPA = 1.0: 1 A polyimide varnish of the chemical formula (7) was prepared and evaluated in the same manner as in Example 1 except that it was blended at a molar ratio of 0.02. The viscosity of the varnish was too low to produce a polyimide film.
NMPとメシチレンを8:2の比率で調整した溶媒中に、APB-Nからなる1種類のジアミンと、s-BPDA,BTDAからなる2種類の酸二無水物とを、APB-N:BPDA:BTDA=0.99:0.7:0.3のモル比で配合した。当該配合比以外は、実施例1と同様にポリイミド樹脂組成物を調製し、ポリイミドフィルムを作製して評価した。 (Comparative Example 5)
In a solvent in which NMP and mesitylene were adjusted at a ratio of 8: 2, one kind of diamine composed of APB-N and two kinds of acid dianhydrides composed of s-BPDA and BTDA were added to APB-N: BPDA: It was blended at a molar ratio of BTDA = 0.99: 0.7: 0.3. Except for the blending ratio, a polyimide resin composition was prepared in the same manner as in Example 1, and a polyimide film was prepared and evaluated.
NMPとメシチレンを8:2の比率で調整した溶媒中に、APB-N,m-BPの2種類のジアミンと、s-BPDA,BTDAからなる2種類の酸二無水物とを、APB-N:m-BP:BPDA:BTDA=0.3:0.7:0.69:0.3のモル比で配合した。当該配合比以外は、実施例1と同様にポリイミド樹脂組成物を調製し、ポリイミドフィルムを作製して評価した。 (Comparative Example 6)
In a solvent prepared by adjusting NMP and mesitylene at a ratio of 8: 2, two kinds of diamines APB-N and m-BP and two kinds of acid dianhydrides composed of s-BPDA and BTDA are added to APB-N. : M-BP: BPDA: BTDA = 0.3: 0.7: 0.69: 0.3. Except for the blending ratio, a polyimide resin composition was prepared in the same manner as in Example 1, and a polyimide film was prepared and evaluated.
NMPとメシチレンを8:2の比率で調整した溶媒中に、APB-Nの1種類のジアミンと、BTDAの1種類の酸二無水物とを、APB-N:BTDA=1.0:0.9のモル比で配合した。当該配合比以外は、実施例1と同様にポリイミド樹脂組成物を調製し、評価した。ワニスの粘度が低すぎて、ポリイミドフィルムを作製することができなかった。 (Comparative Example 7)
In a solvent prepared by adjusting NMP and mesitylene at a ratio of 8: 2, one diamine of APB-N and one acid dianhydride of BTDA were added to APB-N: BTDA = 1.0: 0. It was blended at a molar ratio of 9. Except for the mixing ratio, a polyimide resin composition was prepared and evaluated in the same manner as in Example 1. The viscosity of the varnish was too low to produce a polyimide film.
Claims (19)
- 極性溶媒と、
ポリイミド樹脂と、を少なくとも含む組成物からなり、
前記ポリイミド樹脂の粘度平均分子量ηが、0.6以上、1.60以下であり、
前記ポリイミド樹脂を構成する全モノマーに対して95mol%以上、100mol%以下を、主鎖に炭素数3以上の脂肪族鎖を有さない芳香族モノマーとし、
前記芳香族モノマーは、
化学式(1)及び化学式(2)で表されるベンゾフェノン骨格の少なくともいずれかを有するモノマー(A)を、前記ポリイミド樹脂を構成する全モノマー中に5mol%以上、30mol%以下含み、
ビフェニル骨格を有さず、ジフェニルエーテル骨格を有するモノマー(B)を、前記ポリイミド樹脂を構成する全モノマー中に40mol%以上、95mol%以下含み、
ビフェニル骨格を有するモノマー(C)を、前記ポリイミド樹脂を構成する全モノマー中に0mol%以上、45mol%未満含むものであり、
前記モノマー(B)は、前記ポリイミド樹脂を構成する全モノマー中、20mol%以上が芳香環を3個以上有するモノマー(B-1)であるポリイミド樹脂組成物。
A composition comprising at least a polyimide resin,
The viscosity average molecular weight η of the polyimide resin is 0.6 or more and 1.60 or less,
95 mol% or more and 100 mol% or less with respect to all monomers constituting the polyimide resin as an aromatic monomer having no aliphatic chain having 3 or more carbon atoms in the main chain,
The aromatic monomer is
The monomer (A) having at least one of the benzophenone skeletons represented by the chemical formula (1) and the chemical formula (2) is included in all monomers constituting the polyimide resin in an amount of 5 mol% or more and 30 mol% or less,
A monomer having no diphenyl ether skeleton and a diphenyl ether skeleton (B) is contained in an amount of 40 mol% or more and 95 mol% or less in all monomers constituting the polyimide resin,
The monomer (C) having a biphenyl skeleton is contained in all monomers constituting the polyimide resin in an amount of 0 mol% or more and less than 45 mol%,
The polyimide resin composition, wherein the monomer (B) is a monomer (B-1) in which 20 mol% or more of all monomers constituting the polyimide resin have 3 or more aromatic rings.
- 前記組成物を塗工し、乾燥して得られるポリイミドフィルムが、
(a)ガラス転移温度が130℃以上、260℃未満、
(b)25℃での引張弾性率が2.0GPa以上、4.0GPa未満、
(c)窒素雰囲気下での5%熱重量減少温度が500℃以上、
である請求項1に記載のポリイミド樹脂組成物。 A polyimide film obtained by applying the composition and drying it,
(A) glass transition temperature is 130 ° C. or higher and lower than 260 ° C.,
(B) Tensile modulus at 25 ° C. is 2.0 GPa or more and less than 4.0 GPa,
(C) 5% thermal weight loss temperature in a nitrogen atmosphere is 500 ° C. or higher,
The polyimide resin composition according to claim 1. - 前記ポリイミド樹脂の末端基を構成するモノマーがジアミンである請求項1又は2に記載のポリイミド樹脂組成物。 The polyimide resin composition according to claim 1 or 2, wherein the monomer constituting the terminal group of the polyimide resin is a diamine.
- 前記ベンゾフェノン骨格を有するモノマー(A)は、3,3'-ジアミノベンゾフェノン、3,4'-ジアミノベンゾフェノン、4,4'-ジアミノベンゾフェノン、3,3',4,4'-ベンゾフェノンテトラカルボン酸二無水物、及び2,3',3,4'-ベンゾフェノンテトラカルボン酸二無水物の少なくともいずれかである請求項1~3のいずれか1項に記載のポリイミド樹脂組成物。 The monomer (A) having a benzophenone skeleton includes 3,3′-diaminobenzophenone, 3,4′-diaminobenzophenone, 4,4′-diaminobenzophenone, 3,3 ′, 4,4′-benzophenone tetracarboxylic acid The polyimide resin composition according to any one of claims 1 to 3, which is at least one of an anhydride and 2,3 ', 3,4'-benzophenonetetracarboxylic dianhydride.
- 前記モノマー(B-1)の芳香環がベンゼン環である請求項1~4のいずれか1項に記載のポリイミド樹脂組成物。 The polyimide resin composition according to any one of claims 1 to 4, wherein the aromatic ring of the monomer (B-1) is a benzene ring.
- 前記ビフェニル骨格を有するモノマー(C)は、4,4'-ビス(3-アミノフェノキシ)ビフェニル、4,4'-ビス(4-アミノフェノキシ)ビフェニル、3,3'-ビス(4-アミノフェノキシ)ビフェニル、2,2'-ビス(トリフルオロメチル)-1,1'-ビフェニル-4,4'-ジアミン、4,4'-ビス(3,4-ジカルボキシフェノキシ)ビフェニル二無水物、2,2',3,3'-ビフェニルテトラカルボン酸二無水物、3,3',4,4'-ビフェニルテトラカルボン酸二無水物の少なくともいずれかである請求項1~5のいずれか1項に記載のポリイミド樹脂組成物。 The monomer (C) having a biphenyl skeleton includes 4,4′-bis (3-aminophenoxy) biphenyl, 4,4′-bis (4-aminophenoxy) biphenyl, and 3,3′-bis (4-aminophenoxy). ) Biphenyl, 2,2′-bis (trifluoromethyl) -1,1′-biphenyl-4,4′-diamine, 4,4′-bis (3,4-dicarboxyphenoxy) biphenyl dianhydride, 2 6. At least one of 2,3 ′, 3,3′-biphenyltetracarboxylic dianhydride and 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride The polyimide resin composition described in 1.
- 前記ビフェニル骨格を有するモノマー(C)を、前記ポリイミド樹脂を構成する全モノマー中に10モル%以上含む請求項1~6のいずれか1項に記載のポリイミド樹脂組成物。 The polyimide resin composition according to any one of claims 1 to 6, wherein the monomer (C) having the biphenyl skeleton is contained in an amount of 10 mol% or more in all monomers constituting the polyimide resin.
- 前記ポリイミド樹脂を構成するテトラカルボン酸二無水物の合計モル数が、前記ポリイミド樹脂を構成するジアミンの合計モル数に対して、0.99~0.999である請求項1~7のいずれか1項に記載のポリイミド樹脂組成物。 The total number of moles of tetracarboxylic dianhydride constituting the polyimide resin is 0.99 to 0.999 with respect to the total number of moles of diamine constituting the polyimide resin. The polyimide resin composition according to item 1.
- 前記ポリイミド樹脂の重量平均分子量が、120,000以上、300,000以下であり、Mw/Mn比が10以上、12以下である請求項1~8のいずれか1項に記載のポリイミド樹脂組成物。 The polyimide resin composition according to any one of claims 1 to 8, wherein the polyimide resin has a weight average molecular weight of 120,000 or more and 300,000 or less, and an Mw / Mn ratio of 10 or more and 12 or less. .
- 前記ポリイミドフィルムの300℃での貯蔵弾性率が、1.0×105Pa以上である請求項2に記載のポリイミド樹脂組成物。 The polyimide resin composition according to claim 2, wherein the polyimide film has a storage elastic modulus at 300 ° C. of 1.0 × 10 5 Pa or more.
- さらに、フィラーを含有する請求項1~10のいずれか1項に記載のポリイミド樹脂組成物。 The polyimide resin composition according to any one of claims 1 to 10, further comprising a filler.
- さらに、ビスマレイミド化合物、及びナジイミド化合物より選ばれる1種以上の化合物を含有する請求項1~11のいずれか1項に記載のポリイミド樹脂組成物。 The polyimide resin composition according to any one of claims 1 to 11, further comprising at least one compound selected from a bismaleimide compound and a nadiimide compound.
- さらに、他の樹脂を含有する請求項1~12のいずれか1項に記載のポリイミド樹脂組成物。 The polyimide resin composition according to any one of claims 1 to 12, further comprising another resin.
- 請求項1~13のいずれか1項に記載のポリイミド樹脂組成物から形成されたフィルム。 A film formed from the polyimide resin composition according to any one of claims 1 to 13.
- 請求項14に記載のフィルムは、カバーレイフィルムであることを特徴とするフィルム。 The film according to claim 14 is a coverlay film.
- 請求項1~13のいずれか1項に記載のポリイミド樹脂組成物を含む接着剤。 An adhesive comprising the polyimide resin composition according to any one of claims 1 to 13.
- 請求項16に記載の接着剤は、フレキシブルプリント基板用接着剤、カバーレイフィルム用接着剤、又はボンディングシート用接着剤であることを特徴とする接着剤。 The adhesive according to claim 16, wherein the adhesive is an adhesive for a flexible printed circuit board, an adhesive for a coverlay film, or an adhesive for a bonding sheet.
- 請求項1~13のいずれか1項に記載のポリイミド樹脂組成物から形成された成形体を含む部品。 A part including a molded body formed from the polyimide resin composition according to any one of claims 1 to 13.
- 請求項18に記載の部品は、
電子回路基板部材、半導体デバイス、リチウムイオン電池部材、太陽電池部材、燃料電池部材、モーター巻線、エンジン周辺部材、塗料、光学部品、放熱材、電磁波シールド材、サージ部品、歯科材、摺動コート、及び静電チャックのいずれかであることを特徴とする部品。 The component according to claim 18 comprises:
Electronic circuit board member, semiconductor device, lithium ion battery member, solar cell member, fuel cell member, motor winding, engine peripheral member, paint, optical component, heat radiation material, electromagnetic shielding material, surge component, dental material, sliding coating And an electrostatic chuck.
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WO2018194133A1 (en) * | 2017-04-21 | 2018-10-25 | 三井化学株式会社 | Semiconductor substrate manufacturing method, semiconductor device, and method for manufacturing same |
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