WO2011071087A1 - Procédé pour produire un film de polyimide, et film de polyimide - Google Patents

Procédé pour produire un film de polyimide, et film de polyimide Download PDF

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Publication number
WO2011071087A1
WO2011071087A1 PCT/JP2010/072049 JP2010072049W WO2011071087A1 WO 2011071087 A1 WO2011071087 A1 WO 2011071087A1 JP 2010072049 W JP2010072049 W JP 2010072049W WO 2011071087 A1 WO2011071087 A1 WO 2011071087A1
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Prior art keywords
polyimide
polyimide film
film
self
laminate
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PCT/JP2010/072049
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English (en)
Japanese (ja)
Inventor
信治 久野
慎一郎 小浜
泰造 村上
裕章 山口
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宇部興産株式会社
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Application filed by 宇部興産株式会社 filed Critical 宇部興産株式会社
Priority to CN201080062735.7A priority Critical patent/CN102741330B/zh
Priority to US13/514,756 priority patent/US20120244352A1/en
Priority to JP2011545230A priority patent/JP5609891B2/ja
Publication of WO2011071087A1 publication Critical patent/WO2011071087A1/fr

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    • 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
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
    • Y10T428/2852—Adhesive compositions
    • Y10T428/2896—Adhesive compositions including nitrogen containing condensation polymer [e.g., polyurethane, polyisocyanate, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31678—Of metal
    • Y10T428/31681—Next to polyester, polyamide or polyimide [e.g., alkyd, glue, or nylon, etc.]

Definitions

  • the present invention relates to a method for producing a polyimide film with improved adhesion and a polyimide film. Moreover, this invention relates to the polyimide laminated body formed by laminating
  • Polyimide films are widely used in the fields of electric / electronic devices and semiconductors because they are excellent in heat resistance, chemical resistance, mechanical strength, electrical properties, dimensional stability, and the like.
  • a flexible printed wiring board FPC
  • a copper-clad laminated board formed by laminating a copper foil on one or both sides of a polyimide film is used.
  • a polyimide film generally has a problem in adhesiveness, and a laminate having sufficient adhesive strength when bonded to a metal foil such as a copper foil via a heat-resistant adhesive such as an epoxy resin adhesive. It may not be obtained. Also, when a metal layer is provided on the polyimide film by metal plating or dry plating such as sputtering, or when a metal layer is provided on the polyimide film by wet plating such as electroless plating, a laminate with sufficiently high peel strength is obtained. It may not be obtained.
  • Patent Document 1 discloses that a surface treatment liquid containing a heat-resistant surface treatment agent (coupling agent) is applied to the surface of a solidified film of polyamic acid, and then the surface treatment.
  • a method for producing a polyimide film is disclosed in which the solidified film coated with the liquid is heated to a temperature of 100 to 600 ° C. to imidize the polyamic acid forming the solidified film, and the film is dried and heat treated.
  • the adhesion of the polyimide film is improved by applying a solution of a heat-resistant surface treatment agent (coupling agent) to the surface of the solidified film of polyamic acid.
  • Adhesion may be reduced when placed in a humid environment. For example, when the polyimide metal laminate is treated at 150 ° C. for a long time or treated at 121 ° C. and 100% RH for a long time, the peel strength may be lowered.
  • An object of the present invention is to provide a method for producing a polyimide film having excellent adhesion not only in the initial stage but also after heat treatment or after high temperature and high humidity treatment.
  • a method for producing a polyimide film having excellent adhesiveness by suppressing the occurrence of cracks in the solidified film of polyamic acid and having a uniform surface, a thickness of 20 ⁇ m or less, further 15 ⁇ m or less, and further 10 ⁇ m or less. is to provide.
  • it is providing the polyimide laminated body with big peeling strength with an adhesive bond layer or a metal layer using the polyimide film obtained by this method.
  • the present invention relates to the following matters.
  • the surface treatment agent solution is a water-soluble liquid, and includes a solvent having a surface tension at 20 ° C. of 32 mN / m or less and a boiling point of 125 ° C. or more.
  • the tetracarboxylic acid component contains 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and / or pyromellitic dianhydride as a main component, 3.
  • a polyimide metal laminate obtained by laminating a metal layer on the surface of the polyimide film described in 9 above, to which a solution of a surface treatment agent is applied at the time of production.
  • stacks an adhesive bond layer on the surface which apply
  • a polyimide metal laminate obtained by adhering a metal foil to the adhesive layer of the polyimide laminate described in 12 above.
  • a solution of a surface treatment agent such as a coupling agent is applied to the surface of a solidified film of polyamic acid (also referred to as a self-supporting film), and this is heated.
  • a solvent for the surface treatment agent solution also referred to as coating solvent
  • a water-soluble liquid having a surface tension at 20 ° C. of 32 mN / m or less and a boiling point of 125 ° C. or more is used.
  • a solution of the surface treatment agent is formed on the surface of a thin polyamic acid solidified film having a thickness of 20 ⁇ m or less, further 15 ⁇ m or less, and further 10 ⁇ m or less. It can be applied neatly while suppressing the occurrence. Therefore, according to the present invention, a thin polyimide film having a uniform surface and excellent adhesion and a thickness of 20 ⁇ m or less, further 15 ⁇ m or less, and further 10 ⁇ m or less can be produced. That is, the present invention can be applied to a thin polyimide film, and a laminate can be obtained with almost no limitation on thickness.
  • the present invention is excellent in fire safety even when used in a large amount of film production equipment.
  • the polyimide film of the present invention is obtained by casting a polyamic acid solution obtained by reacting a tetracarboxylic acid component and a diamine component in an organic solvent on a support and heating and drying it to obtain a self-supporting film.
  • a solution of a surface treatment agent on one side or both sides of this self-supporting film and heating to remove the coating solvent mainly as needed, then heating and imidizing this self-supporting film Obtainable.
  • the surface treating agent solution used in the present invention is a water-soluble liquid, and is dissolved or uniformly dispersed in a solvent having a surface tension at 20 ° C. of 32 mN / m or less and a boiling point of 125 ° C. or more. Solution (which may be a suspension).
  • the polyimide film of the present invention is obtained by thermal imidization and / or chemical imidization, and when it contains a plurality of tetracarboxylic acid components and diamine components, it is block copolymerized even if it is randomly copolymerized. Or they may be used in combination.
  • a solution of a surface treatment agent is applied to one or both sides of this self-supporting film, and then thermally dehydrated and desolvated to remove polyimide.
  • a method of obtaining a film (2) A cyclization catalyst and a dehydrating agent are added to the polyamic acid solution, and the polyamic acid solution composition added by selecting inorganic fine particles and the like as necessary is cast on a support in a film form. After dehydrating and cyclizing to obtain a self-supporting film by heating and drying as necessary, a solution of a surface treatment agent is applied to one or both sides of the self-supporting film, A method of obtaining a polyimide film by imidization, Is mentioned.
  • tetracarboxylic dianhydride examples include 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (s-BPDA) and pyromellitic dianhydride (PMDA).
  • s-BPDA 4,4′-biphenyltetracarboxylic dianhydride
  • PMDA pyromellitic dianhydride
  • 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride (a-BPDA) oxydiphthalic dianhydride, diphenylsulfone-3,4,3 ′, 4′-tetracarboxylic dianhydride, Bis (3,4-dicarboxyphenyl) sulfide dianhydride, 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride, 2 , 3,3 ′, 4′-benzophenone te
  • the tetracarboxylic acid component is preferably a tetracarboxylic acid component containing s-BPDA and / or PMDA as a main component.
  • an acid component selected from s-BPDA and PMDA preferably one or more of s-BPDA and PMDA, particularly preferably 50 mol% or more of s-BPDA
  • a tetracarboxylic acid component containing 70 mol% or more, particularly preferably 75 mol% or more is preferable because the resulting polyimide film is excellent in mechanical properties.
  • diamines include 1) One benzene nucleus diamine such as paraphenylenediamine (1,4-diaminobenzene; PPD), 1,3-diaminobenzene, 2,4-toluenediamine, 2,5-toluenediamine, 2,6-toluenediamine, etc.
  • PPD paraphenylenediamine
  • 1,3-diaminobenzene 1,3-diaminobenzene
  • 2,4-toluenediamine 2,4-toluenediamine
  • 2,5-toluenediamine 2,6-toluenediamine, etc.
  • Diaminodiphenyl ethers such as 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4 ' -Diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4 ' -Diaminodiphenylmethane, 3,3'-dicarboxy-4,4'-diaminodiphenylmethane, 3,3 ', 5,5'-tetramethyl-4,4'-diaminodiphenylmethane, bis (4-aminophenyl) sulfide, 4,4'-diaminodip
  • the benzene core of three diamines 4) 3,3′-bis (3-aminophenoxy) biphenyl, 3,3′-bis (4-aminophenoxy) biphenyl, 4,4′-bis (3-aminophenoxy) biphenyl, 4,4′-bis (4-aminophenoxy) biphenyl, 4,4′-bis (4-aminophenoxy) biphenyl, bis [3- (3-aminophenoxy) phenyl] ether, bis [3- (4-aminophenoxy) phenyl] ether, bis [4- (3-aminophenoxy) phenyl] ether, Bis [4- (4-aminophenoxy) phenyl] ether, bis [3- (3-aminophenoxy) phenyl] ketone, bis [3- (4-aminophenoxy) phenyl] ketone, bis [4- (3-amino Phenoxy) phenyl] ketone, bis [4- (4-a
  • a diamine component containing PPD and / or diaminodiphenyl ether as a main component is preferable.
  • a diamine component selected from PPD and diaminodiphenyl ethers, preferably any one or more of PPD, 4,4′-diaminodiphenyl ether, or 3,4′-diaminodiphenyl ether Particularly preferably, a diamine component containing PPD in an amount of 50 mol% or more, more preferably 70 mol% or more, and particularly preferably 75 mol% or more is preferable because the resulting polyimide film is excellent in mechanical properties.
  • the polyimide is preferably a polyimide produced from s-BPDA and PPD, or optionally PPD and diaminodiphenyl ethers such as 4,4'-diaminodiphenyl ether and 3,4'-diaminodiphenyl ether.
  • the PPD / diaminodiphenyl ether (molar ratio) is preferably 100/0 to 85/15.
  • PMDA aromatic tetracarboxylic dianhydride which is a combination of s-BPDA and PMDA, PPD, tolidine (ortho form, meta form), 4,4′-diaminodiphenyl ether, 3,4′-diamino
  • polyimides made from aromatic diamines such as diaminodiphenyl ethers such as diphenyl ether.
  • PPD or an aromatic diamine in which PPD / diaminodiphenyl ethers are 90/10 to 10/90 is preferable.
  • s-BPDA / PMDA is preferably 0/100 to 90/10.
  • diaminodiphenyl ethers such as 4,4'-diaminodiphenyl ether and 3,4'-diaminodiphenyl ether.
  • the diaminodiphenyl ethers / PPD is preferably 90/10 to 10/90.
  • the polyamic acid that is a polyimide precursor can be obtained by reacting the tetracarboxylic acid component and the diamine component as described above by a known method. For example, an approximately equimolar amount of a tetracarboxylic acid component and a diamine component are reacted in an organic solvent to prepare a polyamic acid solution (which may be partially imidized as long as a uniform solution state is maintained). Obtainable. Alternatively, it combines the two or more polyamic acid is excessive advance either component, these polyamic acid solution was combined, it may be mixed under reaction conditions. The polyamic acid solution thus obtained can be used for the production of a self-supporting film as it is or after removing or adding a solvent if necessary.
  • organic solvent of the polyamic acid solution a known solvent can be used, and examples thereof include N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide and the like. It is done. These organic solvents may be used alone or in combination of two or more.
  • an imidization catalyst an organic phosphorus-containing compound, inorganic fine particles, and the like may be added to the polyamic acid solution as long as it is thermal imidization.
  • a cyclization catalyst In the polyamic acid solution, if necessary, a cyclization catalyst, a dehydrating agent, inorganic fine particles, and the like may be added in the case of chemical imidization.
  • the imidization catalyst examples include a substituted or unsubstituted nitrogen-containing heterocyclic compound, an N-oxide compound of the nitrogen-containing heterocyclic compound, a substituted or unsubstituted amino acid compound, an aromatic hydrocarbon compound having a hydroxyl group, or an aromatic heterocyclic compound.
  • Cyclic compounds such as 1,2-dimethylimidazole, N-methylimidazole, N-benzyl-2-methylimidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 5-methylbenzimidazole, etc.
  • Benzimidazoles such as alkylimidazole and N-benzyl-2-methylimidazole, isoquinoline, 3,5-dimethylpyridine, 3,4-dimethylpyridine, 2,5-dimethylpyridine, 2,4-dimethylpyridine, 4-n- Substituted pyridines such as propylpyridine It can be used to apply.
  • the amount of the imidization catalyst used is preferably about 0.01 to 2 times equivalent, particularly about 0.02 to 1 time equivalent to the amic acid unit of the polyamic acid.
  • organic phosphorus-containing compounds examples include monocaproyl phosphate, monooctyl phosphate, monolauryl phosphate, monomyristyl phosphate, monocetyl phosphate, monostearyl phosphate, triethylene glycol monotridecyl Monophosphate of ether, monophosphate of tetraethylene glycol monolauryl ether, monophosphate of diethylene glycol monostearyl ether, dicaproyl phosphate, dioctyl phosphate, dicapryl phosphate, dilauryl phosphate, dimyristyl phosphate, Dicetyl phosphate, distearyl phosphate, diethylene phosphate of tetraethylene glycol mononeopentyl ether, trie Diphosphate of glycol mono tridecyl ether, diphosphate of tetraethyleneglycol monolauryl ether, and phosphoric acid esters such as diphosphate esters of diethylene glycol monostearyl
  • amine ammonia, monomethylamine, monoethylamine, monopropylamine, monobutylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, monoethanolamine, diethanolamine, triethanolamine Etc.
  • Cyclization catalysts include aliphatic tertiary amines such as trimethylamine and triethylenediamine, aromatic tertiary amines such as dimethylaniline, and heterocyclic tertiary amines such as isoquinoline, pyridine, ⁇ -picoline and ⁇ -picoline. Etc.
  • dehydrating agent examples include aliphatic carboxylic acid anhydrides such as acetic anhydride, propionic anhydride, and butyric anhydride, and aromatic carboxylic acid anhydrides such as benzoic anhydride.
  • Inorganic fine particles include fine particle titanium dioxide powder, silicon dioxide (silica) powder, magnesium oxide powder, aluminum oxide (alumina) powder, inorganic oxide powder such as zinc oxide powder, fine particle silicon nitride powder, and titanium nitride powder.
  • Inorganic nitride powder such as silicon carbide powder, inorganic carbide powder such as silicon carbide powder, and inorganic salt powder such as particulate calcium carbonate powder, calcium sulfate powder, and barium sulfate powder.
  • These inorganic fine particles may be used in combination of two or more. In order to uniformly disperse these inorganic fine particles, a means known per se can be applied.
  • the self-supporting film of the polyamic acid solution is a degree to which the polyamic acid solution or the polyamic acid solution composition is cast-coated on the support and becomes self-supporting (meaning a stage before a normal curing process), for example It is manufactured by heating to such an extent that it can be peeled off from the support.
  • the solid content concentration of the polyamic acid solution used in the present invention is not particularly limited as long as it is in a viscosity range suitable for production, but is usually preferably 10% by mass to 30% by mass, and preferably 15% by mass to 27% by mass. More preferably, 18% by mass to 26% by mass is more preferable.
  • the heating temperature and heating time at the time of preparing the self-supporting film can be appropriately determined.
  • the heating may be performed at a temperature of 100 to 180 ° C. for about 1 to 60 minutes.
  • the support is not particularly limited as long as it can cast a polyamic acid solution, but a smooth substrate is preferably used.
  • a metal drum or belt such as stainless steel is used.
  • the self-supporting film is not particularly limited as long as the solvent is removed and / or imidized to such an extent that it can be peeled off from the support, but in thermal imidization, the loss on heating is 20 to 50 mass. %, More preferably, the weight loss on heating is in the range of 20 to 50% by mass, and the imidization ratio is in the range of 7 to 55%. If the weight loss and imidization rate of the self-supporting film are within the above ranges, the mechanical properties of the self-supporting film will be sufficient, and the surface treatment agent solution should be uniformly and clean on the top surface of the self-supporting film. It becomes easy to apply, and generation of foaming, cracks, crazes, cracks, cracks and the like is not observed in the polyimide film obtained after imidization.
  • the loss on heating of the self-supporting film is a value obtained by the following formula from the mass W1 of the self-supporting film and the mass W2 of the film after curing.
  • Heat loss (mass%) ⁇ (W1-W2) / W1 ⁇ ⁇ 100
  • the imidation ratio of the self-supporting film is calculated by measuring the IR spectrum of the self-supporting film and its full-cure product (polyimide film) by the ATR method, and using the ratio of the vibration band peak area or height. be able to.
  • a solution of a surface treatment agent such as a coupling agent is applied to one side or both sides of the self-supporting film thus obtained.
  • an organic solvent which is a water-soluble liquid and has a surface tension at 20 ° C. of 32 mN / m or less and a boiling point of 125 ° C. or more can be used.
  • a water-soluble liquid is one that maintains a uniform appearance even after being left at normal temperature and normal pressure (20 ° C, 1 atm) and gently mixed with the same volume of pure water and allowed to stand.
  • a water-soluble liquid as a coating solvent is also preferable from the viewpoint of safety.
  • the coating solvent has a surface tension at 20 ° C. of 32 mN / m or less, preferably 31.5 mN / m or less, more preferably 31.3 mN / m or less. If the surface tension of the coating solvent is too high, the solution will bounce during coating, and the surface treatment solution may not be evenly and cleanly applied to the surface of the self-supporting film. The remaining polyimide film with a uniform surface may not be obtained.
  • the lower limit of the surface tension of the coating solvent at 20 ° C. is not particularly limited, but is preferably 20 mN / m or more, more preferably 25 mN / m or more.
  • the surface tension can be measured by a capillary rise method, a ring method, a vertical plate method, a liquid suitability method, a bubble pressure method, or the like.
  • the coating solvent has a boiling point of 125 ° C or higher, preferably 130 ° C or higher, more preferably 140 ° C or higher, still more preferably 150 ° C or higher, particularly preferably 160 ° C or higher. If the boiling point of the solvent is too low, after applying the surface treatment agent solution to the self-supporting film, it is too fast to dry, the time for the solvent to exist as a reaction field for the surface treatment agent is insufficient, and the properties of the resulting film are May decrease.
  • the specific evaporation rate of the solvent used in the present invention is 0.5 or less, preferably 0.4 or less, where n-butyl acetate is 1.
  • the evaporation rate is usually represented by a ratio (mass%) of evaporation of the solvent and a time required to evaporate to the ratio.
  • the evaporation rate is often expressed as a specific evaporation rate as compared with a reference solvent such as n-butyl acetate.
  • the evaporation rate and specific evaporation rate can be measured according to ASTM D3539-87.
  • the solvent must be volatilized during the heat treatment for imidization, and in particular, when a polyimide film is continuously produced, a surface treatment agent solution is applied to the surface of the self-supporting film, and then the coater is used. It is preferable to dry the film and then perform heat treatment for imidization in a curing furnace. Therefore, the boiling point of the solvent is preferably 300 ° C. or lower, more preferably 250 ° C. or lower, and particularly preferably 220 ° C. or lower.
  • a coating solvent a solution of a polyamic acid obtained by reacting the same tetracarboxylic acid component and diamine component used for the production of a polyimide film, the final cured polyimide film has a thickness of 10 to 14 ⁇ m.
  • the loss on heating was 39 to 43% by mass, and the imidization of the surface that was in contact with the glass substrate (also referred to as B surface).
  • a coating solvent is applied to the B surface, the four sides of the coating film are fixed with a pin tenter, and immediately heated at 200 ° C. or higher, cracks are observed. It is preferable to use those that are not.
  • the flash point of the coating solvent is preferably 21 ° C. or higher, more preferably 70 ° C. or higher at 1 atmosphere. A solvent with a low flash point is difficult to use from an industrial viewpoint in the industrial film forming process.
  • the contact angle of the coating solvent is preferably 61 ° or less, more preferably 60.5 ° or less at 23 ° C.
  • the contact angle of the coating solvent is within the above range, a more excellent polyimide film can be obtained.
  • the lower limit of the contact angle of the coating solvent is not particularly limited, it is preferably 40 ° or more, more preferably 50 ° or more at 23 ° C.
  • the contact angle of the coating solvent is obtained by measuring the contact angle of the solvent on the polytetrafluoroethylene sheet with, for example, a contact angle meter CA-X manufactured by Kyowa Interface Science Co., Ltd.
  • glycol monoalkyl ethers such as ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, (2) ether alcohols such as glycol dialkyl ethers such as diethylene glycol dimethyl ether and diethylene glycol diethyl ether; (3) ether esters such as diethylene glycol monoethyl ether acetate, (4) Ketones such as diacetone alcohol.
  • glycol monoalkyl ethers such as ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether
  • ether alcohols such as glycol dialkyl ethers such as diethylene glycol dimethyl ether and diethylene glycol diethyl ether
  • ether esters such as diethylene glycol monoethyl ether
  • glycol monoalkyl ethers such as ethylene glycol monoethyl ether and ethylene glycol mono-n-butyl ether, ether esters such as diethylene glycol monoethyl ether acetate, and ketones such as diacetone alcohol can be preferably used.
  • At least one of ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monoethyl ether acetate, and diacetone alcohol can be preferably used.
  • the coating solvent may be a mixed solvent of two or more.
  • the coating solvent satisfies the above conditions, amides such as N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylformamide, alcohols having 1 to 6 carbon atoms, etc. It may contain other organic solvents such as alcohols. However, the amount thereof is preferably 25% by mass or less, more preferably 10% by mass or less, in 100% by mass of the solvent for the solution of the surface treatment agent.
  • the surface treatment agent can be applied to the solidified film without using a surfactant as the coating solvent.
  • a surface treating agent can be applied to the solidified film using a surfactant.
  • the surfactant include silicone, fluorine, and hydrocarbon surfactants, and those that decompose and volatilize during the heat treatment for imidization are preferable.
  • the surface treatment agent segregates on the film surface. Obtainable.
  • the solution of the surface treatment agent applied to the self-supporting film has a water content of 20% by mass or less, more preferably 10% by mass or less, and particularly preferably 5% by mass or less.
  • various coupling agents such as silane coupling agents, borane coupling agents, aluminum coupling agents, aluminum chelating agents, titanate coupling agents, iron coupling agents, copper coupling agents, and chelating agents. Examples thereof include a treatment agent that improves adhesiveness and adhesion of the agent.
  • the surface treatment agents can be used alone or in admixture of two or more.
  • a coupling agent such as a silane coupling agent is preferably used as the surface treatment agent.
  • silane coupling agents include epoxy silane couplings such as ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropylmethyldiethoxysilane, and ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane.
  • Vinyl silane coupling agent such as vinyltrichlorosilane, vinyltris ( ⁇ -methoxyethoxy) silane, vinyltriethoxysilane, vinyltrimethoxysilane; Acrylic silane coupling agent such as ⁇ -methacryloxypropyltrimethoxysilane; N - ⁇ - (aminoethyl) - ⁇ -aminopropyltrimethoxysilane, N- ⁇ - (aminoethyl) - ⁇ -aminopropylmethyldimethoxysilane, N-phenyl- ⁇ -aminopropyltriethoxysilane, N-phenyl- ⁇ -Aminopropyl Limethoxysilane, N- ⁇ - (aminoethyl) - ⁇ -aminopropyltriethoxysilane, N- (aminocarbonyl) - ⁇ -aminopropyltriethoxysilane, N- [ ⁇ - (phenyl
  • Titanate coupling agents include isopropyl triisostearoyl titanate, isopropyl tridecylbenzenesulfonyl titanate, isopropyl tris (dioctylpyrophosphate) titanate, tetraisopropylbis (dioctyl phosphite) titanate, tetra (2,2-diallyloxymethyl- Examples thereof include 1-butyl) bis (di-tridecyl) phosphite titanate, bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate, isopropyltrioctanoyl titanate, isopropyltricumylphenyl titanate, and the like.
  • silane coupling agents particularly N- ⁇ - (aminoethyl) - ⁇ -aminopropyl-triethoxysilane, N- (aminocarbonyl) - ⁇ -aminopropyltriethoxysilane, N- [ ⁇ - (Phenylamino) -ethyl] - ⁇ -aminopropyltriethoxysilane, N-phenyl- ⁇ -aminopropyltriethoxysilane, N-phenyl- ⁇ -aminopropyltrimethoxysilane, N- ⁇ - (aminoethyl) - ⁇ Aminosilane coupling agents such as aminopropyl-trimethoxysilane, ⁇ -aminopropyl-trimethoxysilane, and ⁇ -aminopropyl-triethoxysilane are preferred, and in particular, N-phenyl- ⁇ -aminopropyltrimethoxys
  • the surface treatment agent solution such as a coupling agent or a chelating agent preferably has a surface treatment agent content of 0.1 to 60% by mass, more preferably 0.3 to 20% by mass, particularly preferably 0.5 to 15%. It is in the range of 1% by mass, more preferably 1-10% by mass.
  • the surface treating agent solution has a surface treating agent content of 0.1 to 60% by mass, more preferably 0.3 to It is preferably 20% by mass, more preferably 0.5 to 10% by mass, particularly preferably 1 to 5% by mass.
  • the content of the surface treatment agent is 0.5 to 60% by mass, more preferably 1%. It is preferably 20 to 20% by mass, particularly preferably 1 to 15% by mass, and further preferably 2 to 10% by mass.
  • the content of the surface treatment agent is 1 to 60% by mass, more preferably 2 to 20%. It is preferably 2% by mass, particularly preferably 2 to 15% by mass, and further preferably 2 to 10% by mass.
  • the rotational viscosity (solution viscosity measured with a rotational viscometer at a measurement temperature of 25 ° C.) of the solution of the surface treatment agent may be any viscosity that can be applied to the self-supporting film, and is preferably 0.5 to 50000 centipoise.
  • the solution of the surface treatment agent may contain other additive components in addition to the surface treatment agent as long as the properties of the present invention are not impaired.
  • the coating amount of the surface treatment agent solution can be appropriately determined.
  • the surface on the side of the self-supporting film in contact with the support and the opposite surface are preferably 1 to 50 g / m 2. 30 g / m 2 is more preferable, and 3 to 20 g / m 2 is particularly preferable.
  • the amount applied may be the same on both sides or different.
  • coating should just be the temperature which can apply
  • the solution of the surface treatment agent can be applied to the self-supporting film by a known method, for example, gravure coating method, spin coating method, silk screen method, dip coating method, spray coating method, bar coating method, knife coating.
  • a known method for example, gravure coating method, spin coating method, silk screen method, dip coating method, spray coating method, bar coating method, knife coating.
  • known coating methods such as a method, a roll coating method, a blade coating method, and a die coating method.
  • the self-supporting film coated with the surface treating agent solution is then heat-treated to obtain a polyimide film.
  • the heat treatment it is appropriate to first gradually perform imidization of the polymer and evaporation / removal of the solvent at a temperature of about 100 ° C. to 400 ° C. for about 0.05 to 5 hours, particularly 0.1 to 3 hours. .
  • the heat treatment is stepwise first heat treated at a relatively low temperature of about 100 ° C. to about 170 ° C. for about 0.5-30 minutes, and then at a temperature of 170 ° C.-220 ° C. for about 0.5 ° C. It is preferable that the second heat treatment is performed for ⁇ 30 minutes, and then the third heat treatment is performed at a high temperature of 220 ° C. to 400 ° C. for about 0.5 to 30 minutes. If necessary, the fourth high-temperature heat treatment may be performed at a high temperature of 400 ° C. to 550 ° C.
  • pin ends, clips, frames, etc. are used to fix at least the edges in the direction perpendicular to the longitudinal direction of the long solid film, that is, the width direction of the film, If necessary, the heat treatment may be performed by expanding and contracting in the width direction and / or the length direction.
  • the thickness of the polyimide film of the present invention is not particularly limited, but is about 3 to 250 ⁇ m, preferably about 4 to 150 ⁇ m, more preferably about 5 to 125 ⁇ m, and still more preferably about 5 to 100 ⁇ m. According to the present invention, a polyimide film having excellent adhesiveness can be obtained even with a thin film having a thickness of 20 ⁇ m or less, further 15 ⁇ m or less, and further 10 ⁇ m or less. Even with a thin film of 6 to 16 ⁇ m, a polyimide film having excellent adhesion can be obtained.
  • the surface of the polyimide film of the present invention to which the surface treatment agent is applied may be further subjected to sand plast treatment, corona treatment, plasma treatment, etching treatment or the like.
  • a compound derived from a surface treatment agent for example, Si when a silane coupling agent is used
  • a layer in which Si is present at a high concentration on the coated surface side is 1 nm to 1 ⁇ m, preferably 5 nm to 900 nm, more preferably 10 nm to 800 nm, particularly preferably.
  • a polyimide film having a surface Si concentration (in terms of Si atom) of 0.1 to 50%, preferably 1 to 20%, particularly preferably 2 to 15%, and more preferably 3 to 10% can be obtained.
  • the Si concentration on the surface of the polyimide film can be measured with a scanning X-ray photoelectron spectrometer.
  • the surface of the polyimide film of the present invention on which the surface treatment agent is applied is excellent in adhesiveness with the adhesive. Therefore, an adhesive layer can be provided directly on the surface of the polyimide film surface treatment agent applied, providing excellent initial peel strength between the polyimide film and the adhesive layer and peeling even after high-temperature treatment or high-temperature and high-humidity treatment.
  • a polyimide laminate having excellent strength and a small decrease in peel strength can be obtained.
  • the thickness of the polyimide film is not particularly limited, but may be, for example, 25 ⁇ m or less, further 20 ⁇ m or less, and further 15 ⁇ m or less.
  • the polyimide laminate further laminates other substrates such as glass substrates, silicon wafers and other ceramics, metal foils, resin films, carbon fibers, glass fibers, resin fibers and other woven fabrics and nonwoven fabrics through an adhesive layer. can do.
  • Another base material can be laminated
  • Examples of the pressure member or heating / pressure member include a pair of pressure-bonding metal rolls (the pressure-bonding part may be made of metal or ceramic sprayed metal), a double belt press, and a hot press. Among them, those that can be cooled are preferable, and among them, a hydraulic double belt press is particularly preferable.
  • the surface of the polyimide film on which the surface treatment agent is applied has good adhesion and adhesion, and in addition to the above, a photosensitive material, a thermocompression bonding material, and the like can be directly laminated.
  • the adhesive to be used is not particularly limited as long as it is a heat-resistant adhesive such as polyimide, epoxy, acrylic, polyamide, or urethane used in the electric / electronic field.
  • polyimide adhesive examples thereof include heat-resistant adhesives such as epoxy-modified polyimide adhesives, phenol-modified epoxy resin adhesives, epoxy-modified acrylic resin adhesives, and epoxy-modified polyamide adhesives.
  • the adhesive layer can be provided by an arbitrary method implemented in the electronic field itself. For example, an adhesive solution may be applied and dried on the surface of the polyimide film surface treatment agent to be applied. The film-like adhesive formed on may be bonded together.
  • Examples of the metal foil to be bonded to the polyimide film include single metals or alloys such as copper, aluminum, gold, silver, nickel, and stainless steel, but copper such as rolled copper foil and electrolytic copper foil is preferable. A foil is mentioned.
  • the thickness of the metal foil is not particularly limited, but is preferably 0.1 ⁇ m to 10 mm, particularly 10 to 60 ⁇ m.
  • a metal or resin carrier can be used to improve handling.
  • the surface of the polyimide film of the present invention on which the surface treatment agent is applied is excellent in adhesion to metal. Therefore, the metal layer can be provided directly on the surface of the polyimide film surface treatment agent applied side by metallizing method or wet plating method, and the initial peel strength between the polyimide film and the metal layer is excellent, after high temperature treatment or at high temperature It is possible to obtain a polyimide metal laminate that has excellent peel strength even after high-humidity treatment and has a small decrease in peel strength.
  • the peel strength after high-temperature treatment of the laminate may be higher than that before high-temperature treatment.
  • the metallizing method is a method of providing a metal layer different from the wet plating method or the lamination of metal foil, and known methods such as vacuum deposition, sputtering, ion plating, and electron beam can be used.
  • Metals used in the metalizing method include metals such as copper, nickel, chromium, manganese, aluminum, iron, molybdenum, cobalt, tungsten, vanadium, titanium, tantalum, alloys thereof, oxides of these metals, and the like. Although the metal carbide of these can be used, it is not limited to these materials.
  • the thickness of the metal layer formed by the metalizing method can be appropriately selected according to the purpose of use, and is preferably 1 to 1000 nm, more preferably 5 to 500 nm, because it is suitable for practical use.
  • the number of metal layers formed by the metalizing method can be appropriately selected according to the purpose of use, and may be one layer, two layers, or three or more layers.
  • the first layer is made of nickel, chromium, manganese, aluminum, iron, molybdenum, cobalt, tungsten, vanadium, titanium, tantalum or the like, or an alloy thereof, or an oxide of these metals.
  • These metal carbides are preferably used, and copper or a copper alloy, or an oxide of these metals, a carbide of these metals, or the like is preferably used for the second layer.
  • a metal layer such as copper of about 1 to 40 ⁇ m can be provided on the second layer by wet plating.
  • the wet plating method a known plating method can be used, and examples thereof include electrolytic plating and electroless plating, and these can also be combined.
  • the metal used in the wet plating method is not limited as long as it is a metal that can be wet plated.
  • the thickness of the metal layer formed by the wet plating method can be appropriately selected according to the purpose of use, and is preferably in the range of 0.1 to 50 ⁇ m, more preferably 1 to 30 ⁇ m because it is suitable for practical use.
  • the number of metal layers formed by the wet plating method can be appropriately selected according to the purpose of use, and may be one layer, two layers, or three or more layers.
  • wet plating method there is no particular limitation on the wet plating method, and a known wet plating process can be used.
  • a known wet plating process can be used.
  • an elf seed process manufactured by Sugawara Eugleite Co., Ltd. or a catalyst bond process which is a surface treatment process of Nikko Metal Co., Ltd.
  • Examples include a method of performing electroless copper plating later.
  • the Elf Seed Process (Hagiwara Eugelite Co., Ltd.) is a process in which the surface of a polyimide film is modified, a catalyst is applied and reduced, and then electroless nickel plating is performed. Obtainable. Also, in order to ensure adhesion between the electroless nickel layer and the electrolytic copper plating layer, an electroless copper plating layer is formed between the electroless nickel plating and the electrolytic copper plating by reducing copper plating or displacement copper plating. Moreover, you may put the process of activating an electroless nickel plating membrane
  • the catalyst bond process (Nikko Metals Co., Ltd.) is a pretreatment process for plating. By pretreatment, it improves the adsorptivity of palladium, which is a wet plating catalyst, and provides catalyst after the process, by electroless and electrolytic copper plating. A conductive metal layer can be obtained.
  • the polyimide film, polyimide metal laminate and polyimide laminate of the present invention are printed wiring boards, flexible printed circuit boards, TAB tapes, COF tapes or metal wirings, and covers such as metal wirings and chip members such as IC chips. It can be used as a material for electronic parts such as base materials such as base materials, liquid crystal displays, organic electroluminescence displays, electronic paper, and solar cells, and electronic devices.
  • the linear expansion coefficient of the polyimide film may be appropriately selected according to the purpose of use.
  • the linear expansion coefficient of the polyimide film Is preferably close to the linear expansion coefficient of a chip member such as a metal wiring or an IC chip.
  • both MD and TD are preferably 40 ppm / ° C. or less, more preferably 0 to 30 ppm / ° C. More preferably, it is 5 to 25 ppm / ° C., and particularly preferably 8 to 20 ppm / ° C.
  • the linear expansion coefficient of the polyimide film is preferably close to the linear expansion coefficient of glass or silicon.
  • a polyimide film having a linear expansion coefficient of 0 to 10 ppm / ° C. can also be obtained.
  • the physical properties of the polyimide film were evaluated according to the following methods.
  • the peel strength is a peel strength at 90 ° peel, and was measured at a peel rate of 50 mm / min in an environment of a temperature of 23 ° C. and a humidity of 50% RH.
  • the surface on the air side when the polyamic acid solution was cast on the support was the A surface
  • the surface on the support side was the B surface
  • the adhesion mode is good in the order of 3) ⁇ 4) ⁇ 1) ⁇ 2).
  • the polyimide laminate A was treated in a hot air dryer at 150 ° C. for 24 hours, and then the peel strength was measured.
  • polyimide laminate B (3-layer laminate of polyimide film / adhesive layer / copper foil) (Preparation of polyimide laminate B) Overlay the surface of the polyimide film surface treatment agent in the order of DuPont acrylic adhesive (Pyrarax LF0100) and Nikko Metal Rolled copper foil (BHY-13H-T, 18 ⁇ m thick).
  • the polyimide laminate B was obtained by press-bonding at 180 ° C. and 9 MPa for 5 minutes and further heat-treating at 180 ° C. for 60 minutes.
  • the peel strength of the polyimide laminate B was measured and used as the initial peel strength B.
  • the polyimide laminate B was treated in a hot air dryer at 150 ° C. for 24 hours, and then the peel strength was measured to obtain a post-heat-resistant peel strength B1.
  • the polyimide laminate B was treated in a hot air dryer at 150 ° C. for 168 hours, and then the peel strength was measured to obtain post-heat-resistant peel strength B2.
  • the polyimide laminate B was treated for 24 hours in an environment of 121 ° C. and 100% RH using a pressure cooker test apparatus, and then the peel strength was measured to obtain a cooker peel strength B1.
  • the polyimide laminate B was treated for 96 hours in an environment of 121 ° C. and 100% RH using a pressure cooker test apparatus, and then the peel strength was measured to obtain a cooker peel strength B2.
  • the peel strength of the polyimide metal laminate C was measured and used as the initial peel strength C.
  • the polyimide metal laminate C was treated in a hot air dryer at 150 ° C. for 24 hours, and then the peel strength was measured to obtain a post-heat-resistant peel strength C1.
  • the polyimide metal laminate C was treated in a hot air dryer at 150 ° C. for 168 hours, and then the peel strength was measured to obtain a post-heat-resistant peel strength C2.
  • the polyimide metal laminate C was treated in an environment of 121 ° C. and 100% RH for 24 hours using a pressure cooker test apparatus, and then the peel strength was measured to obtain a cooker peel strength C1.
  • the polyimide metal laminate C was treated for 96 hours in an environment of 121 ° C. and 100% RH using a pressure cooker test apparatus, and then the peel strength was measured to obtain a cooker peel strength C2.
  • the peel strength of the polyimide metal laminate D was measured and used as the initial peel strength D.
  • the polyimide metal laminate D was treated in a hot air dryer at 150 ° C. for 24 hours, and then the peel strength was measured to obtain a post-heat-resistant peel strength D1.
  • the polyimide metal laminate D was treated in a hot air dryer at 150 ° C. for 168 hours, and then the peel strength was measured to obtain a post-heat-resistant peel strength D2.
  • the solution (coating solution) to be applied to the self-supporting film is a mixture of a coating solvent, a silane coupling agent that is a surface treatment agent, and a surfactant (manufactured by Dow Corning Toray: L7001) at a blending ratio shown in Table 1. And stirred until a uniform solution was obtained at room temperature.
  • the FT-IR spectrum of the self-supporting film and its full-cure film was measured by a multiple reflection ATR method using a FT / IR6100 manufactured by JASCO Corporation with a Ge crystal and an incident angle of 45 °, and was 1775 cm ⁇ 1.
  • the imidization ratio was calculated by the following formula (1).
  • Imidation rate (%) ⁇ (X1 / X2) / (Y1 / Y2) ⁇ ⁇ 100 (1)
  • X1 peak height of 1775 cm ⁇ 1 of the self-supporting film
  • X2 peak height of 1515 cm ⁇ 1 of the self-supporting film
  • Y1 peak height of 1775 cm ⁇ 1 of the full cure film
  • Y2 The peak height of 1515 cm ⁇ 1 of the full cure film.
  • the self-supporting films used in the following examples, comparative examples and reference examples have an imidation ratio in the range of 7 to 55% even if not described.
  • Example 1 The polyamic acid solution composition A is continuously cast from the slit of the T-die mold, extruded onto a smooth belt-like metal support in a drying furnace to form a thin film, heated at 145 ° C. for a predetermined time, and then supported. The film was peeled from the body to obtain a self-supporting film. The heat loss of the obtained self-supporting film was 29.0% by mass, and the imidization ratio of the self-supporting film was 13.3% on the A side and 22.0% on the B side.
  • the coating liquid 1 was applied to the B surface of the self-supporting film using a die coater (coating amount: 6 g / m 2 ), and passed through a 40 ° C. drying oven. did.
  • the both ends of the self-supporting film in the width direction are gripped and inserted into a continuous heating furnace (curing furnace), and the film is heated and imidized under a condition that the maximum heating temperature is 480 ° C. from 100 ° C., A long polyimide film (PI-1) having an average film thickness of 8 ⁇ m was produced.
  • a polyimide laminate A (PI-1) in which a coverlay was laminated was obtained in the same manner as in the preparation of the polyimide laminate A.
  • the peel strength of the polyimide laminate A (PI-1) was measured, and the results are shown in Table 2.
  • Example 2 A long polyimide film (PI-2) was produced in the same manner as in Example 1 except that the coating liquid 2 was used instead of the coating liquid 1. Further, a polyimide laminate A (PI-2) was obtained in the same manner as in Example 1. The peel strength of the polyimide laminate A (PI-2) was measured, and the results are shown in Table 2.
  • Example 1 A polyimide film (PI-3) was produced in the same manner as in Example 1 except that the coating liquid 3 was used in place of the coating liquid 1. As a result, repellency and tearing occurred after application of the coating liquid. The film also had repelling marks and tears, and a film having a uniform surface could not be obtained.
  • a polyimide film (PI-4) was produced in the same manner as in Example 1 except that nothing was applied to the self-supporting film and passed through a drying furnace at 40 ° C. Further, a polyimide laminate A (PI-4) was obtained in the same manner as in Example 1. The peel strength of the polyimide laminate A (PI-4) was measured, and the results are shown in Table 2.
  • Example 3 The polyamic acid solution composition A is continuously cast from the slit of the T-die mold, extruded onto a smooth belt-like metal support in a drying furnace to form a thin film, heated at 145 ° C. for a predetermined time, and then supported. The film was peeled from the body to obtain a self-supporting film.
  • the heat loss of the obtained self-supporting film was 30.5% by mass, and the imidization ratio of the self-supporting film was 11.5% on the A side and 30.2% on the B side.
  • the coating liquid 1 was applied to the B surface of the self-supporting film using a die coater (coating amount: 6 g / m 2 ), and passed through a 40 ° C. drying oven. did.
  • a polyimide laminate A (PI-5) in which a coverlay was laminated was obtained in the same manner as in the preparation of the polyimide laminate A.
  • the peel strength of the polyimide laminate A (PI-5) was measured, and the results are shown in Table 2.
  • Example 4 In the same manner as in Example 3, a self-supporting film having a weight loss by heating of 29.0% by mass, an imidization ratio of the self-supporting film of 15.4% on the A side and 34.0% on the B side was obtained.
  • a polyimide film (PI-6) having an average film thickness of 12.5 ⁇ m was obtained in the same manner as in Example 3 except that the coating liquid 2 was used as the coating solution for the self-supporting film.
  • a polyimide laminate A (PI-6) in which a coverlay was laminated was obtained in the same manner as in the preparation of the polyimide laminate A.
  • the peel strength of the polyimide laminate A (PI-6) was measured, and the results are shown in Table 2.
  • Example 5 A long polyimide film (PI-7) having an average film thickness of 12.5 ⁇ m was produced in the same manner as in Example 3 except that the coating liquid 4 was used in place of the coating liquid 1, and a polyimide film ( A polyimide laminate A (PI-7) was produced from PI-7). The peel strength of the polyimide laminate A (PI-7) was measured, and the results are shown in Table 2.
  • Example 6 A long polyimide film (PI-8) having an average film thickness of 12.5 ⁇ m was produced in the same manner as in Example 3 except that the coating liquid 5 was used in place of the coating liquid 1, and a polyimide film ( A polyimide laminate A (PI-8) was produced from PI-8). The peel strength of the polyimide laminate A (PI-8) was measured, and the results are shown in Table 2.
  • Example 2 A polyimide film (PI-9) was produced in the same manner as in Example 3 except that the coating liquid 3 was used instead of the coating liquid 1. As a result, repellency occurred after application of the coating liquid, and the cured film A repelling trace remained and a film having a uniform surface could not be obtained.
  • Example 2 A polyimide film (PI-10) was produced in the same manner as in Example 3 except that nothing was applied to the self-supporting film and passed through a drying furnace at 40 ° C., and further from the polyimide film (PI-10). A polyimide laminate A (PI-10) was produced. The peel strength of the polyimide laminate A (PI-10) was measured, and the results are shown in Table 2.
  • Example 7 The polyamic acid solution composition A was cast into a thin film on a glass plate, heated at 138 ° C. for 60 seconds using a hot plate, and then peeled off from the glass plate. The weight loss on heating was 33.9% by mass, the imidization rate Produced a self-supporting film of 14.9% on the A side and 24.3% on the B side.
  • the coating liquid 6 was applied to the surface B of this self-supporting film using a bar coater no. 3 (coating amount: 6 g / m 2 ), fixing the four sides with a pin tenter, using an oven for 140 seconds at 100 ° C., 50 seconds at 155 ° C., 50 seconds at 210 ° C., 50 seconds at 370 ° C. Heat imidization was carried out stepwise at 490 ° C. for 50 seconds to obtain a polyimide film (PI-11) having an average film thickness of 13 ⁇ m.
  • PI-11 polyimide film having an average film thickness of 13 ⁇ m.
  • a polyimide laminate A (PI-11) having a coverlay laminated was obtained in the same manner as in the preparation of the polyimide laminate A.
  • the peel strength of the polyimide laminate A (PI-11) was measured, and the results are shown in Table 2.
  • Example 8 In the same manner as in Example 7, a self-supporting film having a heat loss of 33.3% by mass was obtained.
  • a polyimide laminate A (PI-12) in which a coverlay was laminated was obtained in the same manner as in the preparation of the polyimide laminate A.
  • the peel strength of the polyimide laminate A (PI-12) was measured, and the results are shown in Table 2.
  • Example 9 In the same manner as in Example 7, a self-supporting film having a loss on heating of 34.5% by mass was obtained.
  • a polyimide laminate A (PI-13) in which a coverlay was laminated was obtained in the same manner as in the preparation of the polyimide laminate A.
  • the peel strength of the polyimide laminate A (PI-13) was measured, and the results are shown in Table 2.
  • Example 10 A self-supporting film having a loss on heating of 35.6% by mass was obtained in the same manner as in Example 7.
  • a polyimide film (PI-14) having an average film thickness of 16 ⁇ m was obtained in the same manner as in Example 7 except that the coating liquid 8 was used as the coating solution for the self-supporting film.
  • a polyimide laminate A (PI-14) having a coverlay laminated was obtained in the same manner as in the preparation of the polyimide laminate A.
  • the peel strength of the polyimide laminate A (PI-14) was measured, and the results are shown in Table 2.
  • Example 3 A self-supporting film having a heat loss of 33.2% by mass was obtained in the same manner as in Example 7.
  • the coating liquid 3 was applied to the surface B of this self-supporting film using a bar coater No.
  • repelling occurred after application of the coating solution.
  • PI-16 polyimide laminate A having a coverlay laminated was obtained in the same manner as in the preparation of the polyimide laminate A.
  • the peel strength of the polyimide laminate A (PI-16) was measured, and the results are shown in Table 2.
  • Example 11 A self-supporting film having a loss on heating of 34.7% by mass was obtained in the same manner as in Example 7.
  • the coating liquid 6 was applied to the A side of this self-supporting film with a bar coater No. 3 (application amount: 6 g / m 2 ), and a polyimide film (PI-17) having an average film thickness of 14 ⁇ m was obtained in the same manner as in Example 7.
  • a polyimide laminate A (PI-17) having a coverlay laminated was obtained in the same manner as in the preparation of the polyimide laminate A.
  • the peel strength of the polyimide laminate A (PI-17) was measured, and the results are shown in Table 2.
  • Example 12 A self-supporting film having a loss on heating of 31.5% by mass was obtained in the same manner as in Example 7.
  • a polyimide film (PI-18) having an average film thickness of 10 ⁇ m was obtained in the same manner as in Example 11 except that the coating liquid 2 was used as the coating solution for the self-supporting film.
  • a polyimide laminate A (PI-18) having a coverlay laminated was obtained in the same manner as in the preparation of the polyimide laminate A.
  • the peel strength of the polyimide laminate A (PI-18) was measured, and the results are shown in Table 2.
  • Example 13 A self-supporting film having a loss on heating of 36.0% by mass was obtained in the same manner as in Example 7.
  • a polyimide film (PI-19) having an average film thickness of 14 ⁇ m was obtained in the same manner as in Example 11 except that the coating liquid 9 was used as a coating solution for the self-supporting film.
  • a polyimide laminate A (PI-19) having a coverlay laminated was obtained in the same manner as in the preparation of the polyimide laminate A.
  • the peel strength of the polyimide laminate A (PI-19) was measured, and the results are shown in Table 2.
  • Example 14 The polyamic acid solution composition A was cast into a thin film on a glass plate, heated at 138 ° C. for 120 seconds using a hot plate, then peeled off from the glass plate, and the loss on heating was 27.4% by mass. Obtained a self-supporting film of A side 17.7% and B side 25.0%.
  • the coating liquid 10 was applied to the surface B of this self-supporting film using a bar coater No. 3 (coating amount: 6 g / m 2 ), fixing the four sides with a pin tenter, and using an oven for 75 seconds at 40 ° C., 50 seconds at 140 ° C., 50 seconds at 210 ° C., 50 seconds at 370 ° C. Heat imidization was carried out stepwise at 490 ° C. for 50 seconds to obtain a polyimide film (PI-20) having an average film thickness of 7 ⁇ m.
  • PI-20 polyimide film having an average film thickness of 7 ⁇ m.
  • a polyimide laminate A (PI-20) having a coverlay laminated was obtained in the same manner as in the preparation of the polyimide laminate A.
  • the peel strength of the polyimide laminate A (PI-20) was measured, and the results are shown in Table 2.
  • Example 15 In the same manner as in Example 14, a self-supporting film having a heat loss of 28.3% by mass was obtained.
  • a polyimide laminate A (PI-21) having a coverlay laminated was obtained in the same manner as in the preparation of the polyimide laminate A.
  • the peel strength of the polyimide laminate A (PI-21) was measured, and the results are shown in Table 2.
  • Example 4 In the same manner as in Example 14, a self-supporting film having a loss on heating of 30.9% by mass was obtained.
  • the coating liquid 3 was applied to the surface B of this self-supporting film using a bar coater No.
  • repelling occurred after application of the coating solution.
  • a repelling mark remained on the polyimide film (PI-22) having an average film thickness of 8 ⁇ m obtained by curing in the same manner as in Example 14, and a film having a uniform surface could not be obtained.
  • a polyimide laminate A (PI-23) having a coverlay laminated was obtained in the same manner as in the preparation of the polyimide laminate A.
  • the peel strength of the polyimide laminate A (PI-23) was measured, and the results are shown in Table 2.
  • Example 7 Comparing Examples 7 to 10, the peel strength after the heat treatment is highest in Example 8, followed by Examples 7 and 9, and then Example 10. This is thought to be due to the difference in coating solvent.
  • Example 16 A self-supporting film was obtained in the same manner as in Example 1 except that the polyamic acid solution composition B was used.
  • the heat loss of the obtained self-supporting film was 29.6% by mass, and the imidization ratio was 15.9% on the A side and 33.0% on the B side.
  • a long polyimide film (PI-24) having an average film thickness of 12.5 ⁇ m was produced in the same manner as in Example 1 except that the coating liquid 12 was used as the coating solution for the self-supporting film.
  • Polyimide laminate B (polyimide film / adhesive layer / copper foil) in which a copper foil is laminated via an adhesive layer in the same manner as in the preparation of polyimide laminate B using a polyimide film (PI-24) (PI -24) was obtained.
  • the peel strength of the polyimide laminate B (PI-24) was measured, and the results are shown in Table 3.
  • Example 17 A polyimide film (PI-25) was produced in the same manner as in Example 16 except that the coating liquid 13 was used instead of the coating liquid 12. Using a polyimide film (PI-25), a polyimide laminate B (PI-25) in which a copper foil was laminated via an adhesive layer was obtained in the same manner as in the preparation of polyimide laminate B. The peel strength of the polyimide laminate B (PI-25) was measured, and the results are shown in Table 3.
  • Example 5 A polyimide film (PI-26) was produced in the same manner as in Example 16 except that the coating liquid 3 was used in place of the coating liquid 12. As a result, repelling occurred after application of the coating liquid, and the cured film was A repelling trace remained and a film having a uniform surface could not be obtained.
  • a polyimide film (PI-27) was produced in the same manner as in Example 16 except that nothing was applied to the self-supporting film and passed through a drying furnace at 40 ° C.
  • a polyimide film (PI-27) a polyimide laminate B (PI-27) in which a copper foil was laminated via an adhesive layer was obtained in the same manner as in the preparation of the polyimide laminate B.
  • the peel strength of the polyimide laminate B (PI-27) was measured, and the results are shown in Table 3.
  • Example 18 Polyamic acid solution A is continuously extruded from a slit of a T-die mold onto a smooth metal support in a casting / drying furnace to form a thin film, heated at 135 ° C. for a predetermined time, peeled off from the support and self-supported. A characteristic film was obtained. The heat loss of the obtained self-supporting film was 37.4% by mass, and the imidization ratio was 10.0% on the A side and 18.8% on the B side.
  • the coating liquid 12 was applied to the B surface using a die coater (coating amount: 6 g / m 2 ) and passed through a drying furnace at 40 ° C.
  • the both ends of the self-supporting film in the width direction are gripped and inserted into a continuous heating furnace (curing furnace), and the film is heated and imidized under a condition that the maximum heating temperature is 480 ° C. from 100 ° C., A long polyimide film (PI-28) having an average film thickness of 35 ⁇ m was produced.
  • PI-28 polyimide laminate B in which a copper foil was laminated via an adhesive layer was obtained in the same manner as in the preparation of the polyimide laminate B.
  • the peel strength of the polyimide laminate B (PI-28) was measured, and the results are shown in Table 3.
  • Example 6 A polyimide film (PI-29) was produced in the same manner as in Example 18 except that the coating liquid 3 was used instead of the coating liquid 12. Since the film thickness of the polyimide film (PI-29) was as thick as 35 ⁇ m, unlike Comparative Example 1 and the like, a film having a good appearance could be obtained. However, the initial peel strength was small.
  • PI-29 a polyimide metal laminate C (PI-29) in which a metal was laminated by a metalizing method was obtained in the same manner as the production of the polyimide metal laminate C.
  • Example 19 the type of coating solvent was changed, and Examples 19 and 20 had higher peel strength after the initial stage, after heat treatment and after high temperature and high humidity treatment than Example 21.
  • Example 19 the concentration of the surface treatment agent was changed, but compared with the results of the adhesives in Table 2, there seems to be no difference in peel strength depending on the concentration in this range.
  • Example 23 the concentration of the surface treatment agent was changed, but compared to the results of the adhesives in Table 2, there seems to be no difference in peel strength depending on the concentration in this range. The same as Table 4.
  • solvent evaporation rate Measured according to ASTM D3539-87.
  • the evaporation rate is data expressed in time (seconds) required for 90% by mass of the amount charged for measurement to evaporate.
  • the specific evaporation rate is data expressed as a specific evaporation rate using n-butyl acetate as a reference solvent.
  • Example 25 The polyamic acid solution A was cast into a thin film on a glass plate, heated at 131 ° C. for 210 seconds using a hot plate, and then peeled from the glass plate. As a result, a self-supporting film having a loss on heating of 38.0% by mass, an imidization ratio of 10.0% on the A side, and 18.0% on the B side was obtained.
  • the coating liquid 2 was applied to the side A of this self-supporting film using a bar coater No. 3 (application amount: 6 g / m 2 ). As a result, the surface treatment agent was not repelled on the surface of the self-supporting film, and the appearance was good.
  • Example 26 The same test as in Example 25 was performed except that the coating liquid 8 was changed. As a result, the surface treatment agent was not repelled on the surface of the self-supporting film, and the appearance was good. Also, the appearance of the cured polyimide film was good with no repelling marks.
  • Example 27 The same test as in Example 25 was performed except that the coating liquid 6 was changed. As a result, the surface treatment agent was not repelled on the surface of the self-supporting film, and the appearance was good. Also, the appearance of the cured polyimide film was good with no repelling marks.
  • Example 7 The same test as in Example 25 was performed except that the coating liquid 16 was changed. As a result, there was no repellency immediately after the surface treatment agent was applied to the self-supporting film, but repellency occurred 30 seconds after application. In addition, the appearance of the polyimide film after curing had a repelling mark, and the appearance was poor.
  • Example 8 The same test as in Example 25 was performed except that the coating liquid 17 was changed. As a result, when the surface treatment agent was applied to the self-supporting film, the coating liquid repelled on the surface of the self-supporting film. In addition, the appearance of the polyimide film after curing had a repelling mark, and the appearance was poor.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Laminated Bodies (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)

Abstract

La présente invention concerne un procédé pour produire un film de polyimide par coulée sur un corps de support d'une solution d'acide polyamique obtenue par réaction d'un composant d'acide tétracarboxylique et d'un composant diamine, séchage de ladite solution pour obtenir un film rigide, et ensuite application d'une solution d'un agent de traitement de surface sur un ou les deux côtés dudit film rigide et application de chaleur. En tant que solvant de la solution d'agent de traitement de surface, un liquide hydrosoluble est utilisé ayant, à 20 °C, une tension superficielle de 32 mN/m ou moins et un point d'ébullition de 125 °C ou plus ; cela permet la production d'un film de polyimide ayant une excellente adhésion.
PCT/JP2010/072049 2009-12-09 2010-12-08 Procédé pour produire un film de polyimide, et film de polyimide WO2011071087A1 (fr)

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CN201080062735.7A CN102741330B (zh) 2009-12-09 2010-12-08 用于制备聚酰亚胺膜的方法和聚酰亚胺膜
US13/514,756 US20120244352A1 (en) 2009-12-09 2010-12-08 Process for producing polyimide film, and polyimide film
JP2011545230A JP5609891B2 (ja) 2009-12-09 2010-12-08 ポリイミドフィルムの製造方法、およびポリイミドフィルム

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CN104292488A (zh) * 2014-08-25 2015-01-21 哈尔滨工业大学 一种表面高导电聚酰亚胺复合薄膜的制备方法
TWI555797B (zh) * 2012-11-08 2016-11-01 Asahi Kasei E Materials Corp A manufacturing method of a flexible device, a laminate, a method for producing the same, and a resin composition

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WO2014034024A1 (fr) * 2012-08-30 2014-03-06 パナソニック株式会社 Boîtier de composant électronique et son procédé de fabrication
JP5651807B2 (ja) 2012-09-05 2015-01-14 パナソニックＩｐマネジメント株式会社 半導体装置およびその製造方法
KR20190017524A (ko) * 2017-08-11 2019-02-20 주식회사 동진쎄미켐 폴리이미드 전구체 조성물 및 이를 이용한 폴리이미드 필름의 제조 방법
TWI685518B (zh) * 2018-07-31 2020-02-21 國立中興大學 電路板及其製備方法
CN112500570B (zh) * 2021-02-04 2021-05-25 武汉柔显科技股份有限公司 柔性显示器件及显示器用聚酰胺酸清漆、聚酰亚胺薄膜
CN113751405A (zh) * 2021-09-04 2021-12-07 四川富乐德科技发展有限公司 一种PI coater装置洗净技术

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JP2000204178A (ja) * 1999-01-08 2000-07-25 Kanegafuchi Chem Ind Co Ltd ポリイミドフィルムの製造方法及び装置
JP2009054608A (ja) * 2007-08-23 2009-03-12 Dainippon Printing Co Ltd 有機エレクトロルミネッセンス素子およびその製造方法
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CN104292488A (zh) * 2014-08-25 2015-01-21 哈尔滨工业大学 一种表面高导电聚酰亚胺复合薄膜的制备方法
CN104292488B (zh) * 2014-08-25 2017-06-27 哈尔滨工业大学 一种表面高导电聚酰亚胺复合薄膜的制备方法

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CN102741330A (zh) 2012-10-17
TW201136764A (en) 2011-11-01
CN102741330B (zh) 2014-07-02

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