JP5699746B2 - Method for producing polyimide film and polyimide film - Google Patents

Description

  The present invention relates to a method for producing a polyimide film excellent in adhesiveness, and a polyimide film. Moreover, this invention relates to the polyimide metal laminated body formed by laminating | stacking a metal layer on a polyimide film.

  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. For example, as 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.

  However, when the polyimide film is bonded to a metal foil such as a copper foil via a heat-resistant adhesive such as an epoxy resin adhesive, a laminate having sufficient adhesive strength may not be obtained. Also, when a metal layer is provided on the polyimide film by dry plating such as metal vapor deposition or sputtering, a laminate having a sufficiently high peel strength may not be obtained.

  As a method for improving the adhesion of a polyimide film, 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. The manufacturing method of the polyimide film which heats the solidified film with which the liquid was apply | coated to the temperature of 100-600 degreeC, imidizes the polyamic acid which forms the solidified film, drys and heat-processes a film is disclosed.

JP-A-62-267330

  An object of the present invention is to provide a method for producing a polyimide film having excellent adhesiveness. Furthermore, it is providing the polyimide metal laminated body with a big peeling strength using the polyimide film obtained by this method.

  The present invention relates to the following matters.

(1) A step of preparing a polyamic acid solution obtained by reacting a tetracarboxylic acid component and a diamine component; casting the polyamic acid solution on a support; drying the solution; and self-supporting film A step of applying a surface treatment agent to at least one surface of the self-supporting film in an environment having an absolute humidity of 13 g / m ³ or less, and a heat treatment of the self-supporting film coated with the surface treatment agent. And a step of obtaining a polyimide film. A method for producing a polyimide film, comprising:

(2) The polyimide as described in (1) above, wherein the self-supporting film is placed in an environment having an absolute humidity of 13 g / m ³ or less from the production of the self-supporting film to at least the application of the surface treatment agent. A method for producing a film.

(3) The self-supporting film is placed in an environment having an absolute humidity of 13 g / m ³ or less from the time of manufacturing the self-supporting film to the start of heat treatment of the self-supporting film after applying the surface treatment agent. The manufacturing method of the polyimide film as described in said (1) or (2).

  (4) The method for producing a polyimide film as described in any one of (1) to (3) above, wherein the surface treatment agent is a silane coupling agent.

  (5) The tetracarboxylic acid component contains 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and / or pyromellitic dianhydride as a main component, and the diamine component is The method for producing a polyimide film as described in any one of (1) to (4) above, which comprises paraphenylenediamine and / or diaminodiphenyl ether as a main component.

  (6) A polyimide film produced by the method according to any one of (1) to (5) above.

  (7) A polyimide metal laminate obtained by laminating a metal layer on the surface of the polyimide film according to (6), to which a surface treatment agent is applied during production.

  (8) The polyimide metal laminate according to (7) above, wherein a metal layer is laminated on a polyimide film via an adhesive.

  (9) The polyimide metal laminate according to (7), wherein a metal layer is formed on a polyimide film by a metalizing method.

  (10) The polyimide metal laminate according to (7), wherein a base metal layer is formed on a polyimide film by a metalizing method, and a metal plating layer is formed thereon by a wet plating method.

In the present invention, in order to improve the adhesion of the polyimide film, a surface treatment agent such as a coupling agent is applied to the surface of the self-supporting film of the polyamic acid solution, and this is heated and imidized. applying the absolute humidity 13 g / ^{m 3} or less agent, preferably under the environment 6 to 12 g / ^{m 3.} Not only when the surface treatment agent is applied, but also during the production of the self-supporting film (for example, when the self-supporting film is peeled off the support) and at least when the surface treatment agent is applied, more preferably after the surface treatment agent is applied. The self-supporting film is transported in an environment with an absolute humidity of 13 g / m ³ or less until the start of the heat treatment for imidization (for example, when inserted into a heating furnace (cure furnace) for imidization). It is preferable. Thus, the absolute humidity at the time of application of the surface treatment agent 13 g / m ³ or less, preferably by applying a surface treatment agent with 6 to 12 g / m ^3, it is possible to improve the adhesion of the polyimide film, A polyimide film having excellent adhesion can be obtained.

  By using the polyimide film of the present invention, a polyimide metal laminate having a practically sufficient peel strength can be obtained. For example, a copper laminated polyimide film having a 90-degree peel strength of 0.42 N / mm or more, further 0.45 N / mm or more, and further 0.5 N / mm or more can be obtained.

  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. The self-supporting film can be obtained by applying a surface treatment agent on one side or both sides of the self-supporting film, drying it as necessary, and then heating and imidizing the self-supporting film.

  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.

As a method for producing the polyimide film of the present invention,
(1) A polyamic acid solution, or a polyamic acid solution composition in which an imidization catalyst, a dehydrating agent, a release aid, inorganic fine particles and the like are selected and added to a polyamic acid solution as necessary on a support in the form of a film After casting and heating and drying to obtain a self-supporting film, a surface treatment agent is applied to one or both sides of this self-supporting film, and then thermally dehydrating and desolvating to remove the polyimide film. How to get,
(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, if necessary, heat drying to obtain a self-supporting film, and then applying a surface treatment agent to one or both sides of this self-supporting film, followed by heat desolvation and imidization. The method of obtaining a polyimide film by doing is mentioned.

  Specific examples of tetracarboxylic dianhydride include 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (s-BPDA) and pyromellitic dianhydride (PMDA). 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 tetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, p-phenylenebis (trimellitic acid monoester acid anhydride), p-biphenylenebis (trimellitic acid monoester acid anhydride), m -Terphenyl-3,4,3 ', 4'-tetracarboxylic dianhydride, p-terphenyl-3,4,3', 4'-tetracarboxylic dianhydride, 1,3-bis (3 , 4-dicarboxyphenoxy) benzene dianhydride, 1,4-bis (3,4-dicarboxyphenoxy) benzene dianhydride, 1,4-bis (3,4-dicarboxyphenoxy) biphenyl dianhydride, 2,2-bis [(3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracathe Bon dianhydride, 4,4 '- (2,2-hexafluoroisopropylidene) diphthalic dianhydride, and the like. These may be used alone or in combination of two or more. The tetracarboxylic dianhydride to be used can be appropriately selected according to desired characteristics.

  As the tetracarboxylic acid component, a tetracarboxylic acid component containing s-BPDA and / or PMDA as a main component is preferable. For example, an acid component selected from s-BPDA and PMDA, preferably 50 mol% or more, more preferably 70 mol% or more, particularly preferably 75 mol% or more of an acid component selected from s-BPDA and PMDA in 100 mol% of the acid component. A carboxylic acid component is preferred because the resulting polyimide film is excellent in mechanical properties.

Specific examples of diamines include
1) One diamine nucleus diamine such as paraphenylenediamine (1,4-diaminobenzene; PPD), 1,3-diaminobenzene, 2,4-toluenediamine, 2,5-toluenediamine, 2,6-toluenediamine, etc. ,
2) 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'-diaminobenzanilide, 3,3'-dichlorobenzidine, 3,3'-dimethylbenzidine, 2,2'-dimethylbenzene Dizine, 3,3'-dimethoxybenzidine, 2,2'-dimethoxybenzidine, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl sulfide 3,4′-diaminodiphenylsulfide, 4,4′-diaminodiphenylsulfide, 3,3′-diaminodiphenylsulfone, 3,4′-diaminodiphenylsulfone, 4,4′-diaminodiphenylsulfone, 3,3 ′ -Diaminobenzophenone, 3,3'-diamino-4,4'-dichlorobenzophenone, 3,3'-diamino-4,4'-dimethoxybenzophenone, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, 2,2-bis (3- Minophenyl) propane, 2,2-bis (4-aminophenyl) propane, 2,2-bis (3-aminophenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (4-aminophenyl) -1,1,1,3,3,3-hexafluoropropane, 3,3′-diaminodiphenyl sulfoxide, 3,4′-diaminodiphenyl sulfoxide, 4,4′-diaminodiphenyl sulfoxide, etc. The benzene core of two diamines,
3) 1,3-bis (3-aminophenyl) benzene, 1,3-bis (4-aminophenyl) benzene, 1,4-bis (3-aminophenyl) benzene, 1,4-bis (4-amino) Phenyl) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (3 -Aminophenoxy) -4-trifluoromethylbenzene, 3,3'-diamino-4- (4-phenyl) phenoxybenzophenone, 3,3'-diamino-4,4'-di (4-phenylphenoxy) benzophenone, 1,3-bis (3-aminophenyl sulfide) benzene, 1,3-bis (4-aminophenyl sulfide) benzene, 1,4-bis (4-aminophenyls) Fido) benzene, 1,3-bis (3-aminophenylsulfone) benzene, 1,3-bis (4-aminophenylsulfone) benzene, 1,4-bis (4-aminophenylsulfone) benzene, 1,3- Bis [2- (4-aminophenyl) isopropyl] benzene, 1,4-bis [2- (3-aminophenyl) isopropyl] benzene, 1,4-bis [2- (4-aminophenyl) isopropyl] benzene, etc. 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, 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-aminophenoxy) phenyl] ketone, bis [3- (3-aminophenoxy) phenyl] Sulfide, bis [3- (4-aminophenoxy) phenyl] sulfide, bis [4- (3-aminophenoxy) phenyl] sulfide, bis [4- (4-aminophenoxy) phenyl] sulfide, bis [3- (3 -Aminophenoxy) phenyl] sulfone, bis [3- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, Bis [3- (3-aminophenoxy) phenyl] methane, bis [3- (4-aminophenoxy) phenyl] methane, bis [4- (3-aminophenoxy) phenyl] methane, bis [4- (4-amino Phenoxy) phenyl] methane, 2,2-bis [3- (3-aminophenoxy) phenyl] propane, , 2-bis [3- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl ] Propane, 2,2-bis [3- (3-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [3- (4-aminophenoxy) Phenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [4- (3-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoro Four diamine diamines such as propane, 2,2-bis [4- (4-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane,
And so on. These may be used alone or in combination of two or more. The diamine to be used can be appropriately selected according to desired characteristics.

  As the diamine component, a diamine component containing PPD and / or diaminodiphenyl ether as a main component is preferable. For example, in 100 mol% of the diamine component, 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.

  Among them, 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 is preferable. In this case, the PPD / diaminodiphenyl ether (molar ratio) is preferably 100/0 to 85/15.

  In addition, PMDA or 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 Also preferred are polyimides made from aromatic diamines such as diaminodiphenyl ethers such as diphenyl ether. As the aromatic diamine, PPD or an aromatic diamine in which PPD / diaminodiphenyl ether is 90/10 to 10/90 is preferable. In this case, s-BPDA / PMDA is preferably 0/100 to 90/10.

  Also preferred are polyimides prepared from PMDA and PPD and diaminodiphenyl ethers such as 4,4'-diaminodiphenyl ether and 3,4'-diaminodiphenyl ether. In this case, the diaminodiphenyl ethers / PPD is preferably 90/10 to 10/90.

  The polyamic acid which is a polyimide precursor can be obtained by reacting the above tetracarboxylic acid component and diamine component 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). Can be obtained. 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.

  As the 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.

  If necessary, 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.

  If necessary, a cyclization catalyst, a dehydrating agent, inorganic fine particles and the like may be added to the polyamic acid solution as long as it is chemical imidization.

  Examples of the imidization catalyst 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 and the like. Benzimidazoles such as alkylimidazole and N-benzyl-2-methylimidazole, isoquinoline, 3,5-dimethylpyridine, 3,4-dimethylpyridine, 2,5-dimethylpyridine, 2,4-dimethylpyridine, 4-n- Preferred are substituted pyridines such as propylpyridine It can be used for. The amount of the imidization catalyst used is preferably about 0.01 to 2 times equivalent, particularly about 0.02 to 1 times equivalent to the amic acid unit of the polyamic acid. By using an imidization catalyst, properties of the resulting polyimide film, particularly elongation and end resistance, may be improved.

  Examples of the organic phosphorus-containing compounds 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, triethyl Diphosphate of glycol mono tridecyl ether, diphosphate of tetraethyleneglycol monolauryl ether, and phosphoric acid esters such as diphosphate esters of diethylene glycol monostearyl ether, amine salts of these phosphates. As 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, α-picoline and β-picoline. Etc.

  Examples of the dehydrating agent 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 the concentration is within a viscosity range suitable for production, but is usually preferably 10% by mass to 30% by mass, and 15% by mass to 27% by mass. More preferably, 18 mass%-26 mass% is further more preferable.

  The heating temperature and heating time during the production of the self-supporting film can be appropriately determined. In the thermal imidization, for example, 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. For example, 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. % Is preferable, the loss on heating is in the range of 20 to 50% by mass, and the imidization ratio is more preferably in the range of 7 to 55%. If the weight loss and imidization ratio of the self-supporting film are within the above ranges, the mechanical properties of the self-supporting film are sufficient, and the surface treatment agent is uniformly and cleanly applied to the upper surface of the self-supporting film. Foaming, cracks, crazes, cracks, cracks and the like are not observed in the polyimide film obtained after imidization.

  Here, the loss on heating of the self-supporting film is a value obtained by the following equation from the mass W1 of the self-supporting film and the mass W2 of the film after curing.

  Loss on heating (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. As the vibration band peak, an asymmetric stretching vibration band of an imide carbonyl group, a benzene ring skeleton stretching vibration band, or the like is used.

In the present invention, on one or both sides of the self-supporting film obtained in this way, the absolute humidity 13 g / ^{m 3} or less, preferably 0~12g / ^{m 3,} more preferably 6 to 12 g ^{/ m} 3, Particularly preferably, a surface treatment agent such as a coupling agent is applied in an environment of 8.5 to 12 g / m ³ .

Here, absolute humidity refers to the amount (g) of water vapor contained in a constant volume of air (m ³ ). The absolute humidity is obtained as follows. The temperature and relative humidity are measured by a known method, and the saturated water vapor amount at the measured temperature is derived from a generally known saturation curve, and is obtained from the saturated water vapor amount by the following equation.

Absolute humidity (g / m ³ ) = saturated water vapor amount (g / m ³ ) × relative humidity (%) ÷ 100

In the present invention, the self-supporting film is produced in an environment having an absolute humidity of 13 g / m ³ or less from the time when the self-supporting film is produced, for example, from the time when the self-supporting film is peeled off the support to the time of applying the surface treatment agent. It is preferable to carry.

In particular, from the production of the self-supporting film to the application of the surface treatment agent, and further to the start of the heat treatment for the subsequent imidization of the self-supporting film, for example, a heating furnace for imidization It is preferable to transport the self-supporting film in an environment having an absolute humidity of 13 g / m ³ or less until it is inserted into the (curing furnace). In addition, during conveyance of a self-supporting film, as long as absolute humidity is in said range, it may not be constant.

  Moreover, the temperature at the time of application | coating of a surface treating agent can be selected suitably.

If the absolute humidity at the time of applying the surface treatment agent is 13 g / m ³ or less, it is not necessary to adjust the humidity. When the absolute humidity exceeds 13 g / m ³ , the absolute humidity under the environment is adjusted so that the absolute humidity is 13 g / m ³ or less. Examples of the adjusting means include a method of blowing dry gas into the environment.

Further, at least one step from the time of manufacturing the self-supporting film to the time of applying the surface treatment agent and the time after the application of the surface treatment agent to the start of the heat treatment for imidization of the self-supporting film. When the absolute humidity exceeds 13 g / m ³ , the absolute humidity under the environment can be adjusted so that the absolute humidity is 13 g / m ³ or less. Examples of the adjusting means include a method of blowing dry gas into the environment.

Here, the “environment” under an environment of an absolute humidity of 13 g / m ³ or less means an atmosphere in which the self-supporting film is transported and coated. More specifically, the self-supporting film is transported and coated. It refers to the gas zone to be worked on, the surface of the film, etc.

  As surface treatment agents, 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.

  In particular, it is preferable to use a coupling agent such as a silane coupling agent as the surface treatment agent.

  Epoxysilane couplings such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, etc. as silane coupling agents Agents; vinyl silane coupling agents such as vinyltrichlorosilane, vinyltris (β-methoxyethoxy) silane, vinyltriethoxysilane, vinyltrimethoxysilane; acrylic silane coupling agents such as γ-methacryloxypropyltrimethoxysilane; N -Β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane, N-phenyl-γ-aminopropyltriethoxysilane, N-phenyl-γ -Aminopropyltri Methoxysilane, N-β- (aminoethyl) -γ-aminopropyltriethoxysilane, N- (aminocarbonyl) -γ-aminopropyltriethoxysilane, N- [β- (phenylamino) -ethyl] -γ- Aminosilane-based coupling agents such as aminopropyltriethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane; γ-mercaptopropyl Mercapto-based silane coupling agents such as trimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane; γ-chloropropyltrimethoxysilane and the like.

  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.

  As coupling agents, silane coupling agents, particularly N-β- (aminoethyl) -γ-aminopropyl-triethoxysilane, N- (aminocarbonyl) -γ-aminopropyltriethoxysilane, N- [β- (Phenylamino) -ethyl] -γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ Aminosilane coupling agents such as aminopropyl-trimethoxysilane, γ-aminopropyl-trimethoxysilane, and γ-aminopropyl-triethoxysilane are preferred, and among them, N-phenyl-γ-aminopropyltrimethoxysilane is particularly preferable. N-β- (aminoethyl) -γ-aminopropyl-trimethoxysilane Lan, γ-aminopropyl-trimethoxysilane is preferred.

  The surface treatment agent is used alone as it is or after being mixed with an appropriate solvent. In the case of using a solvent, examples of the solvent for the surface treatment agent, such as a coupling agent and a chelating agent, include the same organic solvent as the polyimide precursor solution (the solvent contained in the self-supporting film). . The organic solvent may be a solvent compatible with the polyimide precursor solution or a poor solvent not compatible with the polyimide precursor solution. The organic solvent may be a mixture of two or more. Moreover, water can also be used as a solvent. That is, it can be used as an aqueous solution in which a surface treatment agent and water are mixed. In the following description, the surface treatment agent will be described as a solution of a surface treatment agent in which a surface treatment agent and a solvent are mixed.

  In the solution of the surface treatment agent such as a coupling agent or a chelating agent applied to the self-supporting film, the content of the surface treatment agent is 0.1% by mass or more, preferably 0.1 to 60% by mass, more preferably 0. It is preferably 3 to 20% by mass, particularly preferably 0.5 to 15% by mass, and more preferably 1 to 10% by mass. The water content is preferably 20% by mass or less, more preferably 10% by mass or less, and particularly preferably 5% by mass or less.

  The rotational viscosity (solution viscosity measured by 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 0.5 to 50000 centipoise, more preferably 0.8. It is preferably 8 to 5000 centipoise.

  As the organic solvent solution of the surface treatment agent, the surface treatment agent is particularly uniform in an amide solvent at a concentration of 0.1% by mass or more, particularly preferably 0.5 to 15% by mass, and more preferably 1 to 10% by mass. Those having a low viscosity (particularly, a rotational viscosity of 0.8 to 5000 centipoise) are preferable.

  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 solution of the surface treatment agent may be appropriately determined, for example, a surface on the side in contact with the support of the self-supporting film, the surface of both of the opposite side, preferably 1 to 50 g / m ^2,. 2 to more preferably ^{30g / m 2, 3~20g / m} 2 is particularly preferred. The amount applied may be the same on both sides or different.

  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. Examples thereof include known coating methods such as a method, a roll coating method, a blade coating method, and a die coating method.

  In the present invention, the self-supporting film coated with the surface treatment agent solution is then dried as necessary, and then heat-treated to obtain a polyimide film. Drying can be performed by, for example, hot air drying at about 60 to 150 ° C.

  In 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. . In particular, 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. The secondary heat treatment is preferably 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.

  At the time of heat treatment for imidization, in a curing furnace, 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 may be appropriately selected and is not particularly limited, but is about 3 to 250 μm, preferably about 4 to 150 μm, more preferably about 5 to 125 μm, and still more preferably about 5 to 100 μm. It is.

  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.

  The polyimide film of this invention can obtain the polyimide metal laminated body which laminated | stacked the metal layer on the surface which apply | coated the surface treating agent at the time of manufacture.

  In addition, the polyimide film of the present invention has good adhesiveness, sputtering property and metal deposition property, and adheres metal foil such as copper foil as a metal layer using an adhesive, or metallizing such as sputtering or metal deposition. By providing a metal layer such as a copper layer by a method, a metal laminated polyimide film such as a copper laminated polyimide film having excellent adhesion and sufficient peel strength can be obtained. Furthermore, by forming a base metal layer on a polyimide film by a metalizing method and forming a metal plating layer thereon by a wet plating method, a polyimide metal laminate having excellent adhesion and sufficient peel strength is obtained. Can do. Moreover, a metal foil laminated polyimide film can be obtained by laminating a metal foil such as a copper foil on the polyimide film of the present invention using a thermocompression bonding polymer such as a thermocompression bonding polyimide. The metal layer can be laminated according to a known method.

  The thickness of the copper layer of the copper laminated polyimide film can be appropriately selected depending on the purpose of use, but is preferably about 1 μm to 50 μm, and more preferably about 2 μm to 20 μm.

  As the metal foil to be bonded to the polyimide film via an adhesive, the type and thickness of the metal may be appropriately selected depending on the application to be used. For example, rolled copper foil, electrolytic copper foil, copper alloy foil, aluminum foil, stainless steel foil , Titanium foil, iron foil, nickel foil and the like, and the thickness is preferably about 1 μm to 50 μm, and more preferably about 2 μm to 20 μm.

  Further, the polyimide film obtained by the present invention and another resin film, a metal such as copper, or a chip member such as an IC chip can be bonded directly or using an adhesive.

  As the adhesive, known ones can be used depending on the application, such as those having excellent insulation and adhesion reliability, or those having excellent conductivity and adhesion reliability by pressure bonding such as ACF. And a thermosetting adhesive.

  Examples of the adhesive include polyimide-based, polyamide-based, polyimide-amide-based, acrylic-based, epoxy-based, urethane-based adhesives, and adhesives including two or more of these, particularly acrylic-based and epoxy-based adhesives. It is preferable to use a urethane-based or polyimide-based adhesive.

  The metallizing method is a method of providing a metal layer different from metal plating or metal foil lamination, and a known method such as vacuum deposition, sputtering, ion plating, or 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, or alloys thereof, or oxides or metals of these metals. Metal compounds such as carbides can be used, but are not particularly limited to these materials.

  The thickness of the metal layer formed by the metalizing method can be appropriately selected depending on the purpose of use, and is usually preferably 1 nm to 500 nm, more preferably 5 nm to 200 nm because it is suitable for practical use.

  The number of metal layers can be appropriately selected according to the purpose of use, and may be one layer, two layers, or three or more layers.

  In the metal laminated polyimide film obtained by the metalizing method, a metal plating layer of copper, tin or the like can be provided on the surface of the metal layer by a known wet plating method such as electrolytic plating or electroless plating.

  The film thickness of the metal plating layer such as copper plating can be appropriately selected according to the purpose of use, and is usually preferably in the range of 1 μm to 40 μm because it is suitable for practical use.

  According to the present invention, for example, a copper laminated polyimide film having a 90-degree peel strength of 0.42 N / mm or more, further 0.45 N / mm or more, and further 0.5 N / mm or more can be obtained.

  The polyimide film of the present invention is made of an insulating substrate material such as FPC, TAB, COF or a metal wiring base material, a cover base material such as a metal wiring or a chip member such as an IC chip, a liquid crystal display, an organic electroluminescence display, an electronic paper, a solar It can be suitably used as a base substrate for batteries and the like.

  What is necessary is just to select the linear expansion coefficient of a polyimide film suitably according to the objective to be used. For example, in the above applications, it is preferable that the linear expansion coefficient of the polyimide film is close to the linear expansion coefficient of copper. Specifically, both MD and TD are preferably 10 to 40 ppm / ° C. More preferably, it is 30 ppm / ° C, and further preferably 12-25 ppm / ° C. According to this invention, while being excellent in adhesiveness, the polyimide film whose linear expansion coefficient is close to the linear expansion coefficient of copper is obtained.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples.

  The 90 degree peel strength of the copper laminated polyimide film was measured according to the following method. Ink is printed on the copper laminated polyimide film using a screen so that the copper width becomes 3 mm, and copper other than the ink printing part is etched using an etching apparatus. A test piece is fixed to the supporting metal for 90-degree peeling using a double-sided tape, peeled off at a rate of 50 mm / min by 50 mm / min using a tensile tester, and the load therebetween is measured. A value obtained by dividing the peeling load by the peeling width (mm) of the test piece was obtained and set as a 90-degree peel strength.

  Absolute humidity was determined by the following method. The temperature and relative humidity were measured by a known method, and the saturated water vapor amount at the measured temperature was derived from a generally known saturation curve, and calculated from the saturated water vapor amount according to the following equation.

Absolute humidity (g / m ³ ) = saturated water vapor amount (g / m ³ ) × relative humidity (%) ÷ 100

<Example 1>
A predetermined amount of N, N-dimethylacetamide is added to the polymerization tank, then 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and then paraphenylenediamine are added, and a polymerization reaction is performed at 30 ° C. for 10 hours. Polyimide precursor (polyamic acid) having a polymer logarithmic viscosity (measurement temperature: 30 ° C., concentration: 0.5 g / 100 mL solvent, solvent: N, N-dimethylacetamide) of 1.60 and polymer concentration of 18% by mass A solution was obtained. In this polyimide precursor solution, a colloidal having an average particle size of 0.08 μm at a ratio of 0.1 part by mass of monostearyl phosphate ester triethanolamine salt and 0.5 part by mass with respect to 100 parts by mass of the polyimide precursor Silica was added and mixed uniformly to obtain a polyimide precursor solution composition. The rotational viscosity of this polyimide precursor solution composition was 3000 poise.

  This polyimide precursor solution composition was 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. The thin film was heated at 120 to 160 ° C. for 10 minutes and then peeled off from the support to obtain a self-supporting film.

This self-supporting film was conveyed for 3 minutes in an environment of 25 ° C., 52% RH and absolute humidity of 12.0 g / m ³ , and then the B side (support when the polyimide precursor solution composition was cast on the support) 7 g / m ^{2 of} an N, N-dimethylacetamide solution containing a silane coupling agent (N-phenyl-γ-aminopropyltrimethoxysilane) as a surface treatment agent at a concentration of 4% by mass on the body-side surface). The coating amount was applied and dried with hot air at 80 to 120 ° C. The absolute humidity under the environment in which the N, N-dimethylacetamide solution containing a silane coupling agent was applied was 12.0 g / m ³ . Next, after being transported for 3.5 minutes in an environment of 25 ° C., 52% RH and absolute humidity 12.0 g / m ³ , both ends of the dry film in the width direction are gripped and inserted into a continuous heating furnace. The film was heated and imidized under the condition that the maximum heating temperature was about 500 ° C. to continuously produce a long polyimide film having an average film thickness of 34 μm.

  On the B surface of the obtained polyimide film, a sputter base metal layer composed of a Ni / Cr (mass ratio: 8/2) layer having a thickness of 5 nm and a Cu layer having a thickness of 400 nm is formed by a conventional method, and a thickness of 8 μm is formed thereon. Copper plating was performed to obtain a copper laminated polyimide film. The 90 ° peel strength of this copper laminated polyimide film was measured and found to be 0.58 N / mm. The results are shown in Table 1.

<Example 2>
The self-supporting film is transported in an environment of 25 ° C. and 32% RH and an absolute humidity of 10.1 g / m ³ from the time of manufacture to the time of application of the silane coupling agent solution (including the drying step after application). The polyimide film was treated in the same manner as in Example 1 except that it was transported in an environment of 25 ° C., 32% RH and absolute humidity of 10.1 g / m ³ until it was inserted into the continuous heating furnace after application of the silane coupling agent solution. Got. And using this polyimide film, the copper lamination polyimide film was produced like Example 1, and it was 0.59 N / mm when 90 degree peel strength was measured. The results are shown in Table 1.

<Example 3>
The self-supporting film is transported in an environment of 25 ° C. and 37% RH and an absolute humidity of 8.5 g / m ³ from the time of manufacture to the time of application of the silane coupling agent solution (including the drying step after application). The polyimide film was the same as in Example 1 except that it was transported in an environment of 32 ° C., 69% RH and absolute humidity of 23.3 g / m ³ until it was inserted into the continuous heating furnace after application of the silane coupling agent solution. Got. And using this polyimide film, the copper lamination polyimide film was produced like Example 1, and it was 0.45 N / mm when 90 degree peel strength was measured. The results are shown in Table 1.

<Comparative Example 1>
The self-supporting film is transported in an environment of 27 ° C./55% RH and absolute humidity of 13.8 g / m ³ from the time of manufacture to the time of application of the silane coupling agent solution (including the drying step after application), The polyimide film was applied in the same manner as in Example 1 except that it was transported in an environment of 27 ° C./55% RH and absolute humidity of 13.8 g / m ³ from the application of the silane coupling agent solution to the continuous heating furnace. Got. And using this polyimide film, the copper lamination polyimide film was produced like Example 1, and it was 0.41 N / mm when 90 degree peel strength was measured. The results are shown in Table 1.

<Comparative Example 2>
The self-supporting film is transported in an environment of 29 ° C./73% RH and absolute humidity of 21.0 g / m ³ from the production to the application of the silane coupling agent solution (including the drying process after the application) The polyimide film was treated in the same manner as in Example 1 except that it was transported in an environment of 29 ° C./73% RH and absolute humidity 21.0 g / m ³ from the application of the silane coupling agent solution to the continuous heating furnace. Got. And using this polyimide film, the copper lamination polyimide film was produced like Example 1, and it was 0.39 N / mm when 90 degree peel strength was measured. The results are shown in Table 1.

<Comparative Example 3>
The self-supporting film is transported in an environment of 27 ° C./75% RH and absolute humidity of 19.3 g / m ³ from the production to the application of the silane coupling agent solution (including the drying process after the application) The polyimide film was the same as in Example 1 except that it was transported in an environment of 25 ° C., 37% RH, and absolute humidity of 8.5 g / m ³ from the application of the silane coupling agent solution to the continuous heating furnace. Got. And using this polyimide film, the copper lamination polyimide film was produced like Example 1, and it was 0.38 N / mm when 90 degree peel strength was measured. The results are shown in Table 1.

<Comparative Example 4>
The self-supporting film is conveyed in an environment of 36 ° C./44% RH and absolute humidity of 18.4 g / m ³ from the time of manufacture to the time of application of the silane coupling agent solution (including the drying step after application). The polyimide film was applied in the same manner as in Example 1 except that it was transported in an environment of 34 ° C., 70% RH and absolute humidity of 26.3 g / m ³ until it was inserted into the continuous heating furnace after application of the silane coupling agent solution. Got. And using this polyimide film, the copper lamination polyimide film was produced like Example 1, and it was 0.31 N / mm when 90 degree peel strength was measured. The results are shown in Table 1.

<Comparative Example 5>
The self-supporting film is conveyed in an environment of 34 ° C., 70% RH and absolute humidity of 26.3 g / m ³ from the time of manufacture to the time of application of the silane coupling agent solution (including the drying step after application). The polyimide film was applied in the same manner as in Example 1 except that it was transported in an environment of 34 ° C., 70% RH and absolute humidity of 26.3 g / m ³ until it was inserted into the continuous heating furnace after application of the silane coupling agent solution. Got. And using this polyimide film, the copper lamination polyimide film was produced like Example 1, and it was 0.18 N / mm when 90 degree peel strength was measured. The results are shown in Table 1.

The polyimide films of Examples 1 to 3 manufactured by transporting the self-supporting film in an environment having an absolute humidity of 13 g / m ³ or less from the production to the application of the silane coupling agent solution have an absolute humidity of 13 g / m ^3. Compared with the polyimide films of Comparative Examples 1 to 5 manufactured by transporting in an environment exceeding 1, the 90 ° peel strength of the copper laminated polyimide film was large. The polyimide film of Comparative Example 3 was manufactured by transporting a self-supporting film in an environment with an absolute humidity of 13 g / m ³ or less after application of the silane coupling agent solution. It was low.

  As mentioned above, according to this invention, the adhesiveness of a polyimide film can be improved with a simple method. The polyimide film of this invention is excellent in adhesiveness, and can obtain the polyimide metal laminated body which has sufficient peel strength.

Claims (9)

A step of preparing a polyamic acid solution obtained by reacting a tetracarboxylic acid component and a diamine component, and a step of casting the polyamic acid solution on a support and drying it to obtain a self-supporting film And a step of applying a surface treatment agent to at least one surface of the self-supporting film in an environment having an absolute humidity of 13 g / m ³ or less, and heat-treating the self-supporting film coated with the surface treatment agent to obtain a polyimide. obtaining a film was perforated,
A method for producing a polyimide film, characterized in that the self-supporting film is placed in an environment having an absolute humidity of 13 g / m ³ or less from the production of the self-supporting film to at least the application of the surface treatment agent . The self-supporting film is placed in an environment having an absolute humidity of 13 g / m ³ or less from the time of manufacturing the self-supporting film to the start of heat treatment of the self-supporting film after applying the surface treatment agent. Item 2. A method for producing a polyimide film according to Item 1 . The process for producing a polyimide film as described in any one of claims 1-2, wherein the surface treatment agent is a silane coupling agent. The tetracarboxylic acid component contains 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and / or pyromellitic dianhydride as a main component, and the diamine component is paraphenylenediamine. The method for producing a polyimide film according to any one of claims 1 to 3 , comprising diaminodiphenyl ether as a main component. The polyimide film manufactured by the method of any one of Claims 1-4 . The polyimide metal laminated body formed by laminating | stacking a metal layer on the surface which apply | coated the surface treating agent at the time of manufacture of the polyimide film of Claim 5 . The polyimide metal laminate according to claim 6 , wherein a metal layer is laminated on a polyimide film via an adhesive. The polyimide metal laminate according to claim 6 , wherein a metal layer is formed on a polyimide film by a metalizing method. The polyimide metal laminate according to claim 6 , wherein a base metal layer is formed on a polyimide film by a metalizing method, and a metal plating layer is formed thereon by a wet plating method.