JP5468913B2 - Multilayer polyimide film with resist and method for producing the same - Google Patents

Description

  The present invention relates to a multilayer polyimide film and a metal-clad laminate that can be suitably used for flexible printed wiring boards.

  In recent years, the demand for various printed circuit boards has increased along with the reduction in weight, size and density of electronic products. ing. The flexible laminate has a structure in which a circuit made of a metal layer is formed on an insulating film such as a polyimide film.

  The flexible metal-clad laminate that is the basis of the flexible wiring board is generally formed of various insulating materials, and a flexible insulating film is used as a substrate, and metal foil is applied to the surface of the substrate via various adhesive materials. Manufactured by a method of bonding by heating and pressure bonding. A polyimide film or the like is preferably used as the insulating film. As the adhesive material, epoxy-based, acrylic-based thermosetting adhesives are generally used.

  Thermosetting adhesives have the advantage that they can be bonded at relatively low temperatures. However, as the required properties such as heat resistance, flexibility, and electrical reliability become stricter, three types of thermosetting adhesives are used. It is considered difficult to cope with the layer FPC. For this reason, a two-layer FPC has been proposed in which a metal layer is directly provided on an insulating film or a thermoplastic polyimide is used for an adhesive layer. This two-layer FPC has characteristics superior to those of the three-layer FPC, and demand is expected to increase in the future.

  On the other hand, when processing into an FPC, a circuit pattern is formed by etching or the like on the metal layer of the flexible metal-clad laminate, and then the circuit is covered with a coverlay film, a resist film, or a resist solution to protect the circuit. The cover lay or resist is required to be difficult to peel off, but the thermoplastic polyimide of the two-layer FPC may be peeled off due to the low adhesive strength with the cover lay film adhesive or resist. . For example, a polyimide precursor is applied and dried multiple times on a copper foil, and a double-sided metal-clad laminate is obtained by thermocompression bonding. If a resist is formed over the wiring after the wiring pattern is formed, polyimide resin There was a problem that the adhesion between the layer and the resist was weak and the resist peeled off (Cited document 1).

  Therefore, a polyimide adhesive layer having good adhesion to the adhesive and resist of the coverlay film is awaited from the market.

Japanese Patent No. 3934057

  The present invention has been made in view of the above-mentioned problems, and the object thereof is a multilayer in which the coverlay film and resist are difficult to peel off in the form of FPC with high adhesiveness to the adhesive and resist of the coverlay film. A polyimide film and a flexible metal-clad laminate using the same are provided.

  As a result of intensive studies in view of the above problems, the inventors of the present invention have an amine at the end of the thermoplastic polyimide layer of the outermost thermoplastic polyimide layer of the multilayer polyimide film, so that the adhesive and resist of the coverlay film The inventors have found that the adhesion is improved and have arrived at the present invention.

That is, the present invention is a multilayer polyimide film having a thermoplastic polyimide layer on at least one side of the non-thermoplastic polyimide layer,
The aromatic diamine used in the thermoplastic polyimide layer is 4,4′-diaminodiphenyl ether, 1,3-bis (4-aminophenoxy) benzene, and 2,2-bis [4- (4-aminophenoxy) phenyl]. At least one selected from the group consisting of propane,
The aromatic dianhydride used in the thermoplastic polyimide layer is pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-. Is at least one selected from the group consisting of biphenyltetracarboxylic dianhydride and 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride,
Production of a multilayer polyimide film, wherein the thermoplastic polyimide layer comprises a polyimide obtained by imidizing a polyamic acid solution having amino groups at both ends obtained by the following steps (a) and (b) Regarding the method.
(A) reacting an aromatic acid dianhydride with an excess molar amount of an aromatic diamine in an organic polar solvent to obtain a prepolymer having amino groups at both ends;
(B) To the prepolymer, the aromatic acid dianhydride and aromatic diamine have a molar ratio of 97.0: 100.0 to 99.8: 100.0 in all steps. A step of adding an anhydride to react.

As a preferred embodiment, the non-thermoplastic polyimide layer is obtained by imidizing a polyamic acid solution obtained by the following steps (c) to (e), and relates to a method for producing a multilayer polyimide film.
(C) a step of reacting an aromatic acid dianhydride with an excess molar amount of an aromatic diamine in an organic polar solvent to obtain a prepolymer having amino groups at both ends;
(D) adding an aromatic diamine to the prepolymer;
(E) A step of adding and reacting the aromatic acid dianhydride so that the aromatic acid dianhydride and the aromatic diamine in all steps are substantially equimolar.

  In a preferred embodiment, the aromatic diamine used in the non-thermoplastic polyimide layer is 10 to 50 mol% of 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 30 to 30% based on the diamine component. It is related with the manufacturing method of the multilayer polyimide film characterized by being 70 mol% p-phenylenediamine and 10-30 mol% 4,4'- diaminodiphenyl ether.

  In a preferred embodiment, the acid dianhydride used in the non-thermoplastic polyimide layer is 60 to 90 mol% pyromellitic dianhydride, 10 to 40 mol% 3,3 ′ based on the acid dianhydride component. It is related with the manufacturing method of the multilayer polyimide film characterized by being 4,4'-benzophenone tetracarboxylic dianhydride.

  As a preferred embodiment, the present invention relates to a method for producing a multilayer polyimide film, wherein the multilayer polyimide film is obtained by multilayer coextrusion.

  The present invention also relates to a multilayer polyimide film obtained by the production method described above.

  The present invention also relates to a flexible metal-clad laminate obtained by bonding a metal foil to the multilayer polyimide film described above.

  According to the present invention, it is possible to provide a multilayer polyimide film having a high adhesiveness to the adhesive and resist of the cover lay film and in which the cover lay film and the resist are difficult to peel in the form of FPC and a flexible metal-clad laminate using the same it can.

  One embodiment of the present invention will be described below.

The present invention is a multilayer polyimide film having a thermoplastic polyimide layer on at least one side of the non-thermoplastic polyimide layer,
The aromatic diamine used in the thermoplastic polyimide layer is 4,4′-diaminodiphenyl ether, 1,3-bis (4-aminophenoxy) benzene, and 2,2-bis [4- (4-aminophenoxy) phenyl]. At least one selected from the group consisting of propane,
The aromatic dianhydride used in the thermoplastic polyimide layer is pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-. Is at least one selected from the group consisting of biphenyltetracarboxylic dianhydride and 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride,
Production of a multilayer polyimide film, wherein the thermoplastic polyimide layer comprises a polyimide obtained by imidizing a polyamic acid solution having amino groups at both ends obtained by the following steps (a) and (b) Is the method.
(A) reacting an aromatic acid dianhydride with an excess molar amount of an aromatic diamine in an organic polar solvent to obtain a prepolymer having amino groups at both ends;
(B) To the prepolymer, the aromatic acid dianhydride and aromatic diamine have a molar ratio of 97.0: 100.0 to 99.8: 100.0 in all steps. A step of adding an anhydride to react.

The ratio of acid dianhydride to diamine in the thermoplastic polyimide is obtained by peeling or scraping the thermoplastic polyimide, and then heating with a 5N to 10N NaOH aqueous solution to decompose the thermoplastic polyimide into monomers. . The monomer structure of the decomposed monomer is determined by LC-MS (liquid chromatography-mass spectrometry), ¹ H-NMR, or the like. Thereafter, a calibration curve is prepared using the monomer, and the monomer amount is measured by HPLC analysis. Several types of monomers can be used, and the total amount of aromatic dianhydride and aromatic diamine is calculated.

  The ratio of aromatic dianhydride and aromatic diamine was calculated as the ratio of aromatic dianhydride when the aromatic diamine was 100.0. The ratio of aromatic dianhydride and aromatic diamine used in the thermoplastic polyimide of the thermoplastic polyimide layer disposed on both sides of the non-thermoplastic polyimide layer is 97.0: 100.0-99.8: 100. 98.0: 100.0 to 99.8: 100.0 is preferable for increasing the molecular weight and increasing the film strength, and 99.0: 100.0 to 99.8: 100.0 is more preferable. 99.2: 100.0 to 99.8: 100.0 is particularly preferable.

  A method for producing a thermoplastic polyamic acid of a thermoplastic polyimide is as follows: (a) an aromatic acid dianhydride and an excess molar amount of an aromatic diamine are reacted in an organic polarity, and amino groups are formed at both ends. (B) a prepolymer having a molar ratio of aromatic dianhydride to aromatic diamine in all steps of 97.0: 100.0 to 99.8: 100.0. A step of adding an aromatic acid dianhydride to the polymer and reacting the polymer. In (b), there are a method of adding an aromatic acid dianhydride, a method of adding a powder, a method of adding an acid solution in which an acid dianhydride is dissolved in an organic polar solvent in advance, and the reaction is uniform. In view of easy progress, a method of adding an acid solution is preferable.

  The solid component concentration during the polymerization is preferably 10 to 30% by weight. The solid component concentration can be determined by the polymerization rate and the polymerization viscosity. The polymerization viscosity can be set according to the case where the polyamic acid solution of thermoplastic polyimide is applied to the support film, or when it is coextruded with non-thermoplastic polyimide. The polymerization viscosity is preferably 100 poise or less at a component concentration of 14% by weight. In the case of coextrusion, for example, the polymerization viscosity is preferably 100 poise to 1200 poise at a solid component concentration of 14% by weight, and 150 poise to 800 poise is preferable because the film thickness of the resulting multilayer polyimide film can be made uniform.

  As mentioned above, the terminal of thermoplastic polyimide becomes an amino group because more diamine used for thermoplastic polyimide is contained in molar ratio than acid dianhydride. It has been found that the amino group reacts with the adhesive and resist of the coverlay film to form a chemical bond, thereby making it difficult for the coverlay film and the resist to peel off.

  As the preferred solvent for synthesizing the polyamic acid in the present invention, any solvent can be used as long as it dissolves the polyamic acid. However, amide solvents, that is, N, N-dimethylformamide, N, N-dimethyl are used. Examples include acetamide and N-methyl-2-pyrrolidone. Of these, N, N-dimethylformamide and N, N-dimethylacetamide can be particularly preferably used.

  In addition, a filler can be added for the purpose of improving various properties of the film such as slidability, thermal conductivity, conductivity, and corona resistance. The filler is not particularly limited, and preferred examples include silica, titanium oxide, alumina, silicon nitride, boron nitride, calcium hydrogen phosphate, calcium phosphate, mica and the like.

  The particle size of the filler is not particularly limited because it is determined by the film characteristics to be modified and the type of filler to be added, but generally the average particle size is 0.05 to 20 μm, preferably 0.1. It is 10-10 micrometers, More preferably, it is 0.1-7 micrometers, Most preferably, it is 0.1-5 micrometers. If the particle size is below this range, the modification effect is less likely to appear. If the particle size is above this range, the surface properties may be greatly impaired or the mechanical properties may be greatly deteriorated. Further, the number of added parts of the filler is not particularly limited because it is determined by the film properties to be modified, the filler particle diameter, and the like. Generally, the addition amount of the filler is 0.01 to 50 parts by weight, preferably 0.01 to 20 parts by weight, and more preferably 0.02 to 10 parts by weight with respect to 100 parts by weight of the polyimide. If the amount of filler added is less than this range, the effect of modification by the filler hardly appears, and if it exceeds this range, the mechanical properties of the film may be greatly impaired.

Addition of the filler is, for example,
(1) A method of adding to a polymerization reaction solution before or during polymerization (2) A method of kneading fillers using three rolls after the completion of polymerization (3) A dispersion containing fillers is prepared, and this is added to polyamide Method of mixing with acid organic solvent solution (4) Any method such as a method of dispersing by bead mill or the like may be used, but a method of mixing a dispersion containing filler with a polyamic acid solution, particularly a method of mixing just before film formation It is preferable because the contamination by the filler in the production line is minimized.

  When preparing a dispersion containing a filler, it is preferable to use the same solvent as the polymerization solvent for the polyamic acid. Moreover, in order to disperse | distribute a filler favorably and stabilize a dispersion state, a dispersing agent, a thickener, etc. can also be used in the range which does not affect a film physical property.

When added for improving the slidability of the film, the particle size is 0.1 to 10 μm, preferably 0.1 to 5 μm. If the particle diameter is below this range, the effect of improving the slidability is hardly exhibited, and if it exceeds this range, it tends to be difficult to produce a high-definition wiring pattern. Furthermore, in this case, the dispersion state of the filler is also important, and it is preferable that the aggregate of fillers of 20 μm or more is 50 / m ² or less, preferably 40 / m ² or less. If there are more filler aggregates of 20 μm or more than this range, it may cause repellency when the adhesive is applied, or decrease the adhesion area when creating a high-definition wiring pattern, and the insulation reliability of the flexible printed circuit board itself Tend to drop.

  The glass transition temperature of the thermoplastic polyimide is the temperature at the inflection point in DSC (temperature increase rate: 10 ° C./min). The glass transition temperature of the thermoplastic polyimide is preferably 230 ° C to 320 ° C. 280 ° C. to 320 ° C. is more preferable because of high heat resistance.

  The aromatic diamine used in the thermoplastic polyimide layer of the multilayer polyimide film is 4,4′-diaminodiphenyl ether, 1,3-bis (4-aminophenoxy) benzene, and 2,2-bis [4- (4-aminophenoxy). ) Phenyl] propane. At least one selected from the group consisting of Among these, 4,4′-diaminodiphenyl ether and 2,2-bis [4- (4-aminophenoxy) phenyl] propane are more preferable in terms of the obtained film being homogeneous and amorphous and easily obtained. 2-bis [4- (4-aminophenoxy) phenyl] propane is particularly preferred.

  Aromatic acid dianhydrides used in the thermoplastic polyimide layer of the multilayer polyimide film are pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, It is at least one selected from the group consisting of 4′-biphenyltetracarboxylic dianhydride and 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride. Among them, the use of pyromellitic dianhydride and 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride makes it easy to produce a metal-clad laminate by hot roll lamination, It is preferable in terms of a balance between the peel strength of the metal layer and the multilayer polyimide film, and the molar ratio of pyromellitic dianhydride to 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride is 95: 5-65: 35 is more preferable, and 90: 10-80: 20 is particularly preferable.

  The non-thermoplastic polyimide in the present invention generally means a polyimide that does not soften or show adhesiveness even when heated. In the present invention, it refers to a polyimide which is heated at 380 ° C. for 2 minutes in the state of a film and does not wrinkle or stretch and maintains its shape, or a polyimide having substantially no glass transition temperature.

In the present invention, any monomer addition method may be used for the polymerization of the non-thermoplastic polyamic acid. As typical polymerization methods, the following methods may be mentioned. That is,
1) A method in which an aromatic diamine is dissolved in an organic polar solvent, and this is reacted with a substantially equimolar aromatic tetracarboxylic dianhydride for polymerization.
2) An aromatic tetracarboxylic dianhydride is reacted with a small molar amount of an aromatic diamine compound in an organic polar solvent to obtain a prepolymer having acid anhydride groups at both ends. Subsequently, a method of polymerizing with an aromatic diamine compound so that the aromatic tetracarboxylic dianhydride and the aromatic diamine compound are substantially equimolar in all steps,
3) An aromatic tetracarboxylic dianhydride and an excess molar amount of the aromatic diamine compound are reacted in an organic polar solvent to obtain a prepolymer having amino groups at both ends. Subsequently, after adding an aromatic diamine compound here, using the aromatic tetracarboxylic dianhydride so that the aromatic tetracarboxylic dianhydride and the aromatic diamine compound are substantially equimolar in all steps. How to polymerize,
4) A method in which an aromatic tetracarboxylic dianhydride is dissolved and / or dispersed in an organic polar solvent and then polymerized using an aromatic diamine compound so as to be substantially equimolar,
5) A method of polymerizing by reacting a mixture of substantially equimolar aromatic tetracarboxylic dianhydride and aromatic diamine in an organic polar solvent,
And so on. These methods may be used singly or in combination.

Among them, the non-thermoplastic polyamic acid is used in the following steps (c) to (e).
(C) a step of reacting an aromatic acid dianhydride with an excess molar amount of an aromatic diamine in an organic polar solvent to obtain a prepolymer having amino groups at both ends;
(D) Add additional aromatic diamine to the prepolymer (e) Add aromatic dianhydride so that the aromatic dianhydride and aromatic diamine in all steps are substantially equimolar. Reacting,
It is preferable that it is obtained by going through.

  The polyamic acid obtained by the above method is imidized to obtain a multilayer polyimide film.

  The aromatic diamine used in the non-thermoplastic polyimide layer of the multilayer polyimide film is not particularly limited, but is 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, p-phenylenediamine, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenylmethane, benzidine, 3,3'-dichlorobenzidine, 4,4'- Diaminodiphenyl sulfide, 3,3′-diaminodiphenyl sulfone, 4,4′-diaminodiphenyl sulfone, 4,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 1,5- Diaminonaphthalene, 4,4'-diamy Nodiphenyldiethylsilane, 4,4′-diaminodiphenylsilane, 4,4′-diaminodiphenylethylphosphine oxide, 4,4′-diaminodiphenyl N-methylamine, 4,4′-diaminodiphenyl N-phenylamine, 1 , 4-diaminobenzene (p-phenylenediamine), 1,3-diaminobenzene, 1,2-diaminobenzene, 2,2-bis [4- (4-aminophenoxy) phenyl] propane and derivatives thereof. These can be preferably used alone or in a mixture of any proportions. Among them, film strength, linear expansion coefficient, and diamine selected from at least one selected from 2,2-bis [4- (4-aminophenoxy) phenyl] propane, p-phenylenediamine, and 4,4′-diaminodiphenyl ether, It is preferable because of a good balance of viscoelasticity, and 10 to 50 mol% 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 30 to 70 mol% p-phenylenediamine, 10 to 30 mol% 4, 4'-diaminodiphenyl ether is particularly preferred.

  The aromatic dianhydride used in the non-thermoplastic polyimide layer of the multilayer polyimide film is not particularly limited, but pyromellitic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,2', 3,3'-biphenyltetracarboxylic dianhydride, 3 , 3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride , Bis (3,4-dicarboxyphenyl) propane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) D Dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) ethane dianhydride, oxydiphthalic dianhydride, bis (3,4-dicarboxyphenyl) ) Sulfone dianhydride, p-phenylenebis (trimellitic acid monoester acid anhydride), ethylene bis (trimellitic acid monoester acid anhydride), bisphenol A bis (trimellitic acid monoester acid anhydride) and their A mixture containing a derivative and mixing them alone or in an arbitrary ratio can be preferably used. Among them, at least one selected from pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, and 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride is selected. Preferably it is an acid dianhydride, 60-90 mol% pyromellitic dianhydride, 10-40 mol% 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride or 3,3', It is preferable to use 4,4′-biphenyltetracarboxylic dianhydride in terms of ease of manufacturing a metal-clad laminate by hot roll lamination.

  As a method for producing a multilayer polyimide film, after producing a non-thermoplastic polyimide film, a thermoplastic polyamic acid solution is applied to both sides of the film and dried, and then the imidization reaction is advanced by high-temperature heating to obtain a multilayer polyimide film. be able to. A known technique may be used as an imidization method for the thermoplastic polyamic acid. For example, there are thermal imidization in which an imidization reaction is advanced only by heat, and chemical imidation in which an imidization reaction is advanced using a dehydrating agent. When thermoplastic polyamic acid is applied to the support film, either thermal imidization or chemical imidization may be selected in the case of coextrusion. In the case of coextrusion, imidization is performed by chemical imidization. The method is preferred. The imidizing agent may be added to the thermoplastic polyamic acid solution or may be added to the non-thermoplastic polyamic acid solution.

  When the imidization reaction proceeds, when a tertiary heterocyclic amine such as pyridine, picoline, lutidine, or isoquinoline is used, a dehydrating agent such as acetic anhydride can be used in combination.

  The copper foil used in the flexible metal laminate may have a thickness of 1 to 25 μm, and either a rolled copper foil or an electrolytic copper foil may be used. Considering the adhesion strength of the solder resist, it is preferable to use a copper foil having a rough surface.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited only to these Examples. In addition, the evaluation method of the glass transition temperature of the polyimide film in the synthesis example, an Example, and a comparative example, the adhesive strength of a soldering resist, and the peeling strength of metal foil is as follows.

(Glass transition temperature measurement)
The thermoplastic polyamic acid solution was cast on a shine surface of 18 μm rolled copper foil (BHY-22B-T made by Nikko Metal Co., Ltd.) to a final thickness of 20 μm, and the temperature was 130 ° C. for 3 minutes, 200 ° C. for 2 minutes, 250 Drying was performed at 2 ° C. for 2 minutes, 300 ° C. for 2 minutes, and 330 ° C. for 2 minutes. After drying, the copper foil was removed by etching and dried at 50 ° C. for 30 minutes to obtain a thermoplastic polyimide film. Using the obtained thermoplastic polyimide film, using a DSC220 manufactured by Seiko Instruments Inc., using aluminum as a reference, measuring at a temperature increase rate of 10 ° C./min and a temperature decrease rate of 40 ° C./min in the range of 0 ° C. to 450 ° C. The inflection point was taken as the glass transition temperature.

(Method for producing metal-clad laminate)
Laminated copper foil (BHY-22B-T; manufactured by Nikko Metal) on both sides of the multilayer polyimide film, and protective materials (Apical 125NPI; manufactured by Kaneka) are arranged on both sides of the multilayer polyimide film using a hot roll laminator. Thermally laminating was performed continuously under the conditions of a temperature of 380 ° C., a laminating pressure of 196 N / cm (20 kgf / cm), and a laminating speed of 1.5 m / min, and a flexible metal-clad laminate was produced.

(Measurement of adhesion strength of solder resist)
One side of the metal-clad laminate obtained above was etched and washed with water, and then dried at 100 ° C. for 30 minutes. NPR-80 ID-60 (manufactured by Nippon Polytech) was applied to the etched surface with a Baker type applicator so that the dry thickness was 25 μm, and dried at 80 ° C. for 30 minutes. The resist surface was exposed (600 mJ / cm 2), developed (1% Na 2 CO 3 aqueous solution, 30 ° C., 0.2 MPa), and finally dried at 150 ° C. for 60 minutes. Thereafter, the solder resist surface was affixed to the substrate via an adhesive, the interface between the multilayer polyimide film and the resist was peeled off, peeled off in a 180 ° direction with a width of 2 mm, and the adhesion strength was measured.

(Stripping strength of metal foil)
A sample was prepared according to “6.5 Peel Strength” of JIS C6471, and a 5 mm wide metal foil part was peeled off at a peeling angle of 180 degrees and 50 mm / min, and the load was measured.

The abbreviations of monomers used in the synthesis examples are shown below.
DMF: N, N-dimethylformamide BAPP: 2,2-bis [4- (4-aminophenoxy) phenyl] propane ODA: 4,4′-diaminodiphenyl ether PDA: p-phenylenediamine BPDA: 3, 3 ′, 4 , 4'-biphenyltetracarboxylic dianhydride BTDA: 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride PMDA: pyromellitic dianhydride The following is a synthesis example of a polyamic acid solution.

(Synthesis Example 1)
BAPP (57.3 g: 0.140 mol) and ODA (18.6 g: 0.093 mol) were dissolved in DMF (1173.5 g) cooled to 10 ° C. BTDA (30.0 g: 0.093 mol) and PMDA (25.4 g: 0.086 mol) were added thereto, and the mixture was stirred uniformly for 30 minutes to obtain a prepolymer.

  After PDA (25.2 g: 0.232 mol) was dissolved in this solution, PMDA (54.2 g: 0.248 mol) was dissolved and carefully prepared separately with a 7.2 wt% DMF solution of PMDA prepared separately. 0.1 g (PMDA: 0.038 mol) was added, and the addition was stopped when the viscosity reached about 2500 poise. Stirring was performed for 1 hour to obtain a polyamic acid solution having a rotational viscosity at 23 ° C. of 2600 poise.

  50 g of a curing agent composed of acetic anhydride / isoquinoline / DMF (weight ratio 25.6 g / 7.3 g / 67.1 g) is added to 100 g of this polyamic acid solution, and stirring and defoaming are performed at a temperature of 0 ° C. or lower. Thus, a non-thermoplastic polyamic acid solution was obtained.

(Synthesis Example 2)
BAPP (118.6 g: 0.289 mol) was dissolved in 937.6 g of N, N-dimethylformamide (DMF). BPDA (76.5 g: 0.260 mol) was added thereto, heated to 50 ° C. and stirred for 3 hours to obtain a prepolymer.

  Thereafter, BPDA (7.9 g: 0.027 mol) was carefully added to obtain a polyamic acid solution having a solid component concentration of about 17% and a viscosity of 23 p. At this time, the ratio of aromatic dianhydride to aromatic diamine was 99.3: 100.0.

(Synthesis Example 3)
Using the prepolymer obtained in the same manner as in Synthesis Example 2, BPDA (6.2 g: 0.021 mol) was carefully added to obtain a polyamic acid solution having a solid component concentration of about 17% and a viscosity of 10 poise at 23 ° C. It was. At this time, the ratio of the aromatic dianhydride to the aromatic diamine was 97.2: 100.0.

(Synthesis Example 4)
Using the prepolymer obtained in the same manner as in Synthesis Example 2, BPDA (5.6 g: 0.019 mol) was carefully added to obtain a polyamic acid solution having a solid component concentration of about 17% and a viscosity of 3 poise at 23 ° C. It was. At this time, the ratio of the aromatic dianhydride to the aromatic diamine was 96.5: 100.0.

(Synthesis Example 5)
Using a prepolymer obtained in the same manner as in Synthesis Example 2, BPDA (8.5 g: 0.029 mol) was carefully added to obtain a polyamic acid solution having a solid component concentration of about 17%. At this time, the ratio of aromatic dianhydride to aromatic diamine was 100.0: 100.0.

(Synthesis Example 6)
BPDA (85.0 g: 0.289 mol) was added to 937.6 g of N, N-dimethylformamide (DMF), then BAPP (117.8 g: 0.287 mol) was added, and the solid component concentration was about 17%. A polyamic acid solution having a viscosity of 800 poise at 23 ° C. was obtained. At this time, the ratio between the aromatic dianhydride and the aromatic diamine was 100.7: 100.0.

(Synthesis Example 7)
BAPP (118.6 g: 0.289 mol) was dissolved in 843.4 g of N, N-dimethylformamide (DMF). BPDA (17.1 g: 0.058 mol) was added thereto, heated to 50 ° C., cooled to 10 ° C., and PMDA (45.3 g: 0.208 mol) was added to obtain a prepolymer.

  Thereafter, 65.4 g (PMDA: 0.021 mol) of 7 wt% DMF solution of PMDA prepared separately was carefully added to obtain a polyamic acid solution having a solid component concentration of about 17% and a viscosity of 800 poise at 23 ° C. . At this time, the ratio of aromatic dianhydride to aromatic diamine was 99.3: 100.0.

(Synthesis Example 8)
BAPP (118.6 g: 0.289 mol) was dissolved in 838.3 g of N, N-dimethylformamide (DMF). BPDA (12.7 g: 0.043 mol) was added thereto, heated to 50 ° C., cooled to 10 ° C., and PMDA (48.6 g: 0.223 mol) was added to obtain a prepolymer.

  Thereafter, 65.4 g (PMDA: 0.021 mol) of 7 wt% DMF solution of PMDA prepared separately was carefully added to obtain a polyamic acid solution having a solid component concentration of about 17% and a viscosity of 800 poise at 23 ° C. . At this time, the ratio of aromatic dianhydride to aromatic diamine was 99.3: 100.0.

(Synthesis Example 9)
BAPP (118.6 g: 0.289 mol) was dissolved in 855.3 g of N, N-dimethylformamide (DMF). BPDA (5.9 g: 0.020 mol) was added thereto, heated to 50 ° C., cooled to 10 ° C., and PMDA (55.6 g: 0.255 mol) was added to obtain a prepolymer.

  Thereafter, 34.3 g (PMDA: 0.011 mol) of a 7% by weight PMDA solution separately prepared was carefully added to obtain a polyamic acid solution having a solid component concentration of about 17% and a viscosity of 100 poise at 23 ° C. . At this time, the ratio of aromatic dianhydride to aromatic diamine was 99.0: 100.0.

(Synthesis Example 10)
BAPP (118.6 g: 0.289 mol) was dissolved in 855.3 g of N, N-dimethylformamide (DMF). BPDA (4.3 g: 0.015 mol) was added thereto, heated to 50 ° C., cooled to 10 ° C., and PMDA (55.6 g: 0.255 mol) was added to obtain a prepolymer.

  Thereafter, 56.1 g (PMDA: 0.018 mol) of a 7 wt% DMF solution of PMDA prepared separately was carefully added to obtain a polyamic acid solution having a solid component concentration of about 17% and a viscosity of 2000 poise at 23 ° C. . At this time, the ratio of the aromatic dianhydride to the aromatic diamine was 99.7: 100.0.

Example 1
Using a multi-manifold type three-layer coextrusion multilayer die having a lip width of 200 mm, the polyamic acid solution obtained in Synthesis Example 2 / the polyamic acid solution obtained in Synthetic Example 1 / the polyamic acid solution obtained in Synthetic Example 2 It was extruded and cast on an aluminum foil with a three-layer structure in order. Next, after heating this multilayer film at 130 ° C. × 100 seconds, the gel film having self-supporting properties is peeled off and fixed to a metal frame, 250 ° C. × 20 seconds, 300 ° C. × 40 seconds, 350 ° C. × 30 Second, 370 ° C. × 20 seconds, and imidized to obtain a multilayer polyimide film having a thermoplastic polyimide layer / non-thermoplastic polyimide layer / thermoplastic polyimide layer thickness of 2 μm / 10 μm / 2 μm.

  After producing a metal-clad laminate using a multilayer polyimide film, the adhesion strength measurement of the solder resist and the peeling strength of the metal foil were measured. The results are summarized in Table 2.

(Example 2)
The same procedure as in Example 1 was performed except that the polyamic acid solution obtained in Synthesis Example 3 was used instead of Synthesis Example 2. The results are summarized in Table 2.

(Example 3)
The same procedure as in Example 1 was performed except that the polyamic acid solution obtained in Synthesis Example 7 was used instead of Synthesis Example 2. The results are summarized in Table 2.

Example 4
The same procedure as in Example 1 was performed except that the polyamic acid solution obtained in Synthesis Example 8 was used instead of Synthesis Example 2. The results are summarized in Table 2.

(Example 5)
The same procedure as in Example 1 was performed except that the polyamic acid solution obtained in Synthesis Example 9 was used instead of Synthesis Example 2. The results are summarized in Table 2.

(Example 6)
The same procedure as in Example 1 was performed except that the polyamic acid solution obtained in Synthesis Example 10 was used instead of Synthesis Example 2. The results are summarized in Table 2.

(Comparative Example 1)
The same procedure as in Example 1 was performed except that the polyamic acid solution obtained in Synthesis Example 4 was used instead of Synthesis Example 2. The results are summarized in Table 2.

(Comparative Example 2)
The same procedure as in Example 1 was performed except that the polyamic acid solution obtained in Synthesis Example 5 was used instead of Synthesis Example 2. The results are summarized in Table 2.

(Comparative Example 3)
The same procedure as in Example 1 was performed except that the polyamic acid solution obtained in Synthesis Example 6 was used instead of Synthesis Example 2. The results are summarized in Table 2.

Claims (6)

Nonthermal are circuit comprising a metallic layer is formed for the multilayer polyimide film having a thermoplastic polyimide layer on at least one surface of the thermoplastic polyimide layer, having a solder resist formed to further protect the circuit, Les resist A method for producing a multilayer polyimide film with a coating,
Thermoplastic polyimide layer is bonded to the Les resist,
The aromatic diamine used in the thermoplastic polyimide layer is 4,4′-diaminodiphenyl ether, 1,3-bis (4-aminophenoxy) benzene, and 2,2-bis [4- (4-aminophenoxy) phenyl]. At least one selected from the group consisting of propane,
The aromatic dianhydride used in the thermoplastic polyimide layer is pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-. And at least one selected from the group consisting of biphenyltetracarboxylic dianhydride and 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride,
The thermoplastic polyimide layer is made of a polyimide obtained by imidizing a polyamic acid solution having amino groups at both ends obtained by the following steps (a) and (b). Manufacturing method:
(A) reacting an aromatic acid dianhydride with an excess molar amount of an aromatic diamine in an organic polar solvent to obtain a prepolymer having amino groups at both ends;
(B) To the prepolymer, the aromatic acid dianhydride and aromatic diamine have a molar ratio of 97.0: 100.0 to 99.8: 100.0 in all steps. A step of adding an anhydride to react. The method for producing a resist-coated multilayer polyimide film according to claim 1, wherein the non-thermoplastic polyimide layer is obtained by imidizing a polyamic acid solution obtained by the following steps (c) to (e). :
(C) a step of reacting an aromatic acid dianhydride with an excess molar amount of an aromatic diamine in an organic polar solvent to obtain a prepolymer having amino groups at both ends;
(D) adding an aromatic diamine to the prepolymer;
(E) A step of adding and reacting the aromatic acid dianhydride so that the aromatic acid dianhydride and the aromatic diamine in all steps are substantially equimolar.   The aromatic diamine used in the non-thermoplastic polyimide layer is 10-50 mol% 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 30-70 mol% p-phenylene based on the diamine component. The method for producing a resist-coated multilayer polyimide film according to claim 1 or 2, wherein the diamine is 10 to 30 mol% of 4,4'-diaminodiphenyl ether.   The acid dianhydride used in the non-thermoplastic polyimide layer is 60 to 90 mol% pyromellitic dianhydride, 10 to 40 mol% 3,3 ′, 4,4′− based on the acid dianhydride component. It is a benzophenone tetracarboxylic dianhydride, The manufacturing method of the multilayer polyimide film with a resist of any one of Claims 1-3 characterized by the above-mentioned.   The said multilayer polyimide film is obtained by multilayer coextrusion, The manufacturing method of the multilayer polyimide film with a resist of any one of Claims 1-4 characterized by the above-mentioned. The multilayer polyimide film with a resist obtained by the manufacturing method of any one of Claims 1-5.