JP2000080165A - Copolyimide film, preparation thereof and metallic wiring board using same as substrate material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide copolyimide films which equally meet a high modulus, a low coefficient of thermal expansion, a low coefficient of hygroscopic expansion and a low water absorption and further, excel in alkali etching resistance. SOLUTION: Copolyimide films are prepared from a random and/or block four-component copolyamic acid composed of 10-90 mol% 3,3',4,4'- benzophenonetetracarboxylic dianhydride and 10-90 mol% pyromellitic dianhydride on the basis of the dianhydrides, and 10-90 mol% phenylenediamine and 10-90 mol% bisaminophenoxybenzene on the basis of the diamines.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is used as a metal wiring board base material for a flexible printed circuit or a tape automated bonding tape (TAB tape) having a metal wiring on its surface. High elastic modulus,
A copolymerized polyimide film having a low coefficient of thermal expansion, a low coefficient of hygroscopic expansion, and a low water absorption, and further having excellent alkali etching resistance, a method for producing the same, and a flexible printed circuit having the copolymerized polyimide film as a base material or The present invention relates to a metal wiring board for a tape automated bonding tape.

[0002]

2. Description of the Related Art A TAB tape is provided with a very thin metal wiring on the surface of a heat-resistant film as a base material, and has a "window" for mounting an integrated circuit chip (IC) on the base material. Further, sprockets for precisely feeding the TAB tape are provided near both ends of the TAB tape.

In the above TAB tape, an IC is inserted into a "window" opened in the TAB tape, joined to metal wiring provided on the surface of the TAB tape, and then mounted on the TAB tape.
By joining the tape to the printed circuit for wiring electronic devices, the process of mounting the IC on the electronic circuit is automated, the process is simplified, the productivity is improved, and the electrical characteristics of the electronic device on which the IC is mounted are improved. Has been used to improve.

[0004] The TAB tape has a three-layer structure in which a conductive metal foil is laminated on the surface of a heat-resistant base film via an adhesive such as a polyester base, an acrylic base, an epoxy base or a polyimide base. When,
One having a two-layer structure in which a conductive metal layer is directly laminated on the surface of a heat-resistant base film without using an adhesive is used.

[0005] Therefore, the base film of the TAB tape is required to have heat resistance. In particular, the bonding between the IC and the metal wiring on the TAB tape and the connection between the TAB tape mounting the IC and the printed circuit for electronic equipment wiring are required. Conventionally, a polyimide film has been used so as to withstand high temperatures such as solder welding applied to a base film at the time of joining.

However, when a polyimide film and a metal foil or a metal layer are laminated and a metal wiring is formed by chemical etching of the metal foil or the metal layer, the difference in dimensional change between the polyimide film and the metal due to the heat received. If the deformation of the TAB tape is large, the workability is significantly impaired or sometimes impossible when mounting the IC or joining the TAB tape mounting the IC to the printed circuit for wiring the electronic device. Because it will be
It is required that the thermal expansion coefficient of the polyimide film be approximated to that of metal to reduce the deformation of the TAB tape.

Also, by reducing the water absorption and the coefficient of humidity expansion of the polyimide film to reduce the dimensional change of the TAB tape due to the change in the humidity of the working environment, the metal wiring can be made finer and the strain load on the metal wiring can be reduced. In addition, there is a strong demand for reducing the distortion load of the mounted IC.

Further, it is possible to reduce a dimensional change due to a tensile force or a compressive force applied to a TAB tape mounted on an IC and bonded to a printed circuit for electronic device wiring, to reduce the size of the metal wiring and to reduce the distortion to the metal wiring. Load reduction and mounted IC
This is important for reducing the strain load on the substrate, and a higher elastic modulus is required for the polyimide film as the base material.

In addition, when bonding with an IC, there is a case where "gold plating" is formed on the wiring on the polyimide film as a base material and connected, and a strong alkali solution is used as the gold plating solution in some cases. In many cases, when the polyimide film is attacked by a plating solution at that time, the wiring on the polyimide film is easily peeled off. Therefore, a demand for a polyimide film excellent in alkali-resistant etching is increasing.

Conventional methods aimed at obtaining a copolymerized polyimide film satisfying these required properties include:
JP-A-4-299885 discloses 3,3 ', 4,4'
-A copolymerized polyimide film produced from a copolymerized polyamic acid comprising benzophenone tetracarboxylic dianhydride, pyromellitic dianhydride, phenylenediamine and diaminodiphenyl ether has been proposed, and furthermore, a copolymerized polyamic acid film is chemically synthesized. There has been proposed a method of forming a copolymerized polyimide film having excellent chemical etching properties by a conversion method.

Japanese Patent Application Laid-Open No. 148458/1993 discloses 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, pyromellitic dianhydride, phenylenediamine and diaminodiphenyl ether. There has been proposed a TAB tape in which an adhesive layer and a protective layer are provided on a copolymerized polyimide film produced from copolymerized polyamic acid.

However, in the above-mentioned conventional method, when used as a metal wiring board substrate, a high elastic modulus, a low coefficient of thermal expansion, a low coefficient of hygroscopic expansion, a low coefficient of water absorption, and a resistance to alkali etching are highly balanced. A satisfactory copolymerized polyimide film could not be obtained, and further improvement was required.

[0013]

SUMMARY OF THE INVENTION The present invention has been achieved as a result of studying the above-mentioned problems in the prior art as a problem. A flexible printed circuit having metal wiring on the surface thereof has been achieved. Or Tape Auto Join
When applied to metal wiring board base material for mated bonding tape (TAB tape), it satisfies high elastic modulus, low coefficient of thermal expansion, low coefficient of hygroscopic expansion, and low coefficient of water absorption, and has excellent alkali etching resistance. Copolymerized polyimide film,
It is an object of the present invention to provide a method of manufacturing the same and a metal wiring board using the same as a base material.

[0014]

In order to achieve the above-mentioned object, the copolymerized polyimide film of the present invention comprises 10 to 90 mol% of 3,3 ', 4,4'-based on dianhydride.
A benzophenonetetracarboxylic dianhydride and 10 to 90 mol% of pyromellitic dianhydride, and a four component consisting of 10 to 90 mol% of phenylenediamine and 10 to 90 mol% of bisaminophenoxybenzene based on diamine. It is characterized by being produced from a polymerized polyamic acid.

Further, the copolymerized polyimide film of the present invention may contain 10 to 90 mol% of 3,3 based on dianhydride.
', 4,4'-benzophenonetetracarboxylic dianhydride and 10 to 90 mol% of pyromellitic dianhydride, and 10 to 90 mol% of phenylenediamine and 10 to 90 mol% of bisamino based on diamine Characterized in that it is produced from a quaternary polyamic acid having a block copolymer component consisting of phenoxybenzene, in which case 20 to 9 based on dianhydride.
0 mol% of 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride and 10 to 80 mol% of pyromellitic dianhydride and 10 to 70 mol% of phenylenediamine and 30 to 30 mol% based on diamine More preferably, it is prepared from a quaternary polyamic acid having a block copolymerization component comprised of from about 90 mole percent bisaminophenoxybenzene.

In the copolymerized polyimide film of the present invention, the bisaminophenoxybenzene is
1,3-bis (4-aminophenoxy) benzene or 1,4-bis (4-aminophenoxy) benzene, and the phenylenediamine is p-phenylenediamine, and the bisaminophenoxybenzene is 1,3 -Bis (4-aminophenoxy) benzene is a preferable condition, and by applying these conditions, it is possible to expect to obtain a more excellent effect.

The copolymerized polyimide film of the present invention can be obtained by combining a general method for producing polyimide. Preferred production methods for easily obtaining the present invention include the following steps (A) to (A). (D) is sequentially performed.

(A) 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, pyromellitic dianhydride, phenylenediamine and bisaminophenoxybenzene in an inert solvent with phenylenediamine and Pyromellitic dianhydride, or at least twice, to form a quaternary polyamic acid having a block component with phenylenediamine and 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride. (B) mixing the four-component copolymerized polyamic acid solution from the step (A) with a conversion agent capable of converting the copolymerized polyamic acid into a copolymerized polyimide; C) casting or extruding the mixture from step (B) onto a smooth surface to form a copolymer polyamic acid-copolyimide gel fill; Step of Forming, and (D)
The gel film from the step (C) is used for 200 to 500
A step of converting copolymerized polyamic acid into a copolymerized polyimide by heating at a temperature of ° C.

In the method for producing a copolymerized polyimide film according to the present invention, the quaternary copolymerized polyamic acid is used in an amount of 10 to 90 mol% of 3,3 based on dianhydride.
', 4,4'-benzophenonetetracarboxylic dianhydride and 10 to 90 mol% of pyromellitic dianhydride, and 10 to 90 mol% of phenylenediamine and 10 to 90 mol% of bisamino based on diamine A copolymerized polyamic acid having a block copolymerization component composed of phenoxybenzene, wherein the quaternary copolymerized polyamic acid is 20 to 90 mol% of 3,3 ', 4,4'-benzophenone based on dianhydride A block copolymer component comprising tetracarboxylic dianhydride and 10 to 80 mol% of pyromellitic dianhydride, and 10 to 70 mol% of phenylenediamine and 30 to 90 mol% of bisaminophenoxybenzene based on diamine. And that the phenylenediamine is - it is a phenylenediamine,
It is a preferable condition that the bisaminophenoxybenzene is 1,3-bis (4-aminophenoxy) benzene, and by applying these conditions, it is possible to expect to obtain a more excellent effect.

Further, the metal wiring board for a flexible printed circuit or tape automation bonding tape of the present invention is characterized in that the above-mentioned copolymerized polyimide film is used as a base material and metal wiring is applied to the surface thereof. I do.

[0021]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The configuration and effects of the present invention will be described below in detail.

The copolymerized polyimide constituting the film of the present invention may be either a block polymer or a random polymer, but is preferably a copolymerized polyimide having a block copolymer component.

The preferred block copolymer component in this case is a polyamic acid comprising phenylenediamine and pyromellitic dianhydride, or a phenylenediamine and 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride. It is a polyamic acid, and after forming a copolymerized polyamic acid containing these block components, it is imide-converted to a copolymerized polyimide containing a block component.

The reaction for forming the four-component copolymerized polyamic acid is carried out at least in two parts, and the copolymerized polyamic acid containing a block component is formed and imidized to be incorporated into the copolymerized polyimide polymer.

The four-component copolymerized polyimide polymer of the present invention allows flexible printed circuit or tape automated joining (Tape).
Automated Bonding) When applied to metal wiring board base material for TAB tapes, high elastic modulus, low thermal expansion coefficient,
It is possible to realize a copolymerized polyimide film that satisfies a high level by balancing the low coefficient of moisture absorption expansion, the low water absorption and the alkali etching property.

By incorporating a copolymerization block component into the copolymerized polyimide polymer, the above properties can be set in more preferable ranges. Particularly preferred blocking components in this case are those obtained by reaction with phenylenediamine and pyromellitic dianhydride.

The diamine used in the present invention includes:
An inflexible diamine such as phenylenediamine,
With flexible diamines such as bisaminophenoxybenzene. The copolymerized polyimide is used in an amount of about 10 to 90 mol%, preferably 10 to 7 mol%, based on the total molar amount of the diamine.
It is produced by imid conversion of a copolyamide obtained using 0 mol% of phenylenediamine. In the present invention, phenylenediamine acts to increase the modulus of the film.

As the phenylenediamine used in the present invention, in addition to p-phenylenediamine, m-phenylenediamine, o-phenylenediamine and the like, phenylenediamine having a substituent in part can be used, and particularly preferred. Is p-phenylenediamine.

As bisaminophenoxybenzene,
1,3-bis (4-aminophenoxy) benzene, 1,
4-bis (4-aminophenoxy) benzene, 1,2-
Bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 1,4-bis (3
-Aminophenoxy) benzene, 1,2-bis (3-aminophenoxy) benzene, 1,3-bis (2-aminophenoxy) benzene, 1,4-bis (2-aminophenoxy) benzene, 1,2-bis (2-aminophenoxy) benzene, 1,3-bis (3,4′-aminophenoxy) benzene, 1,4-bis (3,4′-aminophenoxy) benzene, 1,2-bis (3,4 ′) -Aminophenoxy) benzene, 1,3-bis (2,4'-aminophenoxy) benzene, 1,4-bis (2,4'-aminophenoxy) benzene, 1,2-bis (2,4'-amino Phenoxy) benzene, 1,3-bis (2,3′-
Aminophenoxy) benzene, 1,4-bis (2,3 ′)
-Aminophenoxy) benzene, 1,2-bis (2,3
In addition to '-aminophenoxy) benzene and the like, bisaminophenoxybenzene partially having a substituent is used,
Particularly preferred is 1,3-bis (4-aminophenoxy)
Benzene is used. In the present invention, bisaminophenoxybenzene acts to lower the water absorption.

The tetracarboxylic dianhydride used in the present invention includes a non-flexible tetracarboxylic dianhydride such as pyromellitic dianhydride, and 3,3 ', 4.
Flexible tetracarboxylic dianhydrides, such as 4'-benzophenone tetracarboxylic dianhydride. The copolymerized polyimide is about 10 to 9 based on the total molar amount of dianhydride.
0 mol%, preferably 20 to 90 mol% of 3,3
It is produced by imide conversion of a quaternary polyamic acid obtained using ', 4,4'-benzophenonetetracarboxylic dianhydride.

The performance of the copolymerized polyimide film depends on the ratio of the phenylenediamine component in the diamine component used in the production of the copolymerized polyamic acid and the 3,3 ′, 4,4 ′ in the tetracarboxylic dianhydride component. -It can be adjusted by the use ratio of benzophenonetetracarboxylic dianhydride. When a large amount of phenylenediamine component is used, high elastic modulus and dimensional stability are improved, but there is a drawback that water absorption is increased. In order to lower water absorption, 3,3 ′, 4,4′-benzophenonetetrane is used. Although a large amount of carboxylic dianhydride can be used, in this case, the elastic modulus and dimensional stability are reduced. Therefore, it is necessary to carefully adjust the molar ratio of each component in order to balance each characteristic value. According to the present invention, by preferably employing a copolymerized polyimide containing a block copolymer component, a low water absorption, a high elastic modulus and dimensional stability can be easily realized in a well-balanced manner.

The four-component copolymeric polyamic acid of the present invention comprises 1
At a temperature of 75 ° C. or lower, preferably 90 ° C. or lower, the molar ratio of the tetracarboxylic dianhydride component and the diamine component is about 0.90 to 1.10, preferably 0.95 to 1.
05, more preferably from 0.98 to 1.02, and produced by reacting each component with a non-reactive organic solvent.

Each of the above-mentioned components may be independently and sequentially supplied to the organic solvent, may be simultaneously supplied, or the organic solvent may be supplied to the mixed components. In order to achieve this, it is preferable to sequentially add each component to the organic solvent.

In the case of sequentially supplying each component, it is preferable to supply the diamine component and the tetracarboxylic dianhydride component, which are to be copolymerized block components, with priority. That is, in order to produce a copolymerized polyamic acid containing a copolymerized block component, the reaction is carried out at least twice, and firstly, a copolymerized polyamic acid containing a copolymerized block component is obtained. Is converted into an imide, whereby a copolymerized block component is incorporated into the obtained copolymerized polyimide.

The time required to form the copolymerized polyamic acid block component may be determined by the reaction temperature and the ratio of the block component in the copolymerized polyamic acid. About 20 hours is appropriate.

Specifically, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride (BTDA), pyromellitic dianhydride (PMDA), and diamine components as tetracarboxylic dianhydride components PMDA and PD using p-phenylenediamine (PDA) and 1,3-bis (4-aminophenoxy) benzene (RODA)
A production example of a copolymerized polyimide polymer containing a copolymerized block component consisting of A will be described below.

First, PDA is dissolved in dimethylacetamide (DMAc) as an organic solvent, and PMDA is added to complete the reaction of the block component. Next, after adding and dissolving RODA in the solution, BTDA is added to the solution and reacted to obtain a four-component copolymer polyamic acid solution containing a copolymer block component of PDA and PMDA.

In this case, a small amount of RODA may be added to the PDA supplied first, or PDA and P
It is also possible to control the size of the copolymer block component by making the molar ratio with MDA unequal, but in order to make the effect of the copolymer block component effective, PDA
It is preferable to make the molar ratio between PMDA and PMDA substantially equal.

The end point of the production of the four-component copolymeric polyamic acid is determined by the polyamic acid concentration of the solution and the viscosity of the solution. In order to accurately determine the viscosity of the solution at the end point, it is effective to add a part of the finally supplied component as a solution of an organic solvent used in the reaction, but it does not significantly reduce the polyamic acid concentration. Such adjustment is necessary.

If the amount of BTDA added is greater than the amount of PMDA added, gelation may occur during the polymerization reaction or during imidization. For the purpose of preventing the gelation by BTDA, it is also preferable to add a terminal blocking agent such as dicarboxylic anhydride and silylating agent in the range of 0.001 to 2% based on the solid content (polymer concentration). I can do it. Acetic anhydride is used as the dicarboxylic anhydride, non-halogen hexamethyldisilazane is used as the silylating agent, N, O-
(Bistrimethylsilyl) acetamide and N, N-bis (trimethylsilyl) urea are particularly preferably used.

The concentration of the copolymerized polyamic acid in the solution is 5 to 40% by weight, preferably 10 to 30% by weight.

The organic solvent is selected from those which are non-reactive with the respective components and the copolymerized polyamic acid as a polymerization product, are capable of dissolving all of the components and dissolve the copolymerized polyamic acid. Is preferred.

Preferred organic solvents include N, N-dimethylacetamide, N, N-diethylacetamide,
N, N-dimethylformamide, N, N-diethylformamide, N-methyl-2-pyrrolidone, and the like,
These can be used alone or as a mixture, and in some cases, can be used in combination with a poor solvent such as benzene.

In producing the copolymerized polyimide film of the present invention, the four-component copolymerized polyamic acid solution thus obtained is pressurized by an extruder or a gear pump and sent to a process for producing a copolymerized polyamic acid film.

The four-component copolymerized polyamic acid solution is filtered to remove foreign substances, solids, high-viscosity impurities, and the like mixed in the raw materials or generated in the polymerization step, and is used for a film forming die or a coating head. Is formed into a film, extruded onto a rotating or moving support, and heated from the support to produce a copolyamide acid-copolyimide gel film in which the copolyamide is partially imidized, When the gel film becomes self-supporting and can be peeled off from the support, it is peeled off from the support, introduced into a drier, heated in a drier, and the solvent is dried to complete the imide conversion. A polymerized polyimide film is produced.

The imide conversion of the copolymerized polyamic acid can be carried out by a thermal conversion method using only heating, a copolyamide acid mixed with an imide conversion agent, or a heat treatment of the copolyamide acid, or a copolyamide acid added to a bath of the imide conversion agent. Although any of the chemical conversion methods of immersion can be adopted, in the present invention, the chemical conversion method is more flexible than the thermal conversion method, and is a flexible printed circuit or Tape Automated Bonding tape (TAB tape). When applied to a metal wiring board substrate for (1), it is suitable for achieving a high degree of elasticity, a low coefficient of thermal expansion, a low coefficient of hygroscopic expansion, a low coefficient of water absorption, and alkali etching resistance.

In addition, the method of mixing the imide conversion agent with the four-component copolymer polyamic acid by a chemical conversion method, forming a film, and then performing a heat treatment, has a short time required for the imide conversion and enables uniform imide conversion. In addition to the advantages, it is easy to peel off from the support, furthermore, it has an advantage such as strong odor and the ability to handle the imide conversion agent requiring isolation in a closed system, etc., after forming the copolymeric polyamic acid film. The method is preferably employed as compared with a method of immersing in a bath of a conversion agent or a dehydrating agent.

In the present invention, a tertiary amine which promotes imide conversion and a dehydrating agent which absorbs water generated by imide conversion are used in combination as the imide conversion agent. The tertiary amines are added and mixed in an approximately equimolar to slightly excessive amount with the copolymerized polyamic acid, and the dehydrating agent is added in an amount about 2 times the molar amount or slightly in excess of the copolymerized polyamic acid. Adjusted appropriately to adjust the points.

The imide conversion agent may be added at any time after the completion of the polymerization of the copolymerized polyamic acid, at which point the copolymerized polyamic acid solution reaches the die for film formation or the coating head. In order to prevent the imide conversion in the above, it is preferable to add the mixture shortly before reaching the die for forming a film or the coating head and mix the mixture with a mixer.

As the tertiary amine, pyridine or β-
Although picoline is preferred, α-picoline, 4-methylpyridine, isoquinoline, triethylamine and the like can also be used. The amount used is adjusted according to the respective activity.

As the dehydrating agent, acetic anhydride is most generally used, but propionic anhydride, butyric anhydride, benzoic acid, formic anhydride and the like can also be used.

The copolymerized polyamic acid film containing the imidization agent is converted into an imidized by the heat received from the support and the space on the opposite side of the support, and a partially imidized copolyamide-copolyimide gel is obtained. It becomes a film and is peeled from the support.

In this case, the larger the amount of heat applied from the support and the space on the opposite surface, the more the imide conversion is promoted and the faster the exfoliation occurs, but if the amount of heat is too large, the gas of the organic solvent between the support and the gel film becomes gel. Since the film is deformed and becomes a defect of the film, it is desirable to determine the amount of heat in consideration of the position of the peeling point and the defect of the film.

The gel film peeled off from the support is introduced into a dryer, where the solvent is dried and the imidization is completed.

This gel film contains a large amount of an organic solvent, and its volume is greatly reduced during the drying process. Therefore, in order to concentrate the dimensional shrinkage due to the volume reduction in the thickness direction, both ends of the gel film are gripped with a tenter clip, and the gel film is introduced into a dryer (tenter) by the movement of the tenter clip. It is common practice to heat and consistently perform solvent drying and imidization.

The drying and the imidization are carried out at a temperature of from 200 to 500 ° C. The drying temperature and the imide conversion temperature may be the same temperature or different temperatures, but in the stage of drying a large amount of the solvent, prevent the bumping of the solvent as a lower temperature, and when there is no possibility of bumping of the solvent, raise the temperature to a higher temperature. Preferably, the temperature is increased stepwise so as to promote imide conversion.

In the tenter, the distance between the tenter clips at both ends of the film can be expanded or reduced to perform stretching or relaxation.

It preferably contains a copolymer block component,
A cut sheet-shaped copolymerized polyimide film obtained by imide conversion by a chemical conversion method can be produced by cutting from a continuous film produced as described above. As shown in the examples, in a resin or glass flask,
Preferably, a copolymerized polyamic acid containing a copolymerized block component is produced, and a mixed solution obtained by mixing a chemical conversion agent with the copolymerized polyamic acid solution is cast on a support such as a glass plate and heated. As a partially imidized self-supporting copolyamide-copolyimide gel film, peeled from the support, fixed to a metal fixing frame or the like and heated while preventing dimensional change, solvent Can be produced by a method of drying and imide conversion.

Thus, the copolymerized polyimide film of the present invention obtained by the imide conversion by the chemical conversion method is more flexible than the copolymerized polyimide film obtained by the thermal conversion method. Automated tape joining
(Tape Automated Bonding) When applied to a metal wiring board base material for tape (TAB tape), it is suitable for achieving a high degree of elasticity, a low coefficient of thermal expansion, a low coefficient of hygroscopic expansion, and a low coefficient of water absorption in a balanced and high degree. And has excellent alkali etching resistance.

Accordingly, a metal wiring board for a flexible printed circuit or a tape automated bonding tape having a metal wiring on the surface using the copolymerized polyimide film of the present invention as a base material has a high elastic modulus and low thermal expansion. It exhibits high-performance characteristics in which the coefficient, low coefficient of hygroscopic expansion, low water absorption and alkali etching resistance are balanced and highly satisfied.

In the copolymerized polyimide film of the present invention, the elastic modulus is preferably 500 kg / cm ² or more, the thermal expansion coefficient is preferably 10 to 20 ppm / ° C., and the water absorption is 2% or less, particularly preferably. 1% or less. As for the alkali etching resistance, it is a preferable condition that the surface is not attacked. The evaluation method is described below, but the evaluation can be performed under alkaline conditions stronger than the plating solution used, and the erosion rate of the surface can be evaluated.

[0062]

EXAMPLES The present invention will now be described in detail with reference to examples, but the present invention is not limited to these examples. In addition, each film characteristic value is measured by the following method.

In the following examples, the abbreviations DMAc are dimethylacetamide, and BTDA is 3,3 ', 4,4
'-Benzophenonetetracarboxylic dianhydride was converted to PM
DA is an abbreviation that indicates pyromellitic dianhydride, PDA is p-phenylenediamine, and RODA is 1,3-bis (4-aminophenoxy) benzene.

(1) Elastic Modulus Elastic modulus was measured at room temperature according to JIS K7113 at room temperature.
It was determined from the slope of the initial rising portion of the tension-strain curve obtained at a tensile speed of 300 mm / min using a Tensilon type tensile tester manufactured by NREC.

(2) Coefficient of thermal expansion The coefficient of thermal expansion was determined using a TMA-50 thermomechanical analyzer manufactured by Shimadzu Corporation at a temperature rising rate of 10 ° C./min and a temperature decreasing rate of 5 ° C./min for the second time. From 50 ° C to 200 ° C when the temperature rises (falls)
It was determined from the dimensional change during.

(3) Hygroscopic Expansion Coefficient The hygroscopic expansion coefficient was determined by using a TM-7000 type thermomechanical analyzer manufactured by Vacuum Riko Co., Ltd. at 25 ° C. at a humidification rate of 0.3% RH / min. From 5% RH to 90% RH.

(4) Water Absorption The water absorption was kept for 48 hours in a thermo-hygrostat (STPH-101, manufactured by Tabai Espec Corp.) conditioned at 25 ° C. and 95% RH, and then dried. The weight difference from the state was determined as a percentage.

(5) Alkali etching resistance Alkali etching resistance is obtained by coating one surface of a polyimide film in an ethanol / water mixed solution having a volume ratio of 80/20.
The thickness of the film before and after contacting with a potassium hydroxide solution of N at 40 ° C. for 120 minutes was measured using a LITE manufactured by Mitutoyo Corporation.
It was determined by measuring with a MATIC thickness gauge. Evaluation criteria were determined as follows according to the thickness change rate. The X level is a level at which the film surface is eroded when immersed in the plating solution, which affects the adhesion to the wiring.

○ Thickness change rate less than 1% △ Thickness change rate 1% or more and less than 5% × Thickness change rate 5% or more.

(6) Evaluation of the amount of warpage of the metal laminate A polyimide-based adhesive was applied to the polyimide film, and a copper foil was bonded thereon at a temperature of 250 ° C. Thereafter, the temperature was raised to a maximum temperature of 300 ° C. to cure the adhesive, and the obtained metal laminate was cut into a sample size of 35 mm × 120 mm, left at 25 ° C. and 60% RH in an atmosphere for 24 hours. Warpage was measured.
For the warpage, the sample was placed on a glass plate, and the heights of the four corners were measured and averaged. The evaluation criteria were determined as follows according to the amount of warpage. × level is used as a metal wiring circuit board,
This is a level that makes handling difficult during transport in the post-process.

○ The amount of warpage is less than 1 mm △ The amount of warpage is 1 mm or more and less than 3 mm × The amount of warpage is 3 mm or more (7) Blister generation at the time of solder float The metal laminate prepared in the above (6) is subjected to a thermo-hygrostat (STP)
H-101, manufactured by Tabai Espec Corp.)
The humidity was adjusted under the conditions of H and 25 ° C. for 48 hours. Solder bath (HT
-01, manufactured by Simpo Industry Co., Ltd.), and the state of blistering of the metal laminate was observed. The temperature of the solder bath is 240
The temperature is raised at 20 ° C increments from ℃ to 280 ° C. The sample after humidity control was floated on a solder bath. The sample surface was visually observed and determined as follows according to the lowest temperature at which blisters were generated. The × level is a level that requires a drying step because blisters are likely to occur during solder float when used as a metal wiring circuit board.

A: No blistering occurs at 280 ° C.

Blistering starts at 280 ° C.

Δ At 260 ° C., blisters begin to occur.

× Blisters are generated at 240 ° C.

Example 1 A 500 cc glass flask was charged with 150 ml of DMAc, and PDA was supplied and dissolved in DMAc, followed by RODA, BTDA and PDA.
MDA is sequentially supplied and stirred at room temperature for about 1 hour. Finally, a solution having a copolymerized polyamic acid concentration of 20% by weight, comprising a tetracarboxylic dianhydride component and a diamine component having a stoichiometry of about 100 mol% and a composition shown in Table 1, was prepared.

30 g of this copolymerized polyamic acid solution was added to 1
2.7 ml of DMAc, 3.6 ml of acetic anhydride and 3.
A mixed solution prepared by mixing with 6 ml of β-picoline was prepared, and the mixed solution was cast on a glass plate, and then heated on a hot plate heated to 150 ° C. for about 4 minutes to form a self-supporting copolymer polyamic acid. -A copolymerized polyimide gel film was formed and peeled from the glass plate.

This gel film was fixed to a metal fixing frame provided with a large number of pins, and heated at a temperature of 250 ° C. to 330 ° C. for 30 minutes, and then heated at 400 ° C. for about 5 minutes.
A copolymerized polyimide film having a thickness of about 25 μm was obtained.

Table 1 shows the characteristic value evaluation results of the obtained copolymerized polyimide film.

[Examples 2 to 4] In a 500 cc glass flask, 150 ml of DMAc was placed, and PDA was added to DMA.
c) to dissolve, followed by PMDA and stirred at room temperature for about 1 hour. ROD is added to this polyamic acid solution.
A, and after completely dissolving, supply BTDA,
Stirred at room temperature for about 1 hour. Subsequently, 1 mol% of acetic anhydride was added to the diamine component, and the mixture was further stirred for about 1 hour.
A solution having a copolyamide acid concentration of 20% by weight was prepared from components having the composition shown in Table 1 in terms of mol% stoichiometry.

This solution having a polyamic acid concentration of 20% by weight was treated in the same manner as in Example 1 to obtain a solution having a thickness of about 25 μm.
Was obtained.

The results of evaluating the characteristic values of the obtained copolymerized polyimide film are also shown in Table 1.

Example 5 A 500 cc glass flask was charged with 150 ml of DMAc, and PDA was supplied and dissolved in DMAc, followed by supplying PMDA, followed by stirring at room temperature for about 1 hour. Subsequently, 1 mol% of acetic anhydride was added to the diamine component, and the mixture was further stirred for about 1 hour. RODA was supplied to the polyamic acid solution, and after completely dissolving, BTDA and PMDA were supplied. The mixture was stirred for a period of time to prepare a solution having a polyamic acid concentration of 23% by weight in which the tetracarboxylic dianhydride component and the diamine component were composed of components having a composition shown in Table 1 with a stoichiometry of about 100 mol%.

This copolymerized polyamic acid solution was prepared in Example 1
To obtain a copolymerized polyimide film having a thickness of about 50 μm.

Table 1 also shows the evaluation results of the characteristic values of the obtained copolymerized polyimide film.

[0086]

[Table 1] [Comparative Example 1] DMA was placed in a 500 cc glass flask.
150 ml, and supply RODA into DMAc to dissolve, then supply BTDA, stir at room temperature for about 1 hour, and mix tetracarboxylic dianhydride component and diamine component at about 100 mol% stoichiometry. A solution having a polyamic acid concentration of 20% by weight comprising components having the compositions shown in Table 1 was prepared.

This polyamic acid solution was treated in the same manner as in Example 1 to obtain a copolymerized polyimide film having a thickness of about 25 μm.

Table 2 shows the characteristic value evaluation results of the obtained copolymerized polyimide film.

[Comparative Examples 2 to 8] 150 ml of DMAc was placed in a 500 cc glass flask, and the raw materials and the compositions shown in Table 2 were sequentially supplied and dissolved in DMAc, and stirred at room temperature for about 1 hour. A solution having a carboxylic acid dianhydride component and a diamine component having a stoichiometry of about 100 mol% and having a composition shown in Table 1 and having a polyamic acid concentration or a copolymerized polyamic acid concentration of 20% by weight was prepared.

This polyamic acid solution or copolymerized polyamic acid solution was treated in the same manner as in Example 1 to obtain a copolymerized polyimide film having a thickness of about 25 μm.

Table 2 also shows the results of evaluating the characteristic values of the obtained copolymerized polyimide film.

[Table 2] As is clear from the results described in Tables 1 and 2,
The four-component random copolymer polyimide film and the four-component block copolymer polyimide film of the present invention obtained by the chemical conversion method comprising BTDA, PMDA, PPD and RODA are compared with the two-component polyimide film or the three-component random copolymer polyimide film. It has a balanced and high balance of high elasticity, low coefficient of thermal expansion, low coefficient of moisture expansion, low water absorption and excellent alkali etching resistance, and can be used for flexible printed circuits or tape automated bonding (Tape Au
It has a suitable performance as a metal wiring board base material for tomated bonding tape (TAB tape).

[0092]

As described above, the copolymerized polyimide film of the present invention is more flexible than a copolymerized polyimide film obtained by a thermal conversion method. ) Tape (T
When applied to a metal wiring board substrate for AB tape), it is suitable for achieving a high and high elasticity, a low coefficient of thermal expansion, a low coefficient of moisture expansion and a low coefficient of water absorption in a balanced manner and at a high level. It has an etching property.

Therefore, a metal wiring board for a flexible printed circuit or a tape automated bonding tape, which is formed by using the copolymerized polyimide film of the present invention as a base material and providing metal wiring on the surface, has a high elastic modulus and low thermal expansion. It exhibits high-performance characteristics that balance the coefficient, the low coefficient of hygroscopic expansion, the low water absorption and the resistance to alkali etching to a high degree.

 ──────────────────────────────────────────────────続 き Continued on the front page F-term (reference) 4F100 AB01B AB33B AK49A AL01A BA02 BA10A BA10B GB43 JB01 JB07 JJ03 JK07 JL04 YY00A 4J043 PA04 PA06 PA08 PA09 QB15 QB26 QB31 RA06 RA35 SA06 SB03 TA22 TB UA 132 UA 121 UA 121 UA 121 UA 121 UA 121 VA021 VA022 VA031 VA041 VA051 VA061 VA062 VA071 VA081 VA091 VA101 XA16 XB35 YA08 ZB11 ZB50

Claims (10)

[Claims] 1. 10 to 90 mol% based on dianhydride
3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride and 10 to 90 mol% of pyromellitic dianhydride, and 10 to 90 mol% of phenylenediamine and 10 to 90 mol based on diamine % Of bisaminophenoxybenzene in a four-component copolymerized polyamic acid. 2. 10 to 90 mol% based on dianhydride
3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride and 10 to 90 mol% of pyromellitic dianhydride, and 10 to 90 mol% of phenylenediamine and 10 to 90 mol based on diamine A copolymerized polyimide film produced from a quaternary copolymerized polyamic acid having a block copolymerized component comprising 2% bisaminophenoxybenzene. 3. 20 to 90 mol% based on dianhydride
3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride and 10 to 80 mol% of pyromellitic dianhydride, and 10 to 70 mol% of phenylenediamine and 30 to 90 mol based on diamine 3. The copolymerized polyimide film of claim 2, wherein the copolymerized polyimide film is made from a quaternary polyamic acid having a block copolymerization component consisting of 2% bisaminophenoxybenzene. 4. The method according to claim 1, wherein the bisaminophenoxybenzene is
The copolymerized polyimide film according to any one of claims 1 to 3, which is 1,3-bis (4-aminophenoxy) benzene or 1,4-bis (4-aminophenoxy) benzene. 5. The method according to claim 1, wherein the phenylenediamine is p-phenylenediamine, and the bisaminophenoxybenzene is 1,3-bis (4-aminophenoxy) benzene. Item 12. The copolymerized polyimide film according to item 1. 6. A method for producing a copolymer polyimide film having a block copolymer component, which comprises sequentially performing the following steps (A) to (D). ◎ (A) 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, pyromellitic dianhydride, phenylenediamine and bisaminophenoxybenzene in an inert solvent with phenylenediamine and pyromellitic Acid dianhydride or phenylenediamine and 3,3 ′, 4
(B) reacting at least two times to form a four-component copolymeric polyamic acid having a block component with 4′-benzophenonetetracarboxylic dianhydride; Mixing a conversion agent capable of converting the copolymerized polyamic acid into a copolymerized polyimide into the component copolymerized polyamic acid solution; (C) casting or extruding the mixture from the step (B) onto a smooth surface; Forming a copolyamide-copolyimide gel film, and (D) forming the gel film from the step (C) in a range of 200 to
Converting the copolyamide to copolyimide by heating at a temperature of 500 ° C. 7. The quaternary polyamic acid is used in an amount of 10 to 90 mol%, based on dianhydride, of 3,3 ′, 4,4.
'-Benzophenonetetracarboxylic dianhydride and 10
A copolymer polyamic acid having a block copolymerization component comprising from 10 to 90 mol% of pyromellitic dianhydride and 10 to 90 mol% of phenylenediamine and 10 to 90 mol% of bisaminophenoxybenzene based on diamine. The method for producing a copolymerized polyimide film according to claim 6, wherein: 8. The quaternary polyamic acid is used in an amount of from 20 to 90 mol% of 3,3 ', 4,4 based on dianhydride.
'-Benzophenonetetracarboxylic dianhydride and 10
To 80% by mole of pyromellitic dianhydride and 10 to 70% by mole of phenylenediamine and 30 to 90% by mole of bisaminophenoxybenzene based on diamine. The method for producing a copolymerized polyimide film according to claim 6, wherein: 9. The method according to claim 6, wherein the phenylenediamine is p-phenylenediamine, and the bisaminophenoxybenzene is 1,3-bis (4-aminophenoxy) benzene. A method for producing the copolymerized polyimide film according to the above. 10. A flexible printed circuit or tape automation comprising the copolymer polyimide film according to any one of claims 1 to 5 as a base material and metal wiring provided on the surface thereof. Metal wiring board for joining tape.