JPH08143688A - Modified polyimide film and laminate - Google Patents

Abstract

PURPOSE: To obtain the subject film having the film surface with a specific element weight ratio, a P content in the film in a specific range, excellent in adhesiveness, chemical resistance and modulus of elasticity, comprising a polymer composed of an aromatic tetracarboxylic acid component and an aromatic diamine. CONSTITUTION: This film comprises a polymer composed of an aromatic tetracarboxylic acid component (composed of preferably >=30mol% of a biphenyltetracarboxylic acid component) and an aromatic diamine (composed of preferably >=50mol% phenylenediamine component) and has a weight ratio of elements C/O of 2.4-3.9 and O/N of 2.9-4.2 at least on one film surface and a content of P of 5-500ppm in the whole film.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a modified polyimide film. More specifically, high adhesiveness is imparted, excellent chemical resistance, high elastic modulus,
It has high adhesive strength even when laminated with other materials, has resistance to chemicals such as alkalis in various manufacturing processes, and has high rigidity, so dimensional accuracy in the manufacturing process is also high, and alignment when mounting other parts The present invention relates to a good modified polyimide film.

[0002]

2. Description of the Related Art Conventionally, a polyimide film having an excellent heat resistance, which is composed of an aromatic tetracarboxylic acid component containing a biphenyltetracarboxylic acid component as a main component and an aromatic diamine component containing a phenylenediamine as a main component, has been known, for example. It is described in Japanese Patent Publication No. 60-42817. Since this biphenyltetracarboxylic acid-based polyimide has extremely excellent heat resistance, mechanical strength, dimensional stability, etc., it can be used in flexible printed wiring copper clad boards (FPC boards) and carrier tapes for TAB. Suitable as a support used for manufacturing. However, this polyimide film has a problem that it is not possible to sufficiently enhance the adhesion between the two when it is bonded to a copper foil or the like via an epoxy-based or thermoplastic polyimide-based adhesive.

Therefore, as described in JP-A-62-267330, it is also known to improve the adhesiveness of a polyimide film by applying a silane coupling agent to a polyamic acid film and heating it. There is. Further, as described in JP-A-62-60416, a method of adding an amine salt of a phosphoric acid ester for the purpose of improving the releasability of a polyamic acid film from a substrate such as a belt is also known. There is.

However, these known techniques have a large adhesive strength when laminated with other materials, and have resistance to chemicals such as alkali in various manufacturing processes,
It is difficult to obtain a polyimide film that has a large balance of the various performances required for practical use that the rigidity is large and the dimensional accuracy in the manufacturing process is high, and the alignment when mounting other parts is also good, High quality, high accuracy, and
It is becoming difficult to satisfy the needs of high productivity.

[0005]

An object of the present invention is to provide the aromatic polyimide film with the excellent physical properties originally possessed by the aromatic polyimide film.
It has a large tensile modulus and excellent chemical resistance while maintaining a high level of heat resistance and the like, has a large adhesive strength even when laminated with other materials, and has little change even after undergoing various manufacturing processes. (EN) Provided are a modified polyimide film having high accuracy and good alignment when mounting other parts, and a laminate thereof.

[0006]

That is, the present invention is a film in which a polymer is composed of an aromatic tetracarboxylic acid component and an aromatic diamine component, and the weight ratio of each element on at least one film surface is C ( Carbon) / O
(Oxygen) is 2.4 to 3.9, O (oxygen) / N (nitrogen)
Is 2.9 to 4.2, and the content of P (phosphorus) in the whole film is 5 to 500 ppm.

The present invention also provides a film in which the polymer is composed of an aromatic tetracarboxylic acid component and an aromatic diamine component, and at least C (carbon) / O on the film surface.
(Oxygen) is 2.4 to 3.9 in weight ratio, and O (oxygen) / N
(Nitrogen) is 2.9 to 4.2, and the content of P (phosphorus) in the total film is 5 to 500 ppm. A modified polyimide film of the same kind or different kinds directly or through an adhesive. The present invention relates to a laminated body in which materials are laminated.

[0008] As the aromatic tetracarboxylic acid component in the present invention, for example 2,3,3 ^{', 4'} - biphenyl tetracarboxylic acid component, 3,3 ^{', 4,4'} - biphenyl and biphenyl tetracarboxylic acid component tetra An aromatic tetracarboxylic acid component containing a carboxylic acid component in an amount of 30 mol% or more, particularly 50 mol% or more, and especially 60 mol% or more based on the total tetracarboxylic acid component is preferable. Further, as the aromatic tetracarboxylic acid component, 3,3 ^{', 4,4'} - benzophenone tetracarboxylic acid component include pyromellitic acid component, bis (3,4-carboxyphenyl) methane component, 2,2, - bis (3,4
-Dicarboxyphenyl) propane component, bis (3,4)
-Dicarboxyphenyl) sulfone and the like may be combined with the biphenyltetracarboxylic acid component. For example,
3,3 ^{', 4,4'} - a combination of biphenyl tetracarboxylic acid component and pyromellitic acid component are preferred. When the proportion of the biphenyltetracarboxylic acid component in the wholly aromatic tetracarboxylic acid component is large, the polyimide film is optimal in terms of elasticity, chemical resistance and the like. On the other hand, when the proportion of the biphenyltetracarboxylic acid component in the wholly aromatic tetracarboxylic acid component decreases, the polyimide film tends to have reduced elastic modulus and chemical resistance.

As the aromatic diamine component in the present invention, for example, m- or p-phenylenediamine component,
A phenylenediamine component such as a 3,5-diaminotoluene component or a 2,5-diaminotoluene component is contained in an amount of 50 mol% or more, particularly 60 mol% or more, and particularly 70 mol% of the total aromatic diamine component. The aromatic diamine component contained above is mentioned suitably. In the present invention, as the aromatic diamine component, an aromatic diamine component containing a p-phenylenediamine component in an amount of 60 mol% or more, and particularly 70 mol% or more is preferably mentioned. 4,4 As aromatic diamine ^components' - diamino diphenyl ether - ether component,
3,4 ^'- diaminodiphenyl et - ether component, ^3,3'
- diamino diphenyl ether - diamino diphenyl ether, such as ether components - ethers component, 4,4 ^'- diaminodiphenylmethane component, ^4,4' - diaminodiphenyl propane component, 4,4 ^'- diaminodiphenyl sulfone component, 4,
4 ^'- such as diaminodiphenyl sulfide component may be combined with phenylenediamines component. Among these combinations, 4,4 ^'- diaminodiphenyl et - diamino diphenyl ether, such as ether components - ethers component and phenylenediamines component are preferred. In particular, the combination of two aromatic diamine component, p- phenylenediamine component and 4,4 ^'- diaminodiphenyl et - are preferred combination of ether. Also in the case of this combination, the ratio of each component is p
-It is particularly preferred that the phenylenediamine content is 50 mol% or more. When the proportion of the phenylenediamine component in the wholly aromatic diamine component is large, the heat resistance of the polyimide film and the mechanical properties are excellent, which is preferable. On the contrary, when this ratio is low, the heat resistance and mechanical properties of the polyimide film tend to be deteriorated.

The polyimide film in this invention is
30 mol% or more of the aromatic tetracarboxylic acid component, especially 5
A polyimide in which 0 mol% or more, especially 60 mol% or more is a biphenyltetracarboxylic acid component, and 50 mol% or more, particularly 60 mol% or more of a aromatic diamine component is a phenylenediamine component is preferable. In such a polyimide film, the weight ratio of each element is C (carbon) / O (oxygen) (the ratio of C to O, the same applies hereinafter) is 4.0 to 5.7, and particularly 4.1 to 5.6. Yes, O / N
(Ratio of O to N) is 1.8 to 2.6, especially 1.9.
It becomes -2.5, and it is preferable to select appropriately within this range. The weight ratio of each element in the polyimide film is substantially equal to the weight ratio of each element in the entire film.

If the C / O is smaller than the lower limit, the tensile modulus of the polyimide film tends to be small, and if the C / O is larger than the upper limit, the flexibility of the polyimide film tends to be lowered, which is not preferable. If the O / N is less than the lower limit, the flexibility of the polyimide film is lowered, and if the O / N is more than the upper limit, the tensile elastic modulus of the polyimide film is reduced, which is not preferable.

In the present invention, the weight ratio of each element on one side or both sides of the polyimide film is C
(Carbon) / O (oxygen) is 2.4 to 3.9, preferably 2.5 to 3.8, particularly preferably 2.6 to 3.7, and O (oxygen) / N (nitrogen) is 2.9 to 4.2, preferably 3.0 to 4.1, particularly preferably 3.1 to 4.0, and the P (phosphorus) content in the entire film is 5 to 500.
ppm (weight ratio), preferably 10 to 400 ppm,
Particularly preferably, it should be 15 to 300 ppm.

If the C / O is smaller than the lower limit, the tensile modulus of the polyimide film is small, and if the C / O is larger than the upper limit, the elongation of the polyimide film is small, which is not suitable. When the above O / N is less than the lower limit, the elongation of the polyimide film becomes small, and the O / N
Is larger than the above upper limit, the tensile elastic modulus of the polyimide film becomes small, which is not suitable. Further, if the content of P in the total polyimide film is less than the lower limit, it is not effective, and if it is more than the upper limit, the physical properties of the polyimide film, particularly elongation is lowered, which is not preferable.

In the present invention, it is necessary that each component be within the above range, whereby the tensile modulus of elasticity is 400 kg / mm ² or more, and the adhesiveness is sufficiently large at a practical level and practical. It is possible to obtain a modified polyimide film having sufficient moldability at various levels and excellent chemical resistance.

The polyimide film of the present invention is obtained, for example, from a phosphorus-containing compound, preferably a phosphoric acid ester and / or an amine salt of a phosphoric acid ester, an aromatic dianhydride and an aromatic diamine in an organic polar solvent. It can be obtained by imidizing the polyamic acid from a polyamic acid solution containing the aromatic polyamic acid obtained by a chemical conversion method or a thermal conversion method. Preferably, the aromatic polyamic acid (20% thereof)
(The following may be imidized) The solution is cast on a substrate in a film form and heated to form a self-supporting film, and the self-supporting film is heated to complete imidization and solvent removal. Then, the surface of the film is subjected to an electric discharge treatment, preferably by a plasma treatment, to obtain C / C of the film surface.
The modified polyimide film of the present invention can be obtained by controlling the O, O / N content and the P content in the entire film within the above ranges. An inorganic filler or the like can be added to the modified polyimide film of the present invention.

The above-mentioned organic polar solvent contains about 2 to 50% by weight, particularly 5 to 4% by weight of the aromatic polyamic acid (this polyamic acid may be imidized to 20% or less).
Any organic polar solvent that can be uniformly dissolved at a concentration of about 0% by weight may be used, and examples thereof include N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethylmethoxyacetamide and the like. There may be mentioned organic polar solvents such as di-lower alkylcarboxylamides, N-methyl-2-pyrrolidone, dimethyl sulfoxide and dimethyl sulfone.

Examples of the phosphorus-containing compound include:
Monocaproyl phosphate, monooctyl phosphate, monolauryl phosphate, monomyristyl phosphate, monocetyl phosphate, monostearyl phosphate, monoethylene ester of triethylene glycol monotridecyl ether, tetra Ethylene glycol monolauryl ether monophosphate, diethylene glycol monostearyl ether monophosphate, dicaproyl phosphate, dioctyl phosphate, dicapryl phosphate, dilauryl phosphate, dimyristyl phosphate, dicetyl phosphorus Acid ester, distearyl phosphate ester, tetraethylene glycol mononeopentyl ester
Phosphoric acid esters such as ter diphosphoric acid ester, triethylene glycol monotridecyl ether diphosphoric acid ester, tetraethylene glycol monolauryl ether diphosphoric acid ester, diethylene glycol monostearyl ether diphosphoric acid ester And amine salts of these phosphoric acid esters. As the amine, ammonia, monomethylamine, monoethylamine, monopropylamine, monobutylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, monoethanolamine, diethylanol, There are triethanolamine and the like.

The above-mentioned aromatic polyamic acid is, for example, a biphenyltetracarboxylic acid type polyimide having an imidization ratio of 20% or less obtained by polymerization at low temperature from the above-mentioned aromatic tetracarboxylic acid component and aromatic diamine component. In addition to being a precursor, logarithmic viscosity (measurement temperature: 30 ° C., concentration: 0.
5 g / 100 ml solution, solvent: N-methyl-2-pyrrolidone) is about 0.1 to 7, especially about 0.2 to 5 and the organic polar solvent has a concentration of about 2 to 50% by weight, particularly 5 to 40% by weight. It is preferably a polymer that can be uniformly dissolved up to%. The logarithmic viscosity is a value calculated by the following equation. Logarithmic viscosity = natural logarithm (solution viscosity / solvent viscosity) / solution concentration

The polyamic acid self-supporting film (70% or less may be imidized) contains 100 parts by weight of the aromatic polyamic acid and 5 to 100 parts of an organic polar solvent.
150 parts by weight, preferably 10 to 120 parts by weight, particularly preferably 20 to 100 parts by weight, and preferably 0.01 to 1 part by weight with respect to 100 parts by weight of the polyamic acid polymer.
In particular 0.02-0.8 parts by weight of phosphate and /
Alternatively, it is a flexible and self-supporting film made of an aromatic polyamic acid composition containing a phosphate ester amine salt, and particularly preferably a long solidified film.

The self-supporting film of the polyamic acid is, for example, approximately equimolar to the above-mentioned aromatic tetracarboxylic acid component and aromatic diamine component (the addition order of each component is not particularly limited, You may add equimolar,
You may add in several steps. In the organic polar solvent at a low temperature of about 100 ° C. or lower, particularly preferably at a temperature of 0 to 80 ° C. for about 0.1 to 10 hours to obtain a high molecular weight aromatic polyamic acid (). Composition obtained by adding the phosphorus-containing compound to an aromatic polyamic acid solution in which an aromatic polyimide precursor) is uniformly dissolved in an organic polar solvent at a concentration of about 2 to 50% by weight and dissolving the solution. Is preferably used as a film forming dope solution, preferably about 150
A liquid thin film is formed on the surface of the support at a casting temperature of not higher than 0 ° C., particularly preferably at a casting temperature of about 0 to 120 ° C., and the thin film is preferably dried at a temperature of not higher than about 150 ° C., particularly preferably. Is preferably a self-supporting solidified film formed by a film-forming method such as a solution casting method in which the film is dried at a drying temperature of about 20 to 140 ° C., preferably for about 0.1 to 1 hour.

In the self-supporting film of polyamic acid, for example, the above-mentioned high molecular weight aromatic polyamic acid (aromatic polyimide precursor) is uniformly dispersed in the organic polar solvent at a concentration of about 2 to 50% by weight. In the aromatic polyamic acid solution dissolved in, the chemical conversion agent such as a tertiary amine compound such as pyridine and betapicoline, an acid anhydride such as acetic anhydride, and the above-mentioned phosphorus-containing compound are dissolved. The obtained composition (the order of addition of each of these components is not particularly limited and may be appropriately selected depending on the stability of the composition) is used as a film-forming dope solution, and preferably about 0 to
A liquid thin film is formed on the surface of the support at a casting temperature of 150 ° C., particularly preferably at a casting temperature of about 5 to 120 ° C., and the thin film is preferably dried at a temperature of about 150 ° C. or lower on the support.
Particularly preferred is a self-supporting solidified film formed by a film-forming method such as a solution casting method, which is preferably dried at a drying temperature of about 20 to 140 ° C., preferably for about 0.1 to 1 hour.

The self-supporting film (polyamic acid or a polyamic acid partially imidized) is heated to imidize the polyamic acid forming the film. The self-supporting film contains polyamic acid at an imidization ratio of 90% or more, and is substantially substantially amide-containing.
It is preferable to obtain a polyimide film by heating the film so that it does not have an acid bond, imidizing it, and drying to evaporate and remove volatile components such as the solvent from the film.

The above-mentioned heat treatment is initially about 100-40.
It is preferable to gradually perform imidization of the polymer and evaporation / removal of the solvent at a temperature of 0 ° C. for about 0.1 to 5 hours, particularly 0.2 to 3 hours. Especially, the heat treatment is about 100
Primary heat treatment at a relatively low temperature of ~ 170 ° C for about 1 to 30 minutes, then about 1 to 30 at a temperature of 170 to 220 ° C.
It is preferable to perform the stepwise secondary heat treatment for about 1 to about 30 minutes at a high temperature of 220 to 400 ° C. for 3 minutes. Further, the self-supporting film is preferably 100 g / mm after being peeled off from the surface of the self-supporting body during heating.
^After drying at about 80 to 250 ° C under a low tension of ² or less to form a solidified film containing a solvent and generated water in a range of about 5 to 25% by weight, both ends of the film may be fixed and heated.
The continuous heat treatment at 250 ° C. or higher is preferably carried out by fixing at least both ends of the long film at right angles to the longitudinal direction with a pin tenter, a clip, a frame or the like. In addition to the heating, the fourth high temperature heating may be performed at a high temperature of 400 to 600 ° C.

In the modified polyimide film of the present invention, at least one side of the film is preferably subjected to plasma treatment so that C / O and O / N are within a specific range. In the plasma treatment, the film surface is not treated, or acetone or isopropyl alcohol is used.
It may be carried out after treatment with an organic solvent such as ethyl alcohol or ethyl alcohol.

The pressure of the atmosphere for performing the plasma treatment is not particularly limited, but is preferably in the range of 0.1 to 1000 Torr. The gas composition of the atmosphere in which the plasma treatment is performed is not particularly limited, but preferably contains oxygen. Further, it may contain at least 20 mol% of a rare gas. Examples of the rare gas include He, Ne, Ar, and Xe, and Ar is preferable. CO ₂ , N in noble gas
_Two or the like may be mixed and used. The plasma irradiation time for performing the plasma treatment is preferably 1 second to 10 minutes.

The analysis of each component in the modified polyimide film of the present invention is carried out by, for example, measuring the weight ratio of each element on the film surface by using an X-ray photoelectron spectrometer (ESCA, VG).
LAB 200X type, Mg Ka X-ray source (300
It can be determined by using W) and examining the elements present on the very surface (up to several tens of A) of the 2 × 3 mm film. For P in all films, a polyimide film was burnt and ashed together with zinc oxide, dissolved in dilute sulfuric acid, ammonium molybdate, sodium sulfite, and hydroquinone were added, and the absorbance (wavelength 655 nm) was measured with a spectrophotometer. It was done by the method.

The laminate of the present invention is obtained, for example, by laminating the above-mentioned polyimide film with a base material of the same kind as a polyimide film or a different kind of base material such as copper directly or through an adhesive. Obtainable.

As the laminate of the present invention, for example, on the modified polyimide film of the present invention (the above-mentioned specific C
/ O, on the surface having a ratio of O / N),
Drying and laminating copper foil, or one or both sides of the modified polyimide film (modified surface)
A heat-resistant adhesive, for example, a solution of a thermoplastic polyimide, or a solution of a polyamic acid which is a precursor thereof,
A metal film (copper, chromium, nickel, etc.) is vapor-deposited or sputtered directly onto the polyimide film with heat-resistant adhesive that has been dried and heated, or onto the modified surface of this modified polyimide film. It can be a two-layer substrate, for example copper) deposited by electrolytic or electroless plating.

The laminated body of the present invention is, for example, FPC, T
It can be preferably used for AB, LOC (read-on-chip) and the like.

[0030]

EXAMPLES Examples of the present invention will be shown below. In the following description, “part” means “part by weight”.

Reference Example 1 3 in 2470 parts of N, N-dimethylacetamide
3 ^{', 4,4'} - biphenyl tetracarboxylic acid and anhydrides 294.22 parts P- phenylenediamine 108.14
Parts were added and reacted for about 10 hours to obtain a polyamic acid solution. The logarithmic viscosity of this polyamic acid is 2.66,
The viscosity of the solution at 30 ° C. was 3100 poise.

Reference Example 2 3,37 parts of N, N-dimethylacetamide was used.
3 ^{', 4,4'} - biphenyltetracarboxylic acid dianhydride 294.22 parts of 4,4 ^'- diaminodiphenyl et - added 200.24 parts of ether is reacted at room temperature for about 10 hours to obtain a polyamic acid solution . The logarithmic viscosity of this polyamic acid solution is 2.71, and the viscosity of the solution at 30 ° C. is 26.
It was 00 poise.

Reference Example 3 4,4 ^'in 2570 parts of N, N-dimethylacetamide
After adding 200.24 parts of diaminodiphenyl ether, 218.14 parts of pyromellitic dianhydride was added, and about 6 parts were added.
The reaction was carried out for a time to obtain a polyamic acid solution. The logarithmic viscosity of this polyamic acid solution is 1.60,
The viscosity at ° C was 300 poise.

Reference Example 4 N-methyl-2-pyrrolidone 1980 parts of 3,3 ^' ,
4,4 ^'- biphenylene dianhydride 147.
2 parts, dianhydrides 100.1 parts pyromellitic acid, 75.7 parts of p-phenylenediamine, 4,4 ^'- diaminodiphenyl et - to obtain a polyamic acid solution by reacting about 6 hours added 60.6 parts of ether . Logarithmic viscosity of this polyamic acid solution (30 ° C., 0.5 g / 100 ml N-methyl-2
-Pyrrolidone) was 2.51 and the viscosity of the solution at 30 ° C was 2900 poise.

Example 1 To the polyamic acid solution prepared in Reference Example 1, 0.1 part of monostearyl phosphate ester triethanolamine salt was added at a ratio to 100 parts of polyamic acid, and the mixture was allowed to stand at room temperature for 6 minutes.
The mixture was stirred for a time to obtain a polyamic acid composition. This composition was cast-coated on a stainless belt and dried at 120 ° C. for 20 minutes, and then peeled from the surface of the stainless belt to obtain a self-supporting film. The peeling was smooth.

The resulting self-supporting film was heated at 150 ° C. for 5 minutes, then heated to 200 ° C. and heated at that temperature for 7 minutes.
After heating for 1 minute, the temperature is further raised to 250 ° C., heated at that temperature for 9 minutes, and finally raised to 450 ° C. for 7 minutes.
It was heat-treated for a minute to imidize the polymer and dry the film to produce a polyimide film having a thickness of 75 μm. The C / O of this film is 5.5 and the O / N is 2.
It was 0 (Yanagimoto Seisakusho, Elemental Analyzer: MT-3 type used).

The obtained polyimide film was immersed in acetone and dried, and then plasma treatment was performed under the conditions of plasma irradiation time of 1 minute, microwave oscillation output of 1 kw, plasma generation vacuum degree of 0.8 Torr, and plasma treatment gas of oxygen. A modified polyimide film was obtained. Table 1 shows the C / O and O / N on the surface of the modified polyimide film and the P content in the film. Moreover, when the C / O and O / N of the entire modified polyimide film were measured, they were in agreement with the respective values of the polyimide film before modification.

An epoxy adhesive (Hisol Japan, Hisol: LOL. No. OX-035) was applied on an electrolytic copper foil having a thickness of 35 μm, and dried by heating at 120 ° C. for 30 minutes for adhesion. An agent layer (thickness 200 μm) was formed. Next, the aromatic polyimide film was superposed on the adhesive layer on the electrolytic copper foil so that the adhesive layer and the plasma-treated surface were in contact with each other, and then the mixture was heated at 170 ° C. and 40 kg / cm ² for 5 minutes.
Pressed for minutes to form a laminate. Then, this laminate was dried at 180 ° C. for 60 minutes and then allowed to stand for 13 hours to allow a T-peeling test (A between the copper foil layer and the polyimide film layer).
STM-D-1876) and 180 degree peel test (ASTM
-D-903) was performed.

The T-peel strength was 1.5 kg / cm on the B side (the surface on the side which was in contact with the stainless belt surface during the production of the self-supporting film by casting) and the F side (the self-supporting film by casting). The surface which was not in contact with the stainless steel belt surface at the time of manufacturing was 1.3, and the 180 degree peel strength was 3.5 kg / cm for B side and 2.9 kg / c for F side.
It was m. The tensile modulus of elasticity of this film is 780.
Even when immersed in a 10% NaOH aqueous solution of kg / mm ² at 60 ° C. for 1 hour, the shape was almost unchanged.

Example 2 To the polyamic acid solution prepared in Reference Example 4, 0.1 part of monostearyl phosphate ester triethanolamine salt was added at a ratio to 100 parts of polyamic acid, and the mixture was allowed to stand at room temperature for 6 minutes.
The mixture was stirred for a time to obtain a polyamic acid composition. The composition was cast-coated on a stainless belt and dried at 120 ° C. for 10 minutes, and then peeled off from the surface of the stainless belt to obtain a self-supporting film. The peeling was smooth. A thickness of 7 was obtained from the obtained self-supporting film in the same manner as in Example 1.
A 5μ modified polyimide film was produced. The C / O of this film was 4.1 and the O / N was 2.3.

The modified polyimide film was used and laminated with an epoxy adhesive in the same manner as in Example 1. The T-peel strength is 1.6 kg / cm on the B side and 1.5 kg / cm on the F side, and the 180 degree peel strength is 3.1 kg / cm on the B side and 3.0 kg / cm on the F side. there were. C / of the surface of the modified polyimide film
Table 1 shows the contents of O, O / N, and P in the film. The tensile elastic modulus of this film is 580 kg / mm.
^In No. ² , even when immersed in a 10% NaOH aqueous solution at 60 ° C. for 1 hour, the shape was maintained with almost no change.

Comparative Example 1 A polyimide film was produced in the same manner as in Example 1 except that the polyamic acid solution prepared in Reference Example 1 was used and no plasma treatment was performed. This polyimide film was used and laminated in the same manner as in Example 1 with an epoxy adhesive. As a result of evaluating the adhesiveness, the T-peel strength was 0.03 kg / cm for the B side and 0.02 kg / cm for the F side, and the 180 degree peel strength was 0.3 kg / cm for the B side and F.
The surface was 0.1 kg / cm. C / O, O / N on the surface of the modified polyimide film, P in the film
Table 1 shows the content rate of. The tensile elastic modulus of this film was 780 kg / mm ² , and it was 6% in 10% NaOH aqueous solution.
Even if it was immersed at 0 ° C. for 1 hour, the shape was maintained with almost no change.

Comparative Example 2 A polyimide film was produced in the same manner as in Example 1 except that the polyamic acid solution prepared in Reference Example 2 was used.
The C / O of this film was 4.2 and the O / N was 2.9. A modified polyimide film was obtained from this polyimide film in the same manner as in Example 1. This modified polyimide film was used and laminated in the same manner as in Example 1 with an epoxy adhesive. As a result of evaluating the adhesiveness, the T-peel strength was 1.4 kg / cm on the B side and 1.5 kg on the F side, and the 180 degree peel strength was 2.2 on the B side.
The F-plane was 2.6 kg / cm at kg / cm. C / O, O / N on the surface of the modified polyimide film,
Table 1 shows the content ratio of P in the film. The tensile elastic modulus of this film was 380 kg / mm ² , 10% NaO.
Even when immersed in the H aqueous solution at 60 ° C. for 1 hour, the shape was maintained with almost no change.

Comparative Example 3 A polyimide film was produced in the same manner as in Example 1 except that the polyamic acid solution prepared in Reference Example 3 was used.
The C / O of this film was 3.3 and the O / N was 2.9. A modified polyimide film was obtained from this polyimide film in the same manner as in Example 1. This modified polyimide film was used and laminated with an epoxy adhesive in the same manner as in Example 1. As a result of evaluating the adhesiveness, the T-peel strength was 1.6 kg / cm on the B side and 1.6 kg / cm on the F side, and the 180 degree peel strength was 3.1 kg / cm on the B side and the F side was 3.1 kg / cm. The surface was 2.9 kg / cm. C / of the surface of the modified polyimide film
Table 1 shows the contents of O, O / N, and P in the film. The tensile modulus of elasticity of this film is 310 kg / mm ² ,
When the film was immersed in a 10% NaOH aqueous solution at 60 ° C. for 1 hour, the film was dissolved.

Comparative Example 4 The polyamic acid solution prepared in Reference Example 3 was cast-coated on a stainless belt without adding monostearyl phosphate ester triethanolamine salt,
After drying at 0 ° C for 10 minutes, it tried to peel from the stainless belt surface, but peeling was difficult and the film was cut or peeling marks were left on the peeling surface, so that a good film could not be manufactured. It was

Examples 3 to 8 Plasma treatment time is from 1 minute to 15 seconds (Example 3)
Or 5 minutes (Example 4) instead of C / O, O /
Whether the ratio of N was changed as shown in Table 1, the monostearyl phosphate ester triethanolamine salt was changed to 0.025 part (Example 5), or the monostearyl phosphate ester triethanolamine salt was changed to 0.5. Part (Example 6) or changed to monostearyl phosphate ester triethanolamine salt to give dioctyl phosphate monoethanol salt.
The same procedure as in Example 1 was performed except that 0.1 part of the ruamine salt was used (Example 7) or 0.1 part of the monophosphate ester of triethylene glycol monotridecyl ether was used (Example 8). did. The results are summarized in Table 1.

[0047]

[Table 1]

Example 9 The modified polyimide films obtained in Examples 1 to 8 were slit to form a tape having a width of 35 mm, and a polyimide adhesive tape having a width of 26 mm ( UPA-322 manufactured by Ube Industries, Ltd. was laminated on the modified surface of the polyimide tape so that the center line of the polyimide tape was overlapped, to prepare a tape with an adhesive (thickness: 95 μm). A sprocket hole and a device hole were punched on the polyimide of the polyimide tape with the adhesive, and copper foil (35 μ) was stuck at 130 ° C. to cure the adhesive. IL is formed on the copper foil by patterning and etching by a conventional method.
Circuits such as (inner lead) and OL (outer lead) were formed to prepare a carrier tape for TAB. This T
When the IC was mounted on the AB carrier tape, the dimensional accuracy of the IC pad and IL was almost constant, and accurate bonding was possible.

After sealing the IC with potting resin,
When mounted on a printed circuit board, the dimension of the circuit of the printed circuit board and the TAB OL was small, and accurate bonding was possible.

Comparative Example 5 A carrier tab for TAB was prepared in the same manner as above except that the modified polyimide films obtained in Comparative Examples 1 to 3 were used.
I made a cup. When the IC is mounted on this TAB carrier tape, the dimensions of the IC pad and the IL are greatly changed,
It could not be bonded accurately and could not be used.

[0051]

Since the present invention is configured as described above, it has the following effects.

This modified polyimide film has a tensile elastic modulus of 400 kg / mm ² or more, is excellent in chemical resistance, has a large adhesive strength even when laminated with other materials, and does not change even after undergoing various manufacturing processes. The dimensional accuracy in the manufacturing process is also high, and the alignment is good when mounting other components.

As this modified polyimide film, at least one of which has the surface of the plasma treated, has a tensile elastic modulus of 400 kg / mm ² or more, is excellent in chemical resistance, and can be bonded to other materials. The adhesive strength is high, it does not change even after various manufacturing processes, the dimensional accuracy in the manufacturing process is high, the alignment when mounting other components is good, and stable and consistent quality can be obtained.

This modified polyimide film comprising a polymer component of 30 mol% or more of biphenyltetracarboxylic acid component and 50 mol% or more of phenylenediamine component has a tensile modulus of 400 kg / mm ² or more. Yes, it has excellent chemical resistance, has high adhesive strength even when laminated with other materials, does not change even after various manufacturing processes, has high dimensional accuracy in the manufacturing process, and can be aligned when mounting other parts. It is good and can be obtained industrially in large quantities with stable and constant quality.

The laminated body using this modified polyimide film has a high adhesive strength, does not change even after various manufacturing processes, has high dimensional accuracy in the manufacturing process, and is aligned when mounting other parts. Is good.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Takashi Kono 10 1978, Koujigushi, Ube City, Yamaguchi Prefecture Ube Kosan Co., Ltd. Ube Chemical Factory

Claims (4)

[Claims] 1. A film in which a polymer is composed of an aromatic tetracarboxylic acid component and an aromatic diamine component, and the weight ratio of each element on the surface of at least one film has a C / O ratio of 2.4 to 3.9. And O / N is 2.9 to 4.2, and the P content in the entire film is 5 to 500 pp.
A modified polyimide film characterized in that it is m. 2. The modified polyimide film according to claim 1, wherein at least one film surface is plasma-treated. 3. Aromatic tetracarboxylic acid component is 30 mol%
3. The modified polyimide film according to claim 1 or 2, comprising the above biphenyltetracarboxylic acid component and the aromatic diamine component comprising 50 mol% or more of the phenylenediamine component. 4. A film in which the polymer is composed of an aromatic tetracarboxylic acid component and an aromatic diamine component, and the weight ratio of each element on at least one film surface has a C / O of 2.4 to 3.9. And O / N is 2.9 to 4.2, and the P content in the entire film is 5 to 500 pp.
A laminated body comprising the modified polyimide film having a thickness of m and a base material of the same kind or different kinds laminated directly or through an adhesive.