JP3235370B2 - Laminate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a modified polyimide film. More specifically, the present invention has a high bonding strength (adhesion strength) when an aromatic polyimide film having excellent chemical resistance and high elastic modulus is bonded (stretched) to another material, and The present invention relates to an aromatic polyimide film modified so as to facilitate operations such as positioning when mounting other components.

[0002]

2. Description of the Related Art Conventionally, a polyimide film having excellent heat resistance comprising 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 proposed. It is described in JP-B-60-42817. Since the biphenyltetracarboxylic acid-based polyimide has extremely excellent heat resistance, mechanical strength, dimensional stability, etc., it can be used for flexible printed wiring copper-clad boards (FPC boards) and carrier tapes for TAB. Suitable as a support for use in production. However, since this polyimide film is bonded to a copper foil or the like via an epoxy-based or thermoplastic polyimide-based adhesive, there is a problem that the adhesion between the two cannot be sufficiently increased.

For this reason, in order to improve the adhesiveness of the polyimide film, attempts have been made to post-treat the surface of the polyimide film such as corona treatment and plasma treatment. However, depending on these technologies, the adhesive strength when bonded to other materials is large, it is resistant to chemicals such as alkali in various manufacturing processes, the rigidity is large and the dimensional accuracy in the manufacturing process is high, In order to obtain a polyimide film that satisfies the various performances required for practical use in a well-balanced manner, such as good alignment when mounting other parts, high cost, high quality, high precision, It has become difficult to satisfy needs such as high productivity and low cost.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide excellent properties inherent to an aromatic polyimide film,
High tensile modulus, excellent chemical resistance, high heat resistance, etc., high adhesive strength when bonded to other materials, little change even after various manufacturing processes, An object of the present invention is to provide a modified polyimide film having high accuracy and good alignment when mounting other components, and a laminate thereof.

[0005]

That is, the present invention provides:
Phosphorus (P) content in all films is 5 to 500 ppm
And an aromatic polyimide film comprising an aromatic tetracarboxylic acid component and an aromatic diamine component having a tensile modulus of 400 kg / mm ² or more, wherein at least one of the film surfaces has an X-ray photoelectron spectrum. Device (V
G company) using a MgKα X-ray source (300 W), the weight ratio of carbon to oxygen (C / O) is 2.9 to
A value in the range of 4.6, the weight ratio of oxygen to nitrogen (O /
N) is a polyimide-based film on the treated surface of the silicon compound-treated film such that the value of N is in the range of 2.4 to 3.5 and the content of Si is in the range of 0.7 to 3.0% by weight. The present invention relates to a laminated body provided with an adhesive and slitted.

[0006] The present invention also relates to a laminate obtained by laminating a copper foil on the laminate described above via a polyimide-based adhesive.

[0007] 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 at least 30 mol%, particularly at least 50 mol%, and especially at least 60 mol%, based on the total tetracarboxylic acid component is preferred. 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 may be combined with a 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 excellent in terms of the modulus of elasticity, chemical resistance and the like, and is therefore optimal. Conversely, when the proportion of the biphenyltetracarboxylic acid component in the wholly aromatic tetracarboxylic acid component is reduced, points such as the modulus of elasticity and chemical resistance of the polyimide film tend to decrease.

[0008] 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 added in an amount of 50 mol% or more, particularly 60 mol% or more, and especially 70 mol%, based on the total aromatic diamine component. The aromatic diamine component contained above is preferably exemplified. 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, particularly 70 mol% or more, is preferably exemplified. 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,
A ^4' -diaminodiphenyl sulfide component or the like may be combined with a phenylenediamine 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 phenylenediamine is at least 50 mol%. It is preferred that the proportion of the phenylenediamine component in the wholly aromatic diamine component be large because the polyimide film has excellent heat resistance and mechanical properties. Conversely, when this ratio decreases, the heat resistance and mechanical properties of the polyimide film tend to decrease.

The polyimide film according to the present invention comprises:
30 mol% or more, especially 5 mol% of the aromatic tetracarboxylic acid component
A polyimide in which 0 mol% or more, especially 60 mol% or more is a biphenyltetracarboxylic acid component, and 50 mol% or more, especially 60 mol% or more of an aromatic diamine component is a phenylenediamine component is preferable. Further, 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) of 4.0 to 5.7, particularly 4.1 to 5.6. Yes, O / N
(The ratio of O to N) is 1.8 to 2.6, particularly 1.9.
To 2.5, and it is preferable to appropriately select within this range.

[0010] The modified polyimide film of the present invention has about 5
The average coefficient of linear expansion at a temperature of 0 to 300 ° C. is 2.5 × 10
^-5 ° C ^-1 or less, preferably -0.1 × 10 ^{-5 to} 2.5 × 1
0 ⁻⁵ ° C. ⁻¹ , particularly preferably 0.1 × 10 ^{−5 to} 2.3 × 1
0 ^-5 ° C.- ¹ and preferably in the longitudinal direction of the film (M
The ratio (MD / TD) of the coefficient of linear expansion between the (D direction) and the transverse direction (TD direction) is about 1/5 to 4/1, particularly preferably about 1/3 to 3/1. The aforementioned thermal dimensional change rate is 0.3% or less, preferably 0.25% or less.

In the present invention, the weight ratio of each element on one or both sides of the polyimide film is C
(Carbon) / O (oxygen) is 2.9 to 4.6, preferably 3.0 to 4.5, particularly preferably 3.1 to 4.4, and O (oxygen) / N (nitrogen) is 2.4 to 3.5, preferably 2.5 to 3.4, particularly preferably 2.6 to 3.3, and the content of Si (silicon) on the film surface is 0.7 to 3.0%. (% By weight), preferably 0.8 to 2.
9%, particularly preferably 0.9 to 2.8%, and the content of P (phosphorus) in the whole film is 5 to 500 ppm (weight ratio), preferably 10 to 400 ppm, particularly preferably 15 to 300 ppm. It is necessary to be.

When the C / O is smaller than the lower limit, the tensile elasticity of the polyimide film becomes small, and when the C / O is larger than the upper limit, the elongation of the polyimide film becomes small. When the O / N is smaller 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 modulus of the polyimide film becomes small, so that it is not appropriate. When the content of Si on the film surface is smaller than the lower limit, the adhesiveness of the polyimide film is small, and when the content of Si is larger than the upper limit, precipitates adhere to the polyimide film surface and the smoothness of the film surface is impaired. Not preferred. Further, if the content of P in the entire polyimide film is less than the lower limit, there is no effect, and if it is more than the upper limit, the physical properties of the polyimide film, particularly elongation, are undesirably reduced.

In the present invention, it is necessary that the respective components and properties are within the above-mentioned ranges, whereby the tensile modulus is preferably 400 kg / mm ² or more, and the adhesiveness is at a practical level. It is possible to obtain a modified polyimide film which is sufficiently large, has sufficient moldability at a practical level, has excellent chemical resistance, and preferably has an elongation of preferably 25% or more.

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. The polyamic acid solution can be obtained from a polyamic acid solution containing the obtained aromatic polyamic acid by a chemical conversion method or by imidizing the polyamic acid by a thermal conversion method. Preferably, the aromatic polyamic acid (20% of which)
The following may be imidized) The solution is cast into a film on a substrate, heated to form a self-supporting film, and a solution of a silane coupling agent is applied to the surface of the self-supporting film. , Heating, C /
The modified polyimide film of the present invention can be obtained by setting the content of O, O / N, Si, and the content of P in the whole film within the above ranges.

The above-mentioned organic polar solvent contains about 2 to 50% by weight, especially 5 to 4% by weight of the above-mentioned aromatic polyamic acid (this polyamic acid may be imidized up to 20%).
Any organic polar solvent that can be uniformly dissolved at a concentration of about 0% by weight may be used. For example, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethylmethoxyacetamide, and other N, N And organic polar solvents such as di-lower alkylcarboxamides, N-methyl-2-pyrrolidone, dimethylsulfoxide and dimethylsulfone.

Examples of the phosphorus-containing compound include, for example,
Monocaproyl phosphate, monooctyl phosphate, monolauryl phosphate, monomyristyl phosphate, monocetyl phosphate, monostearyl phosphate, monoethylene phosphate of triethylene glycol monotridecyl ether, tetraphosphate Monophosphate ester of ethylene glycol monolauryl ether, monophosphate ester of diethylene glycol monostearyl ether, dicaproyl phosphate, dioctyl phosphate, dicaprylic phosphate, dilauryl phosphate, dimyristyl phosphate, dicetyl phosphorus Acid ester, distearyl phosphate, tetraethylene glycol mononeopentyl
Phosphoric esters such as diphosphate of ter, diethylene phosphate of triethylene glycol monotridecyl ether, diphosphate of tetraethylene glycol monolauryl ether, and diphosphate of diethylene glycol monostearyl ether And amine salts of these phosphate esters. As the amine, ammonia, monomethylamine, monoethylamine, monopropylamine, monobutylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, monoethanolamine, diethanolamine, And triethanolamine.

The above-mentioned aromatic polyamic acid is, for example, a biphenyltetracarboxylic acid-based polyimide having an imidation ratio of 20% or less obtained by polymerization at a low temperature from the above-mentioned aromatic tetracarboxylic acid component and aromatic diamine component. It is a precursor and has a logarithmic viscosity (measuring 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 about 2 to 50% by weight, especially 5 to 40% by weight in the organic polar solvent. % Is preferable. The logarithmic viscosity is a value calculated by the following equation. Logarithmic viscosity = natural logarithm (solution viscosity / solvent viscosity) / concentration of solution

The self-supporting film of the polyamic acid (part of which, preferably 70% or less may be imidized) comprises 100 parts by weight of the aromatic polyamic acid and 5 to 150 parts by weight of an organic polar solvent. , Preferably 10
120 parts by weight, particularly preferably 20 to 100 parts by weight,
Aroma containing preferably 0.01 to 1 part by weight, especially 0.02 to 0.8 part by weight of a phosphoric acid ester and / or an amine salt of a phosphoric acid ester based on 100 parts by weight of the polyamic acid polymer. It is a flexible, self-supporting film made of a group III polyamic acid composition, and particularly preferably a long self-supporting film.

The above-mentioned polyamic acid self-supporting film can be formed, for example, by a substantially equimolar amount of the above-mentioned aromatic tetracarboxylic acid component and aromatic diamine component (the order of addition of each component is not particularly limited, and is substantially the same from the beginning). Equimolar may be added,
It may be added in several stages. ) 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 ( A composition obtained by adding and dissolving the above-mentioned 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. Is preferably used as a dope solution for film formation.
Forming a liquid thin film on the surface of the support at a casting temperature of not more than 0 ° C., particularly preferably at a casting temperature of about 0 to 120 ° C., and drying the thin film on the support preferably at a drying temperature of about 150 ° C. or less, particularly preferably A self-supporting film formed by a film forming method such as a solution casting method, which is dried at a drying temperature of about 20 to 140 ° C., preferably for about 0.1 to 1 hour, can be suitably used.

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

The modified polyimide film of the present invention is obtained by firstly forming at least one surface (if necessary, both surfaces) of the self-supporting film (polyamic acid or a polyimide precursor partially imidized). Then, the silicon compound is uniformly distributed and heated to imidize the polyamic acid forming the film.

For example, a solution of a silicon compound containing a silicon compound in a concentration of 0.5% or more and having a water content of 20% or less in the self-supporting film is prepared by a gravure method, a silk screen method. And uniformly distributed by a coating method such as a coating method or a dipping method, and the coated film is preferably 50 to 180 ° C., particularly preferably 60 to 16 ° C.
0 ° C, more preferably at a drying temperature of 70 to 150 ° C, preferably for 0.1 to 20 minutes, particularly preferably 0.2 to 1
Dried for 5 minutes, more preferably 0.3 to 10 minutes, to form a solidified film in which the solvent and product water remain, preferably about 27 to 60% by weight, particularly preferably 30 to 50% by weight, Preferably (1) 100 g / mm ²
Below, particularly preferably in a substantially free state of not more than 80 g / mm ² or under a low tension up to the upper limit, and preferably (2) a drying temperature of about 80 to 250 ° C., particularly preferably 100 to 230 ° C. And preferably about 1-20
After drying for 0 minutes, particularly preferably for 2 to 100 minutes, the solvent and the produced water are preferably about 5 to 25% by weight,
It is particularly preferable to form a solidified film containing 10 to 23% by weight.

The solvent and the produced water are preferably about 2
When the temperature of the solidified film having 7 to 60% by weight, particularly preferably 30 to 50% by weight, remaining is raised to the drying temperature, it is preferable to raise the temperature within a relatively short time.
It is preferable that the temperature is raised at a rate of at least ° C / min. By increasing the tension applied to the solidified film during drying, the coefficient of linear expansion of the finally obtained polyimide film can be reduced. It can be adjusted to the value you want.

The silicon compound has a decomposition temperature of preferably 275 ° C. or higher, particularly preferably 280 to 600.
° C, and particularly preferably, an aminosilane compound and an epoxysilane compound in the range of 290 to 550 ° C. That is, epoxysilane compounds such as β- (3,4-epoxycyclohexyl) -ethyl-trimethoxysilane, γ-glycidoxypropyl-trimethoxysilane, γ-aminopropyl-triethoxysilane, N-β- (amino Ethyl) -γ-aminopropyl-triethoxysilane, N- [β- (phenylamino)
Ethyl] -γ-aminopropyl-triethoxysilane,
Aminosilane compounds such as N-phenyl-γ-aminopropyl-triethoxysilane are preferred. Among them, N-phenyl-γ-aminopropyl-triethoxysilane is particularly preferred.

The above-mentioned silicon compound is used in an amount of 0.1.
A low-viscosity solution which is uniformly dissolved in an organic solvent such as a lower alcohol or an amide solvent at a concentration of 5% by weight or more, particularly preferably 1 to 100% by weight, more preferably 3 to 55% by weight, is preferred. Examples of the solvent include the same types of solvents as the above-mentioned polymerization solvent used for producing the aromatic polyamic acid and the solvent contained in the self-supporting film. Also, ethyl alcohol, methyl alcohol, propyl alcohol
And lower alcohols such as butyl alcohol.

Preferably, the modified polyimide film of the present invention is capable of continuously or intermittently moving at least one pair of both edges of the solidified film together with the film continuously or intermittently after the drying step. In a state fixed by a fixing device or the like, the temperature is higher than the above-mentioned drying temperature, and more preferably in the range of 200 to 500 ° C, particularly preferably in the range of 250 to 450 ° C, preferably 1 to
The solidified film is dried and heat-treated for 200 minutes, especially for 2 to 100 minutes, preferably so that the content of the volatile matter composed of the solvent and the generated water in the finally obtained polyimide film is 1% by weight or less. Then, the solvent and the like are sufficiently removed from the solidified film, and the polymer constituting the film is sufficiently imidized to form a polyimide film which simultaneously satisfies the above-mentioned respective properties.

As a fixing device of the solidified film,
For example, a pair of belt-shaped or chain-shaped ones provided with a large number of pins or holding tools at equal intervals are installed along both longitudinal edges of the solidified film supplied continuously or intermittently. An apparatus capable of fixing the film while moving the film continuously or intermittently with the movement of the film is preferable. In addition, the above-described fixing device for a solidified film may be used to fix the film under heat treatment to an appropriate elongation or shrinkage in the width direction or the length direction (particularly preferably 0.5 to 5%).
A device that can expand and contract at a degree of expansion / contraction may be used.

The modified polyimide film produced in the above step is again preferably 400 g
/ Mm ² or less, particularly preferably at a low tension of 300 g / mm ² or less at 250 to 500 ° C., particularly preferably 3 to 500 ° C.
When heat-treated at a temperature of 00 to 450 ° C., preferably for 1 to 30 minutes, particularly preferably for 2 to 20 minutes, a heat-resistant polyimide film having particularly excellent dimensional stability can be obtained. Also, the manufactured long polyimide film,
It can be wound into a roll by a suitable known method.

The analysis of the element ratio on the surface of the polyimide film whose surface has been modified by the silicon compound treatment can be performed by XPS (X-ray photoelectron spectroscopy) known per se. Specifically, an X-ray photoelectron spectrometer (VG
Using a Mg-Kα X-ray source (300 W) at the ESCA LAB X type) and analyzing the elements present on the surface of the 2 mm × 3 mm film by the ESCA method. . The content of phosphorus (P) in the whole film was determined by burning and ashing a polyimide film together with zinc oxide, dissolving it with dilute sulfuric acid, adding ammonium molybdate, sodium sulfite, and hydroquinone to a spectrophotometer. By measuring the absorbance (wavelength 655 nm).

The average coefficient of linear expansion (α: ° C. ^-1 ) is determined by placing a sample (5 mm × 20 mm) to be measured in a thermomechanical analyzer (manufactured by Rigaku Denki Co., Ltd.) by a tensile load method and measuring the temperature from room temperature to 300 To 10 ° C at a rate of 10 ° C / min,
After holding at 300 ° C. for 1 minute, it is cooled to room temperature at a temperature lowering rate of 5 to 20 ° C./min.
It is calculated from the displacement of the length of the specimen up to 0 ° C. (ΔL ₁ ) and the original length of the specimen (L ₁ ; 10 mm) by the following formula. α = (ΔL ₁ / L ₁ ) / (300-50) The thermal dimensional change rate (A:%) is determined by placing a sample piece (5 mm × 20 mm) in the same thermomechanical analyzer as described above, The temperature is raised to 400 ° C. at a rate of 10 ° C./min,
After holding at 400 ° C. for 2 hours, the sample is cooled to room temperature at a temperature lowering rate of 5 to 20 ° C./min, and the length displacement (ΔL ₂ ) of the sample piece at room temperature (about 25 ° C.) before and after heating. And the original length (L ₂ : 10 mm) of the sample piece was calculated by the following formula. A = (ΔL ₂ / L ₂ ) × 100 The content of the volatile component in the film was calculated by the following formula. Volatile component (% by weight) = (W ₀ −W) / W ₀ × 100 W ₀ : Weight after drying at 150 ° C. × 10 minutes W: Weight after heat treatment at 450 ° C. × 20 minutes

The laminate of the present invention is obtained by, for example, laminating the same kind of polyimide film or a different kind of substrate such as copper on the above-mentioned polyimide film directly by a method such as sputtering or via an adhesive. Obtainable.

As the laminate of the present invention, for example, a method in which an adhesive is applied on the modified polyimide film of the present invention (on the surface having a specific ratio of Si), dried, and a copper foil is laminated, or Heat-resistant adhesive on one or both sides (modified surface) of the modified polyimide film,
For example, a solution of a thermoplastic polyimide or a solution of a polyamic acid as a precursor thereof is applied, dried, and heated. A polyimide film with a heat-resistant adhesive, or a metal (copper, chromium, nickel, etc.) directly on a modified surface of the polyimide film. ) Can be directly deposited by vapor deposition and sputtering, and a metal (for example, copper) is further deposited on the two-layer substrate by electrolytic or electroless plating.

The laminate of the present invention can be made of, for example, FPC, T
It can be suitably used for AB, LOC (lead on chip) and the like.

[0034]

Embodiments of the present invention will be described below. In the following description, “parts” indicates “parts by weight”.

Reference Example 1 3,470 parts of N, N-dimethylacetamide
3 ^{', 4,4'} - biphenyl tetracarboxylic acid and anhydrides 294.22 parts P- phenylenediamine 108.14
The mixture was added and reacted at 25 ° C. for about 10 hours to obtain a polyamic acid solution. The logarithmic viscosity of this polyamic acid is 2.66.
And the viscosity at 30 ° C. of the solution was 3100 poise.

Reference Example 2 4,4 ^'in 2570 parts of N, N-dimethylacetamide
After addition of 200.24 parts of diaminodiphenyl ether,
218.14 parts of pyromellitic dianhydride were added and reacted at 25 ° C. for about 6 hours to obtain a polyamic acid solution. The logarithmic viscosity of this polyamic acid solution is 1.60 and 3
The viscosity at 0 ° C. was 300 poise.

Reference Example 3 N-methyl-2-pyrrolidone contained 1980 parts of 3,3 ^′ ,
4,4 ^'- biphenylene dianhydride 147.
2 parts, 100.1 parts of pyromellitic dianhydride, 75.7 parts of p-phenylenediamine, 4,4 ^'- diaminodiphenyl et - reacted for about 6 hours at 25 ° C. was added 60.6 parts of ether and a polyamic acid solution I got The logarithmic viscosity (30 ° C., 0.5 g / 100 ml N-methyl-2-pyrrolidone) of this polyamic acid solution is 2.51, and
The viscosity at ° C was 2900 poise.

Example 1 Polymer 100 of polyamic acid solution prepared in Reference Example 1
To this part, 0.1 part of monostearyl phosphate triethanolamine salt was added, and the mixture was stirred at room temperature at 25 ° C. for 6 hours to obtain a polyamic acid composition. This composition was cast and applied on a stainless steel belt, dried at 120 ° C. for 20 minutes, and then peeled off from the stainless steel belt surface to obtain a self-supporting film. Peeling was smooth.

On the surface of the obtained self-supporting film, N-
N, N of phenyl-γ-aminopropylethoxysilane
-A dimethylacetamide solution (silane compound concentration: 5% by weight) was applied and heated at 100 ° C for 1 minute. This solidified film was subjected to a low tension of 10 g / mm ² (TD:
Free) into a vertical furnace (drying temperature 180 ° C)
Passed in minutes. Following the drying step, the solidified film is fed into a high-temperature heating furnace, in which the longitudinal edges of the film are gradually moved from about 250 ° C. to 450 ° C. while being moved while being held by a horizontal tenter. The modified aromatic polyimide film was continuously formed by drying, heat treatment and imidation with hot air, and finally the film was rolled up while being cooled. The aromatic polyimide film having a thickness of 50 μm obtained by the above-described film forming method has an imidization ratio of the polymer of 95% or more, and has a heat resistance of 450 ° C. or more as indicated by the thermal decomposition onset temperature of the film. Further, physical properties in the MD direction of the film (20
° C), a tensile strength of 51 kg / mm ² and an elongation of 35
%, And the initial tensile modulus was 810 kg / mm ² . The C / O of this film was 5.5 and the O / N was 2.0 (Yanagimoto Seisakusho, elemental analyzer: MT-3 type used).

An epoxy-based adhesive (Hisol Japan Ltd., Hisol: LOL.NO.OX-035) is applied on a 35 μm-thick electrolytic copper foil, and heated and dried at 120 ° C. for 30 minutes to bond. An agent layer (thickness: 200 μm) was formed. Next, after the above-mentioned aromatic polyimide film was overlaid on the adhesive layer on the electrolytic copper foil, 170 ° C., 40 kg / cm
² for 5 minutes and then left for 13 hours to allow a T-peel test (ASTM D) between the copper foil layer and the polyimide film layer.
-1876) and 180 degree peel test (ASTM D-90)
3) was evaluated.

The T-peel strength was 1.6 kg / cm or more on the B surface (the surface that was in contact with the stainless steel belt surface during the production of the self-supporting film by casting) and the F surface (self-supporting property by casting). The surface which was not in contact with the stainless steel belt surface during the production of the film) was 1.5 kg / cm, and the 180-degree peel strength was 3.8 kg / cm for the B side and 3.0 kg / cm for the F side. Was.

C / on the surface of the modified polyimide film
Table 1 shows the content of O, O / N, and Si, and the content of P in the film. Table 2 shows the coefficient of linear expansion and the rate of change in thermal dimension. Also, the C / O and O / N of the entire modified polyimide film
Was found to be consistent with the respective values of the polyimide film before modification. 10% modified polyimide film
Even when immersed in an aqueous NaOH solution at 60 ° C. for 1 hour, the shape was kept almost unchanged.

Example 2 In the drying step of the film-forming step, the same method as that of Example 1 was used, except that the solidified film was dried while maintaining both ends in the longitudinal direction at a constant interval of about 80 g / mm ^2. To produce an aromatic polyimide film having a thickness of 25 μm. When the aromatic polyimide film was roll-wound, wrinkles did not occur, and the rolled film had a good appearance in a rolled state. Table 1 shows C / O, O / N, Si content of the surface of the modified polyimide film, P content in the film, and physical properties of the film.
The results are shown in Table 2.

Example 3 Polymer 100 of Polyamic Acid Solution Prepared in Reference Example 3
To this part, 0.1 part of monostearyl phosphate triethanolamine salt was added and stirred at room temperature for 6 hours to obtain a polyamic acid composition. The composition was cast on a stainless steel belt and dried at 100 ° C. for 1 minute.
The self-supporting film was peeled off from the stainless belt surface. Peeling was smooth. A solution of N-phenyl-γ-aminopropylethoxysilane in N, N-dimethylacetamide (silane compound concentration: 5% by weight) was applied to the surface of the obtained self-supporting film. A modified polyimide film having a thickness of 50 μm was produced.
The C / O of this film was 4.1 and the O / N was 2.3.

Using this modified polyimide film, it was bonded to an epoxy adhesive in the same manner as in Example 1.
The T-peel strength was 1.7 kg / cm on the B side and 1. kg on the F side.
4 kg / cm, and the 180-degree peel strength of B-side is 3.
At 3 kg / cm, the F-plane was 2.9 kg / cm. Table 1 shows the content of P in the surface of the modified polyimide film and the film, and other characteristics. This film retained its shape with almost no change even when immersed in a 10% aqueous NaOH solution at 60 ° C. for 1 hour. The results are summarized in Tables 1 and 2.

Comparative Example 1 The polyamic acid solution prepared in Reference Example 1 was used, and the N, N-dimethylacetamide solution of N-phenyl-γ-aminopropylethoxysilane was not applied to the surface of the self-supporting film. Produced a polyimide film in the same manner as in Example 1. This polyimide film was bonded to an epoxy adhesive in the same manner as in Example 1. 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 ° peel strength was 0.3 kg / cm for the B side.
The surface was 0.1 kg / cm. Table 1 shows the weight ratio and content of each component in the surface of the polyimide film and in the film. The tensile modulus of this film was 870.
Even when immersed in a 10% aqueous solution of NaOH at 60 ° C. for 1 hour at kg / mm ² , the shape was kept almost unchanged.

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 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 bonded to an epoxy adhesive in the same manner as in Example 1. As a result of evaluating the adhesiveness, the T-peel strength was 1.7 kg / cm on the B side and 1.6 kg / cm on the F side.
cm, and the 180 degree peel strength of the B side is 3.0 kg /
cm and the F-side was 2.9 kg / cm. Weight ratio of each component in the surface of the polyimide film and the film,
Table 1 shows the content, and Table 2 shows other characteristics. The tensile modulus of the film was 310 kg / mm ² ,
When the film was immersed in a 60% aqueous solution of NaOH at 60 ° C. for 1 hour, the film was dissolved.

Comparative Example 3 The polyamic acid solution prepared in Reference Example 2 was cast on a stainless steel belt without adding the monostearyl phosphate triethanolamine salt to form
After drying at 0 ° C for 10 minutes, it was attempted to peel off from the stainless steel belt surface. However, peeling was difficult and the film was cut or peeling marks were formed on the peeled surface, making it impossible to produce a good film. Was.

Examples 4 to 9 The concentration of the silane compound in the N, N-dimethylacetamide solution of N-phenyl-γ-aminopropylethoxysilane was changed to 1% by weight (Example 4), or the concentration of the silane compound was changed to 15% by weight. % (Example 5), or monostearyl phosphate triethanolamine salt was added to 0.025%.
Parts (Example 6) or 0.5 parts (Example 7) of monostearyl phosphate triethanolamine, or monostearyl phosphate triethanolamine.
0.1 part of dioctyl phosphate monoethanolamine salt was used in place of the ruamine salt (Example 8), or 0.1 part of the monophosphate ester of triethylene glycol monotridecyl ether was used (Example 1). Example 9) Other than Example 1
Was performed in the same manner as described above. The results are summarized in Tables 1 and 2.

[0050]

[Table 1]

[0051]

[Table 2]

Example 10 The modified polyimide film obtained in Examples 1 to 9 was slit to form a tape having a width of 35 mm.
A polyimide adhesive tape having a width of m (UPA-322, manufactured by Ube Industries, Ltd.) is laminated on the modified surface of the polyimide tape so that the center line of the adhesive tape is overlapped with the adhesive tape. -A sample was prepared. A sprocket hole and a device hole were punched in the polyimide tape with the adhesive, and a copper foil (35 μm) was stuck at 130 ° C. to cure the adhesive. IL (inner lead) or OL (outer lead) is etched on the copper foil by a conventional method.
The carrier tape for TAB was manufactured by forming circuits such as those described above. When the IC was mounted on the carrier tape for TAB, the dimensional accuracy of the pad and the IL of the IC was hardly deviated, and the bonding could be performed accurately.

After sealing the IC with a potting resin,
When mounted on a printed board, the deviation of the dimensions of the circuit of the printed board and the OL of the TAB was small, and bonding could be performed accurately.

Comparative Example 4 A carrier tape for TAB was prepared in the same manner as described above except that the polyimide films obtained in Comparative Examples 1 to 3 were used. When the IC was mounted on this TAB carrier tape, the dimensional accuracy of the IC pad and the IL was greatly deviated, and the IC could not be bonded accurately and could not be used.

[0055]

Since the present invention is configured as described above, the following effects can be obtained.

This modified polyimide film has a large tensile modulus, excellent chemical resistance, a large adhesive strength even when laminated with other materials, and remains unchanged even after various manufacturing processes.
The dimensional accuracy in the manufacturing process is high, and the alignment when mounting other components is good.

The modified polyimide film comprising a biphenyltetracarboxylic acid component having a polymer component of 30 mol% or more and a phenylenediamine component of 50 mol% or more has a tensile modulus of 400 kg / mm ² or more. Excellent chemical resistance, high adhesive strength even when bonded to other materials, no change even after various manufacturing processes, high dimensional accuracy in manufacturing processes, good alignment when mounting other parts Yes, it can be obtained industrially in large quantities with stable and consistent quality.

The laminate using the modified polyimide film has a high adhesive strength, does not change even after various manufacturing steps, has high dimensional accuracy in the manufacturing steps, and has good alignment when mounting other parts. It is.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI C08J 7/04 C08J 7/04 M // C08L 79:08 C08L 79:08 (56) References JP-A-61-264028 (JP) JP-A-60-244507 (JP, A) JP-A-62-267330 (JP, A) JP-A-8-100072 (JP, A) JP-A-8-134234 (JP, A) 8-143688 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08J 5/18 B32B 27/28 B32B 27/34 C08G 73/10

Claims (2)

(57) [Claims] 1. The content of phosphorus (P) in the whole film is 5 to 5.
In the range of 500 ppm, an average linear expansion coefficient at a temperature of 50 to 300 ° C. is 2.5 × ^{10 -5} ℃ ^-1 or less, before and after subjected to 2 hours of heating at a Atsushi Nobori after the temperature from room temperature to 400 ° C. An aromatic polyimide film comprising an aromatic tetracarboxylic acid component and an aromatic diamine component, wherein the thermal dimensional change rate represented by the dimensional change rate of the film at room temperature is 0.3% or less, and at least one film surface Was determined by X-ray photoelectric pre-analysis (XPS) using an X-ray source of Mg Kα (300
W), the weight ratio of carbon to oxygen (C / O) was in the range of 2.9 to 4.6, and the weight ratio of oxygen to nitrogen (O / N) was 2.4 to 3 A polyimide-based adhesive is provided on the treated surface of the silicon compound-treated film so that the value in the range of 0.5 and the content of Si is in the range of 0.7 to 3.0% by weight; A laminated body formed by slitting. 2. A laminate obtained by laminating a copper foil on the laminate of claim 1 via a polyimide-based adhesive.