KR102423692B1 - Polyimide film - Google Patents

Abstract

[Problem] The dimensional change of the film is reduced, and it is isotropic with a small difference in the thermal expansion coefficients of MD and TD, and dimensional stability is required for semiconductor package applications, semiconductor manufacturing process applications, display applications, solar cell substrates, fine pitch circuit boards, etc. It aims at obtaining the polyimide film suitable for the use to be used.
[Solution]
A polyimide film obtained by using an aromatic diamine component containing paraphenylenediamine and an acid anhydride component, using TMA-50 manufactured by Shimadzu Corporation, in a measurement temperature range: 50 to 200°C, temperature increase rate: 10°C/min. Both the coefficient of thermal expansion α _MD in the machine transport direction ( _MD ) and the coefficient of thermal expansion α _TD in the width direction (TD) of the film measured under the conditions of A polyimide film characterized by satisfying the relation of -α _TD │<3.

Description

Polyimide film {POLYIMIDE FILM}

The present invention relates to a polyimide film having excellent dimensional stability and suitable for applications requiring dimensional stability such as semiconductor package applications, semiconductor manufacturing process applications, display applications, solar cell substrates, and fine pitch circuit boards.

With the increase in the fineness of flexible printed circuit boards (FPCs) and semiconductor packages, the requirements for polyimide films used therein are also increasing, for example, dimensional changes and curl due to bonding with metals. For the properties of the polyimide film, a film having a metal-level coefficient of thermal expansion and a high modulus of elasticity, furthermore, a film with small dimensional change due to absorption is required. A polyimide film has been developed.

For example, in order to raise an elastic modulus, the example of the polyimide film using para-phenylenediamine is known (patent document 1, 2, 3). Moreover, in order to reduce the dimensional change by water absorption while maintaining high elasticity, the example of the polyimide film which added to paraphenylenediamine and used biphenyltetracarboxylic dianhydride is known (patent document 4, 5).

Moreover, in order to suppress the dimensional change in the bonding process with a metal, the thermal expansion coefficient of the machine conveyance direction (henceforth MD) of a film is the thermal expansion coefficient of the width direction (henceforth TD) of a film. An example of a polyimide film in which anisotropy is given by setting smaller is known. This is a phenomenon in which a lamination method in which bonding with a metal is heated and performed by a roll-to-roll method is adopted in a normal FPC manufacturing process, and tension is applied to the MD of the film in this process to cause elongation, while shrinkage occurs in TD It aims to offset the (patent document 6).

Recent uses of polyimide films include, from advantages such as weight reduction and flexibility, semiconductor package uses, semiconductor manufacturing process uses, base films of displays such as electronic paper, and uses of solar cell substrates. Conventionally, polyimide films are often used for circuit board applications, and the coefficient of thermal expansion is often adjusted based on the coefficient of thermal expansion of copper forming wiring. However, in these recent applications, silica and glass, which have a lower coefficient of thermal expansion than copper, are often used, and conventional polyimide films have insufficient dimensional stability or warpage may occur due to the difference in thermal expansion coefficients between MD and TD. there was. Moreover, the case where a fine pitch is calculated|required also in the conventional board|substrate use for circuits has come out, In this case, the dimensional stability of the conventional polyimide film was inadequate.

Japanese Patent Laid-Open Publication No. 60-210629 Japanese Patent Laid-Open Publication No. 64-16832 Japanese Patent Laid-Open No. Hei1-131241 Japanese Patent Laid-Open No. 59-164328 Japanese Patent Laid-Open No. 61-111359 Japanese Patent Laid-Open Publication No. 4-25434

Summary of the invention

The problem the invention is trying to solve

The present invention is the result of studies to solve the problems in the prior art described above, the dimensional change of the film is reduced, and is isotropic with a small difference in the coefficient of thermal expansion between MD and TD, semiconductor package use, semiconductor It aims at obtaining the polyimide film suitable for the use which dimensional stability, such as a manufacturing process use, a display use, a solar cell board|substrate, and the board|substrate for fine-pitch circuits is calculated|required.

means to solve the problem

The inventors of the present invention, as a result of intensive examination to solve the above problems, as a polyimide film obtained using an aromatic diamine component containing paraphenylenediamine and an acid anhydride component, using TMA-50 manufactured by Shimadzu Corporation, Both the thermal expansion coefficient α _MD in the machine transport direction (MD) and the thermal expansion coefficient α _TD in the width direction (TD) of the film measured under the conditions of a measurement temperature range: 50 to 200°C, and a temperature increase rate: 10°C/min. A polyimide film characterized in that it is in the range of 0 ppm/°C or more and less than 7.0 ppm/°C, and satisfies the relation of |α _MD -α _TD |<3, the dimensional change of the film is reduced, and the MD and It was discovered that it is an isotropic film with a small difference in the thermal expansion coefficient of TD.

In addition to the above, the present inventors have obtained various unexpected new knowledge as follows, and further intensive studies have been carried out to complete the present invention.

That is, the present invention relates to the following inventions.

[1] A polyimide film obtained by using an aromatic diamine component containing para-phenylenediamine and an acid anhydride component, using TMA-50 manufactured by Shimadzu Corporation, in a measurement temperature range: 50 to 200°C, temperature increase rate: 10 Both the coefficient of thermal expansion α _MD in the machine transport direction (MD) and the coefficient of thermal expansion α _TD in the width direction (TD) of the film measured under the condition of ° C. / min are in the range of 0 ppm / ° C. or more and less than 7.0 ppm / ° C., A polyimide film characterized by satisfying the relation of |α _MD -α _TD |<3.

[2] A polyimide film obtained by using an aromatic diamine component containing paraphenylenediamine and an acid anhydride component, using TMA-50 manufactured by Shimadzu Corporation, in a measurement temperature range: 50 to 200°C, temperature increase rate: 10 Both the coefficient of thermal expansion α _MD in the machine transport direction (MD) and the coefficient of thermal expansion α _TD in the width direction (TD) of the film measured under the condition of ° C. / min are in the range of 0 ppm / ° C. or more and less than 7.0 ppm / ° C., A polyimide film characterized by satisfying the relation of |α _MD -α _TD |<2.

[3] The polyimide film according to claim 1 or 2, wherein both MD and TD of the film have heat shrinkage at 200°C of 0.05% or less.

[4] The polyimide film according to any one of claims 1 to 3, wherein both MD and TD of the film have a heat shrinkage rate at 200°C of 0.03% or less.

[5] The polyimide film according to any one of claims 1 to 4, wherein the film has a tensile modulus of elasticity of 6.0 GPa or more.

[6] The polyimide film according to any one of claims 1 to 5, wherein the film has a water absorption of 3.0% or less.

[7] The polyimide film according to any one of claims 1 to 6, wherein the amount of paraphenylenediamine is at least 31 mol% or more with respect to the total amount of the aromatic diamine component.

[8] The aromatic diamine component according to any one of claims 1 to 7, wherein at least one selected from the group consisting of 4,4'-diaminodiphenyl ether and 3,4'-diaminodiphenyl ether is added A polyimide film comprising:

[9] The acid anhydride component according to any one of claims 1 to 8, wherein the acid anhydride component is at least one selected from the group consisting of pyromellitic dianhydride and 3,3'-4,4'-diphenyltetracarboxylic dianhydride. Polyimide film, characterized in that.

[10] A copper-clad laminate, wherein the polyimide film according to any one of claims 1 to 9 is used.

[11] A glass/polyimide laminate, wherein the polyimide film according to any one of claims 1 to 10 is used.

Since the polyimide film of the present invention has excellent dimensional stability, it can be suitably used for applications requiring dimensional stability, such as semiconductor package applications, semiconductor manufacturing process applications, display applications, solar cell substrates, and fine pitch circuit boards. .

In addition, since the polyimide film of the present invention is an isotropic film with a small difference in thermal expansion coefficient between MD and TD, it is used for semiconductor package applications, semiconductor manufacturing process applications, display applications, solar cell substrates, fine pitch circuit boards, etc. The occurrence of warpage at the time can be reduced.

implementing the invention form for

The polyimide film of the present invention is a polyimide film obtained by using an aromatic diamine component containing paraphenylenediamine and an acid anhydride component, using TMA-50 manufactured by Shimadzu Corporation, and a measurement temperature range: 50 to 200°C , temperature increase rate: both of the thermal expansion coefficient α _MD in the machine transport direction (MD) and the thermal expansion coefficient α _TD in the width direction (TD) of the film measured under the conditions of 10° C./min. 0 ppm/° C. or more and less than 7.0 ppm/° C. It is characterized in that it satisfies the relation of │α _MD −α _TD │<3.

The thermal expansion coefficient α MD of the polyimide film of the present invention in the machine transport direction ( _MD ) and the thermal expansion coefficient α _TD in the transverse direction (TD) are all usually in the range of 0 ppm/°C or more and less than 7.0 ppm/°C, and 1.0 ppm The range of /°C or more and 7.0 ppm/°C or less is preferable, the range of 2.0 ppm/°C or more and 6.5 ppm/°C or less is more preferable, the range of 2.0 ppm/°C or more and 6.0 ppm/°C or less is still more preferable, 2.0 ppm The range of /°C or more and 5.5 ppm/°C or less is particularly preferable.

When it is less than the said range, since the intensity|strength (for example, tensile elongation etc.) is inferior and it becomes easy to produce a crack in the film obtained, it is unpreferable. By making α _MD and α _TD within the above range and combining with each component of the present invention, regardless of the partner to which the polyimide film adheres (for example, the partner to which the film adheres is a metal (eg, copper)) Since it has excellent dimensional stability, it can be suitably used for applications requiring dimensional stability, such as semiconductor package applications, semiconductor manufacturing process applications, display applications, solar cell substrates, and fine pitch circuit boards.

The measurement conditions of the coefficients of thermal expansion α _MD and α _TD in the present invention are values measured under the conditions of a measurement temperature range: 50 to 200° C. and a temperature increase rate: 10° C./min using TMA-50 manufactured by Shimadzu Corporation. to be.

The polyimide film of the present invention usually satisfies the relation of │α _MD -α _TD │<3 with respect to the α _MD and the α _TD , preferably, the relation of │α _MD -α _TD │<2 , more preferably │α _MD −α _TD │<1.5, and still more preferably │α _MD −α _TD │<1.0.

It is preferable that both MD and TD are 0.05 % or less, and, as for the 200 degreeC heat shrinkage rate of the polyimide film of this invention, it is more preferable that both are 0.03 % or less. In addition, in this invention, the 200 degreeC heating contraction rate is the value computed by the method described in the Example mentioned later.

6.0 GPa or more is preferable, as for the tensile modulus of elasticity of the polyimide film of this invention, 6.5 GPa or more is more preferable, 7.0 GPa or more is still more preferable. Moreover, 6.0 GPa or more is preferable in both MD and TD, 6.5 GPa or more is more preferable in both MD and TD, and 7.0 GPa or more is still more preferable in both MD and TD.

3.0 % or less is preferable and, as for the water absorption of the polyimide film of this invention, 2.8 % or less is more preferable.

Although the tear propagation resistance of the polyimide film of the present invention is not particularly limited, from the viewpoint of good runability of the film, the tear propagation resistance is preferably 3.0 N/mm or more in both MD and TD, and 5.0 N/mm or more This is more preferable. The tear propagation resistance is a value measured using a light load tear tester similar to the Elmendorf tear method. Since the measured value shows resistance when a film is torn, it has shown the difficulty of tearing in consideration of the whole thickness direction, and it means that a film is hard to tear, so that it is large, and it is excellent in running property.

Less than 0.01 % is preferable and, as for the dimensional change rate of the polyimide film of this invention, 0.008 % or less is more preferable.

When manufacturing the polyimide film of this invention, a polyamic-acid solution is obtained by first superposing|polymerizing an aromatic diamine component and an acid anhydride component in an organic solvent.

The polyimide film of this invention contains para-phenylenediamine as said aromatic diamine component. The aromatic diamine component may contain substances other than paraphenylenediamine, and specific examples of the aromatic diamine component other than paraphenylenediamine include metaphenylenediamine, benzidine, paraxylylenediamine, 4,4'-diamino Diphenyl ether, 3, 4'-diaminodiphenyl ether, 4, 4'-diaminodiphenylmethane, 4, 4'-diaminodiphenyl sulfone, 3, 3'-dimethyl-4, 4'-dia minodiphenylmethane, 1,5-diaminonaphthalene, 3,3'-dimethoxybenzidine, 1,4-bis(3methyl-5aminophenyl)benzene, and amide-forming derivatives thereof. These may be used individually by 1 type, and may mix and use 2 or more types. As the aromatic diamine component, a combination of paraphenylenediamine with 4,4'-diaminodiphenyl ether and/or 3,4'-diaminodiphenyl ether is preferable. Among these, by adjusting the amount of the diamine component of paraphenylenediamine and 3,4'-diaminodiphenyl ether, which has the effect of increasing the tensile modulus of elasticity of the film, the tensile modulus of the polyimide film obtained is set to 6.0 GPa or more. , which is preferable because the transportability is also improved.

Specific examples of the acid anhydride component include pyromellitic acid, 3, 3', 4, 4'-diphenyltetracarboxylic acid, 2, 3', 3, 4'-diphenyltetracarboxylic acid, 3, 3', 4 , 4'-benzophenone tetracarboxylic acid, 2, 3, 6, 7-naphthalene tetracarboxylic acid, 2, 2-bis (3,4-dicarboxyphenyl) ether, pyridine-2, 3, 5, 6-tetra and aromatic tetracarboxylic anhydride components such as carboxylic acid and their amide-forming derivatives, and pyromellitic dianhydride and 3,3',4,4'-diphenyltetracarboxylic dianhydride are preferable. These may be used individually by 1 type, and may mix and use 2 or more types.

Among these, a particularly suitable combination of an aromatic diamine component and an acid anhydride component is selected from the group consisting of paraphenylenediamine, 4,4'-diaminodiphenyl ether and 3,4'-diaminodiphenyl ether. a combination of at least one aromatic diamine component and at least one acid anhydride component selected from the group consisting of pyromellitic dianhydride and 3,3',4,4'-diphenyltetracarboxylic dianhydride; .

The blending ratio (molar ratio) of paraphenylenediamine in the aromatic diamine component is the total amount of the aromatic diamine component in terms of obtaining a coefficient of thermal expansion within the above range, imparting an appropriate strength to the film, and preventing poor running performance. , usually at least 31 mol% or more, preferably 33 mol% or more, and more preferably 35 mol% or more.

Although it does not specifically limit as a compounding ratio (molar ratio) in said acid anhydride component, unless the effect of this invention is impaired, For example, 3, 3', 4, 4'- diphenyltetracarboxylic dianhydride When including, the content of 3,3',4,4'-diphenyltetracarboxylic dianhydride is preferably 15 mol% or more, more preferably 20 mol% or more, with respect to the total amount of the acid anhydride component, 25 mol% or more is more preferable.

When the polyimide film of the present invention is made of a polyamic acid comprising these aromatic diamine components and an acid anhydride component, the coefficient of thermal expansion of the polyimide film in the machine transport direction (MD) and width direction (TD) of the film is within the above range. Since it can adjust easily, it is preferable.

In the present invention, specific examples of the organic solvent used for forming the polyamic acid solution include, for example, sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide, N,N-dimethylformamide, N, Formamide solvents such as N-diethyl formamide, acetamide solvents such as N,N-dimethyl acetamide and N,N-diethyl acetamide, N-methyl-2-pyrrolidone, N-vinyl- Pyrrolidone solvents such as 2-pyrrolidone, phenolic solvents such as phenol, o-, m-, or p-cresol, xylenol, halogenated phenol, catechol, hexamethylphosphoramide, Aprotic polar solvents, such as lactone, are mentioned, Although it is preferable to use these individually or as a mixture using 2 or more types, use of aromatic hydrocarbons, such as xylene and toluene, is also possible.

The polymerization method may be any one of known methods, for example,

(1) A method of polymerization by first putting the entire amount of the aromatic diamine component in a solvent, and then adding the acid anhydride component so as to have an equivalent weight (equimolar) with the total amount of the aromatic diamine component.

(2) A method of polymerization by first putting the entire amount of the acid anhydride component in a solvent, and then adding the aromatic diamine component so as to be equivalent to the acid anhydride component.

(3) After putting one aromatic diamine component (a1) in the solvent, one side of the acid anhydride component (b1) is mixed for the time required for the reaction in a ratio of 95 to 105 mol% with respect to the reaction component, and then the other A method in which an aromatic diamine component (a2) is added, and then the other acid anhydride component (b2) is added so that the total aromatic diamine component and the total acid anhydride component are substantially equivalent to each other, followed by polymerization.

(4) After putting one acid anhydride component (b1) in a solvent, one aromatic diamine component (a1) is 95 to 105 mol% with respect to the reaction component, and mixing for the time required for the reaction A method of polymerization by adding an acid anhydride component (b2), then adding the other aromatic diamine component (a2) so that the total aromatic diamine component and the total acid anhydride component are approximately equivalent.

(5) A polyamic acid solution (A) is prepared by reacting one aromatic diamine component and an acid anhydride component in a solvent such that either one becomes excessive, and the other aromatic diamine component and the acid anhydride component are mixed with either one of the other aromatic diamine component and the acid anhydride component in another solvent. It is made to react so that it may become this excess, and a polyamic-acid solution (B) is adjusted. The method of mixing each polyamic-acid solution (A) and (B) obtained in this way, and completing superposition|polymerization. At this time, when the aromatic diamine component is excessive when adjusting the polyamic acid solution (A), the acid anhydride component is excessive in the polyamic acid solution (B), and when the acid anhydride component is excessive in the polyamic acid solution (A), the polyamic acid solution (A) In the mixed acid solution (B), the aromatic diamine component is made excessive, and the polyamic acid solution (A) and (B) are mixed, and the total aromatic diamine component and all the acid anhydride components used for these reactions are adjusted so that they are almost equivalent. In addition, the polymerization method is not limited to these, Other well-known methods may be used.

The polyamic acid solution obtained in this way contains a solid content of 5 to 40 weight% normally, Preferably it contains a solid content of 10 to 30 weight%. In addition, the viscosity is 10-2000 Pa*s normally in the measured value by a Brookfield viscometer, For stable liquid feeding, Preferably it is 100-1000 Pa.s. In addition, in the organic solvent solution, the polyamic acid may be imidated partially.

Next, the manufacturing method of a polyimide film is demonstrated. As a method for forming a polyimide film, a method for obtaining a polyimide film by casting a polyamic acid solution into a film and thermally decyclizing and desolving it, and a method for chemically decyclizing a polyamic acid solution by mixing a cyclization catalyst and a dehydrating agent Although the method of obtaining a polyimide film by producing a gel film and heating and desolving this is mentioned, since the latter can suppress the thermal expansion coefficient of the polyimide film obtained low, it is preferable.

In the method of chemically decyclizing, the said polyamic-acid solution is prepared first. Moreover, this polyamic-acid solution can contain chemically inactive organic fillers and inorganic fillers, such as a titanium oxide, a silica, a calcium carbonate, a calcium phosphate, a calcium hydrogen phosphate, and a polyimide filler, as needed. Content of a filler is not specifically limited unless the effect of this invention is impaired.

Even if the polyamic-acid solution used here may be the polyamic-acid solution which superposed|polymerized previously, what superposed|polymerized in order when making a filler particle contain also may be sufficient as it.

The polyamic acid solution may contain a cyclization catalyst (imidization catalyst), a dehydrating agent, a gelation retardant, and the like.

Specific examples of the cyclization catalyst used in the present invention include aliphatic tertiary amines such as trimethylamine and triethylenediamine, aromatic tertiary amines such as dimethylaniline, and heterocyclic tertiary amines such as isoquinoline, pyridine and betapicoline. Although a quaternary amine etc. are mentioned, A heterocyclic tertiary amine is preferable. These may be used individually by 1 type, and may mix and use 2 or more types.

Specific examples of the dehydrating agent used in the present invention include aliphatic carboxylic anhydrides such as acetic anhydride, propionic anhydride, and butyric anhydride, and aromatic carboxylic anhydrides such as benzoic anhydride. Acetic anhydride and/or benzoic anhydride are preferred. . It does not specifically limit as a gelation retardant, Acetylacetone etc. can be used.

As a method for producing a polyimide film from a polyamic acid solution, the polyamic acid solution containing the cyclization catalyst and the dehydrating agent is cast from a slit-type nozzle onto a support to form a film, and imidized on the support. After partially advancing and setting it as a gel film which has self-supporting property, it peels from a support body, heat-drying / imidation, and the method of heat-processing is mentioned.

The support is a metal rotating drum or an endless belt, the temperature of which is controlled by heat of liquid or gas and/or by radiant heat such as an electric heater.

The gel film is heated to usually 30 to 200° C., preferably 40 to 150° C. by water heat from a support and/or heat from a heat source such as hot air or an electric heater for a ring closure reaction, and free organic By drying volatile matter, such as a solvent, it has self-supporting property and peels from a support body.

Although the gel film peeled from the said support body is not specifically limited, Usually, it is preferable to extend|stretch in a conveyance direction, regulating a traveling speed with a rotating roll. Extending|stretching to a conveyance direction is performed at the temperature of 140 degrees C or less. The draw ratio (MDX) is 1.05-1.9 times normally, Preferably it is 1.1-1.6 times, More preferably, it is 1.1-1.5 times. The gel film stretched in the conveyance direction is introduced into a tenter device, both ends in the width direction are gripped by a tenter clip, and is stretched by a width method while traveling together with the tenter clip. Extending|stretching to the width direction is performed at the temperature of 200 degreeC or more. The draw ratio (TDX) is 1.1 to 1.5 times of MDX normally, Preferably it is 1.2 to 1.45 times. By combining this draw ratio with respect to the gel film obtained by the said compounding, an isotropic film can be obtained and the film which has the effect of this invention can be obtained.

The film dried in said drying zone is heated by a hot air, an infrared heater, etc. for 15 second - 10 minutes. Next, heat treatment is performed for 15 seconds to 20 minutes at a temperature of 250 to 500°C with hot air and/or an electric heater.

Moreover, although traveling speed is adjusted and the thickness of a polyimide film is adjusted, as thickness of a polyimide film, in order to prevent deterioration of film forming property, 3-250 micrometers is preferable and 5-150 micrometers is more preferable.

It is preferable to further perform an annealing process with respect to the polyimide film obtained in this way. By doing so, thermal relaxation of the film occurs and the heat shrinkage rate can be suppressed small. Although it does not specifically limit as temperature of an annealing process, 200 degreeC or more and 500 degrees C or less are preferable, 200 degreeC or more and 370 degrees C or less are more preferable, 210 degreeC or more and 350 degrees C or less are especially preferable. Since the heat shrinkage rate at 200 degreeC can be suppressed within the said range by the thermal relaxation from an annealing process, dimensional accuracy further becomes high and it is preferable. Specifically, it is preferable to carry out the annealing treatment by running the film under the storage force in the furnace heated to the above temperature range. Although the time for which a film stays in a furnace becomes a processing time, it is controlled by changing a running speed, and it is preferable that it is a processing time of 30 second - 5 minutes. If it is shorter than this, heat is not sufficiently transmitted to the film, and if it is longer than this, there is a tendency to overheat and impair the flatness, which is not preferable. Moreover, 10-50 N/m is preferable and, as for the film tension|tensile_strength at the time of running, 20-30 N/m is more preferable. When the tension is lower than this range, the running property of the film deteriorates, and when the tension is high, the thermal contraction rate in the running direction of the obtained film increases, which is not preferable.

In addition, in order to give the obtained polyimide film adhesiveness, the film surface may be subjected to an electrical treatment such as corona treatment or plasma treatment or a physical treatment such as a blast treatment, and these physical treatments can be performed according to a conventional method. . Although the pressure of the atmosphere in the case of plasma processing is not specifically limited, Usually, the range of 13.3-1330 kPa, the range of 13.3-133 kPa (100-1000 Torr) is preferable, 80.0-120 kPa (600-900 Torr) ) is more preferable.

The atmosphere in which the plasma treatment is performed contains at least 20 mol% of an inert gas, preferably contains 50 mol% or more of inert gas, more preferably contains 80 mol% or more, and contains 90 mol% or more Most preferred. The inert gas includes He, Ar, Kr, Xe, Ne, Rn, N ₂ and a mixture of two or more thereof. A particularly preferred inert gas is Ar. In addition, with respect to the inert gas, oxygen, air, carbon monoxide, carbon dioxide, carbon tetrachloride, chloroform, hydrogen, ammonia, tetrafluoromethane (carbon tetrafluoride), trichlorofluoroethane, trifluoromethane, etc. may be mixed. . Preferred combinations of mixed gases used as the atmosphere for the plasma treatment of the present invention are argon/oxygen, argon/ammonia, argon/helium/oxygen, argon/carbon dioxide, argon/nitrogen/carbon dioxide, argon/helium/nitrogen, argon/helium. /nitrogen/carbon dioxide, argon/helium, helium/air, argon/helium/monosilane, argon/helium/disilane, etc. are mentioned.

Although the processing power density at the time of plasma processing is not specifically limited, 200 W min/m<2> or more is preferable, 500 W min/m<2> or more is more preferable, 1000 W min/m<2> or more is the most preferable. . The plasma irradiation time for plasma processing is preferably 1 second to 10 minutes. By setting the plasma irradiation time within this range, the effect of the plasma treatment can be sufficiently exhibited without causing deterioration of the film. The gas type, gas pressure, and processing density of plasma processing are not limited to the above conditions, and may be performed in the atmosphere.

Since the polyimide film obtained in this way is an isotropic polyimide film with little dimensional change of the film and a small difference in thermal expansion coefficient between MD and TD, semiconductor package use, semiconductor manufacturing process use, display use, solar cell substrate, fine It can be suitably used for applications requiring dimensional stability, such as a board|substrate for pitch circuits.

Moreover, this invention also includes the copper clad laminated body in which the polyimide film of this invention mentioned above is used. The manufacturing method of the copper clad laminated body of this invention is not specifically limited, A conventionally well-known manufacturing method may be followed. The copper clad laminate of the present invention can be obtained by, for example, forming the polyimide film of the present invention as a base material and forming copper having a thickness of 1 to 10 µm thereon according to a conventional method.

Moreover, this invention includes the glass/polyimide laminated body in which the polyimide film of this invention mentioned above is used. Although the manufacturing method of the said laminated body is not specifically limited, For example, what bonded together glass and the polyimide film of this invention according to a conventional method may be sufficient, Furthermore, Between glass and the polyimide film of this invention, it is desired Thus, an adhesive or the like may be sandwiched in accordance with a conventional method.

When using the polyimide film of this invention for a display, for example, after laminating|stacking a display on the polyimide film side of the glass/polyimide laminated body of this invention, by removing a glass part, this invention A display using a polyimide film can be obtained.

This invention includes the aspect which combined various said structures within the technical scope of this invention as long as the effect of this invention is effective.

Example

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited by these examples, and many modifications may be made to those of ordinary skill in the art within the technical spirit of the present invention. is possible by

In addition, in Examples, PPD represents paraphenylenediamine, 4,4'-ODA represents 4,4'-diaminodiphenyl ether, PMDA represents pyromellitic dianhydride, and BPDA represents 3,3 ', 4, 4'-biphenyltetracarboxylic dianhydride, and DMAc, N, N-dimethylacetamide, respectively.

In addition, each characteristic in an Example was evaluated by the following method.

(1) coefficient of thermal expansion

Apparatus: Using TMA-50 (trade name, manufactured by Shimadzu Corporation), measurement was performed under the conditions of a measurement temperature range: 50 to 200°C, and a temperature increase rate: 10°C/min.

(2) Heat shrinkage

Measure the film dimension (L1) after leaving it to stand for 2 days in a room adjusted to 25°C and 60%RH, then heated to 200°C for 60 minutes, and then placed in a room adjusted to 25°C and 60%RH for 2 days. After leaving to stand, the film dimension (L2) was measured and evaluated by the following formula calculation.

Heat shrinkage (%) = -(L2-L1)/L1｝×100

(3) tensile modulus of elasticity

Apparatus: RTM-250 (trade name, manufactured by A&D) was used, and measurement was performed under the conditions of tensile speed: 100 mm/min.

(4) Dimensional change rate

A 10 μm thick copper layer was formed on the film by electrolytic plating with a copper sulfate plating solution, pattern etched at 30 μm pitch (15 μm line spacing) to wire copper to the TD, and then .) Tin plating was performed with the electroless tin plating solution LT34, and the dimension of TD at this time was measured (L3). This was placed on a bonding stage at 250°C and the dimensions of the TD after bonding with the chip by a bonding tool at 400°C were measured (L4). The dimensional change rate was calculated|required by the following formula.

Dimensional change rate (%) = ｛(L4-L3)/L3｝×100

(5) Tear propagation resistance

A 63.5 mm x 50 mm test piece was prepared from a polyimide film, a 12.7 mm-length sheath was put in the test piece, and it measured according to JIS P8116 using the Toyo Seiki light load tear tester.

(6) absorption rate

After immersing the film in distilled water for 48 hours, it was taken out, and the water on the surface was quickly wiped off, and a sample was cut into a size of about 5 mm x 15 mm. After the film was applied to Seo Electric, it was measured with a thermogravimetric analyzer TG-50 manufactured by Shimadzu Corporation. The temperature increase rate was increased to 200°C at 10°C/min, and the water absorption was calculated from the change in weight using the following formula.

Water absorption (%) = ｛ (weight before heating) - (weight after heating) ｝/(weight after heating) x 100

[Example 1]

In a 500 ml separable flask, put 238.6 g of DMAc, PPD 5.68 g (0.053 mol), 4,4'-ODA 19.52 g (0.098 mol), BPDA 11.03 g (0.038 mol), PMDA 24.54 g (0.113 mol) ), it was made to react in normal temperature and normal pressure for 1 hour, and it stirred until it became uniform, and obtained the polyamic-acid solution.

After extracting 15 g from this polyamic-acid solution and cooling to minus 5 degreeC, the liquid mixture was obtained by mixing 1.9 g of acetic anhydride and 1.8 g of (beta)-picoline.

The thus-obtained liquid mixture was cast on a rotating drum at 90 DEG C for 30 seconds, and then the resulting gel film was stretched 1.23 times in the traveling direction while heating at 100 DEG C for 5 minutes. Then, both ends in the width direction were gripped and stretched 1.4 times in the width direction while heating at 270°C for 2 minutes, and then heated at 380°C for 5 minutes to obtain a polyimide film having a thickness of 38 µm. After applying the tension of 20 N/m to this polyimide film in the furnace set to 220 degreeC, and annealing it for 1 minute, each characteristic was evaluated as shown in Table 1.

[Examples 2 to 3]

In the same procedure as in Example 1, the aromatic diamine component and the aromatic tetracarboxylic acid anhydride component were each obtained in a polyamic acid solution in the ratio shown in Table 1, and then the draw ratios in the transverse and vertical directions were performed as shown in Table 1. Each characteristic evaluation of the polyimide film obtained by operation similar to 1 was performed, and the result was shown in Table 1.

Example One 2 3 proportion of each raw material
(molar ratio) PPD 35
4, 4'-ODA 65
BPDA 25
PMDA 75 PPD 40
4, 4'-ODA 60
BPDA 25
PMDA 75 PPD 40
4, 4'-ODA 60
BPDA 25
PMDA 75 draw ratio MDX 1.23 1.22 1.18 TDX 1.40 1.44 1.39 coefficient of thermal expansion
(ppm/℃) MD 6.3 4.1 4.5 TD 5.3 2.9 3.8 Heat shrinkage
(%) MD 0.01 0.02 0.02 TD 0.02 0.02 0.02 tensile modulus
(GPa) MD 6.9 7.62 7.5 TD 7.3 8.09 7.69 tear propagation resistance
(N/mm) MD 6.1 6.2 6.1 TD 6.0 5.9 6.1 Dimensional change rate (%) 0.011 0.007 0.009 Absorption rate (%) 2.2 2.4 2.4

(In a table|surface, molar ratio shows the mol% in all the aromatic diamine components, and the mol% in all the acid anhydride components, respectively.)

From the results of Examples 1 to 3, it was confirmed that the polyimide film of the present invention is an isotropic film with little dimensional change and a small difference in the coefficients of thermal expansion between MD and TD.

Since the polyimide film of the present invention is an isotropic film with little dimensional change and a small difference in thermal expansion coefficient between MD and TD, semiconductor package use, semiconductor manufacturing process use, display use, solar cell substrate, fine pitch circuit board, etc. It can be suitably used for applications requiring dimensional stability of

Claims (11)

A polyimide film obtained by using paraphenylenediamine, an aromatic diamine component consisting of at least one selected from the group consisting of 4,4'-diaminodiphenyl ether and 3,4'-diaminodiphenyl ether, and an acid anhydride component As , both of the thermal expansion coefficient α _MD in the machine transport direction (MD) and the thermal expansion coefficient α _TD in the width direction (TD) of the film measured under the conditions of a measurement temperature range: 50 to 200 ° C. and a temperature increase rate: 10 ° C./min. It exists in the range of 2.0 ppm/degreeC or more and less than 6.5 ppm/degreeC, and the relationship of |α _MD -α _TD |<3 is satisfied. The polyimide film characterized by the above-mentioned. A polyimide film obtained by using paraphenylenediamine, an aromatic diamine component consisting of at least one selected from the group consisting of 4,4'-diaminodiphenyl ether and 3,4'-diaminodiphenyl ether, and an acid anhydride component As , both of the thermal expansion coefficient α _MD in the machine transport direction (MD) and the thermal expansion coefficient α _TD in the width direction (TD) of the film measured under the conditions of a measurement temperature range: 50 to 200 ° C. and a temperature increase rate: 10 ° C./min. It exists in the range of 2.0 ppm/degreeC or more and less than 6.0 ppm/degreeC, and satisfy|fills the relationship of |α _MD -α _TD |<2, The polyimide film characterized by the above-mentioned. The polyimide film according to claim 1 or 2, wherein both the MD and TD of the film have heat shrinkage at 200°C of 0.05% or less. The polyimide film according to claim 1 or 2, wherein both MD and TD of the film have heat shrinkage at 200°C of 0.03% or less. The polyimide film according to claim 1 or 2, wherein the film has a tensile modulus of elasticity of 6.0 GPa or more. The polyimide film according to claim 1 or 2, wherein the film has a water absorption of 3.0% or less. The polyimide film according to claim 1 or 2, wherein the amount of paraphenylenediamine is at least 31 mol% or more based on the total amount of the aromatic diamine component. The polyimide film according to claim 1 or 2, wherein the aromatic diamine component consists only of paraphenylenediamine and 4,4'-diaminodiphenyl ether. The polyimide film according to claim 1 or 2, wherein the acid anhydride component is at least one selected from the group consisting of pyromellitic dianhydride and 3,3'-4,4'-diphenyltetracarboxylic dianhydride. . The polyimide film of Claim 1 or 2 is used, The copper clad laminated body characterized by the above-mentioned. A glass/polyimide laminate characterized in that the polyimide film according to claim 1 or 2 is used.