KR20150138032A - Polyimide film - Google Patents

Abstract

The purpose of the present invention is to provide a polyimide film wherein the dimensional change of which is reduced, which is isotropic with a small difference between coefficients of thermal expansion in a machine direction (MD) and in a transverse direction (TD), and is suitable for applications in which dimensional stability is required, such as for a semiconductor package, a semiconductor manufacturing process, a display, a solar cell substrate, a substrate for fine pitch circuits, etc. The polyimide film is obtained by using aromatic diamines including para-phenylenediamine and acid anhydrides. When the polyimide film is measured with TMA-50 manufactured by Shimadzu Co. under the conditions where a measurement temperature range is 50 to 200°C and a rate of temperature increase is 10°C/min., both of α_MD, the coefficient of thermal expansion in the MD, and α_TD, the coefficient of thermal expansion in the TD are 0 ppm/°C or more and less than 7.0 ppm/°C, and ¦α_MD - α_TD¦<3 is satisfied.

Description

POLYIMIDE FILM [0002]

The present invention relates to a polyimide film which is excellent in dimensional stability and suitable for use in semiconductor packages, semiconductor manufacturing process applications, display applications, solar cell substrates, substrates for fine pitch circuits, and the like requiring dimensional stability.

As the flexible printed circuit board (FPC) and the semiconductor package are made highly refined, the requirements for the polyimide film used therefor are increasing. For example, a dimensional change due to bonding with a metal, And a high handling property. Examples of the physical properties of the polyimide film include those having a thermal expansion coefficient of a metal level, a high elastic modulus, and a film having a small dimensional change due to absorption. A polyimide film has been developed.

For example, examples of polyimide films using paraphenylenediamine for increasing the modulus of elasticity are known (Patent Documents 1, 2, and 3). Examples of polyimide films using biphenyltetracarboxylic dianhydride added to paraphenylenediamine in order to reduce dimensional changes due to absorption while maintaining high elasticity are known (Patent Documents 4 and 5).

The thermal expansion coefficient of the film in the machine direction (hereinafter, also referred to as MD) is preferably set so that the thermal expansion coefficient of the film in the width direction of the film (hereinafter also referred to as TD) Anisotropy is set to be smaller than that of the polyimide film. This is because in the ordinary FPC production process, a lamination method is employed in which the fusion with a metal is heated and carried out in a roll-to-roll manner. In this process, tension is applied to the MD of the film in this process, (Patent Document 6).

Recent applications of the polyimide film include use of semiconductor packages, applications of semiconductor manufacturing processes, base films of displays such as electronic paper, and applications of solar cell substrates, from the advantages of weight reduction and flexibility. Conventionally, polyimide films are widely used for circuit boards, and the coefficient of thermal expansion thereof is often adjusted based on the thermal expansion coefficient of copper forming the wiring. However, there are many cases where silica or glass having a thermal expansion coefficient lower than that of copper is used in recent years, and the conventional polyimide film has insufficient dimensional stability or warpage due to the difference in thermal expansion coefficient between MD and TD there was. In addition, a fine pitch is also required for use in conventional circuit boards, and in this case, dimensional stability of the conventional polyimide film is insufficient.

Japanese Patent Application Laid-Open No. 60-210629 Japanese Patent Application Laid-Open No. 64-16832 Japanese Patent Application Laid-Open No. Hei 1-131241 Japanese Patent Application Laid-Open No. 59-164328 Japanese Patent Application Laid-Open No. 61-111359 Japanese Patent Application Laid-Open No. 4-25434

Summary of the Invention

Problems to be solved by the invention

DISCLOSURE OF THE INVENTION It is an object of the present invention to solve the problems in the prior art described above and to provide a method of manufacturing a semiconductor device which can reduce the dimensional change of a film and is isotropic in which the difference in thermal expansion coefficient between MD and TD is small, It is an object of the present invention to obtain a polyimide film suitable for applications requiring dimensional stability such as production process use, display use, solar cell substrate, fine pitch circuit substrate and the like.

Means for solving the problem

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that a polyimide film obtained by using an aromatic diamine component containing paraphenylenediamine and an acid anhydride component is produced by using Shimazu TMA- The thermal expansion coefficient? _MD of the film in the machine direction (MD) and the thermal expansion coefficient? _{TD in} the width direction (TD) of the film measured at () at a measurement temperature range of 50 to 200 占 폚 and a temperature raising rate of 10 占 폚 / Is in the range of 0 ppm / DEG C to less than 7.0 ppm / DEG C, and satisfies the relation of? _{MD -} ? _TD ? <3, TD is an isotropic film having a small difference in thermal expansion coefficient.

The inventors of the present invention have obtained various new and unexpected new discoveries as described below and have completed the present invention by repeatedly examining the examples carefully.

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

[1] A polyimide film obtained by using an aromatic diamine component containing paraphenylenediamine and an acid anhydride component, using a TMA-50 manufactured by Shimazu Seisakusho under the conditions of a measurement temperature range of 50 to 200 ° C and a temperature raising rate of 10 ℃ / and the thermal expansion coefficient α _MD and the thermal expansion coefficient range of both the α _TD 0 ppm / ℃ or more and less than 7.0 ppm / ℃ in the transverse direction (TD) of the machine conveying direction (MD) of the film measured under the conditions of a minute, ? _{MD -} ? _TD ? <3.

[2] A polyimide film obtained by using an aromatic diamine component containing paraphenylenediamine and an acid anhydride component was measured using a TMA-50 manufactured by Shimazu Corporation under the conditions of a measurement temperature range of 50 to 200 ° C and a temperature raising rate of 10 ℃ / and the thermal expansion coefficient α _MD and the thermal expansion coefficient range of both the α _TD 0 ppm / ℃ or more and less than 7.0 ppm / ℃ in the transverse direction (TD) of the machine conveying direction (MD) of the film measured under the conditions of a minute, ? _{MD -} ? _TD ? &Lt; 2.

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

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

[5] The polyimide film according to any one of claims 1 to 4, wherein the tensile modulus of the film is 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 para-phenylenediamine is at least 31 mol% with respect to the total amount of the aromatic diamine component.

[8] The aromatic diamine compound 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 as the aromatic diamine component Wherein the polyimide film is a polyimide film.

[9] The method 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 acid dianhydride and 3,3'-4,4'-diphenyltetracarboxylic dianhydride &Lt; / RTI &gt;

[10] A copper-clad laminate characterized by using the polyimide film according to any one of claims 1 to 9.

[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 is excellent in 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, substrates for fine pitch circuits and the like .

Further, since the polyimide film of the present invention is an isotropic film having a small difference in thermal expansion coefficient between MD and TD, the polyimide film can be used for semiconductor package applications, semiconductor manufacturing process applications, display applications, solar cell substrates, and substrates for fine pitch circuits It is possible to reduce the occurrence of warping.

Carrying out 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 and measuring the temperature range of 50 to 200 DEG C , The thermal expansion coefficient? _{MD in} the machine direction (MD) of the film and the thermal expansion coefficient? _{TD in} the width direction (TD) of the film measured under the condition of a temperature rise rate of 10 占 폚 / , And satisfies a relation of |? _{MD -} ? _TD | <3.

The thermal expansion coefficient? _{MD in} the machine direction (MD) and the thermal expansion coefficient? _TD in the width direction (TD) of the polyimide film of the present invention are generally in the range of 0 ppm / 占 폚 to 7.0 ppm / 占 폚, / C to 7.0 ppm / ° C., more preferably from 2.0 ppm / ° C. to 6.5 ppm / ° C., still more preferably from 2.0 ppm / ° C. to 6.0 ppm / / C &lt; / RTI &gt; and 5.5 ppm / DEG C or less is particularly preferred.

Below the above range, the strength (for example, tensile elongation and the like) is inferior and the resulting film tends to be cracked, which is not preferable. By making α _MD and α _TD fall within the above ranges and by combining with the respective components of the present invention, regardless of the relative to which the polyimide film adheres (for example, the metal to which the film adheres is a metal (for example, copper) Or glass), it can be suitably used for applications requiring dimensional stability, such as semiconductor package applications, semiconductor manufacturing process applications, display applications, solar cell substrates, substrates for fine pitch circuits, and the like.

The measurement conditions of the thermal expansion coefficients α _MD and α _{TD in} the present invention were measured using a TMA-50 manufactured by Shimazu Corporation under the conditions of a measurement temperature range of 50 to 200 ° C. and a temperature increase rate of 10 ° C./min to be.

The polyimide film of the present invention, the relationship between the α _MD and _TD are relative to the α, to satisfy the relationship of the _{normal, │α MD -α TD │ <3} , and preferably, │α _MD -α _TD │ <2 to satisfy, and more preferably satisfy the relation of │α _MD -α _TD │ <satisfies the relationship of 1.5, more preferably │α _MD -α _TD │ <1.0.

The polyimide film of the present invention preferably has a heat shrinkage at 200 ° C of not more than 0.05% in both MD and TD, more preferably not more than 0.03%. In the present invention, the heat shrinkage at 200 캜 is a value calculated by the method described in the following Examples.

The tensile modulus of elasticity of the polyimide film of the present invention is preferably 6.0 GPa or more, more preferably 6.5 GPa or more, and further preferably 7.0 GPa or more. Further, both MD and TD are preferably 6.0 GPa or more, more preferably 6.5 GPa or more in both MD and TD, and more preferably 7.0 GPa or more in both MD and TD.

The water absorption of the polyimide film of the present invention is preferably 3.0% or less, more preferably 2.8% or less.

The tear propagation resistance of the polyimide film of the present invention is not particularly limited, but is preferably 3.0 N / mm or more in both the MD and the TD, more preferably 5.0 N / mm or more in terms of the good running property of the film Is more preferable. The tear propagation resistance is a value measured using a light load tester similar to the Elmendorf tear method. The measured value indicates the resistance when the film is torn, indicating that it is difficult to tear in consideration of the entire thickness direction. The larger the value, the more difficult the film is tearable.

The dimensional change ratio of the polyimide film of the present invention is preferably less than 0.01%, more preferably 0.008% or less.

In producing the polyimide film of the present invention, first, the polyamic acid solution is obtained by polymerizing the aromatic diamine component and the acid anhydride component in an organic solvent.

The polyimide film of the present invention contains paraphenylenediamine as the aromatic diamine component. And aromatic diamine components other than paraphenylenediamine. Specific examples of the aromatic diamine component other than paraphenylenediamine include metaphenylenediamine, benzidine, para-xylylenediamine, 4,4'-diamino Diphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl methane, 4,4'-diaminodiphenyl sulfone, 3,3'-dimethyl-4,4'-dia 1,3-dimethoxybenzidine, 1,4-bis (3-methyl-5-aminophenyl) benzene, and amide-forming derivatives thereof. These may be used singly or in combination of two or more kinds. As the aromatic diamine component, a combination of paraphenylenediamine and 4,4'-diaminodiphenyl ether and / or 3,4'-diaminodiphenyl ether is preferable. Among them, the amount of the diamine component of paraphenylenediamine, 3, 4'-diaminodiphenyl ether, which has an effect of increasing the tensile modulus of the film, is adjusted, and the tensile modulus of the obtained polyimide film is set to 6.0 GPa or more , And conveyability 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'-benzophenonetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 2,2-bis (3,4-dicarboxyphenyl) ether, pyridine-2,3,5,6-tetra And aromatic tetracarboxylic anhydride components such as carboxylic acid and amide-forming derivatives thereof, and pyromellitic dianhydride and 3,3 ', 4,4'-diphenyltetracarboxylic dianhydride are preferable. These may be used singly or in combination of two or more kinds.

Of these, particularly preferred examples of the combination of the aromatic diamine component and the acid anhydride component include a compound 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 with at least one acid anhydride component selected from the group consisting of pyromellitic acid dianhydride and 3,3 ', 4,4'-diphenyltetracarboxylic dianhydride .

The compounding ratio (molar ratio) of the paraphenylenediamine in the aromatic diamine component is preferably in the range of 0.1 to 5 parts by weight, , Usually at least 31 mol%, preferably at least 33 mol%, more preferably at least 35 mol%.

The compounding ratio (molar ratio) in the above-mentioned acid anhydride component is not particularly limited as long as it does not hinder the effect of the present invention. For example, 3,3 ', 4,4'-diphenyltetracarboxylic dianhydride , The content of 3,3 ', 4,4'-diphenyltetracarboxylic dianhydride is preferably at least 15 mol%, more preferably at least 20 mol%, and most preferably at least 25 mol%, based on the total amount of the acid anhydride component. Mol% or more is more preferable.

When the polyimide film of the present invention is made of a polyamic acid comprising these aromatic diamine component and an acid anhydride component, the coefficient of thermal expansion of the polyimide film is set to be in the above range in both the machine direction (MD) and the width direction (TD) It is preferable because it can be easily adjusted.

In the present invention, specific examples of the organic solvent used for forming the polyamic acid solution include sulfoxide type solvents such as dimethylsulfoxide and diethylsulfoxide, N, N-dimethylformamide, N, N-dimethylformamide, N-dimethylacetamide, and N, N-diethylacetamide; organic solvents such as N-methyl-2-pyrrolidone, N-vinyl- Phenol, o-, m-, or a phenol-based solvent such as p-cresol, xylenol, halogenated phenol, catechol or the like, or hexamethylphosphoramide,? -Butyrolactone And non-protonic polar solvents such as lactone. It is preferable to use them as a single or a mixture of two or more kinds, but it is also possible to use aromatic hydrocarbons such as xylene and toluene.

The polymerization may be carried out by any known method. For example,

(1) First, the entire aromatic diamine component is added to a solvent, and then the acid anhydride component is added to the total amount of the aromatic diamine component (equivalent) to effect polymerization.

(2) First, the entire amount of the acid anhydride component is put into a solvent, and then the aromatic diamine component is added so as to be equivalent to the acid anhydride component, and polymerization is carried out.

(3) One aromatic diamine component (a1) is placed in a solvent, and the mixture is stirred for a time required for the reaction to be 95 to 105 mol% of one acid anhydride component (b1) relative to the reaction component. The 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.

(4) One of the acid anhydride components (b1) is put into the solvent, and the mixture is stirred for a time required for the reaction so that one aromatic diamine component (a1) accounts for 95 to 105 mol% Adding the acid anhydride component (b2), and then adding another aromatic diamine component (a2) so that the total aromatic diamine component and the total acid anhydride component are substantially equivalent.

(5) The polyamic acid solution (A) is adjusted by reacting one of the aromatic diamine component and the acid anhydride component in the solvent so that one of the aromatic diamine component and the acid anhydride component is excessive, and the other one of the aromatic diamine component and the acid anhydride component And the polyamic acid solution (B) is adjusted by reacting the excess amount. A method in which each of the polyamic acid solutions (A) and (B) thus obtained is mixed to complete the polymerization. When the aromatic diamine component is excessive in the preparation of the polyamic acid solution (A), the acid anhydride component is excessively used in the polyamic acid solution (B), and when the acid anhydride component is excessive in the polyamic acid solution (A) In the mixed acid solution (B), the aromatic diamine component is excessively mixed, and the polyamic acid solutions (A) and (B) are mixed so that the total aromatic diamine component and the total acid anhydride component used in these reactions are adjusted to be approximately equivalent. The polymerization method is not limited to these, and other known methods may be used.

The polyamic acid solution thus obtained usually contains 5 to 40% by weight of solids, preferably 10 to 30% by weight of solids. The viscosity is a value measured by a Brookfield viscometer, usually 10 to 2000 Pa · s, and preferably 100 to 1000 Pa · s, for stable feeding. In addition, the polyamic acid in the organic solvent solution may be partially imidized.

Next, a method for producing a polyimide film will be described. Examples of the method for forming the polyimide film include a method of casting a polyamic acid solution into a film form to thermally depolarize and desolvate the polyimide film to obtain a polyimide film and a method in which a polyamic acid solution is mixed with a cyclization catalyst and a dehydrating agent, A gel film is prepared, and a polyimide film is obtained by heating and removing the solvent therefrom. However, the latter is preferable because the coefficient of thermal expansion of the polyimide film to be obtained can be suppressed to a low level.

In the method of chemically de-catalyzing, the polyamic acid solution is first prepared. The polyamic acid solution may contain chemically inert organic fillers such as titanium oxide, silica, calcium carbonate, calcium phosphate, calcium hydrogen phosphate and polyimide filler, and inorganic filler, if necessary. The content of the filler is not particularly limited as long as it does not hinder the effect of the present invention.

The polyamic acid solution used herein may be a preliminarily polymerized polyamic acid solution or may be a solution obtained by sequentially polymerizing filler particles.

The polyamic acid solution may contain a cyclization catalyst (imidization catalyst), a dehydrating agent and a gelling retarder.

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 amines such as isoquinoline, pyridine, Tertiary amines, and the like, but heterocyclic tertiary amines are preferred. These may be used singly or in combination of two or more kinds.

Specific examples of the dehydrating agent used in the present invention include an aliphatic carboxylic anhydride such as acetic anhydride, propionic anhydride, butyric anhydride and the like, and an aromatic carboxylic anhydride such as benzoic anhydride, but acetic anhydride and / or benzoic anhydride are preferable . The gelling retarder is not particularly limited, and acetylacetone and the like can be used.

As a method for producing a polyimide film from a polyamic acid solution, a polyamic acid solution containing the above-mentioned cyclization catalyst and the dehydrating agent is formed into a film by molding on a support from a slit-type mouthpiece and imidized on a support To a gel film having a self-supporting property, followed by peeling from the support, heat drying / imidization, and heat treatment.

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

The gel film is heated to a temperature of usually 30 to 200 ° C, preferably 40 to 150 ° C due to hydrothermal heat from a support and / or hydrothermal source such as hot air or an electric heater to effect a ring-closing reaction, The volatile matter such as a solvent is dried to have self-supporting property and peeled off from the support.

The gel film peeled off from the support is not particularly limited, but is preferably stretched in the carrying direction while regulating the traveling speed by a rotary roll. The stretching in the carrying direction is carried out at a temperature of 140 캜 or lower. The draw ratio MDX thereof is usually 1.05 to 1.9 times, preferably 1.1 to 1.6 times, more preferably 1.1 to 1.5 times. The gel film stretched in the carrying direction is introduced into a tenter device, is gripped at both ends in the width direction by a tenter clip, and is stretched by a width method while traveling together with the tenter clip. The stretching in the width direction is carried out at a temperature of 200 DEG C or higher. The stretching magnification (TDX) is usually 1.1 to 1.5 times, preferably 1.2 to 1.45 times the MDX. By applying this stretching magnification ratio combination to the gel film obtained by the above blending, an isotropic film can be obtained and a film having the effect of the present invention can be obtained.

The film dried in the above-mentioned drying zone is heated for 15 seconds to 10 minutes by hot air or an infrared heater. Then, heat treatment is performed at a temperature of 250 to 500 占 폚 for 15 seconds to 20 minutes by hot air and / or an electric heater.

The thickness of the polyimide film is adjusted by adjusting the running speed. However, the thickness of the polyimide film is preferably 3 to 250 占 퐉, more preferably 5 to 150 占 퐉 in order to prevent deterioration of film formability.

The polyimide film thus obtained is preferably subjected to an annealing treatment. As a result, thermal relaxation of the film occurs and the heat shrinkage rate can be suppressed to be small. The temperature of the annealing treatment is not particularly limited, but is preferably 200 ° C to 500 ° C, more preferably 200 ° C to 370 ° C, and particularly preferably 210 ° C to 350 ° C. Thermal shrinkage from the annealing treatment can suppress the heat shrinkage rate at 200 占 폚 within the above-mentioned range, which is preferable because the dimensional accuracy becomes higher. More specifically, it is preferable that the film is run under a storage force in a furnace heated to the above-mentioned temperature range to perform an annealing treatment. It is preferable that the processing time is 30 seconds to 5 minutes since the time required for the film to stay in the furnace is controlled by changing the running speed. If it is shorter than this, heat is not sufficiently transferred to the film, and if it is longer, the film tends to be overheated and the planarity is deteriorated. The film tension at the time of running is preferably 10 to 50 N / m, more preferably 20 to 30 N / m. If the tension is lower than this range, the running property of the film deteriorates, and if the tension is high, the heat shrinkage rate in the running direction of the obtained film becomes high.

In order to impart adhesiveness to the obtained polyimide film, the surface of the film may be subjected to a physical treatment such as an electric treatment or a blast treatment such as a corona treatment or a plasma treatment, and these physical treatments may be carried out according to a conventional method . The pressure of the atmosphere in the case of performing the plasma treatment is not particularly limited, but is usually in the range of 13.3 to 1330 kPa, preferably in the range of 13.3 to 133 kPa (100 to 1000 Torr), more preferably in the range of 80 to 120 kPa ) Is more preferable.

The atmosphere in which the plasma treatment is carried out includes at least 20 mol% of an inert gas, preferably 50 mol% or more, more preferably 80 mol% or more, and 90 mol% or more of an inert gas Most preferred. The inert gas may, include He, Ar, Kr, Xe, Ne, Rn, N ₂ and their two or more mixture. A particularly preferred inert gas is Ar. The inert gas may be mixed with oxygen, air, carbon monoxide, carbon dioxide, carbon tetrachloride, chloroform, hydrogen, ammonia, tetrafluoromethane (carbon tetrafluoride), trichlorofluoroethane, trifluoromethane . A preferred combination of gas mixtures used as the atmosphere for the plasma treatment of the present invention is a combination of argon / oxygen, argon / ammonia, argon / helium / oxygen, argon / carbon dioxide, argon / nitrogen / carbon dioxide, argon / helium / nitrogen, / Nitrogen / carbon dioxide, argon / helium, helium / air, argon / helium / monosilane, argon / helium / disilane and the like.

The treatment power density when plasma treatment is performed is not particularly limited, but is preferably 200 W · min / m 2 or more, more preferably 500 W · min / m 2 or more, and most preferably 1000 W · min / . The plasma irradiation time for plasma treatment 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 involving deterioration of the film. The gas type, the gas pressure, and the processing density of the plasma treatment are not limited to the above-described conditions, and may be performed in the atmosphere.

Since the polyimide film obtained in this way is an isotropic polyimide film having a small dimensional change of the film and a small difference in thermal expansion coefficient between MD and TD, the polyimide film can be suitably used for semiconductor package applications, semiconductor manufacturing process applications, display applications, And can be suitably used for applications requiring dimensional stability, such as substrates for pitch circuits.

The present invention also includes a copper-clad laminate in which the above-described polyimide film of the present invention is used. The method for producing the copper-clad laminate of the present invention is not particularly limited, and can be obtained by conventionally known production methods. The copper-clad laminate of the present invention can be obtained, for example, by using the polyimide film of the present invention as a base and forming a copper layer having a thickness of 1 to 10 탆 according to a conventional method.

The present invention also includes a glass / polyimide laminate in which the above-mentioned polyimide film of the present invention is used. The method for producing the laminate is not particularly limited. For example, the glass and the polyimide film of the present invention may be laminated in accordance with a conventional method. Further, between the glass and the polyimide film of the present invention, An adhesive or the like may be interposed between them in accordance with a conventional method.

When the polyimide film of the present invention is used in a display, for example, by laminating a display on the polyimide film side of the glass / polyimide laminate of the present invention and removing the glass portion, A display using a polyimide film can be obtained.

The present invention includes various combinations of the above configurations within the technical scope of the present invention as long as the effects of the present invention are effective.

Example

The present invention will now be described more specifically with reference to Examples. However, it should be understood that the present invention is not limited to these Examples, and many variations are possible within the technical scope of the present invention. Lt; / RTI &gt;

In the examples, PPD represents paraphenylenediamine, 4,4'-ODA represents 4,4'-diaminodiphenyl ether, PMDA represents pyromellitic acid dianhydride, BPDA represents 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride and DMAc represents N, N-dimethylacetamide, respectively.

Each characteristic in the examples was evaluated by the following method.

(1) Coefficient of thermal expansion

Measurement was conducted under the conditions of a measurement temperature range of 50 to 200 占 폚 and a temperature increase rate of 10 占 폚 / min using a machine TMA-50 (trade name, manufactured by Shimadzu Corporation).

(2) Heat shrinkage

The film dimensions (L1) after being left in a room adjusted to 25 ° C and 60% RH for 2 days were measured. Subsequently, the film was heated at 200 ° C for 60 minutes and then again in a room adjusted at 25 ° C and 60% RH for 2 days After leaving, the film dimension (L2) was measured and evaluated by the following formula.

Heat shrinkage percentage (%) = - (L2-L1) / L1} x 100

(3) Tensile modulus

Instrument: Measured under RTM-250 (trade name, manufactured by A & D) under the conditions of a tensile rate of 100 mm / min.

(4) Dimensional change rate

A copper layer having a thickness of 10 占 퐉 was formed on the film by electroplating with a copper sulfate plating solution and patterned with a 30 占 퐉 pitch (line spacing 15 占 퐉) to wire the copper to TD. .) Electroless plating The tin plating solution LT34 was tin plated, and the dimensions of the TD were measured (L3). This was placed on a bonding stage at 250 占 폚, and dimensions of TD after bonding with a chip by a bonding tool of 400 占 폚 were measured (L4). The dimensional change ratio was obtained by the following formula.

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

(5) Tear propagation resistance

A 63.5 mm 50 mm test piece was prepared from the polyimide film, and a 12.7 mm cut sheath was placed on the test piece. The tensile strength was measured in accordance with JIS P8116 using a light load tester.

(6) Absorption rate

The film was immersed in distilled water for 48 hours and then taken out, the surface water was quickly wiped off, and the sample was cut to a size of about 5 mm x 15 mm. The film was passed through Seo Electric Co., Ltd. and measured by a thermogravimetric analyzer TG-50 manufactured by Shimazu Corporation. The temperature raising rate was raised to 200 占 폚 at 10 占 폚 / min, and the absorptivity was calculated from the change in weight by using the following formula.

Absorption rate (%) = {(weight before heating) - (weight after heating)} / (weight after heating) x 100

[Example 1]

To a 500 ml separable flask was added 238.6 g of DMAc, and 5.68 g (0.053 mole) of PPD, 19.52 g (0.098 mole) of 4,4'-ODA, 11.03 g (0.038 mole) of BPDA and 24.54 g ), And the mixture was reacted for 1 hour at room temperature and normal pressure, and stirred until homogeneous to obtain a polyamic acid solution.

15 g was taken out from the polyamic acid solution, cooled to minus 5 캜, and then mixed with 1.9 g of acetic anhydride and 1.8 g of? -Picoline to obtain a mixed solution.

The thus obtained mixed solution was poured into a rotating drum at 90 DEG C for 30 seconds, and the obtained gel film was stretched 1.23 times in the running direction while heating at 100 DEG C for 5 minutes. Subsequently, both ends in the width direction were held and stretched 1.4 times in the width direction while heating at 270 DEG C for 2 minutes, and then heated at 380 DEG C for 5 minutes to obtain a polyimide film having a thickness of 38 mu m. The polyimide film was subjected to annealing for 1 minute under a tension of 20 N / m in a furnace set at 220 占 폚, and then the properties were evaluated as shown in Table 1.

[Examples 2 to 3]

The aromatic diamine component and the aromatic tetracarboxylic acid anhydride component were respectively subjected to a polyamic acid solution in the ratios shown in Table 1 in the same procedure as in Example 1 and then subjected to stretching magnifications in the transverse direction and the longitudinal direction as shown in Table 1, The polyimide film obtained by the same operation as in Example 1 was evaluated for each characteristic, and the results are shown in Table 1.

Example One 2 3 Percentage of each ingredient
(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 Stretching magnification MDX 1.23 1.22 1.18 TDX 1.40 1.44 1.39 Coefficient of thermal expansion
(ppm / DEG C) MD 6.3 4.1 4.5 TD 5.3 2.9 3.8 Heat Shrinkage Rate
(%) 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 ratio (%) 0.011 0.007 0.009 Absorption Rate (%) 2.2 2.4 2.4

(In the table, the molar ratio represents mol% in the total aromatic diamine component and mol% in the total acid anhydride component).

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

Since the polyimide film of the present invention is an isotropic film having a small dimensional change and a small difference in thermal expansion coefficient between MD and TD, the polyimide film can be suitably used for a semiconductor package application, a semiconductor manufacturing process application, a display application, a solar cell substrate, Can be suitably used for applications requiring dimensional stability.

Claims (11)

A polyimide film obtained by using an aromatic diamine component containing paraphenylenediamine and an acid anhydride component was measured using a TMA-50 manufactured by Shimazu Corporation under the conditions of a measurement temperature range of 50 to 200 DEG C and a temperature raising rate of 10 DEG C / the coefficient of thermal expansion of the film measured under the condition of a machine conveying direction (MD) α _MD and the width direction is more than 0 ppm / ℃ both the coefficient of thermal expansion α of the _TD (TD) is in the range of less than 7.0 ppm / ℃, │α _MD -? _TD ? &Lt; 3. A polyimide film obtained by using an aromatic diamine component containing paraphenylenediamine and an acid anhydride component was measured using a TMA-50 manufactured by Shimazu Corporation under the conditions of a measurement temperature range of 50 to 200 DEG C and a temperature raising rate of 10 DEG C / the coefficient of thermal expansion of the film measured under the condition of a machine conveying direction (MD) α _MD and the width direction is more than 0 ppm / ℃ both the coefficient of thermal expansion α of the _TD (TD) is in the range of less than 7.0 ppm / ℃, │α _MD -? _TD ? &Lt; 2. The polyimide film according to claim 1 or 2, wherein the heat shrinkage ratio of MD and TD at 200 ° C of the film is not more than 0.05%. The polyimide film according to any one of claims 1 to 3, wherein the heat shrinkage ratio at both the MD and the TD of the film at 200 캜 is 0.03% or less. The polyimide film according to any one of claims 1 to 4, wherein the tensile modulus of the film is 6.0 GPa or more. The polyimide film according to any one of claims 1 to 5, wherein the film has a water absorption of 3.0% or less. The polyimide film according to any one of claims 1 to 6, wherein the paraphenylenediamine is at least 31 mol% based on the total amount of the aromatic diamine component. The aromatic diamine component according to any one of claims 1 to 7, wherein the aromatic diamine component further comprises at least one member selected from the group consisting of 4,4'-diaminodiphenyl ether and 3,4'-diaminodiphenyl ether &Lt; / RTI &gt; The acid anhydride component is one or more selected from the group consisting of pyromellitic acid dianhydride and 3,3'- 4,4'-diphenyltetracarboxylic dianhydride. Lt; / RTI &gt; A copper-clad laminate characterized by using the polyimide film according to any one of claims 1 to 9. A glass / polyimide laminate characterized by using the polyimide film according to any one of claims 1 to 10.