TW201605976A - Polyimide film - Google Patents

Abstract

The present invention provides a polyimide film, in which the size change of the film is small, and the difference between thermal expansion coefficients in MD and in TD is so small that they are isotropic, and the film is preferably used for applications requiring a film of stable size, such as semiconductor packaging, semiconductor processing, displays, solar cell substrates, and fine-pitch circuit boards. The polyimide film is characterized by using p-phenylenediamine-containing aromatic diamine and acid anhydride to produce the polyimide film, and when the polyimide film is tested by using a TMA-50 manufactured by the Shimadzu Corporation, at temperatures in the range of 50-200 DEG C and temperature rise rate of 10 DEG C/min, the thermal expansion coefficient in machine direction (MD) [alpha]MD and the thermal expansion coefficient in transverse direction (TD) [alpha]TD are both more than 0ppm/ DEG C and less than 7.0ppm/ DEG C, and satisfy the relationship: |[alpha]MD-[alpha]TD| < 3.

Description

Polyimine film

The present invention relates to a polyimide film which is excellent in dimensional stability and is preferably used for semiconductor package applications, semiconductor process applications, display applications, solar cell substrates, and micro pitch circuit substrates, and the like, which requires dimensional stability.

Along with the high-fibrillation of a flexible printed circuit board (FPC) or a semiconductor package, there is an increasing demand for such a polyimide film, and for example, a dimensional change caused by bonding with a metal or The curl is reduced, the handleability is high, etc., as the physical properties of the polyimide film, it is required to have the same thermal expansion coefficient as the metal, have a high elastic modulus, and the film has less dimensional change caused by water absorption, and the industry continuously develops and satisfies These polyimine films.

For example, an example of a polyimine film using p-phenylenediamine for increasing the modulus of elasticity is known (Patent Documents 1, 2, and 3). Further, an example of a polyimine film in which p-phenylenediamine is added and biphenyltetracarboxylic dianhydride is added in order to maintain high elasticity and reduce dimensional change due to water absorption is known (Patent Documents 4 and 5).

Further, it is known that the thermal expansion coefficient of the mechanical transport direction (hereinafter also referred to as MD (machine direction)) of the film is set to be larger than the width direction of the film in order to control the dimensional change in the step of bonding to the metal (hereinafter also referred to as TD (transverse direction) is an example of a polyimide film having a small thermal expansion coefficient and an anisotropy. In the conventional FPC process, a lamination method in which a roll-to-roll is heated to bond with a metal is used. The purpose of this method is to offset the MD applied tension of the film in this step to cause elongation, and on the other hand, TD production The phenomenon of shrinkage (Patent Document 6).

As a recent use of the polyimide film, the advantages of weight reduction and flexibility include a semiconductor package, a semiconductor process, a base film of a display such as an electronic paper, and a use of a solar cell substrate. Conventionally, polyimide films have been used for circuit substrates, and their thermal expansion coefficients are often adjusted based on the thermal expansion coefficient of copper forming wiring. However, these recent uses mostly use cerium oxide or glass having a lower coefficient of thermal expansion than copper, and the prior polyimine film has insufficient dimensional stability or a difference in thermal expansion coefficient between MD and TD. A situation in which warpage occurs. Further, in the case of the circuit board use of the prior art, a micro pitch is also required. In this case, the dimensional stability of the prior polyimide film is insufficient.

[Advanced technical literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. SHO 60-210629

[Patent Document 2] Japanese Patent Laid-Open No. 64-16832

[Patent Document 3] Japanese Patent Laid-Open No. Hei 1-131241

[Patent Document 4] Japanese Patent Laid-Open No. 59-164328

[Patent Document 5] Japanese Patent Laid-Open No. 61-111359

[Patent Document 6] Japanese Patent Laid-Open No. Hei 4-25434

The present invention has been made in order to solve the problems of the prior art described above as a subject, and an object thereof is to obtain a reduction in dimensional change of a film, and a difference in thermal expansion coefficient between MD and TD is small and isotropic, and is preferably used for a semiconductor. Polyimine film for applications requiring dimensional stability, such as packaging applications, semiconductor process applications, display applications, solar cell substrates, and micro pitch circuit substrates.

The inventors of the present invention have made intensive studies on the above-mentioned problems, and as a result, have found that the following polyimide film is an isotropic film having a small dimensional change of the film and a small difference in thermal expansion coefficient between MD and TD. The amine film is obtained by using an aromatic diamine component and an acid anhydride component containing p-phenylenediamine, and using TMA-50 manufactured by Shimadzu Corporation at a measurement temperature range of 50 to 200 ° C and a temperature increase rate of 10 both the coefficient α _TD thermal expansion measured at ℃ / minute conditions for mechanical membrane of the conveying direction (MD) of the thermal expansion coefficient α _MD and the width direction (TD) of the average at 0ppm / ℃ or more and less than the 7.0ppm / range ℃ of And satisfy the relationship of |α _MD -α _TD |<3.

The inventors of the present invention have obtained unexpected new findings as described above in addition to the above, and have completed the present invention by intensive research.

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

[1] A polyimine film obtained by using an aromatic diamine component and an acid anhydride component containing p-phenylenediamine, and using TMA-50 manufactured by Shimadzu Corporation at a measurement temperature range of 50 both thermomechanical film of measurement at 10 ℃ / minute conditions ~ 200 ℃, the heating rate of the conveyance direction (MD) of the thermal expansion coefficient α _MD and the width direction (TD) of the expansion coefficient α _TD are and not at 0ppm / ℃ above It is in the range of 7.0 ppm/°C and satisfies the relationship of |α _MD -α _TD |<3.

[2] A polyimine film obtained by using an aromatic diamine component and an acid anhydride component containing p-phenylenediamine, and using TMA-50 manufactured by Shimadzu Corporation at a measurement temperature range of 50 both thermomechanical film of measurement at 10 ℃ / minute conditions ~ 200 ℃, the heating rate of the conveyance direction (MD) of the thermal expansion coefficient α _MD and the width direction (TD) of the expansion coefficient α _TD are and not at 0ppm / ℃ above It is in the range of 7.0 ppm/°C and satisfies the relationship of |α _MD -α _TD |<2.

[3] The polyimine film described in the above [1] or [2], wherein the film has a heating shrinkage ratio of MD and TD of 200 ° C of 0.05% or less.

[4] The polyimide film according to any one of the above [1] to [3] wherein the MD of the film is The heating shrinkage rate of TD at 200 ° C is 0.03% or less.

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

[6] The polyimine film according to any one of [1] to [5] wherein the water absorption of the film is 3.0% or less.

[7] The polyimine film according to any one of [1] to [6] wherein the total amount of p-phenylenediamine relative to the aromatic diamine component is at least 31 mol%.

[8] The polyimine film according to any one of the above [1] to [7] further comprising a member selected from the group consisting of 4,4'-diaminodiphenyl ether and 3,4'-diamino group One or more of the group consisting of phenyl ethers is an aromatic diamine component.

[9] The polyimine film according to any one of the above [1] to [8] wherein the acid anhydride component is selected from the group consisting of pyromellitic dianhydride and 3,3'-4,4'-biphenyl One or more of the group consisting of carboxylic acid dianhydrides.

[10] A copper-clad laminate, which is characterized in that the polyimide film according to any one of the above [1] to [9] is used.

[11] A glass/polyimine laminate, which is characterized in that the polyimide film according to any one of the above [1] to [10] is used.

Since the polyimide film of the present invention has excellent dimensional stability, it can be preferably used for semiconductor package applications, semiconductor process applications, display applications, solar cell substrates, and micro pitch circuit substrates, and the like for dimensional stability. .

Moreover, since the polyimide film of the present invention has an isotropic film having a small difference in thermal expansion coefficient between MD and TD, it can be used for semiconductor packaging applications, semiconductor process applications, display applications, solar cell substrates, and fine pitches. Warpage occurs in applications such as circuit boards.

The polyimine film of the present invention is obtained by using an aromatic diamine component and an acid anhydride component containing p-phenylenediamine, and using TMA-50 manufactured by Shimadzu Corporation at a temperature range of 50 to 200. both the coefficient α _TD thermal expansion ℃, the heating rate of the mechanical film's measured at 10 ℃ / minute conditions transportation direction (MD) of the thermal expansion coefficient α _MD and the width direction (TD) of the average at 0ppm / ℃ or more and less than 7.0 Within the range of ppm/°C, and satisfying the relationship of |α _MD -α _TD |<3.

The thermal expansion coefficient α _MD of the mechanical transport direction (MD) of the polyimide film of the present invention and the thermal expansion coefficient α _{TD of the} width direction (TD) are each usually in the range of 0 ppm/° C. or more and less than 7.0 ppm/° C. It is in the range of 1.0 ppm/° C. or more and less than 7.0 ppm/° C., more preferably in the range of 2.0 ppm/° C. or more and 6.5 ppm/° C. or less, and further preferably in the range of 2.0 ppm/° C. or more and 6.0 ppm/° C. or less. It is particularly preferably in the range of 2.0 ppm/° C. or more and 5.5 ppm/° C. or less.

If it is less than the above range, the strength (for example, tensile elongation, etc.) is inferior, and the obtained film is easily broken, which is not preferable. By setting α _MD and α _TD within the above range and combining with the respective constituent elements of the present invention, regardless of the subsequent object of the polyimide film (for example, the film may be made of a metal such as copper) Since it has excellent dimensional stability, it can be preferably used for semiconductor package applications, semiconductor process applications, display applications, solar cell substrates, and micro pitch circuit substrates, etc., which require dimensional stability.

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

The above α _MD and the above α _{TD of the} polyimine film of the present invention generally satisfy the relationship of |α _MD -α _TD |<3, preferably satisfying the relationship of |α _MD -α _TD |<2, and more preferably satisfying |α _MD -α _TD |<1.5 relationship, and further preferably satisfies the relationship of |α _MD -α _TD |<1.0.

The 200 ° C heat shrinkage ratio of the polyimide film of the present invention is preferably MD and TD. 0.05% or less, more preferably 0.03% or less. Further, in the present invention, the 200 ° C heating shrinkage ratio is a value calculated by the method disclosed in the examples described later.

The polyimine film of the present invention preferably has a tensile modulus of 6.0 GPa or more, more preferably 6.5 GPa or more, still more preferably 7.0 GPa or more. Further, it is preferable that both MD and TD are 6.0 GPa or more, more preferably both MD and TD are 6.5 GPa or more, and further preferably both MD and TD are 7.0 GPa or more.

The water absorption of the polyimine 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, and the tear propagation resistance is preferably 3.0 N/mm or more in terms of good migration property of the film. Good is 5.0N/mm or more. The tear propagation resistance was measured using a light weight weight tear tester similar to the Elmendorf tear method. Since the measured value shows the resistance at the time of film breakage, it is shown that the tearing difficulty in consideration of the entire thickness direction is large, and the larger the film is, the more difficult the film is to be broken, and the transition property is excellent.

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

In the production of the polyimine film of the present invention, a polyaminic acid solution is first obtained by polymerizing an aromatic diamine component and an acid anhydride component in an organic solvent.

The polyimine film of the present invention contains p-phenylenediamine as the above aromatic diamine component. Further, examples of the aromatic diamine component other than p-phenylenediamine may be contained, and specific examples of the aromatic diamine component other than p-phenylenediamine include m-phenylenediamine, benzidine, and p-xylylenediamine. 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylanthracene, 3 , 3'-dimethyl-4,4'-diaminodiphenylmethane, 1,5-diaminonaphthalene, 3,3'-dimethoxybenzidine, 1,4-bis(3 methyl -5 aminophenyl)benzene and such guanamine forming derivatives. These may be used alone or in combination of two or more. As the aromatic diamine component, p-phenylenediamine and 4,4'-diaminodiphenyl ether and/or 3,4'-di are preferred. A combination of amino diphenyl ethers. Adjusting the amount of the diamine component of p-phenylenediamine and 3,4'-diaminodiphenyl ether which has the effect of increasing the tensile modulus of the film, and the tensile elasticity of the obtained polyimide film It is preferable that the modulus is set to 6.0 GPa or more because the transportability is also good.

Specific examples of the acid anhydride component include pyromellitic acid, 3,3', 4,4'-biphenyltetracarboxylic acid, 2,3',3,4'-biphenyltetracarboxylic acid, and 3, 3',4,4'-benzophenonetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 2,2-bis(3,4-dicarboxyphenyl)ether, pyridine-2, An aromatic tetracarboxylic anhydride component such as 3,5,6-tetracarboxylic acid and such a guanamine-forming derivative, preferably pyromellitic dianhydride, 3,3',4,4'-biphenyltetra Carboxylic dianhydride. These may be used alone or in combination of two or more.

Among them, a combination of a particularly preferred aromatic diamine component and an acid anhydride component is selected from the group consisting of p-phenylenediamine, 4,4'-diaminodiphenyl ether, and 3,4'-diaminodiphenyl ether. One or more kinds of the aromatic diamine component in the group and one or more selected from the group consisting of pyromellitic dianhydride and 3,3',4,4'-biphenyltetracarboxylic dianhydride A combination of anhydride components.

The ratio of the p-phenylenediamine in the aromatic diamine component (mol ratio) to the total amount of the aromatic diamine component is obtained in terms of obtaining the thermal expansion coefficient of the above range and imparting appropriate strength to the film to prevent poor mobility. The amount is usually at least 31 mol% or more, preferably 33 mol% or more, more preferably 35 mol% or more.

The blending ratio (mol ratio) in the acid anhydride component is not particularly limited as long as the effect of the present invention is not impaired, for example, in the case of containing 3,3',4,4'-biphenyltetracarboxylic dianhydride. The content of the 3,3',4,4'-biphenyltetracarboxylic dianhydride is preferably 15 mol% or more, more preferably 20 mol% or more, and further preferably 20 mol% or more, based on the total amount of the acid anhydride component. 25% or more.

When the polyimine film of the present invention is produced from polyamic acid containing the aromatic diamine component and the acid anhydride component, the thermal expansion coefficient of the polyimide film can be easily transferred to the mechanical transport direction of the film. Both (MD) and width direction (TD) are preferably adjusted within the above range.

Further, in the present invention, as an organic solvent for forming a polyaminic acid solution Examples of the examples include an anthraquinone solvent such as dimethyl hydrazine or diethyl hydrazine, and a carbamide solvent such as N,N-dimethylformamide or N,N-diethylformamide. , N,N-dimethylacetamide, N,N-diethylacetamide, ethamamine solvent, N-methyl-2-pyrrolidone, N-vinyl-2-pyrrolidone Pyrrolidone-based solvent, phenol, o-cresol, m-cresol, or phenolic solvent such as p-cresol, xylenol, halogenated phenol, catechol or hexamethylphosphonium, γ-butyrolactone The aprotic polar solvent is preferably used singly or as a mixture of two or more kinds, and an aromatic hydrocarbon such as xylene or toluene may also be used.

The polymerization method can be carried out by any known method, for example:

(1) First, a total amount of the aromatic diamine component is added to a solvent, and thereafter, an acid anhydride component is added in an amount equivalent to the total amount of the aromatic diamine component (molar) to carry out polymerization.

(2) First, the total amount of the acid anhydride component is added to the solvent, and thereafter, the aromatic diamine component is added in an amount equivalent to the acid anhydride component, and polymerization is carried out.

(3) After adding the aromatic diamine component (a1) to the solvent, the monoacid anhydride component (b1) is mixed at a ratio of 95 to 105 mol% with respect to the reaction component, and then the other is added. The aromatic diamine component (a2) is then added to the other anhydride component (b2) in such a manner that the entire aromatic diamine component and the entire acid anhydride component are almost equivalent to each other and polymerized.

(4) After adding the monoanhydride component (b1) to the solvent, the aromatic diamine component (a1) is mixed at a ratio of 95 to 105 mol% with respect to the reaction component, and then the other is added. The monoanhydride component (b2) is a method in which another aromatic diamine component (a2) is added in such a manner that the entire aromatic diamine component and the entire acid anhydride component are almost equivalent.

(5) reacting an aromatic diamine component and an acid anhydride component in an excess amount in a solvent, adjusting the polyaminic acid solution (A), and allowing another aromatic diamine component and an acid anhydride in another solvent. The component is reacted in an excess of either side to adjust the polyaminic acid solution. (B). The polymerization method is carried out by mixing each of the polyamic acid solutions (A) and (B) thus obtained. In this case, when the polydiamine acid solution (A) is adjusted to have an excess amount of the aromatic diamine component, the acid anhydride component is excessively present in the polyaminic acid solution (B), and further, in the polyaminic acid solution (A). When the amount of the acid anhydride component is excessive, the aromatic diamine component is excessively mixed in the polyaminic acid solution (B), and the polyaminic acid solution (A) and (B) are mixed for use in all the aromatic reactions of the reaction. The group diamine component and all the acid anhydride components are adjusted in an almost equivalent manner. Further, 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 a solid content component, preferably 10 to 30% by weight of a solid content component. Further, the viscosity is usually 10 to 2000 Pa measured by a Brookfield viscometer. s, in order to stabilize the liquid supply, preferably 100~1000Pa. s. Further, the polyamine acid in the organic solvent solution may also be partially imidized.

Next, a method of producing a polyimide film will be described. As a method for producing a polyimide film, a method in which a polyaminic acid solution is cast into a film form, and a thermal de-cyclization solvent is removed to obtain a polyimide film; and a polyamid acid solution is used. Mixing a cyclized catalyst and a dehydrating agent to chemically de-cyclize, preparing a gel film, and heating and desolvating the solvent to obtain a polyimide film; the latter can obtain the obtained polyimide film The coefficient of thermal expansion is preferably suppressed, so that it is preferred.

In the method of chemical decyclization, the above polyamic acid solution is first prepared. Further, the polyamic acid solution may contain a chemically inert organic filler or an inorganic filler such as titanium oxide, cerium oxide, calcium carbonate, calcium phosphate, calcium hydrogen phosphate or a polyimine filler, as needed. The content of the filler is not particularly limited as long as it does not impair the effects of the present invention.

The polyaminic acid solution used herein may be a prepolymerized polylysine solution, or may be sequentially polymerized when the filler particles are contained.

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

Specific examples of the cyclized catalyst used in the present invention include trimethylamine. An aliphatic tertiary amine such as an ethylene diamine, an aromatic tertiary amine such as dimethylaniline, or a heterocyclic tertiary amine such as isoquinoline, pyridine or β-methylpyridine, preferably a heterocyclic ring. Tertiary amine. These may be used alone or in combination of two or more.

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, and preferably acetic anhydride and/or benzoic anhydride. . The gelation retarder is not particularly limited, and acetonitrile or the like can be used.

As a method for producing a polyimide film from a polyaminic acid solution, a method of casting a polyamic acid solution containing the above cyclized catalyst and the above dehydrating agent into a nozzle from a slit into a support can be mentioned. After molding into a film shape, a part of the support is imidized to form a self-supporting gel film, which is then peeled off from the support, heated and dried, and imidized, and heat-treated.

The metal or the ring of the above-mentioned support system is controlled by the heat medium of liquid or gas and/or by the radiant heat of an electric heater or the like.

The gel film is heated by a heat source from a support and/or from a heat source such as a hot air or an electric heater, and is usually heated to 30 to 200 ° C, preferably to a temperature of 40 to 150 ° C to cause a ring closure reaction to dry the free organic solvent. The volatiles are self-supporting and are exfoliated from the support.

It is preferable that the gel film which is peeled off from the support is preferably extended by the rotating roller to the transport direction, but is not particularly limited. The extension to the conveying direction is carried out at a temperature of 140 ° C or lower. The stretching ratio (MDX) is usually 1.05 to 1.9 times, preferably 1.1 to 1.6 times, and more preferably 1.1 to 1.5 times. The gel film which is extended in the conveyance direction is introduced into the tenter apparatus, and both ends of the width direction are grasped by the tenter fabric, and are moved together with the tenter fabric, and one surface extends in the width direction. The extension to the width direction is carried out at a temperature of 200 ° C or higher. The stretching ratio (TDX) is usually 1.1 to 1.5 times, preferably 1.2 to 1.45 times, of MDX. For the gel film obtained by using the above composition, By applying the combination of the stretching ratios, an isotropic film can be obtained, and a film having the effect of the present invention can be obtained.

The film dried in the dry area is heated by hot air, an infrared heater or the like for 15 seconds to 10 minutes. Then, heat treatment is performed at a temperature of 250 to 500 ° C for 15 seconds to 20 minutes by hot air and/or electric heater.

Further, the thickness of the polyimide film is adjusted by adjusting the migration speed, and the thickness of the polyimide film is preferably from 3 to 250 μm, more preferably from 5 to 150 μm, in order to prevent deterioration of film formability.

The polyimide film thus obtained is preferably subjected to an annealing treatment. Thereby, 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. or higher and 500° C. or lower, more preferably 200° C. or higher and 370° C. or lower, and particularly preferably 210° C. or higher and 350° C. or lower. The thermal shrinkage at 200 ° C can be suppressed within the above range by the thermal relaxation caused by the annealing treatment, so that the dimensional accuracy is further improved. Specifically, it is preferred to carry out an annealing treatment by moving the film under a low tension in a furnace heated to the above temperature range. The time during which the film stays in the furnace becomes the processing time, and is controlled by changing the moving speed, preferably from 30 seconds to 5 minutes. If it is shorter than this, it is not possible to transfer heat to the film sufficiently, and if it is longer than this, there is a tendency to overheat and damage planarity, which is not preferable. Further, the film tension at the time of migration is preferably from 10 to 50 N/m, more preferably from 20 to 30 N/m. When the tension is less than the range, the film transition property is deteriorated, and if the tension is higher than the range, the heat shrinkage rate in the traveling direction of the obtained film becomes high, which is not preferable.

Moreover, in order to make the obtained polyimide film have adhesiveness, physical treatment such as electrotreatment or blast treatment such as corona treatment or plasma treatment may be performed on the surface of the film, and the physical treatment may be performed. It is done in the usual way. The pressure of the gas atmosphere in the case of performing the plasma treatment is not particularly limited, and 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 80.0 to 120 kPa (600 to 900 Torr). It range.

The gas atmosphere for plasma treatment is at least 20 mol% of inert gas, preferably 50 mol% or more of inert gas, more preferably 80 mol% or more, and most preferably 90 mol%. More than 8% of the ear. The inert gas includes He, Ar, Kr, Xe, Ne, Rn, N ₂ and a mixture of two or more of these. A particularly preferred inert gas is Ar. Further, as the inert gas, oxygen, air, carbon monoxide, carbon dioxide, carbon tetrachloride, chloroform, hydrogen, ammonia, tetrafluoromethane (carbon tetrafluoride), trichlorofluoroethane, trifluoromethane or the like may be mixed. Preferred combinations of the mixed gas used as the gas atmosphere for the plasma treatment of the present invention include 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/methane, argon/helium/dioxane, and the like.

The processing power density at the time of performing the plasma treatment is not particularly limited, and is preferably 200 W. Min/m ² or more, more preferably 500W. Min / m ² or more, the best is 1000W. Min/m ² or more. The plasma irradiation time for performing the plasma treatment is preferably from 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 accompanying deterioration of the film. The gas type, gas pressure, and treatment density of the plasma treatment are not limited to the above conditions, and may be carried out in the atmosphere.

Since the polyimide film obtained in this manner has a small dimensional change and an isotropic polyimide film having a small difference in thermal expansion coefficient between MD and TD, it can be preferably used for semiconductor packaging applications. Applications such as semiconductor process applications, display applications, solar cell substrates, and micro-pitch circuit substrates that require dimensional stability.

Further, the present invention also encompasses a copper-clad laminate using the above-described polyimine film of the present invention. The method for producing the copper-clad laminate according to the present invention is not particularly limited, and may be a conventionally known production method. The copper-clad laminate of the present invention is obtained, for example, by forming a polyimide having a thickness of 1 to 10 μm by a conventional method using the polyimide film of the present invention as a substrate.

Further, the present invention encompasses a glass/polyimine laminate using the above-described polyimine film of the present invention. The method for producing the laminate is not particularly limited. For example, the glass may be bonded to the polyimide film of the present invention in a conventional manner, and may be formed between the glass and the polyimide film of the present invention as needed. The common method is sandwiched with an adhesive or the like.

When the polyimine film of the present invention is used for a display, for example, by using the polyimide/polyimine laminate of the present invention, the polyimine film side laminate display is removed, and the glass portion is removed, thereby obtaining the use of the present invention. A display of the inventive polyimide film.

As long as the effects of the present invention are exerted, the present invention encompasses various combinations of the above-described configurations within the technical scope of the present invention.

[Examples]

In the following, the present invention will be specifically described by way of examples, but the present invention is not limited to the examples, and a large number of variations can be made by those skilled in the art within the technical idea of the present invention.

Further, in the examples, PPD means p-phenylenediamine, 4,4'-ODA means 4,4'-diaminodiphenyl ether, PMDA means pyromellitic dianhydride, and BPDA means 3,3',4. 4'-biphenyltetracarboxylic dianhydride, DMAc represents N,N-dimethylacetamide.

Further, each characteristic in the examples was evaluated by the following method.

(1) Thermal expansion coefficient

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

(2) Heat shrinkage rate

The film size (L1) after standing for 2 days in a room adjusted to 25 ° C and 60% RH was measured, and then heated at 200 ° C for 60 minutes, and then measured again in a room adjusted to 25 ° C and 60% RH for 2 days. The film size (L2) after that was evaluated by the following formula.

Heating shrinkage rate (%) = -{(L2-L1)/L1}×100

(3) Tensile modulus of elasticity

The measurement was carried out under the conditions of a tensile speed of 100 mm/min using a device RTM-250 (trade name, manufactured by A&D Co., Ltd.).

(4) Dimensional change rate

A copper layer of 10 μm thick was formed on the film by electrolytic plating with a copper sulfate plating solution, and pattern etching was performed at a pitch of 30 μm (line spacing of 15 μm) to form a copper wiring on the TD, and then manufactured by Shipley Far East. The electrolytic tin plating solution LT34 was subjected to tin plating, and the size (L3) of the TD at this time was measured. This was carried on a bonding table at 250 ° C and the dimension (L4) of the TD after bonding to the wafer by a bonding tool at 400 ° C was measured. The dimensional change rate is obtained by the following formula.

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

(5) tear resistance expansion resistance

A 63.5 mm × 50 mm test piece was prepared from the polyimide film, and a slit having a length of 12.7 mm was cut out from the test piece, and measured using a light weight-weight tear tester manufactured by Toyo Seiki Co., Ltd. according to JIS P 8116.

(6) Water absorption rate

The film was immersed in distilled water for 48 hours, and then taken out, the surface water was quickly wiped off, and a sample of about 5 mm × 15 mm in size was cut out. After the film was placed in a static eliminator, it was measured by a thermogravimetric analyzer TG-50 manufactured by Shimadzu Corporation. The temperature was raised to 200 ° C at a temperature increase rate of 10 ° C /min, and the water absorption rate was calculated according to the change in weight using the following formula.

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

[Example 1]

238.6 g of DMAc was added to a 500 ml separable flask, to which was added 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), reacted at normal temperature and normal pressure for 1 hour, and stirred until homogeneous to obtain a polyaminic acid solution.

After removing 15 g of the polyamic acid solution and cooling at -5 ° C, 1.9 g of acetic anhydride and 1.8 were mixed. g β-methylpyridine, thereby obtaining a mixed solution.

The mixture thus obtained was cast in a drum at 90 ° C for 30 seconds, and then the obtained gel film was heated at 100 ° C for 5 minutes, and extended to 1.23 times in the direction of migration. Then, the both ends in the width direction were gripped, and the film was heated at 270 ° C for 2 minutes and extended in the width direction by 1.4 times, and then heated at 380 ° C for 5 minutes to obtain a 38 μm thick polyimide film. Each of the properties was evaluated as shown in Table 1 by applying a tensile force of 20 N/m to the polyimide film in an oven set at 220 ° C for 1 minute.

[Examples 2 to 3]

The aromatic diamine component and the aromatic tetracarboxylic anhydride component were respectively obtained in the ratio shown in Table 1 by the same procedure as in Example 1, and then the transverse and longitudinal stretching ratios were obtained as shown in Table 1. The properties of the polyimide film obtained by the same operation as in Example 1 were evaluated, and the results are shown in Table 1.

(In the table, the molar ratios represent the % and all of the total aromatic diamine components, respectively. % of the anhydride component)

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

[Industrial availability]

Since the polyimide film of the present invention has a small dimensional change and an isotropic film having a small difference in thermal expansion coefficient between MD and TD, it can be preferably used for semiconductor packaging applications, semiconductor process applications, display applications, The use of a solar cell substrate or a substrate for a fine pitch circuit requires dimensional stability.

Claims (11)

A polyimine film obtained by using an aromatic diamine component and an acid anhydride component containing p-phenylenediamine, and using TMA-50 manufactured by Shimadzu Corporation at a measurement temperature range of 50 to 200 ° C both the thermal expansion coefficient α _TD, the heating rate of the mechanical film's measured at 10 ℃ / minute conditions conveying direction (MD) of the thermal expansion coefficient α _MD and the width direction (TD) of the average at 0ppm / ℃ or more and less than 7.0ppm Within the range of /°C, and satisfying the relationship of |α _MD -α _TD |<3. A polyimine film obtained by using an aromatic diamine component and an acid anhydride component containing p-phenylenediamine, and using TMA-50 manufactured by Shimadzu Corporation at a measurement temperature range of 50 to 200 ° C both the thermal expansion coefficient α _TD, the heating rate of the mechanical film's measured at 10 ℃ / minute conditions conveying direction (MD) of the thermal expansion coefficient α _MD and the width direction (TD) of the average at 0ppm / ℃ or more and less than 7.0ppm Within the range of /°C and satisfying the relationship of |α _MD -α _TD |<2. The polyimine film according to claim 1 or 2, wherein the film has a heating shrinkage ratio of MD and TD of 200 ° C of 0.05% or less. The polyimine film according to any one of claims 1 to 3, wherein a heat shrinkage ratio of 200 ° C of both MD and TD of the film is 0.03% or less. The polyimine film according to any one of claims 1 to 4, wherein the film has a tensile elastic modulus of 6.0 GPa or more. The polyimine film according to any one of claims 1 to 5, wherein the water absorption of the film is 3.0% or less. The polyimine film according to any one of claims 1 to 6, wherein the total amount of p-phenylenediamine relative to the aromatic diamine component is at least 31 mol% or more. The polyimine film according to any one of claims 1 to 7, which further comprises a group selected from the group consisting of 4,4'-diaminodiphenyl ether and 3,4'-diaminodiphenyl ether. One or more of them as aroma Group diamine component. The polyimine film according to any one of claims 1 to 8, wherein the acid anhydride component is selected from the group consisting of pyromellitic dianhydride and 3,3'-4,4'-biphenyltetracarboxylic dianhydride. One or more of the groups. A copper clad laminate characterized by using the polyimine film according to any one of claims 1 to 9. A glass/polyimine laminate characterized by using the polyimide film according to any one of claims 1 to 10.