WO2008010409A1 - Film de polyimide - Google Patents

Film de polyimide Download PDF

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Publication number
WO2008010409A1
WO2008010409A1 PCT/JP2007/063272 JP2007063272W WO2008010409A1 WO 2008010409 A1 WO2008010409 A1 WO 2008010409A1 JP 2007063272 W JP2007063272 W JP 2007063272W WO 2008010409 A1 WO2008010409 A1 WO 2008010409A1
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WIPO (PCT)
Prior art keywords
polyimide film
flexible
aromatic diamine
polyamic acid
diamine
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PCT/JP2007/063272
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English (en)
Japanese (ja)
Inventor
Shogo Fujimoto
Hisayasu Kaneshiro
Takashi Kikuchi
Shimizu Masayoshi
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Kaneka Corporation
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Publication of WO2008010409A1 publication Critical patent/WO2008010409A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02118—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer carbon based polymeric organic or inorganic material, e.g. polyimides, poly cyclobutene or PVC

Definitions

  • the present invention relates to a polyimide film that has been widely used as an insulating material in accordance with the reduction in weight and size of various electronic devices. More specifically, the present invention relates to a polyimide film that can be suitably used as a flexible printed circuit board, particularly a TAB (Tape Automated Bonding) type base film, in various uses of polyimide films.
  • TAB Transmission Automated Bonding
  • FPCs flexible printed wiring boards
  • a film made of a polyimide having a high chemical structural flexibility is generally used.
  • polyimide has a large linear expansion coefficient.
  • a flexible printed circuit board using a film as an insulating material has a drawback that it tends to be warped and curled.
  • a polyimide with a small linear expansion coefficient is selected, the flexibility of the film itself is lost and the film becomes very fragile, and the flexibility of the resulting FPC also decreases! .
  • TAB technology uses a film carrier tape (FC tape) that has a three-layer structure of a protective layer, an adhesive layer, and an organic insulating film layer (base film layer).
  • FC tape film carrier tape
  • the process of processing the TAB tape includes (1) a process of forming sprocket holes and device holes by punching, and (2) removing the protective layer and laminating the copper foil, and then applying the adhesive. Curing process, (3) arrangement pattern formation process (resist coating, copper etching, resist stripping), (4) plating process, (5) inner lead bonding process, (6) grease sealing process, (7) This is done in 8 steps: punching process, (8) outer lead bonding process, and LSI is mounted through the above processing steps.
  • Patent Document 1 Japanese Patent Laid-Open No. 9-328544
  • Patent Document 2 Japanese Patent Application Laid-Open No. 2004-124091
  • Patent Document 3 Japanese Patent Laid-Open No. 2000-80178
  • Patent Document 4 Japanese Unexamined Patent Publication No. 2000-119521
  • Patent Document 5 Japanese Unexamined Patent Publication No. 2006-96919
  • An object of the present invention is to provide a polyimide film that can be used for, for example, a flexible printed circuit board, in particular, a TAB-type base film, and in which warpage and curling are suppressed without causing problematic elongation.
  • a polyimide film using a polyamic acid having excellent storage stability, which enables stable continuous production in the polymerization of polyamic acid, which is a polyimide precursor.
  • the present invention is a polyimide film obtained using a polyamic acid solution as a precursor, wherein the polyamic acid comprises (1) at least one flexible aromatic diamine (1-a) and at least After forming a block composed of one kind of linear aromatic diamine (1 b) and at least one kind of aromatic dianhydride (1 c), (2) at least one kind of flexibility Aromatic diamine (2—a) and at least one aromatic dianhydride ( A polyimide film characterized by being obtained by forming a block by adding 2-c) so that the diamine component and the acid dianhydride component in all steps are substantially equimolar.
  • the number of the flexible groups contained in the flexible aromatic diamine (1a) is greater than the number of the flexible groups contained in the flexible aromatic diamine (2-a). It is related with the said polyimide film characterized by few.
  • the embodiment is characterized in that the flexible aromatic diamine (1a) has one flexible group, and the flexible aromatic diamine (2-a) has two or more flexible groups. And relates to the polyimide film.
  • a preferred embodiment relates to the polyimide film, characterized in that it comprises the flexible aromatic diamine (1a) force 4, 4'-diaminodiphenyl ether.
  • a preferred embodiment relates to the polyimide film, wherein the flexible aromatic diamine (1-a) is in the range of 10 to 50 mol% based on the total diamine component.
  • a preferred embodiment relates to the polyimide film, characterized in that it comprises the flexible aromatic diamine (2-a) force 2, 2 bis (4-aminophenoxyphenyl) propane.
  • a preferred embodiment relates to the polyimide film, wherein the flexible aromatic diamine (2-a) is in the range of 10 to 40 mol% based on the total diamine component.
  • the aromatic dianhydride (2-c) includes 3, 3 ', 4, 4' monobenzophenone tetracarboxylic dianhydride, Related to polyimide film.
  • the polyimide film is characterized in that the aromatic acid dianhydride (2-c) is in a range of 15 to 60 mol% based on the total acid dianhydride component. Concerning.
  • a preferred embodiment relates to the polyimide film, wherein the blocking force obtained by (1) is in the range of 40 to 90 mol% based on the total polyamic acid.
  • the embodiment relates to the polyimide film described above, which is used as a base material for a TAB tape.
  • a preferred embodiment relates to the polyimide film described above, wherein the polyimide film is obtained by chemically converting polyamic acid.
  • the average linear expansion coefficient at 100 to 200 ° C is 18 to 25 X 10 " 6 cm.
  • the present invention relates to the polyimide film, characterized by being ZcmZ ° C.
  • a preferred embodiment relates to the polyimide film, wherein the elastic modulus is 4. OGPa or more.
  • a preferred embodiment relates to the above polyimide film, characterized in that the amount of change in thickness when immersed in a 20 ° C IN sodium hydroxide aqueous solution for 6 hours is 5% or less.
  • a preferred embodiment relates to the above polyimide film, characterized in that the amount of change in thickness when immersed in an aqueous solution of sodium hydroxide and sodium hydroxide at 60 ° C for 2 minutes is 5% or less.
  • the dimensional change rate when immersed in an aqueous solution of sodium hydroxide and sodium hydroxide at 20 ° C IN for 6 hours is the film flow direction (MD direction) and the direction perpendicular to the MD direction (TD direction). Both are 0.05% or less of the above polyimide film.
  • a polyamic acid excellent in storage stability can be obtained, which enables stable continuous production while polymerization of polyamic acid which is a precursor of polyimide.
  • the polyimide film according to the present invention obtained using the polyamic acid is used as a flexible printed circuit board, particularly as a TAB-type base film, the occurrence of warpage and curling can be suppressed without causing problematic elongation. Furthermore, even when exposed to an alkaline plating solution, it is possible to suppress a decrease in adhesive strength, dimensional change, and the like.
  • the polyimide film of the present invention is obtained using a specific polyamic acid solution as a precursor, and the polyamic acid comprises (1) at least one flexible aromatic diamine (1-a ) And at least one linear aromatic diamine (1-b) and at least one aromatic dianhydride (1-c), and (2) at least one One kind of flexible aromatic diamine (2-a) and at least one kind of aromatic acid
  • the water product (2-c) is obtained by adding the diamine component and the acid dianhydride component in all steps so as to be substantially equimolar to form a block.
  • the polyamic acid has good storage stability, and the polyimide film obtained using the polyamic acid as a precursor suppresses the occurrence of warpage and curling. It is characterized by being able to produce.
  • step (1) In the production of the polyamic acid, first, in step (1), at least one kind of flexible aromatic diamine (1a), at least one kind of linear aromatic diamine (1b) and at least one kind are used. It is necessary to form a block composed of the aromatic dianhydride (1c).
  • the flexible aromatic diamine (1-a) in the present invention means an ether group, a methylene group, a propargyl group, a hexafluoropropargyl group, a carbonyl group, a sulfone group, a sulfide group, Diamine containing a flexible group such as an ester group in the main chain, or if the main chain does not contain a flexible group, the nitrogen atoms of the two amino groups and the carbon atom bonded to them are aligned.
  • 4, 4'-diaminodiphenyl ether is used in order to improve the storage stability of the polyamic acid and to develop the desired physical properties.
  • 3, 4 'oxydianiline, 3, 4' oxydianiline, 2,4 'oxydianiline are preferred.
  • 4,4′-diaminodiphenyl ether because the final polyimide film can be suitably obtained in addition to the above.
  • the number of the flexible groups contained in the flexible aromatic diamine (1a) used in the step (1) in the synthesis of the polyamic acid is the same as that of the flexible aromatic diamine used in the step (2) described later.
  • the number is preferably smaller than the number of flexible groups contained in (2-a). Furthermore, it is more preferable that the number of the flexible groups contained in the flexible aromatic diamine (1-a) is one U.
  • the amount of the flexible aromatic diamine (1a) used is the total amount used for synthesizing the polyamic acid from the viewpoint of the storage stability of the polyamic acid and the linear expansion coefficient of the finally obtained polyimide film.
  • the range of 10 to 50 mol% based on the diamine component is preferred, and the range of 20 to 40 mol% is more preferred.
  • the linear aromatic diamine (l-b) used in the step (1) is an ether group, a methylene group, a propargyl group, a hexafluoropropargyl group, or a carbo group.
  • the main chain does not contain a flexible group such as a sulfone group, a sulfide group, or an ester group, and the nitrogen atom of two amino groups and the carbon atom to which they are bonded are aligned.
  • a flexible group such as a sulfone group, a sulfide group, or an ester group, and the nitrogen atom of two amino groups and the carbon atom to which they are bonded are aligned.
  • p-phenylenediamine and its nuclear substitution compound benzidine and its nuclear substitution compound and the like can be mentioned. These can be used alone or in combination of two or more.
  • linear aromatic diamines (1-b) it is particularly preferred to use p-phenylenediamine in terms of processability, handleability, and the balance of properties of the final polyimide film.
  • the amount of the linear aromatic diamine (1b) used is preferably in the range of 25 to 60 mol% based on the total diamine components used in the synthesis of the polyamic acid, and more preferably 30 to 50 m. It is more preferable to use in the range of ol%. If the amount of linear aromatic diamine (1-b) used is out of the above range, the linear expansion coefficient of the final polyimide film is preferred and may deviate from the range. In some cases, it is impossible to continuously obtain a film with stable warping.
  • the use ratio of the flexible diamine (1a) and the linear diamine (1b) in the step (1) can be appropriately set.
  • Storage stability of the polyamic acid and finally obtained polyimide film From the standpoint of the linear expansion coefficient, the flexible diamine should be used in the range of 20-50 mol%, preferably 30-40 mol% with respect to the sum of the flexible diamine (1-a) and linear diamine (1-b). Is preferred.
  • Examples of the acid dianhydride that can be used as the aromatic dianhydride (1c) include pyromellitic dianhydride, 2, 3, 6, 7 naphthalene tetracarboxylic dianhydride, 3, 3 ', 4, 4, -biphenyl tetracarboxylic dianhydride, 1, 2, 5, 6 naphthalene tetracarboxylic dianhydride, 2, 2 ', 3, 3, -biphenyl tetracarboxylic dianhydride, 3, 3 ', 4, 4, monobenzophenone tetracarboxylic dianhydride, 2, 2', 3, 3, monobenzophenone tetracarboxylic dianhydride, 4, 4'-oxydiphthalic dianhydride 3, 4'-oxydiphthalic dianhydride, 2, 2 Bis (3,4 dicarboxyphenyl) propane dianhydride, 3, 4, 9, 10 Perylenetetracarboxylic dianhydride, Bis (3,4 di
  • aromatic acid dianhydrides (1c) pyromellitic acid dianhydride, 2, 2 ', 3, 3,-, from the viewpoint of controlling the linear expansion coefficient within the set range.
  • Biphenyltetracarboxylic dianhydride, 3, 3 ', 4, 4, monobenzophenone tetracarboxylic dianhydride, 2, 2', 3, 3, monobenzophenone tetracarboxylic dianhydride A thing can illustrate more preferably.
  • pyromellitic dianhydride is particularly preferred.
  • the amount of the aromatic dianhydride (1c) used is 40 to 85 mol%, more preferably 50 to 70 mol% based on the total acid dianhydride component. Control within the range is preferable from two viewpoints.
  • the present invention is characterized by a method for polymerizing a polyamic acid, which is a polyimide precursor, and in particular in step (1), a flexible aromatic diamine (1-a) and a linear aromatic diamine ( It is characterized by forming blocks using 1-b) and aromatic dianhydride (1c).
  • a polyamic acid which is a polyimide precursor
  • a flexible aromatic diamine (1-a) and a linear aromatic diamine It is characterized by forming blocks using 1-b) and aromatic dianhydride (1c).
  • the linear expansion coefficient of the resulting polyimide film is higher than the target value.
  • the present inventors copolymerized the flexible aromatic diamine (1a), which is a highly flexible diamine, which is more flexible than the linear aromatic diamine (1-b), into the above system, The inventors have found a surprising finding that it is possible to obtain a polyamic acid that can suppress the linear expansion coefficient of the film from becoming too high than the target value and has good storage stability.
  • the flexible aromatic diamine (2-a) in the step (2) will be described.
  • the flexible aromatic diamine (2-a) include the same compounds as the diamine compounds exemplified as the flexible aromatic diamine (1-a). These can be used alone or in combination of two or more. Among these, 2, 2 bis (4 aminophenoxyphenol) propane and 4, 4, 1-diaminodiphenol propane are more preferred from the viewpoint of achieving the target alkali resistance. 4-aminophenol) propane is particularly preferably used.
  • the number of the flexible groups in the flexible aromatic diamine (2-a) used in the step (2) is used in the step (1).
  • the number is preferably larger than the number of flexible groups in the flexible aromatic diamine (1a).
  • the number of flexible groups in the flexible aromatic diamine (2-a) is more preferably 2 or more.
  • the amount of the flexible aromatic diamine (2-a) used is 10% on the basis of all diamine components used in the synthesis of polyamic acid from the viewpoint of suppression of breakage during film formation and linear expansion coefficient. Preferably it is in the range of ⁇ 40 mol%, more preferably in the range of 20-30 mol%.
  • the aromatic acid dianhydride (2-c) in the step (2) is exemplified by the same acid dianhydride compounds exemplified as the aromatic acid dianhydride (1c). it can. These can be used singly or in combination of two or more.
  • the amount of the aromatic dianhydride (2-c) used is preferably 15 to 60 mol% based on the total acid dianhydride component used in the synthesis of the polyamic acid. More preferred is 50mol%. If the amount of aromatic dianhydride (2-c) used is less than 15 mol%, the storage modulus of the film in the high temperature region may become too low, making film formation difficult, and conversely exceeding 60 mol%. And the linear expansion coefficient of the film deviates from the preferred range. In some cases, it takes time to reach a saturated moisture absorption state.
  • the flexible aromatic diamine (2-a) and the aromatic dianhydride (2-c) in the step (2) are the diamine component and acid dianhydride used in all steps of the polyamic acid synthesis. It is necessary to add the physical components so as to be substantially equimolar to form a block.
  • substantially equimolar means that the total diamine component is used in the range of 49.5 to 50.5 mol% with respect to the sum of the total diamine component and the total acid dianhydride component.
  • the total amount of diamine components is less than 49.5 mol%, it may be difficult to produce stably, and if it exceeds 50.5 mol%, the viscosity of the polyamic acid becomes too high, resulting in defects in the polyimide film. Tend to be easier to make.
  • step (1) and step (2) performed in the synthesis of polyamic acid will be described.
  • a flexible aromatic diamine (1-a), a linear aromatic diamine (1 b), and an aromatic acid dianhydride (1 c) are compared.
  • a rigid, non-thermoplastic polyimide block is formed to prevent the final polyimide film from having an excessively high linear expansion coefficient.
  • Block obtained by copolymerizing the aromatic aromatic diamine (2-a) and aromatic acid dianhydride (2-c) to form a relatively soft block can achieve the target linear expansion coefficient of the polyimide film.
  • the blocking force obtained by the step (1) is preferably in the range of 40 to 90 mol% based on the total polyamic acid, and in the range of 50 to 80 mol%. It is more preferable. If the block obtained by the step (1) is less than 40 mol%, the desired physical properties may not be stably expressed. Conversely, if it exceeds 90 mol%, the polyamic acid is stably produced in continuous production. It may be difficult to get
  • any known method can be used.
  • an aromatic dianhydride and an aromatic diamine are dissolved in an organic solvent,
  • the obtained polyamic acid solution can be produced by stirring under controlled temperature conditions until the polymerization of the acid dianhydride and diamine is completed.
  • These polyamic acid solutions are usually obtained at a concentration of 5 to 35% by weight, preferably 10 to 30% by weight. Generally, when the concentration is in the above range, a polyamic acid solution having an appropriate molecular weight and solution viscosity can be obtained.
  • any known method can be used.
  • any solvent that dissolves the resulting polyamic acid can be used.
  • amide solvents that is, N, N-dimethylformamide, N, N N, N-dimethylformamide and N, N-dimethylacetamide are particularly preferably used, such as —dimethylacetamide and N-methyl-2-pyrrolidone.
  • a filler can be added to the polyamic acid solution for the purpose of improving various properties of the film such as slidability, thermal conductivity, conductivity, and corona resistance.
  • Any material may be used as the filler, but preferred examples include silica, titanium oxide, alumina, silicon nitride, boron nitride, calcium hydrogen phosphate, calcium phosphate, mica and the like.
  • the particle diameter of the filler is not particularly limited because it is determined by the film characteristics to be modified and the type of filler to be added, but generally the average particle diameter is 0.05. To 100 ⁇ m, preferably 0.1 to 75 ⁇ m, more preferably 0.1 to 50 ⁇ m, and particularly preferably 0.1 to 25 / ⁇ ⁇ . If the particle diameter is below this range, the effect of improving the film properties is hardly exhibited. Conversely, if it exceeds this range, the surface properties may be greatly impaired or the mechanical properties may be greatly deteriorated.
  • the number of added parts of the filler is not particularly limited because the film characteristics to be modified are determined by the filler particle size and the like.
  • the amount of filler added is from 0.01 to 100 parts by weight of LEO, preferably from 0.01 to 90 parts by weight, and more preferably from 0.02 to 80 parts by weight per 100 parts by weight of positive imide. If the amount of filler added is below this range, the effect of reforming by the filler becomes difficult to be exhibited. Conversely, if it exceeds this range, the mechanical properties of the film may be greatly impaired.
  • the filler may be added by (1) adding a reaction solution before or during the polymerization of polyamic acid. How to add, (2) After polymerization is completed, a method of kneading filler using three rolls, etc., (3) A method of preparing a dispersion containing filler and mixing it with a polyamic acid solution, etc. Although a method may be used, the method of mixing the dispersion containing the filler with the polyamic acid solution, particularly the method of mixing just before the film formation is preferable because the contamination by the filler in the production line is minimized. When preparing a dispersion containing a filler, it is preferable to use the same solvent as the polymerization solvent for the polyamic acid. Further, in order to disperse the filler satisfactorily and stabilize the dispersion state, it is possible to use a dispersant, a thickener, etc. within a range that does not affect the film properties.
  • a conventionally known method can be used without any particular limitation. Examples of this method include a thermal imidization method and a chemical imidization method, but imidization by a chemical imidation method is preferable in terms of thermal dimensional stability and mechanical strength.
  • the method for producing a polyimide film includes the following steps.
  • a polyamic acid solution is mixed with a dehydrating agent typified by an acid anhydride such as acetic anhydride, and an imidic acid catalyst typified by a tertiary amine such as isoquinoline, ⁇ -picoline, and pyridine. It is a method of acting.
  • a thermal imidization method may be used in combination with the chemical imidization method. The heating conditions can vary depending on the type of polyamic acid, the thickness of the film, and the like.
  • a film-forming dope can be obtained by mixing the dehydrating agent and the imido catalyst at a low temperature in a polyamic acid solution. Subsequently, this dope is applied to a glass plate, aluminum foil, endless stainless steel. Casting in the form of a film on a support such as a les belt or stainless drum, and heating on the support in a temperature range of 80 ° C to 200 ° C, preferably 100 ° C to 180 ° C. After partially curing and Z or drying by activating the imidization catalyst, the support force can be peeled off to obtain a polyamic acid film (hereinafter referred to as gel film! /).
  • the gel film is in an intermediate stage of curing to polyamic acid polyimide and has a self-supporting property.
  • the calculated volatile content is in the range of 5 to 500%. Preferably it is 5 to 100%, more preferably 10 to 80%, and most preferably 30 to 60%. It is preferable to use a film in this range, and if it is removed, the mechanical strength of the polyimide film may be lowered.
  • a and B represent the following.
  • the end of the gel film is fixed and dried while avoiding shrinkage during curing, water, residual solvent, residual dehydrating agent and imidization catalyst are removed, and the remaining amic acid unit is completely removed.
  • the polyimide film of the present invention can be obtained by imidization.
  • the heat treatment can be performed under the minimum tension necessary for transporting the film.
  • This heat treatment may be performed in the film manufacturing process, or may be provided separately.
  • the heating conditions vary depending on the film characteristics and the equipment used, and therefore cannot be determined in general. Generally 200 ° C to 500 ° C, preferably 250 ° C to 500 ° C, particularly preferred
  • the internal stress can be relieved by heat treatment at a temperature of 300 ° C. or higher and 450 ° C. or lower for 1 to 300 seconds, preferably 2 to 250 seconds, and particularly preferably 5 to 200 seconds.
  • the film can be stretched before and after fixing the gel film. At this time, preferred!
  • the volatile content is 30 to 200%, preferably 50 to 150%. If the volatile content is below this range, it may be difficult to stretch, and if it exceeds this range, the self-supporting property of the film is poor, and the stretching operation itself may be difficult.
  • Stretching may be performed using a well-known and well-known method such as a method using a differential roll or a method of widening the fixing interval of the tenter.
  • the average linear expansion coefficient of force preferably 18 ⁇ 25 X 10- 6 cm / cm / ° range C in 100 to 200 ° C, more preferably 20 ⁇ 23 X 10- 6 cm /
  • Elastic modulus is preferably 4.0-10.
  • OGPa more preferably 4.5-7.
  • OGPa and (3) Thickness is 10-125 m, preferably ⁇ .
  • a polyimide film of 35 to: LOO m, more preferably 50 to 75 m, can be suitably obtained.
  • Non-thermoplastic refers to a material that melts and maintains the shape of the film when it is heated to about 450-500 ° C. Therefore, the polyimide film should be designed so that it becomes non-thermoplastic by the above-mentioned yarn formation.
  • the polyimide film of the present invention is suitably used as a base material for TAB tape.
  • the adhesive is completely dried after being completely cured, and humidity is adjusted at 60% RH and a temperature of 23 ° C. Saturated moisture absorption when the amount of warpage no longer changes If the amount of warpage in the dry state Xi force Warp change time until the amount of warpage Xe in the saturated moisture absorption state (time from XI to Xe) is within 6 hours Preferably, it is within 5 hours, particularly preferably within 4 hours.
  • Warp change time exceeds the above range, a photomask exposure failure or etching failure occurs during notching due to a dimensional change due to warpage change during the processing process. There is a tendency for defects due to warping to occur, such as good and poor alignment during semiconductor mounting.
  • a polyimide film having a thickness change of 5% or less when immersed in a 20 ° C IN sodium hydroxide aqueous solution for 6 hours can be obtained.
  • a polyimide film having a thickness change of 5% or less when immersed in an aqueous sodium hydroxide solution for 30 minutes can be obtained.
  • the dimensional change rate when immersed in an aqueous solution of sodium hydroxide and sodium hydroxide at 20 ° C IN for 6 hours is 0.05% or less in both the film flow direction (MD direction) and the MD direction (TD direction).
  • MD direction film flow direction
  • TD direction MD direction
  • linear expansion coefficient, elastic modulus, warpage measurement, and storage stability evaluation method in the synthesis examples, examples, and comparative examples are as follows.
  • the linear expansion coefficient at 100 to 200 ° C was measured using a TMA120C manufactured by Seiko Electronics Co., Ltd. (sample size width 3 mm, length 10 mm), 10 ° C to 400 ° at 10 ° C / min with a load of 3 g. The temperature is raised to C once, then cooled to 10 ° C, further heated at 10 ° C / min, and the average value is determined from the coefficient of thermal expansion at 100 ° C and 200 ° C during the second temperature increase. As calculated.
  • the elastic modulus was measured according to ASTM D882.
  • the resulting polyamic acid is allowed to stand at 15 ° C for 4 hours, and then subjected to a leaf filter (leaf diameter: 15 inches, number of leaves: 100 sheets, opening size: 3 m).
  • the storage stability when the filtration time twice as long as the initial filtration time was required was evaluated as NG, and the others were evaluated as good (OK).
  • the value of warpage is 40mm in length X 35mm in width for TAB tape created by the following procedure.
  • the cut and vacuum dried (0. lMPa, 2 hours) state was completely dried, left on a flat surface, and the height of the four corners was measured.
  • the amount of warping is Xi).
  • the amount of warpage was measured while adjusting the humidity of a vacuum-dried sample at a humidity of 60% RH and a temperature of 23 ° C, and the point when the amount of warpage stopped changing was regarded as a saturated moisture absorption state. To do).
  • a TAB tape was prepared as follows.
  • Polyamide resin (Platabond M1276 from Nippon Rilsan) 50 parts by weight, Bisphenol A type epoxy resin (Epicoat 828 from Yuka Shell Epoxy) 30 parts by weight, Cresol novolac epoxy resin 10 parts by weight, toluene
  • An adhesive solution was prepared by mixing 150 parts by weight of a 1Z1 mixed solution of Z isopropyl alcohol with 45 parts by weight of a 20% by weight methylceosolve solution of diaminodiphenylsulfone Z dicyandiamide 4Z1.
  • the adhesive solution was applied on a 25 ⁇ m thick PET film to a thickness of 11 m after drying, and dried at 120 ° C. for 2 minutes.
  • This PET film with B-stage adhesive was slit to a width of 26 mm.
  • the above copper bonded product is heated in steps of 60 ° C for 3 hours, 80 ° C for 3 hours, 120 ° C for 3 hours, 140 ° C for 3 hours, 160 ° C for 4 hours, and then slowly cooled.
  • the adhesive was cured.
  • the 5 ⁇ 5 cm sample was obtained from the following formula from the thickness before and after immersing the sample in a sodium hydroxide aqueous solution.
  • Table 1 shows the results of evaluating film physical properties and storage stability.
  • Table 1 shows the results of evaluating film physical properties and storage stability.
  • TAB tape was prepared according to the reference example.
  • Table 2 shows the characteristics of TAB tape.
  • a film was formed in the same manner as in Example 1, but the film was brittle and fractured in the tenter furnace.
  • Table 3 shows the characteristics of the polyimide film evaluated at the part where the film was formed.

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  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

L'invention concerne un film de polyimide à utiliser, par ex., comme film de base dans le cadre de la technique TAB. Le film de polyimide est obtenu à partir d'une solution d'acide polyamique en tant que précurseur et il est caractérisé en ce que l'acide polyamique est obtenu par (1) formation d'un bloc à partir d'au moins une diamine aromatique flexible (1-a), d'au moins une diamine aromatique linéaire (1-b), et d'au moins un dianhydride acide aromatique (1-c), et (2) par addition subséquente d'au moins une diamine aromatique flexible (2-a) et d'au moins un dianhydride acide aromatique. Ainsi, la quantité molaire des ingrédients diamine ajoutés à toutes les étapes est pratiquement égale à celle des ingrédients de dianhydride acide ajoutés à toutes les étapes pour former un bloc.
PCT/JP2007/063272 2006-07-18 2007-07-03 Film de polyimide WO2008010409A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2006196029 2006-07-18
JP2006-196261 2006-07-18
JP2006196261 2006-07-18
JP2006-196029 2006-07-18

Publications (1)

Publication Number Publication Date
WO2008010409A1 true WO2008010409A1 (fr) 2008-01-24

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PCT/JP2007/063272 WO2008010409A1 (fr) 2006-07-18 2007-07-03 Film de polyimide

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Country Link
TW (1) TW200827387A (fr)
WO (1) WO2008010409A1 (fr)

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CN116444793A (zh) * 2023-03-22 2023-07-18 青岛达亿星电子化工新材料研究院有限公司 一种高性能聚酰亚胺挠性覆铜板及其制备方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI471180B (zh) * 2012-06-04 2015-02-01 Triumphant Gate Ltd Surface treatment of wet process cleaning fluid in the gold and cyanide recycling system

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JPH04161428A (ja) * 1990-10-24 1992-06-04 Kanegafuchi Chem Ind Co Ltd ポリイミドフィルム
JPH0525273A (ja) * 1991-07-18 1993-02-02 Kanegafuchi Chem Ind Co Ltd ポリイミドフイルムとその製造方法
JPH0570591A (ja) * 1991-09-13 1993-03-23 Kanegafuchi Chem Ind Co Ltd ポリアミツク酸共重合体及びそれからなるポリイミドフイルム
JPH10298286A (ja) * 1997-02-25 1998-11-10 Du Pont Toray Co Ltd ブロック成分を有する共重合ポリイミドフィルム、その製造方法およびそれを基材とした金属配線回路板
JPH1180390A (ja) * 1997-07-18 1999-03-26 Du Pont Toray Co Ltd ポリイミドフィルム、その製造方法およびそれを基材とした金属積層板
JPH11152331A (ja) * 1997-11-20 1999-06-08 Kanegafuchi Chem Ind Co Ltd ポリアミド酸およびポリイミドフィルムの製造方法
JP2002155140A (ja) * 2000-08-24 2002-05-28 Du Pont Toray Co Ltd ポリイミドフィルム、その製造方法およびこれを基材とした金属配線板
JP2004124091A (ja) * 2002-09-13 2004-04-22 Kanegafuchi Chem Ind Co Ltd ポリイミドフィルム及びその製造方法並びにその利用

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04161428A (ja) * 1990-10-24 1992-06-04 Kanegafuchi Chem Ind Co Ltd ポリイミドフィルム
JPH0525273A (ja) * 1991-07-18 1993-02-02 Kanegafuchi Chem Ind Co Ltd ポリイミドフイルムとその製造方法
JPH0570591A (ja) * 1991-09-13 1993-03-23 Kanegafuchi Chem Ind Co Ltd ポリアミツク酸共重合体及びそれからなるポリイミドフイルム
JPH10298286A (ja) * 1997-02-25 1998-11-10 Du Pont Toray Co Ltd ブロック成分を有する共重合ポリイミドフィルム、その製造方法およびそれを基材とした金属配線回路板
JPH1180390A (ja) * 1997-07-18 1999-03-26 Du Pont Toray Co Ltd ポリイミドフィルム、その製造方法およびそれを基材とした金属積層板
JPH11152331A (ja) * 1997-11-20 1999-06-08 Kanegafuchi Chem Ind Co Ltd ポリアミド酸およびポリイミドフィルムの製造方法
JP2002155140A (ja) * 2000-08-24 2002-05-28 Du Pont Toray Co Ltd ポリイミドフィルム、その製造方法およびこれを基材とした金属配線板
JP2004124091A (ja) * 2002-09-13 2004-04-22 Kanegafuchi Chem Ind Co Ltd ポリイミドフィルム及びその製造方法並びにその利用

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116444793A (zh) * 2023-03-22 2023-07-18 青岛达亿星电子化工新材料研究院有限公司 一种高性能聚酰亚胺挠性覆铜板及其制备方法

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