JP2006114864A - Two-sided tape for loc and manufacturing method therefor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a two-sided tape for LOC which satisfies both the adhesive characteristics with a metallic lead frame and characteristics with a semiconductor chip insulating film made of a plastic material and enables low-temperature bonding process, and to provide a manufacturing method therefor. <P>SOLUTION: A two-sided tape for LOC consists of a polyimide base film having a glass transition temperature of 300°C or higher and a thickness of 5 to 150 μm, an adhesive layer formed by applying a composition for a polyimide-base adhesive containing an acid end group to one side of the polyimide base film, and an adhesive layer formed by applying a composition for a polyimide-base adhesive containing an amine end group to the other side of the polyimide base film. The adhesive power, between the polyimide base film and each of the adhesive layers, is 0.8 kgf/cm<SP>2</SP>or larger. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a double-sided tape for LOC and a method for manufacturing the same, and more specifically, an adhesive layer having different adhesive components is laminated on both sides of a polyimide base film, and each adhesion surface, that is, a metallic lead. The present invention relates to a double-sided tape for LOC having excellent adhesive properties simultaneously to a frame and a plastic semiconductor chip insulating film, and a method for manufacturing the same.

  In general, in a semiconductor package, a composite film manufactured by coating an adhesive on both sides of a base film is a LOC (lead on chip), COL (chip on lead), window-tube, etc. for bonding a semiconductor chip and a lead frame. Used for.

  In particular, in the LOC semiconductor package process, it is required to lower the bonding process in accordance with the increase in capacity and miniaturization of the semiconductor chip. The lower the bonding temperature between the lead frame and the semiconductor chip, the lower the yield after the semiconductor package. An advantageous result in terms of reliability can be obtained.

  In a conventional LOC double-sided tape for LOC package use, a plastic adhesive component mainly made of polyimide is used as the same adhesive on both sides of a polyimide base film. However, since the lead frame and the semiconductor chip as the base material surface on which the double-sided tape for LOC is affixed are made of different materials, that is, a metal material and a plastic material, respectively, the adhesive properties of one base material are satisfied. The problem arises that the adhesive properties of the other substrate deteriorate.

  Therefore, there is a limit to setting the bonding process temperature to a lower temperature in order to satisfy the bonding characteristics with the metal lead frame and the bonding characteristics with the plastic semiconductor chip insulating film at the same time. This causes problems such as a decrease in the yield of the semiconductor package and a decrease in the reliability of the package.

  Therefore, the present inventors have laminated adhesive layers having different adhesive components on both sides of the polyimide base film, and at the same time have excellent adhesive properties for metal lead frames and plastic semiconductor chip insulating films. The present invention has been completed by manufacturing a double-sided tape for LOC having the above and confirming its physical properties.

  An object of the present invention is to provide a polyimide base film, an adhesive layer formed by applying an acid end group-containing polyimide adhesive composition on one surface of the polyimide base film, and the polyimide base film. An object of the present invention is to provide a double-sided tape for LOC comprising an adhesive layer formed by applying an amine terminal group-containing polyimide adhesive composition on the surface.

  Another object of the present invention is to provide a LOC double-sided tape capable of simultaneously satisfying the adhesive property with a metal lead frame and the adhesive property with a plastic semiconductor chip insulating film and capable of performing a low-temperature adhesive process. There is to do.

  Another object of the present invention is to provide a method for producing the double-sided tape for LOC.

In order to solve the above-mentioned problems, according to an aspect of the present invention, a polyimide base film having a glass transition temperature of 300 ° C. or higher and a thickness of 5 to 150 μm, and an acid end group-containing polyimide on one surface of the polyimide base film An adhesive layer formed by applying a composition for an adhesive based on an adhesive, an adhesive layer formed by applying an amine terminal group-containing composition for an polyimide based adhesive on the other surface of the polyimide base film, and The LOC double-sided tape is characterized in that the adhesive strength between the polyimide base film and the respective adhesive layers is 0.8 kgf / cm ² or more.

  The polyimide adhesive composition is composed of any one selected from 1) dianhydride, 2) diamine, 3) polyamino compound, and 4) diamine containing siloxane structure, triamine, or tetraamine.

  The polyimide adhesive composition further includes at least one selected from the group consisting of an epoxy resin, a bismaleimide resin and a rubber resin, and is a hybrid type of a thermoplastic resin and a thermosetting resin. It is characterized by that.

  The acid end group-containing polyimide adhesive composition has a dianhydride and diamine molar fraction of 0.501: 0.499 to 0.524: 0.476, and an excessive amount of dianhydride is added. Is polymerized. At this time, the acid value is 0.03 to 10.

  In addition, the amine terminal group-containing polyimide adhesive composition has a dianhydride and diamine molar fraction of 0.499: 0.501 to 0.476: 0.524, and an excessive amount of diamine is added. It has been polymerized. At this time, the amine value is 0.03 to 10.

  The adhesive layer coated with the acid-end group-containing polyimide adhesive composition has a metal lead frame attached thereto, and the amine end-group-containing polyimide adhesive composition-coated adhesive layer is a plastic. It is made to adhere to the semiconductor chip insulating film of a material.

  According to another aspect of the present invention, an adhesive is obtained by applying a polyimide adhesive composition containing an acid end group to one surface of a polyimide base film having a glass transition temperature of 300 ° C. or higher and a thickness of 5 to 150 μm. Forming a layer, applying an amine terminal group-containing polyimide adhesive composition on the other surface of the polyimide base film to form an adhesive layer, and applying the polyimide base film to the polyimide base film Applying the adhesive layer at a high temperature of 150 to 350 ° C. for 0.001 to 1 second.

  The double-sided tape for LOC of the present invention is obtained by laminating an adhesive layer having different adhesive components on a polyimide base film, adhesion characteristics with a metal lead frame, and adhesion with a plastic semiconductor chip insulating film. The characteristics can be satisfied at the same time.

  The double-sided tape for LOC of the present invention can increase the reliability and yield of the semiconductor package by lowering the temperature of the high temperature bonding process to the temperature of the relatively low temperature process.

  Hereinafter, the present invention will be described in detail.

  The double-sided tape for LOC of the present invention is a polyimide base film having a glass transition temperature of 300 ° C. or higher and a thickness of 5 to 150 μm, and a polyimide adhesive composition containing acid end groups on one surface of the polyimide base film. And an adhesive layer formed by applying an amine terminal group-containing polyimide adhesive composition to the other surface of the polyimide base film.

  The polyimide adhesive composition is composed of any one selected from 1) dianhydride, 2) diamine, 3) polyamino compound, and 4) diamine having a siloxane structure, triamine, or tetraamine.

  The double-sided tape for LOC of the present invention is characterized in that an adhesive layer having different adhesive components is laminated on both sides of a polyimide base film, and has an adhesive property with an adhesive surface attached to each adhesive layer. Excellent.

The double-sided tape for LOC of the present invention forms an adhesive layer by applying an acid terminal group-containing polyimide adhesive composition on one surface of a polyimide base film having a glass transition temperature of 300 ° C. or higher and a thickness of 5 to 150 μm. Then, an amine end group-containing polyimide adhesive composition is applied to the other surface of the polyimide base film to form an adhesive layer, and each of the adhesive layers is applied to the polyimide base film at 150 to 350. It is made to adhere for 0.001-1 second under high temperature of ° C. The double-sided tape for LOC manufactured in this way has an adhesive force between the polyimide base film and each adhesive layer of 0.8 kgf / cm ² or more.

  The main component of the adhesive layer is a heat-resistant thermoplastic resin having a glass transition temperature of 150 ° C. to 350 ° C., and more preferably polyimide. In this case, the polyimide includes not only a simple polyimide but also a resin having an imide bond such as a polyamideimide, a polyesterimide, or a polyetherimide.

  The composition for polyimide adhesives of the present invention comprises any one selected from 1) dianhydride, 2) diamine, 3) polyamino compound, and 4) diamine containing siloxane structure, triamine or tetraamine.

  A normal polyimide-based adhesive is produced from a polymer obtained by a reaction between dianhydride and dian. When one of the reactants of dianhydride or diamine is added in an excessive amount, an end group of the polymer is acid or Remains in the form of an amine.

  Therefore, the LOC double-sided tape of the present invention forms an adhesive layer by applying an acid terminal group-containing polyimide adhesive composition on one surface of a polyimide base film, and on the other surface of the polyimide base film. By producing an adhesive layer by applying an amine terminal group-containing polyimide adhesive composition, it has an adhesive layer with different adhesive components, and thus has excellent adhesive properties with each adhesion surface.

  That is, the adhesive layer to which the acid-end group-containing polyimide adhesive composition is applied is inferior in adhesive properties with a plastic substrate, but copper, copper alloys, nickel iron alloys (Iron-nickel alloys, so-called “Alloy 42”), excellent adhesion properties to lead frames made of metallic materials including invariant steel (invar, steel nickel alloy).

  In addition, the adhesive layer coated with the amine end group-containing polyimide adhesive composition has a relatively high adhesion process temperature with the metal, and the end group is in the acid form, compared to the metal. It is inferior in the adhesive property to the semiconductor chip insulating film made of plastic material.

  The acid-end group-containing polyimide adhesive composition is polymerized by adding an excessive amount of dianhydride during polyimide polymerization, and the molar fraction of dianhydride and diamine is 0.501: 0.499- 0.524: 0.476, more preferably 0.502: 0.498 to 0.520: 0.480, and most preferably 0.503: 0.497 to 0.517: 0.483. It is a range. At this time, if the molar fraction of dianhydride and diamy is smaller than the range of 0.501: 0.499, the effect of excessive addition of dianhydride is insignificant and shows a great effect in increasing the adhesive strength with metal. If the molar fraction of dianhydride and diamine is larger than the range of 0.524: 0.476, the molar ratio shows a very large difference, so that the molecular weight, mechanical properties and moisture absorption resistance of the polyimide are lowered. Problem occurs.

  The acid value of the acid terminal group-containing polyimide adhesive composition is preferably in the range of 0.03 to 10, more preferably in the range of 0.05 to 7.0. At this time, if the acid value of the composition is smaller than 0.03, the carboxyl group of the terminal group is small and the adhesion property with the metal is not good, and if the acid value is larger than 10, the moisture absorption resistance of the material is lowered. .

  In the above, the acid value means the number of milligrams of alkali necessary for neutralizing the carboxyl group contained in 1 g of resin. After dissolving 50 mL of DMSO in 2 g of polyimide sample, 0.1 Two to three drops of mixed indicator consisting of% thymol blue and phenol red were added, followed by titration with a 0.1 N KOH butoxyethanol mixed solution, and expressed in mg of equivalent potassium hydroxide.

  On the other hand, the amine terminal group-containing polyimide adhesive composition was polymerized by adding an excessive amount of diamine during polyimide polymerization, and the molar fraction of dianhydride and diamine was 0.499: 0. .501 to 0.476: 0.524, more preferably 0.498: 0.502 to 0.480: 0.520, and most preferably 0.497: 0.503 to 0.483. : It is the range of 0.517.

  At this time, if the molar fraction of dianhydride and diamine is smaller than the range of 0.499: 0.501, the effect of the excessive amount of diamine is insignificant and shows a great effect in increasing the adhesive strength with plastic. When the molar fraction of dianhydride and diamine is larger than the range of 0.476: 0.524, the molar ratio is so large that the molecular weight, mechanical properties and moisture absorption resistance of the polyimide are lowered. The problem occurs.

  The amine value of the amine terminal group-containing polyimide adhesive composition is preferably in the range of 0.03 to 10, more preferably in the range of 0.05 to 8.0. If the amine value is smaller than 0.03, there are few amine groups in the terminal group and the adhesive property with the chip insulating polymer film is lowered. If the amine value is larger than 10, the insulating property of the adhesive is lowered. appear.

  The amine value was determined by adding 50 mL of DMSO to 2 g of a polyimide sample, dissolving it, using a 0.1% solution of bromcresol green, and 0.1 mg hydrochloric acid as a titrant, in mg of equivalent potassium hydroxide. displayed.

  In addition, the polyimide adhesive composition of the present invention is polymerized by containing any one selected from 3) a polyamino compound and 4) a diamine, a triamine or a tetraamine containing a siloxane structure.

  As the 3) polyamino compound used in the present invention, a triamino compound represented by the following chemical formula 1 or a tetraamino compound represented by the following chemical formula 2 is preferably used. In the case of the polyamino compound used in the polyimide synthesis of the present invention, Has a role to increase the fluidity during high temperature process by forming a three-dimensional network structure of polyimide and increasing the free volume of molecular units between main chains compared to the structure of polyimide with a linear structure. At the same time, it plays a role of improving high temperature processability and reliability by improving heat resistance characteristics.

  The polyamino compound is preferably used in an amount of 0.01 to 5 mol% based on the aromatic dianhydride used in the polymerization of the present invention. If the polyamino compound is used in an amount of less than 0.01 mol%, it is difficult to expect three-dimensional network characteristics. If the polyamino compound is used in an amount of more than 5 mol%, a problem due to gelation tends to occur during polymerization. The high temperature flow characteristics and adhesive strength of the adhesive are reduced.

式中、Ａ１は３価の作用基、Ａ２は４価の作用基、ｎ１は０または１〜３の整数、ｎ２は０または１〜４の整数、Ｘは酸、ｑは酸の塩基数をそれぞれ示す。

In the formula, A1 is a trivalent functional group, A2 is a tetravalent functional group, n1 is an integer of 0 or 1-3, n2 is an integer of 0 or 1-4, X is an acid, and q is the number of bases of the acid. Each is shown.

  As an example of A1, it is preferable to select and use from the compound of the following chemical formula 3.

Ａ２の一例としては下記化学式４の化合物から選択して使用することが好ましい。

As an example of A2, it is preferable to select and use from the compound of the following chemical formula 4.

式中、Ｒは−Ｏ−、−ＣＨ₂−、−ＣＯ−または−ＳＯ₂−を示し、ｎ３は０または１を示す。
本発明で使用される多官能ポリアミノの具体的な化合物の一例としては、３，３'，４，４'−テトラアミノジフェニルエーテル、３，３’，４，４’−テトラアミノジフェニルメタン、３，３’，４，４’−テトラアミノベンゾフェノン、３，３’，４，４’−テトラアミノジフェニルスルホン、３，３’，４，４’−テトラアミノビフェニル、１，２，４，５−テトラアミノベンゼン、３，３’，４−トリアミノジフェニル、３，３’，４−トリアミノジフェニルメタン、３，３’，４−トリアミノベンゾフェノン、３，３’，４−トリアミノジフェニルスルホン、３，３’，４−トリアミノジビフェニルおよび１，２，４−トリアミノベンゼンからなる化合物、または前記化合物のモノ−、ジ−、トリ−またはテトラ−酸塩である３，３’，４，４’−テトラアミノジフェニルエーテルテトラヒドロクロライド、３，３’，４，４’−テトラアミノジフェニルメタンテトラヒドロクロライド、３，３’，４，４’−テトラアミノベンゾフェノンテトラヒドロクロライド、３，３’，４，４’−テトラアミノジフェニルスルホンテトラヒドロクロライド、３，３’，４，４’−テトラアミノビフェニルテトラヒドロクロライド、１，２，４，５−テトラアミノベンゼンテトラヒドロクロライド、３，３’，４−トリアミノジフェニルトリヒドロクロライド、３，３’，４−トリアミノジフェニルメタントリヒドロクロライド、３，３’，４−トリアミノベンゾフェノントリヒドロクロライド、３，３’，４−トリアミノジフェニルスルホントリヒドロクロライド、３，３’，４−トリアミノジビフェニルトリヒドロクロライドおよび１，２，４−トリアミノベンゼンジヒドロクロライドからなる群より選択されたいずれか１種または２種以上の混合物を使用することが好ましい。さらに好ましくは、前記多官能ポリアミノ化合物の中でも、塩添加物の形になっていない化合物を使用する。この場合、反応の際にゲル化を形成する速度が短縮されるので、３次元ネットワーク構造を形成させるとき、ゲル化の速度調節に応じて塩添加物タイプの化合物を併用して割合を調節することができる。この際、３次元ネットワーク構造を形成すると、ポリイミド主鎖間の結合を成して耐熱性が増大する。

In the formula, R represents —O—, —CH ₂ —, —CO— or —SO ₂ —, and n3 represents 0 or 1.
Examples of specific compounds of polyfunctional polyamino used in the present invention include 3,3 ′, 4,4′-tetraaminodiphenyl ether, 3,3 ′, 4,4′-tetraaminodiphenylmethane, 3,3 ', 4,4'-tetraaminobenzophenone, 3,3', 4,4'-tetraaminodiphenyl sulfone, 3,3 ', 4,4'-tetraaminobiphenyl, 1,2,4,5-tetraamino Benzene, 3,3 ′, 4-triaminodiphenyl, 3,3 ′, 4-triaminodiphenylmethane, 3,3 ′, 4-triaminobenzophenone, 3,3 ′, 4-triaminodiphenylsulfone, 3,3 3,3 ', 4,4' which is a compound consisting of ', 4-triaminodibiphenyl and 1,2,4-triaminobenzene or a mono-, di-, tri- or tetra-acid salt of said compound -Tetra Minodiphenyl ether tetrahydrochloride, 3,3 ′, 4,4′-tetraaminodiphenylmethane tetrahydrochloride, 3,3 ′, 4,4′-tetraaminobenzophenone tetrahydrochloride, 3,3 ′, 4,4′-tetraaminodiphenyl Sulfonetetrahydrochloride, 3,3 ′, 4,4′-tetraaminobiphenyltetrahydrochloride, 1,2,4,5-tetraaminobenzenetetrahydrochloride, 3,3 ′, 4-triaminodiphenyltrihydrochloride, 3, 3 ', 4-triaminodiphenylmethane trihydrochloride, 3,3', 4-triaminobenzophenone trihydrochloride, 3,3 ', 4-triaminodiphenylsulfone trihydrochloride, 3,3', 4-triamino Dibiphenyl trihydrochlora It is preferred to use any one or a mixture of two or more selected from the De and 1,2,4-triaminobenzene dihydrochloride group consisting ride. More preferably, among the polyfunctional polyamino compounds, compounds not in the form of salt additives are used. In this case, the rate at which gelation is formed during the reaction is shortened. Therefore, when a three-dimensional network structure is formed, the ratio is adjusted by using a salt additive type compound in combination according to the gelation rate adjustment. be able to. At this time, if a three-dimensional network structure is formed, bonds between polyimide main chains are formed and heat resistance is increased.

  4) Any one selected from diamines containing a siloxane structure, triamines or tetraamines used in the present invention can be used, and preferably a diamine containing a siloxane structure of the following chemical formula 5 is used.

式中、Ｒ４は炭素数１〜２０のアルキル基を含有するアミンを示し、ｎ’は１〜２０の整数を示す。

In the formula, R4 represents an amine containing an alkyl group having 1 to 20 carbon atoms, and n ′ represents an integer of 1 to 20.

  Among the polyimide adhesive compositions of the present invention, a diamine containing a siloxane structure gives flexibility to the rigid structure of the polyimide, and the flexibility of the polymer is insufficient due to the three-dimensional whatwork molecular structure by gelation. It complements the drawbacks and prevents the deterioration of the mechanical properties of the three-dimensional structure polyimide. In addition, the solubility in polyimide can be increased to increase the content of reactants in the organic solvent during polyamic acid polymerization, and the adhesive strength to various substrates when used in adhesive applications. It plays a role to increase. In particular, when applied as a use of electronic materials, there is an effect that the adhesive properties with a substrate such as a silicon chip, a chip insulating film, and a lead frame are improved.

  As an example of a specific compound of a diamine containing a siloxane structure used in the present invention, bis (γ-aminopropyl) tetramethyldisiloxane (GAPD, n = 1), bis (γ-aminopropyl) polydimethyldi There are siloxane (PSX-4, n = 4), bis (γ-aminopropyl) polydimethyldisiloxane (PSX-8, n = 8), etc., and the diamine containing a siloxane structure is one kind or a mixture of two or more kinds. Can be used.

  The polyimide adhesive composition of the present invention further includes at least one selected from the group consisting of epoxy resin, bismaleimide resin and rubber resin during polyimide polymerization. It is characterized by being a hybrid type of functional resin.

  As an example that can be used as an epoxy resin, there are bisphenol A, F type, phenol novolac type, cresol novolac type, etc., and the content of epoxy resin is preferably in the range of 0.5 to 50 parts by weight with respect to 100 parts by weight of polyimide. More preferably, it is 1-10 weight part.

  As preferable examples of the bismaleimide resin, 4,4′-bis (3-maleimidophenoxy) diphenyl ether, 4,4′-bis (3-maleimidophenoxy) benzophenone, 4,4′-bis (3-maleimidophenoxy) Diphenyl sulfide, 4,4′-bis (3-maleimidophenoxy) diphenylsulfone, 2,2′-bis (p-maleimidophenoxyphenyl) propane, bis (4-maleimido-2,5-dimethylphenyl) methane, bis ( 4-maleimido-2,5-diethylphenyl) methane, bis (4-maleimido-2,5-dipropylphenyl) methane, bis (4-maleimido-2,5-diisopropylphenyl) methane, bis (4-maleimido- 2,5-dibutylphenyl) methane, bis (4-maleimido-2-methyl) 5-ethylphenyl) methane, bis (4-maleimido-2,5-dimethoxyphenyl) methane, bis (4-maleimido-2,5-diethoxyphenyl) methane, bis (4-maleimido-2,5-dipropoxy) Phenyl) methane, bis (4-maleimido-2,5-diisopropoxyphenyl) methane, bis (4-maleimido-2,5-dibutoxyphenyl) methane and bis (4-maleimido-2-methoxy-5-ethoxy) Any one or a mixture of two or more selected from the group consisting of (phenyl) methane can be used. In this case, the content of the bismaleimide resin is preferably in the range of 3 to 3000 parts by weight, and more preferably 1 to 300 parts by weight with respect to 100 parts by weight of the polyimide.

  As the rubber resin, acrylonitrile butadiene rubber can be used, and the content of the rubber resin with respect to 100 parts by weight of polyimide is preferably in the range of 0.5 to 30 parts by weight, and more preferably 1 to 5 parts by weight. .

  In addition to this, an additive that can be used in polyimide polymerization can be additionally added. The additive can be selected according to suitable temperature conditions, moisture content, purity of reactants and reaction solvent and reaction time required for polymerization. Examples thereof include an epoxy resin curing agent, a curing accelerator, a filler, and a silane coupling agent. And surfactants can be used.

  As an example of the epoxy resin curing agent, a phenol curing agent, a phenoxy resin, or an amine curing agent can be used, and the content of the epoxy resin curing agent with respect to 100 parts by weight of polyimide is preferably 0.5 to 30 parts by weight. Preferably it is 1-7 weight part.

  Further, as other additives, a curing accelerator can be used to shorten the curing time and adjust the curing system according to the application, and as a suitable example, imidazole, tertiary amine and the like can be used. . A suitable use amount can be selected within a range that does not cause a problem that the temporal stability of the adhesive is lowered.

  The filler preferably has a particle size of 3 μm or less. Specifically, the filler is selected from the group consisting of ceramic powder, glass powder, silver powder, copper powder, resin powder and gum powder. Use parts by weight.

  Silane coupling agents can also be mixed to increase the adhesive properties between the adhesive and other interfaces, examples of which include vinyl silane, vinyl triethoxy silane, vinyl trimethoxy silane, Y-methacrylate. Rooxypropyltrimethoxysilane, epoxysilane, Y-glycidoxypropyltrimethoxysilane, Y-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, aminosilane, γ- There are aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, mercaptosilane, γ-mercaptopropyltrimethoxysilane, etc., as well as titanate, aluminum chelate, zircoaluminum. Nate etc. can be used.

  In addition, a normal surfactant can be added to increase the compatibility between the polyimide resin and the other resin.

  In order to produce the polyimide-based adhesive composition of the present invention, a low-boiling solvent that can be dried at a temperature lower than the curing temperature is particularly preferred in the case of a hybrid type containing a thermosetting resin such as an epoxy resin. At this time, tetrahydrofuran (THF), methyl ethyl ketone (MEK) and toluene (Toluene) are preferable as the low boiling point solvent. If the boiling point of the solvent is equal to or higher than the curing temperature, the adhesive layer cures as the drying temperature is increased in order to remove the solvent, causing a problem that various physical properties such as stability with time change.

  The polyimide-based adhesive composition of the present invention becomes a polyamic acid that is a precursor of a heat-resistant adhesive after the coating process on the base film, and is converted into polyimide by heat treatment.

  In this case, the heat treatment temperature when the polyamic acid precursor solution is applied as an adhesive must be lower than the glass transition temperature of the polyimide for thermal imidization, and the polyimide solution is applied as an adhesive. The heat treatment temperature may be a temperature at which the solvent can be simply removed.

  Moreover, after an adhesive bond layer is formed on a base film, it is preferable to heat-process at 250 degreeC or more for 1 to 30 minutes in order to increase the interface adhesiveness between a base film and an adhesive bond layer. At this time, the thickness of the adhesive layer is preferably 5 to 50 μm, and more preferably 10 to 30 μm.

  The base film used in the present invention is not particularly limited as long as it is a heat-resistant engineering plastic film such as polyimide, polyamide, polysulfone, polyphenylene sulfide, polyarylate, polyethersulfone, and more preferably a polyimide film. Is used.

  Examples of polyimide films include Regulus (Mitsui Toatsu Chemicals, Inc.), Kapton (Du Pont Co.), Upilex (Ube Industries, Ltd.), Apical AH, NPI, HP (Kanegafuchi Chemical Industry Co., Ltd.), etc. A preferred thickness is 5 to 150 μm, and more preferably 20 to 125 μm.

  It is preferable that the glass transition temperature of a base film is higher than the glass transition temperature of the adhesive layer used by this invention, More preferably, it is 150 degreeC or more. Further, the moisture content of the base film is preferably 3% or less, and more preferably 2% or less.

Therefore, a suitable base film suitable for the present invention is required to have a high glass transition temperature, a low moisture content, and a low coefficient of thermal expansion. Particularly, the glass transition temperature is higher than 300 ° C. and the moisture content is 2%. The coefficient of thermal expansion is preferably 3 × 10 ⁻⁵ / ° C. or less.

  In the present invention, an adhesive layer is formed by applying an acid terminal group-containing polyimide adhesive composition on one surface of a polyimide base film having a glass transition temperature of 300 ° C. or more and a thickness of 5 to 150 μm, A polyimide adhesive composition containing an amine end group is applied to the other surface of the polyimide base film to form an adhesive layer, and each of the adhesive layers is applied to the polyimide base film at a high temperature of 150 to 350 ° C. A method of manufacturing a double-sided tape for LOC by depositing between 0.001 and 1 second is provided.

  In order to increase the adhesive force between the base film and the adhesive layer, it is also preferable to surface-treat the base film. For this reason, a known method can be used as the surface treatment method, and examples thereof include a chemical surface treatment method of alkali treatment or silane coupling treatment, sand blasting, plasma, corona treatment, etc. The physical surface treatment method can be selected and used, and one or more methods can be applied as necessary. More preferably, chemical treatment or plasma treatment methods are used.

  The method for forming the adhesive layer on the base film is not particularly limited, and an example thereof is a method of applying an adhesive solution to the base film and then drying it to remove the solvent. In addition, a doctor blade, a knife coater, a dry coater, or the like, or a method of immersing a base film in an adhesive solution can be used.

  Hereinafter, the present invention will be described in more detail with reference to examples.

  The following examples are provided to illustrate the present invention more specifically and are not intended to limit the scope of the present invention.

<Example 1> Production 1 of polyimide composite film
Step 1: Polyimide liquid polymerized by adding an excess amount of dianhydride A N-methyl-2-pyrrolidone was added to a reactor equipped with a stirrer and a nitrogen gas inlet. Then, 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride (2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride) was added to the container. 3,4′-oxydianiline, bis (γ-aminopropyl) tetramethyldisiloxane, and 3,3 ′, 4,4′-tetraamino Diphenyl ether (3,3 ', 4,4'-tetraaminodiphenylether) was added at 50.5 mol%: 44.6 mol%: 3.7 mol%: 1.2 mol% and stirred vigorously, concentration 20 weight A solution containing% polyamic acid was prepared. Thereafter, 2% by weight of p-toluenesulfonic acid was added to the solution to raise the polymerization temperature to 180 ° C. and imidized for about 8 hours to prepare an imide solution.

  The imide solution is precipitated in methanol and dried to obtain an imide solid, which is further dissolved in N-methyl-2-pyrrolidone and has a viscosity of about 5,000 poise at a concentration of 20% by weight and 25 ° C. The viscous liquid polyimide solution shown was produced.

Step 2: Polyimide solution prepared by polymerization by adding an excessive amount of diamine N-methyl-2-pyrrolidone was added to a reactor equipped with a stirrer and a nitrogen gas inlet. Thereafter, 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 3,4'-oxydianiline, bis (γ-aminopropyl) tetramethyldisiloxane, And 3,3 ′, 4,4′-tetraaminodiphenyl ether at 49.5 mol%: 44.6 mol%: 4.7 mol%: 1.2 mol% and stirred vigorously to a concentration of 20 wt% A solution containing the polyamic acid was prepared. Thereafter, 2% by weight of p-toluenesulfonic acid was added to the solution to raise the polymerization temperature to 180 ° C. and imidized for about 8 hours to prepare an imide solution.

  The imide solution is precipitated in methanol and dried to obtain an imide solid, which is further dissolved in N-methyl-2-pyrrolidone and has a viscosity of about 4,500 poise at a concentration of 20% by weight and 25 ° C. The viscous liquid polyimide solution shown was produced.

Step 3: Manufacture of double-sided tape After applying the polyimide solution prepared by adding an excessive amount of dianhydride in Step 1 on a polyimide film having a thickness of 25 μm, 130 ° C. for 3 minutes at 100 ° C. 4 minutes at 150 ° C, 5 minutes at 150 ° C and 5 minutes at 200 ° C to remove the solvent, and finally heat treatment at 300 ° C for 5 minutes to produce a 12.5 µm thick thermoplastic polyimide adhesive layer did.

  Using a knife coater on the opposite side of the polyimide film, after applying a polyimide solution prepared by adding an excessive amount of diamine in the step 2, it is 3 minutes at 100 ° C, 4 minutes at 130 ° C, and 5 minutes at 150 ° C. And after pre-drying at 200 ° C. for 5 minutes to remove the solvent and finally heat-treating at 300 ° C. for 5 minutes to form a 12.5 μm-thick thermoplastic polyimide adhesive layer to produce a polyimide composite film .

<Example 2> Production 2 of polyimide composite film
Step 1: Polyimide solution prepared by adding dianhydride in excess amount N-methyl-2-pyrrolidone was added to a reactor equipped with a stirrer and a nitrogen gas inlet. Then, 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride (2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride) was added to the container. 2,2-bis (4- [3-aminophenoxy] phenyl) sulfone [2,2-bis (4- [3-aminophenoxy] phenyl) sulfone], bis (γ-aminopropyl) tetramethyldisiloxane [Bis ( γ-aminopropyl) tetramethyldisiloxane], and 3,3 ′, 4,4′-tetraaminodiphenylether (5,3 ′, 4,4′-tetraaminodiphenylether) 50.1 mol%: 43.9 mol%: 5.0 Mol%: 1.0 mol% was charged and stirred vigorously to prepare a solution containing polyamic acid having a concentration of 20% by weight. Thereafter, 2% by weight of p-toluenesulfonic acid was added to the solution to raise the polymerization temperature to 180 ° C. and imidized for about 8 hours to prepare an imide solution.

  The imide solution is precipitated in methanol and dried to obtain an imide solid, which is further dissolved in N-methyl-2-pyrrolidone and has a viscosity of about 4,000 poise at a concentration of 20% by weight and 25 ° C. The viscous liquid polyimide solution shown was produced.

Step 2: Polyimide solution prepared by polymerization by adding an excessive amount of diamine N-methyl-2-pyrrolidone was added to a reactor equipped with a stirrer and a nitrogen gas inlet. Thereafter, 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 2,2-bis (4- [3-aminophenoxy] phenyl) sulfone, bis (γ -Aminopropyl) tetramethyldisiloxane and 3,3 ′, 4,4′-tetraaminodiphenyl ether were charged at 49.9 mol%: 43.9 mol%: 5.2 mol%: 1.0 mol%. The solution was vigorously stirred to produce a solution containing polyamic acid having a concentration of 20% by weight. Thereafter, 2% by weight of p-toluenesulfonic acid was added to the solution to raise the polymerization temperature to 180 ° C. and imidized for about 8 hours to prepare an imide solution.

  The imide solution is precipitated in methanol and dried to obtain an imide solid, which is further dissolved in N-methyl-2-pyrrolidone and has a viscosity of about 3,000 poise at a concentration of 20% by weight and 25 ° C. The viscous liquid polyimide solution shown was produced.

Step 3: Manufacture of double-sided tape The same procedure as in Example 1 was performed except that the polyimide adhesive solution prepared in Step 1 and Step 2 was applied to each surface of a polyimide film having a thickness of 25 μm. A polyimide composite film was produced.

<Example 3> Production 3 of polyimide composite film
Step 1: Polyimide solution prepared by adding dianhydride in excess amount N-methyl-2-pyrrolidone was added to a reactor equipped with a stirrer and a nitrogen gas inlet. Then, 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride (2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride) was added to the container. Bis (4- [4-aminophenoxy] phenyl) ether [Bis (4- [4-aminophenoxy] phenyl) ether], bis (γ-aminopropyl) tetramethyldisiloxane [Bis (γ-aminopropyl) tetramethyldisiloxane], and 3,3 ′, 4,4′-tetraaminodiphenyl ether (3,3 ′, 4,4′-tetraaminodiphenylether) 51.5 mol%: 41.3 mol%: 6.3 mol%: 0.9 mol% And stirred vigorously to prepare a solution containing polyamic acid having a concentration of 20% by weight. Thereafter, 2% by weight of p-toluenesulfonic acid was added to the solution to raise the polymerization temperature to 180 ° C. and imidized for about 8 hours to prepare an imide solution.

  The imide solution is precipitated in methanol and dried to obtain an imide solid, which is further dissolved in N-methyl-2-pyrrolidone and has a viscosity of about 4,000 poise at a concentration of 20% by weight and 25 ° C. The viscous liquid polyimide solution shown was produced.

Step 2: Polyimide solution prepared by polymerization by adding an excessive amount of diamine N-methyl-2-pyrrolidone was added to a reactor equipped with a stirrer and a nitrogen gas inlet. Thereafter, 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride, bis (4- [4-aminophenoxy] phenyl) ether, bis (γ-aminopropyl) was added to the container. Tetramethyldisiloxane and 3,3 ′, 4,4′-tetraaminodiphenyl ether were charged at 48.5 mol%: 42.7 mol%: 7.8 mol%: 1.0 mol% and stirred vigorously. A solution containing a polyamic acid with a concentration of 20% by weight was prepared. Thereafter, 2% by weight of p-toluenesulfonic acid was added to the solution to raise the polymerization temperature to 180 ° C. and imidized for about 8 hours to prepare an imide solution.

  The imide solution is precipitated in methanol and dried to obtain an imide solid, which is further dissolved in N-methyl-2-pyrrolidone to give a viscosity of about 3,500 poise at a concentration of 20% by weight and 25 ° C. The viscous liquid polyimide solution shown was produced.

Step 3: Manufacture of double-sided tape The same procedure as in Example 1 was performed except that the polyimide adhesive solution prepared in Step 1 and Step 2 was applied to each surface of a polyimide film having a thickness of 25 μm. A polyimide composite film was produced.

<Comparative Example 1>
A polyimide adhesive solution prepared by polymerization by adding an excessive amount of the dianhydride prepared in Step 1 of Example 1 above is coated on both sides of a polyimide film having a thickness of 25 μm, and each adhesive has a thickness of 12.5 μm. A polyimide composite film in which layers were laminated was produced.

<Comparative example 2>
A polyimide adhesive solution prepared by polymerization by adding an excessive amount of the diamine prepared in Step 2 of Example 1 was coated on both surfaces of a polyimide film having a thickness of 25 μm, and each adhesive layer was formed to a thickness of 12.5 μm. A polyimide composite film was manufactured.

<Comparative Example 3>
A polyimide adhesive solution prepared by polymerization by adding an excessive amount of the diamine prepared in Step 2 of Example 2 above is coated on both sides of a polyimide film having a thickness of 25 μm, and each adhesive layer has a thickness of 12.5 μm. A polyimide composite film was manufactured.

<Experimental example 1>
The physical properties of the polyimide composite films produced in Examples 1 to 3 and Comparative Examples 1 to 3 were measured as follows.

1. Glass transition temperature The glass transition temperature was measured using DSC (Differential Scanning Calorimetry) for the polyimide composite films produced in Examples 1-3 and Comparative Examples 1-3. At this time, the heating rate was measured in the temperature range of 10 ° C./min and 50 to 300 ° C. and shown in the following table.

2.5% Pyrolysis Temperature The polyimide composite films produced in Examples 1-3 and Comparative Examples 1-3 were measured for 5% pyrolysis temperature using TGA (Thermogravimetry Analysis). At this time, the heating rate was measured in the temperature range of 10 ° C./min and 50 to 900 ° C., and the results were shown in the following tables. The 5% pyrolysis temperature originally indicates the temperature at which the weight is relatively decreased by 5% with respect to the mass as 100%.

3. Elastic Modulus The elastic modulus was measured using DMTA (Dynamic Mechanical Thermal Analysis) for the polyimide composite films produced in Examples 1-3 and Comparative Examples 1-3. Under the present circumstances, the elastic modulus value in 25 degreeC and 190 degreeC was shown in each table | surface as measured in the temperature range of 50-250 degreeC on the conditions of 1 Hz and the temperature increase rate of 5 degreeC / min.

4). Moisture absorption rate The polyimide adhesive solutions produced in Examples 1 to 3 and Comparative Examples 1 to 3 were applied to a peeled glass plate so that the thickness after drying was 60 μm, and a hot-air circulating drier After producing an adhesive sheet by drying at 100 ° C., 130 ° C., 150 ° C., 180 ° C., 210 ° C., 250 ° C. for 5 minutes for each temperature, the adhesive layer is separated from the glass plate, and the moisture absorption rate of the adhesive layer Used as an evaluation sample. The moisture absorption rate evaluation sample of 5 cm × 5 cm was prepared, and a moisture absorption rate evaluation experiment was performed using a constant temperature and humidity oven at a temperature of 121 ° C., a humidity of 100% RH, and a time of 24 hours. Under the present circumstances, the moisture absorption rate was computed from following Numerical formula 1.

(Formula 1)
Moisture absorption rate (%) = [(sample weight after moisture absorption−sample weight before moisture absorption) / sample weight before moisture absorption] × 100

5. Electrical reliability The polyimide adhesive solutions produced in Examples 1 to 3 and Comparative Examples 1 to 3 were applied onto a glass plate that had been subjected to a release treatment so that the thickness after drying was 25 μm, and the hot air circulation type After producing an adhesive sheet by drying at 100 ° C., 130 ° C., 150 ° C., 180 ° C., 210 ° C., 250 ° C. for 5 minutes for each temperature in the dryer, the adhesive layer is separated from the glass plate, and the adhesive layer It was used as an electrical reliability evaluation sample.

  On the other hand, a comb-like circuit having a conductor / conductor distance of 50 μm / 50 μm was manufactured from a metal lead frame made of an alloy 42 material made of nickel-iron alloy. The adhesive sheet was adhesively bonded onto the prepared circuit to prepare an electrical reliability evaluation sample.

  At this time, the evaluation sample was placed for 300 hours while applying a DC voltage of 5 V to the comb-like circuit in a constant temperature and humidity oven adjusted to a temperature of 130 ° C. and a humidity of 85% RH. Thereafter, the comb-like circuit state was evaluated. The results are shown in each table. In the table, “x” indicates a case where migration occurs in the comb-like circuit (copper foil portion), and “◯” indicates a case where migration does not occur.

6). Adhesive strength The polyimide composite films produced in Examples 1 to 3 and Comparative Examples 1 to 3 were either a nickel iron alloy plate or a PIX-3000 solution (Hitachi Chemical Co., Ltd.) at 300 ° C. and 350 ° C. under a pressure of 5 kg / cm ^2. ) Was adhered on the coated plate, and then the T-Peel test was conducted at room temperature at a speed of 50 mm / min to evaluate the adhesive force. The results are shown in the following table.

7). Thermal cycle test The polyimide adhesive solutions prepared in Examples 1 to 3 and Comparative Examples 1 to 3 were coated on both sides of a polyimide film having a thickness of 50 μm so that the thickness of each adhesive layer was 25 μm. An adhesive tape having the structure described above was manufactured.

Thereafter, one surface of the adhesive tape was thermocompression bonded to a nickel iron alloy plate having a thickness of 200 μm and a size of 2.5 cm × 2.5 cm at a temperature of 300 ° C. and a pressure of 5 kg / cm ² . Next, the opposite surface of the double-sided adhesive tape was thermocompression bonded to a glass chip coated with a 2.5 cm × 2.5 cm PIX-3000 solution (Hitachi Chemical) at a temperature of 300 ° C. and a pressure of 5 kg / cm ² . Used as a sample for thermal cycle test.

  A thermal cycle test of −65 ° C. to 150 ° C. was performed using the evaluation sample. At this time, the thermal cycle test was performed under the conditions of 1000 cycles, with each cycle of 30 minutes at 150 ° C. and −65 ° C. as one cycle. After the thermal cycle test, the presence or absence of peeling and foaming was observed, and the results are shown in the following tables.

  Table 1 below shows the results of physical properties for the polyimide composite films produced in Examples 1-3 and Comparative Examples 1-3.

  As can be seen from Table 1, the adhesion characteristics of the polyimide composite films produced in Examples 1 to 3 showed excellent adhesion characteristics at the same time for nickel iron alloy metals and PIX insulating film plastics. On the other hand, in the case of the composite film of Comparative Example 1, the adhesion characteristics with the nickel-iron alloy metals were excellent, but the adhesion characteristics with the PIX insulating film plastics were not good. Although this composite film was excellent in the adhesive properties of the PIX insulating film with the plastic, it showed poor results in the adhesive properties of the nickel iron alloy with metals.

<Example 4> Production 4 of polyimide composite film
Step 1: Polyimide liquid polymerized by adding an excess amount of dianhydride A N-methyl-2-pyrrolidone was added to a reactor equipped with a stirrer and a nitrogen gas inlet. Thereafter, 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] sulfone dianhydride (2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] sulfone dianhydride) was added to the container. 3,4′-oxydianiline, bis (γ-aminopropyl) tetramethyldisiloxane, and 3,3 ′, 4-triaminodiphenyl (3 , 3 ', 4-triaminodiphenyl) at 50.5 mol%: 44.6 mol%: 4.2 mol%: 0.7 mol% and stirred vigorously, containing polyamic acid with a concentration of 20 wt% A solution was prepared. Thereafter, 2% by weight of p-toluenesulfonic acid was added to the solution to raise the polymerization temperature to 180 ° C. and imidized for about 8 hours to prepare an imide solution.

  The imide solution is precipitated in methanol and dried to obtain an imide solid, which is further dissolved in N-methyl-2-pyrrolidone and has a viscosity of about 4,000 poise at a concentration of 20% by weight and 25 ° C. The viscous liquid polyimide solution shown was produced.

Step 2: Polyimide solution prepared by polymerization by adding an excessive amount of diamine N-methyl-2-pyrrolidone was added to a reactor equipped with a stirrer and a nitrogen gas inlet. Thereafter, 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] sulfone dianhydride, 3,4'-oxydianiline, bis (γ-aminopropyl) tetramethyldisiloxane, And 3,3 ′, 4-triaminodiphenyl at 49.5 mol%: 45.0 mol%: 4.7 mol%: 0.8 mol% and stirred vigorously to a polyamic acid having a concentration of 20 wt% A solution containing was prepared. Thereafter, 2% by weight of p-toluenesulfonic acid was added to the solution to raise the polymerization temperature to 180 ° C. and imidized for about 8 hours to prepare an imide solution.

  The imide solution was precipitated in methanol and dried to obtain an imide solid, which was further dissolved in N-methyl-2-pyrrolidone to give a viscosity of about 3,000 poise at a concentration of 20% by weight and 25 ° C. The viscous liquid polyimide solution shown was produced.

Step 3: Manufacture of double-sided tape The same procedure as in Example 1 was performed except that the polyimide adhesive solution prepared in Step 1 and Step 2 was applied to each surface of a polyimide film having a thickness of 25 μm. A polyimide composite film was produced.

<Example 5> Production 5 of polyimide composite film
Step 1: Polyimide solution prepared by adding dianhydride in excess amount N-methyl-2-pyrrolidone was added to a reactor equipped with a stirrer and a nitrogen gas inlet. Thereafter, 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] sulfone dianhydride, 2,2-bis (4- [3-aminophenoxy] phenyl) sulfone, bis (γ -Aminopropyl) tetramethyldisiloxane and 3,3 ', 4-triaminodiphenyl were charged at 51.3 mol%: 41.4 mol%: 6.8 mol%: 0.5 mol% and stirred vigorously. Thus, a solution containing polyamic acid having a concentration of 20% by weight was produced. Thereafter, 2% by weight of p-toluenesulfonic acid was added to the solution to raise the polymerization temperature to 180 ° C. and imidized for about 8 hours to prepare an imide solution.

  The imide solution is precipitated in methanol and dried to obtain an imide solid, which is further dissolved in N-methyl-2-pyrrolidone to give a viscosity of about 3,500 poise at a concentration of 20% by weight and 25 ° C. The viscous liquid polyimide solution shown was produced.

Step 2: N-methyl-2-pyrrolidone was added to a reaction vessel equipped with a polyimide liquid stirrer and a nitrogen gas inlet produced by adding an excessive amount of diamine. Thereafter, 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] sulfone dianhydride, 2,2-bis (4- [3-aminophenoxy] phenyl) sulfone, bis (γ -Aminopropyl) tetramethyldisiloxane and 3,3 ', 4-triaminodiphenyl were charged at 48.6 mol%: 43.1 mol%: 7.8 mol%: 0.5 mol% and stirred vigorously. Thus, a solution containing polyamic acid having a concentration of 20% by weight was produced. Thereafter, 2% by weight of p-toluenesulfonic acid was added to the solution to raise the polymerization temperature to 180 ° C. and imidized for about 8 hours to prepare an imide solution.

  The imide solution was precipitated in methanol and dried to obtain an imide solid, which was further dissolved in N-methyl-2-pyrrolidone to give a viscosity of about 3,000 poise at a concentration of 20% by weight and 25 ° C. The viscous liquid polyimide solution shown was produced.

Step 3: Manufacture of double-sided tape The same procedure as in Example 1 was performed except that the polyimide adhesive solution prepared in Step 1 and Step 2 was applied to each surface of a polyimide film having a thickness of 25 μm. A polyimide composite film was produced.

<Example 6> Production of polyimide composite film 6
Step 1: Polyimide solution prepared by adding dianhydride in excess amount N-methyl-2-pyrrolidone was added to a reactor equipped with a stirrer and a nitrogen gas inlet. Thereafter, 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] sulfone dianhydride, bis (4- [4-aminophenoxy] phenyl) ether, bis (γ-aminopropyl) was added to the container. Tetramethyldisiloxane and 3,3 ′, 4-triaminodiphenyl were charged at 50.2 mol%: 46.3 mol%: 2.7 mol%: 0.8 mol% and stirred vigorously to obtain a concentration of 20 A solution containing wt% polyamic acid was prepared. Thereafter, 2% by weight of p-toluenesulfonic acid was added to the solution to raise the polymerization temperature to 180 ° C. and imidized for about 8 hours to prepare an imide solution.

  The imide solution is precipitated in methanol and dried to obtain an imide solid, which is further dissolved in N-methyl-2-pyrrolidone to give a viscosity of about 3,500 poise at a concentration of 20% by weight and 25 ° C. The viscous liquid polyimide solution shown was produced.

Step 2: Polyimide solution prepared by polymerization by adding an excessive amount of diamine N-methyl-2-pyrrolidone was added to a reactor equipped with a stirrer and a nitrogen gas inlet. Thereafter, 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] sulfone dianhydride, bis (4- [4-aminophenoxy] phenyl) ether, bis (γ-aminopropyl) was added to the container. Tetramethyldisiloxane and 3,3 ′, 4-triaminodiphenyl were charged at 49.8 mol%: 46.7 mol%: 2.7 mol%: 0.8 mol% and stirred vigorously to obtain a concentration of 20 A solution containing wt% polyamic acid was prepared. Thereafter, 2% by weight of p-toluenesulfonic acid was added to the solution to raise the polymerization temperature to 180 ° C. and imidized for about 8 hours to prepare an imide solution.

  The imide solution is precipitated in methanol and dried to obtain an imide solid, which is further dissolved in N-methyl-2-pyrrolidone and has a viscosity of about 3,000 poise at a concentration of 20% by weight and 25 ° C. The viscous liquid polyimide solution shown was produced.

Step 3: Manufacture of double-sided tape The same procedure as in Example 1 was performed except that the polyimide adhesive solution prepared in Step 1 and Step 2 was applied to each surface of a polyimide film having a thickness of 25 μm. A polyimide composite film was produced.

<Comparative example 4>
The polyimide adhesive solution prepared by polymerizing the dianhydride prepared in Step 1 of Example 4 on both sides of the polyimide film having a thickness of 25 μm was coated, and each adhesive was coated to a thickness of 12.5 μm. A polyimide composite film in which layers were laminated was produced.

<Comparative Example 5>
A polyimide adhesive solution prepared by polymerization by adding an excessive amount of the diamine prepared in Step 2 of Example 4 was coated on both surfaces of a polyimide film having a thickness of 25 μm, and each adhesive layer was formed to a thickness of 12.5 μm. A polyimide composite film was manufactured.

<Comparative Example 6>
A polyimide adhesive solution prepared by polymerization by adding an excessive amount of the diamine prepared in Step 2 of Example 5 was coated on both sides of a polyimide film having a thickness of 25 μm, and an adhesive layer was formed to a thickness of 12.5 μm. A laminated polyimide composite film was produced.

  Table 2 below shows the physical property values for the polyimide composite films produced in Examples 4-6 and Comparative Examples 4-6.

  As can be seen from Table 2, the polyimide composite films produced in Examples 4 to 6 showed excellent adhesion properties to nickel iron alloy metals and PIX insulating film plastics simultaneously. On the other hand, the composite film of Comparative Example 4 is excellent in adhesion properties with nickel-iron alloy metals, but is inferior in adhesion properties with PIX insulating film plastics, and the composite films of Comparative Examples 5-6 are PIX. Although the adhesive properties of the insulating film with plastics were excellent, the results showed that the adhesive properties of nickel iron alloy with metals were not good.

<Example 7> Production of polyimide composite film 7
Step 1: Polyimide solution prepared by adding dianhydride in excess amount N-methyl-2-pyrrolidone was added to a reactor equipped with a stirrer and a nitrogen gas inlet. Thereafter, ethylene glycol bis (anhydrotrimellitate), 4,4-diaminodiphenylsulfone, bis (γ-aminopropyl) tetramethyldisiloxane [ Bis (γ-aminopropyl) tetramethydisiloxane] and 3,3 ′, 4,4′-tetraaminobiphenyl (3,3 ′, 4,4′-tetraaminobiphenyl) in 50.2 mol%: 42.3 mol%: 7 0.0 mol%: 0.5 mol% was charged and stirred vigorously to prepare a solution containing polyamic acid having a concentration of 20 wt%, and then 2 wt% of p-toluenesulfonic acid was added to the solution. The polymerization temperature was raised to 180 ° C. and imidized for about 8 hours to produce an imide solution.

  The imide solution is precipitated in methanol and dried to obtain an imide solid, which is further dissolved in N-methyl-2-pyrrolidone to give a viscosity of about 5,500 poise at a concentration of 20% by weight and 25 ° C. The viscous liquid polyimide solution shown was produced.

Step 2: Polyimide solution prepared by polymerization by adding an excessive amount of diamine N-methyl-2-pyrrolidone was added to a reactor equipped with a stirrer and a nitrogen gas inlet. Thereafter, ethylene glycol bis (anhydrotrimellitate), 4,4-diaminodiphenyl sulfone, bis (γ-aminopropyl) tetramethyldisiloxane, and 3,3 ′, 4,4′-tetraaminobiphenyl are added to the container. Of 49.9 mol%: 42.4 mol%: 7.2 mol%: 0.5 mol% and stirred vigorously to prepare a solution containing polyamic acid having a concentration of 20 wt%. Thereafter, 2% by weight of p-toluenesulfonic acid was added to the solution to raise the polymerization temperature to 180 ° C. and imidized for about 8 hours to prepare an imide solution.

  The imide solution is precipitated in methanol and dried to obtain an imide solid, which is further dissolved in N-methyl-2-pyrrolidone and has a viscosity of about 5,000 poise at a concentration of 20% by weight and 25 ° C. The viscous liquid polyimide solution shown was produced.

Step 3: Manufacture of double-sided tape The same procedure as in Example 1 was performed except that the polyimide adhesive solution prepared in Step 1 and Step 2 was applied to each surface of a polyimide film having a thickness of 25 μm. A polyimide composite film was produced.

<Example 8> Polyimide composite film production 8
Step 1: Polyimide solution prepared by adding dianhydride in excess amount N-methyl-2-pyrrolidone was added to a reactor equipped with a stirrer and a nitrogen gas inlet. Thereafter, ethylene glycol bis (anhydrotrimellitate), 2,2-bis [4- (4-aminophenoxy) phenyl] propane (2,2-bis [4- ( 4-aminophenoxy) phenyl] propane), bis (γ-aminopropyl) tetramethyldisiloxane [Bis (γ-aminopropyl) tetramethydisiloxane], and 3,3 ′, 4,4′-tetraaminobiphenyl (3,3 ′, 4,4'-tetraaminobiphenyl) at 50.6 mol%: 44.4 mol%: 4.2 mol%: 0.8 mol% and stirred vigorously, and containing a polyamic acid with a concentration of 20 wt% Thereafter, 2% by weight of p-toluenesulfonic acid was added to the solution to raise the polymerization temperature to 180 ° C. and imidized for about 8 hours to prepare an imide solution.

  The imide solution is precipitated in methanol and dried to obtain an imide solid, which is further dissolved in N-methyl-2-pyrrolidone and has a viscosity of about 4,500 poise at a concentration of 20% by weight and 25 ° C. The viscous liquid polyimide solution shown was produced.

Step 2: Polyimide solution prepared by polymerization by adding an excessive amount of diamine N-methyl-2-pyrrolidone was added to a reactor equipped with a stirrer and a nitrogen gas inlet. Thereafter, ethylene glycol bis (anhydrotrimellitate), 2,2-bis [4- (4-aminophenoxy) phenyl] propane, bis (γ-aminopropyl) tetramethyldisiloxane, and 3,3 ', 4,4'-tetraaminobiphenyl was charged at 49.4 mol%: 45.4 mol%: 4.4 mol%: 0.8 mol% and stirred vigorously to obtain a polyamic acid having a concentration of 20 wt%. A containing solution was prepared. Thereafter, 2% by weight of p-toluenesulfonic acid was added to the solution to raise the polymerization temperature to 180 ° C. and imidized for about 8 hours to prepare an imide solution.

  The imide solution is precipitated in methanol and dried to obtain an imide solid, which is further dissolved in N-methyl-2-pyrrolidone and has a viscosity of about 4,000 poise at a concentration of 20% by weight and 25 ° C. The viscous liquid polyimide solution shown was produced.

Step 3: Manufacture of double-sided tape The same procedure as in Example 1 was performed except that the polyimide adhesive solution prepared in Step 1 and Step 2 was applied to each surface of a polyimide film having a thickness of 25 μm. A polyimide composite film was produced.

<Example 9> Production 9 of polyimide composite film
Step 1: Polyimide solution prepared by adding dianhydride in excess amount N-methyl-2-pyrrolidone was added to a reactor equipped with a stirrer and a nitrogen gas inlet. Thereafter, ethylene glycol bis (anhydrotrimellitate), 4,4-diaminodiphenylmethane, bis (γ-aminopropyl) tetramethyly disiloxane [Bis (γ-aminopropyl) tetramethydisiloxane] , And 3,3 ′, 4,4′-tetraaminobiphenyl (3,3 ′, 4,4′-tetraaminobiphenyl) 51.2 mol%: 42.9 mol%: 5.1 mol%: 0.8 A solution containing polyamic acid having a concentration of 20% by weight was prepared by charging at a mol% and vigorously stirring, and then 2% by weight of p-toluenesulfonic acid was added to the solution to raise the polymerization temperature to 180 ° C. For about 8 hours to produce an imide solution.

  The imide solution is precipitated in methanol and dried to obtain an imide solid, which is further dissolved in N-methyl-2-pyrrolidone to give a viscosity of about 4,000 poise at a concentration of 20% by weight and 25 ° C. The viscous liquid polyimide solution shown was produced.

Step 2: Polyimide solution prepared by polymerization by adding an excessive amount of diamine N-methyl-2-pyrrolidone was added to a reactor equipped with a stirrer and a nitrogen gas inlet. Thereafter, ethylene glycol bis (anhydrotrimellitate), 4,4-diaminodiphenylmethane, bis (γ-aminopropyl) tetramethyldisiloxane, and 3,3 ′, 4,4′-tetraaminobiphenyl are added to the container. 48.8 mol%: 44.9 mol%: 5.6 mol%: 0.7 mol% was charged and stirred vigorously to prepare a solution containing polyamic acid having a concentration of 20 wt%. Thereafter, 2% by weight of p-toluenesulfonic acid was added to the solution to raise the polymerization temperature to 180 ° C. and imidized for about 8 hours to prepare an imide solution.

  The imide solution is precipitated in methanol and dried to obtain an imide solid, which is further dissolved in N-methyl-2-pyrrolidone to give a viscosity of about 4,000 poise at a concentration of 20% by weight and 25 ° C. The viscous liquid polyimide solution shown was produced.

Step 3: Manufacture of double-sided tape The same procedure as in Example 1 was performed except that the polyimide adhesive solution prepared in Step 1 and Step 2 was applied to each surface of a polyimide film having a thickness of 25 μm. A polyimide composite film was produced.

<Example 10> Production of polyimide composite film 10
Step 1: Polyimide solution prepared by adding dianhydride in excess amount N-methyl-2-pyrrolidone was added to a reactor equipped with a stirrer and a nitrogen gas inlet. Thereafter, ethylene glycol bis (anhydrotrimellitate), 2,2-bis [4- (4-aminophenoxy) phenyl] propane (2,2-bis [4- ( 4-aminophenoxy) phenyl] propane), 4,4'-diaminodiphenylmethane, Bis (γ-aminopropyl) tetramethylydisiloxane, and 3,3 ' , 4,4′-tetraaminobiphenyl (3,3 ′, 4,4′-tetraaminobiphenyl) 51.6 mol%: 24.2 mol%: 19.4 mol%: 4.1 mol%: 0.7 A solution containing polyamic acid having a concentration of 20% by weight was prepared by charging at a mol% and vigorously stirring, and then 2% by weight of p-toluenesulfonic acid was added to the solution to raise the polymerization temperature to 180 ° C. For about 8 hours to produce an imide solution It was.

  The imide solution is precipitated in methanol and dried to obtain an imide solid, which is further dissolved in N-methyl-2-pyrrolidone and has a viscosity of about 4,000 poise at a concentration of 20% by weight and 25 ° C. The viscous liquid polyimide solution shown was produced.

Step 2: Polyimide solution prepared by polymerization by adding an excessive amount of diamine N-methyl-2-pyrrolidone was added to a reactor equipped with a stirrer and a nitrogen gas inlet. Thereafter, ethylene glycol bis (anhydrotrimellitate), 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 4,4-diaminodiphenylmethane, bis (γ-aminopropyl) tetramethyl are added to the container. Disiloxane and 3,3 ′, 4,4′-tetraaminobiphenyl were charged at 48.5 mol%: 25.7 mol%: 20.4 mol%: 4.6 mol%: 0.8 mol%. The solution was vigorously stirred to produce a solution containing polyamic acid having a concentration of 20% by weight. Thereafter, 2% by weight of p-toluenesulfonic acid was added to the solution to raise the polymerization temperature to 180 ° C. and imidized for about 8 hours to prepare an imide solution.

  The imide solution is precipitated in methanol and dried to obtain an imide solid, which is further dissolved in N-methyl-2-pyrrolidone to give a viscosity of about 3,500 poise at a concentration of 20% by weight and 25 ° C. The viscous liquid polyimide solution shown was produced.

Step 3: Manufacture of double-sided tape The same procedure as in Example 1 was performed except that the polyimide adhesive solution prepared in Step 1 and Step 2 was applied to each surface of a polyimide film having a thickness of 25 μm. A polyimide composite film was produced.

  Table 3 below shows the results of physical property values for the polyimide composite films produced in Examples 7-10.

<Comparative Example 7>
Step 1: Polyimide solution prepared by adding dianhydride in excess amount N-methyl-2-pyrrolidone was added to a reactor equipped with a stirrer and a nitrogen gas inlet. Thereafter, ethylene glycol bis (anhydrotrimellitate), 4,4′-diaminodiphenylsulfone, and bis (γ-aminopropyl) tetramethyldiethylene are added to the container. Siloxane [Bis (γ-aminopropyl) tetramethydisiloxane] was charged at 50.2 mol%: 42.3 mol%: 7.5 mol% and stirred vigorously to prepare a solution containing polyamic acid having a concentration of 20 wt%. Thereafter, 2% by weight of p-toluenesulfonic acid was added to the solution to raise the polymerization temperature to 180 ° C. and imidized for about 8 hours to prepare an imide solution.

  The imide solution is precipitated in methanol and dried to obtain an imide solid, which is further dissolved in N-methyl-2-pyrrolidone and has a viscosity of about 4,500 poise at a concentration of 20% by weight and 25 ° C. The viscous liquid polyimide solution shown was produced.

Step 2: Polyimide solution prepared by polymerization by adding an excessive amount of diamine N-methyl-2-pyrrolidone was added to a reactor equipped with a stirrer and a nitrogen gas inlet. Thereafter, 49.8 mol%: 42.5 mol%: 7. 6 of ethylene glycol bis (anhydrotrimellitate), 4,4-diaminodiphenylsulfone and bis (γ-aminopropyl) tetramethyldisiloxane were added to the container. The solution was charged at 7 mol% and stirred vigorously to produce a solution containing polyamic acid having a concentration of 20% by weight. Thereafter, 2% by weight of p-toluenesulfonic acid was added to the solution to raise the polymerization temperature to 180 ° C. and imidized for about 8 hours to prepare an imide solution.

  The imide solution is precipitated in methanol and dried to obtain an imide solid, which is further dissolved in N-methyl-2-pyrrolidone and has a viscosity of about 4,000 poise at a concentration of 20% by weight and 25 ° C. The viscous liquid polyimide solution shown was produced.

Step 3: Manufacture of double-sided tape The same procedure as in Example 1 was performed except that the polyimide adhesive solution prepared in Step 1 and Step 2 was applied to each surface of a polyimide film having a thickness of 25 μm. A polyimide composite film was produced.

<Comparative Example 8>
Step 1: Polyimide solution prepared by adding dianhydride in excess amount N-methyl-2-pyrrolidone was added to a reactor equipped with a stirrer and a nitrogen gas inlet. Thereafter, 50.6 mol of ethylene glycol bis (anhydrotrimellitate), 2,2-bis [4- (4-aminophenoxy) phenyl] propane and bis (γ-aminopropyl) tetramethyldisiloxane were added to the container. %: 44.4 mol%: 5.0 mol% was charged and stirred vigorously to prepare a solution containing polyamic acid having a concentration of 20 wt%. Thereafter, 2% by weight of p-toluenesulfonic acid was added to the solution to raise the polymerization temperature to 180 ° C. and imidized for about 8 hours to prepare an imide solution.

  The imide solution is precipitated in methanol and dried to obtain an imide solid, which is further dissolved in N-methyl-2-pyrrolidone and has a viscosity of about 3,500 poise at a concentration of 20% by weight and 25 ° C. The viscous liquid polyimide solution shown was produced.

Step 2: Polyimide solution prepared by polymerization by adding an excessive amount of diamine N-methyl-2-pyrrolidone was added to a reactor equipped with a stirrer and a nitrogen gas inlet. Thereafter, 49.4 mol of ethylene glycol bis (anhydrotrimellitate), 2,2-bis [4- (4-aminophenoxy) phenyl] propane and bis (γ-aminopropyl) tetramethyldisiloxane were added to the container. %: 45.6 mol%: 5.0 mol% was charged and stirred vigorously to prepare a solution containing polyamic acid having a concentration of 20 wt%. Thereafter, 2% by weight of p-toluenesulfonic acid was added to the solution to raise the polymerization temperature to 180 ° C. and imidized for about 8 hours to prepare an imide solution.

  The imide solution is precipitated in methanol and dried to obtain an imide solid, which is further dissolved in N-methyl-2-pyrrolidone and has a viscosity of about 3,000 poise at a concentration of 20% by weight and 25 ° C. The viscous liquid polyimide solution shown was produced.

Step 3: Manufacture of double-sided tape The same procedure as in Example 1 was performed except that the polyimide adhesive solution prepared in Step 1 and Step 2 was applied to each surface of a polyimide film having a thickness of 25 μm. A polyimide composite film was produced.

<Comparative Example 9>
Step 1: Polyimide solution prepared by adding dianhydride in excess amount N-methyl-2-pyrrolidone was added to a reactor equipped with a stirrer and a nitrogen gas inlet. Thereafter, ethylene glycol bis (anhydrotrimellitate), 4,4′-diaminodiphenylmethane and 3,3 ′, 4,4′-tetraaminophenyl were added to the container in 51.2 mol%: 48.0 mol%: A solution containing polyamic acid having a concentration of 20% by weight was prepared by charging at 0.8 mol% and stirring vigorously. Thereafter, 2% by weight of p-toluenesulfonic acid was added to the solution to raise the polymerization temperature to 180 ° C. and imidized for about 8 hours to prepare an imide solution.

  The imide solution is precipitated in methanol and dried to obtain an imide solid, which is further dissolved in N-methyl-2-pyrrolidone and has a viscosity of about 3,000 poise at a concentration of 20% by weight and 25 ° C. The viscous liquid polyimide solution shown was produced.

Step 2: Polyimide solution prepared by polymerization by adding an excessive amount of diamine N-methyl-2-pyrrolidone was added to a reactor equipped with a stirrer and a nitrogen gas inlet. Thereafter, ethylene glycol bis (anhydrotrimellitate), 4,4′-diaminodiphenylmethane and 3,3 ′, 4,4′-tetraaminophenyl were added to the container in 48.8 mol%: 50.5 mol%: A solution containing polyamic acid having a concentration of 20% by weight was prepared by charging at 0.7 mol% and stirring vigorously. Thereafter, 2% by weight of p-toluenesulfonic acid was added to the solution to raise the polymerization temperature to 180 ° C. and imidized for about 8 hours to prepare an imide solution.

  The imide solution is precipitated in methanol and dried to obtain an imide solid, which is further dissolved in N-methyl-2-pyrrolidone and has a viscosity of about 3,000 poise at a concentration of 20% by weight and 25 ° C. The viscous liquid polyimide solution shown was produced.

Step 3: Manufacture of double-sided tape The same procedure as in Example 1 was performed except that the polyimide adhesive solution prepared in Step 1 and Step 2 was applied to each surface of a polyimide film having a thickness of 25 μm. A polyimide composite film was produced.

<Comparative Example 10>
Step 1: Polyimide solution prepared by adding dianhydride in excess amount N-methyl-2-pyrrolidone was added to a reactor equipped with a stirrer and a nitrogen gas inlet. Thereafter, ethylene glycol bis (anhydrotrimellitate), 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 4,4′-diaminodiphenylmethane, bis (γ-aminopropyl) tetra Methyldisiloxane and 3,3 ′, 4,4′-tetraaminobiphenyl were charged at 52.8 mol%: 23.6 mol%: 18.9 mol%: 4.0 mol%: 0.7 mol%. The solution was vigorously stirred to produce a solution containing polyamic acid having a concentration of 20% by weight. Thereafter, 2% by weight of p-toluenesulfonic acid was added to the solution to raise the polymerization temperature to 180 ° C. and imidized for about 8 hours to prepare an imide solution.

  The imide solution was precipitated in methanol and dried to obtain an imide solid, which was further dissolved in N-methyl-2-pyrrolidone and had a viscosity of about 2,000 poise at a concentration of 20% by weight and 25 ° C. The viscous liquid polyimide solution shown was produced.

Step 2: Polyimide solution prepared by polymerization by adding an excessive amount of diamine N-methyl-2-pyrrolidone was added to a reactor equipped with a stirrer and a nitrogen gas inlet. Thereafter, ethylene glycol bis (anhydrotrimellitate), 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 4,4′-diaminodiphenylmethane, bis (γ-aminopropyl) tetra Methyldisiloxane and 3,3 ′, 4,4′-tetraaminobiphenyl were charged at 47.2 mol%: 27.4 mol%: 20.3 mol%: 4.4 mol%: 0.7 mol%. The solution was vigorously stirred to produce a solution containing polyamic acid having a concentration of 20% by weight. Thereafter, 2% by weight of p-toluenesulfonic acid was added to the solution to raise the polymerization temperature to 180 ° C. and imidized for about 8 hours to prepare an imide solution.

  The imide solution is precipitated in methanol and dried to obtain an imide solid, which is further dissolved in N-methyl-2-pyrrolidone to give a viscosity of about 1,500 poise at a concentration of 20% by weight and 25 ° C. The viscous liquid polyimide solution shown was produced.

Step 3: Manufacture of double-sided tape The same procedure as in Example 1 was performed except that the polyimide adhesive solution prepared in Step 1 and Step 2 was applied to each surface of a polyimide film having a thickness of 25 μm. A polyimide composite film was produced.

  Table 4 below shows the results of physical property values for the polyimide composite films produced in Comparative Examples 7-10.

  As can be seen from Table 3 and Table 4, the polyimide composite films produced in Examples 7 to 10 were formed by forming different adhesive layers on the front and back surfaces, so that the nickel iron alloy metals and the PIX insulating film The results show that it has excellent adhesive properties at the same time and excellent electrical reliability and thermal cycle reliability at the same time.

  In contrast, the composite films produced in Comparative Examples 7 to 8 are composed of different adhesive layers and have excellent adhesive properties with respect to the nickel iron alloy metal and the PIX insulating film plastic, but at 190 ° C. The modulus value is relatively low, and the reliability in thermal cycle evaluation is not ensured. Moreover, the composite film manufactured in Comparative Example 9 is a case where a polyimide adhesive liquid polymerized and manufactured by adding an excessive amount of diamine is used, which is based on any of the nickel iron alloy metals and the PIX insulating film. Shows a result of poor adhesion, and reliability in thermal cycle evaluation is not ensured.

  The composite film manufactured in Comparative Example 10 is composed of different adhesive layers and has excellent adhesive properties with respect to nickel-iron alloy metal and PIX insulating film plastic, but has a moisture absorption rate of 0.6% against moisture. As mentioned above, the modulus value at 190 ° C. is relatively low, the reliability in thermal cycle evaluation is not ensured, and when an adhesive solution manufactured by adding an excessive amount of diamine is used, the electrical reliability is The result was also not good.

  As mentioned above, although only the specific example of this invention was demonstrated in detail, it cannot be overemphasized that this invention is not limited to the example which concerns. It will be apparent to those skilled in the art that various changes and modifications can be made within the scope of the claims, and these are naturally within the technical scope of the present invention. Understood.

Claims (10)

A polyimide base film having a glass transition temperature of 300 ° C. or higher and a thickness of 5 to 150 μm;
An adhesive layer formed by applying an acid terminal group-containing polyimide adhesive composition on one surface of the polyimide base film;
An adhesive layer formed by applying an amine terminal group-containing polyimide adhesive composition to the other surface of the polyimide base film; and
The double-sided tape for LOC, wherein the adhesive force between the polyimide base film and the respective adhesive layers is 0.8 kgf / cm ² or more.   The polyimide adhesive composition comprises any one selected from 1) dianhydride, 2) diamine, 3) polyamino compound, and 4) diamine containing siloxane structure, triamine, or tetraamine. The LOC double-sided tape according to claim 1.   The polyimide adhesive composition is a hybrid type of a thermoplastic resin and a thermosetting resin further including at least one selected from the group consisting of an epoxy resin, a bismaleimide resin, and a rubber resin. The LOC double-sided tape according to claim 2.   The acid terminal group-containing polyimide adhesive composition has a molar ratio of dianhydride and diamine of 0.501: 0.499 to 0.524: 0.476, and is polymerized by adding an excessive amount of dianhydride. The LOC double-sided tape according to claim 1, wherein the double-sided tape is for LOC.   The amine terminal group-containing polyimide adhesive composition has a dianhydride and diamine molar fraction of 0.499: 0.501 to 0.476: 0.524, and is polymerized by adding an excessive amount of diamine. 2. The double-sided tape for LOC according to claim 1, wherein the double-sided tape is for LOC.   2. The LOC double-sided tape according to claim 1, wherein the acid end group-containing polyimide adhesive composition has an acid value of 0.03 to 10. 3.   2. The LOC double-sided tape according to claim 1, wherein the amine end group-containing polyimide adhesive composition has an amine value of 0.03 to 10. 3.   2. The LOC double-sided tape according to claim 1, wherein the adhesive layer coated with the acid terminal group-containing polyimide adhesive composition is attached to a metal lead frame.   2. The LOC double-sided tape according to claim 1, wherein the adhesive layer coated with the amine terminal group-containing polyimide adhesive composition is adhered to a plastic semiconductor chip insulating film. A step of applying an acid terminal group-containing polyimide adhesive composition on one surface of a polyimide base film having a glass transition temperature of 300 ° C. or more and a thickness of 5 to 150 μm to form an adhesive layer;
Applying an amine terminal group-containing polyimide adhesive composition to the other surface of the polyimide base film to form an adhesive layer;
And a step of adhering each of the adhesive layers to the polyimide base film at a high temperature of 150 to 350 ° C. for 0.001 to 1 second.