JP2006021455A - Polyimide metal laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyimide metal laminate which has a polyimide resin layer excellent in modulus of elasticity at high temperatures, transparency, and dimensional stability, does not cause problems such as sinking, wiring dislocation, peeling, and plating permeation, and is used widely in a TAB tape processing line and suitable for a substrate for COF. <P>SOLUTION: The polyimide metal laminate having at least one resin layer is produced from a silica-dispersed polyimide composition obtained by reacting an alkoxy silane and/or its partial hydrolysis polycondensation product (A) with a compound (B) having an amino group and a functional group which can form a bond with silica in a polyimide solution and/or a polyamic acid solution and in the presence of water. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a polyimide metal laminate having a silica-dispersed polyimide resin layer excellent in elastic modulus at high temperature, dimensional stability, transparency, and adhesion to an inorganic compound substrate. Specifically, it has at least one layer of the silica-dispersed polyimide resin layer, and when the chip and the metal wiring are bonded by Au—Au bonding or Au—Sn bonding using the inner lead bonder, the chip polyimide is used. The present invention relates to a polyimide metal laminate suitable as a substrate for Chip on Film (hereinafter referred to as COF), which is less sunk into a resin layer and is widely used in a tape automated bonding (TAB) tape processing line.

  The polyimide metal laminate is manufactured by casting a polyimide resin on a metal foil or laminating a polyimide film and a metal foil. Moreover, it manufactures also by forming a metal layer by sputtering, plating, etc. on the polyimide film surface. These polyimide metal laminates are widely used as flexible printed boards and TAB tapes.

  In recent years, the wiring pattern of a flexible printed board obtained from a polyimide film has been finely patterned. From the viewpoint of the mounting method on the TAB line and the connection reliability between the chip and the wiring, Au-Au bonding and Au-Sn bonding are widely used for chip mounting. However, in the polyimide metal laminate in which a thermoplastic polyimide layer is formed on a metal foil in order to improve the adhesion between the metal layer and the polyimide layer, when the chip mounting by Au-Sn bonding is performed, the thermoplasticity There are cases where the wiring and chip bumps sink into the polyimide, the wiring shifts, the wiring peels off from the polyimide, or the plating penetrates. Excessive sinking of the wiring causes problems such as an underfill and an edge short circuit because the gap between the chip and the polyimide layer becomes narrow. In addition, the wiring shift causes problems such as contact with adjacent wiring and causing a short circuit. These problems are thought to be caused by deformation of the polyimide layer during chip mounting, and these problems can be avoided by improving the elastic modulus of the polyimide resin layer at high temperatures (chip mounting temperature). Attempts have been made.

  For example, in the method of laminating polyimide on a metal foil by casting or laminating methods, the following two attempts have been made. First, it is a method for producing a polyimide metal laminate in which an inorganic filler such as silica or alumina is added to a polyimide resin layer to improve the elastic modulus of the polyimide resin layer. However, this method reduces the transparency of the polyimide resin layer due to the addition of the filler, and after the circuit processing, the metal wiring of the polyimide resin layer cannot be recognized from the surface where the metal is not laminated, and the inner lead bonder There is a problem that positioning at the time of chip mounting becomes difficult. Moreover, the method of producing a polyimide metal laminated body using the highly crystalline polyimide which shows a high elasticity modulus as another method is mentioned. However, although this method does not cause the above-mentioned problem, since it is a highly crystalline polyimide, the drying property is poor, and when a polyimide metal laminate is produced, foaming occurs in the polyimide resin. There is a disadvantage of being scarce.

  Further, a method of sputtering metal on a polyimide film is known as a method for producing a metal laminate that does not use thermoplastic polyimide. Since the polyimide metal laminate produced by the sputtering method does not have a thermoplastic resin layer, the phenomenon that metal wiring sinks into the polyimide layer does not occur during chip mounting. However, in the case of the sputtering method, there is a drawback that the yield is likely to deteriorate due to the pinhole of the metal layer. In order to produce a polyimide metal laminate having no pinholes, it is effective to laminate polyimide on a metal foil by casting or laminating methods, but in this case, the above-described problems occur.

  On the other hand, as a technique for improving the elastic modulus, adhesiveness, and dimensional stability of a polyimide resin, a technique in which silica and polyimide are combined by a sol-gel method is known (see Non-Patent Document 1, etc.). To finely disperse the polyimide and silica particles, a sol-gel reaction is usually performed in a polyamic acid solution which is a polyimide precursor, or a polyamic acid grafted with an alkoxysilane oligomer is subjected to a dehydration imidization reaction. Is a typical method.

  For example, as an example of the former, JP-A-8-73739 (Patent Document 1) discloses that an amino group-containing alkoxysilane and an alkoxysilane are reacted in the presence of water in a polyamic acid solution, followed by polyimidization. Thus, a method for producing a polyimide composition in which silica particles are finely dispersed is disclosed. This method emphasizes the importance of using polyamic acid in the production of the composite and the coexistence of the amino group-containing alkoxysilane, and the patent states that the film produced by this method is transparent. However, it is limited to the description, and no specific use is described.

As an example of the latter, JP-A-2002-293933 (Patent Document 2) discloses an imide obtained by thermosetting an alkoxy group-containing silane-modified polyamide acid obtained by reacting a polyamic acid and an epoxy group-containing alkoxysilane partial condensate. Is disclosed. In this method, a step of introducing a precursor of silica fine particles in advance to a specific position of the polyamic acid is required, or since an oligomer is introduced into the polymer, gelation is likely to occur, and there are cases where the type of polyimide that can be used is limited. is there.
Industrial materials, Vol. 46, 32 (1998) JP-A-8-73739 JP 2002-293933 A

  As described above, the conventionally known polyimide metal laminates cause sinking, wiring displacement, peeling, and plating penetration in a method of bonding chips at a high temperature such as Au—Au bonding or Au—Sn bonding. There are problems such as poor transparency of the polyimide layer, poor production efficiency of the laminate, and pinholes in the metal layer. Not supported.

  An object of the present invention is to produce a polyimide metal laminate having a polyimide resin layer excellent in elastic modulus at high temperature, transparency, and dimensional stability. Thereby, the polyimide metal laminated body suitable as a base material for COF currently widely used in the TAB tape processing line which does not generate | occur | produce problems, such as sinking, wiring shift | offset | difference, peeling, and the penetration | infiltration of plating, can be provided. .

  As a result of intensive studies, the present inventors have found that a polyimide metal laminate having one or more silica-dispersed polyimide resin layers prepared by using a sol-gel method can solve the above problems, and completed the present invention. .

  That is, the present invention provides an alkoxysilane and / or a partially hydrolyzed polycondensate (A) thereof and an amino group-containing compound (B) having a functional group capable of forming a bond with silica, a polyimide solution and / or a polyamic acid. A polyimide metal laminate having at least one resin layer produced from a silica-dispersed polyimide composition obtained by reacting in the presence of water in a solution.

  ADVANTAGE OF THE INVENTION According to this invention, the polyimide metal laminated body which has a polyimide resin layer excellent in the elastic modulus at high temperature, dimensional stability, and transparency can be obtained. This polyimide metal laminate does not cause problems such as sinking, misalignment of wiring, peeling, and plating penetration even when Au—Au bonding or Au—Sn bonding is used for chip mounting. Therefore, the polyimide metal laminate of the present invention can cope with the recent increase in chip density and is effective as a polyimide metal laminate for COF widely used in TAB tape processing lines. Can be used for

  Hereinafter, the present invention will be described in detail.

  The polyimide metal laminate of the present invention comprises an alkoxysilane and / or a partially hydrolyzed polycondensate (A) thereof, an amino group-containing compound (B) having a functional group capable of forming a bond with silica, a polyimide solution and / or Or at least one or more resin layers manufactured from the silica dispersion polyimide composition obtained by making it react in presence of water in a polyamic-acid solution are characterized by the above-mentioned.

  The silica-dispersed polyimide resin used in the present invention comprises an alkoxysilane and / or a partially hydrolyzed polycondensate (A) thereof, an amino group-containing compound (B) having a functional group capable of forming a bond with silica, a polyimide solution and It is important to produce by reacting in a polyamic acid solution in the presence of water (sol-gel reaction). By producing by this method, a polyimide composition in which silica having a maximum particle diameter of 100 nm or less is finely dispersed can be obtained, and the elastic modulus, dimensional stability, transparency and inorganic compound substrate at high temperature without impairing transparency. It can be set as the resin layer excellent in adhesiveness. This effect is achieved by using polyimide resin and / or polyamic acid solution containing only polyimide resin produced by simply mixing silica with polyamic acid and / or polyimide, and alkoxysilane and / or its partially hydrolyzed polycondensate (A) component. If only a composite resin of polyimide and silica obtained by reacting in the presence of water is used, it cannot be sufficiently obtained and cannot be used for the polyimide metal laminate of the present invention.

  Examples of the alkoxysilane and / or its partially hydrolyzed polycondensation compound (A) used in the production of the silica-dispersed polyimide composition include tetramethoxysilane (TMOS), tetraethoxysilane (TEOS), tetrapropoxysilane, tetraiso Propoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, isopropyltrimethoxy Silane, isopropyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, trifluoromethyltrimethoxy Lan, trifluoromethyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyl Trimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane Alkoxysilanes such as 3-acryloxypropyltriethoxysilane, 3-chloropropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, The partially hydrolyzed polycondensate is obtained by hydrolyzing and polycondensing these one or more alkoxysilanes using an acid or alkali compound as a catalyst. Tetramethoxysilane or tetraethoxysilane is preferably used because of its great effect on elastic modulus at high temperature and dimensional stability.

  The amino group-containing compound (B) having a functional group capable of forming a bond with silica used in the present invention will be described. In the present invention, the functional group capable of forming a bond with silica is specifically a functional group capable of forming a bond such as a covalent bond, a hydrogen bond, or an ionic bond with silica. Examples of the functional group capable of forming a covalent bond with silica include an alkoxysilyl group and a silanol group. Examples of the functional group capable of forming a hydrogen bond include a hydroxyl group, a carboxyl group, and an amino group. Moreover, as a functional group which can form an ionic bond, an ammonium group etc. are mentioned, for example. The amino group-containing compound (B) having a functional group capable of forming a bond with silica is a compound having the functional group capable of forming a covalent bond, a hydrogen bond, an ionic bond, etc. with the above silica and an amino group in the same molecule. It is.

  Examples of the amino group-containing compound (B) having a functional group capable of forming a bond with silica include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, and 3-aminopropyl. Methyldiethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 2-aminoethylaminomethyltrimethoxysilane, 3 -Aminopropyldimethylethoxysilane, 2- (2-aminoethylthioethyl) triethoxysilane, p-aminophenyltrimethoxysilane, N-phenyl-3-aminopropylmethyldimethoxysilane, N-phenyl-3-aminopropylmethyl Diethoxysilane, N Phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, 2-aminoethanol, 3-amino-1-propanol, 2-amino-1-amino-1-butanol, 1-amino 2-butanol, 2-amino-1-butanol, 3-propanediol, 3-amino-1,2-propanediol, 4,2- (2-aminoethoxy) ethanol, 2-amino-2-methyl-1 -Propanol, 4-amino-2-methylbutanol, 3-aminopropionic acid, 2-aminopropionic acid, 4-amino-n-butyric acid, 5-amino-n-valeric acid, 2-aminoisovaleric acid, asparagine , Aspartic acid, 2-amino-2-methyl-1,3-propanediol, 2- (2-aminoethylamino) Tanol, 2-aminoethanethiol, 2-aminoethanesulfonic acid, N, N-dimethyl-1,3-propanediamine, N- (3-aminopropyl) cyclohexylamine, 4-picolylamine, 3-picolylamine, 2 -Picolylamine, 4- (2-aminoethyl) pyridine, 3- (2-aminoethyl) pyridine, 4-aminomethylpiperidine, 1-amino-4-methylpiperazine, 3-amino-5-methylpyrazole, 1- (3-aminopropyl) imidazole, 2-aminoethane-1-sulfonic acid, 3-aminopropanesulfonic acid, sulfanilic acid, 1,4-diaminobutane dihydrochloride, 1,5-diaminopentane dihydrochloride, etc. However, it is not limited to these. Preferably, one or more amino group-containing compounds selected from these are used. In addition, since the effect on elastic modulus at high temperature, dimensional stability and adhesion is large, the functional group capable of forming a bond with silica is more preferably an alkoxysilyl group, It is more preferable to use 3-aminopropyltrimethoxysilane or 3-aminopropyltriethoxysilane.

  The amount of the amino group-containing compound (B) having a functional group capable of forming a bond with the silica used in the present invention is such that the silica and / or its partially hydrolyzed condensation compound (A) is 100 parts by mass with respect to silica. The total amount of the amino group-containing compound (B) having a functional group capable of forming a bond is preferably 0.1 to 30 parts by mass, more preferably 0.1 to 20 parts by mass, and still more preferably 0.1 to 30 parts by mass. 15 parts by mass. One or more compounds selected from amino group-containing compounds (B) having a functional group capable of forming a bond with silica have a higher effect on elastic modulus and dimensional stability at a high temperature when they are 30 parts by mass or less. When the content is 0.1 parts by mass or more, transparency and adhesiveness are improved.

There is no restriction | limiting in particular in the polyimide solution and / or polyamic acid used when manufacturing a silica dispersion polyimide composition in this invention, The polyimide obtained from well-known diamines and acid dianhydride can be used. A film obtained by imidizing and removing a polyimide solution and / or a polyamic acid solution preferably has a linear expansion coefficient of 1 to 70 × 10 ⁻⁶ / ° C., and 5 to 50 × 10 ⁻⁶ / ° C. Is more preferable, and what is 5-30 * 10 < ^-6 > / degreeC is still more preferable.

  Examples of the diamines used as a raw material for the polyimide solution and / or polyamic acid used in producing the silica-dispersed polyimide composition in the present invention include 1,3-bis (3-aminophenoxy) benzene, 4, 4-Bis (3-aminophenoxy) biphenyl, 3,3′-diamibenzophenone, p-phenylenediamine, 4,4′-diaminodiphenyl ether, 1,3-bis (3- (3-aminophenoxy) phenoxy) benzene 1,3-bis (3- (4-aminophenoxy) phenoxy) benzene, 5,7-diamino-1,1,4,6-tetramethylindyne, 1,3-bis (4- (3-amino) Phenoxy) phenoxy) benzene, 1,3-bis (3- (2-aminophenoxy) phenoxy) benzene, 1,3-bis (4 -(2-aminophenoxy) phenoxy) benzene, 1,3-bis (2- (2-aminophenoxy) phenoxy) benzene, 1,3-bis (2- (3-aminophenoxy) phenoxy) benzene, 1,3 -Bis (2- (4-aminophenoxy) phenoxy) benzene, 1,4-bis (3- (3-aminophenoxy) phenoxy) benzene, 1,4-bis (3- (4-aminophenoxy) phenoxy) benzene 1,4-bis (3- (2-aminophenoxy) phenoxy) benzene, 1,4-bis (4- (3-aminophenoxy) phenoxy) benzene, 1,4-bis (4- (2-aminophenoxy) ) Phenoxy) benzene, 1,4-bis (2- (2-aminophenoxy) phenoxy) benzene, 1,4-bis (2- (3-aminophenoxy) Enoxy) benzene, 1,4-bis (2- (4-aminophenoxy) phenoxy) benzene, 1,2-bis (3- (3-aminophenoxy) phenoxy) benzene, 1,2-bis (3- (4 -Aminophenoxy) phenoxy) benzene, 1,2-bis (3- (2-aminophenoxy) phenoxy) benzene, 1,2-bis (4- (4-aminophenoxy) phenoxy) benzene, 1,2-bis ( 4- (3-aminophenoxy) phenoxy) benzene, 1,2-bis (4- (2-aminophenoxy) phenoxy) benzene, 1,2-bis (2- (2-aminophenoxy) phenoxy) benzene, 1, 2-bis (2- (3-aminophenoxy) phenoxy) benzene, 1,2-bis (2- (4-aminophenoxy) phenoxy) benzene, 1, -Bis (3- (3-aminophenoxy) phenoxy) -2-methylbenzene, 1,3-bis (3- (4-aminophenoxy) phenoxy) -4-methylbenzene, 1,3-bis (4- ( 3-aminophenoxy) phenoxy) -2-ethylbenzene, 1,3-bis (3- (2-aminophenoxy) phenoxy) -5-sec-butylbenzene, 1,3-bis (4- (3-aminophenoxy) Phenoxy) -2,5-dimethylbenzene, 1,3-bis (4- (2-amino-6-methylphenoxy) phenoxy) benzene, 1,3-bis (2- (2-amino-6-ethylphenoxy) Phenoxy) benzene, 1,3-bis (2- (3-aminophenoxy) -4-methylphenoxy) benzene, 1,3-bis (2- (4-aminophenoxy) -4-t ert-butylphenoxy) benzene, 1,4-bis (3- (3-aminophenoxy) phenoxy) -2,5-di-tert-butylbenzene, 1,4-bis (3- (4-aminophenoxy) phenoxy ) -2,3-dimethylbenzene, 1,4-bis (3- (2-amino-3-propylphenoxy) phenoxy) benzene, 1,2-bis (3- (3-aminophenoxy) phenoxy) -4- Methylbenzene, 1,2-bis (3- (4-aminophenoxy) phenoxy) -3-n-butylbenzene, 1,2-bis (3- (2-amino-3-propylphenoxy) phenoxy) benzene and the like Can be mentioned.

  These may be used alone or in combination of two or more. However, when two or more of these are used, it becomes easy to control the drying property and mechanical properties when producing a polyimide film. Two or more types are preferably used.

  Moreover, when using 2 or more types, at least 1 type or more is following General formula (1).

(In formula (1), X ¹ and X ² are each independently selected from the group consisting of a single bond, an oxygen atom, a sulfur atom, a carbonyl group, a sulfonyl group, and a hydrocarbon group optionally substituted with a halogen atom. Each Y is independently selected from the group consisting of a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group, a nitro group, and a hydrocarbon group optionally substituted with a halogen atom, n represents an integer of 0 to 8). Further, when two or more kinds are used, at least one kind is 1,3-bis (3-aminophenoxy) benzene, 4,4-bis (3-aminophenoxy) biphenyl, 3,3′-diamidine. More preferably, it is selected from benzophenone, p-phenylenediamine, and 4,4′-diaminodiphenyl ether.

  In the present invention, the acid dianhydride used as a raw material for the polyimide solution and / or the polyamic acid used in producing the silica-dispersed polyimide composition is not particularly limited, and known ones can be used. Examples include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 2,3, 3 ′, 4′-biphenyltetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) sulfide dianhydride, bis (3,4- Dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (3 , 4-Dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride, 1,3-bis (3,4-dicarboxyphenoxy) benzene dianhydride, 1,4- Screw (3 4-dicarboxyphenoxy) benzene dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) biphenyl dianhydride, 2,2-bis [(3,4-dicarboxyphenoxy) phenyl] propane Anhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, butane-1,2,3,4-tetracarboxylic dianhydride , Pentane-1,2,4,5-tetracarboxylic dianhydride, cyclobutanetetracarboxylic dianhydride, cyclopentane-1,2,3,4-tetracarboxylic dianhydride, cyclohexane-1,2 , 4,5-tetracarboxylic dianhydride, cyclohex-1-ene-2,3,5,6-tetracarboxylic dianhydride, 3-ethylcyclohex-1-ene-3- (1,2) 5,6-tetracarboxylic dianhydride, 1-methyl-3-ethylcyclohexane-3- (1,2), 5,6-tetracarboxylic dianhydride, 1-methyl-3-ethylcyclohexa-1 -Ene-3- (1,2), 5,6-tetracarboxylic dianhydride, 1-ethylcyclohexane-1- (1,2), 3,4-tetracarboxylic dianhydride, 1-propylcyclohexane -1- (2,3), 3,4-tetracarboxylic dianhydride, 1,3-dipropylcyclohexane-1- (2,3), 3- (2,3) -tetracarboxylic dianhydride , Dicyclohexyl-3,4,3 ′, 4′-tetracarboxylic dianhydride, bicyclo [2.2.1] heptane-2,3,5,6-tetracarboxylic dianhydride, bicyclo [2.2 .2] Octane-2,3,5,6-tetracarboxylic acid bismuth Things, bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, and the like. Of these, pyromellitic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, and 3,3', 4,4'-benzophenone tetracarboxylic dianhydride are preferable. The reaction molar ratio of diamines and tetracarboxylic dianhydrides is usually in the range of 0.75 to 1.25.

  In the present invention, the polyimide solution and / or the polyamic acid solution used when producing the silica-dispersed polyimide composition may contain any other component depending on the purpose. For example, the general formula (3)

(In the formula, d represents an integer of 0 or more, and R ₇ may be independently the same or different, and O, SO ₂ , S, CO, CH ₂ , C (CH ₃ ) ₂ , C (CF ₃ ) ₂ or direct connection, and R ₆ is the same or different and each represents a hydrogen atom, a halogen atom, or a hydrocarbon group, and the benzene ring substitution positions are independent of each other. A bismaleimide compound can also be blended. At this time, the bismaleimide compound may be added to either the solution before the sol-gel reaction or the solution after the reaction.

  In the present invention, when producing a silica-dispersed polyimide composition, the hydrolysis / polycondensation reaction of alkoxysilanes is added with a catalyst capable of hydrolysis / polymerization reaction as shown below for the purpose of accelerating the reaction. May be. What is used as a catalyst for hydrolysis / polymerization reaction of alkoxysilanes is “the latest functional sol-gel fabrication technology by sol-gel method” (Satoru Hirashima, General Technical Center, P29) and “sol-gel”. It is a catalyst used in a general sol-gel reaction described in “Science of Law” (Sakuo Sakuhana, Agne Fate, P154). For example, for acid catalysts, hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, acetic acid, oxalic acid, tartaric acid, toluenesulfonic acid and other inorganic and organic acids, for alkali catalysts, alkali metal water such as ammonium hydroxide, potassium hydroxide and sodium hydroxide Oxides, quaternary ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, ammonia, triethylamine, tributylamine, morpholine, pyridine, piperidine, ethylenediamine, diethylenetriamine, ethanolamine, diethanolamine, Amines such as triethanolamine, aminosilanes such as 3-aminopropyltriethoxysilane, N (2-aminoethyl) -3-aminopropyltrimethoxysilane, etc. And the like.

  In addition, organotin compounds, titanium tetraisopropoxide, diisopropoxytitanium bisacetylacetonate, zirconium tetrabutoxide, zirconium tetrakisacetylacetonate, aluminum triisopropoxide, aluminum trisethylacetonate, trimethoxyborane, etc. A metal alkoxide etc. can be used. The preferred amount of catalyst used is 0.5 mole equivalent or less, more preferably 0.1 mole equivalent or less, based on the total alkoxy groups of alkoxysilanes, but an amino group-containing compound having a functional group capable of forming a bond with silica. This does not apply when (B) acts as a catalyst.

  In the present invention, when the silica-dispersed polyimide composition is produced, the preferred amount of water added is alkoxysilane and / or a partially hydrolyzed polycondensate thereof, and an amino group-containing compound having a functional group capable of forming a bond with silica ( It is 10 molar equivalents or less, more preferably 3 molar equivalents or less with respect to the total alkoxysilane groups contained in B). In addition, since the sol-gel reaction proceeds also with water contained in the polyimide solution and / or the polyamic acid solution, it may not be necessary to add water.

  In the present invention, an alkoxysilane and / or its partially hydrolyzed polycondensation compound (A) and an amino group-containing compound (B) having a functional group capable of forming a bond with silica are mixed in a polyimide solution and / or a polyamic acid solution. (1) (A) and (B) are simultaneously added to a polyimide solution and / or a polyamic acid solution and mixed with stirring, and then water and a catalyst are added if necessary. A method of adding and reacting at a predetermined temperature, (2) adding (B) to a polyimide solution and / or a polyamic acid solution, stirring and mixing (A), and then sequentially adding water and a catalyst as necessary. (3) After adding (A) to the polyimide solution and / or the polyamic acid solution (B), water and a catalyst as necessary are sequentially added and reacted at the predetermined temperature. (4) Add (A), water and, if necessary, a catalyst to the polyimide solution and / or polyamic acid solution, react at a predetermined temperature for a certain period of time, and then add (B) to continue the reaction. Any of these methods can be used.

  In the present invention, preferred reaction concentration, temperature, and time for hydrolysis / condensation polymerization of alkoxysilanes cannot be generally described because the molecular weight of polyimide and / or polyamic acid used and the respective conditions are related to each other. That is, when the molecular weight of polyimide and / or polyamic acid is high, or when the reaction concentration is high, if the reaction temperature is set high or the reaction time is excessively long, the reaction product will react with the condensation of alkoxysilane. The molecular weight increases, and there is a possibility of increasing viscosity or gelling. Accordingly, the usual preferable reaction concentration is preferably 1 to 50%, more preferably 5 to 30% in terms of the concentration by weight of the solid content in the solution. Moreover, preferable reaction temperature is 1-100 degreeC, More preferably, it is 20-60 degreeC, and reaction time has a preferable about 1-50 hours.

  As for the size of the silica particles in the silica-dispersed polyimide composition used in the present invention, the maximum particle size is preferably 100 nm or less, more preferably 50 nm or less, still more preferably 20 nm or less. If the particle size exceeds 100 nm, the transparency of the film obtained from the silica-dispersed polyimide composition becomes poor. Therefore, after the polyimide metal laminate provided by the present invention is processed, the chip is mounted with an inner lead bonder. Positioning may be difficult. The size and dispersion state of the silica particles can be confirmed by observation with a transmission electron microscope (TEM), an atomic force microscope (AFM), or X-ray scattering. Further, in the present invention, the silica in the silica-dispersed polyimide composition may not be clearly particulate, but it is considered that the silica phase does not separate with a size of 100 nm or more. In the present invention, silica includes not only silicon dioxide but also a silicon component having a silanol group or an alkoxysilyl group.

In the present invention, the content of silica (SiO ₂ ) in the silica-dispersed polyimide composition is preferably 1 to 50 parts by mass, more preferably 1 to 30 parts by mass with respect to 100 parts by mass of the polyimide. When the amount is 50 parts by mass or less, the film strength is less likely to be impaired. Moreover, by containing 1 mass part or more, the effect on the elasticity modulus and adhesiveness in high temperature, and dimensional stability becomes high. The content of silica here is the content of the silica condensate produced by the sol-gel reaction, and refers to the amount of ash remaining after baking the organic component of the polyimide composition at 800 ° C. in air.

  In the present invention, the silica-dispersed polyimide composition is preferably the following general formula (2)

Wherein W is a tetravalent organic group, Z and R2 are each independently a divalent organic group, R1 is a hydrogen atom, a hydrocarbon group or an aromatic group, and Q is bonded to silica. And m is a rational number of 0.001 or more and 0.5 or less.

In the present invention, when the polyimide solution is used as a starting material when the silica-dispersed polyimide composition is produced, the silica-dispersed polyimide composition is dispersed in the polyimide as described in the general formula (2). Will be. This is because a functional group capable of forming a bond with silica is introduced into the polyimide compound by the reaction of the amino group contained in the compound (B) with the imide ring. As a result, a bond such as a covalent bond, a hydrogen bond or an ionic bond can be formed between silica and polyimide. The reaction between the imide ring and the amino group can be confirmed by solid ¹⁵ N-NMR measurement or FT-IR measurement.

  In general formula (2), W is not particularly limited as long as it is a tetravalent organic group, and is usually a residue of a carboxylic dianhydride residue which is a polyimide raw material, and is a known one. Z is a divalent organic group, which is a part of a diamine residue which is usually a raw material for polyimide, and is a known one. Furthermore, R1 and R2 are monovalent and divalent organic groups, respectively, and have a functional group capable of forming a bond with the amino group and silanol group residue of the amino group-containing alkoxysilane and / or silica. It is a residue of an amino group of an amino group-containing compound and a functional group capable of forming a bond with silica. In addition, when Q is a silanol group, it may react with the dispersed silica particles to form a siloxane bond. Further, m is a rational number of 0.001 or more and 0.5 or less, preferably a rational number of 0.005 or more and 0.1 or less.

  The polyimide metal laminate of the present invention is a laminate having a polyimide layer and a metal layer. If at least one of the polyimide layers is a resin layer obtained from the above silica-dispersed polyimide composition, the others are particularly limited. There is no.

  When an example is given about the specific manufacturing method of the polyimide metal laminated body of this invention, the amino group containing compound (A) which has a functional group which can form a bond with an alkoxysilane and / or its partial hydrolysis polycondensate (A), and a silica ( B) is reacted in the presence of water in a polyimide solution and / or a polyamic acid solution, and the resulting solution is applied onto a metal foil or a polyimide layer, dried and cured to form a silica-dispersed polyimide layer. It is produced by forming. At this time, another polyimide layer or metal layer may be further laminated on the silica-dispersed polyimide layer.

  Moreover, you may produce by thermocompression bonding a metal foil and / or a polyimide metal laminated body to the polyimide film which has a silica dispersion | distribution polyimide layer. In this case, a polyimide or metal layer may be further laminated on the silica-dispersed polyimide layer.

  In the polyimide metal laminate of the present invention, when the polyimide resin layer is a multilayer, the silica-dispersed polyimide layer may be directly laminated on the metal foil, or formed on an adhesive layer such as thermoplastic polyimide. In the resin layer, any number of layers may be used, and more than one may be used. A preferred position of the silica-dispersed polyimide resin layer is on the metal foil or on the thermoplastic polyimide layer produced on the metal foil.

  In addition, the polyimide metal laminate of the present invention includes both a single-sided plate in which only one metal foil layer is laminated on a polyimide resin layer or a double-sided plate in which metal foil is laminated on both sides of a polyimide resin layer. is there.

  When manufacturing the polyimide metal laminate of the present invention, a polyimide solution and / or a polyamic acid solution is applied to a metal foil, polyimide film, or the like as a die coater, comma coater, roll coater, gravure coater, curtain coater, sprayer. A known method such as a coater can be employed. It can be suitably used depending on the thickness to be applied, the viscosity of the varnish and the like. As a method for drying and curing the applied varnish, a normal heating and drying furnace can be used. As the atmosphere of the drying furnace, air, inert gas (nitrogen, argon) or the like can be used. The drying temperature is appropriately selected depending on the boiling point of the solvent, but a temperature range of 60 to 600 ° C. is preferably used. The drying time is appropriately selected depending on the thickness, concentration, and type of solvent, but is preferably about 0.05 to 500 minutes.

  Examples of the thermocompression bonding method of polyimide include a heat press method and / or a continuous laminating method. As a heat press method, it can manufacture, for example, by superimposing the metal foil and polyimide which were cut out to the predetermined size of a press machine, and thermocompression-bonding with a heat press.

  Although there is no restriction | limiting in particular as a continuous laminating method, For example, there exists the method of pinching and sticking between rolls. As this roll, a metal roll, a rubber roll, or the like can be used. Although there is no restriction | limiting in a material, Steel materials and stainless steel material are used as a metal roll. It is preferable to use a processing roll whose surface hardness is increased such as hard chrome plating or tungsten carbide on the surface. As the rubber roll, it is preferable to use heat-resistant silicon rubber or fluorine-based rubber on the surface of the metal roll.

  In addition, two upper and lower metal rolls, called belt laminate, are combined into one set, and two or more seamless stainless steel belts are placed between the upper and lower rolls arranged in series. Pressurization and further laminating may be performed by heating with a metal roll or other heat source. The laminating temperature may be in a temperature range of 200 to 400 ° C. A preferable heating method may be a conduction heating method, a radiant heating method such as far infrared, an induction heating method, or the like.

  When the polyimide resin layer is a multilayer, a layer made of polyimide obtained from a known diamine compound and acid dianhydride may be used in addition to the silica-dispersed polyimide. These polyimides are, for example, 1,3-bis (3-aminophenoxy) benzene, 4,4-bis (3-aminophenoxy) biphenyl, 3,3′-diammibenzophenone, p-phenylenediamine, 4,4 One or more diamines selected from '-diaminodiphenyl ether, and pyromellitic dianhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride, 3,3 ', 4,4' -A polycondensate synthesized from one or more tetracarboxylic dianhydrides selected from benzophenone tetracarboxylic dianhydrides is preferred, but not particularly limited. Further, even a polyimide layer to which the aforementioned bismaleimide compound or the like is added can be used without any problem.

  Moreover, you may use a commercially available polyimide film etc. for another polyimide layer. For example, Upilex (registered trademark) S, Upilex (registered trademark) SGA, Upilex (registered trademark) SN (trade name, manufactured by Ube Industries, Ltd.), Kapton (registered trademark) H, Kapton (registered trademark) V, Kapton (registered) Trademarks) EN (trade name, manufactured by Toray DuPont Co., Ltd.), Apical (registered trademark) AH, Apical (registered trademark) NPI, Apical (registered trademark) HP (trade name, manufactured by Kaneka Chemical Co., Ltd.), etc. It is done. These polyimide films can be used without any problems even if the surface is subjected to plasma treatment, corona discharge treatment or the like.

  In the polyimide metal laminate of the present invention, the metal to be used can be used without particular limitation as long as it is a metal used when used as a flexible wiring board. Preferred examples include copper, nickel, cobalt, chromium and zinc. And at least one metal selected from the group consisting of aluminum and stainless steel, and alloys thereof, more preferably copper and copper alloys, stainless steel and alloys thereof, nickel and nickel alloys (42 alloys also) Including aluminum) and aluminum alloys. More preferred are copper and copper alloys.

  In the polyimide metal laminate of the present invention, the thickness of the metal foil is not limited as long as it can be used in a tape shape, but is preferably 0.1 to 150 μm, preferably 2 to 105 μm, and more preferably 3 μm. For example, a thin foil can be appropriately used for applications that require fine pattern wiring processing, and a thick foil can be appropriately used for wiring that requires rigidity and high current applications.

  In the polyimide metal laminate of the present invention, when considering the balance between curl and dimensional stability, the polyimide layer is preferably 1 layer or more, more preferably 2 layers, and still more preferably 3 layers or more.

  Here, when the preferable aspect in case the polyimide layer of the polyimide metal laminated body of this invention forms three or more layers is shown, it is preferable that the polyimide used for the 1st layer which touches a metal is a thermoplastic polyimide. The thickness is preferably 0.1 or more and 10 μm or less, more preferably 0.2 or more and 5 μm or less, and the glass transition temperature is preferably 150 ° C. or more and less than 350 ° C., more preferably 150 ° C. The average linear expansion coefficient at 100 to 200 ° C. is preferably 20 or more and 70 ppm / ° C. or less.

  Next, the polyimide used in the second layer is preferably a non-thermoplastic polyimide, and the thickness is preferably 1 or more and 250 μm or less, more preferably 4 or more and 50 μm or less, and still more preferably 5 or more and 40 μm or less. The glass transition temperature is preferably 300 ° C. or higher, or preferably has no glass transition temperature, and the average linear expansion coefficient at 100 to 200 ° C. is preferably 5 to 30 ppm / ° C., more preferably 5 to 20 ppm / ° C. The following is preferable.

  The third polyimide layer is preferably non-thermoplastic polyimide when the metal layer is one layer on one side, and preferably has a thickness of 0 to 10 μm, more preferably 0.5 to 5 μm, Those having a glass transition temperature of 300 ° C. or higher or no glass transition temperature are preferred. Moreover, it is preferable that the average linear expansion coefficient of 100-200 degreeC is 10 or more and 60 ppm / degrees C or less, More preferably, it is 20 or more and 40 ppm / degrees C or less.

  When the metal layer is on both sides, the third layer of polyimide is preferably thermoplastic polyimide, and the thickness is preferably 0.1 to 10 μm, more preferably 0.5 to 8 μm. It is as follows. The glass transition temperature is preferably 150 ° C. or higher and lower than 350 ° C., more preferably 150 ° C. or higher and 300 ° C. or lower, and the average linear expansion coefficient at 100 to 200 ° C. is 20 or higher and 70 ppm / ° C. or lower. Is desired.

  The silica-dispersed polyimide used in the present invention is excellent in elastic modulus at high temperature, dimensional stability (low linear expansion coefficient), transparency, and adhesion to an inorganic compound substrate. For this reason, by having at least one layer using this resin in the polyimide layer of the polyimide metal laminate, there is little deformation of the polyimide resin layer even during chip mounting at high temperature and high pressure, wiring displacement and sinking, This has a remarkable effect that problems such as peeling and plating penetration do not occur. In addition, in the silica-dispersed polyimide resin used in the present invention, even when the crystallinity of the polyimide used is low, the elastic modulus at high temperature and the dimensional stability can be improved by compounding with silica. Also, the drying property is good and the productivity is not lowered.

  When the polyimide metal laminate of the present invention is used for COF widely used in a TAB tape processing line, when a silica-dispersed polyimide layer forming at least one layer in the polyimide layer is used as a film, the elastic modulus at high temperature is The following is preferable because the effects of the present invention can be easily obtained. That is, the storage elastic modulus E ′ at a temperature close to the mounting temperature used for Au—Sn bonding or Au—Au bonding is preferably 0.3 GPa to 30 GPa, more preferably 0.5 GPa to 15 GPa. More preferably, it is 0.8 GPa or more and 10 GPa or less. The temperature close to the mounting temperature is 250 to 500 ° C., preferably 300 to 450 ° C., more preferably 350 to 450 ° C.

  In the polyimide metal laminate of the present invention, since the silica-dispersed polyimide layer is transparent, the metal wiring of the polyimide layer can be image-recognized from the surface on which the metal of the polyimide layer is not laminated after circuit processing, and positioning during chip mounting with the inner lead bonder is possible. It becomes possible.

  Since the polyimide metal laminate of the present invention uses a metal foil, it has no pinhole, and has a silica-dispersed polyimide layer excellent in elastic modulus at high temperature, dimensional stability, transparency, and adhesion to an inorganic compound substrate. Therefore, problems such as wiring misalignment, sinking, peeling, and plating penetration do not occur even in chip mounting by Au—Au bonding or Au—Sn bonding.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not restrict | limited at all by this. In addition, the abbreviation in a practical example means the following. Moreover, each evaluation in an Example was performed as follows.
DMAc: dimethylacetamide NMP: N-methyl-2-pyrrolidone TMOS: tetramethoxysilane APTMOS: aminopropyltrimethoxysilane APB: 1,3-bis (3-aminophenoxy) benzene m-BP: 4,4 ′-(3 -Aminophenoxy) biphenyl ODA: 4,4'-oxydianiline (4,4'-diaminodiphenyl ether)
PPD: p-phenylenediamine BTDA: 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride BPDA: 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride PMDA: pyromellitic anhydride APB-BMI: 1,3-bis (3-maleimidophenoxy) benzene

(IC chip mounting evaluation method)
Using a known technique, the polyimide metal laminate is formed into an IC chip (TEG chip Phase 6-50 manufactured by Hitachi Ultra LSI Co., chip thickness: 550 μm, 50 μm pitch Au plated bump, bump size: 30 μm height, 100 μm length, 25 μm width). Circuit processing is performed so that they match, and after treatment with an electroless tin plating solution (model number: LT-34) manufactured by Shinplay Far East Co., Ltd. at 70 ° C. for 3 minutes, thoroughly washed with water and dried at 100 to 130 ° C. It dried for 1-2 hours and obtained the flexible printed wiring board. Thereafter, the circuit of the flexible printed wiring board and the IC chip were aligned, and the IC chip and the flexible printed circuit board were thermocompression bonded under conditions of a temperature of 350 to 450 ° C., a pressure of 100 to 150 MPa, and a time of 1 to 3 seconds. After that, the wiring part where the IC chip was mounted from the polyimide side was confirmed by planar observation with an optical microscope of 1250 times to check whether the wiring misalignment or tin plating did not penetrate the polyimide and metal foil interface, and further cross-sectional observation As a result, the deformation of the wiring, the sinking of the IC chip, and the presence or absence of peeling of the wiring were confirmed with an optical microscope of 1250 times.

(Silica content measurement: thermogravimetry)
The thermogravimetry of the polyimide / silica film is performed in the range of 30 to 800 ° C. with a thermogravimetry device (TGA-50, manufactured by Shimadzu Corporation), and the silica content is determined from the amount of ash remaining after baking at 800 ° C. The content was calculated.

(Viscoelasticity measurement: measurement of storage modulus at 450 ° C)
The elastic modulus was evaluated by measuring temperature dispersion in the tensile deformation mode using RSA-II manufactured by Rheometrics. The measurement was performed under the conditions of a temperature range of 30 to 500 ° C., a temperature increase rate of 3 ° C./min, an Auto-Strain control, a strain of 0.02%, and a frequency of 1 Hz. Further, the sample dimensions were 20 mm in length and 5 mm in width, and the storage elastic modulus E ′ at 450 ° C. was obtained.

(Measurement of linear expansion coefficient)
Using a thermomechanical analyzer (TMA-50, manufactured by Shimadzu Corporation), the linear expansion coefficient is obtained by a tensile method in which a constant load is applied to both ends of the film and the elongation (shrinkage) when the temperature is changed is measured. It was. Under the present circumstances, it measured in the range of 100-200 degreeC, and the range of 380-430 degreeC, and each average linear expansion coefficient was set to (alpha) 1 and (alpha) 2.

Synthesis example 1
To a vessel equipped with a stirrer and a nitrogen introducing tube, DMAc 1532.4 g was added as a solvent, 130.0 g of APB was added thereto, and the mixture was stirred at room temperature until dissolved. Thereafter, 322.22 g of BTDA was added, and the mixture was stirred at 50 to 60 ° C. for about 4 hours to obtain a polyamic acid solution. The obtained polyamic acid solution had a polyamic acid content of 15% by weight and an E-type viscosity at 25 ° C. of 500 mPa · s.

Synthesis example 2
DMAc261.0g was added as a solvent to the container provided with the stirrer and the nitrogen introducing tube, ODA 20.44g and m-BP16.12g were added to this, and it stirred at 20-30 degreeC, and was dissolved. Thereafter, 30.84 g of PMDA was added and the material adhering to the inside of the flask was washed off with 11.0 g of DMAc, heated to 50 to 60 ° C. and stirred for about 1 hour, and then 0.44 g of PMDA was added and the temperature was raised to 60 ° C. The mixture was stirred for about 4 hours while keeping (A) varnish. Next, 263.0 g of NMP was added as a solvent to a container equipped with another stirrer and a nitrogen introduction tube, 19.62 g of PPD was added, and the mixture was stirred and dissolved at 20 to 30 ° C. Thereafter, 37.0 g of BPDA and 11.06 g of PMDA were added, and the raw material adhering to the inside of the flask was washed off with 10.0 g of NMP, heated to 50 to 60 ° C. and stirred for about 4 hours to obtain (B) varnish. Finally, in a container equipped with another stirrer and a nitrogen introduction tube, (B) varnish and (A) varnish are mixed at a weight ratio of 93: 7, heated to 50-60 ° C. and stirred for about 4 hours, A polyamic acid solution was obtained. The obtained polyamic acid solution had a polyamic acid content of 20% by weight and an E-type viscosity at 25 ° C. of 30000 mPa · s. The linear expansion coefficient of the polyimide film obtained from this polyamic acid was 10 ppm / ° C.

Synthesis example 3
After diluting the polyamic acid obtained in Synthesis Example 2 to 15% by weight with NMP, 18 g was charged into a 100 ml reaction vessel, and TMOS (1.245 g) and water (0.631 g) were added, and 1 at 60 ° C. Reacted for hours. Subsequently, amino group-containing alkoxysilane APTMOS (0.138 g) was added and reacted at 60 ° C. for 5 hours to obtain a varnish of a silica-dispersed polyamic acid composition. TMOS, APTMOS, and water were diluted with NMP to 50% by weight and added.

Synthesis example 4
To a container equipped with a stirrer and a nitrogen introduction tube, DMAc 1777.46 g was added as a solvent, ODA 80.0 g and APB 50.06 g were added thereto, and the mixture was stirred at room temperature until dissolved. Thereafter, 123.87 g of PMDA was added and stirred for about 4 hours at 50 to 60 ° C., and further 28.21 g of APB-BMI was added and stirred for about 12 hours to obtain a polyamic acid solution. The resulting polyamic acid solution had a polyamic acid content of 12.5% by weight, and an E-type viscosity at 25 ° C. of 1000 mPa · s.

Synthesis example 5
To a container equipped with a stirrer and a nitrogen introduction tube, DMAc 1777.46 g was added as a solvent, ODA 80.0 g and APB 50.06 g were added thereto, and the mixture was stirred at room temperature until dissolved. Thereafter, 123.87 g of PMDA was added, and the mixture was stirred at 50 to 60 ° C. for about 16 hours to obtain a polyamic acid solution. The resulting polyamic acid solution had a polyamic acid content of 12.5% by weight, and an E-type viscosity at 25 ° C. of 1000 mPa · s.

Example 1
18 g of the polyamic acid / NMP solution (polyamic acid 15 wt%) produced in Synthesis Example 2 was charged into a 100 ml reaction vessel, and TMOS (1.245 g) and water (0.631 g) were added. Reacted for hours. Next, APTMOS (0.138 g) which is an amino group-containing alkoxysilane was added and reacted at 60 ° C. for 5 hours to obtain a solution of a silica-dispersed polyamic acid composition. TMOS, APTMOS, and water were diluted with NMP to 50% by weight and added.

  The obtained polyamic acid solution was applied onto a copper foil using a baker applicator so that the dry film thickness was about 15 μm, and the temperature was increased from 50 ° C. to 180 ° C. under a nitrogen atmosphere using an inert oven. Dry at ° C / min. Next, heat treatment was performed from 280 ° C. to 380 ° C. using an IR reflow furnace to obtain a polyimide metal laminate. The copper foil of the resulting laminate is treated by spraying a ferric chloride solution (40 Baume) from a spray-type nozzle for several minutes until the metal foil is completely removed, washed with water, and then vacuum dried at 60 ° C. A polyimide film was obtained. The physical properties of the obtained film are shown in Tables 1 and 2.

Examples 2-4
The reaction was performed in the same manner as in Example 1 under the conditions shown in Table 1. Further, a polyimide metal laminate was obtained from the solution reacted under the conditions shown in Table 1 in the same manner as in Example 1. A film was produced from the obtained polyimide metal laminate by the same method as in Example 1. The physical properties of the film are shown in Tables 1 and 2.

Comparative Examples 1 and 2
A polyimide metal laminate was obtained in the same manner as in Example 1 except that the conditions were changed to those shown in Table 1. A film was produced from the obtained polyimide metal laminate by the same method as in Example 1. The physical properties of the film are shown in Tables 1 and 2.

Comparative Example 3
2.690 g of colloidal silica / DMAc solution (silica 20% by weight) is added to 18 g of the polyamic acid / NMP solution (polyamic acid 15% by weight) of Synthesis Example 1 and stirred at 60 ° C. for 5 hours to obtain a solution of the polyamic acid composition. Got. A polyimide metal laminate was obtained from the obtained polyamic acid solution in the same manner as in Example 1. A film was produced from the obtained polyimide metal laminate by the same method as in Example 1. The physical properties of the film are shown in Tables 1 and 2.

(Measurement of particle size)
The silica-dispersed polyimide films obtained in Examples 1 and 2 and Comparative Examples 2 and 3 were observed with a TEM to observe the dispersed state of silica. The TEM observation was performed under the following conditions. The prepared polyimide film was embedded with an epoxy resin, trimmed with a glass knife, and then an ultrathin section was prepared with a diamond knife. The prepared ultrathin slice was carbon-reinforced and observed using a transmission electron microscope (TEM) (H-7000, manufactured by Hitachi, Ltd.) at an acceleration voltage of 75 kV.

  As a result of TEM observation, in the films of Examples 1 and 2, clear silica particles were not observed, and a silica phase having a size of 5 to 25 nm was observed, and it was found that silica was uniformly dispersed. On the other hand, in Comparative Example 2, many particles having a particle size of 1 μm or more were observed. In Comparative Example 3, the primary particle diameter was 10 to 20 nm silica particles, but they were agglomerated and the dispersion state was poor.

(Measurement of light transmittance)
Using a UV-visible spectrophotometer (UV2200, manufactured by Shimadzu Corporation), the transmittance of the film having the thickness shown in Table 2 was measured, and the average value of the wavelength of 500 to 800 nm was defined as the light transmittance. Despite the thickest film thickness, the light transmittance of Example 1 was the highest.

Example 5
After concentrating the polyamic acid / DMAc solution prepared in Synthesis Example 5 to 20% by weight of polyamic acid, 50 g was charged into a 100 ml reaction vessel, and TMOS (3.60 g), APTMOS (0 group amino-containing alkoxysilane) (0 .40 g) was added and stirred, and then water (1.83 g) was added and reacted at 60 ° C. for 5 hours to obtain a silica-dispersed polyamic acid composition solution. TMOS, APTMOS, and water were diluted with NMP to 50% by weight and added.

  From the obtained polyamic acid solution, a polyimide metal laminate was obtained in the same manner as in Example 1. A film was produced from the obtained polyimide metal laminate by the same method as in Example 1. Table 3 shows various physical properties of the film.

Comparative Example 4
The polyamic acid solution of Synthesis Example 4 was cast on a copper foil in the same manner as in Example 1 to obtain a polyimide metal laminate. A film was produced from the obtained polyimide metal laminate by the same method as in Example 1. Table 3 shows various physical properties of the film.

Example 6
The thickness after drying the varnish prepared in Synthesis Example 4 with a roll coater to a metal foil of a commercially available copper foil (Furukawa Circuit Foil Co., Ltd., trade name: F0-WS, thickness 9 μm) is 0.5 μm. After coating at 80 to 100 ° C. for 1 minute, the varnish prepared in Synthesis Example 3 was subsequently applied with a comma coater so that the thickness after drying was about 9 μm, and 115 to 130 ° C. for 2 minutes. After drying, the varnish of Synthesis Example 1 was subsequently applied with a roll coater so that the thickness after drying was 4 μm, and then dried at 80 to 100 ° C. for 1 minute and then at 150 to 230 ° C. in an air float type drying furnace. The laminate was obtained by drying and further heat-treating at 280 ° C. to 380 ° C. in a furnace in a nitrogen atmosphere.

  Thereafter, a commercially available polyimide film (manufactured by Toray DuPont Co., Ltd., trade name: Kapton 100EN, thickness 25 μm) is laminated on the polyimide surface of the laminate, and thermocompression bonded at 260 ° C. × 2.5 MPa for 15 minutes, Thereafter, heat treatment was performed at 350 ° C. in a nitrogen atmosphere to obtain a polyimide metal laminate.

  Thereafter, as a result of evaluation of IC chip mounting, there was no misalignment or tinning of the wiring, and the deformation of the wiring or the sinking of the IC chip was 1 μm or less from the cross-sectional observation, and almost no peeling of the wiring was observed.

Comparative Example 5
A polyimide metal laminate was obtained in the same manner as in Example 6 except that the varnish of Synthesis Example 3 of Example 6 was changed to the varnish of Synthesis Example 2.

  Thereafter, as a result of IC chip mounting evaluation, there was no misalignment of the wiring, but tin penetration was observed in the entire wiring width at the wiring and polyimide interface. Further, from the cross-sectional observation, the sink of the IC chip was 1 μm or less, but the deformation of the wiring of about 4 μm was observed, and the peeling of the wiring was also observed.

  INDUSTRIAL APPLICATION This invention can obtain the polyimide metal laminated body which has a polyimide layer excellent in the elasticity modulus in high temperature, dimensional stability, and transparency. Therefore, problems such as wiring misalignment, sinking, peeling and plating penetration do not occur even in chip mounting by Au—Au bonding or Au—Sn bonding. Therefore, the polyimide metal laminate of the present invention can cope with the recent increase in the density of chips, and is widely used in tape automated bonding (TAB) tape processing lines. It can be effectively used as a metal laminate.

Claims (6)

Alkoxysilane and / or its partially hydrolyzed polycondensate (A) and amino group-containing compound (B) having a functional group capable of forming a bond with silica are present in water in a polyimide solution and / or a polyamic acid solution. A polyimide metal laminate comprising at least one resin layer produced from a silica-dispersed polyimide composition obtained by a bottom reaction. The polyimide solution and / or the polyamic acid solution is a solution containing a polyimide copolymer and / or a polyamic acid copolymer synthesized from two or more diamine compounds and one or more tetracarboxylic dianhydrides. The polyimide metal laminate according to the description. As at least one of the diamine compounds, the following general formula (1)

(In formula (1), X ¹ and X ² are each independently selected from the group consisting of a single bond, an oxygen atom, a sulfur atom, a carbonyl group, a sulfonyl group, and a hydrocarbon group optionally substituted with a halogen atom. And each Y is independently selected from the group consisting of a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group, a nitro group, and a hydrocarbon group optionally substituted with a halogen atom, 2. The polyimide metal laminate according to claim 1, wherein a polyimide or a polyamic acid produced using a compound represented by n is an integer of 0 to 8). The polyimide metal laminate according to claim 1, wherein the film obtained by imidizing and removing the polyimide solution and / or the polyamic acid solution has a linear expansion coefficient of 1 to 70 x ^10-6 / ° C. The polyimide metal laminate according to claim 1, wherein the functional group capable of forming a bond with silica is an alkoxysilyl group. The silica-dispersed polyimide composition has the following general formula (2)

Wherein W is a tetravalent organic group, Z and R ² are each independently a divalent organic group, R ¹ is a hydrogen atom, a hydrocarbon group, or an aromatic group, and Q is bonded to silica. The polyimide metal laminate according to claim 1, wherein m is a functional group, and m is a rational number from 0.001 to 0.5.