JP2009060024A - Multilayer board - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a multilayer board reducing the peeling or the like of a polyimide film in a glass board multilayer board with a polyimide film laminated. <P>SOLUTION: The multilayer board has a configuration in which a heat-resistant film is laminated on a glass board. In the multilayer board, the heat-resistant film is a polyimide film obtained through reaction of aromatic diamines having a benzooxazole structure and aromatic tetracarboxylic-acid anhydrides and has a linear expansion coefficient of -2 ppm/°C to 10 ppm/°C. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a multilayer substrate having a multilayer structure using a glass substrate as a core or the like, and more particularly to a multilayer substrate formed by laminating a glass plate and a heat-resistant film by using an adhesive. Is.

As a printed wiring board having a multilayer structure, a multilayer printed wiring board called ML-PWB is known in which a glass cloth reinforced epoxy resin and a copper foil are sequentially laminated and a connection between layers is made through a through-hole. . The through-hole has a problem that the degree of freedom of interlayer conductive connection is low, and a wasteful space for connection is taken even in a layer that is not particularly necessary, so that the wiring density cannot be sufficiently increased.
There is also known a so-called build-up multilayer wiring board in which the above-mentioned multilayer printed wiring board is used as a core and fine circuit layers are formed on the surface in a stacked manner. This is a technique of forming a via hole for interlayer conduction connection using a photosensitive epoxy resin, or a technique of forming a laser via hole using laser processing and forming an interlayer conduction connection and conductor formation by plating. Such a multilayer wiring board is referred to as a first generation build-up multilayer wiring board. Since the first generation build-up multilayer wiring board cannot make a via hole directly above the via hole, the degree of freedom in wiring is somewhat limited.

On the other hand, a multilayer printed wiring board using a conductive paste for interlayer conductive connection is known. B ² it (R) method in which sharpened peaks are made with conductive paste, and prepreg is penetrated to make interlayer conductive connection, and a hole is made by laser in semi-cured epoxy sheet reinforced with aramid nonwoven fabric, and conductive paste is packed into the interlayer conductive connection The ALIVH (R) method, etc., in which a via hole can be formed at an arbitrary position, has a higher degree of freedom in wiring than the first generation build-up multilayer wiring board. However, since the conductive paste is used for the interlayer conductive connection, the conductive resistance between the layers is increased, and the insulation reliability due to the occurrence of migration is lowered. These methods can also be classified as build-up methods in the sense that the conductor layers are sequentially formed and stacked one by one.

In the first generation build-up wiring board, an improved technique has also been proposed so that a via hole can be formed immediately above the via hole by filling the via hole with electroplating. In addition, various material processes have been proposed for build-up multilayer wiring boards. In the build-up method, it is possible to increase the wiring density compared to conventional multilayer wiring boards, but the disadvantage is that the process is very complicated and lengthy because it is necessary to rotate the processing cycle by the number of conductor layers. There is.
In order to solve the long processing process that is a problem of build-up printed wiring boards, circuits corresponding to each conductive layer of build-up multilayer printed wiring boards are formed independently in advance and stacked in a batch to print wiring Research and development related to so-called collective laminating methods for producing plates have been actively conducted (see Patent Documents 1 and 2).
JP 2001-160686 A JP 2000-332369 A

In such a build-up printed wiring board or batch lamination method, the thickness of the insulating layer between layers is related to the characteristic impedance of the transmission line, and if the insulating layer thickness cannot be kept constant, signal transmission is hindered, especially in the high frequency region. Will do. In the batch lamination method, the dimensional stability of the insulating base material is directly linked to the alignment accuracy between the layers. These problems are difficult to solve with glass fiber or aramid fiber reinforced epoxy resin sheets that have been used in the past, and as a material to replace the epoxy resin that is the conventional interlayer insulation material in fields where high accuracy is required. Heat resistant polymer films such as polyimide films have attracted attention.
Polyimide film has excellent heat resistance, electrical properties, mechanical properties, dimensional stability, etc., so various electronic devices including flexible printed wiring boards, TAB tapes, and substrates for semiconductor mounting. It is used in a wide range of fields as high-performance parts such as materials, industrial equipment, and aircraft. In particular, in circuit boards and semiconductor package base materials associated with recent high-density mounting, it has become mainstream to use an insulating resin having a low dielectric constant as an interlayer insulating film in order to increase the speed of signal transmission. However, polyimide is one of the typical insulating materials.
Usually, a polyimide film is bonded to a copper foil using an adhesive, or processed into a laminate (a polyimide film with a copper foil) composed of a film layer and a copper foil by vapor deposition, plating, sputtering, or casting. Or used as a base film (outer layer material or inner layer material) of a flexible printed multilayer circuit board.

When used as an interlayer insulating material for a multilayer substrate, the polyimide film itself does not have adhesiveness like an epoxy semi-cured sheet, and therefore is used in combination with some adhesive.
Insufficient adhesion on the surface of a conventional polyimide film has become a problem, so when performing multilayer lamination via an adhesive, the adhesion reliability between the layers is poor, and as such causes product defects. It was. For this reason, in order to improve the adhesiveness of the polyimide film surface, it has been proposed to use it after performing corona treatment or plasma treatment. In addition, selection of an adhesive is important, and a technique using an adhesive having a polyamide resin and an epoxy resin as main components is disclosed (see Patent Documents 3 to 8).
The above technology has ensured a practical level of adhesion between the polyimide film and the copper foil. However, in recent years, the characteristics required for the base material for semiconductor packages of such multilayer substrates have increased, and conventional lead frames The same reliability as the IC package used has been demanded. Semiconductor package reliability tests require stability in harsh environments such as high-temperature and high-humidity tests and thermal shock tests, and it has become a problem that conventional polyimide films cannot satisfy these requirements.
In order to cope with such a problem, a proposal has been made regarding a specific polyimide film in which a dimensional change due to temperature is suppressed (see Patent Document 9).
In addition, a glass substrate has been proposed for the purpose of providing a substrate that is stable against temperature changes (see Patent Document 10).
In any of the previously proposed technologies, a multilayer substrate that is stable against temperature changes has not been sufficiently achieved. The stability of the multilayer substrate itself with respect to temperature changes and the mutual divergence of the linear expansion coefficients between the multilayer substrates due to temperature changes are not achieved. There is no product that satisfies both the resistance to peeling due to the above.
JP 09-289229 A JP 09-289231 A JP 09-298220 A Japanese Patent Application Laid-Open No. 09-321094 Japanese Patent Laid-Open No. 10-084018 Japanese Patent Laid-Open No. 10-109070 Japanese National Patent Publication No. 11-505184 JP 2003-204152 A

  The present invention has been made to solve the above-described problems, and the thickness accuracy of the insulating layer is high. As a result, the characteristic impedance of the transmission line is stable, and is good even after a temperature cycle is applied. It is an object of the present invention to provide a multilayer substrate that has high reliability under high temperature and high humidity, has a small difference in linear expansion coefficient from a glass substrate, and has high connection reliability during bare chip mounting.

That is, this invention is based on the following structure.
1. A multilayer substrate having a structure in which a heat-resistant film is laminated on a glass substrate through an adhesive, the heat-resistant film reacting an aromatic diamine having a benzoxazole structure with an aromatic tetracarboxylic acid anhydride. A multilayer substrate, wherein the heat-resistant film has a linear expansion coefficient in the range of −2 to 10 ppm / ° C.
2. 1. The adhesive is at least one adhesive selected from thermoplastic polyimide and polyamideimide. Multilayer board.

  In the present invention, as a film in a multilayer substrate in which a heat-resistant film and a glass substrate are laminated, a polyimide film having a specific structure with a low linear expansion coefficient is used, and a specific adhesive is used to further configure the multilayer substrate. The position accuracy between layers is high, high-density wiring can be formed, and the elastic modulus of the film is high, and thermal deformation does not occur within the normal process temperature range. It is possible to keep the thickness accuracy constant, and as a result, it is possible to form a good transmission line with little variation in characteristic impedance. Furthermore, both the stability of the multilayer substrate itself with respect to temperature change and the resistance to peeling due to the mutual divergence of the linear expansion coefficients between the multilayer substrates due to temperature change are satisfied.

In general, it has been difficult to produce fine wiring with a ceramic substrate. Multi-layer stacking is generally performed and is suitable for realizing complicated wiring. The glass substrate has environmental stability, a low linear expansion coefficient, and high reliability, and these performances can be realized in a substrate using this. However, the semiconductor chip wiring has been miniaturized today, and it has been desired to have a rewiring layer capable of drawing a fine pattern when connected to a glass substrate. However, when a material having a physical property different from that of the glass substrate is bonded, there has been no practical use due to a decrease in connection reliability, peeling or lifting at the bonded portion.
The multilayer substrate in which the low linear expansion coefficient film in the present invention is bonded to a glass substrate can produce a substrate with high connection reliability, and also has sufficient adhesive strength with higher heat resistance than a conventional circuit substrate by a build-up method on the glass substrate. The resulting multilayer board has fine wiring, environmental stability, and high reliability.

The polyimide film used in the present invention is specifically a film obtained from a polyimide obtained by condensation of a diamine having a benzoxazole structure and an aromatic tetracarboxylic acid anhydride.
In general, a polyimide is formed into a green film (also referred to as a precursor film or a polyamic acid film) by applying a polyamic acid solution obtained by reacting diamines and tetracarboxylic anhydride in a solvent to a support and drying. In addition, the green film can be obtained by subjecting the green film to a high temperature heat treatment on the support or in a state where the green film is peeled off from the support to perform a dehydration ring closure reaction.
Specific examples of the aromatic diamine having a benzoxazole structure in the present invention include the following, and these diamines may be used alone or in combination of two or more.
Examples of aromatic diamines having a benzoxazole structure include the following compounds.

これらの中でも、合成のし易さの観点から、アミノ（アミノフェニル）ベンゾオキサゾールの各異性体が好ましい。ここで、「各異性体」とは、アミノ（アミノフェニル）ベンゾオキサゾールが有する２つアミノ基が配位位置に応じて定められる各異性体である（例；上記「化１」〜「化４」に記載の各化合物）。これらのジアミンは、単独で用いてもよいし、二種以上を併用してもよい。
本発明においては、前記ベンゾオキサゾール構造を有する芳香族ジアミンを７０モル％以上使用することが好ましい。

Among these, amino (aminophenyl) benzoxazole isomers are preferable from the viewpoint of ease of synthesis. Here, “each isomer” refers to each isomer in which two amino groups of amino (aminophenyl) benzoxazole are determined according to the coordination position (eg, the above “formula 1” to “formula 4”). Each compound described in the above. These diamines may be used alone or in combination of two or more.
In the present invention, it is preferable to use 70 mol% or more of the aromatic diamine having the benzoxazole structure.

The present invention is not limited to the above matters, and the following aromatic diamines may be used, but preferably the benzoxazole structure exemplified below is not provided as long as it is less than 30 mol% of the total aromatic diamines. It is a polyimide film using one or more diamines in combination. If it is less than 30 mol% of all diamines, the polyimide film which used together diamine illustrated below may be sufficient.
Examples of such diamines include 4,4′-bis (3-aminophenoxy) biphenyl, bis [4- (3-aminophenoxy) phenyl] ketone, and bis [4- (3-aminophenoxy) phenyl]. Sulfide, bis [4- (3-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (3-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, m-aminobenzylamine, p-aminobenzylamine,

3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl sulfide, 3,3′-diaminodiphenyl sulfoxide, 3,4′-diaminodiphenyl sulfoxide 4,4'-diaminodiphenyl sulfoxide, 3,3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminobenzophenone, 3,4'- Diaminobenzophenone, 4,4′-diaminobenzophenone, 3,3′-diaminodiphenylmethane, 3,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, bis [4- (4-aminophenoxy) phenyl] methane, 1 , 1-Bi [4- (4-aminophenoxy) phenyl] ethane, 1,2-bis [4- (4-aminophenoxy) phenyl] ethane, 1,1-bis [4- (4-aminophenoxy) phenyl] propane, 1 , 2-bis [4- (4-aminophenoxy) phenyl] propane, 1,3-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl ]propane,

1,1-bis [4- (4-aminophenoxy) phenyl] butane, 1,3-bis [4- (4-aminophenoxy) phenyl] butane, 1,4-bis [4- (4-aminophenoxy) Phenyl] butane, 2,2-bis [4- (4-aminophenoxy) phenyl] butane, 2,3-bis [4- (4-aminophenoxy) phenyl] butane, 2- [4- (4-aminophenoxy) Phenyl] -2- [4- (4-aminophenoxy) -3-methylphenyl] propane, 2,2-bis [4- (4-aminophenoxy) -3-methylphenyl] propane, 2- [4- ( 4-aminophenoxy) phenyl] -2- [4- (4-aminophenoxy) -3,5-dimethylphenyl] propane, 2,2-bis [4- (4-aminophenoxy) -3,5-dimethylphen Le] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane,

1,4-bis (3-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 4,4′-bis (4-aminophenoxy) ) Biphenyl, bis [4- (4-aminophenoxy) phenyl] ketone, bis [4- (4-aminophenoxy) phenyl] sulfide, bis [4- (4-aminophenoxy) phenyl] sulfoxide, bis [4- ( 4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] ether, 1,3-bis [4- (4-aminophenoxy) ) Benzoyl] benzene, 1,3-bis [4- (3-aminophenoxy) benzoyl] benzene, 1,4-bis [4- ( -Aminophenoxy) benzoyl] benzene, 4,4'-bis [(3-aminophenoxy) benzoyl] benzene, 1,1-bis [4- (3-aminophenoxy) phenyl] propane, 1,3-bis [4 -(3-aminophenoxy) phenyl] propane, 3,4'-diaminodiphenyl sulfide,

2,2-bis [3- (3-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, bis [4- (3-aminophenoxy) phenyl] methane, 1,1 -Bis [4- (3-aminophenoxy) phenyl] ethane, 1,2-bis [4- (3-aminophenoxy) phenyl] ethane, bis [4- (3-aminophenoxy) phenyl] sulfoxide, 4,4 '-Bis [3- (4-aminophenoxy) benzoyl] diphenyl ether, 4,4'-bis [3- (3-aminophenoxy) benzoyl] diphenyl ether, 4,4'-bis [4- (4-amino-α) , Α-dimethylbenzyl) phenoxy] benzophenone, 4,4′-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] diphenylsulfone, bis 4- {4- (4-aminophenoxy) phenoxy} phenyl] sulfone, 1,4-bis [4- (4-aminophenoxy) phenoxy-α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-aminophenoxy) phenoxy-α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-amino-6-trifluoromethylphenoxy) -α, α-dimethylbenzyl] benzene, 1,3 -Bis [4- (4-amino-6-fluorophenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-amino-6-methylphenoxy) -α, α-dimethylbenzyl Benzene, 1,3-bis [4- (4-amino-6-cyanophenoxy) -α, α-dimethylbenzyl] benzene,

3,3′-diamino-4,4′-diphenoxybenzophenone, 4,4′-diamino-5,5′-diphenoxybenzophenone, 3,4′-diamino-4,5′-diphenoxybenzophenone, 3, 3'-diamino-4-phenoxybenzophenone, 4,4'-diamino-5-phenoxybenzophenone, 3,4'-diamino-4-phenoxybenzophenone, 3,4'-diamino-5'-phenoxybenzophenone, 3,3 '-Diamino-4,4'-dibiphenoxybenzophenone, 4,4'-diamino-5,5'-dibiphenoxybenzophenone, 3,4'-diamino-4,5'-dibiphenoxybenzophenone, 3,3'- Diamino-4-biphenoxybenzophenone, 4,4′-diamino-5-biphenoxybenzophenone, 3,4 -Diamino-4-biphenoxybenzophenone, 3,4'-diamino-5'-biphenoxybenzophenone, 1,3-bis (3-amino-4-phenoxybenzoyl) benzene, 1,4-bis (3-amino- 4-phenoxybenzoyl) benzene, 1,3-bis (4-amino-5-phenoxybenzoyl) benzene, 1,4-bis (4-amino-5-phenoxybenzoyl) benzene, 1,3-bis (3-amino) -4-biphenoxybenzoyl) benzene, 1,4-bis (3-amino-4-biphenoxybenzoyl) benzene, 1,3-bis (4-amino-5-biphenoxybenzoyl) benzene, 1,4-bis (4-Amino-5-biphenoxybenzoyl) benzene, 2,6-bis [4- (4-amino-α, α-dimethylbenzyl) pheno Si] benzonitrile and some or all of the hydrogen atoms on the aromatic ring in the aromatic diamine are halogen atoms, alkyl groups having 1 to 3 carbon atoms or alkoxyl groups, cyano groups, or alkyl groups or alkoxyl group hydrogen atoms. Examples thereof include aromatic diamines substituted with a halogenated alkyl group having 1 to 3 carbon atoms partially or wholly substituted with a halogen atom or an alkoxyl group.

  The aromatic tetracarboxylic acids used in the present invention are, for example, aromatic tetracarboxylic anhydrides. Specific examples of the aromatic tetracarboxylic acid anhydrides include the following, but it is preferable to use 70 mol% or more in polyimide, and it is particularly preferable to use 70 mol% or more of pyromellitic acid. preferable.

These tetracarboxylic dianhydrides may be used alone or in combination of two or more.
In the present invention, as long as it is less than 30 mol% of the total tetracarboxylic dianhydrides, one or more of the non-aromatic tetracarboxylic dianhydrides exemplified below are used in combination regardless of the above-mentioned limitations. It doesn't matter. Examples of such tetracarboxylic acid anhydrides include butane-1,2,3,4-tetracarboxylic dianhydride, pentane-1,2,4,5-tetracarboxylic dianhydride, and cyclobutanetetracarboxylic acid. Acid 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-ethylcyclohex-1-ene-3- (1,2), 5,6-tetracarboxylic dianhydride 1-ethylcyclohexane -(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, 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 dianhydride, bicyclo [2.2.2] Oct-7-ene-2,3,5,6-tetracarboxylic dianhydride and the like. These tetracarboxylic dianhydrides may be used alone or in combination of two or more.

  The solvent used when the polyamic acid is obtained by reacting (polymerizing) the aromatic diamine and the aromatic tetracarboxylic acid (anhydride) dissolves both the monomer as a raw material and the polyamic acid to be produced. Although it will not specifically limit if it is a thing, A polar organic solvent is preferable, for example, N-methyl- 2-pyrrolidone, N-acetyl- 2-pyrrolidone, N, N- dimethylformamide, N, N- diethylformamide, N, N -Dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoric amide, ethyl cellosolve acetate, diethylene glycol dimethyl ether, sulfolane, halogenated phenols and the like. These solvents can be used alone or in combination. The amount of the solvent used may be an amount sufficient to dissolve the monomer as a raw material. As a specific amount used, the mass of the monomer in the solution in which the monomer is dissolved is usually 5 to 40% by mass, The amount is preferably 10 to 30% by mass.

In order to seal the molecular terminal of the polyimide or linear polyamic acid of the present invention with an end group having a carbon-carbon double bond, maleic anhydride or the like can be used. The amount of maleic anhydride used is 0.001 to 1.0 molar ratio per mole of aromatic diamine component.
The polar organic solvent used in the synthesis of the polyamic acid of the present invention is not particularly limited as long as it dissolves both the raw material monomer and the produced polyamic acid. For example, N-methyl-2-pyrrolidone, N- Acetyl-2-pyrrolidone, N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoric amide, ethyl cellosolve acetate, diethylene glycol dimethyl ether, sulfolane, halogenated phenols, etc. These solvents can be used alone or in combination. The amount of the polar organic solvent used may be an amount sufficient to dissolve the charged monomer, usually 5 to 50% by weight, preferably 10 to 20% by weight. .
The organic solvent solution of the polyamic acid used in the present invention preferably contains 5 to 40% by weight, more preferably 10 to 30% by weight of the solid content, and the viscosity is measured by a Brookfield viscometer. Those having a viscosity of 10 to 2000 Pa · s, preferably 100 to 1000 Pa · s are preferred because stable liquid feeding is possible. The polymerization reaction is continuously carried out in the temperature range of 0 to 80 ° C. for 10 minutes to 30 hours while stirring and / or mixing in an organic solvent. The polymerization reaction can be divided or the temperature can be increased or decreased as necessary. It doesn't matter. In this case, the order of addition of both reactants is not particularly limited, but it is preferable to add aromatic tetracarboxylic anhydrides to the solution of aromatic diamines.

The polyimide film of the present invention is obtained by continuously extruding or applying a polyamic acid solution to a support in the form of a film, followed by drying, peeling the green film from the support, stretching, drying, and heat treatment. As a typical method for producing a polyimide film from an organic solvent of polyamic acid, an organic solvent solution of polyimide acid that does not contain a ring-closing catalyst and a dehydrating agent is cast on a support from a nozzle with a slit. The film is then formed into a film and heated to dry on the support to form a green film having self-supporting properties. Then, the film is peeled off from the support and further heat-dried at a high temperature for imidization, Then, an organic solvent of polydoic acid containing a ring-closing catalyst and a dehydrating agent is cast from a slit base onto a support. Examples include a chemical ring closure method in which a film is formed into a film and partially imidized on a support to form a film having self-supporting properties, then the film is peeled off from the support, dried / imidized by heating, and heat-treated. It is done.
The support in the present invention is a drum or belt-like rotating body used when forming a polyamic acid solution into a film. The polyamic acid solution is applied on a support and is self-supporting by heat drying. The surface of the support may be metal, plastic, glass, porcelain, etc., preferably metal, and more preferably SUS material that does not rust and has excellent corrosion resistance. Further, metal plating such as Cr, Ni, Sn may be performed. The surface of the support in the present invention can be mirror-finished or processed into a satin finish as necessary.
Although the polyimide film in the present invention can be produced as described above, it is essential for the reason described above that the linear expansion coefficient of these films is −2 to 10 ppm / ° C., more preferably −2 ppm. / ° C. to 5 ppm / ° C., more preferably −2 ppm / ° C. to 3 ppm / ° C.
When the linear expansion coefficient of the film is out of the range of −2 to 10 ppm / ° C., the difference between the linear expansion of the film and the glass substrate becomes large, so that a large stress is generated between the film and the glass substrate during heating and cooling. It tends to cause peeling, and as a result, adversely affects the results of the heat cycle test.
For this reason, in the production of the film, it is necessary to control the drying and imidization process so that the disorder of the molecular orientation is reduced and the film has a uniform structure.

The adhesive used in the multilayer substrate having a configuration in which the heat-resistant film in the present invention is laminated on the glass substrate via an adhesive is not particularly limited as long as it is a heat-resistant adhesive. Examples include thermoplastic polyamide-imide, thermoplastic polyimide, thermoplastic polyimide siloxane, thermoplastic polyamide-imide siloxane, polyether ether ketone, liquid crystal polymer, polyphenylene oxide, epoxy resin, and one or more resin blends of these resins. However, an adhesive using one or more of thermoplastic polyimide or polyamideimide is particularly preferable, and an organic or inorganic filler, a flame retardant, or the like can be added to these as necessary. Further, these adhesives preferably have a Tg (glass transition point) of 130 ° C. or higher and lower than 400 ° C., and if it is lower than 130 ° C., the heat resistance of the polyimide film layer is often impaired. When the point is 400 ° C. or higher, problems such as difficulty in handling during lamination with the polyimide film layer increase, which is not preferable. More preferably, it is 240 degreeC or more and 400 degrees C or less.
Further, from the viewpoint of maintaining heat resistance, a 5% weight loss temperature is 400 ° C. or higher, and an adhesive mainly composed of thermoplastic polyimide or thermoplastic polyamideimide and an adhesive obtained by adding a thermosetting component to these are desirable. . When the 5% weight loss temperature is 400 ° C. or less, the deterioration proceeds at a high temperature during the process, and the use becomes difficult.

  The lamination method when the polyimide zenzaxazole film of the present invention, which is a heat-resistant film, is laminated on a glass substrate through an adhesive is not particularly limited. For example, a coextrusion method, one layer A method of casting a polyimide polyamic acid solution of an adhesive layer on a polyimide film and imidizing it, and laminating a precursor film of the other polyimide on a polyimide film precursor film which is one layer A glass substrate using a heat-resistant film layer with an adhesive obtained by imidizing together, a method of imidizing a polyimide film layer by applying a polyimide polyamic acid solution as an adhesive by spray coating, etc. These adhesives may be provided on a glass substrate and a heat resistant film may be laminated later.

As the glass substrate in the present invention, a glass substrate used in a conventionally known glass substrate can be used, but a substrate using photosensitive glass is preferably used. Further, a glass substrate may be provided with through holes, conductor circuits, resistors, inductors, and capacitors. In addition, the manufacturing method of the multilayer substrate which laminated | stacked the heat-resistant film layer on the glass substrate using the adhesive agent in this invention is not limited, Methods, such as buildup and collective lamination, are mentioned as a preferable example.
Multi-layer production with glass substrates is difficult both in terms of cost and technology, so 1 to 8 heat-resistant films are more desirable for bonding one glass or at most two. It is desirable to realize fine wiring by stacking about 1 to 3 layers. With these configurations, a vertically penetrating structure can be realized with fine wiring of an interposer between chips at the time of three-dimensional mounting.
In addition, the structure in which a hole is partially opened in the film is optimal for transmitting an electric signal while transmitting light through a glass substrate and transmitting an optical signal.
In addition, when forming a circuit by superimposing films, a conventionally known build-up method, batch lamination method, etc. may be used. As a build-up method, semi-additive, substruct, full additive , Etc. are known. These may be used as appropriate.

Hereinafter, the effectiveness of the present invention will be described with reference to examples, but the present invention is not limited thereto. In addition, the evaluation method of the physical property in the following examples is as follows.
1. Reduced viscosity of polyamic acid (ηsp / C)
A solution dissolved in N-methyl-2-pyrrolidone so that the polymer concentration was 0.2 g / dl was measured at 30 ° C. using an Ubbelohde type viscosity tube.

2. Film thickness of polyimide film The thickness of the film was measured using a micrometer (Finereuf, Millitron 1245D).

3. Linear expansion coefficient (CTE) of polyimide film
The expansion / contraction rate was measured under the following conditions, and the range from 30 to 300 ° C. was divided at 15 ° C. intervals and obtained from the average value of the expansion / contraction rate / temperature of each divided range.
Device name: TMA4000S manufactured by MAC Science
Sample length; 20mm
Sample width: 2 mm
Temperature rise start temperature: 25 ° C
Temperature rising end temperature: 400 ° C
Temperature increase rate: 5 ° C / min
Atmosphere: Argon

(Polyamide acid polymerization-1) PMDA-DAMBO
<Polymerization of a polyamic acid composed of a diamine having a benzoxazole structure>
The inside of a reaction vessel equipped with a nitrogen introduction tube, a thermometer, and a stirring rod was purged with nitrogen, and then 500 parts by mass of 5-amino-2- (p-aminophenyl) benzoxazole (DAMBO) was charged. Next, after 8000 parts by mass of N, N-dimethylacetamide was added and completely dissolved, 485 parts by mass of pyromellitic dianhydride (PMDA) was added and stirred at a reaction temperature of 25 ° C. for 48 hours. A viscous polyamic acid solution (A) was obtained. The solution obtained had a ηsp / C of 4.0 dl / g.

(Polymerization of polyamic acid-2) PMDA-ODA
A polyamide obtained by dissolving 545 parts by weight of pyromellitic anhydride and 500 parts by weight of 4,4′diaminodiphenyl ether (ODA) in 8000 parts by weight of N, N-dimethylacetamide and reacting in the same manner while maintaining the temperature at 20 ° C. or lower. An acid solution (B) was obtained. The ηsp / C of the obtained solution was 2.2 and was dl / g.

(Preparation of adhesive resin-1: PI)
After the inside of the reaction vessel equipped with a nitrogen introduction tube, a thermometer, and a stirring rod was purged with nitrogen, 368.4 parts by mass of 4,4′-bis (3-aminophenoxy) biphenyl, 59.24 parts by mass of phthalic anhydride, anhydrous 174.5 parts by mass of pyromellitic acid and 2,172 parts by mass of m-cresol were charged, heated to 200 ° C. with stirring, and kept at 200 ° C. for 6 hours. Next, toluene was charged into the reaction solution, the precipitate was filtered off, washed several times with toluene, and then dried at 250 ° C. for 6 hours in a nitrogen atmosphere to obtain 510 parts by mass (yield 90.1). %) Polyimide powder (C).

(Adhesive resin preparation-2: PAI)
After replacing the inside of the reaction vessel equipped with a nitrogen introduction tube, a thermometer, and a stirring rod with nitrogen, 192 parts by mass of trimellitic anhydride, 211 parts by mass of O-tolidine diisocyanate, and 35 parts by mass of 2,4-tolylene diisocyanate were added to the reaction vessel. , 1 part by mass of triethylenediamine and 2500 parts by mass of N-methyl-2-pyrrolidone were added, the temperature was raised to 130 ° C. over 1 hour with stirring, and the reaction was further continued at 130 ° C. for 5 hours, and the logarithmic viscosity was 1.6 dl / g. A polyimide resin solution (D) was obtained.

(Preparation of adhesive resin-3: PAI)
After replacing the inside of the reaction vessel equipped with a nitrogen introduction tube, a thermometer, and a stirring rod with nitrogen, 144 mass parts of trimellitic anhydride (manufactured by Mitsubishi Gas Chemical Co., Inc.), 64 mass of benzophenone tetracarboxylic dianhydride was added to the reaction vessel. Parts (manufactured by Daicel Chemical Industries, Ltd.), 15 parts by mass of biphenyltetracarboxylic dianhydride (manufactured by Mitsubishi Chemical Corporation), 264 parts by mass of o-tolidine diisocyanate (manufactured by Nippon Soda Co., Ltd.), 3 parts by mass of triethylenediamine (Nacalai Tesque Co., Ltd.) and 2300 parts by mass of N-methyl-2-pyrrolidone (Mitsubishi Chemical Co., Ltd.) (polymer concentration 15%) were added, the temperature was raised to 100 ° C. in 2 hours, and 5 Reacted for hours. Next, 726 parts by mass of NMP (polymer concentration: 12% by weight) was added and cooled to room temperature. The obtained liquid was yellowish brown transparent, and the obtained polymer was dissolved in NMP. This is designated as polyimide resin solution (E).

(Preparation of adhesive resin-4: PAI)
After replacing the inside of the reaction vessel equipped with a nitrogen introduction tube, a thermometer, and a stirring rod with nitrogen, 190 mass parts and 250 mass parts of trimellitic anhydride (TMA) and oxydianiline diisocyanate were charged in the reaction vessel, respectively. N-methyl-2-pyrrolidone (NMP) was charged to a polymer concentration of 40% and reacted at 120 ° C. for about 1 hour, then heated to 180 ° C. and allowed to react for 5 hours with stirring. Next, the heating was stopped and the solution was cooled and further diluted with N-methyl-2-pyrrolidone to obtain a polymer solution (F) having a solid content concentration of 20%. After reprecipitation with methanol and drying under reduced pressure, the logarithmic viscosity and the glass transition point were measured and found to be 0.9 dl / g and 290 ° C., respectively. This dried product had a 5% weight loss temperature of 495 ° C and a glass transition point of 290 ° C.

(Creation of adhesive resin-5: PI)
In a 2 liter glass separable flask, 1000 parts by mass of N-methyl-2-pyrrolidone (NMP) was placed, and 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride was added to the solution. (A-BPDA) 73.56 parts by mass, diaminopolysiloxane (DAPS) (Toray Dow Corning Silicone, BY16-853U) 88 parts by mass, 2,2-bis [4- (4 -Aminophenoxy) phenyl] propane (BAPP) 61.58 parts by mass are added and stirred at 60 ° C. for 2 hours under a nitrogen atmosphere. Thereafter, the temperature was further raised to 200 ° C., and the polymerization reaction was carried out for 3 hours while removing water. Finally, the reaction solution was added to 10 liters of water, and using a homomixer, the polymer was precipitated by precipitation for 30 minutes and the polymer powder was isolated. This polymer powder was washed twice at 80 ° C. for 1 hour using a homomixer in 5 liters of 2-propanol, dried with hot air at 120 ° C. for 5 hours, and then vacuum dried at 120 ° C. for 24 hours. 210 parts by mass of polyimide siloxane powder was obtained.
The reaction vessel was charged with 85 parts of polyimidesiloxane, 10 parts by weight of an epoxy resin (manufactured by Yuka Shell, Epicort 828), 5 parts by weight of BT resin (BT2170, manufactured by Mitsubishi Gas Chemical Company), and tetrahydrofuran was further solidified. The mixture was charged so as to have a partial concentration of 25%, and stirred at room temperature (25 ° C.) for 2 hours to obtain a uniformly dissolved polyimidesiloxane composition solution (G). The 5% weight reduction temperature of this cured product was 408 ° C, and the glass transition point was 167 ° C.

(Creation of adhesive resin -6: PI)
The inside of the reaction vessel equipped with a nitrogen introduction tube, a thermometer, and a stirring rod is purged with nitrogen, and then 4,4 ′ diamine is introduced and stirred well to be uniform, and then colloidal silica is dispersed in dimethylacetamide. Snowtex (trade name) DMAC-Zl (manufactured by Nissan Chemical Industries, Ltd.) 40.5 parts by mass (including 8.1 parts by mass of silica) was added, the solution was cooled to 0 ° C., and 4,4′-oxydiphthalic acid 990 parts by weight of anhydride was added and stirred for 24 hours. A pale yellow and viscous polyamic acid solution (H) was obtained. The solution obtained had a ηsp / C of 2.28 dl / g.

(Preparation of adhesive resin-7)
30 parts by mass of bisphenol A type epoxy resin (epoxy equivalent 469, Epicoat 1001 manufactured by Yuka Shell Epoxy), 40 parts by mass of cresol novolac type epoxy resin (epoxy equivalent 215, Epiklon N-673 manufactured by Dainippon Ink & Chemicals, Inc.), triazine 30 parts by mass of a structure-containing phenol novolac resin (phenolic hydroxyl group equivalent 120, manufactured by Dainippon Ink & Chemicals, Phenolite KA-7052) was dissolved in 20 parts by mass of ethyl diglycol acetate and 20 parts by mass of solvent naphtha with stirring. 15 parts by mass of terminal epoxidized polybutadiene rubber (manufactured by Nagase Kasei Kogyo Co., Ltd., Denarex R-45EPT), 1.5 parts by mass of pulverized 2-phenyl-4,5-bis (hydroxymethyl) imidazole, and finely pulverized silica 2 Parts by mass, silicon 0.5 parts by mass of a foaming agent was added to prepare a resin composite solution (I).

(Example of film production-1)
The polyamic acid solution (A) was coated on the non-lubricant surface of polyethylene terephthalate film A-4100 (manufactured by Toyobo Co., Ltd.) using a comma coater, dried at 110 ° C. for 5 minutes, and then peeled off from the support. Without winding up the polyamic acid film. The polyamic acid film is passed through a pin tenter having three heat treatment zones, the first stage 150 ° C. × 2 minutes, the second stage 220 ° C. × 2 minutes, the third stage 475 ° C. × 4 minutes, and slit to 500 mm width. A polyimide film (A) having a thickness of 10 μm was obtained.

(Film creation example-2)
The polyamic acid solution (B) was coated on the non-lubricant surface of polyethylene terephthalate film A-4100 (manufactured by Toyobo Co., Ltd.) using a comma coater, dried at 110 ° C. for 5 minutes, and then peeled off from the support. Without winding up the polyamic acid film. The polyamic acid film is passed through a pin tenter having three heat treatment zones, the first stage 150 ° C. × 2 minutes, the second stage 220 ° C. × 2 minutes, the third stage 460 ° C. × 4 minutes, and slit to 500 mm width. A polyimide film (B) having a thickness of 10 μm was obtained.

(Film creation example-3)
The polyimide powder (C) was kneaded and melted at 380 to 410 ° C. using a twin screw extruder, extruded and granulated to obtain pellets. The obtained pellets were supplied to a single screw extruder (molding temperature 420 ° C.) having a diameter of 50 mm, passed through a 10 μm leaf disk type filter attached to the front of the T die, extruded from a 1100 mm wide T die, and a thickness of 25 μm. The thermoplastic polyimide film (C) was obtained. The 5% weight reduction temperature of the thermoplastic polyimide film (C) was 580 ° C., and the glass transition point was 270 ° C.

(Film creation example-4)
The polyimide resin solution (D) was coated on a non-lubricant surface of polyethylene terephthalate film A-4100 (manufactured by Toyobo Co., Ltd.) using a comma coater, dried at 120 ° C. for 3 minutes, and then 220 ° C. × Heat treatment was performed for 2 hours and slit to a width of 500 mm to obtain a 25 μm polyamideimide film (D). The 5% weight reduction temperature of the polyamideimide film (D) was 485 ° C., and the glass transition point was 320 ° C.

(Example of film production-5)
A polyimide resin solution (E) was coated on a non-lubricant surface of polyethylene terephthalate film A-4100 (manufactured by Toyobo Co., Ltd.) using a comma coater, dried at 120 ° C. for 3 minutes, and then 220 ° C. × Heat treatment was performed for 2 hours and slit to a width of 500 mm to obtain a 25 μm polyamideimide film (E). The 5% weight reduction temperature of the polyamideimide film (E) was 505 ° C., and the glass transition point was 340 ° C.

(Example of film production-7)
The polyamic acid solution (H) was applied on the non-lubricant surface of polyethylene terephthalate film A-4100 (manufactured by Toyobo Co., Ltd.), dried at 120 ° C. for 5 minutes, and then peeled off from polyethylene terephthalate film A-4100. The film was fixed to a SUS frame, heated to 450 ° C. at 20 ° C./min in a muffle furnace, and then held for 10 minutes to obtain a 25 μm polyimide film (H). The 5% weight reduction temperature of the polyimide film (H) was 580 ° C., and the glass transition point was 212 ° C.

(Example of film production-8)
The obtained resin composite solution (I) is applied onto a PET film having a thickness of 38 μm using a roll coater so that the thickness after drying is 20 μm, and then dried at 80 to 120 ° C. for 10 minutes. Thus, an epoxy B stage film (I) of 25 μm was obtained. The 5% weight reduction temperature of this dried cured product was 317 ° C, and the glass transition point was 132 ° C.

<Sputter plating preparation example A>
The film A was slit to a width of 250 mm, put into a sputtering apparatus, evacuated, and then rolled back, gas was discharged from the film, and then the surface of the polyimide film was treated with oxygen glow discharge. Processing conditions are O2 gas pressure 2X10-3Torr, flow rate 50SCCM, discharge frequency 13.56MHz, output 250W, processing time is film feed rate 0.1m / min and effective plasma irradiation width is about 10cm, so plasma irradiation time at one place Is 1 minute. Thereafter, the NiCr base thin film layer having a thickness of 15 nm was formed on one surface of the film by a DC magnetron sputtering method using an argon gas with a NiCr alloy as a target. The degree of vacuum at the time of forming the thin film layer is 3 × 10 −3 Torr. Then, a copper thin film layer having a thickness of 250 nm was immediately formed by DC magnetron sputtering using argon gas with copper as a target. The composition of the target NiCr alloy was Ni 80 wt% and Cr 20 wt% purity 3N. The target Cu was 4N purity. Each target has a rectangular shape with a width of 12 cm in the film feeding direction and a width of 27 cm in the film feeding direction. Four rectangular targets are installed in the film feeding direction. The two targets are approaching each other, but they were used for NiCr. Since the distance between the target and the target used for Cu is separated, the NiCr sputtered atoms and the Cu atoms do not reach the film after being mixed in a vacuum, and the underlying NiCr thin film Each Cu thin film is formed without being mixed with each other to form a two-layer thin film. The sputtering equipment is a roll-to-roll system, and the surface treatment, NiCr layer creation, and Cu layer creation are performed sequentially while the film is moved from the roll to the unwinding chamber, sputtering chamber, spare chamber, and winding chamber. And then wound on a roll. Each chamber is roughly partitioned by a slit. In the sputtering chamber, the film is in contact with the chill roll and is cooled by the temperature of the chill roll (-5 degrees), but it does not use one NiCr target, one target near the unwinding side, and then from the two Cu targets. A thin film is formed by the metal particles.
The plating was performed on one side by bringing the electrode into contact with the sputtering metal layer using a roll-to-roll electroplating apparatus. Thereby, a metallized polyimide film (CCL) (A) was obtained.

<Sputter plating preparation example B>
All the conditions and procedures other than using the film B were the same as in the sputter plating preparation example A, and sputter plating was performed. Thereby, a metallized polyimide film (B) was obtained.

<Sputter plating preparation example D>
All the conditions and procedures other than using the polyamideimide film (D) were the same as in Sputter Plating Preparation Example 1, and sputter plating was performed. Thereby, the metallized polyamideimide film (D) was obtained.

<Pattern creation example 1>
Using the obtained metallized polyimide film (A), photoresist: FR-200, manufactured by Shipley Co., Ltd. was applied and dried, and then closely exposed with a glass photomask, and further developed with a 1.2 mass% KOH aqueous solution. Next, using a cupric chloride etching line containing HCl and hydrogen peroxide, etching is performed at 40 ° C. and a spray pressure of 2 kgf / cm 2, and the “comb pattern” necessary for the evaluation test is the conductor width and conductor spacing. Was 40 μm / 40 μm, and the number of patterns was 20 after one side test pattern was formed, washed, and annealed at 125 ° C. for 1 hour. Thereby, the film (A) with a pattern was obtained.

<Pattern creation example 2>
Using the obtained metallized polyimide film (B), photoresist: FR-200, manufactured by Shipley Co., Ltd. was applied and dried, and then contacted and exposed with a glass photomask, and further developed with a 1.2 mass% KOH aqueous solution. Next, etching is performed at an etching line of cupric chloride containing HCl and hydrogen peroxide at 40 ° C. and a spray pressure of 2 kgf / cm 2, and a “comb pattern” as shown in FIG. 1 is necessary for the evaluation test. The conductor width and conductor spacing were 40 μm / 40 μm, and the number of patterns was 20 test patterns on one side, followed by cleaning and annealing at 125 ° C. for 1 hour. Thereby, the film (B) with a pattern was obtained.

<Pattern creation example 3>
A film with pattern (D) was obtained in the same manner as in Pattern Preparation Example 1 except that the obtained metallized polyamideimide film (D) was used.

(Example of production of film with pattern adhesive layer-1)
The polyimide siloxane composition solution (F) is applied on the non-patterned surface of the patterned film (A) using a bar coater so that the thickness after drying is 25 μm, and then dried at 90 ° C. for 1 hour. Thus, a film with a pattern adhesive layer (F) was obtained.

(Creation example 2 of a film with a pattern adhesive layer)
The polyimide siloxane composition solution (G) is applied on the non-patterned surface of the patterned film (A) using a roll coater so that the thickness after drying is 25 μm, and then dried at 90 ° C. for 5 minutes. As a result, a film with a pattern adhesive layer (G) was obtained.

Example 1
A thermoplastic polyimide film (C) was placed on the glass substrate, and a patterned film (A) was placed on the glass substrate and positioned, followed by pressing at 280 ° C. for 10 minutes. The pressure at this time was 10 MPa. After the pressing, heat treatment was further performed at 400 ° C. for 30 minutes in a muffle furnace flowed with N 2 to obtain a multilayer board for testing (AC) as a laminate.

Example 2
A thermoplastic polyimide film (C) is placed on one surface of a glass substrate, a patterned film (A) is further placed thereon, and a thermoplastic polyimide film (C) and a patterned film (A) are alternately placed, The film with the pattern (A) was piled up to 5 sheets, positioned, and pressed at 280 ° C. for 10 minutes. The pressure at this time was 10 MPa. After pressing, heat treated at 400 ° C. for 30 minutes in a muffle furnace with N2 flow. On the other side of the glass substrate, the thermoplastic polyimide film (C) and the patterned film (A) were alternately placed, The film with the pattern (A) was piled up to 5 sheets, positioned, and pressed at 280 ° C. for 10 minutes. The pressure at this time was 10 MPa. After pressing, heat treatment was further performed at 400 ° C. for 30 minutes in a muffle furnace with N 2 flow, to obtain a test multilayer substrate (AC5) as shown in FIG.

Example 3
A test multilayer substrate (AD5) as a laminate was obtained in the same manner as in Example 2 except that the polyamideimide film (D) was used and the press temperature was 350 ° C.

Example 4
A multilayer test substrate (AE5) as a laminate was obtained in the same manner as in Example 2 except that the polyamideimide film (E) was used and the press temperature was 380 ° C.

Example 5
Place the adhesive layer side of the film with the adhesive layer with pattern (F) on one side of the glass substrate, and then stack the five films with the adhesive layer with pattern (F) in the same manner on the glass substrate. Similarly, five sheets were stacked so that the adhesive surface was on the glass substrate side. Heat treatment was performed at 100 ° C. for 80 minutes and 200 ° C. for 120 minutes by a vacuum press to obtain a test multilayer substrate (AF5) as a laminate.

Example 6
Place the adhesive layer surface of the patterned adhesive layer-attached film (G) on one surface of the glass substrate, and stack 5 films with the patterned adhesive layer (G) in the same manner, and vacuum press at 120 ° C. Then, heat treatment is performed at 80 ° C. for 80 minutes and 120 ° C. for 120 minutes with a hot air dryer, and the adhesive layer surface of the film with the adhesive layer with pattern (G) is similarly placed on the other surface of the glass substrate. In the same manner, 5 films with an adhesive layer with a pattern (G) are stacked, vacuum pressed at 120 ° C., and then heat-treated with a hot air dryer at 80 ° C. for 80 minutes and 120 ° C. for 120 minutes to form a laminate. A test multilayer substrate (AG5) was obtained.

Example 7
A test multilayer substrate (AH5) as a laminate was obtained in the same manner as in Example 2 except that the polyamideimide film (H) was used and the pressing temperature was 250 ° C.

Comparative Example 1
A test multilayer substrate (BC5) as a laminate was obtained in the same manner as in Example 2 except that the patterned film (B) was used.

Comparative Example 2
A thermoplastic polyimide film (C) is placed on a film (D) with a pattern on a glass substrate, and a film (D) with a pattern is placed thereon, and further a thermoplastic polyimide film (C) and a film with a pattern (D ) Were alternately placed and stacked until there were five patterned films (D), and in the same manner as in Example 2, a multilayer board for testing (DC5) as a laminate was obtained.

Comparative Example 3
A test multilayer substrate (AI5) as a laminate was obtained in the same manner as in Example 2 except that the epoxy B stage film (I) was used and the press temperature was 250 ° C.

  The test multilayer substrates obtained above were evaluated according to the following, and the results are shown in Tables 1 to 3.

<Multi-layer board evaluation for testing>
《Reliability after high temperature》
The test multilayer substrate having the structure of the obtained heat-resistant film / adhesive layer / glass is treated under the condition of being left for 1000 hours in an atmosphere having a relative humidity of 85% and a temperature of 85 ° C., and evaluation of reliability after high temperature. Cut the test multilayer board with a diamond cutter, observe the cross section with a microscope, ○ where there is no distortion or peeling at each interface, and what the distortion or peeling at each interface is slightly seen Δ, and those where distortion and peeling at each interface were observed were marked with ×.
<Heat cycle test>
The test multilayer substrate having the structure of the obtained heat-resistant film / adhesive layer / glass was maintained for 3 minutes in an atmosphere of −65 ° C., and then the cycle of maintaining for 3 minutes in an atmosphere of 130 ° C. was repeated 1000 times. . After that, as an evaluation of the heat cycle test, the test multilayer substrate was cut with a diamond cutter, and the cross section was observed with a microscope, where no distortion or peeling was observed at each interface. A case where slight peeling was observed was indicated by Δ, and a case where distortion or peeling was observed at each interface was indicated by ×.

The multilayer substrate of the present invention is a multilayer substrate in which a heat-resistant polyimide film layer having specific physical properties and a glass substrate are laminated, and a circuit, an impedance element and the like are formed on the glass substrate, and the heat-resistant polyimide film The layer is a multilayer substrate on which conductor circuits and electronic components are mounted, and since circuits and impedance elements are formed on the glass substrate, it can be stable against temperature changes and maintain accurate values. Since a conductive circuit can be formed on the polyimide film layer, a fine circuit can be formed, so that the mounting density of the substrate can be improved and miniaturization is possible, and since the glass substrate is included therein, the bending as a multilayer substrate can be suppressed and In addition, there is no difference in the coefficient of linear expansion between the glass substrate and the polyimide film layer, so there is little warping of the multilayer substrate or peeling in the substrate. It is extremely useful as a fry multilayer substrate.
Produces a multilayer substrate for interposers that has good adhesion reliability under high temperature and high humidity even after a temperature cycle is applied, has a small difference in linear expansion coefficient from the glass substrate, and has high connection reliability during bare chip mounting. It is possible to do, and it is a very meaningful thing in the industry.
Since the smoothness and flatness of the glass are used, it is advantageous for fine circuit formation even in the case of build-up by using a glass-up method. By using a photosensitive glass, it is possible to reduce the via diameter. It is possible to form a fine pattern even at the portion.
Utilizing the transparency of glass, it is also effective as a support substrate for light, electrical transmission substrate creation, light emission, and light receiving element alone, which also transmits optical signals.
Because the glass layer has extremely high gas barrier properties, it is ideal for applications that require gas barrier properties, and because it is bonded to a glass with high gas barrier properties, there is less gas permeation at the bonded part, which is extremely high. It has reliability and is very meaningful in industry.

It is the schematic of the multilayer substrate of this invention.

Explanation of symbols

  None

Claims (2)

  A multilayer substrate having a structure in which a heat-resistant film is laminated on a glass substrate through an adhesive, the heat-resistant film reacting an aromatic diamine having a benzoxazole structure with an aromatic tetracarboxylic acid anhydride. A multi-layer substrate, wherein the heat-resistant film has a linear expansion coefficient in the range of −2 to 10 ppm / ° C.   The multilayer substrate according to claim 1, wherein the adhesive is at least one adhesive selected from thermoplastic polyimide and polyamideimide.

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