JP2009182073A - Multilayer substrate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a multilayer substrate in which a polyimide film and an inorganic substrate are stacked, for preventing peeling of the polyimide film, being excellent in productivity. <P>SOLUTION: In the multilayer substrate, the polyimide film is layered on the inorganic substrate with an adhesive in between. The polyimide film contains, as a main component, polyimide that results from reaction between aromatic tetracarboxilic acid and aromatic diamine, with the linear expansion coefficient being ≤10 ppm/°C. The 5% weight reduction temperature of the adhesive is ≥400°C, with the polyimide or polyimidimide being soluble in organic solvent. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a multilayer substrate having a multilayer structure using an inorganic substrate such as a ceramic substrate or a glass substrate as a core, and more specifically, laminating a ceramic substrate or a glass substrate and a heat-resistant film using an adhesive. The present invention relates to a multilayer substrate formed with an insulating layer.

  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. In other words, it is 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.

Conventional polyimide films have a problem of poor surface adhesion. Therefore, when multilayer lamination is performed via an adhesive, the adhesion reliability between the layers is poor, which may cause defective products. 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 constituent components is disclosed (see Patent Documents 1 to 6).
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 7).
In addition, a glass substrate has also been proposed for the purpose of providing a substrate that is stable against temperature changes (see Patent Document 8).
In any of the conventional proposed technologies, the stability against the temperature change is not sufficiently achieved, and the stability against the temperature change of the multilayer substrate itself and the peeling due to the mutual divergence of the linear expansion coefficients between the multilayer substrates due to the temperature change, etc. No one that satisfies both tolerances has been obtained.
In addition, semiconductor chip wiring has been miniaturized today, and when connected to an inorganic substrate such as a ceramic substrate or a glass substrate, a rewiring layer capable of drawing a fine pattern is desired. However, when a material having a physical property different from that of the inorganic substrate is bonded, there is no practical use due to a decrease in connection reliability, peeling or lifting at the bonded portion.

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 in order to solve the above-described problems. The thickness accuracy of the insulating layer is high, and as a result, the characteristic impedance of the transmission line is stable, the temperature cycle, and the high temperature and high humidity. In addition, there is a small difference in linear expansion coefficient from inorganic substrates such as ceramic substrates and glass substrates, high connection reliability when mounting bare chips, and the adhesive is stable in the varnish state, so the yield is high. It is an object of the present invention to provide a multilayer substrate that can be improved, can simplify the manufacturing process (good productivity), does not require imidization, has good insulating layer film quality, and small thickness unevenness.

The present invention that has solved the above-described problems has the following configuration.
1. In a multilayer substrate having a structure in which a polyimide film is laminated on an inorganic substrate through an adhesive, the polyimide film is mainly composed of polyimide obtained by reacting aromatic tetracarboxylic acids and aromatic diamines, and a wire A multilayer substrate characterized in that it is a polyimide film having an expansion coefficient of 10 ppm / ° C. or lower, a 5% weight reduction temperature of the adhesive is 400 ° C. or higher, and is an organic solvent-soluble polyimide or polyamideimide.
2. 1. The polyimide film as described above in which the polyimide film is mainly composed of polyimide benzoxazole obtained by condensation of aromatic tetracarboxylic acid anhydrides and diamines having a benzoxazole structure. The multilayer substrate described in 1.
3. The above-mentioned 1. The adhesive is mainly composed of polyimide obtained by reacting an aromatic tetracarboxylic acid having a benzophenone structure and an aromatic diamine. Or 2. The multilayer substrate described in 1.
4). 1. The inorganic substrate is a ceramic substrate or a glass substrate. ~ 3. A multilayer substrate according to any one of the above.

In the present invention, as a film in a multilayer substrate in which a heat-resistant film and an inorganic substrate are laminated, a polyimide film having a specific structure with a low linear expansion coefficient is used, and a specific adhesive is further used to configure the multilayer substrate. The position accuracy between the 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 against temperature changes and the resistance to peeling due to the mutual divergence of the linear expansion coefficients between the multilayer substrates due to temperature changes are satisfied, and the adhesive is stable in the varnish state, so the yield is high. The manufacturing process can be simplified (productivity is good), imidization is not required, the quality of the insulating layer film is good, and the thickness unevenness is small.
The multilayer substrate in which the low linear expansion coefficient film in the present invention is bonded to an inorganic substrate can produce a substrate with high connection reliability, and has a sufficient heat resistance higher than that of a conventional circuit substrate by a build-up method on the inorganic substrate. The resulting multilayer board has fine wiring, environmental stability, and high reliability.

The polyimide film in the present invention is a polyimide film obtained by reacting aromatic diamines and aromatic tetracarboxylic acids, and is particularly limited as long as it has a linear expansion coefficient of 10 ppm / ° C. or less. However, preferably, the following combinations of aromatic diamines and aromatic tetracarboxylic acids (anhydrides) are preferred examples.
A. Combination with aromatic tetracarboxylic acid having pyromellitic acid residue and aromatic diamine having benzoxazole structure.
B. A combination of an aromatic diamine having a phenylenediamine skeleton and an aromatic tetracarboxylic acid having a biphenyltetracarboxylic acid skeleton.
In particular, A. A combination for producing a polyimide film having an aromatic diamine residue having a benzoxazole structure is preferred.
A particularly preferred polyimide film in the present invention is a film mainly comprising 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 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-closing reaction (imidization).
Specific examples of the aromatic diamine having the benzoxazole structure include the following, and these diamines may be used alone or in combination of two or more.

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。
本発明で用いるポリイミドフィルムにおいては、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 polyimide film used in the present invention, it is preferable to use 70 mol% or more of the aromatic diamine having the benzoxazole structure.

Furthermore, the following aromatic diamines may be used without being limited to the above items, but preferably diamines having no benzoxazole structure exemplified below as long as they are less than 30 mol% of the total aromatic diamines. It is a polyimide film using one or two or more 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 are, for example, aromatic tetracarboxylic acid 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.
The non-aromatic tetracarboxylic dianhydrides exemplified below may be used alone or in combination of two or more, as long as the total tetracarboxylic dianhydride is less than 30 mol%. 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.

Maleic anhydride or the like can be used to seal the molecular ends of polyimide or linear polyamic acid with terminal groups having a carbon-carbon double bond. The amount of maleic anhydride used is 0.001 to 1.0 molar ratio per mole of aromatic diamine component.
The polyamic acid solution preferably contains a solid content of 5 to 40% by mass, more preferably 10 to 30% by mass, and its viscosity is 10 to 2000 Pa · s as measured by a Brookfield viscometer, preferably Is preferably 100 to 1000 Pa · s because stable liquid feeding is possible. The polymerization reaction is continuously carried out for 10 minutes to 30 hours in a temperature range of 0 to 80 ° C. while stirring and / or mixing in an organic solvent. You can move it up and down. 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.

As a method for producing a polyimide film used in the present invention, a green film obtained by continuously extruding or applying a polyamic acid solution to a support in the form of a film and then drying is peeled off from the support, and stretched. A typical method for producing a polyimide film from an organic solvent of polyamic acid, which is produced by drying and heat treatment, is that a solution of an organic solvent of polyimide acid containing no ring closure catalyst and a dehydrating agent is supported from a base with a slit. Cast on top to form a film, heat-dry on the support to form a self-supporting green film, peel off the film from the support, and further heat and dry at a high temperature for imidization The thermal ring closure method and the organic solvent of polydoic acid impregnated with a ring closure catalyst and a dehydrating agent After casting on a support and forming it into a film, after partially imidizing on the support and making it a film having self-supporting properties, the film is peeled off from the support, heat-dried / imidized, There is a chemical ring closure method in which heat treatment is performed.
As a support used for producing the polyimide film, a drum or a belt-like rotating body used when the polyamic acid solution is formed into a film can be used. 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 used in the present invention can be produced as described above, the linear expansion coefficient of these films is essential for the reason described above, preferably −2 to 10 ppm / ° C. More preferably, it is −2 to 8 ppm / ° C., and further preferably −2 to 6 ppm / ° C.

The adhesive used in the multilayer substrate of the present invention is required to be a polyimide or polyamideimide having a 5% weight loss temperature of 400 ° C. or more and being soluble in an organic solvent. If the adhesive is not soluble in an organic solvent, it requires a process in which it is dissolved in an organic solvent in the form of a polyamic acid, applied to a substrate, and then subjected to a high-temperature heat treatment (imidization), which increases the production cost. However, defects may occur after the heat treatment and the quality may deteriorate. Furthermore, since the polyamic acid solution undergoes an imidization reaction slowly even at room temperature, there is a problem in stability in a varnish state.
Examples of the adhesive used in the present invention include thermoplastic polyamide-imide, thermoplastic polyimide, thermoplastic polyimide siloxane, thermoplastic polyamide-imide siloxane, and the like, and one or a mixture of two or more of these resins. However, both must be organic solvent soluble. Particularly preferred is an organic solvent-soluble material mainly composed of polyimide obtained by reacting an aromatic tetracarboxylic acid having a benzophenone structure and an aromatic diamine.

  The method of laminating the polyimide film on the inorganic substrate through the adhesive is not particularly limited. For example, first, the method by coextrusion, the polyimide polyamic acid of the adhesive layer on the polyimide film which is one layer A method of casting a solution and imidizing it, a method of laminating a precursor film of another polyimide on a polyimide film precursor film which is one layer, and imidizing together, a polyimide polyamide on a polyimide film layer A method of laminating a heat-resistant film layer with an adhesive obtained by applying an acid solution by spray coating or the like to imidize, an inorganic substrate, a method of laminating a polyimide film after providing the adhesive on an inorganic substrate, etc. Is mentioned.

As the glass substrate in the inorganic substrate used in the present invention, a conventionally known glass substrate can be used, but a substrate using photosensitive glass is preferably used. A conventionally known ceramic substrate can be used as the ceramic substrate, and it is made of ceramics such as alumina, zirconia, mullite, cordierite, steatite, magnesium titanate, calcium titanate, strontium titanate, aluminum nitride, silicon carbide, silicon nitride, etc. Is mentioned.
Further, the inorganic substrate may be provided with through holes, conductor circuits, resistors, inductors, and capacitors. In addition, the manufacturing method of the multilayer board | substrate of this invention is not limited above, The methods, such as buildup and collective lamination, are also mentioned as a preferable example.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated more concretely, this invention is not limited by a following example. 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 (or N, N-dimethylacetamide) so that the polymer concentration was 0.2 g / dl was measured at 30 ° C. with an Ubbelohde type viscosity tube.

2. The thickness of the polyimide film The polyimide film to be measured was measured using a micrometer (Minetron 1245D, manufactured by Fine Reef).

3. Thickness unevenness of polyimide film About the polyimide film to be measured, in the width direction (TD), measure the full width at intervals of 1 cm in the width direction, and calculate the average thickness, maximum thickness, and minimum thickness between them, and use the following formula Calculated. Moreover, about the longitudinal direction (MD), it measured for 5 m by 5 cm space | interval of the longitudinal direction, the average thickness in the meantime, the maximum thickness, and the minimum thickness were taken out, and it calculated using the following Formula.
Thickness unevenness (%) = ((maximum thickness−minimum thickness) / average thickness) × 100

4). Tensile modulus, tensile breaking strength, and tensile breaking elongation of the polyimide film were measured for the polyimide film to be measured under the following conditions, and the tensile modulus, tensile breaking strength, and tensile breaking elongation were measured in the MD direction. .
Device name: Autograph made by Shimadzu Corporation
Sample length: 100mm
Sample width: 10mm
Pulling speed: 50mm / min
Distance between chucks: 40 mm

5. Linear expansion coefficient (CTE) of polyimide film
For the polyimide film to be measured, the stretch rate in the MD direction and the TD direction is measured under the following conditions, and the stretch rate / temperature at intervals of 90 to 100 ° C., 100 to 110 ° C.,. The measurement was performed up to 400 ° C., and the average value of all measured values from 100 ° C. to 350 ° C. was calculated as CTE (ppm / ° C.).
Device name: TMA4000S manufactured by MAC Science
Sample length: 10mm
Sample width: 2mm
Temperature rise start temperature: 25 ° C
Temperature rise end temperature: 400 ° C
Temperature increase rate: 5 ° C / min
Atmosphere: Argon

6). Water absorption rate of the polyimide film The water absorption rate of the polyimide film was determined by cutting the film to about 10 cm x 10 cm, and drying the test piece for 1 hour in a dry oven at 150 ° C. Then, the test piece was placed in ion exchange water at 25 ° C. for 24 hours, and then water droplets on the surface were sufficiently wiped off and reweighed to obtain a water absorption value. The water absorption was determined from the following formula.
Water absorption rate = 100 × (water absorption value−initial value) / (initial value) [mass%]

7). Glass transition temperature of adhesive The viscoelasticity measurement (DMA) of the adhesive to be measured was performed under the following conditions, and the glass transition temperature (° C.) was determined from the maximum value of the tan δ peak.
Device name: Rheogel-E4000 manufactured by UBM
Jig: Stretch jig
Sample length: 14mm
Sample width: 5 mm
Frequency: 10Hz
Temperature rising start temperature: 30 ° C
Temperature increase rate: 5 ° C / min
Atmosphere: Nitrogen

8). 5% weight reduction temperature of adhesive The adhesive to be measured was subjected to thermobalance measurement (TGA) under the following conditions, and the temperature at which the weight of the sample was reduced by 5% was defined as a 5% weight reduction temperature (° C.).
Device name: TG-DTA2000S manufactured by MAC Science
Bread: Aluminum bread (non-airtight type)
Sample weight: 10mg
Temperature rising start temperature: 30 ° C
Temperature increase rate: 20 ° C / min
Atmosphere: Nitrogen

9. Peel strength The peel strength of the sample was determined by conducting a 180 degree peel test under the following conditions.
Device name: Autograph AG-IS, manufactured by Shimadzu Corporation
Sample length: 100mm
Sample width: 10mm
Measurement temperature: 30 ° C
Peeling speed: 50mm / min
Atmosphere: Atmosphere

[Production Example 1]
(Preparation of polyimide film A)
The inside of the reaction vessel equipped with a nitrogen introduction tube, a thermometer, and a stirring rod was replaced with nitrogen, and then 223 parts by mass of 5-amino-2- (p-aminophenyl) benzoxazole and 4416 parts by mass of N, N-dimethylacetamide were added. 40.5 parts by mass of Snowtex (registered trademark) DMAC-ST30 (Nissan Chemical Industry Co., Ltd.) obtained by dispersing colloidal silica in dimethylacetamide (including 8.1 parts by mass of silica) When 217 parts by mass of pyromellitic dianhydride was added and stirred at a reaction temperature of 25 ° C. for 24 hours, a brown and viscous polyamic acid solution A was obtained. This reduced viscosity was 3.9 dl / g.
This polyamic acid solution A was coated on a 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 not peeled off from the support. The polyamic acid film was wound up. The polyamic acid film is passed through a pin tenter having three heat treatment zones, the first stage is 150 ° C. × 2 minutes, the second stage is 220 ° C. × 2 minutes, the third stage is 475 ° C. × 4 minutes, and 20 minutes after passing through the tenter. Six rolls were passed to give a double-side free process, and finally slit to a width of 500 mm to obtain a polyimide film A having a thickness of 25 μm.
The physical property values of the obtained polyimide film A are shown in Table 1.

[Production Example 2]
(Preparation of polyimide film B)
After the inside of the reaction vessel equipped with a nitrogen introduction tube, a thermometer, and a stirring rod was purged with nitrogen, 200 parts by mass of diaminodiphenyl ether and 4170 parts by mass of N-methyl-2-pyrrolidone were added and completely dissolved, and then colloidal silica was added. 40.5 parts by mass of Snowtex (registered trademark) DMAC-ST30 (manufactured by Nissan Chemical Industries, Ltd.) dispersed in dimethylacetamide (including 8.1 parts by mass of silica), 217 parts by mass of pyromellitic dianhydride In addition, when the mixture was stirred at a reaction temperature of 25 ° C. for 5 hours, a brown viscous polyamic acid solution B was obtained. This reduced viscosity was 3.6 dl / g.
This 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 not peeled off from the support. The polyamic acid film was wound up. The polyamic acid film is passed through a pin tenter having three heat treatment zones, the first stage is 150 ° C. × 2 minutes, the second stage is 220 ° C. × 2 minutes, the third stage is 400 ° C. × 4 minutes, and 20 minutes after passing through the tenter. Six rolls were passed to give a double-side free process, and finally slit to a width of 500 mm to obtain a polyimide film B with a thickness of 25 μm.
Table 1 shows the physical property values of the obtained polyimide film B.

[Production Example 3]
(Preparation of polyimide film C)
After the inside of the reaction vessel equipped with a nitrogen introduction tube, a thermometer, and a stirring rod was replaced with nitrogen, 108 parts by mass of phenylenediamine and 4010 parts by mass of N-methyl-2-pyrrolidone were added and completely dissolved, and then colloidal silica was added. 40.5 parts by mass of Snowtex (registered trademark) DMAC-ST30 (manufactured by Nissan Chemical Industries, Ltd.) dispersed in dimethylacetamide (including 8.1 parts by mass of silica), diphenyltetracarboxylic dianhydride 292. When 5 parts by mass was added and stirred for 12 hours at a reaction temperature of 25 ° C., a brown viscous polyamic acid solution C was obtained. This reduced viscosity was 4.3 dl / g.
This polyamic acid solution C 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 not peeled off from the support. The polyamic acid film was wound up. 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 after passing through the tenter 20 minutes Six rolls were passed to give a double-side free process, and finally slit to a width of 500 mm to obtain a polyimide film C having a thickness of 25 μm.
Table 1 shows the physical property values of the obtained polyimide film C.

[Production Example 4]
(Preparation of solvent-soluble polyimide adhesive A)
After the inside of the reaction vessel equipped with a nitrogen introduction tube, a thermometer, and a stirring rod was purged with nitrogen, 145 g (0.45 mol) of benzophenone-3,3 ′, 4,4′-tetracarboxylic dianhydride, pyromellitic acid 2 Anhydrous 10.91 g (0.05 mol) and sodium methylate 0.2 g (0.0037 mol) were dissolved in 597 g of DMF. The reaction mixture was heated to 80 ° C., and 87.08 g (0.5 mol) of toluene diisocyanate composed of 80% of 2,4-isomer and 20% of 2,6-isomer was added at a constant rate in a nitrogen atmosphere. Add dropwise over 4 hours under stirring. Thereafter, the final polycondensation solution was stirred at 80 ° C. for 1 hour until CO ₂ generation was completed to obtain a solvent-soluble polyimide adhesive A.
The solvent-soluble polyimide adhesive A polymer obtained had a glass transition temperature of 340 ° C. and a 5% weight loss temperature of 450 ° C.

[Production Example 5]
(Preparation of solvent-soluble polyimide adhesive B)
After replacing the inside of the reaction vessel equipped with a nitrogen introduction tube, a thermometer, and a stirring rod with nitrogen, polyetherimide (manufactured by General Electric Co., Ltd., trade name: Ultem1000) was dissolved in dimethylacetamide so as to be 20% by mass, and polyimide A system adhesive B was obtained.
The polymer of the obtained polyimide adhesive B had a glass transition temperature of 228 ° C. and a 5% weight loss temperature of 506 ° C.

[Production Example 6]
(Preparation of solvent-soluble polyimide adhesive C)
After the inside of the reaction vessel equipped with a nitrogen introduction tube, a thermometer, and a stirring rod was purged with nitrogen, 73,56 g of 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 88 g of diaminopolysiloxane, 2,2 61.58 g of bis [4- (4-aminophenoxy) phenyl] propane and 1000 g of N-methyl-2-pyrrolidone were charged. After stirring at 60 ° C. for about 2 hours, the reaction was carried out with stirring at 200 ° C. for 3 hours while removing water. After the reaction, the reaction solution was added to 10 liters of water, precipitated for 30 minutes using a homomixer, and polymer powder was isolated by filtration. 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. Tetrahydrofuran was added to obtain a solvent-soluble polyimide adhesive C having a solid concentration of 20% by mass.
The solvent-soluble polyimide adhesive C polymer obtained had a glass transition temperature of 192 ° C. and a 5% weight loss temperature of 495 ° C.

[Production Example 7]
(Preparation of solvent-soluble polyimide adhesive D)
The inside of the reaction vessel equipped with a nitrogen introduction tube, a thermometer and a stirring rod was purged with nitrogen, and then 63.2 g of 4,4′-benzophenone tetracarboxylic dianhydride, 2,2-bis [4- (4-aminophenoxy) ) Phenyl] propane 63.57 g, 62.11 g of bis (3-aminopropyl) polymethylsiloxane having a molecular weight of 750, and 315 g of xylene were charged. After reacting at 150 ° C. for about 1 hour, the reaction was carried out with stirring at 165 ° C. for 18 hours while removing water. After the reaction, the remaining xylene was distilled off under reduced pressure, and N-methyl-2-pyrrolidone was added to obtain a solvent-soluble polyimide adhesive D having a solid concentration of 20% by mass.
The solvent-soluble polyimide adhesive D polymer obtained had a glass transition temperature of 186 ° C. and a 5% weight loss temperature of 366 ° C.

[Production Example 8]
(Preparation of Solvent Soluble Polyamideimide Adhesive A)
The inside of the reaction vessel equipped with a nitrogen introduction tube, a thermometer, and a stirring rod was purged with nitrogen, and then 190 g of trimellitic anhydride and 250 g of oxydianiline diisocyanate were added, and N-methyl-2-pyrrolidone was added at a polymer concentration of 40. It was charged to become%. After making it react at 120 degreeC for about 1 hour, it heated up at 180 degreeC and made it react, stirring for 5 hours. Next, while heating was stopped and cooling, N-methyl-2-pyrrolidone was further added and diluted to obtain a solvent-soluble polyamideimide-based adhesive A having a solid content concentration of 20% by mass.
The solvent-soluble polyamideimide-based adhesive A polymer obtained had a glass transition temperature of 290 ° C. and a 5% weight loss temperature of 495 ° C.

[Production Example 9]
(Preparation of Solvent-Soluble Polyamideimide Adhesive B)
After the inside of the reaction vessel equipped with a nitrogen introduction tube, a thermometer, and a stirring rod was purged with nitrogen, 192 g of trimellitic anhydride, 211 g of o-tolidine diisocyanate (80 mol%), 35 g of 2,4-tolylene diisocyanate, 1 g of ethylenediamine was charged, and N-methyl-2-pyrrolidone was further charged so that the polymer concentration was 40%. After making it react at 120 degreeC for about 1 hour, it was made to react, further stirring at 180 degreeC for 5 hours. Next, while heating was stopped and cooling, N-methyl-2-pyrrolidone was further added and diluted to obtain a solvent-soluble polyamideimide-based adhesive B having a solid content concentration of 20% by mass.
The solvent-soluble polyamideimide-based adhesive B polymer obtained had a glass transition temperature of 320 ° C. and a 5% weight loss temperature of 485 ° C.

[Production Example 10]
(Preparation of Solvent Soluble Polyamideimide Adhesive C)
After the inside of the reaction vessel equipped with a nitrogen introduction tube, a thermometer, and a stirring rod was purged with nitrogen, 190 g of trimellitic anhydride, 172 g of cyclohexanedicarboxylic acid, 450 g of isophorone diisocyanate, and 7.5 g of terminal amino group silicon were charged. -Methyl-2-pyrrolidone was charged to a polymer concentration of 40%. After making it react at 120 degreeC for about 1 hour, it heated up at 180 degreeC and made it react, stirring for 5 hours. Next, while heating was stopped and cooling, N-methyl-2-pyrrolidone was further added and diluted to obtain a solvent-soluble polyamideimide-based adhesive C having a solid content concentration of 20%.
The solvent-soluble polyamideimide-based adhesive C polymer obtained had a glass transition temperature of 237 ° C. and a 5% weight loss temperature of 360 ° C.

[Production Example 11]
(Preparation of Solvent-Soluble Polyamideimide Adhesive D)
After the inside of the reaction vessel equipped with a nitrogen introduction tube, a thermometer, and a stirring rod was purged with nitrogen, 49.3 parts by mass of 2,2-bis [4- (4-aminophenoxy) phenyl] propane, reactive silicone oil: X -22-161-A (manufactured by Shin-Etsu Chemical Co., Ltd.) 48.3 parts by mass, trimellitic anhydride 60.5 parts by mass, and N-methyl-2-pyrrolidone 474 parts by mass were charged. After reacting at 80 ° C. for 30 minutes, 100 ml of toluene was added, and then the temperature was raised to 160 ° C. and refluxed for 2 hours. Further, the temperature was raised to 190 ° C. to remove toluene. Thereafter, the solution is returned to room temperature, 45.1 parts by mass of 4,4′-diphenylmethane diisocyanate is added, and the mixture is reacted at 190 ° C. for 2 hours. Further, N-methyl-2-pyrrolidone is added to dilute to obtain a solid concentration of 20 A mass% solvent-soluble polyamideimide-based adhesive D was obtained.
The solvent-soluble polyamideimide-based adhesive D polymer obtained had a glass transition temperature of 161 ° C. and a 5% weight loss temperature of 373 ° C.

[Example 1]
A solvent-soluble polyimide-based adhesive A is applied to one side of the polyimide film A, dried at 100 ° C. for 1 hour, further heat-treated at a temperature near Tg (340 ° C.) for 15 minutes, and a thickness of 20 μm. It adjusted so that it might become. Two layers of this polyimide film A / solvent soluble polyimide-based adhesive A and a ceramic substrate (made by Nippon Carbide Industries Co., Ltd., trade name: alumina ceramic, thickness 1.0 mm) are superposed, Tg + 50 ° C. (390 ° C.), The test was performed at 10 MPa for 15 minutes to obtain a test multilayer substrate 1. The obtained test multilayer substrate was evaluated according to the following. The results are shown in Table 2.

[Example 2]
A multilayer substrate 2 was obtained in the same manner as in Example 1 except that the polyimide film C was used. The obtained test multilayer substrate was evaluated according to the following. The results are shown in Table 2.

Example 3
A multilayer substrate 3 was obtained in the same manner as in Example 1 except that a glass substrate (manufactured by Corning, trade name: 1737 glass, thickness 1.0 mm) was used. The obtained test multilayer substrate was evaluated according to the following. The results are shown in Table 2.

[Examples 4 to 7]
Multilayer substrates 4 to 7 were obtained in the same manner as in Example 1 except that solvent-soluble polyimide adhesives B and C and solvent-soluble polyamideimide adhesives A and B were used. The obtained test multilayer substrate was evaluated according to the following. The results are shown in Table 3.

[Comparative Example 1]
A multilayer substrate 8 was obtained in the same manner as in Example 1 except that the polyimide film B was used. The obtained test multilayer substrate was evaluated according to the following. The results are shown in Table 4.

[Comparative Examples 2 to 4]
Multilayer substrates 9 to 11 were obtained in the same manner as in Example 1 except that the solvent-soluble polyimide adhesive D and the solvent-soluble polyamideimide adhesives C and D were used. The obtained test multilayer substrate was evaluated according to the following. The results are shown in Table 4.

<Evaluation of substrate>
The acceleration test of the obtained test multilayer substrate was subjected to the following test.
Obtained above, a polyimide film, an adhesive, for each test piece composed of an inorganic substrate was evaluated for peeling strength after heat treatment 400 ° C. 1 hour under N ₂ atmosphere. The quality after the heat treatment was also evaluated.
Of the obtained peel strengths, those of 5 N / cm or more were evaluated as ◯, those of 1 N / cm or more and less than 5 N / cm were evaluated as Δ, and those of less than 1 N / cm as X. In addition, according to the appearance observation, those in which the adhesive was not discolored were rated as “◯”, those that were browned as “Δ”, and those that were blackened as “×”. In addition, the case where peeling or swelling was not observed at all was rated as ◯, the case where peeling or swelling was slightly observed was indicated as Δ, and the case where peeling or swelling was observed was rated as ×.

The multilayer substrate of the present invention can be stabilized against temperature changes and can maintain an accurate value, and since a conductor circuit can be formed on the polyimide film layer, a fine circuit can be formed, thereby improving the mounting density of the substrate. It is possible to reduce the size, and since the inorganic substrate is included therein, the curvature of the multilayer substrate is suppressed, and there is no difference in the coefficient of linear expansion between the inorganic substrate and the polyimide film layer. Since there is little peeling in the substrate, it is extremely useful as a multilayer substrate. In addition, the adhesive is stable in the varnish state, which improves the yield, simplifies the manufacturing process (good productivity), does not require imidization, has a good insulating layer film quality, and a small thickness variation. Can be obtained.
Furthermore, it is possible to produce a multi-layer substrate for interposers that has adhesive reliability under temperature cycling and high temperature and high humidity, has a small difference in linear expansion coefficient from inorganic substrates, and has high connection reliability when mounting bare chips. Yes, it is very meaningful in industry.
Since the gas barrier property of the inorganic substrate is extremely high, it is optimal for applications that require gas barrier properties, and even the part bonded to it has less gas permeation and has extremely high reliability. Is.

Claims (4)

  In a multilayer substrate having a structure in which a polyimide film is laminated on an inorganic substrate through an adhesive, the polyimide film is mainly composed of polyimide obtained by reacting aromatic tetracarboxylic acids and aromatic diamines, and a wire A multilayer substrate characterized by being a polyimide film having an expansion coefficient of 10 ppm / ° C. or less, a 5% weight reduction temperature of the adhesive of 400 ° C. or more, and an organic solvent-soluble polyimide or polyamideimide.   The multilayer substrate according to claim 1, wherein the polyimide film is a polyimide film mainly composed of polyimide benzoxazole obtained by condensation of aromatic tetracarboxylic acid anhydrides and diamines having a benzoxazole structure.   The multilayer substrate according to claim 1 or 2, wherein the adhesive is mainly composed of polyimide obtained by reacting an aromatic tetracarboxylic acid having a benzophenone structure and an aromatic diamine.   The multilayer substrate according to claim 1, wherein the inorganic substrate is a ceramic substrate or a glass substrate.