JPH0740629B2 - Manufacturing method of multilayer wiring board for electronic devices - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a method for producing a multilayer wiring board for an electronic device, which has an insulating layer made of a polyimide-based low thermal expansion resin having a specific chemical structure and a conductive layer.

[Background of the Invention]

Almost all organic polymers have a thermal expansion coefficient (linear expansion coefficient) of 4 even in the temperature range below the glass transition temperature.
It has a value of × 10 ^-3 K ^-1 or more, which is much larger than those of metals and inorganic substances. It is no exaggeration to say that there are many problems due to the large linear expansion coefficient of organic substances, and all of the reasons why application development of organic polymers does not proceed as expected are here.

When a thin film multilayer wiring is formed on a ceramic substrate with a polyimide insulating layer and a conductive layer of a metal thin film, the thickness of the thin film layer is
When the thickness is 150 μm or more, cracks, peeling, and substrate breakage occur at and near the interface between polyimide and ceramic or the conductive layer and polyimide due to thermal stress due to the difference in thermal expansion coefficient.

For example, how to make the surface of a protective film formed to protect a silicon wafer such as an LSI flat is a problem. That is, in the lithography process at the time of forming the fine wiring, if there is a step, the depth of focus is different and the precision of the fine wiring is lowered. Polyimide is excellent in such flatness,
The wafer may be warped due to thermal stress caused by the difference in thermal expansion coefficient from the silicon wafer, and photolithography for patterning may not be performed, or the silicon wafer may be cleaved and broken.

However, it is common knowledge that organic materials have a large coefficient of thermal expansion. Therefore, the development of low thermal expansion organic materials is the dream of these materials researchers, and their solution will have a great impact on the industry. .

In view of such circumstances, the present inventors first tried many synthetic experiments for heat-resistant resin materials, particularly polyimide, and examined the relationship between raw material components and the coefficient of thermal expansion in detail.
So far, polyimide has been used as U.S. Pat. No. 3,179,614 (duPont), CESroog, "Polyimides", J. Poly.
m.Sci .: Macromol. Rev., 11, 161-208 (1976), NAAd
rova and MMKoton, Dokl.Akad.Nauk.SSSR, 165,1069 (1
965), MMKoton and Yu.N.Sazonov, J.Therm.Analy
s, 7 (1975), 165, MMKoton, Polym.Sci.USSR2
A wide variety is provided as shown in 1,2756 (1979).

However, very few are actually synthesized or put to practical use. So far, the synthesis has been attempted, and as reported or commercially available, aromatic diamines such as diaminodiphenyl ether, diaminodiphenylmethane, paraphenylenediamine or diaminophenylsulfide, pyromellitic dianhydride, and benzophenonetetracarboxylic acid have been reported. There are only polyimides prepared from tetracarboxylic dianhydrides such as acid dianhydride, tetracarboxydiphenyl ether dianhydride or butanetetracarboxylic dianhydride. However, the linear expansion coefficient of these polyimides is 4-6 × 10 ^-5 K
^-1 is extremely large.

However, as a result of further synthetic experiments by the present inventors,
It has been discovered that a polyimide obtained from a specific aromatic diamine and tetracarboxylic dianhydride has a linear expansion coefficient much smaller than that of the above-mentioned polyimide and an extremely excellent tensile strength as described below. The present invention has been made based on these findings.

[Object of the Invention]

An object of the present invention is to provide a low thermal expansion resin having a thermal expansion coefficient close to that of an inorganic (excluding metal) substrate such as a silicon wafer, ceramics or glass, and having excellent mechanical properties. Another object of the present invention is to provide a method for producing a multilayer wiring board for an electronic device, which has an insulating layer and a conductive layer such as a metal thin film and has almost no thermal stress.

[Outline of Invention]

The gist of the present invention for achieving the above object is as follows.

(1) In the method of manufacturing a multilayer wiring board for an electronic device, which has a conductor and an insulating layer on an inorganic (excluding metal) substrate, the insulating layer is represented by the general formula H ₂ N-Ar ¹ -NH ₂ ... ( 1) and Or / and Polyamic acid obtained by reacting with [formula (1)
In (2) and (3), Ar ¹ is R represents a lower alkyl group, a lower alkoxy group, a fluorinated alkoxy group, an acyl group or halogen, and n
Is an integer of 1 to 4, m is 0 or an integer of 1 to 3, X,
Y represents halogen, -OR 'or -OH, R'represents a lower alkyl group or a fluorinated alkoxy group, which may be different from each other. However, when a pyromellitic acid component is included as the tetracarboxylic acid component, the proportion of the pyromellitic acid component is less than 50 mol%. ] Is directly applied and then imidized, or a polyimide film imidized with the polyamic acid is adhered to form an insulating layer having a thickness of 2 μm or more and a linear expansion coefficient of 0.2 to 3.2 × 10 ⁻⁵ K ^−. A method of manufacturing a multilayer wiring board for an electronic device, comprising:

(2) In the method for manufacturing a multilayer wiring substrate for an electronic device, which has a conductor and an insulating layer on an inorganic (excluding metal) substrate, the insulating layer may be the general formula (1) and the general formula (2). ) Or / and a polyamic acid obtained by reacting with the general formula (3) [Explanation of symbols in the above general formulas is the same as in the above item (1)] and 35% by weight of a polyimide precursor other than the polyamic acid. Immediately after coating the copolymerized or blended product, or by imidizing the copolymerized or blended polyamic acid imidized polyimide film, the thickness is 2 μm or more and the linear expansion coefficient is 0.2 ~ 3.2
× 10 ^-5 K ^- the preparation of a multilayer wiring substrate for an electronic device, which comprises forming the insulating layer.

The low thermal expansion polyimide has a substantially linear molecular skeleton and has a rod-shaped molecular chain, so that it may be mechanically brittle or poor in adhesiveness depending on the polyimide. In order to improve this, another flexible polyimide can be copolymerized or blended to the extent that low thermal expansion is not impaired. However, the blending amount is preferably within 35% by weight.

Aromatic polymers such as polyphenylene generally have the drawback of being rigid but brittle, and between aromatic rings
O -, - S -, - (CH 2) P -, Introducing flexible bonds such as, the entire polymer is flexible. Further, the bonding position of the aromatic ring is also made flexible when it is in the ortho position or the meta position. The same applies to polyimide, and all of the polyimides currently industrialized have a bond selected from these. Therefore, the low thermal expansion polymer of the present invention has not been found so far.

FIG. 1 shows the coefficients of thermal expansion of various materials. From this figure, the coefficient of thermal expansion of a general organic polymer is larger than that of metals and ceramics, but it is obvious how small the coefficient of thermal expansion of the polyimide used in the present invention is. When the coefficient of thermal expansion is as small as an inorganic material such as metal or ceramics, when an inorganic material is combined with an organic material, thermal stress and warpage do not occur because the dimensions change as well as the inorganic material even when the temperature changes. , Industrially very useful. The biggest drawback of these organic materials to date is
It is no exaggeration to say that the coefficient of thermal expansion is much higher than that of inorganic materials.

The low thermal expansion polyimide of the present invention can be obtained by reacting an aromatic diamine or aromatic diisocyanate with an aromatic tetracarboxylic acid derivative.

As the tetracarboxylic acid derivative, an ester, an acid anhydride,
Although there are acid chlorides, acid anhydrides are preferred for synthesis. Synthetic reactions are generally N-methylpyrrolidone (NMP), dimethylformamide (DMF), dimethylacetamide (DMA
C), dimethyl sulfoxide (DMSO), dimethyl sulfate, sulfolane, butyrolactone, cresol, phenol, halogenated phenol, cyclohexanone, dioxane and the like at 0 to 200 ° C.

The following are mentioned as aromatic diamine used for this invention.

o-tolidine, m-tolidine, 3,3 ', 5,5'-tetramethylbenzidine, 3,3'-dimethoxybenzidine, 3,3'
-Diacetylbenzidine, 3,3'-difluorobenzidine, octafluorobenzidine, 3,3'-dichlorobenzidine, 4,4 "-diamino-3,3'-dimethylterphenyl, 2,5-diaminodiphenyl, these Diisocyanate compounds can be used as well.

The tetracarboxylic acid derivative used in the present invention includes 3,
3 ', 4,4'-biphenyltetracarboxylic acid, 5,5'-dimethyl-3,3', 4,4'-biphenyltetracarboxylic acid, pyromellitic acid, methylpyromellitic acid, dimethylpyromellitic acid or these Acid anhydrides, acid chlorides, esters and the like.

Among the above derivatives, the acid anhydride having no by-product and high reactivity is the easiest to use. In terms of reactivity, acid chlorides are the strongest and preferred.

Of the above polyimide raw materials, those in which both Ar ¹ and Ar ² components have one benzene ring are not preferable because they are mechanically brittle, especially when formed into a polyimide film.

Further, by modifying with an amine bond such as an ether bond, a thioether bond, a carbonyl bond, a sulfone bond, an isopropylidene bond, or a hexafluoroisopropylidene bond in the skeleton or a tetracarboxylic acid, flexible properties can be improved. . Further, addition of diamine or tetracarboxylic acid having siloxane in the skeleton is effective for improving the adhesiveness. Since these flexible polyimides have a large coefficient of thermal expansion, the amount added is limited to 35% by weight, preferably 25% by weight or less.

Further, in the case of etching with an alkali such as hydrazine, if a pyromellitic acid derivative is used in an amount of less than 50 mol% as a tetracarboxylic acid component, a composition capable of etching is obtained. Beyond that, it becomes brittle.

The low thermal expansion polyimides of the present invention do not lose much of their properties when blended or copolymerized with non-low thermal expansion polymers in significant amounts. Although some polyimides of the present invention are mechanically brittle, it is sometimes preferable to blend or copolymerize a flexible polymer with such a polyimide. Polymers that can be blended or copolymerized include, for example, polyimides obtained from the following diamines and tetracarboxylic acid derivatives.

Specific examples of the aromatic diamine include m-phenylenediamine, 4,4'-diaminodiphenylmethane, 1,2-bis (anilino) ethane, 4,4'-diaminodiphenyl ether, diaminodiphenyl sulfone and 2,2-bis. (P-
Aminophenyl) propane, 2,2-bis (p-aminophenyl) hexafluoropropane, 3,3'-dimethyl-
4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, diaminotoluene, diaminobenzotrifluoride, 1,4-bis (p
-Aminophenoxy) benzene, 4,4'-bis (p-aminophenoxy) biphenyl, 2,2-bis [4- (p-
Aminophenoxy) phenyl] propane, diaminoanthraquinone, 4,4′-bis (3-aminophenoxyphenyl) diphenylsulfone, 1,3-bis (anilino) hexafluoropropane, 1,4-bis (anilino) octafluorobutane, 1,5-bis (anilino) decafluoropentane, 1,7-bis (anilino) tetradecafluoroheptane, (R ₅ and R ₇ are divalent organic groups, R ₄ and R ₆ are monovalent organic groups, p and q
Is an integer greater than 1),
2,2-bis [4- (p-aminophenoxy) phenyl]
Hexafluoropropane, 2,2-bis [4- (3-aminophenoxy) phenyl] hexafluoropropane, 2,
2-bis [4- (2-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) -3,5-dimethylphenyl] hexafluoropropane, 2,2-bis [ 4- (4-aminophenoxy) -3,5-ditrifluoromethylphenyl] hexafluoropropane, p-bis (4-amino-2-trifluoromethylphenoxy) benzene, 4,4'-bis (4-
Amino-2-trifluoromethylphenoxy) biphenyl, 4,4'-bis (4-amino-3-trifluoromethylphenoxy) biphenyl, 4,4'-bis (4-amino-2-trifluoromethylphenoxy) diphenyl Sulfone, 4,4'-bis (3-amino-5-trifluoromethylphenoxy) diphenyl sulfone, 2,2-bis [4
-(4-amino-3-trifluoromethylphenoxy)
Phenyl] diamines such as hexafluoropropane,
And diisocyanates obtained by the reaction of these diamines and phosgene, for example, aromatic compounds such as tolylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, diphenyl ether diisocyanate, phenylene-1,3-diisocyanate, etc. There are diisocyanates.

Moreover, the following are mentioned as tetracarboxylic acid and its derivative (s). Although illustrated as tetracarboxylic acid here, of course, esterified products, acid anhydrides, and acid chlorides thereof can also be used. 2,3,3 ', 4'-tetracarboxydiphenyl, 3,3', 4,4'-tetracarboxyphenyl ether, 2,3,3 ', 4'-tetracarboxydiphenyl ether, 3,3', 4, 4'-tetracarboxybenzophenone, 2,3,3 ', 4'-tetracarboxybenzophenone, 2,3,6,7-tetracarboxynaphthalene, 1,
4,5,7-Tetracarboxynaphthalene, 1,2,5,6-tetracarboxynaphthalene, 3,3 ', 4,4'-tetracarboxydiphenylmethane, 2,2-bis (3,4-dicarboxyphenyl) Propane, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane, 3,3 ', 4,4'-tetracarboxydiphenyl sulfone, 3,4,9,10-tetracarboxyperylene, 2,2 -Bis [4- (3,4-dicarboxyphenoxy) phenyl] propane, 2,2-bis [4-
(3,4-dicarboxyphenoxy) phenyl] hexafluoropropane, butanetetracarboxylic acid, cyclopentanetetracarboxylic acid and the like.

In the present invention, the adhesiveness is important when the low thermal expansion polyimide is integrated with the inorganic material. It is preferable to roughen the surface of the inorganic material or to treat the surface with a silane coupling agent, a titanate coupling agent, an aluminum alcoholate, an aluminum chelate, a zirconium chelate, aluminum acetylacetone, or the like. These surface treatment agents may be added to the low thermal expansion polyimide.

In the present invention, in order to further reduce the coefficient of thermal expansion, increase the elastic modulus, and control the fluidity, it is also possible to mix powders of inorganic, organic, or metal, fibers, chopped strands, and the like.

An example of manufacturing the wiring board of the present invention is shown below.

Figure 2 shows a cross-sectional view of a bipolar LSI. A thermal oxide film 4 is formed on a silicon wafer 3, and a 0.5% aluminum chelate toluene solution is spin-coated on the surface of the substrate on which the first-layer aluminum (Al) wiring 5 is formed, and then in the air.
Heated above 350 ° C.

Next, the polyamic acid varnish of the present invention was spin-coated and heated at 100 ° C., 30 minutes, 200 ° C., 30 minutes, 400 ° C., 30 minutes to form a polyimide film 6 having a thickness of about 2 μm.

A mask pattern was formed on the polyimide film by photolithography, and the polyimide was dry-etched with oxygen ions. Then, the exposed portion of the Al wiring was cleaned with Ar ions, and then the second layer of Al wiring was vapor-deposited to be formed in the same manner as the first layer, and a polyimide film was provided thereon.

The insulating thin film of low thermal expansion polyimide largely reduces the level difference of the Al wiring and flattens it, and the thermal stress to the LSI element is also very small, so that the occurrence of cracks can be prevented.

Further, the low thermal expansion polyimide of the present invention can be easily processed with hydrazine or the like, and has an excellent property that the etching rate is about twice as fast as the conventional polyimide.

An alumina ceramic multilayer wiring board was used in place of the silicon wafer to form a two-layer wiring circuit in the same manner. The circuit thin film conductor in this case was formed by depositing copper. Further, a polyimide thin film of about 25 μm was formed on the insulating layer. The thin film layer of the insulating layer and the conductor layer formed above had a thickness of about 100 μm.
No cracks or peeling on the surface of the ceramic multilayer wiring board were observed in the thin film layer.

FIG. 3 shows a sectional view of a printed wiring board based on an LSI-mounted metal plate. In the carrier film method using the low thermal expansion polyimide 12, the LSI chip 11 is a metal substrate (heat sink) 1
It is mounted on 0. Since the low thermal expansion polyimide is used as the carrier film 12, a highly accurate LSI mounted printed wiring board can be obtained. In addition, fatigue rupture was reduced due to a large reduction in stress applied to the bonding solder ball 14. In addition, the insulating film 16 of the wiring portion 15 formed on the metal substrate 10
In addition, by adopting low thermal expansion polyimide, a printed wiring board without bending can be obtained. Reference numeral 13 is a terminal for external connection.

[Examples 1 to 16 and Comparative Examples 1 to 26] A four-necked flask having a thermometer, a stirrer, a reflux condenser, and a nitrogen blowing port was charged with the amount of diamine shown in Table 1, and N-methyl-2- It was dissolved in 850 g of pyrrolidone (NMP). Then, the flask was immersed in a water bath at 0 to 50 ° C., and tetracarboxylic dianhydride was added while suppressing heat generation. After the tetracarboxylic dianhydride was dissolved, the water bath was removed, and the reaction was continued at room temperature for about 5 hours to obtain the polyamic acid varnish shown in Table 1. When the viscosity of the varnish became very high, the mixture was heated and stirred (cooking) at 80 to 85 ° C until the viscosity at 25 ° C reached 50 poise.

The coefficient of thermal expansion of the polyimide (PI) obtained by heating these polyamic acid varnishes was measured as follows.

Apply evenly on a glass plate using an applicator, 80 ℃
Dry at -100 ° C for 30-60 minutes to form a film, peel it from the glass plate and fix it on an iron frame (fixed hardening or free hardening that can be freely contracted by hanging with a spring), 200 ° C, 300 ° C, 400
The temperature was kept at 60 ° C. for 60 minutes to obtain a polyimide film having a thickness of 30 to 200 μm. Cut this out to 3mm x 80mm,
It is sandwiched between two glass plates, heated again to 400 ° C, slowly cooled to remove residual strain, and then dimensional change is measured with a thermomechanical tester under the condition of 5 ° C / min. It was calculated from the amount of dimensional change.

In this way, an accurate thermal expansion coefficient cannot be measured unless the moisture absorbed by the film, the solvent, or the strain caused by the imidization reaction is sufficiently removed (the imidization reaction is substantially completed). In the range of room temperature to 150 ° C, the coefficient of thermal expansion of the film is apparently small due to dehumidification of moisture absorption. If the residual strain or imidization reaction is not completed, residual strain near Tg is removed or contraction occurs due to dehydration due to the imidization reaction, and the apparent linear expansion coefficient is often observed to be small.

Further, even if it is fixed on an iron frame and hardened, if it breaks during hardening, the orientation treatment is insufficient and the coefficient of thermal expansion becomes somewhat large, so care must be taken. The coefficient of thermal expansion of a film applied on a silicon wafer or a ceramic substrate is almost the same as that when fixed and cured. Here, the thermal expansion coefficient of the film on the substrate to which the adhesive treatment was applied could not be measured directly, so the method of peeling off was adopted.

Next, Table 1 shows the coefficient of thermal expansion of the polyimide film after fixed curing and free curing.

Example 17 Using the NMP varnish of the polyamic acid of Example 1, a mullite multilayer wiring board with a thickness of about 3 mm (coefficient of thermal expansion 3.5 × 10 5
Copper-polyimide four-layer wiring was formed on ^-6 K ^-1 ). Here, the copper-polyimide multilayer wiring is the same as that formed on the above-mentioned ceramic multilayer wiring board. That is, a copper wiring is plated on a pattern formed with a photoresist after forming a copper thin film, Cr is vapor-deposited on the copper wiring, a metal film other than the wiring is removed, and then a polyimide film is formed and flattened by polishing. is there.

The wiring thickness is about 10 μm, and the through hole is also 10
μm and polyimide were formed to a thickness of 25 μm and polished to 20 μm. Therefore, the total thickness is about 30 μm.

In the case of the low thermal expansion polyimide according to the present invention, the thermal expansion coefficient was almost the same as that of the mullite substrate, so that no crack or peeling was observed even after the thin film wiring was formed.

Substrate warpage is extremely small and 100 mm square substrate warpage amount is 20
It was less than μm.

Comparative Example 27 Diaminodiphenyl ether (DDE) as in Example 17
As a result of using the polyimide of Comparative Example 10 having a thermal expansion coefficient of 4.28 × 10 ⁻⁵ K ⁻¹ synthesized from benzophenone tetracarboxylic acid anhydride (BTDA), a substrate was prepared at the time of producing the fourth layer. Peeling occurred at the interface of the polyimide layer.

[Comparative Example 28] Using a polyamic acid having a thermal expansion coefficient of 2.4 x 10 ^-5 K ^-1 (Comparative Example 8) synthesized from DDE and PMDA (Comparative Example 8), a thin-film multilayer wiring board was prepared in the same process as in Example 17. I tried.

As a result, cracks were generated in the first insulating film when the wiring layers were formed up to two layers. As a result of investigating the cause, it was found that not only the insulating film was hydrolyzed in the plating process and the film thickness was decreased, but also the film strength was extremely decreased. When PMDA is heavily used in this way, it becomes impractical due to deterioration due to hydrolysis.

[Comparative Example 29] The same process as in Example 17 using a polyamic acid having a thermal expansion coefficient of 0.35 x 10 ^-5 K ^-1 synthesized from o-TOLID, BPDA and PMDA (molar ratio, 1: 0.4: 0.6) Attempted to make a thin film multilayer wiring board.

As a result, cracks were generated in the insulating film in the process of forming the first wiring layer, although the coefficient of thermal expansion was small. It was found that the cause was hydrolysis in the plating process of the insulating film, and the film strength was extremely reduced. As a result of making a similar multi-layered wiring board with a varnish with a different amount of PMDA, it was found that when it is 40% or less, deterioration due to hydrolysis does not occur so much, but when it is 50% or more, deterioration is severe and practicality is lost.

Example 18 Using NMP varnish of polyamic acid having a thermal expansion coefficient of 1.3 × 10 ⁻⁵ K ⁻¹ of Example 7, a polyimide film having a thickness of about 20 μm was prepared, and the upper and lower surfaces were surface-treated with oxygen plasma asher. After the treatment, Cr and Cu were vapor-deposited to a thickness of about 0.1 μm, respectively, and a Cu plating film was further formed to a thickness of about 15 μm to form a pattern by photolithography. Three double-sided wiring sheets, mullite multilayer wiring board (coefficient of thermal expansion 3.5 × 10
^-6 K ^-1 ) was laminated and molded using the polyamic acid of Comparative Example 22 as an adhesive to form a desired copper-polyimide 6-layer multilayer wiring board. Here, the upper and lower surfaces were connected by copper-plating the inner surface of the through hole opened by the excimer laser beam.

Also using the low thermal expansion polyimide according to the present invention,
Since the thermal expansion coefficient is almost the same as that of the mullite substrate, no crack or peeling was observed even after the thin film wiring was formed. The warp of the substrate was also extremely small.

[Examples 19 to 24 and Comparative Example 30] A polyimide copolymer was synthesized in the same manner as in Example 1.
Table 2 shows the thermal expansion coefficients of these polyimide films. As shown in the table, when a monomer having an extremely rigid skeleton such as DATP (diaminoterphenyl) or PMDA is used, it is mechanically fragile. Therefore, it is desirable to introduce a somewhat flexible skeleton by copolymerization.

[Example 25] Using the polyamic acid of Example 21, a multilayer wiring board having 6 wiring layers was prepared in the same process as in Example 18. A multilayer wiring board made of alumina was used as the substrate. The multilayer wiring board was good with little warpage.

However, when it was adhered on a silicon wafer in the same manner, the warpage was large and a part of the wafer was peeled off at the interface between the insulating film and the insulating film.
The copolymerizable range of flexible polyimide is slightly different depending on the thermal expansion coefficient and adhesiveness of the substrate, but no problem occurs if it is within 30 mol%.

〔The invention's effect〕

According to the present invention, it is possible to obtain a multilayer wiring board having an insulating layer made of polyimide having an extremely small thermal expansion coefficient equivalent to that of an inorganic substance, and it is possible to improve the reliability of an electronic device or the like using the same.

[Brief description of drawings]

FIG. 1 is a graph showing the thermal expansion coefficient of various materials, FIG. 2 is a sectional view of a wiring portion of a bipolar LSI, and FIG. 3 is a sectional view of a printed wiring board based on an LSI-mounted metal plate. 3 ... Silicon wafer, 4 ... Thermal oxide film, 5 ... Aluminum wiring, 6 ... Polyimide film, 10 ... Substrate, 11 ... LSI chip, 1
2 ... PI carrier film, 14 ... bonding solder balls, 15 ... wiring part, 16 ... insulating film.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Tokuyuki Kaneshiro 3-1-1, Saiwaicho, Hitachi City, Ibaraki Hitachi Ltd. Hitachi Research Laboratory (72) Inventor Junichi Imaizumi 1500 Ogawa Ogawa, Shimodate, Ibaraki Hitachi Kasei Kogyo Co., Ltd. Shimodate No. 2 Factory (72) Inventor Yoshikatsu Mikami 1500 Ogawa, Shimodate City, Ibaraki Prefecture Hitachi Chemical Co., Ltd. Shimodate No. 2 Factory (56) Reference JP-A-60-221426 (JP, A) ) JP-A-59-15921 (JP, A)

Claims (2)

[Claims] 1. A method of manufacturing a multilayer wiring board for an electronic device, comprising a conductor and an insulating layer on an inorganic (excluding metal) substrate, wherein the insulating layer has a general formula of H ₂ N--Ar ¹ --NH ₂ … (1), Polyamic acid obtained by reacting with [formula (1)
In (2) and (3), Ar ¹ is R represents a lower alkyl group, a lower alkoxy group, a fluorinated alkoxy group, an acyl group or halogen, and n
Is an integer of 1 to 4, m is 0 or an integer of 1 to 3, X,
Y represents halogen, -OR 'or -OH, R'represents a lower alkyl group or a fluorinated alkoxy group, which may be different from each other. However, when a pyromellitic acid component is included as the tetracarboxylic acid component, the proportion of the pyromellitic acid component is less than 50 mol%. ] Is directly applied and then imidized, or a polyimide film imidized with the polyamic acid is adhered to form an insulating layer having a thickness of 2 μm or more and a linear expansion coefficient of 0.2 to 3.2 × 10 ⁻⁵ K ^−. A method of manufacturing a multilayer wiring board for an electronic device, comprising: 2. A method of manufacturing a multilayer wiring board for an electronic device, comprising a conductor and an insulating layer on an inorganic (but excluding metal) substrate, wherein the insulating layer has the general formula H ₂ N--Ar ¹ --NH ₂ … (1), Polyamic acid obtained by reacting with [formula (1)
In (2) and (3), Ar ¹ is R represents a lower alkyl group, a lower alkoxy group, a fluorinated alkoxy group, an acyl group or halogen, and n
Is an integer of 1 to 4, m is 0 or an integer of 1 to 3, X,
Y represents halogen, -OR 'or -OH, R'represents a lower alkyl group or a fluorinated alkoxy group, which may be different from each other. However, when a pyromellitic acid component is included as the tetracarboxylic acid component, the proportion of the pyromellitic acid component is less than 50 mol%. ], And the polyimide precursor other than the polyamic acid is copolymerized or blended within 35% by weight and then directly imidized, or a polyimide film obtained by imidizing the copolymerized or blended polyamic acid is prepared. Bonded, thickness is 2μm or more, and linear expansion coefficient is 0.2-3.2
× 10 ^-5 K ^- the preparation of a multilayer wiring substrate for an electronic device, which comprises forming the insulating layer.