JP3019166B2 - Method for producing polyimide multilayer film - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a polyimide multilayer film comprising a soluble polyimide, and more particularly to a method for producing a polyimide multilayer film used for electronic parts, electronic / optical parts, and optical parts.

[0002]

2. Description of the Related Art Polyimide has been widely used mainly in the field of space and aviation because of its excellent heat resistance. Recently, it has been used as an interlayer insulating film for electronic components, a material for a multilayer wiring board, and the like, utilizing the characteristics of excellent heat resistance such as withstanding the semiconductor process temperature. These polyimides are required to have a low dielectric constant from the viewpoint of increasing the speed of signals. In addition, polyimide is beginning to be expected as an optical waveguide in electronic / optical components and optical components, and this polyimide is required to have low optical transmission loss, that is, transparency. Various polyimides having such a low dielectric constant and transparency have recently been developed. For example, the Sampe Journal (SAMPE
JOURNAL), July / August (1985), page 28, reports some examples of transparent polyimides. One feature of these transparent polyimides is that they are soluble in solvents. Further, the present inventors have disclosed a transparent fluorinated polyimide having a low dielectric constant in Japanese Patent Application No. 1-120110. Many of these polyimides are soluble in solvents.

When these low dielectric constant and transparent polyimides are used as interlayer insulating films and optical waveguides, they are often required to have a multilayer structure. That is, it is necessary to form at least one more polyimide film on the upper layer of the polyimide film. However, since these low dielectric constant and transparent polyimides have the property of being soluble in a solvent, it is difficult to make them into a multilayer. The present inventors utilize the difference in solubility of polyimide and its precursor in the solvent of polyamic acid as a method for producing these polyimide multilayer films, and do not dissolve polyimide , but dissolve polyamic acid.
A polyamic acid solution is prepared by using a solvent, and a polyimide multilayer film in which a polyimide film is formed on a soluble polyimide has been successfully manufactured. Although this production method is an interesting method for forming a multilayer film of a soluble polyimide, it has a disadvantage that the same solvent cannot be used as a solvent for the polyamic acid and the polyimide.

[0004]

As described above, it was impossible to form a multilayer film of a soluble polyimide using the same solvent. An object of the present invention is to provide a simple method for producing a soluble polyimide multilayer film having a low dielectric constant and excellent transparency.

[0005]

If outlined present invention According to an aspect of the present invention is a in invention relates to a method for manufacturing a polyimide multilayer film
Te in the upper layer of the soluble underlying polyimide film in an organic solvent, a method <br/> for producing a polyimide multilayer film by forming a port re <br/> imide film, prior to forming the upper layer of the polyimide film , the polyimide film of the soluble bottom layer to the organic <br/> solvent, line heat treatment at 380 ° C. or higher, the polyimide film which is insoluble in organic solvent
Characterized in that comprising the step of forming a.

The inventors of the present invention have studied the relationship between the heat treatment temperature of a soluble polyimide and the solubility in a solvent in order to achieve the above object. Disappears, and the fact that multi-layering is possible,
The present invention has been completed.

As the soluble polyimide used in the present invention, all soluble polyimides can be used. For example, polyimides, polyimide copolymers, and polyimide mixtures produced from the following tetracarboxylic acids or their derivatives and diamines that are soluble in solvents can be used.

[0008] Examples of the tetracarboxylic acid and its derivatives such as acid anhydrides, acid chlorides, and esterified compounds include the following. Here, an example of tetracarboxylic acid will be given.

(Trifluoromethyl) pyromellitic acid,
Di (trifluoromethyl) pyromellitic acid, di (heptafluoropropyl) pyromellitic acid, pentafluoroethylpyromellitic acid, bis {3,5-di (trifluoromethyl) phenoxy} pyromellitic acid, 2,3,3 ′,
4'-biphenyltetracarboxylic acid, 3,3 ', 4
4'-tetracarboxydiphenyl ether, 2,
3 ', 3,4'-tetracarboxydiphenyl ether, 3,3', 4,4'-benzophenonetetracarboxylic acid, 2,3,6,7-tetracarboxynaphthalene,
1,4,5,7-tetracarboxynaphthalene, 1,
4,5,6-tetracarboxynaphthalene, 3,3 ′,
4,4'-tetracarboxydiphenylmethane, 3,
3 ', 4,4'-tetracarboxydiphenylsulfone, 2,2-bis (3,4-dicarboxyphenyl) propane, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane, 5,5 '-Bis (trifluoromethyl) -3,3', 4,4'-tetracarboxybiphenyl, 2,2 ', 5,5'-tetrakis (trifluoromethyl) -3,3', 4,4'- Tetracarboxybiphenyl, 5,5'-bis (trifluoromethyl) -3,3 ', 4,4'-tetracarboxydiphenyl ether, 5,5'-bis (trifluoromethyl)-
3,3 ', 4,4'-tetracarboxybenzophenone, bis {(trifluoromethyl) dicarboxyphenoxy} benzene, bis {(trifluoromethyl) dicarboxyphenoxy} (trifluoromethyl) benzene,
Bis (dicarboxyphenoxy) (trifluoromethyl) benzene, bis (dicarboxyphenoxy) bis (trifluoromethyl) benzene, bis (dicarboxyphenoxy) tetrakis (trifluoromethyl) benzene, 3,4,9,10-tetra Carboxyperylene,
2,2-bis {4- (3,4-dicarboxyphenoxy) phenyl} propane, butanetetracarboxylic acid, cyclopentanetetracarboxylic acid, 2,2-bis {4-
(3,4-dicarboxyphenoxy) phenyl {hexafluoropropane, bis (trifluoromethyl) dicarboxyphenoxy} biphenyl, bis {(trifluoromethyl) dicarboxyphenoxy} bis (trifluoromethyl) biphenyl, bis} ( Trifluoromethyl)
Dicarboxyphenoxy diphenyl ether, bis (dicarboxyphenoxy) bis (trifluoromethyl) biphenyl and the like.

[0010] Examples of the diamine include the following. m-phenylenediamine, 2,4-diaminotoluene, 2,4-diaminoxylene, 2,4-diaminodulene, 4- (1H, 1H, 11H-eicosafluoroundecanooxy) -1,3-diaminobenzene, 4-
(1H, 1H-perfluoro-1-butanoxy) -1,
3-diaminobenzene, 4- (1H, 1H-perfluoro-1-heptanoxy) -1,3-diaminobenzene,
4- (1H, 1H-perfluoro-1-octanoxy)
-1,3-diaminobenzene, 4-pentafluorophenoxy-1,3-diaminobenzene, 4- (2,3
5,6-tetrafluorophenoxy) -1,3-diaminobenzene, 4- (4-fluorophenoxy) -1,3
-Diaminobenzene, 4- (1H, 1H, 2H, 2H-
Perfluoro-1-hexanoxy) -1,3-diaminobenzene, 4- (1H, 1H, 2H, 2H-perfluoro-1-dodecanoxy) -1,3-diaminobenzene,
p-phenylenediamine, (2,5-) diaminotoluene, 2,3,5,6-tetramethyl-p-phenylenediamine, (2,5-) diaminobenzotrifluoride, bis (trifluoromethyl) phenylenediamine,
Diaminotetra (trifluoromethyl) benzene, diamino (pentafluoroethyl) benzene, 2,5-diamino (perfluorohexyl) benzene, 2,5-diamino (perfluorobutyl) benzene, benzidine,
2,2'-dimethylbenzidine, 3,3'-dimethylbenzidine, 3,3'-dimethoxybenzidine, 2,2 '
-Dimethoxybenzidine, 3,3 ', 5,5'-tetramethylbenzidine, 3,3'-diacetylbenzidine,
2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 3,3'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, octafluorobenzidine, 4,4'-diamino Diphenyl ether,
4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 2,2-bis (p-aminophenyl) propane, 3,3'-dimethyl-4,4'-diaminodiphenylether, 3,3'- Dimethyl-4,
4'-diaminodiphenylmethane, 1,2-bis (anilino) ethane, 2,2-bis (p-aminophenyl) hexafluoropropane, 1,3-bis (anilino) hexafluoropropane, 1,4-bis (anilino ) Octafluorobutane, 1,5-bis (anilino) decafluoropentane, 1,7-bis (anilino) tetradecafluoroheptane, 2,2'-bis (trifluoromethyl)
-4,4'-diaminodiphenyl ether, 3,3'-
Bis (trifluoromethyl) -4,4'-diaminodiphenyl ether, 3,3 ', 5,5'-tetrakis (trifluoromethyl) -4,4'-diaminodiphenyl ether, 3,3'-bis (trifluoromethyl ) -4,
4'-diaminobenzophenone, 4,4 "-diamino-p-terphenyl, 1,4-bis (p-aminophenyl) benzene, p-bis (4-amino-2-trifluoromethylphenoxy) benzene, bis (Aminophenoxy) bis (trifluoromethyl) benzene, bis (aminophenoxy) tetrakis (trifluoromethyl) benzene, 4,4 ""-diamino-p-quarterphenyl, 4,4'-bis (p-aminophenoxy) ) Biphenyl, 2,2-bis {4- (p-aminophenoxy) phenyl} propane, 4,4'-bis (3-aminophenoxyphenyl) diphenylsulfone, 2,2-bis {4-
(4-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, 4,4'-bis (4-amino-2-trifluoromethylphenoxy) biphenyl, 4,4'-bis (4-amino-3-trifluoromethylphenoxy) ) Biphenyl, 4,4'-bis (4-amino-2-trifluoromethylphenoxy) diphenylsulfone, 4,4 '
-Bis (3-amino-5-trifluoromethylphenoxy) diphenylsulfone, 2,2-bis {4- (4-amino-3-trifluoromethylphenoxy) phenyl}
Hexafluoropropane, bis {(trifluoromethyl) aminophenoxy} biphenyl, bis [{(trifluoromethyl) aminophenoxy} phenyl] hexafluoropropane, diaminoanthraquinone, 1,5-diaminonaphthalene, 2,6-diaminonaphthalene, And bis {2-[(aminophenoxy) phenyl] hexafluoroisopropyl} benzene.

The polyimide layer formed on the soluble polyimide layer is not particularly limited, and any polyimide can be used.

As a method for producing the polyimide multilayer film of the present invention, for example, the following method can be used. Silicon, quartz,
On a substrate such as polyimide, a solution in which a soluble polyimide or a polyamic acid that is a precursor thereof is dissolved in a solvent is applied by a method such as spin coating, and cured at a predetermined temperature condition in which the polyimide is insoluble in an organic solvent. Obtain a membrane. Next, a polyamic acid solution, which is a precursor of polyimide for forming a second layer on the first polyimide film, is obtained. This polyamic acid solution is applied by a method such as spin coating, and then cured to obtain a second layer. If necessary, similarly, a third or more multilayer film is formed.

The present invention is characterized in that the heat treatment temperature of the soluble polyimide is set to a constant condition, and other manufacturing methods can be applied to a general method for manufacturing a polyimide multilayer film.

[0014]

EXAMPLES The present invention will be described in more detail with reference to several examples, but the present invention is not limited to these examples.

EXAMPLE 1 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl as a diamine and 2,2 as an acid anhydride on a 3-inch diameter silicon wafer whose surface is a silicon oxide layer. -Bis (3,4-dicarboxyphenyl)-
15% by weight of polyamic acid, a precursor of soluble polyimide prepared using hexafluoropropane dianhydride
The film thickness after heating the N, N-dimethylacetamide solution is 1
After coating by spin coating so as to have a thickness of 0 μm, heat treatment was performed so that the maximum temperature was 380 ° C. or higher. Thus, a polyimide film obtained from the first soluble polyimide layer was prepared. Next, the same polyamic acid solution was applied by spin coating so that the film thickness after heating became 10 μm, and then heat-treated at a maximum temperature of 350 ° C. As a result, a two-layer film of a soluble polyimide having a thickness of 20 μm was formed. As a result of observing the cross section of the two-layer film with a scanning electron microscope,
It was confirmed that the interface between both layers was formed without being affected by the solvent.

Examples 2 to 9 In Example 1, 2,2'-bis (trifluoromethyl) -polyamide was used as the polyamic acid as the precursor of the soluble polyimide in the first layer and as the polyamic acid as the precursor of the polyimide in the second layer.
Using a polyamic acid produced from 4,4'-diaminobiphenyl and the acid anhydride described in Table 1, the same procedure as in Example 1 was carried out to form a 20-μm-thick polyimide two-layer film. .

[0017]

Table 1 Table 1 Example 1st layer soluble polyimide precursor Acid anhydride used for the second layer polyimide precursor Acid anhydride used for the substrate ────────────────────────────── Example 2 6FDA: PMDA = 1: 0 6FDA: PMDA = 9: 1 Example 3 6FDA: PMDA = 1: 0 6FDA: PMDA = 8: 2 Example 4 6FDA: PMDA = 1: 0 6FDA: PMDA = 7: 3 ─────────────── Example 5 6FDA: PMDA = 1: 0 6FDA: PMDA = 6: 4 ──────────────────────────────────── Example 6 6FDA: PMDA = 9: 1 6FDA: PMDA = 1: 0 Example 7 6FDA: PMDA = 9: 1 6FDA: PMDA = 9: 1 Example 8 6FDA: PMDA = 9: 1 6FDA: PMDA = 8: 2 Example 9 6FDA: PMDA = 8: 2 6FDA: PMDA = 7: 3 ──────────── 6FDA; 2,2-bis (3,4-carboxyphenyl) - Hekisafuru Oropuropan dianhydride * PMDA; pyromellitic dianhydride

Example 10 The polyimide bilayer film obtained in Example 1 was subjected to a heat treatment at 380 ° C. for 1 hour, and a polyamic acid solution as a precursor of the soluble polyimide used in Example 1 was heated thereon. Was applied by spin coating so that the film thickness became 10 μm, and then heat-treated at a maximum temperature of 350 ° C. As a result, a three-layer film of a soluble polyimide having a thickness of 30 μm was formed.
As a result of observing the cross section of the three-layer film with a scanning electron microscope, it was confirmed that the interface of each layer was formed without being affected by the solvent.

Comparative Example 1 A multi-layer film was produced in the same manner as in Example 1 except that the heat treatment temperature was 350 ° C. and the heat treatment time was 1 hour in the preparation of the first polyimide film. However, the first soluble polyimide film was dissolved, and a multilayer film could not be produced.

[0020]

As described above, according to the present invention, 1
By setting the heat treatment time of the soluble polyimide of the layer to 380 ° C. or more, a polyimide multilayer film can be easily provided.
Using the multilayer film according to the present invention, a low optical loss buried polyimide optical waveguide, a low dielectric constant polyimide multilayer wiring board, and the like can be manufactured.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI H05K 1/03 610 H05K 1/03 610N // C08L 79:08 (56) References JP-A-64-81830 (JP, A) JP-A-55-7580 (JP, A) JP-A-4-235034 (JP, A) JP-A-4-8733 (JP, A)

Claims (2)

(57) [Claims] The upper layer of the soluble underlying polyimide film according to claim 1 the organic solvent, a method for <br/> producing a polyimide multilayer film to form a polyimide film to form a layer of polyimide film
Before, the soluble underlying polyimide film to the organic solvent, 3
The heat treatment at 80 ° C. or more I line, insoluble in the organic solvent
A method for producing a polyimide multilayer film, comprising a step of forming a polyimide film. 2. The method according to claim 1, wherein at least one of the polyimide films soluble in the organic solvent is 2,2'-bis (trifluoromethyl)-
The method for producing a polyimide multilayer film according to claim 1, wherein the polyimide is a polyimide containing 4,4'-diaminobiphenyl as a synthesis raw material, a polyimide copolymer, or a polyimide mixture.