JPH01121325A - Polyimidesiloxane and composition containing same - Google Patents

Abstract

PURPOSE:To obtain a polyimidesiloxane outstanding in solubility to organic solvents, adherability and heat resistance, suitable as a material for interlaminar insulation films to be used in electronic parts, surface-protective films etc., by polymerization and imide conversion of each specific aromatic tetracarboxylic acid component and diamine component. CONSTITUTION:(A) An aromatic tetracarboxylic acid component consisting mainly of (pref. containing >=90mol.% of) biphenyltetracarboxylic acids and (B) a diamine component made up of (i) a diaminopolysiloxane of formula (R1 is divalent hydrocarbon; R2 is 1-3C alkyl or phenyl; l is 1-30) and (ii) an aromatic diamine [pref. containing 10-40mol.% of the component (i)] are heated at 140-250 deg.C e.g. in an organic solvent to carry out polymerization and imide conversion, thus obtaining the objective polyimidesiloxane. Said polyimidesiloxane is dissolved in an organic solvent to obtain the other objective homogeneously dissolved polyimidesiloxane composition.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a novel polyimidesiloxane and a composition in which the polyimidesiloxane is uniformly dissolved in an organic solvent. It has excellent solubility in solvents, excellent adhesion, especially excellent moisture-resistant adhesion in humid atmosphere during low-temperature processing, and excellent heat resistance. Used as a forming material for films, etc.

[Conventional technology and its problems]

Various proposals have already been made to use aromatic polyimide as an electrically insulating protective film (for example, an insulating film between the eyebrows).
For example, JP-A-48-34686 and JP-A-49
Publication No. 40077 and others disclose that insulating films for solid-state devices, puffybesilan films, glabella insulating films for semiconductor integrated circuits, etc. are formed using polyimide, which has excellent properties such as heat resistance and insulating properties. .

However, for boat fishing, aromatic polyimide is difficult to dissolve in organic solvents, so a solution of aromatic polyimide precursor (aromatic polyamic acid) is used to form a coating film, and then dried. For imidization, it is necessary to heat-treat the coated film at a fairly high temperature for a long time to form a protective film of aromatic polyimides, and it is necessary to form a protective film of aromatic polyimides at a relatively low temperature with good reproducibility. However, there was a problem in that the electrical or electronic material itself to be protected would be thermally degraded.

On the other hand, as aromatic polyimides soluble in organic polar solvents, for example, polyimides such as those described in Japanese Patent Publication No. 57-41491 are known.

However, these aromatic polyimides did not have sufficient adhesion to the substrates to be coated, such as silicon wafers or glass plates, so it was necessary to treat the substrate with an adhesion promoter beforehand. Ta.

In order to solve these problems, copolymers with silicon compounds have been proposed, for example, in JP-A-57-1
43328 and JP-A-58-13631 disclose polyimide precursors in which one of the raw materials is polysiloxane terminated at both ends with diamine. However, these polyimide precursors have the drawback that the coating film must be treated at high temperature for imidization.

Also, JP-A-61-118424 and JP-A-61
207438 discloses soluble polyimidosiloxanes. However, the former polyimide siloxane has a manufacturing problem in that the manufacturing process involves several steps and takes a long time to manufacture. Furthermore, the latter polyimide siloxane does not contain an aromatic amine as an amine component and has a problem of low heat resistance.

Therefore, the object of the present invention is to provide a polyimide siloxane that does not have the above-mentioned problems, that is, has excellent solubility in organic solvents, excellent adhesion, particularly excellent moisture-resistant adhesion in a humidified atmosphere during low-temperature processing, Another object of the present invention is to provide a novel polyimidesiloxane that has excellent heat resistance and is easy to produce, and a composition containing the same.

c. Means for Solving Problems] As a result of extensive research, the present inventors have discovered that a specific aromatic tetracarboxylic acid component and a diamine component consisting of a specific diaminopolysiloxane and an aromatic diamine can be polymerized and imide. It has been found that the polyimidesiloxane obtained by the above-mentioned method achieves the above object.

The present invention was made based on the above findings, and consists of an aromatic tetracarboxylic acid component whose main component is biphenyltetracarboxylic acids, and a diamine component consisting of a diamino polysiloxane represented by the following general formula (I) and an aromatic diamine. The present invention provides a polyimide siloxane obtained by polymerizing and imidizing the above.

(In the formula, R3 represents a divalent hydrocarbon residue, R independently represents an alkyl group having 1 to 3 carbon atoms or a phenyl group, and l
represents an integer of 1 to 30) The present invention also provides a polyimidosiloxane composition in which the polyimidosiloxane of the present invention described above is uniformly dissolved in an organic solvent.

The polyimide siloxane of the present invention has sufficient melting performance in organic polar solvents such as phenol solvents and amide solvents (pyrrolidone solvents, formamide solvents, acetamide solvents, etc.), and It consists of siloxane and the above-mentioned solvent, and has a relatively low viscosity.
The polyimide siloxane composition (fest) of the present invention can be easily formed.

In addition, the polyimide siloxane of the present invention has excellent adhesion to substrates such as silicon wafers, and
The above method can be used for applications that could not be used without pre-treating the substrate with an adhesion promoter (such as a silane coupling agent), such as passivation films for ICs and LSIs, and junk silane coatings for diodes. It can be used without any processing.

Furthermore, the polyimidesiloxane of the present invention, like conventional aromatic polyimides, maintains excellent performance in terms of mechanical strength, heat resistance, electrical insulation, etc., and can be used as a surface protective film for various electrical or electronic materials. It can be suitably used as a glabellar insulating film, etc.

Therefore, if the polyimide siloxane of the present invention described above is used as
According to the polyimide siloxane composition of the present invention dissolved in a solvent, it can be applied to the surfaces of various electrical or electronic components, etc.
Next, by drying and heating at a relatively low temperature, an excellent protective film (thickness: approximately 0.5 to 500 μm) can be easily formed.

Hereinafter, first, the polyimidosiloxane of the present invention will be explained in detail.

The polyimidosiloxane of the present invention preferably contains an aromatic tetracarboxylic acid component containing preferably 80 mol % or more of biphenyl-tetracarboxylic acids and a diamino polysiloxane represented by the general formula (I) in an amount of preferably 10 to 40 mol %.
mol% and a diamine component consisting of aromatic diamine,
approximately equimolar, in an organic polar solvent at a fairly high temperature (preferably at a temperature of about 100 to 300°C, particularly preferably about 140 to 2
50° C.) and polymerization and imidization in two stages, or alternatively, the above two components are mixed in approximately equimolar amounts in an organic polar solvent, preferably at about 80° C.
Producing aromatic polyamic acid (precursor of aromatic polyimide) by polymerizing at the following temperature, particularly at a temperature of 0 to 60 ° C.,
It is a soluble polyimide siloxane produced by imidizing the aromatic polyamic acid under appropriate conditions.

The above biphenyltetracarboxylic acids include 3.3
°, 4.4'-biphenyltetracarboxylic acid or its acid dianhydride, 2. 3. 3', 4°-biphenyltetracarboxylic acid or its acid dianhydride, or an ester or salt of the above-mentioned aromatic tetracarboxylic acid. Carboxylic acid or its acid dianhydride is optimal because the resulting polyimidesiloxane has excellent solubility.

The aromatic tetracarboxylic acid component is a part of the biphenyltetracarboxylic acids, for example, 3.3°, 4°
, 4°-benzophenonetetracarboxylic acid or its dianhydride, 2,3,3°, 4°-benzophenonetetracarboxylic acid or its acid dianhydride, pyromellitic acid or other aromatic acid dianhydride, etc. The above-mentioned biphenyltetracarboxylic acid #IM
Can be used with The proportion of the above-mentioned "other aromatic tetracarboxylic acids" used is less than about 20 mol%, especially 10% by mole, based on the total aromatic tetracarboxylic acid component.
Preferably, it is less than mol%.

Furthermore, examples of the diaminopolysiloxane represented by the general formula (I) include the following compounds.

These diamino polysiloxanes have a l value in the range of 1 to 30. If a diamino polysiloxane is used with a l value exceeding 30, the resulting polyimidosiloxane will have a low molecular weight and will also have a low solubility in organic solvents.

Further, as the aromatic diamine, for example, 4.4
゛-Diaminodiphenyl ether, 4゜4°-diaminodiphenylmethane, o-F lysine, O-dianisidine, 2,4-diaminotoluene, paraphenylenediamine, bis(4-(4°-aminophenoxy)phenyl)
Sulfone, 2.2-bis[4°-(4″-aminophenoxy)phenyl]propane, 1.4-bis(4′-aminophenoxy)benzene, 4.4°-diamino-3
-monoamide-diphenyl ether, or for example 3,5-diaminobenzyl acrylate, 2-(3,5
Examples include compounds having a hydrocarbon unsaturated group such as -diaminobenzoyloxy)ethyl methacrylate.

As mentioned above, the proportion of the diamino polysiloxane represented by the general formula (I) in the total diamine component is preferably 10 to 40 mol%, and if it is less than 10 mol%, the adhesion of the resulting polyimidosiloxane decreases, When it is more than 40 mol%, it is difficult to obtain sufficient heat resistance.

Examples of the organic polar solvent used in the polymerization include sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide, N,N-dimethylformamide,
Formamide solvents such as N,N-diethylformamide, N,N-dimethylacetamide, acetamide solvents such as N,N-diethylacetamide, N-methyl-
Pyrrolidone solvents such as 2-pyrrolidone and N-vinyl-2-pyrrolidone, hexamethylene phosphoamide, γ-butyllactone, cyclohexanone, etc., or phenol, 0-2m- or p-cresol, xylenol, halogenated phenol (para (chlorophenol, orthochlorophenol, parabromophenol, etc.), phenolic solvents such as catechol, and the like.

The polyimidosiloxane of the present invention is preferably a high molecular weight polymer, for example, concentration: 0.5g/1o
The logarithmic viscosity (indicating the degree of polymerization of the polymer) measured at a measurement temperature of 30°C in a solution of (ld solvent (N-methyl-2-pyrrolidone)) is 0.1 to 2.01, especially 0.2
It is preferable that it is about 1.5 to 1.5.

The polyimidosiloxane of the present invention can be produced using an organic polar solvent similar to the organic polar solvent used in the above-mentioned polymerization, or a mixed solvent in which xylene, ethyl cellosolve, diglyme, dioxane, etc. are partially blended with these organic polar solvents. Since it is very easily soluble, the polyimidosiloxane is preferably uniformly dissolved in the organic polar solvent at a concentration of about 1 to 50% by weight, particularly preferably 3 to 40% by weight, and preferably has a rotational viscosity at 25°C of about A solution (varnish) of polyimidosiloxane having a void size of 0.01 to 10,000, particularly preferably 0.1 to 1,000, ie, a "polyimidosiloxane composition of the present invention" can be prepared.

Next, the polyimidosiloxane composition of the present invention, in which the above-mentioned polyimidosiloxane of the present invention is uniformly dissolved in an organic solvent, will be described in detail.

The polyimidosiloxane composition of the present invention may be a polymerization solution of polyimidosiloxane obtained by polymerizing and imidizing the monomer components in one step in an organic polar solution as described above, or the polymerization solution may be The polyimidesiloxane composition of the present invention may be diluted with a suitable solvent similar to the solvent, or the polyimidesiloxane composition of the present invention may be diluted with a solvent similar to the solvent.
It can also be prepared by dissolving polyimidosiloxane powder, which has been isolated as a powdery precipitate from the above-mentioned polymerization solution, in the above-mentioned organic polar solvent.

According to the polyimide siloxane composition of the present invention, an excellent protective film can be formed on the surface of electrical or electronic components, for example, in the following manner.

The polyimide siloxane composition of the present invention is coated on the surface of the object (circuit board, semiconductor, etc.) at room temperature or under heating, using a spin coating machine, dispenser, printing machine, etc., to achieve a uniform thickness. by applying the composition to form a coating film made of the composition of the present invention, and then drying the coating film at a temperature of about 50°C or higher, particularly 60 to 250°C,
A solidified film (protective film) of polyimide siloxane is obtained.

〔Example〕

The present invention will be explained in more detail with reference to Examples below.

Example 1 2.3.3° to 91.08g of cyclohexanone.

4゛-Biphenyltetracarboxylic dianhydride 10゜0
8 g, and 12.09 g of bis(4-(4'-aminophenoxy)phenyl)sulfone and
) of jl −9,8 w, w” −bis−(
3-aminopropyl)polydimethylsiloxane 6, 17
The reaction solution was maintained at a reaction temperature of 150° C. for 8 hours to carry out polymerization while nitrogen gas was passed through and stirred.

The resulting reaction solution was added to stirring methanol in Step 1 to precipitate polyimidosiloxane, which was filtered and dried.
24.5 g of white polyimidosiloxane powder (polyimidosiloxane of the present invention) was obtained.

This polyimide siloxane powder is 0.5g/100m
The logarithmic viscosity at 30° C. was 0.37 (N-methifle-2- and lolidon solvent). In addition, an infrared absorption spectrum was measured, and it was confirmed that imide group absorption existed at 1770 cm and 730 cm.

The polyimidosiloxane obtained as described above was dissolved in a tit mixed solvent of dioxane and N-vinyl-2-pyrrolidone to form a homogeneous polyimidosiloxane solution (polyimidosiloxane composition of the present invention) with a concentration of 20% by weight. Prepared.

This solution was coated onto a silicon wafer using a spin coater and dried by heating at 80° C. and 230° C. for 30 minutes each to obtain a polyimide siloxane thin film with a thickness of about 3 μm. After the silicon wafer coated with this thin film was left in saturated steam at 120°C for 100 hours, a base tape peel test (JIs D 0202) was immediately performed, and no lifting or blistering of the thin film was observed. The thin film was well adhered to the silicon wafer.

In addition, when the above polyimide siloxane thin film was heated at a rate of 10°C/min using a calorimeter (Model 951 manufactured by DuPont), no weight loss was observed up to 380°C, and differential thermal analysis showed that the glass temperature reached 240°C. There was a transition temperature.

Examples 2 to 5 Polymerization was carried out in the same manner as in Example 1 except that the conditions shown in Table 1 below were used to obtain polyimide siloxanes of the present invention. The yield and the logarithmic viscosity of each of the obtained polyimidesiloxanes are shown in Table 1 below. In addition, the infrared absorption spectra of each of the obtained polyimidesiloxanes were measured, and the results showed that the infrared absorption spectra were 1770 cm + -' and 730 cm
It was confirmed that imide group absorption existed at m-'.

In addition, each of the obtained polyimidosiloxanes was made into a solution with the concentration shown in Table 2 below using the solvent shown in Table 2 below, and Example 1 was prepared using these polyimidosiloxane solutions (polyimidosiloxane compositions of the present invention). rIIM was formed in the same manner as in Example 1.
The film properties were measured in the same manner as above. The results are shown in Table-2 below.
Shown below.

Comparative Example I 2.3°3 in 90.0 g of N-methyl-2-pyrrolidone
',4'-biphenyltetracarboxylic dianhydride 8
．． 20 g and bis(4-(4'-aminophenoxy)phenyl) sulfone t were added, and the mixture was heated at a reaction temperature of 180° C. for 55 minutes with nitrogen gas flowing and stirring.
Polymerization was carried out by holding for a certain period of time.

This polymerization solution was poured into methanol, and the polyimide was precipitated and separated by filtration, followed by drying to obtain 17.5 g of white polyimide powder with a logarithmic viscosity of 0.62.

This polyimide powder was diluted with N-vinyl-2-pyrrolidone.
When the mixture was dissolved to a concentration of 0% by weight and an adhesion test to a silicon wafer was performed in the same manner as in Example 1, blistering was observed and the film was easily peeled off from the substrate with the tape.

〔Effect of the invention〕

The polyimidesiloxane of the present invention has excellent solubility in organic solvents, excellent adhesion, particularly excellent moisture-resistant adhesion in a humidified atmosphere during low-temperature treatment, and excellent heat resistance.
Moreover, it is a new compound that is easy to produce, and can be used as a material for forming glabella insulating films and surface protective films for electronic components.

Moreover, according to the polyimide siloxane composition of the present invention,
A protective film with excellent film properties can be formed on the surfaces of various electrical or electronic components. .

Claims (3)

[Claims] (1) Obtained by polymerizing and imidizing an aromatic tetracarboxylic acid component mainly consisting of biphenyltetracarboxylic acids and a diamine component consisting of a diamino polysiloxane and an aromatic diamine represented by the following general formula (I). polyimide siloxane. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) (In the formula, R_1 represents a divalent hydrocarbon residue, R_2 independently represents an alkyl group or phenyl group having 1 to 3 carbon atoms, and l represents 1 (Indicates an integer between ~30.) (2) Claim No. 1, wherein the proportion of diaminopolysiloxane in the diamine component is 10 to 40 mol%.
Polyimidosiloxane as described in Section 1. (3) Obtained by polymerizing and imidizing an aromatic tetracarboxylic acid component mainly consisting of biphenyltetracarboxylic acids and a diamine component consisting of a diamino polysiloxane and an aromatic diamine represented by the following general formula (I). A polyimidesiloxane composition, wherein the polyimidesiloxane is uniformly dissolved in an organic solvent.