JPH0288677A - Polyimidesiloxane composition - Google Patents

Abstract

PURPOSE:To obtain the title composition capable of providing excellent coating properties to an inorganic or metallic material and forming coating layer having excellent moisture resistance, adhesion and heat resistance and suitable for interlaminar insulation membrane for electronic component by blending a specific soluble polyimide siloxane solution with a specific aminosilicone compound. CONSTITUTION:The aimed composition obtained by uniformly dissolving a soluble polyimide siloxane obtained by polymerizing and imidizing an aromatic tetracarboxylic acid component consisting essentially of biphenyltetracarboxylic acids with a diamine component consisting essentially of diaminopolysiloxane and aromatic diamine in an organic solvent (e.g. dimethyl sulfoxide) at a concentration of 1-50wt.% and adding an aminosilicone compound having one primary amino group to the above-mentioned solution at an amount of 0.01-20wt.%, preferably 0.1-10wt.% based on the polyimidesiloxane.

Description

[Detailed Description of the Invention] [Field of Industrial Application] This invention provides an amino silicon compound having one primary amino group in a polyimide siloxane solution in which a specific soluble polyimide siloxane is uniformly dissolved in an organic solvent. The present invention relates to a polyimidesiloxane composition obtained by adding the following.

The polyimide siloxane composition of the present invention has excellent coating performance such as coating flatness on the surfaces of various inorganic or metallic materials, and also has excellent coating properties by drying and heat-treating the coating layer. It is possible to form a coating layer that has excellent adhesion, especially in a humidified atmosphere by low-temperature treatment, and excellent heat resistance, and is suitable for thin film layers such as interlayer insulation films and surface protection films for electronic components. It is suitably used as a forming material.

[Description of prior art]

Various proposals have already been made to use aromatic polyimide as an electrically insulating protective film (such as an interlayer insulating film); for example, JP-A-48-34686 and JP-A-49-
Publication No. 40077 and the like disclose that insulating films for solid-state devices, passivation films, interlayer insulating films for semiconductor integrated circuits, and the like are formed of polyimide, which has excellent 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 and imide coated. To achieve this, it is necessary to heat-treat the coated film at a fairly high temperature for a long time to form a protective film made of aromatic polyimide. 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 JP-A-57-41491 are known.

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

In order to solve these problems, copolymers with silicon compounds have been proposed as polyimides; for example, JP-A-57-143328 and JP-A-58-
Publication No. 13531 discloses a polyimide precursor in which a polysiloxane terminated at both ends with diamine is used as a monomer raw material. However, these polyimide precursors also had the drawback that the coating film had to be treated at high temperature for imidization.

Also, JP-A-61-118424 and JP-A-61
207438 discloses a soluble polyimide siloxane, but the former polyimide siloxane has manufacturing problems in that the manufacturing process is complicated and takes a long time. Furthermore, since the latter polyimide siloxane does not contain aromatic diamine as an amine component, it has a problem of low heat resistance.

Furthermore, the inventors previously applied for patent application No. 6227868.
As No. 7, we proposed a polyimide precursor acid and a composition containing it. This polyimide siloxane had fairly excellent coating flatness and moisture-resistant adhesion, but when the heating drying temperature was 200°C or lower, the adhesion was insufficient, and unless heated to a higher temperature, It was not reliable as a protective film for electronic components.

[Means for solving problems]

As a result of intensive studies to provide a polyimidesiloxane that solves the above-mentioned problems, the inventors added a specific aminosilicon compound to a polyimidesiloxane solution in which a specific soluble polyimidesiloxane was uniformly dissolved in a solvent. The polyimidesiloxane composition obtained by adding the above has excellent coating flatness on an inorganic or metal plate, and the coating layer formed by drying and heat-treating the coating layer has an excellent coating layer. The present invention was completed based on the discovery that it has moisture-resistant adhesion, as well as excellent heat resistance and electrical insulation.

In this invention, a soluble polyimidosiloxane obtained by polymerizing and imidizing an aromatic tetracarboxylic acid component mainly composed of biphenyltetracarboxylic acids and a diamine component mainly composed of diaminopolysiloxane and aromatic diamine is used. The present invention relates to a polyimidesiloxane composition obtained by adding an aminosilicon compound having one primary amino group to a polyimidesiloxane solution uniformly dissolved in a solvent.

Hereinafter, the polyimide siloxane composition of the present invention will be explained in more detail.

The soluble polyimidosiloxane used in the composition of the present invention includes, for example, an aromatic tetracarboxylic acid component whose main component is biphenyltetracarboxylic acids (preferably containing 80 mol% or more), diamino polysiloxane and A diamine component consisting of an aromatic diamine is mixed in approximately equimolar amounts in an organic polar solvent at a fairly high temperature (preferably 1
00 to 300 °C, especially 140 to 250 °C), and polymerization and imidization in two stages, or the above two components are combined in approximately equimolar, organic polar Aromatic polyamic M (aromatic polyimide precursor) is produced by polymerization in a solvent, preferably at a temperature of about 80°C or less, especially at a temperature of 0 to 60°C, and the aromatic polyamic acid is Manufactured by imidization under certain 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 ester of the above aromatic tetracarboxylic acid It may also be a compound or a salt. In particular, in this invention, polyimidosiloxane obtained using an aromatic tetracarboxylic acid component whose main component is 2,3.3',4'-biphenyltetracarboxylic acid or its acid dianhydride, It is suitable because it has excellent solubility in organic solvents.

The aromatic tetracarboxylic acid component includes a portion of the biphenyltetracarboxylic acids, for example, 3.3'', 4.
．． Other aromatic compounds such as 4'-benzophenonetetracarboxylic acid or its dianhydride, 2.3.3°, 4'-benzophenonetetracarboxylic acid or its acid dianhydride, pyromellitic acid or its acid dianhydride It may be replaced with tetracarboxylic acids and used together with the above-mentioned biphenyltetracarboxylic acids.

The ratio of the amount of the above-mentioned "other aromatic tetracarboxylic acids" used is approximately 2
Preferably it is less than 0 mol%, especially less than 10 mol%.

The diamino polysiloxane has the following general formula (wherein,
R' represents a divalent hydrocarbon residue, and R2 has 1 to 1 carbon atoms.
10 hydrocarbon groups, m is an integer of 1 to 30, especially 2
It is preferable that the polysiloxane is a polysiloxane represented by (representing an integer of 20 to 20).

As the diaminopolysiloxane represented by the above general formula (f), these diaminosiloxanes preferably have m in the range of 1 to 30, and when m exceeds 30 is used in the above polymerization, the diaminosiloxane obtained is This is not preferable because the molecular weight of the polyimidosiloxane becomes low and its solubility in organic solvents also decreases.

Further, as the aromatic diamine, for example, 4.4
-diaminodiphenyl ether, 4,4”-diaminodiphenylmethane, 0-)lysine, 0-dianisidine, 2
, 4-diaminotoluene, bis(4-(4aminophenoxy)phenyl)sulfone, 2.2-bis[4”-(4
"-Aminophenoxy)phenyl]propane, 1.4-
Bis(4′-aminophenoxy)benzene, 4,4”-
Preferred examples include aromatic diamines having two or more benzene nuclei such as diamino-3-monoamide-diphenyl ether.

The polyimidesiloxane used in this invention contains diaminopolysiloxane as a diamine component in a proportion of 40 mol% or less, particularly 5 to 35 mol%, and is polymerized with an aromatic tetracarboxylic acid component. Polymers obtained by this method are preferable, and if the content of the diaminopolysiloxane is too high, it may not be possible to obtain a polyimidosiloxane having sufficient heat resistance, which is not preferable.

Examples of the organic polar solvent for polymerization used in the production of the above-mentioned polyimidosiloxane include sulfochito-based solvents such as dimethyl sulfoxide and diethyl sulfoxide, N
, N-dimethylformamide, formamide-based solvents such as N,N-diethylformamide, acetamide-based solvents such as N,N-dimethylacetamide, N,N-diethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2 - Pyrrolidone-based solvents such as pyrrolidone, hexamethylene phosphoamide, T-butyl lactone, diethyl glycol dimeryl ether, cyclohexanone, etc.
Alternatively, phenolic solvents such as phenol, o-, m- or p-cresol, xylenol, halogenated phenol (para-chlorophenol, ortho-chlorophenol, para-bromophenol, etc.), catechol, etc. can be used.

The soluble polyimidosiloxane used in the composition of this invention is preferably a polymer of high molecular weight, for example in solution at a concentration of 0.5 g/100 ml solvent (N-methyl-2-pyrrolidone). , 30°
The logarithmic viscosity (indicating the degree of polymerization of the polymer) measured at the measurement temperature of C is 0.1 to 2.0, particularly 0.2 to 1.
It is preferable that it is about 5.

The organic solvent used in the composition of the present invention includes the same organic polar solvents as those used in the production of the above-mentioned soluble polyimidosiloxane, or xylene, ethyl cellosolve, dioxane, etc. Examples include mixed solvents partially containing tetrahydrofuran (THF) and the like.

The concentration of soluble polyimidosiloxane in the polyimidosiloxane solution used in preparing the composition of this invention is preferably 1 to 50% by weight, particularly 3 to 50% by weight.

The polyimidosiloxane solution has a rotational viscosity of about 0.02 to 10,000 poise at 25°C, especially 0, 1 to 1 poise.
000 poise is preferable.

The silicon compound having one primary amino group used in the composition of this invention has the general formula (II) Hz N R
3S i (R') x−k(R5)K (II
) (However, R3 is a divalent hydrocarbon residue, or (
C1lz)n+ N H(CHz)nz-, and n
1 and R2 represent integers of 1 to 3, and R4 has 1 to 3 carbon atoms.
3, R5 represents an alkoxy group having 1 to 3 carbon atoms, and k represents an integer of 0 to 3.

As the amino silicon compound, for example, N-β
Examples include (aminoethyl)T-aminopropyltrimethoxysilane, N-β(aminoethyl)γ-aminopropylmethyldimethoxysilane, and T-aminopropyltriethoxysilane.

In the composition of the present invention, the above-mentioned aminosilicon compound is added to the polyimidesiloxane solution in an amount of 0.01 to 20% by weight, particularly 0.1 to 10% by weight based on the polyimidesiloxane.
Preferably, it is added in a proportion of approximately % by weight.

In this invention, if the proportion of the amino silicon compound added is too low, the adhesion of the resulting composition is not improved, and if the proportion of the amino silicon compound added is too large, the resulting composition is not improved. This is undesirable because the stability of the resulting composition deteriorates and a uniform coating film is not formed during application.

In the composition of the present invention, the polyimidesiloxane and the aminosilicon compound having one primary amino group partially react to open the imide bond of the polyimidesiloxane, and the polyimidesiloxane may be partially modified.

The composition of the present invention has a solution viscosity of about 0.
It is preferably about 0.02 to 50,000 voids, particularly about 0.04 to 5,000 voids.

According to the composition of this invention, for example, as follows:
An excellent protective film can be formed on the surface of electrical or electronic materials.

The composition of this invention is applied to the surface of the object to be coated (circuit board, semiconductor, etc.) to a uniform thickness at room temperature or under heating using a method such as a rotary coater, dispenser, or printing machine. , forming a coating film consisting of the composition of the present invention, and then heating the coating film at about 50°C or higher, particularly at 60°C to 2°C.
By drying at a temperature of 50°C, a solidified film (protective film) of polyimide siloxane can be formed.

〔Example〕

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

Example 1 A separable flask (equipped with a stirring rod, a nitrogen gas inlet, and a moisture metering receiver) made of polyimide siloxane was (B) In the above general formula (1), m (average value) was 9
．． 6.17 g of rω,ω°-bis(3-aminopropyl)polydimethylsiloxane J having a value of about 8.

and (C) "Add 12.09 g of bis(4-(4'-aminophenoxy)phenyl)sulfone J and 91.08 g of cyclohexanone, and then add (
A) Add 10.08 g of 2,3.3',4'-biphenyltetracarboxylic dianhydride, and while stirring, flow nitrogen gas into the separable flask, and stir the reaction solution in the flask. The reaction temperature was held at 150° C. for 8 hours to effect polymerization and imidization to produce soluble polyimidosiloxane.

The obtained reaction solution is added little by little into stirring methanol to precipitate the polyimide siloxane produced in the above reaction, and this is filtered. After filtration, the polyimide siloxane powder obtained by filtration was mixed with 80% methanol.
0mj! Wash in a mixer with water. This cleaning is done 2 times.
After repeating this process several times, it was dried under reduced pressure to obtain 24.5 g of soluble polyimidosiloxane powder.

This polyimide siloxane powder has a concentration of 0.5g/1
The logarithmic viscosity (30°C) at 00 mn (N-methyl-2-pyrrolidone solvent) was 0.37. In addition, infrared absorption spectrum analysis was performed, and 1770 cm-' and 73 cm-'
It was confirmed that imide group absorption existed at 0 cm-'.

[Bo-imidosiloxane] 12.5 g of the polyimidosiloxane powder obtained as described above was uniformly dissolved in 50 g of cyclohexanone to prepare a polyimidosiloxane solution, and then (E)) J- β(
0.25 g of γ-aminopropyltrimethoxysilane (aminoethyl) was added and stirred until a homogeneous state was obtained.
．． 3 voices).

[Ken Postmark 11th Kosaku] The polyimide siloxane composition obtained as described above was applied onto a glass plate using a rotary coating machine, and an 80°
After drying at 200°C for 30 minutes at 1300°C or 400°C for 30 minutes, a thin film with a thickness of about 3 μm was formed.

The glass plate coated with the thin film in step 1 was left in saturated steam at 120"C, and 100 crosscuts with IM spacing were made on the surface of the film immediately after removal. ) was applied, the tape was peeled off vigorously in a 90° direction, and the number of coatings that remained on the glass plate without any abnormalities was measured.

As a result, 3
Each sample that was heat-dried for 0 minutes remained 100% adherent even when the sample was left in saturated steam for 700 hours.

Furthermore, the polyimidesiloxane composition was applied on a copper plate, a gold plate, and a ceramic plate in the same way as on a glass plate, then heated and dried, and the same moisture resistance adhesion test as described above was conducted. As a result, each sample In both cases, 100% adhesion was maintained even after the samples were left in saturated water vapor for 700 hours.

Examples 2 to 4 Polymerization and imidization were carried out in the same manner as in Example 1 except that the polymerization conditions shown in Table 1 were used to obtain soluble polyimidosiloxanes.

As a result, the yield and logarithmic viscosity of the obtained soluble polyimidosiloxane are shown in Table 1.

In addition, each of the obtained soluble polyimidesiloxanes was subjected to infrared absorption spectrum analysis, and 1770c+n-' and 7
The presence of imide group absorption at 30 cm-' was confirmed in each case.

Further, polyimidosiloxane compositions were produced in the same manner as in Example 1, except that the types of solvents and the proportions of each component used were as shown in Table 2 for each of the obtained soluble polyimidosiloxanes.

Example 1 using those polyimidesiloxane compositions
A moisture resistant adhesion test similar to that was conducted. The results are shown in Table 3.

Example 5 [Production of soluble polyimide siloxane] In a separable flask, rω, ω whose general formula m (average value) is 9.8
453.60 g of -bis(3-aminopropyl)polydimethylsiloxane, 44.92 g of 1°3-bis(4'-aminophenoxy)benzene, and NMP368.3
Add 7g and 122.79g of diglyme, then add 2.
3. Add 64.82 g of 3',4'-biphenyltetracarboxylic dianhydride, and while flowing nitrogen gas into the separable flask and stirring, the reaction solution in the flask was heated to 190°C. The reaction temperature was held for 7 hours to effect polymerization and imidization to produce soluble polyimidosiloxane.

The resulting reaction solution was added little by little to stirring methanol in 81 to precipitate the polyimide siloxane produced in the above reaction, and this was filtered. After filtration, the polyimide siloxane powder obtained by filtration is mixed with methanol 6! Wash in a mixer with water. After repeating this washing twice, it was dried under reduced pressure to obtain 142.94 g of soluble polyimide siloxane powder.

This polyimidosiloxane powder has a logarithmic viscosity at 30 °C (concentration i 0.5 g / 100 ml solvent, solvent;
N-methyl-2-pyrrolidone) is 0.40, and
As a result of infrared absorption spectrum analysis, 1770cl'
It was confirmed that imide group absorption existed at 130 cm-'.

[Preparation of polyimidosiloxane composition] 2.50 g of the polyimidosiloxane powder obtained as described above was uniformly dissolved in 47.5 g of tetrahydrofuran to prepare a polyimidosiloxane solution, and then (F) γ-amino Add 0.25 g of propyltrimethoxysilane and stir until it becomes homogeneous to form a polyimidosiloxane composition (solution viscosity at 25°C, 0.04 poise).
was prepared.

Further, the above polyimide siloxane composition was applied to a Teflon plate and dried at 80°C for 30 minutes to form a film.

This film was peeled off from the Teflon plate and subjected to infrared absorption spectrum analysis. As a result, a new absorption of the amide group was confirmed at 1650 cm-', and a part of the imide ring of polyimidosiloxane was It is thought that the ring was opened by methoxysilane.

Comparative Example 1 A thin film was formed in the same manner as in Example 1 using the polyimide siloxane solution prepared in Example 1 (a solution containing no aminosilicon compound) instead of the polyimide siloxane composition. A moisture resistant adhesion test was conducted in the same manner as in Example 1. As a result, under each heating drying condition, the time for 100% adhesion was 2.
100 hours at 00°C, 240 hours at 300°C, 40
The temperature was 260 hours at 0°C.

Table 1 A): 2.3.3", 4"-biphenyltetracarboxylic dianhydride B): ω,ω'-bis(3
-Aminopropyl)polydimethylsiloxane C): Bis(4-(4''-aminophenoxy)phenyl)sulfone D): 1,3-bis(4'-aminophenoxy)Hensen*122.79g of Nidiglyme and NMP368
．． Mixed solvent with 37g Table 2 Table 3 E): N-β(aminoethyl)T-aminopropyltrimethoxysilane F): γ-aminopropyltrimethoxysilane NMP: N-methyl-2-pyrrolidone Comparative Example 2 Using N-methyl-2-pyrrolidone as a polymerization solvent,
Polymerization was carried out in the same manner as in Example 1, except that the polymerization reaction temperature was 20°C, and as a result, soluble polyamic acid was produced.

The polyamic acid has a logarithmic viscosity of 0.4 at 30°C.
It was 4.

The amino silicon compound used in Example 1 was added to the polyamic acid solution (reaction liquid) to prepare a polyamic acid composition (solution viscosity at 25° C.; 15 voids).

A thin film was formed using the polyamic acid composition prepared as described above, and the same moisture resistant adhesion test as in Example 1 was conducted on the thin film.

As a result, the time that the thin film remained 100% in contact was 200%.
Less than 20 hours at ℃, 240 hours at 300℃, 400℃
It was 420 hours.

[Actions and effects of the present invention]

The polyimide siloxane composition of the present invention has excellent coating properties on the surfaces of various inorganic or metallic materials,
In addition, the thin film made of polyimide siloxane formed by drying and heat-treating the coating layer exhibits excellent moisture-resistant adhesion even in harsh environments, especially in humidified atmospheres, and also has excellent heat resistance. It is used as a forming material for interlayer insulation films and surface protection films for electronic components.

Patent applicant: Ube Industries Co., Ltd.

Claims (1)

[Claims] A soluble polyimidosiloxane obtained by polymerizing and imidizing an aromatic tetracarboxylic acid component mainly composed of biphenyltetracarboxylic acids and a diamine component mainly composed of diaminopolysiloxane and aromatic diamine is uniformly distributed in an organic solvent. A polyimidesiloxane composition obtained by adding an aminosilicon compound having one primary amino group to a dissolved polyimidesiloxane solution.