KR100434753B1 - Preparation Method of Poly(organofluorosiloxane)-block-Polyimide Copolymer for the Application to Low Dielectric Coating Material - Google Patents

Abstract

It is an object of the present invention to provide a method for producing a fluorinated siloxane modified polyimide having improved water repellency, insulation properties and economic efficiency.

Methyltrifluoropropylcyclotrisiloxane and 1,3-bis-3-aminopropyl- (1,1,3,3 while introducing nitrogen gas into a four-necked flask equipped with a mechanical stirrer, reflux cooler and nitrogen inlet. The molar ratio of tetramethyldisiloxane was set to 6: 1, and 0.02 wt% of KOH catalyst was added thereto, followed by equilibration polymerization at 80 DEG C to 90 DEG C for 24 hours. In order to deactivate the catalyst and to remove unreacted methyltrifluoropropylcyclotrisiloxane, after the reaction was completed, the catalyst was deactivated by standing in a high vacuum at 120 to 30 to 40 torr for 4 hours. Remove roropropylcyclotrisiloxane to prepare alphaomega-aminopropyl terminated poly (methyltripropropylpropylsiloxane),

Meanwhile, 90 ml of a dimethylsulfoxide (DMSO) solvent was introduced while nitrogen gas was introduced into the same reactor as the alpha-omega-aminopropyl terminated poly (methyltrifluoropropylsiloxane) (APMFS). After this, 2.5 g of alpha-omega-aminopropyl-terminated poly ((methyltrifluoropropylsiloxane) (APMFS)) and 6 g of 4,4'oxydianiline (ODA) were completely dissolved at room temperature for 1 hour. . 8 g of 1,2,4,3-benzenetetracarboxylic dianhydride (PMDA) was slowly added thereto and reacted for about 12 hours to prepare a high viscosity poly (amicacid) having a yellowish color. It was added dropwise onto ITO glass, spin coated, and then pre-baked at 70 ° C to 90 ° C for 1 hour under nitrogen atmosphere, and then 150 ° C at a temperature rising rate of 5 ° C per minute. After 200 ° C, 250 ° C, 300 ° C, and 350 ° C, the PSBPI thin film having a thickness of about 1 μm was prepared after an isothermal process for about 30 minutes.

Description

Preparation Method of Poly (organofluorosiloxane) -block-Polyimide Copolymer for the Application to Low Dielectric Coating Material}

The present invention provides a polyorganofluorinated siloxane compound (alphaomega-aminopropyl-terminated poly (methyltripropropylpropyl siloxane)) which has excellent water repellency and thermal stability as fluorine is introduced into a silicon molecule. The present invention relates to a method for producing a silicon fluoride-modified polyimide exhibiting a low dielectric constant value designed to be introduced into a polyimide and to be applied as an electrical / electronic coating material.

In general, polyimide compounds have many advantages such as excellent thermal stability, mechanical properties, and electrical properties, but have the disadvantage of deteriorating electrical properties due to moisture when exposed to the air for a long time due to the vulnerability to moisture. Due to low solubility in solvents and processing difficulties due to high glass transition temperature, many applications are limited to the actual industry. Most of the silicon compound having both organic and inorganic properties are polydimethylsiloxane compounds, which have the characteristics of covalent and ionic bonds at the same time. Therefore, the thermal stability, hydrophobicity, gas permeability and resistance to ozone are superior to general polymers. It has the advantage of easy processing because it has excellent melting characteristics and low glass transition temperature, while the price is expensive and has the disadvantage of low economic efficiency. In the case of fluorine compounds, lubrication, hydrophobicity, flame retardancy, heat resistance, weather resistance, and electrical insulation are known to be excellent.However, fluorinated silicon fluoride modified polyimide obtained by introducing these into polysiloxane is reacted with diacid anhydride. The method of use as a material is not well known.

Recently, U.S. Patent Nos. 4,395,527, 4,670,497, 5,209,981 and 5,317,049 have been described for the preparation of insulating thin films having low dielectric constants by copolymerizing polydimethylsiloxane and polyimide and applying them as organic insulating thin films for semiconductors and electrical and electronic materials. The use of polyimide in them is described in J. Adhes., (Vol. 30, No. 185, 1989). However, in general, polyimide is known to have a relatively high dielectric constant value of about 3.0-3.5 and polydimethylsiloxane modified polyimide copolymer prepared by modifying polydimethyloxane in polyimide. The constant value is 3.2-2.8, which is far below the 2.5-2.0 dielectric constant that is expected to be suitable for application as an insulating coating material in the semiconductor and electric and electronic industries. On the other hand, examples of fluorine-containing polyimides having another form in which polysiloxane is not directly introduced into polyimide are J, Polymer (No. 33, No. 1078, 1992). Fluorine was introduced into polyimide to be used as a coating material for fluoride, but in the case of the fluorine-containing polyimide thus prepared, fluorine was directly added to a monomer such as diamine or diamine such as 2,2-bis (3,4dicarboxyphenyl) hexafluoropropane dianhydride (6FDA) The use of the introduced product is not only economical due to the high cost of these organic monomers, but also a preliminary step of sublimation and purification as a pre-reaction step in order to make them high molecular weight. Their applicability has been very limited.

Therefore, as in the present invention, the fluorine-modified siloxane compound having a very high yield during manufacture and purification is introduced directly into the polyimide main chain, so that the dielectric constant is lower than that of the conventional polyimide material, despite the low content of the fluorine-modified siloxane compound Attempts have not yet been made to economically produce constant value thin film and silicon fluoride modified polyimides.

It is an object of the present invention to provide a method for producing a fluorinated siloxane modified polyimide having improved water repellency, insulation properties, and economy.

Methyltrifluoropropylcyclotrisiloxane and 1,3-bis-3-aminopropyl- (1,1,3,3 while introducing nitrogen gas into a four-necked flask equipped with a mechanical stirrer, reflux cooler and nitrogen inlet. The molar ratio of tetramethyldisiloxane was adjusted appropriately and KOH catalyst was added thereto and equilibrated for 24 hours at 80 ° C to 90 ° C. After completion of the reaction, deactivation of the catalyst and unreacted methyltrifluoropropylcyclotrisiloxane were prepared to prepare alphaomega-aminopropyl terminated poly (methyltripropropylpropylsiloxane),

On the other hand, while injecting nitrogen gas into the same reactor as the alpha-omega-aminopropyl-terminated poly (methyltrifluoropropylsiloxane) (APMFS)), dimethylsulfoxide (DMSO) solvent is added after Here, 2.5 g of alphaomega-aminopropyl-terminated poly (methyltrifluoropropylsiloxane) (APMFS) and 4,4'oxydianiline (ODA) are completely dissolved at room temperature, and 1,2,4 , 3-benzenetetracarboxylic dianhydride (PMDA) was slowly added and reacted to prepare a yellowish high viscosity poly (amicacid), which was added dropwise onto ITO glass and rotated. After coating (coating) and pre-baking at 70 ℃ ~ 90 ℃ under nitrogen atmosphere and then the temperature rising rate to 150 ℃, 200 ℃, 250 ℃, 300 ℃, 350 ℃ step by step After isothermal process, A PSBPI thin film having a thickness of about 1 μm was prepared.

(Example)

For example, the following examples will be described in detail. However, of course, this embodiment does not limit the scope of the present application.

Example 1

Preparation of Alpha Omega-Aminopropyl Terminated Poly (Methyltrifluoropropylsiloxane) [α, ω-aminopropyl terminated poly (methyltrifluoropropylsiloxane, (APMFS))]

Methyltrifluoropropylcyclotrisiloxane and 1,3-bis-3-iminopropyl- (1,1,3, injecting nitrogen gas into a four-necked flask equipped with a mechanical stirrer, a reflux cooler, and a nitrogen inlet. The molar ratio of 3-tetramethyldisiloxane was set to 6: 1, and 0.02 wt% of each KOH catalyst was added thereto, followed by equilibration polymerization at 90 DEG C for 24 hours. In order to deactivate the catalyst and to remove unreacted methyltrifluoropropylcyclotrisiloxane after completion of the reaction, the catalyst was deactivated by being left at 120 to 30 to 40 torr under high vacuum for 4 hours to deactivate the unreacted methyl triple. Loropropylcyclotrisiloxane was removed to prepare alphaomega-aminopropyl terminated poly (methyltripropropylpropylsiloxane). (Yield 85%). FT-IR was measured to confirm the structure of the prepared alpha-omega-aminopropyl-terminated poly (methyltripropropylpropyl siloxane), resulting from primary amine at 3360 cm-1. The absorption peak is newly confirmed.

Polyorganofluorosiloxane-block-polyimide copolymer [Poly

Preparation of Coating Thin Film of (organofluorosiloxane) -block-Polyimide Copolymer, (PSBPI)

Nitrogen gas was introduced into the same reactor as Alpha Omega-Aminopropyl Terminated Poly (methyltrifluoropropylsiloxane) (APMFS)) and 90 mL of dimethylsulfoxide (DMSO) solvent was added thereto. Here, 2.5 g of alphaomega-aminopropyl-terminated poly (methyltrifluoropropylsiloxane) (APMFS) and 6 g of 4,4'oxydianiline (ODA) were completely dissolved at room temperature for 1 hour. 8 g of 1,2,4,3-benzenetetracarboxylic dianhydride (PMDA) was slowly added thereto and reacted for about 12 hours to prepare a high viscosity polyamic acid (poly (amicacid)) having a yellow color. (Yield 98%). This was added dropwise onto ITO glass, spin coated, and then pre-baked at 70 ° C. to 90 ° C. for 1 hour under nitrogen atmosphere. After gradually raising the temperature to ℃, 200 ℃, 250 ℃, 300 ℃, 350 ℃ about 30 minutes isothermal process to prepare a PSBPI thin film having a thickness of about 1 ㎛ coating film. FT-IR was measured to confirm the structure of the fabricated PSBPI. As a result, the absorption peak due to symmetric stretching vibration of C = O group of imide ring at 1778cm-1 was absorbed due to unymmetric stretching vibration at 1728cm-1. As for the peak, the absorption peak resulting from the bending vibration of an imide ring at 723 cm <-1>, and the absorption peak resulting from the stretching vibration of CN of an imide ring at 1370 cm <-1> were confirmed, respectively.

<Test method>

<Method of measuring dielectric constant>

Polyorganofluorosiloxane-Block-Polyimide Copolymer (Poly

The dielectric constant of (organofluorosiloxane) -block-polyimide copolymer (PSBPI) was measured using an impedance analyzer. Aluminum was vacuum-deposited to 5 mm in diameter on ITO glass, and then PSBPI was spin-coated to prepare a cross-linked coating thin film through an imidation reaction. After re-vacuum-depositing aluminum on the coated surface, an electrode was added thereto, and the dielectric constant value was calculated using 1 MHz (1 MHz), and the average value was obtained by performing 10 consecutive measurements.

<Water repellent property>

Polyorganofluorosiloxane-Block-Polyimide Copolymer (Poly

The contact angle of (organofluorosiloxane) -block-polyimide copolymer (PSBPI) was measured using a dynamic contact angle meter at room temperature of 25 ° C. For the solution, 6 µl of deionized distilled water and 6 µl of ethylene glycol were added dropwise to the sample surface in the form of sessile drop, and the contact angle was measured through a monitor where the interface between the sample surface and the solution was enlarged. The average value was taken.

One of the most important physical properties of semiconductor and electrical and electronic insulating materials is low dielectric constant. Pure polyimide produced only with organic monomer has a dielectric constant value of about 3.0-3.5 and polydimethylsiloxane modified polyimide copolymer is about While showing a dielectric constant value of about 3.1-2.8, the polyorganofluorosiloxane-block-polyimide copolymer prepared in the present invention (poly (organofluorosiloxane) -block-polyimide copolymer)

, (PSBPI)) is about 2.3 at 1 megahertz (1 MHz) and shows a very low dielectric constant value compared to conventional polyimide insulating materials, and polydimethyl modified with general polyimide and polydimethylsiloxane. The contact angle of the siloxane modified polyimide was about 60 to 70 ° and about 90 to 100 °, while the polyorganofluorosiloxane-block-polyimide prepared in the present invention was used. In the case of copolymer, (PSBPI), the contact angle of about 120 ° was shown, indicating that the water-repellent properties were very good. From these results, the product has excellent performance that can be used as an insulating material in the semiconductor and electric and electronic industries.

Claims (1)

The molar ratio of methyltrifluoropropylcyclotrisiloxane and 1,3-bis-3-aminopropyl- (1,1,3,3-tetramethyldisiloxane) in the presence of nitrogen gas is controlled in an appropriate manner, and thus the KOH catalyst And equilibration polymerization at 80 ° C to 90 ° C, deactivation of the catalyst after completion of the reaction, and removal of unreacted methyltrifluoropropylcyclotrisiloxane, followed by alphaomega-aminopropyl terminated poly (methyltripro Propylsiloxane), After adding a dimethylsulfooxide solvent in the presence of nitrogen gas, alphaomega-aminopropyl-terminated poly (methyltrifluoropropylsiloxane) and 4,4'oxydianiline are dissolved at room temperature. Yellow, high viscosity polyamic acid by slowly adding and reacting 1,2,4,3-benzenetetracarboxylic dianhydride After preparing (poly (amicacid)), it is added dropwise onto ITO glass, spin-coated, and then prebaked at 70 ° C. to 90 ° C. under nitrogen atmosphere, and then isothermally heated. Method of producing a silicon fluoride-modified polyimide copolymer used as a low dielectric thin film coating material, characterized in that the step of producing a PSBPI thin film after the process.