KR20110109483A - Organic-inorganic hybrid having low coefficients of thermal expansion and method for making the same - Google Patents

Abstract

The present invention comprises the steps of dissolving the core-shell type silica and metal oxide in a solvent to prepare a silica-metal oxide solution; Reacting by adding a poly (amic acid) solution to the silica-metal oxide solution; And heating the obtained solution; and relates to a method for producing an organic-inorganic hybrid and to such an organic-inorganic hybrid, the organic-inorganic hybrid is inorganic particles are uniformly dispersed, the size can be controlled Excellent thermal properties

Description

Organic-Inorganic Hybrid Having Low Coefficients of Thermal Expansion and Method for Making the Same

The present invention relates to organic-inorganic hybrids.

Recently, organic-inorganic hybrids obtained by complexing organic and inorganic components with nanoscale have been noted as new composite materials, and various hybrids have been researched and developed in various fields.

As a method for synthesizing such organic-inorganic hybrids, there are a method of inserting a polymer between layers of an inorganic layer compound such as a clay compound and a sol-gel hybrid method. Among them, the sol-gel method is easy to control and complex the tissue, and relatively simple to control the optical and mechanical properties of the product. In recent years, various organic-inorganic hybrid materials using the sol-gel method have emerged, and various inorganic properties, such as hardness and heat resistance, which are not obtained by the polymer alone can be imparted to the polymer material. Moreover, utilization as a functional material is also examined from various viewpoints. For example, applications are being investigated in a wide range of fields such as low dielectric constant insulating films, optical thin films, sensors, and biomaterials.

Attempts have been made to introduce thermally stable inorganic materials (silica, metal oxides) into the polyimide resin by the sol-gel method, but silica precursors are limited to commercially available products such as some kinds of tetraethoxysilane, tetramethoxysilane, etc. Since it has been used in a limited way, it is impossible to produce a more versatile and highly functional hybrid material. In addition, this method is not easy to control the degree of dispersion because the inorganic particles are physically dispersed in the resin. When using the sol-gel method, there is a problem in that the inorganic particles grow on the PI matrix due to the excess water, thereby deteriorating the physical properties. And to manufacture nano polyimide Only one inorganic particle has been used, and the effect of improving physical properties was not great.

Therefore, efforts have been made to solve such problems in the technical field related to the present invention, and the present invention has been devised under such a technical background.

The present invention for the purpose of providing an organic-inorganic hybrid manufacturing method of excellent physical properties

do.

The method for preparing an organic-inorganic hybrid of the present invention comprises the steps of preparing a silica-metal oxide solution by dissolving a core-shell silica and a metal oxide in a solvent (S1); Reacting by adding a poly (amic acid) solution to the silica-metal oxide solution (S2); And (S3) heating the solution obtained from the step (S2).

Such core-shell type silica preferably has an amino group. As the metal oxide, magnesium oxide, calcium oxide, scandium oxide, barium oxide, titanium dioxide, zirconium dioxide and the like can be used. In addition, as the solvent in which the core-shell silica and the metal oxide are dissolved, THF, CH ₂ Cl _2, and NMP may be used.

In addition, the organic-inorganic hybrid of the present invention consists of a polyimide resin containing core-shell type silica and a metal oxide. Such core-shell type silica preferably has an amino group or a carboxyl group. As the metal oxide, magnesium oxide, calcium oxide, scandium oxide, barium oxide, titanium dioxide, zirconium dioxide and the like can be used.

The organic-inorganic hybrid according to the manufacturing method of the present invention is excellent in thermal properties because the inorganic particles are uniformly dispersed, the size can be controlled.

1 is a chemical structure of core-shell type silica.
2 is a TEM photograph of a silica / metal oxide polyimide film according to Example 3. FIG.

Hereinafter, the present invention will be described in detail. The terms or words used in this specification and claims are not to be construed as limiting in their usual or dictionary meanings, and the inventors may appropriately define the concept of terms in order to best explain their invention in the best way possible. It should be interpreted as meaning and concept corresponding to the technical idea of the present invention based on the principle that the present invention.

The present invention relates to a method for producing an organic-inorganic hybrid consisting of a polyimide resin comprising a core-shell type silica and a metal oxide.

First, a silica-metal oxide solution is prepared by dissolving a core-shell silica and a metal oxide in a solvent (step S1).

Core-shell type silica is silica of the chemical structure shown in FIG. 1. Such core-shell type silicas have functional groups capable of reacting with the polyamic acid backbone. As a functional group of the said core-shell type silica, It is preferable that it is an amino group or a carboxyl group. In addition, the core-shell type silica may be used having a size of 1 to 3 nm. The metal oxide used at this time is not particularly limited but may be magnesium oxide, calcium oxide, scandium oxide, barium oxide, titanium dioxide and zirconium dioxide.

These core-shell type silicas and metal oxides are dissolved in a solvent and can be used in a solvent such as THF, CH ₂ Cl ₂ or NMP. In this case, in order to uniformly mix the core-shell silica and the metal oxide in the solvent, ultrasonication may be used.

Subsequently, a poly (amic acid) solution is added to the silica-metal oxide solution and reacted (step S2).

The poly (amic acid) solution includes a solvent such as N-Methyl-2-Pyrrolidone (NMP). The poly (amic acid) solution is added to the silica-metal oxide solution and reacted at room temperature.

Then, the obtained solution is heated to prepare an organic-inorganic hybrid (step S3).

The obtained solution is heated and thermoset to prepare an organic-inorganic hybrid. At this time, the heating temperature is heated to a constant temperature interval from about 100 ℃ to about 300 ℃ at about 30 minutes intervals to heat curing the obtained solution.

As described above, the organic-inorganic hybrid is composed of a polyimide resin including core-shell type silica and a metal oxide. In order to improve the physical properties, the inorganic particles to be used should be uniformly dispersed in the polymer to nanoparticle size, the organic-inorganic hybrid of the present invention is excellent in thermal properties because the inorganic particles are uniformly dispersed, the size can be controlled. In particular, the inorganic particles are preferably 100 nm or less.

Hereinafter, the present invention will be described in detail with reference to Examples. However, embodiments according to the present invention can be modified in many different forms, the scope of the present invention should not be construed as limited to the embodiments described below. The embodiments of the present invention are provided to more completely explain the present invention to those skilled in the art.

Example

Example 1-5. Silica-Magnesium Oxide / Polyimide Film Preparation

Each Example 1-5 according to the content ratio of Table 1, 1 to 3 nm core-shell type silica having magnesium oxide and amino groups of about 30 nm size modified with a silane coupling agent (core-shell type) A solution of silica) dissolved in THF was mixed and sonicated to prepare a silica-metal oxide solution. Polyamic acid solution (15% by weight, NMP) was added thereto, followed by reaction at room temperature for 2 hours. Thereafter, thermosetting was performed for 1 hour at 100 ° C., 1 hour at 150 ° C., 1 hour at 200 ° C., and 1 hour at 250 ° C. to prepare a silica-metal oxide / polyimide hybrid film. The temperature rise time of each step at the time of thermosetting was 30 minutes.

In Examples 4 and 5 in which the amount of magnesium oxide added was 10% by weight or more, an opaque film was formed after thermosetting, and in Examples 1-3 in which the inorganic material content was less than 10% by weight, a transparent film was produced. .

Magnesium oxide
(weight%) Core-shell silica
(weight%) Glass transition temperature (Tg)
(℃) Coefficient of thermal expansion (CTE)
(mm / m ℃) Example 1 One One 268 90 Example 2 3 3 285 56 Example 3 5 5 301 28 Example 4 10 10 290 38 Example 5 15 15 289 40

Comparative Example 1. Manufacture of Polyimide Film

Using a polyamic acid solution (15% by weight, NMP), a precursor of polyimide, thermal curing was performed for 1 hour at 100 ° C, 1 hour at 150 ° C, 1 hour at 200 ° C, and 1 hour at 250 ° C. The mid hybrid film was prepared. The temperature rise time of each step at the time of thermosetting was 30 minutes.

Comparative Example 2. Preparation of Silica / Polyimide Film

A polyamic acid solution (15% by weight, NMP) was added to a solution in which 1-3 nm of core-shell type silica (10% by weight) having an amino group was dissolved in THF, followed by reaction at room temperature for 2 hours. Silica / polyimide hybrid film was prepared by thermosetting in an electric furnace for 1 hour at 100 ° C, 1 hour at 150 ° C, 1 hour at 200 ° C, and 1 hour at 250 ° C. The temperature rise time of each step at the time of thermosetting was 30 minutes.

Comparative Example 3: Magnesium Oxide / Polyimide Film Preparation

A polyamic acid solution (15 wt%, NMP) was added to a metal oxide (10 wt%) of about 30 nm in size modified with a silane coupling agent, and reacted at room temperature for 2 hours. 1 hour at 100 ℃, 1 hour at 150 ℃, 1 hour at 200 ℃, and 1 hour at 250 ℃ in an electric furnace to prepare a metal oxide / polyimide hybrid film. The temperature rise time for each step of thermosetting is 30 minutes.

Magnesium oxide
(weight%) Silica
(weight%) Glass transition temperature (Tg)
(℃) Coefficient of thermal expansion (CTE)
(mm / m ℃) Comparative Example 1 0 0 265 105 Comparative Example 2 0 10 278 82 Comparative Example 3 10 0 280 90

Test example. Measurement of glass transition temperature and coefficient of thermal expansion

Using a differential scanning calorymeter (DSC), the glass transition temperatures of the polyimide films prepared in Examples 1-5 and Comparative Examples 1-3 were measured and shown in Tables 1 and 2. In addition, the coefficient of thermal expansion of the polyimide film prepared in Examples 1-5 and Comparative Examples 1-3 was measured using a coefficient of thermal expansion (Dilatometer), and shown in Table 1 and Table 2.

The glass transition temperature (Tg) and the coefficient of thermal expansion (CTE) of the silica / magnesium oxide polyimide hybrid film of Example 1-5 obtained from Table 1 were compared with the polyimide resin of Comparative Example 1, and the glass transition temperature (Tg) Was increased and the coefficient of thermal expansion decreased. In the case of Example 3, when the content of the inorganic particles (silica / magnesium oxide) is 10% by weight, the best physical properties were achieved. This is because the inorganic particles are uniformly dispersed in nano size in the polyimide resin as shown in FIG. 2.

In addition, in the case of Example 4-5 having an inorganic particle content of 20% by weight or more, the particles in the polyamide resin became opaque due to the increase in the micron size. It was confirmed that the relative lower than.

On the other hand, in the case of Comparative Example 2-3, which is an organic-inorganic polyimide hybrid film obtained from Table 2, the values of the glass transition temperature (Tg) and the coefficient of thermal expansion (CTE) are thermally compared with those of Comparative Example 1, which is pure polyimide. The characteristic synergistic effect was not large. In the case where silica and metal oxide are used together, the inorganic particles are dispersed in the resin at a nano size when the amount of the inorganic particles is 10% by weight, whereas the size of the micron in Comparative Example 3 is used when the metal oxide is used alone. This is because the particles are dispersed above. In addition, in Comparative Example 2, in which silica is used alone, the reactivity of the amino groups surrounding the silica and the carboxylic acid in the polyamic acid, which is a precursor of the polyimide, is lowered, so that less silica is loaded than expected, thereby improving thermal characteristics. The effect was not good.

Claims (9)

(S1) preparing a silica-metal oxide solution by dissolving the core-shell type silica and the metal oxide in a solvent;
(S2) reacting by adding a poly (amic acid) solution to the silica-metal oxide solution; And
(S3) heating the solution obtained from (S2);
Organic-inorganic hybrid manufacturing method comprising a. The method of claim 1,
The core-shell type silica is an organic-inorganic hybrid production method characterized in that it has an amino group or a carboxyl group. The method of claim 1,
The core-shell type silica is a method for producing an organic-inorganic hybrid, characterized in that 1 to 3 nm in size. The method of claim 1,
The metal oxide is a method of producing an organic-inorganic hybrid, characterized in that the compound or a mixture of two or more selected from magnesium oxide, calcium oxide, scandinanium oxide, barium oxide, titanium dioxide and zirconium dioxide. The method of claim 1,
The solvent of the step (S1) A method for producing an organic-inorganic hybrid, characterized in that the compound or two or more selected from THF, CH ₂ Cl ₂ and NMP. An organic-inorganic hybrid consisting of a polyimide resin comprising a core-shell type silica and a metal oxide. The method of claim 6,
The core-shell type silica is an organic-inorganic hybrid, characterized in that 1 to 3 nm in size. The method of claim 6,
The core-shell type silica is an organic-inorganic hybrid, characterized in that it has an amino group or a carboxyl group. The method of claim 6,
The metal oxide is an organic-inorganic hybrid, characterized in that one compound selected from magnesium oxide, calcium oxide, scandium oxide, barium oxide, titanium dioxide and zirconium dioxide, or a mixture of two or more thereof.

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