KR101335958B1 - Polymer resin composition having high thermal stability and low outgassing rate, prepreg comprising the composition, and carbon fiber-polymer composite laminating the prepreg - Google Patents

Abstract

The present invention relates to a polymer resin composition with cyanate ester resin and a curing catalyst, prepreg in which the polymer resin composition is impregnated into carbon fibers, and a carbon fiber-polymer composite with laminated prepreg. According to one embodiment of the present invention, the polymer-carbon fiber composite has improved heat resistance with a gas release rate of less than 1% at high temperature and high vacuum state using the cyanate ester resin and the cobalt catalyst and thermal decomposition temperature of 300 deg. C or higher and can be widely applied to electricity, electronics, semiconductor materials, and aerospace fields.

Description

A polymer resin composition having high heat resistance and low gas release rate, a prepreg impregnated with the composition, and a carbon fiber-polymer composite material having the prepreg laminated thereon, and a polymer composition having high thermal stability and low outgassing rate, prepreg comprising the composition, and carbon fiber-polymer composite laminating the prepreg}

The present invention relates to a polymer resin composition used as a matrix resin for a carbon fiber-polymer composite material, a prepreg in which the composition is impregnated in carbon fiber, and a carbon fiber-polymer composite material in which the prepreg is laminated.

Fiber-reinforced plastics (FRP) is a composite material that is cured by mixing fibers and thermosetting resins. It is a material different from conventional synthetic resin products.

FRP composites are excellent in corrosion resistance, resistant to corrosion of acids, alkalis, salts, solvents, etc., and are semi-permanent materials with lighter weight than aluminum and higher strength than iron. It is widely used in almost all industrial processes not only in the industry but also in the 21st century high-tech industry.

The excellent physical properties of FRP composites include light weight, excellent stiffness, low thermal strain and electrical insulation. In particular, the specific gravity is about 1/5 the level of iron, about 1.4-1.8, so the specific strength is higher than that of iron, making it easier to manufacture, install, and transport large metals. In addition to corrosion resistance, there is no ion elution, and thermal conductivity is 1/180 of iron, so it is excellent in thermal insulation, making it the most suitable material for storage tanks and water leisure goods. In addition, it is suitable for encapsulation of electrical junction terminals because of its excellent electrical insulation. EMC (epoxy molding compound), which is used as an encapsulant for semiconductor chips, is also possible due to insulation and low thermal strain.

In addition to superior use properties, FRP composite materials can be freely designed and molded for various shapes, and are suitable for making extra large equipment that is difficult to transport by field construction. In addition, it is easy to mix and use with other materials such as steel plate, wood, and concrete because it has strong adhesiveness, and it is possible to manufacture it integrally, so it reduces the parts used at the joint area, ensuring lightweight appearance and neat shape.

Among them, the carbon fiber-polymer matrix composite is light, has excellent elastic modulus and strength, and has a low coefficient of thermal expansion. It has been widely used throughout the industry, such as wind turbines, wind blades and pressure vessels.

Recently, it is expanding its application range to advanced aerospace materials such as aircraft fuselage, main wings, tail wings and satellite platforms and payloads, solar panels, antennas, optical platforms and cryogenic tanks.

Epoxy resin, which is a curable polymer used as a polymer matrix in a carbon fiber composite material, is widely used to reach approximately 80% of the polymer matrix resin. The epoxy resin has the advantages of very small shrinkage during curing reaction, no volatiles, high storage stability after curing, excellent electrical / mechanical properties, excellent chemical resistance and abrasion resistance, and can be used in various industrial fields. .

However, epoxy resins are difficult to use in some fields that require high functionality because of poor water resistance, low temperature resistance, and low operating temperatures at high temperatures. In addition, the outgassing rate (high outgassing rate) is not possible to use in a vacuum condition has been used only for general purposes, such as fishing rods, golf clubs, arrows.

On the other hand, one of the important factors to be considered in the materials for the electrical, electronics, semiconductor industry and aerospace industry is the outgassing characteristics. Outgassing from materials and components becomes a problem in process conditions where high vacuum conditions and constant vacuum conditions are important, which can have a significant impact on product performance and can lead to unpredictable problems in process systems.

For example, in the case of a display panel, when a large amount of gas is emitted from a component material of a device or a product during a manufacturing process, and the vacuum degree is lowered, the display panel affects not only the sharpness of the display panel but also the color of the panel.

In addition, gas emission characteristics are an important issue in aerospace materials to be used in space. In the case of satellite materials, the space is in a high vacuum, so there is always a gas release unlike on the ground, especially when the sun's surface is heated and the emitted gas is adsorbed on the cold side of the shade, which can affect the internal microcircuits. .

In addition, the physical properties required for the evaporator frame used in OLED production are low thermal expansion rate, low outgassing characteristics, and high mechanical rigidity. The mask frame is made of fiber-reinforced polymer composites. In the 5.5 generation, it is expected to be about 317 kg to 70 kg lighter than the metal material, increasing work convenience and supplying the unit price below 50%.

At present, the industrial level of Korea is active in the electric, electronic, and semiconductor industries, but the parts requiring the vacuum or the parts and materials that need to be kept clean still consist of expensive heavy metal products.

Therefore, it is impossible to use conventional epoxy resin only for use in special component materials for aerospace and electronics industries requiring high-performance advanced materials, and matrices having higher water resistance and heat resistance than conventional epoxy resins for development of composite materials that can replace them. The need for resin development is emerging.

The present invention can be used in carbon fiber-polymer composite materials having excellent heat resistance and outgassing properties while maintaining mechanical strength to be used in various materials for electronic, semiconductor and aerospace industries used at high temperature and high vacuum conditions. The purpose is to provide a polymer resin composition.

Another object of the present invention is to provide a prepreg prepared by impregnating the polymer resin composition into carbon fibers.

Moreover, an object of this invention is to provide the composite material which laminated | stacked the said prepreg.

The polymer resin composition used in the polymer matrix according to an embodiment of the present invention for achieving the above object is characterized in that it comprises a cyanate ester resin (cyanate ester resin) and a curing catalyst.

It is preferable that the said cyanate ester resin is a phenol novolak-type or bisphenol-type resin.

The curing catalyst is preferably one or more selected from the group consisting of cobalt (III) acetylacetonate, copper acetylacetonate, manganese acetylacetonate, and zinc acetylacetonate.

The curing catalyst may be included in 1 ~ 200ppm relative to the cyanate ester resin.

According to one embodiment of the present invention, the polymer resin composition may be included in the cyanate ester resin by mixing an epoxy resin within 80% by weight.

The resin composition was heated to 2.5 ℃ / min to room temperature ~ 150 ℃ and then the first curing at 150 ℃ for 0.5 ~ 2 hr, the temperature was raised to 2.5 ℃ / min to 150 ~ 180 ℃ and then at 180 ℃ for 2 ~ 4 hr The second hardening may be performed at a temperature of 2.5 ° C./min to 180 ° C. to 250 ° C., and then hardened at 250 ° C. through a third hr third curing process.

According to an embodiment of the present invention, the polymer resin composition may have a total mass loss (TML, total mass loss) measured by Equation 1 at 125 ° C. and high vacuum to less than 1%:

Equation  One

In the above formula, M is the sample mass before the outgassing test, and M _f is the sample mass after the outgassing test.

In addition, according to an embodiment of the present invention, the polymer resin composition may have a high heat resistance of 300 ℃ or more glass transition temperature.

The present invention can also provide a prepreg in which the polymer resin composition is impregnated into carbon fibers.

The carbon fiber may be selected from a unidirectional (UD) type and a fabric form.

The content of the resin composition impregnated in the carbon fiber may be 30 to 70% by weight.

In addition, the present invention can provide a polymer-carbon fiber composite material in which the prepreg is laminated.

According to an embodiment of the present invention, using a cyanate ester resin and a cobalt-based catalyst, the gas release rate (% TML) at high temperature and high vacuum is less than 1%, and the pyrolysis temperature is 300 ° C. or more, thereby having excellent heat resistance. -Can be used as polymer matrix of polymer matrix composites.

Therefore, the prepreg prepared by impregnating the polymer matrix with carbon fiber, and the polymer-carbon fiber composite material prepared by laminating the polymer matrix have an effect that can be widely applied to electric, electronic, semiconductor component materials and aerospace fields.

1 shows a curing process according to the invention,
2 is an FT-IR measurement result confirming the curing reaction of the cyanate ester resin,
3 is a DSC measurement result of the cured cyanate ester resin cured product of the present invention and the cyanate resin of Comparative Example 1,
4 is a TGA analysis result of the cyanate ester resin cured product of the present invention, the epoxy resin of Comparative Example 2, and the hybrid resin of Example 2,
5 is a composite material prepared according to Example 4 of the present invention, which shows (a) UD plate shape, (b) woven plate shape # 1, and (c) woven plate shape # 2.

Hereinafter, the present invention will be described in more detail.

The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the singular forms "a,""an," and "the" include singular forms unless the context clearly dictates otherwise. Also, " comprise "and / or" comprising "when used herein should be interpreted as specifying the presence of stated shapes, numbers, steps, operations, elements, elements, and / And does not preclude the presence or addition of one or more other features, integers, operations, elements, elements, and / or groups.

The present invention relates to a polymer resin composition used for the polymer matrix of a composite material of a carbon fiber-polymer matrix, a prepreg impregnated with carbon fiber, and a carbon fiber-polymer composite material in which the prepreg is laminated. It is about.

First, the polymer resin composition used as the polymer matrix includes a cyanate ester resin and a curing catalyst.

It is preferable that the said cyanate ester resin is a phenol novolak-type or bisphenol-type resin. The phenol novolac-based cyanate ester resin may be represented by the following Formula 1:

Formula 1

The cyanate ester resin has a high glass transition temperature, and thus has excellent heat resistance, low dielectric loss, excellent processing characteristics, and low water absorption, so that it is suitable for electronic component materials, high temperature adhesives, and structural aerospace materials. Known as In addition, it is known to be excellent in flame retardancy, less toxic smoke generation and less toxicity. In addition, it has a low thermal expansion, as well as the handling and processing convenience corresponding to the epoxy resin used in the conventional polymer matrix.

Accordingly, in the present invention, by using a cyanate ester resin having excellent physical properties as described above by replacing the conventional epoxy resin, various problems of the epoxy resin may be solved, thereby providing a composite material having excellent heat resistance and gas release characteristics.

In addition, the polymer resin composition according to an embodiment of the present invention may be used by using a polymer resin composition including the cyanate ester resin and a curing catalyst or by mixing an epoxy resin within 80% by weight of the composition. When the content of the epoxy resin to be mixed exceeds 80% by weight is not preferable because the increase in heat resistance and decrease in gas release rate is not obvious.

The curing catalyst included in the resin composition of the present invention is at least one selected from the group consisting of cobalt (III) acetylacetonate, copper acetylacetonate, manganese acetylacetonate, and zinc acetylacetonate, wherein the curing catalysts are coordinate complex structures in which octate ligands are bound. It is those that have. Among these, the cobalt (III) acetylacetonate which exists in solid powder form can be used most preferably.

The curing catalyst may be included in 1 ~ 200ppm, preferably 50 ~ 150ppm with respect to the cyanate ester resin. When the content of the curing catalyst has the above range, it is possible to optimize the curing reaction, has the effect of maintaining the overall physical properties such as storage modulus and impact resistance of the final cured product.

In the present invention, in the curing by adding the curing catalyst to the cyanate ester resin, in order to complete the curing reaction sufficiently to obtain a cured product with improved heat resistance such as T _g it is preferable to go through the following step curing process Do.

First step is to heat the resin composition at room temperature ~ 150 ℃ to 2.5 ℃ / min and then the first curing for 0.5 ~ 2 hr at 150 ℃. In the second step, the temperature is increased to 2.5 ° C./min to 150 ° C. to 180 ° C., and the second curing is performed at 180 ° C. for 2 to 4 hr. In addition, the temperature is finally increased to 2.5 ° C./min to 180 ° C. to 250 ° C., and the third curing is performed at 250 ° C. for 1 to 3 hr.

If the curing process of the resin composition according to the present invention does not go through the above stepwise process or out of the temperature raising condition and curing time, there is a problem that the curing time is too long or the curing reaction does not occur, Even if it occurs, problems such as damage to the surface of the specimen due to rapid heat generation such as wrinkles formed on the surface of the cured specimen are not preferable.

By passing through the curing process as described above, the polymer resin composition according to an embodiment of the present invention has an effect of having a high heat resistance of 300 ° C or higher, preferably 350 ° C or higher.

In addition, according to one embodiment of the present invention, the polymer resin composition may be a total mass loss (TML, total mass loss) measured by the following Equation 1 at 125 ° C. and high vacuum to less than 1%:

Equation  One

In the above formula, M is the sample mass before the outgassing test, and M _f is the sample mass after the outgassing test.

The gas permeability test is a method specified in ASTM E595 of the United States is suitable for use in aerospace applications by determining the content of degassing components such as solvents, moisture, unreacted substances, materials having a low vaporization temperature, adsorbed or contained on the part surface It is an analysis item to determine. The test condition of vacuum at 125 ° C is used as a simulation of the vacuum environment in space, and NASA in the United States requires a total mass loss (% TML) of less than 1%.

Therefore, when using the polymer resin composition according to the present invention meets the conditions that can be used in space, the composite material using the polymer resin composition of the present invention as a matrix polymer can be variously applied to the aerospace field. Suggest.

In addition, according to an embodiment of the present invention, there is provided a prepreg impregnated with the carbon resin to the polymer resin composition.

Carbon fiber according to the present invention can be used in both unidirectional (UD) type and woven fabric (fabric) type, the unidirectional type and woven carbon fiber has a Young's modulus of 234 GPa, tensile strength 4.4 ~ 4.8 GPa, density 1.77-1.82 g / cm ³ Have similar properties in the range.

The content of the resin composition impregnated in the carbon fiber is preferably 30 to 70% by weight based on 100 parts by weight of the carbon fiber, and when the content of the resin composition is less than 30% by weight, the prepreg and composite material sufficiently impregnated with the resin. It is difficult to manufacture, and when the content exceeds 70% by weight, the resin content is excessive, and there is a problem that a sufficient strength improvement cannot be obtained after the production of the composite material.

The process of impregnating the polymer resin composition into the carbon fiber is not particularly limited. For example, the polymer resin composition which measures the mass per unit area of the carbon fiber, fixes it to a constant support, and then maintains a constant viscosity of carbon It can manufacture by apply | coating enough to a fiber.

In addition, the present invention can provide a polymer-carbon fiber composite material in which the prepreg is laminated.

The composite material is cut to the required size of the prepreg, and then the release paper on a constant support lower plate is laminated by the thickness of the molded article. The number of layers of the prepregs to be laminated is not limited, and may be appropriately adjusted according to the applied product. Next, place the release paper on the upper part of the molded article and place the top plate of the support. When the laminated composite material is cured based on a curing cycle in a compression press or autoclave, the polymer-carbon fiber composite material according to the present invention can be obtained.

Example  1: Preparation of polymer resin composition

To the phenol-novolak-based cyanate ester resin (PT-30, Lonza) represented by the formula (1), a cobalt (III) acetylacetonate (Aldrich) in the form of a solid powder as a curing catalyst was added to the polymer at 50, 100, 200 ppm, A resin composition was prepared. In addition, the curing reaction after the addition of the curing catalyst was carried out according to the process of FIG.

Comparative Example  One : Cyanate  Ester polymer resin

Only pure cyanate ester resin without the curing catalyst was compared with the polymer resin composition of the present invention.

Comparative Example  2: epoxy resin

Compared with the polymer resin composition of this invention using the epoxy resin (resin which fixed amount added the hardening agent with K51) used conventionally as a polymer matrix.

Example  2: with epoxy resin Cyanate  Suzy Blend

Epoxy resin YD-128 (liquid phase) and YD-011 (solid phase) in a weight ratio of 65:35, respectively, and a hybrid resin (hybrid resin) in which the cyanate ester resin composition of the present invention is mixed at 50:50 Hereinafter referred to as HY).

Experimental Example  One : Cyanate  Confirmation of curing reaction of ester resin

It was confirmed by FT-IR whether the curing reaction of the cyanate ester resin proceeded, and the results are shown in FIG. 2.

Next, as shown in Figure 2, it was confirmed by the production peak of the triazine group (triazine group) present in the polycyanurate network (polycyanurate)

Experimental Example  2: check the thermal characteristics

2-1) polymer resin Cured product Tg  Measure

DSC (Pyris 6, Perkin-Elmer) analysis was used to measure the T _g of the cured cyanate resin cured product and the cyanate resin of Comparative Example 1, and the results are shown in FIG. 3. The temperature increase rate was 10 degrees C / min.

Next, as shown in the results of FIG. 3, both the case of Comparative Example 1 without the catalyst and the resin according to the embodiment of the present invention with the addition of 100 ppm of the curing catalyst did not show a distinct thermal transition peak up to 300 ° C.

From these results, it was confirmed in the present invention that the heat resistance of the cyanate ester resin itself is maintained as it is even when the curing catalyst is added.

2-2) polymer resin Cured product TGA  analysis

Thermogravimetric analysis was used with TGA (Netzsch 409) to confirm the thermal stability of the cured cyanate ester resin. It measured by imposing the temperature rising rate of 10 degree-C / min to 20-600 degreeC in nitrogen atmosphere. The thermogravimetry of Comparative Example 2 (epoxy resin) and Reference Example 1 (hybrid resin) were compared together, and the results are shown in FIG. 4, and the thermal decomposition temperature is summarized in Table 1 below.

Resin type Example 1 (cyanate
Ester resin composition) Comparative Example 2
(Epoxy resin) Example 2
(HY resin) Pyrolysis Temperature (℃) * 385 291 353 * The pyrolysis temperature is defined as the temperature at which mass loss occurs by 2%

As shown in Table 1 and the results of FIG. 4, it can be seen that the thermal decomposition temperature of the cyanate ester resin composition of the present invention is about 100 ° C. higher than that of the epoxy resin of Comparative Example 2. That is, when the cyanate ester resin according to the present invention is used as the polymer matrix of the composite material, it can be seen that the heat resistance can be significantly improved compared to the composite material using the conventional epoxy resin as the polymer matrix.

In addition, in the case of the HY resin (Example 2) in which the epoxy resin and the resin composition of the present invention were mixed at 50:50, it can be seen that the thermal decomposition temperature was improved by about 60 ° C. compared with the epoxy. From these results, it can be confirmed that by using only a conventional epoxy resin as a polymer matrix, by using a cyanate ester resin or a mixed resin with an epoxy resin, it is easy from an economical point of view and can secure heat resistance.

Experimental Example  3: gas release characteristics ( outgassing ) analysis

In order to evaluate the gas release characteristics of the cured resin, the mass change was measured using a TML measuring apparatus. This test measured% TML in a vacuum at 125 ° C. according to “Degassing Characteristics by Mass Change Procedure” (T-01-027-2001) according to the method specified in ASTM E595.

% TML was calculated according to the following equation.

The% TML (total mass loss rate) of the cyanate ester resin of the present invention was determined to be 0.289%. This result satisfies less than 1%, which is a requirement of% TML, and it can be seen that the resin composition of the present invention can be applied to various aerospace materials.

Example  3: Carbon fiber Of Cyanate  Ester Prepreg  Produce

In the present invention, the cyanate ester resin composition prepared in Example 1 1) UD prepreg (resin content 36 wt%) impregnated in one direction (UD) carbon fiber (TR50), 2) fabric carbon fiber ( TR30) fabric prepreg # 1 (resin content 40 wt%), 3) fabric prepreg # 2 (resin content 65 wt%) was impregnated in the fabric carbon fiber (TR30).

Example  4 : Carbon fiber / Polymer Composites Manufacturing

Each of three kinds of prepregs prepared in Example 3 was laminated and cured to prepare a plate-shaped composite material, and each specimen is shown in FIG. 5. The size of each plate is 300x300 and the thickness of the prepreg is different. The average thickness of UD plate is 1.98 mm, woven plate # 1 is 1.83 mm, and woven plate # 2 is 2.86 mm. This plate-shaped composite material was used as a specimen for measuring the mechanical properties.

Claims (12)

delete delete delete delete delete A polymer resin composition comprising a cyanate ester resin and a curing catalyst;
After the polymer resin composition is heated to 2.5 ℃ / min up to room temperature ~ 150 ℃ the first curing for 0.5 ~ 2 hours at 150 ℃,
After the temperature was raised to 2.5 ℃ / min to 150 ~ 180 ℃ second curing for 2 to 4 hours at 180 ℃, and
After heating to 2.5 ° C./min to 180 ° C. to 250 ° C., the polymer resin composition undergoes a third curing process at 250 ° C. for 1 to 3 hours.
A polymer resin composition comprising a cyanate ester resin and a curing catalyst;
The polymer resin composition is a polymer resin composition that satisfies less than 1% of the total mass loss (TML, total mass loss) measured by the following equation (1) at 125 ℃, high vacuum.
Equation 1

(Wherein, M is the sample mass before the outgassing test, M _f is the sample mass after the outgassing test.)
A polymer resin composition comprising a cyanate ester resin and a curing catalyst;
The polymer resin composition is a polymer resin composition having a high heat resistance of 300 ℃ or more glass transition temperature.
delete A polymer resin composition comprising a cyanate ester resin and a curing catalyst;
A prepreg impregnated with the polymer resin composition in carbon fiber;
Wherein the carbon fiber is selected from unidirectional (UD) type and fabric form.
A polymer resin composition comprising a cyanate ester resin and a curing catalyst;
A prepreg impregnated with the polymer resin composition in carbon fiber;
The content of the resin composition impregnated in the carbon fiber is 30 to 70% by weight prepreg. delete

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