KR102297987B1 - Composite material sheet comprising polyetherimide blend and glass fiber mat and method of preparing same - Google Patents

Abstract

Disclosed are a composite material sheet comprising a polyetherimide blend and a glass fiber mat, and a method for manufacturing the same. The composite material sheet of the present invention is a glass fiber mat; and a blend impregnated in the glass fiber mat, wherein the blend is polyetherimide (PEI, Poly Ether Imide), polyethylene naphthalate (PEN, Poly Ethylene Naphthalate) and polyethylene terephthalate (PET, Poly Ethylene). terephthalate). Thereby, it is possible to manufacture a composite material sheet with excellent mechanical properties such as high gas barrier properties and tensile strength while maintaining the excellent durability, rigidity and stability at high temperatures of polyetherimide, and reducing manufacturing costs for automobile, aviation, and electronic parts. It can be used as a material in various fields such as

Description

Composite material sheet comprising polyetherimide blend and glass fiber mat and manufacturing method thereof

The present invention relates to a composite material sheet and a method for manufacturing the same, and more particularly, to a four-component organic-inorganic composite material comprising a polyetherimide blend and a glass fiber mat.

Composite materials may include inorganic fibers dispersed in a resin or polymer matrix. These organic-inorganic composite materials can overcome the physical limitations of polymer resins, and are useful in various industrial fields such as aviation and space, automobiles, sports and leisure.

In the early days of the development of composite materials, thermosetting polymer compositions with relatively easy manufacturing and excellent physical properties were mainly used, but recently, thermoplastic polymer resins that are suitable for mass production, can be recycled, can be recycled, and have advantages such as short curing time and light weight. Composites using as a matrix are expanding their use.

Conventionally, poly(ether-imide) (PEI) has been disclosed as an amorphous polymer resin having a high glass transition temperature (215° C.) as a thermoplastic matrix, and having advantages such as excellent durability, rigidity, and stability at high temperature. . However, the polyetherimide has a problem in that it does not have good blocking properties including moisture for maintaining the physical properties of the composite material, is expensive to manufacture, and has poor solvent resistance.

An object of the present invention is to provide a composite material sheet having excellent mechanical properties such as high gas barrier properties and tensile strength while maintaining excellent durability, rigidity and stability at high temperature of polyetherimide, and a method for manufacturing the same.

Another object of the present invention is to provide a composite material sheet that can be used as a material in various engineering fields such as automobiles, aviation, electronic components, and the like by reducing the manufacturing cost of the final composite material, and a method for manufacturing the same.

According to an aspect of the present invention, a glass fiber mat; and a blend impregnated in the glass fiber mat, wherein the blend is polyetherimide (PEI, Poly Ether Imide), polyethylene naphthalate (PEN, Poly Ethylene Naphthalate) and polyethylene terephthalate (PET, Poly Ethylene). Terephthalate) is provided that contains a composite material sheet.

In addition, the composite material sheet includes the blend, and may further include a blend layer formed on one or more surfaces selected from the group consisting of any one surface and the other surface of the composite material sheet.

In addition, the blend may be impregnated into the empty space of the glass fiber sheet.

In addition, the glass fiber mat may be a surface-modified glass fiber mat.

In addition, the surface-modified glass fiber mat is epoxy, acryl, vinyl, methacrylate, amine, chloropropyl mercapto cationic styryl (chloropropyl mercapto cationic styryl) ) and γ-glycidoxypropyl trimethoxy may include one or more organic functional groups selected from the group consisting of (γ-glycidoxypropyl trimethoxy).

In addition, the blend may be crosslinked, and the blend and the glass fiber mat may be crosslinked.

In addition, the crosslinking may be performed by irradiation with an electron beam.

In addition, the glass fiber mat may be in the form of a plain weave.

In addition, the blend may include 10 to 70 parts by weight of the polyethylene naphthalate and polyethylene terephthalate, based on 100 parts by weight of the blend.

According to another aspect of the present invention, (a) for preparing a blend comprising polyetherimide (PEI, Poly Ether Imide), polyethylene naphthalate (PEN, Poly Ethylene Naphthalate) and polyethylene terephthalate (PET, Poly Ethylene Terephthalate) step; and (b) impregnating the blend into a glass fiber mat to prepare a composite material sheet.

In addition, the blend may include 10 to 70 parts by weight of the polyethylene naphthalate and polyethylene terephthalate, based on 100 parts by weight of the blend.

In addition, the glass fiber mat may be a surface-modified glass fiber mat.

In addition, the surface-modified glass fiber mat is acrylic (acryl), vinyl (vinyl), methacrylate, amine (amine), epoxy (epoxy), chloropropyl mercapto cationic styryl (chloropropyl mercapto cationic styryl) ) and γ-glycidoxypropyl trimethoxy may include one or more organic functional groups selected from the group consisting of (γ-glycidoxypropyl trimethoxy).

In addition, the step (b) may be performed for 1 to 20 minutes at a temperature of 100 to 600 ℃ and a pressure of 0.1 to 5.0 MPa.

In addition, the manufacturing method of the composite material sheet after the step (b), (c) irradiating an electron beam (electron beam) to the manufactured composite material sheet; may further include.

In addition, the irradiation of the electron beam may crosslink the blend and crosslink the blend and the glass fiber mat.

In addition, the electron beam may be irradiated with a dose of 50 to 500 kGy.

The composite material sheet of the present invention has excellent effects such as gas barrier properties and mechanical properties while maintaining the excellent durability, rigidity and stability at high temperatures of polyetherimide.

The composite material sheet and its manufacturing method of the present invention have the effect of reducing the manufacturing cost of the final composite material and can be used as a material in various engineering fields such as automobiles, aviation, and electronic components.

These drawings are for reference in describing an exemplary embodiment of the present invention, and the technical spirit of the present invention should not be construed as being limited to the accompanying drawings.
1 shows a process of manufacturing a composite material sheet using compression molding according to an embodiment of the present invention.
2 shows the shear viscosity measurement results of Preparation Examples 1 to 3 and Comparative Example 1.
Figure 3a shows the tensile strength of Preparation Examples 1 to 3, Examples 1 to 6, and Comparative Example 1.
Figure 3b shows the tensile strain of Preparation Examples 1 to 3, Examples 1 to 6, and Comparative Example 1.
Figure 4a shows the water vapor transmission rate of Preparation Examples 1 to 3, Examples 1 to 6, and Comparative Example 1.
4B shows changes in oxygen gas permeability of Preparation Examples 1 to 3, Examples 1 to 6, and Comparative Example 1.
5 shows the thermal expansion characteristics of Preparation Examples 1 to 3, Examples 1 to 6, and Comparative Example 1.
Figure 6a shows an SEM image of the composite material sheet prepared according to Example 1.
Figure 6b shows an SEM image of the composite material sheet prepared according to Example 4.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those of ordinary skill in the art to which the present invention pertains can easily carry out the present invention.

However, the following description is not intended to limit the present invention to specific embodiments, and when it is determined that a detailed description of a related known technology may obscure the gist of the present invention in describing the present invention, the detailed description thereof will be omitted. .

The terminology used herein is only used to describe specific embodiments, and is not intended to limit the present invention. The singular expression includes the plural expression unless the context clearly dictates otherwise. In the present application, terms such as "comprise" or "have" are intended to designate that a feature, number, step, operation, element, or combination thereof described in the specification exists, but is one or more other features or It should be understood that the existence or addition of numbers, steps, acts, elements, or combinations thereof, is not precluded in advance.

Also, terms including an ordinal number such as first, second, etc. to be used below may be used to describe various elements, but the elements are not limited by the terms. The above terms are used only for the purpose of distinguishing one component from another. For example, without departing from the scope of the present invention, a first component may be referred to as a second component, and similarly, a second component may also be referred to as a first component.

In addition, when it is said that a component is "formed" or "stacked" on another component, it may be formed or laminated directly attached to the front surface or one surface on the surface of the other component. It should be understood that other components may be present in the .

Hereinafter, a composite material sheet comprising the polyetherimide blend and the glass fiber mat of the present invention and a method for manufacturing the same will be described in detail. However, this is provided as an example, and the present invention is not limited thereto, and the present invention is only defined by the scope of the claims to be described later.

The composite material sheet of the present invention includes a polyetherimide blend and a glass fiber mat.

Specifically, the composite material sheet is a glass fiber mat; and a blend impregnated in the glass fiber mat, wherein the blend is polyetherimide (PEI, Poly Ether Imide), polyethylene naphthalate (PEN, Poly Ethylene Naphthalate) and polyethylene terephthalate (PET, Poly Ethylene). terephthalate).

In addition, the composite material sheet includes the blend, and may further include a blend layer formed on one or more surfaces selected from the group consisting of any one surface and the other surface of the composite material sheet.

In addition, the blend may be impregnated into the empty space of the glass fiber sheet.

In addition, the glass fiber mat may be a surface-modified glass fiber mat.

In addition, the surface-modified glass fiber mat is acrylic (acryl), vinyl (vinyl), methacrylate, amine (amine), epoxy (epoxy), chloropropyl mercapto cationic styryl (chloropropyl mercapto cationic styryl) ) and γ-glycidoxypropyl trimethoxy may include at least one organic functional group selected from the group consisting of, preferably, an epoxy functional group.

In addition, the blend may be cross-linked, and the blend and the glass fiber mat may be cross-linked.

In addition, the crosslinking may be performed by irradiation with an electron beam.

In addition, the glass fiber mat may be in the form of a plain weave.

In addition, the blend may include 10 to 70 parts by weight of the polyethylene naphthalate and polyethylene terephthalate, preferably 20 to 60 parts by weight, more preferably 30 to 50 parts by weight, based on 100 parts by weight of the blend. may include When the combined amount of the polyethylene naphthalate and polyethylene terephthalate is less than 10 parts by weight, the effect of blocking gas including moisture is insignificant, and when it exceeds 70 parts by weight, heat resistance deteriorates, which is not preferable.

Hereinafter, a method for manufacturing the composite material sheet of the present invention will be described.

first, polyetherimide ( PEI , Polyetherimide ), polyethylene naphthalate (PEN, Polyethylene naphthalate ) and Polyethylene terephthalate Prepare a blend containing (PET, polyethylene terephthalate) (step a).

In addition, the blend may include 10 to 70 parts by weight of the polyethylene naphthalate and polyethylene terephthalate, preferably 20 to 60 parts by weight, more preferably 30 to 50 parts by weight, based on 100 parts by weight of the blend. may include

When the combined amount of the polyethylene naphthalate and polyethylene terephthalate is less than 10 parts by weight, the effect of blocking gas including moisture is insignificant, and when it exceeds 70 parts by weight, heat resistance deteriorates, which is not preferable.

Finally, the above blend on fiberglass mat impregnate A composite material sheet is prepared (step b).

1 shows a process of manufacturing a composite material sheet using compression molding according to an embodiment of the present invention.

Referring to FIG. 1 , the impregnation may be performed by compression molding.

A release agent may be positioned between the mold and the composite material sheet composition to smoothly remove the composite material sheet from the mold after compression molding. The release agent may include at least one selected from the group consisting of a Teflon film, polyimide (PI), polyamide (PA, polyamide), and silicone.

In addition, the glass fiber mat may be a surface-modified glass fiber mat.

In addition, the surface-modified glass fiber mat is epoxy, acryl, vinyl, methacrylate, amine, chloropropyl mercapto cationic styryl (chloropropyl mercapto cationic styryl) ) and γ-glycidoxypropyl trimethoxy may include at least one organic functional group selected from the group consisting of, preferably, an epoxy functional group.

In addition, the step b may be carried out in a temperature range of 100 to 600 °C, preferably in a temperature range of 200 to 500 °C, more preferably in a temperature range of 300 to 400 °C. When the temperature in step b is less than 100° C., it is not preferable because it is insufficient to impregnate the blend into the glass fiber mat, and when it exceeds 600° C., the thermal decomposition effect of the blend occurs, which is not preferable.

In addition, the step b may be performed in a pressure range of 0.1 to 5.0 MPa, preferably in a pressure range of 0.5 to 4.0 MPa, more preferably in a pressure range of 1.0 to 3.0 MPa. When the pressure in step b is less than 0.1 MPa, it is not preferable because it is insufficient to impregnate the blend into the glass fiber mat, and when it exceeds 5.0 MPa, the impregnation effect of the blend is insignificant compared to the pressure increase.

In addition, the step b may be performed for 1 to 20 minutes, preferably 5 to 15 minutes, more preferably 7 to 12 minutes. Here, when the time of step b is less than 1 minute, it is not preferable because it is insufficient to impregnate the blend into the glass fiber mat, and when it exceeds 20 minutes, the impregnation effect of the blend is insignificant compared to the lapse of time.

In addition, after the step (b), (c) irradiating an electron beam (electron beam) to the manufactured composite material sheet; may further include.

In addition, the irradiation of the electron beam may crosslink the blend and crosslink the blend and the glass fiber mat.

In addition, the electron beam may be irradiated at a dose of 50 to 500 kGy, preferably at a dose of 75 to 300 kGy, more preferably at a dose of 100 to 200 kGy. When the irradiation dose of the electron beam is less than 50 kGy, the crosslinking effect of the blend is insignificant, which is not preferable, and when it exceeds 500 kGy, it is not preferable because cleavage of the polymer chain may occur.

The composite material sheet manufactured by the above method is applied to various industrial fields such as aircraft body, electronic products requiring low coefficient of thermal expansion (CTE) and high heat resistance, or applications that are sensitive to moisture and require high gas barrier properties and tensile strength. can be

[Example]

Hereinafter, a preferred embodiment of the present invention will be described. However, this is for illustrative purposes only, and the scope of the present invention is not limited thereto.

Blend Manufacturing

Preparation Example 1: A blend with a PEI/PEN/PET weight ratio of 70:15:15

Polyetherimide (PEI) (Ultem-1000, Sabic), polyethylene naphthalate (PEN) (SKYNEX, SKC) and polyethylene terephthalate on a twin screw extruder (Hankook EM Ltd) with a screw diameter of 32 mm and a length/diameter ratio of 40 (PET) (BL, Huvis Co.) was added in a weight ratio of 70:15:15 and then extruded to prepare a blend containing polyetherimide, polyethylene naphthalate and polyethylene terephthalate.

Preparation Example 2: A blend with a PEI/PEN/PET weight ratio of 50:25:25

Polyetherimide, polyethylene or polyetherimide was used in the same manner as in Preparation Example 1 except that polyetherimide, polyethylene naphthalate and polyethylene terephthalate were used in a weight ratio of 50:25:25 instead of using a weight ratio of 70:15:15. A blend comprising phthalate and polyethylene terephthalate was prepared.

Preparation Example 3: Blend with PEI/PEN/PET weight ratio of 30:35:35

Polyetherimide, polyethylene or polyetherimide was used in the same manner as in Preparation Example 1 except that polyetherimide, polyethylene naphthalate, and polyethylene terephthalate were used in a weight ratio of 30:35:35 instead of using a weight ratio of 70:15:15. A blend comprising phthalate and polyethylene terephthalate was prepared.

Comparative Example 1: Polyetherimide sheet

Polyetherimide (PEI) (Ultem-1000, Sabic) was put into a twin-screw extruder (Hankook E.M Ltd) having a screw diameter of 32 mm and a length/diameter ratio of 40, and then extruded to prepare a polyetherimide sheet.

Table 1 below summarizes the weight ratios of polyetherimide, polyethylene naphthalate, and polyethylene terephthalate of Preparation Examples 1 to 3 and Comparative Example 1.

division PEI (parts by weight) PEN (parts by weight) PET (parts by weight) Preparation Example 1 70 15 15 Preparation 2 50 25 25 Preparation 3 30 35 35 Comparative Example 1 100 - -

Composite material sheet manufacturing

Example One

Glass fiber mat surface-modified with the blend prepared according to Preparation Example 1 and epoxy silane (2116, Hankuk Advanced Materials, plain weave glass fiber thickness 0.10 mm, warp density 44 count/in, weft density 33 count /in) was heated and pressurized at 320 ° C. at 1.0 to 2.5 MPa pressure for 10 minutes using a compression molding machine to prepare a composite material sheet.

Example 2

A composite material sheet was prepared in the same manner as in Example 1, except that the blend prepared according to Preparation Example 2 was used instead of using the blend prepared according to Preparation Example 1.

Example 3

A composite material sheet was prepared in the same manner as in Example 1, except that the blend prepared according to Preparation Example 3 was used instead of using the blend prepared according to Preparation Example 1.

Example 4

A composite material sheet was prepared in the same manner as in Example 1, except that the composite material sheet was additionally irradiated with an electron beam at a dose of 100 kGy.

Example 5

Example 1, except that the blend prepared according to Preparation Example 2 was used instead of using the blend prepared according to Preparation Example 1, and an electron beam was additionally irradiated to the composite material sheet at a dose of 100 kGy A composite material sheet was prepared in the same manner.

Example 6

Example 1, except that the blend prepared according to Preparation Example 3 was used instead of using the blend prepared according to Preparation Example 1, and an electron beam was additionally irradiated to the composite sheet at a dose of 100 kGy A composite material sheet was prepared in the same manner.

Table 2 below summarizes the proportions by weight of the composite materials according to Examples 1 to 6 and whether or not the electron beam is irradiated.

division PEI (parts by weight) PEN (parts by weight) PET (parts by weight) surface modification
(epoxy silane) electron beam irradiation
(100 kGy) Example 1 70 15 15 ○ - Example 2 50 25 25 ○ - Example 3 30 35 35 ○ - Example 4 70 15 15 ○ ○ Example 5 50 25 25 ○ ○ Example 6 30 35 35 ○ ○

test example One: of blend Thermal stability according to content

Table 3 shows the thermogravimetric analysis results according to the content ratio of the blend including polyetherimide, polyethylene naphthalate and polyethylene terephthalate.

division Preparation Example 1 Preparation 2 Preparation 3 Comparative Example 1 Thermal decomposition temperature (Td, ℃) 405 396 390 505

Specifically, in order to confirm thermal stability according to the content ratio of polyetherimide, polyethylene naphthalate and polyethylene terephthalate, thermogravimetric analyzers (TGA, TA Instrument, Model SDT-Q600) was used to measure weight loss from room temperature to 850°C at a heating rate of 20°C/min in air. The temperature at 1% weight loss is expressed as the thermal decomposition temperature (Td).

Referring to Table 3, in the blends prepared according to Preparation Examples 1 to 3, as the polyethylene naphthalate and polyethylene terephthalate content increased, the thermal decomposition temperature was lower than that of the polyetherimide sheet prepared according to Comparative Example 1 at 505° C. showed a trend. In the blend prepared according to Preparation Examples 1 to 3, it can be seen that the thermal decomposition temperature was 400° C. or higher up to 30 parts by weight of polyethylene naphthalate and polyethylene terephthalate.

Therefore, it can be seen that thermal stability is maintained at a high level up to 30 parts by weight of polyethylene naphthalate and polyethylene terephthalate in the blend.

test example 2: of blend according to the content rheological feature analysis

Figure 2 shows the shear viscosity measurement result of the blend according to the polyetherimide content ratio in the blend. Specifically, in order to analyze the impregnation processability of the blend and the glass fiber mat, for the blends prepared according to Preparation Examples 1 to 3 and Comparative Example 1, the shear viscosity of the polymer was measured using a capillary rheometer (Malvern Instruments, Model RH2000). carried out.

Referring to FIG. 2 , it can be seen that the viscosity of the blends prepared according to Preparation Examples 1 to 3 decreases as the content of polyethylene naphthalate and polyethylene terephthalate increases. In general, since polyetherimide has high viscosity and low fluidity, the glass fiber mat and impregnation processability are low during the manufacturing process of composite material sheet, whereas the viscosity of the blend decreases as the content of polyethylene naphthalate and polyethylene terephthalate increases It can be seen that the impregnation processability of the glass fiber mat for the blend is significantly improved as it penetrates more easily into the mat.

test example 3: blend Measurement of tensile strength and strain according to content, whether glass fiber mat is included, and whether or not electron beam is irradiated

3A shows the change in tensile strength according to the blend content, whether or not the glass fiber mat is included, and whether or not the electron beam is irradiated. 3b shows the change in tensile strain according to the blend content, whether or not the glass fiber mat is included, and whether or not the electron beam is irradiated.

Table 4 below summarizes the tensile strength and strain measurement results of Preparation Examples 1 to 3, Examples 1 to 6, and Comparative Example 1.

division tensile strength
(Tensile Strength, MPa) tensile strain
(Tensile Strain, MPa) water vapor transmission rate
(WVTR,
gm mm/m ² day) oxygen permeability
(O ₂ TR,
cc mm/m ² day) Preparation Example 1 91.0 5.4 1.82 11.2 Preparation 2 76.7 4.1 1.52 5.8 Preparation 3 38.1 2.8 1.46 4.7 Example 1 172.7 3.8 0.63 3.8 Example 2 162.5 3.0 0.44 2.0 Example 3 147.0 2.9 0.39 2.0 Example 4 212.5 3.0 0.34 2.3 Example 5 193.4 2.5 0.24 1.2 Example 6 169.1 2.6 0.26 0.8 Comparative Example 1 68.4 5.7 3.41 22.0

Specifically, in order to measure the tensile strength and strain according to the blend content, whether or not the glass fiber mat is included and whether or not to be irradiated with an electron beam, Preparation Examples 1 to 3, Examples 1 to 6 and Comparative Example 1 were subjected to a cutter according to ASTM D882-12 specification. Using a universal tester (UTM, INSTRON, Model 5543), it was measured at 50 mm/min (cross head speed) and 1 kN (load cell) at room temperature, and the tensile test was performed three times in total. The test was carried out.

Referring to Table 4 and FIG. 3A, the tensile strength of the blend prepared according to Preparation Examples 1 and 2 was higher than that of the polyetherimide sheet prepared according to Comparative Example 1, and the blend prepared according to Preparation Example 3 was compared with Comparative Example It can be seen that it appeared lower than the polyetherimide sheet prepared according to 1.

In addition, it can be seen that the tensile strength of the composite material sheet prepared according to Examples 1 to 3 is more than twice the tensile strength of the polyetherimide sheet prepared according to Comparative Example 1. The tensile strength of the composite material sheet prepared according to Examples 4 to 6 was about 2.5 times higher than the tensile strength of the polyetherimide sheet prepared according to Comparative Example 1, and in particular, the composite material prepared according to Example 4 It can be seen that the sheet has about three times higher tensile strength.

Referring to Table 4 and Figure 3b, the tensile strain of the blends prepared according to Preparation Examples 1 to 3 showed a tendency to decrease as the content of polyethylene naphthalate and polyethylene terephthalate increased, but in Examples 1 to 6 It can be seen that the tensile strain in the composite material sheet manufactured according to this method shows a relatively similar value of about 3%.

Such a result can be considered to be due to the physical properties of the glass fiber mat. Specifically, when the tensile strain is measured, the glass fiber mat is stretched in the fiber orientation direction, and when the tensile strain is about 3%, it is caused by the breakage of the glass fiber mat. can be seen as

test example 4: blend Content, including fiberglass mat and analysis of gas barrier properties according to whether or not irradiation with electron beams

Figure 4a shows the change in water vapor transmission rate according to the blend content, whether or not the glass fiber mat is included and whether or not the electron beam is irradiated. Figure 4b shows the change in oxygen gas transmittance according to the blend content, whether the fiberglass mat is included, and whether the electron beam is irradiated.

Table 4 summarizes the water vapor transmission rate and oxygen transmission rate measurement results of Preparation Examples 1 to 3, Examples 1 to 6, and Comparative Example 1.

In detail, Preparation Examples 1 to 3, Examples 1 to 6, and Comparative Example 1 were used to measure water vapor transmission rate (WVTR) and oxygen gas transmission rate (OTR). Using a test device (Mocon Permatran-W, Model 3/33) and an oxygen gas permeability test device (Mocon OX-TRAN, Model 2/21), at 37.8°C for measuring water vapor transmission rate and 23°C for oxygen gas transmission rate for 30 minutes The water vapor transmission rate and oxygen gas transmission rate were obtained by measuring 20 times in a cycle.

Referring to FIGS. 4A to 4B and Table 4, it can be seen that the blends prepared according to Preparation Examples 1 to 3 exhibit better gas barrier properties than the polyetherimide sheets prepared according to Comparative Example 1.

As a result of this, it can be seen that polyethylene naphthalate and polyethylene terephthalate have better gas barrier properties than polyetherimide, and therefore, the gas barrier properties are considered to be affected by the properties of the resin itself.

In addition, the water vapor transmission rate of Comparative Example 1 was 3.41. gm·mm/m ² ·day, whereas the composite material sheets prepared according to Examples 1 and 4 ^{were reduced to 0.63 and 0.34 gm·mm/m 2} ·day, respectively, and increased water vapor barrier properties by including the glass fiber mat can confirm that In particular, in the case of Example 6 irradiated with electron beams, it can be seen that the moisture barrier properties were significantly improved by more than 12 times compared to the case of the polyetherimide sheet (Comparative Example 1).

In addition, the oxygen gas permeability of Comparative Example 1 was 22.0 gm·mm/m ² ·day, whereas the composite material sheets prepared according to Examples 1 and 4 ^{were reduced to 3.8 and 2.3 gm·mm/m 2} ·day, respectively, and oxygen gas barrier properties by including the glass fiber mat increase can be seen. In particular, in the case of Example 6 irradiated with an electron beam, it can be seen that the oxygen gas barrier property is greatly improved by about 27 times or more than in the case of the polyetherimide sheet (Comparative Example 1).

In other words, it can be seen that the gas barrier properties of the composite sheet are significantly improved by blending polyethylene naphthalate and polyethylene terephthalate with polyetherimide, using a surface-modified glass fiber mat, and irradiating an electron beam, which is a glass fiber mat. It can be considered that this is because the gas permeation path length of the composite material sheet is increased by including , and a three-dimensional network is formed by the cross-linking of the blend and the cross-linking of the blend and the glass fiber mat by irradiating electron beams.

test example 5: blend Analysis of thermal expansion characteristics according to content, whether glass fiber mat is included, and whether or not electron beam is irradiated

5 is a graph showing changes in the coefficient of thermal expansion (Coefficients of Thermal Expansion) according to the blend content, whether or not the glass fiber mat is included, and whether or not the electron beam is irradiated.

Specifically, in order to measure the coefficient of thermal expansion, the composite materials prepared according to Preparation Examples 1 to 3, Examples 1 to 6 and Comparative Example 1 were in the form of a film using thermomechanical analysis equipment (TMA, TA Instruments). The coefficient of thermal expansion was measured from room temperature to 150°C under a force of 0.03N at a heating rate of 10°C/min.

Referring to FIG. 5 , the coefficients of thermal expansion of the blend sheets prepared according to Preparation Examples 1 to 3 tended to increase as the content of polyethylene naphthalate and polyethylene terephthalate increased. The coefficient of thermal expansion of the composite sheet prepared according to Examples 1 to 3 was significantly lower than that of the polyetherimide sheet prepared according to Comparative Example 1. In addition, the coefficient of thermal expansion of the composite material sheets irradiated with electron beams prepared according to Examples 4 to 6 was lower than that of the composite material sheets prepared according to Examples 1 to 3. According to the change of the blend composition in the composite material sheet of Examples 1 to 6, the change in the coefficient of thermal expansion was not large.

This stabilization of the coefficient of thermal expansion can be considered to occur due to the crosslinking effect of using a heat-resistant glass fiber mat that maintains the structure and shape of the composite material at high temperatures and irradiating it with an electron beam.

test example 6: Depending on whether the electron beam is irradiated or not blend and Adhesion analysis between fiberglass mats

Figure 6a shows the SEM image of Example 1, Figure 6b shows the SEM image of Example 4. Specifically, in order to perform an adhesive analysis between the blend and the glass fiber mat according to whether or not electron beam irradiation, the composite material sheets of Examples 1 and 4 were immersed in liquid nitrogen for 10 minutes and then crushed to obtain the crushed surface. Surface observation was performed using a scanning electron microscope (SEM, Hitachi, Model S-4700).

6a to 6b, the interfacial adhesion between the blend of the composite material sheet (Example 4) irradiated with electron beams and the glass fiber mat is the blend of the composite material sheet (Example 1) that is not irradiated with electron beams and the glass fiber mat It was found to be better than interfacial adhesion.

As a result, it can be seen that the composite material sheet irradiated with electron beam is superior to the composite material sheet not irradiated with electron beam in terms of mechanical properties, moisture and oxygen gas barrier properties.

The scope of the present invention is indicated by the following claims rather than the above detailed description, and all changes or modifications derived from the meaning and scope of the claims and their equivalent concepts should be interpreted as being included in the scope of the present invention. do.

Claims (17)

fiberglass mat; and
Including; a blend impregnated in the glass fiber mat;
The blend includes polyetherimide (PEI, Poly Ether Imide), polyethylene naphthalate (PEN, Poly Ethylene Naphthalate) and polyethylene terephthalate (PET, Poly Ethylene Terephthalate),
The glass fiber mat is a glass fiber mat surface-modified with epoxy silane,
the blend is crosslinked, the blend and the glass fiber mat are crosslinked,
The crosslinking is performed by irradiation of electron beams,
composite sheet. According to claim 1,
The composite material sheet includes the blend, and the composite material sheet further comprises a blend layer formed on one or more surfaces selected from the group consisting of one surface and the other surface of the composite material sheet. material sheet. According to claim 1,
The composite material sheet, characterized in that the blend is impregnated in the empty space of the glass fiber mat. delete delete delete delete The method of claim 1
The composite material sheet, characterized in that the glass fiber mat is in the form of a plain weave. According to claim 1,
Composite material sheet, characterized in that the blend contains 10 to 70 parts by weight of the polyethylene naphthalate and polyethylene terephthalate, based on 100 parts by weight of the blend. (a) preparing a blend comprising polyetherimide (PEI, Poly Ether Imide), polyethylene naphthalate (PEN, Poly Ethylene Naphthalate) and polyethylene terephthalate (PET, Poly Ethylene Terephthalate);
(b) manufacturing a composite material sheet by impregnating the blend into a glass fiber mat; and
(c) irradiating an electron beam to the manufactured composite material sheet;
The glass fiber mat is a glass fiber mat surface-modified with epoxy silane,
The irradiation of the electron beam crosslinks the blend and crosslinks the blend and the glass fiber mat,
A method for manufacturing a composite material sheet according to claim 1. 11. The method of claim 10,
The blend is a method of manufacturing a composite material sheet, characterized in that it contains 10 to 70 parts by weight of the polyethylene naphthalate and polyethylene terephthalate, based on 100 parts by weight of the blend. delete delete 11. The method of claim 10,
The method of manufacturing a composite material sheet, characterized in that the step (b) is performed for 1 to 20 minutes at a temperature of 100 to 600 ℃ and a pressure of 0.1 to 5.0 MPa. delete delete 11. The method of claim 10,
The method of manufacturing a composite material sheet, characterized in that the electron beam is irradiated with a dose of 50 to 500 kGy.

Images