KR20220057419A - Thermoplastic resin composition and molded product - Google Patents

Abstract

The present invention relates to a thermoplastic resin composition and a molded article manufactured therefrom. The present invention provides the thermoplastic resin composition particularly suitable for substituting metal parts and having significantly improved tensile strength and light weight while having equal or better impact strength, elongation, workability, and the like compared to a conventional polyamide composite material and the molded article manufactured therefrom.

Description

Thermoplastic resin composition and molded article {THERMOPLASTIC RESIN COMPOSITION AND MOLDED PRODUCT}

The present invention relates to a thermoplastic resin composition and a molded article manufactured therefrom, and more particularly, to a conventional polyamide composite material, such as impact strength, elongation and workability, etc., while significantly improved tensile strength and lightweight metal parts It relates to a thermoplastic resin composition particularly suitable for replacement and a molded article prepared therefrom.

When a metal such as aluminum alloy or magnesium alloy is used as a material for automobile parts, there are disadvantages such as specific gravity, post-processing, price volatility, and environmental problems.

Accordingly, research on replacing the material of automobile parts with plastics is being actively conducted in order to reduce the weight and manufacturing cost, and polyamide resins with excellent mechanical strength, moldability, and long-term physical properties are attracting attention as replacement materials.

Polyamide composite material containing reinforcing fibers such as glass fiber (GF), aramid fiber (AF) and carbon fiber (CF) to apply polyamide resin as a material for automobile safety parts by replacing metals such as aluminum and steel Research is ongoing.

However, carbon fiber (CF) has a disadvantage in that it has low impact strength when applied as a material for automobile structures, and glass fiber (GF) that can realize impact strength is composed of various components such as silica, alumina, calcium oxide, and magnesia. Therefore, it is necessary to develop a polyamide resin composition capable of providing performance improvement specific to the application because different performance is expressed depending on the composition.

Korean Registered Patent No. 1626783

An object of the present invention is to provide a thermoplastic resin composition which is particularly suitable for replacing metal material parts with significantly improved tensile strength and light weight while having equal or greater impact strength, elongation and workability compared to conventional polyamide composite materials, and molded articles manufactured therefrom. will provide

The above and other objects of the present invention can all be achieved by the present invention described below.

In order to achieve the above object, the present invention

20 to 64 wt% of a non-aromatic polyamide resin having a glass transition temperature (Tg) of 50 to 60 °C and a melting temperature (Tm) of 240 to 265 °C; 36 to 80% by weight of glass fibers having a silica content of 52 to 66% by weight; and 0 to 30 wt% of an aromatic polyamide resin;

Provided is a thermoplastic resin composition having a tensile strength of 270 MPa or more at room temperature based on standard measurement ISO 527.

Let the glass transition temperature (Tg) of the non-aromatic polyamide resin be a, the glass transition temperature (Tg) of the aromatic polyamide resin be b, and the melting temperature (Tm) of the non-aromatic polyamide resin is c And, if the silica content included in the glass fiber is d, the following Equations 1 to 3 may be satisfied.

[Equation 1]

4.8a ≤ c ≤ 5.3a

[Equation 2]

2d ≤ b ≤ 2.5d

[Equation 3]

a < b < c

(In the above equations, a, b, c, and d satisfy 50≤a≤60, 106≤b≤150, 240≤c≤265, and 52≤d≤66.)

The glass fiber is 52-66 wt% silica, 12-21 wt% alumina, 0.5-24 wt% calcium oxide, 12 wt% or less magnesia, 0-8 wt% boron trioxide, 3 wt% or less titanium dioxide, Fe ₂ O ₃ 0 to 0.6% by weight, 0 to 8% by weight of boron oxide, 0 to 0.7% by weight of F (fluorine), and 0.8% by weight or less of the total amount of sodium oxide and potassium oxide.

The glass fiber is 58 to 62% by weight of silica, 14 to 18% by weight of alumina, 10 to 13% by weight of calcium oxide, 8 to 10% by weight of magnesia, 0.5 to 2% by weight of titanium dioxide, 0.8% by weight of sodium oxide and potassium oxide % or less, and Fe ₂ O ₃ 0.5 wt% or less.

The glass fiber is 52 to 56% by weight of silica, 12 to 16% by weight of alumina, 20 to 24% by weight of calcium oxide, 1.5% by weight or less of magnesia, 1% by weight or less of titanium dioxide, and 0.8% by weight or less of the total amount of sodium oxide and potassium oxide , Fe ₂ O ₃ 0.4 wt% or less, boron oxide 5-8 wt% and F (fluorine) 0.7 wt% or less may be included.

The glass fiber may be a circular glass fiber having a circular cross section in which the total amount of calcium oxide and magnesium is 17 to 24 wt%.

The glass fiber may be a flat glass fiber having a non-circular cross-section in which the total amount of calcium oxide and magnesium is 21 to 25% by weight.

The glass fiber may have an aspect ratio expressed as a ratio (L/D) of a diameter (D) to a length (L) of 1:1 to 1:4, wherein the diameter (D) may have an average diameter of 6 to 16 μm.

The non-aromatic polyamide resin may be an aliphatic polyamide, and as a specific example has a unit represented by the following Chemical Formula 1, the unit is repeated 50 to 500 times, L is (CH ₂ )n, and n is 3 to 6 It is an integer, and the relative viscosity is 2.3 to 2.8, and the amorphous ratio may be 50 to 60 wt%.

[Formula 1]

The non-aromatic polyamide resin is polyhexamethylene adipamide (PA66), and may be included in an amount of 25 to 60 wt% based on the total weight of the thermoplastic resin composition.

The aromatic polyamide resin may be PA MACM12, PA PACM12, a mixture or copolyamide thereof, or an amorphous resin selected from polyhexamethylene isophthalamide (PA6I), PAMXDI, and PA6I/MXDI.

The aromatic polyamide resin is polyhexamethylene isophthalamide (PA6I), and may be included in an amount of 4 to 25 wt% based on the total weight of the thermoplastic resin composition.

The thermoplastic resin composition may further include one or more additives selected from a flame retardant, a nucleating agent, a heat stabilizer, a light stabilizer, a lubricant, an antioxidant, and a thickener.

The thermoplastic resin composition, 40 to 60% by weight of the non-aromatic polyamide resin; 40 to 60% by weight of the glass fiber; and 0 to 5% by weight of additives, the specific gravity is 1.45 to 1.70 g/cm ³ , the impact strength is 18.5 to 22.5 kJ/m ² , and the elongation at 50 mm in the marked section according to ISO 527 is 2.5 to 3.3 %, and the specific gravity may be 1.45 to 1.70 g/cm ³ .

The thermoplastic resin composition, 30 to 60% by weight of the non-aromatic polyamide resin; 40 to 70% by weight of the glass fiber; And 0 to 5% by weight of additives; containing, the specific gravity of 1.45 to 1.85 g / cm ³ At the same time, the impact strength is 18.5 to 22.5 kJ / m ² , the elongation at 50mm in the marked section based on ISO 527 is 1.9 to 3.3 It can be %.

The thermoplastic resin composition, 25 to 45% by weight of the non-aromatic polyamide resin; 4 to 25% by weight of the aromatic polyamide resin; 50 to 60% by weight of the glass fiber; and 0 to 5% by weight of additives, and may have an elongation of 2.3 to 2.9% in a marked section 50mm based on ISO 527.

The thermoplastic resin composition, 20 to 36% by weight of the non-aromatic polyamide resin; 4 to 20% by weight of the aromatic polyamide resin; 60% by weight of the glass fiber; And 0 to 5% by weight of additives; and, the tensile strength at room temperature according to the standard measurement ISO 527 is 270 MPa or more, and the elongation at 50mm in the marked section according to ISO 527 is 2.2 to 2.5%, according to ASTM D638 Type 1 Based on this, the glass fiber orientation measured at a rate of 5 mm/min in a specimen having a thickness of 3.2 mm and a width of 12.7 mm based on the flow direction (MD) may be 225 to 250 MPa and a perpendicular direction (TD) to 120 to 165 MPa.

The thermoplastic resin composition has a tensile strength at room temperature based on standard measurement ISO 527, a, and an elongation at 50 mm in the marked section based on ISO 527, b, and has a thickness of 3.2 mm and a width of 12.7 based on ASTM D638 Type 1. When c is the difference between the flow direction (MD) and the orthogonal direction (TD) of the glass fiber measured at a speed of 5 mm/min on a mm specimen, the calculated value of a+b/c may be 2.88 or more.

The thermoplastic resin composition may satisfy Equation 1 below in terms of the reduction rate (%) of properties calculated from the normal temperature (23° C.) tensile strength and the high temperature (90° C.) tensile strength based on standard measurement ISO 527.

[Equation 1]

34 ≤ 100 - (high temperature measurement/room temperature measurement x 100) ≤ 44

Also, the present invention

20 to 64 wt% of a non-aromatic polyamide resin having a glass transition temperature (Tg) of 50 to 60 °C and a melting temperature (Tm) of 240 to 265 °C; 36 to 80% by weight of glass fibers having a silica content of 52 to 66% by weight; And 0 to 30% by weight of the aromatic polyamide resin; melt-kneading and extruding; It provides a method for producing a thermoplastic resin composition, characterized in that the tensile strength at room temperature according to standard measurement ISO 527 is 270 MPa or more .

In addition, the present invention provides a molded article prepared from the above-described thermoplastic resin composition.

The molded article may be a high-strength, high-toughness, lightweight automobile part.

According to the present invention, a thermoplastic resin composition which is particularly suitable for replacing metal material parts with a significantly improved tensile strength and light weight while having equal or greater impact strength, elongation and workability compared to conventional polyamide composite materials, and a molded article manufactured therefrom has the effect of providing.

Therefore, the thermoplastic resin composition and the molded article according to the present invention can be widely applied to the automotive industry parts field requiring the same. Specifically, it can be applied as a material for safety parts for automobiles, including seat belts and airbags, which are parts that are subjected to strong force and pressure not only during driving but also in emergency situations such as accidents, as a material for vehicle information guide display and instrument panel, and as a metal replacement material for a digital cockpit.

Hereinafter, the present invention will be described in more detail to help the understanding of the present invention.

The terms or words used in the present specification and claims should not be construed as being limited to conventional or dictionary meanings, and considering that the inventor may appropriately define the concept of the term in order to best describe the invention Therefore, it should be interpreted as meaning and concept consistent with the technical idea of the present invention.

The thermoplastic resin composition according to the present invention contains a non-aromatic polyamide resin, an aromatic polyamide resin, and glass fibers with specified glass transition temperature and melting temperature in a specific composition, and has a tensile strength of 270 MPa based on standard measurement ISO 527 In this case, when product design and design change were considered at the same time, it was confirmed that high rigidity, light weight, and appearance quality that can be substituted for existing metals were secured, and furthermore, certain nucleating agents, flame retardants, and thickeners were optionally included as needed. In this case, the impact strength, elongation and workability of the conventional polyamide composite material are equal to or higher than that of the conventional polyamide composite material, but the tensile strength is greatly improved and it is confirmed that it is particularly suitable for replacing metal material parts with a light weight. Further efforts were made to complete the present invention.

The thermoplastic resin composition of the present invention comprises 20 to 64 wt% of a non-aromatic polyamide resin having a glass transition temperature (Tg) of 50 to 60 °C and a melting temperature (Tm) of 240 to 265 °C; 36 to 80% by weight of glass fibers having a silica content of 52 to 66% by weight; and 0 to 30 wt% of an aromatic polyamide resin; characterized in that the tensile strength at room temperature according to standard measurement ISO 527 is 270 MPa or more, and in this case, impact strength, elongation and workability compared to the conventional polyamide composite material There is an advantage of providing a thermoplastic resin composition suitable for replacing metal parts with a significantly improved tensile strength and light weight while being equal to or more than the same.

In addition, the thermoplastic resin composition of the present invention has a glass transition temperature (Tg) of 50 to 60 ℃ and a melting temperature (Tm) of 20 to 64% by weight of a non-aromatic polyamide resin of 240 to 265 ℃; 36 to 80% by weight of glass fibers of circular or non-circular cross-section, having a silica content of 52 to 66% by weight; and 0 to 30% by weight of an aromatic polyamide resin; wherein the glass fibers contain 52 to 66% by weight of silica, 12 to 21% by weight of alumina, 0.5 to 24% by weight of calcium oxide, 12% by weight or less of magnesia, and 0% by weight of boron trioxide. ~8 wt%, titanium dioxide 3 wt% or less, Fe ₂ O ₃ 0~0.6 wt%, boron oxide 0~8 wt%, F (fluorine) 0~0.7 wt%, and the total amount of sodium oxide and potassium oxide 0.8 wt. % or less, and characterized in that the tensile strength at room temperature according to the standard measurement ISO 527 is 270 MPa or more. There is an advantage of providing a thermoplastic resin composition suitable for replacing metal parts with improved and light weight.

In addition, the thermoplastic resin composition of the present invention has a glass transition temperature (Tg) of 50 to 60 ℃ and a melting temperature (Tm) of 20 to 64% by weight of a non-aromatic polyamide resin of 240 to 265 ℃; 36 to 80% by weight of glass fibers of circular or non-circular cross-section, having a silica content of 52 to 66% by weight; and 0 to 30% by weight of an aromatic polyamide resin; wherein the glass fibers contain 52 to 66% by weight of silica, 12 to 21% by weight of alumina, 0.5 to 24% by weight of calcium oxide, 12% by weight or less of magnesia, and 0% by weight of boron trioxide. ~8 wt%, titanium dioxide 3 wt% or less, Fe ₂ O ₃ 0~0.6 wt%, boron oxide 0~8 wt%, F (fluorine) 0~0.7 wt%, and the total amount of sodium oxide and potassium oxide 0.8 wt. % or less, wherein the non-aromatic polyamide resin contains polyhexamethylene adipamide (PA66) in an amount of 25 to 60 wt% based on the total weight of the thermoplastic resin composition, and tensile temperature at room temperature based on standard measurement ISO 527 It is characterized in that the strength is 270 MPa or more, and in this case, the impact strength, elongation and workability, etc. are equal or more than that of the conventional polyamide composite material, but the tensile strength is greatly improved and a thermoplastic resin composition suitable for replacing metal parts with a light weight has the advantage of providing

In addition, the thermoplastic resin composition of the present invention preferably comprises 20 to 64 wt% of a non-aromatic polyamide resin having a glass transition temperature (Tg) of 50 to 60 °C and a melting temperature (Tm) of 240 to 265 °C; 36 to 80% by weight of glass fibers of circular or non-circular cross-section, having a silica content of 52 to 66% by weight; and 0 to 30% by weight of an aromatic polyamide resin; wherein the glass fibers contain 52 to 66% by weight of silica, 12 to 21% by weight of alumina, 0.5 to 24% by weight of calcium oxide, 12% by weight or less of magnesia, and 0% by weight of boron trioxide. ~8 wt%, titanium dioxide 3 wt% or less, Fe ₂ O ₃ 0~0.6 wt%, boron oxide 0~8 wt%, F (fluorine) 0~0.7 wt%, and the total amount of sodium oxide and potassium oxide 0.8 wt. % or less, and the polyhexamethylene isophthalamide (PA6I) is included in an amount of 4 to 25% by weight based on the total weight of the thermoplastic resin composition, and the tensile strength at room temperature based on standard measurement ISO 527 is 270 MPa or more In this case, there is an advantage of providing a thermoplastic resin composition suitable for replacing metal material parts with significantly improved tensile strength and light weight while having equal or greater impact strength, elongation and workability compared to conventional polyamide composite materials. .

Hereinafter, each component constituting the thermoplastic resin composition of the present disclosure will be described in detail as follows.

Non-aromatic polyamide resin

In one embodiment of the present invention, the non-aromatic polyamide resin is prepared by condensation polymerization of a monomer composed of an aliphatic dicarboxylic acid and an aliphatic or alicyclic diamine in a structure that does not include an aromatic ring in the main chain.

The aliphatic dicarboxylic acid may have, for example, 5 to 7 carbon atoms, preferably 6 carbon atoms.

The aliphatic or alicyclic diamine may have 6 to 20 carbon atoms, for example.

As an example, the non-aromatic polyamide resin may be an aliphatic polyamide, and as a specific example has a unit represented by the following Chemical Formula 1, the unit is repeated 50 to 500 times, L is (CH ₂ ) _n , and n is 3 It is an integer of to 6, and may be semi-crystalline, amorphous, or a mixture thereof.

[Formula 1]

In addition, the non-aromatic polyamide resin has a unit represented by a urethane bond-linker-urethane bond, the linker is (CH ₂ ) ₆ , and the unit is repeated 50 to 500 times, semi-crystalline, amorphous, or a mixture thereof may be

The amorphous polymer in the present disclosure has crystallization (exothermic) or melting (endothermic) peaks during differential scanning calorimetry (DSC) testing for temperatures ranging from values below the glass transition temperature (Tg) to Tg+300°C. A polymer that does not produce peaks is defined as a polymer that, conversely, is a crystalline or semicrystalline polymer if these peaks are recorded in the DSC test. Such DSC tests are known to those skilled in the art.

In the present description, the non-aromatic polyamide resin (A) does not contain aromatics, and the amorphous content in the resin is not simply included, but occupies a substantial portion, for example, in an amorphous content of 50 to 60 wt%. When the amorphous ratio of the non-aromatic polyamide resin satisfies the above range, it is possible to secure a thermoplastic resin composition having excellent balance between mechanical properties and moldability.

In the present invention, the crystalline polymer and the amorphous polymer are crystallized (exothermic) by a differential scanning calorimetry (DSC) test at a temperature ranging from a temperature value below the glass transition temperature (Tg) to Tg + 300 ° C. or a polymer that produces melting (endothermic) peaks and a polymer that does not produce the crystallization (exothermic) or melting (endothermic) peaks.

The non-aromatic polyamide resin may be polyhexamethylene adipamide (PA66) as a specific example.

The non-aromatic polyamide resin may have a glass transition temperature of, for example, 50 to 60°C, preferably 52 to 58°C. When the above-mentioned range is satisfied, excellent heat resistance can be provided, and there is an effect of improving the tensile strength of a molded article manufactured by molding the thermoplastic resin composition of the present invention.

The non-aromatic polyamide resin may have a melting temperature (Tm) of, for example, 240 to 265°C, preferably 245 to 265°C. When the above-mentioned range is satisfied, it is possible to provide better heat resistance along with processability, thereby improving the tensile strength of a molded article manufactured by molding the thermoplastic resin composition of the present invention.

In the present invention, the glass transition temperature (Tg) and the melting temperature (Tm) may be measured by DSC, respectively. As an example, the melting temperature (Tm) is maintained at 330 ° C. for 5 minutes using DSC7 from Perkin-Elemer, then lowered to 23 ° C. at a rate of 10 ° C./min, and then the temperature is raised at 10 ° C./min, Refers to the endothermic peak upon melting.

The non-aromatic polyamide resin of the present substrate may have a glass transition temperature (Tg) of 50 to 60 °C, or 52 to 60 °C, and a melting temperature (Tm) of 240 to 265 °C, or 245 to 265 °C. If the above-mentioned range is satisfied, high rigidity, weight reduction, and appearance quality can be secured to a degree that can replace existing metal when product design and design change are simultaneously considered.

The non-aromatic polyamide resin uses 96wt% sulfuric acid as a solvent based on Sulfuric RV, and the relative viscosity calculated by calculating the resin concentration in the solution as 1.0 w/v% is 2.3 to 2.8, preferably 2.3 to 2.7 .

The relative viscosity (η _ref ) was measured at 20° C. according to DIN EN ISO 307 using, for example, a 0.5 wt% m-cresol solution.

The non-aromatic polyamide resin is 20 to 64 wt%, 20 to 60 wt%, 20 to 45 wt%, 20 to 40 wt%, 25 to 64 wt%, 30 to 64 wt%, 35 to 60% by weight, 40 to 64% by weight, or 40 to 60% by weight. When the non-aromatic polyamide resin is included in the above range, it is possible to secure a thermoplastic resin composition excellent in the balance of physical properties of workability, specific gravity, and mechanical properties, and from this, a high rigidity and high toughness molded article at a level capable of replacing metal can be provided can do.

glass fiber

In the present invention, glass fibers are included in order to increase the mechanical properties, heat resistance and dimensional stability of the polyamide resin composition.

When the inorganic glass fiber is included in the thermoplastic resin composition, mechanical properties such as tensile strength, impact strength, elongation, etc. and heat resistance properties of a molded article formed from the resin composition may be improved.

In particular, in the field of molding parts using the thermoplastic resin composition of the present invention, securing the fluidity of the resin composition is the key.

Among the glass fibers, a specific glass material is introduced to improve the moldability of the polyamide resin composition of the present invention. It was confirmed that heat resistance and mechanical properties were maintained, and processability and moldability were sufficiently secured.

The glass fiber may have, for example, a circular or non-circular cross-section, and in this case, when a circular glass fiber having a circular cross-section is used, it is preferable because it can provide an effect of replacing the metal in high stiffness and elongation values.

In addition, when flat glass fibers having a non-circular type including oval or irregular cross section are used, the appearance of the surface due to the protrusion of glass fibers or poor gas flow marks during injection molding can be reduced, and the glass for each part It is advantageous in terms of flatness and deformation as well as being able to try to commercialize it in consideration of the physical property deviation according to fiber orientation.

In the present disclosure, circular, elliptical, and irregular cross-sections are not particularly limited if they are circular, oval, and irregular cross-sections commonly recognized in the art to which the present invention pertains.

In the present description, a circular shape refers to a case in which a dimensional ratio of a main cross-sectional axis to a secondary cross-sectional axis is close to 1 or 1 while having a circular cross-section, but is not limited thereto.

In the present description, an ellipse refers to a case in which a cross section has an elliptical cross-section and a dimensional ratio of the main cross-sectional axis to the secondary cross-sectional axis is 2 to 6, 3 to 6, or 3.5 to 5.0, but is not limited thereto.

Atypical in the present description refers to a case in which, for example, a cross-section does not have a circular or oval cross-section, but is not limited thereto.

In one embodiment of the present invention, the glass fiber may be used together with other inorganic fibers, and the inorganic fiber is at least one selected from natural fibers such as carbon fiber, basalt fiber, sheep hemp or hemp.

The glass fiber of the present substrate may be a glass fiber of a circular cross-section or a non-circular cross-section having a silica content of 52 wt% or more, or 52 to 66 wt%, in which case, when product design and design change are simultaneously considered, the existing metal High rigidity, light weight, and appearance quality can be secured to a degree that can replace it.

The glass fiber has an aspect ratio expressed as a ratio (L/D) of a diameter (D) to a length (L) as an example 1:1 to 1:4, specifically 1:1 to 1:3, more specifically 1 In the case of 1: 1, the thermoplastic resin composition of the present invention can provide elongation and surface appearance quality improvement along with high strength and high toughness. In addition to performance, it is possible to provide products advantageous in terms of flatness, deformation and orientation.

In the present description, the diameter and length can be measured using a scanning electron microscope (SEM), and specifically, 20 inorganic fillers are selected using a scanning electron microscope, and an icon bar capable of measuring the diameter is selected. Measure each diameter and length using the arithmetic average, and calculate the average diameter and average length.

The D may have, for example, an average diameter of 6 to 16 μm, preferably an average diameter of 7 to 11 μm, and more preferably an average diameter of 10 to 11 μm. When the above-mentioned range is satisfied, there is an effect of improving the processability and improving the tensile strength of a molded article manufactured by molding the thermoplastic resin composition of the present invention.

According to an embodiment of the present invention, the glass fiber is, for example, 52 to 66% by weight of silica, 12 to 21% by weight of alumina, 0.5 to 24% by weight of calcium oxide, 12% by weight or less of magnesia or 8 to 12% by weight of trioxide 0 to 8% by weight of boron, 3% by weight or less of titanium dioxide, 0 to 0.6% by weight of Fe ₂ O ₃ , and 0.8% by weight or less of the total amount of sodium oxide and potassium oxide, in this case processingability, specific gravity, mechanical properties It is possible to secure a thermoplastic resin composition having an excellent balance of physical properties, and from this, it is possible to provide a high rigidity and high toughness molded article at a level capable of replacing metal.

The glass fiber is 52-66 wt% silica, 12-21 wt% alumina, 0.5-24 wt% calcium oxide, 12 wt% or less magnesia, 0-8 wt% boron trioxide, 3 wt% or less titanium dioxide, Fe ₂ O ₃ 0 to 0.6% by weight, boron oxide 0 to 8% by weight, F (fluorine) 0 to 0.7% by weight, and a total amount of sodium oxide and potassium oxide of 0.8% by weight or less, in this case processability, specific gravity, mechanical properties It is possible to secure a thermoplastic resin composition having an excellent balance of physical properties, and from this, it is possible to provide a high rigidity and high toughness molded article at a level capable of replacing metal.

The glass fiber is 58 to 62% by weight of silica, 14 to 18% by weight of alumina, 10 to 13% by weight of calcium oxide, 8 to 10% by weight of magnesia, 0.5 to 2% by weight of titanium dioxide, 0.8% by weight of sodium oxide and potassium oxide % or less, and Fe ₂ O ₃ containing 0.5 wt% or less, in this case, it is possible to secure a thermoplastic resin composition excellent in the balance of physical properties of workability, specific gravity, and mechanical properties, from which high rigidity and A high toughness molded article can be provided.

The glass fiber is 52 to 56% by weight of silica, 12 to 16% by weight of alumina, 20 to 24% by weight of calcium oxide, 1.5% by weight or less of magnesia, 1% by weight or less of titanium dioxide, and 0.8% by weight or less of the total amount of sodium oxide and potassium oxide , Fe ₂ O ₃ 0.4 wt% or less, boron oxide 5-8 wt%, and F (fluorine) 0.7 wt% or less, in this case, it is possible to secure a thermoplastic resin composition with excellent balance of properties of workability, specific gravity, and mechanical properties. and, therefrom, it is possible to provide a high rigidity and high toughness molded article at a level capable of replacing metal.

The glass fiber may be a circular glass fiber having a circular cross-section in which the total amount of calcium oxide and magnesium is 17 to 24 wt%, and in this case, it is possible to secure a thermoplastic resin composition having an excellent balance of properties of workability, specific gravity, and mechanical properties, , it is possible to provide a high rigidity and high toughness molded article at a level capable of replacing metal.

The glass fiber may be a flat glass fiber having a non-circular cross-section in which the total amount of calcium oxide and magnesium is 21 to 25% by weight, and in this case, it is possible to secure a thermoplastic resin composition excellent in the balance of physical properties of workability, specific gravity, and mechanical properties. and, therefrom, it is possible to provide a high rigidity and high toughness molded article at a level capable of replacing metal.

As a specific example, the glass fiber may be represented by the general formula AaBbCcDd.

For reference, in the case of glass fiber marketed as a product, in the case of general-purpose grades, d ≤ 1.5 in the above general formula, and in the case of ultra-high rigidity grades, 0.5 ≤ c ≤ 5, and in the case of another general-purpose grade In the above general formula, 20 ≤ c ≤ 24, 2 ≤ d ≤ 5, and 22 ≤ c+d ≤ 29, it is confirmed that the composition is different.

Contrary to what is known in the art, it is preferable to use a circular cross-section high rigidity grade or a non-circular (flat) general grade strength rather than an ultra-high rigidity grade for the thermoplastic resin composition of the present base to improve tensile strength and injection moldability. It was confirmed through the examples.

In one embodiment of the present invention, the glass fiber may be treated by glass fiber sizing compositions during fiber manufacturing or post-treatment process, and the glass fiber treating agent includes a lubricant, a coupling agent, a surfactant, and the like. .

The lubricant is mainly used to form good strands when manufacturing glass fibers, and the coupling agent enables good adhesion between the glass fibers and the polyamide resin. When used selectively, excellent physical properties can be imparted to the glass fiber-reinforced polyamide resin composition.

As a method of using the coupling agent, there are a method of directly treating the glass fiber, a method of adding it to an organic matrix, and the like, and in order to sufficiently exhibit the performance of the coupling agent, the content thereof must be appropriately selected.

Examples of the coupling agent include amine-based, acrylic and γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-(beta-aminoethyl) γ-aminopropyltriethoxysilane, γ-methacrylic oxypropyl triethoxysilane, γ-glycidoxypropyl trimethoxysilane, and the like.

The glass fiber may include 36 to 80% by weight, 40 to 70% by weight, 50 to 60% by weight, or 60 to 65% by weight of the total weight of the total resin composition. If the above-mentioned range is satisfied, high rigidity, weight reduction, and appearance quality can be secured to a degree that can replace existing metal when product design and design change are simultaneously considered.

Aromatic polyamide resin

The thermoplastic resin composition of the present invention may include an aromatic polyamide resin, if necessary.

The aromatic polyamide resin has an amorphous structure in which crystallization hardly proceeds by including an excess of phthalamide, preferably an amide derived from isophthalic acid, for example. In this case, while providing compatibility with the non-aromatic polyamide resin, the above-described glass fiber provides a bonding site that can be well added, thereby maximizing the glass fiber input effect.

In the present description, the aromatic polyamide resin refers to a resin in which amorphous content is not simply included, but occupies substantially the majority, for example, in which the amorphous content is 90% by weight or more.

In addition, the aromatic polyamide resin may have a glass transition temperature measured by DSC of, for example, 106 to 150°C, preferably 106 to 133°C, and more preferably 117 to 120°C. When the above-mentioned range is satisfied, more excellent heat resistance can be provided along with processability, so that there is an effect of improving the tensile strength of a molded article manufactured by molding the thermoplastic resin composition of the present invention.

The aromatic polyamide resin may be PA MACM12, PA PACM12, a mixture or copolyamide thereof, or an amorphous resin selected from polyhexamethylene isophthalamide (PA6I), PAMXDI, and PA6I/MXDI.

The aromatic polyamide resin may be, for example, polyhexamethylene isophthalamide (PA6I).

The aromatic polyamide resin may be included in an amount of 0 to 30% by weight, 30% by weight or less, 4 to 25% by weight, or 4 to 20% by weight of the total weight of the total resin composition. When the aromatic polyamide resin is included in the above range, excellent mechanical properties, particularly, relatively excellent rigidity and processability may be realized.

Let the glass transition temperature (Tg) of the non-aromatic polyamide resin be a, the glass transition temperature (Tg) of the aromatic polyamide resin be b, and the melting temperature (Tm) of the non-aromatic polyamide resin is c And, if the silica content included in the glass fiber is d, the following Equations 1 to 3 may be satisfied.

[Equation 1]

4.8a ≤ c ≤ 5.3a

[Equation 2]

2d ≤ b ≤ 2.5d

[Equation 3]

a < b < c

(In the above equations, a, b, c, and d satisfy 50≤a≤60, 106≤b≤150, 240≤c≤265, and 52≤d≤66.)

additive

In one embodiment of the present invention, the thermoplastic resin composition may include, for example, at least one selected from a flame retardant, a nucleating agent, a heat stabilizer, a light stabilizer, a lubricant, an antioxidant, and a thickener.

As long as the flame retardant according to the present invention does not adversely affect the thermoplastic resin composition of the present invention, various known types may be used, and Clariant_Exolit-OP-1230 may be typically used among commercially available materials.

As long as the nucleating agent according to the present invention does not adversely affect the thermoplastic resin composition of the present invention, various known types may be used, and BRUGGOLEN_P22 may be typically used among commercially available materials.

As long as the thickener does not adversely affect the thermoplastic resin composition of the present invention, a variety of known thickeners may be used, and Xibond250 may be typically used among commercially available materials.

As long as the antioxidant does not adversely affect the thermoplastic resin composition of the present invention, various known types may be used.

The lubricant according to the present invention may be a lignite-derived mineral wax or an olefin-based wax, and provides the thermoplastic resin composition with a role of maintaining excellent releasability and injection property.

The olefin wax is a polymer having a low melt viscosity and may be an oily solid having sliding properties and plasticity. For example, it may be at least one selected from polyethylene wax and polypropylene wax, and a commercially available product may be used.

The mineral wax has a high melting point and hardness, so it has thermal stability and may be at least one selected from OP and E grades, and a commercially available product may be used as long as it follows the definition of the present invention.

In one embodiment of the present invention, the additive may be included in an amount of, for example, 5 wt% or less, 0.05 to 3 wt%, preferably 0.01 to 2 wt%, based on the total weight of the total thermoplastic resin composition. When the above-mentioned range is satisfied, excellent releasability and injection property can be sufficiently provided.

In addition, if necessary, processing aids, pigments, colorants, etc. may be further included.

Thermoplastic resin composition

The glass fiber-reinforced polyamide resin composition according to the present invention is characterized in that, for example, the tensile strength according to the standard measurement ISO 527 is 270 MPa or more.

The tensile strength may be measured under a mark section (elongation measurement) of 50 mm in a specimen having a thickness of 4 mm and a width of 10 mm.

The thermoplastic resin composition may have a normal temperature tensile strength of 300 MPa or more based on standard measurement ISO 527, and a high temperature tensile strength of 180 MPa or more measured at 90°C. In this case, mechanical properties, in particular, properties having relatively excellent rigidity and workability may be realized.

The thermoplastic resin composition may satisfy Equation 1 below in terms of the reduction rate (%) of properties calculated from the normal temperature (23° C.) tensile strength and the high temperature (90° C.) tensile strength based on standard measurement ISO 527. In this case, mechanical properties, in particular, properties having relatively excellent rigidity and workability may be realized.

[Equation 1]

34 ≤ 100 - (high temperature measurement/room temperature measurement x 100) ≤ 44

The calculated value of Equation 1 may be, for example, 34 to 44, preferably 34.5 to 43.9.

The thermoplastic resin composition of the present invention has a tensile strength at room temperature based on standard measurement ISO 527, a, an elongation at 50 mm in a marked section based on ISO 527, b, and a thickness of 3.2 mm according to ASTM D638 Type 1, When c is the difference between the flow direction (MD) and the orthogonal direction (TD) of the glass fiber measured at a speed of 5 mm/min in a specimen with a width of 12.7 mm, the calculated value of a+b/c is 2.88 or more, 2.88 to 4.0 , or 2.9 to 3.8. In this case, compared to the conventional polyamide composite material, the impact strength, elongation, workability, etc. are equal or higher, but the tensile strength is greatly improved, and it may be particularly suitable for replacing metal material parts with light weight.

As a specific example, the thermoplastic resin composition may include 31 to 41 wt% of the non-aromatic polyamide resin; 4 to 8 wt% of the aromatic polyamide resin; 51 to 55% by weight of the silica-reinforced glass fibers; And when it contains 0.2 to 6 wt% of a flame retardant, impact strength, elongation and workability are equal to or greater than that of a conventional polyamide composite material, but the tensile strength is greatly improved and it is particularly suitable for replacing metal material parts with light weight. .

In addition, the thermoplastic resin composition of the present invention is preferably 40 to 60% by weight of the non-aromatic polyamide resin; 40 to 60% by weight of the glass fiber; and 0 to 5% by weight of additives, the specific gravity is 1.45 to 1.70 g/cm ³ , the impact strength is 18.5 to 22.5 kJ/m ² , and the elongation at 50 mm in the marked section according to ISO 527 is 2.5 to 3.3 %, and when the specific gravity is 1.45 to 1.70 g/cm ³ , the impact strength, elongation, and workability are equal to or higher than that of the conventional polyamide composite material, but the tensile strength is greatly improved and it is suitable for replacing metal parts with light weight It is advantageous to provide a thermoplastic resin composition.

In addition, the thermoplastic resin composition of the present invention is preferably 30 to 60% by weight of the non-aromatic polyamide resin; 40 to 70% by weight of the glass fiber; And 0 to 5% by weight of additives; containing, the specific gravity of 1.45 to 1.85 g / cm ³ At the same time, the impact strength is 18.5 to 22.5 kJ / m ² , the elongation at 50mm in the marked section based on ISO 527 is 1.9 to 3.3 %, there is an advantage of providing a thermoplastic resin composition suitable for replacing metal material parts with significantly improved tensile strength and light weight while having equal or greater impact strength, elongation and workability, etc. compared to conventional polyamide composite materials.

In addition, the thermoplastic resin composition of the present invention is preferably 25 to 45% by weight of the non-aromatic polyamide resin; 4 to 25% by weight of the aromatic polyamide resin; 50 to 60% by weight of the glass fiber; and 0 to 5% by weight of additives, and when the elongation at 50mm in the marked section according to ISO 527 is 2.3 to 2.9%, the impact strength, elongation, and workability are equal to or higher than that of the conventional polyamide composite material. There is an advantage of providing a thermoplastic resin composition that has significantly improved tensile strength and is suitable for replacing metal parts with a light weight.

In addition, the thermoplastic resin composition of the present invention is preferably 20 to 36% by weight of the non-aromatic polyamide resin; 4 to 20% by weight of the aromatic polyamide resin; 60% by weight of the glass fiber; And 0 to 5% by weight of additives; and, the tensile strength at room temperature according to the standard measurement ISO 527 is 270 MPa or more, and the elongation at 50mm in the marked section according to ISO 527 is 2.2 to 2.5%, according to ASTM D638 Type 1 When the glass fiber orientation measured at a rate of 5 mm/min on a specimen having a thickness of 3.2 mm and a width of 12.7 mm based on the flow direction (MD) is 225 to 250 MPa and the perpendicular direction (TD) is 120 to 165 MPa, There is an advantage of providing a thermoplastic resin composition suitable for replacing metal parts with significantly improved tensile strength and light weight while having equal or greater impact strength, elongation and workability compared to conventional polyamide composite materials.

Method for producing a thermoplastic resin composition

The thermoplastic resin composition according to the present invention may be prepared by a method known in the art. For example, the thermoplastic resin composition may be prepared in the form of pellets by melt-extruding a mixture of each component and other additives in an extruder, and the pellets may be used for injection and extrusion molding.

The method for producing the thermoplastic resin composition shares all the technical characteristics of the aforementioned thermoplastic resin composition. Therefore, a description of the overlapping portion will be omitted.

In one embodiment of the present invention, the pellets are extruded at a temperature of 280 to 310 ℃, wherein the temperature means a temperature set in the cylinder.

The extrusion kneader is not particularly limited if it is an extrusion kneader commonly used in the art to which the present invention belongs, and may preferably be a twin-screw extrusion kneader.

The temperature of the mold during injection is preferably in the range of 90 to 150 ℃, preferably 100 to 120 ℃. If the mold temperature is less than 90 ℃, the appearance characteristics may be reduced, and it is difficult to expect the effect of increasing crystallinity and physical properties according to annealing. and can greatly reduce productivity in terms of mass production.

The injection process may be performed using, for example, an injection machine having a hopper temperature or a nozzle temperature of 290°C to 305°C, respectively.

The method for preparing the thermoplastic resin composition of the present invention includes, for example, a non-aromatic polyamide resin; glass fiber; and optionally melt-kneading and extruding a resin composition including a polyphthalamide-based resin and an additive.

As a specific example, the method for preparing the thermoplastic resin composition includes 20 to 64 wt% of a non-aromatic polyamide resin having a glass transition temperature (Tg) of 50 to 60 °C and a melting temperature (Tm) of 240 to 265 °C; 36 to 80% by weight of glass fibers having a silica content of 52 to 66% by weight; and 0 to 30 wt% of the aromatic polyamide resin; melt-kneading and extruding;

<Molded article>

According to another embodiment of the present invention, there is provided a molded article made of the above-described thermoplastic resin composition.

The molded article may be, for example, a high-strength, high-toughness, lightweight automobile part.

As another example, the molded article may be a metal replacement part for an automobile seat belt, and as another example, a metal replacement part for a vehicle information guide display and instrument panel, and a digital cockpit.

The molded article may have a tensile strength of, for example, 270 MPa or more, preferably 300 MPa or more based on standard measurement ISO 527.

In addition, the molded article may have a high-temperature tensile strength of 180 MPa or more measured at 90° C. based on standard measurement ISO 527.

Therefore, the thermoplastic resin composition of the present invention can be used as a material for molded articles requiring excellent moldability, heat resistance, high strength and high toughness.

The thermoplastic resin composition of the present invention can be applied in various ways as long as it is a use that requires high strength, high toughness, and lightweight parts. For example, it can be used not only for automobile parts, but also for electrical and electronic parts, office equipment parts, and the like.

In addition, in describing the thermoplastic resin composition and molded article of the present disclosure, other conditions or equipment not explicitly described may be appropriately selected within the range commonly practiced in the art, and it is specified that there is no particular limitation.

Hereinafter, embodiments of the present invention will be described in detail so that those of ordinary skill in the art can easily carry out the present invention. However, the present invention may be embodied in various different forms and is not limited to the embodiments described herein.

[Example]

Non-aromatic polyamide resin (A), glass fiber (B), polyphthalamide-based resin (C), nucleating agent (D), flame retardant (E), thickener (F) used in Examples and Comparative Examples of the present invention Specifications are as follows.

(A) Non-aromatic polyamide resin

(A-1) PA66 (amorphous ratio 50-60 wt%, Tg 50-60 ° C, Tm 263 ° C, relative viscosity 2.4)

(A-2) PA66 (amorphous ratio 50-60 wt%, Tg 50-60 ° C, Tm 270 ° C, relative viscosity 2.7)

(A-3) PA6 (amorphous ratio 50-60 wt%, Tg 45℃, Tm 220℃, relative viscosity 2.5)

(A-4) PA46 (amorphous ratio 20-30 wt%, Tm 295℃)

(B) Glass fiber

(B-1) rigid glass fiber (circular cross-section, aspect ratio (L/D) 1:1, diameter (D): 10 um): silica 58-62 wt%, alumina 14-18 wt%, calcium oxide 10-13 wt%, magnesia 8 to 10 wt%, titanium dioxide 0.5 to 2 wt%, Fe ₂ O ₃ 0.5 wt% or less, and a total amount of sodium oxide and potassium oxide 0.8 wt% or less

(B-2) rigid glass fiber (circular cross-section, aspect ratio (L/D) 1:1, diameter (D): 10 um): Silica 62-66 wt%, alumina 18-21 wt%, calcium oxide 0.5-5 wt%, magnesia 8-12 wt%, titanium dioxide 0.4-3 wt%, Fe ₂ O ₃ 0.1-0.6 wt%, and sodium oxide 0.1 to 0.8% by weight of the total amount of potassium peroxide

(B-3) Universal glass fiber of circular cross section (aspect ratio (L/D) 1:1, diameter (D): 10 um): Silica 57-61 wt%, alumina 11-15 wt%, calcium oxide 20-24 wt%, magnesia 2-5 wt%, titanium dioxide 1.0 wt% or less, Fe ₂ O ₃ 0.5 wt% or less, and sodium oxide and oxidation 0.8% by weight or less of the total amount of potassium

(B-4) Carbon fiber (Toray's product name T300)

(B-5) Stainless steel fiber (Composite material, product name GR75C16-E4_EN_LR)

(B-6) Wollastonite (Koch, product name: XA-600T)

(B-7) rigid glass fiber (non-circular cross-section, aspect ratio (L/D) 1:3, flat type, diameter (D): 8 um) : silica 58-62 wt%, alumina 14-18 wt%, oxide 10 to 13 wt% of calcium, 8 to 10 wt% of magnesia, 0.2 to 2 wt% of titanium dioxide, 0.6 wt% or less of Fe ₂ O ₃ , and 0.8 wt% or less of the total amount of sodium oxide and potassium oxide

(B-8) General purpose glass fiber of non-circular cross-section (aspect ratio (L/D) 1:4, flat type, diameter (D): 7um): silica 52-56 wt%, alumina 12-16 wt%, calcium oxide 20 to 24 wt%, magnesia 1.5 wt% or less, titanium dioxide 1.0 wt% or less, B ₂ O ₃ 5 to 8 wt%, F (fluorine) 0.7 wt% or less, and the total amount of sodium oxide and potassium oxide 0.8 wt% or less

(B-9) Milled GF: Nittobo's product name EPH-80M

(B-10) Glass Bead

(C) polyphthalamide-based resin

(C-1) amorphous 6I (amorphous 90% by weight or more, Tg 106-150℃)

(C-2) amorphous 6I6T (70:30) (amorphous less than 90% by weight, Tg 115℃ or higher)

(D) Nucleating agent: BRUGGOLEN, product name P22

(E) Flame retardant: Clariant, product name Exolit-OP-1230

(F) thickener: Product name Xibond250

Examples 1 to 3, and Comparative Examples 1 to 6

Each of the components was added according to the contents shown in Table 1 below, and melt-kneaded in a twin-screw extruder heated to 280 to 310° C. to prepare a resin composition in a pellet state.

The prepared pellets were dried at a temperature of 120 ° C. for 4 hours or more, and then the mold temperature condition during injection was 120 ° C. A specimen for evaluation of mechanical properties was prepared using a screw injection machine set at a hopper temperature of 290 ° C to a nozzle temperature of 305 ° C. The physical properties of the prepared specimen having a thickness of 4 mm, a width of 10 mm and a mark section (elongation measurement) of 50 mm were measured in the following manner and are shown in Table 1 below.

*Specific gravity (unit g/cm ³ ): It was measured according to ISO 1183.

*Tensile strength (unit MPa): was measured at room temperature (23 ℃) and high temperature (90 ℃) in accordance with ISO 527.

* Elongation (unit %): Measured according to ISO 527.

* Impact strength (unit KJ/m ² ): It was measured according to ISO 179 (charpy).

*Extrusion workability: The melt strength and single yarn were visually observed, and it was expressed as very good (◎), good (○), poor (Δ), and poor (X) according to melt strength and single yarn or not.

*Injection moldability: The appearance of the injection molded product was observed with the naked eye, and it was expressed as very good (◎), good (○), poor (Δ), poor (X), or scored within 1 to 15. For reference, the lower the value, the better the appearance.

division Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 A-1 60 50 40 40 45 60 40 40 65 B-1 40 50 60 - - - - - - B-2 - - - - - - 50 40 - B-3 - - - 60 40 - - - - B-4 - - - - - 40 10 20 30 B-5 - - - - - - - - 5 B-6 - - - - 15 - - - - importance 1.45 1.55 1.70 1.70 1.71 1.23 1.63 1.59 1.44 room temperature tensile strength 270 292 311 260 190 251 269 213 210 impact strength 18.5 22.5 21.5 19.0 7.0 8.7 10.9 9.4 8.0 elongation 3.3 2.7 2.5 2.0 1.7 1.8 1.5 0.8 1.2

(In Table 1, the content of A-1, A-2, A-3, A-4, B-1, B-2, B-3, B-4, B-5, B-6 is the total amount of the thermoplastic resin. % by weight based on 100% by weight.)

As shown in Table 1, Examples 1 to 3 containing the non-aromatic polyamide resin and glass fiber, which are essential components according to the present invention, in an appropriate composition, have a specific gravity of 1.45 to 1.70 g/cm ³ , and a tensile strength of 270 MPa or more , the elongation is 2.5 to 3.3%, and the impact strength is 18.5KJ/m ² or more, confirming the balance of high strength, high toughness and specific gravity.

On the other hand, in the case of Comparative Example 1 using general-purpose glass fiber as the glass fiber, it was confirmed that the tensile strength was lowered.

In addition, in the case of Comparative Example 2, in which general-purpose glass fibers and wollastonite were mixed as glass fibers, it was confirmed that not only the tensile strength was poor, but also the elongation and impact strength were also reduced.

In addition, in the case of Comparative Example 3 using carbon fiber instead of glass fiber as the glass fiber, it was confirmed that mechanical properties such as tensile strength and impact strength were insufficient.

In addition, in the case of Comparative Example 4 in which an appropriate glass fiber was used as the glass fiber, but some carbon fibers were mixed there, it was confirmed that the elongation and impact strength were lowered, and in Comparative Example 5 in which the carbon fiber blending amount was further increased, the elongation It was confirmed that the tensile strength as well as the impact strength and the impact strength were inferior.

Even in Comparative Example 6, in which carbon fiber and stainless steel fiber were mixed instead of glass fiber as glass fiber, mechanical properties such as tensile strength, elongation and impact strength were found to be insufficient overall.

Examples 4 to 6 and Comparative Examples 7 to 8

A specimen was prepared in the same manner as in the preparation method of Example 1, except that each component was mixed according to the contents shown in Table 2 below, and the physical properties of the prepared specimen were measured in the same manner as in Example 1, It is shown in Table 2 below.

division Example 4 Example 5 Example 6 Comparative Example 7 Comparative Example 8 A-1 36 20 - - - A-2 - - 32 - - A-3 - - - - 40 A-4 - - - 34 - B-1 60 60 60 - - B-2 - - - 50 60 C-1 4 20 8 6 - room temperature tensile strength 310 303 315 275 285 elongation 2.5 2.3 2.6 1.8 2.3 injection moldability 6 4 5 8 7 Extrusion workability ◎ ○ ◎ Х △

(A-1, A-2, A-3, A-4, B-1, B-2, B-3, B-4, B-5, B-6, C-1 and C in Table 2 above The content of -2 is % by weight based on 100% by weight of the total thermoplastic resin.)

As shown in Table 2 above, Examples 4 to 6 containing the polyphthalamide-based resin in an appropriate composition in the non-aromatic polyamide resin and glass fiber, which are essential components according to the present invention, had a tensile strength of 303 MPa or more, and an elongation of 2.3 To 2.6%, the appearance quality of the molded article was excellent or very excellent, and thus it was possible to confirm the balance of physical properties of high strength, high toughness, workability and injection moldability.

On the other hand, in the case of Comparative Example 7 using a non-aromatic polyamide resin having inadequate glass transition temperature and melting temperature, it was confirmed that injection moldability, compression workability, tensile strength, and elongation were generally lowered.

In addition, in the case of Comparative Example 8, in which a non-aromatic polyamide resin having an inappropriate glass transition temperature and melting temperature and an inappropriately rigid glass fiber were mixed, injection moldability and tensile strength were poor, and extrusion workability and elongation were also poor.

Examples 7 to 9 and Comparative Examples 9 to 18

A specimen was prepared in the same manner as in the preparation method of Example 1, except that each component was mixed according to the contents shown in Table 3 below, and the physical properties of the prepared specimen were measured in the same manner as in Example 1, It is shown in Table 3 below.

For reference, the rate of physical property degradation (unit %) shown in Table 3 below is measured by measuring the tensile strength at room temperature (23 ° C.) and then the degree of decrease in high temperature properties compared to room temperature after measuring high temperature (90 ° C) was calculated by Equation 1 below.

[Equation 1]

100 - (high temperature measurement/room temperature measurement x 100)

division Example 7 Example 8 Example 9 Comparative Example 9 Comparative Example 10 Comparative Example 11 Comparative Example 12 Comparative Example 13 Comparative Example 14 Comparative Example 15 Comparative Example 16 Comparative Example 17 Comparative Example 18 A-1 31 37 40 - 60 12 - - 33.8 32 34 33.8 35 A-2 - - - - - - - - - - - - - A-3 - - - 34 - - - - - - - - - A-4 - - - - - - - 40 - - - - - B-1 65 55 60 60 35 60 60 60 60 60 60 60 60 C-1 4 8 - 6 5 - - - 6 5 5 6 5 C-2 - - - - - 28 40 - - - - - - D - - - - - - - - 0.2 2 - - - E - - - - - - - - - - One F - - - - - - - - - - - 0.2 5 room temperature tensile strength 300 320 306 285 240 276 270 270 295 270 260 289 work impossible high temperature tensile strength 180 180 200 - - 115 180 - 165 - 130 151 injection moldability - - - - ◎ - ◎ - - - - - - Extrusion workability ◎ ◎ ○ ○ ○ ○ △ Х ○ △ Х △ Х property degradation rate 40 43.75 34.64 - - 58.33 33.33 - 44.06 - 47.75 - -

(A-1, A-2, A-3, A-4, B-1, B-2, B-3, B-4, B-5, B-6, C-1 and C in Table 3 above The content of -2 is % by weight based on 100 parts by weight of the total thermoplastic resin, and the contents of D, E, and F are parts by weight based on 100 parts by weight of the total thermoplastic resin.)

As shown in Table 3 above, non-aromatic polyamides, which are essential components according to the present invention, are very good (◎), good (○), poor (Δ), and poor (X) polyphthalamide-based resins and additives in the resin and glass fiber Examples 7 to 9 containing in an appropriate composition have a room temperature tensile strength of 300 to 320 MPa, a high temperature tensile strength of 180 MPa or more, excellent extrusion processability, and a decrease in physical properties of 40% or less. The physical property balance could be confirmed.

On the other hand, in the case of Comparative Example 9, in which a small amount of a non-aromatic polyamide resin having inadequate glass transition temperature and melting temperature was used, it was confirmed that injection moldability and room temperature tensile strength were lowered.

In addition, in the case of Comparative Example 10 in which a small amount was used even when appropriate glass fibers were used, it was confirmed that the tensile strength at room temperature was poor.

In addition, in Comparative Examples 11 to 12, in which an inappropriate polyphthalamide-based resin was blended while using a small amount of an appropriate non-aromatic polyamide resin, extrusion processability and room temperature tensile strength were poor or room temperature tensile strength was poor depending on the blending amount of the polyphthalamide-based resin. It was confirmed that the strength, high-temperature tensile strength, and rate of deterioration of properties were poor, and in Comparative Example 14, in which a non-aromatic polyamide resin having an inappropriate glass transition temperature and melting temperature was used while using a small amount of an appropriate non-aromatic polyamide resin, in the case of Comparative Example 14, high-temperature tensile strength It was confirmed that the strength and property deterioration rate were poor.

In addition, in the case of Comparative Example 13 using a non-aromatic polyamide resin having an inappropriate glass transition temperature and melting temperature, extrusion processability and room temperature tensile strength were poor.

In addition, Comparative Examples 15 to 18 examine the effect of adding an additive while using a small amount of a non-aromatic polyamide resin having an inappropriate glass transition temperature and melting temperature. It was confirmed that the tensile strength was poor, and in the case of Comparative Example 16 in which a flame retardant was added, it was confirmed that extrusion processability, room temperature tensile strength, high temperature tensile strength, and the rate of deterioration of physical properties were generally decreased, and in Comparative Example 17 in which a small amount of a thickener was added It was confirmed that the extrusion processability deteriorated, and the high temperature tensile strength and property deterioration rate were poor. In Comparative Example 18, in which an excessive thickener was added, not only the extrusion processability was poor, but also the tensile strength and the rate of deterioration of properties were confirmed to be impossible to measure, etc. It can be seen that the introduction of additives such as a heat-resistant stabilizer and a flame retardant has little effect on the improvement of high temperature and deteriorates the extrusion processability.

Examples 10 to 13 and Comparative Examples 19 to 22

A specimen was prepared in the same manner as in the preparation method of Example 1, except that each of the components was mixed according to the contents shown in Table 4, and the physical properties of the prepared specimen were measured in the same manner as in Example 1. It is shown in Table 4 below.

For reference, the MD orientation and TD orientation shown in Table 4 below are the glass fiber orientation (unit MPa) for MD (flow direction) and TD (perpendicular direction), respectively, based on ASTM D638 Type 1 Physical properties according to orientation under the following conditions was measured, the specimen thickness was 3.2 mm, the specimen width was 12.7 mm, the marked section (elongation measurement) was 50 mm, and the measurement speed was 5 mm/min.

division Example 10 Example 11 Example 12 Example 13 Comparative Example 19 Comparative Example 20 Comparative Example 21 Comparative Example 22 A-1 36 20 34 40 40 32 20 40 B-1 60 - - - - 50 55 - B-3 - - - - 60 - - - B-7 - 60 - - - - - - B-8 - - 60 60 - - - 50 B-9 - - - - - 10 - 10 B-10 - - - - - - 5 - C-1 4 20 6 - - 8 20 - MD orientation 225 235 250 240 190 205 210 230 TD orientation 120 140 165 150 95 100 110 125 room temperature tensile strength 310 300 305 300 260 280 275 273 elongation 2.5 2.2 2.5 2.3 2.0 2.8 2.9 2.6

(A-1, A-2, A-3, A-4, B-1, B-2, B-3, B-4, B-5, B-6, C-1 and C in Table 4 above The content of -2 is % by weight based on 100% by weight of the total thermoplastic resin.)

As shown in Table 4, the non-aromatic polyamide resin and the glass fiber, which are essential components according to the present invention, contain the polyphthalamide-based resin, but the glass fiber is divided by cross-sectional shape and as a result of additional experiments, the non-aromatic polyamide resin and Example 10 in which the glass fiber contains a polyphthalamide-based resin in an appropriate composition range, wherein the glass fiber has a circular cross-section, and Examples 11 to 12 in which the glass fiber has a non-circular non-circular cross-section By minimizing the deviation of MD (flow direction) and TD (perpendicular direction) physical properties according to the cross-sectional shape and aspect ratio, the tensile strength at room temperature was 300 to 310 MPa, and the elongation was 2.2 to 2.5%, confirming the balance between high toughness and workability. .

At this time, even in the case of Example 13 without the polyphthalamide-based resin, the MD (flow direction) and TD (perpendicular direction) physical property deviations were minimized depending on the cross-sectional shape and cross-sectional ratio of the Lee fibers, so that the tensile strength at room temperature was 300 MPa, As the elongation was 2.3%, it was possible to confirm the physical property balance of high toughness and workability.

On the other hand, in the case of Comparative Example 19 using general-purpose glass fibers in a circular cross section, it was confirmed that the orientation, tensile strength, and elongation of the glass fibers were generally lowered.

In addition, in the case of Comparative Examples 20 to 22 having inappropriate types, including glass beads, even if appropriate glass fibers are used, the orientation and tensile strength of the glass fibers are poor, or even though the orientation of the glass fibers is appropriate, the tensile strength is lowered. could confirm that

In conclusion, when the non-aromatic polyamide resin having a specified glass transition temperature and melting temperature disclosed in the present invention is reinforced by using glass fibers, aromatic polyamide resins, additives, etc. in specific compositions, the composition and shape of glass fibers are controlled. As a result, it was confirmed that the resin was suitable for replacement moldings for lightweight metal parts by realizing the balance of the physical properties of the resin with respect to workability and specific gravity and rigidity.

Claims (16)

20 to 64 wt% of a non-aromatic polyamide resin having a glass transition temperature (Tg) of 50 to 60 °C and a melting temperature (Tm) of 240 to 265 °C;
36 to 80% by weight of glass fibers having a silica content of 52 to 66% by weight; and
Contains 0 to 30% by weight of aromatic polyamide resin;
A thermoplastic resin composition having a tensile strength of 270 MPa or more at room temperature according to standard measurement ISO 527. According to claim 1,
Let the glass transition temperature (Tg) of the non-aromatic polyamide resin be a, the glass transition temperature (Tg) of the aromatic polyamide resin be b, and the melting temperature (Tm) of the non-aromatic polyamide resin is c and, when the silica content contained in the glass fiber is d, the following Equations 1 to 3 are satisfied.
[Equation 1]
4.8a ≤ c ≤ 5.3a
[Equation 2]
2d ≤ b ≤ 2.5d
[Equation 3]
a < b < c
(In the above equations, a, b, c, and d satisfy 50≤a≤60, 106≤b≤150, 240≤c≤265, and 52≤d≤66.) According to claim 1,
The glass fiber is 52-66 wt% silica, 12-21 wt% alumina, 0.5-24 wt% calcium oxide, 12 wt% or less magnesia, 0-8 wt% boron trioxide, 3 wt% or less titanium dioxide, Fe ₂ O ₃ 0 to 0.6% by weight, boron oxide 0 to 8% by weight, F (fluorine) 0 to 0.7% by weight, and a thermoplastic resin composition comprising 0.8% by weight or less of the total amount of sodium oxide and potassium oxide. According to claim 1,
The glass fiber is 58 to 62% by weight of silica, 14 to 18% by weight of alumina, 10 to 13% by weight of calcium oxide, 8 to 10% by weight of magnesia, 0.5 to 2% by weight of titanium dioxide, 0.8% by weight of sodium oxide and potassium oxide % or less, and Fe ₂ O ₃ Thermoplastic resin composition comprising 0.5 wt% or less. According to claim 1,
The glass fiber is 52 to 56% by weight of silica, 12 to 16% by weight of alumina, 20 to 24% by weight of calcium oxide, 1.5% by weight or less of magnesia, 1% by weight or less of titanium dioxide, and 0.8% by weight or less of the total amount of sodium oxide and potassium oxide , Fe ₂ O ₃ A thermoplastic resin composition comprising 0.4 wt% or less, 5-8 wt% boron oxide, and 0.7 wt% or less of F (fluorine). According to claim 1,
The glass fiber is a thermoplastic resin composition, characterized in that the total amount of calcium oxide and magnesium is a circular glass fiber having a circular cross section of 17 to 24% by weight. According to claim 1,
The glass fiber is a thermoplastic resin composition, characterized in that the total amount of calcium oxide and magnesium is a flat glass fiber having a non-circular cross section of 21 to 25% by weight. According to claim 1,
The glass fiber has an aspect ratio expressed as a ratio (L/D) of a diameter (D) to a length (L) of 1:1 to 1:4, wherein the diameter (D) has an average diameter of 6 to 16 μm. A thermoplastic resin composition. According to claim 1,
The non-aromatic polyamide resin is polyhexamethylene adipamide (PA66), and the thermoplastic resin composition is included in an amount of 25 to 60 wt% based on the total weight of the thermoplastic resin composition. According to claim 1,
The aromatic polyamide resin is polyhexamethylene isophthalamide (PA6I), and the thermoplastic resin composition is included in an amount of 4 to 25 wt% based on the total weight of the thermoplastic resin composition. According to claim 1,
The thermoplastic resin composition further comprises at least one additive selected from a flame retardant, a nucleating agent, a heat stabilizer, a light stabilizer, a lubricant, an antioxidant and a thickener in an amount of 5 wt% or less based on the total weight of the thermoplastic resin composition. resin composition. According to claim 1,
The thermoplastic resin composition has a tensile strength at room temperature based on standard measurement ISO 527, a, and an elongation at 50 mm in the marked section based on ISO 527, b, and has a thickness of 3.2 mm and a width of 12.7 based on ASTM D638 Type 1. Thermoplastic resin composition, characterized in that the calculated value of a+b/c is 2.88 or more when c is the difference between the flow direction (MD) and the perpendicular direction (TD) of the glass fibers measured at a speed of 5 mm/min on a mm specimen . According to claim 1,
The thermoplastic resin composition is a thermoplastic resin composition, characterized in that the rate of decrease in physical properties (%) calculated from the tensile strength at room temperature (23 ℃) and the tensile strength at high temperature (90 ℃) based on standard measurement ISO 527 satisfies Equation 1 below.
[Equation 1]
34 ≤ 100 - (high temperature measurement/room temperature measurement x 100) ≤ 44 20 to 64 wt% of a non-aromatic polyamide resin having a glass transition temperature (Tg) of 50 to 60 °C and a melting temperature (Tm) of 240 to 265 °C; 36 to 80% by weight of glass fibers having a silica content of 52 to 66% by weight; and 0 to 30 wt% of an aromatic polyamide resin; melt-kneading and extruding;
A method for producing a thermoplastic resin composition, characterized in that the tensile strength at room temperature is 270 MPa or more based on standard measurement ISO 527. A molded article prepared from the thermoplastic resin composition of any one of claims 1 to 13. 16. The method of claim 15,
The molded article is a molded article, characterized in that the high rigidity, high toughness and lightweight automobile parts.