KR20230166753A - Thermoplastic resin composition and molded product manufactured by the same - Google Patents

Abstract

(A) 30 to 65% by weight of polyamide 6 resin; (B) 5 to 30% by weight of a polyamide copolymer resin containing a component derived from isophthalic acid or m-xylylenediamine; and (C) 25 to 60% by weight of glass fiber, wherein the weight ratio of the (A) polyamide 6 resin and (B) the polyamide copolymer resin containing a component derived from isophthalic acid or m-xylylenediamine is A thermoplastic resin composition having a ratio of 6:4 to 9:1 is provided.

Description

Thermoplastic resin composition and molded article manufactured therefrom {THERMOPLASTIC RESIN COMPOSITION AND MOLDED PRODUCT MANUFACTURED BY THE SAME}

The present invention relates to thermoplastic resin compositions and molded articles manufactured therefrom.

Thermoplastic resins, which have recently been widely used in electrical and electronics, automobiles, building materials, and leisure goods, are rapidly replacing existing glass and metal. Accordingly, the demand for thermoplastic resins that can achieve excellent fluidity, impact resistance, and heat resistance is increasing.

In particular, with the recent trend of reducing the weight of automobiles, the metal bonding performance of thermoplastic resins has been improved, and the number of cases of replacing metals with thermoplastic resins is increasing. For example, U.S. Patent Publication No. US 2017/0029615 discloses improving metal bonding strength by blending polyester or polycarbonate with glass fiber-reinforced polybutylene terephthalate resin.

Among thermoplastic resins, polyamide resin provides excellent heat resistance and moldability, so it is useful as a thermoplastic resin composition used in automobile parts or electrical appliances. Polyamide resin is expected to be able to further improve metal bonding properties compared to resins that blend conventional polybutylene terephthalate resin with polyester or polycarbonate.

The purpose of the present invention is to provide a thermoplastic resin composition with excellent mechanical properties and metal bonding properties using a polyamide resin of a specific structure.

According to one embodiment, (A) 30 to 65% by weight of polyamide 6 resin; (B) 5 to 30% by weight of a polyamide copolymer resin containing a component derived from isophthalic acid or m-xylylenediamine; and (C) 25 to 60% by weight of glass fiber, wherein the weight ratio of the (A) polyamide 6 resin and (B) the polyamide copolymer resin containing a component derived from isophthalic acid or m-xylylenediamine is 6. : 4 to 9 : 1, a thermoplastic resin composition is provided.

The weight ratio of (A) the polyamide 6 resin and (B) the polyamide copolymer resin containing a component derived from isophthalic acid or m-xylylenediamine may be 6:4 to 8:2.

The (A) polyamide 6 resin may have an intrinsic viscosity of 1.9 to 3.2 dl/g.

The (B) polyamide copolymer resin containing a component derived from isophthalic acid or m-xylylenediamine may have an intrinsic viscosity of 0.6 to 1.1 dl/g.

The average particle diameter of the (C) glass fiber may be 1 to 20 ㎛, and the average length before processing may be 1 to 10 mm.

The thermoplastic resin composition may further include (D) maleic anhydride-modified ethylene-alpha-olefin copolymer.

The weight average molecular weight of the (D) maleic anhydride-modified ethylene-alpha-olefin copolymer may be 10,000 to 1,000,000 g/mol.

The (D) maleic anhydride-modified ethylene-alpha-olefin copolymer may be a maleic anhydride-modified ethylene-1-octene copolymer.

The thermoplastic resin composition may further include at least one additive selected from flame retardants, nucleating agents, coupling agents, plasticizers, impact modifiers, lubricants, mold release agents, heat stabilizers, antioxidants, ultraviolet stabilizers, pigments, and dyes.

In another embodiment, a molded article manufactured from the thermoplastic resin composition is provided.

The molded product may have a metal bonding force of 50 MPa or more to an aluminum metal specimen measured by the Type A method according to the ISO 19095 standard.

The molded product may have a notched Izod impact strength of 10 kgf·cm/cm or more as measured on a 1/8 inch thick specimen according to the ASTM D256 standard.

A thermoplastic resin composition with excellent mechanical properties and excellent metal bonding properties and a molded article manufactured therefrom can be provided.

Hereinafter, embodiments of the present invention will be described in detail. However, this is presented as an example, and the present invention is not limited thereby, and the present invention is only defined by the scope of the claims to be described later.

Unless otherwise specified herein, “copolymer” means block copolymerization, random copolymerization, and graft copolymerization, and “copolymer” means block copolymer, random copolymer, and graft copolymer.

Unless specifically mentioned herein, intrinsic viscosity is measured at 30°C using an Ubbelohde viscometer after dissolving a powder sample in a 97% sulfuric acid solution to a concentration of 0.5 g/dl.

The thermoplastic resin composition according to one embodiment includes (A) 30 to 65% by weight of polyamide 6 resin; (B) 5 to 30% by weight of a polyamide copolymer resin containing a component derived from isophthalic acid or m-xylylenediamine; and (C) 25 to 60% by weight of glass fiber, wherein the weight ratio of the (A) polyamide 6 resin and (B) the polyamide copolymer resin containing a component derived from isophthalic acid or m-xylylenediamine is It may be 6:4 to 9:1.

Hereinafter, each component included in the thermoplastic resin composition will be described in detail.

(A) Polyamide 6 resin

In one embodiment, (A) polyamide 6 resin, that is, PA6 resin, allows the thermoplastic resin composition to achieve excellent metal bonding properties.

In the present invention, (A) polyamide 6 resin is used as the polyamide resin, and since the (A) polyamide 6 resin has high strength and elasticity and high water absorption, the thermoplastic resin composition is more stable than when using other types of polyamide resin. The metal bonding strength can be further improved.

In one embodiment, the intrinsic viscosity of the polyamide 6 resin (A) may be 1.9 to 3.2 dl/g.

In one embodiment, the (A) polyamide 6 resin may be included in an amount of 30 to 65% by weight, for example, 30 to 60% by weight, for example, 30 to 50% by weight, based on 100% by weight of the thermoplastic resin composition. .

When the content of the polyamide 6 resin (A) satisfies the above-mentioned range, the thermoplastic resin composition and the molded article manufactured therefrom may have excellent metal bonding properties.

(B) Polyamide copolymer resin containing a component derived from isophthalic acid or m-xylylenediamine

In one embodiment, (B) a polyamide copolymer resin containing a component derived from isophthalic acid or m-xylylenediamine is used together with the polyamide 6 resin (A), so that the thermoplastic resin composition can achieve excellent metal bonding properties. make it possible

The (B) polyamide copolymer resin containing a component derived from isophthalic acid or m-xylylenediamine is hexamethylenediamine (HMD) and isophthalic acid (IPA), or m-xylylenediamine (MXD) and adip It can be prepared by copolymerizing acids (ADA) together. When hexamethylenediamine and isophthalic acid are copolymerized together, (B1) polyamide 6I resin, that is, PA6I resin, can be produced, and when adipic acid and m-xylylenediamine are copolymerized together, (B2) polyamide MXD6. Resin, that is, PAMXD6 resin, can be produced.

The (B1) polyamide 6I resin is amorphous, the (B2) polyamide MXD6 resin has low crystallinity, and the (B1) polyamide 6I resin or (B2) polyamide MXD6 resin has high crystallinity (A). When used together with polyamide 6 resin, a synergistic effect can be achieved depending on the unique physical properties of each resin. Therefore, the thermoplastic resin composition according to one embodiment comprising at least one of the (B1) polyamide 6I resin and (B2) polyamide MXD6 resin and polyamide 6 resin in a specific ratio can greatly improve metal bonding properties. there is.

In one embodiment, the (B) polyamide copolymer resin containing a component derived from isophthalic acid or m-xylylenediamine may have an intrinsic viscosity of 0.6 to 1.1 dl/g.

In one embodiment, the polyamide copolymer resin (B) containing a component derived from isophthalic acid or m-xylylenediamine is 5 to 30% by weight, for example, 10 to 30% by weight, based on 100% by weight of the thermoplastic resin composition. It may be included in weight percent, for example 5 to 20 weight percent, for example 10 to 20 weight percent. Within the above weight range, the mechanical properties and metal bonding properties of the thermoplastic resin composition containing it and the molded article manufactured therefrom may be excellent.

In one embodiment, the weight ratio of (A) the polyamide 6 resin and (B) the polyamide copolymer resin containing a component derived from isophthalic acid or m-xylylenediamine may be 6:4 to 9:1, For example it may be 6:4 to 8:2, for example 7:3 to 9:1, for example 7:3 to 8:2. Within the above weight ratio range, the metal bonding properties of the thermoplastic resin composition containing it and the molded article manufactured therefrom can be greatly improved.

(C) Glass fiber

In one embodiment, (C) glass fiber can improve mechanical properties such as rigidity and dimensional stability of a thermoplastic resin composition, and the glass fiber can be glass fiber used in a typical thermoplastic resin composition.

The average diameter of the (C) glass fiber may be in the range of 1 to 20 ㎛, for example, 1 to 15 ㎛, for example 1 to 10 ㎛, for example, 1 to 5 ㎛, but is not limited thereto. .

The (C) average length of the glass fiber before processing may be 1 to 10 mm, for example 1 to 8 mm, for example 1 to 5 mm, for example 1 to 3 mm, but is not limited thereto. No. When the average diameter and average length of the glass fiber are within the above range, the thermoplastic resin composition containing the glass fiber and the molded product manufactured therefrom may have excellent mechanical properties such as rigidity and dimensional stability.

The (C) glass fiber may have a circular, oval, rectangular, or dumbbell-shaped cross-section, and may be a mixture of two or more types with different cross-sectional shapes, diameters, and lengths.

In addition, the (C) average ratio of the length (i.e., the longest axis) to the diameter (i.e., the shortest axis) of the glass fiber, that is, the average aspect ratio is 1 to 10, for example, 1 to 8, for example, 1 to 8. 5, for example 1 to 3. Within the above range, excellent mechanical properties of the thermoplastic resin composition and molded articles manufactured therefrom can be secured.

Meanwhile, (C) the surface of the glass fiber can be treated with a surface treatment agent to improve the adhesion between the glass fiber and the resin.

As the surface treatment agent, urethane-based compounds, epoxy-based compounds, silane-based compounds, etc. can be used, and any compound that is commonly commercialized and used can be used without limitation.

In one embodiment, the (C) glass fiber is 25 to 60% by weight, for example, 30 to 60% by weight, for example, 40 to 60% by weight, for example, 30 to 30% by weight, based on 100% by weight of the thermoplastic resin composition. It may be included at 50% by weight. Within the above weight percent range, the thermoplastic resin composition and molded articles manufactured therefrom can exhibit excellent mechanical properties and dimensional stability.

(D) Maleic anhydride modified ethylene-alpha-olefin copolymer

In one embodiment, the thermoplastic resin composition may further include (D) maleic anhydride-modified ethylene-alpha-olefin copolymer. The (D) maleic anhydride-modified ethylene-alpha-olefin copolymer enables the thermoplastic resin composition to achieve excellent impact resistance.

The (D) maleic anhydride-modified ethylene-alpha-olefin copolymer is prepared by polymerizing maleic anhydride, at least one type of ethylene, and alpha-olefin monomer. The alpha-olefin monomer is not particularly limited, but non-limiting examples include propylene, 1-butene, 1-hexene, and 1-octene.

In one embodiment, the (D) maleic anhydride-modified ethylene-alpha-olefin copolymer may be a maleic anhydride-modified ethylene-1-octene copolymer.

The (D) maleic anhydride-modified ethylene-alpha-olefin copolymer may have a weight average molecular weight of 10,000 to 1,000,000 g/mol, for example, 30,000 to 800,000 g/mol, for example, 60,000 to 500,000 g/mol.

The (D) maleic anhydride-modified ethylene-alpha-olefin copolymer may be included in an amount of 1 to 10 parts by weight, for example, 3 to 10 parts by weight, for example, 5 to 10 parts by weight, based on 100 parts by weight of the thermoplastic resin composition. You can. Within the above weight parts range, the thermoplastic resin composition and molded articles manufactured therefrom can exhibit excellent impact resistance.

(E) Additives

In addition to the components (A) to (D), the thermoplastic resin composition according to one embodiment is capable of exhibiting excellent mechanical properties and metal bonding properties, while maintaining a balance between the properties, or depending on the final use of the thermoplastic resin composition. One or more necessary additives may be further included.

Specifically, the additives may include flame retardants, nucleating agents, coupling agents, plasticizers, impact modifiers, lubricants, mold release agents, heat stabilizers, antioxidants, UV stabilizers, pigments, dyes, etc., and these may be used alone or in combination of two or more types. You can.

These additives may be appropriately included within a range that does not impair the physical properties of the thermoplastic resin composition. Specifically, they may be included in an amount of 20 parts by weight or less per 100 parts by weight of the thermoplastic resin composition, but are not limited thereto.

Meanwhile, the thermoplastic resin composition according to one embodiment can also be used by mixing with other resins or other rubber components.

Meanwhile, another embodiment provides a molded article manufactured using the thermoplastic resin composition according to one embodiment. The molded article can be manufactured using the thermoplastic resin composition by various methods known in the art, such as injection molding and extrusion molding.

The molded article has a metal bonding force to an aluminum metal specimen measured by the Type A method according to the ISO 19095 standard of 50 MPa, for example 51 MPa, for example 52 MPa, for example 53 MPa, for example 54 MPa, for example. For example, it may be 55 MPa or more.

The molded product has a notched Izod impact strength measured on a 1/8 inch thick specimen according to the ASTM D256 standard of more than 10 kgf·cm/cm, for example, more than 11 kgf·cm/cm, e.g. For example, it may be 12 kgf·cm/cm or more, for example, 13 kgf·cm/cm or more, for example, 14 kgf·cm/cm or more, for example, 15 kgf·cm/cm or more.

Hereinafter, preferred embodiments of the present invention will be described. However, the following example is only a preferred example of the present invention, and the present invention is not limited by the following example.

Examples 1 to 7 and Comparative Examples 1 to 5

The thermoplastic resin compositions of Examples 1 to 7 and Comparative Examples 1 to 5 were prepared according to the component content ratios shown in Table 1 below.

After mixing the ingredients listed in Table 1, quantitatively and continuously injected into the feed section of a twin-screw extruder (L/D = 45, Φ = 45 mm) (barrel temperature: about 280°C) and extruded/kneaded to produce a thermoplastic resin composition in the form of a pellet. Next, the pellet-shaped thermoplastic resin composition was dried at about 80°C for about 4 hours, and then the physical properties were measured using a 6 oz injection molding machine set at a cylinder temperature of about 280°C and a mold temperature of about 100°C. A specimen was prepared. The measured physical properties are shown in Table 2 below.

In Table 1, the weights of (A), (B1), (B2), (B3) and (C) are relative to 100% by weight of (A), (B1), (B2), (B3) and (C). It is expressed in weight percent, and the weight of component (D) is expressed in parts by weight based on 100 parts by weight of (A), (B1), (B2), (B3), and (C).

division unit Example
One Example
2 Example
3 Example
4 Example 5 Example
6 Example
7 Comparative example
One Comparative example
2 Comparative example
3 Comparative example
4 Comparative example
5 (A) weight% 50 50 40 40 30 30 30 70 50 50 20 50 (B1) weight% 20 - 10 - 20 - - - - - 30 - (B2) weight% - 20 - 10 - 20 20 - - - - - (B3) weight% - - - - - - - - - - - 20 (C) weight% 30 30 50 50 50 50 50 30 50 50 50 30 (D) weight part - - - - - - 6 - - 6 - -

The description of each component listed in Table 1 is as follows.

(A) Polyamide 6 resin

Polyamide 6 resin (product name: EN 300) from KP Chemtech was used.

(B1) Polyamide copolymer resin

Polyamide 6I resin (product name: TM01) from Shandong Dongcheon was used.

(B2) Polyamide copolymer resin

Polyamide MXD6 resin (product name: S6000) from Mitsubishi Gas Chemical was used.

(B3) Polyamide copolymer resin

Solvay's polyamide 6T/66 resin (product name: A6000) was used.

(C) Glass fiber

568H from China Jushi was used.

(D) Maleic anhydride modified ethylene-alpha-olefin copolymer

Dow's Fusabond™ MN 493 D was used.

Physical property evaluation

The experimental results are shown in Table 2 below.

(1) Metal bondability (unit: MPa)

After bonding GeoNation's TRI surface-treated aluminum (Al7S10) metal specimen and thermoplastic resin composition specimen through insert injection molding, the metal bonding force to the aluminum metal specimen was measured using the Type A method according to ISO 19095 standards.

(2) Impact resistance (unit: kgf·cm/cm)

Notched Izod impact strength was measured for 1/8 inch thick specimens according to ASTM D256 standard.

division Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 metal
bonding force 58 55 56 60 56 64 55 26 30 39 46 15 impact strength 10.5 10.1 13.8 13.7 13.1 12.9 14.9 11.7 12.9 13.7 11.5 9.8

From Tables 1 and 2, it can be seen that the thermoplastic resin compositions of the Examples have excellent impact resistance and excellent metal bonding properties, but Comparative Examples 1 to 5 have lower metal bonding properties compared to the Examples. In particular, in the case of Comparative Example 4 in which the weight ratio of component (A) and component (B) was 2:3 and Comparative Example 5 in which polyamide 6T/66 resin was used as the polyamide copolymer resin, metal bonding property was lower than in the Examples. You can check that.

In addition, it can be confirmed that when (D) maleic anhydride-modified ethylene-alpha-olefin copolymer is further included as in Example 7, metal bonding properties are excellent and impact resistance can also be greatly improved.

Although the preferred embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and improvements can also be made by those skilled in the art using the basic concept of the present invention defined in the appended claims. It falls within the scope of invention rights.

Claims (12)

(A) 30 to 65% by weight of polyamide 6 resin;
(B) 5 to 30% by weight of a polyamide copolymer resin containing a component derived from isophthalic acid or m-xylylenediamine; and
(C) 25 to 60% by weight of glass fiber;
A thermoplastic resin composition wherein the weight ratio of (A) the polyamide 6 resin and (B) the polyamide copolymer resin containing a component derived from isophthalic acid or m-xylylenediamine is 6:4 to 9:1. In paragraph 1:
A thermoplastic resin composition wherein the weight ratio of (A) the polyamide 6 resin and (B) the polyamide copolymer resin containing a component derived from isophthalic acid or m-xylylenediamine is 6:4 to 8:2. In paragraph 1:
The (A) polyamide 6 resin has an intrinsic viscosity of 1.9 to 3.2 dl/g, a thermoplastic resin composition. In paragraph 1:
(B) A thermoplastic resin composition wherein the polyamide copolymer resin containing a component derived from isophthalic acid or m-xylylenediamine has an intrinsic viscosity of 0.6 to 1.1 dl/g. In paragraph 1:
(C) A thermoplastic resin composition in which the average particle diameter of the glass fiber is 1 to 20 ㎛ and the average length before processing is 1 to 10 mm. In paragraph 1:
(D) A thermoplastic resin composition further comprising a maleic anhydride-modified ethylene-alpha-olefin copolymer. In paragraph 6:
The thermoplastic resin composition wherein the (D) maleic anhydride-modified ethylene-alpha-olefin copolymer has a weight average molecular weight of 10,000 to 1,000,000 g/mol. In paragraph 6:
(D) A thermoplastic resin composition in which the maleic anhydride-modified ethylene-alpha-olefin copolymer is a maleic anhydride-modified ethylene-1-octene copolymer. In paragraph 1:
A thermoplastic resin composition further comprising at least one additive selected from antibacterial agents, flame retardants, nucleating agents, coupling agents, fillers, plasticizers, impact modifiers, lubricants, mold release agents, heat stabilizers, antioxidants, ultraviolet stabilizers, pigments, and dyes. A molded article manufactured from the thermoplastic resin composition according to any one of claims 1 to 9. In paragraph 10:
The molded product has a metal bonding force of 50 MPa or more to an aluminum metal specimen measured by the Type A method according to the ISO 19095 standard. In paragraph 10:
The molded product has a notched Izod impact strength of 10.0 kgf·cm/cm or more, measured on a 1/8 inch thick specimen according to the ASTM D256 standard.