KR101777446B1 - Glass fiber reinforced polyamide resin composition, and plastic molded product - Google Patents

Abstract

The present invention relates to a glass fiber-reinforced polyamide resin composition and a plastic molded article, and a glass fiber-reinforced polyamide resin composite having a high content of the glass fiber reinforced polyamide resin composition and a molded article thereof without deteriorating the mechanical properties or heat resistance A glass fiber reinforced polyamide resin composition capable of providing a glass fiber reinforced polyamide resin composition, and a plastic molded article.

Description

TECHNICAL FIELD [0001] The present invention relates to a glass fiber reinforced polyamide resin composition,

The present invention relates to a glass fiber-reinforced polyamide resin composition and a plastic molded article, and more particularly to a glass fiber-reinforced polyamide resin composition for automobile interior and exterior materials having excellent appearance characteristics, fiber reinforced polyamide resin composition capable of providing a glass fiber reinforced polyamide resin composite excellent in appearance characteristics without deterioration of physical properties while avoiding the use of molecular chain cutting additives or low viscosity which have been conventionally added by the introduction of a scission additive, And a plastic molded article obtained therefrom.

The history of polyamide resins as engineering plastics is close to 40 years, but demand is still strong. The polyamide resin is basically classified into nylons 6, 66, 610, 612, 11, 12 and copolymers and blends thereof, and has various useful characteristics and can keep various demands. .

Particularly, by adding an inorganic reinforcing agent such as glass fiber, the polyamide-based resin has been remarkably improved in mechanical stiffness and heat resistance, and has been applied to structural materials and automobile interior-exterior materials.

However, since nylon 66 has relatively low fluidity and high crystallization rate compared to nylon 6, it has relatively poor appearance characteristics. Therefore, when reinforcing with glass fiber, appearance defects due to protrusion of glass fiber are more severe than nylon 6, It is more difficult to improve the appearance when reinforcing a high content of 30% or more.

In addition, the polyamide-based resin has poor dimensional instability and bending property due to its high water absorption rate in molecular structure, and exhibits low fluidity when an inorganic material is added.

Such low fluidity is known to occur because the added inorganic substance interferes with the flow of resin in the molten state, and the deterioration of the external appearance due to protrusion of the inorganic material occurs due to the decrease of the fluidity.

As a method of improving the appearance by improving the flowability, there is a method of improving the appearance by using a low viscosity base or an additive causing chain scission, but there is a limitation in improvement of appearance when a high content of 30% or more glass fiber reinforcement But also seriously deteriorates the physical properties. Therefore, it is urgently required to produce a PA66-based composite reinforced with a high content of glass fibers having excellent appearance characteristics without greatly deteriorating physical properties.

In order to solve the problems of the prior art as described above, the present invention relates to a glass fiber reinforced polyamide resin composition for automobile interior and exterior materials having excellent appearance characteristics, A glass fiber reinforced polyamide resin composition capable of providing a glass fiber reinforced polyamide resin composite excellent in appearance characteristics without deteriorating physical properties while avoiding use of a molecular chain cutting additive added thereto or a low viscosity and a plastic molded article obtained therefrom The purpose is to provide.

In order to achieve the above object,

A glass fiber reinforced polyamide resin composition comprising:

[Formula 1]

로 나타내는 화합물, 및

, And

The following formula 2

[Formula 2]

로 나타내는 화합물 중에서 선택된 1종 이상의 분자쇄절단(chain scission) 첨가제를 포함하는 것을 특징으로 하는 유리섬유 보강 폴리아미드 수지 조성물을 제공한다.

And at least one molecular chain cutting additive selected from the group consisting of compounds represented by the following general formulas (1) and (2).

The present invention also provides a plastic molded article comprising the above-mentioned glass fiber-reinforced polyamide resin composition.

INDUSTRIAL APPLICABILITY According to the present invention, there is provided a glass fiber reinforced polyamide resin composition having a high content of glass fiber-reinforced polyamide resin composition, which can provide appearance required for use in automotive exterior parts without deteriorating mechanical properties or heat resistance, There is an effect to provide.

Hereinafter, the present invention will be described in detail.

The glass fiber reinforced polyamide resin composition of the present invention has the following formula 1

[Formula 1]

로 나타내는 화합물, 및

, And

The following formula 2

[Formula 2]

로 나타내는 화합물 중에서 선택된 1종 이상의 분자쇄절단(chain scission) 첨가제를 포함하는 것을 특징으로 한다.

And at least one chain scission additive selected from the group consisting of compounds represented by the following general formula (1).

The term " chain scission additive "is intended to include, but is not limited to, the molecular chain of the polyamide resin bonded to the glass fiber in the extrusion process, Quot; refers to an additive capable of performing a role.

The compound represented by the above formula 1 or formula 2 is a comonomer used for preparing a polyamide resin. When the polyamide resin is included as a molecular chain breaking additive in the present invention, the advantage of improving the fluidity without changing the physical properties of the polyamide resin Can be provided.

The chain scission additive may be contained in an amount of 0.1 to 1.5% by weight, 0.1 to 1.0% by weight, or 0.3 to 1.5% by weight in 100% by weight of the total amount of the glass fiber reinforced polyamide resin composition, , Excessive molecular chain breakage may occur, resulting in unbalanced property degradation, and moldability may be deteriorated due to excessive gas generation at the time of injection.

As the polyamide resin included in the resin composition of the present invention, for example, lactam or w-amino acid having a cyclic structure may be used, or diacids and diamines may be used have. Further, homopolyamides, copolyamides, and mixtures thereof can be used.

Specific examples of the polyamide resin include polyamide resins such as polyhexamethylene adipamide (nylon 6,6), polyhexamethylene azelamide (nylon 6,7), polyhexamethylene sebacamide (nylon 6,10), polyhexamethylene (Nylon 6), polystyrene (Nylon 6), and polyolinolactam (nylon 12) may be used.

As a specific example, the polyamide resin may be a crystalline, semi-crystalline or amorphous resin.

As the glass fiber-reinforced polyamide resin composition,

(a1) 25 to 75% by weight of a polyamide resin comprising 50 to 100% by weight of polyhexamethylene adipamide (nylon 6,6) and (a2) 0 to 50% by weight of polycaprolactam (nylon 6) (b) 30 to 70% by weight of glass fiber; and (g) a glass fiber.

As another example, the glass fiber-reinforced polyamide resin composition may contain,

(a1) 25 to 75% by weight of a polyamide resin comprising 60 to 100% by weight of polyhexamethylene adipamide (nylon 6,6) and (a2) 0 to 40% by weight of polycaprolactam (nylon 6) (b) 30 to 70% by weight of glass fiber; and (g) a glass fiber.

(A1) polyhexamethylene adipamide (nylon 6,6) has a relative viscosity of 2.0 to 3.8 cP, or 2.3 to 2.5 cP, measured by dissolving it in 85% formic acid at 25 ° C, and a number average molecular weight (Mn ) Of from 16,000 to 200,000 g / mol, or from 20,000 to 180,000 g / mol.

The (a2) polycaprolactam (nylon6) has a relative viscosity of 2.0 to 3.8 cP, or 2.5 to 2.6 cP and a number average molecular weight (Mn) of 16,000 to 200,000, measured by dissolving it in formic acid 85% g / mol, or 20,000 to 180,000 g / mol.

If necessary, the polyamide resin may contain at least one member selected from the group consisting of polyhexamethylene azel amide (nylon 6,7), polyhexamethylene sebacamide (nylon 6,10), polyhexamethylene loramide (nylon 6,12) Methylene adipamide (nylon 4,6) and polyolinolactam (nylon 12).

The glass fiber (b) may have a diameter D of 10 to 20 mu m, 10 to 15 mu m, or 10 to 13 mu m, and a length L of 1 to 5 mm or 2 to 3 mm, for example. And may be a conventional or flat shape.

Specific examples of the glass fiber (b) include those having an aspect ratio of 1.0 to 8.0 in the flat cross-section, and a very strong bonding force between the polymers in the resin composition It is possible to replace resin and metal which are expensive in processing plastic parts such as automobiles in which stiffness is given priority by increasing rigidity.

The cross section D corresponds to the longest side of the cross section when the section cut perpendicularly to the longitudinal direction of the glass fiber is a rectangle, and the longest section length when the cross section is elliptical on the cross section.

As another example, the (b) glass fiber may have a rectangular or elliptical cross section cut perpendicular to the longitudinal direction.

As another example, the glass fiber (b) has a shortest length of 3 to 15 탆, or 7 to 11 탆 when the cross section cut in a direction perpendicular to the longitudinal direction is a rectangle, or a shortest diameter of 5 to 15 Mu m, or 7 to 10 mu m.

As another example, the glass fiber (b) may be surface-treated with a silane-based coupling agent.

As another example, the glass fiber (b) may be surface-treated with an aminosilane-based coupling agent in an amount of 0.1 to 1.5 parts by weight, or 0.1 to 1.0 part by weight, based on 100 parts by weight of the glass fiber.

The composition can be used as a lubricant, an antioxidant, a light stabilizer, a chain extender, a catalyst, a release agent, a pigment, a dye, an antistatic agent, an antimicrobial agent, a processing aid, a metal deactivator, a fuming inhibitor, an inorganic filler, And a coupling agent. The additive may be used within a range that does not adversely affect the physical properties of the glass fiber-reinforced polyamide resin composition of the present invention. As a specific example, the additive may be contained in the range of 0.1 to 70 parts by weight based on 100 parts by weight of the polyamide resin.

Wherein the glass fiber reinforced polyamide resin composition has a Flexural Modulus (FM) measurement value of 12 to 25 GPa or 12 to 20 GPa according to ASTM D790 standard and a heat deflection temperature of 4.5 kgf , ° C) may be 190 ° C or more, or 219 ° C or more.

The glass fiber-reinforced polyamide resin composition is optionally mixed with the additive in a mixer or a super mixer and then mixed with a twin-screw extruder, a single-screw extruder, roll mills, Kneading at 200 to 300 ° C or a temperature range of 280 to 300 ° C using one of various compounding machines such as a kneader or a Banbury mixer to obtain a pellet by extrusion processing, The pellets can be sufficiently dried by using a dehumidifying dryer or a hot-air dryer and then subjected to injection molding to produce a halogen-flame retardant glass fiber-reinforced polyamide resin.

As a specific example, the halogen-flame retardant glass fiber-reinforced polyamide resin may be produced by twin-screw extruding at a barrel temperature of 280 to 300 ° C.

According to the present invention, it is possible to provide a glass fiber reinforced polyamide resin composition which is molded from the above glass fiber-reinforced polyamide resin composition and has high appearance characteristics required for use in automobile interior and exterior parts, mechanical properties such as moldability, tensile properties, flexural strength, flexural modulus, A plastic molded article can be provided.

The molded product may be, for example, an automobile exterior part or an electric / electronic part.

Hereinafter, preferred embodiments of the present invention will be described in order to facilitate understanding of the present invention, but the present invention is not limited thereto.

 [Example]

Examples 1 to 12 and Comparative Examples 1 to 4

The components shown in the following Table 1 were put into a super mixer in the stated amounts and mixed well and then the mixture was extruded by using a twin-screw extruder at a barrel temperature of 250 to 300 ° C After melt-kneading, pellets were obtained by extrusion processing (using a pelletizer). The pellets were dried at 80 ° C. for 4 hours or more, injection molded, and left to stand at room temperature for 1 day. The specimens were used as test specimens.

The materials used in this experiment were as follows:

≪ Polyamide resin: PA >

(A): Polycaprolactam (nylon 6): A product having a relative viscosity of 2.5 to 2.6 cP and an Mn of 20,000 to 180,000 g / mol, as measured in 85% formic acid at 25 ° C.

(B): polyhexamethylene adipamide (nylon 6,6): a product having a relative viscosity of 2.3 to 2.5 cP and an Mn of 20,000 to 180,000 g / mol, as measured in 85% formic acid at 25 ° C.

(C): Glass fiber: Owens Corning Inc. Diameter (D) of 10 to 13 탆, length (L) of 3 mm (spherical with aspect ratio of 1) and general surface treated with an amino silane coupling agent Type glass fiber was used.

(D): Isopthalic acid

(E): Adipic acid

[Test Example]

The properties of the specimens made from the glass fiber-reinforced polyamide resin compositions prepared in Examples 1 to 12 and Comparative Examples 1 to 4 were measured by the following methods, and the results are shown in Table 1 below.

[Property measurement test]

Appearance: The gas mark on the surface was visually observed. In Table 5, the surface protrusion of the inorganic material means 90 to 100% of the total area, 4 means 60 to 90%, 3 means 30 to 60%, 2 means 10 to 30 %, And 1 denotes a state of 0 to 10% as a reference.

Tensile strength (kg / cm 2): Measured according to ASTM D638.

Flexural Strength (kg / cm2) and Flexural Modulus (GPa): Measured according to ASTM D790.

Heat distortion temperature (HDT, ° C): measured under 4.5 kgf according to ASTM D648 standard.

division
(wt%) Example Comparative Example One 2 3 4 5 6 7 8 9 10 11 12 One 2 3 4 A 0 0 0 0 0 19.6 15.8 11.7 19.8 39.2 0 29.6 24.7 40 19.6 79.6 B 39.7 39.5 39.2 39 38.5 19.6 23.4 27.5 19.8 0 39.2 0 15.3 0 0 0 C 60 60 60 60 60 60 60 60 60 60 60 70 60 60 80 20 D 0.3 0.6 0.8 1.0 1.5 0.8 0.8 0.8 0.4 0 0 0.4 0 0 0.4 0.4 E 0 0 0 0 0 0 0 0 0 0.3 0.3 0 0 0 0 0 Exterior 4 3 2 One One 4 4 3 2 3 4 5 5 2 - One Seal
burglar 2143 1918 2135 1749 1420 2327 2273 2250 2297 2100 2040 2542 2300 1850 - 1500 curve
burglar 3654 3465 3635 3507 2870 3335 3055 3000 3280 3430 3611 3821 3415 2800 - 2200 curve
Shout
Rate 18.6 18.6 19.0 20.0 12.0 16.8 15.7 15.8 16.8 18.6 17.9 24.7 17.0 13.5 - 6.8 HDT 252 250 247 247 246 217 219 223 224 210 210 260 213 207 - 205

Examples 1 to 12 using the glass fiber reinforced polyamide resin composition according to the present invention were prepared by mixing polycaprolactam (nylon 6) and polyhexamethylene adipamide (nylon 6,6) in a ratio of 62: And the mechanical properties such as tensile strength, flexural strength and flexural modulus were not lowered and the heat resistance was also improved remarkably as compared with Comparative Example 1 which was used in a weight ratio of 38 (i.e., excessive use of polycaprolactam) I could confirm.

In Examples 1 to 12 using the glass fiber-reinforced polyamide resin composition according to the present invention, polycaprolactam (nylon 6) and polyhexamethylene adipamide (nylon 6,6) were mixed at a weight ratio of 100: 0 , And polycaprolactam alone), the mechanical properties such as tensile strength, flexural strength and flexural modulus were not deteriorated while exhibiting appearance characteristics corresponding to the use of polycaprolactam (nylon 6) alone, and heat resistance was also excellent .

Further, in the case of Comparative Example 3 in which the amount of the glass fiber exceeded the proper amount by more than 80%, extrusion was impossible and it was difficult to measure the physical properties.

Further, Examples 1 to 12 using the glass fiber-reinforced polyamide resin composition according to the present invention exhibited excellent appearance properties, tensile strength, flexural strength, flexural modulus and the like as compared with Comparative Example 4 in which the glass fiber content was less than 20% Mechanical properties, and heat resistance.

Claims (12)

A glass fiber reinforced polyamide resin composition comprising:
[Formula 1]

, And
The following formula 2
[Formula 2]

0.1 to 0.4% by weight of at least one chain scission additive selected from compounds represented by the following general formula
(a1) 30 to 69% by weight of a polyamide resin comprising 50 to 70.2% by weight of polyhexamethylene adipamide (nylon 6,6) and (a2) 29.8 to 50% by weight of polycaprolactam (nylon 6); And
(b) 30 to 69% by weight of glass fiber; , ≪ / RTI &
(A1) polyhexamethylene adipamide (nylon 6,6) has a relative viscosity of 2.0 to 3.8 cp, a number average molecular weight (Mn) of 16,000 to 200,000 g / mol, as measured by dissolving in 85% formic acid at 25 ° C ,
(A2) polycaprolactam (nylon6) having a relative viscosity of 2.0 to 3.8 cp, a number average molecular weight (Mn) of 16,000 to 200,000 g / mol, as measured by dissolving in 85% formic acid at 25 ° C,
The glass fiber (b) is surface-treated using an aminosilane-based coupling agent in a range of 0.1 to 1.0 part by weight relative to 100 parts by weight of glass fiber
Glass fiber reinforced polyamide resin composition. delete delete delete delete The method according to claim 1,
The glass fiber (b) is characterized in that it has a conventional or flat shape with a diameter (D) of 3 to 20 μm and a length (L) of 1 to 5 mm
A glass fiber reinforced polyamide resin composition. The method according to claim 1,
(B) the aspect ratio of the long axis and the minor axis in the flat cross-section of the glass fiber is 1.0 to 8.0
A glass fiber reinforced polyamide resin composition. delete The method according to claim 1,
The composition can be used as a lubricant, an antioxidant, a light stabilizer, a chain extender, a catalyst, a release agent, a pigment, a dye, an antistatic agent, an antimicrobial agent, a processing aid, a metal deactivator, a fuming inhibitor, an inorganic filler, And at least one additive selected from a coupling agent
A glass fiber reinforced polyamide resin composition. The thermoplastic resin composition according to claim 1, characterized by having a Flexural Modulus (FM) measurement value of 12 to 25 GPa according to ASTM D790 and a heat deflection temperature (4.5 kgf, ° C) according to ASTM D648 of 190 ° C or more to
A glass fiber reinforced polyamide resin composition. A glass fiber reinforced polyamide resin composition comprising the glass fiber-reinforced polyamide resin composition of claim 1
Plastic molded articles. 12. The method of claim 11,
Wherein the molded article is an automotive exterior part.