KR20200072225A - Glass fiber reinforced polyamide resin composition, method for preparing thereof and molding product comprising the same - Google Patents

Abstract

The present invention relates to a glass fiber-reinforced polyamide resin composition, a method for producing the same, and a molded article including the resin composition. More particularly, the present invention relates to: a glass fiber-reinforced polyamide resin composition where a molecular chain cutting additive and polyol are blended into a glass fiber-reinforced polyamide resin within a specific range, so as to secure mechanical properties at a level equivalent to or better than those of a conventional glass fiber-reinforced polyamide resin composition, have excellent balance of properties and moldability, and greatly improve appearance quality; a method for producing the same; and a molded article including the same.

Description

Glass fiber-reinforced polyamide resin composition, manufacturing method thereof, and molded article including the same{GLASS FIBER REINFORCED POLYAMIDE RESIN COMPOSITION, METHOD FOR PREPARING THEREOF AND MOLDING PRODUCT COMPRISING THE SAME}

The present invention relates to a glass fiber-reinforced polyamide resin composition, a method for manufacturing the same, and a molded article comprising the same, and more specifically, a molecular chain cutting additive and a polyol are blended within a specific range to maintain mechanical properties high while maintaining physical property balance and molding. It relates to a glass fiber-reinforced polyamide resin composition having excellent properties and excellent appearance quality at the same time.

As an engineering plastic, polyamide resin has excellent mechanical properties and can be used in various fields, so its demand is strong. Polyamide resins include polycaprolactam (nylon 6), polyhexamethyleneadipamide (nylon 6,6), polyhexamethylene sebacamide (nylon 6,10), polyhexamethylene dodeamide (nylon 6,12) , Polyundecanoamide (nylon 11), polylaurolactam (nylon 12) and their copolymers are diverse, and each has useful features and can generate various performances, so it continues to maintain a great demand.

Particularly, by adding an inorganic reinforcing agent such as glass fiber, the polyamide resin can greatly improve mechanical stiffness, dimensional stability, heat resistance, and the like, and has been applied to various industrial fields such as a structural agent or a vehicle's interior and exterior materials.

Among the polyamide resins described above, polyhexamethylene adipamide (nylon 6,6) or polycaprolactam (nylon 6), which is advantageous in terms of reducing manufacturing cost and securing physical properties, is commonly used, but polyhexamethylene adipamide (nylon Since 6,6) has low fluidity and high crystallization rate compared to polycaprolactam (nylon 6), the appearance quality is relatively low, and thus, when reinforcing glass fibers, there is a problem in that appearance defects due to surface protrusion are more severe. Therefore, it was more difficult to secure the appearance quality when reinforcing a high content (more than 30% by weight) of glass fibers in order to impart mechanical rigidity or heat resistance.

In order to improve this problem, a method of improving the appearance quality by improving the fluidity of the base resin has been known, and specifically, a method of using a low viscosity base resin or adding a molecular scission additive has been proposed. However, this method has a limitation in improving the appearance quality of the glass fiber high content resin composition, as well as a problem that mechanical properties are seriously deteriorated.

In particular, when the molecular chain cutting additive is used, as the content thereof increases, the appearance quality of the glass fiber-reinforced polyamide resin material increases significantly, but there is a problem that the physical property balance is broken due to excessive molecular chain cutting, as well as heat such as injection. When the gas was excessively formed, the moldability deteriorated, and the surface was rough and the glossiness was lowered.

Therefore, it is required to develop a glass fiber reinforced polyamide resin composition that greatly improves the appearance characteristics while satisfying all of mechanical properties, heat resistance, and moldability, and in particular, while maintaining high mechanical properties or moldability, the appearance quality is poly. There is an urgent need to develop a high-content glass fiber-reinforced polyhexamethyleneadipamide resin equivalent to or better than caprolactam.

Japanese Patent Application Laid-Open No. 06-313045A

In order to solve the problems of the prior art as described above, the present invention provides a glass fiber-reinforced polyamide resin composition, a method of manufacturing the same, and a molded article comprising the same, which greatly improves appearance characteristics while satisfying all of mechanical properties, heat resistance, and moldability. It is aimed at providing.

In particular, the present invention is a high content (glass fiber 30% by weight or more, preferably 60% by weight or more) glass having an appearance equivalent to or better than polycaprolactam while maintaining high mechanical properties, heat resistance, moldability, etc. It is an object to provide a fiber-reinforced polyhexamethylene adipamide-based resin composition.

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

In order to achieve the above object, the present invention is 100 parts by weight of glass fiber reinforced polyamide resin containing 25 to 70% by weight of polyamide resin and 30 to 70% by weight of glass fiber, isophthalic acid, adipic acid and anhydrides thereof 0.05 to 1 part by weight of one or more chain scission additives selected from; And polyol 0.05 to 1 part by weight; provides a glass fiber reinforced polyamide resin composition comprising a.

In addition, the present invention is one or more molecules selected from isophthalic acid, adipic acid and anhydrides thereof, 100 parts by weight of glass fiber reinforced polyamide resin comprising 25 to 70% by weight of polyamide resin and 30 to 70% by weight of glass fiber Chain scission additives 0.05 to 1 part by weight; And polyol 0.05 to 1 part by weight; provides a method for producing a glass fiber-reinforced polyamide resin composition comprising the step of blending, kneading and extruding it.

In addition, the present invention provides a molded article comprising the glass fiber reinforced polyamide resin composition.

The glass fiber-reinforced polyamide resin composition according to the present invention prescribes molecular slicing additives and polyols within a specific content range to improve the above-mentioned problems of the prior art, and is equivalent to or better than the conventional glass fiber-reinforced polyamide resin composition While maintaining the level of mechanical properties, heat resistance, etc., the moldability is improved, in particular, it provides an advantage that the appearance quality is greatly improved.

In addition, according to the present invention, even if a small amount of the molecular chain cutting additive is added, the synergistic effect of this and the polyol provides excellent mechanical properties, heat resistance, moldability, etc.

In addition, according to the present invention, while maintaining high mechanical properties, heat resistance, moldability, etc., a high content (30% by weight or more, preferably 60% by weight or more) of glass fiber reinforced polyamide resin composition with excellent appearance quality Can provide.

Hereinafter, the glass fiber-reinforced polyamide resin composition of the present disclosure, a method for manufacturing the same, and a molded article containing the same will be described in detail.

In order to solve the problems of the prior art described above, the present inventors prescribe specific molecular chain cutting additives and polyols to the glass fiber reinforced (more than 30% by weight) polyamide resin within a specific content range. In this case, the molecular chain cutting additives and It was confirmed that the synergistic effect of the polyol maintains the physical properties such as mechanical properties and heat resistance while maintaining a high physical property balance, and that the moldability and appearance quality can be improved at the same time, and based on this, it is further sold out to complete the present invention.

The term "chain scission additive" used in the present description is not specifically specified, but serves to prevent surface protrusion due to glass fibers by cutting the molecular chain of the polyamide resin and improving fluidity during the extrusion process. Refers to additives that can be performed.

As used herein, the term "polyol" refers to a polyhydric alcohol compound having two or more hydroxyl groups (-OH) in a molecule, unless specified otherwise.

The glass fiber-reinforced polyamide resin composition of the present disclosure is, for example, 100 to 100 parts by weight of a glass-reinforced polyamide resin containing 25 to 70% by weight of polyamide resin and 30 to 70% by weight of glass fiber, isophthalic acid, adipic acid And 0.05 to 1 part by weight of at least one chain scission additive selected from anhydrides thereof. And 0.05 to 1 part by weight of polyol. In this case, while maintaining high mechanical strength, heat resistance, moldability, and the like, it provides an advantage that the appearance quality is greatly improved.

Hereinafter, the resin composition of the present description will be described in detail for each component.

Polyamide Suzy

The polyamide resin is, for example, 25 to 70% by weight or 28 to 70% by weight, 28 to 65% by weight, 25 to 50% by weight relative to the total weight of the glass fiber-reinforced polyamide resin comprising polyamide resin and glass fibers Or it may be included in a proportion of 50 to 65% by weight, mechanical strength, moldability, heat resistance, etc. of the resin composition within this range are all good, there is an advantage of excellent physical property balance.

The polyamide resin may have a number average molecular weight of 10,000 to 500,000 g/mol, 10,000 to 300,000 g/mol, or 13,000 to 33,000 g/mol, for example, and the composition has excellent physical property balance and moldability. outstanding.

Unless otherwise specified in the present description, the number average molecular weight of the polyamide resin is a value measured at 40°C using gel permeation chromatography. Specifically, 10 mg of the resin is dissolved in 10 g of hexafluoroisopropanol and measured. As the material, polymethyl methacrylate (PMMA) was used.

The polyamide resin is, for example, selected from polyhexamethylene adipamide, polyhexamethylene azelamide, polyhexamethylene sebacamide, polymethylene dodecamide, polytetramethylene adipamide, polycaprolactam, and polylaurolactam. It may be one or more types, preferably may include polyhexamethylene adipamide or polycaprolactam, and more preferably, it includes polyhexamethylremadipamide. In this case, there is an advantage that the physical property balance of the resin composition is more excellent.

As another example, the polyamide resin may be a ring-structured lactam or an amino acid condensed with one or more types, or a polymer containing dicarboxylic acid and diamine.

Further, the polyamide resin may be homo polyamide, copolyamide, or a mixture thereof.

As a preferred example, the polyamide resin may be polyhexamethylene adipamide, polycaprolactam, or a mixture thereof, and in this case, there is an advantage in physical properties such as mechanical strength, moldability, and heat resistance of the resin composition.

When the polyhexamethylene adipamide and the polycaprolactam are mixed and applied as a polyamide resin in the present disclosure, the polyhexamethylene adipamide is included in a ratio of 35 to 85% by weight or 35 to 70% by weight, The polycaprolactam may be included in a ratio of 15 to 65% by weight or 30 to 65% by weight, and within this range, physical properties such as mechanical strength, formability, and heat resistance have more excellent advantages. Here, the content range of each of the polyhexamethylene adipamide and the polycaprolactam is based on the total amount of the polyamide resin.

The polyhexamethylene adipamide may be, for example, a relative viscosity measured by dissolving in a formic acid solution having a concentration of 85% by weight at 25°C, for example, 2.0 to 5.5 cP or 2.2 to 3.2 cP, and the physical property balance of the composition within this range It has the advantage of being excellent and easy to mold.

The polyhexamethylene adipamide may have a number average molecular weight of 10,000 to 500,000 g/mol, 10,000 to 300,000 g/mol, 10,000 to 100,000 g/mol, 10,000 to 50,000 g/mol, or 13,000 to 33,000 g/mol, Within this range, the composition has an excellent balance of physical properties and easy molding.

The polycaprolactam may be, for example, a relative viscosity measured by dissolving in a sulfuric acid solution having a concentration of 96% by weight at 25°C, for example, 2.0 to 5.5cP or 2.2 to 3.2cP, and the composition has excellent physical property balance and molding. The castle is excellent.

The polycaprolactam may have a number average molecular weight of 10,000 to 500,000 g/mol, 10,000 to 300,000 g/mol, 10,000 to 100,000 g/mol, 10,000 to 50,000 g/mol, or 13,000 to 33,000 g/mol, for example. The composition has excellent balance of physical properties within the range, and excellent moldability.

Unless otherwise specified in the present description, the number average molecular weight of the polyamide resin is a value measured at 40°C using gel permeation chromatography. Specifically, 10 mg of the resin is dissolved in 10 g of hexafluoroisopropanol and measured. As the material, polymethyl methacrylate (PMMA) was used.

Glass fiber

The glass fiber is, for example, 30 to 75% by weight, 30 to 72% by weight, 35 to 72% by weight, 50 to 75% by weight, or 50 to 75% by weight, based on the total weight of the glass fiber reinforced polyamide resin comprising polyamide resin and glass fibers, or It may be included in a ratio of 35 to 50% by weight, mechanical strength, moldability, heat resistance, etc. of the resin composition within this range are all good, there is an advantage of excellent physical property balance.

The glass fiber may have an average diameter of 3 to 20 μm, 10 to 20 μm, 10 to 15 μm, or 10 to 13 μm, for example, and an average length of 1 to 5 mm or 2 to 3 mm, for example. It provides the advantage of improving the mechanical strength and heat resistance without deteriorating the appearance quality or formability of the composition.

The average diameter and the average length of the glass fibers in this description are measured by scanning electron microscopy (SEM) for 30 each, unless otherwise specified, to calculate the average value.

The glass fiber may be a glass fiber optionally surface-treated with a coupling agent as needed, and in this case, there is an advantage in that the compatibility with the polyamide resin increases, thereby improving the physical properties balance and appearance quality of the resin composition.

The coupling agent is, for example, silane coupling agents such as aminosilane, epoxysilane, amidesilane, azidesilane, and acrylicsilane; And titanate-based coupling agents; It may be one or more selected from among them, and among them, aminosilane and epoxysilane may be preferable, and in this case, there is an advantage of excellent appearance quality while maintaining a high physical property balance.

The coupling agent may be used in an amount of 0.1 to 1.5 parts by weight or 0.1 to 1.0 parts by weight, for example, compared to 100 parts by weight of glass fiber, but it is not limited thereto.

Additives for molecular scission

The molecular chain cutting additive may be, for example, one or more selected from isophthalic acid, adipic acid, and anhydrides thereof, preferably isophthalic acid, in which case the appearance quality is improved without deteriorating the physical property balance of the composition. There is an advantage.

The isophthalic acid or adipic acid is a compound that can be used as a comonomer when producing a polyamide resin, and when it is included as a molecular chain cutting additive, composition fluidity without adversely affecting physical properties such as mechanical strength and heat resistance of the polyamide resin And improve the appearance quality.

The molecular chain cutting additive, 0.05 to 1 part by weight based on 100 parts by weight of the glass fiber reinforced polyamide resin, 0.07 to 0.7 parts by weight, 0.1 to 0.9 parts by weight, 0.1 to 0.5 parts by weight, 0.1 to 0.4 parts by weight, 0.1 to It may be included in 0.3 parts by weight or 0.2 to 0.3 parts by weight, and within this range, the overall physical property balance of the composition is maintained, while there is an advantage that the appearance quality such as glossiness is greatly improved. If its content is less than 0.05 part by weight, the effect of improving the appearance quality cannot be expected, and if it exceeds 1 part by weight, the resin is excessively decomposed to significantly degrade the physical property balance and gas is excessively generated in a thermoforming process such as injection, resulting in molding. It is not easy and the glossiness is poor, so the appearance defect may increase.

Polyol

In the present description, the polyol has excessive molecular chain cutting as the content of the molecular chain cutting additive increases, and thus, the moldability decreases as the amount of gas generated during thermoforming such as injection increases, and the appearance quality such as glossiness of the product decreases. It is added to supplement.

The polyol may be added in 0.05 to 1 part by weight, 0.07 to 0.7 parts by weight, 0.1 to 0.7 parts by weight, 0.1 to 0.5 parts by weight, or 0.1 to 0.3 parts by weight based on 100 parts by weight of the glass fiber reinforced polyamide resin, and The synergistic effect with the molecular chain cutting additive within the range may provide an advantage that the overall physical property balance of the composition is maintained high, while the moldability is excellent and the appearance quality is greatly improved.

The polyol may be a chain-type polyol or a branched polyol, and in this case, it provides an advantage that the moldability and appearance quality are simultaneously improved while maintaining a high physical property balance.

The chain-type polyol may be, for example, one or more selected from methylene glycol, ethylene glycol, diethylene glycol, polypropylene glycol, polytetramethylene glycol, sugar alcohols, and fatty alcohols. Glycerol, sorbitol, erythritol, etc. may be possible, and the fatty alcohols may include octyl alcohol, decyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, and the like.

The branched polyol includes, for example, trimethylolpropane, pentaerythritol, and the like, but is not limited thereto.

As another example, the branched polyol may be a dendrimer-structured polyol, and in this case, the appearance quality may be further improved while the composition has a high physical property balance.

The polyol of the dendrimer structure may be, for example, a hydroxy terminal dendrimer whose terminal is functionalized with a hydroxy group (-OH), in which case the overall physical property balance of the composition is excellent while providing an excellent appearance.

As a specific example, the hydroxy terminal dendrimer may be a hyperbranched hydroxyl polyester, and more specifically, a hyperbranched 2,2-bis(hydroxylmethyl)propionic acid polyester (where the terminal hydroxyl group is 16 to 16). 128) or Boltorn H20, H30, H40, H2003, H2004, H311, P500 available from Perstorp.

Other examples of the dendrimer structure polyol include adipic acid and glycerol; Or adipic acid, glycerol and ethylene glycol; Or trimethylolpropane and adipic acid; polymerized hydroxy terminated hyperbranched polyesters.

In another example, the dendrimer-structured polyol includes a mixture of one or more selected from hyperbranched polyester and adipic acid and ethylene glycol; Or those produced by reactions thereof; Can be At this time, the hyperbranched polyester may be included in 0.1 to 5% by weight or 1.5 to 2.5% by weight.

The weight ratio of the molecular chain cutting additive and the polyol may be, for example, 1:0.25 to 1:4 or 1:0.3 to 1:3, and within this range, the overall physical property balance is excellent, while the appearance and formability are excellent. to provide.

Other additives

Optionally, the composition of the present disclosure may optionally contain a lubricant, an antioxidant, a light stabilizer, a chain extender, a catalyst, a release agent, a pigment, a dye, an antistatic agent, an antibacterial agent, a processing aid, a metal inactivator, a smoke inhibitor, an inorganic filler (however, Glass fiber is excluded), and one or more additives selected from anti-friction agents and anti-wear agents.

The composition of the present disclosure may include a lubricant for the purpose of further improving fluidity and appearance quality, and the lubricant may be selected from fatty acid, amide, ester, polyethylene, montan wax, and paraffin wax as examples. It is not limited thereto, and may be added without particular limitation as long as it is a type commonly used in the art.

The additive may be used within a range that does not adversely affect the physical properties of the resin composition of the present invention, and as an example, 0.01 to 15 parts by weight, 0.05 to 10 parts by weight or 0.1 to 0.1 parts by weight based on 100 parts by weight of the glass fiber reinforced polyamide resin It may be included in 5 parts by weight.

Hereinafter, various examples of the glass fiber-reinforced polyamide resin composition of the present disclosure are described, but the scope of the present invention is not necessarily limited thereto.

The glass fiber reinforced polyamide resin composition is, for example, 50 to 70% by weight of polyhexamethylene adipamide and 100 to 50 parts by weight of glass fiber reinforced polyamide resin containing 30 to 50% by weight of glass fiber, isophthalic acid, adipic acid And 0.1 to 0.4 parts by weight of at least one chain scission additive selected from anhydrides thereof. And 0.1 to 0.5 parts by weight of a polyol having a dendrimer structure. In this case, there is an advantage in that the physical property balance is uniform, the appearance quality is excellent, and the heat resistance and fluidity are particularly excellent.

In another example, the glass fiber reinforced polyamide resin composition is polyhexamethylene adipamide 55 to 65% by weight and glass fiber reinforced polyamide resin containing 55 to 45% by weight of 100 parts by weight of polyamide resin, isophthalic acid 0.1 to 0.3 Parts by weight; And 0.1 to 0.3 parts by weight of a polyol having a dendrimer structure. In this case, the physical properties of the balance are uniform, particularly excellent in heat resistance and fluidity, and there is an advantage that the appearance quality is more excellent.

In another example, the glass fiber-reinforced polyamide resin composition may include 50 to 70% by weight of polyamide resin and 30 to 50% by weight of glass fiber reinforced polyamide resin, isophthalic acid, adipic acid, and 0.2 to 0.4 parts by weight of at least one chain scission additive selected from anhydrides thereof; And 0.1 to 0.3 parts by weight of a polyol having a dendrimer structure, wherein the polyamide resin is 65 to 85% by weight of polyhexamethylene adipamide and 15 to 35% by weight of polycaprolactam. , In this case, the physical properties such as mechanical strength, heat resistance, and moldability are excellent, but the appearance quality is greatly improved.

In another example, the glass fiber-reinforced polyamide resin composition, polyamide resin 25 to 40% by weight and glass fiber-reinforced polyamide resin 100 parts by weight, including 60 to 75% by weight, isophthalic acid, adipic acid And 0.2 to 0.4 parts by weight of at least one chain scission additive selected from anhydrides thereof. And 0.1 to 0.3 parts by weight of a polyol having a dendrimer structure. In this case, mechanical stiffness such as tensile strength, flexural characteristics, and impact strength is significantly increased while maintaining high heat resistance and moldability of the composition. , Appearance quality can also be improved.

In the description of the glass fiber-reinforced polyamide resin composition of the present disclosure, other additives and the like, which are not separately described, can be appropriately selected within a range commonly practiced in the art, and are not particularly limited.

Hereinafter, a method of manufacturing the glass fiber-reinforced polyamide resin composition of the present disclosure will be described in detail. The method of manufacturing the resin composition of the present disclosure shares all the technical characteristics of the above-mentioned glass fiber-reinforced polyamide resin composition, and a description overlapping with the above will be omitted.

The manufacturing method of the glass fiber reinforced polyamide resin composition is, for example, 25 to 70% by weight of polyamide resin and 30 to 70% by weight of glass fiber reinforced polyamide resin, 100 parts by weight of isophthalic acid, adipic acid And 0.05 to 1 part by weight of at least one chain scission additive selected from anhydrides thereof. And 0.05 to 1 part by weight of polyol; characterized in that it comprises a step of kneading and extruding, in which case, it is excellent in fluidity and has little gas generation during processing, so it is easy to mold and has excellent physical property balance and excellent appearance quality. There is a significant improvement.

The kneading and extrusion may be carried out under a temperature condition of 200 to 300°C or 280 to 300°C using, for example, an extrusion processing machine such as a twin-screw extruder or a single-screw extruder after first mixing in a banbury mixer or a supermixer. It is not necessarily limited to this.

In addition, the kneading may optionally further include the above-described additives as necessary.

Furthermore, the glass fiber reinforced polyamide resin composition of the present substrate may be provided as a molded product through injection molding or the like.

The molded article, including the glass fiber-reinforced polyamide resin composition of the present substrate has excellent mechanical strength, heat resistance, moldability, and the like, and has an excellent appearance quality, and can be used for automotive interior and exterior parts.

In describing the manufacturing method and molded article of the glass fiber-reinforced polymaamide resin composition of the present substrate, process steps, process conditions, equipment, and the like that are not explicitly described may be appropriately selected within a range commonly practiced in the art. , Not specifically limited.

Hereinafter, a preferred embodiment is provided to help the understanding of the present invention, but the following examples are only illustrative of the present invention, and it is apparent to those skilled in the art that various changes and modifications are possible within the scope and technical scope of the present invention. It is no wonder that such variations and modifications fall within the scope of the appended claims.

Materials used in the following examples and comparative examples are as follows.

A) Polyamide resin

A-1) Polyhexamethylene adipamide (nylon 6,6): relative viscosity measured by dissolving in a sulfuric acid solution having a concentration of 96% by weight at 25°C is 2.4 to 2.7cP, and a number average molecular weight of 12,000 to 17,000g/ A product of mol was used.

A-2) Polycaprolactam (nylon 6): a product having a relative viscosity of 2.0 to 2.6 cP measured by dissolving in a formic acid solution having a concentration of 85% by weight at 25°C, and a product having a number average molecular weight of 10,000 to 17,000 g/mol Did.

B) Glass fiber

An average diameter of 10 to 13 μm, an average length of 3 mm, and a surface-treated product with a silane coupling agent were used.

C) Molecular chain cutting additive

C-1) isophthalic acid

C-2) Adipic acid

D) Polyol

A polyol having a dendrimer structure containing 2% by weight of hyperbranched 2,2-bis(hydroxylmethyl)propionic acid polyester-16-hydroxyl (CAS No. 326794-48-3) was used.

[Examples and Comparative Examples]

Examples 1 to 10 and Comparative Examples 1 to 18 to 21

Each component is added to the super mixer at the contents shown in Tables 1 and 2 below, and after primary mixing, the mixture is melt-kneaded and extruded at 250 to 300°C using a twin-screw extruder to pellet the glass fiber reinforced polyamide resin composition. Was prepared. The pellet was dried at 80° C. for 4 hours or more and then injection-molded, and left at room temperature for 1 day, and then used as a specimen for measuring physical properties.

[Test Example]

The physical properties of the specimens prepared according to the Examples and Comparative Examples were measured by the following methods, and the results are shown in Tables 1 and 2 below.

* Tensile strength (unit: kg/cm ² )

A specimen having a thickness of 3.2 mm was prepared according to the method specified in ASTM D638 and measured under a condition of a tensile speed of 5 mm/min.

* Flexural strength (unit: kg/cm ² ) And flexural modulus (unit: kg/cm ² )

It was measured under the condition of a speed of 1.3 mm/min using a specimen having a thickness of 6.4 mm according to the method specified in ASTM D790.

* Heat distortion temperature (HDT, unit: ℃)

A specimen having a thickness of 6.4 mm was prepared according to the method specified in ASTM D648, and the heat deflection temperature was measured under a load of 1.80 MPa.

* Izod impact strength (unit: kgf·cm/cm)

A specimen having a thickness of 6.4 mm was prepared according to the method specified in ASTM D256, and notched on the specimen, then measured at room temperature (23° C.).

* Melt Index (unit: g/10 min)

It was measured under the conditions specified in ASTM D1238 at 275°C and a load of 2.16 kg.

* Gloss (unit: GU)

The gloss meter of the specimen was measured at an angle of 75° using a gloss meter according to the method specified in ASTM D528.

* Gas generation degree

The gas traces on the surface were visually observed to evaluate the degree of gas generation during injection according to the following criteria.

1: No gas trace is observed on the surface

2: occurs within 5% of the total specimen area

3: occurs within 10% of the total specimen area

4: occurs within 20% of the total area of the specimen

5: more than 20% of the total specimen area

division Example One 2 3 4 5 6 7 8 9 10 A-1 65 65 65 65 55 45 45 15 40 0 A-2 0 0 0 0 10 20 20 25 0 30 B 35 35 35 35 35 35 35 60 60 70 C-1 0.1 0.1 0.1 0.3 0.3 0.3 0 0.3 0.3 0.3 C-2 - - - - - - 0.3 0 0 0 D 0.1 0.2 0.3 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Property measurement result Tensile strength (kg/cm ² ) 1990 1970 1920 1990 1990 1990 1930 2450 2750 2630 Flexural strength (kg/cm ² ) 2395 2380 2300 2395 2395 2395 2240 3500 3790 3910 Flexural modulus (kg/cm ² ) 100400 99500 97400 100400 100400 100400 99780 178000 218000 251000 Impact strength (kgfcm/cm) 10 10 9 10 10 10 10 15 15 15 Melt Index (g/10 min) 20 18 20 20 20 20 20 14 12 18 HDT(℃) 260 260 260 260 260 260 260 255 260 220 Glossiness (GU) 50 65 60 70 80 85 72 30 25 45 Gas generation degree One One 2 One One One 2 One One One

(In Table 1, the content units of A and B are% by weight based on the total weight of A + B, and the content units of the remaining components are parts by weight based on 100 parts by weight of A + B.)

division Comparative example One 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 A-1 65 65 65 65 65 55 45 55 0 0 15 40 0 65 65 65 65 40 40 40 40 A-2 0 0 0 0 0 10 20 10 65 65 25 0 30 0 0 0 0 0 0 0 0 B 35 35 35 35 35 35 35 35 35 35 60 60 70 35 35 35 35 60 60 60 60 C-1 - - - - - - - - - - - - 0.4 0.1 0.3 0.5 One 0.02 1.2 0.1 0.1 C-2 - - - - - - - - - - - - - - - - - - - - - D - 0.1 0.2 0.3 One - - 0.1 - 0.1 - - - - - - - 0.1 0.1 0.02 1.2 Property measurement result Tensile strength (kg/cm ² ) 2000 1990 1950 1930 1830 1995 1990 1990 1850 1780 2300 2500 2542 2000 1990 1960 1880 2600 2450 2510 2700 Flexural strength (kg/cm ² ) 2400 2380 2350 2320 2230 2390 2390 2330 2320 2300 3415 3630 3821 2400 2380 2350 2290 3650 6400 3600 3710 Flexural modulus (kg/cm ² ) 105000 100000 99000 98000 92400 100000 100000 99500 95000 94500 170000 188000 247000 105000 102000 100000 95400 217000 181000 185000 200000 Impact strength (kgfcm/cm) 11 10 10 9 8 12 12 10 13 11 15 16 15 11 10 10 9 15 10 15 15 Melt Index (g/10 min) 8 16 18 20 28 10 15 20 28 45 8 5 8 13 16 18 18 8 15 6 20 HDT(℃) 260 260 260 260 255 255 250 255 220 220 260 260 220 260 260 260 260 260 260 260 260 Glossiness (GU) 36 31 33 33 28 50 65 48 80 87 15 8 25 40 45 50 70 10 15 10 20 Gas generation degree One One One 2 3 One One One One One One One 4 One One 4 5 2 3 2 3

(In Table 1, the content units of A and B are% by weight based on the total weight of A + B, and the content units of the remaining components are parts by weight based on 100 parts by weight of A + B.)

Referring to Table 1, in Examples 1 to 10 according to the present invention, tensile strength, flexural strength, flexural modulus, and impact strength are all excellent, but the melt index is high, so it can be confirmed that molding is easy. It can be confirmed that the temperature is high and the heat resistance is excellent and the gloss is excellent. In addition, when the molecular chain cutting additive and the polyol are prescribed together within a specific content range as in Examples 1 to 10, it can be confirmed that no gas traces are observed on the surface or hardly observed within 5% of the total area. It can be seen that a problem in that a large amount of gas is generated due to excessive molecular chain cutting, thereby reducing the formability and physical property balance has been solved.

On the other hand, referring to Comparative Example 1 of Table 2 above, when the molecular chain cutting additive and the polyol are not added, it can be confirmed that other conditions have significantly lower melt index compared to the equivalent Examples 1 to 4, resulting in poor moldability. The gloss is also low, which confirms the poor appearance quality.

In addition, referring to Comparative Examples 2 to 5 in Table 2, when the molecular chain cutting additive is omitted and the polyol is prescribed alone, it can be confirmed that the glossiness is significantly lower than those of Examples 1 to 3 in which other conditions are equivalent. From this, it can be clearly seen that the desired effect of the present invention can be achieved by a combination of a polyol and a specific molecular cleavage additive.

In addition, even when comparing Example 5 and Comparative Example 6 and Example 6 and Comparative Example 7, when using a combination of a polyol and a specific molecular slicing additive, the mechanical properties balance is maintained at a fairly high level while the melt index rises to increase molding. It is easy, and it can be seen that the glossiness is greatly improved.

For reference, it can be seen from Examples 6 and 7 that when using isophthalic acid as a molecular chain cutting additive, it is more advantageous to improve glossiness.

In addition, when comparing Examples 1 to 4 using polyhexamethylene adipamide alone as a polyamide resin and Examples 5 to 7 in which polyhexamethylene adipamide and polycaprolactam were mixed, a proper ratio of polycaprolactam was compared. It can be seen that the overall physical property balance is kept high when mixed and applied, and the appearance quality is particularly excellent, which is more advantageous when applied to products that emphasize more appearance.

In addition, when Example 8 and Comparative Example 11 and Example 9 and Comparative Example 12 are compared, Examples 8 and 9 have better tensile strength and flexural modulus than corresponding Comparative Examples, and have a higher melt index, so that molding is more advantageous. It can be confirmed that the glossiness is excellent.

In addition, even if Example 10 and Comparative Example 13 are compared, the mechanical properties are improved when the polyol and the molecular chain cutting additive are prescribed together as in Example 10, the melting index is high, molding is easy, and gloss is large. It can be seen that it can be improved. In addition, when comparing the gas generation degree of these, it can be confirmed that in the case of Comparative Example 13 in which the polyol was omitted and the molecular chain cutting additive was added alone, the gas generation marks were considerable even though the additive content was the same as in Example 10. It can be seen that excessive gas is generated due to excessive cleavage due to the molecular cleavage additive during molding, and when prescribing two additives together according to the present invention, excessive molecular cleavage is suppressed to contribute to improvement in moldability. You can confirm that you can.

In addition, referring to Example 1 and Comparative Example 14 and Example 4 and Comparative Example 15, Examples 1 and 4 in which polyols were prescribed together under conditions in which the content of molecular slicing additives were equal flowed compared to Comparative Examples 14 and 15, respectively. It can be seen that the index is higher, so that the moldability is excellent and the gloss is also excellent.

Further, when comparing Examples 1 to 4 and Comparative Examples 16 to 17, when the molecular chain cutting additive and the polyol are prescribed together, the amount of additive used (content of the molecular chain cutting additive and the polyol) is small compared to Comparative Examples 16 to 17. It can be seen that the physical property balance is excellent, and the appearance quality is considerably improved, and in particular, the glossiness of 1 to 4, which is relatively small in the amount of the additive used, is almost identical to Comparative Example 17 in which the molecular chain cutting additive is used alone as 1 part by weight. It can be confirmed that the level is equivalent. That is, in order to maximize the appearance quality by prescribing a molecular slicing additive, about 1 part by weight of this should be added (see Comparative Example 17), when prescribing a molecular slicing additive and a polyol together (see Example 4). ), even when a small amount of the molecular chain cutting additive is added in an amount of about 0.3 parts by weight, it is possible to secure an excellent appearance quality of the same level, and the content balance of the entire property is more excellent due to less additive content.

In addition, looking at the degree of gas generation in Comparative Examples 16 and 17, if the polyol is omitted and the molecular chain cutting additive is excessively applied, the gas generation amount is excessive due to excessive chain cutting during injection molding, resulting in poor moldability, and through this, When prescribing the molecular chain cutting additive together, it was confirmed that the overall physical property balance is excellent and the appearance quality and moldability can be simultaneously secured.

In addition, when Examples 5 to 6 and Comparative Examples 9 to 10 are compared, in the case of Examples 5 to 6, although the proportion of polycaprolactam is relatively small compared to Comparative Examples 9 to 10, the gloss is at the same level. That is, according to the present invention, it can be confirmed that the appearance of polyhexamethylene adipamide, which has relatively poor appearance quality, while maintaining a high physical property balance, can be implemented at the same level as polycaprolactam.

In addition, referring to Comparative Examples 18 to 21, it can be seen that even if both of the polyol and the molecular chain cutting additive are included, if their content exceeds the scope of the present invention, the effect of improving physical properties is insufficient.

Specifically, even if both types of additives are included, when the content of the molecular chain cutting additive is small (Comparative Example 18), it can be confirmed that the melt index is lower and the gloss is very low compared to Example 9 having the same basic composition. , Compared to Comparative Example 9 without two additives, it can be seen that the appearance improvement effect is incomplete, and the amount of gas generated increases, resulting in poor moldability. On the contrary, when the molecular chain cutting additive is excessively included (Comparative Example 19), the flexural modulus is very low compared to Example 9, the tensile and flexural strength is poor, the glossiness improvement effect is insufficient, and above all, two additives In the case of not including (Comparative Example 12), it can be confirmed that the gas generation amount is significant, and the moldability is poor.

In addition, even if both types of additives are included, when the content of the polyol is small (Comparative Example 20), the physical property balance such as flexural modulus, flexural strength, tensile strength, and melt index is lower than in Example 9, and the two kinds of additives are added. It can be seen that the effect of improving glossiness compared to Comparative Example 12 not included is insufficient and thus does not contribute to improvement of appearance quality. On the contrary, when the polyol is contained in an excessive amount (Comparative Example 21), the physical properties such as bending and tensile properties are good, but the glossiness improvement effect is inferior to that of Example 9, and the amount of gas generation is significant, indicating that the moldability is poor. have.

Claims (11)

25 to 70% by weight of polyamide resin and 30 to 70% by weight of glass fiber, 100 parts by weight of glass fiber reinforced polyamide resin,
0.05 to 1 part by weight of one or more chain scission additives selected from isophthalic acid, adipic acid, and anhydrides thereof; And polyol 0.05 to 1 part by weight; characterized in that it comprises a
Glass fiber reinforced polyamide resin composition. According to claim 1,
The polyamide resin is characterized in that it comprises 50 to 100% by weight of polyhexamethylene adipamide and 0 to 50% by weight of polycaprolactam.
Glass fiber reinforced polyamide resin composition. According to claim 2,
The polyhexamethylene adipamide is characterized in that the relative viscosity measured by dissolving in a formic acid solution having a concentration of 85% by weight at 25°C is 2.0 to 5.5 cP.
Glass fiber reinforced polyamide resin composition. According to claim 2,
The polycaprolactam is characterized in that the relative viscosity measured by dissolving in a sulfuric acid solution having a concentration of 96% by weight at 25°C is 2.0 to 5.5 cP.
Glass fiber reinforced polyamide resin composition. According to claim 1,
The polyamide resin is characterized in that the number average molecular weight is 10,000 to 500,000g / mol
Glass fiber reinforced polyamide resin composition. According to claim 1,
The glass fiber is characterized in that the average diameter is 3 to 20㎛, the average length is 1 to 5mm
Glass fiber reinforced polyamide resin composition. According to claim 1,
The polyol is characterized in that the chain or branched polyol
Glass fiber reinforced polyamide resin composition. The method of claim 7,
The branched polyol is characterized by being a polyol having a dendrimer structure
Glass fiber reinforced polyamide resin composition. Polyamide resin 25 to 70% by weight and glass fiber containing 30 to 70% by weight of glass fiber reinforced polyamide resin 100 parts by weight, one or more molecular chain cutting (chain scission) selected from isophthalic acid, adipic acid and anhydrides thereof ) 0.05 to 1 part by weight of additives; And 0.05 to 1 part by weight of polyol; characterized in that it comprises a step of kneading and extruding, including
Method for producing glass fiber reinforced polyamide resin composition. It characterized in that it comprises a glass fiber reinforced polyamide resin composition according to any one of claims 1 to 8
Molded article. The method of claim 10,
The molded article is characterized in that the interior and exterior parts of the car
Molded article.