KR20240042276A - Polyamide resin composition, method for preparing the thermoplastic resin composition and molding products thereof - Google Patents

Abstract

The present invention relates to a polyamide resin composition and a molded article manufactured therefrom. According to the present invention, the effect of providing a polyamide resin composition and a molded article manufactured therefrom that shortens cycle time and improves low-temperature impact strength, elongation, etc. there is.

Description

Polyamide resin composition, manufacturing method thereof, and molded product containing the same {POLYAMIDE RESIN COMPOSITION, METHOD FOR PREPARING THE THERMOPLASTIC RESIN COMPOSITION AND MOLDING PRODUCTS THEREOF}

The present invention relates to a polyamide resin composition, a manufacturing method thereof, and a molded article containing the same. More specifically, a polyamide resin composition that shortens cycle time and improves low-temperature impact strength, elongation, etc., a manufacturing method thereof, and a molded article comprising the same. It's about molded products.

Polyphenylene ether resin (hereinafter referred to as 'PPE resin') not only has excellent mechanical properties including impact resistance, heat resistance, and dimensional stability, but also has low moisture absorption rate and heat distortion temperature, so it is used as automobile wheel caps, wheel covers, etc. It is known to be suitable for parts exposed to large temperature and humidity variations in actual operating environments, and to various chemicals such as water, salt water, acids, and bases.

However, PPE resin alone has a high melt viscosity and has poor processability, so it is used as a variety of plastic materials by blending it with polyamide resin (hereinafter referred to as 'PA resin') to improve processability.

Polyamide resin (hereinafter referred to as 'PA resin') is a type of engineering plastic that has excellent mechanical properties, fast injection cycle time, and chemical resistance, and is used in a variety of applications such as electrical/electronic products and automobile interior materials.

Among the PA resins, polyhexamethylene adipamide (hereinafter referred to as 'PA66') and poly(azepan-2-one) (hereinafter referred to as 'PA6') are commonly used.

However, PPE resin and PA resin have a large difference in melt viscosity and greatly different chemical structures, so their compatibility is poor, so the effect of reinforcing physical properties is not sufficient, and the solidification speed is slow, resulting in poor productivity.

Japanese Patent Publication No. 2011-148922

The purpose of the present invention is to provide a polyamide resin composition that shortens cycle time and improves low-temperature impact strength, moisture absorption resistance, heat resistance, etc.

Additionally, an object of the present invention is to provide a method for producing the polyamide resin composition.

Additionally, an object of the present invention is to provide a molded article manufactured from the polyamide resin composition.

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

polyamide resin; polyphenylene ether resin; Styrene-based block copolymer; compatibilizer; and cycle time shortening materials;

Based on ISO 180, the notched Izod impact strength measured at 23 ℃ and the notched Izod impact strength measured at -30 ℃ under the conditions of specimen size 4 Provided is a polyamide resin composition that satisfies the following equation (1) when c is the crystallization temperature (Tc) measured under 20°C/min using a scanning calorimeter.

[Equation 1]

1 ≤ (a

(In Equation 1 above, a, b, and c satisfy 14≤a≤30, 8≤b≤24, and 182≤c≤294, respectively.)

The cycle time shortening material may be one or more selected from alumina silicate-based compounds , phosphate ester metal salts, sorbitol, fatty acid metal salts, and clay minerals.

The alumina silicate-based compound may be added as a masterbatch containing 60 to 97% by weight of polyamide 2.2 and 3 to 40% by weight of alumina silicate.

The fatty acid metal salt may be an alkali metal salt of montanic acid ester.

The alkali metal salt of the montanic acid ester may be at least one selected from sodium montanic acid ester and calcium montanic acid ester.

The clay mineral may be talc, nanoclay, or a mixture thereof.

The cycle time shortening material may include the masterbatch and the alkali metal salt of the montanate ester at a weight ratio of 1:2 to 1:12 (masterbatch: alkali metal salt of the montanate ester).

The styrene-based block copolymers include polystyrene-polybutadiene, polystyrene-poly(ethylene propylene), polystyrene-polyisoprene, polystyrene-polybutidaene-polystyrene, polystyrene-polyisoprene-polystyrene, and polystyrene-poly(ethylene, butylene). -It may be one or more types selected from polystyrene.

The polyamide resin may have a glass transition temperature (Tg) of 50°C or less, a crystallization temperature (Tc) of 190°C or less, and a relative viscosity (RV) of 3.0 or less.

The polyamide resin may include poly(azepan-2-one).

The polyamide resin has a number average molecular weight of 25,000 to 36,000 g/mol and a polydispersity index of 1.3 to 5.0. It can be within range.

The polyphenylene ether resin may have a number average molecular weight of 9,000 to 13,000 g/mol and a polydispersity index in the range of 2.4 to 3.4.

The compatibilizer is a liquid diene polymer, an epoxy compound, an oxidized polyolefin wax, a quinone compound, an organic silane compound, a multifunctional compound consisting of a carbon-carbon double bond and one or more carboxylic acids, a precursor of the multifunctional compound, and the multifunctional compound. It may be one or more types selected from acid anhydride, polyhydric carboxylic acid compound, and functionalized polyarylene ether.

The functionalized polyarylene ether may be a polyarylene ether functionalized with a reactive monomer, where the reactive monomer may be one or more selected from maleic acid, fumaric acid, itaconic acid, maleic anhydride, and citric acid.

The polyamide resin composition includes the styrene-based block copolymer, compatibilizer, and polyphenylene ether resin in a weight ratio of 1:0.5 to 1.0:3.5 to 5 (styrene-based block copolymer: compatibilizer: polyphenylene ether resin). It can be included.

The polyamide resin composition includes one or more additives selected from heat stabilizers, light stabilizers, lubricants, and antioxidants, and all components constituting the polyamide resin composition (polyamide resin; polyphenylene ether resin; styrene-based block) Copolymer; compatibilizer; and cycle time shortening material) may be included in a total amount of 0.01 to 10 wt% of 100 wt%.

The polyamide resin composition may have a heat distortion temperature of 66°C or higher as measured according to ISO 75.

In addition, the present invention

polyamide resin; polyphenylene ether resin; Styrene-based block copolymer; compatibilizer; and a cycle time shortening material, including kneading and extruding,

The cycle time shortening material is at least one selected from alumina silicate-based compounds and alkali metal salts of montanic acid esters,

According to ISO 180, the notched Izod impact strength measured at 23 ℃ and the notched Izod impact strength measured at -30 ℃ under the conditions of specimen size 4 Provided is a method for producing a polyamide resin composition, which satisfies the following equation (1) when c is the crystallization temperature (Tc) measured under 20°C/min using a scanning calorimeter.

[Equation 1]

1 ≤ (a

(In Equation 1 above, a, b, and c satisfy 14≤a≤30, 8≤b≤24, and 182≤c≤294, respectively.)

In addition, the present invention

A molded article comprising the above-described polyamide resin composition is provided.

The molded product is suitable for parts sensitive to moisture absorption, heat resistance, and dimensional stability in electronic devices, automobile parts, etc.

The automobile parts may be automobile wheel caps, automobile wheel covers, or automobile door handle parts.

According to the present invention, there is an effect of providing a polyamide resin composition that shortens cycle time and improves low-temperature impact strength, moisture absorption resistance, heat resistance, etc., and molded articles manufactured therefrom.

Therefore, the polyamide resin composition according to the present invention can be widely applied to fields that require it. In particular, it can be applied as a material for electronic devices and automobile parts that require moisture absorption resistance, heat resistance, and dimensional stability.

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

Terms and words used in this specification and claims should not be construed as limited to their common or dictionary meanings, and the inventor may appropriately define the concept of terms in order to explain the invention in the best way. Therefore, it should be interpreted with meaning and concept consistent with the technical idea of the present invention.

In this description, the "polydispersity index (PDI)" is a parameter representing molecular weight distribution. Unless otherwise specified, the "polydispersity index (PDI)" is the value (Mw/Mn) divided by the weight average molecular weight (Mw) by the number average molecular weight (Mn). refers to

In this description, “content” means weight unless otherwise defined, and “%” means weight% unless otherwise defined.

In this description, unless otherwise specified, 'cycle time' refers to the time it takes to fill, hold, solidify, and extract molten resin from the injection mold until one molded product is manufactured during injection molding, and solidification is generally assumed during these processes. This is the longest.

The present inventors included substances that can improve the solidification speed, salt water resistance, and chemical resistance in polyamide resin, and when controlling the amount of these used, the cycle time is shortened and low-temperature impact strength, moisture absorption resistance, and heat resistance characteristics are improved. After confirming the improvement, the present invention was completed.

One embodiment of the present invention is a polyamide resin; polyphenylene ether resin; Styrene-based block copolymer; compatibilizer; and a polyamide resin composition containing a cycle time shortening material.

The polyamide resin composition according to an embodiment of the present invention improves tensile strength, flexural strength, flexural modulus, impact strength, heat distortion temperature, etc. by mixing one or more cycle time shortening materials with polyamide resin and polyphenylene ether resin. Although it is equal to or higher than this, the crystallization temperature can be improved to shorten the solidification speed and achieve moisture and salt water resistance.

Hereinafter, each component constituting the polyamide resin composition of the present material will be examined in detail as follows.

polyamide resin

The polyamide resin of the present invention has excellent chemical resistance and mechanical properties, maintains high properties for a long time, and can provide a fast injection cycle, so it also has excellent processability.

The polyamide resin of the present invention has a structure that does not contain an aromatic ring in the main chain and is manufactured by ring-opening polymerization.

For example, the polyamide resin has a unit represented by the following formula (1), the unit is repeated 50 to 500 times, L is (CH ₂ ) _n , n is an integer of 3 to 6, and is semi-crystalline, amorphous or It may be a mixture of these.

[Formula 1]

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

In this description, semi-crystalline and amorphous may follow definitions and measurement methods commonly used in the technical field to which the present invention pertains.

The polyamide resin may preferably be poly(azepan-2-one).

The polyamide resin may have a glass transition temperature of, for example, 30 to 50°C, preferably 30 to 45°C. If the above-mentioned range is satisfied, excellent processability can be provided, which has the effect of improving the moldability of molded articles manufactured by molding the polyamide resin composition of the present invention.

The polyamide resin may have a melting temperature (Tm) of, for example, 215 to 245°C, preferably 215 to 225°C. If the above-mentioned range is satisfied, better flow characteristics can be provided along with processability, which has the effect of improving the appearance moldability of molded products manufactured by molding the polyamide resin composition of the present invention.

The polyamide resin may have a crystallization temperature (Tc) of, for example, 170 to 190°C, preferably 177 to 185°C. If the above-mentioned range is satisfied, a faster solidification speed can be provided compared to conventional materials when product design and design changes are considered simultaneously, and high rigidity, flame retardant properties, and fast injection cycle characteristics can be secured.

In the present invention, the melting temperature (Tm) is, for example, raised to 300°C at a rate of 20°C/min using the manufacturer TA, model name Q2000, immediately lowered to 23°C at a rate of 20°C/min, and then reheated to 20°C. Raise the temperature in °C/min and refer to the endothermic peak when melting. The sample amount used at this time is in the range of 2 to 3 mg on average.

In this material, the glass transition temperature can be measured at a temperature increase rate of 10°C/min using TA Instruments Q100 DSC (Differential Scanning Calorimetry) according to ASTM D 3418, for example.

In this material, the crystallization temperature is, for example, melting 5 mg of the specimen at 220 ℃ for 5 minutes, cooling at a cooling rate of 10 ℃/min to completely remove thermal history, and using a Dynamic Scanning Calorimeter (DSC). and measure.

The polyamide resin uses 96 wt% sulfuric acid as a solvent, and has a relative viscosity (20°C) calculated with a resin concentration in the solution of 1.0 w/v%, for example, 3.0 or less, preferably 2.0 to 3.0, more preferably It is preferably 2.4 to 2.7.

The polyamide resin may have a number average molecular weight (Mn) of, for example, 25,000 to 36,000 g/mol, or 28,000 to 36,000 g/mol, preferably 30,000 to 36,000 g/mol, and a polydispersity index of, for example, 1.3. to 5.0, or 2.5 to 5.0, preferably 2.8 to 5.0.

The polyamide resin may comprise, for example, 30 to 55% by weight, preferably 35 to 45% by weight, of the total resin composition. When the polyamide resin is included in the above range, a polyamide resin composition with excellent physical property balance between processability, specific gravity, mechanical properties, and crystallization temperature can be secured, and from this, it can provide a faster solidification speed compared to conventional materials. there is.

polyphenylene ether resin

The polyphenylene ether resin of the present invention exhibits a low moisture absorption rate and also has excellent mechanical properties such as heat distortion temperature, dimensional stability, and impact strength.

The polyphenylene ether resin of the present invention contains a phenyleneoxy repeating unit represented by the following formula (2).

[Formula 2]

In Formula 2, R1 is a halogen, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, and n1 is 0 to 30 carbon atoms. It is an integer of 4.

The polyphenylene ether resin is produced by condensation polymerization of one or more phenolic compounds represented by the following formula (3):

[Formula 3]

In Formula 3, R1, R2, R3, R4, and R5 are independently selected from hydrogen, a halogen atom, and a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms, and R1, R2, R3, R4, and At least one of R5 is hydrogen.

Specifically, in Formula 3, R1, R2, R3, R4, and R5 are the same or different, and are each independently hydrogen, chlorine, bromine, fluorine, iodine, alkyl of 1 to 7 carbon atoms, phenyl, haloalkyl, may be selected from aminoalkyl, hydroxyalkyl, hydrocarbonoxy, and halohydrocarbonoxy.

In Formula 3, specific examples of R1, R2, R3, R4, and R5 include methyl, ethyl, n- or iso-propyl, pri-, sec-, or t-butyl, chloroethyl, hydroxyethyl, and phenylethyl. , benzyl, hydroxymethyl, aminomethyl, aminoethyl, carboxyethyl, methoxycarbonylethyl, cyanoethyl, phenyl, chlorophenyl, methylphenyl, dimethylphenyl, ethylphenyl, allyl, etc., but are limited thereto. no.

Specific examples of the compound represented by Formula 3 include phenol, o-, m-, or p-cresol, 2,6-, 2,5-, 2,4- or 3,5-dimethylphenol, 2-methyl-6 -Phenylphenol, 2,6-diphenylphenol, 2,6,-diethylphenol, 2-methyl-6-ethylphenol, 2,3,5-, 2,3,6-, or 2,4,6 -Trimethylphenol, 3-methyl-6-t-butylphenol, 2-methyl-6-allylphenol, etc. may be mentioned, but are not limited thereto.

Specific examples of the polyphenylene ether resin include poly(1,4-phenylene ether), poly(1,3-phenylene ether), poly(1,2-phenylene ether), and poly(2-methyl-1). ,4-phenylene ether), poly(3-methyl-1,4-phenylene ether), poly(2-methyl-1,3-phenylene ether), poly(4-methyl-1,3-phenylene) ether), poly(5-methyl-1,3-phenylene ether), poly(6-methyl-1,3-phenylene ether), poly(3-methyl-1,2-phenylene ether), poly( 4-methyl-1,2-phenylene ether), poly(5-methyl-1,2-phenylene ether), poly(6-methyl-1,2-phenylene ether), poly(2,6-dimethyl) -1,4-phenylene ether), poly (2,3-dimethyl-1,4-phenylene ether), poly (3,5-dimethyl-1,4-phenylene ether), poly (2,5- dimethyl-1,4-phenylene ether), poly(2,4-dimethyl-1,3-phenylene ether), poly(2,5-dimethyl-1,3-phenylene ether), poly(2, 6-dimethyl-1,3-phenylene ether), poly(4,5-dimethyl-1,3-phenylene ether), poly(4,6-dimethyl-1,3-phenylene ether), poly(5) ,6-dimethyl-1,3-phenylene ether), poly(3,4-dimethyl-1,2-phenylene ether), poly(3,5-dimethyl-1,2-phenylene ether), poly( 3,6-dimethyl-1,2-phenylene ether), poly(4,5-dimethyl-1,2-phenylene ether), poly(4,6-dimethyl-1,2-phenylene ether), poly (5,6-dimethyl-1,2-phenylene ether, etc. may be included, but are not limited thereto.

The polyphenylene ether resin may have a number average molecular weight (Mn) of, for example, 9,000 to 13,000 g/mol, or 9,000 to 12,000 g/mol, preferably 9,500 to 11,500 g/mol, and a polydispersity index of, for example, It may be 2.4 to 3.4, or 2.5 to 3.3, and preferably 2.6 to 3.2. In this case, the difference in melt viscosity with the polyamide resin is reduced during melt kneading, thereby improving compatibility with the polyamide component, and as a result, the moldability and product appearance of the manufactured resin composition can be improved without deteriorating mechanical properties.

The polyphenylene ether resin may be included in, for example, 30 to 55% by weight, preferably 36 to 49% by weight, of the total resin composition. When the polyphenylene ether resin is included in the above range, a polyamide resin composition with excellent physical property balance of processability, low moisture absorption, salt resistance, specific gravity, and mechanical properties can be secured, and from this, it has the property of having a faster solidification speed compared to conventional materials. can be provided.

Styrenic block copolymer

In the present invention, a styrene-based block copolymer is included in order to increase the impact strength and mechanical properties of the polyamide resin composition.

For example, the styrene-based block copolymer may be a diblock copolymer and a triblock copolymer containing two or more blocks selected from aromatic vinyl blocks, olefin blocks, and diene blocks.

Specific examples of the styrene-based block copolymer include polystyrene-polybutadiene, polystyrene-poly(ethylene propylene), polystyrene-polyisoprene, polystyrene-polybutidaene-polystyrene, polystyrene-polyisoprene-polystyrene, and polystyrene-poly(ethylene, butyl). It may be one or more types selected from ren)-polystyrene.

The styrene-based block copolymer may be included, for example, in an amount of 3 to 13% by weight, or 5 to 13% by weight, and preferably 7 to 13% by weight, based on the total resin composition. When the styrene-based block copolymer is included in the above range, a polyamide resin composition with excellent physical property balance of processability, moisture and salt resistance, specific gravity, and mechanical properties can be secured, and this provides the property of a faster solidification speed compared to conventional materials. can do.

compatibilizer

In the present invention, a compatibilizer is included to improve miscibility between the above-described polyamide resin and polyphenylene ether resin.

The compatibilizer is, for example, a liquid diene polymer, an epoxy compound, an oxidized polyolefin wax, a quinone compound, an organic silane compound, a polyfunctional compound consisting of a carbon-carbon double bond and one or more carboxylic acids, a precursor of the polyfunctional compound, the above One or more types of functional compounds selected from acid anhydrides, polyhydric carboxylic acid compounds, and functionalized polyarylene oxides may be used.

The functionalized polyarylene ether may preferably be functionalized polyphenylene oxide.

The functionalized polyphenylene oxide may be a compound grafted with a reactive monomer.

For example, the reactive monomer may be selected from one or more of citric anhydride, maleic anhydride, maleic acid, itagonic anhydride, fumaric acid, (meth)acrylic acid, and (meth)acrylic acid ester, preferably citric anhydride or fumaric acid. In this case, the miscibility between the above-described polyamide resin and polyphenylene ether resin can be sufficiently demonstrated.

The manufacturing method of the compatibilizer may follow a manufacturing method commonly used in the technical field to which the present invention pertains.

For example, the compatibilizer may be included in an amount of 3 to 12% by weight, preferably 5 to 10% by weight, of the total resin composition. When the compatibilizer is included within the above range, a polyamide resin composition with excellent physical property balance of processability, moisture and salt resistance, specific gravity, and mechanical properties can be secured, and from this, it can provide the property of a faster solidification speed compared to conventional materials. .

Cycle time reduction material

In the present invention, a cycle time shortening material is included in order to increase the crystallization temperature and solidification speed of the polyamide resin composition.

When the cycle time shortening material is included in the polyamide resin composition, the mechanical properties such as tensile strength, flexural strength, flexural modulus, and impact strength of the molded article formed from the resin composition, heat resistance properties such as crystallization temperature and heat distortion temperature, and Product appearance can be improved.

In particular, in the field of parts molding using the polyamide resin composition of the present invention, the key is to increase the crystallization temperature of the resin composition, shorten the cycle time, and secure low-temperature impact strength, elongation, and dimensional stability.

In order to provide such crystallization temperature and low-temperature impact strength, specific ingredients are introduced. For example, when using one or more selected from alumina silicate-based compounds , phosphate ester metal salts, sorbitol, fatty acid metal salts, and clay minerals, sufficient basic resin is used. It was confirmed that heat resistance and mechanical properties were maintained, and that formability and low-temperature impact strength were sufficiently secured.

For example, the alumina silicate-based compound may be added as a masterbatch containing 60 to 97% by weight of polyamide 2.2 and 3 to 40% by weight of alumina silicate, and preferably 2.2, 70 to 95% by weight of polyamide and alumina silicate. It may contain 5 to 30% by weight, more preferably 2.2 85 to 93% by weight of polyamide and 7 to 15% by weight of alumina silicate. In this case, a polyamide resin composition with excellent physical property balance of processability, mechanical properties, and flame retardancy can be secured, and from this, a rigid and low-temperature impact-resistant molded product can be provided.

The polyamide 2.2 may be a high-melt polyamide or a material that increases the solidification rate, and commercially available products may also be used as long as they follow the definition of the present invention.

The alumina silicate can be represented by the structural formula 3Al2O3·2SiO2, and can shorten the solidification rate compared to aluminum titanate (Al2O3·TiO2) and exhibit improved reinforcing effects due to excellent dispersibility within the polyamide resin composition. It can be preferably applied because it does not impede the processability of.

For example, the alumina silicate-based compound may be included in an amount of 0.01 to 1% by weight, preferably 0.05 to 0.2% by weight, of the total resin composition. When the alumina silicate-based compound is included in the above range, a polyamide resin composition with excellent physical property balance between processability, specific gravity, mechanical properties, and crystallization temperature can be secured, and from this, it can provide the property of a faster solidification speed compared to conventional materials. You can.

For example, the fatty acid metal salt may be an alkali metal salt of montanic acid ester.

For example, the alkali metal salt of the montanic acid ester may be one or more selected from sodium montanic acid ester and calcium montanic acid ester.

The alkali metal salt of the montanic acid ester may be included, for example, in an amount of 0.01 to 1% by weight, preferably in an amount of 0.2 to 0.7% by weight, based on the total resin composition. When the alkali metal salt of the montanic acid ester is included in the above range, a polyamide resin composition with excellent physical property balance between processability, specific gravity, mechanical properties, and crystallization temperature can be secured, and from this, it has the property of having a faster solidification speed compared to conventional materials. can be provided.

The phosphate ester metal salt, sorbitol, and clay minerals may be those commonly used in the related technical field.

The cycle time shortening material in the present invention is the above-mentioned masterbatch and the alkali metal salt of montanic acid ester, for example, at a weight ratio of 1:2 to 1:12 (masterbatch: alkali metal salt of montanic acid ester), or 1:2.5 to 1. It can be included in a weight ratio of :5 (masterbatch:alkali metal salt of montanic acid ester). When the cycle time shortening material includes the alumina silicate-based compound and the alkali metal salt of montanic acid ester in the above weight ratio, a polyamide resin composition with excellent physical property balance between processability, specific gravity, mechanical properties, and crystallization temperature can be secured, From this, it can provide a faster solidification speed compared to conventional materials.

polyamide resin composition

The polyamide resin composition according to the present invention has a notched Izod impact strength measured at 23°C and a notched Izod impact strength measured at -30°C under the conditions of a specimen size of 4 and b, and c is the crystallization temperature (Tc) measured under conditions of 20°C/min using a differential scanning calorimeter in a nitrogen atmosphere. It is characterized in that it satisfies the following equation 1, and in this case, processability, It is possible to secure a polyamide resin composition with excellent physical property balance between specific gravity, mechanical properties, and crystallization temperature, and this can provide a faster solidification speed compared to conventional materials.

[Equation 1]

1 ≤ (a

In Equation 1, a, b, and c satisfy 14≤a≤30, 8≤b≤24, and 182≤c≤294, respectively.

If the above equation 1 is satisfied, a polyamide resin composition with excellent physical property balance between processability, specific gravity, mechanical properties, and crystallization temperature can be secured, and this can provide a faster solidification speed compared to conventional materials.

The calculated value of Equation 1 may be, for example, 1.5 to 20, or 1.5 to 18, and preferably 1.5 to 15, in which case polyamide has excellent physical property balance between processability, specific gravity, mechanical properties, and crystallization temperature. A resin composition can be secured, which can provide the property of a faster solidification speed compared to conventional materials.

In the polyamide resin composition according to the present invention, the content of the styrene-based block copolymer, compatibilizer, and polyphenylene ether resin is, for example, a weight ratio of 1: 0.5 to 1.0: 3.5 to 5 (styrene-based block copolymer: compatibilized). agent: polyphenylene ether resin), and may preferably be included in a weight ratio of 1:0.5 to 1.0:3.6 to 4 (styrene-based block copolymer: compatibilizer: polyphenylene ether resin). In this case, a polyamide resin composition with excellent physical property balance between processability, specific gravity, mechanical properties, and crystallization temperature can be secured, and this can provide a faster solidification speed compared to conventional materials.

In one embodiment of the present invention, the polyamide resin composition may include, for example, one or more additives selected from stabilizers, lubricants, and antioxidants.

The stabilizer may include, for example, a heat stabilizer (hereinafter also referred to as a primary stabilizer) and a light stabilizer (hereinafter also referred to as a secondary stabilizer).

In one embodiment of the present invention, the additive is the polyamide resin described above. For example, 10% by weight or less, 0.05 to 10% by weight, preferably 0.01% by weight of the total 100% by weight of the polyamide resin composition containing polyphenylene ether resin, styrene-based block copolymer, compatibilizer, cycle time shortening material and additives. It may be included in 10% by weight. If the above-mentioned range is satisfied, excellent release properties and injection properties can be sufficiently provided.

The heat stabilizer is, for example, tris (nonylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite ; TBPP), 2,4,6-tri-tert-butylphenyl-2-butyl-2-ethyl-1,3-propanediol phosphite (2,4,6-tri-tert-butylphenyl-2-butyl- 2-ethyl-1,3-propanediol phosphite), diisodecyl pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, bis (2,4-di- t-butylphenyl) pentaerythritol diphosphite (bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite; PEP24), bis (2,4-di-cumylphenyl) pentaerythritol diphosphite (bis ( 2,4-dicumylphenyl)pentaerythritol diphosphite), and tetrakis(2,4-di-t-butylphenyl)[1,1-biphenyl]-4,4'-diyl bisphosphonite (tetrakis(2,4 It may be one or more types selected from the group consisting of -di-tertbutylphenyl)[1,1-biphenyl]-4,4'-diyl bisphosphonate).

The heat stabilizer is, for example, 0.01 to 2% by weight, preferably 0.01 to 1% by weight, based on 100% by weight of the polyamide resin composition including additives, and within the above range, heat resistance is excellent.

For example, the light stabilizer may be a benzotriazole-based stabilizer.

As a specific example, the light stabilizer is 2-(2'-Hydroxy-5'-t-octylphenyl)-benzotriazole, product name Cyasorb UV-541) 2-(2'-Hydroxy-5'-methylphenyl)benzotriazole, product name Tinuvin- P), 2-(2'-Hydroxy-3'-tert.butyl-5'-methylphenyl)-5-chloro-benzotriazole, product name Tinuvin-326), 2-(2'-Hydroxy-3',5'- ditert.butylphenyl)- 5-chloro-benzotriazole, product name Tinuvin-327), 2-(2'-Hydroxy-3,5-di-tert.amylphenyl) benzotriazole, product name Tinuvin-328), 2-(2'- hydroxy-3',5'-di(1,1-imethylbenzyl)phenyl]-2H-benzotriazole, product name Tinuvin-234), 2-(2'hydroxy-3',5'-di-t-butylphenyl)benzotriazole, It may be one or more selected from product name Tinuvin-320), and 2-(2H-benzotrizol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, product name Tinuvin-329).

The heat stabilizer is, for example, 0.01 to 2% by weight, preferably 0.01 to 1% by weight, based on 100% by weight of the polyamide resin composition including additives, and within the above range, the ultraviolet ray absorption effect can be maximized.

As the light stabilizer, a HALS-type UV stabilizer can be used together.

The lubricant according to the present invention may be a lignite-derived mineral wax or an olefin-based wax, and serves to maintain excellent release properties and injection properties in the polyamide resin composition.

The olefin-based wax is a polymer with a low melt viscosity and may be an oily solid having slipperiness and plasticity. For example, it may be one or more types selected from polyethylene wax and polypropylene wax, and may be a commercially available product as long as it follows the definition of the present invention. You can use it.

The mineral wax may be a heat-stable material due to its high melting point and hardness, and commercially available products may also be used as long as they comply with the definition of the present invention.

The lubricant is the polyamide resin described above. Of the total 100% by weight of the polyamide resin composition including polyphenylene ether resin, styrene-based block copolymer, compatibilizer, cycle time shortening material and additives, for example, 0.01 to 2% by weight, preferably 0.01 to 1% by weight. It may be included, and within this range, it has the effect of improving the wettability of the composition of this base and at the same time providing excellent mechanical properties.

The antioxidant may be of various known types as long as it does not adversely affect the polyamide resin composition of the present invention.

The antioxidant is the polyamide resin described above. Of the total 100% by weight of the polyamide resin composition including polyphenylene ether resin, styrene-based block copolymer, compatibilizer, cycle time shortening material and additives, for example, 0.01 to 2% by weight, preferably 0.01 to 1% by weight. And within the above range, processability is excellent.

In addition, processing aids, pigments, colorants, etc. may be further included as needed.

The polyamide resin composition is characterized in that it is a resin composition having a heat distortion temperature of, for example, 66°C or higher, or 100°C or higher, as measured according to ISO 75.

The polyamide resin composition may be a resin composition having moisture resistance and salt water resistance properties.

As a specific example, the polyamide resin composition is a low moisture absorption salt water (chemical resistance) resin composition that can shorten cycle time and improve low-temperature impact strength, moisture absorption resistance, and heat resistance characteristics.

In this description, the recrystallization temperature refers to the temperature at which recrystallization occurs due to residual heat contained in the resin after melting, and is in series with product productivity.

Method for producing polyamide resin composition

The polyamide resin composition according to the present invention can be prepared by methods known in the art. For example, the polyamide resin composition can be manufactured in the form of pellets by melting and extruding a mixture of each component and other additives in an extruder, and the pellets can be used to manufacture injection or extrusion molded products. there is.

The method for producing the polyamide resin composition shares all technical features of the polyamide resin composition described above. Therefore, description of overlapping parts is omitted.

In the method for producing the polyamide resin composition, kneading and extrusion may be performed through a single-screw extruder, a twin-screw extruder, or a Banbury mixer, and is preferably performed through a twin-screw extruder. In this case, the composition is uniformly dispersed and commercially available. It has excellent effects.

For example, the step of producing pellets using the extrusion kneader may be performed at a barrel temperature of 240 to 300 ° C., or 260 to 290 ° C. In this case, sufficient melt kneading may be possible while the throughput per unit time is appropriate, , it has the effect of not causing problems such as thermal decomposition of the resin component.

The step of producing pellets using the extrusion kneader may be performed under conditions where the screw rotation speed is, for example, 100 to 300 rpm, preferably 210 to 260 rpm, and in this case, the throughput per unit time is appropriate, resulting in excellent process efficiency. There is.

The polypolyamide resin composition pellets can be used as is or after being dehumidified and dried under hot air.

For example, the dehumidifying drying may be performed in a hot air dryer with a temperature range of 80 to 100° C. for 4 hours or more.

For example, the pellet may be manufactured into an injection molded product using an injection molding machine at an injection barrel temperature of 210 to 300° C., or 240 to 290° C.

The method for producing the polyamide resin composition of the present invention includes, for example, polyamide resin; polyphenylene ether resin; Styrene-based block copolymer; compatibilizer; and a cycle time shortening material, including kneading and extruding.

The cycle time shortening material may be one or more selected from alumina silicate-based compounds and alkali metal salts of montanic acid esters.

The polyamide resin composition has the notched Izod impact strength measured at 23 ℃ and the notched Izod impact strength measured at -30 ℃ under the conditions of specimen size 4 When c is the crystallization temperature (Tc) measured under the condition of 20°C/min using a differential scanning calorimeter in a nitrogen atmosphere, the following equation 1 can be satisfied.

[Equation 1]

1 ≤ (a

(In Equation 1 above, a, b, and c satisfy 14≤a≤30, 8≤b≤24, and 182≤c≤294, respectively.)

<Molded product>

According to another embodiment of the present invention, a molded article manufactured from the above-described polyamide resin composition is provided.

The molded article may have a tensile strength of, for example, 46 MPa or more, preferably 46 to 60 MPa or more, as measured at a test speed of 50 mm/min using a test piece with a size of 170

In addition, the molded product has a flexural strength measured at a span length of 64 mm and a test speed of 2 mm/mi using a test piece with a size of 80 It may be from 90 MPa to 90 MPa.

In addition, the molded article may have a flexural modulus of, for example, 1,700 MPa or more, or 1,720 to 2,300 MPa, as measured using a test piece with a size of 80

In addition, the molded product has an impact strength measured at 23°C under the conditions of a specimen size of 4 It may be m2.

In addition, the molded product has a size of 80 For example, the impact strength measured in-chamber may be 8 kJ/m2 or more, or 8 to 20 kJ/m2.

In addition, the molded article may have a crystallization temperature of, for example, 182°C or higher, or 185 to 294°C, as measured under conditions of 20°C/min using a differential scanning calorimeter in a nitrogen atmosphere.

In addition, the molded product has a heat distortion temperature measured by the flatwise method using a high load weight of 1.8 MPa with a stress load of 1.8 MPa on a test piece with a size of 80 , 70 to 110 °C, or 86 to 100 °C.

Therefore, the polyamide resin composition of the present invention can be used as a material for molded articles requiring excellent moldability, heat resistance, high strength, low-temperature impact resistance, moisture resistance, and salt water resistance.

The polyamide resin composition of the present invention can be applied to a variety of applications requiring moisture-resistant, low-moisture-resistance, salt-water-resistant (chemical-resistant) parts. For example, it can be widely applied in the fields of automobile wheel caps, automobile wheel cover parts, or automobile door handle components.

The molded article can be manufactured by extruding the above-described polyamide resin composition into various shapes such as various extruded products, sheets by extrusion molding, and films. The various extrusion molding methods include cold runner method, hot runner method, as well as injection compression molding, injection press molding, gas assisted injection molding, foam molding (including injection molding of supercritical fluid), insert molding, and in-molding. Injection molding methods include decoating molding, insulation mold molding, rapid heating and cooling mold molding, heterochromatic molding, sandwich molding, and ultra-high-speed injection molding.

In addition, inflation, calendar, and casting methods can also be used to form sheets and films.

It is also possible to mold the tube into a heat-shrinkable tube by subjecting it to a specific stretching operation. It is also possible to manufacture a hollow molded product by molding the resin composition of the present invention by rotation molding, blow molding, etc.

In describing the polyamide resin composition, its manufacturing method, and molded article of the present disclosure, other conditions and equipment not explicitly described can be appropriately selected within the range commonly practiced in the industry, and are not particularly limited. Specify.

In addition, when describing the polyamide resin composition and molded article of the present disclosure, it is specified that other conditions or equipment not explicitly described can be appropriately selected within the range commonly practiced in the industry and are not particularly limited. .

Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily practice it. However, the present invention may be implemented in various different forms and is not limited to the embodiments described herein.

[Example]

The specifications of the materials used in the examples and comparative examples of the present invention are as follows.

(A) Polyamide resin: A resin containing poly(azepan-2-one), Tg 50°C or lower, Tc 190°C or lower, relative viscosity (RV) 2.6 to 2.8

(B) Polyphenylene ether resin: Bluestar product name LXR045

(C) Styrene-based block copolymer: Polystyrene-polybutadiene-polystyrene copolymer LG Chemical Company Product name LG501S

(D) Compatibilizer: Gpharm product name SPO2-ZA

(E) Cycle time reduction materials:

(E-1) Alumina silicate-based compound: Compound containing 90% by weight of polyamide 2.2 and 10% by weight of alumina silicate.

(E-2) Calcium salt of montanic acid ester

(F) Stabilizer:

(F-1) Primary stabilizer: BASF product name Irganox 1010

(F-2) Secondary stabilizer: BASF product name Irgafos 168

Examples 1 to 5, Comparative Examples 1 to 6

A resin composition in the form of pellets was prepared by melt-kneading the contents shown in Table 1 below in a twin-screw extruder heated to 260 to 290°C.

The (A) polyamide resin, (B) polyphenylene ether resin, (C) styrene-based block copolymer, (D) compatibilizer, (E) cycle time shortening material, and (F) stabilizer include all of these. The polyamide resin composition was added so that it was 100% by weight. Specifically, a total of 0.4% by weight of (F-1) primary stabilizer and (F-2) secondary stabilizer were added to (A) polyamide resin.

In addition, the manufactured pellets were dried at 100°C for 2 to 4 hours, and then a specimen for evaluating mechanical properties was produced using a screw-type injection machine set at a mold temperature of 80°C, a hopper temperature of 270°C, and a nozzle temperature of 285°C during injection. .

division Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative Example 5 Comparative Example 6 A 38.95 43.90 40.40 36.70 49.00 25.70 35.60 20.67 24.00 39.60 54.97 B 40.00 40.00 45.00 45.00 35.00 60.00 50.00 60.00 60.00 45.00 25.70 C 10.00 10.00 6.00 10.00 10.00 6.00 6.00 6.00 7.50 10.00 6.00 D 10.00 5.00 7.50 7.50 5.00 7.50 7.10 12.50 7.50 4.60 12.50 E-1 0.05 0.20 0.20 0.10 0.20 - 0.50 0.03 0.20 - 0.03 E-2 0.60 0.50 0.50 0.30 0.40 0.40 0.40 0.40 0.40 0.40 0.40 F-1 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 F-2 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20

The raw materials used in Table 1 have a total content of A to F-2 of 100% by weight.

[Test example]

The properties of the pellets and specimens prepared in Examples 1 to 5 and Comparative Examples 1 to 6 were measured by the following method, and the results are shown in Table 2 below.

*Impact strength (unit kJ/m2): Based on ISO 180, conducted at 23 ℃ (room temperature) and -30 ℃ (cold temperature) under the conditions of specimen size of 4

*Crystallization temperature (℃): Conducted under conditions of 20℃/min using differential scanning calorimetry (DSC) in a nitrogen atmosphere.

*Heat distortion temperature (°C): Conducted in a flatwise manner using a high stress weight of 1.8MPa on a test piece with a size of 80

*Cycle time: If the cycle time is shortened based on the cycle time required in Comparative Example 2 below, it is evaluated as ◎ and ○. If the cycle time is at the same level as Comparative Example 2, it is evaluated as △, and the work is impossible. is evaluated as X.

*Crystallization temperature and mechanical property balance: Let the measured impact strength at 23 ℃ be a, the measured impact strength at 30 ℃ be b, and the measured crystallization temperature be c, and the following equation 1 The calculations were made, and the results are shown in Table 3 below.

[Equation 1]

1 ≤ (a

division Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative example 2 Comparative Example 3 Comparative Example 5 Comparative Example 6 Room temperature impact strength (kJ/m2) 24.7 24.6 18.8 23.8 19.5 12.5 12.7 11.6 8.2 22.1 Low-temperature impact strength (kJ/m2) 15.7 18.2 14.9 17.8 16.1 8.5 7.6 9.4 6.4 15.3 Crystallization temperature (℃) 187 189 189 188 189 178 189 179 189 177 Mass production workability ○ ◎ ○ ○ ◎ X △ X X ○ heat distortion temperature 86 101 94 86 110 74 86 66 64 86 (a 2.07 2.36 14.82 2.25 1.66 0.59 0.51 0.6 0.27 1.91

Referring to Tables 1 and 2 above, the polyamide resin, polyphenylene ether resin, styrene-based block copolymer, compatibilizer, and cycle time shortening material, which are essential components according to the present invention, are included in the composition according to the present invention. In Examples 1 to 5, the room temperature impact strength, low temperature impact strength, and crystallization temperature were all increased, confirming the physical property balance of mechanical properties and crystallization temperature, and the cycle time was also satisfactory.

On the other hand, in the case of Comparative Example 1, in which the polyamide resin was used in a small amount outside the appropriate range and the polyphenylene ether resin was used in an excessive amount outside the appropriate range, and at the same time did not contain an alumina silicate-based compound, the room temperature impact strength was lower than that of Examples 1 to 5. It was confirmed that both low-temperature impact strength and crystallization temperature were decreased, and the cycle time was such that work was impossible.

In addition, in the case of Comparative Example 2, which did not include the alkali metal salt of montanic acid ester among the cycle time shortening materials, not only was the cycle time not shortened, but it was confirmed that the room temperature impact strength and low temperature impact strength were lowered compared to Examples 1 to 5. I was able to.

In addition, in the case of Comparative Example 3, where the polyamide resin was used in a small amount outside the appropriate range, the polyphenylene ether resin was used in an excessive amount outside the appropriate range, and the compatibilizer and alkali metal salt of montanic acid ester were used in excessive amounts outside the appropriate range. , not only was the crystallization temperature reduced compared to Examples 1 to 5, but the cycle time was such that work was impossible.

In addition, in the case of Comparative Example 4, in which a small amount of polyamide resin was used outside the appropriate range and an excessive amount of polyphenylene ether resin was used outside the appropriate range, the room temperature impact strength, low temperature impact strength, and crystallization temperature were lower than those of Examples 1 to 5. All were confirmed to be degraded.

In addition, in the case of Comparative Example 5, in which a small amount of polyamide resin was used outside the appropriate range and an excessive amount of polyphenylene ether resin was used outside the appropriate range, and at the same time no cycle time shortening material was used at all, compared to Examples 1 to 5, room temperature Impact strength and low-temperature impact strength were in the same or similar range, but not only was the crystallization temperature reduced, but the cycle time was such that work was impossible.

Furthermore, in the case of Comparative Example 6, in which an excessive amount of polyamide resin was used outside the appropriate range and a small amount of polyphenylene ether resin was used outside the appropriate range, processability and fluidity were significantly improved compared to Examples 1 to 5, and appearance performance was also poor. It was confirmed that it could not be quantified in detail.

In conclusion, when the polyamide resin disclosed in the present invention includes materials capable of improving solidification speed and crystallization characteristics and adjusts the amount of these used, the cycle time is shortened and low-temperature impact strength, moisture absorption resistance, heat resistance properties, etc. are improved. It was confirmed that materials that could be improved were provided.

Claims (14)

polyamide resin; polyphenylene ether resin; Styrene-based block copolymer; compatibilizer; and cycle time shortening materials;
Based on ISO 180, the notched Izod impact strength measured at 23 ℃ and the notched Izod impact strength measured at -30 ℃ under the conditions of specimen size 4 A polyamide resin composition that satisfies the following equation (1) when c is the crystallization temperature (Tc) measured at 20°C/min using a scanning calorimeter.
[Equation 1]
1 ≤ (a
(In Equation 1 above, a, b, and c satisfy 14≤a≤30, 8≤b≤24, and 182≤c≤294, respectively.) According to paragraph 1,
A polyamide resin composition, wherein the cycle time shortening material is at least one selected from alumina silicate-based compounds , phosphate ester metal salts, sorbitol, fatty acid metal salts, and clay minerals. According to paragraph 2,
A polyamide resin composition, wherein the fatty acid metal salt is an alkali metal salt of montanic acid ester. According to paragraph 2,
A polyamide resin composition, characterized in that the alumina silicate-based compound is a masterbatch containing 60 to 97% by weight of polyamide 2.2 and 3 to 40% by weight of alumina silicate. According to clause 4,
The cycle time shortening material is a polyamide resin composition characterized in that it contains the masterbatch and an alkali metal salt of montanic acid ester in a weight ratio of 1:2 to 1:12 (masterbatch: alkali metal salt of montanic acid ester). According to paragraph 1,
The styrene-based block copolymers include polystyrene-polybutadiene, polystyrene-poly(ethylene propylene), polystyrene-polyisoprene, polystyrene-polybutidaene-polystyrene, polystyrene-polyisoprene-polystyrene, and polystyrene-poly(ethylene, butylene). - A polyamide resin composition characterized by one or more types selected from polystyrene. According to paragraph 1,
A polyamide resin composition, characterized in that the polyamide resin has a glass transition temperature (Tg) of 50°C or less, a crystallization temperature (Tc) of 190°C or less, and a relative viscosity (RV) of 3.0 or less. According to paragraph 1,
The polyamide resin is a polyamide resin composition characterized in that it contains poly(azepan-2-one). According to paragraph 1,
The compatibilizer is a liquid diene polymer, an epoxy compound, an oxidized polyolefin wax, a quinone compound, an organic silane compound, a multifunctional compound consisting of a carbon-carbon double bond and one or more carboxylic acids, a precursor of the multifunctional compound, and the multifunctional compound. A polyamide resin composition, characterized in that it is at least one selected from acid anhydride, polyhydric carboxylic acid compound, and functionalized polyarylene oxide. According to clause 9,
The functionalized polyarylene oxide is a polyarylene oxide functionalized with one or more reactive monomers selected from citric anhydride, maleic anhydride, maleic acid, itagonic anhydride, fumaric acid, (meth)acrylic acid, and (meth)acrylic acid ester. A polyamide resin composition characterized in that. According to paragraph 1,
The styrene-based block copolymer, compatibilizer, and polyphenylene ether resin are characterized in that they are included in a weight ratio of 1:0.5 to 1.0:3.5 to 5 (styrene-based block copolymer: compatibilizer: polyphenylene ether resin). Polyamide resin composition. According to paragraph 1,
The polyamide resin composition is characterized in that the heat distortion temperature measured according to ISO 75 is 66 ° C or higher. polyamide resin; polyphenylene ether resin; Styrene-based block copolymer; compatibilizer; and a cycle time shortening material, including kneading and extruding,
The cycle time shortening material is at least one selected from alumina silicate-based compounds and alkali metal salts of montanic acid esters,
According to ISO 180, the notched Izod impact strength measured at 23 ℃ and the notched Izod impact strength measured at -30 ℃ under the conditions of specimen size 4 A method for producing a polyamide resin composition, characterized in that it satisfies the following equation 1, assuming that c is the crystallization temperature (Tc) measured under the condition of 20°C/min using a scanning calorimeter.
[Equation 1]
1 ≤ (a
(In Equation 1 above, a, b, and c satisfy 14≤a≤30, 8≤b≤24, and 182≤c≤294, respectively.) A molded article comprising the polyamide resin composition of any one of claims 1 to 12.