KR20170099297A - Polyamide resin composition and article comprising the same - Google Patents
Polyamide resin composition and article comprising the same Download PDFInfo
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- KR20170099297A KR20170099297A KR1020160021489A KR20160021489A KR20170099297A KR 20170099297 A KR20170099297 A KR 20170099297A KR 1020160021489 A KR1020160021489 A KR 1020160021489A KR 20160021489 A KR20160021489 A KR 20160021489A KR 20170099297 A KR20170099297 A KR 20170099297A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B62—LAND VEHICLES FOR TRAVELLING OTHERWISE THAN ON RAILS
- B62D—MOTOR VEHICLES; TRAILERS
- B62D25/00—Superstructure or monocoque structure sub-units; Parts or details thereof not otherwise provided for
- B62D25/08—Front or rear portions
- B62D25/10—Bonnets or lids, e.g. for trucks, tractors, busses, work vehicles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B62—LAND VEHICLES FOR TRAVELLING OTHERWISE THAN ON RAILS
- B62D—MOTOR VEHICLES; TRAILERS
- B62D29/00—Superstructures, understructures, or sub-units thereof, characterised by the material thereof
- B62D29/04—Superstructures, understructures, or sub-units thereof, characterised by the material thereof predominantly of synthetic material
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- C—CHEMISTRY; METALLURGY
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
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Abstract
Description
The present invention relates to a polyamide resin composition and a molded article containing the same. More specifically, the present invention relates to a polyamide resin composition excellent in heat resistance, rigidity, hydrolysis resistance, moisture absorption resistance, workability and the like, and a molded article comprising the same.
As the polyamide resin (nylon), aliphatic polyamide resins such as PA (polyamide) 66 and PA6 are most well known. Although these aliphatic polyamide resins are widely used for automobile parts, electric appliances, electronic products, and machine parts, they are insufficient in thermal stability because they are applied to fields requiring high heat resistance characteristics.
The high heat resistant polyamide resin (such as polyphthalamide) may have a semiaromatic structure and a semi-crystalline structure, and may be obtained by condensation of an aromatic dicarboxylic acid or an aromatic diamine. The high heat resistant polyamide resin has a heat resistance higher than that of general polyamide resin products and can be applied to various fields requiring high heat resistance characteristics.
However, in order to use a high heat-resistant polyamide resin and a resin composition containing the same in an automobile engine room UTH (under the hood) material, it must be able to be used at a high temperature of 130 ° C or higher for a long period of time and have excellent mechanical properties such as rigidity However, it should be excellent in hydrolysis resistance and hygroscopicity against high temperature cooling water (Long Life Coolant: LLC).
PA9T, PA6T, PA9T, PA10T, PA11T, and PA12T are widely used as high heat-resistant nylon, but in the case of polyamide (nylon) 6T and the like, since the melting temperature is very high and the decomposition temperature is lower than the processing temperature It is generally difficult to use them alone, so that copolymerization monomers such as adipic acid are copolymerized in order to lower the processing temperature. However, when a copolymerizable monomer such as adipic acid is applied to a polyamide resin, it may have a glass transition temperature of less than 100 占 폚, which is disadvantageous in that it is insufficient in heat resistance and the like to be used in automobile engine room UTH materials and the like.
Therefore, there is a need to develop a polyamide resin composition excellent in heat resistance, rigidity, hydrolysis resistance, hygroscopicity, processability, and balance of physical properties such that it can be used for a long period of time at a high temperature of 130 캜 or more.
The background art of the present invention is disclosed in U.S. Patent No. 5,256,719.
An object of the present invention is to provide a polyamide resin composition excellent in heat resistance, rigidity, hydrolysis resistance, moisture absorption resistance, workability, and physical properties balance thereof, and a molded article formed therefrom.
Another object of the present invention is to provide a polyamide resin composition which can be used for a long time at a high temperature of 130 ° C or higher and a molded article formed from the composition.
The above and other objects of the present invention can be achieved by the present invention described below.
One aspect of the present invention relates to a polyamide resin composition. Wherein the polyamide resin composition comprises a first polyamide resin comprising 60 to 90% by mole of a repeating unit represented by the following formula (1) and 10 to 40% by mole of a repeating unit represented by the following formula (2); A second polyamide resin comprising a repeating unit represented by the following formula (3); And an inorganic filler.
[Chemical Formula 1]
(2)
(3)
Wherein R 1 , R 2 and R 3 are each independently a hydrocarbon group having 1 to 5 carbon atoms or a halogen atom, n 1 , n 2 and n 3 are each independently an integer of 0 to 4 to be.
In an embodiment, the second polyamide resin may further include a repeating unit represented by the following formula (4)
[Chemical Formula 4]
In Formula 4, R 4 is a hydrocarbon group having 1 to 5 carbon atoms or a halogen atom, and n 4 is an integer of 0 to 4.
In an embodiment, the polyamide resin composition may comprise 5 to 60 wt% of the first polyamide resin, 5 to 60 wt% of the second polyamide resin, and 10 to 50 wt% of the inorganic filler.
In an embodiment, the inorganic filler may include at least one of glass fiber, talc, wollastonite, whisker, silica and mica.
In an embodiment, the polyamide resin composition may have a glass transition temperature of 120 to 160 ° C and a melting temperature of 280 to 320 ° C.
In a specific example, the polyamide resin composition may have a heat distortion temperature (HDT) of 150 to 280 DEG C measured under the conditions of a load of 1.8 MPa and a temperature raising rate of 120 DEG C / hr according to ASTM D648.
In a specific example, the polyamide resin composition may have a tensile strength retention ratio of 70% or more according to the following formula 1:
[Formula 1]
Tensile strength retention (%) = TS 1 / TS 0 100
TS 0 is the initial tensile strength of the 3.2 mm thick specimen measured according to ISO 527 (23 캜, 5 mm / min) and TS 1 is the initial tensile strength of the specimen measured using a mixed solvent of ethylene glycol and water (weight ratio: 50/50 ), Maintained at 130 캜 for 500 hours, and then tensile strength after heat treatment measured according to ISO 527 (23 캜, 5 mm / min).
In a specific example, the polyamide resin composition may have a water absorption rate of 1% or less according to the following formula 2:
[Formula 2]
Water Absorption Rate (%) = | W 1 -W 0 | / W 0 100
In the formula 2, W 0 is the weight measured after the specimen having a size of 100 mm × 100 mm × 3 mm was prepared and vacuum-dried at 130 ° C. for 4 hours, and W 1 was the measured weight of the dried specimen at 50 ° C. , Relative humidity (RH) 90% for 48 hours.
Another aspect of the present invention relates to a molded article. The molded article is formed from the polyamide resin composition.
In an embodiment, the molded article may be an automotive engine room UTH (under the hood) material.
The present invention provides a polyamide resin composition which is excellent in heat resistance, rigidity, hydrolysis resistance, moisture absorption resistance, processability, physical properties balance thereof and the like and which can be used for a long time at a high temperature of 130 ° C or higher and a molded article formed therefrom .
Hereinafter, the present invention will be described in detail.
The polyamide resin composition according to the present invention comprises (A) a first polyamide resin; (B) a second polyamide resin; And (C) an inorganic filler.
(A) a first polyamide resin
The first polyamide resin according to one embodiment of the present invention can improve the heat resistance, rigidity, hydrolysis resistance, hygroscopic hygroscopicity, processability, physical properties balance of the polyamide resin composition together with the second polyamide resin , A repeating unit represented by the following formula (1), and a repeating unit represented by the following formula (2).
[Chemical Formula 1]
(2)
In the general formulas (1) and (2), R 1 and R 2 are each independently a hydrocarbon group having 1 to 5 carbon atoms or a halogen atom, and n 1 and n 2 are each independently an integer of 0 to 4.
In an embodiment, the first polyamide resin is terephthalic acid or an alkyl ester thereof substituted or unsubstituted phenyl ring as R < 1 >; Isophthalic acid or an alkyl ester thereof substituted or unsubstituted phenyl ring as R 2 ; And 1,6-hexanediamine (hexamethylene diamine: HMDA) according to a known polymerization method.
In a specific example, the repeating unit represented by the formula (1) may be contained in an amount of 60 to 90 mol%, for example, 65 to 85 mol% in 100 mol% of the first polyamide resin, And 10 to 40 mol%, for example, 15 to 35 mol%, of 100 mol% of the first polyamide resin. When the content of the repeating unit represented by the formula (1) is less than 60 mol% (the content of the repeating unit represented by the formula (2) is more than 40 mol%), the tensile strength retention ratio of the polyamide resin composition under high temperature conditions, When the content of the repeating unit represented by the above formula (1) exceeds 90 mol% (the content of the repeating unit represented by the above formula (2) is less than 10 mol%), The processability and impact resistance of the polyamide resin composition may be lowered.
In an embodiment, the first polyamide resin may have a glass transition temperature of 80 to 140 캜, for example 120 to 140 캜, and a melting temperature of 280 to 330 캜, for example, 300 to 325 캜.
The first polyamide resin was dissolved in a concentrated sulfuric acid solution (98%) at a concentration of 0.5 g / dL, and then an intrinsic viscosity [?] Measured by a Ubbelohde viscometer at 25 ° C was 0.7 to 1.2 dL / g, for example 0.8 to 0.9 dL / g. Within the above range, the processability and the like of the polyamide resin composition can be excellent.
In an embodiment, the first polyamide resin may comprise 5 to 60% by weight, for example 15 to 45% by weight, of 100% by weight of the total polyamide resin composition. Within the above range, the polyamide resin composition may be excellent in heat resistance, rigidity, hydrolysis resistance, moisture absorption resistance, processability, physical properties thereof, etc., and may be used for a long period of time at a high temperature of 130 ° C or higher.
(B) a second polyamide resin
The second polyamide resin according to one embodiment of the present invention significantly improves the hydrolysis resistance, hygroscopicity, and the like of the polyamide resin composition against high temperature coolant (LLC) of 130 ° C or higher, And a repeating unit represented by the following formula (3), which can improve the heat resistance, rigidity, hydrolysis resistance, hygroscopicity, workability, physical properties and balance of the polyamide resin composition.
(3)
In Formula 3, R 3 is a hydrocarbon group having 1 to 5 carbon atoms or a halogen atom, and n 3 is an integer of 0 to 4.
In an embodiment, the second polyamide resin may further include a repeating unit represented by the following formula (4). That is, the second polyamide resin may be a polymer containing only a repeating unit represented by the formula (3), a polymer including all repeating units represented by the formulas (3) and (4), or a mixture thereof.
[Chemical Formula 4]
In Formula 4, R 4 is a hydrocarbon group having 1 to 5 carbon atoms or a halogen atom, and n 4 is an integer of 0 to 4.
In an embodiment, the second polyamide resin is terephthalic acid or an alkyl ester thereof substituted or unsubstituted phenyl ring as R < 3 >; And 2-methyl-1,5-pentamethylene diamine according to a known polymerization method, and if necessary, the phenyl ring is substituted with R 4 Unsubstituted isophthalic acid or an alkyl ester thereof.
In a specific example, the repeating unit represented by Formula 3 may be contained in an amount of 40 mol% or more, for example, 50 to 100 mol% in 100 mol% of the second polyamide resin, 1 polyamide resin may be contained in an amount of 60 mol% or less, for example, 0 to 50 mol%, based on 100 mol% of the polyamide resin. When the content of the repeating unit represented by the above-mentioned general formula (3) is less than 40 mol% (the content of the repeating unit represented by the general formula (4) exceeds 60 mol%), the heat resistance of the polyamide resin composition There is a possibility that the water-decomposing property, the moisture-absorbing property and the like are lowered.
In an embodiment, the second polyamide resin may have a glass transition temperature of 140 to 150 ° C, for example 143 to 148 ° C, and the melting temperature may be 290 to 300 ° C, for example 293 to 296 ° C.
The second polyamide resin was dissolved in a concentrated sulfuric acid solution (98%) at a concentration of 0.5 g / dL, and then an intrinsic viscosity [?] Measured by a Ubbelohde viscometer at 25 ° C was 0.7 to 1.0 dL / g, for example 0.73 to 0.78 dL / g. Within the above range, the processability and the like of the polyamide resin composition can be excellent.
In an embodiment, the second polyamide resin may comprise 5 to 60% by weight, for example 20 to 50% by weight, of 100% by weight of the total polyamide resin composition. Within the above range, the polyamide resin composition can be excellent in heat resistance, rigidity, hydrolysis resistance, hygroscopicity, processability, physical properties and balance thereof, and can be used for a long period of time at a high temperature of 130 ° C or higher.
(C) Inorganic filler
The inorganic filler according to one embodiment of the present invention can improve the rigidity and the like of the polyamide resin composition. An inorganic filler used in a conventional thermoplastic resin composition can be used. Examples thereof include glass fiber, talc, wollastonite , Whiskers, silica, mica, mixtures thereof, and the like. Specifically, glass fiber can be used.
In an embodiment, the inorganic filler may have various shapes such as a fiber shape, a particle shape, a rod shape, an acicular shape, a flake shape, and an amorphous shape, and may have various shapes such as a circle, an ellipse, and a rectangle. For example, it may be preferable from the viewpoint of mechanical properties to use a glass fiber which is a fibrous inorganic filler having a circular and / or rectangular cross section.
In a specific example, the glass fiber of the circular cross section may have a cross-sectional diameter of 5 to 20 탆 and a length before shaping of 2 to 20 mm, the glass fiber of the rectangular cross-section has an aspect ratio of 1.5 to 10, May be between 2 and 20 mm. Within the above range, the rigidity, workability and the like of the polyamide resin composition can be improved.
In an embodiment, the inorganic filler may be contained in an amount of 10 to 50% by weight, for example, 15 to 45% by weight, based on 100% by weight of the total polyamide resin composition. Within the above range, heat resistance, rigidity, workability, balance of physical properties and the like of the polyamide resin composition can be excellent.
The polyamide resin composition according to one embodiment of the present invention may further contain conventional additives as necessary insofar as the effect of the present invention is not impaired. The additives include, but are not limited to, flame retardants, antioxidants, lubricants, release agents, nucleating agents, antistatic agents, stabilizers, colorants, and mixtures thereof. When the additive is used, the content thereof may be 10 parts by weight or less based on 100 parts by weight of the first and second polyamide resins.
In a specific example, the polyamide resin composition may have a glass transition temperature measured by a differential scanning calorimeter (DSC) of 120 to 160 ° C, for example, 130 to 150 ° C, and a melt temperature of 280 to 320 ° C, Lt; 0 > C to 320 < 0 > C. Within the above range, the polyamide resin composition can have excellent heat resistance and processability.
In a specific example, the polyamide resin composition has a heat distortion temperature (HDT) of 150 to 280 DEG C, for example, in a range of 170 to 270 DEG C measured under the conditions of a load of 1.8 MPa and a temperature raising rate of 120 DEG C / hr according to ASTM D648 . Within the above range, the heat resistance of the polyamide resin composition may be excellent.
In an embodiment, the polyamide resin composition may have a tensile strength of 200 to 250 MPa, for example, 210 to 240 MPa, of 3.2 mm thick specimen measured according to ISO 527 (23 캜, 5 mm / min). Within the above range, the polyamide resin composition may have excellent mechanical properties such as rigidity.
In a specific example, the polyamide resin composition may have a tensile strength retention ratio of 70% or more, for example, 72 to 90% according to the following formula 1. Within the above range, the polyamide resin may have excellent long-term heat resistance and hydrolysis resistance at a high temperature (130 ° C or higher).
[Formula 1]
Tensile strength retention (%) = TS 1 / TS 0 100
TS 0 is the initial tensile strength of the 3.2 mm thick specimen measured according to ISO 527 (23 캜, 5 mm / min) and TS 1 is the initial tensile strength of the specimen measured using a mixed solvent of ethylene glycol and water (weight ratio: 50/50 ), Maintained at 130 캜 for 500 hours, and then tensile strength after heat treatment measured according to ISO 527 (23 캜, 5 mm / min).
In a specific example, the polyamide resin composition may have a water absorption rate of 1% or less, for example, 0.75 to 0.95% according to the following formula (2). Within the above range, the polyamide resin may have excellent moisture absorption resistance.
[Formula 2]
Water Absorption Rate (%) = | W 1 -W 0 | / W 0 100
In the formula 2, W 0 is the weight measured after the specimen having a size of 100 mm × 100 mm × 3 mm was prepared and vacuum-dried at 130 ° C. for 4 hours, and W 1 was the measured weight of the dried specimen at 50 ° C. , Relative humidity (RH) 90% for 48 hours.
The molded article according to the present invention is formed from the polyamide resin composition. For example, the polyamide resin composition can be used to produce a molded article by a known molding method such as injection molding, double injection molding, blow molding, extrusion molding, and thermoforming. The molded article can be easily formed by a person having ordinary skill in the art to which the present invention belongs.
In a specific example, the molded article can be applied to various fields to which high heat-resistant nylon is applied. In addition, since it is excellent in heat resistance, rigidity, hydrolysis resistance, moisture absorption resistance, processability, physical properties thereof, and can be used for a long period of time at a high temperature of 130 ° C or higher, Materials and the like.
Hereinafter, the present invention will be described in more detail by way of examples, but these examples are for illustrative purposes only and should not be construed as limiting the present invention.
Example
The specifications of each component used in the following examples and comparative examples are as follows.
(A) a first polyamide resin
(A1) polyamide 6T / 6I (manufactured by SOLVAY, product name: A1007, 6T: 6I (molar ratio) = 70: 30) was used.
(A2) polyamide 6T / 6I (6T: 6I (molar ratio) = 55: 45) was used.
(B) a second polyamide resin
(B1) Polyamide DT (manufacturer: INVISTA, product name: NOVADYN DT) was used.
(B2) polyamide DT / DI (manufactured by INVISTA, product name: NOVADYN DT / DI, DT: DI (molar ratio) = 60:40) was used.
(C) Inorganic filler
Glass fiber (manufacturer: Owens corning, product name: 983) was used.
Examples 1 to 6 and Comparative Examples 1 to 4
According to the compositions and contents of Tables 1 and 2, the above components were mixed and then added to a twin screw type extruder having an L / D of 35 and a diameter of 45 mm. The mixture was melted and extruded at 230 DEG C to obtain pellets . The prepared pellets were dried at 80 ° C. for 2 hours or more, and then injected at an injection temperature of 230 ° C. and a mold temperature of 60 ° C. to prepare specimens. The properties of the prepared specimens were evaluated by the following methods, and the results are shown in Tables 1 and 2 below.
Property evaluation method
(1) The melting temperature (Tm) and the glass transition temperature (Tg) (unit: 占 폚) were measured using a differential scanning calorimeter (DSC). A DSC Q20 meter was used, and 5 to 10 mg of a sample was vacuum-dried at 80 DEG C for 4 hours (with a water content of 3,000 ppm or less), heated in a nitrogen atmosphere from 30 DEG C to 400 DEG C at a rate of 20 DEG C / min After staying at 400 ° C for 1 minute, cooling to 30 ° C at a rate of 20 ° C / min, staying at 30 ° C for 1 minute, raising the temperature to 400 ° C at a rate of 20 ° C / min (2nd scan) The glass transition temperature and melting temperature were measured from the maximum point of the endothermic peak.
(2) Heat distortion temperature (HDT, unit: 占 폚): The heat distortion temperature was measured under the conditions of a load of 1.8 MPa and a heating rate of 120 占 폚 / hr in accordance with ASTM D648.
(3) Tensile strength (TS, unit: MPa): The tensile strength of a 3.2 mm thick specimen was measured according to ISO 527 (23 캜, 5 mm / min).
(4) Tensile strength retention (unit:%): The tensile strength retention was calculated in accordance with the following formula (1).
[Formula 1]
Tensile strength retention (%) = TS 1 / TS 0 100
TS 0 is the initial tensile strength of the 3.2 mm thick specimen measured according to ISO 527 (23 캜, 5 mm / min) and TS 1 is the initial tensile strength of the specimen measured using a mixed solvent of ethylene glycol and water (weight ratio: 50/50 ), Maintained at 130 캜 for 500 hours, and then tensile strength after heat treatment measured according to ISO 527 (23 캜, 5 mm / min).
(5) Water Absorption Rate (Unit:%): The water absorption rate was calculated according to the following equation (2).
[Formula 2]
Water Absorption Rate (%) = | W 1 -W 0 | / W 0 100
In the formula 2, W 0 is the weight measured after the specimen having a size of 100 mm × 100 mm × 3 mm was prepared and vacuum-dried at 130 ° C. for 4 hours, and W 1 was the measured weight of the dried specimen at 50 ° C. , Relative humidity (RH) 90% for 48 hours.
From the above results, the polyamide resin composition according to the present invention is excellent in heat resistance (Tg 130 ° C or higher, HDT 137 ° C or higher), rigidity (TS 210 MPa or higher), hygroscopicity (moisture absorption rate 0.92% ), And can be used for a long period of time at a high temperature of 130 ° C or higher (tensile strength retention ratio of 72% or more, high temperature long term heat resistance and hydrolysis resistance).
On the other hand, in the case of Comparative Example 1 in which the second polyamide resin was not used, it was found that the processability, tensile strength retention (high-temperature long-term heat resistance) and moisture absorption resistance of the polyamide resin composition decreased, 1 In Comparative Example 2 using only polyamide DT without using a polyamide resin, it was found that the heat resistance, hygroscopicity, and the like were lowered and the balance of physical properties was lowered, and the polyamide DT / (Comparative Example 3) using only the first polyamide resin (A2) having a repeating structural unit represented by the formula (1) of less than 60 mol% was found to be inferior in workability, heat resistance, , The tensile strength retention (high-temperature long-term heat resistance) and moisture absorption resistance of the polyamide resin composition are lowered and the balance of physical properties is lowered.
It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
A second polyamide resin comprising a repeating unit represented by the following formula (3); And
An inorganic filler comprising: a polyamide resin composition comprising:
[Chemical Formula 1]
(2)
(3)
Wherein R 1 , R 2 and R 3 are each independently a hydrocarbon group having 1 to 5 carbon atoms or a halogen atom, n 1 , n 2 and n 3 are each independently an integer of 0 to 4 to be.
[Chemical Formula 4]
In Formula 4, R 4 is a hydrocarbon group having 1 to 5 carbon atoms or a halogen atom, and n 4 is an integer of 0 to 4.
[Formula 1]
Tensile strength retention (%) = TS 1 / TS 0 100
TS 0 is the initial tensile strength of the 3.2 mm thick specimen measured according to ISO 527 (23 캜, 5 mm / min) and TS 1 is the initial tensile strength of the specimen measured using a mixed solvent of ethylene glycol and water (weight ratio: 50/50 ), Maintained at 130 캜 for 500 hours, and then tensile strength after heat treatment measured according to ISO 527 (23 캜, 5 mm / min).
[Formula 2]
Water Absorption Rate (%) = | W 1 -W 0 | / W 0 100
In the formula 2, W 0 is the weight measured after the specimen having a size of 100 mm × 100 mm × 3 mm was prepared and vacuum-dried at 130 ° C. for 4 hours, and W 1 was the measured weight of the dried specimen at 50 ° C. , Relative humidity (RH) 90% for 48 hours.
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Cited By (5)
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KR101950118B1 (en) * | 2017-12-27 | 2019-02-19 | 롯데첨단소재(주) | Polyamide resin composition and article comprising the same |
WO2020089781A1 (en) * | 2018-10-30 | 2020-05-07 | Sabic Global Technologies B.V. | High flow poly(phthalamide) compositions, and articles made therefrom |
US11565513B2 (en) | 2017-12-31 | 2023-01-31 | Lotte Chemical Corporation | Polyamide resin composition and molded article comprising the same |
US11577496B2 (en) | 2017-12-31 | 2023-02-14 | Lotte Chemical Corporation | Polyamide resin composition and molded article comprising the same |
US11578206B2 (en) | 2017-10-30 | 2023-02-14 | Lotte Advanced Materials Co., Ltd. | Polyamide resin composition and molded article comprising the same |
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2016
- 2016-02-23 KR KR1020160021489A patent/KR20170099297A/en not_active Application Discontinuation
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US11578206B2 (en) | 2017-10-30 | 2023-02-14 | Lotte Advanced Materials Co., Ltd. | Polyamide resin composition and molded article comprising the same |
KR101950118B1 (en) * | 2017-12-27 | 2019-02-19 | 롯데첨단소재(주) | Polyamide resin composition and article comprising the same |
US11565513B2 (en) | 2017-12-31 | 2023-01-31 | Lotte Chemical Corporation | Polyamide resin composition and molded article comprising the same |
US11577496B2 (en) | 2017-12-31 | 2023-02-14 | Lotte Chemical Corporation | Polyamide resin composition and molded article comprising the same |
WO2020089781A1 (en) * | 2018-10-30 | 2020-05-07 | Sabic Global Technologies B.V. | High flow poly(phthalamide) compositions, and articles made therefrom |
CN113166536A (en) * | 2018-10-30 | 2021-07-23 | 高新特殊工程塑料全球技术有限公司 | High flow poly (phthalamide) compositions and articles made therefrom |
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