KR20140079219A - Polyamide resin, method for preparing the same, and article comprising the same - Google Patents

Polyamide resin, method for preparing the same, and article comprising the same Download PDF

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KR20140079219A
KR20140079219A KR1020120148930A KR20120148930A KR20140079219A KR 20140079219 A KR20140079219 A KR 20140079219A KR 1020120148930 A KR1020120148930 A KR 1020120148930A KR 20120148930 A KR20120148930 A KR 20120148930A KR 20140079219 A KR20140079219 A KR 20140079219A
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acid
polyamide resin
component
dicarboxylic acid
mol
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KR1020120148930A
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Korean (ko)
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제진아
권소영
김진규
방승엽
이은주
임상균
이기연
전석민
최성철
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제일모직주식회사
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Publication of KR20140079219A publication Critical patent/KR20140079219A/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C08G69/265—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from at least two different diamines or at least two different dicarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C08G69/32—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from aromatic diamines and aromatic dicarboxylic acids with both amino and carboxylic groups aromatically bound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • 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
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Polyamides (AREA)

Abstract

The polyamide resin of the present invention comprises (a1) a dicarboxylic acid component (A) comprising an aromatic dicarboxylic acid component; And (b1) a diamine component (B) comprising 75 to 85% by mole of an aliphatic diamine component and (b2) 15 to 25% by mole of diaminotoluene are copolymerized to obtain a dicarboxylic acid component (A) And a diamine portion derived from the diamine component (B) are repeated. The polyamide resin is excellent in workability, heat resistance and dimensional stability.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyamide resin, a method of producing the same,

TECHNICAL FIELD The present invention relates to a polyamide resin, a method for producing the same, and a product containing the same, and more specifically, to a high heat-resistant copolymerized polyamide resin having excellent processability, heat resistance and dimensional stability, a method for producing the same, .

As the polyamide resin, aliphatic polyamide resins such as nylon 66 and nylon 6 are most well known. Although these aliphatic polyamide resins are widely used for automobile parts, electric appliances, electronic products, and machine parts, they do not have sufficient thermal stability to be applied to fields requiring high heat resistance characteristics.

The aromatic polyamide resin has a higher melting temperature and higher heat resistance than the aliphatic polyamide resin, but has a poor workability due to a high melting temperature and has been used for limited use.

Generally, in the case of high heat-resistant nylon, it has a semi-crystalline structure and can be used in various fields requiring a high heat resistance characteristic because the heat-resistant temperature is considerably higher than that of general nylon. However, in the case of conventional products, the glass transition temperature (Tg) is in the range of 90 to 120 占 폚 and has a low glass transition temperature.

For example, in the case of polyamide (nylon) 6T, since the melting temperature is very high and the decomposition temperature is lower than the processing temperature, it is difficult to use it alone (that is, since the melting temperature is high, It is more likely to co-polymerize to lower the processing temperature. However, when an aliphatic monomer such as adipic acid is used as the copolymerizable monomer, it has a glass transition temperature of less than 100 占 폚.

Especially, when high heat-resistant nylon is used as an automobile UTH (under the hood) engine room material, high heat resistance characteristics are required due to high engine room temperature. Here, the most important physical properties are glass transition temperature, and conventional high heat-resistant nylon such as polyamide 6T copolymer has low glass transition temperature and is difficult to use.

Therefore, it is necessary to develop a polyamide resin having a high glass transition temperature while improving melt processability.

An object of the present invention is to provide a high heat-resistant copolymerized polyamide resin excellent in workability, heat resistance and dimensional stability with a glass transition temperature of 130 ° C or higher.

Another object of the present invention is to provide a process for producing the polyamide resin.

It is still another object of the present invention to provide a product formed of the polyamide resin.

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

One aspect of the invention relates to polyamide resins. The polyamide resin according to one embodiment of the present invention comprises (a1) a dicarboxylic acid component (A) containing an aromatic dicarboxylic acid component; And (b1) a diamine component (B) comprising 75 to 85% by mole of an aliphatic diamine component and (b2) 15 to 25% by mole of diaminotoluene are copolymerized to obtain a dicarboxylic acid component (A) And a diamine portion derived from the diamine component (B) are repeated.

In an embodiment, the dicarboxylic acid component (A) further comprises 30 mol% or less of (a2) adipic acid, and the dicarboxylic acid component (A) and the diamine component (B) The total content of the adipic acid (a2) and the diaminotoluene (b2) may be 25 mol% or less.

In an embodiment, the aromatic dicarboxylic acid component (a1) may be at least one compound of an aromatic dicarboxylic acid component having 8 to 20 carbon atoms.

In an embodiment, the aliphatic diamine component (b1) may be at least one compound selected from aliphatic diamine components having 4 to 20 carbon atoms.

In an embodiment, the glass transition temperature (Tg) of the polyamide resin may be 130 ° C or higher.

In an embodiment, the crystallization temperature (Tc) of the polyamide resin may be 250 to 300 ° C, and the melting temperature (Tm) may be 300 to 340 ° C.

In an embodiment, the polyamide resin may have a water uptake of 5.0% or less after treatment at 50 ° C and 90% relative humidity for 48 hours.

In an embodiment, the intrinsic viscosity of the polyamide resin may be 0.3 to 2.0 dL / g.

In an embodiment, the polyamide resin may be encapsulated with a terminal blocking agent wherein the terminal group is an aliphatic carboxylic acid or an aromatic carboxylic acid.

Preferably, the end-capping agent is selected from the group consisting of acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, pivalic acid, Benzoic acid, toluic acid,? -Naphthalenecarboxylic acid,? -Naphthalenecarboxylic acid, and methylnaphthalenecarboxylic acid.

The polyamide resin according to another embodiment of the present invention is formed by copolymerizing a diamine component including diaminotoluene and has a glass transition temperature (Tg) of 140 ° C or higher.

Another aspect of the present invention relates to a method for producing the polyamide resin. (B1) 75 to 85 mol% of an aliphatic diamine component and (b2) 15 to 25 mol% of a diaminotoluene, wherein (a1) the dicarboxylic acid component (A) comprising an aromatic dicarboxylic acid component (B) a diamine component.

In an embodiment, the dicarboxylic acid component (A) further comprises 30 mol% or less of (a2) adipic acid, and the dicarboxylic acid component (A) and the diamine component (B) The total content of the adipic acid (a2) and the diaminotoluene (b2) may be 25 mol% or less.

Another aspect of the present invention relates to a molded article formed from the polyamide resin.

The present invention has the effect of providing a high heat-resistant copolymerized polyamide resin excellent in processability, heat resistance and dimensional stability with a glass transition temperature of 130 ° C or higher, a method for producing the same, and a product containing the same.

Hereinafter, the present invention will be described in detail.

A polyamide resin according to an embodiment of the present invention comprises (a1) a dicarboxylic acid component containing an aromatic dicarboxylic acid component and (b1) 75 to 85% by mole of an aliphatic diamine component and (b2) (B) a diamine component containing 15 to 25 mol% of diamino toluene is copolymerized to form a dicarboxylic acid moiety derived from the dicarboxylic acid component (A) and a diamine component derived from the diamine component (B) And the diamine portion is repeated.

The polyamide resin according to another embodiment of the present invention is formed by copolymerizing a diamine component containing diaminotoluene and has a glass transition temperature (Tg) of 140 ° C or higher.

In the present specification, the term dicarboxylic acid component and the like includes dicarboxylic acid, an alkyl ester thereof (lower alkyl ester having 1 to 4 carbon atoms such as monomethyl, monoethyl, dimethyl, diethyl or dibutyl ester) Acid anhydride, and the like, and react with the diamine component to form a dicarboxylic acid moiety. Further, in the present specification, the dicarboxylic acid moiety and the diamine moiety are preferably such that when the dicarboxylic acid component and the diamine component are polymerized, the hydrogen atom, the hydroxyl group or the alkoxy group is removed, Residue. ≪ / RTI >

(A) a dicarboxylic acid component

The dicarboxylic acid component (A) used in the present invention includes a conventional (a1) aromatic dicarboxylic acid component used for producing a high heat-resistant polyamide resin (nylon).

The aromatic dicarboxylic acid component (a1) may be at least one compound of an aromatic dicarboxylic acid component having 8 to 20 carbon atoms, for example, terephthalic acid, isophthalic acid, 2,6-naphthalene dicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,4-phenylenedioxyphenylenic acid, (Benzoic acid), diphenylmethane-4,4'-dicarboxylic acid, diphenylsulfone-4,4'-dicarboxylic acid, 4-4'-diphenylcarboxylic acid, Terephthalic acid, isophthalic acid or a mixture thereof, more preferably terephthalic acid, or a mixture of terephthalic acid and isophthalic acid.

Further, the dicarboxylic acid component (A) is preferably added in an amount of 30 mol% or less of (a2) adipic acid to the total dicarboxylic acid component (A) in order to further increase the workability of the polyamide resin. As shown in FIG.

The content of the aromatic dicarboxylic acid component (a1) in the dicarboxylic acid component (A) is 70 mol% or more, preferably 75 to 97 mol%, and more preferably 85 to 92 mol% The content of adipic acid (a2) is 30 mol% or less, preferably 3 to 25 mol%, more preferably 8 to 15 mol%. Within the above range, a polyamide resin having excellent properties such as crystallinity, workability and heat resistance can be obtained.

(B) a diamine component

The diamine component (B) used in the present invention necessarily contains the diaminotoluene (b2) as a copolymerizable monomer together with the aliphatic diamine component (b1) in order to produce a polyamide resin having high heat resistance.

The aliphatic diamine component (b1) may be at least one compound selected from among aliphatic diamines having 4 to 20 carbon atoms. Examples of the aliphatic diamine component (b1) include 1,4-butanediamine, 1,6-hexanediamine (hexamethylenediamine) , 1,7-hexanediamine, 1,8-octanediamine, 1,10-decanediamine, 3-methyl-1,5-pentanediamine, 2,2,4- 1,6-hexanediamine, 4,4-trimethyl-1,6-hexanediamine, 5-methyl-1,9-nonanediamine, 2,2-oxybis (ethylamine) Aminopropyl) ether (EGBA), 1,7-diamino-3,5-dioxoheptane, mixtures thereof, and the like, but are not limited thereto. Preferably, 1,4-butanediamine, 1,6-hexanediamine, or a mixture thereof can be used, and more preferably 1,6-hexanediamine can be used.

The diaminotoluene (b2) is capable of producing a polyamide resin having a high glass transition temperature (Tg) of 140 ° C or higher upon copolymerization, for example, 2,4-diaminotoluene can be used. In the diaminotoluene copolymerization, the crystallinity of the polyamide resin to be produced may be lowered due to the methyl group and the amine group of the diaminotoluene. In this case, when the polyamide resin is produced, the adipic acid (a2) Thereby making it possible to compensate the deterioration of crystallinity.

The content of the aliphatic diamine component (b1) in the diamine component (B) is 75 to 85 mol%, preferably 76.5 to 83.5 mol%, more preferably 77.5 to 82 mol%, and the diaminotoluene (b2 ) Is from 15 to 25 mol%, preferably from 16.5 to 23.5 mol%, more preferably from 18 to 22.5 mol%. When the content of the aliphatic diamine component (b1) is less than 75 mol%, or when the content of the diaminotoluene (b2) is more than 25 mol%, crystallization and workability of the polyamide resin may be deteriorated. When the content of the aliphatic diamine component (b1) exceeds 85 mol%, or when the content of the diaminotoluene (b2) is less than 15 mol%, the heat resistance of the polyamide resin may decrease.

When the adipic acid (a2) is used, the amount of the adipic acid (a2) and the amount of the diaminotoluene (B) relative to the entire dicarboxylic acid component (A) and the diamine component (B) b2) may be 25 mol% or less, preferably 7.5 to 23 mol%. Within the above range, a polyamide resin having excellent properties such as crystallinity, workability and heat resistance can be obtained.

In the polyamide resin of the present invention, the ratio (molar ratio ratio: diamine component (B) / dicarboxylic acid component (A)) of the dicarboxylic acid component (A) to the diamine 85 minutes (B) , 0.85 to 1.05, preferably 0.90 to 1.03. Within the above range, deterioration of physical properties due to unreacted monomers can be prevented.

The polyamide resin of the present invention may be encapsulated with an end capping agent whose terminal group is an aliphatic carboxylic acid or an aromatic carboxylic acid.

Wherein the end-capping agent is selected from the group consisting of acetic, propionic, butyric, valeric, caproic, caprylic, lauric, tridecanoic, myristic, palmitic, stearic, pivalic, isobutyl, ,? -naphthalenecarboxylic acid,? -naphthalenecarboxylic acid, and methylnaphthalenecarboxylic acid, but the present invention is not limited thereto.

The end-capping agent may be contained in an amount of, for example, 0 to 5 moles, preferably 0.01 to 3 moles, per 100 moles of the dicarboxylic acid component (A) and the diamine component (B).

The glass transition temperature (Tg) of the polyamide resin according to the present invention may be 130 占 폚 or higher, preferably 140 占 폚 or higher, more preferably 141 to 170 占 폚. Within the above range, it may have high heat resistance, thermal refractility, etc. for use in automobile engine room parts and the like.

The crystallization temperature (Tc) of the polyamide resin may be 250 to 300 ° C, preferably 260 to 290 ° C, and the melting temperature (Tm) may be 300 to 340 ° C, preferably 305 to 320 ° C. Within the above range, the processability of the polyamide resin is excellent.

The polyamide resin may have a water absorption rate of 5.0% or less, preferably 0.5% to 3.0% after treatment at 50 ° C and 90% relative humidity for 48 hours. Within this range, there is an advantage that the hygroscopicity is low.

The water absorption rate was 100 mm in length, 100 mm in width, and 3 mm in thickness. The specimen was vacuum dried at 120 ° C. for 4 hours, and the weight (W 0 ) of the dried specimen was measured. ℃, it is possible to measure the weight (W 1) of the specimen after the treatment for 48 hours at 90% RH, and calculating according to the following formula.

Water Absorption Rate (%) = | W 1 -W 0 | / W 0 * 100

The polyamide resin may have an intrinsic viscosity [?] Of from 0.3 to 2.0 dL / g, preferably from 0.6 to 1.0 dL / g, measured by a Ubbelodhde viscometer at 25 ° C using a 98% sulfuric acid solution .

The polyamide resin may have a strength retention ratio of 80% or more, preferably 85 to 95%. The strength retention rate can be measured by the ratio of the tensile strength after treatment to the tensile strength before treatment for 24 hours at 80 ° C and a relative humidity of 95% in a thermo-hygrostat. The tensile strength can be measured according to ISO 527 (23 캜, 5 mm / min).

Another aspect of the present invention relates to a method for producing the polyamide resin. The process for producing a polyamide according to the present invention comprises reacting a dicarboxylic acid component (A) comprising the aromatic dicarboxylic acid component (a1) and from 75 to 85 mol% of the aliphatic diamine component (b1) and diaminotoluene and b2) 15 to 25 mol% of a diamine component (B).

In the specific example, the dicarboxylic acid component (A) may further contain not more than 30 mol% of (a2) adipic acid, and the dicarboxylic acid component (A) and the diamine component , The total content of the adipic acid (a2) and the diaminotoluene (b2) may be 25 mol% or less.

In the method for producing a polyamide resin, the copolymerization may be carried out according to a conventional copolymerization method, and may be carried out, for example, by a melt polymerization method or the like.

In the copolymerization, the polymerization temperature may be 80 to 300 ° C, preferably 80 to 280 ° C, and the polymerization pressure may be 10 to 40 kgf / cm 2 , but is not limited thereto.

In one embodiment, the polyamide resin is prepared by filling the reactor with the dicarboxylic acid component (A), the diamine component (B), the catalyst and water, stirring at 80 to 150 ° C for 0.5 to 2 hours, Maintaining at a temperature of 200 to 280 DEG C and a pressure of 20 to 40 kgf / cm2 for 2 to 4 hours, then lowering the pressure to 10 to 20 kgf / cm < 2 > for 1 to 3 hours (copolymerization) And solid state polymerization of the obtained polyamide at a temperature between the glass transition temperature (Tg) and the melting temperature (Tm) in a vacuum state for 10 to 30 hours.

A catalyst may be used for the copolymerization reaction. As the catalyst, a phosphorous-based catalyst may be used. For example, phosphoric acid, phosphorous acid, hypophosphorous acid or a salt or derivative thereof may be used. As a more specific example, phosphoric acid, phosphorous acid, hypophosphorous acid, sodium hypophosphate, sodium hypophosphonate and the like can be used.

The catalyst may be used in an amount of 0 to 3 parts by weight, preferably 0.001 to 1 part by weight, more preferably 0.01 to 0.5 parts by weight, based on 100 parts by weight of the total monomers ((A) + (B) But is not limited thereto.

In addition, in the method for producing the polyamide resin, the end encapsulant may be used in the above amount, and the viscosity of the synthesized polyamide resin can be controlled by controlling the content of the end encapsulant.

Another aspect of the present invention relates to a product (molded article). The product according to the invention is formed (made) from the polyamide resin. For example, the polyamide resin may be made of an automotive UTH (under the hood) engine room material requiring a high glass transition temperature, but is not limited thereto. The product can be easily formed by a person having ordinary skill in the art to which the present invention belongs.

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

Example  1-7 and Comparative Example  1-6

(TPA) and adipic acid (AA) and a diamine component (Diamine) as a dicarboxylic acid component (Diacid) according to the composition shown in the following Table 1, 1,6-hexamethylene diamine (HMDA) and diamino Toluene (TDA) was added to 1.1 molar parts of acetic acid as a terminal endblocker and 100 parts by weight of a diamine component based on 100 molar parts of the above-mentioned dicarboxylic acid component and diamine component. To the 100 parts by weight of the dicarboxylic acid component and the diamine component, sodium hypophosphonate 0.1 And 74 parts by weight of water were charged in a 1-liter autoclave and filled with nitrogen. At 130 ℃ and stirred for 60 minutes, and reacted for After raising for 2 hours in 230 ℃, and reacted for 3 hours while maintaining the 25 kgf / cm 2, and then, was reduced to 15 kgf / cm 2 1 hours, polyamide A prepolymer was prepared. The prepared polyamide prepolymer was subjected to solid phase polymerization at 250 DEG C for 5 hours to obtain a polyamide resin.

Monomer (mol%) Example Comparative Example One 2 3 4 5 6 7 One 2 3 4 5 6 Diacid TPA 80 75 70 75 100 65 70 100 85 70 55 75 75 AA 20 25 30 25 - 35 30 - 15 30 45 25 25 Diamine HMDA 80 75 80 80 75 85 75 100 100 100 100 90 70 TDA 20 25 20 20 25 15 25 - - - - 10 30 Mole defense [Diamine] / [Diacid] 1.010

Experimental Example

The melting temperature, the heat of fusion, the crystallization temperature, the crystallization heat, the glass transition temperature, the intrinsic viscosity, the flowability, the strength retention and the water absorption rate of the polyamide resin prepared in the above Examples and Comparative Examples were evaluated in the following manner, The results are shown in Table 2 below.

Property evaluation method

(1) Melting temperature, crystallization temperature and glass transition temperature (unit: 占 폚): The polyamide resin obtained after the solid phase polymerization in Examples and Comparative Examples was measured using a different scanning calorimeter (DSC). The DSC was measured under the conditions of a nitrogen atmosphere, a temperature range of 30 to 400 占 폚, a temperature raising rate of 10 占 폚 / min, and a cooling rate of 10 占 폚 / min. At this time, the crystallization temperature was the maximum point of the exothermic peak during cooling, and the melting temperature was determined as the maximum point of the endothermic peak at the second temperature rise. The glass transition temperature was determined as the temperature measured at the second heating.

(2) Intrinsic viscosity (unit: dL / g): Measured using a 97% sulfuric acid solution and a Ubbelodhde viscometer at 25 ° C.

(3) Fluidity (unit: mm): Sumitomo injection molding machine SG75H-MIV was used. The cylinder temperature and mold temperature were set at 320 ° C, and the injection pressure was set at 15 MPa to measure the flow distance.

(4) Water Absorption Rate (Unit:%): A specimen having a length of 100 mm, a width of 100 mm and a thickness of 3 mm was prepared and vacuum-dried at 120 ° C for 4 hours. The weight (W 0 ) of the dried specimen was measured, and the dried specimen was treated in a thermo-hygrostat at 50 ° C and RH 90% for 48 hours, and the weight (W 1 ) of the specimen was measured. The water absorption rate was calculated according to the following formula.

Water Absorption Rate (%) = | W 1 -W 0 | / W 0 * 100

(5) Strength retention ratio (unit:%): The strength retention ratio was obtained by measuring the ratio of the tensile strength after the treatment to the tensile strength before the treatment for 24 hours at a temperature of 80 ° C and a relative humidity of 95% in a thermo-hygrostat. The tensile strength was measured according to ISO 527 (23 캜, 5 mm / min).

Example Comparative Example One 2 3 4 5 6 7 One 2 3 4 5 6 Melting temperature (캜) 323 306 312 315 330 302 310 365 342 322 307 307 310 Crystallization temperature (캜) 285 262 275 273 263 270 259 338 320 290 275 270 252 Glass transition temperature (캜) 141 145 145 143 147 140 142 - 98 99 90 125 145 Intrinsic viscosity (dL / g) 0.70 0.78 0.76 0.82 0.90 0.73 0.72 0.82 0.68 0.71 0.70 0.72 0.73 Flowability (mm) 135 132 138 130 127 140 136 - - - 141 130 132 Strength retention (%) 90 92 90 93 91 90 88 88 89 90 87 88 89 Water Absorption Rate (%) 1.5 1.4 1.2 1.3 1.8 1.3 1.7 1.8 1.7 1.8 1.9 1.8 1.9

From the results shown in Table 2, the polyamide resins (Examples 1 to 7) according to the present invention have excellent heat resistance at a glass transition temperature of 140 ° C or higher and excellent moldability from the results of melting temperature, crystallization temperature, . Further, it can be seen that the water absorption rate is low and the strength retention rate is high. Particularly, when adipic acid is used as a copolymer (Example 2) in a polyamide resin using the same ratio of diaminotoluene copolymer (Examples 2 and 5), the glass transition temperature is somewhat lowered, It can be seen that it is improved.

On the other hand, the polyamide resins of Comparative Examples 1 to 4, in which diaminotoluene was not used as a comonomer, had a glass transition temperature of less than 100 占 폚 and the heat resistance was poor, and the glass transition temperature and the like could not be measured. In Comparative Example 5 in which the content of diaminotoluene was less than 15 mol%, the glass transition temperature dropped to 130 캜 or lower. In Comparative Example 6 in which the content of diaminotoluene exceeded 25 mol%, the crystallization temperature And the molding time is prolonged.

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 (14)

(a1) a dicarboxylic acid component (A) comprising an aromatic dicarboxylic acid component; And
(B) a diamine component comprising (b1) 75 to 85 mol% of an aliphatic diamine component and (b2) 15 to 25 mol% of diaminotoluene,
Wherein the dicarboxylic acid component derived from the dicarboxylic acid component (A) and the diamine portion derived from the diamine component (B) are repeated.
The dicarboxylic acid component (A) according to claim 1, wherein the dicarboxylic acid component (A) further comprises 30 mol% or less of (a2) adipic acid, and the dicarboxylic acid component (A) , The total content of the adipic acid (a2) and the diaminotoluene (b2) is 25 mol% or less.
The polyamide resin according to claim 1, wherein the aromatic dicarboxylic acid component (a1) is at least one compound selected from aromatic dicarboxylic acid components having 8 to 20 carbon atoms.
The polyamide resin according to claim 1, wherein the aliphatic diamine component (b1) is at least one compound selected from aliphatic diamine components having 4 to 20 carbon atoms.
The polyamide resin according to claim 1, wherein the polyamide resin has a glass transition temperature (Tg) of 130 ° C or higher.
The polyamide resin according to claim 1, wherein the polyamide resin has a crystallization temperature (Tc) of 250 to 300 ° C and a melting temperature (Tm) of 300 to 340 ° C.
The polyamide resin according to claim 1, wherein the polyamide resin has a moisture absorption rate of 5.0% or less after being treated at 50 ° C and 90% relative humidity for 48 hours.
The polyamide resin according to claim 1, wherein the polyamide resin has an intrinsic viscosity of 0.3 to 2.0 dL / g.
The polyamide resin according to claim 1, wherein the polyamide resin is encapsulated with an end-capping agent whose terminal group is an aliphatic carboxylic acid or an aromatic carboxylic acid.
10. The composition of claim 9, wherein the endblocking agent is selected from the group consisting of acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, pivalic acid, Wherein the polyamide resin comprises at least one of an acid, benzoic acid, toluic acid,? -Naphthalenecarboxylic acid,? -Naphthalenecarboxylic acid and methylnaphthalenecarboxylic acid.
A diamine component containing diamino toluene is copolymerized and has a glass transition temperature (Tg) of 140 ° C or higher.
(B) a dicarboxylic acid component comprising (a1) an aromatic dicarboxylic acid component and (b1) from 75 to 85 mol% of an aliphatic diamine component and (b2) from 15 to 25 mol% of diaminotoluene, ) ≪ / RTI > diamine component of the polyamide resin.
The dicarboxylic acid component (A) according to claim 12, wherein the dicarboxylic acid component (A) further comprises 30 mol% or less of (a2) adipic acid, and the dicarboxylic acid component (A) , The total content of the adipic acid (a2) and the diaminotoluene (b2) is 25 mol% or less.
A molded article formed from the polyamide resin according to any one of claims 1 to 11.
KR1020120148930A 2012-12-18 2012-12-18 Polyamide resin, method for preparing the same, and article comprising the same KR20140079219A (en)

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