WO2015178560A1

WO2015178560A1 - Copolymerized polyamide resin, method for preparing same, and molded product comprising same

Info

Publication number: WO2015178560A1
Application number: PCT/KR2014/011779
Authority: WO
Inventors: 임상균; 배신효; 권소영; 박태준; 김준성; 김진규; 진영섭
Original assignee: 삼성에스디아이 주식회사
Priority date: 2014-05-23
Filing date: 2014-12-03
Publication date: 2015-11-26

Abstract

A copolymerized polyamide resin of the present invention is characterized by comprising: a repeating unit induced from dicarboxylic acid; a repeating unit induced from diamine; and a repeating unit represented by chemical formula 1, wherein the melting point (Tm) of the copolymerized polyamide resin is about 280℃ to about 330℃. The copolymerized polyamide resin has excellent heat resistance and melt-processability.

Description

Copolyamide Resin, Manufacturing Method thereof And Molded Article Including The Same

The present invention relates to a copolymerized polyamide resin, a method for preparing the same, and a product including the same, and more particularly, to a crystalline high heat-resistant copolymerized polyamide resin, a method for producing the same, and a molded article including the same, having excellent heat resistance and melt processability. will be.

High heat resistant nylon can be obtained by condensation polymerization of aromatic dicarboxylic acid or aromatic diamine. The high heat resistant nylon may have a semi-aromatic structure and a semi-crystalline structure, and the heat resistance temperature is significantly higher than that of general nylon products, and thus may be applied to various fields requiring high heat resistance properties. The high heat resistant nylon has a change in physical properties such as heat resistance and fluidity depending on the comonomer and copolymerization ratio.

Commonly used high heat resistant nylon is PA4T, PA6T, PA9T, PA10T, PA11T, PA12T and the like. In general, in the case of PA4T, PA6T, etc., in which the linear alkylene group has a low carbon number in the main chain, since the melting temperature of the homopolymer is very high, it cannot be processed, a large amount (several%) of comonomer is introduced to improve melt processability. For example, in the case of PA6T, commonly used comonomers are adipic acid, isophthalic acid, and the like, and short and long chain aliphatic diamines, cyclic aliphatic diamines, and crushed aliphatic diamines and short chains. And long chain aliphatic dicarboxylic acids, cyclic aliphatic dicarboxylic acids, ground aliphatic dicarboxylic acids and the like can be used. In particular, adipic acid has the same carbon number as terephthalic acid, so that the melting temperature can be lowered without decreasing the crystallinity.

However, when using a dicarboxylic acid or the like containing a linear aliphatic dicarboxylic acid such as adipic acid as a comonomer, decomposition of high heat resistant nylon may occur through a cyclization reaction at a high temperature, which is a known mechanism. (See Archacher BG, Reinhard FW and Kline GM, J Res Natl Bur Stand 4: 391 (1951)). At the time of decomposition, water vapor, CO, CO ₂ , gas such as NH ₃ is generated, and after such injection molding, it may cause blister failure in some processes.

Therefore, it is necessary to develop a crystalline high heat-resistant copolymerized polyamide resin capable of improving melt processability, heat resistance and the like without such decomposition problems.

An object of the present invention is to provide a crystalline high heat-resistant copolymerized polyamide resin having excellent heat resistance and melt processability and a method for producing the same.

Another object of the present invention is to provide a copolymer polyamide resin and a method for producing the same, which can prevent or reduce gas generation at high temperature processing and have improved discoloration.

Still another object of the present invention is to provide a molded article formed of the copolymerized 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 copolymerized polyamide resins. The copolymerized polyamide resin may include repeating units derived from dicarboxylic acid; Repeat units derived from diamines; And a repeating unit represented by the following Chemical Formula 1, wherein the melting temperature (Tm) is about 280 to about 330 ° C.

[Formula 1]

In Formula 1, R ₁ is a linear, branched or cyclic alkylene group having 3 to 12 carbon atoms.

In an embodiment, the repeating unit represented by Formula 1 may be derived from a cyclic amide compound represented by Formula 2 or an amino acid compound represented by Formula 3 below:

[Formula 2]

[Formula 3]

In Chemical Formulas 2 and 3, R ₁ is as defined in Chemical Formula 1.

In embodiments, the dicarboxylic acid may include one or more aromatic dicarboxylic acids having 8 to 20 carbon atoms.

In embodiments, the dicarboxylic acid may comprise about 60 to about 100 mole percent of the aromatic dicarboxylic acid and about 0 to about 40 mole percent of aliphatic dicarboxylic acid having 4 to 20 carbon atoms.

In embodiments, the diamine may include one or more aliphatic diamines having 4 to 20 carbon atoms.

In an embodiment, the content of the repeating unit represented by Formula 1 is about 5 to about 40 moles, based on about 100 moles of the repeating unit derived from the dicarboxylic acid and the repeating unit derived from the diamine, from the diamine The molar ratio (diamine / dicarboxylic acid) of the repeating unit derived and the repeating unit derived from the dicarboxylic acid may be about 0.95 to about 1.15.

In an embodiment, the copolymerized polyamide resin may be encapsulated with an end capping agent having one or more terminal groups containing an aliphatic carboxylic acid and an aromatic carboxylic acid.

In embodiments, the crystallization temperature (Tc) of the copolymerized polyamide resin may be about 240 to about 300 ℃, the glass transition temperature (Tg) may be about 70 to about 120 ℃.

In embodiments, the intrinsic viscosity of the copolymerized polyamide resin may be about 0.5 to about 2.5 dL / g.

In embodiments, the copolymerized polyamide resin may have a gas generation amount (weight loss amount) of about 8% by weight or less, and a water absorption rate of about 3% or less according to Equation 1 when heated to about 120 to about 350 ° C. for about 30 minutes. have:

[Equation 1]

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

In Formula 1, W ₀ is the initial weight of the specimen, W ₁ is the weight after the specimen was treated for about 24 hours at about 85 ℃, relative humidity (RH) about 85% in a thermo-hygrostat.

Another aspect of the present invention relates to a method for producing the copolymerized polyamide resin. The preparation method is a method for preparing a copolymerized polyamide resin comprising polymerizing a monomer mixture comprising dicarboxylic acid, diamine, and a cyclic amide compound represented by Formula 2 or an amino acid compound represented by Formula 3 above. The copolymerized polyamide resin has a melting temperature (Tm) of about 280 to about 330 ° C.

In an embodiment, the method of preparing the copolymerized polyamide resin may include preparing a prepolymer by polymerizing the monomer mixture; And solid-phase polymerizing the prepolymer.

In an embodiment, the prepolymer can have an intrinsic viscosity of about 0.1 to about 0.3 dL / g.

In embodiments, the solid phase polymerization may be to heat the prepolymer to a temperature of about 150 to about 280 ℃.

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

The present invention is excellent in heat resistance, melt processability and the like, can prevent or reduce the generation of gas during high temperature processing, low hygroscopic crystalline high heat-resistant copolymerized polyamide resin, a method for producing the same and a molded article comprising the same Has

Hereinafter, the present invention will be described in detail.

The copolymerized polyamide resin according to the present invention comprises (A) a repeating unit derived from dicarboxylic acid, (B) a repeating unit derived from diamine, and (C) a repeating unit represented by the following formula (1), and melting Temperature (Tm) is characterized in that about 280 to about 330 ℃.

[Formula 1]

In the present specification, the term dicarboxylic acid or the like refers to dicarboxylic acid, alkyl esters thereof (lower alkyl esters having 1 to 4 carbon atoms such as monomethyl, monoethyl, dimethyl, diethyl or dibutyl ester), and acids thereof. Used in the sense including acid anhydride and the like, and reacted with diamines and cyclic amide compounds or amino acid compounds to form repeating units (dicarboxylic acid moiety) derived from dicarboxylic acids. . In addition, in the present specification, a dicarboxylic acid moiety, a repeating unit derived from a diamine (diamine moiety), and a repeating unit represented by Formula 1 include dicarboxylic acid, diamine and When the amino acid compound is polymerized, it means a residue and a ring-opened cyclic amide moiety in which a hydrogen atom (removed from an amine group), a hydroxy group or an alkoxy group (removed from a carboxylic acid group) is removed.

(A) repeating units derived from dicarboxylic acids

The repeating unit derived from the dicarboxylic acid according to an embodiment of the present invention is a residue remaining after the hydroxy group or the alkoxy group is removed from the carboxylic acid group of the dicarboxylic acid. For example, the repeating unit may be represented by the following formula (4).

[Formula 4]

In Formula 4, R ₂ is the remainder except for the carboxylic acid group of the dicarboxylic acid. For example, a hydrocarbon group having 4 to 30 carbon atoms or a hydrocarbon group having 4 to 30 carbon atoms including a hetero atom such as an oxygen atom or a sulfur atom, specifically, a linear, branched or cyclic alkylene group having 4 to 18 carbon atoms, and a carbon number It may be an arylene group of 6 to 18, a linear, branched or cyclic alkylene group of 4 to 18 carbon atoms containing a hetero atom or an arylene group of 6 to 18 carbon atoms containing a hetero atom.

In embodiments, the dicarboxylic acid may be used without limitation, dicarboxylic acid used in conventional polyamide resin. For example, the dicarboxylic acid may include aromatic dicarboxylic acid.

In embodiments, the aromatic dicarboxylic acid may be a compound containing at least one aromatic dicarboxylic acid having 8 to 20 carbon atoms, for example, terephthalic acid, isophthalic acid, 2,6-naphthalenedicar Acids, 2,7-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,4-phenylenedioxyphenylene acid, 1,3-phenylenedioxydiacetic acid, defenic acid, 4,4 ' -Oxybis (benzoic acid), diphenylmethane-4,4'-dicarboxylic acid, diphenylsulfone-4,4'dicarboxylic acid, 4,4'-diphenylcarboxylic acid, mixtures thereof and the like Can be used, but is not limited thereto. Specifically, it may be terephthalic acid, isophthalic acid or a mixture thereof.

The content of the aromatic dicarboxylic acid may be about 60 to about 100 mol%, for example, about 60 to about 90 mol%, specifically about 60 to about 75 mol%, of the total dicarboxylic acids. It may be excellent in the heat resistance, crystallinity and the like of the copolymerized polyamide resin in the above range.

In addition, the dicarboxylic acid of the present invention may further include an aliphatic dicarboxylic acid in order to further increase the processability of the copolymerized polyamide resin. The aliphatic dicarboxylic acid may be a linear, branched or cyclic aliphatic dicarboxylic acid having 6 to 12 carbon atoms, such as adipic acid, 1,4-cyclohexanedicarboxylic acid, 1,3 -Cyclohexanedicarboxylic acid may be used, but is not limited thereto. The content of the aliphatic dicarboxylic acid may be about 0 to about 40 mol%, for example, about 10 to about 40 mol%, specifically about 25 to about 40 mol%, of the total dicarboxylic acids. In the above range, it is possible to reduce or prevent the gas generation phenomenon during the high-temperature processing of the polyamide resin by aliphatic dicarboxylic acid, it is possible to obtain a copolymerized polyamide resin more excellent in workability.

(B) repeating units derived from diamines

The repeating unit derived from the diamine according to an embodiment of the present invention is a residue remaining after the hydrogen atom is removed from the amine group of the diamine. For example, the repeating unit may be represented by the following formula (5).

[Formula 5]

In Formula 5, R ₃ is the remainder except for the amine group of the diamine. For example, a C4-C30 hydrocarbon group or a C4-C30 hydrocarbon group containing hetero atoms, such as an oxygen atom and a sulfur atom, specifically, a C4-C20 linear, branched or cyclic alkylene group, a carbon number It may be an arylene group having 6 to 30, a linear, branched or cyclic alkylene group having 4 to 20 carbon atoms including a hetero atom, or an arylene group having 6 to 30 carbon atoms including a hetero atom.

In an embodiment, the diamine may be used without limitation the diamine used in conventional polyamide resin. For example, the diamine may include aliphatic diamine.

In embodiments, at least one aliphatic diamine having 4 to 20 carbon atoms may be used as the aliphatic diamine. For example, 1,4-butanediamine, 1,6-hexanediamine (hexamethylene diamine (HMDA)), 1,7-heptane diamine, 1,8-octanediamine, 1,10-decanediamine ( decanediamine (DDA), 1,12-dodecanediamine (DDDA), 3-methyl-1,5-pentanediamine, 2,2,4-trimethyl-1,6-hexanediamine, 2,4,4- Trimethyl-1,6-hexanediamine, 5-methyl-1,9-nonanediamine, 2,2-oxybis (ethylamine), bis (3-aminopropyl) ether, ethylene glycol bis (3-aminopropyl) ether Linear or branched aliphatic diamines such as (EGBA), 1,7-diamino-3,5-dioxoheptane, mixtures thereof, and the like, may be used.

In embodiments, the aliphatic diamine may be a mixture of aliphatic diamine having 4 to 10 carbon atoms and aliphatic diamine having 11 to 20 carbon atoms, but is not limited thereto. In this case, the content of the aliphatic diamine having 4 to 10 carbon atoms in the total aliphatic diamine may be about 1 to about 99 mol%, for example, about 50 to about 95 mol%, specifically about 85 to about 95 mol%. . The content of the aliphatic diamine having 11 to 20 carbon atoms may be about 1 to about 99 mol%, for example, about 5 to about 50 mol%, specifically about 5 to about 15 mol%. In the above range, the copolymer polyamide resin may have excellent heat resistance, moisture absorption rate (water absorption rate), and the like, and a small amount of gas may be generated during high temperature processing.

The content of the aliphatic diamine may be about 70 to about 100 mole%, for example about 85 to about 99 mole%, of the total diamine. It is excellent in melt processability, dimensional stability, heat resistance, such as glass transition temperature, etc. of a copolyamide resin in the said range.

In addition, the diamine (B) of the present invention may further contain an aromatic diamine and / or a cyclic aliphatic diamine in order to increase the heat resistance, crystallinity and the like of the copolymerized polyamide resin.

As the aromatic diamine, one or more kinds of aromatic diamines having 6 to 30 carbon atoms can be used. For example, phenylenediamine compounds, such as m-phenylenediamine and p-phenylenediamine, xylenediamine compounds, such as m-xylenediamine and p-xylenediamine, naphthalenediamine compound, etc. can be illustrated, This is not restrictive.

As the cyclic aliphatic diamine, one or more cyclic aliphatic diamines having 6 to 30 carbon atoms can be used. For example, bis (p-aminocyclohexyl) methane (PACM), bis (p-amino-3-methyl-cyclohexyl) methane (bis (p-amino-3- methyl-cyclohexyl) methane: MACM) and the like, but is not limited thereto.

In embodiments, when the aromatic diamine and / or cyclic aliphatic diamine is used, the content may be about 30 mol% or less, for example, about 1 to about 15 mol% of the total diamine. In the above range, the heat resistance, chemical resistance and the like of the copolymerized polyamide resin may be excellent.

In the copolymerized polyamide resin of the present invention, the molar ratio (diamine (B) / dicarboxylic acid (A)) of the repeating unit (A) derived from the dicarboxylic acid and the repeating unit (B) derived from the diamine is For example, about 0.95 to about 1.15, for example about 1.00 to about 1.10. It is possible to produce a polymer having a degree of polymerization suitable for molding in the above range, it is possible to prevent the degradation of physical properties by the unreacted monomer.

(C) repeating unit represented by formula (1)

The repeating unit represented by Formula 1 according to the present invention is a residue remaining after the hydrogen atom is removed from the amine group of the ring-opened cyclic amide compound part or the amino acid compound and the hydroxy or alkoxy group is removed from the carboxylic acid group.

In a specific embodiment, the cyclic amide (lactam) compound and amino acid compound may be substituted or used together with an aliphatic dicarboxylic acid component used for the purpose of improving melt processability. The melting temperature of the amide resin can be reduced more drastically, which can be used to relatively increase the content of the aromatic dicarboxylic acid moiety in the dicarboxylic acid moiety. Therefore, the copolymerized polyamide of the present invention, in which the cyclic amide compound is ring-opened or the amino acid compound is condensation-polymerized, is superior in heat resistance, crystallinity, and the like to a conventional copolymerized polyamide resin having the same melt processability. In this case, the gas generated by the aliphatic dicarboxylic acid moiety may be reduced or prevented during high temperature processing.

In embodiments, the cyclic amide compound may be used a cyclic amide compound having 4 to 12 carbon atoms, for example, may include a cyclic amide compound represented by the following formula (2).

[Formula 2]

In Formula 2, R ₁ is a linear, branched or cyclic alkylene group having 3 to 12 carbon atoms, for example, a linear alkylene group having 4 to 12 carbon atoms.

Specific examples of the cyclic amide compound may include ε-caprolactam, laurolactam, mixtures thereof, and the like, but are not limited thereto.

In embodiments, the amino acid compound may be a conventional amino acid having 4 to 12 carbon atoms, for example, may include an amino acid compound represented by the following formula (3).

[Formula 3]

In Formula 3, R ₁ may be a linear, branched or cyclic alkylene group having 3 to 12 carbon atoms, for example, a linear alkylene group having 4 to 12 carbon atoms.

Specific examples of the amino acid compound may include 5-aminopentanoic acid, 12-aminododecanoic acid, and mixtures thereof, but are not limited thereto.

In the copolymerized polyamide resin of the present invention, the content of the repeating unit (cyclic amide compound or amino acid compound) represented by Chemical Formula 1 is about 5 to about 40 moles, eg about 100 moles of the dicarboxylic acid and the diamine. For example from about 10 to about 35 moles. Melt processability, heat resistance, crystallinity, and the balance of physical properties in the above range may be excellent.

The copolymerized polyamide resin of the present invention may be one in which the end group is sealed with an end capping agent containing at least one aliphatic carboxylic acid and aromatic carboxylic acid. As the end-sealing agent, for example, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauryl acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, pivalic acid, isobutyl acid , Benzoic acid, toluic acid, α-naphthalenecarboxylic acid, β-naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid, mixtures thereof and the like may be used, but is not limited thereto.

The terminal blocker may be included, for example, about 0.01 to about 3 moles, for example about 0.1 to about 2 moles, based on about 100 moles of the dicarboxylic acid (A) and the diamine (B). This is not restrictive.

The copolymerized polyamide resin of the present invention may be prepared according to a conventional polyamide production method, for example, by polymerizing a monomer mixture including the dicarboxylic acid, the diamine, and the cyclic amide compound or amino acid compound. It can manufacture.

The polymerization may be carried out according to a conventional polymerization method, for example, may be carried out using a melt polymerization method, etc., and the polymerization temperature may be about 80 to about 300 ° C, for example, about 90 to about 280 ° C. The polymerization pressure may be about 10 to about 40 kgf / cm ² , but is not limited thereto.

In an embodiment, the copolymerized polyamide resin may be prepared by polymerizing the monomer mixture to prepare a prepolymer and solidifying the prepolymer. For example, the monomer mixture, catalyst and water are charged to the reactor and stirred at about 80 to about 150 ° C. for about 0.5 to about 2 hours, then at a temperature of about 200 to about 280 ° C. and about 20 to about 40 kgf / After maintaining at a pressure of cm ² for about 2 to about 4 hours, then lowering the pressure to about 10 to about 30 kgf / cm ² and reacting for about 1 to about 3 hours (copolymerization) to obtain a polyamide prepolymer, The temperature between the glass transition temperature (Tg) and the melting temperature (Tm) can be obtained through a solid state polymerization (Solid State Polymerization) for about 5 to about 30 hours in a vacuum state.

The prepolymer was dissolved in about 98% sulfuric acid solution at a concentration of about 0.5 g / dl, and the intrinsic viscosity [η] measured by an Ubbelodhde viscometer at about 25 ° C. was about 0.1 to about 0.3 dL / g, eg For example, about 0.15 to about 0.25 dL / g. Melt processability may be excellent in the above range.

In embodiments, the solid phase polymerization may be to heat the prepolymer to about 150 to about 280 ° C., for example about 180 to about 250 ° C., in a vacuum or in the presence of an inert gas such as nitrogen or argon. In the above range, a copolymerized polyamide resin having a weight average molecular weight of about 5,000 to about 50,000 g / mol can be obtained.

A catalyst may be used in the copolymerization reaction. As the catalyst, a phosphorus-based catalyst may be used. For example, phosphoric acid, phosphorus acid, hypophosphorous acid or salts or derivatives thereof may be used. As a more specific example, phosphoric acid, phosphoric acid, hypophosphorous acid, sodium hypophosphate, sodium hypophosphinate and the like can be used.

For example, the catalyst may be used in an amount of about 3 parts by weight or less, for example, about 0.001 to about 1 part by weight, specifically about 0.01 to about 0.5 part by weight, based on about 100 parts by weight of the total monomer mixture. Do not.

In addition, the terminal blocker may be used as the content in the method for preparing the polyamide resin, and by adjusting the content of the terminal blocker, the viscosity of the copolymerized polyamide resin may be adjusted.

The melting temperature (Tm) of the copolymerized polyamide resin according to the present invention may be about 280 ° C. or more, for example, about 280 ° C. to about 330 ° C. As a high heat resistant resin in the above range, it may be excellent in moldability and heat resistance.

The crystallization temperature (Tc) of the copolyamide resin may be about 240 to about 300 ℃, for example about 245 to about 280 ℃. Copolymer polyamide resin excellent in crystallinity can be obtained in the said range.

In addition, the glass transition temperature (Tg) of the copolymerized polyamide resin may be about 70 to about 120 ℃, for example about 75 to about 115 ℃. Within this range, heat resistance and high processability suitable for use of components for electric and electronic materials can be obtained.

The copolymerized polyamide resin is heated by using TGA (thermogravimetric analysis) at about 120 to about 350 ° C. for about 30 minutes, and the measured gas generation amount (weight loss) is about 8% by weight or less, for example, about 1 to about 1. About 7.5% by weight. In forming the copolymerized polyamide resin in the above range, it is possible to reduce or prevent blister defects.

The copolymerized polyamide resin has a water absorption (moisture absorption) of about 3% or less, for example, about 2% or less, specifically about 0.5 to about 25 hours after the specimen is treated at about 85 ° C. and relative humidity of about 85% for about 24 hours. About 1.5%. The moisture absorption rate is about 90mm × 50mm × about 2mm sized specimens vacuum dried at about 120 ° C. for about 4 hours, then the initial weight (W ₀ ) of the specimen is measured, and the specimen is measured in a constant temperature and humidity chamber. After the treatment for about 24 hours at ℃, relative humidity (RH) of about 85%, the weight (W ₁ ) of the specimen may be measured, and then calculated according to Equation 1 below. In forming the copolymerized polyamide resin in the above range, it is possible to reduce or prevent blister defects.

[Equation 1]

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

The copolymerized polyamide resin was dissolved in about 98% sulfuric acid solution at a concentration of about 0.5 g / dl, and the intrinsic viscosity [η] measured by an Ubbelodhde viscometer at about 25 ° C. was about 0.5 to about 2.5 dL / g. For example, about 0.5 to about 2.0 dL / g.

According to the ASTM E313-73 standard, the copolymerized polyamide resin was measured by heat treatment of a specimen of about 90 mm × about 50 mm × about 2 mm in a heat oven at about 250 ° C. for about 10 minutes. YI) may be about 5 to about 10, for example about 6 to about 9.5.

In addition, the copolymerized polyamide resin may have a weight average molecular weight of about 5,000 to about 50,000 g / mol measured by GPC.

The molded article according to the present invention may be formed from the copolymerized polyamide resin. For example, the polyamide resin may be made of an electric and electronic material (connector, LED diffusion plate, etc.) requiring high processability and low gas generation amount, but is not limited thereto. The molded article can be easily formed by those skilled in the art to which the present invention pertains.

Hereinafter, the present invention will be described in more detail with reference to examples, but these examples are for illustrative purposes only and should not be construed as limiting the present invention.

실시예Example

실시예 1 내지 5 및 비교예 1 내지 5Examples 1-5 and Comparative Examples 1-5

According to the composition of Table 1, as dicarboxylic acid (terephthalic acid (TPA) and adipic acid (AA), diamine (diamine), hexamethylenediamine (HMDA), and cyclic amide, ε-capro To the monomer mixture comprising lactam and 100 mole parts of the dicarboxylic acid and diamine, 1.49 mole parts of benzoic acid as terminal blocker, 0.1 part by weight of sodium hypophosphinate as catalyst and 74 parts by weight of water based on 100 parts by weight of the monomer mixture. Into a 1 liter autoclave with charge and filled with nitrogen. After stirring at 100 ° C. for 60 minutes, the temperature was raised to 250 ° C. for 2 hours, the reaction was continued for 3 hours while maintaining 25 kgf / cm ² , and the pressure was reduced to 15 kgf / cm ² , followed by reaction for 1 hour. By leaching, water and the polyamide precopolymer were separated. The separated polyamide precopolymer (intrinsic viscosity [η] = 0.2 dL / g) was charged to a tumbler reactor and subjected to solid phase polymerization at 230 ° C. for 24 hours. Next, it cooled slowly to room temperature and obtained the copolymer polyamide resin.

Table 1

Monomer		Example					Comparative example
Monomer		One	2	3	4	5	One	2	3	4	5
Diacid	TPA (mol%)	100	100	66.7	76.5	75	100	95	90	65	60
Diacid	AA (mol%)	-	-	33.3	23.5	25	-	5	10	35	40
Diamine	HMDA (mol%)	100	100	100	100	100	100	100	100	100	100
Cyclic amide	ε-caprolactam	15	17.5	11.1	17.6	25	-	-	-	-	-
Molar ratio	[Diamine] / [Diacid]	1.015	1.015	1.015	1.015	1.015	1.015	1.015	1.020	1.010	1.015

* Content unit of cyclic amide: mole part relative to 100 mole parts of dicarboxylic acid and diamine

실험예Experimental Example

The polyamide resins prepared in Examples and Comparative Examples were evaluated for melting temperature, crystallization temperature, glass transition temperature, intrinsic viscosity, moisture absorption rate, and gas generation amount by the following method, and the results are shown in Table 2 below.

Property evaluation method

(1) Melting temperature (Tm), crystallization temperature (Tc) and glass transition temperature (Tg) (unit: ° C): Differential Scanning Calorimeter (DSC) was used for polyamide resin obtained after solid state polymerization in Examples and Comparative Examples. It was measured by. DSC was used for Q20 measuring instrument of TA, and 5-10 mg of the sample was vacuum dried at 80 ° C. for 4 hours (up to 3,000 ppm of water), and then heated in a nitrogen atmosphere at a rate of 10 ° C./min from 30 ° C. to 400 ° C. The crystallization temperature was measured at an exothermic peak coming out while cooling at 10 ° C./min after 1 minute of holding at 400 ° C., and then raising the temperature to 400 ° C. at a temperature rising rate of 10 ° C./min after 1 minute of holding at 30 ° C. (2nd scan), the glass transition temperature and the melting temperature were measured from the maximum transition point and the maximum end point of the endothermic peak.

(2) Intrinsic viscosity (unit: dL / g): The sample was dissolved in 98% sulfuric acid solution at a concentration of 0.5 dL / g and measured at 25 ° C. using an Ubbelodhde viscometer.

(3) Water absorption rate (moisture absorptivity, unit:%): After vacuum drying a specimen of 90 mm × 50 mm × 2 mm at 120 ° C. for 4 hours, the initial weight (W ₀ ) of the specimen was measured, and the specimen was placed in a constant temperature and humidity chamber. After treatment at 85 ° C. and relative humidity (RH) at 85% for 24 hours, the weight (W ₁ ) of the specimen was measured, and then calculated according to the following Equation 1. In forming the copolymerized polyamide resin in the above range, it is possible to reduce or prevent blister defects.

[Equation 1]

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

In Formula 1, W ₀ is the initial weight of the specimen, W ₁ is the weight after the specimen was treated for 24 hours at 85 ℃, relative humidity (RH) 85% in a thermo-hygrostat.

(4) Gas generation amount (unit: weight%): The gas generation amount was measured by measuring Isothermal TGA using TGA Q500 by TA Instruments. Specifically, 20 mg of the polyamide resin was quantified in a sample pan, and then heated up to 120 ° C. at a temperature increase rate of 10 ° C. per minute, held for 30 minutes to dry moisture in the resin, and then at a temperature increase rate of 10 ° C. per minute. It heated up to 350 degreeC and maintained for 30 minutes, and measured the generation amount of decomposition gas (weight reduction amount of resin) which arises at this time.

(5) Yellow Index (YI): 90 mm × 50 mm × 2 mm sized specimens were heat-treated in a 250 ° C. gear oven for 10 minutes, followed by ASTM E313- using a CM-2600d colorimeter from Konica Minolta. Measured to 73 standards.

TABLE 2

	Example					Comparative example
	One	2	3	4	5	One	2	3	4	5
Melting temperature (℃)	316	297	302	305	291	365	352	344	325	304
Crystallization temperature (℃)	269	260	260	257	246	N / D	N / D	N / D	296	261
Glass transition temperature (℃)	115	109	95	101	96	N / D	N / D	N / D	100	92
Intrinsic Viscosity (dL / g)	0.78	0.85	0.91	0.88	0.79	0.81	0.87	0.76	0.84	0.88
Hygroscopicity (%)	1.2	1.2	1.3	1.4	1.3	N / D	N / D	N / D	1.6	1.7
Gas generation amount (% by weight)	5.1	5.7	6.8	6.5	7.1	N / D	N / D	N / D	7.6	8.5
Yellow Index (YI)	8.5	7.5	9.4	7.9	8.2	N / D	N / D	N / D	12.3	11.6

From the results of Table 2, the copolymerized polyamide resin (Examples 1 to 5) according to the present invention is a crystalline copolymerized polyamide resin having a melting temperature (Tm) of about 280 to about 330 ° C, and excellent in heat resistance and melt processability. It can be seen. In addition, the moisture absorption rate is lower than 1.4%, the gas generation amount is 7.1 wt% or less can reduce the amount of gas generated during high temperature processing, it can be seen that the yellow index after heat treatment is excellent in discoloration resistance to 9.4 or less.

Simple modifications or changes of the present invention can be easily carried out by those skilled in the art, and all such modifications or changes can be seen to be included in the scope of the present invention.

Claims

Repeating units derived from dicarboxylic acids;

Repeat units derived from diamines; And

To include a repeating unit represented by the formula (1),

Copolyamide resin characterized in that the melting temperature (Tm) is about 280 to about 330 ℃:

[Formula 1]

In Formula 1, R 1 is a linear, branched or cyclic alkylene group having 3 to 12 carbon atoms.
The copolymerized polyamide resin according to claim 1, wherein the repeating unit represented by Formula 1 is derived from a cyclic amide compound represented by Formula 2 or an amino acid compound represented by Formula 3 below:

[Formula 2]

[Formula 3]

In Chemical Formulas 2 and 3, R 1 is as defined in Chemical Formula 1.
The copolymerized polyamide resin according to claim 1, wherein the dicarboxylic acid comprises at least one aromatic dicarboxylic acid having 8 to 20 carbon atoms.
The copolymer of claim 3, wherein the dicarboxylic acid comprises about 60 to about 100 mole percent of the aromatic dicarboxylic acid and about 0 to about 40 mole percent of aliphatic dicarboxylic acid having 6 to 20 carbon atoms. Polyamide resin.
The copolymerized polyamide resin according to claim 1, wherein the diamine comprises at least one aliphatic diamine having 4 to 20 carbon atoms.
The method of claim 1, wherein the content of the repeating unit represented by Formula 1 is about 5 to about 40 mol parts based on about 100 mol parts of the repeating unit derived from the dicarboxylic acid and the repeating unit derived from the diamine. The molar ratio (diamine / dicarboxylic acid) of the repeating unit derived from the diamine and the repeating unit derived from the dicarboxylic acid is about 0.95 to about 1.15.
The copolymerized polyamide resin according to claim 1, wherein the copolymerized polyamide resin is encapsulated with a terminal sealing agent containing at least one aliphatic carboxylic acid and aromatic carboxylic acid terminal group.
The copolymerized polyamide resin of claim 1, wherein the copolymerization polyamide resin has a crystallization temperature (Tc) of about 240 to about 300 ° C and a glass transition temperature (Tg) of about 70 to about 120 ° C.
The copolymerized polyamide resin of claim 1, wherein the intrinsic viscosity of the copolymerized polyamide resin is about 0.5 to about 2.5 dL / g.
The method of claim 1, wherein the copolymerized polyamide resin has a gas generation amount (weight loss amount) of about 8% by weight or less when heated at about 120 to about 350 ° C. for about 30 minutes, and a moisture absorption rate of about 3% according to Equation 1 below. The copolymerized polyamide resin characterized by the following:

[Equation 1]

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

In Formula 1, W 0 is the initial weight of the specimen, W 1 is the weight after the specimen was treated for about 24 hours at about 85 ℃, relative humidity (RH) about 85% in a thermo-hygrostat.
It is a method for producing a copolymerized polyamide resin comprising the step of polymerizing a monomer mixture comprising a dicarboxylic acid, a diamine, and a cyclic amide compound represented by the formula (2) or an amino acid compound represented by the formula (3),

Method for producing a copolymerized polyamide resin, characterized in that the copolymerization polyamide resin has a melting temperature (Tm) of about 280 to about 330 ℃.

[Formula 2]

[Formula 3]

In Formulas 2 and 3, R 1 is a linear, branched or cyclic alkylene group having 3 to 12 carbon atoms.
The method of claim 11, wherein the method for preparing the copolymerized polyamide resin comprises polymerizing the monomer mixture to prepare a prepolymer; And solid-phase polymerizing the prepolymer.
The method of claim 12, wherein the prepolymer has an intrinsic viscosity of about 0.1 to about 0.3 dL / g.
13. The method of claim 12, wherein said solid phase polymerization heats said prepolymer to a temperature of about 150 to about 280 ° C.
Molded article formed from the copolymerized polyamide resin according to any one of claims 1 to 10.