WO2014104699A1 - Résine de polyamide, son procédé de préparation, et produit moulé la comprenant - Google Patents

Résine de polyamide, son procédé de préparation, et produit moulé la comprenant Download PDF

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Publication number
WO2014104699A1
WO2014104699A1 PCT/KR2013/012067 KR2013012067W WO2014104699A1 WO 2014104699 A1 WO2014104699 A1 WO 2014104699A1 KR 2013012067 W KR2013012067 W KR 2013012067W WO 2014104699 A1 WO2014104699 A1 WO 2014104699A1
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Prior art keywords
acid
polyamide resin
component
dicarboxylic acid
mol
Prior art date
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PCT/KR2013/012067
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English (en)
Korean (ko)
Inventor
임상균
권소영
김진규
장승현
전인식
제진아
진영섭
이기연
전석민
Original Assignee
제일모직 주식회사
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Priority claimed from KR1020130161134A external-priority patent/KR101685244B1/ko
Application filed by 제일모직 주식회사 filed Critical 제일모직 주식회사
Publication of WO2014104699A1 publication Critical patent/WO2014104699A1/fr

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Classifications

    • 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
    • C08G69/28—Preparatory processes
    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
    • C08G73/0633—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only two nitrogen atoms in the ring
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors

Definitions

  • the present invention relates to a polyamide resin, a method for producing the same, and a molded article including the same, and more particularly, to a high heat-resistant copolymerized polyamide resin having excellent processability, heat resistance, and dimensional stability, a method for preparing the same, and a molded article including the same. .
  • polyamide resin aliphatic polyamide resins such as nylon 66 and nylon 6 are best known. Although these aliphatic polyamide resins are widely used in automobile parts, electrical appliances, mechanical parts, and the like, they do not have sufficient thermal stability to be applied to fields requiring high heat resistance.
  • Aromatic polyamide resins have a higher melting temperature and higher heat resistance than aliphatic polyamide resins, but are poor in workability due to high melting temperatures and have been used for limited purposes.
  • high heat resistant nylon has a semi-crystal structure, and thus the heat resistance temperature is considerably higher than that of general nylon, so that it can be used in various fields requiring high heat resistance properties.
  • the glass transition temperature (Tg) is about 90 to about 120 °C, has a low glass transition temperature.
  • polyamide (nylon) 6T since the melting temperature is higher than the decomposition temperature, melt processing is impossible, and it is common to copolymerize to lower the processing temperature.
  • an aliphatic monomer such as adipic acid
  • it has a glass transition temperature of less than about 100 ° C.
  • An object of the present invention is to provide a high heat-resistant copolymerized polyamide resin having a glass transition temperature of about 130 ° C. or more, which is excellent in workability, heat resistance, and dimensional stability.
  • Another object of the present invention is to provide a method for producing the polyamide resin.
  • Another object of the present invention is to provide a molded article formed of the polyamide resin.
  • the dicarboxylic acid moiety derived and the diamine moiety derived from the diamine component (B) are characterized by having a repeating structure.
  • the dicarboxylic acid component (A) further comprises less than about 30 mol% (a2) adipic acid, with respect to all of the dicarboxylic acid component (A) and the diamine component (B)
  • the total content of the adipic acid (a2) and the piperazine (b2) may be about 15 to about 30 mol%.
  • the aromatic dicarboxylic acid component (a1) may include at least one of aromatic dicarboxylic acid components having 8 to 20 carbon atoms.
  • the aliphatic diamine component (b1) may include at least one of aliphatic diamine components having 4 to 20 carbon atoms.
  • the glass transition temperature (Tg) of the polyamide resin may be about 130 °C or more.
  • the crystallization temperature (Tc) of the polyamide resin may be about 240 to about 300 °C
  • the melting temperature (Tm) may be about 300 to about 350 °C.
  • the polyamide resin may have a water absorption of about 3% or less after treatment for about 48 hours at about 50 ° C. and about 90% relative humidity.
  • the polyamide resin may be encapsulated with a terminal blocker in which the terminal group is selected from the group consisting of aliphatic carboxylic acid and aromatic carboxylic acid.
  • the terminal blocker may be acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, loric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, pivalic acid, isobutyl acid, It may include one or more of 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 containing about 30 to about 40 mol% of piperazine, and characterized in that the glass transition temperature (Tg) is about 140 ° C. or more.
  • Another aspect of the present invention relates to a method for producing the polyamide resin.
  • the process comprises (a) a dicarboxylic acid component comprising an aromatic dicarboxylic acid component, and (b1) about 60 to about 70 mole percent aliphatic diamine component and (b2) about 30 to about 40 piperazine. Copolymerizing the diamine component (B) comprising mole%.
  • the dicarboxylic acid component (A) further comprises less than about 30 mol% (a2) adipic acid, with respect to all of the dicarboxylic acid component (A) and the diamine component (B)
  • the total content of the adipic acid (a2) and the piperazine (b2) may be about 15 to about 30 mol%.
  • Another aspect of the present invention relates to a molded article molded from the polyamide resin.
  • the present invention has the effect of the invention to provide a high heat-resistant copolymerized polyamide resin having a glass transition temperature of about 130 ° C. or more, excellent in workability, heat resistance, and dimensional stability, a method for preparing the same, and a molded article including the same.
  • the polyamide resin according to one embodiment of the present invention comprises (a) a dicarboxylic acid component comprising an aromatic dicarboxylic acid component, and (b1) about 60 to about 70 mole% of an aliphatic diamine component and ( b2) a dicarboxylic acid moiety derived from the dicarboxylic acid moiety (A) and the diamine moiety (B), wherein the diamine component (B) comprising from about 30 to about 40 mole% of piperazine is copolymerized
  • the diamine moiety derived from has a repeating structure.
  • the polyamide resin according to another embodiment of the present invention is formed by copolymerizing a diamine component containing about 30 to about 40 mol% of piperazine, and has a glass transition temperature (Tg) of about 140 ° C. or more.
  • dicarboxylic acid component and the like are dicarboxylic acid, alkyl esters thereof (lower alkyl esters having 1 to 4 carbon atoms such as monomethyl, monoethyl, dimethyl, diethyl or dibutyl ester), and their Used to include acid anhydride and the like, and reacts with the diamine component to form a dicarboxylic acid moiety.
  • the dicarboxylic acid moiety and the diamine moiety are left after the hydrogen atom, the hydroxy group or the alkoxy group is removed when the dicarboxylic acid component and the diamine component are polymerized. Means a residue.
  • the dicarboxylic acid component (A) used for this invention contains the normal (a1) aromatic dicarboxylic acid component used for manufacture of high heat resistant polyamide resin (nylon).
  • the aromatic dicarboxylic acid component (a1) may include at least one of aromatic dicarboxylic acid components having 8 to 20 carbon atoms, for example, terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid , 2,7-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,4-phenylenedioxyphenylene acid, 1,3-phenylenedioxydiacetic acid, dipenic acid, 4,4'-oxy Bis (benzoic acid), diphenylmethane-4,4'-dicarboxylic acid, diphenylsulfone-4,4'dicarboxylic acid, 4,4'-diphenylcarboxylic acid or mixtures thereof,
  • it may be terephthalic acid, isophthalic acid or a mixture thereof, in particular terephthalic acid or a mixture of terephthalic acid and isophthalic acid.
  • the dicarboxylic acid component (A) is less than about 30 mol% of adipic acid (a2) based on the total dicarboxylic acid component (A) in order to further increase the processability of the polyamide resin. ) May be further included.
  • the content of the aromatic dicarboxylic acid component (a1) in the dicarboxylic acid component (A) is greater than about 70 mol%, for example, about 75 to about 95 mol%, specifically about 75 to about 90 mole%, and the content of adipic acid (a2) may be less than about 30 mole%, for example, about 5 to about 25 mole%, specifically about 10 to about 25 mole%.
  • a polyamide resin having excellent physical properties such as heat resistance and processability can be obtained.
  • the diamine component (B) used in the present invention necessarily contains the piperazine (b2) as a copolymerization 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 include one or more of aliphatic diamine components having 4 to 20 carbon atoms, for example, 1,4-butanediamine, 1,6-hexanediamine (hexamethylenediamine) ), 1,7-heptane diamine, 1,8-octanediamine, 1,10-decanediamine, 2-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 One or more aliphatic linear diamines, such as -aminopropyl) ether (EGBA), 1,7-diamino-3,5-dioxoheptane, mixtures thereof, can be used, but is not limited thereto.
  • 1,4-butanediamine
  • the piperazine (b2) has a hexagonal ring structure including two nitrogen atoms, and may produce a polyamide resin having a high glass transition temperature (Tg) of about 140 ° C. or more when copolymerized, such as piperazine.
  • Tg glass transition temperature
  • the cyclic secondary amine of may have low crystallinity and crystallization rate due to high heat resistance due to the structure at the time of polymerization and lack of hydrogen atoms at the amide bond.
  • the adipic acid (a2) may be copolymerized to compensate for the decrease in crystallinity and crystallization rate.
  • the content of the aliphatic diamine component (b1) is about 60 to about 70 mol%, for example, about 61.5 to about 68.5 mol%, specifically about 62.5 to about 67.5 mol%
  • the pipe The content of lazine (b2) is about 30 to about 40 mole%, for example about 31.5 to about 38.5 mole%, specifically about 32.5 to about 37.5 mole%. If the content of the aliphatic diamine component (b1) is less than about 60 mol%, or if the content of the piperazine (b2) exceeds about 40 mol%, there is a fear that the crystallinity and processability of the polyamide resin are lowered. When the content of the aliphatic diamine component (b1) is greater than about 70 mol% or the content of piperazine (b2) is less than about 30 mol%, the heat resistance of the polyamide resin may be lowered.
  • the adipic acid (a2) When the adipic acid (a2) is used, the adipic acid (a2) and the piperazine (b2) with respect to the entire dicarboxylic acid component (A) and the diamine component (B) (100 mol%). ) May have a total content of about 15 to about 30 mole%, for example about 17 to about 28 mole%. Within this range, a polyamide resin having excellent physical properties such as crystallinity, processability, heat resistance, and the like can be obtained.
  • the ratio of the dicarboxylic acid component (A) and the diamine component (B) is about 0.93 to about 1.07, for example from about 0.97 to about 1.03. Within this range, it is possible to prevent a decrease in physical properties due to unreacted monomers.
  • the polyamide resin of the present invention may be sealed with an end capping agent selected from the group consisting of aliphatic carboxylic acids and aromatic carboxylic acids.
  • acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, loric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, pivalic acid, isobutyl acid, benzoic acid, toluic acid , ⁇ -naphthalene carboxylic acid, ⁇ -naphthalene carboxylic acid, methylnaphthalene carboxylic acid, mixtures thereof and the like can be exemplified, but is not limited thereto.
  • the terminal encapsulant may be included in an amount of about 0 to about 5 moles, for example about 0.01 to about 3 moles, based on about 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 about 130 ° C. or higher, for example, about 140 ° C. or higher, specifically about 145 to about 170 ° C. In the above range, it may have a high heat resistance, heat resistance, etc. for use in automotive engine room parts and the like.
  • the crystallization temperature (Tc) of the polyamide resin may be about 240 to about 300 °C, for example about 250 to about 290 °C, the melting temperature (Tm) is about 300 to about 350 °C, for example about 305 to About 340 ° C. In the above range, it has heat resistance suitable for use of the product for UTH.
  • the polyamide resin may have a water absorption of about 3% or less, for example about 2.2% or less, specifically about 1.1 to about 2.0% after treatment for about 48 hours at about 50 ° C. and about 90% relative humidity. Within this range, long-term use may be possible under vehicle antifreeze (H 2 O + EG) as an automotive engine room component or the like.
  • vehicle antifreeze H 2 O + EG
  • the water absorption rate is about 100mm in length, about 100mm in width, about 3mm in thickness to produce a specimen and vacuum dried at about 120 °C for about 4 hours, and measure the weight (W0) of the dried specimen, and then dried the dried specimen After treatment for about 48 hours at about 50 °C, relative humidity (RH) about 90% in a humidifier, the weight (W1) of the specimen can be measured and calculated according to the following equation.
  • the polyamide resin may have a measured intrinsic viscosity [ ⁇ ] of about 0.15 to about 1 dL / g using a Ubbelodhde viscometer at about 25 ° C. using about 98% sulfuric acid solution or o -chlorophenol. This is not restrictive.
  • the polyamide resin may have a strength retention of about 82% or more, for example, about 85 to about 95%.
  • the strength retention rate may be measured as the ratio of tensile strength after treatment to tensile strength before treatment for about 24 hours at about 80 ° C. and relative humidity of about 95% in a thermo-hygrostat.
  • the tensile strength can be measured according to ISO 527 (about 23 ° C., about 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 about 60 to about 70 mole% of a dicarboxylic acid component (A) comprising the aromatic dicarboxylic acid component (a1), and the aliphatic diamine component (b1) and piperazine (b2) copolymerizing the diamine component (B) comprising about 30 to about 40 mole%.
  • the dicarboxylic acid component (A) may further comprise less than about 30 mole percent (a2) adipic acid, wherein the dicarboxylic acid component (A) and the diamine component (B) in total With respect to, the total content of the adipic acid (a2) and the piperazine (b2) may be about 15 to about 30 mol%.
  • the copolymerization may be performed according to a conventional copolymerization production method, for example, using a melt polymerization method or the like.
  • the polymerization temperature may be about 80 to about 300 °C, for example about 80 to about 280 °C, the polymerization pressure may be about 10 to about 40 kgf / cm 2 , but is not limited thereto.
  • the polyamide resin is charged to the reactor with the dicarboxylic acid component (A), the diamine component (B), the catalyst and water, and at about 80 to about 150 ° C. for about 0.5 to about 2 hours. After stirring, at a temperature of about 200 to about 280 ° C.
  • a catalyst may be used in the copolymerization reaction.
  • a phosphorus-based catalyst may be used.
  • phosphoric acid, phosphorus acid, hypophosphorous acid or salts or derivatives thereof may be used.
  • phosphoric acid, phosphoric acid, hypophosphorous acid, sodium hypophosphate, sodium hypophosphinate and the like can be used.
  • the catalyst is, for example, about 0 to about 3 parts by weight, for example about 0.001 to about 1 part by weight, specifically about 0.01 to about 1 part by weight, based on about 100 parts by weight of the total monomers ((A) + (B)) 0.5 parts by weight may be used, but is not limited thereto.
  • the terminal blocker may be used as the content in the method of preparing the polyamide resin, and the viscosity of the synthesized polyamide resin may be adjusted by controlling the content of the terminal blocker.
  • the molded article according to the present invention is formed (manufactured) from the polyamide resin.
  • the polyamide resin may be made of an automotive under the hood engine room material that requires a high glass transition temperature, but is not limited thereto.
  • the molded article can be easily formed by those skilled in the art to which the present invention pertains.
  • composition of Tables 1 and 2 as dicarboxylic acid component (Diacid), 1,6-hexamethylenediamine (HMDA), as terephthalic acid (TPA) and adipic acid (AA) and diamine component (Diamine), 2-methylpentanediamine (MPD) and piperazine (PIP) were added to 100 mol parts of the dicarboxylic acid component and the diamine component, to 1.5 mol parts of acetic acid as the end-sealing agent, and 100 parts by weight of the dicarboxylic acid component and the diamine component.
  • HMDA 1,6-hexamethylenediamine
  • TPA terephthalic acid
  • AA adipic acid
  • diamine component Diamine
  • MPD 2-methylpentanediamine
  • PIP piperazine
  • polyamide Precopolymers were prepared.
  • the polyamide prepolymer prepared was subjected to solid phase polymerization at 230 ° C. for 8 hours to obtain a polyamide resin.
  • the melting temperature, the heat of melting, the crystallization temperature, the heat of crystallization, the glass transition temperature, the intrinsic viscosity, the fluidity, the strength retention rate and the water absorption were evaluated by the following method. It is shown in Tables 3 and 4 below.
  • Intrinsic viscosity (unit: dL / g): It measured using 97% sulfuric acid solution and the Ubbelodhde viscometer at 25 degreeC.
  • 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 (W0) of the dried specimen was measured, and the weight (W1) of the specimen was measured after treating the dried specimen for 48 hours at 50 ° C. and RH 90% in a thermo-hygrostat. The water absorption was calculated according to the following formula.
  • Strength retention rate (unit:%): The strength retention rate was obtained by measuring the ratio of tensile strength after treatment to tensile strength before treatment for 24 hours at a temperature of 80 ° C. and a relative humidity of 95% in a constant temperature and humidity chamber. Tensile strength was measured according to ISO 527 (23 ° C., 5 mm / min).
  • the polyamide resins (Examples 1 to 6) according to the present invention have excellent heat resistance and excellent moldability from the results of melting temperature, crystallization temperature, fluidity, and the like. In addition, it can be seen that the water absorption rate is low and the strength retention rate is high.
  • a polyamide resin using the same proportion of piperazine copolymer (Examples 1, 5 and 6, Examples 2 and 4)
  • adipic acid is used as the copolymer (Examples 4 to 6)
  • glass is slightly lowered, it can be seen that the workability is improved.
  • the polyamide resins of Comparative Examples 1 to 3 which do not use piperazine as comonomers, are inferior in heat resistance to a glass transition temperature of less than 100 ° C. or decomposed due to a high melting temperature, thereby causing a glass transition temperature, a heat of fusion, and a heat of crystallization.
  • the polyamide resin of Comparative Example 4 which used MPD instead of piperazine as a comonomer, could not be measured, and there is a concern that the molecular weight increase during solid phase polymerization may be inhibited by the cyclization reaction of MPD.
  • Comparative Example 6 having a piperazine content of less than 30 mol%, it can be seen that it is not suitable for UTH use because of its relatively high melting temperature and low crystallinity.
  • the piperazine content is more than 40 mol% and the total comonomer (adipic acid, piperazine) content is more than 30 mol% with respect to the total dicarboxylic acid component and the diamine component, It became amorphous and could not confirm thermal characteristics other than Tg.

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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)
  • Polyamides (AREA)

Abstract

La présente invention concerne une résine de polyamide obtenue par copolymérisation de : (A) un composant acide dicarboxylique comprenant (a1) un composant acide dicarboxylique aromatique ; et (B) un composant diamine comprenant (b1) environ 60 à environ 70 % en moles d'un composant diamine aromatique et (b2) environ 30 à environ 40 % en moles de pipérazine. La présente invention est en outre caractérisée en ce qu'elle comporte un motif répété d'une fraction acide dicarboxylique dérivée du composant acide dicarboxylique (A) et une fraction diamine dérivée du composant diamine (B). La résine de polyamide présente une aptitude au traitement, une résistance thermique et une stabilité dimensionnelle excellentes.
PCT/KR2013/012067 2012-12-28 2013-12-24 Résine de polyamide, son procédé de préparation, et produit moulé la comprenant WO2014104699A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR10-2012-0157665 2012-12-28
KR20120157665 2012-12-28
KR10-2013-0161134 2013-12-23
KR1020130161134A KR101685244B1 (ko) 2012-12-28 2013-12-23 폴리아미드 수지, 이의 제조방법 및 이를 포함하는 제품

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4433117A (en) * 1982-03-23 1984-02-21 Kuraray Co., Ltd. Copolyesteramide and production of the same
US5516855A (en) * 1987-11-04 1996-05-14 General Electric Company Amide-ester copolymers and process for the preparation thereof
JP2001002917A (ja) * 1999-06-18 2001-01-09 Toyobo Co Ltd ポリアミド組成物
US20030055210A1 (en) * 2000-02-21 2003-03-20 Masahiro Sawada Molding material for electrical and electronic parts
JP2004059829A (ja) * 2002-07-31 2004-02-26 Sumitomo Electric Ind Ltd 有機酸可溶型ポリアミド樹脂、その製造方法、及び三次元射出成形回路部品の製造方法
WO2012093722A1 (fr) * 2011-01-07 2012-07-12 旭化成ケミカルズ株式会社 Polyamide copolymère

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4433117A (en) * 1982-03-23 1984-02-21 Kuraray Co., Ltd. Copolyesteramide and production of the same
US5516855A (en) * 1987-11-04 1996-05-14 General Electric Company Amide-ester copolymers and process for the preparation thereof
JP2001002917A (ja) * 1999-06-18 2001-01-09 Toyobo Co Ltd ポリアミド組成物
US20030055210A1 (en) * 2000-02-21 2003-03-20 Masahiro Sawada Molding material for electrical and electronic parts
JP2004059829A (ja) * 2002-07-31 2004-02-26 Sumitomo Electric Ind Ltd 有機酸可溶型ポリアミド樹脂、その製造方法、及び三次元射出成形回路部品の製造方法
WO2012093722A1 (fr) * 2011-01-07 2012-07-12 旭化成ケミカルズ株式会社 Polyamide copolymère

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