KR950009154B1 - Polyester resin composition - Google Patents
Polyester resin composition Download PDFInfo
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- KR950009154B1 KR950009154B1 KR1019910020210A KR910020210A KR950009154B1 KR 950009154 B1 KR950009154 B1 KR 950009154B1 KR 1019910020210 A KR1019910020210 A KR 1019910020210A KR 910020210 A KR910020210 A KR 910020210A KR 950009154 B1 KR950009154 B1 KR 950009154B1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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Abstract
Description
본 발명은 폴리에스테르 수지 조성물에 관한 것으로서, 더욱 상세하게는 폴리에틸렌 테레프탈레이트 수지에 카르복실기를 함유하는 불포화 탄화수소계 중합체 금속염과 소르비톨계 화합물 및 에폭시 화합물을 첨가함으로써, 결정화 속도가 빠르고 사출성 형성이 우수하여 외관 및 이형성이 우수하고 기계적 강도가 우수하도록 제반물성을 개선한 폴리에스테르 수지조성물에 관한 것이다.The present invention relates to a polyester resin composition, and more particularly, by adding an unsaturated hydrocarbon-based polymer metal salt containing a carboxyl group, a sorbitol-based compound, and an epoxy compound to a polyethylene terephthalate resin, which has a high crystallization rate and excellent injection moldability. The present invention relates to a polyester resin composition having improved appearance properties such as excellent appearance and releasability and excellent mechanical strength.
일반적으로 폴리에틸렌 테레프탈레이트 수지는 내열성, 내약품성, 내광성 및 전기적 특성이 우수해서 섬유, 필름 및 성형품으로 널리 이용되고 있다.In general, polyethylene terephthalate resin is widely used as a fiber, a film and a molded article because of excellent heat resistance, chemical resistance, light resistance and electrical properties.
그러나, 이러한 폴리에틸렌 테레프탈레이트 수지는 낮은 금형온도(100℃ 미만)에서 사출 성형시 결정화 속도가 늦고, 불균일한 결정화에 의해 이형성 및 표면외관이 불량하고 기계적 강도가 저하되는 문제점을 안고 있다.However, such a polyethylene terephthalate resin has a problem in that the crystallization rate is slow during injection molding at a low mold temperature (less than 100 ° C.), poor releasability and surface appearance due to non-uniform crystallization, and a decrease in mechanical strength.
이러한 문제점을 해결하기 위하여 일본특허공개 소60-233148호에서는 폴리에틸렌 테레프탈레이트에 폴리 옥시알킬렌계 물질을 첨가하는 방법을 제시하였고, 일본특허공개 소57-38847호에서는 소르비탄계 유도체, 파리핀왁스, 유기카르본산 금속염 등을 첨가하는 방법을 제시하였으며, 미국특허 제4,448,913호에서 소디움 벤조에이트와 폴리 α-올레핀 등을 핵제로 사용하는 방법을 제시하였다.In order to solve this problem, Japanese Patent Publication No. 60-233148 proposes a method of adding a polyoxyalkylene-based material to polyethylene terephthalate, and Japanese Patent Publication No. 57-38847 discloses a sorbitan derivative, a paraffin wax, A method of adding an organocarboxylic acid metal salt and the like has been proposed, and a method of using sodium benzoate and poly α-olefin as a nucleating agent is disclosed in US Pat. No. 4,448,913.
그러나 이러한 방법들은 수지의 인장강도 및 굴곡강도 등의 기계적 강도를 향상시키지 못하였다.However, these methods did not improve the mechanical strength such as tensile strength and flexural strength of the resin.
또한, 미국특허 제4,435,546호에서는 단분자로된 지방족 카르본산의 에스테르를 첨가하는 방법을 제시하였고, 미국특허 제4,368,288호에서는 블록코폴리에스테르와 유기화합물의 이온화 가능한 금속염 등을 사용하는 방법을 제시하였으나, 이들 방법들에 의하면 수지의 내구성이 떨어지고 물성의 재현성이 떨어졌다.In addition, US Pat. No. 4,435,546 proposes a method for adding an ester of a monomolecular aliphatic carboxylic acid, while US Pat. No. 4,368,288 proposes a method for using ionizable metal salts of block copolyesters and organic compounds. According to these methods, the durability of the resin was inferior and the reproducibility of physical properties was inferior.
한편, 미국특허 제3,368,975호, 제3,575,931호 등에는 탈크, 방해석 등의 무기물을 첨가하는 방법을 제시하였으나 이들 방법 또한 만족할 만한 결정화 속도를 얻을 수 없었다.On the other hand, U.S. Patent Nos. 3,368,975 and 3,575,931 and the like have been proposed to add inorganic materials such as talc, calcite, but these methods also could not obtain satisfactory crystallization rate.
이에, 본 발명에서는 이러한 종래 방법들의 결점을 보완하기 위해서, 폴리에틸렌 테레프탈레이트 수지에 카르복실기를 함유하는 불포화 탄화수소계 중합체금속염과 소르비톨계 화합물 및 에폭시 화합물을 첨가하므로써, 결정화 속도가 빠르고 표면 외관과 이형성 및 기계적 강도가 우수한 폴리에틸렌 테레프탈레이트 수지 조성물을 제공하는데 그 목적이 있다.Accordingly, in the present invention, in order to compensate for the drawbacks of these conventional methods, by adding an unsaturated hydrocarbon-based polymer metal salt containing a carboxyl group, a sorbitol-based compound and an epoxy compound to the polyethylene terephthalate resin, the crystallization rate is fast and the surface appearance, mold release and mechanical properties are increased. It is an object to provide a polyethylene terephthalate resin composition excellent in strength.
이하, 본 발명을 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in detail.
본 발명은 폴리에틸렌 테레프탈레이트 수지 조성물에 있어서, 폴리에틸렌 테레프탈레이트 수지에 전체 조성물 기준으로 다음 a), b), c) 화합물을 동시에 첨가하여서 된 것을 특징으로 한다.The present invention is characterized in that in the polyethylene terephthalate resin composition, the following a), b) and c) compounds are simultaneously added to the polyethylene terephthalate resin based on the total composition.
a) 카르복실산과 불포화 탄화수계 중합체를 1족 금속으로 중화시킨 화합물 2.0∼10중량%a) 2.0 to 10% by weight of a compound in which a carboxylic acid and an unsaturated hydrocarbon-based polymer are neutralized with a Group 1 metal
b) 소르비톨계 화합물 0.05∼10중량%b) 0.05-10 wt% of sorbitol compound
c) 비스페놀A형 에폭시 화합물 0.1∼7중량%c) Bisphenol A epoxy compound 0.1-7 weight%
또한, 본 발명은 폴리에틸렌 테레프탈레이트 수지에 전체 조성물 기준으로 상기 a), b), c) 화합물과 0.5∼10중량%의 폴리옥시알킬렌계 화합물을 동시에 첨가하여서 된 조성물을 포함한다.The present invention also includes a composition obtained by simultaneously adding the above compounds a), b) and c) and 0.5 to 10% by weight of a polyoxyalkylene-based compound to the polyethylene terephthalate resin.
이와같은 본 발명은 더욱 상세히 설명하면 다음과 같다.Such a present invention will be described in more detail as follows.
본 발명에서 카르복실산과 불포화 탄화수소계 중합체로서는 에틸렌/아크릴산 이원공중합체, 에틸렌/메타아크릴산 이원공중합체, 스틔렌/무수말레인산 이원공중합체, 에틸렌/프로필렌/아크릴산 삼원공중합체 중에서 선택된 하나 또는 2이상을 사용하며, 1족 금속으로서는 나트륨 또는 칼륨이 효과적이며, 특히 나프륨이 효과적이다.In the present invention, the carboxylic acid and the unsaturated hydrocarbon-based polymer include one or two or more selected from ethylene / acrylic acid binary copolymer, ethylene / methacrylic acid binary copolymer, squalene / maleic anhydride binary copolymer, and ethylene / propylene / acrylic acid terpolymer. As the Group 1 metal, sodium or potassium is effective, and naphlium is particularly effective.
이러한 카르복실산과 불포화 탄화수소계 중합체를 1족 금속으로 중화시킨 화합물은 폴리에틸렌 테레프탈레이트 수지의 결정화 속도를 빠르게 하고 표면 외관과 이형성을 좋게하기 위하여 20∼10 중량%를 첨가하는 바, 첨가량이 2.0 중량% 미만이면 결정화 속도의 상승 및 사출성형성의 향상효과를 적고, 10중량%를 초과하면 기계적 강도가 떨어진다.The compound in which the carboxylic acid and the unsaturated hydrocarbon-based polymer are neutralized with a Group 1 metal is added in an amount of 20 to 10% by weight in order to speed up the crystallization rate of the polyethylene terephthalate resin and to improve surface appearance and releasability. If less, the effect of increasing the crystallization rate and injection molding is less. If the content exceeds 10% by weight, the mechanical strength is lowered.
또한, 본 발명에서 소르비톨계 화합물로서 비스(p-에틸벤질리덴) 소르비톨(C24H30O6) 및 그의 유도체들을 사용할 수 있으며, 특히 비스(p-에틸벤질리덴)소르비톨이 효과적이다.In the present invention, bis (p-ethylbenzylidene) sorbitol (C 24 H 30 O 6 ) and derivatives thereof can be used as the sorbitol compound, and bis (p-ethylbenzylidene) sorbitol is particularly effective.
이러한 소르비톨계 화합물 역시 폴리에틸렌 테레프탈레이트 수지의 결정화 속도를 빠르게 하고 표면외관과 이형성을 좋게하기 위하여 첨가하는 바, 0.05∼1.0중량%를 첨가하며, 그 첨가량이 0.05 중량% 미만이면 사출 성형성의 향상효과과 떨어지고, 1.0중량%를 초과하면 기계적 강도가 떨어진다.The sorbitol-based compound is also added to speed up the crystallization rate of polyethylene terephthalate resin and improve surface appearance and releasability, and is added in an amount of 0.05 to 1.0% by weight. When it exceeds 1.0 weight%, mechanical strength falls.
그리고, 본 발명에서 비스페놀A형 에폭시 화합물은 에폭시 단량이 500∼3,000인 다음 구조식(I)의 화합물을 사용한다.In the present invention, the bisphenol A epoxy compound uses a compound of the following structural formula (I) having an epoxy unit of 500 to 3,000.
이러한 에폭시 화합물은 기계적 강도를 향상시키기 위하여 0.1∼7중량%를 첨가하는 바, 그 첨가량이 0.1중량% 미만이면 기계적 강도의 향상 효과가 적고 7중량%를 초과하면 사출성형성이 불량해진다.When the epoxy compound is added in an amount of 0.1 to 7% by weight in order to improve the mechanical strength, if the addition amount is less than 0.1% by weight, the effect of improving mechanical strength is small, and when it exceeds 7% by weight, injection molding is poor.
한편, 본 발명은 폴리에틸렌 테레프탈레이트 수지에 상기 a), b), c) 화합물 외에 폴리옥시아릴렌계 화합물을 첨가하는 것을 포함하는 바, 본 발명에서 폴리옥시알킬렌계 화합물로서는 폴리에틸렌글리콜, 폴리프로필렌글리콜 등을 사용하고, 이러한 폴리옥시알킬렌계 화합물을 0.5∼10중량% 첨가하므로써 결정화속도 상승효과를 얻을 수 있으며, 만일 첨가량이 0.5중량% 미만이면 결정화속도 개선에 문제가 있고, 10중량%를 초과하면 내열성 및 기계적 강도가 떨어진다.Meanwhile, the present invention includes adding a polyoxyarylene-based compound to the polyethylene terephthalate resin in addition to the a), b), and c) compounds. In the present invention, the polyoxyalkylene-based compound includes polyethylene glycol, polypropylene glycol, and the like. By using 0.5 to 10% by weight of the polyoxyalkylene compound, a synergistic effect can be obtained. If the amount is less than 0.5% by weight, there is a problem in improving the crystallization rate. And mechanical strength is poor.
이와같은 본 발명에서는 특히 상기 화합물들을 동시에 첨가하는 것이 상술성형성 개선과 동시에 기계적강도 개량면에서 효과적인 것으로 나타났으며, 보강제로서 실란 화합물로 표면처리된 유리단섬유를 사용할 수 있고, 안정제 및 착색제 등을 첨가할 수 있다.In the present invention, in particular, the addition of the compounds at the same time appeared to be effective in improving the mechanical strength at the same time to improve the above-described formability, and can be used as a reinforcing agent short glass fiber surface-treated with a silane compound, stabilizers and coloring agents, etc. Can be added.
이하, 본 발명을 실시예에 의하여 더욱 상세히 설명하겠는 바, 실시예에 의해 본 발명이 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited by Examples.
[실시예 1∼2, 비교예 1∼8]EXAMPLES 1-2, COMPARATIVE EXAMPLES 1-8
폴리에틸렌 테레프탈레이트 수지를 140℃에서 4시간 이상 회전식 건조기에서 건조한 후 다음 표 1의 성분들을 동시에 압출기에서 용융혼합 후 압출하여 칩상태로 만든다. 이 칩을 120℃에서 4시간동안 건조한 후 아래 조성으로 사출성형하여서 UTM으로 물성을 측정하였다.After drying the polyethylene terephthalate resin in a rotary dryer at 140 ℃ for more than 4 hours, the components of Table 1 are melt-mixed and extruded at the same time in an extruder to make a chip state. The chip was dried at 120 ° C. for 4 hours and then injection molded with the following composition to measure physical properties with UTM.
실린더온도 : 260∼285℃Cylinder temperature: 260 ~ 285 ℃
금형온도 : 85∼100℃Mold temperature: 85 ~ 100 ℃
냉각시간 : 10∼15초Cooling time: 10-15 seconds
[표 1]TABLE 1
상기표에서In the table above
PET : 폴리에틸렌 테레프탈레이트PET: Polyethylene Terephthalate
폴리옥시알킬렌계 화합물 : 폴리에틸렌글리콜Polyoxyalkylene compound: polyethylene glycol
소르비톨계 화합물 : 비스(p-에틸 벤질리덴)소르비톨Sorbitol Compound: Bis (p-ethyl benzylidene) sorbitol
에폭시 화합물 : 상기 구조식(I) 화합물Epoxy Compound: Compound of Formula (I)
[참고예][Reference Example]
상기 실시예 및 비교예에서 제조한 조성물의 물성을 다음의 방법으로 측정하여 그 결과를 다음 표 2에 나타내었다.The physical properties of the compositions prepared in Examples and Comparative Examples were measured by the following method, and the results are shown in Table 2 below.
(1) 결정화 특성(1) crystallization characteristics
사출성형시 금형에서의 결정화도, 결정화속도 및 성형성을 간접적으로 측정할 수 있는 파라메타로써 다음 변수를 측정하였다.The following parameters were measured as parameters that can indirectly measure the crystallinity, crystallization rate, and moldability in the mold during injection molding.
H1: 요융온도(Tm)에서의 흡열량(㎈/g)H 1 : endothermic amount (m / g) at the melting temperature (Tm)
H2: 결정화 온도(Tc)에서의 발열량(㎈/g)H 2 : calorific value (㎈ / g) at crystallization temperature (Tc)
Q : 폴리에틸렌 테레프탈레이트 수지의 순수결정을 녹이는데 필요한 열량(=32.14㎈/g)Q: The amount of heat required to melt the pure crystal of polyethylene terephthalate resin (= 32.14 ㎈ / g)
H1과 H2는 시차열분석기(DSC)로 측정하였다.H 1 and H 2 were measured by differential thermal analyzer (DSC).
(2) 이형성(2) release
사출시험을 70회 실시했을 때 사출시편의 금형에서 붙지않고 떨어지는 횟수를 측정하였다.When the injection test was carried out 70 times, the number of times that the non-stick was dropped from the mold of the injection specimen was measured.
(3) 인장강도(3) tensile strength
ASTM D638에 의거 실시하였다.It carried out according to ASTM D638.
[표 2]TABLE 2
본 발명의 수지 조성물의 경우 X파라메타가 0.12이상인 바, X파라메타가 0.12이상인 경우에 결정화 속도, 결정화도 및 사출 성형성이 우수하고 기계적강도 또한 우수하다.In the resin composition of the present invention, when the X parameter is 0.12 or more, when the X parameter is 0.12 or more, the crystallization rate, crystallinity and injection moldability are excellent, and mechanical strength is also excellent.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019910020210A KR950009154B1 (en) | 1991-11-14 | 1991-11-14 | Polyester resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019910020210A KR950009154B1 (en) | 1991-11-14 | 1991-11-14 | Polyester resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR930010119A KR930010119A (en) | 1993-06-22 |
| KR950009154B1 true KR950009154B1 (en) | 1995-08-16 |
Family
ID=19322796
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1019910020210A KR950009154B1 (en) | 1991-11-14 | 1991-11-14 | Polyester resin composition |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR950009154B1 (en) |
-
1991
- 1991-11-14 KR KR1019910020210A patent/KR950009154B1/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| KR930010119A (en) | 1993-06-22 |
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