KR900006302B1 - Polyester resin composition - Google Patents

Polyester resin composition Download PDF

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KR900006302B1
KR900006302B1 KR1019870007847A KR870007847A KR900006302B1 KR 900006302 B1 KR900006302 B1 KR 900006302B1 KR 1019870007847 A KR1019870007847 A KR 1019870007847A KR 870007847 A KR870007847 A KR 870007847A KR 900006302 B1 KR900006302 B1 KR 900006302B1
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compound
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polyester resin
molding
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KR890002333A (en
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한성연
김동일
최인규
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주식회사 삼양사
김상응
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02Polyesters derived from dicarboxylic acids and dihydroxy compounds

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Abstract

Polyester resin compsn. having good moulding properties is improved of the crystalization velocity by, in polyethylene terephthalate resin having 0.4-1.0 dl/gr of inherent viscosity, (i) adding 0.05-30 wt.% of copolyester whose repeating unit mole ratio is 20/80-80/20 of the cpd. of formula (I)/ the cpd. of formula (II) (m=2 or 4, n= 1- 100); (ii) adding 0.1-15 wt.% of inorg, filler selected from talc, titaninm dioxide, calcium carbonate, kaoline, mica etc.; (iii) adding 0.1-15 wt.% of lubricanting agent selected from sodium stearate, magnesium steararate neopentyl glycol dibenzoate; and (iv) adding 5- 50 wt.% of glass single fiber and 5-30 wt.% of bromic flame retardant to give stiffness and flame retardancy.

Description

폴리에스테르 수지의 조성물Composition of polyester resin

본 발명은 성형 재료로 널리 이용되고 있는 폴리에스테르 수지의 조성물, 특히 저온 성형 재료로 적합한고 결정성, 우수한 성형성 및 치수 안정성을 갖는 폴리에틸렌 테레프탈레이트(이하 "PET"라 약칭함) 수지에 관한 것으로서, 더욱 구체적으로는 100℃이하의 낮은 성형 온도에서 성형될때 우수한 이형성을 나타내고 동시에 우수한 표면 특성과 물리적인 성질을 갖는 PET수지의 조성물에 관한 것이다.The present invention relates to a composition of a polyester resin widely used as a molding material, in particular a polyethylene terephthalate (hereinafter referred to as "PET") resin having high crystallinity, excellent moldability and dimensional stability suitable as a low temperature molding material. More specifically, the present invention relates to a PET resin composition which exhibits excellent releasability when molded at a low molding temperature of 100 ° C. or less and at the same time has excellent surface properties and physical properties.

통상적으로 PET는 고유의 우수한 내열성, 내약품성 및 기계적 성질과 전기 특성 등을 가지므로 섬유,필름과 같은 공업용의 용도로 널리 이용된다. 그러나 PET는 성형물을 만들기 의하여 프라스틱과 같이 결정성을 요구하는 분야에 사용되는 경우 성형성에 있어서 수지의 특수한 결정화 거동때문에 많은 문제점들이 발생되는 것이다.In general, PET is inherently excellent in heat resistance, chemical resistance, mechanical properties and electrical properties, and is widely used for industrial applications such as fibers and films. However, when PET is used in a field which requires crystallinity such as plastic by making a molding, many problems arise due to the special crystallization behavior of the resin in moldability.

즉, PET는 원래 결정성 중합체이지만 수지의 높은 이차전이온도 때문에 일반적인 열가소성 수지로 사용하기 위하여 일반 금형 온도인 100℃이하의 낮은 성형온도에서 성형될때 성형물의 형태 및 안정성이 현저히 나빠지며 금형내에서 긴 체류시간을 필요로 하고 이 형성이 나쁘며 성형물은 싱크마크와 줄무늬가 발생하는등 많은 결점이 있다.That is, PET is originally a crystalline polymer, but due to the high secondary transition temperature of the resin, when it is molded at a low molding temperature of less than 100 ° C, which is a general mold temperature, for use as a general thermoplastic resin, the shape and stability of the molded article deteriorate significantly and are long in the mold. It requires residence time and is poorly formed, and moldings have many defects such as sink marks and streaks.

따라서 이러한 결점들을 제거하기 위하여 결정화가 성형물 심층까지 이루어지도록, 결정화 개시 온도를보다 낮은 쪽으로 이동시키고 결정화 속도를 증가시켜야 한다.Therefore, in order to eliminate these defects, the crystallization start temperature must be moved to a lower side and the crystallization rate must be increased so that the crystallization reaches the molding depth.

저온 성형시 결정화 속도를 향상시키기 위하여 탈크, 이산화티탄, 운모, 마그네슘 옥사이드 등의 무기물을 사용하는 것은 미합중국 특허 제3368975호, 제3575931호 등에 기술되어 있으며, 미합중국 특허 제4276208호, 제4215032호, 제4141882호와 한국 특허공고 제83-856호, 제83-973호 등에는 유기물의 고화 촉진제로서 에폭시계 화합물을 첨가하는 것을 기술하고 있다. 또한 미합중국 특허 제4366273호, 영국 특허 제2075301호, 한국 특허공고 제81-1801호 등에는 탄화수소계 금속염이나 카르복실기를 함유하는 불포화 탄화수소계 중합체 금속염이 배합된 조성물이 알려지고 있다.The use of inorganic materials such as talc, titanium dioxide, mica and magnesium oxide to improve the crystallization rate at low temperature molding is described in US Pat. Nos. 3,089,75,357,593, etc., US Pat. Nos. 4276208, 4215032, 4141882, Korean Patent Publication Nos. 83-856, 83-973 and the like describe the addition of an epoxy-based compound as a solidification accelerator for organic matter. In addition, US Patent No. 4366273, UK Patent No. 2075301, Korean Patent Publication No. 81-1801, and the like are known compositions containing a hydrocarbon-based metal salt or an unsaturated hydrocarbon-based polymer metal salt containing a carboxyl group.

그러나 무기물을 사용하는 경우 그것의 입경 분포나 균일 분산성에 따라 결정핵 형성제로서 서로 다른 효과를 나타내고 더우기 첨가량이 증가할지라도 만족할 만한 효과를 나타내지 못한다.However, when inorganic materials are used, they have different effects as nucleation agents depending on their particle size distribution or uniform dispersibility, and even when the amount of addition is increased, they do not show satisfactory effects.

특히, 결정화 개시 온도를 낮은 쪽으로 이동시키기는 어렵고 저온 금형내에 형성된 성형물 표층의 결정화는 아주 나쁘다. 유기물의 결정화 촉진제로 에폭시계 화합물의 경우에는 물리적 성질이 유지되지 않고 탄화수소계 중합체의 금속염을 사용할 경우 성형성이 떨어진다.In particular, it is difficult to shift the crystallization start temperature to a lower side and the crystallization of the molding surface layer formed in the low temperature mold is very bad. As an organic crystallization accelerator, physical properties are not maintained in the case of an epoxy compound, and moldability is deteriorated when a metal salt of a hydrocarbon polymer is used.

본 발명은 이러한 상기의 결점을 해소하기 위한 것으로 저온 성형시 결정화 속도가 빠르고 균일한 고화가 일어나고 결정화도가 높으며 이형성과 표면 상태는 물론 물리적 성질이 우수한 PET 조성물을 제공하는데 그 목적이 있는 것이다.The present invention is to solve the above-mentioned shortcomings, the object of the present invention is to provide a PET composition having a high crystallization rate, high degree of crystallization, excellent releasability and surface state as well as physical properties during low-temperature molding.

또한 본 발명은 고유점도가 0.4∼1.0dl/gr(페놀/테트라클로로 에탄=1 : 1 중량 %의 혼합 용액에 중합체 0.5중량%를 용해 25℃에서 측정)의 분자량을 가지는 폴리 에틸렌 테레프탈레이트 수지와 다음 일반식으로표시되는In addition, the present invention is a polyethylene terephthalate resin having a molecular weight of 0.4 ~ 1.0dl / gr (measured at 25 ℃ dissolved 0.5% by weight of polymer in a mixed solution of phenol / tetrachloroethane = 1% by weight) and Represented by the following general formula:

Figure kpo00001
Figure kpo00001

여기서, m=2 또는 4, n=1∼100Where m = 2 or 4, n = 1-100

Figure kpo00002
Figure kpo00002

화합물을 (II)화합물/(I)화합물 반복 단위의 몰비가 20/80에서 80/20까지 공중합한 고폴리에스터를 0.05중량 %에서부터 30중량 %까지 첨가하는데 화합물(II)/(I)의 반복단위의 몰비가 20/80∼80/20의 범위를벗어날 경우 고폴리에스터의 반응이 불안정하고, 따라서 불안정한 고풀리에스터를 첨가하더라도 결정화 속도가 향상되지 않는다. 무기충진제로서는 탈크, 이산화티탄, 칼슘카보네이트, 카오린 등을 첨가하며 활제로서는 나트륨 스테아레이트, 마그네시움 스테아레이트, 네오펜틸 그리콜 디 벤조에이트 등을 사용하여 폴리에스터의 결정화 속도를 개선한 수지 조성물에 특징이 있는 것이다.Repetition of compound (II) / (I) in order to add 0.05 to 30% by weight of high polyester copolymerized from (II) compound / (I) compound repeating unit from 20/80 to 80/20 When the molar ratio of the unit is out of the range of 20/80 to 80/20, the reaction of the high polyester is unstable, and thus the crystallization rate does not improve even if the unstable high pulley is added. As the inorganic filler, talc, titanium dioxide, calcium carbonate, kaolin, and the like are added, and as a lubricant, sodium stearate, magnesium stearate, neopentyl glycol dibenzoate, and the like are used to improve the crystallization rate of polyester. There is a characteristic.

상기 화합물들은 폴리에스터의 중합반응이 끝난 직후 용융상태에 첨가할 수도 있고, 폴리에스터의 물성을 향상시키기 위하여 유리섬유로 강화시키거나, 난연성을 부여하기 위하여 컴파운딩을 하는 공정에서 첨가하여도 좋다.The compounds may be added in the molten state immediately after the polymerization of the polyester, or may be added in the process of reinforcing the glass fiber to improve the physical properties of the polyester, or compounding to impart flame retardancy.

본 발명의 수지 조성물에 물성을 향상시키기 위하여 유리 단섬유, 탄소섬유, 케블라섬유등의 섬유 강화제를 보강하여 사용될 수도 있고 난연성을 부여하기 위하여 브롬계나 염소계 난연제를 첨가하여 사용하여도 무방하나 이때 사용된 섬유 강화제는 폴리머와의 접착성을 향상시키기 위하여 실란이나 보란으로 처리된 섬유 강화제를 사용하는 것이 바람직하다.In order to improve the physical properties of the resin composition of the present invention may be used by reinforcing fiber reinforcing agents such as short glass fiber, carbon fiber, Kevlar fiber, and bromine or chlorine flame retardant may be added to impart flame retardancy, It is preferable to use a fiber reinforcing agent treated with silane or borane in order to improve the adhesion with the polymer.

이외에도 일반 폴리머에 사용되고 있는 착색제 산화방지제, 이형제등을 첨가할 수도 있다.In addition, the coloring agent antioxidant, mold release agent, etc. which are used for the general polymer can also be added.

본 발명의 조성물로부터 얻은 성형물의 경우 일반 성형 조건하에서도 결정화가 충분히 이루어지고 성형물이 열 존재하에서도 우수한 칫수 안정성과 기계적 성질등을 갖는다.The molded article obtained from the composition of the present invention is sufficiently crystallized even under general molding conditions, and the molded article has excellent dimensional stability and mechanical properties even in the presence of heat.

그러므로 본 발명의 조성물은 각종 성형부품, 시이트상물, 관상물, 적층물, 용기 등의 성형에 광범위하게 이용될 수 있고 우수한 전기적 성질을 고려할때 전기, 전자, 자동차부품등의 성형에 가장 적합하다.Therefore, the composition of the present invention can be widely used in the molding of various molded parts, sheet-like articles, tubular articles, laminates, containers and the like, and is most suitable for molding of electric, electronic and automotive parts in consideration of excellent electrical properties.

본 발명의 실시예를 기술할때 첨가량은 별도의 표시가 없을때 중량 %을 뜻하며, 시험편의 성형과 성형물의 평가는 다음 방법에 따라 수행되었다.When describing an embodiment of the present invention, the addition amount means weight% unless otherwise indicated, and the molding of the test piece and the evaluation of the molded product were performed according to the following method.

(1) 폴리머의 중합 반응(1) Polymerization Reaction of Polymer

교반과 진공이 가능한 5ι 규모의 스텐레스 스티일 반응기를 사용하였다.A 5ι stainless steel stil reactor with stirring and vacuum was used.

(2) 중합체의 첨가제의 혼합(2) mixing of additives of polymers

중합체와 첨가제를 조성비에 따라 자동으로, 컴파운더에 투입하여 혼합한다. 실린더 온도는 260∼280℃로하며 혼합체는 냉각조를 통하여 칩 상태로 자른다.The polymer and the additive are automatically added to the compounder and mixed according to the composition ratio. The cylinder temperature is 260-280 ° C. and the mixture is cut into chips through a cooling bath.

(3) 시험편의 성형(3) forming the test piece

① 칩의 건조① drying of chips

제습식 건조기에 160℃에서 4시간 동안 건조하여 수분율이 0.01중량 %이하가 되도록 건조한다.It is dried in a dehumidifying dryer at 160 ° C. for 4 hours and dried to have a moisture content of 0.01 wt% or less.

② 시험편의 성형② Formation of Test Piece

건조된 싶은 사출기에 의해 시험편으로 성형되며 성형조건은, 실린더 온도 : 280℃, 성형온도 : 85∼110℃, 사출보압시간 : 15초, 냉각시간 : 15초, 사출압력 : 300∼600Kg/Cm²이다.It is molded into a test piece by a desired injection machine, and the molding conditions are: cylinder temperature: 280 ° C, molding temperature: 85 to 110 ° C, injection holding time: 15 seconds, cooling time: 15 seconds, injection pressure: 300 to 600 Kg / Cm². .

(4) 성형물의 표면특성(4) Surface characteristics of moldings

사출 성형후 금형에서 나오는 시험편의 외관 상태를 육안으로 관찰Visually observe the external appearance of the test piece from the mold after injection molding

(5) 성형물의 이형성(5) mold release property

사출 시험을 50회 실시했을때 시험편이 금형에 붙지 않고 떨어지는 횟수를 측정하였다.When the injection test was performed 50 times, the number of times the test piece fell without sticking to the mold was measured.

(6) 성형물의 수축율(6) shrinkage of moldings

성형후 금형에서 나오는 시험편(127×12.7×3.2mm)의 세로길이(ι)의 수축율을 측정한다.The shrinkage ratio of the longitudinal length (ι) of the test piece (127 x 12.7 x 3.2 mm) exiting the mold after molding is measured.

Figure kpo00003
Figure kpo00003

(여기서,ι0는 금형의 길이)Where 0 is the length of the mold

(7) 결정화 속도의 평가(7) evaluation of crystallization rate

시차 주사 열 분석기(Differential Scanning Calorimetry Analysis : D.S.C)를 사용하여 20℃/분으로 280℃까지 승온할때 나타나는 결정화 온도를 Tch, 30℃/분으로 냉각할때 나타나는 결정ghk 온도를 Tcc로하여 Tch의 차이를 △Tc라 하고 이 값을 상대 비교하여 결정화 속도를 평가한다.Tch is the crystallization temperature that appears when heating up to 280 ° C at 20 ° C / min using differential scanning calorimetry analysis (DSC). The difference is called ΔTc and the relative comparison is made to evaluate the crystallization rate.

이 △Tc의 범위를 크게 할수록 결정화 속도는 빨라진다. 이하 실시예로서 본 발명을 상세하게 설명하면다음과 같다. 실시예를 들어가면서 본 발명을 기술한다.The larger the range of ΔTc, the faster the crystallization rate. Hereinafter, the present invention will be described in detail with reference to the following Examples. The present invention will be described with reference to examples.

[실시예 1]Example 1

고유점도가 0.65dl/gr인 폴리에틸렌 테레프탈레이트 수지 98.5그램과 본 발명의 첨가제인 코폴리에스터0.5그램(II화합물 : I화합물의 몰비는 50 : 50), 나트륨 스테아레이트 0.3그램 탈크 0.5그램, 네오펜틸글리콜 디벤조에이트 0.2그램을 컴파운더에서 연속적으로 혼합, 냉각, 펠레이트화한 후 시차주사 열분석기로 결정화도를 평가하였다.98.5 grams of polyethylene terephthalate resin having an intrinsic viscosity of 0.65 dl / gr and 0.5 gram of copolyester (II compound: I compound is 50:50), 0.3 g of sodium stearate, 0.5 grams of talc, neopentyl 0.2 grams of glycol dibenzoate was continuously mixed, cooled, and pelated in a compound, and then the degree of crystallinity was evaluated by a differential scanning thermal analyzer.

[실시예 2]Example 2

본 발명의 첨가제인 코폴리에스터(II화합물/I화합물의 몰비는 65 : 35)만을 사용하고 첨가량을 변경시킨것을 제외하고는 실시예 1과 동일하게 실시하였다.Except for using only the copolyester (mole ratio of II compound / I compound is 65:35) of the additive of the present invention and changing the addition amount was carried out in the same manner as in Example 1.

[실시예 3]Example 3

본 발명의 첨가제인 코폴리에스터(II화합물 : I화합물의 몰비는 50 : 50)만을 사용하고 첨가량을 변경시킨것을 제외하고는 실시예 1과 동일하게 실시하였다.Except that the copolyester (II compound: I compound molar ratio of 50:50) of the additive of the present invention was used and the amount of addition was changed, the same procedure as in Example 1 was carried out.

[실시예 4]Example 4

본 발명의 첨가제인 코폴리에스터(II화합물 : I화합물의 몰비는 75 : 25)만을 사용하고 첨가량을 변경시킨것을 제외하고는 실시예 1과 동일하게 실시하였다.Except that the copolyester (II compound: I compound molar ratio of 75: 25) of the additive of the present invention was used and the addition amount was changed, it was carried out in the same manner as in Example 1.

[실시예 5]Example 5

본 발명의 첨가재인 코폴리에스터(II화합물 : I 화합물의 몰비는 50 : 50)만을 사용하고 첨가량을 변경시킨것을 제외하고는 실시예 1과 동일하게 실시하였다.The same procedure as in Example 1 was carried out except that only the copolyester (the molar ratio of the II compound: I compound was 50:50), which was an additive of the present invention, was changed.

[비교실시예 1∼6]Comparative Examples 1 to 6

본 발명의 첨가제인 코폴리에스터 이외의 첨가제만을 사용하여 실시예 1과 동일한 방법으로 수행하였다.It was carried out in the same manner as in Example 1 using only additives other than copolyesters of the present invention.

[실시예 6∼9][Examples 6-9]

물성을 강화하기 위하여 실란 화합물로 표면 처리된 3mm유리 단섬유(ASAHI Fiber Glass)를 30중량 % 첨가하고 난연성을 부여하기 위하여 브롬계난연제로 데카브로모 바이페널옥사이드를 사용하여 실시예 1의조성물과 함께 컴 파운더에서 혼합, 펠레트화 한 후 사출기로 시험편을 성형하여 결정화 속도와 성형성을평가하였다.In order to enhance the physical properties, 30% by weight of 3 mm AASHI Fiber Glass surface-treated with a silane compound was added, and decabromo biphenyl oxide was used as a brominated flame retardant to impart flame retardancy. After mixing and pelletizing together in a compounder, the test piece was molded by an injection molding machine to evaluate the crystallization rate and formability.

[비교실시예 7∼10]Comparative Examples 7 to 10

본 발명의 코폴리에스터를 사용하지 않았으며 실시예 6∼9와 동일한 방법으로 수행하였다.The copolyester of the present invention was not used and was carried out in the same manner as in Examples 6-9.

상기의 평가 결과는 표 l 및 표 2와 같다.The above evaluation results are shown in Table 1 and Table 2.

[표 1]TABLE 1

Figure kpo00004
Figure kpo00004

[표 2]TABLE 2

Figure kpo00005
Figure kpo00005

Figure kpo00006
Figure kpo00006

1) G/F : 유리 단섬유1) G / F: short glass fiber

2) FR : 난연제2) FR: Flame Retardant

Claims (1)

고유점도가 0.4-1.0dl/gr인 폴리에틸렌 테레프탈레이트 수지에 (i) 다음 식으로 표시되는 (II)화합물/(I)화합물 반복 단위의 몰비가 20/80에서 80/20까지 공중합한 코폴리에스터 0.05중량 %-30중량 %를첨가하고,Copolyester copolymerized with a polyethylene terephthalate resin having an intrinsic viscosity of 0.4-1.0 dl / gr, in which the molar ratio of (i) the compound / (I) compound repeating unit represented by the following formula (i) is from 20/80 to 80/20 Add 0.05% to 30% by weight,
Figure kpo00007
Figure kpo00007
여기서, m=2 또는 4이며 n=1-100이다.Where m = 2 or 4 and n = 1-100.
Figure kpo00008
Figure kpo00008
(ii) 무기 충진제로 탈크, 이산화티탄, 칼슘카보네이트, 카오린, 운모등을 0.1중량 %-15중량 % 첨가하며, (iii) 활제로서 나트륨 스테아레이트, 마그네시움 스테아레이트 네오펜틸 글리콜 디벤조에이트를 0.1중량 %-15중량 % 첨가하고, (iv) 물성을 강화하고 난연성을 부여하기 위하여 유리 단섬유를 5-50중량 %, 브롬계 난연제를 5-30중량 %를 첨가하여, 결정화 속도를 향상시킨 성형성이 우수한 폴리에스테르의 수지조성물.(ii) 0.1 to 15% by weight of talc, titanium dioxide, calcium carbonate, kaolin, mica, etc. are added as inorganic fillers, and (iii) sodium stearate, magnesium stearate neopentyl glycol dibenzoate as lubricant. 0.1 wt% -15 wt% is added, and (iv) 5-50 wt% glass short fibers and 5-30 wt% bromine-based flame retardant are added to enhance physical properties and impart flame retardancy. Polyester resin composition with excellent moldability.
KR1019870007847A 1987-07-20 1987-07-20 Polyester resin composition KR900006302B1 (en)

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