KR940006476B1 - Polyarylene Sulfide Resin Composition - Google Patents
Polyarylene Sulfide Resin Composition Download PDFInfo
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- KR940006476B1 KR940006476B1 KR1019910010482A KR910010482A KR940006476B1 KR 940006476 B1 KR940006476 B1 KR 940006476B1 KR 1019910010482 A KR1019910010482 A KR 1019910010482A KR 910010482 A KR910010482 A KR 910010482A KR 940006476 B1 KR940006476 B1 KR 940006476B1
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- sulfide resin
- polyarylene sulfide
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- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 title claims description 20
- 229920000412 polyarylene Polymers 0.000 title claims description 19
- 239000011342 resin composition Substances 0.000 title claims description 10
- 229920005989 resin Polymers 0.000 claims description 15
- 239000011347 resin Substances 0.000 claims description 15
- 239000012765 fibrous filler Substances 0.000 claims description 7
- 229920001903 high density polyethylene Polymers 0.000 claims description 7
- 239000004700 high-density polyethylene Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 description 5
- 239000004734 Polyphenylene sulfide Substances 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 229920000069 polyphenylene sulfide Polymers 0.000 description 4
- 239000003365 glass fiber Substances 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- -1 polyethylene Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 229920002873 Polyethylenimine Polymers 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- MPRRJXMALKDPON-UHFFFAOYSA-N 3-[[3-(diethylamino)-3-trimethoxysilylpropyl]disulfanyl]-n,n-diethyl-1-trimethoxysilylpropan-1-amine Chemical compound CCN(CC)C([Si](OC)(OC)OC)CCSSCCC(N(CC)CC)[Si](OC)(OC)OC MPRRJXMALKDPON-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- ZLDHYRXZZNDOKU-UHFFFAOYSA-N n,n-diethyl-3-trimethoxysilylpropan-1-amine Chemical compound CCN(CC)CCC[Si](OC)(OC)OC ZLDHYRXZZNDOKU-UHFFFAOYSA-N 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
- C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
- C08L81/04—Polysulfides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
내용 없음.No content.
Description
본발명은 폴리아릴렌 설파이드 수지조성물에 관한 것으로서, 더욱 상세하게는 기존의 폴리아릴렌 설파이드 수지에 고밀도의 폴리에틸렌을 첨가하므로써 타물성은 그대로 유지하면서 사출물로서의 외관과 성형성을 개선시킨 폴리아릴렌 설파이드 수지조성물에 관한 것이다.The present invention relates to a polyarylene sulfide resin composition, and more specifically, polyarylene sulfide which improves the appearance and formability as an injection product while maintaining other properties by adding high density polyethylene to the existing polyarylene sulfide resin. It relates to a resin composition.
일반적으로 폴리아릴렌 설파이드 수지는 내열성이 뛰어나고, 대부분의 용제에 대하여 내화학성을 가지며, 다른 열가소성 수지에 비하여 치수 안정성이 우수하기 때문에 자동차, 전자, 전기부품 뿐만 아니라 정밀사출이 요구되는 커넥터, 보빈류, 기어에 이르기까지 다양한 산업분야에 적용되고 있다.In general, polyarylene sulfide resin has excellent heat resistance, chemical resistance to most solvents, and excellent dimensional stability compared to other thermoplastic resins, so that connectors, bobbins, etc. requiring precise injection as well as automotive, electronic and electrical parts are required. It is applied to various industrial fields such as gears and gears.
이와같이 우수한 물성으로 인하여 종래에는 기능성만이 요구되는 내장부품으로 사용되었으나 최근 들어서는 외장 부품으로까지 응용되고 있다. 따라서, 외관이 양호한 폴리아릴렌 설파이드 수지조성물의 개발이 절실히 요구되고 있다.Due to such excellent physical properties, it was conventionally used as an interior component that requires only functionality, but has recently been applied to exterior components. Therefore, the development of a polyarylene sulfide resin composition with good appearance is urgently required.
종래의 폴리아릴렌 설파이드 수지는 내화학성, 내열성 및 치수 안정성 등은 우수하지만 사출 성형시 외관이 좋지 않아서 외장부품으로 사용하기에는 곤란하였는 바(미국특허 공보 제3,919,177호, 국내특허 공보 제90-912호), 폴리아릴레이트 설파이드 수지가 결정성이 높은 수지로서 양호한 외관 뿐만아니라 특유의 성질인 내열성과 내화학성을 보유하기 위해서는 높은 금형온도에서 사출하는 것이 필요하다.Conventional polyarylene sulfide resin has excellent chemical resistance, heat resistance and dimensional stability, but it is difficult to use as an exterior part due to poor appearance during injection molding (US Patent Publication No. 3,919,177, Domestic Patent Publication No. 90-912) The polyarylate sulfide resin is a resin having high crystallinity, and it is required to be injected at a high mold temperature in order to retain not only a good appearance but also heat resistance and chemical resistance, which are peculiar properties.
그러나, 높은 금형온도에서 사출할 경우에는 성형시간이 길어지고 가스가 발생할 뿐만아니라 금형온도가높기 때문에 고화될 때까지의 시간이 지연된다. 이러한 이유로 사출물이 탈형이 어려워져서 작업성 및 생산성에 치명적인 영향을 미치게 된다.However, in the case of injection at a high mold temperature, not only the molding time is long and gas is generated but also the time until solidification is delayed because of the high mold temperature. For this reason, injection molding becomes difficult to demould, which has a fatal effect on workability and productivity.
본발명자들은 이러한 문제점을 해결하고자 연구 노력한 결과 기존의 폴리아릴렌 설피아드 수지에 폴리에틸렌을 첨가하면 타물성은 그래도 유지되면서 외관과 성형성이 향상된다는 것을 알게 되어 본발명을 완성하였다.The present inventors have completed the present invention by finding out that the addition of polyethylene to the existing polyarylene sulfide resin improves the appearance and formability while maintaining the physical properties.
따라서, 본발명의 목적은 종래의 폴리아릴렌 설파이드 수지조성물에 비하여 타물성은 뒤떨어지지 않으면서 외관과 성형성이 우수한 폴리아릴렌 설파이드 수지조성물을 제공하는데 있다.Accordingly, an object of the present invention is to provide a polyarylene sulfide resin composition having excellent appearance and moldability without being inferior to other polyarylene sulfide resin compositions.
이하, 본발명을 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in detail.
본발명은 폴리아릴렌 설파이드 수지조성물에 있어서, 폴리아릴렌 설파이드 수지 100중량부와 고밀도 폴리에틸렌 0.5∼20중량부, 그리고 섬유상 충전제 25∼150중량부로 이루어진 것을 특징으로 한다.The present invention is characterized in that the polyarylene sulfide resin composition comprises 100 parts by weight of polyarylene sulfide resin, 0.5 to 20 parts by weight of high density polyethylene, and 25 to 150 parts by weight of fibrous filler.
이와같은 본발명은 더욱 상세히 설명하면 다음과 같다.This invention is described in more detail as follows.
본발명에서 기본수지인 폴리아릴렌 설파이드 수지로는 다음에 표시한 방향족 단량체 중 둘이상을 공중합하여서 그 반복단위가 70몰% 이상으로 이루어진 공중합체를 사용한다.As polyarylene sulfide resin which is a basic resin in this invention, the copolymer which copolymerizes 2 or more of the aromatic monomers shown next, and its repeating unit consists of 70 mol% or more is used.
특히, 본 발명에서는 방향족 단량체로서의 반복단위가 90몰%정도로 이루어지 폴리페닐렌 설파이드 수지가 가장 우수하다.In particular, in the present invention, as an aromatic monomer Polyphenylene sulfide resin having the highest repeating unit of about 90 mol% is the best.
이와같이 이루어진 폴리아릴렌 설파이드 수지는 300℃의 온도와 전단속도(Shear rate) 1200/sec에서 측정한 용융점도가 10∼20,000 포아즈인 것이 좋고, 더욱 좋게는 100 내지 5,000 포아즈인 것을 사용하는 바, 용융점도가 10미만일 경우 공정상 어려움이 따라고, 20,000을 초과하면 다른 첨가제와의 혼화성이 불량해진다.The polyarylene sulfide resin thus formed preferably has a melt viscosity of 10 to 20,000 poise measured at a temperature of 300 ° C. and a shear rate of 1200 / sec, and more preferably 100 to 5,000 poise. If the melt viscosity is less than 10, the process is difficult, and if it exceeds 20,000, miscibility with other additives is poor.
또한, 섬유상 충전제는 우수한 기계적 강도와 내열성을 부여하기 위하여 첨가하는 바, 본 발명에서는 유리섬유, 탄소섬유, 실리카섬유, 티탄산칼륨섬유, 티타늄섬유, 아라미드섬유, 아스베스토스섬유 등을 사용하는 것이 좋고, 이중에서도 특히 바람직하기로는 유리섬유를 사용할 경우이다.In addition, the fibrous filler is added in order to give excellent mechanical strength and heat resistance. In the present invention, it is preferable to use glass fiber, carbon fiber, silica fiber, potassium titanate fiber, titanium fiber, aramid fiber, asbestos fiber, etc. Also particularly preferred is the use of glass fibers.
이러한 섬유상 충전제를 폴리아릴렌 설파이드수지 100중량부에 대하여 24∼150중량부를 사용하는 바, 만일 그 함량이 25중량부 미만일 경우에는 목적하는 기계적 강도를 얻을 수 없고, 150중량부를 초과하면 오히려 보강효과가 떨어지고 성형성이 나빠진다.24 to 150 parts by weight of the fibrous filler is used with respect to 100 parts by weight of polyarylene sulfide resin, and if the content is less than 25 parts by weight, the desired mechanical strength cannot be obtained. Falls and moldability deteriorates.
이러한 섬유상 충천제는 표면처리제로 처리된 것을 사용하면 섬유상충전제와 수지와의 접착성이 좋아질 뿐만아니라 물에 대한 저항성과 열팽창 계수등의 물성이 더욱 안정된 제품을 얻을 수 있다.When the fibrous filler is treated with a surface treatment agent, not only the adhesion between the fibrous filler and the resin is improved, but also a product having more stable physical properties such as resistance to water and coefficient of thermal expansion can be obtained.
표면처리된 섬유상 충전제로는 3-글리시드옥시프로필 트리메톡시실란(3-Glycidoxypropyltrimethoxysilane), 3-매켑토프로필 트리메톡시실란(3-Mercaptopropyltrimethoxysilane), 다이에틸아미노-3-트리메톡시실릴프로필 다이설파이드(Diethylamino-3-trimethoxysily｜propydisulfide), 3-(디에틸아미노)프로필트리메톡시실란[3-(Diethylamino) propyltrimethoxysilan여, 3-엔-(트리메톡시실릴프로필) 폴리에틸렌이민[3-N-(Trimethoxysilylpropyl) polyethylenimine]등을 예로 들수 있다.Surface-treated fibrous fillers include 3-glycidoxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, diethylamino-3-trimethoxysilylpropyl di Sulfide (Diethylamino-3-trimethoxysily | propydisulfide), 3- (diethylamino) propyltrimethoxysilane [3- (Diethylamino) propyltrimethoxysilan, 3-ene- (trimethoxysilylpropyl) polyethyleneimine [3-N- (Trimethoxysilylpropyl) polyethylenimine].
한편, 본발명에서 특징적으로 사용되는 고밀도 폴리에틸렌은 폴리아릴렌 설파이드 수지 100중량부에 대하여 0.5∼20중량부를 사용하는 바, 만일 그 함량이 0.5중량부 미만이면 목적하는 성형개선의 효과가 없고, 20중량부를 초과하면 공정중에 분해등의 문제가 발생하여 성형품의 외관 뿐만아니라 기계적 강도, 등이 현저히 저하되는 문제가 생긴다.On the other hand, the high-density polyethylene used in the present invention is 0.5 to 20 parts by weight based on 100 parts by weight of polyarylene sulfide resin, if the content is less than 0.5 parts by weight, there is no effect of the desired molding improvement, 20 If the weight part is exceeded, problems such as decomposition occur during the process, and the problem of not only the appearance of the molded product but also the mechanical strength, etc., is significantly reduced.
이러한 본발명의 고밀도 폴리에틸렌으로는 ASTM D1505에 의해 측정한 밀도가 0.941∼0.965인 것을 사용한다. 이상의 필수성분 이외에도 목적에 따라 산화방지제, 안료, 윤활제, 핵제, 주형부식방지제 등의 성분을 첨가 사용할 수 있다.As the high-density polyethylene of the present invention, a density of 0.941 to 0.965 measured by ASTM D1505 is used. In addition to the above essential components, components such as antioxidants, pigments, lubricants, nucleating agents, and mold corrosion inhibitors may be added and used depending on the purpose.
상기한 바와같이 본발명에 따라 제조된 폴리페닐렌 설파이드 수지조성물은 기계적 강도 등의 물성은 그대로 유지하면서 사출성형시 기준제품에 비하여 이형성이 좋기 때문에 성형시간이 단축되어 생산성이 증가하고, 성형품은 표면광택 등 외관이 현저히 개선된 것이다.As described above, the polyphenylene sulfide resin composition prepared according to the present invention has better release properties than the standard product during injection molding while maintaining physical properties such as mechanical strength, so that molding time is shortened and productivity is increased. The appearance such as gloss is remarkably improved.
이하, 본발명을 실시예를 따라 더욱 상세히 설명한다.Hereinafter, the present invention will be described in more detail with reference to examples.
[실시예 1 내지 4, 비교예][Examples 1 to 4 and Comparative Examples]
다음의 표1에 나타난 각각의 사용량으로 폴리페닐렌 설파이드(일반 절차에 따라 제조된 폴리페닐렌 설파이드, ASTM D1238 시험방법에 따라 측정된 용융흐름속도가 20∼200g/10분)에 상업적으로 구득 가능한 고밀도 폴리에틸렌(일반적으로 ASTM D1505에 의해 결정된 약 0.941∼0.965의 밀도를 갖는 것)을 혼합기에서 잘 혼합하였다. 여기에 평균직경 13μm, 길이 3mm의 유리섬유를 다음 표1에 주어진 양에 따라 각각 상기 혼합물에 넣고 혼합하였다.Commercially available for polyphenylene sulfide (polyphenylene sulfide prepared according to the general procedure, melt flow rate measured according to ASTM D1238 test method 20-200 g / 10 min) at each usage amount shown in Table 1 below High density polyethylene (generally having a density of about 0.941 to 0.965 as determined by ASTM D1505) was mixed well in the mixer. Here, glass fibers having an average diameter of 13 μm and a length of 3 mm were mixed in the mixture according to the amounts given in Table 1 below.
이렇게 얻어진 혼합물을 실린더 온도 320℃의 압출기에서 용융 혼합하여 펠렛으로 만들었다. 상기의 방법으로 제조된 펠렛을 이용하여 실린더 온도 320℃에서 120℃ 정도의 주형온도로 필요한 모양의 시편을 성형하였다.The mixture thus obtained was pelletized by melt mixing in an extruder at a cylinder temperature of 320 ° C. Using the pellet prepared by the above method, a specimen of the required shape was molded at a mold temperature of about 120 ° C. to a cylinder temperature of 320 ° C.
이렇게 하여 제작된 시편을 48시간 동안 실험실 조건에서 방치시킨후 ASTM D638시험법에 규정된 일반적인 방법에 따라 인장강도를 측정하였다. 또한, 표면광택 등의 외관을 측정하기 위하여 판형의 사면을 성형하여 ASTM D523 시험법에 규정된 방법에 따라 60°각도의 Geometry조건에서 Glosmeter를 이용하여 시편의 광택도를 측정하였다. 그리고 성형시 금형으로부터의 탈락성향에 따라 이형성을 평가하여 얻었는바, 이상의 결과를 표1에 기재하였다.The specimen thus prepared was left under laboratory conditions for 48 hours, and then tensile strength was measured according to the general method specified in the ASTM D638 test method. Also, in order to measure the appearance of surface gloss, a plate-shaped slope was formed and the glossiness of the specimen was measured by using a glosmeter under a 60 ° angle of geometry according to the method specified in ASTM D523 Test Method. In addition, as a result of evaluating the release property according to the dropping tendency from the mold during molding, the above results are shown in Table 1.
[표 1]TABLE 1
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| Application Number | Priority Date | Filing Date | Title |
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| KR1019910010482A KR940006476B1 (en) | 1991-06-24 | 1991-06-24 | Polyarylene Sulfide Resin Composition |
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| KR1019910010482A KR940006476B1 (en) | 1991-06-24 | 1991-06-24 | Polyarylene Sulfide Resin Composition |
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