KR100374303B1 - Vinyl chloride resin composition having improved impact resistance and tensile strength - Google Patents
Vinyl chloride resin composition having improved impact resistance and tensile strength Download PDFInfo
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- KR100374303B1 KR100374303B1 KR1019960012602A KR19960012602A KR100374303B1 KR 100374303 B1 KR100374303 B1 KR 100374303B1 KR 1019960012602 A KR1019960012602 A KR 1019960012602A KR 19960012602 A KR19960012602 A KR 19960012602A KR 100374303 B1 KR100374303 B1 KR 100374303B1
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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
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/014—Stabilisers against oxidation, heat, light or ozone
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- 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
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
- C08L33/12—Homopolymers or copolymers of methyl methacrylate
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Abstract
Description
본 발명은 납계 복합 안정제를 포함하는 염화비닐 수지 조성물에 관한 것이며, 더욱 구체적으로는 납계 복합 안정제가 첨가된 염화비닐 수지에 고중합도의 가공조제 및 충격 보강제를 적절한 비율로 배합함으로써 내충격성 및 인장 강도가 동시에 개선된 염화비닐 수지 조성물에 관한 것이다.The present invention relates to a vinyl chloride resin composition comprising a lead-based composite stabilizer, and more specifically, to a vinyl chloride resin to which a lead-based composite stabilizer is added, a high polymerization degree processing aid and an impact reinforcing agent are blended in an appropriate ratio for impact resistance and tensile strength. Relates to an improved vinyl chloride resin composition at the same time.
통상적인 염화비닐 수지는 열안정성이 불량하기 때문에 안정제를 첨가하여 사용해야 하며, 극히 제한된 온도 범위내에서 가공된다. 또한, 염화비닐 수지는 일반적으로 겔 상태에 도달하는 시간이 길고 겔화시 점도가 높아져 흐름성이 극히 불량하기 때문에 압출기 등과 같은 가공기기내에 체류하게 되어 분해 현상이 일어나고, 단시간내에 용융체를 형성하기 어렵기 때문에 최종 제품의 표면이 매끄럽지 못하다.Conventional vinyl chloride resins have poor thermal stability and must be added with stabilizers and processed within extremely limited temperature ranges. In addition, since vinyl chloride resin generally has a long time to reach a gel state, high viscosity during gelation, and extremely poor flowability, the vinyl chloride resin stays in processing equipment such as an extruder, so that decomposition occurs and it is difficult to form a melt in a short time. As a result, the surface of the final product is not smooth.
이러한 단점을 해결하기 위하여 염화비닐 수지 조성물에 소량(조성물 중량을 기준으로 일반적으로 1 내지 3 중량%)의 가공조제를 첨가한다. 이러한 가공조제는 조성물의 다른 물성에는 영향을 미치지 않으면서 가공성을 향상시켜야 한다. 가공성 향상을 위하여 사용되는 가공조제는 가공기기의 형태, 최종 제품의 특성, 염화비닐 수지와의 상용성을 고려하여 선택해야 한다.In order to solve this disadvantage, a small amount (usually 1 to 3% by weight based on the weight of the composition) of the vinyl chloride resin composition is added to the processing aid. Such processing aids should improve processability without affecting other physical properties of the composition. Processing aids used to improve processability should be selected in consideration of the type of processing equipment, the characteristics of the final product, and the compatibility with vinyl chloride resin.
상기 가공조제를 첨가하여 제조된 염화비닐 수지 조성물은 겔화 시간 단축, 고온 신율 증가, 용융 파열(melt fracture) 방지, 열변형 온도 증가, 흐름 자극(flow mark) 감소, 광택 증가, 투명성 및 충격강도 저하와 같은 물성을 나타내게 된다.The vinyl chloride resin composition prepared by adding the processing aid may shorten gelation time, increase high temperature elongation, prevent melt fracture, increase heat deformation temperature, decrease flow mark, increase gloss, decrease transparency and impact strength. It shows the same physical properties.
수지 조성물의 가공시 원하는 충격 강도를 보강하기 위하여 충격보강제를 사용한다. 충격보강제는 염화비닐 수지 조성물중에 어떤 형태로 존재하느냐에 따라 크게 두가지로 분류된다. 즉, 충격보강제 입자가 메트릭스인 염화비닐 수지에 독자적인 분산 형태로 존재하는 입자분산형 및 충격보강제와 염화비닐 수지상 사이에 상전이가 이루어져 충격보강제가 메트릭스 상으로 존재하는 상용 분산형으로 분류되며, 예컨대 ABS, MBS 및 아크릴계 수지는 입자 분산형에 속하며 CPE 및 EVA는 상용 분산형에 속한다.An impact modifier is used to reinforce the desired impact strength in processing the resin composition. Impact modifiers are classified into two types depending on the type of impact modifiers present in the vinyl chloride resin composition. That is, the impact modifier particles are classified into a particle dispersion type in which the impact modifier particles are present in an independent dispersion form in the matrix, and a commercial dispersion type in which the impact modifier is present in the matrix phase due to a phase transition between the impact modifier and the vinyl chloride resin phase. , MBS and acrylic resins belong to particle dispersion and CPE and EVA belong to commercial dispersion.
염화비닐 수지에 사용되는 충격보강제는 제품의 용도, 투입량, 충격보강 효과, 가공성, 내후성, 내응력 백화성, 투명성, 열변형성 등을 고려하여 선택하여야 한다.Impact modifiers used in vinyl chloride resin should be selected in consideration of the intended use of the product, dosage, impact reinforcing effect, processability, weather resistance, stress whitening, transparency, and heat deformation.
한편, 염화비닐 및 수지 조성물에 대한 인장강도와 내충격성은 반비례 관계에 있다. 즉, 일반적으로 염화비닐 수지 조성물에 첨가되는 충격보강제의 양을 증가시킬수록 인장강도는 현저하게 떨어진다. 따라서, 수지 조성물에 충격보강제를 첨가하여 내충격성을 향상시키는 데에는 한계가 있다.On the other hand, the tensile strength and impact resistance of the vinyl chloride and the resin composition are inversely related. That is, in general, as the amount of impact modifier added to the vinyl chloride resin composition increases, the tensile strength is significantly lowered. Therefore, there is a limit in improving impact resistance by adding an impact modifier to the resin composition.
이에, 본 발명자들은 인장강도를 일정한 수준으로 유지하면서 내충결성을 향상시킬 수 있는 방안을 예의 연구한 결과, 염화비닐 수지와의 상용성이 양호한 고중합도의 가공조제를 소정의 비율로 첨가할 경우 소량의 충격보강제를 사용하더라도 내충격성 및 인장강도가 매우 우수한 염화비닐 수지 조성물을 제조할 수 있음을 발견하였다.Accordingly, the present inventors have diligently studied a method of improving the insect resistance while maintaining the tensile strength at a constant level. As a result, a small amount of a high polymerization degree processing aid having good compatibility with vinyl chloride resin is added at a predetermined ratio. It has been found that even when the impact modifier is used, a vinyl chloride resin composition having excellent impact resistance and tensile strength can be prepared.
본 발명은The present invention
i) 염화비닐 수지 100 중량부;i) 100 parts by weight of vinyl chloride resin;
ii) 납계 복합안정제 2 내지 5 중량부;ii) 2 to 5 parts by weight of a lead-based composite stabilizer;
iii) 충격보강제 6 내지 8 중량부; 및iii) 6 to 8 parts by weight of the impact modifier; And
iv) 메틸 아크릴레이트계 또는 메틸 메타아크릴레이트계 수지로 된 가공조제 5 내지 10 중량부iv) 5 to 10 parts by weight of a processing aid made of methyl acrylate or methyl methacrylate resin
를 포함하는, 개선된 내충격성 및 인장강도를 갖는 염화비닐 수지 조성물에 관한 것이다.It relates to a vinyl chloride resin composition having an improved impact resistance and tensile strength.
본 발명에 사용되는 염화비닐 수지는 중합도가 800 내지 1300의 값을 가지는 현탁 중합 또는 괴상 중합된 염화비닐 수지이다.The vinyl chloride resin used in the present invention is a suspension polymerization or bulk polymerization vinyl chloride resin having a degree of polymerization of 800 to 1300.
상기 언급한 납계 복합안정제는 본 기술 분야에 통상적인 안정제이다. 예컨데 이러한 납계 복합안정제로는 KWP(코오롱 유화사제), PS-104(송원산업제)등을 들 수 있다.The above-mentioned lead-based composite stabilizers are common stabilizers in the art. For example, such lead-based complex stabilizers include KWP (Kolon Emulsifier), PS-104 (Songwon Industrial).
본 발명에 사용되는 충격보강제는 본 기술분야에 통상적으로 사용되는 공지의 MBS계 충격보강제로서 메틸메타아크릴레이트-부타디엔-스티렌 고무이다. 특히 바람직한 것은 0.1 내지 0.4㎛의 입경을 갖는 30 내지 80 중량부의 디엔계 고무상에 20 내지 70 중량부의 아크릴레이트 및 방향족 비닐 단량체를 그라프트 중합시켜 제조한 것이며 MB-832(LG 화학 제품)을 예로 들 수 있다. 상기 충격보강제는 외부에서 가해지는 충격에너지를 디엔계 고무상으로 전달하고 그 에너지를 디엔계 고무상에서 흡수 발산함으로써 충격 보강효과를 나타내도록 설계되어 있으며, 특히 할로겐화 폴리에틸렌(CPE계)과 같은 다른 충격보강제에 비하여 0℃ 이하의 저온에서도 우수한 충격보강 효과를 나타낸다.The impact modifier used in the present invention is methylmethacrylate-butadiene-styrene rubber as a known MBS-based impact modifier commonly used in the art. Particularly preferred is prepared by graft polymerization of 20 to 70 parts by weight of acrylate and aromatic vinyl monomer on 30 to 80 parts by weight of diene rubber having a particle diameter of 0.1 to 0.4 µm, and MB-832 (LG Chemical Co., Ltd.) Can be mentioned. The impact modifier is designed to deliver an impact reinforcing effect by transferring the impact energy applied from the outside to the diene rubber phase and absorbing and dissipating the energy from the diene rubber phase, in particular, other impact modifiers such as halogenated polyethylene (CPE-based). Compared to the low temperature of 0 ℃ or less than the excellent impact reinforcing effect.
본 발명의 염화비닐 수지조성물들을 구성하는 성분중의 하나인 가공조제는 본 기술 분야에서 통상적으로 사용되는 공지의 가공조제이며, 이들은 메틸아크릴레이트계 또는 메타메틸아크릴레이트계 수지로서 가소제, 아크릴레이트-메타아크릴레이트, 스티렌-아크릴레이트 또는 스티렌-메타아크릴레이트가 있다. 특히 바람직한 것은 아크릴레이트계 단량체를 유화중합하여 제조한 것이며, PA-820(LG 화학제품)을 예로 들수 있다.The processing aid, which is one of the components constituting the vinyl chloride resin composition of the present invention, is a known processing aid commonly used in the art, and these are a plasticizer, acrylate- as a methyl acrylate or methacrylate resin. Methacrylate, styrene-acrylate or styrene-methacrylate. Particularly preferred are those prepared by emulsion polymerization of acrylate monomers, for example PA-820 (LG Chemicals).
본 발명의 조성물은 상기의 구성성분이외에 활제, 착색제, 충진제. 대전방지제 등과 같은 부가적인 성분들을 목적하는 물성에 따라서 미량으로 사용할수 있다.The composition of the present invention, in addition to the above components, lubricants, colorants, fillers. Additional ingredients such as antistatic agents can be used in trace amounts depending on the desired properties.
본 발명의 염화비닐 수지 조성물은 일반적으로 염화비닐 수지와 납계 복합 안정제를 혼합기중에서 혼합하고 이 혼합물에 충격 보강제 및 가공조제를 첨가한 다음 이를 성형압출기를 통해 압출시켜 원하는 형태의 제품으로 형성한다. 이와 같은 염화비닐 수지 조성물은 각종 산업용 제품, 예를 들면 성형압출 제품, 아파트 및 공공건물의 샤시제품 및 하수도 및 상수도의 파이프 제품에 적용된다.In general, the vinyl chloride resin composition of the present invention is mixed with a vinyl chloride resin and a lead-based composite stabilizer in a mixer, and an impact modifier and a processing aid are added to the mixture, and then extruded through a molding extruder to form a desired product. Such a vinyl chloride resin composition is applied to various industrial products, such as molded extrusion products, chassis products of apartments and public buildings, and pipe products of sewerage and water supply.
이하, 실시예를 통하여 본 발명을 좀 더 구체적으로 예시하고자 하며 본 발명은 이들 실시예에 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to Examples, and the present invention is not limited to these Examples.
실시예 1Example 1
중합도 1000 의 염화비닐 수지(주식회사 LG 화학 제품 LS-100) 100 중량부, 충격보강제(주식회사 LG 화학 제품, MB-832) 7.5 중량부, 가공조제(주식회사 LG 화학 제품, PA-820) 5중량부 및 납계복합안정제(선경화성, SK-303) 3.5 중량부를 헨셀 혼합기에 주입하고 잘 혼합한 다음, 단축 압출기 또는 이축 압출기에서 170 내지 180 ℃ 온도로 1 차 펠렛 컴파운딩하였다. 이 펠렛을 2 본 롤밀을 이용하여 190 ℃에서 3 분간 혼련한 다음 이어 190 ℃ 의 압축기에서 2 분간 압축시켜 3 ㎜ 두께의 시편을 제작하였다.100 parts by weight of polyvinyl chloride resin (LG Chemical, LS-100) with a polymerization degree of 1000, 7.5 parts by weight of impact modifier (LG Chemical, MB-832), 5 parts by weight of processing aid (LG Chemical, PA-820) And 3.5 parts by weight of a lead-based complex stabilizer (precursor, SK-303) were injected into a Henschel mixer, mixed well, and then primary pellet compounded at a temperature of 170 to 180 ° C. in a single screw extruder or a twin screw extruder. The pellets were kneaded at 190 ° C. for 3 minutes using two roll mills, and then compressed for 2 minutes at a 190 ° C. compressor to prepare specimens having a thickness of 3 mm.
상기 시편을 이용하여 하기와 같은 실험을 실시하였다.The following experiment was performed using the specimen.
내동파성 실험: 1 차 컴파운딩된 펠렛을 90 ㎜ 이축 압출기를 이용하여 100 ㎜ 파이프로 제조하고, 이를 1 m 길이로 절단한 다음 이 파이프에 물을 채우고 양 말단을 막은 후 -10 ℃ 저온실에서 급냉시켜 24 시간 보관후 내동파성을 측정하였다.Freeze resistance test: The first compounded pellets were made into 100 mm pipes using a 90 mm twin screw extruder, cut into 1 m lengths, filled with water and blocked at both ends, and then After quenching and storage for 24 hours, freeze resistance was measured.
내충격성 실험: 내충격성 실험은 한국 공업 규격 KSM 3401-95 에 따라 측정하였다.Impact resistance test: The impact resistance test was measured according to Korean Industrial Standard KSM 3401-95.
인장강도 실험: 시편의 인장강도를 하기 방정식에 따라 계산하였다.Tensile Strength Test: The tensile strength of the specimen was calculated according to the following equation.
TS = TSt+ 6.65(t - 15)TS = TS t + 6.65 (t-15)
상기 식에서, TS 는 15 ℃ 에서의 인장강도(kgf/㎠) 이고, TST 는 t ℃ 에서의 인장강도(kgf/㎠) 이고, t 는 실험 온도(5 내지 35 ℃) 이다.In the above formula, TS is tensile strength (kgf / cm 2) at 15 ° C., TST is tensile strength (kgf / cm 2) at t ° C., and t is experimental temperature (5 to 35 ° C.).
실시예 2 및 3Examples 2 and 3
각각 하기 표 1 에 명시된 양의 고분자량 가공조제 및 충격보강제를 사용하여 실시예 1 과 동일하게 시편을 제조하였으며, 이 시편을 이용하여 내동파성, 내충격성 및 인장강도를 측정하였다. 그 결과를 하기 표 1 에 나타내었다.The specimens were prepared in the same manner as in Example 1 using the high molecular weight processing aids and the impact modifiers in the amounts shown in Table 1 below, respectively, and the freeze resistance, impact resistance, and tensile strength were measured. The results are shown in Table 1 below.
비교예 1 내지 7Comparative Examples 1 to 7
표 1 에서와 같은 조성을 사용한 것을 제외하고는 실시예 1 에서와 동일하게 시편을 제조하였으며, 이 시편을 이용하여 내동파성, 내충격성 및 인장강도를 측정하였다. 그 결과를 하기 표 1 에 나타내었다.Specimens were prepared in the same manner as in Example 1 except that the compositions as shown in Table 1 were used, and the resistance to freezing, impact and tensile strength was measured using the specimens. The results are shown in Table 1 below.
표 1Table 1
상기 표에 나타낸 결과로부터 적정량의 고분자량 가공조제 및 충격보강제를 사용함으로써 내충격성 및 인장강도가 동시에 향상되었으며(실시예 1 내지 3), 이와 달리 충격보강제의 양이 과다 또는 과소한 경우 및 고분자량 가공조제를 전혀함유하지 않은 경우(비교예 1 내지 7) 내충격성 및 인장강도는 기대수준 이하로 나타남을 알 수 있다.From the results shown in the above table, by using the appropriate amount of high molecular weight processing aid and impact modifier, the impact resistance and tensile strength were improved simultaneously (Examples 1 to 3), on the contrary, when the amount of the impact modifier was excessive or too low and the high molecular weight It can be seen that the impact resistance and tensile strength are below the expected level when the processing aid is not contained at all (Comparative Examples 1 to 7).
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| KR101898617B1 (en) * | 2018-07-03 | 2018-10-05 | (주)금광이앤티 | Safety cover for grating with luminous part and method for manufacturing the same |
| KR101990119B1 (en) * | 2018-09-07 | 2019-06-20 | (주)금광이앤티 | Safety cover for grating with luminous part and method for manufacturing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR100341868B1 (en) * | 1999-09-06 | 2002-06-24 | 신진욱 | Unplasticised Polyvinyl- chloride with Impact modifier |
| KR101236659B1 (en) * | 2009-03-23 | 2013-02-22 | 주식회사 엘지화학 | Process for Vinyl Chloride Graft Copolymer Resin |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR950006265A (en) * | 1993-08-17 | 1995-03-20 | 이헌조 | Turbo Fan Housing Structure |
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| KR950006265A (en) * | 1993-08-17 | 1995-03-20 | 이헌조 | Turbo Fan Housing Structure |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101898617B1 (en) * | 2018-07-03 | 2018-10-05 | (주)금광이앤티 | Safety cover for grating with luminous part and method for manufacturing the same |
| KR101990119B1 (en) * | 2018-09-07 | 2019-06-20 | (주)금광이앤티 | Safety cover for grating with luminous part and method for manufacturing the same |
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