KR20090023989A - Manufacturing method of paste vinyl chloride resin with excellent initial viscosity and viscosity stability - Google Patents
Manufacturing method of paste vinyl chloride resin with excellent initial viscosity and viscosity stability Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F14/00—Homopolymers and 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
- C08F14/02—Monomers containing chlorine
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
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- C08F2/00—Processes of polymerisation
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- C08J3/12—Powdering or granulating
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Abstract
본 발명은 초기 점도 및 점도 안정성이 우수한 페이스트 염화비닐계 수지의 제조방법에 관한 것으로, 특히 글리세린, 또는 트리메틸롤프로판을 중합 후기에 첨가하는 것을 특징으로 하는, 초기 점도 및 점도 안정성을 현저하게 향상된 염화비닐계 수지의 제조방법에 관한 것이다.The present invention relates to a method for producing a paste vinyl chloride-based resin having excellent initial viscosity and viscosity stability, and in particular, glycerol or trimethylolpropane is added to the late stage of polymerization. It relates to a method for producing a vinyl resin.
Description
본 발명은 플라스티졸을 제공할 수 있는 염화비닐계 수지를 염화비닐계 라텍스로부터 제조하는 방법에 관한 것으로, 보다 상세하게는 염화비닐계 라텍스로부터 플라스티졸 가공 시 작업이 용이한 낮은 점도를 나타내는 염화비닐계 수지를 제조하는 방법에 관한 것이다.The present invention relates to a method for preparing a vinyl chloride-based resin capable of providing a plastisol from a vinyl chloride-based latex, and more particularly, to a low viscosity, which is easy to work when processing a plastisol from a vinyl chloride-based latex. A method for producing a vinyl chloride-based resin.
염화비닐계 수지로부터 제조된 플라스티졸은 예컨대 마루와 벽 코팅, 플라스틱화 된 코팅 직물 및 유향 수지 등과 같은 각종 물품의 가공 시에 사용된다. 상기 염화비닐계 플라스티졸을 이용하여 다양한 물품을 가공하는 경우 양호한 성형성이 필요하고, 이를 위해 상기 염화비닐계 플라스티졸의 낮은 점도가 요구되고 있다.Plastisols made from vinyl chloride-based resins are used in the processing of various articles such as, for example, floor and wall coatings, plasticized coated fabrics and frankincense resins. In order to process various articles using the vinyl chloride plastisol, good moldability is required, and for this, a low viscosity of the vinyl chloride plastisol is required.
통상 염화비닐계 수지의 페이스트 가공 시 졸의 점도를 낮추기 위한 방법으로 유화 중합 방법으로 제조 되는 염화비닐계 페이스트 수지보다 큰 입자를 갖는 수지를 약 10~20 중량% 혼합하여 가소제 및 첨가제와 함께 플라스티졸 상태로 배합하여 사용하는 방법이 있다. (대한민국 공개특허 10-2007-0046707) 이로써 서로 다른 크기의 입자를 가진 수지들의 혼합 및 충진으로 공극을 줄여 가소제 흡수면적을 감소시킴으로써 가공 시 졸의 점도를 낮출 수 있다. 하지만, 이러한 가소제 흡수성은 혼합된 수지 입자의 크기 및 구형성과 연관이 깊어 최종 입자의 구형성과 입경 조절 기술이 요구되고, 서로 달리 중합된 수지들을 혼합하여야 하는 번거로움의 문제점이 있다.In order to reduce the viscosity of the sol during paste processing of vinyl chloride-based resins, a plasticity is mixed with a plasticizer and an additive by mixing about 10 to 20% by weight of a resin having larger particles than the vinyl chloride-based paste resin prepared by an emulsion polymerization method. There is a method of mixing and using in a sol state. This can reduce the viscosity of the sol during processing by reducing the plasticizer absorption area by reducing the voids by mixing and filling of resins having particles of different sizes. However, such plasticizer absorbency is deeply related to the size and spherical shape of the mixed resin particles, requires a sphere shape and particle size control technology of the final particles, there is a problem of the need to mix differently polymerized resin.
상기와 같은 종래 기술의 문제점을 해결하고자, 본 발명의 목적은 페이스트 가공 시 낮은 점도를 갖는 플라스티졸을 제공할 수 있는 염화비닐계 수지의 제조 방법을 제공하는 것이다.In order to solve the problems of the prior art, it is an object of the present invention to provide a method for producing a vinyl chloride-based resin that can provide a plastisol having a low viscosity during paste processing.
상기의 목적을 달성하기 위하여, 본 발명은 페이스트 염화비닐계 수지의 제조 방법에 있어서, 염화비닐계 단량체를 중합하여 염화비닐계 수지 라텍스를 제조하는 단계; 및 상기 라텍스에 글리세린 및 트리메틸롤프로판으로 구성되는 군으로부터 선택되는 하나 이상을 중합 후기에 첨가하는 단계를 포함하는 것을 특징으로 하는 페이스트 염화비닐계 수지의 제조 방법을 제공한다.In order to achieve the above object, the present invention provides a method for preparing a vinyl chloride resin paste, comprising: preparing a vinyl chloride resin latex by polymerizing a vinyl chloride monomer; And adding at least one selected from the group consisting of glycerin and trimethylolpropane to the latex to the latex to the latex.
본 발명은 페이스트 염화비닐계 수지 자체의 초기 BF점도 및 1일 BF점도를 낮출 수 있고, 따라서 상기 플라스티졸의 가공 성형성을 개선시킬 수 있다. 본 발명에 따라 제조된 페이스트 염화비닐계 수지는 중요한 벽지, 상재, 레쟈 가공 등에 광범위하게 이용될 수 있다. The present invention can lower the initial BF viscosity and the daily BF viscosity of the paste vinyl chloride-based resin itself, thus improving the process formability of the plastisol. The paste vinyl chloride resin prepared according to the present invention can be widely used for important wallpaper, material, leather processing and the like.
염화비닐계 수지 라텍스는, 염화비닐 단량체 단독, 또는 염화비닐 단량체와 이것과 공중합이 가능한 단량체의 혼합물(이것들을 합쳐서 염화비닐계 단량체라고 한다)을 수성 매체 중에서, 유화제, 또한 유용성 중합 개시제를 첨가하고 균질화한 뒤, 미세 현탁 중합을 통하여 제조할 수 있다. 이 때, 필요에 따라 고급 알코올(alcohol), 고급 지방산 등의 보조 분산제를 이용해도 좋다. The vinyl chloride resin latex is a vinyl chloride monomer alone or a mixture of vinyl chloride monomer and a copolymerizable monomer (these are called vinyl chloride monomers) by adding an emulsifier and an oil-soluble polymerization initiator in an aqueous medium. After homogenization, it can be prepared via fine suspension polymerization. At this time, if necessary, an auxiliary dispersant such as higher alcohol or higher fatty acid may be used.
다른 중합법으로 상기 염화비닐계 단량체를 수성 매체 중에서 유화제, 수용성 개시제를 첨가하고 유화중합이나 시드(seed) 유화 중합할 수 있다. 이 경우에도 필요에 따라 고급 알코올(alcohol), 고급 지방산 등의 보조 분산제를 첨가할 수 있다. 염화비닐계 수지 라텍스 중합에 있어서 사용된 염화비닐계 단량체는 일반적으로 80~ 98wt% 가 염화비닐계 수지 라텍스로 되고, 나머지 미반응의 단량체는 제거되는 것이 바람직하다. In another polymerization method, the vinyl chloride monomer may be emulsified or seed emulsion polymerized by adding an emulsifier and a water-soluble initiator in an aqueous medium. Also in this case, auxiliary dispersants such as higher alcohols and higher fatty acids may be added as necessary. In general, the vinyl chloride monomer used in the vinyl chloride resin latex polymerization is preferably 80 to 98 wt% of the vinyl chloride resin latex, and the remaining unreacted monomer is preferably removed.
본 발명은 수지의 열안정성을 개선하기 위해 염화비닐계 수지 라텍스를 중합시킨 후, 상기 라텍스에 글리세린, 트리메틸롤프로판 또는 이들의 혼합물을 첨가하는 것을 특징으로 한다. 이 때, 글리세린, 트리메틸롤프로판 또는 이들의 혼합물은 염화비닐계 단량체 100 중량부에 대하여 0.01~2 중량부, 바람직하게는 0.2~0.5 중량부로 첨가할 수 있다.The present invention is characterized in that after polymerizing a vinyl chloride-based resin latex to improve the thermal stability of the resin, glycerin, trimethylolpropane or a mixture thereof is added to the latex. At this time, glycerin, trimethylolpropane or a mixture thereof may be added in an amount of 0.01 to 2 parts by weight, preferably 0.2 to 0.5 parts by weight, based on 100 parts by weight of the vinyl chloride monomer.
글리세린, 트리메틸롤프로판 또는 이들의 혼합물은 중합 후기, 바람직하게는 중합반응의 반응압이 0 kg/㎠ 로 떨어진 후에, 가장 바람직하게는 반응압이 0 kg/㎠ 로 떨어진 직후에 첨가한다. Glycerin, trimethylolpropane or a mixture thereof is added after the polymerization, preferably after the reaction pressure of the polymerization reaction drops to 0 kg / cm 2, and most preferably immediately after the reaction pressure drops to 0 kg / cm 2.
중합된 페이스트 염화비닐계 수지의 라텍스(latex)는 분무 건조를 통해 얻어 진다. 건조할 때 일반적으로 탈수 여과 등을 행하지 않기 때문에 유화제등의 원료는 수지 중에 잔류한다. Latex of the polymerized paste vinyl chloride resin is obtained by spray drying. In drying, dehydration filtration or the like is not generally performed. Thus, raw materials such as an emulsifier remain in the resin.
페이스트 염화비닐계 수지는 기본적으로 입경이 0.1 ~ 50㎛으로 가소제의 분산성이 양호하고 페이스트(paste) 가공에 적합하다. Paste vinyl chloride resin has a particle size of 0.1 to 50 µm, which is good in dispersibility of a plasticizer and suitable for paste processing.
본 발명의 제조방법에 의하여 제조된 페이스트 염화비닐계 수지는 초기 BF 점도가 3000 내지 5000이고, 1일 BF 점도가 4000 내지 7000인 것을 특징으로 한다. Paste vinyl chloride resin prepared by the production method of the present invention is characterized in that the initial BF viscosity is 3000 to 5000, the daily BF viscosity is 4000 to 7000.
이하 본 발명을 보다 구체적으로 설명하기 위하여 실시예를 보이지만 본 발명의 범위를 이하의 실시 예에만 국한하는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to Examples, but the scope of the present invention is not limited to the following Examples.
[실시예 1]Example 1
200 L의 고압반응기에 탈이온수 51 ㎏, KH2PO4 21 g, NaOH 7 g, 고형분이 40 %이고 평균입경이 0.1 ㎛인 심종입자 라텍스 3.4 ㎏ 및 고형분이 40 %이고 평균입경이 0.5 ㎛인 심종입자 라텍스 6.9 ㎏를 투입한 후, 교반하면서 반응기에 진공을 걸었다. 진공상태의 반응기에 염화비닐 단량체 77 ㎏을 투입한 후, 반응기의 온도를 61 ℃로 승온시키고 중합하였다. 상기 중합반응이 시작되면 유화제로 라우릴 설페이트 나트륨염의 5 % 수용액 10.4 ㎏을 4시간 동안 연속적으로 반응기에 투입하였다. 그리고 반응기의 압력이 4 ㎏/㎠에 도달하면 반응을 종결하고 미반응 염화비닐 단량체를 회수하여 제거한다. 압력이 완전히 떨어지면(0 kg/㎠) 글리세린 385 g을 투입 후 20분간 교반 후 분무 건조하여 분체상의 페이스트 염화비닐 수지를 제조하였다.In a 200 L high-pressure reactor, 51 kg of deionized water, 21 g of KH 2 PO 4 , 7 g of NaOH, 40 kg of solid particles 40%, mean particle size of 0.1 kg After adding 6.9 kg of the latex particle latex, a vacuum was applied to the reactor while stirring. 77 kg of a vinyl chloride monomer was added to a reactor in a vacuum state, and the temperature of the reactor was raised to 61 ° C. and polymerized. When the polymerization was started, 10.4 kg of a 5% aqueous solution of lauryl sulfate sodium salt was added to the reactor continuously for 4 hours as an emulsifier. When the pressure of the reactor reaches 4 kg / cm 2, the reaction is terminated and the unreacted vinyl chloride monomer is recovered and removed. When the pressure dropped completely (0 kg / cm 2), 385 g of glycerin was added, stirred for 20 minutes, and then spray-dried to prepare a powdery paste vinyl chloride resin.
[실시예 2]Example 2
상기 실시예 1에서 글리세린을 154 g 투입한 것을 제외하고는 상기 실시예 1과 동일하게 실시하여 분체상의 페이스트 염화비닐 수지를 제조하였다.A powdery paste vinyl chloride resin was prepared in the same manner as in Example 1, except that 154 g of glycerin was added in Example 1.
[실시예 3]Example 3
상기 실시예 1에서 글리세린 대신 트리메틸롤프로판 385 g을 투입한 것을 제외하고는 상기 실시예 1과 동일하게 실시하여 분체상의 페이스트 염화비닐 수지를 제조하였다.Powder paste vinyl chloride resin was prepared in the same manner as in Example 1, except that 385 g of trimethylolpropane was added instead of glycerin.
[실시예4]Example 4
상기 실시예 1에서 글리세린 대신에 트리메틸롤프로판 154 g을 투입한 것을 제외하고는 상기 실시예 1과 동일하게 실시하여 분체상의 페이스트 염화비닐 수지를 제조하였다.Powder paste vinyl chloride resin was prepared in the same manner as in Example 1, except that 154 g of trimethylolpropane was added instead of glycerin.
[비교예 1]Comparative Example 1
상기 실시예 1에서 글리세린을 투입하지 않는 것을 제외하고는 상기 실시예1과 동일하게 실시하여 분체상의 페이스트 염화비닐 수지를 제조하였다.A powdery paste vinyl chloride resin was prepared in the same manner as in Example 1, except that glycerin was not added in Example 1.
상기 실시예 및 비교예에서 제조된 염화비닐 수지의 물성을 아래와 같은 방법으로 측정하였고, 그 결과를 표 1에 나타내었다.The physical properties of the vinyl chloride resins prepared in Examples and Comparative Examples were measured by the following method, and the results are shown in Table 1.
1) 플라스티졸의 제조1) Preparation of Plastisol
페이스트 염화비닐계 수지 100 g에 가소제로 디옥틸프탈레이트 70 중량부, 탄산칼슘 70 중량부, TiO2 10 중량부, 발포제 3 중량부, 점도 저하제 14 중량부, 안정제(Ba-Zn계 스테아레이트) 2 중량부를 첨가한 후 800 rpm에서 10 분간 혼합하여 플라스트졸을 제조하였다. 70 parts by weight of dioctylphthalate, 70 parts by weight of calcium carbonate, 10 parts by weight of TiO2, 3 parts by weight of blowing agent, 14 parts by weight of viscosity reducing agent, and stabilizer (Ba-Zn-based stearate) to 100 g of a paste vinyl chloride resin. After the addition, the mixture was mixed at 800 rpm for 10 minutes to prepare a plassol.
2) BF점도 측정 방법 2) BF viscosity measurement method
초기 BF점도와 1일 BF점도는 상기 제조된 플라스티졸(plastisol)을 25 ℃ 항온 항습기에서에서 1시간과 1일 숙성 후 브룩필드 DV-Ⅲ 점도계의 3번 spindle, 회전수 6 rpm에서 BF점도를 측정하였다. The initial BF viscosity and the daily BF viscosity were measured for 1 hour and 1 day at the constant temperature and humidity of the plastisol prepared above at 25 ° C., and then BF viscosity at 3 rpm of the Brookfield DV-III viscometer at 6 rpm. Was measured.
글리세린 또는 트리메틸롤프로판을 첨가하는 단계를 포함하는 방법에 의하여 제조된 본원 발명의 염화비닐계 수지의 초기 BF점도와 1일 BF점도가 비교예 1의 수지보다 낮음을 확인할 수 있었다. 즉, 초기 점도(초기 BF점도) 및 점도 안정성(1일 BF점도)이 우수한 염화비닐계 수지를 얻을 수 있었다. It was confirmed that the initial BF viscosity and daily BF viscosity of the vinyl chloride-based resin of the present invention prepared by the method comprising the addition of glycerin or trimethylolpropane were lower than the resin of Comparative Example 1. In other words, a vinyl chloride resin having excellent initial viscosity (initial BF viscosity) and viscosity stability (daily BF viscosity) was obtained.
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| WO2010143893A3 (en) * | 2009-06-10 | 2011-04-21 | 주식회사 엘지화학 | Vinyl-chloride-based resin for foaming having outstanding low-viscosity characteristics, and a production method therefor |
| KR20160011347A (en) | 2014-07-22 | 2016-02-01 | 주식회사 엘지화학 | Producing method of vinyl chloride-based resin paste with excellent viscosity stability and foaming properties |
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| KR101424879B1 (en) * | 2012-02-03 | 2014-08-04 | 주식회사 엘지화학 | Viscosity reducing agent for paste vinyl chloride resins and and method for controlling viscosity of paste vinyl chloride resin using thereof |
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| JP2001151969A (en) | 1999-11-24 | 2001-06-05 | Riken Vinyl Industry Co Ltd | Vinyl chloride resin composition for sol |
| DE102004016791A1 (en) | 2004-04-06 | 2005-11-10 | Clariant Gmbh | Use of waxes as a lubricant for filled plastics |
| JP4274098B2 (en) * | 2004-09-30 | 2009-06-03 | 東ソー株式会社 | Vinyl chloride resin for paste processing and production method thereof, vinyl chloride resin composition for paste processing and use thereof |
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| KR20160011347A (en) | 2014-07-22 | 2016-02-01 | 주식회사 엘지화학 | Producing method of vinyl chloride-based resin paste with excellent viscosity stability and foaming properties |
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