KR20130035493A - Ester plasticizer composition - Google Patents
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- KR20130035493A KR20130035493A KR1020110099818A KR20110099818A KR20130035493A KR 20130035493 A KR20130035493 A KR 20130035493A KR 1020110099818 A KR1020110099818 A KR 1020110099818A KR 20110099818 A KR20110099818 A KR 20110099818A KR 20130035493 A KR20130035493 A KR 20130035493A
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- plasticizer composition
- ester plasticizer
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- terephthalate
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- C—CHEMISTRY; METALLURGY
- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
- C07C69/80—Phthalic acid esters
- C07C69/82—Terephthalic acid esters
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- C—CHEMISTRY; METALLURGY
- 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
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0016—Plasticisers
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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
Abstract
Description
본 발명은 에스터 가소제 조성물에 관한 것으로, 보다 구체적으로는 혼성 알킬 치환된 테레프탈레이트 화합물과 비혼성 알킬 치환된 테레프탈레이트 화합물을 유효 성분으로 포함하는 가소제 조성물이 수지에 대한 흡수속도와 짧은 용융 시간을 가져 가공성이 개선되고, 벽지 처방시 고른 발포성을 부여할 수 있는 에스터 가소제 조성물에 관한 것이다.
The present invention relates to an ester plasticizer composition, and more particularly, a plasticizer composition comprising a hybrid alkyl substituted terephthalate compound and a non-hybrid alkyl substituted terephthalate compound as an active ingredient has an absorption rate and a short melting time for the resin. Processability is improved, and relates to an ester plasticizer composition capable of imparting even foamability in wallpaper formulation.
통상적으로 가소제는 알코올이 프탈산 및 아디프산과 같은 폴리카복시산과 반응하여 이에 상응하는 에스터를 형성한다. 상업적으로 중요한 예는 C8, C9 및 C10 알콜의 아디페이트, 예를 들면 디(2-에틸헥실) 아디페이트, 디이소노닐 아디페이트, 디이소데실 아디페이트; 및 C8, C9 및 C10 알콜의 프탈레이트, 예를 들면 디(2-에틸헥실) 프탈레이트, 디이소노닐 프탈레이트, 디이소데실 프탈레이트를 포함한다.
Typically, plasticizers react with alcohols to polycarboxylic acids such as phthalic acid and adipic acid to form the corresponding esters. Commercially important examples include adipates of C8, C9 and C10 alcohols such as di (2-ethylhexyl) adipate, diisononyl adipate, diisodecyl adipate; And phthalates of C8, C9 and C10 alcohols, such as di (2-ethylhexyl) phthalate, diisononyl phthalate, diisodecyl phthalate.
구체적으로 상기 디이소노닐 프탈레이트는 폴리염화비닐(PVC)을 위한 일반적 목적의 가소제이고, 플라스티졸(plastisol) 및 건식 배합 둘 다를 통하여 거의 모든 알려진 가요성 PVC 용도에서 사용된다. 전형적인 용도는 장남감, 필름, 신발, 도료, 바닥재, 장갑, 벽지, 인조 가죽, 실란트, 타포린, 차 바닥 코팅제, 가구, 발포 매트, 및 방음 패널에서 상기 물질을 포함하며, 모두 가소성 PVC에 근거한다. 이는 또한 PVC 케이블의 외장 및 절연, 및 다른 캘린더링된 가요성 PVC 제품을 생산하는 데 사용된다.
In particular, the diisononyl phthalate is a general purpose plasticizer for polyvinyl chloride (PVC) and is used in almost all known flexible PVC applications through both plastisol and dry formulations. Typical uses include such materials in toys, films, shoes, paints, floorings, gloves, wallpaper, artificial leather, sealants, tarpaulins, car floor coatings, furniture, foam mats, and soundproofing panels, all based on plastic PVC. It is also used to produce the sheath and insulation of PVC cables, and other calendared flexible PVC products.
디이소노닐 아디페이트는 특히 필름에서 사용되고, 가소성 PVC에 기초한 벽지, 인조 가죽, 차 바닥 코팅제, 장갑, 및 실란트와 같은 다른 제품에도 낮은 수준으로 사용된다. 디이소노닐 아디페이트는 생성물을 저온에서 사용하고자 하는 경우 및/또는 공정 중간체로서 플라스티졸을 사용하는 경우에 특히 사용된다.Diisononyl adipates are especially used in films and at low levels in other products such as wallpaper, artificial leather, car floor coatings, gloves, and sealants based on plastic PVC. Diisononyl adipate is particularly used when the product is intended to be used at low temperatures and / or when plastisols are used as process intermediates.
상기 디이소노닐 아디페이트와는 별개로 프탈레이트계 가소제의 환경 문제로 인하여 추가로 친환경 가소제에 대한 연구가 계속되고 있는 실정이다.
In addition to the diisononyl adipate, due to the environmental problems of the phthalate-based plasticizer, further studies on environmentally friendly plasticizers are being continued.
이에 본 발명자들은 친환경 가소제에 대한 연구를 계속하던 중 혼성 알킬 치환된 테레프탈레이트 화합물과 비혼성 알킬 치환된 테레프탈레이트 화합물을 유효 성분으로 포함하는 가소제 조성물이 수지에 대한 흡수속도와 짧은 용융 시간을 가져 가공성이 개선되고, 벽지 처방시 고른 발포성을 부여할 수 있는 효과를 제공할 수 있음을 확인하고 본 발명을 완성하기에 이르렀다.
Therefore, the inventors of the present invention continued the research on environmentally friendly plasticizers, and the plasticizer composition including a mixed alkyl substituted terephthalate compound and a non-hybrid alkyl substituted terephthalate compound as an active ingredient has a processability due to absorption rate and short melting time for the resin. This improved and confirmed that it can provide the effect that can give evenly foamability when prescribing wallpaper, and came to complete the present invention.
즉, 본 발명의 목적은 친환경 가소제로서 혼성 알킬 치환된 테레프탈레이트 화합물과 비혼성 알킬 치환된 테레프탈레이트 화합물을 유효 성분으로 포함하는 에스터 가소제 조성물을 제공하려는데 있다.
That is, an object of the present invention is to provide an ester plasticizer composition comprising a hybrid alkyl substituted terephthalate compound and a non-hybrid alkyl substituted terephthalate compound as active ingredients as an environmentally friendly plasticizer.
본 발명에 따르면, According to the present invention,
혼성 알킬 치환된 테레프탈레이트계 화합물과 비혼성 알킬 치환된 테레프탈레이트계 화합물을 유효 성분으로 포함하는 에스터 가소제 조성물을 제공한다.
An ester plasticizer composition comprising a mixed alkyl substituted terephthalate-based compound and an immiscible alkyl substituted terephthalate-based compound as an active ingredient is provided.
이하, 본 발명에 대하여 상세하게 설명한다. EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.
본 발명에서 에스터 가소제 조성물을 이루는 혼성 알킬 치환된 테레프탈레이트계 화합물은 이에 한정하는 것은 아니나, 알코올과 산의 반응에 의해 생성되되, 상기 알코올은 3 내지 4개의 탄소원자를 갖는 비분지된 1차 알코올 및 8 내지 10개의 탄소원자를 갖는 분지된 1차 알코올의 혼합물인 것을 기술적 특징으로 한다.
In the present invention, the hybrid alkyl-substituted terephthalate-based compound constituting the ester plasticizer composition is not limited thereto, but is produced by reaction of an alcohol with an acid, wherein the alcohol is an unbranched primary alcohol having 3 to 4 carbon atoms and It is technically characterized as a mixture of branched primary alcohols having 8 to 10 carbon atoms.
특히, 상기 혼성 알킬 치환된 테레프탈레이트계 화합물은 하기 식 1로 표기된 종류를 사용하는 것이 수지와의 흡수 속도와 이행 손실(migration loss) 정도를 고려할 때 가장 바람직하다. In particular, the hybrid alkyl-substituted terephthalate-based compound is most preferably used in consideration of the absorption rate and the degree of migration loss with the resin represented by the following formula (1).
또한 본 발명에서 에스터 가소제 조성물을 이루는 비혼성 알킬 치환된 테레프탈레이트계 화합물은 비분지된 1차 알코올 유래 테레프탈레이트계 화합물,과 분지된 1차 알코올 유래 테레프탈레이트계 화합물을 배합하여 사용할 수 있다.
In addition, in the present invention, the non-hybrid alkyl-substituted terephthalate-based compound constituting the ester plasticizer composition may be used by combining an unbranched primary alcohol-derived terephthalate-based compound and a branched primary alcohol-derived terephthalate-based compound.
이들 비혼성 알킬 치환된 테레프탈레이트계 화합물은 이에 한정하는 것은 아니나, 알코올과 산의 반응에 의해 생성되되, 상기 알코올은 3 내지 4개의 탄소원자를 갖는 비분지된 1차 알코올 및 8 내지 10개의 탄소원자를 갖는 분지된 1차 알코올 중 1종 이상 선택되어 사용된 것을 기술적 특징으로 한다. 이중 비분지된 1차 알코올은 n-부틸 알코올이고, 분지된 1차 알코올은 2-에틸헥산올인 것이 보다 바람직하다. These non-hybrid alkyl substituted terephthalate-based compounds are not limited thereto, but are produced by the reaction of an alcohol with an acid, wherein the alcohol is an unbranched primary alcohol having 3-4 carbon atoms and 8-10 carbon atoms. One or more of the branched primary alcohol having is selected and used as a technical feature. More preferably, the unbranched primary alcohol is n-butyl alcohol, and the branched primary alcohol is 2-ethylhexanol.
특히, 상기 비혼성 알킬 치환된 테레프탈레이트계 화합물은 상기 알코올로서, 3 내지 4개의 탄소원자를 갖는 비분지된 1차 알코올을 사용하여 수득된 화합물, 과 8 내지 10개의 탄소원자를 갖는 분지된 1차 알코올을 사용하여 수득된 화합물, 을 모두 사용하는 것이 수지와의 빠른 흡수속도에 따른 가공의 용이성(가소화 효율), 이행 손실(Migration loss) 정도를 고려할 때 보다 바람직하다.
In particular, the non-hybrid alkyl substituted terephthalate-based compound is a compound obtained using the unbranched primary alcohol having 3 to 4 carbon atoms as the alcohol, and the branched primary alcohol having 8 to 10 carbon atoms. It is more preferable to use all of the compounds obtained using and considering the ease of processing (plasticization efficiency) and the degree of migration loss depending on the fast absorption rate with the resin.
이때 본 발명에서 사용하는 산은 카복시산, 폴리카복시산 또는 그 무수물을 의미하는 것으로, 이에 한정하는 것은 아니나, 테레프탈산을 사용하는 것이 보다 바람직하다.
In this case, the acid used in the present invention means carboxylic acid, polycarboxylic acid or anhydride thereof, but is not limited thereto, and it is more preferable to use terephthalic acid.
나아가 상기 산은 습식 분쇄에 의해 평균 입경 30 내지 100 ㎛ 범위 내인 것이 반응 시간을 단축하여 생산성을 향상시킬 수 있어 바람직하며, 상기 습식 분쇄는 이에 한정하는 것은 아니나, 캐비트론 및 트리그널 중에서 선택된 고속 회전 습식 분쇄 장치를 사용하여 수행되는 것이 바람직하다. 이때 회전 조건은 3,000 내지 50,000 rpm을 적용할 수 있어 신속하게 원하는 평균 입경 분포에 도달할 수 있는 잇점을 함께 갖는다.
Furthermore, the acid is preferably in the range of an average particle diameter of 30 to 100 μm by wet grinding to shorten the reaction time, thereby improving productivity. The wet grinding is not limited thereto, but a high-speed rotary wet type selected from cavrons and triggers is used. It is preferably carried out using a grinding device. At this time, the rotation conditions can be applied to 3,000 to 50,000 rpm has the advantage that can quickly reach the desired average particle size distribution.
한편, 본 발명에서 상술한 비분지된 1차 알코올 유래 테레프탈레이트계 화합물,과 분지된 1차 알코올 유래 테레프탈레이트계 화합물,간 배합비는 25:75 내지 10 내지 90의 중량비인 것이 바람직하며, 40:60 내지 30:70의 중량비인 것이 보다 바람직하며, 약 50:50의 중량비인 것이 수지와의 흡수 속도를 고려할 때 가장 바람직하다.
Meanwhile, in the present invention, the non-branched primary alcohol-derived terephthalate-based compound and the branched primary alcohol-derived terephthalate-based compound, the liver blending ratio is preferably a weight ratio of 25:75 to 10 to 90, 40: A weight ratio of 60 to 30:70 is more preferable, and a weight ratio of about 50:50 is most preferable when considering the absorption rate with the resin.
이 중에서 비분지된 1차 알코올을 사용하여 수득된 비혼성 알킬 치환된 테레프탈레이트계 화합물로는 하기 [화학식 2]로 표기된 종류를 사용하는 것이 가장 바람직하다.Among them, as the non-hybrid alkyl-substituted terephthalate-based compound obtained using an unbranched primary alcohol, it is most preferable to use a kind represented by the following [Formula 2].
또한 상기 분지된 1차 알코올을 사용하여 수득된 비혼성 알킬 치환된 테레프탈레이트계 화합물로는 하기 [화학식 3]으로 표기된 종류를 사용하는 것이 가장 바람직하다.In addition, as the non-hybrid alkyl-substituted terephthalate compound obtained using the branched primary alcohol, it is most preferable to use the kind represented by the following [Formula 3].
본 발명의 혼성 알킬 치환된 테레프탈레이트계 화합물과 비혼성 알킬 치환된 테레프탈레이트계 화합물은 10:50 내지 50:90의 중량비로 배합하는 것이 가공성 및 발포성의 개선 측면을 고려할 때 바람직하다.
The mixed alkyl substituted terephthalate-based compound and the non-mixed alkyl substituted terephthalate-based compound of the present invention are preferably blended at a weight ratio of 10:50 to 50:90 when considering processability and foamability improvement.
또한 본 발명의 혼성 알킬 치환된 테레프탈레이트계 화합물과 비혼성 알킬 치환된 테레프탈레이트계 화합물은 10 ～ 50 : 10 ～ 50 : 40 ～ 80의 중량비, 나아가 30 ～ 50 : 10 ～ 20 : 40 ～ 50의 중량비로 배합하는 것이 가공성 및 발포성의 개선 측면을 고려할 때 바람직하다.
In addition, the mixed alkyl-substituted terephthalate-based compound and the non-mixed alkyl-substituted terephthalate-based compound of the present invention have a weight ratio of 10 to 50: 10 to 50: 40 to 80, and more preferably 30 to 50: 10 to 20: 40 to 50. It is preferable to mix | blend by weight ratio in consideration of the improvement of workability and foamability.
한편, 본 발명의 에스터 가소제 조성물은 혼성 알킬 치환된 테레프탈레이트계 화합물과 비혼성 알킬 치환된 테레프탈레이트계 화합물을 각각 준비하여 배합할 수도 있으며, 적절한 알코올 혼합물을 사용하여 테레프탈산과의 에스테르화 반응을 통하여 혼성 알킬 치환된 테레프탈레이트계 화합물과 비혼성 알킬 치환된 테레프탈레이트계 화합물이 배합된 혼합물 자체를 사용하여도 좋다.
Meanwhile, the ester plasticizer composition of the present invention may prepare and mix a mixed alkyl substituted terephthalate compound and a non-hybrid alkyl substituted terephthalate compound, respectively, through an esterification reaction with terephthalic acid using an appropriate alcohol mixture. You may use the mixture itself which mixed the hybrid alkyl substituted terephthalate type compound and the non-hybrid alkyl substituted terephthalate type compound.
이들 에스터 가소제 조성물은 이에 한정하는 것은 아니나, 염화비닐계 수지에 대한 가소제로서 적용하기 바람직하다. 상기 에스터 가소제 조성물은 염화비닐계 수지 100 중량부에 대하여 5 내지 100 중량부 범위 내에서 사용될 수 있다. 이때, 에스터 가소제 조성물에는 디옥틸프탈레이트(DOP), 디부틸프탈레이트(DBP), 디옥틸테레프텔레이트(DOTP), 디이소노닐프탈레이트(DINP), 디이소데실프탈레이트(DIDP) 중에서 선택된 가소제를 수지 100 중량부 기준으로 5 내지 100 중량부 범위 내로 더 포함시켜 사용할 수도 있다.
Although these ester plasticizer compositions are not limited to this, it is preferable to apply as a plasticizer with respect to a vinyl chloride type resin. The ester plasticizer composition may be used within the range of 5 to 100 parts by weight based on 100 parts by weight of the vinyl chloride resin. In this case, the plasticizer selected from dioctylphthalate (DOP), dibutyl phthalate (DBP), dioctyl terephthalate (DOTP), diisononyl phthalate (DINP), and diisodecyl phthalate (DIDP) may be used in the ester plasticizer composition. It may be used by including more within the range of 5 to 100 parts by weight based on parts by weight.
또한, 이에 한정하는 것은 아니나, 본 건의 조성물에는 안정화제 0.5 내지 7 중량부, 및 활제 0.5 내지 3 중량부 등을 더 첨가하여 조성할 수 있다.
In addition, although not limited thereto, 0.5 to 7 parts by weight of a stabilizer, 0.5 to 3 parts by weight of a lubricant, and the like may be further added to the composition of the present invention.
특히, 본 발명에서 제공하는 에스터 가소제 조성물은 하기 실시예에서 규명된 바와 같이, 벽지 시트로서 처방될 경우 고른 발포성을 부여할 수 있다.
In particular, the ester plasticizer composition provided in the present invention may impart even foamability when prescribed as a wallpaper sheet, as elucidated in the following examples.
본 발명에 따르면, 혼성 알킬 치환된 테레프탈레이트계 화합물과 비혼성 알킬 치환된 테레프탈레이트계 화합물을 유효 성분으로 포함하는 가소제 조성물이 수지에 대한 흡수속도와 짧은 용융 시간을 가져 가공성이 개선되고, 벽지 처방시 고른 발포성을 부여할 수 있는 잇점을 갖는다.
According to the present invention, a plasticizer composition comprising a mixed alkyl substituted terephthalate-based compound and an immiscible alkyl-substituted terephthalate-based compound as an active ingredient has an absorption rate and a short melting time for the resin, thereby improving processability and prescribing wallpaper. It has the advantage of imparting even foamability.
이하, 실시예를 들어 본 발명을 구체적으로 설명한다. 그러나, 이하 실시예는 본 발명의 예시일 뿐 본 발명을 이에 한정하는 의미는 아니다.
Hereinafter, an Example is given and this invention is demonstrated concretely. However, the following examples are only examples of the present invention and are not meant to limit the present invention thereto.
<< 실시예Example 1> 1>
우선, 테레프탈산으로서 평균 입경이 30 내지 100 ㎛ 범위 내인 분쇄물을 준비하였다. 이같이 준비한 테레프탈산 440 g과 n-부탄올 297 g 및 2-에틸헥산올 530 g을 200 ℃ 하에 3 시간 동안 반응시킨 다음 Na2CO3를 사용하여 중화하고 물로 1회 수세한 다음 감압하에 가열하여 탈알코올시켜 가소제 조성물을 수득하였다.
First, a pulverized product having an average particle diameter in the range of 30 to 100 μm was prepared as terephthalic acid. Thus prepared 440 g of terephthalic acid, 297 g of n-butanol and 530 g of 2-ethylhexanol were reacted under 200 ° C. for 3 hours, neutralized with Na 2 CO 3 , washed with water once, and heated under reduced pressure to remove alcohol. To obtain a plasticizer composition.
수득된 가소제를 GC-Mass 분석기로 분석한 결과 하기 화학식 1, 2, 3을 갖는 물질들로 이루어진 것을 확인하였다. The obtained plasticizer was analyzed by a GC-Mass analyzer, and it was confirmed that the material was composed of the following Chemical Formulas 1, 2, and 3.
[화학식 1][Formula 1]
[화학식 2][Formula 2]
[화학식 3](3)
또한, 상기 화학식 1: 화학식 2: 화학식 3의 중량비는 50 : 10 : 40 인 것을 확인할 수 있었다. In addition, it was confirmed that the weight ratio of Formula 1: Formula 2: Formula 3 is 50:10:40.
이 같은 생성물을 염화비닐계 수지 100 중량부에 5 내지 100 중량부 범위 내로 사용하고, 추가로 안정화제 활제 및 발포제를 더 추가하고 압출시켜 벽지를 제조하였다.
This product is used in 100 parts by weight of the vinyl chloride resin in the range of 5 to 100 parts by weight, and further stabilizer lubricant and blowing agent are added and extruded to prepare a wallpaper.
제조도중 벽지의 흡수 속도는 Mixing (77 ℃ 60rpm/PVC(LS 100 )400 Plasticizer 200 g)되는 시간을 측정한 경우 DOP 단독 대비 10% 단축된 것으로 측정되었으며, 용융 속도는 110 ℃/55g/60 rpm으로 측정한 경우 DOP 단독 사용하여 측정한 경우와 유사하고, DOTP 단독을 사용하여 측정한 경우 대비하여 50% 단축된 것으로 측정되었다. During manufacturing, the absorption rate of wallpaper was measured to be 10% shorter than DOP alone when the mixing time (77 ℃ 60rpm / PVC (LS 100) 400 Plasticizer 200 g) was measured, and the melting rate was 110 ℃ / 55g / 60 rpm. When measured by using a similar to that measured using the DOP alone, it was measured to be reduced by 50% compared to the case measured using the DOTP alone.
제조된 벽지의 발포성은 발포 후 cell 상태를 광학 현미경으로 측정한 경우 DOP 단독, DINP 단독, DOTP 단독을 사용한 경우보다 cell 크기나 모양, 배열이 균일하게 관찰되었다.
The foamability of the prepared wallpaper was observed to be uniform in cell size, shape, and arrangement when the cell state after foaming was measured with an optical microscope than DOP alone, DINP alone, or DOTP alone.
<< 실시예Example 2> 2>
화학식 1로 표기되는 화합물 30 중량부, 화학식 2로 표기되는 화합물 10 중량부, 화학식 3으로 표기되는 화합물 60 중량부를 배합하여 사용한 것을 제외하고는 실시예 1과 동일한 실험을 반복하여 벽지를 제조하였다.
The same experiment as in Example 1 was repeated except that 30 parts by weight of the compound represented by Formula 1, 10 parts by weight of the compound represented by Formula 2, and 60 parts by weight of the compound represented by Formula 3 were used to prepare a wallpaper.
제조도중 벽지의 흡수 속도는 Mixing (77 ℃ 60rpm/PVC(LS 100)400 Plasticizer 200 g)되는 시간을 측정한 경우 DOP 단독을 사용한 경우와 유사하였고, DOTP 단독을 사용한 경우 대비 25% 단축된 것으로 측정되었으며, 용융 속도는 110 ℃/55g/60 rpm으로 측정한 경우 DOTP 단독을 사용하여 측정한 경우 대비하여 37% 단축된 것으로 측정되었다. The absorption rate of wallpaper during manufacture was similar to that of using DOP alone when the mixing time (77 ℃ 60rpm / PVC (LS 100) 400 Plasticizer 200 g) was measured, which was 25% shorter than that of using DOTP alone. The melt rate was measured to be 37% shorter when measured at 110 ° C./55 g / 60 rpm compared to when measured using DOTP alone.
제조된 벽지의 발포성은 발포 후 cell 상태를 광학 현미경으로 측정한 경우 DOP 단독, DINP 단독, DOTP 단독을 사용한 경우보다 cell 크기나 모양, 배열이 균일하게 관찰되었다.
The foamability of the prepared wallpaper was observed to be uniform in cell size, shape, and arrangement when the cell state after foaming was measured with an optical microscope than DOP alone, DINP alone, or DOTP alone.
<< 비교예Comparative example 1> 1>
실시예 1에서 테레프탈산 440 g과 n-부탄올 890 g을 130 ℃ 하에 13 시간 동안 반응시킨 것을 제외하고는 상기 실시예 1과 동일한 공정을 반복하여 가소제를 제조하였다. A plasticizer was prepared in the same manner as in Example 1, except that 440 g of terephthalic acid and 890 g of n-butanol were reacted at 130 ° C. for 13 hours in Example 1.
수득된 가소제를 GC-Mass 분석기로 분석한 결과 하기 화학식 2를 갖는 화합물을 확인할 수 있었다. As a result of analyzing the obtained plasticizer by GC-Mass analyzer, it was confirmed that the compound having the formula (2).
[화학식 2][Formula 2]
이 같은 화합물을 염화비닐계 수지 100 중량부에 5 내지 100 중량부 범위 내로 사용하고, 추가로 안정화제 활제 및 발포제를 더 추가하고 압출시켜 벽지를 제조하였다.
The compound was used in 100 parts by weight of the vinyl chloride resin in the range of 5 to 100 parts by weight, and further stabilizer lubricant and blowing agent were added and extruded to prepare a wallpaper.
제조도중 벽지의 흡수 속도는 Mixing (77 ℃ 60rpm/PVC(LS 100)400 Plasticizer 200 g)되는 시간을 측정한 경우 DOP 단독 대비 67% 단축된 것으로 측정되었으며, 용융 속도는 110 ℃/55g/60 rpm으로 측정한 경우 DOP 단독 사용하여 측정한 경우 대비하여 31% 단축된 것으로 측정되었다. During manufacturing, the absorption rate of wallpaper was measured to be 67% shorter than that of DOP alone when the mixing time (77 ℃ 60rpm / PVC (LS 100) 400 Plasticizer 200 g) was measured.The melt rate was 110 ℃ / 55g / 60 rpm. In the case of the measurement, it was measured to be 31% shorter than that measured using the DOP alone.
또한, DOP 단독을 사용하여 측정한 경우 대비 이행 손실(migration loss)(80 ℃로 72 시간 가열 후 이행으로 인한 가소제의 손실정도를 측정함)은 7% 증가하였다.
In addition, migration loss (measurement of plasticizer loss due to migration after 72 hours of heating at 80 ° C.) was increased by 7% compared to that measured using DOP alone.
제조된 벽지의 발포성은 발포 후 cell 상태를 광학 현미경으로 측정한 경우 DOP 단독, DINP 단독, DOTP 단독을 사용한 경우보다 cell 크기나 모양, 배열이 균일하게 관찰되었다.
The foamability of the prepared wallpaper was observed to be uniform in cell size, shape, and arrangement when the cell state after foaming was measured with an optical microscope than DOP alone, DINP alone, or DOTP alone.
<< 비교예Comparative example 2> 2>
실시예 1에서 테레프탈산 440 g과 2-에틸헥산올 1,060 g을 220 ℃ 하에 5 시간 동안 반응시킨 것을 제외하고는 상기 실시예 1과 동일한 공정을 반복하여 가소제를 제조하였다. A plasticizer was prepared in the same manner as in Example 1, except that 440 g of terephthalic acid and 1,060 g of 2-ethylhexanol were reacted at 220 ° C. for 5 hours in Example 1.
수득된 가소제를 GC-Mass 분석기로 분석한 결과 하기 화학식 3을 갖는 화합물을 확인할 수 있었다. As a result of analyzing the obtained plasticizer by GC-Mass analyzer, it was confirmed that the compound having the formula (3).
[화학식 3] (3)
이 같은 화합물을 염화비닐계 수지 100 중량부에 5 내지 100 중량부 범위 내로 사용하고, 추가로 안정화제 활제 및 발포제를 더 추가하고 압출시켜 벽지를 제조하였다.
The compound was used in 100 parts by weight of the vinyl chloride resin in the range of 5 to 100 parts by weight, and further stabilizer lubricant and blowing agent were added and extruded to prepare a wallpaper.
제조도중 벽지의 흡수 속도는 Mixing (77 ℃ 60rpm/PVC(LS 100)400 Plasticizer 200 g)되는 시간을 측정한 경우 DOP 단독 대비 28% 증가된 것으로 측정되었으며, 용융 속도는 110 ℃/55g/60 rpm으로 측정한 경우 DOP 단독 사용하여 측정한 경우 대비하여 76% 증가된 것으로 측정되었다. During manufacturing, the absorption rate of wallpaper was increased by 28% compared to DOP alone when the mixing time (77 ℃ 60rpm / PVC (LS 100) 400 Plasticizer 200 g) was measured, and the melting rate was 110 ℃ / 55g / 60 rpm. In the case of the measurement, the increase was 76% compared to the measurement using the DOP alone.
그러나 DOP 단독을 사용하여 측정한 경우에 비하여 이행 손실(migration loss)가 1% 감소한 것을 확인하였다.
However, it was confirmed that the migration loss was reduced by 1% compared with the measurement using the DOP alone.
또한, 제조된 벽지의 발포성은 발포 후 cell 상태를 광학 현미경으로 측정한 경우 DOP 단독, DINP 단독, DBTP 단독, BPTP 단독을 사용한 경우보다 cell 크기나 모양, 배열이 열세인 것으로 관찰되었다.
In addition, the foamability of the manufactured wallpaper was observed to be inferior in cell size, shape, and arrangement when the cell state after foaming was measured with an optical microscope than DOP alone, DINP alone, DBTP alone, or BPTP alone.
상기 측정 결과로부터 확인할 수 있듯이, 화학식 2의 화합물을 단독 사용한 비교예 1의 경우에는 흡수와 용융 면에서 탁월하게 시간이 감축되었지만, 그만큼 이행(migration) 정도가 심해지는 단점이 확인되었다.
As can be seen from the above measurement results, in the case of Comparative Example 1 using the compound of Formula 2 alone, the time was reduced significantly in terms of absorption and melting, but it was confirmed that the degree of migration was increased.
또한, 화학식 3의 화합물을 단독 사용한 비교예 2의 경우에는 이행(migration)은 거의 일어나지 않지만, 분자량이 큰 만큼 흡수와 용융 시 많은 시간이 걸리는 단점이 확인되었다.
In addition, in the case of Comparative Example 2 using the compound of the formula (3) alone, the migration (migration) hardly occurs, but the disadvantage that it takes a lot of time for absorption and melting as the molecular weight is large.
한편, 실시예 1 및 2에서와 같이 이들을 모두 포함하고, 나아가 적절한 배합비로 적용될 경우 모든 물성 측면에서 바람직한 결과를 확인할 수 있었다. On the other hand, including all of them as in Examples 1 and 2, and furthermore, when applied in an appropriate blending ratio it could confirm the preferred results in terms of all physical properties.
Claims (15)
An ester plasticizer composition comprising a hybrid alkyl substituted terephthalate compound and a non-hybrid alkyl substituted terephthalate compound as active ingredients.
상기 혼성 알킬 치환된 테레프탈레이트계 화합물은 알코올과 산의 반응에 의해 생성되되, 상기 알코올은 3 내지 4개의 탄소원자를 갖는 비분지된 1차 알코올 및 8 내지 10개의 탄소원자를 갖는 분지된 1차 알코올의 혼합물인 것을 특징으로 하는 에스터 가소제 조성물.
The method of claim 1,
The hybrid alkyl-substituted terephthalate-based compound is produced by reaction of an alcohol with an acid, wherein the alcohol is formed of an unbranched primary alcohol having 3 to 4 carbon atoms and a branched primary alcohol having 8 to 10 carbon atoms. Ester plasticizer composition, characterized in that the mixture.
상기 혼성 알킬 치환된 테레프탈레이트계 화합물은 하기 식 1로 표기된 것을 특징으로 하는 에스터 가소제 조성물
[화학식 1]
The method of claim 1,
Ester plasticizer composition characterized in that the mixed alkyl substituted terephthalate-based compound represented by the following formula
[Formula 1]
상기 비혼성 알킬 치환된 테레프탈레이트계 화합물은 비분지된 1차 알코올 유래 테레프탈레이트계 화합물,과 분지된 1차 알코올 유래 테레프탈레이트계 화합물, 중에서 1종 이상 선택되는 것을 특징으로 하는 에스터 가소제 조성물.
The method of claim 1,
The non-hybrid alkyl-substituted terephthalate compound is an ester plasticizer composition, characterized in that at least one selected from unbranched primary alcohol-derived terephthalate compound, and branched primary alcohol-derived terephthalate compound.
상기 비혼성 알킬 치환된 테레프탈레이트계 화합물은 알코올과 산의 반응에 의해 생성되되, 상기 알코올은 3 내지 4개의 탄소원자를 갖는 비분지된 1차 알코올 및 8 내지 10개의 탄소원자를 갖는 분지된 1차 알코올 중 1종 이상 선택되어 사용된 것을 특징으로 하는 에스터 가소제 조성물.
The method of claim 1,
The non-hybrid alkyl substituted terephthalate compound is produced by reaction of an alcohol with an acid, wherein the alcohol is an unbranched primary alcohol having 3 to 4 carbon atoms and a branched primary alcohol having 8 to 10 carbon atoms Ester plasticizer composition, characterized in that at least one selected from.
상기 산은 테레프탈산인 것을 특징으로 하는 에스터 가소제 조성물.
6. The method according to claim 2 or 5,
The ester plasticizer composition, characterized in that the acid is terephthalic acid.
상기 산은 평균 입경 30 내지 100 ㎛ 범위 내인 것을 특징으로 하는 에스터 가소제 조성물.
The method according to claim 2 or 5
The acid is an ester plasticizer composition, characterized in that in the range of 30 to 100 ㎛ average particle diameter.
상기 비분지된 1차 알코올 유래 테레프탈레이트계 화합물은 하기 [화학식 2]로 표기된 것을 특징으로 하는 에스터 가소제 조성물
[화학식 2]
5. The method of claim 4,
The unbranched primary alcohol-derived terephthalate-based compound is an ester plasticizer composition, characterized in that represented by the following [Formula 2]
(2)
상기 분지된 1차 알코올 유래 테레프탈레이트계 화합물은 하기 [화학식 3]으로 표기된 것을 특징으로 하는 에스터 가소제 조성물
[화학식 3]
5. The method of claim 4,
The branched primary alcohol-derived terephthalate compound is an ester plasticizer composition, characterized in that represented by the following [Formula 3]
(3)
상기 비분지된 1차 알코올 유래 테레프탈레이트계 화합물,과 분지된 1차 알코올 유래 테레프탈레이트계 화합물의 배합비는 25:75 내지 10:90 중량비인 것을 특징으로 하는 에스터 가소제 조성물.
The method of claim 4
Ester plasticizer composition characterized in that the compounding ratio of the non-branched primary alcohol-derived terephthalate-based compound, and the branched primary alcohol-derived terephthalate-based compound is 25:75 to 10:90 weight ratio.
상기 혼성 알킬 치환된 테레프탈레이트계 화합물과 비혼성 알킬 치환된 테레프탈레이트계 화합물의 배합비는 50:50 내지 10:90의 중량비인 것을 특징으로 하는 에스터 가소제 조성물.
The method of claim 1,
Ester plasticizer composition, characterized in that the mixing ratio of the mixed alkyl substituted terephthalate compound and the non-hybrid alkyl substituted terephthalate compound is a weight ratio of 50:50 to 10:90.
상기 혼성 알킬 치환된 테레프탈레이트계 화합물과 비혼성 알킬 치환된 테레프탈레이트계 화합물의 배합비는 10 내지 50: 10 내지 50: 40 내지 80의 중량비인 것을 특징으로 하는 에스터 가소제 조성물.
The method of claim 1,
Ester plasticizer composition characterized in that the mixing ratio of the mixed alkyl substituted terephthalate compound and the non-hybrid alkyl substituted terephthalate compound is 10 to 50: 10 to 50: 40 to 80.
상기 에스터 가소제 조성물은 염화비닐계 수지에 대한 가소제로 사용되는 것을 특징으로 하는 에스터 가소제 조성물.
The method of claim 1,
The ester plasticizer composition is an ester plasticizer composition, characterized in that used as a plasticizer for the vinyl chloride resin.
상기 에스터 가소제 조성물은 염화비닐계 수지 100 중량부에 대하여 5 내지 100 중량부 범위 내로 사용되는 것을 특징으로 하는 에스터 가소제 조성물.
The method of claim 13,
The ester plasticizer composition is an ester plasticizer composition, characterized in that used in the range of 5 to 100 parts by weight based on 100 parts by weight of the vinyl chloride resin.
상기 에스터 가소제 조성물은 벽지 처방을 위한 가소제로 사용되는 것을 특징으로 하는 에스터 가소제 조성물. The method of claim 13,
The ester plasticizer composition is an ester plasticizer composition, characterized in that used as a plasticizer for wallpaper formulation.
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