KR20160112443A - Composite plasticizer composition and polymer resin composition using the same - Google Patents
Composite plasticizer composition and polymer resin composition using the same Download PDFInfo
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- KR20160112443A KR20160112443A KR1020150038201A KR20150038201A KR20160112443A KR 20160112443 A KR20160112443 A KR 20160112443A KR 1020150038201 A KR1020150038201 A KR 1020150038201A KR 20150038201 A KR20150038201 A KR 20150038201A KR 20160112443 A KR20160112443 A KR 20160112443A
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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
- 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
- C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
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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
- C08L101/00—Compositions of unspecified macromolecular compounds
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
The present invention relates to a composite plasticizer composition applied to a polymer resin and a polymer resin composition using the same. More particularly, the present invention relates to a composite plasticizer composition capable of realizing excellent processing characteristics, compatibility, durability and plasticizing efficiency by using tributyl citrate together with di-2-ethylhexyl terephthalate and a polymer resin composition using the same .
Polymer resins are used in a variety of fields such as household goods, home appliances, clothing, automobiles, construction materials, and packaging materials depending on their characteristics. Polyethylene (PE), polypropylene (PP), polystyrene (PP), polyurethane (PU) and polyvinyl chloride (PVC) are widely used. In particular, PVC resin is applicable to various applications ranging from household goods to industrial materials because it has hardness, softness characteristics and various molding ability and is excellent in price competitiveness and has universal utility. Such a PVC resin is not used alone, and a plasticizer is added for various properties. Plasticizers provide flexibility to PVC resins and improve processability and compatibility. However, as the industry has developed, plasticizers have become more flexible not only in flexibility, but also in properties required for their applications, such as resistance to aging, cold resistance, oil resistance, water resistance, resistance to heat and heat.
Generally, the larger the molecular weight of the plasticizer, the better the aging resistance, but the compatibility with the vinyl chloride resin tends to be lowered. Accordingly, plasticizers suitable for aging and compatibility are selected according to application fields. Plasticizers satisfying environmental regulations are excellent at room temperature and aging properties, but tend to have poor processability, and thus have many problems in applying plasticizers to paste resins and straight resins.
Therefore, it is urgent to develop a new plasticizer that meets the requirements of the physical properties and usage of the plasticizer in accordance with such environmental regulations.
SUMMARY OF THE INVENTION The present invention has been conceived to solve the problems as described above, and it is an object of the present invention to provide a composite resin composition which is excellent in processability of paste resin, improves initial viscosity and stability of a sol and can improve gelling characteristics, And to provide a plasticizer composition.
In addition, the present invention has the advantages of plasticizing efficiency and plasticizer absorption rate in a straight resin and realizing the same properties even when used in a small amount, and is excellent in productivity during processing, It is an object of the present invention to provide a composite plasticizer composition.
Another object of the present invention is to develop a polymer resin composition using the composite plasticizer composition as described above.
In order to accomplish the above object, the present invention provides a composite plasticizer composition comprising tributyl citrate (TBC) and di-2-ethylhexyl terephthalate (DOTP) .
The composite plasticizer composition according to the present invention can improve processability and long-term storage stability by combining tibutyl citrate and di-2-ethylhexyl terephthalate, and improve gelling property and migration property. In addition, plasticization efficiency and plasticizer absorption rate in a straight resin can be improved, and productivity can be maximized in the production of a product by using the polymer resin composition containing the same.
In particular, the composite plasticizer composition according to the present invention can realize a synergistic effect of the processability, physical properties, plasticizing efficiency, etc. of the polymer resin as described above by controlling the weight mixing ratio of tributyl citrate and di-2-ethylhexyl terephthalate .
The preferred compositional weight ratio of the composite plasticizer may be 15 to 45 wt% of tributyl citrate and 55 to 85 wt% of di-2-ethylhexyl terephthalate.
The composite plasticizer composition according to an embodiment of the present invention preferably contains 25 to 40% by weight of tributyl citrate (A) and 60 to 75% by weight of the plasticizer compound (B) in order to realize a balance of physical properties and a property- It is better to include it.
The present invention provides a polymer resin composition comprising the composite plasticizer composition. At this time, the polymeric resin composition is not particularly limited, but 30 to 120 parts by weight of the composite plasticizer composition may be added to 100 parts by weight of the polymer resin. When the above range is satisfied, the compatibility with the polymer resin is excellent, and it is better to achieve the desired effects of the present invention such as processability, durability, plasticizing efficiency and the like.
The polymer resin may be any one or more selected from the group consisting of a polyvinyl chloride resin, an olefin resin, an ABS resin, an acrylic resin, and a polyester resin, but is not limited thereto.
The present invention also provides a molded article comprising the polymeric resin composition. Such molded articles include but are not limited to wallpaper, compound, wire compound, sheet, film, tarpaulin, hose, shoe, sealant, office supplies, gloves, cap, mat, gasket, food packaging, medical supplies, automotive supplies, Parts, and the like, but the present invention is not limited thereto.
The composite plasticizer composition according to the present invention is excellent in the processability of the paste resin, can dramatically improve the initial viscosity and stability of the sol, and has the advantage of improving the gelling property and the migration property. In addition, excellent plasticizer absorption rate and plasticizing efficiency in straight resins can realize the same properties in spite of a small amount of use, increase production speed and production during processing, There are advantages.
Hereinafter, the composite plasticizer composition of the present invention will be described in detail. The following embodiments are provided by way of example so that those skilled in the art can fully understand the spirit of the present invention. In addition, technical terms and scientific terms used herein have the same meaning as commonly understood by those of ordinary skill in the art to which this invention belongs, unless otherwise defined.
The present inventors have found that the processability of a paste resin for plasticizer compounds such as a terephthalate-based, phthalate-based, trimellitate-based, and adipate-based ester compound that has been conventionally used as a plasticizer for a polymer resin such as polyvinyl chloride resin The inventors of the present invention have made efforts to improve the plasticizability and plasticizer absorption rate of the plasticizer and the plasticity of the straight resin and the tributyl citrate (TBC) to the di-2-ethylhexyl terephthalate (DOTP) , Tributyl citrate), the processability, physical properties, plasticity and plasticizer absorption rate of the paste resin and the straight resin, as well as the productivity and economical efficiency of the polymer resin composition using the plasticizer composition, can be improved. Completed.
That is, the present invention provides a composite plasticizer composition comprising tributyl citrate and di-2-ethylhexyl terephthalate. At this time, the di-2-ethylhexyl terephthalate can not be replaced from the conventional plasticizer compound group, and the combination of the terephthalate and the terephthalate can be used to obtain the unexpected processability, physical properties, viscosity characteristics, And can maximize the aging resistance, durability, compatibility, long-term storage stability and productivity of the polymer resin composition to which the present invention is applied.
At this time, the composite plasticizer composition contains 5 to 45% by weight of tributyl citrate and 55 to 85% by weight of di-2-ethylhexyl terephthalate. More preferably 25 to 40% by weight of tributyl citrate and 60 to 75% by weight of di-2-ethylhexyl terephthalate because the present invention can satisfy the balance of physical properties of the desired effect.
The composite plasticizer composition according to the present invention may be applied to a polymer resin, and may be contained in 100 parts by weight of the polymer resin and 30 to 120 parts by weight of the composite plasticizer composition. At this time, the polymer resin may include a polyvinyl chloride resin, an olefin resin, an ABS resin, an acrylic resin, a polyester resin, and the like, but is not limited thereto.
The polymer resin composition may further include one or more additives selected from the group consisting of a secondary plasticizer, a stabilizer, a filler, a lubricant, a flame retardant, a viscosity modifier, a foaming agent, an enhancer and a pigment.
The polymer resin composition according to the present invention can be used for a wide variety of applications such as wallpaper, compound, wire compound, sheet, film, tarpaulin, hose, shoe, sealant, office supplies, gloves, bottle cap, mat, gasket, food packaging material, medical supplies, , Flooring materials, electromechanical parts and so on.
Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the scope of the present invention is not limited to the following examples.
[Example 1]
30% by weight of tributyl citrate (TBC) and 70% by weight of di-2-ethylhexyl terephthalate (DOTP) were mixed to prepare a composite plasticizer. Thereafter, 90 parts by weight of the composite plasticizer, 80 parts by weight of a filler (OMYA 10, OMIA KOREA), 100 parts by weight of a stabilizer (CZ-400, Complex of Ca (polyvinyl chloride) 5 parts by weight of a viscosity reducing agent (TXIB, manufactured by EASTMAN), 10 parts by weight of a foaming agent (ACF, manufactured by Kyo Yang Co., Ltd.), 3 parts by weight of a zeolite ≪ / RTI > Storage time was maintained for 1 hour, 1 day, 3 days, and 5 days, respectively, according to the sol viscosity measurement time.
[Example 2]
30 parts by weight of tributyl citrate and 70 parts by weight of DOTP were mixed to prepare a composite plasticizer. Then, 70 parts by weight of the composite plasticizer and 100 parts by weight of a stabilizer (for example, polyvinyl chloride CZ-400) were added and kneaded at 165 ° C for 5 minutes using a Two-Roll Mill. Thereafter, 15 MPa was added at 175 캜 for 3 minutes using a heating press, and after cooling to 90 캜 or lower, a specimen was prepared.
[Comparative Example 1]
90 parts by weight of DOTP, 80 parts by weight of a filler (OMYA 10, OMIA KOREA), a stabilizer (CZ-400, Complex of Ca-Zn organics), 100 parts by weight of a polyvinyl chloride resin (PVC resin, 5 parts by weight of a viscosity reducing agent (TXIB, EASTMAN Co., Ltd.) were added, and the mixture was mixed to prepare a sol. Then, the mixture was stored in an oven at 30 ° C Respectively. Storage time was maintained for 1 hour, 1 day, 3 days, and 5 days, respectively, according to the sol viscosity measurement time.
[Comparative Example 2]
A sol was prepared in the same manner as in Example 1 except that 30% by weight of tributyl citrate and 70% by weight of DOP were mixed to prepare a composite plasticizer, which was then stored in an oven at 30 ° C.
[Comparative Example 3]
A sol was prepared in the same manner as in Example 1, except that 50 wt% of tributyl citrate and 50 wt% of DOTP were mixed as a composite plasticizer, and the sol was stored in an oven at 30 캜.
[Comparative Example 4]
A sol was prepared in the same manner as in Example 1 except that 20% by weight of tributyl citrate and 80% by weight of DOTP were mixed as a composite plasticizer, which was then stored in an oven at 30 占 폚.
[Comparative Example 5]
A specimen was prepared in the same manner as in Example 2, except that DOTP was used as a plasticizer instead of a composite plasticizer.
[Comparative Example 6]
A specimen was prepared in the same manner as in Example 2, except that a composite plasticizer prepared by mixing 30 wt% of tributyl citrate and 70 wt% of DOP as a composite plasticizer was used.
[Comparative Example 7]
A specimen was prepared in the same manner as in Example 2, except that a complex plasticizer prepared by mixing 50 wt% of tributyl citrate and 50 wt% of DOTP (Di-2-ethylhexyl terephthalate) was used.
[Comparative Example 8]
A specimen was prepared in the same manner as in Example 2, except that a composite plasticizer prepared by mixing 20 wt% of tributyl citrate and 80 wt% of DOTP (Di-2-ethylhexyl terephthalate) was used.
(evaluation)
Performance evaluation of polymer resin composition (paste resin)
The sol viscosity was measured at 30 ° C using a Brookfield viscometer 63 spindle. As can be seen from the following Table 1, it was confirmed that Example 1 had a low initial viscosity (elapsed time of 1 hour), and thus had excellent processability and excellent viscosity stability with time. On the other hand, in Comparative Example 1, the initial viscosity was so high that the workability remarkably decreased, and in Comparative Example 2, the viscosity stability with time was degraded. In addition, the initial viscosity of Comparative Example 3 was good, but the viscosity rapidly increased with time. In Comparative Example 4, not only the initial viscosity but also the viscosity increased with time.
[Table 1]
Performance evaluation of polymer resin composition (straight resin)
The tensile strength and elongation were measured at room temperature for 168 hours in a Geer Oven at 100 ° C. The tensile strength and elongation were measured. The tensile strength was measured by tensile test The residual rate and the residual rate were calculated. The 100% modulus is the tensile strength when the material is stretched 100% by tension, which means the plasticization efficiency, and the lower the 100% modulus value, the better the plasticizing efficiency of the material.
In the tensile test after heating, the mechanical properties of the material after a certain aging condition (heat treatment) are measured, for example, the percentage of elongation is measured. The rate of change in elongation is expressed as a percentage of elongation, The mechanical properties similar to those before aging are exhibited. This property means the durability of wire compound can be maintained and used for a long time.
The volatilization loss was calculated as the ratio of the weight of the test piece before aging and the weight of the test piece after aging after the test piece was left in a Geer Oven at 100 ° C for 168 hours.
As can be seen in the following Table 2, the 100% modulus showing the plasticization efficiency was superior to the Comparative Example in Example 2. Aging properties showed better characteristics than DOP used as a general plasticizer. In Comparative Example 7, the physical properties at room temperature were somewhat satisfactory but the properties after aging (test after heating) were sharply lowered. In Comparative Example 8, no usable results were obtained at room temperature properties. In addition, the comparative examples showed that some properties were unsatisfactory in the test at room temperature and after heating. On the contrary, Example 2 shows a result that physical properties are balanced at room temperature and after heating.
The plasticizer absorption rate was measured in accordance with DIN 54802-1. At this time, 400 g of polyvinyl chloride resin (polymerization degree: 1,000) and 200 g of the plasticizer selected from Example 2 and Comparative Examples 4 to 6 were put into a bowl driven at 88 DEG C and 100 rpm. As a result, it was confirmed that the plasticizer of the composition to which tributyl citrate was added had a higher absorption rate than the plasticizer to which tributyl citrate was not added.
[Table 2]
While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, Various modifications and variations are possible in light of the above teachings.
Accordingly, the spirit of the present invention should not be construed as being limited to the embodiments described, and all of the equivalents or equivalents of the claims, as well as the following claims, belong to the scope of the present invention .
Claims (6)
Wherein the composite plasticizer composition comprises 25 to 40 wt% of tributyl citrate and 60 to 75 wt% of di-2-ethylhexyl terephthalate.
Wherein the composite plasticizer composition is contained in an amount of 30 to 120 parts by weight based on 100 parts by weight of the polymer resin.
Wherein the polymer resin is at least one selected from the group consisting of a polyvinyl chloride resin, an olefin resin, an ABS resin, an acrylic resin, and a polyester resin.
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| KR1020150038201A KR101777143B1 (en) | 2015-03-19 | 2015-03-19 | Composite plasticizer composition and polymer resin composition using the same |
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| KR1020150038201A KR101777143B1 (en) | 2015-03-19 | 2015-03-19 | Composite plasticizer composition and polymer resin composition using the same |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109503991A (en) * | 2018-11-26 | 2019-03-22 | 李美兰 | A kind of cold-proof PVC film formula |
| WO2019074300A2 (en) | 2017-10-13 | 2019-04-18 | 주식회사 엘지화학 | Plasticizer composition and resin composition comprising same |
| GB2569608A (en) * | 2017-12-21 | 2019-06-26 | Altro Ltd | Improvements in or relating to organic material |
| KR20190140398A (en) | 2018-06-11 | 2019-12-19 | 주식회사 엘지화학 | Plasticizer composition and resin composition comprising the same |
| KR20190140346A (en) | 2018-06-11 | 2019-12-19 | 주식회사 엘지화학 | Plasticizer composition and resin composition comprising the same |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3949821B2 (en) * | 1998-07-08 | 2007-07-25 | 三菱レイヨン株式会社 | Vinyl chloride resin composition |
| US8372912B2 (en) | 2005-08-12 | 2013-02-12 | Eastman Chemical Company | Polyvinyl chloride compositions |
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| CN111094419A (en) * | 2017-10-13 | 2020-05-01 | 株式会社Lg化学 | Plasticizer composition and resin composition comprising the same |
| WO2019074300A2 (en) | 2017-10-13 | 2019-04-18 | 주식회사 엘지화학 | Plasticizer composition and resin composition comprising same |
| KR20190041932A (en) | 2017-10-13 | 2019-04-23 | 주식회사 엘지화학 | Plasticizer, resin composition and method for preparing them |
| US11702529B2 (en) | 2017-10-13 | 2023-07-18 | Lg Chem, Ltd. | Plasticizer composition and resin composition including the same |
| EP3660088A4 (en) * | 2017-10-13 | 2020-07-29 | LG Chem, Ltd. | Plasticizer composition and resin composition comprising same |
| US10975222B2 (en) | 2017-12-21 | 2021-04-13 | Altro Limited | Organic material |
| EP3502175A1 (en) * | 2017-12-21 | 2019-06-26 | Altro Limited | Improvements in or relating to organic material |
| GB2569608B (en) * | 2017-12-21 | 2022-10-26 | Altro Ltd | Plasticiser composition |
| GB2569608A (en) * | 2017-12-21 | 2019-06-26 | Altro Ltd | Improvements in or relating to organic material |
| KR20190140346A (en) | 2018-06-11 | 2019-12-19 | 주식회사 엘지화학 | Plasticizer composition and resin composition comprising the same |
| KR20190140398A (en) | 2018-06-11 | 2019-12-19 | 주식회사 엘지화학 | Plasticizer composition and resin composition comprising the same |
| US11746079B2 (en) | 2018-06-11 | 2023-09-05 | Lg Chem, Ltd. | Plasticizer composition and resin composition including the same |
| US11753402B2 (en) | 2018-06-11 | 2023-09-12 | Lg Chem, Ltd. | Plasticizer composition and resin composition including the same |
| CN109503991A (en) * | 2018-11-26 | 2019-03-22 | 李美兰 | A kind of cold-proof PVC film formula |
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| KR101777143B1 (en) | 2017-09-18 |
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