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WO2019039879A2 - Composite plasticizer composition, preparation method therefor, and polymer resin composition using same - Google Patents

Composite plasticizer composition, preparation method therefor, and polymer resin composition using same Download PDF

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Publication number
WO2019039879A2
WO2019039879A2 PCT/KR2018/009705 KR2018009705W WO2019039879A2 WO 2019039879 A2 WO2019039879 A2 WO 2019039879A2 KR 2018009705 W KR2018009705 W KR 2018009705W WO 2019039879 A2 WO2019039879 A2 WO 2019039879A2
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Prior art keywords
formula
compound
weight
chemical formula
mixture
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PCT/KR2018/009705
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French (fr)
Korean (ko)
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WO2019039879A3 (en
Inventor
이종화
김영관
정종환
위성유
김장수
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애경유화 주식회사
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Priority claimed from KR1020180032488A external-priority patent/KR102108875B1/en
Application filed by 애경유화 주식회사 filed Critical 애경유화 주식회사
Publication of WO2019039879A2 publication Critical patent/WO2019039879A2/en
Publication of WO2019039879A3 publication Critical patent/WO2019039879A3/en

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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
    • 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
    • C08K5/05—Alcohols; Metal alcoholates
    • 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
    • C08K5/101—Esters; Ether-esters of monocarboxylic acids
    • 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
    • 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

Definitions

  • the present invention relates to a composite plasticizer composition, a method for producing the same, and a polymer resin composition using the same.
  • Polymer resins are used in a variety of fields such as various household goods, clothing, electric and electronic, automobile, civil engineering, and construction depending on physical properties.
  • Examples of such a polymer resin include polyethylene (PE), polypropylene (PP), polystyrene (PP), polyurethane (PU), and polyvinyl chloride (PVC).
  • the double polyvinyl chloride resin has hard or soft characteristics, is excellent in molding processability, is excellent in price competitiveness, and is applied to various applications with general utility.
  • the polyvinyl chloride resin can not be used alone, but is mixed with a plasticizer for various properties.
  • the plasticizer imparts flexibility to the polyvinyl chloride resin and improves physical properties such as processability.
  • Such a plasticizer when applied to various polymer resins including polyvinyl chloride resin, should be capable of satisfying various physical properties such as good compatibility with resins, excellent plasticization efficiency, low volatility, Depending on the characteristics required.
  • plasticizer In general, the larger the molecular weight of the plasticizer is, the better the aging resistance is, but the compatibility with the resin is lowered, and it tends to be difficult to realize various required properties in a balanced manner. Therefore, in order to meet various physical properties or limited use of plasticizers, a variety of plasticizers have been applied to promote research and development in the direction of increasing plasticization efficiency.
  • the plasticizer in the manufacturing process of applying the plasticizer to the resin or using the final product manufactured using the resin, the plasticizer should be capable of maintaining excellent physical properties at a high temperature or a low temperature at a room temperature. That is, it is required to be able to realize long-term durability, quality stability and reliability by being able to realize excellent resistance to aging in various temperature ranges including heat resistance and cold resistance.
  • An object of the present invention is to provide an environmentally friendly plasticizer composition capable of improving mechanical properties such as tensile strength and elongation as well as heat resistance, cold resistance and aging resistance, and a polymer resin composition containing the same.
  • One aspect of the present invention to attain the above object is a process for producing 2-ethyl-1-hexanol, isononyl alcohol, 2-propyl-1-heptyl alcohol (b) a phthalate derivative mixture (a) which is a reaction product of phthalic acid and a phthalic acid and a compound (b) of the following general formula (1).
  • the phthalic acid is selected from terephthalic acid and isophthalic acid
  • the phthalate derivative mixture derived therefrom is a terephthalate derivative mixture or a mixture of isophthalate derivatives.
  • R 1 to R 3 are each independently C 6 to C 12 alkyl.
  • the phthalate derivative mixture may be a mixture of terephthalate derivatives or a mixture of isophthalate derivatives represented by the following formulas (8) to (13) have.
  • the terephthalate derivative mixture may contain 1 to 40 wt% of the compound of Formula 2, 1 to 50 wt% of the compound of Formula 3, 1 to 50 wt% of the compound of Formula 4, 1 to 40% by weight of the compound of the formula (5), 1 to 40% by weight of the compound of the formula (6) and 1 to 40% by weight of the compound of the formula (7), wherein the isophthalate derivative mixture contains 1 to 40 1 to 50% by weight of the compound of the formula (9), 1 to 50% by weight of the compound of the formula (10), 1 to 40% by weight of the compound of the formula (11), 1 to 40% %. ≪ / RTI >
  • the weight ratio of the phthalate derivative mixture to the compound of Formula 1 may be 1: 9 to 9: 1.
  • R 1 to R 3 are each independently C 6 to C 12 alkyl, more preferably the alkyl is C 8 to C 10 . In the above range, it is more effective in improving the mechanical properties, heat resistance, cold resistance and aging resistance, but is not necessarily limited thereto.
  • the phthalate derivative mixture may contain 1 to 50% by weight of 2-ethyl-1-hexanol, 1 to 70% by weight of isononyl alcohol, -Heptyl alcohol and 1 to 70% by weight of heptyl alcohol with phthalic acid.
  • Another aspect of the present invention is to provide a resin composition comprising the composite plasticizer composition and the polymer resin.
  • the polymer resin may include one or more selected from the group consisting of a polyvinyl chloride resin, a polyolefin resin, a polyester resin, an ABS resin, and an acrylic resin.
  • the resin composition according to one embodiment of the present invention may further include at least one component selected from the group consisting of fillers, lubricants, stabilizers, foaming agents, viscosity regulators, processing aids and dispersants.
  • Another aspect of the present invention is to provide a molded article produced from the above resin composition.
  • the composite plasticizer composition according to the present invention is harmless to the human body and environmentally friendly, and has excellent properties in terms of mechanical properties such as tensile strength and elongation, and further has an advantage of improving heat resistance, cold resistance and aging resistance.
  • the present invention can provide excellent physical properties such as mechanical strength, heat resistance, cold resistance, aging resistance, processability, and long-term durability by mixing the composite plasticizer composition with a polymer resin, It is possible to secure the quality stability and reliability of the finished resin product.
  • " phthalic acid " in the present invention includes terephthalic acid or isophthalic acid, and a " phthalate-based derivative mixture " derived therefrom by reaction with a specific alcohol, Phthalate derivative mixture or a mixture of isophthalate derivatives.
  • the present inventors have intensified researches on plasticizers which can be applied to polymer resins such as polyvinyl chloride resins and satisfy various physical properties requirements that are increasing.
  • the inventors of the present invention have found that they are excellent in physical properties balance and are not limited to low temperature or high temperature
  • a plasticizer having excellent heat resistance, cold resistance and aging resistance has been developed.
  • a composite plasticizer composition comprising a combination of a phthalate derivative mixture, which is a reaction product of a specific component of alcohol and phthalic acid, and a specific citrate compound at the same time is superior in physical properties including synergy with heat resistance and aging resistance, And the present invention has been completed.
  • One embodiment of the present invention relates to a phthalate derivative mixture obtained from the reaction of a specific alcohol component of 2-ethyl-1-hexanol, isononyl alcohol and 2-propyl-1-heptyl alcohol with phthalic acid and a compound represented by the following formula , And to provide a polymer resin composition capable of improving various physical properties including excellent heat resistance, cold resistance and aging resistance by using the composite plasticizer composition.
  • R 1 to R 3 are each independently C 6 to C 12 alkyl.
  • the compound of the formula (1) is an ester compound of citric acid and a C 6 to C 12 alcohol. Although it is not limited theoretically, the combination of the phthalate derivative mixture improves cold resistance and heat resistance and further enhances the aging resistance at a high temperature It can be improved.
  • R 1 to R 3 each independently represent C 6 to C 12 alkyl, wherein any one of R 1 to R 3 has a long chain of C 6 to C 12 alkyl It is more effective in improving the thermal resistance of cold resistance and heat resistance without deteriorating physical properties and at the same time improving the aging resistance. That is, when all of R 1 to R 3 are simultaneously C 6 to C 12 alkyl long chains, the present invention is more effective in achieving the desired physical properties.
  • R 1 to R 3 are each independently C 8 to C 10 alkyl.
  • R 1 to R 3 are each independently C 8 to C 10 alkyl.
  • the compound represented by Formula 1 may be, for example, a trihexyl citrate, a triheptyl citrate, a triethylhexyl citrate, a triisononyl citrate, triisononyl citrate, triisodecyl citrate, tripropylheptyl citrate, tridodecyl citrate and trioctyl dodecyl citrate from the group consisting of triisononyl citrate, triisodecyl citrate, tripropylheptyl citrate, tridodecyl citrate and trioctyl dodecyl citrate. And any one or more selected, but not limited thereto.
  • At least one selected from triethyl hexylate, triisononyl citrate, triisodecyltreate, tripropylheptyl citrate, tridodecyltreate and trioctyldodecyltreate is used has an effect of further improving heat resistance, cold resistance and aging resistance when applied to a polymer resin composition.
  • the compound represented by the formula (1) may be a commercial product or an esterified product of citric acid and a C 6 to C 12 alcohol.
  • the phthalate derivative mixture may be a terephthalate derivative compound or an isophthalate derivative compound.
  • the terephthalate derivative mixture or the isophthalate derivative mixture is characterized in that different types of terephthalate derivative components or isophthalate derivative components are mixed, respectively.
  • the phthalate derivative mixture may be an isophthalate derivative comprising at least one selected from the group consisting of terephthalate derivative mixtures containing at least one of the following compounds (2) to (7) And mixtures thereof.
  • the terephthalate derivative mixture is a mixture of the above formulas 2, 3 and 5; The mixture of Formulas 3, 4, and 7; And mixtures of the above formulas (2), (4) and (6);
  • the isophthalate derivative mixture may be a mixture of the above formulas (8), (9) and (11); A mixture of the above formulas (9), (10) and (13); And a mixture of the above formulas (8), (9) and (11); , But the present invention is not limited thereto.
  • each of the compounds may be controlled within a range that achieves the desired physical properties.
  • the content of each compound may be 1 to 50 wt%, preferably 5 to 40 wt% , But are not necessarily limited thereto.
  • the terephthalate derivative mixture may comprise a combination of compounds of the following formulas 2 to 7, and the isophthalate derivative mixture may comprise a combination of compounds of formulas 8 to 13: This is because the terephthalate derivative mixture or the isophthalate derivative mixture has more effective characteristics in terms of improvement of physical properties such as workability, heat loss, heat resistance, cold resistance, aging resistance and weather resistance and balance of physical properties.
  • the terephthalate derivative mixture comprises 1 to 40% by weight of the compound of Formula 2, 1 to 50% by weight of the compound of Formula 3, 1 to 50% by weight of the compound of Formula 4, 1 to 40% by weight of the compound of the formula (6) and 1 to 40% by weight of the compound of the formula (7), wherein the isophthalate derivative mixture comprises 1 to 40% by weight of the compound of the formula 1 to 40% by weight of the compound of the formula (11) and 1 to 40% by weight of the compound of the formula (13), 1 to 50% by weight of the compound .
  • the isophthalate derivative mixture comprises 2 to 30% by weight of the compound of the formula 8, 5 to 40% by weight of the compound of the formula 9, 10 to 40% by weight of the compound of the formula 10, 5 to 30% by weight, the compound of the formula 12 is 5 to 30% by weight, and the compound of the formula 13 is 10 to 30% by weight.
  • the isophthalate derivative mixture may contain 2 to 30% by weight of the compound of Formula 8, 5 to 40% by weight of the compound of Formula 9, 10 to 40% by weight of the compound of Formula 10, 5 to 30% 5 to 30% by weight of the compound of the formula (12) and 10 to 30% by weight of the compound of the formula (13).
  • the phthalate derivative mixture may have a weight mixing ratio with the compound of Formula 1 of 1: 9 to 9: 1, preferably 2: 8 to 8: 2, more preferably 3: 7 to 7: 3 have.
  • the plasticizer applied to the polymer resin has the characteristics of being able to achieve the same level or better mechanical properties while maintaining various physical property balance and at the same time improving the aging resistance at high temperature.
  • Another embodiment of the present invention is a process for synthesizing a phthalate derivative mixture by reacting a reaction solution comprising 2-ethyl-1-hexanol, isononyl alcohol and 2-propyl-1-heptyl alcohol, terephthalic acid or phthalic acid of isophthalic acid And mixing the synthesized phthalate derivative mixture with a compound of the following general formula (1).
  • R 1 to R 3 are each independently C 6 to C 12 alkyl.
  • the phthalate derivative mixture comprises 1 to 50% by weight of 2-ethyl-1-hexanol, 1 to 70% by weight of isononyl alcohol and 1 to 70% by weight of 2-propyl- May be obtained by esterification reaction of a mixed alcohol component with any phthalic acid selected from terephthalic acid and isophthalic acid.
  • the step of synthesizing the phthalate derivative mixture is carried out by adding 0.2 to 0.5 mol of 2-ethyl-1-hexanol, 0.4 to 2 mol of isononyl alcohol to 1 mol of phthalic acid, i.e., terephthalic acid or isophthalic acid, 0.8 mol of 2-propyl-1-heptyl alcohol and 0.8 to 1.2 mol of 2-propyl-1-heptyl alcohol.
  • a mixture of terephthalate derivatives comprising a mixture of compounds of the following formulas (2) to (7) or a mixture of isophthalate derivatives of the following formulas (8) to (13) is obtained through the reaction of phthalic acid with alcohol components in the above- And has effective properties in terms of process efficiency and processability within the above-mentioned molar range, but the molar range is not limited to the above-mentioned numerical range, but is a non-limiting example.
  • the various ester compounds obtained through the esterification reaction using an acid and an alcohol as raw materials may have various properties depending on the kind of the reactants, the molar ratio, the reaction temperature, and the like.
  • the specific alcohol component according to the present invention and the molar ratios of these components The phthalate derivative components obtained according to the reaction of phthalic acid can further improve the plasticizer performance in combination with the compound of Formula 1 in the complex plasticizer composition.
  • the terephthalate derivative mixture obtained through the above-mentioned synthesis step may contain 1 to 40% by weight of the following compound (2), 1 to 50% by weight of the compound of the formula (3), 1 to 50% by weight of the compound of the formula (4) 40% by weight of the compound of the formula (6), and 1 to 40% by weight of the compound of the formula (7).
  • the isophthalate derivative mixture obtained through the above-mentioned synthesis step may contain 1 to 40% by weight of the following compound (8), 1 to 50% by weight of the compound of the formula (9), 1 to 50% by weight of the compound of the formula 1 to 40% by weight of the compound of the formula (12) and 1 to 40% by weight of the compound of the formula (13).
  • the esterification reaction of the alcohol components and the phthalic acid may be carried out under conventional esterification reaction conditions, preferably at 180 to 250 ° C for 6 to 20 hours, but is not limited thereto.
  • the weight ratio of the phthalate derivative mixture to the compound of Formula 1 may be 1: 9 to 9: 1, preferably 2: 8 to 8: 2, more preferably 3: 7 to 7: 3 .
  • the polymer resin may include at least one selected from the group consisting of a polyvinyl chloride resin, a polyolefin resin, a polyester resin, an ABS resin, and an acrylic resin, and is preferably a polyvinyl chloride Resin.
  • the polymeric resin composition according to one embodiment of the present invention includes the composite plasticizer composition of the present invention and is capable of realizing excellent physical properties at high temperature or low temperature and further improving the aging resistance at high temperature.
  • the polymer resin composition according to one embodiment of the present invention may contain 10 to 150 parts by weight, preferably 20 to 140 parts by weight, more preferably 30 to 120 parts by weight, based on 100 parts by weight of the polymer resin, of the composite plasticizer composition have.
  • the desired physical properties of the present invention are more effective in terms of improvement of heat resistance, cold resistance and aging resistance, but this is a non-limiting example and is not limited to the above numerical range.
  • the polymer resin composition may further include at least one selected from the group consisting of a secondary plasticizer, a stabilizer, a filler, a lubricant, a flame retardant, a viscosity regulator, a foaming agent, a promoter and a pigment.
  • the additive is not particularly limited, but may be added in an amount of 0.1 to 10 parts by weight, more preferably 1 to 5 parts by weight, based on 100 parts by weight of the polymer resin. Within this range, each additive can achieve the desired effect.
  • Still another aspect of the present invention is to provide a molded article produced from the above-described polymer resin composition.
  • the molded article may be a wallpaper, a compound, a wire compound, a sheet, a film, a tarpaulin, a hose, a shoe, a sealant, an office supplies, a glove, a bottle cap, a mat, a gasket, a food packaging material, , Electric machine parts, and the like.
  • the tensile strength was measured when the specimen was stretched 100% by tension. This means that the plasticization efficiency is better, and the lower the 100% modulus value, the better the plasticization efficiency of the material.
  • the specimen was aged in an oven (Geer Oven) at 113 DEG C for 168 hours, and then calculated as a value of (elongation of specimen after aging / elongation of specimen before aging) x100. At this time, when the resultant value is close to 100, it means that mechanical properties similar to those before aging are exhibited.
  • the tensile strength of the specimens was measured in accordance with KS M 3156.
  • the specimens were aged in an oven (Geer Oven) at 113 ° C for 168 hours and then calculated as the value of (weight of test piece after aging / weight of test piece before aging) ⁇ 100.
  • the resultant terephthalate derivative mixture was analyzed by a GC-Mass analyzer. As a result, it was found that the weight percentage of the terephthalate derivative mixture was 5: 10: 30: 10: 15: 30.
  • TEHC triethylhexyl citrate
  • Example 1 The same procedure was followed as in Example 1, except that the amounts of the alcohol compound components were varied in Example 1 and the proportions of the respective compounds in the terephthalate derivative mixture were changed as shown in Table 1 below.
  • Example 1 The same procedure as in Example 1 was carried out except that tributyl citrate (TBC) was used instead of triethylhexitrate in Example 1.
  • TBC tributyl citrate
  • the terephthalate derivative mixture thus obtained was analyzed by a GC-Mass analyzer. As a result, it was found that the weight percentage of the terephthalate derivative mixture was 4: 11: 25: 11: 14: 35.
  • TEHC triethylhexyl citrate
  • Example 2 The same procedure as in Example 1 was carried out except that the amounts of the alcohol compound components were varied in Example 10 and the proportions of the respective compounds in the terephthalate derivative mixture were changed as shown in Table 2 below.
  • Example 1 The procedure of Example 1 was repeated, except that tributyl citrate was used instead of triethylhexitrate in Example 10.
  • Example 1 The procedure of Example 1 was repeated, except that di (2-propylheptyl) phthalate was used instead of triethylhexitrate in Example 10.
  • Example 1 The procedure of Example 1 was repeated, except that diisodecyl phthalate (DIDP) was used instead of the composite plasticizer composition as a plasticizer in Example 19.
  • DIDP diisodecyl phthalate
  • the examples using the composite plasticizer composition in which the terephthalate derivative mixture or the isophthalate derivative mixture according to the present invention and TEHC were mixed showed excellent tensile strength and durability when compared with the commercial plasticizer DIDP It was confirmed that the mechanical properties of elongation as well as heat resistance, cold resistance and further aging resistance were remarkably improved.
  • the examples according to the present invention in the case of Comparative Examples 5 and 7 using tributyl citrate instead of triethylhexitrate or Comparative Examples 6 and 8 using a diaphthalate compound, the aging resistance was significantly lowered , And it was confirmed that heat resistance and cold resistance at high temperature were not good.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The present invention relates to an environmentally friendly composite plasticizer composition capable of improving not only mechanical properties, such as tensile strength and elongation, but also heat resistance, cold resistance, and aging resistance, to a preparation method therefor, and a polymer resin composition using the same.

Description

복합 가소제 조성물, 이의 제조방법 및 이를 이용한 고분자 수지 조성물Composite plasticizer composition, process for producing the same, and polymeric resin composition using the same
본 발명은 복합 가소제 조성물, 이의 제조방법 및 이를 이용한 고분자 수지 조성물에 관한 것이다.The present invention relates to a composite plasticizer composition, a method for producing the same, and a polymer resin composition using the same.
고분자 수지는 물성에 따라 각종 생활용품을 비롯하여 의류, 전기전자, 자동차, 토목, 건축 등 다양한 분야에 사용되고 있다. 이러한 고분자 수지로는 폴리에틸렌(PE), 폴리프로필렌(PP), 폴리스티렌(PP), 폴리우레탄(PU), 폴리염화비닐(PVC) 등이 있다.Polymer resins are used in a variety of fields such as various household goods, clothing, electric and electronic, automobile, civil engineering, and construction depending on physical properties. Examples of such a polymer resin include polyethylene (PE), polypropylene (PP), polystyrene (PP), polyurethane (PU), and polyvinyl chloride (PVC).
이중 폴리염화비닐 수지는 경질 또는 연질 특성을 가지며, 성형 가공성이 뛰어나고, 가격 경쟁력이 우수하여 범용적인 효용성으로 여러 응용분야에 적용되고 있다. 하지만, 폴리염화비닐 수지는 단독으로 사용되지 못하고, 다양한 물성 구현을 위하여 가소제와 혼합되어 사용되고 있다.The double polyvinyl chloride resin has hard or soft characteristics, is excellent in molding processability, is excellent in price competitiveness, and is applied to various applications with general utility. However, the polyvinyl chloride resin can not be used alone, but is mixed with a plasticizer for various properties.
가소제는 폴리염화비닐 수지에 유연성을 부여하고, 가공성 등의 물성을 향상시키는 역할을 한다. 이러한 가소제는 폴리염화비닐 수지를 포함하여 다양한 고분자 수지에 적용됨에 있어서, 수지와의 상용성이 좋고, 가소화 효율이 우수하며, 낮은 휘발성을 가지는 등 다양한 물성을 충족시킬 수 있어야 하며, 그 적용 분야에 요구되는 특성에 따라 다양하게 되었다.The plasticizer imparts flexibility to the polyvinyl chloride resin and improves physical properties such as processability. Such a plasticizer, when applied to various polymer resins including polyvinyl chloride resin, should be capable of satisfying various physical properties such as good compatibility with resins, excellent plasticization efficiency, low volatility, Depending on the characteristics required.
일반적으로 가소제는 분자량이 클수록 우수한 내노화성을 가지나 수지와의 상용성이 저하되는 것과 같이 다양한 요구 물성을 균형있게 구현하는 것이 쉽지 않은 경향이 있다. 이에 가소제를 사용하는데 제한적이거나 각종 물성을 충족시키기 위하여 다양한 가소제를 적용함으로써 가소화 효율을 높이는 방향으로 기술 연구개발이 진행되고 있다.In general, the larger the molecular weight of the plasticizer is, the better the aging resistance is, but the compatibility with the resin is lowered, and it tends to be difficult to realize various required properties in a balanced manner. Therefore, in order to meet various physical properties or limited use of plasticizers, a variety of plasticizers have been applied to promote research and development in the direction of increasing plasticization efficiency.
한편, 가소제를 수지에 적용하는 제조공정이나 상기 수지를 이용하여 제조된 최종 제품을 사용함에 있어서 가소제는 상온에서는 물론 고온 혹은 저온에서 우수한 물성 구현을 유지할 수 있어야 한다. 즉, 내열성, 내한성을 비롯하여 다양한 온도 영역에서 우수한 내노화성을 구현할 수 있음으로써 장기 내구성, 품질 안정성 및 신뢰성을 확보할 수 있어야 한다.On the other hand, in the manufacturing process of applying the plasticizer to the resin or using the final product manufactured using the resin, the plasticizer should be capable of maintaining excellent physical properties at a high temperature or a low temperature at a room temperature. That is, it is required to be able to realize long-term durability, quality stability and reliability by being able to realize excellent resistance to aging in various temperature ranges including heat resistance and cold resistance.
이에, 넓은 온도범위에서 우수한 물성을 유지할 수 있으며 나아가 탁월한 물성 밸런스를 구현할 수 있도록 하는 새로운 가소제에 대한 연구개발이 필요하다.Therefore, it is necessary to research and develop new plasticizers that can maintain excellent physical properties over a wide temperature range and realize excellent physical property balance.
본 발명은 인장강도, 신율 등의 기계적 물성은 물론 내열성, 내한성 및 내노화성을 향상시킬 수 있는 친환경 가소제 조성물과 이를 포함하는 고분자 수지 조성물을 제공하는 것을 목적으로 한다.An object of the present invention is to provide an environmentally friendly plasticizer composition capable of improving mechanical properties such as tensile strength and elongation as well as heat resistance, cold resistance and aging resistance, and a polymer resin composition containing the same.
상기와 같은 목적을 달성하기 위한 본 발명의 일 양태는 2-에틸-1-헥산올(2-ethyl-1-hexanol), 이소노닐 알코올(isononyl alcohol), 2-프로필-1-헵틸 알코올(2-propyl-1-heptyl alcohol) 및 프탈산(phthalic acid)의 반응물인 프탈레이트 유도체 혼합물(a) 및 하기 화학식 1의 화합물(b)을 포함하는 복합 가소제 조성물을 제공하는 것이다. 이때, 프탈산은 테레프탈산 및 이소프탈산 중에서 선택되는 것이며, 이들로부터 유도되는 프탈레이트 유도체 혼합물은 테레프탈레이트 유도체 혼합물 또는 이소프탈레이트 유도체 혼합물인 것이다.One aspect of the present invention to attain the above object is a process for producing 2-ethyl-1-hexanol, isononyl alcohol, 2-propyl-1-heptyl alcohol (b) a phthalate derivative mixture (a) which is a reaction product of phthalic acid and a phthalic acid and a compound (b) of the following general formula (1). At this time, the phthalic acid is selected from terephthalic acid and isophthalic acid, and the phthalate derivative mixture derived therefrom is a terephthalate derivative mixture or a mixture of isophthalate derivatives.
[화학식 1][Chemical Formula 1]
Figure PCTKR2018009705-appb-I000001
Figure PCTKR2018009705-appb-I000001
상기 화학식 1에서, R1 내지 R3은 각각 독립적으로 C6 내지 C12 알킬이다.In Formula 1, R 1 to R 3 are each independently C 6 to C 12 alkyl.
본 발명의 일 실시예에 따른 복합 가소제 조성물에 있어서, 상기 프탈레이트 유도체 혼합물은 하기 화학식 2 내지 7의 화합물이 혼합된 테레프탈레이트 유도체 혼합물 또는 화학식 8 내지 13의 화합물이 혼합된 이소프탈레이트 유도체 혼합물인 것일 수 있다.In the composite plasticizer composition according to an embodiment of the present invention, the phthalate derivative mixture may be a mixture of terephthalate derivatives or a mixture of isophthalate derivatives represented by the following formulas (8) to (13) have.
[화학식 2](2)
Figure PCTKR2018009705-appb-I000002
Figure PCTKR2018009705-appb-I000002
[화학식 3](3)
Figure PCTKR2018009705-appb-I000003
Figure PCTKR2018009705-appb-I000003
[화학식 4][Chemical Formula 4]
Figure PCTKR2018009705-appb-I000004
Figure PCTKR2018009705-appb-I000004
[화학식 5][Chemical Formula 5]
Figure PCTKR2018009705-appb-I000005
Figure PCTKR2018009705-appb-I000005
[화학식 6][Chemical Formula 6]
Figure PCTKR2018009705-appb-I000006
Figure PCTKR2018009705-appb-I000006
[화학식 7](7)
Figure PCTKR2018009705-appb-I000007
Figure PCTKR2018009705-appb-I000007
[화학식 8][Chemical Formula 8]
Figure PCTKR2018009705-appb-I000008
Figure PCTKR2018009705-appb-I000008
[화학식 9][Chemical Formula 9]
Figure PCTKR2018009705-appb-I000009
Figure PCTKR2018009705-appb-I000009
[화학식 10][Chemical formula 10]
Figure PCTKR2018009705-appb-I000010
Figure PCTKR2018009705-appb-I000010
[화학식 11] (11)
Figure PCTKR2018009705-appb-I000011
Figure PCTKR2018009705-appb-I000011
[화학식 12][Chemical Formula 12]
Figure PCTKR2018009705-appb-I000012
Figure PCTKR2018009705-appb-I000012
[화학식 13][Chemical Formula 13]
Figure PCTKR2018009705-appb-I000013
Figure PCTKR2018009705-appb-I000013
본 발명의 일 실시예에 따른 복합 가소제 조성물에 있어서, 상기 테레프탈레이트 유도체 혼합물은 상기 화학식 2의 화합물 1 ~ 40 중량%, 화학식 3의 화합물 1 ~ 50 중량%, 화학식 4의 화합물 1 ~ 50 중량%, 화학식 5의 화합물 1 ~ 40 중량%, 화학식 6의 화합물 1 ~ 40 중량% 및 화학식 7의 화합물 1 ~ 40 중량%를 포함하는 것이며, 상기 이소프탈레이트 유도체 혼합물은 상기 화학식 8의 화합물 1 ~ 40 중량%, 화학식 9의 화합물 1 ~ 50 중량%, 화학식 10의 화합물 1 ~ 50 중량%, 화학식 11의 화합물 1 ~ 40 중량%, 화학식 12의 화합물 1 ~ 40 중량% 및 화학식 13의 화합물 1 ~ 40 중량%를 포함하는 것일 수 있다.In the composite plasticizer composition according to one embodiment of the present invention, the terephthalate derivative mixture may contain 1 to 40 wt% of the compound of Formula 2, 1 to 50 wt% of the compound of Formula 3, 1 to 50 wt% of the compound of Formula 4, 1 to 40% by weight of the compound of the formula (5), 1 to 40% by weight of the compound of the formula (6) and 1 to 40% by weight of the compound of the formula (7), wherein the isophthalate derivative mixture contains 1 to 40 1 to 50% by weight of the compound of the formula (9), 1 to 50% by weight of the compound of the formula (10), 1 to 40% by weight of the compound of the formula (11), 1 to 40% %. ≪ / RTI >
본 발명의 일 실시예에 따른 복합 가소제 조성물에 있어서, 상기 프탈레이트 유도체 혼합물과 상기 화학식 1의 화합물의 중량비는 1:9 내지 9:1인 것일 수 있다.In the composite plasticizer composition according to an embodiment of the present invention, the weight ratio of the phthalate derivative mixture to the compound of Formula 1 may be 1: 9 to 9: 1.
본 발명의 일 실시예에 따른 복합 가소제 조성물에 있어서, 상기 화학식 1은 R1 내지 R3은 각각 독립적으로 C6 내지 C12 알킬인 것이며, 보다 바람직하게는 상기 알킬은 C8 내지 C10인 것일 수 있다. 상기 범위에서 기계적 물성은 물론 내열성, 내한성 및 내노화성 향상에 더욱 효과적이나, 반드시 이에 제한되는 것은 아니다.In the composite plasticizer composition according to one embodiment of the present invention, R 1 to R 3 are each independently C 6 to C 12 alkyl, more preferably the alkyl is C 8 to C 10 . In the above range, it is more effective in improving the mechanical properties, heat resistance, cold resistance and aging resistance, but is not necessarily limited thereto.
본 발명의 다른 양태는 2-에틸-1-헥산올, 이소노닐 알코올 및 2-프로필-1-헵틸 알코올 중에서 선택되는 어느 하나 이상의 알코올 성분과, 프탈산을 포함하는 반응용액을 반응시켜 프탈레이트 유도체 혼합물을 합성하는 단계 및 상기 합성된 프탈레이트 유도체 혼합물과 하기 화학식 1의 화합물을 혼합하는 단계를 포함하는 복합 가소제 조성물의 제조방법을 제공하는 것이다.Another embodiment of the present invention is a process for producing a phthalate derivative mixture by reacting a reaction solution containing phthalic acid with at least one alcohol component selected from 2-ethyl-1-hexanol, isononyl alcohol and 2-propyl- And then mixing the synthesized phthalate derivative mixture with a compound of the following formula (I): < EMI ID = 1.0 >
본 발명의 일 실시예에 따른 복합 가소제 조성물의 제조방법에 있어서, 상기 프탈레이트 유도체 혼합물은 2-에틸-1-헥산올 1 내지 50중량%, 이소노닐 알코올 1 내지 70중량% 및 2-프로필-1-헵틸 알코올 1 내지 70중량%를 혼합한 알코올 성분과 프탈산의 에스테르화 반응에 의해 수득되는 것일 수 있다.In the process for preparing a composite plasticizer composition according to an embodiment of the present invention, the phthalate derivative mixture may contain 1 to 50% by weight of 2-ethyl-1-hexanol, 1 to 70% by weight of isononyl alcohol, -Heptyl alcohol and 1 to 70% by weight of heptyl alcohol with phthalic acid.
본 발명의 또 다른 양태는 상기의 복합 가소제 조성물 및 고분자 수지를 포함하는 수지 조성물을 제공하는 것이다.Another aspect of the present invention is to provide a resin composition comprising the composite plasticizer composition and the polymer resin.
본 발명의 일 실시예에 따른 수지 조성물에 있어서, 상기 고분자 수지는 폴리염화비닐 수지, 폴리올레핀 수지, 폴리에스테르 수지, ABS 수지 및 아크릴 수지로 이루어진 군으로부터 선택되는 어느 하나 이상을 포함하는 것일 수 있다.In the resin composition according to an embodiment of the present invention, the polymer resin may include one or more selected from the group consisting of a polyvinyl chloride resin, a polyolefin resin, a polyester resin, an ABS resin, and an acrylic resin.
본 발명의 일 실시예에 따른 수지 조성물은 충진제, 활제, 안정제, 발포제, 점도조절제, 가공조제 및 분산제로 이루어진 군으로부터 선택되는 어느 하나 이상의 성분을 더 포함할 수 있다.The resin composition according to one embodiment of the present invention may further include at least one component selected from the group consisting of fillers, lubricants, stabilizers, foaming agents, viscosity regulators, processing aids and dispersants.
본 발명의 또 다른 양태는 상기의 수지 조성물로부터 제조된 성형품을 제공하는 것이다.Another aspect of the present invention is to provide a molded article produced from the above resin composition.
본 발명에 따른 복합 가소제 조성물은 인체에 무해하여 환경친화적이며, 인장강도, 신율 등의 기계적 물성 면에서 우수한 특성을 가지고, 나아가 내열성, 내한성 및 내노화성을 향상시킬 수 있는 장점을 가진다.The composite plasticizer composition according to the present invention is harmless to the human body and environmentally friendly, and has excellent properties in terms of mechanical properties such as tensile strength and elongation, and further has an advantage of improving heat resistance, cold resistance and aging resistance.
또한, 본 발명은 상기의 복합 가소제 조성물을 고분자 수지와 혼합하여 사용함으로써 기계적 강도, 내열성, 내한성, 내노화성, 가공성, 장기 내구성 등의 우수한 물성을 구현할 수 있으면서 이들 물성 밸런스가 탁월하며 이를 이용하여 제조된 최종 수지 제품의 품질 안정성 및 신뢰성을 확보할 수 있는 장점을 가진다.In addition, the present invention can provide excellent physical properties such as mechanical strength, heat resistance, cold resistance, aging resistance, processability, and long-term durability by mixing the composite plasticizer composition with a polymer resin, It is possible to secure the quality stability and reliability of the finished resin product.
이하 본 발명에 따른 복합 가소제 조성물, 이의 제조방법, 상기 가소제 조성물을 포함하는 고분자 수지 조성물에 대하여 상세하게 설명한다. 본 발명은 하기의 실시예에 의해 보다 더 잘 이해될 수 있으며, 하기 실시예는 본 발명의 예시 목적을 위한 것이고, 첨부된 특허청구범위에 대하여 한정되는 보호범위를 제한하고자 하는 것은 아니다. 이때, 사용되는 기술 용어 및 과학 용어는 다른 정의가 없다면, 이 발명이 속하는 기술 분야에서 통상의 지식을 가진 자가 통상적으로 이해하고 있는 의미를 가진다.Hereinafter, a composite plasticizer composition according to the present invention, a method for producing the same, and a polymer resin composition including the plasticizer composition will be described in detail. The present invention may be better understood by the following examples, which are for the purpose of illustration only and are not intended to limit the scope of protection which is defined by the appended claims. The technical terms and scientific terms used herein have the same meaning as commonly understood by those of ordinary skill in the art to which the present invention belongs, unless otherwise defined.
본 발명에서 “프탈산(phthalic acid)”은 특별한 언급이 없는 한, 테레프탈산(terephthalic acid) 또는 이소프탈산(isophthalic acid)을 포함하며, 이들로부터 특정 알코올과 반응으로 유도되는 “프탈레이트계 유도체 혼합물”은 테레프탈레이트 유도체 혼합물 또는 이소프탈레이트 유도체 혼합물을 포함하는 것을 의미한다.The term " phthalic acid " in the present invention includes terephthalic acid or isophthalic acid, and a " phthalate-based derivative mixture " derived therefrom by reaction with a specific alcohol, Phthalate derivative mixture or a mixture of isophthalate derivatives.
본 발명자들은 폴리염화비닐 수지 등의 고분자 수지에 적용되는 것으로 증대되고 있는 다양한 물성 요구를 충족시킬 수 있는 가소제에 대한 연구를 심화하던 중, 물성 밸런스가 탁월하며, 나아가 저온이나 고온에 제한되지 않고 넓은 온도 영역에서 우수한 물성을 구현할 수 있으며, 내열성, 내한성 및 내노화성이 우수한 가소제를 개발하게 되었다. 구체적으로, 특정 성분의 알코올과 프탈산의 반응물인 프탈레이트 유도체 혼합물과 동시에 특정 시트레이트계 화합물의 조합을 포함하는 복합 가소제 조성물이 종래 기계적 물성에 비하여 열세였던 내열성 및 내노화성을 포함하여 물성 상승효과에 탁월한 특성을 가지는 것을 발견하여 본 발명을 완성하게 되었다.The present inventors have intensified researches on plasticizers which can be applied to polymer resins such as polyvinyl chloride resins and satisfy various physical properties requirements that are increasing. The inventors of the present invention have found that they are excellent in physical properties balance and are not limited to low temperature or high temperature A plasticizer having excellent heat resistance, cold resistance and aging resistance has been developed. Specifically, a composite plasticizer composition comprising a combination of a phthalate derivative mixture, which is a reaction product of a specific component of alcohol and phthalic acid, and a specific citrate compound at the same time is superior in physical properties including synergy with heat resistance and aging resistance, And the present invention has been completed.
본 발명의 일 양태는 2-에틸-1-헥산올, 이소노닐 알코올 및 2-프로필-1-헵틸 알코올의 특정 알코올 성분과 프탈산의 반응으로부터 수득되는 프탈레이트 유도체 혼합물과, 하기 화학식 1로 표기되는 화합물을 포함하는 복합 가소제 조성물에 관한 것으로, 이를 사용함으로써 우수한 내열성, 내한성 및 내노화성을 포함한 다양한 물성을 향상시킬 수 있는 고분자 수지 조성물을 제공하는 것이다.One embodiment of the present invention relates to a phthalate derivative mixture obtained from the reaction of a specific alcohol component of 2-ethyl-1-hexanol, isononyl alcohol and 2-propyl-1-heptyl alcohol with phthalic acid and a compound represented by the following formula , And to provide a polymer resin composition capable of improving various physical properties including excellent heat resistance, cold resistance and aging resistance by using the composite plasticizer composition.
[화학식 1][Chemical Formula 1]
Figure PCTKR2018009705-appb-I000014
Figure PCTKR2018009705-appb-I000014
상기 화학식 1에서, R1 내지 R3은 각각 독립적으로 C6 내지 C12 알킬이다.In Formula 1, R 1 to R 3 are each independently C 6 to C 12 alkyl.
상기 화학식 1의 화합물은 시트르산과 C6 내지 C12 알코올의 에스테르 화합물로서, 이론적으로 제한되는 것은 아니나, 상기 프탈레이트 유도체 혼합물과의 조합으로 내한성 및 내열성의 특성을 향상시키며 나아가 고온에서의 내노화성을 크게 개선할 수 있는 특성을 가진다.The compound of the formula (1) is an ester compound of citric acid and a C 6 to C 12 alcohol. Although it is not limited theoretically, the combination of the phthalate derivative mixture improves cold resistance and heat resistance and further enhances the aging resistance at a high temperature It can be improved.
특히, 상기 화학식 1의 화합물에서 상기 R1 내지 R3은 각각 독립적으로 C6 내지 C12 알킬을 갖는 것을 특징으로 하며, R1 내지 R3 중 어느 하나가 C6 내지 C12 알킬의 장쇄를 갖지 않는 경우보다 물성 저하 없이 내한성, 내열성의 열적 특성을 향상시킬 수 있으면서 동시에 내노화성을 향상시킬 수 있는 측면에서 더욱 효과적이다. 즉, 상기 R1 내지 R3이 모두 동시에 C6 내지 C12 알킬의 장쇄인 경우 본 발명이 목적하는 물성을 달성하는 측면에서 더욱 효과적이다.In particular, in the compound of Formula 1, R 1 to R 3 each independently represent C 6 to C 12 alkyl, wherein any one of R 1 to R 3 has a long chain of C 6 to C 12 alkyl It is more effective in improving the thermal resistance of cold resistance and heat resistance without deteriorating physical properties and at the same time improving the aging resistance. That is, when all of R 1 to R 3 are simultaneously C 6 to C 12 alkyl long chains, the present invention is more effective in achieving the desired physical properties.
바람직하게는, 상기 화학식 1에서, 상기 R1 내지 R3은 각각 독립적으로 C8 내지 C10 알킬인 화합물을 사용하여 내노화성을 비롯하여 가소제 사용에 따른 우수한 물성을 구현할 수 있고, 가공 중이나 가공 후에 블리딩 또는 마이그레이션이 발생하는 것을 방지할 수 있으면서 동시에 우수한 내한성 및 내열성을 구현하는 측면에서 더욱 효과적이다.Preferably, in the formula (1), R 1 to R 3 are each independently C 8 to C 10 alkyl. Thus, it is possible to realize excellent physical properties such as resistance to aging and use of a plasticizer, Or migration can be prevented from occurring, and at the same time, it is more effective in terms of realizing excellent cold resistance and heat resistance.
상기 화학식 1로 표시되는 화합물은 비한정적인 일예로서, 트리헥실시트레이트(trihexyl citrate), 트리헵틸시트레이트(triheptyl citrate), 트리에틸헥실시트레이트(triethylhexyl citrate), 트리이소노닐시트레이트(triisononyl citrate), 트리이소데실시트레이트(triisodecyl citrate), 트리프로필헵틸시트레이트(tripropylheptyl citrate), 트리도데실시트레이트(tridodecyl citrate) 및 트리옥틸도데실시트레이트(trioctyl dodecyl citrate)로 이루어진 군으로부터 선택되는 어느 하나 이상을 들 수 있으며, 이에 제한되는 것은 아니다. 바람직하게는 트리에틸헥실시트레이트, 트리이소노닐시트레이트, 트리이소데실시트레이트, 트리프로필헵틸시트레이트, 트리도데실시트레이트 및 트리옥틸도데실시트레이트 중에서 선택되는 어느 하나 이상인 것을 사용하는 것이 고분자 수지 조성물에 적용 시 내열성, 내한성 및 내노화성을 더욱 향상시키는 효과를 가진다.The compound represented by Formula 1 may be, for example, a trihexyl citrate, a triheptyl citrate, a triethylhexyl citrate, a triisononyl citrate, triisononyl citrate, triisodecyl citrate, tripropylheptyl citrate, tridodecyl citrate and trioctyl dodecyl citrate from the group consisting of triisononyl citrate, triisodecyl citrate, tripropylheptyl citrate, tridodecyl citrate and trioctyl dodecyl citrate. And any one or more selected, but not limited thereto. Preferably at least one selected from triethyl hexylate, triisononyl citrate, triisodecyltreate, tripropylheptyl citrate, tridodecyltreate and trioctyldodecyltreate is used Has an effect of further improving heat resistance, cold resistance and aging resistance when applied to a polymer resin composition.
상기 화학식 1로 표시되는 화합물은 상업화된 제품을 사용하거나 시트르산과 C6 내지 C12 알코올의 에스테르화 반응으로 제조된 것을 사용할 수 있다.The compound represented by the formula (1) may be a commercial product or an esterified product of citric acid and a C 6 to C 12 alcohol.
상기 프탈레이트 유도체 혼합물은 테레프탈레이트 유도체 화합물 또는 이소프탈레이트 유도체 화합물일 수 있다. 상기 테레프탈레이트 유도체 혼합물 또는 이소프탈레이트 유도체 혼합물은 각각 상이한 종류의 테레프탈레이트 유도체 성분 또는 이소프탈레이트 유도체 성분들이 혼합된 것을 특징으로 한다.The phthalate derivative mixture may be a terephthalate derivative compound or an isophthalate derivative compound. The terephthalate derivative mixture or the isophthalate derivative mixture is characterized in that different types of terephthalate derivative components or isophthalate derivative components are mixed, respectively.
비한정적인 일예로서, 상기 프탈레이트 유도체 혼합물은 하기 화학식 2 내지 7의 화합물 중에서 선택되는 어느 하나 이상을 포함하는 테레프탈레이트 유도체 혼합물 또는 화학식 8 내지 13의 화합물 중에서 선택되는 어느 하나 이상을 포함하는 이소프탈레이트 유도체 혼합물을 포함하는 것일 수 있다. 구체적인 일 양태로, 상기 테레프탈레이트 유도체 혼합물은 상기 화학식 2, 3 및5의 혼합물; 상기 화학식 3, 4 및 7의 혼합물; 및 상기 화학식 2, 4 및 6의 혼합물; 중에서 선택되는 어느 하나일 수 있으며, 상기 이소프탈레이트 유도체 혼합물은 상기 화학식 8, 9 및11의 혼합물; 상기 화학식 9, 10 및 13의 혼합물; 및 상기 화학식 8, 9 및 11의 혼합물; 중에서 선택되는 어느 하나일 수 있으나, 반드시 이에 제한되는 것은 아니다. 이때, 상기 각 화합물은 목적하는 물성을 달성할 수 있는 범위 내에서 조절될 수 있으며, 구체적으로 각 화합물의 함량 범위가 1 내지 50중량%, 바람직하게는 5 내지 40중량%인 것을 포함할 수 있으나, 반드시 이에 제한되는 것은 아니다.As a non-limiting example, the phthalate derivative mixture may be an isophthalate derivative comprising at least one selected from the group consisting of terephthalate derivative mixtures containing at least one of the following compounds (2) to (7) And mixtures thereof. In a specific embodiment, the terephthalate derivative mixture is a mixture of the above formulas 2, 3 and 5; The mixture of Formulas 3, 4, and 7; And mixtures of the above formulas (2), (4) and (6); And the isophthalate derivative mixture may be a mixture of the above formulas (8), (9) and (11); A mixture of the above formulas (9), (10) and (13); And a mixture of the above formulas (8), (9) and (11); , But the present invention is not limited thereto. At this time, each of the compounds may be controlled within a range that achieves the desired physical properties. Specifically, the content of each compound may be 1 to 50 wt%, preferably 5 to 40 wt% , But are not necessarily limited thereto.
다른 양태로서, 상기 테레프탈레이트 유도체 혼합물은 하기 화학식 2 내지 7의 화합물의 조합을 포함하는 것일 수 있으며, 상기 이소프탈레이트 유도체 혼합물은 화학식 8 내지 13의 화합물의 조합을 포함하는 것일 수 있다. 이는 테레프탈레이트 유도체 혼합물 또는 이소프탈레이트 유도체 혼합물 각각이 어느 하나의 단독 성분으로 이루어지는 것보다 가공성, 가열감량, 내열성, 내한성, 내노화성 및 내후성 등의 물성 향상 및 물성 밸런스 구현 측면에서 더욱 효과적인 특성을 가진다.In another embodiment, the terephthalate derivative mixture may comprise a combination of compounds of the following formulas 2 to 7, and the isophthalate derivative mixture may comprise a combination of compounds of formulas 8 to 13: This is because the terephthalate derivative mixture or the isophthalate derivative mixture has more effective characteristics in terms of improvement of physical properties such as workability, heat loss, heat resistance, cold resistance, aging resistance and weather resistance and balance of physical properties.
[화학식 2](2)
Figure PCTKR2018009705-appb-I000015
Figure PCTKR2018009705-appb-I000015
[화학식 3](3)
Figure PCTKR2018009705-appb-I000016
Figure PCTKR2018009705-appb-I000016
[화학식 4][Chemical Formula 4]
Figure PCTKR2018009705-appb-I000017
Figure PCTKR2018009705-appb-I000017
[화학식 5][Chemical Formula 5]
Figure PCTKR2018009705-appb-I000018
Figure PCTKR2018009705-appb-I000018
[화학식 6][Chemical Formula 6]
Figure PCTKR2018009705-appb-I000019
Figure PCTKR2018009705-appb-I000019
[화학식 7](7)
Figure PCTKR2018009705-appb-I000020
Figure PCTKR2018009705-appb-I000020
[화학식 8][Chemical Formula 8]
Figure PCTKR2018009705-appb-I000021
Figure PCTKR2018009705-appb-I000021
[화학식 9][Chemical Formula 9]
Figure PCTKR2018009705-appb-I000022
Figure PCTKR2018009705-appb-I000022
[화학식 10][Chemical formula 10]
Figure PCTKR2018009705-appb-I000023
Figure PCTKR2018009705-appb-I000023
[화학식 11](11)
Figure PCTKR2018009705-appb-I000024
Figure PCTKR2018009705-appb-I000024
[화학식 12][Chemical Formula 12]
Figure PCTKR2018009705-appb-I000025
Figure PCTKR2018009705-appb-I000025
[화학식 13][Chemical Formula 13]
Figure PCTKR2018009705-appb-I000026
Figure PCTKR2018009705-appb-I000026
본 발명의 바람직한 일 양태에 따르면, 상기 테레프탈레이트 유도체 혼합물은 상기 화학식 2의 화합물 1 ~ 40 중량%, 화학식 3의 화합물 1 ~ 50 중량%, 화학식 4의 화합물 1 ~ 50 중량%, 화학식 5의 화합물 1 ~ 40 중량%, 화학식 6의 화합물 1 ~ 40 중량% 및 화학식 7의 화합물 1 ~ 40 중량%를 포함하는 것이며, 상기 이소프탈레이트 유도체 혼합물은 상기 화학식 8의 화합물 1 ~ 40 중량%, 화학식 9의 화합물 1 ~ 50 중량%, 화학식 10의 화합물 1 ~ 50 중량%, 화학식 11의 화합물 1 ~ 40 중량%, 화학식 12의 화합물 1 ~ 40 중량% 및 화학식 13의 화합물 1 ~ 40 중량%를 포함하는 것일 수 있다.According to a preferred embodiment of the present invention, the terephthalate derivative mixture comprises 1 to 40% by weight of the compound of Formula 2, 1 to 50% by weight of the compound of Formula 3, 1 to 50% by weight of the compound of Formula 4, 1 to 40% by weight of the compound of the formula (6) and 1 to 40% by weight of the compound of the formula (7), wherein the isophthalate derivative mixture comprises 1 to 40% by weight of the compound of the formula 1 to 40% by weight of the compound of the formula (11) and 1 to 40% by weight of the compound of the formula (13), 1 to 50% by weight of the compound .
보다 바람직한 일 양태로서, 상기 이소프탈레이트 유도체 혼합물은 상기 화학식 8의 화합물이 2 ~ 30 중량%, 화학식 9의 화합물이 5 ~ 40 중량%, 화학식 10의 화합물이 10 ~ 40 중량%, 화학식 11의 화합물이 5 ~ 30 중량%, 화학식 12의 화합물이 5 ~ 30 중량% 및 화학식 13의 화합물이 10 ~ 30 중량%인 것일 수 있다. 또한, 상기 이소프탈레이트 유도체 혼합물은 상기 화학식 8의 화합물이 2 ~ 30 중량%, 화학식 9의 화합물이 5 ~ 40 중량%, 화학식 10의 화합물이 10 ~ 40 중량%, 화학식 11의 화합물이 5 ~ 30 중량%, 화학식 12의 화합물이 5 ~ 30 중량% 및 화학식 13의 화합물이 10 ~ 30 중량%인 것일 수 있다.In a more preferred embodiment, the isophthalate derivative mixture comprises 2 to 30% by weight of the compound of the formula 8, 5 to 40% by weight of the compound of the formula 9, 10 to 40% by weight of the compound of the formula 10, 5 to 30% by weight, the compound of the formula 12 is 5 to 30% by weight, and the compound of the formula 13 is 10 to 30% by weight. The isophthalate derivative mixture may contain 2 to 30% by weight of the compound of Formula 8, 5 to 40% by weight of the compound of Formula 9, 10 to 40% by weight of the compound of Formula 10, 5 to 30% 5 to 30% by weight of the compound of the formula (12) and 10 to 30% by weight of the compound of the formula (13).
상기 범위에서 인장강도, 신장률, 모듈러스, 휘발 감량 등의 물성 측면에서 우수한 효과를 나타내는 것과 동시에 물성 밸런스를 구현할 수 있고, 상기 화학식 1의 화합물과의 조합에 의해 내열성, 내한성의 특성을 가지며, 상온을 포함하여 넓은 온도 범위에서의 가소화 효율을 극대화하는 면에서 효과적이다.In the above range, excellent effects are exhibited in terms of physical properties such as tensile strength, elongation, modulus, and volatilization loss, and at the same time, balance of physical properties can be realized. The combination of the compound of Formula 1 with heat and cold resistance, Which is effective in maximizing the plasticizing efficiency over a wide temperature range.
나아가, 상기 프탈레이트 유도체 혼합물은 상기 화학식 1의 화합물과의 중량혼합비가 1:9 내지 9:1, 바람직하게는 2:8 내지 8:2, 보다 바람직하게는 3:7 내지 7:3인 것일 수 있다. 상기 범위에서 고분자 수지에 적용되는 가소제에 비하여 다양한 물성 밸런스를 유지하면서 동일 수준 또는 보다 우수한 기계적 물성을 구현하면서 동시에 고온에서의 내노화성을 향상시킬 수 있는 특성을 가지나, 이는 비한정적인 일 예일 뿐 상기 수치범위에 제한받지 않는다.Further, the phthalate derivative mixture may have a weight mixing ratio with the compound of Formula 1 of 1: 9 to 9: 1, preferably 2: 8 to 8: 2, more preferably 3: 7 to 7: 3 have. In the above range, the plasticizer applied to the polymer resin has the characteristics of being able to achieve the same level or better mechanical properties while maintaining various physical property balance and at the same time improving the aging resistance at high temperature. However, It is not limited by the numerical range.
본 발명의 다른 일 양태는 2-에틸-1-헥산올, 이소노닐 알코올 및 2-프로필-1-헵틸 알코올, 테레프탈산 또는 이소프탈산의 프탈산을 포함하는 반응용액을 반응시켜 프탈레이트 유도체 혼합물을 합성하는 단계 및 상기 합성된 프탈레이트 유도체 혼합물과 하기 화학식 1의 화합물을 혼합하는 단계를 포함하는 복합 가소제 조성물의 제조방법에 관한 것이다.Another embodiment of the present invention is a process for synthesizing a phthalate derivative mixture by reacting a reaction solution comprising 2-ethyl-1-hexanol, isononyl alcohol and 2-propyl-1-heptyl alcohol, terephthalic acid or phthalic acid of isophthalic acid And mixing the synthesized phthalate derivative mixture with a compound of the following general formula (1).
[화학식 1][Chemical Formula 1]
Figure PCTKR2018009705-appb-I000027
Figure PCTKR2018009705-appb-I000027
상기 화학식 1에서, R1 내지 R3은 각각 독립적으로 C6 내지 C12 알킬이다.In the above formula (1), R 1 to R 3 are each independently C 6 to C 12 alkyl.
본 발명의 일 양태에 따르면, 상기 프탈레이트 유도체 혼합물은 2-에틸-1-헥산올 1 내지 50중량%, 이소노닐 알코올 1 내지 70중량% 및 2-프로필-1-헵틸 알코올 1 내지 70중량%를 혼합한 알코올 성분과 테레프탈산 및 이소프탈산 중에서 선택되는 어느 하나의 프탈산의 에스테르화 반응에 의해 수득되는 것일 수 있다.According to one embodiment of the present invention, the phthalate derivative mixture comprises 1 to 50% by weight of 2-ethyl-1-hexanol, 1 to 70% by weight of isononyl alcohol and 1 to 70% by weight of 2-propyl- May be obtained by esterification reaction of a mixed alcohol component with any phthalic acid selected from terephthalic acid and isophthalic acid.
본 발명의 일 양태에 따르면, 상기 프탈레이트 유도체 혼합물을 합성하는 단계는 프탈산, 즉 테레프탈산 또는 이소프탈산 1몰(mol)에 대하여, 2-에틸-1-헥산올 0.2 ~ 0.5몰, 이소노닐 알코올 0.4 ~ 0.8몰 및 2-프로필-1-헵틸 알코올 0.8 ~ 1.2몰을 에스테르화 반응시켜 제조될 수 있다. 상기 몰 범위의 알코올 성분들을 사용하여 프탈산의 반응을 통해 하기 화학식 2 내지 화학식 7의 화합물의 혼합물을 포함하는 테레프탈레이트 유도체 혼합물 또는 하기 화학식 8 내지 화학식 13의 화합물의 혼합물을 포함하는 이소프탈레이트 유도체 혼합물을 수득할 수 있으며, 상기 몰 범위 내에서 공정 효율 및 가공성 측면에서 효과적인 특성을 가지나, 상기 몰 범위는 비한정적인 일예일 뿐 상기 수치범위에 제한받지 않는다.According to one embodiment of the present invention, the step of synthesizing the phthalate derivative mixture is carried out by adding 0.2 to 0.5 mol of 2-ethyl-1-hexanol, 0.4 to 2 mol of isononyl alcohol to 1 mol of phthalic acid, i.e., terephthalic acid or isophthalic acid, 0.8 mol of 2-propyl-1-heptyl alcohol and 0.8 to 1.2 mol of 2-propyl-1-heptyl alcohol. A mixture of terephthalate derivatives comprising a mixture of compounds of the following formulas (2) to (7) or a mixture of isophthalate derivatives of the following formulas (8) to (13) is obtained through the reaction of phthalic acid with alcohol components in the above- And has effective properties in terms of process efficiency and processability within the above-mentioned molar range, but the molar range is not limited to the above-mentioned numerical range, but is a non-limiting example.
산과 알코올을 원료로 하여 에스테르화 반응을 통해 수득되는 다양한 에스테르 화합물은 반응물의 종류, 몰비, 반응온도 등의 조건에 의해 여러가지 성질들을 가질 수 있는데, 본 발명에 따른 특정 알코올 성분 및 이들 성분들의 몰비들을 포함하여 프탈산의 반응에 따라 수득되는 프탈레이트 유도체 성분들은 복합 가소제 조성물 내에서 상기 화학식 1의 화합물과의 조합으로 가소제 성능을 더욱 향상시킬 수 있는 것이다.The various ester compounds obtained through the esterification reaction using an acid and an alcohol as raw materials may have various properties depending on the kind of the reactants, the molar ratio, the reaction temperature, and the like. The specific alcohol component according to the present invention and the molar ratios of these components The phthalate derivative components obtained according to the reaction of phthalic acid can further improve the plasticizer performance in combination with the compound of Formula 1 in the complex plasticizer composition.
상기 합성 단계를 통해 수득되는 테레프탈레이트 유도체 혼합물은 하기의 화학식 2의 화합물 1 ~ 40 중량%, 화학식 3의 화합물 1 ~ 50 중량%, 화학식 4의 화합물 1 ~ 50 중량%, 화학식 5의 화합물 1 ~ 40 중량%, 화학식 6의 화합물 1 ~ 40 중량% 및 화학식 7의 화합물 1 ~ 40 중량%를 포함하는 것일 수 있다.The terephthalate derivative mixture obtained through the above-mentioned synthesis step may contain 1 to 40% by weight of the following compound (2), 1 to 50% by weight of the compound of the formula (3), 1 to 50% by weight of the compound of the formula (4) 40% by weight of the compound of the formula (6), and 1 to 40% by weight of the compound of the formula (7).
[화학식 2](2)
Figure PCTKR2018009705-appb-I000028
Figure PCTKR2018009705-appb-I000028
[화학식 3](3)
Figure PCTKR2018009705-appb-I000029
Figure PCTKR2018009705-appb-I000029
[화학식 4][Chemical Formula 4]
Figure PCTKR2018009705-appb-I000030
Figure PCTKR2018009705-appb-I000030
[화학식 5][Chemical Formula 5]
Figure PCTKR2018009705-appb-I000031
Figure PCTKR2018009705-appb-I000031
[화학식 6][Chemical Formula 6]
Figure PCTKR2018009705-appb-I000032
Figure PCTKR2018009705-appb-I000032
[화학식 7](7)
Figure PCTKR2018009705-appb-I000033
Figure PCTKR2018009705-appb-I000033
또한, 상기 합성 단계를 통해 수득되는 이소프탈레이트 유도체 혼합물은 하기의 화학식 8의 화합물 1 ~ 40 중량%, 화학식 9의 화합물 1 ~ 50 중량%, 화학식 10의 화합물 1 ~ 50 중량%, 화학식 11의 화합물 1 ~ 40 중량%, 화학식 12의 화합물 1 ~ 40 중량% 및 화학식 13의 화합물 1 ~ 40 중량%를 포함하는 것일 수 있다.Also, the isophthalate derivative mixture obtained through the above-mentioned synthesis step may contain 1 to 40% by weight of the following compound (8), 1 to 50% by weight of the compound of the formula (9), 1 to 50% by weight of the compound of the formula 1 to 40% by weight of the compound of the formula (12) and 1 to 40% by weight of the compound of the formula (13).
[화학식 8][Chemical Formula 8]
Figure PCTKR2018009705-appb-I000034
Figure PCTKR2018009705-appb-I000034
[화학식 9][Chemical Formula 9]
Figure PCTKR2018009705-appb-I000035
Figure PCTKR2018009705-appb-I000035
[화학식 10][Chemical formula 10]
Figure PCTKR2018009705-appb-I000036
Figure PCTKR2018009705-appb-I000036
[화학식 11](11)
Figure PCTKR2018009705-appb-I000037
Figure PCTKR2018009705-appb-I000037
[화학식 12][Chemical Formula 12]
Figure PCTKR2018009705-appb-I000038
Figure PCTKR2018009705-appb-I000038
[화학식 13][Chemical Formula 13]
Figure PCTKR2018009705-appb-I000039
Figure PCTKR2018009705-appb-I000039
상기 알코올 성분들과 프탈산의 에스테르화 반응은 통상적인 에스테르화 반응 조건으로 실시될 수 있으며, 바람직하게는 180 내지 250℃에서 6 내지 20시간 동안 실시될 수 있으며, 이에 제한되는 것은 아니다. The esterification reaction of the alcohol components and the phthalic acid may be carried out under conventional esterification reaction conditions, preferably at 180 to 250 ° C for 6 to 20 hours, but is not limited thereto.
다음으로, 합성된 프탈레이트 유도체 혼합물을 상기 화학식 1의 화합물과 혼합하는 단계를 실시한다. 이때, 상기 프탈레이트 유도체 혼합물과 상기 화학식 1의 화합물의 중량혼합비는 1:9 내지 9:1, 바람직하게는 2:8 내지 8:2, 보다 바람직하게는3:7 내지 7:3인 것일 수 있다. 상기 범위를 만족하는 경우 기계적 물성은 물론 내한성, 고온에서의 내열성 및 내노화성을 향상시키는 측면에서 더욱 효과적이나, 이는 비한정적인 일 예일 뿐 상기 수치범위에 제한받지 않는다.Next, a step of mixing the synthesized phthalate derivative mixture with the compound of Formula 1 is carried out. The weight ratio of the phthalate derivative mixture to the compound of Formula 1 may be 1: 9 to 9: 1, preferably 2: 8 to 8: 2, more preferably 3: 7 to 7: 3 . When the above range is satisfied, it is more effective in terms of improving the cold resistance, the heat resistance at high temperature and the aging resistance as well as the mechanical properties, but this is a non-limiting example and is not limited to the above numerical range.
본 발명의 또 다른 양태는 상술한 복합 가소제 조성물 및 고분자 수지를 포함하는 고분자 수지 조성물을 제공하는 것이다. 이때, 상기 고분자 수지는 크게 제한되는 것은 아니지만, 폴리염화비닐 수지, 폴리올레핀 수지, 폴리에스테르 수지, ABS 수지 및 아크릴 수지로 이루어진 군으로부터 선택되는 어느 하나 이상을 포함할 수 있으며, 바람직하게는 폴리염화비닐 수지일 수 있다.Another aspect of the present invention is to provide a composite resin composition comprising the composite plasticizer composition described above and a polymer resin composition. The polymer resin may include at least one selected from the group consisting of a polyvinyl chloride resin, a polyolefin resin, a polyester resin, an ABS resin, and an acrylic resin, and is preferably a polyvinyl chloride Resin.
본 발명의 일 구현예에 따른 고분자 수지 조성물은 특성의 복합 가소제 조성물을 포함하여 고온 혹은 저온에서 우수한 물성 구현이 가능할 뿐만 아니라 고온에서의 내노화성을 더욱 향상된 특성을 가진다.The polymeric resin composition according to one embodiment of the present invention includes the composite plasticizer composition of the present invention and is capable of realizing excellent physical properties at high temperature or low temperature and further improving the aging resistance at high temperature.
본 발명의 일 구현예에 따른 고분자 수지 조성물은 상기 복합 가소제 조성물이 고분자 수지 100중량부에 대하여 10 내지 150중량부, 바람직하게는 20 내지 140중량부, 보다 바람직하게는 30 내지 120중량부 포함될 수 있다. 상기 범위를 만족하는 경우, 발명의 목적하는 물성 구현은 물론 내열성, 내한성 및 내노화성 향상 측면에서 더욱 효과적이나, 이는 비 한정적인 일예일 뿐 상기 수치범위에 제한받지 않는다.The polymer resin composition according to one embodiment of the present invention may contain 10 to 150 parts by weight, preferably 20 to 140 parts by weight, more preferably 30 to 120 parts by weight, based on 100 parts by weight of the polymer resin, of the composite plasticizer composition have. When the above range is satisfied, the desired physical properties of the present invention are more effective in terms of improvement of heat resistance, cold resistance and aging resistance, but this is a non-limiting example and is not limited to the above numerical range.
또한, 상기 고분자 수지 조성물은 필요에 따라, 2차 가소제, 안정제, 충진제, 활제, 난연제, 점도조절제, 발포제, 증진제 및 안료 등에서 선택된 어느 하나 또는 둘 이상의 첨가제를 더 포함할 수 있다. 첨가제는 특별히 한정하는 것은 아니나, 고분자 수지 100 중량부에 대하여 0.1 ~ 10 중량부로 첨가될 수 있으며, 보다 좋게는 1 ~ 5 중량부로 첨가될 수 있다. 상기 범위에서 각 첨가제가 목적하는 효과를 달성할 수 있다.The polymer resin composition may further include at least one selected from the group consisting of a secondary plasticizer, a stabilizer, a filler, a lubricant, a flame retardant, a viscosity regulator, a foaming agent, a promoter and a pigment. The additive is not particularly limited, but may be added in an amount of 0.1 to 10 parts by weight, more preferably 1 to 5 parts by weight, based on 100 parts by weight of the polymer resin. Within this range, each additive can achieve the desired effect.
또한, 본 발명의 또 다른 양태는 상술한 고분자 수지 조성물로부터 제조된 성형품을 제공하는 것이다. 구체적으로, 상기 성형품은 벽지, 컴파운드, 전선 컴파운드, 시트, 필름, 타포린, 호스, 신발, 실란트, 사무용품, 장갑, 병마개, 매트, 가스켓, 식품포장재, 의료용품, 자동차용품, 장난감, 유아용품, 바닥재, 전기기계 부품 등, 다양하게 사용될 수 있다.Still another aspect of the present invention is to provide a molded article produced from the above-described polymer resin composition. Specifically, the molded article may be a wallpaper, a compound, a wire compound, a sheet, a film, a tarpaulin, a hose, a shoe, a sealant, an office supplies, a glove, a bottle cap, a mat, a gasket, a food packaging material, , Electric machine parts, and the like.
이하, 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자가 용이하게 실시할 수 있도록 본 발명의 실시예에 대하여 상세히 설명한다. 그러나 본 발명은 여러 가지 상이한 형태로 구현될 수 있으며 여기에서 설명하는 실시예에 한정되지 않는다.Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily carry out the present invention. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.
(평가)(evaluation)
(1) 인장강도(kgf/㎟) 및 신율(%)(1) Tensile strength (kgf / mm 2) and elongation (%)
KS M 3156의 규정에 의거하여 측정하였다.Measured according to the provisions of KS M 3156.
(2) 100% 모듈러스(kgf/㎟)(2) 100% modulus (kgf / mm 2)
시편이 인장에 의해 100% 신장될 때의 인장강도를 측정하였다. 이는 가소화 효율을 의미하고, 100% 모듈러스 값이 낮을수록 재료의 가소화 효율이 우수하다고 판단한다.The tensile strength was measured when the specimen was stretched 100% by tension. This means that the plasticization efficiency is better, and the lower the 100% modulus value, the better the plasticization efficiency of the material.
(3) 신장 잔율(%)(3) Renal survival rate (%)
시편을 113℃의 오븐(Geer Oven)에서 168 시간 동안 노화시킨 후, (노화 후 시험편 신장강도/노화 전 시험편 신장강도)×100의 값으로 산출하였다. 이때, 결과값이 100에 가까운 값인 경우 노화 전과 유사한 기계적 물성을 나타내는 것을 의미한다. 시험편의 신장강도는 KS M 3156 준하여 시행하였다.The specimen was aged in an oven (Geer Oven) at 113 DEG C for 168 hours, and then calculated as a value of (elongation of specimen after aging / elongation of specimen before aging) x100. At this time, when the resultant value is close to 100, it means that mechanical properties similar to those before aging are exhibited. The tensile strength of the specimens was measured in accordance with KS M 3156.
(4) 내한성(4) Cold resistance
시편을 JIS K6723의 시험법에 의거하여 Brittleness를 측정하였다.Brittleness was measured for the specimen in accordance with the test method of JIS K6723.
(5) 휘발감량(중량%)(5) Volatilization loss (% by weight)
시편을 113℃의 오븐(Geer Oven)에서 168 시간 동안 노화시킨 후, (노화 후 시험편 무게/노화 전 시험편 무게)×100의 값으로 산출하였다.The specimens were aged in an oven (Geer Oven) at 113 ° C for 168 hours and then calculated as the value of (weight of test piece after aging / weight of test piece before aging) × 100.
(실시예 1)(Example 1)
2-에틸-1-헥산올 158g, 이소노닐 알코올 263g, 2-프로필-1-헵틸 알코올 481g 및 테레프탈산 389g을 240℃에서 18시간 에스테르화 반응하였다.158 g of 2-ethyl-1-hexanol, 263 g of isononyl alcohol, 481 g of 2-propyl-1-heptyl alcohol and 389 g of terephthalic acid were subjected to esterification at 240 DEG C for 18 hours.
반응 종료 후, 정제하여 하기 화학식 2의 화합물 내지 화학식 7의 화합물이 혼합된 테레프탈레이트 유도체 혼합물을 수득하였다.After completion of the reaction, the mixture was purified to obtain a terephthalate derivative mixture in which the compound of the following formula (2) to the compound of the formula (7) were mixed.
[화학식 2](2)
Figure PCTKR2018009705-appb-I000040
Figure PCTKR2018009705-appb-I000040
[화학식 3](3)
Figure PCTKR2018009705-appb-I000041
Figure PCTKR2018009705-appb-I000041
[화학식 4][Chemical Formula 4]
Figure PCTKR2018009705-appb-I000042
Figure PCTKR2018009705-appb-I000042
[화학식 5][Chemical Formula 5]
Figure PCTKR2018009705-appb-I000043
Figure PCTKR2018009705-appb-I000043
[화학식 6][Chemical Formula 6]
Figure PCTKR2018009705-appb-I000044
Figure PCTKR2018009705-appb-I000044
[화학식 7](7)
Figure PCTKR2018009705-appb-I000045
Figure PCTKR2018009705-appb-I000045
수득된 테레프탈레이트 유도체 혼합물을 GC-Mass 분석기로 분석한 결과, 테레프탈레이트 유도체 혼합물 총 중량에 대하여, 화학식 2: 화학식 3: 화학식 4: 화학식 5: 화학식 6: 화학식 7의 중량%가 5: 10: 30: 10: 15: 30인 것을 확인하였다.The resultant terephthalate derivative mixture was analyzed by a GC-Mass analyzer. As a result, it was found that the weight percentage of the terephthalate derivative mixture was 5: 10: 30: 10: 15: 30.
다음으로, 수득된 테레프탈레이트 유도체 혼합물 30 중량부에 대하여 트리에틸헥실시트레이트(TEHC, Triethylhexyl citrate) 70중량부를 혼합하여 복합 가소제 조성물을 제조하였다.Next, 70 parts by weight of triethylhexyl citrate (TEHC) was mixed with 30 parts by weight of the obtained terephthalate derivative mixture to prepare a composite plasticizer composition.
(실시예 2 내지 9)(Examples 2 to 9)
실시예 1에서 알코올 화합물 성분들의 첨가량을 달리하여 테레프탈레이트 유도체 혼합물 내 각 화합물의 성분비를 하기 표 1과 같이 달리한 것을 제외하고는 실시예 1과 동일한 방법으로 실시하였다.The same procedure was followed as in Example 1, except that the amounts of the alcohol compound components were varied in Example 1 and the proportions of the respective compounds in the terephthalate derivative mixture were changed as shown in Table 1 below.
(비교예 1)(Comparative Example 1)
실시예 1에서 트리에틸헥실시트레이트 대신에 트리부틸시트레이트(TBC, Tributyl citrate)를 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 실시하였다.The same procedure as in Example 1 was carried out except that tributyl citrate (TBC) was used instead of triethylhexitrate in Example 1.
(비교예 2)(Comparative Example 2)
실시예 1에서 트리에틸헥실시트레이트 대신에 디(2-프로필헵틸) 프탈레이트(DPHP, Di(2-propylheptyl) phthalate) 를 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 실시하였다.Except that di (2-propylheptyl) phthalate (DPHP, Di (2-propylheptyl) phthalate) was used instead of triethylhexyltracetate in Example 1.
[표 1][Table 1]
Figure PCTKR2018009705-appb-I000046
Figure PCTKR2018009705-appb-I000046
(실시예 10)(Example 10)
2-에틸-1-헥산올 158g, 이소노닐 알코올 263g, 2-프로필-1-헵틸 알코올 481g 및 이소프탈산 389g을 240℃에서 18시간 에스테르화 반응하였다.158 g of 2-ethyl-1-hexanol, 263 g of isononyl alcohol, 481 g of 2-propyl-1-heptyl alcohol and 389 g of isophthalic acid were subjected to an esterification reaction at 240 DEG C for 18 hours.
반응 종료 후, 정제하여 하기 화학식 8의 화합물 내지 화학식 13의 화합물이 혼합된 테레프탈레이트 유도체 혼합물을 수득하였다.After completion of the reaction, the reaction mixture was purified to obtain a mixture of terephthalate derivatives having the following general formula (8) to (13).
[화학식 8][Chemical Formula 8]
Figure PCTKR2018009705-appb-I000047
Figure PCTKR2018009705-appb-I000047
[화학식 9][Chemical Formula 9]
Figure PCTKR2018009705-appb-I000048
Figure PCTKR2018009705-appb-I000048
[화학식 10][Chemical formula 10]
Figure PCTKR2018009705-appb-I000049
Figure PCTKR2018009705-appb-I000049
[화학식 11](11)
Figure PCTKR2018009705-appb-I000050
Figure PCTKR2018009705-appb-I000050
[화학식 12][Chemical Formula 12]
Figure PCTKR2018009705-appb-I000051
Figure PCTKR2018009705-appb-I000051
[화학식 13][Chemical Formula 13]
Figure PCTKR2018009705-appb-I000052
Figure PCTKR2018009705-appb-I000052
수득된 테레프탈레이트 유도체 혼합물을 GC-Mass 분석기로 분석한 결과, 테레프탈레이트 유도체 혼합물 총 중량에 대하여, 화학식 8: 화학식 9: 화학식 10: 화학식 11: 화학식 12: 화학식 13의 중량%가 4: 11: 25: 11: 14: 35인 것을 확인하였다.The terephthalate derivative mixture thus obtained was analyzed by a GC-Mass analyzer. As a result, it was found that the weight percentage of the terephthalate derivative mixture was 4: 11: 25: 11: 14: 35.
다음으로, 수득된 테레프탈레이트 유도체 혼합물 30 중량부에 대하여 트리에틸헥실시트레이트(TEHC, Triethylhexyl citrate) 70중량부를 혼합하여 복합 가소제 조성물을 제조하였다.Next, 70 parts by weight of triethylhexyl citrate (TEHC) was mixed with 30 parts by weight of the obtained terephthalate derivative mixture to prepare a composite plasticizer composition.
(실시예 11 내지 실시예 18)(Examples 11 to 18)
실시예 10에서 알코올 화합물 성분들의 첨가량을 달리하여 테레프탈레이트 유도체 혼합물 내 각 화합물의 성분비를 하기 표 2와 같이 달리한 것을 제외하고는 실시예 1과 동일한 방법으로 실시하였다.The same procedure as in Example 1 was carried out except that the amounts of the alcohol compound components were varied in Example 10 and the proportions of the respective compounds in the terephthalate derivative mixture were changed as shown in Table 2 below.
(비교예 3)(Comparative Example 3)
실시예 10에서 트리에틸헥실시트레이트 대신에 트리부틸시트레이트를 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 실시하였다.The procedure of Example 1 was repeated, except that tributyl citrate was used instead of triethylhexitrate in Example 10.
(비교예 4)(Comparative Example 4)
실시예 10에서 트리에틸헥실시트레이트 대신에 디(2-프로필헵틸) 프탈레이트를 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 실시하였다.The procedure of Example 1 was repeated, except that di (2-propylheptyl) phthalate was used instead of triethylhexitrate in Example 10.
[표 2][Table 2]
Figure PCTKR2018009705-appb-I000053
Figure PCTKR2018009705-appb-I000053
(실시예 19 내지 36 및 비교예 5 내지 8)(Examples 19 to 36 and Comparative Examples 5 to 8)
폴리염화비닐수지(PVC(paste resin), 중합도 1,000) 100 중량부에 대하여, 앞서 실시예 1 내지 36 및 비교예 1 내지 4에서 제조한 복합 가소제 조성물 70 중량부 및 안정제(CZ-400, Complex of Ca-Zn organics, 송원산업) 2.5 중량부를 각각 첨가하고, 이를 Two-Roll Mill을 이용하여 170℃에서 5분 동안 혼련하였다. 이후, 열프레스(Heating Press)를 이용하여 175℃에서 3분 동안 15 MPa의 압력을 가하고, 90℃ 이하로 냉각한 후, 시편을 제작하였다. 시편의 물성을 측정하여 그 값을 하기 표 3 및 표 4에 기재하였다.70 parts by weight of the composite plasticizer composition prepared in Examples 1 to 36 and Comparative Examples 1 to 4 and 100 parts by weight of a stabilizer (CZ-400, Complex of 1000 parts) were added to 100 parts by weight of a polyvinyl chloride resin (PVC resin Ca-Zn organics, Songwon Industries, Ltd.) were added, and the mixture was kneaded at 170 ° C for 5 minutes using a Two-Roll Mill. Thereafter, a pressure of 15 MPa was applied at 175 캜 for 3 minutes using a heating press, and after cooling to 90 캜 or lower, a specimen was prepared. The properties of the specimens were measured and the values thereof are shown in Tables 3 and 4 below.
(비교예 9)(Comparative Example 9)
실시예 19에서 가소제로 복합 가소제 조성물을 사용하는 대신에 디이소데실 프탈레이트 (DIDP, Diisodecyl phthalate)를 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 실시하였다. The procedure of Example 1 was repeated, except that diisodecyl phthalate (DIDP) was used instead of the composite plasticizer composition as a plasticizer in Example 19.
[표 3][Table 3]
Figure PCTKR2018009705-appb-I000054
Figure PCTKR2018009705-appb-I000054
[표 4][Table 4]
Figure PCTKR2018009705-appb-I000055
Figure PCTKR2018009705-appb-I000055
상기 표 3 및 4에서 볼 수 있는 바와 같이, 본 발명에 따른 테레프탈레이트 유도체 혼합물 또는 이소프탈레이트 유도체 혼합물과, TEHC를 혼합한 복합 가소제 조성물을 사용한 실시예들은 상용 가소제인 DIDP와 비교 시 우수한 인장강도 및 신율의 기계적 물성은 물론 내열성, 내한성, 나아가 내노화성 특성이 현저히 향상되었음을 확인할 수 있었다. 반면, 본 발명에 따른 실시예에서 트리에틸헥실시트레이트 대신에, 트리부틸시트레이트를 사용한 비교예 5 및 7 또는 디이프탈레이트계 화합물을 혼합한 비교예 6 및 8의 경우는 내노화성이 현저히 저하되었고, 고온에서의 내열성과 내한성이 좋지 않게 나타남을 확인하였다.As can be seen from Tables 3 and 4, the examples using the composite plasticizer composition in which the terephthalate derivative mixture or the isophthalate derivative mixture according to the present invention and TEHC were mixed showed excellent tensile strength and durability when compared with the commercial plasticizer DIDP It was confirmed that the mechanical properties of elongation as well as heat resistance, cold resistance and further aging resistance were remarkably improved. On the other hand, in the examples according to the present invention, in the case of Comparative Examples 5 and 7 using tributyl citrate instead of triethylhexitrate or Comparative Examples 6 and 8 using a diaphthalate compound, the aging resistance was significantly lowered , And it was confirmed that heat resistance and cold resistance at high temperature were not good.
이상과 같이 특정된 사항들과 한정된 실시예를 통해 본 발명이 설명되었으나, 이는 본 발명의 보다 전반적인 이해를 돕기 위해서 제공된 것일 뿐, 본 발명은 상기의 실시예에 한정되는 것은 아니며, 본 발명이 속하는 분야에서 통상의 지식을 가진 자라면 이러한 기재로부터 다양한 수정 및 변형이 가능하다.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 exemplary embodiments, but, on the contrary, Various modifications and variations may be made thereto by those skilled in the art.
따라서, 본 발명의 사상은 설명된 실시예에 국한되어 정해져서는 아니되며, 후술하는 특허청구범위뿐 아니라 이 특허청구범위와 균등하거나 등가적 변형이 있는 모든 것들은 본 발명 사상의 범주에 속한다고 할 것이다.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 (11)

  1. 2-에틸-1-헥산올, 이소노닐 알코올, 2-프로필-1-헵틸 알코올 및 프탈산의 반응물인 프탈레이트 유도체 혼합물 및 하기 화학식 1의 화합물을 포함하는 복합 가소제 조성물.A mixture of a phthalate derivative which is a reaction product of 2-ethyl-1-hexanol, isononyl alcohol, 2-propyl-1-heptyl alcohol and phthalic acid and a compound represented by the following general formula (1).
    [화학식 1][Chemical Formula 1]
    Figure PCTKR2018009705-appb-I000056
    Figure PCTKR2018009705-appb-I000056
    (상기 화학식 1에서, R1 내지 R3은 각각 독립적으로 C6 내지 C12 알킬이다.)(Wherein R 1 to R 3 are each independently C 6 to C 12 alkyl).
  2. 제1항에 있어서,The method according to claim 1,
    상기 프탈레이트 유도체 혼합물은 하기 화학식 2 내지 7의 화합물이 혼합된 테레프탈레이트 유도체 혼합물 또는 화학식 8 내지 13의 화합물이 혼합된 이소프탈레이트 유도체 혼합물인 복합 가소제 조성물.Wherein the phthalate derivative mixture is a terephthalate derivative mixture or a mixture of isophthalate derivatives represented by the following general formulas (2) to (7) or a mixture of isophthalate derivatives represented by general formulas (8) to (13).
    [화학식 2](2)
    Figure PCTKR2018009705-appb-I000057
    Figure PCTKR2018009705-appb-I000057
    [화학식 3](3)
    Figure PCTKR2018009705-appb-I000058
    Figure PCTKR2018009705-appb-I000058
    [화학식 4][Chemical Formula 4]
    Figure PCTKR2018009705-appb-I000059
    Figure PCTKR2018009705-appb-I000059
    [화학식 5][Chemical Formula 5]
    Figure PCTKR2018009705-appb-I000060
    Figure PCTKR2018009705-appb-I000060
    [화학식 6][Chemical Formula 6]
    Figure PCTKR2018009705-appb-I000061
    Figure PCTKR2018009705-appb-I000061
    [화학식 7](7)
    Figure PCTKR2018009705-appb-I000062
    Figure PCTKR2018009705-appb-I000062
    [화학식 8][Chemical Formula 8]
    Figure PCTKR2018009705-appb-I000063
    Figure PCTKR2018009705-appb-I000063
    [화학식 9][Chemical Formula 9]
    Figure PCTKR2018009705-appb-I000064
    Figure PCTKR2018009705-appb-I000064
    [화학식 10][Chemical formula 10]
    Figure PCTKR2018009705-appb-I000065
    Figure PCTKR2018009705-appb-I000065
    [화학식 11] (11)
    Figure PCTKR2018009705-appb-I000066
    Figure PCTKR2018009705-appb-I000066
    [화학식 12][Chemical Formula 12]
    Figure PCTKR2018009705-appb-I000067
    Figure PCTKR2018009705-appb-I000067
    [화학식 13][Chemical Formula 13]
    Figure PCTKR2018009705-appb-I000068
    Figure PCTKR2018009705-appb-I000068
  3. 제2항에 있어서,3. The method of claim 2,
    상기 테레프탈레이트 유도체 혼합물은 상기 화학식 2의 화합물 1 ~ 40 중량%, 화학식 3의 화합물 1 ~ 50 중량%, 화학식 4의 화합물 1 ~ 50 중량%, 화학식 5의 화합물 1 ~ 40 중량%, 화학식 6의 화합물 1 ~ 40 중량% 및 화학식 7의 화합물 1 ~ 40 중량%를 포함하는 것이며,Wherein the terephthalate derivative mixture comprises 1 to 40 wt% of the compound of Formula 2, 1 to 50 wt% of the compound of Formula 3, 1 to 50 wt% of the compound of Formula 4, 1 to 40 wt% of the compound of Formula 5, 1 to 40% by weight of the compound and 1 to 40% by weight of the compound of the formula (7)
    상기 이소프탈레이트 유도체 혼합물은 상기 화학식 8의 화합물 1 ~ 40 중량%, 화학식 9의 화합물 1 ~ 50 중량%, 화학식 10의 화합물 1 ~ 50 중량%, 화학식 11의 화합물 1 ~ 40 중량%, 화학식 12의 화합물 1 ~ 40 중량% 및 화학식 13의 화합물 1 ~ 40 중량%를 포함하는 복합 가소제 조성물.The isophthalate derivative mixture may contain 1 to 40% by weight of the compound of Formula 8, 1 to 50% by weight of the compound of Formula 9, 1 to 50% by weight of the compound of Formula 10, 1 to 40% by weight of the compound of Formula 11, 1 to 40% by weight of the compound and 1 to 40% by weight of the compound of the formula (13).
  4. 제1항에 있어서,The method according to claim 1,
    상기 프탈레이트 유도체 혼합물과 상기 화학식 1의 화합물의 중량비는 1:9 내지 9:1인 복합 가소제 조성물.Wherein the weight ratio of the phthalate derivative mixture to the compound of Formula 1 is from 1: 9 to 9: 1.
  5. 제1항에 있어서,The method according to claim 1,
    상기 화학식 1은 R1 내지 R3은 각각 독립적으로 C8 내지 C10 알킬인 복합 가소제 조성물. Wherein R 1 to R 3 are each independently C 8 to C 10 alkyl.
  6. 2-에틸-1-헥산올, 이소노닐 알코올, 2-프로필-1-헵틸 알코올 및 프탈산을 포함하는 반응용액을 반응시켜 프탈레이트 유도체 혼합물을 합성하는 단계 및Reacting a reaction solution containing 2-ethyl-1-hexanol, isononyl alcohol, 2-propyl-1-heptyl alcohol and phthalic acid to synthesize a phthalate derivative mixture; and
    상기 합성된 프탈레이트 유도체 혼합물과 하기 화학식 1의 화합물을 혼합하는 단계Mixing the synthesized phthalate derivative mixture with a compound of the following formula 1
    를 포함하는 복합 가소제 조성물의 제조방법.≪ / RTI >
    [화학식 1][Chemical Formula 1]
    Figure PCTKR2018009705-appb-I000069
    Figure PCTKR2018009705-appb-I000069
    (상기 화학식 1에서, R1 내지 R3은 각각 독립적으로 C6 내지 C12 알킬이다.)(Wherein R 1 to R 3 are each independently C 6 to C 12 alkyl).
  7. 제6항에 있어서,The method according to claim 6,
    상기 프탈레이트 유도체 혼합물은 2-에틸-1-헥산올 1 내지 50중량%, 이소노닐 알코올 1 내지 70중량% 및 2-프로필-1-헵틸 알코올 1 내지 70중량%를 혼합한 알코올 성분과 프탈산의 에스테르화 반응에 의해 수득되는 것인 복합 가소제 조성물의 제조방법. Wherein the phthalate derivative mixture is an ester of an alcohol component and phthalic acid mixed with 1 to 50 wt% of 2-ethyl-1-hexanol, 1 to 70 wt% of isonoyl alcohol and 1 to 70 wt% of 2-propyl- By weight of the total weight of the composition.
  8. 제1항 내지 제5항 중에서 선택되는 어느 한 항의 복합 가소제 조성물 및 고분자 수지를 포함하는 수지 조성물.A resin composition comprising a composite plasticizer composition according to any one of claims 1 to 5 and a polymeric resin.
  9. 제8항에 있어서,9. The method of claim 8,
    상기 고분자 수지는 폴리염화비닐 수지, 폴리올레핀 수지, 폴리에스테르 수지, ABS 수지 및 아크릴 수지로 이루어진 군으로부터 선택되는 어느 하나 이상을 포함하는 수지 조성물.Wherein the polymer resin comprises at least one selected from the group consisting of a polyvinyl chloride resin, a polyolefin resin, a polyester resin, an ABS resin, and an acrylic resin.
  10. 제8항에 있어서,9. The method of claim 8,
    상기 수지 조성물은 충진제, 활제, 안정제, 발포제, 점도조절제, 가공조제 및 분산제로 이루어진 군으로부터 선택되는 어느 하나 이상의 성분을 더 포함하는 수지 조성물.Wherein the resin composition further comprises at least one component selected from the group consisting of a filler, a lubricant, a stabilizer, a foaming agent, a viscosity adjusting agent, a processing aid and a dispersing agent.
  11. 제8항의 수지 조성물로부터 제조된 성형품.A molded article produced from the resin composition of claim 8.
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CN103788406A (en) * 2014-02-11 2014-05-14 汤宁 Biological environment-friendly plasticizer capable of completely replacing dioctyl-phthalate (DOP)
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CN113692425A (en) * 2019-05-02 2021-11-23 株式会社Lg化学 Plasticizer composition and resin composition comprising the same
EP3964543A4 (en) * 2019-05-02 2022-06-22 Lg Chem, Ltd. Plasticizer composition and resin composition comprising same
CN113692425B (en) * 2019-05-02 2023-06-30 株式会社Lg化学 Plasticizer composition and resin composition comprising the same
TWI825312B (en) * 2019-05-02 2023-12-11 南韓商Ｌｇ化學股份有限公司 Plasticizer composition and resin composition including the same

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