KR102108875B1 - Composite plasticizer composition, and method for preparing the same, and polymer resin composition using the same - Google Patents

Abstract

The present invention relates to a composite plasticizer composition, a method for manufacturing the same, and a polymer resin composition using the same.

Description

Composite plasticizer composition, method for manufacturing same, and polymer resin composition using same {Composite plasticizer composition, and method for preparing the same, and polymer resin composition using the same}

The present invention relates to a composite plasticizer composition, a method for manufacturing the same, and a polymer resin composition using the same.

Polymer resins are used in various fields such as clothing, electrical and electronics, automobiles, civil engineering, and construction, as well as various household goods depending on their physical properties. Examples of the polymer resin include polyethylene (PE), polypropylene (PP), polystyrene (PP), polyurethane (PU), and polyvinyl chloride (PVC).

Among them, polyvinyl chloride resin has hard or soft properties, has excellent molding processability, and has excellent price competitiveness, and has been applied to various applications with general-purpose utility. However, the polyvinyl chloride resin is not used alone, and is used in combination with a plasticizer for realizing various properties.

The plasticizer imparts flexibility to the polyvinyl chloride resin and serves to improve physical properties such as processability. Since these plasticizers are applied to various polymer resins, including polyvinyl chloride resins, they must be able to meet various physical properties such as good compatibility with resins, excellent plasticization efficiency, and low volatility. It was varied according to the characteristics required for.

In general, the larger the molecular weight, the better the aging resistance, but tends to be difficult to implement various required properties in a balanced manner, such as lower compatibility with resins. Accordingly, the use of plasticizers is limited, or technology research and development is progressing in the direction of increasing plasticization efficiency by applying various plasticizers to satisfy various properties.

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 able to maintain excellent physical properties at high temperature or low temperature as well as at room temperature. That is, it should be possible to secure long-term durability, quality stability, and reliability by being able to implement excellent aging resistance in various temperature ranges, including heat resistance and cold resistance.

Accordingly, it is necessary to research and develop new plasticizers capable of maintaining excellent physical properties in a wide temperature range and further realizing excellent physical property balance.

Korean Patent Publication No. 10-2015-0042159 (2015.04.20)

An object of the present invention is to provide an environmentally friendly plasticizer composition capable of improving heat resistance, cold resistance and aging resistance as well as mechanical properties such as tensile strength and elongation, and a polymer resin composition containing the same.

One aspect of the present invention for achieving the above object is 2-ethyl-1-hexanol (2-ethyl-1-hexanol), isononyl alcohol (isononyl alcohol), 2-propyl-1-heptyl alcohol (2 It is to provide a composite plasticizer composition comprising a mixture of a phthalate derivative (a) which is a reactant of -propyl-1-heptyl alcohol) and phthalic acid (a) and a compound (b) of Formula 1 below. 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 an isophthalate derivative mixture.

[Formula 1]

In Formula 1, R ₁ to R ₃ are each independently C ₆ to C ₁₂ alkyl.

In the composite plasticizer composition according to an embodiment of the present invention, the phthalate derivative mixture may be a terephthalate derivative mixture in which the compounds of Formulas 2 to 7 are mixed or an isophthalate derivative mixture in which the compounds of Formulas 8 to 13 are mixed. have.

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

 [Formula 11]

[Formula 12]

[Formula 13]

In the composite plasticizer composition according to an embodiment of the present invention, the terephthalate derivative mixture is 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 , Compound 1 to 40% by weight of Formula 5, Compound 1 to 40% by weight of Formula 6 and Compound 1 to 40% by weight of Formula 7, and the isophthalate derivative mixture is Compound 1 to 40% by weight of Formula 8 %, Compound 1-50 wt% of Formula 9, Compound 1-50 wt% of Formula 10, Compound 1-40 wt% of Formula 11, Compound 1-40 wt% of Formula 12 and Compound 1-40 wt% of Formula 13 %.

In the composite plasticizer composition according to an embodiment of the present invention, the weight ratio of the phthalate derivative mixture and the compound of Formula 1 may be 1: 9 to 9: 1.

In the composite plasticizer composition according to an embodiment of the present invention, in Chemical Formula 1, R ₁ to R ₃ are each independently C ₆ to C ₁₂ alkyl, and more preferably, the alkyl is C ₈ to C ₁₀ . Can be. Mechanical properties in the above range, of course, are more effective in improving heat resistance, cold resistance and aging resistance, but are not limited thereto.

In another aspect of the present invention, a mixture of phthalate derivatives is reacted 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-1-heptyl alcohol. It provides a method for producing a composite plasticizer composition comprising the step of synthesizing and mixing the compound of Formula 1 with the synthesized phthalate derivative mixture.

In the method for preparing the composite plasticizer composition according to an embodiment of the present invention, the phthalate derivative mixture is 2-ethyl-1-hexanol 1 to 50% by weight, isononyl alcohol 1 to 70% by weight and 2-propyl-1 -Heptyl alcohol 1 to 70% by weight may be obtained by the esterification reaction of an alcohol component and phthalic acid.

Another aspect of the present invention is to provide a resin composition comprising the composite plasticizer composition and the polymer resin.

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 polyvinyl chloride resin, polyolefin resin, polyester resin, ABS resin and acrylic resin.

The resin composition according to an embodiment of the present invention may further include any one or more components selected from the group consisting of fillers, lubricants, stabilizers, blowing agents, viscosity modifiers, processing aids, and dispersants.

Another aspect of the present invention is to provide a molded article made from the above resin composition.

The composite plasticizer composition according to the present invention is harmless to the human body and is environmentally friendly, has excellent properties in terms of mechanical properties such as tensile strength and elongation, and further has the advantage of improving heat resistance, cold resistance and aging resistance.

In addition, the present invention is excellent in the balance of these physical properties while being able to realize excellent physical properties such as mechanical strength, heat resistance, cold resistance, aging resistance, processability, long-term durability, etc. It has the advantage of ensuring the quality stability and reliability of the final resin product.

Hereinafter, a composite plasticizer composition according to the present invention, a method for manufacturing the same, and a polymer resin composition including the plasticizer composition will be described in detail. The present invention can be better understood by the following examples, the following examples are for illustrative purposes of the present invention, and are not intended to limit the protection scope defined with respect to the appended claims. At this time, the technical terms and scientific terms used have a meaning that is generally understood by those of ordinary skill in the technical field to which this invention belongs, unless otherwise defined.

In the present invention, "phthalic acid (phthalic acid)", unless otherwise specified, terephthalic acid (terephthalic acid) or isophthalic acid (isophthalic acid), from which "phthalate-based derivative mixture" derived from the reaction with a specific alcohol is tere It is meant to include phthalate derivative mixtures or isophthalate derivative mixtures.

The present inventors are deepening research on plasticizers capable of meeting various physical property demands that are being applied to polymer resins such as polyvinyl chloride resins, and have excellent physical property balance, and are not limited to low or high temperatures. It is possible to realize excellent physical properties in the temperature range, and to develop a plasticizer having excellent heat resistance, cold resistance and aging resistance. Specifically, the composite plasticizer composition comprising a combination of a specific component of an alcohol and a phthalic acid derivative of a phthalic acid and a specific citrate-based compound at the same time is excellent in synergistic properties, including heat resistance and aging resistance, which were inferior to conventional mechanical properties. The present invention was completed by discovering that it has properties.

One aspect of the present invention is a mixture of a phthalate derivative obtained from the reaction of phthalic acid with a specific alcohol component of 2-ethyl-1-hexanol, isononyl alcohol and 2-propyl-1-heptyl alcohol, and a compound represented by the following formula (1) It relates to a composite plasticizer composition comprising a, by using it to provide a polymer resin composition capable of improving various physical properties including excellent heat resistance, cold resistance and aging resistance.

[Formula 1]

In Formula 1, R ₁ to R ₃ are each independently C ₆ to C ₁₂ alkyl.

The compound of Formula 1 is an ester compound of citric acid and a C ₆ to C ₁₂ alcohol, but is not limited in theory, but in combination with the phthalate derivative mixture, improves the properties of cold resistance and heat resistance, and further increases aging resistance at high temperatures. It has characteristics that can be improved.

In particular, in the compound of Formula 1, R ₁ to R ₃ are each characterized by independently having C ₆ to C ₁₂ alkyl, and any one of R ₁ to R ₃ does not have a long chain of C ₆ to C ₁₂ alkyl It is more effective in terms of being able to improve the thermal properties of cold resistance and heat resistance without deteriorating physical properties than at the same time, while simultaneously improving aging resistance. That is, when R ₁ to R ₃ are both C ₆ to C ₁₂ alkyl long chains at the same time, the present invention is more effective in achieving the desired physical properties.

Preferably, in Chemical Formula 1, the R ₁ to R ₃ may independently implement C ₈ to C ₁₀ alkyl, and thus may exhibit excellent physical properties according to plasticizer use, including aging resistance, and bleeding during or after processing. Or it is more effective in terms of realizing excellent cold resistance and heat resistance while simultaneously preventing migration from occurring.

The compound represented by Formula 1 is a non-limiting example, trihexyl citrate, triheptyl citrate, triethylhexyl citrate, triisononyl citrate ( from the group consisting of triisononyl citrate, triisodecyl citrate, tripropylheptyl citrate, tridodecyl citrate and trioctyl dodecyl citrate Any one or more selected may be mentioned, but is not limited thereto. Preferably, at least one selected from triethylhexyl citrate, triisononyl citrate, triisodecyl citrate, tripropylheptyl citrate, tridodecyl citrate and trioctyldodecyl cate is used. When applied to the polymer resin composition, it has an effect of further improving heat resistance, cold resistance and aging resistance.

The compound represented by Chemical Formula 1 may be a commercial product or a product prepared by esterification of citric acid and C ₆ to C ₁₂ alcohol.

The phthalate derivative mixture may be a terephthalate derivative compound or an isophthalate derivative compound. Each of the terephthalate derivative mixture or the isophthalate derivative mixture is characterized by mixing different types of terephthalate derivative components or isophthalate derivative components.

As a non-limiting example, the phthalate derivative mixture is a terephthalate derivative mixture comprising any one or more selected from compounds of Formulas 2 to 7 or an isophthalate derivative comprising any one or more selected from compounds of Formulas 8 to 13 It may be a mixture containing. In a specific embodiment, the terephthalate derivative mixture is a mixture of Formulas 2, 3 and 5; Mixtures of formulas 3, 4 and 7 above; And mixtures of Chemical Formulas 2, 4 and 6; It may be any one selected from, the isophthalate derivative mixture is a mixture of Formulas 8, 9 and 11; Mixtures of formulas 9, 10 and 13 above; And mixtures of formulas 8, 9 and 11 above; It may be any one selected from, but is not necessarily limited to. At this time, each of the compounds may be adjusted within a range that can achieve the desired physical properties, specifically, the content range of each compound may include 1 to 50% by weight, preferably 5 to 40% by weight, However, it is not necessarily limited thereto.

In another embodiment, the terephthalate derivative mixture may be a combination of compounds of Formulas 2 to 7 below, and the isophthalate derivative mixture may be a combination of compounds of Formulas 8 to 13. This has more effective properties in terms of improving physical properties such as processability, heat loss, heat resistance, cold resistance, aging resistance and weatherability, and realizing physical properties of the balance of the terephthalate derivative mixture or the isophthalate derivative mixture, respectively.

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

 [Formula 11]

[Formula 12]

[Formula 13]

According to one preferred embodiment of the invention, the terephthalate derivative mixture is 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, the compound of Formula 5 1 to 40% by weight, 1 to 40% by weight of the compound of Formula 6 and 1 to 40% by weight of the compound of Formula 7, and the isophthalate derivative mixture is 1 to 40% by weight of the compound of Formula 8 and 9 Compound 1 to 50% by weight, compound 10 to 50% by weight of compound 10, compound 1 to 40% by weight of compound 11, compound 1 to 40% by weight of compound 12 and compound 1 to 40% by weight of compound 13 Can be.

In a more preferred embodiment, the isophthalate derivative mixture includes 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, and the compound of Formula 11 The 5 to 30% by weight, the compound of Formula 12 may be 5 to 30% by weight, and the compound of Formula 13 may be 10 to 30% by weight. In addition, the isophthalate derivative mixture is 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 of the compound of Formula 11 Weight%, the compound of Formula 12 may be 5 to 30% by weight and the compound of Formula 13 may be 10 to 30% by weight.

In the above range, while exhibiting excellent effects in terms of physical properties such as tensile strength, elongation, modulus, volatilization loss, and the like, a physical property balance can be realized, and by combining with the compound of Chemical Formula 1, it has properties of heat resistance and cold resistance, and room temperature. It is effective in maximizing plasticizing efficiency over a wide temperature range.

Furthermore, the phthalate derivative mixture may have a weight mixing ratio with the compound of Formula 1 in the range of 1: 9 to 9: 1, preferably 2: 8 to 8: 2, and more preferably 3: 7 to 7: 3. have. The plasticizer applied to the polymer resin in the above range has the property of improving the aging resistance at high temperature while realizing the same level or better mechanical properties while maintaining various physical properties balance, but this is only a non-limiting example. It is not limited by the numerical range.

Another aspect of the present invention is to synthesize a phthalate derivative mixture by reacting a reaction solution containing 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 the compound of Formula 1 below.

[Formula 1]

In Formula 1, R ₁ to R ₃ are each independently C ₆ to C ₁₂ alkyl.

According to one aspect of the invention, the phthalate derivative mixture is 2-ethyl-1-hexanol 1 to 50% by weight, isononyl alcohol 1 to 70% by weight and 2-propyl-1-heptyl alcohol 1 to 70% by weight It may be obtained by an esterification reaction of a mixed alcohol component with any one of phthalic acid selected from terephthalic acid and isophthalic acid.

According to one aspect of the invention, the step of synthesizing the phthalate derivative mixture is based on phthalic acid, that is, terephthalic acid or isophthalic acid 1 mol (mol), 2-ethyl-1-hexanol 0.2 to 0.5 mol, isononyl alcohol 0.4 to It can be prepared by esterification reaction of 0.8 mol and 0.8 mol of 2-propyl-1-heptyl alcohol. A terephthalate derivative mixture comprising a mixture of compounds of Formulas 2 to 7 or an isophthalate derivative mixture comprising a mixture of compounds of Formulas 8 to 13 through the reaction of phthalic acid using the alcohol components in the molar range: It can be obtained, and has effective properties in terms of process efficiency and processability within the molar range, but the molar range is only one non-limiting example and is not limited by the numerical range.

Various ester compounds obtained through an esterification reaction using an acid and an alcohol as a raw material may have various properties depending on conditions such as the type of reactants, molar ratio, reaction temperature, etc., and specific alcohol components according to the present invention and molar ratios of these components Including the phthalate derivative components obtained according to the reaction of phthalic acid, it is possible to further improve the plasticizer performance in combination with the compound of Formula 1 in the composite plasticizer composition.

The terephthalate derivative mixture obtained through the above synthesis step is 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 50% of the compound of Formula 5 40% by weight, it may be to include a compound of 1 to 40% by weight of Formula 6 and 1 to 40% by weight of Compound of Formula 7.

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

In addition, the isophthalate derivative mixture obtained through the above synthesis step is 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, and the compound of Formula 11 It may be 1 to 40% by weight, 1 to 40% by weight of the compound of Formula 12 and 1 to 40% by weight of the compound of Formula 13.

[Formula 8]

[Formula 9]

[Formula 10]

 [Formula 11]

[Formula 12]

[Formula 13]

The esterification reaction of the alcohol components and 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.

Next, a step of mixing the synthesized phthalate derivative mixture with the compound of Formula 1 is performed. At this time, the weight mixing ratio of the phthalate derivative mixture and 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. . If the above range is satisfied, it is more effective in terms of improving the mechanical properties as well as the cold resistance, heat resistance and aging resistance at high temperatures, but this is only a non-limiting example and is not limited by the numerical range.

Another aspect of the present invention is to provide a polymer resin composition comprising the above-described composite plasticizer composition and a polymer resin. At this time, the polymer resin is not particularly limited, but may include any one or more selected from the group consisting of polyvinyl chloride resin, polyolefin resin, polyester resin, ABS resin and acrylic resin, preferably polyvinyl chloride It can be resin.

The polymer resin composition according to one embodiment of the present invention includes a composite plasticizer composition having properties, and not only enables excellent physical properties at high or low temperatures, but also has improved properties of aging resistance at high temperatures.

In the polymer resin composition according to the embodiment of the present invention, the composite plasticizer composition may include 10 to 150 parts by weight, preferably 20 to 140 parts by weight, and more preferably 30 to 120 parts by weight based on 100 parts by weight of the polymer resin. have. When the above range is satisfied, it is more effective in terms of improving the heat resistance, cold resistance and aging resistance as well as implementing the desired physical properties of the present invention, but this is only a non-limiting example and is not limited to the above numerical range.

In addition, the polymer resin composition may further include any one or more additives selected from secondary plasticizers, stabilizers, fillers, lubricants, flame retardants, viscosity modifiers, blowing agents, enhancers, and pigments, if necessary. The additive is not particularly limited, and may be added in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the polymer resin, and more preferably 1 to 5 parts by weight. Each additive in the above range can achieve the desired effect.

In addition, another aspect of the present invention is to provide a molded article prepared from the polymer resin composition described above. Specifically, the molded article is wallpaper, compound, wire compound, sheet, film, tarpaulin, hose, shoes, sealant, office supplies, gloves, bottle caps, mats, gaskets, food packaging materials, medical supplies, automobile products, toys, baby products, flooring , Electric machine parts, etc. can be used in various ways.

Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art to which the present invention pertains can easily practice. However, the present invention can be implemented in many different forms and is not limited to the embodiments described herein.

(evaluation)

(1) Tensile strength (kgf / ㎟) and elongation (%)

It was measured according to the provisions of KS M 3156.

(2) 100% modulus (kgf / ㎟)

Tensile strength when the specimen was stretched 100% by tensile was measured. This means plasticizing efficiency, and it is judged that the lower the 100% modulus value, the better the plasticizing efficiency of the material.

(3) Elongation residual rate (%)

After the specimen was aged for 168 hours in an oven (Geer Oven) at 113 ° C., it was calculated as a value of Х100 (Elongation strength of test piece after aging / Strength of test piece before aging). At this time, when the result value is close to 100, it means that it exhibits similar mechanical properties as before aging. The tensile strength of the test piece was performed according to KS M 3156.

(4) Cold resistance

Brittleness of the specimen was measured according to the test method of JIS K6723.

(5) Volatile loss (% by weight)

After the specimen was aged for 168 hours in an oven at 113 ° C. (Geer Oven), it was calculated as the value of Х100 (weight of specimen after aging / weight of specimen before aging).

(Example 1)

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 esterified at 240 ° C. for 18 hours.

After completion of the reaction, purification was carried out to obtain a terephthalate derivative mixture in which the compounds of Formula 2 to the compound of Formula 7 are mixed.

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

As a result of analyzing the obtained terephthalate derivative mixture with a GC-Mass analyzer, based on the total weight of the terephthalate derivative mixture, Formula 2: Formula 3: Formula 4: Formula 5: Formula 6: The weight percent of Formula 7 is 5:10: It was confirmed that it was 30: 10: 15: 30.

Next, a composite plasticizer composition was prepared by mixing 70 parts by weight of triethylhexyl citrate (TEHC) with respect to 30 parts by weight of the obtained terephthalate derivative mixture.

(Examples 2 to 9)

It was carried out in the same manner as in Example 1, except that the component ratio of each compound in the terephthalate derivative mixture by varying the amount of the alcohol compound components in Example 1 as shown in Table 1 below.

(Comparative Example 1)

It was carried out in the same manner as in Example 1, except that tributyl citrate (TBC) was used in Example 1 instead of triethylhexyl sulfate.

(Comparative Example 2)

It was carried out in the same manner as in Example 1, except that di (2-propylheptyl) phthalate (DPHP) was used instead of triethylhexyl acrylate in Example 1.

division Terephthalate derivative mixture TEHC TBC DPHP 2 3 4 5 6 7 Parts by weight Parts by weight Parts by weight Parts by weight Example 1 5 10 30 10 15 30 30 70 - - Example 2 7 13 28 10 15 27 30 70 - - Example 3 13 17 30 16 14 10 30 70 - - Example 4 5 10 30 10 15 30 25 75 - - Example 5 5 10 30 10 15 30 10 90 - - Example 6 30 5 10 30 10 15 30 70 - - Example 7 30 40 0 30 0 0 30 70 - - Example 8 0 30 40 0 0 30 30 70 - - Example 9 30 0 40 0 30 0 30 70 - - Comparative Example 1 5 10 30 10 15 30 30 - 70 - Comparative Example 2 5 10 30 10 15 30 30 - - 70

(Example 10)

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 esterified at 240 ° C. for 18 hours.

After completion of the reaction, purification was carried out to obtain a mixture of terephthalate derivatives in which the compounds of Formula 8 to 13 are mixed.

[Formula 8]

[Formula 9]

[Formula 10]

 [Formula 11]

[Formula 12]

[Formula 13]

As a result of analyzing the obtained terephthalate derivative mixture with a GC-Mass analyzer, based on the total weight of the terephthalate derivative mixture, Formula 8: Formula 9: Formula 10: Formula 11: Formula 12: Weight percent of Formula 13 is 4: 11: It was confirmed that it was 25: 11: 14: 35.

Next, a composite plasticizer composition was prepared by mixing 70 parts by weight of triethylhexyl citrate (TEHC) with respect to 30 parts by weight of the obtained terephthalate derivative mixture.

(Examples 11 to 18)

It was carried out in the same manner as in Example 1, except that the component ratio of each compound in the terephthalate derivative mixture by varying the amount of the alcohol compound components in Example 10, as shown in Table 1 below.

(Comparative Example 3)

It was carried out in the same manner as in Example 1, except that tributyl citrate was used in Example 10 instead of triethylhexyl sulfate.

(Comparative Example 4)

It was carried out in the same manner as in Example 1, except that di (2-propylheptyl) phthalate was used in Example 10 instead of triethylhexyl acrylate.

division Isophthalate derivative mixture TEHC TBC DPHP 8 9 10 11 12 13 Parts by weight Parts by weight Parts by weight Parts by weight Example 10 4 11 25 11 14 35 30 70 - - Example 11 7 13 28 10 15 27 30 70 - - Example 12 13 17 30 16 14 10 30 70 - - Example 13 5 10 30 10 15 30 25 75 - - Example 14 5 10 30 10 15 30 10 90 - - Example 15 30 5 10 30 10 15 30 70 - - Example 16 30 40 0 30 0 0 30 70 - - Example 17 0 30 40 0 0 30 30 70 - - Example 18 30 0 40 0 30 0 30 70 - - Comparative Example 3 5 10 30 10 15 30 30 - 70 - Comparative Example 4 5 10 30 10 15 30 30 - - 70

(Examples 19 to 27 and Comparative Examples 5 to 8)

With respect to 100 parts by weight of polyvinyl chloride resin (PVC (paste resin), polymerization degree 1,000), 70 parts by weight of the composite plasticizer composition prepared in Examples 1 to 18 and Comparative Examples 1 to 4 and stabilizer (CZ-400, Complex of Ca-Zn organics, Songwon Industry) 2.5 parts by weight were added, respectively, and kneaded for 5 minutes at 170 ° C using a two-roll mill. Thereafter, a pressure of 15 MPa was applied at 175 ° C. for 3 minutes using a heating press, and after cooling to 90 ° C. or less, a specimen was prepared. The properties of the specimen were measured and the values are shown in Table 2 below.

(Comparative Example 9)

It was carried out in the same manner as in Example 1, except that Diisodecyl phthalate (DIDP) was used instead of using the composite plasticizer composition as the plasticizer in Example 19.

Plasticizer The tensile strength
(kgf / ㎟) Elongation
(%) 100% modulus
(kgf / ㎟) Elongation
(%) Cold resistance
(℃) Volatilization loss
(weight%) Example 19 1.6 354 0.72 96 -49 3 Example 20 1.6 353 0.72 95 -49 3 Example 21 1.6 356 0.72 93 -49 3 Example 22 1.5 345 0.74 93 -47 4 Example 23 1.5 343 0.74 90 -47 4 Example 24 1.5 350 0.73 86 -48 3 Example 25 1.5 349 0.73 86 -48 4 Example 26 1.6 347 0.73 89 -48 4 Example 27 1.6 343 0.73 88 -47 4 Comparative Example 5 1.3 332 0.65 42 -34 11 Comparative Example 6 1.4 330 0.77 84 -39 7

Plasticizer The tensile strength
(kgf / ㎟) Elongation
(%) 100% modulus
(kgf / ㎟) Elongation
(%) Cold resistance
(℃) Volatilization loss
(weight%) Example 28 1.6 340 0.71 93 -42 4 Example 29 1.6 342 0.71 93 -42 4 Example 30 1.6 343 0.71 91 -42 4 Example 31 1.5 335 0.72 88 -43 4 Example 32 1.5 333 0.70 86 -44 4 Example 33 1.6 344 0.68 85 -41 5 Example 34 1.6 341 0.68 84 -41 6 Example 35 1.6 339 0.74 89 -44 4 Example 36 1.6 338 0.72 84 -40 6 Comparative Example 7 1.3 342 0.60 50 -27 11 Comparative Example 8 1.4 327 0.75 81 -35 9 Comparative Example 9 1.5 341 0.79 83 -36 7

As can be seen in Tables 3 and 4, the examples using a composite plasticizer composition in which a mixture of terephthalate derivatives or isophthalate derivatives and TEHC according to the present invention are mixed are excellent tensile strength and when compared with a commercial plasticizer DIDP. It was confirmed that the mechanical properties of the elongation, as well as the heat resistance, cold resistance, and aging resistance characteristics were significantly improved. On the other hand, in the Examples according to the present invention, in the case of Comparative Examples 5 and 7 or the diphthalate-based compounds using tributyl citrate instead of triethylhexyl acrylate, the aging resistance is significantly lowered. It was confirmed that the heat resistance and cold resistance at high temperatures were poor.

Although the present invention has been described through specific matters and limited embodiments as described above, it is provided only to help a more comprehensive understanding of the present invention, and the present invention is not limited to the above embodiments, and the present invention pertains Those skilled in the art can make various modifications and variations from these descriptions.

Accordingly, the spirit of the present invention should not be limited to the described embodiments, and should not be determined, and all claims that are equivalent or equivalent to the scope of the claims as well as the claims described below belong to the scope of the spirit of the invention. .

Claims (11)

Alcohol components consisting of 2-ethyl-1-hexanol, isononyl alcohol and 2-propyl-1-heptyl alcohol; And a phthalate derivative mixture that is a product of phthalic acid; and a compound of Formula 1, wherein the phthalate derivative mixture is a terephthalate derivative mixture containing a compound of Formulas 2 to 7 or an isophthalate containing a compound of Formulas 8 to 13 A composite plasticizer composition that is a derivative mixture.
[Formula 1]

(In Formula 1, R ₁ to R ₃ are each independently C ₆ to C ₁₂ alkyl.)
[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

[Formula 11]

[Formula 12]

[Formula 13]

delete According to claim 1,
The terephthalate derivative mixture is 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 Formula 5, It includes 1 to 40% by weight of the compound and 1 to 40% by weight of the compound of Formula 7,
The isophthalate derivative mixture is 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, A composite plasticizer composition comprising 1 to 40% by weight of a compound and 1 to 40% by weight of a compound of Formula 13. According to claim 1,
The weight ratio of the phthalate derivative mixture and the compound of Formula 1 is 1: 9 to 9: 1 composite plasticizer composition. According to claim 1,
In Formula 1, R ₁ to R ₃ are each independently a C ₈ to C ₁₀ alkyl composite plasticizer composition. Alcohol components consisting of 2-ethyl-1-hexanol, isononyl alcohol and 2-propyl-1-heptyl alcohol; And phthalic acid; synthesizing a phthalate derivative mixture by reacting a reaction solution comprising and
And mixing the synthesized phthalate derivative mixture with the compound of Formula 1, wherein the phthalate derivative mixture is a terephthalate derivative mixture containing the compounds of Formulas 2 to 7 or an iso containing compound of Formulas 8 to 13. Method for preparing a composite plasticizer composition that is a mixture of phthalate derivatives.
[Formula 1]

(In Formula 1, R ₁ to R ₃ are each independently C ₆ to C ₁₂ alkyl.)
[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

[Formula 11]

[Formula 12]

[Formula 13]

The method of claim 6,
The phthalate derivative mixture is an ester of phthalic acid and an alcohol component in which 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-1-heptyl alcohol are mixed. Method for producing a composite plasticizer composition that is obtained by the chemical reaction. A resin composition comprising the composite plasticizer composition of any one of claims 1 and 3 to 5 and a polymer resin. The method of claim 8,
The polymer resin is a resin composition comprising at least one selected from the group consisting of polyvinyl chloride resin, polyolefin resin, polyester resin, ABS resin and acrylic resin. The method of claim 8,
The resin composition further comprises any one or more components selected from the group consisting of fillers, lubricants, stabilizers, blowing agents, viscosity modifiers, processing aids and dispersants. A molded article prepared from the resin composition of claim 8.