Plasticizer composition and resin composition including the same

Abstract

The present invention relates to a plasticizer composition and a resin composition including the same. The compositions comprise a terephthalate-based material, a dibenzoate-based material, and a citrate. The compositions and methods have a weight ratio of the terephthalate-based material to the benzoate-based material of 99:1 to 1:99. The citrate-based material is included at 1 to 80 parts by weight with respect to 100 parts by weight of the total weight of the terephthalate-based material and the dibenzoate-based material.

Claims

1. A plasticizer composition, comprising: a terephthalate-based material; a dibenzoate-based material including a dibenzoate-based compound; and a citrate-based material, wherein a weight ratio of the terephthalate-based material and the dibenzoate-based material is 80:20 to 50:50, and the citrate-based material is included at 20 to 80 parts by weight with respect to 100 parts by weight of the total weight of the terephthalate-based material and the dibenzoate-based material, and is selected from the group consisting of tributyl citrate (TBC), trioctyl citrate (TOC), triheptyl citrate (THpC), tri(2-ethylhexyl)citrate (TEHC), triisononyl citrate (TiNC), and tri(2-propylheptyl) citrate (TPHC): wherein the terephthalate-based material is one or more selected from the group consisting of di(2-ethylhexyl)terephthalate (DEHTP), diisononyl terephthalate (DINTP), diisodecyl terephthalate (DIDTP), di(2-propylheptyl)terephthalate (DPHTP), diamyl terephthalate (DATP), dibutyl terephthalate (DBTP), butylisononyl terephthalate (BINTP), butyl(2-ethylhexyl) terephthalate (BEHTP), amylisononyl terephthalate (AINTP), isononyl(2-propylheptyl) terephthalate (INPHTP), amyl(2-propylheptyl) terephthalate (APHTP), amyl(2-ethylhexyl) terephthalate (AEHTP), (2-ethylhexyl)(2-propylheptyl) terephthalate (EHPHTP) and (2-ethylhexyl)isononyl terephthalate (EHINTP), and wherein the dibenzoate-based compound is diethylene glycol dibenzoate (DEGDB), and DEGDB is the only dibenzoate included in the plasticizer composition.

2. The plasticizer composition of claim 1, wherein the terephthalate-based material is any one selected from the group consisting of di(2-ethylhexyl)terephthalate (DEHTP), diisononyl terephthalate (DINTP), diisodecyl terephthalate (DIDTP), di(2-propylheptyl)terephthalate (DPHTP), diamyl terephthalate (DATP) and dibutyl terephthalate (DBTP).

3. The plasticizer composition of claim 1, wherein the terephthalate-based material is a first mixture of di(2-ethylhexyl)terephthalate (DEHTP), butyl(2-ethylhexyl) terephthalate (BEHTP) and dibutyl terephthalate (DBTP), a second mixture of diisononyl terephthalate (DINTP), butylisononyl terephthalate (BINTP) and dibutyl terephthalate (DBTP), a third mixture of di(2-ethylhexyl)terephthalate (DEHTP), (2-ethylhexyl)isononyl terephthalate (EHINTP) and diisononyl terephthalate (DINTP), a fourth mixture of di(2-propylheptyl)terephthalate (DPHTP), isononyl(2-propylheptyl) terephthalate (INPHTP) and diisononyl terephthalate (DINTP), a fifth mixture of di(2-ethylhexyl)terephthalate (DEHTP), (2-ethylhexyl)(2-propylheptyl) terephthalate (EHPHTP) and di(2-propylheptyl)terephthalate (DPHTP), or a sixth mixture of diamy terephthalate (DATP), amylisononyl terephthalate (AINTP) and diisononyl terephthalate (DINTP).

4. A resin composition, comprising: 100 parts by weight of a polyvinyl chloride; and 5 to 150 parts by weight of the plasticizer composition of claim 1.

5. The resin composition of claim 4, wherein the resin composition is applied to manufacture one or more selected from the group consisting of electric wires, flooring materials, interior materials for automobiles, films, sheets, wall paper and tubes.

6. The plasticizer composition of claim 1, wherein the terephthalate-based material is a first mixture of di(2-ethylhexyl)terephthalate (DEHTP), butyl(2 -ethylhexyl) terephthalate (BEHTP) and dibutyl terephthalate (DBTP).

7. The plasticizer composition of claim 1, wherein the terephthalate-based material is a second mixture of diisononyl terephthalate (DINTP), butylisononyl terephthalate (BINTP) and dibutyl terephthalate (DBTP).

8. The plasticizer composition of claim 1, wherein the terephthalate-based material is a third mixture of di(2-ethylhexyl)terephthalate (DEHTP), (2-ethylhexyl)isononyl terephthalate (EHINTP) and diisononyl terephthalate (DINTP).

9. The plasticizer composition of claim 1, wherein the terephthalate-based material is a fourth mixture of di(2-propylheptyl)terephthalate (DPHTP), isononyl(2-propylheptyl) terephthalate (INPHTP) and diisononyl terephthalate (DINTP).

10. The plasticizer composition of claim 1, wherein the terephthalate-based material is a fifth mixture of di(2-ethylhexyl)terephthalate (DEHTP), (2-ethylhexyl)(2-propylheptyl) terephthalate (EHPHTP) and di(2-propylheptyl)terephthalate (DPHTP).

11. The plasticizer composition of claim 1, wherein the terephthalate-based material is a sixth mixture of diamyl terephthalate (DATP), amylisononyl terephthalate (AINTP) and diisononyl terephthalate (DINTP).

12. The plasticizer composition of claim 1, wherein the terephthalate-based material is one or more selected from the group consisting of: diisodecyl terephthalate (DIDTP), di(2-propylheptyl)terephthalate (DPHTP), diamyl terephthalate (DATP), butylisononyl terephthalate (BINTP), butyl(2-ethylhexyl) terephthalate (BEHTP), amylisononyl terephthalate (AINTP), isononyl(2-propylheptyl) terephthalate (INPHTP), amyl(2-propylheptyl) terephthalate (APHTP), amyl(2-ethylhexyl) terephthalate (AEHTP), (2-ethylhexyl)(2-propylheptyl)terephthalate (EHPHTP) and (2-ethylhexyl)isononyl terephthalate (EHINTP).

13. A plasticizer composition, comprising: a terephthalate-based material; a dibenzoate-based material including a dibenzoate-based compound; and a citrate-based material, wherein a weight ratio of the terephthalate-based material and the dibenzoate-based material is 80:20 to 50:50, and the citrate-based material is included at 20 to 80 parts by weight with respect to 100 parts by weight of the total weight of the terephthalate-based material and the dibenzoate-based material, and is tributyl citrate (TBC): wherein the terephthalate-based material comprises di(2-ethylhexyl)terephthalate (DEHTP), and wherein the dibenzoate-based compound is diethylene glycol dibenzoate (DEGDB), and DEGDB is the only the dibenzoate-based compound included in the plasticizer composition.

14. A plasticizer composition, comprising: a terephthalate-based material; a dibenzoate-based material including a dibenzoate-based compound; and a citrate-based material, wherein a weight ratio of the terephthalate-based material and the dibenzoate-based material is 80:20 to 50:50, and the citrate-based material is included at 20 to 80 parts by weight with respect to 100 parts by weight of the total weight of the terephthalate-based material and the dibenzoate-based material, and is selected from the group consisting of tributyl citrate (TBC), trioctyl citrate (TOC), triheptyl citrate (THpC), tri(2-ethylhexyl)citrate (TEHC), triisononyl citrate (TiNC), and tri(2-propylheptyl) citrate (TPHC): wherein the terephthalate-based material is one or more selected from the group consisting of di(2-ethylhexyl)terephthalate (DEHTP), diisononyl terephthalate (DINTP), diisodecyl terephthalate (DIDTP), di(2-propylheptyl)terephthalate (DPHTP), diamyl terephthalate (DATP), dibutyl terephthalate (DBTP), butylisononyl terephthalate (BINTP), butyl(2-ethylhexyl) terephthalate (BEHTP), amylisononyl terephthalate (AINTP), isononyl(2-propylheptyl) terephthalate (INPHTP), amyl(2-propylheptyl) terephthalate (APHTP), amyl(2-ethylhexyl) terephthalate (AEHTP), (2-ethylhexyl)(2-propylheptyl) terephthalate (EHPHTP) and (2-ethylhexyl)isononyl terephthalate (EHINTP), and wherein the dibenzoate-based compound is triethylene glycol dibenzoate (TEGDB) or dipropylene glycol dibenzoate (DPGDB), and TEGDB or DPGDB is the only the dibenzoate-based compound included in the plasticizer composition.

Description

EXAMPLES

(1) Hereinafter, to explain the present invention in detail, the present invention will be described in detail with reference to examples. However, examples according to the present invention may be modified in a variety of different forms, and the scope of the present invention should not be construed as being limited to the examples to be described below. The exemplary embodiments of the present invention are provided for those of ordinary skill in the art to more fully understand the present invention.

Preparation Example 1: Preparation of di(2-ethylhexyl)terephthalate

(2) 498.0 g of purified terephthalic acid (TPA), 1,170 g of 2-ethylhexyl alcohol (2-EH; a molar ratio of TPA: 2-EH—(1.0):(3.0)), and 1.54 g of a titanium-based catalyst (tetra isopropyl titanate (TIPT); 0.31 parts by weight with respect to 100 parts by weight of TPA) as a catalyst were added to a 4-neck 3 L reaction vessel equipped with a cooler, a condenser, a decanter, a reflux pump, a temperature controller, an agitator, etc., and a temperature was slowly increased to approximately 170° C. At approximately 170° C., water was generated, and esterification was performed for approximately 4.5 hours while a nitrogen gas was continuously added at a reaction temperature of approximately 220° C. under atmospheric pressure, and then terminated when an acid value reached 0.01.

(3) After the reaction was completed, distillation extraction was performed for 0.5 to 4 hours under reduced pressure to remove unreacted components. To remove unreacted components at a predetermined content or less, steam extraction was performed using steam for 0.5 to 3 hours under reduced pressure, and neutralization was performed using an alkali solution after a reaction solution was cooled to approximately 90° C. Additionally, washing could be performed, and then the reaction solution was dehydrated to remove moisture. Filter media were input to the dehydrated reaction solution, stirred for a predetermined time and then filtered, thereby finally obtaining 1,326.7 g of DEHTP (yield: 99.0%).

Preparation Example 2: Preparation of Diisononyl Terephthalate

(4) DINTP was finally obtained using isononyl alcohol, instead of 2-ethylhexanol used in Preparation Example 1.

Preparation Example 3: Preparation of Dibutyl Terephthalate

(5) DBTP was finally obtained using butanol, instead of 2-ethylhexanol used in Preparation Example 1.

Preparation Example 4: Preparation of TP Mixture of DEHTP/BEHTP/DBTP

(6) 2,000 g of DEHTP obtained in Preparation Example 1 and 340 g of n-butanol (17 parts by weight on the basis of 100 parts by weight of DEHTP) were input to a reaction vessel equipped with an agitator, a condensor and a decanter, and allowed to transesterification for 2 hours at a reaction temperature of 160° C. under a nitrogen atmosphere, thereby obtaining a composition including DBTP, butyl(2-ethylhexyl) terephthalate (BEHTP) and DEHTP at 4.0 wt %, 35.0 wt % and 61.0 wt %, respectively.

(7) The reaction product was mixed and distilled to remove butanol and 2-ethylhexyl alcohol, thereby finally preparing a first mixture.

Preparation Example 5: Preparation of TP Mixture of DINTP/EHINTP/DEHTP

(8) A composition including DINTP, (2-ethylhexyl)isononyl terephthalate (EHINTP) and DEHTP at 2.5 wt %, 30.5 wt % and 67.0 wt %, respectively, was obtained using diisononyl terephthalate and 2-ethylhexanol, instead of DEHTP and n-butanol used in Preparation Example 4.

Preparation Example 6: Preparation of TP Mixture of DINTP/EHINTP/DEHTP

(9) A composition including di(2-propylheptyl)terephthalate (DINTP), isononyl(2-propylheptyl)terephthalate (INPHTP) and DINTP at 2.7 wt %, 31.0 wt % and 66.3 wt %, respectively, was obtained using DPHTP and isononyl alcohol, instead of DEHTP and n-butanol used in Preparation Example 4.

Preparation Example 7: Preparation of DEGDB

(10) 1,221 g of purified benzoic acid (BA) and 530.5 g of diethylene glycol (DEG) were added at a molar ratio of BA:DEG (2.0):(1.0), and 2.0 g of a titanium-based catalyst (tetraisopropyltitanate (TIPT)) as a catalyst and a small amount of xylene were added to a 4-neck 2 L reaction vessel equipped with a cooler, a condenser, a decanter, a reflux pump, a temperature controller, an agitator, etc., and then a temperature was slowly elevated to approximately 170° C. When water was generated at approximately 170° C., the amount of xylene was adjusted to facilitate the removal of the generated water, and the reaction was terminated when the content of a monobenzoate as an intermediate among the reactants was 5% or less. Afterward, 1,530 g of the final product DEGDB (yield: 98%) was obtained by a method similar to that described in Preparation Example 1.

Preparation Example 8: Preparation of TBC

(11) 706 g of TBC (yield: 98%) was finally obtained using 384 g of citric acid and 580 g of butanol as reactants.

Preparation Example 9: Preparation of TOC

(12) 1,029 g of TOC (yield: 98%) was finally obtained using 384 g of citric acid and 1,014 g of 2-ethylhexanol as reactants.

Preparation Example 10: Preparation of TiNC

(13) 1,111 g of TiNC (yield: 98%) was finally obtained using 384 g of citric acid and 1,123 g of isononanol as reactants.

Preparation Example 11: Preparation of BOC253

(14) 840 g of BOC was finally obtained by performing transesterification using 1,000 g of TOC prepared in Preparation Example 9 and 300 g of n-butanol as reactants.

(15) The mixture included approximately 20.9 wt % of the combination of three materials including approximately 2.2 wt % of TBC and approximately 18.7 wt % of two types of citrates in which two 2-ethylhexyl groups were replaced by butyl groups, approximately 45.4 wt % of the combination of two types of citrates in which one 2-ethylhexyl group is replaced by a butyl group, and approximately 33.7 wt % of TOC at a weight ratio of approximately 2:5:3 in order of molecular weight.

Examples 1 to 12 and Comparative Examples 1 to 5

(16) Examples and Comparative Examples were prepared using the materials prepared in Preparation Examples 1 to 11 and commercially-available materials as shown in Tables 1 to 3 below. Parts by weight of the citrates shown below are values relative to 100 parts by weight of the total weight of the mixture of a TP-based material and a dibenzoate-based material.

(17) TABLE-US-00001 TABLE 1 Dibenzoate- Citrate based Mixed (parts by TP-based material material ratio weight) Example 1 DEHTP DEGDB 7:3 TBC(10) Example 2 DINTP DEGDB 8:2 TBC(10) Example 3 DEHTP/BEHTP/DBTP DEGDB 6:4 TBC(10) Example 4 DPHTP/INPHTP/DINTP DPGDB 5:5 TBC(20) Example 5 DEHTP DPGDB 8:2 TBC(50) Example 6 DINTP TEGDB 7:3 TBC(25) Example 7 DEHTP DEGDB 7:3 TBC(50) Example 8 DEHTP DEGDB 7:3 TBC(75) *GL300 ™: DEHTP produced by LG Chem Ltd.

(18) TABLE-US-00002 TABLE 2 Dibenzoate- Citrate based Mixed (parts by TP-based material material ratio weight) Example 9 DEHTP DEGDB 5:5 TOC(20) Example 10 DINTP/OINTP/DOTP DEGDB 6:4 BOC(10) Example 11 DEHTP DPGDB 6:4 TOC(25) Example 12 DINTP DPGDB 5:5 TOC(50) *GL300 ™: DEHTP produced by LG Chem Ltd.

(19) TABLE-US-00003 TABLE 3 Citrate Dibenzoate- Mixed (parts by TP-based material based material ratio weight) Comparative GL300* Example 1 Comparative DEHTP DEGDB 75:25 Example 2 Comparative DBTP DEGDB 6:4 Example 3 Comparative DEHTP DEGDB 8:2 TINC(100) Example 4 Comparative DEHTP DPGDB 7:3 TBC(100) Example 5 *GL300 ™: DEHTP produced by LG Chem Ltd.

Experimental Example 1: Preparation of Samples and Performance Evaluation 1

(20) Plasticizers of Examples 1 to 8 and Comparative Examples 1 to 3 and 5 were used as experimental samples. For sample preparation, referring to ASTM D638, 40 parts by weight of a plasticizer and 3 parts by weight of a stabilizer (LOX 912 NP) were mixed with 100 parts by weight of PVC in a mixer, and the resulting mixture was subjected to roll-milling at 170° C. for 4 minutes and pressed for 2.5 minutes (low pressure) and 2 minutes (high pressure) at 180° C., thereby manufacturing 1 T and 3 T sheets. Each sample was subjected to a test for physical properties, and the results are shown in Table 4 below.

(21) <Test Items>

(22) Hardness

(23) According to ASTM D2240, Shore hardness (Shore “D”) was measured at 25° C. under conditions of 3 T and 10 s.

(24) Tensile Strength

(25) According to ASTM D638, each specimen was pulled at a cross head speed of 200 mm/min (1 T) using a tester, U.T.M, (Manufacturer; Instron, Model No.; 4466), and a position at which the specimen was broken was detected. A tensile strength was calculated as follows:
Tensile strength (kgf/mm.sup.2)=Load value (kgf)/Thickness (mm)×Width (mm)

(26) Measurement of Elongation Rate

(27) According to ASTM D638, each specimen was pulled at a cross head speed of 200 mm/min (1 T) using the U.T.M, and a position at which the specimen was broken was detected. An elongation rate was calculated as follows:
Elongation rate (%)=Length after elongation/Initial length×100

(28) Measurement of Migration Loss

(29) An experimental specimen having a thickness of 2 mm or more was obtained according to KSM-3156, and following attachment of glass plates to both sides of the specimen, a weight of 1 kgf/cm.sup.2 was applied to the specimen. The specimen was put in a forced convection oven (80° C.) for 72 hours, and cooled at room temperature for 4 hours. Then, after the glass plates attached to both sides of the specimen were removed, a weight was measured before and after the glass plate and the specimen plate were put in the oven and thus a migration loss was calculated by the equation as follows.
Migration loss (%)=[(Initial weight of specimen at room temperature−Weight of specimen after being put into oven)/Initial weight of specimen at room temperature]×100

(30) Measurement of Volatile Loss

(31) The prepared specimen was processed at 100° C. for 72 hours, and a weight of the specimen was measured as follows:
Volatile loss (wt %)=[(Weight of initial specimen−Weight of specimen after processed at 100° C. for 72 hours)/Weight of initial specimen]×100

(32) Measurement of Absorption Rate

(33) An absorption rate was evaluated by measuring the time taken to stabilize the torque of a mixer in which a resin and an ester compound are mixed together using a planetary mixer (Brabender, P600) at 77° C. and 60 rpm.

(34) TABLE-US-00004 TABLE 4 Tensile Volatile Hardness strength Elongation Migration loss Absorption (Shore D) (kg/cm.sup.2) (%) loss (%) (%) rate (m:s) Example 1 48.0 285.6 311.2 1.32 1.10 4:56 Example 2 48.1 288.1 310.5 1.68 0.98 5:22 Example 3 46.0 285.1 325.4 0.58 1.20 4:33 Example 4 47.6 275.4 298.5 1.88 1.17 4:15 Example 5 44.0 254.7 288.6 2.55 3.04 3:50 Example 6 46.3 260.8 280.9 1.70 2.40 4:18 Example 7 43.5 268.7 293.4 2.60 2.68 4:05 Example 8 42.4 248.0 245.5 3.70 3.20 3:38 Comparative 48.9 236.7 288.6 3.21 1.63 7:15 Example 1 Comparative 48.8 237.5 293.5 2.87 2.23 5:20 Example 2 Comparative 45.5 204.5 256.0 5.20 11.20 2:10 Example 3 Comparative 41.0 235.4 230.5 5.80 17.50 1:35 Example 5

(35) Referring to Table 4, when Comparative Examples 2 and 3 which had no citrate, Comparative Example 5 which had an excessive citrate, and Comparative Example 1 which has been used as a conventional plasticizer, but was in need of improvement in absorption rate, migration, tensile strength or plasticization efficiency (hardness) are compared to Examples 1 to 8, it can be confirmed that Comparative Example 1 is inferior in tensile strength to the Examples as expected, and since an absorption rate is also longer than 7 minutes and thus a processing time is excessively long, the tensile strength or the elongation rate is very low, and the plasticization efficiency is reduced, it can be estimated that there is chance to have problems in processability and productivity, and an increase in production cost.

(36) In addition, it can be confirmed that, since Comparative Example 2 has neither particularly excellent nor good physical properties, it may be difficult to be commercialized even for a use suitable for a certain property, and Comparative Example 3 may have problems in processability due to an ultimately low tensile strength, low migration loss and low volatile loss, and a very high absorption rate.

(37) In addition, it can be seen that Comparative Example 5 has very low volatile loss and very low migration loss because the citrate is excessively added at more than 80 parts by weight up to 100 parts by weight, and also has problems in processability due to a high absorption rate.

(38) On the other hand, the plasticizers of Examples 1 to 8 have basic levels of mechanical properties, and also exhibit considerable levels of physical properties such as volatile loss and migration loss. Therefore, it can be seen that, when used at the same amount, they can control migration loss in a suitable range with smaller amounts than that of a plasticizer having high migration loss, and also can be confirmed that they may not have problems in processing because of overall similar absorption rates. In addition, it can be confirmed that the Examples having a little lower tensile strength or a little lower elongation rate have low hardness, which can be compensated by plasticization efficiency.

Experimental Example 2: Preparation of Samples and Performance Evaluation 2

(39) The plasticizers of Examples 9 to 12 and Comparative Examples 1 to 4 were used as experimental samples. The preparation of samples and the evaluation of physical properties were carried out as described in Experimental Example 1, and the results are shown in Table 5 below.

(40) TABLE-US-00005 TABLE 5 Tensile Volatile Hardness strength Elongation Migration loss Absorption (Shore D) (kg/cm.sup.2) rate (%) loss (%) (%) rate (m:s) Example 9 48.5 295.1 315.0 1.02 0.75 5:55 Example 10 48.2 290.5 304.7 1.42 0.95 5:08 Example 11 47.2 298.7 302.5 0.77 0.60 5:05 Example 12 49.0 317.0 308.5 0.50 0.72 6:44 Comparative 48.9 236.7 288.6 3.21 1.63 7:15 Example 1 Comparative 48.8 237.5 293.5 2.87 2.23 5:20 Example 2 Comparative 45.5 204.5 256.0 5.20 11.20 2:10 Example 3 Comparative 50.3 265.4 245.0 2.50 1.08 9:25 Example 4

(41) Referring to Table 5, when Comparative Examples 2 and 3 which had no citrate, Comparative Example 4 which had an excessive citrate, and Comparative Example 1 which has been used as a conventional plasticizer, but was in need of improvement in absorption rate, migration, tensile strength or elongation rate are compared to Examples 9 to 12, it can be confirmed that, in Comparative Example 1, as expected, all of the physical properties such as tensile strength, an elongation rate, migration loss and volatile loss are in low levels and a hardness is high, and therefore it is difficult to compensate these disadvantages by plasticization efficiency.

(42) In addition, it can be confirmed that Comparative Example 2 has physical properties which are neither particularly excellent nor high, and therefore can be difficult to be commercialized even for a use suitable for a certain property, and Comparative Example 3 may have excellent plasticization efficiency, ultimately low tensile strength and considerably low migration loss and volatile loss, and also have a high absorption rate, thereby causing problems in processability.

(43) In addition, it can be seen that, since Comparative Example 4 has excessively high hardness, although having lower plasticization efficiency, it is considerably decreased in the tensile strength and the elongation rate, compared to the Examples. It can also be confirmed that Comparative Example 4 has a considerably lower absorption rate, and therefore has a serious effect on processability in conjunction with the plasticization efficiency.

(44) On the other hand, the plasticizers of Examples 9 to 12 has basically excellent mechanical properties such as tensile strength and an elongation rate, and favorable physical properties such as volatile loss and migration loss. Therefore, it can be seen that, when used at the same amount, these plasticizers can control the migration loss in a suitable range with a lower amount than that of a plasticizer having high migration loss, and also can be confirmed that they have satisfactory absorption rate and hardness, and excellent processability.

(45) Accordingly, referring to Tables 4 and 5, when a terephthalate-based material and a dibenzoate-based material are used as plasticizers as well as a citrate-based material, it can be confirmed that the migration loss and the volatile loss, as well as the mechanical properties, can be reduced, and processability can be controlled at an excellent level, and it can be seen that the physical properties can be controlled by adjusting the number of carbon atoms of the citrate to a suitable level.