Plasticizer Composition and Resin Composition Including the Same

Abstract

The present invention relates to a tetraester-based plasticizer composition characterized in including a product derived from esterification reaction of an isomer mixture of hexanoic acid and a tetraol, wherein the degree of branching of the isomer mixture of hexanoic acid is 2.0 or less. If the plasticizer composition is applied to a resin, plasticization efficiency and absorption rate may be maintained to equal or better levels when compared to a case applying the conventional plasticizer, and mechanical properties, migration resistance, stress migration and loss properties may be markedly improved.

Claims

1. A plasticizer composition comprising a tetraester-based composition comprising one or more tetraesters represented by the following Formula 1: ##STR00003## wherein: in the Formula 1, R.sub.1 to R.sub.4 are each independently an n-pentyl group, a branched pentyl group or a cyclopentyl group, and alkyl groups of the one of more tetraesters are derived from an isomer mixture of hexanoic acid having a degree of branching of 2.0 or less.

2. The plasticizer composition according to claim 1, wherein the degree of branching is 1.5 or less.

3. The plasticizer composition according to claim 1, wherein the isomer mixture comprises 2-methylpentanoic acid and 3-methylpentanoic acid.

4. The plasticizer composition according to claim 1, wherein the isomer mixture comprises 1-hexanoic acid, 2-methylpentanoic acid, 3-methylpentanoic acid and, and cyclopentyl methanoic acid.

5. The plasticizer composition according to claim 1, wherein the isomer mixture comprises from 20 to 95 parts by weight of a branched hexanoic acid with respect to a total of 100 parts by weight of the isomer mixture.

6. The plasticizer composition according to claim 1, wherein the isomer mixture comprises 30 parts by weight or less of cyclopentyl methanoic acid with respect to a total of 100 parts by weight of the isomer mixture.

7. The plasticizer composition according to claim 1, wherein the isomer mixture comprises 80 parts by weight or less of 1-hexanoic acid with respect to a total of 100 parts by weight of the isomer mixture.

8. The plasticizer composition according to claim 1, wherein a mixture weight of a triester and a diester that are optionally present in the tetraester-based composition is 5.0 wt % or less with respect to a total weight of the tetraester-based composition.

9. A resin composition, comprising: 100 parts by weight of a resin; and from 5 to 150 parts by weight of the plasticizer composition according to claim 1.

10. The resin composition according to claim 9, wherein the resin is one or more selected from the group consisting of a straight vinyl chloride polymer, a paste vinyl chloride polymer, an ethylene vinyl acetate copolymer, an ethylene polymer, a propylene polymer, polyketone, polystyrene, polyurethane, natural rubber, and synthetic rubber.

Description

EXAMPLE

[0071] Hereinafter, embodiments will be explained in detail to particularly explain the present invention. The present invention may, however, be embodied in different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the inventive concept to those skilled in the art.

Example 1

[0072] To a reactor equipped with a stirrer, a condenser and a decanter, 1160 g of 1-hexanoic acid, 272 g of pentaerythritol, and 5 g of methanesulfonic acid were injected, and esterification reaction was performed and finished under a nitrogen atmosphere, while controlling the reaction temperature in a range of 100° C. to 140° C. according to the boiling points of raw materials and the conversion ratio of the reaction. After removing unreacted acid, a catalyst and a product were neutralized and washed with an alkaline aqueous solution, and unreacted raw materials and moisture were purified to finally obtain a tetraester-based plasticizer composition.

Examples 2 to 12

[0073] Tetraester-based plasticizer compositions of Examples 2 to 11 were obtained by preparing ester compositions by the same method as in Example 1 except for injecting carboxylic acids having 6 alkyl carbon atoms or isomer mixtures thereof described in Table 1 below instead of 1-hexanoic acid.

TABLE-US-00001 TABLE 1 No Material Weight ratio Example 2 2-MPA/3-MPA/1-HA/CPMA 15/50/30/5 Example 3 2-MPA/3-MPA/1-HA/CPMA 30/30/30/10 Example 4 2-MPA/3-MPA/1-HA/CPMA 40/40/10/10 Example 5 2-MPA/3-MPA/1-HA/CPMA 30/40/20/10 Example 6 2-MPA/3-MPA/1-HA/CPMA 30/50/5/15 Example 7 2-MPA/3-MPA/1-HA/CPMA 50/40/2/8 Example 8 2-MPA/3-MPA/1-HA/CPMA 60/30/8/2 Example 9 2-MPA/3-MPA/1-HA/CPMA 40/50/10 Example 10 2-MPA/3-MPA/1-HA/CPMA 30/40/30 Example 11 2-MPA/3-MPA/1-HA 40/50/10 * 2-MPA: 2-methylpentanoic acid * 3-MPA: 3-methylpentanoic acid * 1-HA: 1-hexanoic acid * CPMA: cyclopentyl methanoic acid

Comparative Example 1

[0074] Dioctyl phthalate (DOP, LG Chem,) was applied as a plasticizer.

Comparative Example 2

[0075] Diisononyl phthalate (DINP, LG Chem,) was applied as a plasticizer.

Comparative Example 3

[0076] GL300 which is a product of LG Chem, and dioctyl terephthalate was used as a plasticizer.

Comparative Example 4

[0077] GL520 which is a product of LG Chem, and a mixture of dibutyl terephthalate, butyloctyl terephthalate and dioctyl terephthalate was applied as a plasticizer.

Comparative Example 5

[0078] GL330T which is a product of LG Chem, and a mixture of dioctyl terephthalate and tributyl citrate was applied as a plasticizer.

Comparative Example 6

[0079] BET which is a product of LG Chem, and a product derived from esterification of trimethylol propane, 2-ethylhexanoic acid and benzoic acid was applied as a plasticizer.

Comparative Example 7

[0080] Pevalen which is a product of Perstorp Co. and a product derived from esterification of valeric acid and pentaerythritol was applied as a plasticizer.

Comparative Example 8

[0081] To a reactor equipped with a stirrer, a condenser and a decanter, 1350 g of n-heptanoic acid, 272 g of pentaerythritol, and 5 g of methanesulfonic acid were injected, and esterification reaction was performed and finished under a nitrogen atmosphere, while controlling the reaction temperature in a range of 100° C. to 140° C. according to the boiling points of raw materials and the conversion ratio of the reaction. After removing unreacted acid, a catalyst and a product were neutralized and washed with an alkaline aqueous solution, and unreacted raw materials and moisture were purified to finally obtain a tetraester-based plasticizer composition.

Experimental Example 1: Evaluation of Sheet Performance

[0082] By using the plasticizers of the Examples and Comparative Examples, specimens were manufactured according to ASTM D638 and the prescription and manufacturing conditions below.

[0083] (1) Prescription: 100 parts by weight of a straight vinyl chloride polymer (LS100S), 50 parts by weight of a plasticizer and 3 parts by weight of a stabilizer (BZ-153T)

[0084] (2) Mixing: mixing at 98° C. in 700 rpm

[0085] (3) Manufacture of specimen: 1T, 2T and 3T sheets were manufactured by processing at 165° C. for 4 minutes by a roll mill, and at 180° C. for 2.5 minutes (low pressure) and 2 minutes (high pressure) by a press

(4) Test Items

[0086] 1) Hardness: Shore hardness (Shore “A” and “D”) at 25° C. was measured using a 3T specimen for 10 seconds using ASTM D2240. The plasticization efficiency was assessed excellent if the value was small.

[0087] 2) Tensile strength: By an ASTM D638 method, a specimen was drawn in a cross head speed of 200 mm/min using a test apparatus of U.T.M (manufacturer: Instron, model name: 4466), and a point where the 1T specimen was cut was measured. The tensile strength was calculated as follows.

Tensile strength (kgf/cm.sup.2)=load value (kgf)/thickness (cm)×width (cm)

[0088] 3) Elongation rate measurement: By an ASTM D638 method, a specimen was drawn in a cross head speed of 200 mm/min using a test apparatus of U.T.M, and a point where the 1T specimen was cut was measured. The elongation rate was calculated as follows.

Elongation rate (%)=length after elongation/initial length×100

[0089] 4) Migration loss measurement: According to KSM-3156, a specimen with a thickness of 2 mm or more was obtained, glass plates were attached onto both sides of 1T specimen, and a load of 1 kgf/cm.sup.2 was applied. The specimen was stood in a hot air circulation type oven (80° C.) for 72 hours and then taken out and cooled at room temperature for 4 hours. Then, the weights of the specimen from which glass plates attached onto both sides thereof were removed, were measured before and after standing the glass plates and the specimen plate in the oven, and the migration loss was calculated as follows.

Migration loss (%)={[(weight of initial specimen)−(weight of specimen after standing in oven)]/(weight of initial specimen)}×100

[0090] 5) Volatile loss measurement: The specimen manufactured was processed at 80° C. for 72 hours, and the weight of the specimen was measured.

Volatile loss (wt %)={[(weight of initial specimen)−(weight of specimen after processing)]/(weight of initial specimen)}×100

[0091] 6) Stress test (stress resistance): A specimen with a thickness of 2 mm in a bent state was stood at 23° C. for 168 hours, and the degree of migration (degree of oozing) was observed. The results were recorded as numerical values, and excellent properties were shown if the value was closer to 0.

[0092] 7) Absorption rate measurement: Absorption rate was evaluated by measuring the time consumed for mixing a resin and a plasticizer, and stabilizing the torque of a mixer by using a planatary mixer (Brabender, P600) in conditions of 73° C. and 60 rpm to evaluate processability. According to the degree of excellence, evaluation was assessed by the measure of 1 to 5, and excellent one was designated by 5, and inferior one was designated by 1.

(5) Evaluation Results

[0093] The evaluation results on the test items are listed in Table 2 below.

TABLE-US-00002 TABLE 2 Tensile Hardness strength Elongation Migration Volatile Stress Absorption (Shore A) (Shore D) (kgf/cm.sup.2) rate (%) loss (%) loss (%) resistance rate Example 1 84.0 37.8 214.7 320.7 1.40 0.39 0 5 Example 2 84.1 37.9 215.4 321.2 1.41 0.46 0 5 Example 3 84.2 37.8 216.8 320.9 1.45 0.40 0 5 Example 4 84.5 38.1 214.6 317.4 1.40 0.47 0.5 5 Example 5 84.3 37.9 208.6 304.6 1.38 0.38 0.5 5 Example 6 84.2 38.0 215.6 321.1 1.32 0.41 0 5 Example 7 84.5 38.1 220.2 321.5 1.40 0.45 0.5 5 Example 8 84.5 38.0 217.8 320.0 1.41 0.44 0.5 5 Example 9 84.0 37.9 215.6 318.4 1.38 0.41 0 5 Example 10 84.1 38.0 214.9 320.3 1.39 0.42 0.5 5 Example 11 84.0 37.8 213.4 317.9 1.38 0.40 0.5 5 Comparative 84.1 37.9 180.1 316.7 1.49 1.54 0 5 Example 1 Comparative 86.3 39.9 195.0 326.4 2.10 0.72 1.5 3 Example 2 Comparative 88.2 41.7 206.9 328.9 6.45 0.77 3.0 2 Example 3 Comparative 86.1 39.6 202.3 310.9 5.64 2.19 2.5 5 Example 4 Comparative 84.5 37.9 200.2 317.2 4.24 2.50 2.5 5 Example 5 Comparative 91.5 46.4 241.7 289.8 3.86 0.58 0.5 1 Example 6 Comparative 83.4 37.5 209.8 308.6 1.72 0.60 1.5 1 Example 7 Comparative 86.7 41.3 204.6 320.6 5.78 0.30 2.5 3 Example 8

[0094] Referring to the results of Table 2, it could be confirmed that uniform and remarkably excellent physical properties in view of plasticization efficiency, tensile strength, elongation rate, stress resistance, migration loss, and volatile loss are shown in case of applying the plasticizers of Examples 1 to 11 in contrast to cases of applying the plasticizers of Comparative Examples 1 to 8. Particularly, it could be confirmed that processability was excellent in view of the excellent levels of plasticization efficiency and absorption rate. In addition, since it is confirmed that all physical properties were accomplished to equal or better levels as those of the plasticizer of Comparative Example 1, which is the conventional plasticizer having high performance but would induce fatal environmental issues, and it could be confirmed that the plasticizers of the Examples are very suitable as replaceable plasticizers.

[0095] Further, it could be confirmed that Comparative Examples 3 to 6, which correspond to the conventional eco-friendly plasticizers developed as replacements of a phthalate-based plasticizer showed defects relating migration resistance and stress resistance, but the plasticizers of the Examples achieved marked improvement of physical properties in view of such migration resistance and stress resistance.

[0096] In addition, it could be confirmed that, through Comparative Examples 7 and 8, in which a carboxylic acid having not 6 carbon atoms but 5 or 7 carbon atoms was applied, there were defects of inferior plasticization efficiency and migration resistance or inferior mechanical properties, but the Examples according to the present invention, in which a carboxylic acid having 6 carbon atoms was applied did not show such defects. Further, considering stress resistance and absorption rate, it could be confirmed that improving effects were shown for only cases with 6 carbon atoms, but inferior results were shown for cases with 5 or 7 carbon atoms.