TECHNICAL FIELD
[0001] The present invention relates to an isophthalate-based ester compound, a plasticizer
composition including the same, a preparation method of the plasticizer composition and a resin
composition including the plasticizer composition.
BACKGROUND ART
[0002] Polymer resins are used in diverse fields such as daily supplies, home electronic
appliances, clothes, vehicles, construction materials or packing materials, etc. in accordance with
each characteristic.
[0003] Until now, plastic resins such as polyethylene (PE), polypropylene (PP), polystyrene
(PS), polyurethane (PU), polyvinyl chloride (PVC), etc. are widely used. Particularly, since a
PVC resin has hard and soft properties, is capable of being molded in diverse shapes, has good
price competitiveness, and so has a wide range of usability, the PVC resin is applied in diverse
application fields from the daily supplies to the construction materials.
[0004] The PVC resin is used with a plasticizer to realize diverse physical properties rather
than used solely. The PVC resin is imparted with flexibility by the plasticizer, thereby
improving processability and applicability thereof. However, as the industry advances, the role
of the plasticizer becomes diverse, and properties required in applied fields become diverse
including volatility resistance, migration resistance, ageing resistance, cold resistance, oil
resistance, water resistance, heat resistance, etc., other than the flexibility.
[0005] As the ester compound used as the plasticizer recently, di-(2-ethylhexyl) phthalate
(DEHP), diisononyl phthalate (DINP), di-2-propylheptyl phthalate (DPHP), diisodecyl phthalate
(DIDP), etc. are widely used. However, these compounds are environmental hormones
disturbing endocrine system and are harmful to a human body, and have a limit in improving the
processability of a resin, absorption rate with a resin, volatile loss, the degree of migration loss
and heat stability.
[0006] Thus, the development on an ester compound which is eco-friendly, sufficiently
improves all physical properties including the processability of a resin, the absorption rate with a
resin, hardness, tensile strength, elongation rate, volatile loss, the degree of migration loss, heat
stability, etc., and a method of preparing the same is required.
DISCLOSURE OF THE INVENTION
TECHNICAL PROBLEM
[0007] The first technical task intend to solve in the present invention is a novel compound
for a plasticizer, and the present invention provides a novel ester compound for a plasticizer
which is eco-friendly and improves absorption rate with respect to a resin and the processability
of a resin with short melting time when used in a resin composition, thereby providing good
physical properties such as tensile strength, elongation rate, migration resistance, volatility
resistance, etc.
3
[0008] The second technical task intend to solve in the present invention is to provide a
plasticizer composition including the ester compound.
[0009] The third technical task intend to solve in the present invention is to provide a
preparation method of the plasticizer composition.
[0010] The fourth technical task intend to solve in the present invention is to provide a resin
composition including the ester compound.
TECHNICAL SOLUTION
[0011] According to an aspect of the present invention, there is provided an ester compound
of the following Formula 1.

[0012] In the above formula, R1 and R2 are different from each other and are independently
at least one selected from the group consisting of C3-C10 alkyl of a non-branch type or including
at least one branched chain, a substituted or unsubstituted alkyl aryl and a substituted or
unsubstituted aryl.
[0013] In addition, there is provided in the present invention a plasticizer composition
including the ester compound of the above Formula 1.
[0014] In addition, there is provided in the present invention a preparation method of the
plasticizer composition including conducting an esterification reaction of isophthalic acid of the
following Formula 2 with at least one alcohol of the following Formula 3 or a mixture of the
alcohol with at least one isomer thereof in the presence of a catalyst.

R’OH
[0015] In the above formula, R’ is at least one selected from the group consisting of a C3-C10
alkyl of a non-branch type or including at least one branched chain, a substituted or unsubstituted
alkyl aryl and a substituted or unsubstituted aryl.
4
[0016] Also, in an embodiment of the present invention, there is provided a polyvinyl
chloride resin composition including the plasticizer composition.
[0017] Further, in an embodiment of the present invention, there is provided a resin
composition including the plasticizer composition.
ADVANTAGEOUS EFFECTS
[0018] The ester compound according to an embodiment of the present invention is a novel
isophthalate-based ester compound for a plasticizer, and when used in a resin composition,
plasticization efficiency is good and good physical properties such as tensile strength, elongation
rate, migration resistance, volatility resistance, etc. may be provided.
MODE FOR CARRYING OUT THE INVENTION
[0019] Hereinafter, the present invention will be explained in detail to assist the
understanding of the present invention.
[0020] It will be understood that terms or words used in the present disclosure and claims
should not be interpreted as having a meaning that is defined in common or in dictionaries,
however should be interpreted in consistent with the technical scope of the present invention on
the basis of the principle that inventors may appropriately define the concept of the terms to
explain the invention at his best method.
[0021] The term “hybrid type” used in the present invention refers to a structure having
different substituted alkyl groups at symmetric positions of a phenyl group if not specifically
defined.
[0022] In addition, the term “non-hybrid type” used in the present invention refers to a
structure having the same substituted alkyl groups at symmetric positions of a phenyl group if
not specifically defined.
[0023] According to an embodiment of the present invention, an ester compound of the
following Formula 1 is provided.

[0024] In the above formula, R1 and R2 are different from each other and are independently
at least one selected from the group consisting of C3-C10 alkyl of a non-branch type or including
at least one branched chain, a substituted or unsubstituted alkyl aryl and a substituted or
unsubstituted aryl.
[0025] In this case, the branched chain may be C1-C6 alkyl, C2-C6 alkenyl or C2-C6 alkynyl.
[0026] The ester compound of the above Formula 1 according to an embodiment of the
present invention may preferably be an ester compound where R1 and R2 are different from each
5
other and are independently at least one selected from the group consisting of C4-C9 alkyl of a
non-branch type or including at least one branched chain of C1-C4 alkyl, and phenyl or benzyl of
a non-branch type or including at least one branched chain of C1-C4 alkyl.
[0027] The ester compound of the above Formula 1 according to an embodiment of the
present invention may more preferably be at least one ester compound selected from compounds
in the following formulae.

6

7

8

9
[0028] The hybrid type ester compound according to an embodiment of the present
invention is a novel compound for a plasticizer and has high purity, low amount of residual
alcohol and low water content. In the case of using in a resin composition, eco-friendly
characteristics, improved processability of the resin due to short absorption rate and short
melting time with respect to a resin, and good physical properties may be provided.
[0029] The ester compound according to an embodiment of the present invention is an
isophthalate-based ester compound in which ester groups (-COO-) are present at positions 1 and
3 in a benzene ring, that is, at a meta position, and is more eco-friendly and has better physical
properties including tensile strength, elongation rate, migration resistance, volatility resistance,
etc. when compared to a phthalate-based ester compound having ester groups (-COO-) at other
positions, for example an ortho position (positions 1 and 2 in a benzene ring) or a para position
(positions 1 and 4 in a benzene ring).
[0030] Particularly, benzenedicarboxylic acid of an ortho position used as a raw material for
preparing a phthalate-based ester compound having ester groups at the ortho position has a limit
and is not free from a phthalate issue, particularly defects of environmental contamination and
harmfulness to a human body. Meanwhile, the phthalate-based ester compound having ester
groups at para position has relatively deteriorated compatibility and combination stability with
the resin due to the linear structure thereof, and these defects may be adversely affecting factors
to the processability and workability of a product.
[0031] In the case of using the ester compound according to an embodiment of the present
invention as the plasticizer of the resin composition, equivalent tensile strength and elongation
rate may be secured when compared to a phthalate-based compound widely used as a common
plasticizer. Particularly, migration loss (%) and volatile loss (%) are markedly decreased by 1/2
and over than DIDP, and such decrease may mean the decrease of the amount of an ester
compound (plasticizer) present in a specimen. In other words, equal to or better overall physical
properties than a common phthalate-based ester compound may be realized.
[0032] The present invention may provide a plasticizer composition further including at
least one compound selected from the group consisting of the compounds of the following
formulae according to an embodiment.

10

[0033] Here, the non-hybrid type plasticizer compound as in the above Formulae 1-16 to 21
may be included in a final product when conducting an esterification reaction of the hybrid type
11
compound. Particularly, the plasticizer composition may have a configuration including one of
the compounds of Formulae 1-1 to 1-15 as a hybrid type isophthalate compound and at least two
selected from the group consisting of the compounds of Formulae 1-16 to 21 as a non-hybrid
type isophthalate compound.
[0034] The total amount of the hybrid type isophthalate compound and the non-hybrid type
isophthalate compound of the plasticizer composition may be from 5 to 80 wt% of the hybrid
type isophthalate compound and from 20 to 95 wt% of the total non-hybrid type isophthalate
compounds on the basis of the total amount of the plasticizer composition. Preferably, from 10
to 60 wt% of the hybrid type isophthalate compound and from 40 to 90 wt% of the total nonhybrid
type isophthalate compounds may be included. In the case that the amount of the hybrid
type isophthalate-based compound is less than 5 wt% in the total amount of the plasticizer
composition, the improvement of physical properties such as hardness, tensile strength,
elongation rate, viscosity stability, etc. may be insignificant, and in the case that the hybrid type
isophthalate-based compound exceeds 80 wt% in the total amount of the plasticizer composition,
migration resistance, volatile loss and processability may be deteriorated.
[0035] According to another embodiment of the present invention, a plasticizer composition
including compounds of the following formulae may be provided.

and

12
[0036] In addition, the plasticizer composition may include the compounds of the following
formulae.

and

[0037] Alternatively, the compounds of the following formulae may be included.

13

and

[0038] Hereinafter, the ester compound of the above Formula 1 according to an embodiment
of the present invention or a preparation method of the plasticizer composition including the
same will be explained in detail.
[0039] The ester compound or the plasticizer composition according to an embodiment of
the present invention may be obtained by conducting an esterification reaction of isophthalic acid
of the following Formula 2 with at least one alcohol of the following Formula 3 or a mixture of
the alcohol with at least one isomer thereof in the presence of a catalyst.

14
R’OH
[0040] In the above formula, R’ is at least one selected from the group consisting of C3-C10
alkyl of a non-branch type or including at least one branched chain, a substituted or unsubstituted
alkyl aryl and a substituted or unsubstituted aryl.
[0041] In this case, in the alcohol of the above Formula 3, the branched chain which may be
included in R’ may be C1-C6 alkyl, C2-C6 alkenyl or C2-C6 alkynyl.
[0042] The alcohol of the above Formula 2 according to an embodiment of the present
invention may be an alcohol where R’ includes one selected from the group consisting of C4-C9
alkyl of a non-branch type or including at least one C1-C4 alkyl branched chain, and phenyl or
benzyl of a non-branch type or including at least one C1-C4 alkyl branched chain.
[0043] In the esterification reaction, an ester bond may be obtained by a dehydration
condensation reaction of a carboxyl group (-COOH) substituted at a phenyl group in the
isophthalic acid of Formula 2 with a hydroxyl group (OH) in at least 1 alcohol, preferably 1-3
alcohols.
[0044] The esterification reaction is preferably conducted at a temperature range of 80°C to
270°C for 1 to 15 hours. The reaction time may be counted after elevating the temperature of the
reactant from the point reaching the reaction temperature.
[0045] When particularly examining, the isophthalic acid of the above Formula 2 and the
alcohol of the above Formula 3 (or a mixture of the alcohol and at least one isomer thereof) may
be used in a molar ratio of 1 : 0.01 to 5. In addition, according to another embodiment of the
present invention, in the case of using at least two different alcohols as the alcohol of the above
Formula 3, the molar ratio may be 1 : 0.1 to 4.9 : 0.1 to 4.9. For example, in the case that the
isophthalic acid of the above Formula 2, 2-ethylhexanol (2-EH) as the alcohol of the above
Formula 3 and 2-propylheptanol (2-PH) of the above Formula 6 (or a mixture of the 2-
propylheptanol and at least one alcohol isomer thereof) are used according to an embodiment of
the present invention, the molar ratio may be 1 : 0.1 to 4.9 : 0.1 to 4.9.
[0046] According to an embodiment of the present invention, the alcohol of the above
Formula 3 may be prepared by a common method or used by purchasing a commercially
available product. In the case of purchasing the commercially available product, the alcohol of
the above Formula 3 may be included as a mixture with at least one alcohol isomer thereof, and
the amount of the alcohol of the above Formula 3 : the alcohol isomer thereof may be included in
an amount ratio of , for example, 50 to 100 parts by weight : 0 to 50 parts by weight, and
preferably, 70 to 100 parts by weight : 0 to 30 parts by weight.
[0047] For example, in the case that the alcohol of the above Formula 3 is 2-propylheptane-
1-ol, 4-methyl-2-propyl-hexanol of the following Formula 3-1 or 5-methyl-2-propyl-hexanol of
the following Formula 3-2 may be included as the isomer thereof.

15

[0048] Further, as commercially available 2-propylheptane-1-ol, commercially available
products of BASF Co., including the isomer thereof such as CAS No. 10042-59-8, 66256-62-0,
159848-27-8, etc. may be used, and as isononyl alcohol, commercially available products
including the isomer thereof such as CAS No. 68526-84-1 of EXXONMOBILE Co., and CAS
No. 27458-94-2 (68515-81-1) of KYOWA Co., etc. may be used. However, the present
invention is not limited thereto.
[0049] In this case, if the molar ratio of the isophthalic acid and the alcohol is in the above
range, an ester compound for a plasticizer having high purity, yield and process efficiency and
excellent processability improving effects may be obtained.
[0050] The temperature of the esterification reaction after inserting raw materials and a
catalyst may be elevated up to 270°C and maintained for 1 to 15 hours, and unreacted alcohol
evaporated during reaction may be condensed using a condenser and inserted again for
continuous recycle. To effectively remove water generated during conducting the reaction, a
nitrogen gas which is an inert gas may be directly inserted in the reactant until completing the
reaction. Thus, a reaction product having an acid value of about 0.01 and conversion rate of 99%
and over may be effectively obtained after completing the reaction.
[0051] After completing the reaction, a process of removing unreacted materials by
maintaining for about 0.5 to 6 hours in vacuum conditions may be further included.
[0052] In addition, for removing a remaining unreacted acid, a cooling process, a
neutralizing treatment by adding an appropriate amount of an aqueous alkaline solution and a
washing process may be conducted. Then, water may be removed in vacuum for about 30 to 120
minutes until securing the water content to an appropriate degree and less. Finally, an
appropriate amount of a filter medium is inserted, followed by stirring at about 80°C to 110°C
for about 30 minutes and filtering to produce an isophthalate-based ester compound of the above
Formula 1.
16
[0053] The catalyst inserted in the reaction may include a Sn-based or Ti-based
organometallic catalyst, a sulfonic acid-based or sulfuric-based acid catalyst, or a mixture
thereof.
[0054] The organometallic catalyst may include, for example, at least one selected from a
titanium tetraalkoxide [Ti(OR)4] such as tetraisobutyl titanate and tetraisopropyl titanate, a tin
alkoxide [Sn(OR)2] such as dibutyltin oxide, etc.
[0055] In addition, the acid catalyst may include, for example, at least one selected from
paratoluenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid and
sulfuric acid. The reaction catalyst may be included in an amount of 0.01 to 5.0 parts by weight
with respect to 100 parts by weight of the isophthalic acid reaction material. In the case of using
the catalyst less than the lower limit, reaction efficiency may be decreased, and in the case of
exceeding the upper limit, a product may be discolored.
[0056] Further, the present invention may provide a plasticizer composition including the
ester compound of the above Formula 1 and a polyvinyl chloride (PVC) resin composition
including a polyvinyl chloride resin. In the PVC resin composition, the ester compound is added
as a plasticizer.
[0057] The plasticizer composition may be included in an amount of 10 to 150 parts by
weight with respect to 100 parts by weight of the polyvinyl chloride and may preferably be
included in an amount of 20 to 100 parts by weight.
[0058] According to an embodiment of the present invention, in the amount range, hardness,
tensile strength, elongation rate as well as processability with a resin such as short absorption
rate and short melting time may be improved, and particularly, migration loss and volatile loss
may be minimized.
[0059] In addition, the present invention may provide a resin composition including the
plasticizer composition and a resin other than the PVC resin composition, and the resin may be a
known resin in the art. For example, at least one selected from ethylenevinyl acetate,
polyethylene, polypropylene, polystyrene, polyurethane, thermoplastic elastomer, polylactic
acid, a synthetic rubber such as SBR, NBR, BR, etc. may be included, without limitation.
[0060] According to an embodiment of the present invention, the resin composition may
further include a filler.
[0061] The filler may be 0 to 300 parts by weight, preferably, 50 to 200 parts by weight, and
more preferably, 100 to 200 parts by weight on the basis of 100 parts by weight of the resin.
[0062] According to an embodiment of the present invention, the filler may be a known
filler in this art, without specific limitation. For example, a mixture of at least one selected from
silica, magnesium carbonate, calcium carbonate, hard charcoal, talc, magnesium hydroxide,
titanium dioxide, magnesium oxide, calcium hydroxide, aluminum hydroxide, aluminum silicate,
magnesium silicate and barium sulfate, may be used.
[0063] In addition, according to an embodiment of the present invention, the resin
composition may further include other additives such as a stabilizer, as occasion demands.
17
[0064] Each of the other additives such as the stabilizer may be included in an amount of 0
to 20 parts by weight, and preferably 1 to 15 parts by weight on the basis of 100 parts by weight
of the resin.
[0065] The stabilizer used according to an embodiment of the present invention may be Ca-
Zn-based stabilizer such as a composite stearate of calcium-zinc, without specific limitation.
[0066] In addition, according to an embodiment of the present invention, the resin
composition may further include at least one plasticizer composition selected from dioctyl
terephthalate (DOTP), diisononyl phthalate (DINP), diisodecyl phthalate (DIDP), dipropylheptyl
phthalate (DPHP), trioctyltrimellitate (TOTM), di-(2-ethylhexyl) terephthalate (DEHTP), dioctyl
adipate (DOA), butyloctyl terephthalate (BOTP), dioctyl succinate (DOSx), neopentyl glycolbased,
trimethylolpropane-based, diethylene glycol-based, triethylene glycol-based product. The
amount of the plasticizer composition may be 0 to 150 parts by weight and preferably, 5 to 100
parts by weight on the basis of 100 parts by weight of the resin.
[0067] The resin composition has an absorption rate of the ester compound of 3 to 10
minutes, 3 to 8 minutes, and more preferably, 4 to 7 minutes. In the range, workability and
processability are good.
[0068] The absorption rate may be evaluated by measuring a time period of mixing the resin
and the ester compound using a mixer (Product name: Brabender, P600) until the torque of the
mixer is stabilized under the conditions of 77°C and 60 rpm.
[0069] The ester compound according to an embodiment of the present invention has short
absorption rate and short melting time with respect to the resin, and the processability of the
resin may be improved, and good physical properties may be provided when prescribing a sheet
and a compound such as a cable, an interior material of a vehicle, a film, a sheet, a tube, a wall
paper, a toy, a flooring material, etc.
[0070] 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.
Examples
[0071] Hereinafter, examples and experimental examples will be further explained,
however the present invention is not limited to the following examples and experimental
examples.
Example 1
[0072] To a four-necked, 3 liter reactor equipped with a cooler, a water stripper, a
condenser, a decanter, a reflux pump, a temperature controller, a stirrer, etc., 498.0 g of purified
isophthalic acid (PIA), 586 g of 2-ethylhexanol (2-EH), 721 g of 2-propylheptanol (2-PH, BASF
Co.) (the molar ratio of PIA : 2-EH : 2-PH was 1.0 : 1.5 : 1.5) and 1.54 g of tetraisopropyl
titanate (TIPT) as a titanium-based catalyst (0.31 parts by weight on the basis of 100 parts by
weight of PIA) were inserted, followed by slowly elevating the temperature to about 170°C. The
18
generation of water began at about 170°C. An esterification reaction was conducted at the
reaction temperature of about 220°C under an atmospheric pressure while continuously injecting
a nitrogen gas for about 4.5 hours, and the reaction was terminated when an acid value reached
0.01.
[0073] After completing the reaction, a distillation extraction under a reduced pressure was
conducted for 0.5 to 4 hours to remove unreacted raw materials. To remove the unreacted raw
materials to a certain amount degree and less, steam extraction was conducted using steam under
a reduced pressure for 0.5 to 3 hours. The reactant was cooled, and neutralization treatment was
conducted using an alkaline solution. In addition, washing may be conducted, followed by
dehydrating the reactant to remove water. A filter medium was inserted to the dehydrated
reactant, followed by stirring for a certain time and filtering to obtain an isophthal-based
plasticizer composition including 49 wt% of 2-ethylhexyl 2-propylheptyl isophthalate (EHPIP)
of Formula 1-1, 17 wt% of di-(2-ethylhexyl) isophthalate (DEHIP) of Formula 1-20 and 34 wt%
of di-(2-propylheptyl) isophthalate (DPIP) of Formula 1-21 (yield 99.0%).
Examples 2 to 13
[0074] In Examples 2 to 13, plasticizer compositions of the following Table 1 were obtained
by applying the same conditions in Example 1 using the same molar ratio of the isophthalic acid
and the alcohol while changing the kind of the alcohol.
Comparative Example 1
[0075] LGflex DPHP (trade name) of LG Chem. was used.
Comparative Example 2
[0076] Diisodecyl phthalate (DIDP; LGfex DIDP, LG Chem.) was used as a plasticizer.
Comparative Example 3
[0077] Diundecyl isophthalate was prepared by the same preparation method in Example 1
as a plasticizer.
Comparative Example 4
[0078] A plasticizer composition including 50 wt% of undecyl-isotridecyl isophthalate, 23
wt% of diundecyl isophthalate and 27 wt% of diisotridecyl isophthalate was prepared by
conducting the same preparation method in Example 1.
[Table 1]
Ester-based composition (wt%)
Example 1 Formula 1-1 (47%) Formula 1-20 (17%) Formula 1-21 (36%)
Example 2 Formula 1-4 (53%) Formula 1-16 (15%) Formula 1-21 (32%)
Example 3 Formula 1-5 (50%) Formula 1-16 (20%) Formula 1-17 (30%)
Example 4 Formula 1-6 (48%) Formula 1-16 (16%) Formula 1-18 (36%)
Example 5 Formula 1-7 (47%) Formula 1-19 (35%) Formula 1-16 (18%)
Example 6 Formula 1-8 (44%) Formula 1-20 (24%) Formula 1-18 (32%)
Example 7 Formula 1-9 (47%) Formula 1-19 (28%) Formula 1-20 (25%)
Example 8 Formula 1-10 (49%) Formula 1-21 (26%) Formula 1-18 (25%)
Example 9 Formula 1-11 (50%) Formula 1-21 (30%) Formula 1-19 (20%)
19
Example 10 Formula 1-12 (47%) Formula 1-17 (25%) Formula 1-18 (38%)
Example 11 Formula 1-13 (49%) Formula 1-19 (19%) Formula 1-17 (32%)
Example 12 Formula 1-14 (46%) Formula 1-19 (17%) Formula 1-18 (37%)
Example 13 Formula 1-15 (45%) Formula 1-16 (21%) Formula 1-20 (34%)
Comparative
Example 1
DPHP (100%)
Comparative
Example 2
DIDP (100%)
Comparative
Example 3
Diundecyl
isophthalate (100%)
Comparative
Example 4
Undecyl, isotridecyl
isophthalate (50%)
Diundecyl
isophthalate (24%)
Diisotridecyl
isophthalate (26%)

Example 14
[0079] With respect to 100 parts by weight of polyvinyl chloride resin (PVC, LS 130s), 50
parts by weight of an isophthal-based composition including 47 wt% of 2-ethylhexyl 2-
propylheptyl isophthalate (EHPIP) of Formula 1-1, 17 wt% of di-(2-ethylhexyl) isophthalate
(DEHIP) of Formula 1-20 and 36 wt% of di-(2-propylheptyl) isophthalate (DPIP) of Formula 1-
21 prepared in Example 1, 5 parts by weight of a RUP stabilizer (RUP 144, Adeka Korea Co.) as
an additive, 40 parts by weight of calcium carbonate (Omya 1T, BSH) and 0.3 phr of stearic acid
(ST/A) as a stabilizer were mixed and hand mixed. A process was conducted at 160°C for 4
minutes using a roll mill, and at 180°C for 2.5 minutes (low pressure) and for 2 minutes (high
pressure) using a press to manufacture a sheet having a thickness of 1-3 mm.
Examples 15-26
[0080] Sheets were manufactured by conducting the same procedure described in Example
14 except for using the compositions of Examples 2 to 13 as a plasticizer.
Comparative Example 5
[0081] A sheet was manufactured by conducting the same procedure described in Example
14 except for using DPHP of Comparative Example 1 as a plasticizer.
Comparative Example 6
[0082] A sheet was manufactured by conducting the same procedure described in Example
14 except for using diisodecyl phthalate (DIDP; LGfex DIDP, LG Chem) of Comparative
Example 2 as a plasticizer.
Comparative Example 7
[0083] A sheet was manufactured by conducting the same procedure described in Example
14 except for using diundecyl isophthalate of Comparative Example 3 as a plasticizer.
Comparative Example 8
20
[0084] A sheet was manufactured by conducting the same procedure described in Example
14 except for using 50 wt% of undecyl-isotridecyl isophthalate, 24 wt% of diundecyl
isophthalate and 26 wt% of diisotridecyl isophthalate of Comparative Example 5 as a plasticizer.
Experimental Example 1: Evaluation of physical properties
[0085] Evaluation of performance with respect to hardness, tensile strength, elongation rate,
migration loss, sheet volatile loss and plasticizer absorption rate were conducted for the sheets
manufactured in Examples 14 to 26 and Comparative Examples 4 to 8. The results are shown in
Table 2.
[0086] The conditions of each evaluation of performance are as follows.
Measuring hardness
[0087] Shore hardness at 25°C, 3T 10s was measured using ASTM D2240.
Measuring tensile strength
[0088] By ASTM D638 method, a specimen was drawn in a cross head speed of 200
mm/min (1T) using a test apparatus of U.T.M (manufacturer: Instron, model name: 4466), and a
point where the specimen was cut was measured. The tensile strength was calculated as follows.
Tensile strength (kgf/cm2) = load value (kgf)/thickness (cm) x width (cm)
Measuring elongation rate
[0089] By ASTM D638 method, a specimen was drawn in a cross head speed of 200
mm/min (1T) using a test apparatus of U.T.M, and a point where the specimen was cut was
measured. The elongation rate was calculated as follows.
Elongation rate (%) = length after elongation/initial length x 100
Measuring migration loss
[0090] According to KSM-3156, a specimen with a thickness of 2 mm and over was
obtained, PS plates were attached onto both sides of the specimen and a load of 1 kgf/cm2 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, PS plates attached onto both sides
of the specimen were removed, the weights before and after standing in the oven were measured,
and the migration loss was calculated by the following equation.
Migration loss (%) = {(initial weight of specimen at room temperature - weight of specimen after
standing in oven)/initial weight of specimen at room temperature} x 100
Measuring sheet volatile loss
[0091] The specimen thus manufactured was processed at 100°C for 168 hours, and the
weight of the specimen was measured.
21
Volatile loss (wt%) = initial weight of specimen -(weight of specimen after processing at 100°C
for 168 hours)/initial weight of specimen x 100
[Table 2]
Hardness
(Shore “A”)
Tensile
strength
(kg/cm2)
Elongation
rate (%)
Migration
loss (%)
Volatile loss
(%)
Example 14 90.7 183.4 227.8 0.11 2.09
Example 15 87.6 181.5 285.1 0.48 2.35
Example 16 86.7 179.5 282.6 0.56 3.20
Example 17 88.5 182.6 286.9 0.39 1.02
Example 18 87.2 175.6 259.4 0.55 0.88
Example 19 93.5 195.6 288.6 0.08 0.85
Example 20 91.4 194.7 268.9 0.10 0.90
Example 21 93.3 207.9 291.5 0.03 0.35
Example 22 90.3 201.7 268.5 0.15 0.55
Example 23 92.5 208.5 284.6 0.05 0.30
Example 24 91.4 201.3 251.3 0.14 0.56
Example 25 91.5 204.6 260.5 0.15 0.48
Example 26 87.6 182.4 232.5 0.14 2.53
Comparative
Example 6
89.5 185.6 231.7 0.89 1.89
Comparative
Example 7
90.0 183.5 241.2 0.18 1.07
Comparative
Example 8
92.2 210.3 221.5 0.04 0.35
Comparative
Example 9
93.8 214.9 216.5 0.02 0.25
[0092] The sheets of Examples 14 to 26 using the plasticizer compositions (Examples 1 to
13) according to an embodiment of the present invention as a plasticizer had appropriate physical
properties for a resin and were secured to be used for an appropriate use. The isophthalates using
an alcohol having a small molecular weight exhibited relatively good hardness and elongation
property when compared to comparative examples, and the isophthalates using an alcohol having
a large molecular weight exhibited the same or better physical properties of migration loss and
volatile loss when compared to comparative examples. When the novel compound including the
blended alcohol is appropriately applied according to use, good processing physical properties
and physical effects satisfying required properties may be expected.

Examples 27 to 31
22
Example 27
[0093] To a four-necked, 3 liter reactor equipped with a cooler, a water stripper, a
condenser, a decanter, a reflux pump, a temperature controller, a stirrer, etc., 498.0 g of purified
isophthalic acid (PIA), 586 g of 2-ethylhexanol (2-EH), 721 g of 2-propylheptanol (2-PH, BASF
Co. including 85-100 wt% of 2-PH, 0-15 wt% of 4-methyl-2-propyl-hexanol and 0-15 wt% of 5-
methyl-2-propyl-hexanol) (the molar ratio of PIA : 2-EH : 2-PH was 1.0 : 1.5 : 1.5) and 1.24 g of
tetra n-butyl titanate (TNBT) as a titanium-based catalyst (0.25 parts by weight on the basis of
100 parts by weight of PIA) were inserted, followed by slowly elevating the temperature to about
170°C. The generation of water began at about 170°C. An esterification reaction was conducted
at the reaction temperature of about 220°C under an atmospheric pressure while continuously
injecting a nitrogen gas for about 3.5 hours, and the reaction was terminated when an acid value
reached 0.3.
[0094] After completing the reaction, distillation extraction under a reduced pressure was
conducted for 0.5 to 2 hours to remove unreacted raw materials. To remove the unreacted raw
materials to a certain amount degree and less, steam extraction was conducted using steam under
a reduced pressure for 0.5 to 3 hours. The temperature of the reactant was lowered to about
90°C, and neutralization treatment was conducted using an alkaline solution. In addition,
washing may be conducted, followed by dehydrating the reactant to remove water. A filter
medium was inserted to the dehydrated reactant, followed by stirring for a certain time and
filtering to obtain an isophthal-based plasticizer composition including 48 wt% of 2-ethylhexyl
2-propylheptyl isophthalate (EHPIP) of Formula 1, 17 wt% of di-(2-ethylhexyl) isophthalate
(DEHIP) of Formula 2 and 35 wt% of di-(2-propylheptyl) isophthalate (DPIP) of Formula 3.
Example 28
[0095] To a four-necked, 3 liter reactor equipped with a cooler, a water stripper, a
condenser, a decanter, a reflux pump, a temperature controller, a stirrer, etc., 498.0 g of purified
isophthalic acid (PIA), 820 g of 2-ethylhexanol (2-EH, LG Chem.), 428 g of 2-propylheptanol
(2-PH, BASF Co., including 85-100 wt% of 2-PH, 0-15 wt% of 4-methyl-2-propyl-hexanol and
0-15 wt% of 5-methyl-2-propyl-hexanol) (the molar ratio of PIA : 2-EH : 2-PH was 1.0 : 2.1 :
0.9) and 1.24 g of tetra n-butyl titanate (TNBT) as a titanium-based catalyst (0.25 parts by
weight on the basis of 100 parts by weight of PIA) were inserted, followed by slowly elevating
the temperature to about 170°C. The generation of water began at about 170°C. An
esterification reaction was conducted at the reaction temperature of about 220°C under an
atmospheric pressure while continuously injecting a nitrogen gas for about 3 hours, and the
reaction was terminated when an acid value reached 0.3.
[0096] After completing the reaction, a post-treatment such as removing of unreacted raw
materials, neutralization, washing, dehydration, etc. was conducted as in Example 27. Finally,
an isophthal-based plasticizer composition including 41 wt% of 2-ethylhexyl 2-propylheptyl
isophthalate (EHPIP) of Formula 1, 46 wt% of di-(2-ethylhexyl) isophthalate (DEHIP) of
Formula 2 and 13 wt% of di-(2-propylheptyl) isophthalate (DPIP) of Formula 3 was obtained.
23
Example 29
[0097] To a four-necked, 3 liter reactor equipped with a cooler, a water stripper, a
condenser, a decanter, a reflux pump, a temperature controller, a stirrer, etc., 498.0 g of purified
isophthalic acid (PIA), 1,055 g of 2-ethylhexanol (2-EH, LG Chem), 143 g of 2-propylheptanol
(2-PH) (BASF Co., including 85-100 wt% of 2-PH, 0-15 wt% of 4-methyl-2-propyl-hexanol and
0-15 wt% of 5-methyl-2-propyl-hexanol) (the molar ratio of PIA : 2-EH : 2-PH was 1.0 : 2.7 :
0.3) and 1.24 g of tetra n-butyl titanate (TNBT) as a titanium-based catalyst (0.25 parts by
weight on the basis of 100 parts by weight of PIA) were inserted, followed by slowly elevating
the temperature to about 170°C. The generation of water began at about 170°C. An
esterification reaction was conducted at the reaction temperature of about 220°C under an
atmospheric pressure while continuously injecting a nitrogen gas for about 3 hours, and the
reaction was terminated when an acid value reached 0.3.
[0098] After completing the reaction, a post-treatment such as removing of unreacted raw
materials, neutralization, washing, dehydration, etc. was conducted as in Example 27. Finally,
an isophthal-based plasticizer composition including 77 wt% of 2-ethylhexyl 2-propylheptyl
isophthalate (EHPIP) of Formula 1, 22 wt% of di-(2-ethylhexyl) isophthalate (DEHIP) of
Formula 2 and 1 wt% of di-(2-propylheptyl) isophthalate (DPIP) of Formula 3 was obtained.
Example 30
[0099] To a four-necked, 3 liter reactor equipped with a cooler, a water stripper, a
condenser, a decanter, a reflux pump, a temperature controller, a stirrer, etc., 498.0 g of purified
isophthalic acid (PIA), 352 g of 2-ethylhexanol (2-EH, LG Chem), 997 g of 2-propylheptanol (2-
PH) (BASF Co., including 85-100 wt% of 2-PH, 0-15 wt% of 4-methyl-2-propyl-hexanol and 0-
15 wt% of 5-methyl-2-propyl-hexanol) (the molar ratio of PIA : 2-EH : 2-PH was 1.0 : 0.9 : 2.1)
and 1.24 g of tetra n-butyl titanate (TNBT) as a titanium-based catalyst (0.25 parts by weight on
the basis of 100 parts by weight of PIA) were inserted, followed by slowly elevating the
temperature to about 170°C. The generation of water began at about 170°C. An esterification
reaction was conducted at the reaction temperature of about 220°C under an atmospheric
pressure while continuously injecting a nitrogen gas for about 4 hours, and the reaction was
terminated when an acid value reached 0.3.
[00100] After completing the reaction, a post-treatment such as removing of unreacted raw
materials, neutralization, washing, dehydration, etc. was conducted as in Example 27. Finally,
an isophthal-based plasticizer composition including 37 wt% of 2-ethylhexyl 2-propylheptyl
isophthalate (EHPIP) of Formula 1, 6 wt% of di-(2-ethylhexyl) isophthalate (DEHIP) of Formula
2 and 57 wt% of di-(2-propylheptyl) isophthalate (DPIP) of Formula 3 was obtained.
Example 31
[00101] To a four-necked, 3 liter reactor equipped with a cooler, a water stripper, a
condenser, a decanter, a reflux pump, a temperature controller, a stirrer, etc., 498.0 g of purified
24
isophthalic acid (PIA), 117 g of 2-ethylhexanol (2-EH, LG Chem.), 1,287 g of 2-propylheptanol
(2-PH) (BASF Co., including 85-100 wt% of 2-PH, 0-15 wt% of 4-methyl-2-propyl-hexanol and
0-15 wt% of 5-methyl-2-propyl-hexanol) (the molar ratio of PIA : 2-EH : 2-PH was 1.0 : 0.3 :
2.7) and 1.24 g of tetra n-butyl titanate (TNBT) as a titanium-based catalyst (0.25 parts by
weight on the basis of 100 parts by weight of PIA) were inserted, followed by slowly elevating
the temperature to about 170°C. The generation of water began at about 170°C. An
esterification reaction was conducted at the reaction temperature of about 220°C under an
atmospheric pressure while continuously injecting a nitrogen gas for about 3 hours, and the
reaction was terminated when an acid value reached 0.3.
[00102] After completing the reaction, a post-treatment such as removing of unreacted raw
materials, neutralization, washing, dehydration, etc. was conducted as in Example 27. Finally,
an isophthal-based plasticizer composition including 13.5 wt% of 2-ethylhexyl 2-propylheptyl
isophthalate (EHPIP) of Formula 1, 0.5 wt% of di-(2-ethylhexyl) isophthalate (DEHIP) of
Formula 2 and 86.0 wt% of di-(2-propylheptyl) isophthalate (DPIP) of Formula 3 was obtained.
Comparative Example 10
[00103] A phthalate-based plasticizer of diisodecyl phthalate (DIDP) of Exxonmobil was
used.

Examples 32 to 36 and Comparative Example 11
[00104] With respect to 100 parts by weight of polyvinyl chloride resin (PVC, LS 130s), 50
parts by weight of the plasticizer compositions or compounds prepared in Examples 27 to 31 and
Comparative Example 10, 5 parts by weight of a RUP stabilizer (RUP 144, Adeka Korea Co.) as
an additive, 40 parts by weight of calcium carbonate (Omya 1T, BSH) and 0.3 phr of stearic acid
(ST/A) as a stabilizer were mixed. A process was conducted at 160°C for 4 minutes using a roll
mill, and at 180°C for 2.5 minutes (low pressure) and for 2 minutes (high pressure) using a press
to manufacture a sheet having a thickness of 1.3 mm. Sheets manufactured using the plasticizer
compositions of Examples 27 to 31 were considered as Examples 32 to 46 one by one, and the
sheet manufactured using the plasticizer composition of Comparative Example 10 was
considered as Comparative Example 11.
Experimental Example 2: Evaluation of physical properties
[00105] Evaluation of performance on hardness, tensile strength, elongation rate, migration
loss, sheet volatile loss and plasticizer absorption rate were conducted for the sheets
manufactured in Examples 32 to 36 and Comparative Example 11. The results are shown in the
following Table 3.
[Table 3]
Example
32
Example
33
Example
34
Example
35
Example
36
Comparative
Example 11
25
Hardness
(Shore “A”)
89.5 88.5 87.7 90.2 90.5 89.8
Tensile
strength
(kgf/cm2)
196.8 193.9 191.9 190.2 187.0 171.5
Elongation
rate (%)
302.8 303.0 309.1 300.1 300.1 282.6
Migration
loss (%)
0.08 0.10 0.04 0.05 0.06 0.11
Volatile
loss (%)
1.1 1.6 2.5 0.5 0.3 1.4
[00106] As shown in the above Table 3, when comparing the physical properties of the sheet
of Comparative Example 11 obtained by using the plasticizer DIDP of Comparative Example 10
with those of the sheets of Examples 32 to 36 using the plasticizers of the examples of the
present invention, the hardness in the examples was the same or better than that in Comparative
Example 11, and the plasticizing efficiency of the plasticizers of Examples 27 to 31 is better than
that of the plasticizer of Comparative Example 10. The tensile strength of the sheets of
Examples 32 to 36 exhibited better efficiency than that of the sheet of Comparative Example 11,
and the migration loss of the sheets of the examples was better three times than that of the sheet
of Comparative Example 11.
[00107] Volatile loss of the sheets of Examples 35 to 36 was measured to decrease with good
degree when compared to the sheet of Comparative Example 11 using the plasticizer of
Comparative Example 10. The sheets of Examples 32 to 34 were secured to exhibit the same
degree as the sheet of Comparative Example 11. As a result, the sheets of Examples 32 to 36
using the plasticizers of Examples 27 to 31 exhibited better physical properties than the sheet of
Comparative Example 11 using a common plasticizer of Comparative Example 10.
Examples 37 to 40
Example 37
[00108] To a four-necked, 3 liter reactor equipped with a cooler, a water stripper, a
condenser, a decanter, a reflux pump, a temperature controller, a stirrer, etc., 498.0 g of purified
isophthalic acid (PIA), 712.5 g of 2-propylheptanol (2-PH) (BASF Co., including 85-100 wt% of
2-PH, 0-15 wt% of 4-methyl-2-propyl-hexanol and 0-15 wt% of 5-methyl-2-propyl-hexanol) and
649.4 g of isononyl alcohol (INA) (the molar ratio of PIA: 2-PH : INA was 1.0 : 1.5 : 1.5) and
1.54 g of tetra isopropyl titanate (TIPT) as a titanium-based catalyst (0.31 parts by weight on the
basis of 100 parts by weight of PIA) were inserted, followed by slowly elevating the temperature
to about 170°C. The generation of water began at about 170°C. An esterification reaction was
26
conducted at the reaction temperature of about 220°C under an atmospheric pressure while
continuously injecting a nitrogen gas for about 4.5 hours, and the reaction was terminated when
an acid value reached 0.01.
[00109] After completing the reaction, unreacted alcohol in the reactant was removed by
distillation, and the reactant was neutralized/washed, and filtered to finally produce an isophthalbased
plasticizer composition including 42 wt% of 2-propylhepty isononyl isophthalate (PINIP)
of Formula 1, 31 wt% of di-(2-propylheptyl) isophthalate (DPIP) of Formula 2 and 27 wt% of
diisononyl isophthalate (DINIP) of Formula 3.
Example 38
[00110] An isophthal-based plasticizer composition including 42 wt% of 2-propylhepty
isononyl isophthalate (PINIP) of Formula 1, 21 wt% of di-(2-propylheptyl) isophthalate (DPIP)
of Formula 2 and 37 wt% of diisononyl isophthalate (DINIP) of Formula 3 was finally obtained
by conducting the same procedure described in Example 37 except for using, as the alcohol,
427.4 g of 2-propylheptanol (2-PH) (BASF Co., including 85-100 wt% of 2-PH, 0-15 wt% of 4-
methyl-2-propyl-hexanol and 0-15 wt% of 5-methyl-2-propyl-hexanol) and 909.1 g of isononyl
alcohol (INA) (the molar ratio of PIA: 2-PH : INA was 1.0 : 0.9 : 2.1) and filtering.
Example 39
[00111] An isophthal-based plasticizer composition including 23 wt% of 2-propylhepty
isononyl isophthalate (PINIP) of Formula 1, 10 wt% of di-2-propylheptyl isophthalate (DPIP) of
Formula 2 and 67 wt% of diisononyl isophthalate (DINIP) of Formula 3 was finally obtained by
conducting the same procedure described in Example 37 except for using, as the alcohol, 142.5 g
of 2-propylheptanol (2-PH) (BASF Co., including 85-100 wt% of 2-PH, 0-15 wt% of 4-methyl-
2-propyl-hexanol and 0-15 wt% of 5-methyl-2-propyl-hexanol) and 1,168.8 g of isononyl
alcohol (INA) (the molar ratio of PIA: 2-PH : INA was 1.0 : 0.3 : 2.7) and filtering.
Example 40
[00112] An isophthal-based plasticizer composition including 37 wt% of 2-propylhepty
isononyl isophthalate (PINIP) of Formula 1, 55 wt% of di-2-propylheptyl isophthalate (DPIP) of
Formula 2 and 8 wt% of diisononyl isophthalate (DINIP) of Formula 3 was finally obtained by
conducting the same procedure described in Example 37 except for using, as the alcohol, 997.3 g
of 2-propylheptanol (2-PH) (BASF Co., including 85-100 wt% of 2-PH, 0-15 wt% of 4-methyl-
2-propyl-hexanol and 0-15 wt% of 5-methyl-2-propyl-hexanol) and 389.6 g of isononyl alcohol
(INA) (the molar ratio of PIA: 2-PH : INA was 1.0 : 2.1 : 0.9) and filtering.
Comparative Example 12
27
[00113] A phthalate-based plasticizer of diisodecyl phthalate (DIDP) of Exxonmobil was
used.

Examples 41 to 44 and Comparative Example 13
[00114] With respect to 100 parts by weight of polyvinyl chloride resin (PVC, LS 130s), 50
parts by weight of the plasticizer compositions or compounds prepared in Examples 37 to 40 and
Comparative Example 12, 5 parts by weight of a RUP stabilizer (RUP 144, Adeka Korea Co.) as
an additive, 40 parts by weight of calcium carbonate (Omya 1T, BSH) and 0.3 phr of stearic acid
(ST/A) as a stabilizer were mixed. A process was conducted at 160°C for 4 minutes using a roll
mill, and at 180°C for 2.5 minutes (low pressure) and for 2 minutes (high pressure) using a press
to manufacture a sheet having a thickness of 1 mm and 3 mm. Sheets manufactured using the
plasticizer compositions of Examples 37 to 40 were considered as Examples 41 to 44 one by one,
and the sheet manufactured using the plasticizer composition of Comparative Example 12 was
considered as Comparative Example 13.
Experimental Example 3: Evaluation of physical properties
[00115] Evaluation of performance on hardness, tensile strength, elongation rate, migration
loss, sheet volatile loss and plasticizer absorption rate were conducted for the sheets
manufactured in Examples 41 to 44 and Comparative Example 13. The results are shown in the
following Table 4.
[Table 4]
Example 41 Example 42 Example 43 Example 44 Comparative
Example 13
Hardness
(Shore “A”)
91 91.5 90 91.5 91
Tensile
strength
(kgf/cm2)
194.1 189.4 173.8 198.9 193.3
Elongation
rate (%)
293.8 295.2 289.8 300.2 278.2
Migration
loss (%)
0.04 0.08 0.07 0.02 0.10
Volatile
loss (%)
1.03 1.06 1.08 0.97 1.2
28
[00116] As shown in the above Table 4, when comparing the physical properties of the sheet
of Comparative Example 13 obtained by using the plasticizer DIDP of Comparative Example 12
with those of the sheets of Examples 41 to 44 using the plasticizers of the examples of the
present invention, the hardness in the examples was the same or better than that in Comparative
Example 13, and the plasticizing efficiency of the plasticizers of the examples is better than a
common product.
[00117] The tensile strength of the sheets of Examples 41 to 44 exhibited the same or better
efficiency than that of the sheet of Comparative Example 13, and the migration loss in Examples
41 to 44 was better up to five times than in Comparative Example 13.
[00118] Volatile loss of the sheets of Examples 41 to 44 was secured to decrease with good
degree when compared to the sheet of Comparative Example 13 using the plasticizer of
Comparative Example 12.
[00119] As a result, the sheets of Examples 41 to 44 using the plasticizers of Examples 37 to
40 exhibited better physical properties than the sheet of Comparative Example 13 using a
common plasticizer of Comparative Example 12.
Examples 45 to 49
Example 45
[00120] To a four-necked, 3 liter reactor equipped with a cooler, a water stripper, a
condenser, a decanter, a reflux pump, a temperature controller, a stirrer, etc., 498.0 g of purified
isophthalic acid (PIA), 117.2 g of 2-ethylhexanol (2-EH), 1,168.4 g of isononyl alcohol (INA)
(the molar ratio of PIA: 2-EH : INA was 1.0 : 0.3 : 2.7) and 1.54 g of tetra isopropyl titanate
(TIPT) as a titanium-based catalyst (0.31 parts by weight on the basis of 100 parts by weight of
PIA) were inserted, followed by slowly elevating the temperature to about 170°C. The
generation of water began at about 170°C. An esterification reaction was conducted at the
reaction temperature of about 220°C under an atmospheric pressure while continuously injecting
a nitrogen gas for about 4.5 hours, and the reaction was terminated when an acid value reached
0.2.
[00121] After completing the reaction, distillation-extraction under a reduced pressure was
conducted for 0.5 to 4 hours to remove unreacted raw materials. To remove the unreacted raw
materials to a certain amount degree and less, steam extraction was conducted using steam under
a reduced pressure for 0.5 to 3 hours. The temperature of the reactant was lowered to about
90°C, and neutralization treatment was conducted using an alkaline solution. In addition,
washing may be conducted, followed by dehydrating the reactant to remove water. A filter
medium was inserted to the dehydrated reactant, followed by stirring for a certain time and
filtering to obtain an isophthal-based plasticizer composition including 16 wt% of 2-ethylhexyl
29
isononyl isophthalate (EHINIP) of Formula 1, 1 wt% of di-(2-ethylhexyl) isophthalate (DEHIP)
of Formula 2 and 83 wt% of di-isononyl isophthalate (DINIP) of Formula 3.
Example 46
[00122] An isophthal-based plasticizer composition including 44 wt% of 2-ethylhexyl
isononyl isophthalate (EHINIP) of Formula 1, 7 wt% of di-(2-ethylhexyl) isophthalate (DEHIP)
of Formula 2 and 49 wt% of diisononyl isophthalate (DINIP) of Formula 3 was finally obtained
by conducting the same procedure described in Example 45 except for using, as the alcohol,
351.6 g of 2-ethylhexanol (2-EH) and 908.8 g of isononyl alcohol (INA) (the molar ratio of PIA:
2-PH : INA was 1.0 : 0.9 : 2.1) and filtering.
Example 47
[00123] An isophthal-based plasticizer composition including 55 wt% of 2-ethylhexyl
isononyl isophthalate (EHINIP) of Formula 1, 20 wt% of di-(2-ethylhexyl) isophthalate (DEHIP)
of Formula 2 and 25 wt% of diisononyl isophthalate (DINIP) of Formula 3 was finally obtained
by conducting the same procedure described in Example 45 except for using, as the alcohol,
586.0 g of 2-ethylhexanol and 649.1 g of isononyl alcohol (INA) (the molar ratio of PIA: 2-PH :
INA was 1.0 : 1.5 : 1.5) and filtering.
Example 48
[00124] An isophthal-based plasticizer composition including 46 wt% of 2-ethylhexyl
isononyl isophthalate (EHINIP) of Formula 1, 44 wt% of di-(2-ethylhexyl) isophthalate (DEHIP)
of Formula 2 and 10 wt% of diisononyl isophthalate (DINIP) of Formula 3 was finally obtained
by conducting the same procedure described in Example 45 except for using, as the alcohol,
820.5 g of 2-ethylhexanol and 389.5 g of isononyl alcohol (INA) (the molar ratio of PIA : 2-PH :
INA was 1.0 : 2.1 : 0.9) and filtering.
Example 49
[00125] An isophthal-based plasticizer composition including 20 wt% of 2-ethylhexyl
isononyl isophthalate (EHINIP) of Formula 1, 79 wt% of di-(2-ethylhexyl) isophthalate (DEHIP)
of Formula 2 and 1 wt% of diisononyl isophthalate (DINIP) of Formula 3 was finally obtained
by conducting the same procedure described in Example 45 except for using, as the alcohol,
1,054.9 g of 2-ethylhexanol (2-EH) and 129.8 g of isononyl alcohol (INA) (the molar ratio of
PIA : 2-PH : INA was 1.0 : 2.7 : 0.3) and filtering.
Comparative Example 14
[00126] A phthalate-based plasticizer of diisodecyl phthalate (DIDP) of Exxonmobil was
used.
30

Examples 50 to 54 and Comparative Example 15
[00127] With respect to 100 parts by weight of polyvinyl chloride resin (PVC, LS 100s), 50
parts by weight of the plasticizer compositions or compounds prepared in Examples 45 to 49 and
Comparative Example 14, 5 parts by weight of a RUP stabilizer (RUP 144, Adeka Korea Co.) as
an additive, 40 parts by weight of calcium carbonate (Omya 1T, BSH) and 0.3 phr of stearic acid
(ST/A) as a stabilizer were mixed. The mixing was conducted using a 3L super mixer (Korea
EM) at 200 rpm for 2 minutes and at 500 rpm for 3 minutes, and the mixing was conducted while
increasing to 700 rpm to 100°C to produce a final mixture. A process was conducted at 160°C
for 4 minutes using a roll mill, and at 180°C for 2.5 minutes (low pressure) and for 2 minutes
(high pressure) using a press to manufacture a sheet having a thickness of 1 mm and 3 mm.
Sheets thus manufactured were considered as Examples 50 to 54 and Comparative Example 15.
Experimental Example 4: Evaluation of physical properties
[00128] Performance evaluation on hardness, tensile strength, elongation rate, migration loss,
sheet volatile loss and plasticizer absorption rate were conducted for the sheets manufactured in
Examples 50 to 54 and Comparative Example 15. The results are shown in the following Table
5.
[Table 5]
(2-EH :
INA)
Example
50 (1:9)
Example
51 (3:7)
Example
52 (5:5)
Example
53 (7:3)
Example
54 (9:1)
Comparative
Example 15
Hardness
(Shore “A”)
89.2 88.7 88.5 88.0 87.7 90.0
Tensile
strength
(kgf/cm2)
188.7 189.9 194.2 192.5 190.2 183.5
Elongation
rate (%)
298.2 294.9 297.0 303.5 295.5 281.2
Migration
loss (%)
0.12 0.12 0.14 0.15 0.17 0.18
Volatile
loss (%)
1.03 1.34 1.97 2.40 2.70 1.07
[00129] 2-EH : INA represents the molar ratio of 2-ethylhexyl alcohol (2-EH) : isononyl
alcohol (INA) added during preparing a plasticizer.
[00130] As shown in the above Table 5, it could be secured that the sheets of Examples 50 to
54 using the plasticizers of Examples 45 to 49 of the present invention have lower hardness than
31
the sheet of Comparative Example 15 obtained by using the plasticizer of Comparative Example
11.
[00131] When examining the difference of physical properties according to the molar ratio of
2-EH : INA of the sheets of Examples 50 to 54, plasticizing efficiency was increased when the
ratio of 2-EH was increased during preparing the plasticizer. In addition, it could be secured that
the migration loss was improved according to the increase of the ratio of INA during preparing
the plasticizer.
[00132] The tensile strength and the elongation rate of the sheets of Examples 50 to 54 was
somewhat higher and exhibited similar degree without great difference when compared to the
sheet of Comparative Example 15.
[00133] The migration loss of the sheets of Examples 50 to 54 were good when compared to
that of Comparative Example 15, and as a result, it could be secured that good physical
properties were exhibited in the sheets of Examples 50 to 54 using the plasticizers of Examples
45 to 49 when compared to that of Comparative Example 15 using a common plasticizer of
Comparative Example 14.
32
WE CLAIM:
1. An ester compound of the following Formula 1:

in the above formula, R1 and R2 are different from each other and are independently at least one
selected from the group consisting of C3-C10 alkyl of a non-branch type or including at least one
branched chain, a substituted or unsubstituted alkyl aryl and a substituted or unsubstituted aryl.
2. The ester compound of claim 1, wherein the branched chain is C1-C6 alkyl, C2-C6 alkenyl or
C2-C6 alkynyl.
3. The ester compound of claim 2, wherein R1 and R2 are different from each other and are
independently at least one selected from the group consisting of C4-C9 alkyl of a non-branch type
or including at least one branched chain of C1-C4 alkyl, and phenyl or benzyl of a non-branch
type or including at least one branched chain of C1-C4 alkyl.
4. The ester compound of claim 3, wherein the ester compound comprises at least one ester
compound selected from compounds in the following formulae:

33

34

35

36

5. A plasticizer composition comprising the ester compound of claim 1.
6. The plasticizer composition of claim 5, further comprising at least one compound selected
from the group consisting of compounds of the following formulae:

37

38

7. The plasticizer composition of claim 6, wherein the plasticizer composition comprises
compounds of the following formulae:

39
8. The plasticizer composition of claim 6, wherein the plasticizer composition comprises
compounds of the following formulae:

9. The plasticizer composition of claim 6, wherein the plasticizer composition comprises
compounds of the following formulae:

40

10. A method of preparing the plasticizer composition of claim 5, the method comprising:
conducting an esterification reaction of isophthalic acid of the following Formula 2 with at least
one alcohol of the following Formula 3 or a mixture of the alcohol with at least one isomer
thereof in the presence of a catalyst:

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R’OH
in the above formula, R’ is at least one selected from the group consisting of C3-C10 alkyl of a
non-branch type or including at least one branched chain, a substituted or unsubstituted alkyl aryl
and a substituted or unsubstituted aryl.
11. The method of a plasticizer composition of claim 10, wherein the branched chain is C1-C6
alkyl, C2-C6 alkenyl or C2-C6 alkynyl.
12. The method of a plasticizer composition of claim 10, wherein the esterification reaction is
conducted at 80°C to 270°C.
13. The method of a plasticizer composition of claim 10, wherein the catalyst is an
organometallic catalyst comprising a Sn-based or Ti-based catalyst, an acid catalyst comprising a
sulfonic acid-based or sulfuric acid-based catalyst, or a mixture catalyst thereof.
14. The method of a plasticizer composition of claim 10, wherein the isophthalic acid of the
above Formula 2 with at least one alcohol of the above Formula 3 or a mixture of the alcohol
with at least one isomer thereof is used in a molar ratio of 1 : 0.01 to 5.
15. A polyvinyl chloride resin composition comprising the plasticizer composition of claim 5 and
a polyvinyl chloride resin.
16. The polyvinyl chloride resin composition of claim 15, wherein the plasticizer composition is
comprised in an amount of 10 to 150 parts by weight on the basis of 100 parts by weight of the
polyvinyl chloride resin.
17. A resin composition comprising the plasticizer composition of claim 5 and a resin.
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18. The resin composition of claim 17, wherein the resin comprises at least one selected from
ethylenevinyl acetate, polyethylene, polypropylene, polystyrene, polyurethane, thermoplastic
elastomer, polylactic acid, SBR, NBR and BR.
19. The resin composition of claim 17, wherein the plasticizer composition is comprised in an
amount of 10 to 150 parts by weight on the basis of 100 parts by weight of the resin.