TECHNICAL FIELD
[0001] The present invention relates to a novel ester compound, an ester composition
including the same, a preparation method of the plasticizer composition and a resin composition
including the plasticizer composition as a plasticizer, and more particularly, to an ester
composition including three kinds of isophthalate-based compounds, a preparation method of the
plasticizer composition and a resin composition including the plasticizer composition as a
plasticizer.
BACKGROUND ART
[0002] Generally, a plasticizer is a corresponding ester obtained by the reaction of an
alcohol with a polycarboxylic acid such as phthalic acid and adipic acid. Commercially
significant examples include an adipate of C8, C9 and C10 alcohol such as di(2-ethylhexyl)
adipate, diisononyl adipate and diisodecyl adipate; and a phthalate of C8, C9 and C10 alcohol
such as di(2-ethylhexyl) phthalate, diisononyl phthalate and diisodecyl phthalate.
[0003] Particularly, the di(2-ethylhexyl) phthalate is used for manufacturing plastisol and a
toy, a film, shoes, a paint, a flooring material, gloves, a wall paper, a synthetic leather, a sealant,
tarpaulin, a coating agent of the bottom of a vehicle, a furniture, a foamed mat and a soundproof
panel via a dry mixing, and may be used for manufacturing an outer packing and insulation of a
PVC cable, and for producing other calendered PVC products with plasticity.
[0004] Now, di-(2-ethylhexyl) phthalate, etc. are widely used as an ester-based plasticizer,
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, the degree of migration loss and heat stability.
[0005] 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, the degree of migration loss, heat stability, etc., and a method of preparing the same is
required.
DISCLOSURE OF THE INVENTION
TECHNICAL PROBLEM
[0006] A technical task intend to solve in the present invention is to provide a novel esterbased
compound.
[0007] Another technical task to solve in the present invention is to provide an ester–based
composition having good plasticizing efficiency and improved processability of a resin and
providing good physical properties 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.
[0008] Another technical task to solve in the present invention is to provide a preparation
method of the ester-based composition.
[0009] Final technical task to solve in the present invention is to provide a resin composition
including the ester-based composition as a plasticizer.
3
TECHNICAL SOLUTION
[0010] To solve the aspect of the present invention, there is provided an ester composition
including the compounds of the following Formula 1, Formula 2 and Formula 3.

[0011] In the above Formulae 1 to 3, R1 and R2 are independently C1-C20 alkyl, and R1 and
R2 are not the same.
[0012] In addition, there is provided in the present invention a preparation method of the
ester composition including conducting a trans-esterification reaction of a compound of the
following Formula 3 with a first alcohol of the following Formula 4.

R1-OH
[0013] In the above formulae, R1 and R2 are independently C1-C20 alkyl, and R1 and R2 are
not the same.
[0014] Further, there is provided in the present invention at least one ester-based compound
selected from the group consisting of compounds of the following formulae.

4

[0015] Further, there is provided in the present invention a resin composition including the
ester-based composition as a plasticizer and a resin.
ADVANTAGEOUS EFFECTS
[0016] The ester compound according to an embodiment of the present invention improves
plasticization efficiency and the processability of a resin when used as a plasticizer, and provides
good physical properties such as tensile strength, elongation rate, migration resistance, volatile
loss, etc.
MODE FOR CARRYING OUT THE INVENTION
[0017] Hereinafter, the present invention will be explained in detail to assist the
understanding of the present invention.
[0018] 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
based on the principle that inventors may appropriately define the concept of the terms to explain
the invention at his best method.
[0019] According to an embodiment of the present invention, an ester-based composition
5
including the following Formula 1, Formula 2 and Formula 3 is provided.

[0020] In the above Formulae 1 to 3, R1 and R2 are independently C1-C20 alkyl, and R1 and
R2 are not the same.
[0021] The ester-based composition according to an embodiment of the present invention is
characterized in including the isophthalate-based compounds of the above Formulae 1 to 3. That
is, the ester composition includes 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, is more ecofriendly,
has better physical properties including tensile strength, elongation rate, migration loss,
volatile loss, etc., and has good processability and workability of a product 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).
[0022] In contrast, a phthalate-based compound in which ester groups are present at an ortho
position (positions 1 and 2 in a benzene ring) is an environmental hormone disturbing endocrine
system and harmful to a human body, and have a limit in improving the processability of a resin,
absorption rate with a resin, the degree of migration loss, and heat stability.
[0023] In addition, terephthalate-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.
[0024] In the case of using the ester-based compound according to an embodiment of the
present invention as the plasticizer of the resin composition, equivalent tensile strength and
6
elongation rate may be secured when compared to a common phthalate-based compound widely
used as a plasticizer. In addition, volatile loss may be decreased, and migration resistance may
be markedly excellent.
[0025] According to an embodiment of the present invention, in the above Formulae 1 to 3,
R2 may be an alkyl having a more carbon atoms than R1.
[0026] According to another embodiment of the present invention, in the above Formulae 1
to 3, R1 is a non-branch type alkyl, and R2 may be a branch type alkyl.
[0027] The compound of Formula 1 is an alkyl substituted isophthalate-based compound of
a non-hybrid and non-branch type, the compound of Formula 2 is an alkyl substituted
isophthalate-based compound of a hybrid and branch type, and the compound of Formula 3 is an
alkyl substituted isophthalate-based compound of a non-hybrid and branch type.
[0028] According to an embodiment of the present invention, a compound in which R1 is a
non-branch type, and R2 is a branch type may have improved hardness, tensile strength and
elongation rate when compared to a compound in which both R1 and R2 have a branch type or a
non-branch type. In addition, the productivity and processability of a final product may be
improved due to the improved tensile strength and elongation rate.
[0029] The term “non-hybrid and non-branch type” used in the present invention refers to a
structure in which R1 and R2 alkyl groups substituted in ester groups (-COO-) present at
positions 1 and 3, that is, a meta position of a benzene ring are the same and two linear
hydrocarbons without branched chains are included, if not specifically defined.
[0030] In addition, the term “hybrid and branch type” used in the present invention refers to
a structure in which R1 and R2 alkyl groups substituted in ester groups (-COO-) present at
positions 1 and 3, that is, a meta position of a benzene ring are different from each other and one
kind of a branched chain is included. For example, one alkyl group of the R1 and R2 alkyl
groups is a branch type alkyl group, other alkyl group is a non-branch type alkyl group, if not
specifically defined.
[0031] In addition, in an isophthalate-based compound substituted with hybrid and branch
type alkyl groups, the branch type alkyl group may be the same as the branch type alkyl group of
the isophthalate-based compound substituted with the non-hybrid and branch type alkyl group,
and the non-branch type alkyl group may be the same as the non-branch type alkyl group of the
isophthalate-based compound substituted with the non-hybrid and non-branch type alkyl group.
[0032] Further, the term “non-hybrid and branch type” used in the present invention refers to
a structure in which R1 and R2 alkyl groups substituted in ester groups (-COO-) present at
positions 1 and 3, that is, a meta position of a benzene ring are the same and at least two
branched chains are included, if not specifically defined.
[0033] The substituted alkyl may be, for example, a hydrocarbon having 1 to 20 carbon
atoms and particularly, R1 may be C3-C10 alkyl, and R2 may be at least one independently
selected from C6-C12 hydrocarbon, and R1 and R2 may be different from each other in
consideration of the processability according to fast absorption rate with a resin (plasticizing
efficiency) and the degree of migration loss.
7
[0034] According to another embodiment of the present invention, in the above Formulae 1
to 3, R1 may be C3-C5 alkyl, and R2 may be C6-C12 alkyl, and more particularly, R2 may be
selected from ethylhexyl, isononyl, isodecyl and propylheptyl.
[0035] Further, the present invention may provide an ester-based compound of the following
formulae. The ester compounds of the following formulae may be hybrid type compounds.

[0036] According to an embodiment of the present invention, the ester-based composition
may include the compounds of the following Formulae 1-1, 2-1 and 3-1.

8

[0037] According to an embodiment of the present invention, the ester-based composition
may include the compounds of the following Formulae 1-1, 2-2 and 3-2.

[0038] According to an embodiment of the present invention, the ester-based composition
may include the compounds of the following Formulae 1-1, 2-3 and 3-3.

9

[0039] According to an embodiment of the present invention, the ester-based composition
may include the compounds of the following Formulae 1-1, 2-4 and 3-4.

10
[0040] According to an embodiment of the present invention, the compounds of Formula 1,
Formula 2 and Formula 3 may be included in an amount ratio of 0.5 to 50 wt%, 0.5 to 70 wt%
and 0.5 to 85 wt% with respect to the total amount of the ester composition, respectively, and
particularly, in an amount ratio of 0.5 to 50 wt%, 10 to 50 wt% and 35 to 80 wt%.
[0041] According to an embodiment of the present invention, the mixing ratio of the total
amount of the non-hybrid type compounds of Formulae 1 and 3 and the hybrid type compound of
Formula 2 may be 95:5 to 30:70, and preferably, 90:10 to 60:40 by weight.
[0042] According to an embodiment of the present invention, the ester-based composition
includes the isophthalate-based compounds of Formulae 1 to 3 in the above-described specific
amount range and so, is eco-friendly and has short absorption rate and short melting time with
respect to a resin to improve the processability of the resin. In addition, physical properties such
as hardness, tensile strength, elongation rate, migration loss, sheet volatile loss, heat stability,
QUV, etc. may be further improved.
[0043] The ester-based composition according to an embodiment of the present invention
may be an ether-free plasticizer, and in this case, plasticizing efficiency is good, and workability
is good.
[0044] Ether-free composition means an ester-based composition in which an ether
component included in the composition is 1,000 ppm and less, 100 ppm and less, or 10 ppm and
less.
[0045] According to an embodiment of the present invention, there is provided a preparation
method of the ester-based composition including conducting a trans-esterification reaction of a
compound of the following Formula 3 with a first alcohol of the following Formula 4.

R1-OH
[0046] In the above formulae, R1 and R2 are independently C1-C20 alkyl, and R1 and R2 are
not the same.
[0047] The term “trans-esterification reaction” used in the present invention means a
reaction is conducted between an alcohol and an ester as in the following Reaction 1, and R” of
11
the ester and R’ of the alcohol are interchanged.
[Reaction 1]
[0048] According to an embodiment of the present invention, by conducting the transesterification
reaction, the compound of Formula 1 may be produced when the alkoxide of the
first alcohol of Formula 4 attacks two carbon atoms of the ester group (RCOOR”) of the
compound of Formula 3, the compound of Formula 2 may be produced when the alkoxide
attacks one carbon atom of the ester group (RCOOR”) of the compound of Formula 3, and the
compound of Formula 3 may remain as an unreacted part.
[0049] In addition, the trans-esterification reaction may not induce defects concerning waste
water when compared to an esterification reaction between acid-alcohol, and may not induce
defects generated when using an acid catalyst because the trans-esterification reaction may be
conducted without a catalyst.
[0050] According to an embodiment of the present invention, through the trans-esterification
reaction, the compound of Formula 1, the compound of Formula 2 and the compound of Formula
3 may be produced in an amount of 0.5 to 50 wt%, 0.5 to 70 wt% and 0.5 to 85 wt%,
respectively, with respect to the total amount of the ester-based composition, and particularly in
an amount of 0.5 to 50 wt%, 10 to 50 wt% and 35 to 80 wt%.
[0051] In the above-described range, an ester-based composition having high process
efficiency as a plasticizer and having good processability and absorption rate may be obtained.
[0052] According to an embodiment of the present invention, the ester-based composition
prepared by the trans-esterification reaction may include all of the compound of Formula 1, the
compound of Formula 2 and the compound of Formula 3, and the composition of the ester-based
composition may be controlled according to the amount added of the first alcohol of Formula 4.
[0053] According to an embodiment of the present invention, the amount added of the first
alcohol of Formula 4 may be 0.1 to 89.9 parts by weight, particularly, 3 to 50 parts by weight,
and more particularly, 5 to 40 parts by weight with respect to 100 parts by weight of the
compound of Formula 3.
[0054] According to an embodiment of the present invention, as the amount added of the
first alcohol of Formula 4 increases, the mole fraction of the compound of Formula 3
participating in the trans-esterification reaction may be increased, and the amount of the
compound of Formula 1 and the compound of Formula 2 may be increased in the ester-based
composition.
[0055] In addition, the amount of the unreacted compound of Formula 3 may be decreased
correspondingly.
[0056] According to an embodiment of the present invention, the molar ratio of the
compound of Formula 3 and the first alcohol of Formula 4 may be, for example, 1 : 0.005 to 5.0,
1 : 0.05 to 2.5, or 1 : 0.1 to 1.0, and in this range, an ester-based composition having high process
12
efficiency and processability improving effects may be obtained.
[0057] According to an embodiment of the present invention, the trans-esterification
reaction may preferably be conducted under the reaction temperature of 120°C to 190°C,
preferably 135°C to 180°C, and more preferably, 141°C to 179°C, for from 10 minutes to 10
hours, preferably from 30 minutes to 8 hours, and more preferably from 1 to 6 hours. Within the
temperature range and the time period range, an ester-based composition having a desired
composition may be effectively obtained. In this case, the reaction time may be calculated after
elevating the temperature from the time of attainment of the reaction temperature.
[0058] According to an embodiment of the present invention, the trans-esterification
reaction may be conducted in the presence of an acid catalyst or a metal catalyst, and in this case,
the reaction time may be decreased.
[0059] The acid catalyst may be sulfuric acid, methanesulfonic acid, p-toluenesulfonic acid,
etc., and the metal catalyst may be an organometallic catalyst, a metal oxide catalyst, a metal salt
catalyst, a metal itself, etc.
[0060] The metal component may be at least one selected from the group consisting of tin,
titanium and zirconium, or a mixture of at least two thereof.
[0061] In addition, according to an embodiment of the present invention, a removing process
for removing the unreacted alcohol and reaction by-products, for example, the compound of
Formula 3 by distillation may be further included after conducting the trans-esterification
reaction.
[0062] The distillation may be, for example, two-step distillation for separating the first
alcohol of Formula 4 from the by-products using the difference between boiling points thereof.
[0063] In another embodiment, the distillation may be mixed distillation. In this case, the
ester-based composition may be relatively stably secured with desired composition. The mixed
distillation means the distillation of butanol and the by-products at the same time.
[0064] Meanwhile, the compound of Formula 3 used in the trans-esterification reaction of
the present invention may be obtained by conducting an esterification reaction of the compound
of the following Formula 5 with the second alcohol of the following Formula 6 or a mixture of
the second alcohol with at least one isomer thereof in the presence of a catalyst.

13

R2-OH
[0065] In the above formulae, R2 is alkyl of C1-C20.
[0066] The esterification reaction may be conducted under the reaction temperature of 80°C
to 270°C, preferably 150°C to 250°C, for from 10 minutes to 10 hours, preferably from 30
minutes to 8 hours, and more preferably from 1 to 6 hours. Within the temperature range and the
time period range, the compound of Formula 1 may be effectively obtained.
[0067] According to an embodiment of the present invention, the catalyst used in the
esterification reaction may be an organometallic catalyst including a Sn-based or a Ti-based
catalyst, an acid catalyst including a sulfonic acid-based or a sulfuric-based catalyst, or a mixture
catalyst thereof, and the kind of the catalyst is not limited.
[0068] According to an embodiment of the present invention, the compound of Formula 5
and the second alcohol of Formula 6 (or a mixture of the second alcohol and at least one isomer
thereof) may be used in a molar ratio of 1 : 1 to 7, and preferably, 1 : 2 to 5.
[0069] According to an embodiment of the present invention, the second alcohol of the
above Formula 6 may be used by preparing a common method or may be available on the
market. When using the commercially available product, the second alcohol of the above
Formula 6 may be included as a mixture with at least one isomer thereof, and the amount of the
second alcohol of Formula 6 : the isomer thereof may be, 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.
[0070] For example, when the second alcohol of the above Formula 6 is 2-propylheptane-1-
ol, 4-methyl-2-propyl-hexanol of the following Formula 6-1 or 5-methyl-2-propyl-hexanol of the
following Formula 6-2 may be included as the isomer thereof.

[0071] Particularly, the second alcohol of the above Formula 6 or the mixture of the second
14
alcohol and the isomer thereof may be commercially available. For example, in the case of 2-
propylheptane-1-ol, CAS No. 10042-59-8, 66256-62-0, 159848-27-8, etc. of BASF Co.
including the isomer thereof may be purchased and used, and in the case of isononyl alcohol,
CAS No. 68526-84-1 of EXXONMOBILE Co., CAS No. 27458-94-2 (68515-81-1) of KYOWA
Co., etc. including the isomer thereof may be purchased and used. However, the present
invention is not limited thereto.
[0072] According to an embodiment of the present invention, in the case of using the second
alcohol of Formula 6 including the isomer, a mixture of the compound of Formula 3 and the
isomer thereof may be prepared. Thus, the ester-based composition according to an embodiment
of the present invention may further include the compound of the above Formulae 1 to 3,
preferably the compound of Formulae 2 and 3 may further include the isomer thereof,
respectively.
[0073] By the esterification reaction to prepare the compound of the above Formula 3
according to an embodiment of the present invention, the compound of Formula 3 may be
prepared with the yield of about 80% and over. Through the trans-esterification reaction of the
compound of Formula 3 thus prepared and the first alcohol of the above Formula 4, the esterbased
composition having a desired composition may be easily prepared.
[0074] Meanwhile, the present invention provides an ester-based composition prepared by
the above preparation method.
[0075] In addition, the present invention provides a resin composition including the esterbased
composition as a plasticizer and a resin.
[0076] According to an embodiment of the present invention, the resin may use a known
resin in this field. For example, at least one selected from ethylenevinyl acetate, polyethylene,
polypropylene, polyvinyl chloride, polystyrene, polyurethane, thermoplastic elastomer and
polylactic acid, without limitation.
[0077] According to an embodiment of the present invention, the ester-based composition
may be included in an amount of 5 to 100 parts by weight on the basis of 100 parts by weight of
the resin.
[0078] 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.
[0079] 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.
[0080] 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.
[0081] 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.
15
[0082] The stabilizer used according to an embodiment of the present invention may be a
Ca-Zn-based stabilizer such as a composite stearate of calcium-zinc, without specific limitation.
[0083] In addition, according to an embodiment of the present invention, the resin
composition may further include at least one plasticizer selected from dioctyl phthalate (DOP),
dibutyl phthalate (DBP), dioctyl terephthalate (DOTP), diisononyl phthalate (DINP), diisodecyl
phthalate (DIDP) and di-(2-ethylhexyl) terephthalate (DEHTP). The amount of the plasticizer
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.
[0084] According to an embodiment of the present invention, the resin composition has a sol
viscosity of 4,000 to 15,000 cp, 5,000 to 11,000 cp, or 6,000 to 9,000 cp, and in this range, stable
processability may be secured.
[0085] The sol viscosity in this disclosure is measured using a Brookfield (LV type)
viscometer, spindle used is #4, and the measurement is conducted at 6 rpm and 12 rpm. A
specimen may be a plastisol obtained by mixing 100 phr of PVC (PB900, LG Chem), 75 phr of
an ester-based plasticizer, 4 phr of a stabilizer (KSZ111XF), 3 phr of a foaming agent (W1039),
13 phr of TiO2 (TMCA100), 130 phr or CaCO3 (OMYA10), 10 phr of a viscosity lowering agent
(Exa-sol) and 1 phr of a dispersing agent (BYK3160), and the specimen is stored at 25°C for 1
hour and measured.
[0086] The resin composition may be a resin composition obtained by decreasing the
amount added of the viscosity lowering agent when compared to a common product or a resin
composition obtained by excluding the viscosity lowering agent, that is, a viscosity lowering
agent free resin composition.
[0087] The viscosity lowering agent free composition in this disclosure means a
composition not including a viscosity lowering agent for controlling the viscosity of the resin
composition at all.
[0088] The ester-based composition 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.
[0089] Particularly, good physical properties may be obtained when prescribing the resin
composition including the ester-based composition as a plasticizer as the wall paper sheet.
[0090] 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.
16
[Preparation examples, experimental examples, examples and comparative
examples]
Preparation Example 1
[0091] 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., 498.4 g of purified
isophthalic acid (PIA), 1,172.1 g of ethylhexyl alcohol (molar ratio of isophthalic acid :
ethylhexyl alcohol was 1:3) and 1.54 g of tetraisopropyl titanate (TIPT) as a titanium-based
catalyst (0.3 parts by weight on the basis of 100 parts by weight of isophthalic acid) 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 0.01.
[0092] 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 finally obtain 1,162 g of di-(2-ethylhexyl) isophthalate (yield 99.0%).
Preparation Example 2
[0093] Bis-(2-propylheptyl) isophthalate was obtained by conducting the same procedure
described in Preparation Example 1 except for using 2-propylheptyl alcohol (2-propylheptane-1-
ol (85-100 %), 1-hexanol; 4-methyl-2-propyl (0-15%); 1-hexanol, 5-methyl-2-propyl (0-15%))
(CAS No. 10042-59-8, 66256-62-0 and 159848-27-8 of BASF Co.) instead of ethylhexyl
alcohol.
Preparation Example 3
[0094] Bis(isononyl) isophthalate was obtained by conducting the same procedure described
in Preparation Example 1 except for using isononyl alcohol (CAS No. 68526-84-1 of
EXXONMOBILE Co.) instead of ethylhexyl alcohol.
Preparation Example 4
[0095] Bis(isodecyl) isophthalate was obtained by conducting the same procedure described
in Preparation Example 1 except for using isodecyl alcohol instead of ethylhexyl alcohol.
Example 1
[0096] To a reactor equipped with a stirrer, a condenser and a decanter, 1,000 g of di-(2-
ethylhexyl) isophthalate (hereinafter, DEHIP) prepared in Preparation Example 1 and 70 g of
17
butanol (7 parts by weight on the basis of 100 parts by weight of DEHIP) were added, and a
trans-esterification reaction was conducted under a nitrogen atmosphere at the reaction
temperature of 140°C for 5 hours without a catalyst to produce an ester-based composition
including 1.5 wt%, 22.4 wt% and 76.1 wt% of the compounds of the following Formula 1-1,
Formula 2-1 and Formula 3-1, respectively.

[0097] The reaction product was mixed distilled to remove butanol and 2-ethylhexyl alcohol
and to finally prepare an ester-based composition.
Example 2
[0098] An ester-based composition including 1.4 wt%, 20.7 wt% and 77.9 wt% of the
compounds of the following Formula 1-1, Formula 2-2 and Formula 3-2, respectively, was
obtained by conducting the same procedure described in Example 1 except for using bis(2-
propylheptyl) isophthalate obtained in Preparation Example 2 instead of di-(2-ethylhexyl)
isophthalate (hereinafter, DEHIP) obtained in Preparation Example 1.
18

Example 3
[0099] An ester-based composition including 1.5 wt%, 21.3 wt% and 77.2 wt% of the
compounds of the following Formula 1-1, Formula 2-3 and Formula 3-3, respectively, was
obtained by conducting the same procedure described in Example 1 except for using
bis(isononyl) isophthalate obtained in Preparation Example 2 instead of di-(2-ethylhexyl)
isophthalate (hereinafter, DEHIP) obtained in Preparation Example 1.

19

Example 4
[00100] An ester-based composition including 1.4 wt%, 20.5 wt% and 78.1 wt% of the
compounds of the following Formula 1-1, Formula 2-4 and Formula 3-4, respectively, was
obtained by conducting the same procedure described in Example 1 except for using
bis(isodecyl) isophthalate obtained in Preparation Example 4 instead of di-(2-ethylhexyl)
isophthalate (hereinafter, DEHIP) obtained in Preparation Example 1.

20
Examples 5 to 13
[00101] Ester-based compositions having the composition of the compounds of Formula 1,
Formula 2 and Formula 3 were obtained by conducting the same procedure described in Example
1 except for controlling the amount of the butanol as described in the following Table 1.
Comparative Example 1 (Esterification reaction, both R1 and R2 have a branch type)
[00102] 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., 498.4 g of purified
isophthalic acid, 1,015.8 g of ethylhexyl alcohol, 1,067 g of 2-propyheptanol and 15 g of
methanesulfonic acid (MSA) as a catalyst (3 parts by weight on the basis of 100 parts by weight
of PTA) were inserted, followed by slowly elevating the temperature to about 210°C. The
generation of water began at about 170°C. An esterification reaction was conducted at the
reaction temperature of about 210°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 4.
[00103] 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 finally obtain 2 wt% of DEHIP, 25 wt% of 2-propylheptyl ethylhexyl isophthalate
(PHEHIP) and 73 wt% of bis(2-propylheptyl) isophthalate (DPHIP).
Comparative Example 2 (terephthalate-based)
[00104] A reaction product including 75.5 wt% of di-(2-ethylhexyl) terephthalate (DEHTP),
22.8 wt% of 1-butyl 4-(2-ethylhexyl) terephthalate (hereinafter, BEHTP) and 1.7 wt% of dibutyl
terephthalate (hereinafter, DBTP) was obtained by conducting the same procedure described in
Preparation Example 1 and Example 1 using terephthalic acid instead of isophthalic acid
prepared in Preparation Example 1.
Comparative Example 2 (phthalate-based)
[00105] A reaction product including 75.0 wt% of di-(2-ethylhexyl) terephthalate (DEHP),
21
22.5 wt% of 1-butyl 4-(2-ethylhexyl) terephthalate (hereinafter, BEHP) and 2.5 wt% of dibutyl
phthalate (hereinafter, DBP) was obtained by conducting the same procedure described in
Preparation Example 1 and Example 1 using phthalic acid instead of isophthalic acid prepared in
Preparation Example 1.
[Table 1]
Butanol amount
(parts by weight)
Formula 1
(wt%)
Formula 2
(wt%)
Formula 3
(wt%)
Example 1
(1P)
7 parts by weight (Formula 1-1)
1.5
(Formula 2-1)
22.4
(Formula 3-1)
76.1
Example 2
(1P)
7 parts by weight (Formula 1-1)
1.4
(Formula 2-2)
20.7
(Formula 3-2)
77.9
Example 3
(1P)
7 parts by weight (Formula 1-1)
1.5
(Formula 2-3)
21.3
(Formula 3-3)
77.2
Example 4
(1P)
7 parts by weight (Formula 1-1)
1.4
(Formula 2-4)
20.5
(Formula 3-4)
78.1
Example 5
(1P)
4 parts by weight (Formula 1-1)
0.6
(Formula 2-1)
14.4
(Formula 3-1)
85.0
Example 6
(1P)
10 parts by weight (Formula 1-1)
2.8
(Formula 2-1)
28.4
(Formula 3-1)
68.8
Example 7
(1P)
13 parts by weight (Formula 1-1)
3.1
(Formula 2-1)
29.8
(Formula 3-1)
67.1
Example 8
(1P)
15 parts by weight (Formula 1-1)
4.8
(Formula 2-1)
35.1
(Formula 3-1)
60.1
Example 9
(1P)
18 parts by weight (Formula 1-1)
6.9
(Formula 2-1)
39.4
(Formula 3-1)
53.7
Example 10
(1P)
20 parts by weight (Formula 1-1)
7.9
(Formula 2-1)
41.1
(Formula 3-1)
51.0
Example 11
(1P)
22 parts by weight (Formula 1-1)
9.0
(Formula 2-1)
42.7
(Formula 3-1)
48.3
Example 12
(1P)
30 parts by weight (Formula 1-1)
12.5
(Formula 2-1)
46.3
(Formula 3-1)
41.2
Example 13
(1P)
40 parts by weight (Formula 1-1)
17.9
(Formula 2-1)
49.4
(Formula 3-1)
41.7
Comparative
Example 1
(1P)
7 parts by weight (DEHTP)
2.0
(PHEHIP)
25.0
(DPHIP)
73.0
Comparative
Example 2
(TP)
7 parts by weight (DBTP)
1.7
(BEHTP)
22.8
(DEHTP)
75.5
22
Comparative
Example 3
(1P)
7 parts by weight (DBP)
2.5
(BEHP)
22.5
(DEHP)
75.0
Experimental Example 1: Measuring amount of ester-based composition
[00106] In the ester-based compositions of Examples 1 to 13 of the present invention and
Comparative Examples 1 to 3, the amount (wt%) of each compound was measured using a gas
chromatography apparatus of Agilent Co. (Agilent 7890 GC, Column: HP-5, carrier gas:
helium).
[00107] In the ester-based compositions of Examples 1 to 13, ether was not detected.
Experimental Example 2: Manufacture of specimen (sheet) and evaluation of
performance
[00108] For the ester-based compositions prepared in Examples 1 to 13 and Comparative
Examples 1 to 3, 55 parts by weight of a plasticizer, 2 parts by weight of a BZ stabilizer (BZ210,
Songwon Industries) as an additive and 2 parts by weight of an epoxidized soybean oil (ESO,
Songwon Industries) with respect to 100 parts by weight of a polyvinyl chloride resin (PVC, LS
130s) were mixed in a rotational rate of 1,300 rpm at 100°C. A process was conducted using a
roll mill at 175 for 4 minutes and using a press at 185°C for 3 minutes (low pressure) and for 2
minutes and 30 seconds (high pressure) to manufacture a sheet to a thickness of 2 mm.
[00109] With respect to the sheet, hardness, tensile strength, elongation rate, migration loss
and sheet volatile loss was measured.
[00110] The evaluation conditions of each performance were as follows.
Measuring hardness
[00111] Shore hardness (Shore A) at 25°C was measured using ASTM D2240.
Measuring tensile strength
[00112] By 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 sample 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
[00113] By 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 specimen was cut was measured.
The elongation rate was calculated as follows.
Elongation rate (%) = length after elongation/initial length x 100.
Measuring migration loss
23
[00114] According to KSM-3156, a specimen with a thickness of 2 mm and over was
obtained, ABS (natural color) was 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, the ABS attached
onto both sides of the specimen was 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
[00115] The specimen thus manufactured was processed at 70°C for 72 hours, and the weight
of the specimen was measured.
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]
Example/Comparative
Example
Example 1 Example 2 Example 3 Example
4
Comparative
Example 1
R1 and R2 R1: butyl
R2:
ethylhexyl
R1: butyl
R2:
propylhept
yl
R1: butyl
R2:
isononyl
R1: butyl
R2:
isodecyl
R1:
ethylhexyl
R2:
propylheptyl
Reaction Transesterificati
on
Transesterificati
on
Transesterificati
on
Transesterifica
tion
Esterification
reaction
Physical
properties
Hardness
(Shore A)
87.0 90.5 88.5 90.8 91.8
Tensile
strength
(kg/cm2)
223.2 231.2 225.7 230.1 232.9
Elongation
rate (%)
306.5 287.3 290.6 288.5 278.0
[00116] The results of the above Table 2 are obtained by measuring the physical properties
using the ester-based compositions of Examples 1 to 4 and Comparative Example 1 according to
the trans-esterification reaction or esterification reaction, and branch/non-branch type of R1 and
R2.
[00117] As shown in the above Table 2, the ester-based compositions of Examples 1 to 4 of
the present invention prepared by the trans-esterification reaction have markedly improved
hardness, tensile strength and elongation rate when compared to those of the ester-based
24
composition of Comparative Example 1.
[00118] When particularly examining, the ester-based compositions of Examples 1 to 4 of the
present invention, particularly, the ester-based compositions of Examples 1 to 4 in which R1 is a
non-branch type, and R2 is a branch type by the trans-esterification reaction have better hardness,
tensile strength and elongation rate when compared to the ester-based composition of
Comparative Example 1 in which both R1 and R2 have a branch type.
[00119] For example, the hardness of the ester-based compositions of Examples 1 to 4 is
decreased by 5% and over when compared to the ester-based composition of Comparative
Example 1. Since the hardness is decreased as in the examples of the present invention, good
processability and the stabilization of workability may be provided when applied in a practical
product.
[00120] In addition, it would be known that the elongation rate is increased by about 4% and
over for the ester-based compositions of Examples 1 to 4 when compared to that of the esterbased
composition of Comparative Example 1.
[Table 3]
Butanol
amount
Hardness
(Shore A)
Tensile
strength
(kg/cm2)
Elongation
rate (%)
Migration
loss (%)
Example 5 4 parts by
weight
87.5 230.5 309.5 0.08
Example 6 10 parts by
weight
87.0 220.3 305.6 0.11
Example 7 13 parts by
weight
86.7 220.1 306.7 0.13
Example 8 15 parts by
weight
86.5 219.5 304.5 0.13
Example 9 18 parts by
weight
86.4 219.1 307.5 0.14
Example 10 20 parts by
weight
86.2 219.2 305.3 0.16
Example 11 22 parts by
weight
85.8 219.0 296.5 0.30
Example 12 30 parts83.5
by weight
85.0 205.3 285.1 0.60
Example 13 40 parts by
weight
83.5 197.6 272.3 1.23
[00121] The above Table 3 shows the hardness, tensile strength, elongation rate and
migration resistance of the ester-based compositions of Examples 5 to 13 according to the
25
amount added of butanol.
[00122] As shown in the above Table 3, the hardness, tensile strength, elongation rate and
migration resistance are markedly changed according to the amount added of butanol.
[00123] Particularly, the hardness, tensile strength and elongation rate are relatively improved
while the migration resistance is decreased according to the decrease of the amount added of
butanol.
[00124] Accordingly, the physical properties may be controlled according to use by
controlling the amount of butanol, and it would be secured that the ester-based compositions may
be usefully applied.
[Table 4]
Example/Comparative
example
Example 1 Comparative
Example 2
Comparative
Example 3
Acid Isophthalic acid Terephthalic acid Phthalic acid
Reaction Transesterification
Transesterification
Transesterification
Physical
properties
Hardness
(Shore A)
87.0 87.7 87.3
Tensile
strength
(kg/cm2)
223.2 232.1 221.6
Elongation
rate (%)
306.5 278.5 304.8
Migration
loss (%)
0.10 0.08 1.23
Volatile
loss (%)
6.20 7.52 8.96
[00125] Table 4 shows the results of the hardness, tensile strength, elongation rate and
migration resistance of the sheets manufactured using the plasticizers of Example 1 and
Comparative Examples 2 and 3 by changing the kinds of an acid.
[00126] As shown in the above Table 4, the elongation rate is improved, and the effects of
migration resistance and volatile loss are good for the ester-based compositions of the examples
of the present invention using an isophthalate-based ester plasticizers when compared to the
ester-based compositions of Comparative Examples 2 and 3 using terephthalate-based and
phthalate-based ester plasticizers.
[00127] Particularly, for the specimen using the isophthalate-based ester plasticizer of the
present invention, the elongation rate, migration resistance and volatile loss are improved when
compared to the phthalate-based and terephthalate-based ester plasticizer having ester groups at
ortho position and para position. Thus, the processability of a resin, absorption rate with the
26
resin, the degree of migration loss and heat stability are improved.
[00128] Particularly, the migration resistance of the specimen of Example 1 of the present
invention may be decreased 10 times and less when compared to that of Comparative Example 3.
[00129] In addition, the volatile loss of the specimen of Example 1 of the present invention
may decrease to about 20 to 45% when compared to that of Comparative Examples 2 and 3.
[00130] The decrease of the volatile loss as in Comparative Examples 2 and 3 may be a fatal
defect in the processability and the stability for a long time of a final product. That is, the
increase of the volatile loss means the decrease of the amount of the ester-based composition
(plasticizer) present in the specimen and the deterioration of the elongation rate.
[00131] Thus, it would be secured that the physical properties of the isophthalate-based ester
plasticizer of the present invention are markedly increased when compared to a terephthalatebased
and phthalate-based plasticizers.
Preparation Example 5, examples, comparative examples and experimental
examples
Preparation Example 5
[00132] 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., 498.4 g of purified
isophthalic acid (PIA), 1,425 g of 2-propylheptanol (2-PH) (BASF Co., including 80-100 wt% of
2-PH, 0-15 wt% of 4-methyl-2-propyl hexanol and 0-15 wt% of 5-methyl-2-propyl-hexanol)
(molar ratio of isophthalic acid : 2-PH was 1:3) and 1.54 g of tetra isopropyl titanate (TIPT) as a
titanium-based catalyst 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 0.01.
[00133] After completing the reaction, distillation-extraction under a reduced pressure was
conducted for 0.5 to 4 hours to remove unreacted raw materials. The reactant was cooled, and
neutralization treatment was conducted using an alkaline solution. In addition, the reactant was
dehydrated to remove water. A filter medium was inserted to the dehydrated reactant, followed
by stirring for a certain time and filtering to finally obtain 1,162 g of di-(2-propylheptyl)
isophthalate (yield 99.0%).
Example 14
[00134] To a reactor equipped with a stirrer, a condenser and a decanter, 1,000 g of di-(2-
propylheptyl) isophthalate (hereinafter, DPHIP) prepared in Preparation Example 5 and 70 g of
butanol (7 parts by weight on the basis of 100 parts by weight of DPHIP) were added, and a
trans-esterification reaction was conducted under a nitrogen atmosphere at the reaction
temperature of 140°C for 5 hours without a catalyst to produce an ester-based composition
including 21.0 wt%, 1.6 wt% and 77.4 wt% of the compounds of the following Formula 2-2,
27
Formula 1-1 and Formula 3-2, respectively.

Examples 15 to 21
[00135] Ester-based compositions having the compositions of Formula 2-2, Formula 1-1 and
Formula 3-2 in the following Table 5 were obtained by conducting the same procedure described
in Example 14 except for controlling the amount of butanol as described in the following Table
5.
Comparative Example 4 (terephthalate-based)
[00136] A reaction product including 75.4 wt% of di-(2-propylheptyl) terephthalate
(DPHTP), 23.2 wt% of 1-butyl 4-(2-propylheptyl) terephthalate (hereinafter, BPHTP) and 1.4
wt% of dibutyl terephthalate (hereinafter, DBTP) was obtained by conducting the same
procedure described in Preparation Example 2 and Example 14 using terephthalic acid instead of
isophthalic acid prepared in Preparation Example 2.
Comparative Example 5 (phthalate-based)
[00137] A reaction product including 74.5 wt% of di-(2-propylheptyl) phthalate (DPHP),
22.1 wt% of 1-butyl 4-(2-propylheptyl) phthalate (hereinafter, BPHP) and 3.4 wt% of dibutyl
phthalate (hereinafter, DBP) was obtained by conducting the same procedure described in
28
Preparation Example 2 and an example using phthalic acid instead of isophthalic acid prepared in
Preparation Example 2.
[Table 5]
Butanol amount
(parts by
weight)
Formula 1-1
(wt%)
Formula 2-2
(wt%)
Formula 3-2
(wt%)
Example 14
(1P)
7 parts by
weight
Formula 1-1
1.6
Formula 2-2
21.0
Formula 3-2
77.4
Example 15
(1P)
4 parts by
weight
Formula 1-1
0.6
Formula 2-2
14.7
Formula 3-2
84.7
Example 16
(1P)
10 parts by
weight
Formula 1-1
2.6
Formula 2-2
28.5
Formula 3-2
68.9
Example 17
(1P)
15 parts by
weight
Formula 1-1
5.2
Formula 2-2
36.1
Formula 3-2
58.7
Example 18
(1P)
20 parts by
weight
Formula 1-1
8.0
Formula 2-2
41.3
Formula 3-2
50.7
Example 19
(1P)
22 parts by
weight
Formula 1-1
9.2
Formula 2-2
43.0
Formula 3-2
47.8
Example 20
(1P)
30 parts by
weight
Formula 1-1
12.8
Formula 2-2
46.5
Formula 3-2
40.7
Example 21
(1P)
40 parts by
weight
Formula 1-1
18.5
Formula 2-2
49.8
Formula 3-2
31.7
Comparative
Example 4 (TP)
7 parts by
weight
(DBTP)
1.4
(BPHTP)
23.2
(BPHTP)
75.4
Comparative
Example 5 (P)
7 parts by
weight
(DBP)
3.4
(BPHP)
22.1
(DPHP)
74.5
Experimental Example 3: Measuring amount of ester-based composition
[00138] In the ester-based compositions of Examples 14 to 21 of the present invention and
Comparative Examples 4 to 5, the amount (wt%) of each compound was measured using a gas
chromatography apparatus of Agilent Co. (Agilent 7890 GC, column: HP-5, carrier gas: helium).
[00139] In the ester-based compositions of Examples 14 to 21, ether was not detected.
Experimental Example 4: Manufacture of specimen (sheet) and evaluation of
performance
[00140] For the ester-based composition prepared in Examples 14 to 21 and Comparative
Examples 3 to 5, 55 parts by weight of a plasticizer, 2 parts by weight of a BZ stabilizer (BZ210,
Songwon Industries) as an additive and 2 parts by weight of an epoxidized soybean oil (ESO,
Songwon Industries) with respect to 100 parts by weight of a polyvinyl chloride resin (PVC, LS
130s) were mixed in a rotational rate of 1,300 rpm at 100°C. A process was conducted using a
29
roll mill at 175°C for 4 minutes and using a press at 185°C for 3 minutes (low pressure) and for 2
minutes and 30 seconds (high pressure) to manufacture a sheet with a thickness of 2 mm.
[00141] With respect to the sheet, hardness, tensile strength, elongation rate, migration loss
and sheet volatile loss were measured. The results are illustrated in Tables 6 and 7.
[Table 6]
Butanol
amount
Hardness
(Shore A)
Tensile
strength
(kg/cm2)
Elongation
rate (%)
Migration
loss (%)
Example 15 4 parts by
weight
92.6 268.7 256.3 0.02
Example 16 10 parts by
weight
91.2 249.5 267.5 0.03
Example 17 15 parts by
weight
90.3 235.1 280.5 0.03
Example 18 20 parts by
weight
88.7 218.6 296.8 0.05
Example 19 25 parts by
weight
86.9 213.2 316.4 0.07
Example 20 30 parts by
weight
85.8 205.6 320.6 0.10
Example 21 40 parts by
weight
85.0 198.3 332.3 0.18
[00142] The above Table 6 shows the hardness, tensile strength, elongation rate and
migration resistance of the ester-based compositions of Examples 15 to 21 according to the
amount added of butanol.
[00143] As shown in the above Table 6, the hardness, tensile strength, elongation rate and
migration resistance are markedly changed according to the amount added of butanol.
[00144] Particularly, the hardness, tensile strength and elongation rate are relatively improved
while the migration resistance is decreased according to the decrease of the amount added of
butanol.
[00145] Accordingly, the physical properties may be controlled according to use by
controlling the amount of butanol, and it would be secured that the ester-based compositions may
be usefully applied.
30
[Table 7]
Example/Comparative
example
Example 14 Comparative
Example 4
Comparative
Example 5
Acid Isophthalic acid Terephthalic acid Phthalic acid
Reaction Transesterification
Transesterification
Transesterification
Physical
properties
Hardness
(Shore A)
91.8 93.5 92.0
Tensile
strength
(kg/cm2)
256.5 284.3 257.8
Elongation
rate (%)
260.4 235.1 255.8
Migration
loss (%)
0.03 0.07 0.03
Volatile
loss (%)
0.67 1.11 0.87
[00146] Table 7 shows the results of the hardness, tensile strength, elongation rate and
migration resistance of the sheets manufactured using the plasticizers of Example 14 and
Comparative Examples 4 and 5 by changing the kinds of an acid.
[00147] As shown in the above Table 7, the elongation rate is improved, and the effects of
migration resistance and volatile loss are good for the ester-based compositions of the examples
of the present invention using an isophthalate-based ester plasticizers when compared to the
ester-based compositions of Comparative Examples 4 and 5 using terephthalate-based and
phthalate-based ester plasticizers.
[00148] Particularly, for the specimen using the isophthalate-based ester plasticizer of the
present invention, the elongation rate, migration resistance and volatile loss are improved when
compared to the phthalate-based and terephthalate-based ester plasticizer having ester groups at
ortho position and para position. Thus, the processability of a resin, absorption rate with the
resin, the degree of migration loss and heat stability are improved.
[00149] In addition, the volatile loss of the specimen of Example 14 of the present invention
may decrease to about 30 to 65% when compared to that of Comparative Examples 4 and 5.
[00150] The increase of the volatile loss as in Comparative Examples 4 and 5 may be a fatal
defect in the processability and the stability for a long time of a final product. That is, the
increase of the volatile loss means the decrease of the amount of the ester-based composition
(plasticizer) present in the specimen and the deterioration of the elongation rate.
[00151] Thus, it may be secured that the physical properties of the isophthalate-based ester
plasticizer of the present invention be markedly increased when compared to those of a
31
terephthalate-based and phthalate-based plasticizers.
Preparation Example 6, examples, comparative examples and experimental
examples
Preparation Example 6
[00152] 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., 498.4 g of purified
isophthalic acid (PIA), 1,298.3 g of isononyl alcohol (CAS No. 68526-84-1 of EXXONMOBILE
Co.) (molar ratio of isophthalic acid : isononyl alcohol was 1:3) and 1.54 g of tetra isopropyl
titanate (TIPT) as a titanium-based catalyst 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 0.01.
[00153] After completing the reaction, distillation-extraction under a reduced pressure was
conducted for 0.5 to 4 hours to remove unreacted raw materials. The reactant was cooled, and
neutralization treatment was conducted using an alkaline solution. In addition, the reactant was
dehydrated to remove water. A filter medium was inserted to the dehydrated reactant, followed
by stirring for a certain time and filtering to finally obtain 1,243.3 g of di-isononyl isophthalate
(yield 99.0%).
Example 22
[00154] To a reactor equipped with a stirrer, a condenser and a decanter, 1,000 g of diisononyl
isophthalate (hereinafter, DINIP) prepared in Preparation Example 6 and 70 g of
butanol (7 parts by weight on the basis of 100 parts by weight of DINIP) were added, and a
trans-esterification reaction was conducted under a nitrogen atmosphere at the reaction
temperature of 140°C for 5 hours without a catalyst to produce an ester-based composition
including 21.3 wt%, 2.3 wt% and 77.2 wt% of the compounds of the following Formula 2-3,
Formula 1-1 and Formula 3-3, respectively.

32

[00155] The above reaction products were mixed distillated to remove butanol and isononyl
alcohol to finally prepare an ester-based composition.
Examples 23 to 29
[00156] Ester-based compositions having the compositions of Formula 2-3, Formula 1-1 and
Formula 3-3 in the following Table 8 were obtained by conducting the same procedure described
in Example 22 except for controlling the amount of butanol as described in the following Table
8.
Comparative Example 6 (terephthalate-based)
[00157] A reaction product including 75.1 wt% of di-(isononyl) terephthalate (DINTP), 23.0
wt% of 1-butyl 4-(isononyl) terephthalate (hereinafter, BINTP) and 1.9 wt% of dibutyl
terephthalate (hereinafter, DBTP) was obtained by conducting the same procedure described in
Preparation Example 3 and Example 22 using terephthalic acid instead of isophthalic acid
prepared in Preparation Example 3.
33
Comparative Example 7 (phthalate-based)
[00158] A reaction product including 75.9 wt% of di-(isononyl) phthalate (DNIP), 22.0 wt%
of 1-butyl 4-(isononyl) phthalate (hereinafter, BINP) and 2.1 wt% of dibutyl phthalate
(hereinafter, DBP) was obtained by conducting the same procedure described in Preparation
Example 3 and Example 22 using phthalic acid instead of isophthalic acid prepared in
Preparation Example 3.
[Table 8]
Butanol amount
(parts by
weight)
Formula 1-1
(wt%)
Formula 2-3
(wt%)
Formula 3-3
(wt%)
Example 22
(1P)
7 parts by
weight
Formula 1-1
(2.3)
Formula 2-3
(20.5)
Formula 3-3
(77.2)
Example 23
(1P)
4 parts by
weight
Formula 1-1
(0.7)
Formula 2-3
(14.9)
Formula 3-3
(84.4)
Example 24
(1P)
10 parts by
weight
Formula 1-1
(2.9)
Formula 2-3
(28.9)
Formula 3-3
(68.2)
Example 25
(1P)
15 parts by
weight
Formula 1-1
(5.0)
Formula 2-3
(35.3)
Formula 3-3
(59.7)
Example 26
(1P)
20 parts by
weight
Formula 1-1
(7.9)
Formula 2-3
(41.3)
Formula 3-3
(51.8)
Example 27
(1P)
25 parts by
weight
Formula 1-1
(10.5)
Formula 2-3
(43.8)
Formula 3-3
(45.7)
Example 28
(1P)
30 parts by
weight
Formula 1-1
(12.2)
Formula 2-3
(45.8)
Formula 3-3
(42.0)
Example 29
(1P)
40 parts by
weight
Formula 1-1
(18.0)
Formula 2-3
(49.8)
Formula 3-3
(32.2)
Comparative
Example 6 (TP)
7 parts by
weight
(DBTP)
(1.9)
(BINTP)
(23.0)
(DINTP)
(75.1)
Comparative
Example 7 (P)
7 parts by
weight
(DBP)
(2.1)
(BINP)
(22.0)
(DINP)
(75.9
Experimental Example 5: Measuring amount of ester-based composition
[00159] In the ester-based compositions of Examples 22 to 29 of the present invention and
Comparative Examples 6 to 7, the amount (wt%) of each compound was measured using a gas
chromatography apparatus of Agilent Co. (Agilent 7890 GC, column: HP-5, carrier gas: helium).
[00160] In the ester-based compositions of Examples 22 to 29, ether was not detected.
34
Experimental Example 6: Manufacture of specimen and evaluation of performance
[00161] For the ester-based composition prepared in Examples 22 to 29 and Comparative
Examples 6 to 7, 55 parts by weight of a plasticizer, 2 parts by weight of a BZ stabilizer (BZ210,
Songwon Industries) as an additive and 2 parts by weight of an epoxidized soybean oil (ESO,
Songwon Industries) with respect to 100 parts by weight of a polyvinyl chloride resin (PVC, LS
130s) were mixed in a rotational rate of 1,300 rpm at 100°C. A process was conducted using a
roll mill at 175°C for 4 minutes and using a press at 185°C for 3 minutes (low pressure) and for 2
minutes and 30 seconds (high pressure) to manufacture a sheet with a thickness of 2 mm.
[00162] With respect to the sheet, hardness, tensile strength, elongation rate, migration loss
and sheet volatile loss were measured. The results are illustrated in Tables 9 and 10.
[Table 9]
Butanol
amount
Hardness
(Shore A)
Tensile
strength
(kg/cm2)
Elongation
rate (%)
Migration
loss (%)
Example 23 4 parts by
weight
90.3 237.5 291.6 0.05
Example 24 10 parts by
weight
88.5 224.6 303.4 0.06
Example 25 15 parts by
weight
88.2 220.7 310.2 0.10
Example 26 20 parts by
weight
87.6 216.8 316.5 0.14
Example 27 25 parts by
weight
86.8 209.5 321.7 0.16
Example 28 30 parts by
weight
85.9 201.3 330.1 0.17
Example 29 40 parts by
weight
84.5 195.6 345.6 0.20
[00163] The above Table 9 shows the hardness, tensile strength, elongation rate and
migration resistance of the ester-based compositions of Examples 23 to 29 according to the
35
amount added of butanol.
[00164] As shown in the above Table 9, the hardness, tensile strength, elongation rate and
migration resistance are markedly changed according to the amount added of butanol.
[00165] Particularly, the hardness, tensile strength and elongation rate are relatively improved
while the migration resistance is decreased according to the decrease of the amount added of
butanol.
[00166] Accordingly, the physical properties may be controlled according to use by
controlling the amount of butanol, and it may be secured that the ester-based compositions may
be usefully applied.
[Table 10]
Example/Comparative
example
Example 22 Comparative
Example 6
Comparative
Example 7
Acid Isophthalic acid Terephthalic acid Phthalic acid
Reaction Transesterification
Transesterification
Transesterification
Physical
properties
Hardness
(Shore A)
88.5 89.5 88.3
Tensile
strength
(kg/cm2)
225.7 254.6 220.9
Elongation
rate (%)
290.6 240.8 284.3
Migration
loss (%)
0.05 0.09 0.04
Volatile
loss (%)
1.02 1.45 1.23
[00167] Table 10 shows the results of the hardness, tensile strength, elongation rate and
migration resistance of the sheets manufactured using the plasticizers of Example 22 and
Comparative Examples 6 and 7 by changing the kinds of an acid.
[00168] As shown in the above Table 10, the elongation rate is improved, and the effects of
migration resistance and volatile loss are good for the ester-based composition of the example of
the present invention using an isophthalate-based ester plasticizer when compared to the esterbased
compositions of Comparative Examples 6 and 7 using terephthalate-based and phthalate36
based ester plasticizers.
[00169] Particularly, for the specimen using the isophthalate-based ester plasticizer of the
present invention, the elongation rate, migration resistance and volatile loss are improved when
compared to the phthalate-based and terephthalate-based ester plasticizer having ester groups at
ortho position and para position. Thus, the processability of a resin, absorption rate with the
resin, the degree of migration loss and heat stability are improved.
[00170] In addition, the volatile loss of the specimen of Example 22 of the present invention
may decrease to about 20 to 45% when compared to that of Comparative Examples 6 and 7.
[00171] The increase of the volatile loss as in Comparative Examples 6 and 7 may be a fatal
defect in the processability and the stability for a long time of a final product. That is, the
increase of the volatile loss means the decrease of the amount of the ester-based composition
(plasticizer) present in the specimen and the deterioration of the elongation rate.
[00172] Thus, it may be secured that the physical properties of the isophthalate-based ester
plasticizer composition of the present invention may be markedly increased when compared to a
terephthalate-based and phthalate-based plasticizers.
37
WE CLAIM:
1. An ester-based composition comprising compounds of the following Formula 1, Formula 2
and Formula 3:

in the above Formulae 1 to 3, R1 and R2 are independently C1-C20 alkyl, and R1 and R2
are not the same.
2. The ester-based composition of claim 1, wherein R2 comprises more carbon atoms than R1.
3. The ester-based composition of claim 1, wherein R1 is non-branch type alkyl, and R2 is
branch-type alkyl.
4. The ester-based composition of claim 2, wherein R1 is C3-C10 alkyl, and R2 C6-C12 alkyl.
5. The ester-based composition of claim 4, wherein R1 is C3-C5 alkyl, and R2 is C6-C12 alkyl.
6. The ester-based composition of claim 5, wherein R2 is selected from ethylhexyl, isononyl and
propylheptyl.
7. The ester-based composition of claim 1, wherein the compounds of Formula 1, Formula 2 and
Formula 3 are comprised in amounts of 0.5 to 50 wt%, 0.5 to 70 wt% and 0.5 to 85 wt% with
respect to a total amount of the ester-based composition.
38
8. The ester-based composition of claim 7, wherein the compounds of Formula 1, Formula 2 and
Formula 3 are comprised in amounts of 0.5 to 50 wt%, 10 to 50 wt% and 35 to 80 wt% with
respect to a total amount of the ester-based composition.
9. The ester-based composition of claim 7, wherein a ratio of a total amount of the compounds of
Formulae 1 and 3 and an amount of the compound of Formula 2 is 95 : 5 to 30 : 70 by weight.
10. The ester-based composition of claim 1, wherein the ester-based composition comprises
compounds of the following Formula 1-1, Formula 2-1 and Formula 3-1:

11. The ester-based composition of claim 1, wherein the ester-based composition comprises
compounds of the following Formula 1-1, Formula 2-2 and Formula 3-2:

39

12. The ester-based composition of claim 1, wherein the ester-based composition comprises
compounds of the following Formula 1-1, Formula 2-3 and Formula 3-3:

40

13. The ester-based composition of claim 1, wherein the ester-based composition comprises
compounds of the following Formula 1-1, Formula 2-4 and Formula 3-4:

41
14. The ester-based composition of claim 1, wherein the ester-based composition is an ether-free
plasticizer.
15. At least one ester-based compound selected from the group consisting of compounds in the
following formulae:

42
16. A method of preparing the ester-based composition of claim 1 comprising conducting a
trans-esterification reaction of a compound of the following Formula 3 with a first alcohol of the
following Formula 4:

R1-OH
in the above formulae, R1 and R2 are independently C1-C20 alkyl, and R1 and R2 are not
the same.
17. The method of the ester-based composition of claim 16, wherein a molar ratio of the
compound of the above Formula 3 and a first alcohol of the above Formula 4 is 1 : 0.005 to 5.
18. The method of the ester-based composition of claim 16, wherein an amount of the first
alcohol of the above Formula 4 is 0.1 to 89.9 parts by weight with respect to 100 parts by weight
of the compound of the above Formula 3.
19. The method of the ester-based composition of claim 16, wherein the trans-esterification
reaction is conducted in a temperature range of 120°C to 190°C.
20. The method of the ester-based composition of claim 16, wherein the trans-esterification
reaction is a non-catalytic reaction.
21. The method of the ester-based composition of claim 16, further comprising distilling
unreacted first alcohol of Formula 4 and by-products to remove after the trans-esterification
reaction.
22. The method of the ester-based composition of claim 16, wherein R2 comprises more carbon
atoms than R1.
23. The method of the ester-based composition of claim 21, wherein R1 is C3-C10 alkyl, and R2 is
C6-C12 alkyl.
24. The method of the ester-based composition of claim 16, wherein a portion of the compound
of the above Formula 3 is transformed into a compound of the following Formula 1 and a
compound of the following Formula 2:
43

in the above formulae, R1 and R2 are independently C1-C20 alkyl, and R1 and R2 are not
the same.
25. The method of the ester-based composition of claim 16, wherein the compound of the above
Formula 3 is obtained by an esterification reaction of a compound of the following Formula 5
and a second alcohol of the following Formula 6 in the presence of a catalyst:

R2-OH
in the above formula, R2 is C1-C20 alkyl.
26. The method of the ester-based composition of claim 25, wherein the esterification reaction is
conducted in a temperature range of 80°C to 27°C.
27. The method of the ester-based composition of claim 25, wherein the catalyst is an
organometallic catalyst including a Sn-based or Ti-based catalyst, an acid catalyst including a
sulfonic acid-based or sulfuric acid-based catalyst, or a mixture catalyst thereof.
28. The method of the ester-based composition of claim 25, wherein the compound of the above
Formula 5 and the second alcohol of the above Formula 6 are used in a molar ratio of 1 : 1 to 7.
44
29. The method of the ester-based composition of claim 25,
wherein the second alcohol of the above Formula 6 further comprises at least one isomer of the
second alcohol.
30. A resin composition comprising the ester-based composition of claim 1 as a plasticizer and a
resin.
31. The resin composition of claim 30, wherein the resin is at least one selected from
ethylenevinyl acetate, polyethylene, polypropylene, polyvinyl chloride, polystyrene,
polyurethane, thermoplastic elastomer and polylactic acid.
32. The resin composition of claim 30, wherein the ester-based composition is comprised in an
amount of 5 to 100 parts by weight with respect to 100 parts by weight of the resin.