[TECHNICAL FIELD]
Cross-reference to Related Applications
[0001] The present application claims the benefit of priority
based on Korean Patent Application No. 10-2020-0100048, filed
10 on August 10, 2020, the entire contents of which are
incorporated herein by reference.
Technical Field
[0002] The present invention relates to an acetyl citrate15
based plasticizer composition including a hybrid acetyl
citrate of lower and higher alkyl radicals of the components
in the composition, and a resin composition comprising the
same.
20 [BACKGROUND ART]
[0003] Generally, plasticizers are obtained through the
reaction of alcohols with polycarboxylic acids such as phthalic
acid and adipic acid to form corresponding esters. In addition,
considering the internal and external regulations on harmful
25 phthalate-based plasticizers to the human body, studies are
2
being continued on plasticizer compositions which may replace
phthalate-based plasticizers such as terephthalate-based,
adipate-based and other polymer-based plasticizers.
[0004] Meanwhile, regardless of the type of industry
5 including plastisol type of industry of flooring materials,
wallpaper, soft and hard sheets, etc., calendaring type of
industry, extrusion/injection compound type of industry, and
the demand for eco-friendly products is increasing. In order
to reinforce the quality properties, processability and
10 productivity of the finished products, a suitable plasticizer
is required considering discoloration, migration, mechanical
properties, etc.
[0005] According to the properties required by the types of
industry in various areas of usage, such as tensile strength,
15 elongation rate, light resistance, migration, gelling
properties and absorption rate, supplementary materials such
as a plasticizer, a filler, a stabilizer, a viscosity
decreasing agent, a dispersant, a defoaming agent and a foaming
agent are mixed with a PVC resin.
20 [0006] For example, in the case of applying di(2-ethylhexyl)
terephthalate (DEHTP) which is relatively cheap and widely
used among plasticizer compositions which may be applied to
PVC, hardness or sol viscosity was high, absorption rate of a
plasticizer was relatively slow, and migration and stress
25 migration were not good.
3
[0007] As improvements on the above limitations, the
application of a transesterification product with butanol as
a plasticizer, in a composition including DEHTP may be
considered. In this case, plasticization efficiency is
5 improved, but volatile loss or thermal stability is inferior
and mechanical properties are somewhat degraded, and the
improvement of physical properties is required. Accordingly,
generally, there is no solution but employing a method
compensating the defects through mixing with a second
10 plasticizer at the present time.
[0008] However, in the case of applying the second plasticizer,
there are drawbacks of generating unexpected defects as follows:
the change of the physical properties is hard to predict; the
application may become a factor of increasing the unit cost of
15 the product; the improvement of the physical properties is not
clearly shown except for specific cases; and problems relating
to compatibility with a resin may arise.
[0009] In addition, if a material like tri(2-ethylhexyl)
trimellitate or triisononyl trimellitate is applied as a
20 trimellitate-based product in order to improve the inferior
migration and loss properties of the DEHTP products, migration
or loss properties may be improved, but plasticization
efficiency may be degraded, and a great deal of the material
is required to be injected to provide a resin with suitable
25 plasticization effect, and considering the relatively high
4
unit price of the products, commercialization thereof is
impossible.
[0010] Accordingly, the development of products for solving
the environmental issues of the conventional phthalate-based
5 products or products for improving inferior physical
properties of the eco-friendly products for improving the
environmental issues of the phthalate-based products is
required.
10 [DISCLOSURE OF THE INVENTION]
[TECHNICAL PROBLEM]
[0011] The present invention provides a plasticizer
composition which includes an acetyl citrate in which lower
and higher alkyl radicals are suitably controlled and combined,
15 thereby maintaining and improving mechanical properties and
stress resistance to equal or better levels than the
conventional plasticizer and at the same time, markedly
improving light resistance, and heat resistance such as
residual rate and loss properties, while having suitable
20 balance between migration and plasticizer efficiency.
[TECHNICAL SOLUTION]
[0012] To solve the tasks, according to an embodiment of the
present invention, there is provided a plasticizer composition
25 comprising a citrate-based composition comprising three or
5
more citrates of the following Formula 1, wherein an alkyl
group of the citrate is derived from a C4 alcohol and a C6
alcohol, the C4 alcohol comprises one or more selected from
the group consisting of n-butanol and isobutanol, and the C6
5 alcohol comprises one or more selected from the group
consisting of 1-hexanol, 1-methylpentanol, 2-methylpentanol,
3-methylpentanol, 4-methylpentanol, 1,1-dimethylbutanol, 1,2-
dimethylbutanol, 1,3-dimethylbutanol, 2,2-dimethylbutanol,
2,3-dimethylbutanol, 3,3-dimethylbutanol, 1-ethylbutanol, 2-
10 ethylbutanol, 3-ethylbutanol and cyclopentyl methanol:
[0013] [Formula 1]
[0014] in Formula 1, R1 to R3 are each independently an alkyl
group of 4 or 6 carbon atoms, and R4 is an acetyl group.
15 [0015] In order to solve the tasks, according to another
embodiment of the present invention, there is provided a resin
composition comprising 100 parts by weight of a resin, and 5
to 150 parts by weight of the plasticizer composition.
[0016] The resin may be one or more selected from the group
20 consisting of a straight vinyl chloride polymer, a paste vinyl
chloride polymer, an ethylene vinyl acetate copolymer, an
ethylene polymer, a propylene polymer, polyketone, polystyrene,
polyurethane, polylactic acid, natural rubber and synthetic
6
rubber.
[ADVANTAGEOUS EFFECTS]
[0017] The plasticizer composition according to an embodiment
5 of the present invention, if used in a resin composition, may
maintain and improve mechanical properties and stress
resistance to equal or better levels when compared to the
conventional plasticizer, and at the same time, markedly
improve physical properties such as migration and light
10 resistance, while having suitable balance between loss
properties and plasticization efficiency.
[MODE FOR CARRYING OUT THE INVENTION]
[0018] It will be understood that terms or words used in the
15 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
20 explain the invention at his best method.
[0019] Definition of terms
[0020] The term “composition” as used in the present
disclosure includes a mixture of materials including the
25 corresponding composition as well as a reaction product and a
7
decomposition product formed from the materials of the
corresponding composition.
[0021] The term “straight vinyl chloride polymer” as used in
the present disclosure may be one type of vinyl chloride
5 polymers and polymerized by suspension polymerization, bulk
polymerization, etc., and may refer to a polymer having a
porous particle shape in which a large number of pores having
a size of tens to hundreds of micrometers, no cohesiveness,
and excellent flowability are dispersed.
10 [0022] The term “paste vinyl chloride polymer” as used in the
present disclosure may be one type of vinyl chloride polymers
and polymerized by microsuspension polymerization, microseed
polymerization, emulsion polymerization, etc., and may refer
to a polymer having minute particles without pores and a size
15 of tens to thousands of nanometers, cohesiveness, and inferior
flowability.
[0023] The terms "comprising", and “having” and the
derivatives thereof in the present invention, though these
terms are particularly disclosed or not, do not intended to
20 preclude the presence of optional additional components, steps,
or processes. In order to avoid any uncertainty, all
compositions claimed by using the term “comprising” may include
optional additional additives, auxiliaries, or compounds,
including a polymer or any other materials, unless otherwise
25 described to the contrary. In contrast, the term “consisting
8
essentially of ~” excludes unnecessary ones for operation and
precludes optional other components, steps or processes from
the scope of optional continuous description. The term
“consisting of ~” precludes optional components, steps or
5 processes, which are not particularly described or illustrated.
[0024] Measurement methods
[0025] In the present disclosure, the content analysis of the
components in a composition is conducted by gas chromatography
10 measurement using a gas chromatography equipment of Agilent
Co. (product name: Agilent 7890 GC, column: HP-5, carrier gas:
helium (flow rate of 2.4 ml/min), detector: F.I.D., injection
volume: 1 μl, initial value: 70°C/4.2 min, end value: 280°C/7.8
min, program rate: 15°C/min).
15 [0026] In the present disclosure, “hardness” means Shore
hardness (Shore “A” and/or Shore “D”) at 25°C and is measured
in conditions of 3T 10s using ASTM D2240. The hardness may be
an index for evaluating plasticization efficiency, and the
lower the value is, the better the plasticization efficiency
20 is.
[0027] In the present disclosure, “tensile strength” is
obtained according to an ASTM D638 method by drawing a specimen
in a cross head speed of 200 mm/min (1T) using a test apparatus
of U.T.M (manufacturer: Instron, model name: 4466), measuring
25 a point where the specimen is cut, and calculating according
9
to the following Mathematical Formula 1:
[0028] [Mathematical Formula 1]
Tensile strength (kgf/cm2) = load value (kgf)/thickness
(cm) x width (cm)
5 [0029] In the present disclosure, “elongation rate” is
obtained according to an ASTM D638 method by drawing a specimen
in a cross head speed of 200 mm/min (1T) using the U.T.M,
measuring a point where the specimen is cut, and calculating
according to the following Mathematical Formula 2:
10 [0030] [Mathematical Formula 2]
Elongation rate (%) = length after elongation/initial
length x 100
[0031] In the present disclosure, “migration loss” is
obtained according to KSM-3156, by which a specimen with a
15 thickness of 2 mm or more is obtained, glass plates are
attached onto both sides of the specimen, and a load of 1
kgf/cm2 is applied. The specimen is stood in a hot air
circulation type oven (80°C) for 72 hours, then taken out
therefrom and cooled at room temperature for 4 hours. Then,
20 the glass plates attached onto both sides of the specimen are
removed, the weights before and after standing a glass plate
and a specimen plate in the oven are measured, and the
migration loss is calculated according to Mathematical Formula
3 below.
25 [0032] [Mathematical Formula 3]
10
Migration loss (%) = {[(weight of initial specimen) –
(weight of specimen after standing in oven)]/(weight of initial
specimen)} x 100
[0033] In the present disclosure, “volatile loss” is obtained
5 by processing a specimen at 80°C for 72 hours and then,
measuring the weight of the specimen.
[0034] [Mathematical Formula 4]
Volatile loss (wt%) = {[(weight of initial specimen) –
(weight of specimen after processing)]/(weight of initial
10 specimen)} x 100
[0035] In the case of the various measurement conditions, the
details of the conditions of the temperature, the speed of
revolution, the time, etc., may be somewhat changed according
to situations, and if the conditions are different, a
15 measurement method and its conditions are required to be
separately indicated.
[0036] Hereinafter, the present invention will be explained
in more detail to assist the understanding of the present
20 invention.
[0037] According to an embodiment of the present invention,
a plasticizer composition comprises a citrate-based
composition comprising three or more citrates of the following
Formula 1, wherein an alkyl group of the citrate is derived
25 from a C4 alcohol and a C6 alcohol, the C4 alcohol comprises
11
one or more selected from the group consisting of n-butanol
and isobutanol, and the C6 alcohol comprises one or more
selected from the group consisting of 1-hexanol, 1-
methylpentanol, 2-methylpentanol, 3-methylpentanol, 4-
5 methylpentanol, 1,1-dimethylbutanol, 1,2-dimethylbutanol,
1,3-dimethylbutanol, 2,2-dimethylbutanol, 2,3-dimethylbutanol,
3,3-dimethylbutanol, 1-ethylbutanol, 2-ethylbutanol, 3-
ethylbutanol and cyclopentyl methanol:
[0038] [Formula 1]
10
[0039] in Formula 1,
[0040] R1 to R3 are each independently an alkyl group of 4 or
6 carbon atoms, and R4 is an acetyl group.
15 [0041] The plasticizer composition may be a product produced
by direct esterification reaction of citric acid or a citric
acid derivative with a mixture of a C4 alcohol and a C6 alcohol,
or by transesterification reaction of a citrate having an alkyl
group of 4 (or 6) carbon atoms and a C6 (or C4) alcohol, and
20 in this case, the alcohol applied may be a mixture of the
structural isomers or a single material thereof. For example,
the C4 alcohol may be a single material of each of n-butanol
or isobutanol, or a mixture thereof, and the C6 alcohol may be
12
a single material of each of 1-hexanol, 1-methylpentanol, 2-
methylpentanol, 3-methylpentanol, 4-methylpentanol, 1,1-
dimethylbutanol, 1,2-dimethylbutanol, 1,3-dimethylbutanol,
2,2-dimethylbutanol, 2,3-dimethylbutanol, 3,3-dimethylbutanol,
5 1-ethylbutanol, 2-ethylbutanol, 3-ethylbutanol and cyclopentyl
methanol, or a mixture of two or more thereof.
[0042] In addition, the weight ratio of the C4 alcohol and
the C6 alcohol may be 5:95 to 95:5, preferably, 10:90 to 90:10,
particularly preferably, 30:70 to 90:10. By controlling the
10 weight ratio of the C4 alcohol and the C6 alcohol in the
aforementioned range, a plasticizer composition having
excellent balance among physical properties such as
plasticization efficiency, mechanical strength, migration
resistance, thermal stability, stress resistance and
15 carbonization properties may be provided.

CLAIMS
1. A plasticizer composition comprising a citrate-based
composition comprising three or more citrates of the following
5 Formula 1, wherein
an alkyl group of the citrate is derived from a C4 alcohol
and a C6 alcohol,
the C4 alcohol comprises one or more selected from the
group consisting of n-butanol and isobutanol, and
10 the C6 alcohol comprises one or more selected from the
group consisting of 1-hexanol, 1-methylpentanol, 2-
methylpentanol, 3-methylpentanol, 4-methylpentanol, 1,1-
dimethylbutanol, 1,2-dimethylbutanol, 1,3-dimethylbutanol,
2,2-dimethylbutanol, 2,3-dimethylbutanol, 3,3-dimethylbutanol,
15 1-ethylbutanol, 2-ethylbutanol, 3-ethylbutanol and cyclopentyl
methanol:
[Formula 1]
in Formula 1,
20 R1 to R3 are each independently an alkyl group of 4 or 6
carbon atoms, and R4 is an acetyl group.
2. The plasticizer composition according to claim 1, wherein
45
the citrate-based composition comprises:
a lower alkyl-based citrate comprising a lower nonhybrid
citrate having an alkyl group derived from three C4 alcohols,
and a lower hybrid citrate having an alkyl group derived from
5 two C4 alcohols and an alkyl group derived from one C6 alcohol;
and
a higher alkyl-based citrate comprising a higher hybrid
citrate having an alkyl group derived from two C6 alcohols and
an alkyl group derived from one C4 alcohol, and a higher
10 nonhybrid citrate having an alkyl group derived from three C6
alcohols.
3. The plasticizer composition according to claim 1, wherein
a weight ratio of the C4 alcohol and the C6 alcohol is 5:95 to
15 95:5.
4. The plasticizer composition according to claim 1, wherein
the C6 alcohol comprises 1-hexanol, 2-methylpentanol and 3-
methylpentanol.
20
5. The plasticizer composition according to claim 4, wherein
the C6 alcohol further comprises cyclopentyl methanol.
6. The plasticizer composition according to claim 1, wherein
25 the C6 alcohol comprises 1-hexanol, and one or more selected
46
from the group consisting of 2-methylpentanol, 3-
methylpentanol and cyclopentyl methanol, and
the 1-hexanol is comprised in 60 wt% or less based on a
total weight of the C6 alcohol.
5
7. The plasticizer composition according to claim 2, wherein
a weight ratio of the lower alkyl-based citrate and the higher
alkyl-based citrate is 1:99 to 99:1.
10 8. The plasticizer composition according to claim 7, wherein
the weight ratio of the lower alkyl-based citrate and the
higher alkyl-based citrate is 2:98 to 95:5.
9. The plasticizer composition according to claim 2, wherein
15 a weight ratio of the lower nonhybrid citrate and the lower
hybrid citrate in the lower alkyl-based citrate is 2:98 to
90:10.
10. The plasticizer composition according to claim 2, wherein
20 a weight ratio of the higher nonhybrid citrate and the higher
hybrid citrate in the higher alkyl-based citrate is 5:95 to
95:5.
11. A resin composition, comprising:
25 100 parts by weight of a resin; and 5 to 150 parts by
47
weight of the plasticizer composition of claim 1.
12. The resin composition according to claim 11, wherein the
resin is one or more selected from the group consisting of a
5 straight vinyl chloride polymer, a paste vinyl chloride polymer,
an ethylene vinyl acetate copolymer, an ethylene polymer, a
propylene polymer, polyketone, polystyrene, polyurethane,
polylactic acid, natural rubber and synthetic rubber.
10