One]Cross Citation with Related Applications
[2]
This application claims the benefit of priority based on Korean Patent Application No. 10-2019-0069411 dated June 12, 2019, and all contents disclosed in the literature of the Korean patent application are incorporated as a part of this specification.
[3]
[4]
technical field
[5]
The present invention relates to a plasticizer composition and a resin composition comprising the same, and to a plasticizer composition having excellent properties while being environmentally friendly, and a resin composition including the same.
[6]
background
[7]
Plasticizers typically react with alcohols with polycarboxylic acids such as phthalic acid and adipic acid to form the corresponding esters. In addition, in consideration of domestic and international regulations on phthalate-based plasticizers harmful to the human body, research on plasticizer compositions that can replace phthalate-based plasticizers such as terephthalate, adipate, and other polymer-based plasticizers is continuing.
[8]
On the other hand, regardless of the plastisol industry such as flooring, wallpaper, soft and hard sheet, calendaring industry, and extrusion/injection compound industry, the demand for these eco-friendly products is increasing, and the quality characteristics, processability and In order to enhance productivity, an appropriate plasticizer should be used in consideration of discoloration, transferability, and mechanical properties.
[9]
In these various areas of use, additives such as plasticizers, fillers, stabilizers, viscosity reducing agents, dispersants, defoamers, foaming agents, etc. will do
[10]
For example, among the plasticizer compositions applicable to PVC, when di(2-ethylhexyl) terephthalate (DEHTP), which is relatively inexpensive and most commonly used, is applied, hardness or sol viscosity is high and the absorption rate of the plasticizer is relatively slow, and the transferability and stress transferability were not good.
[11]
As an improvement to this, as a composition containing DEHTP, it may be considered to apply the product of the transesterification reaction with butanol as a plasticizer, but while the plasticization efficiency is improved, the reduction in heating or thermal stability is poor, and mechanical properties Improvement of physical properties is required, such as a slight decrease in this, and there is currently no solution other than adopting a method to compensate for this through mixing with other secondary plasticizers in general.
[12]
However, when a secondary plasticizer is applied, it is difficult to predict the change in physical properties, and it may act as a factor in increasing the unit price of the product. The downside is that there are no problems.
[13]
In addition, when a substance such as tri(2-ethylhexyl) trimellitate or triisononyl trimellitate is applied as a trimellitate-based product in order to improve the poor transferability and weight loss characteristics of the DEHTP product, transferability or While the weight loss characteristics are improved, the plasticization efficiency is poor, and there is a problem that a considerable amount must be added to give an appropriate plasticizing effect to the resin. .
[14]
Furthermore, hydrogenated products have been proposed to improve the poor performance of DEHTP products. However, the increase in unit cost due to hydrogenation also remains a problem to be solved.
[15]
Accordingly, as an existing product, there is a need to develop products for solving environmental issues of phthalate-based products or products with improved poor physical properties of eco-friendly products for improving environmental issues of phthalate-based products.
[16]
[17]
[Prior art literature]
[18]
[Patent Literature]
[19]
(Patent Document 1) KR10-0957134B
[20]
DETAILED DESCRIPTION OF THE INVENTION
technical challenge
[21]
An object of the present invention is to provide a plasticizer composition that is environmentally friendly and has excellent physical properties. By controlling the carbon number of the applied citrate-based material and the mixing ratio of the epoxidized oil in a limited manner, mechanical properties are particularly improved and a plasticizer excellent in heat loss properties to provide a composition.
[22]
means of solving the problem
[23]
In order to solve the above problems, the present invention provides an alkyl group bonded to three ester groups, each independently selected from a citrate-based material having 5 to 7 carbon atoms; and an epoxidized oil; wherein the citrate-based material and the epoxidized oil have a weight ratio of 95:5 to 50:50.
[24]
In order to solve the above problems, the present invention provides a resin composition comprising 100 parts by weight of the resin and 5 to 150 parts by weight of the plasticizer composition.
[25]
Effects of the Invention
[26]
The plasticizer composition of the present invention is environmentally friendly, and therefore, when the plasticizer composition of the present invention is included in the resin composition, the tensile strength, elongation, transferability, heat loss and resistance are equivalent to or higher than existing phthalate products or improved products thereof. Physical properties such as stress properties can be remarkably improved.
[27]
In particular, it is possible to improve the heating loss and mechanical properties while maintaining the plasticization efficiency at an excellent level.
[28]
Modes for carrying out the invention
[29]
Hereinafter, the present invention will be described in more detail to help the understanding of the present invention.
[30]
[31]
Definition of Terms
[32]
The term "composition" as used herein includes reaction products and decomposition products formed from materials of the composition, as well as mixtures of materials comprising the composition.
[33]
As used herein, the prefix “iso-” refers to a branched alkyl group in which a methyl group or an ethyl group is branched to the main chain of the alkyl group, and “isoalkyl group (eg, isopentyl group, isohexyl group or iso Heptyl group) may mean a mixture of branched alkyl groups having the same structural isomer relationship.
[34]
The term "straight vinyl chloride polymer" as used herein, as one of the types of vinyl chloride polymer, may mean polymerized through suspension polymerization or bulk polymerization, and has a size of tens to hundreds of micrometers. It refers to a polymer having a form of porous particles with a large amount of pores distributed, no cohesiveness, and excellent flowability.
[35]
The term "paste vinyl chloride polymer" as used herein, as one of the types of vinyl chloride polymer, may mean polymerized through microsuspension polymerization, microseed polymerization, or emulsion polymerization, etc., It refers to a polymer having a size of several thousand nanometers and has poor flowability as fine, dense void-free particles.
[36]
The terms 'comprising', 'having' and their derivatives are not intended to exclude the presence of any additional component, step or procedure, whether or not they are specifically disclosed. For the avoidance of any doubt, all compositions claimed through use of the term 'comprising', unless stated to the contrary, contain any additional additives, adjuvants, or compounds, whether polymeric or otherwise. may include In contrast, the term 'consisting essentially of' excludes from the scope of any subsequent description any other component, step or procedure, except as is not essential to operability. The term 'consisting of' excludes any component, step or procedure not specifically described or listed.
[37]
[38]
How to measure
[39]
In the present specification, analysis of the content of components in the composition that is a product of a specific reaction, such as an esterification reaction, is performed through gas chromatography measurement, and Agilent's gas chromatography instrument (product name: Agilent 7890 GC, column: HP-5, carrier gas) : Analyze with helium (flow rate 2.4mL/min), detector: FID, injection volume: 1uL, initial value: 70℃/4,2min, end value: 280℃/7.8min, program rate: 15℃/min) .
[40]
In the present specification, 'hardness' refers to the shore hardness (Shore “A” and/or Shore “D”) at 25° C. using ASTM D2240, measured under the conditions of 3T 10s, and plasticized It can be an index to evaluate the efficiency, and the lower it is, the better the plasticization efficiency is.
[41]
In the present specification, 'tensile strength' is a test device, UTM (manufacturer; Instron, model name; 4466), according to the ASTM D638 method, and the cross head speed is 200 mm/min (1T) ), measure the point at which the specimen is cut, and calculate by Equation 1 below.
[42]
[Equation 1]
[43]
Tensile strength (kgf/cm 2 ) = load value (kgf) / thickness (cm) x width (cm)
[44]
In the present specification, the 'elongation rate' refers to the point at which the specimen is cut after pulling the cross head speed to 200 mm/min (1T) using the UTM according to the ASTM D638 method. Then, it is calculated by Equation 2 below.
[45]
[Equation 2]
[46]
Elongation (%) = length after stretching / initial length x 100
[47]
In the present specification, 'migration loss' refers to obtaining a test piece having a thickness of 2 mm or more according to KSM-3156, attaching a plate to both sides of the test piece, and applying a load of 1 kgf/cm 2 . After leaving the test piece in a hot air circulation oven (80°C) for 72 hours, take it out and cool it at room temperature for 4 hours. Then, remove the plates attached to both sides of the test piece, measure the weights before and after leaving the plates in the oven, and calculate the transfer loss according to Equation 3 below. Here, the material of the plate may be various, such as PS (Polystyrene), ABS, Glass, and the specimen itself (Specimen plate), and the plate material used for measurement in this specification is Glass.
[48]
[Equation 3]
[49]
Transition loss (%) = {[(initial weight of specimen) - (weight of specimen after leaving in oven)] / (weight of initial specimen)} x 100
[50]
In the present specification, 'volatile loss' refers to measuring the weight of the specimen after working the specimen at 80°C for 72 hours.
[51]
[Equation 4]
[52]
Loss on heating (%) = {[(initial specimen weight) - (test specimen weight after work)] / (initial specimen weight)} x 100
[53]
In the case of the various measurement conditions, detailed conditions such as temperature, rotation speed, time, etc. may be slightly different depending on the case, and in the case of different conditions, the measurement method and conditions are separately specified.
[54]
[55]
Hereinafter, the present invention will be described in more detail to help the understanding of the present invention.
[56]
The terms or words used in the present specification and claims are not to be construed as being limited to their ordinary or dictionary meanings, and the inventor may properly define the concept of the term in order to best describe his invention. Based on the principle that there is, it should be interpreted as meaning and concept consistent with the technical idea of ​​the present invention.
[57]
[58]
The plasticizer composition according to an embodiment of the present invention includes a citrate-based material and an epoxidized oil, wherein the citrate-based material is independently selected from those having 5 to 7 carbon atoms in the alkyl group bonded to three ester groups, The weight ratio of these two components is 95:5 to 50:50.
[59]
According to an embodiment of the present invention, in the citrate-based material, an alkyl group bonded thereto has 5 to 7 carbon atoms, and the alkyl group is, for example, n-pentyl group, isopentyl group, n-hexyl group, isohexyl group. It may be a sil group, n-heptyl group, or isoheptyl group, preferably n-pentyl group, isopentyl group, n-hexyl group or isohexyl group can be applied.
[60]
[Formula 1]
[61]

[62]
In Formula 1, R1 to R3 are each independently the same as or different from each other and represent an alkyl group having 5 to 7 carbon atoms.
[63]
A citrate in which R1 to R3 is an alkyl group having 5 to 7 carbon atoms and different alkyl groups from each other may be referred to as a hybrid citrate, for example, a citrate having a combined substituent of an n-pentyl group and an n-heptyl group; It may be a material in which two different alkyl groups selected from the above substituent groups are bonded, such as citrate having a substituent of a combination of an n-pentyl group and an isopentyl group, and a citrate having a substituent of a combination of an isopentyl group and an n-hexyl group.
[64]
The citrate-based material in which R1 to R3 are identical to each other may be referred to as immiscible citrate, for example, tri(n-pentyl) citrate, triisopentyl citrate, tri(n-hexyl) citrate, triiso Hexyl citrate, tri(n-heptyl) citrate, or triisoheptyl citrate may be applied.
[65]
As described above, when a citrate compound having a small molecular weight with less than 5 carbon atoms is used, the effect of adding a citrate-based material may not be seen due to volatility, and as it volatilizes, weight loss characteristics such as transferability and heat loss may deteriorate. There is a concern, and further deterioration of mechanical properties may reach a serious level, and this change may be clearly expressed starting from the carbon number of 5.
[66]
In addition, when the number of carbon atoms of the alkyl group bonded to the ester group of citrate exceeds 7 and the molecular weight is relatively large, the reduction in plasticization efficiency may be serious, and a problem of deterioration of properties such as stress resistance may occur.
[67]
On the other hand, trialkyl citrate or dinalkyl-malkyl citrate may be applied like the hybrid or non-hybridized alkyl-substituted citrate compound. When an acetyl group is present in the citrate-based material, the physical properties of the plasticizer, especially There is a risk of deterioration of workability and melting properties due to a decrease in plasticization efficiency, mechanical properties such as elongation may decrease, additional manufacturing processes and treatment facilities due to waste acetic acid generation, and increased usage due to poor efficiency As a result, there is a risk of economic deterioration such as cost increase.
[68]
In other words, when the citrate-based material is an acetyl citrate compound in which an acetyl group is substituted with an acetyl group instead of hydrogen of the remaining hydroxy groups in addition to the three ester groups, the decrease in plasticization efficiency, an increase in the amount of the plasticizer to overcome this decrease, and increase in product price through this Due to such problems, deterioration in various aspects such as marketability, economic feasibility and physical properties may be a problem.
[69]
According to an embodiment of the present invention, the citrate-based material represented by Formula 1 may be prepared through a direct esterification reaction. In this case, 3 to 10 moles of the alcohol per 1 mole of citric acid or a derivative thereof , 3 to 8 moles, 3 to 6 moles, or 3 to 5 moles may be used, and it is preferable to use 3 to 5 moles of them.
[70]
The direct esterification reaction may be performed in the presence of a catalyst, and the catalyst may be at least one selected from the group consisting of inorganic acids, organic acids, and Lewis acids, and among them, at least one selected from the group consisting of organic acids and Lewis acids. can
[71]
The inorganic acid may be at least one selected from the group consisting of sulfuric acid, hydrochloric acid and phosphoric acid.
[72]
The organic acid may be at least one selected from the group consisting of p-toluenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, and alkyl sulfuric acid.
[73]
The Lewis acid is an aluminum derivative (aluminum oxide, aluminum hydroxide), a tin derivative (C 3 to C 12 fatty acid tin, tin oxide, tin hydroxide), a titanium derivative (C 3 to C 8 tetraalkyl titanate, titanium oxide, hydroxide titanium), lead derivatives (lead oxide, lead hydroxide), and zinc derivatives (zinc oxide, zinc hydroxide) may be at least one selected from the group consisting of.
[74]
When the catalyst is a homogeneous catalyst, it may be used in an amount of 0.001 to 5 parts by weight or 0.001 to 3 parts by weight based on 100 parts by weight of the sum of the citric acid or its derivative and the alcohol, and it is preferable to use it in an amount of 0.01 to 3 parts by weight. .
[75]
When the catalyst is a heterogeneous catalyst, 0.5 to 200 parts by weight or 0.5 to 100 parts by weight may be used with respect to 100 parts by weight of the total of citric acid or a derivative thereof and alcohol, and 0.5 to 200 parts by weight of them is preferably used.
[76]
The direct esterification reaction may be carried out at 100 to 280 °C, 130 to 250 °C, or 150 to 230 °C, of ​​which it is preferably carried out at 150 to 230 °C.
[77]
The direct esterification reaction may be performed for 3 to 30 hours or 3 to 25 hours, of which 3 to 25 hours is preferable.
[78]
[79]
Meanwhile, the citrate-based material may be prepared by a transesterification reaction, and in this case, it may be prepared by a transesterification reaction of the citric acid derivative and an alcohol. In this case, it may be applicable to preparing a hybrid citrate.
[80]
[81]
The plasticizer composition according to an embodiment of the present invention is characterized in that the epoxidized oil is mixed with the citrate-based material.
[82]
On the other hand, the citrate-based material is superior to the terephthalate-based material in plasticization efficiency and mechanical properties, but has a problem in that it has poor heat resistance to the extent that it is difficult to utilize these excellent properties. It is a material that may be difficult to commercialize as a plasticizer that meets the needs of the actual market because it is difficult to compensate for such poor physical properties.
[83]
In order to compensate for these poor physical properties, there have been attempts to offset this by increasing the number of carbon atoms of the citrate-based material or by applying an excessive amount of epoxidized oil. In contrast, there is a problem in that the mechanical properties are deteriorated.
[84]
In addition, although tributyl citrate or acetyl tributyl citrate is generally used as the citrate-based material, it exhibits a bad effect on various physical properties due to fairly large volatility.
[85]
In the present invention, in order to compensate for the above problems, the citrate prepared by using an alkyl group having 5 to 7 carbon atoms, that is, alcohol having 5 to 7 carbon atoms, is applied to the citrate-based material. In the mixing ratio with the epoxidized oil, the content of the epoxidized oil is characterized in that it does not exceed 50% by weight based on the mixed weight of the two components.
[86]
When the citrate-based material is mixed with the epoxidized oil, it is possible to stably improve the mechanical properties because the carbon number is limited as an appropriate level, and it is also possible to secure the improvement of the stress resistance and the transfer characteristics, and the epoxy By mixing the chemical oil in a limited proportion, it is possible to stably implement improvement of general properties including securing heat resistance and mechanical properties.
[87]
[88]
According to an embodiment of the present invention, the citrate-based material and the epoxidized oil are included in a weight ratio of 90:10 to 50:50. The weight ratio may be, for example, an upper limit of 90:10, 85:15, or 80:20, 75:25, or 70:30, and a lower limit of 50:50, preferably 55:45 or 60: It could be 40. However, in order to maximize the above-described effect, a weight ratio of 90:10 to 55:45, preferably 85:15 to 60:40, may be applied.
[89]
As in the present invention, when the citrate-based material and the epoxidized oil are mixed, it is possible to create a synergistic effect of improving the poor physical properties while maintaining the excellent physical properties of each material. In particular, the improvement of mechanical properties such as tensile strength and elongation is remarkable, while excellent plasticization efficiency is maintained. can
[90]
[91]
The resin composition according to another embodiment of the present invention includes 100 parts by weight of the resin, and 5 to 150 parts by weight of the above-described plasticizer composition. The plasticizer composition may be included in an amount of 5 to 150 parts by weight, preferably 5 to 130 parts by weight, or 10 to 120 parts by weight based on 100 parts by weight of the resin.
[92]
As the resin, a resin known in the art may be used. For example, at least one selected from the group consisting of straight vinyl chloride polymer, paste vinyl chloride polymer, ethylene vinyl acetate copolymer, ethylene polymer, propylene polymer, polyketone, polystyrene, polyurethane, natural rubber, synthetic rubber, and thermoplastic elastomer Mixtures and the like may be used, but the present invention is not limited thereto.
[93]
In general, the resin in which the plasticizer composition is used may be manufactured into a resin product through melt processing or plastisol processing, and the melt processing resin and the plastisol processing resin may be produced differently according to each polymerization method.
[94]
For example, when a vinyl chloride polymer is used for melt processing, solid resin particles with a large average particle diameter are used because it is prepared by suspension polymerization, etc., and this vinyl chloride polymer is called a straight vinyl chloride polymer, and is used for plastisol processing. In this case, a resin in a sol state is used as a fine resin particle prepared by emulsion polymerization, etc., and such a vinyl chloride polymer is called a paste vinyl chloride resin.
[95]
In this case, in the case of the straight vinyl chloride polymer, the plasticizer is preferably included in the range of 5 to 80 parts by weight based on 100 parts by weight of the polymer, and in the case of the paste vinyl chloride polymer, in the range of 40 to 120 parts by weight based on 100 parts by weight of the polymer. It is preferable to include in
[96]
The resin composition may further include a filler. The filler may be 0 to 300 parts by weight, preferably 50 to 200 parts by weight, more preferably 100 to 200 parts by weight based on 100 parts by weight of the resin.
[97]
The plasticizer composition according to an embodiment of the present invention may be preferably applied to a straight vinyl chloride polymer, and thus may be melt-processed, and as a processing method to be described later, a resin product applied to processing such as calendering, extrusion, injection, etc. It can be used as a plasticizer.
[98]
As the filler, any filler known in the art may be used, and the filler is not particularly limited. For example, it may be a mixture of one or more selected from silica, magnesium carbonate, calcium carbonate, coal, talc, magnesium hydroxide, titanium dioxide, magnesium oxide, calcium hydroxide, aluminum hydroxide, aluminum silicate, magnesium silicate and barium sulfate.
[99]
In addition, the resin composition may further include other additives such as a stabilizer, if necessary. Other additives such as the stabilizer may be, for example, 0 to 20 parts by weight, preferably 1 to 15 parts by weight, based on 100 parts by weight of the resin.
[100]
The stabilizer is, for example, a calcium-zinc (Ca-Zn-based) stabilizer such as a calcium-zinc complex stearic acid salt, and a barium-zinc (Ba-Zn-based) stabilizer using barium-zinc as a main metal material. can be used, but is not particularly limited thereto.
[101]
The resin composition may be applied to both melt processing and plastisol processing as described above, for example, melt processing may include calendering processing, extrusion processing, or injection processing, and plastisol processing may include coating processing, etc. This can be applied.
[102]
The resin composition may be used in the manufacture of electric wires, flooring materials, automobile interior materials, films, sheets or tubes.
[103]
[104]
Hereinafter, embodiments of the present invention will be described in detail so that those of ordinary skill in the art can easily carry out the present invention. However, the present invention may be embodied in several different forms and is not limited to the embodiments described herein.
[105]
[106]
Preparation Example 1: Preparation of TnPC
[107]
384 g of citric acid and 780 g of n-pentanol were used as reaction raw materials to finally obtain 792 g of tri(n-pentyl) citrate (TnPC) (yield: 98%).
[108]
[109]
Preparation Example 2: Preparation of TnHxC
[110]
384 g of citric acid and 918 g of n-hexanol were used as reaction raw materials to finally obtain 871 g of tri(n-hexyl) citrate (TnHxC) (yield: 98%).
[111]
[112]
Preparation Example 3: Preparation of TnHpC
[113]
As reaction raw materials, 384 g of citric acid and 1044 g of n-heptanol were used to finally obtain 954 g of tri(n-heptyl) citrate (TnHpC) (yield: 98%).
[114]
[115]
Preparation Example 4: Preparation of ATnHpC
[116]
1,000 g of tri(n-heptyl) citrate (TnHpC) of Preparation Example 3 was acetylated with 230 g of acetic anhydride and 3 g of methanesulfonic acid at 120° C. for 3 hours to acetyl tri(n-heptyl) citrate ( TnHpC) was obtained as 1,062 g.
[117]
[118]
Preparation Example 5: Preparation of eFAEHE
[119]
1,000 g of Epoxidized Soybean Oil (ESO), 500 g of 2-ethylhexanol, and 5.5 g of a metal salt catalyst as a catalyst in a 4-neck 3-liter reactor equipped with a cooler, condenser, decanter, reflux pump, temperature controller, and stirrer. It was put in, and the temperature was gradually raised to about 180°C.
[120]
Through gas chromatograph analysis, it was confirmed that the raw material ESO was completely reacted and consumed, and the reaction was terminated. After completion of the reaction, 1,210 g of an epoxidized fatty acid 2-ethylhexyl ester composition was finally obtained through a step of purifying the product.
[121]
[122]
Examples and Comparative Examples
[123]
Plasticizer compositions of Examples and Comparative Examples were prepared using the materials prepared in Preparation Examples, and are summarized in Table 1 below. The evaluation of the physical properties of the plasticizer composition was performed according to the following experimental items. Commercial products were used for materials other than those prepared in Preparation Example.
[124]
[125]
[Table 1]
　 Citrate-based substances epoxidized oil Etc
Example 1 TPC 90 ESO 2) 10 　
Example 2 TPC 80 ESO 20 　
Example 3 TPC 60 ESO 40 　
Example 4 THxC 90 ESO 10 　
Example 5 THxC 80 ESO 20 　
Example 6 THxC 70 ESO 30 　
Example 7 THxC 60 ESO 40 　
Example 8 THxC 50 ESO 50 　
Example 9 THpC 90 ESO 10 　
Example 10 THpC 80 ESO 20 　
Example 11 THpC 60 ESO 40 　
Example 12 THxC 70 ELO 30 　
Comparative Example 1 - - DEHTP 3)
Comparative Example 2 TPC 95 ESO 5 　
Comparative Example 3 THpC 30 ESO 70 　
Comparative Example 4 THxC 30 ESO 70 　
Comparative Example 5 TBC 4) 70 ESO 30 　
Comparative Example 6 TBC 50 ESO 50 　
Comparative Example 7 TBC 40 ESO 60 　
Comparative Example 8 TEHC 5) 70 ESO 30 　
Comparative Example 9 TEHC 30 ESO 70 　
Comparative Example 10 TINC 6) 50 ESO 50 　
Comparative Example 11 ATHpC 60 ESO 40 　
Comparative Example 12 TPC 70 eFAEHE 30 　
Comparative Example 13 TBC 100 　 　
Comparative Example 14 　 ESO 100 　
[126]
1) The contents in Table 1 above are all in weight %.
[127]
2) ESO: epoxidized oil (Sajohaepyo Co., Ltd.)
[128]
3) DEHTP: di(2-ethylhexyl) terephthalate (LG Chem)
[129]
4) TBC: tributyl citrate (LG Chem)
[130]
5) TEHC: tri(2-ethylhexyl) citrate (LG Chem)
[131]
6) TINC: triisononyl citrate (LG Chem)
[132]
[133]
Experimental Example 1: Performance evaluation
[134]
Using the plasticizers of Examples and Comparative Examples, specimens were manufactured under the following prescription and manufacturing conditions according to ASTM D638.
[135]
(1) Prescription : 100 parts by weight of straight vinyl chloride polymer (LS100S, LG Chem), 40 parts by weight of plasticizer and 3 parts by weight of stabilizer (BZ-153T)
[136]
(2) Mixing : Mixing at 700 rpm at 98℃
[137]
(3) Specimen production : 1T, 2T and 3T sheets were produced by working at 160°C for 4 minutes with a roll mill and 2.5 minutes (low pressure) and 2 minutes (high pressure) at 180°C with a press
[138]
(4) Evaluation items
[139]
1) Hardness: Using ASTM D2240, shore hardness (Shore “A” and “D”) at 25° C. was measured with a 3T specimen for 10 seconds. It is evaluated that the plasticizing efficiency is excellent, so that a numerical value is small.
[140]
2) Tensile strength: After pulling the crosshead speed to 200 mm/min using a test device, UTM (manufacturer; Instron, model name; 4466), according to ASTM D638 method, 1T specimen The cut point was measured. Tensile strength was calculated as follows:
[141]
Tensile strength (kgf/cm 2 ) = load value (kgf) / thickness (cm) x width (cm)
[142]
3) Elongation rate: According to ASTM D638 method, after pulling the cross head speed to 200 mm/min using the UTM, measuring the point at which the 1T specimen is cut, the elongation is calculated as follows Calculated as:
[143]
Elongation (%) = length after stretching / was calculated as initial length x 100.
[144]
4) Measurement of migration loss: A specimen having a thickness of 1 mm was obtained according to KSM-3156, and after attaching a glass plate to both sides of the specimen, a load of 1 kgf/cm 2 was applied. The specimens were left in a hot air circulation oven (80° C.) for 72 hours, then taken out and cooled at room temperature for 4 hours. Then, the weight of the specimen from which the glass plate attached to both sides of the specimen was removed was measured before and after leaving it in the oven to calculate the transfer loss by the following formula.
[145]
Transition loss (%) = {[(Initial specimen weight) - (Specimen weight after leaving the oven)] / (Initial specimen weight)} x 100
[146]
5) volatile loss: After working the prepared specimen at 80° C. for 72 hours, the weight of the specimen was measured.
[147]
Loss on heating (%) = {[(initial specimen weight) - (test specimen weight after work)] / (initial specimen weight)} x 100
[148]
6) Stress test (stress resistance): After a specimen having a thickness of 2 mm was left in a bent state at 23° C. for 72 hours, the degree of transition (the degree of seepage) was observed, and the result was written as a numerical value, at 0 The closer it was, the better the properties were.
[149]
(5) Evaluation results
[150]
The evaluation results of the above items are shown in Table 2 below.
[151]
[Table 2]
Hardness Performance loss (%) Heat loss (%) Tensile strength (kgf/cm 2 ) Elongation (%) stress resistance
division Shore A Shore D
Example 1 90.5 46.0 0.75 0.88 238.4 317.6 0
Example 2 92.1 46.5 0.88 0.98 240.0 314.2 0
Example 3 91.7 46.2 0.61 0.77 245.4 339.7 0.5
Example 4 91.5 46.2 1.00 0.90 238.5 320.0 0
Example 5 92.0 46.4 0.98 0.87 237.9 324.0 0.5
Example 6 92.2 46.7 0.84 0.74 240.2 320.5 0.5
Example 7 92.3 46.8 0.65 0.58 251.6 332.0 0.5
Example 8 92.4 46.7 0.50 0.47 248.9 329.5 0.5
Example 9 93.6 47.7 2.66 0.76 238.1 325.9 1.0
Example 10 93.4 47.4 2.66 0.68 238.1 325.9 1.0
Example 11 92.8 47.0 1.02 0.43 234.8 318.9 0.5
Example 12 92.0 46.5 0.80 0.70 256.3 324.1 0.5
Comparative Example 1 94.6 49.9 3.94 0.86 236.5 314.0 3.0
Comparative Example 2 90.3 45.7 2.54 3.89 201.3 300.5 0
Comparative Example 3 94.7 48.9 0.71 0.23 221.4 320.6 2.5
Comparative Example 4 94.2 48.1 0.52 0.59 208.4 287.8 2.5
Comparative Example 5 91.5 46.0 0.65 4.57 214.5 302.8 0.5
Comparative Example 6 92.8 47.2 1.80 2.03 221.0 290.5 2.0
Comparative Example 7 93.1 47.5 1.84 1.65 238.1 288.2 2.0
Comparative Example 8 95.6 49.7 3.04 0.38 220.5 290.6 3.0
Comparative Example 9 96.8 52.3 0.89 0.32 204.7 268.7 2.0
Comparative Example 10 95.4 49.5 3.56 0.32 232.0 284.6 3.0
Comparative Example 11 95.3 49.4 3.12 0.45 208.6 295.6 2.5
Comparative Example 12 89.7 43.8 1.77 1.94 224.2 309.2 0.5
Comparative Example 13 89.4 43.5 1.02 8.67 202.0 256.4 0.5
Comparative Example 14 96.4 52.5 0.48 0.23 230.4 280.5 2.0
[152]
Referring to Table 2, it is confirmed that the plasticizers of Examples 1 to 12 show significantly superior effects in terms of tensile strength and elongation, particularly elongation, as mechanical properties, compared to the plasticizers of Comparative Examples 1 to 14. Specifically, compared to Comparative Example 1, which is an existing commercial product of the same class, the plasticizers of Examples 1 to 12 according to the present invention not only showed improvement in plasticization efficiency, but also showed excellent effects in migration loss and stress resistance.
[153]
In Comparative Examples 2 to 4, it can be confirmed whether there is an effect depending on the content of the epoxidized oil and the citrate-based material. It was confirmed that the physical properties (tensile strength and elongation) were rather worse than the existing products, and from Comparative Examples 3 and 4 in which the epoxidized oil was used in excess of 50 wt%, the stress resistance deteriorated and at the same time, the carbon number of the citrate-based material was changed. Accordingly, it was confirmed that the range of physical property variation was very large.
[154]
In addition, in the case of Comparative Example 5 using a citrate having a small carbon number, that is, TBC, it was confirmed that additional deterioration of physical properties occurred in the reduction in heating while maintaining the poor mechanical properties. In Comparative Examples 6 and 7, the elongation and stress resistance were rather deteriorated, resulting in a decrease in plasticization efficiency as well.
[155]
In Comparative Examples 8 and 10, TEHC and TINC are applied as citrates having a large number of carbon atoms, and severe loss in plasticization efficiency and migration resistance is confirmed, and mechanical properties are also poor because there is no improvement, and stress resistance is also Example It was confirmed that it was inferior compared to the others. In addition, it is confirmed that even in Comparative Example 9, in which the content is reversed to improve Comparative Example 8, there is a loss of mechanical properties to such an extent that the improvement in migration resistance is insignificant, and the plasticization efficiency is further deteriorated.
[156]
Furthermore, looking at Comparative Example 11 to which the citrate to which the acetyl group is bonded is applied, it is confirmed that the deterioration of the entire physical properties except for the loss of heating is confirmed to such an extent that the deterioration of any one of the physical properties cannot be selected.
[157]
In addition, when applying an epoxidized alkyl monoester obtained by esterifying an epoxidized oil rather than an epoxidized oil as in Comparative Example 12, the effect of improving the plasticization efficiency and heating loss compared to Comparative Example 5 to some extent can be seen. Even so, the improvement of mechanical properties was still not seen, and considering the product price rising due to manufacturing through an additional reaction, the physical properties are rather deteriorated in view of the same economic effect.
[158]
Through this, the plasticizer compositions of the embodiments according to the present invention control the carbon number of the citrate-based material to be 5 to 7, and control the weight ratio with the epoxidized oil so that the content of the citrate-based material is 50% by weight or more If so, it can be confirmed that, in addition to the excellent improvement of mechanical properties, excellent improvement effects can be seen in stress resistance, transferability, and heat loss.
[159]
Finally, as Comparative Examples 13 and 14, when the citrate-based material and the epoxidized oil are used alone, it can also be confirmed that each effect does not change linearly according to the mixing ratio, but produces a synergistic effect.

WE CLAIMS

A citrate-based material selected from the three alkyl groups bonded to the ester groups each independently having 5 to 7 carbon atoms; and an epoxidized oil; wherein the citrate-based material and the epoxidized oil have a weight ratio of 90:10 to 50:50.
[Claim 2]
The plasticizer composition of claim 1, wherein the citrate-based material and the epoxidized oil have a weight ratio of 90:10 to 55:45.
[Claim 3]
The plasticizer composition of claim 1, wherein the citrate-based material and the epoxidized oil have a weight ratio of 85:15 to 55:45.
[Claim 4]
The method according to claim 1, wherein the alkyl group bonded to the citrate-based material is each independently selected from the group consisting of n-pentyl group, isopentyl group, n-hexyl group, isohexyl group, n-heptyl group and isoheptyl group a plasticizer composition.
[Claim 5]
The method according to claim 1, wherein the citrate-based material is tri(n-pentyl) citrate, triisopentyl citrate, tri(n-hexyl) citrate, triisohexyl citrate, tri(n-heptyl) citrate and A plasticizer composition selected from the group consisting of triisoheptyl citrate.
[Claim 6]
The method according to claim 1, wherein the epoxidized oil is epoxidized soybean oil, epoxidized castor oil, epoxidized linseed oil, epoxidized palm oil, and epoxidized A plasticizer composition comprising epoxidized tall oil.
[Claim 7]
The plasticizer composition of claim 1, wherein the citrate-based material is not bound to an acetyl group.
[Claim 8]
100 parts by weight of resin; and 5 to 150 parts by weight of the plasticizer composition according to claim 1 .
[Claim 9]
The method according to claim 8, wherein the resin is a straight vinyl chloride polymer, a paste vinyl chloride polymer, an ethylene vinyl acetate copolymer, an ethylene polymer, a propylene polymer, a polyketone, polystyrene, polyurethane, natural rubber, synthetic rubber and thermoplastic elastomer from the group consisting of A resin composition that is one or more selected.