Detailed description of the invention
Technical challenge
[18]
The present invention was devised to solve the problems of the prior art. When used as a plasticizer of a resin composition, the plasticizer product density is improved while securing the physical properties such as plasticization efficiency, heating loss, light resistance and thermal stability to an excellent level. It is intended to provide a plasticizer composition that can improve the productivity of a final resin product and a resin composition including the same.
[19]
Means of solving the task
[20]
According to an embodiment of the present invention in order to solve the above problems, 70 to 99% by weight of a primary plasticizer comprising a terephthalate-based material and a citrate-based material; And 1 to 30% by weight of a secondary plasticizer comprising an epoxidized alkyl ester composition containing at least one compound represented by the following Formula 1; Including, the terephthalate-based material is di(2-ethylhexyl) terephthalate (DEHTP) and diisononyl terephthalate (DINTP) is at least one selected from the group consisting of, and the citrate-based material is at least one selected from the group consisting of tributyl citrate (TBC) and tripentyl citrate (TPC), and , A plasticizer composition is provided in which the weight ratio of the terephthalate-based material and the tributyl citrate is 90:10 to 60:40.
[21]
[Formula 1]
[22]

[23]
In Formula 1, R 1 is an alkyl group having 8 to 20 carbon atoms containing one or more epoxy groups, and R 2 is an alkyl group having 4, 5 or 8 to 10 carbon atoms.
[24]
Effects of the Invention
[25]
The plasticizer composition according to an embodiment of the present invention can improve the productivity of the final product by reducing the specific gravity of the product while securing the physical properties such as plasticization efficiency, heating loss, light resistance and thermal stability to be used in the resin composition at an excellent level. Plasticizer composition can be provided.
[26]
Mode for carrying out the invention
[27]
Hereinafter, the present invention will be described in more detail to aid in understanding the present invention.
[28]
The terms or words used in the specification and claims should not be construed as limited to their usual or dictionary meanings, and the inventor may appropriately define the concept of terms in order to describe his own invention in the best way. It should be interpreted as a meaning and concept consistent with the technical idea of ​​the present invention based on the principle that there is.
[29]
[30]
Definition of Terms
[31]
As used herein, the term "composition" includes reaction products and decomposition products formed from the materials of the composition, as well as mixtures of materials comprising the composition.
[32]
The prefix "iso-" as used herein refers to an alkyl group in which a methyl group having 1 carbon number is bonded in a branched chain to the main chain of the alkyl group, and generally refers to a methyl branch bonded to the end of the alkyl group, but in the present specification, Alternatively, it may be used as a generic term for an alkyl group in which a methyl group is bonded to the main chain in a branched chain, including those bonded to the terminal as long as there is no alkyl group referred to separately.
[33]
The term "isononyl group" as used herein may mean an alkyl group having a total carbon number of 9 in which one or more of 1 or 2 methyl groups, 1 ethyl group, and 1 propyl group are branched in the main chain, for example , 2-methyloctyl group, 3-methyloctyl group, 4-methyloctyl group, 5-methyloctyl group, 6-methyloctyl group, 3-ethylheptyl group, 2-ethylheptyl group, 2,5-dimethylheptyl group , 2,3-dimethylheptyl group, 4,5-dimethylheptyl group, 3-ethyl-4-methylhexyl group, 2-ethyl-4-methylhexyl group, or 2-propylhexyl group, etc. Isononyl alcohol (CAS No.: 68526-84-1, 27458-94-2) used commercially may mean a composition of isomers having a degree of branching of 1.2 to 1.9, and in the case of the commercial alcohol It may also contain some n-nonyl groups.
[34]
The term "pentyl group" as used herein is an alkyl group having 5 carbon atoms and has a collective meaning of linear and branched alkyl groups, such as n-pentyl group, 2-methylbutyl group, 3-methylbutyl group, 2, The 2-dimethylpropyl group may be collectively referred to, and the pentyl group may be used synonymously with the term'amyl group' as a common name.
[35]
[36]
According to an embodiment of the present invention, 70 to 99% by weight of a primary plasticizer comprising a terephthalate-based material and a citrate-based material; And 1 to 30% by weight of a secondary plasticizer comprising an epoxidized alkyl ester composition containing at least one compound represented by the following Formula 1; Including, the terephthalate-based material is di(2-ethylhexyl) terephthalate (DEHTP) and diisononyl terephthalate (DINTP) is at least one selected from the group consisting of, and the citrate-based material is at least one selected from the group consisting of tributyl citrate (TBC) and tripentyl citrate (TPC), and , A plasticizer composition is provided in which the weight ratio of the terephthalate-based material and the tributyl citrate is 90:10 to 60:40.
[37]
[Formula 1]
[38]

[39]
In Formula 1, R 1 is an alkyl group having 8 to 20 carbon atoms containing one or more epoxy groups, and R 2 is an alkyl group having 4, 5 or 8 to 10 carbon atoms.
[40]
[41]
The plasticizer composition according to an embodiment of the present invention includes a primary plasticizer and a secondary plasticizer, and the primary plasticizer includes a terephthalate-based material and a citrate-based material. In general, di(2-ethylhexyl) terephthalate or diisononyl terephthalate, which is applied as the terephthalate-based material, has poor physical properties such as plasticization efficiency and transferability, so it is suitable for use as a single plasticizer. It is difficult to meet the quality level. Accordingly, in order to improve the plasticization efficiency and transferability, it is preferable to use a citrate-based material together, and in particular, it may be preferable to include tributyl citrate or tripentyl citrate.
[42]
On the other hand, the mixing weight ratio of the terephthalate-based material and the citrate-based material needs to be adjusted in a ratio of 9:1 to 6:4, and when the citrate-based material is contained in excess of 40% by weight, the heating loss characteristics and transition There is a concern that the loss characteristics may be greatly deteriorated, and mechanical properties such as elongation and tensile strength may be deteriorated.
[43]
In addition, when the citrate-based material is mixed with less than 10% by weight, problems such as plasticization efficiency of the terephthalate-based material cannot be solved, and the technical significance of mixing the citrate-based material may be faded. Rather, there is a possibility of causing a decrease in mechanical properties such as elongation. In order to satisfy the above effects, 8:2 to 6:4 may be proposed as a more preferable range.
[44]
In addition, the terephthalate-based material and the citrate-based material need to use a specific material, and as described above, the terephthalate-based material is di(2-ethylhexyl) terephthalate or diisononyl having 8 or 9 alkyl carbon atoms. Terephthalate is applied, and tributyl citrate or tripentyl citrate is applied as a citrate-based material. If these materials are not applied and other terephthalate or citrate is applied, there is a problem that the optimized physical properties such as heating loss, transfer loss, mechanical properties such as tensile strength and elongation, and plasticization efficiency cannot be satisfied. It can be difficult to achieve the goal of balancing important physical properties.
[45]
Meanwhile, the citrate-based material may have a structure represented by Formula 3 below.
[46]
[Chemical Formula 3]
[47]

[48]
In Formula 3, R 5 to R 7 are n-butyl group, isobutyl group, n-pentyl group, 2-methylbutyl group, 3-methylbutyl group or 2,2-dimethylpropyl group, and R 8 is hydrogen to be.
[49]
That is, the R 5 to R 7 may each independently be applied with an alkyl group having 4 or 5 carbon atoms, and may be selected from an alkyl group as described above, in which case the isobutyl group specifically refers to a 2-methylpropyl group, ,'Pentyl group' may be referred to as'amyl group', which is an official name.
[50]
In the case where an acetyl group is bonded to R 8 in Formula 3 and an acetyl group is present in the citrate, that is, when R 8 is an acetyl group, the physical properties of the plasticizer, especially the processability due to the decrease in plasticization efficiency, may be slightly lowered, and elongation There is a fear that this will be greatly inferior. In addition, there may be a burden of adding economical and equipment costs for treating waste acetic acid generated as a by-product in manufacturing the citrate to which the acetyl group is bonded.
[51]
In other words, in the case where R 8 in Formula 3 is an acetyl group in a citrate-based material , there are problems such as a decrease in plasticization efficiency, an increase in the amount of plasticizer to overcome this, and an increase in product price through this, compared to hydrogen. In the case of applying a citrate-based material in which R 8 is an acetyl group, consideration in various aspects such as marketability, economy, and physical properties is required.
[52]
On the other hand, in the case of monohydric alcohols used as raw materials for plasticizers, alcohols with favorable supply and demand conditions in the market are methanol, ethanol, butanol, amyl alcohol (pentanol, 5 carbon atoms), 2-ethylhexanol, isononanol, or There may be 2-propylheptanol and the like, and among them, methanol, ethanol, butanol, pentanol, 2-ethylhexanol, isononanol, and 2-propylheptanol are mainly distributed. Accordingly, the alcohol used as a raw material for the reaction carried out in the process of manufacturing a plasticizer is mainly used as the alcohol described above, and the evaluation of physical properties is generally performed based on the alcohols.
[53]
In this regard, as the primary plasticizers of the plasticizer composition according to the present invention, 2-ethylhexanol or isononanol-derived terephthalate and butanol or pentanol-derived citrate are the most in terms of physical properties and supply and demand in the market. It will be said to be a combination that can show excellent physical properties.
[54]
[55]
The plasticizer composition according to an embodiment of the present invention comprises a primary plasticizer and a secondary plasticizer, and comprises an epoxidized alkyl ester composition as a secondary plasticizer together with the primary plasticizer as described above.
[56]
The epoxidized alkyl ester composition may include one or more epoxidized Fatty Acid Alkyl Ester (eFAAE), and specifically, one or more compounds represented by Formula 1 may be included.
[57]
R 2 in Formula 1 is an alkyl group having 4, 5 or 8 to 10 carbon atoms, and specifically, may be a butyl group, a pentyl group, a 2-ethylhexyl group, an isononyl group, a nonyl group, an isodecyl group or a 2-propylheptyl group And, preferably, a butyl group, a pentyl group, a 2-ethylhexyl group, an isononyl group, or a 2-propylheptyl group.
[58]
When R 2 in Formula 1 is an alkyl group having 4, 5 or 8 to 10 carbon atoms, that is, a butyl group, a 2-ethylhexyl group, an isononyl group or a 2-propylheptyl group, transfer characteristics, plasticization efficiency, and mechanical properties They can be uniformly excellent, and it is possible to eliminate the phenomenon of deteriorating any one specific physical property.
[59]
When a material such as epoxidized fatty acid methyl ester or epoxidized fatty acid ethyl ester is applied as the epoxidized fatty acid alkyl ester, the plasticization efficiency may be improved, but the heating loss may deteriorate, and thus volatile substances during processing There are many problems that can arise.
[60]
Furthermore, when the above-described epoxidized alkyl ester composition is used as a secondary plasticizer, it may have excellent heat resistance and light resistance, and thus, product deformation does not occur even if the final resin product is exposed to ultraviolet rays for a long period of time, so that exposure to light is prolonged. It can be particularly good for products made.
[61]
Therefore, the alkyl of the epoxidized alkyl ester composition that can exhibit the most excellent physical properties by combination with the above-described primary plasticizer may be a butyl group, a pentyl group, a 2-ethylhexyl group, an isononyl group or a 2-propylheptyl group, Particularly more preferably, it may be a butyl group, a pentyl group, or a 2-ethylhexyl group.
[62]
In addition, the epoxidized alkyl ester composition represented by Formula 1 includes two or more compounds, and compounds having two or more compounds having different carbon numbers of R 1 or different numbers of epoxy groups can be formed to form a mixed composition. have.
[63]
Meanwhile, the epoxidized alkyl ester composition may have an oxirane content (OC) of 3.5% or more, 4.0% or more, or 4.2% or more, and preferably 4.5% or more. In addition, the epoxidized alkyl ester composition may have an iodine value of less than 3.5 I 2 g/100g (hereinafter, the unit “I 2 g/100g” is omitted), but preferably 3.2 or less, more preferably 3.0 or less. .
[64]
The epoxidized alkyl ester composition may be an important factor when the measured iodine number and oxirane content rate are applied to the plasticizer composition. In particular, since eco-friendly properties are essential in recent years, the content of iodine and oxirane can have a great influence on the plasticizer properties.
[65]
If the iodine value is 3.5 or more, it may cause discoloration or increase turbidity in the resin product, but if the iodine value is less than 3.5, mechanical properties such as tensile strength and elongation may be improved together. .
[66]
Accordingly, the epoxidized alkyl ester composition may preferably have an iodine value of less than 3.5, more preferably 3.2 or less, and more preferably 3.0 or less. The iodine value represents the content of a double bond present in a molecule, and may be derived from a value measured by a titration method through iodination of the double bond.
[67]
In addition, the oxirane content rate may be changed according to the number of epoxy groups contained in the substituent represented by R 1 in Formula 1, and the oxirane content rate may be 3.5% or more, 4.0% or more, or 4.2% or more. And, preferably, it may be 4.5% or more. The oxirane content may be measured by a titration method, and may be measured by a titration method using a sample and an acid solution.
[68]
The iodine value may represent the content of the double bond, and the content of the double bond may be the content of the double bond remaining after the epoxidation reaction such as epoxidation of vegetable oil or epoxidation of fatty acid alkyl ester is performed. That is, the oxirane content and iodine value may be indices of how much epoxidation has been performed, so they may be partially related to each other, and very theoretically, they may be inversely proportional to each other.
[69]
However, in practice, the double bonds of vegetable oils or fatty acid alkyl esters may vary from substance to substance, so the above two parameters do not form an exact inverse relationship or trade off relationship, and the iodine value between the two substances is higher. The substance may have a higher oxirane content at the same time. Therefore, it may be desirable to apply a plasticizer composition used in a product requiring eco-friendliness in which the iodine value and the oxirane content of the epoxidized fatty acid 2-ethylhexyl ester compound satisfy the above-described range.
[70]
Meanwhile, the oxirane index (OI) of the epoxidized alkyl ester composition may be 1.0 or more.
[71]
As described above, the relationship between the iodine value and the oxirane content is as described above, but at the same time, it may be desirable to satisfy that the oxirane index is 1.0 or more, preferably 1.5 or more, and optimally 2.0 or more. The'oxirane index' is a ratio of the content of oxirane to the iodine value of the epoxidized fatty acid alkyl ester compound, and may be a ratio of a double bond epoxidized through an epoxidation reaction and a residual double bond that has not reacted.
[72]
Specifically, the oxirane index may be 1.0 or more as a ratio of the oxirane content to iodine number. That is, when the value obtained by dividing the oxirane content of the epoxidized fatty acid alkyl ester by the iodine number is 1.0 or more, a more optimized plasticizer composition can be obtained.
[73]
The epoxidized alkyl ester composition includes an epoxidized alkyl ester composition containing at least one compound represented by Formula 1, and additionally, a saturated fatty acid alkyl containing at least one compound represented by the following Formula 2 It may further include an ester composition.
[74]
[Formula 2]
[75]

[76]
In Formula 2, R 3 is an alkyl group having 8 to 20 carbon atoms, and R 4 is an alkyl group having 4, 5 or 8 to 10 carbon atoms.
[77]
The saturated fatty acid alkyl ester composition containing at least one compound represented by Formula 2 may not contain an epoxy group in R 3 , and epoxidized oil in the process of preparing an epoxidized fatty acid alkyl ester using an epoxidized oil and an alcohol. The fatty acid moiety portion of may vary, among which there may be a fatty acid moiety in which an epoxy group is not bonded, and the compound represented by Formula 2 may be a compound resulting from such a fatty acid moiety.
[78]
When such a saturated fatty acid alkyl ester is contained in the epoxidized alkyl ester composition and included in the plasticizer composition, it has a short carbon number of 8 to 18 carbon atoms and does not contain oxirane, so that plasticization efficiency and transferability can be aided. It is beneficial for product cost improvement because separation and purification are unnecessary.
[79]
However, when the content of the saturated fatty acid alkyl ester composition accounts for about 80% by weight or more of the total secondary plasticizer including the epoxidized alkyl ester composition, since a phenomenon of poor compatibility with the vinyl chloride resin may occur, 70% by weight Hereinafter, when it has a content of preferably 50% by weight or less, most preferably 30% by weight or less, compatibility with the resin may be excellent.
[80]
[81]
The plasticizer composition according to an embodiment of the present invention also requires control of the weight ratio of the primary plasticizer and the secondary plasticizer, and may be included in a ratio of 99:1 to 70:30 by weight, and is more preferable than the weight ratio range. The upper limit can be 95:5, 90:10, 85:15, or 80:20.
[82]
When the primary plasticizer and the secondary plasticizer are mixed in the above range to form a plasticizer composition, heat resistance and/or light resistance problems can be solved as a limitation of terephthalate-based materials and citrate-based materials, and epoxidized fatty acid alkyl esters There is an advantage in that it is possible to complement the problems of the transition characteristics or weight loss characteristics of the composition, and at the same time improve mechanical properties as a synergistic effect.
[83]
In particular, the epoxidized alkyl ester composition is a citrate-based material, and when combined with tripentyl citrate or tributyl citrate, its characteristics are optimally expressed and the balance between properties is quite excellent. There is an advantage that can be applied quite universally, up to the resin applied to the sheet of the.
[84]
[85]
The plasticizer composition according to an embodiment of the present invention may be prepared by blending a primary plasticizer and a secondary plasticizer, and the primary plasticizer may also be prepared by blending a terephthalate-based material and a citrate-based material.
[86]
In addition, in the case of the epoxidized alkyl ester composition as the secondary plasticizer, it can be prepared from vegetable natural oils such as soybean oil, linseed oil, and castor oil. It can be prepared by "esterification" using a monohydric alcohol of 8 to 10, and the order of the epoxidation reaction and the esterification reaction is not limited, but the above-described iodine number and oxirane number are prepared to be satisfied. It may be necessary to properly control the method conditions.
[87]
[88]
According to another embodiment of the present invention, 100 parts by weight of a resin; And a resin composition comprising 5 to 150 parts by weight of the plasticizer composition described above is provided.
[89]
The resin may be ethylene vinyl acetate, polyethylene, polyketone, polypropylene, polyvinyl chloride, polystyrene, polyurethane, or thermoplastic elastomer, or a mixture thereof, and the like, preferably polyvinyl chloride.
[90]
For example, the polyvinyl chloride, that is, vinyl chloride resin can be classified into paste vinyl chloride resin and straight vinyl chloride resin depending on the use and processing method, and paste vinyl chloride resin is used in products such as flooring, wallpaper, film, etc. As the applied resin, it is generally prepared according to plastisol processing, and the content of the plasticizer may be about 40 to 150 parts by weight, 60 to 130 parts by weight, and preferably 80 to 120 parts by weight.
[91]
In contrast, straight vinyl chloride resin is a resin that is applied to products such as electric wires and interior materials, and generally, when melt processing is performed, it can be manufactured by processing methods such as injection molding, extrusion molding, and calendering molding. The content of the plasticizer may be applied in an amount of about 5 to 60 parts by weight, preferably 10 to 50 parts by weight.
[92]
The plasticizer composition according to an embodiment of the present invention can be applied to both the pasted vinyl chloride resin and the straight vinyl chloride resin, but it is preferably applied to a straight vinyl chloride resin in which melt processing is performed to maximize the physical properties of the plasticizer. May be appropriate for your needs. In the case of paste vinyl chloride resin, viscosity characteristics are important properties, but in the case of straight vinyl chloride resin, physical properties such as plasticization efficiency and transferability are important. It may be more suitable because it is a product with improved physical properties such as light resistance.
[93]
Further, since most products requiring heat resistance are products subjected to melt processing, it may be appropriate that the plasticizer composition according to the present invention be used for straight vinyl chloride resin.
[94]
Furthermore, in the resin composition, various kinds of additives can be appropriately added to the resin used with the processed product, and physical property aids or processing aids such as fillers, heat stabilizers, auxiliary stabilizers, and foaming agents can be added as additives. , The content can be appropriately applied at a level well known in the art.
[95]
[96]
Example
[97]
Hereinafter, examples will be described in detail to illustrate the present invention in detail. However, the embodiments according to the present invention may be modified in various forms, and the scope of the present invention should not be construed as being limited to the embodiments described below. The embodiments of the present invention are provided to more completely describe the present invention to those of ordinary skill in the art.
[98]
[99]
1. Preparation of plasticizer
[100]
Preparation Example 1: Preparation of di(2-ethylhexyl) terephthalate (DEHTP)
[101]
Purified terephthalic acid (TPA) 498.0 g, 2-ethylhexyl alcohol (2-EH) 1170 g (TPA: 2) in a 4-neck 3-liter reactor equipped with a cooler, condenser, decanter, reflux pump, temperature controller, stirrer, etc. -EH molar ratio (1.0): (3.0)), a titanium-based catalyst (TIPT, tetra isopropyl titanate) as a catalyst was added 1.54 g (0.31 parts by weight per 100 parts by weight of TPA), and the temperature was gradually raised to about 170°C. . Generation of product water started around 170° C., and the reaction was terminated when the reaction temperature reached about 220° C. and nitrogen gas was continuously added at atmospheric pressure for about 4.5 hours, and the acid value reached 0.01.
[102]
After completion of the reaction, distillation extraction was performed for 0.5 to 4 hours under reduced pressure to remove unreacted raw materials. To remove unreacted raw materials below a certain content level, steam extraction was performed for 0.5 to 3 hours under reduced pressure using steam, the reaction solution temperature was cooled to about 90°C, and neutralization treatment was performed using an alkali solution. . In this case, additionally, water washing may be performed, and then the reaction solution may be dehydrated to remove moisture. A filter medium was added to the reaction solution from which moisture was removed, stirred for a certain period of time, and filtered to finally obtain 1161 g of di(2-ethylhexyl) terephthalate (DEHTP) (yield: 99.0%).
[103]
[104]
Preparation Example 2: Preparation of diisononyl terephthalate (DINTP)
[105]
Diisononyl terephthalate (DINTP) 1244 g (yield 99.0 %).
[106]
[107]
Preparation Example 3: Preparation of tributyl citrate (TBC)
[108]
Using 384 g of citric acid and 580 g of butanol as reaction raw materials, 706 g (yield: 98%) of tributyl citrate was finally obtained.
[109]
[110]
Preparation Example 4: Preparation of tri(n-pentyl) citrate (TnPC)
[111]
Using 384 g of citric acid and 686 g of n-pentanol as reaction raw materials, 706 g of tri(n-pentyl) citrate (yield: 98%) was finally obtained.
[112]
[113]
Preparation Example 5: Preparation of eFAEHE
[114]
Epoxidized Soybean Oil (ESO) with an oxirane content of 6.97% and an iodine value of 1.93 (I 2 /100g) in a 4-hole 3-liter reactor equipped with a cooler, condenser, decanter, reflux pump, temperature controller, stirrer, etc. 1000 g, 500 g of 2-ethylhexyl alcohol (2-EH), and 5.5 g of a metal salt catalyst were added as a catalyst, and the temperature was gradually raised to about 180°C.
[115]
Through gas chromatograph analysis, it was confirmed that the raw material ESO was completely reacted and consumed, and the reaction was terminated. After the reaction is complete, the step of removing glycerin as a by-product, removing the unreacted raw materials, and purifying the product, finally, the epoxidized 2-ethylhexyl ester composition 1210 g with an oxirane content of 5.21% and an iodine value of 1.70 Got it.
[116]
[117]
Preparation Example 6: Preparation of eFAINE
[118]
An epoxidized isononyl ester composition having an oxirane content of 5.22% and an iodine of 1.71 in the same manner as in Preparation Example 5, except that isononyl alcohol (Oxocol 900, KH NeoChem) was used instead of using 2-ethylhexanol. Was prepared.
[119]
[120]
Preparation Example 7: Preparation of eFABE
[121]
An epoxidized butyl ester composition having an oxirane content of 5.18% and an iodine value of 1.68 was prepared in the same manner as in Preparation Example 5, except that butanol was used instead of using 2-ethylhexanol.
[122]
[123]
Preparation Example 8: Preparation of eFnPAE
[124]
An epoxidized n-pentyl ester composition having an oxirane content of 5.20% and an iodine value of 1.73 was prepared in the same manner as in Preparation Example 5, except that n-pentanol was used instead of using 2-ethylhexanol.
[125]
[126]
Preparation Example 9: Preparation of eFAPHE
[127]
An epoxidized 2-propylheptyl ester composition having an oxirane content of 5.10% and an iodine value of 1.68 was prepared in the same manner as in Preparation Example 5, except that 2-propylheptanol was used instead of using 2-ethylhexanol. .
[128]
[129]
Comparative Preparation Example 1: Preparation of eFAME
[130]
An epoxidized methyl ester composition having an oxirane content of 5.13% and an iodine value of 1.80 was prepared in the same manner as in Preparation Example 1, except that methanol was used instead of using 2-ethylhexanol.
[131]
[132]
Comparative Preparation Example 2: Preparation of tri(2-ethylhexyl) citrate (TEHC)
[133]
Using 384 g of citric acid and 1014 g of 2-ethylhexanol as raw materials for the reaction, finally 1029 g of tri(2-ethylhexyl) citrate (yield: 98%) was obtained.
[134]
[135]
2. Plasticizer properties evaluation items and measurement method
[136]
1) hardness
[137]
According to ASTM D2240, using a durometer (Mitutoyo), the shore (shore D) hardness at 25 ℃, 3T 10s was measured.
[138]
[139]
2) tensile strength
[140]
According to the ASTM D638 method, the cross head speed was pulled at 200 mm/min (1T) using a test instrument UTM (manufacturer; Instron, model name; 4466), and then the point at which the specimen was cut was measured. . Tensile strength was calculated as follows:
[141]
Tensile strength (kgf/cm 2 ) = load value (kgf) / thickness (cm) x width (cm)
[142]
[143]
3) elongation rate
[144]
According to the ASTM D638 method, after pulling the cross head speed at 200 mm/min (1T) using the UTM (manufacturer; Instron, model name; 4466), the point at which the specimen is cut was measured, The elongation was calculated as follows:
[145]
Elongation (%) = length after elongation / initial length x 100 was calculated.
[146]
[147]
4) migration loss
[148]
According to KSM-3156, a test piece with a thickness of 2 mm or more was obtained, and after attaching a PS plate to both sides of the test piece, a load of 1 kgf/cm 2 was applied. The test piece was allowed to stand at 80° C. for 72 hours in a hot air circulation oven (JISICO (KR), Gear Oven) and then taken out and cooled at room temperature for 4 hours. Then, after removing the PS attached to both sides of the test piece, the weight before and after leaving it in the oven was measured, and the amount of transition loss was calculated by the following equation.
[149]
Transition loss (%) = {(Initial weight of test piece at room temperature-Weight of test piece after leaving the oven) / Initial weight of test piece at room temperature} x 100
[150]
[151]
5) volatile loss
[152]
The specimen prepared in the transition loss evaluation was operated at 80° C. for 72 hours in the same manner as in the transition loss evaluation, and then the weight of the specimen was measured.
[153]
Heating loss (% by weight) = initial specimen weight-(80°C, specimen weight after 72 hours operation) / initial specimen weight x 100.
[154]
[155]
6) Light fastness measurement
[156]
According to the method of ASTM 4329-13, after mounting the specimen in QUV (QUV/se, Q-LAB) and irradiating UV (340 nm) for a certain period of time, the color change is calculated using a Reflectometer (Tintometer, LoviBond). I did.
[157]
[158]
7) Heat resistance measurement
[159]
The prepared specimen was worked in a convection oven (JEIO Tech) at 80°C for a certain period of time, and then the degree of discoloration of the specimen before and after was measured. The measured value was determined by the changed value of the E value for the L,a,b value using a Colormeter (Tintometer, LoviBond).
[160]
[161]
3. Evaluation of physical properties of plasticizer
[162]
1) Configuration of Examples and Comparative Examples
[163]
Using the material prepared in the above Preparation Example, the Examples and Comparative Examples were configured as shown in Table 1 below.
[164]
[Table 1]
Primary plasticizer Weight ratio between primary plasticizer Secondary plasticizer 1st: 2nd weight ratio
Example 1 DEHTP TBC 7:3 eFAEHE 90:10
Example 2 DEHTP TBC 7:3 eFAEHE 80:20
Example 3 DEHTP TBC 7:3 eFABE 90:10
Example 4 DEHTP TPC 7:3 eFAEHE 80:20
Example 5 DEHTP TPC 8:2 eFAINE 90:10
Example 6 DEHTP TBC 9:1 eFAPE 80:20
Example 7 DEHTP TBC 8:2 eFAEHE 70:30
Example 8 DEHTP TPC 6:4 eFAEHE 95:5
Example 9 DINTP TBC 6:4 eFABE 95:5
Example 10 DINTP TBC 8:2 eFAPE 80:20
Example 11 DINTP TPC 7:3 eFAPHE 90:10
Example 12 DINTP TPC 9:1 eFABE 70:30
Comparative Example 1 DEHTP TBC 7:3 X -
Comparative Example 2 DEHTP TBC 7:3 ESO 90:10
Comparative Example 3 DEHTP TBC 7:3 eFAME 70:30
Comparative Example 4 DBTP TBC 7:3 eFAEHE 90:10
Comparative Example 5 DEHTP ATBC 7:3 eFAEHE 90:10
Comparative Example 6 DEHTP X - eFAEHE 80:20
Comparative Example 7 X TBC - eFAEHE 80:20
Comparative Example 8 X X - eFAEHE -
Comparative Example 9 DEHTP TBC 7:3 eFAEHE 50:50
Comparative Example 10 DEHTP TBC 50:50 eFAEHE 90:10
Comparative Example 11 DEHTP TBC 50:50 eFAEHE 50:50
Comparative Example 12 DEHTP TBC 95:5 eFAEHE 90:10
Comparative Example 13 DIDTP TBC 7:3 eFAEHE 90:10
Comparative Example 14 DEHTP TEHC 7:3 eFAPHE 90:10
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Materials not described in Preparation Examples and Comparative Preparation Examples all used materials sold by LG Chem.
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[167]
2) Experimental Example 1: Evaluation of basic physical properties
[168]
The plasticizers of Examples and Comparative Examples were used as test specimens. For the preparation of the specimen, referring to ASTM D638, 30 parts by weight of a plasticizer and 3 parts by weight of a stabilizer (LOX 912 NP) were mixed with a mixer to 100 parts by weight of PVC (LS100S, LG Chem), and then the roll mill was worked at 170° C. for 4 minutes. , 1T and 3T sheets were produced by working at 180° C. for 2.5 minutes (low pressure) and 2 minutes (high pressure) using a press. Each specimen was used to perform the same physical property test as described above, and the results are summarized in Table 2 below.
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[Table 2]
Hardness (Shore D) Tensile strength kgf/cm 2 Elongation (%) Performance loss (%) Heating loss (%)
Example 1 57.8 253.3 288.8 1.74 1.32
Example 2 57.6 251.7 284.0 1.78 1.25
Example 3 57.5 256.4 286.6 1.82 1.43
Example 4 57.7 268.7 295.8 1.41 0.86
Example 5 57.7 270.6 299.7 1.45 0.82
Example 6 57.5 262.3 290.3 1.70 1.20
Example 7 57.5 265.1 298.6 1.50 0.92
Example 8 57.0 264.8 293.5 1.24 1.38
Example 9 57.3 269.7 300.8 1.53 0.63
Example 10 57.5 271.1 301.2 1.56 0.78
Example 11 57.7 280.2 298.0 1.40 0.60
Example 12 57.7 280.3 297.6 1.75 1.20
Comparative Example 1 58.4 256.9 280.7 1.79 1.40
Comparative Example 2 58.7 258.0 289.4 1.71 1.32
Comparative Example 3 55.8 242.1 258.5 3.35 3.48
Comparative Example 4 55.3 230.4 241.0 3.56 6.33
Comparative Example 5 58.3 254.7 265.4 1.90 1.20
Comparative Example 6 61.2 268.8 284.7 3.11 0.64
Comparative Example 7 52.2 221.0 212.3 2.04 16.70
Comparative Example 8 54.3 234.5 256.1 7.45 3.66
Comparative Example 9 57.4 241.0 263.2 3.50 2.01
Comparative Example 10 54.8 247.8 270.6 1.96 4.20
Comparative Example 11 54.2 240.5 258.1 3.21 4.81
Comparative Example 12 56.0 267.3 274.3 2.43 0.96
Comparative Example 13 60.4 264.5 245.7 2.48 0.52
Comparative Example 14 59.4 268.7 254.3 2.03 0.68
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Referring to Table 2, it can be seen that even if the epoxidized alkyl ester is mixed as a secondary plasticizer with the primary plasticizer of DEHTP and TBC, physical properties do not deteriorate due to the decrease in the content of the primary plasticizer. It can be seen that the plasticization efficiency was also improved as this increased and the hardness decreased.
[171]
Specifically, looking at Comparative Example 1, it was confirmed that only the primary plasticizer was included, the plasticization efficiency was poor compared to the examples, and the mechanical properties were equal or less. In addition, looking at Comparative Example 2 in which the epoxidized alkyl ester was not used as the secondary plasticizer and ESO was used as the epoxidized oil, it was confirmed that it was not significantly different from Comparative Example 1, and the effect of adding the secondary plasticizer was It can be seen that it rarely appeared. In addition, in Comparative Example 8 using only the secondary plasticizer, it can be seen that there is a significant problem in mechanical properties, and it can be seen that the transfer loss and heating loss are remarkably poor. In addition, Comparative Example 5 in which an acetyl group was bonded to a citrate-based material included in the primary plasticizer was applied, and all except the acetyl group showed a significant loss in elongation and transition loss compared to Example 1.
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In addition, looking at Comparative Example 3 (the alkyl carbon number of the epoxylated alkyl ester is 1) and Comparative Example 4 (the number of carbon atoms of the terephthalate-based material) in which the number of carbon atoms was not appropriately selected for the above three materials, mechanical properties were poor. In particular, the decrease in elongation is noticeable, and the transfer loss and heating loss are greatly increased, which can infer the difficulty of use as a product.
[173]
On the other hand, Comparative Example 6, which did not contain a citrate-based material, was conspicuous in poor plasticization efficiency (increased hardness), and it was confirmed that the transition characteristics were also poor, and Comparative Example 7 in which a terephthalate-based material was not applied. It is confirmed that represents poor in all physical properties.
[174]
And looking at Comparative Examples 10 and 12, in which the ratio in these primary plasticizers was not well controlled, it was confirmed that a considerable deterioration in elongation was revealed, and characteristic deterioration occurred rapidly in transition loss and heating loss. In addition, in the case of Comparative Example 9, in which the ratio of the primary plasticizer and the secondary plasticizer was not well controlled, it can be confirmed that all physical properties were poor, and Comparative Example 11, in which all the ratios were not controlled, was also carried out in the same manner as other comparative examples. Compared to the examples, it can be seen that mechanical properties and transition loss and heating loss are simultaneously decreased.
[175]
In addition, in the case of Comparative Example 13, which did not satisfy the carbon number of the terephthalate-based material and Comparative Example 14, which did not satisfy the carbon number of the citrate-based material, the plasticization efficiency was poor. It is difficult to see, and it was confirmed that the amount of loss in implementation was not small.
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3) Experimental Example 2: Heat resistance evaluation
[178]
The plasticizers of Examples and Comparative Examples were used as test specimens. For the preparation of the specimen, referring to ASTM D638, 30 parts by weight of plasticizer, 3 parts by weight of stabilizer (LOX 912 NP), and 1.5 parts by weight of TiO 2 were mixed with a mixer to 100 parts by weight of PVC (LS100S, LG Chem), and then a roll mill was used. The work was performed at 170° C. for 4 minutes, and 1T and 3T sheets were produced by working at 180° C. for 2.5 minutes (low pressure) and 2 minutes (high pressure) using a press. Using each specimen, the heat resistance test was performed at 80° C. for 1 week, 2 weeks, 3 weeks and 4 weeks, and the results are summarized in Table 3 below.
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[Table 3]
1 week 2 weeks 3 weeks 4 weeks
Example 1 3.86 6.98 10.14 12.96
Example 2 3.19 6.10 8.99 11.70
Example 3 3.64 6.72 9.81 12.65
Example 4 3.05 6.01 8.56 10.88
Example 5 3.30 6.75 9.24 11.98
Example 6 3.35 6.15 9.04 12.50
Example 7 3.00 6.35 8.50 11.31
Example 8 3.10 5.64 8.02 9.65
Example 9 3.25 5.88 8.24 9.98
Example 10 3.45 6.41 8.60 10.67
Example 11 3.47 6.11 8.37 10.54
Example 12 2.86 5.80 7.98 9.50
Comparative Example 1 4.93 8.67 12.50 16.10
Comparative Example 2 4.61 7.80 10.75 13.41
Comparative Example 6 4.88 7.23 11.20 12.90
[180]
Referring to Table 3, it can be seen that Examples 1 to 12 show superior thermal stability in all period evaluations compared to Comparative Examples 1, 2, and 6. In particular, when looking at Comparative Examples 1 and 2, it was confirmed that thermal stability could be improved by adding a secondary plasticizer. You can see that it works.
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[182]
4) Experimental Example 3: Light fastness evaluation
[183]
The plasticizers of Examples and Comparative Examples were used as test specimens. For the preparation of the specimen, referring to ASTM D638, 30 parts by weight of a plasticizer and 3 parts by weight of a stabilizer (LOX 912 NP) were mixed with a mixer to 100 parts by weight of PVC (LS100S, LG Chem), and then the roll mill was worked at 170° C. for 4 minutes. , 1T and 3T sheets were produced by working at 180° C. for 2.5 minutes (low pressure) and 2 minutes (high pressure) using a press. The heat resistance test was performed using each specimen for 200 hours, 300 hours, 400 hours, 500 hours, 600 hours and 700 hours, and the results are summarized in Table 4 below.
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[Table 4]
200hr 300hr 400hr 500hr 600hr 700hr
Example 1 0.67 4.53 10.28 21.91 27.14 37.79
Example 2 1.42 2.59 7.33 17.08 23.75 34.23
Example 3 0.70 7.67 15.25 22.22 33.49 38.76
Example 4 0.89 3.45 9.68 18.74 25.64 36.20
Example 5 1.40 4.20 11.10 20.13 25.41 36.77
Example 6 1.56 3.80 10.02 17.63 24.50 36.10
Example 7 0.87 2.66 9.40 15.30 22.54 33.20
Example 8 1.34 5.65 12.01 20.87 28.98 40.50
Example 9 1.55 5.60 11.24 22.30 29.14 39.44
Example 10 1.02 2.40 7.85 16.50 21.32 33.11
Example 11 1.14 3.86 9.20 20.31 25.74 38.01
Example 12 0.90 2.87 8.65 14.35 21.30 32.20
Comparative Example 1 5.80 14.44 23.33 32.59 39.66 47.28
Comparative Example 2 1.68 9.37 16.23 26.50 37.01 49.68
Comparative Example 6 3.41 12.32 20.31 29.68 36.85 46.50
[185]
Referring to Table 4, it can be seen that in Examples 1 to 12, photostability is also remarkably improved compared to Comparative Examples 1, 2, and 6.
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[187]
That is, if all the basic physical properties, heat resistance, and light resistance evaluation results are considered, a terephthalate-based material (especially DEHTP or DINTP) and a citrate-based material (especially TBC or TPC) are used as primary plasticizers as in the present invention. In the case of applying an epoxidized alkyl ester having 4, 5 or 8 to 10 carbon atoms of an alkyl as a secondary plasticizer, the heat resistance and light resistance properties are improved without losing the basic properties due to the decrease in the content of the primary plasticizer. You can see that you can.
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[189]
Although the preferred embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and improvements by those skilled in the art using the basic concept of the present invention defined in the following claims are also present. It belongs to the scope of rights of
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Claims
[Claim 1]
70 to 99% by weight of a primary plasticizer including a terephthalate-based material and a citrate-based material; And 1 to 30% by weight of a secondary plasticizer comprising an epoxidized alkyl ester composition containing at least one compound represented by the following formula (1), wherein the terephthalate-based material is di(2-ethylhexyl) terephthalate (DEHTP) and diisononyl terephthalate (DINTP) is at least one selected from the group consisting of, and the citrate-based material is at least one selected from the group consisting of tributyl citrate (TBC) and tripentyl citrate (TPC), and , The terephthalate-based material and the citrate-based material have a weight ratio of 90:10 to 60:40 in a plasticizer composition: [Chemical Formula 1] In Formula 1, R 1 is 8 to 20 carbon atoms containing one or more epoxy groups And R 2 is an alkyl group having 4, 5 or 8 to 10 carbon atoms.
[Claim 2]
The plasticizer composition of claim 1, wherein the epoxidized alkyl ester composition has an iodine value of less than 3.5 I 2 /100 g.
[Claim 3]
The plasticizer composition of claim 1, wherein the epoxidized alkyl ester composition has an oxirane content (OC) of 3.5% or more.
[Claim 4]
The plasticizer composition of claim 1, wherein the epoxidized alkyl ester composition has an oxirane index (OI) of 1.0 or higher.
[Claim 5]
The plasticizer composition of claim 1, wherein R 2 in Formula 1 is selected from the group consisting of a butyl group, a pentyl group, a 2-ethylhexyl group, an isononyl group and a 2-propylheptyl group.
[Claim 6]
The plasticizer composition of claim 1, wherein the weight ratio of the terephthalate-based material and the citrate-based material is 80:20 to 60:40.
[Claim 7]
The plasticizer composition of claim 1, wherein the epoxidized alkyl ester composition further contains a compound represented by the following Formula 2: [Chemical Formula 2] In Formula 2, R 3 is an alkyl group having 8 to 20 carbon atoms, R 4 is an alkyl group having 4, 5 or 8 to 10 carbon atoms.
[Claim 8]
100 parts by weight of resin; And 5 to 150 parts by weight of the plasticizer composition of claim 1.
[Claim 9]
The resin composition of claim 8, wherein the resin is at least one selected from the group consisting of ethylene vinyl acetate, polyethylene, polypropylene, polyketone, polyvinyl chloride, polystyrene, polyurethane, and thermoplastic elastomer.