Detailed description of the invention
Technical challenges
[12]
In the present invention, as a plasticizer applied to a resin composition, mechanical properties such as tensile strength, elongation and modulus can be maintained at an excellent level, excellent in transmittance and transparency, and a plasticizer composition with improved plasticization efficiency, and a resin comprising the same To provide a composition.
[13]
Task resolution
[14]
According to an embodiment of the present invention in order to solve the above problem, a terephthalate-based material including dibutyl terephthalate, butyl (2-ethylhexyl) terephthalate, and di (2-ethylhexyl) terephthalate; And a triethylene glycol diester-based material comprising triethylene glycol bis (2-ethylhexanoate), (2-ethylhexanoyloxy) triethylene glycol benzoate and triethylene glycol dibenzoate; plasticizer composition comprising: Is provided.
[15]
According to an embodiment of the present invention in order to solve the above problem, 100 parts by weight of a resin; And 5 to 150 parts by weight of the plasticizer composition described above; is provided a resin composition comprising.
[16]
Effects of the Invention
[17]
The plasticizer composition according to an embodiment of the present invention, when used in a resin composition, can maintain excellent mechanical properties such as tensile strength, elongation and modulus, has excellent transmittance and transparency, and has excellent plasticizing efficiency. Can provide.
[18]
Mode for carrying out the invention
[19]
Hereinafter, the present invention will be described in more detail to aid in understanding the present invention.
[20]
Terms and words used in the description and claims of the present invention should not be construed as being limited to their usual or dictionary meanings, and the inventors appropriately explain the concept of terms in order to explain their own invention in the best way. Based on the principle that it can be defined, it should be interpreted as a meaning and concept consistent with the technical idea of ​​the present invention.
[21]
In the present specification, the term "butyl" may mean generally referred to as n-butyl, and may also mean "isobutyl", and thus, hereinafter, the term butyl is not limited to n-butyl. It can be used as a term referring to both n-butyl and isobutyl.
[22]
[23]
Plasticizer composition
[24]
According to an embodiment of the present invention, there is provided a mixed plasticizer composition comprising three kinds of terephthalate-based materials and three kinds of triethylene glycol diester-based materials, and specifically, the terephthalate-based material is dibutyl terephthalate, Characterized in that it comprises butyl (2-ethylhexyl) terephthalate and di (2-ethylhexyl) terephthalate, the triethylene glycol diester-based material is triethylene glycol bis (2-ethylhexanoate), ( 2-ethylhexanoyloxy) triethylene glycol benzoate and triethylene glycol dibenzoate.
[25]
The three types of terephthalate-based materials have excellent permeability or transparency and excellent mechanical properties, so they are advantageous in application to products that come into contact with food or products that come into contact with the human body, but have a disadvantage of relatively poor plasticization efficiency. Improvements have been required due to factors such as a further increase in the product cost due to additional process steps in the process.
[26]
On the other hand, in the case of triethylene glycol diester-based material, it is a representative eco-friendly material, which is considerably superior in terms of plasticizing efficiency, but has poor transparency or permeability, which is a fatal disadvantage when applied to products that come into contact with food or products that come into contact with the human body. However, the mechanical properties are quite low.
[27]
The plasticizer composition according to an embodiment of the present invention is a plasticizer composition capable of solving the above problems, and by mixing with a material that does not have environmental issues such as triethylene glycol diester-based material, the plasticizing efficiency can be greatly improved while mechanical It can be solved by maintaining the physical properties, permeability, and transparency at equal or higher levels.
[28]
The weight ratio of the terephthalate-based material and the triethylene glycol diester-based material contained in the plasticizer composition may be 90:10 to 10:90, and the upper limit may be 90:10, 85:15, 80:20, 70:30 or It can be 60:40, and the lower limit can be 10:90, 15:85, 20:80, 30:70 or 40:60. It may be preferably 90:10 to 20:80, more preferably 90:10 to 30:70, and most preferably 90:10 to 50:50.
[29]
When the weight ratio is satisfied, as described above, specific physical properties can be maintained at the level of excellent properties of each compound, and specific physical properties can be further improved.
[30]
The terephthalate-based material is a material in which a diester group is bonded to the para position of the benzene ring, and a 2-ethylhexyl group and a butyl group are bonded to the diester group, and each of two butyl groups, a 2-ethylhexyl group and a butyl group, And a compound in which two 2-ethylhexyl groups are bonded is mixed.
[31]
The composition of the three compounds is preferably 0.5 to 50% by weight of dibutyl terephthalate; 3.0 to 70% by weight of butyl (2-ethylhexyl) terephthalate; And di(2-ethylhexyl) terephthalate may be 0.5 to 85% by weight, and the weight ratio may be controlled by adjusting the input amount of the raw material during the reaction. Further, more preferably, it may be formed in an amount of 0.5% to 50% by weight, 10% to 50% by weight, and 35% to 80% by weight.
[32]
[33]
In addition, the triethylene glycol diester-based material may be a mixture of three compounds represented by the following formula (a).
[34]
[Formula A]
[35]

[36]
In Formula A, Ra and Rb are each independently or .
[37]
The triethylene glycol diester-based material may generally be a mixture of compounds produced by an esterification reaction of triethylene glycol, benzoic acid, and 2-ethylhexanoic acid, whereby Ra and Rb are each a benzoic acid-derived hydrocarbon group or It may be a hydrocarbon group derived from 2-ethylhexanoic acid, and three types of compounds are those in which both Ra and Rb are hydrocarbon groups derived from benzoic acid, both Ra and Rb are hydrocarbon groups derived from 2-ethylhexanoic acid, and Ra and Rb are 2-ethylhexane It may be a hydrocarbon group derived from warm acid and a hydrocarbon group derived from benzoic acid.
[38]
Specifically, the three types of compounds included in the triethylene glycol diester-based material may be the following Formulas A-1 to A-3.
[39]
[Formula A-1]
[40]

[41]
[Formula A-2]
[42]

[43]
[Formula A-3]
[44]

[45]
The composition of the three compounds of the triethylene glycol diester-based material is preferably triethylene glycol bis(2-ethylhexanoate) 0.5 to 85% by weight; (2-ethylhexanoyloxy) triethylene glycol benzoate 3.0-70 wt%; And 0.5 to 50% by weight of triethylene glycol dibenzoate. Further, more preferably, it may be formed in an amount of 20% to 70% by weight, 20% to 70% by weight, and 1% to 40% by weight.
[46]
In the case of mixing three types of mixed terephthalate as triethylene glycol diester-based materials and three types of mixed triethylene glycol diesters as the plasticizer as the terephthalate-based material, as described above, all the excellent properties of each material have While it can be taken, an effect of improving plasticization efficiency can be seen, and if the mixing weight ratio is adjusted in the same ratio as described above, the effect of improving physical properties can be optimized.
[47]
[48]
The plasticizer composition according to another embodiment of the present invention comprises dibutyl terephthalate, butyl (2-ethylhexyl) terephthalate, di (2-ethylhexyl) terephthalate, and terephthalate represented by the following Formula 1 Terephthalate-based substances; And triethylene glycol diester-based materials including triethylene glycol bis (2-ethylhexanoate), (2-ethylhexanoyloxy) triethylene glycol benzoate, and triethylene glycol dibenzoate, and the Di(2-ethylhexyl) terephthalate is 99.0 parts by weight or more, compared to 100 parts by weight of the mixed weight of di(2-ethylhexyl) terephthalate and terephthalate represented by the following formula (1), and terephthalate represented by the following formula (1) is It is characterized in that less than 1.0 parts by weight.
[49]
[Formula 1]
[50]

[51]
In Formula 1, R 1 is a straight-chain or branched alkyl group having 1 to 13 carbon atoms, but not a 2-ethylhexyl group.
[52]
Di(2-ethylhexyl) terephthalate is 99.0 parts by weight or more, based on 100 parts by weight of the mixed weight of the di(2-ethylhexyl) terephthalate and the terephthalate represented by the following Formula 1, and terephthalate represented by the following Formula 1 May be less than 1.0 part by weight, preferably at least 99.2 parts by weight and less than 0.8 parts by weight, more preferably at least 99.5 parts by weight and less than 0.5 parts by weight, optimally at least 99.9 parts by weight and less than 0.1 parts by weight, or 99.95 It may be greater than or equal to 0.05 parts by weight and less than 0.05 parts by weight.
[53]
[54]
[Manufacturing method]
[55]
In the present invention, the method of preparing the plasticizer composition can be applied to a blending method, and a plasticizer composition can be prepared by mixing after each of a terephthalate-based material and a triethylene glycol diester-based material are prepared. have.
[56]
The terephthalate-based material may be prepared by a direct esterification reaction of terephthalic acid and two alcohols, or a transesterification reaction of di(2-ethylhexyl) terephthalate and butyl alcohol.
[57]
In the direct esterification reaction, the alcohol may be 2-ethylhexyl alcohol and butanol, and a mixed alcohol thereof may be directly applied to the esterification reaction.
[58]
In the direct esterification reaction, terephthalic acid is added to alcohol, and then a catalyst is added and reacted in a nitrogen atmosphere; Removing unreacted alcohol and neutralizing unreacted acid; And dehydration and filtering by distillation under reduced pressure; can be prepared as.
[59]
In addition, the alcohol may be used in the range of 150 to 500 mol%, 200 to 400 mol%, 200 to 350 mol%, 250 to 400 mol%, or 270 to 330 mol% based on 100 mol% of terephthalic acid.
[60]
On the other hand, the catalyst of the esterification reaction is, for example, sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, paratoluenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, alkyl sulfates and other acid catalysts, aluminum lactate, lithium fluoride, potassium chloride , Metal salts such as cesium chloride, calcium chloride, iron chloride, aluminum phosphate, metal oxides such as heteropoly acids, natural/synthetic zeolites, cation and anion exchange resins, tetraalkyl titanate, and organic metals such as polymers 1 It can be more than a species. As a specific example, the catalyst may be tetraalkyl titanate.
[61]
The amount of catalyst used may vary depending on the type, for example, in the case of a homogeneous catalyst, in the range of 0.01 to 5% by weight, 0.01 to 3% by weight, 1 to 5% by weight, or 2 to 4% by weight based on the total 100% by weight of the reactants. In the case of inner and heterogeneous catalysts, it may be in the range of 5 to 200% by weight, 5 to 100% by weight, 20 to 200% by weight, or 20 to 150% by weight of the total amount of the reactant.
[62]
At this time, the reaction temperature may be in the range of 180 to 280°C, 200 to 250°C, or 210 to 230°C.
[63]
[64]
In addition, a transesterification reaction may be performed to prepare the terephthalate-based material. In the case of the transesterification reaction, di(2-ethylhexyl) terephthalate and butyl alcohol may react.
[65]
Meanwhile, the "trans-esterification reaction" used in the present invention refers to a reaction in which an alcohol and an ester react as shown in Scheme 1 below, so that R" of an ester is interchanged with R'of an alcohol as shown in Scheme 1 below. :
[66]
[Scheme 1]
[67]

[68]
According to an embodiment of the present invention, when the trans-esterification reaction is performed, the alkoxide of the alcohol attacks the carbon of two ester (RCOOR") groups present in the ester-based compound; as long as it is present in the ester-based compound. Attacking the carbon of the dog's ester (RCOOR") group; As in the case of unreacted reaction in which no reaction has been made; in three cases, three kinds of ester compositions may be produced by number.
[69]
In addition, the trans-esterification reaction has the advantage of not causing a wastewater problem compared to the acid-alcohol esterification reaction, and since it can be carried out without a catalyst, the problem of using an acid catalyst can be solved.
[70]
The composition ratio of the terephthalate-based material prepared through the transesterification reaction as described above is the same as described above, and this composition ratio can control the composition ratio of the mixture according to the amount of alcohol added.
[71]
The amount of the alcohol added may be 0.1 to 89.9 parts by weight, specifically 3 to 50 parts by weight, and more specifically 5 to 40 parts by weight based on 100 parts by weight of the terephthalate compound.
[72]
In the terephthalate, as the amount of alcohol added increases, the mole fraction of the terephthalate compound participating in the trans-esterification reaction will increase, and thus the content of the two terephthalate compounds as products in the mixture may increase, Correspondingly, the content of the unreacted terephthalate compound may tend to decrease.
[73]
According to an embodiment of the present invention, the molar ratio of the reactant terephthalate and alcohol is, for example, 1:0.005 to 5.0, 1:0.05 to 2.5, or 1:0.1 to 1.0, within this range, the process efficiency is high and processability is improved. There is an effect of obtaining an ester plasticizer composition excellent in effect.
[74]
The composition ratio may be a mixed composition ratio generated by an esterification reaction, and may be an intended composition ratio by additionally mixing a specific compound, and the mixed composition ratio may be appropriately adjusted to suit the desired physical properties. The composition ratio of the mixture of the three types of terephthalate-based substances is not limited to the above range, and the composition ratio can be changed by adding any one of the three types of terephthalate, and the possible mixing composition ratio is as described above. .
[75]
According to an embodiment of the present invention, the transesterification reaction is 10 to 10 hours, preferably 30 under a reaction temperature of 120 to 190°C, preferably 135 to 180°C, more preferably 141 to 179°C. It is preferably carried out in minutes to 8 hours, more preferably 1 to 6 hours. It is possible to effectively obtain a mixture of terephthalate-based materials having a desired composition ratio within the above temperature and time range. In this case, the reaction time may be calculated from the point when the reaction temperature reaches the reaction temperature after heating.
[76]
The transesterification reaction may be carried out under an acid catalyst or a metal catalyst, and in this case, the reaction time is shortened.
[77]
The acid catalyst may be, for example, sulfuric acid, methanesulfonic acid, or p-toluenesulfonic acid, and the metal catalyst may be, for example, an organometallic catalyst, a metal oxide catalyst, a metal salt catalyst, or a metal itself.
[78]
The metal component may be, for example, any one selected from the group consisting of tin, titanium, and zirconium, or a mixture of two or more of them.
[79]
The direct esterification reaction and the transesterification reaction may also be used to prepare the aforementioned triethylene glycol diester-based material. That is, conditions such as specific reaction conditions or molar ratio may be similar.
[80]
However, in the case of a triethylene glycol diester-based material, it can be generally prepared by a transesterification reaction, and can be prepared using benzoic acid, 2-ethylhexanoic acid, and triethylene glycol as raw materials, and a terephthalate-based material and There may be differences in using dialcohol rather than using dicarboxylic acid.
[81]
The method for preparing the triethylene glycol diester-based material is not particularly limited, and there is no particular limitation on the production method as long as it is a method capable of providing a material in which three types of triethylene glycol diesters are mixed.
[82]
The terephthalate-based material and the triethylene glycol diester-based material prepared as described above may be blended through a general method, and there is no particular limitation on the blending method.
[83]
[84]
Resin composition
[85]
According to another embodiment of the present invention, the plasticizer composition is 100 parts by weight of a resin such as ethylene vinyl acetate, polyethylene, polyketone, polypropylene, polyvinyl chloride, polystyrene, polyurethane, or a thermoplastic elastomer, or mixtures thereof. With respect to, it may include 5 to 150 parts by weight, 10 to 100 parts by weight, or 30 to 60 parts by weight, and 70 to 130 parts by weight depending on the application to be applied.
[86]
The resin composition may be processed through various methods such as plastisol processing, extrusion or injection processing, and calendering processing, and may be used for wires, automotive interior materials, films, sheets, tubes, wallpaper, toys, flooring, wires, or optical fiber coverings. Can be applied.
[87]
In addition, the resin composition may include those designed for use in the medical or food industry. Gloves, oxygen masks, calibration holding devices, artificial skin and food packaging (eg, packaging for various beverages, meat and frozen vegetables), and the like.
[88]
Preferably, it can be applied to eco-friendly food packaging resins or medical resins, so that it can receive excellent evaluation in sensory evaluation such as transparency and color, excellent adhesion, tensile strength and elongation, and plasticization. Basic mechanical properties such as efficiency and heating loss can also exhibit physical properties equal to or higher than those of conventional plasticizers.
[89]
The resin composition may additionally add a stabilizer or an anti-fogging agent, and other additives may be additionally added.
[90]
[91]
Example
[92]
Hereinafter, examples will be described in detail to specifically describe the present invention. However, the embodiments according to the present invention can be modified in many different 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 fully describe the present invention to those skilled in the art.
[93]
[94]
Preparation Example 1: Preparation of terephthalate-based material
[95]
2000 g of di(2-ethylhexyl) terephthalate (LG Chemical Co., Ltd.) and 340 g of n-butanol (17 parts by weight based on 100 parts by weight of DEHTP) were added to a reactor equipped with a stirrer, condenser, and decanter, and then 160 under nitrogen atmosphere. Transesterification reaction at a reaction temperature of °C for 2 hours, dibutyl terephthalate (DBTP), butyl (2-ethylhexyl) terephthalate (BEHTP) and di(2-ethylhexyl) terephthalate (DEHTP) were each 4.0 A composition comprising in the range of weight percent, 35.0 weight percent and 61.0 weight percent was obtained.
[96]
The reaction product was mixed and distilled to remove butanol and 2-ethylhexyl alcohol, and finally a mixed composition was prepared.
[97]
[98]
Preparation Example 2: Preparation of triethylene glycol diester-based material
[99]
Triethylene glycol 450.5 g 2-ethylhexanoic acid 778.7 g, benzoic acid 293.0 g, and tetranormal butyl titanate 2.0 g as a catalyst were added to a reactor equipped with a stirrer, condenser and decanter, and then heated to 220°C under a nitrogen atmosphere to 10 The esterification reaction was carried out for hours. Thereafter, triethylene glycol bis (2-ethylhexanoate), (2-ethylhexanoyloxy) triethylene glycol benzoate and triethylene glycol dibenzoate were 42.4 wt%, 45.4 wt%, and 12.2 wt%, respectively, through a purification process. A composition comprising in the weight percent range was obtained.
[100]
[101]
The materials prepared in Preparation Examples 1 and 2 were mixed to prepare a plasticizer composition of the Examples, which was summarized in Table 1 below, and the evaluation of physical properties of the plasticizer composition was performed according to the following test items.
[102]
[Table 1]
Substance of Preparation Example 1 Material of Preparation Example 2
Example 1 90 10
Example 2 70 30
Example 3 50 50
Example 4 30 70
Example 5 10 90
Comparative Example 1 100 0
Comparative Example 2 0 100
[103]

[104]
Hardness measurement
[105]
Using ASTM D2240, shore (shore A and D) hardness at 25° C., 3T 10s was measured, and the lower it is, the better it is evaluated.
[106]
[107]
Measurement of tensile strength
[108]
According to the ASTM D638 method, after pulling the cross head speed at 100 mm/min (0.25T) using a test instrument UTM (manufacturer; Instron, model name; 4466), the point at which the specimen is cut is measured. I did. Tensile strength was measured for the TD and MD directions, and was calculated as follows, and the higher the value, the better it is evaluated:
[109]
Tensile strength (kgf/㎟) = load value (kgf) / thickness (mm) x width (mm)
[110]
[111]
Elongation rate measurement
[112]
According to the ASTM D638 method, after pulling the cross head speed at 100 mm/min (0.25T) using the UTM, the point where the specimen is cut is measured, but measured in the TD direction and the MD direction. After that, the elongation was calculated as follows, and the higher it is, the better it is evaluated:
[113]
Elongation (%) = [length after elongation / initial length] x 100
[114]
[115]
Measurement of migration loss
[116]
According to KSM-3156, a specimen (1T) having a thickness of 2 mm or more was obtained, and after attaching PS plates to both sides of the specimen, a load of 1 kgf/cm 2 was applied. The specimen was left in a hot air circulation oven (80°C) for 72 hours, 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 migration loss was calculated by the following equation, and the lower it is, the better it is evaluated.
[117]
Transfer loss (%) = [(Initial weight of specimen at room temperature-weight of specimen after leaving the oven) / Initial weight of specimen at normal temperature] x 100
[118]
[119]
Measurement of volatile loss
[120]
The fabricated specimen was worked at 80° C. for 72 hours, and the weight of the specimen was measured and calculated as follows, and the lower the value, the better the item.
[121]
Heating loss (%) = [(Initial specimen weight-specimen weight after work) / Initial specimen weight] x 100
[122]
[123]
100% modulus measurement
[124]
According to ASTM D638 method, tensile stress (100% modulus) at 100% elongation in the TD and MD directions after pulling the cross head speed at 100 mm/min (0.25T) using the UTM. Was measured, and the lower it is, the better it is evaluated.
[125]
[126]
Haze and transparency
[127]
Haze and transparency were measured using an NDH 7000 Haze Meter. The lower the haze, the better, and the higher the transparency, the better.
[128]
[129]
Evaluation of adhesion and loosening properties
[130]
By direct contact with hands, the excellent degree of adhesion was evaluated as 5 scale, and 1 was excellent and 5 was evaluated as poor, and the excellent degree of loosening was evaluated as 5 scale, and 1 was excellent and 5 was poor.
[131]
[132]
Experimental Example 1: Evaluation of physical properties of resin specimens
[133]
Specimens were prepared using the mixed plasticizer compositions of Examples and Comparative Examples described in Table 1 above.
[134]
For the preparation of the specimen, referring to ASTM D638, based on 100 parts by weight of a polyvinyl chloride resin (PVC (LS100)), 40 parts by weight of the plasticizer composition prepared in the Examples and Comparative Examples, and 10 parts by weight of epoxidized soybean oil (ESO). Parts, 1.5 parts by weight of LTX-630P as a stabilizer and 2 parts by weight of Almax-9280 anti-fogging agent were mixed and mixed at 98° C. at 700 rpm. A specimen was prepared by working at 160° C. for 4 minutes using a roll mill, and working at 180° C. for 2.5 minutes (low pressure) and 2 minutes (high pressure) using a press.
[135]
The test items were evaluated for the specimens, and the results are shown in Table 2 below.
[136]
[Table 2]
Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2
Hardness Shore A 81.5 81.3 81.1 80.6 80.3 83.0 80.3
Shore D 36.2 36.2 36.1 36.1 36.0 37.3 36.0
Tensile strength (kg/cm 2 ) TD 211.5 210.3 208.9 206.8 207.0 210.0 198.2
MD 230.1 223.8 222.7 226.8 227.7 228.7 210.5
Elongation(%) TD 295.0 292.4 293.0 294.5 291.2 293.2 280.4
MD 292.1 290.3 287.9 284.6 285.9 294.0 267.4
100% modulus TD 92.0 91.7 91.7 91.3 91.3 94.0 91.0
MD 98.8 98.8 98.5 98.5 98.5 101.1 94.9
Performance loss (%) 1.37 1.35 1.42 1.43 1.48 1.33 1.78
Heating loss (%) 1.88 2.10 2.14 2.38 2.64 1.90 3.71
Haze (%) 3.21 3.20 3.26 3.44 3.58 3.18 5.21
Transparency (%) 91.0 90.2 89.9 90.7 89.5 91.1 86.2
Stickiness 2 2 One One One 4 One
Loosening 3 2 2 2 2 5 2
[137]
Referring to Table 2, in the case of Examples 1 to 4, it can be seen that the hardness value was evaluated at the same level as the triethylene glycol diester-based material of Comparative Example 2, so that the plasticization efficiency was excellent. , The mechanical properties of tensile strength, elongation, and modulus values ​​were evaluated at the same level as in Comparative Example 1, and it was confirmed that the properties were also superior, and Comparative Example 1 having lower values ​​in the case of transfer loss and heating loss. It can be seen that it has a better value, which is equivalent to that, and the haze value and transparency are also on the same level as those of the superior one.
[138]
In particular, in the case of tensile strength and elongation, triethylene glycol diester-based materials with poor tensile strength and elongation are used when a terephthalate-based material is mixed with a triethylene glycol diester-based material compared to a terephthalate-based material alone. It can also be seen that, despite mixing, the value can be further improved.
[139]
In addition, when the plasticizer compositions of Examples 1 to 5 above were wrapped to perform sensory evaluation of the adhesiveness and loosening properties of the film, it was confirmed that the effect of improving the overall poor properties of the terephthalate-based material of Comparative Example 1 could be obtained. Could
[140]
In other words, as an effect predicted by the mixture of two substances, each of the physical properties does not show a linear change, but the excellent properties of each material are maintained at the same level or higher, and some properties have improved results. I can.
[141]
[142]
Through this, in the case of mixing the terephthalate-based material and the triethylene glycol diester-based material, the excellent physical properties of each material are maintained at the same level or higher, and at the same time, the mechanical properties and sensory properties can exhibit improved values. As can be seen, it can be seen that the plasticizer composition according to the present invention can provide a resin having excellent plasticization efficiency, improved mechanical properties, and excellent heating loss, transfer loss, haze, and transmittance.
Claim
[Claim 1]
Terephthalate-based substances including dibutyl terephthalate, butyl (2-ethylhexyl) terephthalate, and di(2-ethylhexyl) terephthalate; And a triethylene glycol diester-based material including triethylene glycol bis (2-ethylhexanoate), (2-ethylhexanoyloxy) triethylene glycol benzoate and triethylene glycol dibenzoate; plasticizer composition comprising: .
[Claim 2]
The plasticizer composition of claim 1, wherein the terephthalate-based material and the triethylene glycol diester-based material have a weight ratio of 90:10 to 10:90.
[Claim 3]
According to claim 1, The terephthalate-based material is dibutyl terephthalate 0.5 to 30% by weight; Butyl (2-ethylhexyl) terephthalate 10 to 50% by weight; And 40 to 89% by weight of di(2-ethylhexyl) terephthalate.
[Claim 4]
According to claim 1, The triethylene glycol diester-based material is triethylene glycol bis (2-ethylhexanoate) 0.5 to 85% by weight; (2-ethylhexanoyloxy) triethylene glycol benzoate 3.0-70 wt%; And triethylene glycol dibenzoate 0.5 to 50% by weight of the plasticizer composition.
[Claim 5]
Terephthalate-based substances including dibutyl terephthalate, butyl (2-ethylhexyl) terephthalate, di (2-ethylhexyl) terephthalate, and terephthalate represented by the following formula (1); And triethylene glycol diester-based materials including triethylene glycol bis (2-ethylhexanoate), (2-ethylhexanoyloxy) triethylene glycol benzoate, and triethylene glycol dibenzoate, and the The di(2-ethylhexyl) terephthalate is 99.0 parts by weight or more, and the terephthalate represented by the following formula (1) compared to 100 parts by weight of di(2-ethylhexyl) terephthalate and the terephthalate represented by the following formula The plasticizer composition of less than 1.0 part by weight: [Formula 1] In Formula 1, R 1 is a straight-chain or branched alkyl group having 1 to 13 carbon atoms, but not a 2-ethylhexyl group.
[Claim 6]
100 parts by weight of resin; And 5 to 150 parts by weight of the plasticizer composition of claim 1 or 5.
[Claim 7]
The resin composition of claim 6, 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.
[Claim 8]
The resin composition according to claim 6, wherein the resin composition is a material of at least one product selected from the group consisting of electric wires, flooring materials, automobile interior materials, films, sheets, wallpaper, and tubes.