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Plasticizer Composition And Resin Composition Comprising Same

Abstract: The present invention relates to a plasticizer composition and a resin composition comprising the same. The plasticizer composition comprises: a terephthalate-based material comprising dibutyl terephthalate, butyl(2-ethylhexyl) terephthalate and di(2-ethylhexyl) terephthalate; and a glyceride-based material, and the plasticizer composition can improve mechanical properties such as tensile strength, elongation and modulus and can maintain the characteristics of a terephthalate-based material having excellent transmittance, transparency and migration loss characteristics.

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Patent Information

Application #
Filing Date
31 March 2020
Publication Number
40/2020
Publication Type
INA
Invention Field
POLYMER TECHNOLOGY
Status
Email
mahua.ray@remfry.com
Parent Application
Patent Number
Legal Status
Grant Date
2022-08-23
Renewal Date

Applicants

LG CHEM, LTD.
128, Yeoui-daero, Yeongdeungpo-gu, Seoul 07336

Inventors

1. KIM, Hyun Kyu
LG Chem Research Park, 188, Munji-ro, Yuseong-gu, Daejeon 34122
2. MOON, Jeong Ju
LG Chem Research Park, 188, Munji-ro, Yuseong-gu, Daejeon 34122
3. CHO, Yun Ki
LG Chem Research Park, 188, Munji-ro, Yuseong-gu, Daejeon 34122
4. KIM, Joo Ho
LG Chem Research Park, 188, Munji-ro, Yuseong-gu, Daejeon 34122
5. JEONG, Seok Ho
LG Chem Research Park, 188, Munji-ro, Yuseong-gu, Daejeon 34122

Specification

Specification
Title of the invention: plasticizer composition and resin composition comprising the same
Technology field
[One]
Mutual citations with related applications
[2]
This application claims the benefit of priority based on Korean Patent Application No. 10-2017-0165273 filed on December 04, 2017, and all content disclosed in the literature of the Korean patent application is incorporated as part of this specification.
[3]
[4]
Technology field
[5]
The present invention relates to a plasticizer composition and a resin composition comprising the same.
[6]
Background
[7]
Typically plasticizers react with alcohols with polycarboxylic acids such as phthalic acid and adipic acid to form the corresponding esters. In addition, considering the domestic and foreign regulations of phthalate-based plasticizers harmful to the human body, research into plasticizer compositions that can replace phthalate-based plasticizers such as terephthalate-based, adipate-based, and other polymer-based polymers has been continued.
[8]
In general, plasticizers add various additives such as polyvinyl chloride (PVC), fillers, stabilizers, pigments, anti-fogging agents, and other additives to provide various processing properties. , Pipes, flooring, wallpaper, sheet, artificial leather, tarpaulin, tape, and food packaging materials.
[9]
The current plasticizer market situation is that the development of eco-friendly plasticizers is being conducted competitively in the industry due to environmental issues regarding phthalate plasticizers. Products are being developed for plasticizer compositions including products. Accordingly, research on technologies that can be optimally applied as plasticizers for vinyl chloride-based resins is still needed by developing products that are superior to products commonly used in the plasticizer market or products of new compositions containing one or more types. .
[10]
Detailed description of the invention
Technical challenges
[11]
In the present invention, as a plasticizer applied to the resin composition, it is possible to improve the mechanical properties such as tensile strength, elongation and modulus, and plasticizer composition capable of maintaining the properties of a terephthalate-based material having excellent transmittance, transparency and transition loss characteristics, and It is intended to provide a resin composition comprising.
[12]
Task resolution
[13]
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 glyceride-based material comprising at least one compound represented by the following formula (1).
[14]
[Formula 1]
[15]

[16]
In Formula 1, R is a linear or branched alkyl group having 8 to 20 carbon atoms.
[17]
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.
[18]
Effects of the Invention
[19]
The plasticizer composition according to an embodiment of the present invention, when used in a resin composition, can improve mechanical properties such as tensile strength, elongation and modulus, and has excellent properties of a terephthalate-based material having excellent transmittance, transparency, and transition loss characteristics. It can provide a plasticizer that can be maintained.
[20]
Mode for carrying out the invention
[21]
Hereinafter, the present invention will be described in more detail to aid in understanding the present invention.
[22]
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.
[23]
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.
[24]
[25]
Plasticizer composition
[26]
According to an embodiment of the present invention, a mixed plasticizer composition is provided comprising three types of terephthalate-based materials and a glyceride-based material, specifically, the terephthalate-based material is dibutyl terephthalate, butyl (2-ethylhexyl ) Terephthalate and di(2-ethylhexyl) terephthalate, and the glyceride-based material is characterized in that it contains at least one compound represented by the following formula (1).
[27]
The three types of terephthalate-based materials have excellent permeability or transparency and excellent transfer loss characteristics, which makes it advantageous to apply to products that come into contact with food or products that come into contact with the human body, but have relatively poor mechanical properties. When applied to a product in the form of a film, there has been a demand for improvement in the unwinding property of the film.
[28]
On the other hand, in the case of a glyceride-based material, it is a representative eco-friendly material and has excellent plasticization efficiency, but its transparency or permeability is somewhat poor, and this also has poor mechanical properties, which can act as a fatal disadvantage in the commercialization process.
[29]
The plasticizer composition according to an embodiment of the present invention is a plasticizer composition capable of solving the above problems, and by mixing and using materials without environmental issues, the mechanical properties are improved, while the permeability and transparency, transfer loss characteristics and plasticization efficiency are Excellent material properties can be maintained.
[30]
The weight ratio of the terephthalate-based material and the glyceride-based material included in the plasticizer composition may be 90:10 to 10:90, and the upper limit is 90:10, 85:15, 80:20, 70:30 or 60:40 May be, and the lower limit may 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.
[31]
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.
[32]
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.
[33]
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.
[34]
In addition, the glyceride-based material may include one or more compounds represented by the following formula (1).
[35]
[Formula 1]
[36]

[37]
In Formula 1, R is a linear or branched alkyl group having 8 to 20 carbon atoms.
[38]
The glyceride-based material may preferably have an alkyl group having an even number of carbons among those having 8 to 20 carbon atoms of R, and may be preferably linear. In addition, the glyceride-based material may include one or more compounds of the formula (1), in this case, the carbon number of R of each compound may be different from each other, mainly 12 and 14 carbon atoms And 18.
[39]
In general, when two materials are mixed, physical properties of each material may show a linear change according to the mixing ratio of each material. However, in the case of mixing the terephthalate-based material and the glyceride-based material, such as the plasticizer composition according to the present invention, while maintaining excellent properties of the respective materials, in particular, the mechanical properties are improved compared to the mechanical properties of the two materials. I can.
[40]
[41]
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 (2). Terephthalate-based substances; And a glyceride-based material comprising at least one compound represented by Formula 1; and, based on 100 parts by weight of the mixed weight of the di(2-ethylhexyl) terephthalate and the terephthalate represented by the following Formula 2 ( 2-ethylhexyl) terephthalate is 99.0 parts by weight or more, and terephthalate represented by the following formula (2) is characterized in that it is less than 1.0 part by weight.
[42]
[Formula 2]
[43]

[44]
In Formula 2, R 1 is a straight-chain or branched alkyl group having 1 to 13 carbon atoms, but not a 2-ethylhexyl group.
[45]
The di(2-ethylhexyl) terephthalate is 99.0 parts by weight or more, compared to 100 parts by weight of the mixed weight of the di(2-ethylhexyl) terephthalate and the terephthalate represented by the following formula (2), and terephthalate represented by the following formula (2) May be less than 1.0 parts by weight, preferably 99.2 parts by weight or more and less than 0.8 parts by weight, more preferably 99.5 parts by weight or more and less than 0.5 parts by weight, optimally 99.9 parts by weight or more and less than 0.1 parts by weight, or 99.95 It may be more than parts by weight and less than 0.05 parts by weight.
[46]
[47]
Manufacturing method
[48]
In the present invention, the plasticizer composition may be prepared by a blending method, and a terephthalate-based material and a glyceride-based material are each prepared and then mixed to prepare a plasticizer composition.
[49]
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.
[50]
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.
[51]
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.
[52]
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.
[53]
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.
[54]
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.
[55]
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.
[56]
[57]
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.
[58]
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. :
[59]
[Scheme 1]
[60]

[61]
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.
[62]
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.
[63]
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.
[64]
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.
[65]
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.
[66]
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.
[67]
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. .
[68]
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.
[69]
The transesterification reaction may be carried out under an acid catalyst or a metal catalyst, and in this case, the reaction time is shortened.
[70]
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.
[71]
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.
[72]
[73]
The direct esterification reaction and the transesterification reaction may also be used to prepare the above-described glyceride-based material. That is, conditions such as specific reaction conditions or molar ratio may be similar.
[74]
The glyceride-based material may generally be prepared using vegetable oil as a raw material, and substances such as glycerin, acetic acid (or acetic anhydride), and triacetin may be used together as an auxiliary material.
[75]
For example, as a first method, the compound represented by Formula 1 may include a direct esterification step in which glycerin and acetic acid react to produce triacetin in the presence of a catalyst; And a transesterification step in which the vegetable oil and the triacetin react in the presence of a catalyst. That is, it may be prepared by first acetylating glycerin and transesterification of triacetin and vegetable oil in which glycerin is acetylated.
[76]
In addition, as a second method, the step of transesterification reaction between vegetable oil and glycerin; And reacting a product of the transesterification reaction with acetic acid. In the case of the second method, unlike the first method, the esterification reaction and the acetylation may be performed in reverse order.
[77]
The vegetable oil is, for example, almond oil, avocado oil, castor oil, corn oil, cottonseed oil, olive oil, peanut oil. oil), rice bran oil, safflower oil, sesame oil, soybean oil, sunflower oil, refined palm oil, palm kernel oil ), coconut oil or canola oil may be applied.
[78]
The specific esterification reaction conditions and the type of catalyst may not differ significantly from those described above, and the acid may be replaced with an acid anhydride, and after the reaction is completed, a general commercialization process such as purification may be performed.
[79]
The terephthalate-based material and the glyceride-based material prepared as described above may be blended through a general method, and the blending method is not particularly limited.
[80]
[81]
Resin composition
[82]
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.
[83]
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.
[84]
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.
[85]
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.
[86]
The resin composition may additionally add a stabilizer or an anti-fogging agent, and other additives may be additionally added.
[87]
[88]
Example
[89]
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.
[90]
[91]
Preparation Example 1: Preparation of terephthalate-based material
[92]
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.
[93]
The reaction product was mixed and distilled to remove butanol and 2-ethylhexyl alcohol, and finally a mixed composition was prepared.
[94]
[95]
Preparation Example 2: Preparation of glyceride-based material
[96]
1000 g of coconut oil and 300 g of glycerin were added to the same apparatus as in Preparation Example 1, followed by transesterification at a reaction temperature of 100° C. for 4 hours, followed by purification to obtain monoglyceride. Thereafter, acetylation was carried out at 120°C using an excess of acetic anhydride, followed by extraction and purification to obtain 1510 g of a final product.
[97]
[98]
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.
[99]
[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
[100]

[101]
Hardness measurement
[102]
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.
[103]
[104]
Measurement of tensile strength
[105]
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:
[106]
Tensile strength (kgf/㎟) = load value (kgf) / thickness (mm) x width (mm)
[107]
[108]
Elongation rate measurement
[109]
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:
[110]
Elongation (%) = [length after elongation / initial length] x 100
[111]
[112]
Measurement of migration loss
[113]
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.
[114]
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
[115]
[116]
Measurement of volatile loss
[117]
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.
[118]
Heating loss (%) = [(Initial specimen weight-specimen weight after work) / Initial specimen weight] x 100
[119]
[120]
100% modulus measurement
[121]
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.
[122]
[123]
Haze and transparency
[124]
Haze and transparency were measured using an NDH 7000 Haze Meter. The lower the haze, the better, and the higher the transparency, the better.
[125]
[126]
Experimental Example 1: Evaluation of physical properties of resin specimens
[127]
Specimens were prepared using the mixed plasticizer compositions of Examples and Comparative Examples described in Table 1 above.
[128]
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.
[129]
The test items were evaluated for the specimens, and the results are shown in Table 2 below.
[130]
[Table 2]
Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2
Hardness Shore A 82.3 82.3 82.2 82.0 81.8 83.8 81.8
Shore D 36.8 36.7 36.7 36.5 36.4 37.8 36.4
Tensile strength (kg/cm 2 ) TD 208.2 205.9 206.7 206.0 204.5 210.0 196.0
MD 227.0 225.6 225.1 223.9 223.7 228.7 208.3
Elongation(%) TD 292.5 292.7 291.3 292.0 293.0 293.2 293.4
MD 305.0 306.6 307.5 304.0 306.7 294.0 305.4
100% modulus TD 91.5 91.3 91.4 91.2 90.9 94.0 90.8
MD 96.2 94.9 94.6 94.8 94.2 101.1 94.0
Performance loss (%) 1.38 1.42 1.66 1.74 2.21 1.33 4.10
Heating loss (%) 2.01 2.13 2.45 2.50 2.68 1.90 3.25
Haze (%) 3.20 3.33 3.37 3.60 3.80 3.18 5.88
Transparency (%) 91.2 90.5 90.4 89.5 88.7 91.1 85.9
[131]
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 that of the glyceride-based material of Comparative Example 2, so that the plasticization efficiency was excellent, and the mechanical properties In the case of phosphorus tensile strength, elongation, and modulus values, it can be seen that even when compared with all of Comparative Examples 1 and 2, the values ​​are shown at the same level as those of materials having excellent values. In addition, in the case of the transfer loss and the heating loss, it can be confirmed that the excellent physical properties were taken as compared to Comparative Example 1 having a lower value, and the haze value and the transmittance were also at the same level as the values ​​of the superior one.
[132]
In particular, in the case of the elongation property, the terephthalate-based material and the glyceride-based material have similar elongation in the TD direction, but the elongation in the MD direction is superior to the glyceride-based material of Comparative Example 2, but when the two materials are mixed, the TD direction It can be seen that the MD direction has excellent values, and the elongation in the MD direction has a more improved value.
[133]
Through this, when the terephthalate-based material and the glyceride-based material are mixed, it can be seen that the excellent physical properties of the respective materials can be maintained at the same level or higher, and at the same time, the mechanical properties can exhibit more improved values. It can be seen that the plasticizer composition according to the plasticizer composition has excellent plasticization efficiency and improves mechanical properties, and can provide a resin capable of maintaining excellent levels of heating loss, transfer loss, haze, and transmittance.
[134]
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.
Claim
[Claim 1]
Terephthalate-based substances including dibutyl terephthalate, butyl (2-ethylhexyl) terephthalate, and di(2-ethylhexyl) terephthalate; And a glyceride-based material comprising at least one compound represented by the following Formula 1; Plasticizer composition comprising: [Formula 1] In Formula 1, R is a linear or branched alkyl group having 8 to 20 carbon atoms.
[Claim 2]
The plasticizer composition of claim 1, wherein the terephthalate-based material and the glyceride-based material have a weight ratio of 90:10 to 10:90.
[Claim 3]
The plasticizer composition of claim 1, wherein the terephthalate-based material and the glyceride-based material have a weight ratio of 90:10 to 30:70.
[Claim 4]
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 5]
Terephthalate-based materials including dibutyl terephthalate, butyl (2-ethylhexyl) terephthalate, di (2-ethylhexyl) terephthalate, and terephthalate represented by the following formula (2); And a glyceride-based material comprising at least one compound represented by the following formula (1); including, and di(2-ethylhexyl) terephthalate and terephthalate represented by the following formula (2) based on 100 parts by weight of a mixed weight of 100 parts by weight 2-ethylhexyl) terephthalate is 99.0 parts by weight or more, and the terephthalate represented by the following formula (2) is less than 1.0 parts by weight: [Formula 1] In Formula 1, R is a C8 to C18 linear or It is a branched alkyl group. [Chemical Formula 2] In Formula 2, 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.

Documents

Application Documents

# Name Date
1 202017014249-TRANSLATIOIN OF PRIOIRTY DOCUMENTS ETC. [31-03-2020(online)].pdf 2020-03-31
2 202017014249-STATEMENT OF UNDERTAKING (FORM 3) [31-03-2020(online)].pdf 2020-03-31
3 202017014249-PRIORITY DOCUMENTS [31-03-2020(online)].pdf 2020-03-31
4 202017014249-FORM 1 [31-03-2020(online)].pdf 2020-03-31
5 202017014249-DECLARATION OF INVENTORSHIP (FORM 5) [31-03-2020(online)].pdf 2020-03-31
6 202017014249-COMPLETE SPECIFICATION [31-03-2020(online)].pdf 2020-03-31
7 202017014249-Verified English translation [12-06-2020(online)].pdf 2020-06-12
8 202017014249-Proof of Right [12-06-2020(online)].pdf 2020-06-12
9 202017014249-FORM-26 [29-08-2020(online)].pdf 2020-08-29
10 202017014249-Information under section 8(2) [07-09-2020(online)].pdf 2020-09-07
11 202017014249-FORM 3 [07-09-2020(online)].pdf 2020-09-07
12 202017014249-FORM 18 [27-05-2021(online)].pdf 2021-05-27
13 202017014249.pdf 2021-10-19
14 202017014249-FER.pdf 2021-10-19
15 202017014249-OTHERS [09-11-2021(online)].pdf 2021-11-09
16 202017014249-FER_SER_REPLY [09-11-2021(online)].pdf 2021-11-09
17 202017014249-CLAIMS [09-11-2021(online)].pdf 2021-11-09
18 202017014249-ABSTRACT [09-11-2021(online)].pdf 2021-11-09
19 202017014249-PatentCertificate23-08-2022.pdf 2022-08-23
20 202017014249-IntimationOfGrant23-08-2022.pdf 2022-08-23

Search Strategy

1 2021-06-0817-17-38E_08-06-2021.pdf

ERegister / Renewals

3rd: 02 Sep 2022

From 04/12/2020 - To 04/12/2021

4th: 02 Sep 2022

From 04/12/2021 - To 04/12/2022

5th: 02 Sep 2022

From 04/12/2022 - To 04/12/2023

6th: 27 Nov 2023

From 04/12/2023 - To 04/12/2024

7th: 02 Dec 2024

From 04/12/2024 - To 04/12/2025