This application claims the benefit of priority based on Korean Patent Application No. 10-2018-0067653 dated June 12, 2018, and all contents disclosed in the literature of the Korean patent application are incorporated as a part of this specification.
[3]
The present invention relates to a plasticizer composition and a resin composition comprising the same, and to a plasticizer composition having excellent safety and basic physical properties while being environmentally friendly, and a resin composition including the same.
background
[4]
In the polyvinyl chloride compound industry, where high heat resistance and low heat loss are the main required properties, a plasticizer should be used appropriately depending on the purpose. For example, in the case of a polyvinyl chloride compound for use in wires and cables, plasticizers, fillers, stabilizers, At least one selected from the group consisting of a lubricant and a flame retardant may be blended as an additive.
[5]
Currently, diisodecyl phthalate, a plasticizer that is typically used in the wire compound and automobile fabric industries, is an environmental hormone observation substance, so its use is being regulated. Accordingly, there is a demand for the development of an environmentally friendly plasticizer that can replace diisodecyl phthalate.
[6]
However, while having physical properties equal to or superior to that of diisodecyl phthalate, development of an environmentally friendly plasticizer is currently insufficient.
[7]
(Patent Document 1) KR10-0957134B
DETAILED DESCRIPTION OF THE INVENTION
technical challenge
[8]
It is an object of the present invention to provide a plasticizer composition that is environmentally friendly and has excellent safety.
[9]
In addition, it is an object of the present invention to provide a plasticizer composition excellent in basic physical properties such as plasticization efficiency, migration resistance, heat loss, tensile strength, residual tensile rate, elongation, elongation residual rate, absorption rate, and stress resistance.
means of solving the problem
[10]
In order to solve the above problems, the present invention provides a cyclohexane-1,2-diester-based material represented by the following formula (1); And it provides a plasticizer composition comprising a trimellitate-based material represented by the following formula 2:
[11]
[Formula 1]
[12]

[13]
[Formula 2]
[14]

[15]
In Formula 1 and Formula 2,
[16]
R 1 to R 5 are each independently an alkyl group having 8 to 10 carbon atoms.
[17]
[18]
In addition, the present invention provides a resin composition comprising 100 parts by weight of the resin and 5 to 150 parts by weight of the plasticizer composition.
Effects of the Invention
[19]
The plasticizer composition of the present invention is environmentally friendly, and has excellent safety and basic physical properties.
[20]
Accordingly, when the plasticizer composition of the present invention is included in the resin composition, it is environmentally friendly and has excellent safety, and is equivalent to or better than that of diisodecyl phthalate, plasticizing efficiency, migration resistance, heat loss, tensile strength, tensile residual rate, elongation, Stretch residual rate, absorption rate, stress resistance, etc. can be implemented.
Best mode for carrying out the invention
[21]
Hereinafter, the present invention will be described in more detail to help the understanding of the present invention.
[22]
The terms or words used in the present specification and claims are not to be construed as being limited to their ordinary or dictionary meanings, and the inventor may properly define the concept of the term in order to best describe his invention. Based on the principle that there is, it should be interpreted as meaning and concept consistent with the technical idea of ​​the present invention.
[23]
[24]
In the present invention, the alkyl group may be a linear or branched alkyl group, n-octyl group, isooctyl group, tert-octyl group, neo-octyl group, n-nonyl group, isononyl group, tert-nonyl group, neo-no nyl group, n-decyl group, isodecyl group, tert-decyl group, neo-decyl group, 2-propylpentyl group, 1-methyloctyl group, 2-methyloctyl group, 4-methyloctyl group, 5-methyloctyl group, It may be a 6-methyloctyl group, a 7-methyloctyl group, or the like, but is not limited thereto.
[25]
In the present invention, the alcohol may be a linear alcohol or a branched alcohol, n-octanol, isooctanol, tert-octanol, neo-octanol, n-nonanol, isononanol, tert-nonanol, neo- Nonanol, n-decyl alcohol, isodecyl alcohol, tert-decyl alcohol, neo-decyl alcohol, 2-ethylhexanol, 1-methylheptanol, 1-ethylheptanol, 2-ethylheptanol, 2,2- Dimethylheptanol, 2-propylheptanol, 2-propylpentanol, 1-methyloctanol, 2-methyloctanol, 4-methyloctanol, 5-methyloctanol, 6-methyloctanol, 7-methyloctane It may be all or the like, but is not limited thereto.
[26]
[27]
1. Plasticizer composition
[28]
A plasticizer composition according to an embodiment of the present invention comprises: 1) a cyclohexane-1,2-diester-based material represented by the following Chemical Formula 1; and 2) a trimellitate-based material represented by the following Chemical Formula 2:
[29]
[Formula 1]
[30]

[31]
[Formula 2]
[32]

[33]
In Formula 1 and Formula 2,
[34]
R 1 to R 5 are each independently an alkyl group having 8 to 10 carbon atoms.
[35]
[36]
In addition, the plasticizer composition according to an embodiment of the present invention may further include 3) an epoxidized oil.
[37]
[38]
In addition, the plasticizer composition according to an embodiment of the present invention may further include 4) a compound represented by the following formula (3).
[39]
[Formula 3]
[40]
R 6 -OC(=O)-XC(=O)-OR 7
[41]
In the above formula (3)
[42]
X is a linear or branched alkylene group having 2 to 8 carbon atoms, or a linear or branched alkenylene group having 2 to 8 carbon atoms including at least one double bond,
[43]
R 6 and R 7 are each independently an alkyl group having 3 to 5 carbon atoms.
[44]
[45]
Hereinafter, components according to an embodiment of the present invention will be described in detail.
[46]
[47]
1) Cyclohexane-1,2-diester-based material
[48]
The cyclohexane-1,2-diester-based material is represented by Chemical Formula 1, and may give the plasticizer composition an environmentally friendly property excluding a phthalate component. In addition, properties such as plasticizing efficiency and elongation of the plasticizer composition may be further improved.
[49]
[50]
When the bonding position of the diester group in cyclohexane is not the 1 or 2 position, there may be a problem in that compression transferability and stress transferability are poor.
[51]
[52]
In the cyclohexane-1,2-diester-based material, two R 1 and R 2 bonded to the diester group are each independently an alkyl group having 8 to 10 carbon atoms, and when an alkyl group having less than 8 carbon atoms is bonded, heat loss However, mechanical properties such as migration loss and tensile strength are poor, and the absorption rate or gelling is too fast, which may affect processability. can give In order to optimize this effect, an alkyl group having 8 to 10 carbon atoms or an alkyl group having 8 to 9 carbon atoms may be preferably selected.
[53]
[54]
wherein R 1 and R 2 are the same as or different from each other, and each independently a group consisting of n-octyl group, isooctyl group, 2-ethylhexyl group, n-nonyl group, isononyl group, 2-propylheptyl group, isodecyl group It may be one selected from the group consisting of a 2-ethylhexyl group, an isononyl group, a 2-propaneheptyl group, and an isodecyl group.
[55]
When the cyclohexane-1,2-diester-based material represented by the above formula (1) is directly prepared, cyclohexane-1,2-dicarboxylic acid or a derivative thereof and alcohol are directly esterified or transesterified. can
[56]
The derivative of cyclohexane-1,2-dicarboxylic acid may be at least one selected from the group consisting of an anhydride of cyclohexane-1,2-dicarboxylic acid and/or an alkyl ester of cyclohexane-1,2-dicarboxylic acid. have. In this case, the alkyl ester may be an alkyl ester having 1 to 12 carbon atoms.
[57]
The alkyl group of the finally prepared cyclohexane-1,2-dicarboxyl diester preferably has 8 to 10 carbon atoms or 8 to 9 carbon atoms.
[58]
[59]
When the cyclohexane-1,2-diester-based material represented by Formula 1 is prepared by the direct esterification reaction, the alcohol is 2 with respect to 1 mole of the cyclohexane-1,2-dicarboxylic acid or its derivative to 10 moles, 2 to 8 moles, 2 to 6 moles, or 2 to 5 moles may be used, and 2 to 5 moles of these may be used.
[60]
The direct esterification reaction may be carried out in the presence of a catalyst, and the catalyst may be at least one selected from the group consisting of inorganic acids, organic acids, and Lewis acids, among which at least one selected from the group consisting of organic acids and Lewis acids. can
[61]
The inorganic acid may be at least one selected from the group consisting of sulfuric acid, hydrochloric acid and phosphoric acid.
[62]
The organic acid may be at least one selected from the group consisting of p-toluenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid and alkyl sulfuric acid.
[63]
The Lewis acid is an aluminum derivative (aluminum oxide, aluminum hydroxide), a tin derivative (C 3 to C 12 fatty acid tin, tin oxide, tin hydroxide), a titanium derivative (C 3 to C 8 tetraalkyl titanate, titanium oxide, hydroxide Titanium), lead derivatives (lead oxide, lead hydroxide), and zinc derivatives (zinc oxide, zinc hydroxide) may be at least one selected from the group consisting of.
[64]
[65]
When the catalyst is a homogeneous catalyst, 0.01 to 5 parts by weight or 0.01 to 3 parts by weight may be used in an amount of 0.01 to 5 parts by weight or 0.01 to 3 parts by weight, based on 100 parts by weight of the total of the cyclohexane-1,2-dicarboxylic acid or derivative thereof and the alcohol. It is preferably used in an amount of to 3 parts by weight.
[66]
When the catalyst is a heterogeneous catalyst, it may be used in an amount of 0.5 to 200 parts by weight or 0.5 to 100 parts by weight, of which, 0.5 to 200 parts by weight or 0.5 to 100 parts by weight, based on 100 parts by weight of the total of cyclohexane-1,2-dicarboxylic acid or its derivative and alcohol. It is preferably used in 200 parts by weight.
[67]
The direct esterification reaction may be carried out at 100 to 280 °C, 130 to 250 °C, or 150 to 230 °C, of ​​which it is preferably carried out at 150 to 230 °C.
[68]
The direct esterification reaction may be performed for 3 to 30 hours or 3 to 25 hours, of which 3 to 25 hours is preferable.
[69]
[70]
On the other hand, when the cyclohexane-1,2-diester-based material is prepared by the transesterification reaction, it may be prepared by the transesterification reaction of the cyclohexane-1,2-dicarboxylic acid derivative and alcohol.
[71]
The derivative of cyclohexane-1,2-dicarboxylic acid may be an alkyl ester of cyclohexane-1,2-dicarboxylic acid, and preferably cyclohexane-1,2-dicarboxylic acid to facilitate separation of the reaction product. methyl esters of
[72]
Based on 1 mole of the derivative of cyclohexane-1,2-dicarboxylic acid, 2 to 10 moles, 2 to 8 moles, 2 to 6 moles, or 2 to 5 moles of the alcohol may be used, of which 2 to 5 moles It is preferred to use
[73]
The transesterification reaction may be performed in the presence of a catalyst, and in this case, the reaction time may be shortened.
[74]
The catalyst may be at least one selected from the group consisting of a Lewis acid and an alkali metal.
[75]
The Lewis acid is as described in the description of the direct esterification reaction, aluminum derivatives (aluminum oxide, aluminum hydroxide), tin derivatives (C 3 to C 12 fatty acid tin, tin oxide, tin hydroxide), titanium derivatives (C 3 to C 8 may be at least one selected from the group consisting of tetraalkyl titanate, titanium oxide, titanium hydroxide), lead derivatives (lead oxide, lead hydroxide), and zinc derivatives (zinc oxide, zinc hydroxide).
[76]
In addition, the alkali metal may be at least one selected from the group consisting of sodium alkoxide, potassium alkoxide, sodium hydroxide and potassium hydroxide, and a single or mixed catalyst of two or more of the metal catalyst may be used.
[77]
The catalyst may be used in an amount of 0.01 to 5 parts by weight or 0.01 to 3 parts by weight, of which 0.01 to 3 parts by weight, based on 100 parts by weight of the total of the cyclohexane-1,2-dicarboxylic acid derivative and alcohol. it is preferable
[78]
The transesterification reaction may be carried out at 120 to 250 °C, 135 to 230 °C, or 140 to 220 °C, of ​​which 140 to 220 °C is preferable.
[79]
The transesterification reaction may be performed for 0.5 to 10 hours or 0.5 to 8 hours, of which 0.5 to 8 hours is preferable.
[80]
[81]
In the direct esterification reaction or transesterification reaction, at least one selected from the group consisting of benzene, toluene, xylene and cyclohexane is added to promote the outflow of lower alcohols such as water or methanol produced by the reaction. It can be added, and commercially available nitrogen, etc. can be used as entrainment for the same purpose.
[82]
The cyclohexane-1,2-diester-based material represented by Formula 1 prepared by the direct esterification reaction or the transesterification reaction may be purified by performing a separate post-treatment. The post-treatment may be at least one selected from the group consisting of catalyst inactivation treatment (neutralization treatment, base treatment), water washing treatment, distillation (reduced pressure or dehydration treatment), and adsorption purification treatment.
[83]
[84]
Unlike the above manufacturing method, a manufacturing method including a step of converting a dialkyl phthalate-based material into a cyclohexane-1,2-diester-based material by a hydrogenation reaction in the presence of a metal catalyst may be applied.
[85]
The hydrogenation step is a reaction for removing the aromaticity of the benzene ring of phthalate by adding hydrogen in the presence of a metal catalyst, and may be a kind of reduction reaction.
[86]
The hydrogenation reaction synthesizes a cyclohexane-1,2-diester-based material by reacting the phthalate-based material with hydrogen under a metal catalyst, and the reaction condition is a benzene ring without affecting the carbonyl group substituted in benzene. It may include all conventional reaction conditions capable of hydrogenating only .
[87]
The hydrogenation reaction may be carried out further including an organic solvent such as ethanol, but is not limited thereto. As the metal catalyst, a Rh/C catalyst, a Pt catalyst, a Pd catalyst, etc., which are generally used for hydrogenating the benzene ring, may be used, but is not limited thereto as long as the hydrogenation reaction as described above is possible.
[88]
[89]
2) trimellitate-based substances
[90]
The trimellitate-based material is represented by Chemical Formula 2, and may impart environmental-friendly properties and excellent safety to the plasticizer composition. In addition, properties such as migration resistance, heat loss, tensile residual ratio, elongation residual ratio, and oil resistance of the plasticizer composition may be further improved.
[91]
[92]
The R 3 to R 5 are the same as or different from each other, and each independently may be an alkyl group having 8 to 10 carbon atoms or an alkyl group having 8 to 9 carbon atoms, of which it is preferably an alkyl group having 8 to 9 carbon atoms.
[93]
[94]
When the above-mentioned conditions are satisfied, migration resistance, heat loss, elongation residual ratio, oil resistance, and stress migration resistance may be further improved.
[95]
[96]
wherein R 3 to R 5 are the same as or different from each other, and each independently a group consisting of n-octyl group, isooctyl group, 2-ethylhexyl group, n-nonyl group, isononyl group, 2-propylheptyl group and isodecyl group It may be one selected from, among which, 2-ethylhexyl group or isononyl group is preferable. On the other hand, when the alkyl group is linear, cold resistance may be excellent, and when the alkyl group is branched, economic efficiency may be improved.
[97]
[98]
On the other hand, the weight ratio of the cyclohexane-1,2-diester-based material represented by Formula 1 and the trimellitate-based material represented by Formula 2 is 90:10 to 10:90, 80:20 to 20:80, or 70 :30 to 30:70 may be, among which 70:30 to 30:70 is preferable.
[99]
When the above content is satisfied, it is possible to secure the level of plasticization efficiency, migration resistance, heating loss, tensile residual ratio, elongation residual ratio and oil resistance equivalent to or higher than that of diisodecyl phthalate.
[100]
[101]
When the trimellitate-based material represented by Chemical Formula 2 is directly prepared, it may be prepared by direct esterification or transesterification reaction between trimellitic acid or a derivative thereof and alcohol.
[102]
The derivative of trimellitic acid may be at least one selected from the group consisting of an anhydride of trimellitic acid and an alkyl ester of trimellitic acid, wherein the alkyl ester may be an alkyl ester having 1 to 12 carbon atoms.
[103]
The finally prepared alkyl group of trimellitate has 8 to 10 carbon atoms, and preferably has 8 to 9 carbon atoms.
[104]
[105]
When the trimellitate-based material represented by Chemical Formula 2 is prepared by the direct esterification reaction, the alcohol content is 3 to 15 moles, 3 to 12 moles, 3 to 10 moles based on 1 mole of the trimellitic acid or its derivative. It may be used in moles, 3 to 8 moles, or 3 to 6 moles, and it is preferable to use 3 to 6 moles of them.
[106]
In addition, the description of the direct esterification reaction is the same as described in the method for preparing the cyclohexane-1,2-diester-based material.
[107]
[108]
Meanwhile, when the trimellitate-based material represented by Formula 2 is prepared by the transesterification reaction, it may be prepared by transesterification of the trimellitic acid derivative and alcohol. Here, the derivative of trimellitic acid may be an alkyl ester of trimellitic acid.
[109]
Based on 1 mol of the trimellitic acid derivative, 3 to 15 mol, 3 to 12 mol, or 3 to 10 mol of the alcohol may be used, and 3 to 10 mol of the alcohol may be used.
[110]
In addition, the description of the transesterification reaction is the same as described in the method for preparing the cyclohexane-1,2-diester-based material.
[111]
[112]
3) epoxidized oil
[113]
The epoxidized oil can further improve the thermal stability, heat loss, oil resistance and absorption rate of the plasticizer composition. In addition, the epoxy oil can improve mechanical properties such as tensile strength and elongation of the plasticizer composition, and further improvement of heat resistance can be expected.
[114]
[115]
The epoxidized oil is epoxidized soybean oil, epoxidized castor oil, epoxidized linseed oil, epoxidized palm oil, epoxidized stearate ), epoxidized oleate, epoxidized tall oil, and epoxidized linoleate may be at least one selected from the group consisting of, among these, epoxidized soybean oil and epoxidized linoleate oil. At least one selected from the group consisting of is preferable.
[116]
[117]
The epoxidized oil is 1 to 150 parts by weight, 5 to 125 parts by weight, based on 100 parts by weight of the sum of the cyclohexane-1,2-diester-based material represented by Formula 1 and the trimellitate-based material represented by Formula 2 It may be included in parts by weight, 10 to 100 parts by weight, 10 to 80 parts by weight, or 20 to 70 parts by weight, of which it is preferably included in 20 to 70 parts by weight. In addition, when the epoxidized oil is further added to the two materials, there may be fewer restrictions in implementing the effect compared to the composition using the two materials, and thus, when the epoxidized oil is added, the cyclohexane-1,2- It may be easier to control the content ratio of the diester-based material and the trimellitate-based material.
[118]
When the above content is satisfied, the migration resistance and absorption rate of the plasticizer composition are remarkably improved, and basic physical properties such as tensile strength and elongation can be maintained at the same level as that of a conventional plasticizer or plasticizer composition.
[119]
The epoxidized oil may be prepared directly or a commercially available material may be used.
[120]
[121]
4) a compound represented by Formula 3
[122]
The compound represented by the formula (3) improves the processability of the polymer included in the molding material due to a synergistic effect with the cyclohexane-1,2-diester-based material represented by the formula (1), that is, lowers the processing temperature or transfer characteristics can be improved In addition, the compound represented by Formula 3 has excellent compatibility with the polymer to be plasticized, has high durability, and is environmentally friendly.
[123]
[124]
R 6 and R 7 are each independently an alkyl group having 3 to 5 carbon atoms, and the alkyl group may be a linear or branched alkyl group.
[125]
R 6 and R 7 are each independently n-propyl, isopropyl, n-butyl, isobutyl, sec.-butyl, tert.-butyl, n-pentyl, 2-pentyl, 2-methylbutyl, 3-methyl butyl, 1,2-dimethylpropyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl or 1-ethyl-propyl, of which n-butyl, isobutyl, n-pentyl, 2-methylbutyl or 3-methylbutyl is preferable, and n-butyl is more preferable.
[126]
[127]
X is a linear or branched alkylene group having 2 to 8 carbon atoms, or a linear or branched alkenylene group having 2 to 8 carbon atoms including at least one double bond.
[128]
When X is a linear or branched alkylene group having 2 to 8 carbon atoms, linear alkylene having 2 to 5 carbon atoms is preferable, and linear alkylene having 3 to 4 carbon atoms is more preferable.
[129]
When X is a linear or branched alkenylene group having 2 to 8 carbon atoms including at least one double bond, a linear or branched alkenylene group having 2 to 6 carbon atoms is preferable, and an alkenylene group having 2 to 4 carbon atoms is preferable. more preferably.
[130]
[131]
The compound represented by Formula 3 is di(n-butyl)glutarate, diisobutyl glutarate, di(n-pentyl)glutarate, di(2-methylbutyl)glutarate, di(3- methylbutyl)glutarate, di(n-butyl)adipate, di(n-butyl)adipate, diisobutyl adipate, di(n-pentyl)adipate, di(2-methylbutyl)adipate, It may be selected from the group consisting of di(3-methylbutyl)adipate. Among these, di(n-butyl) adipate is preferable.
[132]
[133]
The weight ratio of the cyclohexane-1,2-diester-based material represented by Formula 1 and the compound represented by Formula 3 may be 1:1 to 20:1, preferably 1.5:1 to 10:1, 2:1 to 7:1 are more preferable.
[134]
When the above content is satisfied, the transition characteristics and stress resistance included in the molding material are improved due to the synergistic effect of the cyclohexane-1,2-diester-based material represented by Formula 1 and the compound represented by Formula 3 can do.
[135]
[136]
The compound represented by Formula 3 may be prepared directly or a commercially available material may be used, for example, Cetiol B (trade name, manufacturer: BASF SE) may be used.
[137]
[138]
2. Resin composition
[139]
The resin composition according to another embodiment of the present invention includes 100 parts by weight of the resin, and 5 to 150 parts by weight of the plasticizer composition according to an embodiment of the present invention.
[140]
[141]
The resin may include at least one selected from the group consisting of ethylene-vinyl acetate copolymer, polyethylene, polypropylene, polyketone, polyvinyl chloride, polystyrene, polyurethane, and thermoplastic elastomer, of which polyvinyl chloride is It is preferable to include
[142]
[143]
The resin composition is based on 100 parts by weight of the resin, 5 to 150 parts by weight of the plasticizer composition, 10 to 130 parts by weight, 10 to 100 parts by weight, 20 to 100 parts by weight, 20 to 80 parts by weight, 20 to 70 parts by weight. It may be included in parts or 20 to 60 parts by weight, of which it is preferable to include 20 to 70 parts by weight or 20 to 60 parts by weight.
[144]
When the above-described content is satisfied, it is possible to provide a resin composition effective for both compound processing products, calendering processing products, and extrusion and injection processing.
[145]
The resin composition may be used for manufacturing electric wires, flooring materials, automobile interior materials, films, sheets, or tubes.
Modes for carrying out the invention
[146]
Hereinafter, embodiments of the present invention will be described in detail so that those of ordinary skill in the art can easily carry out the present invention. However, the present invention may be embodied in several different forms and is not limited to the embodiments described herein.
[147]
[148]

[149]
Preparation Example 1
[150]
516.5 g of cyclohexane-1,2-dicarboxylic acid, 1,296 g of isononanol, and 1.55 g of tetraisopropyl titanate as a catalyst were placed in a 4-neck 3 liter reactor equipped with a condenser, decanter, reflux pump, temperature controller, and stirrer. The esterification reaction was carried out directly for about 6 hours while the reaction temperature was set to 230° C. and nitrogen gas was continuously added, and the reaction was completed when the acid value reached 0.1.
[151]
After completion of the reaction, in order to remove unreacted raw materials, distillation extraction was performed under reduced pressure. After distillation extraction, 1,240 g (yield: 97%) of diisononyl cyclohexane-1,2-dicarboxylate was prepared through a neutralization process, a dehydration process, and a filtration process.
[152]
[153]

[154]
Preparation 2
[155]
Tri(2-ethylhexyl) trimellitate (TEHTM) 1,060 g (yield: 97%) in the same manner as in Preparation Example 1, except that 384 g of trimellitic anhydride and 1,170 g of 2-ethylhexanol were added to the reactor. ) was obtained.
[156]
[157]
Preparation 3
[158]
1,140 g (yield: 97%) of triisononyl trimellitate (TINTM) was obtained in the same manner as in Preparation Example 1, except that 384 g of trimellitic anhydride and 1,296 g of isononanol were added to the reactor.
[159]
[160]
Cyclohexane-1,2-diester-based material prepared in Preparation Example 1, tris (2-ethylhexyl) trimellitate prepared in Preparation Example 2, triisononyl trimellitate prepared in Preparation Example 3, epoxidation Oil, diisodecyl phthalate (DIDP) and at least one selected from the group consisting of alkyl sulfonic phenyl ester (ASPE, CAS No. 91082-17-6) was mixed to prepare plasticizer compositions of Examples and Comparative Examples. , which are summarized in Table 1 below. The evaluation of the physical properties of the plasticizer composition was performed according to the following experimental items. Commercialized products were used for materials other than those prepared in Preparation Example.
[161]
[162]
[Table 1]
division Cyclohexane-1,2-diester-based material trimellitate substances epoxidized oil DIDP ASPE
Kinds content 1) Kinds content Kinds content
Example 1 Preparation Example 1 30 Preparation 2 70 - - - -
Example 2 Preparation Example 1 50 Preparation 2 50 - - - -
Example 3 Preparation Example 1 70 Preparation 2 30 - - - -
Example 4 Preparation Example 1 40 Preparation 3 60 - - - -
Example 5 Preparation Example 1 60 Preparation 3 40 - - - -
Example 6 Preparation Example 1 30 Preparation 2 30 ESO 2) 40 - -
Example 7 Preparation Example 1 30 Preparation 2 40 ESO 30 - -
Example 8 Preparation Example 1 30 Preparation 2 50 ESO 20 - -
Example 9 Preparation Example 1 50 Preparation 3 30 ESO 20 - -
Example 10 Preparation Example 1 40 Preparation 3 50 ESO 10 - -
Example 11 Preparation Example 1 40 Preparation 3 10 ESO 50 - -
Comparative Example 1 - - - - - - 100 -
Comparative Example 2 Preparation Example 1 100 - - - - - -
Comparative Example 3 Preparation Example 1 50 - - ESO 50 - -
Comparative Example 4 Preparation Example 1 50 - - - - - 50
Comparative Example 5 - Preparation 2 100 - - - -
Comparative Example 6 - - Preparation 2 30 ESO 70 - -
Comparative Example 7 - - Preparation 3 90 ESO 10 - -
[163]
1) All of the contents in Table 1 above are by weight. 2) ESO: epoxidized soybean oil (CAS No: 8013-07-8)
[164]
[165]

[166]
Hardness (shore A) measurement
[167]
According to ASTM D2240, the hardness of the specimen having a thickness of 3 mm was measured for 10 seconds.
[168]
[169]
Measure migration loss (%)
[170]
In accordance with KSM-3156, after attaching PS plates to both surfaces of a specimen having a thickness of 1 mm, a load of 2 kgf/cm 2 was applied. The specimens were left in a hot air circulation oven (80° C.) for 72 hours, then taken out and cooled at room temperature. Thereafter, the PS plates attached to both sides of the specimen were removed, and the weight of the specimen was measured before and after being left in the oven, and substituted into Equation 1 below to calculate the transfer loss value.
[171]

[172]
Transition loss (%) = [(initial weight of specimen before test) - (weight of specimen after test)] / (initial weight of specimen before test) × 100
[173]
[174]
stress assessment
[175]
After a specimen having a thickness of 2 mm was left in a bent state for 168 hours, the degree of migration (the degree of seepage) was observed, and the result was written as a numerical value.
[176]
[177]
Heat loss measurement (%)
[178]
After exposing a specimen having a thickness of 1 mm at 113° C. for 168 hours, the weight of the specimen was measured, and the weight loss was calculated by substituting it in Equation 2 below.
[179]

[180]
Loss on heating (%) = [(initial weight of specimen) - (weight of specimen after work)]/ (initial weight of specimen before leaving in oven) × 100
[181]
[182]
Tensile strength measurement (kgf/㎠)
[183]
According to ASTM D638, a specimen having a thickness of 1 mm was pulled using a UTM (trade name: 4466, manufacturer: instron) at a cross head speed of 200 mm/min, and then the time at which the specimen was cut was measured.
[184]
[185]
Elongation measurement (%)
[186]
According to ASTM D638, a specimen having a thickness of 1 mm was pulled using a UTM (trade name: 4466, manufacturer: instron) at a cross head speed of 200 mm/min, and then the time at which the specimen was cut was measured. Then, by substituting in Equation 3 below, the elongation was calculated.
[187]

[188]
Elongation (%): [(length at the time the specimen is cut)/(initial length)]×100
[189]
[190]
Tensile and Elongation Residual Measurement
[191]
The measurement of tensile and elongation residual is to measure the tensile strength and elongation remaining in the specimen after applying heat at 100° C. for 168 hours, and the measurement method is the same as that of the tensile strength and elongation measurement method.
[192]
[193]
Experimental example: evaluation of physical properties
[194]
Specimens were prepared using the plasticizer compositions of Examples and Comparative Examples described in Table 1, and the test items were evaluated for the specimens, and the results are shown in Tables 2 and 3 below.
[195]
The specimen preparation is based on ASTM D638, 100 parts by weight of polyvinyl chloride (trade name: LS100, manufacturer: LG Chemical), 50 parts by weight of the plasticizer composition prepared in the Examples and Comparative Examples, a filler (trade name: Omyacrab 1T ® , Manufacturer: OMYA) 40 parts by weight, stabilizer (trade name: RUP-144, manufacturer: ADEKA) 5 parts by weight, and lubricant (trade name: ST-A, manufacturer: Isu Chemical) 0.3 parts by weight, and at 98 ° C. at 700 rpm Mix by stirring at a high speed, roll mill at 160°C for 4 minutes, and use a press to work at 180°C for 3 minutes (low pressure) and 2.5 minutes (high pressure) to 1 mm thick specimens and 3 mm thick specimens were produced respectively.
[196]
[197]
[Table 2]
division Hardness (ShoreA) Performance loss (%) stress transitivity Heat loss (%)
Example 1 93.5 0.72 1.0 3.62
Example 2 93.0 0.81 1.5 3.80
Example 3 92.5 0.83 1.5 4.58
Example 4 93.7 0.90 1.0 3.56
Example 5 93.0 0.85 1.5 4.32
Example 6 92.6 0.62 0.5 2.28
Example 7 92.8 0.60 0 2.35
Example 8 93.1 0.43 0.5 2.30
Example 9 92.3 0.88 0.5 3.30
Example 10 92.8 0.90 0.5 3.10
Example 11 92.0 0.35 0 2.67
Comparative Example 1 93.2 1.17 1.5 4.66
Comparative Example 2 91.2 2.34 2.0 8.65
Comparative Example 3 92.5 1.35 2.0 5.68
Comparative Example 4 89.3 4.62 3.0 10.27
Comparative Example 5 96.3 0.65 1.0 3.42
Comparative Example 6 94.1 0.48 1.0 3.66
Comparative Example 7 96.7 0.69 2.0 2.03
[198]
[Table 3]
division Tensile strength (kgf/㎠) Tensile residual rate (%) Elongation (%) Kidney Residual Rate (%)
Example 1 203.3 98.3 280.3 95.3
Example 2 196.0 102.0 286.1 94.3
Example 3 189.0 103.4 294.3 93.0
Example 4 199.6 100.2 276.5 97.8
Example 5 193.2 108.3 290.1 96.4
Example 6 204.6 98.9 288.3 102.3
Example 7 208.9 97.5 291.0 100.2
Example 8 215.3 98.0 292.3 98.9
Example 9 203.4 100.3 298.4 98.0
Example 10 196.8 102.4 288.7 98.5
Example 11 196.0 97.7 286.4 100.5
Comparative Example 1 188.7 96.6 270.1 93.2
Comparative Example 2 158.3 92.0 303.0 86.0
Comparative Example 3 176.2 96.4 281.5 89.6
Comparative Example 4 150.1 110.3 300.2 73.2
Comparative Example 5 205.1 94.7 265.4 91.6
Comparative Example 6 190.0 94.0 267.2 92.5
Comparative Example 7 192.3 95.7 278.5 97.6
[199]
Referring to Tables 2 and 3, Examples 1 to 5 containing only a cyclohexane-1,2-diester-based material and a trimellitate-based material and a cyclohexane-1,2-diester-based material, trimelli Examples 6 to 11 containing a tate-based material and an epoxidized oil implement the hardness (plasticization efficiency) equivalent to that of Comparative Example 1, which is DIDP, so that there is no loss in the plasticization efficiency, but the transition loss, It was confirmed that stress transferability, loss on heating, tensile strength, tensile residual ratio, elongation and residual elongation were remarkably excellent. In addition, Comparative Example 2 containing only cyclohexane-1,2-diester-based material was compared to Examples It can be seen that all physical properties are significantly reduced, and Comparative Example 3 including a cyclohexane-1,2-diester-based material and epoxidized oil has hardness, tensile residual ratio and elongation at the same level as those of Examples, but other It was confirmed that all the physical properties were significantly lowered.
[200]
In addition, Comparative Example 4 containing a cyclohexane-1,2-diester-based material and an alkyl sulfonic phenyl ester showed a higher tensile residual ratio than in Examples, but this reduced the plasticizer remaining in the specimen due to high heating loss. This was only due to the fact that the specimen hardened and lost its soft properties (aging).
[201]
Comparative Example 5 containing only the trimellitate-based material had the same level of tensile strength, migration loss, stress migration, and heat loss compared to Examples, but had significantly poor hardness (plasticization efficiency) and reduced tensile residual ratio. It can be confirmed that the characteristic disappears in a high-temperature environment, and despite the low elongation, the elongation residual ratio is significantly lowered, and it is confirmed that the soft property is poor due to a further decrease due to the high-temperature environment.
[202]
Comparative Example 6 containing trimellitate-based material and epoxidized oil but containing an excessive amount of epoxidized oil also had the same hardness, transition loss, stress transferability and heat loss compared to Examples, but tensile strength, tensile residual ratio, It can be seen that the elongation and the residual elongation are significantly lowered. It can be seen that the basic physical properties are not good, and at the same time, it can be confirmed that even these poor physical properties cannot be maintained in a high temperature environment.
[203]
In addition, in Comparative Example 7 containing a trimellitate-based material and an epoxidized oil, but containing an excess of a trimellitate-based material, the transition loss, heat loss, elongation, and residual elongation were at the same level or superior to those of Examples, but the hardness , stress transferability, tensile strength, and tensile residual ratio were confirmed to be lowered.
[204]
[205]
Through this, when the plasticizer compositions of the examples are applied, the plasticizing efficiency is basically equivalent to or higher than that of the existing products and can be an excellent substitute, and the basic tensile strength and elongation are excellent, but the tensile residual ratio and elongation residual ratio are high It can be seen that this excellent physical property is maintained in a high-temperature environment, and the loss of the plasticizer can be minimized due to the excellent transfer characteristics (transition loss and stress transferability) and heat loss characteristics.
Claims
[Claim 1]
a cyclohexane-1,2-diester-based material represented by the following formula (1); And a plasticizer composition comprising a trimellitate-based material represented by the following Chemical Formula 2: [Formula 1] [Formula 2] In Chemical Formulas 1 and 2, R 1 to R 5 are each independently an alkyl group having 8 to 10 carbon atoms. .
[Claim 2]
The plasticizer composition according to claim 1, wherein the weight ratio of the cyclohexane-1,2-diester-based material represented by Formula 1 and the trimellitate-based material represented by Formula 2 is 90:10 to 10:90.
[Claim 3]
The plasticizer composition according to claim 1, wherein the weight ratio of the cyclohexane-1,2-diester-based material represented by Formula 1 and the trimellitate-based material represented by Formula 2 is 80:20 to 20:80.
[Claim 4]
The plasticizer composition of claim 1, wherein R 1 to R 5 are each independently an alkyl group having 8 to 9 carbon atoms.
[Claim 5]
The method according to claim 1, wherein R 1 To R 5 are each independently a group consisting of n-octyl group, isooctyl group, 2-ethylhexyl group, n-nonyl group, isononyl group, 2-propylheptyl group and isodecyl group A plasticizer composition which is one selected from
[Claim 6]
The plasticizer composition of claim 1, wherein the plasticizer composition further comprises an epoxidized oil.
[Claim 7]
The method according to claim 6, wherein the epoxidized oil is epoxidized soybean oil, epoxidized castor oil, epoxidized linseed oil, epoxidized palm oil, epoxidized A plasticizer composition that is at least one selected from the group consisting of stearate (epoxidized stearate), epoxidized oleate (epoxidized oleate), epoxidized tall oil (epoxidized tall oil) and epoxidized linoleate (epoxidized linoleate).
[Claim 8]
The method according to claim 6, 1 to 150 parts by weight of the epoxidized oil based on 100 parts by weight of the sum of the cyclohexane-1,2-diester-based material represented by Formula 1 and the trimellitate-based material represented by Formula 2 A plasticizer composition comprising as a part.
[Claim 9]
The method according to claim 1, wherein the plasticizer composition is a plasticizer composition further comprising a compound represented by the following formula 3: [Formula 3] R 6 -OC (=O) -XC (= O) -OR 7 In Formula 3 , X is a linear or branched alkylene group having 2 to 8 carbon atoms or a linear or branched alkenylene group having 2 to 8 carbon atoms including at least one double bond, and R 6 and R 7 are each independently C 3 to 5 alkyl groups.
[Claim 10]
The plasticizer composition of claim 9, wherein the weight ratio of the cyclohexane-1,2-diester-based material represented by Formula 1 to the compound represented by Formula 3 is 1:1 to 20:1.
[Claim 11]
100 parts by weight of resin; and 5 to 150 parts by weight of the plasticizer composition according to claim 1 .
[Claim 12]
The resin composition of claim 11, wherein the resin comprises at least one selected from the group consisting of ethylene-vinyl acetate copolymer, polyethylene, polypropylene, polyketone, polyvinyl chloride, polystyrene, polyurethane, and thermoplastic elastomer. .