The present invention claims the benefit of priority based on Korean Patent Application No. 10-2018-0067654, filed on June 12, 2018 and Korean Patent Application No. 10-2019-0063107, filed on May 29, 2019, All content disclosed in the literature is incorporated herein by reference.
[3]
[Technical field]
[4]
The present invention relates to a plasticizer composition and a resin composition comprising the same, and to a plasticizer composition having excellent stability and basic physical properties while being environmentally friendly, and a resin composition including the same.
background
[5]
Plasticizers typically react with alcohols with polycarboxylic acids such as phthalic acid and adipic acid to form the corresponding esters. In addition, in consideration of domestic and international regulations of phthalate-based plasticizers harmful to the human body, research on plasticizer compositions that can replace phthalate-based plasticizers such as terephthalate, adipate, and other polymer-based plasticizers is continuing.
[6]
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.
[7]
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, development of an environmentally friendly plasticizer that can replace diisodecyl phthalate is required, but development of an environmentally friendly plasticizer while having physical properties equal to or superior to that of diisodecyl phthalate is insufficient.
[8]
On the other hand, even when manufacturing polyvinyl chloride to apply it to the calendaring sheet industry, it is necessary to use an appropriate plasticizer in consideration of discoloration, transferability, processability, and the like. In these various areas of use, plasticizers, fillers, stabilizers, etc. are mixed with PVC resin according to tensile strength, elongation, light resistance, transferability, or processability, which are characteristics required by industry.
[9]
For example, among the plasticizer compositions applicable to polyvinyl chloride, when di(2-ethylhexyl) terephthalate, which is relatively inexpensive, is applied, the viscosity is high, the absorption rate of the plasticizer is relatively slow, and the transferability is not good. Accordingly, by developing a superior product or a product of a new composition containing di(2-ethylhexyl) terephthalate while replacing the di(2-ethylhexyl) terephthalate, it can be optimally applied as a plasticizer for vinyl chloride-based resins. There is a continuing need for research on possible technologies.
DETAILED DESCRIPTION OF THE INVENTION
technical challenge
[10]
It is an object of the present invention to provide a plasticizer composition that is environmentally friendly and has excellent stability.
[11]
In addition, an object of the present invention is to provide a plasticizer composition excellent in basic physical properties such as plasticization efficiency, migration resistance, hardness, loss on heating, tensile strength, residual tensile rate, elongation, elongation residual rate, absorption rate, stress resistance and cold resistance. .
means of solving the problem
[12]
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 citrate-based material represented by the following formula 2:
[13]
[Formula 1]
[14]

[15]
[Formula 2]
[16]

[17]
In Formula 1 and Formula 2,
[18]
R 1 and R 2 are each independently an alkyl group having 8 to 10 carbon atoms,
[19]
R 3 to R 5 are each independently an alkyl group having 5 to 10 carbon atoms.
[20]
[21]
In addition, the present invention is 100 parts by weight of the resin; and 5 to 150 parts by weight of the plasticizer composition.
[22]
Effects of the Invention
[23]
The plasticizer composition of the present invention is environmentally friendly, and has excellent stability and basic physical properties.
[24]
Accordingly, when the plasticizer composition of the present invention is included in the resin composition, it is environmentally friendly and better than existing products, plasticizing efficiency, migration resistance, hardness, loss on heating, tensile strength, residual tensile rate, elongation, elongation residual rate, absorption rate , stress resistance and cold resistance can be implemented.
[25]
Best mode for carrying out the invention
[26]
Hereinafter, the present invention will be described in more detail to help the understanding of the present invention.
[27]
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.
[28]
[29]
Definition of Terms
[30]
The term “composition” as used herein includes reaction products and decomposition products formed from materials of the composition, as well as mixtures of materials comprising the composition.
[31]
The term "polymer," as used herein, refers to a polymer compound prepared by polymerizing monomers, whether of the same or a different type. The generic term polymer thus encompasses the term homopolymer, which is commonly used to refer to polymers prepared from only one monomer, and the term interpolymer, as defined below.
[32]
The term “interpolymer” as used herein refers to a polymer prepared by the polymerization of at least two different monomers. As such, the generic term interpolymer includes copolymers, which are commonly used to refer to polymers prepared from two different monomers, and polymers prepared from two or more different monomers.
[33]
As used herein, the prefix “iso-” refers to an alkyl group in which a methyl group or an ethyl group is branched to the main chain of the alkyl group, and in the present specification, unless there is an alkyl group otherwise referred to herein, it is bound to a terminal. Including, it can be used as a generic term for an alkyl group in which a methyl group or an ethyl group is bonded to the main chain as a branched chain.
[34]
In particular, the term “isononyl group” as used herein may mean an alkyl group having a total of 9 carbon atoms in which at least one branch is substituted with one or two methyl groups, one ethyl group, and one propyl group in the main chain. and, for example, 2-methyloctyl group, 3-methyloctyl group, 4-methyloctyl group, 5-methyloctyl group, 6-methyloctyl group, 3-ethylheptyl group, 2-ethylheptyl group, 2,5- dimethylheptyl group, 2,3-dimethylheptyl group, 4,5-dimethylheptyl group, 3-ethyl-4-methylhexyl group, 2-ethyl-4-methylhexyl group, or 2-propylhexyl group Isononyl alcohol (CAS No.: 68526-84-1, 27458-94-2) used commercially may mean a composition of isomers having a branching degree of 1.2 to 1.9, and the commercial In the case of alcohol, some n-nonyl groups may also be included.
[35]
As used herein, the term "straight vinyl chloride polymer" is one of the types of vinyl chloride polymer, and may mean polymerized through suspension polymerization or bulk polymerization, and has a size of tens to hundreds of micrometers. It refers to a polymer having a form of porous particles with a large amount of pores distributed, no cohesiveness, and excellent flowability.
[36]
As used herein, the term "paste vinyl chloride polymer" is one of the types of vinyl chloride polymer, and may mean polymerized through microsuspension polymerization, microseed polymerization, or emulsion polymerization, etc. It refers to a polymer having a size of several thousand nanometers and has poor flowability as fine, dense, void-free particles.
[37]
The terms 'comprising', 'having' and their derivatives are not intended to exclude the presence of any additional component, step or procedure, whether or not they are specifically disclosed. For the avoidance of any doubt, all compositions claimed through use of the term 'comprising' include, unless stated to the contrary, any additional additives, adjuvants, or compounds, whether polymeric or otherwise. may include In contrast, the term 'consisting essentially of' excludes from the scope of any subsequent description any other component, step, or procedure, except that is not essential to operability. The term 'consisting of' excludes any component, step or procedure not specifically described or listed.
[38]
[39]
How to measure
[40]
In the present specification, analysis of the content of components in the composition is performed through gas chromatography measurement, and Agilent's gas chromatography instrument (product name: Agilent 7890 GC, column: HP-5, carrier gas: helium (flow rate 2.4 mL/min)) , detector: FID, injection volume: 1uL, initial value: 70 °C/4,2 min, end value: 280 °C/7.8 min, program rate: 15 °C/min).
[41]
In the present specification, 'hardness' refers to the shore hardness (Shore “A” and/or Shore “D”) at 25° C. using ASTM D2240, measured under the conditions of 3 mm 10s, and plasticized It can be an index to evaluate the efficiency of plasticization, and the lower it is, the better the plasticization efficiency is.
[42]
In the present specification, 'tensile strength' is a test device, UTM (manufacturer; Instron, model name; 4466), according to the ASTM D638 method, and the cross head speed is 200 mm/min (1T) ), measure the point at which the specimen is cut, and calculate by Equation 1 below.
[43]
[Equation 1]
[44]
Tensile strength (kgf/cm 2 ) = Load value (kgf) / Thickness (cm) × Width (cm)
[45]
In the present specification, 'elongation rate' is measured at the point where the specimen is cut after pulling the cross head speed to 200 mm/min (1 mm) using the UTM according to the ASTM D638 method. After that, it is calculated by Equation 2 below.
[46]
[Equation 2]
[47]
Elongation (%) = length after stretching / initial length × 100
[48]
In this specification, 'migration loss' refers to obtaining a test piece having a thickness of 2 mm or more according to KSM-3156, attaching a glass plate to both sides of the test piece, and applying a load of 1 kgf/cm 2 . After leaving the test piece in a hot air circulation oven (80 °C) for 72 hours, take it out and cool it at room temperature for 4 hours. Then, after removing the glass plate attached to both sides of the test piece, measure the weight before and after leaving the glass plate and the specimen plate in the oven to calculate the transfer loss by Equation 3 below.
[49]
[Equation 3]
[50]
Transition loss (%) = {(initial weight of test piece at room temperature - weight of test piece after leaving in oven) / initial weight of test piece at room temperature} × 100
[51]
In the present specification, 'volatile loss' refers to measuring the weight of the specimen after working the specimen at 80 °C for 72 hours.
[52]
[Equation 4]
[53]
Loss in heating (wt%) = {(initial specimen weight - specimen weight after work) / initial specimen weight} x 100
[54]
In the present specification, the 'absorption rate' is evaluated by measuring the time it takes for the resin and the plasticizer to be mixed with each other and the torque of the mixer is stabilized using a planatary mixer (Brabender, P600) under the conditions of 77°C and 60rpm. do.
[55]
In the case of the various measurement conditions, detailed conditions such as temperature, rotation speed, time, etc. may be slightly different depending on the case, and in different cases, the measurement method and conditions are separately specified.
[56]
[57]
1. Plasticizer composition
[58]
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 citrate-based material represented by the following Chemical Formula 2:
[59]
[Formula 1]
[60]

[61]
[Formula 2]
[62]

[63]
In Formula 1 and Formula 2,
[64]
R 1 and R 2 are each independently an alkyl group having 8 to 10 carbon atoms,
[65]
R 3 to R 5 are each independently an alkyl group having 5 to 10 carbon atoms.
[66]
[67]
The plasticizer composition according to an embodiment of the present invention may further include 3) a trimellitate-based material represented by the following Chemical Formula 3:
[68]
[Formula 3]
[69]

[70]
In Formula 3,
[71]
R 6 to R 8 are each independently an alkyl group having 4 to 10 carbon atoms.
[72]
[73]
Hereinafter, components of the plasticizer composition according to an embodiment of the present invention will be described in detail.
[74]
[75]
1) Cyclohexane -1,2- diester-based material
[76]
The cyclohexane-1,2-diester-based material is represented by Chemical Formula 1, and since the phthalate component is excluded from the plasticizer composition, it can impart environmentally friendly properties. In addition, the plasticizing efficiency, elongation and transfer properties of the plasticizer composition can be further improved. When the bonding position of the diester group in cyclohexane is not the 1 or 2 position, there is a problem in that compression transferability and stress transferability are poor.
[77]
[78]
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, heating 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 9 or 10 carbon atoms may be preferably selected.
[79]
[80]
R 1 and R 2 are each independently selected from the group consisting of n-octyl group, isooctyl group, 2-ethylhexyl group, n-nonyl group, isononyl group, 2-propylheptyl group and isodecyl group Among them, one selected from the group consisting of a 2-ethylhexyl group, an isononyl group, a 2-propylheptyl group and an isodecyl group is preferable, and more preferably an isononyl group or a 2-propylheptyl group can
[81]
[82]
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
[83]
[84]
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.
[85]
The alkyl group of the finally prepared cyclohexane-1,2-dicarboxyl diester preferably has 8 to 10 carbon atoms or 9 or 10 carbon atoms.
[86]
[87]
When the cyclohexane-1,2-diester-based material is prepared by the direct esterification reaction, 2 to 10 moles of the alcohol, 2 to 1 mole of the cyclohexane-1,2-dicarboxylic acid or a derivative thereof to 8 moles, 2 to 6 moles, or 2 to 5 moles may be used, of which 2 to 5 moles are preferably used.
[88]
[89]
The direct esterification reaction may be performed in the presence of a catalyst, and the catalyst may be at least one selected from the group consisting of an inorganic acid, an organic acid, and a Lewis acid.
[90]
The inorganic acid may be at least one selected from the group consisting of sulfuric acid, hydrochloric acid and phosphoric acid.
[91]
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.
[92]
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.
[93]
[94]
When the catalyst is a homogeneous catalyst, it 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 its derivative and alcohol, of which 0.01 to It is preferably used in 3 parts by weight.
[95]
[96]
When the catalyst is a heterogeneous catalyst, it may be used in an amount of 5 to 200 parts by weight or 5 to 100 parts by weight based on 100 parts by weight of the total of cyclohexane-1,2-dicarboxylic acid or a derivative thereof and alcohol, of which 5 to 200 parts by weight. It is preferably used in parts by weight.
[97]
[98]
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.
[99]
[100]
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.
[101]
[102]
On the other hand, when the cyclohexane-1,2-diester-based material represented by Formula 1 is prepared by the transesterification reaction, the transesterification reaction of the cyclohexane-1,2-dicarboxylic acid derivative with the alcohol is used. can be manufactured.
[103]
[104]
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
[105]
[106]
The transesterification reaction may be performed in the presence of a catalyst, and in this case, the reaction time may be shortened.
[107]
The catalyst may be at least one selected from the group consisting of a Lewis acid and an alkali metal.
[108]
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).
[109]
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 a mixed catalyst of two or more of the metal catalysts may be used.
[110]
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
[111]
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.
[112]
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.
[113]
[114]
The direct esterification reaction or transesterification reaction is one or more organic selected from the group consisting of hexane, benzene, toluene, xylene, and cyclohexane having a relatively low boiling point in order to promote the outflow of the lower alcohol produced by the reaction. A solvent may be additionally added, and commercially available nitrogen or the like may be used as entrainment for the same purpose.
[115]
[116]
The cyclohexane-1,2-diester-based material 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.
[117]
[118]
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.
[119]
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.
[120]
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 .
[121]
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 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.
[122]
[123]
2) Citrate-based materials
[124]
The citrate-based material is represented by Chemical Formula 2, and may further improve the absorption rate, plasticization efficiency, migration resistance, and the like of the plasticizer composition.
[125]
[126]
In Chemical Formula 2, the citrate-based material containing an acetyl group instead of a hydroxyl group cannot avoid the deterioration of mechanical properties such as physical properties, tensile strength and elongation of the plasticizer composition, and this problem may be further aggravated due to poor plasticization efficiency. have. In addition, in order to treat waste acetic acid generated as a by-product during the production of a citrate-based material containing an acetyl group, a process, time, and equipment cost may be added, which may increase the manufacturing cost.
[127]
Therefore, in the citrate-based material containing an acetyl group instead of a hydroxyl group in Chemical Formula 2, the plasticization efficiency is lowered compared to the citrate-based material represented by Chemical Formula 2, and the input amount must be increased to overcome this, so that the product price will increase. can Therefore, a citrate-based material containing an acetyl group is not preferable in various aspects such as marketability, economic efficiency, and physical properties.
[128]
[129]
The R 3 to R 5 are each independently preferably an alkyl group having 5 to 10 carbon atoms. When the above-mentioned conditions are satisfied, since the molecular weight of the citrate-based material is appropriate, the plasticizing efficiency and absorption rate of the plasticizer composition may be further improved. When R 3 to R 5 are each independently an alkyl group having less than 5 carbon atoms, the tensile strength and heat loss of the plasticizer composition are lowered, and the residual ratio characteristic is extremely poor. This relatively increases, and not only increases the possibility of adversely affecting the atmosphere, but also has to add an excess amount of the plasticizer composition by the amount of volatilization in order to improve this, which is uneconomical. When R 3 to R 5 are each independently an alkyl group having more than 10 carbon atoms, the molecular weight of the citrate-based material is increased, and the plasticizing efficiency and absorption rate of the plasticizer composition are rather reduced.
[130]
[131]
On the other hand, in order to improve all of these effects between the effects of plasticization efficiency, absorption rate and transferability, and the effects of tensile and tensile residual ratio, elongation and stretch residual ratio, oil resistance and heat loss, R 3 to R 5 must have 5 to 5 carbon atoms. It may be preferable that it is an alkyl group of 10.
[132]
[133]
wherein R 3 to R 5 are each independently a n-pentyl group, an isopentyl group, a n-hexyl group, an isohexyl group, an n-heptyl group, an isoheptyl group, a n-octyl group, an isooctyl group, and a 2-ethylhexyl group , n-nonyl group, isononyl group, 2-propylheptyl group and may be one selected from the group consisting of isodecyl group, among these, n-pentyl group, isopentyl group, n-hexyl group, isohexyl group, One selected from the group consisting of a 2-ethylhexyl group and an isononyl group is preferable.
[134]
Here, a specific example of the isopentyl group may include a 2-methylbutyl group, and specific examples of the isohexyl group include a 2-methylpentyl group, a 3-methylpentyl group, a 4-methylpentyl group, and a 2,2-dimethylbutyl group. , a 2,3-dimethylbutyl group, and 2-ethylbutyl group.
[135]
[136]
Two of R 3 to R 5 may be the same as each other, and the other may be different. In this case, the citrate-based material represented by Formula 2 may be a citrate having two combined substituents selected from the above substituents, In this case, the difference in carbon number of the two substituents may be selected to be 1 to 4.
[137]
[138]
R 3 to R 5 may be the same as each other, and in this case, the citrate-based material represented by Formula 2 is tri n-pentyl citrate (TnPC), triisopentyl citrate (TIPC), trihexyl citrate ( THxC), triisohexyl citrate (TIHxC), triheptyl citrate (THpC), triisoheptyl citrate (TIHpC), tri(2-ethylhexyl)citrate (TEHC) and triisononyl citrate (TINC) , may be at least one selected from the group consisting of triisodecyl citrate (TIDC).
[139]
Specific examples of the triisopentyl citrate include tri(2-methylbutyl) citrate, and specific examples of the triisohexyl citrate include tri(2-methylpentyl) citrate and tri(3-methyl) citrate. pentyl) citrate, tri(4-methylpentyl) citrate, tri(2,2-dimethylbutyl) citrate, tri(2,3-dimethylbutyl) citrate, tri(2-ethylbutyl) citrate, etc. can be heard
[140]
[141]
On the other hand, the weight ratio of the cyclohexane-1,2-diester-based material represented by Formula 1 and the citrate-based material represented by Formula 2 is 95:5 to 5:95, 90:10 to 10:90 or 80 :20 to 20:80, of which 80:20 to 20:80 is more preferable. When the above-mentioned content is satisfied, there is an advantage in that the quality such as plasticization efficiency, absorption rate, and migration resistance is improved.
[142]
[143]
When the citrate-based material represented by Formula 2 is directly prepared, it may be prepared by direct esterification or transesterification reaction between citric acid or a derivative thereof and alcohol.
[144]
[145]
The citric acid derivative may be at least one selected from the group consisting of an anhydride of citric acid and an alkyl ester of citric acid. The alkyl ester may be an alkyl ester having 1 to 6 carbon atoms, and the alcohol is preferably an alcohol having 5 to 10 carbon atoms.
[146]
[147]
When the citrate-based material represented by Chemical Formula 2 is prepared by the direct esterification reaction or the transesterification reaction, the alcohol content is 3 to 15 moles, 3 to 12 moles, or It may be used in an amount of 3 to 10 moles, of which 3 to 10 moles are preferably used.
[148]
[149]
Other than that, the description of the direct esterification reaction and the transesterification reaction is the same as described in the method for preparing the cyclohexane-1,2-diester-based material represented by Chemical Formula 1 above.
[150]
[151]
3) trimellitate-based substances
[152]
The trimellitate-based material is represented by Chemical Formula 3, and may impart environmental-friendly properties and excellent stability to the plasticizer composition. In addition, properties such as migration resistance, heat loss, tensile residual rate and oil resistance of the plasticizer composition can be further improved, and in particular, in the case of a plasticizer composition to which the trimellitate-based material is applied, it may be more advantageous for the compound industry.
[153]
[154]
Each of R 6 to R 8 is independently an alkyl group having 4 to 10 carbon atoms, and may be an alkyl group having 5 to 10 carbon atoms, an alkyl group having 5 to 9 carbon atoms, or an alkyl group having 6 to 9 carbon atoms, among which, an alkyl group having 6 to 9 carbon atoms. It is preferable to be If the above conditions are satisfied, migration resistance, heat loss, elongation residual rate, oil resistance, and stress migration resistance may be further improved.
[155]
[156]
Wherein R 6 To R 8 are each independently n-butyl group, isobutyl group, n-pentyl group, isopentyl group, n-hexyl group, n-heptyl group, isoheptyl group, n-octyl group, isooctyl group, It may be one selected from the group consisting of 2-ethylhexyl group, n-nonyl group, isononyl group, 2-propylheptyl group and isodecyl group, of which 2-ethylhexyl group or isononyl group is preferable.
[157]
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.
[158]
[159]
The trimellitate-based material represented by Formula 3 is 1 to 150 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 citrate-based material represented by Formula 2 It may be included in an amount of 5 to 125 parts by weight, 10 to 100 parts by weight, or 20 to 100 parts by weight, of which 20 to 100 parts by weight is preferable. If the above-described range is satisfied, there is an advantage in that the quality such as oil resistance, tensile and elongation residual ratio, and heat loss can be improved.
[160]
[161]
When the trimellitate-based material represented by Chemical Formula 3 is directly prepared, it may be prepared by direct esterification or transesterification reaction between trimellitic acid or a derivative thereof and alcohol.
[162]
[163]
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. The alkyl ester may be an alkyl ester having 1 to 6 carbon atoms.
[164]
[165]
The alcohol may be an alcohol having 4 to 10 carbon atoms, an alcohol having 5 to 10 carbon atoms, an alcohol having 5 to 9 carbon atoms, or an alcohol having 6 to 9 carbon atoms, of which it is preferably an alcohol having 6 to 9 carbon atoms.
[166]
[167]
When the trimellitate-based material represented by Chemical Formula 3 is prepared by the direct esterification reaction, the alcohol is contained in an amount of 3 to 15 moles, 3 to 12 moles, or 3 to 1 mole of the trimellitic acid or a derivative thereof. It may be used in an amount of 10 moles, of which 3 to 10 moles are preferably used.
[168]
[169]
Other than that, the description of the direct esterification reaction is the same as described in the method for preparing the cyclohexane-1,2-diester-based material.
[170]
[171]
Meanwhile, when the trimellitate-based material represented by Formula 3 is prepared by the transesterification reaction, it may be prepared by the transesterification reaction of the trimellitic acid derivative and alcohol. Here, the derivative of trimellitic acid may be an alkyl ester of trimellitic acid.
[172]
[173]
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 is preferably used.
[174]
Other than that, the description of the transesterification reaction is the same as described in the method for preparing the cyclohexane-1,2-diester-based material represented by Formula 1 above.
[175]
[176]
2. Resin composition
[177]
The resin composition according to another embodiment of the present invention includes 100 parts by weight of a resin; And 5 to 150 parts by weight of the plasticizer composition according to an embodiment of the present invention.
[178]
As the resin, a resin known in the art may be used. For example, at least one selected from the group consisting of straight vinyl chloride polymer, paste vinyl chloride polymer, ethylene vinyl acetate copolymer, ethylene polymer, propylene polymer, polyketone, polystyrene, polyurethane, natural rubber, synthetic rubber, and thermoplastic elastomer Mixtures and the like may be used, but the present invention is not limited thereto.
[179]
The plasticizer composition may be included in an amount of 5 to 150 parts by weight, preferably 5 to 130 parts by weight, or 10 to 120 parts by weight based on 100 parts by weight of the resin.
[180]
In general, the resin in which the plasticizer composition is used may be manufactured into a resin product through melt processing or plastisol processing, and the melt processing resin and the plastisol processing resin may be produced differently according to each polymerization method.
[181]
For example, when a vinyl chloride polymer is used for melt processing, solid resin particles with a large average particle diameter are used because it is prepared by suspension polymerization, etc., and this vinyl chloride polymer is called a straight vinyl chloride polymer, and is used for plastisol processing. In this case, a resin in a sol state is used as a fine resin particle produced by emulsion polymerization, etc., and such a vinyl chloride polymer is called a paste vinyl chloride resin.
[182]
At this time, in the case of the straight vinyl chloride polymer, the plasticizer composition is preferably included in an amount of 5 to 80 parts by weight based on 100 parts by weight of the polymer, and in the case of the paste vinyl chloride polymer, it is included in an amount of 40 to 120 parts by weight based on 100 parts by weight of the polymer. desirable.
[183]
The resin composition may further include a filler. The filler may be 0 to 300 parts by weight, preferably 50 to 200 parts by weight, more preferably 100 to 200 parts by weight based on 100 parts by weight of the resin.
[184]
As the filler, any filler known in the art may be used, and the filler is not particularly limited. For example, it may be a mixture of at least one selected from silica, magnesium carbonate, calcium carbonate, coal, talc, magnesium hydroxide, titanium dioxide, magnesium oxide, calcium hydroxide, aluminum hydroxide, aluminum silicate, magnesium silicate, and barium sulfate.
[185]
In addition, the resin composition may further include other additives such as a stabilizer, if necessary. Other additives such as the stabilizer may be each independently 0 to 20 parts by weight, preferably 1 to 15 parts by weight, based on 100 parts by weight of the resin.
[186]
The stabilizer may include, for example, a calcium-zinc (Ca-Zn-based) stabilizer or a barium-zinc-based (Ba-Zn-based) stabilizer such as a calcium-zinc complex stearate salt, but is not particularly limited thereto. it is not
[187]
The resin composition may be applied to both melt processing and plastisol processing as described above, for example, melt processing may be calendering processing, extrusion processing, or injection processing, and plastisol processing may be coating processing, etc. This can be applied.
[188]
[189]
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.
[190]
[191]
Preparation Example 1: diisononyl cyclohexane -1,2- diester
[192]
516.5 g of cyclohexane-1,2-dicarboxylic acid, 1,296 g of isononyl alcohol, and 1.55 g of tetraisopropyl titanate as 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.
[193]
After completion of the reaction, in order to remove unreacted raw materials, distillation extraction was performed under reduced pressure. After distillation and extraction, 1,240 g (yield: 97%) of diisononyl cyclohexane-1,2-dicarboxylate (D1NCH) was prepared through a neutralization process, a dehydration process, and a filtration process.
[194]
[195]
Preparation Example 2: Di (2-propylheptyl) cyclohexane-1,2-diester
[196]
Di(2-propylheptyl)cyclohexane-1,2-dica in the same manner as in Preparation Example 1, except that 516.5 g of cyclohexane-1,2-dicarboxylic acid and 1,422 g of 2-propylheptanol were added to the reactor. 1,320 g of carboxylate (DPHpCH), (yield: 97%) was obtained.
[197]
[198]
Preparation Example 3: Tri (n-butyl) citrate
[199]
Tri(n-butyl) citrate (TnBC) 700 g, (yield: 97%) was obtained in the same manner as in Preparation Example 1, except that 384.2 g of citric anhydride and 670 g of n-butanol were added to the reactor.
[200]
[201]
Preparation Example 4: Tri (n- pentyl ) citrate
[202]
780 g of tri(n-pentyl) citrate (TnPC), (yield: 97%) was obtained in the same manner as in Preparation Example 1, except that 384.2 g of citric anhydride and 794 g of n-pentanol were added to the reactor. .
[203]
[204]
Preparation Example 5: Tri (n- hexyl ) citrate
[205]
863 g of tri(n-hexyl) citrate (TnHxC), (yield: 97%) was obtained in the same manner as in Preparation Example 1, except that 384.2 g of citric anhydride and 918 g of n-hexanol were added to the reactor. .
[206]
[207]
Preparation 6: Tri (2 -ethylhexyl ) citrate
[208]
1,026 g of tri(2-ethylhexyl) citrate (TEHC), (yield: 97%) was prepared in the same manner as in Preparation Example 1 except that 384.2 g of citric anhydride and 1,170 g of 2-ethylhexanol were added to the reactor. obtained.
[209]
[210]
Preparation 7: triisononyl citrate
[211]
1,108 g of triisononyl citrate (TINC), (yield: 97%) was obtained in the same manner as in Preparation Example 1, except that 384.2 g of citric anhydride and 1,296 g of isononanol were added to the reactor.
[212]
[213]
Preparation 8: Tri (2 -ethylhexyl ) trimellitate
[214]
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.
[215]
[216]
Preparation Example 9: Triisononyl trimellitate
[217]
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.
[218]
[219]
Plasticizer compositions of Examples and Comparative Examples were prepared by mixing one or more of the materials prepared in Preparation Examples 1 to 9, etc., which are summarized in [Table 1] to [Table 5] 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.
[220]
[221]

[222]
Measurement of hardness (shore A and shore D)
[223]
According to ASTM D2240, the hardness of the specimen having a thickness of 3 mm was measured for 10 seconds.
[224]
[225]
Tensile strength measurement ( kgf /㎠)
[226]
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.
[227]
[228]
Elongation measurement ( % )
[229]
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 1 below, the elongation was calculated.
[230]

[231]
Elongation (%): [(length at the time the specimen is cut)/(initial length)]×100
[232]
[233]
Measurement of Tensile and Elongation Residual ( % )
[234]
The measurement of tensile and elongation residual is to measure the tensile strength and elongation remaining in the specimen after applying heat at 113° C. for 168 hours, and the measurement method is the same as the tensile strength and elongation measurement method.
[235]
[236]
Measurement of migration loss ( % )
[237]
According to KSM-3156, after attaching PS plates to both sides of a specimen having a thickness of 1 mm, a load of 1 or 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 leaving it in the oven, and substituted into Equation 2 below to calculate the transfer loss value.
[238]

[239]
Transition loss (%) = [(initial weight of specimen before test) - (weight of specimen after test)] / (initial weight of specimen before test) × 100
[240]
[241]
Heat loss measurement ( % )
[242]
After a specimen having a thickness of 1 mm was exposed at 80° C. for 72 hours or at 113° C. for 168 hours, the weight of the specimen was measured, and the weight loss was calculated by substituting it in Equation 3 below.
[243]

[244]
Loss on heating (%) = [(initial weight of specimen) - (weight of specimen after work)]/ (initial weight of specimen before leaving in oven) × 100
[245]
[246]
stress transitivity
[247]
After a specimen having a thickness of 2 mm was left in a bent state at 23° C. for 168 hours, the degree of migration (the degree of seepage) was observed, and the result was described as a numerical value.
[248]
0: Very good, 1: Excellent, 2: Moderate, 3: Poor
[249]
[250]
Absorption rate evaluation
[251]
Under the conditions of 77 ° C., 60 rpm, using a Planetary Mixer (model name: P600, manufacturer: Brabender), the resin composition and the ester compound were mixed, and the time taken until the torque of the mixer was stabilized was measured and evaluated.
[252]
1: Very good, 2: Excellent, 3: Average, 4: Poor, 5: Poor
[253]
[254]
oil resistance
[255]
After leaving a specimen with a thickness of 1 mm in IRM-902 oil at 70°C for 4 hours, the tensile strength and elongation remaining in the specimen are measured, and the measurement method is the same as that of the tensile strength and elongation measurement method.
[256]
[257]
Experimental Example 1: car rendering properties of the prescribed evaluation
[258]
Specimens were prepared using the plasticizer compositions of Examples and Comparative Examples described in [Table 1] and [Table 2] below.
[259]
According to ASTM D638, 100 parts by weight of polyvinyl chloride (trade name: LS100, manufacturer: LG Chemical), 40 parts by weight of the plasticizer composition prepared in Examples and Comparative Examples, and a stabilizer (trade name: RUP-144, Manufacturer: ADEKA) 3 parts by weight, was mixed, and stirred at 98 ° C. at a speed of 700 rpm. Then, roll milling was carried out at 160 °C for 4 minutes, and using a press at 180 °C for 3 minutes (low pressure) and 2.5 minutes (high pressure), a specimen having a thickness of 1 mm and a specimen having a thickness of 3 mm were manufactured.
[260]
Each of the test items was independently evaluated for the specimen, and the results are shown in [Table 1] and [Table 2] below. Transition loss was measured after applying a load of 1 kgf/cm 3 , and weight loss was measured after exposure to 80° C. for 72 hours.
[261]
[262]
[Table 1]
division Example
One 2 3 4 5
Plasticized composition (parts by weight) Cyclohexane-1,2-diester-based material DINCH 70 30 70 30 -
DPHpCH - - - - 50
Citrate-based substances TnPC 30 70 - - 50
TnHxC - - 30 70 -
Shore hardness A 91.9 89.8 87.7 89.8 90.6
tensile strength 242.9 239.6 230.6 240.6 233.7
elongation 337.1 334.1 337.8 347.8 335.3
performance loss 3.79 3.07 2.52 2.12 3.05
reduction in heating 1.20 1.46 1.85 1.30 0.88
stress transitivity 1.0 0 0 0 0
absorption rate 3 One One One 2
[263]
[Table 2]
division comparative example
One 2 3 4 5 6
Plasticizer composition (parts by weight) Cyclohexane-1,2-diester-based material DINCH - 100 - 50 70 50
Citrate-based substances TnBC - - - 50 - -
TEHC - - 100 - - -
ATBC - - - - 30 -
ATEHC - - - - - 50
diisodecyl phthalate 100 - - - - -
Shore hardness A 94.4 94.3 98.8 88.4 90.8 97.2
tensile strength 235.0 225.0 247.6 207.3 241.9 245.6
elongation 286.3 306.7 274.2 312.0 306.7 274.0
performance loss 2.30 5.10 4.32 2.84 3.80 5.32
reduction in heating 1.64 1.07 0.68 6.74 1.25 1.41
stress transitivity 1.0 2.0 3.0 1.0 0.5 3
absorption rate 4 5 5 One 3 5
[264]
ATBC: Acetyltributyl Citrate
[265]
TEHC: Acetyltri(2-ethylhexyl)citrate
[266]
[267]
Referring to [Table 1] and [Table 2], Examples 1 to 5 are excellent in plasticization efficiency, elongation and absorption rate compared to Comparative Example 1 which is diisodecyl phthalate, and tensile strength and heat loss are at the same level, It was confirmed that the heating loss was slightly lowered. From these results, it was confirmed that the plasticizer composition according to an embodiment of the present invention can replace diisodecyl phthalate because it is environmentally friendly while implementing superior or equivalent physical properties compared to diisodecyl phthalate, which is a conventional plasticizer.
[268]
On the other hand, it was confirmed that Comparative Example 2, which did not contain a citrate-based material, had poor plasticization efficiency, tensile strength, elongation, transfer loss, stress transferability and absorption rate compared to Examples. It can be confirmed that Comparative Example 3, which does not contain the cyclohexane-1,2-diester-based material, has poor plasticization efficiency, elongation, transfer loss, stress transferability and absorption rate compared to Examples. It was confirmed that Comparative Example 4 containing tri(n-butyl)citrate had poor tensile strength, elongation, and heat loss compared to Example.
[269]
Comparative Example 5 containing acetyl tributyl citrate was confirmed to have poor elongation compared to Example. In addition, it was confirmed that Comparative Example 6 containing acetyltri (2-ethylhexyl) citrate was inferior in plasticization efficiency, elongation, migration loss and absorption rate compared to Example. In addition, since the acetylation process is added during the manufacturing process of citrate containing an acetyl group, cost competitiveness may deteriorate due to the generation of by-products and treatment of by-products as well as an increase in cost.
[270]
[271]
Experimental Example 2: Evaluation of compound properties
[272]
Specimens were prepared using the plasticizer compositions of Examples and Comparative Examples described in [Table 3] to [Table 5] below.
[273]
According to ASTM D638, 100 parts by weight of polyvinyl chloride (trade name: LS100, manufacturer: LG Chem), 50 parts by weight of the plasticizer composition prepared in Examples and Comparative Examples, 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, 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 independently fabricated.
[274]
Each of the test items was independently evaluated for the specimen, and the results are shown in [Table 5] to [Table 5] below.
[275]
[276]
[Table 3]
division Example
6 7 8 9
Plasticized composition (parts by weight) Cyclohexane-1,2-diester-based material DINCH 50 30 40 10
Citrate-based substances TEHC 50 70 - -
TINC - - 60 90
Hardness A 92.8 92.7 94.6 95.1
D 45.5 45.4 47.9 48.8
tensile strength 177.2 174.3 179.0 178.3
Tensile residual rate 100.3 98.7 98.7 99.6
elongation 268.4 280.0 272.5 275.5
Kidney Residual Rate 85.9 88.6 81.7 82.1
oil resistance Tensile residual rate 97.7 95.9 85.7 85.9
Kidney Residual Rate 85.4 87.8 72.1 70.9
performance loss 1.86 1.56 1.82 0.95
reduction in heating 4.56 3.94 3.20 3.00
[277]
[Table 4]
division Example
10 11 12 13 14
Plasticized composition (parts by weight) Cyclohexane-1,2-diester-based material DINCH 40 30 50 30 40
Citrate-based substances TEHC 30 20 - - -
TINC - - 30 30 50
trimellitate substances TEHTM 30 50 20 40 10
TINTM - - 20 40 10
Hardness A 92.9 93.4 94.3 95.1 94.5
D 46.4 47.0 48.3 48.9 48.3
tensile strength 171.1 178.6 174.7 187.6 172.3
Tensile residual rate 101.0 100.8 100.5 99.4 98.4
elongation 281.4 294.3 280.9 295.8 281.6
Kidney Residual Rate 87.0 93.5 89.4 95.6 92.4
oil resistance Tensile residual rate 89.9 92.4 86.6 93.4 92.0
Kidney Residual Rate 79.8 86.7 78.6 88.2 85.4
performance loss 1.32 0.86 1.41 0.90 1.02
reduction in heating 4.31 3.25 4.86 2.45 3.14
[278]
[Table 5]
division comparative example
7 8 9 10 11 12
plastic composition Cyclohexane-1,2-diester-based material DINCH - 100 - 50 70 50
Citrate-based substances TnBC - - - 50 - -
TEHC - - 100 - - -
ATBC - - - - 30 -
ATEHC - - - - - 50
Diisodecyl phthalate (parts by weight) 100 - - - - -
Hardness A 93.4 92.3 99.4 89.0 91.4 97.8
D 46.8 45.1 52.3 42.5 43.8 51.0
tensile strength 161.3 154.0 170.2 150.3 148.3 159.7
Tensile residual rate 104.5 74.8 100.1 57.6 61.0 82.4
elongation 267.6 270.1 245.7 250.8 235.9 260.3
Kidney Residual Rate 86.4 58.6 74.2 43.0 44.2 60.2
oil resistance Tensile residual rate 86.2 62.0 82.3 40.8 48.7 75.0
Kidney Residual Rate 72.5 52.8 60.2 35.1 45.6 69.4
performance loss 2.04 2.58 4.58 5.30 6.02 3.88
reduction in heating 4.85 5.06 1.24 15.9 8.66 4.20
[279]
ATBC: Acetyltributyl Citrate
[280]
TEHC: Acetyltri(2-ethylhexyl)citrate
[281]
[282]
Referring to [Table 3] to [Table 5], Examples 6 to 14 have the same level of plasticization efficiency, tensile residual ratio, elongation residual ratio and oil resistance compared to Comparative Example 7 which is diisodecyl phthalate, but tensile strength, elongation, transition It was confirmed that the loss and heating loss were excellent. From these results, it was confirmed that the plasticizer composition according to an embodiment of the present invention can replace diisodecyl phthalate because it is environmentally friendly while implementing superior or equivalent physical properties compared to diisodecyl phthalate, which is a conventional plasticizer.
[283]
On the other hand, it was confirmed that Comparative Example 8, which did not contain a citrate-based material, had poor tensile strength, elongation, and transition loss compared to Example. Comparative Example 9, which did not contain the cyclohexane-1,2-diester-based material, showed poor plasticization efficiency, tensile strength, elongation, elongation residual ratio, oil resistance, and migration loss compared to Example. It was confirmed that Comparative Example 10 containing tri(n-butyl)citrate was inferior in tensile strength, elongation, elongation residual ratio, oil resistance, migration loss and heat loss compared to Example.
[284]
It was confirmed that Comparative Example 11 containing acetyl tributyl citrate was inferior in tensile strength, tensile residual ratio, elongation, elongation residual ratio, oil resistance, transfer loss and heating loss compared to Example. In addition, it was confirmed that Comparative Example 12 containing acetyltri(2-ethylhexyl)citrate had poor plasticization efficiency, tensile strength, tensile residual ratio, elongation, elongation residual ratio, oil resistance and migration loss compared to Example. In addition, since an acetylation process is added during the manufacturing process for citrate containing an acetyl group, cost competitiveness may deteriorate due to the generation of by-products and treatment of by-products as well as an increase in cost.
Claims
[Claim 1]
a cyclohexane-1,2-diester-based material represented by the following formula (1); And a plasticizer composition comprising a citrate-based material represented by the following Chemical Formula 2: [Formula 1] [Formula 2] In Chemical Formulas 1 and 2, R 1 and R 2 are each independently an alkyl group having 8 to 10 carbon atoms, R 3 to R 5 are each independently an alkyl group having 5 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 citrate-based material represented by Formula 2 is 95:5 to 5:95.
[Claim 3]
The plasticizer composition of claim 1, wherein R 1 and R 2 are each independently an alkyl group having 9 or 10 carbon atoms.
[Claim 4]
The method according to claim 1, wherein R 1 and R 2 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 5]
The method according to claim 1, wherein R 3 to R 5 are each independently n-pentyl group, isopentyl group, n-hexyl group, isohexyl group, n-heptyl group, isoheptyl group, n-octyl group, isooctyl group, A plasticizer composition that is one selected from the group consisting of 2-ethylhexyl group, n-nonyl group, isononyl group, 2-propylheptyl group and isodecyl group.
[Claim 6]
The plasticizer composition according to claim 1, wherein the plasticizer composition further comprises a trimellitate-based material represented by the following Chemical Formula 3: [Formula 3] In Chemical Formula 3, R 6 to R 8 are each independently C 4 to It is an alkyl group of 10.
[Claim 7]
The plasticizer composition of claim 6, wherein R 6 to R 8 are each independently an alkyl group having 5 to 10 carbon atoms.
[Claim 8]
The method according to claim 6, wherein R 6 to R 8 are each independently n-butyl group, isobutyl group, n-pentyl group, isopentyl group, n-hexyl group, isohexyl group, n-heptyl group, isoheptyl group , n-octyl group, isooctyl group, 2-ethylhexyl group, n-nonyl group, isononyl group, 2-propylheptyl group, and the plasticizer composition that is one selected from the group consisting of isodecyl group.
[Claim 9]
The method according to claim 6, 100 parts by weight of the sum of the cyclohexane-1,2-diester-based material represented by Formula 1 and the citrate-based material represented by Formula 2; and 1 to 150 parts by weight of the trimellitate-based material represented by Formula 3 above.
[Claim 10]
100 parts by weight of resin; and 5 to 150 parts by weight of the plasticizer composition according to claim 1 .
[Claim 11]
The method according to claim 10, wherein the resin is a straight vinyl chloride polymer, a paste vinyl chloride polymer, an ethylene vinyl acetate copolymer, an ethylene polymer, a propylene polymer, a polyketone, polystyrene, polyurethane, natural rubber, synthetic rubber and a thermoplastic elastomer from the group consisting of One or more selected resin compositions.