Title of the invention: plasticizer composition and resin composition comprising the same
Technical field
[One]
[Mutual citation with related application]
[2]
The present invention claims the benefit of priority based on Korean Patent Application No. 10-2018-0067039 filed on 2018.06.11, and includes all the contents disclosed in the documents of the Korean patent application as part of this specification.
[3]
[Technical field]
[4]
The present invention relates to a plasticizer composition and a resin composition including the same, and to a plasticizer composition that is environmentally friendly and excellent in stability and basic physical properties, and a resin composition including the same.
[5]
Background
[6]
Typically plasticizers react with alcohols with polycarboxylic acids such as phthalic acid and adipic acid to form corresponding esters. In addition, in consideration of domestic and overseas regulations of phthalate plasticizers that are harmful to the human body, studies on plasticizer compositions that can replace phthalate plasticizers such as terephthalate, adipate, and other polymers are continuing.
[7]
On the other hand, in the compound industry whose main properties are high heat resistance and low heat loss, it is necessary to use an appropriate plasticizer in consideration of the required properties. In the case of PCV compounds for wires and cables, third materials such as plasticizers, stabilizers, pigments, etc. are mixed with PVC resin according to the properties required by the applicable standard, such as tensile strength, elongation, plasticization efficiency, heating loss, tensile and elongation residuals do.
[8]
Currently, general-purpose products used in various extrusion, injection, calendering and compound industries such as electric wires, flooring, automotive interior materials, films, hoses and tubes are diisononylphthalate (DINP) or diisodecylphthalate (DIDP). Phthalate products are widely used.
[9]
However, these phthalate products are substances that are regulated or need to be regulated according to the use of the product, and non-phthalate products such as diethylhexyl terephthalate (DOTP or DEHTP) are commonly used in order to meet the demands of the market. However, improvement is required in terms of quality.
[10]
In response to these environmental issues and the demand for quality improvement over the same level as existing products, it is necessary to develop new products that can improve the quality of existing products while based on eco-friendliness. While having, by developing a new plasticizer composition product that is environmentally friendly, research is underway to secure a vinyl chloride-based resin composition that is free from environmental problems and is excellent in quality.
[11]
Detailed description of the invention
Technical challenge
[12]
The present invention was derived to solve the problems of the prior art, and when used as a plasticizer of a resin composition, a plasticizer composition capable of improving physical properties such as plasticization efficiency, heating loss, light resistance, thermal stability and transferability to an excellent level, and It is intended to provide a resin composition comprising this.
[13]
Means of solving the task
[14]
In order to solve the above problems, the present invention provides a cyclohexane-1,2-diester-based material in which two alkyl groups bonded to the diester group are each independently alkyl groups having 4 to 12 carbon atoms; And it provides a plasticizer composition comprising an epoxidized alkyl ester composition comprising at least one compound represented by the following Formula 1:
[15]
[Formula 1]
[16]

[17]
In Formula 1,
[18]
R 1 is an alkyl group having 8 to 20 carbon atoms including one or more epoxy groups,
[19]
R 2 is an alkyl group having 4 to 10 carbon atoms.
[20]
[21]
In addition, the present invention 100 parts by weight of the resin; And it provides a resin composition comprising 5 to 150 parts by weight of the plasticizer composition.
[22]
Effects of the Invention
[23]
The plasticizer composition according to an embodiment of the present invention may be used in a resin composition to provide a plasticizer composition capable of improving physical properties such as plasticization efficiency, heating loss, light resistance and thermal stability to an excellent level.
[24]
Best mode for carrying out the invention
[25]
Hereinafter, the present invention will be described in more detail to aid understanding of the present invention.
[26]
The terms or words used in the specification and claims should not be construed as being limited to their usual or dictionary meanings, and the inventor may appropriately define the concept of terms in order to describe his own invention in the best way. It should be interpreted as a meaning and concept consistent with the technical idea of ​​the present invention based on the principle that there is.
[27]
[28]
The compound names used in this specification may be conventionally used names, and are named according to the substituents characteristically bonded to each compound, and even if the compound name does not correspond to the conventional name, it is named according to the substituents expressed in the structure of the formula. It can be understood as being made.
[29]
[30]
The prefix “iso-” as used herein may mean collectively an alkyl group in which a methyl group or an ethyl group is bonded in a branched chain to the main chain of the alkyl group, and in the present specification, it is bonded to the terminal as long as there is no alkyl group otherwise referred to as otherwise. It may 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 including the ones.
[31]
[32]
"Alkyl group" as used herein is not limited other than the limit of the number of carbons unless otherwise specified, it may be understood as a straight chain or branched chain.
[33]
[34]
In the present invention, the iodine number can be measured according to ASTM D5768-02.
[35]
[36]
In the present invention, the oxirane content can be measured according to ASTM D1652-04.
[37]
[38]
1. Plasticizer composition
[39]
The plasticizer composition according to an embodiment of the present invention includes 1) a cyclohexane-1,2-diester-based material in which two alkyl groups bonded to the diester group are each independently an alkyl group having 4 to 12 carbon atoms; And 2) an epoxidized alkyl ester composition comprising at least one compound represented by the following Formula 1:
[40]
[Formula 1]
[41]

[42]
In Formula 1,
[43]
R 1 is an alkyl group having 8 to 20 carbon atoms including one or more epoxy groups,
[44]
R 2 is an alkyl group having 4 to 10 carbon atoms.
[45]
[46]
In addition, the plasticizer composition according to an embodiment of the present invention may further include 3) a citrate-based material represented by Formula 3 below:
[47]
[Chemical Formula 3]
[48]

[49]
In Chemical Formula 3,
[50]
R 5 to R 7 are each independently an alkyl group having 4 to 10 carbon atoms.
[51]
[52]
Hereinafter, components of the plasticizer composition according to an embodiment of the present invention will be described in detail.
[53]
[54]
1) Cyclohexane -1,2- diester material
[55]
The cyclohexane-1,2-diester-based material can impart environmentally friendly properties and excellent stability to the plasticizer composition. In addition, processing properties such as plasticizing efficiency, light resistance, and absorption rate of the plasticizer composition can be further improved.
[56]
[57]
When the bonding position of the diester group in the cyclohexane is not the 1st or 2nd position, there is a problem that the compression transferability and the stress transferability are typically poor.
[58]
[59]
When the two alkyl groups bonded to the diester group of the cyclohexane-1,2-diester-based material are each independently an alkyl group having 4 to 12 carbon atoms, and when an alkyl group having less than 4 carbon atoms is bonded, heating loss or transition loss characteristics It becomes poor and the absorption rate or gelling is too fast, which may affect processability, and when an alkyl group having more than 12 carbon atoms is bonded, it may adversely affect the elongation or plasticization efficiency. In order to optimize this effect, preferably, an alkyl group having 8 to 12 carbon atoms or an alkyl group having 8 to 10 carbon atoms may be selected.
[60]
[61]
The two alkyl groups bonded to the diester group of the cyclohexane-1,2-diester-based material are each independently n-butyl group, isobutyl group, n-pentyl group, isopentyl group, n-hexyl group, isohex Sil group, n-heptyl group, isoheptyl group, n-octyl group, isooctyl group, 2-ethylhexyl group, n-nonyl group, isononyl group, 2-propylheptyl group, isodecyl group, n-undecyl, iso It may be one selected from the group consisting of undecyl, n-dodecyl and isododecyl, among which is one selected from the group consisting of 2-ethylhexyl group, isononyl group, 2-propaneheptyl group, and isodecyl group. It is desirable.
[62]
[63]
When the cyclohexane-1,2-diester-based material is directly prepared, it can be prepared by direct esterification reaction or transesterification reaction of cyclohexane-1,2-dicarboxylic acid or a derivative thereof and an alcohol.
[64]
[65]
The cyclohexane-1,2-dicarboxylic acid derivative may be at least one selected from the group consisting of an anhydride of cyclohexane-1,2-dicarboxylic acid and an alkyl ester of the cyclohexane-1,2-dicarboxylic acid. The alkyl ester may be an alkyl ester having 1 to 6 carbon atoms.
[66]
[67]
The alcohol is an alcohol having 4 to 12 carbon atoms, may be an alcohol having 8 to 12 carbon atoms or an alcohol having 8 to 10 carbon atoms, among which it is preferably an alcohol having 8 to 10 carbon atoms.
[68]
[69]
In the case of preparing the cyclohexane-1,2-diester-based material by the direct esterification reaction, the alcohol is 2 to 10 mol, 2 to 1 mol 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.
[70]
[71]
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.
[72]
The inorganic acid may be at least one selected from the group consisting of sulfuric acid, hydrochloric acid and phosphoric acid.
[73]
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.
[74]
The Lewis acid is an aluminum derivative (aluminum oxide, aluminum hydroxide), a tin derivative (a 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 one or more selected from the group consisting of.
[75]
[76]
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 derivative thereof and an alcohol, of which 0.01 to It is preferably used in 3 parts by weight.
[77]
[78]
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 sum of cyclohexane-1,2-dicarboxylic acid or a derivative thereof and an alcohol, of which 5 to 200 It is preferably used in parts by weight.
[79]
[80]
The direct esterification reaction may be performed at 100 to 280°C, 130 to 250°C, or 150 to 230°C, of ​​which it is preferably performed at 150 to 230°C.
[81]
[82]
The direct esterification reaction may be performed for 3 to 30 hours or 3 to 25 hours, of which it is preferably performed for 3 to 25 hours.
[83]
[84]
On the other hand, when the cyclohexane-1,2-diester-based material is prepared by a transesterification reaction, it may be prepared by a transesterification reaction of the cyclohexane-1,2-dicarboxylic acid derivative and an alcohol.
[85]
[86]
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. The methyl ester of can be used.
[87]
[88]
With respect to 1 mole of the cyclohexane-1,2-dicarboxylic acid derivative, the alcohol may be used in 2 to 10 moles, 2 to 8 moles, 2 to 6 moles, or 2 to 5 moles, of which 2 to 5 moles It is preferably used.
[89]
[90]
The transesterification reaction may be performed in the presence of a catalyst, and in this case, the reaction time may be shortened.
[91]
The catalyst may be at least one selected from the group consisting of Lewis acids and alkali metals.
[92]
The Lewis acid is as described in the description of the direct esterification reaction.
[93]
The alkali metal may be at least one selected from the group consisting of sodium alkoxide, potassium alkoxide, sodium hydroxide and potassium hydroxide.
[94]
[95]
The catalyst 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 sum of the derivative of cyclohexane-1,2-dicarboxylic acid and alcohol, of which 0.01 to 3 parts by weight It is desirable.
[96]
[97]
The transesterification reaction may be performed at 120 to 250° C., 135 to 230° C., or 140 to 220° C., of which it is preferably performed at 140 to 220° C.
[98]
The transesterification reaction may be performed for 0.5 to 10 hours or 0.5 to 8 hours, of which it is preferably performed for 0.5 to 8 hours.
[99]
[100]
The direct esterification reaction or transesterification reaction further comprises at least one selected from the group consisting of benzene, toluene, xylene and cyclohexane in order to promote the outflow of lower alcohol such as water or methanol generated by the reaction. It can be added, and commercially available nitrogen for the same purpose can be used as an entrainment.
[101]
[102]
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 deactivation treatment (neutralization treatment, base treatment), water washing treatment, distillation (pressure reduction or dehydration treatment), and adsorption purification treatment.
[103]
[104]
Unlike the above manufacturing method, a manufacturing method including converting a dialkyl phthalate-based material into a cyclohexane-1,2-diester-based material by hydrogenating a dialkyl phthalate-based material in the presence of a metal catalyst can be applied.
[105]
The hydrogenation step is a reaction of removing the aromaticity of the benzene ring of the phthalate by adding hydrogen in the presence of a metal catalyst, and may be a kind of reduction reaction.
[106]
The hydrogenation reaction is to synthesize a cyclohexane-1,2-diester-based material by reacting the phthalate-based material with hydrogen in the presence of a metal catalyst, and the reaction conditions do not affect the carbonyl group substituted in benzene. All of the conventional reaction conditions capable of hydrogenating only the benzene ring may be included.
[107]
The hydrogenation reaction may be carried out by further including an organic solvent such as ethanol, but is not limited thereto. As the metal catalyst, an Rh catalyst, a Pt catalyst, a Pd catalyst, and the like, which are generally used to hydrogenate a benzene ring, may be used, but the hydrogenation reaction is not limited thereto.
[108]
[109]
2) Epoxidized alkyl ester composition
[110]
The epoxidized alkyl ester composition is represented by Chemical Formula 1, is environmentally friendly to the plasticizer composition, and can further improve plasticization efficiency, light resistance, and thermal stability.
[111]
[112]
When the epoxidized alkyl ester composition is applied to a plasticizer composition, the iodine value and the oxirane content may be important factors. In particular, in the case of a plasticizer composition included in food packaging materials for which environment-friendly properties are essential, the content of iodine and oxirane may have a great influence on the plasticizer properties.
[113]
The iodine value represents the content of the double bond present in the molecule, and the content of the double bond may be the content of the double bond remaining after the epoxidation reaction such as epoxidation of vegetable oil or epoxidation of fatty acid alkyl ester is performed. have.
[114]
In addition, the oxirane content rate may be changed depending on the number of epoxy groups contained in the substituent represented by R 1 .
[115]
That is, the iodine value and the oxirane content rate may be indices of how much epoxidation has been performed, and thus may be partially related to each other, and theoretically, may be inversely proportional to each other.
[116]
However, in practice, the double bonds of vegetable oils or fatty acid alkyl esters may vary from substance to substance, so the above two parameters do not accurately form an inverse relationship or a trade off relationship, and the iodine number between the two substances is higher. The substance may have a higher oxirane content at the same time. Therefore, it may be desirable to apply the iodine value and oxirane content of the epoxidized fatty acid alkyl ester-based material satisfying the ranges described below to the plasticizer composition used in environmentally friendly food packaging materials.
[117]
[118]
The epoxidized alkyl ester composition may have an iodine value of less than 3.5 I 2 g/100g (hereinafter, the unit'I 2 g/100g' is omitted), 3.2 or less, or 3.0 or less, of which 3.0 or less is preferred. If the above-described conditions are satisfied, the color and transparency of the plasticizer composition may be excellent, adhesion may be improved, and mechanical properties such as tensile strength and elongation may be improved.
[119]
[120]
The epoxidized alkyl ester composition may have an oxirane content (OC) of 3.5% or more, 4.0% or more, 4.2% or more, or 4.5% or more, of which 4.5% is preferable. When the above-described conditions are satisfied, the compatibility between the plasticizer composition and the resin is improved, through which transferability and processability may be improved, and mechanical properties such as tensile strength and elongation may be improved.
[121]
[122]
The quality of the epoxidized alkyl ester compound can be predicted through the iodine number and oxirane content, and an oxirane index (OI) can be used as an index thereof. In general, the oxirane index may be 1.0 or more, 1.5 or more, or 2.0 or more, of which 2.0 or more is preferable.
[123]
[124]
The'oxirane index' is a ratio of the content of oxirane to the iodine value of the epoxidized fatty acid alkyl ester compound, and may be a ratio of a double bond epoxidized by an epoxidation reaction and a residual double bond that has not reacted.
[125]
[126]
The epoxidized alkyl ester composition may include one or more epoxidized Fatty Acid Alkyl Ester (eFAAE), and specifically, one or more compounds represented by Formula 1 may be included.
[127]
The R 2 may be an alkyl group having 4 to 10 carbon atoms or an alkyl group having 4 to 9 carbon atoms, and among them, an alkyl group having 4 to 9 carbon atoms is preferable. If R 2 is an alkyl group having less than 4 carbon atoms, the transferability and heating loss of the plasticizer composition may be considerably poor, and problems such as air pollution through volatilization during processing and a decrease in tensile strength of the finished product may occur. When the R 2 is an alkyl group having more than 10 carbon atoms, the molecular weight is too large, and thus there is a concern that the plasticization efficiency and the transferability due to the decrease in compatibility with the resin may be problematic.
[128]
[129]
R 2 is a butyl group (butyl, abbreviated as B), an isobutyl group (isobutyl, abbreviated as iB), a pentyl group (pentyl, abbreviated as P), a hexyl group (abbreviated as Hx), a heptyl group (heptyl, Abbreviation Hp), isoheptyl (iHp for abbreviation), octyl (nO for abbreviation), 2-ethylhexyl (2-ethylhexyl, EH or O for abbreviation), nonyl group (nonyl for abbreviation) nN), isononyl group (isononyl, abbreviated IN), 6-methyloctyl group (6-methyloctyl, abbreviated MO), decyl group (decyl, abbreviated D), isodecyl group (ID for abbreviation), and It may be one or more selected from the group consisting of 2-propylheptyl group (2-propylheptyl, abbreviated PH), of which butyl group, isobutyl group, 2-ethylhexyl group, octyl group, isononyl group and 2- It may be one or more selected from the group consisting of a propylheptyl group.
[130]
[131]
The epoxidized alkyl ester composition includes an epoxidized alkyl ester composition comprising at least one compound represented by Formula 1, and further comprises a saturated fatty acid alkyl ester composition comprising at least one compound represented by the following Formula 2 Can be:
[132]
[Formula 2]
[133]

[134]
In Formula 2,
[135]
R 3 is an alkyl group having 8 to 20 carbon atoms,
[136]
R 4 is an alkyl group having 4 to 10 carbon atoms.
[137]
[138]
The saturated fatty acid alkyl ester composition containing at least one compound represented by Formula 2 may not contain an epoxy group in R 3 , and epoxidized oil in the process of preparing epoxidized fatty acid alkyl ester using epoxidized oil and alcohol The fatty acid moiety portion of may be various, among which there may be a fatty acid moiety in which an epoxy group is not bonded, and the compound represented by Formula 2 may be a compound resulting from such a fatty acid moiety.
[139]
However, when the content of the saturated fatty acid alkyl ester composition accounts for about 80% by weight or more of the total secondary plasticizer including the epoxidized alkyl ester composition, since a phenomenon of poor compatibility with the vinyl chloride resin may occur, 70% by weight Hereinafter, when it has a content of preferably 50% by weight or less, most preferably 30% by weight or less, compatibility with the resin may be excellent.
[140]
Here, the secondary plasticizer may mean an epoxidized alkyl ester composition including at least one compound represented by Formula 1 among the constituent elements of the plasticizer composition of the present invention.
[141]
[142]
The cyclohexane-1,2-diester-based material and the epoxidized alkyl ester composition have a weight ratio of 99:1 to 1:99, 90:10 to 10:90, 90:10 to 30:70, or 70:30 to 30 :70 may be, of which 90:10 to 30:70 or 70:30 to 30:70 is preferable. If the above-described conditions are satisfied, plasticization efficiency, heating loss, thermal stability, and the like are improved.
[143]
[144]
The epoxidized alkyl ester composition may be a direct esterification or transesterification reaction of an epoxidized oil and an alcohol having 4 to 10 carbon atoms to prepare an epoxidized alkyl ester composition.
[145]
The epoxidized oil may be a compound in which a certain amount of epoxy group is introduced by epoxidation of vegetable oil, and epoxidized soybean oil, epoxidized castor oil, epoxidized linseed oil, epoxidized palm oil, epoxidized stearate, epoxidized oleate It may be at least one selected from the group consisting of eight, epoxidized tall oil, and epoxidized linoleate.
[146]
[147]
The epoxidized oil may be, for example, an epoxidized oil represented by Formula 4 below.
[148]
[Formula 4]
[149]

[150]
[151]
The epoxy oil represented by Formula 4 includes three ester groups and an epoxy group in one molecule.
[152]
When the epoxidized oil represented by Formula 4 and an alcohol having 4 to 10 carbon atoms undergo a transesterification reaction, it can be separated into three ester compounds, and the separated ester compound reacts with the alkyl group of the alcohol to react with the epoxidized alkyl ester It can be made into a composition.
[153]
[154]
The transesterification reaction may be performed at a reaction temperature of 40 to 230°C, 50 to 200°C, or 50 to 180°C for 10 minutes to 10 hours, 30 minutes to 8 hours, or 1 to 6 hours. Within the above temperature and time range, a desired epoxidized alkyl ester-based material can be effectively obtained. In this case, the reaction time may be calculated from the point when the reaction temperature reaches the reaction temperature after heating.
[155]
The transesterification reaction may be carried out under a basic catalyst, an acid catalyst, or a metal catalyst, and in this case, there is an effect of shortening the reaction time.
[156]
The acid catalyst may be, for example, sulfuric acid, methanesulfonic acid, or p-toluenesulfonic acid, and the metal catalyst may be an alkoxide-based organometallic catalyst containing sodium or potassium, for example, a metal oxide catalyst, a metal salt catalyst, or a metal itself. I can.
[157]
The metal component may be, for example, any one selected from the group consisting of sodium, potassium, tin, titanium, and zirconium, or a mixture of two or more of them.
[158]
In addition, a step of separating, washing, and distilling the polyhydric alcohol, reaction by-product, and unreacted alcohol generated after the transesterification reaction may further include removing the reaction by-product.
[159]
In the purification process, specifically, after the transesterification reaction, cooling and standing may be performed at a temperature of 80 to 100° C. for a certain period of time, and in this case, layer separation occurs, and an epoxy-based alkyl ester and alcohol are included in the upper layer. In the lower layer, glycerin and other by-products may be included. Next, neutralization and washing can be induced by introducing an aqueous solution for neutralizing the catalyst to neutralize the catalyst.
[160]
The neutralization and washing process may be performed after first separating the lower layer containing mainly by-products, and during the neutralization and washing process, the by-products of the lower layer may be dissolved in water and discharged, and then unreacted after repeated washing with water. Alcohol and water can be recovered and removed.
[161]
However, depending on the number of carbon atoms in the alcohol used in the transesterification reaction, there may be a need to change the neutralization and washing processes.
[162]
For example, in the case of using butanol having 4 carbon atoms, if the neutralization and washing processes are performed immediately, there is a problem of wastewater generation, and it may be preferable to distill butanol first. However, in this case, since the activity of the catalyst remains, the by-product glycerol and the product, the epoxy-based alkyl ester, react inversely to produce an epoxidized oil-like material such as diglyceride or triglyceride. Therefore, it is necessary to pay attention to the design of the process.
[163]
In addition, as another example, in the case of using 2-ethylhexyl alcohol having 8 carbon atoms, 2-ethylhexyl alcohol has low solubility in water, so there is no problem of wastewater generation. Therefore, in this case, the alcohol is removed after neutralization and washing. In the case of removal, there may be an advantage that neutralization and washing with water after removing the by-product layer of the lower layer can proceed without a fatal problem.
[164]
[165]
3) Citrate-based material
[166]
The citrate-based material is represented by Chemical Formula 3, and the absorption rate, plasticizing efficiency, and migration resistance of the plasticizer composition may be further improved.
[167]
[168]
In Chemical Formula 3, the citrate-based material including an acetyl group instead of a hydroxyl group may reduce physical properties of the plasticizer composition, for example, plasticization efficiency. In addition, in order to treat waste acetic acid generated as a by-product during the manufacture of citrate-based materials, process, time, and equipment cost may be added, which may increase manufacturing cost.
[169]
Accordingly, the citrate-based material containing an acetyl group instead of a hydroxyl group in Chemical Formula 3 decreases the plasticization efficiency compared to the citrate-based material represented by Chemical Formula 3, and the input amount must be increased to overcome this, thereby increasing the product price. Can be. Therefore, a citrate-based material containing an acetyl group is not preferable in various aspects such as marketability, economy, and physical properties.
[170]
[171]
Each of R 5 to R 7 is independently an alkyl group having 4 to 10 carbon atoms, preferably an alkyl group having 4 to 8 carbon atoms or an alkyl group having 5 to 10 carbon atoms. If the above-described conditions are satisfied, since the molecular weight of the citrate-based material is appropriate, the plasticizing efficiency and absorption rate of the plasticizer composition can be further improved. When each of R 5 to R 7 is independently an alkyl group having less than 4 carbon atoms, the tensile strength and heating loss of the plasticizer composition are lowered, resulting in deterioration of the quality of the final product, and the amount of volatilization during processing is relatively increased. In addition to increasing the possibility of adversely affecting the product, it is uneconomical because an excessive amount of the plasticizer composition must be added in an amount to be volatilized to improve this. When the R 5 to R 7 are each independently an alkyl group having more than 10 carbon atoms, the molecular weight of the citrate-based material increases, and the plasticizing efficiency and absorption rate of the plasticizer composition are rather lowered.
[172]
[173]
On the other hand, in the calendering industry in which plasticization efficiency, absorption rate and transferability are key quality factors, the R 5 to R 7 are preferably an alkyl group having 4 to 8 carbon atoms, and more preferably an alkyl group having 4 to 6 carbon atoms. . In addition, in the compound industry in which tensile strength and tensile residual, elongation and elongation residual, and heating loss are the main quality factors, the R 5 to R 7 are preferably an alkyl group having 5 to 10 carbon atoms, and an alkyl group having 8 to 10 carbon atoms. It is more preferable.
[174]
[175]
Each of the R 5 to R 7 is 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 isodecyl group, and may be one selected from the group consisting of, and may be one selected, among which n- At least one selected from the group consisting of a butyl group, an isobutyl group, an n-pentyl group, an isopentyl group 2-ethylhexyl group, and an isononyl group is preferable.
[176]
[177]
Two of R 5 to R 7 may be the same and the other may be different, and in this case, the citrate-based material represented by Formula 3 is an n-butyl group, isobutyl group, n-pentyl group, isopentyl group , It may be a citrate group having a combination substituent of a 2-ethylhexyl group and an isononyl group.
[178]
[179]
The R 5 to R 7 may be the same, and in this case, the citrate-based material represented by Formula 3 is tri n-butyl citrate (TnBC), tri isobutyl citrate (TiBC), and tri n-pentyl sheet Rate (TnPC), triisopentyl citrate (TIPC), trihexyl citrate (THxC), triheptyl citrate (THpC), triisoheptyl citrate (TIHpC), tri(2-ethylhexyl) citrate (TEHC ) And triisononyl citrate (TINC), and triisodecyl citrate (TIDC).
[180]
[181]
The citrate-based material represented by Formula 3 is 1 to 100 parts by weight, 10 to 100 parts by weight, and 10 parts by weight based on 100 parts by weight of the total of the cyclohexane-1,2-diester-based material and the epoxidized alkyl ester composition. It may be included in to 90 parts by weight, or 10 to 70 parts by weight, of which it is preferably included in 10 to 70 parts by weight. If the above-described conditions are satisfied, there is an advantage in that quality such as plasticization efficiency, absorption rate, and migration resistance is improved.
[182]
[183]
When the citrate-based material represented by Formula 3 is directly prepared, citric acid or a derivative thereof and an alcohol may be directly esterified or transesterified.
[184]
[185]
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.
[186]
[187]
The alcohol is an alcohol having 4 to 10 carbon atoms, preferably an alcohol having 4 to 8 carbon atoms or an alcohol having 5 to 10 carbon atoms.
[188]
[189]
When preparing the citrate-based material represented by Formula 3 through the direct esterification reaction or transesterification reaction, the alcohol is 3 to 15 moles, 3 to 12 moles, or It may be used in 3 to 10 moles, of which 3 to 10 moles are preferably used.
[190]
[191]
In addition, the description of the direct esterification reaction and the transesterification reaction is as described in the method for preparing the cyclohexane-1,2-diester-based material.
[192]
[193]
2. Resin composition
[194]
A resin composition according to another embodiment of the present invention comprises 100 parts by weight of a resin; And 5 to 150 parts by weight of a plasticizer composition according to an embodiment of the present invention.
[195]
[196]
The resin may include one or more selected from the group consisting of ethylene-vinyl acetate copolymer, polyethylene, polypropylene, polyketone, polyvinyl chloride, polystyrene, polyurethane, and thermoplastic elastomer, of which polyvinyl chloride It is preferable to include.
[197]
[198]
The resin composition may be 10 to 130 parts by weight, 10 to 100 parts by weight, 10 to 60 parts by weight, or 10 to 50 parts by weight of the plasticizer composition based on 100 parts by weight of the resin, of which 10 to 50 parts by weight is preferable. Do. If the above-described content is satisfied, it is possible to provide a resin composition that is effective in all of the compound resin composition, the calendering resin composition, and the plastisol resin composition.
[199]
[200]
The resin composition may be used to manufacture electric wires, flooring materials, automobile interior materials, films, sheets, or tubes.
[201]
[202]
Hereinafter, embodiments of the present invention will be described in detail so that those of ordinary skill in the art may easily implement the present invention. However, the present invention may be implemented in various different forms, and is not limited to the embodiments described herein.
[203]
[204]
< Preparation of cyclohexane -1,2 -diester-based material>
[205]
Manufacturing Example 1
[206]
516.5 g of cyclohexane-1,2-dicarboxylic acid, 1,296 g of isononyl alcohol, and 1.55 g of tetraisopropyl titanate as a catalyst were added to a 4-neck 3-liter reactor equipped with a cooler, condenser, decanter, reflux pump, temperature controller, stirrer, etc. Then, the reaction temperature was set to 230° C., while nitrogen gas was continuously added, the esterification reaction was performed for about 6 hours, and the reaction was completed when the acid value reached 0.1.
[207]
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 of diisononyl cyclohexane-1,2-dicarboxylate (yield: 97%) was prepared through a neutralization process, a dehydration process, and a filtration process.
[208]
[209]

[210]
Production example 2: the eFAEHE prepared
[211]
Epoxidized Soybean Oil (ESO) with an oxirane content of 6.97% and an iodine value of 1.93 (I 2 g /100g) in a 4-hole 3-liter reactor equipped with a cooler, condenser, decanter, reflux pump, temperature controller, and stirrer. ) 1,000 g, 500 g of 2-ethylhexyl alcohol, and 5.5 g of a metal salt catalyst were added as a catalyst, and the temperature was gradually raised to about 180°C.
[212]
Through gas chromatographic analysis, it was confirmed that the raw material ESO was completely reacted and consumed, and the reaction was terminated. After completion of the reaction, through the steps of removing glycerin as a by-product, removing unreacted raw materials, and purifying the product, finally 1,210 g of an epoxidized fatty acid ethylhexyl ester composition having an oxirane content of 5.21% and an iodine value of 1.70 Got it.
[213]
[214]
Production Example 3: a eFAINE prepared
[215]
An epoxidized fatty acid isononyl ester composition was prepared in the same manner as in Preparation Example 1, except that isononanol was used instead of 2-ethylhexanol. At this time, the epoxidized fatty acid isononyl ester composition had an oxirane content of 5.22% and an iodine value of 1.72.
[216]
[217]
Production Example 4: a eFABE prepared
[218]
An epoxidized fatty acid butyl ester composition was prepared in the same manner as in Preparation Example 1, except that butanol was used instead of 2-ethylhexanol. At this time, the epoxidized fatty acid butyl ester composition had an oxirane content of 5.18% and an iodine value of 1.68.
[219]
[220]
Plasticizer compositions of Examples and Comparative Examples were prepared by mixing the materials prepared in Preparation Examples 1 to 3, and at least one of the materials shown in Table 1 below, and summarized in Table 1 below. Evaluation of physical properties of the plasticizer composition was performed according to the following experimental items. Materials other than those prepared in the above Preparation Example were commercialized products.
[221]
[222]
[Table 1]
division Cyclohexane-1,2-diester-based material Epoxidized Alkyl Ester Composition Citrate material
Kinds Content (parts by weight) Kinds Content (parts by weight) Kinds Content (parts by weight)
Example 1 Manufacturing Example 1 90 Manufacturing Example 2 10 - -
Example 2 Manufacturing Example 1 70 Manufacturing Example 2 30 - -
Example 3 Manufacturing Example 1 50 Manufacturing Example 2 50 - -
Example 4 Manufacturing Example 1 30 Manufacturing Example 2 70 - -
Example 5 Manufacturing Example 1 10 Manufacturing Example 2 90 - -
Example 6 1,2-DEHCH 50 Manufacturing Example 3 50 - -
Comparative Example 1 Manufacturing Example 1 100 - - - -
Comparative Example 2 Manufacturing Example 1 70 eFAME 30 - -
Comparative Example 3 Manufacturing Example 1 70 - - TBC 30
Comparative Example 4 - - Manufacturing Example 3 50 TBC 50
[223]
1,2-DEHCH: di(2-ethylhexyl) cyclohexane-1,2-dicarboxylate (CAS No: 87-71-9)
[224]
TBC: tributyl citrate (CAS No: 77-94-1)
[225]
eFAME: epoxidized fatty acid methyl ester (trade name: HY-S-01, manufacturer: Hebei jingo, CAS No.: 72480-50-3)
[226]
[227]
[Table 2]
division Cyclohexane-1,2-diester-based material Epoxidized Alkyl Ester Composition Citrate material
Kinds Content (parts by weight) Kinds Content (parts by weight) Kinds Content (parts by weight)
Example 7 1,2-DEHCH 60 Manufacturing Example 3 30 TBC 10
Example 8 1,2-DPHCH 40 Manufacturing Example 4 30 TINC 30
Example 9 1,2-DPHCH 60 Manufacturing Example 2 20 TBC 20
Example 10 Manufacturing Example 1 30 Manufacturing Example 2 20 TEHC 50
Example 11 Manufacturing Example 1 80 Manufacturing Example 2 10 ATBC 10
Example 12 1,3-DINCH 80 Manufacturing Example 2 10 ATBC 10
Example 13 1,4-DINCH 80 Manufacturing Example 2 10 ATBC 10
[228]
1,2-DPHCH: di(2-propylheptyl) cyclohexane-1,2-dicarboxylate (LG Chem)
[229]
TEHC: Tris(2-ethylhexyl) citrate (CAS No: 7147-34-4)
[230]
TINC: Tris isononyl citrate (LG Chemical)
[231]
ATBC: acetyltributyl citrate (CAS No: 77-90-7)
[232]
[233]

[234]
Hardness (shore'A', Shore'D') measurement
[235]
According to ASTM D2240, the hardness of the specimen with a thickness of 3 mm was measured for 10 seconds.
[236]
[237]
Measurement of migration loss ( % )
[238]
According to KSM-3156, after attaching a glass plate to both sides of a specimen having a thickness of 1 mm, a load of 1 kgf/cm2 was applied. The specimen was left in a hot air circulation oven (80°C) for 72 hours, then taken out and cooled at room temperature. Thereafter, the glass plates adhered to both sides of the specimen were removed, the weight of the specimen before and after leaving the specimen in an oven was measured, and substituted into the following Equation 1 to calculate the transition loss value.
[239]
[240]

[241]
Transition loss (%) = [(Initial weight of the specimen before leaving the oven)-(Weight of the specimen after leaving the oven)]/ (Initial weight of the specimen before leaving the oven) × 100
[242]
[243]
Heating loss measurement ( % )
[244]
After exposing a specimen having a thickness of 1 mm at 80° C. for 72 hours, the weight of the specimen was measured and substituted into Equation 2 below to calculate a heating loss value.
[245]

[246]
Loss on heating (%) = [(Initial specimen weight)-(Specimen weight after work)]/ (Initial weight of specimen before leaving the oven) × 100
[247]
[248]
Tensile strength measurement ( ㎏f /㎠)
[249]
According to ASTM D638, a specimen having a thickness of 1 mm was pulled at a cross head speed of 200 mm/min using a UTM (brand name: 4466, manufacturer: instron), and then the time point at which the specimen was cut was measured.
[250]
[251]
Elongation measurement ( % )
[252]
According to ASTM D638, a specimen having a thickness of 1 mm was pulled at a cross head speed of 200 mm/min using a UTM (brand name: 4466, manufacturer: instron), and then the time point at which the specimen was cut was measured. And it was substituted into the following formula 3, and the elongation was calculated.
[253]

[254]
Elongation (%): [(length at the time the specimen is cut)/(initial length)]×100
[255]
[256]
Absorption rate
[257]
The absorption rate was evaluated by measuring the time taken to stabilize the torque of the mixer by mixing the resin and the product composition using a planatary mixer (Brabender, P600) under conditions of 77°C and 60 rpm.
[258]
[259]
Experimental Example 1: Evaluation of physical properties
[260]
Specimens were prepared using the plasticizer compositions of Examples and Comparative Examples described in Table 1 above.
[261]
According to ASTM D638, polyvinyl chloride (brand name: LS100, manufacturer: LG Chem) 100 parts by weight, 40 parts by weight of the plasticizer composition prepared in the Examples and Comparative Examples, and a stabilizer (brand name: BZ153T, manufacturer : Songwon Industries) 3 parts by weight are blended, mixed by stirring at 98°C at a speed of 700 rpm, roll milled at 160°C for 4 minutes, and 3 minutes (low pressure) and 2.5 minutes (high pressure) at 180°C using a press A specimen having a thickness of 1 ㎜ and a specimen having a thickness of 3 ㎜ were prepared respectively.
[262]
Each of the test items was evaluated for the specimen, and the results are shown in Table 3 below.
[263]
[Table 3]
division Hardness Performance loss (%) Heating loss (%) Tensile strength (kgf/㎠) Elongation (%) Absorption rate (sec)
Shore'A' Shore'D'
Example 1 94.1 48.3 4.32 0.77 234.9 334.4 402
Example 2 93.2 47.4 4.35 0.70 245.0 341.2 388
Example 3 92.4 46.4 4.65 0.70 244.4 343.3 373
Example 4 91.8 45.6 4.35 0.75 248.3 350.7 351
Example 5 91.3 44.5 4.52 0.73 243.4 359.8 314
Example 6 91.5 44.9 3.24 0.54 247.1 341.3 350
Comparative Example 1 94.5 48.7 4.79 1.00 223.3 314.2 426
Comparative Example 2 90.4 43.5 8.34 10.43 204.6 331.0 284
Comparative Example 3 92.3 46.1 5.16 1.57 246.8 299.2 272
Comparative Example 4 92.4 46.3 5.23 1.66 224.7 287.6 304
[264]
Referring to Table 3, it was confirmed that the plasticization efficiency, transition loss, tensile strength, elongation and absorption rate were all uniformly excellent in Examples 1 to 6.
[265]
On the other hand, in the case of Comparative Example 1 containing only cyclohexane-1,2-diester-based material, plasticization efficiency, transfer loss, heating loss, tensile strength, elongation, and absorption rate were significantly compared to Examples 1 to 6. It could be confirmed that it fell.
[266]
In addition, in the case of Comparative Example 2 containing a cyclohexane-1,2-diester-based material and an epoxidized alkyl ester composition having a carbon number of less than 4, the transition loss, heating loss, and tensile strength were shown in Examples 1 to 6 It was confirmed that the contrast significantly decreased.
[267]
In addition, in the case of Comparative Example 3 containing a cyclohexane-1,2-diester-based material and a citrate-based material, it was confirmed that the transition loss, heating loss, and tensile strength were significantly reduced compared to Examples 1 to 6. Could.
[268]
In addition, in the case of Comparative Example 4 including the epoxidized alkyl ester composition represented by Formula 1 and a citrate-based material, the transition loss, heating loss, tensile strength and elongation were significantly lowered compared to Examples 1 to 6. I could confirm that.
[269]
[270]
Experimental Example 2: Evaluation of physical properties
[271]
Specimens were prepared using the plasticizer compositions of Examples and Comparative Examples described in Table 2 above.
[272]
The specimen preparation was carried out in the same manner as in Experimental Example 1, and the experimental items were evaluated for the specimen under the same conditions as in Experimental Example 1, and the results are shown in Table 4 below.
[273]
[Table 4]
division Hardness Performance loss (%) Heating loss (%) Tensile strength (㎏/㎠) Elongation (%) Absorption rate (sec)
Shore'A' Shore'D'
Example 7 90.2 43.8 2.88 0.82 249.8 357.4 332
Example 8 92.4 46.5 2.64 0.92 245.7 345.1 324
Example 9 91.2 44.3 2.47 0.63 240.9 364.5 342
Example 10 91.7 45.0 1.86 0.34 256.0 348.7 417
Example 11 94.5 48.6 4.01 0.75 236.3 334.0 430
Example 12 93.8 48.0 4.50 0.73 220.5 318.6 478
Example 13 93.0 47.6 5.11 0.70 207.3 302.4 516
[274]
Referring to Table 4, since Examples 7 to 10 further comprise the citrate-based material represented by Chemical Formula 3, it can be seen that the transition loss was significantly improved compared to Examples 1 to 6 of Experimental Example 1. there was.
[275]
On the other hand, Examples 11 to 13 are superior in physical properties as compared to Comparative Examples 1 to 4 as a whole by including the cyclohexane-1,2-diester-based material and the epoxidized alkyl ester composition represented by Formula 1 above. Although there is a possibility to say that, in that a citrate-based material containing an acetyl group was applied as the citrate-based material, it can be seen that the plasticization efficiency became poor (the hardness was increased) and the absorption rate was slow, resulting in poor processability It can be seen that the transition characteristics are poor (increased transition loss) and the tensile strength and elongation are also poor in physical properties, so that there is no advantage in all aspects compared to Examples 7 to 10, but rather, the damage in terms of physical properties is somewhat large.
[276]
Accordingly, in the case of applying a citrate-based material as a third plasticizer, it is possible to take advantage of the basic process (e.g., waste acetic acid treatment) to apply a citrate-based material, and that there is a considerable advantage in plasticizer properties. Can be seen.
Claims
[Claim 1]
A cyclohexane-1,2-diester-based material in which two alkyl groups bonded to the diester group are each independently an alkyl group having 4 to 12 carbon atoms; And a plasticizer composition comprising an epoxidized alkyl ester composition comprising at least one compound represented by the following formula (1). [Chemical Formula 1] In Formula 1, R 1 is an alkyl group having 8 to 20 carbon atoms including one or more epoxy groups, and R 2 is an alkyl group having 4 to 10 carbon atoms.
[Claim 2]
The plasticizer composition of claim 1, wherein the cyclohexane-1,2-diester-based material and the epoxidized alkyl ester composition have a weight ratio of 99:1 to 1:99.
[Claim 3]
The method according to claim 1, wherein the alkyl groups bonded to the diester group of the cyclohexane-1,2-diester-based material are each independently n-butyl group, isobutyl group, n-pentyl group, isopentyl group, n-hex Sil group, isohexyl group, n-heptyl group, isoheptyl group, n-octyl group, isooctyl group, 2-ethylhexyl group, n-nonyl group, isononyl group, 2-propylheptyl group, isodecyl group, n- A plasticizer composition that is one selected from the group consisting of undecyl, isoundecyl, n-dodecyl and isododecyl.
[Claim 4]
The plasticizer composition of claim 1, wherein the epoxidized alkyl ester composition has an iodine value of less than 3.5 I 2 g/100 g.
[Claim 5]
The plasticizer composition of claim 1, wherein the epoxidized alkyl ester composition has an oxirane content (OC) of 3.5% or more.
[Claim 6]
The plasticizer composition of claim 1, wherein R 2 is selected from the group consisting of a butyl group, an isobutyl group, a 2-ethylhexyl group, an octyl group, an isononyl group, and a 2-propylheptyl group.
[Claim 7]
The method according to claim 1, wherein the epoxidized alkyl ester composition comprises an epoxidized alkyl ester composition comprising at least one compound represented by Formula 1, and a saturated fatty acid alkyl ester comprising at least one compound represented by the following Formula 2 Plasticizer composition further comprising the composition: [Formula 2] In Formula 2, R 3 is an alkyl group having 8 to 20 carbon atoms, and R 4 is an alkyl group having 4 to 10 carbon atoms.
[Claim 8]
The plasticizer composition of claim 1, wherein the plasticizer composition further comprises a citrate-based material represented by Formula 3: [Formula 3] In Formula 3, R 5 to R 7 are each independently an alkyl group having 4 to 10 carbon atoms to be.
[Claim 9]
The plasticizer composition of claim 8, wherein R 5 to R 7 are each independently an alkyl group having 4 to 8 carbon atoms.
[Claim 10]
The plasticizer composition of claim 8, wherein R 5 to R 7 are each independently an alkyl group having 5 to 10 carbon atoms.
[Claim 11]
The method according to claim 8, wherein R 5 to R 7 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 isodecyl group consisting of one kind selected from the group consisting of a plasticizer composition.
[Claim 12]
The plasticizer of claim 8, comprising 1 to 100 parts by weight of the citrate-based material represented by Formula 3 based on 100 parts by weight of the total of the cyclohexane-1,2-diester-based material and the epoxidized alkyl ester composition. Composition.
[Claim 13]
100 parts by weight of resin; And a resin composition comprising 5 to 150 parts by weight of the plasticizer composition according to claim 1.
[Claim 14]
The resin composition according to claim 13, 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. .