The present invention claims the benefit of priority based on Korean Patent Application No. 10-2018-0067038, filed on June 11, 2018 and Korean Patent Application No. 10-2019-0063854, filed on May 30, 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.
[5]
background
[6]
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.
[7]
On the other hand, in the compound industry in which high heat resistance and low heat loss are the main required properties, it is necessary to use an appropriate plasticizer in consideration of the required properties. In the case of PCV compounds for use in wires and cables, third materials such as plasticizers, stabilizers, and pigments are mixed with PVC resin according to the characteristics required by the relevant standards, such as tensile strength, elongation, plasticization efficiency, heat loss, and tensile and elongation residual ratio. do.
[8]
At present, general-purpose products used in various extrusion, injection, calendering and compound industries such as electric wires, flooring materials, automobile interior materials, films, hoses and tubes include diisononyl phthalate (DINP) or diisodecyl phthalate (DIDP). Phthalate products are widely used.
[9]
However, these phthalate products are regulated or need to be regulated depending on the purpose of the product. Although it is used for general purpose, improvement is required in terms of quality.
[10]
In response to these environmental issues and the demand for quality improvement equivalent to or higher than that of existing products, it is necessary to develop new products that can improve the quality of existing products while maintaining eco-friendliness as the basis. By developing a novel plasticizer composition product that is environmentally friendly while having
[11]
DETAILED DESCRIPTION OF THE INVENTION
technical challenge
[12]
The present invention has been derived to solve the problems of the prior art, and when used as a plasticizer of a resin composition, a plasticizer composition that can improve physical properties such as plasticization efficiency, heat loss, light resistance, thermal stability and transferability to an excellent level; An object of the present invention is to provide a resin composition comprising the same.
[13]
means of solving the problem
[14]
In order to solve the above problems, the present invention provides a cyclohexane-1,4-diester-based material represented by the following formula (1); an epoxidized alkyl ester composition comprising at least one compound represented by the following formula (2); And it provides a plasticizer composition comprising a citrate-based material represented by the following formula 3:
[15]
[Formula 1]
[16]

[17]
[Formula 2]
[18]

[19]
[Formula 3]
[20]

[21]
[22]
In Formulas 1 to 3,
[23]
R 1 and R 2 are each independently an alkyl group having 8 carbon atoms,
[24]
R 3 is an alkyl group having 8 to 20 carbon atoms including at least one epoxy group,
[25]
R 4 to R 7 are each independently an alkyl group having 4 to 10 carbon atoms.
[26]
[27]
In addition, the present invention is 100 parts by weight of the resin; and 5 to 150 parts by weight of the plasticizer composition.
[28]
Effects of the Invention
[29]
The plasticizer composition according to an embodiment of the present invention can provide a plasticizer composition that can improve physical properties such as plasticization efficiency, heat loss, light resistance and heat resistance to an excellent level when used in a resin composition.
[30]
Best mode for carrying out the invention
[31]
Hereinafter, the present invention will be described in more detail to help the understanding of the present invention.
[32]
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.
[33]
[34]
The compound name used herein may be a commonly used name, and is named according to a substituent characteristically bonded to each compound. can be understood as being
[35]
[36]
As used herein, the term “alkyl group” does not have any limitation other than the number of carbon atoms unless otherwise specified, and may be understood as a straight-chain or branched-chain type.
[37]
[38]
In the present invention, the iodine number may be measured according to ASTM D5768-02.
[39]
[40]
In the present invention, the oxirane content may be measured according to ASTM D1652-04.
[41]
[42]
As used herein, the term "straight vinyl chloride polymer" is one of the types of vinyl chloride polymer, and may mean polymerization through suspension polymerization or bulk polymerization, and a large amount of pores having a size of tens to hundreds of micrometers. It refers to a polymer that has a form of distributed porous particles, has no cohesiveness, and has excellent flowability.
[43]
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, and has a size of tens to thousands of nanometers. It refers to a polymer with poor flowability and cohesiveness as particles without fine and dense pores.
[44]
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', unless stated to the contrary, contain 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.
[45]
[46]
1. Plasticizer composition
[47]
The plasticizer composition according to an embodiment of the present invention comprises: 1) a cyclohexane-1,4-diester-based material represented by the following Chemical Formula 1; 2) an epoxidized alkyl ester composition comprising at least one compound represented by the following formula (2); and 3) a citrate-based material represented by the following Chemical Formula 3:
[48]
[Formula 1]
[49]

[50]
[Formula 2]
[51]

[52]
[Formula 3]
[53]

[54]
[55]
In Formulas 1 to 3,
[56]
R 1 and R 2 are each independently an alkyl group having 8 carbon atoms,
[57]
R 3 is an alkyl group having 8 to 20 carbon atoms including at least one epoxy group,
[58]
R 4 to R 7 are each independently an alkyl group having 4 to 10 carbon atoms.
[59]
[60]
Hereinafter, components of the plasticizer composition according to an embodiment of the present invention will be described in detail.
[61]
[62]
1) Cyclohexane- 1,4 -diester-based material
[63]
The cyclohexane-1,4-diester-based material is represented by Chemical Formula 1, and may impart environmental-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 may be further improved.
[64]
[65]
If the bonding position of the diester group in cyclohexane is not at the 1 or 4 position, there is a problem in that the plasticization efficiency and heating loss are poor.
[66]
[67]
In Formula 1, when R 1 and R 2 are an alkyl group having 9 or more carbon atoms, plasticization efficiency and transferability are poor. increased, and this can lead to air pollution problems.
[68]
[69]
In Formula 1, R 1 and R 2 may each independently be one selected from the group consisting of an n-octyl group, an isooctyl group, and a 2-ethylhexyl group, and may be the same as or different from each other.
[70]
The cyclohexane-1,4-diester-based material may be dioctyl cyclohexane-1,4-dicarboxylate or di(2-ethylhexyl) cyclohexane-1,4-dicarboxylate.
[71]
[72]
The cyclohexane-1,4-diester-based material may be included in an amount of 10 to 90% by weight, 20 to 90% by weight, or 30 to 80% by weight, of which 30 to 80% by weight, based on the total weight of the plasticizer composition. It is preferably included in %. If the above conditions are satisfied, there is an advantage in that it is possible to provide a resin composition having good mechanical properties such as plasticization efficiency, heat loss, light resistance, tensile strength, and elongation.
[73]
[74]
When the cyclohexane-1,4-diester-based material is directly prepared, the cyclohexane-1,4-dicarboxylic acid or derivative thereof and alcohol may be prepared by direct esterification or transesterification.
[75]
[76]
The derivative of cyclohexane-1,4-dicarboxylic acid may be at least one selected from the group consisting of an anhydride of cyclohexane-1,4-dicarboxylic acid and an alkyl ester of cyclohexane-1,4-dicarboxylic acid. The alkyl ester may be an alkyl ester having 1 to 6 carbon atoms.
[77]
[78]
The alcohol is an alkyl alcohol having 8 carbon atoms.
[79]
[80]
When the cyclohexane-1,4-diester-based material represented by Formula 1 is prepared by the direct esterification reaction, the alcohol is 2 with respect to 1 mole of the cyclohexane-1,4-dicarboxylic acid or its derivative to 10 moles, 2 to 8 moles, 2 to 6 moles, or 2 to 5 moles may be used, and 2 to 5 moles of these may be used.
[81]
[82]
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.
[83]
The inorganic acid may be at least one selected from the group consisting of sulfuric acid, hydrochloric acid and phosphoric acid.
[84]
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.
[85]
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.
[86]
[87]
When the catalyst is a homogeneous catalyst, 0.01 to 5 parts by weight or 0.01 to 3 parts by weight may be used in an amount of 0.01 to 5 parts by weight or 0.01 to 3 parts by weight based on 100 parts by weight of the total of the cyclohexane-1,4-dicarboxylic acid or derivative thereof and the alcohol. It is preferably used in 3 parts by weight.
[88]
[89]
When the catalyst is a heterogeneous catalyst, 5 to 200 parts by weight or 5 to 100 parts by weight may be used, of which 5 to 200 parts by weight, based on 100 parts by weight of the total of cyclohexane-1,4-dicarboxylic acid or a derivative thereof and alcohol. It is preferably used in parts by weight.
[90]
[91]
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.
[92]
[93]
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.
[94]
[95]
On the other hand, when the cyclohexane-1,4-diester-based material represented by Chemical Formula 1 is prepared by the transesterification reaction, the transesterification reaction of the cyclohexane-1,4-dicarboxylic acid derivative with the alcohol is used. can be manufactured.
[96]
[97]
The derivative of cyclohexane-1,4-dicarboxylic acid may be an alkyl ester of cyclohexane-1,4-dicarboxylic acid, and preferably cyclohexane-1,4-dicarboxylic acid to facilitate separation of the reaction product. methyl esters of
[98]
[99]
Based on 1 mole of the derivative of cyclohexane-1,4-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
[100]
[101]
The transesterification reaction may be performed in the presence of a catalyst, and in this case, the reaction time may be shortened.
[102]
The catalyst may be at least one selected from the group consisting of a Lewis acid and an alkali metal.
[103]
The Lewis acid is as described in the description of the direct esterification reaction.
[104]
The alkali metal may be at least one selected from the group consisting of sodium alkoxide, potassium alkoxide, sodium hydroxide and potassium hydroxide.
[105]
[106]
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-1,4-dicarboxylic acid derivative and the alcohol. it is preferable
[107]
[108]
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.
[109]
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.
[110]
[111]
In the direct esterification reaction or transesterification reaction, at least one selected from the group consisting of benzene, toluene, xylene and cyclohexane is added to promote the outflow of lower alcohols such as water or methanol produced by the reaction. It can be added, and commercially available nitrogen, etc. can be used as entrainment for the same purpose.
[112]
[113]
The cyclohexane-1,4-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.
[114]
[115]
Unlike the above manufacturing method, a manufacturing method comprising the step of converting a dialkyl terephthalate-based material into a cyclohexane-1,4-diester-based material by hydrogenating the dialkyl terephthalate-based material in the presence of a metal catalyst may be applied.
[116]
The hydrogenation step is a reaction for removing the aromaticity of the benzene ring of terephthalate by adding hydrogen in the presence of a metal catalyst, and may be a kind of reduction reaction.
[117]
The hydrogenation reaction reacts the terephthalate-based material with hydrogen in the presence of a metal catalyst to synthesize a cyclohexane-1,4-diester-based material represented by Chemical Formula 1, and the reaction conditions are benzene-substituted. All conventional reaction conditions capable of hydrogenating only the benzene ring without affecting the carbonyl group may be included.
[118]
The hydrogenation reaction may be carried out 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, 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.
[119]
[120]
2) epoxidized alkyl ester composition
[121]
The epoxidized alkyl ester composition is represented by Chemical Formula 2, and is environmentally friendly to the plasticizer composition, and can further improve plasticization efficiency, light resistance and heat resistance.
[122]
[123]
When the epoxidized alkyl ester composition is applied to the plasticizer composition, the iodine number and the oxirane content may be important factors. In particular, in the case of a plasticizer composition included in packaging materials for food, etc., in which eco-friendly properties are essential, the iodine number and oxirane content may have a significant effect on the plasticizer properties.
[124]
The iodine number represents the content of double bonds present in the molecule, and the content of the double bonds may be the content of double bonds remaining after epoxidation such as epoxidation of vegetable oil or epoxidation of fatty acid alkyl esters. have.
[125]
In addition, the oxirane content may be changed according to the number of epoxy groups contained in the substituent represented by R 3 .
[126]
That is, the iodine number and the oxirane content rate may be indicators 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.
[127]
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 form an exact inverse or trade-off relationship, and between the two substances, the higher iodine number The material may also have a higher oxirane content at the same time. Therefore, it may be preferable to apply a plasticizer composition used in an environmentally friendly food packaging material that satisfies the iodine number and oxirane content of the epoxidized fatty acid alkyl ester-based material within the ranges described below.
[128]
[129]
The epoxidized alkyl ester composition may have an iodine number of less than 3.5 I 2 g/100 g (hereinafter, the unit “I 2 g/100 g” is omitted), 3.2 or less, or 3.0 or less, of which 3.0 or less is preferable. If the above conditions are satisfied, the color of the plasticizer composition is suitable for use as a food packaging material, and mechanical properties such as tensile strength and elongation may be improved together.
[130]
[131]
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. If the above conditions are satisfied, compatibility between the plasticizer composition and the resin is improved, and thus transferability and processability may be improved, and mechanical properties such as tensile strength and elongation may also be improved.
[132]
[133]
The quality of the epoxidized alkyl ester compound can be predicted through the iodine value and the oxirane content, and an oxirane index (OI) can be utilized 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.
[134]
[135]
The 'oxirane index' is a ratio of an oxirane content to an iodine number 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 does not react.
[136]
[137]
The epoxidized alkyl ester composition may include at least one epoxidized Fatty Acid Alkyl Ester (eFAAE), and specifically, at least one compound represented by Formula 2 may be included.
[138]
R 3 may be represented by , L 1 and L 2 are each an alkylene group having 1 to 10 carbon atoms, R 10 is an alkyl group having 1 to 19 carbon atoms, n may be 0 to 5, where L 1 , L The sum of carbon numbers of 2 and R 10 is 8 to 20. Preferably, L 1 is an alkylene group having 5 to 10 carbon atoms, L 2 is an alkylene group having 1 to 3 carbon atoms, and R 10 is an alkyl group having 1 to 10 carbon atoms.
[139]
R 4 may be an alkyl group having 4 to 10 carbon atoms or an alkyl group having 4 to 9 carbon atoms, of which an alkyl group having 4 to 9 carbon atoms is preferable. When R 4 is an alkyl group having less than 4 carbon atoms, the transferability and heat loss of the plasticizer composition may be considerably poor, and problems such as air pollution through volatilization during processing and lowering of the tensile strength of the finished product may occur. When R 4 is an alkyl group having more than 10 carbon atoms, since the molecular weight is too large, there is a fear that plasticization efficiency or transferability due to a decrease in compatibility with the resin may become a problem.
[140]
[141]
R 4 is a butyl group (butyl, abbreviation B), isobutyl group (isobutyl, abbreviation iB), pentyl group (pentyl, abbreviation P), isopentyl group (isopentyl, abbreviation iP), hexyl group (hexyl) , abbreviation Hx), isohexyl group (abbreviation iHx), heptyl group (heptyl, abbreviation Hp), isoheptyl group (isoheptyl, abbreviation iHp), octyl group (octyl, abbreviation nO), isooctyl group (isooctyl, abbreviation iO), 2-ethylhexyl group (2-ethylhexyl, abbreviation EH or O), nonyl group (nonyl, abbreviation nN), isononyl group (isononyl, abbreviation iN), 6-methylox Tyl group (6-methyloctyl, abbreviation MO), decyl group (decyl, abbreviation D), decyl group (decyl, abbreviation D), isodecyl group (isodecyl, abbreviation iD) and 2-propylheptyl group (2- It may be at least one selected from the group consisting of propylheptyl, abbreviation PH), of which a butyl group, an isobutyl group, a 2-ethylhexyl group, an octyl group, an isononyl group, and a 2-propylheptyl group selected from the group consisting of There may be more than one type.
[142]
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.
[143]
[144]
The epoxidized alkyl ester composition may include at least one compound represented by the following Chemical Formulas 2-1 to 2-18:
[145]

[146]

[147]

[148]

[149]

[150]

[151]

[152]

[153]

[154]

[155]

[156]

[157]

[158]

[159]

[160]

[161]

[162]

[163]

[164]

[165]

[166]

[167]

[168]

[169]

[170]

[171]

[172]

[173]

[174]

[175]

[176]

[177]

[178]

[179]

[180]

[181]
[182]
The epoxidized alkyl ester composition comprises an epoxidized alkyl ester composition comprising at least one compound represented by the formula (2), and further comprises a saturated fatty acid alkyl ester composition comprising at least one compound represented by the following formula (4) can:
[183]
[Formula 4]
[184]

[185]
In Formula 4,
[186]
R 8 is an alkyl group having 8 to 20 carbon atoms,
[187]
R 9 is an alkyl group having 4 to 10 carbon atoms.
[188]
[189]
The saturated fatty acid alkyl ester composition containing at least one compound represented by Formula 4 may not include an epoxy group in R 8 , and in the process of preparing an epoxidized fatty acid alkyl ester using an epoxidized oil and an alcohol, an epoxidized oil The fatty acid moiety portion of may be varied, among which there may be a fatty acid moiety to which an epoxy group is not bonded, and the compound represented by Formula 4 may be a compound resulting from such a fatty acid moiety.
[190]
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, compatibility with the vinyl chloride resin may deteriorate, so 70 weight % or less, preferably 50 wt% or less, and most preferably 30 wt% or less, compatibility with the resin may be excellent.
[191]
Here, the secondary plasticizer may refer to an epoxidized alkyl ester composition comprising at least one compound represented by Formula 2 among components of the plasticizer composition of the present invention.
[192]
[193]
The epoxidized alkyl ester composition may further include at least one compound represented by the following Chemical Formulas 4-1 to 4-12.
[194]

[195]

[196]

[197]

[198]

[199]

[200]

[201]

[202]

[203]

[204]

[205]

[206]

[207]

[208]

[209]

[210]

[211]

[212]

[213]

[214]

[215]

[216]

[217]

[218]
[219]
The epoxidized alkyl ester composition may be included in an amount of 5 to 70 wt%, 5 to 60 wt%, or 10 to 50 wt%, based on the total weight of the plasticizer composition, of which 10 to 50 wt% is preferable. do. When the above-described conditions are satisfied, there is an advantage in that plasticization efficiency, heating loss and thermal stability are improved.
[220]
[221]
The epoxidized alkyl ester composition may be prepared by directly esterifying or trans-esterifying an epoxidized oil and an alcohol having 4 to 10 carbon atoms to prepare an epoxidized alkyl ester composition.
[222]
The epoxidized oil may be a compound in which a certain amount of an epoxy group is introduced by subjecting a vegetable oil to an epoxidation reaction, and epoxidized soybean oil, epoxidized castor oil, epoxidized linseed oil, epoxidized palm oil, epoxidized stearate, and epoxidized oleate. It may be at least one selected from the group consisting of ate, epoxidized tall oil, and epoxidized linoleate.
[223]
[224]
The epoxidized oil may be, for example, at least one of epoxidized oils represented by the following Chemical Formulas 5 to 11.
[225]
[Formula 5]
[226]

[227]
[Formula 6]
[228]

[229]
[Formula 7]
[230]

[231]
[Formula 8]
[232]

[233]
[Formula 9]
[234]

[235]
[Formula 10]
[236]

[237]
[Formula 11]
[238]

[239]
[240]
The epoxy oil represented by Chemical Formulas 5 to 11 includes three ester groups and one or more epoxy groups in one molecule.
[241]
When the epoxidized oil represented by Chemical Formulas 5 to 11 and the 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 an alkyl group of the alcohol to be epoxidized alkyl ester compositions.
[242]
[243]
The transesterification reaction may be carried out 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.
[244]
A desired epoxidized alkyl ester-based material can be effectively obtained within the above temperature and time ranges. In this case, the reaction time may be calculated from the point at which the reaction temperature is reached after the reactant is heated.
[245]
The transesterification reaction may be carried out under a basic catalyst, an acid catalyst, or a metal catalyst, and in this case, the reaction time is shortened.
[246]
The acid catalyst may be, for example, sulfuric acid, methanesulfonic acid or p-toluenesulfonic acid, and the metal catalyst is an alkoxide-based organometallic catalyst, metal oxide catalyst, metal salt catalyst or metal itself containing, for example, sodium or potassium. can
[247]
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 thereof.
[248]
In addition, the method may further include removing the polyhydric alcohol, reaction by-product, and unreacted alcohol generated after the transesterification reaction by separating, washing, and distilling the reaction by-product.
[249]
In the purification process, specifically, after the transesterification reaction, cooling and standing for a predetermined time at a temperature of 80 to 100° C. may be performed, and in this case, layer separation occurs, and the upper layer contains an epoxy-based alkyl ester and alcohol. and glycerin and other by-products may be included in the lower layer. Next, neutralization and washing with water can be induced by adding an aqueous solution for catalyst neutralization to neutralize the catalyst.
[250]
The neutralization and washing process may be performed after first separating the lower layer mainly containing by-products, and the by-products of the lower layer may be dissolved in water and discharged during the neutralization and water washing process, and thereafter, unreacted after repeatedly washing with water Alcohol and water can be recovered and removed.
[251]
However, depending on the number of carbon atoms of the alcohol used in the transesterification reaction, it may be necessary to change the neutralization and water washing processes.
[252]
For example, in the case of using butanol having 4 carbon atoms, if the neutralization and water washing processes are immediately performed, there is a problem of wastewater generation, so it may be preferable to first remove the butanol by distillation. However, in this case, since the activity of the catalyst remains, the reverse reaction of glycerol as a by-product and an epoxy-based alkyl ester as a product may also pose a double problem in that an epoxidized oil-like substance such as diglyceride or triglyceride may be produced again. Therefore, it is necessary to pay attention to the design of the process.
[253]
In addition, as another example, when using 2-ethylhexyl alcohol having 8 carbon atoms, 2-ethylhexyl alcohol has low solubility in water, so there is no problem in generating wastewater. In the case of removal, there may be an advantage that both neutralization and washing after removing the by-product layer of the lower layer can proceed without fatal problems.
[254]
[255]
3) Citrate-based materials
[256]
The citrate-based material is represented by Chemical Formula 3, and may further improve the absorption rate, plasticization efficiency, migration resistance, and the like of the plasticizer composition.
[257]
[258]
In Chemical Formula 3, when a citrate-based material containing an acetyl group is used instead of a hydroxyl group, physical properties of the plasticizer composition, for example, plasticization efficiency may be reduced. In addition, in order to treat waste acetic acid generated as a by-product during the production of a citrate-based material, a process, time, and equipment cost may be added, which may increase the manufacturing cost.
[259]
Accordingly, in the citrate-based material containing an acetyl group instead of a hydroxyl group in Chemical Formula 3, the plasticization efficiency is lowered compared to the citrate-based material represented by Chemical Formula 3, and an input amount must be increased to overcome this, and the product price increases. can be Therefore, a citrate-based material containing an acetyl group is not preferable in various aspects such as marketability, economic efficiency, and physical properties.
[260]
[261]
R 5 to R 7 are each 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.
[262]
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.
[263]
When R 5 to R 7 are each independently an alkyl group having less than 4 carbon atoms, the tensile strength and heating loss of the plasticizer composition are lowered, and thereby the quality of the final product is deteriorated, and the amount of volatilization during processing is relatively increased and the atmosphere In addition to increasing the possibility of adversely affecting the , it is uneconomical because an excessive amount of the plasticizer composition must be added as much as the volatilized amount in order to improve it.
[264]
When 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, so that the plasticizing efficiency and absorption rate of the plasticizer composition are rather reduced.
[265]
[266]
On the other hand, in the calendering industry in which plasticization efficiency, absorption rate and transferability are major quality factors, 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 residual tensile rate, elongation and elongation residual rate, and heating loss are major quality factors, 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. more preferably.
[267]
[268]
wherein R 5 to R 7 are each independently an n-butyl group, an isobutyl group, an n-pentyl group, an isopentyl group, an n-hexyl group, an isohexyl group, an n-heptyl group, an isoheptyl group, and a n-octyl group , isooctyl group, 2-ethylhexyl group, n-nonyl group, isononyl group, 2-propylheptyl group and may be one selected from the group consisting of isodecyl group, of which n-butyl group, isobutyl group, At least one selected from the group consisting of an n-pentyl group, an isopentyl group, a 2-ethylhexyl group, and an isononyl group is preferable.
[269]
[270]
Two of R 5 to R 7 may be the same and the other one may be different. In this case, the citrate-based material represented by Chemical Formula 3 is n-butyl group, isobutyl group, n-pentyl group, and isopentyl group. , a citrate group having a combination substituent of a 2-ethylhexyl group and an isononyl group.
[271]
[272]
R 5 to R 7 may be the same as each other, and in this case, the citrate-based material represented by Chemical Formula 3 is tri n-butyl citrate (TnBC), tri-isobutyl citrate (TiBC), and tri n-pentyl sheet. Late (TnPC), triisopentyl citrate (TIPC), trihexyl citrate (THxC), triheptyl citrate (THpC), triisoheptyl citrate (TIHpC), tri(2-ethylhexyl)citrate (TEHC) ) and triisononyl citrate (TINC), and may be at least one selected from the group consisting of triisodecyl citrate (TIDC).
[273]
[274]
The citrate-based material may be included in an amount of 5 to 70 wt%, 5 to 60 wt%, or 10 to 50 wt%, based on the total weight of the plasticizer composition, of which 10 to 50 wt% is preferable. .
[275]
When the above-mentioned conditions are satisfied, there is an advantage in that the quality such as plasticization efficiency, absorption rate and migration resistance is improved.
[276]
[277]
When the citrate-based material represented by Formula 3 is directly prepared, it may be prepared by direct esterification or transesterification reaction between citric acid or a derivative thereof and alcohol.
[278]
[279]
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.
[280]
[281]
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.
[282]
[283]
When the citrate-based material represented by Formula 3 is prepared by the direct esterification reaction or the transesterification reaction, the alcohol is contained in an amount of 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.
[284]
[285]
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-1,4-diester-based material represented by Chemical Formula 1 above.
[286]
[287]
Meanwhile, the sum of the carbon number of the alkyl group of R 4 and the average number of carbon atoms of the alkyl group of R 8 to R 7 may be 10 to 15. When the above-mentioned range is satisfied, the plasticizing efficiency is excellent, and the transfer loss, the heating loss, the tensile strength, the absorption rate, and the heat resistance can be further improved. However, if it is less than the above-mentioned range, the transition loss, tensile strength and elongation may be significantly reduced. If the above-mentioned range is exceeded, the transition loss, tensile strength, elongation, and absorption rate may be significantly lowered.
[288]
[289]
2. Resin composition
[290]
The 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 the plasticizer composition according to an embodiment of the present invention.
[291]
[292]
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.
[293]
[294]
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.
[295]
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.
[296]
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.
[297]
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.
[298]
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.
[299]
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.
[300]
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.
[301]
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
[302]
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.
[303]
[304]
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 various different forms and is not limited to the embodiments described herein.
[305]
[306]
Preparation Example 1
[307]
516.5 g of cyclohexane-1,4-dicarboxylic acid, 1,170 g of 2-ethylhexanol, 1.55 tetraisopropyl titanate as catalyst g was added, the reaction temperature was set to 230 °C, and nitrogen gas was continuously added, the esterification reaction was performed for 6 hours, and the reaction was completed when the acid value reached 0.1.
[308]
After completion of the reaction, in order to remove unreacted raw materials, distillation extraction was performed under reduced pressure. After distillation extraction, 1,154 g (yield: 97%) of di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate (1,4-DEHCH) was prepared through a neutralization process, a dehydration process, and a filtration process .
[309]
[310]
Production example 2: the eFABE prepared
[311]
Epoxidized Soybean Oil with oxirane content of 6.97% and iodine number of 1.93 (I 2 g/100 g) in a 4-neck 3-liter reactor equipped with a cooler, condenser, decanter, reflux pump, temperature controller, and agitator. ESO) 1,000 g, butanol 500 g, and tetra(n-butyl) titanate 5.5 g as a catalyst were added, and the temperature was gradually raised to about 180°C.
[312]
Through gas chromatograph analysis, it was confirmed that the raw material ESO was completely reacted and consumed, and the reaction was terminated. After completion of the reaction, a step of removing glycerin as a by-product, a step of removing unreacted raw materials, and a step of purifying the product, and finally the oxirane content is 5.18%, the iodine number is 1.68, and the following formulas 2-1 and 2- 1,160 g of an epoxidized fatty acid butyl ester composition (eFABE) containing a compound represented by 2, 2-3, 4-1 and 4-2 was obtained.
[313]

[314]

[315]

[316]

[317]

[318]

[319]

[320]

[321]

[322]

[323]
[324]
Production Example 3: a eFAPE prepared
[325]
An epoxidized fatty acid pentyl ester composition was prepared in the same manner as in Preparation Example 2, except that 500 g of 1-pentanol was used instead of butanol. In this case, the epoxidized fatty acid pentyl ester composition had an oxirane content of 5.51%, an iodine value of 1.40, and a compound represented by the following formulas 2-4, 2-5, 2-6, 4-1 and 4-2. 1,180 g of an epoxidized fatty acid pentyl ester composition (eFAPE) was obtained.
[326]

[327]

[328]

[329]

[330]

[331]

[332]

[333]

[334]

[335]

[336]
[337]
Production Example 4: a eFAHxE prepared
[338]
An epoxidized fatty acid pentyl ester composition was prepared in the same manner as in Preparation Example 2, except that 500 g of 1-hexanol was used instead of butanol. In this case, the epoxidized fatty acid pentyl ester composition had an oxirane content of 5.51%, an iodine number of 1.40, and a compound represented by the following formulas 2-7, 2-8, 2-9, 4-5 and 4-6. 1,180 g of an epoxidized fatty acid hexyl ester composition (eFAHxE) was obtained.
[339]

[340]

[341]

[342]

[343]

[344]

[345]

[346]

[347]

[348]

[349]
[350]
Production Example 5: a eFAEHE prepared
[351]
In the same manner as in Preparation Example 2, except that 500 g of 2-ethylhexanol was used instead of butanol, the oxirane content was 5.21%, the iodine number was 1.70, and the following formulas 2-10, 2-11, 2-12, 1,180 g of an epoxidized fatty acid ethylhexyl ester composition (eFAEHE) containing the compound represented by 4-7 and 4-8 was obtained.
[352]

[353]

[354]

[355]

[356]

[357]

[358]

[359]

[360]

[361]

[362]
[363]
Production Example 6: a eFAINE prepared
[364]
In the same manner as in Preparation Example 2, except that 600 g of isononanol was used instead of butanol, the oxirane content was 5.22%, the iodine number was 1.72, and the following Chemical Formulas 2-13, 2-14, 2-15, 4- 1,250 g of an epoxidized fatty acid isononyl ester composition (eFAINE) containing the compound represented by 9 and 4-10 was obtained.
[365]

[366]

[367]

[368]

[369]

[370]

[371]

[372]

[373]

[374]

[375]
[376]
Production Example 7: a eFAPHE prepared
[377]
In the same manner as in Preparation Example 2, except that 600 g of 2-propylheptanol was used instead of butanol, the oxirane content was 5.00%, the iodine number was 1.47, and the following Chemical Formulas 2-16, 2-17, 2-18, 1,280 g of an epoxidized fatty acid propylheptyl ester composition (eFAPHE) containing the compounds represented by 4-11 and 4-12 was obtained.
[378]

[379]

[380]

[381]

[382]

[383]

[384]

[385]

[386]

[387]

[388]
[389]
A plasticizer composition was prepared by mixing and stirring the materials of Preparation Example in the amounts described in [Table 1] to [Table 5]. The evaluation of the physical properties of the plasticizer composition was performed according to the following experimental items.
[390]
[391]

[392]
Hardness (shore 'A', Shore 'D') measurement
[393]
According to ASTM D2240, the hardness of the specimen having a thickness of 3 mm was measured for 10 seconds.
[394]
[395]
Measurement of migration loss ( % )
[396]
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/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 glass 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 1 below to calculate the transfer loss value.
[397]
[398]

[399]
Transition loss (%) = [(initial weight of specimen before leaving in oven) - (weight of specimen after leaving in oven)]/ (initial weight of specimen before leaving in oven) × 100
[400]
[401]
Heat loss measurement ( % )
[402]
After exposing a specimen having a thickness of 1 mm at 80° C. for 72 hours, the weight of the specimen was measured, and the weight loss was calculated by substituting it in Equation 2 below.
[403]

[404]
Loss on heating (%) = [(initial weight of specimen) - (weight of specimen after work)]/ (initial weight of specimen before leaving in oven) × 100
[405]
[406]
Tensile strength measurement ( kgf /㎠)
[407]
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.
[408]
[409]
Elongation measurement ( % )
[410]
According to ASTM D638, a specimen having a thickness of 1 mm was pulled using a UTM (trade name: 4466, manufacturer: instron) at a cross head speed of 200 mm/min, and then the time at which the specimen was cut was measured. Then, by substituting in Equation 3 below, the elongation was calculated.
[411]

[412]
Elongation (%): [(length at the time the specimen is cut)/(initial length)] × 100
[413]
[414]
water speed
[415]
The water absorption rate was evaluated by measuring the time it takes for the resin and the product composition 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 60 rpm.
[416]
[417]
heat resistance
[418]
A 0.5T-thick specimen was operated at 220 °C at a speed of 25 mm/3 min using a Mathis oven to observe heat resistance, and a scale of 1 (excellent) to 5 (poor) was used.
[419]
[420]
Experimental example : evaluation of physical properties
[421]
Specimens were prepared using the plasticizer compositions of Examples and Comparative Examples described in [Table 1] to [Table 5] below.
[422]
The specimen preparation is based on 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 the Examples and Comparative Examples, and a stabilizer (trade name: BZ153T, manufacturer) : Songwon Industrial) 3 parts by weight are blended, mixed by stirring at a speed of 700 rpm at 98°C, 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 mm and a specimen having a thickness of 3 mm were prepared by working with the .
[423]
Each of the test items was evaluated for the specimen, and the results are shown in [Table 1] to [Table 5] below.
[424]
[425]
[Table 1]
division Example
One 2 2 4 5
Plasticizer composition (wt%) Cyclohexane-1,4-diester-based material 1,4-DEHCH 70 70 70 70 70
Epoxidized Alkyl Ester Composition eFAPE 10 - - - -
eFAEHE - 10 - - -
eFAINE - - 10 - -
eFAPHE - - - 10 10
Citrate-based substances TBC 20 20 20 20 -
TPC - - - - 20
The sum of the number of carbon atoms in R 4 and the average number of carbon atoms in R 5 , R 6 and R 7 9 12 13 14 15
Hardness A 87.2 89.2 89.6 89.7 88.0
D 41.5 43.2 43.0 43.1 42.0
performance loss 3.66 3.21 3.11 3.20 2.53
reduction in heating 1.94 1.54 1.35 1.20 1.42
tensile strength 208.1 230.1 235.2 238.6 235.0
elongation 305.6 315.0 313.9 314.8 317.8
absorption rate 205 235 250 256 235
heat resistance One One One One One
[426]
[Table 2]
division Example
6 7 8 9 10
Plasticizer composition (wt%) Cyclohexane-1,4-diester-based material 1,4-DEHCH 70 70 70 70 70
Epoxidized Alkyl Ester Composition eFABE 10 10 - - -
eFAPE - - 10 10 -
pFAHxE - - - - 10
Citrate-based substances THxC 20 - 20 - -
TEHC - 20 - 20 -
TPHC - - - - 20
The sum of the number of carbon atoms in R 4 and the average number of carbon atoms in R 5 , R 6 and R 7 10 12 11 12 16
Hardness A 88.3 90.4 88.5 90.5 92.5
D 42.2 44.6 42.3 44.6 46.2
performance loss 2.74 3.45 2.70 3.42 4.25
reduction in heating 1.27 1.20 1.20 1.05 1.12
tensile strength 234.5 237.8 230.9 235.0 204.6
elongation 325.0 319.5 324.1 320.5 287.5
absorption rate 254 291 262 298 310
heat resistance One One One One One
[427]
[Table 3]
division Example
11 12 13 14 15
Plasticizer composition (wt%) Cyclohexane-1,4-diester-based material 1,4-DEHCH 90 80 60 50 30
Epoxidized Alkyl Ester Composition eFABE - - - - 30
eFAEHE 5 10 20 20 -
Citrate-based substances TBC 5 10 20 30 -
TINC - - - - 40
The sum of the number of carbon atoms in R 4 and the average number of carbon atoms in R 5 , R 6 and R 7 12 12 12 12 13
Hardness A 90.1 89.9 89.3 88.6 89.4
D 43.7 44.0 43.3 43.0 43.3
performance loss 3.46 3.56 3.20 2.53 2.68
reduction in heating 1.27 1.40 1.34 1.60 1.06
tensile strength 230.8 235.1 230.5 235.9 238.6
elongation 304.7 306.6 306.9 315.0 314.3
absorption rate 285 274 248 217 295
heat resistance One One One One One
[428]
[Table 4]
division comparative example
One 2 3 4 5
Plasticizer composition (wt%) Cyclohexane-1,4-diester-based material 1,4-DBCH - - - 80 -
1,4-DEHCH 100 80 80 - -
1,4-DIDCH - - - - 80
Epoxidized alkyl ester composition eFABE - 20 - - -
eFAEHE - - - 10 10
Citrate-based substances TBC - - 20 10 10
The sum of the number of carbon atoms in R 4 and the average number of carbon atoms in R 5 , R 6 and R 7 - 4 4 14 14
Hardness A 90.5 89.7 89.4 86.4 92.8
D 44.8 43.7 4.7 41.6 46.2
performance loss 4.15 3.85 3.68 6.02 2.76
reduction in heating 1.68 1.80 1.75 5.48 0.69
tensile strength 216.3 218.4 216.0 195.6 228.6
elongation 295.0 300.5 295.6 270.6 286.7
absorption rate 307 280 234 190 318
heat resistance 3 One 5 One One
[429]
[Table 5]
division comparative example
6 7 8 9
Plasticizer composition (wt%) Cyclohexane-1,4-diester-based material 1,4-DBCH - 70 - -
1,4-DEHCH - - - 60
1,4-DIDCH - - 70 -
Epoxidized alkyl ester composition eFABE 50 - - -
eFAEHE - 30 30 20
Citrate-based substances TBC 50 - - -
ATBC - - - 20
The sum of the number of carbon atoms in R 4 and the average number of carbon atoms in R 5 , R 6 and R 7 8 8 8 -
Hardness A 84.5 86.1 93.4 90.4
D 40.1 41.5 46.8 44.6
performance loss 8.44 6.34 3.40 3.24
reduction in heating 12.03 5.88 0.67 1.33
tensile strength 180.3 187.6 230.4 221.0
elongation 248.9 265.1 274.8 301.5
absorption rate 157 184 357 270
heat resistance 3 One One 2
[430]
1,4-DBCH: dibutyl cyclohexane-1,4-dicarboxylate (LG Chem) 1,4-DIDCH: diisodecyl cyclohexane-1,4-dicarboxylate (LG Chem)
[431]
TBC: tributyl citrate (LG Chem)
[432]
TPC: Tripentyl Citrate (LG Chem)
[433]
THxC: trihexyl citrate (LG Chem)
[434]
TEHC: tris(2-ethylhexyl) citrate (LG Chem)
[435]
TINC: triisononyl citrate (LG Chem)
[436]
TPHC: tris(2-propylheptyl) citrate (LG Chem)
[437]
ATBC: Acetyltributyl citrate (LG Chem)
[438]
[439]
Referring to [Table 1] to [Table 5], it was confirmed that Examples 1 to 15 were excellent in plasticization efficiency, transfer loss, heating loss, tensile strength, elongation, absorption rate, and heat resistance. Further, in Example 1 Referring to to 10, R 4 of the carbon atoms and, R 5 , R 6 and R 7 embodiments the average number of carbon atoms agreement 10 to 15 of the Examples 2 to 9 Examples 1 and 10 compared to the implementation loss, It was confirmed that the heating loss, tensile strength and elongation were remarkably excellent. In addition, referring to Examples 1 to 4, as the number of carbon atoms of R 4 of the epoxidized alkyl ester composition increased, it was confirmed that the transition loss, loss on heating, tensile strength, and elongation were more improved. In addition, referring to Examples 6 to 9, it can be seen that the smaller the average carbon number of R 5 to R 7, the better the plasticization efficiency, the heating loss, the elongation, and the absorption rate. However, Examples 4 and 5 showed different aspects from Examples 6 to 9, which was due to the properties of tributylcitrate. In addition, referring to Examples 11 to 14, it was confirmed that as the content of the cyclohexane-1,4-diester-based material decreased, the transfer loss, loss on heating, elongation and absorption rate were improved.
[440]
On the other hand, it was confirmed that Comparative Example 1 including only the cyclohexane-1,4-diester-based material had significantly lowered heat resistance compared to the Example. It was confirmed that Comparative Example 2, which does not contain a citrate-based material, significantly lowered the tensile strength compared to Example. Comparative Example 3, which did not include the epoxidized alkyl ester composition, showed that the heat resistance was significantly lower than that of Example. In Comparative Example 4 containing dibutyl cyclohexane-1,4-dicarboxylate, it was confirmed that leaching loss and heating loss were significantly reduced compared to Example. In Comparative Example 5 containing diisodecyl cyclohexane-1,4-dicarboxylate, it was confirmed that plasticization efficiency and absorption rate were significantly lowered compared to Example. In Comparative Example 6, which did not contain the cyclohexane-1,4-diester-based material, it was confirmed that migration loss, heating loss, tensile strength, elongation and heat resistance were significantly lowered compared to Example. In Comparative Example 7 containing dibutyl cyclohexane-1,4-dicarboxylate but not including a citrate-based material, it was confirmed that migration loss, loss on heating, tensile strength and elongation were lowered compared to Example. In addition, in Comparative Example 8 containing diisodecyl cyclohexane-1,4-dicarboxylate and not containing a citrate-based material, it was confirmed that plasticization efficiency was lowered compared to Example, and elongation and absorption rate were significantly reduced. could It was confirmed that Comparative Example 9 containing acetyl tributyl citrate had lower heat resistance compared to Example.
Claims
[Claim 1]
a cyclohexane-1,4-diester-based material represented by the following formula (1); an epoxidized alkyl ester composition comprising at least one compound represented by the following formula (2); And a plasticizer composition comprising a citrate-based material represented by the following Chemical Formula 3: [Formula 1] [Formula 2] [Formula 3] In Chemical Formulas 1 to 3, R 1 and R 2 are each independently an alkyl group having 8 carbon atoms and R 3 is an alkyl group having 8 to 20 carbon atoms including at least one epoxy group, and R 4 to R 7 are each independently an alkyl group having 4 to 10 carbon atoms.
[Claim 2]
The plasticizer composition according to claim 1, wherein R 1 and R 2 are each independently selected from the group consisting of an n-octyl group, an isooctyl group and a 2-ethylhexyl group.
[Claim 3]
The plasticizer composition according to claim 1, wherein the epoxidized alkyl ester composition has an iodine number of less than 3.5 I 2 g/100 g.
[Claim 4]
The plasticizer composition of claim 1, wherein the epoxidized alkyl ester composition has an oxirane content (OC) of 3.5% or more.
[Claim 5]
The method according to claim 1, wherein R 4 is a butyl group, isobutyl group, pentyl group, isopentyl group, hexyl group, isohexyl group, 2-ethylhexyl group, octyl group, isononyl group, decyl group, isodecyl group and A plasticizer composition selected from the group consisting of 2-propylheptyl group.
[Claim 6]
The plasticizer composition of claim 1, wherein R 5 to R 7 are each independently an alkyl group having 4 to 8 carbon atoms.
[Claim 7]
The plasticizer composition of claim 1, wherein R 5 to R 7 are each independently an alkyl group having 5 to 10 carbon atoms.
[Claim 8]
The method according to claim 1, 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 the plasticizer composition that is one selected from the group consisting of isodecyl group.
[Claim 9]
The method according to claim 1, wherein the plasticizer composition, based on the total weight of the plasticizer composition, 10 to 90% by weight of the cyclohexane-1,4-diester-based material; and 5 to 70% by weight of the epoxidized alkyl ester composition; and 5 to 70% by weight of the citrate-based material.
[Claim 10]
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 the formula (2), and a saturated fatty acid alkyl ester comprising at least one compound represented by the following formula (4) The plasticizer composition further comprising a composition: [Formula 4] In Formula 4, R 8 is an alkyl group having 8 to 20 carbon atoms, and R 9 is an alkyl group having 4 to 10 carbon atoms.
[Claim 11]
The plasticizer composition of claim 1, wherein the sum of the carbon number of the alkyl group of R 4 and the average number of carbon atoms of the alkyl group of R 5 to R 7 is 10 to 15.
[Claim 12]
100 parts by weight of resin; and 5 to 150 parts by weight of the plasticizer composition according to claim 1 .
[Claim 13]
The method according to claim 12, 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, polyketone, polystyrene, polyurethane, natural rubber, synthetic rubber, and from the group consisting of a thermoplastic elastomer One or more selected resin compositions.