[Mutual citations and related applications;
[2]
This application is all the information described in the literature of 05.25.2017 chair Korea Patent Application Korea Patent Application claims the benefit, and those of the priority based on the No. 10-2017-0064749 which is incorporated as a part hereof.
[3]
[Technology]
[4]
The present invention relates to a resin composition containing a plasticizer, and this system citrate.
[5]
BACKGROUND
[6]
Typically the plasticizer to form an alcohol and the phthalic acid and adipic acid and poly-carboxylic esters, such as reaction with an equivalent. Commercially important examples are C8, C9 and C10 alcohols adipate, for instance of di (2-ethylhexyl) adipate, diisononyl adipate, diisodecyl adipate; And C8, C9 and C10 phthalates of alcohols, for example, includes a di (2-ethylhexyl) phthalate, diisononyl phthalate, diisodecyl phthalate.
[7]
The di specifically (2-ethylhexyl) phthalate plastisol (plastisol) and dry blended via a toy, films, footwear, coatings, flooring, glove, wallpaper, synthetic leather, sealants, tarpaulins, car floor coatings, furniture, used in the manufacture foam mats, and acoustic panels can also be used to produce exterior and insulation, and other calendered PVC plastic products PVC cable.
[8]
Include isononyl phthalate (DINP), di-2-propyl heptyl phthalate (DPHP), or diisodecyl phthalate (DIDP), - the ester compound used in the present plasticizer di- (2-ethylhexyl) phthalate (DEHP), di many, but used, and other components, which are harmful to the human body to environmental hormones which disturb the endocrine system, and further sikineunde therefore improves the product properties, etc. processability of the resin, the absorption speed, and the volatile loss, the implementation loss and thermal stability to the use limit .
[9]
On the other hand, the citrate is mainly applied to the second purpose of the primary plasticizer for improving the physical properties of the general-purpose plasticizer is, the typically a citrate to the alcohol of the C2 to C4 as the raw material is mainly used. However, due to problems such as transitivity, which cooking loss that these products are difficult to apply to the plasticizer is applied to the high content of plasticizer as the sole or primary plasticizer. Further, when increasing the number of carbon atoms of raw material alcohol in order to improve these properties, it can be expected to have an adverse effect such as plasticizing efficiency.
[10]
Further, in order to improve these problems, but can use a citrate carbon atoms having different alkyl groups each other as the sole plasticizer, in this case is complicated and the manufacturing process, it was difficult to economical reasons due to market according to the manufacturing cost increase problem accordingly.
[11]
Thus, it compounds capable of sufficiently improving the physical properties of existing products in a variety of physical properties of surfaces, such as environmentally friendly or non-phthalate, and the processability of the resin, the absorption speed, hardness, tensile strength, but elongation also, volatilization losses, transition loss and thermal stability this is the situation of development needs.
[12]
Detailed Description of the Invention
SUMMARY
[13]
Present as a plasticizer applied to the resin composition in the invention, the plasticizing efficiency, and to provide the citrate-based plasticizer as a main component citrate as environmentally friendly materials as having excellent reproducibility plasticizer of the inner planet and while being physical properties are improved, such as cooking loss properties do.
[14]
Problem solving means
[15]
According to one embodiment of the present invention to achieve the above object, there is provided a citrate-based plasticizer that contains at least the compound represented by Formula 11.
[16]
Formula 1
[17]

[18]
In Formula 1, R 1 to R 3 is an alkyl group having 7 independently of each other.
[19]
According to one embodiment of the present invention to solve the above problems, the resin 100 parts by weight; And a citrate-based plasticizer 5 to 150 parts by weight of the above; a resin composition comprising is provided.
[20]
Effects of the Invention
[21]
Citrate-based plasticizers, in accordance with an embodiment of the present invention, when used in the resin composition, environment-friendly, yet highly excellent plasticizing efficiency and workability due to the suitable absorption rate, provide excellent properties in such inner planet, cooking loss and resistance to volatile may, this citrate-based plasticizer can be excellent in the reproducibility of quality.
[22]
Best Mode for Carrying Out the Invention
[23]
Hereinafter, the present invention will be described in more detail to aid the understanding of the present invention.
[24]
The terms or words used in the description and claims of the present invention is general and not be construed as limited to the dictionary meanings are not, the inventor accordingly the concept of a term to describe his own invention in the best way on the basis of the principle that can be defined, which must be interpreted based on the meanings and concepts corresponding to technical aspects of the present invention.
[25]
[26]
Citrate-based plasticizers
[27]
According to one embodiment of the invention, there is provided a citrate-based plasticizer that contains at least the compound represented by Formula 11.
[28]
Formula 1
[29]

[30]
In Formula 1, R 1 to R 3 is an alkyl group having 7 independently of each other.
[31]
The general formula (I) of R 1 to R 3 may be each independently, any one of the n- heptyl group and 2-methyl-hexyl group. In this specification a substituent with the "2-methyl hexyl group, is a methyl group is bonded to a conventional chemical structure of the 2-carbon could be fed a hexyl group, but referred to as" iso-heptyl group "structure in the art, but the sheet It may be a 'TiHC' used as a call abbreviated rate, which triisostearate heptyl, and can mean the citrate, the three alkyl substituents of citrate (R in formula (I) 1 to R 3 2- methyl-hexyl group in) that may be to mean compounds of the combined structure.
[32]
On the other hand, the citrate is the first when it is applied as a plasticizer, that is, when applied as the sole plasticizer or high applied in an amount, since the number of carbon atoms is small citrate is too small, volatility size molecular weight, cooking loss and transitivity quite poor level and, if the carbon number is too large, there is a problem with the plasticizing efficiency and mothayeo poor absorption speed processability, it is generally applied as a secondary plasticizer, in order to compensate for this.
[33]
Further, the citrate of carbon atoms with each other are different alkyl groups bonded essentially be subjected to a transesterification reaction, at this time, applying a mixture thereof in the time the prepared product is 6 paper gun, their separation has to be commercialized by not feasible it is common to.
[34]
However, this in accordance with the content or the reaction conditions of alcohol and the ratio between the mixture can be varied, and because of this ratio change changing the overall average molecular weight or changing the like of the branching degree of the alkyl group mothayeo not the final physical properties of the uniformly reproducible It falls there is a problem. In this way the physical properties are factors that change in various cases where the number of carbon atoms of the alkyl groups apply different citrate has a quality guarantee of quality control and a uniform level of product situation somewhat difficult, such as for controlling the process conditions in order to solve this problem, when a supplement, there arises the economic problem, such as a separate process costs.
[35]
However, as applying the citrate-based plasticizer is an alkyl group having a carbon number of 7 according to the present invention, the citrate can improve the workability and to plasticizing efficiency and the absorption rate enough to be excellent as a single plasticizer, heating the implementation characteristics loss also can exhibit equivalent or greater level than the conventional plasticizers. Further, since the number of carbon atoms of the alkyl group are the same but different from each other can provide an excellent reproducibility is also a plasticizer for the product quality.
[36]
[37]
"Non-hybrid citrate" herein, R in formula (I) 1 to R 3 are both and can mean the same alkyl groups of citrate, "mixed-citrate" is R 1 to R 3 as different from each other, R 1 and R 2 is same as R 3 , if different than, R 2 and R 3 are same as R 1 may represent a case is different from the.
[38]
The citrate-based plasticizer to may be one comprising one or more selected from the group consisting of Formula 1-1 to a compound represented by Formula 1-6.
[39]
[Chemical Formula 1-1]
[40]

[41]
[Chemical Formula 1-2]
[42]

[43]
[Chemical Formula 1-3]
[44]

[45]
[Chemical Formula 1-4]
[46]

[47]
[Chemical Formula 1-5]
[48]

[49]
[Chemical Formula 1-6]
[50]

[51]
[52]
Specifically, the citrate-based plasticizer may be a plasticizer containing citrate, one kind of or include citrate of two or more. In this case, the citrate may be a plasticizer that includes both a non-mixed or a citrate plasticizer, or comprising a non-mixed citrates of the formula 1-2, wherein the two materials of the formula 1-1.
[53]
Further, the citrate-based plasticizer may include three or more kinds of citrate, and in this case may be a citrate-based plasticizer that includes both Formula 1-1 to Formula 1-6.
[54]
[55]
As mentioned above, the citrate-based case and a plasticizer as the sole plasticizer or a primary plasticizer for the resin composition used in an amount, phthalate compound and plasticizing efficiency (hardness), tensile strength of the same level are mainly used in conventional plasticizer and it is possible to secure a strain not only can solve the environmental problems can be the basis of improved processability with excellent plasticizing efficiency and excellent absorption rate. In addition, it is possible to reduce the heat loss and significantly superior inner planets.
[56]
Further, the citrate-based compounds are acetyl citrate is an acetyl group is bonded instead of the hydrogen of the hydroxy group (-OH) is preferably not. That is, it probably does not exist, an acetyl group in the molecule, it is preferred to use a citrate-based compounds acetyl groups are not bonded. Sheet When an acetyl group is present in rate-based compound, the processability, the risk of gel ringseong the deterioration according to the plasticizer properties, particularly deterioration of the plasticizer efficiency, and increase of a plasticizer in order to overcome the degradation of the plasticizer efficiency making and consequent due to problems such as product price increases, there may be adverse effects on various aspects such as market, economic and physical properties.
[57]
[58]
On the other hand, but are not limited thereto, the citrate-based plasticizer is a non-mixed citrate 3.0 to 99.0 mol% of the formula 1-1, if they contain three or more kinds of citrate; Formula 1-3 and a mixture of 0.5 to 96.5 mol% of the first mixed citrate as a second hybrid citrate represented by Formula 1-5 and Formula 1-6 of the formula 1-4; And it may include non-hybrid citrate 0.5 to 96.5% by mole of the formula 1-2.
[59]
If the citrate-based plasticizer is applied to the mixture as described above, by being contained within the molar ratio range as above, environmentally friendly, yet were brought to the appropriate rate of absorption and a short melting time for the resin further improves the processability of the resin, the hardness, the implementation loss and it can be the improved physical properties such as heat loss.
[60]
[61]
Sheet production method of rate-based plasticizer
[62]
According to one embodiment of the invention, to direct esterification of citric acid and alcohol, or to screen by transesterification reaction of the compound with an alcohol represented by the general formula (1) can be obtained citrate-based plasticizer.
[63]
Formula 1
[64]

[65]
In Formula 1, R 1 to R 3 is an alkyl group having 7 independently of each other.
[66]
[67]
More specifically, the case of producing a citrate-based plasticizer that includes the above formula 1-1 or a compound of formula 1-2 may be subject to a direct esterification reaction, citric acid and n- heptyl alcohol or 2-methyl-hexyl alcohol use may be made to directly perform an esterification reaction. That is, the non-hybrid sheet and a method for producing the rate may be a direct esterification reaction is carried out, in the case of the citrate-based plasticizer that includes a formula 1-1 and a compound of formula 1-2 is prepared by blending the respective method of the it can be adopted.
[68]
The direct esterification reaction is 80 ℃ to a temperature range of 270 ℃, preferably in a temperature range of 150 ℃ to 250 ℃ 10 minutes to 10 hours, preferably 30 minutes to 8 hours, more preferably 1 to 6 hours it is preferable to perform in.
[69]
The catalyst of the direct esterification reaction may be an acid catalyst or a mixed catalyst containing an organic metal catalyst, a sulfonic acid or sulfuric acid system comprising a Sn-based or Ti-based, but is not limited to the type of catalyst.
[70]
Is preferably used in an amount of 5 molar ratio: the citric acid and the alcohol is from 1: 1 to 1: 7 molar amount of, preferably 1: 2 to 1.
[71]
By the direct esterification reaction for the preparation of the citrate, the citrate may be prepared in a yield of at least about 80%.
[72]
In particular, to the number of carbon atoms is to apply a small citrate-based plasticizer, for example, if a butyl group using butanol in order to apply the citrate-based plasticizer include, butanol having a low boiling point and must be present from the start of the reaction as the first material , may result in a low boiling point, due to the esterification reaction temperature before reaching the catalyst activation temperature is proceeding normally, the problem of butanol was vaporized and does not participate in the reaction continued in the process, only the circulation of butanol. However, eliminating the need for use of the case of the citrate-based plasticizers of the present invention, butanol, and the solubility in water, such as butanol to avoid the generation of waste water containing a higher alcohol, and thus secondarily energy costs or operating costs this can be reduced and more.
[73]
[74]
Further, when containing both the compound of Formula 1-1 to Formula 1-6 to the citrate-based plasticizer may be a carbon number of the direct esterification reaction carried out using a mixture of 7 alcohols.
[75]
May be more efficient than direct esterification reaction is transesterification reaction using a mixture of alcohol, if the carbon number is 7, the alcohol, in the manufactured state the mixture state of a carbon number of 7 alcohols that bypasses a separate purification step (main component n- heptanol and 2-a-methyl-hexanol, additional carbon atoms in the alcohol may be included with 7 to the isomer) may be, and thus by using a mixed alcohol is not carried out the purification process according to the invention according to since the citrate-based plasticizer can be achieved the effect that the purpose to manufacture, there is a direct esterification reaction with an alcohol mixture that did not perform the separate step of purification can be preferably applied.
[76]
[77]
On the other hand, in addition to the direct esterification reaction and the transesterification reaction with the citrate-based plasticizer it can be produced, and the other alkyl group is an alkyl group of the above formula 1-1 or a non-hybrid citrate and the citrate of the formula 1-2 there are with transesterification reaction to the alcohol reaction may be carried out.
[78]
For example, when selecting a compound of Formula 1-1 to a non-hybrid, the citrate can be reacted with 2-methyl-hexyl alcohol, heptyl alcohol is n- When selecting a compound of formula 1-2 in a non-hybrid citrate and it may be reacted.
[79]
"Transesterification reaction" used in the present invention means a reaction in which alcohol and ester are reacted as shown R "is R 'interchangeably with each other in the alcohol of the ester in the following scheme 1 as shown below in Scheme 1:
[80]
[Reaction Scheme 1]
[81]

[82]
For example, the alcohol is 2-ethylhexyl alcohol and the citrate, the tree (n- heptyl) sheet when the rate, the transport of the formula 1-1 is the sheet 2-methylhexahydrophthalic green side of the alcohol When the esterification reaction is conducted to attack both the carbonyl carbon of the three n- heptyl (RCOOR ") groups present on the rate, to form a citrate-based compounds represented by the above formula 1-2, and; two carbonyl n- heptyl group of carbonyl when attacking the carbon, to form a compound represented by the above formula 1-5 or 1-6, and; when attacking the carbonyl carbon of the group one n- heptyl (RCOOR "), the above formula 1-3 or to form a compound represented by 1-4, and; The unreacted portion that is not the reaction is performed may be left in the compound represented by Formula 1-1.
[83]
When preparing a citrate-based plasticizer using a transesterification reaction as described above, there is a reaction time can be greatly shortened.
[84]
According to one embodiment of the present invention, the transesterification reaction of the citrate prepared by plasticizers may include both systems citrate represented by the formula 1-1 to 1-6, the compounds, the amount of alcohol depending it is possible to control the composition ratio of the compounds in the citrate-based composition.
[85]
The amount of the alcohol is in the range of 0.1 to 89.9 based on 100 parts by weight of the citrate parts by weight, specifically, may be an 3 to 50 parts by weight, more specifically 5 to 40 wt.
[86]
When the citrate-based plasticizer that includes all of the mixture was then citrate of Formula 1-1 to Formula 1-6, the larger the added amount of the alcohol, the mole fraction of the reactant, citrate participating in the transesterification reaction (mole fraction) is because large, the amount of mixed citrate may increase as the product.
[87]
In addition, the amount of citrate corresponding to the presence of unreacted This can be seen a tendency to decrease.
[88]
According to one embodiment of the invention, the trans-esterification reaction is 120 ℃ to 190 ℃, preferably from 135 ℃ to 180 ℃, more preferably from 10 minutes to 10 hours in a reaction temperature of 141 ℃ to 179 ℃, preferably carried out from 30 minutes to 8 hours, more preferably 1 to 6 hours. The temperature and time range for the citrate-based composition of a desired composition ratio can be obtained efficiently within. At this time, the reaction time may be calculated from the time the reaction was warmed to reach the reaction temperature.
[89]
According to one embodiment of the invention, the trans-esterification reaction may be carried out in the absence of a catalyst, may be carried out the presence of an acid catalyst or a metal catalyst, in this case, there is an effect, the response time is shortened.
[90]
The acid catalyst and the like, methanesulfonic acid or p- toluenesulfonic acid and sulfuric acid as an example, the metal catalyst may be for example an organic metal catalyst, metal oxide catalyst, a metal salt catalyst or the metal itself.
[91]
The metal component may be any one or a mixture of two or more of those selected from the group consisting of tin, titanium, and zirconium, for example.
[92]
[93]
Resin composition
[94]
The present invention provides a resin composition containing the citrate-based plasticizer and the resin.
[95]
According to one embodiment of the invention, the resin may be a resin known in the art. For it is not as ethylene vinyl acetate, polyethylene, polyketone, polyvinyl chloride, but can be used polystyrene, polyurethanes, thermoplastic elastomers, and poly (lactic acid) and mixtures of one or more selected from, limited.
[96]
The citrate-based plasticizer may be contained 5 to 150 parts by weight based on 100 parts by weight of the resin.
[97]
The resin composition may further include a filler. The filler may be an 0 to 300 parts by weight, preferably 50 to 200 parts by weight, more preferably from 100 to 200 by weight based on 100 parts by weight of the resin.
[98]
The filler may be a filler which is known in the art and not particularly limited. May be, for example, silica, magnesium carbonate, calcium carbonate, marvel, talc, magnesium hydroxide, titanium dioxide, magnesium oxide, calcium hydroxide, aluminum hydroxide, aluminum silicate, magnesium silicate and at least one mixture selected from the group consisting of barium sulfate.
[99]
The resin composition may further contain other additives such as a stabilizer, if necessary.
[100]
The stability of the other additive agents, and the like may each based on 100 parts by weight of the resin for example 0 to 20 parts by weight, preferably 1 to 15 parts by weight. The stabilizing agent such as calcium-calcium compound, such as stearic acid salts of zinc-zinc (Ca-Zn-based) but the use of stabilizing agents, are not particularly limited.
[101]
Sheet of citrate-based plasticizer, in accordance with an embodiment of the invention and obtain the absorption rate and a short melting time for the resin to improve the processability of the resin, wires, automobile interior materials, films, sheets, tubes, wallpaper, toys, flooring etc. when prescription and prescription compounds can provide excellent properties.
[102]
[103]
Example
[104]
Hereinafter, the embodiment example in detail to illustrate the present invention in detail will be described. However, embodiments according to the present invention can be modified in many different forms and the scope of the invention is not to be construed as limited to the embodiments set forth herein. Embodiments of the present invention are provided to more fully illustrate the present invention to those having ordinary skill in the art.
[105]
[106]
Preparation of THC (tree (n- heptyl) citrate): Preparation 1
[107]
Condenser, a water stripper, a condenser, a decanter, a reflux pump, a temperature controller, a 2-hydroxy-1,2,3-propane refining to 4 sphere 3 liter reactor equipped with a stirrer such as tricarboxylic acid (2-hydroxypropane-1,2 , 3-tricarboxylic acid) (citric acid) 576g, n- heptyl alcohol (Aldrich) 1566g (molar ratio 1: 4.5), titanium-containing catalyst (TnBT, tetra nbutyl titanate), a 1.44 g (100 parts by weight of citric acid, 0.25 parts by weight based on the catalyst by parts) was added, and the temperature was raised slowly to about 170 ℃. Was the generation number generated in the vicinity of about 170 ℃ started, reaction temperature of about 220 ℃, while continuing to inject the nitrogen gas from atmospheric pressure was carried out esterification for about 4.5 hours to complete the reaction when the acid value reached 0.1.
[108]
After completion of the reaction, extraction was performed with distillation under reduced pressure to remove the unreacted raw material for 0.5 to 4 hours, cool the reaction mixture, and the mixture was subjected to catalyst neutralization. After the reaction mixture was dehydrated to remove water. After the reaction mixture was dehydrated to remove water. By incorporating a filter material to the moisture is removed the reaction mixture stirred for a while, filtered, finally the tree (n- heptyl) citrate (THC) 1431 g (yield: 98%) was obtained.
[109]
[110]
Preparation of TiHC (tri (2-methylhexyl) citrate): Preparation 2
[111]
And to perform the reaction in the same manner as in Preparation Example 1 except that instead of using 2-methyl-hexyl alcohol using the n- heptyl alcohol in Preparative Example 1, and finally, tri (2-methylhexyl) citrate (TiHC) 1435 g (yield: 98%) was obtained.
[112]
[113]
Preparation Example 3: Preparation of 2-methyl-n- heptyl and hexyl mixture of citrate (THC-1)
[114]
As the reaction raw material of n- heptyl alcohol and 2-hexyl alcohol in place of n- heptyl alcohol of Preparative Example 15: was carried out in the same manner but using a 5. At this time, the citrate, the citrate mixture is represented by the formula 1-1 26.5 mol%, and 1-3 is represented by 1-4 citrate 48.5 mol%, and Formula 1-2, 1.5 and 1 the citrate -6 represented by a mixture of 25.0 mol%.
[115]
[116]
Preparation Example 4: Preparation of 2-methyl-n- heptyl and hexyl mixture of citrate (THC-2)
[117]
After a reaction raw material extraction to remove the unreacted raw material in Preparation Example 1 using a semi-finished product and THC 1000g 240g 2-hexyl alcohol, the transesterification reaction was carried out, and finally, to obtain a mixture 998g of citrate.
[118]
At this time, the citrate, the citrate mixture is represented by the formula 1-1 54.7 mol%, and 1-3 is represented by 1-4 citrate 40.5 mol%, and Formula 1-2, 1.5 and 1 the citrate -6 represented by a mixture of 4.8 mole%.
[119]
[120]
Comparative Preparation Example 1 Preparation of TBC
[121]
As a reaction raw material by using 384 g of citric acid and butanol, 580 g, and finally tributyl citrate (tributyl citrate), 706 g (yield: 98%) was obtained.
[122]
[123]
Comparative Preparation 2: Preparation of TPC
[124]
As a reaction raw material by using 384 g of citric acid and 688 g 1-pentanol, and finally the tree-pentyl citrate (tripentyl citrate), 796 g (yield: 98%) was obtained.
[125]
[126]
Comparative Preparation Example 3: Preparation of THxC
[127]
As a reaction raw material by using 384 g of citric acid and n- hexanol 797 g, finally trihexyl citrate (trihexyl citrate), 878 g (yield: 98%) was obtained.
[128]
[129]
Preparation of TOC: Comparative Preparation Example 4
[130]
As a reaction raw material by using 384 g of citric acid and 1014 g 2-ethylhexanol, and finally tri (2-ethylhexyl) citrate (tri-2-ethylhexyl citrate) 1029 g (yield: 98%) was obtained.
[131]
[132]
Comparative Production Example 5: Preparation of TiNC
[133]
As a reaction raw material by using 384 g of citric acid and iso-nonanol 1123 g, finally teuriyi Sono carbonyl citrate (triisobutyl citrate) 1111 g (yield: 98%) was obtained.
[134]
[135]
Comparative Preparation Example 6: Preparation of BOC253
[136]
As a reaction raw material by using the TOC 1000 g and n- butanol, 300 g obtained in Preparation Example 6, it was carried out the transesterification reaction, and finally, butyl octyl citrate (butyloctyl citrate) to obtain a 840 g.
[137]
The mixture TBC molecular weight of about 2.2% by weight in order, two 2-ethylhexyl group is about 2 weight ratio of the sum of these three substances to a butyl group citrate of about 18.7% by weight of the two kinds of exchange is about 20.9% by weight and, one of a 2-ethylhexyl group is from about 5 weight ratio of the sum of the citrate of the two kinds of replacement butyl group is about 45.4% by weight, TOC is the mixture in a weight ratio of about 3 was obtained as approximately 33.7% by weight.
[138]
[139]
Comparative Production Example 7: Preparation of BOC145
[140]
As a reaction raw material by using the TOC 1000 g and n- butanol, 150 g obtained in Preparation Example 6, it was carried out the transesterification reaction, and finally, butyl octyl citrate (butyloctyl citrate) to obtain a 940 g.
[141]
The mixture TBC molecular weight of about 0.7% by weight in order, two 2-ethylhexyl group, and about 1 weight ratio of the sum of these three substances to a butyl group citrate 9.2% by weight of the two kinds of exchange is about 9.9 wt% and, one of a 2-ethylhexyl group is from about 4 weight ratio of the sum of the citrate of the two kinds of replacement butyl group is about 38.9% by weight, TOC is the mixture in a weight ratio of about 5 was obtained as approximately 51.2% by weight.
[142]
[143]
Examples 1 to 4 and Comparative Examples 1 to 7
[144]
Was applied to the citrate prepared in Preparative Example 1-4 to exemplary plasticizers of Examples 1 to 4, comparison was applied to the citrate prepared in Preparation Examples 1 to 7 with Comparative Examples 1 to 7 plasticizer, the applied citrate in summary the number of carbon atoms given in Table 1 below.
[145]
TABLE 1
The number of carbon atoms of the alkyl citrate
Example 1 7
Example 2 7
Example 3 7
Example 4 7
Comparative Example 1 4
Comparative Example 2 5
Comparative Example 3 6
Comparative Example 4 8
Comparative Example 5 9
Comparative Example 6 4 and 8
Comparative Example 7 4 and 8
[146]

[147]
Hardness (hardness) measurement
[148]
Using the ASTM D2240, it was measured Shore (shore "A") hardness, 3T 10s at 25 ℃.
[149]
[150]
The tensile strength (tensile strength) measurement
[151]
ASTM by D638 method, a test device, the UTM after using (manufacturer;; Instron, Model 4466) pulls the crosshead speed (cross head speed) of 200 ㎜ / min (1T), to measure the point at which the specimen is cut . Tensile strength was calculated as follows:
[152]
Tensile strength (kgf / ㎟) = load (load) value (kgf) / thickness (㎜) x width (㎜)
[153]
[154]
Measure elongation (elongation rate)
[155]
ASTM D638 method by using the UTM, pulls the crosshead speed (cross head speed) of 200 ㎜ / min (1T), and then measuring the point at which the specimen is cut, the elongation at break was calculated as follows:
[156]
Elongation at break (%) = length after elongation / initial length] x 100 was calculated.
[157]
[158]
Implementation losses (migration loss) measured
[159]
KSM-3156 was obtained according to the above 2 mm thick specimens, the specimen-sided 2 kgf / cm after affixed PS Plate 2 was added to the weight of the. Taken out after leaving the test piece in a hot air circulation oven (80 ℃) for 72 hours and cooled for 4 hours at room temperature. Then the test piece after removing the PS attached to both surfaces to measure the weight before and after left in the oven was calculated according to an expression such as the implementation of the loss below.
[160]
Implementation loss (%) = [(initial weight of the sample at room temperature - the weight of the oven and then left to stand sample) / initial weight of the specimen at room temperature] x 100
[161]
[162]
Heating loss (volatile loss) measure
[163]
After the specimen production work at 100 ℃ for 72 hours to measure the weight of the specimen.
[164]
Cooking loss (%) = [(initial sample weight - sample weight after operation) / initial sample weight] was calculated as 100 x.
[165]
[166]
Liquid heating loss measurement
[167]
Insert 40g of a liquid product in a container of 15 center meters in diameter, and then stored at 125 ℃ for 3 hours in the Convection oven was measured in the experiment before and after weights.
[168]
[169]
Stress Test
[170]
After bending the prepared resin sample in 180 ℃, for 72 hours in a chamber fixed to 23, and 50% humidity storage, and then, the amount taken out of the test piece of wiping the folds of the oil paper control plasticizer implementation scale of 0 to 3; It ranks.
[171]
[172]
Experimental Example 1: Evaluation of physical properties of the resin sample
[173]
The specimen using the plasticizers of Examples 1 to 4 and Comparative Examples 1 to 7 were prepared.
[174]
By the specimen produced, see ASTM D638, a polyvinyl chloride resin (PVC (LS100S)) in a citrate-based plasticizer to 60 parts by weight of a stabilizer prepared in 100 parts by weight of the Examples and Comparative, for example BZ153T (Songwon ), 3 parts by weight of the formulation was mixed at 98 to 700 rpm. Was working at 160 ℃ for 4 minutes by using a roll mill (Roll mill), a specimen was produced by working at 2.5 minutes (low-pressure) and 2 minutes (high pressure) at 180 using a press (press).
[175]
Respectively evaluating the tests with respect to the specimen and the results are shown in Table 2 below.
[176]
[177]
TABLE 2
Hardness (Shore A) Tensile strength (kg / cm 2 ) Elongation at break (%) Implementation loss (%) Liquid heating loss (%) Cooking loss (%) Stress Test (72hr)
Example 1 67.5 168.5 305.8 0.39 0.03 0.86 0
Example 2 67.2 163.6 307.4 0.40 0.04 0.93 0
Example 3 67.3 167.9 307.0 0.38 0.03 0.88 0
Example 4 67.4 166.5 306.2 0.40 0.03 0.90 0
Comparative Example 1 64.5 143.6 275.6 2.67 1.33 3.45 0.5
Comparative Example 2 65.8 148.7 283.3 2.11 1.10 2.87 0.5
Comparative Example 3 66.4 156.9 288.6 1.58 0.87 1.50 0.5
Comparative Example 4 69.6 169.7 298.7 2.35 0.05 0.78 2.0
Comparative Example 5 72.8 165.7 306.2 2.88 0.02 0.60 3.0
Comparative Example 6 67.9 154.3 285.4 1.36 0.76 1.37 1.0
Comparative Example 7 69.0 151.6 295.1 1.85 0.24 1.05 1.0
[178]
Referring to Table 2, the carbon number is to check in Examples 1 to 4 is that the resistance to stress excellent and that the transition loss remarkably reduced as compared with Comparative Examples 1 to 7 apply to 7 in the combined citrate-based plasticizer alkyl . Further, the hardness, superior to the comparative example, the tensile strength and elongation properties, and it can be seen that it is also high level liquid heat loss.
[179]
Specifically, the carbon number of the tensile strength and elongation properties significantly inferior level as compared to Comparative Examples 1 to 3 apply to the citrate combination of 4 to 6 alkyl are examples and can be seen that the implementation loss is also larger appears, and cooking loss also be seen that appears to poor, Comparative examples 4 and 5 natjiman receive high bit of the tensile strength and elongation, higher the transition loss greater hardness plasticizing efficiency, the number of carbon atoms is applied to the citrate binding 8 or 9 is an alkyl group the falls can also be found almost no resistance to stress. Further, Comparative Examples 6 and 7, too, can determine that it is not excellent in physical properties as compared to a whole embodiment.
[180]
On the other hand, compared to the embodiment example 3 and 4. Compared to examples 6 and 7, these sets will both apply a mixed citrate is mixed with a non-mixed citrate as a plasticizer composition. Examples 3 and 4 carbon atoms, the same range because the different substituents are combined citrate in is expected that the physical properties change width smaller physical property measurement results also almost the similar level change width physical properties for as described above There is a confirmed to be below 0.5% of the bar, reproducibility to find out that it is extremely excellent in, Comparative example for the 6 and 7 in the case of elongation, and the difference appears by about 5%, liquid amount reduced by heating for about three times the it is confirmed that this difference is to implement this product on an equal level, it can be seen that rather difficult.
[181]
Through this, the number of carbon atoms is 7, the case of alkyl applies to the citrate combination with a plasticizer has a reproducibility of physical properties can be excellent and improved resistance to the overall physical properties, particularly the implementation loss and stress significantly, different physical properties also decrease without which it can be seen that can provide an excellent balance of plasticizers in all aspects of properties.
[182]
[183]
A preferred embodiment but will be described in detail for example the scope of the present invention of the present invention in the above is not rather various changes and modifications in the form of one of ordinary skill in the art using the basic concept of the invention as defined in the following claims is not limited thereto Furthermore, the present invention It belongs to the scope.

WE Claims

To citrate-based plasticizer that contains at least a compound represented by the formula 1: [Formula 1] In Chemical Formula 1, R 1 to R 3 is an alkyl group having 7 independently of each other.
[Claim 2]
According to claim 1, wherein the formula (1) of the R 1 to R 3 are, each independently, n- heptyl and 2-methyl hexyl any one of the citrate-based plasticizer that of the group.
[Claim 3]
According to claim 1 wherein the citrate-based plasticizer to Formula 1-1 to a citrate-based plasticizer comprises one or more selected from the group consisting of compounds represented by the following formulas 1-6: Formula 1-1] [ Chemical formula 1-2] [formula 1-3] [formula 1-4] [formula 1-5] [formula 1-6]
[Claim 4]
The method of claim 1, wherein the compound represented by Formula 1 and Formula 1-1, the citrate-based plasticizer for the non-mixed citrates of the formula 1-2 comprises at least 1: [Chemical Formula 1-1] [ formula 1-2]
[Claim 5]
According to claim 1, wherein the citrate-based plasticizer is a non-mixed citrates of the formula 1-1 to 1-2) and (a; To the first mixed citrates of the formula 1-3) and (1-4; And to the second hybrid citrate represented by formula 1-5) and (1-6; a citrate-based plasticizer comprises: [Chemical Formula 1-1] [Formula 1-2] [Formula 1-3] [Chemical Formula 1-4] [formula 1-5] [formula 1-6]
[Claim 6]
100 parts by weight of the resin; And the first term citrate-based plasticizer 5 to 150 parts by weight of a resin composition comprising a.
[Claim 7]
7. The method of claim 6 wherein the resin is at least one member selected from the group consisting of ethylene-vinyl acetate, polyethylene, polyketone, polyvinyl chloride, polystyrene, polyurethanes, thermoplastic elastomers and polylactic acid resin composition.