Art
[1]
Mutual citations and related applications
[2]
This application claims the benefit of priority based on the February 10th issue of Korea Patent Application No. 10-2017-0018590 2017, and all information disclosed in the literature of the Korea patent application are included as part of the specification.
[3]
[4]
Art
[5]
The present invention relates to a plasticizer composition and a resin composition comprising the same.
[6]
BACKGROUND
[7]
Typically the plasticizer to form an alcohol and the phthalic acid and adipic acid and poly-carboxylic esters, such as reaction with an equivalent. Further research has continued on the plasticizer composition, which can be substituted for the phthalate-based plasticizers, such as consideration of the national and international regulations on harmful phthalate-based plasticizer in the human body, terephthalate-based, adipate-based, or other high molecular weight.
[8]
[9]
On the other hand, in the sector of the high-melting compound, low heat loss in the main physical properties required in consideration of the required properties to be used an appropriate plasticizer. And mixing additives such as a wire and, if PVC compound of cable uses the tensile strength properties required in the specification, the elongation, plasticizing efficiency, and heating loss, plasticizers in PVC resins according to the tensile and elongation survival rate, fillers, stabilizers and flame retardants .
[10]
[11]
The current wire compound and typically use and diisodecyl phthalate (DIDP), which are endocrine disruptors observed substances in industry for automotive fabrics, because the regulations used in accordance with the environmental issues is underway, the development needs of eco-friendly products to replace them but is increased, that is the majority of products and many alternative products are yeoksido products that contain any part of the material still contains the phthalate environmental issues.
[12]
[13]
In the diisopropyl has excellent physical properties than decyl phthalate (DIDP), by developing environment-friendly products of the novel plasticizer composition, the study out to secure the free, high vinyl-based resin composition chloride in quality aspects in environmental issues is in progress .
[14]
[15]
[Prior art document]
[16]
[Patent Document]
[17]
[Patent Document 1] Patent No. 10-0957134 No.
[18]
Detailed Description of the Invention
SUMMARY
[19]
Present as a plasticizer applied to the resin composition in the invention, plasticizing efficiency and the inner planets are excellent and improved tensile strength and elongation, tensile survival rate and renal survival rate and to provide a resin composition comprising the plasticizer composition, and this, the cold resistance is improved.
[20]
Problem solving means
[21]
According to one embodiment of the present invention to solve the above problems, to trimellitate type plasticizer represented by formula (1); And to citrate-based plasticizer represented by the following formula (2); including and is provided with a plasticizer composition characterized in that it does not contain an epoxidized oil.
[22]
Formula 1
[23]
[24]
In Formula 1, R 1 to R 3 is an alkyl group having 4 to 10 carbon atoms independently.
[25]
[Formula 2]
[26]
[27]
In Formula 2, R 4 to R 6 are, each independently, an alkyl group of a carbon number of 5-9, R 7 is hydrogen.
[28]
According to one embodiment of the present invention to solve the above problems, the resin 100 parts by weight; And the aforementioned plasticizer composition 5 to 150 parts by weight of a resin composition containing a is provided.
[29]
Effects of the Invention
[30]
Plasticizer The compositions of the present invention, when used in the resin composition, excellent plasticizing efficiency, and the inner ear and the planet can be improved, improved tensile strength and elongation, tensile survival rate and renal survival rate, and, as well as expect the improvement of the cooking loss and cold resistance can.
[31]
Mode for the Invention
[32]
Hereinafter, the present invention will be described in more detail to aid the understanding of the present invention.
[33]
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.
[34]
[35]
Plasticizer composition
[36]
According to one embodiment of the invention, the plasticizer composition to trimellitate type plasticizer represented by formula (1); And citrate-based plasticizer represented by the following formula (2); including the essential and is characterized in that not containing epoxidized oils.
[37]
Formula 1
[38]
[39]
In Formula 1, R 1 to R 3 is an alkyl group having 4 to 10 carbon atoms independently.
[40]
[Formula 2]
[41]
[42]
In Formula 2, R 4 to R 6 are, each independently, an alkyl group of a carbon number of 5-9, R 7 is hydrogen.
[43]
Often it contains trimellitate-based plasticizers, and citrate-based plasticizer in the plasticizer composition the weight ratio of the two materials is an upper limit of 99: 1, 95: 5, 90:10, 85:15, 80:20, 70:30 or 60 : may be 40 days, it may be a lower limit of 1: 99, 5:95, 10:90, 15:85, 20:80, 30:70 or 40:60. Preferably it may be 90: 10 to 10: 90, more preferably from 80:20 to 20:80, more preferably 70:30 to 30:70.
[44]
Plasticizer composition according to an embodiment of the present invention is characterized in that it does not include the epoxidized oil, i.e., the epoxidized five days did not contain a plasticizer for the composition. Here, means the epoxidation five days is not input is the content also plasticizers within Also, the resin composition in the case as they preclude the application of an epoxidized oil as a component of the plasticizer composition, which plasticizer composition is mixed with the resin during processing composition 100 parts by weight of the preparation, 5 parts by weight or less, can be preferably means that the amount of less than 3 parts by weight or less, more preferably 1 part by weight, and to exclude as far as to inject the manufacture resin composition with a small amount of a stabilizer It is not.
[45]
For the epoxidation five days, but can see the specific effect on properties such as heat resistance, oil resistance, low temperature, for example, it can cause the symptoms to be about -5 ℃ the slurry liquid plasticizer at a temperature below the screen in the storage and transport of the product It may give rise to a big problem, so that there is a case that the epoxidized oil processing the resin with the plasticizer include the possibility that the cold properties of the transfer of the plasticizer composition, handling, and processing the resin composition deteriorates.
[46]
In addition, to the extent that the problems in addition to containing the epoxidized oil to the plasticizer when applied to products that require insulation, volume resistivity can cause the symptoms to be lowered compared with the eco-plasticizer composition that does not use conventional phthalate products and epoxidized five days have.
[47]
Thus, but a plasticizer the composition according to the invention in order to solve the above problems is essentially a trimellitate-based plasticizers, and citrate-based plasticizer as described above, does not contain this way epoxidation five days cold storage properties as this can greatly be improved, it can be expected to improve insulation performance by improving cold resistance of the resulting resin products and the volume resistivity improved.
[48]
[49]
Trimellitate-based plasticizer
[50]
According to one embodiment of the invention, the plasticizer composition can be incorporated include trimellitate-based plasticizers, and trimellitate-based plasticizers This is represented by the following general formula (1) to above the material represented by general formula (1) 1.
[51]
Formula 1
[52]
[53]
In Formula 1, R 1 to R 3 is an alkyl group having 4 to 10 carbon atoms independently.
[54]
The trimellitate-based plasticizers may complement the terephthalate-based as a substance capable of complementing a plasticizer, terephthalate-based as an effective plasticizer that can not be achieved as compared with phthalate-based plasticizer, inner planet or heat loss characteristics as described above .
[55]
In the trimellitate-based plasticizers, the general formula (I) of R 1 to R 3 may be a carbon number of 4 to 10, each of which may be the same with each other, a different case, R each other 1 to R 3 2 of which are the same will, may be a different one is the alkyl group. For example, the alkyl group is n-butyl group, an isobutyl group, a n-pentyl group, isopentyl group, n-hexyl group, n heptyl group, iso-heptyl group, nomalok group, yisook group, a 2-ethylhexyl group, nonyl group n , iso-nonyl group, an alkyl group such as 2-propyl-heptyl or iso-decyl group may be selected.
[56]
Further, when a normal alkyl group that is, linear alkyl groups include, but applied in the alkyl group known to be excellent in properties such as cold resistance and is excellent in a commercially iso branched alkyl group of from an economic point of view. For such trimellitate-based plasticizers, when applied by satisfying the number of carbon atoms, it can be expected to plasticizing efficiency, inner planet, cooking loss, kidney survival rate and stress transitivity improvement of the effect.
[57]
[58]
Citrate-based plasticizers
[59]
According to one embodiment of the invention, the plasticizer composition to is the citrate-based plasticizer, and comprises a citrate-based plasticizer is represented by formula (2) may comprise a material represented by the following formula (2) greater than or equal to 1.
[60]
[Formula 2]
[61]
[62]
In Formula 2, R 4 to R 6 are, each independently, an alkyl group of a carbon number of 5-9, R 7 is hydrogen.
[63]
The citrate-based plasticizer R of formula (II) 4 to R 6 are each independently, a pentyl group, an isopentyl group, a hexyl group, iso-hexyl, heptyl, iso-heptyl group, nomalok group, a 2-ethylhexyl group, n and no group or isononyl group, wherein R 4 to R 6 each may be the same as each other or may be different from each other.
[64]
Wherein R 4 to R 6 is yet an alkyl group having a carbon number of 5 to 9, the citrate is an alkyl group different from each other, for example, isopentyl group and isocitrate having the combination of substituents nonyl, 2-ethylhexyl and isopropyl sonil device having a combination of substituents may be such as citrate, isopentyl group and 2-ethyl-sheet having a combination of substituents hexyl acrylate, the addition is selected from among a carbon number of 5 to 9, the combination of the substituent of the alkyl group having the carbon number of two different the citrate or the like can be applied with, and the alkyl group may be straight linear or branched.
[65]
Wherein R 4 to R 6 is yet an alkyl group having a carbon number of 5 to 9, together with the same citrate alkyl group is, for example, tri-isopentyl citrate (TIPC), trihexyl citrate (THxC), tri-heptyl citrate (THpC ), tri-iso-heptyl citrate (TiHpC), tri (2-ethylhexyl) can be applied, such as the citrate (TEHC), teuriyi Sono carbonyl citrate (TINC), the addition may be applied if an alkyl group having a carbon number of 5 to 9 .
[66]
Preferably may be applied to not less than the number of carbon atoms is 5, in the case of using an alcohol having a carbon number of 5 to 9, more in comparison with the number of carbon atoms is relatively small amount of use as can be seen the equivalent to good effect, etc. plasticizing efficiency and the absorption rate have. In addition, the carbon number of the upper limit of the alkyl group is preferably can be applied to nine individual, when the carbon number exceeds 9, due to the excessive increase in molecular weight can cause a characteristic degradation such as absorption rate, plasticizing efficiency.
[67]
On the other hand, the sheet When an acetyl group is present in rate-based plasticizer, that is, R 7 lungs that occurs in even a by-product in the acetylation if caused, the properties of a plasticizer, in particular can be accompanied by physical properties deterioration such as plasticizing efficiency, and also, the manufacturing process It can be added to the economic, enemy equipment costs for handling acid. When so introduced into the acetyl group, there may result in locations, such as production costs increase due to the processing of the additional process steps and by-products of consideration.
[68]
In other words, citrate-based plasticizer that R in the general formula (2) 7 If the acetyl group, the decrease in the plasticizing efficiency compared to the case of hydrogen, a problem such as increase of the plasticizer added and the product price increases through this associated to overcome this it may be, R 7 is an acetyl group citrate-based plasticizer can not be better than that in which R7 is hydrogen in various aspects such as market, cost-effectiveness and properties.
[69]
[70]
The method
[71]
Method for preparing the plasticizer composition of the present invention has been to apply a blending method, it is possible to prepare a composition by a process of mixing a trimellitate-based plasticizers, and citrate-based plasticizer after the respective manufacturing.
[72]
The trimellitate-based plasticizers when producing a direct furnace esters, isopentyl alcohol, hexyl alcohol, heptyl alcohol, 2-ethylhexyl alcohol, isononyl alcohol, 2-propyl-heptyl alcohol and the general formula (I) of the R 1 to R 3 applying an alcohol having an alkyl group at least 1, and may perform the trimellitic acid and the reaction process.
[73]
The step of adding the above-mentioned direct esterification reaction, In a trimellitic acid in alcohol, and then the catalyst and react under a nitrogen atmosphere; Step of removing unreacted alcohol and neutralizing the unreacted acid; And the step of dehydration, and filtration by vacuum distillation; may be prepared by.
[74]
In addition, the alcohol, trimellitic 100% based on 150 mol% to 500 mol% mol acid, 200 mol% to 400 mol%, 200 mol% to 350 mol%, 250 mol% to 400 mol%, or 270 mole% to 330 mol% may be used within the range.
[75]
On the other hand, wherein the catalyst is one example of the esterification, sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, p-toluenesulfonic acid, methanesulfonic acid, ethane sulfonic acid, propane sulfonic acid, butane sulfonic acid, an acid catalyst such as alkyl sulfate, lactic aluminum, lithium fluoride, potassium chloride , cesium chloride, calcium chloride, iron chloride, aluminum phosphate, such as a metal salt, heteropolyacid, etc. of a metal oxide, a natural / synthetic zeolites, cation and anion exchange resins, tetraalkyl titanate (tetra alkyl titanate) and selected from the group consisting of organic metals of the polymers 1 species may be higher. As specific examples, the catalyst may be a tetra-alkyl titanate.
[76]
The amount of the catalyst used may be different according to the type, in the case of a homogeneous catalyst in one example it is 0.01% to 5% by weight relative to the reaction a total of 100% by weight, 0.01 to 3 wt%, 1 wt% to 5 wt% or 2 wt. for in, and the heterogeneous catalyst.% to 4 wt.% range of 5% to 200% by weight of the reaction product the total amount, 5% to 100% by weight, 20% to 200% by weight, or 20% to 150% by weight range It may be tomorrow.
[77]
At this time, the reaction temperature is in the range 180 ℃ to 280 ℃, 200 ℃ to 250 ℃, or 210 ℃ to 230 ℃ can tomorrow.
[78]
If the trimellitate system to prepare the plasticizer in the mixture, after the production trimellitate compound through the direct esterification described above it may be mixed, or a method of direct application of two or more alcohols in an esterification reaction to be applied It may be, or tri- (2-ethylhexyl) trimellitate or teuriyi Sono carbonyl trimellitic and trimellitate compounds, such as lactate, trans ester to the alcohol, such as 2-propyl-heptyl alcohol, iso-pentyl alcohol, heptyl alcohol reaction Chemistry reaction; through it is possible to manufacture a trimellitate plasticizer.
[79]
[80]
"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:
[81]
[Reaction Scheme 1]
[82]
[83]
For example, three of which alcohol is present in the isononyl alcohol, and trimellitates are tri (2-ethylhexyl) trimellitate is the case, the transesterification reaction is completed, isopropyl alcohol the recording side of the trimellitate 2 -ethylhexyl (RCOOR ") carbonyl both to attack both the carbonyl carbon may be formed with a isononyl trimellitate substituted with the group; if attacking the carbonyl carbon of the two 2-ethylhexyl group, two 2 -ethylhexyl group can form a compound of the three kinds of substitution group, and isononyl; with a single 2-ethylhexyl group if attacking the carbonyl carbon of one of a 2-ethylhexyl group substituted with three kinds isononyl a may form a compound, the unreacted portion that is not the reaction is performed may be left in tri (2-ethylhexyl) trimellitate.
[84]
According to one embodiment of the present invention, the transesterification a trimellitate-based plasticizers prepared by the reaction, it is possible to control the composition ratio of the compounds in the trimellitate-based composition according to the added amount of the alcohol.
[85]
The amount of the alcohol is in the range of 0.1 part by weight to 89.9 parts by weight based on 100 parts by weight of the citrate, and specifically may be 3 parts by weight to 50 parts by weight, more specifically 5 parts by weight to 40 parts by weight.
[86]
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 from 1 hour to 6 hours. A terephthalate-based plasticizer which is a mixture of the desired composition within the temperature and time range can be obtained effectively. At this time, the reaction time may be calculated from the time the reaction was warmed to reach the reaction temperature.
[87]
The trans-esterification reaction 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.
[88]
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.
[89]
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.
[90]
[91]
The screen direct esterification reaction and the transesterification reaction can also be used to manufacture the above citrate-based plasticizer (trimellitic acid instead of citric acid used). In this case, the tree may be made of a mixture of trimellitic citrate-based plasticizers as in the lactate-based plasticizer is also a predetermined ratio, it is also possible to control the composition ratio of the resulting mixture is adjusted according to the content of the alcohol as a reaction raw material. In addition, when producing a citrate plasticizer directly through the esterification or transesterification reaction in the same manner as have been applied to the production of the trimellitate-based plasticizers may be applied to the contents.
[92]
Further, citric acid and trimellitic acid acid in place of material of this acid anhydride series, such as the reaction raw materials may be used as a substitute material.
[93]
[94]
On the other hand, a method for preparing the plasticizer composition can be applied a method of manufacturing, the mixture at the same time the esterification reaction of a raw material can be applied to a method of preparing a blended after each.
[95]
Specifically, the citrate-based plasticizers, and trimellitate-based To apply to all carbon atoms of the alkyl group same in the plasticizer include, citric acid, trimellitic acid mixture, such acid by direct esterification with an alcohol having a specific group prepared can, in which case there is a group of citrates and trimellitates carbon atoms can be both obtained with the same plasticizer composition.
[96]
That is, in case of using the same alcohol, it may be a commercially economical method of reacting two or more acid or anhydride with an alcohol in the manufacturing process at the same time.
[97]
[98]
According to another embodiment of the present invention, on the other a plasticizer composition prepared as the resin 100 parts by weight of the preparation, 5 parts by weight to 150 parts by weight, 20 parts by weight to 100 parts by weight, 30 to 80 parts by weight or 40 parts by weight to 70 parts by weight It is mixed with the resin portion is provided to the resin composition.
[99]
The resin may be selected from ethylene-vinyl acetate, polyethylene, polyketone, polyvinyl chloride, polystyrene, polyurethane, and thermoplastic elastomers.
[100]
Further, the resin composition may be mixed with various additives such as heat stabilizers, stabilizers, lubricants and fillers, the kind and content can be applied, as is known in the art.
[101]
The resin composition prepared as described above, e.g., in calendering or compound formulation may provide for both effective resin composition or the like, for example, through the resin composition, electric wire, flooring, vehicle interior materials, film, sheet, or tube It can be applied to manufacturing.
[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]

[107]
Preparation 1: Preparation of tributyl tree trimellitate (TBTM)
[108]
As a reaction raw material by using trimellitic anhydride and 576.3g 866g n- butyl alcohol, finally tributyl trimellitate 1,112g (yield: 98%) was obtained.
[109]
[110]
Preparation 2: Preparation of isopentyl tree trimellitate (TIPTM)
[111]
As a reaction raw material by using trimellitic anhydride and 576.3g isopentyl alcohol 1,030g, finally tree isopentyl trimellitate 1,236g (yield: 98%) was obtained.
[112]
[113]
Preparation Example 3: Preparation of trihexyl tree trimellitate (THxTM)
[114]
As a reaction raw material by using trimellitic anhydride and 576.3g hexyl alcohol 1,196g, finally trihexyl trimellitate 1,360g (yield: 98%) was obtained.
[115]
[116]
Preparation of tri (2-ethylhexyl) trimellitate (TEHTM): Preparation 4
[117]
As a reaction raw material by using trimellitic anhydride and 576.3g of 2-ethylhexyl alcohol 1,521g, finally tri (2-ethylhexyl) trimellitate 1,607g (yield: 98%) was obtained.
[118]
[119]
Preparation Example 5: Preparation of teuriyi Sono carbonyl trimellitate (TINTM)
[120]
As a reaction raw material by using trimellitic anhydride and 576.3g isononyl alcohol 1,685g, finally teuriyi Sono carbonyl trimellitate 1,731g (yield: 98%) was obtained.
[121]
[122]
Preparation of tri (2-propyl-heptyl) trimellitate (TPHTM): Production Example 6
[123]
As a reaction raw material by using 576.3g of trimellitic anhydride and 2-propyl-heptyl alcohol 1,852g, finally tri (2-propyl-heptyl) trimellitate 1,855g (yield: 98%) was obtained.
[124]
[125]

[126]
Preparation 7: Preparation of a tree isopentyl citrate (TIPC)
[127]
And as a reaction raw material using citric acid 576 g and 1,030 g isopentyl alcohol, and finally the tree isopentyl citrate 1,183g (yield: 98%) was obtained.
[128]
[129]
Preparation Example 8: Preparation of a tree-hexyl citrate (THxC)
[130]
As a reaction raw material by using the citric acid 576 g and 1,196 g hexyl alcohol, finally trihexyl citrate 1,307g (yield: 98%) was obtained.
[131]
[132]
Preparation of tri (2-ethylhexyl) citrate (TEHC): Preparation 9
[133]
And as a reaction raw material using citric acid 576 g and 1,521 g 2-ethylhexyl alcohol, finally tri (2-ethylhexyl) citrate 1,554g (yield: 98%) was obtained.
[134]
[135]
Preparation 10: Preparation of teuriyi Sono carbonyl citrate (TINC)
[136]
As a reaction raw material by using the citric acid 576 g and 1,685 g isononyl alcohol, finally teuriyi Sono carbonyl citrate 1,679 g (yield: 98%) was obtained.
[137]
[138]
By mixing the materials prepared in Preparative Examples 1 to 10 was prepared in the plasticizer composition of the embodiments, the other hand examples and comparative examples, and reference example to a plasticizer composition showed summarized in Table 1 and the properties of the plasticizer composition the evaluation was performed according to the tests below. A substance other than the material prepared in Preparative Example are all ㈜LG chemicals.
[139]
TABLE 1
A plasticizer Plasticizer B Plasticizer C
Example 1 TBTM 60 I'M 40 -
Example 2 TIPTM 50 I'M 50 -
Example 3 THxTM 40 TEHC 60 -
Example 4 TEHTM 30 THxC 70 -
Example 5 TINTM 20 TIPC 80 -
Example 6 TPHTM 10 TIPC 90 -
Example 7 TEHTM 70 TIPC 30 -
Example 8 THxTM 80 TEHC 20 -
Example 9 TBTM 90 I'M 10 -
See, for example, DIDP1) 100 - -
Comparative Example 1 TPHTM 100 - -
Comparative Example 2 TBTM 100 - -
Comparative Example 3 - TIPC 100 -
Comparative Example 4 - I HAVE 100 -
Comparative Example 5 TEHTM 30 TBC2) 70 -
Comparative Example 6 TEHTM 70 TUDC3) 30 -
Comparative Example 7 TEHTM 70 ATIPC 4) 30 -
Comparative Example 8 TBTM 60 ATINC5) 40 -
Comparative Example 9 TIPTM 50 I'M 50 ESO6)
Comparative Example 10 TINTM 20 TIPC 80 ESO6)

[140]
1) DIDP: diisodecyl phthalate
[141]
2) TBC: tributyl citrate
[142]
3) TUDC: tree undecyl citrate
[143]
4) ATIPC: acetyl triisopropyl-pentyl citrate
[144]
5) ATINC: acetyl teuriyi Sono carbonyl citrate
[145]
6) Plasticizer A and B total sum 100 parts by weight of 20 parts by weight of epoxidized soybean oil (ESO) In contrast
[146]
[147]

[148]
Hardness (hardness) measurement
[149]
Using the ASTM D2240, it was measured Shore (shore "A") hardness, 3T 10s at 25 ℃.
[150]
[151]
The tensile strength (tensile strength) measurement
[152]
ASTM by D638 method, a test device, the UTM after using (manufacturer;; Instron, Model 3345) 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:
[153]
Tensile strength (kgf / cm 2 ) = Load (load) value (kgf) / thickness (cm) x width (cm)
[154]
[155]
Measure elongation (elongation rate)
[156]
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:
[157]
Elongation at break (%) = length after elongation / initial length] x 100 was calculated.
[158]
[159]
Implementation losses (migration loss) measured
[160]
KSM-3156 was obtained according to the above 2 mm thick specimens, the specimen-sided 2 kgf / cm and then attached to Plate Glass paper and oil 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 before and after the weight was removed to leave the double-sided attached to things oven was measured by calculating the following equation by the implementation of the loss below.
[161]
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
[162]
[163]
Heating loss (volatile loss) measure
[164]
After a sample was produced at 121 ℃ exposed for 168 hours to measure the weight of the specimen.
[165]
Cooking loss (%) = [(initial sample weight - sample weight after operation) / initial sample weight] was calculated as 100 x.
[166]
[167]
The tensile and elongation measurements survival rate
[168]
Was added to the column is measured for 121 ℃, 168 hours of tensile and elongation survival rate, intended to measure the tensile and elongation properties which remain in the specimen, the measurement method is the same as the method above, the tensile strength and elongation measured.
[169]
[170]
Hardy
[171]
After the fabricated five samples was allowed to stand for 3 minutes at a specific temperature to measure the temperature at the time of hitting damage than three out of five dogs.
[172]
[173]
Experimental Example 1: evaluation of physical properties 1
[174]
A specimen using the mixed plasticizer compositions of Examples and Comparative Examples described in Table 1 was prepared.
[175]
The sample produced was ASTM reference to D638, polyvinyl resins (PVC (LS100)) RUP-144 a plasticizer composition prepared based on 100 parts by weight, in the Examples and Comparative Examples to 50 parts by weight of a stabilizer chloride (ADEKA Korea) were mixed in 5 parts by weight, Omya 1T (Omiya), 40 parts by weight of the St-a (Isu Chemical) 0.3 parts by weight blended with a lubricant 98 ℃ to 700 rpm as the filler. Was working at 160 ℃ for 4 minutes by using a roll mill (Roll mill), a specimen was prepared by working in 3 minutes (the low pressure) and 2.5 minutes (high pressure) at 180 ℃ using a press (press).
[176]
Respectively evaluating the tests with respect to the specimen and the results are shown in Table 2 below.
[177]
[178]
TABLE 2
경도(Shore "A") Tensile strength (kg / cm 2 ) Tensile survival rate (%) Elongation at break (%) Renal survival rate (%) Implementation loss (%) Cooking loss (%) Cold Resistance (℃)
Example 1 87.8 172.3 102.4 310.2 95.6 0.89 2.67 -30
Example 2 88.1 169.8 99.6 308.1 88.3 1.46 2.49 -29
Example 3 88.2 173.5 101.2 307.3 95.8 1.50 2.07 -29
Example 4 88.7 175.8 98.6 298.7 99.5 1.62 2.54 -30
Example 5 88.0 178.2 103.4 310.0 98.5 1.24 2.89 -30
Example 6 88.1 179.8 98.0 302.8 95.9 0.90 2.72 -29
Example 7 88.5 178.9 96.8 305.8 96.0 1.90 1.50 -30
Example 8 86.9 168.9 93.7 280.4 96.1 0.77 1.68 -31
Example 9 85.7 165.3 95.4 311.8 92.5 0.56 3.84 -32
See, for example, 89.1 160.2 90.3 276.1 81.1 1.84 7.35 -26
Comparative Example 1 93.4 180.3 92.3 254.0 88.7 2.75 1.47 -25
Comparative Example 2 85.0 151.3 93.4 302.4 74.2 2.60 5.20 -32
Comparative Example 3 87.8 163.4 88.2 303.4 85.1 1.95 3.67 -29
Comparative Example 4 93.0 172.0 90.5 260.3 80.4 2.80 3.45 -28
Comparative Example 5 88.1 162.4 80.1 288.7 76.5 2.41 8.61 -30
Comparative Example 6 95.4 178.0 93.5 230.4 93.4 3.55 1.20 -25

[179]
[180]
Referring to Table 2, trimellitate type, if the plasticizer and the citrate-based plasticizer-described properly mix the binding material is an alkyl group having a proper number of carbon atoms as the Examples 1 to 9 a, having an equivalent or greater physical properties compared to reference towing DIDP It can be found. The plasticizer DIDP is a product used for a conventional general-purpose quality product is facing environmental problems as a superior one phthalate-based products. That is, it confirmed that the examples 1 to 9. In the case of a plasticizer composition, while maintaining environmental benefits compared DIDP can be improved as equivalent or greater levels of all the physical properties.
[181]
However, in the case of the Examples 1 to 9 comparison, in the case without using solely a trimellitate-based plasticizers, or citrate-based plasticizer mix, the lowering of DIDP contrast transition loss ttuimyeo the eye, in contrast to example 1, plasticizing efficiency ( hardness), elongation at break and a cold resistance is significantly inferior compared to examples 1 to 9, it can be seen the failed good also in case an existing product, DIDP. In the case of Comparative Example 2, it can be seen that at a loss in tensile strength and elongation, and a large loss in the survival rate, in the case of Comparative Example 3 in the tensile survival rate, in the case of Comparative Example 4 plasticizing efficiency and renal survival rate.
[182]
Further, in the case of the comparison are not satisfied the carbon number range of Examples 5 and 6 in ttuimyeo in that eye of harsh the transition loss level, Comparative Example 5, the citrate-based heating loss exemplary carbon number of failure to meet the 5 to 9 as 4 for contrast it can be seen that up to four times a plasticizer loss upon heating considerable processing to increase, it can be seen the survival rate also poor tensile sujunim. In Comparative Example 6, the carbon number of citrate-based plasticizer efficiency, elongation by more than 9 of the plasticizer was extremely lowered cold resistance can also check the lower sujunim.
[183]
[184]
Experimental Example 2: Property Evaluation 2 (difference according to whether or not an acetyl group)
[185]
The embodiment described in Table 1 and Comparative Example using the plasticizer composition blend of Example was produced specimens as Experimental Example 1 to assess the respective test items with respect to the specimens shown in Table 3 and the results.
[186]
TABLE 3
경도(Shore "A") Tensile strength (kg / cm 2 ) Tensile survival rate (%) Elongation at break (%) Renal survival rate (%) Implementation loss (%) Cooking loss (%) Cold Resistance (℃)
Example 1 87.8 172.3 102.4 310.2 95.6 0.89 2.67 -30
Example 7 88.5 178.9 96.8 305.8 96.0 1.90 1.50 -30
See, for example, 89.1 160.2 90.3 276.1 81.1 1.84 7.35 -26
Comparative Example 7 89.7 170.2 95.0 292.5 95.1 2.20 1.45 -27
Comparative Example 8 88.5 158.3 92.6 295.4 94.0 1.35 2.60 -27

[187]
[188]
When the Comparative Examples 7 and 8, see Table 3, geotinde apply that the acetyl group is bonded to the citrate-based plasticizer applied in each of Examples 1 and 7, when the application of citrate the acetyl group is bonded is more legacy product DIDP the physical properties become poor, and some occur, it can be seen that the performance degradation that occurs in all properties without having to cover any property.
[189]
In the case of the acetyl group is the citrate-based plasticizer combined, the process for making them can be complex, and the economic loss corresponds, in that the waste acid generation and performance aspects of the plasticizer as an unresolved also environmental problems due to waste acid as well as economical and environmental aspects can be found that it is preferable to apply the acetyl group is not bonded.
[190]
[191]
Experimental Example 3: Physical property evaluation 3 (unlike with the addition of the epoxidized oil)
[192]
The embodiment described in Table 1 Examples and Comparative Examples of the plasticizer composition were produced by using the mixture of the specimen as shown in Experimental Example 1 to respectively evaluate the tests with respect to the sample are shown in the following Table 4 as a result.
[193]
[194]
TABLE 4
경도(Shore "A") Tensile strength (kg / cm 2 ) Tensile survival rate (%) Elongation at break (%) Renal survival rate (%) Implementation loss (%) Cooking loss (%) Cold Resistance (℃)
Example 2 88.1 169.8 99.6 308.1 88.3 1.46 2.49 -29
Example 5 88.0 178.2 103.4 310.0 98.5 1.24 2.89 -30
See, for example, 89.1 160.2 90.3 276.1 81.1 1.84 7.35 -26
Comparative Example 9 88.7 160.4 93.4 288.5 87.2 1.30 2.41 -24
Comparative Example 10 88.6 170.0 95.2 297.2 96.4 1.44 2.73 -24

[195]
[196]
Comparative Example 9 and 10 is a further added to the epoxidized soybean oil as a plasticizer, an epoxidized oil to the compositions of Examples 2 and 5, respectively. Referring to Table 4, the conventional product can confirm the DIDP become prepare cold resistance is poor, the epoxidation conducted without addition of an oil for example, compared to the plasticizing efficiency was lowered, equivalent to a reduction in tensile survival rate and elongation also greatly decline We can see that occurring.
[197]
[198]
This through, trimellitate type, if the plasticizer and citrate based a mixed plasticizer plasticizer composition, it is necessary to control the number of carbon atoms of each substance, citrate-based plasticizer are to be used that the acetyl group is not bonded, the epoxidation five days If it was confirmed that the addition of the plasticizer that does good in terms of quality.
[199]
[200]
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.

Claims
[Claim 1]
To trimellitate type plasticizer represented by formula (1); And to citrate-based plasticizer represented by the following formula (2); plasticizer composition, characterized in that including the epoxidation five days is not contained, [formula 1] In Formula 1, R 1 to R 3 is a 4-carbon atoms are each independently to an alkyl group of 10. [Chemical Formula 2] In Formula 2, R 4 to R 6 is an alkyl group are each independently, a carbon number of 5 to 9, R 7 is hydrogen.
[Claim 2]
The method of claim 1, wherein the trimellitate-based plasticizers, and citrate-based plasticizer in the plasticizer composition at a weight ratio to a 90: 10 to 10: 90.
[Claim 3]
The method of claim 1, wherein the trimellitate-based plasticizers, and citrate-based plasticizer in the plasticizer composition in a weight ratio of 70:30 to 30:70.
[Claim 4]
The method of claim 1 wherein the general formula (I) of R 1 to R 3 are, each independently, a n-butyl group, an isobutyl group, a n-pentyl group, isopentyl group, n-hexyl group, n heptyl group, iso-heptyl group, nomalok group , yisook group, a 2-ethylhexyl group, n nonyl, iso-nonyl group, the plasticizer composition is selected from the group consisting of 2-propyl-heptyl or iso-decyl group.
[Claim 5]
The method of claim 1, wherein the formula (2) of the R 4 to R 6 are, each independently, a pentyl group, an isopentyl group, a hexyl group, iso-hexyl, heptyl, iso-heptyl group, nomalok group, a 2-ethylhexyl group, the plasticizer composition is selected from the normal nonyl or isononyl group the group consisting of.
[Claim 6]
100 parts by weight of the resin; And a plasticizer composition of claim 1 5 to 150 parts by weight of a resin composition comprising a.
[Claim 7]
7. The method of claim 6 wherein the resin is of not less than one member selected from the group consisting of ethylene-vinyl acetate, polyethylene, polyketone, polyvinyl chloride, polystyrene, polyurethane, and thermoplastic elastomer resin composition.