This application claims the benefit of priority based on Korean Patent Application No. 10-2018-0100356 dated August 27, 2018, and all contents disclosed in the literature of the Korean patent application are incorporated as a part of this specification.
[3]
[4]
technical field
[5]
The present invention relates to a plasticizer composition comprising two or more types of terephthalate having the same carbon number and a type terephthalate having at least one carbon number different from each other, and a resin composition including the same.
[6]
background
[7]
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.
[8]
[9]
On the other hand, regardless of the plastisol industry, calendaring industry, extrusion/injection compound industry that manufactures finished products such as flooring, wallpaper, soft and hard sheets, gloves, wires, hoses, and films, the demand for these eco-friendly products is increasing. In order to strengthen the quality characteristics, processability and productivity of each finished product, an appropriate plasticizer should be used in consideration of discoloration, transferability, and mechanical properties.
[10]
In these various areas of use, additives such as plasticizers, fillers, stabilizers, viscosity reducing agents, dispersants, defoamers, foaming agents, etc. will do
[11]
For example, among the plasticizer compositions applicable to PVC, when di(2-ethylhexyl) terephthalate (DEHTP), which is relatively inexpensive and most commonly used, is applied, hardness or sol viscosity is high and the absorption rate of the plasticizer is relatively slow, and the transferability and stress transferability were not good.
[12]
As an improvement to this, as a composition containing DEHTP, it may be considered to apply a product of a transesterification reaction with butanol as a plasticizer, but while the plasticization efficiency is improved, transferability or thermal stability is poor, and mechanical properties Improvement of physical properties is required, such as a slight decrease in this, and there is currently no solution other than adopting a method that compensates for this through mixing with other secondary plasticizers in general.
[13]
However, in the case of applying the secondary plasticizer, it is difficult to predict the change in physical properties, and it may act as a factor in increasing the unit price of the product, and the research proceeds slowly, such as the improvement of the physical properties is not evident except in certain cases.
[14]
DETAILED DESCRIPTION OF THE INVENTION
technical challenge
[15]
The present invention is a plasticizer composition comprising two or more types having the same type of carbon number as terephthalate and at least one type having a different number of carbon atoms as the terephthalate, wherein the difference in carbon number of the alkyl group bonded to the two ester groups of the different carbon number is 3 or less By applying that, An object of the present invention is to provide a plasticizer composition capable of maintaining and improving plasticizing efficiency and mechanical properties at equal or higher levels compared to existing plasticizers, and improving viscosity stability, migration loss and stress resistance.
[16]
means of solving the problem
[17]
According to one embodiment of the present invention in order to solve the above problems, as terephthalate, the alkyl group bonded to the two ester groups has the same carbon number of the same type; two or more types are included, and the terephthalate is bonded to the two ester groups. Including at least one type of different carbon number of the alkyl group, the different carbon number type includes both higher alkyl and lower alkyl, wherein the higher alkyl has 8 or less carbon atoms, and the lower alkyl has 5 or more carbon atoms. A plasticizer composition is provided.
[18]
According to another embodiment of the present invention in order to solve the above problems, 100 parts by weight of the resin; And 5 to 150 parts by weight of the above-described plasticizer composition; is provided a resin composition comprising.
[19]
The resin is 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. can
[20]
Effects of the Invention
[21]
The plasticizer composition according to an embodiment of the present invention, when used in a resin composition, maintains and improves plasticization efficiency and mechanical properties at equal or higher levels compared to conventional plasticizers, and at the same time improves viscosity stability, migration loss and stress resistance. can
[22]
Modes for carrying out the invention
[23]
The terms or words used in the present specification and claims should not 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.
[24]
[25]
Definition of Terms
[26]
The term "composition" as used herein includes reaction products and decomposition products formed from the materials of the composition, as well as mixtures of materials comprising the composition.
[27]
The prefix "iso-" as used herein refers to an alkyl group in which a methyl group having 1 carbon number is bonded to the main chain of the alkyl group in a branched chain, and in general, it means that a methyl branch is bonded to the terminal of the alkyl group. In , it may be used as a generic term for branched alkyl groups in which a methyl group and/or an ethyl group are bonded to the main chain in a branched chain, including those bonded to a terminal, unless there is an alkyl group otherwise called otherwise.
[28]
As used herein, "the same type of carbon number" and "the type of different carbon number" are terms that distinguish terephthalate, and "the same type of carbon number" refers to an alkyl group bonded to two ester groups of terephthalate, regardless of symmetry and asymmetry. It means that the number of carbon atoms is the same as each other, and "different carbon number type" means that the number of carbon atoms of the alkyl groups bonded to two ester groups of terephthalate is different from each other.
[29]
The term "straight vinyl chloride polymer" as used herein, as one of the types of vinyl chloride polymer, may mean polymerized through suspension polymerization or bulk polymerization, and has a size of several tens to several hundreds of micrometers. It refers to a polymer having a form of porous particles with a large amount of pores distributed, no cohesiveness, and excellent flowability.
[30]
The term "paste vinyl chloride polymer" as used herein, as one of the types of vinyl chloride polymer, may mean polymerized through microsuspension polymerization, microseed polymerization, or emulsion polymerization, It refers to a polymer having a size of several thousand nanometers and has poor flowability as fine, dense, void-free particles.
[31]
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 as is not essential to operability. The term 'consisting of' excludes any component, step or procedure not specifically described or listed.
[32]
[33]
How to measure
[34]
In the present specification, analysis of the content of components in the composition is performed through gas chromatography measurement, and Agilent's gas chromatography instrument (product name: Agilent 7890 GC, column: HP-5, carrier gas: helium (flow rate 2.4 mL/min)) , detector: FID, injection volume: 1uL, initial value: 70℃/4,2min, end value: 280℃/7.8min, program rate: 15℃/min).
[35]
In the present specification, 'hardness' means shore hardness (Shore "A" and/or Shore "D") at 25° C. using ASTM D2240, measured under the conditions of 3T 10s, and plasticized It can be an index to evaluate the efficiency, and the lower it is, the better the plasticization efficiency is.
[36]
In the present specification, 'tensile strength' is a test device, UTM (manufacturer; Instron, model name; 4466), according to the ASTM D638 method, and the cross head speed is 200 mm/min (1T) ), measure the point at which the specimen is cut, and calculate by Equation 1 below.
[37]
[Equation 1]
[38]
Tensile strength (kgf/cm 2 ) = load value (kgf) / thickness (cm) x width (cm)
[39]
In the present specification, the 'elongation rate' refers to the point at which the specimen is cut after pulling the cross head speed to 200 mm/min (1T) using the UTM according to the ASTM D638 method. Then, it is calculated by Equation 2 below.
[40]
[Equation 2]
[41]
Elongation (%) = length after stretching / initial length x 100
[42]
In this specification, 'migration loss' refers to obtaining a test piece having a thickness of 2 mm or more according to KSM-3156, attaching a glass plate to both sides of the test piece, and applying a load of 1 kgf/cm 2 . After leaving the test piece in a hot air circulation oven (80°C) for 72 hours, take it out and cool it at room temperature for 4 hours. Then, after removing the glass plate attached to both sides of the test piece, measure the weight before and after leaving the glass plate and the specimen plate in the oven to calculate the transfer loss by Equation 3 below.
[43]
[Equation 3]
[44]
Transition loss (%) = {(Initial weight of test piece at room temperature - Weight of test piece after leaving the oven) / Initial weight of test piece at room temperature} x 100
[45]
In the present specification, 'volatile loss' refers to measuring the weight of the specimen after working the specimen at 80°C for 72 hours.
[46]
[Equation 4]
[47]
Loss on heating (wt%) = {(initial specimen weight - specimen weight after work) / initial specimen weight} x 100
[48]
In the present specification, the 'absorption rate' is evaluated by measuring the time it takes for the resin and the plasticizer to be mixed with each other and the torque of the mixer is stabilized using a planatary mixer (Brabender, P600) under the condition of 77 ° C. 60 rpm. .
[49]
In the case of the various measurement conditions, detailed conditions such as temperature, rotation speed, time, etc. may be slightly different depending on the case, and in different cases, the measurement method and conditions are separately specified.
[50]
[51]
Hereinafter, the present invention will be described in more detail to help the understanding of the present invention.
[52]
According to an embodiment of the present invention, the plasticizer composition includes two or more types of terephthalate and the same type of carbon number of the alkyl group bonded to the two ester groups as terephthalate, and the number of carbon atoms of the alkyl group bonded to the two ester groups as terephthalate includes at least one type having different carbon number from each other, and the type with different carbon number includes both higher alkyl and lower alkyl, wherein the higher alkyl has 8 or less carbon atoms, and the lower alkyl has 5 or more carbon atoms.
[53]
[54]
According to one embodiment of the present invention, the plasticizer composition includes the same type of carbon number of the alkyl group bonded to the two ester groups having the same number of carbon atoms, and two or more types of terephthalate having the same carbon number are included.
[55]
In the case of the type having the same number of carbon atoms, it means that the alkyl groups bonded to two ester groups present in the terephthalate are identical to each other and thus have an alkyl group having the same number of carbon atoms as the center of the benzene ring, wherein the two types of terephthalate having the same number of carbon atoms is classified into a higher alkyl terephthalate having 8 or less carbon atoms and a lower alkyl terephthalate having 5 or more carbon atoms, and may be included at the same time.
[56]
When a higher alkyl having more than 8 carbon atoms is applied, it is undesirable because it may adversely affect the plasticization efficiency. The solubility of the alcohol to be used in water increases rapidly, and accordingly, it may cause many problems, such as a problem of an increase in cost due to the separation process from water, a problem of increased wastewater treatment in terms of difficulty in separation, and the like.
[57]
The same type of carbon number is an alkyl group bonded to two ester groups, and may be n-pentyl, isopentyl, n-hexyl, isohexyl, n-heptyl, isoheptyl or 2-ethylhexyl, where it may be classified as lower alkyl. Those present may be n-pentyl, isopentyl, n-hexyl, isohexyl, n-heptyl and isoheptyl having 5 to 7 carbon atoms.
[58]
Here, 'isopentyl' refers to an alkyl group having 5 carbon atoms in which the main chain is a propyl group or a butyl group and the branched chain is a methyl group or an ethyl group, for example, 2-methylbutyl group, 3-methylbutyl group, or 2-ethylpropyl group. etc. may be applied.
[59]
In addition, here, 'isohexyl' refers to an alkyl group having 6 carbon atoms in which the main chain is a butyl group or a pentyl group and the branched chain is a methyl group or an ethyl group, for example, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 2-ethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 2,4-dimethylbutyl, 2-ethylbutyl, 3-ethylbutyl and the like may be applied.
[60]
Here, 'isoheptyl' refers to an alkyl group having 7 carbon atoms in which the main chain is a pentyl group or a hexyl group and the branched chain is a methyl group or an ethyl group, for example, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, 2-ethylpentyl, 3-ethylpentyl, 4-ethylpentyl, 2,2-dimethylpentyl, 2,3-dimethylpentyl, 2,4-dimethylpentyl, 2,5-dimethylpentyl, 3, 3-dimethylpentyl, 3,4-dimethylpentyl, 3,5-dimethylpentyl, 4,4-dimethylpentyl, 4,5-dimethylpentyl or 5,5-dimethylpentyl and the like may be applied.
[61]
In addition, those that can be classified as higher alkyl are those having 6 to 8 carbon atoms, and the alkyl group having 6 or 7 carbon atoms is the same as described above, and the alkyl group having 8 carbon atoms may be 2-ethylhexyl.
[62]
In the case of n-pentyl, isopentyl, 2-methylbutyl, n-hexyl, isohexyl, n-heptyl and isoheptyl which may be bound to the lower alkyl terephthalate, 2-ethyl which may be bound to the higher alkyl terephthalate. In that the difference in carbon number with hexyl is 3 or less, the plasticization efficiency is maintained at the same level when applied to resin compared to that of 4 as a carbon number difference of more than 3, but excellent effects in reduction in heating and mechanical properties can be seen. .
[63]
In addition, in another aspect, compared to a carbon number difference of more than 3, when applied to a paste vinyl chloride resin, the viscosity stability may be significantly excellent, and the effect of improving the tensile strength and elongation as well as the transferability may also be excellent.
[64]
More preferably, the difference in the number of carbon atoms between the two alkyl carbon atoms of the different carbon number type may be 2 or 3, and in this case, a more optimal effect can be obtained not only in transferability and stress resistance, but also in mechanical properties such as tensile strength and elongation, and reduction in heating. have.
[65]
In addition to the characteristics of the same type of carbon number as described above, in order to achieve the above-described effect, terephthalate of a different carbon number type must also be included, and in this case, the number of carbon atoms of the alkyl bonded to two ester groups of the terephthalate of the different carbon number type The difference is 3 or less, and each alkyl group having 5 to 7 carbon atoms and 6 to 8 carbon atoms may be applied.
[66]
Here, the two alkyl groups bonded to the ester group of the terephthalate having a different carbon number may be the same as the alkyl group of the lower alkyl terephthalate and the higher alkyl terephthalate having the same carbon number, respectively. When the carbon number different type of terephthalate is included, the above-described effect may be realized.
[67]
Preferably, the lower alkyl may have 5 or 6 carbon atoms among those having 5 to 7 carbon atoms, and the higher alkyl may preferably have 8 carbon atoms among those having 6 to 8 carbon atoms.
[68]
Specifically, the terephthalate having the same carbon number is, for example, di(2-ethylhexyl) terephthalate, di(n-pentyl) terephthalate, diisopentyl terephthalate or di(2-methylbutyl) terephthalate, di( n-hexyl) terephthalate, diisohexyl terephthalate, di(n-heptyl) terephthalate, or diisoheptyl terephthalate.
[69]
That is, in the case of a type having the same number of carbon atoms, there may be a symmetric type in which not only the carbon number of the mutual alkyl group is the same but also the structure is the same, and in some cases, the carbon number is the same but the structure is different, that is, an asymmetric type in which an alkyl group in a structural isomer relationship is bonded. Type terephthalate may also be included.
[70]
Asymmetric terephthalate of the same type of carbon number may be, for example, (n-pentyl)(isopentyl) terephthalate, (n-hexyl)isohexyl terephthalate, or (n-heptyl)isoheptyl terephthalate, Here, the alkyl group of 'iso-' may be selected from among the various types of alkyl groups described above.
[71]
In addition, the type of terephthalate having different carbon number is, for example, (n-pentyl)(2-ethylhexyl) terephthalate, (isopentyl)(2-ethylhexyl) terephthalate, (n-hexyl) (2-ethylhexyl) terephthalate It may be selected from the group consisting of phthalate, isohexyl (2-ethylhexyl) terephthalate, (n-heptyl) (2-ethylhexyl) terephthalate and isoheptyl (2-ethylhexyl) terephthalate, where ' Iso-' is also the same as above.
[72]
Meanwhile, the plasticizer composition according to another embodiment of the present invention may essentially include two types of terephthalate having the same type of carbon number and one type of terephthalate having a different type of carbon number. In addition to this, as the type having the same number of carbon atoms, it may further include one or more types of terephthalate of the same type having the same carbon number and having an alkyl group having another carbon number than the two types of the same type having the same number of carbon atoms, and thus the type having different carbon atoms may also be further included . In this case, the essentially included terephthalate of different carbon number type may be one in which the higher alkyl has 8 carbon atoms, and the terephthalate of the different carbon number type that may be additionally included may be one in which the higher alkyl has 6 or 7 carbon atoms. .
[73]
As such, the inclusion of terephthalate of a carbon number different type, which is generated as one type having a different number of carbon atoms is included in addition to the two types necessarily included in the same type of carbon number, enables more precise control of physical properties, and improves the effect of improving physical properties. It has the advantage of being able to see more optimally.
[74]
The plasticizer composition according to an embodiment of the present invention includes a type having the same number of carbon atoms and a type having a different number of carbon atoms as the terephthalate as described above, but the number of terephthalate of each type, the type of the bonded alkyl group, Due to factors such as the difference in carbon number, it is possible to improve physical properties such as heat loss, migration resistance, and stress resistance, and furthermore, the viscosity stability of the resin can be improved. can be maintained and improved.
[75]
However, preferably, when the lower alkyl, that is, an alkyl having 5 to 7 carbon atoms, may preferably have 5 or 6 carbon atoms, and in the case of an alkyl having 5 carbon atoms, n-pentyl or isopentyl may be applied, respectively. In the case of alkyl having 6 carbon atoms and 6 carbon atoms, n-hexyl or isohexyl may be applied, respectively, but considering the degree of synergistic effect, it may be more preferable to apply a mixture derived from a mixed alcohol thereof.
[76]
In addition, when lower alkyl is applied to the plasticizer composition, as described above, it may be preferable to apply a mixed product derived from a mixed alcohol compared to a single alkyl group from a single alcohol is applied as a product, at this time Based on the three or more terephthalate-based compositions produced, the degree of branching may be preferably 2.0 or less, and more preferably 1.5 or less.
[77]
Here, the 'branching degree' may mean how many branched carbons the alkyl groups bonded to the material included in the composition have, and the degree may be determined according to the weight ratio of the material. For example, assuming that the alcohol mixture contains 60% by weight of n-hexyl alcohol, 30% by weight of methylpentyl alcohol, and 10% by weight of ethylbutyl alcohol, the number of branching carbons of each alcohol is 0, 1, and 2, respectively. , the degree of branching may be 0.5 calculated as [(60x0)+(30x1)+(10x2)] / 100, and this degree of branching is calculated based on the same number of carbons.
[78]
Preferably, when derived from the mixed alcohol, the alkyl group applied to terephthalate includes n-pentyl, 2-methylbutyl and 3-methylbutyl when the number of carbon atoms is 5, and when the number of carbon atoms is 6, the alkyl group includes n-hexyl. , 2-methylpentyl, 2-ethylbutyl, and 2,4-dimethylbutyl, and the like, may include the aforementioned isomers.
[79]
As such, if the mixed alkyl group by the mixed alcohol is implemented in the terephthalate-based plasticizer composition and at the same time satisfies the above-described degree of branching, improvement effects such as plasticization efficiency, transferability, and heating loss can be expected.
[80]
According to an embodiment of the present invention, the plasticizer composition may have a water content of 100 ppm or less based on the total weight of the composition, preferably 70 ppm or less, and more preferably 50 ppm or less. When the water content in the plasticizer is high, the plasticizer is highly likely to be deteriorated by environmental factors, and there is a high possibility of causing problems during processing.
[81]
[82]
More specifically, if the terephthalate contained in the plasticizer composition is viewed as a lower alkyl terephthalate, a terephthalate of a different carbon number, and a higher alkyl terephthalate, each of 0.5 to 50% by weight and 3.0 to 70% by weight relative to the total weight of the plasticizer composition % and 0.5 to 95% by weight, these contents are a value when the sum of the three types of terephthalates is 100% by weight, and the content is not considered until other materials are included in the plasticizer composition.
[83]
In the case of having the above content, as described above, the effect that can be realized from the difference in the number of carbon atoms of the alkyl group bonded to the terephthalate of the different type of carbon number is 3 or less can be more preferably realized, and the reproducibility of the effect is also excellent. can
[84]
Further, in terms of optimizing this effect, the content of the three types of terephthalates may be preferably 0.5 to 30% by weight, 10 to 60% by weight, and 35 to 90% by weight.
[85]
[86]
The method for preparing a plasticizer composition according to an embodiment of the present invention is a method known in the art, and may be applied without particular limitation if it can prepare the above-described plasticizer composition.
[87]
In particular, in the case of the plasticizer composition, including three types of terephthalates as a basis, an esterification reaction may be used, and both a direct esterification reaction and a transesterification reaction may be applied.
[88]
As an example, the direct esterification reaction includes the steps of adding terephthalic acid and two or more alcohols, then adding a catalyst and reacting in a nitrogen atmosphere; removing unreacted alcohol and neutralizing unreacted acid; and dehydration and filtration by vacuum distillation.
[89]
The alcohol may be a single alcohol or a mixed alcohol having the same number of carbon atoms selected from the group consisting of n-pentanol, isopentanol, n-hexanol, isohexanol, n-heptanol and isoheptanol, and a mixed alcohol In this case, it may be a mixture of alcohols in a structural isomer relationship, and in this case, the degree of branching of the mixed alcohol may be 2.0 or less, preferably 1.5 or less, as described above. And, as another one type, 2-ethylhexyl alcohol may be applied. The alcohol may be used within the range of 150 to 500 mol%, 200 to 400 mol%, 200 to 350 mol%, 250 to 400 mol%, or 270 to 330 mol% based on 100 mol% of terephthalic acid.
[90]
The catalyst is, for example, an acid catalyst such as sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, para-toluenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, alkyl sulfuric acid, aluminum lactate, lithium fluoride, potassium chloride, cesium chloride, calcium chloride, It may be at least one selected from metal salts such as iron chloride and aluminum phosphate, metal oxides such as heteropolyacids, natural/synthetic zeolites, cation and anion exchange resins, tetraalkyl titanate, and organometallics such as polymers thereof. As a specific example, the catalyst may be tetraalkyl titanate.
[91]
The amount of catalyst used may vary depending on the type, for example, in the case of a homogeneous catalyst, 0.01 to 5% by weight, 0.01 to 3% by weight, 1 to 5% by weight, or 2 to 4% by weight based on 100% by weight of the total reactants. and in the case of a heterogeneous catalyst, it may be in the range of 5 to 200 wt%, 5 to 100 wt%, 20 to 200 wt%, or 20 to 150 wt% of the total amount of reactants.
[92]
At this time, the reaction temperature may be in the range of 180 to 280 ℃, 200 to 250 ℃, or 210 to 230 ℃.
[93]
In another example, the transesterification reaction is a group consisting of di(2-ethylhexyl) terephthalate, n-pentanol, isopentanol, n-hexanol, isohexanol, n-heptanol and isoheptanol. A terephthalate compound may be prepared through a transesterification reaction in which at least one alcohol selected from the group having the same number of carbon atoms, that is, a single alcohol or a mixed alcohol that is a mixture of structural isomers is reacted. Here, the alkyl group of the terephthalate and the alcohol may cross each other.
[94]
As used in the present invention, "transesterification reaction" refers to a reaction in which an alcohol and an ester are reacted as shown in Scheme 1 below, and as shown in Scheme 1 below, R of an ester is interchanged with R' of an alcohol:
[95]
[Scheme 1]
[96]

[97]
According to an embodiment of the present invention, when the transesterification reaction is carried out, when the alkoxide of alcohol attacks the carbons of two ester (RCOOR") groups present in the ester-based compound; attacking the carbon of the ester (RCOOR") group; In the case of unreacted non-reacted; in three cases, three types of ester compositions can be produced by number. At this time, when two or more types of alcohol are added, it is possible to predict the shape and number of the probabilistically generated composition. It can optionally be prepared.
[98]
In addition, the transesterification reaction has the advantage of not causing a wastewater problem compared to the acid-alcohol esterification reaction, and since it can be carried out in the absence of a catalyst, the problem when using an acid catalyst can be solved.
[99]
In the mixture prepared by the transesterification reaction, the composition ratio of the mixture may be controlled according to the amount of alcohol added. The amount of the alcohol added may be 0.1 to 89.9 parts by weight, specifically 3 to 50 parts by weight, and more specifically 5 to 40 parts by weight based on 100 parts by weight of the terephthalate compound.
[100]
As for the terephthalate compound, the greater the amount of alcohol added, the greater the mole fraction of terephthalate participating in the transesterification reaction will increase. Correspondingly, the content of unreacted terephthalate may show a tendency to decrease.
[101]
According to an embodiment of the present invention, the molar ratio of the reactant terephthalate and alcohol is, for example, 1:0.005 to 5.0, 1:0.05 to 2.5, or 1:0.1 to 1.0, and within this range, fairness and economic efficiency may be excellent. There is an effect of obtaining a plasticizer composition that can implement the above-described effect.
[102]
According to an embodiment of the present invention, the transesterification reaction is carried out at a reaction temperature of 120°C to 190°C, preferably 135°C to 180°C, more preferably 141°C to 179°C for 10 minutes to 10 hours, preferably Preferably, it is carried out in 30 minutes to 8 hours, more preferably in 1 to 6 hours. Within the above temperature and time range, it is possible to efficiently control the component ratio of the final plasticizer composition. In this case, the reaction time may be calculated from the point at which the reaction temperature is reached after the reactant is heated.
[103]
The transesterification reaction may be carried out under an acid catalyst or a metal catalyst, and in this case, the reaction time is shortened.
[104]
The acid catalyst may be, for example, sulfuric acid, methanesulfonic acid or p-toluenesulfonic acid, and the metal catalyst may be, for example, an organometallic catalyst, a metal oxide catalyst, a metal salt catalyst, or a metal itself.
[105]
The metal component may be, for example, any one selected from the group consisting of tin, titanium, and zirconium, or a mixture of two or more thereof.
[106]
In addition, the method may further include distilling and removing unreacted alcohol and reaction by-products after the transesterification reaction. The distillation may be, for example, a two-step distillation in which the alcohol and the reaction by-products are separated using a difference in boiling point. In another example, the distillation may be mixed distillation. In this case, there is an effect that the ester-based plasticizer composition can be secured relatively stably in a desired composition ratio. The mixed distillation means simultaneously distilling unreacted alcohol and reaction by-products.
[107]
[108]
According to another embodiment of the present invention, there is provided a resin composition comprising the above-described plasticizer composition and resin.
[109]
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.
[110]
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.
[111]
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.
[112]
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 fine resin particles prepared by emulsion polymerization, etc., and such a vinyl chloride polymer is called a paste vinyl chloride resin.
[113]
In this case, in the case of the straight vinyl chloride polymer, the plasticizer may be included in an amount of 5 to 150 parts by weight based on 100 parts by weight of the polymer, and is preferably included in the range of 5 to 80 parts by weight, and in the case of a paste vinyl chloride polymer, 100 parts by weight of the polymer It may be included in an amount of 5 to 150 parts by weight based on parts, and is preferably included in a range of 40 to 120 parts by weight.
[114]
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.
[115]
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.
[116]
In addition, the resin composition may further include other additives such as a stabilizer, if necessary. Other additives such as the stabilizer may be, for example, 0 to 20 parts by weight, preferably 1 to 15 parts by weight, based on 100 parts by weight of the resin.
[117]
The stabilizer may include, for example, a calcium-zinc (Ca-Zn-based) stabilizer such as a calcium-zinc complex stearate, but is not particularly limited thereto.
[118]
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.
[119]
[120]
Example
[121]
Hereinafter, examples will be given to describe the present invention in detail. However, the embodiments according to the present invention may be modified in various other forms, and the scope of the present invention should not be construed as being limited to the embodiments described below. The embodiments of the present invention are provided to more completely explain the present invention to those of ordinary skill in the art.
[122]
[123]
Example 1
[124]
2000 g of di(2-ethylhexyl) terephthalate (GL300, LG Chem) and 340 g of n-pentyl alcohol (17 parts by weight based on 100 parts by weight of DEHTP) were added to a reactor equipped with a stirrer, condenser and decanter, and then nitrogen Trans-esterification reaction was performed for 2 hours at a reaction temperature of 160° C. under an atmosphere, and di(n-pentyl)terephthalate (DnPTP), (n-pentyl)(2-ethylhexyl)terephthalate (nPEHTP) and di(2 -Ethylhexyl) terephthalate (DEHTP) was obtained in a composition comprising 6.4 wt%, 38.3 wt%, and 55.3 wt%, respectively.
[125]
[126]
Example 2
[127]
2000 g of di(2-ethylhexyl) terephthalate (GL300, LG Chem) and 340 g of 2-methylbutyl alcohol (17 parts by weight based on 100 parts by weight of DEHTP) were added to a reactor equipped with a stirrer, condenser and decanter, Trans-esterification reaction was performed for 2 hours at a reaction temperature of 160° C. under a nitrogen atmosphere to obtain di(2-methylbutyl)terephthalate (DMBTP), (2-methylbutyl)(2-ethylhexyl)terephthalate (MBEHTP) and A composition comprising di(2-ethylhexyl)terephthalate (DEHTP) in an amount of 6.4 wt%, 38.2 wt%, and 55.4 wt%, respectively, was obtained.
[128]
[129]
Example 3
[130]
The composition prepared in Example 1 and the composition prepared in Example 2 were mixed in a weight ratio of 70:30 to prepare a composition.
[131]
[132]
Example 4
[133]
2000 g of di(2-ethylhexyl) terephthalate (GL300, LG Chem) and 220 g of n-pentyl alcohol (11 parts by weight based on 100 parts by weight of DEHTP) were added to a reactor equipped with a stirrer, condenser and decanter, and then nitrogen Trans-esterification reaction was performed for 2 hours at a reaction temperature of 160° C. under an atmosphere, and di(n-pentyl)terephthalate (DnPTP), (n-pentyl)(2-ethylhexyl)terephthalate (nPEHTP) and di(2 -Ethylhexyl) terephthalate (DEHTP) was obtained in a composition comprising 2.4 wt%, 26.9 wt%, and 70.7 wt%, respectively.
[134]
[135]
Example 5
[136]
Di (2-methylbutyl) terephthalate (DMBTP), (2-methylbutyl) (2-methylbutyl) ( A composition comprising 2-ethylhexyl) terephthalate (MBEHTP) and di(2-ethylhexyl) terephthalate (DEHTP) in an amount of 2.1 wt%, 25.8 wt%, and 72.1 wt%, respectively, was obtained.
[137]
[138]
Example 6
[139]
Di(2-ethylhexyl)terephthalate (GL300, LG Chem) and 340 g of n-hexyl alcohol (17 parts by weight based on 100 parts by weight of DEHTP) were added to a reactor equipped with a stirrer, condenser and decanter, and then nitrogen atmosphere Trans-esterification reaction was carried out for 2 hours at a reaction temperature of 160 ° C., di (n-hexyl) terephthalate (DHxTP), (n-hexyl) (2-ethylhexyl) terephthalate (HxEHTP) and di (2- A composition comprising ethylhexyl) terephthalate (DEHTP) in an amount of 6.8 wt%, 38.8 wt%, and 54.4 wt%, respectively, was obtained.
[140]
[141]
Example 7
[142]
Di (2-ethylhexyl) terephthalate (GL300, LG Chem) and 340 g of n-hexyl alcohol (11 parts by weight based on 100 parts by weight of DEHTP) were added to a reactor equipped with a stirrer, condenser and decanter, and then nitrogen atmosphere Trans-esterification reaction was carried out for 2 hours at a reaction temperature of 160 ° C., di (n-hexyl) terephthalate (DHxTP), (n-hexyl) (2-ethylhexyl) terephthalate (HxEHTP) and di (2- A composition comprising ethylhexyl) terephthalate (DEHTP) in an amount of 1.8 wt%, 25.0 wt%, and 73.2 wt%, respectively, was obtained.
[143]
[144]
Example 8
[145]
2000 g of di(2-ethylhexyl) terephthalate (GL300, LG Chem) and 360 g of n-heptyl alcohol (18 parts by weight based on 100 parts by weight of DEHTP) were added to a reactor equipped with a stirrer, condenser and decanter, and then nitrogen Trans-esterification reaction was performed for 2 hours at a reaction temperature of 160° C. under an atmosphere to di(n-heptyl) terephthalate (DHpTP), (n-heptyl) (2-ethylhexyl) terephthalate (HpEHTP) and di(2 -Ethylhexyl) terephthalate (DEHTP) was obtained in a composition comprising 7.9 wt%, 39.9 wt%, and 52.2 wt%, respectively.
[146]
[147]
Example 9
[148]
2000 g of di(2-ethylhexyl) terephthalate (GL300, LG Chem) and 360 g of n-heptyl alcohol (11 parts by weight based on 100 parts by weight of DEHTP) were added to a reactor equipped with a stirrer, condenser and decanter, and then nitrogen Trans-esterification reaction was performed for 2 hours at a reaction temperature of 160° C. under an atmosphere to di(n-heptyl) terephthalate (DHpTP), (n-heptyl) (2-ethylhexyl) terephthalate (HpEHTP) and di(2 -Ethylhexyl) terephthalate (DEHTP) was obtained in a composition comprising 1.5 wt%, 23.2 wt%, and 75.3 wt%, respectively.
[149]
[150]
Comparative Example 1
[151]
As a product of LG Chem, di(2-ethylhexyl) terephthalate (DEHTP, LGflex GL300) was used as a plasticizer composition.
[152]
[153]
Comparative Example 2
[154]
6.4 wt%, 38.8 wt%, and 54.9 wt% of dibutyl terephthalate (DBTP), butyl (2-ethylhexyl) terephthalate (BEHTP) and di(2-ethylhexyl) terephthalate (DEHTP) as products of LG Chem, respectively A composition (LGflex GL500) containing as a plasticizer composition.
[155]
[156]
Comparative Example 3
[157]
4.1 wt%, 25.7 wt%, and 70.2 wt% of dibutyl terephthalate (DBTP), butyl (2-ethylhexyl) terephthalate (BEHTP) and di(2-ethylhexyl) terephthalate (DEHTP) as a product of LG Chem, respectively A composition (LGflex GL520) containing as a plasticizer composition.
[158]
[159]
Comparative Example 4
[160]
2000 g of diisononyl terephthalate (DINTP) and 360 g of n-pentyl alcohol (18 parts by weight based on 100 parts by weight of DINTP) were added to a reactor equipped with a stirrer, a condenser and a decanter, and then a reaction temperature of 160° C. under a nitrogen atmosphere by trans-esterification reaction for 2 hours in %, a composition comprising 40.1 wt% and 52.8 wt% was obtained.
[161]
[162]
Comparative Example 5
[163]
2000 g of diisononyl terephthalate (DINTP) and 220 g of n-pentyl alcohol (11 parts by weight based on 100 parts by weight of DINTP) were added to a reactor equipped with a stirrer, a condenser and a decanter, followed by a reaction temperature of 160° C. under a nitrogen atmosphere By trans-esterification reaction for 2 hours in %, to obtain a composition comprising 22.7 wt% and 75.7 wt%.
[164]
[165]
Experimental Example 1: Rigid sheet performance evaluation
[166]
Using the plasticizers of Examples and Comparative Examples, specimens were manufactured under the following prescription and manufacturing conditions according to ASTM D638.
[167]
(1) Prescription : 100 parts by weight of straight vinyl chloride polymer (LS100S), 30 parts by weight of plasticizer and 3 parts by weight of stabilizer (BZ-153T)
[168]
(2) Mixing : Mixing at 700 rpm at 98℃
[169]
(3) Specimen production : 1T and 3T sheets were produced by using a roll mill at 160°C for 4 minutes and pressing at 180°C for 2.5 minutes (low pressure) and 2 minutes (high pressure).
[170]
(4) Evaluation items
[171]
1) Hardness : Using ASTM D2240, the shore hardness (Shore "A" and "D") at 25 ℃ was measured for 10 seconds with a 3T specimen. It is evaluated that the smaller the numerical value, the better the plasticization efficiency.
[172]
2) Tensile strength : After pulling the cross head speed to 200 mm/min using a test device, UTM (manufacturer; Instron, model name; 4466), according to ASTM D638 method, 1T specimen The cut point was measured. Tensile strength was calculated as follows:
[173]
Tensile strength (kgf/cm 2 ) = load value (kgf) / thickness (cm) x width (cm)
[174]
3) Measurement of elongation rate : According to the ASTM D638 method, after pulling the cross head speed to 200 mm/min using the UTM, measuring the point at which the 1T specimen is cut, the elongation is measured Calculated as follows:
[175]
Elongation (%) = length after stretching / initial length x 100 was calculated.
[176]
4) Measurement of migration loss : A test piece having a thickness of 2 mm or more was obtained according to KSM-3156, and after attaching a glass plate to both sides of the 1T specimen, 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 for 4 hours. Then, after removing the glass plate attached to both sides of the test piece, the weight before and after leaving the glass plate and the specimen plate in the oven was measured to calculate the transfer loss by the following formula.
[177]
Transition loss (%) = {(Initial weight of test piece at room temperature - Weight of test piece after leaving the oven) / Initial weight of test piece at room temperature} x 100
[178]
5) Measurement of volatile loss : After working the prepared specimen at 80° C. for 72 hours, the weight of the specimen was measured.
[179]
Loss on heating (% by weight) = initial specimen weight - (weight of specimen after working at 80 °C for 72 hours) / initial specimen weight x 100.
[180]
6) Measurement of absorption rate
[181]
The absorption rate was measured by measuring the time (mm:ss) required for the resin and ester compound to be mixed with each other and to stabilize the torque of the mixer using a planatary mixer (Brabender, P600) under the conditions of 77℃ and 60rpm. evaluated.
[182]
[183]
(5) Evaluation results
[184]
The evaluation results of the above items are shown in Table 1 below.
[185]
[Table 1]
Hardness (Shore A) Hardness (Shore D) Performance loss (%) Heat loss (%) Tensile strength (kgf/cm 2 ) Elongation (%)
Example 1 97.5 59.6 1.65 0.98 268.3 308.7
Example 2 97.8 60.0 1.78 1.23 267.9 293.1
Example 3 97.6 59.6 1.67 0.99 268.0 305.7
Example 4 97.8 59.8 1.88 0.86 268.9 310.5
Example 5 98.0 59.6 1.69 0.90 268.2 305.4
Example 6 98.2 59.6 2.12 0.91 265.6 301.2
Example 7 98.4 59.7 2.10 0.80 268.4 305.2
Example 8 98.6 59.9 2.25 0.80 266.2 294.1
Example 9 98.7 59.9 2.37 0.79 266.7 298.6
Comparative Example 1 99.8 61.6 3.81 0.78 264.7 296.9
Comparative Example 2 97.4 59.4 3.12 2.54 248.5 287.7
Comparative Example 3 98.2 59.8 3.54 2.01 250.3 281.4
Comparative Example 4 99.6 61.5 4.62 1.16 257.0 274.3
Comparative Example 5 99.9 61.9 4.41 0.80 253.2 270.2
[186]
Referring to Table 1, in the case of Examples 1 to 9, compared to Comparative Examples 1 to 5, it can be seen that the overall physical properties are balanced. In the case of di(2-ethylhexyl) terephthalate, which is GL300 of Comparative Example 1 as an existing product, there is a problem that the plasticization efficiency is not good and the transferability is poor. In the case of Comparative Example 2 of GL500 and Comparative Example 3 of GL520, plasticization Although the efficiency is improved, there is a problem that the elongation and tensile strength are poor, and Comparative Examples 4 and 5, in which the carbon number of lower alkyl and higher alkyl are 5 and 9, respectively, has no improvement in plasticization efficiency compared to Comparative Example 1, but rather transferability and elongation And it can be seen that the tensile strength shows a worse result. However, in the case of Examples 1 to 9, it can be seen that a significant effect was shown in the transferability, the elongation and tensile strength were greatly improved, and the plasticization efficiency was also maintained at the same level.
[187]
Through this, it was confirmed that it can be a substitute material that can improve the transferability and mechanical properties with poor physical properties without deterioration of excellent physical properties compared to the existing product.
[188]
[189]
Experimental Example 2: Soft sheet performance evaluation
[190]
Using the plasticizers of Examples and Comparative Examples, specimens were manufactured under the following prescription and manufacturing conditions according to ASTM D638.
[191]
(1) Prescription : 100 parts by weight of straight vinyl chloride polymer (LS100S), 60 parts by weight of plasticizer and 3 parts by weight of stabilizer (BZ-153T)
[192]
(2) Mixing : Mixing at 700 rpm at 98℃
[193]
(3) Specimen production : 1T and 3T sheets were produced by using a roll mill at 160°C for 4 minutes and pressing at 180°C for 2.5 minutes (low pressure) and 2 minutes (high pressure).
[194]
(4) Evaluation items
[195]
1) Hardness (plasticization efficiency) (hardness) : Using ASTM D2240, the shore hardness (Shore "A" and "D") at 25 ℃ was measured with a 3T specimen for 10 seconds. It is evaluated that the smaller the numerical value, the better the plasticization efficiency.
[196]
2) Tensile strength : After pulling the cross head speed to 200 mm/min using a test device, UTM (manufacturer; Instron, model name; 4466), according to ASTM D638 method, 1T specimen The cut point was measured. Tensile strength was calculated as follows:
[197]
Tensile strength (kgf/cm 2 ) = load value (kgf) / thickness (cm) x width (cm)
[198]
3) Measurement of elongation rate : According to the ASTM D638 method, after pulling the cross head speed to 200 mm/min using the UTM, measuring the point at which the 1T specimen is cut, the elongation is measured Calculated as follows:
[199]
Elongation (%) = length after stretching / initial length x 100 was calculated.
[200]
4) Measurement of migration loss : After attaching a glass plate to both sides of the 1T specimen, 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 for 4 hours. Then, after removing the glass plate attached to both sides of the test piece, the weight before and after leaving the glass plate and the specimen plate in the oven was measured to calculate the transfer loss by the following formula.
[201]
Transition loss (%) = {(Initial weight of test piece at room temperature - Weight of test piece after leaving the oven) / Initial weight of test piece at room temperature} x 100
[202]
5) Measurement of volatile loss : After working the prepared specimen at 80° C. for 72 hours, the weight of the specimen was measured.
[203]
Loss on heating (% by weight) = initial specimen weight - (weight of specimen after working at 80 °C for 72 hours) / initial specimen weight x 100.
[204]
6) Stress test (stress resistance) : After leaving a specimen with a thickness of 2 mm in a bent state at 23° C. for 168 hours, the degree of transition (the degree of seeping) was observed, and the result was written as a numerical value, at 0 The closer it was, the better the properties were.
[205]
[206]
(5) Evaluation results
[207]
The evaluation results of the above items are shown in Table 2 below.
[208]
[Table 2]
Hardness (Shore A) Hardness (Shore D) Performance loss (%) Heat loss (%) Tensile strength kgf/cm 2 Elongation (%) stress resistance
Example 1 78.1 33.0 5.33 0.92 194.1 359.9 0
Example 2 79.0 33.5 5.80 1.48 189.0 349.8 0
Example 3 78.3 33.1 5.40 0.98 194.2 356.2 0
Example 4 79.0 33.4 5.23 0.76 198.6 346.7 0
Example 5 79.4 33.5 5.25 0.84 192.5 348.2 0
Example 6 79.3 33.4 5.87 0.83 191.9 349.3 0.5
Example 7 79.8 33.6 5.64 0.78 196.4 345.7 0.5
Example 8 80.0 33.9 6.07 0.71 194.7 339.4 1.0
Example 9 80.6 34.2 5.89 0.65 199.2 340.5 1.5
Comparative Example 1 81.0 34.7 8.29 0.76 190.7 319.7 3
Comparative Example 2 77.9 32.3 6.57 2.55 178.0 325.2 0
Comparative Example 3 79.0 33.5 6.89 2.20 180.3 324.5 0
Comparative Example 4 82.0 35.8 7.68 0.53 182.3 324.9 2.5
Comparative Example 5 83.3 36.7 7.89 0.50 184.5 321.4 3
[209]
Referring to Table 2, in the case of Examples 1 to 9, compared to Comparative Examples 1 to 5, it can be confirmed that the overall physical properties are balanced. In the case of di(2-ethylhexyl) terephthalate, which is GL300 of Comparative Example 1 as an existing product, there is a problem that the plasticization efficiency is not good and the transferability is poor. In the case of Comparative Example 2 of GL500 and Comparative Example 3 of GL520, plasticization Although the efficiency is improved, there is a problem that the elongation and tensile strength are poor, and Comparative Examples 4 and 5, in which the carbon number of lower alkyl and higher alkyl are 5 and 9, respectively, has no improvement in plasticization efficiency compared to Comparative Example 1, but rather the transferability and elongation and tensile strength, it can be seen that there is no improvement at all compared to the existing products in stress resistance. However, in the case of Examples 1 to 9, a significant effect was shown in transferability, elongation and tensile strength were greatly improved, stress resistance was also improved, and it can be confirmed that plasticization efficiency was also maintained at the same level.
[210]
Through this, it was confirmed that it can be an alternative material that can improve the transferability, mechanical properties, and stress resistance with poor physical properties without deterioration of excellent properties compared to existing products.
[211]
[212]
Experimental Example 3: Evaluation of plastisol performance for gloves
[213]
Using the plasticizers of Examples and Comparative Examples, specimens were manufactured under the following prescription and manufacturing conditions according to ASTM D638.
[214]
(1) Prescription : 100 parts by weight of paste vinyl chloride polymer (LS170G), 75 parts by weight of plasticizer, 20 parts by weight of viscosity reducing agent (YKD80) and 1 part by weight of stabilizer (CZ400)
[215]
(2) Mixing : Mixing at 1500 rpm for 20 minutes, at 1000 rpm for 20 minutes
[216]
(3) Specimen Preparation : Spread the blended plastisol to a thickness of 0.3 mm, and use an oven to cure it at 230°C for 2 minutes to prepare a specimen.
[217]
(4) Evaluation items
[218]
1) Viscosity : Brookfield viscosity, measured using a Brookfield (LV type) viscometer. #62 was used as the spindle, the measurement speed was 6 rpm, and the measurement temperature was 25°C and 60°C. was measured as
[219]
2) Tensile strength : After pulling the crosshead speed to 100 mm/min using a test device, UTM (manufacturer; Instron, model name; 4466), according to the ASTM D412 method, the specimen was The cut point was measured. Tensile strength was calculated as follows:
[220]
Tensile strength (kgf/cm 2 ) = load value (kgf) / thickness (cm) x width (cm)
[221]
3) Measurement of elongation rate : According to ASTM D412 method, after pulling the cross head speed to 100 mm/min using the UTM, measuring the point at which the specimen is cut, and then measuring the elongation as follows Calculated as:
[222]
Elongation (%) = length after stretching / initial length x 100 was calculated.
[223]
4) Measurement of migration loss : After attaching a glass plate to both sides of the specimen, a load of 1 kgf/cm 2 was applied. The specimens were left in a hot air circulation oven (60° C.) for 72 hours, then taken out and cooled at room temperature for 4 hours. Then, after removing the glass plate attached to both sides of the test piece, the weight before and after leaving the glass plate and the specimen plate in the oven was measured to calculate the transfer loss by the following formula.
[224]
Transition loss (%) = {(Initial weight of test piece at room temperature - Weight of test piece after leaving the oven) / Initial weight of test piece at room temperature} x 100
[225]
[226]
(5) Evaluation results
[227]
The evaluation results of the above items are shown in Table 3 below.
[228]
[Table 3]
25℃ Viscosity (cP)1 hr 25℃ Viscosity (cP)1day 25℃ Viscosity (cP) Change (%) 60℃ Viscosity (cP)1 hr 60℃ Viscosity (cP)1day 60℃ Viscosity (cP) Change (%) Performance loss (%) Tensile strength (MPa) Elongation (%)
Example 1 235 250 6.4 160 205 28.1 9.36 13.2 364.8
Example 2 240 265 10.4 155 215 38.7 9.13 13.9 370.3
Example 3 235 255 8.5 155 210 35.5 9.21 13.5 368.9
Example 4 205 215 4.9 150 175 16.7 9.53 13.3 363.5
Example 5 215 235 9.3 155 185 19.4 9.76 13.5 365.2
Example 6 210 245 16.7 135 170 25.9 10.91 12.5 360.3
Example 7 220 255 15.9 140 170 21.4 10.90 12.8 362.8
Example 8 225 260 15.6 135 160 18.5 10.96 13.4 368.0
Example 9 230 270 17.4 125 160 28.0 10.84 13.5 359.4
Comparative Example 1 225 300 33.3 120 190 58.3 11.34 11.9 320.5
Comparative Example 2 190 240 26.3 130 290 123.0 8.23 11.0 335.5
Comparative Example 3 200 255 27.5 110 190 72.7 10.91 11.6 340.3
Comparative Example 4 225 290 28.9 105 180 71.4 10.96 12.2 348.0
Comparative Example 5 240 300 25.0 110 200 81.8 11.56 12.3 350.3
[229]
[230]
Referring to Table 3, in the case of Examples 1 to 9, it can be seen that the change in viscosity over time exhibits significant stability at both room temperature and high temperature. On the other hand, in the case of Comparative Examples 1 to 5, Comparative Example 1, which is the existing product, GL300, showed a degree of change with time more than twice compared to the Examples, confirming that the stability was somewhat lowered, and Comparative Example 2, an improved product of Comparative Example 1 Even in the case of to 5, it can be confirmed that the change in viscosity over time is at a fairly poor level.
[231]
In addition, in the case of tensile strength and elongation, it can be seen that Comparative Examples 1 to 5 are significantly inferior to Examples 1 to 9, and in particular, it can be confirmed that the elongation exhibits poor physical properties of 10% or more.
[232]
[233]
That is, referring to Experimental Examples 1 to 3, the plasticizer composition according to an embodiment of the present invention includes terephthalate having the same type of carbon number and terephthalate having a different number of carbon atoms, but bonding to two ester groups of the type terephthalate having different carbon number. It can be seen that, when applying the alkyl group having 5 to 7 carbon atoms and 8 carbon atoms, respectively, a significantly superior effect can be achieved compared to the other cases, and the difference in carbon number of the alkyl group is 3 or less, and 4 exceeding it It can be seen that the difference between
Claims
[Claim 1]
As terephthalate, the type having the same carbon number of the alkyl group bonded to the two ester groups is the same; as terephthalate, including two or more types, and as terephthalate, the type having a different carbon number of the alkyl group bonded to the two ester groups is different; including one or more types And, the different carbon number type includes both higher alkyl and lower alkyl, wherein the higher alkyl is selected from those having 8 or less carbon atoms, and the lower alkyl is selected from those having 5 or more carbon atoms.
[Claim 2]
The plasticizer composition according to claim 1, wherein the same type of carbon number comprises one higher alkyl terephthalate and one or more lower alkyl terephthalates.
[Claim 3]
The plasticizer composition according to claim 1, wherein the difference in carbon number between the higher alkyl and the lower alkyl is 3 or less.
[Claim 4]
The plasticizer composition according to claim 1, wherein the higher alkyl is an alkyl group selected from 6 to 8 carbon atoms, and the lower alkyl is an alkyl group selected from 5 to 7 carbon atoms.
[Claim 5]
The plasticizer composition according to claim 1, wherein the different carbon number type includes a higher alkyl having 8 carbon atoms.
[Claim 6]
According to claim 1, wherein the carbon number of the different type, higher alkyl having 8 carbon atoms; And a higher alkyl having 6 or 7 carbon atoms; a plasticizer composition comprising a.
[Claim 7]
The plasticizer composition according to claim 1, wherein the plasticizer composition has a degree of branching based on the entire alkyl group having the same number of carbon atoms in the composition of 2.0 or less.
[Claim 8]
The method according to claim 1, wherein the carbon number of the same type is di(2-ethylhexyl) terephthalate, di(n-pentyl) terephthalate, diisopentyl terephthalate, (n-pentyl) isopentyl terephthalate, and di(n- selected from the group consisting of hexyl) terephthalate, diisohexyl terephthalate, (n-hexyl)isohexyl terephthalate, di(n-heptyl) terephthalate, diisoheptyl terephthalate and (n-heptyl)isoheptyl terephthalate. A plasticizer composition comprising two or more.
[Claim 9]
According to claim 1, wherein the carbon number different type is (n-pentyl) (2-ethylhexyl) terephthalate, (isopentyl) (2-ethylhexyl) terephthalate, (n-hexyl) (2-ethylhexyl) terephthalate Which comprises at least one selected from the group consisting of phthalate, isohexyl (2-ethylhexyl) terephthalate, (n-heptyl) (2-ethylhexyl) terephthalate, and isoheptyl (2-ethylhexyl) terephthalate plasticizer composition.
[Claim 10]
According to claim 2, 0.5 to 50% by weight of a lower alkyl terephthalate, based on the total weight of the plasticizer composition; 3.0 to 70% by weight of terephthalate of different carbon number; And 0.5 to 95% by weight of higher alkyl terephthalate; plasticizer composition comprising a.