[One]Cross Citation with Related Applications
[2]This application claims the benefit of priority based on Korean Patent Application No. 10-2019-0051716 dated May 02, 2019, 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 cyclohexane triester-based plasticizer composition including a cyclohexane triester having the same number of carbon atoms in the alkyl radicals of the components in the composition, 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 on 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 such as flooring, wallpaper, soft and hard sheet, calendaring industry, and extrusion/injection compound industry, the demand for these eco-friendly products is increasing, and the quality characteristics, processability and In order to enhance productivity, 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 the product of the transesterification reaction with butanol as a plasticizer, but while the plasticization efficiency is improved, the reduction in heating 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 to compensate for this through mixing with other secondary plasticizers in general.
[13]
However, when a secondary plasticizer is applied, 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. The downside is that there are no problems.
[14]
In addition, when a substance such as tri(2-ethylhexyl) trimellitate or triisononyl trimellitate is applied as a trimellitate-based product in order to improve the poor transferability and weight loss characteristics of the DEHTP product, transferability or While the weight loss characteristics are improved, the plasticization efficiency is poor, and there is a problem that a considerable amount must be added to give an appropriate plasticizing effect to the resin. .
[15]
Accordingly, as an existing product, there is a need to develop products for solving environmental issues of phthalate-based products or products with improved poor physical properties of eco-friendly products for improving environmental issues of phthalate-based products.
[16]
DETAILED DESCRIPTION OF THE INVENTION
technical challenge
[17]
The present invention is a plasticizer composition, and by including cyclohexane triesters to which isomer radicals having the same alkyl radical carbon number of components are bonded, the adequacy of absorption rate is secured, and mechanical properties and stress resistance compared to conventional plasticizers are equal or higher. It is an object of the present invention to provide a plasticizer composition that can significantly improve light resistance while maintaining and improving the properties, while having an appropriate balance between transferability and weight loss characteristics and plasticizing efficiency.
[18]
means of solving the problem
[19]
According to an embodiment of the present invention in order to solve the above problems, a cyclohexane triester-based composition including one or more cyclohexane triesters of the following Chemical Formula 1 is included, and the alkyl group of the cyclohexane triesters has a degree of branching It is derived from a mixture of isomers of hexyl alcohol less than 2.0, wherein the mixture of isomers of hexyl alcohol is 1-hexanol, 1-methylpentanol, 2-methylpentanol, 3-methylpentanol, 4-methylpentanol, 1,1 -Dimethylbutanol, 1,2-dimethylbutanol, 1,3-dimethylbutanol, 2,2-dimethylbutanol, 2,3-dimethylbutanol, 3,3-dimethylbutanol, 1-ethylbutanol, 2-ethylbutanol, 3 -Provides a cyclohexane triester-based plasticizer composition comprising at least two selected from the group consisting of -ethylbutanol and cyclopentyl methanol.
[20]
[Formula 1]
[21]

[22]
In Formula 1,
[23]
R 1 to R 3 are each independently an n-hexyl group, a branched hexyl group, or a cyclopentyl methyl group.
[24]
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-mentioned plasticizer composition; is provided a resin composition comprising.
[25]
Effects of the Invention
[26]
The plasticizer composition according to an embodiment of the present invention, when used in a resin composition, has excellent processability at an appropriate level of absorption rate compared to existing plasticizers, and maintains and improves mechanical properties and stress resistance at equal or higher levels, It is possible to significantly improve light resistance while having an appropriate balance between transferability and weight loss characteristics and plasticizing efficiency.
[27]
Modes for carrying out the invention
[28]
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.
[29]
[30]
Definition of Terms
[31]
The term "composition" as used herein includes reaction products and decomposition products formed from materials of the composition, as well as mixtures of materials comprising the composition.
[32]
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 tens to 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.
[33]
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, etc., It refers to a polymer with a cohesive property and poor flowability as fine, dense pore-free particles having a size of several thousand nanometers.
[34]
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.
[35]
[36]
How to measure
[37]
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).
[38]
In the present specification, 'hardness' means the 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.
[39]
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.
[40]
[Equation 1]
[41]
Tensile strength (kgf/cm 2 ) = load value (kgf) / thickness (cm) x width (cm)
[42]
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.
[43]
[Equation 2]
[44]
Elongation (%) = length after stretching / initial length x 100
[45]
In the present 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 then 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.
[46]
[Equation 3]
[47]
Transition loss (%) = {[(initial weight of specimen) - (weight of specimen after leaving in oven)] / (weight of initial specimen)} x 100
[48]
In the present specification, 'volatile loss' refers to measuring the weight of the specimen after working the specimen at 80°C for 72 hours.
[49]
[Equation 4]
[50]
Loss on heating (%) = {[(initial specimen weight) - (test specimen weight after work)] / (initial specimen weight)} x 100
[51]
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 the case of different conditions, the measurement method and conditions are separately specified.
[52]
[53]
Hereinafter, the present invention will be described in more detail to help the understanding of the present invention.
[54]
According to an embodiment of the present invention, the plasticizer composition is a cyclohexane triester, and includes a cyclohexane triester-based composition containing one or more cyclohexane triesters of Formula 1, wherein the alkyl group of the cyclohexane triesters, It is derived from an isomeric mixture of hexyl alcohol with a degree of branching less than 2.0.
[55]
[Formula 1]
[56]

[57]
In Formula 1, R 1 to R 3 are each independently an n-hexyl group, a branched hexyl group, or a cyclopentyl methyl group.
[58]
According to an embodiment of the present invention, the isomer mixture of the hexyl alcohol of the plasticizer composition is 1-hexanol, 1-methylpentanol, 2-methylpentanol, 3-methylpentanol, 4-methylpentanol, 1 ,1-dimethylbutanol, 1,2-dimethylbutanol, 1,3-dimethylbutanol, 2,2-dimethylbutanol, 2,3-dimethylbutanol, 3,3-dimethylbutanol, 1-ethylbutanol, 2-ethylbutanol , 3-ethylbutanol and cyclopentyl methanol include two or more selected from the group consisting of.
[59]
Depending on the alcohol contained in the isomer of hexyl alcohol, the alkyl groups of R1 to R3 of Formula 1 may be determined, and in the final composition, 3, 2, or 1 isomeric alkyl groups of hexyl alcohol are bonded to the three alkyl groups, respectively Various compositions may be included, and the ratio of the components in the final composition may be determined according to the component ratio of the reacting alcohols.
[60]
As such, when an alcohol having 6 carbon atoms is used in applying the cyclohexane triester-based plasticizer, processability improvement can be achieved by securing an appropriate level of absorption rate compared to that having less than 6 carbon atoms, and tensile strength, Elongation, heating loss, and transition loss can be greatly improved, and plasticization efficiency can be excellent in comparison with the case where the number of carbons exceeds six.
[61]
In addition, since there is no unsaturated bond in the moiety of the central core, a significant improvement in light resistance can be expected compared to a trimellitate-based plasticizer in which a benzene ring including an unsaturated bond is a core moiety.
[62]
[63]
In the plasticizer composition according to an embodiment of the present invention, an alcohol in which isomers are mixed is applied, and, unlike theoretically predicted, improved effect in tensile strength, plasticization efficiency, and heat loss compared to the case where only linear hexyl alcohol is included can get
[64]
The hexyl alcohol isomer mixture of the plasticizer composition according to an embodiment of the present invention may have a degree of branching of less than 2.0, preferably 1.5 or less. Specifically, the degree of branching may be 1.5 or less, 1.3 or less, and more preferably 1.1 or less. Also, it may be 0.1 or more, may be 0.2 or more, may be 0.3 or more, and most preferably may be 0.7 or more. The degree of branching of the isomer mixture of this hexyl alcohol can be maintained even when converted to the cyclohexane triester-based plasticizer composition. If the degree of branching exceeds 2.0, the balance between physical properties may be broken and the product may fail to meet one or more evaluation criteria. and the balance between physical properties may be excellent.
[65]
Here, the degree of branching may mean how many branching 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 branched carbons of each alcohol is 0, 1, and 2, respectively. , the degree of branching may be 0.5 calculated as [(60x0)+(30x1)+(10x2)] / 100. Here, in the case of cyclopentyl methanol, the number of branching carbons is considered to be zero.
[66]
[67]
The plasticizer composition according to an embodiment of the present invention may include 1-hexanol, 2-methylpentanol and 3-methylpentanol in a hexyl alcohol isomer mixture. Theoretically, it is predicted that the case containing only 1-hexanol will produce the most excellent effect due to excellent linearity. You can get an excellent effect from the side.
[68]
The branched hexyl alcohol containing 2-methylpentanol and 3-methylpentanol may be included in an amount of 40 parts by weight or more, 50 parts by weight or more, 60 parts by weight or more, preferably 65 parts by weight or more, based on 100 parts by weight of the isomer mixture. It may be included in parts by weight or more, and 70 parts by weight or more. The maximum amount may be all branched, and may contain 99 parts by weight or less, 98 parts by weight or less, preferably 95 parts by weight or less, or 90 parts by weight or less. When branched hexyl alcohol is included in this range, improvement in mechanical properties can be expected.
[69]
In addition, the linear alcohol of 1-hexanol may be included in an amount of 50 parts by weight or less based on 100 parts by weight of the isomer mixture, and may be 40 parts by weight or less, preferably 30 parts by weight or less. The 1-hexanol may not be present in the component, but may be included in at least 2 parts by weight or more, and in this case, the mechanical properties may be improved while maintaining the balance between the physical properties. Although it is known that linear alcohol can produce excellent effects in theory, in the present invention, results different from these theoretical results were obtained, and it was confirmed that the balance of physical properties was more excellent when an isomer mixture containing branched alcohol was applied.
[70]
[71]
The plasticizer composition according to an embodiment of the present invention may include 1-hexanol, 2-methylpentanol, 3-methylpentanol and cyclopentyl methanol in the isomer mixture of hexyl alcohol. Preferably, by further including cyclopentyl methanol, heat loss can be further improved while maintaining the balance between physical properties.
[72]
In this case, the amount of cyclopentyl methanol may be 20 parts by weight or less based on 100 parts by weight of the isomer mixture, preferably 15 parts by weight or less, more preferably 10 parts by weight or less, and it is not present, or the minimum amount to obtain the effect is 2 parts by weight.
[73]
Specifically, due to characteristics such as what proportion of the branched alkyl group is present among the total alkyl radicals in the final composition, and furthermore, what proportion of the specific branched alkyl radical is present among the branched alkyl groups, plasticization efficiency and It is possible to balance the physical properties of transferability/reduction properties, and mechanical properties such as tensile strength and elongation and stress resistance can also be maintained at equal or higher levels, and due to the interaction of the four types of cyclohexane triesters included in the composition A remarkable improvement in light resistance can be achieved, which can be achieved from the above-mentioned components of isomers of hexyl alcohol and their ratios.
[74]
Through this, it is possible to implement a product with improved weight loss characteristics while removing the environmental issues of existing phthalate products, and it is possible to significantly improve the transferability and weight loss characteristics of existing terephthalate products, and compared to existing commercial products. Therefore, it may be possible to realize a product with significantly improved light resistance and heat resistance.
[75]
[76]
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.
[77]
That is, by appropriately combining the hydrogenation reaction, the direct esterification reaction, and the transesterification reaction, the plasticizer composition according to the present invention can be prepared, for example, by directly esterifying a mixture of isomers of trimellitic acid and hexyl alcohol. The composition may be prepared by hydrogenating the prepared trimellitate composition, or the composition may be prepared by hydrogenating the trimellitate composition prepared by transesterifying the trimellitate and one alcohol separated with the trimellitate composition.
[78]
In addition, it can be carried out by changing the order of the esterification reaction and the hydrogenation reaction. A method in which trimellitic acid is hydrogenated before the esterification reaction and cyclohexane tricarboxylic acid as a reactant is directly esterified with a mixture of isomers of hexyl alcohol is applied. Alternatively, a method in which trimellitate is hydrogenated before the esterification reaction to transesterify cyclohexane triester with one or more alcohols separated as a reactant may be applied.
[79]
The plasticizer composition according to an embodiment of the present invention is a material prepared by appropriately combining the esterification reaction and the hydrogenation reaction.
[80]
For example, the direct esterification reaction may include adding an isomer mixture of trimellitic acid or cyclohexane tricarboxylic acid or a derivative thereof (ex. anhydride) and hexyl alcohol, then adding a catalyst and reacting under a nitrogen atmosphere; removing unreacted alcohol and neutralizing unreacted acid; and dehydration and filtration by vacuum distillation.
[81]
The components and weight ratios of the components of the isomer mixture of hexyl alcohol are the same as described above. The alcohol is in 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 trimellitic acid or cyclohexane tricarboxylic acid It can be used into the composition, and by controlling the content of this alcohol, it is possible to control the component ratio in the final composition.
[82]
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. Preferably, para-toluenesulfonic acid, methanesulfonic acid, etc. may be suitable as the acid catalyst having a low activation temperature.
[83]
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 reactant. 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.
[84]
At this time, the reaction temperature may be in the range of 180 to 280 ℃, 200 to 250 ℃, or 210 to 230 ℃.
[85]
[86]
In another example, the transesterification reaction is different from the alkyl radical of trimellitate (which may be cyclohexane triester when hydrogenation is first performed, and trimellitate will be used as an example below) and the alkyl radical of trimellitate. An alcohol having an alkyl radical (a linear alcohol in the case of trimellitate to which a branched alkyl group is bonded, and a branched alcohol in the case of trimellitate to which a linear alkyl group is bonded) may be reacted. Here, the alkyl groups of trimellitate and alcohol may cross each other.
[87]
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 the ester is interchanged with R' of the alcohol:
[88]
[Scheme 1]
[89]

[90]
In general, when the transesterification reaction is carried out, when there are two types of alkyl groups, when the alkoxide of the alcohol attacks the carbons of three ester (RCOOR") groups present in the ester compound; two esters present in the ester compound ( RCOOR") when attacking the carbon of the group; In the case of attacking the carbon of one ester (RCOOR") group present in the ester compound; in the case of unreacted unreacted; in four cases, four types of ester compositions can be produced by number. have.
[91]
However, in the case of the cyclohexane triester included in the plasticizer composition according to the present invention, when two ester groups are exchanged and when one ester group is exchanged depending on the ester group bonding position, three types may be formed, respectively. Accordingly, up to 8 types of compounds may be mixed in the final composition. However, in the case of a mixture of isomers of hexyl alcohol according to the present invention, since there are two or more types of alkyl groups, the types may be more diverse.
[92]
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 trimellitate compound. For reference, determining the component ratio in the final composition may be the amount of alcohol added as in the direct esterification reaction.
[93]
That is, as the amount of alcohol added to the trimellitate compound increases, the mole fraction of trimellitate participating in the transesterification reaction will increase. Therefore, the content of trimellitate as a product in the mixture may increase. and, correspondingly, the content of trimellitate present as unreacted may show a tendency to decrease.
[94]
According to an embodiment of the present invention, the molar ratio of the reactant trimellitate and the 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 economy are excellent. It can be, and there is an effect of obtaining a plasticizer composition that can implement the above-described effect.
[95]
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.
[96]
The transesterification reaction may be carried out under an acid catalyst or a metal catalyst, and in this case, the reaction time is shortened.
[97]
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.
[98]
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.
[99]
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 boiling point difference. In another example, the distillation may be mixed distillation. In this case, there is an effect of relatively stably securing the ester-based plasticizer composition in a desired composition ratio. The mixed distillation means simultaneously distilling unreacted alcohol and reaction by-products.
[100]
The hydrogenation step is a reaction for removing the aromaticity of the benzene ring of trimellitate by adding hydrogen in the presence of a metal catalyst, and may be a kind of reduction reaction.
[101]
The hydrogenation reaction synthesizes cyclohexane triester or cyclohexane tricarboxylic acid by reacting the trimellitate with hydrogen under a metal catalyst, and the reaction conditions include a carbonyl group (ester or carboxylic acid) substituted with benzene. All conventional reaction conditions capable of hydrogenating only the benzene ring without affecting them can be included.
[102]
The hydrogenation reaction may be carried out further including an organic solvent such as ethanol, but is not limited thereto. As the metal catalyst, a Rh/C catalyst, a Pt catalyst, a Pd catalyst, etc. which are generally used for hydrogenating the benzene ring may be used, but is not limited thereto as long as the hydrogenation reaction as described above is possible.
[103]
The plasticizer composition according to an embodiment of the present invention may be one to which a direct esterification reaction is preferably applied. In the alcohol applied to the direct esterification reaction, by applying a mixture of an alcohol having a linear and branched alkyl as an alcohol composition, the proportion of cyclohexane triester components to be finally prepared can be controlled, and branched type among the total alkyl radicals The molar ratio of the alkyl group and the molar ratio of a specific branched alkyl group among the branched alkyl radicals can be controlled.
[104]
As described above, with respect to the method for preparing the plasticizer composition according to an embodiment of the present invention, the esterification reaction and the hydrogenation reaction have been described, but in the case of the hydrogenation reaction, a relatively expensive catalyst metal is used and the reaction conditions are severe, so that the unit price is increased. Since there is a disadvantage that it can be a cause, it may be more preferable to prepare through an esterification reaction using a hydrogenated raw material as much as possible.
[105]
[106]
According to another embodiment of the present invention, there is provided a resin composition comprising the above-described plasticizer composition and resin.
[107]
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.
[108]
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.
[109]
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.
[110]
For example, when a vinyl chloride polymer is used for melt processing, solid resin particles with a large average particle diameter are used because it is prepared by suspension polymerization, etc., and this vinyl chloride polymer is called a straight vinyl chloride polymer, and is used for plastisol processing. In this case, a resin in a sol state is used as a fine resin particle prepared by emulsion polymerization, etc., and such a vinyl chloride polymer is called a paste vinyl chloride resin.
[111]
In this case, in the case of the straight vinyl chloride polymer, the plasticizer is preferably included in the range of 5 to 80 parts by weight based on 100 parts by weight of the polymer, and in the case of the paste vinyl chloride polymer, in the range of 40 to 120 parts by weight based on 100 parts by weight of the polymer. It is preferable to include in
[112]
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.
[113]
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 one or more 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.
[114]
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.
[115]
The stabilizer may be, for example, a calcium-zinc (Ca-Zn-based) stabilizer or a barium-zinc (Ba-Zn-based) stabilizer such as a calcium-zinc complex stearate salt, but is not particularly limited thereto. no.
[116]
The resin composition may be applied to both melt processing and plastisol processing as described above, for example, melt processing may include calendering processing, extrusion processing, or injection processing, and plastisol processing may include coating processing, etc. This can be applied.
[117]
[118]
Example
[119]
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 in detail below. The embodiments of the present invention are provided to more completely explain the present invention to those of ordinary skill in the art.
[120]
[121]
Example 1
[122]
In a reactor equipped with a stirrer, condenser and decanter, 595 g of cyclohexane 1,2,4-tricarboxylic acid anhydride, 1,195 g of an isomer mixture of hexyl alcohol, and 2 g of tetrabutyl titanate (TnBT) were added, and then under a nitrogen atmosphere. The reaction was terminated by esterification, the catalyst and the product were neutralized with an aqueous alkali solution, and unreacted alcohol and moisture were purified to finally obtain a plasticizer composition.
[123]
The alcohol composition of the isomer mixture of hexyl alcohol used here is as shown in Table 1 below.
[124]
[125]
Examples 2 to 12
[126]
A plasticizer composition was obtained in the same manner as in Example 1, except that the alcohol composition of the isomer mixture of hexyl alcohol in Example 1 was changed as shown in Table 1 below.
[127]
[128]
[Table 1]
　　 1-hexanol 2-methylpentanol 3-methylpentanol 2-ethylbutanol cyclopentyl methanol
Example 1 30 15 50 - 5
Example 2 30 30 30 - 10
Example 3 10 40 40 - 10
Example 4 20 30 40 - 5
Example 5 5 30 50 - 15
Example 6 2 50 40 - 8
Example 7 8 60 30 - 2
Example 8 10 40 50 - -
Example 9 30 30 40 - -
Example 10 - 40 50 - 10
Example 11 10 - 80 - 10
Example 12 30 - - 70 -
[129]
* The content of the alcohols are all parts by weight. The content of the components in the isomer mixture of hexyl alcohol is measured by gas chromatography, and Agilent's gas chromatography instrument (product name: Agilent 7890 GC, column: HP-5, Carrier gas: helium (flow rate 2.4mL/min), detector: FID, injection volume: 1uL, initial value: 70℃/4,2min, end value: 280℃/7.8min, program rate: 15℃/min) analyzed.
[130]
Comparative Example 1
[131]
As a product of LG Chem, diisononyl phthalate (DINP) was used as a plasticizer composition.
[132]
[133]
Comparative Example 2
[134]
As a product of LG Chem, di(2-ethylhexyl) terephthalate (DEHTP, LGflex GL300) was used as a plasticizer composition.
[135]
[136]
Comparative Example 3
[137]
In Example 1, trimellitic acid was used instead of cyclohexane 1,2,4-tricarboxylic acid anhydride, and branched pentanol (branched 2-methylbutanol 100%) was used instead of the isomer mixture of hexyl alcohol. Except that, a plasticizer composition was obtained in the same manner as in Example 1.
[138]
[139]
Comparative Example 4
[140]
In Example 1, trimellitic acid was used instead of cyclohexane 1,2,4-tricarboxylic acid anhydride, and a mixture of isomers of pentanol instead of a mixture of isomers of hexyl alcohol (weight ratio of n-pentanol and 2-methylbutanol) 5:5), except that a plasticizer composition was obtained in the same manner as in Example 1.
[141]
[142]
Comparative Example 5
[143]
In Example 1, trimellitic acid was used instead of cyclohexane 1,2,4-tricarboxylic acid anhydride, and a mixture of isomers of hexyl alcohol (weight ratio of n-hexanol to 2-ethylbutanol 7:3) was used. Except that, a plasticizer composition was obtained in the same manner as in Example 1.
[144]
[145]
Comparative Example 6
[146]
A plasticizer composition was obtained in the same manner as in Example 1, except that isobutanol was used instead of the isomer mixture of hexyl alcohol in Example 1.
[147]
[148]
Comparative Example 7
[149]
A plasticizer composition was obtained in the same manner as in Example 1, except that n-butanol was used instead of the isomer mixture of hexyl alcohol in Example 1.
[150]
[151]
Comparative Example 8
[152]
A plasticizer composition was obtained in the same manner as in Example 1, except that in Example 1, branched pentanol (100% branched 2-methylbutanol) was used instead of the isomer mixture of hexyl alcohol.
[153]
[154]
Comparative Example 9
[155]
A plasticizer composition was obtained in the same manner as in Example 1, except that n-pentanol was used instead of the isomer mixture of hexyl alcohol in Example 1.
[156]
[157]
Comparative Example 10
[158]
A plasticizer composition was obtained in the same manner as in Example 1, except that n-heptanol was used instead of the isomer mixture of hexyl alcohol in Example 1.
[159]
[160]
Comparative Example 11
[161]
A plasticizer composition was obtained in the same manner as in Example 1, except that n-hexanol was used instead of the isomer mixture of hexyl alcohol in Example 1.
[162]
[163]
Comparative Example 12
[164]
A plasticizer composition was obtained in the same manner as in Example 1, except that 2-ethylbutanol was used instead of the isomer mixture of hexyl alcohol in Example 1.
[165]
[166]
Experimental Example 1: Calendering sheet performance evaluation
[167]
Using the plasticizers of Examples and Comparative Examples, specimens were manufactured under the following prescription and manufacturing conditions according to ASTM D638.
[168]
(1) Prescription : 100 parts by weight of straight vinyl chloride polymer (LS100S), 40 parts by weight of a plasticizer, and 3 parts by weight of a stabilizer (BZ-153T).
[169]
(2) Mixing : Mixing at 700 rpm at 98°C.
[170]
(3) Specimen production : 1T and 3T sheets were produced by working at 160°C for 4 minutes with a roll mill and 2.5 minutes (low pressure) and 2 minutes (high pressure) at 180°C with a press.
[171]
(4) Evaluation items
[172]
1) Hardness : Using ASTM D2240, the shore hardness (Shore "A") at 25 ℃ was measured for 10 seconds with a 3T specimen. It is evaluated that the plasticizing efficiency is excellent, so that a numerical value is small.
[173]
2) Tensile strength : After pulling the crosshead 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:
[174]
Tensile strength (kgf/cm 2 ) = load value (kgf) / thickness (cm) x width (cm)
[175]
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:
[176]
Elongation (%) = length after stretching / initial length x 100 was calculated.
[177]
4) Measurement of migration loss : A test piece with 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.
[178]
Transition loss (%) = {[(initial weight of specimen) - (weight of specimen after leaving in oven)] / (initial weight of specimen)} x 100
[179]
5) Measurement of volatile loss : After working the prepared specimen at 100° C. for 168 hours, the weight of the specimen was measured.
[180]
Loss on heating (%) = {[(initial specimen weight) - (test specimen weight after work)] / (initial specimen weight)} x 100.
[181]
6) Stress test (stress resistance) : After leaving a 2 mm thick specimen in a bent state at 23° C. for 72 hours, observe the degree of transition (the degree of seepage), and display the result as a numerical value (from 0 to 3.0 0.5 unit), and the closer to 0, the better the characteristic.
[182]
7) Measurement of absorption rate
[183]
The absorption rate was evaluated by measuring the time it took for the resin and the ester compound to be mixed with each other and the torque of the mixer was stabilized using a planatary mixer (Brabender, P600) under the conditions of 77° C. and 60 rpm.
[184]
8) Light fastness measurement
[185]
According to the method of ASTM 4329-13, the specimen was mounted in QUV (QUV/se, Q-LAB) and UV (340 nm) was irradiated for 400 hours, and then the color change (E) using a Reflectometer (Tintometer, LoviBond) ) was confirmed.
[186]
(5) Evaluation results
[187]
The evaluation results of the above items are shown in Table 2 below.
[188]
[Table 2]
　　 Hardness (Shore A) Tensile strength (kgf/cm 2 ) Elongation (%) Performance loss (%) Heat loss (%) stress transferability absorption rate light fastness
Example 1 90.5 240.2 311.0 0.42 0.65 0 4m11s 1.02
Example 2 90.6 234.5 308.9 0.44 0.68 0 4m15s 1.05
Example 3 91.0 233.5 308.7 0.65 0.72 0 4m35s 1.05
Example 4 90.8 234.0 306.5 0.50 0.66 0 4m20s 1.10
Example 5 91.3 232.7 305.6 0.53 0.62 0 4m30s 1.01
Example 6 90.5 228.9 302.1 0.44 0.74 0 4m25s 1.00
Example 7 91.1 225.6 302.8 0.64 0.75 0 4m30s 1.05
Example 8 91.3 237.6 309.4 0.66 1.01 0 4m25s 1.10
Example 9 91.0 240.2 308.7 0.58 0.86 0 4m20s 1.02
Example 10 92.2 236.5 315.4 0.66 0.88 0 4m35s 1.08
Example 11 92.2 237.9 314.2 0.59 1.30 0 4m45s 1.17
Example 12 92.0 224.9 310.5 0.62 1.35 0 4m30s 1.14
Comparative Example 1 93.4 234.7 319.6 2.16 3.76 0.5 5m38s 1.52
Comparative Example 2 94.9 234.0 322.1 3.43 4.42 3.0 6m40s 4.87
Comparative Example 3 92.0 220.5 288.6 0.77 1.42 0 4m20s 4.57
Comparative Example 4 92.8 221.6 290.3 1.25 2.38 0.5 4m10s 4.88
Comparative Example 5 93.1 223.4 300.2 0.88 1.25 0.5 5m10s 5.21
Comparative Example 6 91.7 201.6 254.5 0.49 9.84 0 dispose* 1.32
Comparative Example 7 92.4 214.7 260.6 0.38 7.88 0 dispose 1.28
Comparative Example 8 91.2 210.4 266.9 0.56 5.26 0 4m00s 1.10
Comparative Example 9 91.4 209.7 273.7 0.35 2.82 0 4m05s 1.09
Comparative Example 10 94.0 230.2 270.3 1.45 1.01 1.0 6m05s 1.14
Comparative Example 11 92.3 220.8 305.9 0.59 1.24 0 4m46s 1.02
Comparative Example 12 94.2 220.1 298.7 1.54 2.58 1.0 5m15s 1.18
[189]
Referring to the results of Table 2, the case of applying the plasticizer of Examples 1 to 12 showed an excellent effect in most of the physical properties compared to the case of applying the plasticizer of Comparative Examples 1 to 12, and it can be confirmed that the balance between the physical properties is excellent, In particular, it can be seen that excellent effects can be seen in tensile strength, heat loss, transition loss and light resistance. Furthermore, it can be seen that the absorption rate is not too fast as 4 minutes, so there is no fear of being discharged, and the processability is also excellent in that it does not exceed 5 minutes. , it can be confirmed that there is a large improvement in the transition loss and heating loss, and the absorption rate is also improved, so that the processability can also be expected to be improved. .
[190]
In addition, as in the plasticizer composition according to the present invention, when all of the central core moiety is saturated, it can be confirmed that there is a very large effect in improving light resistance compared to Comparative Examples 3 to 5 in which an unsaturated benzene ring is present, and elongation and tensile strength were also improved.
[191]
In addition, as in Comparative Examples 6 and 7, when an alcohol having 4 carbon atoms is applied, the plasticizer is not normally absorbed into the resin during compounding, and the processability to such an extent that it is impossible to measure the absorption rate due to repetition of aggregation and disintegration and repetition of absorption and discharge. It can be confirmed that this is very poor, and it can be confirmed that the mechanical properties and heat loss are at a level that does not satisfy even the basic requirements of the consumer. In Comparative Examples 8 and 9, alcohols having 5 carbon atoms were applied, and it was confirmed that the tensile strength and elongation were very poor due to mechanical properties as in the case of carbon number 4, and the heating loss was also quite poor. In addition, in the case of Comparative Example 10 to which carbon number 7 was applied, the elongation was very poor and the stress resistance was also inferior.
[192]
Furthermore, when alcohol having 6 carbon atoms was applied, but the isomer mixture was not applied, Comparative Example 11, in which only 1-hexanol, which is expected to have an excellent effect, was applied, most of the physical properties compared to Examples to which the isomer mixture was applied It is evaluated at a low level, and it is confirmed that it is particularly inferior in tensile strength, heat loss, and plasticization efficiency (hardness). And, in the case of Comparative Example 12, in which branched 2-ethylbutanol was applied alone, the absorption rate was conspicuously slow, and it was confirmed that all physical properties such as transfer loss, heat loss, and tensile strength were inferior.

WE CLAIMS

A cyclohexane triester-based composition comprising at least one cyclohexane triester of Formula 1 is included, wherein the alkyl group of the cyclohexane triester is derived from a mixture of isomers of hexyl alcohol having a branching degree of 2.0 or less, and The isomer mixture is 1-hexanol, 1-methylpentanol, 2-methylpentanol, 3-methylpentanol, 4-methylpentanol, 1,1-dimethylbutanol, 1,2-dimethylbutanol, 1,3- 2 or more selected from the group consisting of dimethylbutanol, 2,2-dimethylbutanol, 2,3-dimethylbutanol, 3,3-dimethylbutanol, 1-ethylbutanol, 2-ethylbutanol, 3-ethylbutanol and cyclopentyl methanol A cyclohexane triester-based plasticizer composition comprising: [Formula 1] In Formula 1, R 1 to R 3 are each independently an n-hexyl group, a branched hexyl group, or a cyclopentyl methyl group.
[Claim 2]
The plasticizer composition according to claim 1, wherein the isomer mixture of hexyl alcohol has a degree of branching of 1.5 or less.
[Claim 3]
The plasticizer composition of claim 1, wherein the isomer mixture of hexyl alcohol comprises 1-hexanol, 2-methylpentanol and 3-methylpentanol.
[Claim 4]
The plasticizer composition according to claim 1, wherein the isomer mixture of hexyl alcohol contains 40 parts by weight or more of branched alcohol based on 100 parts by weight of the isomer mixture.
[Claim 5]
The plasticizer composition according to claim 1, wherein the isomer mixture of hexyl alcohol contains 50 to 95 parts by weight of the branched alcohol based on 100 parts by weight of the isomer mixture.
[Claim 6]
The plasticizer composition of claim 1, wherein the isomer mixture of hexyl alcohol contains 40 parts by weight or less of 1-hexanol based on 100 parts by weight of the isomer mixture.
[Claim 7]
The plasticizer composition of claim 1, wherein the isomer mixture of hexyl alcohol comprises 1-hexanol, 2-methylpentanol, 3-methylpentanol and cyclopentyl methanol.
[Claim 8]
The plasticizer composition according to claim 7, wherein the isomer mixture of hexyl alcohol contains 20 parts by weight or less of cyclomethyl pentanol based on 100 parts by weight of the isomer mixture.
[Claim 9]
100 parts by weight of resin; And 5 to 150 parts by weight of the plasticizer composition of claim 1; A resin composition comprising a.
[Claim 10]
10. The method of claim 9, wherein the resin is 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 and synthetic rubber. A resin composition that is more than a species.