Title of Invention: Plasticizer composition and resin composition comprising same
technical field
[One]
Cross Citation with Related Applications
[2]
This application claims the benefit of priority based on Korean Patent Application No. 10-2020-0040521 dated April 02, 2020, 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 a tetraester-based composition and a resin composition comprising 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 the plasticization efficiency is improved, but the loss of 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 a tetraester-based composition, which is a product derived from esterification of a mixture of hexanoic acid isomers and a tetrahydric alcohol, the plasticization efficiency and absorption rate can be maintained at equal or higher levels compared to those applied with conventional plasticizers, An object of the present invention is to provide a plasticizer composition that can significantly improve mechanical properties, migration resistance, stress resistance and weight loss characteristics.
[18]
means of solving the problem
[19]
According to an embodiment of the present invention in order to solve the above problems, a tetraester-based composition containing one or more tetraesters of the following Chemical Formula 1 is included, and the alkyl group of the tetraester has a degree of branching of 2.0 or less hexanoic acid (hexanoic acid). ) isomeric mixtures.
[20]
[Formula 1]
[21]

[22]
In Formula 1, R 1 to R 4 are each independently an n-pentyl group, a branched pentyl group, or a cyclopentyl group.
[23]
[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]
The resin may be 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 and synthetic rubber.
[26]
Effects of the Invention
[27]
When the plasticizer composition according to an embodiment of the present invention is used in a resin composition, plasticization efficiency and absorption rate can be maintained at the same level compared to conventional plasticizers, and mechanical properties, migration resistance, stress transferability and weight loss characteristics are significantly improved. can be improved
[28]
Modes for carrying out the invention
[29]
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.
[30]
[31]
Definition of Terms
[32]
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.
[33]
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 end of the alkyl group. In , it can be used as a generic term for an alkyl group in which a methyl group or an ethyl group is bonded to the main chain in a branched chain, including those bonded to the terminal, unless otherwise referred to as an alkyl group.
[34]
As used herein, the term "isomer" is not intended to distinguish isomers in all meanings, but structural isomers, that is, a relationship in which the number of carbon atoms is the same but the bonding structure is different, and is intended to distinguish them, and optical isomers This does not mean that the substance is a distinct substance, even stereoisomers such as diastereomers.
[35]
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.
[36]
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 having a size of several thousand nanometers and has poor flowability as fine, dense void-free particles.
[37]
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.
[38]
[39]
How to measure
[40]
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).
[41]
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.
[42]
In the present specification, 'tensile strength' is a crosshead speed of 200 mm/min (1T) using a test device, UTM (manufacturer; Instron, model name; 4466), according to the ASTM D638 method. ), measure the point at which the specimen is cut and calculate as follows.
[43]
Tensile strength (kgf/cm 2 ) = load value (kgf) / thickness (cm) x width (cm)
[44]
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 as follows.
[45]
Elongation (%) = length after stretching / initial length x 100
[46]
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 as follows.
[47]
Transition loss (%) = [{(weight of initial specimen) - (weight of specimen after leaving in oven)} / (weight of initial specimen)] x 100
[48]
In the present specification, 'volatile loss' is calculated as follows by measuring the weight of the specimen after working the specimen at 80° C. for 72 hours.
[49]
Loss on heating (wt%) = [{(initial specimen weight) - (test specimen weight after work)} / (initial specimen weight)] x 100
[50]
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.
[51]
[52]
Hereinafter, the present invention will be described in more detail to help the understanding of the present invention.
[53]
According to an embodiment of the present invention, the plasticizer composition includes a tetraester-based composition containing one or more tetraesters of the following Chemical Formula 1, and the alkyl group of the tetraester has a degree of branching of 2.0 or less hexanoic acid isomer It is derived from a mixture.
[54]
[Formula 1]
[55]

[56]
In Formula 1, R 1 to R 4 are each independently an n-pentyl group, a branched pentyl group, or a cyclopentyl group.
[57]
The tetraester-based composition may be a product produced by an esterification reaction between a mixture of hexanoic acid isomers and a tetrahydric alcohol, pentaerithritol, and thus, carbon having 6 carbons including the central carbon of the carbonyl group Since it is derived from a carboxylic acid having a chain, a linear, branched or alicyclic alkyl group having 5 carbon atoms is applied to R1 to R4 in Formula 1 above.
[58]
The plasticizer composition according to an embodiment of the present invention includes a tetraester-based composition containing one or more tetraesters represented by Formula 1, but the number of hexanoic acid contained in the hexanoic acid isomer mixture applied to the esterification reaction Accordingly, the number of tetraesters in the finally produced tetraester-based composition may be determined. For example, when a mixture of isomers of hexanoic acid contains two isomers, the plasticizer composition may contain at least 5 tetraesters, and when three isomers are included, the plasticizer composition contains at least 15 tetraesters. may be included.
[59]
In the tetraester-based composition according to an embodiment of the present invention, an alkyl carboxylic acid having 6 carbon atoms, that is, hexanoic acid is applied, so that when used as a plasticizer, a balance between plasticization efficiency and mechanical properties compared to a case where other carbon numbers are applied This can be excellent. When an alkyl carboxylic acid having 5 or less carbon atoms is used, mechanical properties and stress transferability are poor. When an alkyl carboxylic acid having 7 or more carbon atoms is used, the plasticization efficiency is poor and the absorption rate is very slow, so the processability is significantly deteriorated. can be
[60]
In addition, in that the tetraester contained in the tetraester-based composition is a compound having four ester groups, when used as a plasticizer, it has excellent compatibility with resins and excellent compatibility with other additives, and has many ester groups, which makes it a polymer Molecules can be immobilized within the chain, and thus the migration resistance and stress resistance can be excellent, and the plasticization efficiency can be excellent.
[61]
Furthermore, unlike the case in which a benzene ring is present in the molecule like a petroleum-based plasticizer, there is no benzene ring in the molecule, so it is classified as an eco-friendly plasticizer, but its performance can be evaluated as superior compared to that of a petroleum-based plasticizer, which is Unlike the plasticizer prepared from the reaction of the acid and the mono-alcohol, it is understood as an effect resulting from the preparation of the plasticizer from the reaction of the polyhydric alcohol and the mono-carboxylic acid.
[62]
The tetraester-based composition according to an embodiment of the present invention may include a triester and a diester in addition to the tetraester in the composition, and the mixed weight of the triester and the diester included therein is 20.0 based on the total weight of the tetraester-based composition weight % or less. The mixed weight of the triester and diester may be preferably 10.0 wt% or less, more preferably 5.0 wt% or less, and even more preferably 1.0 wt% or less. However, the triesters and diesters included in the tetraester-based composition refer to by-products derived from the reaction of hexanoic acid and pentaerythritol, and other types of ester compounds such as trimellitate, terephthalate, isophthalate, and citrate. does not mean
[63]
[64]
The alkyl group of the tetraester included in the tetraester-based composition according to an embodiment of the present invention is derived from a mixture of hexanoic acid isomers having a degree of branching of 2.0 or less, and preferably the degree of branching may be 1.5 or less, and may be 1.3 or less, It may be 1.2 or less or 1.0 or less. In addition, it may be 0.1 or more, may be 0.2 or more, may be 0.3 or more. The alkyl group may be derived from an esterification reaction from a mixture of isomers of hexanoic acid, and this degree of branching may be maintained even when converted to a tetraester-based composition.
[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 hexanoic acid mixture contains 60% by weight of 1-hexanoic acid, 30% by weight of 2-methylpentanoic acid, and 10% by weight of 2-ethyl butanoic acid, the number of branched carbons of each carboxylic acid is Since they are 0, 1, and 2, respectively, the degree of branching is calculated as [(60x0)+(30x1)+(10x2)] / 100 and may be 0.5.
[66]
Specifically, due to characteristics such as what proportion of the branched alkyl group is present in the total alkyl radicals, and furthermore, what proportion of the specific branched alkyl radical in the branched alkyl group is present, plasticization efficiency and migration resistance / The physical properties of weight loss properties can be more balanced, processability can be optimized, and significant improvements in mechanical properties such as tensile strength and elongation and stress resistance can be achieved due to the interaction of a number of tetraesters contained in the composition. can
[67]
Through this, it is possible to realize a product that is completely free from environmental issues, and has significantly improved the tensile strength of existing phthalate-based products, and can significantly improve migration resistance and stress resistance of existing terephthalate-based products. , it may be possible to realize a product whose level is greatly improved as well as the balance between physical properties compared to existing commercial products.
[68]
[69]
According to an embodiment of the present invention, in order to more optimally and preferably implement the above effects, the hexanoic acid isomer mixture may essentially include 2-methyl pentanoic acid and 3-methyl pentanoic acid. By necessarily including the two isomers among various isomers in the isomer mixture, the above-described effect can be realized with higher reproducibility.
[70]
In addition, the hexanoic acid isomer mixture may further include 1-hexanoic acid and cyclopentyl methanonic acid in 2-methyl pentanoic acid and 3-methyl pentanoic acid. In the case of 1-hexanoic acid, specific physical properties tend to be improved as it is included, but it is necessary to adjust its content in consideration of processability aspects such as absorption rate or plasticization efficiency, and cyclopentyl methanonic acid may also be the same.
[71]
According to an embodiment of the present invention, the hexanoic acid isomer mixture may contain 20 parts by weight or more of branched hexanoic acid based on 100 parts by weight of the total mixture, 30 parts by weight or more, 40 parts by weight or more, 50 parts by weight or more It may be included, and may be 95 parts by weight or less, 90 parts by weight or less, 85 parts by weight or less, 80 parts by weight or less, or 70 parts by weight or less.
[72]
In addition, 1-hexanoic acid may be included in 80 parts by weight or less, 70 parts by weight or less, 60 parts by weight or less, 50 parts by weight or less, and 5 parts by weight or more with respect to 100 parts by weight of the hexanoic acid isomer mixture and 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, or 25 parts by weight or more.
[73]
The branched and linear inclusion amounts can be appropriately adjusted according to the use in which the tetraester-based composition is applied as a plasticizer, and the desired physical properties can be achieved by controlling the ratio thereof.
[74]
Furthermore, the isomer mixture may further include cyclopentyl methanonic acid, and in this case, may be included in an amount of 30 parts by weight or less based on 100 parts by weight of the isomer mixture. Preferably, it may be 20 parts by weight or less, and may be included in 10 parts by weight or less. In the case of cyclopentyl methanoic acid, as long as it is substantially included, processability and mechanical properties may be improved, and the content may be adjusted in consideration of deterioration of physical properties due to a decrease in the relative content of other isomers.
[75]
Various isomers may be included in the mixture of hexanoic acid isomers, which determines the degree of branching of the tetraester-based composition according to an embodiment of the present invention, and although four types of isomers are typically mentioned, excluding the presence of other isomers not.
[76]
[77]
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.
[78]
That is, by appropriately controlling the esterification reaction, the plasticizer composition according to the present invention can be prepared, for example, by directly esterifying a mixture of hexanoic acid isomers and a tetrahydric alcohol, that is, pentaerythritol to prepare the tetraester-based composition. It is possible to prepare a plasticizer composition comprising.
[79]
The plasticizer composition according to an embodiment of the present invention is a material prepared by appropriately performing the esterification reaction, and if it meets the above conditions, in particular, if the ratio of branched hexanoic acid in the isomer mixture is controlled, the manufacturing method is not particularly limited.
[80]
As an example, the direct esterification reaction comprises the steps of adding a mixture of isomers of hexanoic acid and pentaerythritol, then adding a catalyst and reacting in a nitrogen atmosphere; removing unreacted alcohol and neutralizing unreacted acid; and dehydration and filtration by vacuum distillation.
[81]
In the case of the mixture of hexanoic acid isomers, that is, monocarboxylic acid, it can perform a main function of determining the component ratio in the composition to be prepared, and a molar ratio of 4:1 with the tetrahydric alcohol, such as pentaerythritol, can be applied theoretically, If a mixture of hexanoic acid isomers is added more than this molar ratio, it may contribute to improvement of the reaction rate. At this time, the additional amount of the hexanoic acid isomer mixture may be 500 mol% or less, 400 mol% or less, or 300 mol% or less, preferably 200 mol% or less or 100 mol% or less, based on the equivalent of the hexanoic acid isomer mixture can be positive.
[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 an 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 5.00% by weight, 0.01 to 3.00% by weight, 0.1 to 3.0% by weight, or 0.1 to 2.0% 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.
[84]
At this time, the reaction temperature may be in the range of 100 to 280 ℃, 100 to 250 ℃, or 100 to 230 ℃.
[85]
[86]
According to another embodiment of the present invention, there is provided a resin composition comprising the above-described plasticizer composition and resin.
[87]
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.
[88]
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.
[89]
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.
[90]
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.
[91]
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
[92]
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.
[93]
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.
[94]
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.
[95]
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. not.
[96]
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.
[97]
[98]
Example
[99]
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.
[100]
[101]
Example 1
[102]
1160 g of 1-hexanoic acid, 272 g of pentaerythritol, and 5 g of methanesulfonic acid are added to a reactor equipped with a stirrer, a condenser and a decanter, and then, under a nitrogen atmosphere, depending on the boiling point of the raw material and the conversion rate of the reaction, within the range of 100°C to 140°C After controlling the reaction temperature in the esterification reaction to terminate the reaction, remove the unreacted acid, neutralize the catalyst and the product with an aqueous alkali solution and wash with water, and purify the unreacted raw material and moisture to finally obtain a tetraester-based plasticizer composition .
[103]
[104]
Examples 2 to 12
[105]
The tetraester of Examples 2 to 11 by preparing an ester composition in the same manner as in Example 1, except that the carboxylic acid having 6 alkyl carbon atoms or an isomer mixture thereof described in Table 1 was added instead of 1-hexanoic acid in Example 1 A plasticizer composition was obtained.
[106]
[Table 1]
No matter weight ratio
Example 2 2-MPA/3-MPA/1-HA/CPMA 15/50/30/5
Example 3 2-MPA/3-MPA/1-HA/CPMA 30/30/30/10
Example 4 2-MPA/3-MPA/1-HA/CPMA 40/40/10/10
Example 5 2-MPA/3-MPA/1-HA/CPMA 30/40/20/10
Example 6 2-MPA/3-MPA/1-HA/CPMA 30/50/5/15
Example 7 2-MPA/3-MPA/1-HA/CPMA 50/40/2/8
Example 8 2-MPA/3-MPA/1-HA/CPMA 60/30/8/2
Example 9 2-MPA/3-MPA/1-HA/CPMA 40/50/10
Example 10 2-MPA/3-MPA/1-HA/CPMA 30/40/30
Example 11 2-MPA/3-MPA/1-HA 40/50/10
[107]
* 2-MPA: 2-methylpentanoic acid
[108]
* 3-MPA: 3-methylpentanoic acid
[109]
* 1-HA: 1-hexanoic acid
[110]
* CPMA: cyclopentylmethanoic acid
[111]
[112]
Comparative Example 1
[113]
Dioctyl phthalate (DOP, LG Chem) was applied as a plasticizer.
[114]
[115]
Comparative Example 2
[116]
Diisononyl phthalate (DINP, LG Chem) was applied as a plasticizer.
[117]
[118]
Comparative Example 3
[119]
As a plasticizer, GL300 manufactured by LG Chem, which is dioctyl terephthalate, was applied.
[120]
[121]
Comparative Example 4
[122]
As a plasticizer, GL520 manufactured by LG Chem, which is a mixture of dibutyl terephthalate, butyloctyl terephthalate and dioctyl terephthalate, was applied.
[123]
[124]
Comparative Example 5
[125]
As a plasticizer, GL330T manufactured by LG Chem, which is a mixture of dioctyl terephthalate and tributyl citrate, was applied.
[126]
[127]
Comparative Example 6
[128]
As a plasticizer, BET manufactured by LG Chem, which is a product derived from the esterification of trimethylol propane, 2-ethylhexanone and benzoic acid, was applied.
[129]
[130]
Comparative Example 7
[131]
As a plasticizer, Pevalen manufactured by Perstorp, a product derived from the esterification of valeric acid and pentaerythritol, was applied.
[132]
[133]
Comparative Example 8
[134]
1350 g of n-heptanoic acid, 272 g of pentaerythritol, and 5 g of methanesulfonic acid are added to a reactor equipped with a stirrer, a condenser and a decanter, and then, under a nitrogen atmosphere, within the range of 100°C to 140°C depending on the boiling point of the raw material and the conversion rate of the reaction After controlling the reaction temperature in the esterification reaction to terminate the reaction, remove the unreacted acid, neutralize the catalyst and the product with an aqueous alkali solution and wash with water, and purify the unreacted raw material and moisture to finally obtain a tetraester-based plasticizer composition .
[135]
[136]
Experimental Example 1: Evaluation of sheet performance
[137]
Using the plasticizers of Examples and Comparative Examples, specimens were manufactured under the following prescription and manufacturing conditions according to ASTM D638.
[138]
(1) Prescription : 100 parts by weight of straight vinyl chloride polymer (LS100S), 50 parts by weight of plasticizer and 3 parts by weight of stabilizer (BZ-153T)
[139]
(2) Mixing : Mixing at 700 rpm at 98℃
[140]
(3) Specimen production : 1T, 2T, and 3T sheets were produced by working at 165°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
[141]
(4) Evaluation items
[142]
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 plasticizing efficiency is excellent, so that a numerical value is small.
[143]
2) Tensile strength : According to ASTM D638 method, after pulling the cross head speed to 200 mm/min using UTM (manufacturer; Instron, model name; 4466) as a test device, 1T specimen The cut point was measured. Tensile strength was calculated as follows:
[144]
Tensile strength (kgf/cm 2 ) = load value (kgf) / thickness (cm) x width (cm)
[145]
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:
[146]
Elongation (%) = length after stretching / was calculated as initial length x 100.
[147]
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.
[148]
Transition loss (%) = [{(weight of initial specimen) - (weight of specimen after leaving in oven)} / (weight of initial specimen)] x 100
[149]
5) Measurement of volatile loss : After working the prepared specimen at 80° C. for 72 hours, the weight of the specimen was measured.
[150]
Loss on heating (wt%) = [{(initial specimen weight) - (test specimen weight after work)} / (initial specimen weight)] x 100.
[151]
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 seepage) was observed, and the result was written as a numerical value, at 0 The closer it was, the better the properties were.
[152]
7) Absorption rate measurement : The absorption rate is measured by measuring the time it takes for the resin and plasticizer to be mixed with each other and the torque of the mixer is stabilized using a planatary mixer (Brabender, P600) under the conditions of 73℃ and 60rpm. Processability was evaluated, and it was evaluated on a scale of 1 to 5 depending on the degree of excellence, with 5 being excellent and 1 being inferior.
[153]
[154]
(5) Evaluation results
[155]
The evaluation results of the above items are shown in Table 2 below.
[156]
[Table 2]
Hardness Tensile strength
(kgf/cm 2 ) Elongation
(%) Performance loss
(%) Heat loss
(%) stress resistance absorption
rate
(Shore A) (Shore D)
Example 1 84.0 37.8 214.7 320.7 1.40 0.39 0 5
Example 2 84.1 37.9 215.4 321.2 1.41 0.46 0 5
Example 3 84.2 37.8 216.8 320.9 1.45 0.40 0 5
Example 4 84.5 38.1 214.6 317.4 1.40 0.47 0.5 5
Example 5 84.3 37.9 208.6 304.6 1.38 0.38 0.5 5
Example 6 84.2 38.0 215.6 321.1 1.32 0.41 0 5
Example 7 84.5 38.1 220.2 321.5 1.40 0.45 0.5 5
Example 8 84.5 38.0 217.8 320.0 1.41 0.44 0.5 5
Example 9 84.0 37.9 215.6 318.4 1.38 0.41 0 5
Example 10 84.1 38.0 214.9 320.3 1.39 0.42 0.5 5
Example 11 84.0 37.8 213.4 317.9 1.38 0.40 0.5 5
Comparative Example 1 84.1 37.9 180.1 316.7 1.49 1.54 0 5
Comparative Example 2 86.3 39.9 195.0 326.4 2.10 0.72 1.5 3
Comparative Example 3 88.2 41.7 206.9 328.9 6.45 0.77 3.0 2
Comparative Example 4 86.1 39.6 202.3 310.9 5.64 2.19 2.5 5
Comparative Example 5 84.5 37.9 200.2 317.2 4.24 2.50 2.5 5
Comparative Example 6 91.5 46.4 241.7 289.8 3.86 0.58 0.5 One
Comparative Example 7 83.4 37.5 209.8 308.6 1.72 0.60 1.5 One
Comparative Example 8 86.7 41.3 204.6 320.6 5.78 0.30 2.5 3
[157]
Referring to the results of Table 2, compared to the case of applying the plasticizer of Comparative Examples 1 to 8, when the plasticizer of Examples 1 to 11 is applied, plasticization efficiency, tensile strength and elongation, and stress resistance performance, migration loss, It can be seen that it is uniform in terms of heating loss and has excellent physical properties. In particular, it can be confirmed that the processability is excellent in that the plasticization efficiency and absorption rate are excellent. In addition, in all physical properties, it is equivalent to or higher than that of the plasticizer of Comparative Example 1, which is a high-performance plasticizer but may cause fatal environmental problems. As it has been confirmed that it has been implemented, it can be confirmed that it is very suitable as an alternative plasticizer.
[158]
Furthermore, in the case of Comparative Examples 3 to 6, which are existing eco-friendly plasticizers developed as substitute products for phthalate-based plasticizers, there were problems in migration resistance and stress resistance, but the plasticizers of Examples showed significant improvement in physical properties in such migration resistance and stress resistance. You can check that it has been done.
[159]
In addition, through Comparative Examples 7 and 8, when a carboxylic acid having 5 or 7 carbon number instead of 6 is applied, there is a problem that plasticization efficiency and migration resistance are poor or mechanical properties are poor. It was confirmed that the embodiments according to the present invention to which an acid is applied do not have such problems, and further, in the case of stress resistance and absorption rate, an improved effect appears only when the number of carbon atoms is 6, and when the number of carbon atoms is 5 or 7, all poor It can be seen that the results are displayed.
Claims
[Claim 1]
A plasticizer composition comprising a tetraester-based composition comprising at least one tetraester of the following Chemical Formula 1, wherein the alkyl group of the tetraester is derived from a hexanoic acid isomer mixture having a degree of branching of 2.0 or less: [Formula 1 ] In Formula 1, R 1 to R 4 are each independently an n-pentyl group, a branched pentyl group, or a cyclopentyl group.
[Claim 2]
The plasticizer composition according to claim 1, wherein the hexanoic acid isomer mixture has a degree of branching of 1.5 or less.
[Claim 3]
The plasticizer composition of claim 1, wherein the hexanoic acid isomer mixture comprises 2-methylpentanoic acid and 3-methylpentanoic acid.
[Claim 4]
The plasticizer composition of claim 1, wherein the hexanoic acid isomer mixture comprises 1-hexanoic acid, 2-methylpentanoic acid, 3-methylpentanoic acid and cyclopentyl methanonic acid.
[Claim 5]
The plasticizer composition of claim 1, wherein the hexanoic acid isomer mixture contains 20 to 95 parts by weight of branched hexanoic acid based on 100 parts by weight of the total mixture.
[Claim 6]
The plasticizer composition according to claim 1, wherein the hexanoic acid isomer mixture contains 30 parts by weight or less of cyclopentyl methanoic acid based on 100 parts by weight of the total mixture.
[Claim 7]
The plasticizer composition of claim 1, wherein the hexanoic acid isomer mixture contains 80 parts by weight or less of 1-hexanoic acid based on 100 parts by weight of the total mixture.
[Claim 8]
The plasticizer composition according to claim 1, wherein the mixed weight of the triester and the diester contained in the tetraester-based composition is 5.0% by weight or less based on the total weight of the tetraester-based composition.
[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.