[One]Cross Citation with Related Applications
[2]This application claims the benefit of priority based on Korean Patent Application No. 10-2019-0051715 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 plasticizer composition and a resin composition comprising the same, and to a plasticizer composition having excellent properties while being environmentally friendly, 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]
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.
[9]
In these various areas of use, additives such as plasticizers, fillers, stabilizers, viscosity reducing agents, dispersants, defoamers, foaming agents, etc. will do
[10]
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.
[11]
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.
[12]
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.
[13]
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. .
[14]
Furthermore, hydrogenated products have been proposed to improve the poor performance of DEHTP products. However, the increase in unit cost due to hydrogenation also remains a problem to be solved.
[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]
[17]
[Prior art literature]
[18]
[Patent Literature]
[19]
(Patent Document 1) KR10-0957134B
[20]
DETAILED DESCRIPTION OF THE INVENTION
technical challenge
[21]
An object of the present invention is to provide an improved plasticizer composition that is environmentally friendly and has excellent physical properties, improves physical properties such as migration loss, tensile strength, and heat loss, and has excellent directionality in the case of elongation and stress resistance.
[22]
means of solving the problem
[23]
In order to solve the above problems, the present invention is a cyclohexane 1,4-diester-based material, and an alkyl group bonded to two ester groups is each independently selected from a diester-based material having 8 to 10 carbon atoms; and a cyclohexane 1,2,4-triester-based material, wherein the alkyl groups bonded to three ester groups are each independently selected from the group consisting of 4 to 10 carbon atoms; including, the cyclohexane 1,4-di The ester-based material and the cyclohexane 1,2,4-triester-based material have a weight ratio of 95:5 to 5:95.
[24]
In order to solve the above problems, the present invention provides a resin composition comprising 100 parts by weight of the resin and 5 to 150 parts by weight of the plasticizer composition.
[25]
Effects of the Invention
[26]
The plasticizer composition of the present invention is environmentally friendly, and therefore, when the plasticizer composition of the present invention is included in the resin composition, the tensile strength, elongation, transferability, heat loss and resistance are equivalent to or higher than existing phthalate products or improved products thereof. Physical properties such as stress properties can be remarkably improved.
[27]
In particular, migration resistance and heat loss, which were extremely difficult to improve due to the problem of cyclohexane 1,4-diester-based materials, can be improved, and compatibility with resin and plasticization efficiency can be maintained at an excellent level.
[28]
Modes for carrying out the invention
[29]
Hereinafter, the present invention will be described in more detail to help the understanding 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 means an alkyl group in which a methyl group or an ethyl group is branched to the main chain of the alkyl group, and unless there is an alkyl group otherwise referred to as a branched chain, a methyl group or an ethyl group is bonded to the main chain It can be used as a generic term for an alkyl group.
[34]
As used herein, the term “isononyl group” may mean an alkyl group having a total of 9 carbon atoms in which at least one branch is substituted with one or two methyl groups, one ethyl group, and one propyl group in the main chain, For example, 2-methyloctyl group, 3-methyloctyl group, 4-methyloctyl group, 5-methyloctyl group, 6-methyloctyl group, 3-ethylheptyl group, 2-ethylheptyl group, 2,5-dimethylheptyl group Tyl group, 2,3-dimethylheptyl group, 4,5-dimethylheptyl group, 3-ethyl-4-methylhexyl group, 2-ethyl-4-methylhexyl group, or 2-propylhexyl group As a term used, commercially used isononyl alcohol (CAS No.: 68526-84-1, 27458-94-2) may refer to a composition of isomers having a branching degree of 1.2 to 1.9, and In some cases, n-nonyl groups may also be included.
[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 with a cohesive property and poor flowability as fine, dense pore-free particles having a size of several thousand nanometers.
[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 that is a product of a specific reaction, such as an esterification reaction, is performed through gas chromatography measurement, and Agilent's gas chromatography instrument (product name: Agilent 7890 GC, column: HP-5, carrier gas) : Analyze with 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) .
[41]
In the present specification, 'hardness' refers to 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.
[42]
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.
[43]
[Equation 1]
[44]
Tensile strength (kgf/cm 2 ) = load value (kgf) / thickness (cm) x width (cm)
[45]
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.
[46]
[Equation 2]
[47]
Elongation (%) = length after stretching / initial length x 100
[48]
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 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, remove the plates attached to both sides of the test piece, measure the weights before and after leaving the plates in the oven, and calculate the transfer loss according to Equation 3 below. Here, the material of the plate may be various, such as PS (Polystyrene), ABS, Glass, and the specimen itself (Specimen plate), and the plate material used for measurement in this specification is Glass.
[49]
[Equation 3]
[50]
[Equation 3]
[51]
Transition loss (%) = {[(initial weight of specimen) - (weight of specimen after leaving in oven)] / (initial weight of specimen)} x 100
[52]
In the present specification, 'volatile loss' refers to measuring the weight of the specimen after working the specimen at 80°C for 72 hours.
[53]
[Equation 4]
[54]
Loss on heating (%) = {[(initial specimen weight) - (test specimen weight after work)] / (initial specimen weight)} x 100
[55]
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.
[56]
[57]
Hereinafter, the present invention will be described in more detail to help the understanding of the present invention.
[58]
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.
[59]
[60]
The plasticizer composition according to an embodiment of the present invention includes a cyclohexane 1,4-diester-based material and a cyclohexane 1,2,4-triester-based material, wherein the diester-based material is bonded to two ester groups. Each alkyl group is independently selected from those having 8 to 10 carbon atoms, and the triester-based material is independently selected from those having 4 to 10 carbon atoms in the alkyl group bonded to three ester groups.
[61]
The cyclohexane 1,4-diester-based material may have 8 to 10 carbon atoms in the alkyl group bonded thereto, for example, a 2-ethylhexyl group, an isononyl group, an n-nonyl group, a 2-propylheptyl group Or it may be an isodecyl group, preferably a 2-ethylhexyl group, an isononyl group or a 2-propylheptyl group may be applied. In the case of the diester-based material, it can be generally obtained by hydrogenating terephthalate, and as a plasticizer to replace the terephthalate-based plasticizer, plasticization efficiency and light resistance can be quite excellent. In terms of achieving this effect, more preferably, the alkyl group may have 8 or 9 carbon atoms.
[62]
In addition, the diester-based material is one in which an ester group is bonded to the 1st and 4th carbons of cyclohexane, and may be a material derived from hydrogenation from terephthalate, and an ester group is bonded to the 1st and 2nd carbons or 1 Compared to materials in which an ester group is bonded to No. and No. 3 carbons, plasticization efficiency and mechanical properties may be excellent, so it is preferable to apply a diester-based material bonded to No. 1 and No. 4 positions according to the present invention. can
[63]
The diester-based material may be prepared by hydrogenating a terephthalate-based material, or may be prepared by an esterification reaction of cyclohexanedicarboxylic acid, and the diester-based material may be obtained through an appropriate combination of hydrogenation and esterification. can be manufactured.
[64]
When the cyclohexane 1,4-diester-based material is directly prepared, the cyclohexane 1,4-dicarboxylic acid or derivative thereof may be prepared by direct esterification or transesterification reaction with alcohol.
[65]
The cyclohexane derivative of 1,4-dicarboxylic acid may be at least one selected from the group consisting of an anhydride of cyclohexane 1,4-dicarboxylic acid and/or an alkyl ester of 1,4-dicarboxylic acid of cyclohexane. In this case, the alkyl ester may be an alkyl ester having 8 to 10 carbon atoms.
[66]
The finally prepared alkyl group of 1,4-diester of cyclohexane has 8 to 10 carbon atoms. Preferably, the same alkyl group as described above is applied, and these alkyl groups may be derived from the alcohol used in the preparation.
[67]
[68]
When the cyclohexane 1,4-diester-based material represented by Chemical Formula 1 is prepared by the direct esterification reaction, the alcohol is 2 to 10 per 1 mole of the cyclohexane 1,4-dicarboxylic acid or a derivative thereof. It may be used in moles, 2 to 8 moles, 2 to 6 moles, or 2 to 5 moles, of which 2 to 5 moles is preferable.
[69]
The direct esterification reaction may be performed in the presence of a catalyst, and the catalyst may be at least one selected from the group consisting of inorganic acids, organic acids, and Lewis acids, and among them, at least one selected from the group consisting of organic acids and Lewis acids. can
[70]
The inorganic acid may be at least one selected from the group consisting of sulfuric acid, hydrochloric acid and phosphoric acid.
[71]
The organic acid may be at least one selected from the group consisting of p-toluenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, and alkyl sulfuric acid.
[72]
The Lewis acid is an aluminum derivative (aluminum oxide, aluminum hydroxide), a tin derivative (C 3 to C 12 fatty acid tin, tin oxide, tin hydroxide), a titanium derivative (C 3 to C 8 tetraalkyl titanate, titanium oxide, hydroxide titanium), lead derivatives (lead oxide, lead hydroxide), and zinc derivatives (zinc oxide, zinc hydroxide) may be at least one selected from the group consisting of.
[73]
When the catalyst is a homogeneous catalyst, it may be used in an amount of 0.001 to 5 parts by weight or 0.001 to 3 parts by weight based on 100 parts by weight of the total of the cyclohexane 1,4-dicarboxylic acid or derivative thereof and alcohol, of which 0.01 to 3 parts by weight It is preferably used in parts by weight.
[74]
When the catalyst is a heterogeneous catalyst, 0.5 to 200 parts by weight or 0.5 to 100 parts by weight based on 100 parts by weight of the total of cyclohexane 1,4-dicarboxylic acid or a derivative thereof and alcohol, 0.5 to 200 parts by weight of which It is preferable to use it as a part.
[75]
The direct esterification reaction may be carried out at 100 to 280 °C, 130 to 250 °C, or 150 to 230 °C, of ​​which it is preferably carried out at 150 to 230 °C.
[76]
The direct esterification reaction may be performed for 3 to 30 hours or 3 to 25 hours, of which 3 to 25 hours is preferable.
[77]
[78]
On the other hand, when the cyclohexane 1,4-diester-based material is prepared by the transesterification reaction, it may be prepared by the transesterification reaction of the cyclohexane 1,4-dicarboxylic acid derivative and alcohol.
[79]
The derivative of 1,4-dicarboxylic acid of cyclohexane may be an alkyl ester of 1,4-dicarboxylic acid of cyclohexane, and preferably a methyl ester of 1,4-dicarboxylic acid of cyclohexane to facilitate separation of the reaction product. can be used
[80]
Based on 1 mole of the cyclohexane derivative of 1,4-dicarboxylic acid, 2 to 10 moles, 2 to 8 moles, 2 to 6 moles, or 2 to 5 moles of the alcohol may be used, of which 2 to 5 moles are used. It is preferable to be
[81]
The transesterification reaction may be performed in the presence of a catalyst, and in this case, the reaction time may be shortened.
[82]
The catalyst may be at least one selected from the group consisting of a Lewis acid and an alkali metal.
[83]
The Lewis acid is as described in the description of the direct esterification reaction, aluminum derivatives (aluminum oxide, aluminum hydroxide), tin derivatives (C 3 to C 12 fatty acid tin, tin oxide, tin hydroxide), titanium derivatives (C 3 It may be at least one selected from the group consisting of to C 8 tetraalkyl titanate, titanium oxide, titanium hydroxide), lead derivatives (lead oxide, lead hydroxide), and zinc derivatives (zinc oxide, zinc hydroxide).
[84]
In addition, the alkali metal may be at least one selected from the group consisting of sodium alkoxide, potassium alkoxide, sodium hydroxide and potassium hydroxide, and a single or a mixed catalyst of two or more types of the metal catalyst may be used.
[85]
The catalyst may be used in an amount of 0.001 to 5 parts by weight or 0.01 to 3 parts by weight based on 100 parts by weight of the total of the cyclohexane derivative of 1,4-dicarboxylic acid and the alcohol, of which 0.001 to 3 parts by weight is used desirable.
[86]
The transesterification reaction may be carried out at 120 to 250 °C, 135 to 230 °C, or 140 to 220 °C, of ​​which 140 to 220 °C is preferable.
[87]
The transesterification reaction may be carried out for 0.5 to 10 hours or 0.5 to 8 hours, of which it is preferably carried out for 0.5 to 8 hours.
[88]
In the direct esterification reaction or transesterification reaction, at least one selected from the group consisting of benzene, toluene, xylene and cyclohexane is added to promote the outflow of lower alcohols such as water or methanol produced by the reaction. It can be added, and commercially available nitrogen, etc., can be used as entrainment for the same purpose.
[89]
The cyclohexane 1,4-diester-based material represented by Formula 1 prepared by the direct esterification reaction or the transesterification reaction may be purified by performing a separate post-treatment. The post-treatment may be at least one selected from the group consisting of catalyst inactivation treatment (neutralization treatment, base treatment), water washing treatment, distillation (reduced pressure or dehydration treatment), and adsorption purification treatment.
[90]
Unlike the above manufacturing method, a manufacturing method comprising converting a dialkyl terephthalate-based material into a cyclohexane 1,4-diester-based material by hydrogenating it in the presence of a metal catalyst may be applied.
[91]
The hydrogenation step is a reaction for removing the aromaticity of the benzene ring of terephthalate by adding hydrogen in the presence of a metal catalyst, and may be a kind of reduction reaction.
[92]
The hydrogenation reaction synthesizes a cyclohexane 1,4-diester-based material by reacting the terephthalate-based material with hydrogen under a metal catalyst, and the reaction condition is a benzene ring without affecting the carbonyl group substituted in benzene. It may include all the conventional reaction conditions capable of hydrogenating only .
[93]
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.
[94]
[95]
The plasticizer composition according to an embodiment of the present invention is characterized in that the cyclohexane 1,2,4-triester-based material is mixed in addition to the cyclohexane 1,4-diester-based material.
[96]
On the other hand, the diester-based material is a material applied to improve the plasticizing efficiency of the terephthalate-based material, but despite the improvement of the plasticizing efficiency, the transferability and the heating loss are equivalent to or less than the terephthalate-based plasticizer. It may be poor, and it is difficult to compensate for such poor physical properties, so it is a material that may be difficult to commercialize as a plasticizer that meets the needs of the actual market. In addition, although the terephthalate-based plasticizer is an eco-friendly substitute for the phthalate-based plasticizer, the fact that it cannot escape from the petroleum-based plasticizer because it contains a benzene ring may also act as a limitation. Furthermore, the diester-based material is difficult to be applied alone in that it does not have significantly improved physical properties to offset the unit price increased due to hydrogenation of the terephthalate-based material. Blending is required.
[97]
When the diester-based material is mixed with terephthalate, there is no effect in improving physical properties other than unit price competitiveness, and in addition, it is quite difficult to compensate for the lowered mechanical properties, but in the case of the plasticizer composition according to the present invention, As a blending partner material of the diester-based material, it was confirmed that such physical properties could be improved by applying cyclohexane 1,2,4-triester as a triester-based material.
[98]
The cyclohexane 1,2,4-triester-based material may be independently selected from those having 4 to 10 carbon atoms, and preferably the alkyl group bonded to each of the three ester groups, preferably 5 to 9 carbon atoms. . When a triester-based material to which an alkyl group having less than 4 carbon atoms is bonded is applied, the purpose of complementing mechanical properties may not be achieved, and when an alkyl group having more than 10 carbon atoms is applied, there may be a problem in that even excellent plasticization efficiency is offset.
[99]
In order to prevent the above problems and further maximize the effect, the alkyl group may preferably have 5 to 9 carbon atoms, for example, n-pentyl group, isopentyl group, n-hexyl group, isohexyl group, n-heptyl group. , an isoheptyl group, a 2-ethylhexyl group, an isononyl group or a 2-propylheptyl group may be applied.
[100]
According to an embodiment of the present invention, the cyclohexane 1,2,4-triester-based material can be prepared by hydrogenating trimellitate, and cyclohexane tricarboxylic acid is subjected to transesterification or direct esterification reaction. Also, if the sequence of the esterification reaction and the hydrogenation reaction is properly combined and the raw material is appropriately applied accordingly, the cyclohexane 1,2,4-triester-based material can be prepared. For this manufacturing method, substantially the same method as that of the above-described diester-based material can be applied, and cyclohexane 1,2,4-triester-based material can be obtained without difficulty if only fine control of the raw material and reaction temperature is performed. can
[101]
[102]
According to an embodiment of the present invention, the diester-based material and the triester-based material are included in a weight ratio of 95:5 to 5:95. The weight ratio may be, for example, 99:1, 95:5, 90:10, 85:15, 80:20, 75:25, 70:30, or 60:40 as an upper limit, and 1:99, 5 as a lower limit. :95, 10:90, 15:85, 20:80, 25:75, 30:70, 40:60 or 50:50. However, in order to optimize the effect as described above, a weight ratio of 90:10 to 10:90, preferably a weight ratio of 80:20 to 20:80 may be applied, and more preferably 70:30 to 30:70 It can be applied in a weight ratio of
[103]
As in the present invention, when the cyclohexane 1,4-diester-based material and the cyclohexane 1,2,4-triester-based material are mixed, the excellent physical properties of each material are maintained, while the poor physical properties are improved synergy can have an effect. In particular, it is possible to achieve remarkable improvement in mechanical properties such as tensile strength and elongation, while maintaining excellent plasticization efficiency. can
[104]
[105]
The resin composition according to another embodiment of the present invention includes 100 parts by weight of the resin, and 5 to 150 parts by weight of the above-described plasticizer composition. 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.
[106]
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.
[107]
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.
[108]
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.
[109]
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
[110]
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.
[111]
The plasticizer composition according to an embodiment of the present invention can be preferably applied to a straight vinyl chloride polymer, and thus can be melt-processed, and as a processing method to be described later, a resin product applied to processing such as calendering, extrusion, injection, etc. It can be used as a plasticizer.
[112]
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.
[113]
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.
[114]
The stabilizer is, for example, a calcium-zinc (Ca-Zn-based) stabilizer such as a calcium-zinc complex stearic acid salt, and a barium-zinc (Ba-Zn-based) stabilizer using barium-zinc as the main metal material. can be used, but is not particularly limited thereto.
[115]
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.
[116]
The resin composition may be used in the manufacture of electric wires, flooring materials, automobile interior materials, films, sheets or tubes.
[117]
[118]
Hereinafter, embodiments of the present invention will be described in detail so that those of ordinary skill in the art can easily carry out the present invention. However, the present invention may be embodied in several different forms and is not limited to the embodiments described herein.
[119]
[120]
Preparation Example 1: Di (2-ethylhexyl) cyclohexane 1,4-diester (1,4-DEHCH)
[121]
516.5 g of 1,4-dicarboxylic acid cyclohexane, 1,170 g of 2-ethylhexyl alcohol, 1.55 g of tetraisopropyl titanate as catalyst was added, the reaction temperature was set to 230 °C, and nitrogen gas was continuously added, the esterification reaction was performed directly for about 6 hours, and the reaction was completed when the acid value reached 0.1.
[122]
After completion of the reaction, in order to remove unreacted raw materials, distillation extraction was performed under reduced pressure. After distillation and extraction, 1,155 g (yield: 97%) of di(2-ethylhexyl)cyclohexane 1,4-dicarboxylate was prepared through a neutralization process, a dehydration process, and a filtration process.
[123]
[124]
Preparation Example 2: Diisononyl cyclohexane 1,4-diester (1,4-DINCH)
[125]
Diisononyl cyclohexane 1,4-dicarboxylate was prepared in the same manner as in Preparation Example 1, except that isononyl alcohol was used instead of 2-ethylhexyl alcohol in Preparation Example 1.
[126]
[127]
Preparation Example 3: Di (2-propylheptyl) cyclohexane 1,4-diester (1,4-DPHCH)
[128]
Di (2-propylheptyl) cyclohexane 1,4-dicarboxylate was prepared in the same manner as in Preparation Example 1, except that 2-propylheptyl alcohol was used instead of 2-ethylhexyl alcohol in Preparation Example 1.
[129]
[130]
Preparation Example 4: Diisodecyl cyclohexane 1,4-diester (1,4-DIDCH)
[131]
Diisodecyl cyclohexane 1,4-dicarboxylate was prepared in the same manner as in Preparation Example 1, except that isodecyl alcohol was used instead of 2-ethylhexyl alcohol in Preparation Example 1.
[132]
[133]
Preparation Example 5: Tri (2-ethylhexyl) cyclohexane 1,2,4-triester-based material (1,2,4-TEHCH)
[134]
In a 4-neck 3 liter reactor equipped with a condenser, condenser, decanter, reflux pump, temperature controller, stirrer, etc., 432.4 g cyclohexane 1,2,4-tricarboxylic acid, 1014 g 2-ethylhexyl alcohol, tetraisopropyl titanate as catalyst 1.55 g was added, the reaction temperature was set to 230° C., and nitrogen gas was continuously added, the esterification reaction was performed directly for about 6 hours, and the reaction was completed when the acid value reached 0.1.
[135]
After completion of the reaction, in order to remove unreacted raw materials, distillation extraction was performed under reduced pressure. After distillation extraction, 1,072 g (yield: 97%) of tri(2-ethylhexyl)cyclohexane 1,4-tricarboxylate was prepared through a neutralization process, a dehydration process, and a filtration process.
[136]
[137]
Preparation 6: Tripentyl cyclohexane 1,2,4-triester-based material (1,2,4-TPCH)
[138]
Tripentyl cyclohexane 1,4-tricarboxylate was prepared in the same manner as in Preparation Example 5, except that n-pentyl alcohol was used instead of 2-ethylhexyl alcohol in Preparation Example 5.
[139]
[140]
Preparation Example 7: Triisononyl cyclohexane 1,2,4-triester-based material (1,2,4-TINCH)
[141]
Triisononyl cyclohexane 1,4-tricarboxylate was prepared in the same manner as in Preparation Example 5, except that isononyl alcohol was used instead of 2-ethylhexyl alcohol in Preparation Example 5.
[142]
[143]
Preparation 8: tributyl cyclohexane 1,2,4-triester-based material (1,2,4-TBCH)
[144]
Tributyl cyclohexane 1,4-tricarboxylate was prepared in the same manner as in Preparation Example 5, except that n-butyl alcohol was used instead of 2-ethylhexyl alcohol in Preparation Example 5.
[145]
[146]
Preparation Example 9: Tri (2-propylheptyl) cyclohexane 1,2,4-triester-based material (1,2,4-TPHCH)
[147]
Tri (2-propylheptyl) cyclohexane 1,4-tricarboxylate was prepared in the same manner as in Preparation Example 5, except that 2-propylheptyl alcohol was used instead of 2-ethylhexyl alcohol in Preparation Example 5.
[148]
[149]
Examples and Comparative Examples
[150]
Plasticizer compositions of Examples and Comparative Examples were prepared using the materials prepared in Preparation Examples, and are summarized in Table 1 below. The evaluation of the physical properties of the plasticizer composition was performed according to the following experimental items. Commercial products were used for materials other than those prepared in Preparation Example.
[151]
[Table 1]
1,4-diester 1,2,4-triester Etc
Example 1 DEHCH 10 1) TEHCH 90 -
Example 2 DEHCH 30 TEHCH 70 -
Example 3 DEHCH 50 TEHCH 50 -
Example 4 DEHCH 70 TEHCH 30 -
Example 5 DEHCH 90 TEHCH 10 -
Example 6 DINCH 70 TPCH 30 -
Example 7 DEHCH 80 TINCH 20 -
Example 8 DEHCH 40 TBCH 60 -
Example 9 DEHCH 50 TPHCH 50 -
Example 10 DPHCH 80 TINCH 20 -
Example 11 DIDCH 90 TEHCH 10 -
Comparative Example 1 - - DINP 2)
Comparative Example 2 - - DEHTP 3)
Comparative Example 3 - - TEHTM
Comparative Example 4 DEHCH 100 - -
Comparative Example 5 - TEHCH 100 -
Comparative Example 6 DINCH 100 - -
Comparative Example 7 - TPCH 100 -
Comparative Example 8 DEHCH 50 - DEHTP 50
Comparative Example 9 DEHCH 50 - TEHTM 50
Comparative Example 10 DHxCH 50 TEHCH 50 -
[152]
1) All contents in Table 1 above are in weight %. 2) DINP: diisononyl phthalate
[153]
3) DEHTP: di(2-ethylhexyl) terephthalate
[154]
4) TEHTM: tri(2-ethylhexyl) trimellitate
[155]
[156]
Experimental Example 1: Evaluation of sheet performance
[157]
Using the plasticizers of Examples and Comparative Examples, specimens were manufactured under the following prescription and manufacturing conditions according to ASTM D638.
[158]
(1) Prescription : 100 parts by weight of straight vinyl chloride polymer (LS100S, LG Chem), 40 parts by weight of plasticizer and 3 parts by weight of stabilizer (BZ-153T)
[159]
(2) Mixing : Mixing at 700 rpm at 98℃
[160]
(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).
[161]
(4) Evaluation items
[162]
1) Hardness: Using ASTM D2240, shore hardness (Shore “A” and “D”) at 25° C. was measured with a 3T specimen for 10 seconds. It is evaluated that the plasticizing efficiency is excellent, so that a numerical value is small.
[163]
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:
[164]
Tensile strength (kgf/cm 2 ) = load value (kgf) / thickness (cm) x width (cm)
[165]
3) Elongation rate: According to 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 calculated as follows Calculated as:
[166]
Elongation (%) = length after stretching / initial length x 100 was calculated.
[167]
4) Measurement of migration loss: A specimen having a thickness of 1 mm was obtained according to KSM-3156, and 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 (80° C.) for 72 hours, then taken out and cooled at room temperature for 4 hours. Then, the weight of the specimen from which the glass plate attached to both sides of the specimen was removed was measured before and after leaving it in the oven to calculate the transfer loss by the following formula.
[168]
Transition loss (%) = {[(initial weight of specimen) - (weight of specimen after leaving in oven)] / (weight of initial specimen)} x 100
[169]
5) volatile loss: After working the prepared specimen at 113° C. for 72 hours, the weight of the specimen was measured.
[170]
Loss on heating (%) = {[(initial specimen weight) - (test specimen weight after work)] / (initial specimen weight)} x 100
[171]
6) Stress test (stress resistance): After a specimen having a thickness of 2 mm was left in a bent state at 23° C. for 72 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.
[172]
(5) Evaluation results
[173]
The evaluation results of the above items are shown in Table 2 below.
[174]
[Table 2]
Hardness Tensile strength (kgf/cm 2 ) Elongation (%) Performance loss (%) Heat loss (%) stress resistance
division Shore A Shore D
Example 1 93.1 46.5 232.9 318.7 1.82 0.49 0
Example 2 92.5 45.9 230.8 318.3 2.29 0.65 0
Example 3 92.2 45.5 232.4 319.1 2.36 0.81 0
Example 4 90.9 45.0 235.5 315.4 2.86 1.05 0
Example 5 90.1 44.8 234.6 310.1 2.98 1.17 0
Example 6 92.3 45.6 234.7 325.4 2.35 0.70 0
Example 7 90.3 45.0 245.1 320.2 1.95 0.95 0
Example 8 87.8 42.2 238.9 301.0 2.34 2.14 0
Example 9 93.3 46.8 241.0 310.5 2.23 0.56 0.5
Example 10 94.5 47.9 240.7 298.6 3.01 1.02 1.0
Example 11 94.2 47.5 245.3 302.1 2.90 0.45 0.5
Comparative Example 1 92.1 45.9 226.8 289.6 3.24 1.47 0.5
Comparative Example 2 93.4 46.7 234.0 303.2 4.23 1.38 1.5
Comparative Example 3 95.2 47.8 227.6 305.7 1.78 0.52 0.5
Comparative Example 4 89.7 44.5 214.0 297.4 4.20 2.47 2
Comparative Example 5 94.2 47.9 215.6 301.2 1.80 0.60 0.5
Comparative Example 6 92.0 45.7 209.4 274.6 3.68 1.85 2
Comparative Example 7 90.5 45.1 198.6 257.4 1.23 1.30 0
Comparative Example 8 92.3 45.7 220.3 298.1 4.22 2.03 2
Comparative Example 9 93.0 46.2 220.3 301.2 3.65 2.01 1.5
Comparative Example 10 87.9 42.3 220.4 287.6 2.02 4.58 1.5
[175]
Referring to Table 2, in the case of Examples 1 to 11 to which the plasticizer composition according to an embodiment of the present invention is applied, it can be seen that mechanical properties are significantly improved compared to Comparative Example 1, which is DINP used as an existing product, and plasticization efficiency It can be seen that while maintaining the superiority of the stress resistance, there is also a significant improvement.
[176]
In addition, Comparative Examples 2 and 4 are a case in which mixing is not performed, unlike in Examples, and Comparative Example 2 has poor plasticization efficiency due to high hardness, mechanical properties such as elongation, and transfer characteristics, etc. It can be seen that the stress property is also poor, and in Comparative Example 4, only the plasticization efficiency was improved and all other technical characteristics were poorly displayed, so that it was difficult to commercialize it by itself. In addition, in the case of Comparative Example 8, as a mixture of the materials of Comparative Examples 2 and 4, the physical properties appeared to have intermediate values, but the stress resistance was further deteriorated, and no improvement was seen in the transition loss.
[177]
On the other hand, referring to Examples 1 to 5, mechanical properties that could not be improved through 1,4-DEHCH or DEHTP, or a mixed plasticizer thereof, while maintaining the excellent properties possessed by 1,4-DEHCH As it is confirmed that the improved stress resistance is improved, it is possible to selectively have excellent physical properties due to the mutual synergistic effect, and furthermore, it can be confirmed that there is an unexpected improvement. Furthermore, it can be said that this improvement was demonstrated through Comparative Example 9 that the effect could not be significantly improved even if the trimellitate-based material was added.

WE CLAIMS

1,4-Cyclohexane diester-based material, wherein each alkyl group bonded to two ester groups is independently selected from the group consisting of 8 to 10 carbon atoms; and a cyclohexane 1,2,4-triester-based material, wherein the alkyl groups bonded to three ester groups are each independently selected from the group consisting of 4 to 10 carbon atoms; including, the cyclohexane 1,4-di The weight ratio of the ester-based material and the cyclohexane 1,2,4-triester-based material is 95:5 to 5:95.
[Claim 2]
The plasticizer composition according to claim 1, wherein the weight ratio of the cyclohexane 1,4-diester-based material and the cyclohexane 1,2,4-triester-based material is 90:10 to 10:90.
[Claim 3]
The plasticizer composition according to claim 1, wherein the weight ratio of the cyclohexane 1,4-diester-based material and the cyclohexane 1,2,4-triester-based material is 80:20 to 20:80.
[Claim 4]
The plasticizer composition of claim 1, wherein the alkyl group bonded to the triester-based material is each independently selected from those having 5 to 9 carbon atoms.
[Claim 5]
The method according to claim 1, wherein the alkyl group bonded to the triester material, each independently, n-pentyl group, isopentyl group, n-hexyl group, isohexyl group, n-heptyl group, isoheptyl group, 2-ethylhexyl group A plasticizer composition selected from the group consisting of a sil group, an isononyl group and a 2-propylheptyl group.
[Claim 6]
The plasticizer composition of claim 1, wherein the alkyl group bonded to the diester-based material is each independently selected from the group consisting of a 2-ethylhexyl group, an isononyl group and a 2-propylheptyl group.
[Claim 7]
The method according to claim 1, wherein the diester-based material comprises at least one selected from the group consisting of di(2-ethylhexyl) cyclohexane 1,4-diester and diisononyl cyclohexane 1,4-diester Phosphorus plasticizer composition.
[Claim 8]
The method according to claim 1, wherein the triester-based material is triisopentyl cyclohexane 1,2,4-triester, triisohexyl 1,2,4-triester, triisoheptyl cyclohexane 1,2,4-triester , tri(2-ethylhexyl) cyclohexane 1,2,4-triester, triisononyl cyclohexane 1,2,4-triester and tri(2-propylheptyl) cyclohexane 1,2,4-triester A plasticizer composition comprising at least one selected from the group consisting of.
[Claim 9]
The method according to claim 1, wherein the diester-based material comprises di(2-ethylhexyl) cyclohexane 1,4-diester, and the triester-based material is tri(2-ethylhexyl) cyclohexane 1,2,4 - A plasticizer composition comprising a triester.
[Claim 10]
The method according to claim 1, wherein the diester-based material comprises diisononyl cyclohexane 1,4-diester, and the triester-based material comprises triisononyl cyclohexane 1,2,4-triester plasticizer composition.
[Claim 11]
100 parts by weight of resin; and 5 to 150 parts by weight of the plasticizer composition according to claim 1 .
[Claim 12]
The method according to claim 11, wherein the resin is straight vinyl chloride polymer, paste vinyl chloride polymer, ethylene vinyl acetate copolymer, ethylene polymer, propylene polymer, polyketone, polystyrene, polyurethane, natural rubber, synthetic rubber, and from the group consisting of a thermoplastic elastomer A resin composition that is one or more selected.