KR100952491B1 - Ester based plasticizer compounds for PVC resin and preparing method thereof - Google Patents

Abstract

The present invention relates to a novel plasticizer composition for PVC resins obtained by esterifying 1,6-hexanediol and two or more monocarboxylic acid compounds, a preparation method thereof, and a PVC resin composition comprising the same, and more particularly, to the present invention. It relates to an ester plasticizer having a chemical structure represented by the following formula (1).

In Chemical Formula 1, R ₁ and R ₂ may be the same as or different from each other, and a linear, crushed, cyclic alkyl group, or phenyl group having 4 to 10 carbon atoms may be used.

The present invention not only solves the environmental problem, which is a problem of the existing phthalate plasticizer for PVC resin, but also has excellent physical properties such as tensile strength, processability, and elongation while solving the compatibility with the PVC resin of the non-phthalate plasticizer for PVC resin. It is related with the ester plasticizer composition for PVC resin which can process resin.

Plasticizer, 1,6-hexanediol, benzoic acid, 3-ethyl heptanoic acid, polyvinyl chloride resin

Description

Ester-based plasticizer compositions for PPC resins and methods for preparing the same

The present invention relates to a novel plasticizer composition for PVC resins obtained by esterifying 1,6-hexanediol and two or more monocarboxylic acid compounds, and solves environmental problems, which are problems of conventional plasticizers for PVC resins. It is related with the ester plasticizer composition for PVC resin which can process PVC resin excellent in physical properties, such as strength, workability, and elongation.

Polyvinyl chloride resin (PVC resin, hereinafter referred to as "PVC resin") is a plasticizer, as well as various additives such as stabilizers, fillers, pigments, etc. It is a general purpose resin that can give processing properties. Using these various process properties, PVC resin is widely used as a material for a variety of products, from films, hoses, pipes, wires, and artificial leather to wallpaper, gloves, and toys.

Plasticizers used in the processing of such PVC resins are generally added into polar and non-polar parts as materials added to lower the melting temperature and melt viscosity of the polymer to improve processability and to impart flexibility. In addition, the plasticizer is added to improve the function of the polymer, such as electrical insulation, adhesion, cold resistance, phthalates such as DOP (dioctyl phthalate), DBP (dibutyl phthalate), DINP (diisononyl phthalate), DOA (dioctyl adipate), Adipate systems, such as DINA (diisononyl adipate), are widely used.

Among these, phthalate plasticizers have been controversial in terms of safety and toxicity both at home and abroad. In 2004, phthalate plasticizers were banned in children's products. The situation is being watched.

In addition, there is a movement in the Korean Ministry of Environment to designate phthalate-based plasticizers as toxic and restricted substances. Therefore, the development of non-phthalate plasticizers, which are environmentally friendly plasticizers, is urgently needed while avoiding endocrine disruption.

Patents for eco-friendly plasticizers include neopentylglycol ester (Republic of Korea Patent Registration 10-0385731), trimethylolpropane ester (Republic of Korea Patent Publication 2002-0057559), diethylene glycol ester (Republic of Korea Patent Publication 10-2005-0026178), dipropylene Glycol esters (Korean Patent Publication No. 10-2006-0097587), triethylene glycol ester (Korean Patent Publication No. 10-2006-0108210) and the like are introduced, but the environmentally friendly plasticizers are less processed than the conventional plasticizers that are currently commercialized, etc. , PVC resin processing has a problem of poor workability and compatibility.

Plasticizers are mainly used to improve processability of PVC resins and to impart physical properties, and are used in various fields such as wire coating, hoses, films, sheets, wallpaper, artificial leather, and food packaging films. In particular, the plasticizers used to be used vary depending on the use of PVC resins. In general, the plasticizers must have excellent compatibility and plasticization efficiency with the resins, and have low volatility and low temperature flexibility. It should be less polluting, have good electrical insulation, and have good resistance to migration. In particular, in recent years, the provision of special properties (non-toxic, odorless, flame retardant, bacteria resistance, etc.) is required, the development of a plasticizer for PVC that can give such properties is an urgent situation.

In order to solve the above problems and development requirements for the plasticizer for PVC resin, through the continuous research results of the present researchers, as a plasticizer for PVC resin, PVC resin products having excellent physical properties such as sheet hardness, static heat resistance, tensile strength and elongation It is an object of the present invention to provide a plasticizer for eco-friendly PVC resin that can be prepared and does not contain endocrine-based obstructions without using phthalic acid or phthalic anhydride as a raw material of the phthalate-based plasticizer.

This invention can solve the said subject by providing the ester plasticizer composition for PVC resin which has a chemical structure represented by following General formula (1) obtained by esterifying 1, 6- hexanediol and 2 or more types of monocarboxylic acid compounds.

[Formula 1]

In Chemical Formula 1, R ₁ and R ₂ may be the same as or different from each other, and a linear, crushed, cyclic alkyl group, or phenyl group having 4 to 10 carbon atoms may be used.

Another embodiment of the present invention is a method for producing an ester plasticizer composition for a PVC resin having a chemical structure represented by the formula (1) (1) 1,6-hexanediol, two or more monocarboxylic acid compounds 1,6-hexanediol: 2 or more types of monocarboxylic acid compound = 1: 1: mixture in 1.5 to 2.5 molar ratio, (2) tetra-isopropyl titanate and (3) entrained materials were mixed and stirred at 180 to 240 ℃ Characterized in that prepared by esterification for 2 to 8 hours.

In addition, the present invention relates to a PVC resin composition comprising the ester-based plasticizer composition for PVC resin,

It is characterized by including 30 to 80 parts by weight of the ester plasticizer composition for PVC resin and 5 to 20 parts by weight of the stabilizer based on 100 parts by weight of the PVC resin.

The ester plasticizer composition for PVC resin of the present invention not only solves the environmental problem that is the problem of the conventional plasticizer for PVC resin, PVC resin produced using the present invention has excellent effects such as tensile strength, processability, elongation, etc. have.

It is used in various fields such as wire coating, hoses, films, sheets, wallpaper, artificial leather, and food packaging films by processing polyvinyl chloride resin (PVC resin, hereinafter defined as “PVC resin”). These PVC resins have been used by adding plasticizers at the time of processing to improve physical properties such as workability and formability. However, the use of phthalate-based plasticizers is very limited or prohibited as it has been found that phthalate-based plasticizers, which have been mainly used in the past, are toxic to humans. In recent years, non-phthalate plasticizers have been developed under the industrial atmosphere. However, the developed non-phthalate plasticizers have poor compatibility with PVC resins, resulting in poor physical properties of PVC resin products.

As a result of the study by the present inventors, it is possible to produce an ester plasticizer composition for PVC resin as described below, which can manufacture a PVC resin processed product having excellent physical properties while replacing the existing phthalate plasticizer. Hereinafter, the present invention will be described in detail.

The present invention relates to an ester plasticizer composition for PVC resins having a chemical structure represented by the following formula (1) obtained by reacting 1,6-hexanediol and two or more monocarboxylic acid compounds.

[Formula 1]

In Chemical Formula 1, R ₁ and R ₂ may be the same as or different from each other, and may be a straight, crushed, cyclic alkyl group or a phenyl group having 4 to 10 carbon atoms, preferably a butyl group, Pentyl group, hexyl group, heptyl group, heptyl group, octyl group, 6-methyl-2-heptyl group, 6-methyl-2-heptyl group, 4-methyl -3-heptyl group (4-methyl-3-heptyl group), 2,4,4-trimethyl pentyl group (2,4,4-trimethyl pentyl group), 2-propylpentyl group, 2 One kind selected from 2-ethylhexyl group, 3-heptyl group, phenyl group, and derivatives thereof may be used, and more preferably, phenyl group, 3-heptyl group Can be used.

When explaining the mechanism of action of general PVC plasticizer, since PVC is polarized by chlorine atoms in each unit of the molecular chain, the electric chain between them prevents polymer chain movement (micro brown movement), making deformation difficult. In this case, when the PVC is heated, the thermal movement of the molecular chain becomes severe, and the force of interaction between the molecular chains decreases, so that the intermolecular spacing is widened and plasticizer molecules enter between the molecular chains. There is an action between the polarization portion and the polar portion of the plasticizer, so that after cooling, the plasticizer remains in its position, which hinders the access of the molecular chain, which in turn facilitates the polymer chain movement, thereby becoming a flexible plastic. However, the conventional phthalate plasticizer for PVC resin has been mainly used because of excellent physical properties such as compatibility with PVC resin products, but its use has been banned since it has recently been identified as an environmental hormone releasing material.

Accordingly, the inventors of the present invention, by using a linear, crushed, cyclic alkyl group or a phenyl group having 4 to 10 carbon atoms of R ₁ and R ₂ as a non-phthalate compound, the ester plasticizer composition for PVC resin of the present invention Not only prevented the release of environmental pollutants, but also satisfied the compatibility with PVC resin and also can satisfy the physical properties required by PVC resin processed products.

Ester plasticizer for the PVC resin of the present invention is characterized in that represented by the formula (1), the ester plasticizer for the PVC resin of the present invention in the formula 1, R ₁ and R ₂ are the same or the same compound Preference is given to using mixed ones. Plasticizers manufactured using only one type of alcohol have problems such as poor compatibility with PVC resin, weakening of high hardness and mechanical strength, depending on the type and structure of alcohol used, but two or more types of alcohol are used. In addition to the physical properties exhibited by each alcohol, the prepared plasticizer can achieve a compatibility with the physical properties such as compatibility, mechanical strength, and elongation of the plasticizer with the PVC resin.

The present invention is not limited thereto. For example, in Chemical Formula 1, a compound in which R ₁ and R ₂ are phenyl groups, R ₁ is a phenyl group and R ₂ is a 4-methyl-3-heptyl group, and R ₁ and R ₂ It may be a mixed form of two or more compounds selected from compounds which are 4-methyl-3-heptyl groups. That is, according to the present invention, the number of compounds in the mixture may vary depending on what the substituents of R ₁ and R ₂ in Formula 1 are.

By using a non-phthalate-based aliphatic compound having 4 to 10 carbon atoms of R ₁ and R ₂ , which are the substituents of Formula 1, it is possible to avoid controversy about environmental hormone-inducing substances and to maximize compatibility and plasticity with the resin. In this case, when the carbon number is less than 4, the compatibility with the resin increases, but the problem of deterioration resistance and mechanical properties occurs, and when the carbon number exceeds 10, the compatibility with the resin decreases, and the hardness of the resin increases. do. In addition, since the chain length of the substituent moiety can be used as a plasticizer in the PVC resin, it is preferable to use a straight, crushed, cyclic alkyl group or phenyl group having 4 to 10 carbon atoms.

The present invention is described in more detail as follows.

The present invention

(a) benzoic acid, 6- (benzoyl oxy) hexyl ester}; And

(b) benzoic acid, 6- (2-ethyl hexanoyl oxy) hexyl ester {benzoic acid, 6- (2-ethyl hexanoyl oxy) hexyl ester}; At least one ester selected from

(c) 2-ethyl hexanoic acid, 6- (2-ethyl hexanoyl oxy) hexyl ester {2-ethyl hexanoic acid, 6- (2-ethyl hexanoyl oxy) hexyl ester}

It is characterized by including.

In the ester plasticizer, when only one type of ester is included, that is, when only the benzoic acid or ester of (a) or (b) is included, its compatibility with PVC resin is high and its hardness is high, so that it is suitable for use as a plasticizer. Without the above, in the case of containing only 2-ethyl hexanoic acid and ester of (c), the compatibility with the PVC resin is excellent, but there is a problem that the mechanical strength is poor. Therefore, the present invention has been made to manufacture a PVC resin processed article excellent in compatibility with the PVC resin, static heat resistance, tensile strength and elongation by using a plasticizer including two or more esters to solve the above problems.

The composition ratio of the plasticizer for PVC resin of the said invention is demonstrated in detail as follows.

The present invention is based on the total weight of the plasticizer composition for PVC resin

(a) 5 to 70% by weight of benzoic acid, 6- (benzoyloxy) hexyl ester

(b) 15 to 55% by weight of benzoic acid, 6- (2-ethyl hexanoyl oxy) hexyl ester

(c) 5-ethyl hexanoic acid and 6- (2-ethyl hexanoyl oxy) hexyl ester 5 to 65% by weight.

The composition (a) benzoic acid, 6- (benzoyloxy) hexyl ester of the present invention may be used 5 to 70% by weight, more preferably 20 to 50% by weight relative to the total weight of the plasticizer composition for PVC resin, where If it is less than 5% by weight, the effect of using two types of alcohol cannot be expected, and if it exceeds 70% by weight, a problem occurs because the hardness of the PVC resin is too high.

Another composition of the present invention (b) benzoic acid, 6- (2-ethyl hexanoyl oxy) hexyl ester is 15 to 55% by weight, more preferably 25 to 45% by weight relative to the total weight of the plasticizer composition for PVC resin If less than 15% by weight, the content of the plasticizer is less than 15% by weight, because the hardness of the PVC resin is high and the workability is poor, and if it exceeds 55% by weight is due to the problem that the performance resistance is lowered.

In addition, the (c) 2-ethyl hexanoic acid, 6- (2-ethyl hexanoyl oxy) hexyl ester may use 5 to 65% by weight, more preferably 20 to 45% by weight, where less than 5% by weight This is because the effect of using two types of alcohol cannot be expected on the back side, and if it exceeds 65% by weight, a problem of deterioration in compatibility with the resin occurs.

Therefore, it is preferable that this invention contains the composition within each said composition ratio.

Hereinafter, the manufacturing method of the said ester plasticizer composition for PVC resin which is this invention is demonstrated.

The ester plasticizer composition for PVC resins of the present invention can be prepared using a manufacturing method generally performed in the art, and the manufacturing method is not particularly limited, but may be prepared by the following method.

The present invention prepares the plasticizer by reacting two or more monocarboxylic acids with 1,6-hexanediol, wherein the monocarboxylic acids are pentanic acid, hexanoic acid, heptanoic acid, Nonanoic acid, 2-methyl octanoic acid, 2,6-dimethyl heptanoic acid, 3-methyl-2-ethyl hexanoic acid methyl-2-ethyl hexanoic acid), 3,5,5-trimethyl hexanoic acid, 3-propyl hexanoic acid, 3-ethyl hexanoic acid (3 -ethyl hexanoic acid) and benzoic acid (benzoic acid), 2-ethyl hexanoic acid (2-ethyl hexanoic acid) and derivatives thereof may include two or more selected, more preferably benzoic acid, 2-ethyl hexanoic acid And two or more selected from these derivatives.

When using 2 or more types of monocarboxylic acids as a raw material, this invention is not limited to this, For example, when a plasticizer is manufactured by carrying out esterification reaction of hexanoic acid, a pentanic acid, and 1, 6- hexanediol simultaneously. Examples include (a) hexanoic acid, 6- (pentanoyl oxy) hexyl ester, (b) hexanoic acid, 6- (butanoyl oxy) hexyl ester and (c) pentanoic acid, 6- (butanoyl oxy) hexyl ester A mixture of is obtained. However, when mixing the product which esterified 1, 6- hexanediol and hexanoic acid, and the product which esterified 1, 6- hexanediol and pentanoic acid, (a) hexanoic acid and 6- (pentanoyl oxy Only 2 hexyl esters, (b) pentanic acid and 6- (butanoyl oxy) hexyl esters are obtained.

In addition, when two or more monocarboxylic acids are used as raw materials for the preparation of plasticizers, plasticizers can be obtained without ancillary processes, but the product of 1,6-hexanediol and benzoic acid reacted with 1,6-hexanediol and 2-ethylhexanoic acid. In the case of mixing the product reacted with the above product, at least two monocarboxylic acids and 1,6-hexane may be used in the preparation of the plasticizer since the investment and time required for the mixing of the plasticizer and the additional investment and time are required. Preference is given to simultaneously esterifying the diols.

Referring to the production method of the ester plasticizer composition for PVC resins of the present invention represented by the formula (1) more specifically,

(1) a mixture of 1,6-hexanediol and two or more monocarboxylic acid compounds in a 1: 1.5 to 2.5 molar ratio, (2) tetra-isopropyl titanate, and (3) entraining materials Mixing and stirring the esterification reaction at 180 to 240 ° C. for 2 to 8 hours;

After the esterification reaction, removing the unreacted acid under reduced pressure and adding a neutralizing agent to neutralize the excess acid; And

After washing, dehydrating, and decolorizing, filtering with an adsorbent; is characterized by including a.

Here, in the esterification reaction, since the stoichiometric ratio of 1,6-hexanediol: two or more monocarboxylic acid compounds = 1: 1.5 to 2.5 molar ratio, the ratio of monocarboxylic acid compound and 1,6-hexanediol is used according to the stoichiometry. It is good for the esterification reaction to prepare and keep the acid value of the plasticizer low.

In addition, during the esterification reaction, it is preferable to add the catalyst and the entraining material, and stir and mix using a flask equipped with a stirrer, a thermometer, and a generator for removing water, and during the esterification reaction, from 2 to 8 at 180 to 240 ° C. The reaction is carried out for a time, but the present invention is not particularly limited, and is the most efficient reaction condition in the catalyst range.

Here, the tetra isopropyl titanate is added as a catalyst, it is preferable to add 0.5 to 2 parts by weight based on 100 parts by weight of 1,6-hexanediol, where the ester is less than 0.5 parts by weight There is a problem that the reaction rate is insufficient, and it is uneconomical because there is no increase in the reaction rate due to the increase in the amount of the catalyst when more than 2 parts by weight.

The entrainer may be one or more selected from inert gases such as toluene, xylene, nitrogen, argon, and the like, and 40 to 60 parts by weight based on 100 parts by weight of 1,6-hexanediol. It is desirable to. Here, the entrainer is not easy to remove the water present in the reactants when less than 40 parts by weight and there is no significant effect on the effect of the content above 60 parts by weight.

In the manufacturing method of the ester plasticizer composition for PVC resins of this invention,

After the esterification reaction, removing the unreacted acid under reduced pressure and adding a neutralizing agent to neutralize the excess acid; And

After washing, dehydrating, and decolorizing, filtering with an adsorbent may be further included.

Here, the neutralizing agent is preferably used at least one selected from sodium carbonate (Na ₂ CO ₃ ), calcium carbonate (CaCO ₃ ), calcium sulfate (CaSO ₄ ) and sodium bicarbonate (NaHCO ₃ ), the neutralizing agent is 1, It is preferable to add 0.5-2 weight part with respect to 100 weight part of 6-hexanediol. Here, when it exceeds 2 parts by weight, it is preferable to add it within the above range because there is no significant effect on the effect and rather a problem of contaminating the plasticizer occurs.

The adsorbent is not particularly limited, but it is preferable to use at least one selected from diatomaceous earth, activated carbon and zeolite which are widely used as the most economical raw materials.

Hereinafter, a PVC resin composition which is another embodiment of the present invention will be described.

Using the ester plasticizer composition for PVC resins of the present invention described above, a PVC resin composition can be prepared as follows. Another aspect of the present invention is a PVC resin composition.

It is characterized by including 30 to 80 parts by weight of the ester plasticizer composition for PVC resin and 5 to 20 parts by weight of the stabilizer based on 100 parts by weight of the PVC resin.

Herein, the stabilizer may be used at least one selected from calcium-zinc (Ca-Zn) and barium-zinc (Ba-Zn), which are metal stabilizers, or stearic acid salts, basic stearates, calcium stearate, and stearic acid. Using at least one selected from barium, cadmium stearate, zinc stearate, lauric acid, benzoic acid and Ba-Zn-based organic complex stabilizer, or at least one selected from benzophenol, triazole, and acrylonitrile, which are nonmetallic stabilizers It is preferable to use.

In addition, the PVC resin composition may further include a pigment, a lubricant, an impact modifier, and the like as an additive in addition to the composition according to its use.

Herein, when the ester-based plasticizer composition for PVC resin is less than 30 parts by weight, problems such as lowering of plasticity in processability and physical properties of PVC resin, increase in hardness of resin, and decrease in processability due to rise in melting temperature, and when exceeding 80 parts by weight The plasticizer flows out of the resin, and when the stabilizer is less than 5 parts by weight, a problem of decomposition of the resin occurs due to an increase in the frictional heat during processing of the PVC resin, and a problem of deterioration of the physical properties when it exceeds 20 parts by weight. For this reason, it is preferable that the PVC resin composition of this invention contains the said compositions within the range shown above.

Hereinafter, the present invention will be described in more detail based on Examples and Comparative Examples, but the present invention is not limited to the following Examples.

Preparation of plasticizer composition for PVC resin

Example 1

354.5 g (100 parts by weight, 3.0 mole) of 1,6-hexanediol, 432.6 g (3.0 mole) of 2-ethylhexanoic acid, 366.4 g (3.0 mole) of benzoic acid, and 2.7 g (0.7 parts by weight) of tetraisopropyl titanate as a catalyst ), 180 g (50 parts by weight) of the entrained material of the xylene using a flask equipped with a stirrer, a thermometer, and a water removing device for 4 hours at 220 ° C., and the unreacted acid and xylene were decompressed. Removed under Then, neutralized with 4 g (1.1 parts by weight) of sodium carbonate (Na ₂ CO ₃ ), and then washed with water, dehydrated, and decolorized, and then filtered using diatomaceous earth as an adsorbent to form an ester plasticizer composition for PVC resin. Got it.

The composition of the prepared ester-based plasticizer composition for PVC resin was GC (gas chromatography) analysis, and (a) benzoic acid, 6- (benzoyloxy) hexyl ester 26.7 wt% (b) benzoic acid, 6- (2-ethyl hexanoyl oxy 50.2% by weight of hexyl ester and 23.1% by weight of (c) 2-ethyl hexanoic acid and 6- (2-ethyl hexanoyl oxy) hexyl ester, and the results are shown in FIG. ), (c) chemical structures are shown in the following formula (2) -4.

Examples 2 to 5 and Comparative Examples 1 to 4

An ester plasticizer composition for PVC resin was prepared in the same manner as in Example 1, except that the ester plasticizer composition for PVC resin was prepared to have the same composition as in Table 1, and Examples 2 to 5 and Comparative Examples 1 to 4 were performed. .

Results of gas chromatography (GC) analysis of the ester plasticizer composition for PVC resin of Example 2 are shown in Figure 2, (a) benzoic acid, 65.1 wt% of 6- (benzoyloxy) hexyl ester, (b) benzoic acid, 6- 24.5 weight% of (2-ethyl hexanoyl oxy) hexyl ester, (c) 2-ethyl hexanoic acid, and 10.4 weight% of 6- (2-ethyl hexanoyl oxy) hexyl ester.

GC analysis results of the ester plasticizer composition for PVC resin of Example 3 are shown in Figure 3, (a) benzoic acid, 6- (benzoyl oxy) hexyl ester 12.0 wt%, (b) benzoic acid, 6- (2-ethyl 26.3 wt% hexanoyl oxy) hexyl ester, (c) 2-ethyl hexanoic acid, 61.7 wt% 6- (2-ethyl hexanoyl oxy) hexyl ester.

(Unit: g) division Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 1,6-hexanediol 354.5 (3mole) Monocarboxylic acid Benzoic acid 366.4 (3mole) 549.5 (4.4mole) 183.2 (1.5mole) 549.5 (4.4mole) - 61 (0.5mole) 671 (5.5mole) - 732.7 (6mole) 2-ethyl hexanoic acid 432.6 (3mole) 216.3 (1.5mole) 648.9 (4.5mole) 850 (5.3mole) - 792 (5.5mole) 72 (0.5mole) 950 (6.6mole) - Heptanoic acid - - - - 365 (2.8mole) - - - - 2-propyl pentanic acid - - - - 461 (3.2mole) - - - - catalyst Tetra isopropyl titanate  2.7 Entrainment Material Xylene  180 corrector Sodium carbonate 4 The composition used the following product. (1) 1,6-hexanediol: Junsei, primary (2) Benzoic acid: Showa, primary (3) 2-ethyl hexanoic acid: Aldrich, 99% (4) Heptanoic acid: Aldrich (5) 2-propyl pen Carbonic acid: Aldrich (6) Tetra isopropyl titanate: DuPont, Pyzor-TPT (7) Xylene: Junsei, Express (8) Sodium carbonate: Dongyang Steel Chemical

Production Example

Preparation of PVC Resin Composition Sheet

Preparation Example 1

In order to measure physical properties as a plasticizer using the ester-based plasticizer composition for PVC resin prepared in Example 1, a PVC resin composition sheet was prepared by the following method with reference to ASTM D638.

50 parts by weight of ester plasticizer for PVC resin and calcium-zinc stabilizer (manufacturer: Korea Daehyup, trade name: LTX-630) in 100 parts by weight of PVC resin (manufacturer: LG Chemical, trade name: LS-100) After mixing 6 parts by weight using a Haake mixer at a temperature of 160 ° C. to 175 ° C. and 70 rpm, a master batch was obtained using a single extruder, which was then hot pressed at 190 ° C. A 3 mm thick PVC resin composition sheet was prepared by preheating for 3 minutes and heating for 3 minutes using a hot press.

Preparation Examples 2 to 5 and Comparative Production Examples 1 to 5

In the same manner as in Preparation Example 1 to prepare a PVC resin composition sheet using the ester plasticizer for the PVC resin of Examples 2 to 4 and Comparative Examples 1 to 4 Preparation Examples 2 to 5 and Comparative Preparation Examples 1 to 4 Was carried out.

And in the case of Comparative Production Example 5 PVC resin composition sheet was prepared using DEHP (diethylhexyl phthalate, manufacturer: Dongyang Steel Chemical) which is an existing plasticizer in place of the ester plasticizer for PVC resin.

Experimental Example

Physical property measurement experiment of PVC resin composition sheet

The physical properties of the PVC resin composition sheets prepared in Preparation Examples 1 to 4 and Comparative Preparation Examples 1 to 5 were measured by the following methods, and the results are shown in Table 2 below.

(1) hardness measurement

After the Shore A hardness and the saliva were completely lowered, the average value of the hardness values that appeared after 5 seconds for the five places of the PVC resin composition sheet was determined.

(2) sheet heating loss

After maintaining the PVC resin composition sheet (width 5cm × 5cm) for 3 hours in an 130 ℃ oven, stored in a constant temperature and humidity room for 4 hours or more, by measuring the weight change of the PVC resin composition sheet according to the following equation (1) The lower the sheet heating loss value, the better the physical properties.

Loss on heating (%) = {(initial weight-weight after heating) / initial weight} × 100

(3) performance resistance

After putting a sheet of PVC resin composition (3cm × 3cm) in a polystyrene (PS) plate in an 80 ℃ oven, leaving it for 48 hours under a 5kg load, and storing it in a constant temperature and humidity room for 4 hours or more The change was calculated by measuring according to the following equation (2). Here, the lower the resistance value, the better the resistance.

Permeability (%) = {(Initial Weight-Weight after Heating) / Initial Weight} × 100

(4) static heat resistance

Put a sheet for PVC resin (2 cm x 2 cm) into an oven at 195 ° C, take it out after 5 minutes, and measure the discoloration degree (ΔE, color difference) of L, a, and b values using a color meter. It calculated | required by Formula (3). In Equation 3, L _o is the initial brightness, L is the brightness after heat treatment, a _o is the initial redness, a is the redness after heat treatment, b _o is the initial yellowness, b shows yellowness after heat treatment.

Here, as the static heat resistance value is lower, there is no difference from the initial color, and the static heat resistance is excellent.

Static heat resistance (ΔE) = [(L _o -L) ² + (a _o -a) ² + (b _o -b) ² ] ^1/2

(5) tensile strength and elongation

After cutting the specimen into type C type according to ASTM D 638 method, using a universal testing machine (UTM), pull the crosshead speed at a speed of 500 mm / min and measure the strength and elongation at the point where the specimen is cut. It was calculated by the following equations (4) and (5). Here, the higher the measured value of tensile strength and elongation, the better the mechanical properties.

Tensile strength = load value at break (kg _f ) / {thickness (cm) × width (cm)}

Elongation = {length at break / initial length} × 100

(6) 100% modulus measurement

Tensile strength was measured according to ASTM D 638 method and the tensile strength value at 100% elongation was defined as 100% modulus. The higher the 100% modulus value, the higher the hardness of the resin.

division Hardness (Shore A) Sheet heating loss (%) Tolerance (%) Static heat resistance (ΔE) Tensile Strength (kg _f / ㎠) Elongation (%) 100% modulus (kg _f / ㎠) Preparation Example 1 88 1.02 2.63 2.64 180.2 342 95.7 Production Example 2 87 1.05 2.28 2.63 181.3 343 94.8 Production Example 3 88 0.98 2.42 2.48 174.6 325 94.2 Preparation Example 4 88 1.76 2.71 2.74 178.5 340 94.1 Preparation Example 5 89 2.77 3.15 2.26 183.4 344 94.8 Comparative Production Example 1 89 3.46 3.48 2.89 177.4 256 98.6 Comparative Production Example 2 89 3.53 4.78 3.76 160.5 276 101.4 Comparative Production Example 3 91 3.79 4.81 2.98 179.3 267 97.6 Comparative Production Example 4 89 2.87 5.02 3.86 162.8 283 100.7 Comparative Production Example 5 90 3.28 4.92 3.32 170.4 271 105.9

As described in Table 2, in Preparation Examples 1 to 5 prepared by adding the ester plasticizer for PVC resin of the present invention to the PVC resin, sheet heating loss, migration resistance, static heat resistance, Tensile strength and elongation were excellent, and in particular, the sheet heating loss, migration resistance, elongation and the like are excellent.

It can be seen that the physical properties of the ester plasticizer of the present invention is superior to Comparative Preparation Example 3 and Comparative Preparation Example 4 using one type of monocarboxylic acid, and have better physical properties than DEHP of Comparative Preparation Example 5, which is most commonly used. Indicated.

In addition, when the amount of monocarboxylic acid added was higher than the equivalent as in Comparative Example 3 to prepare a plasticizer, as shown in Comparative Preparation Example 3, there was a problem that the heating loss and the migration resistance of the sheet were inferior.

Two or more types of monocarboxylic acids were used as in Comparative Example 1 and Comparative Example 2, but when the contents of (1a) and (1c) of Formula 2 were outside the scope of the present invention, the intended effect of the present invention was achieved. I couldn't see it.

The results of this embodiment can be seen that the physical properties of the equivalent or more compared to the conventional plasticizers without containing endocrine barriers such as phthalate-based plasticizers.

PVC resin composition molded article prepared by using the ester plasticizer for PVC resin of the present invention was confirmed that the physical properties are excellent, can not only replace the existing non-friendly environmental phthalate plasticizer, but also the existing non-phthalate plasticizer It can be seen that the problem can be solved.

1 is a gas chromatography measurement result of the ester plasticizer composition for PVC resin prepared in Example 1.

2 is a gas chromatography measurement result of the ester plasticizer composition for PVC resin prepared in Example 2.

3 is a gas chromatography measurement result of the ester plasticizer composition for PVC resin prepared in Example 3.

Claims (10)

delete delete delete Total weight of ester plasticizer composition for polyvinyl chloride (PVC) resin (a) 5 to 70% by weight of benzoic acid, 6- (benzoyloxy) hexyl ester (b) 15 to 55% by weight of benzoic acid, 6- (2-ethylhexanoyloxy) hexyl ester (c) 2-ethyl hexanoic acid and 5-65 weight% of 6- (2-ethylhexanoyloxy) hexyl esters. The ester plasticizer composition for PVC resins characterized by the above-mentioned. (1) a mixture of 1,6-hexanediol and two or more monocarboxylic acid compounds in a 1: 1.5 to 2.5 molar ratio, (2) tetra-isopropyl titanate, and (3) entraining materials Mixing and stirring the esterification reaction at 180 to 240 ° C. for 2 to 8 hours; After the esterification reaction, removing the unreacted acid under reduced pressure and adding a neutralizing agent to neutralize the excess acid; And After washing with water, dehydrating and decolorizing, filtering with an adsorbent. The method of preparing an ester plasticizer composition for a PVC resin having a chemical structure represented by the following Chemical Formula 1, comprising: a. [Formula 1]

In Formula 1, R ₁ and R ₂ are the same as or different from each other, and are a straight, pulverized, cyclic alkyl group, or phenyl group having 4 to 10 carbon atoms. The method of claim 5, wherein the monocarboxylic acid compound is pentanic acid (pentanoic acid), hexanoic acid (hexanoic acid), heptanoic acid (heptanoic acid), nonanoic acid (nonanoic acid), 2-methyl octanoic acid (2-methyl octanoic acid) ), 2,6-dimethyl heptanoic acid, 3-methyl-2-ethyl hexanoic acid, 3,5,5-trimethyl hexanoic acid (3,5,5-trimethyl hexanoic acid), 3-propyl hexanoic acid, 3-ethyl hexanoic acid and benzoic acid and 2-ethyl hexanoic acid ( 2-ethyl hexanoic acid) method for producing an ester plasticizer composition for PVC resin, characterized in that two or more selected from. The method of claim 5, wherein the entraining material is at least one selected from toluene, xylene, and an inert gas. A PVC resin composition comprising the ester plasticizer composition for PVC resin of claim 4. The PVC resin composition according to claim 8, comprising 30 to 80 parts by weight of the ester plasticizer composition for PVC resin and 5 to 20 parts by weight of the stabilizer based on 100 parts by weight of the PVC resin. The PVC resin composition according to claim 9, wherein the stabilizer is at least one metal stabilizer selected from calcium-zinc (Ca-Zn) and barium-zinc (Ba-Zn).

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