JP2008526959A - Hydroxypivalyl hydroxypivalate ester plasticizer composition and method for producing the same - Google Patents

Abstract

  The present invention relates to a plasticizer composition comprising different hydroxypivalyl hydroxypivalate ester and neopentyl glycol ester and a method for producing the same, and the plasticizer composition according to the present invention has reduced weight loss, migration resistance, and plasticization. It is excellent in efficiency, and the polyvinyl chloride resin containing it is excellent in physical properties such as tensile strength and elongation.

Description

  TECHNICAL FIELD The present invention relates to a hydroxypivalyl hydroxypivalate ester plasticizer composition, and more particularly, to a hydroxypivalyl hydroxypivalate ester plasticizer composition that can be used as a plasticizer for polyvinyl chloride resin (PVC). .

  Polyvinyl chloride resin is a homopolymer of vinyl chloride or a copolymer containing 50% or more of vinyl chloride, and is a general-purpose resin that can be used by processing methods such as extrusion molding, injection molding, and calendering. Through various processes, it is widely used as a material for various products ranging from pipes, electric wires, electromechanical products, toys, films, sheets, artificial leather, taporins, tapes, food packaging materials, and medical supplies. Various processing physical properties can be imparted to such a polyvinyl chloride resin by appropriately adding various additives such as plasticizers, stabilizers, fillers and pigments.

  Among the additives, the plasticizer is an essential additive that is added to the polyvinyl chloride resin and imparts various physical properties and functions such as processability, flexibility, electrical insulation, and adhesiveness. Representative types of such plasticizers include phthalate-based, adipic acid-based (adipates), trimellitic acid-based (trimellates), and the like. Of these, phthalate plasticizers such as diethylhexyl phthalate (DEHP), dibutyl phthalate (DBP), diisodecyl phthalate (DIDP), butyl benzyl phthalate (BBP), diisononyl phthalate (DINP) and adipic acid plasticizer Certain di-2-ethylhexyl adipates (DEHA) are most widely used.

  However, the U.S. Environmental Protection Agency and the Japan National Institute of Pharmaceutical Food Hygiene have classified phthalate and adipic acid compounds as environmental hormone substances. Therefore, development of a plasticizer that does not contain a phthalate-based or adipic acid-based structure is required.

  As an example of a plasticizer not containing a phthalate-based or adipic acid-based structure, 2-ethylhexanoic acid [2- {2- (2-ethylhexanoyloxy) synthesized by reacting triethylene glycol with 2-ethylhexanoic acid is used. ) -Ethoxy} ethoxy] -ethyl ester is excellent in workability during the production of the polymer resin, but is inferior in physical properties such as elongation, tackiness and transparency of the obtained polymer resin.

  In addition, there is a report (Romanian Patent No. 62655) that a single component ester synthesized by reacting neopentyl glycol with aliphatic butyric acid, 2-ethylhexanoic acid or the like can be used as a plasticizer. Compared with phthalate plasticizers, the compatibility with polyvinyl chloride resin is low, and the polyvinyl chloride resin produced by using this has a problem that transparency, elongation and migration resistance are not good.

  Therefore, the technical problem to be solved by the present invention is that it does not have a phthalate-based or adipic acid-based structure known as an endocrine disrupting substance, has excellent compatibility with a polymer resin, and has tensile strength, elongation rate, hardness and resistance. It is providing the plasticizer composition which can provide the polymer resin excellent in transferability, and its manufacturing method.

In order to achieve the above object, in the first aspect of the present invention, (a) a neopentyl glycol ester compound containing at least one of the compounds represented by the following chemical formulas 1 to 3, and (b) the following chemical formula 4 Or a hydroxypivalyl hydroxypivalate ester compound containing one or more of the compounds represented by Chemical Formula 7, and (c) hydroxypivalyl hydroxy containing one or more of the compounds represented by Chemical Formulas 8 to 10 below. A pivalate ester compound;
A hydroxypivalyl hydroxypivalate ester plasticizer composition is provided.
[Chemical 1]
R ₁ OCO—C (CH ₃ ) ₂ —OCOR ₁
[Chemical 2]
_{R 2 OCO-C (CH 3} ) 2 -OCOR 3
[Chemical formula 3]
_{R 4 OCO-C (CH 3} ) 2 -OCOR 4
[Chemical formula 4]
R ₁ OCO—CH ₂ C (CH ₃ ) ₂ —COO—CH ₂ C (CH ₃ ) ₂ —CH ₂ —OCOR ₁
[Chemical formula 5]
_{R 3 OCO-CH 2 C (} CH 3) 2 -COO-CH 2 C (CH 3) 2 -CH 2 -OCOR 2
[Chemical 6]
_{R 2 OCO-CH 2 C (} CH 3) 2 -COO-CH 2 C (CH 3) 2 -CH 2 -OCOR 3
[Chemical 7]
_{R 4 OCO-CH 2 C (} CH 3) 2 -COO-CH 2 C (CH 3) 2 -CH 2 -OCOR 4
[Chemical 8]
_{R 1 OCO-CH 2 C (} CH 3) 2 -COO-CH 2 C (CH 3) 2 -COO-CH 2 C (CH 3) 2 C (CH 3) 2 -CH 2 -OCOR 1
[Chemical 9]
_{R 2 OCO-CH 2 C (} CH 3) 2 -COO-CH 2 C (CH 3) 2 -COO-CH 2 C (CH 3) 2 C (CH 3) 2 -CH 2 -OCOR 3
[Chemical Formula 10]
_{R 4 OCO-CH 2 C (} CH 3) 2 -COO-CH 2 C (CH 3) 2 -COO-CH 2 C (CH 3) 2 C (CH 3) 2 -CH 2 -OCOR 4
In the chemical formula, R ₁ and R ₂ are each independently an alkyl group having 3 to 12 carbon atoms, and R ₃ and R ₄ are aryl groups having 6 to 10 carbon atoms.

  According to an embodiment of the present invention, the hydroxypivalyl hydroxypivalate ester plasticizer composition includes neopentyl glycol ester compounds 1 to 50 including one or more of the compounds represented by Formula 1 to Formula 3. 40% to 90% by weight of a hydroxypivalyl hydroxypivalate ester compound containing at least one of the compounds represented by Chemical Formula 4 to Chemical Formula 7 and a compound represented by Chemical Formula 8 to Chemical Formula 10 1 to 40% by weight of a hydroxypivalyl hydroxypivalate ester compound comprising one or more.

  According to another embodiment of the present invention, 2-ethyl-hexanoic acid 3- (2-ethyl-hexanoyloxy) -2,2-dimethyl-propyl ester, benzoic acid 3- (2-ethyl-hexanoyloxy) ) -2,2-dimethyl-propyl ester, benzoic acid 3-benzoyloxy-2,2-dimethyl-propyl ester, 2-ethyl-hexanoic acid 2- [3- (2-ethyl-hexanoyloxy) -2, 2-Dimethyl-propoxycarbonyl] -2-methyl-propyl ester, benzoic acid 2- [3- (2-ethyl-hexanoyloxy) -2,2-dimethyl-propoxycarbonyl] -2-methyl-propyl ester, benzoic acid Acid 3- [3- (2-ethyl-hexanoyloxy) -2,2-dimethyl-propionyloxy] -2,2-dimethyl-propyl ester Benzoic acid 3- [3- (benzoyloxy) -2,2-dimethyl-propionyloxy] -2,2-dimethyl-propyl ester, 2-ethyl-hexanoic acid 2- {2- [3- (2- Ethyl-hexanoyloxy) -2,2-dimethyl-propoxycarbonyl] -2-methyl-propoxycarbonyl} -2-methyl-propyl ester, benzoic acid 3- {3- [3- (2-ethyl-hexanoyloxy) ) -2,2-dimethyl-propionyloxy] -2,2-dimethyl-propionyloxy} -2,2-dimethyl-propyl ester and benzoic acid 3- {3- [3- (benzoyloxy) -2,2- Dimethyl-propionyloxy] -2,2-dimethyl-propionyloxy} -2,2-dimethyl-propyl ester.

  In the second embodiment of the present invention, 20 to 50% by weight of hydroxypivalylhydroxypivalate or a mixture of hydroxypivalylhydroxypivalate and neopentylglycol, a fatty acid having 3 to 12 carbon atoms, or 6 carbon atoms Or a hydroxypivalyl hydroxypivalate ester plasticizer composition comprising a step of reacting 50 to 80% by weight of an aromatic acid having 3 to 10 carbon atoms or a fatty acid having 3 to 12 carbon atoms with an aromatic acid having 6 to 10 carbon atoms A manufacturing method is provided.

  According to an embodiment of the present invention, the fatty acid may be 2-ethylhexanoic acid and the aromatic acid may be benzoic acid.

  According to another embodiment of the present invention, the hydroxypivalyl hydroxypivalate ester plasticizer composition may be prepared by reacting at a temperature of 100 to 300 ° C. for 4 to 14 hours.

  From 1 to 20 parts by weight of xylene and from 0.0001 to 1 part by weight of tetraisopropyl titanate based on 100 parts by weight of the reactants may be further added to the reaction.

  In a third aspect of the present invention, there is provided a polyvinyl chloride resin comprising the hydroxypivalyl hydroxypivalate ester plasticizer composition.

  In a fourth aspect of the present invention, there is provided the hydroxypivalyl hydroxypivalate ester compound represented by Chemical Formula 5, Chemical Formula 6, Chemical Formula 8, Chemical Formula 9, and Chemical Formula 10.

  The hydroxypivalyl hydroxypivalate ester plasticizer composition according to the present invention can be used as a plasticizer in the production of polyvinyl chloride resin, and in particular, polyvinyl chloride excellent in tensile strength, elongation, hardness, and migration resistance. Resin can be provided.

  By producing a polyvinyl chloride resin using the hydroxypivalyl hydroxypivalate ester plasticizer composition according to the present invention, a product excellent in terms of heat loss, migration resistance, and plasticization efficiency can be obtained. In addition, physical properties such as elongation and tensile strength are improved.

Hereinafter, the present invention will be described in detail.
The present invention is a plasticizer composition that does not have a phthalate or adipic acid structure known as an endocrine disrupting substance and can be applied to a polyvinyl chloride resin having excellent physical properties such as tensile strength, elongation, hardness, and migration resistance. (A) a neopentyl glycol ester compound containing one or more of the compounds represented by the following chemical formulas 1 to 3, and (b) one or more of the compounds represented by the following chemical formulas 4 to 7: A hydroxypivalyl hydroxypivalate ester compound containing (c) a hydroxypivalyl hydroxypivalate ester compound containing one or more of the compounds represented by the following chemical formulas 8 to 10 An ester plasticizer composition is provided.
[Chemical 1]
R ₁ OCO—C (CH ₃ ) ₂ —OCOR ₁
[Chemical 2]
_{R 2 OCO-C (CH 3} ) 2 -OCOR 3
[Chemical formula 3]
_{R 4 OCO-C (CH 3} ) 2 -OCOR 4
[Chemical formula 4]
R ₁ OCO—CH ₂ C (CH ₃ ) ₂ —COO—CH ₂ C (CH ₃ ) ₂ —CH ₂ —OCOR ₁
[Chemical formula 5]
_{R 3 OCO-CH 2 C (} CH 3) 2 -COO-CH 2 C (CH 3) 2 -CH 2 -OCOR 2
[Chemical 6]
_{R 2 OCO-CH 2 C (} CH 3) 2 -COO-CH 2 C (CH 3) 2 -CH 2 -OCOR 3
[Chemical 7]
_{R 4 OCO-CH 2 C (} CH 3) 2 -COO-CH 2 C (CH 3) 2 -CH 2 -OCOR 4
[Chemical 8]
_{R 1 OCO-CH 2 C (} CH 3) 2 -COO-CH 2 C (CH 3) 2 -COO-CH 2 C (CH 3) 2 C (CH 3) 2 -CH 2 -OCOR 1
[Chemical 9]
_{R 2 OCO-CH 2 C (} CH 3) 2 -COO-CH 2 C (CH 3) 2 -COO-CH 2 C (CH 3) 2 C (CH 3) 2 -CH 2 -OCOR 3
[Chemical Formula 10]
_{R 4 OCO-CH 2 C (} CH 3) 2 -COO-CH 2 C (CH 3) 2 -COO-CH 2 C (CH 3) 2 C (CH 3) 2 -CH 2 -OCOR 4
In the chemical formula, R ₁ and R ₂ are each independently an alkyl group having 3 to 12 carbon atoms, and R ₃ and R ₄ are each independently an aryl group having 6 to 10 carbon atoms.

  The neopentyl glycol ester compound including one or more compounds represented by Formulas 1 to 3 may be included in an amount of 1 to 50% by weight, and more preferably 10 to 40% by weight. . If the neopentyl glycol ester compound is less than 1% by weight, when used as a plasticizer for polyvinyl chloride resin, the tensile strength is low, the hardness is high, the physical properties of the product and the plasticizing efficiency are low, and 60% by weight. If it is more, the adhesiveness becomes higher when it is produced with a wrap film.

  The hydroxypivalyl hydroxypivalate ester compound including at least one of the compounds represented by Formulas 4 to 7 is preferably included in an amount of 40 to 90% by weight, more preferably 50 to 80% by weight. Can be. If the amount of the hydroxypivalyl hydroxypivalate ester compound is less than 40% by weight, the compatibility with polyvinyl chloride, which is the basic physical property of the plasticizer, falls, and the basic physical property cannot be satisfied. The physical properties such as tensile strength and elongation of the resin are deteriorated.

  The hydroxypivalyl hydroxypivalate ester compound including at least one of the compounds represented by Formula 8 to Formula 10 is preferably included in an amount of 1 to 40% by weight, more preferably 5 to 20% by weight. It is. If the hydroxypivalyl hydroxypivalate ester compound is less than 1% by weight, the adhesiveness of the wrap film is increased, and a phenomenon that the film is squeezed into the roll occurs during the processing process. The tensile strength is low, the hardness is high, and the physical properties and plasticizing efficiency of the product are low.

In the chemical formula, R ₁ and R ₂ may each independently be an alkyl group having 6 to 10 carbon atoms, more preferably 1-ethylpentyl. In the chemical formula, R ₃ and R ₄ are each independently an aryl group having 6 to 8 carbon atoms, more preferably a phenyl group.

  The hydroxypivalyl hydroxypivalate ester plasticizer composition according to the present invention comprises 2-ethyl-hexanoic acid 3- (2-ethyl-hexanoyloxy) -2,2-dimethyl-propyl ester (compound (1)), benzoic acid. Acid 3- (2-ethyl-hexanoyloxy) -2,2-dimethyl-propyl ester (compound (2)), benzoic acid 3-benzoyloxy-2,2-dimethyl-propyl ester (compound (3)), 2-ethyl-hexanoic acid 2- [3- (2-ethyl-hexanoyloxy) -2,2-dimethyl-propoxycarbonyl] -2-methyl-propyl ester (compound (4)), benzoic acid 2- [3 -(2-Ethylhexanoyloxy) -2,2-dimethyl-propoxycarbonyl] -2-methyl-propyl ester (compound (5)) Benzoic acid 3- [3- (2-ethyl-hexanoyloxy) -2,2-dimethyl-propionyloxy] -2,2-dimethyl-propyl ester (compound (6)), benzoic acid 3- [3- ( Benzoyloxy) -2,2-dimethyl-propionyloxy] -2,2-dimethyl-propyl ester (compound (7)), 2-ethyl-2-hexanoic acid 2- {2- [3- (2-ethyl-hexanoyl) Oxy) -2,2-dimethyl-propoxycarbonyl] -2-methyl-propoxycarbonyl} -2-methyl-propyl ester (compound (8)), benzoic acid 3- {3- [3- (2-ethyl-hexa) Noyloxy) -2,2-dimethyl-propionyloxy] -2,2-dimethyl-propionyloxy} -2,2-dimethyl-propyl ester (compound (9) And benzoic acid 3- {3- [3- (benzoyloxy) -2,2-dimethyl-propionyloxy] -2,2-dimethyl-propionyloxy} -2,2-dimethyl-propyl ester (compound (10)) Can be included.

  The hydroxypivalyl hydroxypivalate ester plasticizer composition according to the present invention comprises 20 to 50% by weight of hydroxypivalyl hydroxypivalate or a mixture of hydroxypivalyl hydroxypivalate and neopentyl glycol, and 3 to 12 carbon atoms. It can be produced by a method comprising a step of reacting a fatty acid, an aromatic acid having 6 to 10 carbon atoms, or a fatty acid having 3 to 12 carbon atoms with 50 to 80% by weight of an aromatic acid having 6 to 10 carbon atoms.

  The mixture of hydroxypivalyl hydroxypivalate and neopentyl glycol may be a mixture of 9.5: 0.5 to 5: 5 by weight. The fatty acid in the reactant is preferably 6 to 10 carbon atoms, and most preferably 2-ethylhexanoic acid. The aromatic acid in the reactant is preferably 6 to 8 carbon atoms, and most preferably benzoic acid.

  When the reactants are reacted at the composition ratio described above, the hydroxypivalyl hydroxypivalate ester plasticizer composition of the embodiment of the present invention can be obtained.

  That is, by reacting hydroxypivalylhydroxypivalate with a fatty acid, a hydroxypivalylhydroxypivalate ester composition containing the three compounds represented by Chemical Formula 1, Chemical Formula 4 and Chemical Formula 8 is obtained. By reacting valylhydroxypivalate with an aromatic acid, a hydroxypivalylhydroxypivalate ester composition containing three types of compounds represented by Formula 3, Formula 7 and Formula 10 is obtained. When barate is reacted with a fatty acid and an aromatic acid, a hydroxypivalyl hydroxypivalate ester composition containing a compound represented by Chemical Formula 1 to Chemical Formula 10 is obtained. In order to obtain a composition of another combination, after obtaining the compounds of Formula 1 to Formula 10, the desired compound can be separated by a method well known in the art, and the separation method is not particularly limited. .

As an example of the separation method, there is a method using column chromatography. As an adsorbent used as a stationary phase, alumina (Al ₂ O ₃ ), silica (SiO ₂ ), charcoal, or magnesium silicate (MgSiO ₂ ) can be used. However, the present invention is not limited to this. As the mobile phase, materials well known in the art such as n-hexane, ethyl acetate, chloroform, or organic solvents such as toluene can be used. In particular, n-hexane or ethyl acetate is desirable, but is not limited thereto. It is not something. In general, the solvent varies depending on the mixture to be separated and the polarity of the stationary phase, but usually the solvent having a high polarity and the solvent having a low polarity are adjusted at an appropriate ratio so as to have an appropriate polarity. To use.

In the compound of the above chemical formula, R ₁ and R ₂ may be a 1-ethylpentyl group, and R ₃ and R ₄ may be a phenyl group, but are not limited thereto.

  The reason why various types of ester compounds are obtained as described above is that by-products of Chemical Formulas 1 to 3 and Chemical Formulas 8 to 10 are obtained by transesterification reaction during the esterification reaction. Transesterification occurs in the process where the ester bond contained in hydroxypivalyl hydroxypivalate is reconstructed by fatty acids and aromatic acids.

  When fatty acids and aromatic acids are used together in the reaction, the weight ratio of the two compounds can be 1:99 to 99: 1.

  The reaction may be performed in a batch reactor, a mixed flow reactor, or a tubular reactor, but is not limited thereto.

  The esterification reaction may be performed at a temperature of 100 to 300 ° C. for 4 to 14 hours. If the reaction temperature is lower than 100 ° C., the reaction rate is too slow and inefficient, and if the reaction temperature is higher than 300 ° C., the product is thermally decomposed to deteriorate the hue of the product. Also, if the reaction time is shorter than 4 hours, the reaction does not take place sufficiently and the conversion rate and yield are low, and if the reaction time is longer than 10 hours, the thermodynamically possible conversion rate is almost reached. It is meaningless to react.

The reaction may further include an entrainer during the reaction in the manufacturing method, and preferably 1 to 20 parts by weight of a liquid entrainer or a gaseous entrainer with respect to 100 parts by weight of the reactant. The reaction can be carried out at a flow rate of 0.1 to 10 times the reactor volume / hour. The entrainer is an auxiliary substance that plays a role of discharging H ₂ O generated in the esterification reaction to the outside of the reaction system. Since the esterification reaction in the above production method is a reversible reaction, if the product water is discharged to the outside of the reaction system, the reverse reaction is reduced according to the Le Chatelier's law, and the desired product is increased. obtain. Thus, the entrainer serves to increase the yield of the desired product. As the entrainer, an organic solvent containing n-hexane, toluene, xylene, or an inert gas such as nitrogen can be used, and n-hexane, toluene, xylene, nitrogen, etc. are particularly preferable. It is not limited to.

  In addition, the production method may further include a catalyst, and the catalyst may be used in an amount of 0.0001 to 1 part by weight with respect to 100 parts by weight of the reactant. The catalyst is a catalyst that promotes the esterification reaction. Acid catalysts such as sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, paratoluenesulfonic acid, methanesulfonic acid, and alkyl sulfuric acid, aluminum sulfate, lithium fluoride, calcium chloride, cesium chloride Metal salts such as calcium chloride, iron chloride, aluminum phosphate, metal oxides such as heteropolyacid, natural / synthetic zeolites, cation and anion exchange resins, organic metals such as tetraalkyl titanates and their polymers, etc. In particular, p-toluenesulfonic acid or tetraisopropyl titanate is desirable, but not limited thereto.

The post-treatment after the esterification reaction is completed is not particularly limited, but excess raw materials are removed by a method such as distillation under reduced pressure, for example, with a basic solution such as NaOH, KOH, Na ₂ CO ₃ aqueous solution. Can neutralize. Thereafter, the resulting product can be washed with water, dried by selectively depressurizing and dehydrating, and adsorbent is added to the resulting product, followed by filtration to obtain a final plasticizer composition, but is not limited thereto. It is not something.

  The production method of one embodiment of the hydroxypivalyl hydroxypivalate ester plasticizer composition according to the present invention will be described in more detail as follows.

  In a flask equipped with a stirrer and a condenser, hydroxypivalylhydroxypivalate or a mixture of hydroxypivalylhydroxypivalate and neopentylglycol 20 to 50% by weight, 2-ethylhexanoic acid 1 to 80% by weight And 1 to 80% by weight of benzoic acid and 1 to 20 parts by weight of xylene, which is a droplet entraining substance, and 0.0001 to 1 part by weight of tetraisopropyl titanate as a catalyst with respect to 100 parts by weight of the reaction product, The temperature is raised to 220 ° C. and the esterification reaction is carried out for 4 to 14 hours. After the esterification reaction, unreacted acid is removed by reducing the pressure with a vacuum pump, and unremoved residual acid is added in an amount of 5 to 50 parts by weight with respect to 100 parts by weight of the total amount of the reaction product. After neutralization, the final hydroxypivalyl hydroxypivalate ester plasticizer composition is obtained by removing by washing, dehydration and filtration.

  Polyvinyl chloride resin can be produced using the hydroxypivalyl hydroxypivalate ester plasticizer composition according to the present invention. Polyvinyl chloride resin produced in this way has tensile strength, elongation, hardness, migration resistance. Excellent in properties. The polyvinyl chloride resin can be produced by an ordinary resin production method using raw materials usually used for resin production in addition to the hydroxypivalyl hydroxypivalate ester plasticizer composition according to the present invention.

  In addition, the hydroxypivalyl hydroxypivalate ester plasticizer composition according to the present invention is not only used as a plasticizer for polyvinyl chloride resin, but also for other resins intended to improve tensile strength, elongation, migration resistance and hardness. Is also applicable. In particular, it is suitable for polyvinyl chloride resin for wrap films used for food packaging materials, and can also be applied to polyethylene foam sheets.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, the scope of the present invention is not limited to the following Example.

In the following examples and comparative examples, the test pieces of polyvinyl chloride resin were evaluated for tensile strength, elongation, hardness, migration resistance, and heat loss by the following methods. The results are shown in Table 2 below.
Tensile Strength According to ASTM D638 method, U. T.A. After setting the crosshead speed to 200 mm / min using M, the point where the test piece is cut is measured, and the tensile strength (kgf / mm ² ) = load value (kgf) / {thickness (mm) × Width (mm)} was calculated.
The test equipment U.S. T.A. After setting the crosshead speed to 200 mm / min using M, the position at which the test piece was cut was measured, and the elongation (%) = {extension / initial length} × 100 was calculated.
The hardness is measured as an index representing the hardness plasticization efficiency, and the hardness value after 5 seconds is read after the needle of the hardness tester (A type) is completely brought into contact with one place of the test piece based on the ASTM D2240 method. The average value was calculated after testing five locations on each test piece. The hardness was measured once immediately after manufacturing the test piece, and further measured once again after one day had passed after the test piece was manufactured.
The above test was performed on the test piece, and the results are shown in Table 2 below.

Heat loss and migration resistance were measured by the following methods.
The composition was worked for 3 minutes at 165 ° C. using a heat loss roll mill to prepare a 0.8 mm thick sheet, then 60 g was taken and again worked at 185 ° C. for 10 minutes using a roll mill. A test piece was manufactured with a thickness of 0.4 mm. Then, after 24 hours, the weight of the test piece was measured, and the weight loss by heating (% by weight) = {1− (weight after working at 185 ° C. for 10 minutes) / 60 g} × 100.
Transfer resistance Transfer resistance is measured by measuring the initial weight (Wi) up to 4 decimal places for each test piece manufactured above, and placing a sheet (3 cm x 3 cm) between the ABS resin plates in a 70 ° C oven. After leaving for 72 hours under a load of 1 kg, the test piece was taken out and stored in a thermostatic bath for 4 hours or more. After measuring the weight (Wo) of the test piece, the transfer amount (% by weight) = { Calculation was performed using (Wi-Wo) / Wi} X100.

<Example 1>
(1) Production of hydroxypivalyl hydroxypivalate ester plasticizer composition A 4-necked 2-liter round flask equipped with a stirrer and a condenser was charged with 2 mol of hydroxypivalyl hydroxypivalate and 1.6 mol of 2-ethylhexanoic acid. Then, 3.6 mol of benzoic acid, 60 g of xylene as an entraining agent, and 1.5 g of tetraisopropyl titanate as a catalyst were added, the temperature was raised to 220 ° C., and an esterification reaction was performed for 8 hours.
After the esterification reaction, unreacted acid was removed at 220 ° C. by reducing the pressure to 5 mmHg with a vacuum pump, and unremoved acid was neutralized with 10% by weight sodium hydroxide, followed by washing and dehydration processes. . After washing and dehydration processes, an adsorbent was added and filtered to produce a hydroxypivalyl hydroxypivalate ester plasticizer composition. As a result of analyzing the resulting hydroxypivalyl hydroxypivalate ester mixture, 2-ethyl-hexanoic acid 3- (2-ethyl-hexanoyloxy) -2,2-dimethyl-propyl ester 0.4% by weight, benzoic acid 3- (2-ethyl-hexanoyloxy) -2,2-dimethyl-propyl ester 2.5% by weight, benzoic acid 3-benzoyloxy-2,2-dimethyl-propyl ester 4.3% by weight, 2-ethyl -Hexanoic acid 2- [3- (2-ethyl-hexanoyloxy) -2,2-dimethyl-propoxycarbonyl] -2-methyl-propyl ester 6.2% by weight, benzoic acid 2- [3- (2- 16.9% by weight of ethyl-hexanoyloxy) -2,2-dimethyl-propoxycarbonyl] -2-methyl-propyl ester, 3- [benzoic acid 3- [ 1- (2-ethyl-hexanoyloxy) -2,2-dimethyl-propionyloxy] -2,2-dimethyl-propyl ester 14.6% by weight, benzoic acid 3- [3- (benzoyloxy) -2,2 -Dimethyl-propionyloxy] -2,2-dimethyl-propyl ester 44.9% by weight, 2-ethyl-hexanoic acid 2- {2- [3- (2-ethyl-hexanoyloxy) -2,2-dimethyl -Propoxycarbonyl] -2-methyl-propoxycarbonyl} -2-methyl-propyl ester 0.6% by weight, benzoic acid 3- {3- [3- (2-ethyl-hexanoyloxy) -2,2-dimethyl -Propionyloxy] -2,2-dimethyl-propionyloxy} -2,2-dimethyl-propyl ester 2.7% by weight and benzoic acid 3- {3- [3 (Benzoyloxy) -2,2-dimethyl - propionyloxy] -2,2-dimethyl - propionyloxy} -2,2-dimethyl - was propyl ester 4.0% by weight.
The said component and content were confirmed with the gas chromatography mass spectrometer (Gas Chromatography Mass Spectrometer, GC-MS).

(2) Production of polyvinyl chloride resin using hydroxypivalyl hydroxypivalate ester plasticizer composition Plasticizer for 100 parts by weight of polyvinyl chloride resin (product name LS100S, manufactured by LG Chemical Co., Ltd., Korea) After blending 60 parts by weight of the hydroxypivalyl hydroxypivalate ester plasticizer composition produced in (1) above and 3 parts by weight of calcium-zinc stabilizer (product name KP-630P, manufactured by Korea Daikyo Kasei) Using a roll mill, the sheet was processed at a temperature of 175 ° C. for 3 minutes to produce a sheet having a thickness of 5 mm. The sheet having a thickness of 5 mm was pressed to produce a sheet having a thickness of 1 mm. The conditions of the pressing operation were preheating at 185 ° C. for 3 minutes, heating for 3 minutes, and cooling for 3 minutes. A C-type (type C) dumbbell-type test piece was prepared from the manufactured 1 mm sheet and tested.

<Example 2>
A hydroxypivalyl hydroxypivalate ester plasticizer composition was produced by the same method as in Example 1 except that the amount of raw material used was changed as shown in Table 1 below. As a result of analyzing the produced hydroxypivalyl hydroxypivalate ester mixture, the compound (1) to the compound (10) were sequentially added in an amount of 1.4% by weight, 3.5% by weight, 2.2% by weight, 20.5%, respectively. % By weight, 19.8% by weight, 21.3% by weight, 20.0% by weight, 2.4% by weight, 5.1% by weight and 2.5% by weight.
Thereafter, a test piece was produced in the same manner as in Example 1 using the hydroxypivalyl hydroxypivalate ester plasticizer composition. The manufactured test piece was subjected to the same test as the test performed in Example 1, and the results are shown in Table 2 below.

<Example 3>
A hydroxypivalyl hydroxypivalate ester plasticizer composition was produced in the same manner as in Example 1 except that the amount of raw material used was changed as shown in Table 1 below. As a result of analyzing the produced hydroxypivalyl hydroxypivalate ester mixture, the compound (1) to the compound (10) were sequentially 2.2% by weight, 3.4% by weight, 1.4% by weight, 32.0% by weight, respectively. %, 19.5% by weight, 17.3% by weight, 10.6% by weight, 4.0% by weight, 5.1% by weight and 1.6% by weight.
Thereafter, test pieces were produced in the same manner as in Example 1 using the hydroxypivalyl hydroxypivalate plasticizer composition. The manufactured test piece was subjected to the same test as the test performed in Example 1, and the results are shown in Table 2 below.

<Example 4>
A hydroxypivalyl hydroxypivalate ester plasticizer composition was produced in the same manner as in Example 1 except that the amount of raw material used was changed as shown in Table 1 below. As a result of analyzing the produced hydroxypivalyl hydroxypivalate ester mixture, 4.2% by weight, 9.5% by weight, 5.1% by weight and 18.1% by weight from the compound (1) to the compound (10), respectively. %, 20.9 wt%, 16.7 wt%, 18.8 wt%, 1.2 wt%, 2.7 wt%, and 1.3 wt%.
Then, the test piece was manufactured by the same method as the method of Example 1 using the hydroxypivalyl hydroxypivalate plasticizer composition. The manufactured test piece was subjected to the same test as the test performed in Example 1, and the results are shown in Table 2 below.

<Example 5>
A hydroxypivalyl hydroxypivalate ester plasticizer composition was produced in the same manner as in Example 1 except that the amount of raw material used was changed as shown in Table 1 below. As a result of analyzing the produced hydroxypivalyl hydroxypivalate ester mixture, compound (1): 5.3% by weight, compound (4): 77.3% by weight, compound (8): 10.7% by weight, etc. It was 6.7% by weight. Here, the other substances are reaction intermediates, not impurities.
Thereafter, test pieces were produced in the same manner as in Example 1 using the hydroxypivalyl hydroxypivalate plasticizer composition. The manufactured test piece was subjected to the same test as the test performed in Example 1, and the results are shown in Table 2 below.

<Example 6>
A hydroxypivalyl hydroxypivalate ester plasticizer composition was produced in the same manner as in Example 1 except that the amount of raw material used was changed as shown in Table 1 below. As a result of analyzing the produced hydroxypivalyl hydroxypivalate ester mixture, compound (3): 5.4% by weight, compound (7): 87.1% by weight, compound (10): 5.1% by weight, others It was 2.4% by weight. Here, the other substances are reaction intermediates, not impurities.
Thereafter, test pieces were produced in the same manner as in Example 1 using the hydroxypivalyl hydroxypivalate plasticizer composition. The manufactured test piece was subjected to the same test as the test performed in Example 1, and the results are shown in Table 2 below.

<Comparative Example 1>
The most widely used di-2-ethylhexyl phthalate (manufactured by Korea Chemical Co., Ltd., LG Chemical Co., Ltd., trade name DOP) plasticizer 60 parts by weight and calcium-zinc stabilizer (manufactured by Daikyo Kasei, Korea) Test pieces were produced in the same manner as in Example 1 using 3 parts by weight of product name KP-630P). The manufactured test piece was subjected to the same test as the test performed in Example 1, and the results are shown in Table 2 below.

<Comparative example 2>
Test piece in the same manner as in Example 1 using di-2-ethylhexyl adipate (LG Chemical Manufacturing Co., Ltd. of Korea, trade name DOA) used as a general-purpose plasticizer. Manufactured. The manufactured test piece was subjected to the same test as the test performed in Example 1, and the results are shown in Table 2 below.

<Comparative Example 3>
A test piece was produced in the same manner as in Example 1 using diisononyl phthalate (LG Chemicals, Inc., Korea Co., Ltd., trade name DINP) used as a general-purpose plasticizer as a plasticizer. The manufactured test piece was subjected to the same test as the test performed in Example 1, and the results are shown in Table 2 below.

<Comparative Example 4>
Test pieces were produced in the same manner as in Example 1 using diisononyl adipate (LG Chemicals, Inc., Korea Co., Ltd., trade name DINA) used as a general-purpose plasticizer. The manufactured test piece was subjected to the same test as the test performed in Example 1, and the results are shown in Table 2 below.

<Comparative Example 5>
A test piece was produced in the same manner as in Example 1 using ATBC (Acetyl tri-butyl citrate), which is mainly used in medical products as a non-phthalate plasticizer, as a plasticizer. The manufactured test piece was subjected to the same test as the test performed in Example 1, and the results are shown in Table 2 below.

  As shown in Table 2, Examples 1 to 6 of the plasticizer composition of the present invention are not only excellent in tensile strength when compared with Comparative Examples, but also other physical properties such as elongation. It was found to be excellent in rate, loss on heating, resistance to migration, etc., and the hardness was comparable to that of existing plasticizers.

  Although preferred embodiments of the present invention have been described in detail above, those skilled in the art will recognize that the invention can be practiced in various modifications without departing from the spirit and scope of the invention as defined in the claims. It will be possible.

Claims (14)

Hydroxypivalyl hydroxypivalate ester compound selected from the group represented by the following chemical formula:
[Chemical formula 5]
_{R 3 OCO-CH 2 C (} CH 3) 2 -COO-CH 2 C (CH 3) 2 -CH 2 -OCOR 2
[Chemical 6]
_{R 2 OCO-CH 2 C (} CH 3) 2 -COO-CH 2 C (CH 3) 2 -CH 2 -OCOR 3
[Chemical 8]
_{R 1 OCO-CH 2 C (} CH 3) 2 -COO-CH 2 C (CH 3) 2 -COO-CH 2 C (CH 3) 2 C (CH 3) 2 -CH 2 -OCOR 1
[Chemical 9]
_{R 2 OCO-CH 2 C (} CH 3) 2 -COO-CH 2 C (CH 3) 2 -COO-CH 2 C (CH 3) 2 C (CH 3) 2 -CH 2 -OCOR 3
[Chemical Formula 10]
_{R 4 OCO-CH 2 C (} CH 3) 2 -COO-CH 2 C (CH 3) 2 -COO-CH 2 C (CH 3) 2 C (CH 3) 2 -CH 2 -OCOR 4
In the chemical formula:
R ₁ and R ₂ are each independently an alkyl group having 3 to 12 carbon atoms, and R ₃ and R ₄ are each independently an aryl group having 6 to 10 carbon atoms. The hydroxypivalyl hydroxypivalate ester compound according to claim _1, wherein R ₁ and R ₂ are 1-ethylpentyl groups, and R ₃ and R ₄ are phenyl groups. (A) a neopentyl glycol ester compound containing one or more compounds represented by the following chemical formulas 1 to 3,
(B) a hydroxypivalyl hydroxypivalate ester compound containing one or more compounds represented by the following chemical formulas 4 to 7;
(C) a hydroxypivalyl hydroxypivalate ester compound containing one or more compounds represented by the following chemical formulas 8 to 10;
Hydroxypivalyl hydroxypivalate ester plasticizer composition comprising:
[Chemical 1]
R ₁ OCO—C (CH ₃ ) ₂ —OCOR ₁
[Chemical 2]
_{R 2 OCO-C (CH 3} ) 2 -OCOR 3
[Chemical formula 3]
_{R 4 OCO-C (CH 3} ) 2 -OCOR 4
[Chemical formula 4]
R ₁ OCO—CH ₂ C (CH ₃ ) ₂ —COO—CH ₂ C (CH ₃ ) ₂ —CH ₂ —OCOR ₁
[Chemical formula 5]
_{R 3 OCO-CH 2 C (} CH 3) 2 -COO-CH 2 C (CH 3) 2 -CH 2 -OCOR 2
[Chemical 6]
_{R 2 OCO-CH 2 C (} CH 3) 2 -COO-CH 2 C (CH 3) 2 -CH 2 -OCOR 3
[Chemical 7]
_{R 4 OCO-CH 2 C (} CH 3) 2 -COO-CH 2 C (CH 3) 2 -CH 2 -OCOR 4
[Chemical 8]
_{R 1 OCO-CH 2 C (} CH 3) 2 -COO-CH 2 C (CH 3) 2 -COO-CH 2 C (CH 3) 2 C (CH 3) 2 -CH 2 -OCOR 1
[Chemical 9]
_{R 2 OCO-CH 2 C (} CH 3) 2 -COO-CH 2 C (CH 3) 2 -COO-CH 2 C (CH 3) 2 C (CH 3) 2 -CH 2 -OCOR 3
[Chemical Formula 10]
_{R 4 OCO-CH 2 C (} CH 3) 2 -COO-CH 2 C (CH 3) 2 -COO-CH 2 C (CH 3) 2 C (CH 3) 2 -CH 2 -OCOR 4
In the chemical formula:
R ₁ and R ₂ are each independently an alkyl group having 3 to 12 carbon atoms, and R ₃ and R ₄ are each independently an aryl group having 6 to 10 carbon atoms. 1 to 50% by weight of a neopentyl glycol ester compound containing at least one of the compounds represented by Chemical Formula 1 to Chemical Formula 3 in (a), and a compound represented by Chemical Formula 4 to Chemical Formula 7 in (b) Of these, hydroxypivalyl hydroxypivalate ester compound containing 40 to 90% by weight of one or more hydroxypivalyl hydroxypivalate ester compounds and one or more of compounds represented by chemical formulas 8 to 10 of (c) above 1 to 40% by weight of the compound,
The hydroxypivalyl hydroxypivalate ester plasticizer composition according to claim 3, comprising:   2-ethyl-hexanoic acid 3- (2-ethyl-hexanoyloxy) -2,2-dimethyl-propyl ester, benzoic acid 3- (2-ethyl-hexanoyloxy) -2,2-dimethyl-propyl ester, Benzoic acid 3-benzoyloxy-2,2-dimethyl-propyl ester, 2-ethyl-hexanoic acid 2- [3- (2-ethyl-hexanoyloxy) -2,2-dimethyl-propoxycarbonyl] -2-methyl -Propyl ester, benzoic acid 2- [3- (2-ethyl-hexanoyloxy) -2,2-dimethyl-propoxycarbonyl] -2-methyl-propyl ester, benzoic acid 3- [3- (2-ethyl- Hexanoyloxy) -2,2-dimethyl-propionyloxy] -2,2-dimethyl-propyl ester, benzoic acid 3- [3- (benzo Zoyloxy) -2,2-dimethyl-propionyloxy] -2,2-dimethyl-propyl ester, 2-ethyl-hexanoic acid 2- {2- [3- (2-ethyl-hexanoyloxy) -2,2- Dimethyl-propoxycarbonyl] -2-methyl-propoxycarbonyl} -2-methyl-propyl ester, benzoic acid 3- {3- [3- (2-ethyl-hexanoyloxy) -2,2-dimethyl-propionyloxy] -2,2-dimethyl-propionyloxy} -2,2-dimethyl-propyl ester and benzoic acid 3- {3- [3- (benzoyloxy) -2,2-dimethyl-propionyloxy] -2,2- Hydroxyl according to claim 3, characterized in that it comprises dimethyl-propionyloxy} -2,2-dimethyl-propyl ester. Valyl hydroxy pivalate ester plasticizer composition.   Hydroxypivalyl hydroxypivalate, or a mixture of hydroxypivalyl hydroxypivalate and neopentyl glycol, 20 to 50% by weight, a fatty acid having 3 to 12 carbon atoms, an aromatic acid having 6 to 10 carbon atoms, or the carbon number The method for producing a hydroxypivalyl hydroxypivalate ester plasticizer composition according to claim 3, comprising a step of reacting 3 to 12 fatty acids with 50 to 80% by weight of an aromatic acid having 6 to 10 carbon atoms.   The process according to claim 6, wherein the mixture of hydroxypivalyl hydroxypivalate and neopentyl glycol is a mixture of 9.5: 0.5 to 5: 5 by weight.   The method according to claim 6, wherein the fatty acid is 2-ethylhexanoic acid and the aromatic acid is benzoic acid.   The process according to claim 6, wherein the reaction is carried out at a temperature of 100 to 300 ° C for 4 to 14 hours.   1 to 20 parts by weight of liquid entrainer is further added to 100 parts by weight of the reactants, or gaseous entrainer is added to the reactants at a rate of 0.1 to 10 times the reactor volume / hour. The manufacturing method according to claim 6.   The production method according to claim 10, wherein the entrainer is selected from the group consisting of n-hexane, toluene, xylene, nitrogen, and helium.   The production method according to claim 6, wherein 0.0001 to 1 part by weight of a catalyst is further added and reacted with respect to 100 parts by weight of the total reactant.   The production method according to claim 12, wherein the catalyst is para-toluenesulfonic acid or tetraisopropyl titanate.   A polyvinyl chloride resin comprising the hydroxypivalyl hydroxypivalate ester plasticizer composition according to any one of claims 3 to 5.