KR20090131529A - A plasticizer and the composition of polyvinylchloride resin comprised the same - Google Patents

Abstract

PURPOSE: A citric ester-based plasticizer is provided to ensure the same or more excellent properties as or than a conventional phthalate-based plasticizer, to obtain a polyvinylchloride resin product with excellent hardness and extraction resistance, and to ensure volatilization loss of the polyvinyl chloride resin. CONSTITUTION: A citric ester-based plasticizer is a citric ester-based compound represented by chemical formula 1. In the chemical formula 1, R1 is C1-4 alkyl group, R2 is C1-8 alkyl group, and n is 1-5. The polyvinyl chloride resin compound includes 10-150 phr of the plasticizer based on the polyvinyl chloride resin. The polyvinyl chloride resin compound includes 30 phr of additives excluding filler and pigment based on the polyvinyl chloride resin.

Description

A plasticizer and the composition of polyvinylchloride resin comprised the same}

The present invention relates to a citric acid ester compound and a plasticizer including the same, particularly a plasticizer for polyvinyl chloride (PVC), and more particularly, to polyvinyl chloride resin having excellent hardness and extraction resistance as well as improved volatile properties. It relates to a citric acid ester plasticizer capable of preparing the composition.

Polyvinyl chloride resin is a homopolymer of vinyl chloride or a hybrid polymer containing 50% or more of vinyl chloride, and is a general-purpose resin that can be used by processing methods such as extrusion, injection molding, calendering, and the like. It is widely used in various products such as electric wires, electromechanical products, toys, films, sheets, artificial leather, tarpaulins, tapes, food packaging materials, and medical supplies. Such a polyvinyl chloride resin may impart various processing properties 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 to impart various physical properties and functions such as processability, flexibility, electrical insulation, and adhesiveness. Low volatility is a very important factor for plasticizers, which is important both during incorporation into plastic compositions and during the actual use of molded articles. In addition, plasticizers provided for application in the food and beverage sector and in the pharmaceutical sector shall be harmless to health. Representative kinds of such plasticizers include phthalates. However, due to controversy over regenerative toxicity under legislation already regulating toxic substances, the use of phthalates is expected to decrease significantly in the future. Therefore, there is a demand for the development of a plasticizer having a plasticization efficiency equivalent to that of a phthalate-based plasticizer while having a non-toxic substance such as citric acid as a basic skeleton.

In order to solve the above problems, the present inventors have conducted an in-depth study of citric acid ester compounds as plasticizers of polyvinyl chloride resins, and as a result, specific novel citric acid ester compounds can be used as plasticizers. It came to complete this invention based on the experiment result which is excellent as a plasticizer. Accordingly, an object of the present invention is to provide a novel citric acid ester plasticizer compound having the same or superior physical properties as the conventional phthalate plasticizer.

Another object of the present invention is to provide a polyvinyl chloride resin containing the novel plasticizer compound.

Plasticizer according to the first aspect of the present invention for achieving the above technical object is a citric acid ester compound represented by the following formula (1),

In the above formula, R ₁ is an alkyl group having 1 to 4 carbon atoms, R ₂ is an alkyl group having 1 to 8 carbon atoms, n is 1 to 5.

A second aspect of the present invention for achieving another object of the present invention is a polyvinyl chloride containing 10 to 150 phr (parts per hundred resin) citric acid ester compound plasticizer according to the formula (1) with respect to the polyvinyl chloride resin It provides a resin composition.

When the polyvinyl chloride resin is manufactured by using the citric acid ester plasticizer according to the present invention, an excellent product in terms of hardness (plasticization efficiency) and extraction resistance can be obtained, and in addition, physical properties such as volatile loss are improved. .

The first aspect of the present invention relates to a citric acid ester compound represented by the formula (1).

<Formula 1>

In the above formula, R ₁ is an alkyl group having 1 to 4 carbon atoms, R ₂ is an alkyl group having 1 to 8 carbon atoms, n is 1 to 5. The said R <_1> and R <_2> may be linear or branched. Preferably, R ₁ is methyl, ethyl, n-propyl, iso-propyl group, R ₂ is ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl group, t- Butyl group etc. are mentioned. Most preferred is the case where R ₁ is a methyl group, R ₂ is a butyl group, and n is 2.

Next, the manufacturing method of the citric acid ester compound which concerns on this invention is demonstrated.

Citric acid ester compounds according to the present invention are prepared by reacting with an alcohol such as Butyl carbitol. The reaction is carried out with excess alcohol in the presence of a catalyst to achieve the maximum acid conversion possible within the allowed time. The molar ratio of alcohol to citric acid 1 is 3 to 8: 1, preferably 4 to 6: 1, and this molar ratio is based on the hydroxy group present in the alcohol. In addition to using excess alcohol for high conversion and associated high production yields, it is desirable to continue to remove the moisture produced. Preferred catalysts are acid catalysts, for example sodium bisulfate. Examples of the catalyst that can be used include, for example, p-toluene sulfonic acid or sulfuric acid, and the catalyst may be used in an amount of 0.5 to 5 phr based on the reaction mixture.

Solvents that can be used are hexane, cyclohexane, toluene and xylene. The preferred temperature range for reacting citric acid with alcohol was found to be 100 to 160 ° C.

After the esterification reaction, the acid catalyst is neutralized by evenly mixing the crude ester with the alkaline solution by the addition of an alkaline reagent such as sodium hydroxide, sodium carbonate or aqueous sodium hydrogen carbonate solution. The crude ester obtained after phase separation is washed with water and dewatered to remove the final traces of alkali and then filtered to give the primary reactant.

Next, in order to convert the OH group of citric acid into ether form, the primary reactant: iodomethane, dimethyl sulfate, dimethyl carbonate or bromomethane: sodium hydroxide was added in a molar ratio of 1: 2 to 5: 1 to 3. After the reaction was conducted at 0 ° C. for 4 to 10 hours, washing with water and dehydration with water to remove unreacted material was followed by filtration to obtain a citric acid ester plasticizer.

The citric acid ester compound according to the present invention has excellent compatibility with the polyvinyl chloride resin, which is believed to be due to the increased intermolecular attraction of the resin and the plasticizer by the contribution of three esters and one ether group.

A second aspect of the present invention is to provide a polyvinyl chloride resin composition having improved hardness, extraction resistance, and reduced volatilization, using the plasticizer of the present invention disclosed above.

The citric acid ester compounds according to the present invention are suitably used for polyvinyl chloride resins, but are not limited to polyvinyl chloride resins, and include chlorine-containing resins such as chlorinated polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene, and vinyl chloride-acetic acid. Vinyl copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride- various vinyl ether copolymers Chlorine-containing resins such as copolymers and their mutual blends, and synthetic resins containing no chlorine-containing resins and chlorine, such as acrylonitrile-styrene copolymers, acrylonitrile-styrene-butadiene terpolymers, and ethylene-acetic acid The present invention can also be applied to blends with vinyl copolymers, polyesters, block copolymers, graft copolymers, and the like.

The polyvinyl chloride resin composition of the present invention comprises 10 to 150 phr of the citric acid ester plasticizer compound according to the present invention as described above with respect to the polyvinyl chloride resin, and an additive component of 0 to 30 phr. The plasticizer compound according to the present invention may be appropriately increased or decreased depending on the use of the resin composition, but when it is added below 10 phr, the plasticizer compound may not achieve the flexibility or processability that can be expressed by the plasticizer. It is not preferable to secure mechanical properties and may also elute.

As an additive which can be included selectively, Plasticizers other than the citric acid compound plasticizer concerning this invention; For example, Adipate type, Sebacate type, hydrocarbon type, vegetable oil type, or TXIB (2,2,4-trimethyl-1,3 pentanediol diisobutylate); Insulation improvers; Various metal salts; Polyols; Epoxy compounds; Phenolic or sulfur antioxidants; Ultraviolet absorbers; Hindered amine light stabilizers; Inorganic stabilizers; Anti-fogging agents; Anti-misting agents; Stabilization aids; Well-known general additive components, such as an organotin compound, are mentioned.

However, unlike the general additives, the filler (filler) and the pigment may be included up to about 200phr relative to the polyvinyl chloride resin. Examples of the fillers include calcium carbonate, silica, cray, glass beads, mica, sericite, glass flake, asbestos, wollastononaite, potassium titanate, PMF, Gypsum fiber, xonotlite, MOS, phosphate fiber, glass fiber, carbonate fiber, aramid fiber and the like.

It is preferable that the usage-amount of the plasticizer added other than the citric acid ester-type plasticizer of this invention shall be 30 phr or less with respect to the plasticizer which concerns on this invention. When the addition range is exceeded, problems such as compatibility or viscosity increase may occur.

As said insulation improving agent, it is described in Unexamined-Japanese-Patent No. 57-177040, Unexamined-Japanese-Patent No. 5-262943, Unexamined-Japanese-Patent No. 5-179090, Unexamined-Japanese-Patent No. 9-324089, etc. The amorphous calcium silicate (hydrate), the composition which consists of (alpha)-dicalcium silicate hydrate and calcium hydroxide, the silicate of aluminum or alkaline-earth metal, etc. are mentioned. Among these, amorphous calcium silicate (hydrate) is preferable because it is excellent in insulation and heat resistance.

As the above various metal salts, for example, metals of organic acids or phenols (Li, Na, K, Ca, Ba, Mg, Sr, Zn, Cd, Sn, Cs, Al, organic Sn) salts and organic phosphates And metal (Li, Na, K, Ca, Ba, Mg, Sr, Cd, Sn, Cs, Al, organic Sn) salts, and the like, and the amount thereof is preferably used based on 100 parts by mass of the chlorine-containing resin. It is 0.05-10 mass parts.

Examples of the organic acids used for the metal salts include capric acid, caprylic acid, pelargonic acid, 2-ethylhexyl acid, capric acid, neodecanoic acid, undecylenic acid, Lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, 12-hydroxystearic acid, chlorostearic acid, 12-ketostearic acid, phenylstearic acid, ricinoleic acid, linoleic acid, linoleic acid, oleic acid , Arakic acid, behenic acid, erucic acid, bracidic acid and similar acids, and resinous fatty acids, coconut oil fatty acids, paulownia oil fatty acids , A mixture of the above-mentioned organic acids, such as soybean oil fatty acid and cottonseed oil fatty acid, benzoic acid, p-tert-butylbenzoic acid, ethylbenzoic acid, isopropyl benzoic acid, toluic acid ( toluic acid, xylylic acid lic acid), salicylic acid, 5-tert-octylsalicylic acid, naphthenic acid, cyclohexanecarboxylic acid, adipic acid, maleic acid, acrylic acid, methacrylic acid, and the like. Moreover, as phenols used for said metal salt, phenol, cresol, ethyl phenol, cyclohexyl phenol, nonyl phenol, lauryl phenol etc. are mentioned, for example. Moreover, as organic phosphoric acid used for said metal salt, a mono or dioctyl phosphoric acid, a mono or dilauryl phosphoric acid, a mono or distearyl phosphoric acid, a mono or di (nonylphenyl) phosphoric acid, a phosphonate nonylphenyl, for example Ester, phosphonic acid stearyl ester, etc. are mentioned.

Among these various metal salts, organic acid zinc salts and / or organic acid alkaline earth metal salts are preferred because they are advantageous in terms of anti-coloring resistance, heat resistance and cost. Examples of the above polyols include trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, polypentaerythritol, pentaerythritol, or dipentaerythritol. (stearic acid half ester), bis (dipentaerythritol) adipate, glycerin, tris (2-hydroxyethyl) isocyanurate, sorbitol, mannitol, trehalose and the like.

Moreover, as said epoxy compound, For example, epoxidized soybean oil, epoxidized linseed oil, epoxidized paulownia oil, epoxidized fish oil, epoxidized fish oil, epoxidized castor oil, epoxy Epoxidized animal and vegetable oils such as safflower oil, epoxidized methyl stearate, epoxidized butyl stearate, epoxidized stearic acid-2-ethylhexyl, epoxidized stearic acid stearyl ester, epoxidized polybutadiene, tris (epoxypropyl) isocyanurate, Epoxidized tall oil fatty acid esters, epoxidized linseed oil fatty acid esters, vinylcyclohexene diepoxide, dicyclohexene diepoxide, 3,4-epoxycyclohexene methylepoxycyclohexanecarboxylate, Bisphenol A diglycidyl ether, trimethylol propane polyglycidyl ether, glycerin polyglycidyl ether, hexanediol Liglycidyl ether, 2,2-dimethyl-1,3-propanediol polyglycidyl ether, hydrogenated bisphenol polyglycidyl ether, cyclohexane dimethanol polyglycidyl ether, etc. Can be.

Moreover, as said organic phosphite compound, for example, a triphenyl phosphite, a tris (2, 4- di- tert butylphenyl) phosphite, a tris (2, 5- di- tert butylphenyl) phosphite, and a tris (nonylphenyl) ) Phosphite, Tris (dinonylphenyl) phosphite, Tris (mono, dimixed nonylphenyl) phosphite, diphenyl acid phosphite, 2,2'-methylenebis (4,6-dije-3 Butylphenyl) octyl phosphite, diphenyldecyl phosphite, diphenyl octyl phosphite, di (nonylphenyl) pentaerythritol diphosphite, phenyl diisodecyl phosphite, tributyl phosphite, tris (2-ethylhexyl) phosphite , Tridecyl phosphite, trilauryl phosphite, dibutyl acid phosphite, dilauryl acid phosphite, trilauryl trithio phosphite, bis (neopentyl glycol), 1, 4- cyclohexane dimethyl diphosphite, bis (2,4-dije tert-butylphenyl) pen Erythritol diphosphite, bis (2,5-dithi-3-butylphenyl) pentaerythritol diphosphite, bis (2,6-dize-3-butyl-4-methylphenyl) pentaerythritoldiphosphite, bis (2,4-dicumylphenyl Pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tetra (C12-15 mixed alkyl) -4,4'-isopropylidenediphenylphosphite, bis [2,2'-methylenebis (4,6) -Diamylphenyl)] isopropylidene diphenyl phosphite, tetratridecyl, 4,4'- butylidenebis (2-tertbutyl-5-methylphenol) diphosphate, hexa (tridecyl) 1,1,3-tris (2-methyl-5-tertbutyl-4-hydroxyphenyl) butanetriphosphite, tetrakis (2,4-dithitertbutylphenyl) biphenylenediphosphonite (diphosphonite ), Tris (2-[(2,4,7,9-tetrakis tert-butyldibenzo [d, f] [1,3,2] dioxaphosphepin-6-yl) oxy] ethyl Amine, 9,10-dihydro-9-oxa-10-phosphaphenant (Phosphaphenanthrene) can be given a 10-oxide, 2-butyl-2-ethyl-propanediol and 2,4,6 tert -butyl phenol mono-phosphite.

Moreover, as said phenolic antioxidant, 2, 6- dize- 3-butyl- p-cresol, 2, 6- diphenyl-4- octadecyloxyphenol, stearyl (3, 5-, for example) Dithibutyl-4-hydroxyphenyl) propionate, distearyl (3,5-dithibutyl-3 hydroxybenzyl) phosphonate, tridecyl 3,5-dithibutyl-3 hydroxy-4- Oxybenzylthioacetate, thiodiethylenebis [(3,5-dizethibutyl-4-hydroxyphenyl) propionate], 4,4′-thiobis (6-tertbutyl-m-cresol), 2 -Octylthio-4,6-di (3,5-dize-3butyl-4-hydroxyphenoxy) -s-triazine, 2,2'-methylenebis (4-methyl-6-tertbutylphenol) , Bis [3,3-bis (4-hydroxy-3-tert-butylphenyl) butyric acid] glycol esters, 4,4′-butylidenebis (2,6-dizet-butylphenol ), 4,4′-butylidenebis (6-tert-butyl-3-methylphenol), 2,2′-ethylidenebis (4,6-dizetertbutylphenol), 1,1,3-tris (2-Methyl-4-hydroxy-5-tertbutylphenyl) butane, bis [2-tertiary Methyl-4-methyl-6- (2-hydroxy-3-tertbutyl-5-methylbenzyl) phenyl] terephthalate, 1,3,5-tris (2,6-dimethyl-3-hydroxy-4 Tert-butylbenzyl) isocyanurate, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (3,5- Didzeylbutyl-3 hydroxybenzyl) -2,4,6-trimethylbenzene, 1,3,5-tris ((3,5-degrose3-butyl-4-hydroxyphenyl) propionyloxy ethyl] isocy Anurate, tetrakis [methylene-3- (3,5-dizetbutyl-4-hydroxyphenyl) propionate] methane, 2-tertbutyl-4-methyl-6- (2-acryloyloxy 3-tert-butyl-5-methylbenzyl) phenol, 3,9-bis [2- (3-tert-butyl-4-hydroxy-5-methylhydrocinnamoyloxy) -1,1- Dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, triethylene glycol bis [β- (3-tertbutyl-4-hydroxy-5-methylphenyl) propionate ] Can be mentioned.

Moreover, as said sulfur type antioxidant, Dialkyl thiodipropionates, such as dilauryl, dimyristyl, myristyl stearyl, and distearyl ester of thiodipropionic acid, for example, and penta, (Beta) -alkyl mercaptopropionic acid ester of polyols, such as erythritol tetra ((beta) -dodecyl mercaptopropionate).

Moreover, as said ultraviolet absorber, 2, 4- dihydroxy benzophenone, 2-hydroxy-4- methoxy benzophenone, 2-hydroxy-4- octyloxy benzophenone (octyloxybenzophenone), 2- Hydroxy-4-tertbutyl-4 ′-(2-methacryloyloxyethoxyethoxy) benzophenone, 5,5′-methylenebis (2-hydroxy-4-methoxybenzophenone) 2-hydroxybenzophenones, such as 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-5-third octylphenyl) benzotriazole, 2- (2- Hydroxy-3,5-di-dibutylbutyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2- (2 -Hydroxy-3-dodecyl-5-methylphenyl) benzotriazole, 2- (2-hydroxy-3- tert-butyl-5-C7-9 mixed alkoxycarbonylethylphenyl) triazole, 2- (2 -Hydroxy-3,5-dicumylphenyl) benzotriazole, 2,2'-methylenebis (4-tert-octyl-6-benzotriazolylphenol), 2- (2-hydroxy-3-third Butyl-5 2- (2-hydroxyphenyl) benzotriazole such as polyethylene glycol ester of -carboxyphenyl) benzotriazole; 2- (2-hydroxy-4-hexyloxyphenyl) -4,6-diphenyl-1 , 3,5-triazine, 2- (2-hydroxy-4-methoxyphenyl) -4,6-diphenyl-1,3,5-triazine, 2- (2-hydroxy-4-octyl Oxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-acryloyloxyethoxyphenyl) -4 2- (2-hydroxyphenyl) -1,3,5-triazines such as, 6-bis (2,4-dimethylphenyl) -1,3,5-triazine, phenylsalicylate, resorcinol Monobenzoate, 2,4-dize-3-butylphenyl-3,5-dize-3butyl-4-hydroxybenzoate, 2,4-dize3-amylphenyl-3,5-dize-3-butyl-4-hydroxybenzo Benzoates, such as ate and hexadecyl-3,5-dizetbutyl-4-hydroxybenzoate, 2-ethyl-2'-ethoxyoxanilide, 2-ethoxy-4'-dode Substituted oxanilides, such as a silane oxanilide; ethyl- (alpha)-cyano- , And the like β- diphenyl acrylate, methyl-2-cyano-3-methyl-3- (p- methoxyphenyl) acrylate, and the like of the cyanoacrylate.

Moreover, as said hindered amine light stabilizer, it is 2,2,6,6- tetramethyl-4- piperidyl stearate, 1,2,2,6,6-pentamethyl, for example. -4-piperidylstearate, 2,2,6,6-tetramethyl-4-piperidylbenzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, Bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate , Tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, tetrakis (1,2,2,6,6-penta Methyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, bis (2,2,6,6-tetramethyl-4-piperidyl) -bis (tridecyl) -1 , 2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) -bis (tridecyl) -1,2,3,4-butane Tetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2-butyl-2- (3,5-dizetbutyl-4-hydroxybenzyl) Malonate, 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol / diethyl zucchini polycondensate, 1,6- Bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / dibromoethane polycondensate, 1,6-bis (2,2,6,6-tetramethyl-4 -Piperidylamino) hexane / 2,4-dichloro-6-morpholino-s-triazine polycondensate, 1,6-bis (2,2,6,6-tetramethyl-4-pi Ferridylamino) hexane / 2,4-dichloro-6-tertiaryctylamino-s-triazine polycondensate, 1,5,8,12-tetrakis [2,4-bis (N-butyl-N- ( 2,2,6,6-tetramethyl-4-piperidyl) amino) -s-triazin-6-yl] -1,5,8,12-tetraazadodecane, 1,5, 8,12-tetrakis [2,4-bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -s-triazin-6-yl ] -1,5,8,12-tetraazadodecane, 1,6,11-tris [2,4-bis (N-butyl-N- (2,2,6,6-tetramethyl-4-pi Ferridyl) amino-s-triazin-6-ylamino] yl Cahn, 1,6,11-tris [2,4-bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino-s-triazine-6 -Ylamino] undecane, 3,9-bis [1,1-dimethyl-2- [tris (2,2,6,6-tetramethyl-4-piperidyloxycarbonyloxy) butylcarbon Carbonyloxy] ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 3,9-bis [1,1-dimethyl-2- [tris (1,2,2,6) , 6-pentamethyl-4-piperidyloxycarbonyloxy) butylcarbonyloxy] ethyl] -2,4,8,10- tetraoxaspiro [5.5] undecane and the like.

As the inorganic stabilizer, for example, hydrotalcite, calcium phosphate, calcium oxide, calcium hydroxide, calcium silicate, magnesium phosphate, magnesium oxide, magnesium hydroxide, aluminum hydroxide, amorphous aluminosilicate, zeolite crystals And aluminosilicates of alkali metals and / or alkaline earth metals having a structure, powder silicic acid (silica), overbased calcium carbonate, sodium perchlorate, magnesium perchlorate and barium perchlorate.

Moreover, as said antifogging agent, For example, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol monopalmitate, polyethylene glycol monostearate, poly Oxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, glycerin monolaurate, glycerin monopalmitate, glycerin monostearate, glycerin monooleate, pentaerythritol monolaurate, sorbitan mono Palmitate, sorbitan monobehenate, sorbitan distearate, diglycerol dioleate sodium laurylsulfate, sodium dodecylbenzenesulfonate, sodium butylnaphthalenesulfonate, cetyltrimethylammonium chloride cetyltrimethylammonium chloride), dodecyl Hydrochloride, lauric laurylamide ethyl phosphate, triethylcetylammonium iodide, oleylaminodiethylamine hydrochloride, dodecylpyridinium salt, and the like.

Moreover, as said anti-rust agent, an anionic fluorine-containing surfactant, a cationic fluorine-containing surfactant, an amphoteric fluorine-containing surfactant, a nonionic fluorine-containing surfactant, fluorine-containing Fluorine-containing compounds, such as an oligomer, are mentioned.

Moreover, as said stabilization adjuvant, diphenylthiourea, diphenylurea, anilinodithiothioazine, melamine, benzoic acid, cinnamic acid, p-third Butyl benzoic acid and an aliphatic organic acid are mentioned.

Moreover, as said organic tin compound, the laurate, maleate, mercapto, maleate polymer of dibutyltin or dioctyl tin is mentioned, for example.

As other additive components, in addition to the components exemplified above, additive components usually used for chlorine-containing resins, for example, crosslinking agents, antistatic agents, thixotropic agents, and anti-plateout agents (anti -plate-out agents, surface treatment agents, lubricants, flame retardants, fluorescent agents, flavoring agents, fungicides, metal deactivators, mold release agents, processing aids, antioxidants, light stabilizers, foaming agents and the like may also be used.

In the polyvinyl chloride resin composition of the present invention, the total amount of the additive component except the filler and the pigment is usually 0 to 30 phr relative to the polyvinyl chloride resin.

As a use of the polyvinyl chloride resin composition of this invention containing the citric acid ester compound plasticizer of this invention, Building materials, such as a wall finishing material, a flooring material, a window frame, and a wallpaper; Wire coating material; Interior and exterior materials for automobiles; Agricultural materials such as houses and tunnels; Food packaging materials such as fish such as wraps and trays; Film forming agents such as underbody sealants, plastisols, paints, and inks; Synthetic leather, coated fabrics, hoses, pipes, sheets, baby toys, gloves, and the like.

The method for producing the polyvinyl chloride resin composition using the plasticizer is not particularly limited and may be prepared by methods well known in the art.

Hereinafter, the structure and effects of the present invention will be described in more detail with specific examples and comparative examples, but these examples are only intended to more clearly understand the present invention and are not intended to limit the scope of the present invention. In Examples and Comparative Examples, physical properties were evaluated in the following manner.

Hardness

Based on the ASTM D2240 method, the needle of the hardness tester (A Type) was completely lowered to one of the specimens, and the hardness value was read after 5 seconds, and the average value was taken after testing three places for each specimen. It is used as an index indicating plasticization efficiency.

Volatilization loss

Samples are taken in clean containers, left at 150 ° C for 24 hours and observed for weight changes.

Extraction Resistance

Based on the ASTM D1239 method, specimens with width, length, thickness of 30mm, 30mm, and 1mm were made and immersed in Hexane, Cottonseed Oil, Water, and Soapy Water, after soaking for a certain temperature for a certain time to dry the surface of the specimen and observe the weight change. do.

Example 1

Citric Acid Ester Plasticizers

In a first step, 1.0 mol of citric acid, 3.0 mol of butyl carbitol (diethylene glycol monobutyl ether; butoxydiglycol), 200 g of toluene as a solvent, and 3.0 g of sodium bisulfate were added to a 2 L round flask equipped with a stirrer and a condenser. The reaction was carried out for 12 hours by heating up to 130 ℃.

After the reaction, the unreacted acid was removed under reduced pressure to 5mmHg with a vacuum pump at 200 ° C, neutralized with 10% by weight aqueous sodium carbonate solution, washed with water and dehydrated, and then adsorbent was added and filtered to obtain a primary reactant.

In the second step, 1 mol of the first reactant, 3 mol of iodomethane, and 0.2 mol of sodium hydroxide were added, and the reaction was performed at 0 degrees for 6 hours. In order to remove the unreacted material, the resultant was washed with water and dehydrated, and then filtered to obtain a citric acid ester plasticizer tris (2- (2-butoxyethoxy) ethyl) 2-methoxypropane-1,2,3-tricarboxylate.

Preparation of Polyvinyl Chloride Resin Composition

Specimens were prepared to evaluate the performance of the citric acid-based plasticizers obtained above. In other words, tris (2- (2-butoxyethoxy) ethyl) 2-methoxypropane-1,2,3-tricarboxylate 50phr obtained as a plasticizer in polyvinyl chloride resin (LG Chem, product name LS-100) and stabilizer LFX- 1100 1phr was formulated and a press machine was used to preheat 1 minute, pressurized 1.5 minutes, and cooled for 2 minutes at 185 degrees to make a 2 mm sheet and to prepare various dumbbell-shaped specimens.

The test was performed as described above with the plasticizer and the specimens, and the results are summarized in Table 1 below.

       Comparative Example 1

Specimens were prepared in the same manner as in Example 1, using the most widely used di-2-ethylhexylphthalate as the plasticizer. The prepared specimens were subjected to the same test as in Example 1, and the results are summarized in Table 1 and Table 2 below.

Comparative Example 2

Di-2-ethylhexyl phthalate The test piece was prepared in the same manner as in Example 1 using diisononyl phthalate, which is widely used as a plasticizer, as a plasticizer. The prepared specimens were subjected to the same test as in Example 1, and the results are summarized in Table 1 and Table 2 below.

 Comparative Example 3

Specimens were prepared in the same manner as in Example 1 using acetyltributylcitrate, a traditional eco-friendly plasticizer, as a plasticizer. The prepared specimens were subjected to the same test as in Example 1, and the results are summarized in Table 1 and Table 2 below.

 Comparative Example 4

Specimens were prepared in the same manner as in Example 1 using trioctyl trimellitate as a plasticizer. The prepared specimens were subjected to the same test as in Example 1, and the results are summarized in Table 1 and Table 2 below.

Measurement item Example 1 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Acid value, mgKOH / g 0.01 0.06 0.03 0.20 0.04 Cloud point, ° C -43 -34 -45 or less -45 or less - Pour point, ° C -45 or less -45 or less -45 or less -45 or less -37.5 Shore A Hardness 85 84 88 83 90 Volatilization loss, 150 ° C / 24hr 6.0 5.3 5.2 12.8 0.7

Extraction resistance (wt. Loss%) Condition Example 1 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Hexane 23 ° C / 4hr 0.2 17.9 22.0 0.2 20.0 Cottonseed oil 60 ° C / 24hr 2.3 4.6 5.7 3.5 4.4 Water 60 ° C / 24hr 0.1 0.1 0.1 0.1 0.0 Soapy water 60 ° C / 24hr 2.0 0.5 0.2 3.3 0.0

From the results of Table 1 and Table 2, Example 1, which is a plasticizer of the present invention, is significantly superior in hardness (plasticization efficiency) as compared to Comparative Example 2 and Comparative Example 4, as well as other physical properties, such as Colud point, loss of volatilization. It can be seen that it is excellent in extraction resistance. In addition, compared to Comparative Example 3, which is a similar series, the amount of volatilization is excellent, more suitable for various moldings according to the use, and the extraction resistance to soap water is better, so that the use of more various applications can be expected.

Although described in detail with respect to preferred embodiments of the present invention as described above, those of ordinary skill in the art, without departing from the spirit and scope of the invention as defined in the appended claims Various modifications may be made to the invention. Therefore, changes in the future embodiments of the present invention will not be able to escape the technology of the present invention.

Claims (5)

Citric acid ester compound plasticizer represented by the following formula (1); <Formula 1>

In the above formula, R ₁ is an alkyl group having 1 to 4 carbon atoms, R ₂ is an alkyl group having 1 to 8 carbon atoms, n is 1 to 5. 2. The citric acid ester plasticizer according to claim 1, wherein R ₁ is a methyl group, R ₂ is a butyl group, and n is 2. A polyvinyl chloride resin composition comprising 10 to 150 phr of the plasticizer according to claim 1 or 2 with respect to the polyvinyl chloride resin. The polyvinyl chloride resin composition according to claim 3, wherein the polyvinyl chloride resin composition further comprises up to 30 phr of an additive except for a filler and a pigment with respect to the polyvinyl chloride resin. The method of claim 4, wherein the additive comprises an additional plasticizer material selected from Adipate-based, Sebacate-based, hydrocarbon-based, vegetable oil-based, and TXIB (2,2,4-trimethyl-1,3pentanedioldiisobutylate). Wherein said additional plasticizer material is contained up to 30 phr of the plasticizer component according to claim 1 or 2.