JPH11349766A - Plasticizer for vinyl chloride-based resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a plasticizer for vinyl chloride-based resins excellent in hygienic property and compatibility with vinyl chloride resin and capable of imparting physical properties to the resins. SOLUTION: This plasticizer for vinyl chloride-based resins comprises (a) 0-3 wt.% triacyl(2-4C)glyceride, (b) 50-85 wt.% diacyl(2-4C).monoacyl(10-30C) glyceride, (c) 10-50 wt.% monoacyl(24C)diacyl(10-30C)glyceride and (d) 0-20 wt.% triacyl(10-30C)glyceride and has >=50 iodine value.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a plasticizer for a vinyl chloride resin, and more particularly, to a plasticizer comprising a mixture of glycerides, having excellent hygiene properties and excellent compatibility with the vinyl chloride resin. The present invention relates to a plasticizer for a vinyl chloride resin capable of imparting excellent physical properties.

[0002]

2. Description of the Related Art Vinyl chloride resins can be used for various purposes because their hardness can be easily adjusted by using a plasticizer at low cost.

Usually, phthalate plasticizers such as dioctyl phthalate and dibutyl phthalate, and adipic acid plasticizers such as dioctyl adipate are used as plasticizers for vinyl chloride resins. It is widely used as a plasticizer that can give excellent properties to the resin.

However, these compounds are suspected to be substances that disturb the endocrine action (so-called environmental hormones), and it is strongly desired to provide a plasticizer for vinyl chloride resin which is excellent in hygiene and replaces them. It is rare.

It has also been proposed to use a triglyceride compound having a structure similar to that of natural fats and oils as a plasticizer. For example, JP-A-58-23845 discloses an epoxidized vegetable oil and a plasticizer having 2 carbon atoms. Extrusion-forming vinylidene chloride copolymer composition comprising a glyceride selected from a glycerol ester having an acyl group formed from lower fatty acids having 1 to 6 carbon atoms and an acyl group formed from higher fatty acids having 8 to 22 carbon atoms. And JP-A-58-32647 and JP-A-58-167.
No. 638 discloses an acyl group having 2 carbon atoms and 10 to 10 carbon atoms.
It has been proposed to add a mixed glyceride having 14 acyl groups to a vinyl chloride resin.
Japanese Patent No. 4918 proposes a vinyl chloride paste resin composition comprising a mixed plasticizer composed of didecyl phthalate and glycerin diacetoxy monolaurate. These glycerides have compatibility and plasticization efficiency. Or, because of poor physical properties, a material having satisfactory performance in practical use has not yet been obtained.

Accordingly, an object of the present invention is to provide excellent hygiene,
Another object of the present invention is to provide a plasticizer for a vinyl chloride resin which has excellent compatibility with a vinyl chloride resin and can impart excellent physical properties to the resin.

[0007]

Means for Solving the Problems As a result of diligent studies, the inventors of the present invention have a structure similar to that of natural fats and oils containing a specific glyceride compound in a specific ratio, and have an iodine value in a specific range. The inventors have found that the mixture can achieve the above object, and have reached the present invention.

That is, the present invention relates to (a) triacyl (C2
-4) glyceride 0-3% by weight, (b) diacyl (C
2-4) monoacyl (C10-30) glyceride 5
0 to 85% by weight, (c) 10 to 50% by weight of monoacyl (C2 to 4) diacyl (C10 to 30) glyceride and (d) 0 to 0 of triacyl (C10 to 30) glyceride
The present invention provides a plasticizer for a vinyl chloride-based resin, which is composed of -20% by weight and has an iodine value of 50 or more.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the plasticizer for a vinyl chloride resin of the present invention will be described in detail.

In the glyceride compound of each of the components (a) to (d) constituting the plasticizer for a vinyl chloride resin of the present invention, the acyl (C2-4) group may be acetyl,
Groups such as propionyl, butyryl, and isobutyryl; and acyl (C10-30) groups include, for example, obutsilic acid, caproleic acid, undecylenic acid, lindelic acid, tuzunic acid, physeteric acid, myristoleic acid, palmitoleic acid, Petroselinic acid, Petroselinic acid, Oleic acid, Petroselinic acid, Oleic acid, Elaidic acid, Asclepic acid, Vaccenic acid, Gadolinic acid, Gondoic acid, Cetreic acid, Erucic acid, Brassic acid, Seracoleic acid, Ximenic acid, Lumecitrate, Linoleic acid , Hiragoic acid, α-eleostearic acid, β-eleostearic acid, punicic acid, linolenic acid, γ-linolenic acid,
The main component is an unsaturated acyl group derived from unsaturated carboxylic acids such as moloctic acid, stearidonic acid, arachidonic acid, succinic acid, and nisinic acid, and decanoic acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, and stearic acid. , Arachinic acid, behenic acid, lignoceric acid, cerotic acid, montanic acid, melicinic acid and the like.

The iodine value of the plasticizer for a vinyl chloride resin of the present invention comprising a mixture of the glycerides of the above components (a) to (d) is 50 or more, preferably 80 or more. If the iodine value is less than 50, the plasticization efficiency may be reduced, and bleeding may be easily caused.

The method for producing the plasticizer for vinyl chloride resin of the present invention comprising a mixture of the glycerides of the above components (a) to (d) is not particularly limited. For example, (1) First, an oil or fat (triacyl (C10 To 30) glyceride), adding glycerin to produce a mixture of mono-, di- and triglycerides, and acylating the mixture with an acid anhydride such as acetic anhydride; (2) fats and oils and triacetin, tripropionin;
It can be easily produced by a method of transesterifying a lower triglyceride such as tributyrin or (3) a method of esterifying glycerin with a mixed acid under a base or acid catalyst. Among these, (2)
Is the simplest method, and it is preferable to use this method. In the method (2), the ratio of each glyceride can be changed by changing the mixing ratio of fats and oils and lower glycerides and / or reaction conditions.

The oils and fats include, for example, soybean oil, linseed oil, tung oil, castor oil, safflower oil, palm oil, rapeseed oil, cottonseed oil, corn oil, rice bran oil, coconut oil, beef tallow, lard oil, fish oil Such as animal and vegetable oils, such that the glyceride mixture has an iodine value of 50 or more,
They can be used alone or as a mixture of several types.
In particular, the use of soybean oil is preferable because the desired triglyceride mixture can be easily obtained.

The plasticizer for the vinyl chloride resin of the present invention has a composition of 0 to 3% by weight, preferably 0 to 2% by weight, and 50 to 85% by weight, preferably 50 to 85% by weight, of the component (b).
80% by weight, 10 to 50% by weight, preferably 15 to 50% by weight of component (c) and 0 to 20% by weight, preferably 0 to 15% by weight of component (d). Here, when the component (b) is less than 50% by weight or when the component (c) is more than 50% by weight, migration to another resin is likely to occur, and when the component (b) is more than 85% by weight. Alternatively, when the component (c) is less than 10% by weight, elongation is reduced or bleeding occurs. When the amount of the component (a) is more than 3% by weight, the anti-tension becomes small, and the physical properties such as the loss of elongation are reduced.
If the amount is larger than the above, the compatibility is reduced, and the plasticizing efficiency cannot be obtained.

The plasticizer for the vinyl chloride resin of the present invention is usually used in an amount of 1 to 100 parts by weight based on 100 parts by weight of the vinyl chloride resin.
It can be appropriately added in the range of parts by weight depending on the use and purpose.

Next, a vinyl chloride resin composition containing the plasticizer for vinyl chloride resin of the present invention will be described in detail.

The above-mentioned vinyl chloride resin is not particularly limited to a polymerization method such as bulk polymerization, solution polymerization, suspension polymerization and emulsion polymerization. Examples thereof include polyvinyl chloride, chlorinated polyvinyl chloride, and polyvinylidene chloride. , Chlorinated polyethylene, vinyl chloride-vinyl acetate copolymer, vinyl chloride
Ethylene copolymer, vinyl chloride-propylene copolymer,
Vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride-vinylidene chloride copolymer,
Vinyl chloride-styrene-maleic anhydride terpolymer,
Vinyl chloride-styrene-acrylonitrile terpolymer, vinyl chloride-butadiene copolymer, vinyl chloride-isoprene copolymer, vinyl chloride-chlorinated propylene copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer Chlorine-containing resins such as coalesce, vinyl chloride-maleic acid ester copolymer, vinyl chloride-methacrylic acid ester copolymer, vinyl chloride-acrylonitrile copolymer, vinyl chloride-various vinyl ether copolymers, and their mutual blends Products or their chlorine-containing resins and other chlorine-free synthetic resins, such as acrylonitrile-
Styrene copolymer, acrylonitrile-styrene-butadiene terpolymer, ethylene-vinyl acetate copolymer,
Examples thereof include ethylene-ethyl (meth) acrylate copolymers, blends with polyester, and the like, block copolymers, graft copolymers, and the like.

A plasticizer other than the plasticizer for vinyl chloride resin of the present invention can be used in combination with the vinyl chloride resin composition, and these plasticizers are usually used for vinyl chloride resin. Any available plasticizer can be used. For example, phthalate plasticizers such as dibutyl phthalate, butylhexyl phthalate, diheptyl phthalate, dioctyl phthalate, diisononyl phthalate, diisodecyl phthalate, dilauryl phthalate, dicyclohexyl phthalate, and dioctyl terephthalate; dioctyl adipate, diisononyl adipate,
Adipate plasticizers such as diisodecyl adipate and di (butyldiglycol) adipate; triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tri (isopropylphenyl) phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tri ( Phosphate plasticizers such as butoxyethyl) phosphate and octyl diphenyl phosphate; polyhydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3
-Propylene glycol, 1,3-butanediol,
1,4-butanediol, 1,5-hexanediol,
1,6-hexanediol, neopentyl glycol and the like, and dibasic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, and isophthalic acid , Terephthalic acid, etc., and a polyester plasticizer using a monohydric alcohol or monocarboxylic acid as a stopper if necessary; other, tetrahydrophthalic acid plasticizer, azelaic acid plasticizer, sebacic acid plasticizer, stearic acid Plasticizers, citric acid plasticizers, trimellitic acid plasticizers, pyromellitic acid plasticizers, and biphenylene polycarboxylic acid plasticizers. Some of these plasticizers are suspected to be endocrine disruptors, but by using the plasticizer of the present invention having a structure similar to that of natural fats and oils, the amount of the plasticizer is reduced and the risk is reduced. Can be done.

Further, the above-mentioned vinyl chloride resin composition includes:
Metals of carboxylic acids or phenols (Li, Na, K, Ca, M)
g, Ba, Sr, Cd, Zn, Al, Sn, organic Sn)
A normal salt, an acidic salt, a basic salt or an overbased salt can be used in combination.

Examples of the carboxylic acid include caproic acid, caprylic acid, pelargonic acid, 2-ethylhexylic 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, arachinic acid, behenic acid, erucic acid, brassic acid and similar acids and mixtures of the above naturally occurring acids such as tallow fatty acid, coconut oil fatty acid, tung oil fatty acid, soybean oil fatty acid and cottonseed oil fatty acid, benzoic acid, p- Tertiary butyl benzoic acid, ethyl benzoic acid, isopropyl benzoic acid, toluic acid, xylic acid, salicylic acid, 5-tert-octyl salicylic acid, naphthenic acid, cyclohexanecarboxylic acid, adipic acid, maleic acid, acrylic acid, methacrylic acid, etc. The phenols include, for example, phenol, cresol, ethylphenol, cyclohexylphenol, nonylphenol, dodecylphenol and the like.

The above-mentioned vinyl chloride resin composition includes:
Further, various additives usually used as additives for vinyl chloride resins, for example, hydrotalcite compounds, β-diketone compounds, perchlorates, zeolite compounds, organic phosphite compounds, phenolic or sulfur-based compounds An oxidizing agent, an epoxy compound, a polyol, an ultraviolet absorber, a hindered amine-based light stabilizer, other inorganic metal compounds, a foaming agent, and the like can also be blended.

The hydrotalcite compound is a complex salt compound comprising magnesium and / or an alkali metal and aluminum or zinc, magnesium and aluminum as represented by the following general formula (I), and is obtained by dehydrating water of crystallization. It may be.

Ia _x1 Mg _x2 Zn _x3 Al _y (OH) _{x1 + 2 (x2 + x3) + 3y-2} · (CO ₃ ) _{1-z / 2} (ClO ₄ ) _z · mH ₂ O (I) In the formula, Ia represents an alkali metal atom, x1, x
2, x3, y, and z each represent a condition represented by the following equation, and m represents a real number. 0 ≦ x1 ≦ 10, 0 ≦ x2 ≦ 1
0, 0 ≦ x3 ≦ 10, 0 ≦ y ≦ 10, 0 ≦ z ≦ 10, provided that x1 and x2 never become 0 at the same time. )

The hydrotalcite compound may be a natural product or a synthetic product. The method for synthesizing the synthetic product is described in JP-B-46-2280, JP-B-50-30039, and JP-B-51-29129.
Gazette, Japanese Patent Publication No. 3-36839, JP-A-61-174
Known methods described in, for example, Japanese Patent Application Laid-Open No. 270, JP-A-5-179052 and the like can be exemplified. Further, the above hydrotalcite compound can be used without being limited by its crystal structure, crystal particle system and the like.

The surface of the hydrotalcite compound may be a higher fatty acid such as stearic acid, a higher fatty acid metal salt such as an alkali metal oleate, an organic metal sulfonate such as an alkali metal dodecylbenzenesulfonate, or a higher salt thereof. It may be one coated with a fatty acid amide, a higher fatty acid ester or a wax.

Examples of the β-diketone compound include dibenzoylmethane, benzoylacetone, stearoylbenzoylmethane, caproylbenzoylmethane, dehydroacetic acid, tribenzoylmethane, 1,3-bis (benzoylacetyl) benzene and the like. Metal salts (lithium, sodium, potassium, calcium, magnesium, barium, zinc, nickel, cobalt, manganese, copper, iron, titanium, etc.).

The above perchlorates include lithium perchlorate, sodium perchlorate, potassium perchlorate, strontium perchlorate, barium perchlorate, zinc perchlorate,
Cadmium perchlorate, aluminum perchlorate, lead perchlorate, ammonium perchlorate and the like. These perchlorates may be anhydrous or hydrated, and may be butyl diglycol, butyl diglycol adipate. Or a dehydrated product thereof dissolved in an alcohol-based or ester-based solvent.

The zeolite compound is an alkali or alkaline earth metal aluminosilicate having a unique three-dimensional zeolite crystal structure.
A-type, X-type, Y-type and P-type zeolites, monodenite, analcite, sodalite family aluminosilicates,
Examples thereof include clinbutyrolite, erionite, and chabazite. Either a hydrous product containing water of crystallization of these zeolite compounds (so-called zeolite water) or an anhydride from which water of crystallization has been removed may be used.

Examples of the organic phosphite compound include, for example, triphenyl phosphite, tris (2,4-ditert-butylphenyl) phosphite, tris (nonylphenyl) phosphite, tris (dinonylphenyl) phosphite, Tris (mono- and di-mixed nonylphenyl) phosphite, bis (2-tert-butyl-4,6-dimethylphenyl) .ethyl phosphite, diphenyl acid phosphite, 2,2'-methylenebis (4,6-di Tributylphenyl) octyl phosphite, diphenyldecyl phosphite, phenyl diisodecyl phosphite, tributyl phosphite, tris (2-ethylhexyl) phosphite, tridecyl phosphite, trilauryl phosphite, dibutyl acid phosphite,
Dilauryl acid phosphite, trilauryl trithiophosphite, bis (neopentyl glycol)
1,4-cyclohexanedimethyldiphosphite, bis (2,4-ditertbutylphenyl) pentaerythritol diphosphite, bis (2,6-ditertbutyl-4-)
Methylphenyl) pentaerythritol diphosphite, distearylpentaerythritol diphosphite, phenyl-4,4'-isopropylidenediphenol pentaerythritol diphosphite, tetra (C
12-15 mixed alkyl) -4,4'-isopropylidenediphenylphosphite, bis [2,2'-methylenebis (4,6-diamylphenyl)] isopropylidenediphenylphosphite, hydrogenated-4,4 ' -Isopropylidene diphenol polyphosphite, bis (octylphenyl) bis [4,4'-n-butylidenebis (
2-tert-butyl-5-methylphenol)] • 1,6-hexanediol • diphosphite, tetratridecyl •
4,4'-butylidenebis (2-tert-butyl-5-methylphenol) diphosphite, hexa (tridecyl)
-1,1,3-tris (2-methyl-5-tert-butyl-
4-hydroxyphenyl) butane triphosphonite,
9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2-butyl-2-ethylpropanediol, 2,4,6-tri-tert-butylphenol monophosphite, and the like.

Examples of the phenolic antioxidants include 2,6-di-tert-butyl-p-cresol and 2,6-di-tert-butyl-p-cresol.
Diphenyl-4-octadecyloxyphenol, stearyl (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, distearyl (3,5-di-tert-butyl-4-hydroxybenzyl) phosphonate, tridecyl-3,3 5-di-tert-butyl-4-hydroxybenzylthioacetate, thiodiethylenebis [(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 4,4′-thiobis (6-tert-butyl-m -Cresol), 2-octylthio-4,6-di (3,5-ditert-butyl-4-hydroxyphenoxy) -s-triazine, 2,2'-methylenebis (4-methyl-6-tert-butylphenol) , Bis [3,3-bis (4-hydroxy-3-tert-butylphenyl) butyric acid]
Glycol ester, 4,4'-butylidenebis (4,
6-di-tert-butylphenol), 2,2′-ethylidenebis (4,6-di-tert-butylphenol), 1,1,3
-Tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, bis [2-tert-butyl-4-methyl-6- (2-hydroxy-3-tert-butyl-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-ditert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,3,5-tris [(3,5-di-tert. Tributyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, 2-tert-butyl-4-methyl- 6- (2-Acroyloxy-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-tert-butyl-4-hydroxy-5-methylphenyl) propionate], tocopherols and the like. Can be

Examples of the sulfur-based antioxidants include dialkylthiodipropionates such as dilauryl, dimyristyl, myristylstearyl, and distearyl esters of thiodipropionic acid, and pentaerythritol tetra (β-dodecylmercaptopropionate). And β-alkyl mercaptopropionate esters of polyols.

Examples of the epoxy compound include epoxidized animal and vegetable oils such as epoxidized soybean oil, epoxidized linseed oil, epoxidized tung oil, epoxidized fish oil, epoxidized tallow oil, epoxidized castor oil, epoxidized safflower oil, and the like. Epoxidized methyl stearate, -butyl, -2
-Ethylhexyl, -stearyl ester, epoxidized polybutadiene, tris (epoxypropyl) isocyanurate, epoxidized tall oil fatty acid ester, epoxidized linseed oil fatty acid ester, bisphenol A diglycidyl ether, vinylcyclohexene diepoxide, dicyclohexene carboxylate , 3,4-epoxycyclohexenemethylepoxycyclohexanecarboxylate, bisphenol type or novolak type epoxy resin.

Examples of the polyols include trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, polypentaerythritol, pentaerythritol or dipentaerythritol half-ester stearic acid, bis (dipentaerythritol) adipate, Glycerin,
Tris (2-hydroxyethyl) isocyanurate, sorbitol, mannitol, trehalose and the like can be mentioned.

As the above-mentioned ultraviolet absorber, for example,
4-dihydroxybenzophenone, 2-hydroxy-4
-Methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-tert-butyl-4 '-(2-methacryloyloxyethoxyethoxy) benzophenone, 5,5'-methylenebis (2-hydroxy-4 2-hydroxybenzophenones such as -methoxybenzophenone); 2- (2-hydroxy-5)
-Methylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-3,5-ditert-butylphenyl) -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-C
7-9 mixed alkoxycarbonylethylphenyl) triazole, 2- (2-hydroxy-3,5-dicumylphenyl) benzotriazole, 2,2′-methylenebis (4-tert-octyl-6-benzotriazolylphenol) 2- (2-hydroxyphenyl) benzotriazoles such as polyethylene glycol ester of 2- (2-hydroxy-3-tert-butyl-5-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-octoxyphenyl) -4,6 -Bis (2,4-dimethylphenyl)-
2- (2-hydroxyphenyl) -1,3,5-triazines such as 1,3,5-triazine; phenyl salicylate, resorcinol monobenzoate, 2,4-di-tert-butylphenyl-3,5-di-tert. Tributyl-4-hydroxybenzoate, 2,4-ditert-amylphenyl-
3,5-di-tert-butyl-4-hydroxybenzoate,
Benzoates such as hexadecyl-3,5-ditert-butyl-4-hydroxybenzoate; 2-ethyl-2 '
Substituted oxanilides such as -ethoxyoxanilide, 2-ethoxy-4'-dodecyloxanilide; ethyl-α
-Cyano-β, β-diphenylacrylate, methyl-
Examples include cyanoacrylates such as 2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate.

Examples of the hindered amine light stabilizer include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, , 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, tetrakis (2,2,6,6-
Tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, tetrakis (1,2,2
2,6,6-pentamethyl-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-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2-butyl-2- (3,5-di-tert-butyl-4-
Hydroxybenzyl) malonate, 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol / diethyl succinate 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-piperidylamino) hexane /
2,4-dichloro-6-tert-octylamino-s-triazine polycondensate, 1,5,8,12-tetrakis [2,
4-bis (N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl) amino) -s-triazine-
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-piperidyl) amino-s-
Triazin-6-ylamino] undecane, 1,6,1
1-tris [2,4-bis (N-butyl-N- (1,
2,2,6,6-pentamethyl-4-piperidyl) amino-s-triazin-6-ylamino] undecane.

The above-mentioned other inorganic metal compounds include
Examples include calcium silicate, calcium phosphate, calcium oxide, calcium hydroxide, magnesium silicate, magnesium phosphate, magnesium oxide, magnesium hydroxide and the like.

Examples of the foaming agent include azo foaming agents such as azodicarbonamide, azobisisobutylnitrile, diazoaminobenzene, diethylazodicarboxylate, diisopropylazodicarboxylate, and azobis (hexahydrobenzonitrile). N, N'-
Nitroso-based blowing agents such as dinitropentamethylenetetramine and N, N'-dimethyl-N, N'-dinitroterephthalamine; benzenesulfonylhydrazide, p-toluenesulfonylhydrazide, 3,3'-disulfonehydrazidephenylsulfone, toluenedisulfonyl Hydrazide-based blowing agents such as hydrazone, thiobis (benzenesulfonylhydrazide), toluenesulfonylazide, toluenesulfonylsemicarbazide, p, p′-bis (benzenesulfonylhydrazide) ether; p-toluenesulfonylsemicarbazide, 4,4′-oxybis ( Carbazide-based blowing agents such as sulfonyl semicarbazide); triazine-based blowing agents such as trihydrazinotriazine and 1,3-bis (o-biphenyltriazine).

Further, other stabilizing aids usually used for vinyl chloride resins can be added. Such stabilizing aids include, for example, diphenylthiourea, diphenylurea, anilinodithiotriazine, melamine, benzoic acid, cinnamic acid, p-tert-butylbenzoic acid and the like.

In addition, if necessary, additives usually used for vinyl chloride resins, for example, fillers, coloring agents, crosslinking agents, antistatic agents, antifogging agents, plateout preventing agents, surface treatment agents, lubricants , A flame retardant, a fluorescent agent, a fungicide, a bactericide, a metal deactivator, a release agent, a pigment, a processing aid, an antioxidant, a light stabilizer and the like.

Further, the vinyl chloride resin composition containing the plasticizer for vinyl chloride resin of the present invention can be used without any limitation in the method of processing the vinyl chloride resin. For example, it can be suitably used for calendering, rolling, extrusion molding, melt rolling, pressure molding, powder molding, and the like.

The vinyl chloride resin composition containing the plasticizer for vinyl chloride resin of the present invention is used for building materials such as wall materials, floor materials, window frames, and wallpaper; electric wire covering materials; Materials: agricultural materials such as houses and tunnels; fish food packaging materials such as wraps and trays; paints, hoses, pipes, sheets, toys and other miscellaneous goods.

[0042]

Next, the present invention will be described in more detail with reference to Production Examples and Examples, but the present invention is not limited by the following Production Examples and Examples.

Production Example 1 Soybean oil and triacetin were mixed in the molar ratio shown in Table 1 below, and 0.1% by weight of sodium methoxide was added thereto, followed by a reaction (ester exchange reaction) at 230 ° C. for 6 hours. Was. After cooling to 80 ° C. or lower, 0.75 mol of phosphoric acid was added to 1 mol of sodium methoxide to inactivate, and purified by steam distillation and dehydration under reduced pressure. The composition (unit;% by weight) and iodine value of the obtained mixed glyceride (GR-1 to 4) are shown in [Table 1] below. Triesterin was used instead of triacetin, or transesterification was similarly performed using beef tallow instead of soybean oil to purify the mixed glyceride. The obtained mixed glyceride (GR-
The composition (unit;% by weight) and iodine value of (5, 6) are shown in Tables 2 and 3 below.

[0044]

[Table 1]

[0045]

[Table 2]

[0046]

[Table 3]

Example 1 Rolls were kneaded with the following composition and pressed to prepare a 1 mm laminated sheet. JIS specified from this sheet
Specimens were prepared according to K 7113, and 100% modulus (kg / cm ² ), anti-tension (kg / cm ² ) and elongation (%) were measured. Further, the press sheet was hung and sealed in a beaker filled with water so as not to come in contact with water, and was placed in a gear oven at 70 ° C. for one week, and then the bleeding state of the sheet surface was visually evaluated. A 5 mm × 35 mm press sheet was placed on an ABS plate, and a 1 kg weight was placed on the press sheet so that the load was evenly applied. The ABS sheet was placed in a 70 ° C. gear oven for 1 week. The state of transition to was evaluated visually. These were represented by ○ (none at all), Δ (somewhat), × (large) and XX (extremely large). Further, the plasticizing efficiency was also obtained by a conventional method. Here, the plasticization efficiency is defined as 10%, which is the same as that of a vinyl chloride resin containing 50 parts by weight of di-2-ethylhexyl phthalate.
This is a value obtained by dividing the blending amount (parts by weight) of the test plasticizer giving 0% modulus by 50, and the smaller the numerical value, the better the plasticization efficiency. The results are shown in Table 4 below.

(Blending) Parts by weight Vinyl chloride resin (degree of polymerization 1050) 100 Barium stearate 1 Zinc stearate 0.8 Plasticizer (see Table 4) 50

[0049]

[Table 4]

As is evident from the above examples, tri-long chain acyl glycerides such as soybean oil have large bleeding and migration properties and insufficient plasticization efficiency. The migration to resin is large, and the physical properties are not satisfactory. Also,
Even mixed acyl glycerides which do not fall within the specific ratio of the present invention are not yet satisfactory in terms of physical properties or compatibility. Further, as in the present invention, even if the acyl glyceride has a short-chain or long-chain acyl group, if the iodine value is less than 50, the compatibility is insufficient and the plasticizing efficiency is poor.

On the other hand, the plasticizer, which is a specific mixed glyceride of the present invention, does not transfer to bleed or other resins even when blended with a vinyl chloride resin, shows a sufficient plasticizing efficiency, and exhibits physical properties. And has performance comparable to that of general-purpose dioctyl phthalate.

[0052]

The plasticizer for vinyl chloride resin of the present invention comprises:
It is excellent in hygiene, excellent in compatibility with a vinyl chloride resin, and can impart excellent physical properties to the resin.

Claims (5)

[Claims] (1) 0 to 3% by weight of triacyl (C2-4) glyceride, (b) 50 to 85% by weight of diacyl (C2 to 4) monoacyl (C10 to 30) glyceride, (c) monoacyl (C2 -4) ・ Diacyl (C10
-30) glyceride 10-50% by weight and (d) triacyl (C10-30) glyceride 0-20% by weight
And a plasticizer for a vinyl chloride resin having an iodine value of 50 or more. 2. The plasticizer for a vinyl chloride resin according to claim 1, which is obtained by transesterification of triacyl (C2-4) glyceride and triacyl (C10-30) glyceride. 3. The plasticizer for a vinyl chloride resin according to claim 2, wherein the triacyl (C10-30) glyceride is a natural fat or oil. 4. The plasticizer for a vinyl chloride resin according to claim 3, wherein the natural fat or oil is soybean oil. 5. The plasticizer 1 for a vinyl chloride resin according to claim 1, wherein 100 parts by weight of the vinyl chloride resin is used.
A vinyl chloride-based resin composition, which is blended with 100 to 100 parts by weight.