JPH11158486A - Epoxidized animal or vegetable oil composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an epoxidized animal or vegetable oil compsn. which improves the heat stability and discoloration resistance of a vinyl chloride resin by subjecting a mixture of a plurality of animal or vegetable oils different in iodine value to transesterification and then to epoxidation. SOLUTION: 100 pts.wt. animal or vegetable oil mixture having an iodine value of 100-150 and prepd. by mixing 10-80 wt.% animal or vegetable oil (e.g. palm oil) having an iodine value lower than 120 and 10-80 wt.% animal or vegetable oil having an iodine value of 150 or higher is mixed with 0.001-10 pts.wt. enzyme (e.g. lipase) immobilized on diatomaceous earth or the like, is thus subjected to transesterification, and is epoxidized with hydrogen peroxide or the like, giving an epoxidized animal or vegetable oil compsn. having an oxirane oxygen content of 3.0 wt.% or higher. Pref., the compsn. is compounded with an antioxidant, an ultraviolet absorber, etc., each in an amt. of 0.01-10 wt.%. 100 pts.wt. vinyl chloride resin is compounded with 0.01-100 pts.wt. above- prepd. compsn., a normal, acidic, or basic metal salt of a carboxylic acid compd., a phosphoric acid compd., or a phenolic compd. to give a vinyl resin compsn.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an epoxidized animal and vegetable oil composition, and more particularly to a vinyl chloride resin obtained by transesterifying a mixture of two or more animal and vegetable oils having different iodine values and then epoxidizing the mixture. The present invention relates to an epoxidized animal or vegetable oil composition which can be suitably used as a stabilizer or a plasticizer for use.

[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.

[0003] However, it is known that vinyl chloride resins are difficult to stabilize against light and heat, and are liable to be decomposed mainly due to dehydrohalogenation during heat molding or use of products. . For this reason, attempts have been made to improve the stability of vinyl chloride resins by using a metal compound as a main stabilizer and various other stabilizing aids in combination.

In recent years, cadmium-based, lead-based, and organotin-based stabilizers which exhibit relatively excellent performance in consideration of the adverse effects on the environment or the human body, but are toxic, have been compared with the former. The development of low-toxic barium / zinc-based and calcium / zinc-based stabilizers is progressing, but has the disadvantage of insufficient heat resistance, and the development of better stabilizing aids is expected. It is rare.

[0005] Epoxidized animal and vegetable oils are widely used as stabilizers or plasticizers for improving the heat resistance of vinyl chloride resins.

Among epoxidized animal and vegetable oils, epoxidized soybean oil, epoxidized linseed oil and the like are widely used, but they have drawbacks such as bleeding, and further improvement in thermal stability is desired.

There have been attempts to use epoxidized animal and vegetable oils obtained by epoxidizing various other animal and vegetable oils as stabilizers or plasticizers for vinyl chloride resins. However, it has disadvantages such as coloration, and satisfactory performance has not been obtained.

Accordingly, an object of the present invention is to provide an epoxidized animal or vegetable oil which has an effect of improving various properties such as heat stability and coloring property, and which can be suitably used as a stabilizer or a plasticizer for a vinyl chloride resin. To provide.

[0009]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors have obtained an epoxidized animal and vegetable oil composition obtained by subjecting a specific animal and vegetable oil mixture to transesterification and epoxidation. The present inventors have found that when blended with a vinyl chloride resin, the resin has an excellent effect of improving various properties such as thermal stability and coloring properties, and have reached the present invention.

[0010] That is, the present invention provides a method for producing a compound having different iodine values.
It is intended to provide an epoxidized animal and vegetable oil composition obtained by transesterifying a mixture of at least one kind of animal and vegetable oils and then epoxidizing the mixture.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the epoxidized animal and vegetable oil composition of the present invention will be described in detail. The animal and vegetable oils used in the present invention include, for example, vegetable oils such as soybean oil, cottonseed oil, palm oil, linseed oil, rapeseed oil, olive oil, corn oil, coconut oil, safflower oil; and animal oils such as tallow, lard, fish oil and the like. Two or more of these compounds having different iodine values are used.

The animal and vegetable oil mixture used for the transesterification in the present invention comprises (a) a mixture having an iodine value of less than 120,
It is preferred to contain 10 to 80% by weight of 80% by weight and (b) those having an iodine value of 150 or more.

As the animal and vegetable oil having an iodine value of less than 120 of the component (a), palm oil, rapeseed oil, tallow, etc. are particularly preferable, and the component (a) has an iodine value of 150 or more as the component (b). It is preferable to transesterify an animal and vegetable oil mixture obtained by mixing linseed oil. Further, the above animal and vegetable oil mixture has an iodine value of 1 as a whole of the mixture.
A mixture obtained by mixing two or more kinds of the above-mentioned animal and vegetable oils having different iodine values so as to be 00 to 150 is preferable.

The method for transesterification of the animal and vegetable oil mixture is not particularly limited, and may be, for example, a method using a chemical catalyst of an alkali metal or alkyl metal alcoholate, or a method using an enzyme such as lipase. However, in the former case, it is necessary to wash with water in order to remove the catalyst from the system at the stage when the transesterification is completed, and there is a drawback such that hydrolysis occurs during the washing and the yield is reduced. The transesterification used is preferably performed.

The lipase used herein is, for example, genus Risopussp., Genus Alcaligenes sp., Genus Chromobacterium.
p. ), Candida sp., Mucor sp., Pancreatic lipase and the like.

These enzymes can be used alone, but usually it is preferable to use them by adsorbing or immobilizing them on diatomaceous earth, alumina, activated carbon or other known supports. Many of these immobilized lipases are commercially available, and include, for example, Lipase QLC (manufactured by Meito Sangyo Co., Ltd.).

The amount of the lipase immobilized here is as follows:
0.001 to 10 per 100 parts by weight of the animal and vegetable oil mixture
Parts by weight, preferably 0.01 to 5 parts by weight,
When the amount is less than 01 parts by weight, the catalytic activity is not sufficiently exhibited.
Not only is it unnecessary to use more than 0 parts by weight,
Since a large amount of water coexisting with the immobilized enzyme is brought into the system, hydrolysis of the animal and vegetable oil mixture may occur, which is not preferable.

The epoxidation of the transesterified animal or vegetable oil mixture can be carried out by a conventional method such as a method using hydrogen peroxide or a method using an organic peracid such as peracetic acid. The method of conversion is not particularly limited.

The epoxidized animal / vegetable oil composition of the present invention has excellent oxirane oxygen content of 3.0% by weight or more, particularly 5.0% by weight or more, in addition to excellent stability. It is preferable to show good performance when blended with vinyl chloride resin.

The epoxidized animal and vegetable oil composition of the present invention preferably has an acid value of less than 1, and when an acid value of more than 1 is used, the thermal stability of the composition itself may be reduced. In addition, when blended with a vinyl chloride resin or the like, the performance may be adversely affected.

The epoxidized vegetable oil composition of the present invention may contain various additives such as an antioxidant and an ultraviolet absorber in order to prevent its deterioration due to heat, light and the like. Is preferably 0.01 to 10% by weight.

The epoxidized animal / vegetable oil composition of the present invention is used as a stabilizer or a plasticizer for a vinyl chloride resin, a reactive diluent for an epoxy resin, and the like, and its use is not particularly limited. However, it can be suitably used especially as a stabilizer or a plasticizer for a vinyl chloride resin.

Here, the 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-chloride Vinylidene copolymer, vinyl chloride-styrene-maleic anhydride terpolymer, vinyl chloride-styrene-acrylonitrile copolymer, 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 vinyl chloride-maleic acid ester copolymer, vinyl chloride-methacrylic acid ester copolymer, vinyl chloride-acrylonitrile copolymer, vinyl chloride-various vinyl ether copolymers, and their blended products or others Chlorine-free synthetic resin, for example,
Examples include acrylonitrile-styrene copolymers, ethylene-vinyl acetate copolymers, ethylene-ethyl (meth) acrylate copolymers, blends with polyester, and the like, block copolymers, graft copolymers, and the like.

The epoxidized animal / vegetable oil composition of the present invention can be used as a stabilizer capable of exhibiting an effect even in a small amount, or as a plasticizer exhibiting an effect when incorporated in a relatively large amount. Is not particularly limited, but is usually 0.1 to 100 parts by weight of the vinyl chloride resin.
0.01 to 100 parts by weight, preferably 0.05 to 80 parts by weight, particularly preferably 0.1 to 60 parts by weight,
If the addition is less than 1 part by weight, a sufficient effect cannot be obtained, and
Even if it is added in more than 0 parts by weight, no improvement in the effect is seen,
It is not preferable because bleeding may occur.

In addition to the epoxidized animal and vegetable oil composition of the present invention, the vinyl chloride resin may contain a metal (Li, Na, K, C) of a carboxylic acid, an organic phosphoric acid or a phenol.
a, Mg, Ba, Sr, Cd, Zn, Al, Sn, organic Sn) normal salt, acidic salt, basic salt or overbased salt can be used in combination.

Examples of the carboxylic acids 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 tallow fatty acids, coconut A mixture of the above naturally occurring acids such as oil fatty acids, tung oil fatty acids, soybean oil fatty acids and cottonseed oil fatty acids, benzoic acid,
p-tert-butylbenzoic acid, ethylbenzoic acid, isopropylbenzoic acid, toluic acid, xylylic acid, salicylic acid, 5
Tertiary octyl salicylic acid, naphthenic acid, cyclohexanecarboxylic acid, adipic acid, maleic acid, acrylic acid,
Examples of the organic phosphoric acids include mono- or dioctyl phosphoric acid, mono- or didodecyl phosphoric acid, mono- or di-octadecyl phosphoric acid, mono- or di- (nonylphenyl) phosphoric acid, phosphonic acid nonyl phenyl ester, and phosphonic acid. Examples of the phenols include phenol, cresol, ethylphenol, cyclohexylphenol, nonylphenol, and dodecylphenol.

Further, various additives usually used as additives for vinyl chloride resins, for example, plasticizers, hydrotalcite compounds, β-diketone compounds, perchlorates, zeolite compounds, organic phosphite compounds, A phenolic or sulfuric antioxidant, an epoxy compound, a polyol, an ultraviolet absorber, a hindered amine light stabilizer, other inorganic metal compounds, a foaming agent, and the like can be used in combination.

As the above-mentioned plasticizer, any plasticizer usually used for vinyl chloride resins 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-based plasticizers such as butoxyethyl) phosphate octyl diphenyl phosphate; polyhydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol, 4
-Butanediol, 1,5-hexanediol, 1,6
Using hexanediol, neopentyl glycol, etc., as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, etc.
Polyester plasticizer using terephthalic acid or the like and 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-based plasticizers, trimellitic acid-based plasticizers, pyromellitic acid-based plasticizers, biphenylene polycarboxylic acid-based plasticizers, and the like.

The hydrotalcite compound is a double salt compound composed of magnesium or / and an alkali metal and aluminum or zinc and aluminum, as represented by the following general formula (I). It may be something.

[0030]

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The hydrotalcite compound may be a natural product or a synthetic product. Examples of the synthesis method include JP-B-46-2280 and JP-B-50-300.
Japanese Patent Publication No. 39, Japanese Patent Publication No. 51-29129, Japanese Patent Publication No. 3
Known methods described in JP-B-36839, JP-A-61-174270, JP-A-5-17952 and the like can be exemplified. Further, they can be used without being limited by their crystal structure, crystal particle diameter, and the like.

The surface of the above hydrotalcite compound may be made of 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 fatty acid amide. And those coated with higher fatty acid esters or waxes.

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.) and the like.

The above perchlorates include lithium perchlorate, sodium perchlorate, potassium perchlorate, strontium perchlorate, barium perchlorate, zinc perchlorate,
Cadmiumium perchlorate, lead perchlorate, aluminum perchlorate, ammonium perchlorate, and the like. These perchlorates may be anhydrous or hydrated, and may be butyl diglycol, butyl diglycol adipate, or the like. And a dehydrate 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, and typical examples thereof include A-type, X-type, Y-type and P-type zeolites. Monodenite, analsite, sodalite aluminosilicate, clinbutyrolite, erionite, chabazite and the like can be mentioned, and hydrated or water of crystallization having water of crystallization of these zeolite compounds (so-called zeolite water) is removed. Any of anhydrides may be used.

Examples of the organic phosphite compound include triphenyl phosphite, tris (2,4-ditert-butylphenyl) phosphite, tris (nonylphenyl) phosphite, tris (dinonylphenyl) phosphite, Tris (mono, 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, tri (2-ethylhexyl) phosphite, tridecyl phosphite, trilauryl phosphite, dibutyl acid phosphite, dilauryl acid phosphite Sphite, trilauryl trithiophosphite, bis (neopentyl glycol) ・ 1,
4-cyclohexanedimethyldiphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-
Methylphenyl) pentaerythritol diphosphite, distearylpentaerythritol diphosphite, phenyl-4,4'-isopropylidenediphenol pentaerythritol diphosphite, tetra (C
₁₂ -C ₁₅ mixed alkyl) -4,4'-isopropylidene diphenyl diphosphite, bis [2,2'-methylenebis (4,6-diamyl phenyl)] - isopropylidene den diphenyl diphosphite, 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.triphosphite, 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 (6-
Tert-butyl-m-cresol), 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-di-tert-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-ditert-butyl-4-hydroxyphenyl) propionate] methane, 2-tert-butyl-4- Methyl-6- (2-acryloyloxy-3-tert-butyl-5-methylbenzyl) phenol, 3,9-bis [1,1-dimethyl-2-hydroxyethyl) -2,
4,8,10-tetraoxaspiro [5,5] undecane-bis [β- (3-tert-butyl-4-hydroxy-5
-Butylphenyl) propionate] and triethylene glycol bis [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate].

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, and epoxidized safflower oil. 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 diepoxide, 3 , 4-epoxycyclohexylmethylepoxycyclohexanecarboxylate, bisphenol type or novolak type epoxy resin.

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

Examples of the ultraviolet absorber include, for example, 2,
4-dihydroxybenzophenone, 2-hydroxy-4
-Methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-tert-butyl-4 '-(2-methacryloyloxyethoxy) benzophenone, 5,5'-methylenebis (2-hydroxy-
2-hydroxybenzophenones such as 4-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-C7-9 mixed alkoxycarbonylethylphenyl) triazole,
2- (2-hydroxy-3,5-dicumylphenyl) benzotriazole, 2,2′-methylenebis (4-tert-octyl-6-benzotriazolylphenol), 2-
2- (2-hydroxyphenyl) benzotriazoles such as polyethylene glycol ester of (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-hydroxy-4-octoxyphenyl) -4,
6-bis (2,4-dimethylphenyl) -1,3,5-
2- (2-hydroxyphenyl)-such as triazine
1,3,5-triazines; phenyl salicylate, resorcinol monobenzoate, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl-3,5-di-tert-butyl -4-
Benzoates such as hydroxybenzoate; 2-ethyl-2'-ethoxyoxanilide, 2-ethoxy-
Substituted oxanilides such as 4'-dodecyl oxanilide; cyanoacrylates such as ethyl-α-cyano-β, β-diphenylacrylate, methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate And so on.

Examples of the hindered amine light stabilizer include, for example, 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) butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4) -Piperidyl) di (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-tetraethyl-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
Tertiary octylamino-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
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, 1,6,11-tris [2,4
And hindered amine compounds such as -bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -s-triazin-6-ylamino] undecane.

Examples of the above-mentioned other inorganic metal compounds 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 foaming agents such as dinitropentamethylenetetramine, N, N'-dimethyl-N, N'-dinitroterephthalamine, benzenesulfonylhydrazide, p-toluenesulfonylhydrazide, 3,3'-disulfonehydrazidephenylsulfone, and toluenedisulfonyl Hydrazone foaming agents such as hydrazone, thiobis (benzenesulfonylhydrazide), toluenesulfonylazide, toluenesulfonylsemicarbazide, p, p'-bis (benzenesulfonylhydrazide) ether, p-toluenesulfonylsemicarbazide, 4,4'-oxybis (sulfonyl) Carbazide-based blowing agents such as semicarbazide),
And 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 used in combination. Examples of such a stabilizing aid include 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.

The epoxidized animal and vegetable oil composition of the present invention can be used irrespective of the processing method of the vinyl chloride resin, for example, calendering, roll processing, extrusion molding, and melt rolling. It can be suitably used in pressure molding, powder molding and the like.

The vinyl chloride resin composition containing the epoxidized animal and vegetable oil composition of the present invention is useful for building materials such as wall materials, floor materials, window frames, and wallpaper; interior materials for automobiles; coating materials for electric wires; And agricultural materials such as tunnels; food packaging materials such as wraps and trays; paints; and hoses, pipes, sheets, and toys.

[0049]

Next, the present invention will be described with reference to examples and use examples, but the present invention is not limited by the following examples and use examples.

Example 1 A mixture of 59 g of linseed oil (iodine value 193.3) and 41 g of tallow (iodine value 49.5) was mixed with 1% by weight of a lipase derived from Alcaligenes sp. (Lipase QLC, manufactured by Meito Sangyo Co., Ltd.). ) Was added and the mixture was stirred and reacted at 60 ° C. for 48 hours to obtain a transesterified oil (iodine value: 132.6).

In the reaction flask, the transesterified oil 100
g, toluene 50 g, 80% aqueous formic acid solution 6.1 g (0.
205 equivalents ^{* 1} ) and 0.8 g of phosphoric acid were taken and heated to 70 ° C. in a hot water bath. 60% aqueous hydrogen peroxide solution 3
8.4 g (1.30 equivalents ^{* 1} ) was gradually added dropwise using a dropping funnel so that the temperature in the tank did not exceed 75 ° C. The product was repeatedly washed with hot water in a separating funnel, desolventized and dehydrated to produce an epoxidized animal and vegetable oil composition (see Table 1 below). * 1: Based on unsaturated bond equivalent in transesterified oil.

Examples 2 and 3 58 g of linseed oil and palm oil (iodine value 48.0) 4
2 g of mixture and linseed oil 29 g, palm oil 21 g
Then, a mixture of 50 g of rapeseed oil (iodine value 115.4) was transesterified and epoxidized in the same manner as in Example 1 to produce an epoxidized animal and vegetable oil composition (see Table 1 below).

Comparative Examples 1-3 Epoxidized animal and vegetable oil compositions obtained by epoxidizing beef tallow, palm oil or rapeseed oil in the same manner as in Example 1 (Table 1 below)
) Was manufactured. However, for tallow and palm oils, 0.300 equivalents of formic acid and 1.40 equivalents of hydrogen peroxide were used at the time of epoxidation in order to decrease the iodine value and increase the oxirane oxygen content.

Comparative Examples 4 to 6 Epoxidized animal and vegetable oil compositions (see Table 1 below) were prepared by epoxidizing animal and vegetable oil mixtures having the same composition as in Examples 1 to 3 without transesterification.

[0055]

[Table 1]

Use Example 1 A sheet was prepared by kneading rolls with the following composition at 170 ° C., and pressed at 180 ° C. for 5 minutes and 20 minutes to measure the yellowness (press coloring) of the pressed sheet using a Hunter colorimeter. It measured using. In addition, the roll-up sheet
C. and placed in a gear oven at 175.degree. C., the blackening time was measured, and the colorability (oven coloring) after 60 minutes at 175.degree. C. was visually evaluated on a scale of 1 (no coloring) to 10 (large coloring). . The results are shown in Table 2 below.

[Blending] Parts by weight Vinyl chloride resin (degree of polymerization 1050) 100 di-2-ethylhexyl phthalate 40 tetra (C ₁₂ -C ₁₅ mixed alkyl) -4,4′-0.5 isopropylidene diphenyl diphosphite di Benzoylmethane 0.05 Zinc stearate 0.5 Barium stearate 1.0 Test compound (see [Table 2] below) 3

[0058]

[Table 2]

Use Example 2 The same test as in Use Example 1 was conducted with the following composition. The results are shown in Table 3 below.

[Blending] parts by weight Vinyl chloride resin (degree of polymerization 1050) 100 di-2-ethylhexyl phthalate 20 epoxidized soybean oil 2 calcium carbonate 10 zinc stearate 0.5 barium stearate 1.0 DHT-4A ^{* 40} .1 Test compound (see [Table 3] below) 2 * 4: Synthetic hydrotalcite manufactured by Kyowa Chemical Industry Co., Ltd.

[0061]

[Table 3]

Use Example 3 A sheet was prepared with the following composition, and placed in a gear oven at 190 ° C. to measure the blackening time. 180 ° C
Milling test with rolls of 5 minutes, 10 minutes, 1 minute
Sampling was performed in 5 minutes and 20 minutes, and the coloring property was 1
(Almost no coloring) 10 to 10 (Large coloration), and the ease of peeling when sampling for 10 minutes and 20 minutes was evaluated as ◎, ○, △ and ×
Was evaluated in four steps. The results are shown in Table 4 below.

[Blending] Parts by weight Vinyl chloride resin (degree of polymerization: 800) 100 Kaneace B-22 ^* 55 Dioctylmercaptotin 1.5 Zinc stearate 0.5 Calcium stearate 1.0 Test compound (Table 4 below) 2) * 5: Resin modifier manufactured by Kanegabuchi Chemical Industry Co., Ltd.

[0064]

[Table 4]

Use Example 4 The same test as in Use Example 1 was conducted with the following composition. Also,
After placing the pressed sheet at 180 ° C. for 5 minutes in a gear oven at 70 ° C. for one week, the presence or absence of bleed was visually checked. The results are shown in the following [Table 5].

[Blending] Parts by weight Vinyl chloride resin (degree of polymerization: 1100) 100 Di-2-ethylhexyl adipate 30 Epoxidized soybean oil 5 Calcium-zinc complex stabilizer 1.0 Stearoyl benzoylmethane 0.05 Test compound (the following [ (See Table 5) 5

[0067]

[Table 5]

Use Example 5 Roll kneading was performed at 170 ° C. with the following composition, and pressing was performed at 180 ° C. to form a 1 mm sheet. Using this,
A tensile test was performed according to JIS K 7118, and tensile strength (MPa) and elongation were measured. In addition, the presence or absence of bleed in the sheet, which was left at room temperature for one week, was visually checked. The results are shown in Table 6 below.

[Blending] Parts by weight Vinyl chloride resin (degree of polymerization: 1100) 100 Calcium-zinc complex stabilizer 1.0 Tris (nonylphenyl) phosphite 0.5 Test compound (see the following [Table 6]) 50

[0070]

[Table 6]

As is clear from the above-mentioned use examples, the epoxidized animal and vegetable oil compositions (compositions of Comparative Examples 1 to 3) obtained by epoxidizing palm oil, beef tallow, rapeseed oil and the like were used as stabilizers for vinyl chloride resins. When used as the above, only those having a completely inadequate performance can be obtained. Further, the effects of the epoxidized animal and vegetable oil compositions (compositions of Comparative Examples 4 to 6) obtained by epoxidizing a mixed oil obtained by simply blending linseed oil with the linseed oil are quite insufficient.

On the other hand, in the present invention, two iodine values different from each other are used.
An epoxidized animal / vegetable oil composition obtained by transesterifying and / or epoxidizing a mixture of at least one animal / vegetable oil (Example 1)
3), the effect is remarkably improved to the extent that it cannot be predicted from the case of simply mixing.

[0073]

The epoxidized animal and vegetable oil composition of the present invention comprises:
It has the effect of improving various properties such as thermal stability and coloring properties,
In particular, it can be suitably used as a stabilizer or a plasticizer for a vinyl chloride resin.

Claims (7)

[Claims] An epoxidized animal or vegetable oil composition obtained by subjecting a mixture of two or more animal and vegetable oils having different iodine values to esterification and then epoxidizing the mixture. 2. The method according to claim 1, wherein the animal and vegetable oil mixture is at least (a)
10 to 80% by weight of an animal or vegetable oil having an iodine value of less than 120 and (b) 10 to 80% by weight of an animal or vegetable oil having an iodine value of 150 or more
The epoxidized animal and vegetable oil composition according to claim 1, comprising: 3. The iodine value of the animal and vegetable oil mixture is 100.
The epoxidized animal and vegetable oil composition according to claim 1 or 2, wherein 4. The epoxidized animal or vegetable oil composition according to claim 1, which is transesterified using a lipase. 5. The epoxidized animal or vegetable oil composition according to claim 2, wherein the component (a) is at least one selected from the group consisting of beef tallow, palm oil and rapeseed oil. 6. The epoxidized animal and vegetable oil composition according to claim 2, wherein the component (b) is linseed oil. 7. The composition according to claim 1, which is blended with a vinyl chloride resin.
An epoxidized animal or vegetable oil composition according to any one of claims 1 to 6.