JPH1149909A - Vinyl chloride resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition excellent in heat stability and colorability by mixing a vinyl chloride resin with an epoxidized palm oil obtained by epoxidizing palm oil having a specified iodine value in a specified ratio. SOLUTION: There is no particular limitation on the method for producing the vinyl chloride resin. It is exemplified by a bulk polymerization process, a solution polymerization process, a suspension polymerization process or an emulsion polymerization process. The amount of the epoxidized palm oil obtained by epoxidizing palm oil having an iodine value of 60 or above is 0.01-50 pts.wt. per 100 pts.wt. vinyl chloride resin. The epoxidation method is not particularly limited. It is exemplified by one using hydrogen peroxide or one using an organic peroxy acid such as peracetic acid. The epoxidized palm oil is desirably one having an oxirane oxygen content of 3.0 wt.% or above and an acid value of below 1. This composition may be used in combination with a normal, acid, basic or over-based salt of a carboxylic acid, an organophosphorus acid or a phenol with a metal (e.g. Li or Na).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a stabilized vinyl chloride resin composition, and more particularly, to a heat-resistant composition comprising an epoxidized palm oil obtained by epoxidizing a palm oil having an iodine value of 60 or more. And a vinyl chloride resin composition having excellent coloring properties.

[0002]

2. Description of the Related Art Vinyl chloride resins are inexpensive and can be easily adjusted in hardness by using a plasticizer, so that they can be used for various purposes.

[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 and 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 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 has been progressing, but has the drawback of insufficient heat resistance, and the development of more excellent stabilizing aids Is desired.

[0005] Epoxidized vegetable oils represented by epoxidized soybean oil have been used as effective heat resistance improvers, and it is also known to use epoxidized palm oil.

[0006] Palm oil is an oil extracted from the fruit portion of oil palm, and the extracted oil usually has an iodine value of about 50. Further, since this is a state in which a liquid and a solid are mixed at room temperature, a liquid portion separated by a method such as a windering method or an emulsification separation method is called so-called palm olein and has an iodine value of 55. Before and after.

However, epoxidized palm oil obtained by epoxidizing palm oil having an iodine value of less than 60 has drawbacks such as insufficient heat resistance and bleeding.

Accordingly, an object of the present invention is to provide a vinyl chloride resin composition having excellent stability in heat stability and coloring properties.

[0009]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that epoxidized palm oil obtained by epoxidizing palm oil having an iodine value of 60 or more is mixed with a vinyl chloride resin. The present inventors have found that a vinyl-based resin composition can achieve the above object, and have reached the present invention.

That is, the present invention relates to a vinyl chloride resin 100
An object of the present invention is to provide a vinyl chloride resin composition in which 0.01 to 50 parts by weight of an epoxidized palm oil obtained by epoxidizing a palm oil having an iodine value of 60 or more is added to parts by weight.

[0011]

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

The epoxidized palm oil used in the present invention is an epoxidized palm oil obtained by epoxidizing palm oil having an iodine value of 60 or more. In particular, excellent effects can be expected by using epoxidized palm oil obtained by epoxidizing palm oil having an iodine value of 65 or more.

Here, the iodine value used in the present invention is 60.
As a method for obtaining palm oil, methods such as a windering method and an emulsification fractionation method, which are methods for obtaining palm olein, can be applied mutatis mutandis. Specifically, it is obtained by leaving palm oil as a raw material at a low temperature of 20 ° C. or lower for several hours to several days to precipitate a solid content and obtain a supernatant.

As the palm oil used as the raw material, ordinary palm oil or palm olein can be used.

The palm oil used as the raw material can be epoxidized by a conventional method such as a method using hydrogen peroxide or a method using an organic peracid such as peracetic acid. The epoxidation method is not particularly limited.

The epoxidized palm oil having an oxirane oxygen content of not less than 3.0% by weight, especially not less than 3.5% by weight, is excellent in its own stability, and further has a vinyl chloride content. It is preferable because it shows good performance when it is blended with a system resin.

The epoxidized palm oil preferably has an acid value of less than 1. If the acid value exceeds 1, the thermal stability of the epoxidized palm oil itself may be reduced, and the performance may be adversely affected even when blended with a vinyl chloride resin. Therefore, it is not preferable.

Particularly, the epoxidized palm oil has an oxirane oxygen content of not less than 3.0% by weight, especially not less than 3.5% by weight, and an acid value not exceeding 1, especially not exceeding 0.5. It is more preferable to use one.

The amount of the epoxidized palm oil is 0.01 to 50 parts by weight, preferably 0.05 to 20 parts by weight, particularly preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the vinyl chloride resin. Department. If the amount is less than 0.01 part by weight, sufficient effects cannot be obtained, and if the amount is more than 10 parts by weight, no improvement in the effect is observed, but rather the coloring property is reduced.

The vinyl chloride resin used in the present invention is not particularly limited to a polymerization method such as bulk polymerization, solution polymerization, suspension polymerization and emulsion polymerization. Examples thereof include polyvinyl chloride and chlorinated polyvinyl chloride. , Polyvinyl 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 copolymer, vinyl chloride-butadiene copolymer, vinyl chloride-isoprene copolymer , Vinyl chloride-chlorinated propylene copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, chloride Chlorine-containing resins such as nyl-maleic acid ester copolymer, vinyl chloride-methacrylic acid ester copolymer, vinyl chloride-acrylonitrile copolymer, vinyl chloride-various vinyl ether copolymers, and their blends or their mutual products Blend products and block copolymers of chlorine-containing resins and other chlorine-free synthetic resins such as acrylonitrile-styrene copolymer, ethylene-vinyl acetate copolymer, ethylene-ethyl (meth) acrylate copolymer, polyester, etc. Examples thereof include polymers and graft copolymers.

Further, the composition of the present invention comprises a carboxylic acid,
Metals of organic phosphoric acids or phenols (Li, Na,
K, Ca, Mg, Ba, Sr, Cd, Zn, Al, S
n, a normal salt, an acidic salt, a basic salt or an overbased salt of organic Sn) 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, arachiic acid, behenic acid, erucic acid, brassic acid and similar acids and Tallow fatty acids, coconut oil fatty acids, tung oil fatty acids, soybean oil fatty acids and cottonseed oil fatty acids such as naturally occurring mixtures of the above acids, benzoic acid, p-tert-butylbenzoic acid, ethylbenzoic acid, isopropylbenzoic acid, toluic acid, Xylylic acid, salicylic acid, 5-tert-octylsalicylic acid, naphthenic acid, cyclohexanecarboxylic acid, adipic acid, maleic acid, acrylic acid, methacrylic acid, and the like.
For example, mono- or dioctyl phosphoric acid, mono- or di-dodecyl phosphoric acid, mono- or di-octadecyl phosphoric acid, mono- or di- (nonylphenyl) phosphoric acid, nonyl phenyl phosphonate, stearyl phosphonate, and the like, and the above-mentioned phenols For example,
Phenol, cresol, ethylphenol, cyclohexylphenol, nonylphenol, dodecylphenol and the like can be mentioned.

The composition of the present invention may further contain various additives usually used as additives for vinyl chloride resins, such as plasticizers, hydrotalcite compounds, β
-Diketone compounds, perchlorates, zeolite compounds,
Organic phosphite compounds, phenolic or sulfuric antioxidants, epoxy compounds, polyols, ultraviolet absorbers, hindered amine light stabilizers, other inorganic metal compounds, foaming agents and the like can also be blended.

As the above-mentioned plasticizer which can be used in the present invention, any plasticizer which is usually used for vinyl chloride resins can be used. For example, dibutyl phthalate, butylhexyl phthalate, diheptyl phthalate, Dioctyl phthalate, diisononyl phthalate,
Phthalate plasticizers such as diisodecyl phthalate, dilauryl phthalate, dicyclohexyl phthalate and dioctyl terephthalate; adipate plasticizers such as dioctyl adipate, diisononyl adipate, diisodecyl adipate, di (butyldiglycol) adipate; triphenyl phosphate, tricresyl phosphate , Trixylenyl phosphate, tri (isopropylphenyl) phosphate, triethyl phosphate,
Tributyl phosphate, trioctyl phosphate,
Phosphate plasticizers such as tri (butoxyethyl) phosphateoctyldiphenyl phosphate; polyhydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, and 1,3-butanediol , 1,4-butanediol, 1,5-hexanediol, 1,6-hexanediol, neopentyl glycol, etc. and dibasic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid Polyester plasticizers using suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, etc., and using monohydric alcohol or monocarboxylic acid as a stopper if necessary; other, tetrahydrophthalic acid plasticizer , Azelaic acid plasticizer, sebacic acid plasticizer, stearic acid plasticizer, citric acid plasticizer, trimellitic acid plasticizer, pyromellitic acid plasticizer, biphenylene polycarboxylic acid plasticizer, etc. .

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

Ia _x1 Mg _x2 Zn _x3 Al _y (OH) _{x1 + 2 (X2 + X3) + 3y-2} · (CO ₃ ) _{1-z / 2} (ClO ₄ ) _Z · m H ₂ O (I) ( In the formula, Ia represents an alkali metal atom, x1, x2, x
3, y and z each represent a condition represented by the following formula;
Indicates a real number. 0 ≦ x1 ≦ 10, 0 ≦ x2 ≦ 10, 0 ≦
x3 ≦ 10, 1 ≦ y ≦ 10, 0 ≦ z ≦ 1, provided that x1 and x2 do not 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.
JP, JP-B-3-36839, JP-A-61-1
Known methods described in JP-A-74270, 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 diameter and the like.

As the hydrotalcite compound, the surface thereof 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, It may be one coated with higher fatty acid amide, higher fatty acid ester or 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.) 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 of these zeolite compounds having water of crystallization (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
_12-15 mixed alkyl) -4,4'-isopropylidenediphenyldiphosphite, bis [2,2'-methylenebis (4,6-diamylphenyl)] isopropylidenediphenyldiphosphite, 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.

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.

The polyols include, for example, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, polypentaerythritol, pentaerythritol or half-stearic acid ester of dipentarisritol, bis (dipentaerythritol) adipate , Glycerin,
Tris (2-hydroxyethyl) isocyanurate, 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-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 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.

The other inorganic metal compounds mentioned above 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 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).

The composition of the present invention may further contain other stabilizing aids usually used for vinyl chloride resins. Examples of such a stabilizing aid include diphenylthiourea, diphenylurea, anilinodithiotriazine, melamine, benzoic acid, cinnamic acid, p-tert-butylbenzoic acid and the like.

In addition, the composition of the present invention may contain, if necessary, additives usually used for vinyl chloride resins, for example,
Fillers, colorants, cross-linking agents, antistatic agents, anti-fogging agents, plate-out preventing agents, surface treatment agents, lubricants, flame retardants, anti-fogging agents,
Fluorescent agents, fungicides, bactericides, metal deactivators, mold release agents, pigments, processing aids, antioxidants, light stabilizers and the like can be added.

The composition of the present invention can be used irrespective of the method for processing a vinyl chloride resin,
For example, calendering, rolling, extrusion molding,
It can be suitably used for melt rolling, pressure molding, powder molding and the like.

The composition of the present invention includes building materials such as wall materials, floor materials, window frames, and wallpaper; interior materials for automobiles; coating materials for electric wires;
Agricultural materials such as tunnels; food packaging materials such as wraps and trays; paints; can be suitably used as miscellaneous goods such as hoses, pipes, sheets, and toys.

[0045]

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 Examples.

Production Example 1 The dissolved palm oil (P-1) having an iodine value of 52 was placed in a vessel maintained at a temperature of 26 ° C. in a vessel and slowly stirred for 10 minutes.
The mixture was left for a while, and the stearin portion was removed with a filter press to obtain palm oil (P-2) having an iodine value of 56. Further, the dissolved P-2 was placed in a container maintained at a temperature of 17 ° C. in a tank, and left for 60 hours while being stirred slowly. The stearin portion was removed by a filter press, and palm oil having an iodine value of 65 (P-3). I got P-3 was left in a vessel maintained at a temperature of 15 ° C. while being slowly stirred for 90 hours, and the stearin portion was removed with a filter press to obtain palm oil (P-4) having an iodine value of 69.

Production Example 2 150 g of P-3, 50 g of toluene, 8
7.5 g of 0% formic acid aqueous solution and 85% of 85% phosphoric acid aqueous solution.
8 g was taken and heated to 70 ° C. in a hot water bath. 60% there
28.3 g of hydrogen peroxide solution (30% excess ^{# 1} ) was gradually dropped with a dropping funnel so that the temperature in the tank did not exceed 75 ° C.
The reaction was further performed at 70 ° C. for 4 hours. The product is repeatedly washed with hot water in a separatory funnel, desolvated and dehydrated to room temperature (25 ° C.).
C) to produce a liquid epoxidized palm oil (PEP-3). # 1: 30% excess of the amount of unsaturated bonds in palm oil that can be completely epoxidized

The same operation as in Production Example 2 was carried out except that the reaction time after the dropwise addition of the 60% hydrogen peroxide solution was extended to 5 hours, to produce a liquid epoxidized palm oil (PEP-4) at room temperature.

Epoxidized palm oils (PEP-1, PEP-2 and PEP-5, respectively) were prepared by epoxidizing P-1, P-2 and P-4 according to the above Preparation Example 2.

[0050]

[Table 1]

Example 1 A sheet was prepared by kneading a roll with the following composition at 170 ° C. and pressed at 180 ° C. for 5 minutes and 20 minutes to measure the yellowness of the pressed sheet using a Hunter colorimeter. . The roll-up sheet was placed in a gear oven at 190 ° C., the blackening time was measured, and the colorability after 60 minutes at 175 ° C. was visually evaluated in 10 stages of 1 (no coloring) to 10 (large coloring). evaluated. Further, the press sheet at 180 ° C. for 5 minutes was placed in a 70 ° C. gear oven for one week, and then the presence or absence of bleed was confirmed. 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 _12-15 mixed alkyl) -4,4′-0.5 isopropylidene diphenyl diphosphite dibenzoyl Methane 0.05 Zinc stearate 0.5 Barium stearate 1.0 Test compound (see [Table 2] below) 3

[0053]

[Table 2]

Example 2 The same test as in 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 ^{* 20} .1 Test compound (see Table 3 below) 2 * 2: Synthetic hydrotalcite manufactured by Kyowa Chemical Industry Co., Ltd.

[0056]

[Table 3]

Example 3 A sheet was prepared with the following composition, and the sheet was placed in a gear oven at 190 ° C., and the blackening time was measured. 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 coloration) Evaluated on a scale of 10 to 10 (large coloration). Further, when sampling for 10 minutes and 20 minutes, easiness of peeling (slipperiness) was evaluated from excellent to ◎, ○, △.
And 4 were evaluated. The results are shown in Table 4 below.

[Blending] Parts by weight Vinyl chloride resin (degree of polymerization: 800) 100 Kaneace B-22 ^* 45 Dioctylmercaptotin 1.5 Zinc stearate 0.5 Calcium stearate 1.0 Test compound (see Table 4 below) 2) * 4: Resin modifier manufactured by Kanegabuchi Chemical Industry Co., Ltd.

[0059]

[Table 4]

Example 4 The same test as in Example 1 was conducted with the following composition. The results are shown in [Table 5] below.

[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

[0062]

[Table 5]

As is evident from the above results, when epoxidized palm oil obtained by epoxidizing palm oil having an iodine value of less than 60 is used, epoxidized soybean oil generally used for vinyl chloride resins is used. It does not have satisfactory performance in terms of heat resistance and the like, and has drawbacks such as occurrence of bloom (Comparative Examples 1-2, 1-4 and 2).
-2, 2-4, 3-2, 3-3, 4-2, 4-4), even when this is blended in such an amount that the oxirane oxygen content is the same as the oxirane oxygen content of the epoxidized soybean oil. The effect of increasing the amount is hardly observed (Comparative Examples 1-3, 1-
5, 2-3, 2-5, 4-3, 4-5).

On the other hand, when the epoxidized palm oil obtained by epoxidizing the palm oil having an iodine value of 60 or more according to the present invention is used, the same heat resistance as the epoxidized soybean oil is used. And coloring properties were improved (Examples 1-1, 1-3, 1-4, 2-1 2-3, 2-4, 3
-1,3-2,3-3,4-1,4-3,4-4), and further, when considered in terms of the oxirane oxygen content, a remarkable heat resistance improving effect is exhibited (Examples 1-2, 2). -2, 4-2).

[0065]

Industrial Applicability The vinyl chloride resin composition of the present invention has excellent heat stability and coloring properties, especially coloring properties after heat history.
It can be suitably used for all applications.

 ────────────────────────────────────────────────── ─── Continuing from the front page (72) Inventor Dai Nishimura 5-2-13 Shirahata, Urawa-shi, Saitama Asahi Denka Kogyo Co., Ltd.

Claims (3)

[Claims] 1. A vinyl chloride resin composition comprising 100 parts by weight of a vinyl chloride resin and 0.01 to 50 parts by weight of an epoxidized palm oil obtained by epoxidizing a palm oil having an iodine value of 60 or more. 2. The vinyl chloride resin composition according to claim 1, wherein the epoxidized palm oil has an oxirane oxygen content of at least 3.0% by weight. 3. The vinyl chloride resin composition according to claim 1, wherein the epoxidized palm oil has an acid value of less than 1.