JP2002155180A - Vinyl chloride based resin composition for food packaging - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a vinyl chloride based resin composition for food packaging to be used in food packaging films which excels in the prevention of yellowing and long-run properties and also easy processability and, in addition, excellent colorability and thermal stability. SOLUTION: The vinyl chloride based resin composition for food packaging comprises 100 pts.wt. vinyl chloride based resin, (a) 10-80 pts.wt. adipic ester based plasticizer, (b) 0.01-10 pts.wt. organic acid calcium salt, (c) 0.01-10 pts.wt. organic acid zinc salt, and 0.001-10 pts.wt. at least one kind to be selected from the phosphite compounds to be represented by the formula (R is a hydrogen atom or a 1-4C alkyl group; R' is a 1-20C alkyl group, an aryl group, an alkylaryl group or an arylalkyl group; n is 0 or 1; and A is a 1-10C alkylene group or -S- when n is 0 and is an alkanetoluyl group when n is 1).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a vinyl chloride resin composition for food packaging, and more particularly, to a foodstuff having excellent coloring properties and heat stability, which comprises a phosphite compound having a specific structure. The present invention relates to a vinyl chloride resin composition for packaging.

[0002]

2. Description of the Related Art Polyvinyl chloride stretch films have excellent transparency, flexibility, gas barrier properties, food preservability, and packaging suitability.
In recent years, it has been used in large quantities as food packaging films for meat, fresh fish, fruits and vegetables, prepared foods and the like in food departments such as department stores and supermarkets.

In producing this polyvinyl chloride stretch film, for example, an inflation method or T-
In a melt extrusion molding such as a die method, there is a problem in long running property due to burning or rusting of the product.
For this reason, attempts have been made to solve these problems by adding various additives and the like.

Further, in order to improve stretchability when molding a stretch film, there is a tendency to use a polyvinyl chloride resin having a high degree of polymerization. Agents have been required.

Various additives including a metal stabilizer are compounded in the vinyl chloride resin in order to prevent deterioration due to heat or light during processing or use. Among these additives, phosphite compounds exhibit an excellent effect of improving thermal stability during processing or use.

[0006] Numerous vinyl chloride resin compositions for food packaging have been proposed, for example, JP-A-62-91548.
In the publication, an adipic acid ester-based plasticizer, an epoxidized vegetable oil, a calcium salt of an organic carboxylic acid, a zinc salt of an organic carboxylic acid, a polyunsaturated fatty acid partial ester of polyglycerol and stearoylbenzoylmethane are added to a vinyl chloride resin. There has been proposed a vinyl chloride resin composition for food packaging which is added. JP-A-3-41142 discloses a food packaging composition comprising a polyvinyl chloride resin and an adipate plasticizer, a calcium salt of an organic carboxylic acid, a zinc salt of an organic carboxylic acid, and a hydrotalcite compound. A polyvinyl chloride resin composition has been proposed. Japanese Patent Application Laid-Open No. 4-59850 discloses that a polyvinyl chloride resin is prepared by adding an adipic ester plasticizer, an epoxidized vegetable oil, a zinc salt of an organic carboxylic acid, a nonionic surfactant and an overbased compound of an alkaline earth metal. There has been proposed a polyvinyl chloride resin composition for food packaging to which a carboxylate / carbonate complex is added. JP-A-6-1007
No. 49 discloses a polyvinyl chloride resin for food packaging comprising an adipic ester plasticizer, a calcium salt of an organic carboxylic acid, a zinc salt of an organic carboxylic acid, and a zinc-modified hydrotalcite compound. Vinyl based resin compositions have been proposed. JP-A-8-27341 discloses that an epoxidized resin produced by a hydrogen peroxide method and having a peroxide value of 13 or less and containing no phenolic antioxidant and no phosphorus antioxidant is added to a chlorine-containing resin. A food packaging material to which soybean oil is added has been proposed. Further, JP-A-10-251469 discloses that an adipic acid ester plasticizer is added to a polyvinyl chloride resin.
There has been proposed a polyvinyl chloride resin composition for a food packaging film, which comprises a zinc salt of an organic carboxylic acid and a cyclic organic phosphate compound. However, the trinonylphenyl phosphite used here is still insufficient in the effect of improving long-run properties, and nonylphenol produced by decomposition is suspected as an estrogen substance, which is in contact with food packaging materials. Therefore, there is a drawback that the phosphite compound is extracted into foods and the like, and a phosphite compound excellent in hygiene has been demanded.

Japanese Patent Application Laid-Open No. 2000-26683 proposes a vinyl chloride resin composition for food packaging comprising a vinyl chloride resin and an adipate ester plasticizer and tocopherols added thereto. Also, Japanese Patent Application Laid-Open
Japanese Patent Application No. 0-239467 proposes to use an alkoxypolyethoxyphosphoric acid or a metal salt thereof in combination with a phenolic antioxidant. Here, as the phosphite compound, diphenol compounds of bisphenols including the phosphite compound used in the present invention are exemplified, but many of the compounds have insufficient extractability and long-run property, It has not been shown that only certain diphosphite compounds have the effect of significantly improving them.

Accordingly, an object of the present invention is to provide a vinyl chloride resin for food packaging used in a food packaging film which is excellent in anti-burn properties and long-run properties, is easy to process, and has excellent coloring properties and heat stability. It is to provide a composition.

[0009]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that the above objects can be achieved by including a phosphite compound having a specific structure, and have reached the present invention. did.

That is, the present invention relates to a vinyl chloride resin 100
(A) adipate plasticizer 1 based on parts by weight
0-80 parts by weight, (b) calcium organic acid salt 0.01-
10 parts by weight, (c) 0.01 to 10 parts by weight of a zinc organic acid salt, and (d) at least one selected from phosphite compounds represented by the following general formula (I): 0.001 to 10
An object of the present invention is to provide a vinyl chloride resin composition for food packaging containing parts by weight.

Embedded image (Wherein, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ′ represents an alkyl group having 1 to 20 carbon atoms, an aryl group, an alkylaryl group, or an arylalkyl group; And A represents an alkylene group having 1 to 10 carbon atoms or -S- when n is 0;
When 1 represents an alkanetriyl group having 1 to 10 carbon atoms)

[0011]

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

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, chlorinated polyvinyl chloride, and the like. , 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, salt Chlorine-containing resins such as vinyl-maleic acid ester copolymer, vinyl chloride-methacrylic acid ester copolymer, vinyl chloride-acrylonitrile copolymer, vinyl chloride-various vinyl ether copolymers, and their mutual blended products or Chlorine-containing resin and another chlorine-free synthetic resin, for example, acrylonitrile-styrene copolymer, acrylonitrile-styrene-
Butadiene terpolymer, ethylene-vinyl acetate copolymer, ethylene-ethyl (meth) acrylate copolymer,
Examples thereof include blends with polyester and the like, block copolymers, graft copolymers, and the like.

The (a) adipic ester plasticizer used in the present invention may be an ester compound obtained by a normal reaction of one or more monohydric alcohols or dihydric or higher polyhydric alcohols with adipic acid, or It is a polyester compound. Here, as the monohydric alcohol,
n-butyl alcohol, n-hexyl alcohol, n-
Octyl alcohol, n-decyl alcohol, isoheptyl alcohol, 2-ethylhexyl alcohol, isooctyl alcohol, isononyl alcohol, isodecyl alcohol, butyldiglycol, and the like are included. Further, as the polyhydric alcohol, ethylene glycol, diethylene glycol, triethylene glycol,
Examples include 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol, neopentyl glycol, 1,6-hexanediol, and the like.

The content of the adipic ester plasticizer is 10 to 8 parts by weight based on 100 parts by weight of the vinyl chloride resin.
0 parts by weight, preferably 20 to 50 parts by weight. If the content is less than 10 parts by weight, the flexibility becomes insufficient, and
If the amount exceeds the weight part, it becomes too soft and the strength becomes insufficient.

The (b) calcium organic acid salt used in the present invention is a salt of calcium carboxylic acid or phenol, and a normal salt, an acid salt, a basic salt or an 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, elaidic acid, arachidic acid, arachidic acid, arachidonic acid, behenic acid, Mixtures of the above naturally occurring acids such as 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, benzoic acid, p-tert-butylbenzoic acid, ethylbenzoic acid Isopropyl benzoic acid, toluic acid, xylic acid, salicylic acid, 5-tert-octylsalicylic acid, naphthenic acid, cyclohexanecarboxylic acid, adipic acid, maleic acid, acrylic acid, methacrylic acid and the like. , For example, phenol, Creso , Ethylphenol, cyclohexylphenol, nonylphenol, dodecylphenol and the like.

Among these calcium organic acid salts, for example, benzoic acid, p-tert-butylbenzoic acid, ethylbenzoic acid, isopropylbenzoic acid, toluic acid, xylic acid,
It is preferable to use calcium of an aromatic carboxylic acid such as salicylic acid, 5-tert-octylsalicylic acid, and naphthenic acid because a material having excellent coloring properties can be obtained.

The content of the calcium organic acid salt is 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the vinyl chloride resin. If the content is less than 0.01 part by weight, the content effect cannot be obtained, and if it exceeds 10 parts by weight, the coloring may be too large, which is not preferable.

The (c) zinc organic acid salt used in the present invention is a salt of calcium carboxylic acid or phenol (each as exemplified above), and may be a normal salt, an acid salt, a basic salt or An overbased salt can be used in combination.

Among these zinc organic acid salts, unsaturated zinc carboxylate salts such as ricinoleic acid, linoleic acid, linoleic acid, oleic acid, elaidic acid, arachiic acid, arachidic acid, arachidonic acid, erucic acid and brassic acid are exemplified. Use is preferred because workability is improved.

The content of the zinc organic acid salt is 0.01 to 10 parts by weight with respect to 100 parts by weight of the vinyl chloride resin.
Preferably it is 0.1 to 5 parts by weight. The content is 0.0
If the amount is less than 1 part by weight, the content effect cannot be obtained. If the amount exceeds 10 parts by weight, blackening due to heat history during processing or use may occur, which is not preferable.

In the (d) phosphite compound used in the present invention, in the general formula (I), the alkyl group having 1 to 4 carbon atoms represented by R includes, for example, methyl,
Examples include groups such as ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl and tert-butyl. R '
Examples of the 1 to 20 alkyl groups represented by are, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, amyl, isoamyl, tert-amyl, hexyl, heptyl, octyl, isooctyl , 2-ethylhexyl, tertiary octyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl and the like. Examples of the aryl group represented by R ′ include groups such as phenyl and naphthyl. Examples of the alkylaryl group represented by R ′ include a phenyl group or a naphthyl group substituted with 1 to 5 alkyl groups exemplified above. R '
Examples of the arylalkyl group represented by include a benzyl group, α-methylbenzyl, α, α-dimethylbenzyl, and a phenylethyl group. Examples of the alkylene group having 1 to 10 carbon atoms represented by A include methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene,
Examples thereof include linear or branched groups such as decylene, and examples of the alkanetriyl group having 1 to 10 carbon atoms include:
Methanetriyl, ethanetriyl, propanetriyl,
Examples thereof include straight-chain or branched groups such as butanetriyl, pentanetriyl, hexanetriyl, heptanetriyl, octanetriyl, nonantriyl, and decanetriyl.

The organic phosphite compound represented by the general formula (I) as the component (c) used in the present invention will be more specifically shown below. However, the organic phosphite compound is not limited to this.

[0024]

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[0025]

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[0026]

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[0027]

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The content of the component (c) used in the present invention is 0.00 0.00 parts by weight based on 100 parts by weight of the vinyl chloride resin.
It is 1 to 10 parts by weight, preferably 0.01 to 5 parts by weight. If the content is less than 0.001 part by weight, the content effect cannot be obtained, and if the content is more than 10 parts by weight, not only is it wasteful but also the coloration may be reduced, which is not preferable.

It is preferable to add an epoxy compound to the vinyl chloride resin composition of the present invention because a more excellent stabilizing effect can be obtained. Examples of the epoxy compound include epoxidized soybean oil, epoxidized linseed oil, and the like. Epoxidized animal and vegetable oils such as epoxidized tung oil, epoxidized fish oil, epoxidized tallow oil, epoxidized castor oil, 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 carboxy Rate, 3,4-epoxycyclohexenemethyl epoxycyclohexanecarboxylate, bisphenol type or novolak type epoxy resin.

Particularly, epoxidized animal and vegetable oils, especially epoxidized soybean oil, are preferable because they have excellent stabilizing effects and are safe from natural fats and oils.

The content of these epoxy compounds is 1 to 30 parts by weight with respect to 100 parts by weight of the vinyl chloride resin.
Particularly, it is 5 to 25 parts by weight. If the content is less than 1 part by weight, the effect of the content may not be sufficiently exhibited.
If the amount is more than the weight part, not only the content effect cannot be obtained any more, but also disadvantages such as bleeding may occur, which is not preferable.

By blending the vinyl chloride resin composition of the present invention with an antifogging agent, fogging can be prevented when the composition is used as a packaging material (transparent film) for displaying fresh foods and the like. As these antifogging agents, preferred are, for example, sorbitan monomyristate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monobehenate or sorbitan-based surfactants such as alkylene oxide adducts thereof; glycerin monopalmitate Glycerin-based interface such as glycerin monostearate, diglycerin monostearate, diglycerin dipalmitate, diglycerin distearate, diglycerin monopalmitate stearate, triglycerin distearate or an alkylene oxide adduct thereof. Activator; polyet Polyethylene glycol surfactants such as lenglycol monostearate and polyethylene glycol monopalmitate; trimethylolpropane surfactants such as trimethylolpropane monostearate; pentaerythritol surfactants such as pentaerythritol monopalmitate; Alkylene oxide adducts of alkylphenols; esters of sorbitan / glycerin condensates with fatty acids; esters of sorbitan / alkylene glycol condensates with fatty acids; diglycerindiolate sodium lauryl sulfate, sodium dodecylbenzenesulfonate, cetyltrimethylammonium chloride , Dodecylamine hydrochloride, lauryl lauramide ethyl phosphate, triethylcetyl ammonium iodide, oleyl Mino diethylamine hydrochloride, and dodecylpyridinium salts and the like.

Of these, it is particularly preferable to use a nonionic surfactant such as a sorbitan-based, glycerin-based, polyethylene glycol-based, trimethylolpropane-based, or pentaerythritol-based surfactant because more excellent effects can be obtained.

The content of these antifogging agents is 0.1 to 10 parts by weight, especially 0.5 to 5 parts by weight, based on 100 parts by weight of the vinyl chloride resin. If the content is less than 1 part by weight, the effect of the content may not be sufficiently exhibited, and if it is used in an amount of more than 10 parts by weight, not only the content effect cannot be obtained any more, but also disadvantages such as bleeding may occur. It is not preferable because there is a possibility of it.

The vinyl chloride resin composition of the present invention may further contain various additives usually used as additives for vinyl chloride resins, for example, a plasticizer other than adipic acid, a β-diketone compound and the like. , A hydrotalcite compound, a zeolite compound, a phenolic or sulfuric antioxidant, a polyol, an ultraviolet absorber, a hindered amine light stabilizer, and other inorganic metal compounds.

As the above-mentioned plasticizer, any plasticizer usually used for vinyl chloride resins can be arbitrarily used. For example, dibutyl phthalate, butylhexyl phthalate, diheptyl phthalate, dioctyl phthalate, diisononyl phthalate, diisodecyl Phthalate-based plasticizers such as phthalate, dilauryl phthalate, dicyclohexyl phthalate, and dioctyl terephthalate; triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tri (isopropylphenyl) phosphate, triethyl phosphate,
Tributyl phosphate, trioctyl phosphate,
Phosphate plasticizers such as tri (butoxyethyl) phosphate and octyl diphenyl phosphate; polyhydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, and 1,3-butane Diol, 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, pimerine acid,
Polyester plasticizer using suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, etc., and using a monohydric alcohol or a monocarboxylic acid as a stopper if necessary; other, a tetrahydrophthalic acid plasticizer, Azelaic acid plasticizer, sebacic acid plasticizer,
Stearic acid plasticizers, citric acid plasticizers, trimellitic acid plasticizers, pyromellitic acid plasticizers, biphenylene polycarboxylic acid plasticizers and the like can be mentioned.

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, zinc, etc.) and the like.

The above hydrotalcite compound is represented by the following general formula (II):
And alkali metal and aluminum or zinc, a complex salt compound consisting of magnesium and aluminum,
The dehydrated water of crystallization may be used.

[0039]

Embedded image (Wherein Ia represents an alkali metal atom, and x1, x
2, x3, y and z indicate the following conditions, respectively, and m
Represents a real number; 0 ≦ x1 ≦ 10, 0 ≦ x2 ≦ 10, 0 ≦
x3 ≦ 10, 0 ≦ y ≦ 10, 0 ≦ z ≦ 10, provided that x1 and x2 are not simultaneously 0.

The above 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-5-17952 and the like can be exemplified. Further, the hydrotalcite compound can be used without being limited by its crystal structure, crystal particle diameter, 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 sulfonate metal salt 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.

The zeolite compound is an alkali or alkaline earth metal aluminosilicate having a unique three-dimensional zeolite crystal structure.
Type, X type, Y type, and P type zeolite, monodenite,
Analsite, sodalite group aluminosilicate, clinbutyrolite, erionite, chabazite and the like can be mentioned, and the hydrate or crystallization water containing crystal water of these zeolite compounds (so-called zeolite water) is removed. Any of anhydrides may be used.

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-ditert-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] and the like.

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 mercaptopropionates of polyols.

The polyols include, for example, 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-ditert-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 ethoxy oxanilide and 2-ethoxy-4'-dodecyl oxanilide; ethyl-α-cyano-β, β-diphenyl acrylate, methyl-2-
And cyanoacrylates such as 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.

The vinyl chloride resin composition of the present invention may 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 vinyl chloride resin composition of the present invention may contain, if necessary, additives usually used for vinyl chloride resins, such as fillers, colorants, crosslinking agents, antistatic agents, and plate-outs. Incorporation of inhibitors, surface treatment agents, lubricants, flame retardants, fluorescent agents, fungicides, bactericides, metal deactivators, release agents, pigments, processing aids, antioxidants, light stabilizers, etc. Can be.

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

The vinyl chloride resin composition of the present invention can be suitably used especially for food packaging such as a wrap film.

[0053]

Next, the present invention will be described in more detail by way of examples, but the present invention is not limited by the following examples.

Example 1 The following components were kneaded at 170 ° C. using a two-roll mill to form a sheet. The sheet was cut into small pieces of about 5 mm square, and a torque rheometer (temperature 200 ° C., rotation speed 80 rpm, input amount 60 g,
The decomposition time was measured at a capacity of 60 cc). Further, the test piece was immersed in distilled water, 4% acetic acid, 20% ethanol and n-heptane, left in a gear oven at 40 ° C. for 10 days, and then the elution amount (ppm) of the test compound was examined. Table 1 shows the results.

(Blending) Parts by weight Vinyl chloride resin 100 (TK-1300 manufactured by Shin-Etsu Chemical Co., Ltd.) Diisononyl adipate 30 Epoxidized soybean oil 8 Calcium benzoate 0.05 Zinc oleate 0.1 Zinc ricinoleate 0.06 Glycerin monooleate 0.5 Polyglycerin oleate 1.0 Polyoxyethylene (s) alkyl ether 0.5 Alkamizer 2 0.02 (Synthetic hydrotalcite manufactured by Kyowa Chemical Industry) Test compounds (Table 1) Table 1

[0056]

[Table 1]

Example 2 The following formulation was mixed at 180 ° C. for 5 minutes.
The mixture was kneaded for 10 minutes and 20 minutes, extruded by a T-die at 190 ° C., and a film having a thickness of 18 μm was produced by a conventional method using a take-up machine. The coloring of the obtained scroll (thickness: about 1 cm) was visually evaluated. The evaluation criterion is a 10-level scale, where 1 represents almost no coloration, and the coloration increases as the numerical value increases. Table 2 shows the results.

(Blending) Parts by weight Vinyl chloride resin 100 (Geon 101EP manufactured by Zeon Corporation) Diisononyl adipate 40 Epoxidized soybean oil 8 Adekastab SC-208 1.2 (Ca-Zn system manufactured by Asahi Denka Kogyo KK) Stabilizer) Glycerin monooleate 1.5 Polyoxyethylene (s) alkyl ether 0.5 Test compound (Table 2) Table 2

[0059]

[Table 2]

Example 3 The following formulation was rolled up at 180 ° C., pressed and visually evaluated for coloring. Pressing conditions and evaluation criteria are the same as in Example 2. One more
The blackening time in a 90 ° C. gear oven was measured. Table 3 shows the results.

(Blending) Parts by weight Vinyl chloride resin 100 (Viniclon 4000M manufactured by Mitsui Chemicals, Inc.) Diisononyl adipate 32 Epoxidized soybean oil 10 Calcium oleate 0.25 Calcium benzoate 0.25 Zinc ricinoleate 0.5 Glycerin Monooleate 1.5 Test compound (Table 3) Table 3

[0062]

[Table 3]

Example 4 The following formulation was rolled up at 180 ° C., pressed and visually evaluated for coloring. Pressing conditions and evaluation criteria are the same as in Example 2. One more
The blackening time in a 90 ° C. gear oven was measured. Table 4 shows the results.

(Blending) Parts by weight Vinyl chloride resin 100 (Viniclon 4000M manufactured by Mitsui Chemicals, Inc.) Diisononyl adipate 32 Epoxidized soybean oil 10 Calcium oleate 0.25 Calcium benzoate 0.25 Zinc ricinoleate 0.5 Glycerin Monooleate 1.5 Alkamizer 2 0.02 Test compound (Table 4) Table 4

[0065]

[Table 4]

As is clear from the above examples, when the phosphite compound was not used, sufficient thermal stability was not obtained, and when trisphenyl phosphite was used, the effect of improving the thermal stability was insufficient. In addition, when it is used as a food packaging film, it is easily extracted with water or alcohol. In addition, thermal coloring is large and thermal stability is insufficient. Further, when the comparative phosphite compounds tetratridecyl / 4,4′-butylidenebisphenoldiphosphite and tetratridecyl / 4,4′-isopropylidenebisphenoldiphosphite are used, the thermal stability is low. Although improved, it is easily extracted by water or alcohol.

On the other hand, when the phosphite compound having a specific structure used in the present invention is used,
When formed into a film for food packaging, it is not extracted by water or alcohol, and is excellent in colorability and heat stability.

[0068]

Industrial Applicability The vinyl chloride resin composition for food packaging of the present invention provides a food packaging film having excellent heat stability and coloring properties without being extracted by water or alcohol.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08K 5/524 C08K 5/524 // (C08L 27/06 (C08L 27/06 63:00) 63:00 A (72) Inventor Akihiro Yakimaki 5-2-13-Shirahata, Urawa-shi, Saitama F-term in Asahi Denka Kogyo Co., Ltd. 4F071 AA24 AA42 AC09 AC10 AC15 AF05 AH04 BA01 BB06 BC01 4J002 BB241 BD031 BD061 BD071 BD081 BD101 BD181 CD052 CD062 CD162 EG007 EG008 EG018 EG037 EG057 EG058 EG077 EG078 EG087 EG088 EH049 EH059 EH096 EJ077 EJ078 EW069 FD020 FD026 FD040 FD050 FD070 FD200 FD319 GG02

Claims (6)

[Claims] 1. An adipic acid ester plasticizer (10) to 80 parts by weight, (b) a calcium organic acid salt 0.01 to 10 parts by weight, based on 100 parts by weight of a vinyl chloride resin.
(C) 0.01 to 10 parts by weight of a zinc organic acid salt and (d) 0.001 to 10 parts by weight of at least one selected from phosphite compounds represented by the following general formula (I). Vinyl chloride resin composition for food packaging. Embedded image (Wherein, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ′ represents an alkyl group having 1 to 20 carbon atoms, an aryl group, an alkylaryl group, or an arylalkyl group; And A represents an alkylene group having 1 to 10 carbon atoms or -S- when n is 0;
When 1 represents an alkanetriyl group having 1 to 10 carbon atoms) 2. The vinyl chloride resin composition for food packaging according to claim 1, wherein the (b) calcium organic acid salt contains at least calcium aromatic carboxylate. 3. The vinyl chloride resin composition for food packaging according to claim 1, wherein (c) the zinc organic acid salt contains at least zinc unsaturated fatty acid. 4. The vinyl chloride resin composition for food packaging according to claim 1, further comprising 1 to 30 parts by weight of epoxidized soybean oil based on 100 parts by weight of the vinyl chloride resin. . 5. The vinyl chloride for food packaging according to claim 1, wherein 0.1 to 10 parts by weight of a nonionic surfactant is contained based on 100 parts by weight of the vinyl chloride resin. -Based resin composition. 6. The polyvinyl chloride resin composition for food packaging according to claim 1, which is used as a polyvinyl chloride stretch film.