JP2001316549A - Vinyl chloride resin composition for packaging food - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve a difficult point, characteristic order, of a composition comprising a vinyl chloride resin composition and an deoxidized vegetable oil, when used as a packaging material. SOLUTION: This vinyl chloride resin composition for packaging foods, characterized by comprising a vinyl chloride resin composition and at least one of (a) an epoxidized vegetable oil, (b) an organic carboxylic acid zinc salt, (c) an organic carboxylic acid calcium salt and (d) an alkyl phosphite compound. The rigid vinyl chloride-based resin composition improves the characteristic odor of the epoxidized vegetable oil and has improved heat resistance and colorability. The resin composition may preferably further contain a β-diketone compound and/or a hydrotalcite compound to reinforce various performances.

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. More specifically, the present invention relates to a vinyl chloride resin composition for food packaging having excellent coloring resistance, heat resistance, and processability, and having a low odor.

[0002]

TECHNICAL BACKGROUND Vinyl chloride resin stretch films are excellent in transparency, flexibility, gas barrier properties, food preservability and packaging suitability, and are widely used as food packaging films. When producing this vinyl chloride resin stretch film, epoxidized soybean oil is used in a relatively large amount. For this reason, inflation or T-die formulation causes eye grease due to the hardening phenomenon of the epoxidized vegetable oil, causing burns to the product, and has a problem in long-run properties.
In addition, it becomes a stretch film having a rough surface, and when this film is used, it has drawbacks such as lack of slipperiness with an article to be packaged and high unwinding resistance of a paper tube wound film. In addition, a large amount of epoxidized soybean oil causes odor to be transferred to food. When these problems are solved with the conventional additives, the initial coloring and transparency are excellent,
It was very difficult to obtain a vinyl chloride resin stretch film suitable for food packaging without plate-out and bloom. Also, recently, stretch films from which tris (nonylphenyl) phosphite has been removed have been produced, but tend to have poor transparency, anti-fogging properties and heat resistance.

[0003]

As a result of intensive studies to solve these problems, a solution was found as follows. That is, a film having a low odor is prepared using a phosphite having a small odor, and the addition of this phosphite leads to an improvement in heat resistance and an improvement in a medium-term coloring, so that the amount of the epoxidized soybean oil is accordingly reduced. The odor of the film can be further reduced.
As a further effect, since the amount of inorganic additives as other heat stabilizers can be reduced, the transparency of the film is improved. The present invention has been achieved in anticipation of these effects.

[0004]

According to the present invention, a vinyl chloride resin stretch film having a low odor and excellent in various properties can be obtained by using a specific phosphite according to the above-mentioned gist. That is, the present invention comprises blending at least one of (a) an epoxidized vegetable oil, (b) a zinc salt of an organic carboxylic acid, (b) a calcium salt of an organic carboxylic acid, and (c) an alkyl phosphite compound with a vinyl chloride resin. Is a vinyl chloride resin composition. By adding a β-diketone compound, a hydrotalcite compound and / or a plasticizer to this vinyl chloride resin composition, an excellent stretch film of vinyl chloride resin for food packaging could be obtained.

The present invention will be described in more detail, but is not limited thereto. The alkyl phosphite compound used in the present invention is a compound represented by the following general formula (1).

[0006]

Embedded image

Specific examples of the alkyl phosphite compound include trioctyl phosphite, tridecyl phosphite, triundecyl phosphite, tridodecyl phosphite, tritridecyl phosphite, tritetradecyl phosphite, and tripentadecyl. Phosphite, trihexadecyl phosphite, triheptadecyl phosphite, trioctadecyl phosphite, trinonadecyl phosphite, triicosyl phosphite,
Tridocosyl phosphite, monooctadecyl didecyl phosphite, monododecyl ditridecyl phosphite, monoheptadecyl didodecyl phosphite, didodecyl phosphite, diundecyl phosphite, didodecyl phosphite, ditridecyl phosphite , Ditetradecyl phosphite, dipentadecyl phosphite, dihexadecyl phosphite, diheptadecyl phosphite, dioctadecyl phosphite, monooctadecyl monododecyl phosphite, monoheptadecyl
There are monohexadecyl phosphite, monododecyl phosphite, monotridecyl phosphite, monotetradecyl phosphite, monohexadecyl phosphite, monooctadecyl phosphite and the like. Phosphite compounds having an alkyl group of 7 or less carbon atoms have a strong odor and are liable to bloom, and those having a carbon number of more than 26 have reduced compatibility with resins and increased activity and have been processed. And the bloom phenomenon occurs. The addition amount of these alkyl phosphite compounds is 10
It is 0.01 to 5.0 parts by weight with respect to 0 parts by weight.

[0008] The vinyl chloride resin used in the present invention is:
It includes homopolymer resins of vinyl chloride, copolymer resins containing vinyl chloride as a main component, and polymer resin blends. Examples of the copolymer resin containing vinyl chloride as a main component include copolymers of vinyl chloride and ethylene, propylene, vinyl acetate, vinylidene chloride, acrylate, methacrylate, maleate, and the like. These vinyl chloride resins may be of any production method as long as they are obtained by a well-known polymerization method to date.

The epoxidized vegetable oil used in the present invention includes epoxidized soybean oil, epoxidized linseed oil, epoxidized castor oil and the like. The addition amount of these epoxidized vegetable oils is based on 100 parts by weight of the vinyl chloride resin.
0.1 to 20 parts by weight.

The organic carboxylic acids of the zinc and calcium salts of the organic carboxylic acid used in the present invention include caproic acid, enanthic acid, caprylic acid, 2-ethylhexanoic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, and tridecanoic acid. , Myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, arachinic acid, heneicosanoic acid, behenic acid, lignoceric acid, cerotic acid, montanic acid, oleic acid, elaidic acid, erucic acid, brassic acid, seracoleic acid, linoleic acid Acid, linolenic acid, ricinoleic acid, 12-hydroxyoctadecanoic acid, tallow fatty acid, coconut oil fatty acid, pearl fatty acid, tung oil fatty acid, mixture of natural fatty acids such as soybean oil fatty acid, cottonseed oil fatty acid, cinnamic acid, benzoic acid, p- Tertiary-butylbenzoic acid, dimethylbenzo Acid, ethyl benzoate, dimethyl hydroxybenzoic acid, toluic acid, acetoxybenzoic acid,
Propylbenzoic acid, 3,5-di-tert-butyl-4-
Monovalent carboxylic acids such as hydroxybenzoic acid, salicylic acid, p-tertiary-octylsalicylic acid, and oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, adilineic acid, sebacic acid, maleic acid Examples include acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, divalent carboxylic acids such as oxyphthalic acid, and monoester compounds of these divalent carboxylic acids with alcohols. The amount of the organic carboxylic acid zinc salt or calcium salt added is,
0.01 parts by weight to 100 parts by weight of vinyl chloride resin.
-5 parts by weight.

As the β-diketone compound used in the present invention, 4-cyclopentene-1,3-dione, 4-methylcyclohexane-1,3-dione, 2-phenylcyclohexane-1,3-dione, 2,2 -Dimethylcyclohexane-1,3,5-trione, 2-benzylcyclohexane-1,3-dione, 2-acetylcyclohexanone, 2-benzoylcyclohexanone, 2-acetylcyclohexane-1,3-dione, 1,4-bis ( 2,6-dioxocyclohexyl) -2-butene, bis (4-butylbenzoyl) methane, benzoylacetylmethane, 4-methoxybenzoylhexanoylmethane, benzoylacetyloctylmethane, tribenzoylmethane, dehydroacetic acid, Dehydropropionyl acetic acid, 2- (2-cyclyl) Hexen-1-yl) cyclohexane-1,3-dione, caproyl acetylmethane, benzoyl diacetylmethane, cyclohexylcarbonyl acetylmethane, cyclohexylcarbonyl benzoylmethane, benzoyltetralone, acetyltetralone, bis (cyclohexylcarbonyl) methane , Dibenzoylmethane, acetylacetone, butanoylacetone, stearoylacetone, lauroylacetone, benzoylphenylacetylmethane, benzoylformylmethane, benzoylpalmitoylmethane, hexadecanoylformylmethane, isovaleryl cyclohexylcarbonylmethane, cyclohexylcarbonylacetyl Ethyl methane and the like can be mentioned. The addition amount of these β-diketone compounds is 0.01 to 0.5 parts by weight based on 100 parts by weight of the vinyl chloride resin.

The hydrotalcite compound used in the present invention is a compound represented by the following formula (2). The addition amount of these compounds is 0.01 to 10 parts by weight based on 100 parts by weight of the vinyl chloride resin.

[0013]

## STR2 ## in _{[Mg a Zn b] 1-} x Al x (OH) 2 A x / 2 · mH 2 O (2) [ thisゝ, A is CO ₃ or SO ₄ anion, a,
b and x are positive numbers each satisfying the following condition. a + b =
1, 0 ≦ b <a, 0 <x ≦ 0.5. m is a number satisfying 0 ≦ m <2. ]

As the plasticizer used in the present invention, phthalate ester plasticizers (dimethyl phthalate, dibutyl phthalate, diheptyl phthalate, di-2-ethylhexyl phthalate, diisooctyl phthalate, di-n-
Octyl phthalate, diisononyl phthalate, didecyl phthalate, diisodecyl phthalate, dilauryl phthalate, dicyclohexyl phthalate, butyl benzyl phthalate, dibenzyl phthalate, etc., ester plasticizers of carboxylic acids other than phthalic acid or polyester plasticizers (di- n-butyl adipate, di-n-octyl adipate, diisononyl adipate, diisodecyl adipate, polypropylene adipate, polybutylene adipate, diisobutyl azelate, di-2-ethylhexyl azelate, dibutyl sebacate, di-2-ethylhexyl sebacate, polypropylene Sebacate,
Tri-2-ethylhexyl trimellitate, triisodecyl trimellitate, di-2-ethylhexyl fumarate, tributyl citrate, dibutyl malate, dioctyl malate, methyl acetyl ricinolate, polypropylene sebacate, etc.). These plasticizers are added in an amount of 0 to 5 based on 100 parts by weight of the vinyl chloride resin.
0 parts by weight.

Since the surface of the synthetic resin itself is hydrophobic, when the molded product is used, depending on conditions such as temperature and humidity, the absorbed or agglomerated water covers the surface as fine water droplets, Various disadvantages occur due to fogging. In order to eliminate these disadvantages, an antifogging agent is added when processing and molding a vinyl chloride resin product. Specific examples of these antifogging agents include cationic surfactants, anionic surfactants, and nonionic surfactants, which can be appropriately used according to the purpose. Nonionic surfactants are preferred because they improve the slipperiness of the film and the unwinding property of the film.

As specific examples of these, glycerin fatty acid esters include glycerin monopalmitate, glycerin monostearate, glycerin monooleate, glycerin monorenote, glycerin mono 12-hydroxystearate, glycerin monocaprylate, and glycerin monolaurate. Monoglyceride, glycerin mono-dipalmate, glycerin mono-distearate, glycerin di-tristearate, glycerin mono-diolate, glycerin di-triolate, glycerin mono-dilinolate, glycerin mono-dibehenate, glycerin mono-diricinolate, glycerin mono- Di-12-hydroxystearate, glycerin mono-
Mono-diglyceride such as diolate stearate, glycerin mono-di-phosphate, glycerin tri-2-
Ethylhexoate, glycerin tricaprylate, triglycerides such as glycerin trifatty acid (C7-11) ester, glycerin diacet monolaurate, glycerin diacet monostearate, glycerin diacet monooleate, glycerin diacet monolinoleate, glycerin diacet mono 12 -Hydroxystearate,
Glycerin diacet monomyristate, glycerin diacet monopalmitate, glycerin diacet monolaurate, glycerin monoacetomonostearate, glycerin monoacetomonomyristate, glycerin monoacetomonopalminate, glycerin monoacetomonoricinoleate, glycerin monoacetomonomono 12-hydroxystearate, glycerin monoacetomonobehenate, glycerin monoacetomonooleate, glycerin monoacetomonolaurate, glycerin monoacetodiolate,
Glycerin monoacetodiricinolate, glycerin monoacetodicaprylate, glycerin monoacetodilaurate, acetylated glycerides such as glycerin monoacetodistearate, succinic acid saturated fatty acid monoglyceride, citric acid saturated fatty acid monoglyceride, citric acid unsaturated fatty acid monoglyceride, Organic acid monoglycerides such as diacetyltartaric acid saturated fatty acid monoglyceride, diacetyltartaric acid unsaturated fatty acid monoglyceride, lactic acid saturated fatty acid monoglyceride, sorbitan fatty acid ester and ethylene oxide adducts thereof, sorbitan laurate, sorbitan palmitate, sorbitan stearate, sorbitan Tristearate, sorbitan oleate, sorbitan triolate, sorbitan behenate, sorbitan Polyoxyethylene (6) sorbitan monolau, such as rebehenate, sorbitan dilaurate, sorbitan distearate, sorbitan dipalminate, sorbitan monoerucinate, sorbitan monoricinoleate, sorbitan palm fatty acid ester, sorbitan palm fatty acid ester, sorbitan bovine fatty acid ester Rate, polyoxyethylene (20) sorbitan monolaurate, polyoxyethylene (20) sorbitan monopalmitate, polyoxyethylene (20) sorbitan monostearate, polyoxyethylene 20) sorbitan tristearate, polyoxyethylene (20) ) Sorbitan triolate, polyoxyethylene (30) sorbitan monomyristate, polyoxyethylene (20) sorbitan tetraoleate, polyoxy Ethylene (40)
As sorbitan dipearl fatty acid ester, polyoxyethylene (60) sorbitan tetraoleate, polyoxyethylene (60) sorbitan tricoco fatty acid ester, and polyglycerin fatty acid ester, diglycerin laurate, diglycerin stearate, diglycerin oleate, Diglycerin caprylate, diglycerin behenate, diglycerin myristate, diglycerin palm fatty acid ester, diglycerin palm fatty acid ester, diglycerin fatty acid ester such as bovine fatty acid ester, tetraglycerin stearate, tetraglycerin oleate, Hexaglycerin laurate,
Decaglycerin laurate, decaglycerin oleate,
Polyglycerin fatty acid esters such as polyglycerin polyricinoleate are exemplified. The addition amount of these antifoggants is 0.5 to 5 parts by weight based on 100 parts by weight of the vinyl chloride resin.

In addition, if necessary, a lubricant, an antioxidant, an antistatic agent, a filler, a reinforcing agent, a release agent, a foaming agent, a crosslinking agent, a fungicide, a processing aid, a plate-out inhibitor, a pigment , A viscosity reducing agent and the like can be included in the vinyl chloride resin for food packaging of the present invention.

[0018]

Next, the effects of the present invention will be described in detail with reference to examples. The evaluation values of thermal stability and coloring property in the examples are as follows. Strong Yu: 5, Excellent: 4, Medium: 3, Weak:
2, poor: 1.

Example 1 The following formulation was kneaded with a two-roll mill at 180 ° C. for 5 minutes to form a sheet having a thickness of 1 mm. The sheet was cut into about 5 cm 2 and placed in a 50 ml bottle from the bottom. Put the bottle at a height of 2 centimeters and
C., and the odor at that time was compared and examined. The evaluation values of the odor are as follows. No odor: 5, weak odor: 4, medium odor: 3, strong odor: 2, very strong odor: 1. Also, this sheet is cut into small pieces, which are
The sheet was placed in a gear oven at 0 ° C. and the thermal stability of the sheet was evaluated over time. In addition, six strips of this sheet were stacked and a pressure of 180 ° C. was applied for 5 minutes to prepare a 5 mm-thick press sheet, and the coloring property was evaluated. [Blending] 100 parts by weight of vinyl chloride resin (degree of polymerization: 1300) Diisononyl adipate 30 Epoxidized soybean oil Table 1 Calcium benzoate Table 1 Calcium ricinoleate Table 1 Zinc oleate Table 1 Zinc octoate 1 Table Alkyl phosphite compounds (Table 1) Table 1

[0020]

[Table 1]

Example 2 The following composition was kneaded by a two-roll mill at 180 ° C. for 5 minutes to prepare a sheet having a thickness of 1 mm. The sheet was cut into small pieces, which were placed in a gear oven at 180 ° C., and the thermal stability of the sheet was evaluated over time. Also, several pieces of this sheet are piled up at 180 ° C.
A press sheet having a thickness of 5 mm was prepared by applying pressure for 5 minutes, and the coloring property was evaluated. [Blending] Vinyl chloride resin (degree of polymerization: 1300) 100 parts by weight diisononyl adipate 30 epoxidized soybean oil 10 calcium benzoate 0.05 calcium ricinoleate 0.1 zinc octylate 0.1 alkyl phosphite compound (Table 2) Table 2 β-diketone compounds (Table 2) Table 2 Hydrotalcite compounds (Table 2) Table 2

[0022]

[Table 2]

Example 3 The following composition was kneaded by a two-roll mill at 180 ° C. for 5 minutes to prepare a sheet having a thickness of 1 mm. The sheet was cut into small pieces, which were placed in a gear oven at 180 ° C., and the thermal stability of the sheet was evaluated over time. Also, several pieces of this sheet are piled up at 180 ° C.
A press sheet having a thickness of 5 mm was prepared by applying a pressure for 10 minutes, and the coloring property was evaluated. [Blending] 100 parts by weight of vinyl chloride resin (degree of polymerization: 800) Epoxidized soybean oil Table 3 Calcium benzoate salt Table 3 Calcium stearate salt Table 3 Zinc stearate phosphate salt 3 Votes Zinc octylate salt Table 3 Alkyl Phosphite compounds (Table 3) Table 3 β-diketone compounds (Table 3) Table 3 Hydrotalcite compounds Table 3

[0024]

[Table 3]

Example 4 The following composition was kneaded by a two-roll mill at 180 ° C. for 5 minutes to prepare a sheet having a thickness of 1 mm. The sheet was cut into small pieces, which were placed in a gear oven at 180 ° C., and the thermal stability of the sheet was evaluated over time. Also, several pieces of this sheet are piled up at 180 ° C.
A press sheet having a thickness of 5 mm was prepared by applying pressure for 5 minutes, and the coloring property was evaluated. [Blending] 100 parts by weight of vinyl chloride resin (degree of polymerization: 1050) Dioctyl phthalate 40 Epoxidized soybean oil Table 4 Calcium benzoate salt Table 4 Calcium stearate salt Table 4 Zinc stearate salt Table 4 Zinc octylate salt Table 4 Alkyl phosphite compounds (Table 4) Table 4 β-diketone compounds (Table 4) Table 4 Hydrotalcite compounds (Table 4) Table 4

[0026]

[Table 4]

[00027]

The odor of the epoxidized vegetable oil is improved by using the epoxidized vegetable oil, the zinc organic carboxylate, the calcium organic carboxylate and the alkyl phosphite compound together with the vinyl chloride resin.
A vinyl chloride resin composition for food packaging having excellent heat stability and coloring properties was obtained.

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Claims (4)

[Claims] 1. A vinyl chloride resin comprising at least one of (a) an epoxidized vegetable oil, (b) a zinc salt of an organic carboxylic acid, (b) a calcium salt of an organic carboxylic acid, and (c) an alkyl phosphite compound. Vinyl chloride resin composition. 2. The vinyl chloride resin composition according to claim 1, further comprising at least one β-diketone compound. 3. The vinyl chloride resin composition according to claim 1, further comprising at least one hydrotalcite compound. 4. A vinyl chloride resin composition wherein at least one plasticizer is added to or added to the above-mentioned claim 1, 2 or 3.