JPH10251469A - Polyvinyl chloride resin composition for food wrapping film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a compsn. which is suitable for stretch film formation and is excellent in scorch resistance, long-run properties, and antibacterial properties by compounding a PVC resin with an adipate plasticizer, a zinc org.-carboxylate, and a specific cyclic org. phosphoric ester compd., each in a specified amt. SOLUTION: This compsn. contains 100 pts.wt. PVC resin (e.g. PVC), 10-50 pts.wt., pref. 20-40 pts.wt., adipate plasticizer (e.g. diisononyl adipate), 0.01-5 pts.wt., pref. 0.05-3 pts.wt., zinc org.-carboxylate (e.g. zinc oleate), and 0.001-10 pts.wt., pref. 0.01-5 pts.wt., cyclic org. phosphoric ester compd. represented by the formula (R<1> to R<3> are each H or 1-8C alkyl; R<4> is H or CH3 ; and when n is 1, then M is an alkali metal and when n is 2, then M is an alkaline earth metal or Zn). If necessary, the compsn. further contains 0.01-5 pts.wt. Ca org.- carboxylate (e.g. Ca benzoate).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polyvinyl chloride resin composition for a food packaging film, and more particularly to a polyvinyl chloride resin composition suitable for molding a polyvinyl chloride stretch film for a food 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 a food packaging film 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 a 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.

Accordingly, an object of the present invention is to provide a polyvinyl chloride resin composition which is easy to process with excellent anti-burn properties and long-run properties, and which is also excellent in antibacterial properties and which is suitable for food packaging films. It is in.

[0006]

Means for Solving the Problems As a result of intensive studies, the inventors of the present invention have found that a polyvinyl chloride resin has an adipic ester plasticizer, a zinc salt of an organic carboxylic acid and a specific cyclic organic phosphate compound. It has been found that the above object can be achieved by including

The present invention has been made based on the above findings, and is based on 100 parts by weight of a polyvinyl chloride resin, 10 to 50 parts by weight of an adipic acid ester plasticizer, 0.01 to 5 parts by weight of a zinc salt of an organic carboxylic acid. And a polyvinyl chloride compound for a food packaging film containing 0.001 to 10 parts by weight of a cyclic organic phosphate compound represented by the following general formula (I) of the following [Chemical formula 2] (the same as the above [Chemical formula 1]). The present invention provides a resin composition.

[0008]

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[0009]

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

The adipic ester plasticizer used in the present invention is an ester compound or a polyester compound obtained by a usual reaction of one or more monohydric alcohols or a dihydric or higher polyhydric alcohol with adipic acid. It is. Here, as the monohydric alcohol, n-
Examples thereof include butyl alcohol, n-hexyl alcohol, n-octyl alcohol, n-decyl alcohol, isoheptyl alcohol, 2-ethylhexyl alcohol, isooctyl alcohol, isononyl alcohol, and isodecyl alcohol. Further, as the polyhydric alcohol, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol and the like.

The content of the adipic ester plasticizer is 10 parts by weight based on 100 parts by weight of the polyvinyl chloride resin.
５０50 parts by weight, preferably 20-40 parts by weight. If the content is less than 10 parts by weight, the flexibility becomes insufficient,
If it exceeds 50 parts by weight, it becomes too soft and the strength becomes insufficient.

The zinc salt of an organic carboxylic acid used in the present invention improves the effects such as the thermal stability of the composition of the present invention. The carboxylic acid constituting the zinc salt of the organic carboxylic oxygen is capron. Acid, caprylic acid, pelargonic acid, 2-ethylhexyl acid, capric acid, neodecanoic acid, undecylenic acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, 12-hydroxystearic acid, 12-ketostearic acid, chloro Stearic acid, phenylstearic acid, ricinoleic acid, linoleic acid, linoleic acid, oleic acid, arachinic acid, behenic acid, erucic acid, brassic acid and similar acids, as well as tallow, coconut, tung, soy and cottonseed fatty acids A mixture of the above naturally occurring acids such as benzoic acid, p Monovalent carboxylic acids such as t-butyl benzoic acid, ethyl benzoic acid, isopropyl benzoic acid, toluic acid, xylyl acid, salicylic acid, 5-t-octyl salicylic acid, naphthenic acid, cyclohexane carboxylic acid, oxalic acid, malonic acid, and succinic acid , Glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, oxyphthalic acid, chlorophthalic acid, aminophthalic acid, maleic acid, fumaric acid, citraconic acid, metaconic acid, itaconic acid And monoesters of divalent carboxylic acids such as acids and aconitic acids.

The content of the zinc salt of the organic carboxylic acid is as follows:
0.01 parts by weight per 100 parts by weight of polyvinyl chloride resin
To 5 parts by weight, preferably 0.05 to 3 parts by weight. When the content is less than 0.01 part by weight, the stabilizing effect is insufficient (coloring property is insufficient), and when it exceeds 5 parts by weight, thermal stability becomes insufficient.

The cyclic organic phosphate compound represented by the general formula (I) used in the present invention is used as an antibacterial agent for imparting antibacterial properties to a polyvinyl chloride resin described below. In the general formula (I), the alkyl groups represented by R ¹ , R ² and R ³ include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, amyl, tert-amyl, hexyl , Octyl,
Examples include 2-ethylhexyl, isooctyl, tertiary octyl, nonyl, decyl, dodecyl, tridecyl, isotridecyl, tetradecyl, hexadecyl, octadecyl and the like.

The alkali metal represented by M includes sodium, potassium, lithium and the like, and the alkaline earth metal includes calcium, magnesium, barium, strontium and the like. In particular, M is an alkali metal atom or What is a zinc atom has a large effect, and is preferable.

Accordingly, specific examples of the cyclic organic phosphate compound represented by the general formula (I) include the following compound Nos. 3 to 10: 1 to No. 8 and the like.

[0017]

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[0018]

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[0019]

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[0020]

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[0021]

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[0022]

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[0023]

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[0024]

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The content of the cyclic organic phosphate compound is based on 100 parts by weight of the polyvinyl chloride resin.
It is 0.001 to 10 parts by weight, preferably 0.01 to 5 parts by weight. If the content is less than 0.001 part by weight, a sufficient effect of improving heat resistance cannot be obtained, and if it exceeds 10 parts by weight, the effect is not so much improved and it is economically disadvantageous.

The polyvinyl chloride resin used in the present invention includes a vinyl chloride homopolymer, a vinyl chloride-vinyl acetate copolymer, a vinyl chloride-ethylene vinyl acetate copolymer, and a vinyl chloride-ethylene copolymer. Copolymer, vinyl chloride-propylene copolymer, vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-urethane copolymer, vinyl chloride-acrylic acid ester copolymer Polymer, vinyl chloride-styrene-maleic anhydride terpolymer, vinyl chloride-styrene-acrylonitrile copolymer, vinyl chloride-butadiene copolymer, vinyl chloride-isoprene copolymer, vinyl chloride-chlorinated propylene copolymer Polymer, vinyl chloride-vinylidene chloride-vinyl acetate copolymer, vinyl chloride-maleic acid Stele copolymer, vinyl chloride-methacrylic acid ester copolymer, vinyl chloride-acrylonitrile copolymer, vinyl chloride copolymer such as vinyl chloride-maleimide copolymer, and the above resin, polyethylene, polypropylene, polybutene, Α-olefin polymers such as poly-3-methylbutene or ethylene-vinyl acetate copolymer, polyolefins such as ethylene-propylene copolymer and copolymers thereof, polystyrene,
Acrylic resin, polyurethane, copolymer of styrene with other monomers (for example, maleic anhydride, butadiene, acrylonitrile, etc.), acrylonitrile-styrene-butadiene copolymer, acrylate-styrene-butadiene copolymer, methacrylic Acid ester-styrene-
Blend products with a butadiene copolymer can be exemplified. The polyvinyl chloride resin may be obtained by any conventionally known polymerization method such as emulsion polymerization, suspension polymerization, solution polymerization, bulk polymerization and the like.

Further, by using a calcium salt of an organic carboxylic acid in combination with the polyvinyl chloride resin composition for a food packaging film of the present invention, more excellent heat resistance can be imparted. Examples of the carboxylic acid constituting the salt include the compounds exemplified as the carboxylic acid constituting the zinc salt of the organic carboxylic acid.

The amount of the calcium salt of the organic carboxylic acid is preferably 0.01 to 5 parts by weight, more preferably 0.05 to 5 parts by weight, based on 100 parts by weight of the polyvinyl chloride resin.
３3 parts by weight. If the content is less than 0.01 part by weight, the thermal stability may be insufficient, and if it exceeds 5 parts by weight, no further effect may be observed.

Various epoxidized vegetable oils can be added to the polyvinyl chloride resin composition of the present invention. Examples of the epoxidized vegetable oil include epoxidized soybean oil, epoxidized linseed oil, epoxidized castor oil, and epoxidized tung oil.

The amount of the epoxidized vegetable oil is preferably 2 to 100 parts by weight of the polyvinyl chloride resin.
30 parts by weight, more preferably 5 to 20 parts by weight.

Further, the polyvinyl chloride resin composition of the present invention may contain, together with the adipic ester plasticizer,
Further, plasticizers such as sebacate, azelate, acetylcitrate and polyester plasticizer can be used in combination according to the purpose.

In order to obtain a suitable polyvinyl chloride resin composition for a food packaging film, the composition of the present invention must be
Furthermore, tris nonylphenyl phosphite, tris (dinonylphenyl) phosphite, C _12-15 alkyl bisphenol A polyphosphite, tris (2,
4-di-t-butylphenyl) phosphite, distearylpentaerythritol diphosphite, bis (2
It is preferable to add an organic phosphite compound such as 4-di-t-butylphenyl) pentaerythritol diphosphite.

The amount of the organic phosphite compound used is as follows:
0.0 parts per 100 parts by weight of polyvinyl chloride resin
1 to 5 parts by weight is preferred.

Further, β-diketones can be added to the polyvinyl chloride resin composition for a food packaging film of the present invention. Examples of the β-diketones include, for example,
Benzoyl-P-chlorobenzoylmethane, benzoylacetylmethane, bis (4-methylbenzoyl) methane, bis (2-hydroxybenzoyl) methane, tribenzoylmethane, diacetylbenzoylmethane, palmitoylbenzoylmethane, stearoylbenzoylmethane, lauroyl. Benzoylmethane, dibenzoylmethane, 4-methoxybenzoylbenzoylmethane,
Bis (4-methoxybenzoyl) methane, bis (4-chlorobenzoyl) methane, bis (3,4-methylenedioxybenzoyl) methane, benzoylacetyloctylmethane, stearoyl-4-methoxybenzoylmethane, bis (4- Examples thereof include tert-butylbenzoyl) methane, benzoylacetylethylmethane, benzoyltrifluoroacetylmethane, 4-tert-butylbenzoylbenzoylmethane, oleylbenzoylmethane, and benzoylphenylacetylmethane. In addition, metals of these β-diketones (lithium,
Sodium, potassium, magnesium, calcium, strontium, barium, zinc, etc.) complex salts can also be added, and alkanoyl / aroylmethanes and their metal complex salts are particularly preferred.

The amount of the β-diketone or metal complex salt thereof is preferably 0.001 to 3.0 parts by weight based on 100 parts by weight of the polyvinyl chloride resin.

Further, an antifogging agent can be added to the polyvinyl chloride resin composition for a food packaging film of the present invention. Examples of the antifogging agent include sorbitan monomyristate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monobehenate and sorbitan-based surfactants such as alkylene oxide adducts thereof; glycerin monopalmitate, glycerin monophosphate Stearates, glycerin dipalmitate, glycerin distearate, diglycerin monostearate, diglycerin dipalmitate, diglycerin distearate,
Glycerin-based surfactants such as diglycerin monopalmitate monostearate, triglycerin monostearate, triglycerin distearate or an alkylene oxide adduct thereof; polyethylene such as polyethylene glycol monostearate and polyethylene glycol monopalmitate Glycol surfactants; trimethylolpropane surfactants such as trimethylolpropane monostearate; pentaerythritol surfactants such as pentaerythritol monopalmitate; alkylphenols and alkylene oxide adducts; sorbitan / glycerin condensates Esters with fatty acids, esters of sorbitan / alkylene glycol condensates with fatty acids; diglycerindiolate sodium lauryl sulfate, dodecyl Sodium benzenesulfonate, cetyltrimethylammonium chloride, dodecylamine hydrochloride, lauric acid lauryl amide ethyl phosphate,
Triethylcetylammonium iodide, oleylaminodiethylamine hydrochloride, dodecylpyridinium salt and the like.

The amount of the antifogging agent is preferably 0.001 to 3.0 parts by weight based on 100 parts by weight of the polyvinyl chloride resin.

Further, a hydrotalcite compound can be added to the polyvinyl chloride resin composition for a food packaging film of the present invention. As the hydrotalcite compound, for example, a double carbonate compound of magnesium, an alkali metal and / or zinc and aluminum represented by the following general formula (II) is used.

Ia _x1 Mg _x2 Zn _x3 Al _y (OH) _{x1 + 2 (X2 + X3) + 3y-2} · CO ₃ · mH ₂ O (II) (wherein Ia represents an alkali metal atom, x1, x2,
x3 and y each represent a condition represented by the following equation, and m represents a real number. 0 ≦ x1 ≦ 10, 0 ≦ x2 ≦ 10, 0 ≦ x
3 ≦ 10, 1 ≦ y ≦ 10, provided that x1 and x2 never become 0 at the same time. )

The above hydrotalcite compound is
It may be a natural product or a synthetic product. Examples of the method for synthesizing the synthetic product include JP-B-46-2280, JP-B-50-30039, and JP-B-51-29.
No. 129, Japanese Patent Publication No. 2-36143,
A publicly known method described in 1-1174270 can be exemplified. Further, the hydrotalcites can be used without being limited by the crystal structure, the crystal particle system, the presence or absence of water of crystallization and the amount thereof.

The surface of the above hydrotalcites 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 dodecylbenzenesulfonic acid, Those coated with fatty acid amides, higher fatty acid esters or waxes can also be used.

In order to facilitate the processing of the composition of the present invention, it is preferable to add one or more of the above-mentioned conventionally known lubricants.

Further, if necessary, the composition of the present invention may contain other thermoplastic resins, rubbers, crosslinking agents, fillers, foaming agents, antistatic agents, plate-out preventing agents, surface treatment agents,
Flame retardants, fluorescent agents, fungicides, fungicides, metal deactivators, mold release agents, pigments, processing aids, antioxidants, ultraviolet absorbers, light stabilizers and the like can be added.

The composition of the present invention is prepared by a generally known method using the above essential components and other components as necessary.

Further, the composition of the present invention is excellent in long-run properties, easy to process, and excellent in antibacterial properties, and therefore, is used for various food packaging films.

[0046]

Next, the present invention will be described specifically with reference to examples. However, the invention is not limited by these examples. The compound N used below
o. 1 to No. 8 is a compound exemplified as the cyclic organic phosphate compound.

Example 1 The following components were kneaded at 170 ° C. using a two-roll mill to form a sheet. The sheet is cut into small pieces of about 5 mm square, and a torque rheometer (temperature: 200 ° C., rotation speed: 80 rpm, input amount: 60 rpm)
g, capacity 60 cc). The results are shown in Table 1 below.

[Combination] Parts by weight Polyvinyl chloride resin (TK-1300 manufactured by Shin-Etsu Chemical Co., Ltd.) 100 Diisononyl adipate 30 Epoxidized soybean oil 8 Calcium benzoate 0.05 Zinc oleate 0.1 Zinc ricinoleate 0 0.06 glycerin monooleate 0.5 polyglycerin oleate 1.0 polyoxyethylene (s) alkyl ether 0.5 trisnonylphenyl phosphite 0.5 test compound (see Table 1 below) 0.3

[0049]

[Table 1]

Example 2 The following formulation was used at 180 ° C.
, And pressed to evaluate the coloring visually. Pressing conditions are 195 ° C, 100 kg / cm ² and 5
Minutes, 10 minutes and 20 minutes. Evaluation criteria is 10
In the stage, 1 represents a state without any coloring, and the coloring increases as the numerical value increases. The results are shown in Table 2 below.

[Combination] Parts by weight Polyvinyl chloride resin (Neon Zeon Co., Ltd.-based Geon-101EP) 100 Diisononyl adipate 40 Epoxidized soybean oil 8 Adekastab SC-208 (Ca-Zn system manufactured by Asahi Denka Kogyo KK) Stabilizer) 1.2 Glycerin monooleate 1.5 Polyoxymethylene (s) alkyl ether 0.5 Test compound (see [Table 2] below) 0.3

[0052]

[Table 2]

Example 3 A sheet was prepared by kneading a roll of the following composition at 170 ° C.
After pressing for 0.5 minutes, a soft PVC sheet having a thickness of 0.5 mm was prepared, and a test piece of 10 mm × 10 mm was prepared from the soft PVC sheet. The test piece was placed at the center of the Petri dish, and the agar medium was poured so that the test piece was covered thinly. After applying the culture solution of the bacteria described in [Table 3] below on the agar medium,
The cells were cultured at 5 ° C. for 2 days, the growth of the bacteria was observed, and the results were evaluated according to the following criteria.
Shown in In addition, "before the test" in the following criteria means immediately after the application of the culture solution of the bacteria. ◎: Only less than 0.1% of the number of bacteria before the test survived. Good: 0.1% or more and less than 1% of the number of bacteria before the test are alive. B: 1% or more and less than 10% of the number of bacteria before the test are alive. X: 10% or more of the number of bacteria before the test is alive.

[Blending] parts by weight Polyvinyl chloride resin (TK-1300 manufactured by Shin-Etsu Chemical Co., Ltd.) 100 diisononyl adipate 30 epoxidized soybean oil 8 calcium benzoate 0.05 zinc oleate 0.1 zinc ricinoleate 0 0.06 glycerin monooleate 0.5 polyglycerin oleate 1.0 polyoxyethylene (s) alkyl ether 0.5 trisnonylphenyl phosphite 0.5 test compound (see Table 3 below) 0.5

[0055]

[Table 3]

As is clear from the examples, a normal organic phosphate compound was added to a polyvinyl chloride resin composition containing a polyvinyl chloride resin, an adipic acid ester plasticizer, and a zinc organic carboxylate. Although some improvement in thermal stability at the time of processing can be seen, there is a disadvantage that coloring by heating is reduced (Comparative Example 1-2,
1-3, 2-2, 2-3).

On the other hand, a polyvinyl chloride resin composition containing a polyvinyl chloride resin, an adipic ester plasticizer and a zinc salt of an organic carboxylic acid is added to the cyclic compound of the general formula (I) according to the present invention. By adding the organic phosphate compound, the stability at the time of processing is remarkably improved, and further, it has an effect of suppressing coloring due to heating, and also exhibits excellent antibacterial properties (see each table). Example).

[0058]

The polyvinyl chloride resin composition for food packaging films of the present invention has excellent heat stability during processing and also has excellent antibacterial properties.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08K 5/11 C08K 5/11 5/521 5/521

Claims (3)

[Claims] 1. 100 parts by weight of a polyvinyl chloride resin, 10 to 50 parts by weight of an adipic ester plasticizer, 0.01 to 5 parts by weight of a zinc salt of an organic carboxylic acid, and
A polyvinyl chloride resin composition for a food packaging film, comprising 0.001 to 10 parts by weight of a cyclic organic phosphate compound represented by the general formula (I). Embedded image 2. The polyvinyl chloride resin composition for a food packaging film according to claim 1, wherein in the general formula (I), M is an alkali metal atom or a zinc atom. 3. The polyvinyl chloride resin composition for a food packaging film according to claim 1, further comprising 0.01 to 5 parts by weight of a calcium salt of an organic carboxylic acid.