JP2909748B2 - Polyvinyl chloride resin composition for food packaging - Google Patents

Description

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

[Conventional technology and its problems]

In recent years, polyvinyl chloride stretch film has been used as a food packaging film for meat, fresh fish, fruits and vegetables, prepared foods, etc. in food stores such as department stores and supermarkets due to its excellent transparency, flexibility, gas barrier properties, food preservability, and packaging suitability. Used in large quantities.

In producing this polyvinyl chloride stretch film, since an epoxidized vegetable oil such as epoxidized soybean oil is used in a relatively large amount, for example, in the melt extrusion molding such as the inflation method or T-die method, the epoxidized vegetable oil is used. The die of the die due to the curing phenomenon of
There was a problem in the long run property due to burning of the product. In addition, a large amount of epoxidized vegetable oil tends to cause a plate-out phenomenon. For this reason, it becomes a stretch film having a rough surface, and when this film is used, there are drawbacks such as lack of slipperiness with a packaged object and high unwinding resistance of a paper tube wound film.

One or more lubricants have been used to solve these problems and disadvantages and facilitate processing. As these lubricants, for example, stearic acid, hydroxystearic acid, higher fatty acids such as behenic acid, oleic acid amide, methylene bisstearamide, fatty acid amides such as ethylenebisstearamide, waxes such as montan wax, Examples include higher alcohols such as stearyl alcohol, paraffins such as liquid paraffin, and fine silica powder. However, it has been very difficult to obtain a polyvinyl chloride stretch film which is excellent in initial coloring property and transparency and suitable for food packaging free of plate-out and bloom with a combination of these conventional lubricants.

For this reason, attempts have been made to solve these problems by adding various additives and the like. For example, polybutadiene (Japanese Patent Application Laid-Open No. 60-108453) and stearoylbenzoylmethane (Japanese Patent Application Laid-Open No. -91548 gazette)
These have been proposed and have been improved to some extent, but are not yet sufficient, and further improvements in burnt and long-run properties of products have been desired.

[Means for solving the problem]

In view of such circumstances, the above-mentioned drawbacks have been improved, and as a result of intensive studies on the development of a polyvinyl chloride resin composition suitable for a stretch film for food packaging, 100 parts by weight of the polyvinyl chloride resin, adipine Acid ester plasticizer 10
5050 parts by weight, epoxidized vegetable oil 5-30 parts by weight, calcium salt of organic carboxylic acid 0.01-5 parts by weight, zinc salt of organic carboxylic acid 0.01-5 parts by weight, tris (alkylphenyl)
By adding 0.1 to 5 parts by weight of a phosphite and 0.01 to 10 parts by weight of a hydrotalcite compound and not adding a thioalcohol compound, it does not cause bloom, prevents burning, long-runs, transparency, and initial coloring. The present inventors have found a new fact that a vinyl chloride resin composition for a food packaging stretch film that is excellent and hardly causes plate-out and is easy to process can be obtained, and has completed the present invention.

The vinyl chloride resin composition of the present invention has particularly excellent suitability for melt extrusion processing.

Hereinafter, the polyvinyl chloride resin composition of the present invention will be described in detail.

The adipate ester plasticizer used in the present invention is 1
It is an ester compound or a polyester compound obtained by the usual reaction of adipic acid with one or more kinds of monohydric alcohols or polyhydric alcohols having two or more valences.

As monohydric alcohols, n-butyl alcohol, n
-Hexyl alcohol, n-octyl alcohol, n-
Examples include decyl alcohol, isoheptyl alcohol, 2-ethylhexyl alcohol, isooctyl alcohol, isononyl alcohol, and isodecyl alcohol.

As polyhydric alcohols, ethylene glycol, diethylene glycol, triethylene glycol,
Examples thereof include 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, and 1,6-hexanediol.

The amount of the adipic ester plasticizer to be added is 10 to 50 parts by weight, preferably 20 to 40 parts by weight, based on 100 parts by weight of the polyvinyl chloride resin.

Examples of the epoxidized vegetable oil used in the polyvinyl chloride resin composition of the present invention include epoxidized soybean oil, epoxidized linseed oil, epoxidized castor oil, and epoxidized tung oil.

The amount of the epoxidized vegetable oil to be added is 5 to 30 parts by weight based on 100 parts by weight of the polyvinyl chloride resin.

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

The carboxylic acids constituting the calcium and zinc salts of the organic carboxylic acids used in the present invention include caproic acid, caprylic acid, pelargonic acid, 2-ethylhexyl acid, capric acid, neodecanoic acid, undecylenic acid, lauric acid, and myristin. Acid, palmitic acid, stearic acid,
Isostearic acid, 12-hydroxystearic acid, 12-
Ketostearic acid, chlorostearic acid, phenylstearic acid, ricinoleic acid, linoleic acid, linoleic acid,
Oleic acid, arachinic acid, behenic acid, erucic acid, brassic acid and similar acids and mixtures of the above naturally occurring acids such as tallow fatty acids, coconut oil fatty acids, tung oil fatty acids, soybean oil fatty acids and cottonseed oil fatty acids, benzoic acid, p -T-
Monovalent arbonic acid such as butylbenzoic acid, ethylbenzoic acid, isopropylbenzoic acid, toluic acid, xylic acid, salicylic acid, 5-t-octylsalicylic acid, naphthenic acid, cyclohexanecarboxylic acid, oxalic acid, malonic acid, succinic acid, glutar Acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, oxyphthalic acid, chlorophthalic acid,
Monoesters of divalent carboxylic acids such as aminophthalic acid, maleic acid, fumaric acid, citraconic acid, metaconic acid, itaconic acid, and aconitic acid.

The amount of the calcium salt and zinc salt of these organic carboxylic acids to be added is 0.01 to 5 parts by weight, preferably 0.05 to 3 parts by weight, based on 100 parts by weight of the polyvinyl chloride resin.

The hydrotalcite compound used in the present invention is a hydrous double salt compound comprising magnesium and aluminum represented by the following general formula (I).

Mg _1-x Al _x (OH) ₂ A _{2 / x} · mH ₂ O (I) (where x is a real number in the range of 0 <x ≦ 0.5, and A is C
O ₃ or SO ₄ is shown, and m shows a real number. The hydrotalcite compound may be natural or synthetic. As the synthesis method, Japanese Patent Publication No. 46-2280, Japanese Patent Publication No. 50-30039, and Japanese Patent Publication
A known method described in, for example, Japanese Patent Application Laid-Open No. 1-29129 can be exemplified. Further, in the present invention, it can be used without being limited to its crystal structure, crystal particle system and the like.

In addition, the surface of the hydrotalcite compound is treated with higher fatty acids such as stearic acid, higher fatty acid metal salts such as alkali metal oleate, organic sulfonic acid metal salts such as alkali metal dodecylbenzenesulfonate, higher fatty acid amides, higher fatty acid amides, and the like. Those coated with fatty acid esters or waxes can also be used. Further, a hydrotalcite compound modified with zinc or the like can also be used.

The amount of these hydrotalcite compounds used is 0.01 to 10 parts by weight, based on 100 parts by weight of the polyvinyl chloride resin,
In particular, it is preferably 0.05 to 5 parts by weight.

Tris (alkylphenyl) phosphite used for obtaining a suitable polyvinyl chloride resin composition for a food packaging stretch film includes trisnonylphenyl phosphite, tris (dinonylphenyl) phosphite, and tris (2,4 -Di-t-butylphenyl) phosphite and the like.

The amount of the organic phosphite compound used is preferably 0.1 to 5 parts by weight based on 100 parts by weight of the polyvinyl chloride resin.

In the polyvinyl chloride resin composition for food packaging of the present invention,
β-diketones can be added. These β-
Examples of diketones include benzoyl-P-chlorobenzoylmethane, benzoylacetylmethane, bis (4-methylbenzoyl) methane, bis (2-hydroxybenzoyl) methane, tribenzoylmethane, diacetylbenzoylmethane, palmitoylbenzoylmethane, Stearoyl benzoylmethane, lauroyl benzoylmethane, dibenzoylmethane, 4-methoxybenzoyl benzoylmethane, bis (4-methoxybenzoyl) methane, bis (4-chlorobenzoyl) methane, bis (3,4-methylenedioxybenzoyl) ) Methane, benzoyl acetyl octyl methane, stearoyl 4-methoxy benzoyl methane, bis (4-tert-butyl benzoyl) methane, benzoyl acetyl ethyl methane, benzoyl Trifluoroacetyl methane, 4-tert-benzoyl-benzoyl methane, oleyl Bezoirumetan can benzoyl-phenylacetyl methane mentioned. In addition, these β
-Metal (salt, sodium, potassium, magnesium, calcium, strontium, barium, zinc, etc.) complex salts of diketones can also be added, and particularly preferred are alkanoyl and aroylmethanes and their metal complex salts.

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

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

Further, if necessary, other thermoplastic resins, rubbers, crosslinking agents, fillers, foaming agents, antistatic agents, antifogging agents, plateout preventing agents, surface treatment agents, flame retardants, fluorescent agents, fungicides Agent,
A bactericide, a metal deactivator, a release agent, a pigment, a processing aid, an antioxidant, a light stabilizer and the like can be added.

Further, as the polyvinyl chloride resin used in the present invention, vinyl chloride homopolymer, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene vinyl acetate copolymer, vinyl chloride-ethylene copolymer, chloride Vinyl-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, 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 copolymer, vinyl chloride-maleate copolymer , Vinyl chloride-methacrylic acid ester copolymer, vinyl chloride copolymer such as vinyl chloride-acrylonitrile copolymer, vinyl chloride-maleimide copolymer, and the above resin and polyethylene, polypropylene, polybutene, poly-3-methylbutene Α-
Olefin polymer or ethylene-vinyl acetate copolymer,
Polyolefins such as ethylene-propylene copolymers and their copolymers, polystyrene, acrylic resin,
Polyurethane, a copolymer of styrene and another monomer (eg, maleic anhydride, butadiene, acrylonitrile, etc.), an acrylonitrile-styrene-butadiene copolymer, an acrylate styrene-butadiene copolymer, a methacrylic acid S-L Blends with a styrene-butadiene copolymer can be mentioned. These vinyl chloride resins are emulsion polymerization, suspension polymerization, solution polymerization,
It may be obtained by any conventionally known polymerization method such as bulk polymerization.

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples.

Example 1 A kneading sample was prepared from the following formulation examples at 170 ° C. using a two-roll mill, and roll dirt and peelability were measured. The results are shown in Table 1 below.

Roll dirt was evaluated on a 10-point scale, 1 was normal,
Hereinafter, as the number increases, the stain becomes more intense, 5 indicates that a thin white film was formed as a whole, and 10 indicates that a thick cloudy film was formed.
In addition, the releasability was evaluated on a six-point scale, and the larger the number, the worse the releasability.

(Combination)

Polyvinyl chloride resin (Geon 103EP) 100 parts by weight Diisononyl adipate 20 Epoxidized soybean oil 30 Calcium benzoate 0.15 Zinc octylate 0.05 Glycerin monooleate 2.0 Trisnonylphenyl phosphite 0.5 Hydrotalcite (Table-1) 0.2 Example 2 A kneading test was performed on the following formulation at 170 ° C. using a two-roll mill to measure the time required for roll staining and white plate-out. The results are shown in Table 2 below.

(Combination)

Polyvinyl chloride resin (TK-1300) 100 parts by weight Di C adipate _6-10 alcohol 35 Epoxidized soybean oil 20 Calcium oleate 0.1 Zinc octylate 0.1 Zinc ricinoleate 0.1 Poly (n: 2-3) glycerol monooleate 1.5 Trisnonylphenyl phosphite 0.5 Hydrotalcite (Table 2) 0.15 Example 3 A kneading test was performed on the following formulation at 170 ° C. using a two-roll mill to measure roll stains and time required for adhesion to the roll. Further, the same composition was compression-molded at 160 ° C. and 150 kg / cm ² for 5 minutes to prepare a 3 mm-thick press sheet, and the initial coloring and transparency were observed. The results are shown in Table 3 below.

(Combination)

100 parts by weight of vinyl chloride resin (Geon 103EP) ADK CIZER PN-400 ^* 25 Epoxidized linseed oil 5 Epoxidized soybean oil 5 Calcium benzoate 0.5 Zinc oleate 1.0 Poly (n: 3-5) glycerol monooleate 1.0 Trisnonylph Enyl phosphite 0.4 Hydrotalcite (Table 3) 0.2 Polyoxyethylene alkyl ether 1.5 * Adipic acid plasticizer made by Adeka Argus Chemicals Example 4 A kneading test was performed at 170 ° C. using a two-roll mill with the following composition to further examine the effect of using β-diketone in combination with the composition of the present invention. Was measured. The results are shown in the following table.
It is shown in FIG.

[Compound] Polyvinyl chloride resin 100 parts by weight Octyl adipate 35 ADK CIZER O-130P ^* 5 Calcium oleate 0.15 Zinc ricinoleate 0.2 Zinc octylate 0.1 Polyoxyethylene alkyl ether 1.5 Trisnonylphenyl phosphite 0.5 Mg _0.7 Al _0.3 (OH) ₂ (CO ₃ ) _0.15・ 0.54H ₂ O 0.15 β-diketones (Table-4) 0.1 * Adeka Argus Chemical's epoxy plasticizer

────────────────────────────────────────────────── (5) Continuation of the front page (51) Int.Cl. ⁶ identification symbol FI C08K 5:11 5:15 5: 526) (56) References JP-A-63-46248 (JP, A) JP-A-62- 91548 (JP, A) JP-A-58-47045 (JP, A) JP-A-60-123545 (JP, A) JP-A-2-222436 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C08L 27/06 C08K 3/18 C08K 5/098 C08K 5/11 C08K 5/15 C08K 5/526

Claims (1)

(57) [Claims] 1. An adipate plasticizer of 10 to 50 parts by weight, an epoxidized vegetable oil of 5 to 30 parts by weight, a calcium salt of an organic carboxylic acid of 0.01 to 5 parts by weight, based on 100 parts by weight of a polyvinyl chloride resin. 0.01 to 5 parts by weight of zinc salt of organic carboxylic acid, 0.1 to 0.1 parts of tris (alkylphenyl) phosphite
A polyvinyl chloride resin composition for a stretch film for food packaging containing 5 parts by weight and 0.01 to 10 parts by weight of a hydrotalcite compound represented by the following general formula (I) and containing no thioalcohol compound. Mg _1-x Al _x (OH) ₂ A _{2 / x} · mH ₂ O (I) (where x is a real number in the range of 0 <x ≦ 0.5, and A is C
O ₃ or SO ₂ is shown, and m shows a real number. )