JP4738204B2 - Vinyl chloride resin composition and stretch film - Google Patents

Description

  The present invention relates to a polyvinyl chloride composition and a stretch film. In particular, even if the amount of plasticizer added is reduced, flexibility and molding processability are not impaired. The present invention relates to a polyvinyl chloride composition and a stretch film which are suitably used for stretch packaging with a small amount of n-heptane extract measured by a defined evaporation residue test method, and thus low migration of plasticizers to fatty foods.

For food packaging, especially fresh food packaging such as meat, fresh fish and fruits and vegetables, many stretch films made of vinyl chloride resin with excellent transparency, flexibility and heat sealability have been developed and widely used as food packaging films. in use. Usually, these films are generally formed by using a polyvinyl chloride resin composition in which an adipic ester plasticizer and an epoxidized vegetable oil are used as plasticizers on a vinyl chloride resin.
Conventionally, these films have been regarded as important for the hygiene of the compounding agent and the transferability to foods. In terms of its hygiene, it has established a non-toxic formulation from the additives described in the US FDA standards (Food and Drug Administration) and Japanese PL standards (self-regulatory standards for vinyl chloride resin packaging containers, etc.) For the transferability to foods, etc., the extraction test is conducted as an evaporation residue test method by the Ministry of Health and Welfare Notification No. 20 test, and in particular, the extraction test using n-heptane as a pseudo extraction solvent for fats and oils and fatty foods is confirmed and confirmed. Yes.

However, due to the recent growing interest in the safety of these plastic materials and their additives, the extraction of additives such as plasticizers, stabilizers, antifogging agents, etc., which are regarded as important by the PL standard and the Ministry of Health and Welfare notification, etc., is extremely difficult. There is a need for fewer food packaging materials.
In order to satisfy these requirements, Patent Document 1 is proposed.
However, in the technique described in Patent Document 1, it is a combination of a polyester plasticizer and a glycerin ester plasticizer, and when the polyester plasticizer is large depending on the ratio, the polarity of the ester portion is strong and a screw or barrel during molding processing, There is a problem in that productivity tends to be poor due to sticking to a metal surface such as a conduit or a metal mold and deterioration. Moreover, when there are many glycerin ester type plasticizers, there exists a problem that the effect of reducing the extraction amount of n-heptane is hard to be acquired. Therefore, there is still no technology that can achieve both high productivity and low extractability.

Japanese Patent No. 2773839

  Under such circumstances, the present invention provides a vinyl chloride resin composition that is suitable for food container packaging, has excellent extrusion processability, and can reduce the amount of n-heptane extracted, and a stretch film using the same. It is intended to do.

As a result of intensive studies to solve the above problems, the inventors of the present invention can obtain a stretch film having excellent molding processability and a small n-heptane extraction amount by combining a specific plasticizer and a compounding agent. And found that the above problems can be solved, and has been completed.
That is, the gist of the present invention is that
1. Including 100 parts by mass of vinyl chloride resin, 1-30 parts by mass of adipate plasticizer, 1-25 parts by mass of epoxidized vegetable oil, 1-60 parts by mass of ethylene-vinyl acetate-carbon monoxide copolymer A vinyl chloride resin composition for food packaging comprising:
2. A stretch film formed by using the vinyl chloride resin composition according to 1 above. 3. 3. The stretch film as described in 2 above, having a thickness of 10 μm or less and an n-heptane extract amount of 50 ppm by mass or less measured by an evaporation residue test method stipulated in Ministry of Health and Welfare Notification No. 20 of 1982.
It is in.

  The polyvinyl chloride composition obtained by the present invention and the stretch film comprising the same are suitably used for food packaging, and are particularly excellent in moldability and have a small n-heptane extract amount as defined in Ministry of Health and Welfare Notification No. 20, and therefore It is possible to obtain a vinyl chloride resin composition and a stretch film with less plasticizer migration to fats and oils and fatty foods.

Hereinafter, the present invention will be described in detail, but the scope of the present invention is not limited to the embodiments described below.
The vinyl chloride resin in the present invention is a vinyl chloride homopolymer, a copolymer with a monomer copolymerizable with vinyl chloride (hereinafter referred to as vinyl chloride copolymer), this vinyl chloride copolymer. Examples include graft copolymers obtained by graft-copolymerizing vinyl chloride to polymers other than polymers, and these copolymers have lower mechanical properties when the content of constituent units other than vinyl chloride in the copolymer increases. Therefore, it is preferable to contain 60% by mass or more of vinyl chloride. Each polymer may be obtained by any polymerization method such as emulsion polymerization method, suspension polymerization method, solution polymerization method, bulk polymerization method, etc., and used alone or in combination of two or more polymers. Is done. The monomer copolymerizable with vinyl chloride is not particularly limited as long as it has a reactive double bond in the molecule. For example, α-olefins such as ethylene, propylene, butylene; vinyl acetate, propionic acid Vinyl esters such as vinyl; vinyl ethers such as butyl vinyl ether and cetyl vinyl ether; unsaturated carboxylic acids such as acrylic acid and methacrylic acid; esters of acrylic acid or methacrylic acid such as methyl acrylate, ethyl methacrylate, and phenyl methacrylate Aromatic vinyls such as styrene and α-methylstyrene; vinyl halides such as vinylidene chloride and vinyl fluoride; N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide; It is used alone or in combination of two or more.
The polymer other than the vinyl chloride copolymer may be any polymer that can be graft copolymerized with vinyl chloride, such as an ethylene-vinyl acetate copolymer, an ethylene-vinyl acetate-carbon monoxide copolymer, Ethylene-ethyl acrylate copolymer, ethylene-ethyl acrylate-carbon monoxide copolymer, ethylene-butyl acrylate copolymer, ethylene-butyl acrylate-carbon monoxide copolymer, ethylene-methyl methacrylate copolymer, ethylene- A propylene copolymer, an acrylonitrile-butadiene copolymer, polyurethane, chlorinated polyethylene, chlorinated polypropylene and the like can be mentioned, and these are used singly or in combination of two or more.

  The average degree of polymerization of the vinyl chloride resin used in the present invention is preferably 700 to 1,500. If the average degree of polymerization is less than 700, the fracture resistance and other mechanical properties are inferior. If the average degree of polymerization exceeds 1,500, the melt viscosity is remarkably increased, the molding processing temperature and the decomposition temperature are close, and the production stability is inferior. . Therefore, the average degree of polymerization of the vinyl chloride resin in the present invention is more preferably 900 to 1,400.

The adipic acid ester plasticizer in the present invention is a mixed adipine of an adipic acid ester plasticizer having an alkyl group having 8 or more carbon atoms, two or more aliphatic alcohols having 10 or less alkyl groups, and adipic acid And at least one selected from acid ester plasticizers, the former adipic acid ester plasticizer includes dioctyl adipate (n-octyl, 2-ethylhexyl; an alcohol having an alkyl group having 8 carbon atoms) Ester), diisononyl adipate (same 9), didecyl adipate (same 10), diisodecyl adipate (same 10), and the like. These are used alone or in combination of two or more. It is done. The latter mixed adipate plasticizer is a reaction product of two or more aliphatic alcohols having an alkyl group having 10 or less carbon atoms and adipic acid, and includes C8,10 adipate (8 carbon atoms, Mixed esters of alcohols having 10 alkyl groups), C7,9 adipate (7,9), C6,8,10 adipate (6,8,10), etc. It is used alone or in combination of two or more.
Among them, diisononyl adipate as an adipate plasticizer and C6,8,10 adipate and C7,9 adipate as mixed adipate plasticizers have the extrudability and stretchability of the stretch film, respectively. It is easy to give and is used suitably. This addition amount is 1 to 30 parts by mass. If it is less than 1 part by mass, the effect of imparting flexibility is not sufficient, and if it exceeds 30 parts by mass, the amount of extraction with n-heptane increases. More preferably, it is 5-20 mass parts.

  The epoxidized vegetable oil in this invention is added in order to improve the extrusion moldability of a stretch film, especially the thermal stability at the time of extrusion molding. Examples of the epoxidized vegetable oil include epoxidized soybean oil, epoxidized linseed oil, epoxidized safflower oil, and the like, among which epoxidized soybean oil is preferably used in terms of the above-described effects. This addition amount is 1 to 25 parts by mass with respect to 100 parts by mass of the polyvinyl chloride resin. If this is less than 1 part by mass, the thermal stability during extrusion molding is poor, and if it exceeds 25 parts by mass, there is a problem that odor generation and n-heptane extraction amount increase. Therefore, it is more preferably 5 to 20 parts by mass.

The ethylene-vinyl acetate-carbon monoxide copolymer in the present invention can impart flexibility to the film even when the amount of plasticizer added is reduced, and also prevents sticking to the metal surface during molding and has a viscosity-reducing effect. It is added to prevent burning, and the amount added is 1 to 60 parts by mass.
If the addition amount of the ethylene-vinyl acetate-carbon monoxide copolymer is less than 1 part by mass, the effect of imparting flexibility until the addition amount of the plasticizer can be reduced cannot be obtained, and if it exceeds 60 parts by mass, the stiffness of the film (stiffness) Will drop too much, resulting in poor finish after packaging. Moreover, the acetic acid odor peculiar to a vinyl acetate type copolymer becomes strong. Therefore, it is more preferably 5 to 50 parts by mass.
The ethylene-vinyl acetate-carbon monoxide copolymer used in the present invention is usually a ternary copolymer comprising 40 to 80% by mass of ethylene units, 10 to 60% by mass of vinyl acetate units and 3 to 30% by mass of carbon monoxide units. A polymer is preferably used. Such a ternary copolymer is a known one, and examples thereof include trade name “Elvaroy 741” manufactured by Mitsui-Deupon Polychemical Co., Ltd.

  In the film of the present invention, in addition to the components described above, an antifogging agent, a stabilizer, a lubricant and the like can be appropriately selected and blended as necessary. Examples of the antifogging agent include monoglycerin fatty acid ester, polyglycerin fatty acid ester, sorbitan fatty acid ester, and polyoxyethylene alkyl ether. The monoglycerin fatty acid ester is preferably a monoglycerin ester of a saturated or unsaturated fatty acid having 12 to 18 carbon atoms. Specific examples include monoglycerol laurate, monoglycerol myristate, monoglycerol palmitate, monoglycerol stearate, monoglycerol oleate, and monoglycerol linoleate. As the polyglycerol fatty acid ester, a polyglycerol ester of a saturated or unsaturated fatty acid having 12 to 18 carbon atoms is preferable. Specific examples include polyglycerol laurate, polyglycerol myristate, polyglycerol palmitate, polyglycerol stearate, polyglycerol oleate, and polyglycerol linoleate. The sorbitan fatty acid ester is preferably a sorbitan ester of a saturated or unsaturated fatty acid having 12 to 18 carbon atoms. Specific examples include sorbitan laurate, sorbitan myristate, sorbitan palmitate, sorbitan stearate, sorbitan oleate, sorbitan renolate and the like. The polyoxyethylene alkyl ether is preferably a saturated alcohol polyoxyethylene alkyl ether having 12 to 18 carbon atoms, more preferably a polyoxyethylene alkyl ether having 3 to 7 added moles of ethylene oxide. Specific examples include polyoxyethylene lauryl ether, polyoxyethylene myristyl ether, polyoxyethylene palmityl ether, and polyoxyethylene stearyl ether.

  Among the above, monoglycerol laurate, monoglycerol oleate, monoglycerol linoleate, polyglycerol laurate, polyglycerol oleate, polyglycerol linoleate, sorbitan laurate, sorbitan oleate, sorbitan linoleate, polyoxyethylene lauryl ether These may be used alone or in combination of two or more.

  Stabilizers used in the present invention include 2-ethylhexyl acid, higher fatty acids having 8 to 22 carbon atoms, citric acid, gluconic acid, sorbic acid, benzoic acid, isodecanoic acid, neodecanoic acid and other calcium salts, and 2-ethylhexyl. Examples thereof include Ca—Zn salts made of zinc salts such as acids, higher fatty acids having 8 to 22 carbon atoms, isodecanoic acid and neodecanoic acid, and these are used alone or in combination of two or more. In addition, phosphorus compounds such as 4,4′isobutylidenebis- (3-methyl 6-tert-butylphenyl-ditridecyl phosphite), stearoylbenzoylmethane ( SBM), β-diketones such as dehydroacetic acid, polyol compounds such as pentaerythritol and dipentaerythritol, and compounds described in the positive list such as antioxidants and ultraviolet absorbers may be used in combination. The amount of these auxiliaries added is preferably 1 part by mass or less with respect to 100 parts by mass of the vinyl chloride resin.

  Examples of the lubricant include higher fatty acids having 8 to 22 carbon atoms such as lauric acid, myristic acid, palmitic acid, stearic acid, and isostearic acid; 12-hydroxystearic acid; and 8 to 8 carbon atoms such as lauric acid amide and stearic acid amide. 22 higher fatty acid amides; aliphatic hydrocarbons such as liquid paraffin, chlorinated liquid paraffin, and synthetic paraffin; monoglycols such as glycerin and propylene glycol; and polyglycols such as polyethylene glycol and polypropylene glycol. Used in combination of two or more. These addition amounts are each preferably 1 part by mass or less with respect to 100 parts by mass of the vinyl chloride resin.

  The vinyl chloride resin composition in the present invention can be obtained by charging the above polymer and additives into a commonly used mixing apparatus such as a super mixer, and heating, stirring and cooling. The formation of the stretch film in the present invention is obtained by forming the obtained compound into a film by a T-die method or an inflation method using a single-screw, twin-screw, or multi-screw extruder.

Hereinafter, although the effect of the present invention is explained in detail based on an example, the present invention is not limited to the following examples.
The compounding agents shown below were weighed at the ratios shown in the table, and mixed using a Henschel mixer to obtain a vinyl chloride resin composition. The composition was supplied to a single-screw extruder equipped with a T die having a width of 300 mm and a lip gap of 0.5 mm, and extrusion molding was performed at a mold setting temperature of 200 ° C. The thickness of the obtained film and the evaluation results are also shown in the table.

Vinyl chloride resin (average polymerization degree 1050): Shin-Etsu Chemical Co., Ltd. (trade name “TK-1000”)
・ Adipate ester plasticizer: Taoka Chemical Co., Ltd. (trade name “DINA”)
C6, 8, 10A: Taoka Chemical Industries, Ltd. (trade name “D-610A”)
・ Ethylene-vinyl acetate-carbon monoxide copolymer: Mitsui, manufactured by Deyupon Polychemical Co., Ltd. (trade name “Elvaroy 741”)
Epoxidized soybean oil (ESBO): manufactured by Kao Corporation (trade name “Capox S-6”)
Polyester plasticizer: manufactured by Asahi Denka Kogyo Co., Ltd. (trade name “PN-310”)
・ Glycerin ester plasticizer: Riken Vitamin Co., Ltd. (trade name “PL-012”)
Ca-Zn stabilizer: manufactured by Asahi Denka Kogyo Co., Ltd. (trade name "SP-76")
Antifogging agent (diglycerin oleate): manufactured by Riken Vitamin Co., Ltd. (trade name “DO-100”)

[Packaging aptitude]
Appropriateness of automatic packaging machine: Eight shishamo were put on a PP tray, and automatic packaging was carried out at a packaging speed of 40 packs / min by an automatic packaging machine “A-18K” manufactured by Fujikikai, and packaging suitability was evaluated according to the following criteria.
What can be packaged without wrinkles or tears: ○
Slight lack of slipping, wrinkles, etc., but can be packaged: △
Wrinkles, tears or lack of tension, unsuitable for packaging: ×

[Anti-fogging property]
The glass dish was filled with 100 g of water at 10 ° C. and wrapped with a stretch film, and this was put in a refrigerator maintained at −2 to 2 ° C., and the state at the time when 1 hour had passed was observed and evaluated according to the following criteria.
Water film is uniform and the contents are visible: ○
There are some water droplets and the contents are a little difficult to see: △
There are large water droplets on the entire surface and the contents cannot be seen: ×

[Food hygiene test]
-N-Heptane extraction test: The extraction amount was measured by the evaporation residue test method defined in the Ministry of Health and Welfare Notification No. 20 in 1982 and indicated as n-heptane extraction amount (ppm) (50 mass ppm or less: ○, 50 mass ppm Super: x).

[Molding processability]
When the extrusion molding was performed, the appearance of the film was observed, the state of occurrence of burning and carbide was observed, and the determination was made according to the following criteria.
No problem with film appearance: ○
The film appearance is slightly yellowish, but there is no problem in quality:
The appearance of the film is strongly reddish and there is a problem in quality due to the appearance of carbides.

It can be seen from Table 1 that Examples 1 to 6 are excellent in all the properties of packaging suitability, antifogging n-heptane extraction amount, and moldability.
On the other hand, in Comparative Example 1, since the amount of adipic ester plasticizer (DINA) added is too large, there is no rigidity (waist) of the film, and therefore the film thickness cannot be reduced to 13 μm or less. The amount of extraction increases. In Comparative Example 2, although the amount of ethylene-vinyl acetate-carbon monoxide copolymer added was excessive, the amount of n-heptane extracted was small enough, but the film was not stiff, the acetic acid odor was strong, and the antifogging agent The migration (bleed) to the film surface is suppressed and the antifogging property is poor. In Comparative Example 3, since the amount of epoxidized soybean oil added is extremely reduced, the thermal stability is poor and the sample cannot be collected. In Comparative Example 4, a polyester plasticizer and a glycerin ester plasticizer are used in combination as a known low extraction technique, but the n-heptane extraction amount is large due to the thick thickness, but even if the wall thickness is reduced (comparison) Example 6) The extraction amount reduction effect is not sufficient. Further, in Comparative Example 5, the ratio of the polyester plasticizer is high and the amount of n-heptane extracted is small, but the adhesion to the extruder die or the like is large, and the film becomes burnt and inferior in moldability.

Claims (3)

Including 100 parts by mass of vinyl chloride resin, 1-30 parts by mass of adipate plasticizer, 1-25 parts by mass of epoxidized vegetable oil, 1-60 parts by mass of ethylene-vinyl acetate-carbon monoxide copolymer A vinyl chloride resin composition comprising A stretch film formed by using the vinyl chloride resin composition according to claim 1. The stretch film according to claim 2, wherein the stretch film has a thickness of 10 μm or less and an n-heptane extraction amount measured by an evaporation residue test method stipulated in Ministry of Health and Welfare Notification No. 20 of 1982 is 50 ppm by mass or less.