JPH07179703A - Vinylidene chloride copolymer resin composition and monolayered film - Google Patents

Abstract

PURPOSE:To obtain the subject composition comprising plural vinylidene copolymers having different number-average mol.wts., respectively, excellent in moldability, giving films good in barrier properties, non-extractability and high-frequency sealability, and useful for food-packaging materials, etc. CONSTITUTION:This composition excellent in moldability, good in barrier properties, non-extractability with oily foods, and high frequency sealability, and useful for barrier packaging materials or wrapping films for foods, etc., comprises (A) 50-98wt.% of a vinylidene chloride copolymer resin composition having a vinylidene chloride content of 50-99wt.% and having a weightaverage mol.wt. of 50000-300000 measured by a gel permeation chromatography method, and (B) 2-50wt.% of a vinylidene chloride copolymer resin composition having a vinylidene chloride content of 50-99wt.% and having a weight-average mol.wt. of 5000 to 80000 or 0.8 times of the weight-average mol.wt. of the vinylidene chloride copolymer resin composition of the component A, measured by a gel- permeation chromatography method.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel vinylidene chloride-based copolymer resin composition having excellent moldability, and a barrier property, non-extractability, mechanical properties, and high frequency property of the vinylidene chloride-based copolymer resin composition. The present invention relates to a single layer film having excellent sealing properties. The monolayer film of the present invention is mainly composed of ham,
It can be used as a wrap film and a packaging material that requires barrier properties such as sausage, cheese, prepared foods and other foods.

In the present invention, the monolayer film used as a packaging material is packaged mainly in a tubular film preformed according to the shape of the food to be packaged with the food, and then both ends thereof are joined with aluminum wires or the like. There are two types: one for punching, and one for forming a tube-shaped film according to the shape of food by high-frequency sealing the original film and automatically filling the food and tying with an aluminum wire or the like.

[0003]

2. Description of the Related Art Films, sheets, and containers produced from vinylidene chloride-based copolymer resin compositions have excellent oxygen barrier properties, moisture resistance, transparency, chemical resistance, oil resistance, adhesion, and heat shrinkability. Since it is highly hygienic, it is used in a wide variety of food packaging materials, wrap films, and the like. But,
Since vinylidene chloride-based copolymer resins have poor thermal stability, conventionally, when producing these films, sheets, and containers, liquid plasticizers have been used to prevent thermal decomposition due to frictional heat during molding. % Addition was essential.

By adding a liquid plasticizer, it has been unavoidable that the vinylidene chloride copolymer resin has the greatest feature of lowering the barrier property and increasing the amount of extraction by oily foods. Also, if the molecular weight of the resin is made extremely small, it is possible to prevent thermal decomposition due to frictional heat during molding, even if almost no liquid plasticizer is added, but the mechanical strength of the obtained film is very small. It was not practical.

Further, as a method for obtaining a vinylidene chloride-based copolymer resin composition which can be molded without adding a liquid plasticizer or by adding a very small amount thereof, JP-A-53-16
No. 753, a method of blending a resin other than a vinylidene chloride copolymer resin having a low softening temperature and a low melt viscosity, a glass transition temperature as described in JP-A-04-72314. It is known that vinylidene chloride-based resins are internally plasticized by copolymerization of acrylic acid ester to reduce the viscosity, but the monolayer films obtained from the resins obtained by these methods all have a reduced barrier property. It was insufficient from the viewpoint of suppressing

Further, a barrier property-imparting layer obtained from a vinylidene chloride copolymer resin composition having a small molecular weight and a small amount of a liquid plasticizer as described in JP-A-55-156058, and a large molecular weight are provided. A multilayer film composed of a mechanical property imparting layer obtained from a vinylidene chloride copolymer resin composition having a large amount of a liquid plasticizer has also been proposed, but the strength of the barrier imparting layer is small, and the cost of the molding apparatus is large. It is a problem.

[0007]

The object of the present invention is to provide a vinylidene chloride copolymer having excellent moldability without adding a liquid plasticizer at all or with an extremely small amount added as compared with the prior art. It is an object of the present invention to provide a resin composition and a monolayer film comprising the vinylidene chloride resin copolymer composition, which is extremely excellent in barrier properties, non-extractability by oily foods, mechanical properties, and high-frequency sealing property. .
The high-frequency sealing property as used herein means that the high-frequency sealing portion does not peel off under the influence of heat or oil content of the contents when a package filled with food such as ham and sausage is heat-sterilized.

[0008]

DISCLOSURE OF THE INVENTION The inventors of the present invention have found that a vinylidene chloride-based copolymer resin having excellent molding processability without adding a liquid plasticizer at all or with an extremely small amount added as compared with the prior art. Composition, and a barrier property comprising the vinylidene chloride resin composition, non-extractability by oily food,
As a result of intensive research to obtain a monolayer film having excellent mechanical properties and high-frequency sealing property, a specific composite vinylidene chloride-based copolymer resin composition and a monolayer film obtained therefrom can achieve the object. The present invention has been completed and the present invention has been completed.

That is, the present invention provides a composite vinylidene chloride-based copolymer resin composition comprising the following vinylidene chloride-based copolymer resin composition A and vinylidene chloride-based copolymer resin composition B: Provided is a composite vinylidene chloride-based copolymer resin composition having a content of 50% by weight or more and 98% by weight or less. In addition, A: vinylidene chloride content is 50% by weight or more and 99% by weight
The following is a vinylidene chloride-based copolymer resin composition B having a weight average molecular weight of 50,000 or more and 300,000 or less by gel permeation chromatography: B: vinylidene chloride content of 50% by weight or more and 99% by weight or less.
The weight average molecular weight by the gel permeation chromatography method is 55,000 or more, and the weight average molecular weight of the vinylidene chloride copolymer resin composition A is 0.8 or less.
Double vinylidene chloride-based copolymer resin composition, which is less than or equal to 80,000

There is also provided a single-layer film comprising the composite vinylidene chloride-based copolymer resin composition described in 1. Hereinafter, the present invention will be described in detail. The composite vinylidene chloride-based copolymer resin composition of the present invention is composed of two types of vinylidene chloride-based copolymer resins having different average molecular weights, and the resin composition A having a larger average molecular weight is a component for imparting mechanical strength and high-frequency sealing property. The resin composition B, which is positioned as an imparting component and has a smaller average molecular weight, is positioned as a plasticizer component during molding. Unlike conventional vinylidene chloride-based copolymer resin compositions, it is not necessary to add a liquid plasticizer at all or almost at the time of molding, so that the monolayer film obtained by molding has reduced barrier properties and oiliness. It is possible to prevent an increase in extractability due to food.

FIG. 1 shows the molecular weight range of the composite vinylidene chloride copolymer resin composition of the present invention. That is, the weight average molecular weight (MwA) of the vinylidene chloride copolymer resin composition A and the weight average molecular weight (MwB) of the vinylidene chloride copolymer resin composition B constituting the composite vinylidene chloride copolymer resin composition of the present invention. In this relation, the range surrounded by a straight line (including the straight line) is the molecular weight range of the composite vinylidene chloride copolymer resin composition of the present invention.

In the composite vinylidene chloride copolymer resin composition of the present invention, both MwA and MwB must satisfy the following formulas (1), (2) and (3). 50,000 ≦ MwA ≦ 300,000 (1) MwA ≧ 100,000 5,000 ≦ MwB ≦ 80,000 (2) MwA <100,000 5,000 ≦ MwB ≦ 0.8 x MwA (3)

FIG. 2 shows a vinylidene chloride copolymer resin composition A having a weight average molecular weight of 148,000 and a number average molecular weight of 510,000, a weight average molecular weight of 46,000 and a number average molecular weight of 2. 20,000 vinylidene chloride-based copolymer resin composition B, and vinylidene chloride-based copolymer resin composition A and vinylidene chloride-based copolymer resin composition B mixed in a weight ratio of 80/20 1 shows the molecular weight distribution of a film obtained by molding a resin composition.
The molecular weight distribution was measured by gel permeation chromatography using polystyrene as a standard.

Generally, a vinylidene chloride copolymer resin composition shows a slight change in molecular weight by molding, but the change is small. Therefore, the molecular weight distribution of the film obtained by molding from the composite vinylidene chloride-based copolymer resin composition of the present invention reflects the molecular weight distribution of the resin composition of the raw material, and is processed from a single resin composition. It is larger than the molecular weight distribution of the resulting film.

Vinylidene chloride copolymer resin composition A constituting the composite vinylidene chloride copolymer resin composition of the present invention
Further, as the vinylidene chloride comonomer for obtaining the vinylidene chloride-based copolymer resin composition B, one or more monomers copolymerizable with vinylidene chloride can be used.

For example, as the monomer copolymerizable with vinylidene chloride, any monomer having a high copolymerizability may be used, but as industrially useful, vinyl chloride; methyl acrylate, butyl acrylate, 2-ethylhexyl. Acrylic esters such as acrylates; Methacrylic esters such as methyl metaacrylate, butyl methacrylate, 2-ethylhexyl methacrylate; vinyl esters of aliphatic carboxylic acids such as vinyl acetate and vinyl propionate;

Acrylic acid, methacrylic acid, itaconic acid,
Unsaturated aliphatic carboxylic acids such as crotonic acid, maleic acid, fumaric acid and maleic anhydride; Half-esters and diesters of unsaturated aliphatic carboxylic acids such as maleic acid and itaconic acid; styrene, (meth) acrylonitrile, (meth)
Olefins having a copolymerizable double bond such as acrylamide; dienes having two copolymerizable double bonds such as isoprene and butadiene; and their chlorides such as chlorobutadiene; glycidyl (meth) acrylate, allyl glycidyl ether A monomer having a copolymerizable double bond and an epoxy group; a monomer having two copolymerizable double bonds in the molecule such as (meth) acrylic acid ester of divinylbenzene or a divalent aliphatic alcohol. Examples thereof include a polymer. Particularly, vinyl chloride, methyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate are preferable.

Vinylidene chloride copolymer resin composition A constituting the composite vinylidene chloride copolymer resin composition of the present invention
When the vinylidene chloride content is less than 50% by weight, the barrier property of the obtained monolayer film is not sufficient, and when the vinylidene chloride content exceeds 99% by weight, the composite vinylidene chloride copolymer resin composition is Moldability is unsatisfactory. A particularly preferable range of the vinylidene chloride-based copolymer resin composition A is 80% by weight or more and 97% by weight or less.

When the vinylidene chloride copolymer resin composition B of the composite vinylidene chloride copolymer resin composition of the present invention has a vinylidene chloride content of less than 50% by weight, the barrier properties of the resulting monolayer film are not sufficient. However, when the vinylidene chloride content exceeds 99% by weight, the molding processability of the composite vinylidene chloride copolymer resin composition is unsatisfactory. The particularly preferable range of the vinylidene chloride-based copolymer resin composition B is 60% by weight or more and 97% by weight or more.
It is less than or equal to weight%.

Vinylidene chloride copolymer resin composition A constituting the composite vinylidene chloride copolymer resin composition of the present invention
When the weight average molecular weight is less than 50,000, the mechanical strength and high-frequency sealing property of the obtained monolayer film are not sufficient, and when the weight average molecular weight exceeds 300,000, the composite vinylidene chloride copolymer resin composition Moldability is unsatisfactory.

When the weight average molecular weight of the vinylidene chloride copolymer resin composition B of the composite vinylidene chloride copolymer resin composition of the present invention is less than 50,000, the resulting monolayer film has a mechanical strength and a high frequency seal. When the weight average molecular weight of the vinylidene chloride copolymer resin composition A is 0.8 times the weight average molecular weight of the vinylidene chloride copolymer resin composition A, which is smaller than 80,000, the composite vinylidene chloride copolymer resin composition is molded. The workability is unsatisfactory.

When the content of the vinylidene chloride copolymer resin composition A in the composite vinylidene chloride copolymer resin composition of the present invention is less than 50% by weight, the mechanical strength and high frequency sealing property of the obtained monolayer film are high. Is not sufficient, and when it exceeds 98% by weight, the moldability of the composite vinylidene chloride copolymer resin composition is unsatisfactory. Further, the vinylidene chloride-based copolymer resin composition A and the vinylidene chloride-based copolymer resin composition B of the composite vinylidene chloride-based copolymer resin composition of the present invention are any of suspension polymerization method, emulsion polymerization method, solution polymerization method and the like. Although the method is also possible, the suspension polymerization method is preferably used.

The suspension polymerization method may be a direct suspension method in which a monomer is added to water in which a suspending agent is dissolved, or a suspension agent may be added to a monomer as described in JP-A-62-280207. Which is a suspension method in which the monomer phase is a continuous phase and the water is a discontinuous phase to form a dispersion in which the monomer is a discontinuous phase and the water is a continuous phase. But good.

Oil solubility used for producing the vinylidene chloride-based copolymer resin composition A and the vinylidene chloride-based copolymer resin composition B of the composite vinylidene chloride-based copolymer resin composition of the present invention by suspension polymerization As the initiator, organic peroxides such as lauroyl peroxide, benzoyl peroxide, t-butylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate, t
-Butyl peroxypivalate, diisopropyl peroxydicarbonate; azobis compounds such as azobisisobutyronitrile can be used.

As the suspending agent, cellulose derivatives such as methyl cellulose, ethyl cellulose and hydroxypropyl methyl cellulose; partially saponified products of polyvinyl alcohol and polyvinyl acetate can be used. As the water-soluble initiator used for producing the vinylidene chloride-based copolymer resin composition A and the vinylidene chloride-based copolymer resin composition B of the composite vinylidene chloride-based copolymer resin composition of the present invention by emulsion polymerization, Inorganic peroxides such as sodium persulfate, potassium persulfate, ammonium persulfate; organic peroxides such as redox systems of t-butyl hydroperoxide and sodium formaldehyde sulfoxide can be used.

As the emulsifier, anionic surfactants such as sodium alkylsulfonate and sodium alkylbenzenesulfonate; nonionic surfactants such as polyoxyethylene alkylphenyl ether can be used. In order to produce the vinylidene chloride-based copolymer resin composition B in the composite vinylidene chloride-based copolymer resin composition of the present invention, trichloroethylene,
A chain transfer agent such as dodecyl mercaptan, octyl mercaptan, thioglycolic acid, and 2-ethylhexyl thioglycolate may be added and mixed at the time of polymerization.

Further, the polymerization temperature for producing the vinylidene chloride copolymer resin composition A and the vinylidene chloride copolymer resin composition B of the composite vinylidene chloride copolymer resin composition of the present invention is not particularly limited, Generally 20-100
C., preferably 40 to 90.degree. C. is suitable. After the completion of the above-mentioned polymerization, filtration, washing with water and drying are carried out if necessary, but in the case of an emulsion, aluminum sulfate, calcium chloride or the like is salted out and then a usual post-treatment is carried out to obtain a powdery or granular resin. You can get it.

The vinylidene chloride-based copolymer resin composition A and the vinylidene chloride-based copolymer resin composition B may be blended in a powder or granular dry state after drying, or in a slurry state before filtration. Although it may be carried out, when the molecular weight of the vinylidene chloride copolymer resin composition B is small, blending in a slurry state is preferable in order to prevent blocking during drying. Furthermore, the vinylidene chloride-based copolymer resin composition A and the vinylidene chloride-based copolymer resin composition B are separately produced and then blended without changing the polymerization conditions in the same reaction tank to change the two-stage polymerization. It is also possible to obtain it.

The obtained composite vinylidene chloride copolymer resin composition may be directly subjected to molding processing, but various additives may be added if necessary. As various additives, liquid plasticizers such as dibutyl sebacate (DBS) and acetyltributyl citrate (ATBC) which are added in extremely small amounts as compared with conventional additives; epoxidized soybean oil, epoxidized linseed oil, bisphenol A diglycidyl Epoxy compounds such as ether, epoxidized polybutadiene and epoxidized octyl stearate; antioxidants such as vitamin E, butylhydroxytoluene (BHT) and thiodipropionic acid alkyl ester; sodium pyrophosphate, sodium tripolyphosphate, ethylenediaminetetraacetic acid 2 Examples thereof include heat stabilizing aids such as sodium (EDTA-2Na) and magnesium oxide; various light stabilizers; various lubricants; various coloring agents.

The single-layer film obtained from the composite vinylidene chloride copolymer resin composition according to the present invention is mainly an extrusion molding method, in particular, an inflation method, that is, it is extruded from a circular die of a screw extruder and a tubular extrudate is obtained at room temperature. After passing through the following first cooling bath and then passing through a second preheating bath, a method of forming a film by forming air bubbles by injecting air between two sets of pinch rollers, or a T-die method, that is, Two types of methods are used: a method of extruding and cooling from a T-die to produce a film. Film is 2
Axial stretching is preferred.

If necessary, the molded film may be subjected to post-processing such as corona discharge treatment. In this way, the obtained monolayer film has excellent barrier properties, non-extractability by oily foods, mechanical properties, and high-frequency sealing properties, and requires barrier properties for ham, sausage, cheese, prepared foods, and other foods. It can be used as a packaging material, a wrap film, and the like.

[0032]

EXAMPLES Next, the present invention will be described in more detail with reference to Examples and Comparative Examples, which do not limit the scope of the present invention. The weight average molecular weight, oxygen permeability, water vapor permeability, olive oil extraction amount, tensile strength, and apparent melt viscosity in the examples were determined by the following methods. Weight average molecular weight It was determined by a gel permeation chromatography method using polystyrene as a standard. Tetrahydrofuran was used as the solvent.

Oxygen permeability According to JIS-K7126 (Mocon method), thickness 40 μm
m film was measured and converted to a thickness of 1 μm. (Unit: cc · μm / m ² · day · atm at 20 ° C.-10
0% RH) Water vapor transmission rate According to JIS-Z0208 (cup method), thickness 40μ
m film was measured and converted to a thickness of 1 μm. (Unit: g ・ μm / m ²・ day ・ atmat 40 ° C-90
H)

Extraction amount of olive oil: A film having a thickness of 40 μm, a length of 5 cm and a width of 5 cm
The film was dipped in 0 cc of olive oil at 100 ° C. for 60 minutes, and the weight loss of the film was taken as the extraction amount. (Unit: mg
/ Square decimeter) Tensile Strength Tensile Testing Machine TENSILON manufactured by Toyo Baldwin
Using UTM-4L type, thickness 40 μm, length 5 cm,
The breaking strength of a film having a width of 1 cm at 20 ° C. and a tensile test at a speed of 100 mm / min was determined. (Unit: k
g / mm ² )

High-frequency sealing property A film having a thickness of 40 μm, a length of 10 cm, and a width of 5 cm is used as a film.
High-frequency welder SP manufactured by Takano Electric Industry Co., Ltd.
Using a -50B type, high frequency sealing was performed in an electrode load of 3.2 kg and an output range of 2210V to 3100V. The electrode material is brass.

Of each film, the one having the highest sealing strength among the above-mentioned output ranges was used as a sample for evaluation of high-frequency sealing property, and the seal portion was cut into a width of 1 cm and a T-type peeling test was conducted. One end of the film was fixed with a clip, a 16 g weight was hung on the other end, and the film was put into pig oil heated to 120 ° C., and the time until the seal portion peeled off was measured. (Unit: seconds)

Apparent Melt Viscosity A flow tester CFT-500 type manufactured by Shimadzu Corporation is used, and a load of 40 kgf and a die size of 1 mmφ at 180 ° C.
It was measured under the condition of -2 mmL. (Unit: Poise)

(Example 1) 120 parts of deionized water in which 0.2 part of hydroxypropylmethylcellulose was dissolved was charged into a reactor equipped with a stirrer, the inner surface of which was glass-lined. After substituting with nitrogen at 30 ° C., a mixture of 90 parts of vinylidene chloride monomer (VdC), 10 parts of vinyl chloride monomer (VC) and 0.2 part of diisopropyl peroxydicarbonate was added, and the inside of the reactor was heated to 45 ° C. The temperature is raised to start the polymerization. After 30 hours, the temperature is lowered and the slurry is taken out. The obtained slurry is separated from water by a centrifugal dehydrator and then dried by a hot air dryer at 80 ° C. for 24 hours to obtain a powdery vinylidene chloride copolymer resin composition A (P
VdC-A) was obtained.

The weight average molecular weight (Mw) of this copolymer was 98,000. Next, 1 part of deionized water in which 0.4 part of hydroxypropylmethyl cellulose was dissolved in the same reactor.
20 parts of the mixture was added, and after stirring was started, the inside of the system was replaced with nitrogen at 30 ° C., then 90 parts of vinylidene chloride monomer, 10 parts of vinyl chloride monomer, t-butylperoxy-2-ethylhexanoate. A mixture of 1.0 parts and 7.0 parts of 2-ethylhexyl thioglycolate is added, and the temperature inside the reactor is raised to 80 ° C. to start polymerization. After 10 hours, the temperature is lowered and the slurry is taken out. The obtained slurry is separated from water by a centrifugal dehydrator and then dried by a hot air dryer at 80 ° C. for 24 hours to obtain a powdery vinylidene chloride copolymer resin composition B (PVd
CB) was obtained. Weight average molecular weight of this copolymer (M
w) was 12,000.

Next, 90/1 vinylidene chloride copolymer resin composition A and vinylidene chloride copolymer resin composition B were added.
After blending at a ratio of 0, 80/20, 60/40 (% by weight), various composite vinylidene chloride copolymer resin compositions were obtained. Further, 1.0 part of bisphenol A diglycidyl ether was added to 100 parts by weight of these composite vinylidene chloride-based copolymer resin compositions, and the mixture was supplied to an ordinary melt extruder, melted, extruded in a tubular shape, and supercooled, Inflation was made into a tubular film, and this tubular film was flattened to obtain a monolayer film having a thickness of 40 μm. This composite vinylidene chloride-based copolymer resin composition was capable of extrusion film formation without adding a liquid plasticizer.

The oxygen transmission rate, water vapor transmission rate, olive oil extraction amount, tensile strength, high frequency sealing property, and apparent melt viscosity of this film were measured by the above-mentioned methods. The results are shown in Table 1 below. This film was excellent in barrier properties, non-extracting properties, and high-frequency sealing properties, and no deterioration in mechanical properties was observed.

Example 2 Example 1 was repeated except that the vinylidene chloride copolymer resin composition B was changed to 90 parts by weight of vinylidene chloride and 10 parts by weight of 2-ethylhexyl acrylate (EHA) as monomers. Various composite vinylidene chloride copolymer resin compositions were obtained in the same manner as in. At this time, the weight average molecular weight of the vinylidene chloride-based copolymer resin composition B is
It was 13,000.

Further, a film was obtained by the same method as in Example 1 and evaluated in the same manner. The results are shown in Table 1. This composite vinylidene chloride-based copolymer resin composition was capable of extrusion film formation without adding a liquid plasticizer. Further, this film was excellent in barrier properties, non-extraction properties, and high frequency sealing properties, and no deterioration in mechanical properties was observed.

Example 3 Various procedures were carried out in the same manner as in Example 1 except that the vinylidene chloride copolymer resin composition B was changed to 70 parts by weight of vinylidene chloride and 30 parts by weight of vinyl chloride. A composite vinylidene chloride-based copolymer resin composition was obtained. However, the vinylidene chloride-based copolymer resin composition A and the vinylidene chloride-based copolymer resin composition B were blended in a slurry state. At this time, the vinylidene chloride-based copolymer resin composition B had a weight average molecular weight of 11,000.

Further, a film was obtained by the same method as in Example 1 and evaluated in the same manner. The results are shown in Table 1. This composite vinylidene chloride-based copolymer resin composition was capable of extrusion film formation without adding a liquid plasticizer. Further, this film was excellent in barrier properties, non-extraction properties, and high frequency sealing properties, and no deterioration in mechanical properties was observed.

Example 4 Vinylidene chloride copolymer resin composition A was obtained by using 96 parts by weight of vinylidene chloride, 4 parts by weight of methyl acrylate (MA) as a monomer, and t-butylperoxy as a polymerization initiator. Various composite vinylidene chloride copolymer resin compositions were obtained in the same manner as in Example 1 except that 0.6 part of 2-ethylhexanoate and the polymerization temperature / hour were 75 ° C./10 hours. At this time, the vinylidene chloride-based copolymer resin composition A had a weight average molecular weight of 115,000.

Further, a film was obtained by the same method as in Example 1 and evaluated in the same manner. The results are shown in Table 1. This composite vinylidene chloride-based copolymer resin composition was capable of extrusion film formation without adding a liquid plasticizer. Further, this film was excellent in barrier property, non-extracting property and high-frequency sealing property, and deterioration of mechanical properties was not observed.

Example 5 Vinylidene chloride copolymer resin composition A was obtained by using 95 parts by weight of vinylidene chloride, 5 parts by weight of 2-ethylhexyl acrylate as a monomer, and t-butylperoxy- as a polymerization initiator. Various composite vinylidene chloride copolymer resin compositions were obtained in the same manner as in Example 1 except that 0.6 part of 2-ethylhexanoate and the polymerization temperature / hour were 75 ° C./10 hours. At this time, the vinylidene chloride-based copolymer resin composition A had a weight average molecular weight of 105,000.

Further, a film was obtained by the same method as in Example 1 and evaluated in the same manner. The results are shown in Table 1. This composite vinylidene chloride-based copolymer resin composition was capable of extrusion film formation without adding a liquid plasticizer. Further, this film was excellent in barrier properties, non-extraction properties, and high frequency sealing properties, and no deterioration in mechanical properties was observed.

Example 6 Chlorination was carried out in the same manner as in Example 1 except that 0.05 part of diisopropyl peroxydicarbonate at the time of obtaining the vinylidene chloride copolymer resin composition A and the polymerization time were 60 hours. A vinylidene-based copolymer resin composition A was obtained. Further, a vinylidene chloride-based copolymer resin composition B was obtained in the same manner as in Example 1 except that 2-ethylhexyl thioglycolate was 11.5 parts when the vinylidene chloride-based copolymer resin composition B was obtained. It was At this time, the weight average molecular weights of the vinylidene chloride copolymer resin composition A and the vinylidene chloride copolymer resin composition B were 28.
It was 50,000 and 60,000.

Further, a composite vinylidene chloride copolymer resin composition was obtained in the same manner as in Example 1. However, the blending ratio of the vinylidene chloride copolymer resin composition A and the vinylidene chloride copolymer resin composition B was 60/40, and the blending was performed in a slurry state. Further, a film was obtained by the same method as in Example 1 and evaluated in the same manner. The results are shown in Table 1. This composite vinylidene chloride-based copolymer resin composition was capable of extrusion film formation without adding a liquid plasticizer. Further, this film was excellent in barrier properties, non-extraction properties, and high frequency sealing properties, and no deterioration in mechanical properties was observed.

[0052]

[Table 1] (Note) *: cc · μm / m ² · day · atm at 20
℃ -100% RH +: g · μm / m ² · day · atm at 40 ℃ -90
% RH

(Example 7) Vinylidene chloride-based copolymer resin composition A was obtained by using 80 parts by weight of vinylidene chloride, 20 parts by weight of vinyl chloride as a monomer, and 0.12 of diisopropyl peroxydicarbonate as a polymerization initiator. Part, polymerization time 60
A vinylidene chloride copolymer resin composition A was obtained in the same manner as in Example 1 except that the time was changed. At this time, the vinylidene chloride copolymer resin composition A has a weight average molecular weight of 12.8.
It was good.

Next, 80 parts by weight of vinylidene chloride and 20 parts by weight of vinyl chloride were used as the monomers for obtaining the vinylidene chloride copolymer resin composition B, and t-butylperoxyisobutyrate of 0.2 part by weight was used as the polymerization initiator. 4 parts, polymerization temperature / hour 80 ° C /
A vinylidene chloride-based copolymer resin composition B was obtained in the same manner as in Example 1 except that the period was 16 hours and no chain transfer agent was used. At this time, the vinylidene chloride-based copolymer resin composition B had a weight average molecular weight of 42,000.

Further, a film was obtained in the same manner as in Example 1 and evaluated in the same manner. The results are shown in Table 2. This composite vinylidene chloride-based copolymer resin composition was capable of extrusion film formation without adding a liquid plasticizer. Further, this film was excellent in barrier properties, non-extraction properties, and high frequency sealing properties, and no deterioration in mechanical properties was observed.

Example 8 Vinylidene chloride-based copolymer resin composition A was obtained by using 95 parts by weight of vinylidene chloride, 5 parts by weight of methyl acrylate as a monomer, and t-butylperoxy-2- as a polymerization initiator. 0.7 parts of ethyl hexanoate,
A composite vinylidene chloride-based copolymer resin composition A was obtained in the same manner as in Example 1 except that the polymerization temperature / hour was 75 ° C./10 hours. At this time, the vinylidene chloride-based copolymer resin composition A had a weight average molecular weight of 101,000.

Next, 95% by weight of vinylidene chloride and 5 parts by weight of methyl acrylate were used as the monomers for obtaining the vinylidene chloride copolymer resin composition B, and t-butylperoxyisobutyrate (0.1% by weight) was used as the polymerization initiator. 6 parts, polymerization temperature / time 8
0 ° C / 12 hours, except that no chain transfer agent is used,
A vinylidene chloride copolymer resin composition B was obtained in the same manner as in Example 1. At this time, the vinylidene chloride-based copolymer resin composition B had a weight average molecular weight of 44,000.

Further, a film was obtained in the same manner as in Example 1 and evaluated in the same manner. The results are shown in Table 2. This composite vinylidene chloride-based copolymer resin composition was capable of extrusion film formation without adding a liquid plasticizer. Further, this film was excellent in barrier properties, non-extraction properties, and high frequency sealing properties, and no deterioration in mechanical properties was observed.

(Example 9) Vinylidene chloride-based copolymer resin composition A was obtained by adding 80 parts by weight of vinylidene chloride, 20 parts by weight of vinyl chloride as a monomer, and diisopropyl peroxydicarbonate of 0.2 as a polymerization initiator. A vinylidene chloride copolymer resin composition A was obtained in the same manner as in Example 1, except that the parts and the polymerization temperature / hour were 33 ° C./64 hours. At this time, the vinylidene chloride-based copolymer resin composition A had a weight average molecular weight of 195,000.

Next, 80 parts by weight of vinylidene chloride and 20 parts by weight of vinyl chloride were used as the monomers for obtaining the vinylidene chloride copolymer resin composition B, and t-butylperoxypivalate 0.3 was used as the polymerization initiator. Parts, polymerization temperature / hour 65 ° C./16
A vinylidene chloride-based copolymer resin composition B was obtained in the same manner as in Example 1 except that the time was set and the chain transfer agent was not used. At this time, the vinylidene chloride-based copolymer resin composition B had a weight average molecular weight of 39,000.

Further, a film was obtained by the same method as in Example 1 and evaluated in the same manner. The results are shown in Table 2. This composite vinylidene chloride-based copolymer resin composition was capable of extrusion film formation without adding a liquid plasticizer. Further, this film was excellent in barrier properties, non-extraction properties, and high frequency sealing properties, and no deterioration in mechanical properties was observed.

Example 10 A vinylidene chloride copolymer resin composition was prepared by blending 100 parts of the vinylidene chloride copolymer resin composition A obtained in Example 6 with 0.5 part of dibutyl sebacate (DBS). A film was obtained in the same manner as in Example 1 and evaluated in the same manner. The results are shown in Table 2.

This composite vinylidene chloride copolymer resin composition was capable of extrusion film formation by adding a very small amount of a liquid plasticizer. Further, this film was excellent in barrier properties, non-extraction properties, and high frequency sealing properties, and no deterioration in mechanical properties was observed.

(Example 11) In a reactor equipped with a stirrer of 50 liters, hydroxypropylmethylcellulose (0.1%) was added.
120 parts of deionized water in which 2 parts were dissolved was added, and after stirring was started, the system was replaced with nitrogen at 30 ° C., 60 parts of vinylidene chloride monomer, 15 parts of vinyl chloride monomer, and diisopropyl peroxydiene. Add a mixture of 0.09 parts of carbonate,
The temperature inside the reactor is raised to 45 ° C. to start polymerization. After 60 hours, the unreacted monomer was recovered, the temperature was lowered to 30 ° C., and a small amount of slurry was extracted so as not to affect the subsequent reaction, dehydrated and dried.

Next, a mixture of 20 parts of vinylidene chloride monomer, 5 parts of vinyl chloride monomer and 0.1 part of t-butylperoxyisobutyrate was charged and the temperature inside the reactor was raised to 80 ° C. Polymerization was restarted. After 16 hours, the temperature was lowered and the slurry was taken out to obtain a composite vinylidene chloride-based copolymer resin composition in the same manner as in Example 1. The weight average molecular weight of the vinylidene chloride-based copolymer resin composition A obtained in the first half reaction is
It was 128,000. The weight average molecular weight of the composite vinylidene chloride copolymer resin composition was 968,000. From this, the weight average molecular weight of the vinylidene chloride-based copolymer resin composition B obtained in the latter half reaction is estimated to be 42,000.

Further, bisphenol A was added to 100 parts by weight of the obtained composite vinylidene chloride copolymer resin composition.
Diglycidyl ether (1.0 part) was blended and a film having a thickness of 40 μm was obtained in the same manner as in Example 1. Next, the same evaluation as in Example 1 was performed. The results are shown in Table 2. This composite vinylidene chloride-based copolymer resin composition was capable of extrusion film formation without adding a liquid plasticizer. Further, this film was excellent in barrier properties, non-extraction properties, and high frequency sealing properties, and no deterioration in mechanical properties was observed.

[0067]

[Table 2] (Note) *: cc · μm / m ² · day · atm at 20
℃ -100% RH +: g · μm / m ² · day · atm at 40 ℃ -90
% RH

Example 12 Chlorination was carried out in the same manner as in Example 7 except that 0.30 part of diisopropyl peroxydicarbonate and 40 minutes of polymerization time were used to obtain the vinylidene chloride copolymer resin composition A. A vinylidene-based copolymer resin composition A was obtained. At this time, the vinylidene chloride-based copolymer resin composition A had a weight average molecular weight of 50,000. next,
When obtaining vinylidene chloride copolymer resin composition B, vinylidene chloride copolymer resin composition was prepared in the same manner as in Example 7 except that 5.0 parts by weight of 2-ethylhexyl thioglycolate was used as a chain transfer agent. B was obtained. At this time, the vinylidene chloride-based copolymer resin composition B had a weight average molecular weight of 55,000.

Further, a composite vinylidene chloride copolymer resin composition was obtained in the same manner as in Example 1. However, the vinylidene chloride-based copolymer resin composition A and the vinylidene chloride-based copolymer resin composition B were blended in a slurry state. Further, a film was obtained by the same method as in Example 1 and evaluated in the same manner. The results are shown in Table 3. This composite vinylidene chloride-based copolymer resin composition was capable of extrusion film formation without adding a liquid plasticizer. Further, this film was excellent in barrier property, non-extracting property, and high frequency sealing property, and no deterioration in mechanical properties was observed.

Example 13 The same procedure as in Example 7 was carried out except that 0.30 part of diisopropyl peroxydicarbonate was used for obtaining the vinylidene chloride copolymer resin composition A and the polymerization time was 40 hours. A vinylidene-based copolymer resin composition A was obtained. At this time, the vinylidene chloride-based copolymer resin composition A had a weight average molecular weight of 50,000. next,
When obtaining the vinylidene chloride-based copolymer resin composition B, t-
A vinylidene chloride-based copolymer resin composition B was obtained in the same manner as in Example 7, except that 0.6 part by weight of butyl peroxyisobutyrate and the polymerization time were 12 hours. At this time, the vinylidene chloride-based copolymer resin composition B had a weight average molecular weight of 35,000.

Further, a film was obtained by the same method as in Example 1 and evaluated in the same manner. The results are shown in Table 3. This composite vinylidene chloride-based copolymer resin composition was capable of extrusion film formation without adding a liquid plasticizer. Further, this film was excellent in barrier property, non-extracting property, and high frequency sealing property, and no deterioration in mechanical properties was observed.

Example 14 A chloride was prepared in the same manner as in Example 7 except that 0.20 part of diisopropyl peroxydicarbonate and 40 hours of polymerization were used to obtain the vinylidene chloride copolymer resin composition A. A vinylidene-based copolymer resin composition A was obtained. At this time, the vinylidene chloride-based copolymer resin composition A had a weight average molecular weight of 10,000,000.

Next, when the vinylidene chloride copolymer resin composition B was obtained, the polymerization initiator was 0.24 parts by weight of diisopropyl peroxydicarbonate, and the polymerization temperature / hour was 45 ° C.
A vinylidene chloride-based copolymer resin composition B was obtained in the same manner as in Example 7 except that the time was set to / 40 hours. The weight average molecular weight of the vinylidene chloride-based copolymer resin composition B at this time was 8.
It was 0,000.

Further, a film was obtained by the same method as in Example 1 and evaluated in the same manner. The results are shown in Table 3. This composite vinylidene chloride-based copolymer resin composition was capable of extrusion film formation without adding a liquid plasticizer. Further, this film was excellent in barrier property, non-extracting property, and high frequency sealing property, and no deterioration in mechanical properties was observed.

(Example 15) When obtaining vinylidene chloride copolymer resin composition A, 0.05 part of diisopropyl peroxydicarbonate and polymerization time / hour were 40 ° C / 90.
A vinylidene chloride-based copolymer resin composition A was obtained in the same manner as in Example 7 except that the time was changed. At this time, the vinylidene chloride-based copolymer resin composition A had a weight average molecular weight of 30,000,000. Next, vinylidene chloride-based copolymer resin composition B
When obtaining, the polymerization initiator is 0.24 parts by weight of diisopropyl peroxydicarbonate, and the polymerization temperature / hour is 45 ° C. /
A vinylidene chloride-based copolymer resin composition B was obtained in the same manner as in Example 7 except that the time was 40 hours. At this time, the vinylidene chloride-based copolymer resin composition B has a weight average molecular weight of 8.0.
It was good.

In the vinylidene chloride copolymer resin composition A,
After blending 0.5 part by weight of DBS, a composite vinylidene chloride copolymer resin composition was obtained in the same manner as in Example 1.
However, the blending ratio of the vinylidene chloride copolymer resin composition A and the vinylidene chloride copolymer resin composition B is 60/4.
It is 0. Further, a film was obtained by the same method as in Example 1 and evaluated in the same manner. The results are shown in Table 3. This composite vinylidene chloride-based copolymer resin composition was capable of extrusion film formation by adding an extremely small amount of a liquid plasticizer. Further, this film was excellent in barrier property, non-extracting property, and high frequency sealing property, and no deterioration in mechanical properties was observed.

Example 16 When the vinylidene chloride-based copolymer resin composition A was obtained, 0.05 part of diisopropyl peroxydicarbonate was used, and the polymerization time / hour was 40 ° C./90.
A vinylidene chloride-based copolymer resin composition A was obtained in the same manner as in Example 7 except that the time was changed. At this time, the vinylidene chloride-based copolymer resin composition A had a weight average molecular weight of 30,000,000. Next, vinylidene chloride-based copolymer resin composition B
Example 7 except that 5.0 parts by weight of 2-ethylhexyl thioglycolate was used as a chain transfer agent when obtaining
A vinylidene chloride-based copolymer resin composition B was obtained in the same manner as in. At this time, the vinylidene chloride-based copolymer resin composition B had a weight average molecular weight of 55,000.

Further, a composite vinylidene chloride copolymer resin composition was obtained in the same manner as in Example 1. However, the blending ratio of the vinylidene chloride-based copolymer resin composition A and the vinylidene chloride-based copolymer resin composition B was 60/40, and the blending was performed in a slurry state. Further, a film was obtained by the same method as in Example 1 and evaluated in the same manner. The results are shown in Table 3.

This composite vinylidene chloride copolymer resin composition was capable of extrusion film formation without adding a liquid plasticizer. Further, this film was excellent in barrier property, non-extracting property, and high frequency sealing property, and no deterioration in mechanical properties was observed.

Example 17 To each composite vinylidene chloride-based copolymer resin composition obtained in Example 7, 2.0 parts by weight of DBS was blended, and a film was obtained in the same manner as in Example 1, Similar evaluation was performed. The results are shown in Table 3. This composite vinylidene chloride-based copolymer resin composition had no problem in extrusion film formation. Further, this film was excellent in barrier properties, non-extraction properties, and high frequency sealing properties, and no deterioration in mechanical properties was observed.

Example 18 2.0 parts by weight of ATBC was blended with each composite vinylidene chloride copolymer resin composition obtained in Example 7, and a film was obtained in the same manner as in Example 1. Similar evaluation was performed. The results are shown in Table 3. This composite vinylidene chloride-based copolymer resin composition had no problem in extrusion film formation. Further, this film was excellent in barrier property, non-extracting property, and high frequency sealing property, and no deterioration in mechanical properties was observed.

[0082]

[Table 3] (Note) *: cc · μm / m ² · day · atm at 20
℃ -100% RH +: g · μm / m ² · day · atm at 40 ℃ -90
% RH

COMPARATIVE EXAMPLE 1 Vinylidene chloride copolymer resin composition A and vinylidene chloride copolymer resin composition B were used as 99
A composite vinylidene chloride-based copolymer resin composition was obtained in the same manner as in Example 1 except that the blending was carried out at / 1 part by weight. This composite vinylidene chloride-based copolymer resin composition had a high melt viscosity and could not be extruded into a film. The results are shown in Table 4.

Comparative Example 2 40% of vinylidene chloride-based copolymer resin composition A and vinylidene chloride-based copolymer resin composition B were prepared.
A composite vinylidene chloride-based copolymer resin composition was obtained in the same manner as in Example 1 except that the blending was carried out at 60 parts by weight.
Further, a film was obtained by the same method as in Example 1 and evaluated in the same manner. The results are shown in Table 4. This film had insufficient mechanical properties and high-frequency sealing property.

(Comparative Example 3) Vinylidene chloride-based copolymer resin composition A was replaced with vinylidene chloride 99.5 as a monomer.
A composite vinylidene chloride copolymer resin composition was obtained in the same manner as in Example 1 except that the amount was 0.5 part by weight and the amount of vinyl chloride was 0.5 part by weight. However, vinylidene chloride-based copolymer resin composition A
The blend ratio of the vinylidene chloride-based copolymer resin composition B is 80/20. At this time, the vinylidene chloride copolymer resin composition A was insoluble in tetrahydrofuran, and the molecular weight could not be measured. This composite vinylidene chloride-based copolymer resin composition had a high melt viscosity and could not be extruded into a film. The results are shown in Table 4.

Comparative Example 4 A composite was prepared in the same manner as in Example 1 except that 40 parts by weight of vinylidene chloride and 60 parts by weight of vinyl chloride were used as monomers for obtaining the vinylidene chloride copolymer resin composition A. A vinylidene chloride-based copolymer resin composition was obtained. However, the blending ratio of the vinylidene chloride copolymer resin composition A and the vinylidene chloride copolymer resin composition B is 8
It is 0/20. At this time, the vinylidene chloride-based copolymer resin composition A had a weight average molecular weight of 85,000. Further, a film was obtained by the same method as in Example 1 and evaluated in the same manner. The results are shown in Table 4. This film had an insufficient gas barrier property.

Comparative Example 5 A composite vinylidene chloride copolymer resin composition was prepared in the same manner as in Example 1 except that 1.0 part of diisopropyl peroxydicarbonate was used when the vinylidene chloride copolymer resin composition A was obtained. I got a thing. However,
The blend ratio of the vinylidene chloride-based copolymer resin composition A and the vinylidene chloride-based copolymer resin composition B is 80/20. At this time, the vinylidene chloride-based copolymer resin composition A had a weight average molecular weight of 39,000. Furthermore, Example 1
A film was obtained by the same method as above, and the same evaluation was performed. The results are shown in Table 4. This film had insufficient mechanical properties and high-frequency sealing property.

(Comparative Example 6) A composite chloride was prepared in the same manner as in Example 6 except that 0.02 part of diisopropyl peroxydicarbonate and 100 hours of polymerization were used to obtain the vinylidene chloride-based copolymer resin composition A. A vinylidene-based copolymer resin composition was obtained. However, the blending ratio of the vinylidene chloride copolymer resin composition A and the vinylidene chloride copolymer resin composition B is 60/40. At this time, the vinylidene chloride-based copolymer resin composition A has a weight average molecular weight of 33.0.
It was good. This composite vinylidene chloride-based copolymer resin composition had a high melt viscosity and could not be extruded into a film. The results are shown in Table 4.

Comparative Example 7 Vinylidene chloride 99.5 was used as a monomer when the vinylidene chloride copolymer resin composition B was obtained.
A composite vinylidene chloride copolymer resin composition was obtained in the same manner as in Example 1 except that the amount was 0.5 part by weight and the amount of vinyl chloride was 0.5 part by weight. However, vinylidene chloride-based copolymer resin composition A
The blend ratio of the vinylidene chloride-based copolymer resin composition B is 80/20. At this time, the vinylidene chloride-based copolymer resin composition B was insoluble in tetrahydrofuran and its molecular weight could not be measured. This composite vinylidene chloride-based copolymer resin composition had a high melt viscosity and could not be extruded into a film. The results are shown in Table 4.

Comparative Example 8 A composite was prepared in the same manner as in Example 1 except that 40 parts by weight of vinylidene chloride and 60 parts by weight of vinyl chloride were used as monomers for obtaining the vinylidene chloride copolymer resin composition B. A vinylidene chloride-based copolymer resin composition was obtained. However, the blending ratio of the vinylidene chloride copolymer resin composition A and the vinylidene chloride copolymer resin composition B is 8
It is 0/20. At this time, the vinylidene chloride-based copolymer resin composition B had a weight average molecular weight of 90,000. Further, a film was obtained by the same method as in Example 1 and evaluated in the same manner. The results are shown in Table 4. This film had an insufficient gas barrier property.

Comparative Example 9 The procedure of Example 1 was repeated except that 2.5 parts of t-butylperoxy-2-ethylhexanoate was used to obtain the vinylidene chloride copolymer resin composition B. A composite vinylidene chloride-based copolymer resin composition was obtained. However, the blending ratio of the vinylidene chloride copolymer resin composition A and the vinylidene chloride copolymer resin composition B is 8
0/20, and blending was performed in a slurry state. At this time, the vinylidene chloride-based copolymer resin composition B had a weight average molecular weight of 0.380 million. Further, a film was obtained by the same method as in Example 1 and evaluated in the same manner. The results are shown in Table 4. This film had insufficient mechanical properties and high-frequency sealing property.

Comparative Example 10 A vinylidene chloride copolymer resin composition A was obtained in the same manner as in Example 6. The vinylidene chloride-based copolymer resin composition A has a weight average molecular weight of 28.
It was 50,000. Next, a vinylidene chloride copolymer resin composition was prepared in the same manner as in Example 1 except that 0.3 part of diisopropyl peroxydicarbonate was used when the vinylidene chloride copolymer resin composition A of Example 1 was obtained. Item B was obtained.
At this time, the vinylidene chloride-based copolymer resin composition B had a weight average molecular weight of 85,000. This composite vinylidene chloride-based copolymer resin composition had a high melt viscosity and could not be extruded into a film. The results are shown in Table 4.

Comparative Example 11 A vinylidene chloride copolymer resin composition A was obtained in the same manner as in Example 1. The weight average molecular weight of the obtained vinylidene chloride-based copolymer resin composition A was 98,000. Next, when the vinylidene chloride-based copolymer resin composition B was obtained, the vinylidene chloride-based copolymer resin composition A of Example 1 was used except that 0.15 parts by weight of diisopropyl peroxydicarbonate was used as the polymerization initiator. A vinylidene chloride-based copolymer resin composition B was obtained by the same method as that for obtaining. At this time, the vinylidene chloride-based copolymer resin composition B had a weight average molecular weight of 96,000.

Further, a composite vinylidene chloride copolymer resin composition was obtained in the same manner as in Example 1. However, the blending ratio of the vinylidene chloride-based copolymer resin composition A and the vinylidene chloride-based copolymer resin composition B is 80/20. This composite vinylidene chloride-based copolymer resin composition had a high melt viscosity and could not be extruded into a film. The results are shown in Table 4.

[0095]

[Table 4] (Note) *: cc · μm / m ² · day · atm at 20
℃ -100% RH +: g · μm / m ² · day · atm at 40 ℃ -90
% RH

Comparative Example 12 To 100 parts of the vinylidene chloride copolymer resin composition A obtained in Example 7, DBS was blended in an amount of 2 parts by weight, 4 parts by weight and 6 parts by weight, respectively. The blend of 2 parts by weight had a high melt viscosity and could not be extruded into a film. With respect to the blended product of 4 parts by weight and 6 parts by weight, a film was obtained in the same manner as in Example 1 and the same evaluation was performed. The results are shown in Table 5. This film had insufficient barrier properties and non-extractability.

COMPARATIVE EXAMPLE 13 100 parts of the vinylidene chloride copolymer resin composition A obtained in Example 7 was mixed with ATBC.
2 parts by weight, 4 parts by weight, and 6 parts by weight were blended. Two
The blended parts by weight had a high melt viscosity and could not be extruded into a film. With respect to the blended product of 4 parts by weight and 6 parts by weight, a film was obtained in the same manner as in Example 1 and the same evaluation was performed. The results are shown in Table 5.
This film had insufficient barrier properties and non-extractability.

[0098]

[Table 5] (Note) *: cc · μm / m ² · day · atm at 20
℃ -100% RH +: g · μm / m ² · day · atm at 40 ℃ -90
% RH

[0099]

INDUSTRIAL APPLICABILITY The vinylidene chloride-based copolymer resin composition of the present invention comprises two types of vinylidene chloride-based resins having different average molecular weights, that is, a resin composition positioned as a mechanical property imparting component having a large average molecular weight and a high frequency sealing component. A compound chloride consisting of A and a resin composition B having a small average molecular weight and positioned as a plasticizer at the time of molding, which is easy to mold without adding a liquid plasticizer at all or in an extremely small amount compared to the conventional one. Vinylidene-based copolymer resin composition,
And a monolayer film obtained therefrom.

Therefore, as compared with the conventional single-layer film obtained from the vinylidene chloride copolymer resin composition, which requires the addition of a liquid plasticizer, it is superior in barrier properties and non-extractability by oily foods. It is suitable as a packaging material for hams, sausages, prepared foods, other foods, and wrap films that require good properties.

[Brief description of drawings]

FIG. 1 is a graph showing the molecular weight range of the composite vinylidene chloride copolymer resin composition of the present invention.

FIG. 2 Representative vinylidene chloride copolymer resin composition A
And the molecular weight distribution of a typical vinylidene chloride-based copolymer resin composition B and this vinylidene chloride-based copolymer resin composition A
And a vinylidene chloride copolymer resin composition B at a weight ratio of 80/20 are graphs showing a relationship with a molecular weight distribution of a film obtained by molding and processing a composite vinylidene chloride copolymer resin composition. .

Claims (2)

[Claims] 1. A composite vinylidene chloride-based copolymer resin composition comprising the following vinylidene chloride-based copolymer resin composition A and vinylidene chloride-based copolymer resin composition B, wherein the content of the resin composition A is 50% by weight or more and 98% by weight or less, a composite vinylidene chloride copolymer resin composition. A: Vinylidene chloride content of 50% by weight or more and 99% by weight
The following is a vinylidene chloride-based copolymer resin composition B having a weight average molecular weight of 50,000 or more and 300,000 or less by gel permeation chromatography: B: vinylidene chloride content of 50% by weight or more and 99% by weight or less.
The weight average molecular weight by the gel permeation chromatography method is 55,000 or more, and the weight average molecular weight of the vinylidene chloride copolymer resin composition A is 0.8 or less.
Double vinylidene chloride-based copolymer resin composition, which is less than or equal to 80,000 2. A single layer film comprising the composite vinylidene chloride copolymer resin composition according to claim 1.