JP2005048109A - Vinylidene chloride-based resin film, casing for meat kneaded product and packaged meat kneaded product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a vinylidene-based resin film excellent in releasing property from meat and suitability for automatic packing and packaging and suitable as a packaging material for meat kneaded products such as boiled fish paste and sausage, casing for meat kneaded products composed of the film and a packaged meat kneaded product packed and packaged in the casing. <P>SOLUTION: The vinylidene chloride-based resin film is formed of a resin composition comprising 100 pts. wt. vinylidene chloride-based resin and 0.05-1.5 pts. wt. ester of a 19-25C fatty acid component with 0.05-1.5 pts. wt. polyglycerol component. The casing for meat kneaded products is composed of the film. The packaged meat kneaded product is obtained by packing and packaging the meat kneaded product into the casing. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a vinylidene chloride-based resin film, and more particularly to a vinylidene chloride-based resin film that is excellent in meat peelability and automatic filling and packaging properties and is suitable as a packaging material for meat paste products such as strawberries and sausages. The vinylidene chloride resin film of the present invention can be suitably used as a casing for meat paste products.

  2. Description of the Related Art Conventionally, meat paste products such as salmon and fish sausages have been manufactured and sold in a plastic film casing formed into a tube shape for the purpose of long-term storage. The plastic film constituting the casing is a vinylidene chloride resin film that has excellent gas barrier properties (oxygen gas barrier properties and water vapor barrier properties), low-temperature flexibility, transparency, heat shrinkability, heat sealability, etc., and good printability. It is widely used.

  However, a packaged meat paste product in which a meat paste product is packed and packaged in a vinylidene chloride resin film casing and sterilized by heating is used. When the consumer peels off the casing due to chemical bonding or the like, the meat paste product adheres to the peeled surface of the casing film. When the meat paste product adheres to the film peeling surface, the contents are reduced, the product appearance is impaired, and the commercial value is lowered. Therefore, in order to prevent the meat paste product from adhering to the casing film peeling surface, a vinylidene chloride-based resin film containing various additives generally called “meat peeling agents” has been proposed.

  For example, a vinylidene chloride resin film for packaging (for example, refer to Patent Document 1), a vinylidene chloride resin formed by forming a resin composition obtained by adding sorbitan fatty acid ester or polyoxyethylene sorbitan fatty acid ester to vinylidene chloride resin A vinylidene chloride resin film (for example, see Patent Document 2) obtained by forming a resin composition in which a nonionic surfactant and other processing aids are mixed with each other by an inflation method, and the number of carbon atoms in the vinylidene chloride resin. A vinylidene chloride resin film (for example, Patent Document 3) obtained by forming a resin composition containing a sorbitan fatty acid ester containing 20 to 24 fatty acid components into a film by an inflation method, polyglycerin stearic acid on a vinylidene chloride resin Vinyl chloride formed by forming a resin composition with added ester Den-based resin film (e.g., see Patent Document 4) it has been proposed.

  Vinylidene chloride resin film containing meat release agents such as sorbitan fatty acid ester and polyglycerin stearic acid ester is provided with meat peelability, and when a meat paste product is filled and packaged using the film casing, casing peeling The adhesion of the meat paste product to the surface can be suppressed.

  However, with the increase in the level of demand for quality improvement in packaged meat paste products, there is an urgent need to develop a vinylidene chloride-based resin film and a casing made of the film that are more excellent in meat peelability than before. More specifically, there is a demand for the development of a novel meat stripper that has no adverse effects on food hygiene and film properties, and has excellent meat stripping properties even when added in a relatively small amount.

  In addition, since meat paste products are filled and packaged at high speed using an automatic filling and packaging machine, the vinylidene chloride resin film used as a packaging material is not only excellent in meat peelability but also suitable for automatic filling and packaging machines. It is required to be excellent.

  A seamless single-layer tube formed by molding a vinylidene chloride resin by an inflation method is sometimes used as an original packaging material. In many cases, a tubular film molded from a vinylidene chloride resin by an inflation method is folded. A long film obtained by slitting the two-layer film to a desired width is used. The slit-processed long film original is generally formed into a tube shape by laminating both ends in the width direction in the form of an envelope stretch with a bag making apparatus attached to an automatic filling and packaging machine. A high-frequency electrode is used for welding the film.

  In the automatic filling and packaging machine, while the tube made of vinylidene chloride resin film is continuously sent from the top to the bottom, the meat paste product material quantified by the metering pump is filled into the tube from the nozzle tip through the flow path. Is done. The tube filled with the raw material is squeezed by a pair of squeezing rollers at a constant cycle, and the squeezed portions are ligated simultaneously at two places by metal clips. The lower metal clip of the two metal clips forms the upper end ligation portion of the previous filling portion, and the upper metal clip forms the lower end ligation portion of the subsequent filling portion. The two ligatures are cut to obtain individual packaged meat paste products.

  In order to perform high-speed filling using such an automatic filling and packaging machine, the slipperiness of the vinylidene chloride resin film is required to be good. When slipperiness of vinylidene chloride resin film is poor, the length of the packaged meat paste product varies, the thinning of the seal wire due to overmelting of the high frequency welded part, pinholes, bag breakage during high-pressure heat sterilization due to poor sealing Problems occur.

  Moreover, when using the slit-processed two-layer film as a raw material, if delamination occurs during bag making with an automatic filling and packaging machine, a satisfactory tubular casing cannot be formed. Furthermore, if the surface of the vinylidene chloride resin film is sticky, it not only adversely affects the slipperiness but also reduces the product value.

However, conventional meat stripping agents have problems such as a relatively large amount of blending to increase the meat stripping property, the slipperiness of vinylidene chloride resin film being reduced, and the surface being sticky The suitability of automatic filling and packaging machines was not always sufficient.
Japanese Examined Patent Publication No. 44-2108 Japanese Patent Publication No.46-2382 Japanese Patent Publication No.55-2266 JP-A-6-316641

  An object of the present invention is to provide a vinylidene chloride-based resin film that is excellent in meat peelability and suitability for automatic filling and packaging and is suitable as a packaging material for meat paste products such as strawberries and sausages.

  Moreover, the objective of this invention is providing the casing for meat paste products which consists of a vinylidene chloride resin film excellent in meat peelability and automatic filling packaging machine suitability. Another object of the present invention is to provide a packaged meat paste product in which the meat paste product is packed and packaged in such a meat paste product casing.

  As a result of diligent research to achieve the above object, the present inventor has shown that a specific polyglycerin fatty acid ester exhibits excellent performance as a meat release agent for vinylidene chloride resin films, and further, automatic filling and packaging of vinylidene chloride resin films It was found that it does not hinder the suitability. The present invention has been completed based on these findings.

  Thus, according to the present invention, a resin composition containing 0.05 to 1.5 parts by weight of an ester of a fatty acid component having 19 to 25 carbon atoms and a polyglycerin component with respect to 100 parts by weight of a vinylidene chloride resin. A vinylidene chloride resin film formed from the above is provided.

  Moreover, according to this invention, the casing for meat paste products formed from the said vinylidene chloride resin film is provided. Furthermore, according to this invention, the packaged meat paste product which packed and packaged the meat paste product in the said casing for meat paste products is provided.

  The vinylidene chloride resin film of the present invention is excellent in meat peelability and suitability for automatic filling and packaging, and is suitable as a packaging material for meat paste products such as strawberries and sausages. The vinylidene chloride resin film of the present invention has good slipperiness, hardly causes delamination, and has no surface stickiness. The vinylidene chloride resin film of the present invention is excellent in transparency, heat sealability (high frequency weldability) and the like.

  When the casing made of the vinylidene chloride-based resin film of the present invention is used, adhesion of the meat paste product to the release surface of the casing film is suppressed at the time of casing peeling, and the commercial value of the packaged meat paste product can be increased.

1. Vinylidene chloride resin :
The vinylidene chloride resin used in the present invention is a copolymer of 60 to 98% by weight of vinylidene chloride and 2 to 40% by weight of another monomer (comonomer) copolymerizable with vinylidene chloride. .

  Examples of the comonomer include vinyl chloride; alkyl acrylate esters such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, stearyl acrylate, and the like. -18); Methyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, methacrylic acid alkyl esters such as stearyl methacrylate (alkyl group having 1 to 18 carbon atoms); cyan such as acrylonitrile and methacrylonitrile Aromatic vinyl such as styrene; vinyl ester of aliphatic carboxylic acid having 1 to 18 carbon atoms such as vinyl acetate; alkyl vinyl ether having 1 to 18 carbon atoms; acrylic acid, methacrylic acid, maleic acid, fumaric acid, itacon Acid Polymerizable unsaturated carboxylic acids; alkyl esters of vinyl polymerizable unsaturated carboxylic acids such as maleic acid, fumaric acid, itaconic acid (including partial esters, having 1 to 18 carbon atoms in the alkyl group); Body, functional group-containing monomer, polyfunctional monomer and the like.

  These comonomers can be used alone or in combination of two or more. Among these comonomers, vinyl chloride, methyl acrylate, and lauryl acrylate are preferable, and vinyl chloride is particularly preferable. When the copolymerization ratio of the comonomer is too small, the internal plasticization becomes insufficient and the melt processability is lowered. When the copolymerization ratio of the comonomer is too large, the gas barrier property is lowered. The copolymerization ratio of the comonomer is preferably 3 to 35% by weight, more preferably 8 to 25% by weight.

  The reduced viscosity [ηsp / C] of the vinylidene chloride-based resin is preferably 0.035 to 0.070, more preferably 0 from the viewpoints of processability when molding into a film, suitability for automatic filling and packaging machines, cold resistance, and the like. 0.040 to 0.065, particularly preferably 0.045 to 0.063. If the reduced viscosity of the PVDC-based resin is too low, the processability is lowered, and if it is too high, a tendency toward coloring is exhibited, so neither is preferable. Two or more types of vinylidene chloride resins having different reduced viscosities can be used in combination, thereby improving workability. When two or more kinds of vinylidene chloride resins are used in combination, the reduced viscosity of the mixed resin is preferably within the above range.

  The vinylidene chloride resin can be blended with other resins as desired. Examples of other resins include ethylene-vinyl acetate copolymer, (meth) acrylic acid ester, preferably (co) polymer of alkyl group (meth) acrylic acid alkyl ester having 1 to 18 carbon atoms [for example, (Methyl (meth) acrylate- (meth) butyl acrylate copolymer), methyl methacrylate-butadiene-styrene copolymer, and the like. The other resin is usually used at a ratio of 20 parts by weight or less with respect to 100 parts by weight of the vinylidene chloride resin.

  The vinylidene chloride resin used in the present invention may be synthesized by any polymerization method such as suspension polymerization, emulsion polymerization, solution polymerization, etc., but in order to form a compound as a powder resin, it is about 40 to 600 μm. And obtained by a suspension polymerization method that does not require a pulverization step.

2. Polyglycerin fatty acid ester :
In the present invention, a specific polyglycerin fatty acid ester is used in order to enhance the meat peelability of the vinylidene chloride resin film. That is, the polyglycerol fatty acid ester used in the present invention is an ester of a fatty acid component having 19 to 25 carbon atoms and a polyglycerol component.

Typical examples of the fatty acid component having 19 to 25 carbon atoms include icosanoic acid and behenic acid. Among these, behenic acid [CH ₃ (CH ₂ ) ₂₀ COOH] is preferable. In the esterification, the fatty acid component may be in a free acid state, or may be in the form of a salt or an alkyl ester.

  As the polyglycerin component, polyglycerin having various degrees of polymerization can be used, but diglycerin, triglycerin, and tetraglycerin are preferable from the viewpoint of meat peelability and compatibility. The polyglycerol fatty acid ester may be any monoester, diester, triester or the like, and may be a mixture thereof.

  If the number of carbon atoms in the fatty acid component of the polyglycerin fatty acid ester is 18 or less (for example, stearic acid), in addition to the fact that the blending ratio needs to be relatively large in order to obtain sufficient meat peelability, vinylidene chloride The suitability of the automatic filling and packaging machine such as the slipperiness of the resin-based resin film is not always sufficient. On the other hand, even if the number of carbon atoms of the fatty acid component is in the range of 19 to 25, for example, using sorbitan behenate other than polyglycerin fatty acid ester, the meat peelability is insufficient and the blending ratio is relatively increased. However, it is difficult to obtain sufficient meat peelability.

  As the polyglycerin fatty acid ester, polyglycerin behenate is preferable. As the polyglycerol behenate, at least one polyglycerol behenate selected from the group consisting of diglycerol monobehenate, diglycerol dibehenate, triglycerol monobehenate, and triglycerol dibehenate is preferable. Also, mixed esters such as diglycerin mono-diester (mixture of diglycerin monoester and diglycerin diester) and triglycerin mono-diester (mixture of triglycerin monoester and triglycerin diester) can be used. The ratio of the monoester or diester component in the mixed ester is arbitrary.

  The chemical structure of polyglycerin fatty acid ester cannot be specified sufficiently because it has a large number of hydroxyl groups, and is often obtained as a mixed ester. For example, as diglycerin monobehenate, (1)

The diglycerin dibehenate ester is represented by the following formula (2):

The triglycerin monobehenate ester is represented by the following formula (3):

The triglycerin dibehenate ester is represented by the following formula (4):

The ester represented by these is mentioned.

  In the present invention, the polyglycerin fatty acid ester is used as a meat release agent for vinylidene chloride-based resin film, and the blending ratio is 0.05 to 1.5 parts by weight with respect to 100 parts by weight of vinylidene chloride-based resin. Preferably it is 0.1-1.3 weight part, More preferably, it is 0.2-1.0 weight part. In many cases, the blending ratio of polyglycerin fatty acid ester with respect to 100 parts by weight of vinylidene chloride resin is in the range of 0.4 to 0.8 parts by weight, and has an excellent balance between meat peelability and suitability for automatic filling and packaging machines, and A vinylidene chloride resin film having excellent film properties such as transparency can be obtained.

3. Various additives :
The vinylidene chloride-based resin can contain various additives such as a plasticizer, a heat stabilizer, an antioxidant, a lubricant, a filler, a satinizer, and a colorant at the time of polymerization and compound formation.

  Examples of the plasticizer include dioctyl phthalate, acetyl tributyl citrate (ie, acetyl tributyl citrate), dibutyl sebacate, dioctyl sebacate, acetylated monoglyceride, acetylated diglyceride, acetylated triglyceride, and two to three of them. Typical examples thereof include polyester plasticizers such as acetylated glycerides, adipic acid and 1,3-butanediol, adipic acid and 1,4-butanediol, and mixtures of two or more thereof. The plasticizer is usually used at a ratio of 0.05 to 10 parts by weight with respect to 100 parts by weight of the vinylidene chloride resin. If the blending ratio of the plasticizer is too large, the plasticizer tends to bleed.

  As the heat stabilizer, for example, epoxidized vegetable oil, epoxidized animal oil, epoxidized fatty acid ester, epoxy resin prepolymer, glycidyl group-containing (meth) acrylic resin and the like are used. Epoxidized vegetable oils and epoxidized animal oils are not particularly limited as long as they are conventionally used as heat stabilizers for vinylidene chloride resins, and natural animal and vegetable oils having unsaturated bonds can be converted to hydrogen peroxide or peracetic acid. By epoxidizing with, for example, a double bond modified to an oxirane ring can be used. Preferred epoxidized vegetable oils include epoxidized soybean oil and epoxidized linseed oil.

  Epoxidized fatty acid esters include epoxidized products of unsaturated fatty acid esters such as epoxidized octyl stearate. Examples of the epoxy resin prepolymer include bisphenol A glycidyl ether. Examples of the glycidyl group-containing (meth) acrylic resin include a copolymer containing, as a copolymerization component, a vinyl-polymerizable unsaturated organic acid glycidyl ester. Among these epoxy compounds, epoxidized vegetable oils widely used in the food packaging field are preferable.

  The heat stabilizer is usually used in a proportion of 0.1 to 5 parts by weight, preferably 0.5 to 4 parts by weight, and more preferably 1 to 3 parts by weight with respect to 100 parts by weight of the vinylidene chloride resin. When the blending ratio of the heat stabilizer is too large, bleeding on the vinylidene chloride-based resin film surface, blocking is likely to occur, and gas barrier properties are likely to be lowered.

  Antioxidants include 2,6-di-tert-butyl-4-methyl-phenol (BHT), triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate (Irganox 245, manufactured by Ciba Geigy), 2,4-dimethyl-6-S-alkylphenol, 2,4-dimethyl-6- (1-methylpentadecyl) phenol, and mixtures thereof (Irganox 1141 manufactured by Ciba Geigy) Phenolic antioxidants; thioether antioxidants such as thiodipropionic acid and distearyl thiodipropionate; phosphite antioxidants such as trisnonylphenyl phosphite and distearyl pentaerythritol diphosphite; It is done. The antioxidant is usually used at a ratio of 0.0001 to 0.05 parts by weight with respect to 100 parts by weight of the vinylidene chloride resin.

  Examples of the lubricant include waxes such as oxidized polyethylene wax, paraffin wax, polyethylene wax, montanic acid ester wax and calcium montanate; fatty acid esters such as glycerin monoester. Moreover, as what is suitable for the melt processing of a PVDC-type resin composition and the secondary processing of a film, the mono- or bisamide of fatty acids, such as a stearic acid amide, is mentioned. These lubricants are usually used in a proportion of 0.001 to 2 parts by weight with respect to 100 parts by weight of vinylidene chloride resin.

  Examples of the filler include silicon dioxide and calcium carbonate. Silicon dioxide and calcium carbonate also act as a satin finishing agent, a film slipperiness imparting (packaging machine suitability) agent and the like. Silicon dioxide also acts as an inorganic lubricant. An appropriate amount of the filler and the finishing agent is usually 1 part by weight or less, preferably 0.5 parts by weight or less based on 100 parts by weight of the vinylidene chloride resin.

  Examples of the ultraviolet absorber include 2- (2′-hydroxy-3 ′, 5′-di-tert-butylphenyl) -5-chlorobenzotriazole, and an appropriate amount is used as necessary.

  As the surfactant, a nonionic surfactant such as sorbitan fatty acid ester, other polyglycerin fatty acid ester, and polyoxyethylene sorbitan fatty acid ester is used in an appropriate amount as required. Since these surfactants also act as meat release agents for packaging films, they can be used in combination with the meat release agent of the present invention as necessary.

  As other stabilizers, inorganic bases such as magnesium hydroxide, magnesium oxide and calcium hydroxyphosphate; organic weak acid salts such as citric acid and alkali metal citrate; ethylenediaminetetraacetate; be able to. Examples of the pH adjuster include sodium pyrophosphate and disodium dihydrogen pyrophosphate. An appropriate amount of 0.5 parts by weight or less is used with respect to 100 parts by weight of vinylidene chloride resin.

  Examples of the colorant include organic pigments such as azo, phthalocyanine, and quinacridone; inorganic pigments such as titanium oxide, aluminum, mica, and carbon black; extender pigments such as calcium carbonate and magnesium oxide. Among these, red pigments such as pigment red and yellow pigments such as pigment yellow are widely used in the field of packaging films for meat paste products such as fish sausage. The colorants can be used alone or in combination of two or more. An appropriate amount of the colorant is usually 1 part by weight or less with respect to 100 parts by weight of the vinylidene chloride resin. However, in the case of a titanium oxide pigment, it may be mixed up to 10 parts by weight.

3. Vinylidene chloride resin film :
In general, when preparing a resin composition containing a vinylidene chloride resin and various additives, various additives are blended with a powdered resin of vinylidene chloride resin to produce a powdery mixture (compound). By the blending, liquid additives such as epoxidized vegetable oil and plasticizer are absorbed by the powder resin of vinylidene chloride resin, and the powder additive adheres around the powder resin of vinylidene chloride resin. If necessary, a vinylidene chloride resin in which a part or all of a liquid plasticizer, a stabilizer or the like is added in the polymer production process at the start of polymerization or at the end of polymerization may be used.

  Each component can be mixed using blenders, such as a blade blender, a ribbon blender, and a Henschel mixer. During this mixing, the additive components tend to aggregate. If a large amount of agglomerates are present in the vinylidene chloride resin composition, processability, extrudability, film formability, stretchability, etc. are impaired, and furthermore, poor appearance due to formation of fish eyes in molded articles such as films. Bring. Therefore, in order to enhance the dispersibility of additive components such as pigments and suppress the formation of aggregates, it is preferable to use a dispersion aid or devise the mixing order. Inevitable agglomerates are removed by sieving.

  The vinylidene chloride resin composition (compound) can be melt-extruded and formed into a stretched or unstretched film, sheet or the like. As a film forming method, for example, an inflation method using a circular die is applied. In the inflation method, the film can be stretched in at least a uniaxial direction, preferably in a biaxial direction. The biaxially oriented film has heat shrinkability and is suitably used as a heat-resistant film that can be retorted. The draw ratio is preferably 2 to 5 times in the longitudinal direction and 2 to 5 times in the transverse direction.

  Film thickness is 5-50 micrometers normally as a single layer film, Preferably it is 10-30 micrometers. A two-layer film obtained by folding a cylindrical film obtained by an inflation method and slitting it to have a desired width can be used. The thickness of the two-layer film is twice that of the single-layer film. The stretch film has a heat shrinkage ratio of preferably about 30 to 60% in both length and width (120 ° C. glycerin bath, 3 minutes).

  The main method of using a vinylidene chloride resin film as a film for packaging meat paste products is to form a biaxially stretched film by the inflation method and then fold it flat to form a double-layered double-layer film (double-ply film). And after slitting the ear | edge part of both ends of a film, it winds around core materials, such as a paper tube, and makes it a roll-shaped original fabric. This raw fabric is supplied to an automatic filling and packaging machine and welded (heat sealed) while overlapping both ends in the width direction in an envelope tension shape to form a tube shape (including a cylindrical shape). A high-frequency electrode is generally used for welding. The tube thus formed is continuously sent to the filling section of the same automatic filling and packaging machine, and after filling the contents, the both ends are ligated to obtain a package.

  More specifically, in the automatic filling and packaging machine, while the tube made of vinylidene chloride resin film is continuously sent from the top to the bottom, the meat paste product quantified by the metering pump passes through the flow path from the nozzle tip. The tube is filled. The tube filled with the raw material is squeezed by a pair of squeezing rollers at a constant cycle, and the squeezed portions are ligated simultaneously at two places by metal clips. The two ligated parts are cut to obtain individual packaged meat paste products.

  The vinylidene chloride-based resin film of the present invention is excellent in meat peelability, and can exhibit a high degree of meat peelability even when the blending ratio of the polyglycerin fatty acid ester is relatively small. The vinylidene chloride resin film of the present invention is excellent in suitability for automatic filling and packaging machines, excellent in slipperiness and delamination prevention properties, and has no surface stickiness. The vinylidene chloride resin film of the present invention is particularly suitable as a packaging casing for meat paste products such as salmon and sausages mainly composed of fish meat.

  The packaged meat paste product in which the vinylidene chloride resin film of the present invention is filled and packaged as a casing can withstand a retort treatment at high pressure and high temperature. The packaged meat paste product that has been subjected to such heat sterilization generally has strong adhesion between the contents and the casing, and shows a tendency for a large amount of meat to adhere to the release surface of the casing film when the casing is peeled off. The casing is remarkably excellent in meat peelability and can solve such a problem. Moreover, the meat peelability is excellent not only when rapidly cooled after heat sterilization, but also when cooled.

  Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. The evaluation methods for various characteristics are as follows. Moreover, the compounding prescription of the meat raw material (boiled raw material and sausage raw material) used for the experiment is as shown in Table 1.

(1) Meat peelability:
A tube formed by high-frequency sealing a vinylidene chloride-based resin film is filled with rice bran raw material or sausage raw material to produce a meat-filled package, and 10 of them (n = 10) are sampled and the following method is used. The meat peelability was evaluated. Both ends of the meat-filled package were cut to a length of 10 cm. Using a cutter, a cut was made in the length direction along the high-frequency seal line of the tube, and the film was peeled off at a constant speed and force in the circumferential direction. After the peeling, the ratio of the area where the meat was attached to the film was measured and evaluated in correspondence with the following evaluation standard values. A sample with a smaller numerical value of the evaluation criterion indicates better meat peelability.
0: No meat adhesion (entire peeling)
1: 1-5% of meat adhesion area (very slightly adhesion)
2: Meat adhesion area 6-25% (slight adhesion),
3: 26-50% meat adhesion area,
4: Meat adhesion area 51-75%,
5: Meat adhesion area 76 to 100% (entire adhesion).

(2) Suitability for automatic filling and packaging machine:
<Slipperiness>
A film with a thickness of 20 μm and a width of 72 mm, stacked on two sheets, is overlapped at both ends via a forming plate with an automatic filling and packaging machine (Kureha KAP), and further sealed with a high frequency on a stuffer nozzle to form a tube with a folding width of 30 mm. Produced. This tube was passed through a tension measuring roller, the tension applied to the measuring roller was measured under the condition of a take-up speed of 30 m / min, and the slipperiness of the film was evaluated according to the following criteria.
A: Sliding tension is 3kg or less and can be used for automatic filling packaging.
B: The sliding tension is 3-4kg and the conditions for automatic filling and packaging need to be adjusted.
C: The sliding tension is 4 kg or more, and it cannot be used even if the load is adjusted.

<Two-layer film peeling; delamination>
A: No peeling of the double-layer film even after passing through the forming plate,
B: After passing through the forming plate, the two-layer film is partially peeled off.
C: After passing through the forming plate, the entire surface of the tube is continuously peeled off from the two-layer film.

<Film stickiness>
A: The touch is relatively dry,
B: The touched feeling is sticky.

[Example 1]
1. Process 1 :
As a plasticizer for 100 parts by weight of vinylidene chloride-vinyl chloride copolymer [89% by weight of vinylidene chloride / 11% by weight of vinyl chloride, 0.060 of reduced viscosity (ηsp / C)] obtained by suspension polymerization. 4 parts by weight of dibutyl sebacate and 3 parts by weight of acetyltributyl citrate, 1.5 parts by weight of epoxidized linseed oil as a heat stabilizer, 0.12 parts by weight of silicon dioxide as a finishing agent, 0.05 weight of stearic acid amide as a lubricant Part, 0.3 parts by weight of Pigment Yellow 95 as a colorant and 0.08 part by weight of Pigment Red 166, and triglycerin mono-dibehenate as a meat release agent (ie, behenic acid) Mono- / di-ester mixture of glycerin and triglycerin; hereinafter abbreviated as “TGGMDB”) 0.5 part by weight The mixture was heated and mixed at 70 ° C. for 30 minutes using a blender. Thereafter, the mixture was cooled and sieved with a 30-mesh wire mesh to remove aggregates. In this way, an extrusion molding mixture (compound) was prepared.

2. Process 2 :
The mixture prepared in step 1 was melt extruded into a tube at a resin temperature of 185 ° C. using a melt extruder having a diameter of 90 mm. The melt-extruded tubular body was quenched in a 6 ° C. bath to be in an amorphous state. After passing the amorphous tubular body through a 20 ° C. preheating bath to raise the temperature, air is blown into the tubular body while passing between two pairs of pinch rolls having different speeds. Biaxial stretching was performed 72 times and 3.63 times in the width direction. The biaxially stretched film was folded by a pinch roll on the winding side to obtain a flat long double ply (double layer) film having a width of 1200 mm and a thickness of 40 μm.

3. Step 3 :
The double-ply film obtained in step 2 was slit to a width of 72 mm, and the slit double-ply film having a length of 1500 m was layered around a paper tube to obtain an original fabric for an automatic filling and packaging machine. This raw fabric is suspended on an automatic filling and packaging machine (KAP manufactured by Kureha Chemical Industry Co., Ltd.), and both ends in the film width direction are overlapped in an envelope-like form via a forming plate (folding width 30 mm), and the overlapping portions on both ends are filled with meat. A tube was formed by welding with a high-frequency electrode disposed on the nozzle for use. One end of this tube was ligated with an aluminum wire, and the other end was filled with a koji material according to the formulation of “蒲 鉾 1” shown in Table 1, and then this end was ligated with an aluminum wire. . In this way, 100 meat-filled packages having a weight of 62 g and a length of 235 mm between two ligatures were prepared. These packages are subjected to a retort treatment at 120 ° C. for 15 minutes at a gauge pressure in the can of 2.5 kg / cm ² , and then cooled to room temperature with water in about 20 minutes. Got. The results are shown in Table 2.

[Example 2]
The same procedure as in Example 1 was performed except that “Samurai 1” was replaced with “Sausage 1” shown in Table 1 in Step 3 of Example 1. The results are shown in Table 2.

[Example 3]
In Step 1 of Example 1, except that the meat stripping agent was changed from TGMDB to diglycerin mono-dibehenate (mixture of diglycerin monobehenate and diglycerin dibehenate; hereinafter abbreviated as “DGMDB”). Performed as in Example 1. The results are shown in Table 2.

[Example 4]
The same procedure as in Example 1 was performed except that the meat stripping agent was changed from TGMDB to DGMDB in Step 1 of Example 1 and “蒲 鉾 1” was changed to “Sausage 1” shown in Table 1 in Step 3. It was. The results are shown in Table 2.

[Comparative Example 1]
Implementation was performed except that in Step 1 of Example 1, the meat stripping agent was changed from TGMDB to triglycerin mono-stearate (mixture of triglycerin monostearate and triglycerin distearate, hereinafter abbreviated as “TGGMDS”). Performed as in Example 1. The results are shown in Table 2.

[Comparative Example 2]
The same procedure as in Example 1 was performed except that the meat stripping agent was changed from TGMDB to TGMDS in Step 1 of Example 1 and “蒲 鉾 1” was changed to “Sausage 1” shown in Table 1 in Step 3. It was. The results are shown in Table 2.

[Comparative Example 3]
Implementation was performed except that in Step 1 of Example 1, the meat stripper was changed from TGMDB to diglycerin mono-stearate (mixture of diglycerin monostearate and diglycerin distearate; hereinafter abbreviated as “DGMDS”). Performed as in Example 1. The results are shown in Table 2.

[Comparative Example 4]
The same procedure as in Example 1 was performed except that the meat stripping agent was changed from TGMDB to DGMDS in Step 1 of Example 1 and “蒲 鉾 1” was changed to “Sausage 1” shown in Table 1 in Step 3. It was. The results are shown in Table 2.

[Comparative Example 5]
Example 1 except that in Step 1 of Example 1, the meat stripper was changed from TGMDB to sorbitan mono-dibehenate (a mixture of sorbitan monobehenate and sorbitan dibehenate; hereinafter abbreviated as “SBBMDB”). The same was done. The results are shown in Table 2.

[Comparative Example 6]
The same procedure as in Example 1 was performed except that the meat stripping agent was changed from TGMDB to SBMDB in Step 1 of Example 1 and “蒲 鉾 1” was changed to “Sausage 1” shown in Table 1 in Step 3. It was. The results are shown in Table 2.

(footnote)
(1) TGMDB: Triglycerin mono-dibehenate
(2) DGMDB: Diglycerin mono-dibehenate
(3) TGMDS: Triglycerin mono-distearate
(4) DGMDS: Diglycerin mono-distearate
(5) SBMDB: Sorbitan mono dibehenate

[Example 5]
1. Process 1 :
As a plasticizer for 100 parts by weight of vinylidene chloride-vinyl chloride copolymer [89% by weight of vinylidene chloride / 11% by weight of vinyl chloride, 0.060 of reduced viscosity (ηsp / C)] obtained by suspension polymerization. 3 parts by weight of dibutyl sebacate and 2.5 parts by weight of acetyltributyl citrate, 1.5 parts by weight of epoxidized linseed oil as a heat stabilizer, 0.15 parts by weight of calcium carbonate as a finishing agent, and stearic acid amide as a lubricant 05 parts by weight, and 0.3 part by weight of triglycerin mono-dibehenate (TGMDB) as a meat stripper were heated and mixed at 70 ° C. for 30 minutes using a ribbon blender. Thereafter, the mixture was cooled and sieved with a 30-mesh wire mesh to remove aggregates. In this way, an extrusion mixture was prepared.

2. Process 2 :
The mixture prepared in step 1 was melt extruded into a tube at a resin temperature of 185 ° C. using a melt extruder having a diameter of 90 mm. The melt-extruded tubular body was quenched in a 6 ° C. bath to be in an amorphous state. After passing the amorphous tubular body through a 20 ° C. preheating bath to raise the temperature, air is blown into the tubular body while passing between two pairs of pinch rolls having different speeds. Biaxial stretching was performed 72 times and 3.63 times in the width direction. The biaxially stretched film was folded by a pinch roll on the winding side to obtain a flat long double ply (double layer) film having a width of 1200 mm and a thickness of 40 μm.

3. Step 3 :
The double-ply film obtained in step 2 was slit to a width of 72 mm, and the slit double-ply film having a length of 1500 m was layered around a paper tube to obtain an original fabric for an automatic filling and packaging machine. This raw fabric is suspended on an automatic filling and packaging machine (KAP manufactured by Kureha Chemical Industry Co., Ltd.), and both ends in the film width direction are overlapped in an envelope-like form via a forming plate (folding width 30 mm), and the overlapping portions on both ends are filled with meat. A tube was formed by welding with a high-frequency electrode disposed on the nozzle for use. One end of this tube was ligated with an aluminum wire, and after filling the sausage raw material according to the formulation of “Sausage 2” shown in Table 1 from the other end, this end was ligated with an aluminum wire. . In this way, 100 meat-filled packages having a weight of 62 g and a length of 235 mm between two ligatures were prepared. These packages were subjected to a retort treatment at 120 ° C. for 15 minutes at a can gauge pressure of 2.5 kg / cm ² , and then cooled in the same manner as in Example 1 to obtain a meat-filled package sample. . The results are shown in Table 3.

[Example 6]
In Step 1 of Example 5, the same procedure as in Example 5 was performed except that the blending ratio of TGMDB of the meat stripper was changed from 0.3 part by weight to 0.4 part by weight. The results are shown in Table 3.

[Example 7]
In Step 1 of Example 5, the same procedure as in Example 5 was performed except that the blending ratio of TGMDB of the meat stripper was changed from 0.3 part by weight to 0.6 part by weight. The results are shown in Table 3.

[Example 8]
In Step 1 of Example 5, the same procedure as in Example 5 was performed except that the blending ratio of TGMDB of the meat stripper was changed from 0.3 part by weight to 0.8 part by weight. The results are shown in Table 3.

[Comparative Example 7]
The same procedure as in Example 5 was conducted except that the meat stripping agent was changed from TGMDB to triglycerin mono-distearate (TGGMDS) in Step 1 of Example 5. The results are shown in Table 3.

[Comparative Example 8]
The same procedure as in Comparative Example 7 was performed except that the blending ratio of TGMDS was changed from 0.3 part by weight to 0.4 part by weight. The results are shown in Table 3.

[Comparative Example 9]
The same procedure as in Comparative Example 7 was performed except that the blending ratio of TGMDS was changed from 0.3 parts by weight to 0.6 parts by weight. The results are shown in Table 3.

[Comparative Example 10]
The same procedure as in Comparative Example 7 was performed except that the blending ratio of TGMDS was changed from 0.3 part by weight to 0.8 part by weight. The results are shown in Table 3.

[Comparative Example 11]
The same procedure as in Example 5 was conducted except that the meat stripping agent was changed from TGMDB to sorbitan mono-dibehenate (SBBMDB) in Step 1 of Example 5. The results are shown in Table 3.

[Comparative Example 12]
The same procedure as in Comparative Example 11 was performed except that the blending ratio of SBMDB was changed from 0.3 parts by weight to 0.4 parts by weight. The results are shown in Table 3.

[Comparative Example 13]
The same procedure as in Comparative Example 11 was performed except that the blending ratio of SBMDB was changed from 0.3 parts by weight to 0.6 parts by weight. The results are shown in Table 3.

[Comparative Example 14]
The same procedure as in Comparative Example 11 was performed except that the blending ratio of SBMDB was changed from 0.3 parts by weight to 0.8 parts by weight. The results are shown in Table 3.

(footnote)
(1) TGMDB: Triglycerin mono-dibehenate
(2) TGMDS: Triglycerin mono-distearate
(3) SBMDB: Sorbitan mono dibehenate

  The vinylidene chloride resin film of the present invention is excellent in meat peelability and suitability for automatic filling and packaging machines, and can be suitably used as a packaging casing for meat paste products such as salmon and sausages mainly composed of fish meat. In addition, the vinylidene chloride resin film of the present invention can be applied to the field of packaging materials that require a high degree of meat peelability.

Claims (7)

  Vinylidene chloride resin formed from a resin composition containing 0.05 to 1.5 parts by weight of an ester of a fatty acid component having 19 to 25 carbon atoms and a polyglycerol component with respect to 100 parts by weight of vinylidene chloride resin the film.   The vinylidene chloride-based resin composition film according to claim 1, wherein the fatty acid component is behenic acid.   The vinylidene chloride resin film according to claim 1 or 2, wherein the polyglycerol component is at least one selected from the group consisting of diglycerol, triglycerol, and tetraglycerol.   The vinylidene chloride resin film according to any one of claims 1 to 3, wherein the ester is a polyglycerin behenate.   2. The polyglycerol behenate is at least one polyglycerol behenate selected from the group consisting of diglycerol monobehenate, diglycerol dibehenate, triglycerol monobehenate, and triglycerol dibehenate. 5. Vinylidene chloride resin film according to any one of items 4 to 4.   The casing for meat paste products formed from the vinylidene chloride resin film of any one of Claims 1 thru | or 5.   The packaged meat paste product which filled and packaged the meat paste product in the casing for meat paste products of Claim 6.