JP6059005B2 - Plant-derived vinylidene chloride copolymer composition and heat-shrinkable film - Google Patents

Description

  The present invention relates to a plant-derived vinylidene chloride copolymer composition and a heat-shrinkable film.

  A vinylidene chloride polymer film is a transparent film excellent in oxygen gas barrier properties and moisture-proof properties (water vapor barrier properties), and is therefore used as a wrap film for business use or home use (sometimes simply referred to as “wrap”). In addition, as a film for automatic filling and packaging of other foods, it is widely used for packaging of fresh fish, raw meat, processed meat, fresh vegetables, prepared foods, etc. for the purpose of blocking oxygen and moisture.

  The homopolymer of vinylidene chloride is easy to crystallize and has a high softening point, and the chlorine content is higher than that of vinyl chloride. Therefore, the softening point and the decomposition temperature (dehydrochlorination reaction) are close to each other, and the extrusion processability of films, etc. There are disadvantages inferior to Therefore, vinylidene chloride is usually copolymerized with vinyl chloride or other monomer (monomer) copolymerizable with vinylidene chloride to form a vinylidene chloride copolymer, and the copolymer is added with a plasticizer, an adhesive, Extrudability is improved by including a tackifier, a stabilizer and the like. Moreover, in order to prevent the trouble in the manufacturing process and packaging process of a film, a lubricant may be included depending on necessity. Therefore, a vinylidene chloride copolymer film is generally obtained by melt-extruding a polymer composition containing a stabilizer, a plasticizer, and other additives, if desired, such as a lubricant and other additives to a vinylidene chloride copolymer. In the case of melt extrusion, it is known that more thermally stable extrudability can be obtained by installing a vacuum hopper in the extruder. Subsequently, it is manufactured by a method of forming a film by an inflation method or the like. Moreover, a heat-shrinkable film can also be manufactured by extending | stretching by the inflation method etc. (patent document 1, 2, 3).

  The vinylidene chloride copolymer film does not cause decomposition or discoloration due to heat or the like when molding a polymer composition, and has physical properties even during distribution and storage of wrap films and packaging materials in midsummer and midwinter. There is no reduction, and for food packaging, there is no need for food hygiene problems.

  A wrap film made of a vinylidene chloride copolymer formed from a vinylidene chloride copolymer composition is required to have adhesiveness to a container or the like and to have a cut property that can be easily cut by a cutter.

  In addition, the packaging material made of vinylidene chloride copolymer formed from the vinylidene chloride copolymer composition is suitable for automatic filling and packaging machinery because of the widespread use of packaging and heat sterilization by automatic filling and packaging machinery. And a film for automatic filling and packaging having sealability and the like that can withstand retort processing (high temperature and high pressure sterilization processing).

[Carbon offset]
When a synthetic resin that is an organic substance such as a vinylidene chloride copolymer or a molded product formed from the synthetic resin is burned, carbon dioxide is generated. Carbon dioxide is one of the gases that warm the global environment, that is, greenhouse gas (also called “green house gas”), and it continues to increase with industrial activities by humans, especially after the industrial revolution. . In order to maintain a global environment where human survival is sustainable, the concept of carbon dioxide that does not increase the total amount of carbon dioxide circulating in the earth's oceans and atmosphere is shared.

  At present, most of synthetic resin materials are manufactured using compounds derived from fossil fuels such as petroleum, coal, and natural gas as starting materials. Fossil fuels contain carbon that has been fixed in the ground for many years. Combustion of a fossil fuel or a product derived from a compound derived from fossil fuel and releasing carbon dioxide into the atmosphere means that carbon that is fixed deep in the ground and does not exist in the atmosphere will Since it is suddenly released into the atmosphere as carbon, carbon dioxide in the atmosphere greatly increases, causing global warming.

  On the other hand, even if organisms (plants, animals) that grow by nutrient sources that absorb carbon dioxide circulating in the global environment and convert it into organic matter are burned in the earth's atmosphere to generate carbon dioxide, Since this is a circulation of carbon dioxide existing in the interior, there is no change in the total amount of carbon constituting the carbon dioxide. This carbon entry / exit is said to be a state of carbon offset (carbon offset) or no entry / exit (carbon neutral), and carbon negative (carbon negative) increases carbon dioxide present in the global environment. ).

  Carbon that circulates in the global environment, and the existing carbon is renewable carbon, modern carbon (contemporary carbon), bio-derived carbon (bio-resourced carbon, biobased carbon, biogenic carbon) ), Biomass derived carbon, green carbon, atmospheric carbon, environmentally friendly carbon, or life-cycle carbon, etc. And carbon (fossil carbon, fossil fuel based carbon, petrochemical based carbon, carbon of fossil origin).

  In particular, plants are organisms that grow by absorbing carbon dioxide circulating in the global environment, performing photosynthesis reactions using carbon dioxide and water as raw materials, and assimilating and fixing as organisms. It is attracting attention as a source. For example, an alcohol component, especially ethyl alcohol (bioethanol) is distilled and separated from a fermented sugar or a cellulose fermented product extracted from plant raw materials such as sugar cane and corn, and ethylene is obtained as an alkene by a dehydration reaction. An ethylene resin or an olefin resin can be obtained through a resin synthesis means (Patent Document 4). Synthetic resins having this history are said to be carbon offset polyolefin, biogenic polyolefin, plant based resin, or the like.

Carbon constituting the carbon dioxide circulating in the global environment is radioactive carbon 14 (also referred to as “ ¹⁴ C”), which is an isotope, and stable carbon 12 (also referred to as “ ¹² C”). ) And metastable carbon 13 (sometimes referred to as “ ¹³ C”), the mass ratio of which is ¹² C (98.892 mass%), ¹³ C (1.18 mass%) and ¹⁴ It is well-known that it is C (a trace amount of 1.2 × 10 ⁻¹² mass% to 1.2 × 10 ⁻¹⁰ mass%). The ratio of ¹² C to ¹³ C is stable. In addition, radioactive ¹⁴ C is generated when neutrons contained in secondary cosmic rays generated by primary cosmic rays in the upper atmosphere collide with nitrogen atoms ( ¹⁴ N) in the atmosphere. Although it fluctuates slightly depending on the level of activity, etc., it continues to be supplied, while it decreases with a half-life of 5730 years.

Living organisms (plants and animals) that continuously grow by using nutrients that have absorbed carbon dioxide circulated in the global environment and converted it into organic matter, make up the three types of carbon dioxide circulated in the global environment. Continue to inherit the carbon isotope mass ratio. When the organism is killed, the mass ratio of the three types of carbon isotopes inside the organism is fixed at the ratio at the time of death. The half-life of ¹⁴ C is 5730 years, and archaeological dating methods that use this to estimate the age of various samples are well known. On the other hand, ¹⁴ C in fossil fuels for a long time is formed elapsed since killing of organisms inhabit the ancient long ago than the half-life 5730 years of ¹⁴ C, isolated from the carbon dioxide modern circulating in the global environment Thus, since it can be regarded as almost 0 (below the detection limit of the measuring instrument), ¹⁴ C in the synthetic resin derived from fossil fuel can be regarded as almost 0.

Therefore, it is possible to distinguish between a synthetic resin derived from a plant and a synthetic resin derived from a fossil fuel by the ratio of ¹⁴ C contained. The growing plant is harvested, saccharified into alcohol (bioethanol), and ethylene, which is an alkene resulting from the dehydration reaction, is used as a raw material through a normal resin synthesis means and The time to do is about a few months and can be ignored from the half-life of ¹⁴ C, 5730 years. The time lag until the production of plant-derived synthetic resin is either plant-derived synthetic resin or fossil fuel-derived There is no substantial effect on the determination of the synthetic resin.

The ratio of radioactive ¹⁴ C composing carbon dioxide circulating in the global environment has been diluted and reduced by humans burning large amounts of fossil fuels since the Industrial Revolution, but the atmosphere since 1950 AD It turned to increase by the inner core experiment. That is, the amount of radioactive ¹⁴ C produced by atmospheric nuclear tests exceeded the amount of radioactive ¹⁴ C produced by the nuclear reaction of ¹⁴ N caused by collision with neutrons produced by the action of cosmic rays. Subsequently, due to the 1964 nuclear test cessation treaty, the ratio of radioactive ¹⁴ C began to decrease after peaking in 1963, and there were fluctuations due to subsequent nuclear accidents, but the ratio of radioactive ¹⁴ C in 1950 Not reached.

Therefore, for the distinction between plant-derived organic substances and fossil fuel-derived organic substances, a standardization method based on the abundance ratio of radioactive ¹⁴ C as of 1950 is known, and the National Bureau of Standards (NIST) ) By ASTM D6866-12 (Determining the Biobased Control of Solid, Liquid, and Gaseous Samples Using Radiocarbon Analysis). ASTM D6866 is an ASTM (American Society for Testing and Materials) standard that determines the biogenic carbon concentration in solid, liquid, and gas samples using radiocarbon dating. Since it was approved, it has been revised and the current latest standard ASTM D6866-12 is the one revised in April 2012.

The principle defined by ASTM D6866-12 is roughly as follows. In other words, organic substances derived from fossil fuels have been killed or cut off by living organisms (animals and plants) in the era before 1950, and the ratio composition of carbon isotopes at that time is fixed. The abundance ratio of carbon constituting the organic substance is 0 (zero). Therefore, the ratio composition of carbon isotopes is derived from fossil fuel using the unit of modern carbon ratio (percent modern carbon: pMC) defined by the function of ¹³ C / ¹² C, which is a stable ratio, and radioactive ¹⁴ C. The modern carbon ratio of the organic substance is 0 pMC (meaning that it is less than the detection limit of the measuring instrument). Further, the modern carbon ratio of a standard substance (oxalic acid supplied by NIST (SRM4990) or an equivalent organic substance) having a carbon isotope ratio composition as of 1950 is defined as 100 pMC. The ratio of the fossil fuel-derived organic substance and the plant-derived organic substance is determined by determining the modern carbon ratio of the sample with reference to 0 to 100 pMC. The modern carbon ratio of plant-derived organic substances produced at present is not lower than at least 102 pMC due to the influence of ¹⁴ C, which has been artificially increased by atmospheric nuclear tests conducted since 1950, with an average of about 107 pMC. is there. The modern carbon ratio in 1963 before the nuclear test termination treaty, at which the ratio of ¹⁴ C was the peak, was 118 pMC. Therefore, if the modern carbon ratio of the organic material is 102 to 118 pMC, it can be said that the organic material is surely composed only of a plant-derived organic material.

  Moreover, from the value of the modern carbon ratio of the known plant-derived synthetic resin, a synthetic resin material (a modern carbon ratio is 0 pMC) which is a mixture of the plant-derived synthetic resin and fossil fuel-derived synthetic resin ( The content ratio of the plant-derived synthetic resin in the resin composition) can be calculated, and the mass ratio of the plant-derived synthetic resin may be described as “% Corg.renew”. For example, the mass ratio of the plant-derived synthetic resin (modern carbon ratio is calculated as 107 pMC × 0.9 = 96.3 pMC) and the synthetic resin derived from fossil fuel in the resin composition of 90% When the ratio is 50:50, the resin composition has a modern carbon ratio of 48.2 pMC (calculated as 107 pMC × 0.9 × 0.50 = 48.15 pMC) and 45% Corg.renew ( It is calculated as 90% × 0.5). When the mass ratio in the resin composition is 60:40, the modern carbon ratio is 57.8 pMC (calculated as 107 pMC × 0.9 × 0.6 = 57.78 pMC). 54% Corg.renew (calculated as 90% × 0.6). Note that the “biologicalization rate” (%) is the mass ratio of the plant-derived synthetic resin in the synthetic resin, and may be referred to as “biomass plastic degree” or “biomass degree”. If the bio-ization rate is 25%, based on the Biomass Plastic Identification and Labeling System established by the Japan Bioplastics Association (established in July 2006), a plastic product with a biomass plastic degree of 25% (mass) or more is designated “Biomass Plastic” Is allowed.

On the other hand, a resin composition containing no synthetic resin derived from plants and containing a synthetic resin derived from fossil fuels is essentially modern when measured separately from the modern carbon dioxide circulating in the global environment as described above. The carbon ratio is 0 pMC. However, in reality, radioactive ¹⁴ C derived from nuclear tests and nuclear accidents conducted after 1950 are mixed in, or carbon isotopes are absorbed or permeated on the surface by carbon dioxide circulating in the modern global environment. The exchange may cause a modern carbon ratio greater than 0 pMC. However, in many cases, the modern carbon ratio of the synthetic resin derived from fossil fuel is in the range of 0.01 to 0.03 pMC, which can be said to be substantially 0 pMC. At least, the modern carbon ratio of the synthetic resin derived from fossil fuel does not exceed 8 pMC. Therefore, if the modern carbon ratio of a certain synthetic resin or a resin composition containing a synthetic resin is 0 to 8 pMC, the synthetic resin or the resin composition containing the synthetic resin is derived from a fossil fuel-derived synthetic resin or a fossil fuel. It can be said that it is a resin composition containing the synthetic resin.

In addition, the influence of radioactive ¹⁴ C derived from inorganic carbon such as calcium carbonate, which is a component of limestone and may be blended in a resin composition containing a synthetic resin derived from fossil fuel for various purposes, is observed. Sometimes, in measuring modern carbon ratios, methods that eliminate the effect are standardized.

In addition, in a resin composition containing a synthetic resin derived from fossil fuel, radioactive ¹⁴ C derived from an additive or compounding agent containing organic carbon is affected and diluted, so that it is larger than 0 pMC. Although a modern carbon ratio may be shown, if it is a normal compounding quantity, the modern carbon ratio of the resin composition containing the synthetic resin derived from fossil fuel will not exceed 8 pMC.

  In principle, fossil fuel-derived synthetic resins and plant-derived synthetic resins differ only in the modern carbon ratio, so they have an impact on the global environment (carbon offset or carbon neutral, or conversely carbon It was thought that there was no change or difference in handling of the production process of the resin product from the synthetic resin and the resin product formed, except for negative). However, in reality, it is also known that there may be a difference in compatibility and mechanical properties (Patent Document 5).

  Molded articles formed from vinylidene chloride copolymer compositions, such as wrap films and packaging materials, and heat shrinkable films suitable for wrap films and packaging materials are also required for resin compositions containing synthetic resins. It is expected to have carbon offset properties. At the same time, in addition to the oxygen gas barrier property required for the vinylidene chloride copolymer composition, (1) following the step of melt-extruding the vinylidene chloride copolymer composition, stretching for imparting heat shrinkability Formability suitable for complicated manufacturing process that goes through the process, (2) Requirements related to physical properties degradation and food hygiene during manufacturing and distribution storage, and (3) Adhesion and cutability in wrap film, or packaging There is a demand for satisfying packaging performance such as automatic filling packaging suitability and sealing suitability of materials.

Japanese Patent Laid-Open No. 10-324809 JP 2005-48109 A JP-A-11-71492 Special table 2010-511634 JP 2011-132525 A

  An object of the present invention is to provide a vinylidene chloride copolymer that has a carbon offset property and can realize a gas barrier property, molding processability, and excellent packaging performance comparable to a resin composition containing a resin derived from a fossil fuel. It is to provide a composition. Moreover, the subject of this invention is providing the heat-shrinkable film formed from this vinylidene chloride copolymer composition.

  As a result of intensive studies on solving the above-mentioned problems, the present inventors have determined that the vinylidene chloride copolymer composition contains a vinylidene chloride copolymer having a modern carbon ratio within a predetermined range. I found that I could solve the problem. In addition, the present inventors have formed a heat-shrinkable film formed from the vinylidene chloride copolymer composition as described above from a resin composition having a carbon offset property and containing a resin derived from fossil fuel. It has been found that it has a gas barrier property, molding processability and excellent packaging performance comparable to those of heat-shrinkable films.

  That is, according to the present invention, there is provided a plant-derived vinylidene chloride copolymer composition comprising a vinylidene chloride copolymer having a modern carbon ratio defined by ASTM D6866-12 of 10 to 118 pMC. Is done.

Moreover, according to this invention, the plant-derived vinylidene chloride copolymer composition of the following (1)-(3) is provided as an embodiment.
(1) The plant-derived vinylidene chloride copolymer composition, wherein the vinylidene chloride copolymer is a vinylidene chloride-vinyl chloride copolymer.
(2) The plant-derived vinylidene chloride copolymer composition, wherein the vinylidene chloride monomer (monomer) is obtained from plant-derived ethylene.
(3) The plant-derived vinylidene chloride copolymer composition as described above, wherein the vinyl chloride monomer (monomer) is obtained from plant-derived ethylene.

  Furthermore, according to this invention, the heat-shrinkable film formed from the said plant-derived vinylidene chloride copolymer composition is provided. According to the present invention, in particular, the heat-shrinkable film formed from the plant-derived vinylidene chloride copolymer composition for wrapping, or the plant-derived vinylidene chloride copolymer for automatic filling and packaging. A heat shrinkable film formed from the combined composition is provided.

  Furthermore, according to the present invention, the plant-derived vinylidene chloride copolymer composition is formed from a plant-derived vinylidene chloride copolymer composition comprising a step of supplying the plant-derived vinylidene chloride copolymer composition to an extruder using a vacuum hopper. A method for producing a heat shrinkable film is provided.

  According to the present invention, it is a plant-derived vinylidene chloride copolymer composition characterized by containing a vinylidene chloride copolymer having a modern carbon ratio of 10 to 118 pMC as defined in ASTM D6866-12. Gas barrier properties, molding processability, and excellent packaging performance that are comparable to resin compositions containing fossil fuel-derived resins with carbon offset properties, that is, as wrapping films, and films for automatic filling packaging However, the effect that the vinylidene chloride copolymer composition which can form the heat-shrinkable film which has the outstanding practical property can be provided is produced.

  In addition, according to the present invention, the heat-shrinkable film formed from the plant-derived vinylidene chloride copolymer composition has a carbon offset property and contains a resin derived from fossil fuel. There is an effect that it is possible to provide a heat-shrinkable film having gas barrier properties, molding processability, and excellent practical characteristics that are comparable to those of a heat-shrinkable film formed from a product.

  Furthermore, according to the present invention, the heat formed from the plant-derived vinylidene chloride copolymer composition comprising the step of supplying the plant-derived vinylidene chloride copolymer composition to an extruder using a vacuum hopper. By being a method for producing a shrinkable film, it is possible to provide a method for producing a heat-shrinkable film formed from a plant-derived vinylidene chloride copolymer composition with good extrudability. Is done.

I. Plant-derived vinylidene chloride copolymer composition The vinylidene chloride copolymer composition of the present invention comprises a vinylidene chloride copolymer having a modern carbon ratio of 10 to 118 pMC as defined in ASTM D6866-12. And a plant-derived vinylidene chloride copolymer composition. Moreover, depending on a use or desired, Preferably it is the said plant-derived vinylidene chloride copolymer composition which contains an organic lubricant 100-6000 ppm with respect to a resin component.

1. Vinylidene chloride copolymer The plant-derived vinylidene chloride copolymer composition of the present invention contains a vinylidene chloride copolymer as a main component, and the vinylidene chloride copolymer is a modern carbon as defined in ASTM D6866-12. It is characterized by containing a vinylidene chloride copolymer having a ratio of 10 to 118 pMC. The vinylidene chloride copolymer is a copolymer formed from 60 to 98% by mass of vinylidene chloride and 2 to 40% by mass of at least one monomer copolymerizable with vinylidene chloride. ) And a monomer copolymerizable with vinylidene chloride are produced by suspension polymerization or emulsion polymerization. Examples of the monomer copolymerizable with vinylidene chloride (hereinafter sometimes referred to as “comonomer”) include, for example, vinyl chloride; methyl acrylate, ethyl acrylate, butyl acrylate, acrylic acid 2 -Acrylic acid alkyl ester (alkyl group having 1 to 18 carbon atoms) such as ethylhexyl, lauryl acrylate or stearyl acrylate; methyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, or stearyl methacrylate Methacrylic acid alkyl ester (alkyl group having 1 to 18 carbon atoms); vinyl cyanide such as acrylonitrile and methacrylonitrile; aromatic vinyl such as styrene; vinyl of aliphatic carboxylic acid having 1 to 18 carbon atoms such as vinyl acetate Esters; C1-C18 alkyl vinyl agents Vinyl polymerizable unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid and itaconic acid; alkyl esters of vinyl polymerizable unsaturated carboxylic acids such as maleic acid, fumaric acid and itaconic acid (partial esters) In addition, the diene monomer, the functional group-containing monomer, the polyfunctional monomer, and the like can be used. These comonomer can be used individually or in combination of 2 or more types. Among the comonomer, vinyl chloride, methyl acrylate, or butyl acrylate is preferable. A vinyl chloride monomer (monomer) is particularly preferable as a monomer copolymerizable with the vinylidene chloride monomer (monomer). Therefore, a particularly preferred vinylidene chloride copolymer is a vinylidene chloride-vinyl chloride copolymer. It is. The content of vinylidene chloride in the vinylidene chloride copolymer is preferably 70% by mass or more, more preferably 80% by mass or more. The upper limit of the content ratio of vinylidene chloride is not particularly limited, but is usually 97% by mass and in many cases 95% by mass from the viewpoint of extrudability.

[Vinylidene chloride copolymer having a modern carbon ratio of 10 to 118 pMC defined in ASTM D6866-12]
The vinylidene chloride copolymer contained in the plant-derived vinylidene chloride copolymer composition of the present invention is a vinylidene chloride copolymer having a modern carbon ratio of 10 to 118 pMC as defined in ASTM D6866-12 (hereinafter referred to as “ It may be referred to as a “vinylidene chloride copolymer having a modern carbon ratio of 10 to 118 pMC”. As described above, the resin composition containing no synthetic resin derived from a plant and containing a synthetic resin derived from a fossil fuel originally has a modern carbon ratio of 0 pMC. However, in reality, radioactive ¹⁴ C derived from nuclear tests and nuclear accidents conducted since 1950 are mixed in, and carbon isotopes are absorbed or permeated on the surface by carbon dioxide circulating in the modern global environment. In many cases, the modern carbon ratio of the synthetic resin derived from fossil fuel is in the range of 0.01 to 0.03 pMC due to the occurrence of the exchange. Therefore, a vinylidene chloride copolymer having a modern carbon ratio of 10 to 118 pMC is necessarily a vinylidene chloride copolymer containing a plant-derived vinylidene chloride copolymer, and is a vinylidene chloride copolymer having a carbon offset property. It can be said. The modern carbon ratio of the vinylidene chloride copolymer is measured by a radiocarbon dating method according to ASTM D6866-12 (revised April 2012). The modern carbon ratio of the vinylidene chloride copolymer does not exceed the modern carbon ratio of 118 pMC in 1963 before the nuclear test termination treaty where the ratio of ¹⁴ C peaked.

  The vinylidene chloride copolymer having a modern carbon ratio of 10 to 118 pMC is at least one of monomers (comonomer) that can be copolymerized with vinylidene chloride 60 to 98% by mass and vinylidene chloride. Since it is a copolymer formed from ˜40% by mass, a plant-derived monomer is used as one or both of vinylidene chloride and / or a comonomer that is a monomer (monomer) forming the copolymer. It can be obtained by using (monomer). That is, the vinylidene chloride copolymer having a modern carbon ratio of 10 to 118 pMC contained in the plant-derived vinylidene chloride copolymer composition of the present invention is a plant-derived vinylidene chloride and / or plant-derived comonomer. It is a vinylidene chloride copolymer formed from a monomer (monomer) containing one or both. A particularly preferred vinylidene chloride copolymer having a modern carbon ratio of 10 to 118 pMC is a vinylidene chloride-vinyl chloride copolymer having a modern carbon ratio of 10 to 118 pMC.

As is well known, vinylidene chloride (CH ₂ = CCl ₂ ) can be obtained by chlorinating vinyl chloride to ethane trichloride and then dehydrochlorinating ethane trichloride. At that time, vinyl chloride (CH ₂ = CHCl) was blown into ethylene (CH ₂ = CH ₂ ) with chlorine gas to form 1,2-dichloroethane (CH ₂ Cl-CH ₂ Cl), and then the temperature was 500 to 550 ° C. Can be obtained by thermal decomposition. As a method for producing vinylidene chloride, a method of dehydrochlorination using calcium hydroxide or sodium hydroxide after blowing chlorine gas into ethylene to form 1,2-dichloroethane is also well known.

  In the above-mentioned method for producing vinylidene chloride, the carbon atom in vinylidene chloride is derived from the carbon atom in ethylene. Therefore, a plant-derived vinylidene chloride monomer (single) that can be used to form a vinylidene chloride copolymer having a modern carbon ratio of 10 to 118 pMC contained in the plant-derived vinylidene chloride copolymer composition of the present invention. In order to obtain a monomer, ethylene derived from the carbon atom of the vinylidene chloride monomer (monomer) may be plant-derived ethylene. That is, the plant-derived vinylidene chloride copolymer composition of the present invention is a vinylidene chloride monomer (monomer) obtained from plant-derived ethylene as a vinylidene chloride copolymer having a modern carbon ratio of 10 to 118 pMC. Can be contained.

  As described above, in order to form a vinylidene chloride copolymer having a modern carbon ratio of 10 to 118 pMC contained in the plant-derived vinylidene chloride copolymer composition of the present invention, The body can be used. Since vinyl chloride is particularly preferred as the comonomer, plant-derived vinyl chloride is particularly preferred as the plant-derived comonomer. Since the carbon atom in the plant-derived vinyl chloride is derived from the carbon atom in ethylene as described above, the plant-derived vinylidene chloride copolymer composition of the present invention has a modern carbon ratio of 10 As the -118 pMC vinylidene chloride copolymer, a vinyl chloride monomer (monomer) obtained from plant-derived ethylene can be contained.

  Further, a vinylidene chloride-vinyl chloride copolymer having a modern carbon ratio of 10 to 118 pMC is particularly preferable as a vinylidene chloride copolymer having a modern carbon ratio of 10 to 118 pMC contained in the plant-derived vinylidene chloride copolymer composition of the present invention. As a combination, a vinylidene chloride monomer (monomer) obtained from plant-derived ethylene or a vinyl chloride monomer (monomer) obtained from plant-derived ethylene or one or both of them can do.

Plant-derived ethylene can be obtained, for example, by the following method, that is, sugar extracted from sugar raw materials such as sugarcane, which is a plant raw material, molasses (waste molasses) after sugar separation or sugarcane squeezed straw Ethyl alcohol (bioethanol) produced by ethanol fermentation using (bagasse) or the like as a fermentation raw material is distilled and separated. Bioethanol can be obtained in the same manner as above by saccharifying a starchy raw material such as corn as a plant raw material. Subsequently, the obtained bioethanol is heated with concentrated sulfuric acid to a temperature of 160 to 170 ° C., whereby the following formula C ₂ H ₅ OH → C ₂ H ₄ + H ₂ O
Plant-derived ethylene can be obtained by producing ethylene by the dehydration reaction. As is clear from the above formula, since carbon atoms in ethylene are derived from carbon atoms in ethanol, plant-derived ethylene is produced from bioethanol.

  Bioethanol can be produced using a plant raw material such as sugar cane as a fermentation raw material by the above method, but a commercially available product may be used. Since commercially available bioethanol is naturally ethanol derived from plants, ethylene produced by bioethanol dehydration is plant-derived ethylene.

[Combination of vinylidene chloride monomer and vinyl chloride monomer]
Accordingly, the vinylidene chloride-vinyl chloride copolymer having a modern carbon ratio of 10 to 118 pMC is particularly preferable as the vinylidene chloride copolymer having a modern carbon ratio of 10 to 118 pMC contained in the plant-derived vinylidene chloride copolymer composition of the present invention. The coalescence is obtained by combining vinylidene chloride monomer and vinyl chloride monomer with the following 1. ~ 8. It can obtain by mixing by the combination of these and making it superpose | polymerize. That is, when the plant-derived vinylidene chloride monomer (A), fossil fuel-derived vinylidene chloride monomer (A ′), plant-derived vinyl chloride monomer (B), fossil fuel-derived vinyl chloride monomer (B ′),
1. (A) + (B)
2. (A) + (B ′)
3. (A ') + (B)
4). (A) + (A ′) + (B)
5. (A) + (A ′) + (B ′)
6). (A) + (B) + (B ′)
7). (A ′) + (B) + (B ′)
8). (A) + (A ′) + (B) + (B ′).

[Mixture of plant-derived vinylidene chloride copolymer and fossil fuel-derived vinylidene chloride copolymer]
Furthermore, as the vinylidene chloride copolymer having a modern carbon ratio of 10 to 118 pMC contained in the plant-derived vinylidene chloride copolymer composition of the present invention, a vinylidene chloride copolymer having a modern carbon ratio of 10 to 118 pMC, A vinylidene chloride copolymer prepared by mixing a vinylidene chloride copolymer having a modern carbon ratio of less than 10 pMC, and in some cases a modern carbon ratio of substantially 0 pMC, so that the modern carbon ratio is 10 to 118 pMC. A vinylidene chloride copolymer having a modern carbon ratio of 10 to 118 pMC, which is a mixture of coalescence, that is, a mixture of a plant-derived vinylidene chloride copolymer and a fossil fuel-derived vinylidene chloride copolymer, can be used. In this case, the mixing ratio of the plant-derived vinylidene chloride copolymer and the fossil fuel-derived vinylidene chloride copolymer is particularly as long as the modern carbon ratio of the obtained vinylidene chloride copolymer is within the range of 10 to 118 pMC. It is not limited.

[Reduced viscosity]
The vinylidene chloride copolymer having a modern carbon ratio of 10 to 118 pMC contained in the plant-derived vinylidene chloride copolymer composition of the present invention has a reduced viscosity of usually 0.035 to 0.07, preferably 0.037. It is -0.067, More preferably, it is the range of 0.039-0.064. If the reduced viscosity is too small, the extrudability to a molded product such as a heat-shrinkable film will be insufficient, and if it is too large, it may have a tendency to be colored or melt molding may be difficult. The reduced viscosity of the vinylidene chloride copolymer is measured by dissolving in tetrahydrofuran at a temperature of 40 ° C.

[Mixture of vinylidene chloride copolymer]
Further, the vinylidene chloride copolymer having a modern carbon ratio of 10 to 118 pMC contained in the plant-derived vinylidene chloride copolymer composition of the present invention is a vinylidene chloride copolymer having two or more modern carbon ratios of 10 to 118 pMC. A polymer can be mixed and used. For example, a mixture of vinylidene chloride copolymers having different monomer ratios of vinylidene chloride and comonomer can be used. Further, a mixture of vinylidene chloride copolymers having different reduced viscosities can be used. For example, a mixture of a vinylidene chloride copolymer having a reduced viscosity of 0.048 or more and 50% by mass or more and a vinylidene chloride copolymer having a reduced viscosity of less than 0.048 (less than 50% by mass). Can be used). When the vinylidene chloride copolymer is mixed, the reduced viscosity of the mixed copolymer is preferably within the above-described range. In this case, more specifically, among the vinylidene chloride copolymers having different reduced viscosities, at least one vinylidene chloride copolymer is a vinylidene chloride copolymer having a modern carbon ratio of 10 to 118 pMC. A vinylidene chloride copolymer can be mixed to obtain a vinylidene chloride copolymer having a modern carbon ratio of 10 to 118 pMC. A vinylidene chloride copolymer having a modern carbon ratio of 10 to 118 pMC with different reduced viscosities may be mixed.

[Acetone extraction amount]
The vinylidene chloride copolymer having a modern carbon ratio of 10 to 118 pMC contained in the plant-derived vinylidene chloride copolymer composition of the present invention has an acetone extraction amount of 1% by mass or more from the viewpoint of extrusion processability. Is preferable, more preferably 1.5% by mass or more, and still more preferably 2% by mass or more. The upper limit of the acetone extraction amount is usually 15% by mass, and in many cases 12% by mass. The amount of acetone extracted from the vinylidene chloride copolymer is measured at a temperature of 70 ° C.

2. Other Polymers The plant-derived vinylidene chloride copolymer composition of the present invention contains, as a resin component, other polymers as desired in addition to a vinylidene chloride copolymer having a modern carbon ratio of 10 to 118 pMC. be able to. Thereby, the extrusion processability of the plant-derived vinylidene chloride copolymer composition of the present invention is improved, and various properties of the heat-shrinkable film formed from the composition are improved in a balanced manner according to the purpose. be able to. Other polymers include ethylene / vinyl acetate copolymers, copolymers of ethylene and acrylic acid, methacrylic acid or their alkyl esters, or MBS resins (methyl methacrylate / butadiene / styrene copolymers). Is mentioned. When these other polymers are contained, the content is usually 0.1 to 20 parts by mass with respect to 100 parts by mass of the vinylidene chloride copolymer having a modern carbon ratio of 10 to 118 pMC. -15 parts by mass.

3. Additives The plant-derived vinylidene chloride copolymer composition of the present invention improves extrudability and improves various properties of the heat-shrinkable film formed from the composition in a well-balanced manner. Therefore, various additives can be further contained. As the additive, either an organic substance (may be a polymer) or an inorganic substance can be used. Examples include plasticizers, stabilizers, antioxidants, pressure-sensitive adhesives, tackifiers, surfactants, fillers (fillers), pigments, and the like, and an optimal combination is selected depending on the application. A lubricant can be contained depending on the application or demand.

  Examples of the plasticizer include acetyl tributyl cytolate (ATBC), glycerin diacetyl monolaurate (GDAML), dibutyl sebacate (DBS), dioctyl sebacate, diacetylated monoglyceride (DALG), and the like. When the plasticizer is contained, the plasticizer is used with respect to 100 parts by mass of a resin component (hereinafter, simply referred to as “resin component”) containing a vinylidene chloride copolymer having a modern carbon ratio of 10 to 118 pMC. Usually, it is used at a ratio of 0.05 to 15 parts by mass. Examples of the stabilizer include epoxidized oils such as epoxidized soybean oil (ESBO) or epoxidized linseed oil (ELO); amide derivatives of fatty acid alkyl esters; magnesium hydroxide; tetrasodium pyrophosphate and the like. A stabilizer is normally used in the ratio of 0.1-5 mass parts with respect to 100 mass parts of resin components. Antioxidants include 2,6-di-tert-butyl-4-methyl-phenol (BHT), triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate 2,4-dimethyl-6-S-alkylphenol, 2,4-dimethyl-6- (1-methylpentadecyl) phenol, and mixtures thereof; thiodipropionic acid, distearylthio And thioether antioxidants such as dipropionate; phosphite antioxidants such as trisnonylphenyl phosphite and distearyl pentaerythritol diphosphite; An antioxidant is normally used in the ratio of 0.0001-0.05 mass part with respect to 100 mass parts of resin components. Examples of the pressure-sensitive adhesive include polyisobutylene (PIB), polybutene (PB), polybutadiene, and polypolyhydric alcohols such as polyethylene glycol, polyglycerin, and polypropylene glycol. Examples of the tackifier include sorbitan fatty acid ester, propylene glycol fatty acid ester, and glycerin fatty acid ester. More specifically, for example, glycerin mono (tri) stearate, glycerin mono (tri) oleate, and the like. There are surfactants (which may also function as meat stripping agents), paraffinic or cycloparaffinic liquid saturated hydrocarbons such as naphthenic process oil, paraffin wax, liquid paraffin (mineral oil), and the like. The content of the pressure-sensitive adhesive and / or tackifier is usually less than 0.2 parts by weight, preferably 0.1 parts by weight or less, with respect to 100 parts by weight of the resin component. Examples of the filler (filler) include silica and calcium carbonate. When the filler (filler) is contained, the content is usually 0.5 parts by mass or less, preferably 0.3 parts by mass or less with respect to 100 parts by mass of the resin component.

If the content of these additives is too large, the additives may bleed or the gas barrier properties of the plant-derived vinylidene chloride copolymer composition may be reduced. It is not essential for the plant-derived vinylidene chloride copolymer composition of the present invention to contain these additives.
4). Lubricant The plant-derived vinylidene chloride copolymer composition of the present invention can contain a lubricant if desired. In particular, when a heat-shrinkable film for automatic filling and packaging is formed from the plant-derived vinylidene chloride copolymer composition of the present invention, the inclusion of a lubricant shall have suitability for automatic filling and packaging. This is preferable because it is possible.

  As a lubricant that can be contained in the plant-derived vinylidene chloride copolymer composition of the present invention, a commonly used lubricant can be selected. That is, as the lubricant, inorganic lubricants and organic lubricants such as silicon dioxide, zeolite, and calcium carbonate can be used, but organic lubricants are preferable.

  As said organic lubricant, the saturated fatty acid amide, unsaturated fatty acid amide, substituted amide, etc. which are conventionally used as an organic lubricant can be used preferably. Examples of saturated fatty acid amides include butyramide, valeric acid amide, caproic acid amide, caprylic acid amide, capric acid amide, lauric acid amide, myristic acid amide, palmitic acid amide, stearic acid amide, arachidic acid amide, and behenic acid amide. Can be used. As the unsaturated fatty acid amide, oleic acid amide, erucic acid amide or the like can be used. Also, N-oleyl palmitate, N-stearyl stearate, N-stearyl oleate, substituted amides such as N-oleyl stearate and N-stearyl erucamide, methylol amide such as methylol stearate, Use saturated fatty acid bisamides such as methylenebisstearic acid amide and ethylene bishydroxystearic acid amide, unsaturated fatty acid bisamides such as ethylene biserucic acid amide, and aromatic bisamides such as m-xylylene bishydroxystearic acid amide. Can do.

[Fatty acid amide having unsaturated cis structure carbon double bond (a)]
In the plant-derived vinylidene chloride copolymer composition of the present invention, more preferably, the organic lubricant is a fatty acid amide (a) having an unsaturated cis structure carbon double bond. In the present invention, the fatty acid amide having an unsaturated cis structure carbon double bond (a) is an unsaturated fatty acid amide having at least one unsaturated cis structure carbon double bond in the molecular structure of the fatty acid amide. . In the case of an unsaturated fatty acid amide having a plurality of carbon double bonds in the molecular structure of the fatty acid amide, all of the carbon double bonds are unsaturated fatty acid amides that are carbon double bonds of an unsaturated cis structure. is there.

Particularly preferably, the fatty acid amide (a) having an unsaturated cis structure carbon double bond is the following (a ₁ ), (a ₂ ) and (a ₃ ):
_{(A 1) H 2 N-} CO - (- CH 2 -) n -CH = CH - (- CH 2 -) n -CH 3 ( where, n is in the range of 6 ≦ n ≦ 10 integer);
_{(A 2) H 2 N-} CO - (- CH 2 -) m-2 -CH = CH - (- CH 2 -) m -CH 3 ( however, m is an integer in the range of 6 ≦ m ≦ 10) And (a ₃ ) H ₂ N—CO — (— CH ₂ —) _{k + 4} —CH═CH — (— CH ₂ —) _k —CH ₃ (where k is in the range of 6 ≦ k ≦ 10); integer);
At least one fatty acid amide compound represented by a formula selected from the group consisting of:

The unsaturated cis structure fatty acid amide having a carbon-carbon double bond (a), specifically, for example, cis-9,10-octadecenoamide formula (a ₁₎ [H ₂ N-CO - (- CH ₂ —) ₇ —CH═CH — (— CH ₂ —) ₇ —CH ₃ ] (corresponding to n = 7), cis-6,7-tetradecenoamide [H ₂ N— represented by the formula (a ₂ ) _{CO - (- CH 2 -)} 4 -CH = CH - (- CH 2 -) 6 -CH 3 ] (corresponding to m = 6) and cis-7,8-hexadecenoamide _{[H 2 N-CO - (-} CH _{2 -) 5 -CH = CH -} (- CH 2 -) 7 -CH 3 ] (corresponding to m = 7), cis-13,14 -docosenoamide of formula (a ₃₎ [H ₂ N-CO _{- (- CH 2 -) 11} -CH = CH - (- CH 2 -) 7 ( corresponding to k = 7) -CH _3], and the like.

  When the unsaturated fatty acid amide has a trans structure carbon double bond, the uniform blending of the resin material becomes insufficient, or the unsaturated fatty acid amide having the trans structure carbon double bond It may bleed and may not function as an organic lubricant because the slipperiness deteriorates, and the die lip may become contaminated during extrusion to produce a heat-shrinkable film. Sometimes.

  The content of the organic lubricant is preferably 150 to 5800 ppm, more preferably 200 to 5600 ppm, still more preferably 250 to 5500 ppm, and particularly preferably 280 to 5400 ppm with respect to the resin component. If the content of the organic lubricant is too small, the heat-shrinkable film is insufficiently slippery and the suitability for automatic filling and packaging is impaired. There is a risk that it may not be smooth or automatic packaging may not be performed smoothly. If there is too much organic lubricant content, stickiness may increase during transportation and packaging operations, and the die lip may become contaminated during extrusion to produce heat-shrinkable films. There is a fear. In addition, content in the case of containing an inorganic lubricant is comparable as content of an organic lubricant.

5. Plant-derived vinylidene chloride copolymer composition The plant-derived vinylidene chloride copolymer composition of the present invention contains a vinylidene chloride copolymer having a modern carbon ratio of 10 to 118 pMC, and if desired, other polymers. And a vinylidene chloride copolymer composition derived from a plant that can contain various additives. The content ratio of the vinylidene chloride copolymer having a modern carbon ratio of 10 to 118 pMC in the plant-derived vinylidene chloride copolymer composition is usually 60% by mass or more, preferably 70% by mass or more, more preferably 75% by mass. Above, more preferably 80% by mass or more, particularly preferably 85% by mass or more. The plant-derived vinylidene chloride copolymer composition of the present invention is a vinylidene chloride copolymer having a modern carbon ratio of 10 to 118 pMC (may be a mixture), and if desired, other polymers and various additives. Depending on the application, for example, a compounding component such as an organic lubricant can be obtained by mixing in a conventional manner.

[Extrudability]
The plant-derived vinylidene chloride copolymer composition of the present invention has moldability comparable to that of a conventionally used fossil fuel-derived vinylidene chloride copolymer composition, and has particularly good extrudability. If the extrusion processability is poor, fluctuations in the motor load of the extruder become large, and unevenness occurs in the melt extrusion amount of the vinylidene chloride copolymer composition, and the extruded film may cause unevenness in the flow direction. . For example, if a heat-shrinkable film formed from a film having thick spots is used as a film for wrapping, there is a risk that spots will be generated in adhesion, and if a film for automatic filling packaging is used, seal spots may be generated.

6). Molded product formed from plant-derived vinylidene chloride copolymer composition The plant-derived vinylidene chloride copolymer composition of the present invention forms a molded product by injection molding, extrusion molding, stretch molding or other conventional molding methods. can do. As the molded article, a film, a sheet, a fiber, or the like is also included. As the film, a stretched film or a heat-shrinkable film formed by melt extrusion and stretching is also included. Furthermore, a multilayer film can also be formed by arrange | positioning the obtained film as a gas barrier layer and performing a coextrusion method or a lamination method.

II. Heat-shrinkable film formed from a plant-derived vinylidene chloride copolymer composition According to the present invention, in particular, a heat-shrinkable film formed from the plant-derived vinylidene chloride copolymer composition of the present invention is provided. The As the heat-shrinkable film formed from the vinylidene chloride copolymer composition, conventionally, heat-shrinkable films for wrapping and heat-shrinkable films for automatic filling packaging are known. A heat-shrinkable film formed from the above-mentioned plant-derived vinylidene chloride copolymer composition for use, or a heat-shrinkable film formed from the above-mentioned plant-derived vinylidene chloride copolymer composition for automatic filling and packaging Provided. That is, the plant-derived vinylidene chloride copolymer composition of the present invention has a carbon offset property and a molding processability comparable to a resin composition containing a resin derived from a fossil fuel, as a film for wrapping. Moreover, it is a vinylidene chloride copolymer composition which can obtain the heat-shrinkable film which has a practical characteristic also as a film for automatic filling packaging.

1. Heat-Shrinkable Film The plant-derived vinylidene chloride copolymer composition of the present invention can form a heat-shrinkable film by extrusion molding and stretching. The plant-derived vinylidene chloride copolymer composition of the present invention has an extrudability comparable to a composition comprising a resin derived from a fossil fuel that has been used to form a heat-shrinkable film or the like. It is possible to form a heat-shrinkable film excellent in practical properties, for example, mechanical properties such as tensile strength, elongation, tensile elastic modulus, shrinkage properties such as hot water shrinkage or dry heat shrinkage, and barrier properties. it can.

[Preparation of sample film]
Practical properties of the heat-shrinkable film formed from the plant-derived vinylidene chloride copolymer composition of the present invention are evaluated and measured using a sample film prepared by the following method. That is, a vinylidene chloride copolymer composition was melt-extruded cyclically at a resin temperature of about 185 ° C. using a φ40 single-screw extruder provided with a vacuum hopper (adjusted to a vacuum pressure of −680 mm mercury column), and a temperature of 10 ° C. After quenching in the cooling bath, inflation biaxial stretching is performed at room temperature to produce a heat-shrinkable film having a thickness of 20 μm and a width of about 110 mm, which is used as a sample film.

[Tensile strength]
The heat-shrinkable film formed from the plant-derived vinylidene chloride copolymer composition of the present invention has a tensile strength of usually 60 to 250 MPa, preferably 80 to 200 MPa. If the tensile strength is too low, the film is easily broken, and bag breakage or the like is generated due to dropping or the like particularly at low temperatures. The tensile strength of the heat-shrinkable film is measured for each of the machine direction (longitudinal direction, MD) and the direction perpendicular to the machine direction (lateral direction, TD) at a temperature of 23 ° C. and a tensile speed of 500 mm / min (unit: : MPa).

[Elongation]
The heat-shrinkable film formed from the plant-derived vinylidene chloride copolymer composition of the present invention has an elongation of usually 60 to 160%, preferably 70 to 150%. The elongation of the heat-shrinkable film is measured for each of MD and TD by the same method as the tensile strength (unit:%).

[Tensile modulus]
The heat-shrinkable film formed from the plant-derived vinylidene chloride copolymer composition of the present invention has a tensile elastic modulus of usually 200 to 600 MPa, preferably 250 to 500 MPa. The tensile elastic modulus of the heat-shrinkable film is measured for each of MD and TD at a temperature of 23 ° C. and a tensile speed of 10 mm / min (unit: MPa).

[Hot water shrinkage]
The heat-shrinkable film formed from the plant-derived vinylidene chloride copolymer composition of the present invention has a hot-water shrinkage at a temperature of 100 ° C. of usually 10 to 40%, preferably 15 to 35%. It has a good hot water shrinkage rate. The hot water shrinkage rate of the heat-shrinkable film is measured for each of MD and TD (unit:%).

[Dry heat shrinkage]
The heat-shrinkable film formed from the plant-derived vinylidene chloride copolymer composition of the present invention has a dry heat shrinkage at a temperature of 95 ° C. of usually 5 to 30%, preferably 7 to 24%. It has a characteristic dry heat shrinkage. The dry heat shrinkage of the heat-shrinkable film is measured for each of MD and TD (unit:%).

[Oxygen barrier properties]
The heat-shrinkable film formed from the plant-derived vinylidene chloride copolymer composition of the present invention has an oxygen permeability of usually 200 cm ³ / m ² · day · atm or less, preferably 150 cm ³ / m ² · day ·. Atm or less, more preferably 100 cm ³ / m ² · day · atm or less, and excellent oxygen barrier properties. In accordance with ASTM D3985-81, the oxygen permeability is measured at a temperature of 20 ° C. for a wrapping film and at a temperature of 30 ° C. for an automatic filling packaging film (unit: cm ³ / m ² · day.atm).

[Moisture permeability]
The heat-shrinkable film formed from the plant-derived vinylidene chloride copolymer composition of the present invention has an excellent moisture permeability of usually 30 g / m ² · day or less, preferably 25 g / m ² · day or less. Has water vapor barrier properties. The moisture permeability is measured in accordance with JIS K7129-1992 under conditions of a temperature of 40 ° C. and a relative humidity (RH) of 90% (unit: g / m ² · day).

[Thickness of heat-shrinkable film]
The thickness of the heat-shrinkable film formed from the plant-derived vinylidene chloride copolymer composition of the present invention is 5 to 50 μm, preferably 10 to 45 μm, as a single film. The heat-shrinkable film of the present invention can be used as a double film depending on applications.

2. Film for wrapping As a heat-shrinkable film formed from the plant-derived vinylidene chloride copolymer composition of the present invention, there is a practical wrapping film (a heat-shrinkable film for wrapping. Can be obtained.) A wrapping film is usually used in a state where it is wound around a cylindrical paper tube in a roll shape, and a user pulls out the film by a predetermined length and cuts it to store food or food. Used for making packaging. Therefore, the practicality as a wrapping film can be confirmed by the adhesion to the container, the touch, and the cutability.

[Lap container adhesion]
The adhesion of the wrapping film to the container is one of the important characteristics as the wrapping film characteristic. It is necessary to adhere to containers used for home use, such as cups, bowls, and dishes made of ceramics and glass. Due to the adhesiveness of the wrap container, the odor of the contents in the container does not leak to the outside, and the flavor of food or the like is maintained.

[Lap film feel]
The touch of the wrap film, that is, the feel of the wrap film is one of the important characteristics as the wrap film characteristics. If the film for wrapping is sticky, it may seem as if impurities exist on the surface. Moreover, as a film for wrapping, it is preferred and required that the film has a slight waist and the surface is smooth.

[Cutability]
The cut property of a wrapping film is one of the important characteristics as a wrapping film characteristic. The wrapping film must be easily cut after it is set in a container of a predetermined size. It does not require a large force or tears at an angle. It is preferable to cut according to the shape of the drawer cutter blade.

3. Automatic Filling Packaging Film As a heat shrinkable film formed from the plant-derived vinylidene chloride copolymer composition of the present invention, a practical automatic filling packaging film (heat shrinkable film for automatic filling packaging) Can be obtained. The film for automatic filling and packaging is, for example, formed into a cylindrical shape by rolling it in the width direction while forming a heat shrinkable film in the longitudinal direction (forming) and sealing it, and the heat shrinkage is in the shape of the cylindrical shape. After filling and wrapping meat paste products such as rice cakes and sausages in a casing made of conductive film, sealing both ends with metal wires, etc., and then heat sterilizing (retort processing), meat paste products, etc. Used for long-term storage. Since automatic filling and packaging is filled and packaged at high speed using an automatic filling and packaging machine and transferred together with the filling, automatic filling and packaging using an automatic filling and packaging machine smoothly and continuously is used for the film for automatic filling and packaging. In addition to the suitability for automatic filling and packaging machines and the good slipperiness of the film, sealability is also required such that the seal portion does not puncture or peel off even by heat sterilization treatment (retort treatment). Sealability can be confirmed by the presence or absence of seal puncture during retort and the peel strength of the seal.

[Applicability to automatic packaging machines]
The suitability of an automatic packaging machine for heat-shrinkable film for automatic filling and packaging is an automatic filling and packaging machine (for example, Kureha manufactured by Kureha Co., Ltd.) that integrates a film supply unit, a high-frequency sealing unit, an automatic filling unit, and a ligating unit. The sample film of the heat-shrinkable film formed from the vinylidene chloride copolymer composition is put on the automatic filling and packaging machine using the above-mentioned automatic filling and packaging machine, and the center is formed by high frequency sealing while rolling the film (forming). Seal to obtain a cylindrical film. The obtained cylindrical film is filled with a filling meat (sausage slide, etc.) as a filling, and both ends are clipped with a metal wire to obtain a filled package. The film for automatic filling and packaging needs to be suitable for continuous filling without stopping the automatic filling and packaging machine in these series of operation steps. If there is no suitability for automatic packaging machines, the film will meander and the seal part will shift, or sparks will occur in the high frequency seal part, the automatic filling and packaging machine will sometimes stop, and continuous filling may not be possible. The film may not run due to slipping failure and may not be continuously filled. The inability to carry out continuous filling is not preferable because of impracticality.

[Sliding property of film]
The heat-shrinkable film formed from the plant-derived vinylidene chloride copolymer composition of the present invention can have good slipperiness suitable for automatic filling packaging. The slipperiness of the film is evaluated based on the slipperiness of the film when passing the forming while rolling the film on the automatic filling and wrapping machine, which is slit to a width of 70 mm. In addition, the heat-shrinkable film formed from the plant-derived vinylidene chloride copolymer composition of the present invention has a coefficient of static friction measured according to JIS K7125 of usually 0.10 to 0.30, preferably 0.00. When the coefficient of dynamic friction is 15 to 0.25 and the dynamic friction coefficient is usually 0.08 to 0.20, preferably 0.10 to 0.18, it can be said that there is practicality as a film for automatic filling and packaging. In order to obtain a heat-shrinkable film having good film slipperiness, for example, a heat-shrinkable film is obtained from a plant-derived vinylidene chloride copolymer composition containing 100 to 6000 ppm of an organic lubricant with respect to the resin component. It can depend on the method of forming. As the organic lubricant, a fatty acid amide (a) having an unsaturated cis structure carbon double bond can be preferably used.

[Seal puncture during retort]
Sealing puncture at the time of retort related to the suitability of heat-shrinkable film for automatic filling and packaging is one of the important characteristics related to suitability for automatic packaging machinery. It is to be avoided as much as possible to cause a puncture and reduce the yield of the product when the automatically packed package is retorted. The factors causing seal puncture during retort are many complex, but by optimizing them to have stable quality and required properties in each of the designed resin composition, resin composition and extrusion process, film slip This can be solved by optimizing performance, reducing variation in thickness, and selecting suitable sealability.

[Seal T peel strength]
The seal T peel strength related to the sealability of the heat-shrinkable film for automatic filling and packaging measures and evaluates in advance the location where the puncture occurs most frequently during the retort. If the seal part is easily peeled off by this evaluation, the occurrence of seal puncture increases during the retort process. Therefore, it is practically necessary to have a seal T peel strength at which the seal portion does not peel off.

III. Method for producing heat-shrinkable film formed from plant-derived vinylidene chloride copolymer composition The heat-shrinkable film formed from the plant-derived vinylidene chloride copolymer composition of the present invention is derived from the plant of the present invention. The vinylidene chloride copolymer composition can be produced by adopting a melt extrusion method and a stretching method known per se, and is not particularly limited. For example, a vinylidene chloride copolymer having a modern carbon ratio of 10 to 118 pMC contained in a plant-derived vinylidene chloride copolymer composition, and other polymers and / or various additives optionally contained (these Are generally referred to as “raw materials”), mixed at a normal temperature to 60 ° C., preferably at a normal temperature to 50 ° C., with a known dry mixing apparatus such as a Henschel high-speed mixer, a blade blender, or a ribbon blender, These raw materials are mixed using a screw feeder or the like in the on-machine hopper of the extruder, and the raw material in the powder mixture or the raw material extruded into pellets is supplied to the extruder and melt-extruded. Then, a heat-shrinkable film can be obtained by stretching.

  Although it does not specifically limit as a extending | stretching method, Preferably the biaxial stretching method by the inflation shaping | molding by a circular die is employ | adopted. The draw ratio is preferably 2 to 4.5 times in the longitudinal direction and 3.0 to 5.0 times in the transverse direction.

  When the raw material is supplied to the extruder, it is preferably formed from a plant-derived vinylidene chloride copolymer composition comprising a step of supplying a plant-derived vinylidene chloride copolymer composition to the extruder using a vacuum hopper. The method for producing a heat-shrinkable film is preferable because the extrudability can be improved. When the vacuum hopper is used, the plant-derived vinylidene chloride copolymer-containing resin composition is stably supplied to the extruder, so fluctuations in the load on the motor of the extruder and fluctuations in the amount of extrusion can be kept small. There are effects such as adhesion and decomposition of the resin at the outlet, reduction of resin coloring and outflow of decomposition products, and reduction of bubble bursting during inflation molding. The vacuum degree of the vacuum hopper is −500 mm or less, preferably −600 to −755 mm in mercury column. Moreover, extrusion processability can be improved by supplying this resin composition to an extruder via a vacuum hopper.

  EXAMPLES The present invention will be further described below with reference to examples and reference examples, but the present invention is not limited to the examples. The measuring method of the characteristic or physical property of the resin raw material and heat-shrinkable film in Examples and Reference Examples is as follows.

[Reduced viscosity]
The reduced viscosity of the vinylidene chloride copolymer was measured by the following method. That is, 1 g of vinylidene chloride copolymer was added to 50 ml of tetrahydrofuran, dissolved at 40 ° C., filtered, precipitated with methanol, washed and dried. Subsequently, 20 ml of cyclohexanone having a temperature of 30 ° C. was added as a solvent to 80 mg of this dried polymer, dissolved by heating at 70 ° C. for 60 minutes, cooled at room temperature, and filtered through a filter paper to obtain a sample solution for solution viscosity measurement. 5 ml of the sample solution was put in an Ubbelohde viscometer, left in a thermostatic bath at a temperature of 30 ° C. for 5 minutes, then the number of seconds flowing down was measured by a normal operation method, and the reduced viscosity was determined by the following formula.
Reduced viscosity = (1/4) × {(T ₂ / T ₁ ) −1}
T ₁ : Number of seconds flowing down of cyclohexanone (solvent) at a temperature of 30 ° C. T ₂ : Number of seconds flowing down of the sample solution at a temperature of 30 ° C.

[Acetone extraction amount]
The amount of acetone extracted from the vinylidene chloride copolymer was measured by the following method. That is,
Weigh 5 g of a vinylidene chloride copolymer sample on a cylindrical filter paper, place absorbent cotton on the top, put it in a Soxhlet extractor, perform methanol extraction (85 ° C, 24 hours), take out the cylindrical filter paper, let it air dry, then extract Soxhlet About 120 ml of acetone was placed in a flat bottom flask set in a vessel, dried and weighed, attached to a Soxhlet extractor, and extracted with acetone at a temperature of 70 ° C. for 24 hours. After completion of the extraction, acetone is dried up at a temperature of 70 ° C., then dried and the mass of the flat bottom flask is weighed. Based on the tare mass of the flat bottom flask, the mass of the sample extracted from the mass change amount to acetone is measured. The percentage of the mass of the sample extracted into acetone relative to 5 g of the sample before extraction was calculated (unit: mass%).

[Extrudability]
The extrusion processability of the vinylidene chloride copolymer composition was evaluated by the following method. That is, the vinylidene chloride copolymer composition was melt-extruded annularly at a resin temperature of about 185 ° C. using a φ40 mm single screw extruder provided with a vacuum hopper (adjusted to a vacuum degree of about −680 mm mercury column). The motor load (A) of the extruder when the screw speed of the single screw extruder was 14 rpm was taken as EXT load, and the stability of the load when extrusion was continued for 30 minutes was evaluated according to the following criteria.
<Evaluation criteria for extrusion processability>
○: Load variation is less than ± 1A.
Δ: Load variation is in the range of ± 1A to ± 2A.
×: Load variation is ± 2 A or more.

[Tensile strength]
The tensile strength of the heat-shrinkable film was measured by the following method. That is, a sample piece cut out in a strip shape having a width of 10 mm from a film is clamped with a tensilon (manufactured by Toyo Baldwin) so that the sample length is 50 mm, at a temperature of 23 ° C. and a tensile speed of 500 mm / min. Measured (unit: MPa). The tensile strength was measured for each of the machine direction (longitudinal direction, MD) of the film and the direction perpendicular to the machine direction (lateral direction, TD).

[Elongation]
The elongation of the heat-shrinkable film was measured by the same method as the tensile strength (unit:%). The elongation was measured for each of the machine direction (longitudinal direction, MD) of the film and the direction perpendicular to the machine direction (lateral direction, TD).

[Tensile modulus]
The tensile elastic modulus of the heat-shrinkable film was measured by the following method. That is, a sample piece cut into a strip shape having a width of 20 mm from a film is clamped with a tensilon (manufactured by Toyo Baldwin) so that the sample length becomes 100 mm, at a temperature of 23 ° C. and a tensile speed of 10 mm / min. Measured (unit: MPa). The tensile modulus was measured for each of the machine direction (MD) and the cross direction (TD) of the film.

[Hot water shrinkage]
The hot water shrinkage rate of the heat-shrinkable film was measured by the following method. That is, a sample marked with a distance of 10 cm in each of the longitudinal direction (MD) and the transverse direction (TD) of the film was immersed in hot water at a temperature of 100 ° C. for 3 minutes, then taken out and immediately rinsed with normal temperature water. Cooled down. Thereafter, the distance between the marks was measured, and a value obtained by subtracting this measured value from 10 cm was obtained and displayed as a percentage with respect to 10 cm. One sample was tested 5 times, and the hot water shrinkage (unit:%) was displayed as an average value for each of MD and TD.

[Dry heat shrinkage]
The dry heat shrinkage rate of the heat-shrinkable film was measured by the following method. That is, 10 cm in each of the longitudinal direction (MD) and the lateral direction (TD) of the film on a corrugated cardboard having a thickness of 3 mm laid on a net shelf of a gear oven of 95 ° C. (manufactured by Robert, MOG-600 type). A sample film marked with a distance of was placed. At this time, the door of the gear oven was immediately closed after the sample film was put in (the open time of the door was within 3 seconds). After closing the door and leaving the measurement sample in the gear oven for 5 minutes, it was taken out and cooled naturally. Thereafter, the marked distance was measured, and the ratio of the decrease from 10 cm to the original length of 10 cm was displayed as a percentage. One sample was tested five times, and the dry heat shrinkage (unit:%) was displayed as an average value for each of MD and TD.

[Oxygen barrier properties]
The oxygen permeability of the heat-shrinkable film is based on ASTM D3985-81, using the OX-TRAN (registered trademark) 2/20 type manufactured by Modern Control, and the temperature of the wrapping film is 20 ° C. And about the automatic filling packaging film, it measured on the conditions of temperature 30 degreeC (unit: cm < ³ > / m < ² > * day * atm).

[Moisture permeability]
The moisture permeability of the heat-shrinkable film is measured under the conditions of a temperature of 40 ° C. and 90% RH using PERMATRAN-W (registered trademark) 3/31 type manufactured by Modern Control in accordance with JIS K7129-1992. (Unit: g / m ² · day).

[Lap container adhesion]
The adhesion of the heat-shrinkable film to the wrap container was measured and evaluated by the following method. That is, a heat-shrinkable film is covered so as to cover and touch an opening of a tea cup (Kasama Yaki) having an outer diameter of 72.5 mm, and the hole of 1 mm thick cardboard having a hole having an inner diameter of 75 mm is formed. By passing, the heat-shrinkable film was attached to the side of the tea cup with a constant force. Next, in this state, the tea cup is placed on a 20 kg scale, the jig in the center of the tea cup is pressed in the vertical direction at a speed of 300 mm / min so that the plane with a diameter of 30 mm is in contact with the film, and the film slides out of the container. The maximum load at the time was read and used as the adhesion of the heat-shrinkable film (N = 5 average value). The lap container adhesion was evaluated according to the following evaluation criteria.
<Evaluation criteria for lap container adhesion>
○: Adhesion strength is 0.1 kg or more.
X: Adhesion force is less than 0.1 kg.

[Lap film feel]
The touch of the wrap film of the heat-shrinkable film was performed by evaluating the touch by the following method. That is, about the touch of the surface of the film after leaving the heat-shrinkable film in an environment of a temperature of 40 ° C. and 50% RH for 10 days, we asked seven adult male and female subjects to evaluate based on the following criteria. The evaluation of the subject was used as the evaluation of the touch of the heat-shrinkable film. If the majority of evaluations cannot be obtained, the evaluation of the maximum number of people shall be the evaluation of the heat-shrinkable film touch. If the evaluation of the touch is `` ○ '', the touch of the heat-shrinkable film wrap film is `` ○ ''. evaluated.
<Evaluation criteria for touch>
○: Smooth (good).
Δ: Sticky (slightly poor)
X: Too sticky (bad).

[Cutability]
The cutability of the heat-shrinkable film was evaluated by the following method. That is, a heat-shrinkable film wound around a paper tube (outer diameter 36 mm, length 308 mm) is a special carton [product name: Kurelap (registered trademark), 2011 commercial carton, cutter shape is V blade. )), The evaluators of five adult men and women evaluated the ease of cutting when unwinding the heat-shrinkable film by hand, “easy to cut 3 points”, “normal 2 points”, “cut Evaluation was made according to the criteria of “difficult 1 point”, the average value of 5 evaluators was obtained, and the cut property of the heat shrinkable film was evaluated according to the following evaluation criteria.
<Evaluation criteria for cutting properties>
○: 2.6 points or more (excellent in practical use).
Δ: 2 or more and less than 2.6 (unsuitable for practical use)
X: Less than 2 points (unsuitable for practical use).

[Applicability to automatic packaging machines]
The suitability of the heat shrinkable film for automatic packaging machinery was evaluated by the following method. That is, a heat-shrinkable film slit to a width of 70 mm by using an automatic filling and packaging machine (Kureha Kureha type KAP500 manufactured by Kureha Co., Ltd.) in which a film supply unit, a high-frequency sealing unit, an automatic filling unit and a ligating unit are integrated. Was put on the automatic filling and packaging machine, and the film was rolled (forming) and center-sealed with a high frequency seal to obtain a cylindrical film. The obtained cylindrical film was filled with 50 g of filled meat (sausage slide) as a filling, and both ends were clipped with metal wires to obtain a filled package. The heat-shrinkable film was flowed 100 m in length to perform automatic filling and packaging, and the presence or absence of suitability for automatic filling and packaging machinery was evaluated according to the following evaluation criteria.
<Evaluation criteria for suitability of automatic packaging machinery>
○: Filling meat (sausage sliding) could be continuously filled without stopping the automatic filling and packaging machine.
(Triangle | delta): The film meandered and the seal | sticker part shifted | deviated, the spark generate | occur | produced in the high frequency seal | sticker part, the automatic filling and packaging machine sometimes stopped, and it was not able to carry out continuous filling.
X: The film did not run due to poor slipping of the forming part, and could not be filled.

[Sliding property of film]
The slipping property of the film was evaluated based on the following criteria when the heat-shrinkable film slit to a width of 70 mm was applied to the automatic filling and packaging machine and the film was passed through forming while rolling. Furthermore, the static friction coefficient and the dynamic friction coefficient of the heat-shrinkable film were measured according to JIS K7125.
<Standard for film slipperiness>
○: Folded well at the forming part, the film passed and ran.
X: The film was detached from the forming part or shifted, and the film running was poor.

[Seal puncture during retort]
The seal puncture during retort of the heat-shrinkable film was evaluated by the following method. In other words, 100 packed packages obtained by evaluating the suitability of the automatic packaging machine described above are arranged in a tray and put into a hot water hot water storage type retort can (RCS-60 / 10 TG manufactured by Nisaka Manufacturing Co., Ltd.). Then, retort treatment was performed at a sterilization temperature of 120 ° C. for 15 minutes. Next, cooling water was added and cooled to obtain 100 filled packages that were retorted. Of the 100 filled packages, the number of filled packages punctured from the seal portion was counted, and the seal puncture during retort was evaluated according to the following criteria.
<Evaluation criteria for seal puncture during retort>
○: The number of punctures is 5 or less.
Δ: The number of punctures is 6 to 10.
X: The number of punctures is 11 or more.

[Seal T peel strength]
The seal T peel strength of the heat-shrinkable film was evaluated by the following method. That is, 100 packed packages obtained by evaluating the suitability of the automatic packaging machine described above were arranged in a tray, put into the hot water hot water storage type retort can, and retorted at a sterilization temperature of 120 ° C. for 15 minutes. Next, cooling water was added and cooled to obtain 100 filled packages that were retorted. Any 5 filled packaging bodies were extracted from the retorted filled packaging body. About each filling packaging body, ten places separated in the seal | sticker part were selected, the ear | edge part of each seal | sticker part was pinched with the finger | toe, and it peeled off, and the strength of the seal | sticker part was evaluated on the following references | standards. When the evaluation of the strength of the seal portion was “◯”, the evaluation of the seal T peel strength of the heat-shrinkable film was evaluated as “◯”.
<Evaluation criteria for strength of seal part>
○: Neither of the five filled packages are peeled off at 10 locations.
X: There is a filled package in which the seal part is peeled off.

I. Production of film for wrapping [Preparation Example 1: Preparation of plant-derived vinylidene chloride-vinyl chloride copolymer (1)]
Vinylidene chloride obtained from plant-derived ethylene produced by dehydration reaction of commercially available bioethanol (hereinafter sometimes referred to as “plant-derived vinylidene chloride”) and vinyl chloride obtained from plant-derived ethylene (hereinafter referred to as “ Plant-derived vinyl chloride ”)) using a polymerization can of 10 L in volume, mixed with plant-derived vinylidene chloride: plant-derived vinyl chloride = 82: 18 (mass ratio), and the initial polymerization temperature Then, the temperature was raised to 45 to 50 ° C., and then the temperature was raised. Suspension polymerization was performed under the conditions of a late polymerization temperature of 60 ° C. to obtain a vinylidene chloride-vinyl chloride copolymer. The polymerization time was 28 hours. The obtained vinylidene chloride-vinyl chloride copolymer had a reduced viscosity of 0.044 and an acetone extraction amount of 7.0% by mass. Since this vinylidene chloride-vinyl chloride copolymer is a polymer formed only from a plant-derived vinylidene chloride monomer and a plant-derived vinyl chloride monomer, the carbon atom in the polymer is a plant-derived vinylidene chloride monomer. Is derived only from plant-derived vinyl chloride monomer, substantially free of carbon atoms derived from other carbon-containing compounds, and the modern carbon ratio defined in ASTM D6866-12 is within the range of 10 to 118 pMC. there were. Hereinafter, the vinylidene chloride-vinyl chloride copolymer prepared in Preparation Example 1 may be referred to as “plant-derived vinylidene chloride-vinyl chloride copolymer (1)” or “plant-derived VD-VC (1)”.

[Example 1]
For 100 parts by mass of the plant-derived vinylidene chloride-vinyl chloride copolymer (1), acetyl tributyl citrate (ATBC), glycerin diacetyl monolaurate (GDAML) and epoxidized linseed oil (ELO) are used as additives. 7 parts by mass in total, 0.16 parts by mass in total of an adhesive [polyisobutylene (PIB)] and a tackifier [sorbitan monooleate], and the compound (vinylidene chloride-vinyl chloride) Polymer composition) was prepared. Next, the compound is supplied to a φ40 single screw extruder equipped with a vacuum hopper (vacuum pressure adjusted to about −680 mm mercury column), melt-extruded in a ring shape at a resin temperature of about 185 ° C., and rapidly cooled in a cooling bath at a temperature of 10 ° C. Inflation biaxial stretching was performed at room temperature to produce a wrapping film having a thickness of 20 μm and a width of 110 mm. Extrudability and tensile strength, elongation, tensile modulus, dry heat shrinkage, oxygen permeability, moisture permeability, wrap container adhesion, wrap film feel and cutability (hereinafter collectively referred to as “wrapping film”) Table 1 shows the results of measurement and evaluation of “characteristics”.

[Example 2]
For 100 parts by mass of the plant-derived vinylidene chloride-vinyl chloride copolymer (1), 4 parts by mass in total of ATBC, GDAML, and ELO as additives, and 0 in total of the adhesive and tackifier A film for wrapping was produced in the same manner as in Example 1 except that 0.09 part by mass was added. Table 1 shows the results of measurement and evaluation of various characteristics of the wrapping film.

[Example 3]
To 100 parts by mass of the plant-derived vinylidene chloride-vinyl chloride copolymer (1), 5 parts by mass in total of ATBC, GDAML and ELO are added as additives, and no adhesive and tackifier are added. A wrapping film was produced in the same manner as in Example 1 except that. Table 1 shows the results of measurement and evaluation of various characteristics of the wrapping film.

[Example 4]
100 parts by weight of the plant-derived vinylidene chloride-vinyl chloride copolymer (1) is obtained by 50 parts by weight of the plant-derived vinylidene chloride-vinyl chloride copolymer (1) by conventional petroleum decomposition and fractionation. Vinylidene chloride-vinyl chloride copolymer produced using vinylidene chloride and vinyl chloride obtained from ethylene derived from the obtained fossil fuel as a polymerization raw material [vinylidene chloride: vinyl chloride = 82: 18 (mass ratio). Hereinafter, it may be referred to as “fossil fuel-derived vinylidene chloride-vinyl chloride copolymer (1)” or “fossil fuel-derived VD-VC (1)”. The modern carbon ratio was 0 pMC. A film for wrapping was produced in the same manner as in Example 2 except that the mixture was changed to a mixture with 50 parts by mass. The modern carbon ratio was in the range of 10 to 118 pMC. Table 1 shows the results of measurement and evaluation of various characteristics of the wrapping film.

[Example 5]
100 parts by mass of the plant-derived vinylidene chloride-vinyl chloride copolymer (1), 10 parts by mass of the plant-derived vinylidene chloride-vinyl chloride copolymer (1), and fossil fuel-derived vinylidene chloride-vinyl chloride copolymer A wrapping film was produced in the same manner as in Example 2 except that the polymer (1) was changed to a mixture with 90 parts by mass. The modern carbon ratio was in the range of 10 to 118 pMC. Table 1 shows the results of measurement and evaluation of various characteristics of the wrapping film.

[Reference Example 1]
Example 1 except that 100 parts by mass of the plant-derived vinylidene chloride-vinyl chloride copolymer (1) was changed to 100 parts by mass of the fossil fuel-derived vinylidene chloride-vinyl chloride copolymer (1). In the same manner as described above, a wrapping film was produced. The modern carbon ratio was substantially 0 pMC. Table 1 shows the results of measurement and evaluation of various characteristics of the wrapping film.

[Reference Example 2]
Example 2 except that 100 parts by mass of the plant-derived vinylidene chloride-vinyl chloride copolymer (1) was changed to 100 parts by mass of the fossil fuel-derived vinylidene chloride-vinyl chloride copolymer (1). In the same manner as described above, a wrapping film was produced. The modern carbon ratio was substantially 0 pMC. Table 1 shows the results of measurement and evaluation of various characteristics of the wrapping film.

II. Production of film for automatic filling and packaging [Preparation Example 2: Preparation of plant-derived vinylidene chloride-vinyl chloride copolymer (2)]
The plant-derived vinylidene chloride and the plant-derived vinyl chloride were mixed in a plant-derived vinylidene chloride: plant-derived vinyl chloride = 81: 19 (mass ratio) using a 10 L polymerization vessel, and the initial polymerization stage The temperature was set to 45 to 50 ° C., then the temperature was raised, and suspension polymerization was performed under the conditions of a late polymerization temperature of 60 ° C. to obtain a vinylidene chloride-vinyl chloride copolymer. The polymerization time was 44 hours. The obtained vinylidene chloride-vinyl chloride copolymer had a reduced viscosity of 0.062 and an acetone extraction amount of 2.5% by mass. This vinylidene chloride-vinyl chloride copolymer had a modern carbon ratio as defined in ASTM D6866-12 of 10 to 118 pMC. Hereinafter, the vinylidene chloride-vinyl chloride copolymer prepared in Preparation Example 2 may be referred to as “plant-derived vinylidene chloride-vinyl chloride copolymer (2)” or “plant-derived VD-VC (2)”.

[Preparation Example 3: Preparation of plant-derived vinylidene chloride-vinyl chloride copolymer (3)]
The plant-derived vinylidene chloride and the plant-derived vinyl chloride were mixed in a plant-derived vinylidene chloride: plant-derived vinyl chloride = 81: 19 (mass ratio) using a 10 L polymerization vessel, and the initial polymerization stage The temperature was set to 45 to 50 ° C., then the temperature was raised, and suspension polymerization was performed under the conditions of a late polymerization temperature of 60 ° C. to obtain a vinylidene chloride-vinyl chloride copolymer. The polymerization time was 38 hours. The obtained vinylidene chloride-vinyl chloride copolymer had a reduced viscosity of 0.056 and an acetone extraction amount of 2.5% by mass. This vinylidene chloride-vinyl chloride copolymer had a modern carbon ratio as defined in ASTM D6866-12 of 10 to 118 pMC. Hereinafter, the vinylidene chloride-vinyl chloride copolymer prepared in Preparation Example 3 may be referred to as “plant-derived vinylidene chloride-vinyl chloride copolymer (3)” or “plant-derived VD-VC (3)”.

[Preparation Example 4: Preparation of plant-derived vinylidene chloride-vinyl chloride copolymer (4)]
The plant-derived vinylidene chloride and the plant-derived vinyl chloride were mixed at a plant-derived vinylidene chloride: plant-derived vinyl chloride = 71: 29 (mass ratio) using a 10 L polymerization vessel, and the initial polymerization stage The temperature was set to 45 to 50 ° C., then the temperature was raised, and suspension polymerization was performed under the conditions of a late polymerization temperature of 60 ° C. to obtain a vinylidene chloride-vinyl chloride copolymer. The polymerization time was 28 hours. The obtained vinylidene chloride-vinyl chloride copolymer had a reduced viscosity of 0.040 and an acetone extraction amount of 9.3% by mass. This vinylidene chloride-vinyl chloride copolymer had a modern carbon ratio as defined in ASTM D6866-12 of 10 to 118 pMC. Hereinafter, the vinylidene chloride-vinyl chloride copolymer prepared in Preparation Example 4 may be referred to as “plant-derived vinylidene chloride-vinyl chloride copolymer (4)” or “plant-derived VD-VC (4)”.

[Preparation Example 5: Preparation of vinylidene chloride-vinyl chloride copolymer (2) derived from fossil fuel]
Fossil fuel-derived vinylidene chloride and fossil fuel-derived vinyl chloride are mixed in a 10 L volume polymerization vessel using fossil fuel-derived vinylidene chloride: fossil fuel-derived vinyl chloride = 81: 19 (mass ratio). The initial polymerization temperature was 45 to 50 ° C., then the temperature was raised, and suspension polymerization was performed under the conditions of a late polymerization temperature of 60 ° C. to obtain a vinylidene chloride-vinyl chloride copolymer. The polymerization time was 44 hours. The obtained vinylidene chloride-vinyl chloride copolymer had a reduced viscosity of 0.062 and an acetone extraction amount of 2.5% by mass. The vinylidene chloride-vinyl chloride copolymer had a modern carbon ratio of 0 pMC as defined in ASTM D6866-12. Hereinafter, the vinylidene chloride-vinyl chloride copolymer prepared in Preparation Example 5 is referred to as “fossil fuel-derived vinylidene chloride-vinyl chloride copolymer (2)” or “fossil fuel-derived VD-VC (2)”. is there.

[Example 6]
11 parts by mass in total of dibutyl sebacate (DBS), ATBC, and epoxidized soybean oil (ESBO) as additives with respect to 100 parts by mass of the plant-derived vinylidene chloride-vinyl chloride copolymer (2) Cis-13,14-docosenoamide [H ₂ N—CO — (— CH ₂ —) ₁₁ —CH═CH — (— CH ₂ —) ₇ —CH ₃ ] [unsaturated cis structure carbon (A ₃ ) H ₂ N—CO — (— CH ₂ —) _{k + 4} —CH═CH — (— CH ₂ —) _k —CH ₃ (where k is a fatty acid amide having a heavy bond (a)) , An integer in the range of 6 ≦ k ≦ 10) and a compound corresponding to k = 7. ] 0.08 parts by mass (corresponding to 800 ppm with respect to the resin component) and 0.1 parts by mass of silicon dioxide as an inorganic lubricant were added and mixed to obtain a compound (vinylidene chloride-vinyl chloride copolymer). Combined composition) was prepared. Next, the compound is supplied to a φ40 single screw extruder equipped with a vacuum hopper (vacuum pressure adjusted to about −680 mm mercury column), melt-extruded in a ring shape at a resin temperature of about 185 ° C., and rapidly cooled in a cooling bath at a temperature of 10 ° C. Inflation biaxial stretching was performed at room temperature to produce a film for automatic filling and packaging having a thickness of 20 μm and a width of 110 mm. Extrudability, tensile strength, elongation, tensile modulus, hot water shrinkage, oxygen permeability, moisture permeability, film slipperiness (coefficient of friction), automatic packaging suitability, seal puncture during retort Table 2 shows the results of measuring and evaluating the seal T peel strength (hereinafter, collectively referred to as “various characteristics” in the same manner as described above).

[Example 7]
As an additive, a film for automatic filling and packaging was prepared in the same manner as in Example 6 except that 0.15 parts by mass of glycerin monostearate (GMS), which is a meat peeling agent, was further added. Table 2 shows the results of measuring and evaluating various characteristics of the film for automatic filling and packaging.

[Example 8]
100 parts by mass of the plant-derived vinylidene chloride-vinyl chloride copolymer (2), 85 parts by mass of the plant-derived vinylidene chloride-vinyl chloride copolymer (3), and plant-derived vinylidene chloride-vinyl chloride copolymer A film for automatic filling and packaging was produced in the same manner as in Example 7 except that the mixture (15) was changed to a mixture with 15 parts by mass. Table 2 shows the results of measuring and evaluating various characteristics of the film for automatic filling and packaging.

[Example 9]
Further, ethylene / vinyl acetate copolymer [vinyl acetate content 33 mass%. Hereinafter, it may be referred to as “EVA”. ] Was added in the same manner as in Example 8 except that 2.5 parts by mass was added. Table 2 shows the results of measuring and evaluating various characteristics of the film for automatic filling and packaging.

[Example 10]
100 parts by weight of the plant-derived vinylidene chloride-vinyl chloride copolymer (2), 30 parts by weight of the plant-derived vinylidene chloride-vinyl chloride copolymer (2), and the fossil fuel derived from Preparation Example 5 A film for automatic filling and packaging was produced in the same manner as in Example 7 except that the mixture was changed to a mixture with 70 parts by mass of vinylidene chloride-vinyl chloride copolymer (2). The modern carbon ratio was in the range of 10 to 118 pMC. Table 2 shows the results of measuring and evaluating various characteristics of the film for automatic filling and packaging.

[Reference Example 3]
The plant-derived vinylidene chloride-vinyl chloride copolymer (2) 100 parts by mass was changed to 100 parts by mass of the fossil fuel-derived vinylidene chloride-vinyl chloride copolymer (2) obtained in Preparation Example 5, A film for automatic filling and packaging was produced in the same manner as in Example 6 except that the organic lubricant was changed to stearamide. The modern carbon ratio was substantially 0 pMC. Table 2 shows the results of measuring and evaluating various characteristics of the film for automatic filling and packaging.

  From Table 1 and Table 2, the plant-derived vinylidene chloride copolymer of the present invention of Examples 1 to 10 containing a vinylidene chloride copolymer having a modern carbon ratio defined by ASTM D6866-12 of 10 to 118 pMC The composition is excellent in carbon offset property, and has a gas barrier property and molding processability comparable to those of a fossil fuel-derived vinylidene chloride copolymer composition, and forms a heat shrinkable film with excellent packaging performance. I found out that I can do it. Moreover, the plant-derived vinylidene chloride copolymer composition of the present invention can be used as a heat-shrinkable film for wrapping or as a heat-shrinkable film for automatic filling packaging by adjusting the composition and molding conditions. It was found that this is a vinylidene chloride copolymer composition capable of forming a heat-shrinkable film having excellent practical properties.

  According to the present invention, it is a plant-derived vinylidene chloride copolymer composition characterized by containing a vinylidene chloride copolymer having a modern carbon ratio of 10 to 118 pMC as defined in ASTM D6866-12. It has a carbon offset property, a resin composition containing a resin derived from fossil fuel, and has a gas barrier property and molding processability comparable to those of a resin composition, and has excellent packaging performance, that is, as a film for wrapping, and automatic filling Since a vinylidene chloride copolymer composition capable of forming a heat-shrinkable film having excellent practical properties can be provided as a packaging film, the industrial applicability is high.

  In addition, according to the present invention, the heat-shrinkable film formed from the plant-derived vinylidene chloride copolymer composition has a carbon offset property and contains a resin derived from fossil fuel. Since a heat-shrinkable film having a gas barrier property, molding processability and excellent practical properties comparable to those of a heat-shrinkable film formed from a product can be provided, the industrial applicability is high.

  Furthermore, according to the present invention, the heat formed from the plant-derived vinylidene chloride copolymer composition comprising the step of supplying the plant-derived vinylidene chloride copolymer composition to an extruder using a vacuum hopper. Since the method for producing a shrinkable film can provide a method for producing a heat-shrinkable film formed from a plant-derived vinylidene chloride copolymer composition with good extrusion processability, High availability.

Claims (2)

A heat-shrinkable film for wraps formed from a plant-derived vinylidene chloride copolymer composition comprising a vinylidene chloride copolymer having a modern carbon ratio of 10 to 118 pMC as defined in ASTM D6866-12 . Heat shrink for automatic filling and packaging formed from a plant-derived vinylidene chloride copolymer composition characterized by containing a vinylidene chloride copolymer having a modern carbon ratio of 10 to 118 pMC as defined in ASTM D6866-12 Sex film .