JP7075714B2 - Extruded laminated film suitable for freshness preservation applications and its applications - Google Patents

Description

The present invention relates to an extruded laminated film suitable for freshness-preserving applications, which can prevent or reduce deterioration of the ability to suppress the growth of germs due to extrusion laminating processing.

Products that require freshness, such as fresh foods such as vegetables and fruits, are distributed in packaging containers made of film. The commercial value of these fresh foods declines when discoloration, deterioration such as wilting, and further spoilage occur over time. Therefore, products such as these fresh foods are required to maintain their freshness by being stored in a packaging container.

Especially in recent years, cut vegetable packaging has been sold in supermarkets and the like, and has been used in chain restaurants to save the trouble of cooking. In the cut vegetable packaging, it is necessary to prevent bacteria from entering the contents that have been sterilized, and to prevent the nutrient solution eluted from the contents from adhering to the inner surface of the packaging material and propagating the bacteria. There is a need to develop films and packaging materials that have high properties and less transfer of antibacterial components to the contents.
As a freshness-preserving film having high antibacterial properties, a freshness-preserving film in which a specific compound is present in a specific amount on at least one surface has been proposed (see, for example, Patent Document 1).

When a laminated film is produced using such a freshness-retaining film, there is a problem that the antibacterial property is lowered in the laminating process. Most of the cut vegetables in Japan are currently sold in the packaging of OPP (biaxially oriented polypropylene) film alone, but overseas, the laminated composition such as OPP layer / adhesive layer / polyethylene layer, nylon layer / adhesive layer / polyethylene layer, etc. It is generally sold in the same packaging, and especially in such a case, it has been required to prevent or reduce the deterioration of the antibacterial property due to the lamination.
On the other hand, regarding the extruded laminated film which is widely used along with the dry laminated film, no concrete measure which can prevent or reduce the deterioration of the antibacterial property due to the laminating has been found, and a solution thereof has been desired.

International Publication No. 2014/142218 A1 Pamphlet

An object of the present invention is to solve the above-mentioned problems, and to provide an extruded laminated film suitable for freshness-preserving applications, which can effectively prevent or reduce the deterioration of antibacterial properties due to laminating in the extruded laminated film, and its use. do.

As a result of diligent studies, the present inventor has effectively prevented or alleviated the deterioration of antibacterial properties due to laminating by blending a specific compound in a specific amount in the extruded polymer film layer constituting the extruded laminated film. We have found that we can solve the problem, and have completed the present invention.

That is, the present invention
[1]
A polymer film in which at least one compound selected from the group consisting of palmityldiethanolamine, stearyldiethanolamine, glycerin monolaurate and diglycerin monolaurate is present on at least one surface in an amount of 0.002-0.5 g / m ² . Layer A and
An extruded laminated film having an extruded polymer film layer B formed on the polymer film layer A.
The extruded polymer film layer B contains 0.01 to 2% of at least one compound selected from the group consisting of palmityldiethanolamine, stearyldiethanolamine, glycerin monolaurate and diglycerin monolaurate. , The above-mentioned extruded laminated film.

Hereinafter, [2] to [13] are each one of the preferred embodiments of the present invention.
[2]
The extruded laminate film according to [1], wherein the stretched film layer C is further laminated on the extruded polymer film layer B.
[3]
The extruded laminated film according to [1] or [2], wherein the polymer film layer A is a polyethylene-based film.
[4]
The extruded laminated film according to any one of [1] to [3], wherein the extruded polymer film layer B contains at least one of linear polyethylene and low density polyethylene.
[5]
The extruded laminated film according to any one of [1] to [4], wherein the stretched film layer C has been subjected to a corona treatment and / or an anchor coating treatment.
[6]
The extruded laminated film according to any one of [1] to [5], wherein the stretched film layer C is a uniaxial or biaxially stretched film of polyamide, polyethylene terephthalate, or polypropylene.
[7]
The extruded laminated film according to any one of [1] to [6], wherein the oxygen permeability at 20 ° C. and 80% RH is 2000 ml / m ² · MPa or less.

[8]
The extruded laminated film according to any one of [1] to [7], which is used for keeping freshness.
[9]
A packaging container comprising the extruded laminated film according to any one of [1] to [7].
[10]
The packaging container according to [9], wherein the extruded laminated film has at least one opening, the length of the opening is 0.5 to 7 mm, and the width of the opening is less than 10 μm.
[11]
The packaging container according to [9] or [10], which is used for maintaining the freshness of cut vegetables or fruits and vegetables.
[12]
A packaging body for maintaining freshness of cut vegetables or fruits and vegetables, wherein the cut vegetables or fruits and vegetables are stored in the packaging container according to any one of [9] to [11].
[13]
The package for maintaining the freshness of fruits and vegetables according to [12], which further contains a hygroscopic agent and / or an antibacterial agent.

According to the present invention, in an extruded laminated film, deterioration of antibacterial properties in the laminating process can be effectively prevented or reduced.
By appropriately designing the layer structure of the extruded laminated film, barrier properties, hand-cutting properties, multicolor printability, surface gloss, etc. can be improved, so that while maintaining sufficient antibacterial properties for maintaining freshness, It is possible to realize an extruded laminated film having excellent barrier properties, hand-cutting properties, multicolor printability, surface gloss and the like.
Since the extruded laminated film of the present invention has the above-mentioned excellent properties, it can be suitably used for a packaging container, particularly a packaging container for maintaining the freshness of fruits and vegetables.

Hereinafter, embodiments for carrying out the present invention will be described.
In the present invention, at least one compound selected from the group consisting of palmityldiethanolamine, stearyldiethanolamine, glycerin monolaurate and diglycerin monolaurate (hereinafter, also referred to as "specific compound") is applied to at least one surface. The polymer film layer A present at 0.002-0.5 g / m ² and
An extruded laminated film having an extruded polymer film layer B formed on the polymer film layer A.
The extruded polymer film layer B contains 0.01 to 2% of at least one compound selected from the group consisting of palmityldiethanolamine, stearyldiethanolamine, glycerin monolaurate and diglycerin monolaurate. , The above-mentioned extruded laminated film.

(Polymer film layer A)
The polymer film layer A constituting the extruded laminated film of the present invention has at least one surface of at least one compound selected from the group consisting of palmityldiethanolamine, stearyldiethanolamine, glycerin monolaurate and diglycerin monolaurate. It is a polymer film layer present in 0.002 to 0.5 g / m ² .
The polymer constituting the polymer film layer A is not particularly limited, and a suitable polymer may be appropriately selected, improved and used in relation to the purpose and application from the conventionally used polymer films. Either a thermoplastic resin or a thermosetting resin may be used, but it is preferable to use a thermoplastic resin from the viewpoint of processability in film formation and the like.
Examples of the thermoplastic resin include homopolymers or copolymers of α-olefins such as ethylene, propylene, 1-butene, 1-hexene, 4-methyl / 1-pentene and 1-octene. Specifically, high-pressure method low-density polyethylene, linear low-density polyethylene (LLDPE), ethylene-based polymers such as high-density polyethylene, propylene homopolymers, propylene / α-olefin random copolymers, and propylene block copolymers. Examples thereof include propylene-based polymers such as, and polyolefins such as poly 1-butene and poly 4-methyl / 1-pentene. Further, as the thermoplastic resin, polyester such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyamide such as nylon-6, nylon-66, polymethoxylen adipamide, polyvinyl chloride, polyimide, ethylene / acetic acid. A vinyl copolymer or a saponified product thereof, a polyvinyl alcohol, a polyacrylonitrile, a polycarbonate, a polystyrene, an ionomer, a polylactic acid, a biodegradable resin such as polybutylene succinate, or a mixture thereof can also be used. One type of these thermoplastic resins may be used, or two or more types may be used in combination. Among these, as the thermoplastic resin, it is preferable to use an ethylene polymer from the viewpoint of cost, processability, transparency and the like.

(Polyethylene film)
The polyethylene-based film preferably used in the polymer film layer A constituting the present invention is mainly composed of an ethylene-based polymer. The ethylene-based polymer means an ethylene homopolymer and / or an ethylene copolymer. Specifically, for example, ethylene-based polymers such as high-pressure low-density polyethylene, linear low-density polyethylene (LLDPE), and high-density polyethylene can be mentioned as suitable examples.
(Ethylene polymer)
The ethylene-based polymer includes a homopolymer of ethylene, a copolymer containing ethylene as a main monomer and at least one of α-olefins having 3 to 8 carbon atoms, an ethylene / vinyl acetate copolymer, and the like. Kensates and ionomers can be mentioned as suitable examples thereof. More specifically, polyethylene, ethylene / propylene copolymer, ethylene / 1-butene copolymer, ethylene / 1-pentene copolymer, ethylene / 1-hexene copolymer, ethylene / 4-methyl-1- A more preferable example thereof is a polymer in which ethylene such as a penten copolymer or an ethylene / 1-octene copolymer is used as a main monomer and at least one of α-olefins having 3 to 8 carbon atoms is used as a main monomer. Can be mentioned. The proportion of α-olefins in these copolymers is preferably 1 to 15 mol%.
Further, as the ethylene-based polymer, a suitable example may be an ethylene polymer manufactured and sold under the name of polyethylene. Specifically, high-pressure method low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), and high-density polyethylene (HDPE) are preferable, and LLDPE is more preferable. LLDPE is a copolymer of ethylene and a small amount of propylene, butene-1, heptene-1, hexene-1, octene-1, 4-methyl-pentene-1, and the like. Further, the ethylene-based polymer may be a homopolymer of ethylene, or may be a polymer mainly composed of ethylene such as LLDPE.
The density of the ethylene polymer is preferably 0.910 to 0.940 g / cm ³ , more preferably 0.920 to 0.930 g / cm ³ . When the density is 0.910 g / cm ³ or more, the heat sealability is improved. Further, when the density is 0.940 g / cm ³ or less, processability and transparency are improved.

(Specific compound)
On the surface of the polymer film layer A constituting the extruded laminated film of the present invention, at least one compound selected from the group consisting of palmityldiethanolamine, stearyldiethanolamine, glycerin monolaurate and diglycerin monolaurate (specific compound). ) Exists in a specific amount.
As the specific compound, palmityldiethanolamine, stearyldiethanolamine, glycerin monolaurate, diglycerin monolaurate may be used alone, or a mixture thereof may be used. Palmityl diethanolamine is an alkyl diethanolamine having a palmityl group, which is a long-chain alkyl group having 16 carbon atoms. Stearyldiethanolamine is an alkyldiethanolamine having a stearyl group having 18 carbon atoms. Glycerin monolaurate is a monoester of lauric acid (12 carbon atoms) and glycerin. Diglycerin monolaurate is a monoester of lauric acid (12 carbon atoms) and diglycerin.
Stearyldiethanolamine and palmityldiethanolamine have a relatively higher melting point than myristyldiethanolamine and lauryldiethanolamine. Therefore, when the polymer film layer A is melt-molded, for example, in heat fixation when the polymer film layer A is a stretched film, stearyldiethanolamine and palmityldiethanolamine are relatively difficult to volatilize. Further, stearyldiethanolamine and palmityldiethanolamine are excellent in antibacterial property and freshness retention property. Further, when the extruded laminated film of the present invention is used as a packaging film, the transfer to the object to be packaged, which is the content that comes into contact with the packaging film, is relatively slow, and the safety is excellent. Can be sustained. In addition, the "packaged object" of the freshness-preserving film may be referred to as "contents".
(Alkyldiethanolamine; carbon number of part of long chain alkyl group; melting point)
Stearyl diethanolamine; 18 pieces; 51 ° C.
Palmityl diethanolamine; 16 pieces; 28 ° C.
Myristyldiethanolamine; 14 pieces; 22-23 ° C
Lauryl diethanolamine; 12 pieces; liquid at room temperature

The specific compounds used in the present invention may individually contain similar compounds. The palmityl diethanolamine (16 carbon atoms) may contain, for example, a small amount of myristyl diethanolamine (14 carbon atoms) or an alkyl diethanolamine having an alkyl group having 12 to 20 carbon atoms such as stearyl diethanolamine (18 carbon atoms). Further, the stearyldiethanolamine (18 carbon atoms) may contain, for example, a small amount of alkyl diethanol having an alkyl group having 16 to 20 carbon atoms. Further, the specific compound may contain a small amount of a compound in which a part of the amines of these similar compounds of palmityldiethanolamine and stearyldiethanolamine form an ester with an aliphatic carboxylic acid. Further, the glycerin monolaurate may contain, for example, a small amount of a monoester of a higher linear aliphatic carboxylic acid having 10 or 14 carbon atoms and glycerin. Further, the diglycerin monolaurate may contain a small amount of a monoester of a higher aliphatic carboxylic acid having 10 or 14 carbon atoms and diglycerin. Further, the (di) glycerin monoester may contain a small amount of a similar compound such as (di) glycerin diester or (di) glycerin triester, and a similar compound in which the glycerin moiety is diglycerin and the diglycerin moiety is triglycerin. good. Similar compounds of these specific compounds are generally synthesized at the same time or difficult to separate in steps such as synthesis and separation of the specific compound. Further, the similar compound may be contained in an amount of 50 parts by mass or less, may be contained in an amount of 40 parts by mass or less, and is preferably not contained, based on 100 parts by mass of the specific compound.
Further, the polymer film layer A constituting the extruded laminated film of the present invention according to the present invention has an antistatic agent and an antifogging agent (excluding the specific compound, if necessary) in addition to the specific compound as described later. .) Other additives such as lubricants can be included. The total of these other additives and the similar compound may be contained in an amount of 50 parts by mass or less, 40 parts by mass or less, or 30 parts by mass or less with respect to 100 parts by mass of the specific compound. May be.

(Adding functions such as antibacterial and freshness retention)
In the polymer film layer A constituting the present invention, 0.002 to 0.5 g / m ² of the specific compound may be present on any surface thereof, but the side not in contact with the extruded polymer film layer B. It is preferable that 0.002 to 0.5 g / m ² of the specific compound is present on the surface of the above (hereinafter, may be referred to as “anti-lame surface”). The polymer film layer A constituting the extruded laminated film of the present invention is preferably a uniaxial or biaxially stretched film such as a corona-treated polyamide, polyethylene terephthalate, or polypropylene, before being laminated with the stretched film layer C. In the state, 0.002 to 0.5 g / m ² of the specific compound is preferably present on the surface of the anti-laminate surface, more preferably 0.004 to 0.4 g / m ² is present, and 0.01 to 0. The presence of 3 g / m ² is more preferable, and the presence of 0.02 to 0.2 g / m ² is most preferable. As a method for allowing the specific compound to exist on the anti-laminate surface of the polymer film layer A, for example, the specific compound may be sprayed on the surface, or a solution or suspension containing the specific compound may be applied to the surface. There is a coating method to be used. Further, by incorporating the specific compound in the polymer film layer A or other layers, the specific compound is bleeded out on the anti-lame surface of the polymer film layer A, so that 0.002 to 0.5 g / g of the specific compound is obtained. m ² may be present. The total content of the specific compound in the extruded laminated film of the present invention is preferably 0.001 to 3% by mass, preferably 0.01 to 3% by mass, from the viewpoint that the specific compound can be bleeded out to the surface in the above range. 3% by mass is more preferable, and 0.1 to 2% by mass is further preferable.

(Method for quantifying specific compounds on the surface of polymer film layer)
The amount of the specific compound on the surface of the polymer film layer A is a value calculated from the amount of the specific compound coated when the specific compound is applied to the surface by the coating method. When the specific compound is blended in the polymer film layer A and / or other layers, the amount of the specific compound on the surface of the polymer film layer A is determined by the surface of the polymer film layer A. It is a value quantified by washing with dichloromethane, collecting the washing liquid, concentrating and constant volume, silylating, and using gas chromatograph mass spectrometry (GC / MS).

(Extruded polymer film layer B)
In the extruded laminated film of the present invention, the extruded polymer film layer B is formed on the polymer film layer A by the extrusion laminating method. In the present invention, by having the extruded polymer film layer B, the extruded polymer film layer B can be made to have a function different from that of the polymer film layer A, and a film having multiple functions can be realized. be able to. Further, the extruded polymer film layer B is different from the polymer film layer A because it is usually excellent not only in the adhesiveness to the polymer film layer A but also in the adhesiveness to other layers. By further laminating another layer having a function, preferably a stretched film layer C, a film having a more complex function can be realized. For example, barrier properties, hand-cutting properties, multi-color printability, surface gloss, and the like can be improved.
Further, according to the extrusion laminating method, a laminated film can be manufactured at high speed, with good adhesion, and without the need for an adhesive or a solvent, so that productivity, cost, quality, working environment, etc. can be obtained. But it is advantageous.

The polymer constituting the extruded polymer film layer B may be any as long as it can be extruded and laminated on the polymer film layer A, and is not particularly limited, but has a melting point, processability, and the polymer film layer A. Polyethylene is preferable because it is excellent in the adhesiveness between the films and the adhesiveness between the stretched film layer C and the like.
(Polyethylene preferably used for the extruded polymer film layer B)
As the polyethylene preferably used for the extruded polymer film layer B constituting the present invention, the melt flow rate (hereinafter abbreviated as MFR) measured at 190 ° C. and a load of 2.16 kg according to ATM D1238 is preferably 1 to 50. Illustrate an ethylene polymer having a density of 3 to 40 (g / 10 minutes) and a density (ASTMD1505) of 0.900 to 0.940, preferably 0.900 to 0.930 (g / cm ³ ). Can be done.
The melt tension (MT) is a value obtained by measuring the stress when the molten ethylene polymer is stretched at a constant speed. Specifically, it is a value measured using an MT measuring machine manufactured by Toyo Seiki under the conditions of a resin temperature of 190 ° C., an extrusion speed of 15 mm / min, a take-up speed of 15 m / min, a nozzle diameter of 2.09 mmφ, and a nozzle length of 8 mm. ..
The polyethylene preferably used for the extruded polymer film layer B constituting the present invention preferably satisfies the above-mentioned physical properties, but the production method thereof is not particularly limited. Therefore, even so-called high-pressure polyethylene (low-density polyethylene) produced under high pressure using a radical catalyst, or using a Ziegler catalyst or a metallocene catalyst, in the presence of ethylene and optionally a comonomer such as α-olefin. It may be so-called medium-low pressure polyethylene manufactured under medium-low pressure. High-pressure polyethylene has long-chain branches in the molecular chain, which exhibits high melt tension, and thus can be particularly preferably used in the present invention. Further, so-called linear low-density polyethylene can also be preferably used in the present invention, and in particular, linear low-density polyethylene having a long-chain branch can be preferably used.
Further, the polyethylene of the extruded lami layer preferably used for the extruded polymer film layer B constituting the present invention is an unsaturated carboxylic acid such as ethylene and a small amount of vinyl acetate as long as the characteristics as a sealant film in the present invention are not impaired. It may be a copolymer with. Since the copolymer of ethylene and a small amount of unsaturated carboxylic acid has excellent adhesion to other resins, it can be suitably used in the extruded polymer film layer B.

(Content of specific compound of extruded polymer film layer B)
The extruded polymer film layer B constituting the extruded laminated film of the present invention is a specific compound, that is, at least one compound selected from the group consisting of palmityl diethanolamine, stearyldiethanolamine, glycerin monolaurate and diglycerin monolaurate. However, 0.01 to 2% by mass is blended.
By blending 0.01 to 2% by mass of the specific compound in the extruded polymer film layer B, deterioration of antibacterial properties due to the extrusion laminating process is effectively prevented or reduced, and the extruded laminate film having stable antibacterial performance for a long period of time. Can be realized.
The mechanism by which the extruded polymer film layer B is blended with a predetermined amount of a specific compound to prevent or reduce the deterioration of antibacterial properties due to the extrusion laminating step is not necessarily clear, but the extruded polymer adjacent to the polymer film layer A is not always clear. The presence of the specific compound in the film layer B at a relatively high concentration causes the concentration gradient of the extruded polymer film layer B (and other layers such as the stretched film layer C) of the specific compound in the polymer film layer A. The size becomes smaller, diffusion into the extruded polymer film layer B (and other layers such as the stretched film layer C) is suppressed, and the concentration of the specific compound inside and on the surface of the polymer film layer A is easily maintained at a relatively high level. It is presumed that there is something to do with that.

When the blending amount of the specific compound is 0.01% by mass or more, the decrease in antibacterial property can be effectively prevented or reduced, while when it is 2% by mass or less, bleed-out at an undesired place is possible. It is possible to effectively suppress unfavorable phenomena such as.
The blending amount of the specific compound in the extruded polymer film layer B is preferably 0.05 to 1.5% by mass, and particularly preferably 0.08 to 1.0% by mass.
The blending amount of the specific compound in the extruded polymer film layer B can be appropriately adjusted by increasing or decreasing the blending amount of the specific compound when preparing the polymer material constituting the extruded polymer film layer B. The specific compound may be directly blended into the polymer material, or a composition (master batch) in which the specific compound is blended in a small amount of the polymer material is prepared, and finally the blending amount of the specific compound is in the desired range. The master batch and the polymer material may be mixed so as to be.
The details of the specific specific compound are the same as those described above for the specific compound used in the polymer film layer A.

(surface treatment)
In forming the extruded polymer film layer B, a surface treatment for improving the adhesiveness may be performed on the polymer film layer prior to the extrusion lamination. As the surface treatment, a corona treatment, an anchor coat treatment and the like can be preferably applied.
(Anchor coating agent)
As the anchor coating agent preferably used in the above embodiment, a coating amount (solid content) of the corona-treated polymer film layer A in which the anchor coating agent is dissolved in an organic solvent at a solid content concentration of 15 to 50% is applied. ) It can be applied so as to be 0.1 to 0.5 g / m ² .
The organic solvent used here can be generally classified as follows.
Hydrocarbon solvents: toluene, xylene, solvent naphtha, normal hexane, isohexane, cyclohexane, methylcyclohexane, normalheptane, isooctane, normaldecane, etc. Alcohol solvents: methanol, ethanol, butanol, IPA (isopropyl alcohol), normal propyl alcohol, Butanol, isobutanol, TBA (tershary butanol), butanediol, ethylhexanol, benzyl alcohol, etc. Ketone solvents: acetone, methyl ethyl ketone, methyl isobutyl ketone, DIBK (diisobutyl ketone), cyclohexanone, DAA (diacetone alcohol), etc. Solvents: ethyl acetate, methyl acetate, butyl acetate, methoxybutyl acetate, cellosolve acetate, amyl acetate, normal propyl acetate, isopropyl acetate, methyl lactate, ethyl lactate, butyl lactate, etc. Ethereal solvents: isopropyl ether, methyl cellosolve, cellosolve, butyl cellosolve , Dioxane, MTBE (methyl tertiary butyl ether), butyl carbitol, etc. From the above, an anchor coating agent, a material for the polymer film layer A and the extruded polymer film layer B, and an organic solvent suitable in relation to the extruded laminating process. Just select.

The resin used as the anchor coating material is not particularly limited, and an appropriate resin may be appropriately selected in relation to the materials of the polymer film layer A and the extruded polymer film layer B and the extrusion laminating process, but is polyester-based. Resins, polyether resins, polyester ether resins, polyurethane resins, polyester urethane resins, polyether urethane resins, polyester ether resins, polyester ether urethane resins, etc. can obtain sufficient laminating strength. It can be preferably used.
These resins may be used alone or in combination with a curing agent containing a polyisocyanate compound or the like, and may be used in a two-component curing type.

Examples of the polyester-based resin include dibasic acids such as terephthalic acid, isophthalic acid, adipic acid, azelaic acid, and sebatic acid, dialkyl esters thereof, or mixtures thereof, and examples thereof include ethylene glycol, propylene glycol, diethylene glycol, butylene glycol, and the like. Glycols such as neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 3,3'-dimethylol heptane, polyoxyethylene glycol, polyoxypropylene glycol, polytetramethylene ether glycol, etc. Alternatively, a polyester resin obtained by reacting with a mixture thereof or a polyester resin obtained by ring-opening polymerization of lactones such as polycaprolactone, polyvalerolactone, and poly (β-methyl-γ-valerolactone) can be obtained. , Can be given as a suitable example.
As the polyether resin, for example, an oxylan compound such as ethylene oxide, propylene oxide, butylene oxide, or tetrahydrofuran is polymerized using a low-volume polyol such as water, ethylene glycol, propylene glycol, trimethylolpropane, or glycerin as an initiator. As a suitable example, the obtained polyether resin or the like can be mentioned.
The polyether ester resin may be obtained by reacting a dibasic acid such as terephthalic acid, isophthalic acid, adipic acid, azelaic acid, or sebatic acid, a dialkyl ester thereof, or a mixture thereof with the polyether resin. A suitable example thereof is a polyether ester resin or the like.

Examples of the organic polyisocyanate include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylenediocyanate, 2,3-butylenediocyanate, 1,3-butylenediocyanate, 2, Aliphatic diisocyanates such as 4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanate methylcaproate, 1,4-cyclohexanediisocyanate, 1,3-cyclohexanediisocyanate, 3-isocyanatemethyl- 3,5,5-trimethylcyclohexylisocyanate, 4,4'-methylenebis (cyclohexylisocyanate), methyl2,4-cyclohexanediisocyanate, methyl2,6-cyclohexanediisocyanate, 1,4-bis (isocyanatemethyl) cyclohexane, 1, Alicyclic diisocyanate such as 3-bis (isocyanatemethyl) cyclohexane, m-phenylenediisocyanate, p-phenylenediisocyanate, 4,4'-diphenyldiisocyanate, 1,5-naphthalenediocyanate, 4,4'-diphenylmethanediisocyanate, 2, Aromatic diisocyanates such as 4- or 2,6-tolylene diisocyanate or a mixture thereof, 4,4'-toluidin diisocyanate, dianisidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 1,3- or 1,4-xylylene diisocyanate. Aromatic aliphatic diisocyanates such as isocyanate or a mixture thereof, ω, ω'-diisocyanate-1,4-diethylbenzene, 1,3- or 1,4-bis (1-isocyanate-1-methylethyl) benzene or a mixture thereof, triisocyanate, tri Organic triisocyanates such as phenylmethane-4,4', 4 "-triisocyanate, 1,3,5-triisocyanatebenzene, 2,4,6-triisocyanatetoluene, 4,4'-diphenyldimethylmethane-2, Polyisocyanate monomer such as organic tetraisocyanate such as 2'-5'-5'-tetraisocyanate, dimer, trimmer, biuret, allophanate, carbon dioxide gas and the polyisocyanate monomer derived from the polyisocyanate monomer. A polyisocyanate having a 2,4,6-oxadiazine trione ring obtained from, for example, ethylene glycol. Ester, propylene glycol, butylene glycol, hexylene glycol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 3,3'-dimethylolpropane, cyclohexanedimethanol, diethylene glycol, Additives with low molecular weight polyols with a molecular weight of less than 200 such as triethylene glycol, dipropylene glycol, glycerol, trimethylolpropane, pentaerythritol, sorbitol, or polyester polyols with a molecular weight of 200 to 20,000, polyether ester polyols, polyesters. Suitable examples include adducts such as amide polyols, polycaprolactone polyols, polyvalerolactone polyols, acrylic polyols, polycarbonate polyols, polyhydroxyalkanes, castor oil, and polyurethane polyols.
Further, the organic polyisocyanate can also be used as a curing agent for an organic solvent type adhesive.

(Stretched film layer C)
In the extruded laminated film of the present invention, it is preferable that the stretched film layer C is further laminated on the extruded polymer film layer B. Since it is easy to impart a function different from that of the polymer film layer A to the stretched film layer C, the stretched film layer C is laminated with the polymer film layer A via the extruded polymer film layer B. Therefore, a film having multiple functions can be realized. For example, by using a stretched film layer C having barrier properties, hand-cutting properties, multicolor printability, and / or surface gloss, these properties can be improved in the extruded laminated film of the present invention. can.

The stretched film used as the stretched film layer C is not particularly limited, and is related to the materials of the polymer film layer A and the extruded polymer film layer B, the use of the extruded laminated film, the properties to be imparted to the extruded laminated film, and the like. Although an appropriate film can be appropriately selected in the above, it is preferable to use a uniaxial or biaxially stretched film of polyamide, polyethylene terephthalate, or polypropylene from the viewpoint of availability, ease of processing, mechanical properties, and the like.
A film made of polyamide typified by nylon 6, nylon 66, etc., a polyethylene terephthalate, a film made of polyester typified by polyethylene naphthalate, and a film made of polypropylene are preferable, but a polyethylene film, a polycarbonate film, and an ethylene / vinyl alcohol co-weight. From coalesced film, polyvinyl alcohol film, polyvinyl chloride film, polyvinylidene chloride film, and polystyrene film, and poly L lactic acid, poly D lactic acid, or stereocomplex crystal poly lactic acid that precisely coordinates poly L lactic acid and poly D lactic acid. A uniaxial or biaxially stretched film such as a stretched film can also be used as the stretched film layer C.
Further, the stretched film layer C may be a stretched film on which an inorganic substance such as aluminum, zinc or silica or an oxide thereof is vapor-deposited.

In order to improve the adhesiveness with the extruded polymer film layer B, it is preferable that the stretched film layer C is subjected to a corona treatment and / or an anchor coating treatment.
The details of the corona treatment and the anchor coating treatment in the stretched film layer C are the same as those described above with respect to the corona treatment and the anchor coating treatment in the polymer film layer A.

<Other additives>
All or any of the polymer film layer A, the extruded polymer film layer B, and the stretched film layer C constituting the extruded laminated film of the present invention are heat-stable and stable as long as the object of the present invention is not impaired. Additives such as agents (antioxidants), weather stabilizers, UV absorbers, lubricants, slip agents, nucleating agents, blocking inhibitors, antistatic agents, antifogging agents, pigments, dyes and the like can be added. Further, various fillers such as talc, silica and diatomaceous earth may be added.

Examples of the heat stabilizer include 3,5-di-t-butyl-4-hydroxytoluene, tetrakis [methylene (3,5-di-t-butyl-4-hydroxy) hydrocinnamate] methane, and n-octadecyl. Phenolic antioxidants such as -3- (4'-hydroxy-3,5-di-t-butylphenyl) propionate, 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2-hydroxy Benzophenone antioxidants such as -4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2,4-dihydroxybenzophenone, 2- (2'-hydroxy-5-methylphenyl) benzotriazole, substituted benzotriazole, etc. Benzotriazole antioxidant, 2-ethylhexyl-2-cyano-3,3-diphenylacrylate, ethyl-2-cyano-3,3-diphenylacrylate, phenylsulfate, 4-t-butylphenylsalicylate Etc. can be given as a preferable example. These may be used alone or in combination of two or more.
Antistatic agents include, for example, alkylamines and their derivatives, higher alcohols, pyridine derivatives, sulfated oils, soaps, olefin sulfate esters, alkyl sulfate esters, fatty acid ethyl sulphonate, alkyl sulphonate, alkyl. Natalen sulphonate, alkylbenzene sulphonate, naphthalen sulphonate, amber acid ester sulphonate, phosphate ester salt, partial fatty acid ester of polyhydric alcohol, ethylene oxide adduct of fatty alcohol, ethylene oxide addition of fatty acid Preferred examples thereof include ethylene oxide adducts of fatty amino or fatty acid amides, ethylene oxide adducts of alkylphenols, ethylene oxide adducts of alkyl naphthols, ethylene oxide adducts of partial fatty acid esters of polyhydric alcohols, polyethylene glycol and the like. Can be mentioned as. These may be used alone or in combination of two or more.

As the lubricant, for example, stearic acid, stearic acid amide, oleic acid amide, higher alcohol, liquid paraffin and the like can be mentioned as preferable examples. These may be used alone or in combination of two or more.
Examples of the ultraviolet absorber include ethylene-2-cyano-3,3'-diphenylacrylate, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, and 2- (2'-hydroxy-3'-. t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, etc. It can be mentioned as a preferable example. These may be used alone or in combination of two or more.
Examples of the antifogging agent include higher aliphatic alcohols, glycerin fatty acids, diglycerin fatty acids, acid esters of these products or diglycerin fatty acids, higher aliphatic amines, and higher fatty acid esters, except for specific compounds. , These mixtures and the like can be mentioned as a preferable example. These may be used alone or in combination of two or more.

<Extruded laminated film and its manufacturing method>
The extruded laminated film of the present invention can be produced by forming an extruded polymer film layer B on the polymer film layer A and further laminating a stretched film layer C as desired.
For example, the stretched film layer C and the polymer film layer A prepared in advance are optionally coated with the above-mentioned anchor coating, and then extrusion lamination using the extruded polymer film layer B is performed to extrude the present invention. Laminated films can be manufactured.
As the laminating resin constituting the extruded polymer film layer B, a polymer resin containing 0.01 to 2% by mass of a specific compound, preferably low density polyethylene (LDPE) containing 0.01 to 2% by mass of a specific compound. By using the above, a particularly good extruded laminated film can be produced with high productivity.
When applying the anchor coating agent, it is preferable to treat the surface of the stretched film layer C with a corona treatment from the viewpoint of adhesive stability. Specifically, from the viewpoint of adhesive stability, the surface tension of the film surface after the corona treatment is preferably 35 mN / m or more, and more preferably 40 mN / m or more.

Further, it is preferable that the thickness of the stretched film layer C is 10 to 50 μm and the thickness of the polymer film layer C is 10 to 120 μm from the viewpoint of the antibacterial performance of the obtained extruded laminated film, but it has a detailed layer structure. Is preferably designed as appropriate according to the barrier performance required for the application, hand-cutting property (easy-opening property), multicolor printing suitability, independence (feeling of waist), gloss of the packaging bag surface, and the like.
When the extruded laminated film of the present invention is used as a freshness-preserving film, the oxygen permeability at 20 ° C. and 80% RH (measured according to JIS K7126) is preferably 2000 ml / m ² · MPa or less. When the oxygen permeability is 2000 ml / m ² · MPa or less, it is easy to keep the packaged object at a low oxygen concentration. Therefore, when packaging cut vegetables such as lettuce, browning is suppressed, and meat and fresh fish are suppressed. , Fresh foods that do not breathe, such as delicatessen, can suppress the growth of bacteria, which is preferable from the viewpoint of improving freshness retention performance.

<Packaging container>
The extruded laminated film of the present invention can be preferably used for packaging containers.
The packaging container containing the extruded laminated film of the present invention can be manufactured, for example, by folding the extruded laminated film in two with the surface layer as the inner surface and sealing both ends with a heat seal, a fusing seal, or the like. can. It can also be manufactured by stacking two extruded laminated films so that the surface layer is on the inner surface and sealing the three sides with a heat seal, a fusing seal, or the like. The back surface layer of the packaging container may be printed, if necessary, before being molded into the packaging container.

Further, in the case of a packaging container for maintaining the freshness of a packaged object that breathes fruits and vegetables, an opening may be provided in the extruded laminated film. In this aspect, it is preferred that the extruded laminated film has at least one opening, the opening having one or more slit-shaped portions having a length of 0.5-7 mm. That is, it is preferable that there is a portion of the length of the opening having a width of less than 10 μm over at least 0.5 mm. From the viewpoint of preventing foreign matter from entering from the outside, it is preferable that the width is less than 10 μm over the entire length of the opening. From the viewpoint of preventing foreign matter from entering, productivity, and handleability, the opening is preferably composed of a slit-shaped portion of 1 or more and 5 or less, and is composed of a slit-shaped portion of 1 or more and 3 or less. It is more preferable that the shape is 1 or 2 and it is more preferable that the shape is composed of 1 or 2 slits.

When the openings are composed of one slit-shaped portion and two or more openings are provided, the length directions of the slit-shaped portions are, for example, perpendicular to each other. Although it can be provided at any angle, it is preferable to provide it so that the length directions of the slit-shaped portions are substantially parallel to each other from the viewpoint of handleability and the like.
Further, when the opening is configured by combining two or more slit-shaped portions, each slit-shaped portion is referred to as, for example, two slit-shaped portions being referred to as "ten" or "10". It may be provided so as to intersect each other as in "X", or may be provided so that three or more slit-shaped portions intersect with each other at one point. Further, for example, the slit-shaped portions such as "T" may be provided so as to be continuous in different length directions without intersecting each other. By having such a slit-shaped opening, the packaging container containing the polymer film has an oxygen permeability at 22 ° C. and 40% RH, which is suitable for maintaining the freshness of contents such as fruits and vegetables. The range is, for example, 500 to 50,000 cc / m ² / day / atm, more preferably 1000 to 5000 cc / m ² / day / atm, while foreign substances from the outside, such as fine inorganic substances and pollen. , It is possible to effectively suppress the invasion of various germs and suspended matter containing germs into the packaging container. Further, by setting the width of the slit-shaped portion forming the opening to less than 10 μm, it is possible to prevent foreign matter and the like in the air having a maximum diameter of 10 μm or more.

The maximum length of the continuous substantially straight portion of the slit-shaped shape forming the slit-shaped opening is typically 0.5 to 7 mm from the viewpoint of ensuring air permeability, and is preferably 0. It is 7 to 7 mm, more preferably 0.8 to 5 mm, still more preferably 1.0 to 3.0 mm, and particularly preferably 1.0 to 2.0 mm. On the other hand, the width of the slit-shaped opening is preferably less than 10 μm, more preferably 7 μm or less, still more preferably 5 μm or less, and particularly preferably 5 μm or less, from the viewpoint of preventing foreign matter from entering from the outside. It is preferably 3 μm or less.

The packaging container of the above aspect has suitable oxygen permeability, whereby antibacterial properties can be maintained while controlling the oxygen concentration in the packaging container, and the growth of germs and the like can be suppressed, so that breathing is performed. It is also preferably used for maintaining the freshness of contents containing a large amount of water, especially for maintaining the freshness of fruits and vegetables.
In this embodiment, the fruits and vegetables stored in the packaging container and kept fresh are not particularly limited, but for example, bananas, mangoes, sea urchins, apples, strawberries, oranges, grapes, Japanese pears, fruits such as western pears, daikon, etc. Root vegetables such as carrots, nagaimo, gobo, tomatoes, cucumbers, eggplants, peppers, edamame, fruit vegetables such as okura, green bean moyashi, soybean moyashi, buds such as tomyo, shiitake, shimeji, eringi, maitake, Fungal mushrooms (mushrooms) such as pine bamboo, broccoli, spinach, komatsuna, chingensai, cabbage, lettuce, leafy stem vegetables such as asparagus, flowers or seedlings such as kiku, lily, carnation, etc. can be mentioned.

In this embodiment, there is no particular limitation on the form of fruits and vegetables stored in a packaging container and kept fresh, but the oxygen concentration is controlled, thereby controlling the respiration of fruits and vegetables, and suppressing the growth of germs and the like to achieve freshness. From the action of the present embodiment of retaining the above, it is particularly effective for maintaining the freshness of fruits and vegetables in a form containing a large amount of water and substantially breathing.
Therefore, the fruits and vegetables may be as-harvested, so-called pretreated vegetables from which outer leaves and the like have been removed, and so-called cut vegetables that have been cut. Further, the fruits and vegetables may be those which have been subjected to any or all of the treatments such as washing, cooling and dehydration, and may not be subjected to any of these treatments.

Demand for cut vegetables has been increasing in recent years because they can be easily served for meals, and they have high economic value. On the other hand, when vegetables are cut, the respiratory action and metabolic reaction are rapidly activated, and the quality tends to be sharply deteriorated. Moreover, since it has a relatively wide cut surface, it is easily affected by germs and putrefactive substances. Further, when an organic component or the like elutes from the cut surface during dew condensation, remarkable propagation of germs or the like using this as a nutrient often occurs. Since this embodiment can be effectively used for maintaining the freshness of such cut vegetables, it has a particularly high economic value.

The preferred oxygen concentration for maintaining freshness varies to some extent depending on the type and form of fruits and vegetables, and accordingly, the preferred oxygen permeability and the preferred size, shape, and number of openings in the polymer film that provide such oxygen permeability. However, by setting these appropriately, the freshness of any of the above-mentioned fruits and vegetables can be effectively maintained by the packaging container containing the extruded laminated film of the present invention.

By storing fruits and vegetables in the packaging container of the above aspect, it is possible to produce a package for maintaining freshness of fruits and vegetables, which is one embodiment of the present invention.
Hereinafter, a method for producing a package for maintaining the freshness of fruits and vegetables of this embodiment will be described by taking a package for maintaining the freshness of cut vegetables as an example.

First, in the pretreatment step, the outer leaves are manually removed, the vegetables are divided into 2 to 4 parts, and the cores are removed, and the vegetables are supplied to the conveyor. Vegetables transported by the conveyor are cut by a slicer, washed in a washing tank filled with cold water for cooling, drained, and then dehydrated by a centrifugal dehydrator or the like. The dehydrated cut vegetables are packed in the packaging container of the present embodiment (one side is not sealed), and after weighing, the packaging container is sealed to produce a package for maintaining the freshness of the cut vegetables.

From the viewpoint of maintaining the freshness of the cut vegetables, it is preferable to use a sharp blade to reduce scratches on the cut surface.
Further, the narrower the cut width, the larger the cut area and the more difficult it is to maintain the freshness. Therefore, from the viewpoint of maintaining the freshness, it is preferable that the cut width is wide as long as it suits the form of demand.
Further, if a large amount of germs are attached to the cut vegetables from the beginning, it becomes more difficult to maintain the freshness. Therefore, it is preferable to wash the cut vegetables thoroughly to reduce the adhesion of the germs as much as possible. Washing is particularly effective for maintaining freshness because it not only reduces the adhesion of various germs but also has the effect of removing cell fluids and the like that contain highly active enzymes and may cause discoloration and the like.
In addition, it is important to sufficiently remove the water adhering to the surface of the cut vegetables after washing in order to maintain the freshness. Even if the vegetables are left to stand after washing and drained, a large amount of water still adheres to the surface of the cut vegetables, so it is effective to remove the water using a centrifugal dehydrator or the like.

The fruit and vegetable freshness-preserving package of the present embodiment may be degassed after storing the fruits and vegetables and sealing the packaging container. By degassing, it is possible to quickly reach the desired oxygen concentration designed as an equilibrium state between the oxygen permeability of the packaging container and the respiratory volume of fruits and vegetables, which is advantageous for maintaining freshness.
Further, from the viewpoint of improving efficiency in the distribution process, saving space, eliminating specific gas, and the like, it is preferable to perform degassing after sealing the packaging container.
As described above, since the opening in the polymer film constituting the packaging container of the present embodiment has a slit-shaped cross-sectional shape, a relatively simple means such as applying mechanical pressure can be used to apply a mechanical pressure to the central portion of the slit. It is possible to increase the width and significantly increase the gas permeability, which makes it possible to degas the package relatively easily and in a short time.

In the fruit and vegetable freshness-preserving package of the present embodiment, only fruits and vegetables may be stored in the packaging container of the present embodiment, or other members may be stored.
For example, in addition to fruits and vegetables, a hygroscopic agent and / or an antibacterial agent may be contained in a packaging container.
The hygroscopic agent is not particularly limited, and a known or commercially available material having a hygroscopic effect or a humidity control effect can be used. Suitable examples of the hygroscopic agent include activated carbon, silica gel, alumina gel, silica alumina gel, anhydrous magnesium sulfate, zeolite, synthetic zeolite, calcium oxide, calcium chloride, and roasted myoban, or a mixture thereof. However, it is not limited to these.
Among these, it is particularly preferable to use activated carbon, which has relatively little concern about its influence on fruits and vegetables and its use near foods such as fruits and vegetables. Activated carbon can be either powdery or granular, and the raw materials can be coconut shells, sawdust, charcoal, bamboo charcoal, lignite, peat, sprinkles, petroleum pitch, etc. It is desirable that the activated carbon is wrapped in non-woven fabric, cellophane, paper, etc. for each unit of use, but the activated carbon itself may be in the form of fibers. The packaging material for activated carbon is preferably a non-woven fabric made of synthetic resin, which has heat-sealing properties, but paper, natural fibers, etc. can be used as long as it has water vapor permeability and does not allow activated carbon to spill. no problem.

The antibacterial agent is not particularly limited, and a substance having an antibacterial action can be used as appropriate, but a natural antibacterial agent having relatively little concern about its influence on fruits and vegetables and its use near foods such as fruits and vegetables is used. It can be preferably used. More specifically, natural antibacterial agents such as chitosan, allyl isothiocyanate, hinokitiol, and limonene can be stored in a packaging container.

Hereinafter, the present invention will be specifically described with reference to Examples / Comparative Examples. The present invention is not limited to the following examples in any sense.

In the following Examples / Comparative Examples, each characteristic was evaluated by the following method.
(Antibacterial test)
(1) Antibacterial test An antibacterial test according to JISZ2801 was performed using Escherichia coli. However, the conditions were partially changed as described below, and the surface condition of the freshness-preserving film was not wiped off with alcohol.
A 1/500 ordinary bouillon medium containing a specified amount of Escherichia coli (a bouillon using 0.4 cc in the JIS test) is dropped onto the surface of a 4 cm square freshness-preserving film to be evaluated and placed on the upper surface. It was sandwiched between another freshness-preserving film. After 24 hours at 35 ° C., the surface of the freshness-preserving film was washed, and the washing solution containing the above-mentioned normal bouillon medium was collected and cultured on a normal agar medium to count the number of colonies.
That is, since it is difficult to count the number of bacteria under a microscope, the number of colonies is visually counted, and the number of colonies per gram (g) thereof is the viable cell number CFU (colony forming unit) (unit). [Individual / g]). In addition, a sample sandwiched between two polyethylene films not containing a specific compound was used as a control and used as a reference for comparison.
Table 2 also shows the average value of n = 3. However, if the variation of the measured values is 10 times or more, the average value cannot be calculated according to the JIS standard.
(Oxygen permeability)
The oxygen permeability was measured by the following method from the change in oxygen concentration after enclosing nitrogen inside.
First, a bag having an inner size of 220 mm × 240 mm was formed by the following method.
Fold one film in half almost evenly, set the scale of heating conditions to 3 with an impulse sealer (manufactured by Fuji Impulse Co., Ltd., product number Fi-200-10WK) with a width of about 5 mm, and perform heat sealing. Heat-seal so that the side is almost in the center. Heat-seal the whole of one of the sides that is almost perpendicular to the side, except for the end about 2 cm that is the communication part of one of the other sides, and heat-seal the whole, inner dimension 220 mm × A 240 mm bag was formed.
Next, nitrogen gas was injected from the communication portion, and after the inside of the bag became saturated, almost all the gas in the bag was discharged from the communication portion. After repeating this operation 5 times, nitrogen gas was injected to saturate the inside of the bag with nitrogen gas, and the communication portion was heat-sealed with the impulse sealer under the same conditions. The bag saturated with nitrogen gas was left in a room at 22 ° C. and a relative humidity of 40% in air (1 atm, oxygen concentration: 21%, nitrogen concentration: 79%) for 6 hours.
Next, about 20 cc of gas in the bag was sampled with a sampling needle tube, and the oxygen concentration in the bag was measured with a zirconia oxygen concentration meter for food packaging (manufactured by Toray Engineering Co., Ltd., model number LC-750F). Furthermore, the volume of the gas in the bag was measured, and the oxygen permeability was calculated from the following formula.
(Equation) Oxygen permeability = Change in internal oxygen concentration (%) / 100 x Volume (cm ³ ) x 24 x 60 / hour (360 minutes) x 10000 cm ² / Area (1232 cm ² ) /0.21 (Oxygen partial pressure) )
(Abundance of specific compound)
The surface of the polymer film was washed with dichloromethane, the washing liquid was recovered, concentrated and set to volume, then silylated and quantified using gas chromatograph mass spectrometry (GC / MS).

(Manufacturing of Polymer Film Layer A)
As the polymer film layer A, a polymer film having a three-layer structure of a back surface layer / an intermediate layer / a front surface layer was produced according to the following conditions.
(1) Intermediate layer The material of the intermediate layer is linear low-density polyethylene (manufactured by Mitsui Chemicals, Inc., density: 0.940 g / cm ³ , MFR: 4.0 g / 10 minutes, melting point: 117.3 ° C). Was used.
(2) Surface layer and back surface layer The surface layer and back surface layer are made of silica (manufactured by Fuji Silysia Chemical Ltd., trade name: Silicia 730 (average particle size 3 μm)) as opposed to the linear low-density polyethylene. And 1000 ppm of erucic acid amide (manufactured by Ciba Speciality Chemicals, trade name: ATMERSA1753) was added to the material.
(3) Additives The following antibacterial components were added to the masterbatch so that each layer contained the following antibacterial components in the amounts shown in Table 1.
(A) Stearyldiethanolamine (C18DEA) manufactured by RIKEN Vitamin Co., Ltd. (4) Production of polymer film layer A Using each of the above materials, a three-layer cast film of back surface layer / intermediate layer / surface layer is formed with a layer thickness ratio of 1/3. The polymer film layer A was produced at 1/1 with an overall thickness of 30, 40, 50, and 70 μm.
The polymer film layer A was produced at a die temperature of an extruder of 200 ° C. and a chill temperature of 50 ° C. The back surface layer side of the obtained polymer film layer A was corona-treated. The wetness index of the corona-treated surface is 38 dyn or more, and the wet tension test mixture NO. Confirmed using 38.0.
As shown in Table 1, the polymer film layer A1 contains 800 ppm of stearyldiethanolamine (C18DEA) in the intermediate layer and the back surface layer (seal layer), and the polymer film layer A2 contains stearyldiethanolamine in both layers. It did not contain (C18DEA).

(Reference example 1)
The polymer film layer A1 prepared above was used as it was, and extrusion laminating was not performed. Moreover, it was not laminated with the OPP film. The evaluation results are shown in Table 2.
As described above, the polymer film layer A1 is a polyethylene film containing 800 ppm of stearyldiethanolamine (C18DEA) in the intermediate layer and the back surface layer (seal layer), and each film of 30 to 70 μm showed sufficient antibacterial properties. That is, although the film is excellent in terms of antibacterial properties, it has not improved barrier properties, hand-cutting properties, multicolor printability, surface gloss, etc. by extrusion laminating.
(Reference example 2)
The polymer film layer A2 prepared above was used as it was, and extrusion laminating was not performed. Moreover, it was not laminated with the OPP film. The evaluation results are shown in Table 2.
As described above, the polymer film layer A2 was a polyethylene film containing no stearyldiethanolamine (C18DEA), and therefore did not exhibit antibacterial properties. Further, the extruded laminate has not improved the barrier property, the hand-cutting property, the multicolor printability, the surface gloss and the like.
(Comparative Example 1)
Extrusion laminating was performed on the polymer film layer A1 prepared above under the following conditions to form an extruded polymer film layer B1. As an anchor coating agent, a mixture of Seikadyne 2710A, 2810C (T) manufactured by Dainichiseika Kogyo Co., Ltd., and ethyl acetate at a ratio of = 1: 2: 15.6 was used before extrusion laminating. The surface of the polymer film layer A1 was subjected to anchor coating treatment.
The thickness of the extruded polymer film layer B1 was about 15 to 20 μm. The resin used for the extrusion laminating was low density polyethylene (LDPE, Novatec LD LC600A) manufactured by Japan Polyethylene Corporation, and no additives such as stearyldiethanolamine (C18DEA) were added.
・ Extrusion temperature (℃)
C1 / C2 / C3 / C4 / AD / D1-4 = 175/257/322/325/325/327-327
・ Molding speed AC 99m / min Take-up 106 / min ・ Aging 40 ℃ × 24h
Further, as the stretched film layer C, a biaxially stretched polypropylene film having a thickness of 15 μm (manufactured by Mitsui Chemicals Tocello Co., Ltd .: U-1) was laminated, subjected to anchor coating treatment, and then extruded laminating to produce an extruded laminated film. ..
The evaluation results are shown in Table 2.
When the thickness of the polymer film layer A1 is 70 μm, sufficient antibacterial properties are exhibited, but the antibacterial properties are unstable due to the movement of specific components to the extruded lami layer (B1), and the thickness becomes small. As the thickness increased, the antibacterial property became difficult to develop, and the antibacterial property did not develop when the thickness was 30 μm.
(Comparative Example 2)
An extruded laminated film was produced in the same manner as in Comparative Example 1 except that the polymer film layer A2 was used instead of the polymer film layer A1.
The evaluation results are shown in Table 2.
Substantial antibacterial properties were not obtained.
(Example 1)
900 ppm of stearyldiethanolamine (C18DEA) was added to the resin used for the extruded laminate (low density polyethylene manufactured by Nippon Polyethylene Co., Ltd., Novatec LD LC600A) to form an extruded polymer film layer B2, which was extruded into a polymer film. An extruded laminated film was produced in the same manner as in Comparative Example 1 except that the layer B1 was replaced.
The evaluation results are shown in Table 2.
It was confirmed that sufficient antibacterial properties were obtained at each thickness of 30 to 70 μm. That is, it is a film excellent in terms of antibacterial properties, and it is also possible to improve barrier properties, hand-cutting properties, multicolor printability, surface gloss, etc. by extrusion laminating.
The oxygen permeability at 22 ° C. and 40% RH was about 500 to 2000 cc / m ² / day / atm , and the film was suitable for packaging cut vegetables, meat, and fresh fish.
(Reference example 3)
900 ppm of stearyldiethanolamine (C18DEA) was added to the resin used for the extruded laminate (low density polyethylene manufactured by Nippon Polyethylene Co., Ltd., Novatec LD LC600A) to form an extruded polymer film layer B2, which was extruded into a polymer film. An extruded laminated film was produced in the same manner as in Comparative Example 2 except that the layer B1 was replaced.
The evaluation results are shown in Table 2.
Substantial antibacterial properties were not obtained.

The extruded laminated film of the present invention can realize an extruded laminated film having excellent barrier properties, hand-cutting properties, multicolor printability, surface gloss, etc. while maintaining sufficient antibacterial properties for maintaining freshness, and thus cut vegetables. While having high economic value such as packaging, meat, and fresh fish, it can be suitably used for maintaining the freshness of contents that are easily affected by germs, and is high in various fields of industries such as food processing, distribution, and eating out. Has availability.

Claims (13)

A polymer film in which at least one compound selected from the group consisting of palmityldiethanolamine, stearyldiethanolamine, glycerin monolaurate and diglycerin monolaurate is present on at least one surface in an amount of 0.002-0.5 g / m ² . Layer A and
An extruded laminate film comprising an extruded polymer film layer B formed by performing extrusion lamination on the polymer film layer A prepared in advance .
In the extruded polymer film layer B, 0.01 to 2% by mass of at least one compound selected from the group consisting of palmityldiethanolamine, stearyldiethanolamine, glycerin monolaurate and diglycerin monolaurate is blended. Yes, the above extruded laminated film. The extruded laminated film according to claim 1, wherein the stretched film layer C is further laminated on the extruded polymer film layer B. The extruded laminated film according to claim 1 or 2, wherein the polymer film layer A is a polyethylene-based film. The extruded laminated film according to any one of claims 1 to 3, wherein the extruded polymer film layer B contains at least one of linear polyethylene and low-density polyethylene. The extruded laminated film according to any one of claims 1 to 4, wherein the stretched film layer C has been subjected to a corona treatment and / or an anchor coating treatment. The extruded laminated film according to any one of claims 1 to 5, wherein the stretched film layer C is a uniaxial or biaxially stretched film of polyamide, polyethylene terephthalate, or polypropylene. The extruded laminated film according to any one of claims 1 to 6, wherein the oxygen permeability at 22 ° C. and 40% RH is in the range of 500 to 50,000 cc / m ² / day / atm. The extruded laminated film according to any one of claims 1 to 7, which is used for keeping freshness. A packaging container comprising the extruded laminated film according to any one of claims 1 to 7. The packaging container according to claim 9, wherein the extruded laminated film has at least one opening, the length of the opening is 0.5 to 7 mm, and the width of the opening is less than 10 μm. The packaging container according to claim 9 or 10, which is used for keeping the freshness of cut vegetables or fruits and vegetables. A package for maintaining freshness of cut vegetables or fruits and vegetables, which comprises storing the cut vegetables or fruits and vegetables in the packaging container according to any one of claims 9 to 11. The fruit and vegetable freshness-preserving package according to claim 12, further containing a hygroscopic agent and / or an antibacterial agent.