JP2016216056A - Soy sauce lees preservation film, soy sauce lees molded body using the same and preservation method of soy sauce lees - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a soy sauce lees preservation film where enclosed soy sauce lees do not bleed out, the generation of offensive odors can be suppressed and the soy sauce lees can be stored for a long term and to provide a soy sauce lees molded body using the same.SOLUTION: A soy sauce lees preservation film using for packaging and preserving soy sauce lees has at least one layer made of a saponified ethylene-vinyl ester-based copolymer. In a soy sauce lees molded body packaging and sealing the soy sauce lees, the soy sauce lees preservation film is used.SELECTED DRAWING: None

Description

  The present invention relates to a soy sauce cake preserving film, a soy sauce cake molded product using the same, and a method for preserving the soy sauce cake, and more specifically, the contained soy sauce cake does not bleed out, and the generation of off-flavors The present invention relates to a soy sauce cake storage film that can be suppressed, a soy sauce cake molded body using the film, and a method for preserving soy sauce cake.

  As soy sauce is brewed, soy sauce cake is produced, and many of them are disposed of by incineration or landfill disposal. On the other hand, the use of soy sauce cake for feed and fertilizer is also under consideration. Soy sauce cake is practically stored for a certain period of time before being used for the above-mentioned use. When preserving soy sauce cake, as a preservation method that reduces the generation of off-flavors, microorganisms, and soot and enables long-term storage, for example, there is a method of roll-bale-molding and storing soy sauce cake using a general-purpose resin film It has been proposed (see, for example, Patent Document 1).

JP 2013-99259 A

  In the technique described in Patent Document 1, a general-purpose resin film such as a polyethylene resin is used for packaging soy sauce cake. However, the above-described storage method has a problem that the soy sauce cake bleeds out because the generation of a strange odor is insufficient and the effect of the soy sauce cake on the packaging film is not taken into consideration. When the soy sauce cake bleeds out, this may cause blocking of the soy sauce cake package (for example, roll bale), which may lead to broken bags during use, which is still satisfactory for practical use. Instead, a solution to the above problem has been desired.

  The present invention has been made in view of such circumstances, soy sauce cake containing the soy sauce cake can be stored for a long period of time without bleed-out, and the generation of a bad odor can be suppressed, and soy sauce cake can be stored for a long time. An object of the present invention is to provide a film for soy sauce, a molded soy sauce cake using the film, and a method for preserving the soy sauce cake.

  In view of the above circumstances, the present inventors have made various studies to obtain a storage film that can suppress the generation of bleed-out of soy sauce cake and the generation of a strange odor and can be stored for a long period of time. In the process, as a result of re-examination of the storage method described in Patent Document 1, regarding the storage method, “soy sauce cake has low soluble hydrocarbon (WSC), protein concentration is relatively high, and salt concentration is high. Therefore, it is conventionally considered that there is no merit in preserving soy sauce cake in a silage fermentation environment, as described in paragraph [0010] of Patent Document 1). It was. On the other hand, the saponified ethylene-vinyl ester copolymer (hereinafter sometimes abbreviated as EVOH) layer-containing film makes the inclusions packaged by the film under an anaerobic environment due to its high gas barrier property. (Ie, silage fermentation) is known. From this, a person skilled in the art usually uses an EVOH layer-containing film that is known to be a soy sauce cake that is generally regarded as having no merit for storage in an environment of silage fermentation. I don't remember to wrap it. However, surprisingly, it has been found that when soy sauce cake is packaged using an EVOH layer-containing film, the generation of off-flavor is suppressed and bleeding out can also be suppressed.

<Summary of the present invention>
That is, the present invention is a soy sauce cake preserving film used for packaging and preserving soy sauce cake, wherein the soy sauce cake preserving film comprising at least one layer made of a saponified ethylene-vinyl ester copolymer is used. The gist of 1 is assumed.

  Moreover, this invention makes the 2nd summary the soy sauce cake molded object formed by packaging and sealing soy sauce cake using the said film for preservation of soy sauce cake. Furthermore, let the 3rd summary the preservation method of the soy sauce cake preserve | saved using the said soy sauce cake molded object.

  The present invention is a soy sauce cake preserving film comprising at least one layer made of a saponified ethylene-vinyl ester copolymer used for packaging and storing soy sauce cake. For this reason, when this film is used to wrap and seal soy sauce cake, for example, when a soy sauce cake such as a roll bale is formed, the contained soy sauce cake does not bleed out and the generation of a strange odor It can be suppressed and the soy sauce cake can be stored for a long time.

  And if a film for preservation of soy sauce cake is a multilayer structure film comprising a layer made of a saponified ethylene-vinyl ester copolymer and a layer made of a thermoplastic resin composition, the strength is further improved.

  Hereinafter, although the structure of this invention is demonstrated in detail, these show an example of a desirable embodiment.

  The present invention is a film used when a soy sauce cake is hermetically packaged and stored, and a film including at least one EVOH layer is used.

  The soy sauce cake to be packaged and stored using the soy sauce cake preservation film of the present invention is not particularly limited, and for example, the soy sauce is produced by various methods such as the main brewing method, the new brewing method, and the amino acid liquid mixing method. It is a by-product in the process of manufacturing (soy sauce brewing). The soy sauce brewing is performed, for example, via a raw material adjustment process, a koji making process, a preparation process, a pressing process, a firing process, a refining process, and a filling process. And normally, after squeezing moromi in the said pressing process, a soy sauce cake arises.

  As the shape of the soy sauce cake, as well as the shape obtained in the squeeze process of soy sauce brewing, the shape of the soy sauce brewed, of course, or a specific shape (for example, plate shape, Flakes, pellets, granules, etc.) are variously shaped and are the subject of the present invention.

<Soy sauce cake preservation film>
The soy sauce cake preserving film of the present invention (hereinafter also referred to as “film”) is a film having at least one EVOH layer as described above.

<EVOH>
First, EVOH that is the EVOH layer forming material will be described.
EVOH used in the present invention is usually a resin obtained by copolymerization of ethylene and a vinyl ester monomer and then saponification, and is a water-insoluble thermoplastic resin. As the polymerization method, any known polymerization method such as solution polymerization, suspension polymerization, and emulsion polymerization can be used. In general, however, solution polymerization using a lower alcohol such as methanol or ethanol, particularly preferably methanol as a solvent. Is used. Saponification of the obtained ethylene-vinyl ester copolymer can also be performed by a known method.
That is, EVOH used in the present invention mainly comprises an ethylene structural unit and a vinyl alcohol structural unit, and contains a slight amount of vinyl ester structural unit remaining without being saponified.

  As the vinyl ester-based monomer, vinyl acetate is typically used because it is easily available from the market and has good treatment efficiency of impurities during production. Other examples include aliphatic vinyl esters such as vinyl formate, vinyl propionate, vinyl valerate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl versatate, and benzoic acid. Examples thereof include aromatic vinyl esters such as vinyl acid, and are usually aliphatic vinyl esters having 3 to 20 carbon atoms, preferably 4 to 10 carbon atoms, and particularly preferably 4 to 7 carbon atoms. These are usually used alone, but a plurality of them may be used simultaneously as necessary.

  The content of the ethylene structural unit in EVOH is a value measured based on ISO 14663, and is usually 20 to 60 mol%, preferably 25 to 50 mol%, particularly preferably 25 to 35 mol%. If the content is too small, the gas barrier property and melt moldability at high humidity tend to decrease, and conversely if too large, the gas barrier property tends to decrease.

  The saponification degree of the vinyl ester component in EVOH is a value measured based on JIS K6726 (where EVOH is a solution uniformly dissolved in water / methanol solvent), and is usually 90 to 100 mol%, preferably 95 -100 mol%, particularly preferably 99-100 mol%. When the degree of saponification is too low, gas barrier properties, thermal stability, moisture resistance and the like tend to decrease.

  Further, the melt flow rate (MFR) (210 ° C., load 2160 g) of the EVOH is usually 0.5 to 100 g / 10 minutes, preferably 1 to 50 g / 10 minutes, particularly preferably 3 to 35 g / 10 minutes. It is. If the MFR is too large, the film forming property tends to be unstable. Moreover, when too small, there exists a tendency for a viscosity to become high too much and for melt extrusion to become difficult.

In addition, the EVOH used in the present invention may further contain structural units derived from the comonomer shown below within a range not inhibiting the effects of the present invention (for example, 10 mol% or less).
The comonomer includes olefins such as propylene, 1-butene, and isobutene, 3-buten-1-ol, 3-butene-1,2-diol, 4-penten-1-ol, 5-hexene-1,2- Hydroxyl group-containing α-olefins such as diols, derivatives such as esterified products, acylated products, acrylic acid, methacrylic acid, crotonic acid, (anhydrous) phthalic acid, (anhydrous) maleic acid, (anhydrous) itaconic acid, etc. Saturated acids or salts thereof, mono- or dialkyl esters having 1 to 18 carbon atoms, acrylamide, N-alkyl acrylamides having 1 to 18 carbon atoms, N, N-dimethylacrylamide, 2-acrylamidopropanesulfonic acid or salts thereof, acrylamidopropyl Acrylamides such as dimethylamine or its acid salts or quaternary salts , Methacrylamide, N-alkylmethacrylamide having 1 to 18 carbon atoms, N, N-dimethylmethacrylamide, 2-methacrylamideamidopropanesulfonic acid or its salt, methacrylamideamidopropylamine or its acid salt or its quaternary salt, etc. Methacrylamides, N-vinylpyrrolidone, N-vinylformamide, N-vinylamides such as N-vinylacetamide, vinyl cyanides such as acrylonitrile and methacrylonitrile, alkyl vinyl ethers having 1 to 18 carbon atoms, hydroxyalkyl vinyl ethers Vinyl ethers such as alkoxyalkyl vinyl ethers, vinyl halides such as vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, vinyl bromide, vinyl sila such as trimethoxyvinyl silane Allyl halides such as allyl acetate, allyl chloride, allyl alcohol such as allyl alcohol, dimethoxyallyl alcohol, trimethyl- (3-acrylamido-3-dimethylpropyl) -ammonium chloride, acrylamido-2-methylpropane And comonomers such as sulfonic acid.

  Furthermore, “post-modified” EVOH such as urethanization, acetalization, cyanoethylation, oxyalkylenation and the like can also be used.

  In particular, EVOH copolymerized with hydroxy group-containing α-olefins is preferable in terms of good secondary moldability. Among them, EVOH having a primary hydroxyl group in the side chain, particularly 1,2-diol is used as the side chain. EVOH contained in is preferable.

  The EVOH having the 1,2-diol in the side chain includes a 1,2-diol structural unit in the side chain. The 1,2-diol structural unit is specifically a structural unit represented by the following general formula (1).

  Examples of the organic group in the 1,2-diol structural unit represented by the general formula (1) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a tert-butyl group. A saturated hydrocarbon group such as a group, an aromatic hydrocarbon group such as a phenyl group and a benzyl group, a halogen atom, a hydroxyl group, an acyloxy group, an alkoxycarbonyl group, a carboxyl group, and a sulfonic acid group.

Among them, in formula (1), R ^{1 to} R ³ are usually a saturated hydrocarbon group or a hydrogen atom having 1 to 30 carbon atoms, particularly 1 to 15 carbon atoms, and more preferably 1 to 4 carbon atoms. Most preferred. In formula (1), R ^{4 to} R ⁶ are preferably an alkyl group or a hydrogen atom having 1 to 30 carbon atoms, particularly 1 to 15 carbon atoms, more preferably 1 to 4 carbon atoms, and most preferably a hydrogen atom. . In particular, it is most preferable that R ^{1 to} R ⁶ are all hydrogen atoms.

Moreover, X in the structural unit represented by the general formula (1) is typically a single bond.
In addition, a bond chain may be used as long as the effect of the present invention is not inhibited. Examples of the bonding chain include hydrocarbon chains such as alkylene, alkenylene, alkynylene, phenylene, and naphthylene (these hydrocarbons may be substituted with halogen such as fluorine, chlorine, and bromine), and -O _{-, - (CH 2 O)} m -, - (OCH 2) m -, - (CH 2 O) mCH 2 - structure containing an ether binding site, such as, -CO -, - COCO -, - CO (CH 2 ) mCO -, - CO (C 6 H 4) CO- structure containing a carbonyl group such as, -S -, - CS -, - SO -, - SO 2 - structure containing a sulfur atom, such as, -NR-, -CONR -, - NRCO -, - CSNR -, - NRCS -, - structure comprising NRNR- such as nitrogen atoms, -HPO ₄ - structure containing a heteroatom structure such as that containing a phosphorus atom, such as, -Si (OR ) _2- , -OSi (OR) _2- , -OSi (OR ) Structure containing ₂ O- such as silicon _{atoms, -Ti (OR) 2 -,} - OTi (OR) 2 -, - OTi ( structure including an OR) ₂ O- or titanium atoms, -Al (OR) - , -OAl (OR)-, -OAl (OR) O-, and the like include structures containing metal atoms such as structures containing aluminum atoms. R is independently an arbitrary substituent, preferably a hydrogen atom or an alkyl group, and m is a natural number, usually 1 to 30, preferably 1 to 15, and more preferably 1 to 10. . Of these, —CH ₂ OCH ₂ — and a hydrocarbon chain having 1 to 10 carbon atoms are preferable from the viewpoint of stability during production or use, and further a hydrocarbon chain having 1 to 6 carbon atoms, particularly 1 carbon atom. It is preferable that

The most preferable structure in the 1,2-diol structural unit represented by the general formula (1) is one in which R ^{1 to} R ⁶ are all hydrogen atoms and X is a single bond. That is, the structural unit represented by the following structural formula (1a) is most preferable.

  In particular, when the 1,2-diol structural unit represented by the general formula (1) is contained, the content thereof is usually 0.1 to 20 mol%, further 0.1 to 15 mol%, and particularly preferably 0.1. The thing of 1-10 mol% is preferable.

  The EVOH used in the present invention may be a mixture with other different EVOH, and the other EVOH includes the content of the 1,2-diol structural unit represented by the general formula (1). May be different, those having different ethylene structural unit contents, those having different degrees of saponification, those having different melt flow rates (MFR), those having different other copolymerization components, and the like.

  The EVOH used in the present invention generally contains a compounding agent such as a heat stabilizer, an antioxidant, etc., which is generally blended with EVOH within a range not inhibiting the effects of the present invention (for example, less than 20% by weight of the entire EVOH layer forming material). , Antistatic agent, colorant, UV absorber, lubricant, plasticizer, light stabilizer, surfactant, antibacterial agent, desiccant, antiblocking agent, flame retardant, crosslinking agent, curing agent, foaming agent, crystal nucleating agent , Antifogging agents, biodegradable additives, silane coupling agents, oxygen absorbers, fillers (for example, inorganic fillers), insoluble inorganic salts, waxes, dispersants, conjugated polyene compounds, and the like may be contained.

The heat stabilizer is an organic acid such as acetic acid, propionic acid, butyric acid, lauric acid, stearic acid, oleic acid, behenic acid, or an alkali thereof for the purpose of improving various physical properties such as heat stability during melt molding. Metal salts (sodium, potassium, etc.), alkaline earth metal salts (calcium, magnesium, etc.), salts such as zinc salts; or inorganic acids such as sulfuric acid, sulfurous acid, carbonic acid, phosphoric acid, boric acid, or alkali metals thereof You may mix | blend additives, such as salt (sodium, potassium, etc.), alkaline-earth metal salt (calcium, magnesium, etc.), and zinc salt.
Among these, it is particularly preferable to blend boron compounds including acetic acid, boric acid and salts thereof, acetates and phosphates.

  When acetic acid is blended, the blending amount is usually 0.001 to 1 part by weight, preferably 0.005 to 0.2 part by weight, particularly preferably 0.01 to 0.1 part by weight based on 100 parts by weight of EVOH. It is. If the blending amount of acetic acid is too small, there is a tendency that the effect of containing acetic acid is not sufficiently obtained.

  When a boron compound is blended, the blending amount is usually 0.001 to 1 part by weight in terms of boron (analyzed by ICP emission analysis after ashing) with respect to 100 parts by weight of EVOH, preferably 0. 0.002 to 0.2 part by weight, particularly preferably 0.005 to 0.1 part by weight. If the compounding amount of the boron compound is too small, the effect of containing the boron compound may not be obtained sufficiently, and conversely if it is too much, it tends to be difficult to obtain a uniform film.

  The amount of acetate and phosphate (including hydrogen phosphate) is usually 0.0005 to 0 in terms of metal with respect to 100 parts by weight of EVOH (after ashing and analyzed by ICP emission spectrometry). 0.1 part by weight, preferably 0.001 to 0.05 part by weight, particularly preferably 0.002 to 0.03 part by weight. If the amount is too small, the content effect may not be sufficiently obtained. Conversely, if the amount is too large, it tends to be difficult to obtain a uniform film. In addition, when mix | blending 2 or more types of salts with EVOH, it is preferable that the total amount exists in the range of said compounding quantity.

The method of adding a heat stabilizer to EVOH, for example, acetic acid, boron compound, acetate, and phosphate, is not particularly limited. I) Porous precipitate of EVOH having a water content of 20 to 80% by weight A method of bringing the porous EVOH into contact with an aqueous solution of the additive and then drying; ii) adding the additive to a uniform EVOH solution (water / alcohol solution, etc.), and then coagulating liquid A method of extruding into strands and then cutting the resulting strands into pellets for further drying treatment; iii) A method of mixing EVOH and additives together and then melt-kneading with an extruder or the like; iv ) During the production of EVOH, the alkali (sodium hydroxide, potassium hydroxide, etc.) used in the saponification step is neutralized with organic acids such as acetic acid to produce residual organic acids such as acetic acid and by-products. It can be mentioned a method in which or adjusted by washing with water the amount of salt.
Among these, in order to obtain the effects of the present invention more remarkably, the methods i) and ii), which are excellent in the dispersibility of additives, and the method iv) are preferable when an organic acid and a salt thereof are contained.

<Plate-like inorganic filler>
EVOH used in the present invention may further contain a plate-like inorganic filler for the purpose of improving gas barrier properties.

  As the plate-like inorganic filler, for example, kaolin whose main component is hydrous aluminum silicate, particles are plate-like, mica and smectite which are layered silicate minerals, talc made of magnesium hydroxide and silicate, etc. Can be given. Of these, kaolin is preferably used. The type of kaolin is not particularly limited and may or may not be calcined, but calcined kaolin is preferred.

  By adding the plate-like inorganic filler, the gas barrier property of EVOH is further improved. Since the plate-like inorganic filler has a multilayer structure, in the case of film forming, the plate-like surface of the plate-like inorganic filler is easily oriented in the plane direction of the film. Thus, it is presumed that the plate-like inorganic filler oriented in the plane direction contributes to oxygen shielding of the EVOH layer (film).

  The addition amount of the plate-like inorganic filler is usually 1 to 20% by weight, preferably 3 to 20% by weight, and more preferably 5 to 15% by weight with respect to EVOH.

<Oxygen absorber>
The EVOH used in the present invention may further contain an oxygen absorbent for the purpose of improving the gas barrier properties after the hot water treatment (retort treatment).

  The oxygen absorber is a compound or compound system that captures oxygen more quickly than the contents to be packaged. Specifically, an inorganic oxygen absorbent, an organic oxygen absorbent, a composite oxygen absorbent using an inorganic catalyst (transition metal catalyst) and an organic compound in combination, and the like can be given.

Examples of the inorganic oxygen absorbent include metals and metal compounds, which absorb oxygen when they react with oxygen. As the metal, a metal (Fe, Zn, Mg, Al, K, Ca, Ni, Sn, etc.) having a higher ionization tendency than hydrogen is preferable, and typically iron. These metals are preferably used in powder form. As the iron powder, any known iron powder, such as reduced iron powder, atomized iron powder, electrolytic iron powder, etc. can be used without particular limitation, regardless of its production method. Moreover, the iron used may be obtained by reducing iron once oxidized. The metal compound is preferably an oxygen deficient metal compound. Here, examples of the oxygen-deficient metal compound include cerium oxide (CeO ₂ ), titanium oxide (TiO ₂ ), and zinc oxide (ZnO). These oxides are reduced by oxygen from the crystal lattice by reduction treatment. It is pulled out to be in an oxygen deficient state and exhibits oxygen absorbing ability by reacting with oxygen in the atmosphere. Such metals and metal compounds also preferably contain a metal halide or the like as a reaction accelerator.

  Examples of the organic oxygen absorber include a hydroxyl group-containing compound, a quinone compound, a double bond-containing compound, and an oxidizable resin. Oxygen can be absorbed when oxygen reacts with a hydroxyl group or a double bond contained therein. As the organic oxygen absorber, ring-opening polymers of cycloalkenes such as polyoctenylene, conjugated diene polymers such as butadiene, and cyclized products thereof are preferable.

  The composite oxygen absorber refers to a combination of a transition metal catalyst and an organic compound, which excites oxygen by the transition metal catalyst and absorbs oxygen by the reaction between the organic compound and oxygen. It is a compound system that captures and absorbs oxygen when the organic compound in the composite oxygen absorbent reacts with oxygen earlier than the food that is the contents to be packaged. Examples of the transition metal constituting the transition metal-based catalyst include at least one selected from titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, zirconium, ruthenium, and palladium. Of these, cobalt is preferred from the viewpoint of compatibility, functionality as a catalyst, and safety. The organic compound is preferably a ring-opening polymer of a cycloalkene such as polyoctenylene, which is an organic oxygen absorber, a conjugated diene polymer such as butadiene, and a cyclized product thereof, and the other organic compound is MXD nylon. Preferred are nitrogen-containing resins such as polypropylene, tertiary hydrogen-containing resins such as polypropylene, polyalkylene ether bond-containing resins such as block copolymers having polyalkylene ether units, and anthraquinone polymers.

  The content ratio (mass ratio) of the transition metal catalyst and the organic compound in the composite oxygen absorbent is 0.0001 to 5% by weight in terms of metal element, more preferably 0.0005, based on the mass of the organic compound. It is contained in a range of ˜1% by weight, more preferably 0.001 to 0.5% by weight.

  The addition amount of such an oxygen absorbent is usually 1 to 30% by weight, preferably 3 to 25% by weight, and more preferably 5 to 20% by weight with respect to EVOH.

<Conjugated polyene compound>
The conjugated polyene compound is a so-called conjugated double bond in which carbon-carbon double bonds and carbon-carbon single bonds are alternately connected, and the number of carbon-carbon double bonds is two or more. It is a compound which has this. The conjugated polyene compound is a conjugated diene having a structure in which two carbon-carbon double bonds and one carbon-carbon single bond are alternately connected, three carbon-carbon double bonds and two carbons. Even a conjugated triene having a structure in which carbon single bonds are alternately connected, or a conjugated polyene compound having a structure in which a larger number of carbon-carbon double bonds and carbon-carbon single bonds are alternately connected Good. However, when the number of conjugated carbon-carbon double bonds is 8 or more, there is a concern that the molded product may be colored by the color of the conjugated polyene compound itself, so the number of conjugated carbon-carbon double bonds is 7 or less. It is preferable that it is polyene which is. Further, a plurality of conjugated double bonds composed of two or more carbon-carbon double bonds may be present in one molecule without being conjugated with each other. For example, a compound having three conjugated trienes in the same molecule such as tung oil is also included in the conjugated polyene compound.

  Specific examples of the conjugated polyene compound include conjugated diene compounds having two carbon-carbon double bonds such as isoprene, myrcene, farnesene, semblene, sorbic acid, sorbic acid ester, sorbate, and abietic acid; Conjugated triene compounds having three carbon-carbon double bonds such as 1,5-hexatriene, 2,4,6-octatriene-1-carboxylic acid, eleostearic acid, tung oil, cholecalciferol, etc .; cyclooctatetraene Conjugated polyene compounds having 4 or more carbon-carbon double bonds such as 2,4,6,8-decatetraene-1-carboxylic acid, retinol and retinoic acid. These conjugated polyene compounds may be used alone or in combination of two or more.

The amount of the conjugated polyene compound is usually 0.000001 to 1 part by weight, preferably 0.00001 to 1 part by weight, particularly preferably 0.0001 to 0.01 part by weight based on 100 parts by weight of EVOH. It is more preferable.
In addition, it is preferable that the said conjugated polyene compound is previously contained in EVOH.

<Method for Preparing EVOH Layer Forming Material>
The EVOH layer forming material is not particularly limited. For example, EVOH and other additives may be blended at a predetermined ratio and prepared by melt kneading or the like (melt kneading method), or each component may be mixed at a predetermined ratio. You may dry blend with (dry blend method).

  As the mixing method, for example, an arbitrary blending method such as a dry blending method using a Banbury mixer or the like, a melt-kneading method using a single or twin screw extruder, and pelletizing is adopted. The said melt kneading temperature is 150-300 degreeC normally, Preferably it is 170-250 degreeC.

  The EVOH layer forming material is usually preferably prepared from EVOH pellets after the melt kneading and subjected to a melt molding method to obtain a film from the viewpoint of industrial handling. From the economical viewpoint, EVOH pellets are preferably melt-kneaded using an extruder, extruded into a strand, and then cut into pellets.

  The shape of the pellet includes, for example, a spherical shape, a cylindrical shape, a cubic shape, a rectangular parallelepiped shape, etc., but is usually a spherical shape (rugby ball shape) or a cylindrical shape, and its size is convenient when used as a molding material later. From the viewpoint of properties, in the case of a spherical shape, the diameter is usually 1 to 6 mm, preferably 2 to 5 mm, and the height is usually 1 to 6 mm, preferably 2 to 5 mm. The length is 1 to 6 mm, preferably 2 to 5 mm, and the length is usually 1 to 6 mm, preferably 2 to 5 mm.

  From the viewpoint of stabilizing the feed property at the time of melt molding, it is also preferable to attach a lubricant to the surface of the obtained EVOH pellets. The types of lubricants include higher fatty acids (for example, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, etc.), higher fatty acid metal salts (higher fatty acid aluminum salts, calcium salts, zinc salts, magnesium salts, Barium salts, etc.), higher fatty acid esters (methyl esters of higher fatty acids, isopropyl esters, butyl esters, octyl esters, etc.), higher fatty acid amides (saturated aliphatic amides such as stearic acid amide, behenic acid amide, oleic acid amide, erucic acid Unsaturated fatty acid amides such as amides, ethylene bis stearic acid amides, ethylene bis oleic acid amides, ethylene biserucic acid amides, bis fatty acid amides such as ethylene bis lauric acid amides), low molecular weight polyolefins (for example, molecular weights of about 500 to 10,000) Low Polyethylene, low molecular weight polypropylene, etc., or acid-modified products thereof), higher alcohols, ester oligomers, fluorinated ethylene resins, and the like, preferably higher fatty acids and / or metal salts, esters, and amides thereof. A higher fatty acid metal salt and / or a higher fatty acid amide is used.

  As the properties of the lubricant, any properties such as solid (powder, fine powder, flakes, etc.), semi-solid, liquid, paste, solution, emulsion (aqueous dispersion) can be used. However, in order to obtain EVOH pellets efficiently, an emulsion is preferable.

  As a method of attaching the lubricant to the surface of the EVOH pellets, a method of adhering the lubricant and EVOH pellets by mixing with a blender or the like, a method of adhering EVOH pellets by immersing the EVOH pellets in a lubricant solution or dispersion, EVOH For example, a method of spraying and adhering a lubricant solution or dispersion to the pellets may be used. Preferably, EVOH pellets are charged into a blender or the like, and an emulsion lubricant is added under stirring, and the solid content of the lubricant is 0.001 to 1 part by weight / hr, based on 100 parts by weight of EVOH pellets. Gradual addition at a rate of 01 to 0.1 parts by weight / hr is preferable for uniform adhesion of the lubricant. Furthermore, in order to obtain an EVOH pellet in which all the lubricant adhered to the EVOH pellet surface is in close contact with the EVOH pellet surface and the lubricant is not released in the melt molding machine, the surface temperature of the EVOH pellet is set as above. The most preferable method is a method in which the lubricant is brought to a high temperature of −50 ° C. or higher and is brought into contact with the lubricant at a temperature lower than the melting point of the EVOH.

  The attached amount of the lubricant is preferably 10 to 1000 ppm, more preferably 20 to 500 ppm, and particularly preferably 50 to 250 ppm with respect to the EVOH pellets, from the viewpoint of stabilizing the feed property at the time of melt molding.

<Soy sauce cake preservation film>
For example, in the case of a single layer film composed of only an EVOH layer, the soy sauce cake storage film of the present invention can be formed into a film by a melt molding method. Examples of the melt molding method include an extrusion molding method (T-die extrusion and the like), an injection molding method, and the like. The melt molding temperature is usually appropriately selected from the range of 150 to 300 ° C.
In the present invention, “film” is not particularly distinguished from “sheet”, and is described as meaning including these.

  The soy sauce cake preserving film of the present invention is a film having at least one EVOH layer, and may be a single-layer film composed of the EVOH layer. However, in order to further increase the strength or to provide other functions. It is preferable to use a film having a multilayer structure of at least two layers formed by laminating other resin layers.

<Multilayer film>

  For example, a thermoplastic resin other than EVOH (hereinafter referred to as “other thermoplastic resin”) is preferably used as the other resin.

When the EVOH layer is a (a1, a2,...) And the other thermoplastic resin layers are b (b1, b2,...), The multilayer structure film has a / b, b / a. / B, a / b / a, a1 / a2 / b, a / b1 / b2, b2 / b1 / a / b1 / b2, b2 / b1 / a / b1 / a / b1 / b2, etc. It is. In addition, when R is a recycle layer obtained by remelt molding an end portion or defective product generated in the process of producing the multilayer structure film, b / R / a, b / R / a / b, b / R / a / R / b, b / a / R / a / b, b / R / a / R / a / R / b, etc. are also possible. The number of layers of the multilayer structure film of the present invention is usually 2 to 15 layers, preferably 3 to 10 layers in total.
In the above layer structure, an adhesive resin layer may be interposed between the respective layers as necessary.

  When the soy sauce cake storage film of the present invention is a multilayer structure film, it is preferable that the unit of the multilayer structure film includes an EVOH layer as an intermediate layer, and is provided with other thermoplastic resin layers as both outer layers of the intermediate layer. A multilayer structure film having (b / a / b or b / adhesive resin layer / a / adhesive resin layer / b) as a basic unit and having this basic unit as at least a constituent unit can be mentioned.

  Examples of the other thermoplastic resins include linear low-density polyethylene, low-density polyethylene, ultra-low-density polyethylene, medium-density polyethylene, high-density polyethylene, ethylene-propylene (block and random) copolymers, and ethylene-α. -Polyethylene resins such as olefin (α-olefin having 4 to 20 carbon atoms) copolymer, polypropylene resins such as polypropylene and propylene-α-olefin (α-olefin having 4 to 20 carbon atoms) copolymer, polybutene (Unmodified) polyolefin resins such as polypentene and polycyclic olefin resins (polymers having a cyclic olefin structure in the main chain and / or side chain), and these polyolefins grafted with unsaturated carboxylic acids or esters thereof Modified unsaturated carboxylic acid modified polyolefin resin, etc. Broadly defined polyolefin resins including modified olefin resins, ionomers, ethylene-vinyl acetate copolymers, ethylene-acrylic acid copolymers, ethylene-acrylic acid ester copolymers, polyester resins, polyamide resins (copolymerized polyamides) ), Polyvinyl chloride, polyvinylidene chloride, acrylic resins, polystyrene resins, vinyl ester resins, polyester elastomers, polyurethane elastomers, chlorinated polyethylene, chlorinated polypropylene and other halogenated polyolefins, aromatic or aliphatic polyketones And the like.

  Of these, polyamide-based resins, polyolefin-based resins, polyester-based resins, polystyrene-based resins, and polycyclic olefin-based resins are preferable, and polyethylene-based resins and polypropylene-based resins are more preferable from the viewpoint of the strength of the multilayer structure film. .

  In addition, as the adhesive resin that is the adhesive resin layer forming material, a known one can be used, and may be appropriately selected according to the type of the thermoplastic resin used for the other thermoplastic resin (b). A typical example is a modified polyolefin polymer containing a carboxyl group obtained by chemically bonding an unsaturated carboxylic acid or its anhydride to a polyolefin resin by an addition reaction or a graft reaction. For example, maleic anhydride graft-modified polyethylene, maleic anhydride graft-modified polypropylene, maleic anhydride graft-modified ethylene-propylene (block and random) copolymer, maleic anhydride graft-modified ethylene-ethyl acrylate copolymer, maleic anhydride graft Examples thereof include a modified ethylene-vinyl acetate copolymer, a maleic anhydride-modified polycyclic olefin resin, a maleic anhydride graft-modified polyolefin resin, and the like. These can be used alone or in combination of two or more.

  In the other thermoplastic resin and adhesive resin layer, a conventionally known plasticizer, filler, clay (within a range not impairing the gist of the present invention (for example, 30% by weight or less, preferably 10% by weight or less)). Montmorillonite, etc.), colorant, antioxidant, antistatic agent, lubricant, core material, antiblocking agent, ultraviolet absorber, wax and the like.

  In the soy sauce cake preserving film of the present invention, a known method is used as a lamination method when a multilayer structure film is produced by laminating an EVOH layer and another thermoplastic resin layer (including the case where an adhesive resin layer is interposed). Can be done. For example, a method of melt extrusion laminating another thermoplastic resin on an EVOH film (sheet) or the like, a method of melt extrusion laminating EVOH on another thermoplastic resin film (sheet), EVOH and another thermoplastic resin A co-extrusion method, EVOH film (layer) and other thermoplastic resin film (layer) were produced, and these were used with known adhesives such as organic titanium compounds, isocyanate compounds, polyester compounds, polyurethane compounds, etc. For example, a method of dry laminating, a method of removing a solvent after coating a solution of EVOH on a film made of another thermoplastic resin, and the like. Among these, the co-extrusion method is preferable from the viewpoint of cost and environment.

  The multilayer structure film is then subjected to (heating) stretching treatment as necessary. The stretching treatment may be either uniaxial stretching or biaxial stretching, and in the case of biaxial stretching, it may be simultaneous stretching or sequential stretching. As the stretching method, a roll stretching method, a tenter stretching method, a tubular stretching method, a stretching blow method, a vacuum / pressure forming method, or the like having a high stretching ratio can be employed. The stretching temperature is usually selected from the range of about 40 to 170 ° C, preferably about 60 to 160 ° C. If the stretching temperature is too low, the stretchability becomes poor, and if it is too high, it becomes difficult to maintain a stable stretched state.

  For the purpose of imparting dimensional stability after stretching, heat setting may be performed. The heat setting can be carried out by a known means. For example, the above-mentioned stretched multilayer structure film (stretched film) is usually 80 to 180 ° C., preferably 100 to 165 ° C., usually 2 to 600 seconds while maintaining a tension state. Heat treatment to a certain extent.

  The thickness of the soy sauce cake storage film of the present invention, and the thickness of the EVOH layer, other thermoplastic resin layer and adhesive resin layer in the case of a multilayer structure film are the layer structure, the type of thermoplastic resin, and the adhesive resin. It is appropriately set depending on the type, packaging form, and required physical properties. In addition, the following numerical value is a total value of the thicknesses of the same kind of layers in the case where two or more kinds of EVOH layers, adhesive resin layers, and other thermoplastic resin layers are present.

  The thickness of the soy sauce cake storage film of the present invention is usually 10 to 3000 μm, preferably 30 to 2000 μm, particularly preferably 50 to 1000 μm, regardless of the single layer structure or the multilayer structure. When the total thickness is too thin, the gas barrier property tends to be lowered or the bleed-out property tends to be insufficient. In addition, when the total thickness of the soy sauce cake preserving film is too thick, the gas barrier property becomes excessive performance, and unnecessary raw materials are used, which tends to be uneconomical. The EVOH layer is usually 1 to 300 μm, preferably 3 to 100 μm, particularly preferably 5 to 50 μm, and the other thermoplastic resin layer is usually 5 to 3000 μm, preferably 10 to 2000 μm, particularly preferably 20 to 1000 μm. The adhesive resin layer is usually 0.5 to 150 μm, preferably 1 to 100 μm, particularly preferably 3 to 50 μm.

  Furthermore, the ratio of the thickness of the EVOH layer to other thermoplastic resin layers in the soy sauce cake storage film having a multilayer structure (EVOH layer / other thermoplastic resin layers) is the thickest layer when there are a plurality of layers. The ratio is usually 1/99 to 50/50, preferably 5/95 to 45/55, particularly preferably 10/90 to 40/60. When the ratio is lower than the lower limit of the thickness ratio between the EVOH layer and the other thermoplastic resin layer, the gas barrier property tends to be lowered or the bleed-out property tends to be insufficient. Moreover, when it exceeds the upper limit of the ratio of the thickness of the said EVOH layer and another thermoplastic resin layer, there exists a tendency which is not economical since gas barrier property becomes excess performance and an unnecessary raw material will be used. And the thickness ratio (EVOH layer / adhesive resin layer) of the EVOH layer and the adhesive resin layer in the soy sauce cake storage film having a multilayer structure is usually the ratio between the thickest layers when there are a plurality of layers. 20/80 to 99/1, preferably 30/70 to 70/30, particularly preferably 40/60 to 60/40. When the thickness ratio is lower than the lower limit of the thickness ratio between the EVOH layer and the adhesive resin layer, the gas barrier property tends to be lowered or the bleed-out property tends to be insufficient. Moreover, when exceeding the upper limit of the thickness ratio between the EVOH layer and the adhesive resin layer, delamination occurs between the film layers, and there is a tendency that it cannot be put into practical use.

<Soy sauce cake molding>
The molded soy sauce cake of the present invention is formed by packaging and sealing a soy sauce cake using the above-mentioned soy sauce cake storage film. The soy sauce cake molded body has, for example, a soy sauce cake having a bulk density of 100 kg / m ³ or more and a surface containing the soy sauce cake as a main raw material and packaged with the soy sauce cake storage film. And as a shape of the said soy sauce koji molded object, although set suitably, for example, when shape | molded by roll bale molding, a substantially cylindrical shape or a spindle type | mold is mention | raise | lifted. The soy sauce cake molded body having such a configuration is suitable for use as a feed or fertilizer because generation of off-flavors or microorganisms after storage for a long period of time is suppressed.

As a method for producing a soy sauce cake molded body, for example, a step of compressing soy sauce cake to a bulk density of 100 kg / m ³ or more to obtain a soy sauce cake compact, and sealing and packaging the surface of the compressed body with a soy sauce cake storage film Including the step of. Or the production method including the process of shape | molding soy sauce cake in a substantially cylindrical shape or a spindle shape, and the process of sealing the surface of the said molded object with a film may be sufficient.

<Preservation method of soy sauce cake>
In the present invention, there is a soy sauce koji preservation method in which the soy sauce koji molded body, for example, the soy sauce koji is stored in a roll bale formed by sealing and sealing the soy sauce koji with a film for soy sauce koji preservation. The preservation | save method which has this structure can suppress effectively generation | occurrence | production of a strange odor when soy sauce cake is preserve | saved for a long period of time.

  In the present invention, the “roll bale” is a general term for those formed by a baler. Although the kind of baler is not specifically limited, For example, Maze baler MP2000 (made by Corns AG) can be used. The packaged roll bale can be obtained, for example, by carrying the soy sauce cake generated in the above-described pressing process to a baler, then carrying out baling, net winding (or twain winding), packaging (or packaging), and roll discharge. . The soy sauce cake is compressed and molded in the above-mentioned bering process. And a high quality roll bale can be made by performing each process of the said bering, net winding, packaging, and roll discharge with one baler. The time from the generation of soy sauce cake to packaging is not particularly limited as long as the soy sauce cake does not rot, but it is preferable to package it as soon as possible. In addition, when baling and packaging are performed at the same time and one roll formation is completed, high productivity can be exhibited in a lean process by immediately starting the next roll formation and packaging. In the above-described packaging operation, the packaging time can be greatly reduced by packaging quickly from both directions with a double mast, compared to a single mast that can be wrapped only from one direction.

  The shape of the packaged roll bale is, for example, a substantially cylindrical shape, a spindle shape (including a shape like a Japanese drum), a substantially spherical shape, or a substantially polygonal column shape (for example, a substantially 3-10 prism shape). Also good. When storing a plurality of packaged roll bales, a substantially cylindrical shape, a spindle shape, or a substantially polygonal column shape is preferable from the viewpoint of easy storage in a stacked manner and a small consumption space. From the viewpoint of film adhesion or high airtightness, a substantially cylindrical shape, spindle shape, or substantially spherical shape is preferred.

The “bulk density” of the soy sauce cake in the packaged roll bale is preferably 100 to 1000 kg / m ³ , for example. The bulk density, from the viewpoint of suppressing generation of an odor or microbial sauce cake, more preferably from 200~1000kg / ^{m 3,} particularly preferably 300~1000kg / ^{m 3.} The bulk density may be a value calculated according to the formula “mass of packaged roll bale / ((diameter / 2) ² × 3.14 × height)”.

  The “salt concentration” of the soy sauce cake in the packaged roll bale is preferably 0.1 to 10% by weight, for example. The salt concentration is more preferably 1 to 8% by weight, particularly preferably 3 to 6% by weight, from the viewpoint of suppressing the off-flavor of soy sauce cake or the generation of microorganisms.

  The “moisture content” of the soy sauce cake in the packaged roll bale is preferably, for example, 3 to 50% by weight of the whole soy sauce cake. Further, the water content is more preferably 3 to 40% by weight, particularly preferably 3 to 30% by weight, from the viewpoint of suppressing the off-flavor of soy sauce cake or the generation of microorganisms.

  The “height” of the packaged roll bale is preferably 0.3 to 2 m, for example.

  The “diameter” of the packaged roll bale is preferably 0.3 to 2 m, for example.

  The “mass” of the packaged roll bale is preferably 25 to 1400 kg, for example, and more preferably 500 to 1000 kg from the viewpoint of convenience during storage and cost.

  It is preferable that the “compressibility” of the soy sauce koji at the time of the above-mentioned beer is, for example, 10 to 90. The degree of compression is more preferably 20 to 90, and particularly preferably 30 to 90, from the viewpoint of suppressing the off-flavor of soy sauce cake or the generation of microorganisms. In the present specification, the degree of compression is a value calculated according to the formula “((bulk density after compression−bulk density before compression) / bulk density after compression) × 100”.

  Moreover, you may preserve | save the said preservation | save method, without passing through the process of silage fermentation. In this case, the cost and time required for silage fermentation can be reduced. In addition, silage fermentation is the operation | work which makes anaerobic bacteria ferment in the raw material, before performing long-term preservation | save of the raw material (for example, grass). The fermentation of anaerobic bacteria increases the component ratio of organic acids such as lactic acid or acetic acid and lowers the pH, thereby suppressing the growth of microorganisms.

The soy sauce cake storage method of the present invention is preserved as a soy sauce cake molded body in which the surface of the soy sauce cake is packaged and sealed with a film and the soy sauce cake has a bulk density of 100 kg / m ³ or more. , How to preserve soy sauce cake. The method having this configuration can suppress the generation of off-flavors and microorganisms after long-term storage.

  The method for preserving soy sauce cake of the present invention is, for example, a method of preserving soy sauce cake formed in a substantially cylindrical or spindle shape with the surface sealed with a film. The method having this configuration can suppress the generation of off-flavors or microorganisms after long-term storage. In the present invention, the term “sealed” means a state in which the film and the soy sauce cake are tightly closed so that no gap is generated. For example, the state in which the film is in close contact with the entire formed soy sauce cake is included.

  In the method for preserving soy sauce cake of the present invention, as described above, the soy sauce cake molded product is preserved in a roll bale state, and this roll bale is packaged in a film containing soy sauce cake as a main raw material. Roll bale. The roll veil having such a configuration is one in which the generation of off-flavors or microorganisms after long-term storage is suppressed.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist. In the examples, “part” is based on weight.

[Production of multilayer structure film]
EVOH resin (A) (ethylene content 32 mol%, saponification degree 99.6 mol%, MFR 3.8 g / 10 min (210 ° C., load 2160 g)), linear low density polyethylene (B) (Nippon Polyethylene Co., Ltd.) Manufactured by NovatecLL UF421) and adhesive resin (C) (manufactured by Mitsui Chemicals, Admer NF528), the layer structure and thickness are (B) / (C) / (A) / (C) / (B) = A multilayer structure film having a folding width of 300 mm having a layer formation of 30 μm / 10 μm / 10 μm / 10 μm / 30 μm was formed by an inflation molding method. Then, the folded part in the multilayer structure film with a folding width of 300 mm was cut to obtain a multilayer structure film with a width of 300 mm.

[Film forming conditions]
A multilayer blown film forming machine (5 types and 5 layers) was used.
Extruder: Diameter (D) 40 mm, L / D = 28
・ Set temperature (℃) and rotation speed:
Linear low density polyethylene (B) layer: C1 / C2 / C3 / C4 / AD / J = 180/190/200/200/200/210 35 rpm
Adhesive resin (C) layer: C1 / C2 / C3 / C4 / AD / J = 170/180/190/200/200/200 20 rpm
EVOH resin (A) layer: C1 / C2 / C3 / C4 / AD / J = 180/190/220/220/220/220 13 rpm
Adhesive resin (C) layer: C1 / C2 / C3 / C4 / AD / J = 170/180/190/200/200/200 20 rpm
Linear low density polyethylene (B): C1 / C2 / C3 / C4 / AD / J = 180/190/200/200/200/210 35 rpm
・ Die: φ150mm, set temperature 210 ℃
-Film take-up speed: 6m / min

  On the other hand, the following soy sauce cake to be packaged was prepared.

<Soy sauce bowl>
A soy sauce bowl made from soybeans and wheat (manufactured by Kaneiwa Soy Sauce) was purchased.

[Example 1]
A soy sauce cake molded body was produced by packaging and sealing the soy sauce cake by the packaging method shown below.
(Packaging method)
The multilayer structure film is folded in half to make it A4 size. After confining 200g of soy sauce cake in the folded film, the three sides of the opening are thermocompression bonded (conditions: 160 ° C, 2 sec, cooling 80 ° C) And sealed.

About the produced soy sauce cake molded object, the odor sensory test and the presence / absence / occurrence time of bleed-out were evaluated, respectively.
<Odor sensory test (evaluation of odor)>
The soy sauce cake molded body immediately after being stored indoors at room temperature and the soy sauce cake molded body after being stored indoors for 3 months were each subjected to a sensory test (indoor evaluation). On the other hand, the soy sauce cake molded body immediately after being stored outdoors and the soy sauce cake molded body after being stored outdoors for 3 months were each subjected to a sensory test (outdoor evaluation).
The average temperature and precipitation during the storage period were as shown in Table 1 below (from the Japan Meteorological Agency public data).

(Evaluation criteria for nasty smell)
○: Odorless (not smelling).
Δ: Slight odor is felt.
X: Strong off-flavor occurs.

<Presence / absence of bleed-out>
The presence or absence of bleed-out was confirmed by palpation and visual observation on the soy sauce cake molded body after being stored indoors at room temperature for 3 months and the soy sauce cake molded body after being stored outdoors for 3 months. For those where bleed out was confirmed, the time when the bleed out occurred was also shown.
The average temperature during the storage period was as shown in Table 2 below (from data released by the Japan Meteorological Agency).

[Example 2]
A soy sauce cake molded body was produced by packaging and sealing the soy sauce cake by the packaging method shown below.
(Packaging method)
The multilayer structure film was used, and the soy sauce cake was sealed by roll bale molding by winding the film twice. That is, the multilayer structure film is folded 10 cm in the longitudinal direction, the two ends in the short direction are thermocompression bonded (conditions: 160 ° C., 2 sec, cooling 80 ° C.), and 200 g of soy sauce cake is added from the opening, Was wound twice by applying tension at room temperature to obtain a soy sauce cake molded body.

  The produced soy sauce cake molded body was subjected to an odor sensory test (indoor / outdoor) and evaluation of the presence / absence / occurrence of bleeding out (indoor / outdoor) in the same manner as in Example 1.

Example 3
A soy sauce cake molded body was produced by packaging and sealing the soy sauce cake by the packaging method shown below.
(Packaging method)
Using a multilayer structure film, the soy sauce cake was sealed in the same manner as in Example 2 by winding the film four times by roll bale molding.

  The produced soy sauce cake molded body was subjected to an odor sensory test (indoor / outdoor) and evaluation of the presence / absence / occurrence of bleeding out (indoor / outdoor) in the same manner as in Example 1.

[Comparative Example 1]
Instead of the five-layered multilayer film, a 90 μm-thick polyethylene resin layer single-layer film (Nippon Polyethylene, NovatecLL UF421) was used. Except that, a soy sauce cake molded body was produced in the same manner as in Example 1.

  The produced soy sauce cake molded body was subjected to an odor sensory test (indoor / outdoor) and evaluation of the presence / absence / occurrence of bleeding out (indoor / outdoor) in the same manner as in Example 1.

[Comparative Example 2]
Instead of the five-layered multilayer film, a 90 μm-thick polyethylene resin layer single-layer film (Nippon Polyethylene, NovatecLL UF421) was used. Otherwise, a soy sauce cake molded body was produced in the same manner as in Example 2.

  The produced soy sauce cake molded body was subjected to an odor sensory test (indoor / outdoor) and evaluation of the presence / absence / occurrence of bleeding out (indoor / outdoor) in the same manner as in Example 1.

[Comparative Example 3]
Instead of the five-layered multilayer film, a 90 μm-thick polyethylene resin layer single-layer film (Nippon Polyethylene, NovatecLL UF421) was used. Otherwise, a soy sauce cake molded body was produced in the same manner as in Example 3.

  The produced soy sauce cake molded body was subjected to an odor sensory test (indoor / outdoor) and evaluation of the presence / absence / occurrence of bleeding out (indoor / outdoor) in the same manner as in Example 1.

[Comparative Example 4]
A soy sauce cake molded body was produced by packaging and sealing the soy sauce cake with the packaging method shown below.
(Packaging method)
A 90 μm thick polyethylene resin layer single-layer film (Nippon Polyethylene, NovatecLL UF421) was used, and the soy sauce cake was sealed by rolling the film 8 times by roll bale molding in the same manner as in Example 2.

  The produced soy sauce cake molded body was subjected to an odor sensory test (indoor / outdoor) and evaluation of the presence / absence / occurrence of bleeding out (indoor / outdoor) in the same manner as in Example 1.

  The above evaluation results [Evaluation of odor sensory test (indoor / outdoor) and presence / absence / occurrence of bleed out (indoor / outdoor)) are shown in Table 3 below.

  From the above results, the soy sauce cake was hermetically packaged using a film having at least one EVOH layer, in particular, a multilayer structure film having a five-layer structure in which polyethylene resin layers are laminated on both sides of the EVOH layer via an adhesive resin layer. The product of this example had no off-flavor and no occurrence of bleed-out even after 3 months, both indoors and outdoors.

  On the other hand, the comparative product obtained by hermetically packaging the soy sauce cake using the polyethylene resin layer single-layer film generated a strange odor and any occurrence of bleed out in any hermetic packaging means.

  The soy sauce cake preserving film of the present invention is used when the soy sauce cake is packaged and stored, and the soy sauce cake formed by using the soy sauce cake storage film is hermetically sealed. It is useful because it does not bleed out and the generation of off-flavors is suppressed, and soy sauce cake can be stored for a long time.

Claims (4)

  A soy sauce cake preserving film used for packaging and preserving soy sauce cake, comprising at least one layer comprising a saponified ethylene-vinyl ester copolymer.   2. The soy sauce according to claim 1, wherein the soy sauce koji preserving film is a multilayer structure film comprising a layer comprising a saponified ethylene-vinyl ester copolymer and a layer comprising a thermoplastic resin composition.粕 Preservation film.   A soy sauce cake formed by packaging and sealing a soy sauce cake using the soy sauce cake storage film according to claim 1 or 2.   A method for preserving soy sauce cake, comprising storing the soy sauce cake molded product according to claim 3.