JPH07258467A - Readily degradable molding and its production - Google Patents

Abstract

PURPOSE:To obtain a readily degradable molding preventing occurrence of a mold in storage, degradable with a microorganism after utilizing the molding, by coating the surface of a molding of a composition comprising a starchy polymer such as a raw starch, water and a thermoplastic resin with a mildewproofing agent. CONSTITUTION:The surface of a molding of a composition comprising 5-80-wt.%, preferably 20-60wt.% of a starchy polymer such as a raw starch and/or a modified starchy polymer prepared by modifying the raw starch, preferably 0.5-30wt.% of water and a biodegradable thermoplastic resin (e.g. a saponified substance of an ethylene-vinyl acetate copolymer, a polycaprolactone, a polylactic acid or a dicarboxylic acid glycol reaction product) is coated with a mildewproofing agent [preferably sorbic acid (salts), epsilon-polylysine or allyl isothiocyanate) to give the objective molding.

Description

Detailed Description of the Invention

[0010]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a mold-disintegrating molded product and a method for producing the same, and more particularly, to a molded product comprising a composition containing a starch-based polymer, which prevents mold from forming during storage. The present invention relates to a disintegrating molded article that disintegrates due to microorganisms and the like after the product is utilized, and a method for producing the same.

[0011]

2. Description of the Related Art Conventional biodegradable molded products containing starch-based polymers are decomposed by microorganisms to form compost, and then naturally decomposed into water and carbon dioxide gas, which have an excellent function of being useful in waste disposal problems. Since it has, mold is likely to occur. As a means for long-term storage of polysaccharides, etc., Japanese Patent Publication No. Sho 63-3214
9 anionic surfactant is included, or Japanese Patent Publication No. 63-63.
Cryogenic storage of -32150 is known.

[0012]

However, a conventional molded article made of a biodegradable molded article has a problem that it loses its utility value because mold is generated during storage, so that the storage management cost is low. It is extremely large and hinders industrial use, and if it contains a long-term preservative, it may impair biodegradability. Therefore, the present inventor has conducted intensive studies to obtain a molded product that does not lose its utility value due to generation of mold during storage and easily disintegrates at the time of disposal after use, and completed the present invention.

[0013]

Means for Solving the Problems The present invention has the following configurations. (1) The content of the starch-based polymer in the composition comprising the starch-based polymer, water and a thermoplastic resin is 5 to 80% by weight,
The starch-based polymer is a raw starch or / and a modified starch-based polymer obtained by modifying the raw starch, and the surface of the molded product of the composition is coated with a fungicide, which is a disintegrating molded product. (2) A composition comprising a starch-based polymer, water and a biodegradable thermoplastic resin, wherein the content of water in the composition is 0.5 to 30% by weight, and the biodegradable thermoplastic resin is The saponified product of ethylene-vinyl acetate copolymer and / or polycaprolactone. The saponified product of ethylene-vinyl acetate copolymer has an ethylene content of 0.01 to 60 mol%, a molecular weight of 100 to 500,000, and a saponification rate of 0. ．
01-99.99% saponified ethylene-vinyl acetate copolymer, in which the modified starch polymer is a chemically modified starch derivative obtained by modifying raw starch, chemically degradable starch, enzyme modified starch, physically modified starch And the amount of the fungicide coated on the surface of the molded article of the composition is ² to 40 μg / cm ² , and the fungicide is sorbic acid, sorbates, ε-polylysine, allyl isothiocyanate and a mixture thereof. (3) a starch-based polymer,
The content of the starch-based polymer in the composition consisting of water and a thermoplastic resin is 5 to 80% by weight, and the starch-based polymer is raw starch or / and a modified starch-based polymer obtained by modifying the raw starch. , Using a composition in which the thermoplastic resin is a biodegradable thermoplastic resin to form a granulated product, and then applying a mold proofing agent or a roll with an antifungal agent aqueous solution having a pH of 3 to 8 and molding using the above granulated product. The method for producing a mold-disintegrating molded article coated with an antifungal agent having a coating amount of ^{2 to} 40 μg / cm ² for transferring the antifungal agent applied to a mold or roll.

The present invention will be described in detail below. In the collapsible molded article of the present invention, the content of the starch-based polymer in the composition comprising the starch-based polymer, water and the thermoplastic resin is 5 to 80.
% By weight, the starch-based polymer is raw starch or / and a modified starch-based polymer obtained by modifying the raw starch, and the surface of the molded article of the composition is coated with a fungicide.

The starch-based polymer used in the present invention is raw starch or a modified starch-based polymer obtained by modifying the raw starch. That is, raw starch is corn starch, bracken starch, kudzu starch, potato starch, wheat starch, kissava starch, sago starch, tapioca starch, sorghum starch, bean starch,
The modified starch-based polymer is a lotus starch, a lotus starch, a sweet potato starch, and the like, and the modified starch-based polymer is a chemically modified starch derivative obtained by modifying raw starch, a chemically-degraded starch, an enzyme-modified starch, and a physically modified starch. As chemically modified starch derivatives, allyl etherified starch, carboxymethyl etherified starch, hydroxyethyl etherified starch, hydroxypropyl etherified starch, methyl etherified starch, phosphoric acid crosslinked starch, formaldehyde crosslinked starch, epichlorohydrin crosslinked starch, acrolein crosslinked starch, Acetoacetic esterified starch, acetic acid esterified starch, succinic acid esterified starch, xatogenic acid esterified starch, nitric acid esterified starch, urea phosphoric acid esterified starch,
Phosphate-esterified starch can be exemplified, dialdehyde starch, acid-treated starch, hypochlorous acid-oxidized starch, etc. can be exemplified as chemically modified starch, and hydrolyzed dextrin, enzymatically decomposed dextrin, amylose etc. can be exemplified as enzyme modified starch,
Examples of the physically modified starch include α-starch, fractionated amylose and heat-moisture treated starch.

The composition of the present invention is a composition containing a starch-based polymer, and the content of the starch-based polymer in the composition is 5 to 80% by weight, more preferably 20 to 6
It is 0% by weight. A starch polymer content of 5% by weight or more is preferable because it has good biodegradability, dimensional stability, and excellent processability. Further, if the blending ratio of the starch-based polymer in the composition of the present invention exceeds 80% by weight, which is 80% by weight or less, the blending ratio of the thermoplastic resin as the fluidity improving agent in the composition is reduced and the flowability is reduced. When the amount of the thermoplastic resin is large, the flowability is improved and the moldability is improved.

The composition of the present invention contains water, preferably 0.5 to 30% by weight, more preferably 2 to 15%.
% By weight. The water content may be that contained in the starch-based polymer, water may be supplied to the composition, or water may be supplied after the granulation product. By containing this water, the moldability and ease of use of the present invention are improved. The thermoplastic resin of the present invention is preferably a biodegradable thermoplastic resin, and examples of the biodegradable thermoplastic resin include saponified ethylene-vinyl acetate copolymer, polycaprolactone, polylactic acid, and glycol dicarboxylic acid reactant.

The saponified ethylene-vinyl acetate copolymer is characterized in that it is composed of a polymer obtained by copolymerizing vinyl acetate and ethylene and then partially hydrolyzing the vinyl ester group. Above all, the ethylene content is 0.01 to 60 mol% and the molecular weight is 100 to 500.
000, a saponification product of an ethylene-vinyl acetate copolymer having a saponification ratio of 0.01 to 99.99%, and an ethylene-vinyl acetate copolymer having an ethylene content of 20 to 60 mol% and a saponification ratio of 50% or more. A saponified product is preferable because it is excellent in biodegradability and fluidity.

Further, a thermoplastic resin may be further added as a fluidity improving agent, and as such a thermoplastic resin, polyolefin, vinyl polymer, polystyrene, polyacrylonitrile, polyacrylate, polymethacrylate, polyacetal, thermoplastic polycondensate may be added. , Polyaryl ether, thermoplastic polyimide, polyethylene, polypropylene, polyisobutylene, polyvinyl chloride, polyvinyl acetate, polystyrene, polyamide, polyester, polyurethane, polycarbonate, polyalkylene terephthalate, alkylene / vinyl ester copolymer, alkylene / acrylate or methacrylate copolymer , ABS copolymers, styrene / acrylonitrile copolymers, amide ethers, amide ester block copolymers, ethylene Len / vinyl acetate copolymer (E
VA), ethylene / acrylic acid copolymer (EAA),
Ethylene / ethyl acrylate copolymer (EEA),
Ethylene / methacrylate copolymer (EMA), styrene / acrylate nitrile copolymer (SAN), ethylene / maleic anhydride copolymer, amide ether,
Examples thereof include amide ester block copolymers, urethane ethers and urethane ester block copolymers. Further, since such a thermoplastic resin has a low molecular weight, it easily becomes a biodegradable thermoplastic resin.

In the composition of the present invention, if necessary, a filler, a lubricant, a release agent, a plasticizer, a foaming agent, a stabilizer, a filler, a modifier, a flow accelerator, a colorant, a pigment. Can be added. Glycerin or stearic acid may be used as a lubricant.

In the disintegratable molded product of the present invention, the surface of the molded product of the above composition is coated with an antifungal agent. The amount of the antifungal agent applied to the surface of the molded product is preferably ² to 40 μg / cm ² . Antifungal agents include sorbic acid, sorbates, ε-
Preservatives for foods such as polylysine and allyl isothiocyanate are preferable, but fungicides having toxicity such as phenols, metal salts of naphthenic acid and salicylanilide may be used. However, it is limited to food preservatives from the viewpoint of safety when using the disintegratable molded article in food containers and the like.

The food preservative according to the present invention means sorbic acid, potassium sorbate, benzoic acid, sodium benzoate, potassium benzoate, propionic acid, calcium propionate, sodium propionate, isobutyl paraoxybenzoate, paraoxybenzoic acid. Isopropyl acid, ethyl paraoxybenzoate, methyl paraoxybenzoate,
Butyl paraoxybenzoate, propyl paraoxybenzoate, dehydroacetic acid, sodium dehydroacetate, orthophenylphenol, orthophenylphenol salt,
Thiabendazole, Diphenyl, Glycine, Acetic acid, Acetate, Lactic acid, Citric acid, Adipic acid, Alcohols, Sodium nitrite, ε-Polylysine, Ethanol, Egonoki extract, Kawamura wormwood extract, Shirakon protein, Hinokitiol extract, Galacturon Pectin degradation product consisting of acid, forsythia extract consisting of fililin, fig leaf extract, oregano extract, citrus seed extract consisting of fatty acids and flavonoids, licorice oil extract consisting of flavonoids, clove extract consisting of eugenol, Mulberry extract consisting of stilbene derivative, kojic acid,
Perilla extract, cinnamon extract, sage extract consisting of cineole and camphor, ginger extract consisting of gingerol and gingerol, sage extract consisting of cineole and camphor, polygonial polyphenol, catechin tea Extract, raw soybean extract, garlic extract, pimenta extract consisting of eugenol and thymol, grape skin extract consisting of polyphenol compounds, propolis extract consisting of flavonoids, etc. Pepper extract consisting of, Bokthiol succulent extract, Moso bamboo extract, Scutellaria extract, lysozyme, rosemary extract consisting of rosemanol and carvacnol, wasabi extract consisting of allyl isothiocyanate, nutmeg extract , Mace extract, peppermint extract, eucalyptus extract, parsley over seed extract, Majuramu extract, thyme extract, coriander extract,
Sassafras extract, laurel extract, caraway extract, dill extract, anise extract, onion extract, clove extract, oregano extract, savory extract, thyme extract, cumin extract, caraway extract, Protamine, chitosan, melanoidin, agar oligosaccharide, betaine used alone or in combination of two or more and pH
Gluconic acid, tartaric acid, lactic acid, glycine, for changing properties
Examples include phytic acid, polymerized phosphoric acid, malic acid, phosphoric acid, tynic acid, gallic acid, fatty acid, ellagic acid, kojic acid and the like.

The molding and processing method of the composition according to the present invention to the disintegratable molded article includes an injection molding method, an extrusion molding method, an inflation film molding method, a deflation film molding method, a T die film molding method, and a coat hanger die film. Molding method, lamination molding method, monofilament extrusion molding method, composite monofilament extrusion molding method, melt fiber spinning molding method, T die type extrusion sheet molding method, coat hanger die type extrusion sheet molding method, extrusion blow molding method, extrusion pipe molding method , Injection blow molding, sheet blow molding, stretch blow molding, multilayer blow molding, direct vacuum molding, drape vacuum molding,
Air lip vacuum forming method, plug assist vacuum forming method,
Air cushion vacuum molding method, pressure molding method, male and female molding method, slip molding method, extrusion profile molding method, extrusion foaming method, extrusion coating molding method, calendered sheet molding method, calendered film molding method, calendered leather It is a molding method, a compression molding method, a transfer molding method, or the like, and does not specify the processing method.

The method for producing a disintegratable molded product according to the present invention is characterized in that the composition is kneaded, processed and molded, and then the surface of the molded product is coated with an antifungal agent. The antifungal agent may be applied directly to the molded article, or may be applied to a mold or roll and then transferred. Among them, in the case of the transfer method, the composition is heat-sterilized in a molten state and molded by a mold coated with an antifungal agent, or molded by using a roll coated with an antifungal agent, so that germs on the surface of the molded article can be adhered. Since the amount can be reduced, a molded product having excellent storage stability can be obtained, which is preferable.

The antifungal agent can be uniformly applied by dissolving it in a solvent such as an ethanol aqueous solution and applying it. The pH of this aqueous solution is preferably 3 to 8, and more preferably 4 to 7. By using an aqueous solution having a pH within this range, the mold and the like are not corroded, and at the same time, an antibacterial action is provided. The method of transferring using a mold is to apply a preservative for food to a molding mold by spray coating with a spray or brush coating, and mold the disintegrating composition onto the coated mold to form only the surface. It is a method for obtaining a mold-disintegrating molded article covered with a food preservative. As a molding method using such a mold, an injection molding method, an extrusion blow molding method, an injection blow molding method, a sheet blow molding method, a stretch blow molding method, a multilayer blow molding method, a direct vacuum molding method, a drape vacuum molding method, Air lip vacuum forming method, plug assist vacuum forming method, air cushion vacuum forming method, pressure forming method, male and female forming method, slip forming method, extrusion profile forming method, extrusion foaming method, compression forming method, transfer forming method There is.

The transfer method of extrusion molding is a manufacturing method in which a mold contacting agent is transferred onto the surface of a molded product by a roll that is in contact with the molded product while being extruded. For example, a method of immersing the mold in a container containing a fungicide, a spray spray coating method and a brush coating method to apply the fungicide to the roll, and by contacting a molded product such as a film to the roll, It is a production method for obtaining a molded product whose surface is covered with a fungicide. Examples of such extrusion molding method include melt fiber spinning molding method, extrusion molding method, inflation film molding method, deflation film molding method, T die film molding method, coat hanger die film molding method, lamination molding method, monofilament extrusion molding method. , Composite monofilament extrusion molding method, melt fiber spinning molding method, T-die extrusion sheet molding method, coat hanger die extrusion sheet molding method, extrusion coating molding method, calendaring sheet molding method, calendaring film molding method, calendaring leather There is a molding method.

Hereinafter, the present invention will be described with reference to examples, but some examples are shown, and the present invention is not limited to these examples.

(Example 1) 40 mm manufactured by Yamaguchi Seisakusho
Lip clearance with single-screw extruder YE-40
Using a 1.2 mm coat hanger die, ethylene 10
Ethylene / vinyl acetate copolymer containing mol%, partially saponified ethylene-vinyl acetate copolymer with 90% saponification rate (specific gravity 1.27) 55.8% by weight, water 6% by weight, corn starch 38% by weight %, Titanium white 0.1% by weight and glycerin 0.1% by weight, a film was obtained. The cylinder temperature was 130 ° C to 146 ° C, and the die was 143 ° C. The screw rotation speed was 31 rotations per minute, and the motor load current was 23A. The thickness of this film was constant, the surface of the film was uniform, and no shark skin was generated. 0.3%
70% containing ε-polylysine (manufactured by Chisso Corporation)
A coated rubber roll was dipped into a container containing an aqueous ethanol solution, and transferred to both sides of the film by the coated rubber roll to produce a final product of 35 μg / cm ² . In addition, a film which was not covered with ε-polylysine was also produced without contacting the coated rubber roll. The take-up speed of the film was 17 m / min, and the thickness of the obtained film was 50 μm.

Each of the two types of films produced was inoculated with Aspergillus suspension water, which is a black mold, to give 28
As a result of culturing in an atmosphere of 90 ° C. and a humidity of 90%, black mold was generated on the film which was not covered with ε-polylysine after 5 days, and the property of disintegration by microorganisms was developed. ε
-The polylysine-covered film was of high commercial value, with no black molds observed even after 60 days had passed. After wiping the surface of the film covered with ε-polylysine with a wet cloth, it was inoculated with Aspergillus suspension water, which is a black mold, in the same manner as above, and the humidity was 90 ° C. at 28 ° C.
When cultured in an atmosphere of 10%, black mold was generated after 5 days elapsed, and the property of disintegration by microorganisms was developed. When decomposed in compost for 25 days, the molding lost its original shape.
From this result, the disintegrating molded article of the present invention was excellent in storability during storage and excellent in disintegrating property after being left for use.

Example 2 A 50 mm diameter screw injection molding machine (maximum injection pressure 14
35Kg / cm ² : FE160S25ASE A16M
221), 5% by weight of partially saponified polyvinyl alcohol having a saponification rate of 85% with a modified ethylene / vinyl acetate copolymer containing 22 mol% of ethylene, 9% of water, 38% by weight of potato starch, and A composition comprising 0.6% by weight of talc was injection molded under the following conditions to obtain a processed molded product. Injection timer 22.0 sec, cooling timer 20.0 sec, intermediate time timer 5.0 se
c, metering start timing timer 0.5 sec, injection device backward start timing timer 0.1 sec, V5 injection fifth order speed 15%, V4 injection fourth order speed 15%, V3 injection third order speed 15%, V2 injection second order speed , 15%, V1
Injection primary velocity 15%, TP2 injection secondary pressure time 2
0 sec, S5 injection secondary pressure switching position 15.0 m
m, S4 injection 5th speed switching position 0.1 mm, S3 injection 4th speed switching position 20.0 mm, S2 injection 3rd speed switching position 30.0 mm, S1 injection 2nd speed switching position 60.0 mm, SM Weighing stop position 130 mm,
SD decompression position 2.0 mm, P3 injection secondary pressure 1%, P2 injection secondary pressure 27%, P3
Injection primary pressure 45%, overback prevention timer
0.1 sec, injection bleed OFF, VS screw rotation speed setting device 17%, screw back pressure setting device
1%, screw rotation switch High speed, heating temperature ℃ 150HN 156H1 151H2 132H
3. The set value of mold temperature is 27 ° C.

A 70% aqueous ethanol solution containing 0.3% potassium sorbate (manufactured by Chisso Corporation) adjusted to pH 5 with gluconic acid was sprayed onto both inner surfaces of the mold,
The above-described commercially available starch-based polymer-containing composition was injection-molded into this mold to produce a tray container coated with a food preservative at 38 μg / cm ² by the transfer method. In addition, a processed molded product of a tray container to which a food preservative was not applied was also produced. Each of the two types of tray containers produced was inoculated with Aspergillus suspension water, which is black mold, and cultured in an atmosphere of 28 ° C. and a humidity of 90%. As a result, black mold was applied to the tray containers not covered with potassium sorbate within 3 days. In the tray container covered with potassium sorbate, no black mold was observed even after 45 days had passed, and it was proved that potassium sorbate manufactured by Chisso Corporation had an antibacterial action and was excellent in storage stability. A collapsible resin container molded product was produced.

After wiping the surface of the tray container covered with 0.3% potassium sorbate adjusted to pH 5 with gluconic acid with a water-wiping cloth, it was inoculated with Aspergillus suspension water that was black mold, and the humidity was 90% at 28 ° C. After culturing in the atmosphere described above, black mold was generated after 3 days passed, the same result as that of the tray container not covered with potassium sorbate was obtained, and the property of disintegration by microorganisms was again expressed.

Example 3 A pH of 8 without pH adjustment
A tray container was obtained by molding in the same manner as in Example 2 except that an aqueous solution of potassium sorbate in ethanol was used. Aspergillus suspension water, which is black mold, was inoculated into this tray container, and cultured in an atmosphere of 28 ° C. and a humidity of 90%. As a result, black mold was generated in the tray container that was not covered with potassium sorbate for 3 days, and sorbic acid was generated. Black mold was generated on the tray container covered with potassium after 5 days elapsed. Thus, a tray container using an aqueous ethanol solution of potassium sorbate having a pH of 8 was proved to have a weak antibacterial action, and a preservative-degradable resin tray container molded product was obtained. Using potassium sorbate whose pH has been adjusted, it is necessary to produce a molded product of a degradable resin tray container having excellent storage stability.

After the surface of the tray container covered with potassium sorbate was wiped with a wet cloth, it was inoculated with Aspergillus suspension water, which is black mold, and cultured at 28 ° C. in an atmosphere of 90% humidity. Black mold developed in the area, and the microbial disintegration property was reappeared.

(Example 4) 40 mm diameter YE-40 single screw extruder manufactured by Yamaguchi Seisakusho Co., Ltd., screw compression ratio 1.
03, L / D = 25 The screw of the double screw with the tip maddock is installed, the screen pack is not removed,
Partially saponified product of 35% saponification rate of vinyl acetate containing ethylene of 20 mol% ethylene from T-die with 350 mm width and lip clearance of 1.0 mm with only breaker 65
An 80 μm thick sheet was extruded from a sheet of a composition comprising the components of 10% by weight, 13% by weight of water, 12% by weight of corn starch and 8% by weight of glycerin at a cylinder temperature of 130 ° C. to 150 ° C. and a screw rotation of 72 rpm. The motor load current at this time was 37 A, and the resin pressure was 80 kg / cm ² .

A pudding cup mold is set on a vacuum processing machine (FVF device: manufactured by Fuse vacuum processing machine) of the manufactured sheet, and 0.3% sorbic acid ethanol aqueous solution adjusted to pH 5 with vinegar is sprayed to spray the mold. A pudding cup container was vacuum-molded from the sheet under the following vacuum molding conditions by spraying on both inner surfaces, and a cup molded product covered with a food preservative was manufactured. Heating temperature 310 ℃, molding cycle
68 to 47 seconds, mold temperature room temperature, pneumatic pressure 4
Kg / cm ² , mold clamping pressure 50 Kg / cm ² , upper heater 32 to 13 seconds, lower heater 32 to 13
Seconds, molding delay 0.1 seconds, molding time difference 1 second, blow delay 0.2 seconds, blow vacuum 0.5 seconds, plug rise 0.3 seconds, vacuum delay 0.1 second, vacuum. cooling
33 seconds, compressed air delay 0.1 seconds, compressed air 6 seconds, cooling delay 10 seconds, cooling fan 0.1 seconds, cooling spray 1 second, cooling extension 1 second, release blow 0.1.
Seconds.

Further, a pudding cup without a food preservative was also manufactured. Each of the two types of pudding cups produced was inoculated with Aspergillus suspension water, which is black mold, and cultured in an atmosphere of 28 ° C and a humidity of 90%. As a result, pudding cups that were not covered with sorbic acid within 3 days had passed. Black mold was generated, and no black mold was observed in the pudding cup container covered with sorbic acid even after 50 days had passed. From this result, it was proved that sorbic acid had an antibacterial action, and a vacuum molded product having excellent storage stability was produced. After wiping the surface of the film covered with sorbic acid with a wet cloth, it was inoculated with Aspergillus suspension water, which is black mold, and cultured in an atmosphere of 28 ° C and a humidity of 90%. Black mold developed after 3 days. , The same result as the film not covered with sorbic acid was obtained, and the microbial disintegration property was again expressed.

Example 5 MODERN MAC
HINERY CO, LTD's EXTRUDER TY
Using a PED-90 uniaxial extrusion air-cooled inflator,
Screen pack with screws with central madock
Put one 40 mesh, pinch pressure 2kg / cm ²
By operating the first pinch roll, 56% by weight of a composition of 78% saponification rate of a modified ethylene / vinyl acetate copolymer containing 55 mol% of ethylene, 2% by weight of water, and 37% of wheat flour starch.
Inflation films of compositions were prepared from the components, wt%, and 5 wt% glycerin. Cylinder temperature is 11
5 ° C to 150 ° C, die temperature is 140 ° C,
The screw rotation speed was 15 rpm and the motor load current was 150A. Film take-up speed is 65
m / min, the thickness of the obtained film is 50μ
It was m.

Allyl isothiocyanate was transferred by a method in which a coating roll dipped into a container containing an ethanol aqueous solution of 0.3% allyl isothiocyanate (Midori Cross Co., Ltd.) was contacted from both sides of the film to obtain the final product. In 1
A film coated with 0 μg / cm ² was produced. A film not covered with allyl isothiocyanate was also prepared. The take-up speed of the film was 65 m 2 / min, and the thickness of the obtained film was 50 μm. Aspergillus suspension water, which is black mold, was inoculated into each of the two kinds of produced films, and cultured in an atmosphere of 28 ° C. and a humidity of 90%. As a result, black mold was generated in the film not covered with allyl isothiocyanate within 3 days. Then
The surface of the film covered with allyl isothiocyanate showed no black mold even after 7 days had passed. From this result, it was proved that allyl isothiocyanate had an antibacterial action, and a soot-disintegrating film molded product excellent in preservability was produced. After wiping the surface of the film covered with 0.3% allyl isothiocyanate manufactured by Midori Cross Co., Ltd. with a wet cloth, inoculated with Aspergillus suspension water which is black mold, and cultured at 28 ° C. in an atmosphere of 90% humidity. After 3 days, black mold was generated, the same result as that of the film which was not covered with allyl isothiocyanate was obtained, and the property of disintegration by microorganisms was developed again.

Example 6 The film not covered with the food preservative of Example 5 was allowed to stand in a polyethylene bag made of highly volatile allyl isothiocyanate. After putting this film and a sheet coated with allyl isothiocyanate, inoculate with Aspergillus suspension water that is black mold, and
As a result of culturing at 8 ° C. in an atmosphere of 90% humidity, no black mold was observed on the film covered with allyl isothiocyanate even after 6 days had passed. Black mold developed on the film not coated with allyl isothiocyanate after 3 days. From this fact, it was proved that allyl isothiocyanate had an antibacterial action, and a soot-disintegrating resin film molded article having excellent storage stability was produced. But,
The films of Examples 5 and 6 had a very strong horseradish odor, and it is unfortunate that the processed moldings whose storage stability was improved by allyl isothiocyanate were restricted in terms of use. The sheet coated with allyl isothiocyanate was taken out of the polyethylene bag, allowed to stand in the air until the odor of horseradish weakened, inoculated with Aspergillus suspension water that was black mold, and cultured at 28 ° C in an atmosphere of 90% humidity,
Black mold was generated after 3 days elapsed, the same result as that of the film which was not covered with allyl isothiocyanate was obtained, and the property of disintegration by microorganisms was again expressed.

(Example 7) YE-4 manufactured by Yamaguchi Seisakusho
0 Single-screw extruder and MBM monofilament stretching machine with a compression ratio of 1.03, L / D = 25 with a small pitch of the compression part and a tip maddock, and the screen pack contains a 40 mesh stainless wire mesh. , A modified ethylene vinyl acetate copolymer containing 7 mol% of ethylene and having a partial saponification rate of 15%, 57.9% by weight, water 14% by weight, flour starch 28% by weight and glycerin 0.1% by weight. Cylinder temperature from 127 ° C to 150
℃, die temperature 145 ℃, screw rotation speed 58 rpm
In 21A, a monofilament having a draw ratio of 10% or more was manufactured. Transfer to the surface of the monofilament with two coating rolls (kiss rolls) that are dipped into a container containing a 70% aqueous ethanol solution of 0.3% ε-polylysine (manufactured by Chisso Corporation), and finish only on the opposite surface. The product produced a monofilament coated at 28 μg / cm ² . Further, a monofilament not covered with ε-polylysine was also produced without contacting the coating roll. The take-up speed of the monofilament was 37 m / min, and the obtained monofilament was 80 denier.

Each of the two types of monofilaments produced was inoculated with Aspergillus suspension water, which is black mold,
After culturing at 28 ° C and 90% humidity for 1 day, replica with a food stamp sold by Chisso Corporation for fungi,
The cells were cultured at 28 ° C. in an atmosphere of 90% humidity for 3 days. An extremely large number of colonies were generated on the monofilament not covered with ε-polylysine, but no colony was formed on the monofilament covered with ε-polylysine even after the lapse of 10 days. A collapsible plastics film molded product which was proved to have an action and was excellent in storability was manufactured. After wiping the surface of the monofilament covered with ε-polylysine with a wet cloth, inoculate with Aspergillus suspension water that is black mold,
After culturing at 28 ° C in an atmosphere of 90% humidity for 1 day, replicating with a food stamp sold by Chisso Co., Ltd., and culturing for 3 days in an atmosphere of 28 ° C and 90% humidity, an extremely large number of colonies were generated, and microorganisms The re-disintegration property of s.

(Embodiment 8) MODERN MAC
HINERY CO, LTD's EXTRUDER TY
Using a PED-90 uniaxial extrusion air-cooled inflator,
Screen pack with screws with central madock
Put one 40 mesh, pinch pressure 2kg / cm ²
Corn starch containing 15% by weight of a vinyl acetate copolymer composition having a 95% saponification rate containing 0.5 mol% of ethylene and 18% by weight of water by activating the first pinch roll at
An inflated film of a composition consisting of 1.9% by weight and 0.1% by weight of glycerin and 45% by weight of polycaprolactone was prepared. Cylinder temperature is 135 ℃ to 1
65 ° C., die temperature 170 ° C., screw rotation speed 25 rpm, motor load current 155
It was A. The film take-off speed is 40 m / mi
n, and the thickness of the obtained film was 65 μm.

The allyl isothiocyanate was transferred by a method in which a coating roll dipped in a container containing an ethanol aqueous solution of 0.3% allyl isothiocyanate (manufactured by Midori Cross) was contacted from both sides of the film to obtain the final product. In 1
A film coated with 0 μg / cm ² was produced. A film free of allyl isothiocyanate was also produced.
The take-up speed of the film was 20 m 2 / min, and the thickness of the obtained film was 60 μm. Manufactured 2
Aspergillus suspension water, which is black mold, was inoculated into each of the various types of films and cultured in an atmosphere of 28 ° C. and a humidity of 90%. As a result, black mold was generated in the film not covered with allyl isothiocyanate within 3 days, and isothiocyanate was generated. No black mold was observed on the film covered with allyl acid even after 5 days had passed. From this result, it was proved that allyl isothiocyanate had an antibacterial action, and a soot-disintegrating film molded product excellent in preservability was produced. After wiping the surface of the film covered with 0.3% allyl isothiocyanate manufactured by Midori Cross with a wet cloth, inoculate with Aspergillus suspension water that is black mold,
When cultured in an atmosphere of 28 ° C. and a humidity of 90%, black mold was generated after 3 days elapsed, the same result as that of the film not covered with allyl isothiocyanate was obtained, and the property of disintegration by microorganisms was again expressed.

Example 9 YE-4 manufactured by Yamaguchi Seisakusho
0 Single-screw extruder and MBM monofilament stretching machine with a compression ratio of 1.03, L / D = 25 with a small pitch of the compression part and a tip maddock, and the screen pack contains a 40 mesh stainless wire mesh. , A natural polymer (starch) as a biodegradable resin, Mater-Bi AF
05H was produced at a cylinder temperature of 148 ° C. to 154 ° C., a die temperature of 155 ° C. and a screw rotation speed of 58 rpm at 21 A to produce a monofilament having a draw ratio of 10% or more. 7% of 0.3% ε-polylysine (manufactured by Chisso Corporation)
Dip into a container containing 0% ethanol aqueous solution and transfer to the surface of monofilament with two coating rolls (kiss roll), and only 28 μg of the final product on the opposite surface.
/ Cm ² coated monofilament was produced. Also,
A monofilament not covered with ε-polylysine was also prepared without contact with the coating roll. The take-up speed of the monofilament was 17 m / min, and the obtained monofilament was 80 denier.

Each of the two types of monofilaments produced was inoculated with Aspergillus suspension water, which is black mold,
After culturing at 28 ° C and 90% humidity for 1 day, replica with a food stamp sold by Chisso Corporation for fungi,
The cells were cultured at 28 ° C. in an atmosphere of 90% humidity for 2 days. An extremely large number of colonies were generated on the monofilament not covered with ε-polylysine, but no colony was formed on the monofilament covered with ε-polylysine even after the lapse of 10 days. A collapsible plastics film molded product which was proved to have an action and was excellent in storability was manufactured. After wiping the surface of the monofilament covered with ε-polylysine with a wet cloth, inoculate with Aspergillus suspension water that is black mold,
After culturing at 28 ° C in an atmosphere of 90% humidity for 1 day and replicating with a food stamp sold by Chisso Co., Ltd., and culturing at 28 ° C in an atmosphere of 90% humidity for 2 days, an extremely large number of colonies were generated The re-disintegration property of s.

(Example 10) 40 m manufactured by Yamaguchi Seisakusho
m Single-screw extruder YE-40 lip clearance
NOVON M4900, a commercially available starch-based polymer-containing easily disintegrating resin, using a 1.2 mm coat hanger die
I got a film of. Cylinder temperature is from 134 ℃ to 16
The temperature was 7 ° C, and the die was 162 ° C. The screw rotation speed is 32 rotations per minute, and the motor load current is 23.
It was A. The coated rubber roll was dipped into a container containing a 70% aqueous ethanol solution containing 0.3% ε-polylysine (manufactured by Chisso Corporation), and transferred to both surfaces of the film by the coated rubber roll, and the final product was 37 μg / c
A m ² film was produced. In addition, a film which was not covered with ε-polylysine was also produced without contacting the coated rubber roll. The take-up speed of the film is 35 m / min,
The thickness of the obtained film was 45 μm.

Each of the two types of films produced was inoculated with Aspergillus suspension water, which is a black mold, to give 28
As a result of culturing in an atmosphere of 90 ° C. and a humidity of 90%, black mold was generated on the film not covered with ε-polylysine after the passage of 3 days, and the property of disintegration by microorganisms was developed. ε
-The polylysine-covered film was of high commercial value, with no black molds observed even after 60 days had passed. After wiping the surface of the film covered with ε-polylysine with a wet cloth, it was inoculated with Aspergillus suspension water, which is a black mold, in the same manner as above, and the humidity was 90 ° C. at 28 ° C.
When cultured in an atmosphere of 10%, black mold was generated after the lapse of 3 days and the property of disintegration by microorganisms was developed. From this result, the disintegrating molded article of the present invention was excellent in storability during storage and excellent in disintegrating property after use.

(Comparative Example) In each of the Examples, the fact that all the black molds were generated in the soot-disintegrating resin in which the surface of the food preservative was not applied by the transfer method is set as a Comparative Example.

[0050]

EFFECTS OF THE INVENTION The so-called collapsible molded article of the present invention has good workability and moldability, the molded article has excellent dimensional stability, and industrial molding is possible. In addition, the disintegratable molded article of the present invention prevents the generation of mold irrespective of the accelerated test of the temperature of 28 ° C. and the humidity of 90%, and the original biodegradability is shown in the test after wiping after using the molded article. Was good and was disintegrated by microorganisms and the like. The biodegradable molded product using the composition comprising the starch-based polymer, the water and the biodegradable thermoplastic resin had better biodegradability. Especially, the saponified ethylene-vinyl acetate copolymer and polycaprolactone were good in biodegradability. The amount of water in the composition is 2 to 15
The disintegrating molded product using the composition in an amount of wt% had excellent moldability and flowability, and the processed molded product had a good appearance. Chemically modified starch derivatives modified from raw starch, chemically degradable modified starch, enzyme modified starch, and physically modified starch modified degradable starch-based disintegrating molded products had excellent appearance and good biodegradability. .

The method of applying the antifungal agent aqueous solution having a pH of 3 to 8 was excellent in antibacterial action without corroding the mold or the like. In the transfer method in which a mold or roll is coated with a mildew-proofing agent and then molded with this mold or roll, the mildew-proofing agent is applied on the surface in the state with the least number of germs, so it is excellent in storage stability without bringing in germs. Molded products can be processed and have excellent industrial productivity. Thus, the disintegratable molded article of the present invention has excellent effects in both industrial and environmental fields and can be widely used industrially.

Claims (3)

[Claims] 1. A composition comprising a starch-based polymer, water and a thermoplastic resin, wherein the content of the starch-based polymer is 5 to 80% by weight, and the starch-based polymer is raw starch or / and the raw starch. A modified disintegrable molded product, which is a modified starch-based polymer obtained by modifying, and the surface of the molded product of this composition is coated with an antifungal agent. 2. The thermoplastic resin is a biodegradable thermoplastic resin, the content of water in the composition is 0.5 to 30% by weight, and the biodegradable thermoplastic resin is ethylene-acetic acid. A saponified vinyl copolymer and / or polycaprolactone, wherein the modified starch polymer is a chemically modified starch derivative obtained by modifying raw starch, a chemically degradable starch, an enzymatically modified starch, a physically modified starch and a mixture thereof. Yes, the amount of antifungal agent applied to the surface of the molded article of the composition is 2 to 40 μg /
2. The disintegratable molded article according to claim 1, wherein the antifungal agent is cm ² and is a food preservative selected from sorbic acid, sorbates, ε-polylysine, allyl isothiocyanate and a mixture thereof. 3. A starch polymer in a composition comprising a starch polymer, water and a thermoplastic resin is contained in an amount of 5 to 80% by weight, and the starch polymer is raw starch or / and this raw starch. Which is a modified starch-based polymer in which the thermoplastic resin is a biodegradable thermoplastic resin, is used as a granulated product, and then a mold or roll is coated with an antifungal agent aqueous solution having a pH of 3 to 8, A method for producing a mold-disintegrating molded product, which comprises transferring the antifungal agent applied to a mold or roll by molding the granulated product.