JPS5833103B2 - Kikaseiten Kazaiofukumakuo Sexositenal Sheet - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a sheet laminated with a film containing a volatile additive and having a large surface area. This is to prevent mold from growing.

Mold grows on all sorts of things, including food.

Leather products, textile products, optical machinery, precision instruments, photographic film, photographic paper, books, stationery, musical instruments, furniture, arts and crafts,
All items, including electronic materials, are not immune to the damage caused by mold.

The growth of mold causes discoloration and deterioration of properties of articles.

Particularly recently, the deterioration of industrial materials including metals due to fungi has become a problem, and preventive measures are being researched in various fields.

For example, there is a problem with the deterioration of the interior of the metal due to the rusting of the metal and the action of mold, and it is even said that in the case of high-purity aluminum, the mold that forms on the rusted areas on the surface of the aluminum can further induce corrosion inside the metal.

The following two methods are currently known as mold control measures.

One of these is pellets, which are made of porous particles such as silica gel and adsorbed with mold inhibitors, but these cannot be considered packaging materials.

The other type is a thermoplastic resin such as polyethylene mixed with a mold inhibitor and a rust inhibitor, kneaded and melted at high temperature, and then formed into a packaging film or sheet.

Since this method involves a heating step, there is a risk that the type of anti-mold agent that can be added is limited, and that the anti-mold agent may vaporize and decompose during kneading.

On the other hand, for the purpose of rust preventing articles, rust preventive paper impregnated with a volatile rust preventive agent and polyethylene film kneaded with a rust preventive agent are known.

However, the former is used as a piece of enclosed paper and is not used for packaging purposes.

In addition, the latter film has a smooth film surface and has a small surface area compared to an uneven surface, and the rust preventive agent evaporates into the atmosphere from the outside surface, so the rust prevention effect remains small.

This invention provides a sheet having a film with a wide surface area to which a volatile additive is added, and when the volatile additive is used, for example, a mold inhibitor or a rust preventive agent, the above-mentioned conventional problems are solved. It was designed so that

The sheet of the present invention has a weight ratio of 100 parts of adhesive to 10 to 400 parts of granules having an average particle size of 0.3 to 40 μm having adsorption ability.
It is a sheet having fine irregularities on the surface, which is formed by laminating a film made of a mixture of these materials, 25 or less of a volatile additive, and a small amount of a non-volatile additive added as appropriate, on the surface of a sheet base material.

A typical method for laminating the film onto the sheet substrate is a method in which the above mixture is applied to the sheet substrate in a fluid state.

However, other methods such as spraying or adhering a separately formed film to the sheet base material may also be used.

The composition of the mixture and the particle size of the granules must satisfy the above-mentioned conditions in order to improve the adhesion to the sheet base material and to effectively exhibit the vaporizing action of the vaporizable additive.

The granular material is required to be capable of adsorbing and retaining at least the volatile additive.

If the average particle size is less than 0.3μ, it tends to aggregate, and if it exceeds 40μ, a film with a wide surface area cannot be formed.

If the weight ratio is less than 10, a large surface area will not be obtained, and if it exceeds 400, the adhesive strength between the sheet base material and the membrane will decrease.

When the amount of the volatile additive exceeds 25%, a similar decrease in adhesive strength is also observed.

As the volatile additive, the most practical are volatile mold inhibitors and rust preventives, as described below, but there is no need to limit the additive to these.

For example, any vaporizable substance that has a useful effect, such as preservatives or fragrances, may be used.

Further, in the present invention, in addition to the volatile additive, non-volatile additives such as pigments, antioxidants, etc. can be appropriately added to the film forming components.

The sheet of this invention has a significantly large surface area with minute irregularities on the surface, and is designed to continuously vaporize the active ingredients of the volatile additive from the film surface. Suitable for packaging.

For example, when a mold inhibitor is used as a volatile additive, even if the additive has low volatility at room temperature, the mold inhibiting component evaporates continuously from the film surface, resulting in a sufficiently effective mold inhibiting effect over a long period of time. demonstrate.

When used as a packaging material, the mold-inhibiting component is present inside the package in an amount of 1 to 1,500 ppm, usually 50 ppm; if it is vaporized 8 degrees, the packaged article can be protected from mold damage.

Next, when a rust preventive agent is used as a volatile additive, or when a mold inhibitor, an antioxidant, etc. are used in combination with this agent, an effect similar to the above-mentioned effect is basically achieved.

As mentioned at the beginning, with metals such as high-purity aluminum, mold that forms on the surface of the metal induces rusting inside the metal with the help of water and humidity in the air.

Furthermore, deterioration phenomena caused by mold and the like that occur in textile products, leather products, and other industrial materials are often related to rust caused by moisture and oxidation effects caused by air.

Therefore, depending on the type of packaged goods, it may be necessary to not only aim for a mold prevention effect, but also to combine mold prevention and rust prevention, mold prevention and oxidation prevention, or even a combination of mold prevention, rust prevention, and oxidation prevention. Effects are also required, and the present invention can also provide a sheet having such multiple functions.

The sheet of the present invention exhibits excellent performance in protecting food, textile products, furniture, and other articles from mold damage, or in protecting metal materials and products from rust.

In addition, in this invention, a film can be formed on the sheet base material by painting, so unlike the conventional method of kneading thermoplastic resins, productivity is high and there are no restrictions on the use of volatile additives, and there is no need to use volatile additives during production. It never loses its effectiveness.

Moreover, since the film can be formed on only one side of the sheet base material, the volatile additive can be used economically and effectively.

Furthermore, since the irregularities on the membrane surface are minute, printing or writing can be performed on the membrane surface by selecting a transparent or translucent adhesive or sheet base material.

Next, details of the raw materials used in this invention will be explained.

(1) Sheet base material: Although no limitations are placed on the material, generally a sheet of synthetic polymer or high molecular weight material is used to support the granular material layer described below.

For example, sheets of polyester, polypropylene, polyethylene, polyvinyl chloride, polyvinyl alcohol, polyvinyl acetate, polyvinylidene chloride, polyamide, etc.
Alternatively, synthetic polymer sheets made of copolymers and composites thereof are generally used, and sheets of natural polymers such as paper and cellophane can also be used.

(2) Granular material: A material that physically or chemically adsorbs and retains the volatile additive and increases the surface area of the sheet base material, thereby facilitating the vaporization of the additive.

Regardless of the shape of the granules, whether microcrystalline or amorphous powder, it is appropriate that the average particle size is in the range of 0.3 to 40μ.

Porous materials are particularly preferred, and more preferably materials that form strong chemical bonds with the adsorbed vaporizable additive through van der Waals forces, hydrogen bonds, etc.

However, the material is not limited to this, as long as it can increase the surface area of the sheet base material and form fine irregularities.

First, aluminum hydroxide [Al(OH)3] and talc (MS'3 (S i
401o) (OH)2).

Since aluminum hydroxide has three OH groups in one molecule and is an amphoteric substance, it forms a chemically weak bond with the adsorbed vaporizable additive and exhibits a sustained vaporization effect.

Talc can have a similar effect, and as its molecular structure suggests, like aluminum hydroxide, it retains volatile additives well due to its weak chemical bonds.

Other inorganic particulates that should be mentioned include alumina, barium carbonate, barium sulfate, calcium carbonate, tricalcium phosphate, calcium hydrogen diphosphate, magnesium oxide, magnesium sulfate, magnesium hydroxide, silicon oxide, and silicon oxide with hydroxyl groups added. Metal oxides and metal hydroxides, such as metal hydroxides, can be used alone or in mixtures.

Furthermore, acid clay, diatomaceous earth, activated clay, activated carbon, zeolite, etc. can also be used.

As the granules, organic granules can also be used in addition to the above-mentioned inorganic granules.

For example, one or a combination of two or more of carbohydrates such as starch and carboxymethyl cellulose, and polar synthetic polymers such as polyamide and polyvinyl chloride are also applicable to the present invention.

(3) Adhesive: A medium or glue for fixing the particulate matter and volatile additive to the surface of the sheet base material.

A typical method for manufacturing the sheet of this invention is to mix particulate matter and a volatile additive with an adhesive, and then apply this mixture to the surface of a substrate.

Therefore, the adhesive in this case must have properties that allow the additives mentioned above to be dispersed uniformly, properties that exhibit appropriate fluidity at least during application, and properties that quickly solidify after application through drying, polymerization, or other chemical reactions. The property of forming a coating film is required.

When selecting polymeric materials such as nitrates and oligomers for adhesives, they must be thermally polymerized using a catalyst or exposed to ultraviolet light or
It is necessary to carry out homopolymerization or copolymerization by irradiating visible light, electron beams, radiation, etc.

Among these types, unsaturated epoxy esters and unsaturated epoxy acrylates can be recommended as excellent adhesives.

Polymer solutions and suspensions that form dry coatings by evaporation are also suitable adhesives, including commonly known rubber adhesives, protein adhesives, starch adhesives, polyvinyl acetate and polyvinyl alcohol. Solutions, suspensions, etc. can be used.

Polyolefin sheets generally have poor chemical adhesion, making it difficult to obtain coatings with high adhesive strength.

The adhesive mixture not only exhibits sufficient adhesive strength to such polyolefin sheets, but also has high workability in the application process, and the process from the start of application to the end of drying can usually be completed in 50 m/min to 150 m/min. can be set.

(4) Volatile additives: When adding the following volatile additives, not only one kind but two or more kinds can be added.

(4a) Anti-mold agent It is preferable that the agent evaporates slowly at room temperature, has a wide spectrum of inhibition against fungi, and has no adverse effect on the human body.

It goes without saying that the latter condition is particularly required for food packaging purposes.

The mold inhibitor may be solid or liquid, and it does not need to be soluble in the above-mentioned adhesive, but it must be sufficiently retained at least in the granular material.

Therefore, when making a selection, consideration should be given to the type of packaged material, the type of mold that should be prevented from occurring, etc.

The mold inhibitors applicable to this invention are listed below.

In addition, chemical formulas are added as appropriate and only one or a few types are listed for each system, but these are only representative examples.
There is no need to limit it to that.

(4a-1) Organic nitrogen compounds: dichloroisocyanurate for cyanuric compounds, sodium azide for potassium azide-based compounds, NaN3, and N(P- or O-phenol)-trichloroethylcyanimidazole-based compounds for alkyl cyanide-based compounds. Most preferred is 2-(4-thiazolyl)-benzimidazole, which has a large amount of carbon dioxide, has low toxicity, and is added to foods.Other examples belonging to this series include 1,3-dinonylbenzimidazolium bromide and 1-(2-thiazolyl)-benzimidazole. -hydroxyethyl)-1-benzyl-2-
Examples include tridecylimidazolium.

Guanidine compounds include dodecylguanidine hydrochloride H3C(CH2)11 NHC(NH) NH20Cl
.

Examples of quaternary ammonium salt compounds include alkyldimethylbenzylammonium phthalimidate, which is a large cationic ammonium salt and is represented by the general formula, where R1 is an aliphatic chain and R2 is an aromatic group.

(4a-2) Halide: α-bromocinnamaldehyde benzylbromoacetate 1-(3-chloroallyl)-3,5,7-triacyl-adamantane chloride N-fluorodichloromethylthiophthalimide N-dimethyl-N'-phenyl- There are many others, such as N/-(fluorodichloromethylthio)sulfamide (bis-(1,4-bromoacetoxy)-2-butene).

4a-3) Sulfur compound: Thiuram compound is N-(-P-phenol)-rmethylthiocarbamate potassium-n to tetramethylthiuram disulfide thiocarbamate compound.
-Hydroxylmethyl-n-methyl-bitiocarbamate.

1,2-ben in benzthiazolone compound Zo-isothiazo suspension methylene-bis-thiocyanide Oceanate H2C(SCN)2.

Others belonging to the series include sodium-2-mercaptobenzothiazole and tetrahydro-3,5-dimethyl-2H-1°3.5-thiadiazine-2-thione.

(4a-4) Organic acid compounds such as phenol: 2.4
．． 5-Trichlorophenol C13C6H20H2 O-phenylphenol C6H5C6H40H.

Pentachlorophenol C6C1! j, OH.

Sorbate H3CCH2CHCH2CHCOOH.

n-Butyl P-hydroxybenzoate HOC6H4COO (CH2)3CH3° (4b) Volatile Rust Inhibitor Many rust inhibitors also have an antioxidant function.

Those that are volatile at room temperature include phenol-based ones, 2,6-di-tert-butylphenol, butylhydroxyanisole, 2,6-tert-butyl-p-cresol, and amine-based ones, such as dicyclohexyl. Ammonium nitrite, N*N'-C5e
c-phthyl-p-phenylene diamine, 6-nitoxy 2,2.4-t-rifthyl-1,2-dihydroquinoline, sulfur-based ones, dilauryl thiodipropionate,
Typical examples include 2-mercaptobenzimidazole, phosphorus-based ones, triphenylphosphite, tridecylphosphite, trilauryltrithiophosphite, and the like.

(4c) Other volatile additives Many of the mold inhibitors mentioned above also have preservative (sterilizing) properties, but other volatile additives include paraoxybenzoic acid esters, dehydroacetic acid esters, etc. , bleaching powder, chloramine T1, chloramine B, etc., and vaporizable insecticides such as piperonyl butoxide, DDT, BHC, pyrethrin, carbon disulfide, and formalin.

Almost all fragrances can be used, regardless of whether they are natural or synthetic.

Fragrances themselves are highly volatile, and only a small amount can be added, but the problem is that the fragrance disappears in a short period of time.

When added to the sheet of this invention, its special surface structure ensures the persistence of the fragrance.

Next, an example will be described.

In the following, [5j refers to "parts by weight".

Example 1 Equimolar reaction product of 01.6-hexanesiol diglycidyl ether and acrylic acid (epoxy group/acrylic acid-1. acid value 64)...
・40 parts ○ Acetone ・・・60 parts ○ Benzene isopropyl ether (initiator for photopolymerization) ・・・・1.0 parts ○ Aluminum hydroxide (average particle size around 2μ, gibbsite crystal structure , Showa Denko Co., Ltd., product name: Heijirai)H-42)...4
0 parts 02-(4-thiazolyl)-benzimidazole (mold inhibitor) 1.0 parts The above formulations are mixed uniformly.

This mixture was uniformly applied using a coating rod to a two-wheeled stretched polypropylene film with a thickness of 50μ that had been previously subjected to a corona discharge treatment, and then ultraviolet rays were applied to the film for 30 minutes using a 2KW mercury lamp from a distance of 20 crrL. Irradiated for seconds.

As a result, a coating film was formed on the surface of the polypropylene film.

As is clear from the scanning electron micrograph in Figure 1, the coating film has a significantly large surface area with countless fine irregularities due to the addition of aluminum hydroxide.

Next, using this film, 10 bags of 5 cIrL x 4 crrL were made with the coating surface facing inside.
A mold inhibition test was conducted as follows.

First, remove commercially available bread from a packaging bag labeled as containing no mold inhibitors, slice it with a sterilized knife, and
Prepare 20 sample pieces crrL×4crn.

This sample piece was left indoors for 30 minutes to allow mold spores floating in the air to fall and adhere to its surface.

Then, 10 of the sample pieces with mold spores were placed in the polypropylene bag that had been prepared earlier, the opening was sealed with adhesive tape, and the bag was placed in a room at a humidity of around 70% and a temperature of 23°C for 5 days. When the bags were left to stand, out of the 10 bags, except for one that had a slight blue mold, no mold developed in the remaining nine bags.

Four of the bags are shown in the top row of Figure 2.

Furthermore, a sample piece extracted from one of the bags is shown in Figure 3A.
Shown below.

In addition, this group of bags did not reduce its mold-inhibiting effect against the following molds for at least 6 months.

The same applies to Examples 2 and 3. Cladosporium resinae, Puliularia pullu
lans), Penicillium citrinum (Penicillium
Illium citrinum), Penicillium luteum, Aspergillus niger (Aspergi flusni)
ger), Aspergillus flavus (Aspe-rg
illus flavus), Aspergillus oryzae, Chaetomium globosum
sum), Trichoderm viride (Trichoderm
a viride).

On the other hand, a comparative test was conducted in accordance with the above.

That is, ten polypropylene bags were made following the same procedure as above, except that the mold inhibitor was omitted from the film-forming formulation described above, and each bag was filled with the remaining material from the previous experiment. When 10 sample pieces with mold spores attached were sealed one by one and a mold suppression test was conducted under the same conditions, all of the 10 sample pieces in the bag had various types of mold, including blue mold, white, red, and black. There was mold.

Four of the bags are shown in the bottom row of Figure 2.

Arrows indicate mold that has grown.

Furthermore, a sample piece extracted from one of the bags is shown in Figure 3B.
Shown below.

From the above, the effect of adding a mold inhibitor has become clear.

2-(4-thiazolyl)-benzimidazole is an excellent mold inhibitor that is stable against strong ultraviolet rays irradiated during coating film formation and is itself harmless.

In the previous experiment, the concentration of the mold inhibitor vaporized inside the bag was less than several tens of meters at room temperature, and it can be said that it would have no effect on the human body even if used for food packaging.

The bag obtained in this example was entirely translucent, and the coated surface was capable of printing, as well as letters and designs on it with a pencil or pen.

Example 2 Sixteen polypropylene film bags were manufactured in the same manner as in Example 1 except that talc with an average particle size of 2 μm was used as the inorganic particulate material instead of aluminum hydroxide.

The coating surface of this film has a finely uneven surface due to the addition of talc, as shown in the scanning electron micrograph of FIG.

Like aluminum hydroxide, talc can chemically strongly retain various mold inhibitors, and since it is a scale-like flexible crystal, there is no risk of it peeling off even when the film is bent.

Vacuum-packed commercially available mochi is sliced with a heat-sterilized knife.
Cut out 16 pieces to a size of rrL x length 3crrL and use them as sample pieces.

Half of the sample pieces were sterilized with boiling water for 3 minutes, and the other half were sterilized for 3 minutes without sterilization.
By leaving the sample in a room for 0 minutes, mold spores floating in the air were allowed to fall and adhere to the sample surface.

When these sample pieces were sealed one by one in the polypropylene bags prepared earlier and the bags were left in a room with a temperature of 23°C and a humidity of around 65% for 7 days, two bags of sample pieces that had not been sterilized were separated. I barely saw the growth of mold mycelium, but none of the remaining bags had mold growth or strange odors.

FIG. 5 C2D shows two examples. A is a sample piece that has been sterilized with boiling water, and B is a sample piece that has not been sterilized with boiling water.

On the other hand, a comparative test was conducted in accordance with the above.

That is, 16 polypropylene bags were made using the same procedure except that the use of a mold inhibitor was omitted from the paint film-forming formulation, and each bag was filled with the mold spore-adhered sample prepared in the previous experiment. Each piece was sealed and a mold inhibition test was conducted.

As a result, mold developed on the sample pieces in all bags.

FIG. 5 C2D shows two examples of these, where C is a sample piece that was sterilized with boiling water as described above, and D is a sample piece that was not subjected to the same treatment.

From the above experimental results, it is clear that the film of this invention exhibits a significant mold inhibiting effect.

The effect remained unchanged even 250 days after the film was produced.

The bag obtained in this example also exhibited almost the same writability as in Example 1.

Example 3 Diacrylate of bisphenol diglycidyl ether (trade name Epicoat 8 from Shell Co.)
28) and reaction product with acrylic acid
...40 parts (the amount of acrylic acid used is the number of moles equivalent to 1 mole of oxygen in the oxirane structure of Epicote 828) ○Aluminum hydroxide ...
40 parts (same as above) ○ Acetone ... 60 parts 02-(4-thiazolyl)benzimidazole (mold inhibitor) 3 parts ○ Azobisisobutyronitrile (polymerization catalyst ) 2 parts of each of the above formulations are mixed uniformly to make a coating material.

In addition, upon mixing, aluminum hydroxide, acetone, and a mold inhibitor were thoroughly mixed in advance, and then this mixture was added to the adhesive monomer, and finally, the polymerization catalyst was added.

The prepared coating material was applied to the surface of a biaxially oriented polypropylene film, which had been previously subjected to a corona discharge treatment, to a thickness of about 50 μm using a coating rod, and then heated at 95° C. for 30 minutes.

As a result, a coating film with fine irregularities was formed on the surface of the polypropylene film.

A bag was manufactured using this film, and according to Example 1,
As a result of the mold deterrent test, it was found that there was a mold inhibitor in the bag.
When present in vaporized form around 70 ppm, there was no decrease in the mold inhibiting effect for at least 6 months.

Example 4 0 Ethyl acetate 15 parts ○ Aluminum hydroxide 50 parts (same as above) ○ α-bromocinnamaldehyde (mold inhibitor) 1 .5 parts Each of the above formulations was thoroughly mixed, and this mixture was added to 50 parts of polypropylene film gravure printing ink medium (trade name: PO8/ETY, Inu Nippon Ink Chemical Co., Ltd.) and thoroughly kneaded in a mortar.

This kneaded material was previously treated with corona discharge to a thickness of 60 μm.
It was coated onto a biaxially oriented polypropylene film using a coating rod.

The coating cured in a few seconds, and the adhesion between the protective coating and the film surface was strong, and no peeling was observed in a peel test using cellophane tape.

A scanning electron micrograph of the coating surface is shown in FIG.

A polypropylene film bag was made with the painted surface inside according to Example 1, and a mold suppression test was conducted.
As shown in the figure, there was no mold growth at all.

On the other hand, in the case of a film bag whose coating film did not contain a mold inhibitor, which was subjected to a comparison test, mold developed on the sample pieces, as indicated by the arrows in Figure 8.

Example 5 100 parts of gravure printing ink medium (polypropylene film medium, Toyo Ink Co., Ltd. trade name J90 PPN5), 15 parts of ethyl acetate, 5 parts of N-(fluorodichloromethylthio)-phthalimide as a mold inhibitor, and the above. Mix each formulation thoroughly.

This kneaded product was applied to a polyester film having a thickness of 50 μm in the same manner as in Example 4.

The coating film cured rapidly, and a peel test using cellophane tape showed no peeling from the film surface.

We conducted a mold inhibition test, which will be discussed later.

Example 6 Medium for gravure printing ink (Dainippon Ink Chemical Co., Ltd. trade name Panacea 5L) 10
0 parts, aluminum hydroxide (mentioned above) 50 parts, acetone 1
Add the following as a mold inhibitor to a mixture consisting of 5 parts of each of the above formulations and knead well.

3 parts of a 60fb aqueous solution of a mixture of potassium N-hydroxymethyl-N-methyldithiocarbamate and sodium 2-mercaptobenzothiazole in a volume ratio of 4:1.

The above kneaded product was applied to the nylon surface of a three-layer film consisting of nylon-polyvinylidene chloride-polyethylene in the same manner as in Example 4 to form a coating film.

A mold inhibition test was conducted using the applied film.

The method and results will be described later.

Example 7 The mold inhibitors shown in (a) to (a) below were added separately to a mixture of 100 parts of brominated cinnamic aldehyde (mentioned above), 40 parts of aluminum hydroxide (mentioned above), and 15 parts of toluene. Mix well.

(a) 2-benzyl-4-chlorophenol...
...5 parts (b)tetrahydro-3,5-dimethyl-2H-1,3
゜5-thiadiazine-2-thione...5 parts (c) 2-(4-thiazolyl)benzimidazole2.
A mixture of 5 parts and 2.5 parts of 0-phenylphenol.
・・・・・・5 parts) screws
(1,4-bromoacetoxy)-2--jthene
・・・・・・1 part of each kneaded product to a thickness of 4
The mixture was applied to four sheets of 0μ biaxially stretched polypropylene film (trade name: Paihan, manufactured by Showa Yuka Co., Ltd.) to form a coating film.

A mold inhibition test was conducted using the applied film.

The results will be described later. A mold inhibition test was conducted using the previously reserved film of Example 5.6.7.

The test method and experimental results will be explained below.

Prepare standard mold mixture spores prior to testing.

For example, a mixed spore suspension of the following four types of molds specified in JIS Z2991 "Mold Resistance Test Method" is prepared in advance according to ASTM D 1924-63.

Group 1: Aspergillus niger ATCC
6275° 2nd group... Penicillium citrinum (Penicillium citrinum) AT
CC9849゜Group 3... Rhizopus nigricans (Rh1zopus nigricans) SN32
゜・Group 4...Pulularia pullulans (Pulularia pullulans) IA
In the MF24° test, the film prepared in Example was pasted on the entire inner surface of a Petri dish with a diameter of 9 cIrL and the lid (bottom of the dish, side walls, and back of the lid), and then a ring shape with a diameter of 3 cm and a width of 0.5 cIrL was attached to the bottom. Place the shaped comparison film in the center of the bottom of the Petri dish.

Note that the comparative film refers to a film produced under the same conditions as each Example except that the use of a mold inhibitor was omitted.

Place the sample piece on top of the ring-shaped comparison film.

The sample piece was 3cr of commercially available bread that was labeled as having no mold inhibitor added.
It is cut to a size of rL x 3crrL x 0.5crIL.

Next, a fixed amount of the mold-mixed spore suspension prepared above is sprayed onto the sample piece.

To prevent the specimen from drying out, pour two volumes of sterile water into the Petri dish.

The mold growth state of the sample piece was monitored after 8 days and 1 day by keeping the lidded bedpan (with a slight amount of outside air flowing in and out) at a temperature of 28℃.
Observations were made twice after 5 days.

The results will be displayed together with those of the comparison test.

However, the comparative example in the table shows a film that does not contain a mold inhibitor produced according to Example 7, and the comparative example 2 shows the results of a mold inhibition test using only a sample piece without using a film. Symbols (a), ** (b), (c) added to
, 2) are for identifying the type of mold inhibitor described in Example 7, respectively.

Depending on the characteristics of the mold inhibitor, some types of fungi may have no effect on mixed spores.

This symbol indicates the degree of growth if any one species grows, so other spore conidia are suppressed.

However, since 7) is a mold inhibitor for food additives, its effect is small compared to the other examples.

Some of the results in the table are shown in photographs: the sample piece of Example 7@) is shown in Figure 9, the sample piece of Example 7 (c) is shown in Figure 10, the sample piece of Comparative Example 1 is shown in Figure 11, The sample piece of Comparative Example 2 is as shown in FIG.

Regarding the coexistence of bacterial species, even when mold was most prominent, the film made with the addition of a mold inhibitor did not have all four groups of bacteria growing together, and black mold was the majority. .

Example 8 50 parts of aluminum hydroxide, 10 parts of toluene, and 7 parts of dicyclohexyl ammonium nitrite as a rust inhibitor were mixed well, and to this was added 100 parts of Polypro G manufactured by Toyo Ink Co., Ltd. as a gravure printing ink medium. In addition, mix thoroughly.

This mixed material is made into a biaxially stretched polypropylene film (see above).
was applied uniformly by the same method as in Example 4.

Thereafter, 5 bags were manufactured in the same manner as in Example 1, and 2.5 cI of a small piece of soft iron well polished with sandpaper was placed in each bag.
rL×4crrL was sealed with 3 drops of water.

When these bags were left in a room at 23° C. and the inside of the bags was changed after 5 days, there was no sign of rust on the soft iron pieces.

On the other hand, a coating film was produced in the same manner as above except that the use of rust preventive agent was omitted, and a similar rusting test was conducted using the bag. Brown rust spots appeared on the small pieces.

Example 9 50 parts of aluminum hydroxide, 10 parts of toluene, 7 parts of the aforementioned dicyclohexyl ammonium nitrite, and 5 parts of α-bromocinnamaldehyde as a mold inhibitor were added to the above mixture, and then 5 parts of α-bromocinnamaldehyde was added as a mold inhibitor. Ink Chemical Co., Ltd. Product name Lami PP) 1
Add 00 parts and mix well.

The kneaded product was uniformly applied to a polyester film having a thickness of 60 μm to form a coating film having a thickness of 25 μm on the surface thereof.

Eight bags were made from this painted film, and each bag was filled with one 2CrrL x 3cIrL dog steel piece with both sides well polished, and one bread sample piece prepared in the same manner as in Example 1 with 3 drops of water. Enclosed with.

As a result of leaving these bags in a room at 23℃, 6 bags showed no abnormality, 1 bag had slight traces of mold, and although it could not be said to be obvious rust, there were several small black spots the size of needle heads. There was only one bag in which this was confirmed.

On the other hand, a painted film was produced using the same procedure as above, except that the use of rust preventive and mold inhibitor was omitted, and the bag 8
As a result of conducting a similar experiment using steel pieces, mold grew on the bread in each bag after 5 days, and brown rust appeared on the entire surface of the steel pieces.

Example 10 To 50 parts of a toluene solution of amorphous polypropylene chloride, 1 part of 2,6-tert-butylphenol, 6 parts of dicyclohexyl ammonium nitrite, and 2-(
2.5 parts of 4-thiazolyl)benzimidazole and 0
- Add 2.5 parts of phenylphenol and mix well, then add 40 parts of talc having an average diameter of 2 μm and knead well.

Next, this kneaded product was uniformly applied on the polypropylene surface of a three-layer laminate film consisting of polypropylene-saponified ethylene/vinyl acetate copolymer-polyethylene according to the same method as in Example 4.

Five bags were made from this film, and a piece of bread, a piece of steel, and a drop of water were sealed in each bag in the same manner as in Example 9.
It was left in a room at 3°C.

After 15 days had passed, the inside of the bag was changed and two pieces of bread had slight mold, but there was no sour or fermented odor, and only three pieces of steel had light brown rust. It is.

On the other hand, a painted film was obtained using the same procedure as above except that the use of the three agents, rust preventive agent, mold inhibitor, and antioxidant was omitted, and a similar experiment was conducted using eight bags. , 15
After a few days, abnormalities were observed in all the bags.

In other words, not only was all the bread covered with multicolored mold (blue, red, black, etc.), but mycelia also formed on the inside of the bag itself, giving off an intolerable sour odor. Rust formed.

Example 11 5 parts of α-bromocinnamaldehyde, 30 parts of toluene, and 300 parts of aluminum hydroxide (Hisilite H-42)
Mix well.

42 parts of diacrylate of bisphenol diglycidyl ether (Epicote 828, trade name of Shell Co.) and 58 parts of dodecynylsuccinic acid, which is a curing agent for the diacrylate, are thoroughly mixed.

This mixture and the previously prepared mixture were sufficiently kneaded, and the mixture was applied to a polyester film in the same manner as in Example 1 and kept at 70°C.

A pale yellow, translucent coating film with a thickness of about 30 μm was adhered to the surface of the polyester film.

A bag was made from this painted film in the same manner as in Example 1, and a mold suppression test was conducted by enclosing a piece of bread.
■A week later, we noticed traces of mold on one bag of bread.
No mold was generated in any of the four containers.

However, when we obtained the same coating film as above, except that we omitted the use of a mold inhibitor, and conducted a similar preservation test with slices of white bread sealed in five bags, the results showed that the bread in all bags remained intact. Mold grew in clumps.

Example 12 In Examples 1 and 2, films with coatings containing no mold inhibitor were produced for comparative tests, but
These two types of films (referred to as film A and film B)
and a biaxially oriented polypropylene film that was not coated as a control example, perfume was sprinkled on the surfaces of each in the following manner, and the change in scent over time was investigated.

The fragrance is eau de cologne (Perfu manufactured by Hasegawa Perfume Co., Ltd.)
Me CB-2280), cypress (Sugi26.227 manufactured by Kensha Co., Ltd.), matsutake (mixture of 80 matsutake all and 20% methyl cinnamate), all of which were prepared using acetone. or 0.0% of methanol.
A 1% solution was prepared, and this solution was sprayed onto the coated surface of the test film 3 to 5 times uniformly. After being sprayed, the film was air-dried.

Next, cut this film into a size of 6c1rL x 15cIrL, put the cut piece in a paper envelope, leave it indoors and in a desk drawer made of lauan wood, and observe the decay of the scent every 5 to 10 days. did.

As a result, although films A and B produced in Examples 1 and 2 lost their strong scents immediately after being sprayed after 10 days, the scents did not change much over time, and three of the scents of eau de cologne, cypress, and cedar were found. Even after a year has passed, they still have a good aroma.

In particular, items placed in the drawers of desks made of lauan wood gave off a scent as if the desk itself was made of cypress or cedar due to the wood fragrance.

Although matsutake mushrooms cannot ignore changes over time compared to the above, they still had a scent even after 180 days.

On the other hand, in the biaxially stretched polypropylene film of the control example, the scents of cypress, cedar, and matsutake began to fade three days after the fragrance was removed, and the scents almost completely disappeared after 30 days.

The scent of eau de cologne starts to fade after 7 days after application.
After a few days, only a slight scent remained.

Film A and Film B produced in Example 1 and Example 2
Because it has a coating film with fine irregularities on its surface, it is easy to dye.

Therefore, in order to improve the aesthetic appearance of the film, a portion of the same film as above was colored with the following acid dye prior to spraying the fragrance, and then the fragrance was removed and the persistence of the fragrance was examined in the same manner as before.

Suminol fast dye (Blue PR
conc.

Both Yellow 2GP and Red B conc y (manufactured by Sumitomo Chemical Co., Ltd.) were used, and the dyeing method was the same as that for fibers.

The results of the test showed that, except for the matsutake mushroom scent, which caused a strange odor and was not practical, the persistence of the other fragrances was unrelated to the dyeing, and the results were the same as those obtained without dyeing.

Note that the biaxially oriented polypropylene film of the control example could not be dyed with acid dye, as a matter of course.

[Brief explanation of drawings]

FIG. 1 is a scanning electron micrograph showing the surface structure of a sheet according to an embodiment of the present invention. Figure 2 is a photograph showing the results of a mold suppression test using a bag made from the above-mentioned sheet compared with a comparison test, Figure 3 is a photograph showing a sample piece taken out from the bag, and Figure 4 is a photograph of the invention. A scanning electron micrograph showing the surface structure of the sheet in another example, FIG. 5 is a photograph showing the results of a mold inhibition test using a bag made from the sheet compared with a comparative test, and FIG. Furthermore, scanning electron micrographs showing the surface structure of sheets of other examples, photographs shown in FIGS. 7 to 12, show the effects of the present invention in comparison with those of comparative examples in a mold suppression test.

Claims (1)

[Claims] 1. A film consisting of a mixture of 100 parts by weight of an adhesive that is assimilated after adhesion, 10 to 400 parts of granules with an average particle size of 0.3 to 40 μm having adsorption capacity, and 25 parts by weight or less of a volatile additive is applied to the surface of the sheet base material. A sheet formed by laminating films containing a vaporizable additive, which are laminated and have fine irregularities on the surface.