JP2014012658A - Active energy ray-curable composition and film for insect proof evasion and antibacterial activity using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a film for insect proof evasion and antibacterial activity that is satisfactorily used as an insect proof evasion and antibacterial sheet, especially the insect proof evasion and antibacterial sheet used for package of food products or the like, and that uses a plant extract as an active ingredient; and technology relating to the same.SOLUTION: An active energy ray-curable composition includes: each extract of Sichuan pepper, uva-ursi, Perilla Herb, a leaf of peach, chili pepper, Phellodendron amurense, Houttuynia Herb, ginger and sophora root as (A) an insect proof evasion and antibacterial active ingredient; and (B) an active energy ray-curable varnish.

Description

  TECHNICAL FIELD The present invention relates to an active energy ray-curable composition and an insect repellent and antibacterial film using the same, and more particularly, an active energy ray curable composition using a specific plant extract as an insect repellent and antibacterial active ingredient. The present invention relates to an insect repellent / antibacterial film having a layer of a cured product composed of the composition, an object which has been subjected to insect repellent and / or antibacterial treatment with the film, and a method of insect repellent and / or antibacterial using the film.

  Conventionally, a plant extract having an insect repellent effect and an antibacterial effect has been known (Patent Document 1).

  However, there is no known example of producing a sheet (film) for use for insect repellent or antibacterial purposes using such an extract. The reasons for this are as follows: (1) These extracts were not of satisfactory quality in terms of the amount of insoluble foreign matter and, in some cases, transparency, for use in the production of the sheet.・ As an antibacterial sheet, in particular, it was considered unsuitable as an insect repellent repellent and antibacterial sheet used for packaging foods etc. where the impression of hygiene is valued. (2) It is necessary to apply the extract to the sheet in some manner so that it does not easily peel off from the sheet, but a simple and efficient means therefor was not specifically known, in particular, When mixing the plant extract with some medium, the compatibility between the plant extract and such a medium is a problem. Using plant extracts using fee and what may be used medium, it is considered such that there was not enough information.

JP 2003-321315 A

  The present invention is an insect repellent / antibacterial sheet, in particular, an insect repellent / antibacterial film using a plant extract as an active ingredient, which is sufficient for use as an insect repellent / antibacterial sheet used for packaging of foods, and the like, and We intend to provide related technology.

  As a result of diligent research to solve the above problems, the present inventor used a plant extract made from a specific plant (herbal medicine) as an active ingredient, and used the plant extract together with an active energy ray-curable varnish. When it was used, it discovered that the said subject could be solved, and repeated examination, and came to complete this invention.

That is, the present invention
(A) As an insect repellent and antibacterial active ingredient, extracts of flower buds, walnuts, soyou, peach leaves, chili peppers, peonies, jujuaks, ginger and kujin, and
(B) The present invention relates to an active energy ray-curable composition comprising an active energy ray-curable varnish.

  The present invention also relates to an insect repellent and / or antibacterial film having a layer of a cured product comprising the active energy ray-curable composition on at least one surface of the film.

  The film is made of ABS (acrylonitrile-butadiene-styrene copolymer) resin, polyethylene, polyetherimide, polyethersulfone, polyethylene terephthalate, polybutylene terephthalate, polypropylene, polyvinyl alcohol, polyvinyl acetate, polyvinyl chloride, polyvinylidene chloride. A monolayer film composed of one material selected from polyvinylidene fluoride, polyethersulfone, polycarbonate, polystyrene and nylon, or a multilayer film obtained by laminating the same or different monolayer films. Is preferred.

  The present invention also relates to an insect repellent and / or antibacterial object wrapped with the film.

  Furthermore, the present invention relates to an insect repellent and / or antibacterial method comprising using said film.

  The active energy ray-curable composition of the present invention has a cured product layer composed of the active energy ray-curable composition, which is simply and efficiently applied to a film and irradiated with active energy rays. Since repellent and / or antibacterial films can be produced, they are extremely useful commercially.

  Moreover, the film of the present invention obtained in this manner exhibits excellent insect repellent and antibacterial activity. Therefore, the film of the present invention can be used in various applications for the purpose of insect repellent and / or antibacterial purposes, and in particular, the object can be easily repelled and repelled by wrapping the object with the film. And / or antibacterial treatment.

  Furthermore, if a highly transparent film is used, the state of the object wrapped with the film can be easily observed and confirmed from the outside, so that the object (for example, food) that needs to be confirmed at any time should be checked. It can be suitably used as a packaging film.

The state of the sample 1 and 2 before a preservation | save is shown. It shows the state of specimens 1 and 2 after storage for 13 days. The state after culture | cultivating by the agar plate culture method about the test bacterial solution of the comparative example immediately after inoculation is shown. The state after culture | cultivating by the agar plate culture method about the test bacterial solution of the comparative example after culture | cultivation (35 degreeC, 24 hours) is shown. The state after culture | cultivating the test bacterial solution of the Example after culture | cultivation (35 degreeC, 24 hours) by the agar plate culture method is shown.

  An extract from a plant (herbal medicine) and an active energy ray curable varnish, which are constituents of the active energy ray curable composition of the present invention, will be described.

(Plant (herbal medicine))
The plants used in the present invention are all known as herbal medicines.

  The flower bud is called Zanthoxylum bungeanum, and is a shrub belonging to the genus Citrus, which is native to East Asia. The site used in the present invention is the pericarp and is said to have a healthy stomach, analgesia, anthelmintic action and the like.

  Arctostaphylos uva-ursi, also known as the bearberry, is an evergreen shrub belonging to the genus Anemoneaceae. However, Japanese azalea (Arctous alpinus var. Japonicus) is another plant although it is sometimes called bearberry. The site used in the present invention is a leaf at the flowering stage, and is considered to have urinary sterilization action, diuretic action and the like.

  Soyo refers to the leaves and branches of Labiatae Perilla frutescens Britton var. Acuta Kudo, an annual plant native to southern China or its related plants. It is said to have antiseptic and bactericidal effects.

  Peach leaves are the leaves of the rosaceae peach (Prunus persica), also known as peach leaves. It is said that there is an insecticidal action of boufra.

  Chili pepper is a fruit of Capsicum that originates in Central and South America. It is said to have a healthy stomach and sweating.

  The grass is a dried bark excluding the pericarp of Phellodendron amurense, a deciduous tree of the genus Citrus. It is said to have effects such as intestinal sterilization.

  Zhuyak (heavy medicine, ten drugs, Houttuyania cordata), also known as Dokudami, is a perennial of the Dokudami family that originates in Japan, China, Southeast Asia, the Himalayas, etc. The site | part used by this invention is the above-ground part of a flowering period. It is said to have diuretic action, arteriosclerosis preventive action and the like.

  Ginger refers to the dried rhizome of Zingiber officinale Roscoe. It is said to have effects such as analgesia, antispasm, and sweating.

  Kujin (bitter ginseng) refers to the roots of the perennial leguminosae (Leguminosae) Clara (Sophora flavescens), cut or dried as it is or after removing most of the pericarp. It is said to have antifungal action.

  In the present invention, the plant extract (A) is prepared using the above plant (herbal medicine) as a raw material.

(Preparation of plant extract)
In the present invention, the preparation of the extract from each plant or herbal medicine (extract raw material) can be carried out by combining conventional methods. In the extraction, it is preferable to use the raw material for extraction after being finely chopped or pulverized. The extraction can be performed by a method of immersing the extraction raw material in a suitable extraction solvent and heating or heating (normal temperature to the boiling point of the solvent) under normal pressure or pressure.

  As an extraction solvent, water; lower alcohols such as methanol, ethanol, propanol and butanol; esters such as ethyl acetate; glycols such as ethylene glycol, butylene glycol, propylene glycol, 1,3-butylene alcohol and glycerin; diethyl ether, Examples include ethers such as petroleum ether; polar solvents such as acetone and acetic acid; hydrocarbons such as benzene, hexane, and xylene. Among these, water or alcohol (lower alcohol or glycols) is preferable, particularly water. Is preferred. These solvents can be used alone or in combination of two or more.

  Although the extraction time varies depending on various conditions such as the type of extraction raw material and extraction solvent, extraction temperature, etc., about 10 times as much water (8 to 12 times amount) as the extraction solvent is used as the extraction temperature. When employ | adopting the temperature of 50-60 degreeC, it is about 2-3 days normally. Those skilled in the art can determine various conditions including the extraction time from such information.

  Extraction may be performed for each raw material, or in the case where a plurality of raw materials are used, they may be appropriately combined.

  The solvent extract thus obtained is preferably freed from solids by filtration, centrifugation or the like. In the case of performing filtration, for example, the filtration device can be filtered with a filtration device prepared so as to be filtered through several exposed layers (for example, about 4 to 6 layers, preferably about 5 layers). In this case, as the exposure, a commercially available exposure, for example, Tamagawa bleach (100% hydrogen-bleached cotton, cooperative Kansai fashion union 0-26) can be preferably used.

  Furthermore, the solvent extract is preferably heated to distill off excess extraction solvent. As a specific example of the heating, for example, when water is used as the extraction solvent, the solvent extract is maintained at a temperature of 40 to 50 ° C. for about 1 to 2 days. In this way, a plant extract can be prepared.

  The plant extract of the present invention may further contain additives usually used in this field. Such additives include pH adjusters (eg, sodium citrate), preservatives (eg, potassium sorbate, sodium dehydroacetate), antioxidants (eg, sodium erythorbate), alcohols (ethanol, isopropyl alcohol, etc.) ) And other salts (sodium chloride). The amount of these additives is appropriately determined within a range that does not substantially affect the effect of the present invention.

  In the case of adding an additive to the plant extract, the additive is dissolved in a solvent in advance (in this case, if necessary, heated at 40 to 50 ° C. for about 2 hours), and then filtered through the above-described filtration device. It is desirable to keep it. In this case, the filtrate thus obtained can be mixed with the filtrate of the solvent extract, and can be subjected to the same steps hereinafter. As the solvent used for dissolving the additive, the above extraction solvent can be used.

(Use ratio)
In the preparation of plant extracts, the proportion (weight basis) of the plant (herbal medicine) used as the raw material is the same amount (basic amount) for each of the flower buds, walnuts, soyou, peach leaves, peonies, jujuaks, and ginger. It is preferable that the amount of chili pepper is 1.5 times the basic amount, and that of kujin is 2.5 times the basic amount, but the amount is varied within a range of ± 20% by weight based on the amount. be able to.

(Active energy ray curable varnish)
The active energy ray-curable varnish (B) refers to a varnish having a property of forming a cured product by irradiation with active energy rays such as ultraviolet rays and visible rays, and is usually a photosensitive monomer (40 to 68% by weight), It contains a photosensitive resin (30 to 40% by weight), a photopolymerization initiator (1 to 10% by weight), silica (1 to 10% by weight), and other appropriate additives usually used in this field. .

  In the present invention, among the active energy ray-curable varnishes, those having excellent compatibility with the plant extract, that is, a mixture that does not separate when mixed (including solutions and dispersions). Any of these can be suitably used, but specific examples of such an active energy ray-curable varnish include, for example, UV gloss OP varnish CP-3 (T & K TOKA Corporation). Dicure R OP Varnish GG, Dicure Avrio OP Varnish Dicure Avrio, Dicure Avrio OP Varnish HG, Dicure RTX OP Varnish RC, Dicure Scepter DT OP Varnish HB, Dicure New Z OP Varnish NW, Dicure WL OP Varnish H, Dicure WL OP Varnish L-T2, UV Carton C Wet OP Varnish, UV Carton C Wet SL OP Varnish, Dicure RX OP Varnish T-DPY, Dicure WL Matte OP Varnish AK, Dicure WL Matte OP Varnish YF, Dicure Abilio Matte OP Varnish ) And the like.

  An active energy ray hardening-type varnish can be used individually or in mixture of 2 or more types.

(Active energy ray-curable composition)
The active energy ray-curable composition of the present invention can be prepared by mixing the plant extract (A) and the active energy ray-curable varnish (B). The mixing ratio is not particularly limited as long as the desired insect repellent and antibacterial effect is exhibited and sufficient curing of the active energy ray-curable composition on the film surface is achieved. The use ratio of the plant extract is in the range of about 5 to 40% by weight with respect to the active energy ray-curable varnish (B). As a specific example, for example, when the plant extract (A) used in the examples of the present specification is used, the preferred use ratio of the plant extract is the active energy ray-curable varnish (B). On the other hand, it is in the range of about 10 to 30% by weight.

  In addition, the additive added to the plant extract is added when preparing the active energy ray-curable composition, in addition to adding it to the plant extract in advance prior to the preparation of the active energy ray-curable composition. May be. In particular, an additive that does not need to be dissolved in a solvent in advance (for example, alcohol) can be suitably added at the stage of preparing the active energy ray-curable composition.

(Preparation of insect repellent and / or antibacterial films)
The active energy ray-curable composition thus obtained is applied to a film and irradiated with active energy rays, whereby the insect repellent and / or antibacterial film of the present invention can be obtained.

(Material of film)
The material of the film used in the present invention is not particularly limited, and the film is composed of any material as long as it does not have a property that is not suitable for packaging an object requiring insect repellent and / or antibacterial properties. However, it can be suitably used. Examples of such materials include ABS (acrylonitrile-butadiene-styrene copolymer) resin, polyethylene, polyetherimide, polyethersulfone, polyethylene terephthalate, polybutylene terephthalate, and polypropylene (for example, YUPO (registered trademark)). , Polyvinyl alcohol, polyvinyl acetate, polyvinyl chloride, polyvinylidene chloride, polyvinylidene fluoride, polyethersulfone, polycarbonate, polystyrene, nylon, pulp (for example, wood pulp, non-wood pulp, waste paper pulp, etc.).

  The film composed of the above materials may be a single layer film composed of a single material, or may be a multilayer film obtained by laminating the same or different single layer films. As a specific example of the multilayer film, for example, a two-layer film in which a layer made of pulp is laminated on a polyethylene film can be mentioned.

  The thickness of the film is not particularly limited, but when used for wrapping an object, it is usually preferable that the thickness is in the range of 0.25 μm to 300 μm.

(Active energy rays)
In the present invention, the active energy ray is not particularly limited as long as it is an electromagnetic wave capable of curing the active energy ray-curable composition, and specific examples include γ rays, X rays, ultraviolet rays (UV), and visible rays. It is done.

(Application, irradiation, etc.)
In the present invention, a series of steps such as application of an active energy ray-curable composition to a film, curing by irradiation with active energy rays, and fixing of a cured layer can be performed by a conventional method, for example, active energy rays. Can be suitably carried out using a UV curable printer (for example, LR25 manufactured by Iwasaki Tekko Co., Ltd.). In this case, the wavelength of ultraviolet rays is in the range of about 100 to about 400 nm, and the intensity of irradiation is in the range of 1.4 to 3.0 KJ / cm ² .

  Since the film of the present invention thus obtained has an excellent insect repellent and antibacterial action, the object (preferably, foods, etc.) requiring such an effect is used for the purpose of repelling insects and / or antibacterial. Can be used.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these examples.

(Materials used in the examples)
Hanatsubaki: Chinese flower walnut: Japanese Pharmacopoeia “Uwaurushi”, Horie Seiyaku Co., Ltd.)
Soyo: Japanese Pharmacopoeia “Soha”, Uchida Wakayaku Co., Ltd.)
Peach leaves: Peach leaves (Tanzaku, made in China, Horie Seiyaku Co., Ltd.)
Pepper: Japanese chili powder powder Awaku: Japanese Pharmacopoeia “Owaku”, Uchida Wakayaku Co., Ltd.)
Juyaku: Japanese Pharmacopoeia “Zyuyaku”, Horie Seiyaku Co., Ltd.)
Ginger: Japanese pharmacopoeia “Ginger”, Uchida Wakayaku Co., Ltd.)
Kujin: Japanese Pharmacopoeia “Kujin”, Uchida Wakan Pharmaceutical Co., Ltd.)
Active energy ray curable varnish: UV gloss OP varnish CP-3 (manufactured by T & K TOKA)

1. Preparation of plant (herbal medicine) extract Flower buds 200g, walnuts 200g, soybeans 200g, peach leaves 200g, chili peppers 300g, peonies 200g, juyaku 200g, ginger 200g and cucumber 500g are immersed in 20 liters of water at a temperature of about 50-60 ° C. And boiled for 3 days with occasional stirring and then cooled to room temperature. The liquid thus obtained was filtered through a filtration apparatus in which five layers of bleaching (Tamagawa bleaching (100% hydrogen bleached cotton), Kansai fashion union 0-26) were layered and filtered. On the other hand, 200 g of sodium citrate, 200 g of potassium sorbate, 200 g of sodium dehydroacetate, 200 g of sodium erythorbate, and 500 g of sodium chloride are dissolved in 2 liters of water, heated at a temperature of about 40-50 ° C. for about 2 hours, and then to room temperature. It was cold. The liquid thus obtained was filtered using the same filtration device as described above. After combining the two filtrates thus obtained, the mixture is kept at a temperature of 40 to 50 ° C. for an additional half a day with occasional stirring to evaporate excess water, and then to a temperature of 20 to 30 ° C. To about 1800 g of plant extract.

2. Preparation of active energy ray-curable composition (active energy ray-curable composition 1)
To 1 liter of active energy ray-curable varnish, 200 g of the plant extract obtained above was added little by little with stirring. The mixture thus obtained was kept at a temperature of 20 to 30 ° C. with occasional stirring for one and a half days to evaporate excess water, thereby obtaining an active energy ray-curable composition 1.

(Active energy ray-curable composition 2)
The active energy ray-curable composition 2 is obtained by treating in the same manner as the preparation of the active energy ray-curable composition 1 except that the amount of the plant extract is changed to 250 g and 70 g of isopropyl alcohol is newly added. It was.

3. Preparation of insect repellent and antibacterial film (insect repellent and antibacterial film 1)
A roll of PET (polyethylene terephthalate) film having a thickness of about 50 μm and a width of about 21.8 cm was applied to a UV curable printer (LR25 manufactured by Iwasaki Tekko Co., Ltd.). Here, the active energy ray-curable composition 1 obtained above was used in place of the normally used ink as an application to the film. By this treatment, an insect repellent / antibacterial film 1 of the present invention was obtained in which a cured layer (thickness: about 5 μm) made of the composition was formed on the film. The intensity of UV irradiation was about 2.75 KJ / cm ² .

(Insect repellent and antibacterial film 2)
A layer made of pulp was formed on a polyethylene film having a thickness of about 90 μm and a size of about 50 mm × 50 mm (square) to obtain a two-layer film. The active energy ray-curable composition 2 was applied and air-dried to obtain the insect repellent / antibacterial film 2 of the present invention. The thickness of the film was about 300 μm.

4). Evaluation 4-1. Insect repellent and antibacterial film 1 (Method)
A bunch of bananas on the market was prepared, and a total of 2 bananas were cut from the bunch. A bag made of the film having the cured layer of the insect repellent / antibacterial film 1 obtained above was made inside, and one banana was put therein (Sample 1). The other banana was wrapped in a commercially available food wrap (Sample 2). The state of the two bananas thus prepared is shown in FIG. In addition, the insect repellent / antibacterial film 1 of the present invention shown in FIG. 1 is excellent in transparency and has an excellent feature that the state of the contents can be easily confirmed when foods are packaged. is there.

(Antimicrobial activity)
Sample 1 and Sample 2 were each placed in a cardboard box and stored at room temperature for 13 days, and the states after storage were compared. The results are as shown in FIG.

  As is clear from the figure, Specimen 1 had a moderately ripe state with brown spots (so-called sugar spots) even after 13 days of storage, but Specimen 2 was darkened as a whole and had a medium content. It was soft and discolored. This shows that the insect repellent and antibacterial film 1 of the present invention has excellent antibacterial activity.

4-2. Insect repellent / antibacterial film 2 According to JIS Z 2801: 2010 “Antimicrobial processed product-Antibacterial test method / antibacterial effect” (mainly “5 test method”) About the film 2, the antibacterial power test was done.

(Method)
The test piece, cover film, and test bacterial solution used in the test are as shown in the table below. However, Escherichia coli ATCC 43895 (E. coli, serotype O157: H7, verotoxin I and type II producing strain) was the only strain in the test bacterial solution. Moreover, the test piece was used for the test without cleaning.

(Antimicrobial activity)
The test bacterial solution of the comparative example immediately after inoculation, and the test bacterial solution of the example and comparative example after inoculation culture (35 ° C., 24 hours) were tested according to a predetermined method (agar plate culture method), respectively. The number of viable bacteria per 1 cm ² piece was measured (n = 3). The results are as shown in the following table and FIGS.

  As is clear from Table 2, the viable cell count immediately after inoculation increased significantly in the comparative example after culturing (35 ° C., 24 hours), but decreased significantly in the examples of the present invention. Therefore, it is clear that the insect repellent and antibacterial film 2 of the present invention has excellent antibacterial activity.

The antibacterial repellent / antibacterial film 2 of the present invention was calculated to have an antibacterial activity value of 3.6 (test bacteria: E. coli (O157: H7)).

Antibacterial activity value (R) = (U _t −U ₀ ) − (A _t −U ₀ ) = U _t −A _t

U ₀ : logarithmic value (average value) of viable cell count (/ cm ² ) for the test bacterial solution of the comparative example immediately after inoculation
U _t : logarithmic value (average value) of viable cell count (/ cm ² ) for the test bacterial solution of the comparative example after culturing (35 ° C., 24 hours)
A _t: After culturing (35 ° C., 24 hours) viable cell count for the test bacterial solution in Example of (/ cm ²⁾ of the logarithmic values (average value)

  The active energy ray-curable composition of the present invention is useful for the production of insect repellent and / or antibacterial films having a layer of a cured product comprising the active energy ray-curable composition. In addition, the film of the present invention obtained as described above can be used for various purposes for insect repellent and / or antibacterial purposes. In particular, by wrapping an object with the film, The object can be insect repellent and / or antibacterial treated. Furthermore, if a highly transparent film is used, the state of the object wrapped with the film can be easily observed and confirmed from the outside, so that the object (for example, food) that needs to be confirmed at any time should be checked. It can be suitably used as a packaging film.

Claims (5)

(A) As an insect repellent and antibacterial active ingredient, extracts of flower buds, walnuts, soyou, peach leaves, chili peppers, peonies, jujuaks, ginger and kujin, and
(B) An active energy ray-curable composition comprising an active energy ray-curable varnish. An insect repellent and / or antibacterial film having a layer of a cured product comprising the active energy ray-curable composition according to claim 1 on at least one surface of the film. The film is made of ABS (acrylonitrile-butadiene-styrene copolymer) resin, polyethylene, polyetherimide, polyethersulfone, polyethylene terephthalate, polybutylene terephthalate, polypropylene, polyvinyl alcohol, polyvinyl acetate, polyvinyl chloride, polyvinylidene chloride. A monolayer film composed of one material selected from polyvinylidene fluoride, polyethersulfone, polycarbonate, polystyrene and nylon, or a multilayer film obtained by laminating the same or different monolayer films. The insect repellent and antibacterial film according to claim 2. An object which has been insect-repellent and / or antibacterial treated, wrapped with the film according to claim 2 or 3. An insect repellent and / or antibacterial method comprising using the film of claim 2 or 3.