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WO2019088199A1 - Matériau antibactérien, et matériau pour maintien de la fraîcheur - Google Patents

Matériau antibactérien, et matériau pour maintien de la fraîcheur Download PDF

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Publication number
WO2019088199A1
WO2019088199A1 PCT/JP2018/040582 JP2018040582W WO2019088199A1 WO 2019088199 A1 WO2019088199 A1 WO 2019088199A1 JP 2018040582 W JP2018040582 W JP 2018040582W WO 2019088199 A1 WO2019088199 A1 WO 2019088199A1
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Prior art keywords
antibacterial
film
surface layer
molecule
material according
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PCT/JP2018/040582
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English (en)
Japanese (ja)
Inventor
中山　勉伸
田中　邦彦
永井　直
森　直樹
清水　正樹
伊東　祐一
Original Assignee
三井化学株式会社
三井化学東セロ株式会社
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Publication of WO2019088199A1 publication Critical patent/WO2019088199A1/fr

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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N63/00—Biocides, pest repellants or attractants, or plant growth regulators containing microorganisms, viruses, microbial fungi, animals or substances produced by, or obtained from, microorganisms, viruses, microbial fungi or animals, e.g. enzymes or fermentates
    • A01N63/50—Isolated enzymes; Isolated proteins
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/34—Shaped forms, e.g. sheets, not provided for in any other sub-group of this main group
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • B65D65/42—Applications of coated or impregnated materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D81/00—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents
    • B65D81/24—Adaptations for preventing deterioration or decay of contents; Applications to the container or packaging material of food preservatives, fungicides, pesticides or animal repellants
    • B65D81/28—Applications of food preservatives, fungicides, pesticides or animal repellants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D85/00—Containers, packaging elements or packages, specially adapted for particular articles or materials
    • B65D85/50—Containers, packaging elements or packages, specially adapted for particular articles or materials for living organisms, articles or materials sensitive to changes of environment or atmospheric conditions, e.g. land animals, birds, fish, water plants, non-aquatic plants, flower bulbs, cut flowers or foliage

Definitions

  • the present disclosure relates to an antimicrobial material and a material for maintaining freshness.
  • Products requiring freshness such as fresh vegetables such as cut vegetables, meat, fresh fish, and processed foods, and processed products, are distributed in bags made of plastic films and the like. These perishable foods and processed products are reduced in their commercial value because when the food rots and bacteria multiply, an offensive odor is generated, the taste is reduced and hygiene problems are caused.
  • various germs multiply more in drips than in meat, fresh fish and processed food bodies (see, for example, Non-Patent Document 1). Therefore, suppressing the growth of bacteria in the drip keeps the atmosphere inside the package clean, and in turn keeps the freshness of cut vegetables, meat, fresh fish and processed food which are to be packaged.
  • Patent Document 1 discloses an antibacterial material using protamine as an antibacterial agent and a processed product thereof.
  • Patent Document 2 discloses an antibacterial agent composition in which (A) ⁇ -polylysine and / or a salt thereof, (B) an electrolyte having a pH buffer capacity, and (C) an amino acid are blended.
  • Patent Document 3 a thin layer (B) containing an ethylene-vinyl alcohol copolymer, a pressure-sensitive adhesive layer (C) containing a chemical, and a protective layer (D) are sequentially laminated on a support layer (A).
  • Patent Document 4 discloses an anionic anticoagulant activity containing a sulfur atom in a cationic polymer containing a compound selected from the group consisting of alkyleneimine, vinylamine, allylamine, lysine, protamine, and diallyldimethyl ammonium chloride as a constituent monomer.
  • An antithrombogenic material is disclosed in which a mesh or the like, which is a substrate, is coated with a coating material in which a compound having an ionic bond is ionically bonded.
  • Patent Document 1 JP-A-8-231327
  • Patent Document 2 JP-A-2004-67586
  • Patent Document 3 JP-A-2017-13309
  • Patent Document 4 International Publication No. 2016/190407
  • Non-patent document 1 Correlation between fish meat bacterial count and drip bacterial count of refrigerated fresh food fresh fish meat (Fukuda Tsubasa, Hoshikawa Naomoto, Tahara Yumiko, Paleo Junk, Shiba Tsuneo, Co-authored)
  • Patent Document 1 and Patent Document 2 disclose that a protamine or an antibacterial agent composition is applied to a container, a film or the like to have an antibacterial effect.
  • Patent Document 1 and Patent Document 2 it is difficult to maintain the antibacterial property and the freshness-keeping property based thereon over a long period of time, and an antibacterial material having higher antibacterial maintenance property is required.
  • Patent Document 3 describes a multilayer laminated film for sticking that prevents scattering of chemical agents
  • Patent Document 4 describes that an anionic compound is ionically bonded to a cationic polymer to be immobilized. There is.
  • these immobilization techniques are applied to an antimicrobial material, there is also a problem that it is difficult to obtain the antimicrobial property itself.
  • This indication is made in view of the above situations, and aims at providing an antibacterial material and a material for maintaining freshness, in which excellent antibacterial properties are maintained over a long period of time.
  • the means for solving the above problems include the following aspects. And at least one structure selected from the group consisting of a structure derived from guanidine, a structure derived from glucosamine, and a structure derived from amino acids, disposed on at least one surface of a ⁇ 1> substrate and the substrate
  • An antibacterial material comprising: a surface layer containing a molecule A having a weight average molecular weight of 500 or more and 10000 or less and a component B comprising a compound other than the molecule A and having a cationic or nonionic property, in the surface layer
  • An antibacterial material wherein the amount of the molecule A per unit area is 0.2 mg / m 2 to 300 mg / m 2 .
  • the antibacterial material as described in ⁇ 1> whose static friction coefficient of the ⁇ 2> above-mentioned surface layer is 0.01 or more and 1.5 or less.
  • the heat seal strength is 3 N / 15 mm when heat fusing is performed under the conditions of a temperature of 140 ° C., a pressure of 0.1 MPa, and a time of 0.5 seconds by bringing the surface layers of the two antibacterial materials into contact with each other.
  • the antimicrobial material as described in ⁇ 1> or ⁇ 2> which is the above.
  • ⁇ 4> The antimicrobial material according to any one of ⁇ 1> to ⁇ 3>, wherein the component B is cationic.
  • ⁇ 5> The antimicrobial material according to ⁇ 4>, wherein the component B comprises a polymer compound and a cationic surfactant other than the polymer compound.
  • ⁇ 6> The antibacterial material according to ⁇ 5>, wherein the weight average molecular weight of the cationic surfactant is 300 to 100,000.
  • ⁇ 7> The antibacterial material according to ⁇ 5> or ⁇ 6>, wherein the weight average molecular weight of the polymer compound is 1,000 to 500,000.
  • ⁇ 8> The antibacterial material according to any one of ⁇ 5> to ⁇ 7>, wherein a content of the cationic surfactant in the component B is 0.1% by mass to 30% by mass.
  • ⁇ 12> The antibacterial material according to any one of ⁇ 1> to ⁇ 11>, wherein the structure derived from guanidine is a structure represented by the following formula (G-1).
  • R 1 to R 4 each independently represent a hydrogen atom or a substituent, and the wavy line portion represents a binding site to another structure.
  • R 1 to R 4 each independently represent a hydrogen atom or a substituent, and the wavy line portion represents a binding site to another structure.
  • the surface layer further includes an antifogging agent A having a polar functional group and having a molecular weight of 100 to 600 and an HLB value of 8 or less, and the antifogging agent A per unit area in the surface layer
  • the antimicrobial material according to any one of ⁇ 1> to ⁇ 14>, wherein the amount is 0.25 mg / m 2 to 50 mg / m 2 .
  • the antibacterial material as described in ⁇ 15> whose equivalent of the polar functional group in ⁇ 16> said antifogging agent A is 20 g / eq-500 g / eq.
  • the surface layer further comprises an antifogging agent B having a polar functional group and having a molecular weight of 100 to 600 and an HLB value of more than 8.
  • the substrate is a polymer film containing at least one polymer selected from the group consisting of polyethylene, polypropylene, polymethylpentene, and polyethylene terephthalate Antibacterial material described in.
  • the substrate is a container-shaped molded article containing at least one polymer selected from the group consisting of polyethylene, polypropylene, polymethylpentene, and polyethylene terephthalate Antibacterial material according to one.
  • ⁇ 20> A material for maintaining freshness comprising the antibacterial material according to any one of ⁇ 1> to ⁇ 19>.
  • ⁇ 21> The material for maintaining freshness according to ⁇ 20>, which is used for packaging an article.
  • ⁇ 22> The material for maintaining freshness according to ⁇ 21>, wherein the surface layer of the antibacterial material is a surface facing the article.
  • an antibacterial material and a material for maintaining freshness in which excellent antibacterial properties are maintained over a long period of time.
  • FIG. 1 is a graph showing the daily change of the antimicrobial activity of the films for preserving freshness (antimicrobial material) of Example 1 and Comparative Example 1.
  • FIG. 2 is a graph showing the daily change of the surface amount of the molecule A in the films for preserving freshness (antibacterial material) of Example 1 and Comparative Example 1.
  • FIG. 3 is a schematic plan view showing an example of a part-coated packaging laminate film.
  • FIG. 4 is a schematic view showing an example of a three-way seal bag formed using the packaging laminated film shown in FIG.
  • a numerical range represented using “to” means a range including numerical values described before and after “to” as the lower limit value and the upper limit value.
  • the “film” is not only generally referred to as “film” (for example, having a thickness of 100 ⁇ m or less) but also generally referred to as “sheet” For example, it is a concept that also includes those having a thickness of 100 ⁇ m or more.
  • the term "process” is included in the term if the intended purpose of the process is achieved, even if it is not only an independent process but can not be clearly distinguished from other processes.
  • the antimicrobial material of the present embodiment comprises a substrate and a surface layer disposed on at least one surface of the substrate.
  • the surface layer has at least one structure selected from the group consisting of a structure derived from guanidine, a structure derived from glucosamine, and a structure derived from an amino acid, and a molecule A having a weight average molecular weight of 500 or more and 10000 or less A cationic or nonionic component B comprising a compound other than the molecule A, and the amount of the molecule A per unit area in the surface layer is 0.2 mg / m 2 to 300 mg / m 2 .
  • the heat seal strength is 3 N / 15 mm or more when heat fusion is performed under the conditions of temperature 140 ° C., pressure 0.1 MPa and time 0.5 seconds by bringing the surface layers of the two antibacterial materials into contact with each other. .
  • the article is kept clean for a long period of time, and particularly when the article is a food, the freshness of the food is maintained.
  • drips from the fresh food are likely to adhere to the inner surface of the package.
  • condensation occurs due to condensation due to condensation caused by respiration.
  • the proportion of drips eluted from the cross section is large, but especially when thawed from the frozen state, the cell wall is broken due to water expansion during freezing, so the amount of drips increases. Although this drip contains many nutrients, it is not protected by the cell wall as per fresh food itself, so it is easy for bacteria to grow. That is, the drip is considered to be the most perishable inside the package.
  • the antimicrobial material in which the molecule A having the antimicrobial effect is simply attached to the surface of the base material, although the antimicrobial effect is obtained initially, for example, the molecule A dissolves in the drip from the fresh food and the molecule A is The antimicrobial effect may decrease with time due to detachment from the surface of the material.
  • the molecule A is immobilized on the polymer using, for example, a polymer which strongly ionically bonds with the molecule A, although the detachment of the molecule A is suppressed, it is difficult to obtain the antimicrobial effect itself from the beginning There is.
  • the cationic molecule A and the adhesive cationic or nonionic component B are used. Therefore, the molecule A is less likely to be detached as compared with the case where the molecule A is simply attached to the surface of the substrate, and the sustained release of the molecule A is obtained as compared with the case of using a polymer which ionically bonds with the molecule A. Cheap. Thereby, an antimicrobial effect is obtained from the beginning, and the antimicrobial effect is likely to be sustained. Therefore, according to the antibacterial material of the present embodiment, even when used for a package for packaging fresh food as described above, the effect of suppressing the growth of bacteria in the drip in contact with the inner surface of the package can be obtained. And, the effect lasts for a long time.
  • the amount of molecule A per unit area in the surface layer (hereinafter, also referred to as" surface amount of molecule A ”) means the surface amount of molecule A when converted to the amount per 1 m 2 of area . Therefore, the area of the surface layer is not necessarily limited to 1 m 2 or more.
  • the “surface amount of molecule A” of the antibacterial material can be measured from the antibacterial material by infrared spectroscopy (ATR-IR method) according to the following total reflection attenuation method.
  • ATR-IR method by total reflection attenuation method- A portion of the antibacterial material is cut out and a sample for measurement is prepared. For the measurement sample, the peak intensity derived from the molecule A is measured by the ATR-IR method. Since there is a correlation between the surface amount of the molecule A and the above peak intensity, the concentration of the molecule A in the coating solution, the amount of the coating solution, etc. are changed to form coating films of various molecule A concentrations on the substrate. By measuring the peak intensity in advance, the surface amount (mg / m 2 ) of the molecule A can be calculated from the peak intensity.
  • heat seal strength (hereinafter referred to as“ surface layer of the surface layer when heat fusing is performed under the conditions of a temperature of 140 ° C., a pressure of 0.1 MPa, and a time of 0.5 seconds by bringing the surface layers of two antibacterial materials into contact with each other The heat seal strength is also referred to as ”)" is measured as follows. Specifically, two pieces of the antibacterial material cut into strips are prepared as test pieces. Next, two prepared test pieces are stacked so that the surface layers face each other, and then a heat seal tester (heat gradient heat seal tester TP-701-G, Tester Sangyo Co., Ltd.) is used.
  • TP-701-G Tester Sangyo Co., Ltd.
  • Heat seal is performed under the conditions of temperature (heat seal temperature, upper portion only) 140 ° C., seal width 10 mm, seal pressure 0.1 MPa, and seal time 0.5 seconds.
  • the heat-fused film is taken out of the tester and cut into a width of 15 mm.
  • This heat-sealed film having a width of 15 mm was heat-sealed using a seal strength tester (force gauge FPG, Nidec Lampo Co., Ltd.) under conditions of a tensile speed of 30 mm / min and a temperature of 23 ° C. Is pulled in the direction of 90 ° with respect to the heat-sealed surface of the sheet to peel, and the maximum value of the peel strength is measured. And let this maximum value be the above-mentioned "heat seal strength (unit: N / 15 mm) of a surface layer".
  • the surface layer has at least one structure selected from the group consisting of a structure derived from guanidine, a structure derived from glucosamine, and a structure derived from an amino acid, and a molecule A having a weight average molecular weight of 500 or more and 10000 or less; And B, a compound which is a compound other than the molecule A.
  • the surface layer is in contact with at least a part of the substrate to be described later, preferably in contact with at least a part of the surface of the substrate.
  • the molecule A is an antibacterial compound having at least one structure selected from the group consisting of a structure derived from guanidine, a structure derived from glucosamine, and a structure derived from an amino acid.
  • the molecule A may be a compound having any one of a structure derived from guanidine, a structure derived from glucosamine, and a structure derived from an amino acid, and is a compound having two or more of these structures. May be
  • the molecule A is preferably at least one compound selected from the group consisting of a compound having a structure derived from guanidine, a compound having a structure derived from glucosamine, and a compound having a structure derived from lysine.
  • a compound having a structure derived from guanidine, a compound having a structure derived from glucosamine, and a compound having a structure derived from lysine are respectively described.
  • -A compound having a structure derived from guanidine- The structure derived from guanidine is not particularly limited, and for example, a structure represented by the following formula (G-1) is preferable.
  • R 1 to R 4 each independently represent a hydrogen atom or a substituent, and the wavy line portion represents a binding site to another structure.
  • R 1 to R 4 contained in Formula (G-1) are preferably each independently a hydrogen atom or an alkyl group from the viewpoint of antibacterial activity, and it is more preferable that all of them be a hydrogen atom.
  • the alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and still more preferably a methyl group.
  • the compound having a structure derived from guanidine is preferably a compound having a structure derived from guanidine and a structure derived from an amino acid, and more preferably a compound having an amino acid having a structure derived from guanidine, arginine More preferably, it is a compound having a derived structure, and particularly preferably a peptide containing a structural unit derived from arginine.
  • the arginine may be arginine having a known substituent, but is preferably unsubstituted arginine.
  • the structure derived from arginine and the structural unit derived from arginine include structures derived from guanidine.
  • an amino acid refers to a compound having an amino group (—NH 2 ) and a carboxy group (—COOH) in one molecule.
  • a peptide refers to a compound in which 2 to 100 amino acid molecules are linked by a peptide bond.
  • the compound having a structure derived from guanidine preferably contains at least one of protamine and a salt of protamine (hereinafter also referred to as “protamine etc.”), and more preferably contains a salt of protamine.
  • the compound having a structure derived from guanidine may be at least one of protamine and a salt of protamine, and preferably a salt of protamine.
  • protamine and the like there is no particular limitation on protamine and the like, and a basic protein obtained by hydrolyzing a nuclear protein present in testis of fish, birds, mammals and the like to DNA and protein; protamine obtained by further hydrolyzing the basic protein; Salt of Examples of salts of protamine include inorganic salts such as hydrochloride, sulfate and phosphate; and organic salts such as acetate, propionate and gluconate.
  • Salt of Examples of salts of protamine include inorganic salts such as hydrochloride, sulfate and phosphate; and organic salts such as acetate, propionate and gluconate.
  • Protamine etc. may be used individually by 1 type, and may use 2 or more types together.
  • protamine etc. may be a commercial item.
  • compounds having a structure derived from glucosamine include chitosan and salts of chitosan, with chitosan being more preferred.
  • chitosan at least one of chitosan and a salt of chitosan may be referred to as "chitosan etc.”
  • salts of chitosan include inorganic salts such as hydrochloride, sulfate and phosphate; and organic salts such as acetate, propionate and gluconate.
  • the chitosan and the like are not particularly limited, and for example, chitin (poly- ⁇ 1-4-N-acetylglucosamine) obtained from the exoskeleton of crustaceans such as crab and shrimp is deacetylated by boiling treatment in concentrated alkali or the like. And salts thereof.
  • the chitosan and the like may be used alone or in combination of two.
  • chitosan etc. may be a commercial item.
  • polylysine and salts of polylysine include polylysine and salts of polylysine, with polylysine being preferred.
  • polylysine salts include inorganic salts such as hydrochloride, sulfate and phosphate; and organic salts such as acetate, propionate and gluconate.
  • polylysine etc. there is no particular limitation on polylysine etc.
  • ⁇ -polylysine ⁇ -poly-L-lysine
  • ⁇ -polylysine produced by chemical synthesis ⁇ -poly-L-lysine, ⁇ - Poly-D-lysine
  • salts thereof It is preferable to select these polylysine etc. according to a use.
  • Polylysine etc. may be used individually by 1 type, and may use 2 types together.
  • polylysine etc. may be a commercial item.
  • molecule A only one type or two or more types of compounds having at least one structure selected from the group consisting of a structure derived from guanidine, a structure derived from glucosamine, and a structure derived from an amino acid may be used. Good.
  • the weight average molecular weight (Mw) of the molecule A is 500 or more and 10000 or less, preferably 1000 or more and 9000 or less, more preferably 2000 or more and 8000 or less, and still more preferably 3000 or more and 7000 or less from the viewpoint of antibacterial activity and antibacterial maintenance. .
  • the measurement of the said molecular weight and molecular weight distribution is performed on condition of the following using GPC (gel permeation chromatography) method.
  • the amount of molecule A per unit area in the surface layer is preferably 0.2 mg / m 2 to 300 mg / m 2 , and 0.3 mg / m 2 to 200 mg / m 2 from the viewpoint of enhancing the antibacterial property and the antibacterial maintenance property.
  • m 2 is more preferable, 0.6 mg / m 2 to 150 mg / m 2 is more preferable, 0.9 mg / m 2 to 50 mg / m 2 is particularly preferable, and 1.0 mg / m 2 More preferably, it is 2 to 30 mg / m 2 .
  • the “surface amount of the molecules A” refers to the total of these surface amounts.
  • content of the molecule A in a surface layer 0.01 mass% or more and 50 mass% or less are mentioned with respect to the whole surface layer, for example, and 0.05 mass% or more and 30 mass% or less from an antimicrobial maintenance viewpoint. Is preferably 0.1% by mass to 10% by mass.
  • the content of the molecule A in the surface layer is 0.01% by mass to 70% by mass with respect to the total content of the molecule A and the component B, and from the viewpoint of antibacterial maintenance property, 0.05% by mass or more and 50%.
  • the mass% or less is preferable, and 0.1 mass% or more and 20 mass% or less is more preferable.
  • the equivalent of the basic group in the molecule A is preferably 50 g / eq to 500 g / eq, more preferably 80 g / eq to 350 g / eq, and still more preferably 100 g / eq to 250 g / eq.
  • the "basic group” refers to a functional group having a pKa of 11 to 14 in the conjugate acid calculated by ACD pKa DB ver. 12.2.0, and examples thereof include an amino group contained in a structure derived from the guanidine.
  • the equivalent of the basic group in the molecule A refers to the mass of the molecule A relative to one molar amount of the basic group. The equivalent of the basic group is calculated by conducting structural analysis of the molecule A.
  • the component B is made of a compound other than the molecule A, and is not particularly limited as long as it is cationic or nonionic. Among them, a cationic component is preferable, and a cationic pressure-sensitive adhesive is more preferable.
  • a component B consisting of a polymer compound having a basic group in addition to a component B consisting of a polymer compound and a cationic surfactant (hereinafter also referred to as “component B-1”) (Hereinafter also referred to as “component B-2”).
  • nonionic component B for example, in addition to the component B (hereinafter also referred to as “component B-3”) consisting of a nonionic polymer compound and a nonionic surfactant, a nonionic polymer
  • component B-3 a nonionic polymer compound
  • component B-4 a compound
  • Examples of the polymer compound constituting Component B-1 include non-ionic polymer compounds.
  • the non-ionic polymer compound includes, in addition to a polymer compound having no ionic group, a polymer compound which is nonionic as the whole polymer compound even if it has an ionic group. If the component B-1 as a whole is cationic, the polymer compound constituting the component B-1 may be an ionic (anionic or cationic) polymer compound.
  • Specific examples of the polymer compound constituting Component B-1 include, for example, polyolefin resins.
  • polyolefin resins examples include ethylene / vinyl acetate copolymer, ethylene / acrylic acid copolymer, ethylene / methacrylic acid copolymer, ethylene / vinyl alcohol copolymer, etc., among which ethylene / vinyl acetate Copolymers are preferred.
  • the weight average molecular weight (Mw) of the polymer compound constituting Component B-1 is, for example, 500 to 500,000, preferably 1000 to 500,000, and more preferably 5,000 to 200,000 from the viewpoint of sustained release of the molecule A. And 10000 to 150000 are more preferable.
  • the measurement of the molecular weight of the polymer compound constituting Component B-1 is carried out by the same method as the measurement of the molecular weight of the above-mentioned protamine or the like.
  • the surfactant which has a nitrogen atom is mentioned, for example, Specifically, for example, an amine salt, a quaternary ammonium salt, a pyridinium salt, an imidazolinium salt Etc.
  • the cationic surfactant constituting the component B-1 is preferably a cationic surfactant having a molecular weight of 100 or more (hereinafter, also referred to as "polymeric cationic surfactant").
  • the weight-average molecular weight (Mw) of the high-molecular weight cationic surfactant is, for example, 300 to 100000.
  • the measurement of the molecular weight in a polymeric cationic surfactant is performed by the method similar to the measurement of the molecular weight in the said protamine etc.
  • high molecular weight cationic surfactants include aminoethylated acrylic polymers, and polyacrylic acid (2-aminoethyl), methyl acrylate-acrylic acid (2-aminoethyl) copolymer, Polyacrylic acid (polyethylenimine), methyl acrylate-acrylic acid (polyethyleneimine) copolymer, polymethacrylic acid (2-aminoethyl), methyl methacrylate-methacrylic acid (2-aminoethyl) copolymer, polymethacrylic acid Examples thereof include acid (polyethyleneimine) and methyl methacrylate-methacrylic acid (polyethyleneimine) copolymer.
  • the content of the cationic surfactant with respect to the entire component B-1 is, for example, 0.1% by mass to 30% by mass, preferably 0.1% by mass to 10% by mass, and the sustained release of the molecule A From the viewpoint, 0.3% by mass to 5% by mass is more preferable, and 0.5% by mass to 3% by mass is more preferable.
  • the polymer compound constituting Component B-1 and the cationic surfactant constituting Component B-1 are chemically
  • a polymer of a compound having a nitrogen atom, a copolymer of a compound having a nitrogen atom and another compound, and the like can be mentioned.
  • the compound having a nitrogen atom include a compound having an amino group, an amine salt, a quaternary ammonium salt, a compound having a cyclic structure having a nitrogen atom such as a pyridine skeleton or an imidazole skeleton, or a salt thereof.
  • Other compounds include, for example, styrene, vinyl naphthalene, butadiene, isoprene, ethylene, propylene, alkyl esters of acrylic acid, alkyl esters of methacrylic acid, and derivatives thereof.
  • the equivalent of the basic group in the “polymer compound having a basic group” constituting Component B-2 is, for example, 50 g / eq to 500 g / eq, and from the viewpoint of sustained release of molecule A, 80 g / g. It is preferably in the range of eq to 350 g / eq, and more preferably in the range of 100 g / eq to 250 g / eq.
  • the equivalent weight of the basic group in the “polymer compound having a basic group” constituting Component B-2 is calculated by conducting structural analysis of Component B.
  • the weight average molecular weight (Mw) of the “polymer compound having a basic group” constituting Component B-2 is preferably over 10000, and from the viewpoint of sustained release of the molecule A, 10000 or more and 500000 or less is more preferable
  • the number is more preferably 15,000 to 300,000, and particularly preferably 20,000 to 200,000.
  • the measurement of the molecular weight and molecular weight distribution of the “polymer compound having a basic group” constituting Component B-2 is carried out by the same method as the measurement of the molecular weight and molecular weight distribution of the above-mentioned protamine or the like.
  • the preferable weight average molecular weight of the “nonionic polymer compound” constituting Component B-3 is also the same as the preferable weight average molecular weight of the polymer compound constituting Component B-1.
  • the nonionic surfactant constituting Component B-3 is not particularly limited, and examples thereof include alkyl ethers such as polyoxyethylene alkyl ether, and alkyl benzene ethers such as polyoxyethylene nonylpropenyl phenyl ether.
  • nonionic surfactant for example, 250 to 1000 can be mentioned.
  • nonionic polymer compound for example, a nonionic polymer compound constituting Component B-3, and a nonionic surfactant constituting Component B-3 And the like.
  • the preferred weight average molecular weight of the "nonionic polymer compound” constituting Component B-4 is the same as the preferred weight average molecular weight of the "polymer compound having a basic group" constituting Component B-2.
  • Component B is preferably a component whose viscosity is reduced by receiving shear stress. Specifically, when the coating liquid is applied to the base material in the process of forming the surface layer, the coating liquid is subjected to shear stress, but the coating liquid receives the shear stress (hereinafter also referred to as “shear stress during application”) It is preferable that the viscosity of the component B contained therein is lower than the viscosity of the component B in the surface layer.
  • component B in a surface layer As content of component B in a surface layer, 50 mass% or more and 99.9 mass% or less are mentioned to the whole surface layer, for example, and 70 mass% or more 99.5 mass% or less is preferable from an antimicrobial maintenance viewpoint. 90 mass% or more and 99 mass% or less are more preferable.
  • the total content of the molecule A and the component B in the surface layer is preferably 90% by mass or more, more preferably 95% by mass or more, and still more preferably 98% by mass or more with respect to the entire surface layer.
  • the surface layer may contain other components other than the molecule A and the component B, as long as the object of the present disclosure is not impaired.
  • Other components include, for example, water-soluble resins such as polyethylene glycol, polyethylene oxide, mono or diglyceride, polyvinyl alcohol (PVA), etc .; antibacterial agents other than the molecule A; other additives;
  • the other components may be used alone or in combination of two or more.
  • the surface layer may further contain an antifogging agent in order to further improve the antifogging property.
  • the antifogging agent is not particularly limited, and examples thereof include nonionic, cationic, anionic and amphoteric antifogging agents, and examples thereof include nonionic, cationic, anionic and amphoteric surfactants.
  • Examples of the antifogging agent include, for example, alkyl diethanolamine, alkyl diethanolamine fatty acid ester, glycerin fatty acid ester, polyglycerin fatty acid ester, sorbitan fatty acid ester, sucrose fatty acid ester and the like.
  • antifogging agent A the antifogging agent
  • the polar functional group is a functional group containing a hetero atom (eg, an oxygen atom, a nitrogen atom, a sulfur atom, etc.), and for example, a hydroxyl group, an acyl group, an acetyl group, a formyl group, a benzoyl group, a carboxy group, a carboxylic acid amide And thioamide, imide, amidine, sulfide, disulfide, sulfenic acid, isonitrile, carbonyl group, amino group, imino group, cyano group, cyano group, azo group, azi group, thiol group, sulfo group, nitro group and the like. Hydroxyl is preferred.
  • a hetero atom eg, an oxygen atom, a nitrogen atom, a sulfur atom, etc.
  • the equivalent weight of the polar functional group in the antifogging agent A is preferably 20 g / eq to 500 g / eq, more preferably 20 g / eq to 350 g / eq, and 20 g / eq to 250 g / eq. More preferable.
  • the equivalent of the polar functional group in the antifogging agent A means the mass of the antifogging agent A with respect to the said polar functional group of 1 molar amount.
  • the molecular weight of the antifogging agent A is preferably 100 to 600, more preferably 100 to 400, and still more preferably 200 to 400.
  • the HLB value of the antifogging agent A is preferably 8 to 1, more preferably 7 to 1, and still more preferably 7 to 3.
  • the above-mentioned HLB value is a numerical value showing the balance of hydrophilicity and hydrophobicity, and when HLB value is low, lipophilicity increases and it becomes difficult to dissolve in water, conversely, when HLB value becomes high, hydrophilicity increases and it dissolves in water It will be.
  • antifogging agent A examples include, for example, stearyl diethanolamine, glycerin fatty acid ester, sorbitan fatty acid ester and the like.
  • the surface layer may contain only one type of antifogging agent A, or may contain two or more types.
  • the content of the antifogging agent A is, for example, 0.01% by mass or more and 20% by mass or less with respect to the entire surface layer, and from the viewpoint of antifogging improvement 0.1 mass% or more and 10 mass% or less are preferable, 0.1 mass% or more and 7 mass% or less are more preferable.
  • the amount of antifogging agent A per unit area in the surface layer is preferably 0.25 mg / m 2 to 1000 mg / m 2 , and 0.25 mg / m 2 to 100 mg / M 2 is more preferable, and 1 mg / m 2 to 60 mg / m 2 is more preferable.
  • the amount of anti-fogging agent A per unit area in the surface layer from the viewpoint of improving the antifogging property of the surface layer containing the molecule A and component B, 0.25mg / m 2 ⁇ 50mg / m 2 is Preferably, 0.25 mg / m 2 to 20 mg / m 2 is more preferable, and 1 mg / m 2 to 20 mg / m 2 is further preferable.
  • the surface layer has a polar functional group and has a molecular weight of 100 to 600 and an HLB value from the viewpoint of further improving the antifogging property of the surface layer containing the molecule A and the component B in addition to the antifogging agent A. It may further contain more than 8 anti-fogging agents (hereinafter also referred to as "anti-fogging agent B"). About the polar functional group which the antifogging agent B has, it is the same as that of the polar functional group which the said antifogging agent A has.
  • the equivalent weight of the polar functional group in the antifogging agent B is preferably 20 g / eq to 500 g / eq, more preferably 20 g / eq to 350 g / eq, and 20 g / eq to 250 g / eq. More preferable.
  • the molecular weight of the antifogging agent B is preferably 100 to 600, more preferably 200 to 600, and still more preferably 200 to 400.
  • the HLB value of the antifogging agent B is preferably more than 8 and 20 or less, more preferably 9 to 20, and still more preferably 10 to 20.
  • antifogging agent B examples include diglycerin monolaurate, diglycerin monooleate, sucrose laurate and the like.
  • anti-fog agent B examples include RIKEN A (sucrose laurate ester) made by Riken Vitamin Co., Ltd., POEM DL-100 (diglycerin monolaurate), POEM DO-100V (diglycerin mono), for example Oleate) etc.
  • the surface layer may contain only one type of antifogging agent B, or may contain two or more types.
  • the total content of the antifogging agent A and the antifogging agent B is, for example, 0.01% by mass or more and 20% by mass with respect to the entire surface layer. % Or less is mentioned, and from a viewpoint of antifogging improvement, 0.1 mass% or more and 10 mass% or less are preferable, 0.1 mass% or more and 7 mass% or less are more preferable.
  • the total amount of the antifogging agent A and the antifogging agent B per unit area in the surface layer is 0.25 mg / m 2 to 1000 mg / m 2 is preferable, 0.25 mg / m 2 to 100 mg / m 2 is more preferable, 1 mg / m 2 to 60 mg / m 2 is more preferable, 1 mg / m 2 to 50 mg / m 2 is particularly preferable, 1 mg / m 2 -20 mg / m 2 is very particularly preferred.
  • the amount of the antifogging agent B with respect to 100 parts by mass of the antifogging agent A may be, for example, 50 parts by mass to 1000 parts by mass. From the viewpoint of antifogging improvement, 50 parts by mass or more and 500 parts by mass or less are preferable, and 50 parts by mass or more and 400 parts by mass or less are more preferable.
  • the antimicrobial material comprises a substrate.
  • the substrate is in contact with the surface layer described above, and at least a portion of the surface of the substrate is in contact with the surface layer described above.
  • the substrate preferably contains a polymer compound (hereinafter also referred to as “polymer”).
  • the polymer is not particularly limited, but, for example, polyolefins such as polyethylene, polypropylene, polymethylpentene, polyethylene terephthalate (hereinafter also referred to as "PET"), ethylene propylene copolymer, polyethylene naphthalate, polybutylene terephthalate, cellophane Rayon, polystyrene, polycarbonate, polyimide, polyamide, polyacryl, polysulfone, polyether, polyurethane, cellulose.
  • PET polyethylene terephthalate
  • polyethylene propylene copolymer polyethylene naphthalate
  • polybutylene terephthalate cellophane Rayon
  • polystyrene polycarbonate
  • polyimide polyamide
  • polyacryl polysulfone
  • polyether polyurethane
  • cellulose polyurethane
  • polyethylene for example, low density polyethylene, medium density polyethylene, high density polyethylene, high pressure low density polyethylene produced by a conventionally known method can be used.
  • polypropylene examples include isotactic polypropylene and syndiotactic polypropylene.
  • the isotactic polypropylene may be a homopolypropylene, a propylene / C-C20 ⁇ -olefin (but excluding propylene) random copolymer, or a propylene block copolymer.
  • polymethylpentenes examples include homopolymers of 4-methyl-1-pentene; structural units derived from 4-methyl-1-pentene, and ⁇ -olefins having 2 to 20 carbon atoms Copolymers having a structural unit derived from -1-pentene).
  • polyamide examples include polyamide obtained by condensation polymerization of dicarboxylic acid and diamine, and polyamide obtained by ring-opening polymerization of lactam.
  • PET Polyethylene terephthalate
  • PET polyethylene terephthalate
  • PET non-crystalline polyethylene terephthalate
  • A-PET is preferable from the viewpoint of formability into a container shape or the like.
  • the substrate may contain other components other than the polymer, as long as the object of the present disclosure is not impaired.
  • Other components include, for example, dispersants, heat stabilizers, weather stabilizers, ultraviolet absorbers, lubricants, slip agents, nucleating agents, antiblocking agents, antistatic agents, antifogging agents, pigments and dyes.
  • the other components may be used alone or in combination of two or more.
  • the content of the other components is preferably 20% by mass or less, more preferably 10% by mass or less, and still more preferably 5% by mass or less based on 100% by mass of the total amount of the antibacterial material. .
  • the substrate is preferably subjected to surface treatment on the portion in contact with the surface layer.
  • the surface treatment is not particularly limited as long as the adhesion between the substrate and the surface layer can be enhanced.
  • corona treatment, itro treatment, ozone treatment, ultraviolet treatment, chemical treatment, high frequency treatment, glow Discharge treatment, plasma treatment, laser treatment and the like can be mentioned.
  • the surface treatment degree of the substrate is preferably 35 dyne or more, more preferably 36 dyne or more, and still more preferably 38 dyne or more from the viewpoint of enhancing the fixability of the surface layer to the substrate .
  • the surface treatment degree of the substrate may be 40 dynes or less.
  • the substrate may be a film (polymer film) containing the aforementioned polymer, preferably at least one polymer selected from the group consisting of polyethylene, polypropylene, polymethylpentene, polyamide, and polyethylene terephthalate.
  • the substrate may be a container-shaped molded article containing the above-described polymer, preferably at least one polymer selected from the group consisting of polyethylene, polypropylene, polymethylpentene, polyamide, and polyethylene terephthalate. Good.
  • the substrate is a container-shaped molded article, the substrate more preferably comprises polyethylene terephthalate (PET).
  • the heat seal strength of the surface layer in the antibacterial material (that is, the heat seal strength when the surface layers are brought into contact with each other and heat-fused) is 3 N / 15 mm or more, preferably 3 N / 15 mm to 8 N / 15 mm, 3N / 15 mm or more and 6N / 15 mm or less are more preferable.
  • the thickness of the surface layer in the antibacterial material is, for example, 0.1 ⁇ m to 5 ⁇ m, preferably 0.3 ⁇ m to 4 ⁇ m, and more preferably 0.5 ⁇ m to 3 ⁇ m.
  • the tackiness of the surface layer represented by the coefficient of static friction in the antibacterial material is preferably 0.01 to 1.5 from the viewpoint of handleability, preferably 0.03 to 1.5 It is more preferably 1.0, and particularly preferably 0.05 to 0.8.
  • the coefficient of static friction of the surface layer was measured by bringing the surface layers of the antibacterial material into contact with each other using a friction measuring device TR-2 manufactured by Toyo Seiki Seisakusho Co., Ltd. as a measuring device according to JIS K7125.
  • an antibacterial film using a polymer film hereinafter, also referred to as a “substrate film”
  • a substrate film an antibacterial using a molded body as a substrate
  • an antibacterial non-woven fabric using a non-woven fabric as a base material.
  • the antimicrobial film examples include packaging films, packaging laminate films, and molding films.
  • the antibacterial film may be a non-stretched film, a uniaxial or biaxial stretched film, or may be a single layer or a plurality of layers (multilayer).
  • a base material is a base film.
  • the polymer contained in the base film (base material) include the polymers exemplified above, and among them, at least one selected from the group consisting of polyethylene, polypropylene, polymethylpentene, polyamide, and polyethylene terephthalate. Polymers are preferred.
  • the substrate film comprises at least one polymer selected from the group consisting of polyethylene, polypropylene, polymethylpentene, polyamide, and polyethylene terephthalate (PET). preferable.
  • the base film preferably contains polyethylene terephthalate (PET) from the viewpoint of formability into a container shape or the like. These polymers may be used alone or in combination of two or more.
  • the thickness of the packaging film is preferably 15 ⁇ m to 200 ⁇ m, more preferably 20 ⁇ m to 120 ⁇ m, and still more preferably 25 ⁇ m to 100 ⁇ m.
  • the packaging laminate film may be, for example, a base film A, a seal layer disposed on the base film A, and a seal layer disposed on the seal layer. And a surface layer containing the molecule A and the component B.
  • the base film A and the seal layer correspond to the base (base film).
  • the base film A and the seal layer may each be a single layer or a multilayer.
  • the thickness ratio of the base film A is preferably 10% to 90%, more preferably 20% to 85%, based on the thickness of the entire antibacterial film.
  • the thickness of the seal layer is preferably 0.5 ⁇ m to 50 ⁇ m, more preferably 1 ⁇ m to 30 ⁇ m, and still more preferably 1.5 ⁇ m to 20 ⁇ m.
  • a surface layer be the opposite surface to the article (preferably fresh food).
  • the antimicrobial film is a packaging laminate film comprising a base film A, a sealing layer, and a surface layer in this order
  • the surface layer may be provided on at least a part of the surface of the sealing layer, and It may be provided on the entire surface.
  • the seal layer is not provided on the area (peripheral part etc.) to be heat sealed at the time of laminating And the like.
  • the seal layer may be exposed without providing a surface layer in the folding area in addition to the outer peripheral part.
  • the laminate film for packaging 10 shown in FIG. 3 has a base film A12, a seal layer 14 provided on one surface of the base film A12, and a surface of the seal layer 14 opposite to the base film A12 (hereinafter It is comprised by the surface layer 16 provided in a part (2 places) of surface layer coating surface (it is also called “surface layer coating surface”).
  • the surface layer 16 is not provided in the outer peripheral portion and the bending region along the bending line M in the surface layer coated surface of the sealing layer 14, and the state where the sealing layer 14 is exposed It has become.
  • the heat seal part 22 is formed in three directions, and the three-way seal bag 20 having the opening 24 is obtained.
  • the surface layer 16 is provided in the region other than the opening 24 in the inner surface.
  • the thickness of the film for molding is preferably selected according to the application of the molded article.
  • the thickness of the film for vacuum forming is preferably 50 ⁇ m to 800 ⁇ m, more preferably 100 ⁇ m to 700 ⁇ m, and still more preferably 200 ⁇ m to 600 ⁇ m.
  • a base film of a film for vacuum forming a base film (a film containing PET (preferably a PET film)) of the embodiment (2) described later is preferable.
  • the surface layer is preferably the inner surface of the container after container formation. That is, it is preferable that the surface layer be the opposite surface to the article (preferably fresh food).
  • Preferred embodiments of the base film in the case where the antibacterial film is a container-forming film include, for example, the following embodiments (1) to (3).
  • the substrate film comprises at least one polymer selected from the group consisting of polyethylene, polypropylene, polyamide and polymethylpentene, and a film (preferably a PET film) comprising PET is laminated on the substrate film side Aspect.
  • the film (especially PET film) containing PET is especially excellent in the moldability to a container shape etc. by bonding.
  • the substrate film contains PET (preferably a PET film).
  • the substrate film of the aspect of the above (2) is particularly excellent in the formability to the container shape and the like, and in particular to the formability to the container shape by vacuum (pressured) forming.
  • molding provided with the base film of the aspect of said (2) apply
  • a film preferably a PET film
  • the formability to a container shape etc. is especially excellent.
  • the antimicrobial molded article is not particularly limited, and examples thereof include container-shaped molded articles; molded articles of parts such as ROBODS and automobiles.
  • the substrate is preferably a molded article (container-shaped molded article, part-shaped molded article, etc.).
  • the polymer contained in the molded body (base material) include the polymers exemplified above, and among them, at least one kind of polymer selected from the group consisting of polyethylene, polypropylene, polymethylpentene, polyamide and polyethylene terephthalate. Molecules are preferred, and polyethylene terephthalate is more preferred.
  • a container-shaped molded product can be obtained by molding the above-described molding film into a container-shaped molded product.
  • molding for the container-shaped molded object the film for shaping
  • a container-shaped molded product is formed on a substrate film (molded product) obtained by molding a coating liquid containing molecules A and components B into a container shape after molding the base film of the molding film into a container shape. It can also be obtained by
  • the base material of the antimicrobial molded article may be a commercially available product.
  • the antibacterial non-woven fabric is not particularly limited, and examples thereof include an antibacterial non-woven fabric (non-woven fabric for drip sheet) used as a drip sheet, an antibacterial non-woven fabric used as a mask, an air filter and the like.
  • an antimicrobial nonwoven fabric may be comprised by multiple layers (multilayer).
  • the base material is a non-woven fabric and the base material (non-woven fabric) contains a polymer composed of fibers.
  • a polymer contained in a nonwoven fabric the thing similar to the polymer illustrated above is mentioned.
  • the thickness of the nonwoven fabric for drip sheet is preferably 50 ⁇ m to 800 ⁇ m, more preferably 100 ⁇ m to 700 ⁇ m, and still more preferably 200 ⁇ m to 600 ⁇ m.
  • the surface layer containing the molecule A and the component B may be formed on any surface of the nonwoven fabric for drip sheet.
  • the antimicrobial material of this embodiment includes, for example, tapes, adhesive tapes, masking tapes, masking films, temporary adhesive films, plastic envelopes, easy open packaging bags, automatic packaging films, shopping bags, standing bags, transparent packaging boxes, building materials , Films for bonding, films for agriculture, materials for maintaining freshness (food packaging materials, vegetable packaging materials, fruit packaging materials, meat packaging materials, fish packaging materials such as fishery products, fishery products such as seafood products, processed food packaging materials, etc .; Materials; Containers for foods, vegetables (cut vegetables, etc.), fruits, meat, fish products, processed foods, etc .; Containers for buckwheat noodles, noodles, lunch boxes, etc.), electronic parts packaging materials, machine parts packaging materials, grain packaging materials, medical films , Medical tapes, cell culture packs, etc.
  • the antibacterial material is an antibacterial non-woven fabric, it can also be used for filters (air conditioning, automobiles, home appliances etc.), food mats, masks, seat covers for seats, table cloths, carpet
  • the antibacterial material of this embodiment has high antibacterial properties, for example, an antibacterial material (for example, fresh food (vegetables, fruits, meat, fresh fish, processed food, etc.), flowers, and antibacterial products for maintaining the freshness of processed products) It can be suitably used as an antimicrobial film, an antimicrobial molded body, an antimicrobial nonwoven fabric). This can maintain the freshness of fresh food and processed products.
  • an antibacterial material for example, fresh food (vegetables, fruits, meat, fresh fish, processed food, etc.), flowers, and antibacterial products for maintaining the freshness of processed products.
  • the freshness maintaining material of the present embodiment includes the antibacterial material of the present embodiment. That is, the material for maintaining freshness of the present embodiment is a material for maintaining freshness obtained using the antibacterial material (for example, an antibacterial film, an antibacterial formed article, an antibacterial non-woven fabric) of the present embodiment. Thereby, the material for maintaining freshness having high antibacterial property and good operability can be obtained. It is preferable that the material for maintaining freshness of the above-mentioned embodiment is used for packing of an article.
  • the material for maintaining freshness of the present embodiment is provided with an antibacterial material having high antibacterial properties, for example, for maintaining freshness of fresh food (vegetables, fruits, meat, fresh fish, processed foods, etc.), flowers and processed products.
  • a packaging material for example, a packaging bag
  • the packaging bag as the packaging material is formed by, for example, bending the antibacterial material so that the surfaces (surface layers including the molecule A and the component B) having the antibacterial action of the antibacterial material (for example, the antibacterial film) face each other After laminating at least two or more antimicrobial materials, it can be obtained by heat-sealing (heat sealing) a predetermined portion by a known method.
  • the surface layer is preferably a surface facing the article. This keeps the surface of the article clean, in particular if the article is a food product, its freshness is maintained.
  • the method for producing the antibacterial material of the present embodiment is not particularly limited, and a step of forming the above-mentioned surface layer by applying a coating solution containing the molecule A and the component B on a substrate (hereinafter referred to as “coating It is preferable to include a film formation step ").
  • coating solution may contain other components, as necessary, together with the molecule A and the component B.
  • the coating solution containing the antifogging agent together with the molecule A and the component B.
  • the method of preparing the coating solution is not particularly limited.
  • the coating solution may be obtained by mixing the obtained mixture, the molecule A and the solvent.
  • the amount of the molecule A is preferably 0.2 mg / m 2 to 300 mg / m 2 , more preferably 0.2 mg / m 2 to 200 mg / m 2 , 0.6 mg / M 2 to 150 mg / m 2 is more preferable, 0.9 mg / m 2 to 50 mg / m 2 is particularly preferable, and 1.0 mg / m 2 to 30 mg / m 2 is more preferable .
  • the application of the coating solution onto the substrate is preferably carried out by adjusting the amount of the molecule A.
  • the coating method of the coating solution is not particularly limited, but, for example, known methods such as spin coating, bar coating, spraying, roller method, dipping, and inkjet method can be applied.
  • the method for producing the substrate is not particularly limited, but when the form of the substrate is a film (non-oriented film, uniaxial or biaxially oriented film), for example, a material (material containing a polymer) constituting the substrate is used.
  • the form of the substrate is a molded article (for example, a container-shaped molded article)
  • the molded article as the substrate can be produced by molding a film (base film) as the substrate by a known method.
  • the form of the substrate is a non-woven fabric
  • a non-woven fabric for example, an air through method, a spun bond method, a needle punch method, a melt blown method, a card method, a heat fusion method, using fibers containing one or more of the above-mentioned polymers.
  • the nonwoven fabric as a base material can be manufactured by well-known methods, such as a water entanglement method and a solvent adhesion method.
  • a commercial item may be used as the above-mentioned substrate (film, molded body, non-woven fabric).
  • the surface treatment of the above-mentioned may be made for the surface of a substrate.
  • the coating solution contains, for example, the molecule A, the component B, and the solvent, and may contain other components as needed.
  • the solvent include water, methanol, ethanol, normal propanol (n-propanol), isopropanol, allyl alcohol, 1-butanol, 2-butanol, cyclopentanol, 1-hexanol, 3-hexanol, ethylene glycol, 1 And 3-propanediol, glycerin, acetone, ethyl methyl ketone, acetonitrile, acrylonitrile, diethyl ether, ethyl acetate, ethylene diamine, dimethyl sulfoxide (DMSO) and the like.
  • the coating solution preferably contains at least water as a solvent.
  • the content of the molecule A in the coating solution is preferably 0.01% by mass to 15% by mass, more preferably 0.01% by mass to 10% by mass, with respect to the total mass of the coating solution, from the viewpoint of improving the operability of the antibacterial material. % Is more preferable, 0.01% by mass to 6.5% by mass is more preferable, and 0.01% by mass to 5% by mass is particularly preferable.
  • the content of component B in the coating solution is preferably 0.1% by mass to 80% by mass, and more preferably 0.3% by mass to the total mass of the coating solution, from the viewpoint of improving the operability of the antibacterial material. 70% by mass is more preferable, 0.5% by mass to 60% by mass is more preferable, and 1% by mass to 50% by mass is particularly preferable.
  • the method for producing the antibacterial material of the present embodiment preferably includes the step of drying at least the surface layer (coated film) at a temperature of 50 ° C. to 120 ° C. (hereinafter also referred to as “drying step”).
  • the drying temperature of the coating film in the drying step is more preferably 50 ° C. to 80 ° C., further preferably 50 ° C. to 60 ° C.
  • the drying time, the drying atmosphere, and the pressure at which drying is performed can be appropriately selected according to the composition of the coating solution, the amount of application, and the like.
  • the method for drying the coating film is not particularly limited as long as it accelerates the evaporation of the solvent contained in the coating solution, but, for example, a method of applying heat to the coating film, a method of blowing warm air to the coating film, Methods that combine Among them, a method of blowing warm air to the coating film is preferable from the viewpoint of suppressing the repelling of the coating liquid on the coating surface.
  • the method of applying heat to the coating film is not particularly limited as long as it is a method using a furnace, a hot plate, a vacuum heater or the like.
  • the method of blowing warm air to the coating film is not particularly limited as long as it is a method using an apparatus capable of heating a gas. In the case of the method of blowing warm air to the coating film, the preferable range of the temperature of the warm air is the same as the preferable range of the above-mentioned drying temperature.
  • the manufacturing method of the antibacterial material of this embodiment further includes a step of performing surface treatment on the substrate before applying the coating liquid (hereinafter also referred to as “surface treatment step”).
  • surface treatment may be performed with respect to the whole surface of a base material, and may be performed with respect to at least one part of a base material.
  • the surface treatment method for the substrate is not particularly limited, but includes surface activation treatments such as corona treatment, itro treatment, ozone treatment, ultraviolet treatment, chemical treatment, high frequency treatment, glow discharge treatment, plasma treatment, laser treatment and the like. .
  • the corona treatment is preferable from the viewpoint of reducing the unevenness of the distribution by increasing the wettability of the component B on the surface and preventing the falling off of the component B.
  • Examples 1 to 2 and Comparative Examples 1 to 3 ⁇ Production of Single-Layer Stretched Polypropylene-Based Film> A propylene homopolymer (melting point (Tm): 160 ° C., MFR: 3 g / 10 minutes (Prime Polymer Co., Ltd. trade name: F300SP)) was prepared. A single-layer stretched polypropylene-based film (hereinafter also referred to as “single-layer OPP film”) is obtained by subjecting a propylene homopolymer to biaxial stretching of 5 times in length and 10 times in width using a biaxial stretching machine. Manufactured.
  • the stretching temperature of the single-layer OPP film was longitudinal stretching: 100 ° C., transverse stretching: 180 ° C., the heat setting temperature was 180 ° C., and the setting time was 10 seconds.
  • the thickness of the single layer OPP film was 30 ⁇ m.
  • corona treatment was performed on one surface of the single layer OPP film so as to obtain a wetting control (wetting index) of 38 dyn (dyne).
  • the measurement of the wetting index was confirmed according to JIS K 6768 (1999) depending on whether or not the mixture for wet tension test (NO. 38.0) of Wako Pure Chemical Industries, Ltd. could be applied.
  • protamine salt As molecule A, the following protamine salt which is an antibacterial agent was used. The weight average molecular weight of the protamine salt was measured by the method described above. Protamine salt: protamine hydrochloride, Maruha Nichiro, Inc., protamine content (content of protamine salt to the whole) 88.3% by mass, ignition residue 11.4%, weight average molecular weight 5800, equivalent weight of basic group 200 g / eq
  • a dispersion liquid containing the component B As a dispersion liquid containing the component B, the following cationic water-based emulsion which is a dispersion liquid containing a high molecular compound and a high molecular cationic surfactant was used.
  • Cationic aqueous emulsion Aquatex EC-1800, Japan Coating Resin Co., Ltd., pH 4.4 ⁇ 1.0, particle diameter of polymer compound 1.0 ⁇ m, solid concentration 50% by mass, ethylene / vinyl acetate copolymer ( Polymer compound)
  • the extruded resin mixture was cooled to 110 ° C. by a jacketed static mixer installed at the same extruder outlet, and then poured into warm water at 80 ° C. to obtain an emulsion.
  • the obtained emulsion had a solid content concentration of 45% by mass, a pH of 10, and a particle size of 0.4 ⁇ m.
  • the maleic anhydride-modified propylene-based polymer is 96 parts by weight of a propylene / butene copolymer, 4 parts by weight of maleic anhydride, and 0.4 parts by weight of Perhexin 25B (manufactured by NOF Corporation) as a polymerization initiator.
  • the mixture was mixed and denatured at a heating temperature of 160.degree. C. for 2 hours.
  • content of the component B in a coating liquid means the ratio with respect to the whole coating liquid of the high molecular compound which is solid content in an emulsion, and a high molecular cationic surfactant, " ⁇ (mass of a high molecular compound It is a value (mass%) represented by + mass of polymeric cationic surfactant) / mass of whole coating liquid ⁇ ⁇ 100 ”.
  • the coating solution was applied at a coating speed of 0.3 (mL / (m 2 ⁇ sec)) by hand coating (coating method) using a coating bar on the corona-treated surface of the single-layer OPP film (base material) It apply
  • warm air at a wind speed of 40 m / min and 120 ° C. was blown onto the coating film for 20 seconds to dry the coating solution. This formed a surface layer on the single layer OPP film.
  • the coating liquid of the quantity adjusted beforehand so that the surface amount (mg / m ⁇ 2 >) of the molecule A became a value shown in Table 1 was mounted on the coating bar.
  • a film for maintaining freshness (antibacterial material) including the single layer OPP film and the surface layer disposed on the single layer OPP film was obtained.
  • the heat seal strength, the static friction coefficient, and the thickness of the surface layer of the surface layer in the film for keeping freshness obtained are shown in Table 1.
  • the result of having performed the following evaluation using the obtained film for freshness holding is shown in Table 1.
  • "immeasurable" means that the stickiness of the surface layer was so great that measurement of the static friction coefficient was impossible.
  • Antimicrobial evaluation With respect to the films for maintaining freshness obtained in Examples and Comparative Examples, an antibacterial test (antibacterial evaluation) was performed using Escherichia coli according to JIS Z2801. In addition, in order to maintain the state of the surface of the film for maintaining freshness, wiping with alcohol was not performed.
  • E. coli Escherichia coli
  • a specified amount a broth using 0.4 mL in the above-mentioned antibacterial test
  • the broth containing the E. coli test bacterial solution
  • a 4 cm square polyethylene film separately prepared was placed on top of the test solution. This was used as an evaluation sample.
  • the surface of the evaluation sample is washed, the washing solution containing the test solution (normal broth medium) is collected, and it is cultured using a normal agar medium to count the number of E. coli colonies. Counted (number of test colonies).
  • the initial number of bacteria was 1.1 E + 5 [cells / g].
  • the antibacterial activity (common logarithm value) was determined by the following equation.
  • antibacterial activity log (number of control bacteria / number of test sample bacteria)
  • the number of control bacteria means the average number of test colonies when a polyethylene film is used instead of the "freshness holding film” described in the above-mentioned ⁇ Antibacterial evaluation>
  • Example 11 to 18 ⁇ Preparation of antibacterial material>
  • a monolayer OPP film corona treated
  • protamine salt molecule A, protamine hydrochloride
  • a cationic aqueous emulsion disersion containing component B, Aquatex EC-1800
  • Antifogging agent 1 (antifogging agent B): Rikemar A (Riken Vitamin Co., Ltd., compound name: sucrose laurate, molecular weight: 525, HLB value: 19.4, polar functional group: hydroxyl group, polar functional group Equivalent weight: 40.7 g / eq)
  • Antifogging agent 2 (antifogging agent A): stearyl diethanolamine (Tokyo Chemical Industry Co., Ltd., molecular weight: 357.61, HLB value: 6.8, polar functional group: equivalent of hydroxyl group, polar functional group: 179 g / eq)
  • Antifogging agent 3 (antifogging agent B): Poem DL-100 (Riken Vitamin Co., Ltd., compound name: diglycerin monolaurate, molecular weight: 392, HLB value: 9.4, polar functional group: hydroxyl group, polar
  • a film for maintaining freshness (antibacterial material) including the single layer OPP film and the surface layer disposed on the single layer OPP film was obtained.
  • Amount of antifogging agent A per unit area in surface layer (“antifogging agent A amount (mg / m 2 )” in Table 3) and antifogging agent A and antifogging agent B per unit area in surface layer
  • the total amount (“total amount of antifogging agent (mg / m 2 )” in Table 3) is shown in Table 3 respectively.
  • the amount of molecule A per unit area in the surface layer was 10 mg / m 2
  • the thickness of the surface layer was 3 ⁇ m.
  • Example 11 5.1 N / 15 mm ⁇
  • Example 12 4.9 N / 15 mm ⁇
  • Example 13 5.2 N / 15 mm ⁇
  • Example 14 5.4 N / 15 mm ⁇
  • Example 15 4.8 N / 15 mm
  • Example 16 4.7 N / 15 mm
  • Example 17 5.2 N / 15 mm
  • Example 18 5.1 N / 15 mm
  • a cylindrical polypropylene container (height 80 mm ⁇ diameter 55 mm) containing 50 mL of water at 25 ° C. is prepared, and the antifogging property of the obtained film for maintaining freshness is evaluated so as to close the opening of the container.
  • the surface of the side was placed toward the container side, and the container was sealed. After sealing, it was left in a refrigerator at 5 ° C. for 2 hours and then evaluated.
  • evaluation can be judged that antifogging property is favorable, when evaluation rank is "3" or more.
  • the evaluation results are shown in Table 3.
  • -Evaluation criteria- 5 The spread of water droplets is good, and it is uniformly wet over the entire surface (diameter 55 mm) of the circular film located at the opening of the container. 4: The spread of the water droplet is good, but a few water droplets are observed. 3 to 4: Water droplets having a diameter of 6 mm to 10 mm are observed, but high transparency is maintained. 3: A water droplet with a diameter of about 5 mm is attached, but high transparency is maintained. 2 to 3: Water droplets having a diameter of about 4 mm are attached, but transparency is maintained. 2: A water droplet of 2 mm to 3 mm in diameter adheres to the entire surface, but the transparency is maintained. 1: Fine water droplets less than 2 mm in diameter adhere to the entire surface and are opaque.
  • Examples 11 to 14 and Examples 17 to 18 containing the antifogging agent 2 which is the antifogging agent A in the surface layer are the antifogging agent 1 which is the antifogging agent B or the antifogging agent It was found that the antifogging properties of the surface layer were superior to Examples 15 and 16 in which only the agent 3 was contained in the surface layer.
  • the three materials of the outermost layer / intermediate layer / heat seal layer are laminated so that the total thickness ratio becomes 1/8/1 using the above-mentioned material, and 5 times long and 10 times wide using a biaxial stretching machine
  • a single-sided heat-sealed multilayer stretched polypropylene-based film (hereinafter also referred to as "single-sided heat-sealed OPP film") was produced.
  • the stretching temperature of the single-sided heat seal OPP film was longitudinal stretching: 100 ° C.
  • transverse stretching 180 ° C.
  • heat setting temperature was 180 ° C.
  • setting time was 10 seconds.
  • the thickness of the single-sided heat seal OPP film was 30 ⁇ m.
  • a corona treatment was performed on both sides of the single-sided heat seal OPP film so as to obtain a wetting control (wetting index) of 38 dyn.
  • the measurement of the wetting index was confirmed according to JIS K 6768 (1999) depending on whether or not the mixture for wet tension test (NO. 38.0) manufactured by Wako Pure Chemical Industries, Ltd. can be applied.
  • a coating solution was prepared in which the content (% by mass) of the molecule A and the content (% by mass) of the component B in the coating solution were the values shown in Table 4.
  • the single-sided heat seal OPP was prepared in the same manner as in Example 1 except that the single-sided heat seal OPP film was used instead of the single-layer OPP film (substrate) and the formation region of the surface layer was as shown in FIG.
  • a film coating solution was applied to form a coating film, and the coating film was dried to form a surface layer.
  • the coating liquid of the quantity adjusted beforehand so that the surface amount (mg / m ⁇ 2 >) of the molecule A became a value shown in Table 4 was mounted on the coating bar.
  • a film for maintaining freshness (antibacterial material) including the single-sided heat seal OPP film and the surface layer disposed on the single-sided heat seal OPP film was obtained.
  • the static friction coefficient of the surface layer and the thickness of the surface layer in the obtained film for maintaining freshness are shown in Table 4, respectively.
  • the heat seal strengths of the surface layers of the films for maintaining freshness obtained in Examples 21 to 22 and Comparative Examples 21 to 23 are for the freshness holding obtained in Examples 1 to 2 and Comparative Examples 1 to 3, respectively.
  • the heat seal strength of the surface layer of the film was comparable.
  • “Same level” means the range within ⁇ 10% with respect to the numerical value to be compared.
  • the result of having evaluated similarly to Example 1 using the obtained film for freshness holding is shown in Table 4.
  • "immeasurable” means that the stickiness of the surface layer was so great that measurement of the static friction coefficient was impossible.

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Abstract

L'invention concerne un matériau antibactérien qui est équipé : d'un matériau de base ; et d'une couche superficielle qui est disposée sur au moins une face dudit matériau de base, et qui contient une molécule (A) possédant au moins une sorte de structure choisie dans un groupe constitué d'une structure dérivée d'une guanidine, d'une structure dérivée d'une glucosamine et d'une structure dérivée d'un acide aminé, et présentant une masse moléculaire moyenne en poids supérieure ou égale à ５００ et inférieure ou égale à １００００, et un composant (B) qui est constitué d'un composé autre que ladite molécule (A), et qui est cationique ou non ionique. Plus précisément, l'invention concerne un matériau antibactérien qui présente une quantité de ladite molécule (A) comprise entre ０,２ｍｇ／ｍ２ et ３００ｍｇ／ｍ２ par surface unitaire dans ladite couche superficielle.
PCT/JP2018/040582 2017-10-31 2018-10-31 Matériau antibactérien, et matériau pour maintien de la fraîcheur WO2019088199A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2022024922A (ja) * 2020-07-28 2022-02-09 アイム株式会社 包装資材及びその製造方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08231327A (ja) * 1995-03-01 1996-09-10 San Purasuto Mikasa:Kk 抗菌性物材及びその加工品
JP2001342435A (ja) * 2000-06-01 2001-12-14 Fujimori Kogyo Co Ltd コーティング剤及び抗菌性シート
JP2002101860A (ja) * 2000-09-28 2002-04-09 Chisso Corp フィルムまたはシート、およびそれを用いた生鮮品の鮮度保持方法
WO2014142218A1 (fr) * 2013-03-14 2014-09-18 三井化学東セロ株式会社 Film fraîcheur
JP2016160350A (ja) * 2015-03-02 2016-09-05 花王株式会社 食品加工設備又は調理器具用殺菌剤組成物

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08231327A (ja) * 1995-03-01 1996-09-10 San Purasuto Mikasa:Kk 抗菌性物材及びその加工品
JP2001342435A (ja) * 2000-06-01 2001-12-14 Fujimori Kogyo Co Ltd コーティング剤及び抗菌性シート
JP2002101860A (ja) * 2000-09-28 2002-04-09 Chisso Corp フィルムまたはシート、およびそれを用いた生鮮品の鮮度保持方法
WO2014142218A1 (fr) * 2013-03-14 2014-09-18 三井化学東セロ株式会社 Film fraîcheur
JP2016160350A (ja) * 2015-03-02 2016-09-05 花王株式会社 食品加工設備又は調理器具用殺菌剤組成物

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2022024922A (ja) * 2020-07-28 2022-02-09 アイム株式会社 包装資材及びその製造方法
JP7385274B2 (ja) 2020-07-28 2023-11-22 アイム株式会社 包装資材及びその製造方法

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