JP2015163686A - Poly(meth)acrylic acid ion complex - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ion complex capable of not only being surface applied to a substrate, compounded or composited, but also direct formed, having low cost property and supply stability and capable of being used in a wide range of fields requiring antibacterial property, and a manufacturing method therefor.SOLUTION: The ion complex contains a poly(meth)acrylic acid having a viscosity average molecular weight of 100,000 to 1,000,000 and quaternary ammonium ion of the following formula (I) and/or formula (II). In the formulas (I) (II), Rto Rrepresent same or different Calkyl group, benzyl group, Caryl group and Rand Rindependently represent a Calkyl group.

Description

  The present invention relates to a poly (meth) acrylate ion complex that can be used as an antibacterial plastic material such as a film or fiber having antibacterial properties, and a sanitary product such as a disinfectant spray.

  In recent years, general living materials processed with antibacterial materials have become indispensable materials from the viewpoint of hygiene. In particular, not only in hospitals such as large-scale hospitals where the prevention and spread of food poisoning and infectious diseases are strongly demanded, but also in the medical field such as nursing care sites, which are rapidly increasing in an aging society, as well as household and toiletries where strong hygiene orientation is seen In this field, the demand for antibacterial products is increasing, and there is a demand for the supply of high-performance and inexpensive antibacterial materials.

  Conventionally, antibacterial materials have been processed mainly by surface coating, blending, compounding, etc. on various types of antibacterial agents.

  Antibacterial agents used in the above-described antibacterial materials are roughly classified into inorganic (metal) antibacterial agents, organic antibacterial agents, and natural antibacterial agents. As inorganic antibacterial agents, metal ions such as silver, copper and zinc have been known for a long time. In particular, since silver ions have a long-lasting effect and excellent heat resistance, they are suitable for molding processing when blended with plastics. However, it has been pointed out that silver ions have a weak antibacterial activity against fungi such as mold.

  Organic antibacterial agents include chemical synthetic products such as nitrogen-containing antibacterial agents, sulfur-containing antibacterial agents, and phosphorus-containing antibacterial agents, and are used as industrial materials for building materials, agricultural chemicals, marine products, and the like. Among them, quaternary ammonium salt antibacterial agents are used for hygiene in, for example, the medical field and the food field because of their higher safety and less environmental impact. However, these antibacterial agents have high water-solubility and thus poor adhesion to the substrate, and are difficult to surface-coat, blend and combine, and have significantly poor antibacterial processability compared to inorganic antibacterial agents. It is. That is, even if an organic antibacterial agent is blended in the base material, the antibacterial component is eluted with water and the sustainability is lowered.

  In addition, natural antibacterial agents such as chitosan, catechin, and hinokitiol have high safety and give users peace of mind, but they are more expensive to manufacture than chemical synthetic products, and have poor heat resistance and processability. But challenges still remain.

  In order to solve the above problems, a technique for immobilizing a quaternary ammonium salt on a base material has been developed. For example, Patent Document 1 discloses a composition containing octadecyldimethyl (3-triethoxysilylpropyl) ammonium chloride. This invention is a technique for fixing octadecyldimethyl (3-triethoxysilylpropyl) ammonium chloride to a base material containing an oxygen functional group such as glass or cellulose. Specifically, the 3-triethoxysilyl group in the molecule is chemically bonded to and bonded to the oxygen functional group on the substrate surface. However, since the chloride ion corresponding to the counter anion of the present compound exhibits strong corrosiveness to the base material containing iron, corrosion resistance becomes a problem.

  In view of the above situation, the antibacterial agent has sufficient antibacterial properties and can be manufactured at low cost, and has effects such as safety to the human body, low environmental impact, simple workability, and low corrosiveness. High functionality is desired.

  As an antibacterial material that solves the above problem, Patent Document 2 describes an ion complex formed from poly-γ-glutamate ions and quaternary ammonium ions (hereinafter sometimes referred to as “PGAIC”). ing. The ion complex is a water-insoluble polymer, has antibacterial properties and safety equivalent to those of organic antibacterial agents, has high adhesion to the base material, and can be painted, compounded, and compounded. Excellent workability. In addition, since it does not contain corrosive halogen, it is a material with excellent low corrosivity. Furthermore, the ion complex itself is a plastic material having physical properties that can be formed into a film, fiber, or the like. This document describes the usefulness of a film formed from the ion complex as a material having antibacterial properties.

  Thus, PGAIC attracts attention as an antibacterial material excellent in moldability. However, the chemical synthesis method of poly-γ-glutamic acid (hereinafter abbreviated as “PGA”), which is the raw material of this drug, has not been established, and microorganisms are used in its industrial production, and conventional chemical synthesis Productivity is low compared to polymers, costs are somewhat inferior, and supply stabilization is an issue. Therefore, it is necessary to find an inexpensive and highly supplyable polymer that can replace PGA. Furthermore, creation of a material having the same level of function as PGAIC is not required.

  Poly (meth) acrylic acid is known as an inexpensive polymer that is industrially available, and is used in various fields. For example, since polyacrylic acid has a carboxy group, it is used as a water-absorbing gel in SAP (super absorbent polymer) such as paper diapers and sanitary products.

  Patent Document 3 discloses a composition formed from polyacrylic acid and quaternary ammonium ions. More specifically, the polymerization degree of the polymer used is preferably 20 to 300, and an antifungal agent is produced from sodium polyacrylate having a polymerization degree of 300 and tetradecyldimethylbenzylammonium chloride. Yes.

JP 2011-98976 A JP 2010-2222496 A Japanese Patent Application Laid-Open No. 64-02824

  As described above, antifungal agents containing polyacrylic acid and quaternary ammonium ions as active ingredients are known (Patent Document 3).

  However, Patent Document 3 only shows that a salt composed of polyacrylic acid and a quaternary ammonium ion is blended into an antifungal agent containing petrolatum or the like as a base material, and the salt is surfaced to the base material. There is no disclosure of a technical idea of processing such as painting or compounding or use as a plastic material or functional fiber material.

  Therefore, the present invention can be applied not only to surface coating, blending, compounding, etc., but also to direct molding, and is widely used in fields requiring low cost and supply stability and requiring antibacterial properties. It is an object of the present invention to provide an ion complex that can be used for the above and a method for producing the same.

  The inventors of the present invention have made extensive studies to solve the above problems. As a result, the present inventors have found that the molecular weight of the poly (meth) acrylic acid is very important for the moldability of an ion complex composed of poly (meth) acrylic acid and quaternary ammonium ions. Under such knowledge, the present inventors have completed the present invention.

  That is, the present invention is as follows.

  [1] A poly (meth) acrylic acid having a viscosity average molecular weight of 100,000 or more and 1,000,000 or less and a quaternary ammonium ion of the following formula (I) and / or formula (II): Characteristic ion complex.

[Wherein R ^{1 to} R ³ represent the same or different C _1-20 alkyl group, benzyl group, C _6-12 aryl group, and R ^{4 to} R ⁵ independently represent a C _12-20 alkyl group. ]

  [2] The ion complex according to [1], including the quaternary ammonium ion (II).

  [3] The ion complex according to [1] or [2], wherein the quaternary ammonium ion is contained in an equimolar or substantially equimolar amount with respect to a (meth) acrylic acid unit constituting the poly (meth) acrylic acid.

  [4] The ion complex according to any one of [1] to [3], wherein the poly (meth) acrylic acid has a viscosity average molecular weight of 400,000 or more.

  [5] The ion complex according to any one of [1] to [4], which is water-insoluble.

  [6] An antibacterial plastic material comprising the ion complex according to any one of [1] to [5].

  Since the ion complex of the present invention does not cause gelation between poly (meth) acrylic acids constituting the ion complex, it can be formed into a film or fiber. In addition, it does not show water solubility, has an affinity for the base material, and can be dissolved in a specific solvent, so it can be easily antibacterial processed by surface coating, blending, and compounding on the base material. . Furthermore, the ion complex of the present invention has excellent characteristics as an antibacterial material similar to PGAIC. On the other hand, since the poly (meth) acrylic acid that is the raw material of the ion complex according to the present invention can be stably mass-produced inexpensively, the ion complex can be stably produced at a low cost. Manufacture and supply are possible. As described above, the ion complex according to the present invention has very excellent characteristics as an antibacterial component and an antibacterial material, and is industrially useful.

FIG. 1 is a photograph of a reaction solution when an ion complex according to the present invention is produced using a polyacrylic acid free body. FIG. 2 is a photograph of a reaction solution when an ion complex according to the present invention is produced using a sodium salt of polyacrylic acid. FIG. 3 is a photograph showing the results of an antibacterial test of (1) a wiping cloth as a control, (2) a PGAIC film, and (3) an ion complex (PACIC) film according to the present invention, respectively.

  The ion complex according to the present invention comprises a poly (meth) acrylic acid having a viscosity average molecular weight of 100,000 or more and 1,000,000 or less and a quaternary ammonium ion of the following formula (I) or formula (II). It is characterized by including. Hereinafter, the ion complex may be abbreviated as “PACIC”.

[Wherein R ^{1 to} R ³ represent the same or different C _1-20 alkyl group, benzyl group, C _6-12 aryl group, and R ^{4 to} R ⁵ independently represent a C _12-20 alkyl group. ]

  In the present invention, “(meth) acrylic acid” refers to acrylic acid and / or methacrylic acid. In addition, “poly (meth) acrylic acid” may be a copolymer of acrylic acid and methacrylic acid in addition to polyacrylic acid and / or polymethacrylic acid.

“C _1-20 alkyl group” means a linear or branched monovalent saturated aliphatic hydrocarbon group having 1 to 20 carbon atoms, and “C _12-20 alkyl group” means carbon A linear or branched monovalent saturated aliphatic hydrocarbon group having a number of 12 or more and 20 or less is meant. For example, the C _1-20 alkyl group includes methyl, ethyl, n-propyl, n-butyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl. , N-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-icosyl and the like linear C _1-20 alkyl group; isopropyl, isobutyl, s-butyl, t-butyl, isopentyl, neopentyl, isohexyl, Isooctyl, isodecyl, isododecyl, isotetradecyl, isopentadecyl, isohexadecyl, isoheptadecyl, isooctadecyl, s-tetradecyl, s-pentadecyl, s-hexadecyl, s-heptadecyl, s-octadecyl, t-tetradecyl, t-pentadecyl , T-hexadecyl, t-hepta Mention may be made of branched C _1-20 alkyl groups such as decyl, t-octadecyl, neotetradecyl, neopentadecyl, neohexadecyl, neoheptadecyl, neooctadecyl. Examples of the C _12-20 alkyl group include those having 12 to 20 carbon atoms.

R ^{1 to} R ³ are preferably a C _1-10 alkyl group, more preferably a C _1-6 alkyl group, still more preferably a C _1-4 alkyl group, and particularly preferably a C _1-2 alkyl group. R ⁴ is preferably a C _15-20 alkyl group, more preferably a C _16-20 alkyl group, and even more preferably a C _17-20 alkyl group. R ⁵ is preferably a C _13-20 alkyl group, more preferably a C _14-19 alkyl group, and particularly preferably a C _15-18 alkyl group.

The “C _6-12 aryl group” refers to a monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms. For example, a phenyl group, a naphthyl group, an indenyl group, a biphenyl group, etc., preferably a phenyl group.

  The viscosity average molecular weight of the poly (meth) acrylic acid constituting the ion complex according to the present invention is 100,000 or more and 1,000,000 or less. When the viscosity average molecular weight is less than 100,000, the strength of the formed ion complex becomes low, and it becomes difficult to form the ion complex alone such as heat forming. On the other hand, when the viscosity average molecular weight exceeds 1,000,000, the solubility is lost and spraying and casting cannot be performed, and the moldability is deteriorated due to gelation.

  The viscosity average molecular weight is an average molecular weight obtained from the viscosity of the polymer. Usually, the viscosity average molecular weight of the polymer is the intrinsic viscosity [η] of a standard sample whose molecular weight is known and the intrinsic viscosity [η of the sample whose molecular weight is to be obtained [η]. ] Is obtained by measuring. In the present invention, the viscosity average molecular weight is used as a reference for the molecular weight of poly (meth) acrylic acid. However, as the average molecular weight of polymers, weight average molecular weight, molecular weight measured by gel filtration chromatography, etc. are used, and the average molecular weight described in the catalog of poly (meth) acrylic acid products is any It may be unclear whether the average molecular weight is measured by such a method. In such a case, in addition to actually measuring the viscosity average molecular weight, such a catalog value may be referred to.

  The viscosity average molecular weight of the poly (meth) acrylic acid is preferably 150,000 or more, more preferably 200,000 or more, further preferably 300,000 or more, particularly preferably 400,000 or more, and 900,000. The following is preferable, 800,000 or less is more preferable, 700,000 or less is more preferable, 600,000 or less is further more preferable, and 500,000 or less is particularly preferable.

In the ion complex according to the present invention, it is unclear in detail what the micro state of poly (meth) acrylic acid is, but in the (meth) acrylic acid monomer unit forming poly (meth) acrylic acid, a carboxy group that forms a quaternary ammonium ion salt is -CO ₂ ^- is considered that the state of. Strictly speaking, although the molecular weight of poly (meth) acrylic acid differs depending on whether the carboxy group is —CO ₂ H or —CO ₂ ^— and the ratio thereof, the amount of change is small compared to the above range. Therefore, the state of the carboxy group can be ignored in the measurement of molecular weight.

  The quaternary ammonium ions (I) and (II) according to the present invention are composed of a tertiary amine and a long chain alkyl group, and are generally used as a surfactant, a phase transfer catalyst or the like. However, it is also used as an antibacterial and antifungal agent.

According to the experimental knowledge of the present inventors, it is preferable to use a quaternary ammonium ion (I) having a long chain alkyl group having a larger number of carbon atoms than the quaternary ammonium ion (II). More specifically, the complex of poly (meth) acrylic acid and quaternary ammonium ion (II) can be thermoformed even at a relatively low temperature of 80 ° C. The complex with the quaternary ammonium ion (I) may be difficult to soften at a relatively low temperature if the carbon number of the long-chain alkyl group is small. Therefore, when importance is attached to easiness of thermoforming, the carbon number of the long-chain alkyl group R ⁴ of the quaternary ammonium ion (I) is preferably 16 or more, and more preferably 17 or more. .

  As the ion complex according to the present invention, those in which poly (meth) acrylic acid is sufficiently modified with quaternary ammonium ions are suitable. More specifically, the ratio of the quaternary ammonium ion in the ion complex is preferably 0.5 times mol or more with respect to the (meth) acrylic acid unit constituting the poly (meth) acrylic acid. It is more preferably 6 times mol or more, and further preferably 0.7 times mol or more.

  In particular, in order to sufficiently modify poly (meth) acrylic acid, those containing equimolar or substantially equimolar amounts of quaternary ammonium ions with respect to the (meth) acrylic acid units constituting poly (meth) acrylic acid. Is preferred. Here, “substantially equimolar” means that the number of moles of both is substantially equal. Specifically, the quaternary ammonium ion relative to the (meth) acrylic acid unit constituting the poly (meth) acrylic acid is 0. It shall be 8 times mol or more and 1.2 times mol or less, especially 0.9 times mol or more and 1.1 times mol or less.

  In addition, a quaternary ammonium ion may be used individually by 1 type, and may mix and use 2 or more types. Further, a mixture of quaternary ammonium ion (I) and quaternary ammonium ion (II) may be used.

  The production method of the ion complex according to the present invention is not particularly limited. For example, a solution of poly (meth) acrylic acid having a viscosity average molecular weight of 100,000 or more and 1,000,000 or less or a salt thereof is added to the formula (I). Alternatively, the ion complex according to the present invention can be produced by adding a salt of a quaternary ammonium ion of the formula (II).

  Examples of the salt of poly (meth) acrylic acid include alkali metal salts and ammonium salts. A solution of poly (meth) acrylic acid is obtained by mixing poly (meth) acrylic acid and a solvent. A solution of a salt of poly (meth) acrylic acid is obtained by mixing poly (meth) acrylic acid, alkali metal salt or ammonium salt and a solvent.

  Alkali metal refers to lithium, sodium, potassium, rubidium, and cesium excluding hydrogen among elements belonging to Group 1 of the periodic table. As the alkali metal used in the present invention, lithium, sodium, potassium and cesium are preferable, lithium, sodium and potassium are more preferable, sodium or potassium is further preferable, and sodium is particularly preferable.

  The counter anion constituting the alkali metal salt and ammonium salt used for preparing the salt of poly (meth) acrylic acid is not particularly limited as long as these salts are soluble in a solvent. Examples thereof include hydroxide ions, carbonate ions, and bicarbonate ions.

  Examples of the alkali metal salt and ammonium salt used in the present invention include hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, ammonium hydroxide; lithium carbonate, sodium carbonate, potassium carbonate, carbonate Carbonates such as cesium and ammonium carbonate; lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, hydrogen carbonate salts such as cesium hydrogen carbonate and ammonium hydrogen carbonate, among which lithium carbonate, sodium carbonate, potassium carbonate, Carbonates such as cesium carbonate are preferred. In addition, an alkali metal salt and ammonium salt may be used individually, and 2 or more types may be mixed and used for them.

  When free poly (meth) acrylic acid does not exhibit sufficient solubility in a solvent, it is preferable to use a solution of a salt of poly (meth) acrylic acid. In addition, it has been found by experiments of the present inventors that the ion complex according to the present invention is more easily generated when a salt of poly (meth) acrylic acid is used. In preparing the poly (meth) acrylic acid salt solution, the order of mixing the poly (meth) acrylic acid, the alkali metal salt or ammonium salt and the solvent is not particularly limited. It is preferable to add (meth) acrylic acid.

The solvent of the free poly (meth) acrylic acid solution or the poly (meth) acrylic acid salt solution is not particularly limited as long as it can dissolve each solute. For example, water; C such as methanol and ethanol _1-4 alcohols can be mentioned, and water is more preferred. This is because, in particular, the salt of poly (meth) acrylic acid can be dissolved well, and the ion complex, which is the target compound, is insoluble in water, which is convenient for isolation and purification of the target compound after the reaction. .

  In the case of adding free poly (meth) acrylic acid to the alkali metal salt and / or ammonium salt solution, the concentration of the alkali metal salt and / or ammonium salt solution may be appropriately adjusted. For example, 0.1 w / What is necessary is just to set it as about v% or more and 5 w / v% or less. The density | concentration and usage-amount of the said solution are suitably adjusted to such an extent that the poly (meth) acrylic acid added can fully be melt | dissolved.

  Next, the salt of the quaternary ammonium ion of the above formula (I) or the above formula (II) is added to the poly (meth) acrylic acid or the salt solution obtained above.

  Examples of the counter anion constituting the salt of the quaternary ammonium ion include halide ions such as chloride ion, bromide ion and iodide ion.

The salt of the quaternary ammonium ion may be added as it is to the solution of the poly (meth) acrylic acid or a salt thereof, but may be added in the form of a solution. The solvent is preferably water, but depending on the water solubility of the quaternary ammonium ion salt, C _1-4 alcohols such as methanol and ethanol; ether solvents such as diethyl ether and THF; A water-soluble organic solvent such as an amide solvent such as dimethylformamide or dimethylacetamide may be added to the reaction solution. However, considering the separation of the ion complex after completion of the reaction, it is preferable to use only water as the solvent.

  The amount of the quaternary ammonium ion salt may be appropriately adjusted according to the desired ion complex as the target compound, but in general, in order to sufficiently modify poly (meth) acrylic acid, A sufficient amount with respect to the (meth) acrylic acid unit constituting the poly (meth) acrylic acid, specifically 1.0 times mol or more, preferably 1.1 times mol or more, more preferably 1.2 times mol or more. Use.

  The amount of quaternary ammonium ion salt used can be adjusted by the concentration and amount of the solution, but the amount of quaternary ammonium ion salt solution used is determined by the concentration of poly (meth) acrylic acid in the reaction solution. It is preferable to adjust so that the salt concentration of the quaternary ammonium ion is about 1.0 w / v% or more and about 10 w / v% or less.

  After the addition of the quaternary ammonium ion salt, the reaction solution is preferably heated appropriately to promote the formation of an ion complex. The heating temperature can be, for example, about 40 ° C. or higher and 80 ° C. or lower. The reaction time may be appropriately adjusted, but can usually be about 30 minutes or longer and about 20 hours or shorter.

  Since the ion complex of the present invention is insoluble in at least water, it precipitates after the reaction when water is used as the main solvent. Moreover, when it does not precipitate even after reaction due to the use of a water-soluble organic solvent, it can be precipitated by adding water as a poor solvent. The precipitated ion complex can be easily separated from the solvent by filtration or centrifugation.

  The ion complex of the present invention may be washed or dried after being separated from the reaction solution. For example, the separated ion complex can be washed with water to remove excess poly (meth) acrylic acid or quaternary ammonium salt and other water-soluble reagents. The aqueous solvent can be easily removed by washing with acetone or the like.

  Since the ion complex of the present invention exhibits excellent antibacterial properties, it can be used as an antibacterial component of antibacterial materials. Specifically, the ion complex of the present invention not only exhibits an excellent bacteriostatic effect against both gram-positive and gram-negative bacteria, but also has an excellent bacteriostatic effect against fungi. It can be used as an antibacterial agent and / or an antifungal agent that can be widely used in fields requiring antibacterial and antifungal properties in terms of health and hygiene. In addition, the antibacterial effect and / or antifungal effect also indirectly shows a deodorizing effect.

  Examples of Gram positive bacteria in which the ion complex of the present invention exhibits an antibacterial effect include Gram positive bacteria belonging to the genus Staphylococcus, Streptococcus, Corynebacterium, Bacillus, Listeria, Clostridium, and Lactobacillus.

  Examples of gram-negative bacteria in which the ion complex of the present invention exhibits an antibacterial effect include, for example, Escherichia, Pseudomonas, Salmonella, Enterobacter, Neisseria, Xanthomonas, Serratia, Campylobacter, and Proteus. Negative bacteria are mentioned.

  Examples of fungi for which the ion complex of the present invention exhibits an antibacterial effect include, for example, zygomycetes such as Absidia, Mucor, and Rhizopus; Aspergillus, Neurospora, Penicillium, Trichoderma, Neosartoria, Candida, Ascomycota such as Pichia genus, Saccharomyces genus; Basidiomycota such as Trametes genus, Cryptococcus genus; Incomplete fungi belonging to Alternaria genus, Fusarium genus, Cladosporium genus, Curvularia genus, Aureobasidium genus, etc.

  The ion complex of the present invention itself can be used as an antibacterial plastic material, and can also be used as an antibacterial active ingredient of an antibacterial material. Examples of the antibacterial material containing the ion complex of the present invention as an active ingredient include those coated, blended and impregnated into a polymer resin, paints and sprays. Since the ion complex of the present invention has adhesiveness and is at least insoluble in water, it does not disappear due to elution of antibacterial components and can be used as a highly durable antibacterial agent.

  When the ion complex of the present invention is used as a material blended with a polymer resin, the type of the polymer resin is not particularly limited and can be freely selected according to the use of the resin composition. Specific examples of the resin that can be used include, for example, vinyl chloride polymers, urethane polymers, acrylic polymers, olefin polymers (such as ethylene polymers and propylene polymers), amide polymers, and ethylene-vinyl acetate copolymers. , Vinylidene chloride polymers, styrene polymers, ester polymers, nylon polymers, cellulose derivatives, carbonate polymers, fluorine resins, silicone resins, vinyl alcohol polymers, vinyl ester polymers, synthetic rubbers, natural rubbers, etc. Can be mentioned. In the resin composition, a plasticizer, a filler, a colorant (such as a dye or a pigment), an ultraviolet absorber, or the like may be appropriately blended as necessary. The blending ratio of the ion complex is preferably within a range in which the antibacterial effect can be expressed and the function as the polymer resin is not impaired, specifically 0.1% by mass or more and 5.0% by mass or less is preferable. More preferably, it is more than mass% and less than 2.0 mass%.

  Said resin composition can be processed into various forms according to the use etc. For example, the resin composition of the present invention is formed into a film shape, a sheet shape, a plate shape, a fiber shape, or a three-dimensional shape by a resin processing method known per se such as extrusion molding, injection molding, solution casting method, and spinning method. can do. For example, it can be used for interior materials, floor materials, textile products, paper products, home appliances, and the like.

  When an antibacterial treatment is applied to an industrial product or a substrate using the ion complex of the present invention, the treatment may be performed by a method such as a brush coating, a spray method, a dipping method, a dipping method, a coating method, or a printing method. Well, not particularly limited.

  The ion complex of the present invention can be made into various forms by dissolving or dispersing in a solvent and blending with other paint additives such as pigments and crosslinking agents as appropriate. Such a form makes it possible to form an antibacterial film on the substrate. In this case, examples of the base material that can be applied include ceramics, metals, metal oxides, plastics, rubbers, ores, and wood. Specifically, examples of ceramics include glass, ceramics, cement, refractory bricks, and firewood. Examples of metals include simple metals such as iron, aluminum, zinc, magnesium, gold, silver, chromium, germanium, molybdenum, nickel, lead, platinum, silicon, titanium, thorium, tungsten, carbon steel, nickel steel, Examples of the alloy include chromium steel, chromium molybdenum steel, stainless steel, aluminum alloy, brass, and bronze. Examples of the metal oxide include alumina, silica, magnesia, tria, zirconia, iron sesquioxide, iron tetroxide, titanium oxide, calcium oxide, zinc oxide, lead oxide and the like. Examples of plastics include general-purpose plastics such as polyvinyl chloride, polyethylene, polypropylene, polystyrene, polyethylene terephthalate, and polyvinyl alcohol; engineering plastics such as polyamide, polycarbonate, polyacetal, polyvinylidene fluoride, polyethersulfone, and polyamideimide; phenol resin And thermosetting resins such as epoxy resins, silicone resins, and polyurethanes. Examples of ores include marble and granite. The ion complex is preferably contained in the paint solvent in an amount of 0.1% by mass or more, and preferably 0.5% by mass or more. If it is less than 0.1% by mass, the antibacterial effect may not be sufficiently exhibited. On the other hand, it is preferably 20% by mass or less in order to be used as a paint.

  Furthermore, the ion complex of the present invention can be used as a spray by dissolving or dispersing in a solvent. Specifically, antibacterial activity can be achieved by spraying directly on bathrooms in sinks, hospitals, public facilities, sinks, and sanitary equipment. In this case, as a dispersion used in the propellant, from the viewpoint of safety, alcohols such as water, ethanol, methanol, isopropanol, and hydrocarbon solvents such as n-hexane are preferable, ketones, Various solvents such as esters, fatty acids and silicone oils can also be used. These solvents may be used alone or in combination of two or more. The ion complex is preferably contained in the propellant in an amount of 0.1% by mass or more, more preferably 0.5% by mass or more. If it is less than 0.1% by mass, the antibacterial and deodorizing effects may not be sufficiently exhibited. Although an upper limit is not specifically limited, When melt | dissolving in a solvent etc., it is preferable that it is 20 mass% or less.

  Alternatively, by spraying onto the inner surface of the mold of a plastic injection molding machine, the antibacterial effect and deodorizing effect can be indirectly transferred to the surface of the molded plastic, and the wall surface and plastic surface can be antibacterial processed for a long time. .

  The ion complex of the present invention can be used after being processed into a film-like molded body as a plastic material by utilizing the property of being heat-moldable.

  The ion complex of the present invention is spun by a solution spinning method such as a wet spinning method, a dry wet spinning method, a dry spinning method, a gel spinning method, a melt spinning method, a charged spinning method, etc., and a fiber structure such as a woven or knitted fabric or a nonwoven fabric It can also be used as As an example, it is dissolved in an alcohol solvent such as methanol or ethanol or an ether solvent such as diethyl ether or THF, and charged spinning (charged repulsion of the solution while discharging a charged polymer solution from the nozzle tip). Nanofibers can be produced by a method of obtaining a fine fibrous material by force) to obtain a non-woven fibrous structure.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited by the following examples, but may be appropriately modified within a range that can meet the purpose described above and below. Of course, it is possible to implement them, and they are all included in the technical scope of the present invention.

Example 1: Production of PACIC (PAC / HDP) from PAC having a viscosity average molecular weight of 450,000 As a raw material polyacrylic acid (hereinafter abbreviated as “PAC”), a material having a viscosity average molecular weight of 450,000 (manufactured by Aldrich) Was used to produce a polyacrylate ion complex (PACIC) with reference to the examples described in Patent Document 2 (Japanese Patent Application Laid-Open No. 2010-222496). Specifically, distilled water (20 mL) was added to PAC (0.4 g) and dissolved over 2 hours at room temperature to prepare a 2.0 w / v% PAC aqueous solution. To this PAC aqueous solution, a solution obtained by adding distilled water (20 mL) to hexadecylpyridinium bromide (2.1 g, hereinafter abbreviated as “HDPB”) was added, and the mixture was allowed to stand at 60 ° C. for 1 hour. . HDPB and polyacrylic acid did not react and a water-insoluble precipitate was not obtained. The state in the system is shown in FIG.

  Therefore, the conditions under which water-insoluble PACIC was obtained were examined. Distilled water (20 mL) was added to sodium carbonate (0.3 g) and stirred for 20 minutes to prepare a 1.5 w / v% sodium carbonate aqueous solution. Add PAC (0.4 g) of viscosity average molecular weight 450,000 made by Aldrich to the sodium carbonate solution so as to be 2.0 w / v%, mix for 2 hours at room temperature, Produced. After preparing a solution obtained by adding HDB (2.1 g) and distilled water (20 mL) equimolar to the total number of carboxy groups of PAC contained in the neutralized solution, add the solution to the PAC neutralized solution at 60 ° C. After standing for 1 hour, an insoluble precipitate was formed. The state in the system is shown in FIG. After the produced precipitate was centrifuged, the supernatant was removed and filtered three times with distilled water. The obtained precipitate was dehydrated by immersing in acetone for 1 hour, and then dried under reduced pressure for 13 hours. The yield of PACIC (PAC / HDP) obtained by this production method was 100%.

Comparative Example 1 Production of PACIC (PAC / HDP) from PAC with Viscosity Average Molecular Weight 1.25 million Similar to Example 1 except that PAC with viscosity average molecular weight 450,000 was used instead of PAC with viscosity average molecular weight 450,000 PACIC (PAC / HDP) was recovered as a precipitate. The PACIC obtained by this production method was obtained in a yield of 74% as a gel-like solid containing water.

Reference Example 1: Production of PGAIC (PGA / HDP) For the production of PGAIC, the example of Patent Document 2 was referred to. That is, PGAIC (PGA / HDP) was used as a water-insoluble precipitate in the same manner as in the first experiment of Example 1 except that poly-γ-glutamic acid (PGA, weight average molecular weight: 1 million) was used instead of PAC. Got.

Test Example 1: Ion Complex Solubility Test The solubility of PACIC and PGAIC produced in Example 1, Comparative Example 1 and Reference Example 1 was tested. Specifically, PACIC or PGAIC was added to each solvent at a rate of 1.0 w / v% and stirred at room temperature for 24 hours or more. The results are shown in Table 1. The evaluation criteria in Table 1 are as follows.
○: When completely dissolved △: Not dissolved, but swollen with a solvent and gelled ×: Not swollen and completely insoluble

  As shown in Table 1, the PACIC according to the present invention showed solubility in ethanol (EtOH). Therefore, it can be expected to be used in a spray or a coating agent using an ethanol solution and can be molded. On the other hand, the PACIC of Comparative Example 1 produced from a PAC having a molecular weight exceeding 1 million was insoluble or gelled and could not be dissolved.

Example 2: Preparation of PACIC (PAC / HDP) film PACIC obtained in Example 1 above was cut into small pieces, placed on a glass petri dish heated on a hot plate (manufactured by Corning) heated to 80 ° C, and PACIC When softened, it was sandwiched between glass plates and stretched as thin as possible into a film by a simple crushing technique. After cooling to room temperature, the resulting film was cut into a 1 cm × 1 cm square.

Comparative Example 2: Production of PACIC (PAC / HDP) film An attempt was made to produce a film in the same manner as in Example 2 except that PACIC produced from PAC having a viscosity average molecular weight of 1.25 million obtained in Comparative Example 1 was used. did. However, since all parts of the preparation were gel-like and contained a lot of moisture, it was not suitable for thermoplastic molding such as so-called “plastic” materials that are insoluble in water and do not swell like gels. It was also difficult to hold. Therefore, PACIC manufactured from 1.25 million PACs was excluded from performance evaluation.

Reference Example 2: Production of PGAIC (PGA / HDP) Film A 1 cm × 1 cm square PGAIC film was produced in the same manner as in Example 2 except that the PGAIC obtained in Reference Example 1 was used.

Test Example 2: Antibacterial test An experiment for confirming the antibacterial properties of PACIC (PAC / HDP) according to the present invention was conducted. First, Bacillus subtilis (B. subtilis), which is a Gram-positive bacterium, was inoculated in a Luria-Bertani (LB) liquid medium and cultured at 37 ° C. for 1 day. Separately, an LB agar plate medium (20 mL) having the same composition was prepared in a petri dish having a diameter of 9 cm. The culture solution (about 20 μL) was applied on LB agar plate medium. The PGAIC film obtained in Reference Example 2 or the PACIC film obtained in Example 2 was placed near the center of the medium, and further cultured at 37 ° C. for 1 day. As a control, the same experiment was performed using a wiping cloth (Nippon Paper Crecia Co., Ltd., Kim Towel) cut into a 1 cm × 1 cm square. A photograph of the culture medium after wiping using the wiping cloth is shown in FIG. 3 (1), a photograph in the case of the PGAIC film is shown in FIG. 3 (2), and a photograph in the case of the PACIC film according to the present invention is shown in FIG. Shown in

  As shown in FIG. 3 (1) using only wiping cloth of the same size, the bacteria are usually confluent until they become confluent on a medium suitable for growth. On the other hand, if it cannot grow, it will be blank. PGAIC is known to exhibit antibacterial properties. As shown in FIGS. 3 (2) and 3 (3), it was confirmed that the PACIC according to the present invention exhibits the same antibacterial properties as PGAIC.

Test Example 3: Antibacterial test-Minimum inhibitory concentration against bacteria According to a general broth dilution method, a test sample obtained by serially diluting a steady-state bacterial solution adjusted to a bacterial suspension concentration of 1000000 cfu / mL using a nutrient broth The solution was applied on an agar medium to which the solution was added, and after static culture at 37 ° C. for 24 hours, the minimum inhibitory concentration (MIC) was determined based on the presence or absence of growth. Staphylococcus aureus (S. aureus), Pseudomonas aeruginosa (P. aeruginosa) and Escherichia coli (E. coli) were used as test bacteria. PACIC (PAC / HDP) of Example 1 was used as a test sample, and PGAIC (PGA / HDP) and HDB were used as comparative examples. As shown in Table 2, PACIC was found to have antibacterial properties equivalent to PGAIC.

Test Example 4: Antifungal Test-Minimum Growth Inhibitory Concentration for Fungi According to a general broth dilution method, a bacterial solution and a spore solution were respectively prepared from precultured fungi. The bacterial solution or spore solution was applied on an agar medium supplemented with a serially diluted test sample solution, allowed to stand at 28 ° C. for 2 to 5 days, and then the minimum inhibitory concentration (MIC) was determined based on the presence or absence of growth. . Candida albicans (C. albicans) and Aspergillus niger (A. niger) were used as test bacteria. PACIC (PAC / HDP) of Example 1 was used as a test sample, and PGAIC (PGA / HDP) and HDB were used as comparative examples. As shown in Table 3, PACIC was found to have antifungal properties equivalent to PGAIC.

Example 3: Production of PACIC (PAC / CP) A PAC (manufactured by Aldrich) having a viscosity average molecular weight of 450,000 (2.0% w / v%) with respect to a 1.5 w / v% sodium carbonate aqueous solution ( 1.0 g) and mixed at room temperature for 2 hours to prepare a PAC neutralization solution. A solution obtained by adding equimolar cetylpyridinium chloride (hereinafter abbreviated as “CPC”) (5.0 g) and distilled water (47.8 mL) to the total carboxy group of the PAC contained in the neutralization solution. It added to the PAC neutralization liquid and left still at 60 degreeC for 1 hour, and the insoluble precipitation was produced | generated. After the produced precipitate was centrifuged, the supernatant was removed, washed with distilled water, and filtered three times. The resulting precipitate was dried under reduced pressure for 24 hours. PACIC (PAC / CP) obtained by this production method was 100% in yield.

Example 4: Production of PACIC (PAC / BA) A PAC having a viscosity average molecular weight of 450,000 (manufactured by Aldrich) was adjusted to 2.0 w / v% with respect to a 1.5 w / v% aqueous sodium carbonate solution. (1.0 g) was added and mixed at room temperature for 2 hours to prepare a PAC neutralization solution. A solution obtained by adding benzalkonium chloride (hereinafter abbreviated as “BAC”) (5.1 g) equimolar to the total carboxy group of PAC contained in the neutralized solution to distilled water (47.8 mL). Was added to the PAC neutralization solution and allowed to stand at 60 ° C. for 1 hour to form an insoluble precipitate. After the produced precipitate was centrifuged, the supernatant was removed, washed with distilled water, and filtered three times. The resulting precipitate was dried under reduced pressure for 24 hours. The yield of PACIC (PAC / BA) obtained by this production method was 89%.

Example 5: Production of PACIC (PAC / LP) A PAC (manufactured by Aldrich) having a viscosity average molecular weight of 450,000 was adjusted to 2.0 w / v% with respect to a 1.5 w / v% aqueous sodium carbonate solution. (1.0 g) was added and mixed at room temperature for 2 hours to prepare a PAC neutralization solution. A solution obtained by adding equimolar laurylpyridinium chloride (hereinafter abbreviated as “LPC”) (4.0 g) to distilled water (47.8 mL) with the total carboxy group of PAC contained in the neutralized solution. It added to the PAC neutralization liquid and left still at 60 degreeC for 1 hour, and the insoluble precipitation was produced | generated. After the produced precipitate was centrifuged, the supernatant was removed, washed with distilled water, and filtered three times. The resulting precipitate was dried under reduced pressure for 24 hours. PACIC (PAC / LP) obtained by this production method was a yield of 100%.

Test Example 5: Antibacterial test-adhesion of PACIC to metal In order to evaluate adhesion of PACIC to metal, a halo test was performed. As PACIC test solutions, solutions were prepared in which various PACICs obtained in Examples 3, 4 and 5 were dissolved in 70% ethanol at 0.1 w / v%. A PACIC test solution was sprayed three times from a spray bottle onto a 10 mm square, 1 mm thick stainless steel piece (SUS304), and then air-dried to obtain a test piece before water washing. Next, these stainless steel pieces dried after spraying were immersed in 25 mL of fresh sterilized distilled water for 5 minutes, washed a total of 3 times, and then air-dried to obtain test pieces after water washing. As a control test solution, a solution in which the quaternary ammonium salt used in Examples 3, 4 and 5 was dissolved in 70% ethanol at 0.1 w / v% was used.

  A suspension of Staphylococcus aureus NBRC13276 was subjected to liquid culture at 37 ° C. for 16 hours in a Soybean Casein Digest (SCD) liquid medium, and then added to an SCD agar medium kept at 50 ° C. to a concentration of 1000000 cfu / mL. A solid medium containing was prepared. Three pieces of each of the above test pieces were placed on the solid medium and cultured at 37 ° C. for 24 hours. The halo width formed around each test piece was measured, and the average value was calculated. The results are shown in Table 4.

  As shown in Table 4, a clear halo was formed around the stainless steel piece sprayed with the PACIC solution, not only before water washing after spraying but also after water washing. On the other hand, no halo was formed on the periphery of the stainless steel piece sprayed with the quaternary ammonium salt solution after washing with water. These results indicate that the adhesion of PACIC to the stainless steel piece is maintained after washing with water as well as antibacterial properties.

Test Example 6: Antibacterial test-Adhesiveness of PACIC to ceramics In order to evaluate the adhesiveness of PACIC to ceramics, a halo test was performed. As in Test Example 5, a PACIC test solution was sprayed three times from a spray bottle onto a 10 mm square tile piece (ceramics), and then air-dried to obtain a test piece before water washing. Next, these tile pieces were immersed in 25 mL of fresh sterilized distilled water for 5 minutes and washed a total of 3 times, and then air-dried to obtain test pieces after water washing. As a control test solution, a solution in which the quaternary ammonium salt used in Examples 3, 4 and 5 was dissolved in 70% ethanol at 0.1 w / v% was used.

  Similarly to Test Example 5, a solid medium containing cells of Staphylococcus aureus NBRC13276 was prepared. Three pieces of each of the above test pieces were placed on the solid medium and cultured at 37 ° C. for 24 hours. The halo width formed around each test piece was measured, and the average value was calculated. The results are shown in Table 5.

  As the results shown in Table 5, a clear halo was formed not only before spraying but also after water cleaning in the periphery of the tile piece sprayed with the PACIC solution. On the other hand, no halo was formed around the tile pieces sprayed with the quaternary ammonium solution after washing with water. These results indicate that the adhesion of PACIC to the tile pieces is maintained after washing with water as well as antibacterial properties.

Test Example 7: Antibacterial test-Adhesiveness of PACIC to polypropylene nonwoven fabric In order to evaluate the adhesiveness of PACIC to polypropylene nonwoven fabric (PP nonwoven fabric), a halo test was performed. As in Test Example 5, a PACIC test solution was sprayed three times from a spray bottle onto a PP nonwoven fabric cut into a circle having a diameter of 10 mm, and then air-dried to obtain a test sample before water washing. Next, these PP nonwoven fabrics were immersed in 25 mL of fresh sterilized distilled water for 5 minutes, washed a total of three times, then air-dried to obtain test samples after water washing. As a control test solution, a solution in which the quaternary ammonium salt used in Examples 3, 4 and 5 was dissolved in 70% ethanol at 0.1 w / v% was used.

  In the same manner as in Test Examples 5 and 6, a solid medium containing cells of Staphylococcus aureus NBRC13276 was prepared. Three pieces of each PP nonwoven fabric sample were placed on the solid medium, and cultured at 37 ° C. for 24 hours. The halo width formed around each test sample was measured, and the average value was calculated. The results are shown in Table 6.

  As the results shown in Table 6, a clear halo was formed not only before water washing after spraying but also after water washing in the periphery of the PP nonwoven fabric sprayed with the PACIC solution. On the other hand, no halo was formed on the periphery of the PP nonwoven fabric sprayed with the quaternary ammonium solution after washing with water. These results indicate that the adhesion of PACIC to PP nonwoven fabric is maintained after washing with water as well as antibacterial properties.

  The ion complex of the present invention can be manufactured using polyacrylic acid that can be supplied at low cost, and can be used as an antibacterial plastic material that can be directly molded into a film, fiber, etc. It can be an extremely useful industrial material as an antibacterial material that can be blended and compounded.

Claims (6)

It contains poly (meth) acrylic acid having a viscosity average molecular weight of 100,000 or more and 1,000,000 or less and a quaternary ammonium ion of the following formula (I) and / or formula (II). Ion complex.

[Wherein R ^{1 to} R ³ represent the same or different C _1-20 alkyl group, benzyl group, C _6-12 aryl group, and R ^{4 to} R ⁵ independently represent a C _12-20 alkyl group. ]   The ion complex according to claim 1, comprising the quaternary ammonium ion (II).   The ion complex according to claim 1 or 2, wherein the quaternary ammonium ion is contained in an equimolar or substantially equimolar amount with respect to a (meth) acrylic acid unit constituting the poly (meth) acrylic acid.   The ion complex according to any one of claims 1 to 3, wherein the poly (meth) acrylic acid has a viscosity average molecular weight of 400,000 or more.   The ion complex according to any one of claims 1 to 4, which is water-insoluble.   An antibacterial plastic material comprising the ion complex according to any one of claims 1 to 5.