JP2000080008A - Inorganic antimicrobial and fungicidal agent, antimicrobial resin composition and antimicrobial resin product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an inorganic antimicrobial and fungicidal agent that can sufficiently manifest its antimicrobial properties in the resin product after the agent is added to the parent resin material and fabricated to the products inexpensively with high safety without adverse effect on the basic performance of the resin products and is useful for protection of food package, vessel and the like from bacteria and fungi by using fired dolomite. SOLUTION: The fired dolomite that is preferably fired at 900-1,200 deg.C, preferably mainly comprises magnesium oxide and calcium oxide is admixed to the composition in an amount of >=25 wt.%. The antimicrobial activity of this agent is preferably >=85% to both colon bacillus and staphylococcus. This agent can retain extremely high antimicrobial effect against the staphylococcus secreting the toxin causing food poisoning and the colon bacillus 0-157 and can be widely applied to a chopping board, kitchenware, refrigerator and the like as well as to the daily necessaries for toilet, bathroom and the like susceptible to the secondary infection.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel inorganic antibacterial / antifungal agent, an antibacterial resin composition using the same, an antibacterial resin product, and a method for producing the resin composition. More specifically, an inorganic antibacterial and antifungal agent capable of sufficiently exhibiting antibacterial properties in a resin product after being added to all kinds of base resin and processed, an antibacterial resin composition using the same, and an antibacterial agent And a method for producing the composition.

[0002]

2. Description of the Related Art Resin (the term "resin" as used in this specification refers to a broader meaning that can be interpreted in a broader sense than generally defined. In addition to the curable resin, the resin composition should include a base resin of a structure forming material such as a plastic or an elastomer material, and the resin composition contains a thermoplastic resin and a thermosetting resin as main components, and further includes a plasticizer as an optional component. In addition, plastics containing compounding agents and additives such as antioxidants, fillers, antistatic agents, etc., as well as structure-forming materials such as elastomeric materials, etc. The resin products are formed using a resin composition. This includes various molded products such as resin and plastic, as well as various processed products such as rubber and fiber.) For processing, plasticizers, antioxidants, fillers, antistatic It is essential compounding ingredients or additives such as agents. Antibacterial and antifungal agents are also one of the essential additives for some resin compositions.
It is an essential component regardless of the type of base resin. For example, microbial damage to resin products is common today, and it often requires some kind of antibacterial treatment besides susceptible resins such as soft vinyl chloride resin and urethane resin.

[0003] Antibacterial and antifungal agents used in currently provided resins can be roughly classified into organic and inorganic.

[0004] Organic antibacterial and antifungal agents, which are conventionally known as bactericides, can withstand heating during processing of resin products and have long lasting properties when kneaded into the resin products. The organic stable antibacterial and antifungal agents include 2- (4-thiazolyl) -benzimidazole, N- (fluorodichloromethylthio) -phthalimide, 2,3,5 and 6-cytochloro-4
-(Methylsulfonyl) -pyridine, 10,10'-
Oxybisphenoxyarsine, trimethoxysilyl-
Propyl octadecyl ammonium chloride, 2-n
-Octyl-4-isothiazolin-3-one, bis (2
-Pyridylthio-1-oxide) zinc and the like.

However, such organic antibacterial and antifungal agents diffuse into the environment from the processed product of the resin composition due to volatilization and elution, and exhibit an immediate effect. Therefore, the expiration date is relatively short, and the effect on the human body and the like is relatively short. It can be said that it is relatively strong. In addition, some of the organic antibacterial and antifungal agents are suspected to be teratogenic, and some of the waste are toxic. Furthermore, it is particularly safe in applications where it is desired to be safe in all stages of processing, use and disposal, such as the potential toxicity of antibacterial and antifungal agents themselves, toxicity when gasifying, and toxicity of thermal decomposition products. It can be said that there is a difficulty in securing the sex. In addition, the organic antibacterial and antifungal agents include a processing temperature of the resin composition (such as 200
Some are below 200 ° C, most are above 200 ° C, and some even close to 300 ° C. )) Has heat resistance as a single product, but when added to the resin composition,
The resin may be decomposed at a lower temperature to yellow the resin or adversely affect the molding. Furthermore, such organic antibacterial and antifungal agents are relatively expensive.

On the other hand, inorganic antibacterial and antifungal agents include silver, copper,
Most metal-substituted antibacterial and antifungal agents carry an antibacterial metal such as zinc on an inorganic ion exchanger or porous carrier such as zirconium phosphate, zeolite, hydroxyapatite, silica / alumina, and silica gel. However, silver-based inorganic antibacterial agents which are effective and highly safe are generally used in many cases. With these inorganic antibacterial and antifungal agents,
Although the above-mentioned problems such as organic antibacterial and antifungal agents do not occur, the metal ion as an active ingredient catalytically degrades the base material resin.
Some of them have difficulty in light fastness, for example, they change into metallic silver and easily discolor. In addition, such an inorganic antibacterial / antifungal agent also needs to be supported on an inorganic ion exchanger or a porous body, and requires a predetermined number of manufacturing steps, and is therefore relatively expensive.
These conventional inorganic antibacterial and antifungal agents are
It hardly volatilizes or dissolves like a fungicide, and the effect of the dispersion on the surface of resin products such as processed products only comes into contact with bacteria and molds. When an antibacterial coating is formed on a resin composition, a known inorganic antibacterial and antifungal agent is added and mixed at a predetermined ratio to the resin composition (or resin surface). However, it is not possible to produce a film having sufficient antibacterial properties even if the antibacterial coating film is processed.
In addition, inorganic antibacterial materials including composite ceramics with a new and extremely high antibacterial property at a predetermined ratio to base resin, etc.
Even if a resin or the like is processed by adding and mixing a fungicide, a product having an antibacterial property exceeding the conventional level cannot be produced.

[0007]

Accordingly, an object of the present invention is to provide a novel inorganic antibacterial / antifungal agent which solves the technical problems of conventional organic and inorganic antibacterial / antifungal agents. It is.

Another object of the present invention is to solve the technical problems of conventional antibacterial resin products using organic and inorganic antibacterial and antifungal agents, and to provide an inorganic antibacterial and antifungal agent having excellent antibacterial properties. Antibacterial resin products having substantially the same antibacterial activity without substantially lowering, and preferably hardly lowering, the antibacterial activity of the product (including the resin formed using inorganic antibacterial and antifungal agents) And an antimicrobial resin composition.

[0009]

Means for Solving the Problems In order to achieve the above object, the present inventors have conducted intensive studies on the technology of inorganic antibacterial and antifungal agents and antibacterial resin compositions. The present inventors have found that an antibacterial resin composition can be realized by adding a solvent (a good solvent having an SP value substantially equal to the solubility parameter of the base resin) to the base resin in addition to the base antibacterial / antifungal agent. The invention has been completed.

An object of the present invention is to provide the following (1) to (2)
3) is achieved.

(1) An inorganic antibacterial / antifungal agent containing calcined dolomite.

(2) An inorganic antibacterial / antifungal agent containing 25% by weight or more of calcined dolomite.

(3) The calcined dolomite has a temperature of 900-900.
The inorganic antibacterial and antifungal agent according to the above (1) or (2), which is fired at 1200 ° C.

(4) The inorganic antibacterial and antifungal agent according to any one of the above (1) to (3), wherein the calcined dolomite is mainly composed of magnesium oxide and calcium oxide. Agent.

(5) The inorganic antibacterial / antifungal agent has an antibacterial activity (X) of 85% or more with respect to both Escherichia coli and staphylococci.
The inorganic antibacterial and antifungal agent according to any one of (4).

(6) A good solvent for the base resin and the above (1) to
(5) An antibacterial resin composition comprising the inorganic antibacterial and antifungal agent according to any one of (1) and (2),
An antibacterial resin composition in which the antifungal agent is 2.5 to 20% by weight based on the base resin and the good solvent is 0.05 to 1.5% by weight based on the base resin.

(7) The calcined dolomite has a temperature of 900-900.
The antibacterial resin composition according to the above (6), which is fired at 1200 ° C.

(8) The antibacterial resin composition according to the above (6) or (7), wherein the polymer resin is at least one selected from an elastomer, a halogen-containing resin and a polymer.

(9) The good solvent according to any one of (6) to (8), wherein the good solvent is a solvent having a solubility parameter (SP ₂ ) substantially equal to the solubility parameter (SP ₁ ) of the resin base material. The antibacterial resin composition according to any one of the above.

(10) The good solvent is SP ₁ and SP
₂ relationship, | SP ₁ -SP ₂ | antibacterial resin composition according to the above (9), characterized in that it is intended to satisfy ≦ 1.

(11) An antibacterial resin product formed by using the antibacterial resin composition according to any one of (6) to (10).

(12) The antibacterial rate (X) of the inorganic antibacterial and antifungal agent alone contained in the antibacterial resin composition and the antibacterial rate of the antibacterial resin product formed using the antibacterial resin composition The antibacterial resin product according to the above (11), wherein the phase relationship with (Y) satisfies Y ≧ 0.6X.

(13) An inorganic antibacterial / antifungal agent as described in any one of (1) to (5) above, which is contained in an amount of 2.5 to 20% by weight based on a base resin. Claim 1
13. The antibacterial resin product according to 1 or 12.

(14) Any one of the above (11) to (13), wherein the particle diameter of the inorganic antibacterial / antifungal agent of any one of the above (1) to (5) is 15 μm or less. The antibacterial resin product according to any one of the above.

(15) A resin product containing the inorganic antibacterial / antifungal agent according to any one of (1) to (5) in an amount of 2.5 to 20% by weight based on a base resin. The antibacterial activity (X) of the inorganic antibacterial and antifungal agent,
An antibacterial resin product characterized in that the correlation with the antibacterial activity (Y) of a resin article containing a fungicide satisfies Y ≧ 0.6X.

(16) The antibacterial resin product according to any one of the above (11) to (15), wherein the inorganic antibacterial and antifungal agent has a particle size of 5 nm to 15 μm.

(17) The correlation between the antibacterial activity (X) of the inorganic antibacterial and antifungal agent and the antibacterial activity (Y) of the resin article satisfies Y ≧ 0.90X. The antibacterial resin product according to any one of the above (11) to (16).

(18) To the base resin, an additive containing a good solvent for the base resin and the inorganic antibacterial / antifungal agent described in any one of the above (1) to (5) is added. A method for producing an antibacterial resin composition, comprising:

(19) The above (1), wherein the addition amount of the good solvent is 0.05 to 1.5% by weight based on the base resin.
A method for producing the antibacterial resin composition according to 8).

(20) The above (18) or (19), wherein the good solvent is a solvent having a solubility parameter (SP ₂ ) substantially equal to the solubility parameter (SP ₁ ) of the base resin. A method for producing an antibacterial resin composition of the invention.

[0031] (21) Relation of the SP ₁ and the SP ₂ is, | SP ₁ -SP ₂ | according to (20), characterized in that it is intended to satisfy ≦ 1 antibacterial resin composition Production method.

(22) A method for producing an antibacterial resin product, which is formed by using the antibacterial resin composition according to any one of (6) to (10).

(23) At least on the surface of the substrate,
A method for producing an antibacterial resin product, comprising forming a film or a laminated portion having antibacterial properties using the antibacterial resin composition according to any one of the above (6) to (10).

[0034]

BEST MODE FOR CARRYING OUT THE INVENTION The inorganic antibacterial and antifungal agent of the present invention is characterized by containing calcined dolomite, and is preferably characterized by containing calcined dolomite at 25% by weight or more. More preferably, the calcined dolomite is calcined at a temperature of 900 to 1200 ° C, or the calcined dolomite is mainly composed of magnesium oxide and calcium oxide. Particularly preferably, the antibacterial activity (X) of the inorganic antibacterial and antifungal agent is at least 85% against Escherichia coli and staphylococci. These details will be described later in the description of the antibacterial resin composition or antibacterial resin product.

The antibacterial resin product of the present invention has an inorganic antibacterial property.
The correlation between the antibacterial rate (X) of the antifungal agent itself and the antibacterial rate (Y) of the resin product using the inorganic antibacterial / antifungal agent is Y ≧
0.6X is satisfied. In such an antibacterial resin product, the antibacterial effect of the inorganic antibacterial and antifungal agent alone can be maintained without significantly impairing it.
High antibacterial activity can be exhibited. Here, the antibacterial resin product is not a temporary effect such as ultraviolet irradiation, gas sterilization, etc., but rather a chemical agent (antibacterial / antifungal agent) to add and blend the effect of suppressing bacteria and mold. What can be sustained.

The antimicrobial activities (X) and (Y) of the present invention
Shall use the measurement method certified by the Japan Society of Bactericidal and Antifungal Studies. In other words, regarding the antibacterial activity against fungi, the inorganic antibacterial and antifungal agent in powder form and the resin in powder form are both measured by the shake method, and for various processed products (having a certain shape) of the resin,
It shall be measured by the pressurization method. For molds, a measurement method according to JIS Z2911 is used. The outline of these measurement methods is briefly described below.

Shake method: A method for evaluating antibacterial activity applicable to processed products in powder form, wherein a sample (a powdery inorganic antibacterial and antifungal agent and a powdery resin product) in a phosphate buffer solution is subjected to a test. The bacteria are allowed to coexist, and the number of viable bacteria is measured after shaking for a certain period of time. That is, a method in which the sample dispersed in the aqueous solution and the test bacteria are forcibly brought into contact with each other by shaking to confirm the effect.

Pressurization method: a method for evaluating antibacterial activity which can be suitably applied to processed products having a certain shape (many processed products of resin correspond to these products).
An appropriate amount (for example, 0.025 mm × 25 mm) of a sample resin suspended in a 1% aqueous solution of peptone was used.
(50 ml) is applied (1.0 × 10 per sample)
⁶ cell count inoculation). Next, a sterilized polyethylene film (30 × 30 mm) is brought into close contact with an appropriate temperature (for example,
0 ° C) and humidity (humidified state), and after 24 hours, an appropriate amount of S
The bacterial solution is washed out with a CDLP medium (for example, 10 ml), appropriately diluted, and then subjected to a plate pour method (SCDLP agar medium culture 3).
(2 ° C. for 48 hours) to measure the viable cell count.

Measurement method according to JIS Z2911; a method for evaluating the growth inhibitory effect of mold specified in JIS Z2911 as a mold resistance test, and various processed products of the inorganic antibacterial / antifungal agent and resin of the present invention (any The present invention is a method for evaluating antibacterial activity that can be applied to various forms of the inorganic antibacterial and antifungal agent or resin of the present invention, which is a sample, on a flat plate agar medium, This is a method in which a spore suspension is inoculated on one side and the growth of the mold on the sample after culturing for 3 to 4 weeks while maintaining an appropriate temperature and humidity is observed visually or by a microscope to judge the result.

In the present invention, the correlation between the antibacterial rate (X) of the inorganic antibacterial / antifungal agent itself and the antibacterial rate (Y) of the resin product using the inorganic antibacterial / antifungal agent is Y ≧ 0. It satisfies 6X, but preferably satisfies Y ≧ 0.75X, more preferably Y ≧ 0.90X.
When Y <0.6X, the antibacterial effect of the inorganic antibacterial and antifungal agent alone is significantly impaired, so that an antibacterial resin product using the conventional inorganic antibacterial and antifungal agent can be achieved. The antimicrobial effect can be expressed only to the same degree as the antimicrobial effect, and no excellent antimicrobial activity can be expected as compared with the conventional antimicrobial resin composition. In addition, Y ≧ 0.75X, and further, Y ≧ 0.
In the one that satisfies the relationship of 90X, inorganic antibacterial
It is possible to realize an extremely excellent antibacterial resin product without substantially impairing the antibacterial activity of the fungicide itself,
Since the antibacterial activity of a certain level or more can be maintained for a long period of time, it is useful in a wide range of fields such as sanitary fields where antibacterial properties are strongly desired, wallpaper, flooring etc., home interior materials, sealing materials etc. Can be used.

In other words, it is particularly preferable that the antibacterial resin product of the present invention has an antibacterial activity substantially the same as that of the inorganic antibacterial and antifungal agent. Therefore, the inorganic antibacterial / fungicide is contained with respect to the value (X) quantified so that the antibacterial properties when the inorganic antibacterial / fungicide alone is used can be objectively determined. Value (Y) quantified so that the antimicrobial activity of resin products can be objectively determined
However, if it satisfies the more preferable range of Y ≧ 0.90X, it can be said that the antibacterial activity is substantially the same. In the present invention, it is not particularly necessary to use the numerical values obtained by the above-described measurement methods as a reference. For example, inorganic measurement can be performed by other measurement methods such as an evaluation method newly certified by the Japanese Society of Antibacterial and Fungicide. A numerical value (X) is given so that the antibacterial activity when the antibacterial and antifungal agent is used alone can be objectively determined.
If numerical values (Y) are given so that the antimicrobial activity of the resin containing the antifungal agent can be objectively determined, the relationship of Y ≧ 0.90X is determined based on these numerical values. In terms of satisfaction, it can be said that "the antibacterial resin composition (or antibacterial resin product) retains substantially the same antibacterial activity as that of the inorganic antibacterial and antifungal agent". .

The antibacterial resin composition of the present invention is an antibacterial resin composition comprising a base resin mixed with a good solvent and an inorganic antibacterial / antifungal agent. The antimicrobial resin composition is 2.5 to 20% by weight based on the material resin and 0.05 to 1.5% by weight based on the good solvent. In the present invention, the term “resin” is a polymer substance that can be dissolved in, mixed with, or absorbs a solvent, and does not include polyamide, DNA and RNA.

The base resin that can be used in the antibacterial resin composition of the present invention is not particularly limited, and resins (polymers) conventionally used as base materials for resin products may be used. can do. If a part (representative example) of such a resin (polymer) is shown, for example, an elastomer such as butyl rubber and natural rubber, a halogen-containing resin such as polytetrachloroethylene, polyvinyl chloride, polyvinyl denchloride, and polyvinyl chloroacetate; And polydimethylsiloxane (silicon), polypropylene, polyethylene, hydrogenated polybutadiene, polybutadiene / styrene (85/15, 7
5/25, 60/40), polyisobutylene, polybutadiene, polybutyl acrylate, polyethylene hexyl methacrylate, polyethoxymethyl methacrylate, polypropyl acrylate, polystyrene, polysulfide (thiochol rubber), polystyrene divinylbenzene, polymethyl methacrylate, neoprene, polybutadiene / Acrylonitrile (75/25), polyvinyl acetate, polyethyl acrylate, polymethyl acrylate, epoxy resin, polyurethane, ethyl cellulose, polyethylene glycol terephthalate, cellulose diacetate, cellulose dinitrate, polymethylenoxide, phenolic resin, nylon, poly Examples include high molecular polymers such as methacrylonitrile and polyacrylonitrile. As exemplified above, the resin material used as the base resin may be used alone, may be a composite of two or more, or may be a copolymer.

The amount of the base resin is 20 to 97.5% by weight, more preferably 30 to 95% by weight, and especially 40 to 90% by weight of the base resin with respect to the antibacterial resin composition. That is.

The inorganic antibacterial and antifungal agent that can be used in the antibacterial resin composition of the present invention is not particularly limited, and may be any of a metal inorganic material having antibacterial activity and a nonmetallic inorganic material. Can also be used, and these can be used in an appropriate combination. this house,
As for the metal-based inorganic material having antibacterial properties, in addition to the various known inorganic antibacterial and antifungal agents as described above, oxides thereof (eg, zinc oxide, titanium oxide, etc.) can be used. Examples of the nonmetallic inorganic material having antibacterial activity include, for example, composite ceramics (specifically, fine particles (preferably, 1 nm to 2 μm) having deodorization and antibacterial properties separately invented by the present inventors. hand,
Magnesia fine powder as a base material, the base material is 35 ~
Γ-alumina of fine grains (preferably 1 nm to 2 μm in diameter), which is a single component ceramic, for 65% by weight,
One kind of fine powder of silica stone, amphibolite, serpentine, zinc oxide, zeolite or Oya stone is used as a mixed material, and the mixed material is added and mixed in the base material at a ratio of 35 to 65% by weight. Composite ceramics), magnesia (Mg) used as a raw material of the composite ceramics,
O), non-metallic inorganic materials having antibacterial activity such as γ-alumina, amphibolite and serpentine, and the like, and a novel nonmetallic inorganic antibacterial and antifungal agent invented by the present inventors.
There are calcined dolomite containing magnesium oxide and calcium carbonate as main components, calcined dolomite containing magnesium oxide and calcium oxide as main components, unfired dolomite, and mixed compositions containing these. These can be said to be more preferable since they have a deodorizing effect in addition to an antibacterial and antifungal effect.

In the present invention, as an inorganic antibacterial and antifungal agent,
The above-mentioned metal-based inorganic material and non-metal-based inorganic material may be used alone or as a composite of two or more.

Here, unfired dolomite is generally a complex carbonate of calcium and magnesium CaMg (CO
₃ ) ₂ or rocks containing this as a main component. When this dolomite is heated, MgCO ₃ is decomposed at 700 to 800 ° C. to release CO _2, and calcium carbonate (CaC
O ₃ ) and a calcined product of magnesium oxide (MgO)
Simply called calcined dolomite A), and 900
At ~ 950 ° C, CaCO ₃ is decomposed to release CO _2, and calcium oxide (CaO) and magnesium oxide (MgO)
(Hereinafter, also simply referred to as calcined dolomite B). Therefore, the calcined dolomite containing magnesium oxide and calcium carbonate as main components refers to calcined dolomite A described above, and the calcined dolomite containing magnesium oxide and calcium oxide as main components refers to calcined dolomite B described above. Among the above-mentioned inorganic antibacterial and antifungal agents, they are particularly excellent in antibacterial activity, can be easily produced, are extremely inexpensive, have excellent safety, and catalytically degrade the base resin. Without
A material containing calcined dolomite B is desirable because it is excellent in light resistance and heat resistance. In particular, ceramics obtained by sintering a composition containing calcined dolomite B by an appropriate method (hereinafter, also simply referred to as antibacterial composite ceramics) may be used. As a method for producing such an antibacterial composite ceramic, a composition containing dolomite blended in an appropriate ratio is charged into a mixer and a pulverizer several times in order, so that the composition has a predetermined particle size. The dolomite may be uniformly and uniformly mixed, and then calcined at a temperature of 900 ° C. or higher, or dolomite may be heated to 900 ° C. or higher, more preferably 900 to 1200 ° C., particularly 1000 to 1100.
Sintering at a temperature of 700 ° C. to obtain sintering dolomite B, and other composition components (when sintering dolomite A is included, sintering dolomite at a sintering temperature of 700 to 800 ° C.)
Are mixed in an appropriate ratio, and are sequentially charged into a mixer and a pulverizer a plurality of times to uniformly and uniformly mix the composition to a predetermined particle size, and then calcined at a calcining temperature of 200 to 500 ° C. May be.

As the inorganic antibacterial and antifungal agent of the present invention, calcined dolomite as a main component is 25 to 100% by weight,
And 90 to 40% by weight, and as other components, 0 to 50% by weight of MgO and 0 to 0% by weight of SiO.
25% by weight, 0 to 10% by weight of ZnO, 0 to 5% of TiO
0% by weight can be contained.

The particle size of the inorganic antibacterial and antifungal agent is 5 nm to 15 μm, preferably 5 nm to 10 μm,
More preferably, it is 5 nm to 1 μm. This is because even with the same amount of inorganic antibacterial / antifungal agent, the surface area decreases as the particle size increases, so that the inorganic antibacterial / antifungal agent dispersed on the resin surface etc. comes into contact with bacteria and molds. When the particle diameter of the inorganic antibacterial and antifungal agent exceeds 15 μm, the surface area of undesired particles and the strength of the resin decrease, which is not preferable. On the other hand, if it is less than 5 nm, the compounding capacity is too large, and the resin strength may be undesirably reduced.

Further, the antibacterial rate (X) of the inorganic antibacterial and antifungal agent is 85% or more, preferably 95% or more, more preferably 97% or more with respect to both Escherichia coli and Staphylococcus. Is desirable. When the antibacterial activity (X) of the inorganic antibacterial / fungicide is less than 85% against any one of Escherichia coli and staphylococcus, the antibacterial activity of the inorganic antibacterial / fungicide is higher than that of the inorganic antibacterial / fungicide itself. Since a resin cannot be applied to a resin, it is difficult to provide a resin having a high antibacterial activity of a certain level or more, which is not preferable. Here, E. coli and staphylococci are usually selected. That is, it is representative of bacilli and cocci. The active oxygen theory, which is a powerful antibacterial agent of inorganic antibacterial and antifungal agents,
It is the theory that active fungi generated by light irradiation in the presence of a fungicide in the presence of oxygen or water is based on a mechanism that oxidizes and kills fungi in general, and according to this, one or two representative bacteria and fungi Is enough.

In the present invention, the content of the inorganic antibacterial and antifungal agent is 2.5 to 20% by weight, preferably 3.5 to 7.5% by weight based on the base resin of the antibacterial resin composition. %, More preferably in the range of 3.5 to 5.0% by weight. When the content of the inorganic antibacterial and antifungal agent is less than 2.5% by weight based on the base material of the antibacterial resin composition, it becomes difficult to sufficiently exhibit a desired antibacterial effect. If it is not preferable, and if it exceeds 20% by weight, the strength of the resin decreases, which is not preferable.

The other compounding agents or additives other than the inorganic antibacterial and antifungal agents that can be used in the antibacterial resin composition of the present invention are not particularly limited, and the compounding agents for conventionally known resins can be used. Additives or additives, for example, diluent monomers, plasticizers, antioxidants, fillers, compounding agents or additives such as antistatic agents can be used as appropriate, if necessary, and new Inorganic materials, such as deodorants and repellents, capable of exhibiting value-added applications can also be added. Among these, inorganic materials such as a deodorant and a repellent can be added to the inorganic antibacterial / antifungal agent as a compounding component of the inorganic antibacterial / antifungal agent.

The use form of the antibacterial resin composition of the present invention is not particularly limited, and it can be applied to any form according to its use.
One example is film materials, food containers, chopping boards, kitchen supplies, daily necessities such as bath products, refrigerators, washing machines, portable terminals (telephones), water purifiers, air conditioners and other appliances suitable for food packaging. Molding materials (molding materials such as plates, bars, and molding materials with shapes suitable for applications) suitable for parts used in parts where antibacterial properties are required, home interior materials such as wallpaper and flooring materials, Molding materials suitable for composite materials of the antibacterial resin composition of the present invention and other materials (mainly film materials, thin sheet materials, building materials such as sealing materials, water treatment materials for various tanks and pipes, etc.) It can be in any form, such as fibrous materials suitable for textiles such as rods, socks, carpets, bedding and the like.

Next, the antibacterial resin product of the present invention described above can be manufactured by the following novel manufacturing method. That is, the antimicrobial resin product of the present invention is manufactured by (1) adding a good solvent to the base resin and an additive containing an inorganic antibacterial and antifungal agent to the base resin and processing the resultant. A method or (2) forming a coating or laminated portion having antibacterial properties on at least a surface portion of the resin product by using a paint containing a good solvent for a resin component of the paint and an inorganic antibacterial / antifungal agent. It can be made by a manufacturing method. In the production method (1), a masterbatch in which an additive containing an inorganic antibacterial and antifungal agent and a good solvent for the base material resin are mixed in a high concentration in advance in a part of the base material resin is used. By diluting with a resin, the resin can be uniformly dispersed throughout the base resin and processed. Add a good solvent to the base resin at a specified ratio when diluting a master batch in which an additive containing an inorganic antibacterial and antifungal agent is partially added to a part of the base resin in advance with the remaining base resin. The addition of a good solvent to the resin component of the paint and the paint containing an inorganic antibacterial and antifungal agent, etc., are particularly limited, as it can be evenly dispersed and processed throughout the base resin. Instead, the most suitable mixing method among conventionally known methods can be applied.

The production method (1) is particularly suitable for imparting antibacterial activity to the whole resin product.
It is a means that allows the resin product to have antibacterial activity at the same time as the resin product is molded. In other words, the conventional manufacturing method simply worked by kneading an additive such as an inorganic antibacterial / mildew-proof agent into the base resin, or using an inorganic antibacterial / mildew-proof agent on the surface of the resin product. While the antibacterial coating film was formed using the paint containing, by adding a good solvent of the base resin or the resin component of the paint newly,
It has been found that it is possible to obtain an antibacterial resin product having substantially the same antibacterial properties without significantly reducing the antibacterial effect of the inorganic antibacterial and antifungal agent itself, and such findings complete the present invention. This is a very important point. That is, based on such knowledge, the antibacterial resin product having the antibacterial property of the present invention was obtained for the first time. In addition, regarding the mechanism of action of the antibacterial activity of the antibacterial resin product of the present invention, which is provided by the good solvent used in the method for manufacturing the antibacterial resin product, the antibacterial resin composition in the final portion using the solvent is extremely low. A porous resin product with a large number of fine pores is completed, which increases the active oxygen generated by light irradiation in the presence of oxygen or water, starting from the inorganic antibacterial / antifungal agent that appeared on the inner surface of the pores However, the effect of oxidizing and sterilizing fungi can be enhanced to a level comparable to the antibacterial effect of the inorganic antibacterial and antifungal agents themselves, or a new effect not based on the active oxygen theory. It is not yet clear whether the mechanism can exert an excellent antibacterial effect in a part that is not foreseen at all, and it is necessary to wait for future research results.

The method suitable for the above-mentioned method (1) is suitable for the case where the surface portion is easily worn and it is difficult to maintain the antibacterial effect for a long time by the method (2), or It is technically possible to apply the manufacturing method (2) after obtaining a resin product, so to speak, such as a molded product having an extremely complicated shape or a large form, or a fine (small) uneven pattern on the surface. In some cases, it is difficult or technically no problem, but it is more expensive than the method (1) in terms of economy. On the other hand, (2)
It is particularly suitable for disposable food containers and packaging materials for disposable food containers unless the usage mode is such that internal and external pressure is applied to the surface portion or the like. A preferred embodiment is one in which both (1) and (2) are performed in combination. That is, it is suitable for textile products such as socks, carpets, and bedding that are repeatedly used after washing, chopping boards, kitchenware, daily necessities for bath products, washing machines (particularly, washing tubs, dehydration tubs, and the like). For example, in the case of a textile product, after forming the fiber itself as an antibacterial fiber, the fiber or the textile product is dipped in a paint containing a good solvent for the resin component of the paint and an inorganic antibacterial / antifungal agent to have a coating having antibacterial properties. It is desirable to form a laminated portion.

The amount of the good solvent added in the method (1) is 0.05 to 1.5% by weight, preferably 0.05 to 1.0% by weight, based on the base resin. Is desirable. When the amount of the good solvent is less than 0.05% by weight based on the weight of the base resin, the desired antibacterial activity can be exhibited without significantly lowering the antibacterial activity of the inorganic antibacterial / antifungal agent itself. Is unfavorable because it becomes difficult.
If the content exceeds% by weight, no further effect commensurate with the addition can be expected, which is not preferable.

On the other hand, the blending amount of the good solvent in the production method of (2) is 0.05 to 0.05 with respect to the resin component of the paint.
It is desirably 1.5% by weight, preferably 0.05 to 1.0% by weight. When the compounding amount of the good solvent is less than 0.05% by weight with respect to the resin component of the paint, the desired antibacterial activity is exhibited without significantly lowering the antibacterial activity of the inorganic antibacterial and antifungal agent itself. If the amount exceeds 1.5% by weight, no further effect commensurate with the addition can be expected, which is not preferable.

Further, the antibacterial resin composition of the present invention is used.
Good solvents that can be used are the base resin or the resin component of the paint.
Solubility parameter (SP₁)
Parameters (SP_TwoA) having a solvent, more specifically,
Note SP₁And the SP_TwoIs | SP₁−SP_Two| ≦
1 is preferably satisfied. In this case, mother
SP of resin material or resin component of paint₁Value and solvent SP_Two
Choose the ones that are as close as possible, preferably the same
That is the principle. That is, SP₁Value and SP _TwoIs different
Inorganic substances added to the base resin or resin component
This is because the antibacterial properties of the fungi and fungicides are lost. What
The solubility parameter of the base resin (including the resin component of the paint)
Data (SP₁) And the solubility parameter of the solvent (S
P_Two), So far so many things
Actual measured values (and theoretical values) are required. Just these
Table 1 (SP value for resin) and Table 2
(SP value for solvent). However, applied to the present invention
Possible solvents are limited to those shown in these tables.
No, the base material to be used is selected from among various known solvents
It can be appropriately selected according to the resin component of the resin or paint.
it can. In addition, the solubility parameter of the resin in Table 1 below is used.
Indicates both actual and theoretical values.
Solubility parameter of resin composition (SP₁About)
Means that, in principle, actual measured values shall be used.
Not listed (in the example of Table 1 below,
Recon (polydimethylsiloxane only)
The theoretical value shall apply only for

[0060]

[Table 1]

[0061]

[Table 2]

The additives other than the inorganic antibacterial and antifungal agents which can be used in the production method of the above (1), the composition and the product are not particularly limited. The antibacterial resin composition and various conventionally known additives that can be added to the product can be appropriately compounded at an appropriate ratio, and in some cases, for the purpose of uniformly dispersing the inorganic antibacterial and antifungal agent. An appropriate dispersing agent may be appropriately blended in an appropriate ratio. Similarly, the above (2)
As for the additives other than the inorganic antibacterial and antifungal agents which can be used in the production method of the above, various known additives are appropriately blended at an appropriate ratio as in the production method of the above (1). In this case, an additive used for molding the resin itself is not particularly required, and an additive necessary for molding an antibacterial coating or a laminated portion formed on at least a surface portion of the resin product is used. What is necessary is just to select and use suitably.

[0063]

Hereinafter, the present invention will be described in detail by describing preferred embodiments of the present invention. However, the present invention is not limited to the embodiments disclosed below, but may be embodied in various different forms, which merely complete the disclosure of the present invention and It is intended to give the owner a complete understanding of the scope of the invention,
Various modifications and improvements are possible by those having ordinary skill in the art within the technical idea and scope of the present invention, and it goes without saying that such modifications and improvements also belong to the technical scope of the present invention. Absent. Example 1 The composition ratios of seven different inorganic antibacterial and antifungal agents A to G used in Example 1 are shown in Table 3 below. 7 of the above A to G
Table 3 shows the different types of inorganic antibacterial and antifungal agents.
The raw materials obtained by preparing the respective raw materials shown in the following to a particle size of 10 μm or less were used.

[0064]

[Table 3]

Table 4 below shows the properties of the seven different inorganic antibacterial and antifungal agents shown in Table 3 alone.

[0066]

[Table 4]

In Table 4, the antibacterial activity against Escherichia coli and Staphylococcus is a value measured and calculated by the above-described shake method. Further, in addition to the deodorization rate for acid-based substances and alkali-based substances serving as odor sources, the repellency, emissivity, surface area and pH are values measured and calculated by the methods described below. In this example, hydrogen sulfide was used as the acid substance and ammonia was used as the alkaline substance.

(1) Deodorization rate measurement method: Measurement was performed using a six-step method.

(2) Measurement method of repellent rate; JIS Z291
1 was measured.

(3) Measurement method of emissivity; sample (sample)
Was measured using a spectrometer.

The surface temperature of the sample is set to a predetermined temperature (100 ° C.)
The emissivity of the virtual black body and that of the sample (processed into a plate of 20 × 30 × 2 mm) were determined by comparing the emissivity with a spectroscope (manufactured by JASCO Corporation).

(4) Method for measuring surface area; BET (Brunauer
-Emmett-Teller) method.

(5) pH measurement method: pH was measured using a pH meter. Examples 1 to 10 From among the seven different types of inorganic antibacterial and antifungal agents A to G having various properties as shown in Table 4 above, those shown in Table 6 below were given at predetermined ratios (base material). 5 to resin
At the time of adding each of the four kinds of base resin (polyethylene, polystyrene, polyurethane, nylon) in a range of 10% by weight, a good solvent of the base resin (here, the solubility of the base resin shown in Table 5 below) Solvent with a solubility parameter (SP ₂ ) equal to the parameter (SP ₁ )
A predetermined ratio shown in Table 6 below (0.5 to
(A range of 1.0% by weight) by a mixing method of diluting a master batch in which an inorganic antibacterial and antifungal agent was previously blended at a high concentration to obtain respective antibacterial resin products. Using the test pieces of the obtained antibacterial resin products, various measurements were made and various properties obtained are shown in Table 6 below. The antibacterial rate against Escherichia coli and staphylococci was measured and calculated by the pressurization method, and the deodorization rate, repellency, emissivity, surface area, and pH were measured by the above-described methods.

[0074]

[Table 5]

[0075]

[Table 6]

As can be clearly seen from Tables 5 and 6,
In any of the antibacterial resin products of Examples 1 to 10, various properties including the antibacterial activity (antibacterial rate, deodorizing rate, repellent rate, and emissivity) of the compounded inorganic antibacterial and antifungal agent alone. It was confirmed that the characteristics were maintained without substantially impairing the characteristics. In particular, regarding the antibacterial rate, the correlation between the antibacterial rate (X) of the inorganic antibacterial / antifungal agent alone and the antibacterial rate (Y) of the resin formed using the inorganic antibacterial / antifungal agent is Y ≧ 0. .6X was sufficiently satisfied, and values satisfying all Y ≧ 0.9X were obtained. Similarly, with respect to the deodorization rate, repellency, emissivity, and the like, it was confirmed that the properties of the inorganic antibacterial and antifungal agent alone were maintained with almost no loss. Comparative Examples 1 to 10 Among the seven different types of inorganic antibacterial and antifungal agents A to G having the various properties shown in Table 4 above, those shown in Table 7 below were given at predetermined ratios (base material). 5 to resin
The masterbatch in which the inorganic antibacterial and antifungal agents are pre-mixed at a high concentration for each of the four different base resin materials (polyethylene, polystyrene, polyurethane, nylon) is diluted so that the concentration becomes 10% by weight. And a molded product of the antibacterial resin composition was manufactured. Using the test pieces of the obtained antibacterial resin products, various measurements were made and various properties obtained are shown in Table 7 below. In addition, each measuring method was performed by the same measuring method as measuring the characteristic of the said inorganic antibacterial and antifungal agent.

[0077]

[Table 7]

As can be clearly seen from Table 7, in each of the antibacterial resin products of Comparative Examples 1 to 10,
The antibacterial property of the compounded inorganic antibacterial and antifungal agent alone could not be maintained, and its properties were significantly reduced,
The correlation between the antibacterial rate (X) of the inorganic antibacterial / antifungal agent alone and the antibacterial rate (Y) of the resin formed using the inorganic antibacterial / antifungal agent satisfies Y ≧ 0.6X No value was obtained. Similarly, with respect to deodorization rate, repellency rate, emissivity, etc., it was also confirmed that various properties possessed by the inorganic antibacterial and antifungal agent alone could not be maintained, and that each property was significantly reduced. Was.

From the above results, when manufacturing and processing the antibacterial resin composition, it has a good solvent for the base resin, more specifically, a solubility parameter (SP ₂ ) almost equal to the solubility parameter (SP ₁ ) of the base resin. It was confirmed that the selection of the solvent was an important point.

[0080]

The antimicrobial resin composition and the antimicrobial resin product of the present invention can withstand heat and pressure during processing, the environment (light, water, etc.) placed during use, and furthermore, the basic properties of the resin product. The antibacterial effect of the inorganic antibacterial and antifungal agent alone can be effectively exerted without significantly impairing the performance without impairing the performance, and the expensive antibacterial metal material such as silver is replaced with a conventional expensive carrier. No complicated operation compared to the conventional method using inorganic antibacterial and antifungal agents that are provided at low cost by a simple operation that only requires firing the natural mineral raw material that is supplied at extremely low cost without performing any operation It is only necessary to add an operation of simply adding a good solvent to a resin component such as a base material resin at a predetermined ratio without newly performing a processing, and it is possible to manufacture at relatively low cost. In addition, it can be processed into various forms (fibers, films, coatings, molded products, etc.) as in the past, and can have extremely high safety (safety in all stages of processing, use and disposal). O-1 that produces toxins that cause food poisoning
Since the antibacterial effect against 57 bacteria can be maintained extremely high, it can be widely used especially for food packaging and containers, chopping boards, kitchenware, refrigerators, as well as daily commodities such as toilets and bathroom products easily susceptible to secondary infection. The inorganic antibacterial and antifungal agent, the antibacterial resin composition and the antibacterial resin product of the present invention can be used in various fields.

Such antibacterial resin products include, for example, daily and household products such as food packaging, food containers, cutting boards, kitchenware, bathroom products, refrigerators, washing machines, portable terminals (telephones), Home appliances such as water purifiers and air conditioners, home interior materials such as wallpaper and flooring, building materials such as sealing agents, textile products such as socks, carpets, bedding, construction machinery, agricultural materials, and industrial products require antibacterial properties. The invention is an epoch-making invention that can be used for any purpose, and can prevent loss of commercial value due to deterioration and discoloration by bacteria and molds for an extremely long time.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) C08L 101/16 C09D 5/14 C09D 5/14 C08L 101/00

Claims (23)

[Claims] 1. An inorganic antibacterial and antifungal agent comprising calcined dolomite. 2. An inorganic antibacterial and antifungal agent containing 25% by weight or more of calcined dolomite. 3. The calcined dolomite has a temperature of 900 to 120.
The inorganic antibacterial and antifungal agent according to claim 1, which is baked at 0 ° C. 4. The inorganic antibacterial composition according to claim 1, wherein the calcined dolomite is mainly composed of magnesium oxide and calcium oxide.
Antifungal agent. 5. The method according to claim 1, wherein the antibacterial activity (X) of the inorganic antibacterial and antifungal agent is 85% or more for both Escherichia coli and Staphylococcus. Inorganic antibacterial and antifungal agents according to Item. 6. An antibacterial resin composition comprising a base material resin and a good solvent and the inorganic antibacterial / antifungal agent according to any one of claims 1 to 5, wherein the inorganic antibacterial and antifungal agent are mixed. An antibacterial resin composition in which the antifungal agent is 2.5 to 20% by weight based on the base resin and the good solvent is 0.05 to 1.5% by weight based on the base resin. 7. The calcined dolomite has a temperature of 900 to 120.
The antibacterial resin composition according to claim 6, which is baked at 0 ° C. 8. The antibacterial resin composition according to claim 6, wherein the polymer resin is at least one selected from an elastomer, a halogen-containing resin, and a polymer. 9. The method according to claim 1, wherein the good solvent has a solubility parameter (SP ₁ ) substantially equal to the solubility parameter (SP ₁ ) of the resin base material.
The antimicrobial resin composition according to any one of claims 6 to 8, which is a solvent having ₂ ). 10.該良solvent, the relationship of the SP ₁ and the SP ₂ is, | SP ₁ -SP ₂ | antibacterial resin according to claim 9, characterized in that to satisfy ≦ 1 Composition. 11. An antibacterial resin product formed by using the antibacterial resin composition according to claim 6. Description: 12. The antibacterial rate (X) of the inorganic antibacterial and antifungal agent alone contained in the antibacterial resin composition and the antibacterial rate of an antibacterial resin product formed by using the antibacterial resin composition ( The antibacterial resin product according to claim 11, wherein a phase relationship with Y) satisfies Y ≧ 0.6X. 13. The inorganic antibacterial and antifungal agent according to any one of claims 1 to 5, wherein the amount of the inorganic antibacterial and antifungal agent is 2.5 to 20 with respect to the base resin.
13. The composition according to claim 11, wherein the content is by weight.
An antibacterial resin product according to item 1. 14. The method according to claim 11, wherein the inorganic antibacterial and antifungal agent according to any one of claims 1 to 5 has a particle size of 15 μm or less. The antibacterial resin product described. 15. The inorganic antibacterial / antifungal agent according to any one of claims 1 to 5, wherein the amount of the inorganic antibacterial / antifungal agent is 2.5 to 20 with respect to the base resin.
% By weight, wherein the antibacterial activity (X) of the inorganic antibacterial / antifungal agent is related to the antibacterial activity (Y) of the resin article containing the inorganic antibacterial / antifungal agent. , Y ≧
An antibacterial resin product satisfying 0.6X. 16. The inorganic antibacterial and antifungal agent having a particle size of 5
The antibacterial resin product according to any one of claims 11 to 15, wherein the particle size is from nm to 15 µm. 17. The correlation between the antibacterial activity (X) of the inorganic antibacterial and antifungal agent and the antibacterial activity (Y) of the resin article satisfies Y ≧ 0.90X. Item 17. The antibacterial resin product according to any one of Items 11 to 16. 18. A base material resin comprising a good solvent for the base material resin and an additive containing the inorganic antibacterial and antifungal agent according to any one of claims 1 to 5. A method for producing an antibacterial resin composition. 19. The method according to claim 18, wherein the amount of the good solvent is 0.05 to 1.5% by weight based on the weight of the base resin. 20. The method according to claim 1, wherein the good solvent is a solvent having a solubility parameter (SP ₂ ) substantially equal to the solubility parameter (SP ₁ ) of the base resin.
20. The method for producing the antibacterial resin composition according to 8 or 19. 21. The relationship between the SP ₁ and the SP ₂ is |
21. The method for producing an antibacterial resin composition according to claim 20, wherein SP ₁ -SP ₂ | ≦ 1 is satisfied. 22. A method for producing an antibacterial resin product, comprising using the antibacterial resin composition according to claim 6. Description: 23. A film or a laminated portion having antibacterial properties is formed on at least a surface portion of a substrate by using the antibacterial resin composition according to any one of claims 6 to 10. Manufacturing method of antibacterial resin products.