JP6630903B2 - Antibacterial powder composition - Google Patents

Description

The present invention relates to an antibacterial powder composition that can impart excellent antibacterial properties to polymer products such as polyvinyl chloride, polyolefin, and synthetic rubber.

Since polymer products such as polyvinyl chloride, polyolefin, and synthetic rubber cause deterioration and contamination due to the growth of mold, antibacterial active ingredients are generally added to polymer raw materials to prevent such deterioration.

When a liquid is used as such an antibacterial active ingredient, it becomes difficult to uniformly mix it depending on the type of the polymer and the method of molding the polymer, and therefore, addition as a powder is preferred.

When the antibacterial active ingredient is provided as a powder, from the viewpoint of compatibility and miscibility with the polymer raw material, it is preferable that the particle size of the powder is smaller, but the powder is packaged with a powder for commercialization. In use, it is easily scattered during various operations such as measurement and preparation, especially when a thiazoline compound having excellent antibacterial activity is used as an active ingredient, such as coughing and sneezing between workers. Environmental problems are more likely to occur.

As a measure to prevent dust from scattering, agricultural chemicals have attempted to use a mineral having a large true specific gravity as a carrier (Patent Document 1). However, in general, the amount of liquid absorbed by a mineral having a large true specific gravity is relatively small. If this method is used for blending an antibacterial agent into a polymer raw material, the amount of the antibacterial active ingredient in the polymer raw material must be reduced. In order to mix the antibacterial agent, a relatively large amount of minerals is compounded, which causes a new problem and is not practical.

JP 2008-239570A

An object of the present invention is to provide an antibacterial powder composition that can impart excellent antibacterial properties to polymer products such as polyvinyl chloride, polyolefin, and synthetic rubber, and that is rich in work safety during the commercialization process and use. It is about things.

（式中、Ｒは炭素数４以上８以下のアルキル基又はフェニル基を示し、Ｘ、Ｙは同一又は異なり、水素もしくはハロゲンを示し、又は互いに炭素とともに結合して芳香族環を形成しても良い）
で示される一種以上のチアゾリン化合物である上記抗菌粉体組成物。
また本発明は、
（４）抗菌活性成分が、２−ｎ−オクチル−４−イソチアゾリン−３−オンおよびＮ−ｎ−ブチル−１，２−ベンズイソチアゾリン−３−オンからなる群より選ばれる一種以上である上記抗菌粉体組成物。
また本発明は、
（５）プラスチックに混錬されて使用される上記抗菌粉体組成物。 The present inventor has conducted intensive studies to solve the above-mentioned problems, and as a result, it has been found that, for a powder exhibiting an oil absorption within a specific range, an antibacterial active ingredient having an oil absorption of 85 to 100% of the powder absorption. By absorbing a liquid agent containing, it has been found that it is possible to obtain an antibacterial powder composition having good workability during preparation, weighing, and handling while maintaining high antibacterial activity, and completed the present invention. It was made. That is, the present invention
(1) A powder containing an antibacterial active ingredient is added to a powder having an oil absorption in the range of 1.5 to 5 ml / g as measured according to JIS K5101-13-1, and the liquid is contained in an amount of 85 to 100 with respect to the oil absorption of the powder. % Antimicrobial powder composition absorbed in the range of%.
Also, the present invention
(2) The powder whose oil absorption measured by JIS K5101-13-1 is in the range of 1.5 to 5 ml / g is one or more inorganic substances selected from the group consisting of calcium silicate and silicic anhydride. The above antibacterial powder composition.
Also, the present invention
(3) The antibacterial active ingredient has the general formula (I)

(In the formula, R represents an alkyl group or a phenyl group having 4 to 8 carbon atoms, X and Y are the same or different and represent hydrogen or halogen, or may form an aromatic ring by bonding together with carbon. good)
The antibacterial powder composition as described above, which is one or more thiazoline compounds.
Also, the present invention
(4) The above antibacterial wherein the antibacterial active ingredient is one or more selected from the group consisting of 2-n-octyl-4-isothiazolin-3-one and Nn-butyl-1,2-benzisothiazolin-3-one. Powder composition.
Also, the present invention
(5) The antibacterial powder composition used by being kneaded with a plastic.

By using the antibacterial powder composition according to the present invention, it is possible to impart excellent antibacterial properties to polymer products such as polyvinyl chloride, polyolefin, and synthetic rubber. Can also be good.

The oil absorption specified in the antibacterial powder composition according to the present invention means the oil absorption measured according to JIS K5101-13-1. In addition, examples of the powder having such an oil absorption amount include calcium silicate and light silicic anhydride, and preferably calcium silicate and / or light silicic anhydride. Calcium silicate can be produced by a known technique, and for example, commercially available from Tomita Pharmaceutical Co., Ltd. as Florite (registered trademark) can also be used. Light silicic anhydride can be produced by a known technique. For example, light anhydrous silicic acid is commercially available as Carplex (registered trademark) from DSL Japan Co., Ltd., and Tokusil (registered trademark) is commercially available from OSC Japan Ltd. And the like can be used.

（式中、Ｒは炭素数４以上８以下のアルキル基又はフェニル基を示し、Ｘ、Ｙは同一又は異なり、水素もしくはハロゲンを示し、又は互いに炭素とともに結合して芳香族環を形成しても良い）で示される一種以上のチアゾリン化合物が好ましく、さらに好ましくは、２−ｎ−オクチル−４−イソチアゾリン−３−オンおよび／又はＮ−ｎ−ブチル−１，２−ベンズイソチアゾリン−３−オンである。２−ｎ−オクチル−４−イソチアゾリン−３−オンは公知の技術によって製造することができ、また市販品を用いることもできる。そのような市販品としては、例えば、ＺＯＮＥＮ（登録商標） Ｏ／１００（ケミクレア社製）が挙げられる。Ｎ−ｎ−ブチル−１，２−ベンズイソチアゾリン−３−オンは公知の技術によって製造する製造することができ、また市販品を用いることもできる。そのような市販品としては、例えば、ＤＥＮＳＩＬ（登録商標） ＤＮ（ロンザジャパン社製）が挙げられる。また、本発明に係る抗菌粉体組成物において、抗菌活性成分として、３−ヨード−２−プロピニルブチルカーバメート、プロピコナゾール、ヘキサコナゾール、テブコナゾール、ｏ−フェニルフェノール、ジヨードメチル−ｐ−トリルスルフォン、２，３，３−トリヨードアリルアルコール等を用いることもでき、この場合、溶剤に溶解乃至分散させて用いられる。本発明に係る抗菌粉体組成物において、抗菌活性成分を含む液剤には、ｐＨ調整剤、紫外線吸収剤、光安定剤、帯電防止剤等を含んでいてもよい。 In the antibacterial powder composition according to the present invention, the liquid preparation containing the antibacterial active ingredient may be used as it is as long as it is a liquid antibacterial active ingredient at room temperature. The antibacterial active ingredient is used by dissolving or dispersing it in a solvent. As the antibacterial active ingredient, it has excellent antibacterial activity in a polymer product.

(In the formula, R represents an alkyl group or a phenyl group having 4 to 8 carbon atoms, X and Y are the same or different and represent hydrogen or halogen, or may form an aromatic ring by bonding together with carbon. Good), more preferably one or more thiazoline compounds represented by the formula: 2-n-octyl-4-isothiazolin-3-one and / or Nn-butyl-1,2-benzisothiazolin-3-one. is there. 2-n-octyl-4-isothiazolin-3-one can be produced by a known technique, or a commercially available product can be used. As such a commercially available product, for example, ZONEN (registered trademark) O / 100 (manufactured by Chemicrea) can be mentioned. Nn-butyl-1,2-benzisothiazolin-3-one can be produced by a known technique, or a commercially available product can be used. Examples of such commercially available products include DENSIL (registered trademark) DN (manufactured by Lonza Japan). In the antibacterial powder composition according to the present invention, as an antibacterial active ingredient, 3-iodo-2-propynylbutylcarbamate, propiconazole, hexaconazole, tebuconazole, o-phenylphenol, diiodomethyl-p-tolylsulfone, 2,3,3-triiodoallyl alcohol or the like can also be used, and in this case, it is used after being dissolved or dispersed in a solvent. In the antibacterial powder composition according to the present invention, the solution containing the antibacterial active ingredient may contain a pH adjuster, an ultraviolet absorber, a light stabilizer, an antistatic agent, and the like.

Examples of the solvent include di-2-ethylhexyl phthalate, dioctyl phthalate, isononyl phthalate, diisodecyl phthalate, and the like, di-2-ethylhexyl adipate, dioctyl adipate, diisononyl adipate, diisodecyl adipate. Adipates, such as acetyltriethyl citrate, acetyltributyl citrate, etc .; dibutyl sebacate, sebacic esters, such as di-2-ethylhexyl sebacate; tri-2-ethylhexyl phosphate, phosphorus Organic solvents having plasticity, such as phosphates such as triphenyl acid and tricresyl phosphate, and trimellitates such as tris-2-ethylhexyl trimellitate.

The antibacterial powder composition according to the present invention can be used in combination with other antibacterial active ingredients in powder. Such antibacterial active ingredients include 2- (4-thiazolyl) benzimidazole, methyl 2-benzimidazolecarbamate, 1- [2- (allyloxy) -2- (2,4-dichlorophenyl) ethyl] imidazole, bis (2 -Pyridylthio-1-oxide) zinc, 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine, 2,4,4'-trichloro-2'-hydroxydiphenyl ether, 1,4-bis (3 , 3 '-(1-decylpyridinium) methyloxybutane) bromide. In addition to the powder that has absorbed the liquid agent, other antibacterial active ingredients that are powder, inorganic extenders such as talc, clay, kaolin, calcium carbonate, and alumina, and polymers such as vinyl chloride resin and vinyl chloride vinyl acetate copolymer And the like can also be blended.

As a method of absorbing the liquid containing the antibacterial active ingredient into the powder, by mixing using a known mixer, such as a ribbon blender, a Nauter mixer, a Henschel mixer, a paddle mixer, a V-type mixer, a kneader and the like. Can be absorbed.

Hereinafter, the present invention will be described specifically with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. Unless otherwise specified, “%” represents “% by weight”.
(Example of antibacterial powder composition)

A solution prepared by mixing and dissolving 10 parts of 2-n-octyl-4-isothiazolin-3-one (hereinafter abbreviated as OIT) in 12.2 parts of diisononyl phthalate (hereinafter abbreviated as DINP) was added to Florite R (oil absorption). (4.6 ml / g) The powder obtained by mixing and stirring 5.2 parts with a ribbon blender was used as the antibacterial powder composition 1 of the present invention.

A liquid obtained by mixing and dissolving 10 parts of OIT in 12.2 parts of DINP was mixed and stirred with 4.9 parts of FLORITE R using a ribbon blender, and the resulting antibacterial powder composition 2 of the present invention was used. And

A liquid obtained by mixing and dissolving 10 parts of OIT in 40 parts of DINP was mixed and stirred with 11.7 parts of FLORITE R using a ribbon blender to obtain an antibacterial powder composition 3 of the present invention. .

The antibacterial powder composition 4 of the present invention was obtained by mixing and stirring 10.2 parts of OIT with 2.3 parts of Florite R using a ribbon blender with a ribbon blender.

A liquid obtained by mixing and dissolving 10 parts of OIT in 12.2 parts of DINP was mixed and stirred with 11.5 parts of Toksir NR (oil absorption 2.0 ml / g) using a ribbon blender to obtain a powder. The antibacterial powder composition 5 of the present invention was obtained.

A liquid obtained by mixing and dissolving 10 parts of OIT in 12.2 parts of diisononyl adipate (hereinafter abbreviated as DINA) was mixed and stirred in 5.2 parts of Florite R using a ribbon blender to obtain a powder obtained by mixing and stirring. The antibacterial powder composition 6 of the present invention was obtained.

A solution prepared by mixing and dissolving 10 parts of OIT in 12.2 parts of DINP was absorbed into 5.2 parts of Florite R by mixing and stirring using a ribbon blender, and then methyl 2-benzimidazolecarbamate was added thereto. The powder obtained by mixing 10 parts (hereinafter abbreviated as BCM) was used as the antibacterial powder composition 7 of the present invention.

A solution prepared by mixing and dissolving 10 parts of OIT in 12.2 parts of DINP is absorbed by mixing and stirring with 5.2 parts of Florite R using a ribbon blender, and then mixed with 25 parts of BCM. The resulting powder was designated as the antibacterial powder composition 8 of the present invention.

A liquid mixture obtained by mixing and dissolving 10 parts of Nn-butyl-1,2-benzisothiazolin-3-one (hereinafter abbreviated as BBIT) in 12.2 parts of DINP, and a ribbon blender in 5.2 parts of Florite R After absorbing by mixing and stirring, a powder obtained by mixing 10 parts of BCM was used as the antibacterial powder composition 9 of the present invention.

A solution prepared by mixing and dissolving 10 parts of BBIT in 12.2 parts of DINP is absorbed into 5.2 parts of Florite R by mixing and stirring using a ribbon blender, and then bis (2-pyridylthio-1-oxide ) A powder obtained by mixing 10 parts of zinc (hereinafter abbreviated as ZPT) was used as the antibacterial powder composition 10 of the present invention.

A solution prepared by mixing and dissolving 10 parts of OIT in 12.2 parts of DINP is absorbed in 5.2 parts of Florite R by mixing and stirring using a ribbon blender, and then 2- (4-thiazolyl) benzimidazole is used. (Hereinafter, abbreviated as TBZ) A powder obtained by mixing 10 parts was used as antibacterial powder composition 11 of the present invention.

A solution prepared by mixing and dissolving 10 parts of OIT in 12.2 parts of DINP was absorbed into 11.5 parts of Toksir NR by mixing and stirring using a ribbon blender, and then mixed with 25 parts of BCM. The powder was designated as the antibacterial powder composition 12 of the present invention.

[Comparative Example 1]
A powder obtained by mixing and stirring 10 parts of OIT in 12.2 parts of DINP with 12.2 parts of DINP and 6 parts of FLORITE R using a ribbon blender was used as Comparative Composition 1.

[Comparative Example 2]
A solution prepared by mixing and dissolving 10 parts of OIT in 12.2 parts of DINP was mixed and stirred with 4.7 parts of FLORITE R using a ribbon blender, but it became a paste and did not become a powder.

[Comparative Example 3]
A powder obtained by mixing and dissolving 10 parts of OIT in 12.2 parts of DINP and 14.8 parts of Toksir NR using a ribbon blender was used as Comparative Composition 3.

[Comparative Example 4]
A powder obtained by mixing and dissolving 10 parts of BBIT in 12.2 parts of DINP and mixing and stirring it with 6 parts of FLORITE R using a ribbon blender was used as Comparative Composition 4.

(Preparation of polyvinyl chloride wallpaper)
100 parts of PQB83 (polyvinyl chloride, manufactured by Shin-Daiichi PVC), 50 parts of DINP, 100 parts of Whiten H (calcium carbonate, manufactured by Shiraishi Kogyo), NV S-9044-W (titanium dioxide slurry, manufactured by Nippon Pigment Corporation) 19 parts, 3 parts of ADK STAB (registered trademark) FL100 (barium / zinc-based stabilizer, manufactured by Adeka), 3 parts of AZH-25 (azodicarbonamide-based foaming agent, manufactured by Otsuka Chemical Co., Ltd.) Was prepared. Next, the antibacterial composition of the present invention and the comparative composition prepared as described above are taken out of the respective storage containers, weighed, and mixed with 100 parts of the PVC sol so as to be 0.03 part in terms of the antibacterial active ingredient. This was applied to paper at a thickness of 150 μm, heated at 150 ° C. for 30 seconds, and further heated at 220 ° C. for 50 seconds to prepare a polyvinyl chloride wallpaper.
(Irritation evaluation of antibacterial powder composition)

In preparing the antimicrobial composition of the present invention and the comparative composition described above, five subjects were present in close proximity to each work place at the time of filling, and the degree of irritation caused by sneezing and coughing was investigated. It was calculated by the average of the evaluation values of five people.

(Antibacterial test)
The polyvinyl chloride wallpaper was cut into a size of 40 mm × 40 mm, and the antibacterial property against mold was evaluated by the method A for the test of plastic products in Annex A of JIS Z2911.

Tables 1 and 2 show the results of the antibacterial powder composition of the present invention and Table 3 show the results of the comparative composition based on the following criteria for the presence or absence and degree of irritation and the antibacterial results on polyvinyl chloride wallpaper. showed that.
(Degree of irritation)
0: No irritation was observed 1: Slight irritation was felt 2: A large irritation was felt (antibacterial property against mold)
0: No mold growth was observed with the naked eye and under the microscope 1: Mold growth was not observed under the naked eye, but was clearly confirmed under the microscope 2: Mold growth was observed under the naked eye, and the area of the developed portion was Less than 25% of the total area of the sample 3: Mold growth is observed with the naked eye, and the area of the growing portion is 25% or more to less than 50% of the total area of the sample 4: Mycelium grows well and the area of the growing portion is the sample 5: More than 50% of the total area of the mycelium 5: Mycelium grows violently and covers the entire surface of the sample

The antibacterial powder composition according to the present invention can maintain a good working environment in each of the working steps of commercialization (preparation to filling in a container) and use (measurement to kneading with a polymer raw material), Since it can impart excellent antibacterial properties to polymer products such as vinyl chloride, polyolefin, and synthetic rubber, it can be widely used for applications such as wallpaper, flooring materials, plastic miscellaneous goods, and transmission belts.

Claims (5)

A powder containing an antibacterial active ingredient is added to a powder having an oil absorption of 1.5 to 5 ml / g as measured by JIS K5101-13-1 in a range of 85 to 100% based on the oil absorption of the powder. An antibacterial powder composition made to be absorbed by. 2. The powder having an oil absorption measured by JIS K5101-13-1 in the range of 1.5 to 5 ml / g is at least one inorganic substance selected from the group consisting of calcium silicate and silicic anhydride. 3. The antibacterial powder composition according to item 1. The antibacterial active ingredient has a general formula (I)

(In the formula, R represents an alkyl group or a phenyl group having 4 to 8 carbon atoms, X and Y are the same or different and represent hydrogen or halogen, or may form an aromatic ring by bonding together with carbon. good)
The antibacterial powder composition according to claim 1, which is one or more thiazoline compounds represented by the following formula: The antibacterial active ingredient is at least one selected from the group consisting of 2-n-octyl-4-isothiazolin-3-one and Nn-butyl-1,2-benzisothiazolin-3-one. The antibacterial powder composition according to any one of the above. The antibacterial powder composition according to any one of claims 1 to 4, which is used after being kneaded with a plastic material.