JPH0637374B2 - Bactericidal water dispersion - Google Patents

Description

TECHNICAL FIELD The present invention relates to a bactericidal aqueous dispersion used for the purpose of imparting bactericidal properties to fibers, films, molded articles and the like.

[Prior Art] In obtaining fibers, films, molded articles, etc. having a bactericidal action, the first method is to add bactericidal metal ions such as silver ions, copper ions, zinc ions to the raw material polymer. Can be mentioned. Recently, a method has also been developed in which a zeolite containing a bactericidal metal ion or the like (hereinafter sometimes referred to as a bactericidal zeolite) is added to a raw material polymer (JP-A-59-13323). However, when these methods are used, the physical properties of the raw material polymer are changed, and the physical properties of the raw material polymer cannot be directly reflected on the fiber or the like.

Therefore, studies have been conducted from the viewpoint of attaching bactericidal metal ions or the like to the surface of fibers or the like. However, simply attaching the bactericidal metal ion or the like to the fiber or the like causes the bactericidal metal ion to gradually drop out, so that the bactericidal zeolite is uniformly dispersed in the polymer for the purpose of improving the duration of action. In addition, a technique has been considered in which a dispersion of this in an organic solvent is applied to a fiber or the like. However, the bactericidal zeolite is separated from the polymer during the dispersion process in the organic solvent, and as a result, a uniform coating state cannot be obtained, and the intended purpose has not been achieved.

[Problems to be Solved by the Invention] The present invention has been made in view of such circumstances, and achieves stable and uniform dispersion of bactericidal zeolite and surely imparts bactericidal effect to fibers and the like. It is intended to provide a bactericidal water dispersion that can be achieved.

[Means for Solving the Problems] The bactericidal water dispersion according to the present invention contains solid zeolite particles holding metal ions having a bactericidal action, a water-insoluble organic polymer, and an emulsifier. The gist is that it is an aqueous dispersion.

[Operation] The present invention provides (1) zeolite-based solid particles retaining metal ions having a bactericidal action, (2) water-insoluble organic polymer,
(3) It is characterized by using an emulsifier and making them an aqueous dispersion.

The above zeolite-based solid particles are used to give a reliable sterilizing action to fibers, films and the like (hereinafter, also referred to as a sterilization subject) through the sterilizing metal ions retained therein. On the other hand, the organic polymer is used as a carrier for holding the zeolite-based solid particles (that is, bactericidal metal ions), and ensures uniform dispersion of the zeolite particles by, for example, stirring operation. Further, since it is insoluble in water, it is possible to achieve stabilization of each emulsion particle when it is made into an aqueous dispersion. Further, the emulsifier is used for maintaining a stable and uniform dispersion state of the organic polymer in water for a long period of time. Therefore, as a result of the features (1) to (3) being effectively exhibited, the dispersion of the bactericidal zeolite in water is stable and uniform, and the bactericidal action is achieved by attaching it to the sterilization target. Expression can be ensured. It should be noted that the mixing ratios of the above-mentioned are not particularly limited, but the zeolite-based solid particles 1 to 20 relative to 100 parts by weight of the organic polymer.
Parts by weight, preferably 3 to 10 parts by weight, 5 to 100 parts by weight, preferably 5 to 100 parts by weight of the mixture.
It is used in an amount of 50 parts by weight, more preferably 10 to 30 parts by weight.

Next, each of the above (1) to (3) will be sequentially described.

The above-mentioned (1) zeolite solid particles are one or two kinds of metal ions (silver ion, copper ion, zinc ion, etc.) having a bactericidal action in the ion-exchangeable part of natural or synthetic zeolite made of aluminosilicate. The one holding the above. The zeolite material used in the present invention may be any of natural and synthetic zeolites as described above. For example, a typical natural zeolite is analcine (Analcine: SiO ₂ / Al ₂ O ₃ =
3.6 to 5.6), Chabasite: SiO ₂ / Al ₂ O ₃ = 8.5
~ 10.5), erionite (Erionite: SiO ₂ / Al ₂ O ₃ = 5.8
~ 7.4), Faujasite: SiO ₂ / Al ₂ O ₃ ＝
4.2 to 4.6), mordenite (mordenite: SiO ₂ / Al ₂ O ₃ ＝
8.34 ~ 10.0), Phillipsite: SiO ₂ / A
l ₂ O ₃ = 2.6 to 4.4) and the like. On the other hand, as a typical synthetic zeolite, A-type zeolite (SiO ₂ / A
l ₂ O ₃ = 1.4 to 2.4), X-type zeolite (SiO ₂ / Al ₂ O ₃ =
2 to 3), Y- type zeolite _{(SiO 2 / Al 2 O 3} = 3~6),
Mordenite _{(SiO 2 / Al 2 O 3} = 9~10) , and the like. Further, the above zeolite is recommended to be in the form of powder or particles. In this case, the particle size is preferably 2 μm or less from the viewpoint of blending uniformity and water dispersion uniformity.
It is more preferably 0.5 μm or less.

Regarding the organic polymer of (2) above, it is necessary that it is insoluble in water in order to ensure a uniform and stable dispersion state of the above zeolite-based solid particles, and as long as this condition is satisfied, it is particularly limited. However, in order to hold the zeolite-based solid particles more stably, and to maintain the texture of the sterilization target, a rubber elastic copolymer having a hard segment and a soft segment appropriately arranged ( (Molecular weight: 3,000 to 100,000, preferably 5,000 to 70,000)
Is recommended. Typical examples thereof include (a) a rubber elastic copolymer (molecular weight of aromatic polyester such as polyethylene terephthalate as a hard segment, (b) soft segment such as polyether such as polytetramethylene oxide or aliphatic polyester such as polyethylene adipate). : 10,000 or more).

Further, typical examples of the monomer for obtaining the above-mentioned copolymer include alkylene oxide repeating units having 3 to 6 carbon atoms such as allene ether glycol and 4 to 8 carbon atoms in lactone. The ratio of the hard segment and the soft segment is not particularly limited.

The emulsifier (or surfactant) in (3) above is not particularly limited as long as it effectively emulsifies the organic polymer, but when a polyester resin is used as the organic polymer. In the above, it is recommended to use a polyethylene glycol ether adduct type surfactant of higher alcohol or a polyethylene ether glycol adduct type surfactant of higher fatty acid. Examples of the higher alcohols include octadecyl alcohol, cetyl alcohol, decanol, oleyl alcohol, lauryl alcohol, octadecane diol, and the like.
The added mole number of ethylene oxide is preferably 6 to 100, and more preferably 10 to 60. Further, a part of ethylene oxide may be replaced with propylene oxide. Such a surfactant has an HLB value of 1 in order to maintain a good dispersion state of each emulsion particle.
It is recommended to use 5 or more. On the other hand, examples of higher fatty acids include saturated or unsaturated fatty acids having 8 to 24 carbon atoms such as lauric acid, myristic acid, palmitic acid, stearic acid, and oleic acid. The addition mole number of ethylene octide is preferably 6 to 100 moles, and particularly 1
0-60 are more preferable. Further, a part of ethylene oxide may be replaced with propylene oxide. As such a surfactant, it is recommended to use one having an HLB value of 10 to 20 in order to maintain a good dispersed state of each emulsion particle.

In order to make the dispersed state of the emulsion particles more stable, it is recommended that an alkanolamine be present in the aqueous dispersion. Alkanolamine [(HOC _n H _2n )
Examples of _m NH _3-m , where m = 1,2,3] include monoethanolamine, diethanolamine, triethanolamine, etc., and the concentration thereof is 0.1 to 20% by weight, preferably 0.5 to 10%. % By weight, more preferably 1 to
Used in the range of 5% by weight.

By the way, the bactericidal water dispersion of the present invention does not specify a production method, but the following method can be given as an example.

Zeolite solid particles are mixed with polyester resin in a specified amount and mixed by stirring while heating and melting in an inert gas such as nitrogen gas, and then a specified amount of surfactant is added and heated and melted in an inert gas. -The above surfactant is uniformly dispersed by stirring. The obtained molten polyester resin is added little by little to the alkanolamine aqueous solution and stirred to obtain a milky white aqueous dispersion.

Hereinafter, the present invention will be specifically described by giving Examples and Comparative Examples, but the present invention is not limited to the properties of the Examples, and may be modified as necessary based on the spirit of the preceding and the following. be able to.

Example 1 100 parts of a block copolymer (molecular weight of about 65,000) consisting of 30 parts by weight of polyethylene terephthalate segment (hereinafter simply referred to as “part”) and 70 parts of polytetramethylene ether glycol segment, and silver having an average particle size of 0.6 μm −
After mixing 5 parts of Y-type zeolite and melt-mixing at 250 ° C. under a nitrogen stream, the mixture was extruded from a nozzle having a diameter of about 3 mm and water-cooled to form pellets (solid zeolite-containing polyester A resin) having a length of about 5 mm. 2.5 parts of polyoxyethylene lauryl ether (HLB value: 20) was added to 10 parts of A resin, and melted again at 250 ° C. under a nitrogen stream,
A white emulsion dispersion can be prepared by injecting this into 90 parts of a 1% aqueous solution of monoethanolamine at 90 ° C. prepared with stirring while stirring. This emulsion dispersion is at room temperature (20
It is stable and the dispersed state does not break even if left at ~ 30 ° C).
This is a solid zeolite-containing polyester aqueous dispersion (A
Liquid).

A jersey made of polyethylene terephthalate fiber
A 10% water-diluted solution of the solution was impregnated with 80% wet pickup, dried at 100 ° C., and then set at 160 ° C. for 30 seconds. The sterilization rate of the jersey thus obtained as a measure of the bactericidal effect was measured and found to be 80%.
On the other hand, it was 0% for the untreated jersey.

Example 2 100 parts of a block copolymer (molecular weight of about 60,000) consisting of 30 parts of polyethylene terephthalate / isophthalate segment (copolymerization ratio 80 parts: 20 parts) and 70 parts of polytetramethylene ether glycol segment was added to the following Table 1. The solid zeolite shown in (1) was added in a predetermined amount and melt-mixed at 280 ° C. under a nitrogen stream to obtain a chip similar to that in Example 1.

Polyoxyethylene oleyl ether (HLB about 22) was added to 12 parts of the solid zeolite-containing polyester thus obtained.
2.5 parts are mixed and melted and mixed at 280 ° C under a nitrogen stream. Meanwhile, 90 parts of a 0.5% aqueous solution of diethanolamine was added to 80 parts.
A stable milky white emulsion was obtained by heating to 0 ° C. and gently adding the melt while stirring with a propeller stirrer. This emulsion was used to give polyester futon cotton (Toyobo Co., Ltd. S-UP: 6d-64 mm) in the amounts shown in Table 2 below, followed by drying and heat treatment (160 ° C. × 60 mm).
Seconds).

The bactericidal properties of the thus obtained polyester futon cotton were sterilized and the results were also shown in the same table.

The sterilization rate of the untreated polyester futon was 0% or less. In addition, the futon cotton in the above table had a good card-passing property in the cotton making process, and had the same bulk characteristics as the untreated cotton.

Comparative Example 1 Polyester resin 30% in dibasic acid occupied by 5-sulfoisophthalic acid 30 parts polyethylene terephthalate / isophthalate / 5-sulfoisophthalate and 70 parts polyethylene glycol ether (molecular weight 20,000) Solid zeolite (Z _{1 in} Table 1 above) was added to the coalesced (molecular weight of about 40,000) to attempt water dispersion.
The polyester resin dissolved in water and solid zeolite separated.

Comparative Example 2 Polyethylene terephthalate-5-sulfoisophthalate (copolymerization ratio 90:10) and ethylene glycol
To 100 parts of a block copolymer (molecular weight of about 30,000) consisting of diethylene glycol (50:50) was added 10 parts of solid zeolite (Z _{1 in} Table 1 above), and the mixture was emulsified and dispersed in the same manner as in Example 1. Although 1% owf was applied to the futon cotton of Example 2, it was not suitable for practical use as the futon cotton because the texture became coarse and hard.

EFFECTS OF THE INVENTION Since the present invention is configured as described above, it is possible to achieve stable and uniform dispersion of bactericidal zeolite and to ensure bactericidal property imparting to the bactericidal target. .

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Claims (1)

[Claims] 1. An aqueous dispersion containing zeolite-based solid particles retaining metal ions having a bactericidal action, a water-insoluble organic polymer as a carrier for retaining the zeolite-based solid particles, and an emulsifier. A bactericidal water dispersion characterized by: