JPS61100254A - Molded product having antibacterial function - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention provides a molded article having antibacterial ability.

[Conventional technology] Conventionally, methods for removing bacteria and other fungi from water include:
There are things like chlorination, ozonation, and ultraviolet treatment,
These are effective for large-scale treatment, and chlorination and ozonation have odor and bad taste. On the other hand, surfactants, which have recently been widely used as disinfectants, are highly toxic because they mix with water and cannot be used to disinfect drinking water.

Therefore, attempts have been made to immobilize substances with antibacterial activity on water-insoluble carriers. Typical examples include those in which silver is fixed to granular activated carbon, and those in which quaternary ammonium salt type surfactants are fixed to cation exchange resins through ionic bonds (Bacterial and Mildew Prevention Journal +L+511 (1979)).
etc.) etc. can be given.

[Problems to be solved by the invention] However, activated carbon-silver products have many unclear points regarding the outflow of silver (and products using cation exchange resins have ionic bonds, so quaternary ammonium salts are released) This is unavoidable and may cause harm to the human body.

[Means for Solving the Problems] The present inventors have made extensive studies to overcome these problems, and as a result, have arrived at the present invention. The present invention relates to a polymonovinyl aromatic compound, which has been crosslinked and insolubilized, and which has an antibacterial ability formed by covalently bonding a quaternary ammonium group having a long-chain alkyl group.

The present invention has surprisingly found that the cross-linked and insolubilized compound exhibits antibacterial activity even when a quaternary ammonium group having a long-chain alkyl group is covalently bonded to the compound.

Generally, antibacterial action includes bacteriostatic action and bactericidal action, and the product of the present invention particularly has bactericidal action.

The polymonovinyl aromatic compound in the present invention includes a styrene-divinylbenzene copolymer, a homopolymer of styrene, vinyltoluene, etc., a copolymer, and a blend thereof. In addition, poly(α-
Other polymer components such as olefins) may also be present as mixtures or complexes.

It is important that the polymonovinyl aromatic compound is crosslinked and insolubilized. The styrene-divinylbenvin copolymer already has a crosslinked structure. For polymers such as styrene and vinyltoluene, 1 m'''61'''
ゝ”′1・ゝ“12ゝ7″8jj etc. are possible.

The quaternary ammonium group in the present invention is given by the following formula.

R1, R2: -Ct-I3, -CH2CH3
Rs: -Cn R2rt+1(n -3~3
0) R1 and R2 are methyl groups or ethyl groups, and if they are too bulky, the reactivity with the polymer will be poor (and the adsorption performance will also be low).

It is the alkyl group of R3 that has a great influence on the antibacterial ability. When π is 1 or 2, adsorption is good, but antibacterial performance is low, and bacteria may propagate. On the other hand, if n is too large, the cationicity will be small and bacteria will not be able to approach it sufficiently. Therefore, π is usually 3 to 30, preferably 6 to 2
0, particularly preferably 10-16.

It is very important that the quaternary ammonium group in the present invention is covalently fixed to the polymonovinyl aromatic compound. However, the aroma
Rather than directly bonding to one nucleus, it is preferable to bond to an aromatic nucleus via methylene or a long-chain spacer. The content of quaternary ammonium groups is usually 0.01 mol to 1 mol per mol of aromatic nucleus, but if the content is too high or too low, the antibacterial ability will decrease, so in particular, 0.01 mol to 1 mol per mol of aromatic nucleus.
The range of 1 mol to 0.8 mol is preferable.

The shape of the molded product in the present invention may be either resin (granular, powder, film, etc.) or 4Xl fibrous (long fiber, short fiber, string, knitted fabric, etc.), but the surface area of the fibrous product is It is preferable in terms of size and flexibility in design of form. especially,
A polymonovinyl aromatic compound is used as a sheath component, and a reinforcing poly(
Multicore composite or mixed fibers containing α-olefin as a core component are preferably used in terms of strength and water permeability.

Although the method for producing the molded article having antibacterial ability of the present invention is arbitrary, it will be explained below by giving an example.

Since gel-type resins and macroreticular (MR)-type resins, which are styrene-divinylbenzene copolymers, have a crosslinked structure, chloromethyl groups are directly introduced into the aromatic nucleus. Furthermore, the resin having antibacterial activity of the present invention is produced by reacting the chloromethylated resin with a tertiary amine based on the above structural formula.

On the other hand, the fibrous material is manufactured as follows.

The yarn is spun so that the polymonovinyl aromatic compound is the main component of the sea component and the reinforcing polymer such as poly(α-olefin) is the island component. After forming the m-fibers into various forms, they are treated with a sulfuric acid solution containing a formaldehyde source to introduce methylene crosslinks and insolubilize the remaining components. Next, a chloromethyl group is introduced in the same manner as in the resin, and the fiber is reacted with a tertiary amine to produce the fiber having antibacterial ability of the present invention.

The molded article having antibacterial ability of the present invention can be applied to any use requiring the removal of fungi such as bacteria from water. Examples include taking drinking water from contaminated water, extracting 1 quart of clean water from drinking water, sterilization when producing purified water for use in hospitals, and sterilization when producing ultrapure water. be able to. It can also be used to sterilize foods and medicines. In addition, various filters,
It can be applied to patent 4a textile products that are characterized by antibacterial properties, such as masks, bandages, cloth+i], etc.

[Example 1] Multicore sea-island type composite fiber! (Undrawn yarn) [Sea component (polystyrene/polypropylene) 7/Island component (polypropylene)
-(47/4), /49 (Image 16, fiber diameter 34μ
)] is cut to length 11 and the cut fiber is 19. 101 parts of the cut fiber was added to a crosslinking solution consisting of 50 volume parts of commercially available primary sulfuric acid, 5.0 volume a parts of water, and 2 parts of paraformaldehyde, and reacted at 60°C for 4 hours, then washed with water and dried. .

Next, 1 part of the crosslinked yarn was added to a chloromethylation solution consisting of 3 parts by volume of chloromethyl needle, 8 parts by volume of ethane tetrachloride, and 0.15 parts by volume of stannic chloride, and reacted at 50°C for 4 hours to form a chloromethylated yarn. Obtained. By adding 1 part by weight of this chloromethyl fiber to 8 parts by volume of N,N-dimethyl n-dodecylamine and reacting at 100°C for 4 hours, a quaternary ammonium group containing a long chain alkyl group (12 carbon atoms) is obtained. 1 u of antibacterial fiber. Mutei chlorine content m t tl! 11
The amount of functional groups introduced was determined by 1.18 (
mm/g-Off).

This antibacterial fiber (type 11) was swollen well in water to a diameter of 1.
Fill a 70"m column and add L/L to a height of 11.5 parts m.
DA(26+DI) 1.11
/hr (SV50hr'), and 3 hours later, the number of countries of birth and the concentration of endotoxin, a pyrogen, were measured.

Number of viable bacteria (cells/100+nl) and endotoxin level (m)
nMml), the raw water is 1400 (pieces/100
m1), 14, 30 (ng/ml) t' treated water was 291 (pieces/ml>, 0.932 (ng/ml)
l) F Atsuta.

[Example 2] The antibacterial fiber (OH type) described in Example 1 was filled in the same manner (26 ml). To this, reverse osmosis membrane → ion exchange resin → 0
．． Water 13α/hr (
Water was passed through the tube at SV500hr', and the number of viable bacteria and endotoxin concentration were measured 8 hours later'! ″′：″・14ゞ4・
1 water “333 pieces/100m1)・1゛0
．． 023 (ng7'n+1), treated water is 01)J/
100ml 1.0,015 (ng/l).

[Comparative Example] The chloromethyl filament type 1 tan part described in Example 1 was added to 10 parts of a 30% trimethylamine aqueous solution, aminated at 30° C. for 1 hour, and washed with water to obtain taIf having a trimethylammonium group. The amount introduced is 2゜6 (mm)/(
J-CI2).

This fiber (Cα type) was packed into a column with a diameter of 1.7 cm and a height of 8 cm (2On+l). Tap water was passed through this at a rate of 0.5 ff/hr (SV25 hrl), and the number of viable bacteria was measured after 6 hours.
0m1 > , 51! 60 pieces of water per 100m1
)Met. Furthermore, it continued to increase as time progressed.

[Effects of the Invention] The molded product having antibacterial ability of the present invention not only has the effect of absorbing bacteria, etc., but also has the effect of sterilizing it.

This effect is highly effective and long-lasting even when the bacteria are at a high concentration or at a low Width. In particular, fibrous materials are suitable for household use because of their large surface area and ease of shaping. s+
A wide range of applications can be considered, including hospitals, industrial use, etc. Furthermore, in the molded product of the present invention, quaternary ammonium U is covalently bonded, and the quaternary ammonium ion does not elute, so it does not affect water quality and is safe and harmless.

Claims (1)

[Claims] A molded product having antibacterial activity, which is a polymonovinyl aromatic compound, which is crosslinked and insolubilized, and has a quaternary ammonium group having a long-chain alkyl group covalently bonded thereto.