JPH02250803A - Bactericide containing resin having antibacterial activity as active component - Google Patents

Abstract

PURPOSE:To provide a metal-free low-toxic bactericide containing an active component consisting of a copolymer of a vinyl monomer and a radically polymerizable vinyl monomer containing amino group or an aqueous dispersion of a cationic polymer produced by quaternarizing the terminal amino group of the above copolymer with an acid. CONSTITUTION:The objective bactericide contains, as active component, a copolymer derived from 20 to 97wt.% of a vinyl monomer (e.g. styrene, vinyl chloride, butadiene or methyl acrylate) and 3 to 80wt.% (preferably 5 to 50wt.%) of a radically polymerizable monomer of formula (R1 is H or CH3; X is 0 or NH; R2 and R3 are 1-4C alkyl; n is 2 to 5). An aqueous dispersion of a cationic polymer produced by quaternarizing the terminal amino group of the copolymer with an acid can be used also as an active component. The obtained bactericide can be used as a bactericide for plant, seed, wood, textile product, cosmetics, paints, etc., or in the form of film, fiber, molded article, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a disinfectant containing as an active ingredient a copolymer of a vinyl monomer, an amino group-containing radically polymerizable monomer, and a vinyl monomer.

<Prior art> Organometallic agents are commonly used as disinfectants with antibacterial activity, but due to the pollution caused by their toxicity, there has been a demand for the development of non-metallic, low-toxicity agents. There is.

<Problems to be Solved by the Invention> The object of the present invention is to develop a non-metallic, low-toxicity fungicide that has excellent pesticidal efficacy.

<Means for Solving the Problems> As a result of intensive studies to find a drug with excellent bactericidal activity, the present inventors found that a copolymer containing the above-mentioned 7-mino group-containing radically polymerizable vinyl monomer It was discovered that this compound has excellent bactericidal activity, leading to the present invention.

That is, in the present invention, 20 to 97% by weight of vinyl nitrate
, general formula (1) C, where R1 is H or CH, X is O or NR1, R2 and R3 are the same or different and represent an alkyl group having 1 to 4 carbon atoms, and n represents an integer of 2 to 5. ] It provides a disinfectant containing as an active ingredient a copolymer containing 3 to 80% by weight of one or more amino group-containing radically polymerizable vinyl monomers shown below.

Furthermore, the terminal amino group of the above copolymer is converted into a quaternary salt with an acid (an aqueous dispersion of a cationic polymer obtained by this process is also included in the disinfectant of the present invention).

The following harmful bacteria can be controlled by the amino group-containing radically polymerizable vinyl monomer-containing copolymer or the aqueous dispersion of its cationic polymer according to the present invention. It is not limited.

Rice blast fungus (Pyricularia oryz)
ae ), Sesame leaf blight fungus (Cochliobolus
mlyabeanus), sheath blight fungus (Rh1zoct)
onia 5olani), Bakanae disease fungus (G 1bb
Gibberella zeae), snow rot fungus (Typhula sp, Micronectri)
ella n1valis), Pseudophylla
cercosporella herpotricho
ides), Rhynchosporiu
m 5ecalis), leaf blight fungus (Septoria
tritici), Pyrenopho fungus (Pyrenopho
ragram 1nea), Leptos blight (Leptos
phaeria nodown), citrus black spot fungus (Diaporthe citri), scab fungus (Elsinoe fawcetti), green mold fungus (Pen1ci II iumdigitatum,
Penicillium italicum), Xanthomonas campestri
s), apple monilinia disease fungus (Sclerotin
ia mali), rot fungus (Valsa mali)
), Alternaria mali
), Venturiainaequal
is ), Agrobacterium tumefaciens
u+nfume fac 1ens), pear scab fungus (Venturia nashicola), black spot fungus (Alternaria ki) cuchiana)
, Gymnosporangium ha
raeanum), peach gray layer fungus (5clerot
inia cinerea), Clado
sporium carpophilum ), Phomopsis rot fungus (Phomops 1ssp, ), grape black rot fungus (Elsinoe ampelina),
Glomerella cingulata
), oyster anthracnose fungus (Gloeosporium ka
ki), Cercospora caki
, Mycosphaerella nawae), Cucurbit anthracnose fungus (Colletotrichum Ia)
genarium), Vine blight fungus (Mycosph)
aerella melonis), Pseudomonas lachrymans,
Tomato rot fungus (Alternaria 5ola)
ni), leaf mold fungus (Cladosporium ful
vum), Phomopsis ve
xans), cruciferous vegetable black spot fungus (Alter
naria japonica), white spot fungus (Cerc
osporella brassicae), Puccinia allii, spring rot fungus (Pseudomonassyringae),
Soybean purpura fungus (Cercospora kiku)
chii), Elsinoe glyci
nes ), Diaporthe pha
Scolorwn var, 5ojae), Colletotrichum linde
Myc muthianum),
osphaerella personatum), Cercospora arachidico
la), potato summer blight fungus (Alternar
ia 5olani), tea net blast fungus (Exob
asidium reticulatum), Elsinoeleucospi la, and Alternarialongipe of tobacco.
s ), Colletotrichum t
abacum), sugar beet brown spot fungus (Cercosp)
ora beticola), = Njin black spot fungus (
Alternaria radicina), Diplocarpon rosae,
Septoria chrysant
hemiindici), gray mold fungus (Botrytis cinerea), and sclerotium fungus (Botrytis cinerea) on various crops.
5clerotinia sclerotiorum
), Rh1zoctonia 5ol
ani, pythium Sp, ), Aspergillus sp, ), Chaetomium sp, ), Cladosporium sp,
), Staphylococcus aureus
s aureus), Escherichia coli (Escherichia
coli), Rhizopus s
l), ), Aureobasidium (Aureobasidium
idium sp, ), Mucor sp.
, ), Penicillium fungi ( Penicillium
Bacillus sp, Enterobacter sp.
, Pseudomonas sp., Saccharomyc sp.
es sp, ), Candida sp.
), Fusarium sp.

Therefore, the copolymer according to the invention or its aqueous dispersion of cationic/polymer can be used as a fungicide for plants or seeds, wood, bamboo products, textile products, paper products, cosmetics, glass, paints, etc.
It can be used as an agent to eradicate harmful bacteria for industrial products such as synthetic resins, other sanitary processing agents, cleaning agents, or "preservatives," and as an active ingredient in disinfectants such as slime control agents and food preservatives.

General formula (
Preferred specific examples of the amino group-containing radically polymerizable vinyl monomer represented by 1) include dimethylaminoethyl acrylamide, dinotylaminopropylacrylamide, dimethylaminobutylacrylamide, diethylaminoethylacrylamide, diethylaminopropylacrylamide, diethylaminobutylacrylamide, dimethylaminobutylacrylamide, -n-propylaminoethyl acrylamide, di-n-propylaminopropylacrylamide, di-n-propylaminobutylacrylamide, di-n-
Butylaminoethyl acrylamide, di-n-glylaminopropylacrylamide, di-n-butylaminobutylacrylamide, N-(1,1-dimethyl-3-dimethylaminofurovir)acrylamide, N-(2-methyl-3- dimethylaminopropyl) acrylamide and their corresponding methacrylamide derivatives,
Dimethylaminoethyl acrylate, dimethylaminofuropyl acrylate, dimethylaminobutyl acrylate, diethylaminoethyl acrylate, diethylaminopropyl acrylate, diethylaminobutyl acrylate, di-n-furopylaminoethyl acrylate,
Di-n-propylaminopropyl acrylate, di-n
-Flopylaminobutyl acrylate, di-n-butyl 7minoethyl acrylate, di-n-butylaminopropyl acrylate, di-n-butylaminobutyl acrylate, N-(1,1-dimethyl-3-dimethylaminopropyl) Examples include acrylate, N-(2-methyl-3-dimethylaminopropyl)acrylate, and the corresponding methacrylate derivatives.

Particularly preferred comonomers include dimethylaminopropylacrylamide, dimethylaminopropylmethacrylamide, diethylaminopropylacrylamide,
Mention may be made of di-n-propylacrylamide, di-n-butylpropylacrylamide, dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate.

The vinyl heptamer copolymerized with the (1) hetamine used in the present invention is not particularly limited, but
The following monomers are suitable due to their copolymerizability. For example, styrene, vinyl toluene, getadiene, isoprene, vinyl chloride, odorous vinyl, vinyl chloride, vinyl halides such as vinylidene chloride, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate, vinyl laurate, versatic acid. Vinyl esters such as vinyl; methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (ivy)acrylate, stearyl (meth)acrylate Ester compounds of (meth)acrylic acid and alkyl alcohol having 1 to 18 carbon atoms, such as (meth)acrylonitrile, etc., and one type or a mixture of two or more of these can be used. . It is also possible to copolymerize functional vinyl monomers containing amide groups, hydroxyl groups, carboxylic acid groups, methoxy groups, etc., if necessary.

Any commonly used polymerization method can be used, such as solution polymerization, bulk polymerization, suspension polymerization, etc., but the most preferred method is synthesis by emulsion polymerization.

As the polymerization initiator used in emulsion polymerization, any compound that generates free radicals can be used; for example, 2,2-azobis(2-amidinopropane) hydrochloride, hydrogen peroxide, or and a reducing agent Benozoyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, or a combination of these and a reducing agent are preferably used. Also, ammonium persulfate, etc. Anionic polymerization initiators can also be used. be.

As a surfactant when carrying out water dispersion polymerization, commonly used cationic or nonionic surfactants are used. A dispersion is obtained.

Furthermore, the use of a cationic surfactant such as alkyldimethylbenzyl chloride or lauryltrimethylammonium chloride, which has bactericidal properties, has the advantage of improving the antibacterial activity of the resulting aqueous dispersion. When the amino group-containing radically polymerizable vinyl monomer is neutralized with an acid during polymerization, a stable cationic polymer aqueous dispersion can be obtained.

The aqueous dispersion of a cationic polymer obtained by emulsion polymerization can be used as it is as an active ingredient of a disinfectant, but the aqueous dispersion may also be used as a molded article as a resin by reprecipitation, salting out drying, or the like. Molded bodies may be used in the form of powder, pellets, films, sheets, fibers, etc., but they can be mixed with solid carriers, liquid carriers, surfactants, other formulation auxiliaries, etc., to produce water use agents, suspensions, etc. agents, powders, aqueous suspensions, etc. (These may also be used in the form of formulations.

The active ingredient content in the above formulation is usually 0.1 to 95% by weight.
0%, preferably in the range of about 0.2-90%.

The solid carriers include kaolin clay, heptadite clay bentonite, acid clay, pyrophyllite, talc, diatomaceous earth, calcite, corncob powder,
Examples include fine powders or granules such as walnut flour, urea, ammonium sulfate, and synthetic hydrated silicon oxide. Examples of liquid carriers include water and the like.

When the aqueous dispersion of a cationic polymer or its copolymer resin according to the present invention is used as an active ingredient of a disinfectant, it can be used in liquid, suspensine, paste, granular, powder, film, porous, etc. formulations. impregnated paper, in the form of flexible films, sheets, fibers, molded articles, or other forms, or in combination with carriers such as paper, plastic, and inorganic boards;
It can be used in disposable diapers, wallpaper, packaging materials for clothing and food, air filters, notebooks, building boards, anti-mold paints, etc.

Moreover, the present invention ◆ The ethylene copolymer can be used in composite yarns such as core-sheath type or parallel type made from polypropylene resin, polyethylene resin, polyamide resin, acrylic resin, etc., and from the composite yarns. By processing it into woven and non-woven fabrics, it can be used for various daily life-related materials such as air conditioner filters, sheets, futons, and sanitary materials.

<Example> The present invention will be described below with reference examples, formulation examples, and test examples.
Although explained in more detail, the present invention is not limited to these descendants.

The analysis method is as follows.

(1) Solid content Compliant with JIS K6839 4.2.

Accurately weigh out the emulsion onto an aluminum foil plate 1
After drying for 3 hours at 05℃ (desiccator)
I left it to cool inside. Weigh the mass and use the following formula to determine the solid content (w
t%) was determined.

D: Mass of sample after drying (2) S; Mass of emulsion (2) (2) Viscosity Compliant with JIS K6838-4.

The emulsion temperature when collecting emulsion soda in a container is 25±0
．． The temperature was adjusted by placing it in a constant temperature bath until the temperature reached 5°C, and the temperature was measured using a BL type rotational viscometer (manufactured by Tokyo Keiki Seisakusho ■).

The rotational speed of the viscometer was 60 rotations/min, and the viscosity was calculated by reading the scale shown on the indicator after rotating for 1 minute and multiplying by a specified conversion multiplier.

(3) Particle size (μ) Water was added to the emulsion solution to adjust the concentration to 0.01%, and then the particle size was determined using the turbidity method G using a UV spectrophotometer (manufactured by Hitachi ■).

Example-1 In a 2-ton separable flask equipped with a reflux condenser, thermometer, and stirrer, 800 tons of water, dimethylaminopropylacrylamide 802, and 36% hydrochloric acid (mole ratio of 1.0 to 7 amino groups of the copolymer) were added. hydrochloric acid), styrene 160
After charging 160 f of butyl acrylate and raising the temperature to 60°C, the inside of the reaction system was purged with nitrogen gas.

Then 5% 2.2'-azobis(2-amidinopropane)
An aqueous hydrochloride solution was fed into the reaction system at a constant rate for 4 hours to cause the reaction. After 4 hours, the temperature was further raised to 80°C, and the reaction was continued for 2 hours. When the residual monomer decreased to 0.5% or less, polymerization occurred. has ended.

This emulsion soda was designated as antibacterial evaluation sample S-1. The evaluation results are shown in Table 1.

Example 2 Polymerization was carried out in the same manner as in Example 1, except that styrene 320f was used in place of styrene 160y and butyl acrylate 602 in Example 1.

This emulsion was designated as antibacterial evaluation sample S-2. The evaluation results are shown in Table 1.

Example-3 The procedure was carried out in the same manner as in Example-1, except that dimethylaminopropylacrylamide 80? Polymerization was performed using diethylaminopropylacrylamide 809 instead of.

This emulgene was designated as antibacterial evaluation sample S-3. The evaluation results are shown in Table 1.

Example 4 Polymerization was carried out in the same manner as in Example 1, except that 802 t of dimethylaminoethyl methacrylate was used in place of 80 t of dimethylaminoflobil acrylamide in Example 1.

This emulgene was designated as antibacterial evaluation sample S-4. The evaluation results are shown in Table 1.

Comparative Example-1 The same procedure as in Example-1 was carried out, except that 8M of methoxyaminopropylacrylamide was used instead of 80t of dinotylaminopropylacrylamide in Example-1.

This emulgene was designated as antibacterial evaluation sample S-5. The evaluation results are shown in Table 1.

Test Example 1 Antibacterial spectrum potato dextrose (PDA) medium against harmful bacteria (5000pp as solid content)
The sample sample (S-1, 3-
2, 5-3, S-4, 5-5) were mixed and poured into a tube with a diameter of 90 mm to solidify.

Thereafter, spores or bacteria were inoculated as a suspension using a platinum loop, and cultured at 27°C for 5 days.

The growth state of the bacteria was observed, and the growth inhibition effect of each test agent was investigated. The results are shown in Table 2. The growth inhibition effect was based on the following standard G.

Index 5 Complete inhibition of bacterial growth 4 99-90% inhibition 3 89-50% inhibition 1 50% or less inhibition <Effect of the invention> The fungicide of the present invention exhibits excellent effects against various harmful bacteria Therefore, it can be used for various purposes as an active ingredient in disinfectants.

\

Claims (4)

[Claims] (1) 20 to 97% by weight of vinyl monomer, general formula [
I 〕▲There are mathematical formulas, chemical formulas, tables, etc.▼〔I〕 [In the formula, R_1 is H or CH_3, X is O or NH, R
_2 and R_3 are the same or different and represent an alkyl group having 1 to 4 carbon atoms, and n represents an integer of 2 to 5. A fungicide characterized by comprising as an active ingredient a copolymer containing ~80% by weight. (2) The terminal amino group of the copolymer according to claim 1 is removed with an acid.
A disinfectant characterized by containing as an active ingredient an aqueous dispersion of a cationic polymer obtained by converting it into a grade salt. (3) A claim in which the amino group-containing radically polymerizable vinyl monomer is one or more selected from the group consisting of dimethylaminopropylacrylamide, dimethylaminopropylmethacrylamide, diethylaminopropylacrylamide, dimethylaminoethyl methacrylate, and diethylaminoethyl methacrylate. The fungicide according to item 1 or 2. (4) Claim 1 or 2 wherein the vinyl monomer is one or more selected from the group consisting of styrene, vinyl chloride, vinyl acetate, butadiene, methyl acrylate, ethyl acrylate, butyl acrylate, and methyl methacrylate. Disinfectants listed.