JPS58183606A - Nonmedical agent inimical to microbe and alga - Google Patents

Abstract

PURPOSE:An improved agent inimical to microbes and algae useful as a slime controlling agent for paper making, lubricant for metal processing, aqueous emulsion, coating compound, paste, etc., obtained by combining a specific acetophenone compound with a compound such as methylenebisthiocyanate, etc. CONSTITUTION:The titled agent inimical to microbes and algae, containing a compound selected from acetophenone compounds(e.g., 2-bromo-4'-hydroxyacetophenone shown by the formula II, etc.) shown by the formula I (X is halogen; Y is halogen or H) and one or more compounds selected from (i) 3,5-dimethyl-1, 3,5-2H-tetrahydro-thiadiazine-2-thione, (ii) methylenebisthiocyanate, (iii) 1,4-bis (bromoacetoxy)2-butene, (iv) 1,2-bis(bromoacetoxy)ethane, and (v) 2-bromo-2- nitro-1,3-propanediol [preferably in a ratio of 1:(0.1-10)]as active ingredients.

Description

[Detailed description of the invention] A compound selected from the acetophenone compounds (hereinafter referred to as group A) shown in (aJ 5.5-
Dimethyl-1,3,5-2H-tetrahydrothyanazine-2-thione (truncated methylenebisnaosilinothione (a) 1,4-bis-(bromoacetoxy)2-butene (dJ 1.2-bis -(pro-7-ethyl)ethane (e) 2-bromo-2-nitro-1,5-probanol and (f) 5-chloro-2-methyl-4-isono-
Complexes of 3-one and metal salts and mixtures of 2-methyl-4-inch-3-one and metal salts. (However, metal salts are alkaline salts,
A non-medical product characterized in that the active ingredient is one or more compounds selected from alkaline earth metal salts (representing heavy metal salts) (compounds a to f above are hereinafter referred to as group B). The present invention relates to a moth-proofing agent for use.

In recent years, the use of water has become indispensable in the chemical industry.
The usage fee is also increasing. Naturally, problems associated with this include microorganisms occurring in cooling towers, etc., which may become clogged with slime caused by filamentous fungi, bacteria, or strong arms, or problems such as a decrease in heat exchange capacity may increase. In addition, in paper and valve factories, slime due to the growth of filamentous fungi and bacteria in the industrial water is produced on the refler walls and screens in the valve white water, which is an important part of the B process. Some of them may fall off and cause problems such as deterioration of paper quality or cause paper breakage during production by high-speed machines.

Furthermore, i14 in metal processing factories? The growth of fungi and bacteria in the recirculating water system of the oil emulsion can corrode metal products by producing slime, which is the home of biological colonies.

There are also problems during storage of the I4 oil emulsion itself.

In addition to these problems in industrial water systems, there have been other disasters caused by the proliferation of microorganisms. For example, industrial materials such as paint, valves, fiber treatment glue 2 and plywood may rot or grow mold, and the damage caused is widespread.

Conventionally, organic mercury compounds such as organic mercury have been used as control agents for these microorganisms. but.

4- It has an adverse effect on seafood. As the impact on the human body becomes clearer throughout history, it has become a serious pollution problem.

Its use is being regulated. For this reason, as alternative agents, autochlorine-based, organic sulfur-based, and quaternary ammonium-based drugs have been studied and used.

Organic chlorine-based chemicals are irritating, sulfur yarns have an effect on the color tone of the product, and quaternary ammonium salts can cause excessive foaming (such as It has all sorts of shortcomings when it comes to use.

The present inventors conducted numerous tests to solve this problem, and found that a composition containing a compound selected from Group A and one or more compounds selected from Group 3 as active ingredients is industrially harmful. The present invention has been completed by discovering that C is extremely effective as a control agent for filamentous fungi, bacteria, and filamentous fungi, compared to when each is used alone.

The compounds of Group A are represented by the general formula (wherein X is a halogen atom and Y is]) a halogen atom or a hydrogen atom. ) is a γ semiphenone compound, and the following compounds are included in Group A.

Compound (11 2-bromo-41-hydroxycetophenone compound (2; 2-chloro-4'-hydrocetophenone compound (3) r 2-3'-dibromo-41-hydrocetophenone compound (4) It'2-3'-chloro-4'-hydrocyrocetophenone The following are also examples of compounds of group B.

(a) OH,' OH-6,5-dimethyl-1,3,5-2H-tetrahydrothiadiazin-2-naone (b) 110sOH,SON Methylenebisthiocyanate (0) BrOHmυ0OOH,OH= 0HOH,0000 )
], Br1.4-bis-(pro-sevenylosetoxy)2-butene (d) Br OL 0000H+OI(+0OO(]Hz B
r1.2-bis=(bromoacetyl)ethane(θ) WO+ HOOHrυOH,OH 3r 2-bromo・2-nitro-1,6-brobaneshiol 7
- complex with 5-chloro-2-methyl-4-isothiazolin-6-one and metal salts, ox and 2-methyl-4-
Mixture of zolin-6-one and complex with metal salts? A mixture of 3:1. (However, M is an alkali metal.

It is an alkaline earth metal cation, and X is an anion that forms a compound with the cation M that has sufficient solubility to form a complex.

a is an integer 1 or 2, and n is an integer that satisfies the valence of the anion, X, or cation M.

The drug of the present invention is prepared by mixing all of the compounds listed in Group A and Group B with a bath agent or a solid fine powder diluent and a surfactant, and making it into a state that can be emulsified or suspended with water. ′
Ru. In addition, in the drug of the present invention, a compound of group A and a compound of group B are prepared separately and mixed at the time of use, or i:i group A,
In group B, some compounds are used first and then other drugs are used.It also includes the case of "f'stone".The drug of "1, and also the dud" is a compound of 2 or more yuzu/@zen direct. Or you can use it by mixing it with 'F8 agent. These drugs are preferably mixed in a ratio of 1 to 10 parts of the former compound of Group A and Group B.

The drug of the present invention exhibits extremely superior efficacy compared to the use of each agent alone.Acetophenone compounds included in the OA group exhibit activity against bacteria, filamentous fungi, and algae in general, but some bacteria and filamentous Low activity against fungi. It is an unsuitable agent as an anti-gravel agent that requires the presence of active metals against bacteria, fungi, and rodents in general, and is of little practical use when used alone. -1 included in group 13
Are the drugs also active to some extent against bacteria, filamentous fungi, and algae at high concentrations? However, it is extremely poor at low concentrations.

However, each of these groups A and B alone has a drawback 't-
It has been discovered that by combining these agents, it is possible to completely control the growth of an unexpectedly wide range of microorganisms.

The non-medical antibacterial and algae agent of the present invention (water in paper manufacturing and bulk manufacturing processes, industrial cooling water, industrial water such as heating and cooling water, lubricating oil for metal processing, water-based emulsions, paper, wood fibers, etc.) 1 board, paint, glue, valve.

During the manufacturing or cutting of fibers, etc., it is also possible to control molds, bacteria, #1 groups, storage materials, etc. that grow parasitically on these finished products.

In particular, one of the agents of the present invention is industrial water, lubricating oil for metal processing, and aqueous emulsion that cannot be controlled by each agent alone.

Main refrigeration for microbial damage such as paper, wood, paint and plywood [[6
6. Svergillus nikah, Benishi IJum stickii, Geotrichum canteidam.

Effectively acts on filamentous bacteria such as Cladosporium herbalum, Erobacter, Erogefus, Bacillus subtilis, etc., and completely suppresses the occurrence of industrially harmful microorganisms with a low-voltage agent. It is something that can be done. Especially l
Slime control agent for c1 paper, 1%1 for metal processing
Lubricating oil, aqueous emulsion.

It has been found to be effective as a preservative for paints and glues. EXAMPLES Next, examples will be shown, and the present invention will not be limited to the scope shown below.

Example 1 Compound +1110 parts (The following parts indicate mold needle percentages -4-)
.

Compound (a) 10'1. Noethylene 1j call'5
0 shame.

Two parts of N, N-dinonalborumamide 48fall tosolphor (product of Sokho Chemical Industry Co., Ltd.) were mixed together to form an emulsion.

Example 2 Compound? I (1115 parts), 5 parts of compound (b), 78 parts of ethylene glycol, and 2 parts of Tsurpol (manufactured by Toho Chemical Industries, Ltd.) were all mixed to form an emulsion.

Example 6 cation@”//I (111 (1 part, compound (o) 10 parts,
Methyl chloroform 6 cB@5 polyethylene glycol 48 ff1 (and 2 parts of Tsuruhole (product of Toho Chemical Industries, Ltd.) are mixed to form an emulsion.

Example 4 Compound @ tl + 10 Is, Compound @ (e) 10 parts, Shie f L, N glycol 78 and Tsuruhole (product of Toho Chemical Industry Co., Ltd.) 2 eIs gold mixed with emulsion and 1
-ru.

1 Example 5 110 parts of compound tl, compound? I(fH metal salt MgO2
using mouse) 3 ff1 (, diethylene glycol 85@
II: Mix 2 parts of Tsuruhole (product of Toho Chemical Industry Co., Ltd.) to make an emulsion.

Example 6 For compound wtl+7≦, compound (e) 7 5. Compound (f
) (function m <-t Mg0n, (i= use) 2
82 parts of Dienalen 11 Coal and 2 parts of Tsuruhole (manufactured by Toho Chemical Industries, Ltd.) were mixed to form an emulsion.

Example 7 Compound i2110 +ylL, compound % (fJ (metal salt used oaoLk) 5N, diethylene glycol +3'', FA and 2 parts of V Lebol (product of Toho Chemical Industries, Ltd.) were mixed together to form an emulsion.

Example 8 Compound 13+ 10 parts, compound (f) (metal salt 63M3
(It, all used) 5 parts, 85 f'tll of diethylene glycol, and 2 parts of Tsuruhole (product of Toho Chemical Industry Co., Ltd.) were mixed together to form an emulsion.

1'i2-1 Example 9 13110 parts of the compound, 10 parts of the compound (c), 30 parts of methyl chloroform, 48 parts of ethylene glycol, and 2 parts of Tsuruhole (manufactured by Toho Chemical Industries, Ltd.) were mixed to prepare an emulsion.

Example 10 Compound (1110 parts, compound (dJ 5 parts, methyl chloroform 30fflS, polyethylene glycol 53
1 part and 2 parts of Tsurupol (manufactured by Toho Chemical Industry Co., Ltd.) are mixed to form an emulsion.

Test Example 1 The minimum growth-inhibiting concentration of the composition of the present invention against each camphor microorganism on a broth liquid medium (PH 7.5 for bacteria, PH 4.5 for filamentous fungi) was measured by the agar dilution method.

The results are shown in Table 1.

Table 1 *1. All drug concentrations (pp+n) are formulation concentrations. , 2-pot reagents 11-20 are all 20% lactose 1 of each compound.

Compounds of 20 sample drugs (fJ uses all metal salts M60.

The test microorganisms are shown in full.

A, A: Aerobacter - Ryoerogefusu E-8: Bacillus subnunarus Elo: Nisu TII Suryo / Soli P-A: Nyuudanasu Erogi/The A-N: Aspergillus niger p-s: Benicillium. It is clear from Table 1 that Lycoderma l5PG・(+ Nigeotrichum canrdam)'I (as the composition of the present invention @ is the compound σ) is more effective in industrial water systems and water treatment than when used alone. Microorganisms in Shiba Accessories?The causative bacteria of the scourge, Aspergillus)/J4. Genus Trichoderma and the genus Trichoderma, Trichoderma spp., adhere to the surface of the paper and exhibit antibacterial properties at low concentrations. The drug of Example 5 was added twice a day to the daily circulating yarn core of a mesh paper machine using a pump. Addition location is approximately 25n
The valley m of "r" is a paper machine chest that costs 1 yen, and each time is 4
Add 1 stiffness to each line by adding 1 stiffness to the time. The test intercostals were washed with water at 11 points for a period of 151 hours. The efficacy of the drug was determined from the number of breaks caused by Sufimhorde suspended on a white water bit and the slime. For comparison, compound (11) and compound (f'+ (metal salt is k1
A similar test was conducted for each 20% emulsion of g+, ]i', ). Sho combination? Addition 1 of N11 and (f) formulation is the same as Example 5. K4$j64k

Table 2 Test Example 6 Misaki Whetstone Coating - Liquid (PH8, 3-powder Coating Liquid) Pour G broth liquid medium and pre-rotted T Coating liquid, stir, and let it cool to a predetermined degree. All drugs were added.

After culturing this 1Lk in an incubator at 50°C for 5 days.

The number of viable bacteria, filamentous fungi, and yeast in each sample was measured to determine the antiseptic efficacy of each drug.

The results are shown in Table 6.

The agent of the present invention was also extremely effective in coating liquids containing starch as the main binder compared to when used alone.

Ice 1. All drug concentrations (ppm) are in the formulation.

2. Test drugs 7 to 12 all have 20% concentration of each compound.

3 Compound of test mulberry agent 12? l (f) is metal salt Mg0M,
Use Q Patent Applicant: Kumiai Chemical Industry Co., Ltd. Procedural Amendment (Voluntary) July 1, 1980 Director-General of the Patent Office Kazuo Wakasugi 1, Indication of Case 1982 Patent Application No. 66908 2, Name of Invention Non-medical Bacterial and algae preventive agent for use 3 Person making the amendment Patent applicant related to the case 1-4-26 Ikenohata, Taito-ku, Tokyo, 05 (823) 1701 4, Details subject to the amendment Homare 1, Title of the invention Medical antibacterial and algae preventive agent 2, claims selected from among acetophenone compounds represented by the general formula (wherein X represents a halogen atom, and Y represents a /1p gene atom or a hydrogen atom) and (alis, 5-dimethyl-1,3,5-21■-
Tetrahydrothiadiadi/-2-thione (b) methylene bisthiocyanate (c114-bis(bromoacetoxy)2-butene (d) 12-bis(bromoacetoxy)ethane and (e
) 2-bromo-2-nitro-1,3-propanediol.

5. Detailed Description of the Invention The present invention represents the general formula (wherein X represents a rogen atom, and Y represents a rogen atom or a hydrogen atom). ) A compound selected from the acetophenone compounds shown in (hereinafter referred to as group A) and (al 3+5
-dimethyl-1,3,5-2H-tetrahydrothiadiazine-2-thione (bl methylene bisthiocyanate tel 1.
4-bis-(bromoacetoxy)2-butene (d) 1,2-bis-(bromoacetoxy)ethane and (e) 2-bromo-2-nitro 1,5-pronoquinediol (fa) to ( The active ingredient is one or more compounds selected from the group el compounds (hereinafter referred to as group B).'4r: Concerning a non-medical antibacterial antifreeze agent, which has been recently used in the chemical industry. In this case, the use of irrigation water is essential.
Its usage is also increasing. A natural problem associated with this is that cooling towers are clogged with slime caused by microorganisms such as filamentous fungi, bacteria, or algae.

Alternatively, problems such as a decrease in heat exchange capacity are increasing. In addition, in paper and pulp mills, slime due to the proliferation of filamentous fungi and agonium in the industrial water is an important part of the manufacturing process.

It occurs on riffer walls and screens, and some of them fall off, causing problems such as deterioration of paper quality and causing paper breakage in production processes using high-speed machines. Additionally, in metal fabrication plants, the growth of fungi and bacteria in the recirculating water system for lubricating oil emulsions can cause the water to spoil and corrode metal products by producing slime, a microbial collection. There are also problems during storage of the lubricating oil emulsion itself. Furthermore, in addition to these disturbances in industrial water systems, there are also disasters caused by the proliferation of #organisms. For example, industrial materials such as paint, pulp, and fiber processing glue 1 plywood may rot or grow mold, and these disasters are widespread.

Conventionally, metal compounds such as organic mercury have been used as control agents for these microorganisms. However, these compounds have strong properties, and if they are directly discharged into rivers during drainage, they can have a negative impact on fish and shellfish.

As its effects on the human body become clearer, it has become a serious issue and its use is being regulated. For this reason, organic chlorine-based, organic sulfur-based, quaternary ammonium salts, etc. have been studied and used as alternative chemicals, but organic chlorine-based chemicals are irritating, and organic sulfur-based chemicals are harmful to products. The effect of quaternary ammonium salts on the color tone of

These drugs also have various disadvantages in use, such as excessive foaming.

The present inventors have conducted various studies to solve this problem, and have found that a composition containing a compound selected from AM and one or more compounds selected from group B as active ingredients is an industrially well-known filamentous fungus. #ITj@.

The present invention was completed by discovering that the combination of an algae control agent and l- is extremely effective compared to when each is used alone.

The following compounds are included in APE.

Compound (1) 2-bromo 4'-hydroxyacetophenone compound (2) 2-chloro-4'-hydroxyacetophenone=5- compound (3) r 2 , s'-sheer Clmo 4'-hydroxyacetophenone compound (4) 2.3'-Dichloro-4'-hydroxyacetophenone The following compounds are also included in Group B.

3.5-Dimethyl-1,3,5-2H-tetrahydrothiadiazin-2-thousand 6- (bl NC8CHtSCN Methylene bisthiocyanate (CI B r CHz COQCHz CH=CHCHz 0
0 CCHt B rl, 4-bis(bromoacetoxy)2-butene dl B rCH, C00CH2CH, 0OCCH, Br1.
2-bis(bromoacetoxy)ethane (e) No.

HOCH, CCH, OH r 2-Bromo 2-nitro-1,3-7'ropanediol The drug of the present invention It is mixed with a surfactant and used in a state that can be emulsified or suspended with water. In addition, the drug of the present invention can be prepared by separately preparing a compound of group A and a compound of group B and mixing them at the time of use, or by using either a compound of group A or group B first and then using another drug immediately. It also includes cases. Furthermore, the uninvented drug is 2N
Compound 4 above J,.l can also be used directly or dissolved in a solvent. For these drugs, compounds of Group A and Group B are preferably mixed in a ratio of 0.1 to 10 for the latter to 1 for the former.

The drug of the present invention is characterized by exhibiting extremely superior efficacy compared to VC used alone.The acetophenone compound contained in group A is directed against bacteria.

It shows activity against all filamentous fungi and algae, but has low activity against some bacteria and filamentous fungi. It is an unsuitable agent as a bactericidal and algae-proofing agent that requires high activity against bacteria, filamentous fungi, and all F4 species, and is of poor practical use when used alone.

On the other hand, drugs included in group B also exhibit some activity against bacteria, filamentous fungi, and algae at high concentrations, but are extremely poor at low concentrations. However, by combining the drugs of groups A and B, each of which has drawbacks when used alone, it is possible to control Ni infestation by a wide range of microorganisms that cannot be predicted.

The non-medical security agent of the present invention is used in paper and pulp manufacturing industries.
Water for VC, industrial cooling water, industrial water such as cooling water for air conditioning, lubricating oil for metal processing, water-based emulsion 1 paper, wood 1 plywood, paint, glue.

Filamentous fungi that grow parasitically on the finished products during the processing or processing of pulp, *fiber, etc.

It is important to control bacteria, yeast, algae, etc. % of industrial water and lubricating oil for metal processing, which cannot be controlled by the agent of the present invention alone.

It is the main cause of microbial damage to aqueous emulsions, paper, wood, paint, plywood, etc. Aspergillus niger. Penicillium sticki, Geotrichum candedum,
Items that are effective against filamentous organisms such as Cladosporium helharum, Aerobacter aerokenes, and Bacillus subtilis, and can completely suppress the occurrence of industrially harmful microorganisms with a small amount of chemicals. It is. In particular, excellent effects have been recognized as a slime control agent for paper manufacturing, lubricating oil for metal processing, aqueous emuldimin, paint, and preservative for glue.

Next, examples will be shown and explained, but the present invention falls within the following range.
It is not limited to IJAK.

Example 1 Compound flllO parts (the following parts indicate parts by weight).

1 allO parts of the compound, 50 parts of diethylene glycol.

48 parts of N,N-dimethylformamide and 2 parts of Tulpol (manufactured by Toho Chemical Industries, Ltd.) are mixed to form an emulsion.

Example 2 A compound (1115 parts, compound (b) 5 parts, 78 parts of ethylene glycol, and 2 parts of Tulpol (Toho Chemical, Kogyo Co., Ltd. product) are mixed to prepare an emulsion.

Example 6 Compound (1110 parts, compound [eNO], 6O parts of methyl chloroform, 48 parts of polyethylene glycol, and 2 parts of Tulpol (manufactured by Toho Chemical Industries, Ltd.) were mixed to prepare an emulsion.

Example 4 Compound (1110 parts, 1 ellO part of compound, 1 part of diethyl)
Mix 78 parts of 0-glycol and 2 parts of Tsurpol (manufactured by Toho Chemical Industries, Ltd.) to prepare an emulsion.

Example 5 10 parts of compound (3), 110 parts of compound (c), methyl chloroborum 3095 ethylene glycol 48 i (1) and 2 parts of Tsurpol (manufactured by Toho Chemical Industries, Ltd.) were mixed to prepare an emulsion.

Example & 1110 parts of compound +, 5 parts of compound (d), 30 parts of methyl chloroform, 55 parts of polyethylene glycol, and 2 parts of Tulpol (manufactured by Toho Chemical Industries, Ltd.) are mixed to prepare an emulsion.

Example Z Compound (1115 parts, Compound (d) 5 parts, 30 parts of methyl chloroform, 48 parts of polyethylene glycol, and 2 parts of Tsurpol (manufactured by Toho Chemical Industry Co., Ltd.) are mixed to prepare an emulsion.

Example 8 Compound (3110 parts, 1 ellO part of compound, ethylene □
An emulsion was prepared by mixing 78 parts of glycol and 2 parts of Tsurupol (manufactured by Toho Kagaku Kogyo Co., Ltd.).

Next, the effect of the drug of the present invention J) will be explained using Test Example 4.
Ru.

Test Example 1 (Growth 1114 inhibition test for each glaze microorganism)
The minimum concentration of the drug of the present invention that inhibits the growth of lilysome organisms on a broth liquid medium (H7.5 for bacteria, pH 45 for filamentous fungi) was determined by the agar dilution method.

The results are shown in Table 1.

Table 1 (1) In the table, test drugs -161 to scrap 1o are the invention group,
/% 11 to /1619 are single comparison plots.

(In Table 21, all nail growth inhibiting nail concentrations (ppm) are concentrations of the pharmaceutical products.

(3) The test microorganisms in the table are as follows.

13- A. Tri: Trichoderma sp G, C Nigeotrichum candedum As is clear from Table 1, the drug of the present invention is more effective against Aerobacterium 1, which is the causative agent of microbial disasters in industrial water systems and industrial products, than when each compound is used alone. -m, Bacillus, Aspergillus, Penicillium, Trichoderma, Geotrichum, etc. exhibited antibacterial activity at extremely low concentrations.

Test Example 2 (Coating liquid preservative test) Add the bouillon liquid medium and the coating liquid to the papermaking coating liquid (PH8.5 starch coating liquid) and stir until the specified concentration is reached. Each drug was added as follows. This is 30°
After culturing for 5 days in incubator C, 441 in each sample
The preservative efficacy of each drug was determined by measuring the number of live yeast cells per field and filamentous cup.

The results are shown in Table 2.

Table 2 The concentration in the table is the concentration of the preparation6 (The number of bacteria in Table 21 indicates the number of bacteria in the sample i mA.

The agent of the present invention was also extremely effective for coating liquids containing starch as the main binder compared to when used alone.

Test Example 6 (Slime generation prevention test) Slime (viscous material formed by microorganisms) and white water produced during the paper manufacturing process of a paper manufacturing company that makes kraft paper were collected and subjected to a test. The slime is pulverized using a homogenizer and dispersed in white water in which 1% of bouillon liquid medium has been dissolved in advance. Add 19 rnl of white water in which slime has been dispersed into a 201 L-shaped tube and dilute it to a predetermined concentration.
Continuous shaking was performed using a mono-shaker whose temperature was adjusted to 60°C. After 24 hours and 72 hours, the number of viable bacteria in the white water was determined. The results are shown in Table 6.

(1) The concentrations in the table are formulation concentrations.

(2) The number of viable bacteria in the table indicates the number of viable bacteria in 111 tons.

As shown in Table 3, the agent of the present invention was extremely effective against slime-forming bacteria that adhered during the papermaking process and microorganisms in white water compared to single agent use.

Test Example 4 (Glue Preservation Test) Each agent was added to a rc office glue made directly from a starch company at a predetermined concentration to achieve a predetermined concentration. Next, equal amounts of the same type of glue that had rotted during the distribution stage were added, stirred well, and left in a warehouse for 2 and 8 weeks. The effectiveness of the drug was determined based on the number of viable bacteria and the smell of rot. .

The results are shown in Table 4.

19- (1) In the table, agt is the formulation concentration.

(The number of viable bacteria in Table 21 indicates the number of viable bacteria in 1 mA.

3) The evaluation of rotten odor in the table is as follows: 1, -2 No odor ±: Slight odor 12 Slight odor H 2 Strong odor T: Strong odor As described above, the drug of the present invention cannot be used alone. It was extremely effective.

Patent applicant Kumiai Chemical Industry Co., Ltd. 21-Continued from page 1 ■Int, C1, 3 identification code Office reference number (A
OIN 37106-35
104) 7419-4H(A
OIN37102-35104) 7419-4H
(AOIN 35104 -
-33/20) 6464-4
H0 Inventor Yoshihiro Konagai 79-9-1 0 Nakanogo, Fujiyo-cho, Ibara-gun, Shizuoka Prefecture Inventor Osamu Takatsuka Inside Giken Chemical Industry Co., Ltd., 328 Shioninden Hamano, Fukuda-machi, Iwata-gun, Shizuoka Prefecture

Claims (1)

[Scope of Claims] A compound selected from among the compounds represented by the general formula (where X is a halogen atom and Y is a norogen atom or a hydrogen atom) and (a ) 5.5-dimethyl-1,3,5-2H-tetrahydrona-2-naone (1)) Menalen bisthiocyanate (a) 1,4-bis-(pro-7-acetoxy) 2-butene (d) 1,2-bis-(bromoacetoxy)ethane (e) 2-bromo-2-nitro-1,3-propanedio and (f) 5-chloro-2-methyl-4-inch. A complex of zolin-5-one and a metal lump, a complex of 2-methyl-4-isothiazo11-6-'A and a metal salt, and a mixture of ox. (However, metal salts represent alkali metal salts, alkaline earth buds, and stop metal salts.) Uchiyo F) J! ! Non-medical use of Bokenbokenchuan, which is characterized by containing more than one citron compound and all active ingredients.