WO2000010394A1 - Industrial, anti-bacterial and -fungal agents, algicides and bioadhesion inhibitors, containing phenyl isothiocyanates - Google Patents

Abstract

Industrial, anti-bacterial and -fungal agents, algicides and bioadhesion inhibitors, containing phenyl isothiocyanates represented by general formula (1) wherein X, Y and Z are each independently C1-C5 alkyl (which may be fluorinated), C1-C5 alkoxy (which may be fluorinated), C2-C6 alkoxycarbonyl, halogeno, nitro, hydroxyl or carboxyl; G is oxygen, sulfur, sulfinyl, sulfonyl or N-R (wherein R is hydrogen, C1-C5 alkyl, C2-C6 alkenyl or C2-C6 alkynyl); j and k are each independently an integer of 0 to 5, with the sum of j and k being 5 or below; and l is an integer of 0 to 4.

Description

 1

 Description Industrial antibacterial and antifungal agents containing phenylisothiocyanates

 Algicides and biofouling inhibitors

 The present invention relates to antibacterial and antifungal agents and algicides for industrial products, antibacterial and antifungal agents and algicides used in the production process of industrial products, and water for preventing harmful aquatic organisms such as shellfish from adhering. It relates to a biofouling inhibitor. In the present invention, the use of industrial antibacterial and antifungal agents covers all uses other than the use of antibacterial and antifungal agents in the pharmaceutical and agrochemical fields, and the use of algicides includes the use of herbicides in the agrochemical field. It covers everything except the application. Background art

 Industrial antibacterial and antifungal agents and algicides are used to eliminate various adverse effects of the growth and growth of bacteria, fungi and algae on various industrial products and facilities. Conventionally, as these industrial antibacterial and antifungal agents and algicides, organic nitrogen compounds, organic nitrogen compounds, organic halogen compounds, nitrogen-containing aliphatic polymers and heavy metal coordination compounds have been used. I have.

 Anti-fouling agents can be found in underwater equipment such as fishing nets, ship bottoms, buoys, marine structures, condenser cooling water systems for thermal or nuclear power plants, heat exchanger cooling water intake channels for the chemical industry, It is used to prevent harmful aquatic organisms such as shellfish from attaching to underwater structures or reservoirs.

 If these aquatic organisms adhere to the cultivation net, the mesh will be clogged, and the growth of the cultivated fish will be hindered due to a decrease in the distribution of seawater, and frequent occurrence of fish diseases will occur.

 The adhesion of these aquatic organisms to ships causes an increase in fluid resistance, resulting in a decrease in navigation speed, an increase in fuel consumption, and a loss of costs for cleaning the bottom of the ship and costs due to suspension of operation.

In marine facilities, marine and underwater structures, the attachment of aquatic organisms causes significant weight gain and inconvenience in handling operations, and attachment to the intake channel causes a decrease in thermal conductivity and blocks the intake channel. Or the amount of water intake decreases. Conventionally, in order to prevent the adhesion and propagation of these organisms in seawater and freshwater water, antifouling paints containing an organotin compound such as pistribyl tilsoxide and a copper compound such as copper sulfate and cuprous oxide have been used.

 The above-mentioned organic nitrogen compounds, organic nitrogen compounds, organic halogen compounds, nitrogen-containing aliphatic polymers, heavy metal coordination compounds, etc. are irritating and cause a problem in the Occupational Safety and Health Law, and the amount of drug used is large. It contains chemicals that are problematic from the viewpoint of environmental protection, releases formalin or halogens, and includes chemicals that may affect the human body and cause environmental pollution and chemicals that cause environmental pollution by heavy metals. Not all fungicides and algicides are composed solely of the preferred agents.

 The above-mentioned organotin compounds as biofouling inhibitors are effective in preventing the fouling of aquatic organisms, but are highly toxic. It has become.

 For example, in the United States, the Organtin Tin Antifouling Paints Control Act (11987) banned the use of organotin marine paints on ships less than 65 feet, and in the United Kingdom, the Food Environmental Protection Act (1998) 7 years) banned the use of antifouling agents containing triptyltin in ships less than 25 meters and in marine agriculture.

 In Japan, triptyl sulphoxide is classified as a Class 1 Specified Chemical Substance, and triphenyltin compounds and triptyl tin compounds are classified as a Class 2 Specified Chemical Substance under the Act on the Regulation of Chemical Substances Examination and Manufacture. The use of fishing nets is prohibited.

 In addition, measures have been taken to curb the use of triptyltin-based bottom paints (Notice of the Ministry of Transport, 1990).

 In addition, the above-mentioned copper compounds widely used in antifouling paints for intake channels and ship bottoms contain copper, which is a heavy metal like tin compounds. Not a biofouling inhibitor.

On the other hand, as prior arts similar to the phenylisothiocyanates of the present invention, Japanese Patent Application Laid-Open No. H11-110550, European Patent Publication No. Patent Publication No. 304042, European Patent Publication No. 282452 and German Patent Publication No.38001395 use as intermediates of insecticides and acaricides. W

Three

A manufacturing method is disclosed.

 However, there is no description of the use of the compounds described in the above publications as industrial antibacterial and antifungal agents, algicides and biofouling inhibitors.

Disclosure of the invention

 The present inventors have conducted intensive studies in order to solve the above-mentioned problems, and as a result, phenylisothiocyanates have high safety and exhibit a wide spectrum at a low dose from the viewpoint of preventing environmental pollution. The present inventors have found that they are highly practical industrial antibacterial and antifungal agents, algicides and biofouling inhibitors, and completed the present invention.

 That is, the present invention provides a compound represented by the following general formula (1):

(Wherein, X, Y and Z each independently represent an alkyl group having 15 carbon atoms (the alkyl group may be optionally substituted by a fluorine atom); An alkoxy group (the alkoxy group may be optionally substituted with a fluorine atom), an alkoxycarbonyl group having 2 to 6 carbon atoms, a halogen atom, a nitro group, a hydroxyl group or a hydroxyl group, and G is an oxygen atom , Io atoms, sulfinyl groups, sulfonyl groups or N-R (R is a hydrogen atom, an alkyl group having 115 carbon atoms, an alkenyl group having 2-6 carbon atoms or an alkynyl group having 2-6 carbon atoms. J and k each independently represent an integer of 0 to 5, j + k is always 5 or less,

1 represents an integer from 0 to 4. The present invention relates to industrial antibacterial and antifungal agents, algicides and biofouling inhibitors characterized by containing phenylisothiocyanates represented by the following formula:

 The compounds used in the present invention are not described in the above-mentioned regulatory law, and in each of the above publications, the phenylisothiocyanates of the present invention contain industrial antibacterial and antifungal agents, algicides and biofouling prevention. There is no description that it is effective as an agent.

 Each substituent represented by the general formula (1) will be specifically described.

In this specification, "n" is normal, "i" is iso, and "s" is secondary. , “C” means cyclo, “t” means tertiary, and “neo” means neo. Examples of the alkyl group having 1 to 5 carbon atoms include methyl, ethyl, n-propyl, i-propyl, c-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, and 2-pentyl , 3-pentyl, i-pentyl, neo-pentyl, t-pentyl, 1-methyl-c-propyl, 2-methyl-c-propyl, c-butyl, c-pentyl and the like.

 Examples of the alkoxy group having 1 to 5 carbon atoms include methoxy, ethoxy, n-propoxy, i-propoxy, c-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, n-pentoxy , 2-pentoxy, 3-pentoxy, i-pentoxy, neo-pentoxy, t-pentoxy, 1-methyl-c-propoxy, 2-methyl-c-propoxy, c-butoxy, c-pentoxy and the like.

 Examples of the alkoxycarbonyl group having 2 to 6 carbon atoms include methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, i-propoxycarbonyl, n-butoxycarbonyl, i-butoxycarbonyl, s-butoxycarbonyl, and t-butoxycarbonyl. , N-pentoxycarbonyl, 2-pentoxycarbonyl, 3-pentoxycarbonyl, i-pentoxycarponyl, neo-pentoxycarponyl, t-pentoxycarponyl, c-propoxyl-ponyl, 1-methyl-c-propoxyl Luponyl, 2-methyl-c-propoxycarbonyl, c-butoxycarbonyl, c-pentoxycarbonyl and the like.

 Halogen atoms include fluorine, chlorine, bromine and iodine.

Examples of the alkenyl group having 2 to 6 carbon atoms include ethenyl, 1-propenyl, 2-propenyl, 1-methylvinyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-ethylvinyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1,2-dimethyl-1-propenyl, 1 , 2-Dimethyl-1-propenyl, 1-ethyl-1-1-propyl, 1-ethyl-2-propenyl, 1_methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-1-butyl Phenyl, 1-i-propylvinyl, 2,4-pentyl genyl, 1-hexenyl, 2 W

Five

Examples include 1-hexenyl, 3-hexenyl, 4-1-hexenyl, 5-hexenyl, 2,4-hexagenyl, 1-methyl-1-pentenyl and the like.

 Examples of the alkynyl group having 2 to 6 carbon atoms include ethynyl, 1-propynyl, 2-propiel, 1-butynyl, 2-butynyl, 3-butynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1 Examples include monohexynyl, 2-hexynyl, 3-hexynyl, 4-hexyl, and 5-hexynyl.

BRIEF DESCRIPTION OF THE FIGURES

 FIG. 1 shows the antifouling effect of Compound 1 (the surface of the test plate 120 days after the application of 35 mg of Compound 1 and immersion in the sea).

 Attachment of compound 1 to the compound 1 application area (slightly below the center of the figure) is not observed.

 In contrast, a large number of fusippo and the like are attached to the peripheral area where no coating is performed.

BEST MODE FOR CARRYING OUT THE INVENTION

 The industrial antibacterial agent, drag agent, algicide and biofouling inhibitor of the present invention may contain phenylisothiocyanates represented by the general formula (1) as an active ingredient. Preferred compounds contained in the active ingredients of the industrial antibacterial and antifungal agents, algicides and biofouling inhibitors of the present invention are listed in Tables 1, 2 and 3 below. The compounds used are not limited to these.

 However, the symbols in the table have the following meanings.

Me: methyl group, Et: ethyl group, Pr-n: normal propyl group, Pr-i: isopropyl group, Bu-n: normal butyl group, Pen-n: normal pentyl group.

Table 1

 A ring B ring Α ring 環 ring

Q4

A ring BA ring B ring

 A ring B A ring B ring

表続き

Table continuation

Substituent on ring A (Xj and _Yk ) Substituent on ring B (I) position 3 position 4 position 5 position 6 position 3 'position 4' position 5 'position 6' position

H H H H H H H H H H

 Me H H H H H H H H H

H Me H H H H H H H H

H H Me H H H H H H

Me Me H H H H H H H H

Me H Me H H H H H H H

Me H H Me H H H H H

Me H H H Me H H H H

H Me Me H H H H H H H

H Me H Me H H H H H

H Me H H Me H H H H

Me Me Me H H H H H H H

Me Me H Me H H H H H H

Me Me H H Me H H H H

Me H Me Me H H H H H H

Me H Me H Me H H H H H

H Me Me Me H H H H H

E t H H H H H H H H

H P r-n H H H H H H H H

H H Bu-n H H H H H H

OMe H H H H H H H H H

H OMe H H H H H H H H

H H OMe H H H H H H H

OMe OMe H H H H H H H H

OMe H OMe H H H H H H H

OMe H H OMe H H H H H

OMe H H H OMe H H H H

H OMe OMe H H H H H H H

H OMe H OMe H H H H H

H OMe H H OMe H H H H

OE t H H H H H H H H H

H OP r-n H H H H H H H H

H H OBu-n H H H H H H H

OMe Me H H H H H H H H

Me H OMe H H H H H H H

OMe H H Me H H H H H

Me H H H OMe H H H H

H Me OMe H H H H H H

H Me H OMe HHHHH 1 table continued

Substituents on ring A (and Y _k ) substituents on ring B (1) z,

 m 412.5 5 6th position 5k 6 'position Π U e η H Me H H H H short 3 n Π H H H H H H u π short 3 π H H H H H H ττ

 η U n S 3 H H H H H u

11 η H H H H H H η υ ϋ

Η HHHHHH π n 1 1 " ₃ HHHHHH Π η nh HHHH a υυϋ π u

 Π H H H H H Π し U Uc ri H H H H H uu Γ η π Π π H H H H H υ π Γ π U

 Me n n H H H H H ττ

Ιυϋ L η Me Π H H H H H π Π UMe H H H H H H U Ui: η f

 Π n UMe H H H H

Γ π Π rl H H H H H η υ Γ Π n H H H H H η υ η Γ h Π H H H H Γ rl rl r?

 Γ H H H H

 Γ r Γ H H H H 1

 1 η Π rl n H H H H η υ 1 1 Π n H H H H η η Π 1 rl Π H H H H 1

 1 Π rl Π H H H H 1 1 π Γ 1 and n n H H H H

 υ

 Then I π n then 1 rl H H H H

 u U

 1 π n 11 1 u

 Π H H H

H C1 Cl H H H H H H

H C1 H Cl H H H H H

H C1 H H Cl H H H H

CI C1 H H Cl H H H H

CI C1 H Cl Cl H H H H

CI C1 Cl Cl Cl H H H H

Br Η H H H H H H H

H ΒΓ H H H H H H H H

H Η Br H H H H H H

H Η IHHHHHH Table continuation

Substituent on ring A (f ヽ

And Y _k ) a substituent on the B ring (1)

3 4th 5th 6th 3 '4th 5' 6 '

Me H H H H H H H

Me H C I H H H H H H H

U e H H F H H H H H H 1 H H H OMe H H H H n F C I H H H H H H H n C I F H H H H H H H

Π COOMe F H H H H H H H

N0 ₂ HHHHHHHH ri N0 ₂ HHHHHHH

Π H N0 ₂ HHHHHH

Un H H H H H H H H u n OH H H H H H H H rl H OH H H H H H H H

 H H H H H H H H

Π COOH H H H H H H H

 n H COOH HHHHHH nu HHHH Me HHH ri HH Π HH Me HH ri HH ri HHH Me H nu HH n HHHH Me n HH n HE t HHH un HH Π Π HP rn HH rl HH n Π HH Bu-n H rl Π H n HHHH Pen-n n HH n H OMe HHH il HH n HH OMe HH nn H n HHH OMe H n Π Π HHHH OMe n H rl un OE t HHH un HH unu HH OP rn HH n HH Π rl HH OBu-n H

H H H H H H H H OPen-n

HHHHH CF ₃ HHH

HHHHHH CF ₃ HH

HHHHHHH CF ₃ H

HHHHHHHH CF ₃

HHHHH 0CF ₃ HHH

HHHHHHH 0CF ₃ H

HHHHH COOMe HHH 1 table continued

Substituent on ring A (and Y _k ) Substituent on ring B (1 \)

 '

 2 3rd 4th 5 6th 3rd 4 \ 5th 6 '

H H H H H H COOE t H H

H H H H H H H COOP r.-n H

H H H H H H H H C00Bu-n

H H H H H F H H H

H H H H H H C I H H

Π H H H H H H B r H

H H H H H H H H I

HHHHH N0 ₂ HHH

HHHHHH N0 ₂ HH

H H H H H H H OH H

H H H H H H H H COOH

 Me H H H H Me H H H

H OMe H H H H Me H H

HH CF ₃ HHHH Me H

0CF ₃ HHHHHHH Me

COOMe H H H H Me H H H

H then 1 HHHH Me HH n Π N0 ₂ HHHH Me H

UH H H H H H H H Me u

 n shi UUH Π ri rl Me H H H

Me H H H H OH H H H

H OMe H H H H COOH H H

HH CF ₃ HHHH 0CF ₃ H

0CF ₃ HHHHHHHF

COOMe H H H H C I H H H

HCIHHHH N0 ₂ HH

HH N0 ₂ HHHH COOMe H

OH H H H H H H H OMe

H COOH HHH CF ₃ HHH 91,0

mvamv

mavamv

 ^ v a ^ v

(HO

 Halla s¾

ΠLPP0 / 66d £ / lDd 6 £ 0l / 00 OW Table continuation

Substituent on ring A (Xj and _Yk ) Substituent on ring B (I)

A r (2 I ^ f

0 lAL Ό 'Z- f. 4 1 A 5 6th

Π U nu fl nn HH

 Up U u

 Π n n u

n 11 HH

 C n U n Mc n n n H H

1YJC n u n Π mc n n H H

 Up u

 lYi C Ώ

 Π Π rl n H H

1 U U Π Mp

 Π n rl H H

11 IVI u Π u il e Π n H H

 rl Π n H H

Mp Mp W n u

 Π Π n n H

1Y1 c 1YIC n 11

 Π e u

 n Π H H

M P u XI M mou MC Π rl Π H H

MP u n Up rl me u

 n rl H H

11 u m «c n h ri H H

F † n Π U u IT

 n II Π n u H H

11 P r-n u u

 Π n n n rl H

1 Π u

 D 1 π u

 U 1 n u

Π n Π H

 11 n u u

 Π fl n Π n H

H 11 H IU c u u

 Π n u

 Π n u

 Π

OMe u LI u u

Π nnn rl H

 OMe H P 11 U n n n u rl Π rl

H OMe U n U n π n n Π ri

H OMe H 1 u u

 n u

 Π n Π ti

H OMe H H OMe H H H H

OE t H H H H H H H H H

H H H H H H H H

H H OBu-n H H H H H H H

OMe Me H H H H H H H H

Me H OMe H H H H H H H

OMe H H Me H H H H H

Me H H H OMe H H H H

H Me OMe H H H H H H

H Me H OMe HHHHH 2 tables continued

Substituents on ring A (Xi and _Yk ) Substituents on ring B (I,)

9 A Ό Ί Δ 4 Lb ¼ fa iL n UiHc u n n Π n n rl

 U n u u

 n n u n u Π n Π Π n u u

 Then n n u

 n n rl Π ri n u u

 n u

 Π n Π n H Π

 u

length n u n u

 Π n rl n n Π u

 n length u n u

 Π n n Π n rl

H π υ u u

 U u

 Π rl Π rl rl u π u u u U

 n Π n rl Π rn rnOF £ 1 u u

 Π n n u

 n Π Π n fOOF f n u n u u u

 n Π u

 rl Π n Π u Π u u

 Π n n rl rl

H 11 π Π Π u n u

 Π u

 Π rl

 ΓΠΠΡρη-η Ll u u

 Π u

nn Π Π

 u u

 n u n u

 n n n rl

COOMe U u u tr

 Ulwc π u

 n n n r nnF † H n U Π Urac u

 fl Π n Π

R U u u

 n n u u

 Π n Π Π Π n u u n U u

 n n Π Π Π

F r u n u u

 n XI rl n n

V r V u

 Γ u

 XI n Π n

F r u u n

 Γ fl n n ri 1 11 u n u u u rr

 n u

 Π n Π n

H Γ 1 Π Π u n u u

 n Π n

H H n n II u tr

 Π n Π ci ci I nT u u

 n Π tr

 fl Π

CI H H u n u u u

 Π n Π

CI H n u fl u

 Π rl Π

CI H H H r 1 Π n u u

 n Π n n then i U u

 Π rl n n rl rl

H CI H CI H H H H H

H CI H H CI H H H H

CI CI H H CI H H H H

CI CI H CI CI H H H H H

CI CI CI CI CI H H H H

 Br H H H H H H H H H

H Br H H H H H H H

H H Br H H H H H H H

HHIHHHHHH Table continuation

Substituent on ring A (Xi and Y _k ) Substituent on ring B ()

 Q, ^ r-. O I-Ό. Έ, r,

 Δ 0 Z. u n π u Π u u

 n ri rl Π

Up u r 1 1J

 Γ1shi 1 11 n n n Π rl uiviu u Π u Π Γ u

 n u y

 n ri n n

C then 1 I Π u n n u

UMe ϋ n rl H

 u π then r n u

 n n Π n H u π G Γ IT u

 n n Π Π n wn u Π u n u Π u n n n 11 rl u n wn u n Π u n u

 il n n rl

H u n wn Π u u n u n n ri Π

Uil Π n u n u Π u n u u

 Π n Π rl

OH n n u u n u n Π u n Π

U n u Π u n u

 n u Π n n n u n u tl n 0 u rl n

P and OOH n u n u n u n n Π n

 H n υ n u n Up u

 n u

 n n

P nununu Π Mc n

 H n n n u E t H n n Π

H H 1 1 H n u n Π P r-n u

 n n

 Π

H H il u n u n H D U rl

HHL Hl π n Π u H u fl Pen ~ n

 H H u U n OMe u n Π

H H n u n H Π u

H H H li u n H u n

 H H H OF t H u Π u

 Π

 u n u n n u

 n n Π n H

H H H H H H H OBu-n H

H H H H H H H H OPen-n

HHHHH CF ₃ HHH

HHHHHH CF ₃ HH

HHHHHHH CF ₃ H

HHHHHHHH CF ₃

HHHHH 0CF ₃ HHH

HHHHHHH 0CF ₃ H

HHHHH COOMe HHH 2 tables continued

Substituent on ring A (and Y _k ) Substituent on ring B (Z,)

2nd 3rd 4th,

 5 6th 3rd 4k 5k 6 '

H H H H H H COOE t H H

H H H H H H H COOP r- -n H

H H H H H H H H COOBu-n

H H H H H F H H H

H H H H H H C I H H

H H H H H H H Br H

H H H H H H H H I

HHHHH N0 ₂ HHH

HHHHHH N0 ₂ HH

H H H H H H H OH H

H H H H H H H H COOH

 Me H H H H Me H H H ri ◦Me H H H H Me H H

HH CF ₃ HHHH Me H

0CF ₃ HHHHHHH Me

CUUMe H H H H Me H H H

Π L I H H H H Me H H

HH N0 ₂ HHHH Me H

UH H H H H H H H Me

H COOH H H H Me H H H

Me H H H H OH H H H

H OMe H H H H COOH H H

HH CF ₃ HHHH 0CF ₃ H

0CF ₃ HHHHHHHF

COOMe H H H H C I H H H

HCIHHHH N0 ₂ HH

HH N0 ₂ HHHH COOMe H

OH H H H H H H H OMe

H COOH HHH CF ₃ HHH Table 3

 Α Ring Β Ring A Ring B Ring

 Ring B Ring Ring

Ring Ring Ring A Ring B

Ring A Ring B Ring B Ring Table continuation

Substituent on ring A (and Y _k ) Substituent on ring B (I)

Ό] \ L 5th 6th υ π u u

 Π n TT TT

 Π n TJ TT TT

n HHH

 u π Up u

 mc fl TT TJ

 Π Π ri H H H π υ U Π Mc u n TT TJ TT

 n rl TT

 H H H

 u u

 mc Π n n rl Π H H

Up U Up u

 Π n TT TT

 n TJ TT

rl HH

 Up u u

 Π n u

 π e n H H H

U u

 Π Mc n u

 n u

 n n H H u n u n Me u

 n Π H H H u n Up n Π n

 Π TT

 Me H H H H

Up Up

 c TT

 rl Π Π H H H

IHc Π e Π rl Π H H

Up Up u n n u

 Me H H H p u

 Π Me Me n H Π H H

Up u n u n Me H H H H

U n Mp iwe TI

 Me n rl H H H

Ώ i u u u

 I Π Π a rl ri Π H H u u

 Π p J r— 11 u

 n n TT

 Π Π n H H u U T u

 Π Π DinU n 11 TT TJ TJ TT

 n n rl H H

OMP u u u u

 Π Π n rl n Π H H

U

 n OMP u

 n n TT TJ TJ TT TT

 Π Π ri H H u n U

 Π TT

UIW c II n TT TJ TT

n rl HH

 OMP £ 1 U u

 n UMc n TT

 n rl Π H

T 1i1 u n u n TT

 n Π Π Π

H OMP Um u n u n rl n Π n

11 OMP U

 11 O UMIYIP u TJ

 c TJ

 n TT TT n rl rl n

H OMe H H OMe H H H H

OE t H H H H H H H H H

H OP r-n H H H H H H H H

H H OBu-n H H H H H H H

OMe Me H H H H H H H H

Me H OMe H H H H H H H

OMe H H Me H H H H H

Me H H H OMe H H H H

H Me OMe H H H H H H

H Me H OMe HHHHH 3 Table a

Substituent on ring A (and Y _k ) Substituent on ring B (1)

9 i ^ r o / J

 1Δ 4 013. D position ό position * _

 Position 5 ilL 6 Ή. U

 π u e Π n Me H H H H

 π rl Π H H H H H π Π Π Π H H H H η n u

 n n H H H H u u n Π n n

 Π H H H H

 υ η U rl rl n H H H H

11 n _{3 3} rl HHHH U UUMc rl Π uu

 Π Π Π H H H

 U ίΐ Π UUc I Π u

 n Π H H H H υ η u n LUUC I n Π rl H H H

 u

 uurr U n u

 Π Π n n H H

U fl then UUI3U H n Π n n H H H

U n u n s UUr CI1 11 n r ul rl H H H s G Π Π n ti H H H s UUE Ine rl n Π H H H

ΓUΠl / Μ u

 IWΡC rl n U e Π n H H H u

UUtl I n Π Π UMe H H H H Γ rl n u

 Π H H H H

 υ η Γ n n rl n H H υ π n u

 r u

 Π Π n H H H

C Γ v

 r u n Γ r n Π H H

Γ Γ D

 r Γ r n n H H i Π u u u u n u

 Π Π Π H H

 υ π r then] 1 u u

 n n n Π H

U π u n u

 1 n u n n n H H 1 1 u u u

 Π u

 n n n 11 Π H 1 X u

 ΠJ r 1 u

 1 1 n n n u n n H u n u fl 1 1 i u

 a rl n rl H π n H n u u n u

 1 u n n rl Π

Η Cl Cl H H H H H H

Η Cl H Cl H H H H H

Η Cl H H Cl H H H H

C1 Cl H H Cl H H H H H

C1 Cl H Cl Cl H H H H

C1 Cl Cl Cl Cl H H H H

ΒΓ H H H H H H H H

Η Br H H H H H H H

Η H Br H H H H H H

Η HIHHHHHH 3 tables continued

Substituent on ring A (and Y _k ) Substituent on ring B (Z,)

 u

 Γ Me n Π n H H H H

Me ri u

 1 n H H H H H H

U e n u Π n H H H H then 1 rl n nil

 Π UMe H H H H n u

1 1 ri Π HHHH rl 1 1 Γ rl HHHHH

 u rl rl u

INU ₂ nn HHH ft JU ₂ n rl rl rl HH Π n Ι ϋ ₂ rl rl HHHH

Un n n rl n u ri H H H n Un n Π Π H H H H n Π Un rl H H H H H

UΠUΙUΙ n Π n Π H H H n Γ UΓUΙHΤ n u

 Π rl Π H H H n し U UUH Π Π ri ri H H u rl Π n n u

Π Me HHH n Π ri Π n H Me HH

 u n n n n H H H u n u n

 n n u

 Π Π rl r r-n F r-n H

Π u u

nn Π n Π r Γ-1 r r- i H

 u u u

 Π n n Π n rl Pen-n Pen-n n u u u u

 Π n Π n n Π D t n n u

 n fl u u

Π n ri nrr ^_ n ri rl ununu Π π uunn rl till n rl nununu Π nnn Pen ^_ n Π rl u 11 unuu

 Π u

 n n uiwe n n ri u n u n n u u u

 n u

 n 11 UMe Π n

H H H H H H OMe OMe H

H H H H H H OP r-n OP r-n H

H H H H H H OE t H H

H H H H H H OP r-n H H

H H H H H H OBu-n H H

H H H H H H OPen-n H H

HHHHH CF ₃ HHH

HHHHHH CF ₃ HH

HHHHHH Me CF ₃ H 3 tables continued

Substituent on ring A (, Substituent on ring (Ζι ヽ ό ό 1S 4 position Ό L 3 position 4 U 5 'position 6 iL

 π Η η π COOMe H H H π τ ητ ττ ττ

 Π π π ττ H COOEt H H π υ η ττ

 π ττ υ η COOPr- -n H H H u ττ

 π Π Η ττ

Π Π H C00Bu-n HH

 υ η η Η η π υ η H CI H H η ττ

 Η ττ ττ ττ

 Π π Br H H H ττ τ ητ

Π Η τ ητ π ττ HIHH

 τ ητ ττ ττ

 Τ τ ητ τ ητ H CI CI H τ ητ ττ ττ

 Π τ τ ητ η ττ

 F F F F

Π Η τ τ ητ

Π CI CI CI CI

η Π π 11 π OH HHH

 Me υ π π τ ττ

 η Π H Me Me H Π η η η H Me Me H π υ π u π

 3 π ί1 Me H H ti τ

 3 η ητ η υ η η H Et Pr-n rl τ ττ

Π η υ π υ

η rl Fr-n Pr-n Π

 u u

 π υ υ

 Π η η rl Pen-n H H η

 Uil η τ ητ u π υ π Me Me H n

U π π

 UUtl π π υ η Me Me H Me

Me Η Η U η υ η H OH H u

 Π

Η OMe Η π u η H C00H H 11

0CF ₃ Η Η Η Η HFHH

COOMe Η Η Η Η H CI H H

Η C1 Η Η Η H N0 ₂ HH

Η Η Ν0 ₂ Η Η H COOMe HH

O Η Η Η Η H OMe Me H

The Η C00H Η Η Η CF ₃ HHH more preferred compounds include a compound shown below (hereinafter In the structural formula shown below, the bond position of NCS may be any of ortho, meta, and para. ).

本発明のフエ二ルイソチオシアナ一ト類は、 日本国特開平 4— 2 1 1 0 5 0号 公報、 欧州公開特許公報 4 8 1 9 2 1号、 欧州公開特許公報 3 0 4 4 0 2号、 欧 州公開特許公報 2 8 2 4 5 2号、 ドイツ公開特許公報 3 8 0 1 3 9 5号等を参考 に、 通常知られた方法により製造できる。

The phenylisothiocyanates of the present invention are disclosed in Japanese Patent Application Laid-Open No. 4-210110, European Patent Application Publication No. 481,921, European Patent Application Publication No. It can be produced by a generally known method with reference to European Patent Publication No. 282425, German Patent Publication No. 3801395, and the like.

The phenylisothiocyanates used as the active ingredient in the present invention are solely When the industrial antibacterial agent, antifungal agent, algicide and biofouling inhibitor of the present invention are used, if necessary, other known industrial antibacterial and antifungal agents, algicidal agents may be used. An agent or a biofouling inhibitor can be further included and used as a mixture.

 The typical examples of the compounds used in combination are listed below, but are not limited thereto.

 N-decyl-N-isononyl-N, N-dimethylammonium chloride, poly [1,2-dienyl (dimethylimino) -1,1,2-ethanediyl (dimethylimino) -1,2, -dimethyl] Quaternary ammonium compounds such as benzyl dichloride;

 Aldehyde compounds such as glutaraldehyde;

 1,2-Jib mouth 2,4,1-dishanbutane, 2,2-Jib mouth 3,2-tripropionamide, 2-bromo-2-dipropanediol, 5-bromo-5-nitro-1,3 —Halogenated compounds such as dioxane;

 N-halogen compounds such as bromochlorodimethylhydantoin and trichloromouth isocyanuric acid;

 Guanide-based compounds such as poly (hexamethylene biguanide) hydrochloride; dimethyldithi, zinc rubamate, getylditi, zinc rubamate, dibutyruditi, zinc rubamate, zinc rubirmate, zinc bismuth, ethylene bisdiene Zinc thiocarbamate, Zinc propylene bisdithiocarbamate, Bis (dimethyldithiol rubamoyl) Ethylene bisdithiol rubbamate, Ethylene bis thiocyanate Manganese rubbamate, Dimethyl dithiate nickle rubinate Nickel, Dibutyl lutetite rubaminic acid Dithiocarbamate-based metal compounds such as nickel, dimethyldithiol copper rubamate, and dimethyldithiol rubamate iron;

 Copper-based metal powders such as copper powder and copper-nickel alloy powder;

 Copper compounds such as cuprous oxide, cuprous thiocyanate (copper rhodan), basic copper carbonate, copper pyrophosphate, copper naphthenate, copper abietic acid, copper oxyquinoline;

 Pyrithione metal compounds such as 2-pyridinethiol zinc oxide and 2-pyridinethiol copper salt;

Tetramethylthiuram disulphide, tetraethylthiuram disulphide, Tetra-n-propylthiuram disulfide, tetraisopropylthiuram disulfide, tetra-n-butylthiuram disulfide, tetraisobutyl thiuram disulfide, N, N'-Ethylenebisthiocarbamoylsulfide, N , N'-Propylenebisthiocarbamoylsulfide, N, N'-Tyuram-based compounds such as butylenebisthiocarbamoyl sulfide;

 2- (4-thiazolyl) benzimidazole, 2— (methoxycarponylamino) benzimidazole, methyl-11- (ω-cyanopentylcarbamoyl) 1-2-benzimidazole, 2-mercaptobenzimidazole zinc, Benzimidazole compounds such as 2-thiocyanomethylthiobenzimidazole;

 2-mercaptobenzothiazole, 2- (thiocyanomethylthio) benzothiazole, 2- (thiocyanomethylsulfonyl) benzothiazol, 2-thiocyanoethylthio-14-chlorobenzoicazole, 2-thiocyanopropyl Benzothiazole compounds such as thio-5,7-dichlorobenzothiazole and 2-thiocyanomethylthio-1,4,5,6,7-tetrachlorobenzothiazole;

 Ditolyl such as tetrafluoroisophthalonitrile, tetrachloroisophthalonitrile, 5-chloro-1,2,4-difluoro-6-methoxyisophthalonitrile, 2,4,5,6-tetrachloroisophthalonitrile System compound;

 5-Chloro-2-methyl-1-3-isothiazolone, 5-Chloro-2-η-decyl-3-isothiazolone, 4,5-dichloro-2- (4-cyclobenzyl) -1,3-isothiazolone, 4,5-dichloro 1 2— (4 monochlorophenyl) 1 3 —isothiazolone, 4, 5 —dichloro-2-η —hexyl 3 —isothiazolone, 4, 5 —trimethylene 1 2—methyl-1 3—isothiazolone, 4-methyl-5— Chloro-2-η-octyl-1-3-isothiazolone, 2-methyl-3-isothiazolone, 4,5-dichloro-2-η-octyl-1-monoisothiazoline-3—one, 2-η—year octyl-4—isothiazoline-1-3 — Isothiazoline-based compounds such as on, 1,2-benzoisothiazolin-3-one;

1- [2- (2,4-dichlorophenyl) -1-4-propyl-1,3-dioxolanyl-2-methyl] -1- 1-1,2,4—triazole, 4,4-dimethyl— 2 (1,2,4—triazole—1—yl) 1 1— (4 1 trifluoromethyl-2-chloro Triazole-based compounds such as 1-phenyl-1-pentene-2-ol;

2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine, 2,3,6-trichloro-4-monopropylsulfonyl pyridine, 2,6-dichloro-3,5—dicyano-4-phenylphenylpyridine A pyridine compound;

 2,4-dichloro-1-6- (o-chloroanilino) -1s-triazine, 2-chloro-4-aminomethyl 6-isopropylamino-1-s-triazine, 2-chloro-, 6-bis (ethylamino) s — triazine, 2-chloro-1,4-bis (isopropylamino) 1 s — triazine, 2-methylthio-1,4,6 —bis (ethylamino) 1 s — triazine, 2-methylthio-4-ethylamino-6 —Isopropylamino-s-triazine, 2-methylthio-4-t-butylamino-6-cyclopropylamino-s—triazine-based compound such as triazine;

 N- (3,4-dichlorophenyl) -1-N, monomethylurea, 3- (3,4-dichlorophenyl) 1-1,1-dimethylurea, 3- (3,4-dichlorophenyl) 1-1-methyl Toxic 1 monomethylurea, 1 — (a, a'-dimethylpentyl) — 3 —methyl-3-phenylurea, 1 — (2 —methylcyclohexyl) — 3-phenylurine, 3 — (4-isopropyl Phenyl) — 1, 1 — urea compounds such as dimethyl urea;

 Quinone compounds such as 2,3-dichloro-1,4-naphthoquinone, 2-amino-1,3-chloro-1,4-naphthoquinone, 2,3-dicyanone 1,4-dithiaanthraquinone;

N-trichloromethylthiotetrahydrophthalimide, N-1,1,2,2-tetrachloroethylthiotetrahydrophthalimide, N-trichloromethylthiophenylimide, N-fluorodichloromethylthiophthalimide, N , N-Dimethyl-1-N'-phenyl-N '-(fluorodichloromethylthio) sulfamide, trichloromethylthiomethanesulfone-p-chloroanilide, N— (1,1,2,2, -tetrachloro- 2-Fluoroethylthio) methanesulfonyl anilide, N-Fluorodichloromethylthio-1-N-3-chlorobenzene Ν'-Dimethylurea, Ν-Fluorodichloromethylthio-1-, 3,4 —Dichlorophenyl N'-methylurea, Ν-fluorodichloromethylthio-1-trisulfonyl Ν—methylamine Any N-octaalkylthio compound;

 N-Phenethyldichloromaleimide, N-benzyldichloromaleimide, N— (2-chlorophenyl) maleide, N— (4-Fluorophenyl) maleimide, N- (3,5-dichlorophne) Enyl) maleimide, N— (2,4,6-trichloro mouth phenyl) maleimide, N—4-tolyl maleimide, N—2,4-xylylmaleimide, 2,3-dichloro-N— (2 ', 6 '-Jetylphenyl) maleimide, 2,3-Dichloro-N- (2'-methyl-6'-Jetylphenyl) maleide, 2,3-Dichloromethyl N- (2', 6'-Dimethylphenyl) maleimide Maleimide compounds such as, 2,3-dichloro-N- (2 ', 4', 6'-trimethylphenyl) maleimide;

 3,5-dimethyl-tetrahydro-1,3,5,2 (H) thiadiazin-2-one, 3,3'-ethylenebis (tetrahydro-4,6-dimethyl-2H-1, 3,5-thiadiazine-1 2 Thiadiazine-based compounds such as —one, 3,5-dimethyl-2-thiotetrahydro-1,3,5-thiadiazine, 3,5-dibenzyltetrahydro-1,3,5-thiadiazine-12-thione;

 Methyl thiocyanate, chloromethyl thiocyanate, thiocyanate butyl, methylene bisthiosinate, chloromethylene bis thiosinate, ethylene bis thiosinate, ethyl ethylene bis thiosinate, isoporyl thiocyanate, methyl isothiocyanate Thiocyanates such as carboxylate, arylisothiosinate, phenylisothionate, and benzylisothiocyanate; alkylphenol compounds such as caprylphenol and nonylphenol; tris (octylphenyl) phosphite, tris (nonylphenyl) Alkyl phenyl phosphite compounds such as phosphite, tris (dinonylphenyl) phosphite, and tris (mono- and di-mixed nonylphenyl) phosphite;

 Alkyl phenyl phosphite compounds such as tris (octyl phenyl) phosphate, tris (nonyl phenyl) phosphate, tris (dinonyl phenyl) phosphate, tris (mono, di-mixed nonyl phenyl) phosphate;

O—3—Iodo 2-propynyl—N—butylcarbamate, N—3—Iodo—2-propynyl—0—butylcarbamate, 2,3,3-tolyot Iodine compounds such as alcohol and jodomethylparatolylsulfone;

 n—a polysulfide compound such as octylchloromethyl disulfide; a boron compound such as pyridinetriphenylporan.

 Bismuth compounds such as phenyl (bispyridyl) bismuth dichloride; and the phenylisothiocyanates used as the active ingredient in the present invention are composed of a single compound or a mixture of several kinds of phenylisothiocyanates. Is also good.

 The phenylisothiocyanates used as the active ingredient in the present invention may be added alone to the system for the use described above, or as a mixture comprising other active ingredients and, if necessary, a suitable carrier or solvent. Alternatively, it may be formulated as an aqueous emulsion or dispersion.

 The formulation of the industrial antibacterial and antifungal agent, the algicide and the biofouling inhibitor of the present invention can be generally used in the field of industrial antibacterial and antifungal agent and the algicide as an active ingredient in the present invention. The phenylisothiocyanates are mixed with suitable carriers and auxiliaries, such as surfactants, binders, stabilizers, etc., and mixed, and wettable powders, emulsions, sols (flowables) and It is used after being formulated into other appropriate dosage forms.

 When preparing these preparations, there is no upper limit on the concentration of the active ingredient phenylisothiocyanate as long as wettable powders, emulsions, solutions, sols and other appropriate preparations can be prepared. However, they are incorporated in a proportion of 190% by weight, preferably 3 to 40% by weight, based on the weight of these preparations.

 As a carrier that can be used, any solid or liquid can be used as long as it is commonly used for industrial antibacterial and antifungal agents and algicides, and it is not limited to a specific one.

 Examples of solid carriers include mineral powders such as lime ore, bentonite, clay, montmorillonite, diatomaceous earth, mica, vermiculite, gypsum, calcium carbonate, phosphate lime, white limestone, slaked lime, silica sand, ammonium sulfate. , Urea, etc., or vegetable powders, for example, soybean powder, starch, crystalline cellulose, etc., alumina, silicates, sugar polymers, highly dispersible silicic acid, waxes and the like.

Examples of liquid carriers include water, alcohols such as methyl alcohol, ethyl Aromatic hydrocarbons such as alcohol, n-propyl alcohol, isopropyl alcohol, ethylene glycol, benzyl alcohol, etc., for example, benzene, toluene, xylene, ethylbenzene, benzene, cumene, methylnaphthylene, and halogenated hydrocarbons , Such as chloroform, dichloromethane, ethylene dichloride, etc., ethers, such as ethyl ether, dioxane, tetrahydrofuran, etc., Ketones, such as acetone, methyl ethyl ketone, cyclohexanone, methyl isobutyl ketone, etc., esters , For example, ethyl acetate, butyl acetate, ethylene glycol acetate, amyl acetate, etc., nitriles, for example, acetonitrile, propionitrile, acrylonitrile, etc., sulfoxides, for example, Alcohol ethers such as methyl sulfoxide, etc., for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, etc., amines, for example, triethyl amine, etc., and aliphatic and alicyclic hydrocarbons, for example, n-hexane , Cyclohexane, etc., as well as industrial gasoline (petroleum ether, solvent naphtha, etc.) and petroleum fractions (paraffins, kerosene, gas oil, etc.).

 In the case of preparations such as emulsions, wettable powders, and sols (flowables), surfactants are incorporated for the purpose of emulsification, dispersion, solubilization, wetting, foaming, spreading, and the like. Examples of such a surfactant include the following, but are not limited thereto.

 Examples of nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene alkyl ester, polyoxyethylene sorbin alkyl ester, and sorbitan alkyl ester.

 Examples of the anionic surfactant include alkyl benzene sulfonate, alkyl sulfosuccinate, alkyl sulfate, polyoxyethylene alkyl sulfate, aryl sulfone and lauryl sulfate. Examples of the cationic surfactant include alkylamines (such as laurylamine, stearyltrimethylammonium chloride and alkyldimethylbenzylammonium chloride).

Examples of amphoteric surfactants include carboxylic acid (bein-in type) sulfate. W 0

28

 In addition to these, polyvinyl alcohol (PVA), carboxymethyl cellulose (CMC), gum arabic, polyvinyl acetate, gelatin, casein, sodium alginate, tragacanth gum, guar gum, xanthan gum and hydroxypropyl cellulose Thickeners and various auxiliaries can be included. Further, if necessary, a suitable amount of a stabilizer such as an antioxidant or an ultraviolet absorber can be added.

 The industrial antibacterial and antifungal agents and algicides of the present invention containing phenylisothiocyanates as an active ingredient can be used for the following applications.

 Waterborne paints, adhesives, latex, emulsion products such as acrylics, starch, pigments, slurry products such as calcium carbonate, and control of the growth of bacteria, fungi and algae in joint cement; building materials (building materials, civil engineering materials, etc.) Preservation of wood; Preservation of cutting oil; Prevention of mold of surfactants; Sterilization and prevention of slime formation in cooling towers, pulp and paper mills in factory manufacturing facilities and building air conditioning; Spraying on textiles, fabrics and leather Antibacterial or anti-fungal treatment by immersion treatment; Bacteria generated when paint film, especially paint film of exterior paint, is exposed to the weather; Protection from attack by fungi and algae; Vinyl chloride, polyurethane, polyethylene, polypropylene Interior and exterior materials (residential, medical facilities, etc.) made of resin such as silicone, modified silicon, nylon, epoxy, etc. ), Building materials (building materials, civil engineering materials, etc.), antibacterial and antifungal and algicidal products for home appliances, household goods, sports equipment, etc .; protection of slime deposition on sugar cane and sugar beet sugar manufacturing equipment; Prevention of accumulation and accumulation of microorganisms in shear and scrubber systems and industrial freshwater supply systems; Preservation of sanitary conditions in food factories; Deodorization and sterilization of sewage treatment plants, human waste treatment plants, etc. when washing production facilities; Oil field cutting oil Prevention of microbial contamination and sedimentation in muddy water and secondary oil recovery processes; Prevention of bacterial and fungal growth in paper coatings and coatings; Prevention of microbial contamination in cosmetics and toiletry products; Algal growth on pools, etc. Control; Prevent microbial contamination of agricultural formulations, electrodeposition systems, diagnostic and pharmaceutical products, medical equipment, etc .; Prevent microbial accumulation in photographic processing.

The formulated industrial antibacterial and antifungal agents and algicides of the present invention can be obtained by diluting various preparations as they are or by diluting them with water or an appropriate organic solvent, and then preparing them in various industrial raw materials or products. To the surface of various industrial raw materials and products. Including the method of fogging or the method of immersing various industrial raw materials and products in the diluent of the industrial antibacterial and antifungal agent and the algicide of the present invention, and the like, It can be used by various methods according to the use of antibacterial and antifungal agents and algicides, but is not limited to any particular method.

 Anti-biofouling agents containing phenylisothiocyanates as active ingredients include: fishing nets, ship bottoms, buoys and other submarine equipment, marine structures, condensers for thermal or nuclear power plants Shells such as blue mussels, fusippo, oysters, hide mouth mussels, hydra, selbra, sea squirts, mosquitoes, and evening reeds for underwater structures such as water intake channels for cooling water for heat exchangers in the chemical industry, facilities attached to dams, etc. It can also be used to prevent the adhesion of harmful aquatic organisms such as algae such as Aosa, Aonori and Shimidro.

 Formulations of the industrial antibacterial and antifungal agents, algicides and biofouling inhibitors of the present invention are outlined in the field of application of biofouling inhibitors.The phenylisothiocyanates used as active ingredients in the present invention are: It is prepared and used in the form of paints, solutions, emulsions and the like. For the preparation of these paints, solutions, emulsions and the like, general recipes usually used can be adopted.

 When the underwater biofouling inhibitor of the present invention is used in the form of an antifouling paint, for example, an active ingredient, phenylisothiocyanate, is mixed with a film-forming agent to prepare a paint, and When applied to marine structures, cooling water intake pipes, or underwater structures, it is possible to prevent adherent propagation of underwater organisms.

 As a coating film forming agent, oil varnish, synthetic resin, artificial rubber and the like are used.

 Further, a solvent, a pigment, or the like may be used as necessary.

 When preparing a paint, the concentration of the phenylisothiocyanate as an active ingredient has no upper limit as long as a coating film can be formed, but it is preferably 1 to 50% by weight, and more preferably 1 to 50% by weight based on the weight of the antifouling paint. It is blended at a ratio of 5 to 20% by weight.

When the underwater biofouling inhibitor of the present invention is used in the form of a solution, for example, a solution in which phenylisothiocyanate, which is an effective component, is dissolved in a solvent together with a film-forming agent is prepared, and aquaculture fishing net, By applying it to a fixed fishing net or the like, it is possible to prevent the adhesion and propagation of aquatic organisms. As the coating film forming agent, synthetic resin, artificial rubber, natural resin, etc. are used, and as the solvent, xylene, toluene, cumene, methylethyl ketone, methyl isobutyl ketone, acetate, etc. are used. .

 Further, if necessary, additives, such as a plasticizer, may be used. When preparing a solution, there is no upper limit to the concentration of the phenylisothiocyanate as an active ingredient as long as a solution can be formed, but 1 to 50% by weight, preferably 5 to 50% by weight, based on the weight of the solution. It is blended at a rate of 30%.

 When the water-based anti-fouling agent of the present invention is used in the form of an emulsion, a surfactant is usually added to a solution of phenylisothiocyanate as an active ingredient in accordance with a general method for preparing an emulsion. However, a desired emulsion can be prepared, and there is no particular limitation on the type of surfactant used.

 The prepared emulsion can be used by kneading it into raw materials such as aquaculture nets and fixed nets used in the ocean or water, for example, polymer resins and the like.

 When an emulsion is prepared, there is no upper limit to the concentration of the phenylisothiocyanate as an active ingredient as long as an emulsion can be formed, but it is 115% by weight, preferably 3% by weight, based on the weight of the emulsion. It is blended at a ratio of 30% by weight.

 Further, the above solution or emulsion of the present invention can also be used by adding to water, storage water, etc. in order to prevent adherent propagation of aquatic organisms in a cooling water intake pipe or a reservoir.

Example

 Hereinafter, the present invention will be described more specifically and in detail with reference to Examples using the compounds of the present invention. However, the present invention is not limited thereto.

Prescription example

Formulation examples when the phenylisothiocyanates of the present invention are used as industrial antibacterial and antifungal agents and algicides are shown below.The mixing ratio of active ingredients, the types of carriers and auxiliary agents, and the amounts added are as follows. It is not limited to these. Formulation Example 1 (emulsion)

 Ingredient

 Compound 5 of the present invention

 Dimethyl sulfoxide 8 5

 Methyl isobutyl ketone 5

 Solpole 8 0 0 A 5

 (Emulsifier manufactured by Toho Chemical Co., Ltd.)

0 0

 By mixing and dissolving the above, an emulsion containing 5% of the active ingredient was obtained <

Formulation Example 2 (Wettable powder)

 Ingredient weight%

 Compound 20 of the present invention

 Lauryl Sulfate 7

 Clay 7 3

 Heavy 27

 1 0 amount 0 o 2251

 The above mixture was uniformly mixed to obtain a wettable powder containing 20% of active ingredient, Formulation Example 3 (Floable)

 Ingredient

 Compound of the present invention

 Lauryl Sulfate

 Xanthan gum

 Hydroxypropyl cellulose

 Distilled water

1 0 0

 The above mixture was placed in a ball mill and pulverized and mixed for 12 hours to obtain a flooring agent containing 20% of the active ingredient.

Formulation examples in the case where the underwater biofouling inhibitor of the present invention is used as an antifouling paint are shown using the compounds of the present invention, but are not limited thereto. Prescription example 4

 Ingredient

 Compound 8 of the present invention

 VYHH (vinyl synthetic resin manufactured by UC C) 7

 Rosin 7

 Tricresyl phosphate 3

 Talc 2 0

 Sulfuric acid barrier 1 5

 Red petals 1 0

 2 0

 Methyl isobutyl ketone 10

1 0 0

Prescription example 5

 Ingredient

 Compound 5 of the present invention

 CR—10 (chlorinated rubber resin, manufactured by Asahi Denka) 1 3

 Zinc flower 2 0

 Talc 2 0

 Plasticizer 2

 Red petals 1 0

 3 0

1 0 0

 Formulation examples in the case of using the underwater biofouling inhibitor of the present invention as an antifouling agent solution are shown using the present invention compound, but the present invention is not limited thereto.

Prescription example 6

 Ingredient

 Compound 15 of the present invention

 Acrylic resin (50% xylene liquid) 50

 Xylene 3 5

1 0 0

Prescription example 7

 Ingredient

 Compound of the present invention 10

 Acrylic resin (50% xylene solution) 40

 The third tertiary nonyl pen sunset 5

 Liquid paraffin 5

 Xylene 40

1 0 0 Test example

 The antibacterial and antifungal activities of the phenylisothiocyanates of the present invention, the growth inhibitory activity against algae, and the anti-biological adhesion activity in water are described in Test Examples using Compounds 1 to 4, but the present invention is not limited thereto. It is not limited.

 Compound 1 and compound 2 are commercially available and readily available.

Compound 1 Compound 2

Compound 3 Compound 4

試験例 1 (抗菌 ·抗カビ活性評価）

Test Example 1 (Evaluation of antibacterial and antifungal activities)

Using dimeter sulfoxide, a dilution series of the compound of the present invention (2000, 10000, 500, 2,500, 2000, 1250, 625, 313, 15 6, 78, 39, 20, 10, 5, 2.5, 1.25 mg / 1) were prepared. For bacteria, use Sensitivity Medium 1N (Nissui Pharmaceutical) and for fungi, use Potato Dextrose Agar Medium (Nissui Pharmaceutical), add 0.5ml to each 9.5ml, mix Into a solidified plate. The concentration of the compound of the present invention in the agar medium was 100, 500, 250, 125, 100, 62.5, 31.3, 15.6, 7.8, respectively. , 3.9, 2.0, 1.0, 0.5, 0.25, 0.125, 0.0 e SmgZl. The inoculated bacteria were cultured at 37 ° C for 20 hours in a broth for sensitivity measurement (Nissui Pharmaceutical), and the fungi were cultured for 10 days on a potato dextrose agar medium (Nissui Pharmaceutical), each with 10 ⁶ C FUZm. One suspension was prepared. The test bacterial suspension was streaked using a platinum loop on a drug-mixed agar plate, and cultured for 18 to 20 hours at 37 ± 1 ° C for bacteria and 27 days for fungi at 27. The development of each The lowest concentration was defined as the minimum inhibitory concentration (MIC). The results are shown in Table 4. However, the symbols in the table mean the following.

 A: Bacillus subtilis

 B: Trichophyton mentagrophytes Table 4 Active compounds against bacteria and fungi MIC (mg / 1)

 N o. A B

1 7.8 0.5

 2 0.5

 3 2.0 Test Example 2 (Evaluation of growth inhibitory activity against freshwater green algae)

The logarithmic growth phase freshwater green alga (Serenasu Torumu Capri Korunutamu, Selenastrum capr icornutum) 1 0 medium containing a ⁵ m 1, respectively to dissolve a predetermined amount of a compound of the present invention, the concentration of each 5 of the present compounds in the medium Samples of 00 ppb and 50 ppb were prepared and cultured at 23 ± 1 for 24 hours under continuous lighting conditions.

 After 72 hours, the proliferation rate was determined by measuring the number of cells using a hemocytometer. The growth inhibition rate was calculated by comparison with the untreated group. The results are shown in Table 5.

 Table 5 Active compounds against freshwater green algae Growth inhibition rate (%)

 N o. 500ppb 50ppb

1 98.6 90.4

 2 98.8 95.1

 3 98.8 97.8

 4 98.6 93.1 Test Example 3 (Evaluation of growth inhibitory activity against seawater diatoms)

Seawater diatoms in the logarithmic growth phase (Nitchia ^{Kurosuteriumu, Nitzschia closterium) 1 0 5 m} 1 in medium containing each dissolved a predetermined amount of a compound of the present invention, concentration of each 5 0 of the present compounds in the medium 0 A sample of ppb was prepared and cultured statically under continuous lighting conditions for 24 hours. After collecting the cells by centrifugation after 72 hours, chlorophyll was extracted by adding methanol to break the cells and the growth rate was determined by measuring the amount of chlorophyll from the absorbance using a spectrophotometer. . The growth inhibition rate was calculated by comparison with the untreated group. The results are shown in Table 6.

 Table 6 Active compounds against seawater diatoms Growth inhibition rate (%)

 No. 500ppb

99.8

 2 100.0

 3 100.0

 4 100.0 Test Example 4 (Evaluation of mussel adhesion prevention activity)

 The compound of the present invention was completely dissolved in 1 ml of acetone and applied uniformly in a 4 cm diameter zone drawn on a test plate. A zone to which only acetone was applied was provided as a blank, and a zone to which 1.0 Omg and 0.5 mg of copper sulfate was applied as a comparative agent. After drying, mussels (Mytilus edulis) having a shell length of about 2-2.5 cm were adhered to the perimeter of each zone using a piece of rubber as a spacer. The prepared test plate was immersed in a water tank into which seawater flows, and allowed to stand in a dark place for 3 hours.

 The anti-adhesion effect (adhesion repellent activity) was determined by comparison with copper sulfate used as a comparative drug.

 The evaluation method of the adhesion activity is described by Kazuo Ina and Hideo Eto, "Searching method for adhesion repellent active substances of marine epiphytes using mussels" (Chemistry and Biology, Vol. 28 (No. 2), 13 22 ~ 1 P. 38 (1990).

 The results are shown in Table 7. However, the symbols in the table mean the following.

 + +: Does not adhere to the zone at all, and a strong repellent effect is observed.

 +: Adhesion inside the zone is also observed, but most adhere outside the zone, and repelling effects are observed.

I: Adhered to the same extent inside and outside the zone, and no repellent effect was observed. Table 7 Repellent activity against mussels Compound Judgment

 N o. (Mg)

1 0 + +

 0 5 + +

 2 1 0 + +

 0 5 + +

 Copper sulfate 0 +

 Five

Test example 5

 Petilal resin (Eslec B L-2 (manufactured by Sekisui Chemical Co., Ltd.)) was prepared at 15% W / W using a mixed solvent of toluene: methyl = 1: 1.

 Next, 70 mg and 35 mg of the compound of the present invention were respectively placed in a disposable culture tube, dissolved in the above resin solution, and tested on a test plate (vinyl chloride plate, 350 mm long × 60 mm wide). 0 mm) was applied in a sample zone of 5 cm diameter drawn above. A sample zone to which only the above resin solution was applied was provided as a blank. After drying, the test plate was immersed at a depth of about 1 m below sea level at the Shizuoka- 巿 Yomune fishing port.

 The presence or absence of antifouling activity was determined by comparing the state of adherence of organisms in the sample zone to the blank, and by the number of days during which adhesion was inhibited.

 The results are shown in Table 8 and FIG.

 This test was conducted from early April when biological activities (adhesion) were active.

 Table 8 Antifouling activity for marine organisms Compounds Antifouling days

 N 0. (Mg;

7 0 1 8 0 days or more

 3 5 1 8 0 days or more

 2 7 0 1 8 0 days or more

3 5 1 8 0 days or more The invention's effect

 The phenylisothiocyanates represented by the general formula (1) are highly safe, exhibit a wide spectrum with a low dose, and are used as industrial antibacterial agents, antifungal agents, algicides, and anti-biological adhesion agents. Useful as

Claims

The scope of the claims -General formula (1)

(Wherein, X, Y and Z each independently represent an alkyl group having 15 carbon atoms (the alkyl group may be optionally substituted with a fluorine atom); An alkoxy group (the alkoxy group may be optionally substituted with a fluorine atom), an alkoxycarbonyl group having 2 to 6 carbon atoms, a halogen atom, a nitro group, a hydroxyl group or a hydroxyl group, and G is an oxygen atom , Io atom, sulfinyl group, sulfonyl group or N-R (R is a hydrogen atom, an alkyl group having 15 carbon atoms, an alkenyl group having 2-6 carbon atoms or an alkynyl group having 2-6 carbon atoms. J and k each independently represent an integer of 0 to 5, j + k is always 5 or less, 1 represents an integer from 0 to 4. An industrial antibacterial and antifungal agent, an algicide or a biofouling inhibitor, characterized by containing phenylisothiocyanates represented by the formula:  2. An industrial antibacterial / antifungal agent, algicide or biofouling inhibitor comprising phenylisothiocyanate of formula (1) according to claim 1, wherein G is an oxygen atom.  3. An industrial antibacterial / antifungal agent, algicidal agent, or an antifungal agent, which comprises phenylisothiocyanates of the formula (1) according to claim 1, wherein G is a thio atom, a sulfiel group or a sulfonyl group. Biofouling inhibitor.  4. G is N—R (R represents a hydrogen atom, an alkyl group having 15 to 15 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or an alkynyl group having 2 to 6 carbon atoms). An industrial antibacterial and antifungal agent, algicide or biofouling inhibitor, comprising the phenylisothiocyanate of the formula (1) according to 1. 5. An industrial antibacterial and antifungal agent comprising the compound of the formula (1) according to claim 1. 6. An algicide comprising the compound of the formula (1) according to claim 1. 7. A biofouling inhibitor comprising the compound of the formula (1) according to claim 1.  8. An industrial antibacterial and antifungal agent comprising the compound of the formula (1) according to claim 2.  9. An algicide comprising the compound of the formula (1) according to claim 2. 10. An anti-biofouling agent comprising the compound of the formula (1) according to claim 2.  1 1. An industrial antibacterial and antifungal agent comprising the compound of the formula (1) according to claim 3.  1 2. An algicide comprising the compound of the formula (1) according to claim 3. 1 3. An anti-biofouling agent comprising the compound of formula (1) according to claim 3.  14. An industrial antibacterial and antifungal agent comprising the compound of the formula (1) according to claim 4.  1 5. An algicide comprising the compound of the formula (1) according to claim 4. 1 6. An anti-biofouling agent comprising the compound of the formula (1) according to claim 4.