CA1174005A - Fungicidal composition - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE

A fungicidal composition contains as the effective components a halogenated phenol compound, an alkyl tin compound and/or a phenyl tin compound, and an iodopropargyl-based compound. A water-soluble bactericidal composition is obtained by using as the solvent water, and a surfactant and a stabilizer.

Description

~ ~ 11740~5

- 2 -BACKGROUND OF THE INVENTION

The present invention relates to a funqicidal c ~ osition finding its suitable use in industrial raw materials such as wood, synthetic resin, leather and the like.

As well-known, the prior art fungicides contain as their effective components phenol-, organic tin-, oranic iodine-, carbamate-, anilide-, phenyl urea- and naphthalene-based compounds as well as metal salts of naphtathenic acid, creosote oil, etc. Among the phenol- and the organic tin-based compounds, there are particularly known a halogenated phenol compound and an alkyl tin compound and a phenyl tin compound, respectively.

These -fungicides are considerably effective in certain or higher concentrations, but less effective in lower concentrations. There is thus a demand for the development for fun~icides which are effective in low concentrations to reduce toxicity and make handling easy. Most of the prior art fungicides use as~ their solvents combustible petrolic substances, and are very dangerous in handling. For this reason, fungici~es using water as a solvent are~developed.
Since there is a possibility that the water used is then not only purified water but also hard water such as well water, however, it is desired that such fungicides are stable against hard water. Preferably, the Afungici~es are not affected by chemical substances contained in industrial raw materials such as wood extracts, fats contained in leather, free monomers contained in synthetic fibers and synthetic resins, etc.

~' 1~74V(35 5UM~IARY OF THE INVENTION
It would be advantageous to have a solution to the above mentioned problems.
In particular it would be advantageous to have a fungicidal composition which is sufficiently effective in a low concentration and a-water-soluble fungicidal com postionlwhich is rendered stable by adding thereto a combination of an activator and a stabilizer.
In general thepresent invention relates to a fungicidal composition containing as the effective compo-nents a phenol halide compound, an alkyl tin compound and/or a phenyl tin compound.
In particular, the present invention provides a fungicidal composition comprising lS (A) at least one halogenated phenol compound selected from the group consisting of trichlorophenol, tribromophenol, chloro-o-phenylphenol, pentachlorophenol, and pentabromophenol, (B) at least one alkyl or phenyl tin compound selected from the group consisting of tributyl tin oxide, tributyl oxide, tributyl tin acetate, tributyl tin oleate, tributyl tin chloride, tripropyl tin acetate, tripropyl tin chloride, tripropyl tin hydroxide, triethyl tin acetate, triphenyl tin acetate, and triphenyl tin hydroxide, and (C) at leastone iodopropargyl compound selected from the class consisting of (i) an iodopropargyl ether having the general formula ArOCH2C-CI wherein Ar stands for a group selected from the class consisting of a phenyl group, a naphthyl group, a quinoline group and a pyrimidyl group, said group Ar being unsubsti-tuted or substituted with one or more members selected from the class consisting of a nitro group, alkyl groups __.. .. . . . . . . . . .

~17401~5 having 1 to 4 carbo~ atoms and halogen atoms, and (ii) an iodopropargyl formal having the general . formula ArOCH2OCH2C-CI wherein Ar is as defined above/
with the weight ratio of (A) to (B) to (C) being in the range of 1Ø01-0.5:0.1-0.5.
The present invention also provides a fungicidal composition comprising ~A) at least one halogenated phenol compound selected from the group consisting of trichlophenol, tri-bromophenol, chloro-o-phenylphenol, pentachlorophenol, and pentabromophenol, (B) at least one alkyl or phenyl tin compound selected from the group consisting of tributyl tin oxide, tributyl oxide, tributyl tin acetate, tributyl tin oleate, tributyl tin chloride, tripropyl tin acetate, tripropyl tin chloride, tripropyl tin hydroxide, triethyl tin acetate, triphenyl tin acetate, and triphenyl tin hydroxide (C) at least one iodopropargyl compound selected from the class consisting of (i) an iodopropargyl ether having the general formula ArOCH2 CI wherein Ar stands for a group selected from the class consisting of a phenyl group, a naphthyl group, a quino-line group and a pyrimidyl group, said group Ar being unsubstituted or substituted with one or more members selected from the class consisting of a nitro group, alkyl groups having 1 to 4 carbon atoms and halogen atoms;
and (ii) an iodopropargyl formal having the general formula ArOCH2OCH2C _CI wherein Ar is- as defined above, and (D) a suitable sol~7ent.

_ 4 _ ,D'' 117~10~5 with the weight ration of (A) to (B) to (C) being in the range of 1:Ø01-0.5- 0-.01-C~5.
The present invention further provides a fungicidal composition comprising, (A) at least one halogenated phenol compound selected from the group consisting of trichlorophenol, tribromophenol, chloro-o-phenylphenol, pentachlorophenol, and pentabromophenol, (B) at least one alkyl or phenyl tin eompound selected fromthe group consisting of tributyl tin oxide, tributyl oxide, tributyl tin acetate, tributyl tin oleate, tributyl tin chloride, tripropvl tin acetate, tripropyl tin chloride, tripropyl tin hydroxide, triethyl tin acetate, triphenyl tin acetate, and trishenyl tin hydroxide, (C) at least one iodopropargyl compound selected from the class consisting of (i) an iodopropargvl ether having the general formula ArOCH2C_CI wherein Ar stands for a group selected from the class con-sisting of a phenyl group, a naphthyl group, a quinoline group and a pyrimydyl group, said group Ar being unsubstituted or substituted with one or more members selected from the class consisting of a nitro group, alkyl groups having 1 to 4 carbon atoms and halogen atoms, and (ii) an iodopropargyl formal having the general formula ArOCH20CH2C CI wherein Ar is as defined above, (D) a surface-active agent selected from the class consisting of ethylene oxide type, diethanol amine type, anhydrosorbitol type, glucoside type,and glycerin type nonionic surface-active agents, (E) a water solubilizing agent for said halogenated phenol, said agent being selected from the class consisting of alkali metal hydroxides, (F) a solvent in the form of water, with the weight ratio of (A) to (B) to (C) being in the range of - 4a -117'~ 5 1: 0.01-0.5 :. 0.01~0.5..
- . DETAILED PESCRIPTI.ON. OF THE IN~ENTION

According to the present invention, a fungicidal .formulation obtained by dissolving halogenated phenol compound, an alkyl.tin compound and/or a phenyl tin compound in an organic solvent such as kero'sene has an increased synergistic fungicidal effect, is sufficiently effective in a low concentration, and is of less toxicity.
A fungicidal composition which is safe to handle with no catch fire and extremely stable in properties is also obtained by using water as a solvent and adding a nonionic surfactant, a stabilizer and the like.
The halogenated phenol compound used in the present invention includes trichlorophenol, tribromophenol, chloro-O-phenylphenol, pentachlorophenol, pentabromophenol, etc. The alkyl tin compound includes tributyl tin oxide, tributyl tin acetate, tributyl tin oleate, tributyl tin chloride, tripropyl tin acetate, tripropyl tin chloride, tripropyl tin hydroxide, triethyl tin acetate, etc. The phenyl tin compound includes triphenyl tin acetate, tri- -phenyl tin hydroxide, etc. The iodopropargyl-based compound includes an iodopropargyl ether expressed bv the following formula: ArOCH2C-CI wherein Ar stands for a phenyl group a naphthyl group, a quinoline group, or a pyrimydyl group with or without an alkyl group, a halogen atom or a nitro group such as dichlorophenyl-3-iodopropargyl ether,and an iodopropargyl formal expressed by the following formula:
ArOCH2OCH2C-CI wherein Ar is as defined above, such as

3~ paranitrophenyl-3-iodopropargyl formal, parachlorophenyl-3-iodopropargyl formal, 3-naphthyl-3-iodopropargyl formal, and 8-quinolyl-3-iodopropargyl formula. Ar can also be, for example, m-cresyl-3-iodopropargyl ether (or) formal or xyenol-3-iodopropargyl ether(and formal) Where water is used as the solvent, the surface - 4b -~7~005 active agent to be used includes a nonionic surface acti~e agent based on ethylene oxide, diethanolamine, anhydrosor-bitol, glucoside and glycerol, such as polyethylene glycol alkylphenyl ether, polyethylene glycol fatty acid ester, ~-polyethylene glycol alkylamine, sorbitan fatty (i.e. aliphatic) acid ester, fatty (i.e. aliphatic) acid diethanol amide, etc. Suitable examples of the stabilizer used with hard water etc. are salts of alkali metals such as sodium chloride,potassium chloride, sodium sulfate, potassium sulfate, sodium phosphate, potassium phosphate, sodium nitrate, potassium nitrate, e-tc. It is noted that the fungicidal composition of the present invention is not limited to the above-mentioned compounds, and may contain other fungicides and pesticides.
The fungicidal composition according to the present invention may be formulated in known manner by, for instance, dissolving the above-mentioned halogenated phenol compound, alkyl tin compound and/or phenyl tin compound, and iodopropargyl-based compound in an organic solvent such as kerosene etc. followed by agitation.

/

~. - 5 -" 11740(~5 To obtain the water-soluble fungicidal composition in which water is used as the solvent, the halogenated phenol compound is converted into its salt, soluble in water, by the addition of analkali, to which the nonionic surface active agent and the alkali metal salt are added.

The inventive composition comprising the combination of the halogenated phenol compound, the alkyl tin compound and/or the phenyl tin compound, and the iodopropargyl-based compound produces a synergistic effect, and can be used in a considerably low concentration as compared with the separate use of the respective components. The components should preferably be used in a weight ratio of 1 : (0.01 - 0.5) :
~0.01 - 0.05). If the composition ratio is in a constant range, then the components can be maintained in higher concentrations during formulation. The resulting formulation may be diluted to a suitable degree of dilution during use. This is true of the water-soluble bactericidal composition.

The present invention will now be elucidated with reference to the following non-restrictive examples.

Example 1 Five fungicidal compositions were prepared from tri-bromophenol, triphenyl tin acetate and paranitrophenyl-3-iodopropargyl formal in the constant ratio but in varying concentrations ~ppm), using as the solvent kerosene.
Tribromophenol Triphenyl Paranitrophenyl Tin Acetate 3-iodopropargyl formal Composition 1 lO000 20 10 2 7500 15 7.5 3 5000 lO 5

4 2500 5 2.5 1500 3 1.5 11740(35 .~ - 6 -, Examples 2 to 12 inclusive Like Example 1, kerosene was used as the solvent, and tribromophenoll triphenyl tin acetate and paranitrophenyl-3-iodoproparagyl formal used as the effective components.
In these examples, the starting concentrations of the three components were varied.. While the three components were maintained in a substantially constant ratio, they were diluted to prepare five fungicidal compositions in each example. These compositions, numbered serially, are shown in Table 1 - 1.

Table 1 - 1 ExamplelComposi- Tribromophenol Triphenyl tin Paranitrophenyl-tion . acetate 3-io opropargyl I (ppm) ( ppm) (ppm) 1 7 7500 7.5 - 37.5 9 2500 2.5 12.5 I 10 500 0.52.5 I

1 12 3000 7.590 14 1000 2.530 1 15 200 0.56 I

; 1~740(~5 - 7 ~

Examplel Composi- Tribromopllenol Triphenyl tin Paranitrophenyl-1 tion acetate 3-iodopropargyl : (ppm) (ppm) (ppm) 21 200 26.7 32 1 23 100 :13.3 16 6.7 8 .
31100~ 20 20 I ~

8 1 38 60 lS 6 1 44 25 lS 15 I . ' 1 47 30 20 lS

49 lS 10 7.5 S0 9 6 4.5 . .

740~5 Examplel Composi- Tribromophenol Triphenyl tin 3-iod pr p rgyl l (ppm) (ppm) (ppm) I I ~
51 50 37.5 25 11 1 53 30 22.5 15 7.5 5 1 57 50 12.5 36 1 59 30 7.5 24 I _ Example 13 Five fungicidal compositions were preparedfrom chloro-o-phenylphenol, tri~ro~yl tin acetate and dichlorophenyl-3-io~o~opargyl ether in the constant ratio but in varying concentrations (ppm), using kerosene as the solvent.
Dichloro-3-Chloroo-o-phenylphnenol Triprophyl tin iodopropargyl acetateether Composition 61 120 30 90 Example 14 to 24 inclusive - The solvent and effective components as used in Example 13 were used. Like Example 13, the starting concentration of the three components were varied. While the three c~onents were maintained in a substantially constant ratio, they were diluted to prepare five f~nqicidal compositions in each example. mese compositions, numbered serially, are shown in Table 1-2.

1~ 74V~S
t ' _ 9 ~

Table 1 - 2 . Examplel Composi- Chloro-o-phynylphenol Triprophyl tin DichloroPheny~
'I tion acetate -3-iodopro-(ppm) ~ppm)pargyl ether l _ 1 66 30 . 30 30 1 67 , 25 25 25 . 1 80 20 8 15 _ . 17 1 83 800 16 16 I

. , 91 120 9 60 .
92 100 7.5 50 1 94 60 4.5 30 l 95 40 3 20 I

Example I Composi- Chloro-o-phynylphenol Triprophyl tin Dichlorophen~
tion acetate 3- ~o~or~ro-~argyl ether , (ppm) (ppm) (pFm) , 96 ` 2000 20 40 I99 ' 800 8 16 I l j 101 9000 9 90 I

109 6000 . 3 3 I

. 1 115 3000 12 24 I .
116 7000 3.5 350 241 118 5000 2~5 250 120 1 3000 1.5 150 117~0C5 ; ` . - 11 -Example 25 .
Like Examples 1 to 24, the following five fungici~al compositions 121 - 125 were prepared using kerosene as the solvent and three different active components Composition 121 Trichlorophenol 30 ppm Triphenyl tin oxide 10 ppm ~-naphthyl-3-iodopropargyl formal 5 ppm Composition 122 Pentachlorophenol 20 ppm Tributyl tin oxide 7 ppm 8-quinolyl-3-iodopropargyl formal 10 ppm Composition 123 30 ppm Trichlorophenol

5 ppm Tributyl tin oxide Parachlorophenyl-3-iodopropargyl formal 11 ppm - Composition 124 Tribromophenol 13.5 wt%
Tripropyl tin hydroxide 3.0 wt%
Parachlorophenyl-3-iodopropargyl formal 4.5 wt%
Kerosene 77.0 wt%

Composition 125 Chloro-o-phenylphenol 20.0 wt%
Triphenyl tin-oxide 1.0 wt%
~-naphthyl-3-iodopropargyl formal 5.0 wt%
Kerosene 64.0 wt%

"9r ~ .

74V1~5 Example 26 The nonionic surfactan~ and stabilizer werç used to obtain the following two water-soluble funyicidal compositions 126 and 127.

Composition 126 Trichlorophenol 18.0 wt%
TriprophyI tin chloride 3.0 wt%
Paranitrophenyl-3-iodopropargyl formal 2.0 wt%
Polyethylene glycol nonylphenyl ether 10.0 wt%
Sodium hydroxide 5.0 wt%
Potassium sulfate 2.0 wt%
Water 5~.0 wt%
.
Composition 127 Trichlorophenol 20.0 wt%
Triphenyl tin oxide 2.0 wt~
~-naphthyl-3-iodopropargyl formal1.0 wt%
Polyethylene glycol nonylphenyl ether 9.0 wt%
Sodium hydroxide 4.0 wt%
Sodium sulfate 1.0 wt%
Water 63.0 wt%

Com arative Exa les 1 to 6 inclusive p mp , For the purpose of comparision with Exemples 1 to 12, un~icidal compositions comprising one or two of three components tribromophenol, triphenyl tin acetate and para-nitrophenyl-3-iodopropargyl formal were prepared in varying concentrations (ppm), using kerosene as the solvent. These compositions, numbered serially, are shown in Table 2-1.

~ 13 -, , 1~740(~5 lab le 2 - 1 .
_ : Compar. tlve~ osi- Tribramophenol 'I~ipht_nyl tin 3aOio~dlop~Pph~gyl~ t . I (pplll) (ppm) (ppm) - t I ,, I (1) 4000!), _ _ j (2) ~oo~'o _ _ 11 (3) ~oono _ (4) 100~0 _ _ I (5) 7500 I - _ i~ (6) _ 200 _ I (7) _ 100 2 1 (8) _ 50 _ (9) _ 30 (10) _ 20 . I _ (11) _ _ 1000 I (12) _ _ 750 3 1 (13) _ _ 500 : I (14) _ _ 300 (15) _ _ 100 (16) 5000 50 (17) 4000 40 4 1 (18) 30no 30 _ . I (19) 20l.~0 20 _ (20) I10()0 10 I _ (21) 200()0 _ 100 (22) 18000 _ 90 1 (23) 160~)0 _ 80 (24) 14000 _ 70 (25) 12000 _ 60 I I .
I (26) _ 50 50 . I (27) _ ~0 40

6 ' (28) _ 30 30 (29) _ 20 20 (30) _ j 10 10 _. ... _. .

` 1~740QS

Comparative Examples 7 to 12 inclusive `
For the purpose of comparison with Examples 13 to 24 compositions comprising one or two of three active COMpO~
nents chloro-o-phenylphenol, tripropyl tin acetate and dichlorophenyl-3-iodopropargyl formal were prepared in varying concentrations (ppm), using kerosene as the solvent. These compositions, numbered serially, are shown in Table 2-2.
Table 2 - 2 I
G~arative~ Composi Chloro-o-phenylphenol Tripropyl Dichlorophenyl-E~ple I tion tin 3-1odo-, acetate propargyl (ppm) (ppm) (ppm) (31) soooo _ I (32) 40000 _ _

7 1 (33) 30000 _ _ I (34) 20000 _ I (35) 10000 _ _ I
(36) _ 300 I (37) _ 200

8 1 (38) _ lO0 (39) _ 50 _ (41) _ _ 1500 I (42) _ _ lO00

9 1 (43) _ _ 750 I `(44) _ _ 500 (45) I _ _ 300 I (46) 5000 100 I (47) 4000 80 ` 10 1 (48) 3000 60 (49) 2000 40 _ (50) 1000 20 . I .' .

`~ 11740(35 ¦Comparativel Ccmposi- ~ c-t3~c ~ ITripropyl Dichlorophenyl-E~mple I tion . t nproparagy . ¦ (ppm) (ppm) (ppm) l I
~51) 21000 _ 700 I (52) , 18000 _ 600 11 ~ (53) 15000 _ 500 I (54) 12000 _ 400 (55) 9000 _ 300 I l ~56~ _ 100 50 (57) _ 80 40 . 12 1 (58) _ 60 30 (59) _ . 40 20 (60) _ 20 . 10 l _ ~omparative Example 13 For the purpose of comparison with Examples 25 and 26~
a ~.ungicidal~composition ~61), (62) in which kerosene was as the solvent, and water-soluble bactericidal compositions (63) - (66) were prepared.

- Composition ~61) Tribromophenol 30.0 wt%
Tripropyl tin oxide 5.0 wt%
Kerosene 65.0 wt%

Composition (62) Chloro-o-phenylphenol 35.0 wt%
~-naphthyl-3-iodopropargyl formal ~ 5.0 wt%
kerosene 60.0 wt%

` ~740~5 Composition (63) . Tripropyl tin chlori-le 5.0 wt~
Poranitrophenyl-3-iodopropargyl formal 3.0 wt%
Polyethylene glycol nonyluhenyl ether 10.0 wt~
Sodium hydroxide 5.0 wt%
Potassium sulfate . 2.0 wt%
Water ', 74.0 wt%
.. .
Composition (64) Trichlorophenol 20.0 wt%
T~iphenyl tin hydro:ide 2.0 wt%
~-naphthyl-3-iodopropargyl formal 3.0 wt~
Sodium dioctylsulfo.~uccinic acid 15.0 wt%
Sodium hydroxide 6.0 wt%
Potassium sulfate 3.0 wt%
Water 36.0 wt%

Composition (65) Trichlorophenol 20.0 wt%
Triphenyl tin hydroside 2.0 wt%
3-naphthyl-3-iodopropargyl formal 3.0 wt%
Hexadecyltrimethylalllmonium chloride 15.0 wt%
Sodium hydroxide 6.0 wt~
Sodium sulfate 3.0 wt%
Water 36.0 wt%

Composition (66) Trichlorophenol 20.0 wt%
Triphenyl tin hydro~ide 2.0 wt%
~-naphthyl-3-iodopropargyl formal 3.0 wt%
Polyethylene glycol nonylphenyl ether 15.0 wt~
Sodium hydroxide 6.0 wt~
Water 39.0 wt%

40(~5 esting 1: Comparison test on the effect of fungicidal compositions according to the paper disc method ln this testing, use was made of compositions 1 to 12 of Examples 1 to 12 and compositions (1) to (60) of Comparative Examples 1 to 12. A paper disc for the testing of antibiotics was immersed in each co~position for five (5) seconds, air-dried for about twelve (12) hours, and used for testing.
One of the thus treated discs was placed over a Petri dish into which 20 ml of a PDA culture medium was filled, and was uniformly sprayed with about 2 ml of a spore suspension of Aspergillus niger ATCC 6275, and allowed to stand in a thermostat adjusted to 28 + 2 C for 48 hours.
The growth of hyphae was observed after 24 hours and 48 hours. Similar testing was carried out with Rhizopus nigricans S.N. 32, Fusarium moniliforme USDA 1004.1 and Trichoderma T-l ATCC 9645.

The results of testing are shown in Tables 3-1 to 3-6 and Tables 4-1 to 4-4.

The test results are assayed as follows:
- : The growth of hyphae is inhibited, and inhibit~v zones are formed around the paper disc.

: The effect of funqicides ; is found, although any inhibitorv zones are not observed visually.

: The growth of hyphae is not inhibited, and any inhibitory zones are not formed.

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From Table 4-1, it is found that the tribromophenol, triphenyl tin acetate and,paranitrophenyl-3-iodopropargyl formal have a fungicidal effect o.n Aspergillus niger ATCC 6275 in concentrations of 20000 ppm, 30 ppm and 300 ppm, respectively. Hence, 1 ppm of triphenyl tin acetate corresponds to 666.7 ppm of tribromophenol, whereas 1 ppm of paranitrophenyl-3-iodoprppargyl formal is equivalent to 66.7 ppm of tribromphenol.

Table 5 show the inhibition concentrations - calculated as tribromophenol - of the compositions comprising two or three of tribromophenol, triphenyl tin acetate and paranitrophenyl-3-iodopropargyl as shown in Tables 3-1 and 3-2 and 3-3.

Table 6 shows the inhibition concentrations - calculated as chloro-o-phenylphenol - of the compositions comprising two or three of chloro-o-phenyl, tripropryl tin acetate and dichlorophenyl-3-iodopropargyl ether as shown in Tables 3-4 to 3-6.

Tables 7 and 8 show the inhibition concentrations calcu-lated for Rhizopurs nigricans S.N. 32, while Tables 9 and 10 show the inhibitions concentrations calculated for Fusarium moniliforme USDA 1004.1 and Trichoderma T-l ATCC 9645.

In Tables 5, 7 and 9, ~,B, and D stand for tribromophenol triphenyl tin acetate and paranitrophenyl-3-iodopropargyl formal, respectively. The inhibition concentrations -calculated as tribromophenol - are determined from the following calculation: -W = X + 666.7 Y ~ 66.7 Z.

'`.

~ 2g . 1~740Q5 wherein X is the concentratir~n of tribromophenol (ppm),Y is the concentration of tripohenyl tin acetate (ppm),~
and Z is the concentration oE paranitrophenyl-3-iodopropargyl formal (ppm).

In Tables 6, 8 and 10, n.E. and F stand for chloro-o-phenylphenol, tripropyl tin ~cetate and dichlorophenyl-3-iodopropargyl formal, respec~-.ively. The calculation formula is omitted.

Table 11 shows the inhjl:)ition concentrations oE composi-tions 121 - 123 of ~xample 2r~.

74~5 3~ -Table 5 _ ~
C,omposition,ratio of Inhibition concentra-fungicidaltion-calculated as compositiontribromophenol . A ¦ B 1 C (ppm) I
1 0.6 ¦0~61 1 0 3 0 1 0.~7 0.51 4 3 3 1 0.75 0.51 0 6 9 0 1 0.25 0.8 8 8 4 0 1 U.13 j 0.16 7 5 4 Q
1 0.08 0.04 8 5 5 0 1 4.02 0.02 7 8 3 0 1 0.2 5 0.1 6 9 7 0 t 0.001 l0.0051 Q 0 0 0 1 0.002510.u3-q 3 4 0 1 O.OQ1 Q.0029 0 0 0 1 0.01 _1 5 3 3 0 1 _ O.OOS1 6 0 0 0 _ 1 1t 5 3 3 0 .
-2 0 D 0 0 l 11740(~5 Table 6 .
ComPosition ratio of Inhibition concentration fungicidal -calculated as chloro-o-composition , phenylphenol D ll ~ 1 F (ppm) 1 , U.25 l0.75 1 0 8 6 0 1 ! 1 1 9 6 2 0 1 ' 0.6 0.8 1 1 7 9 U
1 ¦ a.4 0~75 1 0 8 4 0 ll _ __ _ 1 li 0.U2 0.02 ~ 8 4 ~ 0 1 ~ 0.1 0.U2 ~ 9 3 9 0 1 1 0~075 j0.5 17 9 2 0 1 ! ' ! 0-02 1~ 6 1 0 ., . I I
1 , 0.001 10.01 ¦1 2 0 0 0 1 , 0.0005 0.0005 11 0 5 6 0 1 i 0.004 0-008 11 3 0 2 U ¦
1 ~ 0.0005 U.005 ¦1 5 2 8 0 ~, . 1 i 0.02 - 12 6 0 0 ~ !

_ li 2 1 2 4 8 0 0 l l . 1 1 - ~ _ 3 0 0 0 0 1~740~5 .

T ble 7 Composition ratio of Inhibition concentra- ;
fun~icidal tion-calculated as composition tribromophenol . .
B ¦ C (ppm) : I
1 0-6 ~ 9 8 4 0 1 0.67 15 9 0 3 0 t ¦ 0.75 j 0.5 1 0 0 3 0 1 j 0.25 ~ 0.8 9 2 6 0 1 U.1 3 11 0.1 6 6 4 9 0 1 j 0.08 14 5 3 5 0 1 ~ 0.02 '0.02 775~
1 ! 0.25 ¦ 0.1 6 4 G O
I 1. .
1 0.û02 i~.U005 9 3 3 0 1 0.001 ',O.OD5 1 3 0 0 0 1 0.0025,û.03 8 0 0 0 1 ¦ 0.005 10.0059 0 0 0 I i l 1 . 0.01 ¦ - 1 5 0 0 0 1 _ 0.0051 8 6 7 0 _ 1 11 4 0 0 0 1 _ _ 2UOOO
_ ~ i 1~74~ 5 Table 8 _ Composition ratio of ¦ Inhibition concentration i fungicidal -calculated as chloro-o-composition , phenylphenol D ¦ E I F (ppm) ._ I I
1 l 0.25 1 07 5 !1 1 8 2 0 -1 ~ 9 9 3 0 1 1 0.6 ,0.8 1 1 0 25 0 1 1 0.4 0.75 1 9 8 5 0 l l l 1 ¦ 0.0 2 U.0 2 ~ 7 6 0 0 1 1 0.1 0.02 1 ~320 1 0.075 j~-5 ! _ I
1 0.01 10.02 ! 80U0 .. . ~
1 0.001 0.01 j 1 ~ 4 0 0 1 0.0005 0.0005 l 1 3 0 0 0 1 ~ 0.004 0.008 j 1 2 2 0 0 1 0.000 5 0.00 5 'I 1 5 9 0 0 o:oi _ 2 8 0 0 0 1 _ 0.033 2 4 0 0 0 _ 2 1 2S200 _ _~_ l _ _ 30U00 _ _ ..

` 1~ 7~0(~5 . , `

Table . _ Composition ratio of Inhibition concentra-~fungicidal tion-calculated as composition tribromophenol .__ _ I B ¦ C l tppm) 1 U.60.6 1 3 5 3 0 1 0.67 O.S 9 g 2 ~
t 0.75 0.5 1 2 0 2 0 1 0.25 1 0.8 1 1 1 3 û
_ 1 U.13 0.16 9 6 8 0 1 0.0 8 O.D~ 9 1 5 0 1 0.02 j 0.02 9 S 0 0 1 0.25 ~-1 10860 l i 1 0.002 0.0005 1 2 5 0 0 1 0.001 0.005 1 5 5 0 0 `1 0.0025 0.03 1 1 5 0 0 1 0.005 0.005 .1 1 0 0 0 .
1 0.01 _ 2 8 0 0 0 1 _ 0.005 _ _ 1 1 2 7 0 0 0 .
1 ~ _ 3 0 0 0 0 _ _~

:~i - 11740(~5 T ble lO

Com~ositi nn ratio of Inhibition concentration funaicidal -calculated as chloro-o-composition phenylphenol D ~ ¦ ~ (ppm) 1 1 0.25 ~ 0.75 - 1 1 3 1 0 0 1 0.6 ~ 0.8 1 3 6 5 0 1 0.4 ¦ 0.75 1 3 1 0 0 !
1 0.02 ~0.02 9 8 0 0 1 0.1 1 0.02 8 3 6 0 1 U.075 l0.56 1 2 0 t 0.01 ~.02 9 2 8 0 1 0.001 ~0.011. 6 2 0 0 1 0.0005 O.OOOS1 4 6 4 0 1 0.004 0.0081 4 6 0 0 1 0.0005 0.0051 6 0 0 0 i ' 10.02 _3 6 0 0 0 1 0.0333 5 0 U 0 . 2 13 3 6 0 0 L_______l -4 0 0 0 0 _ :

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1~740(35 From Tables 5 to 11, it is found that the inventive fungicidal composition comprising a halogenated phenol, an alkyl tin compound and/or phenyl tin compound and an iodopropargyl -formula produces a fungicidal effect by far greater than one or two of these compounds do From Tables - 5 to 10, it is also found that, when the above-mentioned three components is in a composition range of 1 : 0.01 -0.5 : 0.01 -0.5, they have a marked effect.
Testing 2: Comparison test on the effect of lo fungicidal compositions on various indus-trial raw materials The fungicidal effect of compositions 121 to 123 and (62) and (63) of Example 25 and Comparative Example 13 on synthetic fibers, leather and wood was examined according to JIS Z 2911. Polyester fiber specimensandwestern hemlock specimenswereused as the synthetic fiber and wood, and Aspergillus niger ATCC 6275 was used as a testing fungus.
As will be evident from Table 12, the results indicate that the inventive fungicidal composition containing as the active components a halogenated phenol, an alkyl tin compound or a phenyl compound, and an iodopropargyl-based compound exhibits an excellent fungicidal effect. There-fore, the inventive composition has an excellent effect on the prevention of deterioration of wood, synthetic fiber and leather . ~ - 37 -., li74VC~S
~ -- 38 --_ _ ~"Pro 'o ~r~GrO, e~,~'o o ~ I ~ æ~ D~ ~P c ~ a O ` r~ V VN r ~ d ~ S r~ 1~ rrl ~: o .: o , ' o o o I o L A~, a ~ a 8 ~ ~B ~ ~j 7 ~ ~ y ~ ~la ? v ~s ~B~ ~v~ ~ w c c c c c c c c c c e O ~u e~ o ~ o o o 8i a~ e ~o e e~ E e e ~ 1~ 7 ~ s c c ~o ~ ~,o ~ e ~ c ~

_ c ~ a ~ c ~ I a ,,, 'uO O O ~0 0 0 O O ~o 80 ~ dP 83 ~ ~eO ~o ~e ro e3 ~P 8 e e .(1 V V ~ V ~ V U~ L S ~C 3 U~ 3 tb O O O O O ' O ~ ~ O , O
E~ C ~0~ ,0~, o~ o ~3 8~o~ ~ ~,0 ~0 ~,0 ~,~,0 ~, 0 ~0~,,0 ~ Z~ z ~Z~ Z~u, ZO,~ ~ zo ~j~ z ~ ,ZO~ ~ -S ~ a S .S S S ~rl . _ r V A V V V V V V V V V V V U C C C
V ¦`U C ru C ru C,V V V V V V V V V V V U i U C W o U i ~ U i C C C
~; I ~ ~n ,~ rn _I rn _I rn _~ rn ~ rn _~ rn ~1 n _I rn ,~ ~n _~ r3 ,~ rn ,~ rn _I rn ~ rn ,_~ rn ,~ n ,I rn r4 1 ' ~ e~ e e8 o ~ ea a eD e~ ~ e l ~ '' eD~ ~ e -~ e~ o o ~ ~
l "p eO ~P 8 ~ U ~ ~ 8 ~ 8 ~ u ~ u ~ u ~ u rlD u ~P o ~ ,, ~ U ~ u ~ u ~ u l -~u ~u u ~o ~ ~uo ~ ~u IU ~ru ~u u ~ o ~ t,~ o ~3 ~ _ ~ 33 e ~ g~ e ; 1~740(~5 _ 39 _ Testing 3: Stability test of rungici~al compositions In general, the water-soluble fun~icidal compositions are diluted with water for use. However, the rungici~.al power of the compositions is largely affected by the hard-ness of watr, the klnd~~f cllemical components contained in industrial raw materials, the temperature applied, and the like factors, as mentioned above. In this test, composition 127 of Example 26 and compositions (64) - (66) of comparative Example 13 were diluted 50 and 100 times with tap water, 10 hard water and western hemlockextract liquids (powdered woo~/water = 1/1 by volume), and allowed to stand at room temperature and 50C for one month for the determination of stability.

Stability is assayed as follows:
: The diluted liquid is satisfactory, and shows no sign of precipitation.

O : The diluted liquid is satisfactory, but shows signs of slight precipitation.

: The diluted liquid shows signs of destruction and rather much precipitation.

X : The diluted liquid shows signs of complete destruction and much precipitation.

~ s will be evident from Table 13, the results indicate that the i,nventive funaicidal composition excels not only in ;fungicidal ~ effect but also in stability.

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Claims (15)

The embodiments of the invention in which an ex-clusive property or privilege is claimed are defined as follows:

1. A fungicidal composition comprising (A) at least one halogenated phenol compound selected from the group consisting of trichlorophenol, tribromophenol, chloro-o-phenylphenol, pentachlorophenol, and pentabromophenol, (B) at least one alkyl or phenyl tin compound selected from the group consisting of tributyl tin oxide, tributyl oxide, tributyl tin acetate, tributyl tin oleate, tributyl tin chloride, tripropyl tin acetate, tripropyl tin chloride, tripropyl tin hydroxide, triethyl tin acetate, triphenyl tin acetate, and triphenyl tin hydroxide, and (C) at least one iodopropargyl compound selected from the class consisting of (i) an iodopropargyl ether having the general formula ArOCH2C?CI wherein Ar stands for a group selected from the class consisting of a phenyl group, a naphthyl group, a quinoline group and a pyrimidyl group, said group Ar being unsubstituted or substituted with one or more members selected from the class consisting of a nitro group, alkyl groups having 1 to 4 carbon atoms and halogen atoms, and (ii) an iodopropargyl formal having the general formula ArOCH2OCH2C?CI wherein Ar is as defined above, with the weight ratio of (A) to (B) to (C) being in the range of 1:0.01-0.5:0.1-0.5.

2. A fungicidal composition comprising (A) at least one halogenated phenol compound selected from the group consisting of trichlorophenol, tri-bromophenol, chloro-o-phenylphenol, pentachlorophenol, and pentabromophenol, (B) at least one alkyl or phenyl tin compound selected from the group consisti.ng of tributyl tin oxide, tributyl oxide, tributyl tiri acetate, tributyl tin oleate, tributyl tin chloride, tripropyl tin acetate, tripropyl tin chloride, tripropyl tin hydroxide, triethyl tin acetate, triphenyl tin acetate, and triphenyl tin hydroxide (C) at least one iodopropargyl compound selected from the class consisting of (i) an iodopropargyl ether having the general formula ArOCH2?CI wherein Ar stands for a group selected from the class consisting of a phenyl group, a naphthyl group, a quinoline group and a pyrimidyl group, said group Ar being unsubstituted or substituted with one or more members selected from the class consisting of a nitro group, alkyl groups having 1 to 4 carbon atoms and halogen atoms, and (ii) an iodopropargyl formal having the general formula ArOCH2OCH2C?CI wherein Ar is as defined above and (D) a suitable solvent, with the weight ratio of (A) to (B) to (C) being in the range of 1 : 0.01-0.5 : 0.01-0.5.

3. A fungicidal composition comprising, (A) at least one halogenated phenol compound selected from the group consisting of trichlorophenol, tri-bromophenol, chloro-o-phenylphenol, pentachlorophenol, and pentabromophenol, (B) at least one alkyl or phenyl tin compound selected from the group consisting of tributyl tin oxide, tributyl oxide, tributyl tin acetate, tributyl tin oleate, tributyl tin chloride, tripropyl tin acetate, tripropyl tin chloride, tripropyl tin hydroxide, triethyl tin acetate, triphenyl tin acetate, and triphenyl tin hydroxide, (C) at least one iodopropargyl compound selected from the class consisting of (i) an iodopropargyl ether having the general formula ArOCH2C ? CI wherein Ar stands for a group selected from the class consisting of a phenyl group, a naphthyl group, a quinoline group and a pyrimidyl group, said group Ar being unsubs-tituted or substituted with one or more members selected from the class consisting of a nitro group, alkyl groups having 1 to 4 carbon atoms and halogen atoms, and (ii) an iodopropargyl formal having the general formula ArOCH2OCH2C?CI wherein Ar is as defined above, (D) a surface-active agent selected from the class consisting of ethylene oxide type, diethanol amine type, anhydrosorbitol type, glucoside type, and glycerin type nonionic surface-active agents, (E) a water solubilizing agent for said halogenated phenol, said agent being selected from the class consisting of alkali metal hydroxides, and (F) a solvent in the form of water, with the weight ratio of (A) to (B) to (C) being in the range of 1 : 0.01-0.5 : 0.01-0.5.

4. A fungicidal composition according to claim 3 which further comprises a stabilizer selected from the group consisting of suitable alkali metal salts in a concentration of not more than 3% by weight of the composition.

5. A fungicidal composition according to claim 1 or claim 2 wherein said at least one iodopropargyl compound is selected from the class consisting of dichlorophenyl-3-iodopropargyl ether/p-nitrophenyl-3-iodopropargyl formal, p-chlorophenyl-3-iodopropargyl formal, .beta.-naphthyl-3-iodopro-pargyl formal and 8-quinolyl-3-iodopropargyl formal.

6. A fungicidal composition according to claim 3 wherein said at least one iodopropargyl compound is selected from the class consisting of dichlorophenyl-3-iodopropargyl ether,p-nitrophenyl-3-iodopropargyl formal, p-chlorophenyl-3-iodopropargyl formal,.beta.-naphthyl-3-iodopropargyl formal and 8-quinolyl-3-iodoproparyyl formal.

7. A fungicidal composition according to claim 6 wherein the surface active agent is selected from the class consisting of polyethylene glycol alkyl phenyl ethers, polyethylene glycol aliphatic acid esters, N-polyethylene glycol alkyl amines, sorbitan aliphatic acid esters and aliphatic acid diethanol amides.

8. A fungicidal composition according to claim 7 which further comprises a stabilizer selected from the group consisting of-suitable alkali metal salts in a concentration of not more than 3% by weight of the compo-sition.

9. A fungicidal composition according to claim 8 wherein said stabilizer is selected from the class consisting of sodium chloride, potassium chloride, sodium sulfate, potassium sulfate, sodium phosphate, potassium phosphate, sodium nitrate, and potassium nitrate.

10. A fungicidal composition according to any one of cIaims 1, 2 and 3 wherein said group Ar is unsubsti-tuted or substituted with a nitro group or one or more halogen atoms.

11. A fungicidal composition according to claim 4, wherein said group Ar is unsubstituted or substituted with a nitro group or one or more halogen atoms.

12. A fungicidal composition according to claim 2 wherein the solvent is kerosene.

13. A fungicidal composition according to claim 12 wherein said at least one iodopropargyl compound is selected from the class consisting of dichlorophenyl-3-iodopropargyl ether, p-nitrophenyl-3-iodopropargyl formal, p-chlorophenyl-3-iodopropargyl formal, .beta.-naphthyl-3-iodopropargyl formal and 8-quinolyl-3-iodopropargyl formal.

14. A fungicidal composition as according to any one of claims 3, 4 and 6 wherein said solubi-lizing agent is sodium hydroxide.

15. A fungicidal composition as according to any one of claims 7, 8 and 9 wherein said solubili-zing agent is sodium hydroxide.