JP2003012418A - Composition for industrial use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition for industrial use excellent in heat resistance, water resistance, weather resistance and alkali resistance, capable of expressing seaweed proofing and fungicidal effects. SOLUTION: This composition for industrial use includes a triazine based compound and a triazole based compound. This composition for industrial use is preferably used in an indoor-outdoor environment suffering from rain water, humidity or exposed to UV such as sun light or the like because the composition is excellent in heat resistance, water resistance, weather resistance and alkali resistance, expresses seaweed proofing and fungicidal effects and the composition is capable of effectively expressing the effects not only to an oil-soluble subject but also to a water-soluble subject because the composition is excellent in alkali resistance. The composition can be applied to a water-soluble or oil-soluble paint, adhesive or plastic product used in these environments.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an industrial composition, and more particularly to an industrial composition suitable for use as an algae-proofing agent and / or fungicide.

[0002]

2. Description of the Related Art Conventionally, various industrial waters such as paper pulp mills and cooling water circulation processes, metal working oils such as cutting oils, casein, starch paste, glue, coated paper, paper coating liquid, surface Sizing agent, paint, adhesive, synthetic rubber latex, printing ink, polyvinyl alcohol film, vinyl chloride film, plastic product, cement admixture,
A variety of industrial products such as sealing agents and jointing agents are prone to the propagation of harmful microorganisms such as algae and molds, which causes deterioration of productivity and quality and generation of bad odor. Therefore, in order to control the reproduction of such microorganisms, algae-proofing agents and fungicides which exhibit an algae-proofing effect and a fungus-proofing effect are widely used.

[0003]

However, existing anti-algae and anti-fungal agents have their anti-algae and anti-fungal effects in indoor and outdoor environments where they are exposed to rainwater, moisture, or ultraviolet rays such as sun rays. In many cases, the value is significantly reduced.

In recent years, from the viewpoint of environmental protection, the use of water-based paints and water-based adhesives is increasing,
It is desired to develop an antialgal agent and a fungicide which can be effectively used not only in oil-based paints and oil-based adhesives but also in alkaline water-based paints and water-based adhesives.

Therefore, the present invention has been made in view of such circumstances, and an object thereof is to exhibit excellent heat resistance, water resistance, weather resistance and alkali resistance, and to exhibit an antialgal effect and an antifungal effect. It is to provide an industrial composition capable of

[0006]

In order to achieve the above object, the present invention provides (1) an industrial composition containing a triazine compound and a triazole compound, and (2) a triazine compound. Is the general formula (1)

[0007]

[Chemical 4] (Wherein R 1, R 2, R 3 and R 4 represent a hydrogen atom or a hydrocarbon group which may have a substituent, and X represents a halogen atom or an alkylthio group). In the industrial composition according to (1) above, (3) in the formula (1), R1 and R2 are a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R3.
And R4 is an alkyl group having 1 to 5 carbon atoms which may be substituted by an alkoxy group having 1 to 4 carbon atoms or a cycloalkyl having 3 to 6 carbon atoms which may be substituted by an alkoxy group having 1 to 4 carbon atoms Group, wherein X is a halogen atom or an alkylthio group having 1 to 4 carbon atoms, and the industrial composition as described in (2) above, (4)
The triazine-based compound is 2-methylthio-4-t-butylamino-6-cyclopropylamino-s-triazine, 2-chloro-4,6-diethylamino-s-triazine, 2-chloro-4-ethylamino-6. -Isopropylamino-s-triazine and 2-methylthio-4-ethylamino-6- (1,2-dimethylpropylamino)
At least one selected from the group consisting of -s-triazine
The industrial composition according to any one of (1) to (3) above, wherein the triazole-based compound is (5) is a general formula (2).

[0008]

[Chemical 5] (In the formula, Y1, Y2 and Y3 are the same or different and each represents a hydrogen atom or a hydrocarbon group which may have a substituent, and A1 represents an aryl group or a substituent which may have a substituent. An optionally substituted aralkyl group, n is 1 to 3
Indicates an integer. ) And / or general formula (3)

[0009]

[Chemical 6] (In the formula, Y4 and Y5 are the same or different and each represents a hydrogen atom or a hydrocarbon group which may have a substituent,
Represents an aryl group which may have a substituent or an aralkyl group which may have a substituent, and n represents an integer of 1 to 3. ) Is a compound represented by
The industrial composition according to any one of (1) to (4) above, and the triazole-based compound (6) is a compound represented by the general formula (2), and in the formula of the general formula (2), Y1 , Y
2 and Y3 are the same or different and each is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, and A1 is a halogen-substituted phenyl group or a halogen-substituted phenylalkyl group, (5) above. An industrial composition of
(7) The triazole-based compound is a compound represented by the general formula (3), and in the formula of the general formula (3), Y4 and Y4
5 is both a hydrogen atom, or one is a hydrogen atom and the other is a hydrocarbon group having 1 to 4 carbon atoms, A2 is a halogen-substituted phenyl group, the industrial according to the above (5), Composition, (8) triazole compound is α
-[2- (4-chlorophenyl) ethyl] -α- (1,
1-dimethylethyl) -1H-1,2,4-triazole-1-ethanol, 1-[[2- (2,4-dichlorophenyl) -4-n-propyl-1,3-dioxolan-2-yl] Methyl] -1H-1,2,4-triazole, 1-[[2- (2,4-dichlorophenyl) -1,
3-dioxolan-2-yl] methyl] -1H-1,
2,4-triazole, α- (4-chlorophenyl)-
α- (1-cyclopropylethyl) -1H-1,2,4
-Triazole-1-ethanol is at least one selected from the group consisting of the above (1)
~ The industrial composition according to any one of the above (7), (9)
The present invention relates to the industrial composition according to any one of (1) to (8), which is an antialgal agent and / or antifungal agent.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The industrial composition of the present invention is not particularly limited, but is useful as an industrial algae-proofing agent and / or fungicide, and its active ingredient is a triazine-based compound or a triazole-based compound. Contains.

In the present invention, examples of the triazine compound include compounds represented by the following general formula (1).

[0012]

[Chemical 7] (In the formula, R1, R2, R3 and R4 represent a hydrogen atom or a hydrocarbon group which may have a substituent, and X represents a halogen atom or an alkylthio group.) The above general formula (1).
Examples of the hydrocarbon group represented by R1, R2, R3 and R4, which may have a substituent, include an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group and an aryl group. Can be mentioned.

Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl,
Examples thereof include alkyl groups having 1 to 10 carbon atoms such as sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, isooctyl, sec-octyl, tert-octyl, nonyl and decyl.

As the alkenyl group, for example, vinyl,
C2-C4 such as allyl, isopropenyl, 1-propenyl, 2-propenyl, 2-methyl-1-propenyl
Alkenyl groups of

Examples of the alkynyl group include alkynyl groups having 2 to 5 carbon atoms such as ethynyl, 1-propynyl, 2-propynyl, butynyl and pentynyl.

Examples of the cycloalkyl group include cycloalkyl groups having 3 to 8 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.

As the aryl group, for example, phenyl,
6 carbon atoms such as naphthyl, anthryl and phenanthryl
To 14 aryl groups.

The substituent of the optionally substituted hydrocarbon group represented by R1, R2, R3 and R4 is
For example, a hydroxyl group, a halogen atom (for example, chlorine, fluorine, bromine and iodine), a cyano group, an amino group, a carboxyl group, an alkoxy group (for example, methoxy, ethoxy, propoxy, butoxy and the like, having 1 to 1 carbon atoms).
4 alkoxy group, etc.), an aryloxy group (eg,
Examples thereof include a phenoxy group), an alkylthio group (for example, an alkylthio group having 1 to 4 carbon atoms such as methylthio, ethylthio, propylthio, and butylthio) and an arylthio group (for example, a phenylthio group).
These substituents may be the same or different and may be substituted by 1 to 5, preferably 1 to 3.

As the above-mentioned hydrocarbon group which may have a substituent represented by R1 and R2, a hydrocarbon group which does not have a substituent is preferable, and among them, an alkyl group is preferable. The alkyl group has 1 carbon atom such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl.
Alkyl groups of 4 are preferred.

The above-mentioned hydrocarbon group which may have a substituent represented by R3 and R4 is an alkyl group which may have a substituent or a cycloalkyl which may have a substituent. Groups are preferred.

Examples of the alkyl group represented by R3 and R4 which may have a substituent include, for example,
Examples thereof include alkyl groups having 1 to 5 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-pentyl and isopentyl.
In addition, examples of the substituent include the same ones as described above.

The cycloalkyl group of the cycloalkyl group which may have a substituent represented by R3 and R4 includes, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and other cycloalkyl groups having 3 to 6 carbon atoms. Groups. In addition, examples of the substituent include the same ones as described above.

Examples of the halogen atom represented by X include fluorine, chlorine, bromine, iodine and the like. Examples of the alkylthio group represented by X include an alkylthio group having 1 to 4 carbon atoms such as methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio and isobutylthio.

In a preferred embodiment of the general formula (1), R1 and R2 are hydrogen atoms or alkyl groups having 1 to 4 carbon atoms, and R3 and R4 are not substituted or have 1 to 4 carbon atoms. An alkyl group having 1 to 5 carbon atoms which is substituted with an alkoxy group, or a cycloalkyl group having 3 to 6 carbon atoms which is unsubstituted or substituted with an alkoxy group having 1 to 4 carbon atoms, An embodiment in which X is a halogen atom or an alkylthio group having 1 to 4 carbon atoms can be mentioned. Among these, particularly preferred is an embodiment in which the cycloalkyl group having 3 to 6 carbon atoms is a cyclopropyl group, and X is a chlorine atom, or methylthio or ethylthio.

Such a triazine compound can be produced by a known method according to the following specific compounds. Specific examples thereof include 2-methylthio-4-t-butylamino-6-cyclopropylamino-s-triazine, 2-chloro-4,6-diethylamino-s-triazine and 2-chloro-4-ethyl. Amino-6-isopropylamino-s-triazine, 2-methylthio-4-ethylamino-6- (1,2-dimethylpropylamino) -s-triazine and the like can be mentioned. Of these, more preferred is 2-methylthio-4-t.
-Butylamino-6-cyclopropylamino-s-triazine. These triazine compounds may be used alone or in combination of two or more.

The triazine-based compound may be used as a base, or may be a salt with an inorganic acid such as hydrochloric acid, sulfuric acid, nitric acid or phosphoric acid, or, for example, acetic acid, propionic acid, paratoluenesulfonic acid or the like. You may use it as a salt with the organic acid of.

In the present invention, examples of the triazole compound include compounds represented by the following general formula (2) and / or the following general formula (3).

[0028]

[Chemical 8] (In the formula, Y1, Y2 and Y3 are the same or different and each represents a hydrogen atom or a hydrocarbon group which may have a substituent, and A1 represents an aryl group or a substituent which may have a substituent. An optionally substituted aralkyl group, n is 1 to 3
Indicates an integer. ),

[0029]

[Chemical 9] (In the formula, Y4 and Y5 are the same or different and each represents a hydrogen atom or a hydrocarbon group which may have a substituent,
Represents an aryl group which may have a substituent or an aralkyl group which may have a substituent, and n represents an integer of 1 to 3. ) In the general formula (2), examples of the hydrocarbon group represented by Y1, Y2 and Y3 which may have a substituent include, for example, an alkyl group, an alkenyl group, an alkynyl group and a cycloalkyl group. And aryl groups and the like.

Examples of the alkyl group represented by Y1, Y2 and Y3 include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl and te.
Examples thereof include alkyl groups having 1 to 10 carbon atoms such as rt-butyl, pentyl, hexyl, heptyl, octyl, isooctyl, sec-octyl, tert-octyl, nonyl and decyl.

Examples of the alkenyl group represented by Y1, Y2 and Y3 include vinyl, allyl, isopropenyl, 1-propenyl, 2-propenyl and 2-methyl-1.
-C2-C4 alkenyl groups such as propenyl.

Examples of the alkynyl group represented by Y1, Y2 and Y3 include ethynyl, 1-propynyl and 2
-With 2 to 2 carbon atoms such as propynyl, butynyl, pentynyl, etc.
And the alkynyl group of 5.

Examples of the cycloalkyl group represented by Y1, Y2 and Y3 include cycloalkyl groups having 3 to 8 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.

Examples of the aryl group represented by Y1, Y2 and Y3 include aryl groups having 6 to 14 carbon atoms such as phenyl, naphthyl, anthryl and phenanthryl.

Examples of the substituent of the optionally substituted hydrocarbon group represented by Y1, Y2 and Y3 include a hydroxyl group, a halogen atom (eg chlorine, fluorine, bromine and iodine) and cyano. Group, amino group,
Carboxyl group, alkoxy group (for example, methoxy, ethoxy, propoxy, butoxy and other C1-4 alkoxy group), aryloxy group (for example, phenoxy group), alkylthio group (for example, methylthio,
1 carbon atom such as ethylthio, propylthio, butylthio
~ 4 alkylthio groups) and arylthio groups (eg phenylthio groups). Preferred are a halogen atom and an alkoxy group.
These substituents may be the same or different and may be substituted by 1 to 5, preferably 1 to 3.

Among the above-mentioned hydrocarbon groups which may have a substituent represented by Y1, Y2 and Y3, a hydrocarbon group which does not have a substituent is preferable, and among them, an alkyl group and a cyclo group are preferable. Alkyl groups are preferred. Y1,
The alkyl group represented by Y2 and Y3 is preferably an alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, and particularly preferably methyl. . Further, as the cycloalkyl group represented by Y1, Y2 and Y3, cyclopropyl is preferable.

Preferred examples of Y1, Y2 and Y3 include a hydrogen atom, an alkyl group and a cycloalkyl group. In a preferred embodiment, for example, Y1, Y2 and Y3 are both hydrogen atoms, Y1, Y2 and Y3. An embodiment in which both are alkyl groups and Y1, Y2 and Y3 are all cycloalkyl groups, for example, any two of Y1, Y2 and Y3 are alkyl groups and the rest are cycloalkyl groups or hydrogen atoms, Y1, Y2 and Y3. Of these, any two are cycloalkyl groups, the rest is an alkyl group or a hydrogen atom, and any two of Y1, Y2 and Y3 are hydrogen atoms and the rest are a cycloalkyl group or an alkyl group, for example, Of Y1, Y2 and Y3, any one is an alkyl group and any one is a cycloalkyl group, Include aspects is Riga hydrogen atom. Of these embodiments, Y1, Y2 and Y3 are all alkyl groups, and Y1, Y2 and Y
It is more preferable that any one of 3 is an alkyl group, any one is a cycloalkyl group, and the rest are hydrogen atoms.

Examples of the aryl group represented by A1 which may have a substituent include aryl groups having 6 to 14 carbon atoms such as phenyl, naphthyl, anthryl and phenanthryl. Preferably,
Examples include phenyl. Further, examples of the aralkyl group of the aralkyl group which may have a substituent represented by A1 include, for example, benzyl, 1-phenylethyl, 2-phenylethyl, 1-phenylpropyl, 2-phenylpropyl and 3-phenylpropyl. Ru, 1-phenylbutyl, 2
Examples thereof include aralkyl groups having 7 to 13 carbon atoms such as -phenylbutyl, 3-phenylbutyl, 4-phenylbutyl and diphenylmethyl. Preferred is 1-phenylethyl. Further, the substituent of the aryl group which may have a substituent or the aralkyl group which may have a substituent, which is represented by A1, is, for example, a hydroxyl group or a halogen atom (for example, chlorine, fluorine or bromine). And iodine), a cyano group, an amino group, a carboxyl group, an alkoxy group (for example, a C1-C4 alkoxy group such as methoxy, ethoxy, propoxy, butoxy), an aryloxy group (for example, a phenoxy group), Examples thereof include an alkylthio group (eg, an alkylthio group having 1 to 4 carbon atoms such as methylthio, ethylthio, propylthio and butylthio) and an arylthio group (eg, a phenylthio group). Preferred is a halogen atom. These substituents may be the same or different and may be substituted by 1 to 5, preferably 1 to 3.

Of these, the most preferable examples of the aryl group which may have a substituent or the aralkyl group which may have a substituent, represented by A1, are halogen-substituted phenyl and halogen-substituted. Has been 1-
Phenylethyl may be mentioned.

In the triazole compound represented by the general formula (2), n is preferably 1.

In the triazole compound represented by the general formula (3), the hydrocarbon group which may have a substituent represented by Y4 and Y5 is Y1,
Examples of the hydrocarbon group which may have a substituent represented by Y2 and Y3 include the same ones as described above, and among them, a hydrocarbon group having no substituent is preferable, and particularly, Alkyl groups are preferred. More preferably, methyl, ethyl, propyl, isopropyl,
n-butyl, isobutyl, sec-butyl, tert-
Examples thereof include alkyl groups having 1 to 4 carbon atoms such as butyl.
Preferred examples of Y4 and Y5 include a hydrogen atom and an alkyl group, and a preferred embodiment is, for example, Y
4 and Y5 are both hydrogen atoms, one of Y4 and Y5 is a hydrogen atom, the other is an alkyl group, and Y4 and Y5 are both alkyl groups.

Further, the aryl group optionally represented by A2 or the aralkyl group optionally substituted may be an aryl group optionally represented by A1. Examples of the aralkyl group which may have a substituent include the same ones as described above, preferably an aryl group which may have a substituent, and more preferably a halogen-substituted group. Examples include phenyl.

In the triazole compound represented by the general formula (3), n is preferably 1.

Such a triazole compound can be produced by a known method according to the specific compounds shown below. As a specific example thereof, for example, α- [2- (4-chlorophenyl) ethyl] -α- (1,1-dimethylethyl) -1H-1, represented by the following formula (4),
2,4-triazole-1-ethanol (conventional name: tebuconazole),

[0045]

[Chemical 10] 1-[[2- (2,4-dichlorophenyl) -4-n-propyl-1,3-dioxolan-2-yl] methyl] -1H-1,2,4-triazole represented by the following formula (5) (Common name: propiconazole),

[0046]

[Chemical 11] 1-[[2- (2,4-dichlorophenyl) -1,3-dioxolan-2-yl] methyl] -1H-1,2,4-triazole represented by the following formula (6) (conventional name: azaconazole) ,

[0047]

[Chemical 12] Α- (4-chlorophenyl) -α represented by the following formula (7)
-(1-Cyclopropylethyl) -1H-1,2,4-
Triazole-1-ethanol (common name: cyproconazole)

[0048]

[Chemical 13] And so on. More preferably, α- [2- (4-
Chlorophenyl) ethyl] -α- (1,1-dimethylethyl) -1H-1,2,4-triazole-1-ethanol (conventional name: tebuconazole). These triazole compounds may be used alone,
You may use 2 or more types together.

The ratio of the triazine compound and the triazole compound to be blended is, for example, 10 to 300 parts by weight, preferably 40 to 240 parts by weight of the triazole compound based on 100 parts by weight of the triazine compound.
Parts by weight, more preferably 50 to 200 parts by weight.

The triazine-based compound and the triazole-based compound may be blended, for example, by physically mixing them.
A known blending method may be used.

The industrial composition of the present invention obtained in this manner has excellent efficacy in antifungal and antialgae, and is therefore preferably used effectively as an antialgal agent and / or antifungal agent.

The industrial composition of the present invention may be prepared by blending a triazine-based compound and a triazole-based compound in advance and added to the object of application, or the triazine-based compound and the triazole-based compound may be added. The compound and the compound to be applied may be added individually to each other to act in the object to be applied.

When the industrial composition of the present invention is used as an antifungal agent and / or an antialgal agent, it may be, for example, a liquid agent (including a water suspension agent and an oil agent), depending on its purpose and use. It can be formulated into known dosage forms such as pastes, powders, granules, and microcapsules and used. Further, it may be prepared as an inclusion compound, and further, montmorillonite such as layered silicate (smectites, etc.)
It may be prepared by supporting it on, or adsorbing it on clay, silica, white carbon, talc, or the like.

Of these, for example, for formulation as a liquid preparation, the triazine-based compound and the triazole-based compound may be dissolved or dispersed in a solvent in the above-described proportions. More specifically, for example, if the triazine-based compound and the triazole-based compound are mixed in a proportion of 1 to 20% by weight and 1 to 20% by weight with respect to 60 to 98% by weight of the solvent and dissolved or dispersed, Good.

The solvent used at this time is not particularly limited as long as it can dissolve or disperse the triazine compound and the triazole compound.

Examples of such a solvent include water such as methanol, ethanol, n-propanol, and i.
Alcoholic solvents such as so-propanol, n-butanol, tert-butanol, 3-methyl-3-methoxybutanol, such as ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, Glycol-based solvents such as 1,4-butanediol, 1,5-pentanediol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, tripropylene glycol monomethyl ether,
For example, acetone, methyl ethyl ketone, methyl isobutyl ketone, ketone solvents such as propylene carbonate, for example, dioxane, tetrahydrofuran, ether solvents such as ethyl ether, for example, ethyl acetate,
Ester solvents such as butyl acetate, isobutyl acetate, 3-methyl-3-methoxybutyl acetate, γ-butyrolactone, dimethyl adipate, dimethyl glutarate, dimethyl succinate, for example, benzene, toluene, xylene, methylnaphthalene, dimethylnaphthalene. Aromatic solvents such as isopropylnaphthalene, diisopropylnaphthalene, ethylbiphenyl, diethylbiphenyl and solvent naphtha, for example, carbon tetrachloride, chloroform, halogenated hydrocarbon solvents such as methylene chloride, for example, dimethylformamide, dimethylacetamide,
Examples thereof include polar solvents such as dimethyl sulfoxide, acetonitrile and N-methylpyrrolidone.

Further, an industrially used aliphatic petroleum solvent or aromatic petroleum solvent may be used. Examples of the aliphatic petroleum solvent include mineral spirits. As the aromatic petroleum solvent, commercially available products such as MSP (distillation range (° C) 90 to 120,
Specific gravity (15/4 ° C) 0.820 or more, mixed aniline point (° C) 26 or less, aromatic content (volume%) 70 or more), Superzole 100 (distillation range (° C) 95 to 111, specific gravity (15/4) ℃) 0.825, mixed aniline point (℃) 2
6.0, aromatic content (volume%) 75 or more), pegazole ARO-80 (distillation range (° C) 104 to 123, specific gravity (15/4 ° C) 0.832, mixed aniline point (° C) 2
6, aromatic content (volume%) 75.9), Swazol 10
0 (distillation range (° C) 106 to 116, specific gravity (15/4
C) 0.835, mixed aniline point (C) 24.6, aromatic content (volume%) 76.4), Swazol 200 (distillation range (C) 132 to 144, specific gravity (15/4 C) 0.8.
44, mixed aniline point (° C) 23.8, aromatic content (volume%) 80.9), MHS (distillation range (° C) 140-1)
70, specific gravity (15/4 ° C.) 0.86 to 0.88, mixed aniline point (° C.) 11 to 12, aromatic content (volume%) 98
Above), high arom 2S (distillation range (° C) 152 to 18)
7, specific gravity (15/4 ° C.) 0.816, mixed aniline point (° C.) 47 or less, aromatic content (volume%) 45 to 55),
Swazol 310 (distillation range (° C) 153-177, specific gravity (15/4 ° C) 0.817, mixed aniline point (° C) 4
3.6, aromatic content (volume%) 51.0), Superzole 150 (distillation range (° C) 153-197, specific gravity (1
5/4 ° C.) 0.815, mixed aniline point (° C.) 21.
5, aromatic content (volume%) 50 or more), Shoishi Hysol (distillation range (° C) 153-198, specific gravity (15.6 / 1)
5.6 ° C) 0.818, aromatic content (volume%) 55),
HAWS (distillation range (° C) 154-190, specific gravity (15
/ 4 ° C) 0.822, aromatic content (volume%) 50), Superzol 1500 (distillation range (° C) 155-17
1, specific gravity (15/4 ° C) 0.869, mixed aniline point (° C) 14.6, aromatic content (volume%) 98 or more), Nisseki Hysol 100 (distillation range (° C) 155 to 180,
Specific gravity (15/4 ° C.) 0.870 to 0.880, mixed aniline point (° C.) 15 or less, aromatic content (volume%) 99.0
Above), Vegasol R-100 (distillation range (° C) 156
˜174, specific gravity (15/4 ° C.) 0.874, mixed aniline point (° C.) 14, aromatic content (volume%) 96.4), Solvesso 100 (distillation range (° C.) 158 to 177, specific gravity (15 / 4 ℃) 0.870, mixed aniline point (℃) 1
4, aromatic content (volume%) 98.0), MSS (distillation range (° C) 158 to 180, specific gravity (15.6 / 15.6)
C) 0.86-0.89, mixed aniline point (C) 13-
14, aromatic content (volume%) 98 or more), SHELLS
OL A (distillation range (° C) 160 to 182, specific gravity (15
/ 4 ° C) 0.873, aromatic content (volume%) 98), Swazol 1000 (distillation range (° C) 162 to 176, specific gravity (15/4 ° C) 0.878, mixed aniline point (° C) 1
2.7, aromatic content (volume%) 99.7), Idemitsu Ipsol 100 (distillation range (° C) 162 to 179, specific gravity (1
5/4 ° C.) 0.875, mixed aniline point (° C.) 13.
5, aromatic content (volume%) 99.5 or more), Shoishi Tokusol (distillation range (° C) 162-180, specific gravity (15 /
4 ° C.) 0.881, mixed aniline point (° C.) 12.6, aromatic content (volume%) 99.99), Swazol 1500
(Distillation range (° C) 180-207 Specific gravity (15/4 ° C)
0.886, mixed aniline point (° C) 16.5, aromatic content (volume%) 98.8), Nisseki Hysol 150 (distillation range (° C) 182 to 216, specific gravity (15/4 ° C) 0.8)
87 to 0.904, mixed aniline point (° C) 17 or less, aromatic content (volume%) 99.0 or more), Superzole 1
800 (distillation range (° C) 183-208, specific gravity (15 /
4 ° C.) 0.889, mixed alinine point (° C.) 15.7, aromatic content (volume%) 99 or more), Solvesso 150 (distillation range (° C.) 185-211, specific gravity (15/4 ° C.) 0.
896, mixed aniline point (° C) 18.3, aromatic content (volume%) 97.3), Idemitsu Ipsol 150 (distillation range (° C) 186 to 205, specific gravity (15.6 / 15.6).
℃) 0.895, mixed aniline point (℃) 15.2, aromatic content (volume%) 99.5 or more), SHELLSOL
AB (distillation range (° C) 187 to 213, specific gravity (15/4
C.) 0.894, aromatic content (volume%) 99.5), Pegazole R-150 (distillation range (C) 191-212,
Specific gravity (15/4 ℃) 0.890, mixed aniline point (℃)
18, aromatic content (volume%) 97.2), Swazol 1
800 (distillation range (° C) 197 to 237, specific gravity (15 /
4 ° C.) 0.940, mixed aniline point (° C.) 14.0, aromatic content (volume%) 99.6).

Of these, glycol solvents, aromatic solvents and aromatic petroleum solvents are preferable. These solvents may be used alone or in combination of two or more kinds.

Further, the industrial composition of the present invention has known additives such as other anti-algal and / or antifungal agents, surfactants, antioxidants and light stabilizers depending on its purpose and use. Etc. may be added.

Other algae and / or fungicides include, for example, 3-iodo-2-propynyl-butyl-carbamate, diiodomethyl-p-tolylsulfone and p-chlorophenyl-3-iodopropargylformal. Organic iodine compounds such as 4,5-dichloro-1,2-dithiol-3-one and other dithiol compounds such as 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide Thiophene-based compounds, for example, thiocarbamate-based compounds such as tetramethylthiuram disulfide, for example, 2,
Nitrile compounds such as 4,5,6-tetrachloroisophthalonitrile, such as N- (fluorodichloromethylthio) -phthalimide and N- (fluorodichloromethylthio) -N, N'-dimethyl-N-phenyl-sulfamide. A haloalkylthio compound of, for example,
Pyridine compounds such as 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine, for example, pyrithione compounds such as zinc pyrithione and sodium pyrithione, such as 2- (4-thiocyanomethylthio) benzothiazole A benzothiazole compound, for example, 3- (3,4-dichlorophenyl) -1,
Urea compounds such as 1-dimethylurea, for example, methyl-2-benzimidazole carbamate, 2- (4-
Imidazole compounds such as thiazolyl) -benzimidazole, eg 2-n-octyl-4-isothiazolin-3-one, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, Nn Isothiazoline compounds such as -butyl-benzisothiazolin-3-one and 1,2-benzisothiazolin-3-one, for example, 3-benzo [b] thien-2-yl-5,6-dihydro-1,4. Examples thereof include oxathiazine compounds such as 2-oxathiazine 4-oxide.

These other algae and / or fungicides may be used alone or in combination of two or more. Further, the blending ratio of these is appropriately determined depending on the dosage form, purpose and use.

As the surface active agent, for example, known surface active agents such as soaps, nonionic surface active agents, anionic surface active agents, cationic surface active agents, amphoteric surface active agents, polymeric surface active agents, etc. An activator can be used, and preferably, a nonionic surfactant and an anionic surfactant are used.

Examples of nonionic surfactants include:
Examples thereof include polyoxyalkylene aryl phenyl ethers, polyoxyethylene nonyl phenyl ethers, and block copolymers of ethylene oxide and propylene oxide.

Examples of anionic surfactants include:
Examples thereof include alkylbenzene sulfonic acid metal salts, alkylnaphthalene sulfonic acid metal salts, polycarboxylic acid type surfactants, dialkyl sulfosuccinic acid ester metal salts, polyoxyethylene distyrenated phenyl ether sulfate ammonium salts, and lignin sulfonic acid metal salts. Examples of these metal salts include sodium salt, potassium salt, magnesium salt and the like.

As the antioxidant, for example, 2,
6-di-t-butyl-4-methylphenol, 2,2 '
-Phenolic antioxidants such as methylenebis [4-methyl-6-t-butylphenol], for example, amine antioxidants such as alkyldiphenylamine and N, N'-di-s-butyl-p-phenylenediamine. Can be mentioned.

These surfactants and antioxidants are
For example, in the case of a liquid agent, 0.1 to 5 parts by weight is added to 100 parts by weight of the liquid agent.

Examples of the light stabilizers include hindered amine light stabilizers such as bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate.

In the case of a liquid agent, such a light stabilizer is added in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the liquid agent.

The industrial composition of the present invention thus obtained is excellent in heat resistance, water resistance, weather resistance and alkali resistance and can exhibit an antialgal effect and a fungicide effect.

Therefore, for example, various industrial waters such as a pulp and paper mill, a cooling water circulation process, an oil agent for metal processing such as cutting oil, casein, starch paste, glue, coated paper, coating liquid for paper, surface size Effective in anti-algal and anti-fungal applications such as agents, paints, adhesives, synthetic rubber latex, printing inks, polyvinyl alcohol films, vinyl chloride films, plastic products, cement admixtures, sealants, joint products, and other industrial products. Can be used.

In particular, since the industrial composition of the present invention is excellent in water resistance and weather resistance, it can be used in rainwater, moisture, or
It can be preferably used even in indoor and outdoor environments where it receives ultraviolet rays such as sunlight, and moreover, since it is particularly excellent in alkali resistance (pH 8 to 12), its application target is:
The effect can be effectively exhibited not only in oiliness but also in water. Therefore, it can be suitably used for water-based and oil-based paints and adhesives used in such an environment, or plastic products.

Therefore, more specifically, the industrial composition of the present invention is an oil-based or water-based outdoor paint (outer wall paint, etc.), outdoor adhesive, ship bottom paint, outdoor vinyl film (agricultural vinyl film, etc.). It can be suitably used for various plastic products, sealing agents, jointing agents and the like.

The amount of the industrial composition of the present invention to be added may be appropriately determined depending on the object of application, but is 10 to 2
It is preferable to use a concentration of 0000 mg (active ingredient) / kg (product), preferably 200 to 10000 mg (active ingredient) / kg (product).

[0074]

EXAMPLES The present invention will be described more specifically with reference to Examples and Comparative Examples.

(1) Preparation of Industrial Compositions of Examples and Comparative Examples Using the following as active ingredients and solvents, these were blended in the proportions shown in Table 1 and then stirred. The industrial compositions of Examples 1 and 2 and Comparative Examples 1 and 2 were prepared.

Triazine compound: Irgalol 107
1 (trade name, manufactured by Ciba Specialty Chemicals, 2
-Methylthio-4-t-butylamino-6-cyclopropylamino-s-triazine, containing 98% by weight) Triazole compound: tebuconazole (manufactured by Bayer, containing 98% by weight) Solvent: methyl carbitol (diethylene glycol monomethyl ether) Example 1 90 g of methyl carbitol and 5 g of irgarol 1
071 and 5 g of tebuconazole were added and stirred at room temperature to obtain 100 g of an almost transparent liquid industrial composition.

Example 2 To 90 g of methyl carbitol, 7.5 g of irgalol 1071 and 2.5 g of tebuconazole were added and stirred at room temperature to obtain 100 g of an almost transparent liquid industrial composition. .

Comparative Example 1 To 90 g of methyl carbitol was added 10 g of Irgalol 1071 and the mixture was stirred at room temperature to obtain 100 g of an almost transparent liquid industrial composition.

Comparative Example 2 To 90 g of methyl carbitol was added 10 g of tebuconazole, and the mixture was stirred at room temperature to obtain 100 g of an almost transparent liquid industrial composition.

[0080]

[Table 1] (2) Preparation of test coating film 1) To the acrylic / styrene emulsion coating composition having the composition shown in Table 2, 1.0% by weight of the industrial composition of each Example and each Comparative Example was added and mixed.

2) Each coating material was uniformly applied to a 3 cmφ filter paper, and after the coating film was prepared, it was dried for 24 hours to obtain a test coating film.

[0082]

[Table 2] (Mill base) Dispersant: polycarboxylic acid sodium salt (trade name: Orotan 850, manufactured by Rohm and Haas) Wetting agent: alkyl ether sulfate (trade name: Triton CF-10, manufactured by Union Carbide) Defoamer : Mixture of mineral oil and polyethylene glycol type nonionic surfactant (trade name: Nopco 8043-L, manufactured by San Nopco Ltd.) Titanium white: rutile titanium oxide (trade name: TITANI
X JR-900, manufactured by Teika Co., Ltd. (let down) Emulsion: acrylic / styrene emulsion (trade name: Ultrasol C-62, manufactured by Ganz Kasei Co., Ltd.) Film forming aid: 2,2 4-Trimethyl-1,3-pentanediol monoisobutyrate (trade name: CS-12, manufactured by Chisso Corporation) Defoaming agent: Mixture of mineral oil and polyethylene glycol type nonionic surfactant (Product surface: Nopco 8034-L, manufactured by San Nopco) Preservative: Nitrogen halide sulfur compound (trade name: Slaoff CA, manufactured by Takeda Pharmaceutical Co., Ltd.) Thickener: Hydroxyethyl cellulose (trade name: SP-
600, a 2% by weight aqueous solution of Daicel Co., Ltd. (3) Algae control test 1) Each test coating film obtained in (2) above is left in a thermostat at 150 ° C. for 24 hours, and then at room temperature. A heat resistance test sample was prepared by leaving it to stand for 24 hours.

2) Each test coating film obtained in the above (2) was
A water resistance test sample was prepared by immersing it in a 200 mL water tank at 40 ° C. for 3 days and then leaving it at room temperature for 24 hours.

3) The test coating films obtained in (2) above were
After exposure to the germicidal lamp of a clean bench for 7 days, at room temperature, 2
A UV resistance test sample was prepared by leaving it to stand for 4 hours.

4) Three kinds of mixed algae liquid (Chlamydomonas reinhardtii) (C-
238), Euglena gracili
s) (NIES-47), Chlorel SP
la sp.)) is sprayed onto an arene medium to which each test sample (heat resistance test sample, water resistance test sample and UV resistance test sample) is attached, and light irradiation (bright state: 16 hours, dark state: Culturing was carried out for 8 hours), and then the growth state of algae was judged. The results are shown in Table 1.

In Table 1, the result of the algae control test of the heat resistance test sample is "heat resistant and algae resistance", the result of the algae test of the water resistance test sample is "water resistance and algae resistance", and the algae resistance of the ultraviolet light resistance test sample is The result of the test is shown as "UV algae resistance". In addition, in Table 1, an algae control test example in which the industrial composition of each Example and each Comparative Example is not added is also shown as a “control”.

Further, in Table 1, the judgment of the growth state is
According to the following criteria.

-: No algae growth is observed on the surface of the test sample.

±: Growth of algae is slightly observed on the surface of the test sample.

+: Growth of algae is observed in an area of 1/3 or less of the surface of the test sample.

++: Growth of algae is observed in an area less than 2/3 of the surface of the test sample.

+++: Growth of algae is observed in an area of 2/3 or more of the surface of the test sample.

(4) Antifungal test 1) Each test coating film obtained in (2) above was allowed to stand in a thermostat at 150 ° C. for 24 hours, and then allowed to stand at room temperature for 24 hours to obtain a heat resistance test sample. Was prepared.

2) The test coating films obtained in (2) above were
A water resistance test sample was prepared by immersing it in a 200 mL water tank at 40 ° C. for 3 days and then leaving it at room temperature for 24 hours.

3) Each test coating film obtained in the above (2) was
After exposure to the germicidal lamp of a clean bench for 7 days, at room temperature, 2
A UV resistance test sample was prepared by leaving it to stand for 4 hours.

4) Four-type mixed spore suspension (Aspergillus niger, black mold) (IFO-63
41), Penicillium citrinum
num, blue mold) (IFO-6352), Cladosporium cladosporioi
des Kurokawa fungus) (IFO-6348), and Alternaria sp. Cultured at 28 ° C. Four weeks after culturing, the mold growth state on each test sample was determined. The results are shown in Table 1.

In Table 1, the results of the antifungal test of the heat resistance test sample are "heat and mold resistance", the results of the antifungal test of the water resistance test sample are "water resistance and fungus resistance", and the antifungal properties of the ultraviolet resistance test sample are shown. The result of the test is shown as "UV resistance". In Table 1, the antifungal test examples to which the industrial compositions of Examples and Comparative Examples are not added are also shown as “control”.

Further, in Table 1, the determination of the growth state is
According to the following criteria.

-: No mold growth was observed on the test sample surface.

±: Very little mold growth is observed on the test sample surface.

+: Mold growth is observed in an area of 1/3 or less of the test sample surface.

++: Mold growth is observed in an area of less than 2/3 of the test sample surface.

+++: Mold growth is observed in an area of 2/3 or more of the surface of the test sample.

As is clear from Table 1, in the test samples to which the industrial composition of each example was added, the antifungal effect and the antifungal effect were obtained with respect to the test samples to which the industrial composition of each comparative example was added. It can be seen that the algae effect is excellent. From this, the industrial composition of each example was added to an alkaline coating, the resulting coating film was heated, immersed in water, and even after irradiation with ultraviolet rays, a good algae preventive action was obtained. It can be seen that the effect and antifungal effect can be exhibited.

[0105]

Industrial Applicability As described above, the industrial composition of the present invention is excellent in heat resistance, water resistance, weather resistance and alkali resistance, and can exhibit an antialgal effect and a fungicide effect. Therefore, it can be suitably used even in indoor and outdoor environments where it receives ultraviolet rays such as rainwater and moisture, or sun rays. Furthermore, since it has excellent alkali resistance, its application target is not only oiliness. Even if it is water-based,
The effect can be effectively expressed. Therefore,
It can be suitably used for water-based and oil-based paints and adhesives used in such an environment, or plastic products.

Claims (9)

[Claims] 1. An industrial composition containing a triazine compound and a triazole compound. 2. A triazine-based compound is represented by the general formula (1): (Wherein R 1, R 2, R 3 and R 4 represent a hydrogen atom or a hydrocarbon group which may have a substituent, and X represents a halogen atom or an alkylthio group). The industrial composition according to claim 1, wherein 3. In the formula of the general formula (1), R1 and R2 are a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R3
And R4 is an alkyl group having 1 to 5 carbon atoms which may be substituted by an alkoxy group having 1 to 4 carbon atoms or a cycloalkyl having 3 to 6 carbon atoms which may be substituted by an alkoxy group having 1 to 4 carbon atoms It is a group, X is a halogen atom or a C1-C4 alkylthio group, The industrial composition of Claim 2 characterized by the above-mentioned. 4. The triazine-based compound is 2-methylthio-4-t-butylamino-6-cyclopropylamino-
s-triazine, 2-chloro-4,6-diethylamino-
s-triazine, 2-chloro-4-ethylamino-6-
It is at least one kind selected from the group consisting of isopropylamino-s-triazine and 2-methylthio-4-ethylamino-6- (1,2-dimethylpropylamino) -s-triazine, and 1-3
The industrial composition according to any one of 1. 5. A triazole-based compound is represented by the general formula (2): (In the formula, Y1, Y2 and Y3 are the same or different and each represents a hydrogen atom or a hydrocarbon group which may have a substituent, and A1 represents an aryl group or a substituent which may have a substituent. An optionally substituted aralkyl group, n is 1 to 3
Indicates an integer. ) And / or general formula (3) (In the formula, Y4 and Y5 are the same or different and each represents a hydrogen atom or a hydrocarbon group which may have a substituent,
Represents an aryl group which may have a substituent or an aralkyl group which may have a substituent, and n represents an integer of 1 to 3. ) Is a compound represented by
The industrial composition according to any one of claims 1 to 4. 6. The triazole-based compound has the general formula (2):
Is a compound represented by the formula (2):
1, Y2 and Y3 are the same or different and each is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, and A1 is a halogen-substituted phenyl group or a halogen-substituted phenylalkyl group. The industrial composition described. 7. The triazole-based compound has the general formula (3):
Is a compound represented by the formula (3), wherein Y4
And Y5 are both hydrogen atoms, or one is a hydrogen atom and the other is a hydrocarbon group having 1 to 4 carbon atoms, and A2 is a halogen-substituted phenyl group. Composition. 8. The triazole compound is α- [2-
(4-Chlorophenyl) ethyl] -α- (1,1-dimethylethyl) -1H-1,2,4-triazole-1-
Ethanol, 1-[[2- (2,4-dichlorophenyl) -4-n-propyl-1,3-dioxolane-2-
Iyl] methyl] -1H-1,2,4-triazole, 1
-[[2- (2,4-Dichlorophenyl) -1,3-dioxolan-2-yl] methyl] -1H-1,2,4-
Triazole, α- (4-chlorophenyl) -α- (1
-Cyclopropylethyl) -1H-1,2,4-triazole-1-ethanol, which is at least one selected from the group consisting of the chemical compositions according to any one of claims 1 to 7. object. 9. The industrial composition according to any one of claims 1 to 8, which is an antialgal agent and / or an antifungal agent.