JPH11292724A - Mold removing agent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a compound having neither pungent odor nor reduction in mold removing ability with time, suitable for essential removal of mold, by formulating a peroxy compound and a metal complex with a specific amount of an oxide or a hydroxide of the same metal as that of the metal complex. SOLUTION: This mold removing agent composition is obtained by formulating a mold removing agent composition containing (A) a peroxy compound and a (B) a metal complex with (c) 0.005-0.25 wt.% of an oxide or a hydroxide of the same metal as that of the metal complex. For example, the metal complex is preferably a metal complex of the formula; [LnMmXp]<z> Yq M is a divalent to tetravalent transition metal selected from V, Cr, Mn, Fe, Co, Ni and Cu in an oxidation state; (n) and (m) are each 1-4; X is a coordination species or a cross-linking species; (p) is 0-12; Y is a counterion and is dependent on an electric charge (Z) of the complex; (q) is z/(the electric charge of Y); L is a ligand containing the formula [R<1> and R<2> are each O, H, a (substituted) alkyl or the like; (t) an (t') are each 2-3; each D is N, O, S or the like; (s) is 2-5] containing a ligand which is a macrocyclic organic molecule.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an oxygen-based mold remover composition which is suitable for removing mold without generating harmful gas during use and without irritating odor.

[0002]

2. Description of the Related Art Bathrooms, bathtubs, toilets around houses,
Stain, such as sinks, especially where water is used frequently, is often due to organic or insoluble inorganic substances caused by mold,
Since ordinary detergents containing surfactants as the main component cannot be easily removed, to remove these stains, use a chlorine- or oxygen-based bleaching agent as the main component, and bleach it. A method has been adopted in which the effect makes the color of the mold inconspicuous.

[0003] However, those containing a chlorine bleach such as sodium hypochlorite as a main component are excellent in the bleaching power of mold dye and the performance of removing mold, but have a great risk of damaging eyes and skin. Above all, it has a strong chlorine smell, and must be carefully ventilated when used, and has the drawback of generating harmful chlorine gas when used incorrectly with an acidic cleaning agent. .

[0004] On the other hand, those containing an oxygen-based bleaching agent represented by hydrogen peroxide as a main component do not have a drawback of generating chlorine gas, but can provide a sufficient bleaching effect of a mold dye by themselves. Therefore, various bleach activators had to be used in combination (for example, see JP-A-2-225).
No. 600, JP-A-2-196896, JP-A-62-4
No. 794).

However, even when these organic peracid-based bleaching activators are used in combination, the bleaching effect on mold dyes is only slightly improved, and it is still insufficient in terms of removal of mold itself. The drawback that it is easy to stick remains.

In order to solve the above-mentioned drawbacks, the present inventors have previously proposed an oxygen-based mold remover composition using a metal complex, particularly a metal complex having a ligand which is a macrocyclic organic molecule. (Japanese Patent Application No. 9-62272, Japanese Patent Application No. 9-87)
778, etc.). However, when the metal complex is used in the mold remover composition, although it is excellent in removing the mold itself, there is a disadvantage that the mold removing ability decreases with time.

[0007]

SUMMARY OF THE INVENTION Accordingly, the present invention has been made in view of the above-mentioned circumstances of the prior art, and has no irritating odor and is suitable for the removal of mold itself without a decrease in mold removing ability with time. It is an object of the present invention to provide a composition in which

[0008]

Means for Solving the Problems In the development of a composition exhibiting a strong mold removing ability and having no irritating odor, in order to develop a composition whose mold removing ability does not decrease over time, As a result of intensive research, the peroxy compound and the metal complex, particularly a metal complex having a ligand that is a macrocyclic organic molecule, are allowed to coexist in a specific range with an oxide or hydroxide of the same kind of metal as the complex, The present inventors have found that it is possible to prevent the deterioration of the mold removing ability over time while maintaining the mold removing ability, and have completed the present invention based on this finding.

That is, according to the present invention, first, in a mold remover composition containing (A) a peroxy compound and (B) a metal complex, (C) a mold removal agent composition containing the same metal as the above metal complex A fungicide composition comprising 0.005 to 0.25% by weight of an oxide or hydroxide. Second, the metal complex is a metal complex having a ligand which is a macrocyclic organic molecule, and is a compound represented by the following general formula [A]. An absorbent composition is provided.

Embedded image [Wherein, M is V, Cr, Mn, Fe, Co, Ni, Cu
A transition metal in the II- to V-valent oxidation state selected from the group consisting of, or a mixture thereof, n and m each represent an integer of 1 to 4, X represents a coordinating species or a crosslinking species, and p represents 0 to 12 Is an integer and Y is a counter ion, the type of which depends on the charge z of the complex, which can be positive, zero or negative, where q is z / (Y
And L is the following general formula [B]:

Embedded image (Wherein R ¹ and R ² are O, H, an optionally substituted alkyl group or aryl group, and t and t ′ are each 2 to
And each D is N, NR, PR, O or S, where R is H, an optionally substituted alkyl or aryl group, and s is an integer of 2-5 ,)
Is a ligand having ]

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The mold remover composition of the present invention is a metal complex having (A) a peroxy compound and (B) a metal complex, preferably a ligand which is a macrocyclic organic molecule, and is represented by the general formula [A]. A mold remover composition comprising: (C) 0.005 to 0.25% by weight of an oxide or hydroxide of the same kind of metal as the metal complex. I do.

In the present invention, the peroxy compound used as the component (A) includes hydrogen peroxide, a hydrogen peroxide releasing compound, a hydrogen peroxide generating system, peroxy acids and salts thereof, peroxy acid precursor systems, and mixtures thereof. There is.

Examples of the hydrogen peroxide source include peroxides of alkali metals, organic peroxides such as urea peroxide, and inorganic peroxides such as alkali metal perborates, percarbonates, perphosphates and the like. Persulfates. Two or more of these compounds may be mixed. Among them, particularly preferred are hydrogen peroxide, sodium percarbonate, sodium perborate and potassium persulfate.

These compounds may be used alone or in combination with a peroxyacid precursor. These peroxyacid precursors include those used with hydrogen peroxide and hydrogen peroxide releasing compounds to produce organic peracids in the bath. Specifically, esters such as acyl phenol sulfonate, acyl alkyl phenol sulfonate, acyl phenol carboxylate, acylated citrate, acyl alkyl phenol carboxylate, ester of aromatic divalent carboxylic acid and alcohol having quaternized amine, etc. , Sodium-4-benzoyloxybenzenesulfonate, sodium-1-
Methyl-2-benzoyloxybenzene-4-sulfonate, sodium nonanoyloxybenzenecarboxylate, sodium decanoyloxybenzenecarboxylate, acetyltriethyl citrate, 2- (4-
Methoxycarbonylbenzoyloxy) -N, N, N-
Trimethylethaneaminium methosulfate and the like.

Further, acylamides include N, N,
N ′, N′-tetraacetylethylenediamine, and quaternary ammonium-substituted peroxy precursors include:
N, N, N, -trimethylammonium toluyloxybenzenesulfonate, 2- (N, N, N-trimethylammonium) ethyl-4-sulfophenyl carbonate and the like can be mentioned.

The content of these peroxy compounds is not particularly limited, but may be 1 to 3 in the mold remover composition bath.
0% by weight, preferably 5 to 20% by weight.

In the present invention, examples of the metal complex used as the component (B) include those in which a ligand is bonded around a central metal. Specifically, bidentate ligands such as pyridine and ethylenediamine, tridentate or more planar ligands such as terpyridine and porphyrin, tridentate or more steric ligands such as cyclic amines, and ligands such as dinuclear defined ligands and the like One in which a ligand is bonded to a metal is exemplified.

Here, the center metal includes transition metals, and among them, V, Cr, Mn, Fe, C
o, Ni, Cu, Zn, Mo, Tc, Ru, Rh, P
II-VII selected from d, W, Re, Ir, Pt, Au
Transition metals in the multivalent oxidation state are preferred.

Among these, a preferred metal complex is a metal complex having a ligand which is a macrocyclic organic molecule, and examples thereof include those represented by the following general formula [A].

Embedded image [Wherein, M is V, Cr, Mn, Fe, Co, Ni, Cu
A transition metal in the II- to V-valent oxidation state selected from the group consisting of, or a mixture thereof, n and m each represent an integer of 1 to 4, X represents a coordinating species or a crosslinking species, and p represents 0 to 12 Is an integer and Y is a counter ion, the type of which depends on the charge z of the complex, which can be positive, zero or negative, where q is z / (Y
And L is the following general formula [B]:

Embedded image (Wherein R ¹ and R ² are O, H, an optionally substituted alkyl group or aryl group, and t and t ′ are each 2 to
And each D is N, NR, PR, O or S, where R is H, an optionally substituted alkyl or aryl group, and s is an integer of 2-5 ,)
Is a ligand having ]

That is, V, Cr, Mn, F
Based on e, Co, Ni, Cu, the following general formula [A]:

Embedded image Wherein M is II, III, IV or V
X represents a metal in a multivalent oxidation state or a mixture thereof, wherein X is a coordinating species or a bridging species, for example, H ₂ O, OH ⁻ , O ²⁻ ,
S ²⁻ ,> S = O, N ³⁻ , HOO ⁻ , O ₂ ²⁻ , O ₂ ⁻ , RC
OO ^-, NR ₃ (where, R represents H or a substituted or unsubstituted alkyl group or aryl ^group), Cl -, SCN ^-, etc.,
Or a combination thereof, wherein p is 0 to 12, preferably 3
And Y represents a counter ion having a property based on the charge z of the complex, z represents the charge of the complex as a positive integer, 0 or a negative integer, and when z is positive, Y is an anion, Cl ^{-,
_{Br -, I -, NO 3}} -, ClO 4 -, NCS -, PF 6 -, R
SO ₄ ⁻ , OAc ⁻ , CF ₃ SO ₃ ⁻ , RSO ₃ ^{− and the} like, and z
Is negative, Y represents a cation such as an alkali metal, alkaline earth metal or ammonium cation, and q represents z /
(Charge of Y), and L is the following general formula [B]:

Embedded image (Wherein each of R ¹ and R ² represents O, H, a substituted or unsubstituted alkyl group or an aryl group, D is each independently N, NR, PR, O or S, and R is H Represents a substituted or unsubstituted alkyl group or aryl group,
D is one of -N unsaturated = CR heteroatom carbon atoms bound to the D when N ₁ - fragment is formed, each of t and t 'is an integer independently 2 or 3, s is 2 ,
3, 4 or 5), which is a ligand comprising a macrocyclic organic molecule represented by the following formula:

In the general formula [A] of the metal complex shown above, the coordinating species or bridging species X is preferably a small coordinating ion or bridging molecule or a combination thereof.
Is preferably the following general formula [C]:

Embedded image (Wherein each of R ¹ and R ² represents O, H, a substituted or unsubstituted alkyl or aryl group, and each of D and D ′ is individually N, NR, PR, O or S; R represents H, a substituted or unsubstituted alkyl group or an aryl group, each of t and t ′ is independently an integer of 2 or 3, and s is an integer of 2 to 4) Formula organic molecules.

In the general formula [A], preferably n
= M = 2. Further, preferred ligands are those in which D or D ′ is NH or N in the general formula [B] or [C].
R is a complex in which t and t ′ are 2 or 3, s is 2, R ¹ and R ² are H or an alkyl group, and a more preferred ligand is D or D ′ is NCH ₃ and t = t '= 2,
s is 2, and each of R ¹ and R ² is a complex showing H or an alkyl group.

Examples of the simplest form of ligand include:
Those represented by the following formulas (I) to (IV) are exemplified.

[0023]

Embedded image

[0024]

Embedded image

[0025]

Embedded image

[0026]

Embedded image

The metal complex having these ligands may be formed in advance or formed in a mold remover composition bath. The metal complex having these ligands may be mononuclear or polynuclear. Depending on the type of ligand and the oxidation state of the metal, a binuclear or polynuclear metal complex can be formed. In the complex, the coordinating species and / or the bridging species form a bridge between the metal centers.

The most preferred of these ligands are 1,4,7-trimethyl-1,1 of the formula (III)
4,7-Triazacyclononane (abbreviation Me-TACN)
Is mentioned.

Specific examples of the metal complex include those shown in Table 1 below.

[0030]

[Table 1]

Although the content of the metal complex is not particularly limited,
In the mold remover composition bath, 0.01 to 1000 p
pm, preferably 1 to 500 ppm.

In the present invention, the metal oxide or hydroxide as the component (C) must have the same central metal as the metal complex of the component (B), but the valence is not necessarily the same. No need.

These metal oxides or metal hydroxides are
Generally, it is hardly soluble, and it is not always necessary to dissolve all of them in the mold remover composition bath, but its content needs to be 0.005 to 0.25% by weight. 0.
When the amount is less than 005% by weight, the effect of suppressing the decrease in mold removing ability over time is small, and when the amount exceeds 0.25% by weight, the decrease in mold removing ability over time is observed.

Specific examples of these metal oxides or metal hydroxides include vanadium (V) oxide and chromium oxide (II
I), chromium (IV) oxide, chromium (III) hydroxide hydrate,
Manganese (IV) oxide, iron (III) oxide, iron (II) oxide,
Ferric oxide (III), iron hydroxide (II), iron hydroxide oxide (II
I), cobalt (II) oxide, cobalt (III) oxide, nickel (II) oxide, nickel (II) hydroxide, copper (I) oxide, copper (II) oxide, copper (II) hydroxide and the like. .

In the present invention, the pH of the mold remover solution is arbitrary, but is preferably alkaline. As the alkaline substance for this purpose, hydroxides of alkali metals and ammonium, carbonates, bicarbonates, and the like may be used as long as they dissolve in water and exhibit alkalinity, but are easy to handle and easy to adjust pH. Sodium carbonate or potassium carbonate is preferred in this respect. Particularly preferred is potassium carbonate.

The content of these alkaline substances is not particularly limited, but is 0.1 to 0.1% in the mold remover composition bath.
It is 20% by weight, preferably 1 to 10% by weight.

The mold remover composition of the present invention may optionally contain a surfactant, a builder, a radical scavenger, an alcohol, a thickener, a fragrance, a coloring agent, for the purpose of improving storage stability, usability, and the like. Enzymes and the like can be appropriately compounded.

The use form of the fungicide composition of the present invention is not particularly limited, but the use form differs depending on the properties of the peroxy compound. That is, when a solution of hydrogen peroxide or the like is used as the peroxy compound, a hydrogen peroxide solution is used as the component (a), and a mixture of a metal complex, a metal (hydroxide), and optionally an alkali agent or the like is used as the component (b). It may be prepared, mixed before use, and sprayed using a spray container or the like.

When a powder of sodium percarbonate or the like is used as the peroxy compound, a metal complex, metal (water)
An oxide, a component mixed with an alkali agent or the like in some cases may be prepared, mixed with water before use, and sprayed using a spray container or the like.

[0040]

Next, the present invention will be described in more detail by way of examples, which should not be construed as limiting the present invention.

The components and symbols in each table have the following meanings, and TPDC and metal complexes A to C are synthetic products. H ₂ O ₂ : hydrogen peroxide; Mitsubishi Gas Chemical Co., Ltd. PC: sodium percarbonate; Mitsubishi Gas Chemical Co., Ltd. TAED: N, N, N ′, N′-tetraacetylethylenediamine; Hoechst TPDC: dicholine terephthalate Ester metal complex A: Mn complex; [Mn ₂ (μ-OXO) ₃ (Me-
TACN) ₂ ] (PF ₆ ) ₂ metal complex B: Fe complex; [Fe ₂ (μ-OH) ₃ (Me-T
ACN) ₂ ] (ClO ₄ ) ₂ .2MeOH.2H ₂ O Metal complex C: Cu complex; [Cu ₂ (μ-OH) ₂ (Me-T
ACN) ₂ ] (ClO ₄ ) ₂ MnO ₂ ; reagent Fe ₂ O ₃ ; reagent CuO; reagent Cu (OH) ₂ ; reagent potassium carbonate; manufactured by Asahi Glass Co., Ltd.

The effect of removing mold and the absence of irritating odor in each example were measured as follows.

(A) Mold removing effect; black mold (Clad)
osporium cladosporioides)
The unglazed tile surface adjusted by culturing and attaching (2.
An equivalent amount (0.5 mL) of the fungicide solution immediately after the preparation of the mixture of the peroxy compound of the present invention and the metal complex and the like after 30 minutes was dropped onto 5 × 2.5 cm), and left for 15 minutes. Thereafter, it was washed with water and dried at 30 ° C. for 2 hours. A food stamp (for fungus: Sabouraud agar) was adhered to the tile for 1 hour, and a change with time (2 days) at 30 ° C. was observed, and the evaluation was made according to the following evaluation criteria.

[0044]

(B) No irritating odor; the degree of irritating odor when 200 mL of each sample was evenly sprayed from a spray container onto the entire side surface of a 5.5 m ³ sealed bathroom and kept as it was for 3 minutes Was determined organoleptically according to the following evaluation criteria. The test was performed by five people.

[0046]

Examples 1 to 4 and Comparative Examples 1 to 4 In a hydrogen peroxide aqueous solution having a concentration of 5% by weight, a peroxy compound having a composition shown in Table 2 (% by weight based on the aqueous solution), a metal complex, and a metal of the same kind as the metal complex were used. Compounds and the like were mixed, and a test was carried out for the effect of removing mold and no irritating odor. Table 2 shows the results.

[0048]

[Table 2]

Examples 5 to 12 A peroxy compound having the composition shown in Table 3 (% by weight based on the total aqueous solution) was mixed with a metal complex and a metal compound of the same kind as the metal complex to remove mold and to have no irritating odor. Was tested. Table 3 shows the results.

[0050]

[Table 3]

From the results in Tables 2 and 3, it can be seen that the fungicide composition of the present invention can be used regardless of the time after preparation of the fungicide solution.
It shows that it shows strong mold removing power for a long time and has no irritating odor.

[0052]

As described above, the mold remover composition of the present invention has a high mold removal ability irrespective of the time after preparation of the mold remover solution. In addition, it is practically extremely useful because there is no irritating odor and there is no danger of generating harmful gas during use.

Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI A01N 55/02 A01N 55/02 AG 57/36 57/36 Z 59/16 59/16 Z 59/20 59/20 Z (72) Invention Kazumi Yajima 1-7-3 Honjo, Sumida-ku, Tokyo Inside Lion Corporation

Claims (2)

[Claims] 1. A mold remover composition comprising (A) a peroxy compound and (B) a metal complex, wherein (C) an oxide or hydroxide of a metal of the same kind as the metal complex is further added in an amount of 0.005 to 0.005. A mold remover composition characterized by being blended in an amount of 0.25% by weight. 2. The metal complex having a ligand that is a macrocyclic organic molecule, wherein the metal complex has the following general formula [A]:
The fungicide composition according to claim 1, which is a compound represented by the formula: Embedded image [Wherein, M is V, Cr, Mn, Fe, Co, Ni, Cu
A transition metal in the II- to V-valent oxidation state selected from the group consisting of, or a mixture thereof, n and m each represent an integer of 1 to 4, X represents a coordinating species or a crosslinking species, and p represents 0 to 12 Is an integer and Y is a counter ion, the type of which depends on the charge z of the complex, which can be positive, zero or negative, where q is z / (Y
And L is the following general formula [B]: (Wherein R ¹ and R ² are O, H, an optionally substituted alkyl group or aryl group, and t and t ′ are each 2 to
And each D is N, NR, PR, O or S, where R is H, an optionally substituted alkyl or aryl group, and s is an integer of 2-5 ,)
Is a ligand having ]