JPH10279412A - Mildew-removing agent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition free from stimulating odor, having excellent adhesivity and retention on a wall surface when sprayed against the surface and exhibiting excellent mildew-removing power by including a peroxy compound, a metal complex, a thickener and an alkaline substance. SOLUTION: This composition contains (A) a peroxy compound (e.g. hydrogen perooxide), (B) a metal complex [e.g. the complex of the formula (Me-TACN is 1,4,7-trimethyl-1,4,7-triazacyclononane)], (C) a thickener [e.g. guar gum and xanthan gum (natural thickener); ammonium alginate (semisynthetic thickener); polyvinyl alcohol (synthetic thickener); beegum (inorganic thickener); etc.] and (D) an alkaline substance (e.g. sodium carbonate). The contents of the components A, B, C and D are preferably 1-30 wt.%, 0.01-1,000 ppm, 0.01-10 wt.% and 0.1-20 wt.%, respectively.

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 free from generation of harmful gas and irritating odor at the time of use, has good adhesion and retention on wall surfaces, and is suitable for mold removal. .

[0002]

2. Description of the Related Art Bathrooms, bathtubs, toilets around houses,
Stain, especially in places where water is frequently used, such as sinks, is often due to organic substances 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. In addition, when using a chlorine odor strongly, it is necessary to pay attention to sufficient ventilation, and there is a drawback that harmful chlorine gas is generated when used in combination with an acidic cleaning agent by mistake.

[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 if these organic peracid bleach activators are used in combination, the bleaching effect on mold dyes is only slightly improved, and the removal of mold by itself is still insufficient. Breeding,
Even if the mold remover composition is sprayed onto a wall surface, the mold remover immediately drips, resulting in a remarkably poor adhesion retention property.

[0006]

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 has a very excellent mold sensation when the composition is sprayed on a wall surface. It is an object of the present invention to provide a composition exhibiting removal performance.

[0007]

DISCLOSURE OF THE INVENTION The present inventors have enthusiastically developed a composition which shows a strong mold removing power when a mold removing composition is sprayed on a wall surface and has no irritating odor. As a result of repeated studies, they have found that the object can be achieved by combining a peroxy compound, a metal complex, a thickener, and an alkaline substance, and have completed the present invention based on this finding. .

That is, according to the present invention, (A) a peroxy compound, (B) a metal complex, (C) a thickener, and (D)
A fungicide composition comprising an alkaline substance is provided.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The mold remover composition of the present invention comprises (A) a peroxy compound, (B) a metal complex, (C) a thickener, and (D)
It is characterized by containing an alkaline substance.

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, a peroxy acid precursor system, and mixtures thereof. There is.

Examples of the hydrogen peroxide source include alkali metal oxides, organic peroxides such as urea peroxide, inorganic peroxides,
Examples include alkali metal perborates, percarbonates, perphosphates and 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 acylphenol sulfonate, acylalkylphenol sulfonate, acylphenol carboxylate, acylated citrate, acylalkylphenol carboxylate, ester of aromatic divalent carboxylic acid and alcohol having quaternized amine, etc. Sodium benzoyloxybenzenesulfonate, sodium-1-methyl-2-benzoyloxybenzene-4-sulfonate, sodium nonanoyloxybenzenecarboxylate, sodium decanoyloxybenzenecarboxylate, acetyltriethylcitrate, 2- (4 -Methoxycarbonylbenzoyloxy) -N, N, N-trimethylethanaminium methosulfate and the like.

The 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-sulfophenylcarbonate and the like can be mentioned.

The content of these peroxy compounds is not particularly limited, but may be 1 to 3 in the bath of the fungicide composition.
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 to VI selected from d, W, Re, Ir, Pt, and Au
Transition metals in the I-valent oxidation state are preferred.

Particularly preferred among these metal complexes are metal complexes having a ligand which is a macrocyclic organic molecule, for example, those represented by the following general formula [A].

Embedded image [Wherein M is V, Cr, Mn, Fe, Co, Ni, C
u, Zn, Mo, Ru, Rh, Pd, W, or a transition metal in the oxidation state of a valence of II to V selected from Re, or a mixture thereof, n and m are each an integer of 1 to 4, and X is Represents a coordinating species or a crosslinking species, p is an integer of 0 to 12,
Is a counter ion, the type of which depends on the charge z of the complex, which can be positive, zero or negative, q is z / (charge of 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
e, Co, Ni, Cu, Zn, Mo, Ru, Rh, P
Based on d, W and Re, preferably 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 1-, R-
R is H or a substituted or unsubstituted alkyl or aryl group in COO ⁻ , RO ⁻ , NR ₃ , or R is an H or a substituted or unsubstituted alkyl or aryl group in an aromatic nitrogen compound, an acetylacetonate group, oxalic ^acid, Cl -, SCN ^-, etc., or show a combination thereof, p
Represents an integer of 0 to 12, preferably 3 to 6, 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 z represents a positive integer. When Y is an anion, for example, Cl ⁻ , Br ⁻ , I ⁻ , NO ₃ ⁻ , Cl
O ₄ ⁻ , NCS ⁻ , PF ₆ ⁻ , RSO ₄ ⁻ , OAc ⁻ , CF ₃ S
O ₃ ⁻ , RSO ₃ ⁻ , RSO ₄ ^{− and the} like. When z is negative, Y represents a cation, for example, an alkali metal, alkaline earth metal or ammonium cation, and q represents z / (charge of Y). , 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, and the ligand L
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.

[0022]

Embedded image

[0023]

Embedded image

[0024]

Embedded image

[0025]

Embedded image

The metal complex having these ligands may be formed in advance or may be 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.

[0029]

[Table 1]

The content of these metal complexes is not particularly limited, but may be 0.01 to 10 in the mold remover composition bath.
00 ppm, preferably 1 to 500 ppm.

In the present invention, the thickener used as the component (C) is not particularly limited, but natural thickeners of plant, microbial or animal systems, semi-synthetic thickeners, synthetic thickeners, Series thickeners and inorganic series thickeners.

Specifically, as the natural thickener, plant-based polysaccharides derived from seeds such as guar gum, locust bean gum, quince sheet gum, tara gum and the like, and seaweeds derived from carrageenan, alginic acid, phaselan, agar, etc. Polysaccharides, arabinogalactan gum, gum arabic, gum tragacanth, polysaccharides derived from resins such as gum karaya, starch, konjac, polysaccharides derived from rhizomes such as trolloay,
Examples include fruit-derived polysaccharides such as pectin.

Microbial systems include Xanthan gum, Zancoat, Zanflo, curdlan, succinoglucan, schizophyllan and the like, and animal systems include gelatin, casein, albumin, shellac and the like.

Examples of the semi-synthetic system include starch derivatives, derivatives such as guar gum and locust bean gum, and alginic acid derivatives such as ammonium alginate and propylene glycol alginate.

As the synthesis system, polyvinyl alcohol,
Examples include vinyl polymers such as polyvinyl pyrrolidone and polyvinyl methacrylate, acrylic polymers such as sodium polyacrylate and acrylic acid-maleic acid copolymer, and polyethylene oxide.

Examples of the inorganic type include veegum, bentonite, hectonite, montmorillonite, clay, talc and the like.

The content of these thickeners is not particularly limited, but is 0.01 to 10% by weight, preferably 0.1 to 5% by weight in the fungicide composition bath.

In the present invention, the alkaline substance used as the component (D) may be an alkali metal or ammonium hydroxide, carbonate, bicarbonate or the like, as long as it is soluble in water and exhibits alkalinity. Sodium carbonate or potassium carbonate is preferred because it is easy to adjust pH. Particularly preferred is potassium carbonate.

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

The fungicide-removing composition of the present invention may optionally contain a surfactant, a builder, a radical scavenger, an alcohol, a fragrance, a dye, an enzyme and the like for the purpose of improving storage stability, usability and the like. Can be blended.

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, an aqueous solution of hydrogen peroxide is prepared as the component (a), and a mixture of an alkali agent, a metal complex, a thickener and the like is prepared as the component (b). It may be mixed before use and sprayed on the wall.

When a powder of sodium percarbonate or the like is used as the peroxy compound, a component prepared by mixing the powder with a thickener, an alkali agent, a metal complex, etc. is prepared, and mixed with water before use to prepare a wall surface. It should just be injected.

[0043]

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 CF are synthetic products. Hydrogen peroxide; PC manufactured by Mitsubishi Gas Chemical Company; sodium percarbonate; TAED manufactured by Mitsubishi Gas Chemical Company: N, N, N ', N'-tetraacetylethylenediamine; TPDC manufactured by Hoechst TPDC: 2- (4-methoxycarbonylbenzoyloxy) ) -N, N, N- trimethyl ethanaminium methosulfate A: [Ru (OH) ( NH 3) 4 (NO)] (NO 3) 2;
NECHEMCAT B: [Rh (NH ₃ ) ₅ (H ₂ O)] Cl ₃ ; NECHEMCAT
C: [Mn ₂ (μ-O) ₃ (Me-TACN) ₂ ] (P
F ₆ ) ₂ D: [Mn ₂ (μ-O) ₃ (Me / Me-TACN) ₂ ]
(PF ₆ ) ₂ E: [Co ₂ (μ-OH) ₃ (Me-TACN) ₂ ] (C
10 ₄ ) ₃ F: [Fe ₂ (μ-OH) ₃ (Me-TACN) ₂ ] (C
lO ₄ ) Thickener X: sodium polyacrylate; Toagosei Chemical Co., Ltd. thickener Y: smectite type; VAN GEL O; Sanyo Kasei Kogyo Co., Ltd. thickener Z: xanthan gum; Somal potassium carbonate; Asahi Glass Co., Ltd. Sodium carbonate manufactured by Asahi Glass

The mold removing effect and the adhesion retention property in each example were measured as follows.

(A) Mold removing effect; black mold (Clad)
osporium cladosporioides)
Each sample was sprayed from a shower bottle on a surface (3 × 3 cm) in which an unglazed tile adjusted by culturing and applied was vertically erected (3 × 3 cm), and left for 15 minutes.
It was washed with water and dried at 30 ° C. for 2 hours. In this tile,
A food stamp (for fungus: Sabouraud agar) was adhered 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.

[0047]

(B) Adhesion retention property: The distance from the shower bottle adjusted so that the sample is jetted in a steady state is 2
From the position of 0 cm, the spray is sprayed on the central part of a vertically laid spray panel (30 × 30 cm), and after 10 seconds, the weight of the panel is measured. This test was performed three times, the adhesion retention rate was calculated by the following equation, and the evaluation was made according to the following evaluation criteria.

(Equation 1)

[0049]

Examples 1 to 6 and Comparative Example 1 A hydrogen peroxide solution having a concentration of 5% by weight was mixed with a peroxy compound (T
AED), a metal complex, a thickener, and an alkaline substance were mixed, and a test for removing mold and an adhesive retention test were conducted.
Table 2 shows the results.

[0051]

[Table 2]

Examples 7 to 12 In a hydrogen peroxide aqueous solution having a concentration of 5% by weight, a peroxy compound (T) having a composition shown in Table 3 (% by weight based on the aqueous solution) was added.
(AED, TPDC), a metal complex, a thickener and an alkaline substance were mixed, and a test for removing mold and an adhesive retention test were conducted. Table 3 shows the results.

[0053]

[Table 3]

Examples 13 to 18 and Comparative Example 2 A peroxy compound having the composition shown in Table 4 (% by weight based on the total aqueous solution), a metal complex, a thickener and an alkaline substance were mixed with water to remove mold and adhere. A retention test was performed. Table 4 shows the results.

[0055]

[Table 4]

From the results shown in Tables 2 to 4, the mold remover composition of the present invention containing the above components (A), (B), (C) and (D) was prepared using a container such as a shower bottle. It can be seen that, when adhered to, for example, it has a high mold removal ability, coupled with an improvement in the adhesion retention property.

[0057]

The mold remover composition of the present invention contains (A) a peroxy compound, (B) a metal complex, (C) a thickener, and (D) an alkaline substance.
When it is attached to a wall or the like using a container such as a shower bottle, it has a high mold removal ability, coupled with an improvement in the adhesion retention property, and in addition to reducing mold reproduction as much as possible, there is no irritating odor, and Since there is no danger of generating harmful gas during use, it is extremely useful in practice.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI A01N 59/00 A01N 59/00 C 59/02 59/02 Z 59/14 59/14 59/26 59/26 C11D 3/48 C11D 3/48 7/54 7/54 7/56 7/56 (72) Inventor Takamichi Hasegawa 1-3-7 Honjo, Sumida-ku, Tokyo Inside Lion Corporation

Claims (1)

[Claims] 1. A mold remover composition comprising (A) a peroxy compound, (B) a metal complex, (C) a thickener, and (D) an alkaline substance.