JP5419754B2 - Mold stain removing composition - Google Patents

Description

  The present invention relates to a mold stain removing composition.

  Among the hard surface stains, dark stains derived from bacteria and fungi are difficult to remove sufficiently with a detergent mainly composed of a surfactant or an abrasive.

  Conventionally, many bleaching compositions based on alkali metal hypochlorite are known, and it is also known to apply them to dark stains derived from bacteria and fungi.

  In Patent Document 1, mold stain removal excellent in bleaching of mold stains in resin parts, containing alkali metal hypochlorite, alkali metal chloride, alkali metal hydroxide and quaternary ammonium salt of a specific structural formula A composition for use is disclosed. Patent Document 2 contains an alkali metal hypochlorite salt, an amphoteric polymer compound having a specific structural unit, and a quaternary ammonium type surfactant, and is particularly excellent in bleaching power against mold grown on the resin part. A bleach composition is described. Patent Document 3 includes an alkali metal hypochlorite salt, a quaternary ammonium salt having a specific structural formula, and a polyvinyl alcohol having a specific saponification rate, and a markedly blackened mold stain generated in a deteriorated portion of the resin. A liquid bleach composition having an excellent bleaching effect is described.

JP 2002-212593 A JP 2008-133453 A

  Recently, in addition to tiles and joints, there is an increasing number of cases where mold occurs in resin parts such as silicone resin caulking and polyvinyl chloride resin packing used in the joints between walls and bathtubs. . It is desirable to have an excellent bleaching effect against mold stains generated in such resin parts.

  Accordingly, an object of the present invention is to provide a mold stain removing composition having a sufficient bleaching effect not only on hard surfaces in a bathroom but also on mold stains generated on soft parts such as resins.

  The present invention provides (a) alkali metal hypochlorite (hereinafter referred to as component (a)) 0.1 to 5% by mass, (b) a quaternary ammonium type interface represented by the following general formula (b1) Activator [hereinafter referred to as component (b)] 0.01 to 1% by mass, and (c) HLB11 or more polyether-modified silicone represented by the following general formula (c1) [hereinafter referred to as component (c)] The present invention relates to a mold stain removing composition containing 0.01 to 1% by mass.

[Wherein, R ¹ represents an alkyl group having 6 to 16 carbon atoms, R ² represents a methyl group, an ethyl group, or an alkyl group having 6 to 16 carbon atoms, and R ³ represents a methyl group or an ethyl group. R ⁴ is a methyl group, an ethyl group, or a benzyl group, and X ⁻ is a counter ion. ]

[Wherein, m is a number of 0 to 15, n is a number of 1 to 100, R ⁵ is an alkyl group having 1 to 20 carbon atoms, R ⁶ is a hydrogen atom, a methyl group or an ethyl group, AO is a polyether group composed of one or more groups selected from an ethyleneoxy group and a propyleneoxy group. a is a number from 1 to 50. The ratio of m / n is 0 to 4.5, and m / (n × a) is 0 to 0.3. ]

  ADVANTAGE OF THE INVENTION According to this invention, the composition for mold | fungi stain removal excellent in the bleaching effect with respect to the mold | fungi which generate | occur | produced in soft parts, such as resin, and penetrate | invaded the inside of resin is provided.

[(A) component]
The mold stain removing composition of the present invention contains an alkali metal hypochlorite as the component (a). As the alkali metal, sodium and potassium are preferable, and sodium is more preferable. The component (a) preferably has a low sodium chloride content. Specific examples of the alkali metal hypochlorite of component (a) include sodium hypochlorite and potassium hypochlorite, with sodium hypochlorite being particularly preferred. The content of the component (a) in the mold stain removing composition of the present invention is 0.1 to 5% by mass, preferably 0.5 to 4% by mass, more preferably 2 to 3% by mass. It is. When the content of component (a) is 0.1% by mass or more, sufficient bleaching power is obtained, and when it is 5% by mass or less, good stability is obtained.

[Component (b)]
The composition for removing mold stains of the present invention contains a quaternary ammonium type surfactant represented by the following general formula (b1) as the component (b).

[Wherein, R ¹ represents an alkyl group having 6 to 16 carbon atoms, R ² represents a methyl group, an ethyl group, or an alkyl group having 6 to 16 carbon atoms, and R ³ represents a methyl group or an ethyl group. R ⁴ is a methyl group, an ethyl group, or a benzyl group, and X ⁻ has a halide ion, an alkyl sulfate ion having 1 to 5 carbon atoms, or an alkyl group having 1 to 3 carbon atoms as a substituent. Counter ions such as alkyl-substituted benzenesulfonate ions. ]

In the formula (b1), R ¹ is preferably an alkyl group having 8 to 12 carbon atoms, more preferably an alkyl group having 8 to 10 carbon atoms, and most preferably an alkyl group having 8 carbon atoms, from the viewpoint of improving the bleaching performance of the resin material. R ² is preferably a methyl group or an ethyl group, more preferably a methyl group, R ³ is preferably a methyl group, and R ⁴ is preferably a methyl group or a benzyl group, particularly preferably Is a benzyl group, X ⁻ is preferably an alkyl sulfate ion having 1 to 3 carbon atoms, a benzenesulfonate ion having an alkyl group having 1 to 3 carbon atoms as a substituent, Cl ⁻ , or Br ⁻ , more preferably Cl ^- it is. Of these, octyldimethylbenzylammonium chloride and decyldimethylammonium chloride are preferred from the viewpoint of obtaining high bleaching power.

  The content of the component (b) in the mold stain removing composition of the present invention is 0.01 to 1% by mass, preferably 0.02 to 0.5% by mass, more preferably 0.05 to 0%. .4 mass%, more preferably in the range of 0.1-0.3 mass%. When the content of the component (b) is 0.01% by mass or more, sufficient bleaching power is obtained, and when it is 1% by mass or less, good storage stability is obtained.

[Component (c)]
The mold dirt removing composition of the present invention contains a polyether-modified silicone of HLB11 or higher represented by the following formula (c1) as the component (c).

  The HLB of the component (c) is preferably in the range of 11.5 to 19.5, more preferably 12 to 19, and still more preferably 13.5 to 18. HLB is determined by the method described in the examples.

[Wherein, m is a number of 0 to 15, n is a number of 1 to 100, R ⁵ is an alkyl group having 1 to 20 carbon atoms, R ⁶ is a hydrogen atom, a methyl group or an ethyl group, AO is a polyether group composed of one or more groups selected from an ethyleneoxy group and a propyleneoxy group. a is a number from 1 to 50. The ratio of m / n is 0 to 4.5, and m / (n × a) is 0 to 0.3. ]

  In the general formula (c1), m is preferably a number of 0 to 10, more preferably 0 to 5, from the viewpoint of obtaining high bleaching power. N is preferably a number of 2 to 50, more preferably 3 to 30.

In general formula (c1), R ⁶ is preferably a hydrogen atom, and AO is preferably a propyleneoxy group.

  In general formula (c1), the value of m / n is preferably 0 to 4, more preferably 0 to 3.5, still more preferably 0 to 3, particularly preferably 0 to 2. from the viewpoint of obtaining high bleaching power. The range is 6.

  In the general formula (c1), the value of m / (n × a) represents the balance of hydrophobicity / hydrophilicity, and the smaller the value, the more hydrophilic the component (c). From the viewpoint of obtaining high bleaching power, it is preferably 0 to 0.28, more preferably 0 to 0.27, and particularly preferably 0 to 0.26.

  The content of the component (c) in the mold stain removing composition of the present invention is 0.01 to 1% by mass, preferably 0.01 to 0.5% by mass, more preferably 0.01 to 0%. .4 mass%, more preferably in the range of 0.1-0.3 mass%. When the content of the component (c) is 0.01% by mass or more, sufficient bleaching power is obtained, and when it is 1% by mass or less, good stability of the alkali metal hypochlorite is obtained.

  Resin such as silicone resin-based caulking or polyvinyl chloride resin-based packing, which is difficult to remove in the prior art by using both component (b) and component (c) in the composition for removing mold stains of the present invention. This improves the bleaching and washing effect on mold stains generated on soft parts such as.

  The mass ratio of the component (b) to the component (c) is preferably (b) / (c) from the viewpoint of obtaining high bleaching power, preferably 0.1 to 100, more preferably 0.15 to 50, and still more preferably 0. .2 to 10, particularly preferably 0.3 to 5. The total content of the component (b) and the component (c) [(b) + (c)] in the composition is preferably 0.02 to 1.5% by mass from the viewpoint of obtaining high bleaching power. More preferably, it is 0.04-1.3 mass%, More preferably, it is 0.05-1.2 mass%, Especially preferably, it is 0.06-1.1 mass%, Most preferably, it is 0.08-1 % By mass.

[Component (d)]
From the viewpoint of improving the stability of the component (a), the mold stain removing composition of the present invention preferably contains an alkali metal hydroxide as the component (d). Specific examples of the component (d) include sodium hydroxide and potassium hydroxide, and sodium hydroxide is particularly preferable. The content of the component (d) in the mold stain removing composition of the present invention is preferably 0.1 to 1% by mass, more preferably 0.3 to 0.9% by mass, and 0.4 to 0.8. Mass% is particularly preferred. When the content is 0.1% by mass or more, good alkali metal hypochlorite stability is obtained. When the content is 1% by mass or less, good bleaching performance is obtained.

[(E) component]
The mold stain removing composition of the present invention preferably contains water as the component (e). The component (e) is usually the remainder of the composition, but the content of the component (e) in the mold stain removing composition of the present invention is preferably 80 to 98% by mass, more preferably 90 to 98% by mass. % Range. From the viewpoint of storage stability, ion-exchanged water or distilled water from which metal ions are removed is preferable.

[Other ingredients]
The composition for removing mold stains of the present invention is an amine oxide type having one alkyl group having 8 to 16 carbon atoms as the component (f) in order to improve the adhesion to walls and the like without affecting storage stability. A surfactant may be contained. The content of the component (f) in the mold stain removing composition of the present invention is preferably 0.05 to 5% by mass, more preferably 0.8%, from the viewpoint of improving adhesion without impairing storage stability. It is 05-3 mass%, Most preferably, it is 0.05-1 mass%.

  Furthermore, the mold stain removing composition of the present invention may contain a fatty acid having 6 to 14 carbon atoms or an alkali metal salt thereof as the component (g). Specific examples of the component (g) include caproic acid, caprylic acid, pelargonic acid, capric acid, undecylic acid, myristic acid laurate, or a sodium salt or potassium salt thereof. In particular, caprylic acid, capric acid, lauric acid or their sodium salts are preferred. The content of the component (g) in the mold stain removing composition of the present invention is preferably 0.05 to 5% by mass, more preferably 0.8%, from the viewpoint of exhibiting excellent storage stability and foaming power. It is 05-3 mass%, Most preferably, it is 0.05-1 mass%.

  In the composition for removing mold stains of the present invention, surfactants other than the components (b), (f), and (g) may be used, but the total amount of the surfactant in the composition is storage stable. From the surface, the total amount including the components (b), (f) and (g) is preferably 5% by mass or less, more preferably 3% by mass or less, and further preferably 1.5% by mass or less.

Furthermore, the composition for removing mold stains of the present invention is represented by the following general formula (h1) as the component (h) from the viewpoint of further improving foam foaming properties and foam density during trigger spraying. It is preferable to contain a compound.
_{^{X 1 -O (AO) n -X}} 2 (h1)
(In the formula, AO represents an alkyleneoxy group having 2 to 4 carbon atoms, and n represents an average addition mole number of the alkyleneoxy group. X ¹ and X ² are each a hydrogen atom, —SO ₃ H or —CH _2. COOH or an alkali metal salt thereof is indicated, and X ¹ and X ² are not simultaneously hydrogen atoms.)

AO is preferably an ethyleneoxy group. n is preferably 5 to 1000, more preferably 10 to 100, and particularly preferably 10 to 40. Good adhesion retention is obtained at 5 or more, white turbidity is suppressed at 1000 or less, and good storage stability is obtained. It is preferable that at least one of X ¹ and X ² is —SO ₃ H or an alkali metal salt thereof.

  Furthermore, the mold stain removing composition of the present invention may contain a hydrotrope having a benzene ring as the component (i). By containing a hydrotrope agent such as xylene sulfonic acid, toluene sulfonic acid, cumene sulfonic acid, benzoic acid as the component (i), low temperature stability and foaming ability can be further improved. Among these, metaxylene sulfonic acid is particularly preferable. The content of the component (i) in the mold stain removing composition of the present invention is preferably 0.1 to 3% by mass, more preferably 0.2 to 2% by mass, and particularly preferably 0.3 to 1% by mass. preferable. (I) When the content of the component is 0.1% by mass or more, low temperature stability, foaming power when sprayed with a sprayer such as a trigger, and foam density can be further improved. Good stability of the acid alkali metal salt is obtained.

  Furthermore, the mold stain removing composition of the present invention may contain a fragrance. The content of the fragrance component in the mold stain removing composition of the present invention is preferably 0.001 to 0.5 mass%.

  The composition for removing mold stains of the present invention preferably has a pH at 20 ° C. of 11 to 14, more preferably 12.5 to 13.5, from the viewpoint of bleaching effect and storage stability. For adjusting the pH, the component (d) can be used.

  In order to apply the composition for removing mold stains of the present invention to an object, there are methods such as spraying with a trigger, application of a water-absorbing material carrying the composition, and immersion of the object in the composition. Spraying by is preferable from the viewpoint of simplicity. Furthermore, the trigger type spray which can spray a composition in foamy form is preferable. The mold dirt removing composition of the present invention is suitable for hard surfaces such as bathrooms, kitchens and toilets, and these hard surfaces include a surface made of a soft member such as a resin used for the purpose of preventing water leakage. You may go out. Specifically, the mold stain removing composition of the present invention is preferably applied to mold generated in a soft resin sealing material and / or a soft resin caulking material. Therefore, the mold dirt removing composition of the present invention can be used for soft resin articles. Examples of the soft resin include a silicone resin and a polyvinyl chloride resin.

  The composition for removing mold stains shown in Table 1 was prepared. HLB is a calculated value according to the Griffin equation. The mass% in a table | surface is the density | concentration of each component in a composition. Each composition had a pH (20 ° C.) in the range of 12.5 to 13.5. Sodium hypochlorite was used in an aqueous solution having a concentration of 13% by mass so that the concentration in the composition would be the value in the table. About these compositions, the bleaching power (the bleaching removal effect of mold soil) was evaluated by the following method. The results are shown in Table 1. In some of the comparative examples, (b) / (c) mass ratio and (b) + (c) mass% were calculated with component (c ′) as component (c). In addition, the polyether-modified silicone of component (c) is a polyoxyethylene allyl ether to a polymethylhydrogensiloxane blocked with a trimethylsiloxy group blocked at both ends of a molecular chain using a platinum / 1,2-divinyl-tetramethyldisiloxane complex as a catalyst. Was produced by addition polymerization.

<Bleaching power>
Soft polyvinyl chloride resin that has been used for 15 years as a sealing material (caulking material) for bathroom doors in general households is collected, and the part that has turned black due to the occurrence of mold is selected and cut to about 1 cm for evaluation. A sample was used. The lightness (L value) of the evaluation sample was measured using a colorimetric color difference meter (ND-300A, manufactured by Nippon Denshoku Industries Co., Ltd.). Evaluation was performed using only test pieces having a difference in L value within ± 2. Evaluation was made by wiping Kimwilique made by Kimberly Clark (paper wiping cloth) cut into 3 cm x 3 cm on a test piece, dropping 500 μl of the composition, pouring it for 10 minutes, then washing with water and air-drying for bleaching. It was. The bleaching treatment was performed on the composition immediately after preparation and the composition after storage at 50 ° C. for 1 week. The brightness of each evaluation sample after the treatment was measured.
Bleaching rate (%) = [(lightness after bleaching−lightness of contaminated site before bleaching) / (lightness of uncontaminated site−lightness of contaminated site before bleaching)] × 100
The larger the value, the higher the bleaching performance against mold stains. This value is desirably 80% or more at the initial stage and 70% or more after storage.

* 1 Amino-modified silicone: Water-soluble amino-modified silicone with a polyether group at the end of the main chain and a primary amino group at the side chain * 2 Amide-modified silicone: A water-soluble product with an amide group and a polyether group at the end of the main chain Amide-modified silicone * 3 PE group: a group represented by-(AO) _a -R ⁶ .
* 4 PO: Abbreviation for propyleneoxy group.

  Examples 1 to 11 of the present invention are excellent in bleaching power. Moreover, it turns out that Examples 1-11 are excellent also in the sustainability of bleaching power. On the other hand, it turns out that Comparative Examples 1-8 is inferior to bleaching power.

Claims (3)

(A) Alkali metal hypochlorite 0.1-5 mass%, (b) Quaternary ammonium type surfactant 0.01-1 mass% represented by the following general formula (b1), and ( c) A composition for removing mold stains, containing 0.01 to 1% by mass of a polyether-modified silicone of HLB11 or more represented by the following general formula (c1).

[Wherein, R ¹ represents an alkyl group having 6 to 16 carbon atoms, R ² represents a methyl group, an ethyl group, or an alkyl group having 6 to 16 carbon atoms, and R ³ represents a methyl group or an ethyl group. R ⁴ is a methyl group, an ethyl group, or a benzyl group, and X ⁻ is a counter ion. ]

[Wherein, m is a number of 0 to 15, n is a number of 1 to 100, R ⁵ is an alkyl group having 1 to 20 carbon atoms, R ⁶ is a hydrogen atom, a methyl group or an ethyl group, AO is a polyether group composed of one or more groups selected from an ethyleneoxy group and a propyleneoxy group. a is a number from 1 to 50. The ratio of m / n is 0 to 4.5, and m / (n × a) is 0 to 0.3. ]   The mold according to claim 1, wherein the total content of (b) and (c) is 0.02 to 1.5 mass%, and the mass ratio of (b) / (c) is 0.1 to 100. A composition for removing dirt.   The composition for removing mold stains according to claim 1 or 2, which is applied to mold generated in a soft resin sealing material and / or a soft resin caulking material.